CN106543744A - A kind of preparation method of fibroin albumen and polyurethane mixture film - Google Patents
A kind of preparation method of fibroin albumen and polyurethane mixture film Download PDFInfo
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- CN106543744A CN106543744A CN201611055941.0A CN201611055941A CN106543744A CN 106543744 A CN106543744 A CN 106543744A CN 201611055941 A CN201611055941 A CN 201611055941A CN 106543744 A CN106543744 A CN 106543744A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L89/00—Compositions of proteins; Compositions of derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2389/00—Characterised by the use of proteins; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/02—Applications for biomedical use
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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Abstract
The invention provides a kind of fibroin albumen and the preparation method of polyurethane mixture film, silkworm silk first to be added to the Na of cellulase2CO3In aqueous solution, 110 120 DEG C of insulations are warming up to, deionized water cleaning, obtains fibroin albumen after cooling；Again polypropylene glycol, dihydromethyl propionic acid are mixed, 120 DEG C of insulations are warming up to, 85 DEG C is cooled to and is added phenylene diisocyanate to be reacted, be cooled to room temperature, add acrylic acid, acetone, trihexylamine, stirring to stand in ice-water bath, filter, obtain polyurethane prepolymer；Then fibroin albumen is added in lithium-bromide solution, is stirred, mixed liquor imports ceramic super-filtering film and filtered, and obtains concentrated solution；Finally polyurethane prepolymer is added in gained concentrated solution, dispersion stands, and obtains final product blend film after being dried.The blend film of the present invention had both had higher intensity, while also maintaining excellent toughness, can be widely applied to biomedical materials field.
Description
Technical field
The invention belongs to biological medical polymer material technical field, and in particular to a kind of fibroin albumen and polyurethane comixing
The preparation method of film.
Background technology
Biological medical polymer material of the exploitation with good biocompatibility and good mechanical performance, is in recent years domestic and international
One study hotspot of technical field of biological material.Natural silk and spider silk due to high mechanical strength and toughness, well
Biological degradability and draw attention.Silkworm silk is made up of fibroin and sericin two parts, and sericin bag is accounted in the outside of fibroin albumen
The 25%～30% of silkworm silk weight, fibroin fiber is bonded together the silkworm silk to be formed with very high strength and toughness for it.But by
It is a kind of potential anaphylactogen in sericin, I type (Type-I) anaphylaxiss, therefore the presence of sericin can be caused to have impact on silkworm silk and exist
The application of biomedicine field.Fibroin albumen is the natural polymer fibrin obtained after natural silk degumming, and it contains two hatching egg
White matter chain, i.e. heavy chain (H-, about 390kDa) and light chain (L-, about 26kDa). both protein chains are by disulfide bond one
Rise.In addition, also there is a kind of glycoprotein of P25 (about 25kDa) in fibroin albumen, and in the way of non-covalent bond and heavy chain
It is connected with light chain.Fibroin albumen is mainly present with random coil, alpha-helix and beta sheet chain conformation form.Research shows silk fibroin
The mechanical property of dimension depends primarily on beta sheet chain structure therein and its along the height-oriented aggregated structure of fiber direction of principal axis.
Fibroin has unique molecular structure and good biocompatibility, can be processed into powder body, gel, microsphere, porous support, nanometer
Fiber and film, for the development of artificial organ and other composites, are with a wide range of applications.
The content of the invention
The technical problem of solution：The invention provides the preparation method of a kind of fibroin albumen and polyurethane mixture film, gained
Blend film had both had higher intensity, while also maintaining excellent toughness, can be widely applied to biomedical materials field.
Technical scheme：A kind of fibroin albumen and the preparation method of polyurethane mixture film, comprise the following steps：
Silkworm silk is added to the Na containing 0.5wt.% cellulase by step 12CO3In aqueous solution, 110-120 DEG C of insulation is warming up to
30min, after cooling, deionized water cleaning, obtains fibroin albumen；
Step 2, in parts by weight, polypropylene glycol 5-10 parts, dihydromethyl propionic acid 4-8 parts is mixed, 120 DEG C of guarantors are warming up to
Warm 30min, is cooled to 85 DEG C and adds phenylene diisocyanate 3-9 parts to be reacted, be cooled to room temperature, add acrylic acid 0.5-1.2
Part, acetone 2-5 parts, trihexylamine 1-6 parts, stirring are stood in ice-water bath, are filtered, are obtained polyurethane prepolymer；
Step 3, in parts by weight, step 1 gained fibroin albumen 4-10 parts is added in lithium-bromide solution 3-9 parts, stirring,
Mixed liquor imports ceramic super-filtering film and is filtered, and obtains concentrated solution；
Step 4, step 2 gained polyurethane prepolymer 10-20wt.% is added in step 3 gained concentrated solution, dispersion, quiet
Put, after being dried, obtain final product blend film.
Further, Na in step 12CO3Na in aqueous solution2CO3Concentration is 10-15wt.%.
Further, in step 2, the response time is 40-70min.
Further, in step 3, the scope of ceramic micro filter film average pore size is 200-500nm.
Further, in step 4, dispersion condition is 800-1000rpm, 10-15min.
Further, in step 4, baking temperature is 50-60 DEG C.
Beneficial effect：The blend film of the present invention had both had higher intensity, while also maintaining excellent toughness, extensively can answer
For biomedical materials field.
Specific embodiment
Embodiment 1
A kind of fibroin albumen and the preparation method of polyurethane mixture film, comprise the following steps：
Silkworm silk is added to the Na containing 0.5wt.% cellulase by step 12CO3In aqueous solution, 110 DEG C of insulations are warming up to
30min, after cooling, deionized water cleaning, obtains fibroin albumen；
Step 2, in parts by weight, by 5 parts of polypropylene glycol, 4 parts of mixing of dihydromethyl propionic acid, is warming up to 120 DEG C of insulations
30min, is cooled to 85 DEG C and adds 3 parts of phenylene diisocyanate to be reacted, be cooled to room temperature, add 0.5 part of acrylic acid, acetone 2
Part, 1 part of trihexylamine, stirring are stood in ice-water bath, are filtered, are obtained polyurethane prepolymer；
Step 3, in parts by weight, by step 1 gained fibroin albumen, 4 parts add in 3 parts of lithium-bromide solution, stirring, mixing
Liquid imports ceramic super-filtering film and is filtered, and obtains concentrated solution；
Step 4, step 2 gained polyurethane prepolymer 10wt.% is added in step 3 gained concentrated solution, dispersion, is stood,
Blend film is obtained final product after drying.
Wherein, Na in step 12CO3Na in aqueous solution2CO3Concentration is 10wt.%；In step 2, the response time is 40min；
In step 3, the scope of ceramic micro filter film average pore size is 200-500nm；In step 4, dispersion condition is 800rpm, 15min, is dried
Temperature is 50-60 DEG C.
Embodiment 2
A kind of fibroin albumen and the preparation method of polyurethane mixture film, comprise the following steps：
Silkworm silk is added to the Na containing 0.5wt.% cellulase by step 12CO3In aqueous solution, 115 DEG C of insulations are warming up to
30min, after cooling, deionized water cleaning, obtains fibroin albumen；
Step 2, in parts by weight, by 6 parts of polypropylene glycol, 7 parts of mixing of dihydromethyl propionic acid, is warming up to 120 DEG C of insulations
30min, is cooled to 85 DEG C and adds 4 parts of phenylene diisocyanate to be reacted, be cooled to room temperature, add 0.7 part of acrylic acid, acetone 4
Part, 4 parts of trihexylamine, stirring are stood in ice-water bath, are filtered, are obtained polyurethane prepolymer；
Step 3, in parts by weight, by step 1 gained fibroin albumen, 7 parts add in 5 parts of lithium-bromide solution, stirring, mixing
Liquid imports ceramic super-filtering film and is filtered, and obtains concentrated solution；
Step 4, step 2 gained polyurethane prepolymer 13wt.% is added in step 3 gained concentrated solution, dispersion, is stood,
Blend film is obtained final product after drying.
Wherein, Na in step 12CO3Na in aqueous solution2CO3Concentration is 12wt.%；In step 2, the response time is 60min；
In step 3, the scope of ceramic micro filter film average pore size is 200-500nm；In step 4, dispersion condition is 900rpm, 10min, is dried
Temperature is 50-60 DEG C.
Embodiment 3
A kind of fibroin albumen and the preparation method of polyurethane mixture film, comprise the following steps：
Silkworm silk is added to the Na containing 0.5wt.% cellulase by step 12CO3In aqueous solution, 110 DEG C of insulations are warming up to
30min, after cooling, deionized water cleaning, obtains fibroin albumen；
Step 2, in parts by weight, by 8 parts of polypropylene glycol, 7 parts of mixing of dihydromethyl propionic acid, is warming up to 120 DEG C of insulations
30min, is cooled to 85 DEG C and adds 7 parts of phenylene diisocyanate to be reacted, be cooled to room temperature, add 0.9 part of acrylic acid, acetone 4
Part, 5 parts of trihexylamine, stirring are stood in ice-water bath, are filtered, are obtained polyurethane prepolymer；
Step 3, in parts by weight, by step 1 gained fibroin albumen, 8 parts add in 7 parts of lithium-bromide solution, stirring, mixing
Liquid imports ceramic super-filtering film and is filtered, and obtains concentrated solution；
Step 4, step 2 gained polyurethane prepolymer 18wt.% is added in step 3 gained concentrated solution, dispersion, is stood,
Blend film is obtained final product after drying.
Wherein, Na in step 12CO3Na in aqueous solution2CO3Concentration is 13wt.%；In step 2, the response time is 40min；
In step 3, the scope of ceramic micro filter film average pore size is 200-500nm；In step 4, dispersion condition is 800rpm, 15min, is dried
Temperature is 50-60 DEG C.
Embodiment 4
A kind of fibroin albumen and the preparation method of polyurethane mixture film, comprise the following steps：
Silkworm silk is added to the Na containing 0.5wt.% cellulase by step 12CO3In aqueous solution, 120 DEG C of insulations are warming up to
30min, after cooling, deionized water cleaning, obtains fibroin albumen；
Step 2, in parts by weight, by 10 parts of polypropylene glycol, 8 parts of mixing of dihydromethyl propionic acid, is warming up to 120 DEG C of insulations
30min, is cooled to 85 DEG C and adds 9 parts of phenylene diisocyanate to be reacted, be cooled to room temperature, add 1.2 parts of acrylic acid, acetone 5
Part, 6 parts of trihexylamine, stirring are stood in ice-water bath, are filtered, are obtained polyurethane prepolymer；
Step 3, in parts by weight, by step 1 gained fibroin albumen, 10 parts add in 3 parts of lithium-bromide solution, stirring, mixing
Liquid imports ceramic super-filtering film and is filtered, and obtains concentrated solution；
Step 4, step 2 gained polyurethane prepolymer 20wt.% is added in step 3 gained concentrated solution, dispersion, is stood,
Blend film is obtained final product after drying.
Wherein, Na in step 12CO3Na in aqueous solution2CO3Concentration is 15wt.%；In step 2, the response time is 70min；
In step 3, the scope of ceramic micro filter film average pore size is 200-500nm；In step 4, dispersion condition is 1000rpm, 10min, is done
Dry temperature is 50-60 DEG C.
After testing, the fracture strength of 1 to 4 gained blend film of embodiment up to 4.60MPa, Young's moduluss 1.71MPa with
Upper, elongation at break is more than 1065%.
Claims (6)
1. the preparation method of a kind of fibroin albumen and polyurethane mixture film, it is characterised in that：Comprise the following steps：
Silkworm silk is added to the Na containing 0.5wt.% cellulase by step 12CO3In aqueous solution, 110-120 DEG C of insulation is warming up to
30min, after cooling, deionized water cleaning, obtains fibroin albumen；
Step 2, in parts by weight, polypropylene glycol 5-10 parts, dihydromethyl propionic acid 4-8 parts is mixed, 120 DEG C of insulations are warming up to
30min, is cooled to 85 DEG C and adds phenylene diisocyanate 3-9 parts to be reacted, be cooled to room temperature, add acrylic acid 0.5-1.2 parts,
Acetone 2-5 parts, trihexylamine 1-6 parts, stirring are stood in ice-water bath, are filtered, are obtained polyurethane prepolymer；
Step 3, in parts by weight, step 1 gained fibroin albumen 4-10 parts is added in lithium-bromide solution 3-9 parts, stirring, mixing
Liquid imports ceramic super-filtering film and is filtered, and obtains concentrated solution；
Step 4, step 2 gained polyurethane prepolymer 10-20wt.% is added in step 3 gained concentrated solution, dispersion, is stood, and is done
Blend film is obtained final product after dry.
2. the preparation method of fibroin albumen according to claim 1 and polyurethane mixture film, it is characterised in that：In step 1
Na2CO3Na in aqueous solution2CO3Concentration is 10-15wt.%.
3. the preparation method of fibroin albumen according to claim 1 and polyurethane mixture film, it is characterised in that：In step 2
Response time is 40-70min.
4. the preparation method of fibroin albumen according to claim 1 and polyurethane mixture film, it is characterised in that：In step 3
The scope of ceramic micro filter film average pore size is 200-500nm.
5. the preparation method of fibroin albumen according to claim 1 and polyurethane mixture film, it is characterised in that：In step 4
Dispersion condition is 800-1000rpm, 10-15min.
6. the preparation method of fibroin albumen according to claim 1 and polyurethane mixture film, it is characterised in that：In step 4
Baking temperature is 50-60 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611055941.0A CN106543744A (en) | 2016-11-25 | 2016-11-25 | A kind of preparation method of fibroin albumen and polyurethane mixture film |
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| CN201611055941.0A CN106543744A (en) | 2016-11-25 | 2016-11-25 | A kind of preparation method of fibroin albumen and polyurethane mixture film |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109179640A (en) * | 2018-10-31 | 2019-01-11 | 浙江工业大学上虞研究院有限公司 | A kind of cellular polyurethane foam beads filler of suitable for movable bed biofilm reactor and preparation method thereof |
| CN109439219A (en) * | 2018-10-25 | 2019-03-08 | 常州昊天新材料科技有限公司 | A kind of stretchable removal heat conductive flame-retarding double faced adhesive tape |
| CN109722039A (en) * | 2018-12-07 | 2019-05-07 | 厦门大学 | A kind of silk fibroin composite membrane and preparation method thereof, application |
| CN112175379A (en) * | 2020-09-30 | 2021-01-05 | 潘肖芬 | Biological membrane material |
| CN114989622A (en) * | 2022-07-15 | 2022-09-02 | 西南大学 | Isocyanate/silk fibroin composite film and preparation method thereof |
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| EP0875523A1 (en) * | 1993-05-24 | 1998-11-04 | Idemitsu Petrochemical Co. Ltd. | Process for producing fine silk fibroin powder |
| JP3502149B2 (en) * | 1994-04-28 | 2004-03-02 | セーレン株式会社 | Hygroscopic polyurethane foam and method for producing the same |
| CN102702727A (en) * | 2012-06-26 | 2012-10-03 | 重庆理工大学 | Preparation method for antibacterial composite material |
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2016
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|---|---|---|---|---|
| EP0875523A1 (en) * | 1993-05-24 | 1998-11-04 | Idemitsu Petrochemical Co. Ltd. | Process for producing fine silk fibroin powder |
| JP3502149B2 (en) * | 1994-04-28 | 2004-03-02 | セーレン株式会社 | Hygroscopic polyurethane foam and method for producing the same |
| CN102702727A (en) * | 2012-06-26 | 2012-10-03 | 重庆理工大学 | Preparation method for antibacterial composite material |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109439219A (en) * | 2018-10-25 | 2019-03-08 | 常州昊天新材料科技有限公司 | A kind of stretchable removal heat conductive flame-retarding double faced adhesive tape |
| CN109179640A (en) * | 2018-10-31 | 2019-01-11 | 浙江工业大学上虞研究院有限公司 | A kind of cellular polyurethane foam beads filler of suitable for movable bed biofilm reactor and preparation method thereof |
| CN109179640B (en) * | 2018-10-31 | 2021-08-06 | 浙江工业大学上虞研究院有限公司 | Porous polyurethane foam particle filler suitable for moving bed biofilm reactor and preparation method thereof |
| CN109722039A (en) * | 2018-12-07 | 2019-05-07 | 厦门大学 | A kind of silk fibroin composite membrane and preparation method thereof, application |
| CN112175379A (en) * | 2020-09-30 | 2021-01-05 | 潘肖芬 | Biological membrane material |
| CN114989622A (en) * | 2022-07-15 | 2022-09-02 | 西南大学 | Isocyanate/silk fibroin composite film and preparation method thereof |
| CN114989622B (en) * | 2022-07-15 | 2023-03-03 | 西南大学 | Isocyanate/silk fibroin composite film and preparation method thereof |
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