CN108517028A - A method of silk gum membrane material is prepared based on enzymatic graft copolymerization - Google Patents
A method of silk gum membrane material is prepared based on enzymatic graft copolymerization Download PDFInfo
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- CN108517028A CN108517028A CN201810329413.2A CN201810329413A CN108517028A CN 108517028 A CN108517028 A CN 108517028A CN 201810329413 A CN201810329413 A CN 201810329413A CN 108517028 A CN108517028 A CN 108517028A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H1/00—Macromolecular products derived from proteins
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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
- 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 kind of methods preparing silk gum membrane material based on enzymatic graft copolymerization, belong to technical field of textile chemistry.The method of the present invention reduces sericin water solubility, improves silk gum membrane material molding effect by coupling reaction and catalysis and vinyl ester monomer graft copolymerization.Diazol is prepared by containing vinyl arylamine diazotising, then with sericin coupling reaction, last enzymatic silk gum and vinyl ester monomer graft copolymerization, prepares silk gum membrane material.Concrete technology with steps are as follows：(1) preparation of the aryldiazonium salt containing ethylene；(2) sericin coupling reaction；(3) enzymatic silk gum and monomer graft copolymerization；(4) molding of silk gum membrane material.Vinyl monomer is introduced with using chemical crosslink technique, persulfate or Ultraviolet irradiation method etc. is recycled to cause silk gum compared with vinyl ester monomer graft copolymerization, the method graft copolymerization that the present invention addresses is efficient, and enzymatic treatment condition mitigates, and silk gum membrane material mouldability improves.
Description
Technical field
The present invention relates to a kind of methods preparing silk gum membrane material based on enzymatic graft copolymerization, belong to textile chemistry technology neck
Domain.
Background technology
Silk is made of fibroin with the silk gum two parts for being covered in fibroin surface.The linear structure of fibroin albumen, crystallinity
It is higher, it is chiefly used in textile fabric processing；Silk gum is globular protein, contains more Hydrophilic polar amino acid, supramolecular structure is with nothing
It is water-soluble higher based on rule curling.For silk after alkaline process or protease method degumming process, the silk gum of silk outer layer is dissolved in heat
Water, and be used as in waste discharge to industrial wastewater, cause the great wasting of resources and environmental pressure. more.
Polar amino acid is more in silk gum, including carboxylic glutamic acid, glutamine and asparatate, phenolic hydroxy group
Tyrosine and amino-containing lysine residue etc..Due to sericin water solubility height, when being applied to regenerated protein material preparation, knot
Structure stability is poor, material molding difficulty is larger, constrains the recycling of silk gum resource.To improve the molding effect of sericin material
Fruit, researcher the methods of use with other polymer blended, physically trappings or chemical crosslinking, carry out sericin hydrophobization and change
Property.Chemical crosslink technique efficiency is higher, silk gum material mouldability can be improved, but there is also certain deficiencies, as reaction condition is more severe
It carves, partial cross-linked dose of residual can be such that the biocompatibility of silk gum material declines.
Invention content
To solve the above-mentioned problems, the present invention provides a kind of sides preparing silk gum membrane material based on enzymatic graft copolymerization
Method reduces sericin water solubility, improves silk gum membrane material by coupling reaction and catalysis and vinyl ester monomer graft copolymerization
Expect molding effect.
Contain 5~10% tyrosine in silk gum, contain phenolic hydroxyl group on tyrosine side group phenyl ring, there is higher reactivity,
Coupling reaction can occur with the diazol of a variety of arylamine.If by the arylamine diazotising containing vinyl, and with tyrosine in silk gum
Coupling reaction is carried out, then can introduce vinyl group on sericin；At the same time, horseradish peroxidase (HRP) has relatively strong
Catalytic activity, with hydrogen peroxide (H2O2) it is oxidant, acetylacetone,2,4-pentanedione (ACAC) is that can be catalyzed vinyl in the system of initiator
Between monomer occur polymerization (such as：It is catalyzed sericin containing vinyl and graft copolymerization between vinyl ester monomer).With use
Chemical graft is copolymerized or Ultraviolet irradiation method causes silk gum compared with graft copolymerization of vinyl monomer, and this method can be in mild lower realization
Silk gum is modified and prepared by membrane material, has many advantages, such as that reaction efficiency height, treatment conditions are mild.
According to above-mentioned thinking, the present invention develops the following method for carrying out silk gum membrane material preparation：
The first step：Arylamine diazotising containing vinyl is prepared into diazol, and coupling reaction is carried out with sericin, in silk
Vinyl is introduced on xanthan molecule；
Second step：On the basis of the above, with HRP/H2O2/ ACAC catalyst system and catalyzings, enzymatic silk gum and vinyl ester monomer it
Between graft copolymerization, realize sericin hydrophobic modification, prepare silk gum membrane material.
The first purpose of the invention is to provide a kind of preparation methods of silk gum membrane material, and the method includes using containing second
Alkenyl diazol and sericin coupling reaction, then enzymatic silk gum and vinyl ester monomer graft copolymerization, prepare silk gum film
Material.
In one embodiment, the method further includes the molding of silk gum membrane material.
In one embodiment, the aryldiazonium salt containing ethylene is diazonium prepared by the diazotising of arylamine containing vinyl
Salt.
In one embodiment, the preparation of the aryldiazonium salt containing ethylene：With dissolving with hydrochloric acid arylamine containing vinyl, it is added
Sodium nitrite carries out arylamine diazotising, prepares diazonium salt solution.
In one embodiment, the aryldiazonium salt containing ethylene prepares treatment process prescription and condition：Containing vinyl aromatic (co)
5~15g/L of amine, 4~15g/L of hydrochloric acid, 4~20g/L of sodium nitrite, 0~5 DEG C of temperature, 15~60min of time；After reaction,
Nitrous acid in diazonium salt solution is detected with starch-kalium iodide test paper, excessive nitrous acid is removed with urea, adjusts diazonium salt solution
PH to 7.0~9.0.
In one embodiment, the coupling reaction be by sericin be added the aryldiazonium salt containing ethylene solution in into
Row coupling reaction.
In one embodiment, the technology preparation and condition of the coupling reaction processing：5~15g/L of sericin, place
Manage 0~5 DEG C of temperature, 5~30min of time；Then silk gum solution was with deionized water dialysis 24~48 hours.
In one embodiment, the graft copolymerization is included in the silk gum after coupling reaction and vinyl ester is added
Hydrogen peroxide is added in monomer, horseradish peroxidase and acetylacetone,2,4-pentanedione under the protection of protective gas, promotes silk gum and contains vinyl
Esters monomer graft copolymerization.
In one embodiment, the graft copolymerization treatment process prescription and condition：5~10g/L of sericin, horseradish
2~20U/mL of peroxidase, 5~10g/L of acetylacetone,2,4-pentanedione, 5~10g/L of hydrogen peroxide, vinyl ester 2.0~20g/L of monomer,
20~45 DEG C, pH 6.0~8.0 of temperature, 0.5~15 hour processing time.
In one embodiment, the molding of the silk gum membrane material：By the silk gum solution after graft copolymerization -50
DEG C~-20 DEG C under the conditions of be freeze-dried film forming；The self-aggregate for removing silk gum film medium vinyl esters monomer, then exists silk gum film
It impregnates 0.25~1 hour in 50~80% alcoholic solutions, finally dries.
In one embodiment, the concrete technology of the method with steps are as follows：
(1) preparation of the aryldiazonium salt containing ethylene：With dissolving with hydrochloric acid arylamine containing vinyl, sodium nitrite is added and carries out arylamine weight
Nitridation, prepares diazonium salt solution；
Treatment process prescription and condition：5~the 15g/L of arylamine containing vinyl, 4~15g/L of hydrochloric acid, 4~20g/ of sodium nitrite
L, 0~5 DEG C of temperature, 15~60min of time；After reaction, nitrous in diazonium salt solution is detected with starch-kalium iodide test paper
Acid removes excessive nitrous acid with urea, adjusts diazonium salt solution pH to 7.0~9.0；
(2) sericin coupling reaction：It is molten by diazol prepared by step (1) is added from the sericin of mulberry silk
Coupling reaction is carried out in liquid；
Treatment process prescription and condition：5~15g/L of sericin, 0~5 DEG C for the treatment of temperature, 5~30min of time；Then
Silk gum solution was with deionized water dialysis 24~48 hours；
(3) enzymatic silk gum and monomer graft copolymerization：Be added in step (2) treated silk gum vinyl ester monomer,
Hydrogen peroxide is added in horseradish peroxidase and acetylacetone,2,4-pentanedione under nitrogen protection, and silk gum is promoted to be connect with monomer containing vinyl ester
Branch copolymerization；
Treatment process prescription and condition：5~10g/L of sericin, 2~20U/mL of horseradish peroxidase, acetylacetone,2,4-pentanedione 5
~10g/L, 5~10g/L of hydrogen peroxide, vinyl ester 2.0~20g/L of monomer, 20~45 DEG C, pH 6.0~8.0 of temperature, processing
0.5~15 hour time；
(4) molding of silk gum membrane material：Silk gum solution after step (3) is reacted freezes under the conditions of -50 DEG C~-20 DEG C
Drying and forming-film；The self-aggregate of silk gum film medium vinyl esters monomer is removed using acetone extraction, then by silk gum film 50~
It impregnates 0.25~1 hour in 80% ethanol solution, is dried at 30 DEG C.
In one embodiment, the arylamine containing vinyl includes 3- vinyl aniline, 4- vinyl aniline.
In one embodiment, the vinyl ester monomer includes methyl acrylate, methyl methacrylate, acetic acid
Vinyl acetate.
In one embodiment, the horseradish peroxidase derives from animal, plant or microorganism.
Second object of the present invention is to provide the silk gum membrane material being prepared according to the method described above.
Third object of the present invention is to provide the pharmaceutical products containing the silk gum membrane material, such as dressing.
Fourth object of the present invention is to provide the method or the silk gum membrane material and is led in daily use chemicals or medical material
The application in domain.
The present invention passes through the diazol of the arylamine containing vinyl and silk gum coupling reaction, then enzymatic silk gum and vinyl ester list
Body graft copolymerization prepares silk gum membrane material.Vinyl monomer is introduced on silk gum with using chemical crosslink technique, recycles persulfuric acid
The chemical methodes such as salt or Ultraviolet irradiation method cause silk gum compared with vinyl ester monomer graft copolymerization, and the present invention has following excellent
Point：
(1) graft copolymerization is efficient, introduces vinyl on silk gum using the method for coupling reaction, improves horseradish peroxide
Compound enzymatic silk gum carries out the reaction efficiency of graft copolymerization with esters monomer；
(2) enzymatic treatment condition mitigates, and carries out coupling reaction under cryogenic, is connect by means of horseradish peroxidase enzyme catalytic
Branch copolymerization has the advantages that low energy consumption, treatment process safety, avoids chemical method or Ultraviolet irradiation method is also easy to produce sericin change
The defects of property；
(3) silk gum membrane material mouldability improves, and addressing method with the present invention is catalyzed silk gum grafting vinyl esters monomer, drop
Low sericin water solubility, improves the mouldability of silk gum material, improves silk gum membrane material mechanical property.
Specific implementation mode
Detection method：
(1) fracture strength：ISO 13934-1-2013；
(2) hot water dissolve-loss ratio：It is impregnated 30 minutes in 30 DEG C of water.
It is grafted with vinyl ester monomer using the diazol and silk gum coupling reaction of the arylamine containing vinyl, then enzymatic silk gum
Copolymerization, prepares silk gum membrane material, specific embodiment is as follows：
Embodiment 1
Silk gum membrane material is prepared in the method that the present invention addresses, specific process step is as follows：
(1) preparation of the aryldiazonium salt containing ethylene：With the 5g/L dissolving with hydrochloric acid vinyl aniline of 3- containing 10g/L, 7.5g/L is added
Sodium nitrite prepares diazonium salt solution, 0 DEG C for the treatment of temperature, time 40min；After reaction, it is detected with starch-kalium iodide test paper
Nitrous acid in diazonium salt solution removes excessive nitrous acid with urea, adjusts diazonium salt solution pH to 9.0；
(2) sericin coupling reaction：It is molten by diazol prepared by step (1) is added from the sericin of mulberry silk
In liquid, in 0 DEG C of coupling reaction 10min, wherein sericin 10g/L；Then silk gum solution was with deionized water dialysis 24 hours；
(3) enzymatic silk gum and monomer graft copolymerization：Be added in step (2) treated silk gum methyl methacrylate,
Hydrogen peroxide is added in horseradish peroxidase and acetylacetone,2,4-pentanedione under nitrogen protection, promotes silk gum and methyl methacrylate-grafted
Copolymerization, wherein sericin 8.5g/L, horseradish peroxidase 4.5U/mL, acetylacetone,2,4-pentanedione 5g/L, hydrogen peroxide 6g/L, methyl-prop
E pioic acid methyl ester 2g/L is handled 8 hours under the conditions of 30 DEG C, pH 7.0；
(4) molding of silk gum membrane material：By step (3) react after silk gum solution be freeze-dried under the conditions of -50 DEG C at
Film；The self-aggregate that methyl methacrylate in silk gum film is removed using acetone extraction, then by silk gum film in 70% ethanol solution
Middle dipping 0.5 hour is dried at 30 DEG C.
Sample 1：Without step (1), (2), (3) processing, only handled by step (4) condition with 8.5g/L sericins；
Sample 2：It is handled without step (1), (2), only with 8.5g/L silk gum by step (3), the processing of (4) condition；
Sample 3：It is handled through step (1), (2), (3) and (4)；
After above-mentioned process, the various sample impregnation 1h in 40 DEG C of hot water respectively measures the dissolve-loss ratio of sample
And fracture strength, wherein 1 hot water dissolve-loss ratio 50.2% of sample, membrane material fracture strength 5.6MPa；2 hot water dissolve-loss ratio of sample
40.9%, membrane material fracture strength 5.9MPa, 3 hot water dissolve-loss ratio 7.5% of sample, membrane material fracture strength 6.4MPa.
Embodiment 2
Silk gum membrane material is prepared in the method that the present invention addresses, specific process step is as follows：
(1) preparation of the aryldiazonium salt containing ethylene：With the 7.5g/L dissolving with hydrochloric acid vinyl aniline of 4- containing 12g/L, 8g/L is added to enter
Sodium nitrite prepares diazonium salt solution, 0 DEG C for the treatment of temperature, time 50min；After reaction, it is detected with starch-kalium iodide test paper
Nitrous acid in diazonium salt solution removes excessive nitrous acid with urea, adjusts diazonium salt solution pH to 8.5；
(2) sericin coupling reaction：It is molten by diazol prepared by step (1) is added from the sericin of mulberry silk
In liquid, in 0 DEG C of coupling reaction 15min, wherein sericin 12g/L；Then silk gum solution was with deionized water dialysis 20 hours；
(3) enzymatic silk gum and monomer graft copolymerization：Methyl acrylate, horseradish are added in step (2) treated silk gum
Hydrogen peroxide is added in peroxidase and acetylacetone,2,4-pentanedione under nitrogen protection, promotes silk gum and methyl acrylate graft copolymerization,
In, sericin 10g/L, horseradish peroxidase 5U/mL, acetylacetone,2,4-pentanedione 6g/L, hydrogen peroxide 7.5g/L, methyl acrylate 4g/
L is handled 12 hours under the conditions of 30 DEG C, pH 7.5；
(4) molding of silk gum membrane material：By step (3) react after silk gum solution be freeze-dried under the conditions of -50 DEG C at
Film；The self-aggregate that methyl acrylate in silk gum film is removed using acetone extraction, is then soaked silk gum film in 70% ethanol solution
Stain 0.5 hour is dried at 30 DEG C.
Sample 4：Without step (1), (2), (3) processing, handled by step (4) condition with 10g/L sericins；
Sample 5：It is handled without step (1), (2), with 10g/L silk gum by step (3), the processing of (4) condition；
Sample 6：It is handled through step (1), (2), (3) and (4)；
After above-mentioned process, the various sample impregnation 1h in 40 DEG C of hot water respectively measures the dissolve-loss ratio of sample
And fracture strength, wherein 4 hot water dissolve-loss ratio 43.0% of sample, membrane material fracture strength 5.9MPa；5 hot water dissolve-loss ratio of sample
41.8%, membrane material fracture strength 6.1MPa, 6 hot water dissolve-loss ratio 10.1% of sample, membrane material fracture strength 7.3MPa.
By to embodiment data analysis：The unmodified and dissolve-loss ratio of silk gum film (sample 1, sample 4) that directly prepares compared with
Height, membrane material fracture strength are minimum；It is not coupled with the diazol of the arylamine containing vinyl and is only grafted altogether with vinyl ester monomer
The poly- more untreated sample of silk gum film (sample 2, sample 5) dissolve-loss ratio slightly reduces, and fracture strength increases less；It is addressed with the present invention
Silk gum film (sample 3, sample 6) dissolve-loss ratio for preparing of method it is relatively low, fracture strength increases apparent, shows sericin and ethylene
Base esters monomer graft copolymerization effect is preferable.It can be seen that having with silk gum membrane material prepared by the method that the present invention addresses relatively low
Water-soluble and preferable mouldability.
Although the present invention has been described by way of example and in terms of the preferred embodiments, it is not limited to the present invention, any to be familiar with this skill
The people of art can do various change and modification, therefore the protection model of the present invention without departing from the spirit and scope of the present invention
Enclosing be subject to what claims were defined.
Claims (10)
1. a kind of preparation method of silk gum membrane material, which is characterized in that the method includes utilizing aryldiazonium salt containing ethylene and silk
Glue protein coupling reaction, then enzymatic silk gum and vinyl ester monomer graft copolymerization, prepare silk gum membrane material.
2. according to the method described in claim 1, its feature is, the aryldiazonium salt containing ethylene is the weight of arylamine containing vinyl
Nitrogenize the diazol prepared.
3. according to the method described in claim 1, its feature is, the method further includes the molding of silk gum membrane material.
4. according to the method described in claim 1, its feature is, the coupling reaction is that sericin is added to contain ethylene
Coupling reaction is carried out in the solution of aryldiazonium salt.
5. method according to any one of claims 1 to 4, feature is, the technology preparation of the coupling reaction processing
And condition：5~15g/L of sericin, 0~5 DEG C for the treatment of temperature, 5~30min of time；Then silk gum solution with water dialysis 24~
48 hours.
6. according to the method described in claim 1, its feature is, the graft copolymerization is included in the silk after coupling reaction
Vinyl ester monomer, horseradish peroxidase and acetylacetone,2,4-pentanedione are added in glue, hydrogen peroxide is added under the protection of protective gas,
Promote silk gum and the graft copolymerization of monomer containing vinyl ester.
7. according to the method described in claim 2, its feature is, the arylamine containing vinyl include 3- vinyl aniline,
4- vinyl aniline.
8. the silk gum membrane material that any the methods of claim 1-7 are prepared.
9. the dressing containing silk gum membrane material described in claim 8.
10. silk gum membrane material is in daily use chemicals or field of medical materials described in any the methods of claim 1-7 or claim 8
Application.
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| CN201810329413.2A CN108517028B (en) | 2018-04-13 | 2018-04-13 | Method for preparing sericin membrane material based on enzymatic graft copolymerization |
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Cited By (1)
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| CN109281166A (en) * | 2018-09-17 | 2019-01-29 | 江南大学 | A kind of protein fibre antibiotic finishing method based on enzymatic graft copolymerization |
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| CN108517028B (en) | 2020-01-07 |
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