CN106637969A - Tussah fibroin protein microsphere including three-dimensional porous structure and production method thereof - Google Patents
Tussah fibroin protein microsphere including three-dimensional porous structure and production method thereof Download PDFInfo
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- CN106637969A CN106637969A CN201610838925.2A CN201610838925A CN106637969A CN 106637969 A CN106637969 A CN 106637969A CN 201610838925 A CN201610838925 A CN 201610838925A CN 106637969 A CN106637969 A CN 106637969A
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/15—Proteins or derivatives thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Cosmetics (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
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Abstract
The invention provides a tussah fibroin protein microsphere including a three-dimensional porous structure and a production method thereof. The method comprises the steps of using tussah silk as raw material, degumming the tussah silk, placing degummed tussah silk into solvent to dissolve completely, dialyzing, separating, adding enzyme solution for enzymolysis, heating, and concentrating to obtain tussah fibroin protein solution; adding a foaming agent and a cross-linking agent into the tussah fibroin protein solution, standing, stirring and centrifugally separating to form tussah fibroin protein particles; and adding the tussah fibroin protein particles into sodium chloride solution, heating, stirring, centrifugally separating sediments, washing with ethyl alcohol, taking the washed sediments out, drying and placing into a low temperature environment to cool and dry, thus acquiring the tussah fibroin protein microspheres with three-dimensional porous structures. The production method provided by the invention is simple, and the produced silk fibers are good in porosity and have the properties of being skin-friendly, air and vapor permeable and adsorptive.
Description
Technical field
The invention belongs to textile material technical field, and in particular to a kind of tussah silk fibroin containing three-dimensional pore space structure is micro-
Ball and preparation method thereof.
Background technology
A kind of animal protein from silk fiber of fibroin albumen, either mulberry silk or tussah silk, fibroin albumen
All mainly it is made up of 18 kinds of amino acid such as glycine, alanine and serine, fibroin albumen has good degradability, life
Thing compatibility and mouldability etc., fibroin albumen has many applications in terms of textile finishing.
Fibroin albumen textile finishing is mostly mixed silk fibroin protein solution with other functions agent as finishing agent, using leaching
The method of stain, coating or spraying is arranged to fabric, and the fibroin albumen in the method for sorting is more to be covered in fabric with membranaceous
Surface, be unfavorable for the feel and breathable moisture permeability of fabric.Fibroin albumen particle is one kind of the form of fibroin albumen, fibroin
The preparation method of protein body has emulsion-solvent evaporation method, phase separation method, high-pressure electrostatic method and spray drying process etc., but system at present
Standby silk particle is all full particle, and compared with full particle, its air-moisture-permeable, absorption property and feature are more for porous particle
It is good, but currently for fibroin porous particle in terms of research and few.
Disclosed in Chinese patent CN 104436284A it is a kind of load insulin/fibroin microsphere fibroin porous material and its
Preparation method, will add glycerine as outer layer solution in silk fibroin solution, insulin is dissolved in into formation sandwich layer solution in hydrochloric acid, by two
, used as raw material, Jing coaxial electrostatic spinnings technique obtains microballoon in liquid nitrogen again, and freeze-dried and Balance Treatment is obtained not for kind of solution
The fibroin microsphere of the load insulin of water is dissolved in, the silk fibroin solution surface laying of crosslinking the fibroin microsphere of insulin is carried into, at freezing
After reason, re-radiation crosslinking silk fibroin solution, then it is freeze-dried process obtain load insulin/fibroin microsphere fibroin porous material
Material.The preparation side of silk fibroin/hydroxyapatite/collagen composite porous stent disclosed in Chinese patent CN102331270B
Method, after silk fibroin water solution is mixed with collagen aqueous solution, adds the mixture of sodium chloride and hydroxyapatite, room temperature
Coherent mass is settled into, after being cleaned with ethanol immersion and ultra-pure water product is obtained.It is a kind of disclosed in Chinese patent CN105413728A
Titanium dioxide hollow microballoon being combined with carbon nitrogen and preparation method thereof, the silk gum solution after natural silk degumming is concentrated, and adds alcohol
Precipitate silk gum, freeze-dried formation sericin powder dissolves in sericin powder to form sericin solution, then
Add magnesium ion, precipitation and separation to obtain silk sericin microballoon, butyl titanate ethanol is added dropwise Jing after ethanol washing dispersion molten
Liquid, is centrifugally separating to obtain precipitation after reaction, the titanium dioxide hollow microballoon being combined with carbon nitrogen is obtained Jing after high temperature sintering.By above-mentioned
Prior art understands that the microballoon for being currently based on fibroin preparation is a lot, and the porous support based on fibroin is also a lot, but
Research based on the porous microsphere of fibroin is simultaneously few.
The content of the invention
The technical problem to be solved in the present invention be to provide a kind of Wild antheraea pernyi silk fibroin microsphere containing three-dimensional pore space structure and its
Preparation method, after tussah silk peptide is digested, is acted on by crosslinking agent, and foaming agent cladding is wherein formed into tussah silk fibroin
Grain, then the heating of Jing sodium chloride, make foaming agent form bubble, make the micro-bubble effusion formed in tussah silk peptide particle, shape
Into the Wild antheraea pernyi silk fibroin microsphere containing three-dimensional pore space structure.
To solve above-mentioned technical problem, the technical scheme is that：
A kind of Wild antheraea pernyi silk fibroin microsphere containing three-dimensional pore space structure, the tussah silk fibroin containing three-dimensional pore space structure
Microballoon includes tussah silk fibroin, and the form of the tussah silk fibroin is containing the spherical of three-dimensional pore space structure, the tussah
Fibroin albumen Jing enzymes are pre-processed.
Used as the preferred of above-mentioned technical proposal, the tussah silk fibroin is crosslinked, foaming and freeze-drying process.
The present invention also provides a kind of preparation method of the Wild antheraea pernyi silk fibroin microsphere containing three-dimensional pore space structure, including following step
Suddenly：
(1) using tussah silk as raw material, Jing after degumming, it is placed in solvent and dissolves complete, dialysis is separated, and adds enzyme solutions
Enzymolysis, heating, is concentrated to give tussah silk fibroin solution；
(2) foaming agent and crosslinking agent are added in the tussah silk fibroin solution for preparing step (1), is stood, stirring, centrifugation
Separation forms tussah silk fibroin particle；
(3) the tussah silk fibroin particle for preparing step (2) is added in sodium chloride solution, heating stirring, centrifugation
Precipitation, is washed with ethanol, is taken out, drying, then is placed in frozen drying process, obtains the tussah silk peptide containing three-dimensional pore space structure
Protein microsphere.
Used as the preferred of above-mentioned technical proposal, in the step (1), enzyme solutions are elastin laminin enzyme solutions, and the enzyme is molten
The mass fraction of liquid is 0.5-2%.
Used as the preferred of above-mentioned technical proposal, in the step (1), the temperature of enzymolysis is 10-15 DEG C, and the time of enzymolysis is
30-60min。
As the preferred of above-mentioned technical proposal, in the step (1), tussah silk fibroin in tussah silk fibroin solution
Molecular weight is 15-30kDa.
Used as the preferred of above-mentioned technical proposal, in the step (2), foaming agent is azodiisobutyronitrile, and crosslinking agent is penta
Dialdehyde and citric acid.
Used as the preferred of above-mentioned technical proposal, in the step (2), the temperature of standing is 20-25 DEG C, the time 2- of standing
5min, the time of stirring is 60-90min.
Used as the preferred of above-mentioned technical proposal, in the step (3), the temperature of heating stirring is 95-98 DEG C, mixing speed
For 200-500rpm, the time is 20-30min.
Used as the preferred of above-mentioned technical proposal, in the step (3), the temperature of frozen drying process is -4--10
DEG C, the time is 1-2h.
Compared with prior art, the invention has the advantages that：
(1) present invention prepare the Wild antheraea pernyi silk fibroin microsphere containing three-dimensional pore space structure raw material be tussah silk peptide, tussah
Fibroin inherently contains microcellular structure, and Jing elastic force enzymes digest to form fibroin small molecule structure, then recycles crosslinking agent to make fibroin
Small molecule crosslinking restructuring, foaming agent is coated wherein, forms fibroin microsphere, and foaming agent is in azodiisobutyronitrile, with crosslinking agent
Citric acid a small amount of reaction can occur, generate micro-bubble, make fibroin microsphere internal structure loose, then by glutaraldehyde and lemon
Crosslinking of the acid to fibroin small molecule, forms stable fibroin microsphere, and again Jing sodium chloride heats fibroin microsphere, makes fibroin microsphere
In azodiisobutyronitrile fully react, generate bubble, bubble effusion forms three-dimensional pore space structure, then Jing in fibroin microsphere
Freeze-drying process takes out a small amount of moisture in fibroin microsphere, increases the porosity in fibroin microsphere.
(2) primary raw material in the Wild antheraea pernyi silk fibroin microsphere containing three-dimensional pore space structure prepared by the present invention is tussah silk
Element, also with pore space structure, therefore the Wild antheraea pernyi silk fibroin microsphere for preparing has good pro-skin and breathable moisture permeability, moreover it is possible to
Adsorption function material, is conducive to the postfinishing process of fabric, and does not affect the wearability of fabric itself.
Specific embodiment
Describe the present invention, the illustrative examples of the here present invention and explanation in detail below in conjunction with specific embodiment
It is for explaining the present invention but not as a limitation of the invention.
Embodiment 1：
(1) using tussah silk as raw material, Jing after degumming, with solid-liquid ratio as 1g:10ml, is placed in lithium bromide solvent at 60 DEG C
Middle dissolving is complete, and dialysis is separated, and the elastin laminin enzyme solutions for adding mass fraction to be 0.5% digest 30min at 10 DEG C,
Heat inactivation at 80 DEG C, is concentrated to give tussah silk fibroin solution, and the wherein molecular weight of tussah silk fibroin is 15-30kDa.
(2) by mass parts agent, send out 0.5 part of azodiisobutyronitrile is added in the aqueous solution containing 1 part of tussah silk fibroin
Infusion and 1 part of glutaraldehyde and lemon acid crosslinking agent, stand 2min at 20 DEG C, stir 60min, and centrifugation forms tussah silk
Fibroin particle.
(3) by mass parts agent, 1 part of tussah silk fibroin particle is added in the aqueous solution containing 6 parts of sodium chloride, at 95 DEG C
At a temperature of and 200rpm speed under heating stirring 20min, centrifugation precipitation, wash with ethanol, take out, at 60 DEG C baking
It is dry, then frozen drying processes 1h at being placed in -4 DEG C, obtains the Wild antheraea pernyi silk fibroin microsphere containing three-dimensional pore space structure.
Embodiment 2：
(1) using tussah silk as raw material, Jing after degumming, with solid-liquid ratio as 1g:10ml, is placed in lithium bromide solvent at 60 DEG C
Middle dissolving is complete, and dialysis is separated, and the elastin laminin enzyme solutions for adding mass fraction to be 2% digest 60min, 80 at 15 DEG C
Heat inactivation at DEG C, is concentrated to give tussah silk fibroin solution, and the wherein molecular weight of tussah silk fibroin is 15-30kDa.
(2) by mass parts agent, send out 0.8 part of azodiisobutyronitrile is added in the aqueous solution containing 1 part of tussah silk fibroin
Infusion and 2 parts of glutaraldehyde and lemon acid crosslinking agent, stand 5min at 25 DEG C, stir 90min, and centrifugation forms tussah silk
Fibroin particle.
(3) by mass parts agent, 1 part of tussah silk fibroin particle is added in the aqueous solution containing 10 parts of sodium chloride, 98
With heating stirring 30min under the speed of 500rpm at a temperature of DEG C, centrifugation precipitation is washed with ethanol, is taken out, and is dried at 60 DEG C
It is dry, then frozen drying processes 2h at being placed in -10 DEG C, obtains the Wild antheraea pernyi silk fibroin microsphere containing three-dimensional pore space structure.
Embodiment 3：
(1) using tussah silk as raw material, Jing after degumming, with solid-liquid ratio as 1g:10ml, is placed in lithium bromide solvent at 60 DEG C
Middle dissolving is complete, and dialysis is separated, and the elastin laminin enzyme solutions for adding mass fraction to be 1% digest 45min, 80 at 12 DEG C
Heat inactivation at DEG C, is concentrated to give tussah silk fibroin solution, and the wherein molecular weight of tussah silk fibroin is 15-30kDa.
(2) by mass parts agent, send out 0.6 part of azodiisobutyronitrile is added in the aqueous solution containing 1 part of tussah silk fibroin
Infusion and 1.5 parts of glutaraldehyde and lemon acid crosslinking agent, stand 3min at 23 DEG C, stir 70min, and centrifugation forms tussah
Fibroin albumen particle.
(3) by mass parts agent, 1 part of tussah silk fibroin particle is added in the aqueous solution containing 8 parts of sodium chloride, at 97 DEG C
At a temperature of and 400rpm speed under heating stirring 25min, centrifugation precipitation, wash with ethanol, take out, at 60 DEG C baking
It is dry, then frozen drying processes 1.5h at being placed in -6 DEG C, obtains the Wild antheraea pernyi silk fibroin microsphere containing three-dimensional pore space structure.
Embodiment 4：
(1) using tussah silk as raw material, Jing after degumming, with solid-liquid ratio as 1g:10ml, is placed in lithium bromide solvent at 60 DEG C
Middle dissolving is complete, and dialysis is separated, and the elastin laminin enzyme solutions for adding mass fraction to be 1.5% digest 30min at 15 DEG C,
Heat inactivation at 80 DEG C, is concentrated to give tussah silk fibroin solution, and the wherein molecular weight of tussah silk fibroin is 15-30kDa.
(2) by mass parts agent, send out 0.7 part of azodiisobutyronitrile is added in the aqueous solution containing 1 part of tussah silk fibroin
Infusion and 2 parts of glutaraldehyde and lemon acid crosslinking agent, stand 4min at 20 DEG C, stir 70min, and centrifugation forms tussah silk
Fibroin particle.
(3) by mass parts agent, 1 part of tussah silk fibroin particle is added in the aqueous solution containing 8 parts of sodium chloride, at 95 DEG C
At a temperature of and 350rpm speed under heating stirring 30min, centrifugation precipitation, wash with ethanol, take out, at 60 DEG C baking
It is dry, then frozen drying processes 2h at being placed in -8 DEG C, obtains the Wild antheraea pernyi silk fibroin microsphere containing three-dimensional pore space structure.
Embodiment 5：
(1) using tussah silk as raw material, Jing after degumming, with solid-liquid ratio as 1g:10ml, is placed in lithium bromide solvent at 60 DEG C
Middle dissolving is complete, and dialysis is separated, and the elastin laminin enzyme solutions for adding mass fraction to be 0.8% digest 50min at 12 DEG C,
Heat inactivation at 80 DEG C, is concentrated to give tussah silk fibroin solution, and the wherein molecular weight of tussah silk fibroin is 15-30kDa.
(2) by mass parts agent, send out 0.7 part of azodiisobutyronitrile is added in the aqueous solution containing 1 part of tussah silk fibroin
Infusion and 2 parts of glutaraldehyde and lemon acid crosslinking agent, stand 5min at 20 DEG C, stir 60min, and centrifugation forms tussah silk
Fibroin particle.
(3) by mass parts agent, 1 part of tussah silk fibroin particle is added in the aqueous solution containing 8 parts of sodium chloride, at 98 DEG C
At a temperature of and 200rpm speed under heating stirring 30min, centrifugation precipitation, wash with ethanol, take out, at 60 DEG C baking
It is dry, then frozen drying processes 1.5h at being placed in -8 DEG C, obtains the Wild antheraea pernyi silk fibroin microsphere containing three-dimensional pore space structure.
Embodiment 6：
(1) using tussah silk as raw material, Jing after degumming, with solid-liquid ratio as 1g:10ml, is placed in lithium bromide solvent at 60 DEG C
Middle dissolving is complete, and dialysis is separated, and the elastin laminin enzyme solutions for adding mass fraction to be 1.5% digest 60min at 15 DEG C,
Heat inactivation at 80 DEG C, is concentrated to give tussah silk fibroin solution, and the wherein molecular weight of tussah silk fibroin is 15-30kDa.
(2) by mass parts agent, send out 0.5 part of azodiisobutyronitrile is added in the aqueous solution containing 1 part of tussah silk fibroin
Infusion and 2 parts of glutaraldehyde and lemon acid crosslinking agent, stand 2min at 25 DEG C, stir 90min, and centrifugation forms tussah silk
Fibroin particle.
(3) by mass parts agent, 1 part of tussah silk fibroin particle is added in the aqueous solution containing 10 parts of sodium chloride, 95
With heating stirring 20min under the speed of 400rpm at a temperature of DEG C, centrifugation precipitation is washed with ethanol, is taken out, and is dried at 60 DEG C
It is dry, then frozen drying processes 2h at being placed in -7 DEG C, obtains the Wild antheraea pernyi silk fibroin microsphere containing three-dimensional pore space structure.
Embodiment 7：
(1) using tussah silk as raw material, Jing after degumming, with solid-liquid ratio as 1g:10ml, is placed in lithium bromide solvent at 60 DEG C
Middle dissolving is complete, and dialysis is separated, and the elastin laminin enzyme solutions for adding mass fraction to be 1% digest 30min, 80 at 10 DEG C
Heat inactivation at DEG C, is concentrated to give tussah silk fibroin solution, and the wherein molecular weight of tussah silk fibroin is 15-30kDa.
(2) by mass parts agent, send out 0.6 part of azodiisobutyronitrile is added in the aqueous solution containing 1 part of tussah silk fibroin
Infusion and 1 part of glutaraldehyde and lemon acid crosslinking agent, stand 4min at 25 DEG C, stir 80min, and centrifugation forms tussah silk
Fibroin particle.
(3) by mass parts agent, 1 part of tussah silk fibroin particle is added in the aqueous solution containing 10 parts of sodium chloride, 98
With heating stirring 25min under the speed of 500rpm at a temperature of DEG C, centrifugation precipitation is washed with ethanol, is taken out, and is dried at 60 DEG C
It is dry, then frozen drying processes 1.5h at being placed in -8 DEG C, obtains the Wild antheraea pernyi silk fibroin microsphere containing three-dimensional pore space structure.
Embodiment 8：
(1) using tussah silk as raw material, Jing after degumming, with solid-liquid ratio as 1g:10ml, is placed in lithium bromide solvent at 60 DEG C
Middle dissolving is complete, and dialysis is separated, and the elastin laminin enzyme solutions for adding mass fraction to be 2% digest 60min, 80 at 10 DEG C
Heat inactivation at DEG C, is concentrated to give tussah silk fibroin solution, and the wherein molecular weight of tussah silk fibroin is 15-30kDa.
(2) by mass parts agent, send out 0.8 part of azodiisobutyronitrile is added in the aqueous solution containing 1 part of tussah silk fibroin
Infusion and 2 parts of glutaraldehyde and lemon acid crosslinking agent, stand 5min at 20 DEG C, stir 60min, and centrifugation forms tussah silk
Fibroin particle.
(3) by mass parts agent, 1 part of tussah silk fibroin particle is added in the aqueous solution containing 10 parts of sodium chloride, 95
With heating stirring 25min under the speed of 250rpm at a temperature of DEG C, centrifugation precipitation is washed with ethanol, is taken out, and is dried at 60 DEG C
It is dry, then frozen drying processes 1h at being placed in -7 DEG C, obtains the Wild antheraea pernyi silk fibroin microsphere containing three-dimensional pore space structure.
After testing, the hole situation of the Wild antheraea pernyi silk fibroin microsphere containing three-dimensional pore space structure prepared by embodiment 1-8, absorption
The result of situation and pro-skin situation is as follows：
As seen from the above table, the porosity of the Wild antheraea pernyi silk fibroin microsphere containing three-dimensional pore space structure prepared by the present invention is good, inhales
It is attached functional, it is non-stimulated to skin, also with good permeability.
The principle and its effect of above-described embodiment only illustrative present invention, it is of the invention not for limiting.It is any ripe
Know the personage of this technology all can carry out modifications and changes under the spirit and the scope without prejudice to the present invention to above-described embodiment.Cause
This, such as those of ordinary skill in the art is complete with institute under technological thought without departing from disclosed spirit
Into all equivalent modifications or change, should by the present invention claim be covered.
Claims (10)
1. a kind of Wild antheraea pernyi silk fibroin microsphere containing three-dimensional pore space structure, it is characterised in that：The toothed oak containing three-dimensional pore space structure
Fibroin protein microballoon includes tussah silk fibroin, and the form of the tussah silk fibroin is the ball containing three-dimensional pore space structure
Shape, the tussah silk fibroin Jing enzymes pretreatment.
2. a kind of Wild antheraea pernyi silk fibroin microsphere containing three-dimensional pore space structure according to claim 1, it is characterised in that：It is described
Tussah silk fibroin is crosslinked, foaming and freeze-drying process.
3. a kind of preparation method of the Wild antheraea pernyi silk fibroin microsphere containing three-dimensional pore space structure, it is characterised in that：Comprise the following steps：
(1) using tussah silk as raw material, Jing after degumming, it is placed in solvent and dissolves complete, dialysis is separated, and adds enzyme solutions enzymolysis,
Heating, is concentrated to give tussah silk fibroin solution；
(2) foaming agent and crosslinking agent are added in the tussah silk fibroin solution for preparing step (1), is stood, stirring, centrifugation
Form tussah silk fibroin particle；
(3) the tussah silk fibroin particle for preparing step (2) is added in sodium chloride solution, heating stirring, centrifugation precipitation,
Washed with ethanol, taken out, drying, then frozen drying process is placed in, obtain the tussah silk fibroin containing three-dimensional pore space structure
Microballoon.
4. the preparation method of a kind of Wild antheraea pernyi silk fibroin microsphere containing three-dimensional pore space structure according to claim 3, it is special
Levy and be：In the step (1), enzyme solutions are elastin laminin enzyme solutions, and the mass fraction of the enzyme solutions is 0.5-2%.
5. the preparation method of a kind of Wild antheraea pernyi silk fibroin microsphere containing three-dimensional pore space structure according to claim 3, it is special
Levy and be：In the step (1), the temperature of enzymolysis is 10-15 DEG C, and the time of enzymolysis is 30-60min.
6. the preparation method of a kind of Wild antheraea pernyi silk fibroin microsphere containing three-dimensional pore space structure according to claim 3, it is special
Levy and be：In the step (1), the molecular weight of tussah silk fibroin is 15-30kDa in tussah silk fibroin solution.
7. the preparation method of a kind of Wild antheraea pernyi silk fibroin microsphere containing three-dimensional pore space structure according to claim 3, it is special
Levy and be：In the step (2), foaming agent is azodiisobutyronitrile, and crosslinking agent is glutaraldehyde and citric acid.
8. the preparation method of a kind of Wild antheraea pernyi silk fibroin microsphere containing three-dimensional pore space structure according to claim 3, it is special
Levy and be：In the step (2), the temperature of standing is 20-25 DEG C, the time 2-5min of standing, and the time of stirring is 60-
90min。
9. the preparation method of a kind of Wild antheraea pernyi silk fibroin microsphere containing three-dimensional pore space structure according to claim 3, it is special
Levy and be：In the step (3), the temperature of heating stirring is 95-98 DEG C, and mixing speed is 200-500rpm, and the time is 20-
30min。
10. the preparation method of a kind of Wild antheraea pernyi silk fibroin microsphere containing three-dimensional pore space structure according to claim 3, it is special
Levy and be：In the step (3), the temperature of frozen drying process is -4--10 DEG C, and the time is 1-2h.
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| CN112779777A (en) * | 2021-01-04 | 2021-05-11 | 陕西科技大学 | Preparation method of vinyl collagen microsphere/polyamide fiber composite material |
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| CN111647176A (en) * | 2020-05-27 | 2020-09-11 | 浙江理工大学 | Preparation method of sericin microspheres |
| CN111647176B (en) * | 2020-05-27 | 2022-12-06 | 浙江理工大学 | Preparation method of sericin microspheres |
| CN112663344A (en) * | 2020-12-29 | 2021-04-16 | 泉州市伊呗思谷化妆品科技有限公司 | Waterproof moisture-permeable film and preparation method thereof |
| CN112779777A (en) * | 2021-01-04 | 2021-05-11 | 陕西科技大学 | Preparation method of vinyl collagen microsphere/polyamide fiber composite material |
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