CN116355560B - Environment-friendly adhesive for organic acid-polyol-based formaldehyde-free high-performance plywood, and preparation method and application thereof - Google Patents

Environment-friendly adhesive for organic acid-polyol-based formaldehyde-free high-performance plywood, and preparation method and application thereof Download PDF

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CN116355560B
CN116355560B CN202310144673.3A CN202310144673A CN116355560B CN 116355560 B CN116355560 B CN 116355560B CN 202310144673 A CN202310144673 A CN 202310144673A CN 116355560 B CN116355560 B CN 116355560B
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parts
adhesive
plywood
polyol
organic acid
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CN116355560A (en
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蔡雯倩
赵中元
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Nanjing Forestry University
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Nanjing Forestry University
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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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27D—WORKING VENEER OR PLYWOOD
    • B27D1/00—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring
    • B27D1/04—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring to produce plywood or articles made therefrom; Plywood sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27D—WORKING VENEER OR PLYWOOD
    • B27D1/00—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring
    • B27D1/04—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring to produce plywood or articles made therefrom; Plywood sheets
    • B27D1/08—Manufacture of shaped articles; Presses specially designed therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
    • B32B21/04—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
    • B32B21/14—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood board or veneer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/87—Non-metals or inter-compounds thereof
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Forests & Forestry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention discloses an environment-friendly adhesive for an organic acid-polyol-based formaldehyde-free high-performance plywood, a preparation method and application thereof, belonging to the technical field of adhesives, wherein the adhesive comprises the following components in parts by weight: 150-300 parts of organic acid, 150-300 parts of polyol, 50-150 parts of quaternary composite cross-linking agent, 5-30 parts of ternary composite catalyst and 630-2314.5 parts of water. The hot-pressing temperature of the adhesive is as low as 110 ℃, the hot-pressing rate can be accelerated to 0.5-1mm/min, the problems of high curing temperature and long curing time of the adhesive for the traditional plywood are solved, and the heat-curing rate and the bonding strength of the plywood are improved. Meanwhile, the adhesive solves the problem of overlarge viscosity of the adhesive taking the polyol as the main raw material by adding the cross-linking agent, and the storability of the polyol adhesive is improved.

Description

Environment-friendly adhesive for organic acid-polyol-based formaldehyde-free high-performance plywood, and preparation method and application thereof
Technical Field
The invention relates to an environment-friendly adhesive for an organic acid-polyol-based formaldehyde-free high-performance plywood, a preparation method and application thereof, and belongs to the technical field of adhesives.
Background
Formaldehyde is one of the important problems required to be solved in the current adhesive research, and research of a formaldehyde-free adhesive is an important research method, and most of traditional adhesives are developed around biomass raw materials such as plant proteins, but plant protein-based adhesives have the defects of poor water resistance, small initial adhesion, low adhesive strength, high curing temperature, low curing speed, low hot pressing rate (the reason of the low hot pressing rate is that the heat curing rate of the adhesives is low, namely the reaction time between the raw materials of the adhesives is low), high cost after modification, poor mildew resistance and corrosion resistance and the like. The adhesive produced by taking the polyol as the main raw material can overcome the defects, but the adhesive produced by taking the polyol as the main raw material has the problem of lump glue, and the adhesive can not be stored, so the development of the formaldehyde-free high-performance adhesive which can improve the incapability of storing the polyol adhesive has important significance.
Disclosure of Invention
The invention aims to solve the technical problem of providing an environment-friendly adhesive for organic acid-polyol-based formaldehyde-free high-performance plywood, which utilizes epoxy resin, diphenylmethane diisocyanate and toluene diisocyanate to catalyze esterification reaction between organic acid and polyol, and after the components are added, the hot pressing temperature of the adhesive is as low as 110 ℃, the hot pressing rate can be increased to 0.5-1mm/min, so that the problems of high curing temperature and long curing time of the adhesive for the traditional plywood are solved, and the heat curing rate and the bonding strength of the plywood are improved. Meanwhile, the adhesive improves the problem of lump glue existing in adhesives with polyol as a main raw material by adding the cross-linking agent, and the storability of the polyol adhesive is improved.
Meanwhile, the invention provides a preparation method of the environment-friendly adhesive for the organic acid-polyol-based formaldehyde-free high-performance plywood, which is simple and easy to operate and is suitable for industrial mass production.
Meanwhile, the invention provides application of the environment-friendly adhesive for the organic acid-polyol-based formaldehyde-free high-performance plywood.
In order to solve the technical problems, the invention adopts the following technical scheme:
An environment-friendly adhesive for organic acid-polyol-based formaldehyde-free high-performance plywood comprises the following components in parts by weight: 150-300 parts of organic acid, 150-300 parts of polyol, 50-150 parts of quaternary composite cross-linking agent, 5-30 parts of ternary composite catalyst and 630-2314.5 parts of water; the quaternary composite cross-linking agent is N, N-methylene bisacrylamide, N-dimethylacetamide, divinylbenzene and diisocyanate in a weight ratio of 1:1:1:1; the ternary composite catalyst is epoxy resin, diphenylmethane diisocyanate and toluene diisocyanate in a weight ratio of 2:1:2.
The organic acid comprises citric acid or tartaric acid.
The polyol comprises polyvinyl alcohol or polyethylene glycol.
The water is distilled water.
The solid content of the adhesive is 25-50%, and the viscosity is more than 33625 mPa.s.
The preparation method of the environment-friendly adhesive for the organic acid-polyol-based formaldehyde-free high-performance plywood comprises the following steps:
s01, mixing organic acid, polyalcohol and water, and stirring at a low speed at 80-90 ℃ for reaction for 1-2 hours;
s02, adding a quaternary composite cross-linking agent into the reaction system obtained in the S01, and stirring at a high speed at 100-120 ℃ for reaction for 2-4 hours;
S03, adding a ternary composite catalyst into the reaction system obtained in the step S02, and stirring at a high speed at 50-70 ℃ for reaction for 1-1.5 hours; obtaining the product.
The low-speed stirring is 160-200 r/min, and the high-speed stirring is 420-500 r/min.
The application of the environment-friendly adhesive for preparing the plywood by using the organic acid-polyol-based formaldehyde-free high-performance plywood comprises the following steps of: and (3) coating the adhesive on the veneers, assembling at least 3 layers of veneers based on a vertical texture mode, obtaining the plywood, performing hot press molding, wherein the single-sided sizing amount is 140-220 g/m 2, the hot press temperature is 110 ℃, the pressure is 1-1.5 MPa, and the hot press rate is 0.5-1 mm/min.
A plywood is formed by hot-pressing the adhesive and a veneer.
A plywood with formaldehyde release of 0.002-0.005mg/m 3 and adhesive strength of more than 1.58MPa.
The invention has the following beneficial effects:
The adhesive disclosed by the invention utilizes the esterification reaction between the epoxy resin, the diphenylmethane diisocyanate and the toluene diisocyanate to catalyze the organic acid and the polyalcohol, formaldehyde is not generated in the reaction process of the raw materials used by the adhesive, after the components are added, the hot-pressing temperature of the adhesive is as low as 110 ℃, the hot-pressing rate can be increased to 0.5-1mm/min, the problems of high curing temperature and long curing time of the adhesive for the traditional plywood are solved, and the heat-curing rate and the bonding strength of the plywood are improved. Meanwhile, the adhesive improves the problem of lump glue existing in adhesives with polyol as a main raw material by adding the cross-linking agent, and the storability of the polyol adhesive is improved.
Drawings
FIG. 1 is a storage test diagram of a comparative example;
FIG. 2 is a storage test chart of an embodiment of the present invention.
Detailed Description
The invention will be further described with reference to the accompanying drawings.
Comparative example 1
The environment-friendly adhesive for the formaldehyde-free high-performance organic acid-polyol plywood comprises the following components in parts by weight: 150 parts of tartaric acid, 300 parts of polyethylene glycol, 150 parts of N, N-methylene bisacrylamide, 15 parts of epoxy resin and 750 parts of distilled water.
The preparation process of the adhesive comprises the following steps: the preparation method comprises the steps of weighing corresponding raw material components according to parts by weight, firstly mixing tartaric acid, polyethylene glycol and water, reacting for 1 hour under the low-speed stirring condition of 90 ℃ and 170r/min, then adding N, N-methylene bisacrylamide into a reaction system, reacting for 2 hours under the high-speed stirring condition of 100 ℃ and 450r/min, then adding epoxy resin into the reaction system, and reacting for 1.5 hours under the high-speed stirring condition of 50 ℃ and 450 r/min.
The prepared adhesive has a solid content of 44.85%.
The viscosity number of the prepared adhesive is 15956.431 mPa.s at 25 ℃, and the testing method is a rotational viscometer.
Comparative example 2
The environment-friendly adhesive for the formaldehyde-free high-performance organic acid-polyol plywood comprises the following components in parts by weight: 150 parts of tartaric acid, 150 parts of polyvinyl alcohol, 50 parts of N, N-dimethylacetamide, 10 parts of diphenylmethane diisocyanate and 1080 parts of distilled water.
The preparation process of the adhesive comprises the following steps: the preparation method comprises the steps of weighing corresponding raw material components according to parts by weight, firstly mixing tartaric acid, polyvinyl alcohol and water, reacting for 1 hour at 90 ℃ under 160r/min of low-speed stirring, then adding N, N-dimethylacetamide into a reaction system, reacting for 2 hours at 100 ℃ under 420r/min of high-speed stirring, then adding diphenylmethane diisocyanate into the reaction system, and reacting for 1 hour at 50 ℃ under 420r/min of high-speed stirring.
The prepared adhesive has a solid content of 25%.
The viscosity number of the prepared adhesive is 417.196 mPa.s at 25 ℃, and the testing method is a rotational viscometer.
Comparative example 3
The environment-friendly adhesive for the formaldehyde-free high-performance organic acid-polyol plywood comprises the following components in parts by weight: 150 parts of tartaric acid, 150 parts of polyethylene glycol, 100 parts of N, N-dimethylacetamide, 15.5 parts of diphenylmethane diisocyanate and 864.5 parts of distilled water.
The preparation process of the adhesive comprises the following steps: the preparation method comprises the steps of weighing corresponding raw material components according to parts by weight, firstly mixing tartaric acid, polyethylene glycol and water, reacting for 1.5 hours at 90 ℃ under 180r/min of low-speed stirring, then adding N, N-dimethylacetamide into a reaction system, reacting for 4 hours at 110 ℃ under 470r/min of high-speed stirring, then adding diphenylmethane diisocyanate into the reaction system, and reacting for 1.5 hours at 70 ℃ under 470r/min of high-speed stirring.
The prepared adhesive has a solid content of 35%.
The viscosity number of the prepared adhesive is 2382.424 mPa.s at 25 ℃, and the testing method is a rotational viscometer.
Comparative example 4
The environment-friendly adhesive for the formaldehyde-free high-performance organic acid-polyol plywood comprises the following components in parts by weight: 150 parts of tartaric acid, 300 parts of polyethylene glycol, 150 parts of diisocyanate, 10 parts of epoxy resin, 5 parts of diphenylmethane diisocyanate and 1435 parts of distilled water.
The preparation process of the adhesive comprises the following steps: the preparation method comprises the steps of weighing corresponding raw material components according to parts by weight, firstly mixing tartaric acid, polyethylene glycol and water, reacting for 1 hour under the low-speed stirring condition of 80 ℃ and 160r/min, then adding diisocyanate into a reaction system, reacting for 2 hours under the high-speed stirring condition of 100 ℃ and 450r/min, then adding epoxy resin and diphenylmethane diisocyanate into the reaction system, and reacting for 1 hour under the high-speed stirring condition of 50 ℃ and 450 r/min.
The prepared adhesive has a solid content of 30%.
The viscosity number of the prepared adhesive is 3857.487 mPa.s at 25 ℃, and the testing method is a rotational viscometer.
Comparative example 5
The environment-friendly adhesive for the formaldehyde-free high-performance organic acid-polyol plywood comprises the following components in parts by weight: 150 parts of citric acid, 150 parts of polyethylene glycol, 50 parts of N, N-methylene bisacrylamide, 17.5 parts of toluene diisocyanate and 1102.5 parts of distilled water.
The preparation process of the adhesive comprises the following steps: the preparation method comprises the steps of weighing corresponding raw material components according to parts by weight, firstly mixing citric acid, polyethylene glycol and water, reacting for 2 hours at 90 ℃ under the condition of low-speed stirring at 200r/min, then adding N, N-methylene bisacrylamide into a reaction system, reacting for 3 hours at 110 ℃ under the condition of high-speed stirring at 480r/min, then adding toluene diisocyanate into the reaction system, and reacting for 1.5 hours at 60 ℃ under the condition of high-speed stirring at 480 r/min.
The prepared adhesive has a solid content of 25%.
The viscosity number of the prepared adhesive is 854.859 mPa.s at 25 ℃, and the testing method is a rotational viscometer.
Comparative example 6
The environment-friendly adhesive for the formaldehyde-free high-performance organic acid-polyol plywood comprises the following components in parts by weight: 150 parts of citric acid, 150 parts of polyvinyl alcohol, 150 parts of N, N-dimethylacetamide, 22.5 parts of diphenylmethane diisocyanate and 728.5 parts of distilled water.
The preparation process of the adhesive comprises the following steps: when the adhesive is prepared, citric acid, polyvinyl alcohol and water are mixed, reacted for 1 hour under the low-speed stirring condition of 80 ℃ and 160r/min, then N, N-dimethylacetamide is added into a reaction system, reacted for 2 hours under the high-speed stirring condition of 120 ℃ and 450r/min, and then diphenylmethane diisocyanate is added into the reaction system, and reacted for 1 hour under the high-speed stirring condition of 60 ℃ and 450 r/min.
The solid content of the prepared adhesive is 39.34%.
The viscosity number of the prepared adhesive is 10434.844 mPa.s at 25 ℃, and the testing method is a rotational viscometer.
Comparative example 7
The environment-friendly adhesive for the formaldehyde-free high-performance organic acid-polyol plywood comprises the following components in parts by weight: 150 parts of citric acid, 300 parts of polyethylene glycol, 200 parts of N, N-dimethylacetamide, 10 parts of toluene diisocyanate and 1540 parts of distilled water.
The preparation process of the adhesive comprises the following steps: the preparation method comprises the steps of weighing corresponding raw material components according to parts by weight, firstly mixing citric acid, polyethylene glycol and water, reacting for 2 hours at 90 ℃ under 180r/min low-speed stirring, then adding N, N-dimethylacetamide into a reaction system, reacting for 3 hours at 110 ℃ under 470r/min high-speed stirring, then adding toluene diisocyanate into the reaction system, and reacting for 1 hour at 60 ℃ under 470r/min high-speed stirring.
The prepared adhesive has a solid content of 30%.
The viscosity number of the prepared adhesive is 14562.297 mPa.s at 25 ℃, and the testing method is a rotational viscometer.
Comparative example 8
The environment-friendly adhesive for the formaldehyde-free high-performance organic acid-polyol plywood comprises the following components in parts by weight: 150 parts of citric acid, 150 parts of polyvinyl alcohol, 100 parts of N, N-dimethylacetamide, 50 parts of diisocyanate, 5 parts of diphenylmethane diisocyanate and 1365 parts of distilled water.
The preparation process of the adhesive comprises the following steps: when the adhesive is prepared, citric acid, polyvinyl alcohol and water are mixed, reacted for 1.5 hours at 90 ℃ and 190r/min under low-speed stirring, then N, N-dimethylacetamide and diisocyanate are added into a reaction system, reacted for 3 hours at 100 ℃ and 450r/min under high-speed stirring, and then diphenylmethane diisocyanate is added into the reaction system, and reacted for 1.5 hours at 70 ℃ and 450r/min under high-speed stirring.
The prepared adhesive has a solid content of 25%.
The viscosity number of the prepared adhesive is 2587.579 mPa.s at 25 ℃, and the testing method is a rotational viscometer.
Comparative example 9
The environment-friendly adhesive for the formaldehyde-free high-performance organic acid-polyol plywood comprises the following components in parts by weight: 200 parts of tartaric acid, 150 parts of polyvinyl alcohol, 50 parts of divinylbenzene, 20 parts of toluene diisocyanate and 980 parts of distilled water.
The preparation process of the adhesive comprises the following steps: the preparation method comprises the steps of weighing corresponding raw material components according to parts by weight, firstly mixing tartaric acid, polyvinyl alcohol and water, reacting for 1 hour at 80 ℃ under 160r/min of low-speed stirring, then adding divinylbenzene into a reaction system, reacting for 3 hours at 100 ℃ under 430r/min of high-speed stirring, then adding toluene diisocyanate into the reaction system, and reacting for 1 hour at 60 ℃ under 430r/min of high-speed stirring.
The prepared adhesive has a solid content of 30%.
The viscosity number of the prepared adhesive is 15724.745 mPa.s at 25 ℃, and the testing method is a rotational viscometer.
Comparative example 10
The environment-friendly adhesive for the formaldehyde-free high-performance organic acid-polyol plywood comprises the following components in parts by weight: 200 parts of tartaric acid, 300 parts of polyethylene glycol, 150 parts of divinylbenzene, 28.5 parts of toluene diisocyanate and 1077 parts of distilled water.
The preparation process of the adhesive comprises the following steps: the preparation method comprises the steps of weighing corresponding raw material components according to parts by weight, firstly mixing tartaric acid, polyethylene glycol and water, reacting for 1.5 hours at 90 ℃ under 200r/min low-speed stirring, then adding divinylbenzene into a reaction system, reacting for 2.5 hours at 110 ℃ under 480r/min high-speed stirring, then adding toluene diisocyanate into the reaction system, and reacting for 1.5 hours at 70 ℃ under 480r/min high-speed stirring.
The solid content of the prepared adhesive is 38.65%.
The viscosity number of the prepared adhesive is 15251.793 mPa.s at 25 ℃, and the testing method is a rotational viscometer.
Comparative example 11
The environment-friendly adhesive for the formaldehyde-free high-performance organic acid-polyol plywood comprises the following components in parts by weight: 200 parts of tartaric acid, 150 parts of polyvinyl alcohol, 50 parts of N, N-dimethylacetamide, 50 parts of diisocyanate, 22.5 parts of epoxy resin and 877.5 parts of distilled water.
The preparation process of the adhesive comprises the following steps: the preparation method comprises the steps of weighing corresponding raw material components according to parts by weight, firstly mixing tartaric acid, polyvinyl alcohol and water, reacting for 1 hour under the condition of low-speed stirring at 80 ℃ and 200r/min, then adding N, N-methylene bisacrylamide into a reaction system, reacting for 3 hours under the condition of high-speed stirring at 110 ℃ and 460r/min, then adding N, N-dimethylacetamide and diisocyanate into the reaction system, and reacting for 1.5 hours under the condition of high-speed stirring at 60 ℃ and 460 r/min.
The prepared adhesive has a solid content of 35%.
The viscosity number of the prepared adhesive is 14653.432 mPa.s at 25 ℃, and the testing method is a rotational viscometer.
Comparative example 12
The environment-friendly adhesive for the formaldehyde-free high-performance organic acid-polyol plywood comprises the following components in parts by weight: 200 parts of citric acid, 150 parts of polyethylene glycol, 150 parts of diisocyanate, 15 parts of epoxy resin and 630 parts of distilled water.
The preparation process of the adhesive comprises the following steps: when the adhesive is prepared, citric acid, polyethylene glycol and water are mixed, reacted for 1 hour under the low-speed stirring condition of 90 ℃ and 180r/min, diisocyanate is added into a reaction system, reacted for 2.5 hours under the high-speed stirring condition of 100 ℃ and 450r/min, and epoxy resin is added into the reaction system, and reacted for 1 hour under the high-speed stirring condition of 50 ℃ and 450 r/min.
The solid content of the prepared adhesive is 44.98%.
The viscosity number of the prepared adhesive is 19624.596 mPa.s at 25 ℃, and the testing method is a rotational viscometer.
Comparative example 13
The environment-friendly adhesive for the formaldehyde-free high-performance organic acid-polyol plywood comprises the following components in parts by weight: 200 parts of citric acid, 300 parts of polyvinyl alcohol, 50 parts of N, N-methylene bisacrylamide, 50 parts of divinylbenzene, 12.5 parts of epoxy resin and 1837.5 parts of distilled water.
The preparation process of the adhesive comprises the following steps: when the adhesive is prepared, citric acid, polyvinyl alcohol and water are mixed, reacted for 1.5 hours at 90 ℃ and under the condition of low-speed stirring at 170r/min, then N, N-methylene bisacrylamide and divinylbenzene are added into a reaction system, reacted for 3 hours at 100 ℃ and under the condition of high-speed stirring at 480r/min, and then epoxy resin is added into the reaction system, and reacted for 1 hour at 60 ℃ and under the condition of high-speed stirring at 480 r/min.
The prepared adhesive has a solid content of 25%.
The viscosity number of the prepared adhesive is 356.487 mPa.s at 25 ℃, and the testing method is a rotational viscometer.
Comparative example 14
The environment-friendly adhesive for the formaldehyde-free high-performance organic acid-polyol plywood comprises the following components in parts by weight: 300 parts of tartaric acid, 200 parts of polyethylene glycol, 150 parts of diisocyanate, 22.5 parts of epoxy resin and 1248 parts of distilled water.
The preparation process of the adhesive comprises the following steps: the preparation method comprises the steps of weighing corresponding raw material components according to parts by weight, firstly mixing tartaric acid, polyethylene glycol and water, reacting for 1 hour under the low-speed stirring condition of 90 ℃ and 180r/min, then adding diisocyanate into a reaction system, reacting for 2 hours under the high-speed stirring condition of 100 ℃ and 450r/min, then adding epoxy resin into the reaction system, and reacting for 0.5 hour under the high-speed stirring condition of 50 ℃ and 450 r/min.
The prepared adhesive has a solid content of 35%.
The viscosity number of the prepared adhesive is 23089.531 mPa.s at 25 ℃, and the testing method is a rotational viscometer.
Comparative example 15
The environment-friendly adhesive for the formaldehyde-free high-performance organic acid-polyol plywood comprises the following components in parts by weight: 300 parts of tartaric acid, 150 parts of polyvinyl alcohol, 100 parts of N, N-methylene bisacrylamide, 7.5 parts of diphenylmethane diisocyanate and 1300 parts of distilled water.
The preparation process of the adhesive comprises the following steps: the preparation method comprises the steps of weighing corresponding raw material components according to parts by weight, firstly mixing tartaric acid, polyvinyl alcohol and water, reacting for 2 hours at 90 ℃ under 200r/min low-speed stirring, then adding N, N-methylene bisacrylamide into a reaction system, reacting for 4 hours at 100 ℃ under 500r/min high-speed stirring, then adding diphenylmethane diisocyanate into the reaction system, and reacting for 1.5 hours at 50 ℃ under 500r/min high-speed stirring.
The prepared adhesive has a solid content of 30%.
The viscosity number of the prepared adhesive is 6692.796 mPa.s at 25 ℃, and the testing method is a rotational viscometer.
Comparative example 16
The environment-friendly adhesive for the formaldehyde-free high-performance organic acid-polyol plywood comprises the following components in parts by weight: 300 parts of tartaric acid, 200 parts of polyethylene glycol, 25 parts of N, N-methylene bisacrylamide, 25 parts of divinylbenzene, 10 parts of toluene diisocyanate and 840 parts of distilled water.
The preparation process of the adhesive comprises the following steps: the preparation method comprises the steps of weighing corresponding raw material components according to parts by weight, firstly mixing tartaric acid, polyethylene glycol and water, reacting for 1 hour under the condition of low-speed stirring at 80 ℃ and 180r/min, then adding N, N-methylene bisacrylamide and divinylbenzene into a reaction system, reacting for 2.5 hours under the condition of high-speed stirring at 100 ℃ and 480r/min, then adding toluene diisocyanate into the reaction system, and reacting for 1.5 hours under the condition of high-speed stirring at 50 ℃ and 480 r/min.
The prepared adhesive has a solid content of 40%.
The viscosity number of the prepared adhesive is 13121.333 mPa.s at 25 ℃, and the testing method is a rotational viscometer.
Comparative example 17
The environment-friendly adhesive for the formaldehyde-free high-performance organic acid-polyol plywood comprises the following components in parts by weight: 300 parts of tartaric acid, 150 parts of polyethylene glycol, 100 parts of N, N-dimethylacetamide, 2.5 parts of diphenylmethane diisocyanate, 17.5 parts of toluene diisocyanate and 855 parts of distilled water.
The preparation process of the adhesive comprises the following steps: the preparation method comprises the steps of weighing corresponding raw material components according to parts by weight, firstly mixing tartaric acid, polyethylene glycol and water, reacting for 1 hour at 90 ℃ under the condition of low-speed stirring at 200r/min, then adding N, N-dimethylacetamide into a reaction system, reacting for 4 hours at 100 ℃ under the condition of high-speed stirring at 450r/min, then adding diphenylmethane diisocyanate and toluene diisocyanate into the reaction system, and reacting for 1.5 hours at 50 ℃ under the condition of high-speed stirring at 450 r/min.
The prepared adhesive has a solid content of 30%.
The viscosity number of the prepared adhesive is 8562.285 mPa.s at 25 ℃, and the testing method is a rotational viscometer.
Comparative example 18
The environment-friendly adhesive for the formaldehyde-free high-performance organic acid-polyol plywood comprises the following components in parts by weight: 300 parts of citric acid, 200 parts of polyethylene glycol, 300 parts of divinylbenzene, 30 parts of epoxy resin and 1245 parts of distilled water.
The preparation process of the adhesive comprises the following steps: the preparation method comprises the steps of weighing corresponding raw material components according to parts by weight, firstly mixing citric acid, polyethylene glycol and water, reacting for 2 hours at 80 ℃ under the condition of low-speed stirring at 180r/min, then adding divinylbenzene into a reaction system, reacting for 4 hours at 110 ℃ under the condition of high-speed stirring at 450r/min, then adding epoxy resin into the reaction system, and reacting for 1.5 hours at 50 ℃ under the condition of high-speed stirring at 450 r/min.
The prepared adhesive has a solid content of 40%.
The viscosity number of the prepared adhesive is 13104.102 mPa.s at 25 ℃, and the testing method is a rotational viscometer.
Comparative example 19
The environment-friendly adhesive for the formaldehyde-free high-performance organic acid-polyol plywood comprises the following components in parts by weight: 300 parts of citric acid, 150 parts of polyvinyl alcohol, 300 parts of divinylbenzene, 21.5 parts of epoxy resin and 2314.5 parts of distilled water.
The preparation process of the adhesive comprises the following steps: when the adhesive is prepared, citric acid, polyvinyl alcohol and water are mixed, reacted for 1 hour under the low-speed stirring condition of 90 ℃ and 160r/min, divinylbenzene is added into a reaction system, reacted for 2 hours under the high-speed stirring condition of 120 ℃ and 450r/min, epoxy resin is added into the reaction system, and reacted for 1 hour under the high-speed stirring condition of 50 ℃ and 450 r/min.
The prepared adhesive has a solid content of 25%.
The viscosity number of the prepared adhesive is 6899.531 mPa.s at 25 ℃, and the testing method is a rotational viscometer.
Comparative example 20
The environment-friendly adhesive for the formaldehyde-free high-performance organic acid-polyol plywood comprises the following components in parts by weight: 300 parts of citric acid, 300 parts of polyvinyl alcohol, 150 parts of N, N-methylene bisacrylamide, 7.5 parts of diphenylmethane diisocyanate and 1138.5 parts of distilled water.
The preparation process of the adhesive comprises the following steps: when the adhesive is prepared, citric acid, polyvinyl alcohol and water are mixed, reacted for 2 hours at 90 ℃ under 200r/min low-speed stirring, then N, N-methylene bisacrylamide is added into a reaction system, reacted for 3 hours at 110 ℃ under 500r/min high-speed stirring, and then diphenylmethane diisocyanate is added into the reaction system, and reacted for 1 hour at 50 ℃ under 500r/min high-speed stirring.
The prepared adhesive has a solid content of 39.95%.
The viscosity number of the prepared adhesive is 12464.398 mPa.s at 25 ℃, and the testing method is a rotational viscometer.
Comparative example 21
The environment-friendly adhesive for the formaldehyde-free high-performance organic acid-polyol plywood comprises the following components in parts by weight: 300 parts of citric acid, 150 parts of polyethylene glycol, 50 parts of N, N-methylene bisacrylamide, 22.5 parts of epoxy resin, 7.5 parts of toluene diisocyanate and 795 parts of distilled water.
The preparation process of the adhesive comprises the following steps: the preparation method comprises the steps of weighing corresponding raw material components according to parts by weight, firstly mixing citric acid, polyethylene glycol and water, reacting for 1 hour under the low-speed stirring condition of 80 ℃ and 180r/min, then adding N, N-methylene bisacrylamide into a reaction system, reacting for 2 hours under the high-speed stirring condition of 110 ℃ and 500r/min, then adding epoxy resin and toluene diisocyanate into the reaction system, and reacting for 1.5 hours under the high-speed stirring condition of 50 ℃ and 500 r/min.
The prepared adhesive has a solid content of 40%.
The viscosity number of the prepared adhesive is 8586.787 mPa.s at 25 ℃, and the testing method is a rotational viscometer.
Comparative example 22
The environment-friendly adhesive for the formaldehyde-free high-performance organic acid-polyol plywood comprises the following components in parts by weight: 300 parts of citric acid, 150 parts of polyethylene glycol, 50 parts of N, N-methylene bisacrylamide, 12 parts of epoxy resin, 6 parts of diphenylmethane diisocyanate, 12 parts of toluene diisocyanate and 795 parts of distilled water.
The preparation process of the adhesive comprises the following steps: the preparation method comprises the steps of weighing corresponding raw material components according to parts by weight, firstly mixing citric acid, polyethylene glycol and water, reacting for 1 hour under the low-speed stirring condition of 80 ℃ and 180r/min, then adding N, N-methylene bisacrylamide into a reaction system, reacting for 2 hours under the high-speed stirring condition of 110 ℃ and 500r/min, then adding epoxy resin, diphenylmethane diisocyanate and toluene diisocyanate into the reaction system, and reacting for 1.5 hours under the high-speed stirring condition of 50 ℃ and 500 r/min.
The prepared adhesive has a solid content of 42%.
The viscosity number of the prepared adhesive is 13245 mPa.s at 25 ℃, and the testing method is a rotational viscometer.
Comparative example 23
The environment-friendly adhesive for the formaldehyde-free high-performance organic acid-polyol plywood comprises the following components in parts by weight: 300 parts of citric acid, 150 parts of polyethylene glycol, 25 parts of N, N-methylene bisacrylamide, 25 parts of N, N-dimethylacetamide, 12 parts of epoxy resin, 6 parts of diphenylmethane diisocyanate, 12 parts of toluene diisocyanate and 795 parts of distilled water.
The preparation process of the adhesive comprises the following steps: the preparation method comprises the steps of weighing corresponding raw material components according to parts by weight, firstly mixing citric acid, polyethylene glycol and water, reacting for 1 hour under the low-speed stirring condition of 80 ℃ and 180r/min, then adding N, N-methylene bisacrylamide and N, N-dimethylacetamide into a reaction system, reacting for 2 hours under the high-speed stirring condition of 110 ℃ and 500r/min, then adding epoxy resin, diphenylmethane diisocyanate and toluene diisocyanate into the reaction system, and reacting for 1.5 hours under the high-speed stirring condition of 50 ℃ and 500 r/min.
The prepared adhesive has a solid content of 31%.
The viscosity number of the prepared adhesive is 5402.83 mPa.s at 25 ℃, and the testing method is a rotational viscometer.
Comparative example 24
The environment-friendly adhesive for the formaldehyde-free high-performance organic acid-polyol plywood comprises the following components in parts by weight: 300 parts of citric acid, 150 parts of polyethylene glycol, 17 parts of N, N-methylene bisacrylamide, 17 parts of N, N-dimethylacetamide, 17 parts of divinylbenzene, 12 parts of epoxy resin, 6 parts of diphenylmethane diisocyanate, 12 parts of toluene diisocyanate and 795 parts of distilled water.
The preparation process of the adhesive comprises the following steps: the preparation method comprises the steps of weighing corresponding raw material components according to parts by weight, firstly mixing citric acid, polyethylene glycol and water, reacting for 1 hour under the low-speed stirring condition of 80 ℃ and 180r/min, then adding N, N-methylene bisacrylamide, N-dimethylacetamide and divinylbenzene into a reaction system, reacting for 2 hours under the high-speed stirring condition of 110 ℃ and 500r/min, and then adding epoxy resin, diphenylmethane diisocyanate and toluene diisocyanate into the reaction system, and reacting for 1.5 hours under the high-speed stirring condition of 50 ℃ and 500 r/min.
The prepared adhesive has a solid content of 44%.
The viscosity number of the prepared adhesive is 21148.25 mPa.s at 25 ℃, and the testing method is a rotational viscometer.
Comparative example 25
The environment-friendly adhesive for the formaldehyde-free high-performance organic acid-polyol plywood comprises the following components in parts by weight: 300 parts of citric acid, 150 parts of polyethylene glycol, 20 parts of N, N-methylene bisacrylamide, 10 parts of N, N-dimethylacetamide, 10 parts of divinylbenzene, 10 parts of diisocyanate, 12 parts of epoxy resin, 6 parts of diphenylmethane diisocyanate, 12 parts of toluene diisocyanate and 795 parts of distilled water.
The preparation process of the adhesive comprises the following steps: the preparation method comprises the steps of weighing corresponding raw material components according to parts by weight, firstly mixing citric acid, polyethylene glycol and water, reacting for 1 hour under the low-speed stirring condition of 80 ℃ and 180r/min, then adding N, N-methylene bisacrylamide, N-dimethylacetamide, divinylbenzene and diisocyanate into a reaction system, reacting for 2 hours under the high-speed stirring condition of 110 ℃ and 500r/min, then adding epoxy resin, diphenylmethane diisocyanate and toluene diisocyanate into the reaction system, and reacting for 1.5 hours under the high-speed stirring condition of 50 ℃ and 500 r/min.
The prepared adhesive has a solid content of 42%.
The viscosity number of the prepared adhesive is 18045.19 mPa.s at 25 ℃, and the testing method is a rotational viscometer.
Comparative example 26
The environment-friendly adhesive for the formaldehyde-free high-performance organic acid-polyol plywood comprises the following components in parts by weight: 300 parts of citric acid, 150 parts of polyethylene glycol, 12.5 parts of N, N-methylene bisacrylamide, 12.5 parts of N, N-dimethylacetamide, 12.5 parts of divinylbenzene, 12.5 parts of diisocyanate, 30 parts of epoxy resin and 795 parts of distilled water.
The preparation process of the adhesive comprises the following steps: the preparation method comprises the steps of weighing corresponding raw material components according to parts by weight, firstly mixing citric acid, polyethylene glycol and water, reacting for 1 hour under the low-speed stirring condition of 80 ℃ and 180r/min, then adding N, N-methylenebisacrylamide, N-dimethylacetamide, divinylbenzene and diisocyanate into a reaction system, reacting for 2 hours under the high-speed stirring condition of 110 ℃ and 500r/min, then adding epoxy resin into the reaction system, and reacting for 1.5 hours under the high-speed stirring condition of 50 ℃ and 500 r/min.
The prepared adhesive has a solid content of 40%.
The viscosity number of the prepared adhesive is 8732.16 mPa.s at 25 ℃, and the testing method is a rotational viscometer.
Comparative example 27
The environment-friendly adhesive for the formaldehyde-free high-performance organic acid-polyol plywood comprises the following components in parts by weight: 300 parts of citric acid, 150 parts of polyethylene glycol, 12.5 parts of N, N-methylene bisacrylamide, 12.5 parts of N, N-dimethylacetamide, 12.5 parts of divinylbenzene, 12.5 parts of diisocyanate, 20 parts of epoxy resin, 10 parts of diphenylmethane diisocyanate and 795 parts of distilled water.
The preparation process of the adhesive comprises the following steps: the preparation method comprises the steps of weighing corresponding raw material components according to parts by weight, firstly mixing citric acid, polyethylene glycol and water, reacting for 1 hour under the low-speed stirring condition of 80 ℃ and 180r/min, then adding N, N-methylene bisacrylamide, N-dimethylacetamide, divinylbenzene and diisocyanate into a reaction system, reacting for 2 hours under the high-speed stirring condition of 110 ℃ and 500r/min, then adding epoxy resin and diphenylmethane diisocyanate into the reaction system, and reacting for 1.5 hours under the high-speed stirring condition of 50 ℃ and 500 r/min.
The prepared adhesive has a solid content of 40%.
The viscosity number of the prepared adhesive is 8815.36 mPa.s at 25 ℃, and the testing method is a rotational viscometer.
Comparative example 28
The environment-friendly adhesive for the formaldehyde-free high-performance organic acid-polyol plywood comprises the following components in parts by weight: 300 parts of citric acid, 150 parts of polyethylene glycol, 12.5 parts of N, N-methylene bisacrylamide, 12.5 parts of N, N-dimethylacetamide, 12.5 parts of divinylbenzene, 12.5 parts of diisocyanate, 15 parts of epoxy resin, 5 parts of diphenylmethane diisocyanate, 10 parts of toluene diisocyanate and 795 parts of distilled water.
The preparation process of the adhesive comprises the following steps: the preparation method comprises the steps of weighing corresponding raw material components according to parts by weight, firstly mixing citric acid, polyethylene glycol and water, reacting for 1 hour under the low-speed stirring condition of 80 ℃ and 180r/min, then adding N, N-methylene bisacrylamide, N-dimethylacetamide, divinylbenzene and diisocyanate into a reaction system, reacting for 2 hours under the high-speed stirring condition of 110 ℃ and 500r/min, then adding epoxy resin, diphenylmethane diisocyanate and toluene diisocyanate into the reaction system, and reacting for 1.5 hours under the high-speed stirring condition of 50 ℃ and 500 r/min.
The prepared adhesive has a solid content of 43%.
The viscosity number of the prepared adhesive is 9417.25 mPa.s at 25 ℃, and the testing method is a rotational viscometer.
Comparative example 29
The environment-friendly adhesive for the formaldehyde-free high-performance organic acid-polyol plywood comprises the following components in parts by weight: 300 parts of citric acid, 150 parts of polyethylene glycol, 12.5 parts of N, N-methylene bisacrylamide, 12.5 parts of N, N-dimethylacetamide, 12.5 parts of divinylbenzene, 12.5 parts of diisocyanate, 10 parts of epoxy resin, 5 parts of diphenylmethane diisocyanate, 15 parts of toluene diisocyanate and 795 parts of distilled water.
The preparation process of the adhesive comprises the following steps: the preparation method comprises the steps of weighing corresponding raw material components according to parts by weight, firstly mixing citric acid, polyethylene glycol and water, reacting for 1 hour under the low-speed stirring condition of 80 ℃ and 180r/min, then adding N, N-methylene bisacrylamide, N-dimethylacetamide, divinylbenzene and diisocyanate into a reaction system, reacting for 2 hours under the high-speed stirring condition of 110 ℃ and 500r/min, then adding epoxy resin, diphenylmethane diisocyanate and toluene diisocyanate into the reaction system, and reacting for 1.5 hours under the high-speed stirring condition of 50 ℃ and 500 r/min.
The prepared adhesive has a solid content of 40%.
The viscosity number of the prepared adhesive is 8147.20 mPa.s at 25 ℃, and the testing method is a rotational viscometer.
After the adhesives obtained in comparative examples 1 to 29 were stored for one week, the adhesive was lump-adhered, and the storage method was as follows: sealing and storing in clean wide-mouth plastic bottle for one week. As shown in fig. 1, in the case of comparative example 29, the adhesive of comparative example 29 showed a significant blocking phenomenon.
Example 1
The environment-friendly adhesive for the formaldehyde-free high-performance organic acid-polyol plywood comprises the following components in parts by weight: 150 parts of citric acid, 300 parts of polyvinyl alcohol, 37.5 parts of N, N-methylene bisacrylamide, 37.5 parts of N, N-dimethylacetamide, 37.5 parts of divinylbenzene, 37.5 parts of diisocyanate, 10.2 parts of epoxy resin, 5.1 parts of diphenylmethane diisocyanate, 10.2 parts of toluene diisocyanate and 1162 parts of distilled water.
The preparation process of the adhesive comprises the following steps: the preparation method comprises the steps of weighing corresponding raw material components according to parts by weight, firstly mixing citric acid, polyvinyl alcohol and water, reacting for 1.5 hours at the temperature of 80 ℃ under the condition of 160r/min low-speed stirring, then adding N, N-methylene bisacrylamide, N, N-dimethylacetamide, divinylbenzene and diisocyanate into a reaction system, reacting for 3 hours at the temperature of 100 ℃ under the condition of 430r/min high-speed stirring, and then adding epoxy resin, diphenylmethane diisocyanate and toluene diisocyanate into the reaction system, and reacting for 1.5 hours at the temperature of 60 ℃ under the condition of 430r/min high-speed stirring.
The prepared adhesive has a solid content of 34.99%.
The viscosity number of the prepared adhesive at 25 ℃ is 33625 mPa.s, and the test method is a rotational viscometer.
Example 2
The environment-friendly adhesive for the formaldehyde-free high-performance organic acid-polyol plywood comprises the following components in parts by weight: 300 parts of citric acid, 150 parts of polyethylene glycol, 12.5 parts of N, N-methylene bisacrylamide, 12.5 parts of N, N-dimethylacetamide, 12.5 parts of divinylbenzene, 12.5 parts of diisocyanate, 12 parts of epoxy resin, 6 parts of diphenylmethane diisocyanate, 12 parts of toluene diisocyanate and 795 parts of distilled water.
The preparation process of the adhesive comprises the following steps: the preparation method comprises the steps of weighing corresponding raw material components according to parts by weight, firstly mixing citric acid, polyethylene glycol and water, reacting for 1 hour under the low-speed stirring condition of 80 ℃ and 180r/min, then adding N, N-methylene bisacrylamide, N-dimethylacetamide, divinylbenzene and diisocyanate into a reaction system, reacting for 2 hours under the high-speed stirring condition of 110 ℃ and 500r/min, then adding epoxy resin, diphenylmethane diisocyanate and toluene diisocyanate into the reaction system, and reacting for 1.5 hours under the high-speed stirring condition of 50 ℃ and 500 r/min.
The prepared adhesive has a solid content of 48%.
The prepared adhesive has a viscosity value of (citric acid, polyvinyl alcohol are taken as an example) combined linear molecule crosslinking at 25 ℃ to form a low molecular weight prepolymer; in the curing process, a ternary composite catalyst is utilized, so that the reaction time is reduced; the viscosity of the adhesive is more than 33625 mPa.s, and the solid content is 25-50%. The invention develops a novel formaldehyde-free adhesive, the bonding system improves the formaldehyde hazard caused by the traditional aldehyde-based adhesive to human bodies, overcomes the defects of long curing time and high curing temperature of the formaldehyde-free adhesive, simultaneously solves the problem that the polyol adhesive cannot be stored by adding the cross-linking agent, and can better match the production process of the existing artificial board. s, the test method is a rotary viscometer.
Example 3
The environment-friendly adhesive for the formaldehyde-free high-performance organic acid-polyol plywood comprises the following components in parts by weight: 300 parts of tartaric acid, 150 parts of polyvinyl alcohol, 25 parts of N, N-methylene bisacrylamide, 25 parts of N, N-dimethylacetamide, 25 parts of divinylbenzene, 25 parts of diisocyanate, 2 parts of epoxy resin, 1 part of diphenylmethane diisocyanate, 2 parts of toluene diisocyanate and 2314.5 parts of distilled water.
The preparation process of the adhesive comprises the following steps: the preparation method comprises the steps of weighing corresponding raw material components according to parts by weight, firstly mixing citric acid, polyvinyl alcohol and water, reacting for 2 hours at 90 ℃ under the condition of low-speed stirring at 200r/min, then adding N, N-methylene bisacrylamide, N-dimethylacetamide, divinylbenzene and diisocyanate into a reaction system, reacting for 4 hours at 120 ℃ under the condition of high-speed stirring at 420r/min, and then adding epoxy resin, diphenylmethane diisocyanate and toluene diisocyanate into the reaction system, and reacting for 1 hour at 70 ℃ under the condition of high-speed stirring at 500 r/min.
The prepared adhesive has a solid content of 25%.
The viscosity number of the prepared adhesive at 25 ℃ is 35401 mPa.s, and the test method is a rotational viscometer.
Example 4
The environment-friendly adhesive for the formaldehyde-free high-performance organic acid-polyol plywood comprises the following components in parts by weight: 200 parts of tartaric acid, 200 parts of polyethylene glycol, 20 parts of N, N-methylenebisacrylamide, 20 parts of N, N-dimethylacetamide, 20 parts of divinylbenzene, 20 parts of diisocyanate, 6 parts of epoxy resin, 3 parts of diphenylmethane diisocyanate, 6 parts of toluene diisocyanate and 630 parts of distilled water.
The preparation process of the adhesive comprises the following steps: the preparation method comprises the steps of weighing corresponding raw material components according to parts by weight, firstly mixing tartaric acid, polyethylene glycol and water, reacting for 2 hours at a low rotation speed of 85 ℃ and 190r/min under stirring, then adding N, N-methylenebisacrylamide, N-dimethylacetamide, divinylbenzene and diisocyanate into a reaction system, reacting for 3 hours at a high speed of 110 ℃ and 450r/min under stirring, then adding epoxy resin, diphenylmethane diisocyanate and toluene diisocyanate into the reaction system, and reacting for 1.2 hours at a high speed of 60 ℃ and 480r/min under stirring.
The prepared adhesive has a solid content of 50%.
The viscosity number of the prepared adhesive at 25 ℃ is 36187 mPa.s, and the test method is a rotational viscometer.
As shown in fig. 2, the adhesives obtained in examples 1 to 4 were not lump-adhered after being stored for one week, so as to solve the problem that the polyol adhesives could not be stored. The storage method comprises the following steps: sealing and storing in clean wide-mouth plastic bottle for one week. As shown in fig. 2, taking example 1 as an example, the adhesive of example 1 does not stick together, and the storability of the polyol adhesive is increased.
Example 5
And (3) preparing a plywood: according to GB/T9846.7-2004 standard hot pressing, preparing eucalyptus plywood, wherein the technological parameters of the pressing plate are as follows: the sizes of test pieces are 300mm multiplied by 9mm, the adhesives obtained in the comparative examples 1 to 29 and the examples 1 to 4 are uniformly coated on eucalyptus veneers by adopting a manual brushing mode, 3 layers of veneers are assembled based on a vertical texture mode, the single-sided sizing amount is 140g/m 2, the hot pressing temperature is 110 ℃, the pressure is 1.5MPa, and the hot pressing rate is 0.5mm/min. The resulting plywood was subjected to the following performance test, respectively.
Performance testing and characterization
The eucalyptus plywood prepared by the adhesive disclosed by the invention has the relevant performance tested according to the class II plywood bonding strength test method specified in GB/T9846-2015. The bonding strength of the product meets the relevant standards of the national class II plywood, and the performance test results of eucalyptus plywood prepared by the adhesives of comparative examples and examples are shown in table 1.
Table 1 performance table of eucalyptus plywood
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Example 6
And (3) preparing a plywood: according to GB/T9846.7-2004 standard hot pressing, preparing eucalyptus plywood, wherein the technological parameters of the pressing plate are as follows: the test piece size is 300mm multiplied by 9mm, the adhesive prepared in the example 1 is uniformly coated on eucalyptus veneers by adopting a manual brushing mode, 3 layers of veneers are assembled based on a vertical texture mode, the single-sided sizing amount is 220g/m 2, the hot pressing temperature is 110 ℃, the pressure is 1MPa, and the hot pressing rate is 0.6mm/min.
Example 7
And (3) preparing a plywood: according to GB/T9846.7-2004 standard hot pressing, preparing eucalyptus plywood, wherein the technological parameters of the pressing plate are as follows: the test piece size is 300mm multiplied by 9mm, the adhesive prepared in the example 1 is uniformly coated on eucalyptus veneers by adopting a manual brushing mode, 5 layers of veneers are assembled based on a vertical texture mode, the single-sided sizing amount is 160g/m 2, the hot pressing temperature is 110 ℃, the pressure is 1.2MPa, and the hot pressing rate is 0.6mm/min.
Example 7
And (3) preparing a plywood: according to GB/T9846.7-2004 standard hot pressing, preparing eucalyptus plywood, wherein the technological parameters of the pressing plate are as follows: the test piece size is 300mm multiplied by 9mm, the adhesive prepared in the example 1 is uniformly coated on eucalyptus veneers by adopting a manual brushing mode, 7 layers of veneers are assembled based on a vertical texture mode, the single-sided sizing amount is 180g/m 2, the hot pressing temperature is 110 ℃, the pressure is 1.5MPa, and the hot pressing rate is 1mm/min.
The crosslinking effect of the quaternary composite crosslinking agent of the invention crosslinks linear molecules combined by citric acid and polyvinyl alcohol (taking citric acid and polyvinyl alcohol as examples) to form a low molecular weight prepolymer; in the curing process, a ternary composite catalyst is utilized, so that the reaction time is reduced; the viscosity of the adhesive is more than 33625 mPa.s, and the solid content is 25-50%. The invention develops a novel formaldehyde-free adhesive, the bonding system improves the formaldehyde hazard caused by the traditional aldehyde-based adhesive to human bodies, overcomes the defects of long curing time and high curing temperature of the formaldehyde-free adhesive, simultaneously solves the problem that the polyol adhesive cannot be stored by adding the cross-linking agent, and can better match the production process of the existing artificial board.
In the invention, the eucalyptus veneer raw material of the plywood contains a certain amount of free formaldehyde, the adhesive does not contain formaldehyde, the formaldehyde release amount of the plywood is 0.002-0.005mg/m 3, and the invention meets the formaldehyde release amount grading requirements of ENF-grade indoor artificial boards and products thereof.
The low molecular weight prepolymer formed from organic acid, polyol and isocyanate groups has the structural formula:
In the above formula, the middle The radical being a polyol, left/>Radical organic acid, right/>The group is an isocyanate group.
The foregoing is only a preferred embodiment of the invention, it being noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the invention.

Claims (10)

1. The environment-friendly adhesive for the organic acid-polyol-based formaldehyde-free high-performance plywood is characterized by comprising the following components in parts by weight: 150-300 parts of organic acid, 150-300 parts of polyol, 50-150 parts of quaternary composite cross-linking agent, 5-30 parts of ternary composite catalyst and 630-2314.5 parts of water; the quaternary composite cross-linking agent is N, N-methylene bisacrylamide, N-dimethylacetamide, divinylbenzene and diisocyanate in a weight ratio of 1:1:1:1; the ternary composite catalyst is epoxy resin, diphenylmethane diisocyanate and toluene diisocyanate in a weight ratio of 2:1:2.
2. The environment-friendly adhesive for organic acid-polyol-based formaldehyde-free high-performance plywood according to claim 1, wherein the organic acid comprises citric acid or tartaric acid.
3. The environmentally friendly adhesive for organic acid-polyol-based formaldehyde-free high performance plywood according to claim 1, wherein the polyol comprises polyvinyl alcohol or polyethylene glycol.
4. The environment-friendly adhesive for organic acid-polyol-based formaldehyde-free high-performance plywood as claimed in claim 1, wherein the water is distilled water.
5. The environment-friendly adhesive for organic acid-polyol-based formaldehyde-free high-performance plywood, according to claim 1, wherein the solid content of the adhesive is 25-50%, and the viscosity is more than 33625 mPa.s.
6. The preparation method of the environment-friendly adhesive for the organic acid-polyol-based formaldehyde-free high-performance plywood, which is disclosed in any one of claims 1 to 5, is characterized by comprising the following steps:
S01, mixing organic acid, polyalcohol and water, and stirring at a low speed at 80-90 ℃ for reaction for 1-2 hours;
S02, adding a quaternary composite cross-linking agent into the reaction system obtained in the S01, and stirring at a high speed at 100-120 ℃ for reacting for 2-4 hours;
S03, adding a ternary composite catalyst into the reaction system obtained in the step S02, and stirring at a high speed at 50-70 ℃ for reaction for 1-1.5 hours; obtaining the product.
7. The method for preparing the environment-friendly adhesive for the organic acid-polyol-based formaldehyde-free high-performance plywood, which is characterized in that the low-speed stirring is 160-200 r/min, and the high-speed stirring is 420-500 r/min.
8. The application of the environment-friendly adhesive for organic acid-polyol-based formaldehyde-free high-performance plywood as claimed in any one of claims 1 to 5 in the preparation of plywood, wherein the step of preparing plywood comprises the following steps: and (3) coating the adhesive on the veneers, assembling at least 3 layers of veneers based on a vertical texture mode, obtaining the plywood, performing hot press molding, wherein the single-sided sizing amount is 140-220 g/m 2, the hot press temperature is 110 ℃, the pressure is 1-1.5 MPa, and the hot press rate is 0.5-1 mm/min.
9. A plywood characterized by being formed by hot pressing the adhesive according to any one of claims 1 to 5 with a veneer.
10. A plywood according to claim 9, wherein the formaldehyde emission of the plywood is 0.002-0.005mg/m 3 and the glue strength is greater than 1.58MPa.
CN202310144673.3A 2023-02-21 2023-02-21 Environment-friendly adhesive for organic acid-polyol-based formaldehyde-free high-performance plywood, and preparation method and application thereof Active CN116355560B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109593508A (en) * 2018-12-19 2019-04-09 山东农业大学 A kind of wood-based plate biology base is without aldehyde adhesive and preparation method thereof
CN113861935A (en) * 2021-09-27 2021-12-31 西南林业大学 Vegetable protein-furfuryl alcohol wood adhesive and preparation method thereof

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US8022164B1 (en) * 2010-03-04 2011-09-20 Microvast, Inc. Two-component solvent-free polyurethane adhesives

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109593508A (en) * 2018-12-19 2019-04-09 山东农业大学 A kind of wood-based plate biology base is without aldehyde adhesive and preparation method thereof
CN113861935A (en) * 2021-09-27 2021-12-31 西南林业大学 Vegetable protein-furfuryl alcohol wood adhesive and preparation method thereof

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