IIIHIIII US005541346A United States Patent (19) 11 Patent Number: 5,541,346 Drysdale et al. 45) Date of Patent: Jul. 30, 1996

(54) POLYMERIZATION OF, AND 24.59163 12/1974 Germany. DEPOLYMERIZATION TO, CYCLIC ETHERS 59 SS' 3. Stay SSSI CTED METAL COMPOUND 60-109584 6/1985 Japan ...... 549/509 C WO88/02661 4/1988 WIPO. 75) Inventors: Neville E. Drysdale; Norman Herron, OTHER PUBLICATIONS both of Newark, Del. Grant & Hackh's Chemical Dictionary, Fifth Edition, McGraw-Hill Book Co., New York, 1987, p. 373. 73) Assignee: E. A. FileNet, and Habermeier, J. etal, J. Poly. Science: Part C, 16, 2131-2141 Oechsner et al, "Reaction Pathway of the Cationically 21 Appl. No.: 424,918 Initiated Ring-Opening Copolymerization of THF and 1- Dicarboxylic Anhydrides', MAKROMOL CHEM., 150, 22 Filed: Apr. 19, 1995 1-23 (1971). O WPI Derwent Acc. No. 94-068607 (1994). Related U.S. Application Data WPI Acc. No. 76-67625x/36 (1976). 60 Division of Ser. No. 283,108, Jul. 29, 1994, which is a WE A. N. ST: $33. continuation-in-part of Ser. No. 198,024, Feb. 17, 1994, ce No. 1 (1987). - 9 abandoned, Ser. No. 141,160, Oct. 21, 1993, abandoned, Ser. Hayase, S. et al., “Photopolymerization of Epoxides', Mac No. 93,243, Jul. 16, 1993, abandoned, Ser. No. 93, 19, Jul. rolecules, 18(10), 1799–1804 (1985). 16, 1993, abandoned, Ser. No. 21,368, Feb. 23, 1993, Crivello, J. V. et al, "Novel Platinum Initiators for Rin abandoned, and Ser. No. 964,313, Oct. 21, 1992, abandoned. g-Opening Polymerizations', DIE Makromol. Chemie: I51) Int. Cl. 6 ...... COTD 307/08 Macromolecular9-188 Symposia, No. 54/55, (1992), BAsel, CH, pp. 179-188. 58) FaisField of Search h...... 5950s. Maeda,call Abstracts, S. etal, 85C18), "Polymerization Nov. 1, 1976, Catalysts Abstract for THF, No. 12466lr. Chemi 549/429 Hilt, et al, "Synthesis of Polyester by Copolymerization of Dicarboxylic Anhydrides and Cyclic Ethers', MAKROMOL (56 References Cited CHEM., 101, 246-270 (1967). U.S. PATENT DOCUMENTS Christen, H. R., "Grundlagen der Organischen Chemie', 4. Auflage, (1977), p. 386, Otto Salle Verlag und Verlag Sav 2,394.910 2/1946 Greshan ...... 568/613 erlander. 2,811,512 10/1957 Austin et al. ... 260.78:1 Lee, H. et al, Handbook of Epoxy Resins, McGraw-Hill 3,344,088 E. Mille a..."35i Book Co., New York, NY, Section 15-14 (Reissue 1982). 3:38 10/1974 tra et al. .528/410 Lenz, R. W., Organic Chemistry Synthetic High Polymers, 37: "5,437 SEAGA". " .5; Interscience Publishers, New York, NY, 531-532 (1967). 3507,766 9/1975 Robins. 252,431 Bowden, K. Chem. Rev., 66(2), 119-131 (1966). 3,925,484 12/1975 Baker ...... 549/509 Olah, G. A. et al., J. Appl. Polym. Sci., 45, 1355-1360 (1992). 4,115,408 9/1978 Baker ...... 260/346.11 Hirkach et al, Macromolecules, 23, 4042-4046 (1990). 4,153,786 571979 Pruckmayr ...... 528,408 Dreyfuss et al, Polymer Letters Ed., 14, 139-142 (1976). $39, 12, E. MEs al...... 32.8 Matsukura et al, Chemical Abstracts, 78(16), Apr. 23, 1973; sava is ada et al...... Abstract No. 98454. SE 12.3 Mills et al...... : Borowsky et al, Organometal, 10, 1268-1274 (1991). E. E. S. Misaki etal, Nippon Kagaku Kaishi, 168-174 (1973) 4.728.722 3/1988 Mueller. 56867 (Abstract Only). SE, AS ME. E. Primary Examiner-Romulo H. Delmendo 5,084,586 1/1992 Farooq ...... 556/181 5,102,849 4/1992 Kemp...... (57) ABSTRACT 5,124,417 6/1992 Farooq ...... 2 A process for polymerizing oxiranes, oxetanes, oxepanes, E. AE S. et al...... Se: dioxolanes, trioxanes, and tetrahydrofurans to their respec 33.5 5/1993 Fre. A a a - a a a ------a - - - 525,415 tive polymers by contacting them with a selected metal 5,208,385 5/1993 Kahnet al.. .568/617 compound is disclosed; and also a process for depolymer 520283 5/1993 Kahn et al... 568/617 izing polytetrahydrofurans to monomeric tetrahydrofurans

5,225,521 7/1993 Spinu ...... 525/45 by contacting the polymer with a selected metal compound 5,235,031 8/1993 Drysdale et al. 525/45 at a temperaturep of about 100° C. to about 250° C. The 5,250,188 10/1993 Bruening et al...... 20/672 catalysts may be in solution or part of a heterogeneous solid, 5,430,122 7/1995 Drysdale. and selected organic compounds are used as accelerators in 5,478,920 12/1995 Drysdale ...... 528/410 the polymerizations. The polymeric products, some of which are novel, may be used as polyether monomers for further FOREIGN PATENT DOCUMENTS polymerization,y as by reactionpolyeiner with isocyanates to produce 01.05080 4/1984 European Pat. Off.. polyurethanes, and other useful polymers. Some of the 048.5637 5/1992 European Pat. Off.. polymeric products are relatively high in molecular weight

55: t E. E.aCe and are suitable for direct use, for instance as spandex fibers. 886304 7/1953 Germany. w 1915117 10/1969 Germany. 12 Claims, No Drawings 5,541,346 1 2 POLYMERIZATION OF, AND U.S. Pat. Nos. 5,084,586 and 5,124,417 describe the DEPOLYMERIZATION TO, CYCLIC ETHERS cationic polymerization of various monomers, including USING SELECTED METAL COMPOUND cyclic ethers, using onium cations, whose corresponding CATALYSTS anions are fluoroalkylsulfatometallates. Onium ion cata lyzed cationic polymerizations are well known, and there is CROSS-REFERENCE TO RELATED no mention in these patents of the use of metal salts not APPLICATIONS containing onium ions, such as metal trifiates, as catalysts for the polymerization of cyclic ethers. This application is a division of U.S. Ser. No. 08/283,108 filed Jul. 29, 1994 pending; which is, in-turn, a continuation Japanese Patent Application 51-82397 describes the poly in-part of Ser. No. 08/198,024 filed Feb. 17, 1994, now 10 merization of tetrahydrofuran using a combination of fluo abandoned; Ser. No. 08/141,160 filed Oct. 21, 1993, now rosulfonic acid and a carboxylic acid as catalysts. No abandoned; PCT/US93/09808 filed Oct. 20, 1993; Ser. No. mention is made of metal salts, such a metal triflates as 08/093,243 filed Jul. 16, 1993, now abandoned; Ser. No. catalysts. 08/093,119 filed Jul. 16, 1993, now abandoned; Ser. No. J. S. Hirkach, et al., Macromolecules, vol. 23, p. 08/021,368 filed Feb. 23, 1993, now abandoned; and Ser. 15 4042–4046 (1990) describe the polymerization of tetrahy No. 07/964,313 filed Oct. 21, 1992, now abandoned. drofuran using trimethylsilyl trifluoromethanesulfonate as the initiator. No mention is made of any other triflates as FIELD OF THE INVENTION catalysts for this polymerization. German Patent Application 2,459,163 describes the poly This invention concerns the polymerization of oxiranes, 20 oxetanes, oxepanes, 1,3-dioxolanes, 1,3,5-trioxanes, and tet merization of THF using a combination of ferric chloride rahydrofurans to linear polyethers, and the depolymerization and carboxylic anhydride as catalyst. of polytetrahydrofurans to tetrahydrofurans, both catalyzed G. A. Olah, et al., J. Appl. Polym. Sci., Vol. 45, by selected metal compounds. The catalysts may be in 1355-1360 (1992) describe the use of boron, aluminum and solution or part of a heterogeneous solid, and selected 25 gallium tristrifiate to catalyze the polymerization of THF. organic compounds are used as accelerators in the polymer S. L. Borkowsky, et al., Organometal.., Vol. 10, p. izations. Novel polymeric products are produced in some of 1268-1274 (1991) report that certain zirconium complexes the polymerizations. can initiate the polymerization of tetrahydrofuran. No men tion is made of zirconium perfluoroalkylsulfonates, or of BACKGROUND OF THE INVENTION 30 copolymers. Cyclic ethers are polymerized by various means to give T. Misaki, et al., Nippon Kagaku Kaishi, p. 168-174 products of widespread utility. For instance, ethylene oxide (1973) report on the polymerization of THF using a com is polymerized to polyethylene oxide which is useful, in bination of metal aceylacetonates and acetyl chloride. lower molecular weight grades, for ceramics (as a binder), U.S. Pat. No. 4,303,782 describes the use of Zeolites to cosmetics, lubricants, polyurethanes; and in higher molecu 35 catalyze the polymerization of tetrahydrofuran. These poly lar weight grades, for packaging film, denture adhesives, merization appear to proceed very slowly. lubricants, flocculation and for other articles and products. SUMMARY OF THE INVENTION Tetrahydrofuran (THF) is polymerized to poly(tetramethyl ene ether) glycol which is useful in the preparation of This invention concerns a first process for the polymer Spandex fibers; polyurethane resins which are useful in 40 ization of cyclic ethers, comprising, contacting at a tem elastomeric parts; and thermoplastic elastomers which are perature of about -80 C. to about 150° C. one or more useful for molding various mechanical parts. Therefore, in, oxiranes, oxetanes, tetrahydrofurans, OXepanes, 1,3-diox roved methods of making these polymers are sought. Also olanes or 1,3,5-trioxanes with a catalyst system consisting useful are methods of depolymerizing the polyethers to essentially of a compound of the formula MZQ, and an useful products, such as the cyclic ethers from which they 45 accelerator selected from the group consisting of carboxylic were originally made. Such depolymerizations allow for the acids whose pKa in water is less than 6, carboxylic anhy recycle of off specification or used polyethers to useful drides and acyl halides, wherein: products such as polyethers, thereby reducing waste. M is a metal selected from the group consisting of cobalt, Block copolymers, of polytetrahydrofurans (usually as the 50 vanadium, copper, mischmetall, niobium, tungsten, diols) and polyesters or poly(urea-urethanes) are commonly strontium, barium, scandium, yttrium, the rare earth used in commercial products, such as thermoplastic elas metals, titanium, zirconium, hafnium, chromium, tomers (Hytrel(B) thermoplastic elastomer), spandex fibers molybdenum, tantalum, rhenium, iron, ruthenium, (Lycrag spandex fiber) and urethane rubbers (Adiprene(E) osmium, rhodium, iridium, palladium, platinum, gold, urethane rubber). The usual procedure in making these 55 Zinc, cadmium, mercury, aluminum, gallium, indium, products is to combine a polyether diol with suitable reac thulium, germanium, tin, lead, arsenic, antimony and tants, such as ester segment forming compounds, or urea bismuth, and/or urethane forming compounds such as amines and/or at least one of Z is an anion of the formula RSOs, diols with diisocyanates. Improved methods of making such wherein R is perfluoroalkyl containing 1 to 12 carbon commercially important polymers are sought by the artisan. 60 atoms or part of a fluorinated polymer wherein the U.S. Pat. No. 3,842,019 describes the polymerization of carbon atoms alpha and beta to the sulfonate group are oxiranes and other small ring compounds by a presumed together bonded to at least four fluorine atoms, or cationic mechanism, using as the catalyst the decomposition tetraphenylborate, and the remainder of Z is oxo or one products of metal perfluoroalkylsulfonates. These catalysts or more monovalent anions; are described as "latent', that is no reaction occurs until the 65 s is 2 when M is strontium, barium, cobalt, rhodium, metal salt is decomposed. The reactions reported are rela iridium, palladium, platinum, chromium, zinc, cad tively slow, even at elevated temperatures. mium or mercury; 5,541,346 3 4. s is 3 when M is scandium, yttrium, a rare earth metal, halides and carboxylic acids whose pKa in water is less than arsenic, antimony, bismuth, gold, iron, ruthenium, about 6. osmium, aluminum, gallium, indium or thulium; This invention also concerns a third process for the s is 4 when M is titanium, zirconium, hafnium, molyb polymerization of cyclic ethers, comprising, contacting, at a denun, germanium, tin, or lead; temperature of about -80° C. to about 130° C., one or more oxiranes, oxetanes, tetrahydrofurans, oxepanes, 1,3-diox s is 5 when M is rhenium, vanadium, niobium ortantalum; olanes, or 1,3,5-trioxanes; with a catalytic system consisting s is 6 when M is tungsten; essentially of a heterogeneous catalyst containing a metal Q is a neutral ligand; perfluoroalkylsulfonate attached to the surface of said cata t is 0 or an integer of 1 to 6; and lyst through said metal, and an accelerator, said metal provided that each oxo group present counts as two of s. 10 selected from the group consisting of strontium, vanadium, This invention also involves a first process for the depo copper, mischmetall, niobium, tungsten, cobalt, barium, lymerization of a polyether to a tetrahydrofuran, comprising, scandium, yttrium, the rare earth metals, titanium, zirco contacting at a temperature of about 100° C. to about 250 nium, hafnium, chromium, molybdenum, tantalum, rhe C., a polymer consisting essentially of one or more repeat nium, iron, ruthenium, osmium, rhodium, iridium, palla units of the formula 15 dium, platinum, gold, zinc, cadmium, mercury, indium, thulium, germanium, tin, lead, arsenic, antimony and bis -CHRCRRCRRCHRO muth, said accelerator selected from the group consisting of carboxylic anhydrides, acyl halides, and carboxylic acids a compound of the formula MZ-Q, wherein: whose pKa in water is less than about 6. each R', R', R and R is independently hydrogen or 20 This invention also concerns a second process for the hydrocarby containing 1 to 20 carbon atoms; depolymerization of a polyether to a tetrahydrofuran, com M is a metal selected from the group consisting of cobalt, prising, contacting at a temperature of about 100° C. to about vanadium, copper, mischmetall, niobium, tungsten, 250 C., a polymer consisting essentially of one or more strontium, barium, scandium, yttrium, the rare earth repeat units of the formula metals, titanium, Zirconium, hafnium, chromium, 25 -CHRCRRCRRCHRO molybdenum, tantalum, rhenium, iron, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, wherein each R', R, R and R' is independently hydrogen gold, zinc, cadmium, mercury, aluminum, gallium, or hydrocarbyl containing 1 to 20 carbon atoms, with a indium, thulium, silicon, germanium, tin, lead, arsenic, heterogeneous catalytic system consisting essentially of a antimony and bismuth; 30 catalyst containing a metal perfluoroalkylsulfonate attached to the surface of said catalyst through said metal; said metal at least one of Z is an anion of the formula RSO, selected from the group consisting of strontium, vanadium, wherein R is perfluoroalkyl containing 1 to 12 carbon copper, niobium, tungsten, cobalt, barium, scandium, atoms or part of a fluorinated polymer wherein the yttrium, the rare earth metals, titanium, Zirconium, hafnium, carbon atoms alpha and beta to the sulfonate group are 35 chromium, silver, molybdenum, tantalum, rhenium, iron, together bonded to at least four fluorine atoms, or ruthenium, osmium, rhodium, iridium, palladium, platinum, tetraphenylborate, and the remainder of Z is oxo or one silver, gold, zinc, cadmium, mercury, aluminum, gallium, or more monovalent anions; indium, thulium, germanium, tin, lead, arsenic, antimony s is 2 when M is strontium, barium, cobalt, rhodium, and bismuth. iridium, palladium,-platinum, chromium, zinc, cad 40 This invention also concerns a fourth polymerization mium or mercury; process for the production of poly(etheresters), comprising, s is 3 when M is scandium, yttrium, a rare earth metal, contacting a tetrahydrofuran with a catalyst system consist arsenic, antimony, bismuth, gold, iron, ruthenium, ing essentially of a polycarboxylic acid of the formula osmium, aluminum, gallium, indium or thulium; A(CO2H), and a catalyst of the formula MZQ, wherein: S is 4 when M is titanium, zirconium, hafnium, molyb 45 M is a metal selected from the group consisting of cobalt, denum, silicon, germanium, tin, or lead; tungsten, vanadium, copper, mischmetall, niobium, S is 5 when M is rhenium, vanadium, niobium ortantalum; strontium, barium, scandium, yttrium, the rare earth metals, titanium, Zirconium, hafnium, chromium, s is 6 when M is tungsten; molybdenum, tantalum, rhenium, iron, ruthenium, Q is a neutral ligand; 50 osmium, rhodium, iridium, palladium, platinum, silver, t is 0 or an integer of 1 to 6; gold, Zinc, cadmium, mercury, indium, thulium, ger and provided that each oxo group present counts as two of manium, tin, lead, arsenic, antimony and bismuth; S. Z is an anion of the formula RSO, wherein R is This invention also concerns a second process for the perfluoroalkyl containing 1 to 12 carbon atoms or part polymerization of cyclic ethers, comprising, contacting one, 55 of a fluorinated group wherein the carbon atoms alpha at a temperature of about-80° C. to about 130° C., or more and beta to the sulfonate group are together bonded to oxiranes, oxetanes, tetrahydrofurans, oxepanes, 1,3-diox at least four fluorine atoms; olanes, or 1,3,5-trioxanes; with a zeolite which contains ad metal cation selected from the group consisting of strontium, s is 1 when M is silver, vanadium, copper, mischmetall, niobium, tungsten, cobalt, 60 S is 2 when M is strontium, barium, cobalt, rhodium, barium, scandium, yttrium, the rare earth metals, titanium, iridium, palladium, platinum, chromium, zinc, cad Zirconium, hafnium, chromium, molybdenum, tantalum, mium or mercury; rhenium, iron, ruthenium, osmium, rhodium, iridium, pal s is 3 when M is scandium, yttrium, a rare earth metal, ladium, platinum, silver, gold, zinc, cadmium, mercury, arsenic, antimony, bismuth, gold, iron, ruthenium, aluminum, gallium, indium, thulium, germanium, tin, lead, 65 osmium, aluminum, gallium, indium or thulium; arsenic, antimony and bismuth; and an accelerator selected s is 4 when M is titanium, zirconium, hafnium, molyb from the group consisting of carboxylic anhydrides, acyl denum, germanium, tin, or lead; 5,541,346 S 6 S is 5 when M is rhenium, vanadium, niobium ortantalum; -continued s is 6 when M is tungsten; H O H Q is a neutral ligand; R- N-R t is 0 or an integer of 1 to 6; and O x O each A is independently an organic radical having X free valencies; H R1 each x is independently 2, 3, 4, 5 or 6; and provided that: wherein n is 2 or 4 and each R', R, R and R' is A is bound to carboxyl groups through a carbon atom; independently hydrogen or hydrocarbyl containing 1 to 20 said polycarboxylic acid has a pKa of about 6 or less, 10 carbon atoms. Some of these cyclic ethers Eyre tO said polycarboxylic acid does not by itself catalyze give repeat units of the formula-(CHR (CRR ),CHRO) polymerization of the tetrahydrofuran; and --. In a more preferred cyclic ether all of R', R, R and R' the ratio of equivalents of carboxyl groups of said are hydrogen. In another more preferred cyclic ether where polycarboxylic acid to moles of said catalyst is less n=2, R', one of R', both of RandR are hydrogen, and the than 6. 15 remaining R’ is alkyl containing 1-4 carbon atoms, espe This invention also concerns a polymer consisting essen cially preferably the remaining R is methyl. By hydrocarbyl tially of a repeat unit of the formula herein is meant a univalent radical containing carbon and hydrogen. (-CHRCRRCRRCHRO-),C(O)AC(O)O- The first polymerization is run in the presence of an 20 accelerator. Suitable accelerators are carboxylic anhydrides, wherein: acyl halides, and carboxylic acids with a pk of less than each R', R, R and R is hydrogen or hydrocarbyl about 6 in water. containing 1 to 20 carbon atoms; By a carboxylic anhydride is meant a compound contain each n is independently an integer of 1 or more; ing the grouping -CO)O(O)C-, wherein the free valen each A is independently hydrocarbylene or substituted 25 cies are to other carbon atoms. A preferred carboxylic hydrocarbylene containing one or more functional anhydride is an anhydride of an alkyl carboxylic acid or a groups selected from the group consisting of imide, halogen substituted alkyl carboxylic acid, and particularly amide, urea and urethane; preferred anhydrides are acetic anhydride and trifluoroacetic and provided that each A is bound to an ester group through anhydride. a carbon atom. 30 By an acyl halide is meant a compound containing the grouping-C(O)X, where X is chlorine or bromine and the free valence is to another carbon atom. In preferred acyl halides, X is chlorine. Preferred acyl halides are alkyl acyl DETAILS OF THE INVENTION halides, and especially preferred are acetyl halides, more In the first polymerization process described herein one or 35 preferably acetyl chloride. more cyclic ethers, oxiranes, oxetanes, 1,3-dioxolanes, 1,3, By a carboxylic acid is meant a compound containing the 5-trioxanes, or tetrahydrofurans are polymerized to form a grouping-C(O)CH, wherein the free valence is to another polyether. For all processes herein, oxirane (more commonly carbon atom. Preferred carboxylic acids have a pKa of less called epoxide) is herein given its usual structure, a saturated than 5 in water. Useful carboxylic acids include, but are not three membered ring containing two carbon atoms and one 40 limited to acetic, trifluoroacetic, chloroacetic, benzoic, oxygen atom. Oxetane is also given its common meaning, a trichloroacetic, p-nitrobenzoic, butyric, formic, cyanoacetic, saturated four membered ring containing three carbon atoms nitropropionic, acrylic, methacrylic, and napthoic acids. and one oxygen atom. The term oxepane means a saturated Preferred carboxylic acids are trifluoroacetic, acetic, formic, seven membered ring containing six carbon atoms and one cyanoacetic, nitropropionic, acrylic and methacrylic acids. oxygen atoms. The term 1,3-dioxolane means a saturated 45 When carboxylic anhydride is present one half or more of five membered ring which contains two oxygen atoms the end groups are carboxylic esters. As is known to the separated by 1 carbon atom. The term 1,3,5-trioxane means artisan, these may be hydrolyzed to hydroxyl groups by a six membered ring containing 3 oxygen atoms in which the reaction with water, preferably in the presence of a catalyst, oxygen atoms and carbons atoms are alternated. All of these such as a strong acid (sulfuric acid for instance) or a strong terms include compounds containing those ring systems 50 base (such as NaOH). The proportion of acetate ends which are substituted with hydrocarbyl or hydrocarbylene increases the longer the polymerization is allowed to pro groups containing 1 to 20 carbon atoms. The hydrocarbylene ceed. Although the polymeric diol is often the desired groups may form carbocyclic rings, which include bicyclic, product (it can be used to make other polymers, such as tricyclic, etc., systems. By a hydrocarbylene group herein is polyurethanes and polyesters), the half ester or diester is also meant a divalent radical containing carbon and hydrogen 55 useful, as in relatively low molecular polymers which can be which is part of a carbocyclic ring. used as solvents. Preferred cyclic ethers for the first polymerization have When an acyl halide is used as the accelerator, the end the formula groups are usually ester on one end, and the halide, X, on the other. Thus the complete formula for such a polymer could 60 be X-CHR (CRR). CHRO-C(O)Y, where Y is the group to which the acyl group of the acyl halide was bound. Such polymers are useful as intermediates for the prepara tion of polymers containing different functional groups. For example, the ester may be hydrolyzed to a hydroxyl group, 65 and the halide may be reacted to form another functional group such as nitrile. If a bis(acyl halide), X(O)CYC(O)X, is used as the accelerator, the product of the polymerization 5,541,346 7 8 will be a polyether with halide (X) end groups which tetrafluoroborate, although at least one of triflate or tetrafluo contains two internal ester groups, and may have the formula roborate anions must be present. Some other useful anions X-CHR' (CRR). CHRO-C(O)YC(O)- are alkoxide, particularly lower alkoxide containing 1-4 (OCHR (CRR). CHR -X. Useful bis(acyl halides) carbon atoms, acetylacetonate, cyclopentadieneide, pentam include adipoyl chloride, terephthaloyl chloride, and digly ethylcyclopentadieneide, t-butylacetylacetonate, and halide. colyl chloride Cl(O)CCHOCHC(O)Cl]. It is preferred if all of the anions are triflate. In the first polymerization when a carboxylic acid is used In general, in the first polymerization the higher the molar ratio of metal compound to cyclic ether monomer originally as the accelerator, both end groups are usually mostly ester. present, the lower the molecular weight of the resulting Thus the complete formula for such a polymer could be polyether will be. Similarly, the higher the ratio of accel Y(O)CO-CHR (CRR). CHRO-C(O)Y, where Y is 10 erator (if present) to monomer originally present, the lower the group to which the acyl group of the carboxylic acid was the molecular weight of the polyether will be. It is believed bound. the effects of these two ratios are cumulative. For these An important consideration in the preparation of poly effects see Examples 7 and 8. ethers is the number average molecular weight (Mn) of the The first polymerization may be run at a temperature of polyether and its molecular weight distribution. When the 15 about -80° C. to about 130° C. If this temperature is above polyether is to be used as a monomer in the preparation of the boiling point of the cyclic ether monomer, a pressure another polymer (usually in the diol form), it is often vessel may be used. A preferred temperature is ambient to preferred in the first polymerization that the Mn of the the boiling point of the monomer, or 110° C., whichever is polyether be in the range of about 400 to about 20,000, lower. An inert solvent such as di-n-butyl ether, diethyl ether preferably about 500 to about 5,000. 20 or toluene may be used, but it is preferred if solvents are not In the first polymerization the catalyst may be yttrium or present. Protic compounds such as water, methanol and rare earth compound of the formula MZ where M is a ethanol should preferably not be present, and it is convenient trivalention of yttrium, or one of the rare earths, lanthanum, to exclude them by drying the starting materials and keeping cerium, praeseodymium, neodymium, promethium, the process under an inert dry gas such as nitrogen. As in samarium, europium, gadolinium, terbium, dysprosium, hol most chemical processes, the ingredients should be mixed at mium, erbium, thulium, ytterbium, and lutetium. least initially. Continued agitation is preferred to assure that In the first polymerization preferred metals, M, are stron the process materials remain well mixed, and to avoid tium, scandium, yttrium, the rare earth metals, titanium, overheating. The polymerization is mildly exothermic. If the zirconium, hafnium, vanadium, niobium, tantalum, chro polymerization temperature goes up appreciably, refluxing mium, molybdenum, tungsten, rhenium, iron, ruthenium, 30 of the monomer may be used to help cool the process. palladium, copper, gold, zinc, tin and bismuth. More pre The polymers produced in the first polymerization often ferred metals are yttrium, the rare earth metals, and scan have polydispersities significantly less than 2, which is dium. Especially preferred metals are yttrium, ytterbium, possibly indicative of a "Living polymerization'. Also dysprosium, erbium, neodymium, lanthanum, and scan indicative of this is the fact that as the polymerization dium. Another preferred metal is "mischmetall' (sometimes 35 proceeds, the molecular weight, particularly the number also called "didymium"), which is a mixture of rare earth average molecular weight, increases. metals as obtained from the ore. In the second and third polymerizations, the terms It is believed monovalent anions that are relatively non oxirane, oxetane, oxepane, 1,3-dioxolane, 1,3,5-trioxane, nucleophilic are useful as Z. Examples of such anions are and tetrahydrofuran include compounds containing those tetraphenylborate, RSO, wherein R is perfluoroalkyl, or 40 ring systems which are substituted with hydrocarbyl or wherein R is part of a fluorinated polymer wherein the hydrocarbylene groups containing 1 to 20 carbon atoms. The carbon atoms alpha and beta to a Sulfonate group are hydrocarbylene groups form carbocyclic rings, which together bonded to at least 4 fluorine atoms (as in include bicyclic, tricyclic, etc. systems. By a hydrocarbylene -CFCFSO). It is preferred if R is perfluoroalkyl. In a group herein is meant a divalent radical containing carbon particularly preferred R is trifluoromethyl, and the anion is 45 and hydrogen which is part of a carbocyclic ring. herein called 'trifiate'. In the second and third polymerizations preferred cyclic Generally speaking, in the first polymerization any metal ethers have the formula lic compound in which the correct metal in the correct oxidation state (see above) is present and bonded to a triflate R1 or similar anion will be a catalyst. Such a compound must 50 R1 R1 H R1 of course be reasonably stable during the polymerization (or CH depolymerization, see below), or decompose to another O / (CR2R3), H-H-H or O X O compound which is still a triflate (or similar anion) com O O pound of the metal in the correct oxidation state. It has been CH x 1s O 1st found that, in general, the greater the number of triflate 55 R4 H R1 H H groups bonded to the metal cation, the more active the metal compound will be as a catalyst. It is preferred if half or more wherein n is 2 or 4, and each R', R', R and R is of the anions (Z) bound to each metal cation is triflate or a independently hydrogen or hydrocarbyl containing 1 to 20 similar anion. carbon atoms. Some cyclic ethers polymerize to give repeat The metal catalysts of the first polymerization may units of the formula -(CHR' (CRR),CHRO-. In a optionally contain one or more neutral ligands coordinated more preferred cyclic ether all of R', R, R and R' are to the metal. By a neutral ligand is meant a neutral com hydrogen. In another more preferred cyclic ether where n=2, pound that can coordinate with the catalysts, usually the R', one of R, both of R and R are hydrogen, and the metal cation. Neutral ligands include water, and ethers such remaining R is alkyl containing 1-4 carbon atoms, espe as dimethyl ether and tetrahydrofuran. 65 cially preferably the remaining R is methyl. By hydrocarbyl The metals catalysts of the first polymerization may herein is meant a univalent radical containing carbon and contain other anions than triflate and similar anions, and hydrogen. 5,541,346 9 10 The second and third polymerizations are carried out in products when a carboxylic anhydride is used as the accel the presence of an accelerator (sometimes also called a erator. co-catalyst). Suitable accelerators are carboxylic anhy The second and third polymerizations may be run at a drides, acyl halides and carboxylic acids whose pKa is less temperature of about -80° C. to about 130° C. If this than about 6 in water. temperature is above the boiling point of the cyclic ether By a carboxylic anhydride is meant a compound contain monomer, a pressure vessel may be used. A preferred temperature is ambient to the boiling point of the monomer ing the grouping -C(O)O(O)C-, wherein the free valen or 110° C., whichever is lower. An inert solvent such as cies are to other carbon atoms. A preferred carboxylic di-n-butyl ether, diethyl ether or toluene may be used, but it anhydride is an anhydride of an alkyl carboxylic acid or a is preferred if solvents are not present. Protic compounds halogen substituted alkyl carboxylic acid, and particularly 10 such as water, methanol and ethanol should preferably not be preferred anhydrides are acetic anhydride and trifluoroacetic present, and it is convenient to exclude them by drying the anhydride. starting materials and keeping the process under an inert dry By an acyl halide is meant a compound containing the gas such as nitrogen or dry air. As in most chemical grouping-C(O)x, where X is chlorine or bromine and the processes, the ingredients should be mixed. Continued agi free valence it to another carbon atom. In preferred acyl 15 tation is preferred to assure contact of the process liquids halides X is chlorine. Preferred acyl halides are alkyl acyl with the heterogeneous catalyst, and to avoid overheating. halides, and especially preferred are acetyl halides, more The polymerization is mildly exothermic. If the polymer preferably acetyl chloride. ization temperature goes up appreciably, refluxing of the In the second and third polymerizations, by a carboxylic monomer may be used to help cool the process. acid is meant a compound containing the grouping 20 The second and third polymerizations may be run in a -C(O)CH, wherein the free valence is to another carbon variety of methods, such as batch, semi-continous, or con atom. Preferred carboxylic acids have a pKa of less than 5 tinuous. While the heterogeneous catalyst may be recovered in water. Useful carboxylic acids include, but are not limited each time, as by filtration, and reused, in another embodi to formic, acetic, trifluoroacetic, chloroacetic, benzoic, ment the catalyst is fixed in place and the polymerization trichloroacetic, p-nitrobenzoic, butyric, and naphthoic acids. 25 mass circulated or agitated so that uniform contact with the Preferred carboxylic acids are trifluoroacetic, formic, acetic, catalyst surface is obtained. In this way, the catalyst may be cyanoacetic, nitropropionic, nitrobenzoic, acrylic and meth used for long periods in a continuous process, or for many acrylic. These and other acids that themselves don't cause batches in a batch polymerization, without the need to polymerization of the cyclic ethers are also believed to be recover the catalyst. Contact time of the liquid reaction mass accelerators, especially if their pKa in water is about 6 or 30 with the catalyst will depend on many factors, such as the less. catalytic metal used, its concentration on the catalyst, the When carboxylic anhydride is present one half or more of temperature, cyclic ether being polymerized, etc., but will the end groups are carboxylic esters. As is known to the usually be in the range of a few minutes to a few hours. artisan, these may be hydrolyzed to hydroxyl groups by Catalysts used herein in the second and third polymer reaction with water, preferably in the presence of a catalyst, 35 izations contain selected metal cations. Preferred metal such as a strong acid (sulfuric acid for instance) or a strong cations are those of strontium, scandium, yttrium, the rare base (such as NaOH). The proportion of acetate ends earth metals, titanium, zirconium, hafnium, vanadium, nio increases the longer the polymerization is allowed to pro bium, tantalum, chromium, molybdenum, tungsten, rhe ceed. Although the polymeric diol is often the desired nium, iron, ruthenium, palladium, copper, gold, zinc, tin and product (it can be used to make other polymers, such as bismuth. More preferred metals are yttrium, the rare earth polyurethanes and polyesters), the half ester or diester is also metals, scandium and Zirconium. Especially preferred met useful, as in relatively low molecular weight polymers als are yttrium, ytterbium, dysprosium, erbium, neodymium, which can be used as solvents. lanthanum, scandium and zirconium. Another preferred When acyl halides are used as the accelerator, the end metal is "mischmetall' (sometimes also called "didy groups are usually ester on one end, and the halide, X, on the 45 mium'), which is a mixture of rare earth metals as obtained other. Thus the complete formula for such a polymer could from the ore. By rare earths herein is meant lanthanum, be X-CHR (CRR). CHRO-C(O)Y, where Y is the cerium, praeseodymium, neodymium, promethium, group to which the acyl group of the acyl halide was bound. samarium, europium, gadolinium, terbium, dysprosium, hol Such polymers are useful as intermediates for the prepara mium, erbium, thulium, ytterbium, and lutetium. By a per tion of polymers containing different functional groups. For 50 fluoroalkylsulfonate herein is meant a metal salt of a per example, the ester may be hydrolyzed to a hydroxyl group, fluoroalkylsulfonate in which the metal is bonded to one or and the halide may be reacted to form another functional more perfluoroalkylsulfonate groups. group such as nitrile. If a bis (acyl halide), X(O)CYC(O)X, The catalyst used in the second polymerization herein is is used as the accelerator, the product of the polymerization a zeolite in which some of the metal cations present are the will be a polyether with halide (X) end groups which 55 cations listed above. The anions of such cations are not contains two internal ester groups, and may have the formula critical, and may be those normally found in zeolites. The X-(CHR' (CRR). CHRO-C(O)YC(O)- Zeolites containing the appropriate metal cations can be (OCHR (CRR). CHR-X. Useful bis(acyl halides) made by the ion exchange of cations in known zeolites. Such include adipoyl chloride, terephthaloyl chloride, and digly ion exchange processes are know to the artisan, see for colyl chloride Cl(O)CCHOCHC(O)Cl]. 60 instance D. W. Breck in Zeolite Molecular Sieves, R. E. In the second and third polymerizations, when a carboxy Krieger Publishing Co., Malabar, Fla., 1984 and Examples lic acid is used as the accelerator, the end groups are usually 7, 9, 12, 14, 16, 18, and 20. It is preferred if at least 0.5 atom mostly ester. Thus the complete formula for such a polymer percent of the metals and metalloids in the zeolite are one of could be Y-C(O)-O-(CHR (CRR). CHRO the useful "catalytic' metals, more preferably at least 5 atom C(O)Y, where Y is the group to which the acyl group of the 65 percent. It has been found that the zeolite catalysts usually carboxylic acid was bound. The ester group may be hydro yield polyethers with bimodal molecular weight distribu lyzed as described above in the paragraph describing the tions. 5,541,346 11 12 The catalyst of the third polymerization, a "catalytic' A(CO2H), wherein A is an organic radical, and wherein A metal perfluoroalkylsulfonate is attached to the surface of a is bound to each carboxyl group through a carbon atom. By material that in effect acts as a heterogeneous support for the "through a carbon atom' is meant that each carboxyl group metal perfluoroalkylsulfonate. The metal is not attached to is bound to a carbon atom which is part of A. A may contain the surface through the perfluoroalkylsulfonate, but through 5 any substituent which does not react during, or disturb, the another bond or ligand. The catalytic metal should have at least one perfluoroalkylsulfonate anion attached to it, and fourth polymerization. Suitable functional groups include preferably, except for the group attaching the metal to the halo, ester, amide, urethane, urea, keto, ether, imide, and support surface, all of the groups should be perfluoroalkyl Sulfone, and hydrocarbon based "functional groups' such as Sulfonate. olefins, aromatic rings, and acetylenic bonds. Especially In the third polymerization catalyst, the metal may be 10 preferred functional groups are ester, amide, imide, urethane attached to the surface by a covalent bond, or coordination, and urea. The functional groups should be picked so that or any other method. It is preferred if significant amounts they don't undergo an acid base reaction with the carboxyl (>25%, preferably <10%) of the catalytic metal cannot be groups of the polycarboxylic acid. Thus aliphatic amine leached from the heterogeneous catalyst by the polymeriza groups should not be present and are classified as among tion process liquids. In one method of attachment, a ligand 15 those groups which interfere with the polymerization. which can coordinate with the metal cation is attached via Useful polycarboxylic acids include, but are not limited one or more covalent bonds to the surface of the support, and to, maleic acid, fumaric acid, succinic acid, adipic acid, then the metal cation is coordinated to the ligand, thereby isophthalic acid, terephthalic acid, and 1,2,4-benzenetricar fixing the metal cation on the support surface. Particularly boxylic acid. Preferred polycarboxylic acids are adipic, useful for such are silicon compounds to which the ligand is 20 isophthalic and terephthalic acids. attached by a stable (to hydrolysis and the polymerization The polycarbOxylic acid has a pKa of less than 6, process conditions) bond, and in which the silicon is directly preferably less than 5, and should not by itself catalyze the attached to groups which are readily hydrolyzed. When polymerization of the tetrahydrofuran. In preferred polycar these hydrolytically unstable groups are hydrolyzed from the boxylic acids, X is 2 (a dicarboxylic acid). When x is more silicon atom, the resulting "compound" can readily bond to 25 than two, a branched and/or crosslinked poly(ether-ester) Surfaces which have hydroxyl groups present. Many com will be produced. mon Supports, such as alumina, silica (gel), many metal The catalyst for the fourth polymerization may be a oxides, and others have such surfaces. After the ligand is yttrium or rare earth compound of the formula MZ where attached to the surface, an appropriate metal compound is M is a trivalent ion of yttrium, or one of the rare earths, contacted with the surface containing the ligands, and the 30 lanthanum, cerium, praeseodymium, neodymium, prome metal cation becomes fixed to the support surface. See thium, Samarium, europium, gadolinium, terbium, dyspro Examples 177, 179, 181, and 183 for such processes. sium, holmium, erbium, thulium, ytterbium, and lutetium. The heterogeneous supports for such third polymerization Preferred metals in the fourth polymerization, M, are catalysts can be those which are commonly used for sup Strontium, Scandium yttrium, the rare earth metals, titanium, ported catalysts. It is preferred if they have a relatively large 35 Zirconium, hafnium, vanadium, niobium, tantalum, chro surface area, at least 25 m/gm, and it is also preferred if the mium, molybdenum, tungsten, rhenium, iron, ruthenium, Support is inorganic (inorganic includes various forms of palladium, copper, gold, zinc, tin and bismuth. More pre carbon, such as activated carbon, graphite, etc.). Useful ferred metals are yttrium, the rare earth metals, and scan Supports include alumina, silica, silica-aluminates, carbon, dium. Especially preferred metals are yttrium, ytterbium, Zirconia, yttria, magnesia, ceria, aluminum fluoride and 40 dysprosium, erbium, neodymium, lanthanum, and scan barium sulfate. Preferred supports are alumina, silica, silica dium. Another preferred metal is "mischmetall' (sometimes aluminates, carbon and zirconia. It is preferred if the sup also called "didymium'), which is a mixture of rare earth ports themselves are acidic. Although not critical, a conve metals as obtained from the ore. nient amount of the catalytic metal on the catalyst is about It is believed monovalent anions that are relatively non 0.1 to about 20 weight percent, measured as catalytic metal. 45 nucleophilic are useful as Z. Examples of such anions are In the fourth polymerization process a tetrahydrofuran is tetraphenylborate, RSO, wherein R is perfluoroalkyl, or Copolymerized with a polycarboxylic acid to yield a poly wherein R is part of a fluorinated polymer wherein the (ether-ester). By a tetrahydrofuran (THF) is meant the carbon atoms alpha and beta to a sulfonate group are common meaning, a compound containing a saturated five together bonded to at least 4 fluorine atoms (as in membered ring in which one of the ring atoms is oxygen and 50 -CFCFSO). It is preferred if R is perfluoroalkyl. In a the other four ring atoms are carbon. Preferred tetrahydro particularly preferred R is trifluoromethyl, and that anion is furans have the formula I herein called "trifiate'. Generally speaking, any metallic compound in which the R3 R3 I correct metal in the correct oxidation state (see above) is 55 present and bonded to a triflate or a similar anion will be a catalyst in the fourth polymerization. Such a compound must of course be reasonably stable during the polymeriza H O H tion or decompose to another compound which is still a wherein each R', R, R and R is independently hydrogen triflate (or similar anion) compound of the metal in the or hydrocarbyl containing 1 to 20 carbon atoms. In espe 60 correct oxidation state. cially preferred THFs, R', one of R and all of R and Rare The metal catalysts in the fourth polymerization may hydrogen, and the remaining R is alkyl containing 1-4 optionally contain one or more neutral ligands, Q, coordi carbon atoms, particularly the remaining R is methyl. In nated to the metal. By a neutral ligand is meant a neutral another especially preferred embodiment all of R, R, R compound that can coordinate with the catalysts, usually the and R' are hydrogen 65 metal cation. Neutral ligands include water, and ethers such In the fourth polymerization a tetrahydrofuran is copoly as dimethyl ether and tetrahydrofuran. Useful compounds merized with a polycarboxylic acid of the formula containing neutral ligands include bis(n-cyclopentadi 5,541,346 13 14 enyl)tetrahydrofuranbis(trif luoromethanesulfonate)Zirconium and bis(n-cyclopentadi enyl)tetrahydrofuran wherein each R, R and R is independently hydrocarby bis(trifluoromethanesulfonate)hafnium. lene or substituted hydrocarbylene containing 2 to 25 carbon In general, in the fourth polymerization the higher the atoms, E is -O- or -NR'-, wherein R' is as defined molar ratio of metal compound to cyclic ether monomer above, and m is an average of 0 to 10. Such polymers are originally present, the lower the molecular weight of the made from dicarboxylic acids A(COH), whereinx is 2, and resulting polyether will be. A has the formula shown above. Such diacids can be made The fourth polymerization may be run at a temperature of by the reaction of one or more diisocyanates with one or about -80° C. to about 130° C. If this temperature is above more aminocarboxylic acids, hydroxy carboxylic acids, the boiling point of the cyclic ether monomer, a pressure 10 diamines, aminoalcohols and diols. The group R is derived vessel may be used. A preferred temperature is ambient to from the amino- or hydroxycarboxylic acid, R is derived the boiling point of the monomer, or 110° C., whichever is from an organic diisocyanate, and R is derived from a lower. An inert solvent such as di-n-butyl ether, diethyl ether diamine or diol. When a particular E is -O-, it can be or toluene may be used, but it is preferred if solvents are not derived from the reaction of an isocyanate group and a present. Protic compounds such as water, methanol and 15 hydroxy group to form a urethane. When a particular E is ethanol should preferably not be present, and it is convenient -NR it can be derived from the reaction of an isocy to exclude them by drying the starting materials and keeping anate and a primary amino group when R' is hydrogen, and the process under an inert dry gas such as nitrogen. As in a secondary amino group when R' is hydrocarbyl, to form most chemical processes, the ingredients should be mixed at a urea. All preferred formulas for dicarboxylic acids also least initially. Continued agitation is preferred to assure that 20 refer to "A' in the polymer. the process materials remain well mixed, and to avoid Dicarboxylic acids containing various functional groups overheating. The polymerization is mildly exothermic. If the can be made by methods known in this art. See, for instance, polymerization temperature goes up appreciably, refluxing Chem. Abs., Vol. 44, 5104 b-d (1950), S. Hsiao, et al., J. of the monomer may be used to help cool the process. Polym. Sci., Part A, Vol. 28, pp. 2169-2178 (1990), and R. The molar ratio of THF to polycarboxylic acid at the 25 E. Asay et al., J. Heterocyclic Chem., Vol. 14, pp. 85–90 beginning of the fourth polymerization can be about 0.2 to (1977). about 60, preferably about 2 to about 15. Generally speak To give a concrete example, if it is desired to make the ing, the higher the relative molar amount of polycarboxylic dicarboxylic acid wherein both of R are 1,4-phenylene, R' acid present, the greater the incorporation (per THF unit) of 1S ester units (from polycarboxylic acid) will be. The desired amount of ester present will depend on the polycarboxylic 30 acid used, and the use of the polymeric product. CH2 However, in the fourth polymerization the ratio of equiva lents of carboxylic acid groups (in the polycarboxylic acid) to the number of moles of catalyst (MZQ) should be less 35 Ris 1,4-phenylene, every Eis-NH-, and m is an average than six (i.e., carboxyl present/moles catalyst <6). In a of 1, one could react (preferably in solution) one mole of simple batch reaction this means this ratio will be less than p-phenylene diamine, two moles of p-aminobenzoic acid, 6 at the start of the polymerization, and decrease as the and two moles of bis (4-isocyanatophenyl)methane. To polycarboxylic acid is polymerized, and its carboxyl groups prepare the corresponding polymer where every E is-O-, are "used up' and converted to ester groups. However, as the one would use hydroquinone and p-hydroxybenzoic acid in carboxyl groups are used up by polymerization, they may be 40 place of p-phenylenediamine and p-aminobenzoic acid, respectively. To vary m, the ratio of diamine, diol and/or replaced by the addition of polycarboxylic acid, so long as aminomonool to aminocarboxylic acid and/or hydroxyacid the above ratio is less than 6. would be varied. The amount of diisocyanate would also be In the fourth polymerization when a dicarboxylic acid changed so it could react with all of the amino and/or (x=2) is used in the polymerization, a (product) polymer 45 hydroxy groups present. As the art skilled will understand, repeat unit can be represented by the general formula in reactions of this type, a distribution of m values will be obtained (except when m is 0) for individual molecules, and (-CHRCRRCRRCHRO-),C(O)AC(O)O- overall, m is the arithmetic average of the values for wherein all of the symbols have the definitions as given individual molecules. Fractional values of mare possible by above, and n is an integer of 1 or more. In preferred 50 varying the stoichiometry. Experiment 1 illustrates the polymers, n is about 5 to about 500, more preferably about preparation of such a dicarboxylic acid. 8 to about 100. Useful A groups include tetramethylene, In preferred dicarboxylic acids: p-phenylene, and m-phenylene. R and R are each independently 14-phenylene, 1,3- In another preferred polymer product of the fourth poly phenylene, and n-alkylene containing 2 to 6 carbon merization, n is 5 or more, more preferably 10 or more. It is 55 atons; preferred if A contains urea or urethane groups. By a urea R" is 1,4-phenylene, 1,3-phenylene, n-alkylene contain group is meant -NH-C(O)-NR'-, and by a urethane ing 2 to 6 carbon atoms, or group is meant-O-C(O)-NH-, wherein R' is hydro gen or hydrocarbyl containing 1 to 20 carbon atoms. It is preferred if R' is hydrogen. In other preferred polymers, all 60 CH of R', R', RandR are hydrogen, or one of R’ is methyl, the other R is hydrogen, and all of R', R, and R' are hydrogen. A preferred polymer product of the fourth polymerization In especially preferred dicarboxylic acids: is one in which A has the formula 65 R and R are each independently 1,4-phenylene, 1,3- phenylene, and n-alkylene containing 2 to 6 carbon atoms, 5,541,346 15 16 R’ is ethylene, or water. In both instances, the recovered catalyst may be used again in a polymerization or depolymerization process. In both instances the aqueous washings may be concentrated CH2 by removal of the wager (as by evaporation) and the solid catalyst recovered. See Examples 20, and 28-32 for recov ery and reuse of catalyst. In other preferred dicarboxylic acids E is -NR' - The second depolymerization process is carried out at wherein R' is hydrogen, or m is an average of 0 to about about 100° C. to about 250° C., preferably about 130° C. to 3. about 200° C. Although air can be used to blanket the By hydrocarbylene in the fourth polymerization and its 10 process, it is preferred to use an inert atmosphere such as products is meant a divalent radical containing only carbon nitrogen to avoid possible side reactions. A solvent may be and hydrogen. A substituted hydrocarbylene is a radical used, but it is preferred to carry out the process without which also contains substituent groups that do not interfere solvent. with any of the reactions, including polymerization, The amount of catalyst compared to polyether present is described herein. Suitable functional groups have been listed 15 not critical, 0.1-15% by weight (percent of the catalyst to above. polyether) being useful, preferably about 1 to 3% by weight The polymeric product of the fourth polymerization, of catalyst. particularly one made from dicarboxylic acids containing The second depolymerization process may be carried out other functional groups, is useful as a thermoplastic elas by just heating the polyether in the presence of the hetero tomer, urethane rubber or in spandex fiber. The ester groups 20 geneous catalyst. In order to avoid boiling off the often of the poly(ester-ether) may be hydrolyzed to form polyether volatile tetrahydrofurans, a pressure vessel may be needed. diols. However, it is preferred to carry out the depolymerization This invention is also concerned with the first depolymer while constantly distilling off the (substituted) tetrahydro ization of a polymer consisting essentially of the repeat unit furan as it forms. It is believed that this ensures driving this -(CHRCRRCRRCHRO- wherein R, R, R, and 25 process to produce the monomeric tetrahydrofuran. R" are defined above, and preferred combinations are as In both the second and third polymerization and second given above for the first polymerization process when n=2. depolymerization processes disclosed herein heterogeneous A catalyst designated MZQ, is used, wherein M, S, Q, t, catalysts may be recovered and reused in any of the pro and Z, and their preferred embodiments, are as given above cesses. It may be recovered from the processes by filtration, for the first polymerization. 30 and if desired, drying. The recovered catalyst may be used The first depolymerization process is carried out at about again in the polymerization or depolymerization processes. 100° C. to about 250° C., preferably about 130° to about All of the above processes may be carried out as batch, 200° C. Although air can be used to blanket the process, it semibatch or continuous processes. For all of the processes, is preferred to use an inert atmosphere such as nitrogen to continuous type processes are preferred. avoid possible side reactions. The polytetrahydrofuran need 35 In the Examples, the following abbreviations are used: not be dried before use. A solvent may be used, but it is ACA-acetic anhydride preferred to carry out the process without solvent. The amount of catalyst compared to polyether present in DETM-diethyl 2-3-(triethoxysilyl)propyl)malonate the first depolymerization is not critical, 0.1-15% by weight DMAC-N,N-dimethylacetamide being useful, preferably about 1 to 3% by weight of catalyst. 40 GPC-gel permeation chromatography The first depolymerization process may be carried out by MDI-bis(4-isocyanatophenyl)methane just heating the polyether in the presence of the catalyst. In NafionTM-a sulfonated perfluoropolymer produced by E. order to avoid boiling off the often volatile tetrahydrofurans, I. du Pont de Nemours and Company, Wilmington, a pressure vessel may be needed. However, it is preferred to Del., U.S.A. carry out the depolymerization while constantly distilling off 45 the (substituted) tetrahydrofuran as it forms. It is believed Mn-number average molecular weight that this ensures driving this process to produce the mono Mw-weight average molecular weight meric tetrahydrofuran. The recovered monomeric tetrahy RB-round bottom drofuran may be used in the polymerization to form a PD-polydispersity (Mw/Mn) polytetrahydrofuran. 50 PS-polystyrene Both the first polymerization and first depolymerization processes can be done in a variety of ways known to the SS-stainless steel artisan. The first polymerization can be done by batch, STD-standard semi-batch and continuous processes. Continuous processes Tf -triflate include continuous stirred tank reactor(s) with one or more 55 THF-tetrahydrofuran stages, and/or plug flow reactors (see Example 19). The first depolymerization process can also be done by similar meth EXAMPLE 1. ods. In this process, a continuous process could be constant addition of polyether to the reactor, while distilling off a Polymerization of THF with Yttrium Triflate and similar amount of a monomeric tetrahydrofuran. Other 60 variations will be evident to one skilled in this art. Acetic Anhydride In both the first polymerization and first depolymerization In a dry box, yttrium triflate (0.75 g) was added to each processes disclosed herein the catalyst may be recovered and of three separate oven dried 100 mL RB flasks equipped reused in either process. It may be recovered from the with stirring bars. The flasks were sealed with rubber septa polymerization process by extracting the polymer formed 65 and removed from the dry box and nitrogen bleeds attached. with water, while it can be recovered from the depolymer THF (20 mL) followed by acetic anhydride (0.75 mL) were ization process by extracting the distillation residue with added to each flask. After 15, 30 and 45 minutes, a poly 5,541,346 17 18 merization was terminated via the addition of 5% NaOH (10 removed from the dry box. Nitrogen bleeds were attached mL) and THF (50 mL). The resulting organic phases were and THF (20 mL) followed by acetic anhydride (0.75 mL) separated and concentrated at reduced pressure and then were added to each flask. After 15, 30, 45 and 60 minutes, dried under vacuum. Polymer yields and GPC analysis: a polymerization was terminated via the addition of 5% NaOH (10 mL) and THF (50 mL). The resulting organic Polymer, Polymer Mn phases were separated, concentrated at reduced pressure and Time Yield (%) (PSSTD) Mw PD then dried under vacuum. Polymer yields and GPC analysis: 15 mins. 56.76 880 17100 2.09 Polymer, Polymer Mn 30 mins. 67.02 6630 14600 2.20 O 45 mins. 73.1 6210 13300 2.02 Time Yield (%) (PSSTD) Mw PD 15 mins. 52.82 8460 15900 1.89 30 mins. 62.96 7390 17100 2.32 EXAMPLE 2 45 mins. 66.79 8070 16400 2.04 60 mins. 68.20 7250 16100 2.22 Polymerization of THF with Ytterbium Triflate and 15 Acetic Anhydride In a dry box, ytterbium triflate (0.75 g) was added to each EXAMPLE 5 of four separate oven dried 100 mLRB flasks equipped with stirring bars. The flasks were sealed with rubber septa and 20 Polymerization of THF with Lanthanum Triflate removed from the dry box. Nitrogen bleeds were attached and Acetic Anhydride and THF (20 mL) followed by acetic anhydride (0.75 mL) In a dry box, lanthanum triflate (0.75 g) was added to each were added to each flask. After 15, 30, 45 and 60 minutes, of four separate oven dried 100 mLRB flasks equipped with a polymerization was terminated via the addition of 5% stirring bars. The flasks were sealed with rubber septa and NaOH (10 mL) and THF (50 mL). The resulting organic 25 then removed from the dry box. Nitrogen bleeds were phases were separated, concentrated at reduced pressure and attached and THF (20 mL) and acetic anhydride (0.75 mL) then dried under vacuum. Polymer yields and GPC analysis: were added to each flask. After 15, 30, 45 and 60 minutes, a polymerization was terminated via the addition of 5% Polymer. Polymer Mn NaOH (10 mL) and THF (50 mL). The resulting organic Time Yield (%) (PSSTD) Mw P 30 phases were separated, concentrated at reduced pressure and 15 mins. 56.09 8400 16200 1.93 then dried under vacuum. Polymer yields and GPC analysis: 30 mins. 67.98 7360 14900 2.03 45 mins. 69.67 5890 13100 2.22 Polymer, Polymer MI 60 mins. 71.31 6010 12800 2.15 Time Yield (%) (PSSTD) Mw PD 35 15 mins. 5.60 9780 13900 142 EXAMPLE 3 30 mins. 1.2T 13700 20900 153 45 mins. 40.30 17000 28100 1.65 Polymerization of THF with Dysprosium Triflate 60 mins. 59.24 15800 33400 2.11 and Acetic Anhydride 40 In a dry box, dysprosium triflate (0.75 g) was added to EXAMPLE 6 each of four separate oven dried 100 mLRB flasks equipped with stirring bars. The flasks were sealed with rubber septa Polymerization of THF with Neodymium Triflate and removed from the dry box. After the attachment of and Acetic Anhydride nitrogen bleeds THF (20 mL) followed by acetic anhydride 45 (0.75 mL) were added to each flask. After 15, 30, 45 and 60 In a dry box, to an oven dried 100 mLRB flask equipped minutes, a polymerization was terminated via the addition of with a stirring bar was added neodymium triflate (0.75 g). 5% NaOH (10 mL) and THF (50 mL). The resulting organic The flask was sealed with a rubber septum and removed phases were separated, concentrated at reduced pressure and from the dry box. A nitrogen bleed was attached and THF then dried under vacuum. Polymer yields and GPC analysis: 50 (20 mL) followed by acetic anhydride (0.75 mL) were added. After 30 minutes the polymerization was terminated via the addition of 5% NaOH (10 mL) and THF (50 mL). Polymer. Polymer Mn The resulting organic phase was separated, concentrated at Time Yield (%) (PSSTD) Mw PD reduced pressure and then dried under vacuum yielding 7.56 15 mins. 5203 7260 15700 2.17 55 g (42.6%) of polymer. GPC analysis: Mn=8460, 30 mins. 63.86 7220 15700 2.18 45 mins. 70.05 62.50 14300 2.30 Mw-22300, PD=2.65 (PSSTD). 60 mills. 736 6010 3700 2.29 EXAMPLE 7 60 EXAMPLE 4 Polymerization of THF with Yttrium Triflate and Acetic Anhydride Polymerization of THF with Erbium Triflate and Acetic Anhydride In a dry box, yttrium trifiate (0.75 g) was added to each of three oven dried 100 mLRB flasks equipped with stirring In a dry box, erbium triflate (0.75 g) was added to each of 65 bars. The flasks were sealed with rubber septa and removed four separate oven dried 100 mL RB flasks equipped with from the dry box. Nitrogen bleeds were attached and THF stirring bars. After sealing with rubber septa the flasks were (20 mL) added to each flasks. Acetic anhydride (0.25, 0.50 5,541,346 19 20 and 0.75 mL) was added respectively to each flask. After 60 reduced pressure and then dried under vacuum. Yield: 1.73 minutes the polymerizations were quenched via the addition g (9.75%). GPC analysis: Mn=1150, Mw-2700, PD=2.34 of 5% NaOH (10 mL) and THF (50 mL), the resulting (PSSTD). organic phases were separated, concentrated at reduced pressure and then dried in vacuo overnight. Polymer yields and GPC analysis: EXAMPLE 11

Acetic Polymer Mn Copolymerization of THF/3-Methyl-THF with Anhydride Yield (%) (PSSTD) Mw PD O Yttrium Triflate and Acetic Anhydride 0.25 mL 75.02 8080 1800 2.25 0.50 IL 73.33 6940 14900 2.15 In a dry box, yttrium triflate (0.75 g) was added to each 0.75 IL 75.20 5080 13600 2.68 of three separate oven dried 100 mL RB flasks equipped with stirring bars. The flasks were sealed with rubber septa and removed from the dry box wherein nitrogen bleeds were 5 attached. THF (15 mL) and 3-methyl-THF (5 mL) followed EXAMPLE 8 by acetic anhydride (0.75 mL) were added to each flask. Polymerization of THF with Yttrium Triflate and After 15, 30 and 45 minutes, a polymerization was termi nated via the addition of 5% NaOH (10 mL) and THF (50 Acetic Anhydride mL). The resulting organic phases were separated, concen In a dry box, to three 100 mL RB flasks equipped with 20 trated at reduced pressure and then dried under vacuum. stirring bar were added 0.25, 0.50 and 1.00 g yttrium triflate Polymer yields and GPC analysis: respectively. The flask were sealed with rubber septa and removed from the dry box. Nitrogen bleeds were attached Polymer. Polymer Mn and THF (20 mL) and acetic anhydride (1.00 mL) were Time Yield (%) (PSSTD) Mw PD added to each flask. After 60 minutes the polymerizations 25 were terminated via the addition of 5% NaOH (10 mL) and 15 mins. 39.50 6920 2400 180 THF (50 mL). The resulting organic phases were separated, 30 mins. 51.63 6280 3200 2.1 concentrated at reduced pressure and dried under vacuum 45 mins. 57.27 5860 12700 2.17 overnight. Polymer yields and GPC analysis: H NMR analysis showed -12-13% incorporation of 3-methyl-THF in the 30 polymers. Yttrium Polymer Mn Triflate Yield (%) (PSSTD) Mw PD EXAMPLE 12 0.25 g 50.11 1300 26.200 2.02 0.50 g 70.79 8060 17600 2.16 35 1.00 g 81.96 4.820 10500 2.09 Polymerization of THF with Yttrium Triflate and Trifluoroacetic Anhydride EXAMPLE 9 In a dry box, yttrium triflate (0.75 g) was weighed in an 40 oven dried 100 mL RB flask equipped with a stirring bar. Polymerization of THF with Yttrium Triflate and After sealing with a rubber septum and removal from the dry Acetic Anhydride in Diethyl Ether box and attachment of a nitrogen bleed THF (20 mL) was added followed by trifluoroacetic anhydride (3.00 mL). In a dry box, yttrium triflate (0.75 g) was weighed into an After 2 hrs. the polymerization was quenched by the addi oven dried 100 mL RB flask equipped with stirring bar. A tion of 5% NaOH (10 mL) and THF (50 mL). Diethyl ether reflux condenser was attached and the apparatus sealed with 45 (50 mL) was added to effect separation of the organic/ a rubber septum and removed from the dry box. A nitrogen aqueous phase. The organic phase was separated, concen bleed was attached and diethyl ether (20 mL), THF (20 mL) trated at reduced pressure and then dried under vacuum. and acetic anhydride (0.75 mL) were added. After 60 Yield: 5.40 g (30.44%). GPC analysis: Mn=53900, minutes the polymerization was quenched via the addition of Mw-86200, PD=1.78 (PS STD). 5% NaOH (10 mL) and diethyl ether (50 mL). The resulting 50 organic phase was separated, concentrated and dried under vacuum. Yield: 3.86 g (21.76%). GPC analysis: Mn=2960, EXAMPLE 13 Mw=7800, PD=2.63 (PSSTD). EXAMPLE 10 55 Polymerization of THF with Ytterbium Triflate and Propionic Anhydride Polymerization of THF with Yttrium Triflate and Acetic Anhydride in Toluene In a dry box, ytterbium triflate (1.00 g) was weighed into an oven dried 100 mLRB flask equipped with a stirring bar. In a dry box, yttrium triflate (0.75 g) was weighed into an 60 The flask was stoppered with a rubber septum and removed oven dried. 100 mL RB flask equipped with a stirring bar. from the dry box and a nitrogen bleed was attached. THF (20 After sealing with a rubber septum, removal from the dry mL) and propionic anhydride (1.00 mL) were added via box, and attachment of a nitrogen bleed, toluene (20 mL), syringes. After 60 minutes the polymerization was quench THF (20 mL) and acetic anhydride (0.75 mL) were added. with 5% NaOH (10 mL) and THF (50 mL). The resulting After 60 minutes the polymerization was terminated via the 65 organic phase was separated, concentrated at reduced pres addition of 5% NaOH (10 mL) and toluene (50 mL). The sure and then dried in vacuo. Yield: 12.69 g (71.5%). GPC resulting organic phase was separated, concentrated at analysis: Mn=6520, Mw-14500, PD=2.23. 5,541,346 21 22 EXAMPLE 14 EXAMPLE 18

Polymerization of 3-Methyl-THF with Yttrium Polymerization of Cyclohexene Oxide with Triflate and Acetic Anhydride Lanthanium Triflate In a dry box, yttrium triflate (0.75 g) was weighed into an In a dry box, lanthanum triflate (0.75 g) was weighed in oven dried 100 mL RB flask equipped with a stirring bar. a oven dried 100 mL three neck flask equipped with a The flask was sealed with a rubber septum and removed stirring bar, reflux condenser and addition funnel. Toluene from the dry box. A nitrogen bleed was attached and (20 mL) was added via syringe and cyclohexene oxide (20 3-methyl-THF (20 mL) was added followed by acetic anhy- 10 mL) was slowly added via the addition funnel. The poly dride (0.75 g). After stirring overnight the polymerization merization was terminated after 2.75 hrs. via the addition of was terminated by the addition of 5% NaOH (10 mL) and HO (10 mL) and toluene (100 mL). The organic phase was THF (25 mL). The resulting organic phase was separated, separated, concentrated at reduced pressure and then dried concentrated at reduced pressure and dried under vacuum. under vacuum. Polymer yield: 12.4 g (63.9%). GPC analysis Yield: 6.12 g (34.50%). GPC analysis: Mn=437, Mw-808, 15 (bimodal distribution): Mn=4510, Mw-25700, PD-5.70 (PS PD=1.85. STD). EXAMPLE 1.5 EXAMPLE 19 Polymerization of THF with Yttrium Triflate and 20 Acetic Anhydride Continuous Polymerization of THF with Ytterbium In a dry box, yttrium triflate (0.75 g) was weighed into an Triflate and Acetic Anhydride oven dried 100 mL RB flask equipped with a stirring bar. A solution of THF (-500 mL) and ytterbium triflate (25 g) After sealing with a rubber septum the flask was removed 25 was charged into a 500 mL capacity ISCO pump, which was from the dry box and a nitrogen bleed attached. THF (20 connected to a 3 way 3.2 mm SS connector (“T” mixer) via mL) and acetic anhydride (1.00 mL) were added. After 17.5 8 cm of 3.2 mm SS tubing containing a check valve. A hrs. THF (20 mL) and acetic anhydride (1.00 mL) were second ISCO pump (500 mL capacity) was charged with added to the thick viscous solution. After an additional 2 hrs -100 mL of acetic anhydride and this was connected to the THF (20 mL) and acetic anhydride were again added to the 30 "T" mixer by 75 cm of 3.2 mm SS tubing also containing a polymerized solution. The polymerization was terminated check valve. The feed rate of the THFlytterbium triflate 2.5 hrs later via the addition of 5% NaOH (20 mL) and THF solution was 3.3 mL/min and that of the acetic anhydride (100 mL). The organic phase was separated, concentrated at was 0.25 mL/min. The "T" mixer was connected to a glass reduced pressure and dried under vacuum. Polymer yield: stirred holdup tank (approximately 60 mL volume) by 12 cm 32.3 g (61.23%). GPC analysis: Mn=2490, Mw-8440, 35 of 3.2 mm SS tubing. This tank was then connected to a PD-3.39 (PSSTD). second stirred holdup tank (approximately 55 mL volume) via Cajon flex tubing with ultra torr fitting (6.4 mm, 13 cm). EXAMPLE 16 This in turn was connected to a third glass reactor, plug flow (approximately 60 mL volume), again via Cajon flex tubing Polymerization of THF with Ytterbium Triflate 40 with ultra tort fitting (6.4 mm, 13 cm). The polymerized In a dry box, ytterbium triflate (1.00 g) was weighed in a solution exiting from the third reactor was fed to a stirred 100 mLRB flask equipped with a stirring bar. After sealing beaker containing water/diethyl ether. Each reactor was with a rubber septum the flask was removed from the dry equipped with thermal well port. During the polymerization box and a nitrogen blecd attached. THF (20 mL) was then the temperature in the first reactor stabilized to 41-42 C. added via syringe. The polymerization was allowed to 45 and that of the second reactor to 31-32° C. and that of the proceed overnight and then terminated via the addition of third reactor 26-27 C. After the contents of the THF/ HO (25 mL) and diethyl ether (75 mL). The organic phase ytterbium triflate pump was discharged, and two fractions of was separated, concentrated at reduced pressure and then polymer were collected, the pump was again refilled with a dried under vacuum. Polymer yield: 0.520 g (2.93%). GPC solution of THF (-500 mL) and ytterbium triflate (25 g). analysis: Mn=416000, Mw-842000, PD=2.02 (PSSTD). 50 Three fractions were collected. The last fraction was obtained by purging the system with diethyl ether. EXAMPLE 17 The organic phases were separated, concentrated at reduced pressure and then dried under vacuum giving the Polymerization of 7-Oxabicyclo[2.2.1]heptane with following: Ytterbium Triflate and Acetic Anhydride 55 In a dry box, ytterbium triflate (0.5 g) was weighed into Fraction Weight a 100 mLRB flask equipped with a stirring bar. After sealing 1. 106.86 g with a rubber septum, the flask was remove from the dry box 2 79.59 g and a nitrogen bleed attached. 7-Oxabicyclo2.2.1]heptane 60 3 56.97g (10 mL, distilled from potassium carbonate) was added 4 220.2 g followed by acetic anhydride (0.5 mL). After 1 hr. the 5 97.2 g polymerization was terminated by the addition of 5% NaOH (10 mL), THF (75 mL) and diethyl ether (-50 mL). The The aqueous phases from above were collected, concen organic phase was separate, concentrated at reduced pres- 65 trated at reduced pressure and then dried under vacuum at sure and then dried under vacuum, Polymer yield: 1.00 g. 180° C. giving a cream solid, 46.98g, representing a 93.94% GPC analysis: Mn=233, Mw-522, PD=2.24 (PS STD). recovery of the total ytterbium triflate catalyst used. 5,541,346 23 24 EXAMPLE 20 Polymer Time Polymer Yield (%) Polymerization of THF with Ytterbium Triflate 15 mins. 3.92 (Recovered from Example 19) and Acetic 30 mins. 34.94 Anhydride 45 mins. 43.74 In a dry box, ytterbium triflate (1.00g), recovered catalyst 60 mins 49.4 from Example 19, was weighed out in a 100 mL RB flask equipped with a stirring bar. A rubber septum was attached EXAMPLE 24 and the flask removed from the dry box. A nitrogen bleed 10 was attached and THF (20 mL) added followed by acetic anhydride (1.00 mL). After 1 hr. the polymerization was Polymerization of Refluxing THF with Yttrium terminated by the addition of water (25 mL), THF (25 mL) Triflate and Acetic Anhydride and diethyl ether (50 mL), the resulting organic phase was In a dry box, yttrium triflate (0.75 g) was weighed into an separated, concentrated at reduced pressure, then dried 15 oven dried 100 mL flask equipped with a stirred bar, a reflux under vacuum affording 13.42 g (75.65%) of polymer. condenser was attached, the flask sealed with rubber septum and removed from the dry box and a nitrogen bleed attached. EXAMPLE 21 THF (20 mL) was added and the resulting mixture heated to reflux via an oil bath (temp. -80° C.). Acetic anhydride (0.75 20 mL) was added to the stirred refluxing mixture. After 30 Polymerization of THF with Yttrium Triflate and minutes the polymerization was terminated via the addition Acetic Andyride at -78° C. of 5% NaOH (10 mL) and THF (50 mL). The cooled organic phase was separated, concentrated at reduced pressure, then In a dry box, yttrium triflate (0.75 g) was weighed in an dried under vacuum giving 6.44 g (36.30%) of polymer. oven dried 100 mL RB flask equipped with a stirring bar. 25 After sealing with a rubber septum, removal from the dry EXAMPLE 25 box and the attachment of a nitrogen bleed, THF (20 mL) was added. The resulting mixture was cooled to -78° C. Preparation of Ytterbium NafionQ Salt Acetic anhydride (0.75 mL) was then added, the polymer ization was terminated 5 hrs. later by the addition of water In a 300 mL RB flask were added ytterbium oxide (0.75 (25 mL) and diethyl ether (50 mL). After warming to room 30 g) and Nafion() perfluorinated ion exchange resin powder temperature the resulting organic phase was separated, con (300 mL, 5 wt.% solution in a mixture of lower aliphatic centrated at reduced pressure, then dried under vacuum alcohols and 10% water). The resulting mixture was heated affording 0.58 g (3.27%) of polymer. to 100° C. and stirred overnight. The resulting solution was 35 filtered and dried under vacuum at 150° C., affording 9.21 g EXAMPLE 22 of a light brown solid. EXAMPLE 26 Preparation of Didymium (Mischmetall) Triflate Polymerization of THF with Ytterbium Nafiong) Didymium (mischmetall) oxide (17 g) and water (50 mL) 40 Salt and Acetic Anhydride were added to a 200 mLRB flask equipped with stirring bar and an addition funnel and reflux condenser. Triflic acid (50 In a dry box, the ytterbium Nafion?) salt (1.00 g, from g) was slowly added via the addition funnel to the resulting Example 25) was added to each of four oven dried 100 mL stirred slurry. After the addition was completed a homoge RB flasks equipped with stirring bars. The flasks were sealed neous solution resulted, thus an additional 2.0 g of the oxide 45 with rubber septa and removed from the dry box and was added and the slurry heated to reflux for 2 hrs. The nitrogen bleeds attached. THF (20 mL) followed by acetic cooled slurry was filtered, the filtrate concentrated at anhydride (1.00 mL) were added to each flask. After 2, 3, 4 reduced pressure and then dried under vacuum at 50°-210 and 5 hrs. a polymerization was terminated by the addition C. affording 58.4 g of a pink solid. of water (25 mL) and diethyl ether (50 mL). The organic 50 phases were separated, concentrated at reduced pressure and then dried under vacuum to give the following: EXAMPLE 23 Polymer Time Polymer Yield (%) Polymerization of THF with Didymium 55 2 hrs, 5.24 (Mischmetall) Triflate Polymerization Time on 3 hrs. 1139 Polymer Yield 4 hrs. 17.08 In a dry box, didymium triflate (0.75 g) was added to each 5hrs. 22.66 of four separate oven dried 100 mLRB flasks equipped with stirring bars. The flasks were sealed with rubber septa and 60 removed from the dry box and nitrogen bleeds attached. EXAMPLE 27 THF (20 mL) followed by acetic anhydride (0.75 mL) were added to each flask. After 15, 30, 45 and 60 minutes, a Depolymerization of PolyTHF with Yttrium Triflate polymerization was terminated via the addition of 5% NaOH Polytetrahydrofuran 1000 (300 g, Aldrich) and yttrium (10 mL) and THF (50 mL). The resulting organic phases 65 triflate (9 g) were placed in a 500 mL three neck flask were separated, concentrated at reduced pressure and then equipped with a stirring bar, Vigreaux column (30.5 cm) and dried under vacuum. Polymer yields: a fractional distillation head. A nitrogen purge was then 5,541,346 25 26 attached and all other openings glass stoppered. The result was then added, after 1 hour the polymerization was termi ing mixture was then heated by an oil bath and the water nated via the addition of 5% NaOH and THF (50 mL), the clear distillate fractions collected as follows: organic phase separated and concentrated at reduced pres sure and then in vacuo, affording 13.32 g (78.08%) of Oil Bath Head Temp polymer. GPC analysis: Mn=4110, Mw-8860, PD=2.15 (PS Fraction Temp (°C) (°C) Weight STD). 1 171-75 64.5 67.49 2 176 64.5 71.84 EXAMPLE 31 3 176 64.5 32.84 4 178 64.5 58.67 10 5 178 64.5 56,71 Recovery of Catalyst from Depolymerization Total weight of distillate collected: 287.55 H NMR analyses of all five fractions confirmed the product to be THF. Water (100 mL) was added to the residue from Example Yield (Recovery): 95.85% 28, the resulting mixture was stirred at room temperature for 15 approximately 1 hour, the aqueous phase separated and EXAMPLE 28 concentrated at reduced pressure and dried in vacuo at 180° C. overnight affording a brown solid. This solid was again Depolymerization of Poly-THF with Yttrium dissolved in water, then filtrated, the filtrated concentrated at Triflate: Reuse of Catalyst reduced pressure. The resulting solid was dried under 20 vacuum at 180° C. overnight affording a cream solid: 6.48 To the residue remaining from Example 27 was added g (72%) of recovered catalyst. polytetrahydrofuran 1000 (300 g, Aldrich). The apparatus was reassembled the resulting mixture heated by an oil bath, and the resulting water clear distillate fractions were col EXAMPLE 32 lected as follows: 25

Oil Bath Head Temp Activity of Recovered Catalyst in the Fraction Temp (°C) (°C) Weight Polymerization of THF 170-174 63-64 43.39 30 In a dry box, the recovered catalyst of Example 31 (1 g) 2 174 64. 62.68 3 175 65 66.15 was placed in an oven dried 100 mL flask equipped with a 4 177 65 55.5 stirring bar. The flask was sealed with a rubber septum and 5 177 65 32.58 removed from the dry box and a nitrogen purge attached. THF (20 mL) was then added followed by acetic anhydride Total weight of distillate collected: 259.95g 35 Yield (Recovery): 86.65% (1 mL). After 1 hour the polymerization was terminated via Total time elapsed from start of collection to termination of Example: 2 hrs. the the addition of 5% NaOH and THF (50 mL), the organic 50 mins. phase separated, concentrated and dried in vacuo overnight affording 13.86 g (78.13%) of polymer. GPC Analysis: Mn=4460, Mw-9280, PD=2.08 (PS STD). EXAMPLE 29 40 Polymerization of Recovered THF with Ytterbium Triflate and Acetic Anhydride EXAMPLE 33 In a dry box, ytterbium triflate (1.00 g) was added to an oven dried 100 mL flask equipped with a stirring bar. The 45 Depolymerization of Poly-THF/3-Methyl-THF flask was then sealed with a rubber septum and removed Copolymer with Yttrium Triflate from the dry box and a nitrogen purge attached. Tetrahyd ofuran (20 mL) from the fourth fraction of Example 27 was Poly-tetrahydrofuran/3-methyl-tetrahydrofuran copoly added followed by 1 mL of acetic anhydride. After 1 hour no mer (308.6 g) containing 3385 ppm water and yttrium trifiate polymerization was apparent, thus an additional 1 mL of 50 (9 g) were placed in a 500 mL three neck flask equipped with acetic anhydride added. After 1 hour the polymerization was a stirring bar, Vigreaux column (30.5 cm), a thermometer terminated via the addition of 5% NaOH and THF (50 mL), and a fractional distillation head. A nitrogen purge was the organic phase separated, concentrated at reduced pres attached and all other opening glass stoppered. The resulting sure and then dried in vacuo overnight affording 10.31 g mixture was heated by an oil bath and the water clear (58%) of polymer. GPC analysis: Mn=1970, Mw-6650, 55 distillate fractions collected as follows: PD=3.38 (PS STD). Oil Bath Rxn. Head Weight EXAMPLE 30 Fraction Temp (C) Temp. (°C) Temp. (C.) (g)

60 1. 180-182 140-145 65-70 64.35 Polymerization of Recovered Purified THF with 2 182-84 140 69-70 T1.03 Ytterbium Triflate and Acetic Anhydride 3 183-185 140-144 70 69.35 4. 185 143 70 TO.12 Fractions 2-4 of experiment Example 27 were combined 5 185 70 22.35 and distilled from sodium/benzophenone. Twenty mL of this Total weight collected: 297.20 g dried THF was added to ytterbium triflate (1 g), previously 65 % Yield (Recovery): 96.47 weighed out in an oven dried 100 mL flask equipped with Total depolymerization time: 2 hrs. 25 mins. stirring bar and a nitrogen purge. Acetic anhydride (1 mL) 5,541,346 27 28 EXAMPLE 34 under vacuum. Polymer yields and GPC analysis:

Depolymeriation of PolyTHF, Diacetate Capped, Polymer, Polymer Mn with Yttrium Triflate Tine Yield (%) (PSSTD) Mw PD Polytetrahydrofuran which was diacetate capped (300 g, 15 mins. 39.35 O700 2000 2 Mn 1850) and yttrium triflate (9 g) were placed in a 500 mL 30 mills. 61.33 3900 7300 1.25 three-flask equipped with a stirring bar, Vigreaux (30.5 cm), 45 mins. 67.08 4200 19300 1.35 a thermometer and a fractional distillation head. A nitrogen T0 mins. 65.50 12400 19300 56 purge was attached and all other openings glass stoppered. The resulting mixture was heated by an oil bath and the 10 water clear distillate fractions collected as follows: EXAMPLE 37 Oil Bath Rxn. Head Weight Fraction Temp (°C) Temp. (°C) Temp. (°C) (g) 15 Polymerization of THF with 158-160 105-129 64 82.78 Bis(n-cyclopentadienyl)tetrahydrofuran-bis(trifluoro 2 160-16 16-129 64-66 62.91 3 161 6 64-67 77.71 methanesulfonato)Zirconium and Acetyl Chloride 4. 161-180 w 67-69 51.50 In a dry box, bis(n-cyclopentadienyl)tetrahydrofuran-bis Total weight Collected: 274.90 g 20 (trifluoromethanesulfonato)Zirconium (0.50 g) was added to % Yield (Recovery): 91.63 each of three separate oven dried 100 mL RB flasks Total depolymerization time: 1 hr. 25 mins. equipped with stirring bars. The flasks were sealed with rubber septa and removed from the dry box. After the EXAMPLE 35 attachment of nitrogen bleeds, THF (10 mL) and acetyl 25 chloride (0.375 mL) were added to each flask. After 15, 30, Polymerization of THF with and 45 minutes, a polymerization was terminated via the Bis(n-cyclopentadienyl)tetrahydrofuran-bis(trifluoro addition of water (25 mL), THF (50 mL) and ether (25 mL). methanesulfonato)Zirconium and Acetic Anhydride The resulting organic phases were washed repeatedly with water (3x25 mL), separated, concentrated at reduced pres In a dry box, bis (n-cyclopentadienyl)tetrahydrofuran 30 sure and then dried under vacuum. Polymer yields and GPC bis(trifluoromethanesulfonato)zirconium (0.50 g) was added analysis: to each of four separate oven dried 100 mL RB flasks equipped with stirring bars. The flasks were sealed with Polymer. Polymer Mn rubber septa and removed from the dry box. After the Time Yield (%) (PSSTD) Mw PD attachment of nitrogen bleeds THF (10 mL) and acetic 35 anhydride (0.50 mL) were added to each flask. After 15, 30, 5 mins. 59.85 T98O 0800 35 45 and 60 minutes, a polymerization was terminated via the 30 mins. 68.88 7470 1000 48 addition of water (25 mL), THF (50 mL) and ether (25 mL). 45 mins. 68.65 5620 992O T6 The resulting organic phases were separated, concentrated at reduced pressure and then dried under vacuum. Polymer 40 yields and GPC analysis: EXAMPLE 38 Polymer. Polymer Mn Time Yield (%) (PSSTD) Mw PD 45 Polymerization of THF with 5 mins. 39.34 12700 14100 111 Bis(n-cyclopentadienyl)-bis(trifluoromethanesulfonato)- 30 mins. 54.79 5000 19000 27 45 mins. 63.92 16000 2200 1.38 titanium and Acetyl Chloride 60 mins. 64.26 17200 24500 1.4 In a dry box, bis(n-cyclopentadienyl)-bis(trifluo 50 romethanesulfonato)titanium (0.50 g) was added to each of three separate oven dried 100 mL RB flasks equipped with EXAMPLE 36 stirring bars. The flasks were sealed with rubber septa and Polymerization of THF with then removed from the dry box. Nitrogen bleeds were Bis(n-cyclopentadienyl)-bis(trifluoromethanesulfonato)- attached and THF (10 mL) and acetyl chloride (0.375 mL) 55 were added to each flask. After 15, 30, and 45 minutes a titanium and Acetic Anhydride polymerization was terminated via the addition of water (25 In a dry box, bis(n-cyclopentadienyl)-bis(trifluo mL), ether (25 mL) and THF (50 mL). The separated organic romethanesulfonato) titanium (0.50 g) was added to each of phases were washed repeatedly with water (3x25 mL), then four separate oven dried 100 mL RB flasks equipped with separated, concentrated at reduced pressure and then dried stirring bars. The flasks were sealed with rubber septa and 60 under vacuum. Polymer yields: then removed from the dry box. Nitrogen bleeds were attached and THF (10 mL) and acetic anhydride (0.50 mL) Polymer. Time Polymer Yield (%) were added to each flask. After 15, 30, 45, 70 minutes a polymerization was terminated via the addition of water (25 15 mins. 46.11 mL), ether (25 mL) and THF (50 mL). The separated organic 65 30 mins. 66.85 phases were washed repeatedly with water (3x25 mL), then 45 mins. 7497 separated, concentrated at reduced pressure and then dried 5,541,346 29 30 EXAMPLE 39 and the resulting mixture placed in the freezer. The resulting precipitate was filtered and then dried under vacuum. Yield: Polymerization of THF with 10.02g. 'HNMR (CDC): 6.68 (s, 10H), 3.76 (m, 4H), 1.84 Bis(n-cyclopentadienyl)tetrahydrofuran-bis(trifluoro (m, 4H). methanesulfonato)zirconium and Acetic Anhydride 5 In a dry box, bis (n-cyclopentadienyl)tetrahydrofuran EXAMPLE 42 bis(trifluoromethanesulfonato)zirconium (0.50 g) was added to each of three separate oven dried 100 mL RB flasks equipped with stirring bars. The flasks were sealed with Preparation of rubber septa and removed from the dry box. After the 10 Bis(pentamethyl-n-cyclopentadienyl)-bis(trifluoro attachment of nitrogen bleeds THF (20 mL) and acetic methanesulfonato)Zirconium anhydride (1.00 mL) were added to each flask. After 15, 30, In a dry box, bis(pentamethylcyclopentadienyl)Zirconium and 45 minutes, a polymerization was terminated via the dichloride (10.00 g) was dissolved in THF (300 mL). To this addition of water (25 mL), THF (50 mL) and ether (25 mL). 15 solution, with stirring, was added a solution of silver triflate The resulting organic phases were separated, concentrated at (12.46 g) in THF (100 mL). After 15 minutes the precipi reduced pressure and then dried under vacuum. Polymer tated silver chloride was filtered off and the resulting filtrate yields and GPC analysis: concentrated to approximately half its volume at reduced pressure. Hexane (250 mL) was added and the resulting Polymer. Polymer M 20 mixture placed in the freezer. The resulting yellow precipi Time Yield (%) (PSSTD) Mw PD tate was filtered and then dried under vacuum. Yield: 6.02 g. 15 mins. 15.22 11300 11900 1.05 H NMR (CDC1): 2.12 (s). 30 mins. 30.50 18100 20300 1.12 45 mins. 39.35 21300 25500 120 25 EXAMPLE 43

EXAMPLE 40 Preparation of Bis(n-cyclopentadienyl)-bis(trifluoro methanesulfonato)vanadium Copolymerization of THF and 3-Methyl-THF with Bis (n-cyclopentadienyl)tetrahydrofuran-bis(trifluo 30 In a dry box, vanadocene dichloride (5.00 g) was dis romethanesulfonato)zirconium and Acetic Anhy solved in THF (300 mL). To this solution, with stirring, was dride added a solution of silver triflate (11.19 g) in THF (100 mL). After 15 minutes the precipitated silver chloride was filtered In a dry box, bis(n-cyclopentadienyl)tetrahydrofuran-bis off and the resulting filtrate concentrated to approximately (trifluoromethanesulfonato)Zirconium (0.50 g) was added to 35 half its volume at reduced pressure. Hexane (250 mL) was each of three separate oven dried 100 mL RB flasks added and the resulting mixture placed in the freezer. The equipped with stirring bars. The flasks were sealed with resulting green precipitate was filtered and then dried under rubber septa and removed from the dry box. After the vacuum. Yield: 6.99g. attachment of nitrogen bleeds THF (7.5 mL), 3-Methyl-THF (2.5 mL) and acetic anhydride (0.10 mL) were added to each flask. After 15, 30, and 45 minutes, a polymerization was 40 EXAMPLE 44 terminated via the addition of water (25 mL), THF (50 mL) and ether (25 mL). The resulting organic phases were separated, concentrated at reduced pressure and then dried Polymerization of THF with under vacuum. "H NMR analysis indicates ~10.5% incor bis(n-cyclopentadienyl)tetrahydrofuranbis(trifluoro poration of 3-methyl-THF in the polymers. Polymer yields 45 methanesulfonato)zirconium and Acetic Anhydride and GPC analysis: in Hexane In a dry box, bis(n-cyclopentadienyl)tetrahydrofuran-bis Polymer, Polymer MI (trifluoromethanesulfonato)Zirconium (0.50 g) was added to Time Yield (%) (PSSTD) Mw PD 50 each of three separate oven dried 100 mL RB flasks equipped with stirring bars. The flasks were sealed with 15 mins. 24.8 8500 9430 1.11 30 mins. 41.15 1400 13300 1.17 rubber septa and removed from the dry box. After the 45 mins. 49.15 12200 15500 1.27 attachment of nitrogen bleeds hexane (10 mL), THF (20 mL) and acetic anhydride (0.10 mL) were added to each flask. 55. After 15, 30, and 45 minutes, a polymerization was termi nated via the addition of water (25 mL), THF (50 mL) and EXAMPLE 41 ether (25 mL). The resulting organic phases were separated, Preparation of concentrated at reduced pressure and then dried under Bis(n-cyclopentadienyl)tetrahydrofuran-bis vacuum. Polymer yields and GPC analysis: (trifluoromethanesulfonato)hafnium 60 Polymer. Polymer M In a dry box, hafnocene dichloride (9.93 g) was dissolved Time Yield (%) (PSSTD) Mw PD in THF (300 mL). To this solution, with stirring, was added a solution of silver triflate (14.12 g) in THF (100 mL). After 15 mins. 4.96 1390 2020 1.45 10 minutes the precipitated silver chloride was filtered off 65 30 mins. 9.24 2980 3470 1.16 and the resulting filtrate concentrated to approximately half 45 mins. 20.40 3410 4030 1.18 its volume at reduced pressure. Hexane (250 mL) was added 5,541,346 31 32 EXAMPLE 45 Polymer. Polymer Mn Polymerization of Cyclohexene Oxide with Time Yield (%) (PSSTD) Mw PD bis(n-cyclopentadienyl)tetrahydrofuran-bis(trifluoro 15 mins. 17.59 10600 13000 122 methanesulfonato)Zirconium 30 mins. 45.32 14100 18800 134 45 mins. 60.43 15100 2700 1.44 In a dry box, bis (n-cyclopentadienyl)tetrahydrofuran 60 mins. 62.57 10500 21000 2.00 bis(trifluoromethanesulfonato)Zirconium (0.50 g) was added to an oven dried 100 mLRB flask equipped with stirring bar, reflux condenser and addition funnel. The flask was sealed 10 EXAMPLE 48 with a rubber septum and removed from the dry box. After the attachment of a nitrogen bleed, toluene (10 mL) was Polymerization of THF with added. Then a solution of cyclohexene oxide (20 mL) and Bis(pentamethylcyclopentadienyl)bis(trifluoro toluene (10 mL) was slowly added via the addition funnel. methanesulfonato)zirconium and Acetic Anhydride After 60 minutes the polymerization was terminated by the 15 addition of water (25 mL) and toluene (100 mL). The In a dry box, bis(pentamethylcyclopentadi separated organic phase was concentrated at reduced pres enyl)bis(trifluoromethanesulfonato)zirconium (0.50 g) was sure and then dried under vacuum. Polymer yield: 2.28 g. added to each of four separate oven dried 100 mLRB flasks GPC analysis (PSSTD): Mn=13600, Mw-24500, PD=1.80. equipped with stirring bars. The flasks were sealed with 20 rubber septa and removed from the dry box. After the attachment of nitrogen bleeds THF (10 mL) and acetic EXAMPLE 46 anhydride (0.50 mL) were added to each flask. After 15, 30, 45 and 60 minutes, a polymerization was terminated via the addition of water (25 mL), THF (50 mL) and ether (25 mL). Polymerization of THF with 25 The resulting organic phases were separated, concentrated at Bis(n-cyclopentadienyl)tetrahydrofuran-bis(trifluoro reduced pressure and then dried under vacuum. Polymer methanesulfonato)hafnium and Acetic Anhydride yields and GPC analysis: In a dry box, bis (n-cyclopentadienyl)tetrahydrofuran bis(trifluoromethanesulfonato)hafnium (0.50 g) was added Polymer. Polymer Mn to each of four separate oven dried 100 mL RB flasks 30 Time Yield (%) (PSSTD) Mw PD equipped with stirring bars. The flasks were sealed with 15 mins. 33.26 0600 1900 12 rubber septa and removed from the dry box. After the 30 mins. 44.64 2100 14800 1.23 attachment of nitrogen bleeds THF (10 mL) and acetic 45 mins. 60.09 3400 17600 1.31 anhydride (0.50 mL) were added to each flask. After 15, 30, 60 mins. 70.23 15100 20900 1.38 45 and 60 minutes, a polymerization was terminated via the 35 addition of water (25 mL), THF (50 mL) and ether (25 mL). The resulting organic phases were separated, concentrated at EXAMPLE 49 reduced pressure and then dried under vacuum. Polymer yields and GPC analysis: Polymerization of THF with 40 Bis(pentamethylcyclopentadienyl)bis(trifluoro Polymer. Polymer Mn methanesulfonato)Zirconium and Adipoyl Chloride Time Yield (%) (PSSTD) Mw PD In a dry box, bis(pentamethylcyclopentadi 5 mins. 32.13 1200 12200 1.09 enyl)bis(trifluoromethanesulfonato)zirconium (0.50 g) was 30 mins. 48.TO 5200 18600 1.22 45 45 mins. 58.74 17400 23100 1.33 added to an oven dried 100 mL RB flask equipped with a 60 mins. 60.54 7000 24100 1.42 stirring bar. The flask was sealed with a rubber septum and removed from the dry box. After the attachment of a nitrogen bleed THF (10 mL) and adipoyl chloride (0.50 mL) were added. After 45 minutes, the polymerization was 50 EXAMPLE 47 terminated via the addition of water (25 mL), THF (50 mL) and ether (25 mL). The resulting organic phase was sepa rated, concentrated at reduced pressure and then dried under Polymerization of THF with vacuum. Polymer yield: 5.87 g (66.17%). Bis(n-cyclopentadienyl)-bis(trifluoromethanesulfonato)- vanadium and Acetic Anhydride 55 EXAMPLE 50 In a dry box, bis(n-cyclopentadienyl)-bis(trifluo Polymerization of THF with romethanesulfonato)vanadium (0.50 g) was added to each of Bis(pentamethylcyclopentadienyl)bis(trifluoro four separate oven dried 100 mL RB flasks equipped with methanesulfonato)Zirconium and Acetyl Bromide stirring bars. The flasks were sealed with rubber septa and 60 removed from the dry box. After the attachment of nitrogen In a dry box, bis(pentamethylcyclopentadi bleeds THF (10 mL) and acetic anhydride (0.50 mL) were enyl)bis(trifluoromethanesulfonato)zirconium (0.50 g) was added to each flask. After 15, 30, 45 and 60 minutes, a added to an oven dried 100 mL RB flask equipped with a polymerization was terminated via the addition of water (25 stirring bar. The flask was sealed with rubber septum and mL), THF (50 mL) and ether (25 mL). The resulting organic 65 removed from the dry box. After the attachment of a phases were separated, concentrated at reduced pressure and nitrogen bleed THF (10 mL) and acetyl bromide (0.50 mL) then dried under vacuum. Polymer yields and GPC analysis: were added. After 45 minutes, the polymerization was 5,541,346 33 34 terminated via the addition of water (25 mL), THF (50 mL) The flask was sealed with a rubber septum and removed and ether (25 mL). The resulting organic phase was sepa from the dry box. After the attachment of a nitrogen bleed rated, concentrated at reduced pressure and then dried under THF (10 mL) and diglycolyl chloride (1.00 mL) were added vacuum. Polymer yield: 2.20 g. to the flask. After 45 minutes the polymerization was ter minated via the addition of water (25 mL), THF (50 mL) and EXAMPLE 51 ether (25 mL). The resulting organic phase was separated, concentrated at reduced pressure and then dried under Polymerization of THF with vacuum. Polymer yield: 0.64 g. Bis(n-cyclopentadienyl)-bis(trifluoromethanesulfonato)- vanadium and Acetyl Bromide 10 EXAMPLE 55 In a dry box, bis(n-cyclopentadienyl)-bis(trifluo romethanesulfonato)vanadium (0.50 g) was added to an oven dried 100 mL RB flask equipped with a stirring bar. Copolymerization of THF/3-Methyl-THF with The flask was sealed with rubber septum and removed from Bis(n-cyclopentadienyl)tetrahydrofuran-bis(trifluoro the dry box. After the attachment of a nitrogen bleed THF 15 methanesulfonato)Zirconium and Diglycolyl (10 mL) and acetyl bromide (0.50 mL) were added. After 60 Chloride minutes, the polymerization was terminated via the addition of water (25 mL), THF (50 mL) and ether (25 mL). The In a dry box, bis(n-cyclopentadienyl)tetrahydrofuran-bis resulting organic phase was separated, concentrated at (trifluoromethanesulfonato)Zirconium (0.50 g) was added an 20 oven dried 100 mL RB flask equipped with a stirring bar. reduced pressure and then dried under vacuum. Polymer The flask was sealed with a rubber septum and removed yield: 3.68 g. from the dry box. After the attachment of a nitrogen bleed THF (7.5 mL), 3-methyl-THF (2.5 mL) and diglycolyl EXAMPLE 52 chloride (1.00 mL) were added to the flask. After 45 minutes Polymerization of THF with 25 the polymerization was terminated via the addition of water Bis(n-cyclopentadienyl)tetrahydrofuran-bis(trifluoro (25 mL), THF (50 mL) and ether (25 mL). The resulting organic phase was separated, concentrated at reduced pres methanesulfonato)hafnium and Acetyl Bromide sure and then dried under vacuum. Polymer yield: 0.63 g. In a dry box, bis(n-cyclopentadienyl)tetrahydrofuran-bis (trifluoromethanesulfonato)hafnium (0.50 g) was added to 30 an oven dried 100 mLRB flask equipped with a stirring bar. EXAMPLE 56 The flask was sealed with a rubber septum and removed from the dry box. After the attachment of a nitrogen bleed Polymerization of THF With THF (10 mL) and acetyl bromide (0.50 mL) were added. Bis(pentamethylcyclopentadienyl)-bis(trifluoro After 30 minutes, the polymerization was terminated via the 35 methanesulfonato)Zirconium and Trifluoroacetic addition of water (25 mL), THF (50 mL) and ether (25 mL). Anhydride The resulting organic phase was separated, concentrated at reduced pressure and then dried under vacuum. Polymer In a dry box, bis(pentamethylcyclopentadienyl)-bis(trif yield: 2.29 g. luoromethanesulfonato)Zirconium (0.50 g) was added to an 40 oven dried 100 mL RB flask equipped with a stirring bar. EXAMPLE 53 The flask was sealed with a rubber septum and removed from the dry box. After the attachment of a nitrogen bleed Polymerization of Oxepane with THF (10 mL) and trifluoroactic anhydride (0.50 mL) were bis(n-cyclopentadienyl)tetrahydrofuran-bis(trifluoro added. After 3 hrs., the polymerization was terminated via methanesulfonato)Zirconium and Acetic anhydride 45 the addition of water (25 mL), THF (50 mL) and ether (25 In a dry box, bis(n-cyclopentadienyl)tetrahydrofuran-bis mL). The resulting organic phase was separated, concen (trifluoromethanesulfonato)Zirconium (0.05 g) was added to trated at reduced pressure and then dried under vacuum. an oven dried 50 mL RB flask equipped with stirring bar. Polymer yield: 4.89 g. The flask was sealed with a rubber septum and removed 50 from the dry box. After the attachment of a nitrogen bleed EXAMPLE 57 oxepane (1.00 mL) and acetic anhydride (0.05 mL) were added via syringe. After 60 minutes the polymerization was terminated by the addition of water (10 mL) and ether (25 Copolymerization of THF/3-Methyl-THF with mL). The separated organic phase was concentrated at Bis(n-cyclopentadienyl)tetrahydrofuran-bis(trifluoro reduced pressure and then dried under vacuum. Polymer 55 methanesulfonato)Zirconium and Adipoyl Chloride yield: 0.87 g. In a dry box, bis(n-cyclopentadienyl)tetrahydrofuran-bis (trifluoromethanesulfonato)Zirconium (0.50 g) was added an EXAMPLE 54 oven dried 100 mL RB flask equipped with a stirring bar. Polymerization of THF with 60 The flask was sealed with a rubber septum and removed Bis(n-cyclopentadienyl)tetrahydrofuran-bis(trifluoro from the dry box. After the attachment of a nitrogen bleed methanesulfonato)Zirconium and Diglycolyl THF (7.5 mL), 3-methyl-THF (2.5 mL) and adipoyl chloride (1.00 mL) were added to the flask. After 60 minutes the Chloride polymerization was terminated via the addition of water (25 In a dry box, bis(n-cyclopentadienyl)tetrahydrofuran-bis 65 mL), THF (50 mL) and ether (25 mL). The resulting organic (trifluoromethane-sulfonato)Zirconium (0.50 g) was added phase was separated, concentrated at reduced pressure and an oven dried 100 mLRB flask equipped with a stirring bar, then dried under vacuum. Polymer yield: 5.98 g. 5,541,346 35 36 EXAMPLE 58 Polymer. Polymer Mn Time Yield (%) (PSSTD) Mw PD Polymerization of THF with Yttrium Triflate and Acetyl Chloride 15 mins. 21.98 O20 2000 95 30 mins. 26.94 926 780 192 In a dry box, yttrium trifiate (0.75 g) was added to each 45 mins. 32.86 1040 2060 1.97 of four separate oven dried 100 mLRB flasks equipped with stirring bars. The flasks were sealed with rubber septa and then removed from the dry box. Nitrogen bleeds were EXAMPLE 6 attached and THF (20 mL) and acetyl chloride (0.75 mL) 10 were added to each flask. After 15, 30, 45 and 60 minutes a Polymerization of THF with Erbium Triflate and polymerization was terminated via the addition of water (25 Acetyl Chloride mL), ether (25 mL) and THF (50 mL). The resulting organic phases were separated, concentrated at reduced pressure and In a dry box, erbium triflate (0.75 g) was added to each of then dried under vacuum. Polymer yields and GPC analysis: 5 three separate oven dried 100 mL RB flasks equipped with stirring bars. The flasks were sealed with rubber septa and then removed from the dry box. Nitrogen bleeds were Polymer. Polymer Ma attached and THF (20 mL) and acetyl chloride (0.75 mL) Time Yield (%) (PSSTD) Mw PD were added to each flask. After 15, 30 and 45 minutes a 20 5 mins. 49.21 1610 3470 2.15 polymerization was terminated via the addition of water (25 30 mins. 50.05 1520 3390 2.22 mL), ether (25 mL) and THF (50 mL). The resulting organic 45 mins. 49.77 1510 3570 2.36 phases were separated, concentrated at reduced pressure and 60 mins. 52.76 1740 3940 2.26 then dried under vacuum. Polymer yields and GPC analysis: 25 Polymer. Polymer Mn EXAMPLE 59 Time Yield (%) (PSSTD) Mw PD 15 mins. 53.83 1570 3400 2.7 30 mins. 56.09 1650 4090 2.47 Polymerization of THF with Ytterbium Triflate and 30 45 mins. 56.99 1710 4310 2.5 Acetyl Chloride In a dry box, ytterbium triflate (0.75 g) was added to each EXAMPLE 62 of three separate oven dried 100 mL RB flasks equipped with stirring bars. The flasks were sealed with rubber septa 35 . Polymerization of THF with Scandium Triflate and and then removed from the dry box. Nitrogen bleeds were Acetyl Chloride attached and THF (20 mL) and acetyl chloride (0.75 mL) were added to each flask. After 15, 30 and 45 minutes a In a dry box, scandium trifiate (0.75 g) was added to each polymerization was terminated via the addition of water (25 of three separate oven dried 100 mL RB flasks equipped mL), ether (25 mL) and THF (50 mL). The resulting organic 40 with stirring bars. The flasks were sealed with rubber septa phases were separated, concentrated at reduced pressure and and then removed from the dry box. Nitrogen bleeds were then dried under vacuum. Polymer yields and GPC analysis: attached and THF (20 mL) and acetyl chloride (0.75 mL) were added to each flask. After 15, 30 and 45 minutes a polymerization was terminated via the addition of water (25 Polymer. Polymer Mn mL), ether (25 mL) and THF (50 mL). The resulting organic Time Yield (%) (PSSTD) Mw PD 45 phases were separated, concentrated at reduced pressure and 15 mins. 52.59 170 3790 2.22 then dried under vacuum. Polymer yields and GPC analysis: 30 mins. 52.82 1730 4540 2.6 45 mins. 52.25 1730 4690 2.7 Polymer. Polymer Mn 50 Time Yield (%) (PSSTD) Mw PD 15 mins. 53.33 1750 4180 2.38 EXAMPLE 60 30 mins. 54.17 1690 4630 2.73 45 nins. 53.49 1570 5660 3.6 Polymerization of THF with Didymium 55 (Mischmetall) Triflate and Acetyl Chloride EXAMPLE 63 In a dry box, didymium triflate (0.75 g) was added to each Polymerization of THF with Copper Triflate and of three separate oven dried 100 mL RB flasks equipped Acetyl Chloride with stirring bars. The flasks were sealed with rubber septa 60 and then removed from the dry box. Nitrogen bleeds were In a dry box, copper triflate (0.75 g) was added to each of attached and THF (20 mL) and acetyl chloride (0.75 mL) three separate oven dried 100 mL RB flasks equipped with were added to each flask. After 15, 30 and 45 minutes a stirring bars. The flasks were sealed with rubber septa and polymerization was terminated via the addition of water (25 then removed from the dry box. Nitrogen bleeds were mL), ether (25 mL) and THF (50 mL). The resulting organic 65 attached and THF (20 mL) and acetyl chloride (0.75 mL) phases were separated, concentrated at reduced pressure and were added to each flask. After 15, 30 and 45 minutes a then dried under vacuum. Polymer yields and GPC analysis: polymerization was terminated via the addition of water (25 5,541,346 37 38 mL), ether (25 mL) and THF (50 mL). The resulting organic were added to each flask. After 45, 60 and 75 minutes a phases were separated, concentrated at reduced pressure and polymerization was terminated via the addition of water (25 then dried under vacuum. Polymer yields and GPC analysis: mL), ether (25 mL) and THF (50 mL). The resulting organic phases were separated, concentrated at reduced pressure and Polymer. Polymer Mn then dried under vacuum. Polymer yields: Time Yield (%) (PSSTD) Mw PD 15 mins. 23.56 1010 2150 2.3 Polymer. Time Polymer Yield (%) 30 mins. 3174 1250 2720 2.8 45 mins. 43.24 1390 3180 2.29 15 mins. 5.64 O 30 mins. 6.88 45 mins. 7.6

EXAMPLE 64 EXAMPLE 67 Polymerization of THF with Tin Trifiate and Acetyl 15 Chloride Polymerization of THF with Yttrium Triflate and In a dry box, tintriflate (0.75 g) was added to each of three Adipoyl Chloride separate oven dried 100 mLRB flasks equipped with stirring In a dry box, yttrium triflate (1.00 g) was added to each bars. The flasks were sealed with rubber septa and then of three separate oven dried 100 mL RB flasks equipped removed from the dry box. Nitrogen bleeds were attached 20 with stirring bars. The flasks were sealed with rubber septa and THF (20 mL) and acetyl chloride (0.75 mL) were added and then removed from the dry box. Nitrogen bleeds were to each flask. After 15, 30 and 45 minutes a polymerization attached and THF (20 mL) and adipoly chloride (1.00 mL) was terminated via the addition of water (25 mL), ether (25 were added to each flask. After 15, 30 and 45 minutes a mL) and THF (50 mL). The resulting organic phases were polymerization was terminated via the addition of water (25 separated, concentrated at reduced pressure and then dried 25 mL), ether (25 mL) and THF (50 mL). The resulting organic under vacuum. Polymer yields: phases were separated, concentrated at reduced pressure and then dried under vacuum. Polymer yields and GPC analysis: Polymer. Time Polymer Yield (%) 30 Polymer. Polymer MI 15 mins. 23.96 Tine Yield (%) (PSSTD) Mw PD 30 mins. 40.53 45 mins. 41.60 15 mins. 56.20 2020 5340 2.6 30 mins. 58.62 2350 4790 2.04 45 mins. 58.40 1910 5250 2.75 EXAMPLE 65 35 Polymerization of THF with Zirconium Triflate and EXAMPLE 68 Acetyl Chloride Polymerization of THF with Terephthaloyl Chloride In a dry box, zirconium triflate (0.75 g) was added to each 40 and Yttrium Triflate of three Separate oven dried 100 mL RB flasks equipped with stirring bars. The flasks were sealed with rubber septa In a dry box, yttrium triflate (0.75 g) and terephthaloyl and then removed from the dry box. Nitrogen bleeds were chloride (2.00 g) were added to a 100 mLRB flask equipped attached and THF (20 mL) and acetyl chloride (0.75 mL) with a stiring bar. The flask was sealed with a rubber septum were added to each flask. After 15, 30 and 45 minutes a 45 and removed from the dry box. A nitrogen purge was polymerization was terminated via the addition of water (25 attached and THF (20 mL) addeded via syringe. After 90 mL), ether (25 mL) and THF (50 mL). The resulting organic minutes the polymerization was terminated by the addition phases were separated, concentrated at reduced pressure and of water (25 mL) and THF (25 mL) and ether (50 mL). The then dried under vacuum. Polymer yields and GPC analysis: separated organic phase was concentrated at reduced pres sure and then dried under vacuum. Polymer yield: 2.25 g. 50 GPC Analysis (PS STD.): Mn=40900, Mw-63000, Polymer, Polymer MI PD=154. Time Yield (%) (PSSTD) Mw PD 5 mins. 49.04 2040 4320 2.12 EXAMPLE 69 30 mins. 64.43 2200 4880 22 45 mins. 65.84 2290 5190 2.27 55 Polymerization of THF with Neodymium Triflate and Acetyl Bromide In a dry box, neodymium triflate (0.75 g) was added to EXAMPLE 66 each of four separate oven dried 100 mLRB flasks equipped Polymerization of THF with Zinc Triflate and 60 with stirring bars. The flasks were sealed with rubber septa Acetyl Chloride and then removed from the dry box. Nitrogen bleeds were attached and THF (20 mL) and acetyl bromide (1.50 mL) In a dry box, Zinc triflate (0.75 g) was added to each of were added to each flask. After 15, 30, 45 and 60 minutes a three separate oven dried 100 mL RB flasks equipped with polymerization was terminated via the addition of water (25 stirring bars. The flasks were sealed with rubber septa and 65 mL), ether (25 mL) and THF (50 mL). The resulting organic then removed from the dry box. Nitrogen bleeds were phases were separated, concentrated at reduced pressure and attached and THF (20 mL) and acetyl chloride (0.75 mL) then dried under vacuum. Polymer yields: 5,541,346 39 40 mL) and THF (50 mL). The resulting organic phases were separated, concentrated at reduced pressure and then dried Polymer. Time Polymer Yield (%) under vacuum. Polymer yields and GPC analysis: 15 mins. 27.11 30 mins, 27.06 45 mins. 28.3 Polymer. Polymer M 60 mins. 27.28 Time Yield (%) (PSSTD) Mw PD 15 mills. 63.64 3780 11000 2.91 30 mins. 70.85 3270 92.70 2.82 EXAMPLE 70 45 mins. 70.85 2780 97.40 3.49 O 60 mins. 74.18 2930 8330 2.84 Polymerization of THF with Diglycolyl Chloride and Ytterbium Trifate EXAMPLE 74 In a dry box, ytterbium triflate (1.00 g) was added to a 100 mL RB flask equipped with a stirring bar. The flask was 15 Polymerization of THF with Copper Triflate and sealed with a rubber septum and removed from the dry box. Acetic Anhydride A nitrogen purge was attached and THF (20 mL) addeded via syringe, followed by diglycolyl chloride (2.00 mL, In a dry box, copper triflate (0.75 g) was added to each of 97%). After 60 minutes the polymerization was terminated four separate oven dried 100 mL RB flasks equipped with by the addition of water (25 mL) and THF (25 mL) and ether 20 stirring bars. The flasks were sealed with rubber septa and (50 mL). The separated organic phase was concentrated at then removed from the dry box. Nitrogen bleeds were reduced pressure and then dried under vacuum. Polymer attached and THF (20 mL) and acetic anhydride (0.75 mL) yield: 9.53 g. were added to each flask. After 45, 60, 75 and 90 minutes a polymerization was terminated via the addition of water (25 EXAMPLE 71 25 mL) and THF (50 mL). The separated organic phases were separated, concentrated at reduced pressure and then dried Polymerization of THF with Diglycolyl Chloride under vacuum. Polymer yields and GPC analysis: and Zirconium Triflate Polymer. Polymer M In a dry box, zirconium triflate (1.00 g) was added to a 100 30 mL RB flask equipped with a stiring bar. The flask was Tine Yield (%) (PSSTD) Mw PD sealed with a rubber septum and removed from the dry box. 45 nins. 23.90 10500 2100 2.01 60 mins. 30.0 2000 23400 1.95 A nitrogen purge was attached and THF (20 mL) added via 75 mins. 35.00 11400 23500 2.07 syringe, followed by diglycolyl chloride (2.00 mL, 97%). 90 mins. 53.2 3900 25900 .86 After 60 minutes the polymerization was terminated by the 35 addition of water (25 mL) and THF (25 mL) and ether (50 mL). The separated organic phase was concentrated at reduced pressure and then dried under vacuum. Polymer EXAMPLE 75 yield: 7.32 g. Polymerization of THF with Zirconium Triflate and 40 Acetic anhydride EXAMPLE 72 In a dry box, zirconium triflate (0.75 g) was added to each Copolymerization of THF/3-Methyl-THF with of four separate oven dried 100 mLRB flasks equipped with Ytterbium Triflate and Adipoyl Chloride stirring bars. The flasks were sealed with rubber septa and In a dry box, ytterbium triflate (0.50 g) was added an oven 45 removed from the dry box. Nitrogen bleeds were attached dried 100 mLRB flask equipped with a stirring bar. The flask and THF (20 mL) and acetic anhydride (0.75 mL) were was sealed with a rubber septum and removed from the dry added to each flask. After 15, 30, 45 and 60 minutes, a box. After the attachment of a nitrogen bleed THF (7.5 mL), polymerization was terminated via the addition of water (25 3-methyl-THF (2.5 mL) and adipoyl chloride (1.00 mL) mL) and THF (50 mL). The resulting organic phases were 50 separated, concentrated at reduced pressure and then dried were added to the flask. After 60 minutes the polymerization under vacuum. Polymer yields: was terminated via the addition of water (25 mL), THF (50 mL) and ether (25 mL). The resulting organic phase was separated, concentrated at reduced pressure and then dried Polymer. Time Polymer Yield (%) under vacuum. Polymer yield: 5.2 g. 55 15 mins. 58.06 30 mins. 65.84 EXAMPLE 73 45 mins. 66.91 60 mins. 7.87 Polymerization of THF with Scandium Triflate and Acetic Anhydride 60 In a dry box, scandium triflate (0.75 g) was added to each EXAMPLE 76 of four separate oven dried 100 mLRB flasks equipped with Polymerization of THF with Tin Trifiate and Acetic stirring bars. The flasks were sealed with rubber septa and Anhydride removed from the dry box. After the attachment of nitrogen bleeds THF (20 mL) and acetic anhydride (0.75 mL) were 65 In a dry box, tin triflate (0.75 g) was added to each of four added to each flask. After 15, 30, 45 and 60 minutes, a separate oven dried 100 mLRB flasks equipped with stirring polymerization was terminated via the addition of water (25 bars. The flasks were sealed with rubber septa and removed 5,541,346 41 42 from the dry box. Nitrogen bleeds were attached and THF merization was terminated via the addition of water (25 mL) (20 mL) and acetic anhydride (0.75 mL) were added to each and THF (50 mL). The resulting organic phase was sepa flask. After 15, 30, 45 and 90 minutes, a polymerization was rated, concentrated at reduced pressure and then dried under terminated via the addition of water (25 mL) and THF (50 vacuum. Polymer yield: 5.68 g. mL). The resulting organic phases were separated, concen trated at reduced pressure and then dried under vacuum. EXAMPLE 80 Polymer yields: Copolymerization of THF/3-Methyl-THF with Polymer. Time Polymer Yield (%) Copper Triflate and Acetic Anhydride 10 15 mins. 24.01 In a dry box, copper triflate (0.50 g) was added to an oven 30 mins. 44.08 dried 100 mLRB flask equipped with a stirring bar. The flask 45 mins. 54.68 was sealed with a rubber septum and removed from the dry 60 mins. 58.40 box. A nitrogen bleed was attached and THF (7.5 mL) and 15 3-methyl-THF (2.5 mL) were added followed by acetic anhydride (1.00 mL). After 60 minutes the polymerization EXAMPLE 77 was terminated via the addition of water (25 mL) and THF Polymerization of THF with Zinc Triflate and (50 mL). The resulting organic phase was separated, con Acetic Anhydride centrated at reduced pressure and then dried under vacuum. 20 Polymer yield: 2.48 g. In a dry box, Zinc triflate (0.75 g) was added to an oven dried 100 mLRB flask equipped with a stirring bar. The flask EXAMPLE 81 was sealed with a rubber septum and removed from the dry box. A nitrogen bleed was attached and THF (20 mL) and Copolymerization of THF/3-Methyl-THF with Tin acetic anhydride (0.75 mL) were added. After stirring over 25 night the polymerization was terminated via the addition of Triflate and Acetic Anhydride water (25 mL) and THF (50 mL). The resulting organic In a dry box, tin triflate (0.50 g) was added to an oven phase was separated, concentrated at reduced pressure and dried 100 mLRB flask equipped with a stirring bar. The flask then dried under vacuum. Polymer Yield: 3.17 g (17.87%). was sealed with a rubber septum and removed from the dry 30 box. A nitrogen bleed was attached and THF (7.5 mL) and EXAMPLE 78 3-methyl-THF (1.6 mL) were added followed by acetic anhydride (1.00 mL). After 60 minutes the polymerization Depolymerization of Polytetrahydrofuran with was terminated via the addition of water (25 mL) and THF Copper Triflate (50 mL). The resulting organic phase was separated, con 35 centrated at reduced pressure and then dried under vacuum. Polytetrahydrofuran diol, Mn=-1,000, and copper triflate Polymer yield: 442 g. (9 g) were placed in a 500 mL three neck flask equipped with a stirring bar, Vigreaux column (12") and a fractional distillation head. A nitrogen purge was attached and all other EXAMPLE 82 openings were glass stoppered. The resulting mixture was heated by an oil bath and the resulting water clear distillate 40 Copolymerization of THF/3-Methyl-THF with fractions collected as follow: Scandium Trifate and Acetic Anhydride In a dry box, scandium triflate (0.50 g) was added to an Oil Bath Rxn Temp. Head Temp. Weight oven dried 100 mL RB flask equipped with a stirring bar. Fraction Temp (C.) (°C) (°C) (g) 45 The flask was sealed with a rubber septum and removed 168 135-139 64 47.85 from the dry box. A nitrogen bleed was attached and THF 2 168 128-135 64 57.09 (7.5 mL) and 3-methyl-THF (2.5 mL) were added followed 3 168 18-128 66 53.67 by acetic anhydride (1.00 mL). After 45 minutes the poly 4. 168 106-128 66 57.77 merization was terminated via the addition of water (25 mL) 5 168 106 66 76.30 50 and THF (50 mL). The resulting organic phase was sepa rated, concentrated at reduced pressure and then dried under Total weight of distillate collected: 292.68 g vacuum. Polymer yield: 5.81 g. Yield (Recovery): 97.56% Total depolymerization time from start of collection to EXAMPLE 83 termination of experiment: 1 hr. 45 mins. 55 Polymerization of THF with Copper Triflate and EXAMPLE 79 Trifluoroacetic Anhydride Copolymerization of THF/3-Methyl-THF with In a dry box, copper trifiate (1.00 g) was added to an oven Zirconium Triflate and Acetic Anhydride 60 dried 100 mLRB flask equipped with a stirring bar. The flask was sealed with a rubber septum and removed from the dry In a dry box, zirconium triflate (0.50 g) was added to an box. A nitrogen bleed was attached and THF (20 mL) and oven dried 100 mL RB flask equipped with a stirring bar. trifluoroacetic anhydride (2.00 mL) were added. After stir The flask was sealed with a rubber septum and removed ring for 3 hrs. the polymerization was terminated via the from the dry box. A nitrogen bleed was attached and THF 65 addition of water (25 mL) and THF (50 mL). The resulting (7.5 mL) and 3-methyl-THF (2.5 mL) were added followed organic phase was separated, concentrated at reduced pres by acetic anhydride (1.00 mL). After 45 minutes the poly sure and then dried under vacuum. Polymer Yield: 7.5 g. 5,541,346 43 44 EXAMPLE 84 and removed from the dry box. After the attachment of nitrogen bleeds THF (20.00 mL) and trifluoroacetic acid Polymerization of THF with Trifluoroacetic Acid (5.00 mL) were added to each flask. After 120, 150 and 180 and Ytterbium Triflate at 45° C. minutes a polymerization was terminated via the addition of water (25 mL), THF (50 mL) and ether (25 mL). The In a dry box, ytterbium triflate (5.00 g) was added to an resulting organic phases were separated, concentrated at oven dried 100 mL RB flask equipped with a stirring bar. reduced pressure and then dried under vacuum. Polymer The flask was sealed with rubber septa and removed from yields and GPC analyses: the dry box. After the attachment of nitrogen bleeds THF (20.00 mL) and trifluoroacetic acid (4.00 mL) were added to the flask. Then flask was them immediately placed in an oil 10 Polymer. Polymer Mn bath maintained at 45° C. After 120 minutes the polymer Time Yield (g) (PSSTD) Mw PD ization was terminated via the addition of water (25 mL), 120 mins. 57 22700 32900 1.45 THF (50 mL) and ether (25 mL). The resulting organic phase 50 mins. 2.75 24600 37900 154 was separated, concentrated at reduced pressure and then 80 mins. 3.69 30300 4.6400 54 dried under vacuum. Polymer yield: 6.61 g. GPC analysis 5 (PSSTD.): Mn=5680, Mw-9090, PD=1.60. EXAMPLE 88 EXAMPLE 85 Polymerization of THF with Trifluoroacetic Acid 20 Polymerization of THF with Trifluoroacetic Acid and Ytterbium Triflate at 45 C. and Erbium Triflate In a dry box, ytterbium triflate (5.00 g) was added to an In a dry box, erbium triflate (4.00 g) was added to each of oven dried 100 mL RB flask equipped with a stirring bar. five separate oven dried 100 mL RB flasks equipped with The flask was sealed with rubber septa and removed from 25 stirring bars. The flasks were sealed with rubber septa and the dry box. After the attachment of a nitrogen bleed THF removed from the dry box. After the attachment of nitrogen (20.00 mL) and trifluoroacetic acid (5.00 mL) were added to bleeds THF (20.00 mL) and trifluoroacetic acid (5.00 mL) the flask. The flask was then immediately placed in an oil were added to each flask. After 60, 90, 120, 150 and 180 bath maintained at 45° C. After 120 minutes the polymer minutes a polymerization was terminated via the addition of ization was terminated via the addition of water (25 mL), 30 water (25 mL), THF (50 mL) and ether (25 mL). The THF (50 mL) and ether (25 mL). The resulting organic phase resulting organic phases were separated, concentrated at was separated, concentrated at reduced pressure and then reduced pressure and then dried under vacuum. Polymer dried under vacuum. Polymer yield: 3.07 g. GPC analysis yields and GPC analyses: (PSSTD.): Mn=3290, Mw-4810, PD=1.46. 35 Polymer. Polymer Mn EXAMPLE 86 Time Yield (g) (PD STD.) Mw PD 60 mins. 2.02 3300 20900 57 Polymerization of THF with Trifluoroacetic Acid 90 mins, 3.3 26500 36900 39 and Ytterbium Triflate 120 mins. 4.84 26600 39700 49 40 150 mins. 5.08 30600 49600 1.62 In a dry box, ytterbium triflate (2.00, 3.00, 4.00 and 5.00 80 mins. 5.58 27900 45700 1.63 g) was added to each of four separate oven dried 100 mLRB flasks equipped with stirring bars. The flasks were sealed with rubber septa and removed from the dry box. After the attachment of nitrogen bleeds THF (20.00 mL) and trifluo 45 EXAMPLE 89 roacetic acid (2.00 mL) were added to each flask. After 90 minutes the polymerizations were terminated via the addi Copolymerization of THF/3-Methyl-THF with tion of water (25 mL), THF (50 mL) and ether (25 mL). The resulting organic phases were separated, concentrated at Trifluoroacetic Acid and Ytterbium Triflate reduced pressure and then dried under vacuum. Polymer 50 In a dry box, ytterbium triflate (5.00 g) was added to yields and GPC analyses: separate oven dried 100 mLRB flasks equipped with stirring bars. The flasks were sealed with rubber septa and removed Ytterbium Polymer Mn from the dry box. After the attachment of nitrogen bleeds Triflate (g) Yield (g) (PSSTD.) Mw PD THF (15.00 mL and 3-methyl-THF (5.00 mL) were added to 55 each flask. Trifluoroacetic acid (3 and 4 mL) was then added 2.00 5.32 60200 95600 1.59 to each flask. After 120 minutes the polymerizations were 3.00 5.95 58500 894.00 153 terminated via the addition of water (25 mL), THF (50 mL) 4.00 6.70 4600 T6700 166 and ether (25 mL). The resulting organic phases were separated, concentrated at reduced pressure and then dried under vacuum. Polymer yields and GPC analyses: EXAMPLE 87 60 Polymerization of THF with Trifluoroacetic Acid Trifluoroacetic Polymer MI and Yttrium Triflate Acid Yield (g) (PSSTD.) Mw PD 3 InL 5.37 24500 3.7500 1.53 In a dry box, yttrium triflate (3.00 g) was added to each 65 of three separate oven dried 100 mL RB flasks equipped 4 I. 3.9 20900 30300 1.45 with stirring bars. The flasks were sealed with rubber septa 5,541,346 45 46 EXAMPLE 90 EXAMPLE 93 Polymerization of THF with Pentafluoropropionic Polymerization of THF with Trifluoroacetic Acid and Ytterbium Trifate Anhydride/Trifluoroacetic Acid and Ytterbium 5 Triflate In a dry box, ytterbium triflate (5.00 g) was added to an oven dried 100 mL RB flask equipped with a stirring bar. In a dry box, ytterbium triflate (3.00 g) was added to each The flask was sealed with a rubber septum and removed of four separate oven dried 100 mLRB flasks equipped with from the dry box. After the attachment of a nitrogen bleed stirring bars. The flasks were sealed with rubber septa and 10 THF (20.00 mL) and pentafluoropropionic acid (5.00 mL) removed from the dry box. After the attachment of nitrogen were added via syringe. After 150 minutes the polymeriza bleeds THF (20.00 mL) was added to each flask. Trifluora tion was terminated via the addition of water (25 mL), THF cetic anhydride and trifluoroacetic acid were added together (50 mL) and ether (25 mL). The resulting organic phase was via syringes in the ratios shown below. After 60 minutes the Separated, concentrated at reduced pressure and then dried polymerizations were terminated via the addition of water 15 under vacuum. Polymer yield; 7.00 g. GPC analysis: (25 mL), THF (50 mL) and ether (25 mL). The resulting Mn=20100, Mw-38700, PD=1.92 (PS STD.). organic phases were separated, concentrated at reduced pressure and then dried under vacuum. Polymer yields and GPC analyses: EXAMPLE 94 20 Polymerization of THF with Cyanoacetic Acid and Trifluoroacetic Ytterbium Triflate Anhydrided Polymer Mn Trifluoroacetic Acid (mL) Yield (g) (PSSTD.) Mw PD In a dry box, ytterbium triflate (5.00 g) and cyanoacetic 512 10.66 8090 13400 66 acid (5.00 g) were added to an oven dried 100 mL RB flask 5/3 9.2 6600 10100 154 25 equipped with a stirring bar. The flask was sealed with a 514 7.13 5200 8150 157 rubber septum and removed from the dry box. After the 515 4.86 4200 59100 41 attachment of a nitrogen bleed THF (20.00 mL) was added via syringe. After 150 minutes the polymerization was terminated via the addition of water (25 mL), THF (50 mL) 30 and ether (25 mL). The resulting organic phase was sepa EXAMPLE 91 rated, concentrated at reduced pressure and then dried under vacuum. Polymer yield: 6.15g. GPC analysis: Mn=22900, Mw=33900, PD=148 (PSSTD). Polymerization of THF with Trifluoroacetic Anhydride/Trifluoroacetic Acid and Ytterbium 35 EXAMPLE 95 Trifate In a dry box, ytterbium triflate (3.00 g) was added to an Polymerization of THF with Trifluoroacetic Acid oven dried 100 mL RB flask equipped with a stirring bar. and Aluminum Triflate The flask was sealed with a rubber septum and removed from the dry box. After the attachment of a nitrogen bleed 40 In a dry box, aluminum triflate (1.5 g) was added to an THF (20.00 mL) was added to the flask. Trifluoracetic oven dried 100 mL RB flask equipped with a stirring bar. anhydride (3.00 mL) and trifluoroacetic acid (5.00 mL) were The flask was sealed with a rubber septum and removed added together via syringe. After 60 minutes the polymer from the dry box. After the attachment of a nitrogen bleed ization was terminated via the addition of water (25 mL), THF (10 mL) and trifluoroacetic acid (1.5 mL) were added 45 via syringe. After 120 minutes the polymerization was THF (50 mL) and ether (25 mL). The resulting organic phase terminated via the addition of water (25 mL), THF (50 mL) was separated, concentrated at reduced pressure and then and ether (25 mL). The resulting organic phase was sepa dried under vacuum. Polymer yield: 6.85g. GPC analysis: rated, concentrated at reduced pressure and then dried under Mn-5910, Mw-9970, PD=1.50 (PS STD.). vacuum. Polymer yield: 4.17 g. GPC analysis: Mn=28500, 50 Mw=52000, PD=1.82 (PSSTD.). EXAMPLE 92 EXAMPLE 96 Polymerization of THF with Pentafluoropropionic Polymerization of THF with Trifluoroacetic Acid Acid and Ytterbium Triflate 55 and Zirconium Trifate In a dry box, ytterbium triflate (5.00 g) was added to an In a dry box, Zirconium triflate (1.5 g) was added to an oven dried 100 mL RB flask equipped with a stirring bar. oven dried 100 mL RB flask equipped with a stirring bar. The flask was sealed with a rubber septum and removed The flask was sealed with a rubber septum and removed from the dry box. After the attachment of a nitrogen bleed 60 from the dry box. After the attachment of a nitrogen bleed THF (20.00 mL) and pentafluoropropionic acid (2.00 mL) THF (10 mL) and trifluoroacetic acid (1.5 mL) were added were added via syringe. After 150 minutes the polymeriza via syringe. After 120 minutes the polymerization was tion was terminated via the addition of water (25 mL), THF terminated via the addition of water (25 mL), THF (50 mL) (50 mL) and ether (25 mL). The resulting organic phase was and ether (25 mL). The resulting organic phase was sepa separated, concentrated at reduced pressure and then dried 65 rated, concentrated at reduced pressure and then dried under under vacuum. Polymer yield: 9.42 g. GPC analysis: vacuum. Polymer yield: 5.63 g. GPC analysis: Mn=33300, Mn-71500, Mw-126000, PD=1.77 (PSSTD.). Mwa-52600, PD=1.58 (PS STD.). 5,541,346 47 48 EXAMPLE 97 EXAMPLE 101 Polymerization of THF with Pentafluoropropionic Copolymerization of THF/3-Methyl-THF with Acid and Aluminum Triflate Trifluoroacetic Acid and Ytterbium Triflate In a dry box, aluminum triflate (2.5 g) was added to an In a dry box, ytterbium triflate (5.00 g) was added to an oven dried 100 mL RB flask equipped with a stirring bar. oven dried 100 mL RB flask equipped with a stirring bar. The flask was sealed with a rubber septum and removed The flask was sealed with a rubber septum and removed from the dry box. After the attachment of a nitrogen bleed from the dry box. After the attachment of a nitrogen bleed THF (10.00 mL) and pentafluoropropionic acid (0.90 mL) THF (15.00 mL), 3-methyl-THF (5.00 mL) and trifluoro were added via syringe. After 120 minutes the polymeriza 10 acetic acid (3.00 mL) were added via syringe. After 120 tion was terminated via the addition of water (25 mL), THF minutes the polymerization was terminated via the addition (50 mL) and ether (25 mL). The resulting organic phase was of water (25 mL), THF (50 mL) and ether (25 mL). The separated, concentrated at reduced pressure and then dried resulting organic phase was separated, concentrated at under vacuum. Polymer yield: 6.73 g. GPC analysis: 15 reduced pressure and then dried under vacuum. Polymer Mn=11700, Mw-20600, PD=1.76 (PSSTD.). yield: 5.37 g. GPC analysis: Mn=24500, Mwe37500, PD=1.53 (PSSTD.). EXAMPLE 98 EXAMPLE 102 Polymerization of THF with Chlorodifluoroacetic 20 Acid and Zirconium Triflate Polymerization of THF with Acetic Acid and Ytterbium Triflate In a dry box, zirconium triflate (2.5 g) was added to an oven dried 100 mL RB flask equipped with a stirring bar. In a dry box, ytterbium triflate (5.00 g) was added to each The flask was sealed with a rubber septum and removed of four separate oven dried 100 mLRB flasks equipped with from the dry box. After the attachment of a nitrogen bleed 25 stirring bars. The flasks were sealed with rubber septa and THF (10.00 mL) and chlorodifluoroacetic acid (2.50 mL) removed from the dry box. After the attachment of nitrogen were added via syringe. After 120 minutes the polymeriza bleeds THF (20.00 mL) and acetic acid (5.00 mL) were tion was terminated via the addition of water (25 mL), THF added to each flask. After 3, 4, 5 and 24 hours a polymer (50 mL) and ether (25 mL). The resulting organic phase was ization was terminated via the addition of water (25 mL), separated, concentrated at reduced pressure and then dried 30 THF (50 mL) and ether (25 mL). The resulting organic under vacuum. Polymer yield: 5.55 g. GPC analysis: phases were separated, washed with water (2x50 mL), Mn=19600, Mw-35300, PD=1.80 (PSSTD.). concentrated at reduced pressure and then dried under vacuum. Polymer yields and GPC analyses: EXAMPLE 99 35 Polymer. Polymer Mn Polymerization of THF with 4-Nitrobenzoic Acid Time (Hrs.) Yield (g) (PSSTD.) Mw PD and Aluminum Triflate 3 1.15 17900 34,600 1.93 In a dry box, aluminum trifiate (1.50 g) and 4-nitroben 4. 1.38 18400 33700 183 40 5 1.7 16400 34000 2.07 zoic acid (4.50 g) were added to an oven dried 100 mL RB 24 5.29 13000 30400 2.33 flask equipped with a stirring bar. The flask was sealed with a rubber septum and removed from the dry box. After the attachment of a nitrogen bleed THF (20.00 mL) was added via syringe. After 30 minutes the polymerization was ter EXAMPLE 103 minated via the addition of water (25 mL), THF (50 mL) and 45 ether (25 mL). The resulting organic phase was washed with Polymerization of THF with Formic Acid (96%) water (2X1000 mL), separated, concentrated at reduced Acid and Ytterbium Trifiate pressure and then dried under vacuum. Polymer yield: 4.43 In a dry box, ytterbium triflate (5.00 g) was added to each g. GPC analysis: Mn=37000, Mw-51000, PD=1.38 (PS of six separate oven dried 100 mL RB flasks equipped with STD.). 50 stirring bars. The flasks were sealed with rubber septa and removed from the dry box. After the attachment of nitrogen EXAMPLE 100 bleeds THF (20.00 mL) and formic acid (96%, 0.75 mL) were added to each flask. After 2, 3, 4, 5, 6 and 24 hours a Polymerization of THF with Trifluoroacetic Acid polymerization was terminated via the addition of water (25 and Yttrium Triflate 55 mL), THF (50 mL) and ether (25 mL). The resulting organic phases were separated, washed with water (2x50 mL), In a dry box, yttrium triflate (3.00 g) was added to an oven concentrated at reduced pressure and then dried under dried 100 mLRB flask equipped with a stirring bar. The flask vacuum. Polymer yields and GPC analyses: was sealed with a rubber septum and removed from the dry box. After the attachment of a nitrogen bleed THF (20.00 60 mL) and trifluoroacetic acid (5.00 mL) were added via syringe. After 180 minutes the polymerization was termi Polymer. Polymer M nated via the addition of water (25 mL), THF (50 mL) and Time (Hrs.) Yield (g) (PSSTD.) Mw PD ether (25 mL). The resulting organic phase was separated, 2 125 4300 29500 2.06 concentrated at reduced pressure and then dried under 65 3 1.65 15100 30300 2.00 vacuum. Polymer yield: 3.69g. GPC analysis: Mn=30300, 4 2.27 17600 32700 1.88 Mw-46400, PD=1.54 (PSSTD.). 5,541,346 49 SO under vacuum. Polymer yield: 7.32 g. GPC analysis: -continued Mn=2470, Mw-5250, PD=2.13 (PSSTD.). Polymer. Polymer M EXAMPLE 107 Time (Hrs.) Yield (g) (PSSTD.) Mw PD 5 2.72 16700 30800 85 Polymerization of THF with Trichloroacetic Acid 6 3.29 15300 298.00 1.95 and Aluminum Trifiate 24 7.93 10700 23100 2.6 In a dry box, aluminum triflate (4.5 g) and trichloroacetic acid (4.5 g) were added to an oven dried 100 mL RB flask 10 equipped with a stirring bar. The flask was sealed with a EXAMPLE 104 rubber septum and removed from the dry box. After the Polymerization of THF with Formic Acid (96%) attachment of a nitrogen bleed THF (10.00 mL) was added Acid and Ytterbium Triflate via syringe. After 120 minutes the polymerization was 15 terminated via the addition of water (25 mL), THF (50 mL) In a dry box, ytterbium triflate (15.77 g) was added to and ether (25 mL). The resulting organic phase was washed each of six separate oven dried 100 mLRB flasks equipped with water (2x50 mL), separated, concentrated at reduced with stirring bars. The flasks were sealed with rubber septa pressure and then dried under vacuum. Polymer yield: 5.0 g. and removed from the dry box. After the attachment of GPC analysis: Mn=33500, Mw-801.00, PD=2.39 (PSSTD). nitrogen bleeds THF (20.00 mL) and formic acid (96%, 2.00 20 mL) were added to each flask. After 2, 3, 4, 5, 6 and 24 hours EXAMPLE O8 a polymerization was terminated via the addition of water (25 mL), THF (50 mL) and ether (25 mL). The resulting Polymerization of THF with organic phases were separated, washed with water (2x50 11-Cyano-1-undecanoic Acid and Ytterbium Triflate mL), concentrated at reduced pressure and then dried under 25 In a dry box, ytterbium triflate (10.00 g) and 11-cyano vacuum. Polymer yields and GPC analyses: 1-undecanoic acid (5.00 g) were added to an oven dried 100 mL RB flask equipped with a stirring bar. The flask was Polymer. Polymer Mn sealed with a rubber septum and removed from the dry box. Time (Hrs.) Yield (g) (PSSTD) Mw PD After the attachment of a nitrogen bleed THF (20.00 mL) 30 2 167 4350 10900 2.51 was added via syringe. After 6 hrs. the polymerization was 3 2.22 5560 12000 2.6 terminated via the addition of water (25 mL), THF (50 mL) 4. 2.83 5320 12400 2.34 and ether (25 mL). The resulting organic phase was sepa 5 3.09 54.60 12100 2.22 rated, washed with 5% sodium bicarbonate (2x2.5 mL), 6 3.28 5390 11700 2.9 24 5.82 3050 7860 2.58 concentrated at reduced pressure and then dried under 35 vacuum. Polymer yield: 5.61 g. EXAMPLE 109 EXAMPLE 105 Polymerization of THF with 4-Acetylbutyric Acid Polymerization of THF with Pyruvonitrile and 40 and Ytterbium Triflate Ytterbium Triflate In a dry box, ytterbium triflate (10.00 g) was added to an In a dry box, ytterbium triflate (3.00 g) was added to a 100 oven dried 100 mL RB flask equipped with a stirring bar. mL round bottom flask equipped with a stirring bar. The The flask was sealed with a rubber septum and removed flask was sealed with a rubber septum and removed from the from the dry box. After the attachment of a nitrogen bleed dry box. After the attachment of a nitrogen bleed THF (20.00 45 THF (20.00 mL) and 4-acetylbutyric (1.00 mL) were added mL) was added followed by pyruvonitrile (95%, 2.00 mL). via syringe. After 90 minutes the polymerization was ter After 60 minutes the polymerization was terminated by the minated via the addition of water (25 mL), THF (50 mL) and addition of water (10 mL), THF (25 mL) and diethyl ether ether (25 mL). The resulting organic phase was separated, (25 mL). The resulting organic phase was separated, con washed with 5% sodium bicarbonate (2x2.5 mL), concen centrated at reduced pressure and then dried under vacuum. 50 trated at reduced pressure and then dried under vacuum. Polymer yield: 1.44 g. GPC analysis: Mn=52700, Polymer yield: 3.25 g. Mw-67000, PD=1.27 (PSSTD.). EXAMPLE 110 EXAMPLE 106 55 Polymerization of THF with Glycolic Acid and Polymerization of THF with Acetic Acid/Acetic Ytterbium Trifate Anhydride and Yttrium Triflate In a dry box, ytterbium triflate (10.00 g) and glycolic acid In a dry box, yttrium triflate (1.00 g) was added to an oven (99%, 1.00 g) were added to an oven dried 100 mLRB flask dried 100 mLRB flask equipped with a stirring bar. The flask 60 equipped with a stirring bar. The flask was sealed with a was sealed with a rubber septum and removed from the dry rubber septum and removed from the dry box. After the box. After the attachment of a nitrogen bleed THF (20.00 attachment of a nitrogen bleed THF (20.00 mL) was added mL), acetic acid (2.00 mL) and acetic anhydride (2.00 mL) via syringe. After 90 minutes the polymerization was ter were added via syringe. After 60 minutes the polymerization minated via the addition of water (25 mL), THF (50 mL) and was terminated via the addition of water (25 mL), THF (50 65 ether (25 mL). The resulting organic phase was separated, mL) and ether (25 mL). The resulting organic phase was concentrated at reduced pressure and then dried under separated, concentrated at reduced pressure and then dried vacuum. Polymer yield: 4.76 g. 5,541,346 S1 52 EXAMPLE 11 EXAMPLE 116 Polymerization of THF with Gold(III) Triflate and Preparation of Bismuth Triflate Acetic Anhydride BiCl, (630 mg, 2 mmol) was slurried in CHCl (20 mL). 5 In a dry box, gold(III) trifiate (0.5 g) was added to an oven Triflic acid (900 mg, 6 mmol) was added dropwise, and the dried 100 mLRB flask equipped with a stirring bar. The fiask mixture was stirred overnight at room temperature. The was sealed with a rubber septum and removed from the dry solvent was removed to give 0.9 g of an off white solid. 'F box. A nitrogen bleed was attached and THF (10.00 mL) and NMR (DMSO-d): 8–77.3. acetic anhydride (1.00 mL) were added. After stirring for 60 O minutes the polymerization was terminated via the addition EXAMPLE 12 of water (25 mL), ether (25 mL) and THF (50 mL). The resulting organic phase was separated, concentrated at reduced pressure and then dried under vacuum. Polymer Polymerization of THF with Bismuth Triflate and 5 Yield: 6.04 g. GPC analysis: Mn=5240, Mw=9060, PD=1.73 Acetic Anhydride (PSSTD.). In a dry box, bismuth triflate (0.5 g) was added to an oven dried 100 mLRB flask equipped with a stirring bar. The flask EXAMPLE 117 was sealed with a rubber septum and removed from the dry box. A nitrogen bleed was attached and THF (10.00 mL) and 20 Preparation of Y(OSOCF)Cl acetic anhydride (1.00 mL) were added. After stirring for 60 Solid Y(OTf) (540 mg, 1 mmol) and YCl (98 mg, 0.5 minutes the polymerization was terminated via the addition mmol) were mixed, and this mixture was poured into stirred of water (25 mL), ether (25 mL) and THF (50 mL). The THF (30 mL). The mixture became warm as the solid resulting organic phase was separated, concentrated at dissolved. The Solution was stirred for 15 min, and the THF reduced pressure and then dried under vacuum. Polymer 25 was removed. 'F NMR (DMSO-d): 8-77.3. Yield: 5.71 g. GPC analysis: Mn=8350, Mw-12400, PD=149 (PS STD.). EXAMPLE 118

EXAMPLE 3 Polymerization of THF with Y(OSOCF)Cl and 30 Acetic Anhydride Preparation of Zr(OSOCF)Zr(OCOCH.) In a dry box, Y(OSOCF)2Cl (0.5 g) was added to an oven dried 100 mL RB flask equipped with a stirring bar. Solid Zr(OTf) (0.5 g) and Zr(CFCO) (0.5 g) were The flask was sealed with a rubber septum and removed mixed and THF (25 mL) was added. The mixture was stirred 35 from the dry box. A nitrogen bleed was attached and THF for 15 minutes at room temperature. The solvent was (10.00 mL) and acetic anhydride (1.00 mL) were added. removed and 0.9 g of off white solid was collected. 'F After stirring for 60 minutes the polymerization was termi NMR (CDCl): 8-78.3, -76.2 (Zr(CFCO) comes at nated via the addition of water (25 mL), ether (25 mL) and 8-75.8). THF (50 mL). The resulting organic phase was separated, 40 concentrated at reduced pressure and then dried under EXAMPLE 1.4 vacuum. Polymer Yield: 2.95 g. GPC analysis: Mn=7390, Mw-12800, PD-1.73 (PS STD.). Polymerization of THF with EXAMPLE 119 Zr(OSOCF)Zr(OCOCH) and Acetic Anhydride 45 In a dry box, Zr(OSOCF)Zr(OCOCH) (0.5 g) was Preparation of Y(OSOCF)Cl. added to an oven dried 100 mL RB flask equipped with a Solid Y(OTf) (540 mg, 1 mmol) and YCl (390 mg, 2 stirring bar. The flask was sealed with a rubber septum and mmol) Were mixed, and this mixture was poured into stirred removed from the dry box. A nitrogen bleed was attached THF (30 mL). The mixture became warm as the solid and THF (10.00 mL) and acetic anhydride (1.00 mL) were 50 dissolved. The solution was stirred for 15 min, and the THF added. After stirring for 60 minutes the polymerization was was removed. 'F NMR (DMSO-d): 8-77.2 terminated via the addition of water (25 mL), ether (25 mL) and THF (50 mL). The resulting organic phase was sepa EXAMPLE 120 rated, concentrated at reduced pressure and then dried under vacuum. Polymer Yield: 5.01 g. GPC analysis: Mn=6900, 55 Polymerization of THF with Y(OSOCF)Cl and Mw-10500, PD=1.53 (PS STD.). Acetic Anhydride In a dry box, Y(OSOCF)Cl. (0.5 g) was added to an EXAMPLE 115 oven dried 100 mL RB flask equipped with a stirring bar. 60 The flask was sealed with a rubber septum and removed Preparation of Gold Triflate from the dry box. A nitrogen bleed was attached and THF (10.00 mL) and acetic anhydride (1.00 mL) were added. AuBr (0.90g, 2.1 mmol) was slurried in CHCl (20 mL) After stirring for 60 minutes the polymerization was termi and triflic acid (0.90 g, 6.3 mmol) was added dropwise. The nated via the addition of water (25 mL), ether (25 mL) and mixture was stirred overnight at room temperature. The 65 THF (50 mL). The resulting organic phase was separated, solvent was removed and 0.77 g of black solid was collected. concentrated at reduced pressure and then dried under 'F NMR (DMSO-d): 8-76.9. vacuum. Polymer Yield: 0.09 g. 5,541,346 S3 54 EXAMPLE 121 EXAMPLE 126 Polymerization of THF with Ruthenium(III) Triflate Preparation of Ta(OSOCF).OCHCH and Acetic Anhydride Ta(OEt) (813 mg, 2 mmol) was dissolved in CHCl2 (20 In a dry box, ruthenium(III) triflate (0.5 g) was added to mL). Triflic acid (1.5g, 10 mol) was added dropwise and the an oven dried 100 mLRB flask equipped with a stirring bar. solution stirred overnight at room temperature. The solvent The flask was sealed with a rubber septum and removed was removed to produce a colorless oil. H and 'F NMR from the dry box. A nitrogen bleed was attached and THF show a mixture of compounds. H NMR (CDC): 81.85 (t), (10.00 mL) and acetic anhydride (1.00 mL) were added. 1.9 (t), 4.1, (q), 4.15 (broad, q). 10 After stirring for 30 minutes the polymerization was termi nated via the addition of water (25 mL), ether (25 mL) and EXAMPLE 122 THF (50 mL). The resulting organic phase was separated, concentrated at reduced pressure and then dried under 5 vacuum. Polymer Yield: 5.25 g. GPC analysis: Mn=7960, Polymerization of THF with Mw-12400, PD=1.56 (PS STD.). Ta(OSOCF).OCHCH and Acetic Anhydride EXAMPLE 127 In a dry box, Ta(OSOCF).OCHCH (0.5 g) was added to an oven dried 100 mL RB flask equipped with a stirring Preparation of Palladium(II) Triflate bar. The flask was sealed with a rubber septum and removed 20 from the dry box. A nitrogen bleed was attached and THF PdCl2 (1.0g, 5.6 mmol) was slurried in CHCl (20 mL) (10.00 mL) and acetic anhydride (1.00 mL) were added. and triflic acid (1.7g, 11.3 mmol) was added dropwise. The After stirring for 60 minutes the polymerization was termi mixture was stirred at room temperature overnight. The nated via the addition of water (25 mL), ether (25 mL), and solvent was removed and 0.9 g of rust color solid was THF (50 mL). The resulting organic phase was separated, 25 collected. 'F NMR (CDCl): 8–78.5. concentrated at reduced pressure and then dried under vacuum. Polymer Yield: 6.29 g. GPC analysis: Mn=2320, EXAMPLE 128 Mw-5400, PD=2.33 (PS STD.). Polymerization of THF with Palladium(II) Triflate 30 and Acetic Anhydride EXAMPLE 123 In a dry box, palladium(II) triflate (0.5 g) was added to an oven dried 100 mL RB flask equipped with a stirring bar. Preparation of Iron(III) Bis-triflate-acetylacetonate The flask was sealed with a rubber septum and removed Fe (acac) (1.0g, 2.8 mmol) was dissolved in CHCl (15 35 from the dry box. A nitrogen bleed was attached and THF mL), and triflic acid (850 mg, 5.7 mmol) was added drop (10.00 mL) and acetic anhydride (1.00 mL) were added. wise. The purple solution was stirred overnight at room After stirring for 60 minutes the polymerization was termi temperature. The solvent was removed to give a dark oil. nated via the addition of water (25 mL), ether (25 mL) and THF (50 mL). The resulting organic phase was separated, 40 concentrated at reduced pressure and then dried under EXAMPLE 124 vacuum. Polymer Yield: 0.73 g. GPC analysis: Mn=27100, Mw=32500, PD=1.20 (PS STD.). Polymerization of THF with Iron(III) Bis-Triflate-Acetylacetonate and Acetic Anhydride EXAMPLE 29 45 In a dry box, iron(III) bis-triflate-acetylacetonate (0.5 g) Polymerization of THF with Niobium(V). Trifiate was added to an oven dried 100 mLRB flask equipped with and Acetic Anhydride a stirring bar. The flask was sealed with a rubber septum and In a dry box, niobium(V) triflate (0.5 g) was added to an removed from the dry box. A nitrogen bleed was attached oven dried 100 mL RB flask equipped with a stirring bar. and THF (10.00 mL) and acetic anhydride (1.00 mL) were 50 The flask was sealed with a rubber septum and removed added. After stirring for 60 minutes the polymerization was from the dry box. A nitrogen bleed was attached and THF terminated via the addition of water (25 mL), ether (25 mL) (10.00 mL) and acetic anhydride (1.00 mL) were added. and THF (50 mL). The resulting organic phase was sepa After stirring for 60 minutes the polymerization was termi rated, concentrated at reduced pressure and then dried under nated via the addition of water (25 mL), ether (25 mL) and vacuum. Polymer Yield: 5.63 g. GPC analysis: Mn=8330, 55 THF (50 mL). The resulting organic phase was separated, Mw-16100, PD=1.94 (PS STD.). concentrated at reduced pressure and then dried under vacuum. Polymer Yield: 6.41 g. GPC analysis: Mn=1580, EXAMPLE 125 Mw-5810, PD-3.67 (PS STD.). 60 EXAMPLE 130 Preparation of Ruthenium(III) Triflate Polymerization of THF with Tungsten(VI) Triflate RuCl (1.0 g, 4.6 mmol) was slurried in CHCl (20 mL) and Acetic Anhydride and triflic acid (2.0 g, 13.6 mmol) was added dropwise. The mixture was stirred at room temperature overnight. The 65 In a dry box, tungsten(VI) triflate (0.5 g) was added to an solvent was removed and 1.15g of black solid was collected. oven dried 100 mL RB flask equipped with a stirring bar. °F NMR (CDC1): 8 -76.7. The flask was sealed with a rubber septum and removed 5,541,346 55 56 from the dry box. A nitrogen bleed was attached and THF EXAMPLE 135 (10.00 mL) and acetic anhydride (1.00 mL) were added. After stirring for 60 minutes the polymerization was termi Preparation of nated via the addition of water (25 mL), ether (25 mL) and n-Cyclopentadienyl-tris(trifluoromethanesulfonato)- THF (50 mL). The resulting organic phase was separated, Zirconium concentrated at reduced pressure and then dried under Cp*ZrCl (1.0 g, 3 mmol) was slurried in CHCl2 (40 vacuum. Polymer Yield: 6.12 g. GPC analysis: Mn=4430, mL). THF (10.00 mL) was added to dissolve the yellow Mw-8330, PD=1.88 (PS STD.). solid. Solid AgOTf (2.3g, 9 mmol) was added; a white solid 10 formed immediately. The mixture was stirred 15 min, and EXAMPLE 31 the orangish solution was filtered. The solvent was removed to produce an orangish oil. The material was crystallized from ether and 1.1 g of yellow solid was collected. "H NMR Preparation of Rhenium(V) Triflate. showed several peaks around 2 ppm. Coordinated THF is observed by H NMR (near 83.5 and 1.2). ReCls (1.0g, 2.75 mmol) was slurried in CHCl (25 mL) 15 and triflic acid (2. lg, 13.7 mmol) was added dropwise. The EXAMPLE 136 mixture was stirred overnight at room temperature. The solvent was removed and 0.9 g of black solid was collected. Polymerization of THF with 'F NMR (CDC1): 8-744, -76.3 (small peak). n-pentamethylcyclopentadienyl-tris-(trifluoro 20 methanesulfonato)Zirconium and Acetic Anhydride EXAMPLE 132 In a dry box, n-pentamethylcyclopentadienyl-tris(trifluo romethanesulfonato)Zirconium (0.5 g) was added to an oven dried 100 mLRB flask equipped with a stirring bar. The flask Polymerization of THF with Rhenium(V) Triflate 25 was sealed with a rubber septum and removed from the dry and Acetic Anhydride box. A nitrogen bleed was attached and THF (10.00 mL) and In a dry box, rhenium(V) triflate (0.5 g) was added to an acetic anhydride (1.00 mL) were added. After stirring for 60 oven dried 100 mL RB flask equipped with a stirring bar. minutes the polymerization was terminated via the addition The flask was sealed with a rubber septum and removed of water (25 mL), ether (25 mL) and THF (50 mL). The from the dry box. A nitrogen bleed was attached and THF 30 resulting organic phase was separated, concentrated at (10.00 mL) and acetic anhydride (1.00 mL) were added. reduced pressure and then dried under vacuum. Polymer After stirring for 60 minutes the polymerization was termi Yield: 6.49 g. GPC analysis: Mn-4350, Mw=7930, PD=1.82 nated via the addition of water (25 mL), ether (25 mL) and (PSSTD.). THF (50 mL). The resulting organic phase was separated, concentrated at reduced pressure and then dried under 35 EXAMPLE 1.37 vacuum. Polymer Yield: 5.60 g. GPC analysis: Mn=7170, Mw-13500, PD=1.89 (PS STD.). Preparation of Strontium Triflate SrCl (790 mg, 5 mmol) was slurried in CHCl (20 mL) and trific acid (1.5g, 10 mmol) was added dropwise. The EXAMPLE 133 mixture was stirred overnight at room temperature. The solvent was removed and 1.7 g of white solid was collected. °F NMR (DMSO-d): 8–77.4. Preparation of Chromium(II) Triflate CrCl (0.62g, 5 mmol) was slurried in CHCl (20 mL) EXAMPLE 138 and trific acid (2.3 g, 15 mmol) was added dropwise. The 45 mixture was stirred overnight at room temperature. The Polymerization of THF with Strontium Tri?late and solvent was removed and 1.25g of gray solid was collected. Acetic Anhydride 'F NMR (DMSO-d): 8–76.65, -76.72. In a dry box, strontium trifiate (0.5 g) was added to an 50 oven dried 100 mL RB flask equipped with a stirring bar. The flask was sealed with a rubber septum and removed EXAMPLE 134 from the dry box. A nitrogen bleed was attached and THF (10.00 mL) and acetic anhydride (1.00 mL) were added. After stirring for 60 minutes the polymerization was termi Polymerization of THF with Chromium(II) Triflate nated via the addition of water (25 mL), ether (25 mL) and and Acetic Anhydride 55 THF (50 mL). The resulting organic phase was separated, In a dry box, chromium(II) triflate (0.5 g) was added to an concentrated at reduced pressure and then dried under oven dried 100 mL RB flask equipped with a stirring bar. vacuum. Polymer Yield: 5.44 G. GPC analysis: Mn=6630, The flask was sealed with a rubber septum and removed Mw-11500, PD=1.73 (PS STD.). from the dry box. A nitrogen bleed was attached and THF 60 (10.00 mL) and acetic anhydride (1.00 mL) were added. EXAMPLE 139 After stirring for 60 minutes the polymerization was termi nated via the addition of water (25 mL), ether (25 mL) and Preparation of CP(OTf)2r-O-Zr(OTf)Cp THF (50 mL). The resulting organic phase was separated, Cp2Zr(Cl)-O-(Cl)ZrCp (1.3 g, 2.5 mmol) was dis concentrated at reduced pressure and then dried under 65 solved in CHCl (40 mL), and AgOTf (1.3g, 5 mmol) was vacuum. Polymer Yield: 4.87 g. GPC analysis: Mn=9210, added. The mixture was stirred over a weekend. The mixture Mw-18800, PD=2.05 (PS STD.). was filtered and the solvent was removed. A white solid 5,541,346 57 58 formed as the solvent evaporated. The mixture was filtered EXAMPLE 144 and the solid was washed with EtO. 1.4g of white solid was collected. H NMR (toluene-d): 86.0 (s). Preparation of EXAMPLE 140 Bis(trifluoromethanesulfonato)-bis(acetylacetonate)- Zirconium Polymerization of THF with Zr(acac) (1.46g, 3 mmol) was dissolved in CHCl (5 Cp2(OTf)2r-O-Zr(OTf)Cp and Acetic Anhydride mL). A solution of triflic acid (0.9 g, 6 mmol) in CHCl (1 10 mL) was added to the Zr(acac) solution. The solution was In a dry box, Cp2(OTf)2r-O-Zr(OTf)Cp (0.5 g) was stirred 2 hours at room temperature. The solvent was added to an oven dried 100 mL RB flask equipped with a removed and 1.79g of yellow solid was collected. 'F NMR stirring bar. The flask was sealed with a rubber septum and (CDC1): 8–784; H NMR (CDC):82.15 (s), 5.82 (broad). removed from the dry box. A nitrogen bleed was attached and THE (10.00 mL) and acetic anhydride (1.00 mL) were added. After stirring for 60 minutes the polymerization was 15 EXAMPLE 145 terminated via the addition of water (25 mL), ether (25 mL) and THF (50 mL). The resulting organic phase was sepa rated, concentrated at reduced pressure and then dried under Polymerization of THF with vacuum. Polymer Yield: 1.84 g. GPC analysis: Mn=22600, Bis(trifluoromethanesulfonato)-bis(acetylacetonate)- Mw-28800, PD=1.28 (PSSTD.). 20 zirconium and Acetic Anhydride In a dry box, bis(trifluoromethanesulfonato)-bis(acetylac EXAMPLE 141 etonate)Zirconium (0.50 g) was added to an oven dried 100 mL RB flask equipped with a stirring bar. The flask was Polymerization of THF with CpMeZr(THF)BPh4 25 sealed with a rubber septum and removed from the dry box. and Acetic Anhydride A nitrogen bleed was attached and THF (10.00 mL) and acetic anhydride (1.00 mL) were added. After stirring for 60 In a dry box, CpMeZr(THF)BPhi (0.5 g) was added to an minutes the polymerization was terminated via the addition oven dried 100 mL RB flask equipped with a stirring bar. of water (25 mL), ether (25 mL) and THF (50 mL). The The flask was sealed with a rubber septum and removed resulting organic phase was separated, concentrated at from the dry box. A nitrogen bleed was attached and THF 30 (10.00 mL) and acetic anhydride (1.00 mL) were added. reduced pressure and then dried under vacuum. Polymer After stirring for 60 minutes the polymerization was termi Yield: 5.27 g. GPC analysis: Mn=13400, Mw-20200, nated via the addition of water (25 mL), ether (25 mL) and PD=1.51 (PSSTD.). THF (50 mL). The resulting organic phase was separated, concentrated at reduced pressure and then dried under 35 vacuum. Polymer Yield: 0.78 g. GPC analysis: Mn=4840, EXAMPLE 1.46 Mw-7390, PD=1.53 (PS STD.). Preparation of Yttrium EXAMPLE 1.42 Bis(trifluoromethanesulfonato)-2,2,6,6-tetramethyl 40 3.5-heptanedionate Preparation of Bis-(n-Cyclopentadienyl)-bis(trifluoromethane (t-Buacac)Y (0.64g, 1... mmol) was dissolved in CHCl sulfonato)molybdenum (5 mL). A solution of trific acid (0.3g, 2 mmol) in CHCI (1 mL) was added and the solution was stirred 2 hours at Solid Cp2MoCl2 (500 mg, 1.7 mmol) and AgOTf (0.91 g, 45 room temperature. The solvent was removed and a white 3.5 mmol) were mixed and CHCl (30 mL). The mixture solid was collected. 'H NMR (CDC): 81.2, 1.1 (broads); stirred overnight at room temperature. The white solid was 'F NMR (CDC): 8-78.4. filtered off and the solvent was evaporated to give 300 mg of a green solid. 'H NMR (CDC1): 86.4 (s). 50 EXAMPLE 1.47 EXAMPLE 143 Polymerization of THF with Yttrium Polymerization of THF with Bis(trifluoromethanesulfonato)-2,2,6,6-tetramethyl Bis-(n-Cyclopentadienyl)-bis-(trifluoromethane 3,5-heptanedionate and Acetic Anhydride sulfonato)molybdenum and Acetic Anhydride 55 In a dry box, bis-(n-Cyclopentadienyl)-bis-(trifluo In a dry box, yttrium bis(trifluoromethanesulfonato)-2,2, romethanesulfonato)molybdenum (0.275 g) was added to an 6,6-tetramethyl-3,5-heptanedionate (0.50 g) was added to an oven dried 100 mL RB flask equipped with a stirring bar. oven dried 100 mL RB flask equipped with a stirring bar. The flask was sealed with a rubber septum and removed The flask was sealed with a rubber septum and removed from the dry box. A nitrogen bleed was attached and THF 60 from the dry box. A nitrogen bleed was attached and THF (10.00 mL) and acetic anhydride (1.00 mL) were added. (10.00 mL) and acetic anhydride (1.00 mL) were added. After stirring for 60 minutes the polymerization was termi After stirring for 60 minutes the polymerization was termi nated via the addition of water (25 mL), ether (25 mL) and nated via the addition of water (25 mL), ether (25 mL) and THF (50 mL). The resulting organic phase was separated, THF (50 mL). The resulting organic phase was separated, concentrated at reduced pressure and then dried under 65 concentrated at reduced pressure and then dried under vacuum. Polymer Yield: 0.77 g. GPC analysis: Mn=15000, vacuum. Polymer Yield: 1.26 g. GPC analysis: Mn=17200, Mw=21600, PD=144 (PS STD.). Mw-25300, PD=1.47 (PSSTD.). 5,541,346 59 60 EXAMPLE 1.48 EXAMPLE 153 Preparation of Yttrium Polymerization of THF with Silicon Triflate and Trifluoromethanesulfonato-bis(2,2,6,6- Acetic Anhydride tetramethyl-3,5-heptanedionate) In a dry box, silicon triflate (0.50 g) was added to an oven (t-Buacac)Y (0.64g, 1 mmol) was dissolved in CHCl2 dried 100 mLRB flask equipped with a stirring bar. The flask (5 mL). A solution of triflic acid (0.15g, 1 mmol) in CH2Cl2 was sealed with a rubber septum and removed from the dry (1 mL) was added dropwise and the solution was stirred 2 h box. A nitrogen bleed was attached and THF (10.00 mL) and at room temperature. The solvent was removed and a white acetic anhydride (1.00 mL) were added. After stirring for 60 solid was collected. "H NMR (CDC): 81.15, 1.02; 'F 10 minutes the polymerization was terminated via the addition NMR (CDC1): 8-78.6 (small, broad), -76.7. of water (25 mL), ether (25 mL) and THF (50 mL). The resulting organic phase was separated, concentrated at EXAMPLE 149 reduced pressure and then dried under vacuum. Polymer 15 Yield: 7.76 g. GPC analysis: Mn=1450, Mw-3170, PD=2.18 Polymerization of THF with Yttrium (PSSTD). Trifluoromethanesulfonato-bis(2,2,6,6-tetramethyl 3,5-heptanedionate) and Acetic Anhydride EXAMPLE 154

In a dry box, yttrium trifluoromethanesulfonato-bis(2.2, 20 Polymerization of 1,3-Dioxolane with Ytterbium 6,6-tetramethyl-3,5-heptanedionate) (0.50 g) was added to Triflate an oven dried 100 mLRB flask equipped with a stirring bar. In a dry box, ytterbium triflate (1.5 g) was added to an The flask was sealed with a rubber septum and removed oven dried 100 mL RB flask equipped with a stirring bar. from the dry box. A nitrogen bleed was attached and THF The flask was sealed with a rubber septum and removed (10.00 mL) and acetic anhydride (1.00 mL) were added. from the dry box. After the attachment of nitrogen bleeds After stirring for 60 minutes the polymerization was termi 1,3-dioxolane (10.00 mL) was added to the flask. After 60 nated via the addition of water (25 mL), ether (2.5 mL) and minutes the polymerization was terminated via the addition THF (50 mL). The resulting organic phase was separated, of water (25 mL), THF (50 mL) and ether (25 mL). The concentrated at reduced pressure and then dried under resulting aqueous phase was separated, concentrated at vacuum. Polymer Yield: 0.18 g. 30 reduced pressure and then dried under vacuum. Yield: 8.89 g (no attempt was made to remove the catalyst from the EXAMPLE 150 polymer). GPC analysis (PSSTD): Mn=4170, Mw-8550, PD-2.05. Preparation of VO(OTf),(OCHMe) 35 EXAMPLE 155 V(O)(OnPr) (1.2g, 5 mmol) was dissolved in CHCl, (30 mL). Triflic acid (2.2g, 15 mmol) was added dropwise Polymerization of 1,3,5-Trioxane with Ytterbium to produce a dark red solution. The solvent was removed and Triflate a dark oil was produced. In a dry box, ytterbium triflate (1.5 g) was added to an 40 oven dried 100 mLRB flask equipped with a stirring bar. In EXAMPLE 51 a separate 100 mL RB flask 1,3,5-trioxane (20.00 g) was added. The flasks were sealed with a rubber septum and Polymerization of THF with removed from the dry box. To the flask containing the VO(OTf),(OCHMe) and Acetic Anhydride 45 trioxane cyclohexane (20 mL) was added, and the resulting In a dry box, VO(OTf)(OCHMe) (0.50 g) was added mixture heating to 60° C. via an oil bath until an homoge to an oven dried 100 mL RB flask equipped with a stirring neous solution resulted. This solution (20.00 mL) was then bar. The flask was sealed with a rubber septum and removed added via syringe to the flask with ytterbium triflate at this from the dry box. A nitrogen bleed was attached and THF temperature. The resulting mixture was then placed in an oil (10.00 mL) and acetic anhydride (1.00 mL) were added. 50 bath maintained at 60° C. After 60 minutes, the polymer After stirring for 60 minutes the polymerization was termi ization was terminated by the addition of water (25 mL) and nated via the addition of water (25 mL), ether (25 mL) and ether (25 mL). The resulting solid was separated and dried THF (50 mL). The resulting organic phase was separated, under vacuum, giving 4.74 g of polymer. concentrated at reduced pressure and then dried under EXAMPLE 1.56 vacuum. Polymer Yield: 6.07 g. GPC analysis: Mn-4770, 55 Mw-291 10, PD-191 (PS STD.). Heterogeneous 10 wt % Yttrium triflate on alumina catalyst preparation EXAMPLE 152 25g commercial alumina pellets AL-3945 (3.2 mm diax Preparation of Silicon Trifiate 60 3.2 mm) was placed in 250 mL water and the pH adjusted to 3 with acetic acid. After stirring 15 mins the pellets were SiCl (3 g, 17.6 mmol) was dissolved in CHCl2 (75 mL) collected by filtration and suction dried. A solution of 190 and triflic acid (10.6 g., 70.7 mmol) was added dropwise. The mL ethanol and 10 mL water had its apparent pH adjusted mixture was stirred at room temperature over the weekend. to 5 with acetic acid and 5 g of DETM was added. After The solvent was removed and 4.8 g of brown liquid was 65 stirring for 5 minutes the alumina pellets were added and collected. 'F NMR (DMSO-d): 8-76.4 (intense), small agitated for 30 minutes. The supernatant liquid was then broad peaks at -77.8 and -77.95. decanted and the pellets washed with 2x2.5 mL ethanol and 5,541,346 61 62 suction dried. The solid was dried in flowing nitrogen by EXAMPLE 158 heating to 110° C. for 1 hour and then sealed and taken into Heterogeneous 10 wt % Yttrium triflate on a nitrogen glove box. 5 g yttrium triflate was dissolved in 50 silica-alumina catalyst preparation mL acetonitrile and added to the dry alumina pellets. This 25 g commercial silica-alumina pellets (Alfa cat #31269; slurry was allowed to sit undisturbed overnight in the glove 91% AO, 6% SiO) was placed in 250 mL water and the pH adjusted to 3 with acetic acid. The pellets were then box and then evaporated to dryness in vacuo. The solid was treated in a manner identical to that described in Example then extracted with 2x2.5 mL acetonitrile, filtered and 156 above. washed with acetonitrile. Evaporation of all washings and 10 EXAMPLE 1.59 extracts indicated that ~50% of the original yttrium triflate Polymerization of THF over 10% Yttrium on had been retained on the pellets. The pellets were suction Silica-Alumina Pellets with Acetic Anhydride dried and then dried in flowing nitrogen at 110° C. for 1 hour All of the catalyst of Example 158, 10% yttrium triflate on 15 silica-alumina pellets (20.8 g) was charged in the reactor. before returning to the glove box for collection and storage The apparatus was as described in Example 156. The prior to testing. following are the conditions under which polymer was collected, together with weight of polymer obtained and GPC analysis.

THF ACA Polymer. Flow Rate Flow Rate Wit. Mn. Fraction Time (mL/min) (mL/min) (g) (PSSTD) Mw PD 1 94.5 mins. 0.50 0.05 148.78 4370 8790 2.0 2 466 mins. 0.50 0.05 1213 17000 33000 194 3 990 mills. 0.50 0.05 177.17 24800 48900 97 4 449 mins. 0.50 0.05 70.05 10000 26800 2.66

EXAMPLE 1.57 30 EXAMPLE 160 Polymerization of THF over 10% Yttrium Triflate Heterogeneous 10 wt % Zirconium triflate on on Alumina Pellets with Acetic Anhydride alumina catalyst preparation THF was charged into a 500 mL capacity ISCO pump, which was connected to a 3 way 0.3 cm SS connector (“T” 35 25 g commercial alumina pellets (Al-3945, 3.2 mm dia.X mixer) via 8 cm of 0.3 cm SS tubing containing a check 3.2 mm)) was placed in 250 mL water and the pH adjusted valve. A second ISCO pump was charged with acetic anhy to 3 with acetic acid. The pellets were then treated in a dride and this was connected to the “T” mixer by 75 cm of manner identical to that described in Example 156 above 0.3 cm SS tubing also containing a check valve. In a dry box, except substituting zirconium triflate for yttrium triflate. all of the catalyst made in Example 1 (23.9 g) was charged 40 into the reactor. This was in turn connected to the 'T' mixer EXAMPLE 6 by 12 cm of SS tubing. This reactor was then connected to a holdup tank (approximately 60 mL volume) via Cajon flex Polymerization of THF over 10%. Zirconium tubing with ultra torr fitting (0.6 cm, 13 cm. Polymerization Triflate on Alumina Pellets with Acetic Anhydride was started by first filling the reactor with THF (approxi 45 All of the catalyst of Example 160, 10% zirconium triflate mately 83 mL). Then THF was fed at a rate of 0.75 mL/min on alumina pellets (22.74 g), was charged in the reactor. The and acetic anhydride at a rate of 0.075 mL/min. The exiting apparatus was as described in Example 156. The following polymerized solution was fed to a beaker. After each frac are the conditions under which polymer was collected, tion, the pumps were refilled and the collected polymer together with weight of polymer obtained. solution diluted with diethyl ether and washed with water, 50 separated, concentrated at reduced pressure and then dried under vacuum. The following are the conditions under which the various fractions were collected, together with weight of polymer obtained and GPC analysis:

THF ACA Polymer. Flow Rate Flow Rate Wit. Mn Fraction Time (mLimin) (mL/min) (g) (PSSTD.) Mw PD 1. 372 mins. O.75 0.075 108.9 0800 22800 2. 2 899 mins. 0.50 0.05 139.2 15800 36800 2.32 3 491 mins. 0.50 0.05 17.73 27400 92300 3.37 4. 975 mins. 0.50 0.05 74.19 284.00 60200 2.12 5 464 mins. 0.50 0.05 20.6 6. 935mins 0.50 0.05 38.25 5,541,346 63 64

THF ACA Polymer. Flow Rate Flow Rate Wit. Mn. Fraction Time (mL/min) (mL/min) (g) (PSSTD) Mw PD 928 mins. 0.50 0.05 247.97 9010 22500 2.51 2 498 mins. 0.50 0.05 75.00 0800 32500 2.99 3 94.8 mins. 0.50 0.05 164.3 29000 55800 192 4 482 Imins. 0.50 0.05 58.91 45000 80700 79 5 896 Ilins. 0.50 0.05 2015 4100 80600 1.96

EXAMPLE 162 complete the exchange. The solid was collected by filtration and washed with 1 liter distilled water then suction dried. Preparation of La loaded zeolite HY for THF The wet solid was loaded into a horizontal tube furnace and polymerization 5 fired as follows in flowing dry air (flow rate 200 mL/min): 10 g of zeolite LZY-82 (NH, ion form of zeolite Y) was Room temperature to 500° C. at 12°C/min. slurried into 1 liter distilled water and the pH was adjusted Hold at 500 C. for 2 hours. to 4 with nitric acid. 1.56 g lanthanum nitrate hexahydrate Cool to room temperature over 1 hour and collect white (calculated to give a final product having -5 wt % La) was powder. added and the slurry stirred and warmed for 4 hours. The 20 The cool powder was quickly transferred to a tightly stirring was stopped and the mixture left to sit overnight to capped sample vial in order to minimize exposure to atmo complete the exchange. The solid was collected by filtration spheric moisture. A small portion of the material was sent for and washed with 1 liter distilled water then suction dried. X-ray diffraction analysis and showed that the zeolite crys The wet solid was loaded into a horizontal tube furnace and tallinity had been maintained during the ion-exchange and fired as follows in flowing dry air (flow rate 200 mL/min): 25 calcination procedure and that there was no presence of a Room temperature to 500° C. at 12° C./min. bulk Y.O. phase. Hold at 500° C. for 2 hours Cool to room temperature over 1 hour and collect white powder. 30 EXAMPLE 165 The cool powder was quickly transferred to a tightly capped sample vial in order to minimize exposure to atmo spheric moisture. A small portion of the material was sent for Polymerization of THF with 5% Yttrium Zeolite x-ray diffraction analysis and showed that the zeolite crys and Acetic Anhydride tallinity had been maintained during the ion-exchange and 35 calcination procedure and that there was no presence of a In a dry box, the yttrium zeolite of Example 164 (5.00 g) bulk LaO phase. was added to an oven dried 100 mL round bottom flask equipped with a stirring bar. The flask was sealed with a EXAMPLE 163 rubber septum and removed from the dry box. A nitrogen 40 bleed was attached and THF (20.00 mL) and acetic anhy Polymerization of THF with Lanthanum Zeolite dride (1.00 mL) were added. After stirring overnight ether and Acetic Anhydride (50 mL was added to the resulting polymerized solution. After filtering, ether (50 mL) and water (25 mL) were added In a dry box, the lanthanum zeolite of Example 162 (2.00 and the organic phase separated, concentrated at reduced g) was added to an oven dried 100 mL round bottom flask 45 pressure and then dried under vacuum. Polymer yield: 2.21 equipped with a stirring bar. The flask was sealed with a g. GPC analysis: Mn=840, Mw-4600, PD=5.48 (PS STD., rubber septum and removed from the dry box. A nitrogen bimodal distribution). bleed was attached and THF (20.00 mL) and acetic anhy dride (1.00 mL) were added. After stirring overnight the resulting material was diluted with THF (50 mL) and filtered. The resulting filtrate was concentrated at reduced 50 EXAMPLE 166 pressure. The vicous liquid was dissolve in THF (50 mL) and dried over anhydrous NaHCO, filtered concentrated at reduced pressure and then dried under vacuum. Polymer Polymerization of THF with 5% Yttrium Zeolite yield: 3.86 g. GPC analysis: Mn=969, Mw-5970, PD=6.17 55 HY and Acetic Anhydride (PSSTD., bimodal distribution). In a dry box, the 5% yttrium zeolite HY of Example 164 EXAMPLE 164 (10.00 g) was added to an oven dried 100 mL round bottom flask equipped with a stirring bar. The flask was sealed with Preparation of 5% Y loaded zeolite HY for THF a rubber septum and removed from the dry box. A nitrogen polymerization 60 bleed was attached and THF (20.00 mL) and acetic anhy dride (1.00 mL) were added. After stirring overnight ether 10 g of zeolite LZY-82 (NH, ion form of zeolite Y) was (50 mL) was added to the resulting polymerized solution. slurried into 1 liter distilled water and the pH was adjusted After filtering, ether (50 mL) and water (25 mL) were added to 4 with nitric acid. 2.20 g yttrium nitrate pentahydrate and the organic phase separated, concentrated at reduced (calculated to give a final product having -5 wt % Y) was 65 pressure and then dried under vacuum. Polymer yield: 7.29 added and the slurry stirred and warmed for 4 hours. The g. GPC analysis: Mn=1350, Mw-14800, PD-10.94 (PS stirring was stopped and the mixture left to sit overnight to STD., bimodal distribution). 5,541,346 65 66 EXAMPLE 167 tallinity had been maintained during the ion-exchange and calcination procedure and that there was no presence of a Preparation of 10 wt % Y loaded Zeolite HY for bulk Y.O. phase. THF polymerization 50 g of zeolite LZY-82 (NH, ion form of zeolite Y) was EXAMPLE 70 slurried into 1 liter distilled water and the pH was adjusted to 4 with nitric acid. 22.0 g yttrium nitrate pentahydrate Polymerization of THF with Yttrium Mordenite and (calculated to give a final product having ~10 wt % Y) was Acetic Anhydride added and the slurry stirred and warmed for 4 hours. The 10 In a dry box, the yttrium mordenite of Example 169 (5.00 stirring was stopped and the mixture left to sit overnight to g) was added to an oven dried 100 mL round bottom flask complete the exchange. The solid was collected by filtration equipped with a stirring bar. The flask was sealed with a and washed with 1 liter distilled water then suction dried. rubber septum and removed from the dry box. A nitrogen The wet solid was loaded into a horizontal tube furnace and bleed was attached and THF (20.00 mL) and acetic anhy fired as follows in flowing dry air (flow rate 200 mL/min): 15 dride (1.00 mL) were added. After stirring overnight ether Room temperature to 500° C. at 12°C/min. (50 mL) was added to the resulting polymerized solution. Hold at 500° C. for 2 hours. After filtering, ether (50 mL) and water (25 mL) were added Cool to room temperature over 1 hour and collect white and the organic phase separated, concentrated at reduced powder. pressure and then dried under vacuum. Polymer yield: 1.43 The cool powder was quickly transferred to a tightly 20 g. GPC analysis: Mn=6020, Mw=15500, PD=2.58 (PS capped sample vial in order to minimize exposure to atmo STD.). spheric moisture. A small portion of the material was sent for X-ray diffraction analysis and showed that the zeolite crys EXAMPLE 171 tallinity had been maintained during the ion-exchange and calcination procedure and that there was no presence of a 25 Preparation of -10 wt % Didymium loaded zeolite bulk Y.O. phase. HY for THF polymerization 50 g of Zeolite LZY-82 (NH, ion form of zeolite Y) was EXAMPLE 168 slurried into 1 liter distilled water and the pH was adjusted 30 to 4 with nitric acid. 10g didymium chloride was added and Polymerization of THF with 10 wt % Yttrium the slurry stirred and warmed for 1 hour. The zeolite was Zeolite MY and Acetic Anhydride recovered by filtration washed with 1 liter distilled water and In a dry box, the 10% yttrium zeolite HY of Example 167 then re-slurried into 1 liter fresh distilled water. Another 10 (10.00 g) was added to an oven dried 100 mL round bottom g didymium chloride was added and the pH adjusted to 4 flask equipped with a stirring bar. The flask was sealed with 35 with nitric acid and this slurry was stirred for 1 hour. The a rubber septum and removed from the dry box. A nitrogen stirring was stopped and the mixture left to sit overnight to bleed was attached and THF (20.00 mL) and acetic anhy complete the exchange. The solid was collected by filtration dride (1.00 mL) were added. After 4 hrs. ether (50 mL) was and washed with 1 liter distilled water then suction dried. added to the resulting polymerized solution. After filtering, The wet solid was loaded into a horizontal tube furnace and the organic phase was washed with 5% NaOH (10 mL), 40 fired as follows in flowing dry air (flow rate 200 mL/min): separated concentrated at reduced pressure then dried under Room temperature to 500° C. at 12° C./min. vacuum. Polymer yield: 6.11 g. GPC analysis: Mn=690, Hold at 500 C. for 2 hours. Mw=4120, PD=10.94 (PS STD., bimodal distribution). Cool to room temperature over 1 hour and collect white powder. EXAMPLE 169 45 The cool powder was quickly transferred to a tightly capped sample vial in order to minimize exposure to atmo Preparation of Y loaded Zeolite mordenite for THF spheric moisture. The powder was then pressed to 10 tons polymerization and the resultant cake sieved through 10-20 mesh to give 10 g of zeolite H-mordenite was slurried into 1 liter granulated catalyst. distilled water and the pH was adjusted to 4 with nitric acid. 50 2.20 g yttrium nitrate pentahydrate (calculated to give a final EXAMPLE 172 product having -5 wt % Y) was added and the slurry stirred and warmed for 4 hours. The stirring was stopped and the Polymerization of THF with 10% Didymium mixture left to sit overnight to complete the exchange. The Zeolite HY and Acetic Anhydride solid was collected by filtration and washed with 1 liter 55 distilled water then suction dried. The wet solid was loaded In a dry box, the 10% Didymium zeolite HY of Example into a horizontal tube furnace and fired as follows in flowing 171 (10.00 g) was added to an oven dried 100 mL round dry air (flow rate 200 mL/min): bottom flask equipped with a stirring bar. The flask was sealed with a rubber septum and removed from the dry box. Room temperature to 500° C. at 12°C/min. 60 A nitrogen bleed was attached and THF (20.00 mL) and Hold at 500 C. for 2 hours. acetic anhydride (1.00 mL) were added. After stirring over Cool to room temperature over 1 hour and collect white night the polymerized solution was firered, then ether (25 powder. mL), THF (25 mL) and water (25 mL) were added the The cool powder was quickly transferred to a tightly organic phase separated concentrated at reduced pressure capped sample vial in order to minimize exposure to atmo 65 then dried under vacuum. Polymer yield: 7.56 g. GPC spheric moisture. A small portion of the material was sent for analysis: Mn=1010, Mw-7150, PD=7.08 (PSSTD., bimodal X-ray diffraction analysis and showed that the zeolite crys distribution). 5,541,346 67 68 EXAMPLE 73 EXAMPLE 176 Polymerization of THF with 10% Yttrium Tri?late Preparation of 5 wt % Sc loaded zeolite HY for on Zeolite NaY Pellets and Acetic Anhydride THF polymerization In a dry box, the 10% yttrium triflate on Zeolite NaY 5g of zeolite LZY-82 (NH, ion form of zeolite Y) was pellets of Example 175 (10.00 g) was added to an oven dried slurried into 1 liter distilled water and the pH was adjusted 100 mL round bottom flask equipped with a stirring bar. The to 4 with nitric acid. 1.44 g scandium chloride (calculated to flask was sealed with a rubber septum and removed from the give a final product having -5 wt % Sc) was added and the dry box. A nitrogen bleed was attached and THF (20.00 mL) slurry stirred and warmed for 4 hours. The stirring was O and acetic anhydride (1.00 mL) were added. After stirring stopped and the mixture left to sit overnight to complete the for 1 hour THF (50 mL) the polymerized solution then exchange. The solid was collected by filtration and washed filtered. The filtrate was washed with water (25 mL), then with 1 liter distilled water then suction dried. The wet solid ether (50 mL) was added. The organic phase was separated was loaded into a horizontal tube furnace and fired as concentrated at reduced pressure then dried under vacuum. follows in flowing dry air (flow rate 200 mL/min): 5 Polymer yield: 0.700 g. GPC analysis: Mn=18800, Room temperature to 500° C. at 12° C./min. Mw-27100, PD=1.44 (PS STD.). Hold at 500 C. for 2 hours. EXAMPLE 177 Cool to room temperature over 1 hour and collect white powder. Preparation of yttrium triflate supported on alumina The cool powder was quickly transferred to a tightly derivatized with diethylmalonate capped sample vial in order to minimize exposure to atmo spheric moisture. A small portion of the material was sent for 95 mL ethanol and 5 mL water were mixed and the pH x-ray diffraction analysis and showed that the Zeolite crys adjusted to 5 with acetic acid. 2 g DETM was added and the tallinity had been maintained during the ion-exchange and 25 mix stirred for 5 minutes. 10 gy-alumina was added and the calcination procedure and that there was no presence of a slurry stirred a further 3 min. The solid was allowed to settle bulk ScC) phase. and the supernatant liquid decanted. The recovered solid was then washed with two portions of 25 mLethanol and suction dried. The solid was finally dried in flowing nitrogen (200 EXAMPLE 74 30 mL/min) by heating to 110° C. and holding at that tempera ture for 1 hour. The cooled powder was immediately trans ferred to a nitrogen glove box. Polymerization of THF with 5% Scandium Zeolite Under a dry nitrogen atmosphere inside a glove box, 0.5 HY and Acetic Anhydride g yttrium triflate was dissolved in 25 mL acetonitrile and 5 35 g of the alumina powder prepared above was added. The In a dry box, the 5% scandium zeolite HY of Example 173 slurry was stirred for 1 hour and then filtered, rinsed with 25 (3.94 g) was added to an oven dried 100 mL round bottom mL acetonitrile and suction dried. The powder was then flask equipped with a stirring bar. The flask was sealed with pumped to dryness in vacuum and stored under nitrogen. a rubber septum and removed from the dry box. A nitrogen bleed was attached and THF (20.00 mL) and acetic anhy 40 EXAMPLE 1.78 dride (1.00 mL) were added. After stirring overnight the polymerized solution was filtered, then ether (25 mL), THF Polymerization of THF with Yttrium Triflate (25 mL) and water (25 mL) were added the organic phase Supported on Alumina Derivatized with Diethyl separated concentrated at reduced pressure then dried under Malonate vacuum. Polymer yield: 4.48 g. GPC analysis: Mn=736, 45 Mw-7890, PD=10.72 (PS STD., bimodal distribution). In a dry box, the yttrium triflate supported on diethylma lonate derivatized alumina of Example 177 (5.00 g) was weighed in an oven dried 100 mL RB flask. The flask was EXAMPLE 175 sealed with a rubber septum and removed from the dry box. A nitrogen purge was attached and THF (15.00 mL) and 50 acetic anhydride (2.00 mL) added via syringe. After 360 Preparation of 10 wt % Y on zeolite NaY pellets minutes the polymerization was terminated by decanting, followed by concentration at reduced pressure and then 12.5g yttrium nitrate pentahydrate was dissolved in 1 liter drying under vacuum. Polymer yield: 2.53 g. GPC analysis: distilled water and the pH adjusted to 4 with nitric acid. 25 Mn=8300, Mw-20900, PD-2.52 (PSSTD.). g zeolite LZY-52 (NAY) pellets (3 mm diax3 mm) was 55 added and the mixture allowed to sit overnight. The pellets EXAMPLE 179 were then filtered and washed with 1 liter distilled water and suction dried. The pellets were then calcined in flowing dry Preparation of air (flow rate 200 mL/min): bis(n-cyclopentadienyl)tetrahydrofuran-bis(trifluoro Room temperature to 500° C. at 12°C/min. 60 methanesulfonato)Zirconium supported on silica Hold at 500° C. for 2 hours. derivatized with DETM Cool to room temperature over 1 hour and collect white 95 mL ethanol and 5 mL water were mixed and the pH powder. adjusted to 5 with acetic acid. 2 g DETM was added and the The cool pellets were quickly transferred to a tightly 65 mix stirred for 5 minutes. 10 g silica was added and the capped sample vial in order to minimize exposure to atmo slurry stirred a further 3 mins. The solid was allowed to spheric moisture. settle and the supernatant liquid decanted. The recovered 5,541,346 69 70 solid was then washed with two portions of 25 mL ethanol 100 mLRB flask. The flask was sealed with a rubber septum and suction dried. The solid was finally dried in flowing and removed from the dry box. A nitrogen purge was nitrogen (200 mL/min) by heating to 110° C. and holding at attached and THF (15.00 mL) and acetic anhydride (2.00 that temperature for 1 hour. The cooled powder was imme mL) added via syringe. After 360 minutes the polymeriza diately transferred to a nitrogen glove box. tion was terminated by decanting, followed by concentration Under a dry nitrogen atmosphere inside a glove box, 0.5 at reduced pressure and then drying under vacuum. Polymer g bis(n-cyclopentadienyl)tetrahydrofuran-bis(trifluo yield: 1.99 g. GPC analysis: Mn=9600, Mw-25800, romethanesulfonato)Zirconium was dissolved in 25 mL. PD=2.69 (PSSTD.). acetonitrile and 5 g of the silica powder was added. The slurry was stirred for 1 hour and then filtered, rinsed with 25 10 EXAMPLE 1.83 mL acetonitrile and suction dried. The powder was then pumped to dryness in vacuum and stored under nitrogen. Preparation of ~10 wt % Ytterbium triflate supported on silica-alumina EXAMPLE 180 15 50 g silica-alumina pellets (3.2 mm dia.X3.2 mm) were Polymerization of THF with placed in 250 mL distilled water. The pH was adjusted to 3 Bis(n-cyclopentadienyl)tetrahydrofuran-bis(trifluoro with acetic acid and the slurry was stirred for 15 mins. The methanesulfonato)Zirconium Supported on Silica pellets were collected by filtration and then added to a Derivatized with Diethyl Malonate solution of 190 mL ethanol, 10 mL water in which the pH 20 was adjusted to 5 with acetic acid and then 5g DETM was In a dry box, the bis(n-cyclopentadienyl)tetrahydrofuran added. Stirred for 30 min and then the supernatant liquid was bis(trifluoromethane-sulfonato)zirconium supported on decanted. The pellets were washed with two portions of 25 silica of Example 179 (5.00 g) was weighed in an oven dried mLethanol and then suction dried prior to drying in flowing 100 mLRB flask. The flask was sealed with a rubber septum nitrogen (200 mL/min) at 110° C. for 1 hour. The pellets and removed from the dry box. A nitrogen purge was 25 were then transferred to a nitrogen glove box. Inside the attached and THF (15.00 mL) and acetic anhydride (2.00 glove box 10 g ytterbium triflate was dissolved in 100 mL mL) were added via syringe. After 360 minutes the poly dry acetonitrile and this solution was added to the dry merization was terminated by decanting, followed by con pellets. The slurry then sat overnight under nitrogen before centration at reduced pressure and then drying under being evaporated to dryness. The recovered solid was vacuum. Polymer yield. 2.06 g. GPC analysis: Mn=7620, 30 washed with three 25 mLportions of dry acetonitrile, suction Mw-19000, PD=2.29 (PS STD.). dried and then dried in flowing nitrogen to 110° C. for 1 hour. The dry pellets were stored under nitrogen in a glove EXAMPLE 181 box.

Preparation of EXAMPLE 1.84 bis(n-cyclopentadienyl)tetrahydrofuran-bis(trifluoro 35 methanesulfonato)zirconium supported on alumina Depolymerization of Polytetrahydrofuran derivatized with DETM (Terathane(R) 1000) with 10% Ytterbium Triflate 95 mL ethanol and 5 mL water were mixed and the pH Supported on Silica-Alumina adjusted to 5 with acetic acid. 2 g DETM was added and the 40 Polytetrahydrofuran with hydroxyl ends (Terathane() mix stirred for 5 minutes. 10 g A-alumina was added and the 1000, 300 g, Aldrich) and the 10% ytterbium triflate sup slurry stirred a further 3 mins. The solid was allowed to ported on silica-alumina of Example 183 (10 g) were placed settle and the supernatant liquid decanted. The recovered in a 500 mL three neck flask equipped witch a stirring bar, solid was then washed with two portions of 25 mL ethanol Vigreaux column (12") and a fractional distillation head. A and suction dried. The solid was finally dried in flowing 45 nitrogen purge was attached and all other openings were nitrogen (200 mL/min) by heating to 110° C. and holding at glass stoppered. The resulting mixture was heated with an that temperature for 1 hour. The cooled powder was imme oil bath and the resulting water clear distillate fractions diately transferred to a nitrogen glove box. collected as follows: Under a dry nitrogen atmosphere inside a glove box, 0.5 50 g bis(n-cyclopentadienyl)tetrahydrofuran-bis(trifluo Oil Bath Rxn Temp Head Temp Weight romethanesulfonato)Zirconium was dissolved in 25 mL Fraction Temp (°C) (°C) (°C) (g) acetonitrile and 5 g of the alumina powder prepared above was added. The slurry was stirred for 1 hour and then 1 180 152 64 70.72 filtered, rinsed with 25 mL acetonitrile and Suction dried. 2 198 163 66 112.0 55 3 96 124 66 59.00 The powder was then pumped to dryness in vacuum and 4. 202 149 66 55.00 stored under nitrogen. Total weight of distillate collected: 296.72 g % Yield (Recovery): 98.9% EXAMPLE 182 GC analyses of the various fractions confirm the product to be THF Polymerization of THF with 60 Bis(n-cyclopentdienyl)tetrahydrofuran-bis(trifluoro COMPARATIVE EXAMPLE 1 methanesulfonato)Zirconium Supported on Alumina In a dry box, zeolite HY (1.00 g) was added to an oven dry Derivatized with Diethyl Malonate 100 mLRB flask equipped with a stirring bar. The flask was In a dry box, the bis(n-cyclopentdienyl)tetrahydrofuran 65 sealed with a rubber septum and removed from the dry box. bis(trifluoromethanesulfonato)Zirconium supported on alu After the attachment of a nitrogen bleed THF (20.00 mL) mina of Example 181 (5.00g) was weighed in an oven dried was added by syringe. After 45 minutes acetic anhydride 5,541,346 71 72 (1.00 mL) was added. After filtering off the zeolite catalyst EXAMPLE 1.88 and concentration of the filtrate, no polymer was obtained. Polymerization of THF with Ytterbium Triflate and Isophthalic Acid EXAMPLE 185 In a dry box, ytterbium triflate (5.0 g) and isophthalic acid (2.76 g) were added to an oven dried 100 mL RB flask equipped with a stirring bar. The flask was sealed with Polymerization of THF with Ytterbium Triflate and rubber septum and then removed from the dry box, a 3-Methyladipic Acid 10 nitrogen bleed was attached and THF (20.0 mL) added. After In a dry box, ytterbium triflate (10.0 g) and 3-methyla 60 minutes the polymerization was terminated via the addi dipic acid (5.0 g) were added to each of three separate oven tion of water. The polymer was dissolved in methylene dried 100 mL RB flasks equipped with stirring bars. The chloride. The resulting organic solution was washed with flasks were sealed with rubber septa and then removed from water (2x200 mL), then concentrated at reduced pressure the dry box. Nitrogen bleeds were attached and THF (20.0 15 and then dried under vacuum. Polymer yield: 12.24 g. GPC mL) was added to each flask. After 2, 4, and 6 hours a analysis (PS STD): Mn=258000, Mw-559000, PD=2.16. polymerization was terminated via the addition of water (25 mL), ether (25 mL) and THF (50 mL). The resulting organic EXAMPLE 1.89 phases were separated, concentrated at reduced pressure and Polymerization of THF with Ytterbium Triflate and then dried under vacuum. Polymer yields and GPC analysis: 20 Terephthalic Acid Polymerization Mn In a dry box, ytterbium triflate (5.0 g) and terephthalic Time Polymer Yicld (g) (PS*STD) Mw PD acid (2.76 g) were added to an oven dried 100 mL RB flask equipped with a stirring bar. The flask was sealed with 2 hrs. 2.96 8630 13800 1.61 25 rubber septum and then removed from the dry box, a 4 hrs. 3.15 8170 13300 1.63 nitrogen bleed was attached and THF (20.0 mL) was added. 6 hrs. 4.79 7230 2600 1.75 After 60 minutes the polymerization was terminated via the *Polystyrene standard addition of water. The polymer was dissolved in methylene chloride. The resulting organic solution was washed with 30 water (2x200 mL), then concentrated at reduced pressure and then dried under vacuum. Polymer yield: 3.66 g. GPC EXAMPLE 86 analysis (PS STD): Mn=308000, Mw-744000, PD=2.42. EXAMPLE 190 Polymerization of THF with Ytterbium Triflate and 35 Adipic Acid Polymerization of THF with Ytterbium Triflate and In a dry box, ytterbium triflate (5.0 g) and adipic acid A (1.21 g) were added to an oven dried 100 mL RB flask equipped with a stirring bar. The flask was sealed with 40 rubber septum and then removed from the dry box, a nitrogen bleed was attached and THF (20.0 mL) added. After 60 minutes the polymerization was terminated via the addi tion of water (25 mL), ether (25 mL) and THF (50 mL). The resulting organic phase was separated, concentrated at 45 reduced pressure and then dried under vacuum. Polymer yield: 7.65 g. GPC analysis (PS STD.): Mn=14000, In a dry box, ytterbium triflate (5.0 g) and A (1.5 g) were Mw=39300, PD=2.80, IR analysis (CHCl, cm): 2860, added to an oven dried 100 mL RB flask equipped with a 1727 (C=O), 1370, 1100. stirring bar. The flask was sealed with rubber septum and then removed from the dry box, a nitrogen bleed was 50 attached and THF (20.0 mL) added. After 120 minutes the polymerization was terminated via the addition of water, EXAMPLE 1.87 THF and ether. The resulting separated organic solution was washed with sodium bicarbonate (2x2.5 mL), then concen trated at reduced pressure and dried under vacuum. Polymer Polymerization of THF with Ytterbium Triflate and 55 yield: 2.37 g. Maleic Acid In a dry box, ytterbium triflate (5.0 g) and maleic acid (1.9 EXAMPLE 191 g) were added to an oven dried 100 mL RB flask equipped Polymerization of THF with Ytterbium Triflate and with a stirring bar. The flask was sealed with rubber septum 60 and then removed from the dry box, a nitrogen bleed was A attached and THF (20.0 mL) added. After 60 minutes the In a dry box, ytterbium triflate (5.0 g) and A (0.5 g) were polymerization was terminated via the addition of water (25 added to an oven dried 100 mL RB flask equipped with a mL), ether (25 mL) and THF (50 mL). The resulting organic stirring bar. The flask was sealed with rubber septum and phase was separated, concentrated at reduced pressure and 65 then removed from the dry box, a nitrogen bleed was then dried under vacuum. Polymer yield: 3.98 g. GPC attached and THF (20.0 mL) was added. After 60 minutes analysis (PS STD): Mn=8950, Mw-16800, PD=1.88. the polymerization was terminated via the addition of water, 5,541,346 73 74 THF and ether. The resulting separated organic solution was EXAMPLE 195 washed with sodium bicarbonate (2x25 mL), then concen trated at reduced pressure and then dried under vacuum. Polymerization of THF with Ytterbium Triflate and Polymer yield: 1.97 g. GPC analysis (PSSTD): Mn=72200, Isophthalic Acid and Terephthalic Acid Mw-173000, PD-2.39. 5 In a dry box, ytterbium triflate (5.0 g), terephthalic acid (2.00 g) and isophthalic acid (0.5 g) were added to an oven EXAMPLE 192 dried 100 mLRB flask equipped with a stirring bar. The flask was sealed with rubber septum and then removed from the Polymerization of THF with Ytterbium Triflate and 10 dry box, a nitrogen bleed was attached and THF (20.0 mL) B added. After stirring overnight the polymerization was ter O O B minated via the addition of water. The polymer was dis N / solved in methylene chloride. The resulting organic solution O C C O was washed with water (2x200 mL), then concentrated at reduced pressure and then dried under vacuum. Polymer yield: 7.38 g. GPC analysis (PS STD): Mn=42000, C C Mw-138000, PD-3.30. / W O O EXAMPLE 1.96 In a dry box, ytterbium triflate (5.0 g) and B (1.5 g) were 20 added to an oven dried 100 mL RB flask equipped with a Polymerization of THF with Ytterbium Triflate and stirring bar. The flask was sealed with rubber septum and N-Acetyl-L-glutamic Acid then removed from the dry box, a nitrogen bleed was In a dry box, ytterbium triflate (15.0 g) and N-acetyl-L- attached and THF (20.0 mL) added. After 120 minutes the glutamic acid (1.0 g) were added to an oven dried 100 mL. polymerization was terminated via the addition of water, 25 RB flask equipped with a stirring bar. The flask was sealed THF and ether. The resulting separated organic solution was with rubber septum and then removed from the dry box, a washed with sodium bicarbonate (2x25 mL), then concen nitrogen bleed was attached and THF (20.0 mL) added. After trated at reduced pressure and then dried under vacuum. stirring overnight the polymerization was terminated via the Polymer yield: 8.49 g, GPC analysis (PS STD): addition of water, THF and ether. The resulting organic Mn=127000, Mw-341000, PD-2.67. 30 solution was washed with water, then concentrated at reduced pressure and then dried under vacuum. Polymer EXAMPLE 193 yield: 2.82 g. GPC analysis (PS STD): Mn=16600, Mw-80500, PD=4.83. Polymerization of THF with Ytterbium Triflate and 1,2,4-Benzenetricarboxylic Acid 35 EXPERIMENT 1 In a dry box, ytterbium triflate (5.0 g) and 1,2,4-benzen etricarboxylic acid (2.0 g) were added to an oven dried 100 Preparation of mL RB flask equipped with a stirring bar. The flask was (HOCOPh-NHC(O)NH-Ph)-CH, sealed with rubber septum and then removed from the dry 40 In a dry box, MDI (25.0 g) was weighed into a 500 mL box, a nitrogen bleed was attached and THF (20.0 mL) RB flask equipped with a stirrer, dimethylacetamide added. After 21 hours the polymerization was terminated via (DMAC, 75 mL) was then added. A solution of 4-aminoben the addition of water, THF and ether. The resulting separated zoic acid (27.8 g) in DMAC (25 mL) was slowly added to organic solution was washed with sodium bicarbonate (25 the stirred MDI/DMAC solution. The reaction was allowed mL) upon which a gelatinous material resulted. HCl was 45 to stir overnight, then the reaction mixture was poured into then added and the organic phase separated, then concen diethyl ether. The resulting precipitate was filtered and dried trated at reduced pressure and finally dried under vacuum. under vacuum at 100° C. In this compound all phenyl rings Polymer yield: 8.91 g. GPC analysis (PS STD): are para substituted. Mn=100000, Mw-227000, PD=2.26. 50 EXAMPLE 1.97 EXAMPLE 194 Polymerization of THF with Polymerization of THF with Ytterbium Triflate and (HOCPh-NHC(O)NH-Ph), CH, and 1,1-Ethylenebis(5-oxo-3-pyrrollidecarboxylic Acid) 55 Ytterbium Trifate In a dry box, ytterbium triflate (5.0 g) and 1,1'-ethyl In a dry box, ytterbium triflate (5.00 g) and (HOOPh enebis(5-oxo-3-pyrrollidecarboxylic acid) (1.0 g) were NHC(O)NH-Ph)-CH (1.0 g) were added to an oven added to an oven dried 100 mL RB flask equipped with a dried 100 mLRB flask equipped with a stirring bar. The flask stirring bar. The flask was sealed with rubber septum and was sealed with a rubber septum and removed from the dry then removed from the dry box, a nitrogen bleed was 60 box. After the attachment of a nitrogen bleed THF (20.00 attached and THF (20.0 mL) added. After 3 hours the mL) was added via syringe. After 18 hrs. the resulting solid polymerization was terminated via the addition of water, mass was dissolved in THF (-800 mL) and water (-10 mL). THF and ether. The resulting separated organic solution was The resulting mixture was filtered through Celite and then washed with sodium bicarbonate then the organic phase concentrated at reduced pressure to ~200 mL, then poured separated, concentrated at reduced pressure and finally dried 65 into a Waring blender containing water (-500 mL). The under vacuum. Polymer yield: 5.21 g. GPC analysis (PS resulting precipitated polymer was recovered via filtration STD): Mn=73200, Mw=194000, PD=2.65. and dried under vacuum affording 10.30g of white material. 5,541,346 75 76 EXAMPLE 198 indium, thulium, silicon, germanium, tin, lead, arsenic, antimony and bismuth; Polymerization of THF/3-Me-THF with at least one of Z is an anion of the formula-OSOR, (HOCPh-NHC(O)NH-Ph)-CH and wherein R is perfluoroalkyl containing 1 to 12 carbon Ytterbium Triflate atoms or part of a fluorinated polymer wherein the carbon atoms alpha beta to the sulfonate group are In a dry box, ytterbium triflate (5.00 g) and (HOCPh together bonded to at least four fluorine atoms, or NHC(O)NH-Ph)-CH (1.0 g) were added to an oven tetraphenylborate, and the remainder of Z is oxo or one dried 100 mLRB flask equipped with a stirring bar. The flask or more monovalent anions; was sealed with a rubber septum and removed from the dry 10 s is 1 when M is silver, box. After the attachment of a nitrogen bleed THF (15.00 s is 2 when M is strontium, barium, cobalt, rhodium, mL) and 3-Me-THF (5.0 mL) were added via syringe. After iridium, palladium, platinum, chromium, zinc, cad 18 hrs. the resulting solid mass was dissolved in THF (-800 mium or mercury; mL) and water (-10 mL). The resulting mixture was filtered through Celite and then concentrated at reduced pressure to s is 3 when M is scandium, yttrium, a rare earth metal, -200 mL, then poured into a Waring blender containing 15 arsenic, antimony, bismuth, gold, iron, ruthenium, water (-500 mL). The resulting precipitated polymer was osmium, aluminum, gallium, indium or thulium; recovered via filtration and dried under vacuum affording s is 4 when M is titanium, zirconium, hafnium, molyb 7.38g of white material. denum, silicon, germanium, tin, or lead; 20 s is 5 when M is rhenium, vanadium, niobium ortantalum; EXPERIMENT 2. s is 6 when M is tungsten; Q is a neutral ligand; Preparation of t is 0 or an integer of 1 to 6; (HOCC(CH),CHO-C(O)NH-Ph)-CH and provided that each oxo group present as part of Z is In a dry box, MDI (25.0 g) was weighed into a 500 mL 25 considered to account for two of s. RB flask equipped with a stirrer, dimethylacetamide 2. The process as recited in claim 1 wherein R and Rare (DMAC, 70 mL) was then added followed by hydroxypiv each hydrogen, and all of R and Rare hydrogen. alic acid (23.8g). The reaction was allowed to stir overnight, 3. The process as recited in claim 1 wherein RandR' are then the reaction mixture was poured into water. The result each hydrogen, one of R is hydrogen, the other R’ is ing precipitate was filtered and dried under vacuum at 100 30 methyl, and both R are hydrogen. C., affording 46.28 g (94.84%) of product. All phenyl rings 4. The process as recited in claim 1 wherein R is in this compound are para substituted. trifluoromethyl. 5. The process as recited in claim 1 wherein said tem EXAMPLE 199 perature is about 130° C. to about 200° C. 35 6. The process as recited in claim 1 wherein said com Polymerization of THF with (HOCC pound of formula MZ'Q, is about 1 to about 3% by weight (CH),CHO-C(O)NH-Ph)-CH and of said polyether. Ytterbium Triflate 7. The process as recited in claim 1 wherein M is strontium, scandium, yttrium, the rare earth metals, titanium, In a dry box, ytterbium triflate (10.00 g) and 40 zirconium, hafnium, vanadium, niobium, tantalum, chro (HOCC(CH)2CHO-C(O)NH-Ph)-CH (1.0 g) were mium, molybdenum, tungsten, rhenium, iron, ruthenium, added to an oven dried 100 mL RB flask equipped with a palladium, copper, gold, zinc, tin, bismuth or mischmetall. stirring bar. The flask was sealed with a rubber septum and 8. A process for the depolymerization of a polyether to a removed from the dry box. After the attachment of a tetrahydrofuran, comprising, contacting at a temperature of nitrogen bleed THF (20.00 mL) was added via syringe. After 45 about 100° C. to about 250° C., a polymer consisting 16 hrs. the resulting solid mass was repeatedly washed with essentially of one or more repeat units of the formula water, then dried under vacuum affording 6.40 g of white material. NMR and GPC analysis showed the product to be -CHRCRRCRRCHRO contaminated with a small amount of the starting diacid. What is claimed is: 50 wherein each R', R, R and R' is independently hydro 1. A process for the depolymerization of a polyether to a gen or hydrocarbyl containing 1 to 20 carbon atoms, tetrahydrofuran, comprising, contacting at a temperature of with a heterogeneous catalyst containing a metal per about 100° C. to about 250 C., a polymer consisting fluoroalkylsulfonate attached to the surface of said essentially of one or more repeat units of the formula catalyst through said metal; said metal selected from 55 the group consisting of strontium, vanadium, copper, -(CHRCRRCRRCHRO niobium, tungsten, cobalt, barium, scandium, yttrium, the rare earth metals, titanium, zirconium, hafnium, with a compound of the formula MZ'Q, wherein: chromium, molybdenum, tantalum, rhenium, iron, each R', R, R and R' is independently hydrogen or ruthenium, osmium, rhodium, iridium, palladium, hydrocarbyl containing to 20 carbon atoms; 60 platinum, silver, gold, zinc, cadmium, mercury, alumi M is a metal selected from the group consisting of cobalt, num, gallium, indium, thulium, germanium, tin, lead, vanadium, copper, mischmetall, niobium, tungsten, arsenic, antimony and bismuth. strontium, barium, scandium, yttrium, the rare earth 9. The process as recited in claim 8 wherein R', one of R, metals, titanium, zirconium, hafnium, chromium, both of R and R' are hydrogen, and the remaining R is molybdenum, tantalum, rhenium, iron, ruthenium, 65 alkyl containing 1-4 carbon atoms. osmium, rhodium, iridium, palladium, platinum, silver, 10. The process as recited in claim 8 wherein said metal gold, zinc, cadmium, mercury, aluminum, gallium, cation is strontium, scandium, yttrium, a rare earth metal, 5,541,346 titanium, Zirconium, hafnium, vanadium, niobium, tantalum, 12. The process as recited in claim 8 wherein said chromium, molybdenum, tungsten, rhenium, iron, ruthe- heterogeneous catalyst is alumina, silica, silica-aluminate, nium, palladium, copper, gold, Zinc, tin or bismuth. carbon or Zirconia. 11. The process as recited in claim 8 wherein all of R', R, R and R are hydrogen. ck c k sk