CN101367921A - Method for synthesis of polylactic acid with lactide opened loop - Google Patents
Method for synthesis of polylactic acid with lactide opened loop Download PDFInfo
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- CN101367921A CN101367921A CNA2008102007847A CN200810200784A CN101367921A CN 101367921 A CN101367921 A CN 101367921A CN A2008102007847 A CNA2008102007847 A CN A2008102007847A CN 200810200784 A CN200810200784 A CN 200810200784A CN 101367921 A CN101367921 A CN 101367921A
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Abstract
The invention relates to the technical filed of high polymer chemistry, pertaining to a method for preparing biological medical degradation material polylactic acid, currently used as the catalyst for synthesizing lactide open-loop into polylactic acid, and stannous octoate is known to have the highest catalytic efficiency, but the catalyst results in metallic residue in the polylactic acid. The invention discloses a method to synthesize lactide open-loop into polylactic acid under the catalysis of amino acid. The method takes nontoxical and metal-free amino acid needed by human body as the catalyst for lactide ring-opening polymerization, thereby, metallic catalyst is avoided to be used, and the prepared polylactic acid is free of metallic compound residue. The achieved polylactic acid can be used as the carrier for drug control and release as well as tissue engineering material.
Description
Technical field
The present invention relates to technical field of polymer chemistry, is a kind of preparation method of bio-medical degradation property material poly(lactic acid), is specifically related to use the method for amino acid catalytic synthesis of polylactic acid with lactide opened loop.
Background technology
Poly(lactic acid) (PLA) is a class degradable biomedical macromolecular material.Poly(lactic acid) has excellent biodegradability, biocompatibility and biological safety, its degraded product lactic acid can participate in carbohydrate metabolism in the human body, noresidue, safety non-toxic has extensive studies and application as medicine sustained release carrier, operating sutures, tissue engineering bracket material and bone renovating material etc. at biomedical sector.The preparation method of poly(lactic acid), general is to adopt bulk polymerization, is monomer with the rac-Lactide, uses catalyzer, under the certain reaction condition, makes rac-Lactide generation ring-opening polymerization generate poly(lactic acid).Rac-Lactide has L, L-rac-Lactide (LLA claims levorotatory lactide again), D, D-rac-Lactide (DLA claims the dextrorotation rac-Lactide again) and D, three kinds of steric isomers of L-rac-Lactide (DLLA claims Study of Meso-Lactide again).
The catalyzer that is used for synthesis of polylactic acid with lactide opened loop at present, be known as catalytic efficiency best be stannous octoate (Kricheldorf H R, et al, Polylactones 48.SnOct
2-initiated polymerizationof lactide:A mechanistic study, Macromolecules, 2000,33,702.), its reaction scheme is as follows:
But in above-mentioned polymerization process, metal catalyst thoroughly can't be removed from synthetic polymer, cause in the polymkeric substance kish compound inevitably, and according to research stannous octoate have cytotoxicity (Saunders I K, et al, Polylactones, 39.Zn lactate-catalyzed copolymerization ofL-lactide with glycolide or ε-caprolactone, Macromol.Chem.Phys, 1998,199,1081; Schwarch G, et al, Ring opening polymerization of D, L-lactide in the presence ofzinc metal and zinc lactate.Polym.Int, 1998,46,177.), this makes and uses this class material to bring insecurity hidden danger as pharmaceutical material, particularly longer-term (taking the carrier of medicine, the property implanted medical material etc. for a long time) this type of material.
The poly(lactic acid) that the interior security requirement of the body of bio-medical material is used for this field does not have metallic compound residual.But nearest result of study shows all catalyzing ring-opening polymerization of lactide reactions such as some nonmetallic compounds such as creatinine, guanidine compound etc., avoids the possibility of kish compound in the poly-lactic acid material.
(Chenhong?Wang，et?al，Ring?opening?polymerization?of?L-lactide?initiated?bycreatinine，Biomaterials，2004，25，5797；Hong?Li，et?al，Living?Ring?OpeningPolymerization?of?Lactides?Catalyzed?by?Guanidinium?Acetate，J.Polym.Sci.PartA：Polym.Chem，2004，42，3775)。
Summary of the invention
The object of the present invention is to provide a kind of method of synthesis of polylactic acid with lactide opened loop, it is residual that this method can obtain not have metallic compound, and the poly(lactic acid) of productive rate 〉=90%.
The present invention adopts bulk polymerization, is catalyzer with the amino acid of nontoxic, no metal, needed by human body, is monomer with the rac-Lactide; the two mixture is 140-200 ℃ in temperature of reaction; under the vacuum protection condition, reacted 24～96 hours, rac-Lactide generation ring-opening polymerization generates poly(lactic acid).
Above-mentioned rac-Lactide is L preferably, L-rac-Lactide or D, and the L-rac-Lactide also can be D, the D-rac-Lactide.
Above-mentioned amino acid can be arginine or Histidine, and various configurations all can.
Above-mentioned temperature of reaction the best is 160 ℃.
Above-mentioned reaction times the best is 48 hours.
Concrete technical scheme of the present invention: with rac-Lactide (D, L-rac-Lactide or L, the L-rac-Lactide) and amino acid (50～1000) in molar ratio: 1 drops in the reactor, vacuumize to remove and fill again behind the air with high pure nitrogen (purity〉99.9999 for high-purity), so triplicate is closed reactor under the last vacuum.Reactor is under agitation slowly heated up, under steady temperature 140～200 ℃ then, reacted 24～96 hours, behind the stopped reaction, with the polymkeric substance acetone solution, pour in the deionized water then and precipitate, filtering water postprecipitation vacuum-drying at room temperature 24～72 hours, obtain white or faint yellow solid, be the synthesising biological degradation polymer PLA of institute.
With the tetrahydrofuran (THF) is solvent, and μ-Styragel packed column measures institute's synthetic polymer molecule amount with the Agilent-1100 gel chromatograph under 35 ℃, (be with the monodisperse polystyrene standard specimen and proofread and correct through pervasive value).Institute's synthetic polymer molecule amount can be controlled in M
w=1.0～2.0 * 10
4, molecular weight distributing index (PDI) is 1.20～1.60, and productive rate 〉=90%, product are white or faint yellow.
Since the present invention use be simple and easy to amino acid needed by human body 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.Advantages such as catalyst system therefor of the present invention has cheapness, is easy to get, stablizes, biological safety.Use productive rate 〉=90% of the inventive method gained poly(lactic acid).
The poly(lactic acid) that makes with the inventive method is suitable to medicine controlled release carrier and tissue engineering material.
Embodiment
Embodiment 1:
Pack in the reactor rac-Lactides of 14.4 grams, press monomer: catalyzer=100:1 (mol ratio) adds 174 milligrams of arginine.Reactor is vacuumized, use the nitrogen replacement repetitive operation then three times, close reactor under the vacuum, reactor is slowly heated, 160 ℃ were reacted 48 hours under steady temperature.Behind the stopped reaction, reactor is chilled to room temperature, adds acetone solution still interpolymer then.Add deionized water then, polymer precipitation is come out.The filtering water places vacuum drying oven with precipitation at last, 40 ℃ of vacuum-dryings 48 hours, obtains the white powder solid, productive rate 92%.Polymericular weight is 1.0～1.5 * 10
4, PDI≤1.50.
Embodiment 2:
Pack in the reactor rac-Lactides of 14.4 grams, press monomer: catalyzer=50:1 (mol ratio) adds 348 milligrams of arginine.The following 140 ℃ of reactions of temperature of reaction 96 hours.Productive rate 91%, polymericular weight are 1.0～1.2 * 10
4, PDI≤1.40.All the other are with embodiment 1.
Embodiment 3
Pack in the reactor rac-Lactides of 14.4 grams, press monomer: catalyzer=100:1 (mol ratio) adds 155 milligrams of Histidines.Reactor is vacuumized, use the nitrogen replacement repetitive operation then three times, close reactor under the vacuum, reactor is slowly heated, 160 ℃ were reacted 72 hours under steady temperature.Behind the stopped reaction, reactor is chilled to room temperature, adds acetone solution still interpolymer then.Add deionized water then, polymer precipitation is come out.The filtering water places vacuum drying oven with precipitation at last, 40 ℃ of vacuum-dryings 48 hours, obtains pale yellow powder shape solid, productive rate 94%.Polymericular weight is 1.0～1.5 * 10
4, PDI≤1.40.
Embodiment 4:
Pack in the reactor rac-Lactides of 14.4 grams, press monomer: catalyzer=500:1 (mol ratio) adds 31 milligrams of Histidines.The following 200 ℃ of reactions of temperature of reaction 24 hours.Productive rate 92%.Polymericular weight is 1.8～2.0 * 10
4, PDI≤1.60.All the other are with embodiment 3.
Claims (4)
1. the method for a synthesis of polylactic acid with lactide opened loop is characterized in that with amino acid being catalyzer, and with rac-Lactide and amino acid (50～1000) in molar ratio: 1 drops in the reactor, and under the vacuum condition, temperature of reaction is 140-200 ℃, reacts 24～96 hours.
2. the method for a kind of synthesis of polylactic acid with lactide opened loop according to claim 1 is characterized in that amino acid is arginine or Histidine.
3. the method for a kind of synthesis of polylactic acid with lactide opened loop according to claim 1 and 2 is characterized in that temperature of reaction is 160 ℃.
4. the method for a kind of synthesis of polylactic acid with lactide opened loop according to claim 1 and 2 is characterized in that the reaction times is 48 hours.
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| CNA2008102007847A CN101367921A (en) | 2008-10-06 | 2008-10-06 | Method for synthesis of polylactic acid with lactide opened loop |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102161752A (en) * | 2011-03-14 | 2011-08-24 | 南京大学 | Process method for synthesizing medical biodegradable polylactic acid by polycondensation of lactic acid in presence of creatinine catalyst |
| CN102596973A (en) * | 2009-09-02 | 2012-07-18 | Lg化学株式会社 | Organotin compound, method for preparing same, and method for preparing polylactide using same |
| CN105906789A (en) * | 2016-05-26 | 2016-08-31 | 常州大学 | High-efficiency catalyst for synthesizing polyglycollic acid |
| JP2017507229A (en) * | 2014-12-12 | 2017-03-16 | 南京大学 | High performance high molecular weight poly L-lactic acid synthesis process |
| CN110078634A (en) * | 2019-05-23 | 2019-08-02 | 大连汇鹏达化工有限公司 | A kind of preparation method and application of amino acid stannous complex |
| CN110885430A (en) * | 2019-12-18 | 2020-03-17 | 大连大学 | Method for initiating lactide ring-opening dispersion polymerization by using arginine |
| 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 |
| CN117903441A (en) * | 2024-03-19 | 2024-04-19 | 苏州禾润昌新材料有限公司 | Biodegradable polymer material and preparation method thereof |
| CN117903441B (en) * | 2024-03-19 | 2024-05-28 | 苏州禾润昌新材料有限公司 | Biodegradable polymer material and preparation method thereof |
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2008
- 2008-10-06 CN CNA2008102007847A patent/CN101367921A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102596973A (en) * | 2009-09-02 | 2012-07-18 | Lg化学株式会社 | Organotin compound, method for preparing same, and method for preparing polylactide using same |
| CN102596973B (en) * | 2009-09-02 | 2016-01-20 | Lg化学株式会社 | Organo-tin compound, its preparation method and use this organo-tin compound to prepare the method for polylactide |
| CN102161752A (en) * | 2011-03-14 | 2011-08-24 | 南京大学 | Process method for synthesizing medical biodegradable polylactic acid by polycondensation of lactic acid in presence of creatinine catalyst |
| CN102161752B (en) * | 2011-03-14 | 2013-02-27 | 南京大学 | Process method for synthesizing medical biodegradable polylactic acid by polycondensation of lactic acid in presence of creatinine catalyst |
| JP2017507229A (en) * | 2014-12-12 | 2017-03-16 | 南京大学 | High performance high molecular weight poly L-lactic acid synthesis process |
| CN105906789A (en) * | 2016-05-26 | 2016-08-31 | 常州大学 | High-efficiency catalyst for synthesizing polyglycollic acid |
| CN110078634A (en) * | 2019-05-23 | 2019-08-02 | 大连汇鹏达化工有限公司 | A kind of preparation method and application of amino acid stannous complex |
| CN110078634B (en) * | 2019-05-23 | 2022-05-17 | 大连汇鹏达化工有限公司 | Preparation method and application of stannous amino acid complex |
| CN110885430A (en) * | 2019-12-18 | 2020-03-17 | 大连大学 | Method for initiating lactide ring-opening dispersion polymerization by using arginine |
| 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 |
| CN117903441A (en) * | 2024-03-19 | 2024-04-19 | 苏州禾润昌新材料有限公司 | Biodegradable polymer material and preparation method thereof |
| CN117903441B (en) * | 2024-03-19 | 2024-05-28 | 苏州禾润昌新材料有限公司 | Biodegradable polymer material and preparation method thereof |
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