CN112322254A - Biomass aldehyde-free adhesive and preparation and application methods thereof - Google Patents
Biomass aldehyde-free adhesive and preparation and application methods thereof Download PDFInfo
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- CN112322254A CN112322254A CN202011266581.5A CN202011266581A CN112322254A CN 112322254 A CN112322254 A CN 112322254A CN 202011266581 A CN202011266581 A CN 202011266581A CN 112322254 A CN112322254 A CN 112322254A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J189/00—Adhesives based on proteins; Adhesives based on derivatives thereof
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- 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
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N1/00—Pretreatment of moulding material
- B27N1/02—Mixing the material with binding agent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N1/00—Pretreatment of moulding material
- B27N1/02—Mixing the material with binding agent
- B27N1/0209—Methods, e.g. characterised by the composition of the agent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
- B27N3/08—Moulding or pressing
- B27N3/10—Moulding of mats
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention relates to the technical field of processing of formaldehyde-free adhesives, in particular to a biomass formaldehyde-free adhesive based on a cellulose extracting solution and a preparation method and an application method thereof. The biomass aldehyde-free adhesive prepared by the cellulose extracting solution has the advantages of wide raw material source, low preparation cost, environmental protection and no pollution, can fully utilize natural resources, reduces the dependence of adhesive wood on petroleum resources, can realize high-value utilization of plant fibers with natural antibacterial action, and has important significance for environmental protection.
Description
Technical Field
The invention relates to a preparation method of a biomass aldehyde-free adhesive, and particularly relates to a biomass aldehyde-free adhesive and preparation and application methods thereof.
Background
With the enhancement of environmental awareness of people and the soundness of environmental regulations of various countries around the world, adhesives prepared from petroleum byproduct high molecular materials are increasingly restricted by more policies, and the traditional formaldehyde-free adhesives are gradually eliminated by the market due to the problem of formaldehyde release. In recent years, environment-friendly aldehyde-free adhesives prepared from biomaterials are favored by researchers and markets because of their advantages of being aldehyde-free, non-toxic, low in cost, and the like. The biomass adhesive in the current market is composed of biomass powder and resin with a crosslinking and curing function, so that the problems of easy moth eating, easy mildew and the like generally exist, the problem of mildew is more serious particularly in a highly humid environment in south China, and a bactericide needs to be additionally added to improve and relieve the mildew-proof and sterilization performance of the biomass adhesive. However, the addition of the assistants such as the mildew-proof bactericide and the like cannot completely solve the problem of avoiding mildew in a humid environment fundamentally, and meanwhile, the cost is further increased, and the bonding strength of the glue and other physical performance indexes of the board are reduced.
Disclosure of Invention
The invention aims to overcome the defects that a biomass adhesive in the prior art is easy to damage by worms and mildew and has high cost, and provides a biomass aldehyde-free adhesive which does not need to be additionally added with a bactericide and has worm-damage prevention and mildew prevention performances, and a preparation method and application thereof.
In order to solve the technical problem, the technical scheme is that the preparation method of the biomass formaldehyde-free adhesive comprises the following steps:
s1, airing and drying the plant fiber until the water content is lower than 5 wt%, obtaining dried plant fiber, crushing the dried plant fiber, filtering the crushed plant fiber by using a 100-mesh and 200-mesh filter screen to obtain plant fiber coarse material powder and coarse particle residue 1, mixing the plant fiber coarse material powder with a fiber solvent activation system according to the mass ratio of (0.5-2) to (5-35), carrying out heat treatment on the mixture at the temperature of 80-150 ℃ for 1-10h, and then carrying out ultrasonic treatment at the temperature of 25-35 ℃ for 1-3h to obtain an activated cellulose solution;
s2, filtering the activated cellulose solution prepared in the step S1 by using a 100-mesh 200-mesh filter screen, drying the filtrate in an oven at the temperature of 120-mesh 150 ℃ to obtain activated cellulose powder, mixing the activated cellulose powder and a cellulose dissolving system according to the mass ratio of (1-10) - (10-100), thermally dissolving the mixture at the temperature of 80-180 ℃ for 3-10h, then carrying out ultrasonic treatment for 1-2h, filtering the mixture by using a 100-mesh 200-mesh filter screen, wherein the filtrate is the cellulose solution with the concentration of 10-50wt, and collecting filtered coarse particle residues 2;
s3, carrying out vacuum freeze drying on the cellulose solution obtained in the step S2 at 80-50 ℃ below zero for 3-8h to remove the solvent, carrying out heat drying at 120-150 ℃ to obtain cellulose fine powder, mixing the cellulose fine powder and a fiber acetylation solvent system according to the mass ratio of 0.5:5, and carrying out acetylation modification treatment at 85-90 ℃ for 1-3h to obtain an acetylated cellulose solution;
s4, mixing acetic acid, nitromethylmorpholine and water according to the mass ratio of (1-3) to (4-6) to (1-5) to prepare a three-system mixed aqueous solution, carrying out vacuum freeze drying on the acetylated cellulose solution prepared in the step S3 at the temperature of-120 ℃ to-50 ℃ for 5-24h to obtain acetylated cellulose powder, mixing the acetylated cellulose powder and the three-system mixed aqueous solution according to the mass ratio of (1-5) to (20-50), and slowly stirring and dissolving at the temperature of 80-120 ℃ for 5-8h to obtain a three-system-cellulose mixed aqueous solution;
s5, taking 150 parts by mass of the three-system-cellulose mixed aqueous solution obtained in the step S4, sequentially adding 30-85 parts by mass of plant protein powder, 30-80 parts by mass of a cross-linking agent, 1-10 parts by mass of a curing agent, 5-15 parts by mass of a tackifying assistant, 1-5 parts by mass of a stabilizer, 0.5-5 parts by mass of a surfactant and 5-15 parts by mass of plant fiber residue filling powder, stirring and dispersing for 5-10min at room temperature, placing in a far infrared sterilization disinfection box for 5-10h, and aging for 3-8h at 25-35 ℃ to obtain the biomass aldehyde-free adhesive.
The preparation method of the biomass formaldehyde-free adhesive is further improved as follows:
preferably, in step S1, the plant fiber is one or a combination of two or more of bamboo leaf fiber, Chinese fan palm leaf fiber, and ramie fiber.
Preferably, the fiber solvent activation system in step S1 is a combination of two or more of morpholine oxynitride, NN dimethylacetamide, potassium permanganate, lithium chloride/zinc chloride, ethylenediamine, paraformaldehyde, dimethyl sulfoxide, sodium hydroxide, urea, and an ionic liquid.
Preferably, the cellulose dissolving system in step S2 is a combination of two or more of morpholine oxynitride, NN dimethylacetamide, potassium permanganate, lithium chloride/zinc chloride, ethylenediamine, paraformaldehyde, dimethyl sulfoxide, sodium hydroxide, urea, and an ionic liquid.
Preferably, the fiber acetylation solvent system in step S3 is one of an acetic anhydride-concentrated sulfuric acid system, a maleic anhydride-concentrated sulfuric acid system, an acetic anhydride-p-toluenesulfonic acid system, and a phthalic anhydride-phosphoric acid system.
Preferably, in step S5, the plant protein powder is biomass powder with a protein content of not less than 8 wt% and a protein molecular weight of not less than 6 ten thousand, and is one or a combination of two or more of corn flour, wheat flour, peanut powder, walnut powder, sesame powder, soybean flour, sunflower seed powder, almond powder, lotus seed powder, black bean powder, egg white protein powder, green bean powder, pine nut powder, macaroni, mung bean powder, kidney bean powder, agaric powder, red bean powder, coix seed powder, melon seed powder and spirulina powder.
Preferably, the crosslinking agent in step S5 is one or a combination of two or more of silicone resin, polyamide resin, cationic polyacrylamide resin, polyamide polyamine epichlorohydrin resin, acrylic resin, polyamide polyurea epichlorohydrin resin, polyethyleneimine resin, chitosan, dialdehyde starch, maleic acid homopolymer and terpolymer resin, polyethylene maleic acid resin, zirconium titanate amine resin, benzoxazine Pickering emulsion; alternatively, the curing agent in step S5 is one or a combination of two or more of glyoxal, glutaraldehyde or trialdehyde, aluminum potassium sulfate dodecahydrate, TDI trimer, HDI trimer, MDI trimer, and aziridine.
Preferably, in step S5, the tackifying assistant is one or a combination of two or more of maleic anhydride block copolymer, isobutylene-maleic anhydride copolymer ammonium salt, polyisobutylene maleic anhydride modified copolymer ammonium salt, polyisobutylene succinic anhydride modified copolymer ammonium salt, isoprene maleic anhydride copolymer ammonium salt, alcohol-soluble high molecular weight polyurethane emulsion, hydrophilic rosin resin, carrageenan, xanthan gum, agar, guar gum, arabic gum, loxin gum, gelatin, egg white, rosin gum, konjac gum, pectin, chitin, sodium alginate, cyclodextrin, terpene resin emulsion, styrene-acrylic emulsion, aloe, mugwort, and ethylene vinyl acetate maleic anhydride modified copolymer amine salt; or in the step S5, the stabilizer is one or a combination of two or more of sodium bicarbonate, sodium carbonate, sodium dihydrogen phosphate, disodium hydrogen phosphate, ammonia water, urea and sodium bisulfite; or, in the step S5, the surfactant is one or a combination of two or more of OP-10, peregal O, stearic acid, sodium dodecyl benzene sulfonate, guanidine hydrochloride and octadecyl dimethyl ammonium chloride.
Preferably, the preparation method of the plant fiber residue filling powder in step S5 is as follows: and (4) drying the coarse particle residues 2 obtained in the step S2 at 150 ℃ for 4-7h, mixing the dried coarse particle residues with the coarse particle residues 1 obtained in the step S1, and treating the mixture for 25-30min by using a ball mill to obtain the plant fiber residue filling powder.
In order to solve another technical problem, the invention adopts the technical scheme that the biomass aldehyde-free adhesive prepared by any one of the preparation methods is prepared.
In order to solve another technical problem, the technical scheme is that the application of the biomass aldehyde-free adhesive prepared by any one of the preparation methods specifically comprises the following steps:
drying the blockboard or the plywood to be bonded by means of hot drying at the temperature of 60-85 ℃ until the water content is less than or equal to 25 wt%, and then uniformly coating the biomass aldehyde-free adhesive on the surface of the blockboard or the plywood plate, wherein the adhesive application amount is 280-650 g/m-2Placing the glued board at room temperature, controlling the curing and opening period at 20-60min, then laminating multiple layers of the glued and aged board, cold-pressing for 40min-1.5h, then hot-pressing by a vulcanizing machine, wherein the hot-pressing pressure is 1.0-2.0MPa, the hot-pressing temperature is 110 plus material 165 ℃, the gradient heating is 1.5-4.5h, the heating rate of 110 plus material at 150 ℃ is 2 ℃/min, and the heating rate of 150 plus material at 165 ℃ is 1.5 ℃/min, then keeping the temperature at 165 ℃ for 6min, taking out, and cooling to form;
or diluting the biomass aldehyde-free adhesive by 0.5-1 time, drying the wood shavings by hot drying at 60-85 ℃ until the water content is less than or equal to 25 wt%, uniformly mixing the biomass aldehyde-free adhesive with the wood shavings, wherein the using amount of the biomass aldehyde-free adhesive is 5-12% of the total amount of the wood shavings, cold-pressing the glued wood shavings for 3.5-6.5h under the pressure of 1.5-2.0MPa, then carrying out hot pressing, wherein the hot pressing pressure is 1.0-2.0MPa, the hot pressing temperature is 110-165 ℃ gradient hot pressing, the temperature rise rate of 110-150 ℃ is 2 ℃/min, the temperature rise rate of 150-165 ℃ is 1.5 ℃/min, then carrying out heat preservation at 175 ℃ of 155-180 ℃ for 5-10min, taking out, and cooling to form.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides a preparation method of a biomass formaldehyde-free adhesive of a cellulose extracting solution, which is characterized by comprising the following steps and raw materials of (1) physical crushing treatment and activation of plant fibers; (2) dissolving activated cellulose; (3) acetylation of cellulose and preparation of a cellulose aqueous solution; (4) compounding cellulose biological glue. The purpose of the cellulose activation treatment is to complete degumming of bamboo leaves, ramie and Chinese fan palm leaves, remove impurities and hemicellulose in the bamboo leaves, reduce the crystallinity and hydrogen bond action of fibers and enable the fibers to be more easily dissolved; the cellulose is difficult to dissolve in water due to extremely strong hydrogen bond acting force, and meanwhile, the strong hydrophilicity of the cellulose also causes the cellulose to influence the water resistance of the glue after solidification; the cellulose solution is subjected to acetylation treatment, and the cellulose is modified by adopting an acetylation reagent under the condition of acid catalysis, so that the reaction activity of the cellulose is improved, and the dissolving difficulty of the cellulose in a water system mixed solvent is further reduced; plant powder protein, a cross-linking agent, a curing agent, a tackifying assistant, a surfactant, a stabilizer, plant fiber residue filling powder and the like are added into a three-system-cellulose mixed aqueous solution to complete the compounding of cellulose biological glue, wherein the cross-linking agent is characterized in that the cross-linking agent can further react with wood fiber, cellulose in glue and various functional groups (amino, hydroxyl, carboxyl and the like) in the plant powder protein to form functional resin of a three-dimensional cross-linking network, so that the engaging force of the cellulose glue on the glued surface of the wood is further increased, and the gluing strength of the cellulose glue is improved; the curing agent is an auxiliary agent for promoting the cross-linking and curing degree among the cross-linking agent, the vegetable protein, the cellulose and the wood fiber; the tackifying assistant is characterized in that the initial viscosity performance of the cellulose biological glue is further improved; the surfactant is characterized in that the surface energy of the glue is further reduced, so that the glue compounded by adding the powder is more easily absorbed by wood fibers of a glued surface; the purpose of the stabilizer is to reduce the viscosity of the cellulose colloid after powder addition and stabilize the standing period (more than or equal to 48h) after colloid preparation.
2. The cellulose is extracted from fiber raw materials (bamboo leaves, ramie and Chinese fan palm leaves) with natural antibacterial effect in the nature and acetylated, a multi-solvent mixed system cellulose solution compatible with water is obtained, the cellulose solution is taken as a main material and is compounded with plant powder to obtain cellulose biological glue, a tackifier component, a cross-linking agent, a curing agent and a stabilizing agent component are introduced, a three-dimensional cross-linking network of a wood cementing layer and a board layer is realized, the tackifying and the performance stabilizing of cellulose biomass water are realized, and the biomass cellulose glue with good initial adhesion, easy gluing and water resistance and excellent natural antibacterial performance of the prepared board is obtained; the biomass aldehyde-free adhesive is aldehyde-free and environment-friendly, the raw material source for preparation is wide, the antibacterial effect of the cellulose enables the adhesive to have natural antibacterial property, an artificially synthesized antibacterial agent does not need to be added, the mildew condition of a glued layer of a board after glue application is greatly improved, and the application value and the application range of a plant fiber material are further improved and widened. Meanwhile, the sources of the main raw materials such as the Chinese fan palm, the bamboo fiber, the ramie and the like are also locally obtained (especially in the south China area of China), the method has the characteristics of wide raw material sources, low preparation cost, environmental protection and no pollution, can fully utilize natural resources, reduces the dependence of the wood adhesive on petroleum resources, realizes the formaldehyde-free property of the cellulose adhesive, simultaneously enables a large amount of waste biological resources to be highly utilized in a planting manner, and can hopefully reduce the cost of the biomass formaldehyde-free adhesive while reducing the environmental pollution.
3. The plant fiber residue filling powder added in the preparation process is residue in the preparation process of the cellulose solution, and the plant fiber residue filling powder can be used as a filler to further reduce the glue cost and improve the utilization rate of cellulose raw materials.
4. The invention also realizes the high-efficiency bonding of the cellulose biological glue on the wood board, the plywood and the flakeboard by carrying out the gradient heat treatment program (110-, the 24-hour water absorption expansion rate is less than or equal to 10 percent, the performance of the I-type shaving board is achieved, compared with the existing commercial board glue, the glue has the characteristics of zero formaldehyde content, high bonding strength, good water resistance, easy gluing, difficult mildewing and the like, and the bonding strength reaches the relevant standard of household boards, can simultaneously meet the bonding performance requirements of different artificial boards such as shaving boards, blockboards, plywood and the like and the environmental protection requirements of household boards.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Note that "%" and "parts by mass" shown in the description herein mean "% by mass" and "parts by mass", respectively, unless otherwise specified.
Example 1
The invention relates to a preparation and application method of a biomass formaldehyde-free adhesive, which specifically comprises the following steps:
(1) firstly, airing the prepared Chinese fan palm leaves for 1-2 weeks at the external environment temperature of 25-35 ℃, then placing the Chinese fan palm leaves in a high-temperature oven for drying for 8 hours at the temperature of 100-110 ℃, controlling the water content of the Chinese fan palm leaves to be below 5%, then crushing the Chinese fan palm leaves for 10 minutes at the speed of 10000-15000 r/min by using a four-cutter-head high-speed crusher, filtering the Chinese fan palm leaves by using a 200-mesh filter screen to obtain plant fiber coarse material powder, and taking out the filtered coarse particle residue 1 as plant fiber residue filling powder for later use after 25-30 minutes by using a ball mill. Mixing and stirring 5 parts by mass of the obtained plant fiber coarse powder and a fiber solvent activation system according to the mass ratio of solid to liquid of 0.5:5, wherein the fiber solvent activation system consists of 48 parts by mass of nitromethylmorpholine and 2 parts by mass of lithium chloride, stirring and dissolving for 5 hours at the temperature of 150 ℃, cooling to the room temperature of 25-35 ℃, and carrying out ultrasonic treatment for 1 hour to prepare an activated cellulose solution.
(2) Filtering the activated cellulose solution obtained in the above step by using a 200-mesh filter screen, drying at 150 ℃ to remove the solvent, and weighing for multiple times until the weight is constant to obtain activated cellulose powder. Then 5 parts by mass of activated cellulose powder is weighed and mixed with 45 parts by mass of a cellulose dissolving system, the cellulose dissolving system consists of NN dimethyl acetamide and 5 parts by mass of zinc chloride, the mixture is dissolved for 6 hours at 165 ℃, then the mixture is subjected to ultrasonic treatment for 1 hour again to obtain a slightly transparent or semitransparent cellulose solution, and residues are filtered out by a 200-mesh filter screen to obtain the cellulose solution. Drying the filtered coarse particle residue 2 at 150 ℃ for 5h, and grinding and refining the coarse particle residue by using a ball mill to obtain plant fiber residue filling powder for later use.
(3) The cellulose solution obtained in the last step is subjected to vacuum freeze drying for 8 hours at the temperature of-80 ℃ to remove the solvent, and is subjected to heat drying for 1 hour at the temperature of 150 ℃ to obtain cellulose fine powder, then the cellulose fine powder is added into concentrated sulfuric acid, acetic anhydride is added at the temperature of 85-90 ℃ to carry out acetylation modification treatment for 2 hours, wherein the mass ratio of the cellulose fine powder to the concentrated sulfuric acid to the acetic anhydride is 0.5:5, and the acetylated cellulose solution is obtained.
(4) And (2) carrying out vacuum freeze drying on the acetylated cellulose solution obtained in the last step for 24h under the conditions of-0.1 MPa and-120 ℃ to obtain acetylated cellulose powder, then dispersing 5 parts by mass of the cellulose powder into a three-system mixed aqueous solution according to the mass ratio of solid to liquid of 5:50, wherein the three-system mixed aqueous solution contains 10 parts by mass of acetic acid, 30 parts by mass of N-methylmorpholine and 10 parts by mass of deionized water, and then slowly stirring and reacting for 8h at 80 ℃ to obtain a three-system-cellulose mixed aqueous solution.
(5) And (2) taking 100 parts by mass of the three-system-cellulose mixed aqueous solution, respectively adding 35 parts by mass of soybean flour, 10 parts by mass of corn flour, 5 parts by mass of flour, 50 parts by mass of polyamide polyurea epichlorohydrin resin, 5 parts by mass of TDI trimer, 8 parts by mass of polyisobutylene maleic anhydride modified copolymer ammonium salt, 5 parts by mass of peregal O3, 2 parts by mass of sodium bicarbonate and 5 parts by mass of plant fiber residue filling powder prepared in the steps (1) and (2), stirring and dispersing at room temperature for 5-10min, and placing in a far infrared sterilization disinfection box for aging at 25-35 ℃ for 2h to obtain the biomass aldehyde-free adhesive.
(6) After the glue is prepared, firstly, the blockboard or the plywood or the wood shavings to be bonded are subjected to hot drying pretreatment at 60-85 ℃ for drying for 3-5 hours to remove excessive water, the water content is controlled to be lower than 20%, then the biomass formaldehyde-free adhesive is uniformly coated on the surface of the blockboard or the plywood, and the glue application amount is 280g/m2After-ripening of the coated boardThe melting and opening period can be controlled to be 45-60min, and then the glued and aged plates are laminated in multiple layers and are cold-pressed for 40min-1.5 h; and then carrying out hot pressing on the plate under the pressure of 1.5MPa, carrying out gradient hot pressing for 1.5h at the temperature of 110-.
When the particle board is prepared, the biomass aldehyde-free adhesive is diluted by 1 time, then the biomass aldehyde-free adhesive and the wood shavings, which account for the total amount of the wood shavings, are pre-stirred, shaken up and sprayed and mixed for 60min in a high-voltage electrostatic spraying (45KV, the current is 0A, and the bottom dispersion tray is grounded by adopting an ore oxygen red copper mesh cushion layer), and the glue spraying amount of the particle board is 5% of the total amount of the wood shavings. Then cold pressing is carried out for 3.5h under the pressure of 1.5MPa, then hot pressing is carried out, the hot pressing pressure is 1.0-2.0MPa, the heating rate of the hot pressing temperature is 2 ℃/min at the temperature of 110 plus materials and 150 plus materials and 165 ℃ is 1.5 ℃/min, then the temperature is kept for 6min at 165 ℃, and then the product is taken out and cooled to be formed.
Example 2
The invention relates to a preparation and application method of a biomass formaldehyde-free adhesive, which specifically comprises the following steps:
(1) firstly, airing bamboo leaves prepared in advance for 1-2 weeks at the external environment temperature of 25-35 ℃, then placing the bamboo leaves in a high-temperature oven for drying for 10 hours at the temperature of 100-20000 ℃, controlling the water content of the bamboo leaves to be below 5%, then crushing the bamboo leaves for 10 minutes at the speed of 15000-20000 revolutions/min by using a four-cutter-head high-speed crusher, filtering the bamboo leaves by using a 200-mesh filter screen to obtain plant fiber coarse material powder, and taking out the filtered coarse particle residue 1 after 25-30 minutes by using a ball mill as plant fiber residue filling powder for later use. Mixing and stirring the obtained 5 parts by mass of the plant fiber coarse powder and a fiber solvent activation system according to the mass ratio of 2:35, wherein the fiber solvent activation system consists of 135 parts by mass of N-methylmorpholine oxide, 25 parts by mass of dimethyl sulfoxide, 5 parts by mass of ionic liquid and 5 parts by mass of lithium chloride, stirring and dissolving for 6 hours at the temperature of 150 ℃, cooling to the room temperature of 25-35 ℃, and carrying out ultrasonic treatment for 2 hours to obtain an activated cellulose solution.
(2) Filtering the activated cellulose solution obtained in the above step by using a 200-mesh filter screen, drying at 150 ℃ to remove the solvent, and weighing for multiple times until the weight is constant to obtain activated cellulose powder. Then 10 parts by mass of activated cellulose powder is weighed and mixed with 100 parts by mass of a cellulose dissolving system, the cellulose dissolving system consists of 60 parts by mass of NN dimethyl acetamide, 20 parts by mass of N-methylmorpholine oxide and 20 parts by mass of lithium chloride, the mixture is dissolved for 6 hours at 165 ℃, then the solution is subjected to ultrasonic treatment for 1 hour again to obtain a slightly transparent or semitransparent cellulose solution, and residues are filtered out by a 200-mesh filter screen to obtain the cellulose solution. And drying the filtered coarse particle residue 2 at 160 ℃ for 5h, and grinding and refining the coarse particle residue by using a ball mill to obtain plant fiber residue filling powder for later use.
(3) The cellulose solution obtained in the last step is subjected to vacuum freeze drying for 6 hours at the temperature of 70 ℃ below zero to remove the solvent, and is subjected to heat drying for 1 hour at the temperature of 150 ℃ to obtain cellulose fine powder, then the cellulose fine powder is added into concentrated sulfuric acid, maleic anhydride is added at the temperature of 85 ℃ to 90 ℃ to perform acetylation modification treatment for 2 hours, wherein the mass ratio of the cellulose fine powder to the concentrated sulfuric acid to the acetic anhydride is 0.5:5, and the acetylated cellulose solution is obtained.
(4) And (2) carrying out vacuum freeze drying on the acetylated cellulose solution obtained in the last step for 10h under the conditions of-0.1 MPa and-100 ℃ to obtain acetylated cellulose powder, then dispersing 10 parts by mass of cellulose powder into a three-system mixed aqueous solution according to the mass ratio of solid to liquid of 10:100, wherein the three-system mixed aqueous solution contains 20 parts by mass of acetic acid, 60 parts by mass of N-methylmorpholine and 20 parts by mass of deionized water, and then slowly stirring and reacting at 105 ℃ for 6h to obtain a three-system-cellulose mixed aqueous solution.
(5) Taking 150 parts by mass of a three-system-cellulose mixed aqueous solution, respectively adding 55 parts by mass of soybean flour, 15 parts by mass of egg white powder, 5 parts by mass of flour, 70 parts by mass of polyamide polyurea epichlorohydrin resin, 8 parts by mass of TDI trimer, 15 parts by mass of polyisobutylene maleic anhydride modified copolymer ammonium salt, 105 parts by mass of OP, 3 parts by mass of sodium bisulfite and 10 parts by mass of plant fiber residue filling powder, stirring and dispersing for 5-10min at room temperature, placing in a far infrared sterilization disinfection box, and aging for 2h at 25-35 ℃ to obtain the biomass aldehyde-free adhesive.
(6) After the glue is prepared, the glue to be bonded is first preparedDrying the blockboard or the plywood or the wood shavings at 60-85 ℃ for 3-5h to remove excessive water, controlling the water content to be lower than 20%, then uniformly coating the biomass formaldehyde-free adhesive on the surface of the blockboard or the plywood plate, wherein the adhesive application amount is 550g/m2Curing and opening period of the coated board can be controlled to be 45-60min, and then the glued and aged board is subjected to multi-layer lamination and cold pressing for 40min-1.5 h; and then carrying out hot pressing on the plate under the pressure of 1.5MPa, carrying out gradient hot pressing for 2.0h at the temperature of 110-.
When the shaving board is prepared, after the biomass aldehyde-free adhesive is diluted by 0.5 time, the biomass aldehyde-free adhesive and the wood shavings are stirred, shaken and uniformly sprayed and mixed for 60min in a high-voltage electrostatic spraying (45KV, current of 0A, and a bottom dispersion tray is grounded by adopting an ore oxygen red copper mesh cushion layer) mode, wherein the total amount of the wood shavings is the total amount of the wood shavings, and the glue spraying amount of the shaving board is 8 percent of the total amount of the wood shavings. Then cold pressing for 4.5h under the pressure of 2.0MPa, then hot pressing, wherein the hot pressing pressure is 1.0-2.0MPa, the heating rate of the hot pressing temperature is 2 ℃/min at the temperature of 110-plus-150 ℃ and the heating rate of the hot pressing temperature is 1.5 ℃/min at the temperature of 150-plus-165 ℃, then heat preservation is carried out for 6min at the temperature of 165 ℃, and then the mixture is taken out and cooled to form the composite material.
Example 3
The invention relates to a preparation and application method of a biomass formaldehyde-free adhesive, which specifically comprises the following steps:
(1) firstly, airing the prepared ramie at the external environment temperature of 25-35 ℃ for 1-2 weeks, then placing the ramie in a high-temperature oven for drying for 8 hours at the temperature of 100-. Mixing and stirring 5 parts by mass of the obtained plant fiber coarse powder and a fiber solvent activation system according to the mass ratio of solid to liquid of 5:100, wherein the fiber solvent activation system consists of 75 parts by mass of nitromethylmorpholine oxide, 5 parts by mass of dimethyl sulfoxide, 15 parts by mass of NN dimethyl acetamide and 5 parts by mass of zinc chloride, and preparing the activated cellulose solution.
(2) Filtering the activated cellulose solution obtained in the above step by using a 200-mesh filter screen, drying at 150 ℃ to remove the solvent, and weighing for multiple times until the weight is constant to obtain activated cellulose powder. Then 5 parts by mass of activated cellulose powder is weighed and mixed with 350 parts by mass of a cellulose dissolving system, the cellulose dissolving system consists of 330 parts by mass of NN dimethyl acetamide and 20 parts by mass of lithium chloride, the mixture is dissolved for 6 hours at 165 ℃, then the mixture is subjected to ultrasonic treatment for 1 hour again to obtain a slightly transparent or semitransparent cellulose solution, and residues are filtered out by a 200-mesh filter screen to obtain the cellulose solution. And drying the filtered coarse particle residue 2 at 160 ℃ for 5h, and grinding and refining the coarse particle residue by using a ball mill to obtain plant fiber residue filling powder for later use.
(3) The cellulose solution obtained in the last step is subjected to vacuum freeze drying for 8 hours at the temperature of-80 ℃ to remove the solvent, and is subjected to heat drying for 1 hour at the temperature of 150 ℃ to obtain cellulose fine powder, then the cellulose fine powder is added into toluenesulfonic acid, acetic anhydride is added at the temperature of 85-90 ℃ to perform acetylation modification treatment for 2 hours, wherein the mass ratio of the cellulose fine powder to the toluenesulfonic acid to the acetic anhydride is 0.5:5, and the acetylated cellulose solution is obtained.
(4) And (2) carrying out vacuum freeze drying on the acetylated cellulose solution obtained in the last step at-0.1 MPa and-90 ℃ for 3h to obtain acetylated cellulose powder, then dispersing 17.5 parts by mass of the acetylated cellulose powder into a three-system mixed aqueous solution according to the mass ratio of solid to liquid of 10:100, wherein the three-system mixed aqueous solution contains 40 parts by mass of acetic acid, 100 parts by mass of azomethylmorpholine and 35 parts by mass of deionized water, and then slowly stirring and reacting at 120 ℃ for 5h to finally obtain a three-system-cellulose mixed aqueous solution.
(5) Taking 150 parts by mass of a three-system-cellulose mixed aqueous solution, respectively adding 60 parts by mass of soybean flour, 10 parts by mass of corn flour, 5 parts by mass of flour, 50 parts by mass of polyamide polyamine epichlorohydrin resin, 20 parts by mass of silicone-acrylic emulsion resin, 10 parts by mass of HDI trimer, 20 parts by mass of polyisobutylene maleic anhydride modified copolymer ammonium salt, 6 parts by mass of sodium dodecyl benzene sulfonate, 3 parts by mass of sodium bisulfite and 15 parts by mass of plant fiber residue filling powder, stirring and dispersing for 5-10min at room temperature, placing in a far infrared sterilization disinfection box, and standing for 2h at 25-35 ℃ to obtain the biomass aldehyde-free adhesive.
(6) After the glue is prepared, firstly, the blockboard or the plywood or the wood shavings to be bonded are dried for 3-5 hours at the temperature of 60-85 ℃ to remove excessive water, the water content is controlled to be lower than 20%, then the biomass formaldehyde-free adhesive is uniformly coated on the surface of the blockboard or the plywood, and the glue application amount is 650g/m2Curing and opening period of the coated board can be controlled to be 45-60min, and then the glued and aged board is subjected to multi-layer lamination and cold pressing for 40min-1.5 h; and then carrying out hot pressing on the plate under the pressure of 1.8MPa, carrying out gradient hot pressing for 4.5h at the temperature of 110-.
When the particle board is prepared, the biomass aldehyde-free adhesive is diluted by 0.8 time, then the biomass aldehyde-free adhesive and the wood shavings, which account for the total amount of the wood shavings, are sprayed and mixed for 60min in a high-voltage electrostatic spraying mode (45KV, the current is 0A, and the bottom dispersion tray is grounded by adopting an ore oxygen red copper mesh cushion layer), and the glue spraying amount of the particle board is 12% of the total amount of the wood shavings. Then cold pressing is carried out for 6.5h under the pressure of 2.0MPa, then hot pressing is carried out, the hot pressing pressure is 1.0-2.0MPa, the heating rate of the hot pressing temperature is 2 ℃/min at the temperature of 110 plus materials and 150 plus materials and 165 ℃ is 1.5 ℃/min, then the temperature is kept for 6min at 165 ℃, and then the product is taken out and cooled to be formed.
Blank control example
The invention relates to preparation of a common biomass formaldehyde-free adhesive, which is obtained by the following method, and specifically comprises the following steps:
(1) respectively adding the prepared biomass powder into 20 parts by mass of purified water, adding other curing agents and cross-linking agents, and uniformly stirring at room temperature, specifically adding 60 parts by mass of soybean flour, 10 parts by mass of corn flour, 5 parts by mass of flour, 50 parts by mass of polyamide polyamine epichlorohydrin resin, 20 parts by mass of silicone-acrylic emulsion resin, 10 parts by mass of HDI trimer, 20 parts by mass of polyisobutylene maleic anhydride modified copolymer ammonium salt, 6 parts by mass of sodium dodecyl benzene sulfonate and 3 parts by mass of sodium bisulfite, stirring and dispersing at room temperature for 5-10min, and placing in a far infrared sterilization disinfection box for aging at 25-35 ℃ for 2h to obtain the common biomass aldehyde-free adhesive.
(6) After the glue is prepared, firstly, the blockboard or the plywood or the wood shavings to be bonded are subjected to hot drying pretreatment at 60-85 ℃ for drying for 3-5 hours to remove excessive water, the water content is controlled to be lower than 20%, then the common biomass formaldehyde-free adhesive is uniformly coated on the surface of the blockboard or the plywood, and the glue application amount is 650g/m2Curing and opening period of the coated board can be controlled to be 45-60min, and then the glued and aged board is subjected to multi-layer lamination and cold pressing for 40min-1.5 h; then, the plate is hot-pressed under the pressure of 1.8MPa, the plate is hot-pressed at the temperature of 110-.
When the particle board is prepared, after the common biomass aldehyde-free adhesive is diluted by 0.8 time, the biomass aldehyde-free adhesive and the wood shavings which account for the total amount of the wood shavings are stirred, shaken and sprayed for 60min while being uniformly stirred and mixed in a high-voltage electrostatic spraying (45KV, the current is 0A, and the bottom dispersion tray adopts a mineral oxygen red copper mesh cushion layer and is grounded), and the glue spraying amount of the particle board is 12% of the total amount of the wood shavings. Then cold pressing is carried out for 6.5h under the pressure of 2.0MPa, then hot pressing is carried out, the hot pressing pressure is 1.0-2.0MPa, the heating rate of the hot pressing temperature is 2 ℃/min at the temperature of 110 plus materials and 150 plus materials and 165 ℃ is 1.5 ℃/min, then the temperature is kept for 6min at 165 ℃, and then the product is taken out and cooled to be formed.
Table 1 performance test chart for biomass non-aldehyde adhesives prepared in examples 1-3
Note: the blank control sample is the common biomass formaldehyde-free adhesive prepared in the blank control example, and no antibacterial cellulose powder is introduced. The test data are tested by adopting the carpentry board or the shaving board after hot pressing.
From the test results in table 1, the biomass aldehyde-free adhesive prepared by the method has the advantages of no aldehyde and no toxicity of a common biomass aldehyde-free adhesive system, and the plant fiber powder with natural antibacterial effect is introduced into an adhesive system by combining a freeze drying technology and a plant cellulose extraction technology, so that a good sterilization and mildew prevention effect can be obtained without adding a sterilization and mildew prevention auxiliary agent for a second time. The prepared board has natural antibacterial performance, good mildew resistance in a humid environment, water resistance and high bonding strength, and is particularly suitable for improving the mildew resistance of the board in the high-humidity environment in the central and south China, particularly in the south China. Meanwhile, abundant forest lands, palm livistona, bamboo, hemp and other plant resources with natural antibacterial effects in south China also provide convenience for local materials, are favorable for further reducing the cost, and utilize natural low-cost and abundant-source plant resources to a greater extent.
It should be understood by those skilled in the art that the foregoing is only illustrative of several embodiments of the invention, and not of all embodiments. It should be noted that many variations and modifications are possible to those skilled in the art, and all variations and modifications that do not depart from the gist of the invention are intended to be within the scope of the invention as defined in the appended claims.
Claims (11)
1. The preparation method of the biomass formaldehyde-free adhesive is characterized by comprising the following steps:
s1, airing and drying the plant fiber until the water content is lower than 5 wt%, obtaining dried plant fiber, crushing the dried plant fiber, filtering the crushed plant fiber by using a 100-mesh and 200-mesh filter screen to obtain plant fiber coarse material powder and coarse particle residue 1, mixing the plant fiber coarse material powder with a fiber solvent activation system according to the mass ratio of (0.5-2) to (5-35), carrying out heat treatment on the mixture at the temperature of 80-150 ℃ for 1-10h, and then carrying out ultrasonic treatment at the temperature of 25-35 ℃ for 1-3h to obtain an activated cellulose solution;
s2, filtering the activated cellulose solution prepared in the step S1 by using a 100-mesh 200-mesh filter screen, drying the filtrate in an oven at the temperature of 120-mesh 150 ℃ to obtain activated cellulose powder, mixing the activated cellulose powder and a cellulose dissolving system according to the mass ratio of (1-10) - (10-100), thermally dissolving the mixture at the temperature of 80-180 ℃ for 3-10h, then carrying out ultrasonic treatment for 1-2h, filtering the mixture by using a 100-mesh 200-mesh filter screen, wherein the filtrate is a cellulose solution with the concentration of 10-50 wt%, and collecting filtered coarse particle residues 2;
s3, carrying out vacuum freeze drying on the cellulose solution obtained in the step S2 at 80-50 ℃ below zero for 3-8h to remove the solvent, drying at 120-150 ℃ to obtain cellulose fine powder, mixing the cellulose fine powder and a cellulose acetylation solvent system according to the mass ratio of 0.5:5, and carrying out acetylation modification treatment at 85-90 ℃ for 1-3h to obtain an acetylated cellulose solution;
s4, mixing acetic acid, nitromethylmorpholine and water according to the mass ratio of (1-3) to (4-6) to (1-5) to prepare a three-system mixed aqueous solution, carrying out vacuum freeze drying on the acetylated cellulose solution prepared in the step S3 at the temperature of-120 ℃ to-50 ℃ for 5-24h to obtain acetylated cellulose powder, mixing the acetylated cellulose powder and the three-system mixed aqueous solution according to the mass ratio of (1-5) to (20-50), and slowly stirring and dissolving at the temperature of 80-120 ℃ for 5-8h to obtain a three-system-cellulose mixed aqueous solution;
s5, taking 150 parts by mass of the three-system-cellulose mixed aqueous solution obtained in the step S4, sequentially adding 30-85 parts by mass of plant protein powder, 30-80 parts by mass of a cross-linking agent, 1-10 parts by mass of a curing agent, 5-15 parts by mass of a tackifying assistant, 1-5 parts by mass of a stabilizer, 0.5-5 parts by mass of a surfactant and 5-15 parts by mass of plant fiber residue filling powder, stirring and dispersing for 5-10min at room temperature, placing in a far infrared sterilization box for 5-10h, and aging for 3-8h at 25-35 ℃ to obtain the biomass aldehyde-free adhesive.
2. The method of claim 1, wherein the plant fiber in step S1 is one or a combination of two or more of bamboo leaf fiber, Chinese fan palm leaf fiber, and ramie fiber.
3. The method of claim 1, wherein the fiber solvent activation system in step S1 is selected from morpholine n-methyl oxide, NN dimethylacetamide, potassium permanganate, lithium chloride/zinc chloride, ethylenediamine, paraformaldehyde, dimethyl sulfoxide, sodium hydroxide, urea, and ionic liquids.
4. The method of claim 1, wherein the cellulose dissolving system in step S2 is selected from morpholine n-methyl oxide, NN-dimethylacetamide, potassium permanganate, lithium chloride/zinc chloride, ethylenediamine, paraformaldehyde, dimethylsulfoxide, sodium hydroxide, urea, and ionic liquids.
5. The method for preparing biomass aldehyde-free adhesive according to claim 1, wherein the fiber acetylation solvent system in step S3 is one of acetic anhydride-concentrated sulfuric acid system, maleic anhydride-concentrated sulfuric acid system, acetic anhydride-p-toluenesulfonic acid system, phthalic anhydride-phosphoric acid system.
6. The method for preparing biomass aldehyde-free adhesive according to claim 1, wherein the plant protein powder in step S5 is biomass powder with a protein content of not less than 8 wt% and a protein molecular weight of not less than 6 ten thousand, and is one or a combination of two or more of corn flour, wheat flour, peanut powder, walnut powder, sesame powder, soybean powder, sunflower seed powder, almond powder, lotus seed powder, black bean powder, egg white protein powder, green bean powder, pine nut powder, macaroni, mung bean powder, kidney bean powder, agaric powder, red bean powder, coix seed powder, melon seed powder and spirulina powder.
7. The method for preparing biomass aldehyde-free adhesive according to claim 1, wherein the cross-linking agent in step S5 is one or a combination of two or more of silicone resin, polyamide resin, cationic polyacrylamide resin, polyamide polyamine epichlorohydrin resin, acrylic resin, polyamide polyurea epichlorohydrin resin, polyethyleneimine resin, chitosan, dialdehyde starch, maleic acid homopolymer and terpolymer resin, polyethylene maleic acid resin, zirconium titanate amine resin, benzoxazine Pickering emulsion; alternatively, the curing agent in step S5 is one or a combination of two or more of glyoxal, glutaraldehyde or trialdehyde, aluminum potassium sulfate dodecahydrate, TDI trimer, HDI trimer, MDI trimer, and aziridine.
8. The method of claim 1, wherein in step S5, the adhesion promoter is one or a combination of two or more of maleic anhydride block copolymer, isobutylene-maleic anhydride copolymer ammonium salt, polyisobutylene maleic anhydride modified copolymer ammonium salt, polyisobutylene succinic anhydride modified copolymer ammonium salt, isoprene maleic anhydride copolymer ammonium salt, alcohol-soluble high molecular weight polyurethane emulsion, hydrophilic rosin resin, carrageenan, xanthan gum, agar, guar gum, gum arabic, gellan gum, gelatin, egg white, rosin gum, konjac gum, pectin, chitin, sodium alginate, cyclodextrin, terpene resin emulsion, styrene-acrylic emulsion, aloe, mugwort, and ethylene vinyl acetate maleic anhydride modified copolymer amine salt; or in the step S5, the stabilizer is one or a combination of two or more of sodium bicarbonate, sodium carbonate, sodium dihydrogen phosphate, disodium hydrogen phosphate, ammonia water, urea and sodium bisulfite; or, in the step S5, the surfactant is one or a combination of two or more of OP-10, peregal O, stearic acid, sodium dodecyl benzene sulfonate, guanidine hydrochloride and octadecyl dimethyl ammonium chloride.
9. The method for preparing biomass aldehyde-free adhesive according to claim 1, wherein the method for preparing the plant fiber residue filling powder according to step S5 is as follows: and (4) drying the coarse particle residues 2 obtained in the step S2 at 150 ℃ for 4-7h, mixing the dried coarse particle residues with the coarse particle residues 1 obtained in the step S1, and treating the mixture for 25-30min by using a ball mill to obtain the plant fiber residue filling powder.
10. A biomass aldehyde-free adhesive prepared by the preparation method of any one of claims 1 to 9.
11. The application method of the biomass aldehyde-free adhesive on the board or the wood shavings as claimed in claim 10, which is characterized by comprising the following steps: drying the blockboard or the plywood to be bonded by means of hot drying at the temperature of 60-85 ℃ until the water content is less than or equal to 25 wt%, and then uniformly coating the biomass aldehyde-free adhesive on the surface of the blockboard or the plywood plate, wherein the adhesive application amount is 280-650 g/m-2Placing the glued board at room temperature, controlling the curing and opening period at 20-60min, then laminating multiple layers of the glued and aged board, cold-pressing for 40min-1.5h, then hot-pressing by a vulcanizing machine, wherein the hot-pressing pressure is 1.0-2.0MPa, the hot-pressing temperature is 110 plus material 165 ℃, the gradient heating is 1.5-4.5h, the heating rate of 110 plus material at 150 ℃ is 2 ℃/min, and the heating rate of 150 plus material at 165 ℃ is 1.5 ℃/min, then keeping the temperature at 165 ℃ for 6min, taking out, and cooling to form;
or diluting the biomass aldehyde-free adhesive by 0.5-1 time, drying the wood shavings by hot drying at 60-85 ℃ until the water content is less than or equal to 25 wt%, uniformly mixing the biomass aldehyde-free adhesive with the wood shavings, wherein the using amount of the biomass aldehyde-free adhesive is 5-12% of the total amount of the wood shavings, cold-pressing the glued wood shavings for 3.5-6.5h under the pressure of 1.5-2.0MPa, then carrying out hot pressing, wherein the hot pressing pressure is 1.0-2.0MPa, the hot pressing temperature is 110-165 ℃ gradient hot pressing, the temperature rise rate of 110-150 ℃ is 2 ℃/min, the temperature rise rate of 150-165 ℃ is 1.5 ℃/min, then carrying out heat preservation at 175 ℃ of 155-180 ℃ for 5-10min, taking out, and cooling to form.
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