CN106479195A - A kind of nano-cellulose strengthens fibroin albumen composite material and preparation method thereof - Google Patents
A kind of nano-cellulose strengthens fibroin albumen composite material and preparation method thereof Download PDFInfo
- Publication number
- CN106479195A CN106479195A CN201610948121.8A CN201610948121A CN106479195A CN 106479195 A CN106479195 A CN 106479195A CN 201610948121 A CN201610948121 A CN 201610948121A CN 106479195 A CN106479195 A CN 106479195A
- Authority
- CN
- China
- Prior art keywords
- cellulose
- fibroin
- nano
- solution
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- 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
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
- C08L1/04—Oxycellulose; Hydrocellulose, e.g. microcrystalline cellulose
-
- 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
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/048—Elimination of a frozen liquid phase
- C08J2201/0484—Elimination of a frozen liquid phase the liquid phase being aqueous
-
- 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
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/04—Oxycellulose; Hydrocellulose
-
- 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
-
- 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
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
- C08J2401/04—Oxycellulose; Hydrocellulose
-
- 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
- C08J2489/00—Characterised by the use of proteins; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The present invention relates to technical field of polymer materials, specifically related to a kind of nano-cellulose strengthens fibroin albumen composite material and preparation method thereof, fibroin fiber and cellulose are dissolved for cosolvent with LiBr, by controlling the dissolution degree of cellulosic material, retains the nanostructured of cellulose；The solution temperature of wherein cellulose controls at 80 ~ 150 DEG C；The fibroin obtaining/cellulose blending solution can quickly form gel, it is to avoid in solution, nano-cellulose is assembled and skewness phenomenon；This gel can prepare film forming and porous material after being further dried, and obtains the enhanced fibroin albumen composite material of nano-cellulose.The preparation process of the present invention is simple, controlled；The composite inner of gained comprises equally distributed nano-cellulose, and intensity and extension at break are remarkably reinforced compared with regenerated silk fibroin material.
Description
Technical field
The present invention relates to technical field of polymer materials is and in particular to a kind of nano-cellulose strengthens fibroin albumen composite wood
Material and preparation method thereof.
Background technology
Silkworm fibroin is the high-purity protein of the secretion by silk fabric gland, miscellaneous without organelle and other biological
Matter, biological safety is high.Silkworm fibroin is made up of 20 kinds of aminoacid such as aminoacetic acid, alanine, serine, can be biological
Degraded and finally catabolite are for polypeptide and free amino acid easily by organism metabolism.Fibroin albumen biocompatibility is good, silkworm
Silk fiber is used for medical operation suture thread many decades, and clinical effectiveness is long-tested.Experiment in vitro and internal as a result, it was confirmed that
Regenerated silk material can support the growth of various kinds of cell, shows immunology inertia and relatively low inflammatory reaction.Therefore, fibroin
Albumen is a kind of ideal macromolecule raw material preparing bio-medical material.At present, silk fibroin material has been widely used for skin
The research of the tissue repair such as skin, ligament, blood vessel.
As a kind of natural protein fibre, silk fiber has excellent mechanical property.However, in order to obtain not similar shape
The material of formula, such as film, porous support, tubular bracket etc., need for fibroin fiber to dissolve formation regenerated silk fibroin solution.Molten
In solution regenerative process, the crystalline texture of fibroin fiber is substantially destroyed, and fibroin macromole is degraded, molecular weight and molecular weight.By
The material mechanical performance natural silk fiber that compares of regenerated silk fibroin preparation is decreased obviously it is difficult to meet some organizational projects
The demand of material, such as bone tissue engineering scaffold and artificial blood vessel.
Nano-cellulose is a kind of a diameter of 1-30 nm extracting from native cellulose, and length arrives several for tens nanometers
Hundred microns of rigid rod fiber element or cellulose nanometer fibril.The nano-cellulose degree of polymerization and degree of crystallinity are high, have high-strength
Degree, the feature of high-moduluss, and nano-cellulose degradable, renewable and biocompatibility are good, in high-performance biomaterial
Huge application prospect is shown in field.Due to high performance mechanical characteristics, strengthen regeneration with nano-cellulose dispersion phase
Fibroin material, is obtained in that the composite of excellent in mechanical performance.And, cellulose contains substantial amounts of-OH, can be with silk
- the COOH and-NH of fibroin2Group can form substantial amounts of hydrogen bond, and the increase of this intermolecular interaction can be further
Improve the mechanical property of material.On the other hand, in the application process of tissue engineering bracket, it is compound to the nanometer in timbering material
Cellulose can for cell stick and migrate offer guiding signal.
In order to obtain the enhanced composite of nano-cellulose, current main method is first to extract Cellulose nanocrystal palpus
Or fibril, then it is blended with high polymer.Not only technique is loaded down with trivial details for this method, and the nano-cellulose of typically acquisition is difficult in height
Dispersed in copolymer solution, greatly limit its range.Therefore, development is a kind of can obtain stable cellulose nanometer
Fibril and make its in fibroin albumen matrix homodisperse simple effective ways for preparation high-performance fibroin albumen composite wood
Material has great importance.Before making the present invention, Chinese invention patent（CN103498210）It is prepared for a kind of high intensity fibroin egg
White fiber, Cellulose nanocrystal must be carried out wet spinning with the silk fibroin protein solution blending concentrating and prepare composite fibre.But,
The method first have to extract Cellulose nanocrystal must, complex process, and, Cellulose nanocrystal must easily be reunited, and is difficult to uniformly
Be dispersed in silk fibroin solution and form uniform fiber.
In view of disadvantages described above, the present inventor pass through positive study and innovated, invented one kind and prepared nano-cellulose
Strengthen the method for fibroin albumen composite material so as to fibroin material has more the value in industrialization.
Content of the invention
It is an object of the invention to overcoming the deficiencies in the prior art, providing simple effective method, preparing nano-cellulose
Strengthen fibroin albumen composite material.
The purpose of the present invention is achieved through the following technical solutions：
A kind of nano-cellulose strengthens the preparation method of fibroin albumen composite material, comprises the following steps：
S1. uniformly, dissolving bath raio is 1 the natural silk fiber of degumming to be dissolved in mixed dissolution in LiBr：4-20, obtains fibroin egg
White solution；
S2. uniformly, dissolving bath raio is 1 cellulose to be dissolved in mixed dissolution in LiBr：50-200, obtains the cellulose of homogeneous transparent
Solution；
S3. by silk fibroin protein solution and cellulose solution mix homogeneously, process through deaeration, obtain blended liquid；
S4. blended liquid is cooled down, formed gel, then by gel mass concentration 50-100% alcohol solution for soaking 0.5-5h,
Rinsed with water again, obtain the fibroin/cellulose gel of purification.
Further, in described step S1 and S2, the concentration of LiBr is 5-10mol/L.
Further, in described step S1, the dissolution conditions of fibroin fiber are that stirring at 40-70 DEG C mixes 0.5-4h,
Too high temperature and long time is avoided to cause the decline of silk fibroin molecular amount.
Further, in described step S2, the dissolution conditions of cellulose are that stirring at 80-150 DEG C mixes 0.5-5h,
Too high temperature and long time is avoided to destroy cellulose nanostructured.
Further, in described step S3, the condition of silk fibroin protein solution and cellulose solution mixing is, at 80-110 DEG C
Lower stirring mixing 3-10min.
Further, the cellulose described in described step S2 is derived from least one in following cellulosic materials：Cotton Gossypii,
Cotton linter, Cotton Pulp, wood pulp cellulose, wood pulps, absorbent cotton, cellulosic filter paper, Microcrystalline Cellulose, timber, straw and its
Cellulosicss.
Further, described cellulosic degree of polymerization is in 150-1500.
Further, described state in step S3, by fibroin albumen and cellulose mass ratio be 0.25-4：1 being blended silk
Fibroin solution and cellulose solution.
Further, in described step S4 alcoholic solution be methanol, ethanol, isopropanol, butanol, isobutanol, in the tert-butyl alcohol
At least one.
A kind of nano-cellulose strengthens fibroin albumen composite material, is prepared from by said method.
Above-mentioned nano-cellulose strengthens the application of fibroin albumen composite material, makes film including drying, or lyophilization system
Standby porous material.
The invention has the beneficial effects as follows：
1. the present invention dissolves cellulose with LiBr, remains the nanostructured of native cellulose, pass through simultaneously in course of dissolution
Control dissolution conditions can directly obtain nano-cellulose suspension；
2., in the preparation method of the present invention, cellulose solution quickly can form gel after the cooling period, so that nanofiber
Element is evenly dispersed in fibroin/cellulose mixed gel, it is to avoid nano-cellulose in dried composite and gathers
Collection and skewness phenomenon；
3. the present invention dissolves fibroin and cellulose using LiBr as cosolvent it is not necessary to being used in combination of multiple chemical reagent,
Preparation process is simple, controlled, safety.
Brief description
Fig. 1 is the electron microscope on the surface of fibroin/cellulose blending film in embodiment 1 preparation process；
Fig. 2 is the electron microscope in the section of fibroin/cellulose blending film in embodiment 1 preparation process；
The load-deformation curve of the fibroin that Fig. 3 obtains for embodiment 1/cellulose blending film；
The electron microscope of the fibroin that Fig. 4 obtains for embodiment 2/fibrination Porous materials.
Specific embodiment
Below by way of specific embodiment and accompanying drawing, the present invention is described in further detail, but should not be interpreted as this
The scope of the present invention is only limitted to Examples below.In the case of without departing from said method thought of the present invention, general according to this area
Various replacements or change that logical technological know-how and customary means are made, should be included in the scope of the present invention.
Embodiment 1
100 g silkworm raw silks are immersed the 0.05%NaCO of 5 L3In solution, boil process 30 min in 98 ~ 100 DEG C, repeat 3
Secondary, make natural silk degumming, fully wash and obtain pure silk cellulose fiber after being dried；The fibroin fiber of 10 g degummings is added to 50 mL's
In the LiBr solution of 9.3 mol/L, at 60 DEG C, stirring and dissolving 55 min obtains fibroin albumen mixed solution；
In the LiBr solution of 9.3 mol/L that 1 g Microcrystalline Cellulose powder is added to 80 mL, stirring and dissolving 55 at 110 DEG C
Min obtains cellulose solution；
Silk fibroin protein solution and cellulose solution are pressed the mass ratio 50 of fibroin and fiber:50 mixing, stir 5 at 110 DEG C
Min mix homogeneously, obtains fibroin albumen/cellulose mixed solution, cools down under room temperature, forms the gel of blending；
Above-mentioned gel is soaked 2 h with 75% ethanol, then soaks 48 h in the deionized water with flowing, remove LiBr；
48 hs will be dried at 37 DEG C in vacuum drying oven of fibroin/cellulose gel after purification, obtain nano-cellulose and strengthen
Fibroin membrane.
The enhanced fibroin membrane of nano-cellulose obtaining in embodiment 1 preparation process is done Electronic Speculum detection, testing result is such as
Shown in Fig. 1 and Fig. 2；The enhanced fibroin membrane of nano-cellulose that embodiment 1 is obtained carries out mechanical test, and with LiBr dissolving thoroughly
The pure fibroin membrane analysing the regenerated silk solution preparation obtaining compares, and testing result is as shown in Figure 3.
Embodiment 2
In the LiBr solution of 10 mol/L fibroin fiber of 20 g degummings being added to 100 mL, stirring and dissolving 58 at 60 DEG C
Min obtains fibroin albumen mixed solution；
In the LiBr solution of 10 mol/L that 2 g Microcrystalline Cellulose powder are added to 160 mL, stirring and dissolving 58 at 110 DEG C
Min obtains cellulose solution；
Silk fibroin protein solution and cellulose solution are pressed the mass ratio 20 of fibroin and fiber:80 mixing, stir 3 at 110 DEG C
Min mix homogeneously, obtains fibroin albumen/cellulose mixed solution.Cool down under room temperature, form the gel of blending；
Above-mentioned gel is soaked 2 h with 50% ethanol, in flowing water, then soaks 48 h, remove LiBr；
By fibroin/cellulose gel after purification respectively with 50%, 75% the tert-butyl alcohol and anhydrous tertiary butanol processed successively
30 min, then freeze 24 h at -20 DEG C, obtain the solid freezing.
By the solid of above-mentioned freezing freeze-drying process 48 h according to a conventional method, obtain nano-cellulose enhanced fibroin egg
White porous material.
The enhanced silk fibroin porous material of nano-cellulose obtaining in embodiment 2 preparation process is done Electronic Speculum detection,
Testing result is as shown in Figure 4.
Embodiment 3
In the LiBr solution of 8 mol/L fibroin fiber of 10 g degummings being added to 40 mL, stirring and dissolving 120 at 60 DEG C
Min obtains fibroin albumen mixed solution；
In the LiBr solution of 8 mol/L 1 g cellulosic filter paper being added to 100 mL, at 90 DEG C, stirring and dissolving 4 h, obtains
Cellulose solution；
Silk fibroin protein solution and cellulose solution are pressed the mass ratio 80 of fibroin and fiber:20 mixing, stir 5 min at 90 DEG C
Mix homogeneously, obtains fibroin albumen/cellulose mixed solution；Cool down under room temperature, form the gel of blending；
Above-mentioned gel is soaked 1 h with 90% methanol, in flowing water, then soaks 72 h, remove LiBr；
48 hs will be dried at 37 DEG C in vacuum drying oven of fibroin/cellulose gel after purification, obtain nano-cellulose and strengthen
Fibroin membrane.
Embodiment 4
In the LiBr solution of 5 mol/L fibroin fiber of 10 g degummings being added to 40 mL, stirring and dissolving 120 at 60 DEG C
Min obtains fibroin albumen mixed solution；
In the LiBr solution of 5 mol/L 1 g cellulosic filter paper being added to 100 mL, at 90 DEG C, stirring and dissolving 4 h, obtains
Cellulose solution；
Silk fibroin protein solution and cellulose solution are pressed the mass ratio 80 of fibroin and fiber:20 mixing, stir 10 at 90 DEG C
Min mix homogeneously, obtains fibroin albumen/cellulose mixed solution；Cool down under room temperature, form the gel of blending；
Above-mentioned gel is soaked 1 h with 100% methanol, in flowing water, then soaks 72 h, remove LiBr；
48 hs will be dried at 37 DEG C in vacuum drying oven of fibroin/cellulose gel after purification, obtain nano-cellulose and strengthen
Fibroin membrane.
The above be only the preferred embodiment of the present invention it should be understood that the present invention be not limited to described herein
Form, is not to be taken as the exclusion to other embodiment, and can be used for various other combinations, modification and environment, and can be at this
In the described contemplated scope of literary composition, it is modified by the technology or knowledge of above-mentioned teaching or association area.And those skilled in the art are entered
The change of row and change, then all should be in the protection domains of claims of the present invention without departing from the spirit and scope of the present invention
Interior.
Claims (10)
1. a kind of nano-cellulose strengthens the preparation method of fibroin albumen composite material it is characterised in that comprising the following steps：
S1. uniformly, dissolving bath raio is 1 the natural silk fiber of degumming to be dissolved in mixed dissolution in LiBr：4-20, obtains fibroin egg
White solution；
S2. uniformly, dissolving bath raio is 1 cellulose to be dissolved in mixed dissolution in LiBr：50-200, obtains the cellulose of homogeneous transparent
Solution；
S3. by silk fibroin protein solution and cellulose solution mix homogeneously, process through deaeration, obtain blended liquid；
S4. blended liquid is cooled down, formed gel, then by gel mass concentration 50-100% alcohol solution for soaking 0.5-5h,
Rinsed with water again, obtain the fibroin/cellulose gel of purification.
2. a kind of nano-cellulose according to claim 1 strengthens the preparation method of fibroin albumen composite material, its feature
It is, in described step S1 and S2, the concentration of LiBr is 5-10mol/L.
3. a kind of nano-cellulose according to claim 1 strengthens the preparation method of fibroin albumen composite material, its feature
It is, in described step S1, the dissolution conditions of fibroin fiber are that stirring at 40-70 DEG C mixes 0.5-4h；Described step S2
In, the dissolution conditions of cellulose are that stirring at 80-150 DEG C mixes 0.5-5h.
4. a kind of nano-cellulose according to claim 1 strengthens the preparation method of fibroin albumen composite material, its feature
It is, in described step S3, the condition of silk fibroin protein solution and cellulose solution mixing is that stirring at 80-110 DEG C mixes 3-
10min.
5. a kind of nano-cellulose according to claim 1 strengthens the preparation method of fibroin albumen composite material, its feature
It is, the cellulose described in described step S2 is derived from least one in following cellulosic materials：Cotton Gossypii, cotton linter, cotton pulp
The dregs of rice, wood pulp cellulose, wood pulps, absorbent cotton, cellulosic filter paper, Microcrystalline Cellulose, timber, straw and its cellulosicss.
6. a kind of nano-cellulose according to claim 5 strengthens the preparation method of fibroin albumen composite material, its feature
It is, described cellulosic degree of polymerization is in 150-1500.
7. a kind of nano-cellulose according to claim 1 strengthens the preparation method of fibroin albumen composite material, its feature
Be, described state in step S3, by fibroin albumen and cellulose mass ratio be 0.25-4：1 come to be blended silk fibroin protein solution and
Cellulose solution.
8. a kind of nano-cellulose according to claim 1 strengthens the preparation method of fibroin albumen composite material, its feature
Be, in described step S4 alcoholic solution be methanol, ethanol, isopropanol, butanol, isobutanol, at least one in the tert-butyl alcohol.
9. a kind of nano-cellulose strengthens fibroin albumen composite material it is characterised in that described in claim 1-8 any one
Method is prepared from.
10. a kind of nano-cellulose strengthens the application of fibroin albumen composite material it is characterised in that film is made in inclusion drying, or
Porous material is prepared in lyophilization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610948121.8A CN106479195B (en) | 2016-10-26 | 2016-10-26 | A kind of nano-cellulose enhancing fibroin albumen composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610948121.8A CN106479195B (en) | 2016-10-26 | 2016-10-26 | A kind of nano-cellulose enhancing fibroin albumen composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106479195A true CN106479195A (en) | 2017-03-08 |
| CN106479195B CN106479195B (en) | 2019-01-15 |
Family
ID=58271771
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610948121.8A Active CN106479195B (en) | 2016-10-26 | 2016-10-26 | A kind of nano-cellulose enhancing fibroin albumen composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106479195B (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107012525A (en) * | 2017-06-01 | 2017-08-04 | 合肥创沃科技有限公司 | A kind of preparation method of the composite regenerated cellulose tissue repair materials of chitosan |
| CN107287689A (en) * | 2017-06-26 | 2017-10-24 | 苏州威尔德工贸有限公司 | A kind of preparation method of the composite silk fiber of high-flexibility |
| CN107348885A (en) * | 2017-07-13 | 2017-11-17 | 芜湖慧宇商贸有限公司 | A kind of preparation method of fibroin albumen towel |
| CN107419515A (en) * | 2017-09-17 | 2017-12-01 | 赵兵 | A kind of amphoteric cellulose composite of graphene coated and preparation method thereof |
| CN107446165A (en) * | 2017-09-17 | 2017-12-08 | 赵兵 | A kind of graphene oxide fibroin amphoteric cellulose composite and preparation method |
| CN107556759A (en) * | 2017-09-17 | 2018-01-09 | 钱景 | A kind of titania nanotube silk salix monogolica composite |
| CN107599544A (en) * | 2017-09-13 | 2018-01-19 | 江苏科技大学 | Ramulus Mori fiber fibroin albumen multilayer complex films and preparation method thereof |
| CN108219408A (en) * | 2017-12-20 | 2018-06-29 | 南通理工学院 | Degradable 3d printing material and preparation method thereof |
| CN108853594A (en) * | 2018-06-25 | 2018-11-23 | 东莞市联洲知识产权运营管理有限公司 | A kind of preparation method of the porous Medical rack dressing of cellulose of nanometer of silk protein powder enhancing |
| CN109369961A (en) * | 2018-10-16 | 2019-02-22 | 河南工程学院 | A kind of nano-cellulose based film material and preparation method thereof of polypeptide enhancing |
| CN109594325A (en) * | 2018-12-11 | 2019-04-09 | 佛山市名洲纺织有限公司 | A kind of nanometic zinc oxide rod array it is modified lead wet cotton fiber or its fabric and preparation method thereof |
| CN110144123A (en) * | 2019-04-08 | 2019-08-20 | 复旦大学 | A kind of fibroin/cellulose derivative composite material and preparation method |
| CN110215351A (en) * | 2019-06-06 | 2019-09-10 | 杭州贝高母婴用品有限公司 | A kind of soft, paper diaper of pro-skin and its production technology |
| CN111499927A (en) * | 2020-06-24 | 2020-08-07 | 内蒙古科技大学 | Cellulose/silk fibroin composite aerogel long fiber and preparation method thereof |
| CN113174074A (en) * | 2021-02-08 | 2021-07-27 | 四川大学华西医院 | Conductive silk fibroin film and preparation method and application thereof |
| CN114249982A (en) * | 2022-01-25 | 2022-03-29 | 武汉纺织大学 | Preparation method and application of high-strength high-modulus silk material |
| CN114958009A (en) * | 2022-05-24 | 2022-08-30 | 浙江理工大学 | Preparation method of silk-based high-strength ionic gel flexible sensing material |
| CN115558151A (en) * | 2022-08-25 | 2023-01-03 | 江苏省农业科学院 | Aerogel taking mung bean protein and burdock nanocellulose as template for synergistically stabilizing foam |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101205367A (en) * | 2007-12-06 | 2008-06-25 | 复旦大学 | Total-fibroin albumen composite material and preparation method thereof |
| CN102344685A (en) * | 2010-08-05 | 2012-02-08 | 中国科学院化学研究所 | Method for preparing nano cellulose microfibril reinforced polymer composite material |
| CN102719103A (en) * | 2012-06-21 | 2012-10-10 | 浙江大学 | Preparation method of plastic sericin film |
| CN103498210A (en) * | 2013-08-21 | 2014-01-08 | 浙江理工大学 | Biomimetic preparation method of high-strength regenerated silk protein fiber |
| CN104448844A (en) * | 2014-11-17 | 2015-03-25 | 浙江大学 | Preparation method of water-insoluble flexible silk fibroin membrane |
| WO2015137170A1 (en) * | 2014-03-12 | 2015-09-17 | 富士フイルム株式会社 | Method for producing porous cellulose particles, and porous cellulose particles |
-
2016
- 2016-10-26 CN CN201610948121.8A patent/CN106479195B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101205367A (en) * | 2007-12-06 | 2008-06-25 | 复旦大学 | Total-fibroin albumen composite material and preparation method thereof |
| CN102344685A (en) * | 2010-08-05 | 2012-02-08 | 中国科学院化学研究所 | Method for preparing nano cellulose microfibril reinforced polymer composite material |
| CN102719103A (en) * | 2012-06-21 | 2012-10-10 | 浙江大学 | Preparation method of plastic sericin film |
| CN103498210A (en) * | 2013-08-21 | 2014-01-08 | 浙江理工大学 | Biomimetic preparation method of high-strength regenerated silk protein fiber |
| WO2015137170A1 (en) * | 2014-03-12 | 2015-09-17 | 富士フイルム株式会社 | Method for producing porous cellulose particles, and porous cellulose particles |
| CN104448844A (en) * | 2014-11-17 | 2015-03-25 | 浙江大学 | Preparation method of water-insoluble flexible silk fibroin membrane |
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107012525A (en) * | 2017-06-01 | 2017-08-04 | 合肥创沃科技有限公司 | A kind of preparation method of the composite regenerated cellulose tissue repair materials of chitosan |
| CN107287689A (en) * | 2017-06-26 | 2017-10-24 | 苏州威尔德工贸有限公司 | A kind of preparation method of the composite silk fiber of high-flexibility |
| CN107348885A (en) * | 2017-07-13 | 2017-11-17 | 芜湖慧宇商贸有限公司 | A kind of preparation method of fibroin albumen towel |
| CN107599544A (en) * | 2017-09-13 | 2018-01-19 | 江苏科技大学 | Ramulus Mori fiber fibroin albumen multilayer complex films and preparation method thereof |
| CN107599544B (en) * | 2017-09-13 | 2020-06-16 | 江苏科技大学 | Mulberry twig bark fiber silk fibroin multi-layer composite membrane and preparation method thereof |
| CN107419515A (en) * | 2017-09-17 | 2017-12-01 | 赵兵 | A kind of amphoteric cellulose composite of graphene coated and preparation method thereof |
| CN107556759A (en) * | 2017-09-17 | 2018-01-09 | 钱景 | A kind of titania nanotube silk salix monogolica composite |
| CN107446165A (en) * | 2017-09-17 | 2017-12-08 | 赵兵 | A kind of graphene oxide fibroin amphoteric cellulose composite and preparation method |
| CN108219408A (en) * | 2017-12-20 | 2018-06-29 | 南通理工学院 | Degradable 3d printing material and preparation method thereof |
| CN108853594A (en) * | 2018-06-25 | 2018-11-23 | 东莞市联洲知识产权运营管理有限公司 | A kind of preparation method of the porous Medical rack dressing of cellulose of nanometer of silk protein powder enhancing |
| CN109369961A (en) * | 2018-10-16 | 2019-02-22 | 河南工程学院 | A kind of nano-cellulose based film material and preparation method thereof of polypeptide enhancing |
| CN109369961B (en) * | 2018-10-16 | 2020-11-20 | 河南工程学院 | Polypeptide-enhanced nanocellulose-based thin film material and preparation method thereof |
| CN109594325A (en) * | 2018-12-11 | 2019-04-09 | 佛山市名洲纺织有限公司 | A kind of nanometic zinc oxide rod array it is modified lead wet cotton fiber or its fabric and preparation method thereof |
| CN109594325B (en) * | 2018-12-11 | 2021-07-16 | 佛山市名洲纺织有限公司 | Zinc oxide nanorod array modified moisture-conductive cotton fiber or fabric thereof and preparation method thereof |
| CN110144123A (en) * | 2019-04-08 | 2019-08-20 | 复旦大学 | A kind of fibroin/cellulose derivative composite material and preparation method |
| CN110215351A (en) * | 2019-06-06 | 2019-09-10 | 杭州贝高母婴用品有限公司 | A kind of soft, paper diaper of pro-skin and its production technology |
| CN111499927A (en) * | 2020-06-24 | 2020-08-07 | 内蒙古科技大学 | Cellulose/silk fibroin composite aerogel long fiber and preparation method thereof |
| CN113174074A (en) * | 2021-02-08 | 2021-07-27 | 四川大学华西医院 | Conductive silk fibroin film and preparation method and application thereof |
| CN113174074B (en) * | 2021-02-08 | 2022-05-27 | 四川大学华西医院 | Conductive silk fibroin film and preparation method and application thereof |
| CN114249982A (en) * | 2022-01-25 | 2022-03-29 | 武汉纺织大学 | Preparation method and application of high-strength high-modulus silk material |
| CN114249982B (en) * | 2022-01-25 | 2023-05-09 | 武汉纺织大学 | Preparation method and application of high-strength high-modulus silk material |
| CN114958009A (en) * | 2022-05-24 | 2022-08-30 | 浙江理工大学 | Preparation method of silk-based high-strength ionic gel flexible sensing material |
| CN114958009B (en) * | 2022-05-24 | 2024-01-16 | 浙江理工大学 | Preparation method of silk-based high-strength ionic gel flexible sensing material |
| CN115558151A (en) * | 2022-08-25 | 2023-01-03 | 江苏省农业科学院 | Aerogel taking mung bean protein and burdock nanocellulose as template for synergistically stabilizing foam |
| CN115558151B (en) * | 2022-08-25 | 2024-02-06 | 江苏省农业科学院 | Aerogel taking mung bean protein and burdock nanocellulose synergistically stabilized foam as template |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106479195B (en) | 2019-01-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106479195A (en) | A kind of nano-cellulose strengthens fibroin albumen composite material and preparation method thereof | |
| CN103806123B (en) | Fibroin albumen/sodium alginate composite fiber and preparation method thereof | |
| CN103341209B (en) | Silk fibroin nanofiber membrane and preparation method thereof | |
| CN104436285B (en) | A kind of regenerated silk fibroin gel mould and preparation method thereof | |
| CN103320886B (en) | Bionic regenerated silk fibroin filament fiber and preparation method thereof | |
| CN104264369B (en) | The method of keratin/PEO biological nano fibrous membrane is prepared in two step crosslinkings | |
| CN106243376B (en) | A kind of silk fibroin nano-fiber porous support and preparation method thereof | |
| CN102121133B (en) | Antigen-free porcine dermal collagen fibers | |
| CN106589091A (en) | Method for dissolving fiber of natural silk | |
| CN106913910A (en) | A kind of preparation method of fibroin albumen/Graphene composite nano-fiber support material | |
| Ng et al. | Wet spinning of silk fibroin-based core–sheath fibers | |
| CN110453378A (en) | A kind of sulfonic acid based quantum dot/fibroin albumen composite nano-fiber membrane and its preparation method and application | |
| CN106139246A (en) | A kind of regenerated silk azelon support and preparation method thereof | |
| CN109180988A (en) | A kind of functionalized nano-fiber hydrogel and preparation method thereof | |
| CN107320762A (en) | Collagen/bacteria cellulose composite membrane dressing and preparation method thereof | |
| CN105970344B (en) | A kind of fibroin acid fiber by polylactic of the polydactyl acid containing fibroin albumen | |
| Dai et al. | Improved thermostability and cytocompatibility of bacterial cellulose/collagen composite by collagen fibrillogenesis | |
| CN107325303B (en) | Degumming-free silk fiber solution, preparation method and application thereof | |
| CN105839294A (en) | Method for preparing nanocrystalline cellulose-fibroin film by electrostatic spinning method | |
| CN106589977B (en) | A kind of fibroin/nylon composite materials and preparation method thereof | |
| CN101503834B (en) | Collagen - Na-MMT complex fiber, and spinning technological process thereof | |
| CN109972233A (en) | The preparation method of the biodegradable alginic acid fibre with high-intensity and high-tenacity | |
| CN1544728A (en) | Process for preparing regenerated cocoon fiber | |
| CN109667062A (en) | The preparation method of SF-PHBV composite nano-fiber membrane | |
| CN108624984B (en) | Preparation method of cellulose silkworm silk protein composite fiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |