JP2012524149A - Improved catalyst for the production of polymers of tetrahydrofuran - Google Patents

Abstract

  The present invention relates to an improved catalyst useful for preparing tetrahydrofuran homopolymers and copolymers, a process for its preparation, and its use as a catalyst in the process of making tetrahydrofuran homopolymers and copolymers. provide. More specifically, the present invention relates to a treated perfluoro having a most soluble component reduced by about 2 to about 20% by weight and an increased average equivalent weight compared to the perfluorosulfonic acid resin before treatment. The present invention relates to sulfonic acid resins, methods for preparing treated perfluorosulfonic acid resins, and their use as catalysts in methods for preparing homopolymers and copolymers of tetrahydrofuran in the presence of said catalysts.

Description

  The present invention relates to an improved catalyst for the production of polyether glycols, a process for the preparation thereof, and a catalyst for the production of polyether glycols by polymerization of tetrahydrofuran or tetrahydrofuran with at least one other cyclic ether such as alkylene oxide. As for its use as. More specifically, the present invention relates to a catalyst for a treated perfluorosulfonic acid resin, the most soluble component reduced by about 2 to about 20% by weight compared to the perfluorosulfonic acid resin before treatment. And a process for preparing a catalyst of the treated perfluorosulfonic acid resin, and a polyether by polymerization of tetrahydrofuran or tetrahydrofuran with at least one other alkylene oxide in the presence of the catalyst. It relates to its use as a catalyst in a process for producing glycols.

  A homopolymer of tetrahydrofuran (THF), also known as polytetramethylene ether glycol (PTMEG), is well known for use as a soft segment in polyurethanes and other elastomers. These homopolymers provide excellent kinetic properties to polyurethane elastomers and fibers. Copolymers of THF and at least one other cyclic ether, also known as copolyether glycols, have a reduced crystallinity imparted by cyclic ethers in particular, such copolymers as soft segments. It is known for use in similar applications that can improve the specific kinetic properties of the containing polyurethane. Among the cyclic ethers used for this purpose are ethylene oxide and propylene oxide.

  Homopolymers of THF and copolymers of THF with at least one other cyclic ether are well known in the art. Their preparation is disclosed, for example, in Heinsohn in Patent Document 1, by Puckmayr in Patent Documents 2 and 3, and in Patent Document 4 (see Patent Documents 1, 2, 3 and 4). Such homopolymers and copolymers can be prepared by any known method of cyclic ether polymerization described in Non-Patent Document 1, for example (see Non-Patent Document 1). Such polymerization methods include catalysis with strong protons or Lewis acids, with heteropoly acids, as well as with perfluorosulfonic acids or acid resins. In some cases, it may be beneficial to use a polymerization accelerator, such as carboxylic anhydride, as disclosed in US Pat. In these cases, the main polymer product is a diester, which needs to be hydrolyzed in subsequent steps to obtain the desired polyether glycol.

  When an acid catalyst comprising a perfluorosulfonic acid resin is used for the polymerization of THF or the copolymerization of THF with other alkylene oxides as in Patent Documents 3 and 1, for example, leaching of the resin may be avoided. It was found difficult (see Patent Documents 3 and 1). This results in an overall reduction in the commercial effect of the polymerization process, a hazy product and an increase in downtime and costs associated with cleaning.

US Pat. No. 4,163,115 U.S. Pat. No. 4,120,903 US Pat. No. 4,139,567 U.S. Pat. No. 4,153,786

P. “Polytetrahydrofuran” by Dreyfuss (Gordon & Breach, NY 1982)

SUMMARY OF THE INVENTION The present invention is a simple and economical method for preparing an improved catalyst comprising a perfluorosulfonic acid resin, the resulting improved catalyst, and minimizing resin leaching during the polymerization process. It is provided that its use in the polymerization of THF or the copolymerization of THF with at least one other cyclic ether, such as alkylene oxide, which results in, or avoids, a commercially desirable transparent product. The process treats a catalyst of perfluorosulfonic acid resin, for example having an average equivalent weight (EW) of about 600 to about 2000 g / mol H ⁺ , and then about 2 to about 20% by weight, for example about 2 to about 15% by weight. A step of removing the most soluble component of the perfluorosulfonic acid resin. The process removes the perfluorosulfonic acid resin under conditions of temperature, pressure and contact time sufficient to remove about 2 to about 20% by weight of the most soluble component and increase its average equivalent weight. Contacting with ionic water.

  A THF polymerization or copolymerization process utilizing an improved catalyst can be a specific method of operation, i.e. a batch process or a continuous process, or an acetic anhydride promoted process as disclosed in U.S. Pat. No. 4,163,115, Or a non-promoted method as disclosed in US Pat. No. 4,120,903 for the polymerization of THF or described in US Pat. Nos. 4,139,567 and 6,989,432 There is no limitation on the method for such THF copolymerization.

DETAILED DESCRIPTION OF THE INVENTION As a result of intensive research considering the above, we have obtained polyether glycols or copolyether glycols having an average molecular weight of about 200 Daltons to about 5000 Daltons, such as poly (tetramethylene-co-ethylene ether) PROBLEM TO BE SOLVED: To provide an improved catalyst comprising perfluorosulfonic acid resin for use in a process for producing glycol (tetramethylene-co-ethyleneether) glycol, which is not hindered by significant leaching of the catalyst resin. I found what I could do. A method for providing an improved catalyst is to treat a perfluorosulfonic acid resin, such as one having an average equivalent weight (EW) of about 600 to about 2000 g / mole of H ⁺ to give at least about 2% by weight, for example about 2 to 2%. About 20% by weight, for example about 2 to about 15% by weight, with the step of removing the most soluble components of the perfluorosulfonic acid resin therefrom to provide an improved catalyst. The polymerization process utilizing the improved catalyst of the present invention can suitably be any known process for the use of a perfluorosulfonic acid resin catalyst, such as those mentioned herein.

  The term “polymerization” as used herein includes the term “copolymerization” in its meaning unless otherwise indicated.

  The term “PTMEG” as used herein means polytetramethylene ether glycol unless otherwise stated. PTMEG is also known as polyoxybutylene glycol.

The term “copolyether glycol” as used herein in the singular, unless otherwise stated, means a copolymer of tetrahydrofuran and at least one other cyclic ether, such as 1,2-alkylene oxide, Is also known as polyoxybutylene, polyoxyalkylene glycol. An example of a copolyether glycol is a copolymer of tetrahydrofuran and ethylene oxide. This copolyether glycol is also known as poly (tetramethylene-co-ethylene ether) glycol.

  The term “THF” as used herein, unless otherwise stated, means tetrahydrofuran, in that sense an alkyl-substituted tetrahydrofuran, such as 2-methyltetrahydrofuran, 3-methyltetrahydrofuran and 3 -Contains ethyltetrahydrofuran.

  The term “alkylene oxide” as used herein, unless otherwise stated, means a compound containing 2, 3 or 4 carbon atoms in the alkylene oxide ring. Alkylene oxide may be unsubstituted or aryl, for example, linear or branched alkyl of 1 to 6 carbon atoms, or unsubstituted or substituted by alkyl and / or alkoxy of 1 or 2 carbon atoms Or substituted with a halogen atom such as chlorine or fluorine. Examples of such compounds are ethylene oxide, 1,2-propylene oxide, 1,3-propylene oxide, 1,2-butylene oxide, 1,3-butylene oxide, 2,3-butylene oxide, styrene oxide, oxidized 2,2-bis-chloromethyl-1,3-propylene, epichlorohydrin, perfluoroalkyloxiranes such as (1H, 1H-perfluoropentyl) oxirane and combinations thereof.

  The present invention comprises a method for preparing an improved acid catalyst comprising a perfluorosulfonic acid resin. The method treats the perfluorosulfonic acid resin to remove at least about 2% by weight of the most soluble component of the perfluorosulfonic acid resin, such as from about 2 to about 20% by weight, for example from about 2 to about 15% by weight. And providing a process for providing an improved catalyst. The present invention further comprises an improved treated catalyst provided by this method. The present invention also further provides for the polymerization of THF, or THF and at least one other cyclic ether, such as oxidation, to minimize or avoid leaching of the resin during the polymerization process, resulting in a commercially desirable clear product. The use of this improved catalyst in the process of copolymerization with alkylene comprises.

One embodiment of the present invention is (1) about 1/1 to about 1/20, such as about 1/2 to about 1/15 in a pressure vessel, such as an autoclave, for example with a pressure rating of at least about 500 psig. Perfluorosulfonic acid resin, for example having an average equivalent weight (EW) of H ⁺ of about 600 to about 2000 g / mol, for example having an equivalent weight of about 600 to about 1070 g / mol H ⁺ And water, for example deionized water, and (2) heating the contents of the pressure vessel to a sufficiently high temperature to produce from about 2 to 20%, for example from about 2 to about 15% by weight from the perfluorosulfonic acid resin. Removing the most soluble components of the perfluorosulfonic acid resin to produce a treated perfluorosulfonic acid resin product, and (3) recovering the treated perfluorosulfonic acid resin product That, comprising the step. The weight ratio of resin / water in step (1) can be, for example, about 1/4 to about 1/10. The elevated temperature of step (2) is, for example, preferably from about 150 ° C. to about 210 ° C. sufficient to maintain the contents of the pressure vessel in at least partially liquid form. The contact time of step (2) can be up to about 12 hours, such as about 1 to about 12 hours, such as about 1 to about 8 hours, and removes at least a portion of the most soluble components of the resin. Enough. In this embodiment, the contents of the pressure vessel can be agitated, for example, by shaking or mixing, for example at about 60 to about 300 rpm. The pressure in the pressure vessel is maintained sufficiently to provide liquid water in the pressure vessel.

The improved perfluorosulfonic acid resin catalyst of the present invention comprises such a resin having the most soluble components reduced from the original material resin. The decrease in the most soluble component from the initial perfluorosulfonic acid resin is at least about 2%, such as from about 2 to about 20%, such as from about 2 to about 15% by weight of the first soluble component. Non-limiting examples of the improved perfluorosulfonic acid resin catalyst of the present invention comprise such a resin that is about 3, 5 or 10% by weight of the first most soluble component removed. Other properties that distinguish the improved perfluorosulfonic acid resin catalyst of the present invention from the initial perfluorosulfonic acid resin include an increased average equivalent weight such as at least about 10 g / mol H ⁺ . If the EW of the initial acid resin is from about 600 to about 2000 g / mole H ⁺ , the improved perfluorosulfonic acid resin catalyst is considered to have an average equivalent weight of, for example, from about 610 to about 2010 g / mole H ^+. It is done. More specifically, the catalyst of the first perfluorosulfonic acid resin with about 1070 g / mol ^{H +} of EW, after the treatment according to the present invention are believed to have at least about 1080 g / mole of ^{H +} of EW.

  Another embodiment of the present invention is a method of polymerization of THF, or copolymerization of THF with other cyclic ethers such as alkylene oxide, which minimizes or avoids leaching of the catalyst resin during the polymerization process. .

  The THF used as a reactant in the process of the present invention using an improved catalyst can be any commercially available one. Typically, THF contains less than about 0.03% by weight water and less than about 0.005% by weight peroxide. If the THF contains unsaturated compounds, their concentration must be such that they have no detrimental effect on the polymerization process of the present invention or their polymerization products. For example, for some applications, the polyether or copolyether glycol product of the present invention preferably has a very low APHA color, eg, less than about 40 APHA units. If desired, one or more alkyl-substituted THF copolymerizable with THF in an amount of about 0.1 to about 70% by weight of THF can be used as a co-reactant. Examples of such alkyl substituted THF include 2-methyltetrahydrofuran, 3-methyltetrahydrofuran and 3-ethyltetrahydrofuran.

  As described above, the alkylene oxide used as the reactant of the cyclic ether in the present process using an improved catalyst is a compound containing 2, 3 or 4 carbon atoms in the alkylene oxide ring. Can do. For example, it 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. can do. The alkylene oxide preferably 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 must have a low color and non-volatile residue.

  For example, if the alkylene oxide reactant is ethylene oxide (EO), it can be any commercially available product. The EO can have, for example, 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. EO should be low in color and non-volatile residue.

  Examples of compounds containing reactive hydrogen atoms suitable for use in the polymerization process of the present invention include water, 1,4-butanediol, PTMEG having a molecular weight of about 162 to about 400 daltons, and a molecular weight of about 134 to about 400 daltons. Copolyether glycols and combinations thereof. An example of a copolyether glycol suitable for use as a compound containing a reactive hydrogen atom is poly (tetramethylene-co-ethylene ether) glycol having a molecular weight of about 134 to about 400 daltons.

Suitable polymeric catalysts containing sulfonic acid groups which may or may not contain carboxylic acid groups and which may be modified according to the present invention include US Pat. Nos. 4,163,115 and 5,118,869. And is traded under the trade name Nafion®. I. du
Their polymer chain, as marketed by Pont de Nemours and Company, contains tetrafluoroethylene or chlorotrifluoroethylene and a precursor of a sulfonic acid group (again, with or without a carboxylic acid group). Some are copolymers with perfluoroalkyl vinyl ethers. Such polymeric catalysts are also referred to as polymers comprising alpha-fluorosulfonic acid. An example of this type of catalyst for use in this process is a resin of perfluorosulfonic acid, i.e. it comprises a perfluorocarbon backbone and the side chain of the formula _{-O-CF 2 CF (CF 3} ) -O- It is represented by CF ₂ CF ₂ SO ₃ H. This type of polymer is disclosed in US Pat. No. 3,282,875, where tetrafluoroethylene (TFE) and perfluorovinyl ether CF ₂ ═CF—O—CF ₂ CF (CF ₃ ) — _{O-CF 2 CF 2 SO 2} F, perfluoro (3,6-dioxa-4-methyl-7-octene sulfonyl fluoride) and (PDMOF), a copolymer, then sulfonic acid by hydrolysis of the sulfonyl fluoride groups Can be prepared by conversion to a group and, if necessary, ion exchange to convert them to the desired acidic form.

  The improved catalysts which can be used according to the 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.

  The polymerization process of the present invention can be carried out with or without a solvent. Excess THF can serve as a solvent for the polymerization process step, or an inert solvent such as one or more aliphatic, cycloaliphatic or aromatic hydrocarbons can be used as desired. Further, in the case of ethylene oxide, as a solvent, one or more dimers of one or more alkylene oxide comonomers, such as 1,4-dioxane, alone or another solvent such as THF, Can also be used together.

  The polymerization process of the present invention is generally carried out at about 0 ° C to about 120 ° C, such as about 40 ° C to about 80 ° C, such as about 40 ° C to about 72 ° C. The pressure used in the polymerization process is generally not critical to the outcome of the polymerization, and pressures such as atmospheric pressure, the self-regulating pressure of the polymerization system and high pressure can be used.

  In order to avoid the formation of peroxides, the polymerization step of the process can be carried out under an inert gas atmosphere. Non-limiting examples of inert gases suitable for use in the present method include nitrogen, carbon dioxide or noble gases.

  The polymerization process of the present invention can also be carried out in the presence of hydrogen under a hydrogen pressure of about 0.1 to about 10 bar.

  The process of the present invention can be carried out continuously or using one or more steps of a process carried out in a batch process.

  The polymerization reaction is carried out in a conventional reactor or reactor assembly suitable for continuous processes in suspension or fixed bed processes, for example in the case of suspension processes, in loop reactors or stirred reactors, or in fixed beds. In the case of the process, it can be carried out in a tube reactor or a fixed bed reactor. A continuous stirred tank reactor (CSTR) is desirable, especially when the product is produced by a single pass process, because the present polymerization process requires good mixing.

When a continuous polymerization reactor apparatus is used, the improved catalyst can be preconditioned, if desired, after it has been introduced into one or more reactors. Examples of catalyst preconditioning include drying with a gas heated to 80-200 ° C., such as air or nitrogen. The improved catalyst can also be used without preconditioning.

  In the fixed bed process, the polymerization reactor apparatus can be operated in the reverse flow mode, i.e. the reaction mixture can be transported upwards from the bottom or can be operated in the down flow mode, i.e. the reaction mixture can be operated from the top. It is conveyed down through the reactor.

  The polymerization reactor can be operated using a single pass method without using internal product recycle, as in CSTR. The polymerization reactor can also be operated in a circulating mode, i.e. the polymerization mixture leaving the reactor is circulated. In circulation mode, the ratio of recycle to feed is less than 100: 1, such as less than 50: 1, or such as less than 40: 1.

  The feed can be introduced into the polymerization reactor using a delivery system common to recent engineering practices, either batch or continuous.

  The following examples illustrate the invention and its potential for use. The invention is capable of other and different embodiments, and its several details are capable of modifications in various obvious respects, without departing from the scope and spirit of the invention. Accordingly, the examples should be regarded as illustrative in nature and not as restrictive.

The material THF was obtained from Chemcentral. NR50 Nafion (registered trademark) of perfluorosulfonic acid resin is E.I. I. obtained from du Pont de Nemours, Wilmington, Delaware, USA. Acetic anhydride and acetic acid were purchased from Aldrich Chemical. Deionized water was used.

Conversion to analytical copolymer is defined by the weight percent of non-volatiles in the crude product mixture recovered from the reactor outlet, typically in the crude product mixture for more than about 2 hours. The volatiles were measured by removal of a vacuum oven (130 ° C., about 200 mm Hg).

  The turbidity of the crude THF polymerization solution is determined according to VWR catalog no. Determined in NTU units with a turbidity meter of 66120-200.

  All parts and percentages are based on weight unless otherwise stated.

Catalyst pretreatment
Examples 1-9
Nine separate weighed 1 part Nafion® perfluorinated sulfonic acid resins with an equivalent weight (EW) of 1070 g / mol H ⁺ , Examples 1-9 and 2 or 6 parts Deionized water was charged into a clean 500 ml stainless steel autoclave having a pressure rating of at least about 500 psig at separate times. The contents of the autoclave were heated to various temperatures ranging from 170 ° C. to 210 ° C. with stirring by stirring at about 200 rpm and maintained at the respective temperatures for various times of 2, 4 or 8 hours. Next, the treated perfluorosulfonic acid resin was recovered from the autoclave and weighed. The EW of the recovered material from samples 2, 3, 7, and 8 was also measured. The results of these processing examples are shown in Table 1 below.

  The results of Examples 1-9, resin samples 1-9 show that the treated resin / water ratio, temperature and time have a significant effect on the amount of dissolved and most soluble resin components removed. Show. Notably, lower processing resin / water ratios, higher processing temperatures and longer processing times result in higher dissolution amounts of the most soluble resin components.

Examples 10-12
Prepare three separate weighed one part Nafion® brand perfluorosulfonic acid resin catalysts NR50, Examples 10-12, with an equivalent weight (EW) of 1060 g / mol H ⁺ did. The part of Example 10 was set aside. In two separate experiments, portions of Examples 11 and 12 and 6 parts of deionized water were individually loaded into a clean 300 ml Hastelloy-C autoclave with a pressure rating of at least about 500 psig. The total charge in the autoclave for the experiment of Example 11 was twice that of the experiment of Example 12. The contents of the autoclave were heated to 180 ° C. with stirring by stirring at about 250 rpm and maintained at that temperature for 2.5 hours. Next, the treated perfluorosulfonic acid resin was recovered from the autoclave, washed 5 times with deionized water, and weighed.

  Each of the resins was dried in a vacuum oven at 130 ° C. for 3 hours and then tested as a THF polymerization catalyst. The THF polymerization was carried out for 2.5 hours at room temperature under stirring with a magnetic stir bar using 10 parts dry catalyst, 84 parts THF, 3 parts acetic acid and 3 parts acetic anhydride at about 250 rpm. Test polymer conversion of liquid product by drying off about 2 grams of a small sample of volatiles, first dried at room temperature under a nitrogen stream and then dried in a 130 ° C. vacuum oven for 2 hours. did. The liquid product was also measured for turbidity using a VWR 66120-200 turbidimeter. Although not intended to be limited by reiterating the theory, turbidity is believed to be an indicator of catalyst dissolution during the THF polymerization process.

  The turbidity of the THF polymerization feed was also measured and found to be 0.1 NTU. The turbidity results for the use of untreated catalyst (Example 10) and treated catalyst (Examples 11 and 12) are shown in Table II below. The untreated catalyst resulted in significantly lower THF conversion. Although not intended to be limited by the reiterative of the theory, the lower conversion observed with the untreated catalyst is due to the depolymerization of the THF polymer catalyzed by the resin catalyst dissolved in the product mixture. It is believed that there is. This depolymerization was observed during the oven drying process.

  The results of Examples 10 to 12 show the effectiveness of the treatment method of the present invention in reducing the amount of perfluorosulfonic acid resin leaching in the THF polymerization process. This results in improved stability of the THF polymerization or copolymerization. Compared to the untreated resin catalyst, the resin catalyst treated according to the present invention resulted in a very significant reduction in catalyst leaching during the polymerization of THF, as indicated by the turbidity of the solution of the polymerization product.

  All patents, patent applications, test methods, priority literature, articles, publications, manuals and other references cited herein are to the extent that their disclosures are consistent with the present invention and such incorporation. For all jurisdictions where is allowed to be incorporated herein by reference.

  When numerical lower limits and numerical upper limits are described herein, ranges from any lower limit to any upper limit are contemplated.

  While illustrative embodiments of the present invention have been described with particularity, various other modifications will be apparent to and readily made by those skilled in the art without departing from the spirit and scope of the invention. It will be appreciated that changes can be made. Therefore, it is not intended that the scope of the invention be limited to the examples and description provided herein, but rather, the scope of the claims is equivalent to those of ordinary skill in the art to which this invention pertains. It is intended that all features of the patentable novelty present in the present invention be included, including all features that are considered to be treated as.

Claims (22)

a) filling the pressure vessel with perfluorosulfonic acid resin together with water in a resin / water weight ratio of about 1/1 to about 1/20;
b) removing the contents of the pressure vessel from the perfluorosulfonic acid resin from about 2 to about 20% by weight of the most soluble component of the perfluorosulfonic acid resin and increasing its average equivalent weight to about 2 to about Heating to a sufficient temperature and for a sufficient time to produce a product of a treated perfluorosulfonic acid resin having a soluble component reduced by 20% by weight and an increased average equivalent weight; c) the treated perfluorosulfone of step b) Collect the acid resin product:
A method of treating a perfluorosulfonic acid resin comprising the steps.   The resin / water weight ratio in step a) is about 1/2 to about 1/15, and the high temperature of step b) is sufficient to maintain the autoclave contents at least partially in liquid form. Item 2. The method according to Item 1.   The method of claim 1, wherein the contents of the pressure vessel are mechanically agitated during step b).   The process of claim 2, wherein the elevated temperature of step b) is from about 150 ° C to about 210 ° C and about 2 to about 15% by weight of the most soluble component of the perfluorosulfonic acid resin is removed.   The method of claim 1, wherein step a) is maintained for a period of up to about 12 hours.   6. The method of claim 5, wherein the time is from about 1 to about 8 hours.   A treated perfluorosulfonic acid resin, the most soluble component of which is reduced by about 2 to about 20% by weight and the average equivalent weight is increased compared to the perfluorosulfonic acid resin before treatment.   8. The perfluorosulfonic acid resin of claim 7, wherein its most soluble component is reduced by about 2 to about 15% by weight compared to the perfluorosulfonic acid resin prior to treatment.   In the presence of a catalyst comprising a treated perfluorosulfonic acid resin, the most soluble component of which is reduced by about 2 to about 20% by weight relative to the perfluorosulfonic acid resin prior to treatment, and the average equivalent is increased. A polymer having an average molecular weight of from about 200 Daltons to about 5000 Daltons comprising polymerizing at least one tetrahydrofuran, or at least one tetrahydrofuran and at least one alkylene oxide, at a polymerization temperature of 0 ° C. to about 120 ° C. A method of making an ether glycol or copolyether glycol, wherein the treatment is sufficient to remove about 2 to about 20% by weight of the most soluble component and increase the average equivalent weight, pressure and contact. Contacting the perfluorosulfonic acid resin with deionized water under conditions of time; Process comprising the, process.   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. 10. The method of claim 9, wherein:   The process of claim 9 wherein the polymerization temperature is from about 40C to about 80C.   The method 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.   11. The method of claim 10, wherein the alkylene oxide comprises ethylene oxide.   The process of claim 10, wherein the temperature of the polymerization step is from about 40C to about 72C.   The process of claim 9 wherein the polymerization step is carried out in a continuous stirred tank reactor.   At least one compound containing a reactive hydrogen atom and a treated perfluorosulfonic acid resin in which the most soluble components are reduced by about 2 to about 20% by weight and the average equivalent weight is increased as compared to the perfluorosulfonic acid resin before treatment; Having an average molecular weight of about 650 daltons to about 5000 daltons comprising polymerizing tetrahydrofuran and at least one alkylene oxide at a polymerization temperature of about 40 ° C. to about 80 ° C. in the presence of a catalyst comprising A process for producing a copolyether glycol, wherein the treatment removes from about 2 to about 20% by weight of its most soluble component and conditions of temperature, pressure and contact time sufficient to increase its average equivalent weight A process comprising: contacting the perfluorosulfonic acid resin with deionized water under.   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. The method of claim 16, wherein:   The compound containing a reactive hydrogen atom is water, 1,4-butanediol, poly (tetramethylene ether) glycol having a molecular weight of about 130 daltons to about 400 daltons, copolyether glycol having a molecular weight of about 130 daltons to about 400 daltons The method of claim 16, wherein the method is selected from the group consisting of: and combinations thereof.   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.   The process of claim 16, wherein the polymerization step is carried out in a continuous stirred tank reactor.   18. The method of claim 17, wherein the alkylene oxide comprises ethylene oxide.   The process of claim 17, wherein the temperature of the polymerization step is from about 40C to about 72C.