CN106435818A - Gelatin-based regenerated silk protein fibers and preparation method thereof - Google Patents
Gelatin-based regenerated silk protein fibers and preparation method thereof Download PDFInfo
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- CN106435818A CN106435818A CN201610839813.9A CN201610839813A CN106435818A CN 106435818 A CN106435818 A CN 106435818A CN 201610839813 A CN201610839813 A CN 201610839813A CN 106435818 A CN106435818 A CN 106435818A
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- gelatin
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- 108010010803 Gelatin Proteins 0.000 title claims abstract description 129
- 239000008273 gelatin Substances 0.000 title claims abstract description 129
- 229920000159 gelatin Polymers 0.000 title claims abstract description 129
- 235000019322 gelatine Nutrition 0.000 title claims abstract description 129
- 235000011852 gelatine desserts Nutrition 0.000 title claims abstract description 129
- 239000000835 fiber Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 108090000623 proteins and genes Proteins 0.000 title abstract description 8
- 102000004169 proteins and genes Human genes 0.000 title abstract description 8
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 31
- 238000009987 spinning Methods 0.000 claims abstract description 23
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims abstract description 22
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 238000012545 processing Methods 0.000 claims abstract description 3
- 108010022355 Fibroins Proteins 0.000 claims description 142
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 45
- 238000003756 stirring Methods 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000000499 gel Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 20
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical group O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 14
- 235000015110 jellies Nutrition 0.000 claims description 10
- 239000008274 jelly Substances 0.000 claims description 10
- 229940059936 lithium bromide Drugs 0.000 claims description 10
- 238000001891 gel spinning Methods 0.000 claims description 4
- 238000007711 solidification Methods 0.000 claims description 3
- 230000008023 solidification Effects 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 80
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 239000004744 fabric Substances 0.000 abstract description 2
- 239000012460 protein solution Substances 0.000 abstract 2
- 238000000502 dialysis Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 238000010041 electrostatic spinning Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 4
- 239000004753 textile Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 210000000845 cartilage Anatomy 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000018102 proteins Nutrition 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical group CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- SQDAZGGFXASXDW-UHFFFAOYSA-N 5-bromo-2-(trifluoromethoxy)pyridine Chemical compound FC(F)(F)OC1=CC=C(Br)C=N1 SQDAZGGFXASXDW-UHFFFAOYSA-N 0.000 description 1
- 241000255789 Bombyx mori Species 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical group [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920001287 Chondroitin sulfate Polymers 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 description 1
- 239000001354 calcium citrate Substances 0.000 description 1
- 229940059329 chondroitin sulfate Drugs 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 230000005847 immunogenicity Effects 0.000 description 1
- 210000003041 ligament Anatomy 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- YWIVKILSMZOHHF-QJZPQSOGSA-N sodium;(2s,3s,4s,5r,6r)-6-[(2s,3r,4r,5s,6r)-3-acetamido-2-[(2s,3s,4r,5r,6r)-6-[(2r,3r,4r,5s,6r)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2- Chemical compound [Na+].CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 YWIVKILSMZOHHF-QJZPQSOGSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000013337 tricalcium citrate Nutrition 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention provides gelatin-based regenerated silk protein fibers and a preparation method thereof. The preparation method comprises the following steps: degummed silk fibers are added to a lithium bromide solution and heated and stirred until the fibers are dissolved completely, and a silk protein solution is obtained after filtration, dialysis and concentration; gelatin powder is added to deionized water and heated and stirred until the gelatin powder is dissolved completely, a gelatin aqueous solution is formed, the silk protein solution and a crosslinking agent are added and stirred sufficiently, and a silk protein/gelatin solution is formed; the silk protein/gelatin solution is stirred to be gelatinous in an environment at the temperature of 5-10 DEG C, placed in spinning equipment and spun into gelatinous silk strands, and the gelatin-based regenerated silk protein fibers are obtained by soaking and processing the gelatinous silk strands in ethanol water at the temperature of 2-4 DEG C. The preparation method is simple and fast, the rapid forming property is good, and the prepared gelatin-based regenerated silk protein fibers have good mechanical property and skin-friendly performance and can be used for preparing clothing fabric.
Description
Technical field
The invention belongs to textile material technical field and in particular to a kind of regenerated fibroin fiber based on gelatin and its
Preparation method.
Background technology
Silk is a kind of natural protein fibre, is made up of 18 kinds of amino acid in fibroin, such as glycine, alanine
With serine etc., fibroin can form α spiral, β-pleated sheet and random coil structure, make fibroin albumen have water resistant dissolubility,
Antibiotic property and skin-friendly, and the mechanical property of silk fiber is determined by the structure and composition composition of fibroin.In order to fully sharp
Use fibroin resource, the research of the composite aspect based on fibroin gets more and more.
Gelatin is a kind of a kind of denaturation derivative of animal collagen, has abundance, low cost, biocompatibility
Good, the more low function of immunogenicity, therefore the composite of gelatin and fibroin preparation not only can be improved fibroin
The performance of material, and do not interfere with its environmental protection performance.
Also more with the research of the composite fibre aspect of gelatin based on fibroin.Chinese patent CN 104562438A is public
Gelatin-based micro/nano fibrous membrane material opened and its production and use, by gelatin, other biological molecule, additive, emulsifying agent
With medicine as raw material, other biological molecule can be silk-fibroin, and additive is calcium chloride, glycerine, calcium citrate etc., and emulsifying agent is
Glycerin monostearate, sorbierite or tween etc., medicine is the effective component extracts for the treatment of second third, and these raw materials are prepared shape
Become spinning solution, through sea whelk formula electrostatic spinning, spring electrostatic spinning, drum-type electrostatic spinning, screw electrostatic spinning, rotary shaft
Electrostatic spinning or the preparation of gear type electrostatic spinning form micro/nano fibrous membrane material, and the micro/nano fibrous membrane material of preparation has well
Biocompatibility, Bioabsorbable and biodegradability, can be used for biologic medical field.Chinese patent CN
Silk stent, preparation method, application and three-phase silk ligament graft, preparation method disclosed in 1035505762B, by silk
It is woven into the network with macroporous structure, more netted silk stent is divided into tough zone, cartilage area, bone to modify according to purposes
Different cells are planted in area respectively, then tough zone are modified using fibroin albumen, and cartilage area adopts gelatin, hyaluronic acid
Sodium and chondroitin sulfate are modified, and bone modified region is modified using fibroin albumen and hydroxyapatite.There is above-mentioned existing skill
Art understands, the composite being mixed with fibroin and gelatin materials at present is used for biologic medical field, in weaving clothes
Seldom, the composite prepared in addition is in the majority with planar and three-dimensional shape, fibrous composite for the application in dress field
Seldom it is difficult to apply to textile garment field.
, using gelatin and fibroin as primary raw material, auxiliary crosslinking agent and sub-cooled technology, through gel spinning for the present invention
Silk technology prepares the regenerated fibroin fiber based on gelatin so as to can apply in textile garment fabric.
Content of the invention
The technical problem to be solved in the present invention is to provide a kind of regenerated fibroin fiber based on gelatin and its preparation side
Method, will add gelatin and crosslinking agent in regenerated fibroin solution, using the gelatin feature that rapid curing is formed under low temperature,
Solve the technical problem of regenerated fibroin fiber rapid shaping, and the regenerated fibroin fiber mechanical property prepared and parent
Skin is good, can be used for preparing garment material.
For solving above-mentioned technical problem, the technical scheme is that：
A kind of regenerated fibroin fiber based on gelatin, described contains silkworm based in the regenerated fibroin fiber of gelatin
Silk-fibroin and gelatin, the described regenerated fibroin fiber stated based on gelatin adopts gel spinning process to prepare, and described stating is based on
The regenerated fibroin fiber of gelatin is based on freezing processing solidification and forms.
Preferred as technique scheme, described also contain crosslinking agent based in the regenerated fibroin fiber of gelatin,
Described crosslinking agent is glutaraldehyde and citric acid.
The present invention also provides a kind of preparation method of the regenerated fibroin fiber based on gelatin, comprises the following steps：
(1) silk fiber after degumming is added in lithium-bromide solution, at 60-65 DEG C heating stirring to being completely dissolved,
Filter, dialyse and be concentrated to give fibroin solutions；
(2) jelly powder is added in deionized water, heating stirring, to being completely dissolved formation aqueous gelatin solution, adds step
(1) fibroin solutions prepared, add crosslinking agent, are sufficiently stirred for, and form fibroin/gelatin solution；
(3) fibroin/gelatin solution preparing step (2) is placed in stirring gel in 5-10 DEG C of environment, then
It is placed in spinning equipment, forms gel strand through spinning, gelatinous strand be impregnated in place in 2-4 DEG C of ethanol water
Reason obtains the regenerated fibroin fiber based on gelatin.
Preferred as technique scheme, in described step (1), the mass fraction of fibroin solutions is 3-8%.
Preferred as technique scheme, in described step (2), the mass fraction of aqueous gelatin solution is 3-5%.
Preferred as technique scheme, in described step (2), fibroin, gelatin in fibroin/gelatin solution
Mass ratio with crosslinking agent is 10:3-5:1.
Preferred as technique scheme, in described step (2), crosslinking agent is glutaraldehyde and citric acid, described penta 2
The volume ratio of aldehyde and citric acid is 1:1.
Preferred as technique scheme, in described step (3), the speed of stirring is 250-500rpm, and the time is 3-
5min.
Preferred as technique scheme, in described step (3), the bath raio of dipping is 1:30-50.
Preferred as technique scheme, in described step (3), in ethanol water, the mass fraction of ethanol is 5-
15%, the time of process is 5-10min.
Compared with prior art, the invention has the advantages that：
(1) containing fibroin, gelatin and crosslinking agent in the regenerated fibroin fiber based on gelatin of present invention preparation,
Fibroin and gelatin are primary raw material, and fibroin and gelatin broadly fall into native protein macromolecular, can lead between the two
Cross hydrogen bond to connect, do not affect fibroin and the structure of gelatin itself, and the crosslinking agent selected is glutaraldehyde and citric acid, will
Carry out crosslinking between fibroin macromolecular, gelatin is coated the fibroin/gelatin solution wherein forming stable uniform.
(2) gelatin in the fibroin/gelatin solution of present invention preparation, through meeting gel in the environment of 5-10 DEG C, forms solidifying
Glue, is extruded into gel strand through spinning, gel strand solidify to form fiber through 2-4 DEG C of ethanol water, and ethanol
The aqueous solution also can solidify arrangement further to strand, strengthens the mechanical property of regenerated fibroin fiber.
(3) regenerated fibroin fiber based on gelatin of present invention preparation is combined the low temperature of gelatin by gel spinning technology
The rapid curing of solidification technology promotion regenerated fibroin fiber, and remain the primary characteristic of fibroin and gelatin, preparation
The regenerated fibroin fiber mechanical property based on gelatin good, pro-skin performance is good.
Specific embodiment
To describe the present invention, the illustrative examples of the here present invention and explanation below in conjunction with specific embodiment in detail
It is used for explaining the present invention, but not as a limitation of the invention.
Embodiment 1：
(1) silk fiber after the degumming of 1g is added in the lithium-bromide solution of 20ml, at 60 DEG C, heating stirring 2h is extremely
It is completely dissolved, filter, dialyse and be concentrated to give the fibroin solutions that mass fraction is 3%.
(2) jelly powder is added in deionized water, at 40 DEG C, to being completely dissolved, form mass fraction is heating stirring
3% aqueous gelatin solution, adds fibroin solutions, adds volume ratio to be 1:1 glutaraldehyde and the crosslinking agent of citric acid, fully stir
Mix, form fibroin/gelatin solution, wherein, the quality of fibroin, gelatin and crosslinking agent in fibroin/gelatin solution
Than for 10:3:1.
(3) fibroin/gelatin solution is placed in 5 DEG C of environment, with 250rpm speed stir 3min, make fibroin/
Gelatin solution gel, is subsequently placed in spinning equipment, forms gel strand through spinning, with bath raio for 1:30, by gel
The mass fraction that the strand of shape impregnated in 2 DEG C of ethanol be 5% ethanol water in process 5min, obtain based on gelatin again
Raw fibroin fiber.
Embodiment 2：
(1) silk fiber after the degumming of 1g is added in the lithium-bromide solution of 25ml, at 65 DEG C, heating stirring 4h is extremely
It is completely dissolved, filter, dialyse and be concentrated to give the fibroin solutions that mass fraction is 8%.
(2) jelly powder is added in deionized water, at 50 DEG C, to being completely dissolved, form mass fraction is heating stirring
5% aqueous gelatin solution, adds fibroin solutions, adds volume ratio to be 1:1 glutaraldehyde and the crosslinking agent of citric acid, fully stir
Mix, form fibroin/gelatin solution, wherein, the quality of fibroin, gelatin and crosslinking agent in fibroin/gelatin solution
Than for 10:5:1.
(3) fibroin/gelatin solution is placed in 10 DEG C of environment, with 500rpm speed stir 5min, make fibroin/
Gelatin solution gel, is subsequently placed in spinning equipment, forms gel strand through spinning, with bath raio for 1:50, by gel
The mass fraction that the strand of shape impregnated in 4 DEG C of ethanol be 15% ethanol water in process 10min, obtain based on gelatin
Regenerated fibroin fiber.
Embodiment 3：
(1) silk fiber after the degumming of 1g is added in the lithium-bromide solution of 22ml, at 63 DEG C, heating stirring 3h is extremely
It is completely dissolved, filter, dialyse and be concentrated to give the fibroin solutions that mass fraction is 5%.
(2) jelly powder is added in deionized water, at 45 DEG C, to being completely dissolved, form mass fraction is heating stirring
4% aqueous gelatin solution, adds fibroin solutions, adds volume ratio to be 1:1 glutaraldehyde and the crosslinking agent of citric acid, fully stir
Mix, form fibroin/gelatin solution, wherein, the quality of fibroin, gelatin and crosslinking agent in fibroin/gelatin solution
Than for 10:4:1.
(3) fibroin/gelatin solution is placed in 7 DEG C of environment, with 300rpm speed stir 4min, make fibroin/
Gelatin solution gel, is subsequently placed in spinning equipment, forms gel strand through spinning, with bath raio for 1:40, by gel
The mass fraction that the strand of shape impregnated in 3 DEG C of ethanol be 10% ethanol water in process 7min, obtain based on gelatin
Regenerated fibroin fiber.
Embodiment 4：
(1) silk fiber after the degumming of 1g is added in the lithium-bromide solution of 25ml, at 60 DEG C, heating stirring 4h is extremely
It is completely dissolved, filter, dialyse and be concentrated to give the fibroin solutions that mass fraction is 6%.
(2) jelly powder is added in deionized water, at 50 DEG C, to being completely dissolved, form mass fraction is heating stirring
3.5% aqueous gelatin solution, adds fibroin solutions, adds volume ratio to be 1:1 glutaraldehyde and the crosslinking agent of citric acid, fully
Stirring, forms fibroin/gelatin solution, wherein, the matter of fibroin, gelatin and crosslinking agent in fibroin/gelatin solution
Amount ratio is 10:3.5:1.
(3) fibroin/gelatin solution is placed in 8 DEG C of environment, with 300rpm speed stir 4min, make fibroin/
Gelatin solution gel, is subsequently placed in spinning equipment, forms gel strand through spinning, with bath raio for 1:35, by gel
The mass fraction that the strand of shape impregnated in 2 DEG C of ethanol be 8% ethanol water in process 7min, obtain based on gelatin again
Raw fibroin fiber.
Embodiment 5：
(1) silk fiber after the degumming of 1g is added in the lithium-bromide solution of 25ml, at 65 DEG C, heating stirring 3h is extremely
It is completely dissolved, filter, dialyse and be concentrated to give the fibroin solutions that mass fraction is 7%.
(2) jelly powder is added in deionized water, at 50 DEG C, to being completely dissolved, form mass fraction is heating stirring
4.5% aqueous gelatin solution, adds fibroin solutions, adds volume ratio to be 1:1 glutaraldehyde and the crosslinking agent of citric acid, fully
Stirring, forms fibroin/gelatin solution, wherein, the matter of fibroin, gelatin and crosslinking agent in fibroin/gelatin solution
Amount ratio is 10:5:1.
(3) fibroin/gelatin solution is placed in 6 DEG C of environment, with 350rpm speed stir 4min, make fibroin/
Gelatin solution gel, is subsequently placed in spinning equipment, forms gel strand through spinning, with bath raio for 1:40, by gel
The mass fraction that the strand of shape impregnated in 4 DEG C of ethanol be 8% ethanol water in process 10min, obtain based on gelatin
Regenerated fibroin fiber.
Embodiment 6：
(1) silk fiber after the degumming of 1g is added in the lithium-bromide solution of 20ml, at 65 DEG C, heating stirring 2h is extremely
It is completely dissolved, filter, dialyse and be concentrated to give the fibroin solutions that mass fraction is 5.5%.
(2) jelly powder is added in deionized water, at 50 DEG C, to being completely dissolved, form mass fraction is heating stirring
3% aqueous gelatin solution, adds fibroin solutions, adds volume ratio to be 1:1 glutaraldehyde and the crosslinking agent of citric acid, fully stir
Mix, form fibroin/gelatin solution, wherein, the quality of fibroin, gelatin and crosslinking agent in fibroin/gelatin solution
Than for 10:4.5:1.
(3) fibroin/gelatin solution is placed in 10 DEG C of environment, with 350rpm speed stir 5min, make fibroin/
Gelatin solution gel, is subsequently placed in spinning equipment, forms gel strand through spinning, with bath raio for 1:45, by gel
The mass fraction that the strand of shape impregnated in 4 DEG C of ethanol be 10% ethanol water in process 8min, obtain based on gelatin
Regenerated fibroin fiber.
Embodiment 7：
(1) silk fiber after the degumming of 1g is added in the lithium-bromide solution of 20ml, at 65 DEG C, heating stirring 4h is extremely
It is completely dissolved, filter, dialyse and be concentrated to give the fibroin solutions that mass fraction is 7.5%.
(2) jelly powder is added in deionized water, at 50 DEG C, to being completely dissolved, form mass fraction is heating stirring
4.5% aqueous gelatin solution, adds fibroin solutions, adds volume ratio to be 1:1 glutaraldehyde and the crosslinking agent of citric acid, fully
Stirring, forms fibroin/gelatin solution, wherein, the matter of fibroin, gelatin and crosslinking agent in fibroin/gelatin solution
Amount ratio is 10:4:1.
(3) fibroin/gelatin solution is placed in 10 DEG C of environment, 4.5min is stirred with 400rpm speed, makes silk egg
In vain/gelatin solution gel, is subsequently placed in spinning equipment, forms gel strand through spinning, with bath raio for 1:40, will coagulate
The mass fraction of the ethanol that gluey strand impregnated in 4 DEG C be 10% ethanol water in process 10min, obtain based on gelatin
Regenerated fibroin fiber.
Embodiment 8：
(1) silk fiber after the degumming of 1g is added in the lithium-bromide solution of 25ml, at 60 DEG C, heating stirring 3h is extremely
It is completely dissolved, filter, dialyse and be concentrated to give the fibroin solutions that mass fraction is 4%.
(2) jelly powder is added in deionized water, at 50 DEG C, to being completely dissolved, form mass fraction is heating stirring
4.5% aqueous gelatin solution, adds fibroin solutions, adds volume ratio to be 1:1 glutaraldehyde and the crosslinking agent of citric acid, fully
Stirring, forms fibroin/gelatin solution, wherein, the matter of fibroin, gelatin and crosslinking agent in fibroin/gelatin solution
Amount ratio is 10:5:1.
(3) fibroin/gelatin solution is placed in 6 DEG C of environment, with 400rpm speed stir 4min, make fibroin/
Gelatin solution gel, is subsequently placed in spinning equipment, forms gel strand through spinning, with bath raio for 1:40, by gel
The mass fraction that the strand of shape impregnated in 4 DEG C of ethanol be 5% ethanol water in process 8min, obtain based on gelatin again
Raw fibroin fiber.
After testing, the silk fibroin of the regenerated fibroin fiber based on gelatin of embodiment 1-8 preparation and prior art
Dimension, regenerated fibroin fiber (partial data with reference to Chinese document " performance study of regenerated fibroin fiber ", Lin Shaojian,
Cotton textile technology, the 18-21 page, the 8th phase of volume 39, in August, 2011) diameter, mechanical property and pro-skin performance result such as
Shown in lower：
As seen from the above table, the silk fiber of the regenerated fibroin fiber based on gelatin of present invention preparation and prior art
Compare with regenerated fibroin fiber, diameter and mechanical property close to silk fiber, better than regenerated fibroin fiber, its pro-skin
Property and degradability keep constant.
Above-described embodiment only principle of the illustrative present invention and its effect, not for the restriction present invention.Any ripe
The personage knowing this technology all can carry out modifications and changes without prejudice under the spirit and the scope of the present invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete with institute under technological thought without departing from disclosed spirit such as
All equivalent modifications becoming or change, must be covered by the claim of the present invention.
Claims (10)
1. a kind of regenerated fibroin fiber based on gelatin it is characterised in that：The described regenerated fibroin based on gelatin is fine
Fibroin and gelatin is contained, the described regenerated fibroin fiber stated based on gelatin adopts gel spinning process to prepare in dimension,
The described regenerated fibroin fiber stated based on gelatin is based on freezing processing solidification and forms.
2. a kind of regenerated fibroin fiber based on gelatin according to claim 1 it is characterised in that：Described based on bright
Also crosslinking agent is contained, described crosslinking agent is glutaraldehyde and citric acid in the regenerated fibroin fiber of glue.
3. a kind of preparation method of the regenerated fibroin fiber based on gelatin is it is characterised in that comprise the following steps：
(1) silk fiber after degumming is added in lithium-bromide solution, at 60-65 DEG C, heating stirring, to being completely dissolved, filters,
Dialyse and be concentrated to give fibroin solutions；
(2) jelly powder is added in deionized water, heating stirring, to being completely dissolved formation aqueous gelatin solution, adds step (1) system
Standby fibroin solutions, add crosslinking agent, are sufficiently stirred for, and form fibroin/gelatin solution；
(3) fibroin/gelatin solution preparing step (2) is placed in stirring gel in 5-10 DEG C of environment, is subsequently placed in
In spinning equipment, form gel strand through spinning, process in the ethanol water that gelatinous strand be impregnated in 2-4 DEG C
To the regenerated fibroin fiber based on gelatin.
4. a kind of regenerated fibroin fiber based on gelatin according to claim 3 preparation method it is characterised in that：
In described step (1), the mass fraction of fibroin solutions is 3-8%.
5. a kind of regenerated fibroin fiber based on gelatin according to claim 3 preparation method it is characterised in that：
In described step (2), the mass fraction of aqueous gelatin solution is 3-5%.
6. a kind of regenerated fibroin fiber based on gelatin according to claim 3 preparation method it is characterised in that：
In described step (2), in fibroin/gelatin solution, the mass ratio of fibroin, gelatin and crosslinking agent is 10:3-5:1.
7. a kind of regenerated fibroin fiber based on gelatin according to claim 3 preparation method it is characterised in that：
In described step (2), crosslinking agent is glutaraldehyde and citric acid, and the volume ratio of described glutaraldehyde and citric acid is 1:1.
8. a kind of regenerated fibroin fiber based on gelatin according to claim 3 preparation method it is characterised in that：
In described step (3), the speed of stirring is 250-500rpm, and the time is 3-5min.
9. a kind of regenerated fibroin fiber based on gelatin according to claim 3 preparation method it is characterised in that：
In described step (3), the bath raio of dipping is 1:30-50.
10. the preparation method of a kind of regenerated fibroin fiber based on gelatin according to claim 3, its feature exists
In：In described step (3), in ethanol water, the mass fraction of ethanol is 5-15%, and the time of process is 5-10min.
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| CN112746350A (en) * | 2020-12-17 | 2021-05-04 | 嘉兴学院 | Composite fiber with nanofiber surface modified and preparation method thereof |
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