CN117645859B - Formaldehyde-free environment-friendly wood veneer board and preparation process thereof - Google Patents
Formaldehyde-free environment-friendly wood veneer board and preparation process thereof Download PDFInfo
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- CN117645859B CN117645859B CN202311635453.7A CN202311635453A CN117645859B CN 117645859 B CN117645859 B CN 117645859B CN 202311635453 A CN202311635453 A CN 202311635453A CN 117645859 B CN117645859 B CN 117645859B
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- 239000002023 wood Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 62
- 239000000178 monomer Substances 0.000 claims abstract description 50
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229920002635 polyurethane Polymers 0.000 claims abstract description 33
- 239000004814 polyurethane Substances 0.000 claims abstract description 33
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 25
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000005770 Eugenol Substances 0.000 claims abstract description 24
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229960002217 eugenol Drugs 0.000 claims abstract description 24
- 238000007731 hot pressing Methods 0.000 claims abstract description 23
- IIYDTSAAECYHAE-UHFFFAOYSA-N 2-methylidenebutanoyl chloride Chemical compound CCC(=C)C(Cl)=O IIYDTSAAECYHAE-UHFFFAOYSA-N 0.000 claims abstract description 22
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000004513 sizing Methods 0.000 claims abstract description 17
- 238000004132 cross linking Methods 0.000 claims abstract description 16
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 14
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims description 52
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 44
- 239000000758 substrate Substances 0.000 claims description 44
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 34
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 31
- 239000011248 coating agent Substances 0.000 claims description 27
- 238000000576 coating method Methods 0.000 claims description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 26
- 239000003999 initiator Substances 0.000 claims description 24
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000003995 emulsifying agent Substances 0.000 claims description 16
- 239000003973 paint Substances 0.000 claims description 15
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 13
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 13
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 12
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 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 12
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 11
- 238000007599 discharging Methods 0.000 claims description 11
- 230000001804 emulsifying effect Effects 0.000 claims description 11
- 238000007689 inspection Methods 0.000 claims description 11
- 238000003475 lamination Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- -1 sanding Substances 0.000 claims description 11
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 11
- 238000003892 spreading Methods 0.000 claims description 11
- 230000007480 spreading Effects 0.000 claims description 11
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 10
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000010025 steaming Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229920001971 elastomer Polymers 0.000 claims description 8
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 3
- 229920000053 polysorbate 80 Polymers 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 12
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 7
- 239000000376 reactant Substances 0.000 abstract description 6
- 238000010382 chemical cross-linking Methods 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000003292 glue Substances 0.000 description 20
- 230000001070 adhesive effect Effects 0.000 description 15
- 239000000853 adhesive Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000011203 carbon fibre reinforced carbon Chemical group 0.000 description 4
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- 230000036541 health Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- GLGIHGJHHSONCV-UHFFFAOYSA-N 1-sulfanylpropane-1,2-diol Chemical compound CC(O)C(O)S GLGIHGJHHSONCV-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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- 239000013067 intermediate product Substances 0.000 description 1
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
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Landscapes
- Chemical And Physical Treatments For Wood And The Like (AREA)
Abstract
The invention relates to the field of wood veneer boards, in particular to a formaldehyde-free environment-friendly wood veneer board and a preparation process thereof. Firstly, reacting 3-mercapto-1, 2-propanediol with eugenol according to a molar ratio of 1:1, and then reacting a reactant with 2-ethyl acryloyl chloride according to a molar ratio of 1:1 to obtain a functional monomer; polymerizing functional monomers, water, methyl methacrylate, ethyl acrylate, crosslinking monomers and the like to obtain polyacrylate, introducing polyurethane prepolymer into the side chain of the polyacrylate, and forming the polyurethane modified polyacrylate sizing material with a three-dimensional network structure through chemical crosslinking. The polyurethane modified polyacrylate sizing material is coated on the surface of a wood panel, and the wood facing board with strong adhesion performance and good antibacterial effect is obtained through hot pressing and post-treatment. In the preparation process, the traditional formaldehyde-containing sizing material is not added, and the invention is healthy, environment-friendly and pollution-free.
Description
Technical Field
The invention relates to the technical field of wood veneer, in particular to a formaldehyde-free environment-friendly wood veneer board and a preparation process thereof.
Background
With the continuous improvement of living standard, the requirements of consumer groups on interior decoration are changed from the aspect of pursuing beauty to the aspect of pursuing beauty and health. The wood veneer is usually made of an artificial wood board as a base layer, a veneer can be selected as a decoration panel according to design requirements, and finally the wood veneer is applied to wood veneer corners hung on keels, so that indoor effects are pleasant. However, the decorative panels existing in the market at present usually adopt formaldehyde-containing trialdehyde glue in the production process, and free formaldehyde released by the glue exceeds standard, so that the problem of indoor environmental pollution is often caused, and the direct threat to human health is formed. For this reason, it is important to prepare an environment-friendly panel using an aldehyde-free adhesive. The adhesive with stable performance and high bonding strength can ensure that the panel is normal in production operation, and the quality of the prepared product meets the standard. Compared with the trialdehyde glue, the water-based adhesive takes water as a medium, is more environment-friendly and healthy, and can be used for preparing formaldehyde-free environment-friendly wood veneer.
Disclosure of Invention
The invention aims to provide a formaldehyde-free environment-friendly wood veneer board and a preparation process thereof, which are used for solving the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: a formaldehyde-free environment-friendly wood veneer board and a preparation process thereof comprise the following steps:
step 1:
S1: mixing 3-mercapto-1, 2-propanediol and eugenol, adding an initiator azodiisobutyronitrile, reacting for 3-5 hours under the irradiation of a 100-120W ultraviolet lamp, adding triethanolamine and methylene dichloride, stirring under the ice bath condition, adding 2-ethyl acryloyl chloride for 3-5 times, and reacting for 10-15 minutes under single stirring; then heating to 25-35 ℃ for reaction for 48-55 h, extracting with saturated brine, drying, rotary steaming, distilling under reduced pressure, purifying to obtain functional monomers;
S2: mixing water, methyl methacrylate, ethyl acrylate, a crosslinking monomer DS-65, a functional monomer and an emulsifier, heating to 45-65 ℃, emulsifying for 1-2 h, adding an initiator, heating to 70-80 ℃, reacting for 0.5-1 h, drying and discharging to obtain polyacrylate;
S3: dehydrating raw materials, mixing polytetrahydrofuran ether glycol 2000 and isophorone diisocyanate in a nitrogen environment, heating to 70-80 ℃, adding dibutyltin dilaurate, and reacting for 2-3 hours to obtain a polyurethane prepolymer;
S4: mixing polyurethane prepolymer, polyacrylate and acetone, reacting for 1-2 hours at 70-80 ℃, adding triethylamine, reacting for 5-10 minutes, adding deionized water and ethylenediamine, reacting for 3-5 minutes, heating to remove acetone, and obtaining polyurethane modified polyacrylate sizing material;
step 2:
Selecting a wood board as a panel substrate, repairing and flattening the uneven part of the surface of the panel substrate, sanding, and coating polyurethane modified polyacrylate rubber on the panel substrate; spreading the veneer on the surface of the panel substrate to be glued, and performing hot pressing lamination; and (3) carrying out UV paint surface curing on the surface of the wood veneer after manual inspection and finishing to obtain the formaldehyde-free environment-friendly wood veneer.
Further, in S1, the molar ratio of 3-mercapto-1, 2-propanediol, eugenol and 2-ethyl acryloyl chloride is 1:1:1.
In S2, the weight percentage of each component is 7-10 percent of methyl methacrylate, 30-45 percent of ethyl acrylate, 3-8 percent of crosslinking monomer DS-65, 5-10 percent of functional monomer, 1-3 percent of emulsifier, 0.1-0.3 percent of initiator azodiisobutyronitrile, and the balance of water.
In S2, the emulsifier is any one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, tween 80 and span 80.
In S3, the mass ratio of polytetrahydrofuran ether glycol 2000 to isophorone diisocyanate is (80-100) (50-60).
Further, in S4, the amounts of the components in the polyurethane modified polyacrylate rubber material are 23-36 parts of polyurethane prepolymer, 72-85 parts of polyacrylate, 100 parts of acetone, 5-8 parts of triethylamine, 30-40 parts of deionized water and 2-3 parts of ethylenediamine in percentage by weight.
Further, in the step2, the thickness of the wood board is 5-15 mm.
Further, in the step 2, the coating thickness of the coating is 2-3 mm.
Further, in the step 2, the hot pressing temperature is 100-120 ℃; the pressure is 8-10 Mpa.
Compared with the prior art, the invention has the following beneficial effects: the invention prepares the sizing material with strong adhesive property, water resistance and excellent antibacterial effect, replaces the traditional sizing material containing formaldehyde, and is used for preparing wood veneer boards. According to the invention, 3-mercapto-1, 2-propanediol and eugenol are reacted according to a molar ratio of 1:1, then reactants are reacted with 2-ethyl acryloyl chloride according to a molar ratio of 1:1, and a functional monomer is obtained. The functional monomer retains the antibacterial property of eugenol, and simultaneously introduces 2 hydroxyl groups and carbon-carbon double bonds. The functional monomer is mixed with the soft monomer, the hard monomer and the crosslinking monomer to prepare polyacrylate, then the polyurethane prepolymer blocked by the terminal isocyanate group is added to modify the polyacrylate, after the isocyanate group and the hydroxyl react, the polyurethane is connected to the side chain of the polyacrylate, and the polyurethane of the side chain is further crosslinked with the polyacrylate of other main chains, so that a three-dimensional network structure is formed.
In the preparation of functional monomers, the reaction sequence of the reactants cannot be changed or the reactants cannot be directly reacted by blending. On one hand, since eugenol has a unique allyl structure, electron-rich carbon-carbon double bonds and olefin substituents can stabilize a carbon center free radical intermediate, chain transfer reaction between sulfhydryl groups and carbon-carbon double bonds is taken as the main part in the reaction process, so that homopolymerization reaction among eugenol is inhibited, if the sequence of reactants is changed, sulfhydryl-1, 2-propanediol and 2-ethyl acryloyl chloride react first, 2-ethyl acryloyl chloride is copolymerized, and functional monomers cannot be obtained, so that subsequent eugenol grafting reaction and polymerization reaction are influenced; if 2-ethyl acryloyl chloride reacts with eugenol firstly and then reacts with mercapto-1, 2-propylene glycol, intermediate products of the reaction of 2-ethyl acryloyl chloride and eugenol can undergo self-polymerization, and target functional monomers can not be obtained; on the other hand, if the reactants are directly blended, eugenol and 2-ethyl acryloyl chloride polymerize, and the functional monomer is not obtained as well. In addition, the amount of 3-mercapto-1, 2-propanediol also has an effect, and if the amount is too large, unreacted 3-mercapto-1, 2-propanediol subsequently reacts with 2-ethyl acryloyl chloride, consuming carbon-carbon double bonds, reducing the purity of the functional monomer, so that the 3-mercapto-1, 2-propanediol and eugenol must be reacted first, while the molar ratio of the three is strictly controlled to be 1:1:1.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the invention, the materials and sources thereof are as follows: polytetrahydrofuran ether glycol 2000 from new materials, model number DYT-005; the emulsifier is Tween 80, and is derived from Chinese medicinal materials; the wood board is from a Shenbo wood product factory, and the thickness of the pine wood strips is 5mm; the bark is from Jiayao bark with thickness of 0.25mm.
Example 1: a formaldehyde-free environment-friendly wood veneer board and a preparation process thereof comprise the following steps:
step 1:
S1: 1mol of 3-mercapto-1, 2-propanediol and 1mol of eugenol are mixed, 0.03mol of initiator azodiisobutyronitrile is added, after the reaction is carried out for 3 hours under the irradiation of a 100W ultraviolet lamp, 0.8mol of triethanolamine and 1.7mol of dichloromethane are added, stirring is carried out under the ice bath condition, 1.6mol of 2-ethyl acryloyl chloride is added for 3 times, and single stirring reaction is carried out for 10 minutes; then heating to 25 ℃ for reaction for 48 hours, extracting with saturated brine, drying, rotary steaming, distilling under reduced pressure, and purifying to obtain a functional monomer;
S2: mixing 32.7% of water, 10% of methyl methacrylate, 45% of ethyl acrylate, 5% of crosslinking monomer DS-65, 5% of functional monomer and 2% of emulsifying agent according to weight percentage, heating to 45 ℃, emulsifying for 1h, adding 0.3% of initiator azodiisobutyronitrile, heating to 70 ℃, reacting for 0.5h, drying and discharging to obtain polyacrylate;
S3: dehydrating raw materials, mixing 80g of polytetrahydrofuran ether glycol 2000 and 65g of isophorone diisocyanate in a nitrogen environment, heating to 70 ℃, adding dibutyl tin dilaurate accounting for 3% of the total mass of a mixed system, and reacting for 2 hours to obtain a polyurethane prepolymer;
s4: mixing 23g of polyurethane prepolymer, 85g of polyacrylate and 100g of acetone, reacting for 1h at 70 ℃, adding 5g of triethylamine, reacting for 5min, adding 40g of deionized water and 3g of ethylenediamine, reacting for 5min, and heating to remove acetone to obtain polyurethane modified polyacrylate sizing material;
step 2:
Selecting a wood board with the thickness of 5mm as a panel substrate, repairing and flattening the uneven part of the surface of the panel substrate, sanding, and coating polyurethane modified polyacrylate glue on the panel substrate, wherein the coating thickness is 2mm; spreading veneer on the surface of the panel substrate coated with glue, and performing hot-pressing lamination, wherein the hot-pressing temperature is 100 ℃; the pressure is 8Mpa; and (3) carrying out UV paint surface curing on the surface of the wood veneer after manual inspection and finishing to obtain the formaldehyde-free environment-friendly wood veneer.
Example 2: a formaldehyde-free environment-friendly wood veneer board and a preparation process thereof comprise the following steps:
step 1:
S1: 1mol of 3-mercapto-1, 2-propanediol and 1mol of eugenol are mixed, 0.03mol of initiator azodiisobutyronitrile is added, after reaction for 4 hours under the irradiation of a 110W ultraviolet lamp, 0.8mol of triethanolamine and 1.7mol of dichloromethane are added, stirring is carried out under the ice bath condition, 1.6mol of 2-ethyl acryloyl chloride is added for 4 times, and single stirring reaction is carried out for 13 minutes; then heating to 30 ℃ for reaction for 52 hours, extracting with saturated brine, drying, rotary steaming, distilling under reduced pressure, and purifying to obtain a functional monomer;
S2: mixing 32.7% of water, 10% of methyl methacrylate, 45% of ethyl acrylate, 5% of crosslinking monomer DS-65, 5% of functional monomer and 2% of emulsifying agent, heating to 55 ℃, emulsifying for 1.5h, adding 0.3% of initiator azodiisobutyronitrile, heating to 75 ℃, reacting for 0.5h, drying and discharging to obtain polyacrylate;
S3: dehydrating raw materials, mixing 80g of polytetrahydrofuran ether glycol 2000 and 65g of isophorone diisocyanate in a nitrogen environment, heating to 75 ℃, adding dibutyl tin dilaurate accounting for 3% of the total mass of the mixed system, and reacting for 2.5h to obtain a polyurethane prepolymer;
S4: mixing 23g of polyurethane prepolymer, 85g of polyacrylate and 100g of acetone, reacting for 1.5 hours at 75 ℃, adding 5g of triethylamine, reacting for 8 minutes, adding 40g of deionized water and 3g of ethylenediamine, reacting for 5 minutes, and heating to remove the acetone to obtain polyurethane modified polyacrylate sizing material;
step 2:
Selecting a wood board with the thickness of 5mm as a panel substrate, repairing and flattening the uneven part of the surface of the panel substrate, sanding, and coating polyurethane modified polyacrylate glue on the panel substrate, wherein the coating thickness is 2mm; spreading veneer on the surface of the panel substrate coated with glue, and performing hot-pressing lamination, wherein the hot-pressing temperature is 110 ℃; the pressure is 9Mpa; and (3) carrying out UV paint surface curing on the surface of the wood veneer after manual inspection and finishing to obtain the formaldehyde-free environment-friendly wood veneer.
Example 3: a formaldehyde-free environment-friendly wood veneer board and a preparation process thereof comprise the following steps:
step 1:
S1: 1mol of 3-mercapto-1, 2-propanediol and 1mol of eugenol are mixed, 0.03mol of initiator azodiisobutyronitrile is added, after reaction for 5 hours under the irradiation of a 120W ultraviolet lamp, 0.8mol of triethanolamine and 1.7mol of dichloromethane are added, stirring is carried out under the ice bath condition, 1.6mol of 2-ethyl acryloyl chloride is added for 5 times, and single stirring reaction is carried out for 15 minutes; then heating to 35 ℃ for reaction for 55 hours, extracting with saturated brine, drying, rotary steaming, distilling under reduced pressure, and purifying to obtain a functional monomer;
s2: mixing 32.7% of water, 10% of methyl methacrylate, 45% of ethyl acrylate, 5% of crosslinking monomer DS-65, 5% of functional monomer and 2% of emulsifying agent according to weight percentage, heating to 65 ℃, emulsifying for 2 hours, adding 0.3% of initiator azodiisobutyronitrile, heating to 80 ℃, reacting for 1 hour, drying and discharging to obtain polyacrylate;
S3: dehydrating raw materials, mixing 80g of polytetrahydrofuran ether glycol 2000 and 65g of isophorone diisocyanate in a nitrogen environment, heating to 80 ℃, adding dibutyl tin dilaurate accounting for 3% of the total mass of the mixed system, and reacting for 3 hours to obtain a polyurethane prepolymer;
s4: mixing 23g of polyurethane prepolymer, 85g of polyacrylate and 100g of acetone, reacting for 2 hours at 80 ℃, adding 5g of triethylamine, reacting for 10 minutes, adding 40g of deionized water and 3g of ethylenediamine, reacting for 5 minutes, and heating to remove acetone to obtain polyurethane modified polyacrylate sizing material;
step 2:
selecting a wood board with the thickness of 5mm as a panel substrate, repairing and flattening the uneven part of the surface of the panel substrate, sanding, and coating polyurethane modified polyacrylate glue on the panel substrate, wherein the coating thickness is 2mm; spreading veneer on the surface of the panel substrate coated with glue, and performing hot-pressing lamination, wherein the hot-pressing temperature is 120 ℃; the pressure is 10Mpa; and (3) carrying out UV paint surface curing on the surface of the wood veneer after manual inspection and finishing to obtain the formaldehyde-free environment-friendly wood veneer.
Example 4: a formaldehyde-free environment-friendly wood veneer board and a preparation process thereof comprise the following steps:
step 1:
S1: 1mol of 3-mercapto-1, 2-propanediol and 1mol of eugenol are mixed, 0.03mol of initiator azodiisobutyronitrile is added, after the reaction is carried out for 3 hours under the irradiation of a 100W ultraviolet lamp, 0.8mol of triethanolamine and 1.7mol of dichloromethane are added, stirring is carried out under the ice bath condition, 1.6mol of 2-ethyl acryloyl chloride is added for 3 times, and single stirring reaction is carried out for 10 minutes; then heating to 25 ℃ for reaction for 48 hours, extracting with saturated brine, drying, rotary steaming, distilling under reduced pressure, and purifying to obtain a functional monomer;
S2: mixing 32.7% of water, 10% of methyl methacrylate, 45% of ethyl acrylate, 5% of crosslinking monomer DS-65, 5% of functional monomer and 2% of emulsifying agent according to weight percentage, heating to 45 ℃, emulsifying for 1h, adding 0.3% of initiator azodiisobutyronitrile, heating to 70 ℃, reacting for 0.5h, drying and discharging to obtain polyacrylate;
S3: dehydrating raw materials, mixing 80g of polytetrahydrofuran ether glycol 2000 and 65g of isophorone diisocyanate in a nitrogen environment, heating to 70 ℃, adding dibutyl tin dilaurate accounting for 3% of the total mass of a mixed system, and reacting for 2 hours to obtain a polyurethane prepolymer;
s4: mixing 28g of polyurethane prepolymer, 85g of polyacrylate and 100g of acetone, reacting for 1h at 80 ℃, adding 5g of triethylamine, reacting for 10min, adding 40g of deionized water and 3g of ethylenediamine, reacting for 5min, and heating to remove acetone to obtain polyurethane modified polyacrylate sizing material;
step 2:
selecting a wood board with the thickness of 5mm as a panel substrate, repairing and flattening the uneven part of the surface of the panel substrate, sanding, and coating polyurethane modified polyacrylate glue on the panel substrate, wherein the coating thickness is 2mm; spreading veneer on the surface of the panel substrate coated with glue, and performing hot-pressing lamination, wherein the hot-pressing temperature is 120 ℃; the pressure is 8Mpa; and (3) carrying out UV paint surface curing on the surface of the wood veneer after manual inspection and finishing to obtain the formaldehyde-free environment-friendly wood veneer.
Example 5: a formaldehyde-free environment-friendly wood veneer board and a preparation process thereof comprise the following steps:
step 1:
S1: 1mol of 3-mercapto-1, 2-propanediol and 1mol of eugenol are mixed, 0.03mol of initiator azodiisobutyronitrile is added, after reaction for 5 hours under the irradiation of a 120W ultraviolet lamp, 0.8mol of triethanolamine and 1.7mol of dichloromethane are added, stirring is carried out under the ice bath condition, 1.6mol of 2-ethyl acryloyl chloride is added for 5 times, and single stirring reaction is carried out for 10 minutes; then heating to 30 ℃ for reaction for 50 hours, extracting with saturated brine, drying, rotary steaming, distilling under reduced pressure, and purifying to obtain a functional monomer;
s2: mixing 32.7% of water, 10% of methyl methacrylate, 45% of ethyl acrylate, 5% of crosslinking monomer DS-65, 5% of functional monomer and 2% of emulsifying agent, heating to 55 ℃, emulsifying for 1.5h, adding 0.3% of initiator azodiisobutyronitrile, heating to 75 ℃, reacting for 1h, drying and discharging to obtain polyacrylate;
S3: dehydrating raw materials, mixing 80g of polytetrahydrofuran ether glycol 2000 and 65g of isophorone diisocyanate in a nitrogen environment, heating to 80 ℃, adding dibutyl tin dilaurate accounting for 3% of the total mass of the mixed system, and reacting for 3 hours to obtain a polyurethane prepolymer;
s4: mixing 32g of polyurethane prepolymer, 85g of polyacrylate and 100g of acetone, reacting for 1h at 80 ℃, adding 5g of triethylamine, reacting for 10min, adding 40g of deionized water and 3g of ethylenediamine, reacting for 5min, and heating to remove acetone to obtain polyurethane modified polyacrylate sizing material;
step 2:
Selecting a wood board with the thickness of 5mm as a panel substrate, repairing and flattening the uneven part of the surface of the panel substrate, sanding, and coating polyurethane modified polyacrylate glue on the panel substrate, wherein the coating thickness is 2mm; spreading veneer on the surface of the panel substrate coated with glue, and performing hot-pressing lamination, wherein the hot-pressing temperature is 110 ℃; the pressure is 9Mpa; and (3) carrying out UV paint surface curing on the surface of the wood veneer after manual inspection and finishing to obtain the formaldehyde-free environment-friendly wood veneer.
Example 6: a formaldehyde-free environment-friendly wood veneer board and a preparation process thereof comprise the following steps:
step 1:
S1: 1mol of 3-mercapto-1, 2-propanediol and 1mol of eugenol are mixed, 0.03mol of initiator azodiisobutyronitrile is added, after reaction for 4 hours under the irradiation of a 100W ultraviolet lamp, 0.8mol of triethanolamine and 1.7mol of dichloromethane are added, stirring is carried out under the ice bath condition, 1.6mol of 2-ethyl acryloyl chloride is added for 5 times, and single stirring reaction is carried out for 15 minutes; then heating to 35 ℃ for reaction for 55 hours, extracting with saturated brine, drying, rotary steaming, distilling under reduced pressure, and purifying to obtain a functional monomer;
s2: mixing 32.7% of water, 10% of methyl methacrylate, 45% of ethyl acrylate, 5% of crosslinking monomer DS-65, 5% of functional monomer and 2% of emulsifying agent according to weight percentage, heating to 65 ℃, emulsifying for 2 hours, adding 0.3% of initiator azodiisobutyronitrile, heating to 80 ℃, reacting for 1 hour, drying and discharging to obtain polyacrylate;
S3: dehydrating raw materials, mixing 80g of polytetrahydrofuran ether glycol 2000 and 65g of isophorone diisocyanate in a nitrogen environment, heating to 80 ℃, adding dibutyl tin dilaurate accounting for 3% of the total mass of the mixed system, and reacting for 3 hours to obtain a polyurethane prepolymer;
s4: mixing 36g of polyurethane prepolymer, 85g of polyacrylate and 100g of acetone, reacting for 1h at 80 ℃, adding 5g of triethylamine, reacting for 10min, adding 40g of deionized water and 3g of ethylenediamine, reacting for 5min, and heating to remove acetone to obtain polyurethane modified polyacrylate sizing material;
step 2:
selecting a wood board with the thickness of 5mm as a panel substrate, repairing and flattening the uneven part of the surface of the panel substrate, sanding, and coating polyurethane modified polyacrylate glue on the panel substrate, wherein the coating thickness is 2mm; spreading veneer on the surface of the panel substrate coated with glue, and performing hot-pressing lamination, wherein the hot-pressing temperature is 120 ℃; the pressure is 10Mpa; and (3) carrying out UV paint surface curing on the surface of the wood veneer after manual inspection and finishing to obtain the formaldehyde-free environment-friendly wood veneer.
Comparative example 1: the modification of the polyacrylate size without the addition of polyurethane prepolymers was carried out, the remaining parameters being the same as in example 1.
Step 1:
S1: 1mol of 3-mercapto-1, 2-propanediol and 1mol of eugenol are mixed, 0.03mol of initiator azodiisobutyronitrile is added, after the reaction is carried out for 3 hours under the irradiation of a 100W ultraviolet lamp, 0.8mol of triethanolamine and 1.7mol of dichloromethane are added, stirring is carried out under the ice bath condition, 1.6mol of 2-ethyl acryloyl chloride is added for 3 times, and single stirring reaction is carried out for 10 minutes; then heating to 25 ℃ for reaction for 48 hours, extracting with saturated brine, drying, rotary steaming, distilling under reduced pressure, and purifying to obtain a functional monomer;
s2: mixing 32.7% of water, 10% of methyl methacrylate, 45% of ethyl acrylate, 5% of crosslinking monomer DS-65, 5% of functional monomer and 2% of emulsifying agent according to weight percentage, heating to 45 ℃, emulsifying for 1h, adding 0.3% of initiator azodiisobutyronitrile, heating to 70 ℃, reacting for 0.5h, cooling and discharging to obtain polyacrylate sizing material;
step 2:
Selecting a wood board with the thickness of 5mm as a panel substrate, repairing and flattening the uneven part of the surface of the panel substrate, sanding, and coating polyacrylate rubber on the panel substrate, wherein the coating thickness is 2mm; spreading veneer on the surface of the panel substrate coated with glue, and performing hot-pressing lamination, wherein the hot-pressing temperature is 100 ℃; the pressure is 8Mpa; and (3) carrying out UV paint surface curing on the surface of the wood veneer after manual inspection and finishing to obtain the formaldehyde-free environment-friendly wood veneer.
Comparative example 2: in S4 the polyurethane was physically blended with the polyacrylate size and the remaining parameters were the same as in example 2.
Step 1:
S1: 1mol of 3-mercapto-1, 2-propanediol and 1mol of eugenol are mixed, 0.03mol of initiator azodiisobutyronitrile is added, after reaction for 4 hours under the irradiation of a 110W ultraviolet lamp, 0.8mol of triethanolamine and 1.7mol of dichloromethane are added, stirring is carried out under the ice bath condition, 1.6mol of 2-ethyl acryloyl chloride is added for 4 times, and single stirring reaction is carried out for 13 minutes; then heating to 30 ℃ for reaction for 52 hours, extracting with saturated brine, drying, rotary steaming, distilling under reduced pressure, and purifying to obtain a functional monomer;
S2: mixing 32.7% of water, 10% of methyl methacrylate, 45% of ethyl acrylate, 5% of crosslinking monomer DS-65, 5% of functional monomer and 2% of emulsifying agent, heating to 55 ℃, emulsifying for 1.5h, adding 0.3% of initiator azodiisobutyronitrile, heating to 75 ℃, reacting for 0.5h, drying and discharging to obtain polyacrylate;
S3: dehydrating raw materials, mixing 80g of polytetrahydrofuran ether glycol 2000 and 65g of isophorone diisocyanate in a nitrogen environment, heating to 75 ℃, adding dibutyl tin dilaurate accounting for 3% of the total mass of the mixed system, and reacting for 2.5h to obtain a polyurethane prepolymer;
S4: mixing 23g of polyurethane prepolymer with 100g of acetone, reacting for 1.5 hours at 75 ℃, adding 5g of triethylamine, reacting for 8 minutes, adding 40g of deionized water and 3g of ethylenediamine, reacting for 5 minutes, adding 85g of polyacrylate, stirring for 30 minutes, and heating to remove acetone to obtain polyurethane modified polyacrylate sizing;
step 2:
Selecting a wood board with the thickness of 5mm as a panel substrate, repairing and flattening the uneven part of the surface of the panel substrate, sanding, and coating polyurethane modified polyacrylate glue on the panel substrate, wherein the coating thickness is 2mm; spreading veneer on the surface of the panel substrate coated with glue, and performing hot-pressing lamination, wherein the hot-pressing temperature is 110 ℃; the pressure is 9Mpa; and (3) carrying out UV paint surface curing on the surface of the wood veneer after manual inspection and finishing to obtain the formaldehyde-free environment-friendly wood veneer.
Comparative example 3: in S1, eugenol is reacted with 2-ethyl acryloyl chloride and then with 3-mercapto-1, 2-propanediol, and the other parameters are the same as in example 3.
Step 1:
S1: 1mol of 3-mercapto-1, 2-propanediol, 0.8mol of triethanolamine, 0.03mol of initiator azodiisobutyronitrile and 1.7mol of dichloromethane are mixed, stirred under ice bath condition, 1.6mol of 2-ethyl acryloyl chloride is added for 3 times, the mixture is stirred for reaction for 10min once, then the temperature is raised to 25 ℃ for reaction for 48h, saturated brine is extracted, dried, distilled under reduced pressure, purified and then 1mol of eugenol is added for mixing, and the mixture is reacted for 3h under the irradiation of a 100W ultraviolet lamp to obtain a reaction product;
S2: mixing 32.7% of water, 10% of methyl methacrylate, 45% of ethyl acrylate, 5% of crosslinking monomer DS-65, 3% of reaction product and 2% of emulsifier, heating to 45 ℃, emulsifying for 1h, adding 0.3% of initiator azodiisobutyronitrile, heating to 70 ℃, reacting for 0.5h, drying and discharging to obtain polyacrylate;
S3: dehydrating raw materials, mixing 80g of polytetrahydrofuran ether glycol 2000 and 65g of isophorone diisocyanate in a nitrogen environment, heating to 70 ℃, adding dibutyl tin dilaurate accounting for 3% of the total mass of a mixed system, and reacting for 2 hours to obtain a polyurethane prepolymer;
s4: mixing 23g of polyurethane prepolymer, 85g of polyacrylate and 100g of acetone, reacting for 1h at 70 ℃, adding 5g of triethylamine, reacting for 5min, adding 40g of deionized water and 3g of ethylenediamine, reacting for 5min, and heating to remove acetone to obtain polyurethane modified polyacrylate sizing material;
step 2:
Selecting a wood board with the thickness of 5mm as a panel substrate, repairing and flattening the uneven part of the surface of the panel substrate, sanding, and coating polyurethane modified polyacrylate glue on the panel substrate, wherein the coating thickness is 2mm; spreading veneer on the surface of the panel substrate coated with glue, and performing hot-pressing lamination, wherein the hot-pressing temperature is 100 ℃; the pressure is 8Mpa; and (3) carrying out UV paint surface curing on the surface of the wood veneer after manual inspection and finishing to obtain the formaldehyde-free environment-friendly wood veneer.
Experiment: the polyurethane modified polyacrylate compounds prepared in examples 1 to 6 and comparative examples 1 to 3 were subjected to performance tests in which:
coating adhesion test: according to GB/T9286-1998 Standard "cross-cut test of paint and varnish film", a cutting tool is used for dividing the coating into square grids, an adhesive tape is adhered to the grids, and the adhesive force grade between the coating and a wood board is judged according to the damage condition of the grids after the adhesive tape is torn off. The experimental results are classified into 0 level to 5 level according to the damage degree of the paint film, wherein the 0 level is the level that the paint film is complete and has no drop, the highest adhesive force level is obtained, the 5 level is the level that the drop area is larger than 65% of the area of the complete paint film, and the worst adhesive force level is obtained;
Water resistance: after preparing a sample by the method in the coating adhesive force test, putting the sample into clear water for soaking for 24 hours, taking out the sample, drying the sample for 24 hours, testing the adhesive force, comparing the adhesive force grade change before and after the soaking in the clear water, and if the adhesive force grade change is unchanged, marking the sample as good water resistance, and if the adhesive force grade change is reduced, marking the sample as poor water resistance;
Antibacterial test: and (3) taking escherichia coli as a test strain, drying a polyurethane modified polyacrylate sizing material to prepare a sample, adding 1g of the sample into 10mL of escherichia coli strain liquid, standing at the constant temperature of 37 ℃ for 24 hours, and testing the bacterial inhibition rate.
Conclusion: the data of examples 1-6 show that the polyurethane modified polyacrylate rubber material prepared by the invention has good adhesive property, water resistance and antibacterial effect, can replace the traditional formaldehyde-containing rubber material, can effectively bond wood veneer, and improves the antibacterial property and service life of the material. The data of example 1 and comparative example 1 show that the adhesive properties of the compounds are stronger after the polyacrylate is modified by polyurethane; the data of example 2 and comparative example 2 show that the resulting compounds have stronger adhesion properties after crosslinking the polyurethane and polyacrylate via chemical bonds compared to physical blending; the data of example 3 and comparative example 3 show that functional monomers cannot be synthesized efficiently after changing the reaction sequence of the raw materials in S1, and thus the adhesive property and antibacterial property of the compound are poor.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A preparation process of formaldehyde-free environment-friendly wood veneer is characterized by comprising the following steps of: the method comprises the following steps:
step 1:
S1: mixing 3-mercapto-1, 2-propanediol and eugenol, adding an initiator azodiisobutyronitrile, reacting for 3-5 hours under the irradiation of a 100-120W ultraviolet lamp, adding triethanolamine and methylene dichloride, stirring under the ice bath condition, adding 2-ethyl acryloyl chloride for 3-5 times, and reacting for 10-15 minutes under single stirring; then heating to 25-35 ℃ for reaction for 48-55 h, extracting with saturated brine, drying, rotary steaming, distilling under reduced pressure, and purifying to obtain a functional monomer; wherein the molar ratio of the 3-mercapto-1, 2-propylene glycol, eugenol and 2-ethyl acryloyl chloride is 1:1:1;
S2: mixing water, methyl methacrylate, ethyl acrylate, a crosslinking monomer DS-65, a functional monomer and an emulsifier, heating to 45-65 ℃, emulsifying for 1-2 hours, adding an initiator, heating to 70-80 ℃, reacting for 0.5-1 hour, drying and discharging to obtain polyacrylate;
S3: dehydrating raw materials, mixing polytetrahydrofuran ether glycol 2000 and isophorone diisocyanate in a nitrogen environment, heating to 70-80 ℃, adding dibutyltin dilaurate, and reacting for 2-3 hours to obtain a polyurethane prepolymer;
s4: mixing polyurethane prepolymer, polyacrylate and acetone, reacting for 1-2 hours at 70-80 ℃, adding triethylamine, reacting for 5-10 minutes, adding deionized water and ethylenediamine, reacting for 3-5 minutes, and heating to remove acetone to obtain polyurethane modified polyacrylate sizing material;
step 2:
Selecting a wood board as a panel substrate, repairing and flattening the uneven part of the surface of the panel substrate, sanding, and coating polyurethane modified polyacrylate rubber on the panel substrate; spreading the veneer on the surface of the panel substrate to be glued, and performing hot pressing lamination; and (3) carrying out UV paint surface curing on the surface of the wood veneer after manual inspection and finishing to obtain the formaldehyde-free environment-friendly wood veneer.
2. The process for preparing formaldehyde-free environment-friendly wood veneer according to claim 1, which is characterized in that: in the S2, the dosages of the components are, by weight, 7-10% of methyl methacrylate, 30-45% of ethyl acrylate, 3-8% of crosslinking monomer DS-65, 5-10% of functional monomer, 1-3% of emulsifier, 0.1-0.3% of initiator azodiisobutyronitrile, and the balance of water.
3. The process for preparing formaldehyde-free environment-friendly wood veneer according to claim 1, which is characterized in that: in S2, the emulsifier is any one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, tween 80 and span 80.
4. The process for preparing formaldehyde-free environment-friendly wood veneer according to claim 1, which is characterized in that: and S3, the mass ratio of the polytetrahydrofuran ether glycol 2000 to the isophorone diisocyanate is (80-100) (50-60).
5. The process for preparing formaldehyde-free environment-friendly wood veneer according to claim 1, which is characterized in that: and S4, the dosages of all components in the polyurethane modified polyacrylate rubber material are 23-36 parts of polyurethane prepolymer, 72-85 parts of polyacrylate, 100 parts of acetone, 5-8 parts of triethylamine, 30-40 parts of deionized water and 2-3 parts of ethylenediamine in parts by weight.
6. The process for preparing formaldehyde-free environment-friendly wood veneer according to claim 1, which is characterized in that: in the step 2, the thickness of the wood board is 5-15 mm.
7. The process for preparing formaldehyde-free environment-friendly wood veneer according to claim 1, which is characterized in that: in the step 2, the coating thickness of the polyurethane modified polyacrylate rubber material is 2-3 mm.
8. The process for preparing formaldehyde-free environment-friendly wood veneer according to claim 1, which is characterized in that: in the step 2, the hot pressing temperature is 100-120 ℃; the pressure is 8-10 mpa.
9. The wood veneer prepared by the preparation process of the formaldehyde-free environment-friendly wood veneer according to any one of claims 1-8.
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CN101402714A (en) * | 2008-11-08 | 2009-04-08 | 佛山市顺德区巴德富实业有限公司 | Polyurethane-acrylic ester emulsion for watersoluble wood lacquer and method of producing the same |
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