CN115838576B - Aldehyde-free adhesive and application thereof in preparation of P2-P12-grade particle board - Google Patents
Aldehyde-free adhesive and application thereof in preparation of P2-P12-grade particle board Download PDFInfo
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- CN115838576B CN115838576B CN202211607273.3A CN202211607273A CN115838576B CN 115838576 B CN115838576 B CN 115838576B CN 202211607273 A CN202211607273 A CN 202211607273A CN 115838576 B CN115838576 B CN 115838576B
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 39
- 239000000853 adhesive Substances 0.000 title claims abstract description 38
- 239000002245 particle Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims description 9
- 239000000839 emulsion Substances 0.000 claims abstract description 157
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 20
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 16
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000005977 Ethylene Substances 0.000 claims abstract description 13
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims abstract description 6
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 claims abstract description 3
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 claims abstract description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002023 wood Substances 0.000 claims description 33
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 27
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 21
- 239000011256 inorganic filler Substances 0.000 claims description 16
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 16
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000007800 oxidant agent Substances 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000003431 cross linking reagent Substances 0.000 claims description 12
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- 238000013329 compounding Methods 0.000 claims description 6
- 239000003995 emulsifying agent Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000011790 ferrous sulphate Substances 0.000 claims description 5
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- 239000001632 sodium acetate Substances 0.000 claims description 4
- 235000017281 sodium acetate Nutrition 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 230000009477 glass transition Effects 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 3
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 3
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 3
- 125000005442 diisocyanate group Chemical group 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 27
- 239000011093 chipboard Substances 0.000 abstract description 8
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000011120 plywood Substances 0.000 abstract description 2
- 239000003292 glue Substances 0.000 description 26
- 239000012792 core layer Substances 0.000 description 20
- 238000003756 stirring Methods 0.000 description 12
- 239000002344 surface layer Substances 0.000 description 12
- 238000005507 spraying Methods 0.000 description 10
- 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 description 7
- 239000003063 flame retardant Substances 0.000 description 7
- 229920001807 Urea-formaldehyde Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000428 dust Substances 0.000 description 6
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 6
- 239000004814 polyurethane Substances 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000000844 anti-bacterial effect Effects 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 125000003172 aldehyde group Chemical group 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 235000018102 proteins Nutrition 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 230000000391 smoking effect Effects 0.000 description 3
- VAPKHDZBJXRVNG-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene;1-ethenyl-4-methylbenzene Chemical group CC1=CC=C(C=C)C=C1.CC1=CC=CC(C=C)=C1 VAPKHDZBJXRVNG-UHFFFAOYSA-N 0.000 description 2
- 108010073771 Soybean Proteins Proteins 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- DOUHZFSGSXMPIE-UHFFFAOYSA-N hydroxidooxidosulfur(.) Chemical class [O]SO DOUHZFSGSXMPIE-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- QROGIFZRVHSFLM-UHFFFAOYSA-N prop-1-enylbenzene Chemical compound CC=CC1=CC=CC=C1 QROGIFZRVHSFLM-UHFFFAOYSA-N 0.000 description 2
- 235000019710 soybean protein Nutrition 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- -1 antibacterial Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000007688 edging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical group C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000017854 proteolysis Effects 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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- Adhesives Or Adhesive Processes (AREA)
- Dry Formation Of Fiberboard And The Like (AREA)
Abstract
The invention discloses an aldehyde-free adhesive and application thereof in preparing P2-P12-grade chipboards, and belongs to the technical field of plywood. The emulsion comprises emulsion A and emulsion B, wherein the emulsion A is prepared by solution polymerization of vinyl acetate, vinyl chloride and ethylene; the emulsion B is obtained by solution polymerization of a rigid monomer and butadiene, wherein the rigid monomer comprises at least one of styrene, p-methylstyrene, o-methylstyrene and m-methylstyrene. Under the synergistic effect of the emulsion A and the emulsion B, the particle board has excellent flame retardance, water resistance and physical and mechanical properties.
Description
Technical Field
The invention belongs to the technical field of plywood, and particularly relates to an aldehyde-free adhesive and application thereof in preparing P2-P12-grade chipboards.
Background
The main raw materials of the shaving board are wood fiber materials and adhesives, and some additives are added. The adhesive capability of the adhesive directly influences the strength, water resistance and other physical properties of the shaving board, and the environment-friendly characteristic of the adhesive also determines whether the shaving board is environment-friendly. In China, urea-formaldehyde glue, phenolic glue, melamine formaldehyde glue and the like with relatively low price are mainly used at present to produce the 'aldehyde-containing glue' which is mainly used for producing the shaving board used for furniture. However, as the name suggests, these adhesives all contain "aldehyde groups" which inevitably emit formaldehyde into the atmosphere during drying, resulting in health problems for the human body in such a household furniture environment.
With the improvement of people's environmental protection consciousness and the importance of self health, formaldehyde-free adhesives are gradually applied to the production of particle boards in the market. Among them, polyurethane adhesives, soybean protein adhesives, isocyanate adhesives (MDI) are the most predominant representatives. Polyurethane adhesives cure at a fast rate but at a high cost, and the too fast cure rate results in a short open time for the glue, which is not suitable for mass production. For example, patent CN108219714B uses polyurethane, acrylic emulsion, vinyl acetate-ethylene emulsion, and MDI to prepare an aldehyde-free adhesive, but the polyurethane itself dries fast, and MDI is matched to further accelerate the drying speed, resulting in uncontrollable production; on the other hand, the reaction of polyurethane and emulsion is random, and the quality of the obtained adhesive is unstable, resulting in poor reproducibility of each batch. Although the soybean protein adhesive is low in cost, the board is easy to be corroded by bacteria and mould in the environment to generate bacterial plaque due to organic components such as starch and protein degradation products, and the adhesive strength and the water resistance are poor, so that the shaving board is barely P2-grade. The patent CN111909653B uses aqueous polyether polyurethane and protein powder to prepare aldehyde-free adhesive, essentially uses the adhesive property of protein, and ethers have certain antibacterial property but are hydrophilic, and the existence of protein leads the adhesive to have the defect of insufficient water resistance. The MDI glue has strong crosslinking effect, the wood shaving board can reach P2 level with small dosage, and the dosage is up to P6 level with more dosage (with other inorganic fillers). The MDI glue used alone has certain limitation, the MDI glue used alone is easy to crack and the MDI glue itself is not water-resistant, so the water absorption expansion rate of the MDI glue cannot reach the standard, and the grade of the MDI glue is always wandering between P2 and P6.
Based on the above, there is a need to develop an adhesive which does not contain aldehyde groups, has moderate drying speed, and can ensure that the prepared shaving board has good water resistance, high strength and high grade up to P12 grade.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the formaldehyde-free adhesive which does not contain aldehyde groups and has moderate drying speed, and the prepared shaving board has good water resistance, high strength and the highest grade of P12.
In order to achieve the above purpose, the specific technical scheme of the invention is as follows:
the formaldehyde-free adhesive comprises emulsion, a cross-linking agent and inorganic filler, wherein the emulsion comprises emulsion A and emulsion B, and the emulsion A is prepared by solution polymerization of vinyl acetate, vinyl chloride and ethylene; the emulsion B is obtained by solution polymerization of a rigid monomer and butadiene, wherein the rigid monomer comprises at least one of styrene, p-methylstyrene, o-methylstyrene and m-methylstyrene.
According to the invention, the emulsion A is obtained by polymerizing vinyl acetate, vinyl chloride and ethylene, the emulsion B is obtained by polymerizing (methyl) styrene and butadiene, and the introduction of the vinyl chloride ensures that the emulsion contains chlorine element, so that the adhesive has antibacterial property; under the combined action of chlorine element and carboxyl in vinyl acetate, inorganic filler is externally added, so that the board has better flame-retardant property. The styrene monomer is adopted, and the benzene ring in the emulsion endows the sheet with high strength characteristics; the use of the vinyl chloride and the methyl styrene monomer ensures that the emulsion has strong hydrophobicity after being dried into a film, thus endowing the board with excellent water resistance. The inorganic filler is used, so that the plate is lubricated and is less prone to cracking during planing and edging, and the one-time production qualification rate of the plate is improved.
Under the synergistic effect of the emulsion A and the emulsion B, the particle board has excellent flame retardance, water resistance and physical and mechanical properties.
Preferably, the mass ratio of the emulsion A to the emulsion B is (1-3): 1-9. Particle boards with different performances can be obtained by adjusting the mass ratio of the emulsion A to the emulsion B; if the emulsion A in the shaving board is higher than the emulsion B, the shaving board has excellent flame retardant property; emulsion B in the particle board is higher than emulsion A, so that the particle board has high strength.
Preferably, the preparation method of the emulsion A comprises the following steps: adding solvent, emulsifier, acetic acid, sodium acetate and ferrous sulfate into a reaction container, and uniformly mixing; then adding vinyl acetate, vinyl chloride and ethylene, heating to 40-60 ℃, then dripping a reducing agent and an oxidizing agent, and reacting for 10-12 hours to obtain the emulsion A. Acetic acid, sodium acetate and ferrous sulfate are added in the reaction, so that the polymerization reaction of vinyl acetate can be promoted.
Preferably, the preparation method of the emulsion B comprises the following steps: adding a solvent, an emulsifying agent, an oxidizing agent and a rigid monomer into a reaction container, and heating to 80 ℃ for reaction for 1-2 h to obtain emulsion seeds; adding a solvent, emulsion seeds, an emulsifying agent, sodium metabisulfite and ferrous sulfate into a reaction container, then adding a rigid monomer and butadiene, heating to 55-75 ℃, then dripping a reducing agent and an oxidizing agent, and reacting for 8-10 hours to obtain the emulsion B.
Preferably, the mass percentage of the ethylene monomer is 30-50%, the mass percentage of the vinyl acetate monomer is 30-50%, and the mass percentage of the acrylic monomer is 15-30% based on the total mass of the ethylene monomer, the vinyl acetate monomer and the acrylic monomer.
Preferably, the mass ratio of the vinyl acetate to the vinyl chloride to the ethylene is (2-3): 3-5): 1.
Preferably, the mass ratio of the rigid monomer to butadiene is (1-1.5): 1.
Preferably, the oxidant is potassium persulfate or sodium persulfate, and the reducing agent is ascorbic acid or sulfinate derivatives.
Preferably, the mass ratio of the emulsion, the cross-linking agent and the inorganic filler is 83 (9-14): 9-42.
Preferably, the solid content of the emulsion A is 50-70% and the solid content of the emulsion B is 50-70% by weight.
Preferably, the viscosity of the emulsion is 500-20000 mPas and the glass transition temperature is 20-45 ℃.
Preferably, the crosslinking agent comprises at least one of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polydiphenylmethane diisocyanate (pMDI), isophorone diisocyanate (IPDI), hexamethylene Diisocyanate (HDI); the inorganic filler is calcium carbonate, and the particle size of the calcium carbonate is 400-4000 meshes.
The invention also provides application of the formaldehyde-free adhesive in preparing P2-P12-grade shaving boards, wherein the mass ratio of emulsion A to emulsion B in the surface layer of the shaving board is (2-3): 1, and the mass ratio of emulsion A to emulsion B in the core layer of the shaving board is (3-9).
The specific application method is as follows:
s1, mixing the emulsion A and the emulsion B according to the mass ratio of (2-3) to 1, and then adding the emulsion obtained by compounding, the cross-linking agent and the inorganic filler into the wood shavings, and uniformly mixing to obtain the surface wood shavings;
s2, mixing the emulsion A and the emulsion B according to the mass ratio of 1 (3-9), and then adding the emulsion obtained by compounding, the cross-linking agent and the inorganic filler into the wood shavings, and uniformly mixing to obtain the core wood shavings;
s3, paving and pressing to form.
By limiting the mass ratio of the emulsion A and the emulsion B in the core layer and the surface layer of the shaving board respectively, the shaving board with flame retardance, antibacterial property, water resistance and high strength can be obtained. The emulsion A in the surface layer of the shaving board is higher than the emulsion B, so that the surface layer of the shaving board has excellent flame retardant property; the emulsion B in the wood shaving board core layer occupies higher than the emulsion A, so that the wood shaving board core layer has high strength.
More preferably, the formaldehyde-free adhesive is applied to the preparation of P12-grade chipboards, wherein the mass ratio of emulsion A to emulsion B in the surface layer of the chipboard is 3:1, and the mass ratio of emulsion A to emulsion B in the core layer of the chipboard is 1:6.
The specific application method is as follows:
mixing the emulsion A and the emulsion B according to a mass ratio of 3:1, adding the emulsion obtained by compounding, a cross-linking agent and an inorganic filler into wood shavings, and uniformly mixing to obtain surface wood shavings;
m2, mixing the emulsion A and the emulsion B according to a mass ratio of 1:6, and then adding the emulsion obtained by compounding, the cross-linking agent and the inorganic filler into the wood shavings, and uniformly mixing to obtain core layer wood shavings;
and M3, paving and pressing to form.
When the mass ratio of emulsion A to emulsion B in the surface layer of the shaving board is 3:1 and the mass ratio of emulsion A to emulsion B in the core layer of the shaving board is 1:6, the produced shaving board has the advantages of optimal performance, highest strength and optimal water resistance, and all performance indexes can reach the P12 level standard. Compared with the prior art, the invention has the following advantages:
the invention adopts vinyl acetate, vinyl chloride and ethylene to obtain emulsion A through polymerization, adopts (methyl) styrene and butadiene to obtain emulsion B through polymerization, and the introduction of the vinyl chloride ensures that the emulsion contains chlorine element, so that the adhesive has antibacterial property; under the combined action of chlorine element and carboxyl in vinyl acetate, inorganic filler is externally added, so that the board has excellent flame-retardant property. The styrene monomer is adopted, and the benzene ring in the emulsion endows the sheet with high strength characteristics; the use of the vinyl chloride and the methyl styrene monomer ensures that the emulsion has strong hydrophobicity after being dried into a film, thus endowing the board with excellent water resistance.
Under the synergistic effect of the emulsion A and the emulsion B, the particle board has excellent flame retardance, water resistance and physical and mechanical properties.
Drawings
FIG. 1 is a pre-fired board, wherein A is a commercially available urea-formaldehyde board, B is a commercially available MDI board, and C is a board of the present invention;
fig. 2 shows a board after 60s of firing of an alcohol lamp, wherein a is a commercially available urea-formaldehyde glue board, B is a commercially available MDI glue board, and C is a glue board of the present invention.
Detailed Description
The following description of the present invention will be made clearly and fully, and it is apparent that the embodiments described are only some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by one of ordinary skill in the art without undue burden on the person of ordinary skill in the art based on embodiments of the present invention, are within the scope of the present invention.
In the following examples and comparative examples, emulsion A was prepared as follows:
using autoclaves with agitators, temperature controllers, pressure controllers and feed/discharge portsAs a reaction vessel, N is firstly used as air in the kettle 2 And replacing for three times, and vacuumizing. Then 1500g of pure water, 122g of sodium dodecyl sulfate, 2g of acetic acid, 1g of sodium acetate and 0.05g of ferrous sulfate hydrate are added into the autoclave under stirring, and uniformly mixed; by N 2 220g of vinyl acetate, 350g of vinyl chloride and 160g of ethylene are added after replacement deoxidization, 81.2g of reducing agent ascorbic acid (3.65% concentration water solution) and 80g of low concentration oxidant sodium persulfate (3.75% concentration water solution) are added at the same time after the temperature is raised to 50 ℃, the adding time is 450min, the monomers including 500g of vinyl acetate, 900g of vinyl chloride and 160g of ethylene are continuously added while the low concentration oxidant is added at the same time to keep the pressure in the kettle constant at 25bar, the adding time of the monomers is 360min, and 43g and 120min of high concentration oxidant sodium persulfate (8.3% concentration water solution) are added after the adding of the low concentration oxidant is finished. And (3) after all the oxidizing agents are added dropwise, curing for 60min, and discharging after pressure relief, so as to obtain emulsion A with the solid content of 55%, the viscosity of 850 mPa.s and the Tg of 30 ℃.
The preparation method of the emulsion B comprises the following steps:
(1) Preparing emulsion seeds: 1257g of pure water, 0.7g of sodium dodecyl sulfate, 62.37g of styrene and 20g of potassium persulfate are added into a reaction kettle, and the mixture is heated to 80 ℃ and then reacted for 90 minutes to obtain emulsion seeds;
(2) An autoclave with a stirrer, a temperature controller, a pressure controller and a feed inlet and a feed outlet is used as a reaction vessel, and N is firstly used as air in the autoclave 2 And replacing for three times, and vacuumizing. Then 396g of pure water, 1007.3g of emulsion seeds, 15g of sodium dodecyl sulfate, 2.2g of sodium metabisulfite and 0.066g of ferrous sulfate hydrate were added to the autoclave under stirring; by N 2 528g of styrene and 528g of butadiene are added after replacement and deoxidization, 140.8g of the sulfinate derivative (3% concentration water solution) of the reducing agent and 264.2g of the sodium persulfate (7.5% concentration water solution) of the low concentration oxidizing agent are added dropwise after the temperature is raised to 65 ℃, the dropwise adding time is 720min, the monomers including 792g of styrene and 528g of butadiene are continuously added when the reaction starts for 180min, and the adding time of the monomers is 240min. And discharging after all the oxidizing agents are added dropwise, and obtaining emulsion B with the solid content of 55%, the viscosity of 600 mPa.s and the Tg of 38 ℃.
The viscosity of the above emulsion was measured at room temperature using a BROOKFIELD viscometer, the glass transition temperature was measured by DSC, and the solid content was measured according to GB/T27573-2011.
Example 1
The embodiment provides an application of an aldehyde-free adhesive in preparing P2 particle boards, which comprises the following steps:
s1, mixing emulsion A and emulsion B according to a mass ratio of 1:1 to obtain mixed emulsion, and then spraying 450g of mixed emulsion, 50g of toluene diisocyanate and 50g of heavy calcium carbonate into 1368g of surface fine wood dust respectively, and fully and uniformly stirring for later use;
s2, mixing the emulsion A and the emulsion B according to a mass ratio of 1:1 to obtain mixed emulsion, and then respectively spraying 380g of mixed emulsion, 40g of toluene diisocyanate and 40g of heavy calcium carbonate into 2046g of core layer coarse wood chips, and fully and uniformly stirring for later use;
s3, pressing the wood chips after the glue mixing into a plate with the breadth of 520 x 18mm by adopting an oil pressure forming machine produced by tin-free yangming rubber machinery Co-efficient, and curing for 72 hours.
Example 2
The embodiment provides an application of an aldehyde-free adhesive in preparing P6 particle boards, which comprises the following steps:
s1, mixing emulsion A and emulsion B according to a mass ratio of 3:1 to obtain mixed emulsion, and then spraying 450g of mixed emulsion, 68g of toluene diisocyanate and 112g of heavy calcium carbonate into 1368g of surface fine wood dust respectively, and fully and uniformly stirring for later use;
s2, mixing the emulsion A and the emulsion B according to the mass ratio of 1:3 to obtain mixed emulsion, and then respectively spraying 380g of mixed emulsion, 57g of toluene diisocyanate and 95g of heavy calcium carbonate into 2046g of core layer coarse wood chips, and fully and uniformly stirring for later use;
s3, pressing the wood chips after the glue mixing into a plate with the breadth of 520 x 18mm by adopting an oil pressure forming machine produced by tin-free yangming rubber machinery Co-efficient, and curing for 72 hours.
Example 3
The embodiment provides an application of an aldehyde-free adhesive in preparing P12 particle boards, which comprises the following steps:
s1, mixing emulsion A and emulsion B according to a mass ratio of 3:1 to obtain mixed emulsion, then spraying 450g of mixed emulsion, 70g of diphenylmethane diisocyanate and 200g of heavy calcium carbonate into 1368g of surface fine wood dust respectively, and fully and uniformly stirring for later use;
s2, mixing the emulsion A and the emulsion B according to the mass ratio of 1:6 to obtain mixed emulsion, then respectively spraying 380g of mixed emulsion, 60g of diphenylmethane diisocyanate and 200g of heavy calcium carbonate into 2046g of core layer coarse wood chips, and fully and uniformly stirring for later use;
s3, pressing the wood chips after the glue mixing into a plate with the breadth of 520 x 18mm by adopting an oil pressure forming machine produced by tin-free yangming rubber machinery Co-efficient, and curing for 72 hours.
Example 4
The embodiment provides an application of an aldehyde-free adhesive in preparing P10 particle boards, which comprises the following steps:
s1, mixing emulsion A and emulsion B according to a mass ratio of 3:1 to obtain mixed emulsion, then spraying 450g of mixed emulsion, 70g of toluene diisocyanate and 200g of heavy calcium carbonate into 1368g of surface fine wood dust respectively, and fully and uniformly stirring for later use;
s2, mixing the emulsion A and the emulsion B according to the mass ratio of 1:9 to obtain mixed emulsion, then respectively spraying 430g of mixed emulsion, 65g of toluene diisocyanate and 215g of heavy calcium carbonate into 2046g of core layer coarse wood chips, and fully and uniformly stirring for later use;
s3, pressing the wood chips after the glue mixing into a plate with the breadth of 520 x 18mm by adopting an oil pressure forming machine produced by tin-free yangming rubber machinery Co-efficient, and curing for 72 hours.
Comparative example 1
S1, respectively spraying 450g of emulsion A, 70g of diphenylmethane diisocyanate and 200g of heavy calcium carbonate into 1368g of surface fine wood dust, and fully and uniformly stirring for later use;
s2, respectively spraying 380g of emulsion B, 60g of diphenylmethane diisocyanate and 200g of heavy calcium carbonate into 2046g of core layer coarse wood dust, and fully and uniformly stirring for later use;
s3, pressing the wood chips after the glue mixing into a plate with the breadth of 520 x 18mm by adopting an oil pressure forming machine produced by tin-free yangming rubber machinery Co-efficient, and curing for 72 hours.
The performance of the chipboard of examples and comparative examples was tested according to the requirements related to GB/T4897-2015 particle board and the test results are shown in Table 1.
TABLE 1 particle Board Performance results
As can be seen from the data in Table 1, examples 1 to 4 of the present invention can obtain flame-retardant, antibacterial, water-resistant, high-strength particle boards by adjusting the mass ratio of the emulsions A and B in the core layer and the surface layer of the wood shaving board. As can be seen from comparative examples 2 to 4 and comparative example 1, the strength and water resistance of the chipboard are firstly enhanced and then reduced with the increase of the emulsion B ratio in the chipboard core layer; when the mass ratio of emulsion A to emulsion B in the surface layer of the shaving board is 3:1 and the mass ratio of emulsion A to emulsion B in the core layer of the shaving board is 1:6 (example 3), the produced shaving board has the advantages of best performance, highest strength and best water resistance, and all performance indexes can reach the P12 level standard.
Although the emulsion A in the surface layer of the shaving board is higher than the emulsion B, the surface layer of the shaving board can have excellent flame retardant property; the emulsion B in the wood shaving board core layer occupies higher than the emulsion A, so that the wood shaving board core layer has high strength. However, when the surface layer of the particle board contains only emulsion A and the core layer contains only emulsion B (comparative example 1), the performance of the particle board can only marginally meet the P2 requirement. The defect that the shaving board with good water resistance and high strength cannot be obtained due to too much or too little emulsion B in the shaving board core layer is overcome; emulsion A and emulsion B in the core layer and the surface layer of the shaving board are required to be within the proportion range defined by the invention so as to obtain the shaving board with flame retardance, water resistance and high strength.
Comparing the flame retardancy of the commercial urea-formaldehyde glue board, the commercial MDI glue board and the board of example 3, fig. 1 is a board before firing, wherein a is the commercial urea-formaldehyde glue board, B is the commercial MDI glue board, and C is the glue board of the present invention; fig. 2 shows a board after the alcohol lamp burns for 60s, the urea-formaldehyde glue board A sold in the market burns for 60s through the alcohol lamp, smoke starts at 15s, smoke starts at 30s, the smoke is bigger and bigger, and the carbonized area of the board is bigger. The commercial MDI glue board material B is burnt for 60s by an alcohol lamp, the 16 th s starts smoking, the 33 th s starts smoking to be bigger and bigger, and the carbonization area of the board surface is maximum. The sheet C of example 3 was burned by an alcohol burner for 60 seconds without smoking, and the burned area was slightly carbonized, and the carbonized area was small. Therefore, the particle board prepared from the adhesive has excellent flame retardant property.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. The formaldehyde-free adhesive is characterized by comprising emulsion, a cross-linking agent and an inorganic filler, wherein the emulsion comprises emulsion A and emulsion B, and the emulsion A is prepared by solution polymerization of vinyl acetate, vinyl chloride and ethylene; the emulsion B is obtained by solution polymerization of a rigid monomer and butadiene, wherein the rigid monomer comprises at least one of styrene, p-methylstyrene, o-methylstyrene and m-methylstyrene;
the mass ratio of the emulsion A to the emulsion B is (1-3): 1-9;
the mass ratio of the vinyl acetate to the vinyl chloride to the ethylene is (2-3): 3-5): 1; the mass ratio of the rigid monomer to butadiene is (1-1.5): 1;
the mass ratio of the emulsion to the cross-linking agent to the inorganic filler is 83 (9-14) to 9-42.
2. The formaldehyde-free adhesive according to claim 1, wherein the preparation method of the emulsion a comprises the following steps: adding solvent, emulsifier, acetic acid, sodium acetate and ferrous sulfate into a reaction vessel, uniformly mixing, then adding vinyl acetate, vinyl chloride and ethylene, heating to 40-60 ℃, then dripping reducing agent and oxidizing agent, and reacting for 10-12 h to obtain the emulsion A.
3. The formaldehyde-free adhesive according to claim 1, wherein the preparation method of the emulsion B comprises the following steps: adding a solvent, an emulsifying agent, an oxidizing agent and a rigid monomer into a reaction container, and heating to 80 ℃ for reaction for 1-2 h to obtain emulsion seeds; adding a solvent, emulsion seeds, an emulsifying agent, sodium metabisulfite and ferrous sulfate into a reaction container, then adding a rigid monomer and butadiene, heating to 55-75 ℃, then dripping a reducing agent and an oxidizing agent, and reacting for 8-10 hours to obtain the emulsion B.
4. The formaldehyde-free adhesive according to claim 1, wherein the emulsion has a viscosity of 500 to 20000 mPa-s and a glass transition temperature of 20 to 45 ℃.
5. An aldehyde-free adhesive according to claim 1, wherein the cross-linking agent comprises at least one of toluene diisocyanate, diphenylmethane diisocyanate, polydiphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate; the inorganic filler is calcium carbonate, and the particle size of the calcium carbonate is 400-4000 meshes.
6. Use of an aldehyde-free adhesive according to any one of claims 1 to 5 for the preparation of P2-P12 particle board, characterized in that the method of application is as follows:
s1, mixing the emulsion A and the emulsion B according to the mass ratio of (2-3) to 1, and then adding the emulsion obtained by compounding, the cross-linking agent and the inorganic filler into the wood shavings, and uniformly mixing to obtain the surface wood shavings;
s2, mixing the emulsion A and the emulsion B according to the mass ratio of 1 (3-9), and then adding the emulsion obtained by compounding, the cross-linking agent and the inorganic filler into the wood shavings, and uniformly mixing to obtain the core wood shavings;
s3, paving and pressing to form.
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| CN114213999A (en) * | 2021-12-13 | 2022-03-22 | 云南正邦科技有限公司 | Water-based formaldehyde-free adhesive |
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Denomination of invention: A formaldehyde free adhesive and its application in the preparation of P2-P12 grade particleboard Granted publication date: 20230606 Pledgee: Kunming Branch of China Minsheng Bank Co.,Ltd. Pledgor: YUNNAN ZHENGBANG TECHNOLOGY CO.,LTD. Registration number: Y2023530000069 |