CN111040663B - A kind of bean-based protein adhesive for artificial board and preparation method thereof - Google Patents
A kind of bean-based protein adhesive for artificial board and preparation method thereof Download PDFInfo
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- CN111040663B CN111040663B CN201911381520.0A CN201911381520A CN111040663B CN 111040663 B CN111040663 B CN 111040663B CN 201911381520 A CN201911381520 A CN 201911381520A CN 111040663 B CN111040663 B CN 111040663B
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- based protein
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- linking agent
- protein adhesive
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- 239000000853 adhesive Substances 0.000 title claims abstract description 83
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 83
- 108090000623 proteins and genes Proteins 0.000 title claims abstract description 66
- 102000004169 proteins and genes Human genes 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 244000046052 Phaseolus vulgaris Species 0.000 title description 20
- 235000010627 Phaseolus vulgaris Nutrition 0.000 title description 20
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 71
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 42
- 239000004202 carbamide Substances 0.000 claims description 42
- 239000011259 mixed solution Substances 0.000 claims description 32
- 239000002994 raw material Substances 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 27
- 239000003513 alkali Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- QAIPRVGONGVQAS-DUXPYHPUSA-N trans-caffeic acid Chemical compound OC(=O)\C=C\C1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-DUXPYHPUSA-N 0.000 claims description 11
- 239000007800 oxidant agent Substances 0.000 claims description 10
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 claims description 10
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 9
- 239000000920 calcium hydroxide Substances 0.000 claims description 9
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 9
- YQUVCSBJEUQKSH-UHFFFAOYSA-N 3,4-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- IBGBGRVKPALMCQ-UHFFFAOYSA-N 3,4-dihydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1O IBGBGRVKPALMCQ-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 6
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- ACEAELOMUCBPJP-UHFFFAOYSA-N (E)-3,4,5-trihydroxycinnamic acid Natural products OC(=O)C=CC1=CC(O)=C(O)C(O)=C1 ACEAELOMUCBPJP-UHFFFAOYSA-N 0.000 claims description 4
- 229940074360 caffeic acid Drugs 0.000 claims description 4
- 235000004883 caffeic acid Nutrition 0.000 claims description 4
- QAIPRVGONGVQAS-UHFFFAOYSA-N cis-caffeic acid Natural products OC(=O)C=CC1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-UHFFFAOYSA-N 0.000 claims description 4
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 4
- 238000010907 mechanical stirring Methods 0.000 claims description 4
- PCYGLFXKCBFGPC-UHFFFAOYSA-N 3,4-Dihydroxy hydroxymethyl benzene Natural products OCC1=CC=C(O)C(O)=C1 PCYGLFXKCBFGPC-UHFFFAOYSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 229960003638 dopamine Drugs 0.000 claims description 2
- 239000004971 Cross linker Substances 0.000 claims 5
- 239000002245 particle Substances 0.000 claims 1
- 235000018553 tannin Nutrition 0.000 claims 1
- 229920001864 tannin Polymers 0.000 claims 1
- 239000001648 tannin Substances 0.000 claims 1
- 239000002023 wood Substances 0.000 abstract description 5
- 238000011161 development Methods 0.000 abstract description 4
- 239000002028 Biomass Substances 0.000 abstract description 2
- 239000004826 Synthetic adhesive Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000010908 plant waste Substances 0.000 abstract description 2
- 235000018102 proteins Nutrition 0.000 description 41
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 27
- 235000010469 Glycine max Nutrition 0.000 description 27
- 244000068988 Glycine max Species 0.000 description 12
- 239000011120 plywood Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 108010073771 Soybean Proteins Proteins 0.000 description 4
- 229920001807 Urea-formaldehyde Polymers 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 235000019710 soybean protein Nutrition 0.000 description 4
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 3
- 239000001263 FEMA 3042 Substances 0.000 description 3
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 3
- -1 amino, carboxyl Chemical group 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- LRBQNJMCXXYXIU-QWKBTXIPSA-N gallotannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@H]2[C@@H]([C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-QWKBTXIPSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229940033123 tannic acid Drugs 0.000 description 3
- 235000015523 tannic acid Nutrition 0.000 description 3
- 229920002258 tannic acid Polymers 0.000 description 3
- 241000237536 Mytilus edulis Species 0.000 description 2
- 235000019764 Soybean Meal Nutrition 0.000 description 2
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000020638 mussel Nutrition 0.000 description 2
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000004455 soybean meal Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- PFTAWBLQPZVEMU-DZGCQCFKSA-N (+)-catechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-DZGCQCFKSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 108010064851 Plant Proteins Proteins 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- QKIRHLCRDJURQV-UHFFFAOYSA-K calcium;sodium;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Na+].[Ca+2] QKIRHLCRDJURQV-UHFFFAOYSA-K 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229950001002 cianidanol Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007728 cost analysis Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011094 fiberboard Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000004630 mental health Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 235000021118 plant-derived protein Nutrition 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000012855 volatile organic compound Substances 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
- 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
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
本发明涉及一种人造板用的豆基蛋白胶黏剂用交联剂及其制备方法、人造板用的豆基蛋白胶黏剂及其制备方法，本发明主要原料豆粕是粮食作物加工剩余物，是一种可再生的资源，可以同时解决粮食作物废料的资源化问题和生物质胶黏剂的成本较高问题，解决合成胶黏剂对化石资源的过度依赖问题，符合环境保护与可持续发展要求，具有重要的经济与社会效益。The invention relates to a cross-linking agent for a soy-based protein adhesive for wood-based panels and a preparation method thereof, a soy-based protein adhesive for wood-based panels and a preparation method thereof. , is a renewable resource that can simultaneously solve the problem of resource utilization of food crop waste and the high cost of biomass adhesives, and solve the problem of excessive dependence of synthetic adhesives on fossil resources, which is in line with environmental protection and sustainable Development requirements, with important economic and social benefits.
Description
Technical Field
The invention relates to an adhesive and a preparation method thereof, in particular to a bean-based protein adhesive for an artificial board and a preparation method thereof.
Background
Most of adhesives for the artificial board industry in China are synthetic resin adhesives releasing formaldehyde, and the problems of formaldehyde, volatile organic compounds and the like generated in the production and use processes of wooden products can seriously harm the physical and mental health of industrial workers and consumers. In order to solve the problems and the hazards of the existing adhesive for the artificial board industry, the development of the green and environment-friendly aldehyde-free adhesive has important significance.
The soybean is the most abundant plant protein source in the world, the soybean has high protein content, and the soybean protein molecules have a large amount of polar groups such as amino, carboxyl, hydroxyl, sulfydryl and the like, and can form strong hydrogen bonds, van der waals force, hydrophobic effect and a small amount of covalent bonds with wood components in the artificial board, so the artificial board is a very good aldehyde-free adhesive raw material. However, the bean-based adhesive has the problems of low bonding strength and poor water resistance, so that the popularization and the application of the bean-based adhesive are greatly limited, and people adopt various methods to modify the bean-based adhesive. Researches prove that cross-linking agents with the functionality of more than or equal to 2, such as glyoxal, glutaraldehyde, dicyandiamide, maleic anhydride, polyisocyanate and the like, can react with soybean protein residues, and the bonding strength and the water resistance of the bean-based adhesive are improved through the increase of the cross-linking density. However, the crosslinking agents of the several types generally have the problems of high toxicity, environmental pollution and the like, and the development of environment-friendly and low-toxicity green crosslinking agents is significant. Inspired by nature, the marine mussel byssus protein has excellent waterproof adhesive bonding performance. After the catechol structure in the mussel byssus protein is oxidized and polymerized, the catechol structure can form physical and chemical combination with amino, sulfydryl, hydroxyl, carboxyl and the like on a soybean molecular chain, so that the crosslinking density is improved, and the water-resistant bonding strength is greatly improved.
The invention provides a crosslinking agent for a bean-based protein adhesive for an artificial board and a preparation method thereof, and the bean-based protein adhesive for the artificial board and the preparation method thereof.
Disclosure of Invention
The invention aims to provide a crosslinking agent for a soy-based protein adhesive and a preparation method thereof, wherein the crosslinking agent is green, environment-friendly, healthy and low in toxicity, and has an excellent crosslinking effect; the invention also aims to provide the bean-based protein adhesive and the preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a crosslinking agent for a soy-based protein adhesive, which comprises the following raw materials in parts by weight:
a crosslinking agent component A5-20
10-15 of cross-linking agent component B
1 to 5 parts of an oxidizing agent
The raw material proportion is preferably as follows:
10-15 parts of cross-linking agent component A
10-13 parts of a cross-linking agent component B
2-4 of an oxidant
Wherein the cross-linking agent component A is polycarbodiimide.
Wherein the cross-linking agent component B is one or a mixture of more of dopamine, caffeic acid, hydrogenated caffeic acid, tannic acid, protocatechuic acid, plateau catechuic acid and 3, 4-dihydroxy benzaldehyde.
Wherein, the oxidant is one or a mixture of more of ferric chloride, sodium periodate and hydrogen peroxide.
Further, the polycarbodiimide has a solid content of 30 to 50 wt%, a viscosity (at 25 ℃) of 60 to 250mPa · s, and an active period of 60 to 120 days.
The invention further provides a preparation method of the crosslinking agent for the soy-based protein adhesive, which comprises the following steps:
weighing the cross-linking agent component A, the cross-linking agent component B and the oxidant according to the weight parts of the raw materials.
And (3) placing the raw materials into a reaction kettle, stirring, and uniformly mixing to obtain the crosslinking agent for the soybean-based protein adhesive.
Preferably, the stirring condition is mechanical stirring, and the rotating speed is 600-1000 r/min.
Preferably, the stirring temperature is 75-85 ℃ and the stirring time is 0.5-1 hour.
The invention further provides a soy-based protein adhesive, which comprises the following raw materials in parts by weight:
the raw material proportion is preferably as follows:
wherein the soybean protein-based raw material is defatted soybean meal with the granularity of 50-400 meshes.
Wherein the alkali is one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide and barium hydroxide.
Wherein the cross-linking agent is prepared by the preparation method of the cross-linking agent for the soybean-based protein adhesive.
Further, the solid content of the soy-based protein adhesive is 30-50 wt%, the viscosity (at 25 ℃) is 200-2000 mPa & s, and the active period is 15-30 days.
The invention further provides a preparation method of the soy-based protein adhesive, which comprises the following steps:
weighing the bean-based protein raw material, alkali, urea, a cross-linking agent and water according to the weight parts of the raw materials.
Dispersing alkali and urea in water, and uniformly stirring to obtain a mixed solution of the alkali and the urea.
Adding the cross-linking agent into the mixed solution under the condition of stirring to obtain the mixed solution of the alkali and the urea in which the cross-linking agent is dispersed.
And adding the mixed solution of the alkali containing the cross-linking agent and the urea into the solid of the soybean-based protein raw material under the condition of stirring, refluxing, reacting, and cooling to obtain the soybean-based protein adhesive.
Preferably, the stirring condition is mechanical stirring, and the rotating speed is 600-1800 rpm.
Preferably, the temperature of the stirring reflux reaction is 50-100 ℃, and the time is 1-3 hours.
The soy-based protein adhesive of the invention is subjected to cost analysis as follows:
at present, the price of the urea-formaldehyde adhesive with low free formaldehyde content is about 2400 yuan/ton, the price of the soy-based protein adhesive prepared by the optimization scheme of the invention is about 1800-3000 yuan/ton, the existing equipment (equivalent to urea-formaldehyde resin) does not need to be modified, and the use cost is equivalent to that of the urea-formaldehyde adhesive with low free formaldehyde content.
The invention has the following beneficial effects:
the cross-linking agent for the soy-based protein adhesive is environment-friendly, low in toxicity and harmless to human bodies and the environment; the soybean-based protein adhesive is free from formaldehyde release, and the manufactured artificial board is free from formaldehyde release, so that the problem of formaldehyde release of the artificial board is thoroughly solved; the adhesive has high bonding strength and excellent water resistance, can meet the requirements of II-type plywood, does not crack after being boiled in water at 100 ℃, and can be used for producing artificial boards such as plywood, shaving board, medium-density fiberboard, laminated wood board and the like; in the invention, the raw materials in the cross-linking agent are set as follows in parts by weight: 5-20 parts of a cross-linking agent component A, 10-15 parts of a cross-linking agent component B and 1-5 parts of an oxidizing agent, preferably 10-15 parts of the cross-linking agent component A, 10-13 parts of the cross-linking agent component B and 2-4 parts of the oxidizing agent, and the adhesive strength and the water resistance of the adhesive can be remarkably improved.
The main raw material soybean meal of the invention is grain crop processing residues, is a renewable resource, can simultaneously solve the problems of recycling of grain crop wastes and higher cost of the biomass adhesive, solves the problem of excessive dependence of the synthetic adhesive on fossil resources, meets the requirements of environmental protection and sustainable development, and has important economic and social benefits.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
1. Preparing materials (Kg) according to the following weight ratio:
1. 10Kg of polycarbodiimide, 12Kg of tannic acid and 2Kg of ferric chloride are put in a reaction kettle and stirred uniformly at 800 rpm to obtain the crosslinking agent for the soy-based protein adhesive.
2. 5Kg of sodium hydroxide and 10Kg of urea are dispersed in water and stirred uniformly at a rotation speed of 900 rpm to obtain a mixed solution of sodium hydroxide and urea.
3. And (3) dispersing the cross-linking agent prepared in the step one into the mixed solution of the sodium hydroxide and the urea, and uniformly stirring at 1000 revolutions per minute to obtain the mixed solution of the sodium hydroxide and the urea in which the cross-linking agent is dispersed.
4. Adding the mixed solution of the alkali containing the cross-linking agent and the urea into 25Kg of soybean-based protein raw material at the rotating speed of 1000 r/min, and copolymerizing at 60 ℃ to obtain the soybean-based protein adhesive.
The performance indexes of the adhesive prepared by the method are shown in table 1.
Table 1 performance index of adhesive of example 1 of the present invention
Example 2
1. Preparing materials (Kg) according to the following weight ratio:
1. 12Kg of polycarbodiimide, 12Kg of caffeic acid and 2Kg of sodium periodate are put into a reaction kettle and stirred uniformly at 1000 rpm to obtain the cross-linking agent for the soy-based protein adhesive.
2. 10Kg of potassium hydroxide and 15Kg of urea are dispersed in water and stirred uniformly at the rotation speed of 1100 rpm to obtain a mixed solution of potassium hydroxide and urea.
3. And (3) dispersing the cross-linking agent prepared in the step one into the mixed solution of the potassium hydroxide and the urea, and uniformly stirring at 1000 revolutions per minute to obtain the mixed solution of the potassium hydroxide and the urea in which the cross-linking agent is dispersed.
4. Adding the mixed solution of the alkali containing the cross-linking agent and the urea into 20Kg of bean-based protein raw material at the rotation speed of 1200 r/min, and copolymerizing at 70 ℃ to obtain the bean-based protein adhesive.
The performance index of the adhesive prepared by the method is shown in table 2.
Table 2 performance index of adhesive of example 2 of the present invention
Example 3
1. Preparing materials (Kg) according to the following weight ratio:
1. 10Kg of polycarbodiimide, 10Kg of protocatechuic acid and 3Kg of hydrogen peroxide are put in a reaction kettle and stirred uniformly at 1100 r/min to obtain the cross-linking agent for the soy-based protein adhesive.
2. Dispersing 8Kg of calcium hydroxide and 15Kg of urea in water, and stirring uniformly at the rotation speed of 1000 rpm to obtain a mixed solution of calcium hydroxide and urea.
3. And (3) dispersing the cross-linking agent prepared in the step one into the mixed solution of the calcium hydroxide and the urea, and uniformly stirring at 900 revolutions per minute to obtain the mixed solution of the calcium hydroxide and the urea in which the cross-linking agent is dispersed.
4. Adding the mixed solution of the alkali containing the cross-linking agent and the urea into 20Kg of bean-based protein raw material at the rotating speed of 1000 r/min, and copolymerizing at 90 ℃ to obtain the bean-based protein adhesive.
The performance indexes of the adhesive prepared by the method are shown in table 3.
Table 3 performance index of adhesive of example 3 of the present invention
Example 4
1. Preparing materials (Kg) according to the following weight ratio:
1. and putting 13Kg of polycarbodiimide, 11Kg of hydrogenated caffeic acid and 4Kg of hydrogen peroxide into a reaction kettle, and uniformly stirring at 600 revolutions per minute to obtain the crosslinking agent for the soy-based protein adhesive.
2. Dispersing 9Kg of barium hydroxide and 20Kg of urea in water, and stirring uniformly at the rotation speed of 1000 rpm to obtain a mixed solution of barium hydroxide and urea.
3. And (3) dispersing the cross-linking agent prepared in the step one into the mixed solution of the barium hydroxide and the urea, and uniformly stirring at 900 revolutions per minute to obtain the mixed solution of the barium hydroxide and the urea in which the cross-linking agent is dispersed.
4. Adding the mixed solution of the alkali containing the cross-linking agent and the urea into 35Kg of bean-based protein raw material at the rotation speed of 1200 r/min, and copolymerizing at 60 ℃ to obtain the bean-based protein adhesive.
The performance index of the adhesive prepared is shown in table 4.
Table 4 performance index of adhesive of example 4 of the present invention
Example 5
1. Preparing materials (Kg) according to the following weight ratio:
1. and (3) putting 14Kg of polycarbodiimide, 12Kg of 3, 4-dihydroxybenzaldehyde and 3Kg of sodium periodate into a reaction kettle, and uniformly stirring at 1000 revolutions per minute to obtain the crosslinking agent for the soybean-based protein adhesive.
2. 6Kg of sodium hydroxide and 10Kg of urea are dispersed in water and stirred uniformly at a rotation speed of 1500 rpm to obtain a mixed solution of sodium hydroxide and urea.
3. And (3) dispersing the cross-linking agent prepared in the step one into the mixed solution of the sodium hydroxide and the urea, and uniformly stirring at 1500 revolutions per minute to obtain the mixed solution of the sodium hydroxide and the urea in which the cross-linking agent is dispersed.
4. Adding the mixed solution of the alkali containing the cross-linking agent and the urea into 30Kg of bean-based protein raw material at the rotating speed of 1500 rpm, and copolymerizing at 100 ℃ to obtain the bean-based protein adhesive.
The performance index of the adhesive prepared is shown in table 5.
Table 5 performance index of adhesive of example 5 of the present invention
Example 6
1. Preparing materials (Kg) according to the following weight ratio:
1. 12Kg of polycarbodiimide, 5Kg of tannic acid, 5Kg of caffeic acid and 3Kg of sodium periodate are put into a reaction kettle and stirred uniformly at 750 revolutions per minute to obtain the cross-linking agent for the soy-based protein adhesive.
2. Dispersing 7Kg of calcium hydroxide and 10Kg of urea in water, and stirring uniformly at a rotation speed of 1600 rpm to obtain a mixed solution of calcium hydroxide and urea.
3. And (3) dispersing the cross-linking agent prepared in the step one into the mixed solution of the calcium hydroxide and the urea, and uniformly stirring at 1600 revolutions per minute to obtain the mixed solution of the calcium hydroxide sodium and the urea in which the cross-linking agent is dispersed.
4. Adding the mixed solution of the alkali containing the cross-linking agent and the urea into 25Kg of bean-based protein raw material at the rotating speed of 1600 revolutions per minute, and copolymerizing at 90 ℃ to obtain the bean-based protein adhesive.
The performance index of the adhesive prepared is shown in table 6.
Table 6 performance index of adhesive of example 6 of the present invention
Examples of the experiments
Comparative example 1: the urea-formaldehyde resin adhesive conventionally used in the manufacture of artificial boards is adopted.
Comparative example 2: the melamine resin adhesive conventionally used in the manufacture of artificial boards is adopted.
The three-layer plywood is manufactured by respectively using the soy-based protein adhesives prepared in the embodiments 1-6 and the adhesives prepared in the comparative examples 1-2, and the following preparation process parameters are adopted:
veneer: poplar with water content of 8-12% and thickness of 1.6 mm;
sizing: the core plate is coated with glue with the glue coating amount of 270-2(double-sided);
aging time: 30-90 min;
hot pressing: the hot pressing temperature is 120 ℃; the hot pressing pressure is 1.0-1.3 Mpa; the hot pressing time is 10min (100s/min)
The three-layer plywood manufactured by the process is detected to release formaldehyde and bond strength (class II) according to GB/T17657-1999 test method for physical and chemical properties of artificial boards and facing artificial boards, and the results are shown in Table 7.
Table 7: main performance test results of plywood prepared in examples 1 to 6 and comparative examples 1 to 2
| Detecting items | Bonding strength/MPa | Formaldehyde emission amount/mg/L |
| Example 1 | 1.33 | Not detected out |
| Example 2 | 1.32 | Not detected out |
| Example 3 | 1.45 | Not detected out |
| Example 4 | 1.42 | Not detected out |
| Example 5 | 1.43 | Not detected out |
| Example 6 | 1.28 | Not detected out |
| Comparative example 1 | 1.37 | 5.9 |
| Comparative example 2 | 1.15 | Not detected out |
Note 1: type ii plywood standard: e0 standard is less than or equal to 0.5 mg/L; e1 standard is 0.5-1.5 mg/L; e2 standard is 1.5-5.0 mg/L.
Note 2: formaldehyde emissions from the wood itself, as follows.
The detection result shows that no formaldehyde is released in the plywood prepared by the soybean protein-based adhesive, and the manufactured plywood has high water resistance and meets the requirements of II-type plywood; as can be seen from the above table in particular, the plywood was optimized in terms of the bonding strength under the condition of the composition combinations of the examples.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (9)
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