CN108517028B - Method for preparing sericin membrane material based on enzymatic graft copolymerization - Google Patents
Method for preparing sericin membrane material based on enzymatic graft copolymerization Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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Abstract
The invention discloses a method for preparing a sericin membrane material based on enzymatic graft copolymerization, and belongs to the technical field of textile chemistry. The method reduces the water solubility of sericin and improves the molding effect of the sericin film material through coupling reaction and catalysis and vinyl ester monomer graft copolymerization. Diazo salt is prepared by diazotization of vinyl-containing arylamine, then the diazo salt is coupled with sericin to react, and finally the enzymatic sericin and vinyl ester monomer are grafted and copolymerized to prepare the sericin film material. The specific process and steps are as follows: (1) preparing vinyl-containing diazonium salt; (2) carrying out sericin coupling reaction; (3) grafting and copolymerizing the enzymatic sericin and a monomer; (4) and (5) forming the sericin film material. Compared with the method that a chemical crosslinking method is adopted to introduce a vinyl monomer and then the persulfate or ultraviolet irradiation method and the like are utilized to initiate the graft copolymerization of the sericin and the vinyl ester monomer, the method has the advantages of high graft copolymerization efficiency, mild enzyme treatment conditions and improved sericin film material formability.
Description
Technical Field
The invention relates to a method for preparing a sericin membrane material based on enzymatic graft copolymerization, belonging to the technical field of textile chemistry.
Background
The silk consists of two parts, namely silk fibroin and sericin covered on the surface of the silk fibroin. The silk fibroin is in a linear structure, has higher crystallinity and is mainly used for processing textile fibers; sericin is spherical protein, contains more hydrophilic polar amino acids, has a supermolecular structure mainly based on random coil, and has high water solubility. After the silk is degummed by an alkaline method or a protease method, sericin on the outer layer of the silk is dissolved in hot water and is mostly discharged into industrial wastewater as waste, so that great resource waste and environmental pressure are caused.
The sericin has more polar amino acids, including glutamic acid, glutamine and aspartic acid containing carboxyl, tyrosine containing phenolic hydroxyl and lysine residue containing amino, etc. Because the sericin has high water solubility, when the sericin is applied to the preparation of regenerated protein materials, the sericin has poor structural stability and higher material forming difficulty, and restricts the reutilization of sericin resources. In order to improve the molding effect of sericin protein materials, researchers adopt methods such as blending with other macromolecules, physical embedding or chemical crosslinking to perform hydrophobization modification on sericin protein. The chemical crosslinking method has high efficiency, can improve the formability of the sericin material, but has certain defects, such as harsh reaction conditions, and the biocompatibility of the sericin material is reduced due to partial crosslinking agent residues.
Disclosure of Invention
In order to solve the problems, the invention provides a method for preparing a sericin membrane material based on enzymatic graft copolymerization, which reduces the water solubility of sericin protein and improves the forming effect of the sericin membrane material by coupling reaction and catalysis and vinyl ester monomer graft copolymerization.
The sericin contains 5-10% of tyrosine, and the tyrosine side group benzene ring contains phenolic hydroxyl, so that the sericin has high reaction activity and can generate coupling reaction with various diazonium salts of arylamine. If arylamine containing vinyl is diazotized and carries out coupling reaction with tyrosine in sericin, then vinyl groups can be introduced on sericin protein; meanwhile, horseradish peroxidase (HRP) has strong catalytic activity and is treated with hydrogen peroxide (H)2O2) Systems in which acetylacetone (ACAC) is the initiator, which is an oxidant, are capable of catalyzing the polymerization between vinyl monomers (for example: catalyzing the graft copolymerization between the vinyl-containing sericin and the vinyl ester monomer). Compared with the method of initiating the graft copolymerization of the sericin and the vinyl monomer by adopting a chemical graft copolymerization method or an ultraviolet irradiation method, the method can realize the sericin modification and the film material preparation under mild conditionsHas the advantages of high reaction efficiency, mild treatment condition and the like.
According to the above thought, the invention develops the following method for preparing the sericin membrane material:
the first step is as follows: diazotizing arylamine containing vinyl to prepare diazonium salt, carrying out coupling reaction with sericin, and introducing vinyl on sericin molecules;
the second step is that: based on the above, HRP/H is used2O2The ACAC catalytic system is used for promoting graft copolymerization between sericin and vinyl ester monomers to realize hydrophobization modification of sericin protein and prepare a sericin membrane material.
The first purpose of the invention is to provide a preparation method of a sericin membrane material, which comprises the steps of utilizing a coupling reaction of a diazo salt containing vinyl and sericin protein, and then carrying out graft copolymerization of enzymatic sericin and a vinyl ester monomer to prepare the sericin membrane material.
In one embodiment, the method further comprises shaping the sericin film material.
In one embodiment, the vinyl-containing diazonium salt is a diazonium salt prepared by diazotization of a vinyl-containing aromatic amine.
In one embodiment, the preparation of the vinyl-containing diazonium salt: dissolving arylamine containing vinyl by hydrochloric acid, and adding sodium nitrite to carry out arylamine diazotization to prepare a diazonium salt solution.
In one embodiment, the vinyl-containing diazonium salt preparation treatment process recipe and conditions are as follows: 5-15 g/L of vinylamine-containing aromatic amine, 4-15 g/L of hydrochloric acid and 4-20 g/L of sodium nitrite, wherein the temperature is 0-5 ℃, and the time is 15-60 min; after the reaction is finished, detecting the nitrite in the diazonium salt solution by using starch-potassium iodide test paper, removing excessive nitrite by using urea, and adjusting the pH value of the diazonium salt solution to 7.0-9.0.
In one embodiment, the coupling reaction is carried out by adding sericin to a solution containing a vinyl diazonium salt.
In one embodiment, the process recipe and conditions for the coupling reaction treatment are: 5-15 g/L of sericin, and treating at 0-5 ℃ for 5-30 min; then the sericin solution is dialyzed by deionized water for 24-48 hours.
In one embodiment, the graft copolymerization comprises adding a vinyl ester monomer, horseradish peroxidase and acetylacetone into sericin after the coupling reaction, and adding hydrogen peroxide under the protection of protective gas to promote the graft copolymerization of the sericin and the vinyl ester monomer.
In one embodiment, the graft copolymerization process recipe and conditions: 5-10 g/L of sericin, 2-20U/mL of horseradish peroxidase, 5-10 g/L of acetylacetone, 5-10 g/L of hydrogen peroxide, 2.0-20 g/L of vinyl ester monomer, 20-45 ℃ of temperature, 6.0-8.0 of pH, and 0.5-15 hours of treatment time.
In one embodiment, the forming of the sericin film material: the sericin solution after the graft copolymerization reaction is frozen and dried to form a film at the temperature of between 50 ℃ below zero and 20 ℃ below zero; removing self-aggregation of vinyl ester monomers in the silk glue film, then soaking the silk glue film in 50-80% alcoholic solution for 0.25-1 hour, and finally drying.
In one embodiment, the method comprises the following specific steps:
(1) preparation of vinyl-containing diazonium salt: dissolving arylamine containing vinyl by hydrochloric acid, and adding sodium nitrite to carry out arylamine diazotization to prepare a diazonium salt solution;
the processing process prescription and conditions are as follows: 5-15 g/L of vinylamine-containing aromatic amine, 4-15 g/L of hydrochloric acid and 4-20 g/L of sodium nitrite, wherein the temperature is 0-5 ℃, and the time is 15-60 min; after the reaction is finished, detecting the nitrite in the diazonium salt solution by using starch-potassium iodide test paper, removing excessive nitrite by using urea, and adjusting the pH value of the diazonium salt solution to 7.0-9.0;
(2) sericin coupling reaction: adding sericin derived from mulberry silk into the diazonium salt solution prepared in the step (1) to perform coupling reaction;
the processing process prescription and conditions are as follows: 5-15 g/L of sericin, and treating at 0-5 ℃ for 5-30 min; then dialyzing the sericin solution for 24-48 hours by deionized water;
(3) grafting copolymerization of enzymatic sericin and monomers: adding a vinyl ester monomer, horseradish peroxidase and acetylacetone into the sericin treated in the step (2), and adding hydrogen peroxide under the protection of nitrogen to promote the graft copolymerization of the sericin and the monomer containing the vinyl ester;
the processing process prescription and conditions are as follows: 5-10 g/L of sericin, 2-20U/mL of horseradish peroxidase, 5-10 g/L of acetylacetone, 5-10 g/L of hydrogen peroxide, 2.0-20 g/L of vinyl ester monomer, 20-45 ℃ of temperature, 6.0-8.0 of pH and 0.5-15 hours of treatment time;
(4) molding the sericin membrane material: freezing and drying the sericin solution reacted in the step (3) at the temperature of between 50 ℃ below zero and 20 ℃ below zero to form a membrane; and (3) removing self-aggregates of the vinyl ester monomers in the silk glue film by adopting acetone extraction, then soaking the silk glue film in 50-80% ethanol solution for 0.25-1 hour, and drying at 30 ℃.
In one embodiment, the vinyl aromatic amine comprises 3-vinylaniline, 4-vinylaniline.
In one embodiment, the vinyl ester monomers include methyl acrylate, methyl methacrylate, vinyl acetate.
In one embodiment, the horseradish peroxidase is derived from an animal, plant, or microorganism.
The second purpose of the invention is to provide the sericin membrane material prepared by the method.
It is a third object of the present invention to provide a pharmaceutical formulation, such as a dressing, containing the sericin material.
The fourth purpose of the invention is to provide the application of the method or the sericin membrane material in the field of daily chemical or medical materials.
The invention prepares the sericin film material by coupling reaction of diazonium salt containing vinyl arylamine and sericin and graft copolymerization of enzymatic sericin and vinyl ester monomer. Compared with the method that a chemical crosslinking method is adopted to introduce vinyl monomers on the sericin and then a persulfate or ultraviolet irradiation method and other chemical methods are utilized to initiate the graft copolymerization of the sericin and the vinyl ester monomers, the method has the following advantages:
(1) the graft copolymerization efficiency is high, and the reaction efficiency of the graft copolymerization of the horseradish peroxidase catalyzed sericin and an ester monomer is improved by introducing vinyl on the sericin by adopting a coupling reaction method;
(2) the enzyme treatment condition is mild, the coupling reaction is carried out under the low-temperature condition, and the horseradish peroxidase is used for catalyzing the graft copolymerization, so that the method has the advantages of low energy consumption and safe treatment process, and avoids the defects that a chemical method or an ultraviolet irradiation method is easy to generate sericin denaturation and the like;
(3) the formability of the sericin membrane material is improved, and the method provided by the invention is used for catalyzing sericin to graft vinyl ester monomers, so that the water solubility of the sericin is reduced, the formability of the sericin material is improved, and the mechanical property of the sericin membrane material is improved.
Detailed Description
The detection method comprises the following steps:
(1) breaking strength: ISO 13934-1-2013;
(2) hot water loss rate: immersed in water at 30 ℃ for 30 minutes.
The sericin membrane material is prepared by coupling reaction of diazonium salt containing vinyl arylamine and sericin and graft copolymerization of enzymatic sericin and vinyl ester monomers, and the specific embodiment is as follows:
example 1
The sericin membrane material is prepared by the method provided by the invention, and the specific process steps are as follows:
(1) preparation of vinyl-containing diazonium salt: dissolving 3-vinylaniline with the concentration of 10g/L by using hydrochloric acid with the concentration of 5g/L, and adding sodium nitrite with the concentration of 7.5g/L to prepare a diazonium salt solution, wherein the treatment temperature is 0 ℃, and the treatment time is 40 min; after the reaction is finished, detecting the nitrite in the diazonium salt solution by using starch-potassium iodide test paper, removing excessive nitrite by using urea, and adjusting the pH value of the diazonium salt solution to 9.0;
(2) sericin coupling reaction: adding sericin derived from mulberry silk into the diazonium salt solution prepared in the step (1), and performing coupling reaction at 0 ℃ for 10min, wherein the sericin content is 10 g/L; then the sericin solution is dialyzed for 24 hours by deionized water;
(3) grafting copolymerization of enzymatic sericin and monomers: adding methyl methacrylate, horseradish peroxidase and acetylacetone into the sericin treated in the step (2), and adding hydrogen peroxide under the protection of nitrogen to promote the graft copolymerization of the sericin and the methyl methacrylate, wherein the sericin is 8.5g/L, the horseradish peroxidase is 4.5U/mL, the acetylacetone is 5g/L, the hydrogen peroxide is 6g/L and the methyl methacrylate is 2g/L, and the sericin is treated for 8 hours at the temperature of 30 ℃ and the pH value of 7.0;
(4) molding the sericin membrane material: freezing and drying the sericin solution reacted in the step (3) at-50 ℃ to form a membrane; acetone is adopted to extract and remove the self-polymerization substance of the methyl methacrylate in the silk glue film, and then the silk glue film is soaked in 70 percent ethanol solution for 0.5 hour and dried at 30 ℃.
Sample 1: treating the sericin with 8.5g/L only according to the condition of the step (4) without the treatment of the steps (1), (2) and (3);
sample 2: treating the sericin with the concentration of 8.5g/L according to the conditions of the steps (3) and (4) without the treatment of the steps (1) and (2);
sample 3: processing by steps (1), (2), (3) and (4);
after the treatment by the process, different samples are respectively immersed in hot water at 40 ℃ for 1h, and the dissolution rate and the breaking strength of the samples are measured, wherein the dissolution rate of the sample 1 in hot water is 50.2%, and the breaking strength of a membrane material is 5.6 MPa; the hot water dissolution rate of the sample 2 is 40.9 percent, the breaking strength of the membrane material is 5.9MPa, the hot water dissolution rate of the sample 3 is 7.5 percent, and the breaking strength of the membrane material is 6.4 MPa.
Example 2
The sericin membrane material is prepared by the method provided by the invention, and the specific process steps are as follows:
(1) preparation of vinyl-containing diazonium salt: dissolving 4-vinylaniline with a concentration of 12g/L with hydrochloric acid of 7.5g/L, adding sodium nitrite with a concentration of 8g/L to prepare a diazonium salt solution, and treating at 0 ℃ for 50 min; after the reaction is finished, detecting the nitrite in the diazonium salt solution by using starch-potassium iodide test paper, removing excessive nitrite by using urea, and adjusting the pH value of the diazonium salt solution to 8.5;
(2) sericin coupling reaction: adding sericin derived from mulberry silk into the diazonium salt solution prepared in the step (1), and performing coupling reaction at 0 ℃ for 15min, wherein the sericin content is 12 g/L; then the sericin solution is dialyzed for 20 hours by deionized water;
(3) grafting copolymerization of enzymatic sericin and monomers: adding methyl acrylate, horseradish peroxidase and acetylacetone into the sericin treated in the step (2), and adding hydrogen peroxide under the protection of nitrogen to promote the graft copolymerization of the sericin and the methyl acrylate, wherein the sericin is 10g/L, the horseradish peroxidase is 5U/mL, the acetylacetone is 6g/L, the hydrogen peroxide is 7.5g/L and the methyl acrylate is 4g/L, and the sericin is treated for 12 hours at the temperature of 30 ℃ and the pH value of 7.5;
(4) molding the sericin membrane material: freezing and drying the sericin solution reacted in the step (3) at-50 ℃ to form a membrane; acetone is adopted to extract and remove the self-aggregation of methyl acrylate in the silk glue film, and then the silk glue film is soaked in 70 percent ethanol solution for 0.5 hour and dried at 30 ℃.
Sample 4: treating the sericin with 10g/L without the treatment of the steps (1), (2) and (3) according to the condition of the step (4);
sample 5: treating the sericin with the concentration of 10g/L according to the conditions of the steps (3) and (4) without the treatment of the steps (1) and (2);
sample 6: processing by steps (1), (2), (3) and (4);
after the treatment by the process, different samples are respectively soaked in hot water at 40 ℃ for 1h, and the dissolution rate and the breaking strength of the samples are measured, wherein the dissolution rate of the sample 4 in hot water is 43.0%, and the breaking strength of a membrane material is 5.9 MPa; the hot water dissolution rate of the sample 5 is 41.8 percent, the breaking strength of the membrane material is 6.1MPa, the hot water dissolution rate of the sample 6 is 10.1 percent, and the breaking strength of the membrane material is 7.3 MPa.
By analyzing the example data: the silk glue films (sample 1 and sample 4) prepared directly without modification have high dissolution rate and the film material has the lowest breaking strength; the dissolution rate of the sericin films (samples 2 and 5) which are not coupled with the diazonium salt containing the vinyl arylamine and are only graft copolymerized with the vinyl ester monomer is slightly reduced compared with that of the sericin films without being processed, and the breaking strength is slightly increased; the sericin films (sample 3 and sample 6) prepared by the method have low dissolution rate and obvious increase of fracture strength, and show that the grafting copolymerization effect of sericin and vinyl ester monomers is good. Therefore, the sericin film material prepared by the method has lower water solubility and better formability.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (8)
1. The preparation method of the sericin membrane material is characterized by comprising the steps of carrying out coupling reaction on diazo salt containing vinyl and sericin, and then carrying out graft copolymerization on the sericin and a vinyl ester monomer through enzyme to prepare the sericin membrane material; the coupling reaction is to add sericin into a solution containing vinyl diazonium salt to carry out coupling reaction; the vinyl aromatic amine comprises 3-vinylaniline and 4-vinylaniline; the process prescription and conditions of the coupling reaction treatment are as follows: 5-15 g/L of sericin, and treating at 0-5 ℃ for 5-30 min; then the sericin solution is dialyzed with water for 24-48 hours.
2. The process of claim 1, wherein the vinyl-containing diazonium salt is a diazonium salt prepared by diazotization of a vinyl-containing aromatic amine.
3. The method of claim 1, further comprising shaping the sericin material.
4. The method according to claim 1, wherein the graft copolymerization comprises adding a vinyl ester monomer, horseradish peroxidase and acetylacetone into the sericin after the coupling reaction, and adding hydrogen peroxide under the protection of a protective gas to promote the graft copolymerization of the sericin and the monomer containing the vinyl ester.
5. A sericin material prepared by the method as defined in any one of claims 1 to 4.
6. A dressing comprising the sericin material as defined in claim 5.
7. The application of the sericin membrane material prepared by the method of any one of claims 1 to 4 in the field of daily chemicals or medical materials.
8. The sericin membrane material as set forth in claim 5, which is used in the field of daily chemicals or medical materials.
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