CN100404580C - Method for preparing L-lactic acid and amino acid copolymer by melt-solid phase condensation polymerization - Google Patents
Method for preparing L-lactic acid and amino acid copolymer by melt-solid phase condensation polymerization Download PDFInfo
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- CN100404580C CN100404580C CNB2005101106273A CN200510110627A CN100404580C CN 100404580 C CN100404580 C CN 100404580C CN B2005101106273 A CNB2005101106273 A CN B2005101106273A CN 200510110627 A CN200510110627 A CN 200510110627A CN 100404580 C CN100404580 C CN 100404580C
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- amino acid
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Abstract
The present invention discloses a method for preparing a novel biodegradation material comprising hydrogen bond polylactic acid-L-lactic acid and an amino acid copolymer by melt-solid phase condensation polymerization, which has the steps: 1) melt condensation polymerization: 1) melt condensation polymerization: L-Lactic acid as a raw material is gradually depressurized and dehydrated, and then, amino acid and catalysts are added for condensation polymerization; 2) solid phase polymerization: prepolymers are pulverized, and solid phase polymerization is carried out under the condition that a molecular sieve exists. Since dissolvent is not utilized in the whole technology, a lactic acid-amino acid copolymer having a high molecular weight can be prepared with low cost.
Description
Technical field
The present invention relates to macromolecular material and preparation method thereof, relate in particular to polydactyl acid and preparation method thereof.
Background technology
Along with the development of Science ﹠ Society, environment and resource problem more and more are subject to people's attention, and become global problem.The plastic material that with the oil is raw material is widely used, and this class material uses the back to be difficult to recycle, and has caused present more serious " white pollution " problem; And this class resource of oil is non-renewable, and a large amount of irrational uses has brought serious shortage of resources problem to the mankind.The raw-material recyclability of the appearance of degradable material, especially degradable material is for the effective means that provide are provided.Poly(lactic acid) (PLA) is that more relatively a kind of degradable material is used in research at present, it is to be a kind of environment-friendly material that basic raw material prepares with the lactic acid that amylofermentation (or chemosynthesis) obtains, it not only has good physicals, also have excellent biological compatibility and degradation property, and nontoxic non-stimulated to human body.At medicine controlled releasing, surgical sutures, aspects such as bone fracture internal fixation material are widely used, and have become a kind of high polymer material very important in the bio-medical material.It also is a substrate material main in the organizational project simultaneously, has made the various form supports that are used for body.But along with the continuous developing of poly(lactic acid) Application Areas, independent poly(lactic acid) homopolymer can not satisfy application requiring, and for example: biocompatibility is also not really desirable, because the shortcoming good hydrophilicity is unfavorable for cell adhesion, and propagation and differentiation; In the organism environment, can not get rid of fully and cause scorching effect; Degradation speed is difficult to control, and intensity and toughness are not enough etc.People carry out study on the modification in large quantities to poly(lactic acid) for this reason, for example: Chinese patent CN1367189A, Penise.C, employing free radical grafting methods such as Ejuibura.JL are used for polydactyl acid with polyvinyl alcohol, vinylformic acid, unsaturated cyclic acid anhydrides or unsaturated cyclic imide, on side chain, introduce OH, COOH or inferior amide group, improved the wetting ability situation of poly(lactic acid); Veenstra.H, Breitenbach.A etc. adopt rac-Lactide and copolymerization such as glycollide, caprolactone, phosphorous acid ester, polyoxyethylene glycol or polyvalent alcohol, poly(lactic acid) is introduced main chain because of comonomer has increased the kindliness of molecular chain, and has improved wetting ability and degradation property to a certain extent.The Bmera of Massachusetts Institute Technology teaches synthesizing lactic acid/Methionin multipolymer (PLAL), Chinese patent CN03135454.8 discloses lactic acid/amino acid ester blend and preparation method thereof, Chinese patent CN1435438A discloses preparation method for diamine polydactyl acid, the polymer performance of above method preparation has to a certain degree improvement, but all has complex process, cost height point really.Therefore, that this area presses for is easy, synthetic method cheaply, in order to prepare high performance polydactyl acid.
Summary of the invention
One of purpose of the present invention provides a kind of easy, synthetic method of polydactyl acid cheaply, to improve the deficiency of prior art;
Another object of the present invention provides a kind of new modified poly(lactic acid) with polyester and polymeric amide performance.
A first aspect of the present invention discloses a kind of polydactyl acid synthetic method, comprises the steps:
(1) dehydration: the L-lactic raw material is that 100～140 ℃, pressure are 0～1.0 * 10 in temperature
-3Under the condition of MPa, decompression dehydration 4～8 hours;
(2) melt phase polycondensation: in the quality of L-lactic acid after the dehydration, add 0.1～10% amino acid, 0.1～1.0% catalyzer in the L-lactic acid after the dehydration, temperature is 140～200 ℃ and reacts 5～30h; In multipolymer, add 0.1～3% catalyzer, continue reaction 0.5～2h, obtain lactic acid-amino acid prepolymer;
(3) solid state polymerization: above-mentioned prepolymer is pulverized, at 80～150 ℃, pressure less than 5x10
-4Under the condition that the water-retaining agent molecular sieve that MPa, prepolymer quality are 1～3 times exists, solid state polymerization 5～35h makes L-lactic acid-amino acid copolymer;
Catalyzer among the preparation method comprises stannous octoate, tin protochloride, tin tetrachloride, tin protoxide, tetra-n-butyl titanate, titanium isopropylate;
Water-retaining agent molecular sieve among the preparation method is the mixture that elements such as the oxide compound of oxide compound, aluminium of silicon and sodium, potassium, calcium form.
A second aspect of the present invention discloses a kind ofly by aforesaid method synthetic polydactyl acid, has following structure:
X wherein, y is integer and x＞y;
R
1For
The integer of n=2～11.
In a preferred scheme, R
1For
N=5.
Measure polymericular weight, the weight-average molecular weight of the prepolymer behind melt phase polycondensation is 0.1～20,000, and the final polymkeric substance weight-average molecular weight behind solid state polymerization is 2～6.5 ten thousand.
The method of synthesis modification poly(lactic acid) disclosed by the invention can obtain molecular weight and reach high molecular L-lactic acid-amino acid copolymer of 60,000, and technology is simple, and is easy to operate.Owing to adopt fusion-solid state polymerization, overcome the defective that the solvent in the finished product multipolymer is difficult to remove fully, also greatly reduce cost.
L-lactic acid-the amino acid copolymer that adopts method of the present invention to obtain is a kind of new bio degradable material with polyester and polymeric amide performance.Compare with the poly(lactic acid) homopolymer, because amino introducing makes polymkeric substance have better biocompatibility, wetting ability, has suppressed the degraded feature of poly(lactic acid) autoacceleration, simultaneously because amino introducing has increased the Application Areas that the reactive force of hydrogen bond between the polymer molecule is widened the poly(lactic acid) homopolymer.
Description of drawings
Fig. 1 is the lactic acid homopolymer nuclear magnetic spectrogram.
Fig. 2 is the polydactyl acid nuclear magnetic spectrogram.
Embodiment
L-lactic acid lactic acid is Purac company product, and 3-alanine, 4-aminobutyric acid, 6-aminocaprolc acid are biochemical reagents Shanghai chemical reagents corporation product, water-retaining agent 5
Molecular sieve is a Shanghai chemical reagents corporation product, and stannous octoate analytical pure, tin protochloride analytical pure, tin tetrachloride analytical pure, tin protoxide analytical pure, tetra-n-butyl titanate analytical pure, titanium isopropylate analytical pure are Shanghai chemical reagents corporation product.
Disclosed GPC method in " the directly research of the synthetic low molecular weight of condensation method " such as polymer molecule flow measurement employing Wang Zheng specifically sees " ion-exchange and absorption " 2000,16 (4): 311-317.
Below in conjunction with embodiment, the present invention is described further, but the present invention is not limited to following embodiment.
Measure 700mL 85%L-lactic acid (Purac company product) and in the 1000mL single necked round bottom flask, flask is placed on the rotatory evaporator, the rotating speed of rotatory evaporator is 200rpm/min, 130 ℃ oil bath heating, and the pressure that progressively reduces pressure is less than 1.0 * 10
-3MPa continues to stop behind the dehydration 4h.The inflated with nitrogen release adds the stannous octoate of dehydration back L-lactic acid quality 0.5%, 0.5% 6-aminocaprolc acid, and oil bath temperature rises to 180 ℃, and the rotating speed of rotatory evaporator still is 200rpm/min, progressively is decompressed to pressure less than 5.0 * 10
-4MPa adds 0.5% stannous octoate behind the reaction 10h, continues reaction 0.5h end reaction and pours in the Stainless Steel Disc.
Above-mentioned prepolymer pulverizing is placed vacuum drying oven, put into 5 of one times of prepolymer quality again
Molecular sieve is evacuated to less than 5.0 * 10
-4MPa is warming up to 80 ℃, and every then 1h heats up 10 ℃.When temperature rises to 150 ℃, stop to heat up.Solid state polymerization 20h.
Disclosed GPC method in " the directly research of the synthetic low molecular weight of condensation method " such as employing Wang Zheng, the weight-average molecular weight (M of the multipolymer of test preparation
w) be 6.1 ten thousand.
The lactic acid homopolymer nuclear magnetic spectrogram is seen Fig. 1.Measure the polymkeric substance mass spectrum with UNITY plus-500M nuclear magnetic resonance, spectrometer, room temperature is with CDCl
3Be solvent, sweep rate 500MHZ the results are shown in Figure 2.
Embodiment 2
The preparation of L-lactic acid prepolymer, the condition that reaches solid state polymerization are with embodiment 1, and the 3-alanine replaces 6-aminocaprolc acid, and the GPC method records the M of multipolymer
wBe 5.3 ten thousand.
The preparation of L-lactic acid prepolymer, the condition that reaches solid state polymerization are with embodiment 1, and the 4-aminobutyric acid replaces 6-aminocaprolc acid, and the GPC method records the M of multipolymer
wBe 5.6 ten thousand.
The preparation of L-lactic acid prepolymer, the condition that reaches solid state polymerization are with embodiment 1, and tin protochloride replaces stannous octoate, and the GPC method records the M of multipolymer
wBe 4.3 ten thousand.
The preparation of L-lactic acid prepolymer, and the condition of solid state polymerization is with embodiment 1, tin protochloride replaces stannous octoate, and the amount of twice adding is respectively 0.5%, 1%, and the GPC method records the M of multipolymer
wBe 4.5 ten thousand.
The preparation of L-lactic acid prepolymer, the condition that reaches solid state polymerization is with embodiment 1, and the 6-aminocaprolc acid add-on is 1%, and the GPC method records the M of multipolymer
wBe 5.7 ten thousand.
Embodiment 7
The preparation of L-lactic acid prepolymer, the condition that reaches solid state polymerization is with embodiment 1, and the 6-aminocaprolc acid add-on is 4%, and the GPC method records the M of multipolymer
wBe 3.2 ten thousand.
Claims (4)
1. a method for preparing L-lactic acid-amino acid copolymer is characterized in that, comprises the steps:
(1) dehydration: the L-lactic raw material is that 100～140 ℃, pressure are 0～1.0 * 10 in temperature
-3Under the condition of MPa, decompression dehydration 4～8 hours;
(2) melt phase polycondensation: in the quality of L-lactic acid after the dehydration, add 0.1～10% amino acid, 0.1～1.0% catalyzer in the L-lactic acid after the dehydration, temperature is 140～200 ℃ and reacts 5～30h; In multipolymer, add 0.1～3% catalyzer, continue reaction 0.5～2h, obtain lactic acid-amino acid prepolymer;
(3) solid state polymerization: above-mentioned prepolymer is pulverized, at 80～150 ℃, pressure less than 5 * 10
-4Under the condition that the water-retaining agent molecular sieve that MPa, prepolymer quality are 1～3 times exists, solid state polymerization 5～35h makes L-lactic acid-amino acid copolymer;
Catalyzer is selected from a kind of in stannous octoate, tin protochloride, tin tetrachloride, tin protoxide, tetra-n-butyl titanate, the titanium isopropylate;
Water-retaining agent 5
, 3
Molecular sieve is a kind of in the mixture that forms of the oxide compound of oxide compound, aluminium of silicon and sodium, potassium, calcium constituent.
2. method according to claim 1 is characterized in that amino acid structure is
The integer of n=2～11.
3. the polymkeric substance of method preparation according to claim 1 is characterized in that having following structure:
X wherein, y is integer and the x＞y greater than 0;
R
1For
The integer of n=2～11.
4. polymkeric substance according to claim 3 is characterized in that, the molecular weight of polymkeric substance is 2～6.5 ten thousand dalton.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100424112C (en) * | 2007-01-05 | 2008-10-08 | 华南师范大学 | Preparation method of amino acid and lactic acid copolymer |
| CN101429325B (en) * | 2007-11-05 | 2012-01-18 | 东丽纤维研究所（中国）有限公司 | Crystallization modified polylactic acid coblended matter and molding product thereof |
| CN104877130B (en) * | 2015-03-11 | 2018-02-06 | 华东理工大学 | A kind of synthetic method of PLA gamma aminobutyric acid copolymeric material |
| CN106798950A (en) * | 2016-11-30 | 2017-06-06 | 浙江工业大学 | A kind of preparation method of the guide tissue regeneration film repaired for periodontitis |
| KR102241367B1 (en) | 2018-01-05 | 2021-04-15 | 주식회사 엘지화학 | Block copolymer |
| KR20200115166A (en) | 2019-03-26 | 2020-10-07 | 주식회사 엘지화학 | Tri block copolymer and process for preparation thereof |
| CN112646151B (en) * | 2020-12-09 | 2022-08-02 | 华南师范大学 | A degradable bio-based slow-release lead ion chelating agent and its preparation method and application |
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Assignee: Shanghai Tiantan Auxiliaries Co., Ltd. Assignor: Shanghai Chlor-Alkali Chem. Co., Ltd. Contract fulfillment period: 2009.5.4 to 2014.5.3 contract change Contract record no.: 2009310000160 Denomination of invention: Method for preparing L-lactic acid and amino acid copolymer by melt-solid phase condensation polymerization Granted publication date: 20080723 License type: Exclusive license Record date: 2009.8.12 |
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