WO2010120292A1 - Improved catalyst for manufacturing polymers of tetrahydrofuran - Google Patents
Improved catalyst for manufacturing polymers of tetrahydrofuran Download PDFInfo
- Publication number
- WO2010120292A1 WO2010120292A1 PCT/US2009/040654 US2009040654W WO2010120292A1 WO 2010120292 A1 WO2010120292 A1 WO 2010120292A1 US 2009040654 W US2009040654 W US 2009040654W WO 2010120292 A1 WO2010120292 A1 WO 2010120292A1
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- WO
- WIPO (PCT)
- Prior art keywords
- acid resin
- perfluorosulfonic acid
- oxide
- soluble components
- polymerization
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/08—Saturated oxiranes
- C08G65/10—Saturated oxiranes characterised by the catalysts used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/16—Cyclic ethers having four or more ring atoms
- C08G65/20—Tetrahydrofuran
Definitions
- 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.
- 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.
- 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.
- the cyclic ethers used for this purpose are ethylene oxide and propylene oxide.
- 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.
- a polymerization promoter such as a carboxylic acid anhydride, as disclosed in U.S. Pat. No. 4,163,115.
- the primary polymer products are diesters, which need to be hydrolyzed in a subsequent step to obtain the desired polyether glycols.
- 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.
- 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.
- 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.
- EW average equivalent weight
- 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.
- PTMEG polytetramethylene ether glycol.
- PTMEG is also known as polyoxybutylene glycol.
- 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.
- THF tetrahydrofuran and includes within its meaning alkyl substituted tetrahydrofuran capable of copolymerizing with THF, for example 2- methyltetrahydrofuran, 3-methyltetrahydrofuran, and 3-ethyltetrahydrofuran.
- alkylene oxide 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.
- 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.
- 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.
- EW average equivalent weight
- 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 150 0 C to about 210 0 C, 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.
- 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.
- 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 + .
- 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 + .
- 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.
- 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.
- another cyclic ether e.g. alkylene oxide
- the THF used as a reactant in the process of the invention utilizing the improved catalyst can be any of those commercially available.
- 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.
- 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.
- 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.
- 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.
- alkyl substituted THF's include 2-methyltetrahydrofuran, 3- methyltetrahydrofuran, and 3-ethyltetrahydrofuran.
- 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.
- 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.
- the alkylene oxide reactant is ethylene oxide (EO), it can be any of those commercially available.
- 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.
- 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.
- 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.
- a perfluorosulfonic acid resin i.e. it comprises a perfluorocarbon backbone and the side chain is represented by the formula - 0-CF 2 CF(CF 3 )O-CF 2 CF 2 SO 3 H.
- Polymers of this type are disclosed in U.S. Patent No.
- TFE tetrafluoroethylene
- PDMOF perfluoro (3,6-dioxa-4-methyl-7-octenesulfonyl fluoride)
- 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.
- the polymerization step of the present invention may be carried out with or without a solvent.
- 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.
- an inert solvent such as one or more aliphatic, cycloaliphatic, or aromatic hydrocarbons
- 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.
- the polymerization step of the present invention is generally carried out at from about O 0 C to about 12O 0 C, such as from about 4O 0 C to about 8O 0 C, e.g. from about 4O 0 C to about 72 0 C.
- 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.
- the polymerization step of the present process may be conducted under an inert gas atmosphere.
- suitable inert gases for use herein include nitrogen, carbon dioxide, or the noble gases.
- 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.
- the process of the invention can be carried out continuously, or with one or more steps of the process being carried out batchwise.
- 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.
- the improved catalyst can, if desired, be preconditioned after it has been introduced into the reactor(s).
- catalyst preconditioning include drying by means of gases, for example air or nitrogen, which have been heated to 80-200 0 C.
- the improved catalyst can also be used without preconditioning.
- 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.
- 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.
- Feeds can be introduced to the polymerization reactor using delivery systems common in current engineering practice either batchwise or continuously.
- THF was obtained from Chemcentral.
- the acetic anhydride and acetic acid were purchased from Aldrich Chemicals. Deionized water was used.
- 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.
- the turbidity of the crude THF polymerization solution was determined by a VWR Catalog No. 66120-200 Turbidimeter in NTU units.
- sample 6 was a consecutive run of sample 1 , so the weight loss is cumulative.
- the resins were each dried at 130 0 C 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.
- 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
- 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.
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BRPI0923998A BRPI0923998A2 (en) | 2009-04-15 | 2009-04-14 | method for treating perfluorosulfonic acid resin, perfluorosulfonic acid resin and process for making polyether glycol or copolyether glycol |
JP2012505866A JP5599868B2 (en) | 2009-04-15 | 2009-04-15 | Improved catalyst for the production of polymers of tetrahydrofuran |
PCT/US2009/040654 WO2010120292A1 (en) | 2009-04-15 | 2009-04-15 | Improved catalyst for manufacturing polymers of tetrahydrofuran |
MX2011010775A MX2011010775A (en) | 2009-04-15 | 2009-04-15 | Improved catalyst for manufacturing polymers of tetrahydrofuran. |
CN200980158716.1A CN102395430B (en) | 2009-04-15 | 2009-04-15 | Improved catalyst for manufacturing polymers of tetrahydrofuran |
EP09843449.1A EP2419214A4 (en) | 2009-04-15 | 2009-04-15 | Improved catalyst for manufacturing polymers of tetrahydrofuran |
KR1020117027021A KR20120017424A (en) | 2009-04-15 | 2009-04-15 | Improved catalyst for manufacturing polymers of tetrahydrofuran |
HK12104881.0A HK1164211A1 (en) | 2009-04-15 | 2012-05-18 | Improved catalyst for manufacturing polymers of tetrahydrofuran |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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PCT/US2009/040654 WO2010120292A1 (en) | 2009-04-15 | 2009-04-15 | Improved catalyst for manufacturing polymers of tetrahydrofuran |
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WO2010120292A1 true WO2010120292A1 (en) | 2010-10-21 |
WO2010120292A8 WO2010120292A8 (en) | 2011-12-29 |
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PCT/US2009/040654 WO2010120292A1 (en) | 2009-04-15 | 2009-04-15 | Improved catalyst for manufacturing polymers of tetrahydrofuran |
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EP (1) | EP2419214A4 (en) |
JP (1) | JP5599868B2 (en) |
KR (1) | KR20120017424A (en) |
CN (1) | CN102395430B (en) |
BR (1) | BRPI0923998A2 (en) |
HK (1) | HK1164211A1 (en) |
MX (1) | MX2011010775A (en) |
WO (1) | WO2010120292A1 (en) |
Families Citing this family (4)
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US8450450B2 (en) * | 2009-08-24 | 2013-05-28 | Invista North America S.A R.L. | Polyether glycol manufacturing process |
CN103554464A (en) * | 2013-11-14 | 2014-02-05 | 国电新能源技术研究院 | Catalytic system for catalyzing ring opening polymerization of tetrahydrofuran |
CN103601880A (en) * | 2013-11-14 | 2014-02-26 | 国电新能源技术研究院 | Polymerization technology and reaction device for tetrahydrofuran |
CN110291132B (en) * | 2017-02-16 | 2021-12-14 | 株式会社可乐丽 | Copolymerized polyether polyol, polyurethane, and method for producing copolymerized polyether polyol |
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JPS52138598A (en) * | 1976-03-31 | 1977-11-18 | Du Pont | Process for preparing poly*tetramethylene ether*glycol |
US4163115A (en) * | 1976-03-31 | 1979-07-31 | E. I. Du Pont De Nemours And Company | Preparation of esters of poly-(tetramethylene ether) glycol |
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US4120903A (en) * | 1977-03-30 | 1978-10-17 | E. I. Du Pont De Nemours And Company | Method for preparing poly(tetramethylene ether) glycol |
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JP4360870B2 (en) * | 2003-09-10 | 2009-11-11 | 旭化成イーマテリアルズ株式会社 | Method for producing dispersion containing sulfonic acid type perfluoro copolymer |
CN100386367C (en) * | 2006-06-16 | 2008-05-07 | 武汉理工大学 | Preparation process of composite proton exchanging member based on hydrophilic porous poly tetrafluoro ethylene matrix |
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2009
- 2009-04-14 BR BRPI0923998A patent/BRPI0923998A2/en not_active IP Right Cessation
- 2009-04-15 CN CN200980158716.1A patent/CN102395430B/en active Active
- 2009-04-15 EP EP09843449.1A patent/EP2419214A4/en not_active Withdrawn
- 2009-04-15 WO PCT/US2009/040654 patent/WO2010120292A1/en active Application Filing
- 2009-04-15 JP JP2012505866A patent/JP5599868B2/en active Active
- 2009-04-15 MX MX2011010775A patent/MX2011010775A/en active IP Right Grant
- 2009-04-15 KR KR1020117027021A patent/KR20120017424A/en active IP Right Grant
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2012
- 2012-05-18 HK HK12104881.0A patent/HK1164211A1/en not_active IP Right Cessation
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WO1981000846A1 (en) * | 1979-09-27 | 1981-04-02 | Union Carbide Corp | The use of perfluorosulfonic acid resins as catalysts for preparing esters |
EP0032318A1 (en) * | 1979-12-31 | 1981-07-22 | E.I. Du Pont De Nemours And Company | Catalytic preparation of toluic acid, perfluorinated polymeric sulfonic acids and salts, and catalytic processes using them |
KR20000048902A (en) * | 1996-10-04 | 2000-07-25 | 그레이스 스티븐 에스. | A method for producing glycols |
US20060263674A1 (en) * | 2003-04-17 | 2006-11-23 | Mamoru Hosoya | Catalyst and process for producing the same, catalytic electrode and process for producing the same, membrane/electrode union, and electrochemical device |
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Also Published As
Publication number | Publication date |
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JP5599868B2 (en) | 2014-10-01 |
JP2012524149A (en) | 2012-10-11 |
BRPI0923998A2 (en) | 2016-01-26 |
HK1164211A1 (en) | 2012-09-21 |
WO2010120292A8 (en) | 2011-12-29 |
EP2419214A4 (en) | 2013-07-24 |
CN102395430B (en) | 2014-02-26 |
CN102395430A (en) | 2012-03-28 |
EP2419214A1 (en) | 2012-02-22 |
MX2011010775A (en) | 2012-02-08 |
KR20120017424A (en) | 2012-02-28 |
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