CN113652196B - Formaldehyde-free soybean glue and preparation method and application thereof - Google Patents
Formaldehyde-free soybean glue and preparation method and application thereof Download PDFInfo
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- CN113652196B CN113652196B CN202110901227.3A CN202110901227A CN113652196B CN 113652196 B CN113652196 B CN 113652196B CN 202110901227 A CN202110901227 A CN 202110901227A CN 113652196 B CN113652196 B CN 113652196B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J189/00—Adhesives based on proteins; Adhesives based on derivatives thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27D—WORKING VENEER OR PLYWOOD
- B27D1/00—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring
- B27D1/04—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring to produce plywood or articles made therefrom; Plywood sheets
- B27D1/08—Manufacture of shaped articles; Presses specially designed therefor
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
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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
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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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2170/00—Compositions for adhesives
Abstract
The invention relates to the technical field of biomass adhesives, and particularly discloses an aldehyde-free soybean adhesive as well as a preparation method and application thereof. The soybean glue comprises soybean meal, a dispersing agent, a toughening agent, a reinforcing agent and water; the dispersing agent is a glucose/guanidine hydrochloride eutectic solvent, and the toughening agent is aminated graphene; the reinforcing agent is an aqueous solution of modified polyamide polyamine epichlorohydrin. The soybean glue prepared by the method has stable performance, obviously reduced weak interface layer, good dry strength, good water-resistant bonding performance and stable product quality. The water-resistant and technological requirements of the plywood adhesive can be met, and the practical performance of the biomass adhesive is ensured.
Description
Technical Field
The invention relates to the technical field of biomass adhesives, in particular to an aldehyde-free soybean adhesive and a preparation method and application thereof.
Background
Precious wood resources are relatively deficient, artificial forest resources are rich, artificial boards prepared from fast growing woods of the artificial forests through adhesives are main raw materials for furniture floors and indoor decoration in human living environments, the total yield of the artificial boards is large, and most of the artificial boards are plywood products. The consumption of the adhesive for the plywood is huge (the solid content is 50%) according to the average production of 9 cubic meters of artificial boards by each ton of the adhesive, wherein the urea-formaldehyde resin and modified products thereof occupy the dominant position of the adhesive. The urea-formaldehyde resin adhesive is widely used in the wood industry due to the advantages of sufficient raw materials, low price, good water solubility and the like, but has the problem of formaldehyde release of products.
With the improvement of living standard of people, people pay attention to the problem of environmental pollution. The artificial board prepared by the biomass adhesive can solve the problem of the release amount of free formaldehyde of the artificial board, and is an important way for solving the problem, but most biomass adhesives have the problems of poor water-resistant adhesive bonding performance, poor strength and the like, so that the industrial application of the biomass adhesives is limited.
Therefore, it is desirable to provide a new formaldehyde-free soy gum, and a method for preparing and using the same to solve the problems of the prior art.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide the formaldehyde-free soybean glue which has good bonding strength and is environment-friendly.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a soybean glue comprises soybean meal, a dispersing agent, a toughening agent, a reinforcing agent and water; the dispersing agent is a glucose/guanidine hydrochloride eutectic solvent, and the toughening agent is aminated graphene; the reinforcing agent is an aqueous solution of modified polyamide polyamine epichlorohydrin.
In the invention, the aminated graphene is prepared by modifying graphite oxide with polyamide, and the mass ratio of the polyamide to the graphite oxide is (1-2): 1; the polyamide is prepared by condensation polymerization of diethylenetriamine and succinic anhydride, wherein the molar ratio of the diethylenetriamine to the succinic anhydride is (1.01-1.05): 1.
the method prepares the aminated graphite in a specific modification mode, can perform modification reaction under mild conditions, and well maintains the lamellar structure of the graphene. The surface of the modified graphite has a specific hyperbranched branched chain structure, and the modified graphite and the specific reinforcing agent can be matched to form a specific multi-branched cross-linking structure, so that the graphite with good toughness and CA cooperate to construct a tough cross-linking structure in a cross-linking system, and the cohesion and toughness of soybean gum are improved.
In the invention, the modified polyamide polyamine epichlorohydrin is prepared from epichlorohydrin and a polyamide prepolymer, wherein the polyamide prepolymer is prepared from adipic acid, polysebacic anhydride and diethylenetriamine; the mass ratio of the epichlorohydrin to the polyamide prepolymer is (1.2-1.3): 1, the molar ratio of the adipic acid to the polysebacic anhydride to the diethylenetriamine is (0.9-0.95): (0.05-0.10): (1.01-1.05).
The water-soluble modified polyamide polyamine epichlorohydrin (CA) synthesized by the invention is a reinforcing agent with a specific flexible long-chain polyepoxy group structure formed by modifying with a specific modifier (polysebacic polyanhydride and the like), and can perform specific crosslinking reaction or hydrogen bond combination with each component of soybean meal, so that the system has specific compatibility, the crosslinking density of soybean glue is improved, and the toughness of the adhesive is improved.
Preferably, the mass ratio of the polyamide to the graphite oxide is 2:1; the polyamide is prepared by condensation polymerization of diethylenetriamine and succinic anhydride, wherein the molar ratio of the diethylenetriamine to the succinic anhydride is 1.05:1; the mass ratio of the epichlorohydrin to the polyamide prepolymer is 1.3:1, the molar ratio of the adipic acid to the polysebacic anhydride to the diethylenetriamine is 0.9:0.1:1.05.
in the invention, the mass ratio of glucose to guanidine hydrochloride in the glucose/guanidine hydrochloride eutectic solvent is (0.9-1.1): 1, and is preferably 1:1.
The preparation method of the dispersant comprises the following steps: mixing glucose/guanidine hydrochloride in a weight ratio of 1:1, and heating to 70 ℃.
The dispersant of the invention adopts a specific eutectic solvent, has simple and efficient synthesis process, can be compatible with bean pulp and other components, can promote Schiff base reaction of polysaccharide and protein in the system of the invention at the same reaction temperature, and can promote cross-linking reaction of the protein and specific CA of the invention, so that the polysaccharide in the system participates in the cross-linking reaction in a specific form, thereby further improving the cross-linking density of the solidified soybean gum, successfully constructing a specific branched cross-linking network structure in the bean pulp system, and improving the water-resistant cementing property of the soybean gum.
In the invention, the soybean meal is low-temperature soybean meal powder with the average protein content of 43% and the average particle size of 250 meshes.
As an example of a specific embodiment, the method for preparing the soybean meal powder of the present invention comprises: processing peeled low-temperature defatted soybean meal into 40 meshes by a pulverizer, mixing the soybean meal with water 3:1 in a weight ratio, processing the soybean meal into 100 meshes by a colloid mill, processing the soybean meal into 250 meshes by a high-pressure homogenizer, and then spraying and drying the soybean meal into powder.
The soybean gum comprises the following components in parts by weight: 18-22 parts of soybean meal, 48-52 parts of dispersing agent, 0.7-0.9 part of toughening agent, 9-11 parts of reinforcing agent and 8-12 parts of water; the reinforcing agent has a solids content of 12.5%.
Preferably, the composition comprises the following components in parts by weight: 20 parts of soybean meal, 50 parts of dispersing agent, 0.8 part of toughening agent, 10 parts of reinforcing agent and 10 parts of water.
The components of the invention are matched according to specific dosage, the matching effect of the components can be fully exerted, the effect can be ensured, and the cost can be saved.
The invention also provides a method for preparing the soybean gum, which comprises the steps of preparing the toughening agent, the reinforcing agent and the dispersing agent;
the preparation method of the toughening agent comprises the following steps:
1) Reacting diethylenetriamine and succinic anhydride in an oil bath kettle at the temperature of 48-52 ℃ for 1.8-2.2h, and then heating to 138-142 ℃ for melt polycondensation for 2.8-3.2h to obtain polyamide;
2) Ultrasonically dispersing graphite oxide in N, N-dimethylformamide;
3) Adding the polyamide, heating to 48-52 ℃, and reacting for 7.5-8.5h;
and/or the preparation method of the reinforcing agent comprises the following steps:
1) Firstly, polysebacic anhydride, diethylenetriamine and adipic acid with the formula amount of 44-45% are mixed with sulfuric acid, heated to 128-132 ℃, then the adipic acid with the rest formula amount is added, and the reaction is carried out for 1.8-2.2h at 160-170 ℃; the mass ratio of the mixed system to the sulfuric acid is 100 (0.8-1.2);
2) Adjusting the solid content of the product by water to obtain a polyamide prepolymer with the solid content of 48-52% (beneficial to the subsequent reaction);
3) Dropwise adding epoxy chloropropane for reaction, wherein the reaction temperature is 58-62 ℃, and the reaction time is 1.8-2.2h;
4) Adjusting the pH value of the product to 5.8-6.2;
and/or the preparation method of the dispersant comprises the following steps: mixing glucose and guanidine hydrochloride, and heating to 68-72 ℃.
Preferably, the solids content of the reinforcing agent of the invention is 12.5% in order to improve the storage stability.
The method comprises the following steps: firstly, the toughening agent is ultrasonically dispersed in water, and then the dispersing agent, the bean pulp and the reinforcing agent are sequentially added.
The invention also provides an application of the soybean gum or the soybean gum prepared by the method in preparing plywood.
When in application, the processing condition is mild, the curing is fast, and the industrial application is facilitated.
The invention has the beneficial effects that:
the soybean gum disclosed by the invention is free of toxic substances, high in synthesis efficiency, free of harmful substance release substances, stable in performance of each batch, low in cost and beneficial to industrial application.
The test proves that: the soybean gum of the invention is easy to form a cross-linked structure, has high cross-linking density, stable performance, obviously reduced weak interface layer, good dry strength, good water-resistant bonding performance and stable product quality. Can satisfy the water-fast and the technological requirement of plywood gluing agent, guaranteed the practicality of living beings gluing agent.
Detailed Description
Preferred embodiments of the present invention will be described in detail with reference to the following examples. It is to be understood that the following examples are given for illustrative purposes only and are not intended to limit the scope of the present invention. Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the spirit and scope of this invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
In the present invention, the% is a mass percentage unless otherwise specified; but the percentage of the solution, unless otherwise specified, means that 100ml of the solution contains several grams of solute; the percentage between the liquids refers to the ratio of the volumes at 20 ℃.
The soybean meal used in the embodiment of the invention has the average protein content of 43 percent and the particle size of 250 meshes, and is purchased from Shandong Yuwang ecological food industry Co.
Example 1
This example provides a soy gum of the present invention and a method of making the same.
The specific formula comprises the following components in parts by weight:
20 parts of soybean meal; 50 parts of a dispersing agent; 0.8 part of a toughening agent; 10 parts of a reinforcing agent; and 10 parts of water.
The preparation method comprises the following steps:
1. preparation of glucose/guanidine hydrochloride eutectic solvent as dispersant: mixing glucose/guanidine hydrochloride in a weight ratio of 1:1, and heating to 70 ℃.
2. Preparing toughening agent aminated graphene:
in a four-neck flask provided with an electric stirrer, a condenser tube and a thermometer, 1.05 mol of diethylenetriamine and 1 mol of succinic anhydride are added into the four-neck flask for stirring, after the reaction is carried out for two hours in an oil bath kettle at 50 ℃, the temperature is raised to 140 ℃ for melt polycondensation reaction for three hours, the heating is stopped, and the flask and reactants are cooled in a room temperature environment to obtain yellow solid, thus obtaining the polyamide.
Graphite oxide (0.1 g) was dispersed in 100ml of n, n-dimethylformamide, the solution was subjected to ultrasonic dispersion treatment on a cell disruptor (ultrasonic power 100 watts), after half an hour the reagent was transferred to a four-necked flask, and the polyamide obtained in the above step was added to the flask in a mass ratio of 2:1, heating the mixture to 50 ℃ under magnetic stirring, reacting for 8 hours, centrifuging the reactant in a separation centrifuge, and washing away residual chemical reagents by deionized water to obtain modified graphite oxide (EGO) -aminated graphene.
3. Preparation of the reinforcing agent modified polyamide polyamine epichlorohydrin aqueous solution:
first 0.4 mol of adipic acid, 0.1 mol of polysebacic anhydride, 1.05 mol of diethylenetriamine and 1 wt.% (based on the total mass of 0.4 mol of adipic acid, 0.1 mol of polysebacic anhydride and 1.05 mol of diethylenetriamine) of H 2 SO 4 Adding into a three-neck flask, stirring and heating to 130 ℃, adding 0.5 mol of adipic acid, continuing to heat to 165 ℃, and carrying out melt dehydration polycondensation reaction for 2h. After the reaction is finished, distilled water is added to adjust the solid content, and the polyamide prepolymer with the solid content of 50% is obtained. 50g of polyamide prepolymer with 50% of solid content is taken and transferred into a clean three-neck flask, epichlorohydrin is added dropwise while the solution is stirred, and the mass ratio of the epichlorohydrin to the polyamide prepolymer is 1.3:1, the solution was allowed to react at a temperature of 60 ℃ for 2 hours. Finally, using H 2 SO 4 The pH value is reduced to 6, and distilled water is added to adjust the solid content of the solution to 12.5 percent, so as to obtain red viscous solution.
4. Preparing soybean gum:
the components are weighed according to the formula, firstly, the toughening agent is ultrasonically dispersed in water, then, the dispersing agent is added and uniformly stirred, then, the soybean meal is added and uniformly stirred for 15min, then, the reinforcing agent is added into the mixed solution and uniformly stirred for 10min at room temperature, and the rotating speed is 1200r/min, so that the soybean gum is prepared.
Example 2
This example provides a soy gum of the present invention and a method of making the same.
The specific formula comprises the following components in parts by weight:
20 parts of soybean meal; 50 parts of a dispersing agent; 0.8 part of a toughening agent; 10 parts of a reinforcing agent; and 10 parts of water.
The preparation method comprises the following steps:
1. preparation of glucose/guanidine hydrochloride eutectic solvent as dispersant: mixing glucose/guanidine hydrochloride in a weight ratio of 1:1 and heating to 70 ℃.
2. Preparing toughening agent aminated graphene:
in a four-neck flask provided with an electric stirrer, a condenser tube and a thermometer, 1.01 mol of diethylenetriamine and 1 mol of succinic anhydride are added into the four-neck flask for stirring, after the reaction is carried out for two hours in an oil bath kettle at 50 ℃, the temperature is raised to 140 ℃ for melt polycondensation reaction for three hours, the heating is stopped, and the flask and reactants are cooled in a room temperature environment to obtain yellow solid, thus obtaining the polyamide.
Graphite oxide (0.1 g) is dispersed in 100ml of N, N-dimethylformamide, the solution is subjected to ultrasonic dispersion treatment on a cell disruptor (ultrasonic power of 100 watts), after half an hour the reagent is transferred to a four-necked flask, and the polyamide obtained in the above step is added to the flask, the polyamide and graphite oxide being present in a mass ratio of 1:1, heating the mixture to 50 ℃ under magnetic stirring, reacting for 8 hours, centrifuging the reactant in a separation centrifuge, and washing away residual chemical reagents by deionized water to obtain modified graphite oxide (EGO) -aminated graphene.
3. Preparation of the reinforcing agent modified polyamide polyamine epichlorohydrin aqueous solution:
first 0.45 mole of adipic acid, 0.05 mole of polysebacic anhydride, 1.01 mole of diethylenetriamine and 1 wt.% (based on the total mass of 0.45 mole of adipic acid, 0.05 mole of polysebacic anhydride and 1.01 mole of diethylenetriamine) of H 2 SO 4 Adding into a three-neck flask, stirring and heating to 130 ℃, adding 0.5 mol of adipic acid, continuing to heat to 165 ℃, and carrying out melt dehydration polycondensation reaction for 2h. After the reaction is finished, distilled water is added to adjust the solid content, and the polyamide prepolymer with the solid content of 50% is obtained. 50g of polyamide prepolymer with 50% of solid content is taken and transferred into a clean three-neck flask, epichlorohydrin is added dropwise while the solution is stirred, and the mass ratio of the epichlorohydrin to the polyamide prepolymer is 1.2:1, the solution was allowed to react at a temperature of 60 ℃ for 2 hours. Finally, using H 2 SO 4 The pH value is reduced to 6, and distilled water is added to adjust the solid content of the solution to 12.5 percent, so as to obtain red viscous solution.
4. Preparing soybean gum:
the components are weighed according to the formula, firstly, the toughening agent is ultrasonically dispersed in water, then, the dispersing agent is added and uniformly stirred, then, the soybean meal is added and uniformly stirred for 15min, then, the reinforcing agent is added into the mixed solution and uniformly stirred for 10min at room temperature, and the rotating speed is 1200r/min, so that the soybean gum is prepared.
Comparative example 1
The comparative example provides a soybean glue, which comprises the following components in parts by weight: 20 parts of soybean meal; 60 parts of water; 0.8 part of a toughening agent; 10 parts of reinforcing agent. When preparing soybean gum, weighing the components according to a formula, firstly dispersing a toughening agent in water by ultrasound, then adding soybean meal powder, stirring for 15min to mix uniformly, then adding a reinforcing agent into the mixed solution, stirring uniformly for 10min at room temperature at the rotation speed of 1200r/min to prepare the soybean gum. The details are not described in detail and are the same as in example 1.
Comparative example 2
The comparative example provides a soybean glue, which comprises the following components in parts by weight: 20 parts of soybean meal; 50 parts of a dispersing agent. When preparing soybean gum, the components are weighed according to the formula, the soybean meal is dispersed in the dispersing agent, and the mixture is stirred to be uniformly mixed. The details are not described in detail and are the same as in example 1.
Comparative example 3
The comparative example provides a soybean glue, which comprises the following components in parts by weight: 20 parts of soybean meal; 50 parts of a dispersing agent; 0.8 part of a toughening agent; and 10 parts of water. When preparing soybean gum, the components are weighed according to the formula, firstly, the toughening agent is ultrasonically dispersed in water, then, the toughening agent is added into the dispersing agent to be uniformly stirred, and then, the soybean meal powder is added to be uniformly stirred to be uniformly mixed. The details are not described in detail and are the same as in example 1.
Comparative example 4
The comparative example provides a soybean glue, which comprises the following components in parts by weight: 20 parts of soybean meal; 50 parts of a dispersing agent; 10 parts of a reinforcing agent. When preparing soybean gum, weighing the components according to the formula, adding soybean meal powder into the dispersant, stirring to mix uniformly, adding the reinforcing agent into the mixed solution, and stirring to mix uniformly. The details are not described in the same manner as in example 1.
Comparative example 5
This comparative example is a conventional E0 grade urea formaldehyde resin adhesive (available from Qiansheng, inc., shandong).
Comparative example 6
This comparative example provides a soy gum of the same formulation and method of preparation as example 1 except that the same moles of maleic anhydride were substituted for succinic anhydride in the preparation of the toughener.
Comparative example 7
This comparative example provides a soy gum of the same formulation and method of preparation as example 1 except that, in the preparation of the toughener, diethylenetriamine was used in an amount of 1.5 moles and succinic anhydride was used in an amount of 1 mole.
Comparative example 8
This comparative example provides a soy gum of the same formulation and method of preparation as example 1 except that the same moles of adipic anhydride were substituted for polysebacic anhydride in the preparation of the reinforcing agent.
Comparative example 9
This comparative example provides a soy gum of the same formulation and method of preparation as example 1 except that the same moles of phthalic anhydride were substituted for polysebacic anhydride in the preparation of the reinforcing agent.
Comparative example 10
This comparative example provides a soy gum of the same formulation and method of preparation as example 1 except that the reinforcing agent was prepared with varying molar ratios of adipic acid, polysebacic anhydride and diethylenetriamine.
Specifically, in preparing the reinforcing agent, 0.2 mol of adipic acid, 0.4 mol of polysebacic anhydride, 1.05 mol of diethylenetriamine and 1wt% were first subjected to 2 SO 4 Adding into a three-neck flask, stirring and heating to 130 ℃, adding 0.4 mol of adipic acid, continuing to heat to 165 ℃, and carrying out melt dehydration polycondensation reaction for 2h. The procedure was then the same as in example 1.
Experimental example 1
This experimental example was conducted to test the soybean gums obtained in the above-described examples and comparative examples.
Specifically, three-ply plywood was prepared using the soybean glue obtained in each of the above examples and comparative examples to test the bonding strength.
Basswood veneer: drying to 10% of water content; the size was 40cm 0.15cm.
The lamination is carried out according to the following normal preparation process:
sizing: the glue coating amount is 360g/m 2 。
Hot pressing conditions are as follows: the pressure is 0.8MPa, the temperature is 110 ℃, and the time is 8 minutes.
The performance of the cross joint material product is tested according to the method for testing the performance of the cross joint material product in GB/T17657-1999 test method for physical and chemical properties of artificial boards and facing artificial boards, all the plywood samples are repeatedly measured for six times, and the average value is taken.
The soybean gum toughness test is to mix soybean gum with glycerol according to the weight ratio of 1.
Formaldehyde emission was tested according to GB/T17657-1999.
The results are shown in Table 1.
TABLE 1
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (8)
1. The soybean glue is characterized by comprising soybean meal, a dispersing agent, a toughening agent, a reinforcing agent and water; the dispersing agent is a glucose/guanidine hydrochloride eutectic solvent, and the toughening agent is aminated graphene; the reinforcing agent is an aqueous solution of modified polyamide polyamine epichlorohydrin;
the aminated graphene is prepared by modifying graphite oxide with polyamide, wherein the mass ratio of the polyamide to the graphite oxide is (1-2): 1; the polyamide is prepared by condensation polymerization of diethylenetriamine and succinic anhydride, wherein the molar ratio of the diethylenetriamine to the succinic anhydride is (1.01-1.05): 1;
the modified polyamide polyamine epichlorohydrin is prepared from epichlorohydrin and a polyamide prepolymer, wherein the polyamide prepolymer is prepared from adipic acid, polysebacic anhydride and diethylenetriamine; the mass ratio of the epichlorohydrin to the polyamide prepolymer is (1.2-1.3): 1, the molar ratio of the adipic acid to the polysebacic anhydride to the diethylenetriamine is (0.9-0.95): (0.05-0.10): (1.01-1.05);
comprises the following components in parts by weight: 18-22 parts of soybean meal, 48-52 parts of dispersing agent, 0.7-0.9 part of toughening agent, 9-11 parts of reinforcing agent and 8-12 parts of water; the reinforcing agent has a solids content of 12.5%.
2. The soybean glue of claim 1, wherein the mass ratio of the polyamide to the graphite oxide is 2:1; the polyamide is prepared by condensation polymerization of diethylenetriamine and succinic anhydride, wherein the molar ratio of the diethylenetriamine to the succinic anhydride is 1.05:1; the mass ratio of the epichlorohydrin to the polyamide prepolymer is 1.3:1, the molar ratio of the adipic acid to the polysebacic anhydride to the diethylenetriamine is 0.9:0.1:1.05.
3. the soybean glue according to claim 1, characterized in that the mass ratio of glucose to guanidine hydrochloride in the glucose/guanidine hydrochloride eutectic solvent is (0.9-1.1): 1.
4. The soybean gum according to claim 3, wherein the mass ratio of glucose to guanidine hydrochloride in the glucose/guanidine hydrochloride eutectic solvent is 1:1.
5. A soybean gum according to any one of claims 1 to 4, comprising, in parts by weight: 20 parts of soybean meal, 50 parts of dispersing agent, 0.8 part of toughening agent, 10 parts of reinforcing agent and 10 parts of water.
6. A method of preparing the soybean glue of any one of claims 1 to 5, comprising the steps of preparing the toughening agent, the reinforcing agent and the dispersing agent;
the preparation method of the toughening agent comprises the following steps:
1) Reacting diethylenetriamine and succinic anhydride in an oil bath kettle at the temperature of 48-52 ℃ for 1.8-2.2h, and then heating to 138-142 ℃ for melt polycondensation for 2.8-3.2h to obtain polyamide;
2) Ultrasonically dispersing graphite oxide in N, N-dimethylformamide;
3) Adding the polyamide, heating to 48-52 ℃, and reacting for 7.5-8.5h;
and/or the preparation method of the reinforcing agent comprises the following steps:
1) Firstly, polysebacic anhydride, diethylenetriamine and adipic acid with the formula amount of 44-45 percent are formed into a mixed system to be mixed with sulfuric acid, the mixed system is heated to 128-132 ℃, then the adipic acid with the rest formula amount is added, and the reaction is carried out for 1.8-2.2h at 160-170 ℃; the mass ratio of the mixed system to the sulfuric acid is 100 (0.8-1.2);
2) Adjusting the solid content of the product by water to obtain a polyamide prepolymer with the solid content of 48-52%;
3) Dropwise adding epoxy chloropropane for reaction, wherein the reaction temperature is 58-62 ℃, and the reaction time is 1.8-2.2h;
4) Adjusting the pH value of the product to 5.8-6.2;
and/or the preparation method of the dispersant comprises the following steps: mixing glucose and guanidine hydrochloride, and heating to 68-72 ℃.
7. The method of claim 6, comprising: firstly, the toughening agent is ultrasonically dispersed in water, and then the dispersing agent, the bean pulp and the reinforcing agent are sequentially added.
8. Use of a soy glue as claimed in any one of claims 1 to 5 or produced by the method of claim 6 or 7 for the production of plywood.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110901227.3A CN113652196B (en) | 2021-08-06 | 2021-08-06 | Formaldehyde-free soybean glue and preparation method and application thereof |
Applications Claiming Priority (1)
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