CN101302290B - Method for preparing polytetramethylene terephthalat ether glycol using heteropolyacid catalyst - Google Patents
Method for preparing polytetramethylene terephthalat ether glycol using heteropolyacid catalyst Download PDFInfo
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- CN101302290B CN101302290B CN2008100848227A CN200810084822A CN101302290B CN 101302290 B CN101302290 B CN 101302290B CN 2008100848227 A CN2008100848227 A CN 2008100848227A CN 200810084822 A CN200810084822 A CN 200810084822A CN 101302290 B CN101302290 B CN 101302290B
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- catalyzer
- heteropolyacid
- hpa
- ptmg
- thf
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- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 23
- -1 polytetramethylene terephthalat Polymers 0.000 title claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims description 7
- 239000003054 catalyst Substances 0.000 title abstract description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 title description 2
- 229920000874 polytetramethylene terephthalate Polymers 0.000 title 1
- 238000003980 solgel method Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- AVFBYUADVDVJQL-UHFFFAOYSA-N phosphoric acid;trioxotungsten;hydrate Chemical compound O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O AVFBYUADVDVJQL-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 238000009826 distribution Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 abstract 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract 2
- 229920001577 copolymer Polymers 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract 1
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 29
- 238000002360 preparation method Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 229920002334 Spandex Polymers 0.000 description 3
- 239000004759 spandex Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- RVGLUKRYMXEQAH-UHFFFAOYSA-N 3,3-dimethyloxetane Chemical compound CC1(C)COC1 RVGLUKRYMXEQAH-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000013460 polyoxometalate Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000003527 tetrahydropyrans Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Images
Classifications
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- 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
- C08G65/04—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
- C08G65/26—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 and other compounds
- C08G65/2642—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 and other compounds characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2666—Hetero polyacids
-
- 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
- C08G65/26—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 and other compounds
- C08G65/2696—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 and other compounds characterised by the process or apparatus 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
- C08G65/32—Polymers modified by chemical after-treatment
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Polyethers (AREA)
Abstract
The invention relates to a method for preparing tetrahydrofuran polymer by adjusting the grain dimension of heteropoly acid catalyst, in particular to a method for preparing pyromellitic dianhydride or pyromellitic dianhydride copolymer by using grain-shaped heteropoly acid made by sol-gel method as catalyst. The activity of the heteropoly acid catalyst made by the method is improved and pyromellitic dianhydride with narrow molecular weight distribution is obtained.
Description
Technical field
The present invention relates to a kind ofly, The present invention be more particularly directed to a kind of through using the heteropolyacid subparticle to prepare the method for PTMG or PTMG multipolymer as catalyzer through using heteropolyacid to prepare the method for polytetramethylene ether diol (hereinafter being called " PTMG ") or PTMG multipolymer as catalyzer.
Background technology
Because PTMG is ductile, it is used as main raw, softening agent and the emulsifying agent of spandex usually.
Can prepare PTMG by THF (hereinafter being called " THF "), and can be with heteropolyacid as catalyzer.In many prior aries, all disclose and used heteropolyacid to prepare the method for PTMG by THF as catalyzer.
In Japanese Patent No.S58-89081, No.S59-013523 and No.S59-058485, disclosed and used heteropolyacid to prepare the method for PTMG by THF as catalyzer with certain water cut.Though in these inventions, do not describe the preparation method of heteropolyacid, the water cut that wherein is described to heteropolyacid can influence the physical property of activity of such catalysts and PTMG.
Disclose the impurity in the heteropolyacid among the Korean Patent No.358552 and can influence physical property and reaction efficiency.
In general, the reaction of catalyzer can receive the influence of catalyst particle size.Especially when reacting through reaction stirred and catalyzer, less catalyst particle size makes reaction efficiency improve easily.
Though the multiple method for preparing the catalyzer subparticle is arranged, preferably sol-gel method.
Using heteropolyacid to be prepared by THF in the process of PTMG as catalyzer, the water molecules in the catalyzer combines with the end group of PTMG, so the water molecules in the catalyzer has determined chain length or the molecular weight of PTMG.So according to thinking, be adjusted to uniform level, can make PTMG, thereby can prepare PTMG with narrow molecular weight distributions with even chain length through water cut with catalyzer.In addition, known viscosity by the prepared spandex of PTMG with narrow molecular weight distributions is low, and therefore the efficient of weaving processing is improved.
According to the present invention, through using the catalyzer by the prepared subparticle shape of sol-gel method, reaction efficiency is improved, and said MWD narrows down.Therefore, through the subparticle that in reaction, uses heteropolyacid catalyst dispersity is increased, and can control MWD through the water cut of regulating catalyzer.
According to the present invention,, a kind of method that is prepared PTMG through the HPA catalyzer that uses the subparticle shape by THF is proposed in order to regulate the MWD of PTMG.The preparation method of the high yield of a kind of PTMG with narrow molecular weight distributions is also proposed in addition.
Summary of the invention
According to the preferred embodiments of the invention, provide a kind of through using heteropolyacid to prepare the method for polytetramethylene ether diol by THF as catalyzer, it is characterized in that using the subparticle of said heteropolyacid catalyst.
Another preferred embodiment according to the present invention, said heteropolyacid is prepared by sol-gel method.
Another preferred embodiment according to the present invention, said heteropolyacid are tungstophosphoric acid, molybdophosphate or tungstosilicic acid.
Another preferred embodiment according to the present invention, the ligancy of said heteropolyacid are 5 to 8.
Description of drawings
Fig. 1 is the diagrammatical synoptic diagram of the sol-gel method of preparation HPA catalyzer subparticle.
Fig. 2 is tungstophosphoric acid particulate ESEM (SEM) photo by the inventive method preparation.
Fig. 3 is common tungstophosphoric acid particulate ESEM (SEM) photo.
Embodiment
To describe the present invention hereinafter.
According to the present invention, can be through only THF being carried out polymerization, perhaps to THF with as carrying out polymerization and make PTMG with cyclic ethers or the mixture of glycol that the comonomer of copolyreaction takes place THF.Said comonomer can be selected from disclosed those comonomers in this area, and particularly 3,3-dimethyl-trimethylene oxide, methyltetrahydrofuran, 1,3-dioxolane, tetrahydropyrans, terepthaloyl moietie, Ucar 35,1, ammediol, 1,3 butylene glycol etc.
Through using heteropolyacid (hereinafter being called " HPA ") to prepare PTMG as catalyzer.Usually HPA and 20 to 40 water molecules coordinations, but this HPA is not effective HPA in this polyreaction.Therefore, in order to reach effective polymerization, need be to regulating with the water molecule number of HPA anion binding.In order to regulate and HPA coordinate water molecule number, usually can be with HPA 100 ℃ to 300 ℃ heating down.Can regulate Heating temperature and heat-up time according to the ligancy of water molecules, for example can be with being adjusted to 3 to 18 with HPA coordinate water molecule number.
Among the present invention used HPA can for through will be selected among Mo (molybdenum), W (tungsten) and the V (vanadium) at least a oxide compound be selected from a kind of among P (phosphorus), Ti (antimony), Si (silicon), B (boron), As (arsenic), Ge (germanium), Ti (titanium), Ce (cerium) and the Co (cobalt) and carry out the oxygen acid that condensation is processed.
Can use any known HPA that satisfies above-mentioned condition among the present invention.
Preferably (but being not limited to this), HPA has following chemical formula (1).Particularly, the HPA that has a structure shown in the following chemical formula (1) can be used for preparing PTMG and spandex.
Ha(XbMcOd)
-a …(1)
In formula 1, " X " expression phosphorus, antimony, silicon or boron, " M " representes molybdenum, tungsten or vanadium, and " O " representes oxygen, and " b, c and d " representes each atoms of elements ratio, and the value of " a " representative is by each element valence decision.
For example, " b " in the chemical formula (1) can be 1 to 5, is preferably 1 to 2." c " in the chemical formula (1) can be 5 to 20, and " d " can be 18 to 62, is preferably 40 to 62.The negative charge of " a " in the chemical formula (1) expression heteropolyanion, and the value of " a " can change according to the difference of each condition, but it is always identical with proton number, to keep the balance of chemical formula.HPA and polyoxometallate (polyoxometalate) have various structures, but in these structures, the HPA compound with Keggin structure can be used for preparing PTMG.
According to the present invention, adopt sol-gel method to prepare HPA with single-size, wherein said particulate is of a size of 1 μ m to 5 μ m or littler.
According to the present invention, preferably, use by the prepared HPA catalyzer of sol-gel method, at 0 ℃ under 150 ℃, preferably under 30 ℃ to 80 ℃, carried out the THF polyreaction 3 hours to 7 hours.
Describe in the face of the method for preparing the HPA catalyzer by sol-gel method down.
The method for preparing the HPA catalyzer through sol-gel method
The schematically illustrated HPA for preparing the subparticle shape through sol-gel method of Fig. 1.0.1 mole of HPA aqueous solution is joined in the container (1).With the effusive while of the flow velocity of 35ml/min, the flow velocity with 100ml/min from the container (2) that pressurized gas is housed is exported nitrogen at the HPA aqueous solution.The HPA aqueous solution sprays through nozzle (3), and the HPA aqueous solution that ejects drop in the electric furnace (4), is of a size of 1 μ m to 5 μ m or littler HPA subparticle thereby made it.
Fig. 2 is ESEM (SEM) photo through the HPA catalyzer of the subparticle shape of the inventive method preparation.
Fig. 3 is ESEM (SEM) photo through the HPA catalyzer of ordinary method preparation.Fig. 2 and Fig. 3 are compared and can find, compare with the particle size for preparing by ordinary method, littler and more even through the particle size of sol-gel method preparation of the present invention.
Hereinafter, will describe the present invention with reference to example.Provide these examples only to be used for the present invention is carried out the purpose of example description, be confined to this and should not be construed as scope of the present invention.
Example
(embodiment 1 to 3)
In the THF polymerization technology, the HPA catalyzer that THF (it contains the water of 300ppm) and the 100g of 200g made through said sol-gel method joins in the 500ml container that is equipped with whipping appts and reflux exchanger.Mixture was stirred 4 hours down in 60 ℃ in reactor drum, subsequently it is at room temperature left standstill, thereby make this mixture separation become the upper and lower.Through distillation, unreacted THF is removed from the upper strata, so just obtain the polymkeric substance of PTMG or THF.Number-average molecular weight (Mn), the MWD (MWD) of the PTMG that obtains through GPC (GPC) are shown in Table 1.
(Comparative Examples 1-3)
According to carrying out the preparation method of PTMG with embodiment 1 identical mode, difference is to use the HPA catalyzer (tungstophosphoric acid, molybdophosphate or tungstosilicic acid) by the ordinary method preparation.
Table 1
Measure transformation efficiency through following method.
(mensuration transformation efficiency)
After the polyreaction of THF, mixture is at room temperature left standstill 10 hours, thereby make this mixture separation become the upper and lower.The upper strata is taken out, and, stirred 5 hours down at 30 ℃ subsequently to wherein adding the octane that is equivalent to this upper strata doubling dose.Through mean diameter is that the ZX 21 filter membrane of 2 μ m is removed catalyzer, concentrates through rotary vacuum evaporator then, obtains PTMG thus.Thereby the weight through measuring PTMG obtains transformation efficiency.
The invention effect
According to the present invention; Through using subparticle by the HPA catalyzer of sol-gel method preparation, can advantageously prepare PTMG by THF, wherein the dispersity of catalyzer is improved in the polyreaction; Therefore transformation efficiency improves, and can obtain having the PTMG of narrow molecular weight distributions.
Claims (2)
1. one kind through using heteropolyacid to be prepared the method for polytetramethylene ether diol by THF as catalyzer; It is characterized in that; The heteropolyacid that uses the subparticle shape is as catalyzer; The heteropolyacid of wherein said subparticle shape prepares through sol-gel method, and is adjusted to 3 to 18 with said heteropolyacid coordinate water molecule number.
2. the method for preparing polytetramethylene ether diol according to claim 1, wherein said heteropolyacid are tungstophosphoric acid, molybdophosphate or tungstosilicic acid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020070044183A KR100870532B1 (en) | 2007-05-07 | 2007-05-07 | Process of preparing polytetramethylene ether glycol with heteropoly acid catalyst |
| KR10-2007-0044183 | 2007-05-07 |
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| Publication Number | Publication Date |
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| CN101302290A CN101302290A (en) | 2008-11-12 |
| CN101302290B true CN101302290B (en) | 2012-07-11 |
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| CN103360594B (en) * | 2013-07-18 | 2015-08-12 | 吕涛 | A kind of method using heteropolyacid imidazole salts catalyst preparing polytetramethylene ether diol |
| CN113563575B (en) * | 2021-07-29 | 2023-04-28 | 浙江皇马科技股份有限公司 | Alkylene oxide-tetrahydrofuran copolymer and preparation method thereof |
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| KR20080098834A (en) | 2008-11-12 |
| CN101302290A (en) | 2008-11-12 |
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