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IIIHIIII US005541346A United States Patent (19) 11 Patent Number: 5,541,346 Drysdale Et Al

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IIIHIIII US005541346A United States Patent (19) 11 Patent Number: 5,541,346 Drysdale Et Al 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
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