CN116536024A - Plate adhesive and preparation method thereof - Google Patents

Plate adhesive and preparation method thereof Download PDF

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Publication number
CN116536024A
CN116536024A CN202310647554.XA CN202310647554A CN116536024A CN 116536024 A CN116536024 A CN 116536024A CN 202310647554 A CN202310647554 A CN 202310647554A CN 116536024 A CN116536024 A CN 116536024A
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modified
stirring
parts
mass
certain mass
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董毅
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Anji Yixin Furniture Co ltd
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Anji Yixin Furniture Co ltd
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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
    • C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/48—Polymers modified by chemical after-treatment
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention relates to the technical field of adhesives, in particular to a plate adhesive and a preparation method thereof; comprises the following raw materials, by mass, 50-80 parts of modified polyamide, 8-15 parts of polyisocyanate, 20-30 parts of modified soybean protein, 20-40 parts of modified polyurethane and 3-5 parts of curing agent; the prepared plate adhesive has the performances of wear resistance and high temperature resistance, enhances the water resistance, increases the adaptability of the plate adhesive, is convenient to transport and store, enlarges the service operation time, reserves the operation space for the sizing process, and has good bonding performance.

Description

Plate adhesive and preparation method thereof
Technical Field
The invention relates to the technical field of adhesives, in particular to a plate adhesive and a preparation method thereof.
Background
Solid wood materials are renewable resources, but still are difficult to meet the use demands of human beings, and artificial boards woven by forestry wastes fill the gaps of solid wood boards. With the improvement of environmental protection and health consciousness, people pay more and more attention to indoor living environment and air quality, and GB/T39600-2021 classification of formaldehyde release amount of artificial boards and products thereof, traditional adhesives such as urea-formaldehyde resin adhesives, phenolic resin adhesives and melamine formaldehyde resin adhesives for artificial boards are gradually not applicable any more, and the use of environment-friendly adhesives for artificial board processing is a necessary choice for artificial boards.
Currently, the invention and use of environmentally friendly adhesives tend to use biomass-based adhesives, and the types developed include starch, vegetable protein, wood fiber, vegetable oil, shan Ningjiao adhesives, and the like. However, the existing biomass-based adhesives have a great number of problems, firstly, the adhesion performance of the biomass-based adhesives is poor, and the sizing amount needs to be great. In addition, the environment-friendly adhesive has larger viscosity, the fluidity and the bonding performance cannot be well balanced, and the adhesive with larger viscosity often needs to be sacrificed in order to ensure the better bonding performance, so that the adhesive has higher requirements on the sizing process and the sizing process. In addition, the environment-friendly adhesive has the defects of poor wear resistance, poor water resistance and poor high temperature resistance, and the bonding capacity of the adhesive is reduced rapidly in a higher-temperature and higher-humidity environment, so that the structural stability of the plywood can not be well maintained.
In order to further develop the environment-friendly adhesive, fully utilize natural resources, solve the problems of poor cohesiveness and poor fluidity of the bio-based adhesive, develop an adhesive with better fluidity and convenient sizing, ensure good gluing capability in high-temperature and high-humidity environment, have good wear resistance and durable adhesive, and have positive significance for the development and practical use of the adhesive.
Disclosure of Invention
The invention aims to provide a plate adhesive and a preparation method thereof, and the prepared plate adhesive has the performances of wear resistance and high temperature resistance, enhances the water resistance, increases the adaptability of the plate adhesive, is convenient for transportation and storage, enlarges the service operation time, reserves enough operation space for the sizing process, and has good bonding performance.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the plate adhesive comprises the following raw materials in parts by weight: 50-80 parts of modified polyamide, 8-15 parts of polyisocyanate, 20-30 parts of modified soybean protein, 20-40 parts of modified polyurethane and 3-5 parts of curing agent;
the preparation method of the plate adhesive comprises the following steps:
step one: taking the mass portion of modified polyamide, adding deionized water with the mass of 0.5-0.8 times of the modified polyamide, stirring for 3-5 min at the speed of 80-100 r/min, adding the mass portion of polyisocyanate, and stirring for 5-10 min at the speed of 80-100 r/min to obtain a mixture A;
step two: taking the modified soybean protein and the modified polyurethane in parts by weight, and stirring at a speed of 80-100 r/min for 5-15 min to obtain a mixture B;
step three: and (3) taking the curing agent in parts by weight, adding ethylene glycol with the mass which is 3-5 times that of the curing agent, uniformly stirring, adding the mixture A obtained in the step (A) and the mixture B obtained in the step (I), and uniformly mixing and stirring to obtain the plate adhesive.
Further preferably, the modified polyamide is prepared by taking a certain mass of polyamide epichlorohydrin, adipic acid, diethylenetriamine and distilled water, adding the mixture into a high-pressure reaction kettle, reacting at 260-300 ℃ under a nitrogen atmosphere for 10-20 hours under high pressure, taking out and adding a proper amount of H 2 SO 4 Regulating the pH value to 2-3, adding polyvinyl alcohol with a certain mass, and regulating the pH value to 2-3 again to obtain the modified polyamide.
Further preferably, the mass ratio of the raw materials in the modified polyamide is polyamide epichlorohydrin: adipic acid: diethylenetriamine: distilled water: polyvinyl alcohol = 10: 8-10: 10 to 15:5:10.
further preferably, the modified soy protein is glycidyl methacrylate grafted soy protein isolate, which is:
taking a certain mass of soybean protein isolate, adding a certain mass of sodium bisulphite and a certain mass of deionized water, heating to 60-80 ℃ in a water bath, stirring for 2-3 hours at a speed of 80-100 r/min, centrifuging for 20min at a speed of 8000/min, and freeze-drying to obtain pretreated soybean protein isolate;
taking a certain mass of pretreated soybean protein isolate, adding a certain mass of 2-bromo isobutyryl bromide, 4-dimethylaminopyridine and N, N-dimethylformamide, magnetically stirring for 20 hours at room temperature, then adding a certain mass of glycidyl methacrylate and copper bromide, and stirring for 3-4 hours at a speed of 80-100 r/min under a nitrogen atmosphere at a temperature of 80-100 ℃ to obtain modified soybean protein.
Further preferably, the mass ratio of the modified soy protein raw material is soy protein isolate: sodium bisulfite: deionized water = 10:1:20, a step of; pretreatment of isolated soy protein: 2-bromoisobutyryl bromide: 4-dimethylaminopyridine: n, N-dimethylformamide: glycidyl methacrylate: copper bromide = 100: 2-3: 1:20:50:1.
the complex structure of the soybean protein isolate is destroyed under the pretreatment of sodium bisulphite, so that more amino groups and carboxyl groups are exposed, reactive sites are increased, the pretreated soybean protein isolate is obtained, and then the hydrogen of the amino group on the soybean protein isolate is reacted with bromine on 2-bromoisobutyryl bromide in the presence of 4-dimethylaminopyridine to form a macromolecular initiatorThen, the modified soybean protein is obtained through a polymerization reaction with glycidyl methacrylate, wherein the polymerization reaction is as follows:
further preferably, the modified polyurethane is prepared by taking isophorone diisocyanate and 2, 2-dimethylolpropionic acid with certain mass, placing the isophorone diisocyanate and the 2, 2-dimethylolpropionic acid in a reaction kettle, adding dibutyl tin dilaurate with certain mass, stirring for 3-4 hours at a speed of 100-150 r/min under a nitrogen atmosphere at a temperature of 70-90 ℃, adding a chain extender 1, 4-butanediol with certain mass, continuing stirring for 3-4 hours, adding a capping agent aminopropyl triethoxysilane with certain mass, and continuing stirring for 0.5-1 hour.
Further preferably, the modified polyurethane comprises the following raw materials in mass ratio: 2, 2-bis-hydroxymethyl propionic acid: dibutyl tin dilaurate: 1, 4-butanediol: aminopropyl triethoxysilane = 50:5:1: 2-3: 3 to 5.
The modified polyurethane is siloxane functional polyurethane, isophorone diisocyanate and 2, 2-dimethylolpropionic acid react to generate polyurethane under the initiation of dibutyl tin dilaurate, the molecular chain of the polyurethane is further lengthened under the action of a chain extender 1, 4-butanediol, and finally the polyurethane is blocked under the action of a blocking agent aminopropyl triethoxysilane, and a silane group is added into the polyurethane molecular chain to obtain the modified polyurethane, wherein the reaction is as follows:
further preferably, the curing agent is one of polyetheramine, divinyl triamine, ethylenediamine and vinyl triamine.
The invention has the beneficial effects that:
1. the modified polyamide is mixed with the polyisocyanate, and a crosslinking reaction occurs in the mixing process, so that the concentration of the polyisocyanate is reduced, the water resistance of the adhesive of the polyisocyanate is increased, the adaptability is improved, the using operation time is prolonged, and the operation space is reserved for the sizing process; modified soybean protein and modified polyurethane are added to prepare a composite adhesive, silane groups are introduced into the composite adhesive, the wear resistance and high temperature resistance of the adhesive are improved, the modified soybean protein can permeate into a gap of a plate, the interface effect is exerted, the adhesive performance is enhanced, the raw material source of the adhesive is enlarged, and the bonding effect of the adhesive to different raw materials is enhanced.
2. The modified polyamide adopted by the invention is a mixed solution of a polyamide solution and a polyvinyl alcohol solution, the modified polyamide is aqueous polyamide, a solution system formed by polyamide and polyvinyl alcohol is a basis for mainly exerting aqueous performance, the aqueous polyamide and the polyisocyanate are mixed to form an aqueous polymer-isocyanate adhesive, and meanwhile, the pH is adjusted to be acidic, so that the modified polyamide and the polyisocyanate undergo a crosslinking reaction to form larger molecules, part of isocyanic acid radicals are consumed, the concentration of the polyisocyanate is reduced, the aqueous polymer-isocyanate adhesive cannot be solidified when meeting water Ma Nianjie, the water resistance of the adhesive is increased, the adaptability of the adhesive is increased, the adhesive is convenient to transport and store, the service operation time is prolonged, and the operation space is reserved for the sizing process.
3. The modified soybean protein adopted by the invention is prepared by pretreating soybean protein isolate in sodium bisulphite, exposing more amino and carboxyl, increasing reactive sites, reacting with 2-bromoisobutyryl bromide and glycidyl methacrylate, grafting the glycidyl methacrylate onto the surface of soybean protein molecules to obtain a soybean protein-glycidyl methacrylate grafted copolymer, so that the permeation energy of the modified soybean protein to a plate is enhanced, the structural stability of the modified soybean protein is enhanced, the modified soybean protein permeates the plate, the interface effect is better exerted, and the bonding performance is enhanced.
4. According to the invention, the modified polyurethane is adopted, and the silane groups are mainly introduced into the molecular chain of the modified polyurethane, so that the bonding range of the modified polyurethane can be expanded, the modified polyurethane has the same bonding capability to inorganic substances, and the good bonding capability to organic polymer materials and inorganic materials is realized.
5. Through modifying polyamide and crosslinking the polyamide with polyisocyanate to form a water-based polymer-isocyanate adhesive, adding modified soybean protein and modified polyurethane to compound the adhesive for the plates, the prepared adhesive has good adaptability, the adhesive performance is not easy to lose in the storage and transportation processes, meanwhile, the penetrability of the adhesive to the plates is enlarged, the bonding performance is improved, and the adhesive has certain wear resistance and high temperature resistance.
Detailed Description
The following description of the present invention will be made clearly and fully, and it is apparent that the embodiments described are only some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The plate adhesive comprises the following raw materials in parts by weight: 50 parts of modified polyamide, 8 parts of polyisocyanate, 20 parts of modified soybean protein, 20 parts of modified polyurethane and 3 parts of curing agent;
the modified polyamide is prepared by taking a certain mass of polyamide epichlorohydrin, adipic acid, diethylenetriamine and distilled water, adding into a high-pressure reaction kettle, reacting for 10 hours at 260 ℃ under the nitrogen atmosphere and taking out, and adding a proper amount of H 2 SO 4 Regulating the pH value to 2, adding polyvinyl alcohol with a certain mass, and regulating the pH value to 2 again to obtain modified polyamide; wherein the mass ratio of the raw materials in the modified polyamide is polyamide epichlorohydrin: adipic acid: diethylenetriamine: distilled water: polyvinyl alcohol = 10:8:10:5:10;
the modified soy protein is glycidyl methacrylate grafted soy protein isolate, which is:
taking a certain mass of soybean protein isolate, adding sodium bisulphite and deionized water, heating to 60 ℃ in a water bath, stirring for 2 hours at a speed of 80r/min, centrifuging for 20 minutes at a speed of 8000/min, and freeze-drying to obtain pretreated soybean protein isolate;
taking a certain mass of pretreated soybean protein isolate, adding a certain mass of 2-bromo isobutyryl bromide, 4-dimethylaminopyridine and N, N-dimethylformamide, magnetically stirring for 20 hours at room temperature, then adding a certain mass of glycidyl methacrylate and copper bromide, and stirring for 3 hours at a speed of 80r/min under a nitrogen atmosphere at 80 ℃ to obtain modified soybean protein; wherein the mass ratio of the modified soy protein raw materials is soy protein isolate: sodium bisulfite: deionized water = 10:1:20, a step of; pretreatment of isolated soy protein: 2-bromoisobutyryl bromide: 4-dimethylaminopyridine: n, N-dimethylformamide: glycidyl methacrylate: copper bromide = 100:2:1:20:50:1, a step of;
the modified polyurethane is prepared by taking isophorone diisocyanate and 2, 2-dimethylolpropionic acid with certain mass, placing the isophorone diisocyanate and the 2, 2-dimethylolpropionic acid in a reaction kettle, adding dibutyl tin dilaurate with certain mass, stirring for 3 hours at the speed of 100r/min at the temperature of 70 ℃ under the nitrogen atmosphere, adding a chain extender 1, 4-butanediol with certain mass, continuously stirring for 3 hours, adding a capping agent aminopropyl triethoxysilane with certain mass, and continuously stirring for 0.5 hour; wherein the mass ratio of raw materials in the modified polyurethane is isophorone diisocyanate: 2, 2-bis-hydroxymethyl propionic acid: dibutyl tin dilaurate: 1, 4-butanediol: aminopropyl triethoxysilane = 50:5:1:2:3, a step of;
the curing agent is polyetheramine;
the preparation method of the plate adhesive comprises the following steps:
step one: taking the mass parts of modified polyamide, adding deionized water with the mass of 0.5 times of the modified polyamide, stirring at the speed of 80r/min for 3min, adding the mass parts of polyisocyanate, and stirring at the speed of 80r/min for 5min to obtain a mixture A;
step two: taking the modified soybean protein and the modified polyurethane in parts by weight, and stirring at the speed of 80r/min for 5min to obtain a mixture B;
step three: and (3) taking the curing agent in parts by weight, adding ethylene glycol with the mass which is 3 times that of the curing agent, uniformly stirring, adding the mixture A obtained in the step (A) and the mixture B obtained in the step (I), and uniformly mixing and stirring to obtain the plate adhesive.
Example 2
The plate adhesive comprises the following raw materials in parts by weight: 80 parts of modified polyamide, 15 parts of polyisocyanate, 30 parts of modified soybean protein, 40 parts of modified polyurethane and 5 parts of curing agent;
the modified polyamide is prepared by taking a certain mass of polyamide epichlorohydrin, adipic acid, diethylenetriamine and distilled water, adding into a high-pressure reaction kettle, reacting for 20 hours at 300 ℃ under the nitrogen atmosphere and high pressure, taking out and adding a proper amount of H 2 SO 4 Regulating the pH value to 3, adding polyvinyl alcohol with a certain mass, and regulating the pH value to 3 again to obtain modified polyamide; wherein the mass ratio of the raw materials in the modified polyamide is polyamide epichlorohydrin: adipic acid: diethylenetriamine: distilled water: polyvinyl alcohol = 10:10:15:5:10;
the modified soy protein is glycidyl methacrylate grafted soy protein isolate, which is:
taking a certain mass of soybean protein isolate, adding sodium bisulphite and deionized water, heating to 80 ℃ in a water bath, stirring for 3 hours at a speed of 100r/min, centrifuging for 20 minutes at a speed of 8000/min, and freeze-drying to obtain pretreated soybean protein isolate;
taking a certain mass of pretreated soybean protein isolate, adding a certain mass of 2-bromo isobutyryl bromide, 4-dimethylaminopyridine and N, N-dimethylformamide, magnetically stirring for 20 hours at room temperature, then adding a certain mass of glycidyl methacrylate and copper bromide, and stirring for 4 hours at a speed of 100r/min under a nitrogen atmosphere at a temperature of 100 ℃ to obtain modified soybean protein; wherein the mass ratio of the modified soy protein raw materials is soy protein isolate: sodium bisulfite: deionized water = 10:1:20, a step of; pretreatment of isolated soy protein: 2-bromoisobutyryl bromide: 4-dimethylaminopyridine: n, N-dimethylformamide: glycidyl methacrylate: copper bromide = 100:3:1:20:50:1, a step of;
the modified polyurethane is prepared by placing isophorone diisocyanate and 2, 2-dimethylolpropionic acid with certain mass in a reaction kettle, adding dibutyl tin dilaurate with certain mass, stirring at a speed of 150r/min under a nitrogen atmosphere at 90 ℃ for 4 hours, adding a chain extender 1, 4-butanediol with certain mass, continuously stirring for 4 hours, adding a capping agent aminopropyl triethoxysilane with certain mass, and continuously stirring for 1 hour; wherein the mass ratio of raw materials in the modified polyurethane is isophorone diisocyanate: 2, 2-bis-hydroxymethyl propionic acid: dibutyl tin dilaurate: 1, 4-butanediol: aminopropyl triethoxysilane = 50:5:1:3:5, a step of;
the curing agent is divinyl triamine;
the preparation method of the plate adhesive comprises the following steps:
step one: taking the mass parts of modified polyamide, adding deionized water with the mass of 0.8 times of the modified polyamide, stirring at the speed of 100r/min for 5min, adding the mass parts of polyisocyanate, and stirring at the speed of 100r/min for 10min to obtain a mixture A;
step two: taking the modified soybean protein and the modified polyurethane in parts by weight, and stirring at a speed of 100r/min for 15min to obtain a mixture B;
step three: and (3) taking the curing agent in parts by weight, adding ethylene glycol with the mass which is 5 times that of the curing agent, uniformly stirring, adding the mixture A obtained in the step (A) and the mixture B obtained in the step (I), and uniformly mixing and stirring to obtain the plate adhesive.
Example 3
The plate adhesive comprises the following raw materials in parts by weight: 60 parts of modified polyamide, 12 parts of polyisocyanate, 25 parts of modified soybean protein, 30 parts of modified polyurethane and 4 parts of curing agent;
the modified polyamide is prepared by taking a certain mass of polyamide epichlorohydrin, adipic acid, diethylenetriamine and distilled water, adding into a high-pressure reaction kettle, reacting for 15 hours at 280 ℃ under the nitrogen atmosphere and high pressure, taking out and adding a proper amount of H 2 SO 4 Regulating the pH value to 3, adding polyvinyl alcohol with a certain mass, and regulating the pH value to 3 again to obtain modified polyamide; wherein the mass ratio of the raw materials in the modified polyamide is polyamide epichlorohydrin: adipic acid: diethylenetriamine: distilled water: polyvinyl alcohol = 10:9:13:5:10;
the modified soy protein is glycidyl methacrylate grafted soy protein isolate, which is:
taking a certain mass of soybean protein isolate, adding sodium bisulphite and deionized water, heating to 70 ℃ in a water bath, stirring for 3 hours at a speed of 90r/min, centrifuging for 20 minutes at a speed of 8000/min, and freeze-drying to obtain pretreated soybean protein isolate;
taking a certain mass of pretreated soybean protein isolate, adding a certain mass of 2-bromo isobutyryl bromide, 4-dimethylaminopyridine and N, N-dimethylformamide, magnetically stirring for 20 hours at room temperature, then adding a certain mass of glycidyl methacrylate and copper bromide, and stirring for 4 hours at a speed of 90r/min under a nitrogen atmosphere at a temperature of 90 ℃ to obtain modified soybean protein; wherein the mass ratio of the modified soy protein raw materials is soy protein isolate: sodium bisulfite: deionized water = 10:1:20, a step of; pretreatment of isolated soy protein: 2-bromoisobutyryl bromide: 4-dimethylaminopyridine: n, N-dimethylformamide: glycidyl methacrylate: copper bromide = 100:2:1:20:50:1, a step of;
the modified polyurethane is prepared by taking isophorone diisocyanate and 2, 2-dimethylolpropionic acid with certain mass, placing the isophorone diisocyanate and the 2, 2-dimethylolpropionic acid in a reaction kettle, adding dibutyl tin dilaurate with certain mass, stirring for 4 hours at a speed of 120r/min at 80 ℃ under a nitrogen atmosphere, adding a chain extender 1, 4-butanediol with certain mass, continuously stirring for 3 hours, adding a capping agent aminopropyl triethoxysilane with certain mass, and continuously stirring for 0.7 hour; wherein the mass ratio of raw materials in the modified polyurethane is isophorone diisocyanate: 2, 2-bis-hydroxymethyl propionic acid: dibutyl tin dilaurate: 1, 4-butanediol: aminopropyl triethoxysilane = 50:5:1:3:4, a step of;
the curing agent is vinyl triamine;
the preparation method of the plate adhesive comprises the following steps:
step one: taking the mass parts of modified polyamide, adding deionized water with the mass of 0.6 times of the modified polyamide, stirring at the speed of 90r/min for 4min, adding the mass parts of polyisocyanate, and stirring at the speed of 90r/min for 7min to obtain a mixture A;
step two: taking the modified soybean protein and the modified polyurethane in parts by weight, and stirring at a speed of 90r/min for 10min to obtain a mixture B;
step three: and (3) taking the curing agent in parts by weight, adding ethylene glycol with the mass which is 4 times that of the curing agent, uniformly stirring, adding the mixture A obtained in the step (A) and the mixture B obtained in the step (I), and uniformly mixing and stirring to obtain the plate adhesive.
And (3) testing: the performance of the plate adhesives prepared in examples 1 to 3 was tested, wherein the viscosity was tested by reference to the standard GB/T2794-2013 Single Cylinder rotational viscometer method for measuring adhesive viscosity, three-ply boards were produced, the glue strength of the plate adhesives prepared in examples 1 to 3 was tested by reference to the method for testing class II plywood specified in the general plywood of GB/T9846-2015, the plywood size of the three-ply boards was 300X 300mm, the average thickness was 1.7mm, the water content of the veneer was 6% -8%, and the single-sided glue size was 180-220g/m 2 Aging at room temperature for 20min, hot-pressing at 120deg.C under 1MPa for 60s, and standing at room temperature for 3d for detection; testing the water resistance, namely manufacturing the three-ply board, referring to the bonding strength test, soaking the three-ply board after 3d in water for 60 hours, taking out, drying, and testing the bonding strength to represent the water resistance; manufacturing a three-ply board, referring to a bonding strength test, placing a 3d plywood at room temperature, transferring the plywood to an environment with the temperature of 85 ℃ and the humidity of 90%, placing for 1h, testing the bonding strength, and marking the bonding strength as the bonding strength after high temperature so as to represent the high temperature resistance; the wear-resistant performance is that the board adhesive prepared in the embodiment 1-3 with the thickness of 3mm is coated on a board, standard weights with different mass are used for pressing on 80-mesh sand paper on the surface of the board adhesive, the standard weights are pushed at the speed of 1cm/min for 10cm, whether scratches exist on the surface of the board adhesive is observed, the weight mass when the scratches exist is recorded, and the larger weight mass indicates that the better wear-resistant performance of the board adhesive; the results obtained are shown in the table:
as shown in the table, the adhesive for the plates, prepared by the method, has the advantages of lower viscosity than 1000 mPa.s, smaller viscosity, higher fluidity, convenience in sizing, high bonding strength of the plates, strong adhesive property, high bonding strength after soaking for 60 hours, good water resistance, high bonding strength of more than 1MPa after high temperature, good high temperature resistance of the adhesive for the plates, high weight quality when scratches appear, and good wear resistance of the adhesive for the plates.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (8)

1. The plate adhesive is characterized by comprising the following raw materials in parts by weight: 50-80 parts of modified polyamide, 8-15 parts of polyisocyanate, 20-30 parts of modified soybean protein, 20-40 parts of modified polyurethane and 3-5 parts of curing agent;
the preparation method of the plate adhesive comprises the following steps:
step one: taking the mass portion of modified polyamide, adding deionized water with the mass of 0.5-0.8 times of the modified polyamide, stirring for 3-5 min at the speed of 80-100 r/min, adding the mass portion of polyisocyanate, and stirring for 5-10 min at the speed of 80-100 r/min to obtain a mixture A;
step two: taking the modified soybean protein and the modified polyurethane in parts by weight, and stirring at a speed of 80-100 r/min for 5-15 min to obtain a mixture B;
step three: and (3) taking the curing agent in parts by weight, adding ethylene glycol with the mass which is 3-5 times that of the curing agent, uniformly stirring, adding the mixture A obtained in the step (A) and the mixture B obtained in the step (I), and uniformly mixing and stirring to obtain the plate adhesive.
2. A sheet material glue according to claim 1The adhesive is characterized in that the modified polyamide is prepared by taking a certain mass of polyamide epichlorohydrin, adipic acid, diethylenetriamine and distilled water, adding the mixture into a high-pressure reaction kettle, reacting for 10 to 20 hours at a temperature of between 260 and 300 ℃ under the nitrogen atmosphere, taking out and adding a proper amount of H 2 SO 4 Regulating the pH value to 2-3, adding polyvinyl alcohol with a certain mass, and regulating the pH value to 2-3 again to obtain the modified polyamide.
3. The plate adhesive according to claim 2, wherein the modified polyamide comprises the following raw materials in mass ratio: adipic acid: diethylenetriamine: distilled water: polyvinyl alcohol = 10: 8-10: 10 to 15:5:10.
4. the board adhesive of claim 1, wherein the modified soy protein is glycidyl methacrylate grafted soy protein isolate, which is:
taking a certain mass of soybean protein isolate, adding a certain mass of sodium bisulphite and a certain mass of deionized water, heating to 60-80 ℃ in a water bath, stirring for 2-3 hours at a speed of 80-100 r/min, centrifuging for 20min at a speed of 8000/min, and freeze-drying to obtain pretreated soybean protein isolate;
taking a certain mass of pretreated soybean protein isolate, adding a certain mass of 2-bromo isobutyryl bromide, 4-dimethylaminopyridine and N, N-dimethylformamide, magnetically stirring for 20 hours at room temperature, then adding a certain mass of glycidyl methacrylate and copper bromide, and stirring for 3-4 hours at a speed of 80-100 r/min under a nitrogen atmosphere at a temperature of 80-100 ℃ to obtain modified soybean protein.
5. The plate adhesive according to claim 4, wherein the modified soy protein material comprises soy protein isolate: sodium bisulfite: deionized water = 10:1:20, a step of; pretreatment of isolated soy protein: 2-bromoisobutyryl bromide: 4-dimethylaminopyridine: n, N-dimethylformamide: glycidyl methacrylate: copper bromide = 100: 2-3: 1:20:50:1.
6. the board adhesive according to claim 1, wherein: the modified polyurethane is prepared by taking isophorone diisocyanate and 2, 2-dimethylolpropionic acid with certain mass, placing the isophorone diisocyanate and the 2, 2-dimethylolpropionic acid in a reaction kettle, adding dibutyl tin dilaurate with certain mass, stirring for 3-4 hours at a speed of 100-150 r/min at a temperature of 70-90 ℃ in a nitrogen atmosphere, adding a chain extender 1, 4-butanediol with certain mass, continuously stirring for 3-4 hours, adding a blocking agent aminopropyl triethoxysilane with certain mass, and continuously stirring for 0.5-1 hour.
7. The plate adhesive according to claim 6, wherein: the modified polyurethane comprises the following raw materials in percentage by mass: 2, 2-bis-hydroxymethyl propionic acid: dibutyl tin dilaurate: 1, 4-butanediol: aminopropyl triethoxysilane = 50:5:1: 2-3: 3 to 5.
8. The board adhesive according to claim 1, wherein: the curing agent is one of polyetheramine, divinyl triamine, ethylenediamine and vinyl triamine.
CN202310647554.XA 2023-06-02 2023-06-02 Plate adhesive and preparation method thereof Withdrawn CN116536024A (en)

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Application publication date: 20230804