CN1239613C - Polylactic acid/amino acid ester blend and its preparing method - Google Patents
Polylactic acid/amino acid ester blend and its preparing method Download PDFInfo
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- CN1239613C CN1239613C CN 03135454 CN03135454A CN1239613C CN 1239613 C CN1239613 C CN 1239613C CN 03135454 CN03135454 CN 03135454 CN 03135454 A CN03135454 A CN 03135454A CN 1239613 C CN1239613 C CN 1239613C
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- acid ester
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Abstract
The present invention discloses a polylactic acid / amino acid ester blend and a preparation method thereof. The blend is polylactic acid modified by a solution blending method and is characterized in that 50 to 95 portions of polylactic acid (PLA) and 50 to 5 portions of amino acid or amino acid ester are dissolved by 150 to 300 portions of solvent and then are uniformly mixed. After the mixture reacts for 30 to 90 minutes at the temperature of 30 to 150 DEG C, the heating process is carried out to remove most of solvent, and then the pressure is reduced to 0.8 to 0.09MPa; the solvent is completely removed to obtain the polylactic acid / amino acid ester blend. The blend material has high biocompatibility and interface compatibility and can be used as a tissue support material.
Description
One, technical field
The present invention relates to a kind of poly(lactic acid)/amino acid ester blend and preparation method thereof, belong to polymer blended modification field.
Two, background technology
Poly(lactic acid) (PLA) has degradability and excellent biological compatibility, at medicine controlled releasing, and surgical sutures, aspects such as bone fracture internal fixation material are widely used, and have become epochmaking a kind of high polymer material 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 biocompatibility is also not really desirable, because the shortcoming good hydrophilicity is unfavorable for cell adhesion, and propagation and differentiation; In giving birth to the body environment, can not get rid of fully and cause scorching effect.This is because the substrate material of synthetic lacks the distinctive molecular recognition sequence of natural substrates, the cell response of material surface be at random, unordered.For this reason, people carry out study on the modification in large quantities to poly(lactic acid).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 introducing-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 chain, and has improved wetting ability and degradation property to a certain extent.The Barrera of Massachusetts Institute Technology professor, Cook synthesizing lactic acid/Methionin multipolymer (PLAL).
But chemic modified method is all used in above research, and complex process, cost are higher.The domestic people of having adopts polyoxyethylene glycol, polyvinyl alcohol and polylactic acid blend, but these researchs only rest on crystallinity, wetting ability and the degradation property aspect of poly(lactic acid).
Recently Chinese patent CN1272383A discloses nanometer phase calcium phosphoric acid salt/collagen/poly(lactic acid) and has prepared bone compounded porous material, the raw material that adopts, preparation technology, application and the present invention all inequality.
Three, summary of the invention
The objective of the invention is provides a kind of poly(lactic acid)/amino acid ester blend and preparation method thereof at the deficiencies in the prior art
The present inventor thinks, give full play to the application potential of poly(lactic acid) in organizational project, must be based on material structure and physiologically acceptable sexual intercourse, thereby in the growth of material surface conjunctive tissue specific recognition biomolecules inducing cell and tissue, this is that tissue engineering material is studied key issue to be solved.
The present inventor finds that introduce modifier in poly(lactic acid), this modifier can be necessary amino acid or the nonessential amino acid or their ester derivative of needed by human body.Make it become a kind of poly(lactic acid)/amino acid esters blend.Because of containing more reaction active groups-NH in the blend
3,-COOH.On the one hand, degradation property, wetting ability and the biocompatibility of poly(lactic acid) have been improved to a certain extent.The more important thing is that active group provides and outside biomolecules connecting portion in this material, make poly(lactic acid) have modifiability.Poly(lactic acid)/modifier has better biocompatibility and interface compatibility, can be used for tissue stent material.
Purpose of the present invention can realize that wherein said raw material umber is parts by weight except that specified otherwise with following technical measures.
The composition of raw materials of poly(lactic acid)/amino acid ester blend is:
Poly(lactic acid) molecular-weight average=1000～10,0000 remnant is less than 5% 50～95 part
Amino acid or amino acid ester analog derivative white powder or white crystal, content is greater than 98% 50～5 part
150～300 parts of solvents
Poly(lactic acid) is the L-poly(lactic acid), D-poly(lactic acid) and/or DL-poly(lactic acid) and/or at least a.
Modifier is L-amino acid or L-amino acid ester analog derivative: L-amino acid is at least a in L-glycine, L-aspartic acid, L-Methionin, L-arginine, L-tryptophane, L-phenylalanine, L-methionine(Met), L-Threonine, L-leucine and the L-a word used in person's names propylhomoserin.It also can be the L-amino acid ester analog derivative that L-amino acid and alcohols thing C1～C7-first alcohol or polyol reaction generate.
Solvent is methylene dichloride, trichloromethane, tetrahydrofuran (THF), 1,4-diox, ethyl acetate, butylacetate, dimethyl formamide and/or 1,2-ethylene dichloride at least a.
The preparation method of poly(lactic acid)/amino acid ester blend:
With 50～95 parts of poly(lactic acid), 50～5 parts of modifiers, solvent adds stirring and dissolving in the mixing kettle for 150～300 parts, mix, the evaporating solvent temperature must not surpass 180 ℃ then, and it is unstable that the too high meeting of temperature causes poly(lactic acid) to form, and it is too slow and be difficult for eliminating solvent that temperature is crossed low evaporating solvent speed.Most of solvent is removed in general the first step heating, and temperature control is at 30～180 ℃, and the blend of second step with heating makes remaining solvent distillation eliminate under the reduced vacuum condition.Control vacuum tightness is at 0.8Mpa～0.09Mpa.
Polylactic acid blend glass transition temp after modification is 40～60 ℃, can adopt extrude, method such as blowing, curtain coating carries out machine-shaping.Obtain the porous foam timbering material through lyophilize again, can be used as the medical material of organizational project.
Four, embodiment
Below by embodiment the present invention is specifically described: be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment
1, DL-poly(lactic acid) (PLA) 52g, L-glycine ethyl ester 26g, methylene chloride 200g, adding has in the reaction flask of agitator, thermometer and reflux exchanger, is stirred to dissolving fully, progressively be heated to 40 ℃ again, behind the reaction 90min, solvent evaporated is decompressed to 0.01Mpa, residual solvent is fallen in distillation, obtains DL-poly(lactic acid)/L-glycine ethyl ester blend.
2, with L-poly(lactic acid) 51g, L-Methionin benzyl ester 20g, be dissolved in respectively in tetrahydrofuran (THF) 100g and tetrahydrofuran (THF) 100g, the methylene dichloride 100g mixed solvent, put in the reaction flask that has agitator, thermometer and reflux exchanger, stir fully dissolving, temperature of reaction to 60 ℃ is behind the insulation 80min, solvent evaporated is removed at vacuum tightness 0.05Mpa and to be desolvated.Obtain L-poly(lactic acid)/L-Methionin benzyl ester blend.
3, in the identical equipment of embodiment 1, add D-poly(lactic acid) 49 grams and L-Threonine 15 and restrain 1, the mixed solvent of 4-diox 250g and tetrahydrofuran (THF) 50g, 80 ℃ of temperature, react after 30 minutes, in 110 ℃ of solvent evaporated of temperature, to 0.08Mpa, obtain D-poly(lactic acid)/L-Threonine blend at vacuum decompression.
4, in embodiment 1 identical device, add and embodiment 1 equivalent poly(lactic acid) L-aspartic acid list benzyl ester 10g, 1,4-diox 250g, be stirred to dissolving fully, progressively be heated to 80 ℃ again, behind the reaction 60min, solvent evaporated, to 0.05Mpa, residual solvent is removed in distillation, obtains DL-poly(lactic acid)/L-aspartic acid list benzyl ester blend at vacuum decompression.
5, in embodiment 1 identical device, add and embodiment 1 equivalent poly(lactic acid), L-arginine tert-butyl ester 5g, dimethyl formamide 220g is stirred to dissolving fully, progressively be heated to 120 ℃ again, behind the reaction 30min,, be decompressed to 0.08Mpa in 150 ℃ of solvent evaporated of temperature, residual solvent is fallen in distillation, obtains DL-poly(lactic acid)/L-arginine tert-butyl ester blend.
6, embodiment 1,2, and 3,4,5 poly(lactic acid)/amino acid that obtain or poly(lactic acid)/amino acid ester blend obtains the porous foam timbering material through lyophilize, can be used as the medical material of organizational project.
Claims (6)
1, poly(lactic acid)/amino acid ester blend is characterized in that the recipe ingredient of this blend is by weight:
Poly(lactic acid) molecular-weight average=1000～10,0,000 50～95 part
L-amino acid or L-amino acid ester, content is greater than 98% 50～5 part
150～300 parts of solvents.
2, poly(lactic acid)/amino acid ester blend according to claim 1 is characterized in that poly(lactic acid) is at least a in L-poly(lactic acid), D-poly(lactic acid) and/or the DL-poly(lactic acid).
3, according to claim 1, poly(lactic acid)/amino acid ester blend, it is characterized in that L-amino acid is at least a in L-glycine, L-aspartic acid, L-Methionin, L-arginine, L-tryptophane, L-phenylalanine, L-methionine(Met), L-Threonine, L-leucine and/or the L-a word used in person's names propylhomoserin, or L-amino acid and alcohols thing C
1～C
7Monohydroxy-alcohol or the L-amino acid ester derivative that generates of polyol reaction.
4, poly(lactic acid)/amino acid ester blend according to claim 1, it is characterized in that solvent is methylene dichloride, trichloromethane, tetrahydrofuran (THF), 1,4-diox, ethyl acetate, butylacetate, dimethyl formamide and/or 1, at least a in the 2-ethylene dichloride.
5, as the preparation method of poly(lactic acid)/amino acid ester blend as described in one of claim 1～4, it is characterized in that with 150～300 parts of 50～95 parts of poly(lactic acid), L-amino acid or 50～5 parts of L-amino acid esters, solvents add in the mixing kettle, agitator dissolves fully, mixes, in 30～150 ℃ of temperature, reacted 30～90 minutes, most of solvent ℃ is removed in heat temperature raising to 30～180 then, be decompressed to 0.8～0.09MPa again and eliminate solvent, obtain poly(lactic acid)/amino acid ester blend.
6, the polydactyl acid that the method for any one qualification obtains in the claim 1-4 item is used for the medical material of organizational project.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 03135454 CN1239613C (en) | 2003-07-22 | 2003-07-22 | Polylactic acid/amino acid ester blend and its preparing method |
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| CN 03135454 CN1239613C (en) | 2003-07-22 | 2003-07-22 | Polylactic acid/amino acid ester blend and its preparing method |
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| CN1491988A CN1491988A (en) | 2004-04-28 |
| CN1239613C true CN1239613C (en) | 2006-02-01 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100404580C (en) * | 2005-11-23 | 2008-07-23 | 上海氯碱化工股份有限公司 | Method for preparing L-lactic acid and amino acid copolymer by melt-solid phase condensation polymerization |
| US20070231362A1 (en) * | 2006-04-04 | 2007-10-04 | 3M Innovative Properties Company | Schistose microfibrillated article for cell growth |
| 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 |
| CN101851424B (en) * | 2009-03-31 | 2011-08-10 | 西南科技大学 | Thermoplastic plant protein/polylactic acid blend material and preparation method thereof |
| CN104497512B (en) * | 2015-01-12 | 2017-01-11 | 杨凌瑞丰环保科技有限公司 | Method for preparing degradable material modified polylactic acid polymer |
| CN108752887B (en) * | 2018-06-20 | 2021-03-26 | 台州市中心医院（台州学院附属医院） | Environment-friendly degradable composite material for disposable vaginal dilator |
| CN109535670B (en) * | 2018-11-16 | 2021-10-08 | 广东众塑降解材料有限公司 | Full-degradable simulation material and preparation method thereof |
| CN109897353B (en) * | 2019-03-19 | 2021-04-20 | 安徽倍健特生物科技有限公司 | High-strength biodegradable nano plastic and preparation method thereof |
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