CN107417903A - The preparation technology of polytetrahydrofuran diol - Google Patents
The preparation technology of polytetrahydrofuran diol Download PDFInfo
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- CN107417903A CN107417903A CN201710764040.7A CN201710764040A CN107417903A CN 107417903 A CN107417903 A CN 107417903A CN 201710764040 A CN201710764040 A CN 201710764040A CN 107417903 A CN107417903 A CN 107417903A
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- Prior art keywords
- polytetrahydrofuran diol
- catalyst
- organic phase
- preparation technology
- solution
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920000909 polytetrahydrofuran Polymers 0.000 title claims abstract description 63
- 150000002009 diols Chemical class 0.000 title claims abstract description 60
- 238000005516 engineering process Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 32
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000012074 organic phase Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012071 phase Substances 0.000 claims abstract description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 230000001186 cumulative effect Effects 0.000 claims abstract description 4
- 239000012530 fluid Substances 0.000 claims abstract description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- 238000000605 extraction Methods 0.000 claims description 15
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000003377 acid catalyst Substances 0.000 claims description 3
- 239000003463 adsorbent Substances 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 239000013557 residual solvent Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 3
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 238000007171 acid catalysis Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 13
- -1 poly-tetramethylene ether diol Chemical class 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- USHBCJKLMPPLOX-UHFFFAOYSA-N acetyl acetate;perchloric acid Chemical compound OCl(=O)(=O)=O.CC(=O)OC(C)=O USHBCJKLMPPLOX-UHFFFAOYSA-N 0.000 description 3
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910021653 sulphate ion Inorganic materials 0.000 description 3
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002614 Polyether block amide Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C08G65/30—Post-polymerisation treatment, e.g. recovery, purification, drying
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses the preparation technology of polytetrahydrofuran diol, comprise the following steps：Put into heteropolyacid catalyst, tetrahydrofuran and proton donor successively into reactor and obtain reaction solution, the volume of the heteropolyacid catalyst accounts for the 40 60% of heteropolyacid catalyst, tetrahydrofuran and proton donor cumulative volume；Stirring reaction liquid, heteropolyacid catalyst is set to become quasi-fluid under stirring, obvious organic phase and catalyst phase are formed in reactor, and detect the water content of organic phase, the water content of organic phase is adjusted 0.1 0.2%, organic phase is extracted, the organic phase is rough polytetrahydrofuran diol solution；Rough polytetrahydrofuran diol solution is mixed with extractant, obtains purified polytetrahydrofuran diol product.The preparation technology of polytetrahydrofuran diol of the present invention has changed catalyst and has solved the shortcomings that polytetrahydrofuran diol solution high viscosity, distribution is wide.
Description
Technical field
The present invention relates to a kind of preparation technology, and in particular to the preparation technology of polytetrahydrofuran diol.
Background technology
(polyteramethylene etherglycol, are abbreviated as PTMG to polytetrahydrofuran diol, and pertinent literature is also known as
PolyTHF, poly-tetramethylene ether diol, PEO macromonomer, polytetramethylene ether diol, polyoxytetramethylene glycol
Deng), it is high-performance block polyether-polyurethane, polyetheramides, polyester elastomer, thermoplasticity polyurethane and cast elasticity
The primary raw material of body etc..It may be utilized in fabricating artificial leather, elastic coating and adhesive etc..
PTMG traditional processing technologies are to use all kinds of superpower mineral acid as catalyst, and this technological process is longer, technical process
More complicated, raw material and energy expenditure are all higher, and product index control difficulty is also larger, and product purity is low；Using fluosulfonic acid
Polytetrahydrofuran diol distribution prepared by method, acetic anhydride-perchloric acid method and sulphate method is wide, and viscosity is very high, necessary when in use
Its thawing is set to use with higher temperature.
The content of the invention
The technical problems to be solved by the invention are that conventionally produced polytetrahydrofuran diol purity is low, and viscosity is high,
The preparation technology, and it is an object of the present invention to provide polytetrahydrofuran diol is not convenient to use, solution polytetrahydrofuran diol purity is low, viscosity
The problem of high.
The present invention is achieved through the following technical solutions：
The preparation technology of polytetrahydrofuran diol, comprises the following steps：
S1, put into heteropolyacid catalyst, tetrahydrofuran and proton donor acquisition reaction solution successively into reactor, it is described miscellaneous
The volume of more acid catalysts accounts for the 40-60% of heteropolyacid catalyst, tetrahydrofuran and proton donor cumulative volume；
Reaction solution in S2, stirring S1, makes heteropolyacid catalyst become quasi-fluid under stirring, the shape in reactor
Into obvious organic phase and catalyst phase, and the water content of organic phase is detected, adjusts the water content of organic phase in 0.1-0.2%,
Organic phase is extracted, the organic phase is rough polytetrahydrofuran diol solution；
S3, rough polytetrahydrofuran diol solution mixed with extractant, the extractant is hydrocarbon compound and water
Saturation or supersaturated solution, the weight percentage of extractant reclaimed water is 0.03-0.8%；
S4, the extraction phase containing extractant and tetrahydrofuran, the extraction containing polytetrahydrofuran diol are obtained by extraction by step S3
Take phase, catalyst phase；
S5, the extraction phase containing polytetrahydrofuran diol in step S4 is removed into remaining heteropoly acid by alkaline adsorbent urged
Agent, after evaporation removes residual solvent, obtain purified polytetrahydrofuran diol product.
The PolyTHF that the present invention is prepared using heteropoly acid method has low viscosity, the characteristic of narrowly distributing, solves use
The problem of polytetrahydrofuran diol distribution prepared by fluosulfonic acid method, acetic anhydride-perchloric acid method and sulphate method is wide, and viscosity is very high；
Yishui of the present invention adjusts the water content of machine phase during the course of the reaction as end-blocking, improves the conversion ratio of tetrahydrofuran, from
And improve the purity of polytetrahydrofuran diol solution；The present invention has carried out purifying, extraction to polytetrahydrofuran diol solution, carries
The high purity of polytetrahydrofuran diol product.The present invention has changed catalyst, and to solve polytetrahydrofuran diol solution high viscous
Spend, be distributed the shortcomings that wide；The present invention improves its purity by being purified to polytetrahydrofuran diol solution.
Heteropolyacid catalyst described in step S1 is phosphorus heteropoly tungstic acid catalyzer, and the Al content in heteropolyacid catalyst is
0-2ppm, Fe content are 0-3ppm, and Cu contents are 0-2ppm, and Na contents are 0-30ppm, and dissociate phosphate radical in heteropolyacid catalyst
Content≤1mol/L, other metal ion contents in addition to tungsten are 0-50ppm, and heteropolyacid catalyst purity is more than
96%.The preferred heteropolyacid catalyst of the present invention, improve the conversion ratio of tetrahydrofuran.
Proton donor is water in the step S1.
Hydrocarbon compound described in step S3 is the straight chain fatty alkane with 5-12 carbon atom, hexamethylene, benzene, first
One or more in benzene, ethylbenzene.The dosage of the extractant is 5-8 times of rough polytetrahydrofuran diol solution weight.
The preferred dosage of extractant and extractant of the present invention, improve the purity of polytetrahydrofuran diol solution.
The present invention compared with prior art, has the following advantages and advantages：
1st, the preparation technology of polytetrahydrofuran diol of the present invention has changed catalyst and has solved polytetrahydrofuran diol solution
The shortcomings that high viscosity, wide distribution；
2nd, the preparation technology of polytetrahydrofuran diol of the present invention is improved by being purified to polytetrahydrofuran diol solution
Its purity；
3rd, the preparation technology flow of polytetrahydrofuran diol of the present invention is simple, and raw material, energy expenditure are low.
Embodiment
For the object, technical solutions and advantages of the present invention are more clearly understood, with reference to embodiment, the present invention is made
Further to describe in detail, exemplary embodiment of the invention and its explanation are only used for explaining the present invention, are not intended as to this
The restriction of invention.
Embodiment 1
The preparation technology of polytetrahydrofuran diol of the present invention, comprises the following steps：
S1, put into heteropolyacid catalyst, tetrahydrofuran and proton donor acquisition reaction solution successively into reactor, it is described miscellaneous
The volume of more acid catalysts accounts for the 40-60% of heteropolyacid catalyst, tetrahydrofuran and proton donor cumulative volume；
Reaction solution in S2, stirring S1, makes heteropolyacid catalyst become quasi-fluid under stirring, the shape in reactor
Into obvious organic phase and catalyst phase, and the water content of organic phase is detected, adjusts the water content of organic phase in 0.1-0.2%,
Organic phase is extracted, the organic phase is rough polytetrahydrofuran diol solution；
S3, rough polytetrahydrofuran diol solution mixed with extractant, the extractant is hydrocarbon compound and water
Saturation or supersaturated solution, the weight percentage of extractant reclaimed water is 0.03-0.8%；
S4, the extraction phase containing extractant and tetrahydrofuran, the extraction containing polytetrahydrofuran diol are obtained by extraction by step S3
Take phase, catalyst phase；
S5, the extraction phase containing polytetrahydrofuran diol in step S4 is removed into remaining heteropoly acid by alkaline adsorbent urged
Agent, after evaporation removes residual solvent, obtain purified polytetrahydrofuran diol product.
The PolyTHF that the present invention is prepared using heteropoly acid method has low viscosity, the characteristic of narrowly distributing, solves use
The problem of polytetrahydrofuran diol distribution prepared by fluosulfonic acid method, acetic anhydride-perchloric acid method and sulphate method is wide, and viscosity is very high；
Yishui of the present invention adjusts the water content of machine phase during the course of the reaction as end-blocking, improves the conversion ratio of tetrahydrofuran, from
And improve the purity of polytetrahydrofuran diol solution；The present invention has carried out purifying, extraction to polytetrahydrofuran diol solution, carries
The high purity of polytetrahydrofuran diol product.The present invention has changed catalyst, and to solve polytetrahydrofuran diol solution high viscous
Spend, be distributed the shortcomings that wide；The present invention improves its purity by being purified to polytetrahydrofuran diol solution.
Embodiment 2
Based on embodiment 1, the heteropolyacid catalyst described in step S1 is phosphorus heteropoly tungstic acid catalyzer, heteropolyacid catalyst
In Al content be 0-2ppm, Fe contents are 0-3ppm, and Cu contents are 0-2ppm, and Na contents are 0-30ppm, heteropolyacid catalyst
In dissociate content≤1mol/L of phosphate radical, other metal ion contents in addition to tungsten are 0-50ppm, heteropolyacid catalyst
Purity is more than 96%.The preferred heteropolyacid catalyst of the present invention, improve the conversion ratio of tetrahydrofuran.Proton supplies in the step S1
Body is water.Hydrocarbon compound described in step S3 is the straight chain fatty alkane with 5-12 carbon atom, hexamethylene, benzene, first
One or more in benzene, ethylbenzene.The dosage of the extractant is 5-8 times of rough polytetrahydrofuran diol solution weight.
The preferred dosage of extractant and extractant of the present invention, improve the purity of polytetrahydrofuran diol solution.Make in the prior art
Standby polytetrahydrofuran diol solution viscosity is generally 1000-1500 centipoises, polytetrahydrofuran diol solution prepared by the present invention
Viscosity is 480-600 centipoises, and product purity is up to more than 95%.
Above-described embodiment, the purpose of the present invention, technical scheme and beneficial effect are carried out further
Describe in detail, should be understood that the embodiment that the foregoing is only the present invention, be not intended to limit the present invention
Protection domain, within the spirit and principles of the invention, any modification, equivalent substitution and improvements done etc., all should include
Within protection scope of the present invention.
Claims (5)
1. the preparation technology of polytetrahydrofuran diol, it is characterised in that comprise the following steps：
S1, put into heteropolyacid catalyst, tetrahydrofuran and proton donor acquisition reaction solution, the heteropoly acid successively into reactor
The volume of catalyst accounts for the 40-60% of heteropolyacid catalyst, tetrahydrofuran and proton donor cumulative volume；
Reaction solution in S2, stirring S1, makes heteropolyacid catalyst become quasi-fluid under stirring, is formed in reactor bright
Aobvious organic phase and catalyst phase, and the water content of organic phase is detected, the water content of organic phase is adjusted in 0.1-0.2%, extraction
Organic phase, the organic phase are rough polytetrahydrofuran diol solution；
S3, rough polytetrahydrofuran diol solution mixed with extractant, the extractant is the full of hydrocarbon compound and water
And/or supersaturated solution, the weight percentage of extractant reclaimed water is 0.03-0.8%；
S4, be obtained by extraction by step S3 the extraction phase containing extractant and tetrahydrofuran, the extraction phase containing polytetrahydrofuran diol,
Catalyst phase；
S5, the extraction phase containing polytetrahydrofuran diol in step S4 is passed through to the heteropoly acid catalysis that alkaline adsorbent removes remnants
Agent, after evaporation removes residual solvent, obtain purified polytetrahydrofuran diol product.
2. the preparation technology of polytetrahydrofuran diol according to claim 1, it is characterised in that miscellaneous described in step S1
More acid catalysts are phosphorus heteropoly tungstic acid catalyzer, and the Al content in heteropolyacid catalyst is 0-2ppm, and Fe contents are 0-3ppm, Cu
Content is 0-2ppm, and Na contents are 0-30ppm, the content≤1mol/L for the phosphate radical that dissociates in heteropolyacid catalyst, in addition to tungsten
Other metal ion contents be 0-50ppm, heteropolyacid catalyst purity is more than 96%.
3. the preparation technology of polytetrahydrofuran diol according to claim 1, it is characterised in that proton in the step S1
Donor is water.
4. the preparation technology of polytetrahydrofuran diol according to claim 1, it is characterised in that the hydrocarbon described in step S3
Class compound is the one or more in the straight chain fatty alkane with 5-12 carbon atom, hexamethylene, benzene, toluene, ethylbenzene.
5. the preparation technology of polytetrahydrofuran diol according to claim 4, it is characterised in that the dosage of the extractant
For 5-8 times of rough polytetrahydrofuran diol solution weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710764040.7A CN107417903A (en) | 2017-08-30 | 2017-08-30 | The preparation technology of polytetrahydrofuran diol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710764040.7A CN107417903A (en) | 2017-08-30 | 2017-08-30 | The preparation technology of polytetrahydrofuran diol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107417903A true CN107417903A (en) | 2017-12-01 |
Family
ID=60435489
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710764040.7A Pending CN107417903A (en) | 2017-08-30 | 2017-08-30 | The preparation technology of polytetrahydrofuran diol |
Country Status (1)
| Country | Link |
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| CN (1) | CN107417903A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111574703A (en) * | 2020-04-21 | 2020-08-25 | 杭州三隆新材料有限公司 | High-production-efficiency preparation method of polytetramethylene ether glycol |
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|---|---|---|---|---|
| CN1368990A (en) * | 1999-08-19 | 2002-09-11 | 旭化成株式会社 | Polyoxytetramethylene glycol and process for producing the same |
| CN1884339A (en) * | 2006-06-07 | 2006-12-27 | 张永梅 | Polytetrahydrofuran diol and its preparation and purification method |
| CN102504236A (en) * | 2011-12-09 | 2012-06-20 | 太仓中化环保化工有限公司 | Preparation method of polytetramethylene ether glycol (PTMEG) |
| CN103214667A (en) * | 2013-03-14 | 2013-07-24 | 杭州三隆新材料有限公司 | Polymerization method of polytetrahydrofuran single alcohol and diol mixture |
| CN103357434A (en) * | 2013-07-18 | 2013-10-23 | 吕涛 | Synthesizing method of heteropolyacid imidazolium salt catalyst |
-
2017
- 2017-08-30 CN CN201710764040.7A patent/CN107417903A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1368990A (en) * | 1999-08-19 | 2002-09-11 | 旭化成株式会社 | Polyoxytetramethylene glycol and process for producing the same |
| CN1884339A (en) * | 2006-06-07 | 2006-12-27 | 张永梅 | Polytetrahydrofuran diol and its preparation and purification method |
| CN102504236A (en) * | 2011-12-09 | 2012-06-20 | 太仓中化环保化工有限公司 | Preparation method of polytetramethylene ether glycol (PTMEG) |
| CN103214667A (en) * | 2013-03-14 | 2013-07-24 | 杭州三隆新材料有限公司 | Polymerization method of polytetrahydrofuran single alcohol and diol mixture |
| CN103357434A (en) * | 2013-07-18 | 2013-10-23 | 吕涛 | Synthesizing method of heteropolyacid imidazolium salt catalyst |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111574703A (en) * | 2020-04-21 | 2020-08-25 | 杭州三隆新材料有限公司 | High-production-efficiency preparation method of polytetramethylene ether glycol |
| CN111574703B (en) * | 2020-04-21 | 2022-04-12 | 杭州三隆新材料有限公司 | High-production-efficiency preparation method of polytetramethylene ether glycol |
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