CN108285528A - A kind of preparation method of the medical polylactic acid of super high molecular weight - Google Patents
A kind of preparation method of the medical polylactic acid of super high molecular weight Download PDFInfo
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- CN108285528A CN108285528A CN201810188924.7A CN201810188924A CN108285528A CN 108285528 A CN108285528 A CN 108285528A CN 201810188924 A CN201810188924 A CN 201810188924A CN 108285528 A CN108285528 A CN 108285528A
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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
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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
- C08G63/78—Preparation processes
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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
- C08G63/78—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
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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
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/87—Non-metals or inter-compounds thereof
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Abstract
The invention discloses a kind of preparation method of the medical polylactic acid of super high molecular weight, steps 1：A certain proportion of lactide monomer, catalyst and initiator are launched into polymerization container；Step 2：Heating makes the mixture in polymerization container that polymerisation occur and obtains polymer；Step 3：Obtained polymer is dissolved with dichloromethane or chloroform, and poor solvent is added, polylactic acid crude product is precipitated；Step 4：The polylactic acid crude product of precipitation is dried in vacuo to obtain the medical polylactic acid of the super high molecular weight；Catalyst is at least one of stannous octoate, stannous acetate and stannous chloride；Initiator is at least one of lauryl alcohol, Isosorbide-5-Nitrae butanediol and inositol.The present invention is reacted without being segmented, and is conducive to improve production efficiency, is reduced production cost；Using high-purity lactide as raw material, the vacuum degree of reaction system is improved, is conducive to the polylactic acid of synthesizing super high molecular weight.
Description
Technical field
The present invention relates to macromolecule material preparation area more particularly to a kind of preparation sides of the medical polylactic acid of super high molecular weight
Method.
Background technology
Polylactic acid is as a kind of chemically synthesized biodegradated polymer materal, because having extraordinary biocompatibility,
Good mechanical performance, catabolite are carbon dioxide and water, and safety and environmental protection is nontoxic, in surgical sewing thread, hand
Art suturing nail, bone immobilizing material, medical stick film, drug release, the medical fields such as tissue engineering bracket have a wide range of applications.
Wherein surgical sewing thread, operation stitching nail, bone immobilizing material field needs the polylactic acid of high molecular weight, just can guarantee material
With excellent thermodynamic property, applied in medical application as high-strength high-performance material.
There are mainly two types of methods for polylactic acid synthesis, the first is that acid through direct polycondensation by lactic obtains polylactic acid, and another kind is to utilize
Lactide ring-opening polymerisation obtains polylactic acid.First method severe reaction conditions, the reaction time is long, and temperature is high, and vacuum degree is high, and
Since the increase of late phase reaction viscosity causes water in products to be difficult to remove, obtained polylactic acid molecule amount is all relatively low.It is domestic at present
It is generally used second outside, i.e., medical polylactic acid is obtained by lactide monomer ring-opening polymerisation.But in lactide ring-opening polymerisation
In reaction process, because of monomer purity, anhydrous and oxygen-free degree and reaction vacuum degree are not sufficiently high, and polymerisation can not generally obtain
To the polylactic acid of super high molecular weight (the equal molecular weight≤400KDa of weight).
For this problem of preparation super high molecular weight polylactic acid, Chinese patent CN106279643A discloses a kind of by lactic acid
Dehydrating polycondensation obtains lactic acid oligomer, and lactic acid oligomer is mixed with catalyst, and poly- breast is obtained by the reaction in heating under vacuum
Sour intermediate product continuously adds chain extender HDI, continues heating in vacuum weight average molecular weight is obtained by the reaction to be 350KDa~410KDa's
Polylactic acid.
Chinese patent CN 104448261A disclose it is a kind of using biological organic guanidine compound and nontoxic hydrochlorate as being catalyzed
Agent, by being divided to two sections of decompression high temperature lactide ring-opening polymerisations, first segment decompression, which polymerize, obtains the polylactic acid of intermediate molecular weight, and second
Duan Jixu heating decompressions obtain the polylactic acid that weight average molecular weight is 400KDa~550KDa.
The preparation method of above two super high molecular weight polylactic acid is both needed to multistep reaction, and process is complicated, and energy expenditure is huge,
Production cost is higher, and reaction reagent is not easy to obtain, such as the chain extender HDI that patent CN106279643A is mentioned, patent CN
The biological organic guanidine compound catalyst that 104448261A is mentioned, is both needed to specific synthesis.
Invention content
The technical problem to be solved by the present invention is to：A kind of superelevation that can be improved reaction efficiency, reduce cost point is provided
Son measures the preparation method of medical polylactic acid, and the preparation method is not necessarily to the catalyst and initiator of specific synthesis.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is：A kind of medical polylactic acid of super high molecular weight
Preparation method,
Step 1：A certain proportion of lactide monomer, catalyst and initiator are launched into polymerization container；
Step 2：Heating makes the mixture in polymerization container that polymerisation occur and obtains polymer；
Step 3：Obtained polymer is dissolved with dichloromethane or chloroform, and poor solvent is added, polylactic acid is precipitated
Crude product；
Step 4：The polylactic acid crude product of precipitation is dried in vacuo to obtain the medical polylactic acid of the super high molecular weight；
Wherein, step 1 and step 2 carry out under anaerobic anhydrous condition；
Molar ratio is 8000~60000 between lactide monomer and catalyst in step 1：1, lactide monomer and initiator
Between molar ratio be 4000~30000：1；The purity of lactide monomer is 95%~100%；
Catalyst is at least one of stannous octoate, stannous acetate and stannous chloride；Initiator is lauryl alcohol, Isosorbide-5-Nitrae-fourth
At least one of glycol and inositol；
Polymerisation carries out in the vacuum environment that pressure is 1~1000Pa in step 2.
The beneficial effects of the present invention are：The preparation side of substep synthesizing super high molecular weight polylactic acid is different from the prior art
Method, one-step synthesis of the present invention are conducive to improve production efficiency, reduce production cost without being segmented reaction；It is handed over using high-purity third
Ester improves the vacuum degree of reaction system as raw material, is conducive to the polylactic acid of synthesizing super high molecular weight；Tin compound is used as and urges
As initiator, catalyst, initiator abundance are not necessarily to specific synthesis, are suitble to heavy industrialization for agent, alcohol compound
Production.
Specific implementation mode
To explain the technical content, the achieved purpose and the effect of the present invention in detail, it is explained below in conjunction with embodiment.
The design of most critical of the present invention is：Entire polymerization process carries out in anaerobic water-less environment；It is suitable single
The control of the reaction conditions such as body, catalyst and ratio of initiator and suitable temperature, time.
A kind of preparation method of the medical polylactic acid of super high molecular weight,
Step 1：A certain proportion of lactide monomer, catalyst and initiator are launched into polymerization container；
Step 2：Heating makes the mixture in polymerization container that polymerisation occur and obtains polymer；
Step 3：Obtained polymer is dissolved with dichloromethane or chloroform, and poor solvent is added, polylactic acid is precipitated
Crude product；
Step 4：The polylactic acid crude product of precipitation is dried in vacuo to obtain the medical polylactic acid of the super high molecular weight；
Wherein, step 1 and step 2 carry out under anaerobic anhydrous condition；
Molar ratio is 8000~60000 between lactide monomer and catalyst in step 1：1, lactide monomer and initiator
Between molar ratio be 4000~30000：1；The purity of lactide monomer is 95%~100%；
Catalyst is at least one of stannous octoate, stannous acetate and stannous chloride；Initiator is lauryl alcohol, Isosorbide-5-Nitrae-fourth
At least one of glycol and inositol；
Polymerisation carries out in the vacuum environment that pressure is 1~1000Pa in step 2.
As can be seen from the above description, the beneficial effects of the present invention are：Substep synthesizing super high molecular weight is different from the prior art
The preparation method of polylactic acid, one-step synthesis of the present invention are conducive to improve production efficiency, reduce production cost without being segmented reaction；
Using high-purity lactide as raw material, the vacuum degree of reaction system is improved, is conducive to the polylactic acid of synthesizing super high molecular weight；Tin
For class compound as catalyst, alcohol compound as initiator, catalyst, initiator abundance are not necessarily to specific synthesis, fit
Close large-scale industrial production.
Further, the lactide monomer is levorotatory lactide monomer or dextrorotation lactide monomer.
Further, in step 2, polymerisation carries out under 100 DEG C~180 DEG C of temperature condition.
Further, polymerisation carries out under 130~150 DEG C of temperature condition.
Further, in step 2, the reaction time of polymerisation is 6-120h.
Further, the reaction time of polymerisation is 12-72h.
Further, polymerisation carries out in the vacuum environment that pressure is 1~20Pa in step 2.
Further, in step 3, poor solvent is ethyl alcohol, methanol or isopropanol.
Further, high temperature spray gun is used to carry out tube sealing processing to polymerization container in step 2.
Seen from the above description, polymerisation can be improved by carrying out tube sealing processing to polymerization container using high temperature spray gun
Vacuum degree in container, so that it is guaranteed that polymerization reaction system carries out in sufficiently high vacuum environment.
The present invention comparative example be：
(1) under the conditions of anhydrous and oxygen-free, 5kg levorotatory lactides (L- lactides) are added in polymerization container, L- third is handed over
Ester purity is 92.5%.Continuously add 1.40ml stannous octoates and 1.98ml lauryl alcohols, L- lactides, stannous octoate, lauryl alcohol
Molar ratio is respectively 8000：1：2.Vacuumize water removal deoxygenation.
Monomer is dissolved at (2) 130 DEG C, reacts 48h under the conditions of 1000~30000Pa low vacuum, it is adjoint in reaction process
Magneton stirring.
(3) chloroform dissolves polymerizate, and absolute ethyl alcohol is precipitated, and obtains the polylactic acid that weight average molecular weight is 210KDa.
Embodiment 1
A kind of preparation method of the medical polylactic acid of super high molecular weight, the specific steps are：
(1) under the conditions of anhydrous and oxygen-free, 5kg levorotatory lactides (L- lactides), L- lactides are added in polymerisation bottle
Purity is 99.8%.Continuously add 1.40ml stannous octoates and 1.98ml lauryl alcohols, L- lactides, stannous octoate, lauryl alcohol rubs
You are than being respectively 8000：1：2.Vacuumize water removal deoxygenation.
Monomer is dissolved at (2) 130 DEG C, high temperature spray gun tube sealing, the vacuum of guarantee system are used under 500~1000Pa high vacuum
Degree reacts 48h, is stirred along with magneton in reaction process.
(3) chloroform dissolves polymerizate, and methanol is precipitated, and it is poly- to obtain the super high molecular weight that weight average molecular weight is 410KDa
Lactic acid.
Embodiment 2
A kind of preparation method of the medical polylactic acid of super high molecular weight, the specific steps are：
(1) under the conditions of anhydrous and oxygen-free, 5kg levorotatory lactides (L- lactides), L- lactides are added in polymerisation bottle
Purity is 99.8%.Continuously add 1.40ml stannous octoates and 1.98ml lauryl alcohols, L- lactides, stannous octoate, lauryl alcohol rubs
You are than being respectively 8000：1：2.Vacuumize water removal deoxygenation.
Dissolve monomer at (2) 130 DEG C, under 1~20Pa high vacuum use high temperature spray gun tube sealing, the vacuum degree of guarantee system,
48h is reacted, is stirred along with magneton in reaction process.
(3) chloroform dissolves polymerizate, and isopropanol is precipitated, and obtains the super high molecular weight that weight average molecular weight is 490KDa
Polylactic acid.
Embodiment 3
A kind of preparation method of the medical polylactic acid of super high molecular weight, the specific steps are：
(1) under the conditions of anhydrous and oxygen-free, 5kg levorotatory lactides (L- lactides), L- lactides are added in polymerisation bottle
Purity is 99.8%.Continuously add 1.40ml stannous octoates and 1.98ml lauryl alcohols, L- lactides, stannous octoate, lauryl alcohol rubs
You are than being respectively 8000：1：2.Vacuumize water removal deoxygenation.
Dissolve monomer at (2) 130 DEG C, under 1~20Pa high vacuum use high temperature spray gun tube sealing, the vacuum degree of guarantee system,
72h is reacted, is stirred along with magneton in reaction process.
(3) chloroform dissolves polymerizate, and absolute ethyl alcohol is precipitated, and obtains the supra polymer that weight average molecular weight is 510KDa
Measure polylactic acid.
Embodiment 4
A kind of preparation method of the medical polylactic acid of super high molecular weight, the specific steps are：
(1) under the conditions of anhydrous and oxygen-free, 5kg dextrorotation lactide (D- lactides), D- lactides are added in polymerisation bottle
Purity is 96.5%.Continuously add 0.33ml stannous octoates and 0.46ml lauryl alcohols, D- lactides, stannous chloride, Isosorbide-5-Nitrae-fourth two
Alcohol molar ratio is respectively 34000：1：2.Vacuumize water removal deoxygenation.
Monomer is dissolved at (2) 130 DEG C, high temperature spray gun tube sealing, the vacuum of guarantee system are used under 500~1000Pa high vacuum
Degree reacts 48h, is stirred along with magneton in reaction process.
(3) chloroform dissolves polymerizate, and absolute ethyl alcohol is precipitated, and obtains the supra polymer that weight average molecular weight is 850KDa
Measure polylactic acid.
Embodiment 5
A kind of preparation method of the medical polylactic acid of super high molecular weight, the specific steps are：
(4) under the conditions of anhydrous and oxygen-free, 5kg dextrorotation lactide (D- lactides), D- lactides are added in polymerisation bottle
Purity is 99.9%.Continuously add 0.33ml stannous octoates and 0.46ml lauryl alcohols, D- lactides, stannous chloride, Isosorbide-5-Nitrae-fourth two
Alcohol molar ratio is respectively 34000：1：2.Vacuumize water removal deoxygenation.
Monomer is dissolved at (5) 130 DEG C, high temperature spray gun tube sealing, the vacuum of guarantee system are used under 500~1000Pa high vacuum
Degree reacts 48h, is stirred along with magneton in reaction process.
(6) chloroform dissolves polymerizate, and methanol is precipitated, and obtains the super high molecular weight that weight average molecular weight is 1050KDa
Polylactic acid.
Embodiment 6
A kind of preparation method of the medical polylactic acid of super high molecular weight, the specific steps are：
(1) under the conditions of anhydrous and oxygen-free, 5kg dextrorotation lactide (D- lactides), D- lactides are added in polymerisation bottle
Purity is 99.9%.Continuously add 0.33ml stannous octoates and 0.46ml lauryl alcohols, D- lactides, stannous chloride, Isosorbide-5-Nitrae-fourth two
Alcohol molar ratio is respectively 34000：1：2.Vacuumize water removal deoxygenation.
Dissolve monomer at (2) 130 DEG C, under 1~20Pa high vacuum use high temperature spray gun tube sealing, the vacuum degree of guarantee system,
48h is reacted, is stirred along with magneton in reaction process.
(3) chloroform dissolves polymerizate, and isopropanol is precipitated, and obtains the supra polymer that weight average molecular weight is 1650KDa
Measure polylactic acid.
Embodiment 7
A kind of preparation method of the medical polylactic acid of super high molecular weight, the specific steps are：
(1) under the conditions of anhydrous and oxygen-free, 5kg levorotatory lactides (L- lactides), L- lactides are added in polymerisation bottle
Purity is 95.8%.Continuously add 0.19ml stannous octoates and 0.26ml lauryl alcohols, L- lactides, stannous acetate, inositol
Molar ratio is respectively 60000：1：2.Vacuumize water removal deoxygenation.
Monomer is dissolved at (2) 130 DEG C, high temperature spray gun tube sealing, the vacuum of guarantee system are used under 500~1000Pa high vacuum
Degree reacts 48h, is stirred along with magneton in reaction process.
(3) chloroform dissolves polymerizate, and methanol is precipitated, and obtains the super high molecular weight that weight average molecular weight is 1125KDa
Polylactic acid.
Embodiment 8
A kind of preparation method of the medical polylactic acid of super high molecular weight, the specific steps are：
(1) under the conditions of anhydrous and oxygen-free, 5kg levorotatory lactides (L- lactides), L- lactides are added in polymerisation bottle
Purity is 99.9%.Continuously add 0.19ml stannous octoates and 0.26ml lauryl alcohols, L- lactides, stannous acetate, inositol
Molar ratio is respectively 60000：1：2.Vacuumize water removal deoxygenation.
Monomer is dissolved at (2) 130 DEG C, high temperature spray gun tube sealing, the vacuum of guarantee system are used under 500~1000Pa high vacuum
Degree reacts 48h, is stirred along with magneton in reaction process.
(3) chloroform dissolves polymerizate, and isopropanol is precipitated, and obtains the supra polymer that weight average molecular weight is 1670KDa
Measure polylactic acid.
Embodiment 9
A kind of preparation method of the medical polylactic acid of super high molecular weight, the specific steps are：
(1) under the conditions of anhydrous and oxygen-free, 5kg levorotatory lactides (L- lactides), L- lactides are added in polymerisation bottle
Purity is 99.9%.Continuously add 0.19ml stannous octoates and 0.26ml lauryl alcohols, L- lactides, stannous acetate, inositol
Molar ratio is respectively 60000：1：2.Vacuumize water removal deoxygenation.
Dissolve monomer at (2) 130 DEG C, under 1~20Pa high vacuum use high temperature spray gun tube sealing, the vacuum degree of guarantee system,
48h is reacted, is stirred along with magneton in reaction process.
(3) chloroform dissolves polymerizate, and absolute ethyl alcohol is precipitated, and obtains the superelevation point that weight average molecular weight is 2160KDa
Son amount polylactic acid.
In conclusion the preparation method of medical polylactic acid provided by the invention, is different from the prior art substep synthesis superelevation
The preparation method of molecular weight polylactic acid, one-step synthesis of the present invention are conducive to improve production efficiency, reduce life without being segmented reaction
Produce cost；Using high-purity lactide as raw material, the vacuum degree of reaction system is improved, is conducive to the poly- of synthesizing super high molecular weight
Lactic acid；Tin compound is as catalyst, alcohol compound as initiator, catalyst, initiator abundance, without specific
Synthesis is suitble to large-scale industrial production.Polymerization can be improved by carrying out tube sealing processing to polymerization container using high temperature spray gun
Vacuum degree in reaction vessel, so that it is guaranteed that polymerization reaction system carries out in sufficiently high vacuum environment.
Example the above is only the implementation of the present invention is not intended to limit the scope of the invention, every to utilize this hair
Equivalents made by bright description are applied directly or indirectly in relevant technical field, are similarly included in this hair
In bright scope of patent protection.
Claims (9)
1. a kind of preparation method of the medical polylactic acid of super high molecular weight, it is characterised in that：
Step 1：A certain proportion of lactide monomer, catalyst and initiator are launched into polymerization container；
Step 2：Heating makes the mixture in polymerization container that polymerisation occur and obtains polymer；
Step 3：Obtained polymer is dissolved with dichloromethane or chloroform, and poor solvent precipitation polylactic acid is added and slightly produces
Product；
Step 4：The polylactic acid crude product of precipitation is dried in vacuo to obtain the medical polylactic acid of the super high molecular weight；
Wherein, step 1 and step 2 carry out under anaerobic anhydrous condition；
Molar ratio is 8000~60000 between lactide monomer and catalyst in step 1：1, between lactide monomer and initiator
Molar ratio is 4000~30000：1；The purity of lactide monomer is 95%~100%；
Catalyst is at least one of stannous octoate, stannous acetate and stannous chloride；Initiator is lauryl alcohol, 1,4-butanediol
At least one of with inositol；
Polymerisation carries out in the vacuum environment that pressure is 1~1000Pa in step 2.
2. the preparation method of the medical polylactic acid of super high molecular weight according to claim 1, it is characterised in that：The lactide
Monomer is levorotatory lactide monomer or dextrorotation lactide monomer.
3. the preparation method of the medical polylactic acid of super high molecular weight according to claim 1, it is characterised in that：In step 2, gather
Reaction is closed to carry out under 100 DEG C~180 DEG C of temperature condition.
4. the preparation method of the medical polylactic acid of super high molecular weight according to claim 3, it is characterised in that：Polymerisation exists
It is carried out under 130~150 DEG C of temperature condition.
5. the preparation method of the medical polylactic acid of super high molecular weight according to claim 1, it is characterised in that：In step 2, gather
The reaction time for closing reaction is 6-120h.
6. the preparation method of the medical polylactic acid of super high molecular weight according to claim 5, it is characterised in that：Polymerisation
Reaction time is 12-72h.
7. the preparation method of the medical polylactic acid of super high molecular weight according to claim 1, it is characterised in that：Gather in step 2
Reaction is closed to carry out in the vacuum environment that pressure is 1~20Pa.
8. the preparation method of the medical polylactic acid of super high molecular weight according to claim 1, it is characterised in that：In step 3, no
Good solvent is ethyl alcohol, methanol or isopropanol.
9. the preparation method of the medical polylactic acid of super high molecular weight according to claim 1, it is characterised in that：In step 2
Tube sealing processing is carried out to polymerization container using high temperature spray gun.
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| CN114213638A (en) * | 2021-11-16 | 2022-03-22 | 元嘉生物科技(浙江)有限公司 | Method for improving polylactic acid molecular weight based on in-situ drying dehydration |
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| CN113512181B (en) * | 2021-08-09 | 2022-08-12 | 重庆大学 | Polylactic acid capable of being processed at low temperature and preparation method thereof |
| CN114773811B (en) * | 2022-06-27 | 2022-09-02 | 广东美联新材料股份有限公司 | Color master batch taking polylactic acid recovered waste material as carrier and preparation method thereof |
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| CN113788938A (en) * | 2021-09-15 | 2021-12-14 | 杭州锐健马斯汀医疗器材有限公司 | Medical lactide polymer and preparation method thereof |
| CN114213638A (en) * | 2021-11-16 | 2022-03-22 | 元嘉生物科技(浙江)有限公司 | Method for improving polylactic acid molecular weight based on in-situ drying dehydration |
| CN114752048A (en) * | 2022-04-11 | 2022-07-15 | 深圳光华伟业股份有限公司 | Catalyst and application of preparation method thereof in preparation of biomedical polylactic acid |
| CN117089051A (en) * | 2023-10-20 | 2023-11-21 | 山东谷雨春生物科技有限公司 | Method for synthesizing high molecular weight polylactic acid by solution polymerization method |
| CN117089051B (en) * | 2023-10-20 | 2024-01-26 | 山东谷雨春生物科技有限公司 | Method for synthesizing high molecular weight polylactic acid by solution polymerization method |
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| CN111499844A (en) | 2020-08-07 |
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