CN104558504A - Preparation method of polylactic acid and polyethylene glycol copolymer - Google Patents
Preparation method of polylactic acid and polyethylene glycol copolymer Download PDFInfo
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- CN104558504A CN104558504A CN201510011315.0A CN201510011315A CN104558504A CN 104558504 A CN104558504 A CN 104558504A CN 201510011315 A CN201510011315 A CN 201510011315A CN 104558504 A CN104558504 A CN 104558504A
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4283—Hydroxycarboxylic acid or ester
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- 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
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
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Abstract
The invention discloses a preparation method of a polylactic acid and polyethylene glycol copolymer. The preparation method comprises the following steps: heating lactic acid at the temperature of 80-100 DEG C in the atmosphere of nitrogen, and dehydrating at a reduced pressure to obtain a polylactic acid; adding polyethylene glycol and a catalyst into the polylactic acid to carry out reaction to obtain a terminal hydroxyl modified polylactic acid; and adding polyethylene glycol and a chain extender into the terminal hydroxyl modified polylactic acid to carry out reaction to obtain the polylactic acid and polyethylene glycol copolymer. The lactic acid is subjected to copolymerization reaction after being polymerized, thus the loss due to evaporation can be avoided. The molecular chains of the obtained copolymer comprise lipophilic hard lactic acid segments and hydrophilic soft polyethylene glycol segments, thus the obtained copolymer has a certain flexibility and good hydrophilicity.
Description
Technical field
The present invention relates to a kind of preparation method of PLA-PEG copolymer, belong to macromolecule synthesising technology field.
Background technology
Poly(lactic acid) (PLA) is a kind of biodegradable thermoplastic polymer, has broad application prospects in fields such as surgical repair, drug delivery systems, organizational projects.But because its degree of crystallinity is higher, matter hard and poor toughness, because containing a large amount of hydrophobic ester bond in molecule, reduces its biocompatibility, limiting Application Areas and effect.Therefore, plasticising, copolymerization, blended, molecular modification, compound etc. are adopted to carry out to poly(lactic acid) the focus that modification becomes research at present.
It is reactive that polyoxyethylene glycol (PEG) has amphipathic, biocompatibility and end group preferably, molecular weight ranges is wide, choice is large, and be can be used for human body by U.S.'s approval, pretend as one of the most frequently used polylactic acid modified means, polyethylene glycol modified polylactide comes into one's own day by day.Polyethylene glycol modified polylactide can effectively improve its hydrophilicity, thus effectively improves the biocompatibility of material.The method of polyethylene glycol modified polylactide is mainly divided into blending and modifying and modification by copolymerization two kinds.Shanghai Communications University, Wuhan University of Technology, Zhejiang Polytechnical University etc. are to the just research of polyethylene glycol blending polydactyl acid, and result shows, polyoxyethylene glycol add the crystallization velocity significantly improving poly(lactic acid), effectively can improve the elongation at break of modified polylactic acid material, second-order transition temperature reduces, and polylactic acid molecule inter-chain action power weakens, and normal temperature plasticity strengthens, and improve the hydrolysis rate of poly(lactic acid) in soil, thus accelerate its degradation rate.
Summary of the invention
The object of the present invention is to provide a kind of preparation method being easy to the PLA-PEG copolymer of biological degradation and better processing characteristics.
Implementation procedure of the present invention is as follows:
A preparation method for PLA-PEG copolymer, comprises the following steps:
(1) in a nitrogen atmosphere, by lactic acid 80 ~ 100 DEG C of heating, decompression dehydration obtains poly(lactic acid);
(2) in poly(lactic acid), polyoxyethylene glycol and catalyzer is added, through being obtained by reacting terminal hydroxy group polydactyl acid;
(3) in terminal hydroxy group polydactyl acid, polyoxyethylene glycol, chainextender is added again, through being obtained by reacting PLA-PEG copolymer.
Catalyzer described in above-mentioned steps (2) is selected from stannous octoate or tin protochloride, molecular weight polyethylene glycol is that 200 ~ 1000(is as PEG-200, PEG-400, PEG-600, PEG-800, PEG-1000), the mass ratio of poly(lactic acid) and polyoxyethylene glycol is 6:1 ~ 10:1, and temperature of reaction is 140 ~ 170 DEG C;
Chainextender described in step (3) is selected from 1,6-hexamethylene diisocyanate, 2,4-tolylene diisocyanate, the mass ratio of terminal hydroxy group polydactyl acid, polyoxyethylene glycol and chainextender is 10 ~ 20:10 ~ 20:1 ~ 2, molecular weight polyethylene glycol is that 2000 ~ 20000(is as PEG-2000, PEG-4000, PEG-6000, PEG-8000, PEG-10000, PEG-20000), temperature of reaction is 160 ~ 180 DEG C.
Advantage of the present invention and positively effect: (1) lactic acid as raw material, inexpensive and wide material sources; (2) preparing the different polyoxyethylene glycol reaction of terminal hydroxy group polydactyl acid and PLA-PEG copolymer two differential responses stage use molecular weight, the product obtained is easier to degraded; (3) lactic acid participates in copolyreaction after polymerization, not easily occurs to evaporate and loss; (4), in the copolymer molecule chain obtained, because of simultaneously containing the hard section of lipophilic lactic acid and soft section of hydrophilic polyoxyethylene glycol, there is certain snappiness and good wetting ability.
Embodiment
By following examples, the invention will be further described.
Embodiment 1
10g lactic acid is obtained poly(lactic acid) in 4 hours 90 DEG C of reactions, then adds 1.5g polyoxyethylene glycol (PEG-400) and 0.1g stannous octoate catalyst, 150 DEG C of reactions 10 hours, obtain terminal hydroxy group polydactyl acid; Add 10g polyoxyethylene glycol (PEG-12000), 1,6-hexamethylene diisocyanate chainextender 1g again, through 180 DEG C of reactions 5 hours, obtain PLA-PEG copolymer.
Embodiment 2
10g lactic acid is obtained poly(lactic acid) in 4 hours 100 DEG C of reactions, then adds 1.0g polyoxyethylene glycol (PEG-800) and 0.1g stannous octoate catalyst, 150 DEG C of reactions 10 hours, obtain terminal hydroxy group polydactyl acid; Add 8g polyoxyethylene glycol (PEG-4000), 1,6-hexamethylene diisocyanate chainextender 1g again, through 180 DEG C of reactions 5 hours, obtain PLA-PEG copolymer.
Embodiment 3
10g lactic acid is obtained poly(lactic acid) in 4 hours 90 DEG C of reactions, then adds 1.5g polyoxyethylene glycol (PEG-600) and 0.1g stannous octoate catalyst, 160 DEG C of reactions 10 hours, obtain terminal hydroxy group polydactyl acid; Add 10g polyoxyethylene glycol (PEG-20000), 1,6-hexamethylene diisocyanate chainextender 1g again, through 175 DEG C of reactions 5 hours, obtain PLA-PEG copolymer.
Comparison example 1
10g lactic acid is obtained poly(lactic acid) in 4 hours 90 DEG C of reactions, then adds 1.5g polyoxyethylene glycol (PEG-12000) and 0.1g stannous octoate catalyst, 150 DEG C of reactions 10 hours, obtain terminal hydroxy group polydactyl acid; Add 10g polyoxyethylene glycol (PEG-12000), 1,6-hexamethylene diisocyanate chainextender 1g again, through 180 DEG C of reactions 5 hours, obtain PLA-PEG copolymer.
Comparative example 2
10g lactic acid is obtained poly(lactic acid) in 4 hours 90 DEG C of reactions, then adds 1.5g polyoxyethylene glycol (PEG-200) and 0.1g stannous octoate catalyst, 150 DEG C of reactions 10 hours, obtain terminal hydroxy group polydactyl acid; Add 10g polyoxyethylene glycol (PEG-200), 1,6-hexamethylene diisocyanate chainextender 1g again, through 180 DEG C of reactions 5 hours, obtain PLA-PEG copolymer.
Embodiment 4
Test differential responses condition synthesizes the degradation property of the product obtained, and different polymers is made diaphragm, immerses result in the phosphate buffer soln of the pH=7.3 of 37 DEG C, observes diaphragm degraded situation, as shown in table 1.
Claims (6)
1. a preparation method for PLA-PEG copolymer, comprises the following steps:
(1) in a nitrogen atmosphere, by lactic acid 80 ~ 100 DEG C of heating, decompression dehydration obtains poly(lactic acid);
(2) in poly(lactic acid), polyoxyethylene glycol and catalyzer is added, through being obtained by reacting terminal hydroxy group polydactyl acid;
(3) in terminal hydroxy group polydactyl acid, polyoxyethylene glycol, chainextender is added again, through being obtained by reacting PLA-PEG copolymer.
2. the preparation method of PLA-PEG copolymer according to claim 1, is characterized in that: in above-mentioned steps (2), described catalyzer is selected from stannous octoate or tin protochloride, and temperature of reaction is 140 ~ 170 DEG C.
3. the preparation method of PLA-PEG copolymer according to claim 1, is characterized in that: in above-mentioned steps (2), and molecular weight polyethylene glycol is 200 ~ 1000, and the mass ratio of poly(lactic acid) and polyoxyethylene glycol is 6:1 ~ 10:1.
4. the preparation method of PLA-PEG copolymer according to claim 1, is characterized in that: in above-mentioned steps (3), described chainextender is selected from 1,6-hexamethylene diisocyanate, 2,4 toluene diisocyanate.
5. the preparation method of PLA-PEG copolymer according to claim 4, its feature in: the mass ratio of terminal hydroxy group polydactyl acid, polyoxyethylene glycol and chainextender is 10 ~ 20:10 ~ 20:1 ~ 2.
6. the preparation method of PLA-PEG copolymer according to claim 1, is characterized in that: in above-mentioned steps (3), and molecular weight polyethylene glycol is 2000 ~ 20000, and temperature of reaction is 160 ~ 180 DEG C.
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| CN201510011315.0A CN104558504B (en) | 2015-01-12 | 2015-01-12 | A kind of preparation method of polylactic acid poly glycol copolymer |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105294970A (en) * | 2015-11-24 | 2016-02-03 | 深圳光华伟业股份有限公司 | Bio-based thermoplastic polyurethane elastomer material and preparation method thereof |
| CN105348501A (en) * | 2015-08-17 | 2016-02-24 | 宁波天益医疗器械有限公司 | Bisoxazoline chain-extending polylactic acid polyhydric alcohol with low-acid value and preparation method for bisoxazoline chain-extending polylactic acid polyhydric alcohol with low-acid value |
| CN105924635A (en) * | 2016-07-13 | 2016-09-07 | 蚌埠学院 | Method for tin catalyst catalyzed synthesis of polylactic acid copolymerization modification product |
| CN108003321A (en) * | 2017-12-21 | 2018-05-08 | 中国科学院长春应用化学研究所 | A kind of preparation method of poly-lactic acid in high molecular weight segmented copolymer |
| CN110054875A (en) * | 2018-01-18 | 2019-07-26 | 深圳市七号科技有限公司 | A kind of poly (lactic acid) composition and preparation method thereof for 3D printing |
| CN114479139A (en) * | 2022-01-14 | 2022-05-13 | 江西冠德新材科技股份有限公司 | Fiber-based degradable film and preparation method thereof |
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| CN1412220A (en) * | 2002-07-12 | 2003-04-23 | 天津大学 | Preparation method of polyethylene-b-polylactic acid amphiphilic diblock copolymer |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105348501A (en) * | 2015-08-17 | 2016-02-24 | 宁波天益医疗器械有限公司 | Bisoxazoline chain-extending polylactic acid polyhydric alcohol with low-acid value and preparation method for bisoxazoline chain-extending polylactic acid polyhydric alcohol with low-acid value |
| CN105294970A (en) * | 2015-11-24 | 2016-02-03 | 深圳光华伟业股份有限公司 | Bio-based thermoplastic polyurethane elastomer material and preparation method thereof |
| CN105924635A (en) * | 2016-07-13 | 2016-09-07 | 蚌埠学院 | Method for tin catalyst catalyzed synthesis of polylactic acid copolymerization modification product |
| CN105924635B (en) * | 2016-07-13 | 2017-12-29 | 蚌埠学院 | The method of tin catalyst catalyzing and synthesizing polylactic acid modification by copolymerization product |
| CN108003321A (en) * | 2017-12-21 | 2018-05-08 | 中国科学院长春应用化学研究所 | A kind of preparation method of poly-lactic acid in high molecular weight segmented copolymer |
| CN110054875A (en) * | 2018-01-18 | 2019-07-26 | 深圳市七号科技有限公司 | A kind of poly (lactic acid) composition and preparation method thereof for 3D printing |
| CN110054875B (en) * | 2018-01-18 | 2021-10-29 | 深圳市七号科技有限公司 | Polylactic acid composition for 3D printing and preparation method thereof |
| CN114479139A (en) * | 2022-01-14 | 2022-05-13 | 江西冠德新材科技股份有限公司 | Fiber-based degradable film and preparation method thereof |
| CN114479139B (en) * | 2022-01-14 | 2023-08-25 | 江西冠德新材科技股份有限公司 | Fiber-based degradable film and preparation method thereof |
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