CN115029102B - High-initial-viscosity plant protein adhesive and preparation method and application thereof - Google Patents
High-initial-viscosity plant protein adhesive and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
- B27N3/002—Manufacture of substantially flat articles, e.g. boards, from particles or fibres characterised by the type of binder
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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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- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/325—Calcium, strontium or barium phosphate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
- Y02P60/80—Food processing, e.g. use of renewable energies or variable speed drives in handling, conveying or stacking
- Y02P60/87—Re-use of by-products of food processing for fodder production
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Abstract
The invention provides a high-initial-viscosity plant protein adhesive and a preparation method and application thereof. The adhesive is prepared by mixing soybean meal protein and calcium chloride in water, adding a phosphoric acid solution to perform in-situ deposition, adding catechol comb polymer and a cross-linking agent into a reaction system, and stirring at normal temperature. The soybean meal protein adhesive provided by the invention has the advantages of high water-resistant adhesive strength, good coating performance, high mildew resistance, good flame retardance and high quality stability of a plywood product prepared from the soybean meal protein adhesive.
Description
Technical Field
The invention relates to the technical field of biomass adhesives, in particular to a high-initial-viscosity vegetable protein adhesive and a preparation method and application thereof.
Background
The total annual artificial board yield in China exceeds 2.9X10 8 Cubic meters is a main raw material for furniture, floors and interior decoration in living environment. 90% of the adhesive consumed in the preparation process of the artificial board is the aldehyde resin adhesive which is not renewable, and the free aldehyde released by the product in the production and use processes causes serious environmental pollution and simultaneously endangers human health. Therefore, the development of the environment-friendly biomass adhesive becomes a development trend.
The soybean meal protein is a common biomass resource, is widely available and easy to process, and is widely applied to the research of biomass environment-friendly adhesives. The epoxy crosslinking modification can consume hydrophilic groups in the soybean meal protein to form a compact water-resistant structure, so that the water-resistant cementing property of the soybean meal protein adhesive is effectively improved. The chemical crosslinking modification method has been successfully applied to the industrial production of plywood. However, the initial viscosity of the soybean meal protein adhesive is low, so that the coating performance of the soybean meal protein adhesive is poor, the production efficiency is reduced, and the wide application of the soybean meal protein adhesive in the artificial board industry is limited. In addition, the soybean meal protein adhesive has the common problem of easy mildew and flammability. Therefore, developing a multifunctional soy protein adhesive with good coating properties is an important and very challenging task.
Disclosure of Invention
The invention aims to provide a novel high-initial-viscosity plant protein adhesive, and a preparation method and application thereof.
The inventors have inspired by the strong adhesion structure of mussel proteins, the use of polymers with catechol groups to improve the initial tack of adhesives is an effective and practical method. The invention is characterized in that: the adhesion substance secreted by the oyster contains a large amount of inorganic components (up to 50%) and phosphorylated proteins, and the organic-inorganic hybridization adhesion structure is favorable for adhesion of other materials and capture of sand to form large-piece connected coral reefs. The reason for the superior mechanical properties of oyster is that it secretes organic and inorganic phases uniformly distributed in the adhesive composite material. Therefore, the inventor deposits inorganic substances on an organic matrix through an in-situ deposition method to form an organic-inorganic hybrid system, the simulated biomineralization structure constructs an organic-inorganic hybrid structure, and a uniform and stable calcium phosphate deposition phase is generated in the organic material, so that the high strength and the multifunction of the organic material are provided. Wherein, calcium chloride and phosphoric acid react and are uniformly deposited and combined on the template soybean meal protein serving as a biological macromolecule, thereby providing a good physical enhancement effect for the system. Meanwhile, the comb-shaped polymer with catechol end groups is prepared by inspired by mussel strong adhesion and gecko adhesion structures, the strong adhesion characteristic is generated in a system through the unique main chain and side chain structures of the polymer, and the comb-shaped polymer is combined with an organic-inorganic hybrid structure, so that the coating performance, mildew resistance and adhesive strength of the soybean meal protein adhesive are hopefully improved, and meanwhile, the soybean meal adhesive has flame retardance.
In order to achieve the aim of the invention, in a first aspect, the invention provides a high initial viscosity vegetable protein adhesive, which is prepared by mixing soybean meal protein and calcium chloride in water, adding 96% phosphoric acid solution to perform in-situ deposition, adding catechol comb-shaped polymer and a cross-linking agent into a reaction system, and stirring at normal temperature.
The weight portions of the components are as follows: 30 parts of soybean meal protein, 70 parts of water (dispersion medium), 0.3-0.4 part of calcium chloride, 0.1-0.2 part of phosphoric acid solution, 1-2 parts of catechol comb polymer and 1-2 parts of cross-linking agent (glycerol triglycidyl ether).
The crosslinking agent may be at least one selected from glycerol triglycidyl ether, ethylene glycol diglycidyl ether, pentanediol diglycidyl ether, and the like.
The preparation method of the catechol comb polymer comprises the following steps:
(1) 75-85g of diethylenetriamine is added into a three-neck flask, a condenser and a thermometer are inserted into the three-neck flask, the three-neck flask is heated to 80 ℃, 103g of adipic acid and 2.68g of paratoluenesulfonic acid monohydrate are added while stirring;
(2) Heating to 150-170 ℃, continuously stirring for 2-3h, removing the condenser and the thermometer, and continuing to react for 3-4h; then stopping heating, and naturally cooling to 110-130 ℃;
(3) Adding 70-90g of water with the temperature of 100 ℃ and 70-90g of water with the temperature of 70 ℃ into the reaction system, stirring for 0.5-1.5h at the temperature of 70 ℃, and then cooling to 20-40 ℃ to obtain a long-chain polyamide solution with the concentration of 45-55 wt%;
(4) Reacting long-chain polyamide solution with dialdehyde starch and distilled water according to the mass ratio of 1 (1.5-2) to 9.5 at 60 ℃ for 3-4 hours to obtain an amination dialdehyde starch solution;
(5) 6-7g of 3, 4-dihydroxybenzaldehyde is dissolved in a mixed solution of 200mL of absolute ethyl alcohol and 100mL of water under the nitrogen environment, 40g of the amination dialdehyde starch solution is added, the reaction is carried out for 20-24h at 70-90 ℃, and the catechol comb polymer is obtained after the reaction product is dried in vacuum.
The soybean meal protein is defatted soybean meal powder, the particle size is smaller than 200 meshes, and the protein content is 50-53%.
Catechol is readily oxidized to quinone in air, so the reaction proceeds under nitrogen, protecting the catechol group.
In the invention, 3, 4-dihydroxybenzaldehyde can be replaced by 3, 4-dihydroxybenzoic acid, 3, 4-dihydroxybenzonitrile, caffeic acid, urushiol and 4-allylcatechol, and catechol groups are modified at the end groups of comb-shaped polymers.
In the second aspect, the invention provides a preparation method of the adhesive, which comprises the steps of weighing each component according to the mass ratio, mixing bean pulp protein and calcium chloride in water, adding 96% phosphoric acid solution, stirring for 10-20min to perform in-situ deposition, adding catechol comb-shaped polymer and cross-linking agent into a reaction system, and stirring at normal temperature to obtain the adhesive.
In a third aspect, the invention provides application of the adhesive in artificial board processing.
By means of the technical scheme, the invention has at least the following advantages and beneficial effects:
according to the invention, the catechol functional group is grafted on the amino dialdehyde starch end group to obtain the catechol comb-shaped polymer, so that the initial viscosity, the coating performance and the adhesive layer toughness of the adhesive are improved.
The invention is inspired by the biological organic-inorganic hybrid structure, calcium phosphate is deposited on soybean meal molecules in situ by utilizing in-situ mineralization to form an inorganic reinforcing phase, and the adhesive bonding performance is improved by constructing the organic-inorganic hybrid structure.
And thirdly, the catechol comb-shaped polymer added into the adhesive improves the mildew resistance of the soybean meal protein adhesive.
And fourthly, the internal toughening effect of the catechol comb polymer in the invention generates strong hydrogen bond combination in the system through the catechol end group and the structural characteristic of the polymer, improves the energy dissipation of the system, effectively conducts and disperses the internal stress generated in the system, and improves the toughness of the adhesive.
And (V) mineralized calcium phosphate and catechol comb-shaped polymer added into the adhesive improve the flame retardant property of the soybean meal protein adhesive.
Drawings
FIG. 1 shows a preferred embodiment of the present invention 1 H NMR characterizes the structure of catechol comb polymers. Wherein, DBA:3, 4-dihydroxybenzaldehyde, ADAS: aminated dialdehyde starch, ADD: catechol comb polymers. (B) (C), (F), (G), and (H) each represent-CH, -CHO, -NH 2 、-CH 2 -CH; (B '), (C '), (F '), (G '), (H ') each represents-CH, -CHO, -NH 2 、-CH 2 、-CH。
Detailed Description
The following examples are illustrative of the invention and are not intended to limit the scope of the invention. Unless otherwise indicated, the technical means used in the examples are conventional means well known to those skilled in the art, and all raw materials used are commercially available.
The percentage "%" referred to in the present invention refers to mass percent unless otherwise specified; however, the percentage of the solution, unless otherwise specified, means that 100ml of the solution contains a plurality of grams of solute; the percentage between liquids refers to the ratio of the volumes at 20 ℃.
The soybean powder used in the following examples was defatted soybean meal powder having a particle size of less than 200 mesh and a protein content of 53%. Purchased from Shandong Yongwang Biotechnology Co.
The crosslinker glycerol triglycidyl ether was purchased from national pharmaceutical chemicals company.
Calcium chloride and phosphoric acid, available from Shanghai Meilin reagent company.
Example 1 preparation method of high initial viscosity soybean meal protein adhesive
The embodiment provides a preparation method of a soybean meal protein adhesive, which comprises the following steps of:
weighing the components according to the mass ratio, mixing soybean powder and calcium chloride in water, adding a phosphoric acid solution, stirring for 10min to perform in-situ deposition, adding catechol comb polymer and a cross-linking agent into a reaction system, and stirring at normal temperature to obtain the modified soybean powder.
The preparation method of the catechol comb polymer comprises the following steps:
(1) Diethylenetriamine (76 g,0.74 mol) was charged into a three-necked flask, a condenser and a thermometer were inserted into the three-necked flask, and heated to 80℃and 103g,0.7mol of adipic acid and p-toluenesulfonic acid monohydrate (2.68 g,0.014 mol) were added while stirring;
(2) Heating to 160 ℃, continuously stirring for 2 hours, taking down the condenser and the thermometer, and continuing to react for 3-4 hours. Then stopping heating and naturally cooling to 120 ℃;
(3) 80g of water at 100 ℃ and 80g of water at 70 ℃ are added into the reaction system, stirred for 0.5h at 70 ℃, and then cooled to 30 ℃ to obtain a long-chain polyamide aqueous solution (50 wt%);
(4) Reacting long-chain polyamide with dialdehyde starch and distilled water for 3 hours at 60 ℃ according to the mass ratio of 1:1.5:9.5 to obtain an amination dialdehyde starch solution;
(5) 3, 4-dihydroxybenzaldehyde (6.25 g) was dissolved in a mixed solution of absolute ethanol (200 mL)/water (100 mL) under a nitrogen atmosphere, 40g of an aminated dialdehyde starch solution was added, and reacted at 80℃for 20 hours to obtain a crude catechol comb polymer product. And washing the crude catechol comb polymer product with acetone, and vacuum drying to obtain the final catechol comb polymer product.
By passing through 1 H NMR characterizes the structure of catechol comb polymers. As shown in fig. 1, a strong proton peak corresponding to catechol group appears in the catechol comb polymer profile, compared to the profile of the aminated dialdehyde starch.
Example 2 preparation method of high initial viscosity soybean meal protein adhesive
The embodiment provides a preparation method of a soybean meal protein adhesive, which comprises the following steps of:
the preparation method of the adhesive is the same as that described in the example 1.
The preparation method of the catechol comb polymer comprises the following steps:
(1) Diethylenetriamine (76 g,0.74 mol) was charged into a three-necked flask, a condenser and a thermometer were inserted into the three-necked flask, and heated to 80℃and 103g,0.7mol of adipic acid and p-toluenesulfonic acid monohydrate (2.68 g,0.014 mol) were added while stirring;
(2) Heating to 160 ℃, continuously stirring for 2 hours, taking down the condenser and the thermometer, and continuing to react for 3-4 hours. Then stopping heating and naturally cooling to 120 ℃;
(3) 80g of water at 100 ℃ and 80g of water at 70 ℃ are added into the reaction system, stirred for 0.5h at 70 ℃, and then cooled to 30 ℃ to obtain a long-chain polyamide aqueous solution (50 wt%);
(4) Reacting long-chain polyamide with dialdehyde starch and distilled water for 3 hours at 60 ℃ according to the mass ratio of 1:1.5:9.5 to obtain an amination dialdehyde starch solution;
(5) 3, 4-dihydroxybenzaldehyde (6.25 g) was dissolved in a mixed solution of absolute ethanol (200 mL)/water (100 mL) under a nitrogen atmosphere, 40g of an aminated dialdehyde starch solution was added, and reacted at 80℃for 20 hours to obtain a crude catechol comb polymer product. And washing the crude catechol comb polymer product with acetone, and vacuum drying to obtain the final catechol comb polymer product.
Comparative examples 1 to 4:
comparative example 1 is a uniform mixture of 30kg of soybean powder and 70kg of water; comparative example 2 compared to example 1, there was no calcium chloride and phosphoric acid solution; comparative example 3 in comparison with example 1, there is no catechol comb polymer. Comparative example 4 was a melamine modified urea formaldehyde resin (grade E0) having a formaldehyde to melamine molar ratio of 1.01, available from shandong kusen wood limited. Comparative example 5 is a uniform mixture of 30kg of soybean flour, 50kg of water and 20kg of PAE (polyamide epichlorohydrin). Comparative example 6 is a uniform mixture of 30kg of soybean flour, 70kg of water and 8kg of isocyanate. Comparative example 7 was a uniform mixture of 30kg of soybean powder, 70kg of water and 8kg of a silane coupling agent.
Test example:
three-layer plywood was prepared using the adhesives of examples 1-2 and comparative examples 1-5, respectively.
Poplar veneer: drying the water content to 10%; the dimensions are 40cm by 0.15cm.
The preparation method comprises the following steps:
sizing: the glue coating amount is 180g/m 2 . (good adhesive coating property and less sizing amount)
Technological conditions for processing the three-layer plywood are as follows: the pressure is 1.0-1.2MPa, the temperature is 120 ℃ and the time is 6min.
The test was carried out according to the standard of class II plywood in GB/T17657-2013. Each set of samples was averaged in 12 replicates.
And (3) testing mildew resistance: after weighing 5g of the adhesive and uniformly placing the adhesive on a culture dish, placing the culture dish in a constant temperature and humidity box with the relative humidity of 100% at 35 ℃. The status was observed and recorded with a digital camera every 24 hours.
Flame retardant performance test: the limiting oxygen index of the adhesive samples was measured using a limiting oxygen index meter (FTT 0077, fire Testing Technology, uk) according to national standard GB/T2406.2-2009.
The detection results are shown in Table 1.
TABLE 1
The test results show that the soybean meal protein adhesive prepared by the invention has high water-resistant adhesive strength, good coating performance, high mildew resistance, good flame retardant property and high quality stability of the prepared plywood product.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (4)
1. The high-initial-viscosity plant protein adhesive is characterized in that the adhesive is prepared by mixing soybean meal protein and calcium chloride in water, adding 96% phosphoric acid solution to perform in-situ deposition, adding catechol comb-shaped polymer and cross-linking agent into a reaction system, and stirring at normal temperature;
the weight portions of the components are as follows: 30 parts of soybean meal protein, 70 parts of water, 0.3-0.4 part of calcium chloride, 0.1-0.2 part of phosphoric acid solution, 1-2 parts of catechol comb polymer and 1-2 parts of cross-linking agent;
the cross-linking agent is at least one selected from glycerol triglycidyl ether, ethylene glycol diglycidyl ether and pentanediol diglycidyl ether;
the preparation method of the catechol comb polymer comprises the following steps:
(1) 75-85g of diethylenetriamine is added into a three-neck flask, a condenser and a thermometer are inserted into the three-neck flask, the three-neck flask is heated to 80 ℃, 103g of adipic acid and 2.68g of paratoluenesulfonic acid monohydrate are added while stirring;
(2) Heating to 150-170 ℃, continuously stirring for 2-3h, removing the condenser and the thermometer, and continuing to react for 3-4h; then stopping heating, and naturally cooling to 110-130 ℃;
(3) Adding 70-90g of water with the temperature of 100 ℃ and 70-90g of water with the temperature of 70 ℃ into the reaction system, stirring for 0.5-1.5h at the temperature of 70 ℃, and then cooling to 20-40 ℃ to obtain a long-chain polyamide solution with the concentration of 45-55 wt%;
(4) Reacting long-chain polyamide solution with dialdehyde starch and distilled water according to the mass ratio of 1 (1.5-2) to 9.5 at 60 ℃ for 3-4 hours to obtain an amination dialdehyde starch solution;
(5) 6-7g of 3, 4-dihydroxybenzaldehyde is dissolved in a mixed solution of 200mL of absolute ethyl alcohol and 100mL of water under the nitrogen environment, 40g of the amination dialdehyde starch solution is added, the reaction is carried out for 20-24h at 70-90 ℃, and the catechol comb polymer is obtained after the reaction product is dried in vacuum.
2. The adhesive of claim 1, wherein the soybean meal protein is defatted soybean meal powder, the particle size is less than 200 meshes, and the protein content is 50-53%.
3. The preparation method of the adhesive according to claim 1 or 2, which is characterized in that the components are weighed according to the mass ratio, bean pulp protein and calcium chloride are mixed in water, 96% phosphoric acid solution is added to be stirred for 10-20min for in-situ deposition, then catechol comb polymer and cross-linking agent are added to a reaction system, and the adhesive is obtained after stirring at normal temperature.
4. Use of the adhesive according to claim 1 or 2 in the processing of artificial boards.
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| CN113493678A (en) * | 2021-07-28 | 2021-10-12 | 南京林业大学 | Formaldehyde-free soy protein adhesive and preparation method thereof |
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| CN101475691A (en) * | 2009-01-23 | 2009-07-08 | 成都理工大学 | Acrylic amide modified polymer micro-crosslinking gel and preparation thereof |
| CN110003848A (en) * | 2019-04-24 | 2019-07-12 | 李亚军 | A kind of preparation method of the modified legumin adhesive of no aldehyde |
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| CN113493678A (en) * | 2021-07-28 | 2021-10-12 | 南京林业大学 | Formaldehyde-free soy protein adhesive and preparation method thereof |
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