CN116622060B - Multifunctional biomass crosslinking agent, vegetable protein adhesive and preparation method thereof - Google Patents
Multifunctional biomass crosslinking agent, vegetable protein adhesive and preparation method thereof Download PDFInfo
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- CN116622060B CN116622060B CN202210976077.7A CN202210976077A CN116622060B CN 116622060 B CN116622060 B CN 116622060B CN 202210976077 A CN202210976077 A CN 202210976077A CN 116622060 B CN116622060 B CN 116622060B
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- protein adhesive
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Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 84
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 84
- 239000003431 cross linking reagent Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 49
- 239000002028 Biomass Substances 0.000 title claims abstract description 45
- 108010082495 Dietary Plant Proteins Proteins 0.000 title claims abstract description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 45
- MWDZOUNAPSSOEL-UHFFFAOYSA-N kaempferol Natural products OC1=C(C(=O)c2cc(O)cc(O)c2O1)c3ccc(O)cc3 MWDZOUNAPSSOEL-UHFFFAOYSA-N 0.000 claims abstract description 34
- IQPNAANSBPBGFQ-UHFFFAOYSA-N luteolin Chemical compound C=1C(O)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(O)C(O)=C1 IQPNAANSBPBGFQ-UHFFFAOYSA-N 0.000 claims abstract description 34
- LRDGATPGVJTWLJ-UHFFFAOYSA-N luteolin Natural products OC1=CC(O)=CC(C=2OC3=CC(O)=CC(O)=C3C(=O)C=2)=C1 LRDGATPGVJTWLJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 235000009498 luteolin Nutrition 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 32
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 108010064851 Plant Proteins Proteins 0.000 claims abstract description 20
- 235000012054 meals Nutrition 0.000 claims abstract description 20
- 235000021118 plant-derived protein Nutrition 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 239000003398 denaturant Substances 0.000 claims abstract description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 17
- 244000105624 Arachis hypogaea Species 0.000 claims description 17
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 17
- 235000018262 Arachis monticola Nutrition 0.000 claims description 17
- 235000020232 peanut Nutrition 0.000 claims description 17
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 9
- 108090000526 Papain Proteins 0.000 claims description 5
- 239000004365 Protease Substances 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 229940055729 papain Drugs 0.000 claims description 5
- 235000019834 papain Nutrition 0.000 claims description 5
- 235000019764 Soybean Meal Nutrition 0.000 claims description 4
- 239000004455 soybean meal Substances 0.000 claims description 4
- 235000012343 cottonseed oil Nutrition 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 abstract description 8
- 125000003700 epoxy group Chemical group 0.000 abstract description 6
- 239000004593 Epoxy Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000011120 plywood Substances 0.000 description 29
- 241000219000 Populus Species 0.000 description 25
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 20
- 230000000694 effects Effects 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000003203 everyday effect Effects 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 125000001165 hydrophobic group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 235000018102 proteins Nutrition 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 102000005698 Frizzled receptors Human genes 0.000 description 1
- 108010045438 Frizzled receptors Proteins 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000014102 seafood Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2615—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen the other compounds containing carboxylic acid, ester or anhydride groups
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
- B32B21/13—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board all layers being exclusively wood
-
- 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
-
- 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
Abstract
The invention discloses a multifunctional biomass crosslinking agent and a preparation method thereof, wherein the preparation method comprises the following steps: s1, adding luteolin into epichlorohydrin, stirring and slowly dripping sodium hydroxide solution to obtain a reaction solution; s2, removing unreacted epichlorohydrin after the reaction liquid is extracted, and obtaining a brownish red viscous liquid. A vegetable protein adhesive and a preparation method thereof, wherein the preparation method comprises the following steps: adding plant protein meal powder into deionized water, stirring, adding a denaturant, stirring, and adding a multifunctional biomass crosslinking agent, and stirring, wherein the addition amount of the luteolin epoxy mixture accounts for 8-12% of the mass of the plant protein adhesive. The invention has the advantages of realizing the grafting epoxy group of the luteolin by a one-step method, obtaining the luteolin epoxy mixture, simultaneously having the functions of crosslinking and mildew proofing, replacing the existing crosslinking agent and mildew proofing agent, improving the water resistance, the bonding strength and the mildew proofing performance of the plant protein adhesive, along with environmental protection and health.
Description
Technical Field
The invention relates to the field of adhesive preparation. More specifically, the invention relates to a multifunctional biomass crosslinking agent, a plant protein adhesive and a preparation method thereof.
Background
The use amount of the commercially available trialdehyde (melamine formaldehyde adhesive, phenolic resin adhesive and urea formaldehyde adhesive) adhesives reaches more than 90 percent, but the production thereof depends on petroleum resources, has the problems of formaldehyde release and the like, and restricts the development of the artificial board industry. Therefore, development of healthy and environment-friendly vegetable proteins, starches and other bio-based adhesives is a necessary trend and a strong demand for development of adhesives for artificial boards.
At present, the plant protein is used as a raw material for preparing the adhesive, so that the problems of low bonding strength and poor mildew resistance are solved, the method is the simplest and effective method for solving the two problems, namely adding the cross-linking agent and the mildew-proof antibacterial agent, but most of the cross-linking agent and the mildew-proof agent come from petroleum resources, and potential safety risks are brought to human beings. Therefore, the development of the environment-friendly and healthy multifunctional biomass cross-linking agent has the cross-linking, mildew-proof and antibacterial effects, and is a difficult problem to be solved in industry.
Disclosure of Invention
It is an object of the present invention to solve at least the above problems and to provide at least the advantages to be described later.
The invention also aims to provide a multifunctional biomass cross-linking agent and a preparation method thereof, which are used for realizing the grafting of the epoxy groups on the luteolin by a one-step method to obtain the luteolin epoxy mixture and have the cross-linking and mildew-proof effects.
The invention also aims to provide the vegetable protein adhesive and the preparation method thereof, and the prepared vegetable protein adhesive has excellent water resistance, high bonding strength and good mildew resistance.
To achieve these objects and other advantages and in accordance with the purpose of the invention, there is provided a method for preparing a multifunctional biomass crosslinking agent, comprising the steps of:
s1, adding luteolin into epichlorohydrin, stirring at a constant temperature of 80-100 ℃, slowly dripping 1M sodium hydroxide solution while stirring, and stirring for 5-7h to obtain a reaction solution, wherein the mass ratio of the luteolin to the sodium hydroxide solution to the epichlorohydrin is 1:4-8:8-12;
s2, removing unreacted epichlorohydrin after the reaction liquid is extracted, and obtaining a brownish red viscous liquid.
Preferably, in the step S1, stirring is carried out at a constant temperature of 80 ℃ for 6 hours, wherein the mass ratio of luteolin to sodium hydroxide solution to epichlorohydrin is 1:4.5:8.
Preferably, the preparation method of luteolin comprises the following steps:
pulverizing peanut shells to 100 meshes, adding the peanut shells into a 1M sodium hydroxide solution, stirring at 60 ℃ for 5 hours to obtain an extracting solution, and then performing spray drying on the extracting solution to obtain luteolin, wherein the mass ratio of the peanut shells to the sodium hydroxide solution is 1:10.
The multifunctional biomass crosslinking agent is prepared by using the preparation method of the multifunctional biomass crosslinking agent.
The preparation method of the vegetable protein adhesive comprises the following steps:
90-110 parts of plant protein meal powder is added into 280-320 parts of deionized water and stirred for 20-25min, then 3-4 parts of denaturant is added and stirred for 20-25min, and then the multifunctional biomass cross-linking agent is added and stirred for 20-25min, wherein the addition amount of the multifunctional biomass cross-linking agent accounts for 8-12% of the mass of the plant protein adhesive.
Preferably, 100 parts of vegetable protein meal is crushed to 200 meshes according to parts by weight, added into 300 parts of deionized water and stirred uniformly, then 3.5 parts of denaturant is added and stirred for 20min, and then the multifunctional biomass crosslinking agent according to claim 4 is added and stirred for 20min.
Preferably, the addition amount of the multifunctional biomass crosslinking agent accounts for 10% of the mass of the vegetable protein adhesive.
Preferably, the denaturant is one or more of urea, sodium dodecyl sulfate and papain.
Preferably, the plant protein meal is one of high-temperature peanut meal, soybean meal and cottonseed meal.
The plant protein adhesive is prepared by using the preparation method of the plant protein adhesive.
The invention at least comprises the following beneficial effects:
the method has the advantages that the epoxy groups are grafted by the luteolin through a one-step method, the luteolin epoxy mixture is obtained, the crosslinking and mildew-proof effects are achieved, the existing crosslinking agent and mildew-proof agent are replaced, the water resistance, the bonding strength and the mildew resistance of the plant protein adhesive are improved, and the method is environment-friendly and healthy;
further, compared with the existing crosslinking agent, under the condition of less usage amount, (1) the adhesive has good viscosity, so that the smearing property of the adhesive in the preparation of the plywood is ensured; (2) the prepared three-layer poplar plywood meets the requirement of class I plywood; (3) the better crosslinking effect can be realized at room temperature without heating assistance;
still further, the low-substituted cross-linking agent is compared with the high-substituted cross-linking agent, the adhesive is prepared, and when the adhesive is further used for preparing the plywood, the obtained three-layer poplar plywood has better bonding strength, and the preparation process of the cross-linking agent is simplified while a better effect is obtained.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is an infrared spectrogram of a multifunctional biomass crosslinking agent prepared by different mass ratios of epichlorohydrin to luteolin;
FIG. 2 is an infrared spectrogram of the multifunctional biomass crosslinking agent prepared by different mass ratios of epichlorohydrin to luteolin;
fig. 3 is a schematic structural view of the bonding strength of the plywood of the invention.
Detailed Description
The present invention is described in further detail below with reference to examples to enable those skilled in the art to practice the same by referring to the description.
Reagent(s)
High-temperature peanut meal: shandong Yuhuang grain and oil Co., ltd
Soybean meal: qin Royal gold sea food industry Co.Ltd
Cotton seed meal: hebei morning light Biotechnology group Co., ltd
Epichlorohydrin, urea, papain: soy chemical Co., ltd
Sodium dodecyl sulfate: michelin chemical Co., ltd
Poplar veneer: river north Wenjia jia Hui veneer factory.
Example 1 ]
The preparation method of the multifunctional biomass crosslinking agent comprises the following steps:
firstly, crushing peanut shells to 100 meshes, adding the crushed peanut shells into a 1M sodium hydroxide solution, magnetically stirring the solution at 60 ℃ for 5 hours to obtain an extracting solution, and then performing spray drying on the extracting solution to obtain luteolin (in a powdery state), wherein the mass ratio of the peanut shells to the sodium hydroxide solution is 1:10;
adding luteolin powder into epichlorohydrin, magnetically stirring at a constant temperature of 80 ℃, uniformly and slowly dripping sodium hydroxide solution into a funnel while stirring, and stirring for 6 hours to obtain a reaction solution, wherein the mass ratio of the luteolin to the sodium hydroxide solution to the epichlorohydrin is 1:4.5:8;
and thirdly, extracting the reaction liquid by using acetone and water, and removing excessive unreacted epichlorohydrin by a rotary evaporator under the condition of reduced pressure to obtain brownish red viscous liquid, namely the multifunctional biomass crosslinking agent.
Example 2 ]
The preparation method of the multifunctional biomass crosslinking agent is the same as in example 1, except that the mass ratio of luteolin to epichlorohydrin is 1:10.
Example 3 ]
The preparation method of the multifunctional biomass crosslinking agent is the same as in example 1, except that the mass ratio of luteolin to epichlorohydrin is 1:12.
Example 4 ]
The preparation method of the vegetable protein adhesive comprises the following steps:
100g of high-temperature peanut meal is crushed to 200 meshes, 300g of deionized water is added, stirring is carried out for 20min at 60 ℃, then 3.5g of sodium dodecyl sulfate is added, stirring is carried out for 20min, and then the multifunctional biomass crosslinking agent prepared in the example 1, of which the mass of the adhesive is 10%, is added, and stirring is carried out for 20min.
Example 5 ]
The preparation method of the vegetable protein adhesive is the same as that of the example 4, except that the multifunctional biomass crosslinking agent prepared in the example 1, of which the mass is 8% of that of the adhesive, is added.
Example 6 ]
The preparation method of the vegetable protein adhesive is the same as that of the example 4, except that the multifunctional biomass crosslinking agent prepared in the example 1, of which the mass is 12%, is added.
Example 7 ]
The preparation method of the vegetable protein adhesive is the same as that of the example 4, except that: sodium dodecyl sulfate is replaced with urea.
Example 8 ]
The preparation method of the vegetable protein adhesive is the same as that of the example 4, except that: sodium dodecyl sulfate was replaced with papain.
Example 9 ]
The preparation method of the multifunctional biomass crosslinking agent is the same as in example 1, except that in step two, luteolin powder is added into epichlorohydrin, and magnetic stirring is performed at a constant temperature of 90 ℃.
Example 10 ]
The preparation method of the multifunctional biomass crosslinking agent is the same as in example 1, except that in step two, luteolin powder is added into epichlorohydrin, and magnetic stirring is performed at a constant temperature of 100 ℃.
Example 11 ]
The preparation method of the vegetable protein adhesive is the same as that of example 4, except that the high-temperature peanut meal is replaced by soybean meal.
Example 12 ]
The preparation method of the vegetable protein adhesive is the same as that of example 4, except that the high-temperature peanut meal is replaced by cottonseed meal.
Comparative example 1 ]
The preparation method of the vegetable protein adhesive is the same as that of the example 4, except that the multifunctional biomass crosslinking agent prepared in the example 1 is added, wherein the mass of the adhesive is 4%.
Comparative example 2 ]
The preparation method of the vegetable protein adhesive is the same as that of the example 4, except that the multifunctional biomass crosslinking agent prepared in the example 1 is added, wherein the mass of the adhesive is 6%.
Comparative example 3 ]
The preparation method of the vegetable protein adhesive is the same as that of example 4, except that sodium dodecyl sulfate is not added.
Comparative example 4 ]
The preparation method of the multifunctional biomass crosslinking agent is the same as in example 1, except that in step two, luteolin powder is added into epichlorohydrin, and magnetic stirring is performed under the constant temperature condition of 110 ℃.
Comparative example 5 ]
The preparation method of the multifunctional biomass crosslinking agent is the same as in example 1, except that in step two, luteolin powder is added into epichlorohydrin, and magnetic stirring is performed under the constant temperature condition of 120 ℃.
Comparative example 6 ]
The preparation method of the vegetable protein adhesive is the same as that of example 4, except that the stirring reaction temperature is controlled to be 60 ℃, and the multifunctional biomass crosslinking agent prepared in example 1, of which the mass of the adhesive is 10%, is replaced by polyamide epichlorohydrin (PAE) of which the mass of the adhesive is 16%.
Comparative example 7 ]
The preparation method of the vegetable protein adhesive is the same as that of example 4, except that the stirring reaction temperature is controlled to be 60 ℃, and the multifunctional biomass crosslinking agent prepared in example 1, of which the mass of the adhesive is 10%, is replaced by polyamide epichlorohydrin (PAE) of which the mass of the adhesive is 32%.
1. Synthesis detection
Taking the multifunctional biomass crosslinking agent prepared in examples 1-3 and luteolin prepared in example 1, performing FTIR spectrum analysis on the obtained multifunctional biomass crosslinking agent on a Nicolet 6700 spectrometer, and measuring the wavelength range of 4000-600cm -1 A total of 64 scans were performed with a resolution of 2cm -1 As shown in fig. 1-2, it can be seen from fig. 1-2:
characteristic absorption peak of epoxy group is 839cm -1 、912cm -1 And 1253cm -1 ;
At 1035cm -1 The absorption peak at which represents an ether bond connecting an epoxy group and a benzene ring;
in spectrum 1211cm of luteolin -1 An absorption peak of C-O bond was observed at 1211cm in the infrared absorption spectrum of the multifunctional biomass crosslinking agent due to the connection between the phenolic hydroxyl group and the benzene ring -1 The C-O absorption peak at this point disappeared.
The variation of the peaks demonstrates that epoxy groups are successfully grafted to luteolin, and at the same time, it can be seen that the peaks are most pronounced when the mass ratio of luteolin to epichlorohydrin is 1:8, respectively.
2. Performance detection
2.1 preparation of three-layer poplar plywood
According to the preparation methods of the vegetable protein adhesives described in examples 4-8, 11, 12 and 1-3, the corresponding vegetable protein adhesives (referred to as adhesives for short) are prepared respectively, and then three-layer poplar plywood is prepared, wherein the preparation method of the three-layer poplar plywood comprises the following steps:
drying the poplar veneer until the moisture content is 10%, wherein the drying temperature is 40 ℃ and the wind speed is 10m/s;
the adhesive is respectively smeared on the opposite sides of the 3 poplar veneers, and the smearing amount of each layer of adhesive is 180g/m 2 ;
Prepressing after every two vertical assembling of 3 poplar veneer lines, wherein the prepressing temperature is as follows: 25 ℃, prepressing pressure: 1-1.2 MPa, pre-pressing time: 10min, hot pressing the pre-pressed wood at the hot pressing temperature: 120 ℃, hot pressing time: 70s/mm, hot-pressing pressure: 1.2MPa, and obtaining the three-layer poplar plywood.
2.2 measurement of the bond Strength according to GB/T9846-2015
The bonding strength data of examples 4-6 and comparative examples 1-2 are shown in fig. 2, and it is known from fig. 2 that as the amount of the multifunctional biomass crosslinking agent added relative to the adhesive increases, the bonding strength tends to increase and then decrease, wherein when the amount of the multifunctional biomass crosslinking agent added is 10%, the optimal effect is achieved;
the bond strength data for examples 4, 7, 8, 11, 12, comparative example 3 are shown in Table 1 below:
table 1 three-layer poplar plywood bonding strength
As can be seen from table 1, the adhesive dry bond strengths of examples 4, 7, 8, 11, 12, the wet bond strength at 63 ℃ and the wet bond strength at 100 ℃ all meet the class I plywood requirement, which is far superior to comparative example 3, because: the addition of urea or sodium dodecyl sulfate promotes the expansion of globular frizzled proteins, exposes more hydrophobic groups, is favorable for the cross-linking reaction of active sites of the hydrophobic groups and a cross-linking agent, forms a dense network structure, and improves the water resistance and strength of the adhesive; the papain is added to promote the degradation of the protein, so that the protein is degraded from large molecular weight to small molecular weight, the reaction area is increased, the active site of the hydrophobic group and the crosslinking agent are also beneficial to the crosslinking reaction, a dense network structure is formed, and the water resistance and the strength of the adhesive are improved.
2.3 determination of formaldehyde emission
The measuring method comprises the following steps: measuring formaldehyde release according to GB/T39600-2021;
the formaldehyde emission data for examples 4, 7, 8, comparative example 3 are shown in Table 2 below:
table 2 three-layer poplar plywood bonding strength
Vegetable protein adhesive source | Example 4 | Example 7 | Example 8 | Comparative example 3 |
Formaldehyde emission (mg/m) 3 ) | 0.004 | 0.004 | 0.005 | 0.003 |
As can be seen from Table 2, the adhesives prepared in examples 4, 7, 8 and comparative example 3 have formaldehyde emissions of substantially 0, and satisfy E NF A level.
3. Determination of mildew-proof and antibacterial effects
A blank control group was constructed, specifically: crushing 100g of high-temperature peanut meal to 200 meshes, adding the crushed high-temperature peanut meal into 300g of deionized water, stirring for 20min at 60 ℃, and then adding 3.5g of sodium dodecyl sulfate and stirring for 40min;
putting the vegetable protein adhesive prepared by the preparation method of the vegetable protein adhesive in a clean culture dish at room temperature, and observing every day until the 37 th day starts to generate mould;
putting the vegetable protein adhesive prepared by the preparation method of the vegetable protein adhesive in a clean culture dish at room temperature, and observing every day until the 35 th day starts to generate mould;
putting the vegetable protein adhesive prepared by the preparation method of the vegetable protein adhesive in a clean culture dish at room temperature, and observing every day until the 35 th day starts to generate mould;
the blank control assembly is placed in a clean culture dish at room temperature, and is observed every day, and mould is generated on the 2 nd day;
according to the observation results, the plant protein adhesive prepared by the preparation methods of the plant protein adhesives described in examples 4, 7 and 8 has good mildew resistance.
4. Grafting efficiency determination
The grafting efficiency of the multifunctional biomass crosslinking agents of examples 1, 9, 10, comparative examples 4, 5 was calculated as = [ grafted monomer mass/actual product mass ]. 100%, as shown in table 3 below:
TABLE 3 grafting efficiency of multifunctional Biomass crosslinking agents
Example 1 | Example 9 | Example 10 | Comparative example 4 | Comparative example 4 | |
Definition of the definition | Product A | Product B | Product C | Product D | Product E |
Grafting efficiency (%) | 64.37% | 68.54% | 69.83% | 72.65% | 75.32% |
As can be seen from table 3, as the reaction temperature increases, the grafting efficiency increases, i.e., the content of highly substituted (number of hydroxyl groups successfully grafted with luteolin and epichlorohydrin) products, which are formed by the reaction of branched or functional side groups bound by chemical bonds on the macromolecular chains, called graft copolymers, increases with the increase of the reaction temperature, and the mass of grafted monomers is the mass of the product obtained by theoretical calculation with 4 hydroxyl groups grafted in this reaction, i.e., the theoretical yield.
5: the adhesive was prepared according to the procedure of example 4, using the products a, B, C, D, and E as the crosslinking agents, respectively, and the corresponding three-layer poplar plywood was prepared according to the preparation method of the three-layer poplar plywood described in "preparation of 2.1 three-layer poplar plywood", which was defined as three-layer poplar plywood a, three-layer poplar plywood B, three-layer poplar plywood C, three-layer poplar plywood D, and three-layer poplar plywood E in this order, and the measured bonding strength and formaldehyde release amount were measured, respectively, as shown in table 4 below:
table 4 bonding strength and formaldehyde release amount of three-layer poplar plywood A, B, C, D, E
As can be seen from table 4, the low-substituted cross-linking agent has better bonding strength than the high-substituted cross-linking agent, and the prepared adhesive is further used in the preparation of plywood.
6. The vegetable protein adhesives (abbreviated as adhesives) prepared in example 4 and comparative examples 6 to 7 were used for measuring viscosity by a rotational viscometer (CAP2000+H cone viscometer) method, as shown in Table 5 below:
table 5 viscosimetry
Example 4 | Comparative example 6 | Comparative example 7 | |
Viscosity of the product | 11412mP·s | 10796mP·s | 7263mP·s |
Further, the vegetable protein adhesives (abbreviated as adhesives) prepared in example 4 and comparative examples 6-7 were used to prepare corresponding three-layer poplar plywood according to the preparation method of 2.1 three-layer poplar plywood, and the measured bonding strength was measured respectively as shown in the following table 6:
table 6 determination of bond strength
As can be seen from table 5 in combination with table 6, compared with the PAE crosslinking agent, the multifunctional biomass crosslinking agent has good viscosity under the condition of less usage amount, and ensures the smearing property of the prepared adhesive when preparing the plywood; meanwhile, the prepared three-layer poplar plywood meets the requirement of the class I plywood, and the effect of the three-layer poplar plywood is superior to that of an adhesive prepared from PAE with quite smearing property;
furthermore, the multifunctional biomass crosslinking agent can carry out crosslinking reaction with the vegetable protein meal at room temperature, has better reaction effect and does not need heating assistance.
Although embodiments of the present invention have been disclosed above, it is not limited to the details and embodiments shown, it is well suited to various fields of use for which the invention is suited, and further modifications may be readily made by one skilled in the art, and the invention is therefore not to be limited to the particular details and examples shown and described herein, without departing from the general concepts defined by the claims and the equivalents thereof.
Claims (8)
1. The preparation method of the vegetable protein adhesive is characterized by comprising the following steps:
adding 90-110 parts of plant protein meal powder into 280-320 parts of deionized water, stirring for 20-25min, adding 3-4 parts of denaturant, stirring for 20-25min, and adding a multifunctional biomass crosslinking agent, stirring for 20-25min, wherein the addition amount of the multifunctional biomass crosslinking agent accounts for 8-12% of the mass of the plant protein adhesive;
the preparation method of the multifunctional biomass crosslinking agent comprises the following steps:
s1, adding luteolin into epichlorohydrin, stirring at a constant temperature of 80-100 ℃, slowly dripping 1-M sodium hydroxide solution while stirring, and stirring 5-7h to obtain a reaction solution, wherein the mass ratio of the luteolin to the sodium hydroxide solution to the epichlorohydrin is 1:4-8:8-12;
s2, removing unreacted epichlorohydrin after the reaction liquid is extracted, and obtaining a brownish red viscous liquid.
2. The method for preparing the plant protein adhesive according to claim 1, wherein in the step S1, stirring is performed at a constant temperature of 80 ℃, the mass ratio of luteolin to sodium hydroxide solution to epichlorohydrin is 1:4.5:8, and the stirring is performed at a temperature of 6 h.
3. The method for preparing the plant protein adhesive according to claim 1, wherein the method for preparing the luteolin comprises the following steps:
pulverizing peanut shells to 100 meshes, adding the peanut shells into a 1M sodium hydroxide solution, stirring at 60 ℃ for 5 hours to obtain an extracting solution, and then performing spray drying on the extracting solution to obtain luteolin, wherein the mass ratio of the peanut shells to the sodium hydroxide solution is 1:10.
4. The preparation method of the vegetable protein adhesive according to claim 1, wherein 100 parts of vegetable protein meal is crushed to 200 meshes according to parts by weight, 300 parts of deionized water is added to stir uniformly, 3.5 parts of denaturant is added to stir for 20min, and the multifunctional biomass crosslinking agent according to claim 1 is added to stir for 20min.
5. The method for preparing the plant protein adhesive according to claim 1, wherein the addition amount of the multifunctional biomass crosslinking agent is 10% of the mass of the plant protein adhesive.
6. The method for preparing the plant protein adhesive according to claim 1, wherein the denaturing agent is one or more of urea, sodium dodecyl sulfate and papain.
7. The method for preparing a vegetable protein adhesive according to claim 4, wherein the vegetable protein meal is one of high-temperature peanut meal, soybean meal and cottonseed meal.
8. A vegetable protein adhesive prepared by the method of preparing a vegetable protein adhesive according to any one of claims 1-7.
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