CN114231226A - Low-cost modified urea-formaldehyde resin adhesive - Google Patents
Low-cost modified urea-formaldehyde resin adhesive Download PDFInfo
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- CN114231226A CN114231226A CN202111613498.5A CN202111613498A CN114231226A CN 114231226 A CN114231226 A CN 114231226A CN 202111613498 A CN202111613498 A CN 202111613498A CN 114231226 A CN114231226 A CN 114231226A
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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
- C09J161/32—Modified amine-aldehyde condensates
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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
- C08G12/40—Chemically modified polycondensates
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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
- C09J11/04—Non-macromolecular additives inorganic
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Abstract
The invention relates to an adhesive, in particular to a low-cost modified urea-formaldehyde resin adhesive. The paint comprises the following components in percentage by mass: 300 parts of formaldehyde 240-containing material, 0.1-2.5 parts of polyvinyl alcohol, 200 parts of urea 180-containing material, 15-25 parts of melamine and 1-2 parts of strength enhancer; the preparation method of the strength improver comprises the following steps: s1, reacting phthalic acid, maleic anhydride and diethylenetriamine at the temperature of 130-160 ℃, cooling and diluting to obtain a hyperbranched amino polymer; s2, mixing epoxy chloropropane, a solvent and the hyperbranched amino polymer, reacting at 40-80 ℃, and adjusting the pH to 7.5-8.5 to obtain a branched polymer cross-linking agent-assistant A; s3, selecting biomass tannin as an auxiliary B; s4, selecting silicate as an auxiliary agent C; and S5, mixing the ABC three auxiliary agents in proportion to obtain the ABC auxiliary agent. The adhesive prepared by the invention has high reaction activity, adjustable viscosity, good initial viscosity, good bonding force, excellent prepressing performance and bonding performance, can reduce the dosage of melamine, reduces the cost of the adhesive and can be applied industrially.
Description
Technical Field
The invention relates to an adhesive, in particular to a low-cost modified urea-formaldehyde resin adhesive.
Background
Since the urea-formaldehyde (UF) resin adhesive is used as a wood adhesive for the first time in the early 20 th century, the UF resin adhesive is rapidly developed due to the advantages of readily available raw materials, low price, simple manufacturing process, convenience in use and the like, is widely used for manufacturing artificial boards such as shaving boards, plywood, Medium Density Fiber (MDF) boards and laminated wood boards and the like and bonding materials such as mineral wool, mineral fibers, cast sand molds and the like, and is one of the synthetic adhesives with the largest market consumption. UF resin glues have been reported for 80% plywood and 100% particle board in japan, 75% particle board in germany, and 100% particle board in the uk. Therefore, UF resin glues have become the dominant glue species in the wood-based panel industry.
In recent years, with the continuous development and perfection of production equipment and technology of the urea glue, the production capacity of the urea glue is increased day by day. However, the homogenization of the urea-formaldehyde glue is serious, so that the price of production raw materials is high, the product selling price is low, and the reduction of the production cost is urgent. As one of the main raw materials for urea adhesive production, melamine is always a considerable cost, so that a part of melamine is replaced by an intensity improver, and a urea adhesive system is optimized, so that the development of low-cost modified urea adhesive is a trend of the wood adhesive industry on the premise of ensuring the product quality.
Disclosure of Invention
The invention aims to provide a low-cost modified urea-formaldehyde resin, and the formaldehyde release amount of the modified urea-formaldehyde resin accords with the national E in the using process0The standard, the bonding strength and the dipping and peeling meet the national II-type standard.
The technical purpose of the invention is realized by the following technical scheme:
a low-cost modified urea-formaldehyde resin adhesive comprises the following components in parts by mass: 300 parts of formaldehyde 240-containing material, 0.1-2.5 parts of polyvinyl alcohol, 200 parts of urea 180-containing material, 15-25 parts of melamine and 1-2 parts of strength enhancer;
the preparation method of the strength improver comprises the following steps:
s1, reacting phthalic acid, maleic anhydride and diethylenetriamine at the temperature of 130-160 ℃, cooling and diluting to obtain a hyperbranched amino polymer;
s2, mixing epoxy chloropropane, a solvent and the hyperbranched amino polymer, reacting at 40-80 ℃, and adjusting the pH to 7.5-8.5 to obtain a branched polymer cross-linking agent-assistant A;
s3, selecting biomass tannin as an auxiliary B;
s4, selecting silicate as an auxiliary agent C;
and S5, mixing the ABC three auxiliary agents in proportion to obtain the strength improver.
Preferably, the low-cost modified urea-formaldehyde resin adhesive comprises the following components in percentage by mass: 260 parts of formaldehyde, 1 part of polyvinyl alcohol, 191 parts of urea, 18 parts of melamine and 1-2 parts of strength improver.
Preferably, the preparation method of the strength improver comprises the following steps:
s1, reacting phthalic acid, maleic anhydride and diethylenetriamine at 150 ℃, cooling and diluting to obtain a hyperbranched amino polymer;
s2, mixing epoxy chloropropane, a solvent and the hyperbranched amino polymer, reacting at 60 ℃, and adjusting the pH to 8 to obtain a branched polymer cross-linking agent-assistant A;
s3, selecting biomass tannin as an auxiliary B;
s4, selecting silicate as an auxiliary agent C;
and S5, mixing the ABC three auxiliary agents in proportion to obtain the strength improver.
Preferably, the formaldehyde is at a concentration of 37%; the polyvinyl alcohol is numbering 2189, and the purity is over 99 percent of industrial grade; the melamine is in industrial grade with the purity of more than 99 percent; the urea is of industrial grade with purity of more than 99%.
Preferably, the molar ratio of the phthalic acid to the maleic anhydride to the diethylenetriamine is 9:1: 1.4; the mass ratio of the epoxy chloropropane to the solvent to the hyperbranched amino polymer is 2:3:1, and the solvent is water.
Preferably, the mass fraction of the hyperbranched amino polymer is 25% -30%.
Preferably, the biomass tannin is black wattle condensed tannin, the purity is more than 98%, and the granularity is 100-120 meshes; the silicate is industrial grade aluminum silicate with the purity of more than 99 percent and the granularity of more than 3000 meshes.
Preferably, the preparation method of the low-cost modified urea-formaldehyde resin comprises the following steps:
K1. completing the first feeding in a reaction kettle under the condition of stirring, adding 300 parts of formaldehyde 240-40%, adjusting the reaction pH to 8-9, adding 0.1-2.5 parts of polyvinyl alcohol and 80-100 parts of urea, heating to 50-70 ℃, adding 9-13 parts of melamine and 0.6-1.6 parts of first strength promoter, heating to 85-95 ℃, and preserving heat for 30-40min to obtain a K1 reaction product;
K2. adjusting the reaction product of K1 with acid to pH 5.5-6.5, and carrying out K2 polycondensation reaction at 85-90 deg.C for 40-60min to obtain K2 reaction product;
K3. regulating the pH value of a K2 reaction product to 6-7 by using alkali, carrying out secondary feeding at the temperature of 80-90 ℃, adding 5-12 parts of melamine and 50-55 parts of urea, and carrying out K3 polycondensation reaction for 20-40min at the temperature of 80-90 ℃ to obtain a K3 reaction product;
K4. regulating the reaction product of K3 with alkali to pH 6-7, feeding for the third time at 70-80 deg.c, adding urea 30-35 weight portions, and maintaining for 25-35min to obtain reaction product of K4;
K5. regulating the reaction product of K4 with alkali to pH 7.5-8.5, feeding for the fourth time at 70-80 deg.c, adding urea 12-20 weight portions and second strength promoter 0.1-0.4 weight portions, and maintaining for 10-20min to obtain K5 reaction product;
K6. regulating the reaction product of K5 with alkali to pH 7.5-8.5, and cooling; discharging when the temperature is reduced to 35-45 ℃.
In the steps K1 and K5, the addition amount of the additive A and the additive B in the strength improver is too much, so that the glue cost is too high, and the cost advantage is reduced; when the addition amount of the additive C is too large, a precipitation phenomenon can occur. According to the invention, substances in a specific proportion are firstly reacted with formaldehyde to form a stable chemical bond, so that the performance of the glue is improved, and then after the addition polycondensation reaction of the glue is completed, a second strength improver is added after the glue is in a heat preservation stage, so that the stability of the glue is improved.
Preferably, the preparation method of the low-cost modified urea-formaldehyde resin comprises the following steps:
K1. completing the first feeding in a reaction kettle under the condition of stirring, adding 260 parts of formaldehyde with the concentration of 37%, adjusting the pH value of the reaction to 8.5, adding 1 part of polyvinyl alcohol and 90 parts of urea, heating to 60 ℃, adding 11 parts of melamine and 0.8 part of strength improver, heating to 90 ℃, and keeping the temperature for 35 min;
K2. adjusting the pH of the K1 reactant to 6.0 with acid, and performing polycondensation reaction at 88 deg.C (40-60 min);
K3. adjusting the pH of a reactant K2 to 6.5 by using alkali, feeding for the second time at 85 ℃, adding 7 parts of melamine and 52 parts of urea, and performing polycondensation reaction at 85 ℃ (20-40 min);
K4. regulating the reactant of K3 with alkali to pH 6.5, feeding for the third time at 75 deg.c, adding 33 parts of urea and maintaining for 30 min;
K5. regulating the reactant of K4 with alkali to pH 8.0, feeding for the fourth time at 75 deg.c, adding urea 16 weight portions and strength promoter 0.2 weight portions, and maintaining for 15 min;
K6. the reaction product of K5 was adjusted to pH 8.0 with base and the temperature was reduced. And discharging when the temperature is reduced to 40 ℃.
Preferably, the acid for adjusting the pH in the steps K1, K2, K3, K4, K5 and K6 is a formic acid solution diluted to 30% concentration, and the alkali is a sodium hydroxide solution diluted to 30% concentration.
Preferably, the first strength-enhancing agent ratio in the step K1 is: and (3) auxiliary agent A: and (3) auxiliary agent B: auxiliary agent C = 1: 1:0.
The auxiliary agent C is aluminum silicate powder and does not participate in formaldehyde reaction, but the glue becomes turbid, so that the glue observation phenomenon has errors, the auxiliary agent C is not added in the step, the auxiliary agent A is an epoxy chloropropane compound, the auxiliary agent B is black wattle tannin, and the auxiliary agent A and the auxiliary agent B need to react with formaldehyde to form stable chemical bonds, so that the performance of the glue is improved, and the auxiliary agents A and B are added in the step.
Preferably, the second strength-enhancing agent ratio in the step K5 is: and (3) auxiliary agent A: and (3) auxiliary agent B: auxiliary agent C = 0: 0:1.
The auxiliary agent A is an epichlorohydrin compound, the auxiliary agent B is black wattle tannin, the two auxiliary agents are required to participate in formaldehyde reaction, the step is at the end stage of heat preservation, the performance of the glue can not be improved by adding the two auxiliary agents, so the auxiliary agents A and B are not added in the step, the auxiliary agent C is aluminum silicate powder, and after the addition polycondensation reaction of the glue is completed, the aluminum silicate powder is added in the heat preservation stage, which is beneficial to improving the stability of the glue, so the auxiliary agent C is added in the step.
The invention has the beneficial effects that:
1. the branched polymer cross-linking agent with flexible double ethylenic bonds is prepared from phthalic acid and maleic anhydride, so that on one hand, a flexible structure is favorable for forming a flexible reinforced structure in an adhesive, on the other hand, a hyperbranched structure is formed, the molecular weight of the adhesive is increased, the viscosity is reduced, the two are favorable for eliminating stress, the bonding performance of the plywood is improved, the use amount of melamine is reduced, and the cost is saved;
2. after the aldehyde compound (formaldehyde) is added in the vegetable tanning, the main reaction group is still the amino group of the skin collagen; however, when the tannin molecules contain reactive groups with high nucleophilic activity, the aldehyde compounds can form cross-linking bonds between the collagen and the tannin molecules; the crosslinking effect can generate a synergistic effect on improving the thermal stability of the collagen, further enhance the combination stability of the tannin and the collagen, and resist the effects of a hydrogen bond breaking reagent and a hydrophobic bond breaking reagent; the black wattle tannin adopted by the invention is easy to react with formaldehyde to form collagen-aldehyde-tannin cross-linked bonds, but when other wood tannin (hydrolytic species) is adopted, the probability of forming the cross-linked bonds is very low; therefore, the black wattle tannin improves the bonding performance of the plywood to a great extent, reduces the usage amount of melamine and saves the cost;
3. the industrial silicate is used as a filling agent of the glue, so that the price is low, the hardness, whiteness, wear resistance, weather resistance, storage stability and the like can be improved, the storage period of the glue is prolonged, good flow time is provided for a factory, the cost is indirectly reduced, and the production process requirement of the factory is met;
4. the adhesive prepared by the invention has high reaction activity, adjustable viscosity, good initial viscosity, good bonding force, excellent prepressing performance and bonding performance, can reduce the dosage of melamine, reduces the cost of the adhesive and can be applied industrially.
Detailed Description
Example 1
The preparation method of the low-cost modified urea-formaldehyde resin comprises the following steps:
K1. completing the first feeding in a reaction kettle under the condition of stirring, adding 240 parts of formaldehyde with the concentration of 35%, adjusting the reaction pH to 8, adding 0.1 part of polyvinyl alcohol and 80 parts of urea, heating to 50 ℃, adding 9 parts of melamine and 0.6 part of first strength improver, heating to 85 ℃, and preserving heat for 30min to obtain a K1 reaction product;
K2. adjusting the reaction product of K1 with acid to pH 5.5, and carrying out K2 polycondensation reaction at 85 deg.C for 40min to obtain reaction product of K2;
K3. regulating the reaction product of K2 with alkali to pH 6, feeding for the second time at 80 deg.C, adding 6 parts of melamine and 50 parts of urea, and performing K3 polycondensation at 80 deg.C for 20min to obtain K3 reaction product;
K4. regulating the reaction product of K3 with alkali to pH 6, feeding for the third time at 70 deg.c, adding urea in 30 weight portions and maintaining for 25min to obtain reaction product of K4;
K5. regulating the reaction product of K4 with alkali to pH 7.5, feeding for the fourth time at 70 deg.c, adding urea in 20 weight portions and the second strength promoter in 0.4 weight portion, and maintaining for 20min to obtain K5 reaction product;
K6. regulating the reaction product of K5 with alkali to pH8.5, and cooling; and discharging when the temperature is reduced to 45 ℃.
The preparation method of the first/second strength improver comprises the following steps:
s1, reacting phthalic acid, maleic anhydride and diethylenetriamine at 130 ℃, cooling and diluting to obtain a hyperbranched amino polymer;
s2, mixing epoxy chloropropane, a solvent and the hyperbranched amino polymer, reacting at 40 ℃, and adjusting the pH to 7.5 to obtain a branched polymer cross-linking agent-assistant A;
s3, selecting biomass tannin as an auxiliary B;
s4, selecting silicate as an auxiliary agent C;
and S5, mixing the ABC three auxiliary agents in proportion to obtain the strength improver.
Example 2
The preparation method of the low-cost modified urea-formaldehyde resin comprises the following steps:
K1. finishing the first feeding in a reaction kettle under the condition of stirring, adding 300 parts of 40% formaldehyde, adjusting the reaction pH to 9, adding 2.5 parts of polyvinyl alcohol and 100 parts of urea, heating to 70 ℃, adding 13 parts of melamine and 1.6 parts of a first strength improver, heating to 95 ℃, and preserving heat for 40min to obtain a K1 reaction product;
K2. adjusting the reaction product of K1 with acid to pH 6.5, and carrying out K2 polycondensation reaction at 90 ℃ for 60min to obtain a K2 reaction product;
K3. regulating the reaction product of K2 by alkali to ensure that the pH value is 7, feeding for the second time at the temperature of 90 ℃, adding 12 parts of melamine and 55 parts of urea, and carrying out K3 polycondensation reaction for 40min at the temperature of 90 ℃ to obtain a reaction product of K3;
K4. regulating the reaction product of K3 with alkali to pH 7, feeding for the third time at 70-80 deg.c, adding 35 portions of urea and maintaining for 35min to obtain K4 reaction product;
K5. regulating the reaction product of K4 with alkali to pH 7.5, feeding for the fourth time at 70-80 deg.c, adding 12 portions of urea and 0.4 portion of second strength promoter, and maintaining for 10min to obtain reaction product of K5;
K6. regulating the reaction product of K5 with alkali to pH 7.5, and cooling; discharging when the temperature is reduced to 35 ℃.
The preparation method of the first/second strength improver comprises the following steps:
s1, reacting phthalic acid, maleic anhydride and diethylenetriamine at 160 ℃, cooling and diluting to obtain a hyperbranched amino polymer;
s2, mixing epoxy chloropropane, a solvent and the hyperbranched amino polymer, reacting at 80 ℃, and adjusting the pH to 8.5 to obtain a branched polymer cross-linking agent-assistant A;
s3, selecting biomass tannin as an auxiliary B;
s4, selecting silicate as an auxiliary agent C;
and S5, mixing the ABC three auxiliary agents in proportion to obtain the strength improver.
Example 3
The low-cost modified urea-formaldehyde resin adhesive comprises the following components in percentage by mass: 260 parts of formaldehyde, 1 part of polyvinyl alcohol, 191 parts of urea, 18 parts of melamine and 1-2 parts of strength improver.
The preparation method of the strength improver comprises the following steps:
s1, reacting phthalic acid, maleic anhydride and diethylenetriamine at 150 ℃, cooling and diluting to obtain a hyperbranched amino polymer;
s2, mixing epoxy chloropropane, a solvent and the hyperbranched amino polymer, reacting at 60 ℃, and adjusting the pH to 8 to obtain a branched polymer cross-linking agent-assistant A;
s3, selecting biomass tannin as an auxiliary B;
s4, selecting silicate as an auxiliary agent C;
and S5, mixing the ABC three auxiliary agents in proportion to obtain the strength improver.
Formaldehyde concentration is 37%; the polyvinyl alcohol is numbering 2189, and the purity is more than 99% of industrial grade; the melamine is in industrial grade with the purity of more than 99 percent; the urea is industrial grade with purity of more than 99%.
The molar ratio of the phthalic acid to the maleic anhydride to the diethylenetriamine is 9:1: 1.4; the mass ratio of the epichlorohydrin to the solvent to the hyperbranched amino polymer is 2:3:1, and the solvent is water.
The mass fraction of the hyperbranched amino polymer is 25-30%.
The biomass tannin is condensed tannin of black wattle, the purity is more than 98 percent, and the granularity is 100-; the silicate is industrial grade aluminum silicate with the purity of more than 99 percent and the granularity of more than 3000 meshes.
In the steps K1 and K5, the addition amount of the additive A and the additive B in the strength improver is too much, so that the glue cost is too high, and the cost advantage is reduced; when the addition amount of the additive C is too large, a precipitation phenomenon can occur. According to the invention, substances in a specific proportion are firstly reacted with formaldehyde to form a stable chemical bond, so that the performance of the glue is improved, and then after the addition polycondensation reaction of the glue is completed, a second strength improver is added after the glue is in a heat preservation stage, so that the stability of the glue is improved.
The preparation method of the low-cost modified urea-formaldehyde resin comprises the following steps:
K1. completing the first feeding in a reaction kettle under the condition of stirring, adding 260 parts of formaldehyde with the concentration of 37%, adjusting the pH value of the reaction to 8.5, adding 1 part of polyvinyl alcohol and 90 parts of urea, heating to 60 ℃, adding 11 parts of melamine and 0.8 part of strength improver, heating to 90 ℃, and keeping the temperature for 35 min;
K2. adjusting the pH of the K1 reactant to 6.0 with acid, and performing polycondensation reaction at 88 deg.C (40-60 min);
K3. adjusting the pH of a reactant K2 to 6.5 by using alkali, feeding for the second time at 85 ℃, adding 7 parts of melamine and 52 parts of urea, and performing polycondensation reaction at 85 ℃ (20-40 min);
K4. regulating the reactant of K3 with alkali to pH 6.5, feeding for the third time at 75 deg.c, adding 33 parts of urea and maintaining for 30 min;
K5. regulating the reactant of K4 with alkali to pH 8.0, feeding for the fourth time at 75 deg.c, adding urea 16 weight portions and strength promoter 0.2 weight portions, and maintaining for 15 min;
K6. the reaction product of K5 was adjusted to pH 8.0 with base and the temperature was reduced. And discharging when the temperature is reduced to 40 ℃.
The acid for adjusting the pH in the steps K1, K2, K3, K4, K5 and K6 is a formic acid solution diluted to 30% concentration, and the alkali is a sodium hydroxide solution diluted to 30% concentration.
The first strength-enhancing agent ratio in step K1 is: and (3) auxiliary agent A: and (3) auxiliary agent B: auxiliary agent C = 1: 1: 0; the second strength-enhancing agent ratio in step K5 is: and (3) auxiliary agent A: and (3) auxiliary agent B: auxiliary agent C = 0: 0:1.
Comparative example 1
The low-cost modified urea-formaldehyde resin adhesive comprises the following components in percentage by mass: 200 parts of formaldehyde, 3 parts of polyvinyl alcohol, 150 parts of urea, 10 parts of melamine and 1 part of strength improver. The strength improver adopts the conventional strength improver on the market.
Comparative example 2
The low-cost modified urea-formaldehyde resin adhesive comprises the following components in percentage by mass: 350 parts of formaldehyde, 0.01 part of polyvinyl alcohol, 215 parts of urea, 30 parts of melamine and 2 parts of strength improver. The strength improver adopts chitosan grafted organosilicon modified amphoteric polyacrylamide.
The adhesives prepared in examples 1,2 and 3 were used, respectively; the adhesives prepared in comparative examples 1,2 were used to prepare five ply-wood and to test the properties of the ply-wood.
The method comprises the steps of preparing the five-layer plywood by using eucalyptus veneers with the size of 400mm x 1.7mm, the adhesive and flour as raw materials, wherein the water content of the eucalyptus veneers is 10%, the proportion of the flour is 30%, the glue application amount is 400g/m2, the pressure, the temperature and the time are respectively 0.65MPa, 120 ℃ and 12 minutes, and the performance of the plywood product is detected according to the detection method of artificial boards and facing artificial boards physical and chemical performance experimental method GB/T17657-1999, and the detection results are shown in a table.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (10)
1. The low-cost modified urea-formaldehyde resin adhesive is characterized by comprising the following components in percentage by mass: 300 parts of formaldehyde 240-containing material, 0.1-2.5 parts of polyvinyl alcohol, 200 parts of urea 180-containing material, 15-25 parts of melamine and 1-2 parts of strength enhancer;
the preparation method of the strength improver comprises the following steps:
s1, reacting phthalic acid, maleic anhydride and diethylenetriamine at the temperature of 130-160 ℃, cooling and diluting to obtain a hyperbranched amino polymer;
s2, mixing epoxy chloropropane, a solvent and the hyperbranched amino polymer, reacting at 40-80 ℃, and adjusting the pH to 7.5-8.5 to obtain a branched polymer cross-linking agent-assistant A;
s3, selecting biomass tannin as an auxiliary B;
s4, selecting silicate as an auxiliary agent C;
and S5, mixing the ABC three auxiliary agents in proportion to obtain the strength improver.
2. The low-cost modified urea-formaldehyde resin adhesive according to claim 1, characterized by comprising the following components in parts by mass: 260 parts of formaldehyde, 1 part of polyvinyl alcohol, 191 parts of urea, 18 parts of melamine and 1-2 parts of strength improver.
3. The low-cost modified urea-formaldehyde resin adhesive according to claim 2, wherein the strength enhancer is prepared by the following steps:
s1, reacting phthalic acid, maleic anhydride and diethylenetriamine at 150 ℃, cooling and diluting to obtain a hyperbranched amino polymer;
s2, mixing epoxy chloropropane, a solvent and the hyperbranched amino polymer, reacting at 60 ℃, and adjusting the pH to 8 to obtain a branched polymer cross-linking agent-assistant A;
s3, selecting biomass tannin as an auxiliary B;
s4, selecting silicate as an auxiliary agent C;
and S5, mixing the ABC three auxiliary agents in proportion to obtain the strength improver.
4. The low-cost modified urea-formaldehyde resin adhesive according to claim 2, wherein the formaldehyde is present at a concentration of 37%; the polyvinyl alcohol is numbering 2189, and the purity is over 99 percent of industrial grade; the melamine is in industrial grade with the purity of more than 99 percent; the urea is of industrial grade with purity of more than 99%.
5. The low-cost modified urea-formaldehyde resin adhesive according to claim 2, wherein the molar ratio of phthalic acid, maleic anhydride and diethylenetriamine is 9:1: 1.4; the mass ratio of the epoxy chloropropane to the solvent to the hyperbranched amino polymer is 2:3:1, and the solvent is water.
6. The low-cost modified urea-formaldehyde resin adhesive according to claim 2, wherein: the mass fraction of the hyperbranched amino polymer is 25-30%; the biomass tannin is condensed tannin of black wattle, the purity is more than 98 percent, and the granularity is 100-120 meshes; the silicate is industrial grade aluminum silicate with the purity of more than 99 percent and the granularity of more than 3000 meshes.
7. The low-cost modified urea-formaldehyde resin adhesive according to any one of claims 1 to 6, wherein: the preparation method of the low-cost modified urea-formaldehyde resin comprises the following steps:
K1. completing the first feeding in a reaction kettle under the condition of stirring, adding 300 parts of formaldehyde 240-40%, adjusting the reaction pH to 8-9, adding 0.1-2.5 parts of polyvinyl alcohol and 80-100 parts of urea, heating to 50-70 ℃, adding 9-13 parts of melamine and 0.6-1.6 parts of first strength promoter, heating to 85-95 ℃, and preserving heat for 30-40min to obtain a K1 reaction product;
K2. adjusting the reaction product of K1 with acid to pH 5.5-6.5, and carrying out K2 polycondensation reaction at 85-90 deg.C for 40-60min to obtain K2 reaction product;
K3. regulating the pH value of a K2 reaction product to 6-7 by using alkali, carrying out secondary feeding at the temperature of 80-90 ℃, adding 5-12 parts of melamine and 50-55 parts of urea, and carrying out K3 polycondensation reaction for 20-40min at the temperature of 80-90 ℃ to obtain a K3 reaction product;
K4. regulating the reaction product of K3 with alkali to pH 6-7, feeding for the third time at 70-80 deg.c, adding urea 30-35 weight portions, and maintaining for 25-35min to obtain reaction product of K4;
K5. regulating the reaction product of K4 with alkali to pH 7.5-8.5, feeding for the fourth time at 70-80 deg.c, adding urea 12-20 weight portions and second strength promoter 0.1-0.4 weight portions, and maintaining for 10-20min to obtain K5 reaction product;
K6. regulating the reaction product of K5 with alkali to pH 7.5-8.5, and cooling; discharging when the temperature is reduced to 35-45 ℃.
8. The low-cost modified urea-formaldehyde resin adhesive according to claim 7, wherein: the preparation method of the low-cost modified urea-formaldehyde resin comprises the following steps:
K1. completing the first feeding in a reaction kettle under the condition of stirring, adding 260 parts of formaldehyde with the concentration of 37%, adjusting the pH value of the reaction to 8.5, adding 1 part of polyvinyl alcohol and 90 parts of urea, heating to 60 ℃, adding 11 parts of melamine and 0.8 part of strength improver, heating to 90 ℃, and keeping the temperature for 35 min;
K2. adjusting the pH of the K1 reactant to 6.0 with acid, and performing polycondensation reaction at 88 deg.C (40-60 min);
K3. adjusting the pH of a reactant K2 to 6.5 by using alkali, feeding for the second time at 85 ℃, adding 7 parts of melamine and 52 parts of urea, and performing polycondensation reaction at 85 ℃ (20-40 min);
K4. regulating the reactant of K3 with alkali to pH 6.5, feeding for the third time at 75 deg.c, adding 33 parts of urea and maintaining for 30 min;
K5. regulating the reactant of K4 with alkali to pH 8.0, feeding for the fourth time at 75 deg.c, adding urea 16 weight portions and strength promoter 0.2 weight portions, and maintaining for 15 min;
K6. adjusting the reactant of K5 to pH 8.0 with alkali, and cooling; and discharging when the temperature is reduced to 40 ℃.
9. The low-cost modified urea-formaldehyde resin adhesive according to claim 8, wherein: the first strength-enhancing agent proportion in the step K1 is as follows: and (3) auxiliary agent A: and (3) auxiliary agent B: auxiliary agent C = 1: 1:0.
10. The low-cost modified urea-formaldehyde resin adhesive according to claim 9, wherein: the second strength-enhancing agent ratio in the step K5 is: and (3) auxiliary agent A: and (3) auxiliary agent B: auxiliary agent C = 0: 0:1.
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| CN1884418A (en) * | 2006-07-07 | 2006-12-27 | 南阳师范学院 | Amino resin binding agent for preparing superstrong water-tight bamboo-wood sheet and sheet production process |
| CN103666351A (en) * | 2013-12-13 | 2014-03-26 | 广西大学 | Modified urea-formaldehyde glue for base material laminated board of laminated solid wood floor and preparation method thereof |
| CN107987766A (en) * | 2017-12-14 | 2018-05-04 | 南京林业大学 | A kind of method that biomass adhesive is prepared using formaldehyde slag |
| CN111675998A (en) * | 2020-07-03 | 2020-09-18 | 德华兔宝宝装饰新材股份有限公司 | Bean pulp adhesive for blockboard and preparation method thereof |
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- 2021-12-27 CN CN202111613498.5A patent/CN114231226A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1884418A (en) * | 2006-07-07 | 2006-12-27 | 南阳师范学院 | Amino resin binding agent for preparing superstrong water-tight bamboo-wood sheet and sheet production process |
| CN103666351A (en) * | 2013-12-13 | 2014-03-26 | 广西大学 | Modified urea-formaldehyde glue for base material laminated board of laminated solid wood floor and preparation method thereof |
| CN107987766A (en) * | 2017-12-14 | 2018-05-04 | 南京林业大学 | A kind of method that biomass adhesive is prepared using formaldehyde slag |
| CN111675998A (en) * | 2020-07-03 | 2020-09-18 | 德华兔宝宝装饰新材股份有限公司 | Bean pulp adhesive for blockboard and preparation method thereof |
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