EP2419214A1

EP2419214A1 - Improved catalyst for manufacturing polymers of tetrahydrofuran

Info

Publication number: EP2419214A1
Application number: EP09843449A
Authority: EP
Inventors: Qun Sun
Original assignee: Invista Technologies SARL Switzerland; Invista Technologies SARL USA
Current assignee: Invista Technologies Sarl
Priority date: 2009-04-15
Filing date: 2009-04-15
Publication date: 2012-02-22
Also published as: JP2012524149A; WO2010120292A1; CN102395430A; CN102395430B; MX2011010775A; BRPI0923998A2; JP5599868B2; WO2010120292A8; HK1164211A1; KR20120017424A; EP2419214A4

Abstract

The present invention provides an improved catalyst useful for manufacturing homopolymers and copolymers of tetrahydrofuran, the method for its preparation, and its use as catalyst in a process for manufacturing homopolymers and copolymers of tetrahydrofuran. More particularly, the invention relates to a treated perfluorosulfonic acid resin having the most soluble components reduced by from about 2 to about 20 wt% and an increased average equivalent weight compared to said perfluorosulfonic acid resin prior to treatment, the method for preparing the treated perfluorosulphonic acid resin, and its use as catalyst in a process for manufacturing homopolymers and copolymers of tetrahydrofuran in the presence of said catalyst.

Description

IMPROVED CATALYST FOR MANUFACTURING POLYMERS OF TETRAHYDROFURAN

FIELD OF THE INVENTION

[0001] The present invention relates to an improved catalyst for manufacturing polyether glycols, the method for its preparation, and its use as catalyst in a process for manufacturing polyether glycols by polymerization of tetrahydrofuran or tetrahydrofuran and at least one other cyclic ether, for example aikylene oxide. More particularly, the invention relates to a treated perfluorosulfonic acid resin catalyst having its most soluble components reduced by from about 2 to about 20 wt% and an increased average equivalent weight compared to said perfluorosulfonic acid resin prior to treatment, the method for preparing said treated perfluorosulphonic acid resin catalyst, and its use as catalyst in a process for manufacturing polyether glycols by polymerization of tetrahydrofuran or tetrahydrofuran and at least one other aikylene oxide in the presence of said catalyst.

BACKGROUND OF THE INVENTION

[0002] Homopolymers of tetrahydrofuran (THF), also known as polytetramethylene ether glycols (PTMEG), are well known for use as soft segments in polyurethanes and other elastomers. These homopolymers impart superior dynamic properties to polyurethane elastomers and fibers. Copolymers of THF and at least one other cyclic ether, also known as copolyether glycols, are known for use in similar applications, particularly where the reduced crystallinity imparted by the cyclic ether may improve certain dynamic properties of a polyurethane which contains such a copolymer as a soft segment. Among the cyclic ethers used for this purpose are ethylene oxide and propylene oxide.

[0003] The THF homopolymer and copolymers of THF and at least one other cyclic ether are well known in the art. Their preparation is disclosed, for example, by Heinsohn et al. in U.S. Pat. No. 4,163,115, by Pruckmayr in U.S. Pats. Nos. 4,120,903 and 4,139,567, and U.S. Pat. No. 4,153,786. Such homopolymer and copolymers can be prepared by any of the known methods of cyclic ether polymerization, described for instance in "Polytetrahydrofuran" by P. Dreyfuss (Gordon & Breach, N.Y. 1982). Such polymerization methods include catalysis by strong proton or Lewis acids, by heteropoly acids, as well as by perfluorosulfonic acids or acid resins. In some instances it may be advantageous to use a polymerization promoter, such as a carboxylic acid anhydride, as disclosed in U.S. Pat. No. 4,163,115. In these cases the primary polymer products are diesters, which need to be hydrolyzed in a subsequent step to obtain the desired polyether glycols.

[0004] It has been discovered that when acid catalysts comprising perfluorosulphonic acid resins are used for polymerization of THF or copolymerization of THF and another alkylene oxide, such as in U.S. Pat. Nos. 4,139,567 and 4,163,115, for example, resin leaching is difficult to avoid. This leads to overall reduction of commercial effectiveness of the polymerization process, cloudy product and increases of costs associated with down time and clean up.

SUMMARY OF THE INVENTION

[0005] The present invention provides a simple economical method for preparing improved catalyst comprising perfluorosulphonic acid resin, the improved catalyst obtained, and its use in a process for the polymerization of THF or copolymerization of THF and at least one other cyclic ether, for example alkylene oxide, which minimizes or avoids resin leaching during the polymerization process, leading to commercially desirable clear product. The method involves treating perfluorosulphonic acid resin catalyst having, for example, an average equivalent weight (EW) of from about 600 to about 2000 g/mol H⁺ to remove from about 2 to about 20 wt%, for example from about 2 to about 15 wt%, of the most soluble components of the perfluorosulfonic acid resin therefrom. The treatment method comprises contacting the perfluorosulfonic acid resin with deionized water at conditions of temperature, pressure and contact time sufficient to remove from about 2 to about 20 wt% of its most soluble components and increase its average equivalent weight.

[0006] The THF polymerization or copolymerization process utilizing the improved catalyst is not limited to a particular mode of operation, i.e. batch or continuous process, or acetic anhydride promoted process as disclosed in U.S. Pat. No. 4,163,115 or the unpromoted process as disclosed in U.S. Pat. No. 4,120,903 for THF polymerization or that for THF copolymerization as disclosed in U.S. Pat. Nos. 4,139,567 and 6,989,432.

DETAILED DESCRIPTION OF THE INVENTION

[0007] As a result of intense research in view of the above, we have found that we can provide improved catalysts comprising perfluorosulphonic acid resins for use in a process for manufacturing polyether glycols or copolyether glycols, for example poly(tetramethylene-co-ethyleneether) glycol, having a mean molecular weight of from about 200 dalton to about 5000 dalton, said process unencumbered by significant catalyst resin leaching. The method for providing the improved catalyst involves treating perfluorosulphonic acid resin, such as, for example, one having an average equivalent weight (EW) of from about 600 to about 2000 g/mol H⁺, to remove at least about 2 wt%, such as from about 2 to about 20 wt%, for example from about 2 to about 15 wt%, of the most soluble components of the perfluorosulfonic acid resin therefrom to provide an improved catalyst. The polymerization process utilizing the improved catalyst of the invention can suitably be any of the known processes, such as for example those mentioned herein, for use of perfluorosulfonic acid resin catalyst.

[0008] The term "polymerization", as used herein, unless otherwise indicated, includes the term "copolymerization" within its meaning.

[0009] The term "PTMEG", as used herein, unless otherwise indicated, means polytetramethylene ether glycol. PTMEG is also known as polyoxybutylene glycol. [00010] The term "copolyether glycol", as used herein in the singular, unless otherwise indicated, means copolymers of tetrahydrofuran and at least one other cyclic ether such as 1 ,2-alkylene oxide, which are also known as polyoxybutylene polyoxyalkylene glycols. An example of a copolyether glycol is a copolymer of tetrahydrofuran and ethylene oxide. This copolyether glycol is also known as poly(tetramethylene-co-ethyleneether) glycol.

[00011] The term "THF", as used herein, unless otherwise indicated, means tetrahydrofuran and includes within its meaning alkyl substituted tetrahydrofuran capable of copolymerizing with THF, for example 2- methyltetrahydrofuran, 3-methyltetrahydrofuran, and 3-ethyltetrahydrofuran.

[00012] The term "alkylene oxide", as used herein, unless otherwise indicated, means a compound containing two, three or four carbon atoms in its alkylene oxide ring. The alkylene oxide can be unsubstituted or substituted with, for example, linear or branched alkyl of 1 to 6 carbon atoms, or aryl which is unsubstituted or substituted by alkyl and/or alkoxy of 1 or 2 carbon atoms, or halogen atoms such as chlorine or fluorine. Examples of such compounds include ethylene oxide; 1 ,2-propylene oxide; 1 ,3-propylene oxide; 1 ,2-butylene oxide; 1 ,3-butylene oxide; 2,3-butylene oxide; styrene oxide; 2,2-bis-chloromethyl-1 ,3-propylene oxide; epichlorohydrin; perfluoroalkyl oxiranes, for example (1 H,1 H-perfluoropentyl) oxirane; and combinations thereof.

[00013] The present invention comprises a method for preparing improved acid catalysts comprising perfluorosulphonic acid resins. The method involves treating perfluorosulphonic acid resin to remove at least about 2 wt%, such as from about 2 to about 20 wt%, for example from about 2 to about 15 wt%, of the most soluble components of the perfluorosulfonic acid resin therefrom to provide an improved catalyst. The present invention further comprises the improved treated catalyst provided by this method. The present invention still further comprises use of this improved catalyst in a process for polymerization of THF or copolymerization of THF and at least one other cyclic ether, for example alkylene oxide, which minimizes or avoids resin leaching during the polymerization process, leading to commercially desirable clear product.

[00014] One embodiment of the present invention comprises the steps of (7) charging perfluorosulphonic acid resin, for example one having an average equivalent weight (EW) of from about 600 to about 2000 g/mol H⁺, such as one having an equivalent weight of from about 600 to about 1070 g/mol H⁺, and water, for example deionized water, at a resin/water weight ratio of from about 1/1 to about 1/20, for example from about 1/2 to about 1/15, into a pressure vessel, for example an autoclave, with a pressure rating of, for example, at least about 500 psig, (2) heating the contents of the pressure vessel to elevated temperature sufficient to remove from about 2 to about 20 wt%, for example from about 2 to about 15 wt%, of the most soluble components of the perfluorosulfonic acid resin from the perfluorosulfonic acid resin resulting in a treated perfluorosulfonic acid resin product, and (3) recovering the treated perfluorosulfonic acid resin product. The resin/water weight ratio in step (7) may be, for example, from about 1/4 to about 1/10. The elevated temperature of step (2) is for example from about 150⁰C to about 210⁰C, preferably sufficient to maintain the pressure vessel content in at least partial liquid form. The contact time for step (2) may be up to about 12 hours, for example from about 1 to about 12 hours, e.g. from about 1 to about 8 hours, and is sufficient to remove at least a portion of the most soluble components of the resin. In this embodiment, the contents of the pressure vessel may be agitated, for example by shaking or mixing, for example at from about 60 to about 300 rpm. The pressure in the pressure vessel is maintained sufficient to provide liquid water in the pressure vessel.

[00015] The improved perfluorosulphonic acid resin catalyst of the present invention comprises such a resin having reduced most soluble components from that of the original material. The reduction in most soluble components from the original perfluorosulphonic acid resin is at least about 2 wt% of the original soluble components, such as from about 2 to about 20 wt%, e.g. from about 2 to about 15 wt%. Non-limiting examples of improved perfluorosulphonic acid resin catalyst of the present invention comprise such a resin having about 3, 5 or 10 wt% of the original most soluble components removed. Another property which distinguishes the improved perfluorosulphonic acid resin catalyst of the present invention from the original perfluorosulphonic acid resin includes an increased average equivalent molecular weight, such as of at least about 10 g/mol H⁺. For example, an improved perfluorosulphonic acid resin catalyst will have an average equivalent molecular weight of from about 610 to about 2010 g/mol H⁺ if the EW of the original acid resin was from about 600 to about 2000 g/mol H⁺. More particularly, an original perfluorosulphonic acid resin catalyst having an EW of about 1070 g/mol H⁺ will have an EW of at least about 1080 g/mol H⁺ after treatment according to this invention.

[00016] Another embodiment of the present invention is a process for the polymerization of THF or copolymerization of THF and another cyclic ether, e.g. alkylene oxide, which minimizes or avoids catalyst resin leaching during the polymerization process.

[00017] The THF used as a reactant in the process of the invention utilizing the improved catalyst can be any of those commercially available. Typically, the THF has a water content of less than about 0.03% by weight and a peroxide content of less than about 0.005% by weight. If the THF contains unsaturated compounds, their concentration should be such that they do not have a detrimental effect on the polymerization process of the present invention or the polymerization product thereof. For example, for some applications it is preferred that the polyether or copolyether glycol product of the present invention has very low APHA color, such as, for example less than about 40 APHA units. If desired, one or more alkyl substituted THF's capable of copolymerizing with THF can be used as a co-reactant, in an amount from about 0.1 to about 70% by weight of the THF. Examples of such alkyl substituted THF's include 2-methyltetrahydrofuran, 3- methyltetrahydrofuran, and 3-ethyltetrahydrofuran.

[00018] The alkylene oxide used as a cyclic ether reactant in the present process utilizing the improved catalyst, as above indicated, may be a compound containing two, three or four carbon atoms in its alkylene oxide ring. It may be selected from, for example, the group consisting of ethylene oxide; 1 ,2-propylene oxide; 1 ,3-propylene oxide; 1 ,2-butylene oxide; 2,3- butylene oxide; 1 ,3-butylene oxide and combinations thereof. Preferably, the alkylene oxide has a water content of less than about 0.03% by weight, a total aldehyde content of less than about 0.01 % by weight, and an acidity (as acetic acid) of less than about 0.002% by weight. The alkylene oxide should be low in color and non-volatile residue.

[00019] If, for example, the alkylene oxide reactant is ethylene oxide (EO), it can be any of those commercially available. For example, the EO may have water content of less than about 0.03% by weight, a total aldehyde content of less than about 0.01 % by weight, and an acidity (as acetic acid) of less than about 0.002% by weight. The EO should be low in color and non-volatile residue.

[00020] Examples of compounds containing reactive hydrogen atoms which are suitable for use in the polymerization process of this invention include water, 1 ,4-butanediol, PTMEG having a molecular weight of from about 162 to about 400 dalton, copolyether glycols having a molecular weight of from about 134 to 400 dalton, and combinations thereof. An example of a suitable copolyether glycol for use as a compound containing reactive hydrogen atoms is poly(tetramethylene-co-ethyleneether) glycol having a molecular weight of from about 134 to about 400 dalton.

[00021] Among the suitable polymeric catalysts which contain sulfonic acid groups to be improved by the present invention, optionally with or without carboxylic acid groups, are those whose polymer chains are copolymers of tetrafluoroethylene or chlorotrifluoroethylene and a perfluoroalkyl vinyl ether containing sulfonic acid group precursors (again with or without carboxylic acid groups) as disclosed in U.S. Pat. Nos. 4,163,115 and 5,118,869, and as supplied commercially by E. I. du Pont de Nemours and Company under the trade name Nafion®. Such polymeric catalysts are also referred to as polymers comprising alpha-fluorosulfonic acids. An example of this type of catalyst for use herein is a perfluorosulfonic acid resin, i.e. it comprises a perfluorocarbon backbone and the side chain is represented by the formula - 0-CF₂CF(CF₃)O-CF₂CF₂SO₃H. Polymers of this type are disclosed in U.S. Patent No. 3,282,875 and can be made by copolymerization of tetrafluoroethylene (TFE) and the perfluorinated vinyl ether CF₂=CF-O- CF₂CF(CF₃)-O-CF₂CF₂SO₂F, perfluoro (3,6-dioxa-4-methyl-7-octenesulfonyl fluoride) (PDMOF), followed by conversion to sulfonate groups by hydrolysis of the sulfonyl fluoride groups and ion exchanged as necessary to convert them to the desired acidic form.

[00022] The improved catalysts which can be employed according to the present invention can be used in the form of powders or as shaped bodies, for example in the form of beads, cylindrical extrudates, spheres, rings, spirals, or granules.

[00023] The polymerization step of the present invention may be carried out with or without a solvent. Excess THF may serve as a solvent for the polymerization process step, or an inert solvent, such as one or more aliphatic, cycloaliphatic, or aromatic hydrocarbons, may be used if desired. It is also possible to use the dimer(s) of the alkylene oxide(s) comonomers, for example 1 ,4-dioxane in the case of ethylene oxide, as a solvent, alone or in conjunction with another solvent, for example THF.

[00024] The polymerization step of the present invention is generally carried out at from about O⁰C to about 12O⁰C, such as from about 4O⁰C to about 8O⁰C, e.g. from about 4O⁰C to about 72⁰C. The pressure employed in the polymerization step is generally not critical to the result of the polymerization, and pressures such as atmospheric pressure, the autogenous pressure of the polymerization system, and elevated pressures may be used.

[00025] To avoid the formation of peroxides, the polymerization step of the present process may be conducted under an inert gas atmosphere. Non- limiting examples of suitable inert gases for use herein include nitrogen, carbon dioxide, or the noble gases. [00026] The polymerization step of the present invention can also be carried out in the presence of hydrogen at hydrogen pressure of from about 0.1 to about 10 bar.

[00027] The process of the invention can be carried out continuously, or with one or more steps of the process being carried out batchwise.

[00028] The polymerization reaction can be carried out in conventional reactors or reactor assemblies suitable for continuous processes in a suspension or fixed-bed mode, for example in loop reactors or stirred reactors in the case of a suspension process or in tube reactors or fixed-bed reactors in the case of a fixed-bed process. A continually stirred tank reactor (CSTR) is desirable due to the need for good mixing in the present polymerization process, especially when the products are produced in a single pass mode.

[00029] When a continuous polymerization reactor apparatus is used, the improved catalyst can, if desired, be preconditioned after it has been introduced into the reactor(s). Examples of catalyst preconditioning include drying by means of gases, for example air or nitrogen, which have been heated to 80-200⁰C. The improved catalyst can also be used without preconditioning.

[00030] In a fixed-bed process, the polymerization reactor apparatus can be operated in the upflow mode, that is, the reaction mixture is conveyed from the bottom upward, or in the downflow mode, that is, the reaction mixture is conveyed through the reactor from the top downward.

[00031] The polymerization reactor can be operated using a single pass without internal recirculation of product, such as in a CSTR. The polymerization reactor can also be operated in the circulation mode, i.e. the polymerization mixture leaving the reactor is circulated. In the circulation mode, the ratio of recycle to feed is less than 100:1 , for example less than 50:1 , or for example less than 40:1. [00032] Feeds can be introduced to the polymerization reactor using delivery systems common in current engineering practice either batchwise or continuously.

[00033] The following Examples demonstrate the present invention and its capability for use. The invention is capable of other and different embodiments, and its several details are capable of modifications in various apparent respects, without departing from the scope and spirit of the present invention. Accordingly, the Examples are to be regarded as illustrative in nature and not as restrictive.

Materials

[00034] THF was obtained from Chemcentral. The perfluorinated sulfonic acid resin, NR50 Nafion®, was obtained from E. I. du Pont de Nemours, Wilmington, Delaware, USA. The acetic anhydride and acetic acid were purchased from Aldrich Chemicals. Deionized water was used.

Analytical Methods

[00035] The conversion to copolymers is defined by the weight percent of non-volatiles in the crude product mixture collected from the reactor exit, which was measured by a vacuum oven (130°C and about 200 mmHg) removal of the volatiles in the crude product mixture typically for greater than about 2 hours.

[00036] The turbidity of the crude THF polymerization solution was determined by a VWR Catalog No. 66120-200 Turbidimeter in NTU units.

EXAMPLES

[00037] All parts and percentages are by weight unless otherwise indicated. Catalyst Pretreatment

Examples 1 - 9

[00038] Nine separate weighed 1 part portions of the Nation® perfluorinated sulfonic acid resin, having an equivalent weight (EW) of 1070 g/mol H⁺, Examples 1 - 9, and either 2 or 6 parts of deionized water were charged into a clean 500 ml stainless steel autoclave with a pressure rating of at least about 500 psig at separate times. The contents of the autoclave were heated to various temperatures ranging from 17O⁰C to 21O⁰C under agitation by stirring at about 200 rpm, and held at the respective temperature for various times of 2, 4 or 8 hours. The treated perfluorinated sulfonic acid resins were then recovered from the autoclave and weighed. The EW of recovered materials from samples 2, 3, 7 and 8 were also measured. The results of these treatment examples are presented in Table I below.

Table I

*Sample 6 was a consecutive run of sample 1 , so the weight loss is cumulative.

[00039] The results of Examples 1 through 9, resin samples 1 through 9, show that treatment resin/water ratio, temperature and time have important impact on the amount of dissolved most soluble resin components removed. In particular, lower treatment resin/water ratio, higher treatment temperature and longer treatment time lead to higher amounts of most soluble resin component dissolution.

Examples 10 - 12

[00040] Three separate weighed 1 part portions of the Nafion® brand perfluorinated sulfonic acid resin catalyst NR50, having an equivalent weight (EW) of 1060 g/mol H⁺, Examples 10 - 12, were prepared. The Example 10 portion was set aside. In two separate experiments the Example 11 and 12 portions and 6 parts of deionized water were individually charged into a clean 300 ml Hastelloy-C autoclave with a pressure rating of at least about 500 psig. The total charge to the autoclave for the Example 11 experiment was twice that of the Example 12 experiment. The contents of the autoclave were heated to 18O⁰C under agitation by stirring at about 250 rpm, and held at that temperature for 2.5 hours. The treated perfluorinated sulfonic acid resins were then recovered from the autoclave, washed with deionized water five times each and weighed.

[00041] The resins were each dried at 130⁰C in a vacuum oven for 3 hours and then tested as THF polymerization catalysts. The THF polymerizations were carried out at room temperature using 10 parts dried catalyst, 84 parts THF, 3 parts acetic acid and 3 parts acetic anhydride for 2.5 hours under agitation with a magnetic stir bar at about 250 rpm. The liquid product was checked for polymer conversion by drying off the volatiles of a small sample of about 2 grams, which was first dried at room temperature under a flow of nitrogen and then dried in a 130°C in a vacuum oven for 2 hours. The liquid product was also measured for turbidity using a VWR 66120-200 Turbidimeter. While not intending to be bound by a recitation of theory, it is believed that turbidity is an indication of the catalyst dissolution during the THF polymerization process.

[00042] The turbidity of the THF polymerization feed was also measured, and found to be 0.1 NTU. The turbidity results for use of the untreated catalyst (Example 10) and the treated catalysts (Examples 11 and 12) are presented in Table Il below. The untreated catalyst produced significantly lower THF conversion. While not intending to be bound by a recitation of theory, it is believed that the lower conversion observed with the untreated catalyst was due to the depolymerization of the THF polymer catalyzed by resin catalyst dissolved in the product mixture. This depolymerization was observed during the oven drying step. Table Il

[00043] The results of Examples 10 through 12 show the effectiveness of the treatment method of the present invention in reducing the amount of perfluorosulfonic acid resin catalyst leaching in the THF polymerization process. This results in improved stability for THF polymerization or copolymerization. Compared to the untreated resin catalyst, the resin catalysts treated according to the present invention provided very significant reduction in catalyst leaching during polymerization of THF as illustrated by the turbidity of the polymerization product solutions.

[00044] All patents, patent applications, test procedures, priority documents, articles, publications, manuals, and other documents cited herein are fully incorporated by reference to the extent such disclosure is not inconsistent with this invention and for all jurisdictions in which such incorporation is permitted.

[00045] When numerical lower limits and numerical upper limits are listed herein, ranges from any lower limit to any upper limit are contemplated.

[00046] While the illustrative embodiments of the invention have been described with particularity, it will be understood that various other modifications will be apparent to and may be readily made by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is not intended that the scope of the claims hereof be limited to the examples and descriptions set forth herein but rather that the claims be construed as encompassing all the features of patentable novelty which reside in the present invention, including all features which would be treated as equivalents thereof by those skilled in the art to which the invention pertains.

Claims

CLAIMSWhat is claimed is:

1. A method for treating perfluorosulfonic acid resin which comprises the steps of:

a) charging the perfluorosulfonic acid resin along with water at a resin/water weight ratio of from about 1/1 to about 1/20 into a pressure vessel,

b) heating the pressure vessel contents to elevated temperature and for a time sufficient to remove from about 2 to about 20 wt% of the most soluble components of the perfluorosulfonic acid resin from the perfluorosulfonic acid resin and increase the average equivalent weight thereof resulting in a treated perfluorosulfonic acid resin product having reduced soluble components by from about 2 to about 20 wt% and an increased average equivalent weight, and

c) recovering the treated perfluorosulfonic acid resin product of step b).

2. The method of claim 1 wherein the resin/water weight ratio in step a) is from about 1/2 to about 1/15, and the elevated temperature of step b) is sufficient to maintain the autoclave contents in at least partial liquid form.

3. The method of claim 1 wherein the pressure vessel contents are mechanically agitated during step b).

4. The method of claim 2 wherein the elevated temperature of step b) is from about 150⁰C to about 210⁰C and from about 2 to about 15 wt% of the most soluble components of the perfluorosulfonic acid resin are removed.

5. The method of claim 1 wherein step b) is maintained for a time of up to about 12 hours.

6. The method of claim 5 wherein the time is from about 1 to about 8 hours.

7. A treated perfluorosulfonic acid resin having its most soluble components reduced by from about 2 to about 20 wt% and an increased average equivalent weight compared to said perfluorosulfonic acid resin prior to treatment.

8. The perfluorosulfonic acid resin of claim 7 having its most soluble components reduced by from about 2 to about 15 wt% compared to said perfluorosulfonic acid resin prior to treatment.

9. A process for manufacturing polyether glycol or copolyether glycol having a mean molecular weight of from about 200 dalton to about 5000 dalton comprising the step of polymerizing at least one tetrahydrofuran or at least one tetrahydrofuran and at least one alkylene oxide at a polymerization temperature of from about O⁰C to about 120⁰C in the presence of catalyst comprising treated perfluorosulfonic acid resin having its most soluble components reduced by from about 2 to about 20 wt% and an increased average equivalent weight compared to said perfluorosulfonic acid resin prior to treatment, said treatment comprising contacting said perfluorosulfonic acid resin with deionized water at conditions of temperature, pressure and contact time sufficient to remove from about 2 to about 20 wt% of its most soluble components and increase its average equivalent weight.

10. The process of claim 9 wherein the alkylene oxide is selected from the group consisting of ethylene oxide; 1 ,2-propylene oxide; 1 ,3-propylene oxide; 1 ,2-butylene oxide; 2,3-butylene oxide; 1 ,3-butylene oxide; and combinations thereof.

11. The process of claim 9 wherein the polymerization temperature is from about 40⁰C to about 80⁰C.

12. The process of claim 9 wherein the tetrahydrofuran further comprises at least one alkyltetrahydrofuran selected from the group consisting of 2- methyltetrahydrofuran, 3-methyltetrahydrofuran, 3-ethyltetrahydrofuran and combinations thereof.

13. The process of claim 10 wherein the alkylene oxide comprises ethylene oxide.

14. The process of claim 10 wherein the temperature of the polymerization step is from about 40⁰C to about 72⁰C.

15. The process of claim 9 wherein the polymerization step is conducted in a continually stirred tank reactor.

16. A process for manufacturing copolyether glycol having a mean molecular weight of from about 650 dalton to about 5000 dalton comprising the step of polymerizing tetrahydrofuran and at least one alkylene oxide at a polymerization temperature of from about 40⁰C to about 80⁰C in the presence of at least one compound containing reactive hydrogen atoms and catalyst comprising treated perfluorosulfonic acid resin having most soluble components reduced by from about 2 to about 20 wt% and an increased average equivalent weight compared to said perfluorosulfonic acid resin prior to treatment, said treatment comprising contacting said perfluorosulfonic acid resin with deionized water at conditions of temperature, pressure and contact time sufficient to remove from about 2 to about 20 wt% of its most soluble components and increase its average equivalent weight.

17. The process of claim 16 wherein the alkylene oxide is selected from the group consisting of ethylene oxide; 1 ,2-propylene oxide; 1 ,3-propylene oxide; 1 ,2-butylene oxide; 2,3-butylene oxide; 1 ,3-butylene oxide; and combinations thereof.

18. The process of claim 16 wherein the compound containing reactive hydrogen atoms is selected from the group consisting of water, 1 ,4- butanediol, poly(tetramethylene ether) glycol having a molecular weight of from about 130 dalton to about 400 dalton, copolyether glycols having a molecular weight of from about 130 dalton to about 400 dalton, and combinations thereof.

19. The process of claim 16 wherein the tetrahydrofuran further comprises at least one alkyltetrahydrofuran selected from the group consisting of 2- methyltetrahydrofuran, 3-methyltetrahydrofuran, 3-ethyltetrahydrofuran and combinations thereof.

20. The process of claim 16 wherein the polymerization step is conducted in a continually stirred tank reactor.

21. The process of claim 17 wherein the alkylene oxide comprises ethylene oxide.

22. The process of claim 17 wherein the temperature of the polymerization step is from about 40⁰C to about 72⁰C.