CN105694801A - Preparation method of protein-base adhesive - Google Patents
Preparation method of protein-base adhesive Download PDFInfo
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- CN105694801A CN105694801A CN201610210428.8A CN201610210428A CN105694801A CN 105694801 A CN105694801 A CN 105694801A CN 201610210428 A CN201610210428 A CN 201610210428A CN 105694801 A CN105694801 A CN 105694801A
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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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J189/00—Adhesives based on proteins; Adhesives based on derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P21/00—Preparation of peptides or proteins
- C12P21/06—Preparation of peptides or proteins produced by the hydrolysis of a peptide bond, e.g. hydrolysate products
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Wood Science & Technology (AREA)
- Biochemistry (AREA)
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- General Chemical & Material Sciences (AREA)
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- Genetics & Genomics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a preparation method of a protein-base adhesive, belonging to the field of adhesives. The preparation method comprises the following steps: carrying out enzymolysis on high proteins in high gluten flour, centrifuging to obtain a precipitate, adding garlic, ginger, chitosan and the like into the precipitate, and fermenting so that the mixture has the anticorrosive effect; centrifuging to obtain a supernate, regulating the pH value, adding a surfactant, oscillating, carrying out crosslinking reaction with glutaric acid, adding konjaku flour to increase the viscosity, mixing the viscous substance and fermentation product, and carrying out acylation modification with acetic anhydride, thereby obtaining the adhesive. By combining bioenzyme modification and chemical modification, the method draws on each other's strength, and thus, has better effects. The chemical modification endows the proteins with new functional groups and lowers the hydrophilicity; and the bioenzyme modification is utilized to partially degrade the proteins, thereby increasing the intermolecular groups. The method has the advantages of mild acting conditions and high catalytic efficiency, and enhances the adhesiveness and storage time of the adhesive.
Description
Technical field
The preparation method that the invention discloses a kind of protein matrix adhesive, belongs to adhesive field。
Background technology
China's wood-based plate adhesive is mainly based on " three-aldehyde glue ", and the wood-based plate that this type of adhesive produces is producing, transporting and the continuous release formaldehyde of meeting in use procedure。Albumen base adhesive, owing to having that raw material sources are wide, nontoxic and the advantage such as degradability, increasingly comes into one's own at present。Then, the water resistance of albumen base adhesive is poor, and the many employings of people improve its water resistance with synthetic resin copolymerization or blended mode, can cause that it exists volatile toxic substance, and consume mass energy, contaminated environment。
Biomass, from animal and plant and microorganism etc. in nature, are inexhaustible, nexhaustible Renewable resources。Can be used for preparing glue, to wear the Renewable resource of agent of a great variety, such as plant amylum, vegetable protein, vegetable oil, pectin, lignin, tannin etc.。Wherein, vegetable protein becomes important object of study because functional group is many, active big。Along with using the exploitation of reproducible biomass to apply colloid all nontoxic, free of contamination and become trend from producing to, vegetable protein colloid studies the extensive concern causing people。
Summary of the invention
The technical problem that present invention mainly solves: poor for traditional starch glue resistance to water and gumminess, cause cohesive force in wood-based plate gluing process poor, the problem that storage period is short, the preparation method providing a kind of protein matrix adhesive, the present invention utilizes the high protein in gluten flour first to carry out enzymolysis, after enzymolysis, the centrifugal thing that is precipitated adds Bulbus Allii, Rhizoma Zingiberis Recens, the fermentation such as chitosan makes it have preservative efficacy, with 1,3-propanedicarboxylic acid cross-linking reaction after regulating pH value and add surfactant vibration after centrifugal supernatant, add Rhizoma amorphophalli powder, increase its toughness, dope and fermented product are mixed, acylation modification is carried out with acetic anhydride, to adhesive, enzyme modified and chemical modification are combined by the present invention, learn from other's strong points to offset one's weaknesses, effect is more preferably, not only given the new functional group of protein by chemical modification and reduce its hydrophilic, again through enzyme modified Partial digestion protein, increase intermolecular group, action condition is gentle, catalytic efficiency is high, and strengthen its gumminess and period of storage。
In order to solve above-mentioned technical problem, the technical solution adopted in the present invention is:
(1) 300~500g gluten flour is weighed, pressed solid-to-liquid ratio 1:8 to mix with distilled water, after stirring mixing 10~15min, mixture mass fraction 15% sodium hydroxide solution is regulated pH value 8.0~9.0, being added thereto to gross mass 1.0~1.5% enzyme and gross mass 3~5% sucrose after adjustment, carry out enzymolysis 1~2h at 35~37 DEG C, enzymolysis is cooled to room temperature after terminating, and under 6500~7500r/min rotating speed centrifugation 15~30min, respectively supernatant and precipitate;
(2) 10~12g Bulbus Allii, 12~15g Rhizoma Zingiberis Recens are weighed, Bulbus Allii is put in mortar and is ground, and by ginger crush, after squeezing the juice, Rhizoma Zingiberis Recens and garlic residue mix, mixture 1:20 in mass ratio is mixed with above-mentioned precipitate, adds 3~5g chitosan and gross mass 0.5% acetum after stirring, mixture is put in fermentation tank, add gross mass 1.2~1.5% lactobacillus leaven, be arranged at 30~35 DEG C and carry out fermentation 5~8h;
(3) taking the supernatant that step (1) obtains, first to regulate pH with mass fraction 20% hydrochloric acid solution be 4.5~6.0, it is added thereto to dodecylbenzene sodium sulfonate by liquid-solid ratio 8:1 again after adjustment, put into after stirring and Ultrasound Instrument carries out sonic oscillation 10~15min under 160~180W, solution after vibration is mixed with the 1,3-propanedicarboxylic acid of its mass fraction 1.0%, and to regulate pH value be 10.0, it is maintained at 35 DEG C and is stirred reaction 1~2h, reaction adds after terminating and reactant and Rhizoma amorphophalli powder 3:1 is in mass ratio mixed, put into after mixing in refrigerator, cold preservation 8~10h at 0~5 DEG C;
(4) fermented product after having been fermented with step (2) by the product after above-mentioned cold preservation is to mix in mass ratio 1:2, the polyvinyl alcohol adding gross mass 10~15% mass fraction 5% in mixture is stabilizer, again with mass fraction be 15% sodium hydroxide solution adjust pH value to 6.4~6.8, grafted monomers acetic anhydride it is slowly added to until pH becomes 3.5~4.0 after adjustment, keep addition gross mass 0.3~0.5% ammonium persulfate initiator under this pH, put in water-bath, stirring reaction 100~120min at 50~60 DEG C, reaction is cooled to discharging after room temperature after terminating, protein matrix biology adhesive can be obtained。
The application process of the present invention: the protein matrix biology adhesive present invention prepared is applied to compacting three layers plywood, and glue-spread is 200~250g/m2(two-sided), closes assembly time 10~15min, and hot pressing temperature 120~140 DEG C, unit pressure are 1.0~1.2MPa, hot pressing time 1.2~1.5min/mm, are pressed;The water absorption rate 5.16~6.02% of protein matrix adhesive, bonding strength is 0.58~0.69MPa respectively。
The invention has the beneficial effects as follows:
(1) enzyme modified and chemical modification are combined by the present invention, learn from other's strong points to offset one's weaknesses, and more preferably, the functional group giving protein new by chemical modification reduces its hydrophilic to effect;
(2) present invention passes through enzyme modified Partial digestion protein, increases intermolecular group, and action condition is gentle, catalytic efficiency is high, strengthens its gumminess and period of storage;
(3) raw material sources of the present invention are extensive, and preparation technology is simple, and cost is low。
Detailed description of the invention
First 300~500g gluten flour is weighed, pressed solid-to-liquid ratio 1:8 to mix with distilled water, after stirring mixing 10~15min, mixture mass fraction 15% sodium hydroxide solution is regulated pH value 8.0~9.0, being added thereto to gross mass 1.0~1.5% enzyme and gross mass 3~5% sucrose after adjustment, carry out enzymolysis 1~2h at 35~37 DEG C, enzymolysis is cooled to room temperature after terminating, and under 6500~7500r/min rotating speed centrifugation 15~30min, respectively supernatant and precipitate;Weigh 10~12g Bulbus Allii, 12~15g Rhizoma Zingiberis Recens, Bulbus Allii is put in mortar and is ground, and by ginger crush, after squeezing the juice, Rhizoma Zingiberis Recens and garlic residue mix, mixture 1:20 in mass ratio is mixed with above-mentioned precipitate, adds 3~5g chitosan and gross mass 0.5% acetum after stirring, mixture is put in fermentation tank, add gross mass 1.2~1.5% lactobacillus leaven, be arranged at 30~35 DEG C and carry out fermentation 5~8h;It is 4.5~6.0 that the supernatant obtained first regulates pH with mass fraction 20% hydrochloric acid solution, it is added thereto to dodecylbenzene sodium sulfonate by liquid-solid ratio 8:1 again after adjustment, put into after stirring and Ultrasound Instrument carries out sonic oscillation 10~15min under 160~180W, solution after vibration is mixed with the 1,3-propanedicarboxylic acid of its mass fraction 1.0%, and to regulate pH value be 10.0, it is maintained at 35 DEG C and is stirred reaction 1~2h, reaction adds after terminating and reactant and Rhizoma amorphophalli powder 3:1 is in mass ratio mixed, put into after mixing in refrigerator, cold preservation 8~10h at 0~5 DEG C;By the product after above-mentioned cold preservation with fermented after fermented product so that mass ratio 1:2 to mix, the polyvinyl alcohol adding gross mass 10~15% mass fraction 5% in mixture is stabilizer, again with mass fraction be 15% sodium hydroxide solution adjust pH value to 6.4~6.8, grafted monomers acetic anhydride it is slowly added to until pH becomes 3.5~4.0 after adjustment, keep addition gross mass 0.3~0.5% ammonium persulfate initiator under this pH, put in water-bath, stirring reaction too 100~120min at 50~60 DEG C, reaction is cooled to discharging after room temperature after terminating, protein matrix biology adhesive can be obtained。
Example 1
First 300g gluten flour is weighed, pressed solid-to-liquid ratio 1:8 to mix with distilled water, after stirring mixing 10min, mixture mass fraction 15% sodium hydroxide solution is regulated pH value 8.0, being added thereto to gross mass 1.0% enzyme and gross mass 3% sucrose after adjustment, carry out enzymolysis 1h at 35 DEG C, enzymolysis is cooled to room temperature after terminating, and under 6500r/min rotating speed centrifugation 15min, respectively supernatant and precipitate;Weigh 10g Bulbus Allii, 12g Rhizoma Zingiberis Recens, Bulbus Allii is put in mortar and is ground, and by ginger crush, after squeezing the juice, Rhizoma Zingiberis Recens and garlic residue mix, mixture 1:20 in mass ratio is mixed with above-mentioned precipitate, adds 3g chitosan and gross mass 0.5% acetum after stirring, mixture is put in fermentation tank, add gross mass 1.2% lactobacillus leaven, be arranged at 30 DEG C and carry out fermentation 5h;It is 4.5 that the supernatant obtained first regulates pH with mass fraction 20% hydrochloric acid solution, it is added thereto to dodecylbenzene sodium sulfonate by liquid-solid ratio 8:1 again after adjustment, put into after stirring and Ultrasound Instrument carries out sonic oscillation 10min under 160W, solution after vibration is mixed with the 1,3-propanedicarboxylic acid of its mass fraction 1.0%, and to regulate pH value be 10.0, it is maintained at 35 DEG C and is stirred reaction 1h, reaction adds after terminating and reactant and Rhizoma amorphophalli powder 3:1 is in mass ratio mixed, put into after mixing in refrigerator, cold preservation 8h at 0 DEG C;By the product after above-mentioned cold preservation with fermented after fermented product so that mass ratio 1:2 to mix, the polyvinyl alcohol adding gross mass 10% mass fraction 5% in mixture is stabilizer, again with mass fraction be 15% sodium hydroxide solution adjust pH value to 6.4, grafted monomers acetic anhydride it is slowly added to until pH becomes 3.5 after adjustment, keep addition gross mass 0.3% ammonium persulfate initiator under this pH, put in water-bath, stirring reaction 100min at 50 DEG C, reaction is cooled to discharging after room temperature after terminating, can obtain protein matrix biology adhesive。
The protein matrix biology adhesive present invention prepared is applied to compacting three layers plywood, and glue-spread is 200g/m2(two-sided), closes assembly time 10min, and hot pressing temperature 120 DEG C, unit pressure are 1.0MPa, hot pressing time 1.2min/mm, are pressed;The water absorption rate 5.16% of protein matrix adhesive, bonding strength is 0.58MPa respectively。
Example 2
First 400g gluten flour is weighed, pressed solid-to-liquid ratio 1:8 to mix with distilled water, after stirring mixing 13min, mixture mass fraction 15% sodium hydroxide solution is regulated pH value 8.5, being added thereto to gross mass 1.3% enzyme and gross mass 4% sucrose after adjustment, carry out enzymolysis 1.5h at 36 DEG C, enzymolysis is cooled to room temperature after terminating, and under 7000r/min rotating speed centrifugation 25min, respectively supernatant and precipitate;Weigh 11g Bulbus Allii, 13g Rhizoma Zingiberis Recens, Bulbus Allii is put in mortar and is ground, and by ginger crush, after squeezing the juice, Rhizoma Zingiberis Recens and garlic residue mix, mixture 1:20 in mass ratio is mixed with above-mentioned precipitate, adds 4g chitosan and gross mass 0.5% acetum after stirring, mixture is put in fermentation tank, add gross mass 1.3% lactobacillus leaven, be arranged at 33 DEG C and carry out fermentation 5~8h;It is 5.5 that the supernatant obtained first regulates pH with mass fraction 20% hydrochloric acid solution, it is added thereto to dodecylbenzene sodium sulfonate by liquid-solid ratio 8:1 again after adjustment, put into after stirring and Ultrasound Instrument carries out sonic oscillation 13min under 170W, solution after vibration is mixed with the 1,3-propanedicarboxylic acid of its mass fraction 1.0%, and to regulate pH value be 10.0, it is maintained at 35 DEG C and is stirred reaction 1.5h, reaction adds after terminating and reactant and Rhizoma amorphophalli powder 3:1 is in mass ratio mixed, put into after mixing in refrigerator, cold preservation 9h at 3 DEG C;By the product after above-mentioned cold preservation with fermented after fermented product so that mass ratio 1:2 to mix, the polyvinyl alcohol adding gross mass 13% mass fraction 5% in mixture is stabilizer, again with mass fraction be 15% sodium hydroxide solution adjust pH value to 6.6, grafted monomers acetic anhydride it is slowly added to until pH becomes 3.8 after adjustment, keep addition gross mass 0.4% ammonium persulfate initiator under this pH, put in water-bath, stirring reaction too 110min at 55 DEG C, reaction is cooled to discharging after room temperature after terminating, can obtain protein matrix biology adhesive。
The protein matrix biology adhesive present invention prepared is applied to compacting three layers plywood, and glue-spread is 225g/m2(two-sided), closes assembly time 13min, and hot pressing temperature 130 DEG C, unit pressure are 1.1MPa, hot pressing time 1.3min/mm, are pressed;The water absorption rate 5.58% of protein matrix adhesive, bonding strength is 0.62MPa respectively。
Example 3
First 500g gluten flour is weighed, pressed solid-to-liquid ratio 1:8 to mix with distilled water, after stirring mixing 15min, mixture mass fraction 15% sodium hydroxide solution is regulated pH value 9.0, being added thereto to gross mass 1.5% enzyme and gross mass 5% sucrose after adjustment, carry out enzymolysis 2h at 37 DEG C, enzymolysis is cooled to room temperature after terminating, and under 7500r/min rotating speed centrifugation 30min, respectively supernatant and precipitate;Weigh 12g Bulbus Allii, 15g Rhizoma Zingiberis Recens, Bulbus Allii is put in mortar and is ground, and by ginger crush, after squeezing the juice, Rhizoma Zingiberis Recens and garlic residue mix, mixture 1:20 in mass ratio is mixed with above-mentioned precipitate, adds 5g chitosan and gross mass 0.5% acetum after stirring, mixture is put in fermentation tank, add gross mass 1.5% lactobacillus leaven, be arranged at 35 DEG C and carry out fermentation 8h;It is 6.0 that the supernatant obtained first regulates pH with mass fraction 20% hydrochloric acid solution, it is added thereto to dodecylbenzene sodium sulfonate by liquid-solid ratio 8:1 again after adjustment, put into after stirring and Ultrasound Instrument carries out sonic oscillation 15min under 180W, solution after vibration is mixed with the 1,3-propanedicarboxylic acid of its mass fraction 1.0%, and to regulate pH value be 10.0, it is maintained at 35 DEG C and is stirred reaction 2h, reaction adds after terminating and reactant and Rhizoma amorphophalli powder 3:1 is in mass ratio mixed, put into after mixing in refrigerator, cold preservation 10h at 5 DEG C;By the product after above-mentioned cold preservation with fermented after fermented product so that mass ratio 1:2 to mix, the polyvinyl alcohol adding gross mass 15% mass fraction 5% in mixture is stabilizer, again with mass fraction be 15% sodium hydroxide solution adjust pH value to 6.8, grafted monomers acetic anhydride it is slowly added to until pH becomes 4.0 after adjustment, keep addition gross mass 0.5% ammonium persulfate initiator under this pH, put in water-bath, stirring reaction too 120min at 60 DEG C, reaction is cooled to discharging after room temperature after terminating, can obtain protein matrix biology adhesive。
The protein matrix biology adhesive present invention prepared is applied to compacting three layers plywood, and glue-spread is 250g/m2(two-sided), closes assembly time 15min, and hot pressing temperature 140 DEG C, unit pressure are 1.2MPa, hot pressing time 1.5min/mm, are pressed;The water absorption rate 6.02% of protein matrix adhesive, bonding strength is 0.69MPa respectively。
Claims (1)
1. the preparation method of a protein matrix adhesive, it is characterised in that concrete preparation process is:
(1) 300~500g gluten flour is weighed, pressed solid-to-liquid ratio 1:8 to mix with distilled water, after stirring mixing 10~15min, mixture mass fraction 15% sodium hydroxide solution is regulated pH value 8.0~9.0, being added thereto to gross mass 1.0~1.5% enzyme and gross mass 3~5% sucrose after adjustment, carry out enzymolysis 1~2h at 35~37 DEG C, enzymolysis is cooled to room temperature after terminating, and under 6500~7500r/min rotating speed centrifugation 15~30min, respectively supernatant and precipitate;
(2) 10~12g Bulbus Allii, 12~15g Rhizoma Zingiberis Recens are weighed, Bulbus Allii is put in mortar and is ground, and by ginger crush, after squeezing the juice, Rhizoma Zingiberis Recens and garlic residue mix, mixture 1:20 in mass ratio is mixed with above-mentioned precipitate, adds 3~5g chitosan and gross mass 0.5% acetum after stirring, mixture is put in fermentation tank, add gross mass 1.2~1.5% lactobacillus leaven, be arranged at 30~35 DEG C and carry out fermentation 5~8h;
(3) taking the supernatant that step (1) obtains, first to regulate pH with mass fraction 20% hydrochloric acid solution be 4.5~6.0, it is added thereto to dodecylbenzene sodium sulfonate by liquid-solid ratio 8:1 again after adjustment, put into after stirring and Ultrasound Instrument carries out sonic oscillation 10~15min under 160~180W, solution after vibration is mixed with the 1,3-propanedicarboxylic acid of its mass fraction 1.0%, and to regulate pH value be 10.0, it is maintained at 35 DEG C and is stirred reaction 1~2h, reaction adds after terminating and reactant and Rhizoma amorphophalli powder 3:1 is in mass ratio mixed, put into after mixing in refrigerator, cold preservation 8~10h at 0~5 DEG C;
(4) fermented product after having been fermented with step (2) by the product after above-mentioned cold preservation is to mix in mass ratio 1:2, the polyvinyl alcohol adding gross mass 10~15% mass fraction 5% in mixture is stabilizer, again with mass fraction be 15% sodium hydroxide solution adjust pH value to 6.4~6.8, grafted monomers acetic anhydride it is slowly added to until pH becomes 3.5~4.0 after adjustment, keep addition gross mass 0.3~0.5% ammonium persulfate initiator under this pH, put in water-bath, stirring reaction 100~120min at 50~60 DEG C, reaction is cooled to discharging after room temperature after terminating, protein matrix biology adhesive can be obtained。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109251710A (en) * | 2018-09-21 | 2019-01-22 | 佛山皖和新能源科技有限公司 | A kind of preparation method of high-cooling property crystal-bonding adhesive |
CN114474267A (en) * | 2022-02-26 | 2022-05-13 | 漳州市桥头木业有限公司 | Corrosion-resistant plywood and preparation method thereof |
-
2016
- 2016-04-07 CN CN201610210428.8A patent/CN105694801A/en not_active Withdrawn
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109251710A (en) * | 2018-09-21 | 2019-01-22 | 佛山皖和新能源科技有限公司 | A kind of preparation method of high-cooling property crystal-bonding adhesive |
CN114474267A (en) * | 2022-02-26 | 2022-05-13 | 漳州市桥头木业有限公司 | Corrosion-resistant plywood and preparation method thereof |
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