CN114736651B - Tough soybean protein adhesive and preparation method and application thereof - Google Patents
Tough soybean protein adhesive and preparation method and application thereof Download PDFInfo
- Publication number
- CN114736651B CN114736651B CN202210396853.6A CN202210396853A CN114736651B CN 114736651 B CN114736651 B CN 114736651B CN 202210396853 A CN202210396853 A CN 202210396853A CN 114736651 B CN114736651 B CN 114736651B
- Authority
- CN
- China
- Prior art keywords
- soybean meal
- soybean
- water
- dispersion liquid
- protein
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 34
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 34
- 108010073771 Soybean Proteins Proteins 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 235000019710 soybean protein Nutrition 0.000 title claims abstract description 17
- 235000019764 Soybean Meal Nutrition 0.000 claims abstract description 52
- 239000004455 soybean meal Substances 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000006185 dispersion Substances 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 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
- 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
- 238000000265 homogenisation Methods 0.000 claims abstract description 8
- 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 20
- 239000004952 Polyamide Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 229920002647 polyamide Polymers 0.000 claims description 13
- 229920000768 polyamine Polymers 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 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
- 239000002245 particle Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 8
- 239000003292 glue Substances 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
- 239000007787 solid Substances 0.000 claims description 5
- 229940001941 soy protein Drugs 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 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 2
- 239000002131 composite material Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 235000018102 proteins Nutrition 0.000 abstract description 23
- 108090000623 proteins and genes Proteins 0.000 abstract description 23
- 102000004169 proteins and genes Human genes 0.000 abstract description 23
- 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
- 150000003384 small molecules Chemical class 0.000 abstract description 3
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 2
- 238000005452 bending Methods 0.000 abstract description 2
- 230000002209 hydrophobic effect Effects 0.000 abstract description 2
- 229920000570 polyether Polymers 0.000 abstract description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000243 solution Substances 0.000 description 9
- 239000011120 plywood Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 238000007731 hot pressing Methods 0.000 description 4
- 230000003116 impacting effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 3
- 238000003825 pressing Methods 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
- 239000000227 bioadhesive Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000010410 layer Substances 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
- 238000010025 steaming Methods 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
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000126 substance Substances 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 invention carries out high-pressure homogenization treatment on the soybean meal dispersion liquid, because the soybean meal protein is a macromolecule formed by bending and folding polypeptide, after the high-pressure shearing homogenization treatment, the soybean meal dispersion liquid is subjected to mechanical stress and centrifugal extrusion, and the macromolecule is sheared into small molecules, so that the protein forms a compact interface layer, the interaction opportunity among protein molecules is increased, and the grain size is reduced. On the basis of adopting the modified PAE resin cross-linking agent and the ethylene glycol diglycidyl ether, the hydrophobic polyether castor oil is added, so that a cross-linked network structure is easier to form, the water resistance is improved, and the bonding strength is further enhanced.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a soybean protein adhesive and a preparation method and application thereof.
Background
The plywood is widely used, but has a problem of restricting the application because of the formaldehyde. The formaldehyde contained in the plywood is mainly derived from the adhesive except for a trace amount from the wood itself. The formaldehyde content in the indoor air is easily exceeded for a long time due to high formaldehyde content in the trialdehyde glue, which causes threat to human health. Therefore, environmental protection type adhesives are attracting attention in various industries.
The protein adhesive is a general name of a natural adhesive which takes protein as a main raw material, and can be divided into an animal protein adhesive and a plant protein adhesive, and the soybean adhesive which belongs to the plant protein adhesive has great development potential because of being capable of replacing fossil resources, being rich in raw material sources, low in price, safe, environment-friendly and the like, and has the defects of low bonding strength, poor water resistance and the like, but is increasingly focused because of the limitation of global petroleum resources, the environmental pollution problem and the like, so that the environment-friendly natural adhesive is considered again in industrial application, and the soybean protein adhesive becomes a research hot spot again.
The existing aldehyde-free soybean protein adhesives have the defects of poor adhesive capacity and poor water resistance, so that larger prepressing and hot pressing pressure are needed in the process of preparing the light-weight plate to achieve the required adhesive strength and mechanical strength.
Disclosure of Invention
In view of the above, the invention aims to provide a tough soybean protein adhesive, and a preparation method and application thereof.
The aim of the invention is realized by the following technical scheme:
a soybean protein adhesive comprises soybean meal dispersion liquid, modified PAE resin cross-linking agent, ethylene glycol diglycidyl ether and castor oil.
The soybean 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 soybean meal into soybean meal powder, and dispersing the soybean meal powder in water to prepare soybean meal dispersion liquid;
s2, carrying out high-pressure shearing homogenization treatment on the soybean meal dispersion liquid.
In the step S2, the homogenization treatment is carried out for 5-10min under the condition of 10-20 Mpa.
The grain 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, heating to evaporate water in the solution, immediately stopping heating after the water is evaporated to dryness, cooling to below 120 ℃, adding water to adjust the solid content to 20-30wt%, stirring until the materials are homogeneous, and stopping stirring to prepare the polyamide polyamine intermediate solution;
step 2, preparation of grafted catechol group prepolymer: adding a 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 a 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 the dropwise adding, preserving heat for 1-2h, and then dropwise adding HCL to adjust the pH value to 3-4 to obtain the modified PAE resin crosslinking agent.
Adding adipic acid and diethylenetriamine into a reaction kettle, stirring uniformly after the raw materials are completely mixed, heating to 150-180 ℃, steaming to remove water in the solution, immediately stopping heating after the water is evaporated, cooling to below 120 ℃, adding a certain proportion of water to adjust the solid content to 20-30wt%, stirring until the materials are homogeneous, and stopping stirring to prepare the polyamide polyamine intermediate solution.
And step 2, specifically, adding the polyamide polyamine intermediate solution and 3, 4-dihydroxybenzaldehyde into a reaction kettle, and stirring for reaction to obtain a 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 soybean meal dispersion liquid, and finds out the optimal process, and the obtained soybean meal dispersion liquid is homogenized for 5-10min under 10-20Mpa, and has better physicochemical properties, because the soybean meal protein is a macromolecule formed by folding polypeptide disc, after the high-pressure shearing homogenization treatment, the soybean meal dispersion liquid is subjected to mechanical stress and centrifugal extrusion, and the macromolecule is sheared into small molecules, so that the protein forms a compact interface layer, the interaction opportunity among protein molecules is increased, and the grain size is reduced. In addition, soybean meal particles are subjected to huge shearing and impacting actions in the high-pressure homogenizing process, so that the homogenizing time is prolonged, the times of impacting and shearing the soybean meal are continuously increased, and the particle sizes of the soybean meal particles are smaller and smaller. And the disulfide bonds in protein molecules are broken by mechanical shearing force, so that 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 rate of soybean meal is improved; however, the better the heterogeneous pressure is, the longer the heterogeneous time is, the too large pressure or too long homogeneous time can damage the mechanical structure inside the protein, and the water absorption performance is reduced;
2. the catechol functional group is grafted on the PAE, the initial viscosity of the prepared protein adhesive is obviously improved, the pre-pressing forming time is greatly shortened, and the water-resistant bonding strength is improved;
3. the ethylene glycol diglycidyl ether is a protein molecule 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 the ethylene glycol diglycidyl ether, the hydrophobic polyether castor oil is added, so that a cross-linked network structure is more easily formed, 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 present invention, but are not intended to limit the invention in any way. It should be noted that several modifications and improvements can be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
EXAMPLE 1 preparation of a soybean meal Dispersion
The preparation method comprises the following steps:
(1) Pulverizing soybean meal, sieving with 200 meshes, and dispersing the soybean meal powder in water to prepare soybean meal dispersion liquid with the mass concentration of 10%;
(2) Treating the soybean meal dispersion liquid by using a high-pressure shearing homogenizer, 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 obtained in each experimental group were measured.
TABLE 1
Wherein, the control group is a soybean meal dispersion liquid which is not treated.
The water absorption test method is as follows:
step 1, drying samples of each experimental group in table 1 to obtain cured protein samples, and weighing;
step 2, placing the solidified protein sample into a constant temperature and humidity box with the relative humidity of 80% and the temperature of 50 ℃;
and step 3, weighing after 4 hours.
The protein water absorption is calculated according to ase:Sub>A formulase:Sub>A, and the water absorption= (B-A)/A multiplied by 100 percent is obtained
A mass of the sample before water absorption and B mass of the sample after water absorption
The results in Table 1 show that the obtained soybean meal dispersion liquid has good physical and chemical properties after being homogenized for 5-10min under 10-20 Mpa. The reason is that:
1) The untreated soybean meal has the largest particle size, because the soybean meal protein is a macromolecule formed by polypeptide bending and folding, after high-pressure shearing and homogenizing treatment, the soybean meal dispersion liquid is subjected to mechanical stress and centrifugal extrusion, and the macromolecule is sheared into small molecules, so that the protein forms a compact interface layer, the interaction opportunity among protein molecules is increased, and the particle size is reduced. In addition, soybean meal particles are subjected to huge shearing and impacting actions in the high-pressure homogenizing process, so that the homogenizing time is prolonged, the times of impacting and shearing the soybean meal are continuously increased, and the particle sizes of the soybean meal particles are smaller and smaller.
2) The water absorption of the unmodified soybean meal is the lowest, and after high-pressure shearing and homogenizing treatment, the water absorption of the soybean meal is improved, because the disulfide bonds in protein molecules are broken 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 improved.
However, the larger the heterogeneous pressure is, the better the heterogeneous time is, and the too large pressure or too long homogeneous time damages the mechanical structure inside the protein, which in turn reduces the water absorption performance.
Examples2-5
Examples 2-5 relate to a tough soy protein adhesive and a method of preparation.
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, with "-" in Table 1 indicating no addition.
Table 1 (Unit: parts by weight)
Wherein 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 ℃, steaming to remove water in the solution, immediately stopping heating after the water is evaporated to dryness, cooling to below 120 ℃, adding a certain proportion of water to adjust the solid content to 20-30wt%, stirring to be homogeneous, stopping stirring, and preparing the polyamide polyamine intermediate solution
Step 2, preparation of grafted catechol group prepolymer: adding a 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 a modified PAE resin cross-linking agent: and (3) adding water into the grafted catechol group prepolymer, slowly dropwise adding 10kg of epichlorohydrin, heating to 60-65 ℃ after the dropwise adding is finished, preserving heat for 1-2h, and then dropwise adding HCL to adjust the pH value to 3-4, thus obtaining the modified PAE resin cross-linking agent.
2. Preparation method
Step 1, preparing materials according to the formula of the table 1;
step 2, stirring the soybean meal dispersion liquid, the modified PAE resin crosslinking agent polyacrylate and the ethylene glycol diglycidyl ether for 20min by a magnetic stirrer, and uniformly mixing to prepare a mixed solution;
and step 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 was added.
Comparative example 2
This comparative example differs from example 2 in that the modified PAE resin crosslinker is replaced by 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 was replaced with Neopentyl Glycol Diglycidyl Ether (NGDE).
Comparative example 5
This comparative example differs from example 2 in that ethylene glycol diglycidyl ether was replaced with bisphenol a diglycidyl ether.
Application effect test
The glue prepared in examples 2-5 and comparative examples 1-5 were used to prepare three-ply plywood, respectively, by:
drying wood veneer until the water content is 5-7% by weight, uniformly coating the glue prepared in examples 2-5 and comparative examples 1-5 on both sides of the veneer core layer, wherein the glue coating amount is 280g/m 2 And stacking the veneers coated with the glue, putting the laminated veneers into a cold press for cold pressing for 30min, repairing the surfaces of the veneers after cold pressing, putting the veneers into a hot press for hot pressing at 130 ℃ after repairing, wherein the hot pressing time is 1.5min/mm, and obtaining the plywood after hot pressing. Through detection, the plywood can meet the requirements of national standard GB/T9846-2016 type II plywood, and meanwhile, the wet bonding strength is measured by soaking the plywood in water at 80 ℃ for 3 hours, and the result is shown in Table 2.
The foregoing describes specific embodiments of the present invention. It is to be understood that the invention is not limited to the particular embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the claims without affecting the spirit of the invention.
Claims (7)
1. The soybean protein adhesive is characterized by comprising soybean meal dispersion liquid, a modified PAE resin cross-linking agent, ethylene glycol diglycidyl ether and castor oil; the composite material comprises the following components in parts by weight:
the preparation method of the soybean meal dispersion liquid comprises the following steps:
s1, crushing soybean meal into soybean meal powder, and dispersing the soybean meal powder in water to prepare soybean meal dispersion liquid;
s2, carrying out high-pressure shearing homogenization treatment on the soybean meal dispersion liquid;
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, heating to evaporate water in the solution, immediately stopping heating after the water is evaporated to dryness, cooling to below 120 ℃, adding water to adjust the solid content to 20-30wt%, stirring until the materials are homogeneous, and stopping stirring to prepare the polyamide polyamine intermediate solution;
step 2, preparation of grafted catechol group prepolymer: adding a 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 a 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 the dropwise adding, preserving heat for 1-2h, and then dropwise adding HCL to adjust the pH value to 3-4 to obtain the modified PAE resin crosslinking agent.
2. The soybean protein adhesive according to claim 1, wherein the mass concentration of the soybean meal powder in the soybean meal dispersion is 10-20%.
3. The soybean protein adhesive according to claim 1, wherein in step S2, the homogenization treatment is carried out under a condition of 10 to 20Mpa for 5 to 10 minutes.
4. The soy protein adhesive of claim 1 wherein the soybean meal has a particle size of 100-200 mesh.
5. The soybean protein adhesive according to claim 1, wherein step 1 is specifically characterized in that adipic acid and diethylenetriamine are added into a reaction kettle, after raw materials are completely mixed and melted, stirring is uniform, heating is carried out to 150-180 ℃, water in the solution is evaporated, heating is immediately stopped after the water is evaporated to dryness, water with a certain proportion is added to adjust the solid content to 20-30wt% when the temperature is reduced to below 120 ℃, stirring is stopped after the mixture is stirred to be homogeneous, and the polyamide polyamine intermediate solution is prepared.
6. The soybean protein adhesive according to claim 1, wherein step 2 is specifically that a polyamide polyamine intermediate solution and 3, 4-dihydroxybenzaldehyde are added into a reaction kettle to be stirred and reacted to obtain a grafted catechol group prepolymer.
7. Use of the soy protein glue of any of claims 1-6 as a wood glue.
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 |
Applications Claiming Priority (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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114736651A CN114736651A (en) | 2022-07-12 |
| CN114736651B true CN114736651B (en) | 2024-01-05 |
Family
ID=82282512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210396853.6A Active CN114736651B (en) | 2022-04-15 | 2022-04-15 | Tough soybean protein adhesive and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114736651B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| KR102366394B1 (en) * | 2021-01-05 | 2022-02-23 | 조광용 | A hyaluronic acid bead gel having high swelling characteristics |
Family Cites Families (4)
| 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 |
| CN105585996B (en) * | 2009-03-06 | 2019-04-05 | 爱福特立 | Lotion and adhesive and their manufacture and purposes containing albumen |
| WO2011116363A1 (en) * | 2010-03-19 | 2011-09-22 | E2E Materials, Inc. | Biodegradable resin composites |
| EP3884007A4 (en) * | 2018-11-20 | 2022-07-27 | Oregon State University | Ultraviolet radiation-cured pressure sensitive adhesives from plant oils or animal fats |
-
2022
- 2022-04-15 CN CN202210396853.6A patent/CN114736651B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
|---|
| 聚酰胺多胺环氧氯丙烷树脂大豆胶黏剂制备及性能研究;程佳慧等;林产工业;第57卷(第01期);08-11、28 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114736651A (en) | 2022-07-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5490240B2 (en) | Stable acid-modified soybean / urea adhesive and method for producing the same | |
| CA2526420C (en) | Formaldehyde-free lignocellulosic adhesives and composites made from the adhesives | |
| Leiva et al. | Medium‐density particleboards from rice husks and soybean protein concentrate | |
| Lu et al. | Preparation and characterization of wood-plastic plywood bonded with high density polyethylene film | |
| Chen et al. | A sustainable bio-based adhesive derived from defatted soy flour and epichlorohydrin | |
| CN111171314B (en) | Modified PAE resin crosslinking agent, modified adhesive and application | |
| Younesi-Kordkheili et al. | Improving the properties of urea-lignin-glyoxal resin as a wood adhesive by small addition of epoxy | |
| US20040089418A1 (en) | Formaldehyde-free lignocellulosic adhesives and composites made from the adhesives | |
| EP2619277B1 (en) | Soy adhesives and composites made from the adhesives | |
| Li et al. | Effects of typical soybean meal type on the properties of soybean-based adhesive | |
| Luo et al. | A high solid content bioadhesive derived from soybean meal and egg white: Preparation and properties | |
| CN114736651B (en) | Tough soybean protein adhesive and preparation method and application thereof | |
| CN110272715B (en) | High-temperature peanut meal-based formaldehyde-free adhesive and preparation method and application thereof | |
| CN110079269B (en) | Oil-tea-cake adhesive and preparation method and application thereof | |
| WO2010065758A2 (en) | Soy adhesives | |
| CN111849187A (en) | Water-resistant formaldehyde-free high-density fiberboard and preparation process thereof | |
| Wang et al. | Water-resistant whey protein based wood adhesive modified by post-treated phenol-formaldehyde oligomers (PFO). | |
| Sulaiman et al. | Rubberwood particleboard manufactured using epichlorohydrin-modified rice starch as a binder | |
| Fagbemi et al. | Evaluation of waste chicken feather protein hydrolysate as a bio-based binder for particleboard production | |
| Chen et al. | Effects of assembly time on wet shear strength and formaldehyde emission of plywood bonded by urea formaldehyde resin | |
| CN111844338A (en) | Preparation method of mould-proof shaving board | |
| CN107312182B (en) | Thermochemical modified bean flour and preparation method thereof | |
| CN110734741B (en) | Prepressing formaldehyde-free soy protein adhesive and plate forming process thereof | |
| CN114752348A (en) | ultralow-VOC (volatile organic compound) plant protein adhesive for I-type plywood and preparation method thereof | |
| CN113861937A (en) | Phenolic epoxy resin soy protein adhesive, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |