CN101186687A - Method for preparing polylactic acid by lactide open loop polymerization reaction - Google Patents
Method for preparing polylactic acid by lactide open loop polymerization reaction Download PDFInfo
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- CN101186687A CN101186687A CNA2007101685805A CN200710168580A CN101186687A CN 101186687 A CN101186687 A CN 101186687A CN A2007101685805 A CNA2007101685805 A CN A2007101685805A CN 200710168580 A CN200710168580 A CN 200710168580A CN 101186687 A CN101186687 A CN 101186687A
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- phosphorous acid
- polylactic acid
- dialkyl ester
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Abstract
The invention discloses a process for preparing polylactic acid, which uses dialkyl ester phosphite to catalyze lactide to do ring-opening polymerization reaction, uses lactide as monomer and uses dialkyl ester phosphite as catalyst, wherein when the reacting temperature of their mixtures is 25-280 DEG C, the polylactic acid is generated by lactide through ring-opening polymerization reaction in the vacuum or inert gas protecting condition. The invention uses the lactide as raw material, in which the dialkyl ester phosphite is charged to generate ring-opening polymerization reaction in the decompression or inert gas protecting condition to obtain the polylactic acid. The invention uses simply obtained dialkyl ester phosphite as the catalyst for the open ring and polymerize of the lactide, which avoids the usage of metal catalyst and residuals for preparing polylactic acid metal-free compound. The obtained polylactic acid fits for electronic product material and biological medical material.
Description
Technical field
The present invention relates to the preparation method of poly(lactic acid), belong to chemical field.
Background technology
Poly(lactic acid) is a class biodegradable polymer.Poly(lactic acid) has excellent biological compatibility, degraded product lactic acid safety non-toxic, and it has extensive studies, application prospect as drug controlled release material, operating sutures, tissue engineering bracket material and bone renovating material at biomedical sector.Substitute conventional plastics with poly(lactic acid) in recent years and also be subjected to special concern as the electronic product material.The poly(lactic acid) that the electronic security(ELSEC) of security and electronic product material all requires to be used for this field in the body of biomedical material does not have metallic compound residual fully.The main method of present industrial preparation poly(lactic acid) is the ring-opening polymerization of the catalytic rac-Lactide body of stannous iso caprylate, cause in the polymerisate kish compound inevitably, can't satisfy biomedical material and the requirement of electronic product material aspect security.The catalytic rac-Lactide ring-opening polymerization of nonmetallic compound does not then use metallic compound fully, has stopped the possibility of kish compound the poly-lactic acid material from the source.But result of study shows some transesterification reaction reagent such as 4-dimethylaminopyridine, phosphine compound and N-heterocycle carbine etc. all catalyzing ring-opening polymerization of lactide reaction (Hedrick etc.: Angew.Chem.Int.Ed.2001,40,2712-2715 in recent years; J.Polym.Sci.Polym.Chem.2002,40,844-851; J.Am.Chem.Sci.2002,124 (6), 914-915).Main difficulty one by the reaction of transesterification reaction reagent catalyzing ring-opening polymerization of lactide is that this type of reagent preparation is comparatively loaded down with trivial details, and another is that the reaction times is longer.
Summary of the invention
The objective of the invention is to overcome above-mentioned the deficiencies in the prior art, a kind of method of preparing polylactic acid by lactide open loop polymerization reaction is provided, this method be simple and easy to phosphorous acid dialkyl ester (also can be described as dialkyl phosphorous acid) as the catalyzer of rac-Lactide ring-opening polymerization, prepare the residual poly(lactic acid) of no metallic compound.
The technical scheme that realizes the object of the invention is: the method for preparing polylactic acid by lactide open loop polymerization reaction; with the rac-Lactide is monomer; with phosphorous acid dialkyl ester is catalyzer; the two mixture is 25-280 ℃ in temperature of reaction; under vacuum or the protection of inert gas condition, rac-Lactide generation ring-opening polymerization generates poly(lactic acid).
The mol ratio of above-mentioned rac-Lactide and phosphorous acid dialkyl ester is 25～1000: 1, and vacuum tightness is that the pressure of 1～500 handkerchief or rare gas element is the 100-101325 handkerchief.
Above-mentioned rac-Lactide ring-opening polymerization carries out under microwave exposure, and microwave exposure power is 50-1000 watt; Microwave irradiation time is 20-120 minute.
Above-mentioned rac-Lactide can be rac-lactide, Study of Meso-Lactide, levorotatory lactide or dextrorotation rac-Lactide, or any two kinds, three kinds or four kinds mixture in these four kinds of rac-Lactides.
Above-mentioned phosphorous acid dialkyl ester is dialkyl phosphite, phosphorous acid dialkylene ester, phosphorous acid diynyl ester, phosphorous acid diaryl ester, and the carbon atom number of alkyl is from 1-20.
Two alkyl of above-mentioned phosphorous acid dialkyl ester are identical or different.
The present invention is a raw material with the rac-Lactide, makes it that ring-opening polymerization takes place under decompression or protection of inert gas condition behind the adding phosphorous acid dialkyl ester in rac-Lactide, obtains poly(lactic acid).The present invention be simple and easy to phosphorous acid dialkyl ester as the catalyzer of rac-Lactide ring-opening polymerization, avoided the use metal catalyst, it is residual that the poly(lactic acid) of preparation does not have metallic compound.Resulting poly(lactic acid) is suitable to electronic product material and bio-medical material.In addition, when the present invention adopts microwave exposure to make it that ring-opening polymerization take place, because the microwave polyreaction is compared with conventional heat polymerization, microwave heating is a kind of intramolecularly type of heating, can reduce energy waste significantly, and also there is non-thermal effect in microwave to chemical reaction, can play the effect that promotes reaction.Compare with the conventional thermopolymerization of the catalytic rac-Lactide of aforesaid a few class transesterification reagent, the inventive method has that catalyzer is easy to get, saves time, advantage such as energy-conservation.
Embodiment
Below by embodiment the present invention is elaborated, but should not be considered as limitation of the present invention.
Embodiment 1
The dimethylphosphite of rac-lactide and 2% (mol ratio) places a glass-tube, vacuum (1 handkerchief) down tube sealing after 50 watts of microwave irradiatings 60 minutes.After the question response mixture was chilled to room temperature, the solid that is generated dissolved with methylene dichloride, used the methyl alcohol reprecipitation subsequently, and the white solid that leaches is through vacuum-drying, its weight-average molecular weight Mw 39100, heterogeneity index Mw/Mn 1.83.
Embodiment 2
The phosphorous acid two propylene esters of levorotatory lactide and 0.1% (mol ratio) place a glass-tube, vacuum (50 handkerchief) down tube sealing after 150 watts of microwave irradiatings 30 minutes.After the question response mixture was chilled to room temperature, the solid that is generated dissolved with methylene dichloride, used the methyl alcohol reprecipitation subsequently, and the white solid that leaches is through vacuum-drying, its weight-average molecular weight Mw 21800, heterogeneity index Mw/Mn 1.67.
Embodiment 3
Phosphorous acid two propynyl esters of levorotatory lactide and 4% (mol ratio) place a glass-tube, and tube sealing under 100 handkerchief nitrogen is after 400 watts of microwave irradiatings 20 minutes.After the question response mixture was chilled to room temperature, the solid that is generated dissolved with methylene dichloride, used the methyl alcohol reprecipitation subsequently, and the white solid that leaches is through vacuum-drying, its weight-average molecular weight Mw 17400, heterogeneity index Mw/Mn 1.62.
Embodiment 4
The phosphorous acid diphenyl ester of dextrorotation rac-Lactide and 1% (mol ratio) places a glass-tube, under 101325 handkerchief argon gas through 400 watts of microwave irradiatings 90 minutes.Reaction finishes the solid that the back is generated with the methylene dichloride dissolving, and filtrate is filtered after the methyl alcohol reprecipitation leaches white solid, vacuum-drying, its weight-average molecular weight Mw 10500, heterogeneity index Mw/Mn 1.86.
Embodiment 5
The diisopropyl phosphite of Study of Meso-Lactide and 1/100 (mol ratio) in sealed tube under 100 handkerchiefs through 300 watts of microwave irradiatings 50 minutes.Reaction finishes the solid that the back is generated with the methylene dichloride dissolving, and solution filters after the methyl alcohol reprecipitation.Leach white solid, vacuum-drying, its weight-average molecular weight Mw 18500, heterogeneity index Mw/Mn 1.80.
Embodiment 6
The mixture of the O-eicosyl-O-butenyl-phosphorous acid of rac-lactide and 0.1% (mol ratio) in sealed tube in the solid that is generated with methylene dichloride dissolving after 60 minutes through 250 watts of microwave irradiatings under 30 handkerchiefs, through the methyl alcohol reprecipitation, leach white solid, vacuum-drying, its weight-average molecular weight Mw 16400, heterogeneity index Mw/Mn 1.66.
Embodiment 7
The mixture of the O-phenyl-O-proyl-phosphorous acid of rac-lactide and 1% (mol ratio) in sealed tube in the solid that is generated with methylene dichloride dissolving after 60 minutes through 250 watts of microwave irradiatings under 30 handkerchiefs, through the methyl alcohol reprecipitation, leach white solid, vacuum-drying, its weight-average molecular weight Mw 14300, heterogeneity index Mw/Mn 1.71.
Embodiment 8
Levorotatory lactide and rac-lactide mix behind the diisopropyl phosphite that the back adds 1% (mol ratio) tube sealing under vacuum condition with arbitrary proportion, reaction mixture earlier was preheated to fusion in 10 minutes through 50 watts of microwave irradiatings, used 150 watts of microwaves irradiation 20 minutes more subsequently instead.The solid that reaction generates leaches white solid, vacuum-drying, its weight-average molecular weight Mw 20500, heterogeneity index Mw/Mn 1.83 with methylene dichloride dissolving, methyl alcohol reprecipitation.
Embodiment 9,10,11 is a monomer with dextrorotation rac-Lactide/rac-lactide mixture, levorotatory lactide/Study of Meso-Lactide mixture, dextrorotation rac-Lactide/Study of Meso-Lactide mixture respectively, step according to embodiment 8 is carried out ring-opening polymerization, microwave irradiation time 20-120 minute again, resulting polylactic acid molecule amount and molecular weight distribution are also close with embodiment 8 results.
Embodiment 13
Levorotatory lactide, dextrorotation rac-Lactide and Study of Meso-Lactide are handled equally according to embodiment 8 steps after mixing with arbitrary proportion, and resulting polylactic acid molecule amount and molecular weight distribution are close with embodiment 8 results.
Embodiment 14,15,16 handles according to embodiment 13 steps equally with dextrorotation rac-Lactide/Study of Meso-Lactide/rac-lactide mixture, levorotatory lactide/inward turning rac-Lactide/rac-lactide mixture and levorotatory lactide/dextrorotation rac-Lactide/rac-lactide mixture respectively, can obtain respectively that molecular weight is about 20000, the poly(lactic acid) of molecular weight distribution 1.78-1.86.
Claims (6)
1. the method for preparing polylactic acid by lactide open loop polymerization reaction; it is characterized in that: being monomer with the rac-Lactide, is catalyzer with phosphorous acid dialkyl ester, and the two mixture is 25-280 ℃ in temperature of reaction; under vacuum or the protection of inert gas condition, rac-Lactide generation ring-opening polymerization generates poly(lactic acid).
2. method according to claim 1 is characterized in that: the mol ratio of rac-Lactide and phosphorous acid dialkyl ester is 25～1000: 1, and vacuum tightness is that the pressure of 1～500 handkerchief or rare gas element is the 100-101325 handkerchief.
3. method according to claim 1 and 2 is characterized in that: the rac-Lactide ring-opening polymerization carries out under microwave exposure, and microwave exposure power is 50-1000 watt; Microwave irradiation time is 20-120 minute.
4. method according to claim 1 and 2 is characterized in that: rac-Lactide is that rac-lactide, Study of Meso-Lactide, levorotatory lactide are or/and the dextrorotation rac-Lactide.
5. method according to claim 1 and 2 is characterized in that: phosphorous acid dialkyl ester is dialkyl phosphite, phosphorous acid dialkylene ester, phosphorous acid diynyl ester, phosphorous acid diaryl ester, and the carbon atom number of alkyl is from 1-20.
6. method according to claim 1 and 2 is characterized in that: two alkyl of phosphorous acid dialkyl ester are identical or different.
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| CN2007101685805A CN101186687B (en) | 2007-12-04 | 2007-12-04 | Method for preparing polylactic acid by lactide open loop polymerization reaction |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010022683A1 (en) * | 2008-09-01 | 2010-03-04 | 南京工业大学 | Method for preparing polylactic acid and products thereof using a twin-screw extruder |
| CN102627754A (en) * | 2012-04-24 | 2012-08-08 | 江苏天仁生物材料有限公司 | Method for preparing flexible polylactic acid copolymer |
| 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 |
| CN113512181A (en) * | 2021-08-09 | 2021-10-19 | 重庆大学 | Polylactic acid capable of being processed at low temperature and preparation method thereof |
| CN117164550A (en) * | 2023-11-02 | 2023-12-05 | 华东理工大学 | Preparation method of high-purity lactide and application of high-purity lactide in polylactic acid synthesis |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1284778C (en) * | 2004-05-26 | 2006-11-15 | 武汉大学 | Method for preparing lactide by microwave radiation |
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2007
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010022683A1 (en) * | 2008-09-01 | 2010-03-04 | 南京工业大学 | Method for preparing polylactic acid and products thereof using a twin-screw extruder |
| CN102627754A (en) * | 2012-04-24 | 2012-08-08 | 江苏天仁生物材料有限公司 | Method for preparing flexible polylactic acid copolymer |
| 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 |
| CN111499844A (en) * | 2018-03-08 | 2020-08-07 | 深圳市立心科学有限公司 | Medical polylactic acid and preparation method thereof |
| CN111499844B (en) * | 2018-03-08 | 2022-12-09 | 深圳市立心科学有限公司 | Medical polylactic acid and preparation method thereof |
| CN113512181A (en) * | 2021-08-09 | 2021-10-19 | 重庆大学 | Polylactic acid capable of being processed at low temperature and preparation method thereof |
| 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 |
| CN117164550A (en) * | 2023-11-02 | 2023-12-05 | 华东理工大学 | Preparation method of high-purity lactide and application of high-purity lactide in polylactic acid synthesis |
| CN117164550B (en) * | 2023-11-02 | 2024-01-26 | 华东理工大学 | Preparation method of high-purity lactide and application of high-purity lactide in polylactic acid synthesis |
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