CN117089051B - Method for synthesizing high molecular weight polylactic acid by solution polymerization method - Google Patents
Method for synthesizing high molecular weight polylactic acid by solution polymerization method Download PDFInfo
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 51
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000010528 free radical solution polymerization reaction Methods 0.000 title claims abstract description 12
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003999 initiator Substances 0.000 claims abstract description 16
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002608 ionic liquid Substances 0.000 claims abstract description 14
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000002425 crystallisation Methods 0.000 claims abstract description 7
- 230000008025 crystallization Effects 0.000 claims abstract description 7
- 238000004090 dissolution Methods 0.000 claims abstract description 7
- 239000013078 crystal Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 12
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 5
- 235000011150 stannous chloride Nutrition 0.000 claims description 5
- 239000001119 stannous chloride Substances 0.000 claims description 5
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 claims description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 4
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 4
- ZXLOSLWIGFGPIU-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;acetate Chemical compound CC(O)=O.CCN1CN(C)C=C1 ZXLOSLWIGFGPIU-UHFFFAOYSA-N 0.000 claims description 3
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 claims description 3
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 6
- 238000001291 vacuum drying Methods 0.000 abstract description 5
- 239000007810 chemical reaction solvent Substances 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 230000036632 reaction speed Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000004321 preservation Methods 0.000 abstract 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 14
- 238000009826 distribution Methods 0.000 description 8
- 235000014655 lactic acid Nutrition 0.000 description 7
- 239000004310 lactic acid Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- VSTXCZGEEVFJES-UHFFFAOYSA-N 1-cycloundecyl-1,5-diazacycloundec-5-ene Chemical compound C1CCCCCC(CCCC1)N1CCCCCC=NCCC1 VSTXCZGEEVFJES-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 1
- 239000002473 artificial blood Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- -1 guanidine compound Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 210000004872 soft tissue Anatomy 0.000 description 1
- 239000012974 tin catalyst Substances 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
- C08G63/02—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
- C08G63/81—Preparation processes using solvents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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 discloses a method for synthesizing high molecular weight polylactic acid by a solution polymerization method, belonging to the technical field of high molecular synthesis. Mixing and stirring methylimidazole ionic liquid and lactide monomer, adding an initiator and a catalyst under stirring, replacing air with nitrogen, heating to 110 ℃ under the protection of nitrogen, carrying out heat preservation reaction for 8-10 h, cooling, adding dichloromethane for dissolution, adding absolute ethyl alcohol for crystallization, and carrying out crystal vacuum drying to obtain the high molecular weight polylactic acid. The methylimidazole ionic liquid can be used as a reaction solvent, has certain solubility to polylactic acid, reduces the use of dichloromethane, can be recycled, plays a double role of a solvent and a catalyst in the reaction process, has high reaction speed, low reaction cost, high yield and high safety, and is suitable for large-scale production.
Description
Technical Field
The invention belongs to the technical field of high molecular synthesis, and particularly relates to a method for synthesizing high molecular weight polylactic acid by a solution polymerization method.
Background
Polylactic acid is an important biodegradable material, has degradability, biocompatibility, good mechanical property and machinability, and is mainly used in the medical fields of surgical suture lines, dentistry, ophthalmology, medical controlled release systems, artificial skin, artificial blood vessels, bone and soft tissue defect part filling agents, bioabsorbable stents and the like. Polylactic acid can be synthesized by two methods, namely a direct polymerization method, namely, lactic acid is directly polycondensed under the action of a catalyst to obtain a low-molecular-weight lactic acid polymer; secondly, a ring-opening polymerization method is adopted, namely lactic acid is synthesized into lactide through dehydration, polycondensation and depolymerization processes, and the lactide is purified by a solvent and then subjected to ring-opening polymerization reaction to obtain polylactic acid. The method can obtain high molecular weight products with millions of molecular weight through ionic polymerization or coordination polymerization, and is a main method for preparing polylactic acid currently.
Chinese patent CN101429276a discloses a method for synthesizing polylactic acid with controllable molecular weight and no metal residue, which uses lactide as monomer, 1, 8-diazabicyclo undec-7-ene as catalyst, alcohol as initiator, and obtains polylactic acid with number average molecular weight of 1000-50000. Chinese patent CN102702488A discloses a method for preparing polylactic acid, which uses lactide as monomer, dodecanol or ethylene glycol as initiator, under the protection of 100-150 ℃ and normal pressure inert gas, reacting for 24-48h to prepare polylactic acid with weight average molecular weight of 80000-600000, chinese patent CN106279643a discloses a method for dehydrating and polycondensing lactic acid to obtain lactic acid oligomer, mixing lactic acid oligomer with catalyst, heating and reacting under vacuum condition to obtain polylactic acid intermediate product, continuously adding chain extender HDI, and continuously vacuum heating and reacting to obtain polylactic acid with weight average molecular weight of 350KDa-410 KDa. Chinese patent CN104448261a discloses a method for preparing polylactic acid with medium molecular weight by ring-opening polymerization of lactide at high temperature under reduced pressure in two stages by using bio-organic guanidine compound and nontoxic acid salt as catalysts, wherein the polylactic acid with weight average molecular weight of 400KDa-550KDa is obtained by continuously heating and decompressing in the first stage. Chinese patent CN108285528A discloses a preparation method of medical polylactic acid with ultra-high molecular weight, which takes dodecanol as an initiator and stannous octoate as a catalyst, and the polylactic acid with the weight average molecular weight of 210-2160kDa is prepared by reacting for 6-120h at the temperature of 100-180 ℃ and the vacuum degree of 1-1000 pa. Chinese patent CN111499844A discloses a medical polylactic acid and a preparation method thereof, wherein an alcohol initiator and a tin catalyst are adopted to react for 12-72 hours under the conditions of 130-150 ℃ and 1-20pa of vacuum degree, so as to prepare the polylactic acid with high molecular weight. Chinese patent CN111690124A discloses a medical polylactic acid with controllable molecular weight and a preparation method thereof, wherein 0.005-10 parts of lactic acid, 0.1-1 part of catalyst and 150 parts of lactide are adopted to react for 5-24 hours under the conditions that the temperature is 120-180 ℃ and the vacuum degree is not lower than 0.07MPa, and a polylactic acid product with weight average molecular weight of 5-500 kDa is prepared. Chinese patent CN 113512180A discloses a preparation method of ultra-high molecular weight levorotatory polylactic acid, which uses n-octanol as initiator and stannous octoate as catalyst, synthesizes polylactic acid by microwave ultrasonic heating, obtains block after the reaction is completed, and purifies after pulverizing to obtain the weight average molecular weight range of 30000-3000000.
The technical schemes for preparing the polylactic acid disclosed in the above patent are all melt polymerization, the viscosity of the high molecular weight polylactic acid is increased along with the progress of the reaction, the yield of the polylactic acid is low, the safety risk is increased, the usage amount of an initiator and a catalyst is high, the reaction time is long, the molecular weight distribution is wide, specific equipment is required, the production cost is high, and the centralized large-scale production is not facilitated.
Disclosure of Invention
Aiming at the problems that the melt polymerization method for preparing polylactic acid in the prior art has high production cost, large molecular weight distribution range, high safety risk and difficult centralized and large-scale production, the invention provides a method for synthesizing high molecular weight polylactic acid by solution polymerization, which adopts a solution polymerization method and methylimidazole ionic liquid as a solvent, the obtained polylactic acid has narrow molecular weight distribution, high reaction speed, low reaction cost, high yield and high safety, and is suitable for large-scale production.
The invention is realized by the following technical scheme:
the method for synthesizing the high molecular weight polylactic acid by the solution polymerization method comprises the steps of mixing and stirring methylimidazole ionic liquid and lactide monomer, adding an initiator and a catalyst under the stirring condition, replacing air with nitrogen, heating to 110 ℃ under the protection of nitrogen, preserving heat for reaction for 8-10 hours, cooling, adding methylene dichloride for dissolution, adding absolute ethyl alcohol for crystallization, and carrying out vacuum drying on the crystals to obtain the high molecular weight polylactic acid; the ionic liquid of methylimidazole can be used as a reaction solvent, has certain solubility to polylactic acid, reduces the use of dichloromethane, can be recycled, and plays a double role of a solvent and a catalyst in the reaction process.
Further, the initiator is more than one of dodecanol, hexadecanol and octadecanol; the catalyst is more than one of stannous chloride, stannous octoate and stannous acetate.
Further, the lactide monomer is D-lactide or L-lactide.
Further, the mass ratio of the lactide monomer to the catalyst is 2000-5000: 1, the mass ratio of the lactide monomer to the initiator is 2000-5000: 1.
further, the methylimidazole ionic liquid is 3-dimethyl-2-imidazolidinone or 1-ethyl-3-methylimidazole acetate.
Further, the charging ratio of the methylimidazole ionic liquid to the lactide monomer is 2-4L: 1kg.
Further, the moisture content of the methylimidazole ionic liquid is lower than 10ppm.
The beneficial effects obtained by the invention are as follows:
(1) The invention adopts solution polymerization, the viscosity is reduced, the stirring is uniform and sufficient, and the molecular weight distribution of the obtained high molecular weight polylactic acid is narrowed;
(2) The invention can be used for a common glass reaction kettle or a stainless steel reaction kettle without specific equipment, thereby being convenient for large-scale production;
(3) The methylimidazole ionic liquid can be used as a reaction solvent, has certain solubility to polylactic acid, reduces the use of methylene dichloride, can be recycled, plays a double role of a solvent and a catalyst in the reaction process, has high reaction speed, low reaction cost, high yield and high safety, and is suitable for large-scale production.
Detailed Description
The above-described matters of the present invention will be described in further detail by way of examples, but it should not be construed that the scope of the above-described subject matter of the present invention is limited to the following examples, and all techniques realized based on the above-described matters of the present invention are within the scope of the present invention.
Example 1
15L 3-dimethyl-2-imidazolinone (moisture content is less than or equal to 10 ppm) and 5kg L-lactide are added into a dry and clean stainless steel reaction kettle, 2.0g of initiator dodecanol and 2.5g of catalyst stannous chloride are added during stirring, 3 times of nitrogen replacement are carried out, the temperature is raised to 110 ℃ under the protection of nitrogen, the temperature is kept for 10 hours, after the reaction is finished, the temperature is reduced, dichloromethane is added for dissolution, then absolute ethyl alcohol is added for crystallization, the high molecular weight polylactic acid is obtained through vacuum drying of crystals, the weight average molecular weight of the high molecular weight polylactic acid is 604082, the distribution coefficient is 1.32, and the yield is 92%.
Example 2
15L of 1-ethyl-3-methylimidazole acetate (the moisture content is less than or equal to 10 ppm) and 5kg of D-lactide are added into a dry and clean stainless steel reaction kettle, mixed and stirred, 2.0g of hexadecanol serving as an initiator and 2.5g of stannous chloride serving as a catalyst are added in the stirring process, the mixture is replaced by nitrogen for 3 times, the temperature is raised to 110 ℃ under the protection of nitrogen, the reaction is kept for 10 hours, the temperature is reduced after the reaction is finished, methylene dichloride is added for dissolution, then absolute ethyl alcohol is added for crystallization, and the crystal is dried in vacuum to obtain the high molecular weight polylactic acid, wherein the weight average molecular weight of the high molecular weight polylactic acid is 610463, the distribution coefficient is 1.34, and the yield is 94%.
Example 3
15L 3-dimethyl-2-imidazolinone (moisture content is less than or equal to 10 ppm) and 5kg L-lactide are added into a dry and clean stainless steel reaction kettle, and are mixed and stirred, 1.2g of initiator dodecanol and 1.6g of catalyst stannous chloride are added in the stirring process, 3 times of nitrogen replacement are carried out, the temperature is raised to 130 ℃ under the protection of nitrogen, the temperature is kept for 8 hours, after the reaction is finished, the temperature is reduced, dichloromethane is added for dissolution, then absolute ethyl alcohol is added for crystallization, and the high molecular weight polylactic acid is obtained through vacuum drying, wherein the weight average molecular weight of the high molecular weight polylactic acid is 841028, the distribution coefficient is 1.36, and the yield is 94%.
Comparative example 1
15L of 3-dimethyl-2-imidazolidinone (the water content is less than or equal to 10 ppm) and 5 kgL-lactide are added into a dry and clean stainless steel reaction kettle, mixed and stirred, nitrogen is replaced for 3 times, the temperature is raised to 110 ℃ under the protection of nitrogen, the temperature is kept for 10 hours for reaction, after the reaction is finished, the temperature is reduced, dichloromethane is added for dissolution, then absolute ethyl alcohol is added for crystallization, the polylactic acid is obtained through crystal vacuum drying, the weight average molecular weight of the polylactic acid is 2356, the molecular weight distribution coefficient is 1.1, and the yield is 90%.
Claims (5)
1. A method for synthesizing high molecular weight polylactic acid by a solution polymerization method is characterized in that methylimidazole ionic liquid is used as a solvent, methylimidazole ionic liquid and lactide monomer are mixed and stirred, an initiator and a catalyst are added under the stirring condition, nitrogen replaces air, the temperature is raised to 110 ℃ under the protection of nitrogen, the temperature is kept for reaction for 8-10 hours, the temperature is lowered, dichloromethane is added for dissolution, then absolute ethanol is added for crystallization, and the crystals are dried in vacuum to obtain the high molecular weight polylactic acid;
the initiator is more than one of dodecanol, hexadecanol and octadecanol; the catalyst is more than one of stannous chloride, stannous octoate and stannous acetate;
the methylimidazole ionic liquid is 1, 3-dimethyl-2-imidazolidinone or 1-ethyl-3-methylimidazole acetate.
2. The method for synthesizing high molecular weight polylactic acid according to claim 1, wherein the lactide monomer is D-lactide or L-lactide.
3. The method for synthesizing high molecular weight polylactic acid by a solution polymerization method according to claim 1, wherein the mass ratio of the lactide monomer to the catalyst is 2000-5000: 1, the mass ratio of the lactide monomer to the initiator is 2000-5000: 1.
4. the method for synthesizing high molecular weight polylactic acid by using the solution polymerization method according to claim 1, wherein the feeding ratio of the methylimidazole ionic liquid to the lactide monomer is 2-4L: 1kg.
5. The method for synthesizing high molecular weight polylactic acid according to the solution polymerization method of claim 1, wherein the water content of the methylimidazole ionic liquid is lower than 10ppm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202311364829.5A CN117089051B (en) | 2023-10-20 | 2023-10-20 | Method for synthesizing high molecular weight polylactic acid by solution polymerization method |
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| CN202311364829.5A CN117089051B (en) | 2023-10-20 | 2023-10-20 | Method for synthesizing high molecular weight polylactic acid by solution polymerization method |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702488A (en) * | 2012-06-07 | 2012-10-03 | 上海绿色盛世生态材料有限公司 | Preparation method for polylactic acid |
| BRPI1106280A2 (en) * | 2011-10-11 | 2013-08-20 | Univ Fed Do Rio Grande Do Sul | Production process of a high molecular weight poly (lactic acid) and high molar mass poly (lactic acid) |
| CN108285528A (en) * | 2018-03-08 | 2018-07-17 | 深圳市迈启生物材料有限公司 | A kind of preparation method of the medical polylactic acid of super high molecular weight |
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| JP7000631B1 (en) * | 2020-04-06 | 2022-02-10 | 帝人株式会社 | Method for Producing Aliphatic Polyester, Aliphatic Polyester Resin and Aliphatic Polyester Resin Composition |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BRPI1106280A2 (en) * | 2011-10-11 | 2013-08-20 | Univ Fed Do Rio Grande Do Sul | Production process of a high molecular weight poly (lactic acid) and high molar mass poly (lactic acid) |
| CN102702488A (en) * | 2012-06-07 | 2012-10-03 | 上海绿色盛世生态材料有限公司 | Preparation method for polylactic acid |
| CN108285528A (en) * | 2018-03-08 | 2018-07-17 | 深圳市迈启生物材料有限公司 | A kind of preparation method of the medical polylactic acid of super high molecular weight |
Non-Patent Citations (3)
| Title |
|---|
| Lipase-catalyzed polymerization ofL-lactide in ionic liquids;Masahiro Yoshizawa-Fujita;POLYMERS FOR ADVANCED TECHNOLOGIES(第19期);1396-1400 * |
| The Effect of Solvent Hydrophilicity on the Enzymatic Ring-Opening Polymerization of L-Lactide by Candida rugosa Lipase;Catia Angli Curie;Polymer(第14期);3856 * |
| 丙交酯在离子液体中的开环聚合反应研究;张超;2005年全国高分子学术论文报告会 * |
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