CN113214115A - Low-cost environment-friendly incremental resin and preparation method and application thereof - Google Patents
Low-cost environment-friendly incremental resin and preparation method and application thereof Download PDFInfo
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- C07C275/10—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton being further substituted by singly-bound oxygen atoms
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Abstract
The invention discloses a low-cost environment-friendly incremental resin and a preparation method and application thereof, and relates to an incremental resin for an aldehyde-free adhesive and a preparation method and application thereof. The invention aims to solve the problems that the existing formaldehyde-free environment-friendly soybean adhesive is too high in cost and cannot be widely applied. The low-cost environment-friendly incremental resin is prepared from epoxy chloropropane, a reaction promoter and an amino-containing monomer; the preparation method comprises the following steps: heating epoxy chloropropane, adding a reaction promoter and an amino-containing monomer, stirring for reaction to obtain a transparent homogeneous solution, continuously reacting the transparent homogeneous solution, controlling residual epoxy groups, keeping for a certain time, and finally cooling to obtain the low-cost environment-friendly incremental resin; the application comprises the following steps: the low-cost environment-friendly incremental resin is applied to preparing the soybean adhesive.
Description
Technical Field
The invention relates to an incremental resin for an aldehyde-free adhesive, and a preparation method and application thereof.
Background
The yield of the artificial board in 2019 is about 3.08 billion cubic meters in China, which is the first major country of artificial board production, consumption and import and export trade. However, the production of the artificial board in China mainly uses urea-formaldehyde resin adhesive, which accounts for about 90% of the adhesive for the artificial board. The urea-formaldehyde resin adhesive and the artificial board thereof release free formaldehyde in the processes of production, transportation, use and the like, not only pollute the environment, but also harm the health of people, so that the new standard GB18580-2017 of 'the formaldehyde release limit in the artificial board of indoor decoration materials and products thereof' is issued in 2017, more strict requirements are provided for the formaldehyde release amount of the artificial board and a test method, and the environment-friendly formaldehyde-free adhesive and the formaldehyde-free artificial board are eagerly demanded by the society and the industry.
The development and the use of the formaldehyde-free environment-friendly adhesive become an effective way for solving the problem of formaldehyde release of the artificial board and the products thereof. The soybean adhesive is an aldehyde-free environment-friendly adhesive prepared by using oil-pressing soybean meal or defatted soybean meal as a main raw material, and has the advantages of no formaldehyde addition, rich and renewable raw materials, excellent bonding performance and the like, so that the industrial production application in artificial boards such as common plywood, furniture boards, laminated wood boards, solid wood composite floor base materials, shaving boards and the like in China is realized in recent years. Currently, the soybean adhesive applied to industrial production of artificial boards in China is prepared by mainly using polyamide polyamine-epichlorohydrin resin as a dispersing agent and a crosslinking agent and stirring the polyamide polyamine-epichlorohydrin resin and defatted soybean powder or oil-extracted soybean meal powder at room temperature.
The polyamide polyamine-epichlorohydrin resin is a substance which is synthesized by diethylenetriamine, triethylene tetramine, organic dibasic acid and epichlorohydrin and can be efficiently crosslinked with amino and carboxyl of soybean flour, and the price is high. Based on the market price of the chemical raw materials in China at the beginning of 3 months in 2021, the raw material cost of the polyamide polyamine-epichlorohydrin resin solid is about 17000 yuan/ton, so that the raw material cost of the formaldehyde-free soybean adhesive is about 2565 yuan/ton, which is higher than the price (2400 yuan/ton) of E0-grade urea-formaldehyde resin, and the wide application of the soybean adhesive in the artificial board industry is limited in price. Especially, during 3-5 months in 2021, the price of the raw material diethylenetriamine for producing the polyamide polyamine-epichlorohydrin resin rises from 28000 yuan/ton to more than 42000 yuan/ton, so that the raw material cost of the polyamide polyamine-epichlorohydrin resin is further increased by about 23.5 percent, and the raw material cost of the soybean adhesive is increased by about 6.5 percent.
However, with the increase of environmental awareness of people, the demand of the society and industry for formaldehyde-free environment-friendly adhesives and formaldehyde-free artificial board products is increasing. Therefore, on the premise of ensuring the bonding performance and the service performance of the soybean adhesive, how to effectively reduce the cost of the soybean adhesive becomes a bottleneck problem of wide application of the soybean adhesive in the artificial board industry. Only soybean adhesives with excellent bonding performance, good process service performance and production cost accepted by artificial board production enterprises can be widely applied in the artificial board industry, so that high-quality formaldehyde-free artificial boards and green environment-friendly building materials can be provided for the society, formaldehyde emission is thoroughly eliminated, and a healthy and safe human living environment is created.
Disclosure of Invention
The invention provides an environment-friendly incremental resin with low cost and a preparation method and application thereof, aiming at solving the problems that the existing formaldehyde-free environment-friendly soybean adhesive is too high in cost and cannot be widely applied.
The low-cost environment-friendly incremental resin is prepared from 100 parts by mass of epoxy chloropropane, 5-15 parts by mass of a reaction promoter and 25-75 parts by mass of an amino-containing monomer; the low-cost environment-friendly incremental resin comprises 60-95% of solid by mass and 6000-10000 mPa.s of viscosity at 25 ℃; the low-cost environment-friendly incremental resin is a liquid product which is easily dissolved in water.
A preparation method of low-cost environment-friendly incremental resin is completed according to the following steps:
weighing 100 parts of epoxy chloropropane, 5-15 parts of a reaction promoter and 25-75 parts of an amino-containing monomer according to the mass parts;
secondly, firstly heating 100 parts of epoxy chloropropane to 60-120 ℃, adding 5-15 parts of reaction accelerator and 25-75 parts of amino-containing monomer, then reacting for 2-4 h under the condition of stirring and temperature of 60-120 ℃ to obtain a transparent homogeneous solution, continuously reacting the transparent homogeneous solution under the condition of stirring and temperature of 60-120 ℃ until the mass percentage of residual epoxy groups in the system is lower than 0.05%, then keeping for 20-40 min under the condition of stirring and temperature of 60-120 ℃, and finally stopping heating and cooling to below 45 ℃ to obtain the low-cost environment-friendly incremental resin.
The application of the low-cost environment-friendly incremental resin is to prepare the soybean adhesive.
The invention has the beneficial effects that:
1) because the increment resin contains alkyl chloride, amino and hydroxyl, wherein the alkyl chloride can react with protein in defatted soybean flour or oil-pressing soybean meal, and the amino can generate a co-crosslinking reaction with azetidinyl in the polyamide polyamine-epichlorohydrin resin (as verified by an infrared spectrogram in a figure 4), the crosslinking density and the cohesive strength of the polyamide polyamine-epichlorohydrin resin are improved; in addition, the extended resin of the present invention is excellent in water solubility and is completely miscible with the polyamide polyamine-epichlorohydrin resin, as shown in fig. 1B. Therefore, the composite crosslinking agent formed by blending the extender resin and the polyamide polyamine-epichlorohydrin resin can effectively crosslink defatted soybean flour or oil-pressing soybean meal to form the soybean adhesive shown in the figure 1C, and the bonding performance and the use performance of the soybean adhesive are the same as those of the soybean adhesive modified by singly using the polyamide polyamine-epichlorohydrin resin.
2) The raw materials used for synthesizing the polyamide polyamine-epichlorohydrin resin are diethylenetriamine, adipic acid and epichlorohydrin, and the raw materials used for synthesizing the incremental resin are epichlorohydrin, urea or thiourea. Because the raw material cost of urea and thiourea is lower than that of diethylenetriamine and adipic acid, the incremental resin cost of the invention is obviously lower than that of polyamide polyamine-epichlorohydrin resin. The price of the chemical raw materials in China is 5 months in 2021, the raw material cost of the polyamide polyamine-epichlorohydrin resin solid is 21000 yuan/ton, while the raw material cost of the incremental resin solid is 9400-11000 yuan/ton, and the cost is reduced by 47-55%. Therefore, on the premise of ensuring the gluing performance, the adhesive can replace 70% of expensive polyamide polyamine-epichlorohydrin resin, so that the raw material cost of the soybean adhesive can be reduced to 17.7%, and the raw material cost can be lower than the cost (about 2400 yuan/ton) of E0-grade urea-formaldehyde resin adhesive.
3) The extender resin is free from formaldehyde in the preparation process, the product is easy to dissolve in water, can be blended with polyamide polyamine-epichlorohydrin resin in any proportion, and is synergistic with cross-linked defatted soybean powder or oil-pressing soybean meal powder, so that the extender resin is a low-cost green environment-friendly extender with the bonding performance and the use performance completely meeting the requirements of aldehyde-free artificial board production.
Drawings
FIG. 1 is an appearance diagram of an environment-friendly extender resin, a cross-linking agent solution containing the extender resin and a soybean adhesive, wherein A is the environment-friendly extender resin with low cost prepared in the first embodiment, B is the cross-linking agent solution containing the extender resin prepared in the fourth step of the first embodiment, and C is the soybean adhesive prepared in the fourth step of the second embodiment;
fig. 2 is a picture of fluidity of an environment-friendly incremental resin, a cross-linking agent solution containing the incremental resin and a soybean adhesive, wherein a is the environment-friendly incremental resin with low cost prepared in the first embodiment, B is the cross-linking agent solution containing the incremental resin prepared in the fourth step (C) of the first embodiment, and C is the soybean adhesive prepared in the fourth step (C) of the first embodiment;
FIG. 3 is a schematic diagram of the reaction of the present invention; (1) the synthetic schematic diagram of the environment-friendly incremental resin, (2) the cross-linking schematic diagram of the environment-friendly incremental resin and the polyamide polyamine-epichlorohydrin resin, (3) the cross-linking schematic diagram of the environment-friendly incremental resin and the bean flour;
FIG. 4 is an infrared spectrum of the cured product of example four, wherein a is the cured extender resin, b is the cured polyamidoamine-epichlorohydrin resin, and c is the cured composite crosslinker resin.
Detailed Description
The technical solution of the present invention is not limited to the specific embodiments listed below, and includes any combination of the specific embodiments.
The first embodiment is as follows: the low-cost environment-friendly incremental resin is prepared from 100 parts by mass of epoxy chloropropane, 5-15 parts by mass of a reaction promoter and 25-75 parts by mass of an amino-containing monomer; the low-cost environment-friendly incremental resin comprises 60-95% of solid by mass and 6000-10000 mPa.s of viscosity at 25 ℃; the low-cost environment-friendly incremental resin is a liquid product which is easily dissolved in water.
The purpose of the present embodiment is to provide a novel environment-friendly incremental resin with low cost, to perform incremental modification on a polyamide polyamine-epichlorohydrin resin, so as to effectively reduce the raw material cost of a soybean adhesive and make the raw material cost lower than that of E0-grade urea-formaldehyde resin on the premise of ensuring effective crosslinking of the polyamide polyamine-epichlorohydrin resin on defatted soybean flour and the gluing performance and usability of the prepared soybean adhesive, thereby promoting wide application of the formaldehyde-free environment-friendly soybean adhesive in the artificial board industry.
FIG. 3 is a schematic diagram of the reaction of the present invention; (1) the synthetic schematic diagram of the environment-friendly incremental resin, (2) the cross-linking schematic diagram of the environment-friendly incremental resin and the polyamide polyamine-epichlorohydrin resin, (3) the cross-linking schematic diagram of the environment-friendly incremental resin and the bean flour;
the reaction promoter of the embodiment can promote the reaction of the amino monomer and the epichlorohydrin to form a product which is homogeneous, transparent and easily soluble in water. Water, ethylene glycol, glycerol and mixtures thereof are preferably selected for environmental protection and cost.
It is preferred to use urea, thiourea or a mixture of the two for the amino group-containing monomer due to the irritating ammonia odor of aqueous ammonia and for cost reasons. The amino group on the urea or thiourea reacts with the epichlorohydrin to form products shown in a reaction formula (1) in figure 3, and the products can respectively react with a soybean protein amino group or a polyamide polyamine-epichlorohydrin resin azetidinyl group in the soybean adhesive to form a cross-linked network structure shown in reaction formulas (2) and (3) in figure 3, so that the soybean adhesive is endowed with a good cross-linked network structure.
Therefore, the extender resin of the present embodiment contains three groups, namely alkyl chloride, amino and hydroxyl, wherein the alkyl chloride can react with protein in the defatted soybean flour or oil-pressing soybean meal to form a cross-linked structure as shown in the reaction formula (3) in fig. 3, and the polar amino and hydroxyl can form hydrogen bonds with polar groups in the wood, the defatted soybean flour or oil-pressing soybean meal to provide a good bonding effect through an adsorption bonding mechanism, so that the extender resin itself serves as a crosslinking modifier of the soybean adhesive, but the crosslinking effect is weaker than that of the polyamide polyamine-epichlorohydrin resin (see examples and verification experiment results). Meanwhile, the amine group contained in the incremental resin can generate a co-crosslinking reaction with the azetidinyl group in the polyamide polyamine-epichlorohydrin resin, as shown in a reaction formula (2) in figure 3 and verified in an infrared spectrogram in figure 4, so that the crosslinking density and the cohesive strength of the polyamide polyamine-epichlorohydrin resin can be improved. Therefore, the composite cross-linking agent formed by blending the increment resin and the polyamide polyamine-epichlorohydrin resin can generate a synergistic effect with the polyamide polyamine-epichlorohydrin resin, so that defatted soybean flour or oil-pressing soybean meal powder can be effectively cross-linked, and the novel soybean adhesive with good bonding performance is formed.
The beneficial effects of the embodiment are as follows:
1) because the incremental resin of the embodiment contains alkyl chloride, amino and hydroxyl, wherein the alkyl chloride can react with protein in defatted soybean flour or oil-pressing soybean meal, and the amino can generate a co-crosslinking reaction with azetidinyl in the polyamide polyamine-epichlorohydrin resin (as verified by an infrared spectrogram in fig. 4), the crosslinking density and the cohesive strength of the polyamide polyamine-epichlorohydrin resin are improved; in addition, the extended resin of the present embodiment has excellent water solubility and is completely miscible with the polyamide polyamine-epichlorohydrin resin, as shown in fig. 1B. Therefore, the composite crosslinking agent formed by blending the extender resin and the polyamide polyamine-epichlorohydrin resin can effectively crosslink defatted soybean flour or oil-pressing soybean meal to form the soybean adhesive shown in the figure 1C, and the bonding performance and the use performance of the soybean adhesive are the same as those of the soybean adhesive modified by singly using the polyamide polyamine-epichlorohydrin resin.
2) The raw materials used for synthesizing the polyamide polyamine-epichlorohydrin resin are diethylenetriamine, adipic acid and epichlorohydrin, and the raw materials used for synthesizing the incremental resin of the embodiment are epichlorohydrin, urea or thiourea. Because the raw material cost of urea and thiourea is lower than that of diethylenetriamine and adipic acid, the incremental resin cost of the embodiment is obviously lower than that of the polyamide polyamine-epichlorohydrin resin. The price of the chemical raw materials in China is 5 months in 2021, the raw material cost of the polyamide polyamine-epichlorohydrin resin solid is 21000 yuan/ton, while the raw material cost of the incremental resin solid is 9400-11000 yuan/ton, and the cost is reduced by 47-55%. Therefore, on the premise of ensuring the gluing performance, the adhesive can replace 70% of expensive polyamide polyamine-epichlorohydrin resin, so that the raw material cost of the soybean adhesive can be reduced to 17.7%, and the raw material cost can be lower than the cost (about 2400 yuan/ton) of E0-grade urea-formaldehyde resin adhesive.
3) The extender resin is free from formaldehyde in the preparation process, the product is easy to dissolve in water, can be blended with polyamide polyamine-epichlorohydrin resin in any proportion, and is synergistic with cross-linked defatted soybean powder or oil-pressing soybean meal powder, so that the extender resin is a low-cost green environment-friendly extender with the bonding performance and the use performance completely meeting the requirements of aldehyde-free artificial board production.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the reaction promoter is a polar micromolecular substance containing hydroxyl or amino. The rest is the same as the first embodiment.
The third concrete implementation mode: this embodiment is different from the first or second embodiment in that: the reaction promoter is one or a mixture of a plurality of water, ethylene glycol, propylene glycol, butanediol, glycerol, monoethanolamine, diethanolamine, triethanolamine and formamide. The other is the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: the amino-containing monomer is a monomer containing two or more amino groups in the molecule. The others are the same as the first to third embodiments.
The fifth concrete implementation mode: the first to fourth differences of this embodiment from the first to fourth embodiments are: the amino-containing monomer is one or a mixture of two of urea and thiourea. The rest is the same as the first to fourth embodiments.
The sixth specific implementation mode: the embodiment is a preparation method of low-cost environment-friendly incremental resin, which is completed by the following steps:
weighing 100 parts of epoxy chloropropane, 5-15 parts of a reaction promoter and 25-75 parts of an amino-containing monomer according to the mass parts;
secondly, firstly heating 100 parts of epoxy chloropropane to 60-120 ℃, adding 5-15 parts of reaction accelerator and 25-75 parts of amino-containing monomer, then reacting for 2-4 h under the condition of stirring and temperature of 60-120 ℃ to obtain a transparent homogeneous solution, continuously reacting the transparent homogeneous solution under the condition of stirring and temperature of 60-120 ℃ until the mass percentage of residual epoxy groups in the system is lower than 0.05%, then keeping for 20-40 min under the condition of stirring and temperature of 60-120 ℃, and finally stopping heating and cooling to below 45 ℃ to obtain the low-cost environment-friendly incremental resin.
The seventh embodiment: the sixth embodiment is different from the sixth embodiment in that: in the first step, 100 parts of epoxy chloropropane, 5-10 parts of reaction accelerator and 25-44 parts of amino-containing monomer are weighed according to the mass parts. The rest is the same as the sixth embodiment.
The specific implementation mode is eight: the embodiment is an application of the low-cost environment-friendly incremental resin, and the low-cost environment-friendly incremental resin is applied to preparation of the soybean adhesive.
The specific implementation method nine: the eighth embodiment is different from the eighth embodiment in that: the application of the low-cost environment-friendly incremental resin to the preparation of the soybean adhesive is carried out according to the following steps:
preparing a crosslinking agent solution containing an incremental resin:
a. diluting polyamide polyamine-epichlorohydrin resin with water to a solid content of 5-12% by mass to obtain a diluted polyamide polyamine-epichlorohydrin resin solution;
b. diluting the low-cost environment-friendly incremental resin with water to a solid mass percent of 5-12% to obtain a diluted environment-friendly incremental resin solution;
c. mixing the diluted polyamide polyamine-epichlorohydrin resin solution with the diluted environment-friendly incremental resin solution to obtain a crosslinking agent solution containing the incremental resin;
the mass ratio of the diluted polyamide polyamine-epichlorohydrin resin solution to the diluted environment-friendly incremental resin solution is 1 (0.25-4);
preparing soybean adhesive:
weighing 100 parts of crosslinking agent solution containing the incremental resin and 30-50 parts of bean flour according to the parts by weight, adding 30-50 parts of bean flour into 100 parts of crosslinking agent solution containing the incremental resin, and stirring uniformly at room temperature to obtain the soybean adhesive. The rest is the same as the embodiment eight.
The detailed implementation mode is ten: this embodiment differs from one of the eighth or ninth embodiments in that: the bean flour in the second step is defatted bean flour or oil-pressing bean cake flour. The others are the same as the embodiments eight or nine.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows:
a low-cost environment-friendly incremental resin is prepared by the following steps:
weighing 100 parts of epoxy chloropropane, 10 parts of a reaction promoter and 44 parts of an amino-containing monomer according to the mass parts;
heating 100 parts of epoxy chloropropane to 75 ℃, adding 10 parts of reaction accelerator and 44 parts of amino-containing monomer, reacting for 2.5 hours under the conditions of stirring and 75 ℃ to obtain a transparent homogeneous solution, continuously reacting the transparent homogeneous solution under the conditions of stirring and 75-85 ℃ until the mass percentage of residual epoxy groups in the system is lower than 0.05 percent, keeping for 30 minutes under the conditions of stirring and 75-85 ℃, and finally stopping heating and cooling to below 45 ℃ to obtain the low-cost environment-friendly incremental resin; the mass percent of the solid in the low-cost environment-friendly incremental resin is 91.6%, and the viscosity at 25 ℃ is 7600 mPa.s; the low-cost environment-friendly incremental resin is a light-yellow liquid product which is homogeneous, transparent and easily soluble in water;
the reaction promoter is water;
the amino-containing monomer is urea.
And in the second step, the reaction is carried out in a reaction kettle provided with a thermometer, a reflux device and a stirring device.
And in the second step, when the reaction lasts for about 3 hours, the mass percent of the residual epoxy groups in the system is lower than 0.05 percent.
Based on the price of the chemical raw materials in China at 5 months in 2021, the solid raw material cost of the low-cost environment-friendly incremental resin prepared in the first embodiment is 9450 yuan/ton, which is reduced by 55% compared with the solid raw material cost (21000 yuan/ton) of the commercially available polyamide polyamine-epichlorohydrin resin.
Example two:
a low-cost environment-friendly incremental resin is prepared by the following steps:
weighing 100 parts of epoxy chloropropane, 8 parts of a reaction promoter and 31.1 parts of an amino-containing monomer according to the mass parts;
heating 100 parts of epoxy chloropropane to 95 ℃, adding 8 parts of reaction accelerator and 31.1 parts of amino-containing monomer, reacting for 4 hours under the conditions of stirring and 95 ℃ to obtain a transparent homogeneous solution, continuously reacting the transparent homogeneous solution under the conditions of stirring and 95-105 ℃ until the mass percentage of residual epoxy groups in the system is lower than 0.05 percent, keeping for 30 minutes under the conditions of stirring and 95-105 ℃, and finally stopping heating and cooling to below 45 ℃ to obtain the low-cost environment-friendly incremental resin; the mass percentage of the solid in the low-cost environment-friendly incremental resin is 94.7%, and the viscosity at 25 ℃ is 9360 mPa.s; the low-cost environment-friendly incremental resin is a light-yellow liquid product which is homogeneous, transparent and easily soluble in water;
the reaction promoter is glycol;
the amino-containing monomer is urea.
And in the second step, the reaction is carried out in a reaction kettle provided with a thermometer, a reflux device and a stirring device.
And in the second step, when the reaction lasts for about 3.5 hours, the mass percent of the residual epoxy groups in the system is lower than 0.05 percent.
Based on the price of the chemical raw materials in China at 5 months in 2021, the solid raw material cost of the low-cost environment-friendly incremental resin prepared in the second embodiment is 10500 yuan/ton, which is reduced by 50% compared with the solid raw material cost (21000 yuan/ton) of the commercially available polyamide polyamine-epichlorohydrin resin.
Example three:
a low-cost environment-friendly incremental resin is prepared by the following steps:
weighing 100 parts of epoxy chloropropane, 10 parts of a reaction promoter and 37.8 parts of an amino-containing monomer according to the mass parts;
heating 100 parts of epoxy chloropropane to 95 ℃, adding 10 parts of reaction accelerator and 37.8 parts of amino-containing monomer, reacting for 2.8 hours under the conditions of stirring and 80 ℃ to obtain a transparent homogeneous solution, continuously reacting the transparent homogeneous solution under the conditions of stirring and 80-95 ℃ until the mass percentage of residual epoxy groups in the system is lower than 0.05 percent, keeping for 30 minutes under the conditions of stirring and 80-95 ℃, and finally stopping heating and cooling to below 45 ℃ to obtain the low-cost environment-friendly incremental resin; the mass percent of the solid in the low-cost environment-friendly incremental resin is 93.1%, and the viscosity at 25 ℃ is 8480 mPa.s; the low-cost environment-friendly incremental resin is a light-yellow liquid product which is homogeneous, transparent and easily soluble in water;
the reaction accelerator is a mixture of glycol and water in equal mass ratio;
the amino-containing monomer is urea.
And in the second step, the reaction is carried out in a reaction kettle provided with a thermometer, a reflux device and a stirring device.
And in the second step, when the reaction lasts for about 3 hours, the mass percent of the residual epoxy groups in the system is lower than 0.05 percent.
Based on the price of the chemical raw materials in China at 5 months in 2021, the solid raw material cost of the low-cost environment-friendly incremental resin prepared in the third embodiment is 9920 yuan/ton, which is 53% lower than that of the commercially available polyamide polyamine-epichlorohydrin resin (21000 yuan/ton).
Example four:
the low-cost environment-friendly incremental resin prepared in the first embodiment is blended with commercially available polyamide polyamine-epichlorohydrin resin, and the soybean adhesive is prepared by using the blended resin, and the specific method is as follows:
preparing a crosslinking agent solution containing an incremental resin:
a. diluting a commercially available polyamide polyamine-epichlorohydrin resin with the mass percent of 15.2% to the mass percent of solid parts of 8% by using water to obtain a diluted polyamide polyamine-epichlorohydrin resin solution;
b. diluting the low-cost environment-friendly incremental resin prepared in the first embodiment with water to 8 mass percent of solid to obtain a diluted environment-friendly incremental resin solution;
c. mixing the diluted polyamide polyamine-epichlorohydrin resin solution with the diluted environment-friendly incremental resin solution to obtain a crosslinking agent solution containing the incremental resin; the mass ratio of the diluted polyamide polyamine-epichlorohydrin resin solution to the diluted environment-friendly incremental resin solution is 30: 70;
preparing soybean adhesive:
weighing 100 parts by mass of a crosslinking agent solution containing the incremental resin and 40 parts by mass of defatted soybean flour, adding 40 parts by mass of defatted soybean flour into 100 parts by mass of the crosslinking agent solution containing the incremental resin, and uniformly stirring at room temperature to obtain the soybean adhesive.
Weighing 50 parts by mass of the diluted polyamide polyamine-epichlorohydrin resin solution prepared in the step a in the fourth step of the example, 50 parts by mass of the diluted environment-friendly incremental resin solution prepared in the step b in the fourth step of the example and 50 parts by mass of the crosslinking agent solution containing the incremental resin prepared in the step c in the fourth step of the example, respectively putting the diluted environment-friendly incremental resin solution and the crosslinking agent solution into a polytetrafluoroethylene dish, and keeping the mixture in an oven at the temperature of 120 +/-2 ℃ for 5 hours to obtain the cured incremental resin, the cured polyamide polyamine-epichlorohydrin resin and the cured composite crosslinking agent resin. The infrared spectra of the three cured samples were measured using a Magna-ir560e.s.p type FT-IR spectrometer using KBr sheeting method.
FIG. 4 is an infrared spectrum of the cured product of example four, wherein a is the cured extender resin, b is the cured polyamidoamine-epichlorohydrin resin, and c is the cured composite crosslinker resin. The infrared spectrum analysis result shows that: cured extended resin at 3332cm-1The infrared absorption peak represents the stretching vibration of NH, but in the cured composite crosslinking agent resin, the maximum infrared absorption peak of the region is shifted to 3260cm-1At least one of (1) and (b); cured polyamidoamine-epichlorohydrin resin at 1222cm-1The infrared absorption peak at (B) represents the stretching vibration of C-O, but in the cured composite crosslinking agent resin, the infrared absorption peak is shifted to 1258cm-1At least one of (1) and (b); and the cured extender resin and the cured polyamidopolyamine-epichlorohydrin resin are at 1000cm-1～1100cm-1And (b) represents an absorption double peak of C-N bending vibration, and in the cured composite cross-linking agent resin, the absorption double peak becomes a single peak structure. These shifts of the infrared absorption peaks confirm that the co-crosslinking reaction between the extended resin and the polyamide polyamine-epichlorohydrin resin occurs, as shown in reaction formula (2) of fig. 3.
FIG. 1 is an appearance diagram of an environment-friendly extender resin, a cross-linking agent solution containing the extender resin and a soybean adhesive, wherein A is the environment-friendly extender resin with low cost prepared in the first embodiment, B is the cross-linking agent solution containing the extender resin prepared in the fourth step of the first embodiment, and C is the soybean adhesive prepared in the fourth step of the second embodiment; fig. 2 is a picture of fluidity of an environment-friendly incremental resin, a cross-linking agent solution containing the incremental resin and a soybean adhesive, wherein a is the environment-friendly incremental resin with low cost prepared in the first embodiment, B is the cross-linking agent solution containing the incremental resin prepared in the fourth step (C) of the first embodiment, and C is the soybean adhesive prepared in the fourth step (C) of the first embodiment; as can be seen from the figure, the low-cost environment-friendly incremental resin prepared in the first embodiment is a light yellow homogeneous transparent liquid product, the crosslinking agent solution containing the incremental resin is a homogeneous solution, and the soybean adhesive is good in uniform fluidity.
Example five:
the evaluation of the gluing performance of the soybean adhesive by using the amount of the prepared low-cost environment-friendly incremental resin in the first embodiment:
preparing a crosslinking agent solution containing an incremental resin:
a. diluting a commercially available polyamide polyamine-epichlorohydrin resin with the mass percent of 15.2% to the mass percent of solid parts of 8% by using water to obtain a diluted polyamide polyamine-epichlorohydrin resin solution;
b. diluting the low-cost environment-friendly incremental resin prepared in the first embodiment with water to 8 mass percent of solid to obtain a diluted environment-friendly incremental resin solution;
c. mixing the diluted polyamide polyamine-epichlorohydrin resin solution with the diluted environment-friendly incremental resin solution to obtain 7 crosslinking agent solutions with different dosage of incremental resins;
the mass ratio of the diluted polyamide polyamine-epichlorohydrin resin solution to the diluted environment-friendly incremental resin solution is respectively 0:100 (100% incremental resin reference), 15:85, 30:70, 45:55, 60:40, 80:20 and 100:0 (100% polyamide polyamine-epichlorohydrin resin reference);
preparing soybean adhesive:
respectively weighing 100 parts of cross-linking agent solutions of 7 different-dosage incremental resins and 35 parts of defatted soybean flour according to the mass parts, respectively adding 35 parts of defatted soybean flour into the cross-linking agent solutions of the 7 different-dosage incremental resins, and uniformly stirring at room temperature to obtain the 7 soybean adhesives.
Preparing a three-layer plywood by using birch veneers with the thickness of 1.6mm, drying the birch veneers in advance until the water content is 5% -7%, and then respectively coating the 7 soybean adhesives prepared in the embodiment on two surfaces of a veneer core layer, wherein the adhesive application amount is 380g/m2(double-side sizing amount, liquid glue solution metering); and (3) forming a slab blank by the glued birch veneers, prepressing for 30min under the condition of the pressure of 1.2MPa, and then hot-pressing for 4.5min under the conditions of the temperature of 120 ℃ and the pressure of 1.3MPa to obtain 7 types of three-layer plywood. The plywood was tested for dry bond strength and 63 ℃ wet bond strength by the method specified in the national standard GB/T17657-2015, as shown in Table 1.
Table 1 example five different amounts of crosslinker solution for extender resin to modulate the adhesive properties of soy adhesives
Note: the number in brackets (x/10) indicates the x pieces remaining after 28h "boil-dry-boil" treatment of 10 test pieces.
The results show that: although the soybean adhesive prepared by using the extender resin of the embodiment alone can be pressed to obtain plywood, the dry strength of the plywood exceeds the national standard requirement value (1.00MPa), the water resistance (63 ℃ water bubble wet strength) of the plywood cannot reach the national standard requirement value of type II plywood because the enhanced resin cannot completely crosslink the soybean protein in the defatted soybean flour and the crosslinking degree is insufficient. The water resistance of the composite material can be effectively improved by blending and compounding the incremental resin and the polyamide polyamine-epichlorohydrin resin, the dry strength and the water bubble wet strength at 63 ℃ of the composite material are basically and gradually increased along with the increase of the dosage of the polyamide polyamine-epichlorohydrin resin, and the water resistance of the composite material is basically maximized when the dosage of the polyamide polyamine-epichlorohydrin resin reaches more than 60 percent (the dosage of the incremental resin is reduced to less than 40 percent), and the composite material is equivalent to the pure polyamide polyamine-epichlorohydrin resin. Based on the national standard requirement, when the dosage of the increment resin in the blended composite crosslinking agent solution is reduced to 70%, the 63 ℃ blister wet strength of the prepared plywood reaches 1.31MPa, is 31 percent higher than the national standard requirement value (1.00MPa) of the II-type plywood, has enough strength surplus and can meet the production requirement.
Based on the price of the chemical raw materials in China at 5 months in 2021, the cost of the solid raw material of the low-cost environment-friendly incremental resin prepared in the first embodiment is 9450 yuan/ton, the cost of the solid raw material of the commercially available polyamide polyamine-epichlorohydrin resin is 21000 yuan/ton, the price of the commercially available bean flour is about 6000 yuan/ton, the mass ratio of the diluted polyamide polyamine-epichlorohydrin resin solution to the diluted environment-friendly incremental resin solution is 30:70, the cost of the prepared soybean adhesive is 2320 yuan/ton, which is equivalent to the cost of the E0 grade urea-formaldehyde resin adhesive (about 2400 yuan/ton), and is higher than the cost of the soybean adhesive prepared by singly using the polyamide polyamine-epichlorohydrin resin (prepared by 100 parts of the polyamide polyamine-epichlorohydrin resin with the mass percentage of 6% and 45 parts of the bean flour), about 2730 yuan/ton) was reduced by 17.7%.
Example six:
evaluation of the bonding performance of the soybean adhesive by the low-cost environment-friendly incremental resin prepared in the first to third embodiments:
preparing a crosslinking agent solution containing an incremental resin:
a. diluting a commercially available polyamide polyamine-epichlorohydrin resin with the mass percent of 15.2% to the mass percent of solid parts of 6% by using water to obtain a diluted polyamide polyamine-epichlorohydrin resin solution;
b. diluting the low-cost environment-friendly incremental resin prepared in the first to third embodiments with water respectively until the mass percent of the solid is 6% to obtain diluted environment-friendly incremental resin solutions of the first to third embodiments;
c. respectively mixing the diluted polyamide polyamine-epichlorohydrin resin solution with the diluted environment-friendly incremental resin solutions of the first to third 3 embodiments to obtain cross-linking agent solutions of 3 different incremental resins;
the mass ratio of the diluted polyamide polyamine-epichlorohydrin resin solution to the diluted environment-friendly incremental resin solution is 30:70 respectively;
preparing soybean adhesive:
respectively weighing 100 parts of each of the cross-linking agent solutions of the 3 different incremental resins and 40 parts of defatted soybean flour according to the mass parts, respectively adding 40 parts of defatted soybean flour into the cross-linking agent solutions of the 3 different incremental resins, and uniformly stirring at room temperature to obtain the 3 soybean adhesives.
Preparing three-layer plywood by using birch veneers with the thickness of 1.6mm, drying the birch veneers to the water content of 5% -7% in advance, and then respectively coating the 3 soybean adhesives prepared in the embodiment on two surfaces of a veneer core layer, wherein the adhesive application amount is 380g/m2(double-side sizing amount, liquid glue solution metering); the glued birch veneer is combined into a plate blank,prepressing for 30min under the pressure of 1.2MPa, and hot pressing for 4.5min under the conditions of temperature of 120 ℃ and pressure of 1.3MPa to obtain 3 kinds of three-layer plywood. The plywood was tested for dry bond strength and 63 ℃ wet bond strength by the method specified in the national standard GB/T17657-2015, as shown in Table 2.
Table 2 examples effect of extender resin types in hexacrosslinker solution on the bonding properties of modulated soy adhesives
Note: the number in brackets (x/10) indicates the x pieces remaining after 28h "boil-dry-boil" treatment of 10 test pieces.
The results show that: the increment resin prepared by three different synthesis technologies is blended and compounded with 30% of polyamide polyamine-epichlorohydrin resin, the obtained soybean adhesive modulated by the composite crosslinking agent has little difference of bonding performance, the water resistance of the soybean adhesive is higher than the requirement value (1.00MPa) of the national standard on the II-type plywood, the performance margin is 22% -34%, and the soybean adhesive can meet the production requirement.
Based on the price of Chinese chemical raw materials of 5 months in 2021, the solid raw material cost of the three incremental resins is 9450-10500 yuan/ton, the solid raw material cost of the commercially available polyamide polyamine-epichlorohydrin resin is 21000 yuan/ton, the commercially available soybean powder is about 6000 yuan/ton, the raw material cost of the soybean adhesive prepared by using the cross-linking agent with the mass percent of 6% in the six solid parts in the embodiment is 2265-2300 yuan/ton, and the raw material cost (about 2400 yuan/ton) of the urea-formaldehyde resin adhesive lower than that of E0 grade is equivalent, and is reduced by about 15.8-17% compared with the raw material cost of the soybean adhesive prepared by using the polyamide polyamine-epichlorohydrin resin alone (100 parts of the polyamide polyamine-epichlorohydrin resin with the mass percent of 6% and 45 parts of the prepared soybean powder, about 2730 yuan/ton).
Claims (10)
1. The low-cost environment-friendly incremental resin is characterized in that the low-cost environment-friendly incremental resin is prepared from 100 parts of epoxy chloropropane, 5-15 parts of reaction promoter and 25-75 parts of amino-containing monomer according to the mass parts; the low-cost environment-friendly incremental resin comprises 60-95% of solid by mass and 6000-10000 mPa.s of viscosity at 25 ℃; the low-cost environment-friendly incremental resin is a liquid product which is easily dissolved in water.
2. The environment-friendly extender resin with low cost as claimed in claim 1, wherein the reaction promoter is a polar small molecular substance containing hydroxyl or amino.
3. The environment-friendly and low-cost extender resin as claimed in claim 2, wherein the reaction accelerator is one or a mixture of water, ethylene glycol, propylene glycol, butylene glycol, glycerol, monoethanolamine, diethanolamine, triethanolamine and formamide.
4. The environment-friendly extender resin with low cost according to claim 1, wherein the amino group-containing monomer is a monomer having two or more amino groups in the molecule.
5. The environmentally friendly extender resin of claim 4, wherein the amino group containing monomer is one or a mixture of urea and thiourea.
6. The method for preparing the environment-friendly and environment-friendly incremental resin with low cost as claimed in claim 1 is characterized by comprising the following steps of:
weighing 100 parts of epoxy chloropropane, 5-15 parts of a reaction promoter and 25-75 parts of an amino-containing monomer according to the mass parts;
secondly, firstly heating 100 parts of epoxy chloropropane to 60-120 ℃, adding 5-15 parts of reaction accelerator and 25-75 parts of amino-containing monomer, then reacting for 2-4 h under the condition of stirring and temperature of 60-120 ℃ to obtain a transparent homogeneous solution, continuously reacting the transparent homogeneous solution under the condition of stirring and temperature of 60-120 ℃ until the mass percentage of residual epoxy groups in the system is lower than 0.05%, then keeping for 20-40 min under the condition of stirring and temperature of 60-120 ℃, and finally stopping heating and cooling to below 45 ℃ to obtain the low-cost environment-friendly incremental resin.
7. The method for preparing the environment-friendly incremental resin with low cost according to claim 6, wherein 100 parts of epichlorohydrin, 5-10 parts of reaction accelerator and 25-44 parts of amino-containing monomer are weighed according to the mass parts in the step one.
8. The use of a low-cost environmentally friendly extender resin as claimed in claim 1, wherein the low-cost environmentally friendly extender resin is used in the preparation of soybean adhesives.
9. The application of the low-cost environment-friendly extender resin as claimed in claim 8, wherein the application of the low-cost environment-friendly extender resin to the preparation of the soybean adhesive is carried out according to the following steps:
preparing a crosslinking agent solution containing an incremental resin:
a. diluting polyamide polyamine-epichlorohydrin resin with water to a solid content of 5-12% by mass to obtain a diluted polyamide polyamine-epichlorohydrin resin solution;
b. diluting the low-cost environment-friendly incremental resin with water to a solid mass percent of 5-12% to obtain a diluted environment-friendly incremental resin solution;
c. mixing the diluted polyamide polyamine-epichlorohydrin resin solution with the diluted environment-friendly incremental resin solution to obtain a crosslinking agent solution containing the incremental resin;
the mass ratio of the diluted polyamide polyamine-epichlorohydrin resin solution to the diluted environment-friendly incremental resin solution is 1 (0.25-4);
preparing soybean adhesive:
weighing 100 parts of crosslinking agent solution containing the incremental resin and 30-50 parts of bean flour according to the parts by weight, adding 30-50 parts of bean flour into 100 parts of crosslinking agent solution containing the incremental resin, and stirring uniformly at room temperature to obtain the soybean adhesive.
10. The use of the low-cost environmentally friendly extender resin as claimed in claim 9, wherein the soy flour in step (ii) is defatted soy flour or oil mill meal flour.
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