CN112142967A - Synthesis method of polycaprolactone polyol - Google Patents
Synthesis method of polycaprolactone polyol Download PDFInfo
- Publication number
- CN112142967A CN112142967A CN202010879970.9A CN202010879970A CN112142967A CN 112142967 A CN112142967 A CN 112142967A CN 202010879970 A CN202010879970 A CN 202010879970A CN 112142967 A CN112142967 A CN 112142967A
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- Prior art keywords
- catalyst
- acid
- polycaprolactone polyol
- polyol
- poly
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- 229920001610 polycaprolactone Polymers 0.000 title claims abstract description 29
- 239000004632 polycaprolactone Substances 0.000 title claims abstract description 27
- 229920005862 polyol Polymers 0.000 title claims abstract description 26
- 150000003077 polyols Chemical class 0.000 title claims abstract description 26
- 238000001308 synthesis method Methods 0.000 title claims description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 4
- 230000002194 synthesizing effect Effects 0.000 claims abstract 5
- IWHLYPDWHHPVAA-UHFFFAOYSA-N 6-hydroxyhexanoic acid Chemical compound OCCCCCC(O)=O IWHLYPDWHHPVAA-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 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
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-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
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-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
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 2
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-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
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-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
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 239000003729 cation exchange resin Substances 0.000 claims description 2
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 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
- OJLGWNFZMTVNCX-UHFFFAOYSA-N dioxido(dioxo)tungsten;zirconium(4+) Chemical compound [Zr+4].[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O OJLGWNFZMTVNCX-UHFFFAOYSA-N 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 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
- 239000002808 molecular sieve Substances 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 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
- 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
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims 1
- 229940035437 1,3-propanediol Drugs 0.000 claims 1
- 230000002378 acidificating effect Effects 0.000 claims 1
- 229940093476 ethylene glycol Drugs 0.000 claims 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims 1
- 235000013772 propylene glycol Nutrition 0.000 claims 1
- IWHLYPDWHHPVAA-UHFFFAOYSA-M 6-hydroxyhexanoate Chemical compound OCCCCCC([O-])=O IWHLYPDWHHPVAA-UHFFFAOYSA-M 0.000 abstract 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002253 acid Substances 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G63/02—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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a method for synthesizing polycaprolactone polyol, which comprises the following steps of mixing poly-6-hydroxyhexanoate with polyol, a first catalyst and a solvent at 300 ℃ for transesterification reaction for 1-20h, adding a second catalyst at 300 ℃ of 250 ℃ and 0.0005-0.1MPa for molecular weight modulation for 1-5h, distilling the solvent after the reaction is finished, and finally obtaining the polycaprolactone polyol: the cost is lower, the yield of polycaprolactone polyol is improved, the whole reaction risk is low, and the method is environment-friendly and pollution-free.
Description
Technical Field
The invention belongs to the chemical industry, and particularly relates to a synthetic 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: firstly, mixing the poly 6-hydroxy caproate with polyhydric alcohol, a first catalyst and a solvent at the temperature of 220-300 ℃ for transesterification reaction for 1-20h, then adding a second catalyst at the temperature of 250-300 ℃ under the absolute pressure of 0.0005-0.1Mpa for molecular weight modulation for 1-5h, and distilling the solvent after the reaction is finished to finally obtain the polycaprolactone polyhydric alcohol.
The polyalcohol used for ester exchange is one or more selected from ethylene glycol, 1, 3-propylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, glycerol, 1, 4-cyclohexanediol, and 1, 4-cyclohexanedimethanol.
The amount of the polyhydric alcohol is 50-300% of the poly-6-hydroxycaproic acid.
The first catalyst is selected from one or more of concentrated sulfuric acid, sulfonic acid, strong acid cation exchange resin, zirconium sulfate, tin sulfate, zirconium oxide, zirconium tungstate, formic acid, acetic acid, propionic acid and p-toluenesulfonic acid.
The first catalyst is 0.005-5% of poly-6-hydroxycaproic acid.
The solvent is one or more selected from THF, acetone, DMSO, DMF, and chloroform, and the amount of the solvent is 0-200% of that of the poly-6-hydroxycaproic acid.
The ester exchange reaction temperature is 220-300 ℃, and the reaction time is 1-20 h.
The second catalyst is selected from one or more of 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 second catalyst is 0.005-5% of that of the 6-hydroxycaproic acid.
The invention has the beneficial effects that:
compared with most of polycaprolactone polyol products on the market, the technology has lower cost, solves the problem of cost of a route which depends on caprolactone as a raw material, provides a new technical route for the diversified production of the polycaprolactone polyol, improves the yield of the polycaprolactone polyol, has small risk of the whole reaction, is environment-friendly and has no pollution.
Detailed Description
The invention is further described below with reference to examples. The scope of the invention is not limited thereto.
Example 1
30g of polycaprolactone, 20g of ethylene glycol, 0.5g of formic acid and 20g of THF are mixed and added into a 250ml round-bottom flask, the flask is placed in a heat collection type constant temperature heating magnetic stirring instrument for reaction at 250 ℃ for 3h, then 0.5g of ethylene glycol antimony is added for reaction at 255 ℃ and absolute pressure of 0.05Mpa for 1h, and after the reaction is finished, redundant solvent is distilled and removed to obtain 28.9g of polycaprolactone polyol, wherein the yield is 96.3%.
Examples 2 to 5
The quality of polycaprolactone is the same as that of example 1, and is different from that of example 1 in the following table 1.
Examples 6 to 10
The mass of polycaprolactone was 40g, which is otherwise different from example 1 and is specified in Table 1.
Examples 11 to 15
The mass of polycaprolactone was 50g, which is different from example 1 and is shown in Table 1.
The experimental data for examples 1-15 are detailed in Table 1.
Table 1 summary of experimental data of examples
As can be seen from the table, the yield of polycaprolactone polyol was over 95%.
Claims (7)
1. A synthesis method of polycaprolactone polyol is characterized in that poly-6-hydroxyhexanoate is firstly mixed with polyol, a first catalyst and a solvent at the temperature of 220 ℃ and 300 ℃ for transesterification reaction for 1-20h, then a second catalyst is added for molecular weight modulation at the temperature of 250 ℃ and 300 ℃ and the absolute pressure of 0.0005-0.1Mpa for 1-5h, and the solvent is distilled after the reaction is finished, so that the polycaprolactone polyol is finally obtained.
2. The method for synthesizing polycaprolactone polyol according to claim 1, wherein the polyol used for the transesterification is one or more selected from ethylene glycol, 1, 3-propanediol, 1, 2-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, glycerol, 1, 4-cyclohexanediol, and 1, 4-cyclohexanedimethanol.
3. The method of claim 1, wherein the polyol is present in an amount of 50% to 300% of the poly-6-hydroxycaproic acid.
4. The method for synthesizing polycaprolactone polyol according to claim 1, wherein the first catalyst is one or more selected from concentrated sulfuric acid, sulfonic acid, strongly acidic cation exchange resin, zirconium sulfate, tin sulfate, zirconium oxide, zirconium tungstate, formic acid, acetic acid, propionic acid and p-toluenesulfonic acid.
5. The method of claim 1, wherein the first catalyst is present in an amount of 0.005% to 5% of the poly-6-hydroxycaproic acid.
6. The method for synthesizing polycaprolactone polyol according to claim 1, wherein the solvent is one or more selected from THF, acetone, DMSO, DMF and chloroform, and the amount is 0-200% of poly-6-hydroxycaproic acid.
7. The method for synthesizing polycaprolactone polyol according to claim 1, wherein the second catalyst is one or more selected from cobalt acetate, ethylene glycol antimony, manganese, zinc, calcium, cobalt, lead acetate, amorphous aluminum silicate, and ZSM-5 type molecular sieve, and the amount of the second catalyst is 0.005% -5% of 6-hydroxycaproic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010879970.9A CN112142967A (en) | 2020-08-27 | 2020-08-27 | Synthesis method of polycaprolactone polyol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010879970.9A CN112142967A (en) | 2020-08-27 | 2020-08-27 | Synthesis method of polycaprolactone polyol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112142967A true CN112142967A (en) | 2020-12-29 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010879970.9A Pending CN112142967A (en) | 2020-08-27 | 2020-08-27 | Synthesis method of polycaprolactone polyol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112142967A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114044886A (en) * | 2021-12-01 | 2022-02-15 | 青岛科技大学 | Production method of polycaprolactone |
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 |
-
2020
- 2020-08-27 CN CN202010879970.9A patent/CN112142967A/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 (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114044886A (en) * | 2021-12-01 | 2022-02-15 | 青岛科技大学 | Production method of polycaprolactone |
| CN114044886B (en) * | 2021-12-01 | 2023-08-29 | 青岛科技大学 | Production method of polycaprolactone |
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Application publication date: 20201229 |
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