CN101245136B - Process for producing tetrahydrofuran polymer - Google Patents
Process for producing tetrahydrofuran polymer Download PDFInfo
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- CN101245136B CN101245136B CN2007101037766A CN200710103776A CN101245136B CN 101245136 B CN101245136 B CN 101245136B CN 2007101037766 A CN2007101037766 A CN 2007101037766A CN 200710103776 A CN200710103776 A CN 200710103776A CN 101245136 B CN101245136 B CN 101245136B
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- hpa
- thf
- ptmg
- heteropolyacid
- catalyzer
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- 238000000034 method Methods 0.000 title claims abstract description 29
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 title abstract description 62
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 title abstract description 5
- 229920000642 polymer Polymers 0.000 title abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 12
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 12
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 10
- -1 polytetramethylene terephthalate Polymers 0.000 claims abstract description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims description 15
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus 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
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 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 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 15
- 239000003054 catalyst Substances 0.000 abstract description 9
- 229920001577 copolymer Polymers 0.000 abstract 1
- 229920001519 homopolymer Polymers 0.000 abstract 1
- 229920000874 polytetramethylene terephthalate 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 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 238000002360 preparation method Methods 0.000 description 10
- 208000012839 conversion disease Diseases 0.000 description 9
- 229920002334 Spandex Polymers 0.000 description 8
- 239000004759 spandex Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 241001550224 Apha Species 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 238000000622 liquid--liquid extraction Methods 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- 238000007738 vacuum evaporation Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000002926 oxygen Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 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
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000000129 anionic group Chemical group 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
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 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
- 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
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001879 gelation Methods 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
- 230000005283 ground state Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 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
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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)
- Polyethers (AREA)
Abstract
The invention relates to a method for prepare tetrahydrofuran polymer using heteropolyacid (HPA), specifically, the invention relates to a method of polytetramethylene terephthalate glycol to prepare tetrahydrofuran homopolymer or copolymer using high purity HPA as the catalyst, wherein the content of the basic impurities such as NA, Mg and Ca in the high purity HPA is 100 ppm or less.
Description
Technical field
The present invention relates to the method that a kind of use heteropolyacid (hereinafter is called " HPA ") prepares tetrahydrofuran polymer; Particularly, the present invention relates to the high purity HPA that a kind of use comprises 100ppm or alkaline impurities still less (for example Na, Mg or Ca) and prepare polytetramethylene glycol (polytetramethyleneglycol) method of (hereinafter is called " PTMG ") by THF (hereinafter is called " THF ") as catalyzer.
In general, PTMG has elasticity (or can form multiple shape and can not rupture), and is used as main raw material and the softening agent or the tenderizer of spandex (a kind of spandex fiber).PTMG is prepared by THF, particularly under the condition of use HPA as catalyzer, prepares.
Background technology
Known systems has disclosed the method that is prepared PTMG by THF.For example, United States Patent(USP) No. 4,568,775, No.4,658,065 and No.5,416,240 have disclosed the method for using HPA to prepare polyether glycol, have particularly disclosed the working method of the THF polymkeric substance that comprises PTMG.Method according to above-mentioned reference discloses prepares polymkeric substance through first step by THF, and according to other existing known technology, then prepares polymkeric substance through second step by THF.
United States Patent(USP) No. 6,414,109 have disclosed another kind of use HPA makes THF polymeric method, and the Al content of wherein said HPA is 4ppm or lower, and Cr content is 1ppm or lower.According to this reference, in the ring-opening polymerization process,, not only can make HPA painted, and also can make resulting polymkeric substance have color sometimes, so the problem of existing if the amount of contained Cr is big in the HPA catalyzer.In addition,, think that the amount conference of Al causes the problem that is generated the reaction conversion ratio reduction of polymkeric substance by THF though do not know it is what reason.
In general, the HPA catalyzer is by alkaline precursor preparation; Therefore may contain a certain amount of alkaline impurities in the HPA catalyzer.Although the amount of contained this alkaline impurities is that hundreds of arrives several ten thousand ppm among the HPA, these alkaline impurities are not still ad hoc reported the influence of THF polyreaction.
Yet the inventor has been noted that a kind of like this result: in HPA, contain under the situation of a large amount of alkaline impurities such as Na, Mg or Ca, the reaction conversion ratio of THF reduces.By inference, following factors possibly impel reaction conversion ratio to reduce.In the THF polymerization process, HPA is ionized and forms hydrogen ion and heteropolyanion, and in this case, along with the concentration rising of Ionized HPA, the yield of THF polyreaction is also high more.The concentration of Ionized HPA depends on the pH of solution to a great extent, particularly, the ionization constant of HPA pH be 7 or higher basic soln in reduce, the result makes the performance degradation of an acidic catalyst.
Another problem possibly be the problem of end product quality deterioration, and the deterioration of this end product quality is to cause owing to the alkaline impurities such as Na, Mg or Ca remains among the PTMG by the preparation of THF polyreaction.PTMG can be used as the main raw material of the polymkeric substance for preparing spandex as a kind of THF polymkeric substance.In the process of preparation spandex, basylous element contained among the PTMG causes gel phenomenon, and the result makes the quality deterioration of spandex product.Owing to these reasons, the alkaline impurities that is included in the HPA catalyzer possibly be a big obstacle of preparation high quality spandex.Therefore, need in the process of preparation PTMG, remove the basic metal composition among the HPA.
The object of the present invention is to provide a kind of HPA of use to prepare the method for PTMG as catalyzer, the alkaline impurities content of wherein said HPA is lower than alkaline impurities content of the prior art.
Summary of the invention
According to the preferred embodiments of the invention, use HPA to prepare PTMG by THF as catalyzer, the content of the Na among the wherein said HPA, Mg or Ca is 100ppm or still less.
According to the preferred embodiments of the invention, use Zeo-karb or liquid-liquid extraction to come purifying HPA.
According to the preferred embodiments of the invention, HPA can be tungstophosphoric acid, molybdophosphate or tungstosilicic acid.
According to the preferred embodiments of the invention, the HPA ligancy is adjusted to 5 to 8.
Below, the present invention will be described in detail with reference to example.It only is for illustrative purposes that these examples are provided, and should not be understood as that it limits scope of the present invention.
According to the method for preparing PTMG of the present invention, HPA is used as catalyzer.Usually, HPA and 20 to 40 water molecules coordinations, but resulting HPA maybe not can make THF realize effective polyreaction.Therefore, the number of necessary adjusting and heteropolyanion coordinate water molecules.In order to regulate the number with heteropolyanion coordinate water molecules, can use the method that changes catalyst activity usually, for example under 100 ℃ to 300 ℃ temperature, heat HPA.Heating temperature and heat-up time can be regulated according to the coordinated water molecule number, for example, can be adjusted to 3 to 18 to the number with HPA coordinate water molecules.
HPA of the present invention can be a kind of like this oxygen acid condenses, and this oxygen acid condenses is obtained with a kind of oxygen acid condensation that is selected among P (phosphorus), As (arsenic), Ge (germanium), Ti (titanium), Ce (caesium) and the Co (cobalt) by at least a oxide compound that is selected among Mo (molybdenum), W (tungsten) and the V (vanadium).
For HPA, can use any known HPA that satisfies the above-mentioned condition of the present invention.Its preferred (but not being defined) is for having following chemical molecular formula (1).Particularly, the HPA that has a following chemical formula (1) can be used for preparing PTMG and spandex:
Ha(XbMcOd)
-a……(1)。
In formula 1, " X " represents phosphorus, antimony, silicon or boron, and " M " represents molybdenum, tungsten or vanadium, and " O " represents oxygen, and " b ", " c " and " d " represent each atoms of elements ratio, and " a " representative is by the value of the valency decision of each element.
For example, " b " in the chemical formula (1) can be 1 to 5, be preferably 1 to 2." c " in the chemical formula (1) can be 5 to 20, and " d " can be for 18 to 62, be preferably 40 to 62." a " in the chemical formula (1) is meant the anionic negative charge of polyoxy, and its value can change along with various conditions, and still, in order to keep the balance of said molecular formula, this value always equates with proton number.HPA and polyoxometallate have multiple structure, but in these structures, the HPA compound with Keggin structure can be used for preparing PTMG.
According to the present invention, at first answer purifying HPA.Come purifying HPA according to Zeo-karb that is described below or liquid-liquid extraction method.
Use the Zeo-karb purified catalyst
HPA catalyst dissolution through comprising impurity prepares the 1mol aqueous solution in zero(ppm) water.Sulfonated phenol formaldehyde resin or sulphonated polystyrene resin are filled in vertical sending at 5cm * 100cm in Simon Rex (pyrex) glass column.Make the aqueous solution flow through this vertical Simon Rex glass column of sending, remove moisture with rotation vacuum-evaporation appearance then, the result obtains highly purified HPA.
Use liquid-liquid extraction method purified catalyst
HPA catalyst dissolution through comprising impurity prepares the 1mol aqueous solution in zero(ppm) water.In this aqueous solution, add isopyknic 24% hydrochloric acid, and with the solution stirring that obtains 5 hours.With the ether equal-volume join in the gained HPA solution, and the solution room temperature that obtains is placed 3 hours with layering.Extract the lower floor of solution, use rotation vacuum-evaporation appearance to remove moisture then, the result obtains highly purified HPA.In this case, residual if ether still has, then add zero(ppm) water and process solution, use rotation vacuum-evaporation appearance then, the result obtains highly purified HPA.
According to the present invention, use HPA following as the method for Preparation of Catalyst PTMG.
Fig. 1 illustrates the equipment 1 that is used to prepare PTMG that uses in the present invention.
THF is introduced in the reactor drum 11.THF can be by (for example) 1, the preparation of 4-butyleneglycol.But can be according to the THF of known choice of technology the present invention use.THF and water are introduced in the reactor drum, and coordination has the HPA of water molecules also to introduce in the reactor drum then.In reactor drum, the amount of the water in the catalyzer can be adjusted to 3 to 18 coordinated water molecules.In polymerization process, the amount of water may reduce.For the number that makes coordinated water keeps constant, introduce water extraly with water supply device 13.Under the coordinated water molecule surpasses 20 situation, perhaps the mol ratio of water and HPA less than 0.1 situation under, the performance of polymerization reaction system is understood obvious deterioration.The amount of the water of extra introducing is confirmed by polymerization process.When HPA is introduced in the reactor drum, under 40 ℃ to 80 ℃ temperature, stirred the reaction mixture that forms by THF, water and HPA 2 to 6 hours.Reaction mixture placed phase-separating device 12 thereafter.HPA layer in the reaction mixture and THF monomer layer homogeneous reaction, and reaction mixture separates into the upper and lower in phase-separating device 12.From phase-separating device 12 collection upper stratas, and remaining THF monomer removed through still column 14, the result obtains PTMG.
Hereinafter will be explained the measuring method of reaction conversion ratio and the colourity of the PTMG that obtains.
Measure reaction conversion ratio
After polyreaction, reaction mixture is at room temperature placed 10 hours, so that it is two-layer that it is separated into.After isolating the upper strata, only in this upper strata, add the octane of two volumes, and gains were stirred 5 hours at 30 ℃.Through mean diameter is that the polytetrafluoroethylene filter of 0.2 μ m comes separating catalyst, then, will concentrate through the gains of this strainer with rotary vacuum evaporator.The weight of the PTMG of measurement gained is to calculate reaction conversion ratio.
Measure colourity (APHA)
Use Lovibond PFX 195 tintometers, measure the colourity of PTMG through APHA (APHA) colour code system.
Measure the content of impurity in the HPA catalyzer
Through inductively coupled plasma (ICP, OPTIMA 3000, produced by Perkin-Elemer company) analytical method, measure the content of the alkaline impurities such as Na, Mg and Ca in the HPA catalyzer.According to inductively coupled plasma (ICP) analytical method, sample is introduced by in the radio-frequency induction coil inductive plasma body.Then, the atom that under 6000-8000K, is excited can be luminous when getting back to ground state.At this moment, measure the spectral line of emission and emissive porwer, resulting data are used for the qualitative analysis and the quantitative analysis of atom.
Hereinafter will specify the present invention with reference to example.Provide these examples to be only used for illustrative purpose, and should not be understood as that it limits scope of the present invention.
Example
(embodiment 1)
The 200 gram THF that will contain 300ppm water pack in the 500mL reactor drum that is provided with whisking appliance and reflux exchanger, then, and to wherein adding 100g HPA.This HPA is made with extra care in the Zeo-karb of aqueous solution form, and the ligancy of its water is adjusted in electric furnace.The content of contained Na, Mg and Ca is shown in Table 1 among the HPA.The content of contained Na, Mg and Ca can be measured through icp analysis among the HPA.The temperature of reaction of reactor drum is set at 60 ℃, and made the reactor drum continuously stirring 4 hours, then the material that obtains is placed under the room temperature to isolate the upper and lower.Remove unreacted THF in the upper strata through distillation, the result obtains the polymkeric substance of THF---polytetramethylene glycol (PTMG).Through measuring number-average molecular weight (Mn), reaction conversion ratio and the colourity (APHA) that the OH value obtains this polymkeric substance.The result is shown in Table 1.
(embodiment 2 to 4 and Comparative Examples 1 to 3)
Implementing to prepare the process of PTMG with embodiment 1 identical mode, difference is to regulate the number of content and the coordinate water of Na, Mg and Ca, and is as shown in table 1.
Table 1. embodiment and Comparative Examples
As shown in table 1, in the process of preparation PTMG, use the low relatively HPA catalyzer of content of Na, Mg and Ca, reaction conversion ratio improves, and correspondingly increases the number-average molecular weight of product.
The effect of invention
In the process of preparation PTMG, use the HPA catalyzer comprise a small amount of alkaline impurities (for example Na, Mg and Ca), reaction conversion ratio improves, and the problem of the gained PTMG gelation that can avoid in preparation spandex process, causing.
Claims (3)
1. method of using heteropolyacid to prepare polytetramethylene glycol by THF as catalyzer; The content of the sodium in the wherein said heteropolyacid, magnesium and calcium is 100ppm or still less, and said heteropolyacid is the tungstophosphoric acid through the Zeo-karb purifying.
2. the method for preparing polytetramethylene glycol according to claim 1, wherein said heteropolyacid have following chemical formula (1):
Ha(XbMcOd)
-a......(1)
Wherein, in the described formula (1), " X " represents phosphorus, antimony, silicon or boron, and " M " represents molybdenum, tungsten or vanadium, and " O " represents oxygen, and " b ", " c " and " d " represent each atoms of elements ratio, and " a " representative is by the value of the valency decision of each element.
3. the method for preparing polytetramethylene glycol according to claim 1, the ligancy in the wherein said heteropolyacid is adjusted to 5 to 8.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020070016286 | 2007-02-16 | ||
| KR1020070016286A KR100841603B1 (en) | 2007-02-16 | 2007-02-16 | Process for producing tetrahydrofuran polymer |
| KR10-2007-0016286 | 2007-02-16 |
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| Publication Number | Publication Date |
|---|---|
| CN101245136A CN101245136A (en) | 2008-08-20 |
| CN101245136B true CN101245136B (en) | 2012-02-08 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2007101037766A Expired - Fee Related CN101245136B (en) | 2007-02-16 | 2007-05-29 | Process for producing tetrahydrofuran polymer |
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| Country | Link |
|---|---|
| KR (1) | KR100841603B1 (en) |
| CN (1) | CN101245136B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1272856A (en) * | 1998-06-15 | 2000-11-08 | 旭化成工业株式会社 | Process for producing tetrahydrofuran polymer |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3446577A (en) | 1966-12-22 | 1969-05-27 | Sylvania Electric Prod | Process for producing heteropoly metal acids |
| CA1216597A (en) | 1983-05-23 | 1987-01-13 | Atsushi Aoshima | Process for producing polyetherglycol |
| GB9828020D0 (en) * | 1998-12-18 | 1999-02-10 | Bp Chem Int Ltd | Synthesis of heteropolyacids |
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- 2007-02-16 KR KR1020070016286A patent/KR100841603B1/en active IP Right Grant
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1272856A (en) * | 1998-06-15 | 2000-11-08 | 旭化成工业株式会社 | Process for producing tetrahydrofuran polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101245136A (en) | 2008-08-20 |
| KR100841603B1 (en) | 2008-06-26 |
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