CN116875276B - Low-cost soybean-based adhesive modified by synergistic effect and preparation method thereof - Google Patents
Low-cost soybean-based adhesive modified by synergistic effect and preparation method thereof Download PDFInfo
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- 235000010469 Glycine max Nutrition 0.000 title claims abstract description 173
- 244000068988 Glycine max Species 0.000 title claims abstract description 145
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 136
- 239000000853 adhesive Substances 0.000 title claims abstract description 135
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 238000004132 cross linking Methods 0.000 claims abstract description 76
- 239000000843 powder Substances 0.000 claims abstract description 70
- 239000003607 modifier Substances 0.000 claims abstract description 53
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 238000005303 weighing Methods 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 230000004048 modification Effects 0.000 claims abstract description 16
- 238000012986 modification Methods 0.000 claims abstract description 16
- 239000004952 Polyamide Substances 0.000 claims description 48
- 229920002647 polyamide Polymers 0.000 claims description 48
- 229920003180 amino resin Polymers 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 235000013312 flour Nutrition 0.000 claims description 29
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 19
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 14
- 239000004202 carbamide Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical group O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 13
- 229920000877 Melamine resin Polymers 0.000 claims description 11
- 229940015043 glyoxal Drugs 0.000 claims description 11
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 125000003172 aldehyde group Chemical group 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 25
- 238000002474 experimental method Methods 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 17
- 238000009396 hybridization Methods 0.000 description 16
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 239000011120 plywood Substances 0.000 description 13
- 238000004026 adhesive bonding Methods 0.000 description 12
- 238000009835 boiling Methods 0.000 description 10
- 125000003277 amino group Chemical group 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 229920001807 Urea-formaldehyde Polymers 0.000 description 7
- 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 7
- 239000011256 inorganic filler Substances 0.000 description 6
- 229910003475 inorganic filler Inorganic materials 0.000 description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 5
- 125000002393 azetidinyl group Chemical group 0.000 description 5
- 238000010382 chemical cross-linking Methods 0.000 description 5
- 230000002687 intercalation Effects 0.000 description 5
- 238000009830 intercalation Methods 0.000 description 5
- 239000004455 soybean meal Substances 0.000 description 5
- 238000013007 heat curing Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000004513 sizing Methods 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000007731 hot pressing Methods 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 241000219000 Populus Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- 235000012216 bentonite Nutrition 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000012792 core layer Substances 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000019764 Soybean Meal Nutrition 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000001029 thermal curing 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
- C09J189/04—Products derived from waste materials, e.g. horn, hoof or hair
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a low-cost soybean-based adhesive modified by synergistic effect and a preparation method thereof, and relates to a low-cost soybean-based adhesive and a preparation method thereof. The invention aims to solve the practical problem that the current soybean-based adhesive for industrialization is limited to be widely applied due to higher cost. The soybean-based adhesive is prepared by mixing a co-crosslinking modifier solution and an inorganic ore powder-defatted soybean powder mixture; the preparation method comprises the following steps: 1. preparing a co-crosslinking modifier solution; 2. preparing an inorganic ore powder-defatted soybean powder mixture; 3. weighing and mixing. The invention is a low-cost soybean-based adhesive for synergistic modification and a preparation method thereof.
Description
Technical Field
The invention relates to a low-cost soybean-based adhesive and a preparation method thereof.
Background
The artificial board is an important civil material applied in the fields of furniture, interior decoration and the like, but formaldehyde synthetic resin adhesives are mainly used in the production of the artificial board, so that the problem of formaldehyde release caused by the formaldehyde synthetic resin adhesives is of great concern. The new standard of artificial board and formaldehyde release grading of products thereof is issued and implemented in 2021 in China, and grade classification of E NF (formaldehyde-free) grade artificial board is first formally proposed in the world. The formaldehyde-free adhesive is an effective way for solving formaldehyde release of the artificial board, for example, the soybean-based adhesive prepared by taking oil-pressed soybean meal as a main raw material is not used or added with formaldehyde and formaldehyde derivatives in the production and application process, so that the formaldehyde-free adhesive has the characteristics of no formaldehyde and environment friendliness, and has the advantages of renewable raw materials, low carbon emission in production and application, excellent gluing performance and the like, so that the formaldehyde-free adhesive can be industrially applied to the formaldehyde-free artificial board.
However, the cost of raw materials (such as defatted soybean powder, modified polyamide polyamine-epichlorohydrin resin and the like) for preparing the soybean-based adhesive is higher than that of urea-formaldehyde resin, so that the raw material cost of the soybean-based adhesive is obviously higher than that of the urea-formaldehyde resin adhesive. According to the market price of raw materials in China of 7 months in 2023, the solid cost of polyamide polyamine-epichlorohydrin (PAE) resin is about 18000 yuan/ton, the price of defatted soybean powder is about 6500 yuan/ton, the raw material cost of the prepared soybean-based adhesive is about 2880-2960 yuan/ton, which is 28.0-31.6% higher than that of E 0 -level urea-formaldehyde resin adhesive (about 2250 yuan/ton), and the wide industrial application of the soybean-based adhesive on formaldehyde-free artificial boards is restricted in cost.
In order to reduce the cost of the soybean-based adhesive, people mainly consider that the cost of the soybean-based adhesive is reduced by preparing the low-cost crosslinking modifier, such as a composite aqueous crosslinking agent described in the invention patent CN113322024B, a preparation method and application thereof, and a low-cost incremental resin described in the invention patent CN113214115B, and a preparation method and application thereof. However, the cost accounting for the cross-linking modifier costs about 30% to 40% of the total cost of the soy-based adhesive and the defatted soy flour costs about 60% to 70% of the composition. The cost of the single reduced crosslinking modifier still does not allow the cost of the soy-based adhesive to achieve the desired reduction, which means: on the premise of ensuring the excellent gluing performance of the soybean-based adhesive, the cost of the crosslinking modifier and the defatted soybean powder is required to be reduced sufficiently, so that the cost of the soybean-based adhesive is lower than that of the urea-formaldehyde resin adhesive, and the wide industrial application of the soybean-based adhesive in the formaldehyde-free artificial board industry is promoted effectively, more formaldehyde-free artificial boards are provided for society, and the personal safety and environmental safety problems caused by formaldehyde release of the artificial boards are eliminated.
Disclosure of Invention
The invention aims to solve the practical problem that the current soybean-based adhesive for industrialization is limited in wide application due to high cost, and further provides a low-cost soybean-based adhesive modified by synergistic effect and a preparation method thereof, and meanwhile, the cost is reduced by starting from a crosslinking modifier and defatted soybean flour.
The low-cost soybean-based adhesive with synergistic modification is prepared by mixing 100 parts by weight of a co-crosslinking modifier solution and 35-55 parts by weight of an inorganic ore powder-defatted soybean powder mixture;
The co-crosslinking modifier solution is prepared by mixing 50 parts by mass of polyamide polyamine-epichlorohydrin solution, 35-60 parts by mass of amino resin solution and 255-630 parts by mass of water.
A preparation method of a synergistic modified low-cost soybean-based adhesive is completed according to the following steps:
1. Weighing 50 parts by mass of polyamide polyamine-epichlorohydrin solution, 35-60 parts by mass of amino resin solution and 255-630 parts by mass of water, and uniformly mixing at room temperature to obtain a co-crosslinking modifier solution;
2. Weighing 50 parts of defatted soybean flour and 5-40 parts of inorganic ore powder according to parts by weight, and uniformly mixing at room temperature to obtain an inorganic ore powder-defatted soybean flour mixture;
3. weighing 100 parts of the co-crosslinking modifier solution and 35-55 parts of the inorganic ore powder-defatted soybean powder mixture according to the parts by weight, and mechanically stirring uniformly at room temperature to obtain the low-cost soybean-based adhesive with synergistic modification.
The beneficial effects of the invention are as follows:
1) The amino resin is used as a co-crosslinking modifier obtained by blending a co-crosslinking extender and a polyamide polyamine-epichlorohydrin solution, double high-efficiency crosslinking of defatted soybean powder can be realized during heat curing, meanwhile, organic-inorganic hybridization modification of inorganic ore powder is realized through intercalation, a stable three-dimensional network structure is formed in a system, and finally, good gluing performance of the synergistic modified adhesive is endowed.
2) The soybean-based adhesive is synergistically modified by using the low-cost co-crosslinking modifier and the low-cost inorganic ore powder with the layered silicate structure, so that the adhesive cost can be sufficiently reduced while the bonding strength meets the requirements of class II plywood, and the adhesive dosage is saved, thereby effectively reducing the adhesive cost of the soybean-based adhesive for preparing the formaldehyde-free artificial board. Taking the second example as an example, the cost of the prepared co-crosslinked-montmorillonite hybridized synergistic modified soybean-based adhesive is about 2100 yuan/ton, the cost is reduced by 27.1-29.0%, and the cost is about 150 yuan/ton lower than that of the current E0-level urea-formaldehyde resin adhesive (about 2250 yuan/ton); and the glue-applying amount of the synergetic modified soybean-based adhesive can be reduced from the conventional 400g/m 2 to 320g/m 2, so that the same glue-bonding performance can still meet the requirement of class II water-resistant plywood, the cost of the soybean-based adhesive is reduced, and the glue-applying amount is reduced by 20%.
3) The co-crosslinking modifier obtained by blending the amino resin and the polyamide polyamine-epichlorohydrin solution is easy to dissolve in water, is easy to mix with the defatted soybean powder and the inorganic ore powder to prepare the soybean-based adhesive, does not need to carry out complex modification treatment on the defatted soybean powder and the inorganic ore powder, has the advantages of simple preparation process, low cost, environmental protection and good performance, and can promote wider application of the soybean-based adhesive in the formaldehyde-free artificial board industry.
Drawings
FIG. 1 shows the nuclear magnetic resonance spectrum, A is the amino resin solution prepared in example one, B is the polyamide polyamine-epichlorohydrin solution described in example one, and C is the co-crosslinking modifier solution prepared in example one step one;
FIG. 2 is a curing crosslinking reaction of a co-crosslinking modifier to defatted soy flour;
FIG. 3 is a schematic diagram of inorganic mineral powder inorganic hybridization to a soy-based adhesive;
FIG. 4 is a FTIR spectrum, 1 is a solution of a co-crosslinking modifier prepared in step one of example I, 2 is defatted soy flour, 3 is a co-crosslinking modified soy-based adhesive prepared in comparative experiment II, 4 is a synergistically modified low cost soy-based adhesive prepared in example I, and 5 is montmorillonite;
FIG. 5 is a graph comparing boiling water insolubles content of different modified soy-based adhesives, A is a reference soy-based adhesive prepared in comparative experiment one, B is a co-crosslinked modified soy-based adhesive prepared in comparative experiment three, C is an inorganic filler hybrid enhanced soy-based adhesive prepared in comparative experiment four, and D is a synergistically modified low cost soy-based adhesive prepared in example one.
Detailed Description
The technical scheme of the invention is not limited to the specific embodiments listed below, but also includes any combination of the specific embodiments.
The first embodiment is as follows: the low-cost soybean-based adhesive with synergistic modification is prepared by mixing 100 parts by weight of a co-crosslinking modifier solution and 35-55 parts by weight of an inorganic ore powder-defatted soybean powder mixture;
The co-crosslinking modifier solution is prepared by mixing 50 parts by mass of polyamide polyamine-epichlorohydrin solution, 35-60 parts by mass of amino resin solution and 255-630 parts by mass of water.
The polyamide polyamine-epichlorohydrin solution is used for preparing soybean-based adhesive crosslinking dispersant or commercial solution for papermaking wet strength agent, and is prepared by synthesizing diethylenetriamine, adipic acid and epichlorohydrin.
Because aldehyde groups (glyoxal reaction residues), amide groups (urea reaction residues) and amino groups (melamine reaction residues) contained in the molecules of the amino resin can all react with the amino groups and the azetidinyl groups of the polyamide polyamine-epichlorohydrin resin, the amino resin can generate a co-crosslinking reaction with the polyamide polyamine-epichlorohydrin resin in the hot pressing process to form a double-chemical crosslinking network structure with higher crosslinking density and cohesive strength, and therefore, the excellent gluing performance of the soybean-based crosslinking agent is ensured.
Because the raw material urea price of the amino resin is about 2300 yuan/ton, the melamine price is about 7000 yuan/ton and the 40% glyoxal price is about 6700 yuan/ton, which are obviously lower than the raw material cost (18000-20000 yuan/ton) of the solid matters of the polyamide polyamine-epichlorohydrin resin, the amino resin is used for partially replacing the polyamide polyamine-epichlorohydrin solution to prepare the low-cost co-crosslinking modifier, and the cost of the modified soybean-based adhesive can be effectively reduced on the premise of ensuring the gluing performance.
The inorganic ore powder is low-cost inorganic ore with a layered silicate structure, such as montmorillonite, kaolin, bentonite, talcum and the like. The price of various inorganic ore powders is between 1000 and 1200 yuan/ton, which is obviously lower than the price of defatted soybean powder (about 6500 yuan/ton), so that the inorganic ore powder is used for modifying the soybean-based adhesive, the filling increment is realized by increasing the content of a solid substance, the cost of the modified adhesive is reduced, and the ore powder with the layered silicate structure can also generate intercalation with a cross-linking agent and dissolved and unfolded soybean powder molecules in the preparation process of the soybean-based adhesive in the step three, thereby forming inorganic hybridization enhancement, reducing the cost of the soybean-based adhesive and improving the water resistance of the soybean-based adhesive. To ensure the cost reduction and the reinforcing effect of the soybean-based adhesive.
The beneficial effects of this concrete implementation are:
1) The amino resin is used as a co-crosslinking modifier obtained by blending a co-crosslinking extender and a polyamide polyamine-epichlorohydrin solution, double high-efficiency crosslinking of defatted soybean powder can be realized during heat curing, meanwhile, organic-inorganic hybridization modification of inorganic ore powder is realized through intercalation, a stable three-dimensional network structure is formed in a system, and finally, good gluing performance of the synergistic modified adhesive is endowed.
2) The soybean-based adhesive is synergistically modified by using the low-cost co-crosslinking modifier and the low-cost inorganic ore powder with the layered silicate structure, so that the adhesive cost can be sufficiently reduced while the bonding strength meets the requirements of class II plywood, and the adhesive dosage is saved, thereby effectively reducing the adhesive cost of the soybean-based adhesive for preparing the formaldehyde-free artificial board. Taking the second example as an example, the cost of the prepared co-crosslinked-montmorillonite hybridized synergistic modified soybean-based adhesive is about 2100 yuan/ton, the cost is reduced by 27.1-29.0%, and the cost is about 150 yuan/ton lower than that of the current E0-level urea-formaldehyde resin adhesive (about 2250 yuan/ton); and the glue-applying amount of the synergetic modified soybean-based adhesive can be reduced from the conventional 400g/m 2 to 320g/m 2, so that the same glue-bonding performance can still meet the requirement of class II water-resistant plywood, the cost of the soybean-based adhesive is reduced, and the glue-applying amount is reduced by 20%.
3) The co-crosslinking modifier obtained by blending the amino resin and the polyamide polyamine-epichlorohydrin solution is easy to dissolve in water, is easy to mix with the defatted soybean powder and the inorganic ore powder to prepare the soybean-based adhesive, does not need to carry out complex modification treatment on the defatted soybean powder and the inorganic ore powder, has the advantages of simple preparation process, low cost, environmental protection and good performance, and can promote wider application of the soybean-based adhesive in the formaldehyde-free artificial board industry.
The second embodiment is as follows: the first difference between this embodiment and the specific embodiment is that: the inorganic ore powder-defatted soybean powder mixture is prepared by mixing 50 parts of defatted soybean powder and 5-40 parts of inorganic ore powder according to parts by weight; the defatted soybean flour is obtained after passing through a 120-mesh screen, and the water content is 5% -8%. The other is the same as in the first embodiment.
And a third specific embodiment: this embodiment differs from one or both of the embodiments in that: the inorganic ore powder is one or a mixture of a plurality of montmorillonite, kaolin, bentonite and talcum powder; the inorganic ore powder is obtained after grinding and passing through a screen with the mesh number not less than 1250 meshes. The other is the same as the first or second embodiment.
The specific embodiment IV is as follows: this embodiment differs from one of the first to third embodiments in that: the mass percentage of the solid in the co-crosslinking modifier solution is 5.5-8%, and the amino resin solution accounts for 40-55% of the total mass of the polyamide polyamine-epichlorohydrin solution and the amino resin solution. The other embodiments are the same as those of the first to third embodiments.
Fifth embodiment: this embodiment differs from one to four embodiments in that: the addition amount of the inorganic ore powder in the inorganic ore powder-soybean meal mixture is 9-12% of the mass of the low-cost soybean-based adhesive modified by synergistic effect. The other embodiments are the same as those of the first to fourth embodiments.
Specific embodiment six: this embodiment differs from one of the first to fifth embodiments in that: the amino resin solution is specifically prepared by the following steps:
① Weighing urea, glyoxal and melamine; the molar ratio of the urea to the glyoxal is 1 (1.8-2.0); the molar ratio of urea to melamine is 1:0.03;
② And (3) at room temperature, feeding the weighed urea, glyoxal and melamine at one time, and then reacting for 2 hours at the temperature of 55-85 ℃ to obtain the low-viscosity amino resin solution. The other embodiments are the same as those of the first to fifth embodiments.
Seventh embodiment: this embodiment differs from one of the first to sixth embodiments in that: the mass percentage of solid matters in the low-viscosity amino resin solution in the step ② is 45-50%; the mass percentage of aldehyde groups in the low-viscosity amino resin solution is 1.5% -5.5%; and the pH value of the low-viscosity amino resin solution is 3.5-4.5. The other embodiments are the same as those of the first to sixth embodiments.
Eighth embodiment: this embodiment differs from one of the first to seventh embodiments in that: the mass percentage of solid matters in the polyamide polyamine-epichlorohydrin solution is 12% -20%, and the pH value of the polyamide polyamine-epichlorohydrin solution is 2.5-4.5. The other is the same as in embodiments one to seven.
Detailed description nine: the preparation method of the low-cost soybean-based adhesive with synergistic modification in the embodiment is completed according to the following steps:
1. Weighing 50 parts by mass of polyamide polyamine-epichlorohydrin solution, 35-60 parts by mass of amino resin solution and 255-630 parts by mass of water, and uniformly mixing at room temperature to obtain a co-crosslinking modifier solution;
2. Weighing 50 parts of defatted soybean flour and 5-40 parts of inorganic ore powder according to parts by weight, and uniformly mixing at room temperature to obtain an inorganic ore powder-defatted soybean flour mixture;
3. weighing 100 parts of the co-crosslinking modifier solution and 35-55 parts of the inorganic ore powder-defatted soybean powder mixture according to the parts by weight, and mechanically stirring uniformly at room temperature to obtain the low-cost soybean-based adhesive with synergistic modification.
And thirdly, mechanically stirring at room temperature to ensure that the defatted soybean powder and the inorganic ore powder are uniformly dispersed in the co-crosslinking resin modifier to form a homogeneous colloid without obvious particles, in the process, aldehyde groups and azetidinyl groups in the co-crosslinking resin can realize double crosslinking of amino groups in the defatted soybean powder, and simultaneously, the inorganic ore powder with a layered silicate structure can be subjected to organic-inorganic hybridization to finish co-crosslinking and inorganic hybridization synergistic modification of the soybean-based adhesive, so that a stable and compact three-dimensional network structure is formed among the co-crosslinking modifier, the defatted soybean powder and the inorganic ore powder, and good water resistance is given to the synergistic modified soybean-based adhesive.
Detailed description ten: this embodiment differs from the ninth embodiment in that: and thirdly, mechanically stirring for 10-15 min at room temperature and stirring speed of 80-160 r/min. The other is the same as in the ninth embodiment.
The following examples are used to verify the benefits of the present invention:
embodiment one:
A preparation method of a synergistic modified low-cost soybean-based adhesive is completed according to the following steps:
1. Weighing 50 parts by mass of polyamide polyamine-epichlorohydrin solution, 50 parts by mass of amino resin solution and water, and uniformly mixing at room temperature to obtain a co-crosslinking modifier solution; the mass percentage of the solid in the co-crosslinking modifier solution is 6%;
2. weighing 50 parts of defatted soybean flour and 18.5 parts of inorganic ore powder according to parts by weight, and uniformly mixing at room temperature to obtain an inorganic ore powder-defatted soybean flour mixture;
3. weighing 100 parts of the co-crosslinking modifier solution and 50 parts of the inorganic ore powder-defatted soybean powder mixture according to the parts by weight, and mechanically stirring for 15min at room temperature at a stirring speed of 120r/min to obtain a low-cost soybean-based adhesive with synergistic modification;
The amino resin solution in the first step is specifically prepared by the following steps:
① Weighing urea, glyoxal and melamine; the molar ratio of urea to glyoxal is 1:2.0; the molar ratio of urea to melamine is 1:0.03;
② At room temperature, adding the weighed urea, glyoxal and melamine at one time, and then reacting for 2 hours at the temperature of 80 ℃ to obtain an amino resin solution with low viscosity; the mass percentage of solids in the low-viscosity amino resin solution is 49.5%; the mass percentage of aldehyde groups in the low-viscosity amino resin solution is 3.5% -4.0%; and the pH value of the low-viscosity amino resin solution is 3.5-4.5.
The mass percentage of solids in the polyamide polyamine-epichlorohydrin solution in the step one is 15 percent, and the pH value of the polyamide polyamine-epichlorohydrin solution is 2.5-3.
The defatted soybean flour in the second step is obtained after passing through a 120-mesh screen, and the water content is 5% -8%.
The inorganic ore powder in the second step is montmorillonite; the inorganic ore powder is obtained after grinding and passing through a screen with the mesh number of 1250 meshes;
in the third step, the adding amount of the inorganic ore powder in the inorganic ore powder-soybean meal mixture is 9% of the mass of the low-cost soybean-based adhesive modified by synergistic effect.
Embodiment two: the first difference between this embodiment and the first embodiment is that: weighing 50 parts of defatted soybean flour and 28.1 parts of inorganic ore powder according to parts by weight, and uniformly mixing at room temperature to obtain an inorganic ore powder-defatted soybean flour mixture; the adding amount of the inorganic ore powder in the inorganic ore powder-soybean meal mixture is 12% of the mass of the low-cost soybean-based adhesive modified by synergistic effect. The other is the same as in the first embodiment.
Comparative experiment one:
1. Weighing 50 parts by mass of polyamide polyamine-epichlorohydrin solution and water, and uniformly mixing and stirring at room temperature to obtain polyamide polyamine-epichlorohydrin solution with the solid mass percent of 6%;
2. 100 parts of polyamide polyamine-epichlorohydrin solution with the mass percent of 6% and 50 parts of defatted soybean flour mixture are weighed according to the parts by mass, and mechanically stirred for 15min at room temperature under the condition that the stirring speed is 120r/min, so as to obtain the reference soybean-based adhesive.
The mass percentage of solids in the polyamide polyamine-epichlorohydrin solution in the step one is 15 percent, and the pH value of the polyamide polyamine-epichlorohydrin solution is 2.5-3.
The defatted soybean flour in the second step is obtained after passing through a 120-mesh screen, and the water content is 5% -8%.
Comparison experiment II: the first difference between this example and the comparative experiment is: weighing 50 parts of polyamide polyamine-epichlorohydrin solution, 30 parts of amino resin solution and water according to the parts by weight, and uniformly mixing at room temperature to obtain a co-crosslinking modifier solution; the mass percentage of the solid in the co-crosslinking modifier solution is 6%; and step two, weighing 100 parts of the co-crosslinking modifier solution and 50 parts of defatted soybean flour according to the parts by weight, and finally obtaining the co-crosslinking modified soybean-based adhesive. The others are the same as in the first comparative experiment.
Comparison experiment three: the first difference between this example and the comparative experiment is: weighing 50 parts of polyamide polyamine-epichlorohydrin solution, 50 parts of amino resin solution and water according to the parts by weight, and uniformly mixing at room temperature to obtain a co-crosslinking modifier solution; the mass percentage of the solid in the co-crosslinking modifier solution is 6%; and step two, weighing 100 parts of the co-crosslinking modifier solution and 50 parts of defatted soybean flour according to the parts by weight, and finally obtaining the co-crosslinking modified soybean-based adhesive. The others are the same as in the first comparative experiment.
The preparation method of the amino resin solutions prepared in comparative experiments two and three was the same as in example one.
Comparison experiment four:
1. Weighing 50 parts by mass of polyamide polyamine-epichlorohydrin solution and water, and uniformly mixing and stirring at room temperature to obtain polyamide polyamine-epichlorohydrin solution with the solid mass percent of 6%;
2. weighing 50 parts of defatted soybean flour and 18.5 parts of inorganic ore powder according to parts by weight, and uniformly mixing at room temperature to obtain an inorganic ore powder-defatted soybean flour mixture;
3. Weighing 100 parts by mass of polyamide polyamine-epichlorohydrin solution with the mass percent of 6% and 50 parts by mass of inorganic ore powder-defatted soybean powder mixture, and mechanically stirring for 15min at room temperature at the stirring speed of 120r/min to obtain the inorganic filler hybridization reinforced soybean-based adhesive;
The mass percentage of solids in the polyamide polyamine-epichlorohydrin solution in the step one is 15 percent, and the pH value of the polyamide polyamine-epichlorohydrin solution is 2.5-3.
The defatted soybean flour in the second step is obtained after passing through a 120-mesh screen, and the water content is 5% -8%.
The inorganic ore powder in the second step is montmorillonite; the inorganic ore powder is obtained after grinding and passing through a screen with the mesh number of 1250 meshes.
In the third step, the adding amount of the inorganic ore powder in the inorganic ore powder-soybean meal mixture is 9% of the mass of the low-cost soybean-based adhesive modified by synergistic effect.
The reference soybean-based adhesive prepared in the first comparative experiment is named A1; the co-crosslinking modified soybean-based adhesives prepared in the second and third comparative experiments are named A2 and A3 respectively; the inorganic filler hybridization reinforced soybean-based adhesive prepared in the fourth comparative experiment is named as B1; the synergistically modified low cost soy-based adhesives prepared in examples one and two were designated C1 and C2, respectively.
Coating the prepared soybean-based adhesive on two sides of a poplar single-board core layer with the thickness of 1.7mm according to the double-sided sizing amount of 400g/m 2, forming a board blank in a mode that the wood grain direction is vertical, prepressing for 30min under the condition of single-board pressure of 0.6MPa, and then hot-pressing for 4.5min under the condition of 120 ℃ and single-board pressure of 0.6MPa to obtain the three-layer plywood pressed by the soybean-based adhesive; the dry strength and the bubble strength of the plywood were then tested separately according to the methods specified in the national standard GB/T17657-2015 (test pieces were soaked in water at 63+ -2deg.C for 3h and then in cold water at 25deg.C for 10 min).
TABLE 1 gluing Properties of different Co-crosslinked modified Soybean-based adhesives
TABLE 2 hybridization of inorganic fillers to enhance the adhesive Properties of Soybean-based adhesives
TABLE 3 gluing Properties of different synergistically modified Low cost Soybean-based adhesives
The mass of the co-crosslinking modifier in tables 2 and 3 is the total mass of the polyamide polyamine-epichlorohydrin solution and the amino resin solution.
Placing different modified soybean-based adhesives into an oven at 120+/-2 ℃ for thermal curing for 4 hours, crushing and grinding to obtain particles capable of passing through a 120-mesh screen, and recording spectral peaks of different samples at 4000-500 cm -1 wavelength by using a Fourier infrared spectrometer, wherein the spectral peaks are shown in figure 4; boiling the ground sample in boiling water for 4 hours, weighing insoluble matters through filtering and drying treatment, and calculating the boiling water insoluble matter content of the modified soybean-based adhesive;
FIG. 1 shows the nuclear magnetic resonance spectrum, A is the amino resin solution prepared in example one, B is the polyamide polyamine-epichlorohydrin solution described in example one, and C is the co-crosslinking modifier solution prepared in example one step one;
FIG. 2 is a curing crosslinking reaction of a co-crosslinking modifier to defatted soy flour;
FIG. 3 is a schematic diagram of inorganic mineral powder inorganic hybridization to a soy-based adhesive;
FIG. 4 is a FTIR spectrum, 1 is a solution of a co-crosslinking modifier prepared in step one of example I, 2 is defatted soy flour, 3 is a co-crosslinking modified soy-based adhesive prepared in comparative experiment II, 4 is a synergistically modified low cost soy-based adhesive prepared in example I, and 5 is montmorillonite; in fig. 4, the co-crosslinking modifier solution, defatted soy flour, and montmorillonite were not heat treated.
FIG. 5 is a graph comparing boiling water insolubles content of different modified soy-based adhesives, A is a reference soy-based adhesive prepared in comparative experiment one, B is a co-crosslinked modified soy-based adhesive prepared in comparative experiment three, C is an inorganic filler hybrid enhanced soy-based adhesive prepared in comparative experiment four, and D is a synergistically modified low cost soy-based adhesive prepared in example one.
Experimental results for example one and example two: since the aldehyde group and the amino group contained in the amino resin can react with the amino group and the azetidinyl of the polyamide polyamine-epichlorohydrin resin respectively, the nuclear magnetic hydrogen spectrum of the prepared co-crosslinking modifier weakens at 8.4ppm of aldehyde group signal peak, at 3.6ppm and 3.9ppm of amino group signal peak in the amino resin and at 4.3ppm of azetidinyl signal peak, and the appearance of new hydrogen proton peak at 4.1ppm can be proved (as shown in figure 1), so that the amino resin can generate co-crosslinking reaction with the polyamide polyamine-epichlorohydrin resin in the heat curing process, and a double chemical crosslinking network structure with higher crosslinking density and cohesive strength is formed (as shown in figure 2); the co-crosslinking modifier can realize organic-inorganic hybridization modification on montmorillonite through intercalation, so that absorption peaks of hydroxyl groups represented by montmorillonite at 3620cm -1 and 991cm -1 are disappeared in a spectrogram (figure 4) of the co-crosslinking-montmorillonite inorganic hybridization modified soybean-based adhesive, covalent chemical crosslinking (figure 1) formed in the system is combined with organic-inorganic hybridization (figures 2 and 3) to increase the crosslinking density of the modified soybean-based adhesive, the boiling water insoluble content of the synergistic modified soybean-based adhesive is increased to 68.3%, and the montmorillonite addition is 9-12% of the mass of the soybean-based adhesive, so that the bonding performance of the modified soybean-based adhesive can be ensured.
Comparison experiment one experiment result: when no ore powder exists, the polyamide polyamine-epichlorohydrin resin can be well dissolved and dispersed on defatted soybean powder, and chemical crosslinking is generated in the heat curing process, so that the reference soybean-based adhesive prepared by the polyamide polyamine-epichlorohydrin resin with the concentration of 6 percent has certain boiling water resistance (65.2 percent of boiling water insoluble matter content) and bubble wet bonding strength (0.98 MPa) meeting the class II plywood standard.
Comparing the experimental results of the second experiment and the third experiment: the residual aldehyde groups and azetidinyl groups in the prepared co-crosslinking modifier can be respectively crosslinked with the amino groups in the defatted soy flour, so that the absorption peak intensity of the amino groups represented by the defatted soy flour at 1049cm -1 is reduced (figure 4). Based on the good crosslinking property of the co-crosslinking resin modifier on defatted soybean powder, 50% of expensive polyamide polyamine-epichlorohydrin solution is replaced by amino resin with low cost, the boiling water insoluble content of the prepared co-crosslinking modified soybean-based adhesive is 64.7%, and the blister strength (0.87 MPa) is higher than 24.3% of the water resistance requirement of the national standard on class II plywood.
Comparison of experimental results of experiment four: because the polyamide polyamine-epichlorohydrin solution can have intercalation effect with inorganic montmorillonite with a layered structure (figure 3), and simultaneously has chemical crosslinking reaction with defatted soybean powder, the crosslinking density of the soybean-based adhesive after inorganic hybridization modification is improved, and the boiling water insoluble content of the adhesive is increased to 67.1 percent; and the water bubble strength of the montmorillonite hybridization modified adhesive is optimal (1.09 MPa), which is improved by 11.2 percent compared with that of the water bubble strength (0.98 MPa) of the modified adhesive without adding inorganic filler, and is 55.7 percent higher than the water resistance requirement of the national standard on class II plywood.
Coating the soybean-based adhesive prepared in the second embodiment on two sides of a poplar single-board core layer with the thickness of 1.7mm according to the double-sided sizing amounts of 320, 360 and 400g/m 2 respectively, forming a board blank in a mode of being perpendicular to the wood grain direction, prepressing for 30min under the condition of single-board pressure of 0.6MPa, and hot-pressing for 4.5min under the condition of 120 ℃ and single-board pressure of 0.6MPa to obtain the three-layer plywood pressed by the soybean-based adhesive; the dry strength and the bubble strength of the plywood were then tested separately according to the methods specified in the national standard GB/T17657-2015 (test pieces were soaked in water at 63+ -2deg.C for 3h and then in cold water at 25deg.C for 10 min). The experimental results are shown in Table 4, and after the sizing amount of the co-crosslinked-montmorillonite hybrid synergistic modified soybean-based adhesive is reduced from 400g/m 2 to 320g/m 2, the bubble strength of the adhesive is reduced by 12.2%, but is still higher than 22.8% of the standard requirement value of the class II plywood.
TABLE 4 gluing Properties of synergistically modified Low cost Soybean-based adhesives of different sizing amounts
The mass of the co-crosslinking modifier in Table 4 is the total mass of the polyamide polyamine-epichlorohydrin solution and the amino resin solution.
The cost accounting shows that the price of defatted soybean powder is about 6500 yuan/ton, the cost of polyamide polyamine-epichlorohydrin resin is about 18000-20000 yuan/ton, and the cost of the prepared soybean-based adhesive is about 2880-2960 yuan/ton; the cost of the co-crosslinking-montmorillonite hybridization synergistic modified soybean-based adhesive prepared in the second embodiment is about 2100 yuan/ton, the cost is reduced by 27.1-29.0%, and the cost is lower than that of the current E0-grade urea-formaldehyde resin adhesive (about 2250 yuan/ton) by about 150 yuan/ton; in addition, the glue application amount of the synergistic modified soybean-based adhesive can be reduced from the conventional 400g/m 2 to 320g/m 2, and still the plywood with the gluing performance meeting the II type water resistance can be produced, so that the cost of the soybean-based adhesive is reduced, the glue application amount of the soybean-based adhesive is reduced by 20%, and the production cost of producing the formaldehyde-free artificial board by the synergistic modified soybean-based adhesive is further effectively reduced.
Claims (4)
1. The synergistic modified low-cost soybean-based adhesive is characterized by being prepared by mixing 100 parts by weight of a co-crosslinking modifier solution and 35-55 parts by weight of an inorganic ore powder-defatted soybean powder mixture;
The co-crosslinking modifier solution is prepared by mixing 50 parts by mass of polyamide polyamine-epichlorohydrin solution, 35-60 parts by mass of amino resin solution and water; the mass percentage of the solid in the co-crosslinking modifier solution is 6%;
the amino resin solution is specifically prepared by the following steps:
① Weighing urea, glyoxal and melamine; the molar ratio of urea to glyoxal is 1:2.0; the molar ratio of urea to melamine is 1:0.03;
② At room temperature, adding the weighed urea, glyoxal and melamine at one time, and then reacting for 2 hours at the temperature of 80 ℃ to obtain an amino resin solution with low viscosity; the mass percentage of solids in the low-viscosity amino resin solution is 49.5%; the mass percentage of aldehyde groups in the low-viscosity amino resin solution is 3.5% -4.0%; the pH value of the amino resin solution with low viscosity is 3.5-4.5;
the mass percentage of solid matters in the polyamide polyamine-epichlorohydrin solution is 15%, and the pH value of the polyamide polyamine-epichlorohydrin solution is 2.5-3;
The inorganic ore powder-defatted soybean powder mixture is prepared by mixing 50 parts of defatted soybean powder and 18.5-28.1 parts of inorganic ore powder according to parts by weight; the inorganic ore powder is montmorillonite; the defatted soybean flour is obtained after passing through a 120-mesh screen, and the water content is 5% -8%.
2. The synergistically modified low cost soybean-based adhesive according to claim 1, wherein said inorganic mineral powder is obtained by grinding and passing through a mesh of not less than 1250 mesh.
3. The method for preparing a synergistically modified low cost soy-based adhesive according to claim 1, which is characterized by comprising the steps of:
1. Weighing 50 parts by mass of polyamide polyamine-epichlorohydrin solution, 35-60 parts by mass of amino resin solution and water, and uniformly mixing at room temperature to obtain a co-crosslinking modifier solution; the mass percentage of the solid in the co-crosslinking modifier solution is 6%;
2. Weighing 50 parts of defatted soybean flour and 18.5-28.1 parts of inorganic ore powder according to parts by weight, and uniformly mixing at room temperature to obtain an inorganic ore powder-defatted soybean flour mixture;
3. weighing 100 parts of the co-crosslinking modifier solution and 35-55 parts of the inorganic ore powder-defatted soybean powder mixture according to the parts by weight, and mechanically stirring uniformly at room temperature to obtain the low-cost soybean-based adhesive with synergistic modification.
4. The method for preparing a low-cost soybean-based adhesive with synergistic modification according to claim 3, wherein the third step is performed under the conditions of room temperature and stirring speed of 80-160 r/min for 10-15 min.
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| CN102876284A (en) * | 2012-10-10 | 2013-01-16 | 东北林业大学 | Water resistant soy protein adhesive for wood processing and preparation method thereof |
| CN113322024A (en) * | 2021-06-08 | 2021-08-31 | 东北林业大学 | Composite water-based crosslinking modifier and preparation method and application thereof |
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| CN102876284A (en) * | 2012-10-10 | 2013-01-16 | 东北林业大学 | Water resistant soy protein adhesive for wood processing and preparation method thereof |
| CN113322024A (en) * | 2021-06-08 | 2021-08-31 | 东北林业大学 | Composite water-based crosslinking modifier and preparation method and application thereof |
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