CN114736651A - Tough soybean protein adhesive and preparation method and application thereof - Google Patents
Tough soybean protein adhesive and preparation method and application thereof Download PDFInfo
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- CN114736651A CN114736651A CN202210396853.6A CN202210396853A CN114736651A CN 114736651 A CN114736651 A CN 114736651A CN 202210396853 A CN202210396853 A CN 202210396853A CN 114736651 A CN114736651 A CN 114736651A
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- soybean meal
- protein adhesive
- soybean
- tough
- dispersion liquid
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- 239000000853 adhesive Substances 0.000 title claims abstract description 39
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 39
- 108010073771 Soybean Proteins Proteins 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 235000019710 soybean protein Nutrition 0.000 title claims abstract description 11
- 235000019764 Soybean Meal Nutrition 0.000 claims abstract description 46
- 239000004455 soybean meal Substances 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000006185 dispersion Substances 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 238000000265 homogenisation Methods 0.000 claims abstract description 18
- 239000011347 resin Substances 0.000 claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 17
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 13
- 238000010008 shearing Methods 0.000 claims abstract description 13
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004359 castor oil Substances 0.000 claims abstract description 7
- 235000019438 castor oil Nutrition 0.000 claims abstract description 7
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 17
- 229940001941 soy protein Drugs 0.000 claims description 13
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000004952 Polyamide Substances 0.000 claims description 11
- 229920002647 polyamide Polymers 0.000 claims description 11
- 229920000768 polyamine Polymers 0.000 claims description 11
- IBGBGRVKPALMCQ-UHFFFAOYSA-N 3,4-dihydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1O IBGBGRVKPALMCQ-UHFFFAOYSA-N 0.000 claims description 10
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- PCYGLFXKCBFGPC-UHFFFAOYSA-N 3,4-Dihydroxy hydroxymethyl benzene Natural products OCC1=CC=C(O)C(O)=C1 PCYGLFXKCBFGPC-UHFFFAOYSA-N 0.000 claims description 5
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 5
- 235000011037 adipic acid Nutrition 0.000 claims description 5
- 239000001361 adipic acid Substances 0.000 claims description 5
- 239000002023 wood Substances 0.000 claims description 4
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 235000018102 proteins Nutrition 0.000 abstract description 24
- 108090000623 proteins and genes Proteins 0.000 abstract description 24
- 102000004169 proteins and genes Human genes 0.000 abstract description 24
- 229920002521 macromolecule Polymers 0.000 abstract description 6
- 238000001125 extrusion Methods 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 3
- 229920001184 polypeptide Polymers 0.000 abstract description 3
- 102000004196 processed proteins & peptides Human genes 0.000 abstract description 3
- 108090000765 processed proteins & peptides Proteins 0.000 abstract description 3
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 2
- 230000002209 hydrophobic effect Effects 0.000 abstract description 2
- 229920000570 polyether Polymers 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 11
- 239000011120 plywood Substances 0.000 description 9
- 244000046052 Phaseolus vulgaris Species 0.000 description 8
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 239000003292 glue Substances 0.000 description 4
- 230000003116 impacting effect Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical group C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- 108010064851 Plant Proteins Proteins 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000021118 plant-derived protein Nutrition 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical group C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000021120 animal protein Nutrition 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000227 bioadhesive Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- CUHVTYCUTYWQOR-UHFFFAOYSA-N formaldehyde Chemical compound O=C.O=C CUHVTYCUTYWQOR-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
- C08G69/50—Polymers modified by chemical after-treatment with aldehydes
-
- 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
- C09J11/06—Non-macromolecular additives organic
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a soybean protein adhesive, a preparation method and application thereof, wherein the soybean protein adhesive comprises soybean meal dispersion liquid, a modified PAE resin cross-linking agent, ethylene glycol diglycidyl ether and castor oil; the soybean meal dispersion liquid is subjected to high-pressure homogenization treatment, because the soybean meal protein is a macromolecule formed after polypeptide is coiled and folded, after the high-pressure shearing homogenization treatment, the soybean meal dispersion liquid is subjected to mechanical stress and centrifugal extrusion, the macromolecule is sheared into micromolecules, the protein forms a compact interface layer, the interaction chance among protein molecules is increased, and the particle size is reduced. On the basis of adopting the modified PAE resin cross-linking agent and the ethylene glycol diglycidyl ether, a cross-linked network structure is more easily formed by adding the castor oil serving as a hydrophobic polyether substance, so that the water resistance is improved and the bonding strength is further enhanced.
Description
Technical Field
The invention relates to the technical field of adhesives, and particularly relates to a soy protein adhesive as well as a preparation method and application thereof.
Background
The plywood is widely used, but the formaldehyde is contained in the plywood, so that the application of the plywood is limited. The formaldehyde contained in the plywood comes mainly from the adhesive except for a trace amount from the wood. The formaldehyde content of the formaldehyde-formaldehyde adhesive is high, so that the formaldehyde content in the indoor air is easy to exceed the standard for a long time, and the human health is threatened. Therefore, environmental friendly adhesives have attracted increasing attention from various industries.
The protein adhesive is a general name of a natural adhesive taking protein as a main raw material, which can be divided into an animal protein adhesive and a plant protein adhesive, and a soybean adhesive belonging to the plant protein adhesive shows greater development potential due to the reasons of capability of replacing fossil resources, rich raw material sources, low price, safety, environmental protection and the like.
The existing formaldehyde-free soybean protein adhesive has the defects of poor adhesive capacity and poor water resistance, so that the required adhesive strength and mechanical strength can be achieved only by large prepressing and hot pressing pressure in the process of preparing a light board.
Disclosure of Invention
In view of the above, the present invention aims to provide a tough soy protein adhesive, and a preparation method and an application thereof.
The purpose of the invention is realized by the following technical scheme:
a soy protein adhesive comprises a soybean meal dispersion liquid, a modified PAE resin cross-linking agent, ethylene glycol diglycidyl ether and castor oil.
The soy protein adhesive comprises the following components in parts by weight:
the mass concentration of the soybean meal powder in the soybean meal dispersion liquid is 10-20%.
The preparation method of the soybean meal dispersion liquid comprises the following steps:
s1, crushing the soybean meal into soybean meal powder, and then dispersing the soybean meal powder into water to prepare a soybean meal dispersion liquid;
and S2, carrying out high-pressure shearing and homogenizing treatment on the soybean meal dispersion liquid.
In step S2, homogenizing under 10-20Mpa for 5-10 min.
The particle size of the soybean meal powder is 100-200 meshes.
The preparation method of the modified PAE resin cross-linking agent comprises the following steps:
step 1, preparation of a polyamide polyamine intermediate: adding adipic acid and diethylenetriamine into a reaction kettle, stirring uniformly after the raw materials are completely mixed and melted, heating to evaporate water in the solution, evaporating the water to dryness, immediately stopping heating, cooling to below 120 ℃, adding water to adjust the solid content to 20-30 wt%, stirring to a homogeneous phase, and stopping stirring to prepare a polyamide polyamine intermediate solution;
step 2, preparing a prepolymer of the grafted catechol group: adding the polyamide polyamine intermediate solution and 3, 4-dihydroxybenzaldehyde into a reaction kettle, and stirring and reacting at 25-30 ℃ to obtain a grafted catechol group prepolymer;
step 3, preparing the modified PAE resin cross-linking agent: and adding water into the grafted catechol group prepolymer, slowly dropwise adding epoxy chloropropane, heating to 60-65 ℃ after dropwise adding, keeping the temperature for 1-2h, and dropwise adding HCl to adjust the pH value to 3-4 to obtain the modified PAE resin crosslinking agent.
Step 1 specifically, adding adipic acid and diethylenetriamine into a reaction kettle, stirring uniformly after the raw materials are completely mixed and melted, heating to 150-.
And step 2, adding the polyamide polyamine intermediate solution and 3, 4-dihydroxybenzaldehyde into a reaction kettle, and stirring to react to obtain the grafted catechol group prepolymer.
The application of the tough soybean protein adhesive as a wood adhesive also belongs to the protection scope of the invention.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention carries out high-pressure homogenization treatment on the bean pulp dispersion liquid, searches out the optimal process, and homogenizes the bean pulp dispersion liquid for 5-10min under 10-20Mpa to obtain the bean pulp dispersion liquid with better physicochemical properties, because the bean pulp protein is a macromolecule formed after the polypeptide is coiled and folded, after the high-pressure shearing homogenization treatment, the bean pulp dispersion liquid is subjected to mechanical stress and centrifugal extrusion, the macromolecule is sheared into micromolecules, so that the protein forms a compact interface layer, the interaction chance among the protein molecules is increased, and the particle size is reduced. In addition, in the high-pressure homogenization process, the soybean meal particles are subjected to huge shearing and impacting effects, the homogenization time is prolonged, the impacting and shearing times of the soybean meal are continuously increased, and the particle size of the soybean meal particles is smaller and smaller. Because the disulfide bonds in the protein molecules are destroyed by mechanical shearing force, the exposed hydrophilic groups are increased, the hydrophobicity of the protein surface is reduced, the hydrophilic groups are easy to combine with water, and the water absorption of the soybean meal is favorably improved; however, if the homogenization pressure is not higher, or the homogenization time is longer, the homogenization is better, and if the pressure is too high or the homogenization time is too long, the mechanical structure in the protein is damaged, and the water absorption performance is reduced;
2. the catechol functional group is grafted on the PAE, so that the initial viscosity of the prepared protein adhesive is obviously improved, the prepressing forming time is greatly shortened, and the water-resistant bonding strength is improved;
3. ethylene glycol diglycidyl ether is a protein molecular recombination agent, so that hydrolyzed small molecular proteins can be recombined to form a prepolymer with a certain molecular weight, and the cohesive force of adhesive molecules is increased;
4. according to the invention, on the basis of adopting the modified PAE resin cross-linking agent and ethylene glycol diglycidyl ether, a cross-linked network structure is more easily formed by adding castor oil serving as a hydrophobic polyether substance, so that the water resistance is improved and the bonding strength is further enhanced.
Detailed Description
The present invention will be described in detail with reference to examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept. All falling within the scope of the invention.
Example 1 preparation of a Dispersion of soybean meal
The preparation method comprises the following steps:
(1) crushing the soybean meal, sieving the crushed soybean meal with a 200-mesh sieve, and then dispersing the soybean meal powder in water to prepare a soybean meal dispersion liquid with the mass concentration of 10%;
(2) treating the soybean meal dispersion liquid by using a homogenizer with high-pressure shearing, wherein the homogenizing pressure and the homogenizing time are shown in table 1;
(3) the particle size and water absorption of the soybean meal in the soybean meal dispersion liquid obtained in each experimental group were measured.
TABLE 1
Wherein the control group is soybean meal dispersion liquid without treatment.
The water absorption test method is as follows:
step 1, drying samples of each experimental group in table 1 to obtain a solidified protein sample and weighing the solidified protein sample;
2, putting the solidified protein sample into a constant temperature and humidity box with the relative humidity of 80% and the temperature of 50 ℃;
and 3, weighing after 4 hours.
Calculating the protein water absorption rate according to a formula, wherein the water absorption rate is (B-A)/A multiplied by 100 percent
A mass of sample before water absorption and B mass of sample after water absorption
The results in Table 1 show that the obtained soybean meal dispersion liquid has good physicochemical properties after being homogenized for 5-10min under 10-20 MPa. The reason is that:
1) the particle size of the bean pulp which is not processed is the largest, because the bean pulp protein is a macromolecule formed after polypeptide coiling and folding, after high-pressure shearing homogenization treatment, the bean pulp dispersion liquid is subjected to mechanical stress and centrifugal extrusion, the macromolecule is sheared into micromolecules, so that the protein forms a compact interface layer, the interaction chance among protein molecules is increased, and the particle size is reduced. In addition, in the high-pressure homogenization process, the soybean meal particles are subjected to huge shearing and impacting effects, the homogenization time is prolonged, the impacting and shearing times of the soybean meal are continuously increased, and the particle size of the soybean meal particles is smaller and smaller.
2) The unmodified soybean meal has the lowest water absorption rate, and the soybean meal is improved after high-pressure shearing homogenization treatment, because the disulfide bonds in protein molecules are destroyed by mechanical shearing force, the exposed hydrophilic groups are increased, the hydrophobicity of the surface of the protein is reduced, and the hydrophilic groups are easy to combine with water, so that the improvement of the soybean meal water absorption rate is facilitated.
However, if the homogenization pressure is not increased, or if the homogenization time is increased, the homogenization time is not increased, the mechanical structure inside the protein is destroyed, and the water absorption performance is rather decreased.
Examples2-5
Embodiments 2-5 relate to a tough soy protein adhesive and a preparation method thereof.
1. Tough soy protein adhesive formula
The components and amounts of the tough soy protein adhesives of examples 2-6 are shown in table 1, where "-" in table 1 means no addition.
TABLE 1 (Unit: parts by weight)
The soybean meal dispersion was prepared by the method provided in test group 7 of example 1.
The preparation method of the modified PAE resin cross-linking agent comprises the following steps:
step 1, preparation of a polyamide polyamine intermediate: adding adipic acid and diethylenetriamine into a reaction kettle, stirring uniformly after the raw materials are completely mixed and melted, heating to 150-180 ℃, evaporating water in the solution, immediately stopping heating after the water is evaporated, adding a certain proportion of water when the temperature is reduced to below 120 ℃, adjusting the solid content to 20-30 wt%, stirring to a homogeneous phase, and stopping stirring to prepare the polyamide polyamine intermediate solution
Step 2, preparing a prepolymer of the grafted catechol group: adding the polyamide polyamine intermediate solution and 3, 4-dihydroxybenzaldehyde into a reaction kettle, and stirring for reaction at 25-30 ℃ to obtain a grafted catechol group prepolymer;
step 3, preparing the modified PAE resin cross-linking agent: and adding water into the grafted catechol group prepolymer, slowly dropwise adding 10kg of epoxy chloropropane, heating to 60-65 ℃ after dropwise adding, keeping the temperature for 1-2h, and dropwise adding HCl to adjust the pH value to 3-4 to obtain the modified PAE resin crosslinking agent.
2. Preparation method
Step 1, preparing materials according to the formula in table 1;
step 2, stirring the soybean meal dispersion liquid, the modified PAE resin cross-linking agent polyacrylate and ethylene glycol diglycidyl ether for 20min by using a magnetic stirrer, and uniformly mixing to prepare a mixed solution;
and 3, dropwise adding castor oil into the mixed solution prepared in the step 2, uniformly stirring at 50-55 ℃, and adding a defoaming agent to prepare the tough soybean protein adhesive.
Comparative example 1
This comparative example differs from example 2 in that no modified PAE resin crosslinker polyacrylate is added.
Comparative example 2
This comparative example differs from example 2 in that the modified PAE resin crosslinker was replaced with a polyacrylate emulsion (AE).
Comparative example 3
This comparative example differs from example 2 in that no castor oil was added.
Comparative example 4
This comparative example differs from example 2 in that ethylene glycol diglycidyl ether is replaced with Neopentyl Glycol Diglycidyl Ether (NGDE).
Comparative example 5
This comparative example differs from example 2 in that ethylene glycol diglycidyl ether is replaced with bisphenol a diglycidyl ether.
Application effect testing
The glue prepared in the examples 2-5 and the comparative examples 1-5 is respectively used for preparing three-layer plywood, and the specific method comprises the following steps:
drying the wood veneer until the water content is 5-7%, and uniformly coating the glue prepared in the examples 2-5 and the comparative examples 1-5 on the two sides of the veneer core layer, wherein the glue application amount is 280g/m2The veneers coated with the glue are stacked, three layers of the veneers form a plate blank, the plate blank is placed into a cold press to be cold-pressed for 30min, the plate surface is repaired after the cold pressing is finished, the plate blank is placed into a hot press to be hot-pressed at 130 ℃ after the repairing is finished, the hot pressing time is 1.5min/mm, and the plywood is obtained after the hot pressing is finished. The detection shows that the plywood can meet the requirements of II types of plywood specified in GB/T9846-2016, and the wet bonding strength is measured after the plywood is soaked in water at the temperature of 80 ℃ for 3 hours, and the results are shown in Table 2.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (10)
1. The soy protein adhesive is characterized by comprising a soybean meal dispersion liquid, a modified PAE resin cross-linking agent, ethylene glycol diglycidyl ether and castor oil.
2. The soy protein adhesive as claimed in claim 1, which comprises the following components in parts by weight:
3. the soy protein adhesive as claimed in claim 1 or 2, wherein the mass concentration of the soybean meal powder in the soybean meal dispersion is 10-20%.
4. The tough soybean protein adhesive according to claim 2, wherein the preparation method of the soybean meal dispersion liquid comprises the following steps:
s1, crushing the soybean meal into soybean meal powder, and then dispersing the soybean meal powder into water to prepare a soybean meal dispersion liquid;
and S2, carrying out high-pressure shearing and homogenizing treatment on the soybean meal dispersion liquid.
5. The tough soybean protein adhesive of claim 4, wherein in the step S2, the homogenization treatment is performed under 10-20MPa for 5-10 min.
6. The tough soy protein adhesive as claimed in claim 4, wherein the particle size of the soybean meal is 100-200 mesh.
7. The tough soy protein adhesive of claim 2, wherein the modified PAE resin cross-linking agent is prepared by a method comprising the following steps:
step 1, preparation of a polyamide polyamine intermediate: adding adipic acid and diethylenetriamine into a reaction kettle, stirring uniformly after the raw materials are completely mixed and melted, heating to evaporate water in the solution, evaporating the water to dryness, immediately stopping heating, cooling to below 120 ℃, adding water to adjust the solid content to 20-30 wt%, stirring to a homogeneous phase, and stopping stirring to prepare a polyamide polyamine intermediate solution;
step 2, preparing a prepolymer of the grafted catechol group: adding the polyamide polyamine intermediate solution and 3, 4-dihydroxybenzaldehyde into a reaction kettle, and stirring for reaction at 25-30 ℃ to obtain a grafted catechol group prepolymer;
step 3, preparing the modified PAE resin cross-linking agent: and adding water into the grafted catechol group prepolymer, slowly dropwise adding epoxy chloropropane, heating to 60-65 ℃ after dropwise adding, keeping the temperature for 1-2h, and dropwise adding HCl to adjust the pH value to 3-4 to obtain the modified PAE resin crosslinking agent.
8. The tough soybean protein adhesive as claimed in claim 7, wherein the step 1 is specifically that adipic acid and diethylenetriamine are added into a reaction kettle, after the raw materials are completely mixed and melted, the mixture is uniformly stirred, the temperature is raised to 150-.
9. The tough soybean protein adhesive according to claim 7, wherein the step 2 is to add the polyamide polyamine intermediate solution and 3, 4-dihydroxybenzaldehyde into a reaction kettle, and stir to react to obtain the grafted catechol group prepolymer.
10. Use of the tough soy protein adhesive of any one of claims 1-9 as a wood adhesive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210396853.6A CN114736651B (en) | 2022-04-15 | 2022-04-15 | Tough soybean protein adhesive and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210396853.6A CN114736651B (en) | 2022-04-15 | 2022-04-15 | Tough soybean protein adhesive and preparation method and application thereof |
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| Publication Number | Publication Date |
|---|---|
| CN114736651A true CN114736651A (en) | 2022-07-12 |
| CN114736651B CN114736651B (en) | 2024-01-05 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116535874A (en) * | 2023-06-14 | 2023-08-04 | 东北林业大学 | Waterproof biodegradable wood flour and bean pulp composite material and preparation method thereof |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040173306A1 (en) * | 2002-10-24 | 2004-09-09 | University Of Southern Mississippi | Particleboard and method for forming a particleboard |
| US20100310877A1 (en) * | 2009-03-06 | 2010-12-09 | Parker Anthony A | Protein-Containing Emulsions and Adhesives, and Manufacture and Use Thereof |
| US20110229698A1 (en) * | 2010-03-19 | 2011-09-22 | E2E Materials, Inc. | Biodegradable resin composites |
| CN105542710A (en) * | 2016-02-03 | 2016-05-04 | 北京林业大学 | Waterproof soybean meal adhesive and preparation method thereof |
| CN106589295A (en) * | 2016-12-29 | 2017-04-26 | 嘉兴德扬生物科技有限公司 | Nanometer oxide and castor oil modified polyurethane adhesive and preparation method thereof |
| CN106811171A (en) * | 2016-12-23 | 2017-06-09 | 北京林业大学 | A kind of modified timber-used dregs of beans base adhesive and preparation method thereof |
| CN109401704A (en) * | 2018-10-30 | 2019-03-01 | 湖南柯盛新材料有限公司 | A kind of high solid content water epoxy adhesive and preparation method thereof |
| CN109504343A (en) * | 2018-11-23 | 2019-03-22 | 北京林业大学 | A kind of aldehyde-free gum and preparation method thereof |
| CN110484193A (en) * | 2019-08-28 | 2019-11-22 | 韦权 | A kind of preparation method of the moisture-proof glass cement of high cohesive force |
| CN111171783A (en) * | 2020-01-20 | 2020-05-19 | 北京林业大学 | Modified wood fiber reinforced plant protein adhesive and preparation method and application thereof |
| CN111171314A (en) * | 2020-01-20 | 2020-05-19 | 北京林业大学 | Modified PAE resin crosslinking agent, modified adhesive and application |
| US20220017788A1 (en) * | 2018-11-20 | 2022-01-20 | Oregon State University | Ultraviolet radiation-cured pressure sensitive adhesives from plant oils or animal fats |
| KR102366394B1 (en) * | 2021-01-05 | 2022-02-23 | 조광용 | A hyaluronic acid bead gel having high swelling characteristics |
-
2022
- 2022-04-15 CN CN202210396853.6A patent/CN114736651B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040173306A1 (en) * | 2002-10-24 | 2004-09-09 | University Of Southern Mississippi | Particleboard and method for forming a particleboard |
| US20100310877A1 (en) * | 2009-03-06 | 2010-12-09 | Parker Anthony A | Protein-Containing Emulsions and Adhesives, and Manufacture and Use Thereof |
| US20110229698A1 (en) * | 2010-03-19 | 2011-09-22 | E2E Materials, Inc. | Biodegradable resin composites |
| CN105542710A (en) * | 2016-02-03 | 2016-05-04 | 北京林业大学 | Waterproof soybean meal adhesive and preparation method thereof |
| CN106811171A (en) * | 2016-12-23 | 2017-06-09 | 北京林业大学 | A kind of modified timber-used dregs of beans base adhesive and preparation method thereof |
| CN106589295A (en) * | 2016-12-29 | 2017-04-26 | 嘉兴德扬生物科技有限公司 | Nanometer oxide and castor oil modified polyurethane adhesive and preparation method thereof |
| CN109401704A (en) * | 2018-10-30 | 2019-03-01 | 湖南柯盛新材料有限公司 | A kind of high solid content water epoxy adhesive and preparation method thereof |
| US20220017788A1 (en) * | 2018-11-20 | 2022-01-20 | Oregon State University | Ultraviolet radiation-cured pressure sensitive adhesives from plant oils or animal fats |
| CN109504343A (en) * | 2018-11-23 | 2019-03-22 | 北京林业大学 | A kind of aldehyde-free gum and preparation method thereof |
| CN110484193A (en) * | 2019-08-28 | 2019-11-22 | 韦权 | A kind of preparation method of the moisture-proof glass cement of high cohesive force |
| CN111171783A (en) * | 2020-01-20 | 2020-05-19 | 北京林业大学 | Modified wood fiber reinforced plant protein adhesive and preparation method and application thereof |
| CN111171314A (en) * | 2020-01-20 | 2020-05-19 | 北京林业大学 | Modified PAE resin crosslinking agent, modified adhesive and application |
| KR102366394B1 (en) * | 2021-01-05 | 2022-02-23 | 조광용 | A hyaluronic acid bead gel having high swelling characteristics |
Non-Patent Citations (1)
| Title |
|---|
| 程佳慧等: "聚酰胺多胺环氧氯丙烷树脂大豆胶黏剂制备及性能研究", 林产工业, vol. 57, no. 01, pages 08 - 11 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116535874A (en) * | 2023-06-14 | 2023-08-04 | 东北林业大学 | Waterproof biodegradable wood flour and bean pulp composite material and preparation method thereof |
| CN116535874B (en) * | 2023-06-14 | 2024-03-29 | 东北林业大学 | Waterproof biodegradable wood flour and bean pulp composite material and preparation method thereof |
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| CN114736651B (en) | 2024-01-05 |
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