CN104558504B - A kind of preparation method of polylactic acid poly glycol copolymer - Google Patents
A kind of preparation method of polylactic acid poly glycol copolymer Download PDFInfo
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- CN104558504B CN104558504B CN201510011315.0A CN201510011315A CN104558504B CN 104558504 B CN104558504 B CN 104558504B CN 201510011315 A CN201510011315 A CN 201510011315A CN 104558504 B CN104558504 B CN 104558504B
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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
- C08G18/70—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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- 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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- 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
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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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
- 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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- 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
- C08G63/91—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 kind of preparation method of polylactic acid poly glycol copolymer, it in a nitrogen atmosphere heats lactic acid at 80~100 DEG C, and decompression dehydration obtains PLA;Polyethylene glycol and catalyst are added in PLA, it is reacted to obtain terminal hydroxy group polydactyl acid;Polyethylene glycol, chain extender are added in terminal hydroxy group polydactyl acid, it is reacted to obtain polylactic acid poly glycol copolymer.Copolyreaction is participated in after lactic acid of the present invention is aggregated, is not susceptible to evaporate and be lost, in the copolymer molecule chain of acquisition, because containing lipophilic lactic acid hard section and hydrophilic polyethylene glycol soft segment simultaneously, with certain pliability and good hydrophily.
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
PLA(PLA)It is a kind of biodegradable thermoplastic polymer, in surgical repair, medicament transport system
The fields such as system, organizational project have broad application prospects.But because its crystallinity is higher, matter hard and poor toughness, because containing in molecule
There are a large amount of hydrophobic ester bonds, reduce its biocompatibility, limit application field and effect.Therefore, using plasticising, altogether
Poly-, blending, molecular modification, compound etc. are modified to PLA as the focus studied at present.
Polyethylene glycol(PEG)With preferable amphipathic, biocompatibility and end group reactivity, molecular weight ranges are wide, choosing
Select leeway big, and human body can be used for by U.S.'s approval, pretend as one of the most frequently used polylactic acid modified means, polyethylene glycol changes
Property PLA be increasingly subject to pay attention to.Polyethylene glycol modified polylactide can effectively improve its hydrophilicity, so as to effectively improve material
Biocompatibility.The method of polyethylene glycol modified polylactide is broadly divided into two kinds of blending and modifying and modification by copolymerization.Shanghai traffic
As a result university, Wuhan University of Technology, Zhejiang Polytechnical University etc. show the just research of polyethylene glycol blending polydactyl acid,
The addition of polyethylene glycol significantly improves the crystallization rate of PLA, can effectively improve the extension at break of modified polylactic acid material
Rate, glass transition temperature reduction, polylactic acid molecule chain intermolecular forces weaken, the enhancing of normal temperature plasticity, and improve PLA in soil
Hydrolysis rate, so as to accelerate its degradation rate.
The content of the invention
It is total to it is an object of the invention to provide a kind of be readily biodegradable with the polylactic acid-polyglycol of preferable processing characteristics
The preparation method of polymers.
The implementation process of the present invention is as follows:
A kind of preparation method of PLA-PEG copolymer, comprises the following steps:
(1)In a nitrogen atmosphere, by lactic acid in 80~100 DEG C of heating, decompression dehydration obtains PLA;
(2)Polyethylene glycol and catalyst are added in PLA, it is reacted to obtain terminal hydroxy group polydactyl acid;
(3)Polyethylene glycol, chain extender are added in terminal hydroxy group polydactyl acid, it is reacted to obtain PLA-poly- second two
Alcohol copolymer.
Above-mentioned steps(2)Described catalyst be selected from stannous octoate or stannous chloride, molecular weight polyethylene glycol be 200~
1000(Such as PEG-200, PEG-400, PEG-600, PEG-800, PEG-1000), the mass ratio of PLA and polyethylene glycol is 6:
1~10:1, reaction temperature is 140~170 DEG C;
Step(3)Described chain extender is selected from 1,6- hexamethylene diisocyanates, 2,4- toluene di-isocyanate(TDI)s, holds hydroxyl
The mass ratio of base polydactyl acid, polyethylene glycol and chain extender is 10~20:10~20:1~2, molecular weight polyethylene glycol is
2000~20000(Such as PEG-2000, PEG-4000, PEG-6000, PEG-8000, PEG-10000, PEG-20000), reaction temperature
Spend for 160~180 DEG C.
Advantages and positive effects of the present invention:(1)Lactic acid is as raw material, inexpensive and wide material sources;(2)Preparing terminal hydroxy group
Two differential responses stages of polydactyl acid and PLA-PEG copolymer are anti-using the different polyethylene glycol of molecular weight
Should, obtained product is easier to degraded;(3)Copolyreaction is participated in after lactic acid is aggregated, is not susceptible to evaporate and be lost;(4)Obtain
In the copolymer molecule chain obtained, because containing lipophilic lactic acid hard section and hydrophilic polyethylene glycol soft segment simultaneously, with certain
Pliability and good hydrophily.
Embodiment
By following examples, the invention will be further described.
Embodiment 1
10g lactic acid is obtained into PLA in 4 hours in 90 DEG C of reactions, 1.5g polyethylene glycol is then added(PEG-400)With
0.1g stannous octoate catalysts, react 10 hours at 150 DEG C, obtain terminal hydroxy group polydactyl acid;Add 10g polyethylene glycol
(PEG-12000), 1,6- hexamethylene diisocyanate chain extender 1g, through 180 DEG C react 5 hours, obtain PLA-poly- second two
Alcohol copolymer.
Embodiment 2
10g lactic acid is obtained into PLA in 4 hours in 100 DEG C of reactions, 1.0g polyethylene glycol is then added(PEG-800)With
0.1g stannous octoate catalysts, react 10 hours at 150 DEG C, obtain terminal hydroxy group polydactyl acid;Add 8g polyethylene glycol
(PEG-4000), 1,6- hexamethylene diisocyanate chain extender 1g, through 180 DEG C react 5 hours, obtain PLA-poly- second two
Alcohol copolymer.
Embodiment 3
10g lactic acid is obtained into PLA in 4 hours in 90 DEG C of reactions, 1.5g polyethylene glycol is then added(PEG-600)With
0.1g stannous octoate catalysts, react 10 hours at 160 DEG C, obtain terminal hydroxy group polydactyl acid;Add 10g polyethylene glycol
(PEG-20000), 1,6- hexamethylene diisocyanate chain extender 1g, through 175 DEG C react 5 hours, obtain PLA-poly- second two
Alcohol copolymer.
Comparison example 1
10g lactic acid is obtained into PLA in 4 hours in 90 DEG C of reactions, 1.5g polyethylene glycol is then added(PEG-12000)With
0.1g stannous octoate catalysts, react 10 hours at 150 DEG C, obtain terminal hydroxy group polydactyl acid;Add 10g polyethylene glycol
(PEG-12000), 1,6- hexamethylene diisocyanate chain extender 1g, through 180 DEG C react 5 hours, obtain PLA-poly- second two
Alcohol copolymer.
Comparative example 2
10g lactic acid is obtained into PLA in 4 hours in 90 DEG C of reactions, 1.5g polyethylene glycol is then added(PEG-200)With
0.1g stannous octoate catalysts, react 10 hours at 150 DEG C, obtain terminal hydroxy group polydactyl acid;Add 10g polyethylene glycol
(PEG-200), 1,6- hexamethylene diisocyanate chain extender 1g, through 180 DEG C react 5 hours, obtain polylactic acid-polyglycol
Copolymer.
Embodiment 4
The degradability for the product that test differential responses condition synthesis is obtained, diaphragm, immersion 37 are made by different macromolecules
DEG C pH=7.3 phosphate buffer solution in result, observation diaphragm degraded situation, as shown in table 1.
Claims (1)
1. a kind of preparation method of PLA-PEG copolymer, comprises the following steps:
(1)In a nitrogen atmosphere, by lactic acid in 80~100 DEG C of heating, decompression dehydration obtains PLA;
(2)Polyethylene glycol and catalyst are added in PLA, it is reacted to obtain terminal hydroxy group polydactyl acid, described catalyst
Selected from stannous octoate or stannous chloride, reaction temperature is 140~170 DEG C;Molecular weight polyethylene glycol is 200~1000, PLA
Mass ratio with polyethylene glycol is 6:1~10:1;
(3)Polyethylene glycol, chain extender are added in terminal hydroxy group polydactyl acid, the reacted polylactic acid-polyglycol that obtains is total to
Polymers, described chain extender is selected from 1,6- hexamethylene diisocyanates, 2,4- toluene di-isocyanate(TDI)s;Terminal hydroxy group is modified poly- breast
The mass ratio of acid, polyethylene glycol and chain extender is 10~20:10~20:1~2;Molecular weight polyethylene glycol is 2000~20000,
Reaction temperature is 160~180 DEG C.
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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 |
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 |
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 |
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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CN1412220A (en) * | 2002-07-12 | 2003-04-23 | 天津大学 | Preparation method of polyethylene-b-polylactic acid amphiphilic diblock copolymer |
CN101054440A (en) * | 2007-04-24 | 2007-10-17 | 上海同杰良生物材料有限公司 | Method for preparing polylactic acid/polyether divalent alcohol copolymers |
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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 |
CN101054440A (en) * | 2007-04-24 | 2007-10-17 | 上海同杰良生物材料有限公司 | Method for preparing polylactic acid/polyether divalent alcohol copolymers |
Non-Patent Citations (1)
Title |
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