CN104530670A - Fibroin/polylactic acid blend material and melt-blending preparation method thereof - Google Patents
Fibroin/polylactic acid blend material and melt-blending preparation method thereof Download PDFInfo
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- CN104530670A CN104530670A CN201410814946.1A CN201410814946A CN104530670A CN 104530670 A CN104530670 A CN 104530670A CN 201410814946 A CN201410814946 A CN 201410814946A CN 104530670 A CN104530670 A CN 104530670A
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Abstract
The invention belongs to the technical field of high polymer materials. The invention discloses a fibroin/polylactic acid blend material, wherein the mass content of fibroins in the blend is 0.1-99.9%, and the mass content of polylactic acid is 99.9-0.1%; the copolymer (PSFLA) of fibroins and polylactic acid is added in the blend as a compatibilizer; the molecular chains of the compatibilizer contain silk fibroin chain segments and polylactic acid chain segments, thus the compatibility between the fibroin component and the polylactic acid component can be improved; the dosage of the compatibilizer is 0.01-100.0% of the total mass of the fibroins and the polylactic acid; the fibroins, the polylactic acid and the PSFLA are mixed together, heated until the polylactic acid is completely melted, and subjected to extrusion granulation to obtain the fibroin/polylactic acid blend material. The fibroin raw material can be in the shape of fibres, powder, slices, blocks and the like prepared from silk, and the polylactic acid can be a homopolymer or a copolymer or the blend thereof.
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 (l-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.
At present, 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, biocompatibility, the cellular affinity of poly-lactic acid material, control the degradation speed (ZL200810242819.3 of 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 Applied Polymer Science, 2009,113:2675 ~ 2682; Journalof 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)., there is the problems such as component mixing is uneven, interface defectiveness, solvent removal, environmental pollution, cause the performance of blend material, cost etc. to be difficult to meet the demands in the fibroin/polylactic acid coblended matter material adopting solution blending mode to prepare.
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.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, fibroin of the present invention (SF) and poly(lactic acid) (PLA) are raw material, with the multipolymer (PSFLA) of fibroin protein and poly(lactic acid) for expanding material, adopt melt-mixing method, 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 comprises with the step of preparation process of polylactic acid blend: fibroin, poly(lactic acid), fibroin are mixed in high-speed mixer with copolymer of poly lactic acid (PSFLA), then be heated to poly(lactic acid) melting, stir and obtain the blend of poly(lactic acid) and silk fibroin.By the blend of gained after forcing machine granulation, obtain fibroin/polylactic acid coblended matter material.
Further, described fibroin and polylactic acid blend also can adopt the following step to prepare: fibroin, poly(lactic acid), expanding material PSFLA are added in forcing machine simultaneously, more than higher than the melt temperature of poly(lactic acid), extruding pelletization, obtains fibroin/polylactic acid coblended matter material.
Further, described fibroin and polylactic acid blend also can adopt the following step to prepare: fibroin, poly(lactic acid), fibroin are carried out high-speed mixing, the blend composition of gained, after forcing machine granulation, obtains fibroin/polylactic acid coblended matter material.
Further, the expanding material of described fibroin and polylactic acid blend is fibroin and copolymer of poly lactic acid (PSFLA), containing silk fibroin segment and polylactic acid chain segment in the molecular chain of this multipolymer, the consistency between fibroin and poly(lactic acid) two components can be improved, improve the performance of blend.PSFLA can adopt following technique to prepare: with rac-Lactide, silk fibroin for raw material, and with stannous octoate/naphthalene disulfonic acid system for catalyzer, ring-opening polymerization obtains fibroin/copolymer of poly lactic acid (PSFLA).
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, it is shaping that described fibroin and polylactic acid blend can take the method such as extrusion moulding, injection moulding to carry out.
The present invention adopts the mode of melt 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:
Be that the poly (l-lactic acid) (PLLA) of 80,000,0.2 part of poly(lactic acid) and fibroin copolymer compatibilizing agent (PSFLA) add in homogenizer by 10 parts of silk fibroin powders, 190 parts of number average mol weights, stir after 2 hours, obtain PLLA, fibroin, PSFLA compound.By this mixed material heating to 180 DEG C, PLLA melting, after stirring, cooling is also broken, obtains fibroin/poly (l-lactic acid) blend.By this blend extruding pelletization, obtain fibroin/poly (l-lactic acid) blend pellet.The tensile strength of this fibroin/poly (l-lactic acid) blend is 4.05MPa, and maximum elongation at break is 35.82%.
Embodiment 2:
Be that the poly (l-lactic acid) (PLLA) of 80,000,1.0 parts of poly(lactic acid) and fibroin copolymer compatibilizing agent (PSFLA) add in homogenizer by 50 parts of silk fibroin powders, 50 parts of number average mol weights, stir after 1 hour, obtain PLLA, fibroin, PSFLA compound, again by this mixed material heating to 185 DEG C, PLLA melting, after stirring, cooling is also broken, obtains fibroin/poly (l-lactic acid) blend.By this blend extruding pelletization, obtain fibroin/poly (l-lactic acid) blend pellet.The tensile strength of this fibroin/poly (l-lactic acid) blend is 4.15MPa, and maximum elongation at break is 40.35%.
Embodiment 3:
190 parts of silk fibroin powders, 10 parts of poly (l-lactic acid)s (PLLA), 2 parts of expanding materials (PSFLA) are added in homogenizer, stir after 2 hours, by the PLLA of gained, fibroin, PSFLA mixed material heating to 190 DEG C, PLLA melting, after stirring, cooling is also broken, obtains fibroin/poly (l-lactic acid) blend.By this blend extruding pelletization, obtain fibroin/poly (l-lactic acid) blend pellet.The tensile strength of this fibroin/poly (l-lactic acid) blend is 4.36MPa, and maximum elongation at break is 60.13%.
Embodiment 4:
After 10 parts of silk fibroin powders, 190 parts of poly (l-lactic acid)s, 0.02 part of expanding material (PSFLA) are simply mixed, add in forcing machine, extruding pelletization simultaneously, obtain fibroin/poly (l-lactic acid) blend pellet.The tensile strength of this fibroin/poly (l-lactic acid) blend is 4.00MPa, and maximum elongation at break is 35.11%.
Embodiment 5:
Be the poly (l-lactic acid) of 30,000 by 50 parts of silk fibroin powders, 50 parts of number average mol weights, after 5 parts of poly(lactic acid) simply mix with fibroin copolymer compatibilizing agent (PSFLA), add in forcing machine simultaneously, extruding pelletization, obtains fibroin/poly (l-lactic acid) blend pellet.The tensile strength of this blend is 4.85MPa, and maximum elongation at break is 72.36%.
Embodiment 6:
Be the poly (l-lactic acid) (PLLA) of 30,000 by 100 parts of silk fibroin powders, 50 parts of number average mol weights, after 1 part of poly(lactic acid) simply mixes with fibroin copolymer compatibilizing agent (PSFLA), add in forcing machine simultaneously, extruding pelletization, obtains fibroin/poly (l-lactic acid) blend pellet.The tensile strength of this fibroin/poly (l-lactic acid) blend is 4.35MPa, and maximum elongation at break is 56.48%.
Embodiment 7:
Be that the poly (l-lactic acid) of 100,000,20 parts of expanding materials (PSFLA) are through high-speed mixer by 20 parts of silk fibroin powders, 80 parts of number average mol weights, mix after 2 hours, compound adds extruding pelletization in forcing machine, obtains fibroin/poly (l-lactic acid) blend pellet.The intensity of stretching of this blend is 4.86MPa, and maximum elongation at break is 78.32%.
Embodiment 8:
Be that the poly (l-lactic acid) of 100,000,100 parts of expanding materials (PSFLA) are through high-speed mixer by 50 parts of silk fibroin powders, 50 parts of number average mol weights, mix after 3 hours, compound adds extruding pelletization in forcing machine, obtains the blended material of fibroin/poly (l-lactic acid).The tensile strength of this fibroin/poly (l-lactic acid) blend is 4.80MPa, and maximum elongation at break is 73.42%.
Embodiment 9:
Be that the poly (l-lactic acid) of 100,000,5 parts of poly(lactic acid) and fibroin copolymer compatibilizing agent (PSFLA) are through high-speed mixer by 10 parts of silk fibroin powders, 90 parts of number average mol weights, mix after 1 hour, compound adds extruding pelletization in forcing machine, obtains fibroin/poly (l-lactic acid) blend pellet.The tensile strength of this fibroin/poly (l-lactic acid) blend is 5.02MPa, and maximum elongation at break is 81.64%.
Embodiment 10:
Be the poly-D of 150,000 by 50 parts of silk fibroin powders, 100 parts of number average mol weights, Pfansteihl (PDLLA), 6 parts of poly(lactic acid) and fibroin copolymer compatibilizing agent (PSFLA) are through high-speed mixer, mix after 0.5 hour, compound adds extruding pelletization in forcing machine, obtains fibroin/polylactic acid blend pellet.The tensile strength of this fibroin/polylactic acid blend is 5.02MPa, maximum elongation at break 92.13%.
Embodiment 11:
Be the poly (l-lactic acid) (PLLA) of 100,000 by 20 parts of useless silk short fibers, 80 parts of number average mol weights, 6.5 parts of expanding material PSFLA mix 1 hour through high-speed mixer, compound adds forcing machine extruding pelletization, obtains fibroin/polylactic acid blend pellet.The tensile strength of this fibroin/polylactic acid blend is 5.24MPa, maximum elongation at break 112.30%.
Embodiment 12:
Be that the poly (l-lactic acid) (PLLA) of 100,000,5 parts of expanding material PSFLA are after high-speed mixer mixes 1 hour by 50 parts of useless silk short fibers, 50 parts of number average mol weights, compound adds extruding pelletization in forcing machine, obtains fibroin/polylactic acid blend pellet.The tensile strength of this blend is 4.96MPa, maximum elongation at break 84.20%.
Embodiment 13:
Be that the poly (l-lactic acid) (PLLA) of 100,000,10 parts of expanding material PSFLA are after high-speed mixer mixes 1 hour by 20 parts of useless silk short fibers, 80 parts of number average mol weights, compound adds extruding pelletization in forcing machine, obtains fibroin/polylactic acid blend pellet.The tensile strength of this blend is 4.79MPa, maximum elongation at break 68.80%.
Embodiment 14:
By 60 parts of useless silk short fibers, 40 parts of number average mol weights be the poly (l-lactic acid) of 100,000,8 parts of expanding material PSFLA after high-speed mixer mixes 1.5 hours, compound adds extruding pelletization in forcing machine, obtains fibroin/polylactic acid blend pellet.The tensile strength of this fibroin/poly (l-lactic acid) blend is 4.00MPa, maximum elongation at break 35.82%.
Embodiment 15:
Be the poly (l-lactic acid) (PLLA) of 100,000 by 20 parts of silk fibroin powders, 50 parts of number average mol weights, 50 parts of number average mol weights be 100,000 poly-D, Pfansteihl (PDLLA), 3 parts of expanding material PSFLA are after high-speed mixer mixes 0.5 hour, compound adds extruding pelletization in forcing machine, obtains fibroin/polylactic acid blend pellet.The tensile strength of this fibroin/polylactic acid blend is 4.96MPa, and maximum elongation at break is 78.12%.
Claims (9)
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, it is characterized in that: realize with the following step: first fibroin, poly(lactic acid), fibroin and copolymer of poly lactic acid (PSFLA) are carried out high-speed mixing, then be heated to poly(lactic acid) melting, mix the blend obtaining poly(lactic acid) and silk fibroin.The blend of gained, after forcing machine granulation, obtains 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 manner to prepare: 1) fibroin, poly(lactic acid), PSFLA are added in forcing machine simultaneously, be heated to above more than the melt temperature of poly(lactic acid), extruding pelletization, obtains fibroin/polylactic acid coblended matter material.2) or by fibroin, poly(lactic acid), fibroin carry out high-speed mixing, the blend composition of gained, after forcing machine granulation, obtains fibroin/polylactic acid coblended matter material.
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, 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. fibroin according to claim 1 and polylactic acid blend, is characterized in that: it is shaping that fibroin and polylactic acid blend can take the method such as extrusion moulding, injection moulding to carry out.
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| CN105133117A (en) * | 2015-07-07 | 2015-12-09 | 宁波武田纺织有限公司 | Method for preparing high-elastic wrap yarn |
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| CN105970344A (en) * | 2016-05-13 | 2016-09-28 | 东莞市联洲知识产权运营管理有限公司 | Fibroin polylactic acid fiber containing silk fibroin modified polylactic acid |
| CN105970344B (en) * | 2016-05-13 | 2018-07-20 | 广州迪柯尼服饰股份有限公司 | A kind of fibroin acid fiber by polylactic of the polydactyl acid containing fibroin albumen |
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| CN113773624A (en) * | 2021-09-14 | 2021-12-10 | 中南大学 | Polylactic acid blending modified material and preparation method thereof |
| CN114045038A (en) * | 2021-12-31 | 2022-02-15 | 广东工业大学 | Cottonseed protein composite material and preparation method and application thereof |
| CN114045038B (en) * | 2021-12-31 | 2022-05-03 | 广东工业大学 | Cottonseed protein composite material and preparation method and application thereof |
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