CN109957848A - A kind of preparation method of modification regeneration fibroin fiber - Google Patents
A kind of preparation method of modification regeneration fibroin fiber Download PDFInfo
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- 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
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- 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
- D01F4/00—Monocomponent artificial filaments or the like of proteins; Manufacture thereof
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Abstract
The invention discloses a kind of preparation methods of modification regeneration fibroin fiber, belong to textile technology field.The present invention passes through first carries out degumming process to silk using sodium bicarbonate solution, oxidation processes are carried out followed by sodium hypochlorite, finally and dimethylaminoethyl methacrylate, acrylamide, styrene etc. is mixed, pass through the effect using initiator, cause polymerization, form the Block copolymer for having positive charge, simultaneously because silk surface carboxyl isoreactivity group rich in, it can be effectively combined with polymer, improve the water resistance and toughness of silk, the modified addition particle additionally incorporated, particle surface active group rich in simultaneously, and then it can further be combined with polymer and silk, improve the mechanical property of silk, enhance the breaking strength and elongation at break of regenerated silk, the present invention solves during the method for current regenerated silk enhancing, breaking strength, fracture is stretched Long rate improves limited problem.
Description
Technical field
The present invention relates to a kind of preparation methods of modification regeneration fibroin fiber, belong to textile technology field.
Background technique
Silk is " perfection " that animal is brought up after 1 years natural evolutions and adaptation as a kind of native protein
Fiber, it has had both the perfectly balanced of intensity and first property.Silk-fibroin not only has biocompatibility, biological degradability and outstanding
Comprehensive mechanical property and abundance.Importantly, can be each through regeneration preparation under conditions of this kind of natural fiber is certain
Protein material in class macro-scale, such as regenerated fiber, gel, film, microballoon and porous support.In recent decades, with
Deepen continuously to its hierarchical organization (amino acid composition, conformation and aggregated structure etc.) and the understanding of property relationship, silk in addition to
Outside the extensive use of field of textiles, grinds and made internal disorder or usurp also continuous in the application of the sciemtifec and technical spheres such as medicine, biotechnology and daily-use chemical industry
It explores and develops, such as medical slow-released carrier, enzyme immobilization material, cosmetics and food or even photoelectric field etc.
Silk fiber also has excellent mechanical performance (fracture strength 400MPa, breaking strain 15%), and is easy to obtain
, although weaker than best spider silk fiber, toughness is worse, silk fiber is still a kind of very high natural fiber of intensity,
And it is expected to that it is made to obtain the general outstanding performance of spider silk fiber by the modification to silk fiber.Today there is also many grind
Study carefully and how high performance regenerated silk fiber is obtained by artificial spinning.Chinese patent CN102912470A uses sodium carbonate liquor
It dissolves, dialyse after degumming, calcium chloride solution is added and metal oxide nanoparticles are modified it, is obtained eventually by dry spinning
The regenerated silk fiber breaking strength arrived is 50~250MPa, and elongation at break is 50%~150%.Chinese patent
CN106435818A is obtained regenerated silk fiber breaking strength and is reached as high as using gelatin and crosslinking agent doping silk solution-polymerized SBR
420MPa, elongation at break 12%.Chinese patent CN104264263A is obtained using carbon nano tube-doped silk solution-polymerized SBR
Regenerated silk fiber breaking strength is 100~500MPa, and elongation at break is 30%~120%.These methods are to regenerated silk
The method of enhancing is all based on physical doping or chemical crosslinking, compared to the breaking strength of corresponding natural silk fibroin fiber, breaks
It is very limited to split elongation raising.
Summary of the invention
The technical problems to be solved by the invention: during the method for current regenerated silk enhancing, breaking strength is broken
It splits elongation and improves limited problem, this application provides a kind of preparation methods of modification regeneration fibroin fiber.
In order to solve the above technical problems, the present invention is using technical solution as described below:
A kind of preparation method of modification regeneration fibroin fiber, the preparation method include the following steps:
(1) by Raw Silk and mixed solution 1:4~9 in mass ratio, Hybrid Heating is carried out, filtering soaks filter residue into the water
Bubble, every 1~2h replace a water, replace 2~4 times, filter, and air-dry, obtain pre- modified boiled silk；
(2) pre- modified boiled silk, formic acid solution, additive 6:15~20:1~2 in mass ratio are mixed, 50~60
DEG C stand, centrifuge separation, collect solids, by solids, sodium hydroxide solution and sodium hypochlorite 4~6:12:1 in mass ratio into
Row mixing, stands, and filters, and washs, dry, collects dried object；
(3) according to parts by weight, 200~230 parts of mixed solvents, 40~50 parts of dried objects, 13~15 parts of methacrylic acids two are taken
Methylamino ethyl ester, 10~12 parts of modified addition particles, 7~13 parts of acrylamides, 6~8 parts of styrene, 1~3 part of initiator, 1~
3 parts of adjuvants, 0.3~0.5 part of surfactant；
(4) mixed solvent, dried object, dimethylaminoethyl methacrylate, modified addition particle, acrylamide are put into first
In reaction kettle, nitrogen protection preheats at 50~55 DEG C, adds styrene, initiator, adjuvant, surfactant, be warming up to
It 120~125 DEG C, is stirred to react, cooling, discharging is collected out material, is mixed with petroleum ether 2:1~3 in mass ratio, 1~
3 DEG C staticly settle, filtering, collect sediment, and washings is collected in washing；
(5) washings, lysate 1:7~9 in mass ratio are mixed, and 80~90 DEG C of heating, spinning solution is obtained, by spinning
Liquid is squeezed out from spinning nozzle at room temperature, and solidification winding, then immerses in ethanol solution in air, is stretched, fixed length, take out to get
Modification regeneration fibroin fiber.
Mixed solution is by sodium bicarbonate solution, dodecyl trithiocarbonate 7:1 in mass ratio in the step (1)
~3 mix.
Additive is dimethylformamide, tridecafluoro-n-octyltriethoxysilane 10:1 in mass ratio in the step (2)
~3 mix.
The mixed solvent is the 6~9:3~6:4 mixing by volume of tetrahydrofuran, N,N-dimethylformamide, cyclohexanone
It forms.
The modified addition particle the preparation method comprises the following steps: by magnesium nitride, modifying agent and ethanol solution 4~6:1 in mass ratio:
3 carry out mixing and ball milling, dry to add particle to get modified.
The modifying agent is maleic anhydride, n-butyl acrylate 2:1~3 in mass ratio mix.
The initiator is 2- bromoacetate, azo-bis-isobutyl cyanide 3:2~4 in mass ratio mix.
The adjuvant is copper bromide, calcium sulphoaluminate, salicylic acid and ethanol solution 3:2:5:13 in mass ratio~15 mixing
It forms.
The surfactant is neopelex, any one in lauryl sodium sulfate.
Lysate is AmimCl solution in the step (5), N- (4- sulfonic acid butyl) pyridine hydrogen sulphate ionic liquid is pressed
Mass ratio 6:1~2 mix.
The present invention is compared with other methods, and advantageous effects are:
The application passes through first carries out degumming process to silk using sodium bicarbonate solution, joined dodecane in scouring processes
Silk after base trithiocarbonate and degumming carries out micro combination, then is carrying out discongesting processing to it using formic acid, together
When joined dimethylformamide, tridecafluoro-n-octyltriethoxysilane as additive, realize the further modification to silk,
Water resistance is improved, while its surface being made to increase amide group, oxidation processes is carried out followed by sodium hypochlorite, increases
Carboxyl-content, and make silk with negative electrical charge, finally with dimethylaminoethyl methacrylate, acrylamide, styrene etc. into
Row mixing causes polymerization by the effect using initiator, the Block copolymer for having positive charge is formed, simultaneously because silkworm
Silk table face carboxyl isoreactivity group rich in, can effectively be combined with polymer, improve the toughness of silk, separately
Outside since the modified addition particle of addition has positive charge performance well, can be adsorbed well, while
Grain surface active group rich in, and then can further be combined with polymer and silk, to improve silkworm
The mechanical property of silk, enhances the breaking strength and elongation at break of regenerated silk, and the adjuvant being secondly added can be well
Metal ion is released, effectively silk fiber is improved, improves comprehensive performance.
Specific embodiment
Mixed solution is to mix 1.3mol/L sodium bicarbonate solution, dodecyl trithiocarbonate 7:1~3 in mass ratio
It closes.
Additive is dimethylformamide, tridecafluoro-n-octyltriethoxysilane 10:1~3 in mass ratio mix.
Mixed solvent be the 6~9:3~6:4 mixing by volume of tetrahydrofuran, N,N-dimethylformamide, cyclohexanone and
At.
Modified addition particle the preparation method comprises the following steps: by magnesium nitride, modifying agent and 1.1mol/L ethanol solution in mass ratio 4~
6:1:3 is mixed, dry to add particle to get modified with 800r/min ball milling 30min.
Modifying agent is maleic anhydride, n-butyl acrylate 2:1~3 in mass ratio mix.
Initiator is 2- bromoacetate, azo-bis-isobutyl cyanide 3:2~4 in mass ratio mix.
Adjuvant is copper bromide, calcium sulphoaluminate, salicylic acid and 1.5mol/L ethanol solution 3:2:5:13~15 in mass ratio
It mixes.
Surfactant is neopelex, any one in lauryl sodium sulfate.
Lysate is AmimCl solution, (4- sulfonic acid butyl) pyridine hydrogen sulphate ionic liquid 6:1~2 in mass ratio N- are mixed
It closes.
A kind of preparation method of modification regeneration fibroin fiber, the preparation method include the following steps:
(1) by Raw Silk and mixed solution 1:4~9 in mass ratio, in 100 DEG C of progress 3~9h of Hybrid Heating, filtering will be filtered
Slag impregnates into the water, and every 1~2h replaces a water, replaces 2~4 times, filters, and air-dries, obtains pre- modified boiled silk；
(2) pre- modified boiled silk, 1.6mol/L formic acid solution, additive 6:15~20:1~2 in mass ratio are mixed,
In 50~60 DEG C of standing 10h, centrifuge separation collects solids, by solids, 1.2mol/L sodium hydroxide solution and sodium hypochlorite
4~6:12:1 is mixed in mass ratio, stands 6h, is filtered, and is washed, dry, collects dried object；
(3) according to parts by weight, 200~230 parts of mixed solvents, 40~50 parts of dried objects, 13~15 parts of methacrylic acids two are taken
Methylamino ethyl ester, 10~12 parts of modified addition particles, 7~13 parts of acrylamides, 6~8 parts of styrene, 1~3 part of initiator, 1~
3 parts of adjuvants, 0.3~0.5 part of surfactant；
(4) mixed solvent, dried object, dimethylaminoethyl methacrylate, modified addition particle, acrylamide are put into first
In reaction kettle, nitrogen protection adds styrene, initiator, adjuvant, surfactant in 50~55 DEG C of preheating 50min,
Be warming up to 120~125 DEG C, be stirred to react 13h, be cooled to room temperature, discharge, collect out material, with petroleum ether 2:1 in mass ratio~
3 are mixed, and are staticly settled at 1~3 DEG C for 24 hours, and sediment is collected in filtering, using water washing, collect washings；
(5) washings, lysate 1:7~9 in mass ratio are mixed, and 80~90 DEG C of heating 13h, obtains spinning solution, it will
Spinning solution is squeezed out from spinning nozzle at room temperature, in air solidification winding, then is immersed in ethanol solution, is stretched, fixed length, is taken out,
Up to modification regeneration fibroin fiber.
Embodiment 1
Mixed solution is to mix 1.3mol/L sodium bicarbonate solution, dodecyl trithiocarbonate 7:3 in mass ratio.
Additive is dimethylformamide, tridecafluoro-n-octyltriethoxysilane 10:3 in mass ratio is mixed.
Mixed solvent is tetrahydrofuran, N,N-dimethylformamide, 9:6:4 is mixed cyclohexanone by volume.
Modified addition particle the preparation method comprises the following steps: by magnesium nitride, modifying agent and 1.1mol/L ethanol solution in mass ratio 6:
1:3 is mixed, dry to add particle to get modified with 800r/min ball milling 30min.
Modifying agent is maleic anhydride, n-butyl acrylate 2:3 in mass ratio is mixed.
Initiator is 2- bromoacetate, azo-bis-isobutyl cyanide 3:4 in mass ratio is mixed.
Adjuvant is copper bromide, calcium sulphoaluminate, salicylic acid and 1.5mol/L ethanol solution 3:2:5:15 in mass ratio mixing
It forms.
Surfactant is neopelex.
Lysate is AmimCl solution, N- (4- sulfonic acid butyl) pyridine hydrogen sulphate ionic liquid 6:2 in mass ratio mixing
It forms.
A kind of preparation method of modification regeneration fibroin fiber, the preparation method include the following steps:
(1) by Raw Silk and mixed solution 1:9 in mass ratio, in 100 DEG C of progress 3~9h of Hybrid Heating, filter residue is put in filtering
Enter in water and impregnate, every 2h replaces a water, replaces 4 times, filters, and air-dries, obtains pre- modified boiled silk；
(2) pre- modified boiled silk, 1.6mol/L formic acid solution, additive 6:20:2 in mass ratio are mixed, at 60 DEG C
10h is stood, solids is collected in centrifuge separation, by solids, 1.2mol/L sodium hydroxide solution and sodium hypochlorite in mass ratio 6:
12:1 is mixed, and 6h is stood, and is filtered, and is washed, dry, collects dried object；
(3) according to parts by weight, 230 parts of mixed solvents, 50 parts of dried objects, 15 parts of dimethylaminoethyl methacrylates, 12 are taken
The modified addition particle, 13 parts of acrylamides, 8 parts of styrene, 3 parts of initiators, 3 parts of adjuvants, 0.5 part of surfactant of part；
(4) mixed solvent, dried object, dimethylaminoethyl methacrylate, modified addition particle, acrylamide are put into first
In reaction kettle, nitrogen protection adds styrene, initiator, adjuvant, surfactant in 55 DEG C of preheating 50min, heating
To 125 DEG C, it is stirred to react 13h, is cooled to room temperature, discharged, collect out material, mixed with petroleum ether 2:3 in mass ratio,
3 DEG C staticly settle for 24 hours, and sediment is collected in filtering, using water washing, collect washings；
(5) washings, lysate 1:9 in mass ratio are mixed, and 90 DEG C of heating 13h, obtains spinning solution, spinning solution is existed
It squeezes out, in air solidification winding, then immerses in ethanol solution from spinning nozzle at room temperature, stretch, fixed length, take out to get modification
Regenerated fibroin fiber.
Embodiment 2
Mixed solution is to mix 1.3mol/L sodium bicarbonate solution, dodecyl trithiocarbonate 7:2 in mass ratio.
Additive is dimethylformamide, tridecafluoro-n-octyltriethoxysilane 10:2 in mass ratio is mixed.
Mixed solvent is tetrahydrofuran, N,N-dimethylformamide, 7:5:4 is mixed cyclohexanone by volume.
Modified addition particle the preparation method comprises the following steps: by magnesium nitride, modifying agent and 1.1mol/L ethanol solution in mass ratio 5:
1:3 is mixed, dry to add particle to get modified with 800r/min ball milling 30min.
Modifying agent is maleic anhydride, n-butyl acrylate 2:2 in mass ratio is mixed.
Initiator is 2- bromoacetate, azo-bis-isobutyl cyanide 3:3 in mass ratio is mixed.
Adjuvant is copper bromide, calcium sulphoaluminate, salicylic acid and 1.5mol/L ethanol solution 3:2:5:14 in mass ratio mixing
It forms.
Surfactant is lauryl sodium sulfate.
Lysate is AmimCl solution, N- (4- sulfonic acid butyl) pyridine hydrogen sulphate ionic liquid 6:1.5 in mass ratio is mixed
It closes.
A kind of preparation method of modification regeneration fibroin fiber, the preparation method include the following steps:
(1) by Raw Silk and mixed solution 1:6 in mass ratio, in 100 DEG C of progress Hybrid Heating 8h, filter residue is put by filtering
It is impregnated in water, every 1.5h replaces a water, replaces 3 times, filters, and air-dries, obtains pre- modified boiled silk；
(2) pre- modified boiled silk, 1.6mol/L formic acid solution, additive 6:18:1.5 in mass ratio are mixed, 55
DEG C stand 10h, centrifuge separation, collect solids, in mass ratio by solids, 1.2mol/L sodium hydroxide solution and sodium hypochlorite
5:12:1 is mixed, and 6h is stood, and is filtered, and is washed, dry, collects dried object；
(3) according to parts by weight, 215 parts of mixed solvents, 45 parts of dried objects, 14 parts of dimethylaminoethyl methacrylates, 11 are taken
The modified addition particle, 10 parts of acrylamides, 7 parts of styrene, 2 parts of initiators, 2 parts of adjuvants, 0.4 part of surfactant of part；
(4) mixed solvent, dried object, dimethylaminoethyl methacrylate, modified addition particle, acrylamide are put into first
In reaction kettle, nitrogen protection adds styrene, initiator, adjuvant, surfactant in 53 DEG C of preheating 50min, heating
To 123 DEG C, it is stirred to react 13h, is cooled to room temperature, discharged, collect out material, mixed with petroleum ether 2:2 in mass ratio,
2 DEG C staticly settle for 24 hours, and sediment is collected in filtering, using water washing, collect washings；
(5) washings, lysate 1:8 in mass ratio are mixed, and 85 DEG C of heating 13h, obtains spinning solution, spinning solution is existed
It squeezes out, in air solidification winding, then immerses in ethanol solution from spinning nozzle at room temperature, stretch, fixed length, take out to get modification
Regenerated fibroin fiber.
Embodiment 3
Mixed solution is to mix 1.3mol/L sodium bicarbonate solution, dodecyl trithiocarbonate 7:1 in mass ratio.
Additive is dimethylformamide, tridecafluoro-n-octyltriethoxysilane 10:1 in mass ratio is mixed.
Mixed solvent is tetrahydrofuran, N,N-dimethylformamide, 6:3:4 is mixed cyclohexanone by volume.
Modified addition particle the preparation method comprises the following steps: by magnesium nitride, modifying agent and 1.1mol/L ethanol solution in mass ratio 4:
1:3 is mixed, dry to add particle to get modified with 800r/min ball milling 30min.
Modifying agent is maleic anhydride, n-butyl acrylate 2:1 in mass ratio is mixed.
Initiator is 2- bromoacetate, azo-bis-isobutyl cyanide 3:2 in mass ratio is mixed.
Adjuvant is copper bromide, calcium sulphoaluminate, salicylic acid and 1.5mol/L ethanol solution 3:2:5:13 in mass ratio mixing
It forms.
Surfactant is neopelex.
Lysate is AmimCl solution, N- (4- sulfonic acid butyl) pyridine hydrogen sulphate ionic liquid 6:1 in mass ratio mixing
It forms.
A kind of preparation method of modification regeneration fibroin fiber, the preparation method include the following steps:
(1) by Raw Silk and mixed solution 1:4 in mass ratio, in 100 DEG C of progress Hybrid Heating 3h, filter residue is put by filtering
It is impregnated in water, every 1h replaces a water, replaces 2 times, filters, and air-dries, obtains pre- modified boiled silk；
(2) pre- modified boiled silk, 1.6mol/L formic acid solution, additive 6:15:1 in mass ratio are mixed, at 50 DEG C
10h is stood, solids is collected in centrifuge separation, by solids, 1.2mol/L sodium hydroxide solution and sodium hypochlorite in mass ratio 4:
12:1 is mixed, and 6h is stood, and is filtered, and is washed, dry, collects dried object；
(3) according to parts by weight, 200 parts of mixed solvents, 40 parts of dried objects, 13 parts of dimethylaminoethyl methacrylates, 10 are taken
The modified addition particle, 7 parts of acrylamides, 6 parts of styrene, 1 part of initiator, 1 part of adjuvant, 0.3 part of surfactant of part；
(4) mixed solvent, dried object, dimethylaminoethyl methacrylate, modified addition particle, acrylamide are put into first
In reaction kettle, nitrogen protection adds styrene, initiator, adjuvant, surfactant in 50 DEG C of preheating 50min, heating
To 120 DEG C, it is stirred to react 13h, is cooled to room temperature, discharged, collect out material, mixed with petroleum ether 2:1 in mass ratio,
1 DEG C staticly settles for 24 hours, and sediment is collected in filtering, using water washing, collects washings；
(5) washings, lysate 1:7 in mass ratio are mixed, and 80 DEG C of heating 13h, obtains spinning solution, spinning solution is existed
It squeezes out, in air solidification winding, then immerses in ethanol solution from spinning nozzle at room temperature, stretch, fixed length, take out to get modification
Regenerated fibroin fiber.
Comparative example 1
It is substantially the same manner as Example 2, only the difference is that lacking modified addition particle.
Comparative example 2
Commercially available regenerated fibroin fiber.
Embodiment and the regenerated fibroin fiber of comparative example preparation are according to its mechanical property of SNT 1567-2005 standard detection
Can, as a result as shown in table 1 below.
Table 1:
In summary, regenerated fibroin fiber effect of the invention is more preferable as can be seen from Table 1, is worth of widely use, above
Described is only preferred mode of the invention, is not intended to limit the invention, all within the spirits and principles of the present invention, made
Any modification, equivalent substitution, improvement and etc. should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of modification regeneration fibroin fiber, which is characterized in that the preparation method includes the following steps:
(1) by Raw Silk and mixed solution 1:4~9 in mass ratio, Hybrid Heating is carried out, filtering soaks filter residue into the water
Bubble, every 1~2h replace a water, replace 2~4 times, filter, and air-dry, obtain pre- modified boiled silk；
(2) pre- modified boiled silk, formic acid solution, additive 6:15~20:1~2 in mass ratio are mixed, 50~60
DEG C stand, centrifuge separation, collect solids, by solids, sodium hydroxide solution and sodium hypochlorite 4~6:12:1 in mass ratio into
Row mixing, stands, and filters, and washs, dry, collects dried object；
(3) according to parts by weight, 200~230 parts of mixed solvents, 40~50 parts of dried objects, 13~15 parts of methacrylic acids two are taken
Methylamino ethyl ester, 10~12 parts of modified addition particles, 7~13 parts of acrylamides, 6~8 parts of styrene, 1~3 part of initiator, 1~
3 parts of adjuvants, 0.3~0.5 part of surfactant；
(4) mixed solvent, dried object, dimethylaminoethyl methacrylate, modified addition particle, acrylamide are put into first
In reaction kettle, nitrogen protection preheats at 50~55 DEG C, adds styrene, initiator, adjuvant, surfactant, be warming up to
It 120~125 DEG C, is stirred to react, cooling, discharging is collected out material, is mixed with petroleum ether 2:1~3 in mass ratio, 1~
3 DEG C staticly settle, filtering, collect sediment, and washings is collected in washing；
(5) washings, lysate 1:7~9 in mass ratio are mixed, and 80~90 DEG C of heating, spinning solution is obtained, by spinning
Liquid is squeezed out from spinning nozzle at room temperature, and solidification winding, then immerses in ethanol solution in air, is stretched, fixed length, take out to get
Modification regeneration fibroin fiber.
2. the preparation method of modification regeneration fibroin fiber according to claim 1, which is characterized in that the step (1)
Middle mixed solution is to mix sodium bicarbonate solution, dodecyl trithiocarbonate 7:1~3 in mass ratio.
3. the preparation method of modification regeneration fibroin fiber according to claim 1, which is characterized in that the step (2)
Middle additive is dimethylformamide, tridecafluoro-n-octyltriethoxysilane 10:1~3 in mass ratio mix.
4. the preparation method of modification regeneration fibroin fiber according to claim 1, which is characterized in that the mixed solvent
For tetrahydrofuran, N,N-dimethylformamide, cyclohexanone, 6~9:3~6:4 is mixed by volume.
5. the preparation method of modification regeneration fibroin fiber according to claim 1, which is characterized in that the modified addition
Particle the preparation method comprises the following steps: magnesium nitride, modifying agent and ethanol solution 4~6:1:3 in mass ratio are carried out mixing and ball milling, it is dry,
Particle is added up to modified.
6. the preparation method of modification regeneration fibroin fiber according to claim 5, which is characterized in that the modifying agent is
Maleic anhydride, n-butyl acrylate 2:1~3 in mass ratio mix.
7. the preparation method of modification regeneration fibroin fiber according to claim 1, which is characterized in that the initiator is
2- bromoacetate, azo-bis-isobutyl cyanide 3:2~4 in mass ratio mix.
8. the preparation method of modification regeneration fibroin fiber according to claim 1, which is characterized in that the adjuvant is
Copper bromide, calcium sulphoaluminate, salicylic acid and ethanol solution 3:2:5:13~15 in mass ratio mix.
9. the preparation method of modification regeneration fibroin fiber according to claim 1, which is characterized in that the surface-active
Agent is neopelex, any one in lauryl sodium sulfate.
10. the preparation method of modification regeneration fibroin fiber according to claim 5, which is characterized in that the step (5)
Middle lysate be AmimCl solution, N- (4- sulfonic acid butyl) pyridine hydrogen sulphate ionic liquid 6:1 in mass ratio~2 mixing and
At.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724920A (en) * | 2009-11-13 | 2010-06-09 | 东华大学 | Method for preparing regenerated silk fiber by means of dry spinning |
| CN102220650A (en) * | 2011-04-29 | 2011-10-19 | 西南科技大学 | Soy protein fibers and preparation method thereof |
| CN102250281A (en) * | 2011-06-21 | 2011-11-23 | 上海三瑞高分子材料有限公司 | Cation acrylate emulsion |
| CN107083674A (en) * | 2017-05-25 | 2017-08-22 | 南京林业大学 | A kind of preparation method of silk nanofiber dispersion liquid |
-
2019
- 2019-02-28 CN CN201910150360.2A patent/CN109957848A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724920A (en) * | 2009-11-13 | 2010-06-09 | 东华大学 | Method for preparing regenerated silk fiber by means of dry spinning |
| CN102220650A (en) * | 2011-04-29 | 2011-10-19 | 西南科技大学 | Soy protein fibers and preparation method thereof |
| CN102250281A (en) * | 2011-06-21 | 2011-11-23 | 上海三瑞高分子材料有限公司 | Cation acrylate emulsion |
| CN107083674A (en) * | 2017-05-25 | 2017-08-22 | 南京林业大学 | A kind of preparation method of silk nanofiber dispersion liquid |
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