CN115491175A - Flame-retardant waterproof soybean-based adhesive as well as preparation method and application thereof - Google Patents
Flame-retardant waterproof soybean-based adhesive as well as preparation method and application thereof Download PDFInfo
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- CN115491175A CN115491175A CN202211349338.9A CN202211349338A CN115491175A CN 115491175 A CN115491175 A CN 115491175A CN 202211349338 A CN202211349338 A CN 202211349338A CN 115491175 A CN115491175 A CN 115491175A
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- 239000000853 adhesive Substances 0.000 title claims abstract description 58
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 58
- 235000010469 Glycine max Nutrition 0.000 title claims abstract description 45
- 244000068988 Glycine max Species 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 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 title claims abstract description 25
- 239000003063 flame retardant Substances 0.000 title claims abstract description 24
- 239000002105 nanoparticle Substances 0.000 claims abstract description 54
- 239000004952 Polyamide Substances 0.000 claims abstract description 48
- 229920002647 polyamide Polymers 0.000 claims abstract description 48
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 34
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims abstract description 34
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 31
- 229920000642 polymer Polymers 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 21
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 125000003277 amino group Chemical group 0.000 claims abstract description 11
- 244000046052 Phaseolus vulgaris Species 0.000 claims abstract description 10
- 235000010627 Phaseolus vulgaris Nutrition 0.000 claims abstract description 10
- 235000013312 flour Nutrition 0.000 claims abstract description 8
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 27
- 235000011037 adipic acid Nutrition 0.000 claims description 16
- 239000001361 adipic acid Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 9
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 7
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 20
- 239000002023 wood Substances 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 108010073771 Soybean Proteins Proteins 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 235000019710 soybean protein Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 241000219000 Populus Species 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 239000011120 plywood Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 244000166124 Eucalyptus globulus Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001279 adipic acids Chemical class 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- -1 amino, carboxyl Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound 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 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920002755 poly(epichlorohydrin) Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229940001941 soy protein Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
- B27N3/002—Manufacture of substantially flat articles, e.g. boards, from particles or fibres characterised by the type of binder
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Wood Science & Technology (AREA)
- Forests & Forestry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a flame-retardant waterproof soybean-based adhesive as well as a preparation method and application thereof, wherein the preparation raw materials of the soybean-based adhesive comprise: bean flour and organic-inorganic hybrid modified polyamide epichlorohydrin resin; the preparation raw materials of the organic-inorganic hybrid modified polyamide epichlorohydrin resin comprise: modified polyamide polymers, modified polyvinyl alcohols; the modified polyamide polymer is prepared from the following raw materials: modified inorganic nanoparticles; the modified inorganic nano particles are modified with amino groups; the modified polyvinyl alcohol is modified with epoxy group. The flame-retardant waterproof soybean-based adhesive disclosed by the invention can improve the water resistance and the bonding strength of the soybean-based adhesive and enhance the flame-retardant function of an artificial board product.
Description
Technical Field
The invention belongs to the technical field of adhesives, and particularly relates to a flame-retardant waterproof soybean-based adhesive as well as a preparation method and application thereof.
Background
The traditional wood board usually uses high-quality wood as raw material, and on the premise of not changing wood structure the invented wood board with a certain decorative property and usability is made up, so that it has the advantages of low utilization rate of wood, large consumption, long growth period of high-quality wood and short resource. The artificial board is made by using a solid wood jointed board or a veneer as a surface layer, a solid wood strip as a core layer and a veneer as a bottom layer, a large amount of fast-growing wood is utilized on raw materials, the use of high-quality wood can be reduced and saved, compared with the solid wood board, a certain amount of adhesive is needed in the process of compounding the artificial board, wherein the soybean adhesive without formaldehyde is favored in the production and application of the artificial board, but the high relative molecular weight of the soybean gum adhesive enables the entanglement and adsorption aggregation among soybean protein molecular chains to be obvious, so that the soybean gum adhesive has the characteristics of high viscosity (more than 75000mPa.s) and low solid content (generally between 20 and 35 percent). The high viscosity makes the bean gum adhesive unfavorable for wetting to influence the bonding strength and the sizing performance, so that the bean gum cannot be suitable for artificial boards made of different raw materials.
Therefore, the development of the flame-retardant waterproof soybean-based adhesive and the preparation method and the application thereof are urgent, and the problems of insufficient bonding strength and poor water resistance of the adhesive in the prior art can be solved.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the flame-retardant waterproof soybean-based adhesive provided by the invention can improve the water resistance and the bonding strength of the soybean-based adhesive.
According to the first aspect of the invention, the flame-retardant waterproof soybean-based adhesive is prepared by the following raw materials: soybean powder and organic-inorganic hybrid modified polyamide epichlorohydrin resin;
the preparation raw materials of the organic-inorganic hybrid modified polyamide epichlorohydrin resin comprise: modified polyamide polymers, modified polyvinyl alcohols;
the modified polyamide polymer is prepared from the following raw materials: modified inorganic nanoparticles;
the modified inorganic nano particles are modified with amino groups;
the modified polyvinyl alcohol is modified with epoxy group.
The flame-retardant waterproof soybean-based adhesive disclosed by the embodiment of the invention at least has the following beneficial effects:
epoxy group modified polyvinyl alcohol (PVA) is modified by a high-reactivity epoxy group, and the PVA is favorable for the stability of a modified bean gum composite emulsion system, the viscosity of the emulsion is improved, and the initial viscosity and the sizing performance of bean gum are improved based on the performance of the PVA; PVA as a long-chain polymer cannot generate polymerization reaction with polyamide, but after epoxidation modification, an epoxy group can react with active groups (hydroxyl, amino, carboxyl and the like) on components (soybean protein, polysaccharide and the like) in bean gum to form covalent bond connection, and a stable three-dimensional network structure is formed through synergistic reaction, so that the number of hydrophilic groups is effectively reduced, the water resistance and the bonding strength are improved, and compared with the single PVA, the effect is obviously enhanced.
According to some embodiments of the invention, the modified inorganic nanoparticles are prepared from the following raw materials: inorganic nanoparticles and a silane coupling agent.
According to some embodiments of the invention, the raw materials for preparing the modified inorganic nanoparticles further comprise a solvent.
According to some embodiments of the present invention, the solvent in the raw material for preparing the modified inorganic nanoparticles comprises at least one of ethanol and toluene.
According to some embodiments of the present invention, the modified inorganic nanoparticles are prepared from the following raw materials in parts by weight: 10-20 parts of silane coupling agent, 30-50 parts of absolute ethyl alcohol, 10-30 parts of toluene and 3-8 parts of inorganic nano particles.
According to some embodiments of the invention, the inorganic nanoparticles comprise at least one or more of copper-supported nano montmorillonite, nano zinc oxide, nano titanium oxide, and nano silver.
The inorganic nano particles can enhance the mechanical strength of the modified polyamide polymer, so that the hardness and the rigidity strength of the adhesive are improved.
The inorganic particles have enhanced thermal stability and flame retardant property, and the inorganic nanoparticles contain a large amount of bound water, so that more water vapor molecules can be released during combustion, and heat generated by a large amount of combustion interfaces can be absorbed and taken away, thereby reducing the combustion strength; in addition, the inorganic nano particles can form a barrier layer during combustion, and oxygen is prevented from further contacting and combusting with combustible substances, so that the inorganic nano particles have a remarkable flame-retardant effect through dehydration and formation of the barrier layer, and the thermal stability and the flame-retardant property of the adhesive are enhanced. On the other hand, the inorganic nanoparticles can enhance the rigidity strength of the soybean-based adhesive, and can reduce the absorption and permeation of water molecules in the adhesive through physical filling and steric hindrance effects, so that the bonding strength of the adhesive is enhanced, and the water resistance of the adhesive is simultaneously enhanced. However, the inorganic nanoparticles can not directly perform a direct chemical reaction with adipic acid to generate hybrid modified polyamide, the surfaces of the inorganic nanoparticles are modified through KH792, long-chain amino groups are modified on the particle surfaces, and the particles can react with the adipic acid through amino groups to generate the hybrid modified polyamide through the reaction, and participate in subsequent synthesis reaction.
According to some embodiments of the invention, the silane coupling agent comprises KH792.
And (3) carrying out surface modification on the inorganic nanoparticles by KH792 to obtain the amino surface modified inorganic nanoparticles. Under the action of the KH792 long-chain aminosilane coupling agent, the steric hindrance problem caused by large space occupation of inorganic nanoparticles can be effectively solved, and amino groups can be effectively exposed to participate in subsequent reactions.
According to some embodiments of the invention, the step of preparing the modified inorganic nanoparticles comprises mixing a silane coupling agent and inorganic nanoparticle particles.
According to some embodiments of the invention, the temperature of the mixing in the preparation of the modified inorganic nanoparticles is 80 to 90 ℃.
According to some embodiments of the invention, in the preparation of the modified inorganic nanoparticles, the mixing time is 1 to 3 hours.
According to some embodiments of the invention, the modified polyamide polymer is prepared from a feedstock comprising: adipic acid.
According to some embodiments of the invention, the adipic acid and the modified inorganic nanoparticles are present in an amount of 1:0.3 to 0.6.
According to some preferred embodiments of the present invention, the adipic acid and the modified inorganic nanoparticles are in a weight ratio of 1:0.3 to 0.4.
According to some embodiments of the invention, the method of preparing the modified polyamide polymer comprises: mixing and reacting the adipic acid and the modified inorganic nanoparticles.
In the preparation of the modified polyamide polymer, the amino groups in the modified inorganic nanoparticles are reacted with adipic acid to form the modified polyamide polymer. Through organic-inorganic hybrid reaction, the obtained polyamide polymer not only has stronger reactivity, but also has the performance of inorganic nanoparticles.
According to some embodiments of the invention, the temperature of the mixing in the process for preparing the modified polyamide polymer is 150 to 175 ℃.
According to some embodiments of the invention, in the method for preparing the modified polyamide polymer, the mixing time is 1 to 3 hours.
According to some embodiments of the invention, the mixing comprises stirring and mixing in the process for preparing the modified polyamide polymer.
According to some embodiments of the invention, in the method for preparing the modified polyamide polymer, the rotation speed of the stirring and mixing is 300r/min.
According to some preferred embodiments of the present invention, mixing and reacting the adipic acid and the modified inorganic nanoparticles further comprises cooling the temperature of the reacted system to 100 to 105 ℃.
According to some preferred embodiments of the present invention, the cooling further comprises adjusting the solid content of the system to 50-60%.
The dispersibility of the system is ensured under the solid content, and the subsequent reaction of the system is facilitated.
According to some preferred embodiments of the invention, the solids content adjusting solvent comprises boiling water.
According to some embodiments of the invention, the modified polyvinyl alcohol is prepared from raw materials comprising polyvinyl alcohol, diethylenetriamine and ethylene glycol diglycidyl ether.
According to some embodiments of the invention, the method of preparing the modified polyvinyl alcohol comprises:
s1: mixing the diethylenetriamine and the ethylene glycol diglycidyl ether to obtain a prepolymer;
s2: and (3) mixing and reacting the prepolymer obtained in the step S1 and polyvinyl alcohol.
According to some embodiments of the invention, in step S1, the diethylenetriamine is 0.5 to 1 part by weight, and the ethylene glycol diglycidyl ether is 10 to 20 parts by weight.
According to some embodiments of the invention, the temperature of the mixing in step S1 is 40 to 50 ℃.
According to some embodiments of the invention, in step S1, the mixing time is 15 to 30min.
According to some embodiments of the invention, in step S2, the prepolymer is 5 to 20 parts by weight and the polyvinyl alcohol is 5 to 15 parts by weight.
According to some embodiments of the invention, the weight ratio of the prepolymer to the polyvinyl alcohol in step S2 is not less than 1.
According to some embodiments of the invention, the temperature of the reaction in step S2 is 70 to 80 ℃.
According to some embodiments of the invention, in step S2, the reaction time is 1 to 2 hours.
In the step S2, the reaction temperature and the reaction time are strictly controlled, and the excessive reaction temperature causes excessive reaction, and colloidal bodies with too large molecular weight and incapable of being dissolved in water are formed, so that the subsequent reaction activity is remarkably reduced.
According to some embodiments of the invention, the method for preparing the organic-inorganic hybrid modified polyamide epichlorohydrin resin comprises: mixing and reacting modified polyvinyl alcohol with the modified polyamide polymer.
According to some embodiments of the invention, in the preparation method of the organic-inorganic hybrid modified polyamide epichlorohydrin resin, the ratio by mass of the modified polyvinyl alcohol to the modified polyamide polymer is 1.
According to some embodiments of the invention, in the preparation method of the organic-inorganic hybrid modified polyamide epichlorohydrin resin, the mixing temperature is 60-80 ℃.
According to some embodiments of the invention, in the preparation method of the organic-inorganic hybrid modified polyamide epichlorohydrin resin, the mixing time is 2-6 h.
In the preparation method of the organic-inorganic hybrid modified polyamide epichlorohydrin resin, the reaction system is more complicated due to the addition of the inorganic nanoparticles, and the organic-inorganic hybrid modified polyamide epichlorohydrin resin is obtained by the reaction at the reaction temperature.
According to a second aspect of the invention, a method for preparing a flame-retardant waterproof soybean-based adhesive comprises the following steps: mixing the bean flour and the organic-inorganic hybrid modified polyamide epichlorohydrin resin.
According to some embodiments of the invention, the soybean flour is 10 to 20 parts by weight and the modified polyamide epichlorohydrin resin is 10 to 30 parts by weight.
According to some embodiments of the invention, the soy flour comprises at least one of defatted soy flour and soy protein flour.
According to the artificial board of the third aspect of the embodiment of the invention, the raw materials for preparing the artificial board comprise the soybean-based adhesive.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the same or similar elements or elements having the same or similar functions throughout. The embodiments described below by reference are exemplary only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
Example 1
The embodiment discloses a preparation method of a flame-retardant waterproof soybean-based adhesive, which comprises the following specific steps:
a1, modifying the surface amino of the inorganic nano particles: performing surface modification on inorganic nanoparticles by using KH792 to obtain modified inorganic nanoparticles, wherein the specific conditions are that KH792 10 parts, anhydrous ethanol 30 parts, toluene 10 parts and inorganic nanoparticles (nano zinc oxide) 3 parts are mixed, heated to 80 ℃ and reacted for 1h;
a2, condensation polymerization of amino acid: mixing the components in a mass ratio of 1:0.3 of adipic acid and modified inorganic nanoparticles are respectively added into a three-neck flask with a condenser, a mechanical stirrer (stirring speed is more than 300 r/min) is adopted, the temperature is heated to 160 ℃, the oil bath pot is closed after the reaction is carried out for 2h, boiling water is added when the temperature is cooled to about 100 ℃, and the solid content of the system is adjusted to 50 percent to obtain the modified polyamide polymer.
A3, pre-polymerizing diethylenetriamine and ethylene glycol diglycidyl ether to obtain a prepolymer, and reacting 10 parts of ethylene glycol diglycidyl ether and 0.5 part of diethylenetriamine at 50 ℃ for 10min;
and A4, reacting 10 parts of prepolymer and 10 parts of polyvinyl alcohol for 1 hour at the temperature of 70 ℃ under reflux to obtain the modified polyvinyl alcohol. And (3) mixing 10 parts of modified polyvinyl alcohol with 12 parts of modified polyamide polymer in the step A2, and then reacting for 3 hours at 80 ℃ under the reflux condition to obtain the organic-inorganic hybrid modified polyepichlorohydrin resin (modified PAE resin).
The step A3 and the step A1 are not separated in sequence.
Example 2
The embodiment discloses a preparation method of a flame-retardant waterproof soybean-based adhesive, and the difference between the embodiment and the embodiment 1 is that: the mass ratio of adipic acid to the modified inorganic nanoparticles is 1.6, and the other conditions are the same.
Example 3
The embodiment discloses a preparation method of a flame-retardant waterproof soybean-based adhesive, and the difference between the embodiment and the embodiment 1 is that: the mass ratio of adipic acid to the modified inorganic nanoparticles is 0.5, and the rest conditions are the same.
Example 4
The embodiment discloses a preparation method of a flame-retardant waterproof soybean-based adhesive, and the difference between the embodiment and the embodiment 1 is that: 5 parts of prepolymer and 15 parts of polyvinyl alcohol in the step A4, and the rest conditions are the same.
Example 5
The embodiment discloses a preparation method of a flame-retardant waterproof soybean-based adhesive, and the difference between the embodiment and the embodiment 1 is that: 15 parts of prepolymer and 5 parts of polyvinyl alcohol in the step A4, and the rest conditions are the same.
Comparative example 1
The comparative example discloses a preparation method of a flame-retardant waterproof soybean-based adhesive, and the differences between the comparative example and the example 1 are as follows: the inorganic nanoparticles were not modified with KH792, and the rest conditions were the same.
Comparative example 2
The comparative example discloses a preparation method of a flame-retardant waterproof soybean-based adhesive, and the difference between the comparative example and the example 1 is that epichlorohydrin is used for replacing modified polyvinyl alcohol, and the other conditions are the same.
Comparative example 3
The comparative example is different from the example 1 in that a polyamide polymer is used for replacing a modified polyamide polymer, and the rest conditions are the same.
Comparative example 4
The comparative example discloses a preparation method of a flame-retardant waterproof soybean-based adhesive, and is different from the comparative example 1 in that KH550 is used for replacing KH792, and other conditions are the same.
Test example 1
The performance of the soybean-based adhesives obtained in examples 1 to 4 and comparative examples 1 to 4 was tested, and the test results are shown in table 1:
table 1 performance testing of soy-based adhesives in eucalyptus plywood (type i plywood)
In the comparative example 1, no KH792 modification is carried out on the surface of the inorganic nanoparticles to modify amino groups, so that the inorganic nanoparticles cannot participate in subsequent reaction, and the reaction effect is influenced because the inorganic nanoparticles are purely physically filled in the whole system; in the comparative example 2, the stability of the bean gum composite emulsion system is reduced and the viscosity of the emulsion is reduced due to the fact that epichlorohydrin is used for replacing modified polyvinyl alcohol; comparative example 3 the amide polymer is used to replace the modified polyamide polymer, and modified inorganic nanoparticles are not contained, so that the rigidity and bonding strength of the adhesive are reduced; in comparative example 4, KH550 was used instead of KH792, and after the silane coupling agent was replaced, the amino group was not sufficiently contacted with adipic acid due to the short length of the molecule having the amino group and steric hindrance effect, so that the reaction was insufficient, and compared with KH792, the KH550 modified amino group was not sufficiently involved in the subsequent reaction.
Test example 2
The performance of the soybean-based adhesives obtained in examples 1 to 4 and comparative examples 1 to 4 in the poplar shaving board was tested, and the test results are shown in table 2.
TABLE 2 Performance testing of soy-based adhesives on poplar flakeboards (P6-type flakeboard, thickness > 6-13 mm)
Through test investigation and optimization, the use amount of adipic acid is required to exceed the use amount of inorganic particles by a certain proportion to realize a better modification effect, so that the strength, the water resistance and the flame retardant property of the modified adipic acid are obviously improved compared with those of 2,3 in example 1; in comparative example 1, inorganic nanoparticles without surface modification cannot participate in subsequent reaction, and only physical filling is performed, so that the finally prepared adhesive is simple and does not have any simple mixing of components capable of reacting with each other, and has certain strength because the soybean protein in the adhesive is formed after heat curing, but does not have water resistance and high bonding strength at all; compared with the comparative example 2, the modified PVA can improve the initial viscosity of the adhesive and improve the dispersibility and stability of an adhesive system after replacing epichlorohydrin. Meanwhile, PVA is used as a long-chain molecule, modifies an epoxy group, participates in the reaction with modified polyamide, and can obviously improve the density of the interpenetrating network structure of the curing adhesive, so that inorganic nanoparticles are more stable in the curing adhesive system. In the comparative example 3, the conventional polyamide is used, and no inorganic nano particles participate in the reaction, so that the flame retardant property is remarkably reduced to B3 level; and no nano particles participate in the reaction, and the overall strength and the water resistance of the adhesive are weaker than those of the scheme in the embodiment.
While the embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (10)
1. The flame-retardant waterproof soybean-based adhesive is characterized in that the preparation raw materials of the soybean-based adhesive comprise: bean flour and organic-inorganic hybrid modified polyamide epichlorohydrin resin;
the preparation raw materials of the organic-inorganic hybrid modified polyamide epichlorohydrin resin comprise: modified polyamide polymers, modified polyvinyl alcohols;
the modified polyamide polymer is prepared from the following raw materials: modified inorganic nanoparticles;
the modified inorganic nano particles are modified with amino groups;
the modified polyvinyl alcohol is modified with epoxy group.
2. The soy-based adhesive of claim 1, wherein the modified inorganic nanoparticles are prepared from the following raw materials: inorganic nanoparticles and a silane coupling agent; preferably, the silane coupling agent comprises KH792.
3. The soy-based adhesive of claim 1, wherein the modified polyamide polymer is prepared from the following raw materials: adipic acid, preferably, the adipic acid and the modified inorganic nanoparticles are in a weight ratio of 1:0.3 to 0.6.
4. The soy-based adhesive of claim 3, wherein the modified polyamide polymer is prepared by a process comprising: mixing and reacting the adipic acid and the modified inorganic nanoparticles.
5. The soy-based adhesive as defined in claim 2, wherein the modified polyvinyl alcohol is prepared from polyvinyl alcohol, diethylenetriamine and ethylene glycol diglycidyl ether.
6. The soy-based adhesive of claim 5, wherein the modified polyvinyl alcohol is prepared by a method comprising:
s1: mixing the diethylenetriamine and the ethylene glycol diglycidyl ether to obtain a prepolymer;
s2: and (3) mixing and reacting the prepolymer obtained in the step S1 and polyvinyl alcohol.
7. The soybean-based adhesive according to claim 1, wherein the preparation method of the organic-inorganic hybrid modified polyamide epichlorohydrin resin comprises the following steps: mixing and reacting modified polyvinyl alcohol with the modified polyamide polymer.
8. The soy-based adhesive according to claim 7, wherein in the preparation method of the organic-inorganic hybrid modified polyamide epichlorohydrin resin, the mixing temperature is 60-80 ℃.
9. A process for preparing a soy-based adhesive as claimed in any one of claims 1 to 8, comprising: mixing the bean flour and the organic-inorganic hybrid modified polyamide epichlorohydrin resin.
10. An artificial board, characterized in that the raw materials for preparing the artificial board comprise the soy-based adhesive of any one of claims 1 to 8.
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