CN114807252B - Synthesis method of four-arm star polylactic acid in supercritical carbon dioxide - Google Patents
Synthesis method of four-arm star polylactic acid in supercritical carbon dioxide Download PDFInfo
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- CN114807252B CN114807252B CN202210440822.6A CN202210440822A CN114807252B CN 114807252 B CN114807252 B CN 114807252B CN 202210440822 A CN202210440822 A CN 202210440822A CN 114807252 B CN114807252 B CN 114807252B
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- lactide
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- polylactic acid
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 22
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 12
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 12
- 238000001308 synthesis method Methods 0.000 title abstract description 3
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 102000004882 Lipase Human genes 0.000 claims abstract description 16
- 108090001060 Lipase Proteins 0.000 claims abstract description 16
- 239000004367 Lipase Substances 0.000 claims abstract description 16
- 235000019421 lipase Nutrition 0.000 claims abstract description 16
- 239000004386 Erythritol Substances 0.000 claims abstract description 13
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 229940009714 erythritol Drugs 0.000 claims abstract description 13
- 235000019414 erythritol Nutrition 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000003381 stabilizer Substances 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 8
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 6
- 230000035484 reaction time Effects 0.000 claims abstract description 6
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 5
- 238000012674 dispersion polymerization Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000010926 purge Methods 0.000 claims description 10
- 239000012043 crude product Substances 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 abstract description 8
- 238000009826 distribution Methods 0.000 abstract description 6
- 239000002861 polymer material Substances 0.000 abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005481 NMR spectroscopy Methods 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 238000001228 spectrum Methods 0.000 abstract description 3
- 238000012512 characterization method Methods 0.000 abstract 1
- 238000005227 gel permeation chromatography Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 4
- 229920001610 polycaprolactone Polymers 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- 239000004632 polycaprolactone Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000009931 harmful effect Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/62—Carboxylic acid esters
- C12P7/625—Polyesters of hydroxy carboxylic acids
-
- 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
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- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Zoology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Microbiology (AREA)
- General Chemical & Material Sciences (AREA)
- Biotechnology (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Polyesters Or Polycarbonates (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention belongs to the technical field of biomedical polymer material preparation, and discloses a synthesis method of four-arm star polylactic acid in supercritical carbon dioxide. Lactide is used as a raw material, erythritol is used as an initiator, immobilized lipase is used as a catalyst, triblock polymer PCL-PDMS-PCL is used as a stabilizer, and a ring-opening dispersion polymerization method is used for synthesizing the polylactide. The structure and performance of the obtained polymer are characterized by characterization means such as nuclear magnetic resonance hydrogen spectrum, gel chromatography and the like, when the reaction temperature is 120 ℃, the pressure is 16MPa, the mass ratio of lipase to lactide is 2%, the reaction time is 24 hours, the obtained polymer product is granular powder, the product yield is 79.46%, the number average molecular weight of the polymer is 6108, and the molecular weight distribution is 1.26. The initiator, the catalyst and the solvent used in the invention are all green reagents, and the preparation method is simple and efficient, thus being a preparation method of biomedical polymer material with wide application prospect.
Description
Technical Field
The invention relates to the technical field of biomedical polymer material preparation, in particular to a method for synthesizing four-arm star polylactic acid in supercritical carbon dioxide.
Background
Polylactic acid in aliphatic polyester is called as bio-plastic, is a thermoplastic polymer with high strength and high modulus, and has the advantages of good biocompatibility, biodegradability, melt processability and the like. Supercritical carbon dioxide (ScCO) 2 ) The technology has become a popular subject of many scholars' researches, and is green due to the advantages of wide sources, gas-like diffusivity, liquid density, non-toxicity, inertness, easy separation and purification of reaction products and the likeSolvents have been widely studied and used in place of many toxic and harmful organic solvents, and have been popularized and used particularly in the field of dispersion polymerization.
The existing catalysts for synthesizing biomedical high molecular materials mostly adopt metal catalysts, and the problems of the metal catalysts, such as biosafety and difficult removal in products, make researchers focus on using biological catalysts. The enzyme is used as an inherent protein in a human body, does not have harmful effect on the human body, has specific cleavage in the reaction, and has less severe requirements on the reaction conditions. The immobilized lipase has outstanding characteristics and obvious advantages.
However, the use of enzymes for the synthesis of polylactic acid is not known in the prior art.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention introduces the enzyme into the ScCO 2 In the synthesis of middle biological high molecular material, the ScCO is widened 2 Is applicable to the range of application. These will all be driven to ScCO 2 The research work of the synthetic biomedical materials is advanced, and a solid foundation is laid for the industrialized production of the biomedical polymer materials of green polymerization.
The preparation method adopts immobilized lipase as a catalyst, synthesizes the non-linear biomedical material polylactide in supercritical carbon dioxide, uses the environment-friendly reagent as an initiator, the catalyst and a solvent, is simple and efficient, and has wide application prospect.
In order to achieve the above object, the present invention has the following technical scheme:
a method for synthesizing four-arm star polylactic acid in supercritical carbon dioxide adopts lactide as a raw material, erythritol as an initiator, immobilized lipase as a catalyst, triblock polymer PCL-PDMS-PCL as a stabilizer, and a ring-opening dispersion polymerization method is adopted to synthesize the polylactic acid; wherein the molar ratio of erythritol to lactide is 2%, the mass ratio of immobilized lipase to lactide is 1-3%, and the mass ratio of stabilizer to lactide is 5%.
The method specifically comprises the following steps:
(1) 1.5g of lactide, the molar ratio of erythritol to lactide is 2%, the mass ratio of immobilized lipase to lactide is 1-3%, the mass ratio of stabilizing agent to lactide is 5% are added into a reaction kettle, the reaction kettle is installed, and CO is introduced 2 Stopping purging after purging the reaction kettle for 5min, adjusting the rotation speed of the stirrer to 400rpm, starting heating, and starting a plunger pump to pressurize the system to 10-16 MPa when the temperature reaches 110-120 ℃ for 24-48 h;
(2) Stopping heating after the reaction of the step (1) is finished, stopping stirring after the system temperature is cooled to room temperature, simultaneously slowly deflating to normal pressure, collecting a crude product in a beaker, slowly dropwise adding dichloromethane until the product is completely dissolved, precipitating to white powder in 10 times of volume of frozen methanol, and then placing the obtained polymer in a vacuum drying oven at 40 ℃ for drying to constant weight to obtain the product polylactide.
Preferably, the mass ratio of immobilized lipase to lactide in step (1) is 2%.
Preferably, the reaction temperature in step (1) is 120 ℃, the reaction pressure is 16MPa, and the reaction time is 24 hours.
Compared with the prior art, the invention has the advantages that:
according to the invention, erythritol is used as an initiator, immobilized lipase is used as a catalyst, lactide is catalyzed to be subjected to ring opening dispersion in supercritical carbon dioxide to synthesize the polylactide, the product yield reaches 79.46%, the number average molecular weight of the polymer is 6108, and the molecular weight distribution is 1.26. The initiator, the catalyst and the solvent are all green reagents, and the preparation method is simple and efficient, so that the preparation method is a preparation method of the biomedical polymer material with wide application prospect.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of the synthesized product polylactide.
Detailed Description
The present invention is described in detail below by way of specific examples, but the scope of the present invention is not limited thereto. Unless otherwise specified, the experimental methods used in the present invention are all conventional methods, and all experimental equipment, materials, reagents, etc. used can be obtained from commercial sources.
Example 1
Adding 1.5g of lactide, erythritol and lactide with a molar ratio of 2%, immobilized lipase and lactide with a mass ratio of 2% and stabilizer and lactide with a mass ratio of 5% into a reaction kettle, installing the reaction kettle, and introducing CO 2 And stopping purging after purging the reaction kettle for 5 min. The rotation speed of the stirrer is regulated to 400rpm, heating is started, a plunger pump is started to pressurize the system to 16MPa after the temperature reaches 120 ℃, and the reaction time is 24 hours; stopping heating after the reaction is finished, stopping stirring after the temperature of the system is cooled to room temperature, and slowly deflating to normal pressure. Collecting the crude product in a beaker, slowly dropwise adding dichloromethane until the product is completely dissolved, precipitating in 10 times of frozen methanol to obtain white powder, and then placing the obtained polymer in a vacuum drying oven at 40 ℃ to dry to constant weight, thereby obtaining the product polycaprolactone with the yield of 79.46%, the number average molecular weight of 6108 and the molecular weight distribution of 1.26.
Example 2
Adding 1.5g of lactide, erythritol and lactide with a molar ratio of 2%, immobilized lipase and lactide with a mass ratio of 1% and stabilizer and lactide with a mass ratio of 5% into a reaction kettle, installing the reaction kettle, and introducing CO 2 And stopping purging after purging the reaction kettle for 5 min. The rotation speed of the stirrer is regulated to 400rpm, heating is started, a plunger pump is started to pressurize the system to 13MPa when the temperature reaches 120 ℃, and the reaction time is 48 hours; stopping heating after the reaction is finished, stopping stirring after the temperature of the system is cooled to room temperature, and slowly deflating to normal pressure. Collecting the crude product in a beaker, slowly dropwise adding dichloromethane until the product is completely dissolved, precipitating in 10 times of frozen methanol to obtain white powder, and then placing the obtained polymer in a vacuum drying oven at 40 ℃ to dry to constant weight, thereby obtaining the product polycaprolactone with the yield of 83.91%, the number average molecular weight of 4578 and the molecular weight distribution of 2.60.
Example 3
1.5g of lactide and erythroseThe molar ratio of alcohol to lactide is 2%, the mass ratio of immobilized lipase to lactide is 2%, the mass ratio of stabilizer to lactide is 5%, adding into a reaction kettle, installing the reaction kettle, and introducing CO 2 And stopping purging after purging the reaction kettle for 5 min. The rotation speed of the stirrer is regulated to 400rpm, heating is started, a plunger pump is started to pressurize the system to 10MPa after the temperature reaches 110 ℃, and the reaction time is 48 hours; stopping heating after the reaction is finished, stopping stirring after the temperature of the system is cooled to room temperature, and slowly deflating to normal pressure. Collecting the crude product in a beaker, slowly dropwise adding dichloromethane until the product is completely dissolved, precipitating in 10 times of frozen methanol to obtain white powder, and then placing the obtained polymer in a vacuum drying oven at 40 ℃ for drying to constant weight to obtain the product polycaprolactone, wherein the product yield is 34.79%, the number average molecular weight is 4209, and the molecular weight distribution is 1.22.
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of the synthetic product polylactide of example 1. Characteristic peaks in erythritol appear in the figures at 4.18pm (-CH) and 3.72pm (-CH) 2 ) About, the terminal methine of the polylactic acid appears at about 4.36pm, the ratio of the three components is about 1:2:2, the ratio accords with the four-arm star-shaped polylactic acid structure ratio, the peak appearing in about 5.21pm is the characteristic peak ratio of the repeating unit (-CH) and the erythritol methine in the product, which is 25:1, accords with the relation of the feeding ratio of reactants, so that the four hydroxyl groups of the erythritol can be judged to participate in the reaction, and the final product is of a 4-arm structure.
According to the invention, erythritol is used as an initiator, immobilized lipase is used as a catalyst, lactide is initiated to be subjected to ring opening dispersion in supercritical carbon dioxide to synthesize the polylactide, the product yield reaches 79.46%, the number average molecular weight of the polymer is 6108, and the molecular weight distribution is 1.26.
The above-described embodiments are only preferred embodiments of the invention, and not all embodiments of the invention are possible. Any obvious modifications thereof, which would be apparent to those skilled in the art without departing from the principles and spirit of the present invention, should be considered to be included within the scope of the appended claims.
Claims (3)
1. A method for synthesizing four-arm star polylactic acid in supercritical carbon dioxide is characterized in that lactide is adopted as a raw material, erythritol is adopted as an initiator, immobilized lipase is adopted as a catalyst, triblock polymer PCL-PDMS-PCL is adopted as a stabilizer, and ring-opening dispersion polymerization is adopted to synthesize polylactide;
the method specifically comprises the following steps:
(1) 1.5g of lactide, the molar ratio of erythritol to lactide is 2%, the mass ratio of immobilized lipase to lactide is 1-3%, the mass ratio of stabilizing agent to lactide is 5% are added into a reaction kettle, the reaction kettle is installed, and CO is introduced 2 Stopping purging after purging the reaction kettle for 5min, adjusting the rotation speed of the stirrer to 400rpm, starting heating, and starting a plunger pump to pressurize the system to 10-16 MPa when the temperature reaches 110-120 ℃ for 24-48 h;
(2) Stopping heating after the reaction of the step (1) is finished, stopping stirring after the system temperature is cooled to room temperature, simultaneously slowly deflating to normal pressure, collecting a crude product in a beaker, slowly dropwise adding dichloromethane until the product is completely dissolved, precipitating to white powder in 10 times of volume of frozen methanol, and then placing the obtained polymer in a vacuum drying oven at 40 ℃ for drying to constant weight to obtain the product polylactide.
2. The method for synthesizing four-arm star polylactic acid in supercritical carbon dioxide according to claim 1, wherein the mass ratio of immobilized lipase to lactide in the step (1) is 2%.
3. The method for synthesizing the four-arm star polylactic acid in supercritical carbon dioxide according to claim 1, wherein the reaction temperature in the step (1) is 120 ℃, the reaction pressure is 16MPa, and the reaction time is 24 hours.
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