CN111995736A - Preparation method of polycaprolactone polyol - Google Patents
Preparation method of polycaprolactone polyol Download PDFInfo
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- CN111995736A CN111995736A CN202010853786.7A CN202010853786A CN111995736A CN 111995736 A CN111995736 A CN 111995736A CN 202010853786 A CN202010853786 A CN 202010853786A CN 111995736 A CN111995736 A CN 111995736A
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- catalyst
- polycaprolactone
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- polyol
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- 229920001610 polycaprolactone Polymers 0.000 title claims abstract description 39
- 239000004632 polycaprolactone Substances 0.000 title claims abstract description 37
- 229920005862 polyol Polymers 0.000 title claims abstract description 26
- 150000003077 polyols Chemical class 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 10
- 230000007062 hydrolysis Effects 0.000 claims abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229960005147 calcium acetate Drugs 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- 239000000413 hydrolysate Substances 0.000 claims description 2
- 229940046892 lead acetate Drugs 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- 229960004063 propylene glycol Drugs 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/826—Metals not provided for in groups C08G63/83 - C08G63/86
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/84—Boron, aluminium, gallium, indium, thallium, rare-earth metals, or compounds thereof
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/87—Non-metals or inter-compounds thereof
Abstract
The invention provides a preparation method of polycaprolactone polyol, which comprises the steps of mixing polycaprolactone, water and a first catalyst, adding the mixture into a reactor, hydrolyzing at a certain temperature and under a certain pressure, removing water after the hydrolysis is finished, adding polyol, a second catalyst and a solvent, mixing, placing the mixture into the reactor, esterifying at a proper temperature, removing the solvent and the water after the reaction is finished, adding the catalyst and the solvent, reacting for a period of time at a certain temperature and under a certain pressure, modulating the molecular weight, and separating to obtain the polycaprolactone polyol after the reaction is finished. The invention has the beneficial effects that: compared with most of polycaprolactone polyol products on the market, the method has the advantages that the cost is lower, the experimental conditions are milder compared with other synthesis modes, the solvent and the reaction product are easy to separate, the whole reaction process is controllable, the environment is not influenced, and the environment pollution is avoided.
Description
Technical Field
The invention belongs to the chemical industry, and particularly relates to a preparation method of polycaprolactone polyol.
Background
Polycaprolactone Polyol (PCL) is an aliphatic linear polyester, is very soft and has extremely high stretchability, and PCL having a molecular weight of several thousand or less has a wide range of applications and a wide range of applications in resin modification, paints, adhesives, polyurethane artificial leathers, leather finishing agents, and the like, and is a very useful organic material. At present, caprolactone monomers are used as raw materials for preparing polycaprolactone polyol, different catalysts and initiators are used for researching the production process of polycaprolactone polyol, and the best materials and methods are selected, for example, patents CN108424512A, CN108912316A and CN109054001A are provided, but only holy petrochemical seeds and Hunan polymer seeds can industrially produce caprolactone at home, the holy petrochemical seeds are 200t/a, the Hunan polymer seeds are few, and only Swedish Basito (PERSTORP) is produced at home and can be 15000t/a abroad, and other three large enterprises are also producing caprolactone, so that the home price of caprolactone is always high, the production of polycaprolactone polyol has the problem of high raw material price, and the production of polycaprolactone polyol applied in different aspects needs to be controlled, and the reaction can be controlled according to the monomer purity, the initiator proportion, the amount of the catalysts, the reaction time and the like, The reaction temperature and the like are controlled in various aspects, and the experimental conditions are harsh.
Disclosure of Invention
In order to solve the above problems, the present invention provides a specific experimental scheme: mixing polycaprolactone, water and a first catalyst, adding the mixture into a reactor, hydrolyzing at a certain temperature and under a certain pressure, removing water after the hydrolysis is finished, adding polyol, a second catalyst and a solvent, mixing, placing the mixture into the reactor, esterifying at a proper temperature, removing the solvent and the water after the reaction is finished, adding the catalyst and the solvent, reacting for a period of time at a certain temperature and under a certain pressure, modulating the molecular weight, and separating to obtain the polycaprolactone polyol after the reaction is finished.
The first catalyst is one or more selected from sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, formic acid, acetic acid and propionic acid, and the amount of the first catalyst is 1-5% of caprolactone.
The adding amount of water is 50 to 500 percent of that of polycaprolactone
The hydrolysis temperature is 40-320 ℃, the reaction time is 1-8h, and the reaction pressure is 0.0005MPa-5 MPa.
The solvent is one or more of THF, acetone, DMSO, DMF and chloroform, and the addition amount is 50-200% of that of polycaprolactone.
The second catalyst is selected from one or more of concentrated sulfuric acid, terephthalic acid and macroporous cation resin, and the dosage of the second catalyst is 1-8% of the mass of polycaprolactone.
The polyalcohol is one or more selected from ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol and glycerol, and the amount of polyalcohol is 80-200% of the mass of hydrolysate.
The esterification temperature is 40-220 ℃, and the reaction time is 1-8 h. The molecular weight regulating catalyst is one or several selected from cobalt acetate, ethylene glycol antimony, manganese, zinc, calcium, cobalt and lead acetate, amorphous aluminum silicate and ZSM-5 type molecular sieve, and the dosage of the catalyst is 0.005-5% of that of polycaprolactone.
The molecular weight modulation reaction temperature is between 250 ℃ and 300 ℃, the reaction pressure is 0.005-0.1MPa, and the reaction time is 1-5 h.
The invention has the beneficial effects that:
compared with most of polycaprolactone polyol products on the market, the method has the advantages that the cost is lower, the experimental conditions are milder compared with other synthesis modes, the solvent and the reaction product are easy to separate, the whole reaction process is controllable, the environment is not influenced, and the environment pollution is avoided.
Detailed Description
The invention is further described below with reference to examples. The scope of the invention is not limited thereto.
Example 1
Adding 30g of polycaprolactone, 30g of water and 0.3g of sulfuric acid into a reactor, reacting for 3 hours in a heat collection type constant temperature heating magnetic stirring instrument at 50 ℃ and 0.01MPa, distilling to remove water, adding 0.3g of terephthalic acid, 30g of ethylene glycol and 15g of THF, reacting for 5 hours at 50 ℃, distilling to remove water and solvent, adding 0.2g of zinc acetate, reacting for 2 hours at 260 ℃ and 0.01MPa absolute pressure in the reactor, and removing water and redundant solvent by using a rotary evaporator to obtain 29.3g of polycaprolactone diol with the yield of 97.7%.
Examples 2 to 6
20g of polycaprolactone, and the rest parameters are shown in table 1.
Examples 7 to 11
Polycaprolactone 30g, the remaining parameters are shown in Table 1.
Examples 12 to 16
Polycaprolactone 40g, the remaining parameters are shown in Table 1.
As can be seen from the table, the yield of polycaprolactone polyol was more than 96%.
Claims (9)
1. A preparation method of polycaprolactone polyol is characterized in that polycaprolactone, water and a first catalyst are mixed and added into a reactor to be hydrolyzed under certain temperature and pressure, water is removed after the hydrolysis is finished, then polyol, a second catalyst and a solvent are added to be mixed and placed into the reactor to be esterified at proper temperature, the solvent and the water are removed after the reaction is finished, the catalyst and the solvent are added to react for a period of time under certain temperature and pressure to carry out molecular weight modulation, and the polycaprolactone polyol is obtained after the reaction is finished and separated.
2. The method for preparing polycaprolactone polyol according to claim 1, wherein the first catalyst is one or more selected from sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, formic acid, acetic acid and propionic acid, and the amount of the first catalyst is 1-5% of caprolactone.
3. The method of claim 1, wherein the amount of water added is 50% to 500% of the amount of polycaprolactone.
4. The method for preparing polycaprolactone polyol according to claim 1, wherein the hydrolysis temperature is 40-320 ℃, the reaction time is 1-8h, and the reaction pressure is 0.0005-5 MPa.
5. The method for preparing polycaprolactone polyol according to claim 1, wherein the solvent is one or more selected from THF, acetone, DMSO, DMF and chloroform, and the amount of the solvent added is 50% -200% of that of polycaprolactone.
6. The method of claim 1, wherein the second catalyst is selected from one or more of concentrated sulfuric acid, terephthalic acid, and macroporous cationic resin, and the amount of the second catalyst is 1-8% of the mass of polycaprolactone.
7. The method for preparing polycaprolactone polyol according to claim 1, wherein the polyol is one or more selected from ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, and glycerol, and the amount of the polyol is 80-200% of the mass of the hydrolysate.
8. The process for preparing polycaprolactone polyol according to claim 1, wherein the esterification temperature is 40-220 ℃ and the reaction time is 1-8 h. The molecular weight regulating catalyst is one or several selected from cobalt acetate, ethylene glycol antimony, manganese, zinc, calcium, cobalt and lead acetate, amorphous aluminum silicate and ZSM-5 type molecular sieve, and the dosage of the catalyst is 0.005-5% of that of polycaprolactone.
9. The method of claim 1, wherein the reaction temperature for molecular weight modification is between 250 ℃ and 300 ℃, the reaction pressure is 0.005-0.1MPa, and the reaction time is 1-5 h.
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| CN202010853786.7A CN111995736A (en) | 2020-08-24 | 2020-08-24 | Preparation method of polycaprolactone polyol |
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| CN202010853786.7A CN111995736A (en) | 2020-08-24 | 2020-08-24 | Preparation method of polycaprolactone polyol |
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| CN202010853786.7A Pending CN111995736A (en) | 2020-08-24 | 2020-08-24 | Preparation method of polycaprolactone polyol |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115160547A (en) * | 2022-07-27 | 2022-10-11 | 湖南聚仁化工新材料科技有限公司 | Polycaprolactone polyol, preparation method thereof and coating |
| CN115873494A (en) * | 2022-12-09 | 2023-03-31 | 福建东泰高分子材料有限公司 | Organic silicon modified waterborne polyurethane antifouling coating and preparation method thereof |
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| CN1397577A (en) * | 2002-08-23 | 2003-02-19 | 清华大学 | Process for synthesizing polyurethane elastomer containing poly-beta-hydroxybutyrate block |
| CN101450989A (en) * | 2008-12-19 | 2009-06-10 | 东华大学 | Method for synthesizing poly hydroxy fatty acid ester block copolymers in situ |
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2020
- 2020-08-24 CN CN202010853786.7A patent/CN111995736A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1397577A (en) * | 2002-08-23 | 2003-02-19 | 清华大学 | Process for synthesizing polyurethane elastomer containing poly-beta-hydroxybutyrate block |
| CN101450989A (en) * | 2008-12-19 | 2009-06-10 | 东华大学 | Method for synthesizing poly hydroxy fatty acid ester block copolymers in situ |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115160547A (en) * | 2022-07-27 | 2022-10-11 | 湖南聚仁化工新材料科技有限公司 | Polycaprolactone polyol, preparation method thereof and coating |
| CN115160547B (en) * | 2022-07-27 | 2023-05-09 | 湖南聚仁化工新材料科技有限公司 | Polycaprolactone polyol, preparation method thereof and coating |
| CN115873494A (en) * | 2022-12-09 | 2023-03-31 | 福建东泰高分子材料有限公司 | Organic silicon modified waterborne polyurethane antifouling coating and preparation method thereof |
| CN115873494B (en) * | 2022-12-09 | 2024-02-09 | 福建东泰高分子材料有限公司 | Organosilicon modified waterborne polyurethane antifouling coating and preparation method thereof |
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