CN113072903B - Preparation method of decorative wood board waterproof adhesive - Google Patents
Preparation method of decorative wood board waterproof adhesive Download PDFInfo
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- CN113072903B CN113072903B CN202110447535.3A CN202110447535A CN113072903B CN 113072903 B CN113072903 B CN 113072903B CN 202110447535 A CN202110447535 A CN 202110447535A CN 113072903 B CN113072903 B CN 113072903B
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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
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C09J161/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C09J161/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/10—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with acyclic compounds having the moiety X=C(—N<)2 in which X is O, S or —N
- C08G12/12—Ureas; Thioureas
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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Abstract
A preparation method of a decorative wood board waterproof adhesive belongs to the field of adhesives. Adding weighed formaldehyde into a flask, adjusting the pH value of the formaldehyde to 7.5-8.0 by using a sodium hydroxide solution, heating to 35-40 ℃ under the condition of stirring, slowly dripping a first part of urea solution into the flask, then heating to 45-50 ℃ for constant temperature reaction for 1-1.5h, adding acetic acid to adjust the pH value to 6-6.5, then adding a certain mass of zinc stearate, uniformly stirring, heating to 55-60 ℃ after the reaction temperature is raised, then slowly dripping a second part of urea solution into the flask, then performing constant temperature reaction for 1-1.5h, adding a certain mass of modified nano titanium dioxide, then adding a third part of urea solution, adding a mildew preventive, a flame retardant and a stabilizer after the reaction, stirring for constant temperature reaction for 2-5h, cooling to normal temperature, and discharging to obtain the product. The invention is used in the field of wood adhesives.
Description
Technical Field
The invention belongs to the field of adhesives; in particular to a preparation method of a decorative wood board waterproof adhesive.
Background
The urea-formaldehyde resin adhesive is an indispensable product in the industries of buildings, wood processing industry, light industry, aviation technology and the like, has very wide application, is the most widely applied adhesive, and has the characteristics of high curing speed, simple synthesis process, convenient use, good performance, low cost, high bonding strength and low price. In China, the usage amount of the urea resin adhesive in the wood adhesive reaches more than 80%.
The urea-formaldehyde resin adhesive is used for solving three problems in product quality, namely free formaldehyde emission, bonding strength and waterproofness. The existing urea-formaldehyde resin adhesive manufacturers can not solve the three problems at the same time, and particularly have more problems in the aspects of formaldehyde release and waterproof performance.
How to prepare the urea-formaldehyde resin adhesive which can ensure low formaldehyde emission and good waterproof performance is a difficult problem faced by current urea-formaldehyde resin adhesive manufacturers.
Disclosure of Invention
The invention aims to provide a decorative wood board waterproof adhesive with good waterproof performance and a preparation method thereof.
The invention is realized by the following technical scheme:
a preparation method of a decorative wood board waterproof adhesive comprises the following steps:
step 1, weighing formaldehyde and urea with certain mass according to a molar ratio, preparing the weighed urea into a urea solution, and then evenly dividing the urea solution into four equal parts according to the volume ratio for later use;
step 2, adding the formaldehyde weighed in the step 1 into a flask, adjusting the pH value of the formaldehyde to 7.5-8.0 by using a sodium hydroxide solution, heating to the temperature of 35-40 ℃ under the condition of stirring, slowly dripping a first urea solution into the flask, then heating to the temperature of 45-50 ℃ for constant-temperature reaction for 1-1.5h to obtain a first reaction solution for later use;
step 3, adding acetic acid into the first reaction liquid obtained in the step 2 to adjust the pH value to 6-6.5, then adding zinc stearate with a certain mass, uniformly stirring, raising the reaction temperature to 55-60 ℃, then slowly dripping a second part of urea solution into the flask, and then reacting at constant temperature for 1-1.5 hours to obtain a second reaction liquid for later use;
step 4, adding a certain mass of modified nano titanium dioxide into the second reaction solution obtained in the step 3, adjusting the pH to 7.5-8.0 by using a sodium hydroxide solution under the condition of ultrasonic stirring, adding a third part of urea solution, heating to 60-70 ℃, and reacting at constant temperature for 1 hour to obtain a third reaction solution for later use;
and 5, regulating the pH value of formaldehyde to 8.0-8.5 by using a sodium hydroxide solution in the third reaction solution obtained in the step 4, slowly dripping a fourth urea solution into the flask under the stirring condition, then adding a mildew inhibitor, a flame retardant and a stabilizer, stirring for reacting at a constant temperature for 2-5h, cooling to the normal temperature, and discharging to obtain the decorative wood board waterproof adhesive.
The preparation method of the decorative wood board waterproof adhesive comprises the following steps of 1-1.1 mol ratio of formaldehyde to urea in step 1, 37-40wt% of formaldehyde and 0.2-0.25mol/l of urea.
The preparation method of the decorative wood board waterproof adhesive comprises the steps of 2, adding weighed formaldehyde into a flask, adjusting the pH value of the formaldehyde to 8.0 by using a sodium hydroxide solution, heating to 38 ℃ under the stirring condition, slowly dripping a first urea solution into the flask, then heating to 46 ℃ and reacting for 1 hour at constant temperature to obtain a first reaction solution.
According to the preparation method of the decorative wood board waterproof adhesive, zinc stearate is added in the step 3, wherein the mass of the zinc stearate is 1-5wt% of that of the first reaction liquid.
According to the preparation method of the decorative wood board waterproof adhesive, the modified nano titanium dioxide is added in the step 4, and the mass of the modified nano titanium dioxide is 0.1-1wt% of that of the second reaction solution.
The invention relates to a preparation method of a decorative wood board waterproof adhesive, and the preparation method of modified nano titanium dioxide in step 4 is that 1-2 parts of nano titanium dioxide are ultrasonically dispersed in dry toluene for 15-30min, then the nano titanium dioxide is connected to a reflux device, argon is introduced, the nano titanium dioxide is mechanically stirred and heated to 120-125 ℃, 0.01-0.02 part of hexamethyldisilazane is dropwise added, after reflux reaction is carried out for 2-3h, centrifugation and washing with toluene are carried out for 2-3 times, and the nano titanium dioxide is dried in a drying oven at 100-120 ℃ for 1-2h to obtain the modified nano titanium dioxide.
The preparation method of the decorative wood board waterproof adhesive comprises the following steps that in step 5, the mass ratio of the mixed solution, the mildew preventive, the flame retardant and the stabilizer is (100) to 0.1-1.
According to the preparation method of the decorative wood board waterproof adhesive, in the step 5, the mildew inhibitor is chitosan quaternary ammonium salt.
According to the preparation method of the decorative wood board waterproof adhesive, 0.5wt% of thiophanate methyl, 1wt% of propiconazole, 1wt% of tebuconazole, 5wt% of didecyl dimethyl ammonium chloride and 5wt% of ethanolamine are added into chitosan quaternary ammonium salt in the mildew preventive in the step 5, and the mass fraction of the thiophanate methyl, the propiconazole, the tebuconazole, the didecyl dimethyl ammonium chloride and the ethanolamine are 100wt%.
According to the preparation method of the decorative wood board waterproof adhesive, in the step 5, the flame retardant is a melamine and pentaerythritol copolymerization halogen-free flame retardant.
The invention relates to a preparation method of a decorative wood board waterproof adhesive, which comprises the following steps of weighing melamine, pentaerythritol and phenyl trichlorosilane according to the mass ratio of 2.5.
According to the preparation method of the decorative wood board waterproof adhesive, in the step 5, the stabilizer is a dimethylhydrazine stabilizer.
The invention relates to a preparation method of a decorative wood board waterproof adhesive, and in the step 5, a preparation method of a stabilizer is that the stabilizer is placed in a 500ml four-neck mechanical stirring bottle and placed in an N-shaped stirring bottle 2 Adding 250ml of toluene and 0.238mol of 1, 6-hexyl diisocyanate under protection, slowly dripping 0.2383mol of 1, 1-dimethyl hydrazine at normal temperature, naturally heating to 50-55 ℃, reacting for 1h, then adding 37.3g of tetramethyl piperidinol, maintaining the temperature at 55-60 ℃ for reaction for 3h, heating to 90 ℃, reacting for 2h, heating to 112 ℃, and distilling off toluene to obtain the stabilizer.
The invention has the beneficial effects that:
according to the preparation method of the decorative wood board waterproof adhesive, the prepared decorative wood board waterproof adhesive is good in waterproof performance, can prevent mildew and is flame-retardant, can be used in wood adhesives, and is good in bonding strength.
The invention relates to a preparation method of a decorative wood board waterproof adhesive.
Detailed Description
The first specific implementation way is as follows:
a preparation method of a decorative wood board waterproof adhesive comprises the following steps:
step 1, weighing formaldehyde and urea with certain mass according to a molar ratio, preparing the weighed urea into a urea solution, and then evenly dividing the urea solution into four equal parts according to the volume ratio for later use;
step 2, adding the formaldehyde weighed in the step 1 into a flask, adjusting the pH value of the formaldehyde to 8.0 by using a sodium hydroxide solution, heating to 38 ℃ under the stirring condition, slowly dripping a first part of urea solution into the flask, then heating to 46 ℃ to perform constant-temperature reaction for 1 hour, and obtaining a first reaction solution for later use;
step 3, adding acetic acid into the first reaction liquid obtained in the step 2 to adjust the pH value to 6.5, then adding zinc stearate with a certain mass, uniformly stirring, heating the reaction temperature to 60 ℃, then slowly dripping a second part of urea solution into the flask, and then reacting at constant temperature for 1.5 hours to obtain a second reaction liquid for later use;
step 4, adding modified nano titanium dioxide with a certain mass into the second reaction liquid obtained in the step 3, adjusting the pH to 7.8 by using a sodium hydroxide solution under the condition of ultrasonic stirring, adding a third urea solution, heating to 65 ℃, and reacting at constant temperature for 1 hour to obtain a third reaction liquid for later use;
and 5, regulating the pH value of formaldehyde to 8.2 by using a sodium hydroxide solution in the third reaction solution obtained in the step 4, slowly dripping a fourth part of urea solution into the flask under the stirring condition, adding a mildew preventive, a flame retardant and a stabilizer into the obtained mixed solution, stirring for reacting at a constant temperature for 3 hours, cooling to the normal temperature, and discharging to obtain the decorative wood board waterproof adhesive.
In the preparation method of the decorative wood board waterproof adhesive in the embodiment, in the step 1, the molar ratio of formaldehyde to urea is 1.1, the concentration of formaldehyde is 38wt%, and the concentration of urea is 0.25mol/l.
In the preparation method of the decorative wood board waterproof adhesive according to the embodiment, zinc stearate is added in the step 3, wherein the added zinc stearate accounts for 2wt% of the first reaction liquid.
In the preparation method of the decorative wood board waterproof adhesive according to the embodiment, the modified nano titanium dioxide is added in the step 4, and the mass of the modified nano titanium dioxide is 0.2wt% of that of the second reaction solution.
In the preparation method of the decorative wood board waterproof adhesive in the embodiment, the preparation method of the modified nano titanium dioxide in the step 4 is that 1 part of nano titanium dioxide is ultrasonically dispersed in dry toluene for 20min, then the nano titanium dioxide is connected to a reflux device, argon is introduced, mechanical stirring is carried out, the temperature is raised to 125 ℃, 0.01 part of hexamethyldisilazane is dropwise added, after reflux reaction is carried out for 2h, centrifugation is carried out, toluene is used for washing for 3 times, and drying is carried out in a 120 ℃ drying oven for 1h, so that the modified nano titanium dioxide is obtained.
In the preparation method of the decorative wood board waterproof adhesive according to the embodiment, in the step 5, the mass ratio of the mixed solution, the mildew preventive, the flame retardant and the stabilizer is 100.2.
In the preparation method of the decorative wood board waterproof adhesive in the embodiment, in the step 5, the mildew preventive is chitosan quaternary ammonium salt.
In the preparation method of the decorative wood board waterproof adhesive in the embodiment, in the step 5, 0.5wt% of thiophanate-methyl, 1wt% of propiconazole, 1wt% of tebuconazole, 5wt% of didecyl dimethyl ammonium chloride and 5wt% of ethanolamine are added into the chitosan quaternary ammonium salt in the mildew preventive, and the mass fraction of the adhesive is 100wt% of the chitosan quaternary ammonium salt.
In the preparation method of the decorative wood board waterproof adhesive according to the embodiment, in the step 5, the flame retardant is a melamine and pentaerythritol copolymerization halogen-free flame retardant.
According to the preparation method of the decorative wood board waterproof adhesive, in the step 5, melamine, pentaerythritol and phenyl trichlorosilane are weighed according to the mass ratio of 2:1, the weighed melamine and pentaerythritol are placed in a high-speed crusher to be fully crushed, the mixture is uniformly mixed and then transferred into a reaction system with a stirrer, a temperature controller and a condenser tube, cyclohexane is added to react for 3.5 hours at 85 ℃, the phenyl trichlorosilane is added, the mixture is stirred and heated, the reaction temperature is controlled to be 80 ℃, the discharged HCl gas is absorbed by alkali liquor until no HCl gas is discharged, a diluent solvent is evaporated, a product is washed until no chloride ions exist in filtrate, and the product is dried to obtain the melamine and pentaerythritol copolymerized halogen-free flame retardant.
In the preparation method of the decorative wood board waterproof adhesive according to the embodiment, the stabilizer in the step 5 is a dimethylhydrazine type stabilizer.
In the preparation method of the decorative wood board waterproof adhesive according to the embodiment, the stabilizer is prepared in a 500ml four-neck mechanical stirring bottle in an N (N/N) manner in the step 5 2 Adding 250ml of toluene and 0.238mol of 1, 6-hexyl diisocyanate under protection, slowly dripping 0.2383mol of 1, 1-dimethylhydrazine at normal temperature, naturally raising the temperature to 50-55 ℃, adding 37.3g of tetramethylpiperidinol after reacting for 1h, maintaining the temperature at 55-60 ℃ for reacting for 3h, raising the temperature to 90 ℃, reacting for 2h, raising the temperature to 112 ℃, and evaporating toluene to obtain the stabilizer.
According to the preparation method of the decorative wood board waterproof adhesive, the prepared decorative wood board waterproof adhesive is good in waterproof performance, can be mould-proof and flame-retardant, is used in wood adhesives, and is good in bonding strength.
The second embodiment is as follows:
a preparation method of a decorative wood board waterproof adhesive comprises the following steps:
step 1, weighing formaldehyde and urea with certain mass according to a molar ratio, preparing the weighed urea into a urea solution, and then evenly dividing the urea solution into four equal parts according to the volume ratio for later use;
step 2, adding the formaldehyde weighed in the step 1 into a flask, adjusting the pH value of the formaldehyde to 7.5 by using a sodium hydroxide solution, heating to 3 ℃ under the stirring condition, slowly dripping a first part of urea solution into the flask, then heating to 50 ℃ to perform constant temperature reaction for 1.5 hours, and obtaining a first reaction solution for later use;
step 3, adding acetic acid into the first reaction liquid obtained in the step 2 to adjust the pH value to 6.5, then adding a certain mass of zinc stearate, uniformly stirring, raising the reaction temperature to 60 ℃, then slowly dripping a second part of urea solution into the flask, and then reacting at constant temperature for 1 hour to obtain a second reaction liquid for later use;
step 4, adding a certain mass of modified nano titanium dioxide into the second reaction solution obtained in the step 3, adjusting the pH to 8.0 by using a sodium hydroxide solution under the condition of ultrasonic stirring, adding a third urea solution, heating to 60 ℃, and reacting at constant temperature for 1 hour to obtain a third reaction solution for later use;
and 5, regulating the pH value of formaldehyde to 8.5 by using a sodium hydroxide solution in the third reaction solution obtained in the step 4, slowly dripping a fourth part of urea solution into the flask under the stirring condition, adding a mildew preventive, a flame retardant and a stabilizer into the obtained mixed solution, stirring for reacting at a constant temperature for 5 hours, cooling to the normal temperature, and discharging to obtain the decorative wood board waterproof adhesive.
In the preparation method of the decorative wood board waterproof adhesive according to the embodiment, in the step 1, the molar ratio of formaldehyde to urea is 1, the concentration of formaldehyde is 40wt%, and the concentration of urea is 0.25mol/l.
In the preparation method of the decorative wood board waterproof adhesive according to the embodiment, zinc stearate is added in the step 3, wherein the mass of the zinc stearate is 1wt% of that of the first reaction solution.
In the preparation method of the decorative wood board waterproof adhesive according to the embodiment, the mass of the modified nano titanium dioxide added in the step 4 is 1wt% of the second reaction solution.
In the preparation method of the decorative wood board waterproof adhesive in the embodiment, the preparation method of the modified nano titanium dioxide in the step 4 is that 2 parts of nano titanium dioxide are ultrasonically dispersed in dry toluene for 30min, then the nano titanium dioxide is connected to a reflux device, argon is introduced, mechanical stirring is carried out, the temperature is raised to 120 ℃, 0.01 part of hexamethyldisilazane is dropwise added, after reflux reaction is carried out for 3h, centrifugation is carried out, toluene is used for washing for 2 times, and drying is carried out in a drying oven at 100-120 ℃ for 1h, so that the modified nano titanium dioxide is obtained.
In the preparation method of the decorative wood board waterproof adhesive according to the embodiment, in the step 5, the mass ratio of the mixed solution, the mildew preventive, the flame retardant and the stabilizer is 100.1.
In the preparation method of the decorative wood board waterproof adhesive according to the embodiment, in the step 5, the mildew preventive is chitosan quaternary ammonium salt.
According to the preparation method of the decorative wood board waterproof adhesive, in the step 5, 0.5wt% of thiophanate methyl, 1wt% of propiconazole, 1wt% of tebuconazole, 5wt% of didecyl dimethyl ammonium chloride and 5wt% of ethanolamine are added into chitosan quaternary ammonium salt in the mildew preventive, and the mass fraction of the thiophanate methyl, the propiconazole, the tebuconazole, the didecyl dimethyl ammonium chloride and the ethanolamine are 100wt%.
In the preparation method of the decorative wood board waterproof adhesive according to the embodiment, in the step 5, the flame retardant is a melamine and pentaerythritol copolymerization halogen-free flame retardant.
According to the preparation method of the decorative wood board waterproof adhesive, in the step 5, melamine, pentaerythritol and phenyltrichlorosilane are weighed according to a mass ratio of 2.
In the preparation method of the decorative wood board waterproof adhesive according to the embodiment, the stabilizer in the step 5 is a dimethylhydrazine type stabilizer.
In the preparation method of the decorative wood board waterproof adhesive according to the embodiment, the stabilizer is prepared in a 500ml four-neck mechanical stirring bottle in an N (N/N) manner in the step 5 2 Adding 250ml of toluene and 0.238mol of 1, 6-hexyl diisocyanate under protection, slowly dripping 0.2383mol of 1, 1-dimethyl hydrazine at normal temperature, naturally raising the temperature to 50-55 ℃, reacting for 1h, then adding 37.3g of tetramethyl piperidinol, maintaining the temperature at 55-60 ℃, reacting for 3h, raising the temperature againThe temperature is raised to 90 ℃, the reaction is carried out for 2 hours, and then the temperature is raised to 112 ℃ to distill out toluene, thus obtaining the stabilizing agent.
According to the preparation method of the decorative wood board waterproof adhesive, the prepared decorative wood board waterproof adhesive is good in waterproof performance, can be mould-proof and flame-retardant, is used in wood adhesives, and is good in bonding strength.
Detailed description of the invention
A preparation method of a decorative wood board waterproof adhesive comprises the following steps:
step 1, weighing formaldehyde and urea with certain mass respectively according to a molar ratio, preparing the weighed urea into a urea solution, and then averagely dividing the urea solution into four equal parts according to the volume ratio for later use;
step 2, adding the formaldehyde weighed in the step 1 into a flask, adjusting the pH value of the formaldehyde to 7.5 by using a sodium hydroxide solution, heating to the temperature of 35 ℃ under the condition of stirring, slowly dripping a first urea solution into the flask, then heating to the temperature of 45 ℃ for constant-temperature reaction for 1 hour to obtain a first reaction solution for later use;
step 3, adding acetic acid into the first reaction liquid obtained in the step 2 to adjust the pH value to 6, then adding a certain mass of zinc stearate, uniformly stirring, raising the reaction temperature to 55 ℃, then slowly dripping a second part of urea solution into the flask, and then reacting at constant temperature for 1 hour to obtain a second reaction liquid for later use;
step 4, adding modified nano titanium dioxide with a certain mass into the second reaction liquid obtained in the step 3, adjusting the pH to 7.5 by using a sodium hydroxide solution under the condition of ultrasonic stirring, adding a third urea solution, heating to 60 ℃, and reacting at constant temperature for 1 hour to obtain a third reaction liquid for later use;
and 5, regulating the pH value of formaldehyde to 8.0 by using a sodium hydroxide solution in the third reaction solution obtained in the step 4, slowly dripping a fourth part of urea solution into the flask under the stirring condition, adding a mildew preventive, a flame retardant and a stabilizer into the obtained mixed solution, stirring for reacting at a constant temperature for 2 hours, cooling to the normal temperature, and discharging to obtain the decorative wood board waterproof adhesive.
In the preparation method of the decorative wood board waterproof adhesive in the embodiment, in the step 1, the molar ratio of formaldehyde to urea is 1.05, the concentration of formaldehyde is 37wt%, and the concentration of urea is 0.2mol/l.
In the preparation method of the decorative wood board waterproof adhesive according to the embodiment, the mass of the zinc stearate added in the step 3 is 3wt% of the first reaction solution.
In the preparation method of the decorative wood board waterproof adhesive according to the embodiment, the mass of the modified nano titanium dioxide added in the step 4 is 0.1wt% of the second reaction solution.
In the preparation method of the decorative wood board waterproof adhesive in the embodiment, the preparation method of the modified nano titanium dioxide in the step 4 is that 1.5 parts of nano titanium dioxide is ultrasonically dispersed in dry toluene for 30min, then the nano titanium dioxide is connected to a reflux device, argon is introduced, mechanical stirring is carried out, the temperature is increased to 120 ℃, 0.01 part of hexamethyldisilazane is dropwise added, after reflux reaction is carried out for 3h, centrifugation is carried out, toluene is used for washing for 3 times, and drying is carried out in a drying oven at 100-120 ℃ for 1h, so that the modified nano titanium dioxide is obtained.
According to the preparation method of the decorative wood board waterproof adhesive, in the step 5, the mass ratio of the mixed solution, the mildew preventive, the flame retardant and the stabilizer is (100.2).
In the preparation method of the decorative wood board waterproof adhesive in the embodiment, in the step 5, the mildew preventive is chitosan quaternary ammonium salt.
According to the preparation method of the decorative wood board waterproof adhesive, in the step 5, 0.5wt% of thiophanate methyl, 1wt% of propiconazole, 1wt% of tebuconazole, 5wt% of didecyl dimethyl ammonium chloride and 5wt% of ethanolamine are added into chitosan quaternary ammonium salt in the mildew preventive, and the mass fraction of the thiophanate methyl, the propiconazole, the tebuconazole, the didecyl dimethyl ammonium chloride and the ethanolamine are 100wt%.
In the preparation method of the decorative wood board waterproof adhesive according to the embodiment, in the step 5, the flame retardant is a copolymerized halogen-free flame retardant of melamine and pentaerythritol.
According to the preparation method of the decorative wood board waterproof adhesive, in the step 5, melamine, pentaerythritol and phenyltrichlorosilane are weighed according to a mass ratio of 2.
In the preparation method of the decorative wood board waterproof adhesive according to the embodiment, the stabilizer in the step 5 is a dimethylhydrazine type stabilizer.
In the preparation method of the decorative wood board waterproof adhesive according to the embodiment, the stabilizer is prepared in a 500ml four-neck mechanical stirring bottle in an N (N/N) manner in the step 5 2 Adding 250ml of toluene and 0.238mol of 1, 6-hexyl diisocyanate under protection, slowly dripping 0.2383mol of 1, 1-dimethylhydrazine at normal temperature, naturally raising the temperature to 50-55 ℃, adding 37.3g of tetramethylpiperidinol after reacting for 1h, maintaining the temperature at 55-60 ℃ for reacting for 3h, raising the temperature to 90 ℃, reacting for 2h, raising the temperature to 112 ℃, and evaporating toluene to obtain the stabilizer.
According to the preparation method of the decorative wood board waterproof adhesive, the prepared decorative wood board waterproof adhesive is good in waterproof performance, can be mould-proof and flame-retardant, can be used in wood adhesives, and is good in bonding strength.
In the first to third embodiments, the performance of the decorative wood board waterproof adhesive prepared by the preparation method of the decorative wood board waterproof adhesive is tested, and the mechanical test method comprises the following steps: the wood plates coated with the adhesive are beneficial to the condition that the pH value of the wood plates is 7, the wood plates are soaked for 70 hours in water at the temperature of 20 ℃, the distance between the wood plates and the bottom of a water tank is 15mm, the distance between the wood plates and the bottom of the water tank is 25mm, the wood plates are taken out of the water tank after soaking, water attached to the surfaces of the wood plates is wiped off, the wood plates are placed into a freezing refrigerator at the temperature of-12 ℃, the wood plates are mutually spaced for 15mm and are frozen for 24 hours, the wood plates are taken out of the low-temperature refrigerator after freezing and are immediately placed into a drying box at the temperature of 70 ℃, the wood plates are mutually spaced for 15mm, the total volume of the wood plates is not more than 10 percent of the volume of the drying box, the wood plates are dried for 70 hours, the wood plates are taken out of the drying box and are placed at room temperature for cooling for 4 hours, and primary circulation is completed. After circulating for 3 times, testing at a shearing speed of 10mm/min by using a tensile machine in a shearing mode to obtain the wet adhesion strength of the adhesive, wherein the comparative example is the performance of a commercial urea-formaldehyde resin adhesive, and the test result is shown in table 1:
TABLE 1 comparison of mechanical properties
| Bonding Strength (MPa) | Wet bond Strength (MPa) | |
| Detailed description of the invention | 3.51 | 3.12 |
| Detailed description of the invention | 3.48 | 3.07 |
| Detailed description of the invention | 3.45 | 3.05 |
| Comparative example | 1.01 | 0.51 |
As can be seen from the table, the prepared decorative wood board waterproof adhesive has good waterproof performance.
The performance of the decorative wood board waterproof adhesive prepared by the preparation method of the decorative wood board waterproof adhesive according to the first to third specific embodiments is tested, and the antibacterial performance test method comprises the following steps: according to the requirements and specific test steps of the national standard 31402-2015 plastic surface antibacterial property test method, the anti-mold property of the adhesive to aspergillus niger is mainly tested, the comparative example is the property of a commercial urea-formaldehyde resin adhesive, and the test results are shown in table 2:
TABLE 2 comparison table of antibacterial property
| Has sterile surface | Presence or absence of bacterial colony around | |
| Detailed description of the invention | Is free of | Is free of |
| Detailed description of the invention | Is free of | Is free of |
| Detailed description of the invention | Is free of | Is free of |
| Comparative example | Is provided with | Is provided with |
As can be seen from the table, the prepared decorative wood board waterproof adhesive can prevent mold.
In the first to third embodiments, the performance of the decorative wood board waterproof adhesive prepared by the preparation method of the decorative wood board waterproof adhesive is tested, and the flame retardant performance test method comprises the following steps: the flame burn time was tested, the comparative example is the performance of a commercial urea formaldehyde resin adhesive, and the test results are shown in table 3:
TABLE 3 comparative table of flame retardant properties
| Flaming combustion time(s) | |
| Detailed description of the invention | 4.9 |
| Detailed description of the invention | 4.8 |
| Detailed description of the invention | 4.7 |
| Comparative example | 35.1 |
As can be seen from the table, the prepared decorative wood board waterproof adhesive can resist flame.
The fourth concrete implementation mode is as follows:
a preparation method of a decorative wood board waterproof adhesive comprises the following steps:
step 1, weighing formaldehyde and urea with certain mass according to a molar ratio, preparing the weighed urea into a urea solution, and then evenly dividing the urea solution into four equal parts according to the volume ratio for later use;
step 2, adding the formaldehyde weighed in the step 1 into a flask, adjusting the pH value of the formaldehyde to 7.5-8.0 by using a sodium hydroxide solution, heating to the temperature of 35-40 ℃ under the condition of stirring, slowly dripping a first urea solution into the flask, then heating to the temperature of 45-50 ℃ for constant-temperature reaction for 1-1.5h to obtain a first reaction solution for later use;
step 3, adding acetic acid into the first reaction liquid obtained in the step 2 to adjust the pH value to 6-6.5, then adding zinc stearate with a certain mass, uniformly stirring, heating the reaction temperature to 55-60 ℃, then slowly dripping a second part of urea solution into the flask, and then reacting at constant temperature for 1-1.5 hours to obtain a second reaction liquid for later use;
step 4, adding a certain mass of modified nano titanium dioxide into the second reaction solution obtained in the step 3, adjusting the pH value to 7.5-8.0 by using a sodium hydroxide solution under the condition of ultrasonic stirring, adding a third part of urea solution, heating to 60-70 ℃, reacting at constant temperature for 1 hour, and obtaining a third reaction solution for later use;
and 5, regulating the pH value of formaldehyde to 8.0-8.5 by using a sodium hydroxide solution in the third reaction solution obtained in the step 4, slowly dripping a fourth part of urea solution into the flask under the stirring condition, adding a mildew preventive, a flame retardant and a stabilizer into the obtained mixed solution, stirring for reacting at a constant temperature for 2-5 hours, cooling to the normal temperature, and discharging to obtain the decorative wood board waterproof adhesive.
According to the preparation method of the decorative wood board waterproof adhesive, the prepared decorative wood board waterproof adhesive is good in waterproof performance, can be mould-proof and flame-retardant, is used in wood adhesives, and is good in bonding strength.
The fifth concrete implementation mode:
according to a fourth specific embodiment, in the step 1, the molar ratio of formaldehyde to urea is 1 to 1.1, the concentration of formaldehyde is 37 to 40wt%, and the concentration of urea is 0.2 to 0.25mol/l.
The sixth specific implementation mode:
according to a fourth specific embodiment, in the step 2, the weighed formaldehyde is added into a flask, the pH value of the formaldehyde is adjusted to 8.0 by using a sodium hydroxide solution, the mixture is heated to 38 ℃ under a stirring condition, then a first urea solution is slowly dripped into the flask, and the temperature is raised to 46 ℃ for a constant-temperature reaction for 1 hour, so as to obtain a first reaction solution.
The seventh concrete implementation mode:
according to a fourth specific embodiment, in the step 3, the added zinc stearate accounts for 1-5wt% of the first reaction liquid.
The specific implementation mode is eight:
according to a fourth specific embodiment, in the step 4, the modified nano titanium dioxide is added in an amount of 0.1-1wt% of the second reaction solution.
The specific implementation method nine:
according to a fourth specific embodiment, in the step 4, the modified nano titanium dioxide is prepared by ultrasonically dispersing 1-2 parts of nano titanium dioxide in dry toluene for 15-30min, introducing a reflux device, introducing argon, mechanically stirring, heating to 120-125 ℃, dropwise adding 0.01-0.02 part of hexamethyldisilazane, performing reflux reaction for 2-3h, centrifuging, washing with toluene for 2-3 times, and drying in a drying oven at 100-120 ℃ for 1-2 h.
The detailed implementation mode is ten:
according to a fourth specific embodiment, in the step 5, the mass ratio of the mixed solution, the mildew preventive, the flame retardant and the stabilizer is 100, and the ratio is 0.1-1.
The concrete implementation mode eleven:
according to a fourth specific embodiment, in the step 5, the mildew preventive is chitosan quaternary ammonium salt.
The specific implementation mode twelve:
according to the fourth specific embodiment, in the step 5, the flame retardant is a halogen-free flame retardant copolymerized by melamine and pentaerythritol.
The specific implementation mode is thirteen:
according to a fourth specific embodiment of the method for preparing the decorative wood board waterproof adhesive, in the step 5, the stabilizer is a dimethylhydrazine stabilizer.
Claims (3)
1. A preparation method of decorative wood board waterproof adhesive is characterized by comprising the following steps: the method comprises the following steps:
step 1, weighing formaldehyde and urea with certain mass according to a molar ratio, preparing the weighed urea into a urea solution, and then evenly dividing the urea solution into four equal parts according to the volume ratio for later use;
in the step 1, the molar ratio of formaldehyde to urea is 1-1.1;
step 2, adding the formaldehyde weighed in the step 1 into a flask, adjusting the pH value of the formaldehyde to 7.5-8.0 by using a sodium hydroxide solution, heating to the temperature of 35-40 ℃ under the condition of stirring, slowly dripping a first urea solution into the flask, then heating to the temperature of 45-50 ℃ for constant-temperature reaction for 1-1.5h to obtain a first reaction solution for later use;
step 3, adding acetic acid into the first reaction liquid obtained in the step 2 to adjust the pH value to 6-6.5, then adding zinc stearate with a certain mass, uniformly stirring, raising the reaction temperature to 55-60 ℃, then slowly dripping a second part of urea solution into the flask, and then reacting at constant temperature for 1-1.5 hours to obtain a second reaction liquid for later use;
step 4, adding a certain mass of modified nano titanium dioxide into the second reaction solution obtained in the step 3, adjusting the pH value to 7.5-8.0 by using a sodium hydroxide solution under the condition of ultrasonic stirring, adding a third part of urea solution, heating to 60-70 ℃, reacting at constant temperature for 1 hour, and obtaining a third reaction solution for later use;
step 5, adjusting the pH value of formaldehyde to 8.0-8.5 by using a sodium hydroxide solution in the third reaction solution obtained in the step 4, slowly dripping a fourth part of urea solution into a flask under the stirring condition, adding a mildew preventive, a flame retardant and a stabilizer into the obtained mixed solution, stirring for reacting at a constant temperature for 2-5 hours, cooling to the normal temperature, and discharging to obtain the decorative wood board waterproof adhesive;
in the step 3, zinc stearate is added, and the mass of the zinc stearate is 1-5wt% of that of the first reaction liquid;
in the step 4, the mass of the added modified nano titanium dioxide is 0.1-1wt% of that of the second reaction solution;
the preparation method of the modified nano titanium dioxide in the step 4 comprises the steps of ultrasonically dispersing 1-2 parts of nano titanium dioxide in dry toluene for 15-30min, connecting into a reflux device, introducing argon, mechanically stirring and heating to 120-125 ℃, dropwise adding 0.01-0.02 part of hexamethyldisilazane, carrying out reflux reaction for 2-3h, centrifuging, washing for 2-3 times by using toluene, and drying in a drying oven at 100-120 ℃ for 1-2h to obtain the modified nano titanium dioxide;
in the step 5, the mass ratio of the mixed solution, the mildew preventive, the flame retardant and the stabilizer is (100);
in the step 5, the mildew preventive is chitosan quaternary ammonium salt;
in the step 5, the flame retardant is a melamine and pentaerythritol copolymerization halogen-free flame retardant;
the stabilizer in the step 5 is a dimethylhydrazine type stabilizer.
2. The preparation method of the decorative wood board waterproof adhesive according to claim 1, wherein the preparation method comprises the following steps: the concentration of formaldehyde is 37-40wt%, and the concentration of urea is 0.2-0.25mol/l.
3. The preparation method of the decorative wood board waterproof adhesive according to claim 2, wherein the preparation method comprises the following steps: adding the weighed formaldehyde into a flask, adjusting the pH value of the formaldehyde to 8.0 by using a sodium hydroxide solution, heating to 38 ℃ under the stirring condition, slowly dripping a first urea solution into the flask, then heating to 46 ℃ and reacting at constant temperature for 1h to obtain a first reaction solution.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB521380A (en) * | 1938-11-17 | 1940-05-20 | Beck Koller & Co England | A process for the manufacture of urea-formaldehyde condensation products |
| CN108794712A (en) * | 2018-07-11 | 2018-11-13 | 四川农业大学 | A kind of modified urea-formaldehyde resin preparation method used for bottom plate of container |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB552744A (en) * | 1941-10-16 | 1943-04-22 | Neville Esmond Challenger | Improvements in or relating to the manufacture of synthetic resins from urea-formaldehyde |
| CN101175832A (en) * | 2005-07-06 | 2008-05-07 | 一方社油脂工业株式会社 | Aldehyde collector and manufacturing method of woody panel using it |
| CN101475676B (en) * | 2009-01-20 | 2011-06-29 | 江苏工业学院 | Preparation of urea-formaldehyde resin for environment-friendly artificial board |
| CN101696348B (en) * | 2009-10-29 | 2012-08-22 | 杨济优 | Urea resin adhesive capable of removing formaldehyde |
| CN102086295B (en) * | 2010-06-28 | 2013-05-08 | 永港伟方（北京）科技股份有限公司 | Urea-formaldehyde resin for non-dewatering particleboard and preparation method thereof |
| CN103627355B (en) * | 2013-12-04 | 2015-05-27 | 江苏锋芒复合材料科技集团有限公司 | Efficient superstrong tackiness agent for emery cloth |
| CN104531015B (en) * | 2014-12-22 | 2017-01-11 | 中国神华能源股份有限公司 | Phenolic resin adhesive as well as preparation method and application thereof |
| CN107746696A (en) * | 2017-09-07 | 2018-03-02 | 柳州市林道科技有限公司 | A kind of wood-based plate urea-formaldehyde resin adhesive and its preparation technology |
| CN107793974A (en) * | 2017-10-24 | 2018-03-13 | 鹤山市永达化工有限公司 | A kind of nanometer galapectite and titania modified urea-formaldehyde resin adhesive and preparation method thereof |
| CN107984561B (en) * | 2017-11-30 | 2021-03-16 | 中南林业科技大学 | Method for preparing environment-friendly plywood through auxiliary heating and environment-friendly plywood |
-
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- 2021-04-25 CN CN202110447535.3A patent/CN113072903B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB521380A (en) * | 1938-11-17 | 1940-05-20 | Beck Koller & Co England | A process for the manufacture of urea-formaldehyde condensation products |
| CN108794712A (en) * | 2018-07-11 | 2018-11-13 | 四川农业大学 | A kind of modified urea-formaldehyde resin preparation method used for bottom plate of container |
Non-Patent Citations (1)
| Title |
|---|
| Urea-formaldehyde resin modified by nano-TiO2 under ultrasonic treatment;Xia SongHua 等;《Journal of Beijing Forestry University》;20091231;第31卷(第4期);第123-129页 * |
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