CN114958298A - High-coating prepressing-property vegetable protein adhesive and preparation method and application thereof - Google Patents
High-coating prepressing-property vegetable protein adhesive and preparation method and application thereof Download PDFInfo
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- CN114958298A CN114958298A CN202210670587.1A CN202210670587A CN114958298A CN 114958298 A CN114958298 A CN 114958298A CN 202210670587 A CN202210670587 A CN 202210670587A CN 114958298 A CN114958298 A CN 114958298A
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- adhesive
- vegetable protein
- solution
- urushiol
- uniformly dispersing
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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
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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
- C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
The invention provides a high-coating prepressability vegetable protein adhesive and a preparation method and application thereof. The adhesive is obtained by uniformly dispersing vegetable protein and a cross-linking agent in deionized water, uniformly dispersing a urushiol-acrylamide copolymer in the system, and uniformly dispersing nano-hydroxyapatite in the mixed system. The vegetable protein adhesive prepared by the invention has good coating performance, high prepressing performance, high waterproof adhesive bonding performance, mildew resistance, antibiosis and flame retardance, and the prepared plywood can meet the requirements of practical application of artificial boards.
Description
Technical Field
The invention relates to the technical field of biomass adhesives and high polymer materials, in particular to a high-coating prepressing-property vegetable protein adhesive and a preparation method and application thereof.
Background
In recent years, the annual output of artificial boards in China is about 3 billion cubic meters, and the artificial boards are widely applied to interior decoration and furniture manufacture. The consumption of the artificial board adhesive is about 1500 ten thousand tons, wherein the synthetic raw materials are taken as aldehyde resin adhesives and modified products thereof (urea-formaldehyde resin, phenolic resin and melamine formaldehyde resin) which are taken as main materials and account for more than 90 percent of the adhesive for the artificial board, and the problem of formaldehyde pollution of human living environment is brought. The vegetable protein adhesive becomes the research focus of the world wood industry due to the advantages of rich raw materials, reproducibility, safety, environmental protection and the like, and is the adhesive which is most hopeful to replace aldehyde resin in the artificial board industry to produce green and environment-friendly wood products in a large scale. The cross-linking modification is often used for improving the water resistance of the traditional vegetable protein adhesive and is widely used in actual production, but the cross-linking modified adhesive has weak interaction with a wood adhesion interface, so that the prepressing performance is low, the coating uniformity is poor, the distribution of a cured adhesive layer is uneven, and the characteristics of antibiosis and mould proofing are not provided, so that the vegetable protein adhesive is poor in glued board stability, the product machining performance is poor, and the large-scale industrial application of the glued board is limited.
Disclosure of Invention
The invention aims to provide a novel high-coating prepressing-property vegetable protein adhesive and a preparation method and application thereof.
The inventor is inspired by topological adhesion, a molecular topological structure is constructed in a plant protein adhesive system to enhance the adhesive property of the plant protein adhesive and a wood interface, the problems of poor coating prepressing performance and unstable adhesive bonding of the adhesive are solved while the adhesive bonding property of the plant protein adhesive is maintained, and the adhesive functionality is expanded.
In order to achieve the purpose of the invention, in a first aspect, the invention provides a high-coating prepressing-property vegetable protein adhesive, wherein the adhesive is a vegetable protein adhesive obtained by uniformly dispersing vegetable protein and a cross-linking agent in deionized water (a dispersion medium) to obtain a solution I, uniformly dispersing a urushiol-acrylamide copolymer in the solution I to obtain a solution II, and uniformly dispersing nano-hydroxyapatite in the solution II.
The weight of each component is as follows: 15 parts of vegetable protein, 1-3 parts of cross-linking agent, 53-85 parts of deionized water, 7-21 parts of urushiol-acrylamide copolymer and 1-3 parts of nano-hydroxyapatite.
The preparation method of the urushiol-acrylamide copolymer comprises the following steps:
(1) mixing 1-3g of sodium dodecyl sulfate and 2-4g of urushiol with 30ml of water, and emulsifying and dispersing at 10000-20000rpm at room temperature for 5-10 min;
(2) dissolving 15g of acrylamide, 0.06g N, N' -methylene bisacrylamide and 1g of ammonium persulfate in the dispersion system, and uniformly stirring at 25 ℃.
FIG. 1 is a graph showing the structure of urushiol-acrylamide copolymer characterized by ATR-FTIR according to the present invention. Wherein, U: urushiol, PUAM: urushiol-acrylamide copolymers.
The vegetable protein is water soluble isolated protein of soybean, peanut and cottonseed, and can be used alone or in combination. The particle size of the vegetable protein is less than 200 meshes, and the mass percentage content of the protein is higher than 90%.
The cross-linking agent can be selected from at least one of polyamide epichlorohydrin, trimethylolpropane triglycidyl ether, triglycidyl amine and the like.
In a second aspect, the invention provides a preparation method of the adhesive, which comprises the following steps:
(1) weighing the components according to the mass ratio, and uniformly dispersing the vegetable protein and the polyamide epichlorohydrin in deionized water to obtain a solution I;
(2) uniformly dispersing the urushiol-acrylamide copolymer in the solution I, and stirring for 15-20min at room temperature to obtain a solution II;
(3) and (3) uniformly dispersing the nano hydroxyapatite in the solution II, and stirring for 15-20min at room temperature to obtain the nano hydroxyapatite.
FIG. 2 is a scanning electron microscope image of the vegetable protein adhesive prepared by the present invention. The result of a microscopic scanning electron microscope shows that the vegetable protein adhesive prepared by the invention has a compact cross-linked structure, and the water-resistant adhesive bonding performance of the vegetable protein adhesive is improved.
FIG. 3 is a graph of the coating performance of the vegetable protein adhesive prepared according to the present invention.
In a third aspect, the invention provides an application of the adhesive in artificial board processing.
By the technical scheme, the invention at least has the following advantages and beneficial effects:
the urushiol-acrylamide copolymer is prepared by free radical polymerization, is simple and efficient, forms topological entanglement with a plant protein network, forms ionic bonds with nano-hydroxyapatite, and improves the cohesive force of the adhesive by cooperating with the physical enhancement effect of the nano-hydroxyapatite. The result of a microscopic scanning electron microscope shows that the vegetable protein adhesive prepared by the invention has a compact cross-linked structure, and the water-resistant adhesive bonding performance of the vegetable protein adhesive is improved.
The urushiol-acrylamide copolymer prepared by the invention has a large number of catechol groups, so that the adhesive has excellent initial adhesion and interface interaction, the adhesive has excellent coating performance and prepressing performance, and the bonding force between the adhesive and a wood interface can be effectively improved after curing.
And thirdly, the urushiol-acrylamide copolymer prepared by the invention endows the adhesive with antibacterial property and mildew resistance, and is cooperated with the nano hydroxyapatite to endow the adhesive with flame retardance.
And (IV) the vegetable protein adhesive prepared by the invention is green and environment-friendly, has no harmful substance release, has good performance, and further expands the practical application range of the vegetable protein adhesive.
The vegetable protein adhesive prepared by the invention has good coating performance, high prepressing performance, high waterproof bonding performance, mildew resistance, antibiosis and flame retardance, and the prepared plywood can meet the requirements of practical application of artificial boards.
Drawings
FIG. 1 is a graph showing the structure of urushiol-acrylamide copolymer characterized by ATR-FTIR according to the present invention. Wherein, U: urushiol, PUAM: urushiol-acrylamide copolymers.
FIG. 2 is a scanning electron microscope image of the vegetable protein adhesive prepared by the present invention.
FIG. 3 is a graph of the coating performance of the vegetable protein adhesive prepared according to the present invention.
Detailed Description
The following examples are intended to illustrate the invention, but are not intended to limit the scope of the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art, and the raw materials used are commercially available products.
The percent in the present invention means mass percent 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 25 ℃.
The vegetable protein used in the following examples was soy protein isolate, purchased from Shandong mountain pine soy protein Co., Ltd, having a particle size of 200 mesh and a protein content of 90% by mass.
The cross-linking agent polyamide epichlorohydrin is purchased from Shandong Tian chemical industry Co., Ltd, the pH value is about 4.5, and the solid content is about 12.0 wt%.
The nano-hydroxyapatite was purchased from Tianjin Xiansi Biotechnology Ltd.
The dispersion medium used was deionized water.
Example 1 preparation method of high coating prepressing Property vegetable protein adhesive
The embodiment provides a preparation method of a multifunctional plant protein adhesive with excellent coating performance and prepressing performance, wherein the plant protein adhesive is prepared according to the following weight ratio:
the preparation method of the vegetable protein adhesive comprises the following steps:
(1) weighing the components according to the weight ratio, dispersing the soy protein isolate and the cross-linking agent polyamide epichlorohydrin in deionized water (dispersion medium), and uniformly stirring.
(2) And (2) uniformly dispersing the urushiol-acrylamide copolymer in the dispersion liquid obtained in the system in the step (1), and stirring for 15min at 25 ℃.
(3) And (3) uniformly dispersing the nano hydroxyapatite in the dispersion liquid obtained in the system in the step (2), and stirring for 15min at 25 ℃ to obtain the soybean protein adhesive.
The preparation method of the urushiol-acrylamide copolymer comprises the following steps:
(1) mixing 1g of sodium dodecyl sulfate and 2g of urushiol with 30ml of water, and emulsifying and dispersing at 25 ℃ and 20000rpm for 8 min;
(2) dissolving 15g of acrylamide, 0.06g N, N' -methylene bisacrylamide and 1g of ammonium persulfate in the dispersion system, and uniformly stirring at 25 ℃.
Example 2
The embodiment provides a preparation method of a multifunctional plant protein adhesive with excellent coating performance and prepressing performance, wherein the plant protein adhesive is prepared according to the following weight ratio:
the preparation method of the vegetable protein adhesive is the same as that described in example 1.
The preparation method of the urushiol-acrylamide copolymer comprises the following steps:
(1) mixing 2g of sodium dodecyl sulfate and 3g of urushiol with 30ml of water, and emulsifying and dispersing at the temperature of 25 ℃ and the rpm of 15000 for 10 min;
(2) dissolving 16g of acrylamide, 0.07g N, N' -methylene bisacrylamide and 0.8g of ammonium persulfate in the dispersion system, and uniformly stirring at 25 ℃.
Comparative examples 1 to 4:
comparative example 1 was a mixture of 15g of soy protein isolate and 85g of dispersion medium; comparative example 2 is prepared by uniformly mixing 15g of soy protein isolate, 70g of dispersion medium and 15g of cross-linking agent polyamide epichlorohydrin; comparative example 3 is prepared by uniformly mixing 15g of soy protein isolate, 66g of dispersion medium, 15g of cross-linking agent polyamide epichlorohydrin, 4g of acrylamide, 0.2g of ammonium persulfate and 0.06g of N, N' -methylene bisacrylamide at 25 ℃), which are all purchased from Tianjin Xienchi Biotechnology, Inc. Comparative example 4 a melamine modified urea formaldehyde resin (grade E0) having a phenol/aldehyde molar ratio of 1.01 was purchased from knighton wood ltd.
Test example:
(1) three-layer plywood prepared by using the adhesives of examples 1-2 and comparative examples 1-4 of the invention was subjected to a bonding strength test.
Poplar veneer: drying to water content of 12%; the dimensions 40cm by 0.15 cm.
The preparation method comprises the following steps:
sizing: the glue coating amount is 180g/m 2 。
The processing conditions of the three-layer plywood are as follows: the pressure is 1MPa, the temperature is 120 ℃, and the time is 6 min.
And (3) performing performance detection on the transverse spliced material product according to a detection method of GB/T17657-1999 physical and chemical performance experimental methods of the artificial board and the facing artificial board.
(2) Three-layer plywood prepared by the adhesives of examples 1-2 and comparative examples 1-4 of the invention respectively is subjected to prepressing performance test.
The preparation method comprises the following steps:
sizing: the glue coating amount is 180g/m 2 。
The processing conditions of the three-layer plywood are as follows: the pressure is 1MPa, the temperature is 25 ℃, and the time is 1 h.
(3) Mildew resistance tests were carried out using the adhesives of examples 1-2 of the present invention and comparative examples 1-4, respectively.
15g of the synthetic binder was transferred to a petri dish and then stored in a constant temperature and humidity cabinet with a relative humidity of 50% and a temperature of 30 ℃.
The adhesives of examples 1-2 and comparative examples 1-4 of the present invention were used to perform antimicrobial activity tests on staphylococcus aureus, escherichia coli, and candida albicans, respectively.
The results of the above tests are shown in Table 1.
TABLE 1 Overall Properties of vegetable protein Adhesives
The test results show that the vegetable protein adhesive has low formaldehyde release compared with the aldehyde adhesive. In addition, the plant protein adhesive has good coating performance and high pre-pressing bonding strength, because the urushiol-acrylamide copolymer is provided with a large amount of catechol groups, the cohesion of the adhesive is effectively improved after the urushiol-acrylamide copolymer forms topological entanglement with a plant protein network, and meanwhile, the adhesive is endowed with excellent initial adhesion, and the interface interaction between the adhesive and wood is enhanced. The adhesive is applied to the plywood, the water-resistant bonding strength of the plywood can reach 1.22MPa according to the requirement of the type II plywood, the dry strength can reach 2.41MPa, and the standard requirement (more than or equal to 0.7MPa) of the type II plywood is met. Due to the characteristics of urushiol, the adhesive is endowed with excellent antibacterial and mildew-proof properties.
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 (5)
1. The high-coating prepressing-property vegetable protein adhesive is characterized in that the adhesive is a vegetable protein adhesive obtained by uniformly dispersing vegetable protein and a cross-linking agent in deionized water to obtain a solution I, uniformly dispersing a urushiol-acrylamide copolymer in the solution I to obtain a solution II, and uniformly dispersing nano-hydroxyapatite in the solution II;
the weight portions of the components are as follows: 15 parts of vegetable protein, 1-3 parts of a cross-linking agent, 53-85 parts of deionized water, 7-21 parts of urushiol-acrylamide copolymer and 1-3 parts of nano hydroxyapatite;
the preparation method of the urushiol-acrylamide copolymer comprises the following steps:
(1) mixing 1-3g of sodium dodecyl sulfate and 2-4g of urushiol with 30ml of water, and emulsifying and dispersing at 10000-;
(2) dissolving 15g of acrylamide, 0.06g N, N' -methylene bisacrylamide and 1g of ammonium persulfate in the dispersion system, and uniformly stirring at 25 ℃.
2. The adhesive according to claim 1, wherein the vegetable protein is water-soluble soybean, peanut and cottonseed protein isolate used singly or in a mixture; the particle size of the vegetable protein is less than 200 meshes, and the mass percentage content of the protein is higher than 90%.
3. The adhesive of claim 1, wherein the crosslinking agent is selected from at least one of polyamide epichlorohydrin, trimethylolpropane triglycidyl ether, and triglycidyl amine.
4. A process for the preparation of the adhesive according to any one of claims 1 to 3, comprising the steps of:
(1) weighing the components according to the mass ratio, and uniformly dispersing the vegetable protein and the cross-linking agent in deionized water to obtain a solution I;
(2) uniformly dispersing the urushiol-acrylamide copolymer in the solution I, and stirring for 15-20min at room temperature to obtain a solution II;
(3) and (3) uniformly dispersing the nano hydroxyapatite in the solution II, and stirring for 15-20min at room temperature to obtain the nano hydroxyapatite.
5. Use of the adhesive according to any one of claims 1-3 in the processing of artificial boards.
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| CN202210670587.1A CN114958298B (en) | 2022-06-14 | 2022-06-14 | High-coating pre-pressing vegetable protein adhesive and preparation method and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115595119A (en) * | 2022-09-14 | 2023-01-13 | 湖北福汉木业有限公司（Cn） | High-prepressing-property waterproof mildew-proof antibacterial vegetable protein adhesive as well as preparation method and application thereof |
Citations (3)
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| US5178646A (en) * | 1992-01-22 | 1993-01-12 | Minnesota Mining And Manufacturing Company | Coatable thermally curable binder presursor solutions modified with a reactive diluent, abrasive articles incorporating same, and methods of making said abrasive articles |
| CN107049959A (en) * | 2017-03-02 | 2017-08-18 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation method for the targeted nano gingko spherex for loading laccol |
| 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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2022
- 2022-06-14 CN CN202210670587.1A patent/CN114958298B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5178646A (en) * | 1992-01-22 | 1993-01-12 | Minnesota Mining And Manufacturing Company | Coatable thermally curable binder presursor solutions modified with a reactive diluent, abrasive articles incorporating same, and methods of making said abrasive articles |
| CN107049959A (en) * | 2017-03-02 | 2017-08-18 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation method for the targeted nano gingko spherex for loading laccol |
| CN113493678A (en) * | 2021-07-28 | 2021-10-12 | 南京林业大学 | Formaldehyde-free soy protein adhesive and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王冬晖;张萌;白卫斌;徐艳莲;林金火;: "具类辣素漆酚衍生物的制备及其抑菌性能", 中国生漆, no. 03, pages 47 - 51 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115595119A (en) * | 2022-09-14 | 2023-01-13 | 湖北福汉木业有限公司（Cn） | High-prepressing-property waterproof mildew-proof antibacterial vegetable protein adhesive as well as preparation method and application thereof |
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