CN116925684A - Vegetable protein-based adhesive and preparation method and application thereof - Google Patents
Vegetable protein-based adhesive and preparation method and application thereof Download PDFInfo
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- CN116925684A CN116925684A CN202310670151.7A CN202310670151A CN116925684A CN 116925684 A CN116925684 A CN 116925684A CN 202310670151 A CN202310670151 A CN 202310670151A CN 116925684 A CN116925684 A CN 116925684A
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- 239000000853 adhesive Substances 0.000 title claims abstract description 84
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 84
- 108010082495 Dietary Plant Proteins Proteins 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 108010064851 Plant Proteins Proteins 0.000 claims abstract description 52
- 235000021118 plant-derived protein Nutrition 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 239000002253 acid Substances 0.000 claims abstract description 31
- -1 primary amine compounds Chemical class 0.000 claims abstract description 30
- FXWFZIRWWNPPOV-UHFFFAOYSA-N 2-aminobenzaldehyde Chemical compound NC1=CC=CC=C1C=O FXWFZIRWWNPPOV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- 239000012711 adhesive precursor Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 238000010992 reflux Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 15
- 230000015556 catabolic process Effects 0.000 claims description 12
- 238000006731 degradation reaction Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004327 boric acid Substances 0.000 claims description 8
- 235000018102 proteins Nutrition 0.000 claims description 8
- 108090000623 proteins and genes Proteins 0.000 claims description 8
- 102000004169 proteins and genes Human genes 0.000 claims description 8
- 108010073771 Soybean Proteins Proteins 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000008139 complexing agent Substances 0.000 claims description 6
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 5
- 229960001124 trientine Drugs 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- 235000019764 Soybean Meal Nutrition 0.000 claims description 3
- 244000269722 Thea sinensis Species 0.000 claims description 3
- 229940001941 soy protein Drugs 0.000 claims description 3
- 239000004455 soybean meal Substances 0.000 claims description 3
- 235000012424 soybean oil Nutrition 0.000 claims 1
- 239000003549 soybean oil Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 49
- 239000011347 resin Substances 0.000 abstract description 49
- 239000003063 flame retardant Substances 0.000 abstract description 25
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 23
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 20
- 238000007731 hot pressing Methods 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 241000219927 Eucalyptus Species 0.000 description 10
- 239000011120 plywood Substances 0.000 description 10
- 239000000178 monomer Substances 0.000 description 9
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 8
- 239000005011 phenolic resin Substances 0.000 description 8
- 229920001568 phenolic resin Polymers 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 6
- 230000009471 action Effects 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 235000013824 polyphenols Nutrition 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000002023 wood Substances 0.000 description 6
- 235000010469 Glycine max Nutrition 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 4
- 235000017491 Bambusa tulda Nutrition 0.000 description 4
- 241001330002 Bambuseae Species 0.000 description 4
- 239000002841 Lewis acid Substances 0.000 description 4
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 4
- 241000219000 Populus Species 0.000 description 4
- 125000003172 aldehyde group Chemical group 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 239000011425 bamboo Substances 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 150000007517 lewis acids Chemical class 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 4
- 238000007142 ring opening reaction Methods 0.000 description 4
- 238000004513 sizing Methods 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- 235000019710 soybean protein Nutrition 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004026 adhesive bonding Methods 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 125000005605 benzo group Chemical group 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 235000013312 flour Nutrition 0.000 description 3
- 150000002391 heterocyclic compounds Chemical class 0.000 description 3
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 244000068988 Glycine max Species 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000011951 cationic catalyst Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001953 sensory effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 1
- 235000011609 Pinus massoniana Nutrition 0.000 description 1
- 241000018650 Pinus massoniana Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 235000006694 eating habits Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000004078 waterproofing 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
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C09J161/32—Modified amine-aldehyde condensates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27D—WORKING VENEER OR PLYWOOD
- B27D1/00—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring
- B27D1/04—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring to produce plywood or articles made therefrom; Plywood sheets
- B27D1/08—Manufacture of shaped articles; Presses specially designed therefor
-
- 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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/06—Amines
-
- 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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/40—Chemically modified polycondensates
Abstract
The invention provides a vegetable protein-based adhesive, and a preparation method and application thereof. The plant protein-based adhesive comprises plant proteins, o-aminobenzaldehyde, 4, 5-trihydroxybenzaldehyde, acid and primary amine compounds. The plant protein-based adhesive disclosed by the invention is modified by using the polybenzoxazine resin generated by the reaction of raw materials, so that the mechanical strength and the water resistance of the plant protein-based adhesive are synchronously enhanced, and the plant protein-based adhesive has remarkable flame retardant property. The invention also provides a preparation method and application of the vegetable protein-based adhesive.
Description
Technical Field
The invention belongs to the technical field of bamboo wood artificial boards, and particularly relates to a vegetable protein-based adhesive, a preparation method and application thereof.
Background
In the manufactured board product, an adhesive is a necessary auxiliary material. As early as the early twentieth century, people used soybean flour as a base material to make wood adhesives for plywood, which have been gradually replaced by developed "trialdehyde glue" due to the defects of soybean glue itself.
In the related art, although the adhesive for the artificial board is mainly made of 'trialdehyde glue', the 'trialdehyde glue' mainly uses formaldehyde, urea, melamine, phenol and the like as raw materials, and toxic and harmful substances such as formaldehyde, phenol and the like can be released in the production, transportation and use processes and the application processes of related products. Because of the shortage of petroleum resources and the gradual enhancement of environmental awareness of people, the search for novel natural environment-friendly adhesives to replace the trialdehyde glue becomes a necessary trend, so that the adhesives prepared by taking plant proteins as raw materials become research hotspots of people.
At present, the plant protein-based adhesive needs to be additionally added with flame retardant to have obvious flame retardant property. On one hand, the cost is high; on the other hand, some flame retardants are toxic and have potential threat to human health, so that the application range of the products is limited. Therefore, there remains a need to develop an adhesive that is free of flame retardants.
Disclosure of Invention
The present invention aims to solve at least one of the above technical problems in the prior art. To this end, the present invention provides a vegetable protein-based adhesive.
The invention also provides a method for preparing the vegetable protein-based adhesive.
The invention also provides application of the vegetable protein-based adhesive.
In a first aspect, the present invention provides a vegetable protein-based adhesive, the preparation raw materials comprising vegetable protein, o-aminobenzaldehyde, 4, 5-trihydroxybenzaldehyde, acid and primary amine compound.
The invention relates to one of the technical schemes of vegetable protein-based adhesives, which has at least the following beneficial effects:
the plant protein-based adhesive provided by the invention is characterized in that a benzoxazine monomer of a benzo six-membered heterocyclic compound is synthesized by taking primary amine compounds and aldehydes as raw materials, and the benzoxazine monomer can undergo a ring-opening polymerization reaction under the action of heating and/or a catalyst to form the polybenzoxazine resin. Compared with common phenolic resin, the polybenzoxazine resin has no small molecule release in the molding and curing process, low product porosity, near zero shrinkage and low water and moisture absorption rate. In addition, the polybenzoxazine resin has greater flexibility in molecular design, and is a novel phenolic resin. The plant protein-based adhesive is prepared by modifying the plant protein adhesive by using the polybenzoxazine resin, so that the mechanical strength and the water resistance of the plant protein-based adhesive are synchronously enhanced, and the plant protein-based adhesive has remarkable flame retardant property.
The benzoxazine resin is a generic name containing N and O six-membered oxazine ring compounds, the benzoxazine has higher heat resistance, the glass transition temperature is above 150 ℃, the shrinkage rate after curing is almost zero, the B1 level is flame-retardant, and the water absorption and the moisture absorption are low.
The curing mode of the benzoxazine resin comprises the following steps:
and (3) thermally self-curing: the benzoxazine monomer is subjected to ring opening under the heating condition to form phenolic hydroxyl groups, and a structure similar to a polyphenol aldehyde is formed in a catalysis mode, so that a three-dimensional crosslinked network structure is formed.
Thermocatalytic curing: the benzoxazine ring-opening curing is catalyzed by the addition of a cationic catalyst, such as a lewis acid, imidazole, iodonium salt, sulfonium salt, and the like, which generates active cations in a heated environment.
The preparation raw materials of the vegetable protein-based adhesive comprise:
the plant protein has the function of utilizing amino, mercapto, hydroxyl and the like on protein molecules to participate in the curing reaction of the benzoxazine resin, and is connected with the resin through covalent bonds to form a three-dimensional network structure, and meanwhile, the cost of the resin can be reduced, and the resin has degradability.
The function of the o-aminobenzaldehyde is to provide amino and aldehyde groups in the reaction process, so that the reaction can be normally carried out.
The 4, 5-trihydroxybenzaldehyde serves as a multifunctional chemical substance, and simultaneously provides aldehyde groups and phenolic hydroxyl groups in the reaction process.
The roles of the acids include:
(1) As a catalyst, providing an acidic environment for the curing reaction of the resin;
(2) Part of the resin is involved in the curing of the resin so that the resin also has acid functionality (acid selective phosphoric acid, boric acid).
Specifically, the addition of boric acid or phosphoric acid, the actions including:
(1) As Lewis acid to participate in and catalyze the curing reaction of the resin smoothly;
(2) The flame retardant property is realized by the P and B elements contained in the flame retardant material. As the curing component of the resin, the acidic substance can be fully and uniformly dispersed in the resin and the artificial board, and the flame retardant effect is remarkable.
The primary amine compound functions to provide an amino group for the curing reaction of the resin.
According to some embodiments of the invention, the preparation raw materials comprise, by weight:
vegetable protein: 10 to 20 parts of the components in parts by weight,
o-aminobenzaldehyde: 0.5 to 6 parts of the components,
4, 5-trihydroxybenzaldehyde: 1 to 8 parts of a mixture of components,
acid: 0.5 to 3 parts of the components,
primary amine compound: 0.5 to 4 parts.
According to some embodiments of the invention, the vegetable protein source includes soy protein, soybean meal, defatted soy flour, and other oil processing residue cake proteins, such as oil tea cake proteins.
According to some embodiments of the invention, the source of vegetable proteins further includes isolated proteins of various post-processing residues of oils.
According to some embodiments of the invention, the acid comprises boric acid or phosphoric acid.
According to some embodiments of the invention, the primary amine compound comprises at least one of triethylene tetramine and diethylene triamine.
In a second aspect, the present invention provides a method for preparing the vegetable protein-based adhesive, comprising the steps of:
s1: blending the vegetable protein with water, and carrying out heating degradation under an alkaline condition to obtain a vegetable protein adhesive precursor;
s2: mixing the o-aminobenzaldehyde, 4, 5-trihydroxybenzaldehyde, acid and a complexing agent, reacting under a reflux condition, adding the plant protein adhesive precursor, stirring uniformly, and continuing to heat for reaction.
The invention relates to a technical scheme in a preparation method of a vegetable protein-based adhesive, which has at least the following beneficial effects:
the preparation method of the vegetable protein-based adhesive comprises the steps of firstly blending vegetable protein with water, and carrying out heating degradation under alkaline conditions to obtain a precursor of the vegetable protein adhesive; and then mixing the o-aminobenzaldehyde, 4, 5-trihydroxybenzaldehyde, acid and a complexing agent, reacting under a reflux condition, adding the plant protein adhesive precursor, uniformly stirring, and continuing to heat for reaction. According to the preparation method disclosed by the invention, the polybenzoxazine resin pair and the plant protein are not simply mixed, but the characteristic of the plant protein is utilized, and active groups such as amino groups, hydroxyl groups and the like inherent on a macromolecular chain of the plant protein are utilized to participate in the synthesis of the polybenzoxazine resin, so that the modified plant protein-based adhesive is obtained.
The preparation method of the vegetable protein-based adhesive does not need to add an additional flame retardant, has excellent mechanical property and physical property, has higher flame retardance and better cost advantage, and can be applied to the gluing of Yu Zhumu artificial boards.
According to some embodiments of the invention, in step S1:
blending the vegetable protein and water, wherein the ratio of the vegetable protein to the water is 1:4-1:6.
The pH range of the alkaline condition is 8-10.
The temperature of the heating degradation is 50-60 ℃.
The time of heating degradation is 30-60 min.
In some embodiments of the invention, in step S2:
the reaction temperature under the reflux condition is 80-100 ℃.
The reaction time under the reflux condition is 0.5 h-1 h.
After the reaction under the reflux condition, the precursor of the plant protein adhesive is added, and the precursor is slowly added, so that the reaction is fully carried out.
After the plant protein adhesive precursor is added, the plant protein adhesive precursor is stirred rapidly and uniformly, and then the plant protein adhesive precursor is kept at the temperature of 60 ℃ for reaction for 1 to 2 hours.
The speed of rapid stirring is 1500 rpm-3000 rpm.
The time of rapid stirring is 30 min-90 min.
According to some embodiments of the invention, the method further comprises adding a curing agent to the cooled product after step S2 to promote curing of the product.
The curing agent comprises imidazole compounds or amine compounds such as diaminodiphenyl methane, so that the curing of the adhesive can be promoted, and the curing time and the curing temperature can be reduced.
In a third aspect, the invention provides a synthetic panel prepared from the vegetable protein-based adhesive.
The invention relates to one of the technical schemes of a composite board, which has at least the following beneficial effects:
the synthetic board of the invention has all the beneficial effects of the vegetable protein-based adhesive because the vegetable protein-based adhesive of the invention is used. Specifically:
the synthetic board provided by the invention is characterized in that the adhesive is a vegetable protein-based adhesive, and a benzoxazine monomer of a benzo six-membered heterocyclic compound is synthesized by taking primary amine compounds and aldehyde as raw materials, and can undergo ring-opening polymerization reaction under the action of heating and/or a catalyst to form the benzoxazine resin. Compared with common phenolic resin, the polybenzoxazine resin has no small molecule release in the molding and curing process, and the product has low porosity and near zero shrinkage. In addition, the polybenzoxazine resin has greater flexibility in molecular design, and is a novel phenolic resin. The plant protein-based adhesive is prepared by modifying the plant protein adhesive by using the polybenzoxazine resin, so that the mechanical strength and the water resistance of the plant protein-based adhesive are synchronously enhanced, and the plant protein-based adhesive has remarkable flame retardant property.
The composite board of the invention has lower cost and safer cost because no flame retardant is added. Meanwhile, the flame retardant has better mechanical property, physical property and flame retardant property.
According to some embodiments of the invention, the composite board comprises a multi-ply plywood and a particle board.
According to some embodiments of the invention, the multi-ply plywood may be eucalyptus three-ply plywood.
According to some embodiments of the invention, the particle board may be poplar particle board.
Detailed Description
The following are specific embodiments of the present invention, and the technical solutions of the present invention will be further described with reference to the embodiments, but the present invention is not limited to these embodiments.
In some embodiments of the present invention, a vegetable protein-based adhesive is provided, the preparation raw materials including vegetable protein, o-aminobenzaldehyde, 4, 5-trihydroxybenzaldehyde, acid, and primary amine compounds.
It can be understood that the vegetable protein-based adhesive of the invention synthesizes the benzoxazine monomer of the benzo six-membered heterocyclic compound by taking primary amine compounds and aldehyde as raw materials, and the benzoxazine monomer can undergo ring-opening polymerization reaction under the action of heating and/or a catalyst to form the polybenzoxazine resin. Compared with common phenolic resin, the polybenzoxazine resin has no small molecule release in the molding and curing process, and the product has low porosity and near zero shrinkage. In addition, the polybenzoxazine resin has greater flexibility in molecular design, and is a novel phenolic resin. The plant protein-based adhesive is prepared by modifying the plant protein adhesive by using the polybenzoxazine resin, so that the mechanical strength and the water resistance of the plant protein-based adhesive are synchronously enhanced, and the plant protein-based adhesive has remarkable flame retardant property.
The benzoxazine resin is a generic name containing N and O six-membered oxazine ring compounds, and has the advantages of higher heat resistance, higher glass transition temperature of above 150 ℃, almost zero curing shrinkage, V1 level flame retardance, low water absorption, high modulus and small dielectric property.
The curing mode of the benzoxazine resin comprises the following steps:
and (3) thermally self-curing: the benzoxazine monomer is subjected to ring opening under the heating condition to form phenolic hydroxyl groups, and a structure similar to a polyphenol aldehyde is formed in a catalysis mode, so that a three-dimensional crosslinked network structure is formed.
Thermocatalytic curing: the benzoxazine ring-opening curing is catalyzed by the addition of a cationic catalyst, such as a lewis acid, imidazole, iodonium salt, sulfonium salt, and the like, which generates active cations in a heated environment.
The preparation raw materials of the vegetable protein-based adhesive comprise:
the plant protein has the function of utilizing amino, mercapto, hydroxyl and the like on protein molecules to participate in the curing reaction of the benzoxazine resin, and is connected with the resin through covalent bonds to form a three-dimensional network structure, and meanwhile, the cost of the resin can be reduced, and the resin has degradability.
The function of the o-aminobenzaldehyde is to provide amino and aldehyde groups in the reaction process, so that the reaction can be normally carried out.
The 4, 5-trihydroxybenzaldehyde serves as a multifunctional chemical substance, and simultaneously provides aldehyde groups and phenolic hydroxyl groups in the reaction process.
The roles of the acids include: (1) As a catalyst, providing an acidic environment for the curing reaction of the resin; (2) Part of the resin is involved in the curing of the resin so that the resin also has acid functionality (acid selective phosphoric acid, boric acid).
The addition of boric acid or phosphoric acid, the actions including: (1) As Lewis acid to participate in and catalyze the curing reaction of the resin smoothly; (2) The flame retardant property is realized by the P and B elements contained in the flame retardant material. As the curing component of the resin, the acidic substance can be fully and uniformly dispersed in the resin and the artificial board, and the flame retardant effect is remarkable.
The primary amine compound functions to provide an amino group for the curing reaction of the resin.
In some embodiments of the present invention, the preparation raw materials include, by weight:
vegetable protein: 10 to 20 parts of the components in parts by weight,
o-aminobenzaldehyde: 0.5 to 6 parts of the components,
4, 5-trihydroxybenzaldehyde: 1 to 8 parts of a mixture of components,
acid: 0.5 to 3 parts of the components,
primary amine compound: 0.5 to 4 parts.
In some embodiments of the invention, the source of vegetable proteins includes soy protein, soy meal, defatted soy flour, and oil tea cake proteins.
In some embodiments of the invention, the source of vegetable proteins further includes isolated proteins that remain after various grease processing.
In some embodiments of the invention, the acid comprises boric acid or phosphoric acid.
In some embodiments of the invention, the primary amine compound comprises at least one of triethylene tetramine and diethylene triamine.
In still other embodiments of the present invention, the present invention provides a method of preparing the vegetable protein-based adhesive of the present invention, comprising the steps of:
s1: blending vegetable protein and water, and heating and degrading under alkaline conditions to obtain a precursor of the vegetable protein adhesive;
s2: mixing o-aminobenzaldehyde, 4, 5-trihydroxybenzaldehyde, acid and a complexing agent, reacting under a reflux condition, adding a plant protein adhesive precursor, stirring uniformly, and continuing to heat for reaction.
It can be understood that the preparation method of the vegetable protein-based adhesive comprises the steps of firstly blending vegetable protein and water, and carrying out heating degradation under alkaline conditions to obtain a precursor of the vegetable protein-based adhesive; then mixing the o-aminobenzaldehyde, 4, 5-trihydroxybenzaldehyde, acid and a complexing agent, reacting under a reflux condition, adding a plant protein adhesive precursor, uniformly stirring, and continuing to heat and react. According to the preparation method disclosed by the invention, the polybenzoxazine resin pair and the plant protein are not simply mixed, the characteristic of the plant protein is utilized, and the inherent amino, hydroxyl and other active groups on the macromolecular chain are utilized to participate in the synthesis of the polybenzoxazine resin, so that a modified plant protein-based adhesive is obtained, no additional flame retardant is needed, excellent mechanical properties and physical properties are achieved, and the adhesive has higher flame retardance and better cost advantage, and can be applied to the gluing of Yu Zhumu artificial boards.
In some embodiments of the invention, in step S1:
blending the vegetable protein and water, wherein the ratio of the vegetable protein to the water is 1:4-1:6.
The pH range of the alkaline condition is 8-10.
The temperature of the heating degradation is 50-60 ℃.
The time of heating degradation is 30-60 min.
In some embodiments of the invention, in step S2:
the reaction temperature under the reflux condition is 80-100 ℃.
The reaction time under the reflux condition is 0.5 h-1 h.
After the reaction under the reflux condition, the plant protein adhesive precursor is added, and the reaction is slowly added, so that the reaction is fully carried out.
After the plant protein adhesive precursor is added, the plant protein adhesive precursor is stirred rapidly and uniformly, and then the plant protein adhesive precursor is kept at the temperature of 60 ℃ for reaction for 1 to 2 hours.
The speed of rapid stirring is 1500 rpm-3000 rpm.
The time of rapid stirring is 30 min-90 min.
In some embodiments of the invention, the method of preparation further comprises adding a curing agent to the cooled product after step S2 to promote curing of the product.
The curing agent comprises imidazole compounds or amine compounds such as diaminodiphenyl methane, so that the curing of the adhesive can be promoted, and the curing time and the curing temperature can be reduced.
In still other embodiments of the present invention, the present invention provides a synthetic panel prepared from the plant protein based adhesive of the present invention.
It will be appreciated that the synthetic panel of the present invention, due to the use of the vegetable protein based adhesive of the present invention, provides all of the beneficial effects of the vegetable protein based adhesive. Specifically:
it can be further understood that the synthetic board of the invention, wherein the adhesive is a vegetable protein-based adhesive, and is a benzoxazine monomer synthesized by using primary amine compounds and aldehyde as raw materials, wherein the benzoxazine monomer can undergo ring-opening polymerization reaction under the action of heating and/or a catalyst to form the benzoxazine resin. Compared with common phenolic resin, the polybenzoxazine resin has no small molecule release in the molding and curing process, and the product has low porosity and near zero shrinkage. In addition, the polybenzoxazine resin has greater flexibility in molecular design, and is a novel phenolic resin. The plant protein-based adhesive is prepared by modifying the plant protein adhesive by using the polybenzoxazine resin, so that the mechanical strength and the water resistance of the plant protein-based adhesive are synchronously enhanced, and the plant protein-based adhesive has remarkable flame retardant property.
In addition, the composite board of the invention has lower cost and safer cost because no flame retardant is added. Meanwhile, the flame retardant has better mechanical property, physical property and flame retardant property.
In some embodiments of the invention, the composite board comprises plywood and particle board.
In some embodiments of the invention, the plywood may be eucalyptus plywood.
The eucalyptus plywood is made by rotary-cutting eucalyptus sections into eucalyptus veneers or cutting eucalyptus sections Cheng Baomu, and then gluing with adhesives to form three or more layers of plate-like materials, usually using odd-layer veneers, and making the fiber directions of adjacent layers of veneers mutually perpendicular.
In some embodiments of the invention, the particle board may be poplar particle board.
In some embodiments of the present invention, the particle board may also be other fast-growing wood materials including, but not limited to, pinus massoniana, bamboo shavings, eucalyptus shavings, and the like.
The particle board is also called a particle board, and is manufactured by cutting various branches and buds, small-diameter wood, fast-growing wood, wood dust and the like into fragments with a certain specification, drying, mixing with sizing materials, hardening agents, waterproofing agents and the like, and pressing at a certain temperature and under a certain pressure.
The technical solutions of the present invention will be better understood by the following specific examples and comparative examples.
Example 1
The vegetable protein-based adhesive is prepared from the following raw materials in parts by weight:
vegetable protein: 15 parts of a mixture of two or more components,
o-aminobenzaldehyde: 3 parts of the components in parts by weight,
4, 5-trihydroxybenzaldehyde: 4 parts of the total weight of the powder,
acid: 2 parts of the components are mixed together,
primary amine compound: 3 parts.
Wherein the vegetable protein is soybean protein isolate.
The acid is phosphoric acid.
The specific preparation method comprises the following steps:
s1: blending vegetable protein and water, and heating and degrading under alkaline conditions to obtain a precursor of the vegetable protein adhesive;
s2: mixing o-aminobenzaldehyde, 4, 5-trihydroxybenzaldehyde, acid and a complexing agent, reacting under a reflux condition, adding a plant protein adhesive precursor, stirring uniformly, and continuing to heat for reaction.
In step S1:
the vegetable protein and water were blended at a ratio of 1:5.
The pH range of the alkaline condition is 8-10.
The temperature of the thermal degradation was 50 ℃.
The time of thermal degradation was 45min.
In step S2:
the temperature of the reaction under reflux was 90 ℃.
The reaction time under reflux was 0.5h.
After the reaction under the reflux condition, the plant protein adhesive precursor is added, and the reaction is slowly added, so that the reaction is fully carried out.
After the plant protein adhesive precursor is added, the plant protein adhesive precursor is stirred rapidly and uniformly, and then the plant protein adhesive precursor is kept at the temperature of 60 ℃ for reaction for 1h.
The speed of rapid stirring was 2000rpm.
The time of rapid stirring was 60min.
Example 2
The vegetable protein-based adhesive is prepared from the following raw materials in parts by weight:
vegetable protein: 10 parts of a powder for injection,
o-aminobenzaldehyde: 3 parts of the components in parts by weight,
4, 5-trihydroxybenzaldehyde: 4 parts of the total weight of the powder,
acid: 2 parts of the components are mixed together,
primary amine compound: 3 parts.
Wherein the vegetable protein is soybean protein isolate.
The acid is boric acid.
The primary amine compound is triethylene tetramine.
The specific preparation method is the same as that of example 1.
Example 3
The vegetable protein-based adhesive is prepared from the following raw materials in parts by weight:
vegetable protein: 15 parts of a mixture of two or more components,
o-aminobenzaldehyde: 1 part of the total weight of the mixture,
4, 5-trihydroxybenzaldehyde: 4 parts of the total weight of the powder,
acid: 2 parts of the components are mixed together,
primary amine compound: 3 parts.
Wherein the vegetable protein is soybean protein isolate.
The acid is phosphoric acid.
The primary amine compound is triethylene tetramine.
The specific preparation method is the same as that of example 1.
Example 4
The vegetable protein-based adhesive is prepared from the following raw materials in parts by weight:
vegetable protein: 15 parts of a mixture of two or more components,
o-aminobenzaldehyde: 3 parts of the components in parts by weight,
4, 5-trihydroxybenzaldehyde: 1 part of the total weight of the mixture,
acid: 2 parts of the components are mixed together,
primary amine compound: 3 parts.
The specific preparation method is the same as that of example 1.
Example 5
The vegetable protein-based adhesive is prepared from the following raw materials in parts by weight:
vegetable protein: 15 parts of a mixture of two or more components,
o-aminobenzaldehyde: 3 parts of the components in parts by weight,
4, 5-trihydroxybenzaldehyde: 4 parts of the total weight of the powder,
acid: 0.5 part of the total weight of the mixture,
primary amine compound: 3 parts.
Wherein the vegetable protein is soybean protein isolate.
The acid is phosphoric acid.
The specific preparation method is the same as that of example 1.
Comparative example 1
The difference between this comparative example and example 1 is that no acidic component is added, and the remaining conditions are the same.
Comparative example 2
The difference between this comparative example and example 1 is that no anthranilaldehyde was added, and the remaining conditions were the same.
Comparative example 3
The difference between this comparative example and example 1 is that 4, 5-trihydroxybenzaldehyde is not added, and the other conditions are the same.
Comparative example 4
The difference between this comparative example and example 1 is that the acidic component is replaced with sodium hydroxide, and the remaining conditions are the same.
Test example 1
The adhesive strength of the adhesives prepared in examples and comparative examples was tested according to GB/T17657-2022 method for testing physicochemical properties of artificial boards and veneers, and the results are shown in Table 1.
Three-layer eucalyptus plywood was prepared from eucalyptus veneers (dimensions length, width, thickness 600 mm. Times.600X 1.6 mm).
Hot pressing conditions: the hot pressing temperature is 120 ℃, the hot pressing time is 5-6min, the hot pressing pressure is 1-1.2MPa, and the sizing amount is 210g/m 2 (double sided).
Table 1 performance test in eucalyptus three-layer plywood
Test example 2
The adhesives of examples and comparative examples were tested for their adhesion strength, moisture resistance, static bending strength, elastic modulus, 24-hour water absorption thickness expansion and flame retardant property grade in poplar particle board (P6 type shaving board, thickness 10 mm) according to GB/T4897-2015 particle board. The results are shown in Table 2.
The hot pressing conditions of the shaving board are as follows: the hot pressing temperature is 130 ℃, the hot pressing time is 25-30min, and the sizing amount is 9-12% (dry basis).
Table 2 performance test in poplar particle board
Test example 3
And (3) forming the bamboo fiber by hot pressing (a die) to prepare a veneer with the thickness of 2mm.
Hot pressing conditions: the hot pressing temperature is 110 ℃, the hot pressing time is 4-6 min, the hot pressing pressure is 0.8-1.2 MPa, and the sizing amount is 6-8% (dry basis).
The sample was sawed into a sheet of dimensions of 170mm by 30mm length and width. Breaking test, drop test, heat distortion resistance and sensory index test were performed.
Wherein:
breaking test:
1 sample was taken, picked up by hand according to normal eating habits, and then a 500g weight was applied to the forefront of the dish, kept horizontal for 1min to see if the sample was broken.
Drop test:
at normal temperature, 1 sample is 1.2m high from the flat cement floor, and falls horizontally and freely for 5 times, and whether the samples have phenomena of incomplete, fracture and the like is observed.
Heat distortion resistance:
the sample is completely immersed in boiling water at 100 ℃ for 10min and then taken out, and whether the sample has obvious deformation, discoloration, peeling and other abnormal phenomena or not is observed.
Sensory index:
color measurement was carried out according to the method prescribed in GB 31604.7-2016 (positive for colored judgment and negative for non-colored judgment), and odor was not abnormal in terms of the soaking liquid obtained by the migration test.
The results are shown in Table 3.
Table 3 test of the performance of the bamboo fiber disposable tableware plate
The present invention has been described in detail with reference to the embodiments, but the present invention is not limited to the embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.
Claims (10)
1. The vegetable protein-based adhesive is characterized in that the preparation raw materials comprise vegetable protein, o-aminobenzaldehyde, 4, 5-trihydroxybenzaldehyde, acid and primary amine compounds.
2. The vegetable protein-based adhesive according to claim 1, wherein the preparation raw materials comprise, by weight: vegetable protein: 10 to 20 parts of the components in parts by weight,
o-aminobenzaldehyde: 0.5 to 6 parts of the components,
4, 5-trihydroxybenzaldehyde: 1 to 8 parts of a mixture of components,
acid: 0.5 to 3 parts of the components,
primary amine compound: 0.5 to 4 parts.
3. The vegetable protein-based adhesive according to claim 1 or 2, wherein the vegetable protein source comprises soy protein, soybean meal, defatted soybean meal, and oil tea cake protein.
4. The vegetable protein-based adhesive according to claim 1 or 2, wherein the acid comprises boric acid or phosphoric acid.
5. The vegetable protein-based adhesive according to claim 1 or 2, wherein the primary amine compound comprises at least one of triethylene tetramine and diethylene triamine.
6. A method for preparing the vegetable protein-based adhesive according to any one of claims 1 to 5, comprising the steps of:
s1: blending the vegetable protein with water, and carrying out heating degradation under an alkaline condition to obtain a vegetable protein adhesive precursor;
s2: mixing the o-aminobenzaldehyde, 4, 5-trihydroxybenzaldehyde, acid and a complexing agent, reacting under a reflux condition, adding the plant protein adhesive precursor, stirring uniformly, and continuing to heat for reaction.
7. The method according to claim 6, wherein in step S1, the temperature of the thermal degradation is 50 ℃ to 60 ℃; and/or the time of the heating degradation is 30-60 min.
8. The method according to claim 6, wherein in step S2, the temperature of the reaction under the reflux condition is 80 ℃ to 100 ℃; and/or the reaction time under the reflux condition is 0.5-1 h.
9. The method of claim 6, further comprising adding a curing agent to the cooled product after step S2 to promote product curing.
10. An artificial board, characterized in that the raw material for preparation comprises the vegetable protein-based adhesive as claimed in any one of claims 1 to 5.
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