CN109439276B - Formaldehyde-free soybean protein-based adhesive and preparation method thereof - Google Patents
Formaldehyde-free soybean protein-based adhesive and preparation method thereof Download PDFInfo
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- CN109439276B CN109439276B CN201811422256.6A CN201811422256A CN109439276B CN 109439276 B CN109439276 B CN 109439276B CN 201811422256 A CN201811422256 A CN 201811422256A CN 109439276 B CN109439276 B CN 109439276B
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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
- 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
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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
- C09J11/04—Non-macromolecular additives inorganic
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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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Abstract
The invention discloses an aldehyde-free soybean protein-based adhesive and a preparation method thereof, wherein the adhesive comprises soybean meal powder, bromelain, chitinase, dispersion medium water, sodium periodate, diethylenetriamine, glutaraldehyde diglycidyl ether and a curing agent. According to the formaldehyde-free soybean protein-based adhesive prepared by the preparation method, soybean meal molecules are degraded and then modified and recombined to form a prepolymer, so that the protein is fully unfolded, the molecular active groups are obviously increased, the reaction activity is improved, the solubility and the water retention are improved, the toughness is increased, and the adhesive prepared by adding the elastomer-based curing agent has high toughness, high water-resistant adhesive bonding performance and high stability; the waterproof requirement of the artificial board adhesive can be met, the consumption of the cross-linking agent is reduced, so that the cost of the adhesive is reduced, and the practicability of the protein adhesive is ensured.
Description
Technical Field
The invention relates to the technical field of artificial board adhesives, in particular to an aldehyde-free soy protein-based adhesive and a preparation method thereof.
Background
China is deficient in precious wood resources, but has abundant artificial forest resources, artificial boards prepared from artificial forest fast growing wood and agricultural forest processing residues through adhesives are main raw materials for furniture floors and indoor decoration in human living environment, the total yield of the artificial boards in China is 3.2 billion cubic meters in 2016 years, and accounts for about 50% of the total yield in the world. According to the calculation that an artificial board with 9 cubic meters is produced on average per ton of adhesive, the wood adhesive consumption in 2015 in China is about 4000 ten thousand tons (solid content is 50%), wherein the urea-formaldehyde resin and modified products thereof account for more than 90% of the total output of the adhesive and dominate. The urea-formaldehyde resin adhesive is widely used in the wood industry due to the advantages of sufficient raw materials, low price, good water solubility, light color of an adhesive layer and the like. However, the urea-formaldehyde resin also has obvious defects, such as poor aging resistance and water resistance, and the like, and cannot be used for preparing outdoor artificial boards, and the like, and the fatal defects of the urea-formaldehyde resin are that the glued artificial boards have the problem of formaldehyde release, pollute the living environment and damage the body health of people.
The artificial board prepared by adopting the vegetable protein adhesive can solve the problem of free formaldehyde emission of the artificial board, but has the problems of poor water-resistant adhesive bonding performance and unstable production, which are caused by poor protein solubility, large particles and large molecular weight of raw materials such as bean pulp, cotton pulp and peanut pulp for preparing the protein adhesive, and the modification method of adding the external cross-linking agent cannot modify a matrix, so that the cross-linking structure of the protein adhesive is unevenly distributed, the toughness is poor, a large number of weak interface layers are formed, the water retention capacity is poor, and although the average strength meets the requirement, the adhesive bonding quality difference of different areas of the artificial board is large, the adhesive bonding strength is unstable, and the production efficiency is low.
Disclosure of Invention
Aiming at the defects, the invention aims to provide the formaldehyde-free soy protein-based adhesive and the preparation method thereof, the adhesive has the characteristics of small molecular weight, high activity, high curing speed, strong water retention capacity, high water-resistant bonding performance and high stability, and also has high toughness, can effectively reduce the internal stress of the prepared artificial board, has high dry strength and water-resistant bonding performance of the prepared board, and can meet the water-resistant requirement of the artificial board adhesive; and the preparation method has low cost and is easy to realize.
In order to achieve the purpose, the technical scheme of the invention is as follows:
an aldehyde-free soy protein-based adhesive is composed of the following raw materials in parts by weight:
35 parts of soybean meal, 0.1-0.3 part of bromelain, 0.1-0.3 part of bean chitinase, 70 parts of dispersion medium water, 2-5 parts of sodium periodate, 0.2-0.5 part of diethylenetriamine, 0.3-0.8 part of glutaraldehyde diglycidyl ether and 0.6-1.0 part of curing agent.
The preferable mode is that the feed is composed of the following raw materials in parts by weight: 35 parts of soybean meal, 0.1 part of bromelain, 0.1 part of bean chitinase, 70 parts of dispersion medium water, 2 parts of sodium periodate, 0.2 part of diethylenetriamine, 0.3 part of glutaraldehyde diglycidyl ether and 0.6 part of a curing agent.
The preferable mode is that the feed is composed of the following raw materials in parts by weight: 35 parts of soybean meal, 0.1 part of bromelain, 0.3 part of bean chitinase, 70 parts of dispersion medium water, 5 parts of sodium periodate, 0.5 part of diethylenetriamine, 0.8 part of glutaraldehyde diglycidyl ether and 1 part of a curing agent.
Preferably, the content of protein in the soybean meal accounts for 52% by mass, and the particle sizes are all 180-200 meshes.
Preferably, the bromelain and the bean chitinase are molecular weight reducing agents.
Preferably, the sodium periodate and the diethylenetriamine are both activators.
Preferably, the glutaraldehyde diglycidyl ether is a protein molecule recombination agent.
Preferably, the curing agent is a copolymer of ammonia water, polyether sulfone and epichlorohydrin, and the curing agent is prepared by the following method:
putting 90kg of epoxy chloropropane into a reaction kettle, heating to 60 ℃, adding 16kg of 25% ammonia water solution, reacting for 2 hours, dropwise adding 45kg of 25% ammonia water within 6 hours, controlling the temperature of the reaction kettle to be 60 ℃, preserving the temperature for 1 hour, adding 15kg of polyether sulfone and 10kg of ethanol, reacting for 1 hour at 60 ℃, adding 15kg of water, adjusting the pH value to be 9.0, cooling to 30 ℃, and discharging.
Preferably, the dispersion medium water is selected from common tap water or softened water.
A preparation method of the aldehyde-free soy protein-based adhesive comprises the following steps:
(1) weighing the components according to the weight ratio in the formaldehyde-free soy protein based adhesive to prepare raw materials;
(2) uniformly dispersing soybean meal powder, water, bromelain and chitinase in dispersion medium water, heating to 40 ℃ in a water bath, stirring for 30 minutes, heating to 80 ℃, and preserving heat for 10 minutes to inactivate enzyme;
(3) adding sodium periodate into the mixture obtained in the step 2, heating to 50 ℃, adjusting the pH value to 4.0, reacting for 3 hours, adding diethylenetriamine, reacting for 2 hours at 50 ℃, heating to 90 ℃, reacting for 5 hours, and reacting for 5 hours;
(4) heating the mixture obtained in the step (3) to 80 ℃, adjusting the pH to =10, adding glutaraldehyde diglycidyl ether to react for 1 hour, cooling and discharging to obtain an aldehyde-free soy protein-based adhesive prepolymer;
(5) and (4) adding a curing agent into the prepolymer obtained in the step (4) during the use process, and performing hot-pressing curing.
After the technical scheme is adopted, the invention has the beneficial effects that:
the formaldehyde-free soy protein based adhesive and the preparation method thereof are characterized in that the formaldehyde-free soy protein based adhesive is prepared from the following raw materials in parts by weight: bean pulp powder, bromelain, bean chitinase, dispersion medium water, sodium periodate, diethylenetriamine, glutaraldehyde diglycidyl ether and a curing agent. The adhesive disclosed by the invention has the characteristics of small molecular weight, high activity, high curing speed, strong water retention capacity, high water-resistant bonding performance and high stability, and also has high toughness, the internal stress of a prepared artificial board can be effectively reduced, the dry strength and the water-resistant bonding performance of the prepared board are high, and the water-resistant requirement of the artificial board adhesive can be met.
The bromelain in the raw material enables the protein to be unfolded and hydrolyzed into small molecular polypeptide chains, and internal active groups are fully exposed; the sodium periodate oxidizes inert hydroxyl groups on polypeptides, polysaccharides and fibers, improves the reactivity, and the diethylenetriamine can be grafted on the oxidized polypeptides, proteins and fibers to provide a large amount of amino groups. The activating agent can effectively stretch and break the soybean meal molecules, increase the number and types of reactive groups on the soybean meal molecules, improve the reactivity of the soybean meal molecules and reduce the viscosity of the adhesive.
The glutaraldehyde diglycidyl ether in the raw materials is a protein molecule recombination agent, so that hydrolyzed small molecule protein can be recombined to form a prepolymer with a certain molecular weight, and the cohesive force of adhesive molecules is increased.
The curing agent in the raw material is a copolymer of ammonia water, polyether sulfone and epichlorohydrin, and can effectively react with hydroxyl and amino in the bean pulp molecules to form a cross-linked network structure so as to cure the adhesive.
The invention has the advantages that:
1) according to the invention, the degradation agent and the activating agent are adopted, so that the soybean meal molecules are fully stretched and broken to form soybean meal micromolecules, the number and the types of active groups of a molecular system are increased, and the reaction activity is improved;
2) according to the invention, activated small-molecular soybean meal is connected into the soybean meal protein adhesive prepolymer with a certain molecular weight by adopting the epoxide, so that the problem of low adhesive strength caused by adhesive penetration caused by hydrolysis of the soybean meal into small molecules is solved. In addition, the formed prepolymer of the soybean meal protein adhesive has uniform molecular weight, good permeability, good water solubility and good water-retaining property, the problems of low adhesive dry strength, poor adhesive stability, poor water-retaining property and poor water solubility of the common protein adhesive are solved by the prepared adhesive, the reaction activity is improved, the types and the number of the soybean meal molecules are increased, the reaction capacity with a cross-linking agent is increased, and the using amount of a curing agent is reduced.
3) The invention adopts the polyether sulfone-based multifunctional curing agent which can be uniformly mixed with an adhesive system to form a toughness crosslinking system with a microphase separation structure after curing, thereby improving the toughness of the adhesive and reducing the internal stress of the prepared artificial board, and further improving the water-resistant cementing property of the adhesive.
4) According to the preparation method, toxic substances are not added, the molecules of the soybean meal are degraded by using protease, the types and the number of reactive groups of the soybean meal are effectively improved by using an activating agent on the basis of degrading small molecules, the molecules of the soybean meal are recombined by using epoxide to form a prepolymer of a soybean meal raw material, and finally, a toughness curing agent is added to cure the soybean meal protein adhesive, so that the efficiency is high, no harmful substance is released, and the product has high reaction activity, good solubility, good water retention and good toughness. The adhesive prepared can effectively improve the performance of the adhesive and promote the application of the protein adhesive;
the test proves that: the bean pulp protein adhesive has the advantages of good water retention, high solubility, high curing speed, easy formation of a cross-linked structure, high cross-linked density, good toughness and water resistance after curing, stable performance and stable and improved quality of prepared plywood products.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following embodiments further describe the present invention in detail. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The percent in the present invention means mass percent unless otherwise specified; but the percentage of the solution, unless otherwise specified, means that 100ml of the solution contains several grams of solute; the percentage between the liquids refers to the ratio of the volumes at 20 ℃.
The general scheme is as follows:
an aldehyde-free soy protein-based adhesive is composed of the following raw materials in parts by weight:
35 parts of soybean meal, 0.1-0.3 part of bromelain, 0.1-0.3 part of bean chitinase, 70 parts of dispersion medium water, 2-5 parts of sodium periodate, 0.2-0.5 part of diethylenetriamine, 0.3-0.8 part of glutaraldehyde diglycidyl ether and 0.6-1.0 part of curing agent.
The content of protein in the soybean meal accounts for 52% by mass, and the particle sizes are all 180-200 meshes.
The bromelain and the bean chitinase are molecular weight reducing agents.
The sodium periodate and the diethylenetriamine are both activating agents.
The glutaraldehyde diglycidyl ether is a protein molecule recombination agent.
The curing agent is a copolymer of ammonia water, polyether sulfone and epoxy chloropropane, and is prepared by the following method:
putting 90kg of epoxy chloropropane into a reaction kettle, heating to 60 ℃, adding 16kg of 25% ammonia water solution, reacting for 2 hours, dropwise adding 45kg of 25% ammonia water within 6 hours, controlling the temperature of the reaction kettle to be 60 ℃, preserving the temperature for 1 hour, adding 15kg of polyether sulfone and 10kg of ethanol, reacting for 1 hour at 60 ℃, adding 15kg of water, adjusting the pH value to be 9.0, cooling to 30 ℃, and discharging.
The dispersion medium water is selected from common tap water or softened water.
According to the formaldehyde-free soybean protein-based adhesive, soybean meal molecules are degraded firstly and then modified and recombined to form a prepolymer, so that the protein is fully extended, the molecular active groups are obviously increased, the reaction activity is improved, the solubility and the water retention are improved, the toughness is increased, and the prepared adhesive is high in toughness, high in water-resistant bonding performance and high in stability after an elastomer-based curing agent is added; the waterproof requirement of the artificial board adhesive can be met, the consumption of the cross-linking agent is reduced, so that the cost of the adhesive is reduced, and the practicability of the protein adhesive is ensured.
Example 1
An aldehyde-free soy protein-based adhesive is composed of the following raw materials by weight:
70 kg of softened water;
35 kg of defatted soybean protein powder;
bromelain 0.1 kg;
0.1kg of bean husk polysaccharase;
2kg of sodium periodate;
0.2kg of diethylenetriamine;
0.3kg of glutaraldehyde diglycidyl ether;
0.6kg of curing agent.
The preparation method of the soybean meal protein adhesive in the embodiment comprises the following steps: stirring the prepared soybean meal protein adhesive prepolymer and the curing agent for 10 minutes at normal temperature, and uniformly stirring for use.
Example 2
An aldehyde-free soy protein-based adhesive is composed of the following raw materials by weight:
70 kg of softened water;
35 kg of defatted soybean protein powder;
bromelain 0.3 kg;
0.3kg of bean husk polysaccharase;
5kg of sodium periodate;
0.5kg of diethylenetriamine;
0.8kg of glutaraldehyde diglycidyl ether;
1kg of curing agent.
Example 3
A preparation method of the aldehyde-free soy protein-based adhesive comprises the following steps:
(1) weighing the respective component preparation materials in the weight ratio in the aldehyde-free soy protein-based adhesive according to any one of claims 1 to 9;
(2) uniformly dispersing soybean meal powder, water, bromelain and chitinase in dispersion medium water, heating to 40 ℃ in a water bath, stirring for 30 minutes, heating to 80 ℃, and preserving heat for 10 minutes to inactivate enzyme;
(3) adding sodium periodate into the mixture obtained in the step 2, heating to 50 ℃, adjusting the pH value to 4.0, reacting for 3 hours, adding diethylenetriamine, reacting for 2 hours at 50 ℃, heating to 90 ℃, reacting for 5 hours, and reacting for 5 hours;
(4) heating the mixture obtained in the step (3) to 80 ℃, adjusting the pH to =10, adding glutaraldehyde diglycidyl ether to react for 1 hour, cooling and discharging to obtain an aldehyde-free soy protein-based adhesive prepolymer;
(5) and (4) adding a curing agent into the prepolymer obtained in the step (4) during the use process, and performing hot-pressing curing.
Comparative examples 1 to 3
Compared with examples 1-2, control 1 was a mixture of common soybean meal powder, water and curing agent; the control group 2 is the soybean meal powder which is not degraded and is mixed with activated water and curing agent; the control group 3 is a soybean meal protein adhesive which is degraded and activated to generate a prepolymer but is not added with a curing agent.
Test examples
Three-layer plywood was prepared using the adhesives of examples 1-2 and comparative examples 1-3, respectively, of the present invention.
Poplar veneer: drying to 10% of water content; size 40cm by 0.15 cm.
The preparation method comprises the following normal preparation processes:
sizing: the glue coating amount is 400g/m2。
Pressure, temperature, time: 0.8MPa, 120 ℃ for 6 minutes.
The performance of the transverse spliced product is detected according to the detection method of GB/T17657-1999 test method for physical and chemical properties of artificial boards and facing artificial boards, and the detection result is shown in Table 1.
TABLE 1 plywood bond Strength
The experimental result shows that the water-resistant bonding performance of the prepared plywood can be effectively improved by the bean pulp protein adhesive, the bonding strength is more than 1.48MPa and the dry strength is more than 1.79 according to the detection of a II plywood, and the standard deviation calculation shows that the stability of the adhesive prepared from activated bean pulp protein is obviously improved, and the reinforcing effect is obvious. The breaking elongation reaches more than 10 percent, and the high-temperature curing speed reaches within 4 minutes.
The above-described preferred embodiments of the present invention are not intended to limit the present invention, and any modification, equivalent to the aldehyde-free soy protein based adhesive and the structural improvement of the method for preparing the same, made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (4)
1. A preparation method of an aldehyde-free soy protein-based adhesive is characterized in that,
the formaldehyde-free soy protein based adhesive is prepared from the following raw materials in parts by weight: 35 parts of soybean meal, 0.1-0.3 part of bromelain, 0.1-0.3 part of bean chitinase, 70 parts of dispersion medium water, 2-5 parts of sodium periodate, 0.2-0.5 part of diethylenetriamine, 0.3-0.8 part of glutaraldehyde diglycidyl ether and 0.6-1.0 part of curing agent; the content of protein in the soybean meal accounts for 52% by mass, and the particle sizes are all 180-200 meshes;
the preparation method comprises the following steps:
(1) weighing the components according to the weight ratio in the formaldehyde-free soy protein based adhesive to prepare raw materials;
(2) uniformly dispersing soybean meal powder, water, bromelain and chitinase in dispersion medium water, heating to 40 ℃ in a water bath, stirring for 30 minutes, heating to 80 ℃, and preserving heat for 10 minutes to inactivate enzyme;
(3) adding sodium periodate into the mixture obtained in the step 2, heating to 50 ℃, adjusting the pH value to 4.0, reacting for 3 hours, adding diethylenetriamine, reacting for 2 hours at 50 ℃, heating to 90 ℃, reacting for 5 hours, and reacting for 5 hours;
(4) heating the mixture obtained in the step (3) to 80 ℃, adjusting the pH to =10, adding glutaraldehyde diglycidyl ether to react for 1 hour, cooling and discharging to obtain an aldehyde-free soybean protein-based adhesive prepolymer;
(5) and (3) adding a curing agent into the prepolymer obtained in the step (4) during the use process, and performing hot-pressing curing, wherein the curing agent is a copolymer of ammonia water, polyether sulfone and epoxy chloropropane, and is prepared by the following method: putting 90kg of epoxy chloropropane into a reaction kettle, heating to 60 ℃, adding 16kg of 25% ammonia water solution, reacting for 2 hours, dropwise adding 45kg of 25% ammonia water within 6 hours, controlling the temperature of the reaction kettle to be 60 ℃, keeping the temperature for 1 hour, adding 15kg of polyether sulfone and 10kg of ethanol, reacting for 1 hour at 60 ℃, adding 15kg of water, adjusting the pH value to be 9.0, cooling to 30 ℃, and discharging.
2. The method for preparing the aldehyde-free soy protein based adhesive according to claim 1, wherein the aldehyde-free soy protein based adhesive is prepared from the following raw materials in parts by weight: 35 parts of soybean meal, 0.1 part of bromelain, 0.1 part of bean chitinase, 70 parts of dispersion medium water, 2 parts of sodium periodate, 0.2 part of diethylenetriamine, 0.3 part of glutaraldehyde diglycidyl ether and 0.6 part of a curing agent.
3. The method for preparing the aldehyde-free soy protein based adhesive according to claim 1, wherein the aldehyde-free soy protein based adhesive is prepared from the following raw materials in parts by weight: 35 parts of soybean meal, 0.1 part of bromelain, 0.3 part of bean chitinase, 70 parts of dispersion medium water, 5 parts of sodium periodate, 0.5 part of diethylenetriamine, 0.8 part of glutaraldehyde diglycidyl ether and 1 part of a curing agent.
4. The method for preparing the aldehyde-free soy protein-based adhesive according to any one of claims 1 to 3, wherein the dispersion medium water is selected from common tap water or softened water.
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| CN110982487B (en) * | 2019-12-27 | 2021-05-25 | 北京林业大学 | Formaldehyde-free soy protein adhesive with multiple network structures and preparation method thereof |
| CN112048280A (en) * | 2020-08-21 | 2020-12-08 | 安徽三和工艺品有限公司 | Preparation method of dopamine hydrochloride-based adhesive for willow |
| CN113105847B (en) * | 2021-03-24 | 2022-07-05 | 北京林业大学 | Protein-based adhesive as well as preparation method and application thereof |
| CN113652196B (en) * | 2021-08-06 | 2023-03-21 | 湖北福汉木业有限公司 | Formaldehyde-free soybean glue and preparation method and application thereof |
| CN114656896A (en) * | 2022-05-24 | 2022-06-24 | 北京林业大学 | Oil-tea-meal-based aldehyde-free self-mildew-proof water-resistant adhesive |
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