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United States Patent (19) 11 Patent Number: 6,111,147 Sigwart Et Al

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United States Patent (19) 11 Patent Number: 6,111,147 Sigwart Et Al USOO6111147A United States Patent (19) 11 Patent Number: 6,111,147 Sigwart et al. (45) Date of Patent: Aug. 29, 2000 54 PROCESS FOR PREPARING 4,485,005 11/1984 O’Hara. POLYTETRAHYDROFURAN AND 5,773,648 6/1998 Becker et al.. DERVATIVES THEREOF FOREIGN PATENT DOCUMENTS 75 Inventors: Christoph Sigwart, Schriesheim; Karsten Eller, Ludwigshafen; Rainer 4433 606 3/1996 Germany. Becker, Bad Duerkheim; Klaus-Dieter 19507399 9/1996 Germany. Plitzko, Limburgerhof, Rolf Fischer, 19527 532 1/1997 Germany. Heidelberg; Frank Stein, Bad WO 96/09335 3/1996 WIPO. Duerkheim; Ulrich Mueller, Neustadt; Michael Hesse, Worms, all of Germany Primary Examiner Johann Richter 73 Assignee: BASF Aktiengesellschaft, ASSistant Examiner Brian J. Davis Ludwigshafen, Germany Attorney, Agent, or Firm-Oblon, Spivak, McClelland, 21 Appl. No.: 09/269,210 Maier & Neustadt, P.C. 22 PCT Filed: Sep. 23, 1997 57 ABSTRACT 86 PCT No.: PCT/EP97/05204 Polytetrahydrofuran, copolymers of tetrahydrofuran and S371 Date: Apr. 1, 1999 2-butyne-1,4-diol, diesters of these polymers with C-Co monocarboxylic acids or monoesters of these polymers with S 102(e) Date: Apr. 1, 1999 C1-Co-monocarboxylic acids are prepared by polymeriza 87 PCT Pub. No.: WO98/15589 tion of tetrahydrofuran in the presence of one of the telogens water, 1,4-butanediol, 2-butyne-1,4-diol, polytetrahydrofu PCT Pub. Date: Apr. 16, 1998 ran having a molecular weight of from 200 to 700 Dalton, 30 Foreign Application Priority Data a C-Co-monocarboxylic acid or an anhydride of a C-Co monocarboxylic acid or a mixture of these telogens over a Oct. 9, 1996 DEI Germany ........................... 196 41481 heterogeneous Supported catalyst which comprises a cata 51 Int. Cl." ........................... C07C 43/10; CO7C 43/11; lytically active amount of an oxygen-containing molybde CO7C 69/76; CO7C 67/24 num and/or tungsten compound on an oxidic Support mate 52 U.S. Cl. .......................... 568/617; 568/606; 560/103; rial and which has been calcined at from 5OO C. to 1 OOO 560/240 C. after application of the precursor compounds of the 58 Field of Search ..................................... 560/240, 103; oxygen-containing molybdenum and/or tungsten com 568/609, 617 pounds onto the Support material precursor, wherein the 56) References Cited catalyst is activated by treatment with a reducing agent before it is used as a polymerization catalyst. U.S. PATENT DOCUMENTS 3,893,947 7/1975 Young ..................................... 252/439 8 Claims, No Drawings 6,111,147 1 2 PROCESS FOR PREPARING monoesters of C1-Co-monocarboxylic acids by polymer POLYTETRAHYDROFURAN AND ization of tetrahydrofuran over a heterogeneous catalyst in DERVATIVES THEREOF the presence of one of the telogens water, 1,4-butanediol, PTHF having a molecular weight of from 200 to 700 Dalton, This application is a 371 of PCT/EP97/05204 filed Sep. 5 a C-Co-monocarboxylic acid or an anhydride of a C-Co 23, 1997. monocarboxylic acid or a mixture of these telogens, with the catalyst being a Supported catalyst which comprises a cata FIELD OF THE INVENTION lytically active amount of an oxygen-containing tungsten or The present invention relates to an improved proceSS for molybdenum compound or a mixture thereof on an oxidic preparing polytetrahydrofuran, copolymers of tetrahydrofu support material and which has been calcined at from 500 ran and 2-butyne-1,4-diol, diesters of these polymers with C. to 1000 C. after application of the precursor compounds C-Co-monocarboxylic acids or monoesters of these poly of the oxygen-containing molybdenum and/or tungsten mers with C-C-monocarboxylic acids by polymerization compounds onto the Support material precursor. of tetrahydrofuran in the presence of one of the telogens WO 96/09335 teaches a process for preparing PTHF or water, 1,4-butanediol, 2-butyne-1,4-diol, polytetrahydrofu 15 PTHF monoesters of C1-Co-monocarboxylic acids by ran having a molecular weight of from 200 to 700 Dalton, polymerization of tetrahydrofuran over a heterogeneous a C-Co-monocarboxylic acid or an anhydride of a C-Co catalyst in the presence of one of the telogens water, monocarboxylic acid or a mixture of these telogens over a 1,4-butanediol, PTHF having a molecular weight of from heterogeneous Supported catalyst which comprises a cata 200 to 700 Dalton, a C-C-monocarboxylic acid or a lytically active amount of an oxygen-containing molybde mixture of these telogens, with the catalyst being a Sup num and/or tungsten compound on an oxidic Support mate ported catalyst which comprises a catalytically active rial and which has been calcined at from 500 C. to 1000 amount of an oxygen-containing tungsten or molybdenum C. after application of the precursor compounds of the compound or a mixture thereof on an oxidic Support material oxygen-containing molybdenum and/or tungsten com and which has been calcined at from 500 C. to 1000 C. pounds onto the Support material precursor. 25 after application of the precursor compounds of the oxygen Polytetrahydrofuran (“PTHF"), also known as poly containing molybdenum and/or tungsten compounds onto (oxybutylene glycol), is a versatile intermediate in the the Support material precursor. plastics and Synthetic fibers industries and Serves, inter alia, for the preparation of polyurethane, polyester and polyamide SUMMARY OF THE INVENTION elastomers for whose preparation it is used as diol compo It is an object of the present invention to increase the nent. In addition, polytetrahydrofuran as well as Some of its catalytic activity of the THF polymerization catalysts derivatives is a valuable auxiliary in many applications, for described in DE 44 33 606 or WO 96/09335 in order to example as dispersant or for deinking waste paper. achieve higher polymer yields and/or space-time yields, thus In industry, PTHF is advantageously prepared by poly 35 improving the economics of the proceSS which depend merization of tetrahydrofuran over Suitable catalysts in the decisively on the productivity of the catalyst. presence of reagents whose addition makes it possible to control the length of the polymer chains and thus to Set the DETAILED DESCRIPTION OF THE mean molecular weight to the desired value (chain PREFERRED EMBODIMENTS termination reagents or "telogens'). The control is effected 40 We have found that this object is achieved by an improved here by Selection of type and amount of the telogen. Selec process for preparing polytetrahydrofuran, copolymers of tion of Suitable telogens makes it possible to introduce tetrahydrofuran and 2-butyne-1,4-diol, diesters of these additional functional groups at one end or both ends of the polymers with C-Co-monocarboxylic acids or monoesters polymer chain. Thus, for example, the monoesters or of these polymers with C1-Co-monocarboxylic acids by diesters of PTHF can be prepared by using carboxylic acids 45 polymerization of tetrahydrofuran in the presence of one of or carboxylic anhydrides as telogens. Other telogens, for the telogens water, 1,4-butanediol, 2-butyne-1,4-diol, poly example those having two hydroxy groupS Such as 1,4- tetrahydrofuran having a molecular weight of from 200 to butanediol, 2-butyne-1,4-diol or low molecular weight 700 Dalton, a C-Co-monocarboxylic acid or an anhydride PTHF not only act as chain-termination reagents, but are of a C-Co-monocarboxylic acid or a mixture of these also incorporated into the growing polymer chain of the 50 telogens over a heterogeneous Supported catalyst which PTHF. In this way, the PTHP can also be chemically comprises a catalytically active amount of an oxygen modified. An example of this is the use of the telogen containing molybdenum and/or tungsten compound on an 2-butyne-1,4-diol whose addition leads to the presence of a oxidic Support material and which has been calcined at from proportion of CEC triple bonds in the polymer chains of the 500° C. to 1000° C. after application of the precursor PTHF. 55 compounds of the oxygen-containing molybdenum and/or PTHF modified in this way can be further altered chemi tungsten compounds onto the Support material precursor, cally at these points by means of the reactivity of these triple wherein the catalyst is activated by treatment with a reduc bonds, for example by hydrogenation of the triple bonds to ing agent before it is used as a polymerization catalyst. double bonds, by Subsequent grafting-on of other monomers Polymerization catalysts used in the process of the present for adjusting the properties of the polymer, crosslinking to 60 invention are Supported catalysts which comprise an oxidic form polymers having a comparatively rigid structure, or Support material and oxygen-containing molybdenum or other conventional procedures of polymer chemistry. The tungsten compounds or mixtures thereof as catalytically complete hydrogenation of the triple bonds present is like active compounds and which can, if desired, additionally be wise possible and generally leads to PTHF having a par doped with Sulfate and/or phosphate groups. To convert ticularly low color number. 65 them into their catalytically active form, the Supported DE-A 4433 606 describes a process for preparing PTHF, catalysts are subjected to calcination at from 500 C. to PTHF diesters of C-C-monocarboxylic acids or PTHF 1000 C. after application of the precursor compounds of the 6,111,147 3 4 catalytically active, oxygen-containing molybdenum and/or tetrahydridoborates Such as Sodium tetrahydridoborate, tungsten compounds onto the Support material, with the 9-borabicyclononane, catecholborane, a Solution of diborane Support material and the precursor compound being con in tetrahydrofuran or in other ethers, alkali metal tetrahy verted into the catalyst. dridoaluminates Such as lithium tetrahydridoaluminate, or The catalysts, their preparation and their use in the simple binary hydrides such as the hydrides of the alkali or processes for preparing polytetrahydrofuran, polytetrahy alkaline earth metals, e.g.
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