CN114958298B - High-coating pre-pressing vegetable protein adhesive and preparation method and application thereof - Google Patents
High-coating pre-pressing vegetable protein adhesive and preparation method and application thereof Download PDFInfo
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- CN114958298B CN114958298B CN202210670587.1A CN202210670587A CN114958298B CN 114958298 B CN114958298 B CN 114958298B CN 202210670587 A CN202210670587 A CN 202210670587A CN 114958298 B CN114958298 B CN 114958298B
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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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Wood Science & Technology (AREA)
- Forests & Forestry (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides a high-coating pre-pressing vegetable protein adhesive and a preparation method and application thereof. The adhesive is prepared by uniformly dispersing vegetable protein and a cross-linking agent in deionized water, uniformly dispersing urushiol-acrylamide copolymer in the system, and finally uniformly dispersing nano hydroxyapatite in the mixed system. The prepared vegetable protein adhesive has good coating performance, high prepressing performance, high water-resistant cementing performance, mildew resistance, antibacterial property and flame retardance, and the prepared plywood can meet the actual application requirements of the artificial board.
Description
Technical Field
The invention relates to the technical field of biomass adhesives and high polymer materials, in particular to a high-coating pre-pressing 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 hundred million cubic meters, and the artificial boards are widely applied to indoor decoration and furniture manufacturing. The consumption of the adhesive for the artificial board is about 1500 ten thousand tons, wherein the synthetic raw material is an aldehyde resin adhesive and modified products (urea-formaldehyde resin, phenolic resin and melamine formaldehyde resin) thereof are mainly, and the consumption of the adhesive for the artificial board is more than 90 percent of the adhesive for the artificial board, thereby bringing the problem of formaldehyde pollution of the human living environment. The plant protein adhesive has the advantages of abundant raw materials, reproducibility, safety, environmental protection and the like, becomes the focus of wood industry research worldwide, and is the adhesive for producing green environmental protection wood products by replacing aldehyde resin in a large scale most hopefully in the artificial board industry. The crosslinking modification is often used for improving the water resistance of the traditional plant protein adhesive, but the interaction between the crosslinking modified adhesive and a wood adhesion interface is weak, so that the prepressing property is low, the coating uniformity is poor, the cured adhesive layer is unevenly distributed, and the adhesive has no antibacterial and mildew-proof characteristics, so that the adhesive glued by the plant protein adhesive has poor stability and poor product machining performance, and the large-scale industrial application of the adhesive is limited.
Disclosure of Invention
The invention aims to provide a novel high-coating pre-pressing plant 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 interfacial adhesion performance of the plant protein adhesive and the wood, so that the problems of poor pre-compaction and unstable adhesive coating while maintaining the adhesive bonding performance of the plant protein adhesive are solved, 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 pre-pressing plant protein adhesive, wherein the plant protein adhesive is obtained by uniformly dispersing plant protein and a crosslinking 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 finally 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 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 sodium dodecyl sulfate and 2-4g urushiol with 30ml water, emulsifying and dispersing at 10000-20000rpm at room temperature for 5-10min;
(2) 15g of acrylamide, 0.06g of N, N' -methylene bisacrylamide and 1g of ammonium persulfate are dissolved in the dispersion system, and the mixture is stirred uniformly at 25 ℃ to obtain the catalyst.
FIG. 1 is a representation of the structure of urushiol-acrylamide copolymer characterized by ATR-FTIR according to the present invention. Wherein, U: urushiol, PUAM: urushiol-acrylamide copolymer.
The plant protein is water-soluble soybean, peanut and cotton seed isolated protein which are used singly or in a mixed mode. The particle size of the vegetable protein is smaller than 200 meshes, and the mass percentage of the protein is higher than 90%.
The crosslinking agent may be at least one selected from the group consisting of polyamide epichlorohydrin, trimethylolpropane triglycidyl ether, triglycidyl amine, and the like.
In a second aspect, the present invention provides a method for preparing the adhesive, comprising the steps of:
(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 urushiol-acrylamide copolymer in the solution I, and stirring at room temperature for 15-20min to obtain a solution II;
(3) Uniformly dispersing 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 invention. The microscopic scanning electron microscope result shows that the plant protein adhesive prepared by the invention has a compact cross-linked structure, and improves the water-resistant adhesive property.
FIG. 3 is a graph showing the coating properties of the vegetable protein adhesive prepared according to the present invention.
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:
the urushiol-acrylamide copolymer prepared by free radical polymerization is simple and efficient, forms topological entanglement with a vegetable protein network, forms an ionic bond with nano hydroxyapatite, and improves cohesive force of the adhesive in cooperation with physical enhancement of the nano hydroxyapatite. The microscopic scanning electron microscope result shows that the plant protein adhesive prepared by the invention has a compact cross-linked structure, and improves the water-resistant adhesive property.
The urushiol-acrylamide copolymer prepared by the method has a large number of catechol groups, so that the adhesive is endowed with excellent initial viscosity 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 the adhesive is cured.
And thirdly, the urushiol-acrylamide copolymer prepared by the invention endows the adhesive with antibacterial property and mildew resistance, and cooperates with nano hydroxyapatite to endow the adhesive with flame retardance.
The prepared plant protein adhesive is environment-friendly, free of harmful substances and good in performance, and further expands the practical application range of the plant protein adhesive.
And fifthly, the prepared vegetable protein adhesive has good coating performance, high prepressing performance, high water-resistant adhesive bonding performance, mildew resistance, antibacterial property and flame retardance, and the prepared plywood can meet the requirements of actual application of the artificial board.
Drawings
FIG. 1 is a representation of the structure of urushiol-acrylamide copolymer characterized by ATR-FTIR according to the present invention. Wherein, U: urushiol, PUAM: urushiol-acrylamide copolymer.
FIG. 2 is a scanning electron microscope image of the vegetable protein adhesive prepared by the invention.
FIG. 3 is a graph showing the coating properties of the vegetable protein adhesive prepared according to the present invention.
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 25 ℃.
The vegetable protein used in the following examples was isolated soy protein, purchased from Shandong Soy protein Limited, having a particle size of 200 mesh and a protein mass percentage of 90%.
The cross-linking agent polyamide epichlorohydrin is purchased from Shandong Chemicals Co., ltd, and has a pH of about 4.5 and a solid content of about 12.0 wt%.
Nano hydroxyapatite was purchased from the company Tianjin saohen biochemical technology limited.
The dispersion medium used was deionized water.
Example 1 preparation method of high coating Pre-pressure 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 by the following components in parts by weight:
the preparation method of the vegetable protein adhesive comprises the following steps:
(1) Weighing the components according to the weight ratio, dispersing the soybean protein isolate and the cross-linking agent polyamide epichlorohydrin in deionized water (dispersion medium) and uniformly stirring.
(2) Uniformly dispersing the urushiol-acrylamide copolymer in the dispersion liquid obtained in the system of the step (1), and stirring for 15min at 25 ℃.
(3) Uniformly dispersing nano hydroxyapatite in the dispersion liquid obtained in the system of 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, emulsifying and dispersing for 8min at 20000rpm at 25 ℃;
(2) 15g of acrylamide, 0.06g of N, N' -methylene bisacrylamide and 1g of ammonium persulfate are dissolved in the dispersion system, and the mixture is stirred uniformly at 25 ℃ to obtain the catalyst.
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 by the following components in parts by weight:
the preparation method of the vegetable protein adhesive is the same as that described in the example 1.
The preparation method of the urushiol-acrylamide copolymer comprises the following steps:
(1) 2g of sodium dodecyl sulfate and 3g of urushiol are mixed with 30ml of water, and emulsified and dispersed for 10min at 15000rpm at 25 ℃;
(2) 16g of acrylamide, 0.07g of N, N' -methylenebisacrylamide and 0.8g of ammonium persulfate were dissolved in the above dispersion, and stirred uniformly at 25 ℃.
Comparative examples 1 to 4:
comparative example 1 was a uniform mixture of 15g of soy protein isolate and 85g of dispersion medium; comparative example 2 was a uniform mixture of 15g of soy protein isolate, 70g of dispersion medium, and 15g of cross-linking agent polyamide epichlorohydrin; comparative example 3 was prepared by uniformly mixing 15g of isolated soybean protein, 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' -methylenebisacrylamide at 25 ℃, all of which were purchased from Tianjin Seen Biochemical technology Co., ltd. Comparative example 4 was a melamine modified urea formaldehyde resin (grade E0) having a phenol/aldehyde molar ratio of 1.01, available from shandong kusen wood limited.
Test example:
(1) Three-layer plywood was prepared using the adhesives of examples 1-2 and comparative examples 1-4, respectively, for the bond strength test.
Poplar veneer: drying the water content to 12%; the dimensions are 40cm by 0.15cm.
The preparation method comprises the following steps:
sizing: the glue coating amount is 180g/m 2 。
Technological conditions for processing the three-layer plywood are as follows: the pressure is 1MPa, the temperature is 120 ℃ and the time is 6min.
The performance of the transverse spliced product is detected according to the detection method of GB/T17657-1999 artificial board and decorative artificial board physical and chemical Property experiment method.
(2) The prepressing test was performed by preparing three-layer plywood using the adhesives of examples 1-2 and comparative examples 1-4, respectively.
The preparation method comprises the following steps:
sizing: the glue coating amount is 180g/m 2 。
Technological conditions for processing the three-layer plywood are as follows: the pressure is 1MPa, the temperature is 25 ℃ and the time is 1h.
(3) Mildew resistance tests were performed using the adhesives of examples 1-2 and comparative examples 1-4, respectively.
15g of the synthetic adhesive were transferred to a petri dish and then stored in a constant temperature and humidity cabinet having a relative humidity of 50% and a temperature of 30 ℃.
Antibacterial activity tests were performed on staphylococcus aureus, escherichia coli and candida albicans using the adhesives of examples 1-2 and comparative examples 1-4, respectively.
The results of the above test are shown in Table 1.
TABLE 1 comprehensive Properties of plant protein adhesives
The test results show that the plant protein adhesive has low formaldehyde release compared with aldehyde adhesives. In addition, the vegetable protein adhesive has good coating performance and high pre-pressing bonding strength, and because the urushiol-acrylamide copolymer is provided with a large number of catechol groups, the cohesive force of the adhesive is effectively improved after topological entanglement is formed with a vegetable protein network, and meanwhile, the adhesive is endowed with excellent initial viscosity, and the interface interaction between the adhesive and wood is enhanced. When the adhesive is applied to the plywood, the waterproof bonding strength of the plywood can reach 1.22MPa according to the requirement of the class II plywood, the dry strength can reach 2.41MPa, and the waterproof bonding strength meets the standard requirement (more than or equal to 0.7 MPa) of the class II plywood. Due to the self-characteristics of urushiol, the adhesive is endowed with excellent antibacterial and mildew-proof properties.
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 (5)
1. The high-coating pre-pressing plant protein adhesive is characterized in that the adhesive is prepared by uniformly dispersing plant 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 finally 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 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 sodium dodecyl sulfate and 2-4g urushiol with 30ml water, emulsifying and dispersing at 10000-20000rpm at room temperature for 5-10min;
(2) 15g of acrylamide, 0.06g of N, N' -methylene bisacrylamide and 1g of ammonium persulfate are dissolved in the dispersion system, and the mixture is stirred uniformly at 25 ℃ to obtain the catalyst.
2. The adhesive according to claim 1, wherein the vegetable protein is water-soluble soybean, peanut, cottonseed protein isolate alone or in combination; the particle size of the vegetable protein is smaller than 200 meshes, and the mass percentage of the protein is higher than 90%.
3. The adhesive according to claim 1, wherein the crosslinking agent is at least one selected from the group consisting of polyamide epichlorohydrin, trimethylolpropane triglycidyl ether and triglycidyl amine.
4. A method for preparing 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 urushiol-acrylamide copolymer in the solution I, and stirring at room temperature for 15-20min to obtain a solution II;
(3) Uniformly dispersing 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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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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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| 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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| CN114958298A CN114958298A (en) | 2022-08-30 |
| CN114958298B true CN114958298B (en) | 2023-08-01 |
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| 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)
| 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 |
-
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- 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 |
|---|
| 具类辣素漆酚衍生物的制备及其抑菌性能;王冬晖;张萌;白卫斌;徐艳莲;林金火;;中国生漆(第03期);第47-51页 * |
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