CN113493664A - Water-based formaldehyde-free adhesive and preparation method and application thereof - Google Patents
Water-based formaldehyde-free adhesive and preparation method and application thereof Download PDFInfo
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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
- C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
- C09J129/02—Homopolymers or copolymers of unsaturated alcohols
- C09J129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
- B27G—ACCESSORY MACHINES OR APPARATUS FOR WORKING WOOD OR SIMILAR MATERIALS; TOOLS FOR WORKING WOOD OR SIMILAR MATERIALS; SAFETY DEVICES FOR WOOD WORKING MACHINES OR TOOLS
- B27G11/00—Applying adhesives or glue to surfaces of wood to be joined
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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
- C09J101/00—Adhesives based on cellulose, modified cellulose, or cellulose derivatives
- C09J101/08—Cellulose derivatives
- C09J101/26—Cellulose ethers
- C09J101/28—Alkyl ethers
- C09J101/284—Alkyl ethers with hydroxylated hydrocarbon radicals
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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
- C09J101/00—Adhesives based on cellulose, modified cellulose, or cellulose derivatives
- C09J101/08—Cellulose derivatives
- C09J101/26—Cellulose ethers
- C09J101/28—Alkyl ethers
- C09J101/286—Alkyl ethers substituted with acid radicals
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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
- C09J103/00—Adhesives based on starch, amylose or amylopectin or on their derivatives or degradation products
- C09J103/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- 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
Abstract
The invention discloses a water-based formaldehyde-free adhesive and a preparation method and application thereof. The method comprises the following steps: (1) dissolving a water-soluble poly-element structure compound in water at 0-200 ℃ to obtain a high polymer solution; (2) adjusting the temperature to 0-200 ℃, adding a reactive assistant into the high polymer solution, adjusting the pH value to 2-10, and stirring for reaction for 1.0 min-72 h to obtain a hydrogel-like product; (3) the quasi-hydrogel reacts with the emulsion and the surfactant to form an emulsion/composite hydrogel system; (4) adding a reinforcing material into the emulsion/composite water-based adhesive system, adjusting the pH value to 2-11, and reacting to obtain the water-based aldehyde-free adhesive. The invention constructs the co-embedded film structure of water molecules, emulsion and quasi-hydrogel, and solves the problem that water-reactive compounds and water-based compounds are difficult to coexist. Moreover, the aqueous formaldehyde-free adhesive prepared by the invention has the effects of high stability, long activity period, toughening, water resistance, high adhesion and no formaldehyde release, and is suitable for artificial boards.
Description
Technical Field
The invention belongs to the technical field of polymers, and particularly relates to a water-based formaldehyde-free adhesive as well as a preparation method and application thereof.
Background
The wood adhesive is the key core technology of the artificial board industry. For a long time, the adhesive of the artificial boards produced in China still mainly comprises "formaldehyde adhesive", and harmful gas "free formaldehyde" can be volatilized in the production and use processes, so that the common grade of the artificial boards in China is low, the hidden danger of harm to human living environment is great, such as leukemia baby incidents and the like. The traditional three-aldehyde resin adhesive of urea-formaldehyde resin, phenolic resin and melamine still occupies most share in the wood and artificial board market in China due to the advantages of low price, simple manufacturing process, convenient use and the like. The high-performance and high-quality aldehyde-free adhesive has high development difficulty and high cost due to the complex technology, and the aldehyde-free wood adhesive replacing the 'three-aldehyde adhesive' is difficult to break through. At present, only E1-grade boards can be obtained by adopting the traditional manufacturing technology, the level of the green adhesive can not be far reached, the glue can reach the level of E0 by adding more phenol in the prior art, but a certain distance is still reserved from the formaldehyde-free release, a large amount of phenol and an aldehyde removing agent are introduced, and although a large amount of formaldehyde is not released, the toxic action of the phenol does not cause enough attention at present. Therefore, the waterborne formaldehyde-free plywood adhesive with proper development cost meets the development requirements of the times under the condition of ensuring that the process is not changed greatly. At present, the national is developing the green aldehyde-free artificial board products vigorously, and the products will be the mainstream of the market in a period of time in the future.
The current requirements of the plywood industry on glue are that the initial viscosity is higher, the glue viscosity is more than 8000mpa.s, the water boiling performance is excellent, the active period is long, and the technical requirements of the existing common production process flow and equipment are met. The formaldehyde-free adhesives appearing in the formaldehyde-free adhesive market mainly comprise bio-based (soybean, starch and tannin are main) formaldehyde-free adhesives, isocyanate MDI adhesives and modified adhesives thereof, but various problems can occur in the continuous production of an actual common production line. The isocyanate MDI glue has high curing speed and high cost, is sensitive to moisture in air or glue, and is partially prepared into aldehyde-free glue by adopting a mode of mixing the isocyanate MDI glue and a water-based auxiliary agent, but the defect of quick reaction of the isocyanate MDI glue and water molecules cannot be overcome, particularly the isocyanate MDI glue has short active period and is easy to bond rubber rolls and the like, so the isocyanate MDI glue is difficult to be applied in the plywood industry.
The bio-based formaldehyde-free glue on the market is mainly prepared from soybean raw materials for modification, is low in price and quick in drying, is easy to mildew and moth-eaten on a glue layer, and is excellent in safety and environmental protection due to the fact that a large amount of flour is added to improve initial viscosity, but is poor in water resistance and unstable in bonding strength. CN110922941A patent document discloses modifying soybean and other proteins with alkali, adding cross-linking agent resin such as silicone resin, polyamide resin, polyethyleneimine, wet strength agent, dialdehyde starch, etc., adding colloid (carrageenan, xanthan gum, agar, arabic gum) to increase viscosity, and adding bactericide and neutralizer. The method has the advantages of high cost, great construction difficulty, limited strength increase, poor water boiling resistance and insufficient pre-curing period. Patent documents "a prepressing formaldehyde-free soybean protein adhesive and its sheet material forming process" (CN110734741A), "a preparation process of formaldehyde-free raw wood particle board" (CN110480784A), "a low-cost formaldehyde-free soybean meal adhesive and its preparation method" (CN110272717A) and "a toughness formaldehyde-free soybean meal-based wood adhesive and its preparation method" (CN110257005A) the formaldehyde-free technology mainly adopts the addition of various reinforcing glues and isocyanate MDI glue, etc. as main raw materials to reinforce the soybean protein. The CN105670535A patent document adopts butyl acrylate and styrene as core monomers, the reaction is carried out at the temperature of 80-86 ℃, the pre-emulsification seed dropping method is adopted, the shell layer adopts styrene and methyl methacrylate as main materials, and the prepared adhesive and isocyanate curing agent are mixed according to the proportion of 1: 10 to form a two-component adhesive. Although the strength reaches the standard, the operation time is short, the factory is difficult to complete all operation procedures within the preset time, and the cleaning of the rubber roller is very difficult. The CN201810928064.6 patent document discloses an aldehyde-free adhesive technology formed by adding acrylic polymer emulsion and nano mica powder or nano talcum powder into emulsion obtained by polymerizing alkali lignin and ethyl acetate monomers, but the technology has the defects of poor initial adhesion, high cost, short pre-curing time, poor stability and the like. It can be seen from the above that, in the process of preparing artificial board formaldehyde-free adhesives at home and abroad, compounds containing isocyanate and other water-reactive compounds are usually used for doping reinforcement, but because the glue for artificial boards mostly mainly comprises water-based resin, and the isocyanate and other water-reactive compounds can rapidly react with water molecules due to extremely high active groups-NCO, the reaction activity of the isocyanate and the like in the glue is greatly reduced or the glue gelling phenomenon is caused, and meanwhile, the glue adhesion performance is reduced or the common problems of gluing rubber rollers and metal mechanical equipment are solved. These defects make it difficult to perform normal operations in actual industrial production processes and to meet the technical requirements of the existing industrial production.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a water-based aldehyde-free adhesive and a preparation method and application thereof. The invention constructs the co-embedded structure of water molecules, emulsion and quasi-hydrogel, and solves the coexistence problem between water-reactive compounds and water-based compounds.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a water-based formaldehyde-free adhesive comprises the following steps:
(1) completely dissolving a water-soluble poly-element structure compound in water at 0-200 ℃ to obtain a high polymer solution;
(2) adjusting the temperature to 0-200 ℃, adding a reactive assistant into the high polymer solution, adjusting the pH value to 2-10, and stirring and reacting for 1.0 min-72 h under the conditions of gas atmosphere, pressure of-30 MPa-10 MPa and temperature of-10-170 ℃ to obtain hydrogel-like product;
(3) adding emulsion and surfactant into the quasi-hydrogel prepared in the step (2) under the conditions of gas atmosphere, pressure of-10 MPa to 8MPa and temperature of-15 ℃ to 250 ℃, then mixing and reacting for 1.0min to 72h under the conditions of pressure of-15 MPa to 15MPa and temperature of-10 ℃ to 200 ℃, and adjusting the pH value to 3 to 12 after the reaction is finished to form an emulsion/composite hydrogel system;
(4) adding a reinforcing material into an emulsion/composite water-based adhesive system to adjust the pH value to 2-11, and then mixing and reacting for 0.1 min-72 h under the conditions of gas atmosphere, pressure of-20 MPa and temperature of-30 ℃ to 180 ℃ to obtain the water-based aldehyde-free adhesive.
The preparation method of the water-based aldehyde-free adhesive comprises the steps of firstly locking a part of water molecules in a system in a network nano structure of hydrogel in a physical and ionic bonding mode, forming a special water molecule-polymer grid co-embedded film structure through a process technology, then embedding the other part of water molecules in the hydrogel structure in a micro-emulsion combination mode to form a layer of regular nano water film structure, and finally forming a stable water-based emulsion/composite gel system through a surfactant and the process technology thereof, wherein the system structure has good structural strength and a water molecule nano film structure. The water molecules of the water-based emulsion/composite gel system are embedded in the water gel structure in a multi-layer nano water film mode, so that the common problems that the reaction activity of the water-reactive compound in the glue is greatly reduced or the glue is gelled due to the fact that the water-reactive compound can rapidly react with the water molecules because of the extremely high active groups of the water-reactive compound, and meanwhile the gluing performance of the glue is reduced or glue rollers and metal mechanical equipment are glued are solved. The invention synthesizes the emulsion/composite water-gel system and water reactive compound into the water-based formaldehyde-free adhesive with a co-embedded structure, and has the effects of high stability, long activity period, toughening, water resistance, high adhesion and no formaldehyde release.
In a preferred embodiment of the present invention, in the step (1), the water-soluble polybasic structure compound is completely dissolved in water at 50 to 120 ℃ to obtain a polymer solution.
In the step (2), the temperature is adjusted to 20 to 120 ℃, and the coagent is added to the polymer solution.
In a preferred embodiment of the present invention, in the step (2), the hydrogel-like product is obtained by stirring and reacting the mixture in a gas atmosphere at a pressure of-1 MPa to 10MPa and a temperature of 0 ℃ to 80 ℃ for 1.0min to 72 hours.
In a preferred embodiment of the present invention, in the step (3), the emulsion and the surfactant are added to the hydrogel-like product obtained in the step (2) in a gas atmosphere at a pressure of 1MPa to 8MPa and a temperature of 0 ℃ to 80 ℃.
In a preferred embodiment of the present invention, in the step (4), the reaction is carried out in a gas atmosphere at a pressure of 1 to 10MPa and at a temperature of 0 to 80 ℃ for 0.1 to 72 hours to obtain the aqueous aldehyde-free adhesive.
As a preferred embodiment of the invention, the aqueous aldehyde-free adhesive comprises the following preparation raw materials in percentage by mass: 1 to 98 percent of water-soluble poly-multi-element structure compound, 0.01 to 80 percent of active additive, 0.1 to 80 percent of emulsion, 0 to 10 percent of surfactant and 0.1 to 80 percent of reinforcing material; the mass concentration of the high polymer in the high polymer solution is 0.1-50%.
More preferably, in the step (1), the mass concentration of the polymer in the polymer solution is 1-30%.
In a preferred embodiment of the present invention, in the steps (1) to (4), the gas atmosphere is at least one of air, nitrogen, oxygen, argon, and carbon dioxide.
As a preferred embodiment of the present invention, in the step (2), a coagent is added to the polymer solution, and in the step (3), an emulsion and a surfactant are added to the hydrogel-like solution; and (4) adding the water-reactive compound and the enhancement aid into the emulsion/composite water gel system in the step (4) in modes respectively selected from gradual dropwise adding, batch adding and one-time rapid feeding.
As a preferred embodiment of the present invention, in the steps (1) to (4), the mixing manner is independently selected from mechanical stirring, ultrasonic stirring, air-float stirring, and convection stirring.
As a preferred embodiment of the present invention, in the steps (1) to (4), the heating manner of the temperature is independently selected from electric heating, steam heating, microwave heating, and open fire heating.
In a preferred embodiment of the present invention, the water-soluble poly-structural compound is at least one of starch, gum arabic, sodium alginate, bone meal, gelatin, cyclodextrin, casein, carboxymethyl cellulose, carboxyethyl cellulose, carboxypropyl cellulose, carboxybutyl cellulose, methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxybutyl cellulose, polyacrylamide, polypropyleneimine, polyacrylamide, polyvinylpyrrolidone, polyvinyl alcohol, polyallyl alcohol, polypropylene vinyl alcohol, polyvinyl chloride alcohol, polyethyleneimine, soybean protein, zein, polymaleic anhydride, polyquaternary ammonium salt, polyethylene glycol, a starch derivative, and a modified product of the above-mentioned compounds.
In a preferred embodiment of the present invention, the coagent is at least one of acetate, sulfate, bisulfate, chloride, bromide, iodide, carbonate, bicarbonate, nitrate, tetrabutylammonium halide, sodium acylpyridinium hydrochloride, alkyl sodium, ammonium salt, thiocarbonate, thiocyanate, sulfur phosphate, borate, citrate, phosphate, hydrogen phosphate, dodecyl potassium salt, dodecyl sodium salt, tetraalkyl quaternary ammonium salt, octadecyl amine acetate, coco amine acetate, oleyl amine hydrochloride, hydrogenated tallow amine hydrochloride.
The free hydrogel structure of the active auxiliary agent establishes the strength of a more perfect polymer-water molecule nano network structure and the effect of interpenetrating molecular chain networks, and the addition of the active auxiliary agent is beneficial to increasing the active period and the bonding strength of the glue.
The acetate is at least one of sodium acetate, potassium acetate, calcium acetate, magnesium acetate, cobalt acetate, copper acetate and zinc acetate; the sulfate is at least one of sodium sulfate, potassium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate, copper sulfate and zinc sulfate; the bisulfate is at least one of sodium bisulfate, potassium bisulfate, calcium bisulfate, magnesium bisulfate, cobalt bisulfate, copper bisulfate and zinc bisulfate; the chloride salt is at least one of sodium chloride, potassium chloride, calcium chloride, magnesium chloride, cobalt chloride, copper chloride and zinc chloride; the bromide salt is at least one of lithium bromide, sodium bromide, potassium bromide, calcium bromide, zinc bromide, magnesium bromide, ferrous bromide and copper bromide; the iodide salt is at least one of lithium iodide, sodium iodide, potassium iodide, calcium iodide, zinc iodide, magnesium iodide, ferrous iodide and copper iodide; the carbonate is at least one of lithium carbonate, sodium carbonate, potassium carbonate and magnesium carbonate; the bicarbonate is at least one of lithium bicarbonate, sodium bicarbonate and potassium bicarbonate; the nitrate is at least one of sodium nitrate, potassium nitrate, calcium nitrate, magnesium nitrate, cobalt nitrate, copper nitrate and zinc nitrate; the halogenated tetrabutylammonium is at least one of tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide and tetrabutylammonium fluoride; the acid pyridine sodium hydrochloride is at least one of acetic acid pyridine sodium hydrochloride, formic acid pyridine sodium hydrochloride and propionic acid pyridine sodium hydrochloride; the alkyl sodium is at least one of methyl sodium, ethyl sodium, propyl sodium and butyl sodium; the ammonium salt is at least one of ammonium chloride, ammonium sulfate, ammonium bisulfate, ammonium nitrate, ammonium carbonate, ammonium bicarbonate, ammonium fluoride, ammonium iodide and ammonium bromide; the thiocarbonate is at least one of sodium thiocarbonate, potassium thiocarbonate, calcium thiocarbonate, magnesium thiocarbonate, cobalt thiocarbonate, copper thiocarbonate and zinc thiocarbonate; the thiocyanate is at least one of potassium thiocyanate, ammonium thiocyanate, sodium thiocyanate, potassium thiocyanate, calcium thiocyanate, magnesium thiocyanate, cobalt thiocyanate, copper thiocyanate and zinc thiocyanate; the borate is at least one of sodium borate, potassium borate, calcium borate, magnesium borate, cobalt borate, copper borate and zinc borate; the citrate is at least one of sodium citrate, potassium citrate, calcium citrate, magnesium citrate, cobalt citrate, copper citrate and zinc citrate; the silicate is at least one of sodium silicate, potassium silicate, calcium silicate, magnesium silicate, cobalt silicate, copper silicate, zinc silicate and lithium silicate; the phosphoric acid is at least one of sodium phosphate, potassium phosphate, magnesium phosphate, calcium phosphate, zinc phosphate, ferrous phosphate, copper phosphate, lithium phosphate and lithium iron phosphate; the hydrogen phosphate is at least one of sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, magnesium hydrogen phosphate, calcium hydrogen phosphate, zinc hydrogen phosphate, ferrous phosphate, lithium dihydrogen phosphate and lithium hydrogen phosphate.
As a preferred embodiment of the invention, the emulsion is polyvinyl acetate emulsion, vinyl acetate/acrylate copolymer emulsion, vinyl acetate/ethylene copolymer emulsion, styrene/acrylate copolymer emulsion, organosilicon modified acrylate emulsion, styrene-acrylic emulsion, polyurethane emulsion, acrylic emulsion, silicone-acrylic emulsion, polyisocyanate emulsion, at least one of epoxy resin modified acrylate emulsion, fluorine-containing styrene-acrylic emulsion, starch and polyvinyl acetal modified polyvinyl acetate emulsion, vinyl acetate butyl acrylate tertiary carbonate copolymer emulsion, rosin emulsion, polysiloxane emulsion, organic silicon emulsion, styrene-butadiene latex, polyvinyl acetate emulsion, neoprene latex, (methyl) acrylate copolymer emulsion, vinyl acetate-acrylic emulsion and modified substances of the above emulsions.
The emulsion has the function of reinforcing a hydrogel-like structure, helps the hydrogel-like structure to form a point-line mixed functional structure, controllably breaks the emulsion and releases polymer structures containing different functional functions in the later cold pressing and hot press molding processes, and promotes the hydrogel-like high-molecular network structures forming different functional structures and the rapid reaction of the hydrogel-like high-molecular network structures with the reinforcing material under the conditions of normal temperature, cold pressing, high temperature and high pressure.
The preparation method of the emulsion is at least one of free radical emulsion polymerization, inverse emulsion polymerization, miniemulsion polymerization, microemulsion polymerization, soap-free emulsion polymerization and core-shell type composite emulsion polymerization.
As a preferred embodiment of the present invention, the surfactant is disodium lauryl sulfosuccinate monoester, disodium fatty alcohol polyoxyethylene ether (3) sulfosuccinate monoester, disodium cocomonoethanolamide sulfosuccinate monoester, monolauryl phosphate, potassium monolauryl phosphate, alcohol ether phosphate, potassium lauryl alcohol ether phosphate, fatty alcohol polyoxyethylene ether (E0 ═ 3) ammonium sulfate, cocomonoethanolamide, cocodiethanolamide, cocoamidopropyl betaine, lauramidopropyl betaine, cocoamidopropyl hydroxysultaine, lauramidopropyl amine oxide, sodium lauryl amphoacetate, potassium soap fatty acid, sodium lauryl sulfate, sodium cetyl sulfate, sodium stearyl sulfate, sucrose fatty acid ester, sorbitan fatty acid, polyoxyethylene sorbitan fatty acid ester, sodium lauryl sulfosuccinate, sodium lauryl alcohol ether phosphate, sodium cocoamidopropyl hydroxysultaine, sodium lauryl alcohol ether phosphate, sodium lauryl ether phosphate, fatty alcohol polyoxyethylene sorbitan fatty acid ester, sodium lauryl sulfate, sodium lauryl amphoacetate, sodium lauryl alcohol sulfate, sodium stearyl alcohol sulfate, sucrose fatty acid ester, sorbitan fatty acid ester, sodium lauryl ether, sodium lauryl sulfate, sodium lauryl hydroxysultaine, sodium hydroxysultaine, and sodium hydroxysultaine, At least one of polyoxyethylene fatty acid ester, polyoxyethylene fatty alcohol ether, polyoxyethylene-polyoxypropylene copolymer, sodium octyl sulfonate, sodium octyl sulfate, potassium stearate, potassium oleate, potassium laurate, dodecylamine chloride, sugarcane laurate, and modified surfactant.
The surfactant disclosed by the invention is mainly used for reducing the layering phenomenon of the adhesive and improving the stability of the glue during the storage period.
As a preferred embodiment of the present invention, the reinforcing material comprises a water-reactive compound and an auxiliary reinforcing aid; the weight ratio of the water-reactive compound to the auxiliary reinforcing auxiliary agent is 70-100: 0 to 30; the water-reactive compound is one or two-component isocyanate resin and a modified product thereof, preferably, the water-reactive compound is at least one of diphenylmethane-4, 4-diisocyanate resin, trimethylhexamethylene diisocyanate resin, 1, 6-hexamethylene diisocyanate, toluene diisocyanate resin, 4-dicyclohexylmethane diisocyanate resin, p-tetramethylxylene diisocyanate, isophorone diisocyanate resin, methylene polyphenyl isocyanate adhesive, water-soluble isocyanate adhesive and a modified product of the water-reactive compound; the auxiliary reinforcing additive is at least one of bisphenol A type epoxy resin, bisphenol F type epoxy resin, polyphenol type glycidyl ether epoxy resin, aliphatic glycidyl ether epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, epoxidized olefin compound, unsaturated polyester, heterocyclic polymer, melamine resin, chloroprene rubber, butyl nitrile ethylene propylene rubber, fluorine rubber, polyisobutylene, polysulfide rubber, natural rubber, chlorosulfonated polyethylene rubber, polyvinyl chloride, cellulose ester, vinyl polymer, polyester, polyether, polyamide, polyacrylate, a-cyanoacrylate, polyvinyl acetal and ethylene-vinyl acetate copolymer.
When the auxiliary reinforcing auxiliary agent is added into the system, the bonding strength of the glue and the storage stability of the glue are improved.
The invention also claims the aqueous aldehyde-free adhesive prepared by the preparation method of the aqueous aldehyde-free adhesive.
In addition, the invention also protects the application of the water-based aldehyde-free adhesive in preparing the artificial board.
The artificial board is a plywood, a shaving board or a fiberboard.
The preparation method of the plywood comprises the following steps:
s1: uniformly mixing the water-based formaldehyde-free adhesive and the flour, and then performing single-side sizing or double-side sizing on the veneer to obtain a sized veneer;
s2: the glued veneers are subjected to assembly and splicing for 0.5-10 hours, and then are subjected to cold pressing for 0.5-6 hours under the pressure of 8-18 Mpa;
s3: and (3) carrying out hot pressing on the board treated by the S2 at the pressure of 5.0-25.0 Mpa and the temperature of 50-250 ℃, wherein the hot pressing rate is 0.5-2.0 mm/min, thus obtaining the plywood.
As a preferred embodiment of the invention, the mass ratio of the water-based formaldehyde-free adhesive to the flour is 1: 0.01 to 0.5.
In S1, a single-side sizing or a double-side sizing is performed on the veneer by using a rubber roll size press.
In a preferred embodiment of the present invention, the amount of the sizing agent in S1 is 50 to 500g/m2. The amount of the glue applied is within the above range, and the prepared plate has initial viscosity, bonding strength and activity periodBetter and lower cost.
More preferably, in the S1, the glue application amount is 100-180 g/m2. The glue application amount is in the range, the initial viscosity, the bonding strength and the activity period of the prepared plate are optimal, and the cost is lowest.
Compared with the prior art, the invention has the beneficial effects that:
(1) the preparation method of the water-based aldehyde-free adhesive comprises the steps of firstly locking a part of water molecules in a system in a network nano structure of hydrogel in a physical and ionic bonding mode, forming a special water molecule-polymer grid co-embedded film structure through a process technology, then embedding the other part of water molecules in the hydrogel structure in a micro-emulsion combination mode to form a layer of regular nano water film structure, and finally forming a stable water-based emulsion/composite gel system through a surfactant and the process technology thereof, wherein the system structure has good structural strength and a water molecule nano film structure. The water molecules of the water-based emulsion/composite gel system are embedded in the water gel structure in a multi-layer nano water film mode, so that the common problems that the reaction activity of the water-reactive compound in the glue is greatly reduced or the glue is gelled due to the fact that the water-reactive compound can rapidly react with the water molecules because of the extremely high active groups of the water-reactive compound, and meanwhile the gluing performance of the glue is reduced or glue rollers and metal mechanical equipment are glued are solved.
(2) The water-based formaldehyde-free adhesive with the co-embedded structure prepared by the invention has the effects of good initial viscosity, high stability, long activity period, toughening, water resistance, high adhesion and no formaldehyde release, and can meet the technical requirements of the continuous production process of common veneers.
(3) The preparation method of the water-based formaldehyde-free adhesive has the characteristics of no toxicity, no pollution and low cost, does not need to change the use habit of a factory, and does not need new equipment investment and increase the operation amount of workers.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Example 1
The preparation method of the aqueous aldehyde-free adhesive comprises the following steps:
(1) dissolving polyvinyl alcohol in water at 100 ℃ to obtain a high polymer solution, wherein the mass concentration of a high polymer in the high polymer solution is 40%;
(2) reducing the temperature to 80 ℃, adding sodium acetate into the high polymer solution, adjusting the pH value to 7, and stirring and reacting for 10 hours under the conditions of nitrogen atmosphere, 10MPa of pressure and 80 ℃ to obtain the hydrogel-like substance;
(3) adding vinyl acetate/acrylate copolymer emulsion and disodium lauryl sulfosuccinate monoester into the hydrogel under the conditions of the pressure of 8MPa and the temperature of 80 ℃ in the nitrogen atmosphere, then reacting for 8 hours under the conditions of the pressure of 10MPa and the temperature of 0 ℃, and adjusting the pH value to 7 to form an emulsion/composite water gel system;
(4) adding 1, 6-hexamethylene diisocyanate and polyvinyl chloride into the emulsion/composite water-gel system to adjust the pH value to 7, and reacting for 7 hours under the conditions of nitrogen atmosphere, 10MPa of pressure and 60 ℃ of temperature to obtain the water-based aldehyde-free adhesive.
The aqueous formaldehyde-free adhesive comprises the following preparation raw materials in percentage by mass: 68.9 percent of polyvinyl alcohol, 10 percent of sodium acetate, 20 percent of vinyl acetate/acrylate copolymer emulsion, 1 percent of disodium lauryl sulfosuccinate monoester, 10 percent of 1, 6-hexamethylene diisocyanate and 0.1 percent of polyvinyl chloride.
The preparation method of the plywood comprises the following steps:
s1: uniformly mixing the water-based formaldehyde-free adhesive and flour, and performing single-side gluing on the veneer by using a rubber roller glue applicator to obtain a glued veneer; the adding amount of the flour accounts for 20% of the mass of the water-based formaldehyde-free adhesive; the amount of glue applied to one side was 160g/m2；
S2: the glued veneers are assembled and spliced for 6 hours and then are cold-pressed for 2 hours under the pressure of 10.0 MPa;
s3: and (3) carrying out hot pressing on the board treated by the S2 at the pressure of 15.0Mpa and the temperature of 120 ℃, wherein the hot pressing speed is 1.0mm/min, thus obtaining the plywood.
Example 2
The preparation method of the aqueous aldehyde-free adhesive comprises the following steps:
(1) dissolving carboxymethyl cellulose in water at 50 ℃ to obtain a high polymer solution, wherein the mass concentration of a high polymer in the high polymer solution is 30%;
(2) reducing the temperature to 20 ℃, adding sodium silicate into the high polymer solution, adjusting the pH value to 2, and stirring and reacting for 72 hours under the conditions of nitrogen atmosphere, pressure of-1 MPa and temperature of 0 ℃ to obtain the hydrogel-like substance;
(3) under the conditions of 1MPa of pressure and 0 ℃ of temperature in nitrogen atmosphere, adding polyvinyl acetate emulsion and potassium monododecyl phosphate into the hydrogel, then reacting for 12 hours under the conditions of 1MPa of pressure and 80 ℃ of temperature, and adjusting the pH value to 12 to form an emulsion/composite hydrogel system;
(4) adding a water-soluble isocyanate adhesive into the emulsion/composite water adhesive system to adjust the pH value to 11, and reacting for 0.1min under the conditions of nitrogen atmosphere, pressure of-20 MPa and temperature of 180 ℃ to obtain the water-based aldehyde-free adhesive.
The aqueous formaldehyde-free adhesive comprises the following preparation raw materials in percentage by mass: 98% of carboxymethyl cellulose, 0.01% of sodium silicate, 0.1% of polyvinyl acetate emulsion, 0.89% of potassium monododecyl phosphate and 1% of water-soluble isocyanate adhesive.
The preparation method of the plywood comprises the following steps:
s1: uniformly mixing the water-based formaldehyde-free adhesive and flour, and then carrying out double-side gluing on the veneer by using a rubber roller glue applicator to obtain a glued veneer; the adding amount of the flour accounts for 1 percent of the mass of the water-based formaldehyde-free adhesive; the amount of glue applied was 100g/m2；
S2: the glued veneers are assembled and spliced for 0.5 hour, and then cold-pressed for 0.5 hour under 18 Mpa;
s3: and (3) carrying out hot pressing on the board treated by the S2 at the pressure of 5.0Mpa and the temperature of 250 ℃, wherein the hot pressing speed is 0.5mm/min, thus obtaining the plywood.
Example 3
The preparation method of the aqueous aldehyde-free adhesive comprises the following steps:
(1) dissolving carboxymethyl cellulose in water at 200 ℃ to obtain a high polymer solution, wherein the mass concentration of a high polymer in the high polymer solution is 0.1%;
(2) adjusting the temperature to 200 ℃, adding sodium silicate into the high polymer solution, adjusting the pH value to 2, and stirring and reacting for 0.1min under the conditions of nitrogen atmosphere, 10MPa of pressure and 170 ℃ to obtain the hydrogel-like substance;
(3) under the conditions of nitrogen atmosphere, pressure of-10 MPa and temperature of 250 ℃, adding polyvinyl acetate emulsion and potassium monododecyl phosphate into the hydrogel, then reacting for 12 hours under the conditions of pressure of 15.0MPa and temperature of 200 ℃, and adjusting the pH value to 12 to form an emulsion/composite water gel system;
(4) adding a water-soluble isocyanate adhesive into the emulsion/composite water adhesive system to adjust the pH value to 11, and reacting for 0.1min under the conditions of a nitrogen atmosphere, a pressure of 20.0MPa and a temperature of 180 ℃ to obtain the water-based aldehyde-free adhesive.
The aqueous formaldehyde-free adhesive comprises the following preparation raw materials in percentage by mass: 98% of carboxymethyl cellulose, 0.01% of sodium silicate, 0.1% of polyvinyl acetate emulsion, 0.89% of potassium monododecyl phosphate and 1% of water-soluble isocyanate adhesive.
The preparation method of the plywood comprises the following steps:
s1: uniformly mixing the water-based formaldehyde-free adhesive and flour, and then carrying out double-side gluing on the veneer by using a rubber roller glue applicator to obtain a glued veneer; the adding amount of the flour accounts for 50% of the mass of the water-based formaldehyde-free adhesive; the amount of glue applied was 180g/m2；
S2: the glued veneers are assembled and spliced for 10 hours, and then cold-pressed for 5 hours under 10 Mpa;
s3: and (3) carrying out hot pressing on the board treated by the S2 at the pressure of 25.0Mpa and the temperature of 50 ℃, wherein the hot pressing speed is 2.0mm/min, thus obtaining the plywood.
Example 4
The preparation method of the aqueous aldehyde-free adhesive comprises the following steps:
(1) dissolving starch in water at 120 ℃ to obtain a high polymer solution, wherein the mass concentration of a high polymer in the high polymer solution is 50%;
(2) adjusting the temperature to 120 ℃, adding sodium chloride into the high polymer solution, adjusting the pH value to 10, and stirring and reacting for 12 hours under the conditions of nitrogen atmosphere, pressure of-30 MPa and temperature of-10 ℃ to obtain hydrogel-like substance;
(3) adding silicone-acrylic emulsion and potassium lauryl alcohol ether phosphate into the hydrogel under the conditions of the pressure of 8.0MPa and the temperature of-15 ℃, then reacting for 0.1min under the conditions of the pressure of-15 MPa and the temperature of-10 ℃, and adjusting the pH value to 3 to form an emulsion/composite water gel system;
(4) adding trimethylhexamethylene diisocyanate resin into the emulsion/composite water-gel system to adjust the pH value to be 2, and reacting for 72 hours under the conditions of nitrogen atmosphere, pressure of-20 MPa and temperature of-30 ℃ to obtain the water-based aldehyde-free adhesive.
The aqueous formaldehyde-free adhesive comprises the following preparation raw materials in percentage by mass: 1% of starch, 8.9% of sodium chloride, 0.1% of silicone-acrylic emulsion, 10% of potassium lauryl alcohol ether phosphate and 80% of trimethyl hexamethylene diisocyanate resin.
The plywood was prepared in the same manner as in example 1.
Example 5
The preparation method of the aqueous aldehyde-free adhesive comprises the following steps:
(1) dissolving hydroxypropyl cellulose in water at 100 ℃ to obtain a high polymer solution, wherein the mass concentration of a high polymer in the high polymer solution is 40%;
(2) cooling to 80 ℃, adding calcium citrate into the high polymer solution, adjusting the pH value to 7, and stirring under the conditions of nitrogen atmosphere, pressure of 6.0MPa and temperature of 100 ℃ until the reaction is complete to obtain the hydrogel-like product;
(3) under the conditions of nitrogen atmosphere, pressure of 4.0MPa and temperature of 150 ℃, adding styrene-butadiene latex into the quasi-hydrogel, then reacting for 8 hours under the conditions of pressure of 10.0MPa and temperature of 100 ℃, and adjusting the pH value to be 7 to form an emulsion/composite water gel system;
(4) adding tetramethylene xylene diisocyanate and chloroprene rubber into the emulsion/composite water-based adhesive system to adjust the pH value to 7, and reacting for 7 hours under the conditions of nitrogen atmosphere, pressure of 8.0MPa and temperature of 120 ℃ to obtain the aqueous aldehyde-free adhesive.
The aqueous formaldehyde-free adhesive comprises the following preparation raw materials in percentage by mass: 19.64 percent of hydroxypropyl cellulose, 80 percent of calcium citrate, 0.1 percent of styrene-butadiene latex, 0.1 percent of tetramethylene xylene diisocyanate and 0.16 percent of chloroprene rubber.
The plywood was prepared in the same manner as in example 1.
Example 6
The preparation method of the aqueous aldehyde-free adhesive comprises the following steps:
(1) dissolving polyvinyl alcohol in water at 120 ℃ to obtain a high polymer solution, wherein the mass concentration of a high polymer in the high polymer solution is 15%;
(2) reducing the temperature to 80 ℃, adding sodium acetate into the high polymer solution, adjusting the pH value to 7, and stirring and reacting for 10 hours under the conditions of air atmosphere, pressure of 10MPa and temperature of 80 ℃ to obtain hydrogel-like substance;
(3) adding vinyl acetate/acrylate copolymer emulsion and disodium lauryl sulfosuccinate monoester into the quasi-hydrogel under the conditions of air atmosphere, pressure of 1MPa and temperature of 80 ℃, then reacting for 8 hours under the conditions of pressure of 10MPa and temperature of 0 ℃, and adjusting the pH value to 7 to form an emulsion/composite water gel system;
(4) adding 1, 6-hexamethylene diisocyanate into the emulsion/composite water-gel system to adjust the pH value to 7, and reacting for 7 hours under the conditions of air atmosphere, pressure of 10MPa and temperature of 80 ℃ to obtain the water-based aldehyde-free adhesive.
The aqueous formaldehyde-free adhesive comprises the following preparation raw materials in percentage by mass: 68.9 percent of polyvinyl alcohol, 10 percent of sodium acetate, 20 percent of vinyl acetate/acrylate copolymer emulsion, 1 percent of disodium lauryl sulfosuccinate monoester, 10 percent of 1, 6-hexamethylene diisocyanate and 0.1 percent of polyvinyl chloride.
The preparation method of the plywood comprises the following steps:
s1: uniformly mixing the water-based formaldehyde-free adhesive and flour, and then carrying out double-side gluing on the veneer by using a rubber roller glue applicator to obtain a glued veneer; the adding amount of the flour accounts for 20% of the mass of the water-based formaldehyde-free adhesive; the amount of glue applied was 160g/m2；
S2: the glued veneers are assembled and spliced for 6 hours, and then cold-pressed for 6 hours under 8 Mpa;
s3: and (3) carrying out hot pressing on the board treated by the S2 at the pressure of 15.0Mpa and the temperature of 120 ℃, wherein the hot pressing speed is 1.0mm/min, thus obtaining the plywood.
Comparative example 1
The preparation method of the aqueous aldehyde-free adhesive comprises the following steps:
(1) dissolving polyvinyl alcohol in water at 100 ℃ to obtain a high polymer solution, wherein the mass concentration of a high polymer in the high polymer solution is 40%;
(2) reducing the temperature to 80 ℃, adjusting the pH value to 7, and stirring and reacting for 10 hours under the conditions of nitrogen atmosphere, pressure of 10.0MPa and temperature of 80 ℃ to obtain hydrogel-like compound;
(3) adding vinyl acetate/acrylate copolymer emulsion and disodium lauryl sulfosuccinate monoester into the hydrogel under the conditions of nitrogen atmosphere, pressure of 8.0MPa and temperature of 80 ℃, then reacting for 8 hours under the conditions of pressure of 10.0MPa and temperature of 0 ℃, and adjusting the pH value to 7 to form an emulsion/composite water gel system;
(4) adding 1, 6-hexamethylene diisocyanate and polyvinyl chloride into the emulsion/composite water adhesive system to adjust the pH value to 7, and reacting for 7 hours under the conditions of nitrogen atmosphere, pressure of 10.0MPa and temperature of 60 ℃ to obtain the water-based aldehyde-free adhesive.
The aqueous formaldehyde-free adhesive comprises the following preparation raw materials in percentage by mass: 78.9 percent of polyvinyl alcohol, 20 percent of vinyl acetate/acrylate copolymer emulsion, 1 percent of lauryl sodium sulfosuccinate monoester, 10 percent of 1, 6-hexamethylene diisocyanate and 0.1 percent of polyvinyl chloride.
The plywood was prepared in the same manner as in example 1.
Comparative example 2
The preparation method of the aqueous aldehyde-free adhesive comprises the following steps:
(1) dissolving polyvinyl alcohol in water at 100 ℃ to obtain a high polymer solution, wherein the mass concentration of a high polymer in the high polymer solution is 40%;
(2) cooling to 80 ℃, adding sodium acetate into the high polymer solution, adjusting the pH value to 7, and stirring and reacting for 10 hours under the conditions of nitrogen atmosphere, pressure of 10.0MPa and temperature of 80 ℃ to obtain hydrogel-like substance;
(3) adding 1, 6-hexamethylene diisocyanate and polyvinyl chloride into the hydrogel to adjust the pH value to 7, and reacting for 7 hours under the conditions of nitrogen atmosphere, pressure of 10.0MPa and temperature of 60 ℃ to obtain the aqueous aldehyde-free adhesive.
The aqueous formaldehyde-free adhesive comprises the following preparation raw materials in percentage by mass: 68.9 percent of polyvinyl alcohol, 10 percent of sodium acetate, 21 percent of 1, 6-hexamethylene diisocyanate and 0.1 percent of polyvinyl chloride.
The plywood was prepared in the same manner as in example 1.
Test example 1
Test samples: the aqueous aldehyde-free adhesives and plywood prepared in examples 1-6 and comparative examples 1-2; the control group is raw veneer of plywood.
The test method comprises the following steps: and (3) testing the formaldehyde emission: according to the standard GB/T39600-2021 Classification of formaldehyde emission of artificial boards and products thereof, a climatic box method is adopted to test the formaldehyde emission.
And (3) viscosity testing: the viscosity test of the aqueous aldehyde-free adhesives prepared in examples 1-6 and comparative examples 1-2 is carried out according to GB/T14074-2017, the aqueous aldehyde-free adhesives are respectively stirred uniformly, three samples are taken from each group, the samples are tested by a rotary viscometer at 23 ℃, and the average value of 3 tests is taken.
Testing internal bonding strength: respectively cutting 15 parts of the plywood prepared in the examples 1-6 and the comparative examples 1-2, adopting the detection requirements of GB/T9846-2015 common plywood and the sample processing steps and methods, testing by using a universal mechanics experiment, tightening the plywood, uniformly loading, breaking the test piece within 60 +/-30 s from loading, recording the maximum load value, and dividing by the area of the test piece to obtain the bonding strength in the test piece. The average value of each test piece was taken as the internal bond strength.
And (3) testing the boiling resistance: 15 parts of the plywood prepared in the examples 1-6 and the comparative examples 1-2 are respectively cut, the sample is immersed in boiling water for boiling, the boiling time is calculated for 80 hours, the condition of breakage is observed, and the internal bonding strength is detected according to the detection requirement of GB/T9846-2015 ordinary plywood, the sample processing steps and the method.
Testing the using activity cycle performance of the glue: applying glue to a single wood board with the water content of 5-20 wt% on a gluing machine at a single side of 160g/m2After gluing, according to a 9-layer structure of a plywood assembly, timing is started after gluing is finished, cold pressing (the cold pressing pressure is 13.0MPa) is carried out for 1 hour within 1-10 hours of the calculated time, then the plywood is repaired and kept stand, hot pressing treatment (110 ℃, 12.0MPa and 1min/mm) is carried out until the time reaches 35 hours, and after the hot pressing is finished for 48 hours, the internal shearing and gluing strength is detected according to GB/T9846-2015 'common plywood'.
Testing the glue storage activity period: storing the adhesive in a plastic barrel or a metal barrel under the condition of normal temperature and normal humidity, starting to calculate time, sampling every 1 day to check whether the color of the adhesive is changed and whether the adhesive is layered, testing the quality of the adhesive and the strength of a plate according to a method for testing the using activity period performance of the adhesive, prolonging the storage time until the strength of the hot-pressed plate is not lost, and recording the longest storage activity period.
The test results are shown in table 1:
table 1 Performance test results for the aqueous aldehyde-free adhesive and plywood
According to the data results in the table 1, the aqueous aldehyde-free adhesive prepared by the invention has the effects of good initial viscosity, high stability, long activity period, water resistance, high adhesion and no formaldehyde release, and can meet the technical requirements of the continuous production process of common artificial boards.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The preparation method of the water-based formaldehyde-free adhesive is characterized by comprising the following steps:
(1) completely dissolving a water-soluble poly-element structure compound in water at 0-200 ℃ to obtain a high polymer solution;
(2) adjusting the temperature to 0-200 ℃, adding a reactive assistant into the high polymer solution, adjusting the pH value to 2-10, and stirring and reacting for 1.0 min-72 h under the conditions of gas atmosphere, pressure of-30 MPa-10 MPa and temperature of-10-170 ℃ to obtain hydrogel-like product;
(3) adding emulsion and surfactant into the quasi-hydrogel prepared in the step (2) under the conditions of gas atmosphere, pressure of-10 MPa to 8MPa and temperature of-15 ℃ to 250 ℃, then mixing and reacting for 1.0min to 72h under the conditions of pressure of-15 MPa to 15MPa and temperature of-10 ℃ to 200 ℃, and adjusting the pH value to 3 to 12 after the reaction is finished to form an emulsion/composite hydrogel system;
(4) adding a reinforcing material into an emulsion/composite water-based adhesive system to adjust the pH value to 2-11, and then mixing and reacting for 0.1 min-72 h under the conditions of gas atmosphere, pressure of-20 MPa and temperature of-30 ℃ to 180 ℃ to obtain the water-based aldehyde-free adhesive.
2. The preparation method of the aqueous aldehyde-free adhesive as claimed in claim 1, wherein the aqueous aldehyde-free adhesive comprises the following preparation raw materials in percentage by mass: 1 to 98 percent of water-soluble poly-multi-element structure compound, 0.01 to 80 percent of active additive, 0.1 to 80 percent of emulsion, 0 to 10 percent of surfactant and 0.1 to 80 percent of reinforcing material; the mass concentration of the high polymer in the high polymer solution is 0.1-50%.
3. The method of claim 1, wherein the water-soluble polyaldehyde binder is at least one of starch, gum arabic, sodium alginate, bone meal, gelatin, cyclodextrin, casein, carboxymethyl cellulose, carboxyethyl cellulose, carboxypropyl cellulose, carboxybutyl cellulose, methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxybutyl cellulose, polyacrylamide, polypropyleneimine, polyacrylamide, polyisobutylene amine, polyvinylpyrrolidone, polyvinyl alcohol, polypropylene alcohol, polyvinyl chloride alcohol, polyethyleneimine, soy protein, zein, polymaleic anhydride, polyquaternary ammonium salts, polyethylene glycol, starch derivatives, and modifications thereof.
4. The method of claim 1, wherein the coagent is at least one of acetate, sulfate, bisulfate, chloride, bromide, iodide, carbonate, bicarbonate, nitrate, tetrabutylammonium halide, sodium picolinate, alkyl sodium, ammonium salt, thiocarbonate, thiocyanate, phosphate, borate, citrate, phosphate, hydrogen phosphate, potassium dodecyl salt, sodium dodecyl salt, quaternary tetraalkylammonium salt, octadecyl amine acetate, cocoamine acetate, oleyl amine hydrochloride, hydrogenated tallow amine hydrochloride.
5. The method for preparing the aqueous aldehyde-free adhesive according to claim 1, wherein the emulsion is a polyvinyl acetate emulsion, a vinyl acetate/acrylate copolymer emulsion, a vinyl acetate/ethylene copolymer emulsion, a styrene/acrylate copolymer emulsion, an acrylate copolymer emulsion, a silicone-modified acrylate emulsion, a styrene-acrylic emulsion, a urethane emulsion, an acrylic emulsion, a silicone-acrylic emulsion, a polyisocyanate emulsion, an epoxy resin-modified acrylate emulsion, a fluorine-containing styrene-acrylic emulsion, a starch and polyvinyl acetal-modified polyvinyl acetate emulsion, a vinyl acetate butyl acrylate-t-carbonate copolymer emulsion, a rosin emulsion, a polysiloxane emulsion, an organosilicon emulsion, a styrene-butadiene latex, a polyvinyl acetate emulsion, a chloroprene latex, a (meth) acrylate copolymer emulsion, a silicone-modified acrylic emulsion, a styrene-butadiene latex, a polyvinyl acetate emulsion, a chloroprene latex, a (meth) acrylate copolymer emulsion, a silicone-modified acrylic copolymer emulsion, a silicone-acrylate copolymer emulsion, a silicone-modified acrylic copolymer, a silicone-acrylate copolymer emulsion, a silicone-modified acrylic copolymer, a silicone copolymer, and a silicone copolymer, and a silicone copolymer, a copolymer, and a copolymer, and a copolymer, Vinyl acetate-acrylic emulsion and/or modified product of the above emulsion.
6. The method of preparing the aqueous aldehyde-free adhesive of claim 1, wherein the surfactant is disodium lauryl sulfosuccinate, disodium fatty alcohol polyoxyethylene (3) sulfosuccinate, disodium cocomonoethanolamide sulfosuccinate, monolauryl phosphate, potassium monolauryl phosphate, alcohol ether phosphate, potassium lauryl alcohol ether phosphate, fatty alcohol polyoxyethylene ether (E0 ═ 3) ammonium sulfate, cocomonoethanolamide, cocodiethanolamide, cocoamidopropyl betaine, lauramidopropyl betaine, cocamidopropyl hydroxysultaine, lauramidopropyl amine oxide, sodium lauryl acetate, fatty acid potassium soap, sodium lauryl sulfate, sodium cetyl sulfate, sodium stearyl sulfate, sucrose fatty acid esters, fatty acid sorbitan, At least one of polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty alcohol ether, polyoxyethylene-polyoxypropylene copolymer, sodium octyl sulfonate, sodium octyl sulfate, potassium stearate, potassium oleate, potassium laurate, dodecylamine chloride, sugarcane laurate, and modified substance of the above surfactant.
7. The method of preparing the aqueous aldehyde-free adhesive of claim 1, wherein the reinforcing material comprises a water-reactive compound, a co-reinforcing aid; the weight ratio of the water-reactive compound to the auxiliary reinforcing auxiliary agent is 70-100: 0 to 30 parts by weight; the water-reactive compound is at least one of diphenylmethane-4, 4-diisocyanate resin, trimethylhexamethylene diisocyanate resin, 1, 6-hexamethylene diisocyanate, toluene diisocyanate resin, 4-dicyclohexylmethane diisocyanate resin, p-tetramethylene xylene diisocyanate, isophorone diisocyanate resin, methylene polyphenyl isocyanate adhesive, water-soluble isocyanate adhesive and a modified product of the water-reactive compound; the auxiliary reinforcing additive is at least one of bisphenol A type epoxy resin, bisphenol F type epoxy resin, polyphenol type glycidyl ether epoxy resin, aliphatic glycidyl ether epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, epoxidized olefin compound, unsaturated polyester, heterocyclic polymer, melamine resin, chloroprene rubber, butyl nitrile ethylene propylene rubber, fluorine rubber, polyisobutylene, polysulfide rubber, natural rubber, chlorosulfonated polyethylene rubber, polyvinyl chloride, cellulose ester, vinyl polymer, polyester, polyether, polyamide, polyacrylate, a-cyanoacrylate, polyvinyl acetal and ethylene-vinyl acetate copolymer.
8. The method for preparing the aqueous aldehyde-free adhesive according to claim 1, wherein the gas atmosphere is at least one of normal air, nitrogen, oxygen, argon and carbon dioxide.
9. An aqueous aldehyde-free adhesive prepared by the process for preparing an aqueous aldehyde-free adhesive according to any one of claims 1 to 8.
10. Use of the aqueous aldehyde-free adhesive of claim 9 in the preparation of an artificial board.
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