CN106702517A - Medical textile material and preparation method thereof - Google Patents
Medical textile material and preparation method thereof Download PDFInfo
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- CN106702517A CN106702517A CN201611109402.0A CN201611109402A CN106702517A CN 106702517 A CN106702517 A CN 106702517A CN 201611109402 A CN201611109402 A CN 201611109402A CN 106702517 A CN106702517 A CN 106702517A
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- Prior art keywords
- silk
- solution
- preparation
- tensile properties
- fibroin
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Classifications
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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
-
- 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
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
-
- 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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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Artificial Filaments (AREA)
- Cosmetics (AREA)
Abstract
The invention discloses a medical textile material and a preparation method thereof. The preparation method comprises the following steps: mixing formic acid, water, lithium bromide, a trihydroxymethyl aminomethane buffer solution and iso-tridecanol polyoxyethylene ether to form a mixed solution; degumming silks, dissolving in the mixed solution, and adding calcium chloride; dropwise adding into a carbonate solution to obtain a reaction solution; filtering the reaction solution, washing and drying filter cakes, and thus obtaining calcium carbonate nanowires; dissolving the degummed silks in the mixed solution, adding disodium hydrogen phosphate dodecahydrate, and stirring for 1 to 1.5 hours, thus obtaining a fibroin solution; adjusting mass concentration of the fibroin solution to be 35 to 40 percent; adding a chemical reagent; and adding chitosan and calcium carbonate nanowire to obtain a spinning solution, and electrostatically spinning to obtain the medical textile material. The sterilization rate (escherichia coli) of the medical textile material prepared by the method in 24 hours is 99 percent or higher; the thermal deformation temperature is higher than 108 DEG C; the breaking strength is higher than 10MPa, and the elongation at break is 10 percent or higher; and Young modulus is 0.1GPa or higher.
Description
Technical field
The invention belongs to technical field of macromolecules, and in particular to a kind of Tensile properties and preparation method thereof.
Background technology
Silk has wide as a kind of natural protein fibre of excellent in mechanical performance in fibrous composite field
Application prospect, particularly in technical field of biological material；However, the multilevel hierarchy that silk is possessed in itself, particularly internal in nanometer
The beta sheet crystalline texture that size is formed so that Tensile properties are difficult to mutually be merged with macromolecular material, it is impossible to form phase
The combination interface of appearance, causes silk to strengthen composite materials property poor.The preparation of macromolecular fibre generally comprises material modification
Modifier is obtained, then carries out spinning；Or modifier mix with other additives again after carry out spinning again.Existing medical textile
Material is generally cotton fiber, because its biocompatibility is preferable；But cotton fiber be abiotic medical material, biocompatibility compared with
Difference, non-degradable, cotton fiber is short fibre in addition, and mechanical property is poor, and hot property is poor, therefore is mainly used as medical dressing,
Such as gauze.
The content of the invention
It is an object of the invention to provide a kind of Tensile properties and preparation method thereof, with excellent biocompatibility with
And mechanical property.
To achieve the above object of the invention, the technical solution adopted by the present invention is：
A kind of preparation method of Tensile properties, comprises the following steps：
(1) formic acid, water, lithium bromide and TRIS buffer are mixed, adds isomerous tridecanol polyoxy second
Alkene ether constitutes mixed liquor；
（2）It is dissolved in mixed liquor after natural silk degumming, adds calcium chloride, obtains silk fibroin protein solution；Then it is fibroin albumen is molten
Drop is added in carbonate solution, obtains reaction solution；Then filtering reacting liquid, filter cake by washing, dry after obtain calcium carbonate
Nano wire；
（3）It is dissolved in mixed liquor after natural silk degumming, adds disodium hydrogen phosphate, stirring obtains fibroin after 1~1.5 hour
Solution；The mass concentration for adjusting silk fibroin solution is 35~40%；It is subsequently adding double (2,3- epoxies cyclopentyl) ether, 2- vinyl
Pyrroles, two（4- methoxyphenyls）Phosphine oxide, N hydroxymethyl acrylamide, stir 40~55 minutes；It is subsequently adding shitosan and carbon
Sour calcium nano wire, heating stirring obtains spinning solution in 10 minutes, then obtains Tensile properties by Static Spinning.
In the present invention, in step (1), formic acid, water, lithium bromide, TRIS buffer, isomerous tridecanol gather
The mass ratio of oxygen vinethene is 70: 80: 18: 50: 5.The present invention adds organic component in silk lysate, increased lithium bromide
Activity, and avoid silk from being completely dissolved so that fibroin keeps certain fibrillar structure, carried to improve product mechanical property
For basis.
In the present invention, in step (2), the time that silk fibroin protein solution is added dropwise in carbonate solution is 30 minutes；Carbonic acid
Salt is sodium acid carbonate.The present invention obtains natural fibroin albumen fibril with calcium salt/mixed liquor dissolving silk, and then with fibril as template
Induction calcium ion mineralising generation calcium carbonate nano wire, the calcium carbonate nano wire of preparation is in nano-scale, and diameter most I is extremely
10nm, with excellent high length-diameter ratio.
In the present invention, in step (2), the silk is tussah silk, ricinus silk or wild silk yarn；It is described in step (3)
Silk is tussah silk, ricinus silk or wild silk yarn.
In the present invention, in step (2), silk, calcium chloride, the mass ratio of carbonate are 10: 70: 50.Under the ratio, knot
Time for adding is closed, the formation of calcium carbonate nano wire can be effectively induced.
In the present invention, in step (3), silk is 10: 7 with the mass ratio of disodium hydrogen phosphate.Ten hydrogen phosphate dihydrates
Disodium can be effectively increased the solute effect of silk so that fibrillar structure is swelling thoroughly, beneficial to follow-up addition reagent and fibroin
Mixing.In step (3), the molecular weight of the shitosan is 2600；The temperature of the heating stirring is 60 DEG C.Low-molecular-weight shell gathers
Sugar avoids interference of the spinning process to fibroin fiber, can be activated instead beneficial to fibroin fiber globality, preferably heating-up temperature is kept
Reagent is answered, for the product for preparing excellent in mechanical performance provides basis.
In the present invention, in step (3), fibroin, double (2,3- epoxy cyclopentyl) ethers, 2- vinyl pyrroles, two（4- methoxies
Base phenyl）The mass ratio of phosphine oxide, N hydroxymethyl acrylamide, shitosan and calcium carbonate nano wire is 100: 62: 32: 28: 18: 78
∶18；The technological parameter of the Static Spinning is：15~25 kilovolts of voltage, receive 8~12 centimetres of distance, liquid inventory be 0.3~
0.4 mL/h.The present invention can prepare mechanical property, biocompatibility good under addition reagent effect using Static Spinning
Fibrous material.
The invention also discloses the Tensile properties prepared according to the preparation method of above-mentioned Tensile properties.
Because above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：
（1）The present invention is used with fibroin as primary raw material, and by adding rational material, electrostatic spinning obtains fibroin fiber, solution
Determine the existing problem that fibroin fiber processability is poor, mechanical strength is low, particularly added the modified fibre of calcium carbonate nano wire
Tie up and improve mechanical strength while certain biocompatibility is kept；
（2）The present invention based on fibroin albumen, it is swelling in mixed liquor, at the same add chemical reagent, fibroin albumen it is swelling but
It is insoluble, and by adding calcium chloride and disodium hydrogen phosphate, has respectively reached fibril template-mediated calcium carbonate and received
The swelling effect of rice noodles generation, fibril, the mixing of growth and fibroin albumen and chemical reagent beneficial to nano wire；
（3）Prepared by the preparation method of Tensile properties disclosed by the invention convenient, by electrostatic apparatus, you can easily prepare；
Beneficial to industrial applications.
Specific embodiment
With reference to embodiment, the invention will be further described：
Embodiment one
(1) 7Kg formic acid, 8Kg water, 1.8Kg lithium bromides and 5Kg TRIS buffers are mixed, is added
500g isomerous tridecanol polyoxyethylene ethers constitute mixed liquor；
（2）It is dissolved in mixed liquor after tussah degumming of silk, adds calcium chloride, obtains silk fibroin protein solution；Then by fibroin albumen
Solution is added dropwise in sodium bicarbonate aqueous solution in 30 minutes, obtains reaction solution；Then filtering reacting liquid, filter cake is by washing, dry
Calcium carbonate nano wire is obtained after dry；Silk, calcium chloride, the mass ratio of carbonate are 10: 70: 50；
（3）It is dissolved in mixed liquor after tussah degumming of silk, adds the disodium hydrogen phosphate of tussah yarn quality 70%, stirring 1 is small
When after obtain silk fibroin solution；The mass concentration for adjusting silk fibroin solution is 35%；Be subsequently adding double (2,3- epoxies cyclopentyl) ethers,
2- vinyl pyrroles, two（4- methoxyphenyls）Phosphine oxide, N hydroxymethyl acrylamide, stir 40 minutes；It is subsequently adding molecular weight
It is 2600 shitosan and calcium carbonate nano wire, 60 DEG C of heating stirrings obtain spinning solution in 10 minutes, then are cured by Static Spinning
Use textile material；Fibroin, double (2,3- epoxies cyclopentyl) ethers, 2- vinyl pyrroles, two（4- methoxyphenyls）Phosphine oxide, N- hydroxyls
The mass ratio of Methacrylamide, shitosan and calcium carbonate nano wire is 100: 62: 32: 28: 18: 78: 18；The technique of Static Spinning
Parameter is：25 kilovolts of voltage, receives 8 centimetres of distance, and liquid inventory is 0.3mL/h.
Embodiment two
(1) 7Kg formic acid, 8Kg water, 1.8Kg lithium bromides and 5Kg TRIS buffers are mixed, is added
500g isomerous tridecanol polyoxyethylene ethers constitute mixed liquor；
（2）It is dissolved in mixed liquor after ricinus silk degumming, adds calcium chloride, obtains silk fibroin protein solution；Then by fibroin egg
White solution is added dropwise in sodium bicarbonate aqueous solution in 30 minutes, obtains reaction solution；Then filtering reacting liquid, filter cake by washing,
Calcium carbonate nano wire is obtained after drying；Silk, calcium chloride, the mass ratio of carbonate are 10: 70: 50；
（3）It is dissolved in mixed liquor after ricinus silk degumming, adds the disodium hydrogen phosphate of ricinus silk quality 70%, is stirred
Silk fibroin solution is obtained after mixing 1 hour；The mass concentration for adjusting silk fibroin solution is 40%；It is subsequently adding double (2,3- epoxies basic rings penta
Base) ether, 2- vinyl pyrroles, two（4- methoxyphenyls）Phosphine oxide, N hydroxymethyl acrylamide, stir 40 minutes；It is subsequently adding
Molecular weight is 2600 shitosan and calcium carbonate nano wire, and 60 DEG C of heating stirrings obtain spinning solution in 10 minutes, then by Static Spinning
Obtain Tensile properties；Fibroin, double (2,3- epoxies cyclopentyl) ethers, 2- vinyl pyrroles, two（4- methoxyphenyls）Oxygen
The mass ratio of phosphine, N hydroxymethyl acrylamide, shitosan and calcium carbonate nano wire is 100: 62: 32: 28: 18: 78: 18；Electrostatic
The technological parameter of spinning is：25 kilovolts of voltage, receives 12 centimetres of distance, and liquid inventory is 0.3 mL/h.
Embodiment three
(1) 7Kg formic acid, 8Kg water, 1.8Kg lithium bromides and 5Kg TRIS buffers are mixed, is added
500g isomerous tridecanol polyoxyethylene ethers constitute mixed liquor；
（2）It is dissolved in mixed liquor after giant silkworm degumming of silk, adds calcium chloride, obtains silk fibroin protein solution；Then by fibroin albumen
Solution is added dropwise in sodium bicarbonate aqueous solution in 30 minutes, obtains reaction solution；Then filtering reacting liquid, filter cake is by washing, dry
Calcium carbonate nano wire is obtained after dry；Silk, calcium chloride, the mass ratio of carbonate are 10: 70: 50；
（3）It is dissolved in mixed liquor after giant silkworm degumming of silk, adds the disodium hydrogen phosphate of giant silkworm yarn quality 70%, stirring 1 is small
When after obtain silk fibroin solution；The mass concentration for adjusting silk fibroin solution is 38%；Be subsequently adding double (2,3- epoxies cyclopentyl) ethers,
2- vinyl pyrroles, two（4- methoxyphenyls）Phosphine oxide, N hydroxymethyl acrylamide, stir 55 minutes；It is subsequently adding molecular weight
It is 2600 shitosan and calcium carbonate nano wire, 60 DEG C of heating stirrings obtain spinning solution in 10 minutes, then are cured by Static Spinning
Use textile material；Fibroin, double (2,3- epoxies cyclopentyl) ethers, 2- vinyl pyrroles, two（4- methoxyphenyls）Phosphine oxide, N- hydroxyls
The mass ratio of Methacrylamide, shitosan and calcium carbonate nano wire is 100: 62: 32: 28: 18: 78: 18；The technique of Static Spinning
Parameter is：25 kilovolts of voltage, receives 12 centimetres of distance, and liquid inventory is 0.3 mL/h.
Example IV
(1) 7Kg formic acid, 8Kg water, 1.8Kg lithium bromides and 5Kg TRIS buffers are mixed, is added
500g isomerous tridecanol polyoxyethylene ethers constitute mixed liquor；
（2）It is dissolved in mixed liquor after giant silkworm degumming of silk, adds calcium chloride, obtains silk fibroin protein solution；Then by fibroin albumen
Solution is added dropwise in sodium bicarbonate aqueous solution in 30 minutes, obtains reaction solution；Then filtering reacting liquid, filter cake is by washing, dry
Calcium carbonate nano wire is obtained after dry；Silk, calcium chloride, the mass ratio of carbonate are 10: 70: 50；
（3）It is dissolved in mixed liquor after ricinus silk degumming, adds the disodium hydrogen phosphate of ricinus silk quality 70%, is stirred
Silk fibroin solution is obtained after mixing 1 hour；The mass concentration for adjusting silk fibroin solution is 40%；It is subsequently adding double (2,3- epoxies basic rings penta
Base) ether, 2- vinyl pyrroles, two（4- methoxyphenyls）Phosphine oxide, N hydroxymethyl acrylamide, stir 40 minutes；It is subsequently adding
Molecular weight is 2600 shitosan and calcium carbonate nano wire, and 60 DEG C of heating stirrings obtain spinning solution in 10 minutes, then by Static Spinning
Obtain Tensile properties；Fibroin, double (2,3- epoxies cyclopentyl) ethers, 2- vinyl pyrroles, two（4- methoxyphenyls）Oxygen
The mass ratio of phosphine, N hydroxymethyl acrylamide, shitosan and calcium carbonate nano wire is 100: 62: 32: 28: 18: 78: 18；Electrostatic
The technological parameter of spinning is：25 kilovolts of voltage, receives 12 centimetres of distance, and liquid inventory is 0.4 mL/h.
Embodiment five
(1) 7Kg formic acid, 8Kg water, 1.8Kg lithium bromides and 5Kg TRIS buffers are mixed, is added
500g isomerous tridecanol polyoxyethylene ethers constitute mixed liquor；
（2）It is dissolved in mixed liquor after giant silkworm degumming of silk, adds calcium chloride, obtains silk fibroin protein solution；Then by fibroin albumen
Solution is added dropwise in sodium bicarbonate aqueous solution in 30 minutes, obtains reaction solution；Then filtering reacting liquid, filter cake is by washing, dry
Calcium carbonate nano wire is obtained after dry；Silk, calcium chloride, the mass ratio of carbonate are 10: 70: 50；
（3）It is dissolved in mixed liquor after tussah natural silk degumming, adds the disodium hydrogen phosphate of tussah silk quality 70%, is stirred
Silk fibroin solution is obtained after mixing 1 hour；The mass concentration for adjusting silk fibroin solution is 36%；It is subsequently adding double (2,3- epoxies basic rings penta
Base) ether, 2- vinyl pyrroles, two（4- methoxyphenyls）Phosphine oxide, N hydroxymethyl acrylamide, stir 40 minutes；It is subsequently adding
Molecular weight is 2600 shitosan and calcium carbonate nano wire, and 60 DEG C of heating stirrings obtain spinning solution in 10 minutes, then by Static Spinning
Obtain Tensile properties；Fibroin, double (2,3- epoxies cyclopentyl) ethers, 2- vinyl pyrroles, two（4- methoxyphenyls）Oxygen
The mass ratio of phosphine, N hydroxymethyl acrylamide, shitosan and calcium carbonate nano wire is 100: 62: 32: 28: 18: 78: 18；Electrostatic
The technological parameter of spinning is：15 kilovolts of voltage, receives 8 centimetres of distance, and liquid inventory is 0.3 mL/h.
24 hours sterilizing rates of above-mentioned Tensile properties（Escherichia coli）It is more than 99%；Heat distortion temperature is more than 108 DEG C；
Fracture strength is more than 10MPa, elongation at break more than 10%；More than Young's modulus 0.1GPa.
Claims (10)
1. a kind of preparation method of Tensile properties, it is characterised in that comprise the following steps：
（1）Formic acid, water, lithium bromide and TRIS buffer are mixed, isomerous tridecanol polyoxy second is added
Alkene ether constitutes mixed liquor；
（2）It is dissolved in mixed liquor after natural silk degumming, adds calcium chloride, obtains silk fibroin protein solution；Then it is fibroin albumen is molten
Drop is added in carbonate solution, obtains reaction solution；Then filtering reacting liquid, filter cake by washing, dry after obtain calcium carbonate
Nano wire；
（3）It is dissolved in mixed liquor after natural silk degumming, adds disodium hydrogen phosphate, stirring obtains fibroin after 1~1.5 hour
Solution；The mass concentration for adjusting silk fibroin solution is 35~40%；It is subsequently adding double (2,3- epoxies cyclopentyl) ether, 2- vinyl
Pyrroles, two（4- methoxyphenyls）Phosphine oxide, N hydroxymethyl acrylamide, stir 40~55 minutes；It is subsequently adding shitosan and carbon
Sour calcium nano wire, heating stirring obtains spinning solution in 10 minutes, then obtains Tensile properties by Static Spinning.
2. the preparation method of Tensile properties according to claim 1, it is characterised in that：In step (1), formic acid, water, bromine
It is 70: 80: 18: 50: 5 to change lithium, TRIS buffer, the mass ratio of isomerous tridecanol polyoxyethylene ether.
3. the preparation method of Tensile properties according to claim 1, it is characterised in that：In step (2), fibroin albumen is molten
It is 30 minutes that drop adds the time in carbonate solution；Carbonate is sodium acid carbonate.
4. the preparation method of Tensile properties according to claim 1, it is characterised in that：In step (2), the silk is
Tussah silk, ricinus silk or wild silk yarn；In step (3), the silk is tussah silk, ricinus silk or wild silk yarn.
5. the preparation method of Tensile properties according to claim 1, it is characterised in that：In step (2), silk, chlorination
Calcium, the mass ratio of carbonate are 10: 70: 50.
6. the preparation method of Tensile properties according to claim 1, it is characterised in that：In step (3), silk and 12
The mass ratio of water disodium hydrogen phosphate is 10: 7.
7. the preparation method of Tensile properties according to claim 1, it is characterised in that：In step (3), the shitosan
Molecular weight be 2600；The temperature of the heating stirring is 60 DEG C.
8. the preparation method of Tensile properties according to claim 1, it is characterised in that：In step (3), fibroin, it is double (2,
3- epoxies cyclopentyl) ether, 2- vinyl pyrroles, two（4- methoxyphenyls）Phosphine oxide, N hydroxymethyl acrylamide, shitosan with
The mass ratio of calcium carbonate nano wire is 100: 62: 32: 28: 18: 78: 18.
9. the preparation method of Tensile properties according to claim 1, it is characterised in that：In step (3), the Static Spinning
Technological parameter be：15~25 kilovolts of voltage, receives 8~12 centimetres of distance, and liquid inventory is 0.3~0.4 mL/h.
10. the Tensile properties that according to claim 1 prepared by the preparation method of Tensile properties.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611109402.0A CN106702517A (en) | 2016-12-06 | 2016-12-06 | Medical textile material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611109402.0A CN106702517A (en) | 2016-12-06 | 2016-12-06 | Medical textile material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
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| CN106702517A true CN106702517A (en) | 2017-05-24 |
Family
ID=58935829
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
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| CN201611109402.0A Pending CN106702517A (en) | 2016-12-06 | 2016-12-06 | Medical textile material and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108193312A (en) * | 2017-12-29 | 2018-06-22 | 付主枝 | A kind of preparation method and applications of composite fibre textile material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2958606A (en) * | 1952-06-06 | 1960-11-01 | Lever Brothers Ltd | Preparation of protein solutions |
| CN101081932A (en) * | 2007-06-06 | 2007-12-05 | 浙江理工大学 | Silk fibroin /calcium carbonate nano composite material and preparation method thereof |
| CN103341209A (en) * | 2013-07-08 | 2013-10-09 | 苏州大学 | Silk fibroin nanofiber membrane and preparation method thereof |
| CN103341214A (en) * | 2013-07-08 | 2013-10-09 | 苏州大学 | Silk fibroin membrane and preparation method thereof |
| CN104436285A (en) * | 2014-12-12 | 2015-03-25 | 苏州大学 | Regenerated silk fibroin gel mask and preparation method thereof |
-
2016
- 2016-12-06 CN CN201611109402.0A patent/CN106702517A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2958606A (en) * | 1952-06-06 | 1960-11-01 | Lever Brothers Ltd | Preparation of protein solutions |
| CN101081932A (en) * | 2007-06-06 | 2007-12-05 | 浙江理工大学 | Silk fibroin /calcium carbonate nano composite material and preparation method thereof |
| CN103341209A (en) * | 2013-07-08 | 2013-10-09 | 苏州大学 | Silk fibroin nanofiber membrane and preparation method thereof |
| CN103341214A (en) * | 2013-07-08 | 2013-10-09 | 苏州大学 | Silk fibroin membrane and preparation method thereof |
| CN104436285A (en) * | 2014-12-12 | 2015-03-25 | 苏州大学 | Regenerated silk fibroin gel mask and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108193312A (en) * | 2017-12-29 | 2018-06-22 | 付主枝 | A kind of preparation method and applications of composite fibre textile material |
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