CN104877352A - Compatibilizer-containing fibroin/polylactic acid blended material and preparation method thereof - Google Patents
Compatibilizer-containing fibroin/polylactic acid blended material and preparation method thereof Download PDFInfo
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- CN104877352A CN104877352A CN201410814947.6A CN201410814947A CN104877352A CN 104877352 A CN104877352 A CN 104877352A CN 201410814947 A CN201410814947 A CN 201410814947A CN 104877352 A CN104877352 A CN 104877352A
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Abstract
The invention belongs to the technical field of polymers. The invention discloses a fibroin/polylactic acid blended material. The fibroin/polylactic acid blended material has fibroin mass content of 0.1-99.9% and polylactic acid mass content of 99.9-0.1%. Through use of the fibroin/polylactic acid copolymer (PSFLA) as a compatibilizer in the blended material, fibroin and polylactic acid compatibility is improved. A use ratio of the compatibilizer to all the polylactic acid is in a range of 0.01-100.0% by mass. Fibroin, polylactic acid and PSFLA are added into hexafluoroisopropanol and the materials are dissolved at a temperature of 20-60 DEG C so that the blended solution is prepared. The blended solution is dried at a temperature of 20-150 DEG C under normal pressure or in vacuum for 0.5-24h so that the fibroin/polylactic acid blended material is obtained. The fibroin raw material comprises fibers, powder, slices or blocks. The polylactic acid is a homopolymer, a copolymer or a blended material.
Description
Technical field:
The invention belongs to technical field of polymer materials, be specifically related to blend material of a kind of fibroin and poly(lactic acid) and its preparation method and application.
Background technology:
Poly(lactic acid) (PLA) is a kind of biodegradable aliphatic poly ester material, has good biocompatibility, degraded product is water and carbonic acid gas, the advantages such as environmentally safe, be widely used in organizational project and other biological field of medicaments.Poly(lactic acid) has hydrophobicity, and the adhesivity of its cell is poor, as the reaction that may cause inflammation after tissue engineering material implantable bioartificial body.In addition, it is very slow that pure PLA resin has crystallization velocity, and moulded products shrinking percentage is large, poor dimensional stability, processing heat stability are poor, and the shortcomings such as goods poor durability, these limit the application of poly(lactic acid).Therefore, poly-lactic acid material must carry out modification, and conventional method of modifying comprises modification by copolymerization method and blending and modifying.Wherein, utilizing other macromolecular material to carry out blending and modifying to poly(lactic acid), is one of simple effective ways improving poly(lactic acid) performance.The modification by copolymerization of poly(lactic acid), the wetting ability, crystallinity etc. that can be changed material by the copolymerization of poly(lactic acid) and other monomers or oligopolymer, the degradation speed of polymkeric substance can be controlled according to the molecular weight of multipolymer and comonomer or oligopolymer kind and proportioning etc., thus realizes the widespread use of poly-lactic acid material in organizational project.The modification by copolymerization operational path of poly(lactic acid) comprises the ring-opening polymerization of rac-Lactide/comonomer and the copolycondensation two kinds of lactic acid/comonomer.Rac-Lactide or lactic acid and hydrophilic monomer or polymkeric substance, as polyoxyethylene glycol, amino acid, the poly-copolymerization such as peptide and polyose, are introduced hydrophilic polymer segment, can be improved the biocompatibility of material, regulate its degradation rate in hydrophobic polylactic acid chain segment.
Fibroin protein (SF) is a kind of native amino acid copolymer, has excellent mechanical property and biocompatibility.Containing 18 seed amino acids in fibroin protein, wherein glycine (36%), L-Ala (28%), Serine (14%) and tyrosine (10%) content are more.Some amino acid of fibroin are extensively present in people and vertebrate tissue, have affinity to human body cell.Fibroin can make according to different object becomes the various ways such as fiber, powder, gel, silk peptide powder and fibroin membrane, can be used as makeup base material, foodstuff additive and medical material etc.In recent years, the gel of fibroin protein and porous material have been developed as drug release carrier, Three-dimensional cell culture base, artificial skin, anticoagulant material and dialysis membrane etc., but regenerated silk protein material remains in mechanical property and the unmanageable problem of degradation speed.And pure fibroin membrane dissolve-loss ratio is very high, can not directly use, after insoluble process, intensity is comparatively large, but extends very little.Therefore, the modification of regenerated fibroin material require could meet the requirement of practical application.
The research of fibroin polydactyl acid causes concern day by day.The fibroins such as Gao Qinwei are as hydrophilic radical, copolymerization segmented copolymer is carried out with poly(lactic acid), to improve wetting ability and the biocompatibility (ZL200810242819.3 of poly-lactic acid material, ZL200810242818.9, ZL200910232602.9, ZL200910232601.4, ZL200810242817.4).In addition, in addition fibroin and poly(lactic acid) are mixed, prepare the research report of the bio-medical material that cell adhesion is excellent, degradation property is good.The poly (l-lactic acid) such as Chen Jianyong, Zhang Jiazhong carries out modification to fibroin membrane, and the mechanical property of co-blended film significantly improves, and vapour permeability also increases, (Journal of Chemical Industry and Engineering, 2008,3 (59): 773 ~ 777 but water vapour permeability slightly declines; Functional materials, 2007,12 (38): 2048 ~ 2051).Zhou Yan, Liu Yang etc. utilize fibroin solutions and PLA solution fully to mix obtained blend film, change the structure properties effect of fibroin protein, prepare Biodegradable films (silk monthly magazine, 2007,4:16 ~ 18).The people such as Zhang Youzhu, Wu Jialin have carried out poly(lactic acid) and silk fibroin is blended, electrostatic spinning prepares blended nanofibre or the research of bioengineered scaffolds, and analyze (the synthetic fiber industry such as biocompatibility and mechanical property of blend, 2008,31 (3): 1 ~ 3; Journal of AppliedPolymer Science, 2009,113:2675 ~ 2682; Journal of Materials Science, 2010,93A:158 ~ 163).Zhang Feng, left guarantor are neat etc. has reported electrostatic spinning and has prepared silk fibroin/polylactic acid blend nanofiber, but the blended of SF and PLA can not form compatible system, there are two crystallizing field (polymer material science and the engineerings that are separated in blended SF/PLA nanofiber, 2009,25 (5): 75 ~ 78).At present, adopt in fibroin/polylactic acid coblended matter material of preparing of solution blending process, exist silk fibroin poor with poly(lactic acid) component compatibility, mix the problems such as inequality, boundary defect, cause the performance of blend material to be difficult to meet service requirements.
The serious scarcity of China's oil resource governs expanding economy, and China has the Biological resources of abundant lactic acid class, can substitute petroleum chemicals.Meanwhile, China is silk big country in the world, and the waste silk in production and waste cocoon can prepare fibroin peptide chain.Fibroin/modified polylactic acid material is all with a wide range of applications in fields such as bio-medical material, textile materials, plastics and coating.
Summary of the invention:
The object of the invention is the preparation method and the performance Problems existing that overcome above-mentioned existing fibroin/polylactic acid blend, fibroin and poly(lactic acid) is adopted to be raw material, preparation poly(lactic acid)/fibroin blending thing material, there is provided a kind of preparation method of fibroin/polylactic acid coblended matter material, the blend of gained has good processing characteristics, mechanical property and other performances.
Realize the technical scheme that the object of the invention adopts as follows:
A kind of fibroin gathers/preparation method of lactic acid blend, the present invention take hexafluoroisopropanol as solvent, fibroin (SF) and poly(lactic acid) (PLA) are raw material, with the multipolymer (PSFLA) of fibroin and poly(lactic acid) for expanding material, adopt solution blending process, preparation PLA/SF blend material, gained blend component comprises the fibroin of 0.1 ~ 99.9% weight and the poly(lactic acid) of 99.9 ~ 0.1% weight, and the consumption of expanding material (PSFLA) is 0.01 ~ 100.0% of poly(lactic acid) and fibroin total mass in co-mixing system.
Described fibroin and the step of preparation process of polylactic acid blend comprise: added by fibroin in hexafluoroisopropanol, stir, dissolve completely to fibroin at 20 ~ 60 DEG C of constant temperature.The poly(lactic acid) being 0.1 ~ 99.9% by the massfraction occupying fibroin/polylactic acid blend adds in this solution, and at 20 ~ 60 DEG C, constant temperature stirs, and dissolves completely to poly(lactic acid).Finally add fibroin and copolymer of poly lactic acid (PSFLA), its consumption is 0.01 ~ 100.0% of poly(lactic acid) and fibroin total mass in co-mixing system, at 20 ~ 60 DEG C, constant temperature stirs, dissolve completely to PSFLA, obtain the fibroin/polylactic acid blend solution containing PSFLA.The mass concentration of the hexafluoroisopropanol solution of fibroin and polylactic acid blend is 0.1 ~ 40%.By this blend solution normal pressure or vacuum-drying 0.5 ~ 24 hour at 20 ~ 150 DEG C, reclaim hexafluoroisopropanol, obtain the blend of poly(lactic acid) and silk fibroin.The blend of gained is through granulation and after vacuum-drying, obtain fibroin/polylactic acid coblended matter material.
Further, described fibroin and poly(lactic acid) mixing solutions also can adopt the following step to prepare: fibroin, poly(lactic acid), expanding material (PSFLA) are added in proportion in hexafluoroisopropanol simultaneously, be heated to constant temperature after certain temperature, to dissolving completely, obtain fibroin/polylactic acid blend solution.
Further, described fibroin and poly(lactic acid) mixing solutions also can adopt the following step to prepare: fibroin, poly(lactic acid), expanding material (PSFLA) are dissolved in respectively in hexafluoroisopropanol, again the fibroin solutions of gained, PLA solution are mixed with the hexafluoroisopropanol solution of expanding material PSFLA, obtain fibroin/polylactic acid blend solution.
Further, described fibroin and poly(lactic acid) mixing solutions also can adopt the following step to prepare: fibroin powder, PSFLA add in hexafluoroisopropanol simultaneously, the swelling certain hour of heated constant temperature or dissolve after, add poly(lactic acid) again, constant temperature dissolves completely to fibroin, poly(lactic acid), PSFLA, obtains fibroin/polylactic acid blend solution.
Further, described fibroin and poly(lactic acid) mixing solutions also can adopt the following step to prepare: fibroin powder, poly(lactic acid) are added in hexafluoroisopropanol simultaneously, the swelling certain hour of heated constant temperature or dissolve after, add PSFLA again, constant temperature dissolves completely to fibroin, poly(lactic acid), PSFLA, obtains fibroin/polylactic acid blend solution.
Further, described fibroin and poly(lactic acid) mixing solutions also can adopt the following step to prepare: poly(lactic acid), PSFLA are added in hexafluoroisopropanol simultaneously, the swelling certain hour of heated constant temperature or dissolve after, add fibroin again, constant temperature dissolves completely to fibroin, poly(lactic acid), PSFLA, obtains fibroin/polylactic acid blend solution.
Further, the expanding material of described fibroin and polylactic acid blend is fibroin and copolymer of poly lactic acid (PSFLA).This multipolymer can adopt following technique to prepare: with rac-Lactide, fibroin protein for raw material, and with stannous octoate/naphthalene disulfonic acid system for catalyzer, ring-opening polymerization obtains fibroin/copolymer of poly lactic acid (PSFLA).Containing silk fibroin segment and polylactic acid chain segment in PSFLA molecular chain, the consistency between fibroin and poly(lactic acid) two components can be improved, improve the performance of blend.
Further, described poly(lactic acid) is homopolymer, the multipolymer of Pfansteihl and D-ALPHA-Hydroxypropionic acid, or the blend of arbitrary proportion between poly(lactic acid) homopolymer, between poly(lactic acid) homopolymer and multipolymer.
Further, described fibroin can be fibrous, Powdered, that sheet, bulk etc. are different forms, and the relative molecular mass of fibroin is 1000 ~ 300000.
Further, the methods such as described fibroin and polylactic acid blend solution can be taked to be coated with, flow casting molding, extrusion moulding are carried out shaping.
Further, the hexafluoroisopropanol waste liquid that production process produces, can reclaiming, thus reduces production cost and environmental pollution.
The present invention adopts the mode of solution blending to prepare fibroin and polylactic acid blend, and technique is simple, and fibroin abundant raw material source, forming method are simple.The features such as fibroin of the present invention and polylactic acid coblended matter material have even structure, cost is low, physical strength is high, good moldability, environmental pollution are little, environmentally degradable.
Embodiment:
Below in conjunction with specific embodiment, technical scheme of the present invention is described further.According to following embodiment, the present invention may be better understood.But concrete material proportion, processing condition and result thereof described by embodiment are only for illustration of the present invention, and embodiment not limits scope of the present invention.
Embodiment 1:
5 parts of silk fibroin powders are added in 50 parts of hexafluoroisopropanols, be warming up to 50 DEG C and dissolve 10 and littlely to dissolve completely up to fibroin, adding 15 parts of number average mol weights is again the poly (l-lactic acid) (PLLA) of 80,000,0.02 part of poly(lactic acid) and fibroin copolymer compatibilizing agent (PSFLA), continue to be stirred to PLLA, fibroin, PSFLA dissolve completely, obtain blended liquid.Be coated with on constant temp. heating sheet glass by this blended liquid and scrape film forming, be evaporated to gel at normal temperatures and pressures, the blend film of gained, 50 DEG C of vacuum-dryings 10 hours, obtains fibroin/poly (l-lactic acid) blend material.
Embodiment 2:
1 part of silk fibroin powder is added in 50 parts of hexafluoroisopropanols, be warming up to 50 DEG C and dissolve 5 and littlely to dissolve completely up to fibroin, add poly (l-lactic acid) (PLLA), 0.02 part of expanding material (PSFLA) that 1 part of number average mol weight is 80,000 again, continue to be stirred to PLLA, fibroin, PSFLA dissolve completely, obtain blended liquid.This blended liquid is coated with on constant temp. heating sheet glass and scrapes film forming, be evaporated to gel at normal temperatures and pressures.Gained blend membrane, 60 DEG C of vacuum-dryings 10 hours, obtains fibroin/poly (l-lactic acid) blend.
Embodiment 3:
19 parts of silk fibroin powders are added in 50 parts of hexafluoroisopropanols, be warming up to 30 DEG C and dissolve 100 and littlely to dissolve completely up to fibroin, adding 1 part of number average mol weight is again the poly (l-lactic acid) (PLLA) of 80,000,0.2 part of poly(lactic acid) and fibroin copolymer compatibilizing agent (PSFLA), continue to be stirred to PLLA, fibroin, PSFLA dissolve completely, obtain blended liquid.This blended liquid is coated with on constant temp. heating sheet glass and scrapes film forming, be evaporated to gel at normal temperatures and pressures.The blend membrane of gained, 50 DEG C of vacuum-dryings 24 hours, obtains fibroin/poly (l-lactic acid) blend material.
Embodiment 4:
2 parts of silk fibroin powders are added in 100 parts of hexafluoroisopropanols, be warming up to 50 DEG C and dissolve 5 and littlely to dissolve completely up to fibroin, adding 38 parts of number average mol weights is again the poly (l-lactic acid) (PLLA) of 80,000,0.004 part of poly(lactic acid) and fibroin copolymer compatibilizing agent (PSFLA), continue to be stirred to PLLA, fibroin, PSFLA dissolve completely, obtain blended liquid.This blended liquid is evaporated to gel at normal temperatures and pressures.The blend membrane of gained, 60 DEG C of vacuum-dryings 10 hours, obtains fibroin/poly (l-lactic acid) blend material.
Embodiment 5:
1 part of silk fibroin powder is added in 50 parts of hexafluoroisopropanols, under agitation be warming up to 50 DEG C and swelling 5 littlely dissolve completely up to fibroin, then 60 DEG C are warming up to, add the poly (l-lactic acid) (PLLA) that 1 part of number average mol weight is 30,000 again, continuation constant temperature is stirred to PLLA and dissolves completely, add 0.1 part of expanding material PSFLA again, continue to be stirred to PLLA, fibroin and PSFLA and dissolve completely, obtain PLLA/SF blended liquid.This blend solution is evaporated to gel at normal temperatures and pressures, extrusion moulding, by extrudate 50 DEG C of vacuum-dryings 10 hours, obtains fibroin/polylactic acid coblended matter material.
Embodiment 6:
19 parts of silk fibroin powders are added in 50 parts of hexafluoroisopropanols, under agitation be warming up to 60 DEG C and swelling 20 littlely dissolve completely up to fibroin, then 60 DEG C are warming up to, add the poly (l-lactic acid) (PLLA) that 1 part of number average mol weight is 30,000 again, continuation constant temperature is stirred to PLLA and dissolves completely, add 8 parts of expanding material PSFLA again, continue to be stirred to PLLA, fibroin and PSFLA and dissolve completely, obtain PLLA/SF blended liquid.This blend solution is evaporated to gel at normal temperatures and pressures, extrusion moulding, by extrudate 50 DEG C of vacuum-dryings 10 hours, obtains fibroin/polylactic acid coblended matter material.
Embodiment 7:
10 parts of silk fibroin powders are added in 50 parts of hexafluoroisopropanols, under agitation be warming up to 55 DEG C and swelling 9 littlely dissolve completely up to fibroin, add the poly (l-lactic acid) (PLLA) that 10 parts of number average mol weights are 30,000 again, continuation constant temperature is stirred to PLLA and dissolves completely, add 1 part of expanding material PSFLA again, continue to be stirred to PLLA, fibroin and PSFLA to dissolve completely, obtain PLLA/SF blended liquid.This blend solution is evaporated to gel at normal temperatures and pressures, then 50 DEG C of vacuum-dryings 10 hours, obtains fibroin/polylactic acid coblended matter material.
Embodiment 8:
1 part of silk fibroin powder is added in 20 parts of hexafluoroisopropanols, is under agitation warming up to 45 DEG C and dissolves completely to fibroin.By 1 part of number average mol weight be 100,000 poly (l-lactic acid) (PLLA) add in 20 parts of hexafluoroisopropanols, be under agitation warming up to 50 DEG C and dissolve completely to PLLA.0.1 part of expanding material PSFLA is added in 10 parts of hexafluoroisopropanols, is under agitation warming up to 50 DEG C and dissolves completely to PSFLA.The fibroin solutions of gained, PLLA solution, PSFLA are mixed, obtains PLLA/SF blended liquid.This blend solution is evaporated to gel at normal temperatures and pressures, then 150 DEG C of vacuum-dryings 0.5 hour, obtains fibroin/polylactic acid coblended matter material.
Embodiment 9:
10 parts of silk fibroin powders are added in 30 parts of hexafluoroisopropanols, is under agitation warming up to 50 DEG C and dissolves completely to fibroin.By 10 parts of number average mol weights be 100,000 poly (l-lactic acid) (PLLA) add in 15 parts of hexafluoroisopropanols, be under agitation warming up to 50 DEG C and dissolve completely to PLLA.1 part of expanding material PSFLA is added in 5 parts of hexafluoroisopropanols, is under agitation warming up to 50 DEG C and dissolves completely to PSFLA.The fibroin solutions of gained, PLLA solution, PSFLA are mixed, obtains PLLA/SF blended liquid.This blend solution is evaporated to gel at normal temperatures and pressures, then 150 DEG C of vacuum-dryings 0.5 hour, obtains fibroin/polylactic acid coblended matter material.
Embodiment 10:
2 parts of silk fibroin powders are added in 20 parts of hexafluoroisopropanols, is under agitation warming up to 50 DEG C and dissolves completely to fibroin.By 2 parts of number average mol weights be 100,000 poly (l-lactic acid) (PLLA) add in 10 parts of hexafluoroisopropanols, be under agitation warming up to 50 DEG C and dissolve completely to PLLA.4 parts of expanding material PSFLA are added in 20 parts of hexafluoroisopropanols, is under agitation warming up to 55 DEG C and dissolves completely to PSFLA.The fibroin solutions of gained, PLLA solution, PSFLA are mixed, obtains PLLA/SF blended liquid.This blend solution is evaporated to gel at normal temperatures and pressures, after 95 DEG C of vacuum-dryings 6 hours, obtain fibroin/polylactic acid coblended matter material.
Embodiment 11:
Be the poly (l-lactic acid) (PLLA) of 100,000 by 1 part of silk fibroin powder, 1 part of number average mol weight, 0.1 part of expanding material PSFLA adds in 50 parts of hexafluoroisopropanols simultaneously, under agitation be warming up to 50 DEG C to dissolve completely to fibroin, PLLA, PSFLA, obtain PLLA/SF blended liquid.This blend solution is evaporated to gel at normal temperatures and pressures, by the extrusion moulding of PLLA/SF blended liquid, by extrudate 50 DEG C of vacuum-dryings 10 hours, obtains fibroin/polylactic acid coblended matter material.
Embodiment 12:
Be the poly (l-lactic acid) (PLLA) of 100,000 by 10 parts of silk fibroin powders, 10 parts of number average mol weights, 1 part of expanding material PSFLA adds in 50 parts of hexafluoroisopropanols simultaneously, under agitation be warming up to 55 DEG C to dissolve completely to fibroin, PLLA, PSFLA, obtain PLLA/SF blended liquid.This blend solution is evaporated to gel at normal temperatures and pressures, then 100 DEG C of vacuum-dryings 3 hours, obtains fibroin/polylactic acid coblended matter material.
Embodiment 13:
Be the poly (l-lactic acid) (PLLA) of 200,000 by 2 parts of silk fibroin powders, 2 parts of number average mol weights, 4 parts of expanding material PSFLA add in 50 parts of hexafluoroisopropanols simultaneously, under agitation be warming up to 55 DEG C to dissolve completely to fibroin, PLLA, PSFLA, obtain PLLA/SF blended liquid.By PLLA/SF blended liquid 95 DEG C of vacuum-dryings 6 hours, obtain fibroin/polylactic acid coblended matter material.
Embodiment 14:
The poly (l-lactic acid) (PLLA) being 100,000 by 1 part of silk fibroin powder and 1 part of number average mol weight adds in 50 parts of hexafluoroisopropanols simultaneously, under agitation be warming up to 50 DEG C, after constant temperature dissolves 3 hours, add 0.1 part of expanding material PSFLA again, dissolve completely to silk fibroin powder, PLLA, PSFLA at 50 DEG C of constant temperature, obtain PLLA/SF blended liquid.By PLLA/SF blended liquid 50 DEG C of vacuum-dryings 15 hours, obtain fibroin/polylactic acid coblended matter material.
Embodiment 15:
The poly (l-lactic acid) (PLLA) being 100,000 by 10 parts of silk fibroin powders and 10 parts of number average mol weights adds in 50 parts of hexafluoroisopropanols simultaneously, under agitation be warming up to 50 DEG C, after constant temperature dissolves 10 hours, add 1 part of expanding material PSFLA again, dissolve completely to silk fibroin powder, PLLA, PSFLA at 50 DEG C of constant temperature, obtain PLLA/SF blended liquid.By PLLA/SF blended liquid 100 DEG C of vacuum-dryings 3 hours, obtain fibroin/polylactic acid coblended matter material.
Embodiment 16:
The poly (l-lactic acid) (PLLA) being 100,000 by 2 parts of silk fibroin powders and 2 parts of number average mol weights adds in 50 parts of hexafluoroisopropanols simultaneously, under agitation be warming up to 50 DEG C, after constant temperature dissolves 6 hours, add 4 parts of expanding material PSFLA again, dissolve completely to silk fibroin powder, PLLA, PSFLA at 55 DEG C of constant temperature, obtain PLLA/SF blended liquid.By PLLA/SF blended liquid 95 DEG C of vacuum-dryings 6 hours, obtain fibroin/polylactic acid coblended matter material.
Embodiment 17:
1 part of silk fibroin powder and 0.1 part of expanding material PSFLA are added in 50 parts of hexafluoroisopropanols simultaneously, under agitation be warming up to 50 DEG C, after constant temperature dissolves 3 hours, add the poly (l-lactic acid) (PLLA) that 1 part of number average mol weight is 100,000 again, dissolve completely to silk fibroin powder, PLLA, PSFLA at 50 DEG C of constant temperature, obtain PLLA/SF blended liquid.By PLLA/SF blended liquid 50 DEG C of vacuum-dryings 15 hours, obtain fibroin/polylactic acid coblended matter material.
Embodiment 18:
10 parts of silk fibroin powders and 1 part of expanding material PSFLA are added in 50 parts of hexafluoroisopropanols simultaneously, under agitation be warming up to 50 DEG C, after constant temperature dissolves 10 hours, add the poly (l-lactic acid) (PLLA) that 10 parts of number average mol weights are 100,000 again, dissolve completely to silk fibroin powder, PLLA, PSFLA at 55 DEG C of constant temperature, obtain PLLA/SF blended liquid.By PLLA/SF blended liquid 100 DEG C of vacuum-dryings 3 hours, obtain fibroin/polylactic acid coblended matter material.
Embodiment 19:
2 parts of silk fibroin powders and 4 parts of expanding material PSFLA are added in 50 parts of hexafluoroisopropanols simultaneously, under agitation be warming up to 54 DEG C, after constant temperature dissolves 8 hours, adding 2 parts of number average mol weights is again the poly (l-lactic acid) of 100,000, dissolve completely to silk fibroin powder, PLLA, PSFLA at 50 DEG C of constant temperature, obtain PLLA/SF blended liquid.By PLLA/SF blended liquid 95 DEG C of vacuum-dryings 6 hours, obtain fibroin/polylactic acid coblended matter material.
Embodiment 20:
By 1 part of number average mol weight be 100,000 poly (l-lactic acid) and 0.1 part of expanding material PSFLA add in 50 parts of hexafluoroisopropanols simultaneously, under agitation be warming up to 50 DEG C, after constant temperature dissolves 3 hours, add 1 part of silk fibroin powder again, dissolve completely to silk fibroin powder, PLLA, PSFLA at 50 DEG C of constant temperature, obtain PLLA/SF blended liquid.By PLLA/SF blended liquid 50 DEG C of vacuum-dryings 24 hours, obtain fibroin/polylactic acid coblended matter material.
Embodiment 21:
By 10 parts of number average mol weights be 100,000 poly (l-lactic acid) and 1 part of expanding material PSFLA add in 50 parts of hexafluoroisopropanols simultaneously, under agitation be warming up to 50 DEG C, after constant temperature dissolves 10 hours, add 10 parts of silk fibroin powders again, dissolve completely to silk fibroin powder, PLLA, PSFLA at 55 DEG C of constant temperature, obtain PLLA/SF blended liquid.By PLLA/SF blended liquid 100 DEG C of vacuum-dryings 3 hours, obtain fibroin/polylactic acid coblended matter material.
Embodiment 22:
By 2 parts of number average mol weights be 100,000 poly (l-lactic acid) and 4 parts of expanding material PSFLA add in 50 parts of hexafluoroisopropanols simultaneously, under agitation be warming up to 50 DEG C, after constant temperature dissolves 8 hours, add 2 parts of silk fibroin powders again, dissolve completely to silk fibroin powder, PLLA, PSFLA at 50 DEG C of constant temperature, obtain PLLA/SF blended liquid.By PLLA/SF blended liquid 95 DEG C of vacuum-dryings 6 hours, obtain fibroin/polylactic acid coblended matter material.
Embodiment 23:
Be the poly (l-lactic acid) of 100,000 by the useless silk after 1 part of purifying, 1 part of number average mol weight, 0.1 part of expanding material PSFLA adds in 50 parts of hexafluoroisopropanols simultaneously, under agitation be warming up to 50 DEG C, constant temperature dissolves completely to silk, PLLA, PSFLA, obtains PLLA/SF blended liquid.By PLLA/SF blended liquid 50 DEG C of vacuum-dryings 15 hours, obtain fibroin/polylactic acid coblended matter material.
Embodiment 24:
Useless silk after 10 parts of purifying and 1 part of expanding material PSFLA are added in 50 parts of hexafluoroisopropanols simultaneously, under agitation be warming up to 50 DEG C, after constant temperature dissolves 10 hours, add the poly-D that 10 parts of number average mol weights are 100,000 again, Pfansteihl, dissolve completely to silk fibroin powder, PLLA, PSFLA at 55 DEG C of constant temperature, obtain PLLA/SF blended liquid.By PLLA/SF blended liquid 100 DEG C of vacuum-dryings 1 hour, obtain fibroin/polylactic acid coblended matter material.
Embodiment 25:
Useless silk after 2 parts of purifying and 4 parts of expanding material PSFLA are added in 50 parts of hexafluoroisopropanols simultaneously, under agitation be warming up to 54 DEG C, after constant temperature dissolves 8 hours, add 2 parts of poly (l-lactic acid)s and 2 parts of poly-D again, Pfansteihl, dissolve completely to silk fibroin powder, PLLA, PSFLA at 50 DEG C of constant temperature, obtain PLLA/SF blended liquid.By PLLA/SF blended liquid 95 DEG C of vacuum-dryings 6 hours, obtain fibroin/polylactic acid coblended matter material.
Embodiment 26
10 parts of poly (l-lactic acid)s, 5 parts of sheet fibroins, 5 parts of expanding material PSFLA are added in 50 parts of hexafluoroisopropanols simultaneously, be under agitation warming up to 50 DEG C, constant temperature dissolves, and silk fibroin powder, PLLA, PSFLA dissolve completely, obtain PLLA/SF blended liquid.By the extrusion moulding of PLLA/SF blended liquid, by PLLA/SF blend 95 DEG C of vacuum-dryings 6 hours, obtain fibroin/polylactic acid coblended matter material.
Embodiment 27:
Be the poly (l-lactic acid) of 100,000 by the useless silk after 1 part of purifying, 1 part of number average mol weight, 0.1 part of expanding material PSFLA adds in 50 parts of hexafluoroisopropanols simultaneously, at 20 DEG C, constant temperature stirs 40 hours, at being warming up to 50 DEG C again, constant temperature dissolves completely to silk, PLLA, PSFLA, obtains PLLA/SF blended liquid.By PLLA/SF blended liquid 50 DEG C of vacuum-dryings 24 hours, obtain fibroin/polylactic acid coblended matter material.
Claims (10)
1. a blend for fibroin and poly (l-lactic acid), is characterized in that: in described blend, and the mass content of fibroin is 0.1 ~ 99.9%, and the mass content of poly(lactic acid) is 99.9 ~ 0.1%.
2. fibroin according to claim 1 and polylactic acid blend, is characterized in that: in fibroin and polylactic acid blend, with the addition of expanding material.This expanding material is the multipolymer (PSFLA) of fibroin and poly(lactic acid), containing silk fibroin segment and polylactic acid chain segment in its molecular chain.In fibroin and polylactic acid blend, add PSFLA, the fibroin in increase blend and the consistency between poly(lactic acid), improve the performance of fibroin and polylactic acid blend material.
3. the expanding material of fibroin according to claim 2 and polylactic acid blend, it is characterized in that: this expanding material is the multipolymer (PSFLA) of fibroin and poly(lactic acid), following technique is adopted to prepare: with rac-Lactide, silk fibroin for raw material, with stannous octoate/naphthalene disulfonic acid system for catalyzer, ring-opening polymerization obtains fibroin/copolymer of poly lactic acid (PSFLA).
4. fibroin according to claim 1 and polylactic acid blend, is characterized in that: the consumption of expanding material (PSFLA) is 0.01 ~ 100.0% of poly(lactic acid) and fibroin total mass in blend.
5. fibroin according to claim 1 and polylactic acid blend, is characterized in that: realize with the following step: first add in hexafluoroisopropanol by fibroin, is heated to 20 ~ 60 DEG C, and constant temperature is stirred to fibroin dissolves completely; Then add poly(lactic acid), constant temperature is stirred to poly(lactic acid) and dissolves completely; Finally add fibroin and copolymer of poly lactic acid (PSFLA), constant temperature is stirred to PSFLA and dissolves completely, finally obtains the fibroin/polylactic acid blend solution containing expanding material PSFLA.By this blend solution 20 ~ 150 DEG C of normal pressures or vacuum-drying 0.5 ~ 24 hour, obtain the blend of poly(lactic acid) and silk fibroin.The blend of gained is through granulation and after vacuum-drying, obtain fibroin/polylactic acid coblended matter material.
6. fibroin according to claim 1 and polylactic acid blend, it is characterized in that: described fibroin and poly(lactic acid) mixing solutions also can adopt following five kinds of modes to prepare: 1) add in hexafluoroisopropanol solution by fibroin, poly(lactic acid), fibroin and copolymer of poly lactic acid (PSFLA) simultaneously, constant temperature after being heated to 20 ~ 60 DEG C, dissolve completely to fibroin, poly(lactic acid), PSFLA, obtain blend solution.2) or by fibroin, poly(lactic acid), PSFLA be dissolved in hexafluoroisopropanol respectively, then the hexafluoroisopropanol solution of the hexafluoroisopropanol solution of the hexafluoroisopropanol solution of the fibroin of gained, poly(lactic acid), PSFLA is mixed, obtain blend solution.3) or by fibroin powder, PSFLA add in hexafluoroisopropanol simultaneously, after being heated to 20 ~ 60 DEG C, after swelling certain hour or completely dissolving, then add poly(lactic acid), constant temperature dissolves completely to fibroin, poly(lactic acid), PSFLA, obtains fibroin/polylactic acid blend solution.4) or by fibroin powder, poly(lactic acid) add in hexafluoroisopropanol simultaneously, after being heated to 20 ~ 60 DEG C, the swelling certain hour of constant temperature or after dissolving, then adds PSFLA, constant temperature dissolves completely to fibroin, poly(lactic acid), PSFLA, obtains fibroin/polylactic acid blend solution.5) or by poly(lactic acid), PSFLA add in hexafluoroisopropanol simultaneously, after being heated to 20 ~ 60 DEG C, the swelling certain hour of constant temperature or after dissolving, then adds fibroin, constant temperature dissolves completely to fibroin, poly(lactic acid), PSFLA, obtains fibroin/polylactic acid blend solution.
7. fibroin according to claim 1 and polylactic acid blend, is characterized in that: described fibroin can be the forms such as fiber, powder, thin slice or bulk, and its relative molecular mass is 1000 ~ 300000.
8. fibroin according to claim 1 and polylactic acid blend, is characterized in that: poly(lactic acid) be the homopolymer of Pfansteihl and D-ALPHA-Hydroxypropionic acid, multipolymer or these they between blend.
9. claim 5 and described fibroin and polylactic acid blend solution, is characterized in that: the concentration of the fibroin of gained and the hexafluoroisopropanol blend solution of poly(lactic acid) is 0.1 ~ 40%.
10. fibroin according to claim 1 and polylactic acid blend, is characterized in that: described fibroin and polylactic acid blend solution can be taked to extrude, curtain coating, coating process carry out shaping.Mold compound can be prepared into fibroin and polylactic acid blend pellet further.
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