CN101302290A - 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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- CN101302290A CN101302290A CNA2008100848227A CN200810084822A CN101302290A CN 101302290 A CN101302290 A CN 101302290A CN A2008100848227 A CNA2008100848227 A CN A2008100848227A CN 200810084822 A CN200810084822 A CN 200810084822A CN 101302290 A CN101302290 A CN 101302290A
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- Prior art keywords
- hpa
- catalyzer
- ptmg
- heteropolyacid
- thf
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- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 24
- -1 polytetramethylene terephthalat Polymers 0.000 title claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims description 8
- 239000003054 catalyst Substances 0.000 title abstract description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 title description 2
- 229920000874 polytetramethylene terephthalate Polymers 0.000 title 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 44
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000003980 solgel method Methods 0.000 claims abstract description 14
- 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 8
- 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
- 229920001577 copolymer Polymers 0.000 abstract 1
- 229920000642 polymer Polymers 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229920002334 Spandex Polymers 0.000 description 3
- 239000004759 spandex Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 230000009466 transformation Effects 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
- 238000005227 gel permeation chromatography Methods 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
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 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
- 239000004744 fabric 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
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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)
- Polyethers (AREA)
- Catalysts (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 by using the heteropolyacid subparticle to prepare the method for PTMG or PTMG multipolymer as catalyzer by 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 often used as main raw, softening agent and the emulsifying agent of spandex.
Can prepare PTMG by tetrahydrofuran (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 content.Though do not describe the preparation method of heteropolyacid in these inventions, the water content 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 be subjected to the influence of catalyst particle size.Especially when reacting by 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 it is believed that, be adjusted to uniform level by water content with catalyzer, PTMG can be made, thereby PTMG can be prepared with narrow molecular weight distributions with even chain length.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, by using the catalyzer by the prepared subparticle shape of sol-gel method, reaction efficiency is improved, and described molecular weight distribution narrows down.Therefore, by the subparticle that in reaction, uses heteropolyacid catalyst dispersity is increased, and can control molecular weight distribution by the water content of regulating catalyzer.
According to the present invention,, a kind of method that is prepared PTMG by the HPA catalyzer that uses the subparticle shape by THF is proposed in order to regulate the molecular weight distribution 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 by using heteropolyacid to prepare the method for polytetramethylene ether diol by tetrahydrofuran (THF) as catalyzer, it is characterized in that using the subparticle of described heteropolyacid catalyst.
Another preferred embodiment according to the present invention, described heteropolyacid is prepared by sol-gel method.
Another preferred embodiment according to the present invention, described heteropolyacid are tungstophosphoric acid, molybdophosphate or tungstosilicic acid.
Another preferred embodiment according to the present invention, the ligancy of described heteropolyacid are 5 to 8.
Description of drawings
Fig. 1 is the summary synoptic diagram of the sol-gel method of preparation HPA catalyzer subparticle.
Fig. 2 is tungstophosphoric acid particulate scanning electron microscope (SEM) photo by the inventive method preparation.
Fig. 3 is common tungstophosphoric acid particulate scanning electron microscope (SEM) photo.
Embodiment
To describe the present invention hereinafter.
According to the present invention, can be by only THF being carried out polymerization, perhaps to THF with as can the cyclic ethers of comonomer of copolyreaction taking place with THF or the mixture of glycol carries out polymerization and makes PTMG.Described comonomer can be selected from disclosed those comonomers in this area, and particularly 3,3-dimethyl trimethylene oxide, methyltetrahydrofuran, 1,3-dioxolane, tetrahydropyrans, ethylene glycol, propylene glycol, 1, ammediol, 1,3 butylene glycol etc.
By 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 will be adjusted to 3 to 18 with HPA coordinate water molecule number.
Among the present invention used HPA can for by 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 made.
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 with 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 " represents molybdenum, tungsten or vanadium, and " O " represents oxygen, and " b, c and d " represents 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.
Below the method that is prepared the HPA catalyzer by sol-gel method is described.
The method for preparing the HPA catalyzer by sol-gel method
The schematically illustrated HPA for preparing the subparticle shape by 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 by 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 scanning electron microscope (SEM) photo by the HPA catalyzer of the subparticle shape of the inventive method preparation.
Fig. 3 is scanning electron microscope (SEM) photo by 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 by the particle size of sol-gel method preparation of the present invention.
Hereinafter, describe the present invention with reference to example.Provide these examples only to be used for the present invention is carried out the example illustrative purposes, 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 by described 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, subsequently it is at room temperature left standstill, thereby make this mixture separation become the upper and lower.By 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 molecular weight distribution (MWD) of the PTMG that obtains by gel permeation chromatography (GPC) are shown in Table 1.
(Comparative Examples 1-3)
Carry out the preparation method of PTMG according to the mode identical with embodiment 1, difference is to use the HPA catalyzer (tungstophosphoric acid, molybdophosphate or tungstosilicic acid) by the ordinary method preparation.
Table 1
Measure transformation efficiency by 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.By mean diameter is that the teflon filter membrane of 2 μ m is removed catalyzer, concentrates by rotary vacuum evaporator then, obtains PTMG thus.Thereby obtain transformation efficiency by the weight of measuring PTMG.
The invention effect
According to the present invention, by using fine by the HPA catalyst of sol-gel process preparation Particle can advantageously prepare PTMG by THF, wherein the branch of catalyst in the polymerisation Divergence is improved, so conversion ratio improves, and can obtain having the narrow molecular-weight branch The PTMG of cloth.
Claims (3)
1. one kind by using heteropolyacid to prepare the method for polytetramethylene ether diol as catalyzer by tetrahydrofuran (THF), it is characterized in that the heteropolyacid that uses the subparticle shape is as catalyzer.
2. the method for preparing polytetramethylene ether diol according to claim 1, wherein said heteropolyacid prepares by sol-gel method.
3. 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 |
|---|---|
| CN101302290A true CN101302290A (en) | 2008-11-12 |
| CN101302290B CN101302290B (en) | 2012-07-11 |
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| CN2008100848227A Active CN101302290B (en) | 2007-05-07 | 2008-03-27 | Method for preparing polytetramethylene terephthalat ether glycol using heteropolyacid catalyst |
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| CN (1) | CN101302290B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103360594A (en) * | 2013-07-18 | 2013-10-23 | 吕涛 | Method for preparing polytetramethylene ether glycol by using imidazole polyoxometalate catalyst |
| CN113563575A (en) * | 2021-07-29 | 2021-10-29 | 浙江皇马科技股份有限公司 | Alkylene oxide-tetrahydrofuran copolymer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100558707B1 (en) * | 1999-11-16 | 2006-03-10 | 주식회사 효성 | Method for preparing polytetramethylene ether glycol diester |
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- 2007-05-07 KR KR1020070044183A patent/KR100870532B1/en active IP Right Grant
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103360594A (en) * | 2013-07-18 | 2013-10-23 | 吕涛 | Method for preparing polytetramethylene ether glycol by using imidazole polyoxometalate catalyst |
| CN113563575A (en) * | 2021-07-29 | 2021-10-29 | 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 |
| CN101302290B (en) | 2012-07-11 |
| KR100870532B1 (en) | 2008-11-26 |
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