CN106009011A - Method for preparing vinyl modified collagen membrane - Google Patents
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- CN106009011A CN106009011A CN201610393908.2A CN201610393908A CN106009011A CN 106009011 A CN106009011 A CN 106009011A CN 201610393908 A CN201610393908 A CN 201610393908A CN 106009011 A CN106009011 A CN 106009011A
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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
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- 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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Abstract
The invention discloses a method for preparing a vinyl modified collagen membrane; firstly, a vinyl collagen solution is prepared; in the presence of a photoinitiator with a certain concentration, the vinyl collagen solution is placed under ultraviolet irradiation and is cross-linked into a membrane after hours of irradiation; the obtained membrane is not dissolved in water, and has greater strength. Collagen is modified by vinyl, and after ultraviolet crosslinking is initiated by an initiator, the vinyl collagen has a dense network structure. The mechanical properties of the collagen membrane are improved, and the problem of insufficient mechanical properties of the collagen membrane is successfully solved. The method has the advantages of simple process, less required raw materials, and good economic benefits and social application value.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to the preparation method of a kind of vinyl modified collagen film.
Background technology
Collagen protein is rich in skin, cartilage, ligament, tendon and other connective tissue of animal, and domestic have extremely rich in natural resources.Owing to China's most skin resource is all used with forms such as process hides, utilization rate is extremely low, and the Leather Solid Waste produced is not if recycled, the most not only can occupied ground, pollute environment, and be the significant wastage to collagen protein resource.Over nearly 20 years, along with the development of molecular biology, people are more and more deep to the understanding of collagen character, and its application is the most extensive.
For collagen film, the forming method of home and overseas has a variety of.The method that domestic major part research all uses casting film, the external then more method using machinery extrusion.The research such as Ma Chunhui is thought, the ideal process conditions preparing collagen film are: the collagen protein of preparation 4.5% is molten → it is sequentially added into 0.4% starch, 0.25% glutaraldehyde, 0.25% plasticizer thickening → vacuum outgas → coat on smooth glass plate → be dried → take off film.Luo Aipings etc. are thought, cross-linking agent is made for strengthening the pliability of collagen film, mechanical performance more preferably with glycerol, calcium chloride, filming technology is: 12% collagen solution → heat treatment (70~100 DEG C, 15min) → add glycerol, calcium cross-linking agent → dissolve, mix → filter → thickening → vacuum outgas → coating → drying (60~70 DEG C, 5h) → superposition class lipid layer → be dried → take off film → ethanol solution volatilization process → natural drying again.External and domestic manufacturing process is the most dramatically different, and its key points for operation are: acid-swellable skin corium → grind to form slurry → filtration, homogenizing → extrusion → cohesion → tanning → plasticising → be dried → film forming.Although this method imparts collagen film mechanical strength, but the collagen film preparation process of the most this excellent mechanical strength is relative complex, wherein needs equipment the most more.Lu Huanghua et al. is with extracting collagen protein in the fish scale of Ctenopharyngodon idellus, employing pours into embrane method and makes collagen film, being embodied as step is: fish scale collagen is made 2% collagen aqueous solution and 2% chitosan (deacetylation is not less than 90.0%) aqueous solution compares mix homogeneously by different quality, regulate membrance casting condition, 800r/min high-speed stirred 10min in high-speed refrigerated centrifuge simultaneously.Using tilt-pour process will to prepare and be placed horizontally in plastic disc through the film forming liquid of vacuum outgas, be dried through ancient customs and be followed by film and be sample, sample is placed in exsiccator and saves backup.Its verification experimental verification obtains: be 45 DEG C at film-forming temperature, and the fish glue from scale collagen protein film properties that pH is 5, collagen protein is prepared with during proportioning 6:4 of chitosan is best, and tensile strength 61.27MPa, elongation at break is 5.17%.And the present invention uses simple method, the less collagen protein of consumption forms the collagen film that elongation at break is about 7%.Define the vinyl collagen film of better mechanical property so that carbon-carbon double bond is grafted on the strand of collagen protein, and then crosslinking forms the structure of densification on collagen protein surface.
The present invention passes through ultraviolet lighting vinyl collagen protein film forming, successfully prepares the collagen film that a kind of mechanical performance is excellent, and this technique is simple, environmental sound, has preferable economic benefit and social benefit.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of vinyl modified collagen film, solve the complicated process of preparation of existing collagen film, and the problem of the collagen film physical and mechanical properties difference prepared.
The technical solution adopted in the present invention is, the preparation method of a kind of vinyl modified collagen film, specifically implements according to following steps:
Step 1, prepares vinyl collagen solution;
Step 2, takes light trigger and joins in step 1 gained vinyl collagen solution, ultrasonic wave concussion 30min at 40 DEG C, and mix homogeneously is standby;
Step 3, in the solution of mix homogeneously pours the mould of politef into after step 2, is placed in UV-crosslinked instrument and carries out illumination film forming, after drying, to obtain final product.
Inventive feature also resides in,
In step 1, the concrete preparation process of vinyl collagen solution is:
Step 1.1: weigh collagen protein and be placed in phosphate buffer solution, under the conditions of 70 DEG C ± 2 DEG C, stirs 0.5~1h so that it is fully dissolve, obtain collagen solution;
Step 1.2: be added drop-wise to by methacrylic anhydride under water bath condition in step 1.1 gained collagen solution at a temperature of 50 DEG C, reacts 3h, after dialysis, to obtain final product.
In step 1.1, the weight average molecular mass of collagen protein is 145508~181266.
In step 1.1, collagen protein is 1:8~1:12 (g/mL) with the mass volume ratio of phosphate buffer solution.
In step 1.2, the mass concentration of methacrylic anhydride is 94%, and methacrylic anhydride is 0.1:5~2.4:5 (mL/g) with the mass volume ratio of collagen protein, and rate of addition is 1mL/min.
In step 1.2, dialysis procedure is: poured into by solution in bag filter (trapped molecular weight is 3500D), and with deionized water as dialysis solution, at a temperature of 40 DEG C ± 2 DEG C, dialyse 24h.
The solid content of the vinyl collagen solution of step 1 gained is 5.5%~6.5%.
In step 2, light trigger is ultraviolet initiatorLight trigger concentration in vinyl collagen solution is 0.0005%~0.05%.
In step 3, membrance casting condition cross-links film forming for irradiation 1~7h under wavelength is 365nm ultraviolet light.
The invention has the beneficial effects as follows, collagen protein is carried out vinyl modified, after initiator initiation is UV-crosslinked, vinyl collagen protein has the network structure of densification.Improve the mechanical property of collagen film, successfully solve the problem that collagen protein film dynamic performance is not enough.This technique is simple, and needed raw material is less, has good economic benefit and social application is worth.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the preparation method gained collagen film of the present invention a kind of vinyl modified collagen film;
Fig. 2 is to scheme without the SEM of ultraviolet crosslinking with radiation gained collagen film;
Fig. 3 is that the preparation method gained collagen film of the present invention a kind of vinyl modified collagen film contrasts with the infrared spectrum without ultraviolet crosslinking with radiation gained collagen film;
Fig. 4 is the ESEM figure of the preparation method embodiment 1 gained collagen film of the present invention a kind of vinyl modified collagen film;
Fig. 5 is the ESEM figure of the preparation method embodiment 2 gained collagen film of the present invention a kind of vinyl modified collagen film;
Fig. 6 is the ESEM figure of the preparation method embodiment 3 gained collagen film of the present invention a kind of vinyl modified collagen film;
Fig. 7 is the ESEM figure of the preparation method embodiment 4 gained collagen film of the present invention a kind of vinyl modified collagen film;
Fig. 8 is the ESEM figure of the preparation method embodiment 5 gained collagen film of the present invention a kind of vinyl modified collagen film;
Fig. 9 is the ESEM figure of the preparation method embodiment 6 gained collagen film of the present invention a kind of vinyl modified collagen film;
Figure 10 is that the substitution value preparing medium vinyl collagen protein of the present invention a kind of vinyl modified collagen film affects graph of a relation to gained collagen film tensile strength and elongation at break;
Figure 11 is that the substitution value preparing medium vinyl collagen protein of the present invention a kind of vinyl modified collagen film affects graph of a relation to gained collagen film swellbility;
Figure 12 is that the substitution value preparing medium vinyl collagen protein of the present invention a kind of vinyl modified collagen film affects graph of a relation to gained collagen film weight-loss ratio;
Figure 13 is that the preparation medium ultraviolet exposure time of the present invention a kind of vinyl modified collagen film affects graph of a relation to gained collagen film tensile strength and elongation at break;
Figure 14 is that the preparation medium ultraviolet exposure time of the present invention a kind of vinyl modified collagen film affects graph of a relation to gained collagen film swellbility;
Figure 15 is that the preparation medium ultraviolet exposure time of the present invention a kind of vinyl modified collagen film affects graph of a relation to gained collagen film weight-loss ratio;
Figure 16 be the present invention a kind of vinyl modified collagen film preparation in initiator concentration gained collagen film swellbility affected graph of a relation;
Figure 17 be the present invention a kind of vinyl modified collagen film preparation in initiator concentration gained collagen film weight-loss ratio affected graph of a relation.
Detailed description of the invention
The present invention is described in detail with detailed description of the invention below in conjunction with the accompanying drawings.
The present invention is the preparation method of a kind of vinyl modified collagen film, specifically implements according to following steps:
Step 1, weighs collagen protein (weight average molecular mass is 145508~181266) and is placed in phosphate buffer solution, under the conditions of 70 DEG C ± 2 DEG C, stirs 0.5~1h so that it is fully dissolve, obtain collagen solution;Under water bath condition, methacrylic anhydride is added drop-wise in collagen solution at a temperature of 50 DEG C, methacrylic anhydride is that 0.1:5~2.4:5 (mL/g) stirs 3h with the mass volume ratio of collagen protein, to collagen protein dialysis treatment, obtain vinyl collagen protein (CMA) solution of different degree of substitution.
Step 2, weighs light trigger and joins in step 1 gained vinyl collagen solution, ultrasonic wave concussion 30min at 40 DEG C, and mix homogeneously is standby;Wherein, the concentration of light trigger is 0.0005%~0.05%;Light trigger is ultraviolet initiator
Step 3, pours into the solution of step 2 mix homogeneously in the mould of politef, is placed in UV-crosslinked instrument, is that 365nm ultraviolet light carries out illumination 1~7h crosslinking film forming at wavelength, takes out nature and dry, obtain CMA film.
In terms of principle, the present invention will be described below:
1) preparation of vinyl collagen protein
Collagen protein is 1:8~1:12 (g/mL) with the mass volume ratio of phosphate buffer solution, stirs 0.5~1h at a temperature of being placed in 70 DEG C ± 2 DEG C.Wherein, the pH of phosphate buffer solution is 7.4, and main purpose is fully to be dissolved by collagen protein, it is provided that metastable pH environment.
Methacrylic anhydride can be with primaquine-NH in the lysine residue in collagen protein under conditions of heating2React generation amido link, makes the C=C in methacrylic anhydride be incorporated in collagen structure.In course of reaction, phosphate buffer solution is primarily used to dissolve collagen protein, it is provided that a relatively mild reaction environment.Methacrylic anhydride consumption number be directly connected to grafting after C=C double key number purpose how many, very little, the C=C double bond number formed at collagen protein surface grafting is the fewest for methacrylic anhydride consumption, will not form crosslinked action between collagen protein again.Between response time and reaction temperature be generally have interactive, temperature Macromolecular motion accelerate, reaction efficiency promote, the response time shorten;The motion of temperature low molecule is slowed down, and reaction efficiency reduces, and the response time increases.
2) preparation principle of vinyl collagen film is shown below, and the C=C on vinyl collagen molecules chain causes respectively through chain, chain increases and chain termination three phases crosslinking film forming.
(1) chain causes
(2) chain increases
(3) chain termination
Embodiment 1
Step 1, weighs the collagen protein 5.0g that molecular mass is 181266, is placed in 50mL phosphate buffer solution (pH 7.4), stirs 0.5h so that it is fully dissolve, obtain collagen solution at 70 DEG C;When its temperature is down to stable, under water bath condition, 0.1mL methacrylic anhydride is added drop-wise in collagen solution with 1mL/min speed at a temperature of 50 DEG C, reaction 2h, modified collagen solution is placed in the bag filter of molecular size range 3500D, with deionized water as dialysis solution, dialyse at a temperature of 40 DEG C 24h, takes out to obtain the vinyl collagen solution of different degree of substitution;
Step 2, the concentration in collagen solution choosing light trigger is 0.006%, by light triggerIt is added in the vinyl collagen solution of step 1, ultrasonic wave concussion 30min, mix homogeneously at 40 DEG C.
Step 3, pours in Teflon mould by the collagen solution of mix homogeneously in step 2, is positioned in UV-crosslinked instrument irradiation 3h, naturally dries after taking-up, the CMA film of different degree of substitution.
Embodiment 2~6
See embodiment 1, as different from Example 1, in step 1, successively 0.3mL, 0.6mL, 1.2mL, 1.5mL and 1.8mL methacrylic anhydride is added drop-wise in collagen solution with 1mL/min speed under water bath condition at a temperature of 50 DEG C.
Embodiment 7
Step 1, weighs the collagen protein 5.0g that molecular mass is 145508, is placed in 50mL phosphate buffer solution (pH 7.4), stirs 0.5h so that it is fully dissolve, obtain collagen solution at 70 DEG C;When its temperature is down to stable, under water bath condition, 1.2mL methacrylic anhydride is added drop-wise in collagen solution with 1mL/min speed at a temperature of 50 DEG C, reaction 2h, modified collagen solution is placed in the bag filter of molecular size range 3500D, with deionized water as dialysis solution, dialyse at a temperature of 40 DEG C 24h, takes out to obtain the vinyl collagen solution that substitution value is 73%;
Step 2, the concentration in collagen solution choosing light trigger is 0.006%, by light triggerIt is added in the vinyl collagen solution of step 1, ultrasonic wave concussion 30min, mix homogeneously at 40 DEG C.
Step 3, pours in Teflon mould by the collagen solution of mix homogeneously in step 2, is positioned in UV-crosslinked instrument, is that 365nm ultraviolet light irradiates 1h at wavelength, naturally dries, obtain CMA film after taking-up.
Embodiment 8~13
See embodiment 7, as different from Example 7, in step 3, be positioned in UV-crosslinked instrument irradiation 2h, 3h, 4h, 5h, 6h and 7h, naturally dry after taking-up.
Embodiment 14
Step 1, weighs the collagen protein 5.0g that molecular mass is 160000, is placed in 50mL phosphate buffer solution (pH 7.4), stirs 0.5h so that it is fully dissolve, obtain collagen solution at 70 DEG C;When its temperature is down to stable, under water bath condition, 1.2mL methacrylic anhydride is added drop-wise in collagen solution with 1mL/min speed at a temperature of 50 DEG C, reaction 2h, modified collagen solution is placed in the bag filter of molecular size range 3500D, with deionized water as dialysis solution, dialyse at a temperature of 40 DEG C 24h, obtains the vinyl collagen solution that substitution value is 73%;
Step 2, is the ratio of 0.0005% according to light trigger concentration in collagen solution, by light triggerIt is added in the vinyl collagen solution of step 1, ultrasonic wave concussion 30min, mix homogeneously at 40 DEG C.
Step 3, pours in Teflon mould by the collagen solution of mix homogeneously in step 2, is positioned in UV-crosslinked instrument irradiation 3h, naturally dries, obtain CMA film after taking-up.
Embodiment 15~21
Seeing embodiment 14, as different from Example 14, in step 2, light trigger concentration in collagen solution is 0.001%, 0.005%, 0.01%, 0.015%, 0.02% and 0.05%.
Fig. 1 is the SEM figure of the preparation method gained collagen film of the present invention a kind of vinyl modified collagen film, Fig. 2 schemes without the SEM of ultraviolet crosslinking with radiation gained collagen film, as can be seen from the figure, vinyl collagen protein (Fig. 1) after UV-crosslinked has obvious mesh, has the network structure of densification.Prove that the C=C double bond on ultraviolet irradiation, modified collagen albumen there occurs polyreaction, and cross-link the fine and close network structure of rule.Meanwhile, it also having carried out examination of infrared spectrum respectively, such as Fig. 3, result shows: uncrosslinked CMA is at 925cm-1And 955cm-1There is peak at place, and this peak is RCH3C=CH2The out-of-plane bending vibration peak of hydrogen on double key carbon in structure, but these peaks all disappear after CMA is caused crosslinking by ultraviolet, illustrates that C=C take part in reaction in ultraviolet initiation cross-linking reaction, it was demonstrated that CMA there occurs crosslinking.
In addition, the present invention has carried out relative analysis to the ESEM figure of gained collagen film under different degree of substitution, seeing Fig. 4~Fig. 9, its substitution value respectively is 15% (Fig. 4), 50% (Fig. 5), 67% (Fig. 6), 73% (Fig. 7), 79% (Fig. 8), 83% (Fig. 9).4 identical with the amplification of 5 (× 2000) in figure, and can will be apparent from see network structure, and there is the mesh of regular homogeneous size, particularly substitution value is the modified collagen film of 15%.Substitution value is that the mesh of modified collagen film of 50% (Fig. 5) is the least by contrast, and cross-linked network is fine and close, can see the most mesh-structured.Increase (× 4000) under bigger amplification along with substitution value, it can be seen that the network structure of modified collagen film dense uniform.And along with the increase of substitution value, the mesh of modified collagen film is the least, and network structure is the finest and close.
Further tensile strength and elongation at break, swellbility, the relation that affects of weight-loss ratio of gained collagen film are studied by the vinyl collagen protein of different degree of substitution, result shows: along with the tensile strength of substituted increase modified collagen film is being continuously increased, and elastic extension is constantly declining.Modified collagen albumen substitution value is the biggest, and the crosslinking degree of film is the biggest, thus causes the increase (as shown in Figure 10) of the tensile strength of film.Along with the increase of substitution value, collagen film swellbility in water also gradually decreases (see Figure 11), weight-loss ratio also gradually decreases (see Figure 12).
In addition, in the present invention, ultraviolet irradiation time and initiator concentration are also the key factors determining gained collagen protein film properties, wherein, the relation that affects of gained collagen film tensile strength and elongation at break, swellbility and weight-loss ratio is studied by the ultraviolet irradiation time, result shows: along with the tensile strength extending modified collagen film of exposure time is being continuously increased, elastic extension is constantly declining.When exposure time is at 3h~5h, the tensile strength of modified collagen film is relatively big, and elastic extension is relatively small simultaneously.When exposure time is further continued for increasing, the tensile strength of modified collagen albumen is reducing, and elastic elongation flow process reduces (see Figure 13) at the same time;Along with the increase of ultraviolet irradiation time, swellbility and the weight-loss ratio of collagen film are being gradually reduced, little more than 3 constantly when the ultraviolet irradiation time, and the swellbility of collagen film and weight-loss ratio change are little (as shown in Figure 14 and Figure 15).As shown in figure 16, along with the increase of initiator concentration, collagen film weight-loss ratio in water is the trend presenting first increases and then decreases, and initiator concentration efficiency of initiation in the range of 0.005%~0.01 is best.Figure 17 is the variation tendency of initiator concentration and modified collagen film weight-loss ratio, can be drawn by figure, along with the increase of initiator concentration, the trend of collagen film swellbility first increases and then decreases in water, initiator concentration efficiency of initiation in the range of 0.005%~0.01% is best.
The preparation method of the present invention a kind of vinyl modified collagen film, collagen protein is carried out vinyl modified, penetrating collagen cross-linking reaction, film forming with ultraviolet lighting, the film significantly improving the swellbility of collagen film, physical and mechanical properties, and gained is water insoluble.
Claims (9)
1. the preparation method of a vinyl modified collagen film, it is characterised in that specifically according to following step
Rapid enforcement:
Step 1, prepares vinyl collagen solution;
Step 2, takes light trigger and joins in step 1 gained vinyl collagen solution, at 40 DEG C
Ultrasonic wave concussion 30min, mix homogeneously, standby;
Step 3, in the solution of mix homogeneously pours the mould of politef into after step 2, is placed on purple
External crosslinking instrument carries out illumination film forming, after drying, to obtain final product.
The preparation method of a kind of vinyl modified collagen film the most according to claim 1, its feature
Being, the solid content of the vinyl collagen solution of step 1 gained is 5.5%~6.5%.
The preparation method of a kind of vinyl modified collagen film the most according to claim 2, its feature
Being, in step 1, the concrete preparation process of vinyl collagen solution is:
Step 1.1: weigh collagen protein and be placed in phosphate buffer solution, under the conditions of 70 DEG C ± 2 DEG C, stirring
0.5~1h so that it is fully dissolve, obtain collagen solution;
Step 1.2: under water bath condition, methacrylic anhydride is added drop-wise at a temperature of 50 DEG C step 1.1 gained
In collagen solution, react 3h, after dialysis, to obtain final product.
The preparation method of a kind of vinyl modified collagen film the most according to claim 3, its feature
Being, in step 1.1, the weight average molecular mass of collagen protein is 145508~181266.
The preparation method of a kind of vinyl modified collagen film the most according to claim 4, its feature
Being, in step 1.1, collagen protein is 1:8~1:12 with the mass volume ratio of phosphate buffer solution.
The preparation method of a kind of vinyl modified collagen film the most according to claim 3, its feature
Being, in step 1.2, the mass concentration of methacrylic anhydride is 94%, methacrylic anhydride and collagen egg
White mass volume ratio is 0.1:5~2.4:5, and rate of addition is 1mL/min.
The preparation method of a kind of vinyl modified collagen film the most according to claim 6, its feature
Being, in step 1.2, dialysis procedure is: poured into by solution in bag filter, with deionized water as dialysis
Liquid, at a temperature of 40 DEG C ± 2 DEG C, dialyse 24h.
The preparation method of a kind of vinyl modified collagen film the most according to claim 1, its feature
Being, in step 2, light trigger is ultraviolet initiator2959, light trigger is at vinyl
Concentration in collagen solution is 0.0005%~0.05%.
The preparation method of a kind of vinyl modified collagen film the most according to claim 1, its feature
Being, in step 3, membrance casting condition cross-links film forming for irradiation 1~7h under wavelength is 365nm ultraviolet light.
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Cited By (7)
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CN107118375A (en) * | 2017-06-20 | 2017-09-01 | 青岛金典生化器材有限公司 | A kind of vinyl modified fish scale protein film and preparation method thereof |
CN108486881A (en) * | 2018-03-20 | 2018-09-04 | 陕西科技大学 | A kind of preparation method of collagen/PA superfine fibre non-woven materials |
CN110407933A (en) * | 2019-06-26 | 2019-11-05 | 江苏悦智生物医药有限公司 | Graft product and method for the production thereof |
CN111714680A (en) * | 2020-06-30 | 2020-09-29 | 福隆医疗器械集团有限公司 | Recombinant human-derived collagen membrane and preparation method and application thereof |
CN112717898A (en) * | 2019-10-28 | 2021-04-30 | 四川大学 | Preparation method of collagen-based hydrogel adsorbent for treating Cr (III) in leather-making wastewater |
CN112755924A (en) * | 2021-01-04 | 2021-05-07 | 陕西科技大学 | Preparation method of vinyl collagen microspheres |
CN114975944A (en) * | 2022-06-08 | 2022-08-30 | 陕西科技大学 | Silicon-carbon negative electrode material with high-strength carbon matrix and preparation method thereof |
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Cited By (10)
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CN107118375A (en) * | 2017-06-20 | 2017-09-01 | 青岛金典生化器材有限公司 | A kind of vinyl modified fish scale protein film and preparation method thereof |
CN108486881A (en) * | 2018-03-20 | 2018-09-04 | 陕西科技大学 | A kind of preparation method of collagen/PA superfine fibre non-woven materials |
CN110407933A (en) * | 2019-06-26 | 2019-11-05 | 江苏悦智生物医药有限公司 | Graft product and method for the production thereof |
CN112717898A (en) * | 2019-10-28 | 2021-04-30 | 四川大学 | Preparation method of collagen-based hydrogel adsorbent for treating Cr (III) in leather-making wastewater |
CN112717898B (en) * | 2019-10-28 | 2022-03-04 | 四川大学 | Preparation method of collagen-based hydrogel adsorbent for treating Cr (III) in leather-making wastewater |
CN111714680A (en) * | 2020-06-30 | 2020-09-29 | 福隆医疗器械集团有限公司 | Recombinant human-derived collagen membrane and preparation method and application thereof |
CN111714680B (en) * | 2020-06-30 | 2022-02-01 | 江苏创健医疗科技有限公司 | Recombinant human-derived collagen membrane and preparation method and application thereof |
CN112755924A (en) * | 2021-01-04 | 2021-05-07 | 陕西科技大学 | Preparation method of vinyl collagen microspheres |
CN114975944A (en) * | 2022-06-08 | 2022-08-30 | 陕西科技大学 | Silicon-carbon negative electrode material with high-strength carbon matrix and preparation method thereof |
CN114975944B (en) * | 2022-06-08 | 2023-08-29 | 陕西科技大学 | Silicon-carbon negative electrode material with high-strength carbon matrix and preparation method thereof |
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