KR20120017424A - Improved catalyst for manufacturing polymers of tetrahydrofuran - Google Patents

Abstract

The present invention provides improved catalysts useful for preparing homopolymers and copolymers of tetrahydrofuran, methods for their preparation, and their use as catalysts in the process for preparing homopolymers and copolymers of tetrahydrofuran. More specifically, the present invention relates to a treated perfluorosulfonic acid resin, a treated perfluorosulfonic acid resin, wherein the maximum soluble component 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. To a process for the preparation of homopolymers and copolymers of tetrahydrofuran in the presence of said catalyst.

Description

Improved catalyst for the production of polymers of tetrahydrofuran {IMPROVED CATALYST FOR MANUFACTURING POLYMERS OF TETRAHYDROFURAN}

The present invention provides an improved catalyst for producing polyether glycols, a process for preparing the same, and the preparation of polyether glycols by polymerization of tetrahydrofuran or tetrahydrofuran with one or more other cyclic ethers such as alkylene oxides. To the use thereof as a catalyst in the process. More specifically, the present invention provides a treated perfluorosulfonic acid resin catalyst, the treated perfluoro, wherein the maximum soluble component is reduced by about 2 to about 20 weight percent and the average equivalent is increased compared to the perfluorosulfonic acid resin before treatment. A process for preparing a sulfonic acid resin catalyst and its use as a catalyst in a process for producing polyether glycol by polymerization of tetrahydrofuran or tetrahydrofuran with at least one other alkylene oxide in the presence of the catalyst.

Homopolymers of tetrahydrofuran (THF), also known as polytetramethylene ether glycol (PTMEG), are well known for use as soft segments in polyurethanes and other elastomers. Such homopolymers impart excellent dynamic properties to polyurethane elastomers and fibers. Copolymers of THF with one or more other cyclic ethers (also known as copolyether glycols) are polyurethanes containing similar copolymers, especially the reduced degree of crystallinity imparted by cyclic ethers, containing such copolymers as soft segments. It is known to use for applications that can improve the specific dynamic properties of. Among the cyclic ethers used for this purpose are ethylene oxide and propylene oxide.

THF homopolymers and copolymers of THF with one or more other cyclic ethers are well known in the art. Their preparation is disclosed, for example, in US Pat. No. 4,163,115 to Heinsohn et al., US Pat. Nos. 4,120,903 and 4,139,567, and US Pat. No. 4,153,786 to Pruckmayr. Such homopolymers and copolymers can be prepared by any known cyclic ether polymerization process, such as described in "Polytetrahydrofuran" by P. Dreyfuss (Gordon & Breach, N.Y. 1982). Such polymerization methods include catalysis with strong protonic or Lewis acids, with heteropolyacids, and with perfluorosulfonic acid or acid resins. In some cases, it may be beneficial to use polymerization promoters such as carboxylic anhydrides disclosed in US Pat. No. 4,163,115. In this case, the main polymer product is the diester, which needs to be hydrolyzed in a subsequent step to obtain the desired polyether glycol.

For example, when an acid catalyst including a perfluorosulfonic acid resin is used for polymerization of THF or copolymerization of THF with other alkylene oxides, as in US Pat. Nos. 4,139,567 and 4,163,115, it is difficult to prevent resin leaching. I found that. This leads to an overall reduction in the commercial effectiveness of the polymerization process, cloudy products, and an increase in costs associated with downtime and washing.

The present invention provides a simple and economical process for producing an improved catalyst comprising a perfluorosulfonic acid resin, the improved catalyst obtained, and the polymerization of THF or copolymerization of THF with one or more other cyclic ethers such as alkylene oxides. Its use in the process provides, which prevents or minimizes resin leaching during the polymerization process to produce commercially desirable transparent products. The process comprises, for example, treating a perfluorosulfonic acid resin catalyst having an average equivalent weight (EW) of about 600 to about 2000 g / mol H ⁺ , from about 2 to about 20 weight percent of the maximum soluble component of the perfluorosulfonic acid resin. Such as removing from about 2 to about 15 weight percent. The treatment method comprises contacting the perfluorosulfonic acid resin with deionized water at conditions of temperature, pressure and contact time sufficient to remove about 2 to about 20 weight percent of its maximum soluble component and increase its average equivalent weight.

The THF polymerization or copolymerization process using an improved catalyst is described in certain modes of operation, namely batch or continuous processes, or acetic anhydride disclosed in US Pat. No. 4,163,115 for THF polymerization or THF copolymerization as disclosed in US Pat. Nos. 4,139,567 and 6,989,432. It is not limited to a facilitation method or a non-promoting method disclosed in US Pat. No. 4,120,903.

As a result of the intensive study in consideration of the above, for use in a method of preparing polyether glycol or copolyether glycol, such as poly (tetramethylene-co-ethyleneether) glycol, having an average molecular weight of about 200 Daltons to about 5000 Daltons, It was found that improved catalysts can be provided that include perfluorosulfonic acid resins, and that the process is not disturbed by significant catalyst resin leaching. The process for providing an improved catalyst comprises treating a perfluorosulfonic acid resin, such as a perfluorosulfonic acid resin having an average equivalent weight (EW) of about 600 to about 2000 g / mol H ⁺ , from which the maximum of perfluorosulfonic acid resin is obtained. Removing at least about 2%, such as about 2% to about 20%, such as about 2% to about 15% by weight of the soluble component to provide an improved catalyst. The polymerization process using the improved catalyst of the present invention may suitably be any known method for using a perfluorosulfonic acid resin catalyst, such as the method mentioned herein.

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

As used herein, the term "PTMEG" means polytetramethylene ether glycol unless otherwise indicated. PTMEG is also known as polyoxybutylene glycol.

As used herein in the singular form "copolyether glycol" means a copolymer of tetrahydrofuran and one or more other cyclic ethers, such as 1,2-alkylene oxide, unless otherwise indicated, which refers to polyoxybutylene Also known as polyoxyalkylene glycols. Examples of copolyether glycols are copolymers of tetrahydrofuran and ethylene oxide. Such copolyether glycols are also known as poly (tetramethylene-co-ethyleneether) glycols.

As used herein, the term “THF” means tetrahydrofuran, unless otherwise indicated, and alkyl substituted tetrahydrofuran copolymerizable with THF within the meaning, such as 2-methyltetrahydrofuran, 3-methyltetrahydrofuran and 3 Ethyltetrahydrofuran.

As used herein, the term "alkylene oxide" means a compound containing two, three or four carbon atoms in the alkylene oxide ring unless otherwise indicated. Alkylene oxides are unsubstituted or linear or branched alkyl having 1 to 6 carbon atoms, or alkyl and / or alkoxy having unsubstituted or 1 or 2 carbon atoms, or halogen atoms such as chlorine Or aryl substituted with 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 such as (1H, 1H-perfluoropentyl) oxirane; And combinations thereof.

The present invention includes a process for preparing an improved acid catalyst comprising a perfluorosulfonic acid resin. The process treats the perfluorosulfonic acid resin to provide an improved catalyst, from which at least about 2% by weight, such as about 2 to about 20% by weight, such as about 2, of the maximum soluble component of the perfluorosulfonic acid resin To about 15% by weight. The present invention further includes a treated and improved catalyst provided by this process. The present invention further includes the use of such an improved catalyst in the polymerization of THF or copolymerization of THF with one or more other cyclic ethers, such as alkylene oxides, which prevents or minimizes leaching of the resin during the polymerization process. To produce the desired clear product.

In one embodiment of the invention, (1) a perfluorosulfonic acid resin, such as a perfluorosulfonic acid resin having an average equivalent weight (EW) of about 600 to about 2000 g / mol H ⁺ , such as an equivalent of about 600 to about 1070 g / Molar H ⁺ phosphorus perfluorosulfonic acid resin and water, such as deionized water, are added to a pressure vessel such as an autoclave at a resin / water weight ratio of about 1/1 to about 1/20, such as about 1/2 to about 1/15. For example, filling with a pressure rating of at least about 500 psig, (2) from about 2 to about 20 weight percent, such as from about 2 to about 15 weight, of the maximum soluble component of the perfluorosulfonic acid resin from the perfluorosulfonic acid resin Heating the contents of the pressure vessel to an elevated temperature sufficient to remove the% to produce a treated perfluorosulfonic acid resin product, and (3) recovering the treated perfluorosulfonic acid resin product. The resin / water weight ratio of step (1) may be for example about 1/4 to about 1/10. The elevated temperature of step (2) is preferably sufficient, such as from about 150 ° C to about 210 ° C, to maintain the pressure vessel contents in at least partial liquid form. The contact time of step (2) may be about 12 hours or less, such as about 1 to about 12 hours, such as about 1 to about 8 hours, which is sufficient to remove at least some of the maximum soluble components of the resin. In such embodiments, the contents of the pressure vessel may be stirred at, for example, about 60 to about 300 rpm, such as by shaking or mixing. The pressure in the pressure vessel is maintained sufficient to provide liquid water to the pressure vessel.

The improved perfluorosulfonic acid resin catalyst of the present invention comprises a resin in which the maximum soluble component is reduced compared to the original material. The reduction rate of the maximum soluble component from the original perfluorosulfonic acid resin is at least about 2% by weight, such as about 2 to about 20% by weight, such as about 2 to about 15% by weight, of the original soluble component. Non-limiting examples of improved perfluorosulfonic acid resin catalysts of the present invention include resins in which about 3, 5, or 10 weight percent of the original maximum soluble component is removed. Other properties that distinguish the improved perfluorosulfonic acid resin catalyst of the present invention from the original perfluorosulfonic acid resins include, for example, increased average molecular equivalents of at least about 10 g / mol H ⁺ . For example, if the EW of the original acid resin is about 600 to about 2000 g / mol H ⁺ , the average molecular equivalent of the improved perfluorosulfonic acid resin catalyst will be about 610 to about 2010 g / mol H ⁺ . More specifically, the original perfluorosulfonic 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 the invention.

Another embodiment of the invention relates to a process for the polymerization of THF or a copolymerization of THF with other cyclic ethers such as alkylene oxides, which prevents or minimizes leaching of the catalyst resin during the polymerization process.

The THF used as reactant in the process of the present invention using an improved catalyst can be any of those commercially available. Typically, THF has a water content of less than about 0.03 weight percent and a peroxide content of less than about 0.005 weight percent. If THF contains an unsaturated compound, the concentration of the unsaturated compound should be such that it does not adversely affect the polymerization method or the polymerization product thereof. For example, for some applications it is desirable for the polyether or copolyether glycol products of the invention to have very low APHA colors, such as less than about 40 APHA units. If desired, one or more alkyl substituted THFs, copolymerizable with THF, may be used as the co-reactant in an amount from about 0.1 to about 70 weight percent of THF. Examples of such alkyl substituted THFs include 2-methyltetrahydrofuran, 3-methyltetrahydrofuran and 3-ethyltetrahydrofuran.

The alkylene oxide used as the cyclic ether reactant in the process of the invention using an improved catalyst may be a compound containing two, three or four carbon atoms in the alkylene oxide ring as indicated above. Alkylene oxides are, for example, 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 (acetic acid) of less than about 0.002% by weight. Alkylene oxides should be low in color and nonvolatile residues.

For example, if the alkylene oxide reactant is ethylene oxide (EO), it may be any of those commercially available. For example, EO may have a water content of less than about 0.03 weight percent, a total aldehyde content of less than about 0.01 weight percent, and an acidity (acetic acid) of less than about 0.002 weight percent. EO should be low in color and nonvolatile residues.

Examples of compounds containing reactive hydrogen atoms suitable for use in the polymerization process of the invention include water, 1,4-butanediol, PTMEG having a molecular weight of about 162 to about 400 daltons, copolyethers having a molecular weight of about 134 to 400 daltons Glycols and combinations thereof. Examples of suitable copolyether glycols for use as compounds containing reactive hydrogen atoms are poly (tetramethylene-co-ethyleneether) glycols having a molecular weight of about 134 to about 400 daltons.

Among suitable polymeric catalysts containing sulfonic acid groups and optionally having or without carboxylic acid groups, which are improved by the present invention, disclosed in U.S. Patent Nos. 4,163,115 and 5,118,869 and disclosed in Idupont Nemoir and Campani (EI) Copolymerization of tetrafluoroethylene or chlorotrifluoroethylene with perfluoroalkyl vinyl ethers containing sulfonic acid group precursors containing polymer chains commercially supplied under the trade name Nafion® by du Pont de Nemours and Company There are chain ones (with or without carboxylic acid groups). Such polymeric catalysts are also referred to as polymers including alpha-fluorosulfonic acid. An example of this type of catalyst for use herein is a perfluorosulfonic acid resin, ie comprising a perfluorocarbon backbone and the side chain is of the formula -O-CF ₂ CF (CF ₃ ) -O-CF ₂ CF ₂ SO ₃ It is represented by H. Polymers of this type are disclosed in U.S. Patent No. 3,282,875, wherein tetrafluoroethylene (TFE) and perfluorinated vinyl ethers CF ₂ = CF-O-CF ₂ CF (CF ₃ ) -O-CF ₂ CF ₂ SO _2F , conversion of perfluoro (3,6-dioxa-4-methyl-7-octensulfonyl fluoride) (PDMOF) to conversion to sulfonate groups by hydrolysis of sulfonyl fluoride groups, and It can be prepared by the ion exchange required for the conversion to the desired acid form.

The improved catalysts that can be used according to the invention can be used in powder form or in the form of shaped bodies such as beads, cylindrical extrudates, spheres, rings, helixes or granules.

The polymerization step of the present invention can be carried out with or without solvent. Excess THF can serve as a solvent for the polymerization process step, or if necessary an inert solvent such as one or more aliphatic, cycloaliphatic or aromatic hydrocarbons can be used. In addition, dimer (s) of alkylene oxide (s) comonomers, such as 1,4-dioxane for ethylene oxide, may be used alone or in combination with other solvents such as THF.

The polymerization step of the present invention may generally be 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 step is generally not critical to the result of the polymerization and pressures such as atmospheric pressure, autogenous pressure of the polymerization system and elevated pressure may be used.

In order to prevent the formation of peroxides, the polymerization step of the process of the invention can be carried out under an inert gas atmosphere. Non-limiting examples of inert gases suitable for use herein include nitrogen, carbon dioxide or rare gases.

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

The method of the invention can be carried out continuously or one or more steps of the method can be carried out in a batch manner.

The polymerization reaction can be carried out in a conventional reactor or reactor assembly suitable for continuous processes in suspension or fixed bed mode, such as in a loop reactor or a stirred reactor in the case of a suspension process, or in a tube reactor or a fixed bed reactor in the case of a fixed bed process. . In the polymerization process of the present invention, continuous stirred tank reactors (CSTRs) are preferred because of the need for good mixing, especially when the product is produced in single pass mode.

If a continuous polymerization reactor apparatus is used, the improved catalyst may be preconditioned after introduction into the reactor (s), if necessary. Examples of catalyst preconditioning include drying with a gas, such as air or nitrogen, heated to 80 to 200 ° C. Improved catalysts can also be used without preconditioning.

In a fixed bed process, the polymerization reactor apparatus may be operated in an upflow mode (i.e., the reaction mixture is passed from bottom to top) or in a downflow mode (i.e., the reaction mixture is passed from top to bottom through the reactor). Can be.

The polymerization reactor can be operated using a single pass without internal recycle of the product as in CSTR. The polymerization reactor can also be operated in a circulation mode, ie the polymerization mixture leaving the reactor is circulated. In the 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 may be introduced into the polymerization reactor either batchwise or continuously using a transfer system conventional to existing engineering practice.

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

matter

THF was obtained from Chemcentral. The NR50 Nafion® perfluorinated sulfonic acid resin was obtained from Idupont Nemoasa (Wilmington, Delaware, USA). Acetic anhydride and acetic acid were purchased from Aldrich Chemicals. Deionized water was used.

Analytical Method

Conversion to copolymer is defined as the weight percent of nonvolatiles in the crude product mixture collected from the reactor outlet, typically a vacuum oven (130 ° C. and about 200 mm Hg) that removes volatiles in the crude product mixture for more than about 2 hours. Was measured by.

The turbidity of the crude THF polymerization solution was determined by VWR Catalog No. Determined by 66120-200 turbidimeter (in NTU).

Example

All parts and percentages are by weight unless otherwise indicated.

Catalyst Pretreatment

Example 1-9

Nine separate portions (Examples 1-9) weighed with 1 part of Nafion® perfluorinated sulfonic acid resin having an equivalent weight (EW) of 1070 g / mol H ⁺ and 2 or 6 parts of deionized water at an individual time of about 500 psig Filled in clean 500 ml stainless steel autoclave at pressure rating. The contents of the autoclave were stirred at about 200 rpm, heated to various temperatures in the range of 170 ° C. to 210 ° C. under stirring and maintained at each temperature for various times of 2, 4 or 8 hours. The treated perfluorinated sulfonic acid resin was then recovered from the autoclave and weighed. In addition, EW of materials recovered from Samples 2, 3, 7 and 8 were measured. The results of these treated samples are shown in Table I below.

TABLE I

The results of Examples 1-9 (Resin Samples 1-9) show that the treatment resin / water ratio, temperature and time have a significant impact on the dissolution amount of the maximum soluble resin component removed. In particular, low treatment resin / water ratios, high treatment temperatures and longer treatment times lead to higher amounts of soluble resin component dissolution.

Example 10-12

Three separate portions (Examples 10-12) were weighed with 1 part of Nafion® brand perfluorinated sulfonic acid resin catalyst NR50 having an equivalent weight (EW) of 1060 g / mol H ⁺ . The part of Example 10 was left to one side. In two separate experiments, 11 and 12 parts and 6 parts of deionized water were each filled in a clean 300 ml Hastelloy-C autoclave at a pressure rating of at least about 500 psig. For Example 11 experiments the total charge of the autoclave was twice that of the Example 12 experiment. The contents of the autoclave were stirred at about 250 rpm, heated to 180 ° C. under stirring and held at that temperature for 2.5 hours. The treated perfluorinated sulfonic acid resin was then recovered from the autoclave and weighed by washing five times with deionized water each.

The resins were each dried at 130 ° C. in a vacuum oven for 3 hours and then tested as THF polymerization catalysts. THF polymerization was performed at room temperature using 10 parts of dried catalyst, 84 parts of THF, 3 parts of acetic acid and 3 parts of acetic anhydride for 2.5 hours under stirring using a magnetic stir bar at about 250 rpm. The polymer conversion of the liquid product was confirmed by drying about 2 grams of small sample of volatiles first dried at room temperature under nitrogen flow and then dried at 130 ° C. for 2 hours in a vacuum oven. In addition, the turbidity of the liquid product was measured using a VWR 66120-200 turbidimeter. While not wishing to be bound by theory, the turbidity is believed to be an indicator of catalyst dissolution during the THF polymerization process.

In addition, the turbidity of the THF polymerization feed was measured and found to be 0.1 NTU. Turbidity results when using an untreated catalyst (Example 10) and a treated catalyst (Examples 11 and 12) are shown in Table II below. Untreated catalysts showed significantly lower THF conversion. While not wishing to be bound by theory, it is believed that the low conversion observed in the untreated catalyst is due to the depolymerization of the THF polymer catalyzed by the resin catalyst dissolved in the product mixture. This depolymerization was observed during the oven drying step.

TABLE II

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

All patents, patent applications, test procedures, priority documents, articles, publications, manuals, and other documents cited herein are hereby incorporated by reference in their entirety to the extent that their descriptions do not contradict the present invention and in all countries where introduction is permitted. Is introduced.

Where numerical lower and numerical upper limits are listed herein, ranges from any lower limit to any upper limit are considered.

While exemplary embodiments of the invention have been described with specificity, it will be understood that various other modifications will be apparent and may be readily made by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, the scope of the claims herein is not limited to the examples and descriptions set forth herein, and the claims are patentable novelty belonging to the present invention, including all features that are treated as equivalents by those skilled in the art to which this invention relates. It is intended to be interpreted to include all features of.

Claims (22)

a) filling the pressure vessel with a perfluorosulfonic acid resin and water at a resin / water weight ratio of about 1/1 to about 1/20,
b) heating the pressure vessel contents at elevated temperature and for a time sufficient to remove about 2 to about 20 weight percent of the maximum soluble component of the perfluorosulfonic acid resin from the perfluorosulfonic acid resin and to increase the average equivalent, thereby reducing the soluble component to about 2 Producing a treated perfluorosulfonic acid resin product that is reduced to about 20 weight percent and increases in average equivalent weight, and
c) recovering the treated perfluorosulfonic acid resin product of step b)
A method of treating perfluorosulfonic acid resin comprising a. The method of claim 1 wherein the resin / water weight ratio of 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. The method of claim 1 wherein the pressure vessel contents are mechanically stirred 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 from about 2 to about 15 weight percent of the maximum soluble component of the perfluorosulfonic acid resin is removed. The method of claim 1, wherein step b) is maintained for up to about 12 hours. The method of claim 5, wherein said time is about 1 to about 8 hours. A treated perfluorosulfonic acid resin, wherein the maximum soluble component is reduced by about 2 to about 20 weight percent and the average equivalent weight is increased compared to the perfluorosulfonic acid resin before treatment. 8. The perfluorosulfonic acid resin of claim 7, wherein the maximum soluble component is reduced by about 2 to about 15 weight percent relative to the perfluorosulfonic acid resin before treatment. Between about 0 ° C. and about 120 ° C., in the presence of a catalyst comprising the treated perfluorosulfonic acid resin, having a reduced maximum soluble component by about 2 to about 20 weight percent and an increased average equivalent weight relative to the perfluorosulfonic acid resin before treatment. Polymerizing at least one tetrahydrofuran or at least one tetrahydrofuran and at least one alkylene oxide at a polymerization temperature, wherein the treatment removes about 2 to about 20 weight percent of the maximum soluble component and averages the equivalent weight. Preparation of polyether glycols or copolyether glycols having an average molecular weight of about 200 Daltons to about 5000 Daltons, comprising contacting said perfluorosulfonic acid resin with deionized water at conditions of temperature, pressure and contact time sufficient to increase the Way. 10. The process of claim 9 wherein the alkylene oxide is 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 process of claim 9 wherein the polymerization temperature is from about 40 ° C to about 80 ° C. 10. 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. How. 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 40 ° C to about 72 ° C. 10. The process of claim 9, wherein the polymerization step is carried out in a continuous stirred tank reactor. The presence of a catalyst comprising at least one compound containing a reactive hydrogen atom and a treated perfluorosulfonic acid resin having a reduced maximum soluble component of about 2 to about 20 weight percent and an increased average equivalent weight as compared to the perfluorosulfonic acid resin before treatment Under polymerization, polymerizing tetrahydrofuran and at least one alkylene oxide at a polymerization temperature of from about 40 ° C. to about 80 ° C., wherein the treatment removes and averages about 2 to about 20% by weight of the maximum soluble component. A process for preparing copolyether glycols having an average molecular weight of from about 650 daltons to about 5000 daltons, comprising contacting said perfluorosulfonic acid resin with deionized water at conditions of temperature, pressure and contact time sufficient to increase the equivalent weight. The compound of claim 16, wherein the alkylene oxide is 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 compound of claim 16 wherein the compound containing a reactive hydrogen atom is water, 1,4-butanediol, a poly (tetramethylene ether) glycol having a molecular weight of about 130 Daltons to about 400 Daltons, a molecular weight of about 130 Daltons to about 400 Daltons Copolyether glycol, and combinations thereof. The method 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. How. 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. 18. The process of claim 17, wherein the temperature of the polymerization step is from about 40 ° C to about 72 ° C.