CN103146327B - A kind of preparation method of adhesive for wood - Google Patents
A kind of preparation method of adhesive for wood Download PDFInfo
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- CN103146327B CN103146327B CN201310117575.7A CN201310117575A CN103146327B CN 103146327 B CN103146327 B CN 103146327B CN 201310117575 A CN201310117575 A CN 201310117575A CN 103146327 B CN103146327 B CN 103146327B
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- monomer
- mass parts
- initiator
- emulsifying agent
- wood
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- 239000002023 wood Substances 0.000 title claims abstract description 59
- 239000000853 adhesive Substances 0.000 title claims abstract description 53
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 93
- 239000003999 initiator Substances 0.000 claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- -1 aromatic ethenyl compound Chemical class 0.000 claims abstract description 44
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 44
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 24
- 239000003002 pH adjusting agent Substances 0.000 claims abstract description 21
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 21
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 13
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 13
- 229920001567 vinyl ester resin Polymers 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 238000004945 emulsification Methods 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 21
- 229920002554 vinyl polymer Polymers 0.000 claims description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 239000012874 anionic emulsifier Substances 0.000 claims description 9
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical group [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 6
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 6
- 235000019800 disodium phosphate Nutrition 0.000 claims description 6
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229940065472 octyl acrylate Drugs 0.000 claims description 6
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 claims description 6
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000000839 emulsion Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 3
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 3
- 239000002904 solvent Substances 0.000 abstract description 9
- 230000001846 repelling effect Effects 0.000 abstract description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 31
- 238000012360 testing method Methods 0.000 description 19
- 239000003795 chemical substances by application Substances 0.000 description 17
- 239000002994 raw material Substances 0.000 description 16
- 238000003756 stirring Methods 0.000 description 12
- 235000019256 formaldehyde Nutrition 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 238000004513 sizing Methods 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 229960004279 formaldehyde Drugs 0.000 description 9
- 235000010469 Glycine max Nutrition 0.000 description 8
- 229920001807 Urea-formaldehyde Polymers 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 230000009466 transformation Effects 0.000 description 8
- 244000068988 Glycine max Species 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000010008 shearing Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000004160 Ammonium persulphate Substances 0.000 description 4
- 239000004836 Glue Stick Substances 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 235000019395 ammonium persulphate Nutrition 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-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
- 239000004141 Sodium laurylsulphate Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229920002522 Wood fibre Polymers 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 3
- 210000000481 breast Anatomy 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000005496 tempering Methods 0.000 description 3
- LKOVPWSSZFDYPG-WUKNDPDISA-N trans-octadec-2-enoic acid Chemical compound CCCCCCCCCCCCCCC\C=C\C(O)=O LKOVPWSSZFDYPG-WUKNDPDISA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides a kind of preparation method of adhesive for wood, comprise the following steps: monomer, emulsifying agent, initiator, pH adjusting agent are mixed with water, carry out letex polymerization, obtain adhesive for wood; Described monomer comprises main monomer and function monomer, and described main monomer is one or more of vinyl esters of unsaturated carboxylic acids and aromatic ethenyl compound, and described function monomer is one or more in unsaturated carboxylic acid and unsaturated carboxylic acid acid amides.Adhesive for wood prepared by the present invention, not containing formaldehyde, has excellent cohesive force and water repelling property, and has excellent solvent resistance.
Description
Technical field
The invention belongs to sizing agent technical field, be specifically related to a kind of preparation method of adhesive for wood.
Background technology
China's wood working uses sizing agent mainly wood-based plate manufacture and woodwork production two large fields, and along with the sustainable development of wood processing industry, the consumption of based Wood Adhesives is at continuous enlargement, and kind is also being on the increase.
The production glue of timber industry is mainly urea-formaldehyde glue and sticks agent.It is urea and formaldehyde under acid or basic catalyst effect that urea-formaldehyde glue sticks agent, and polycondensation becomes initial stage urea-formaldehyde resin, and then under solidifying agent or promoter effect, forms molten, insoluble urea-formaldehyde adhesive.Urea-formaldehyde glue sticks agent, and because it has, price is low, raw material is easy to get, bonding strength is high, manufacture the advantages such as simple, easy to use, larger proportion is occupied in wood working production sizing agent, become the main glue kind of China's wood producing, wherein, urea-formaldehyde glue sticks agent and accounts for wood-based plate glue consumption more than 90% in timber industry.But, it is that main raw material is prepared from formaldehyde that urea-formaldehyde glue sticks agent, this just makes to have Form aldehyde release out in himself and goods thereof, the regulation if burst size of methanal is above standard, can cause damage to HUMAN HEALTH, thus organizational strength to research and develop the hypotoxic adhesive for wood of integrating with the world market significant.
Along with the continuous research of technician, also have not containing the sizing agent of formaldehyde in the market, as rubber made from soybean cake.Rubber made from soybean cake is by hydrolyzed soy powder and resol coreaction, obtains soya-based sizing agent resin, i.e. rubber made from soybean cake.Owing to not containing formaldehyde in rubber made from soybean cake, it is made more and more to be paid attention in the applied research in timber industry field, but rubber made from soybean cake is in cohesive force and water repelling property, far do not reach the performance needed for wood processing field, limit its application in based Wood Adhesives field.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is the preparation method providing a kind of adhesive for wood, and the adhesive for wood prepared by the present invention, not containing formaldehyde, has excellent cohesive force and water repelling property, and has excellent solvent resistance.
The invention provides a kind of preparation method of adhesive for wood, comprise the following steps:
Monomer, emulsifying agent, initiator, pH adjusting agent are mixed with water, carries out letex polymerization, obtain adhesive for wood;
Described monomer comprises main monomer and function monomer, and described main monomer is one or more of vinyl esters of unsaturated carboxylic acids and aromatic ethenyl compound, and described function monomer is one or more in unsaturated carboxylic acid and unsaturated carboxylic acid acid amides.
Preferably, described preparation method is specially:
A) by the monomer of pH adjusting agent, the first mass parts, the emulsifying agent of the first mass parts, the initiator of the first mass parts mix with the water of the first mass parts, react, obtain reaction solution;
B) in described reaction solution, add the initiator of pre-emulsification material and the second mass parts, carry out letex polymerization, obtain adhesive for wood;
Described pre-emulsification material comprises the water of the monomer of the second mass parts, the emulsifying agent of the second mass parts and the second mass parts;
The monomer of described first mass parts is (10 ~ 50) with the ratio of the consumption of the monomer of the second mass parts: (50 ~ 90);
The emulsifying agent of described first mass parts is (10 ~ 50) with the ratio of the consumption of the emulsifying agent of the second mass parts: (50 ~ 90);
The initiator of described first mass parts is (10 ~ 50) with the ratio of the consumption of the initiator of the second mass parts: (50 ~ 90);
The water of described first mass parts is (10 ~ 50) with the ratio of the consumption of the water of the second mass parts: (50 ~ 90).
Preferably, described function monomer also comprises vinyl unsaturated nitrile compounds.
Preferably, the mass ratio of described monomer, emulsifying agent, initiator, pH adjusting agent and water is 100:(0.3 ~ 7): (0.15 ~ 0.95): (0.1 ~ 0.5): (100 ~ 150).
Preferably, the mass ratio of described vinyl esters of unsaturated carboxylic acids and described monomer is (40 ~ 70): 100;
The mass ratio of described aromatic ethenyl compound and described monomer is (30 ~ 50): 100;
The mass ratio of described unsaturated carboxylic acid and described monomer is (0.1 ~ 5): 100;
The mass ratio of described unsaturated carboxylic acid acid amides and described monomer is (0.1 ~ 5): 100;
The mass ratio of described vinyl unsaturated nitrile compounds and described monomer is (0 ~ 10): 100.
Preferably, described vinyl esters of unsaturated carboxylic acids is one or more in methyl methacrylate, butyl acrylate, ethyl propenoate and Octyl acrylate;
Described aromatic ethenyl compound is one or more in vinylbenzene and alpha-methyl styrene;
Described vinyl unsaturated nitrile compounds is vinyl cyanide or methacrylonitrile;
Described unsaturated carboxylic acid is vinylformic acid, methylene-succinic acid or methacrylic acid;
Described unsaturated amides is acrylamide or N hydroxymethyl acrylamide.
Preferably, described emulsifying agent is the compound emulsifying agent that anionic emulsifier and nonionic emulsifying agent are formed.
Preferably, described anionic emulsifier is one or more in alkyl-sulphate, polyvinyl alcohol, Seconary Alkane Sulphonate Sodium compound and derivative thereof and (z)-9-octadecenic acid sylvite;
Described nonionic emulsifying agent is one or more in alkylaryl Soxylat A 25-7 compounds.
Preferably, described initiator is water-soluble heat decomposition type persulphate.
Preferably, described pH adjusting agent is Sodium phosphate dibasic.
Compared with prior art, monomer, emulsifying agent, initiator, pH adjusting agent are mixed with water, carry out letex polymerization, obtain adhesive for wood; Described monomer comprises main monomer and function monomer, and described main monomer is one or more of vinyl esters of unsaturated carboxylic acids and aromatic ethenyl compound, and described function monomer is one or more in unsaturated carboxylic acid and unsaturated carboxylic acid acid amides.The present invention with vinyl esters of unsaturated carboxylic acids and/or aromatic ethylene compound for main monomer, be aided with one in vinyl unsaturated nitrile, unsaturated carboxylic acid and unsaturated carboxylic acid acid amides and multiple as function monomer, avoid using formaldehyde to be raw material, and adopt the method for letex polymerization, make the adhesive for wood prepared have excellent water tolerance, cohesiveness, solvent resistance.
Result shows, the viscosity >=269mpas of the adhesive for wood prepared by the present invention, remaining unsaturated volatile matter≤300ppm, and particle diameter is 1.0 ~ 2.2 μm, and total solid content is 40% ~ 45%.Further, have good physical strength, Formaldehyde emission rate is low.
Embodiment
The invention provides a kind of preparation method of adhesive for wood, comprise the following steps:
Monomer, emulsifying agent, initiator, pH adjusting agent are mixed with water, carries out letex polymerization, obtain adhesive for wood;
Described monomer comprises main monomer and function monomer, and described main monomer is one or more of vinyl esters of unsaturated carboxylic acids and aromatic ethenyl compound, and described function monomer is one or more in unsaturated carboxylic acid and unsaturated carboxylic acid acid amides.
First monomer, emulsifying agent, initiator, pH adjusting agent mix with water by the present invention, carry out letex polymerization, obtain adhesive for wood.
Monomer of the present invention comprises main monomer and function monomer, wherein, in described main monomer, described vinyl esters of unsaturated carboxylic acids be preferably in methyl methacrylate, butyl acrylate, ethyl propenoate and Octyl acrylate one or more, be more preferably in ethyl propenoate, butyl acrylate and Octyl acrylate one or more; The mass ratio of described vinyl esters of unsaturated carboxylic acids and described monomer is preferably (40 ~ 70): 100, is more preferably (50 ~ 60): 100;
Described aromatic ethenyl compound be preferably in vinylbenzene and alpha-methyl styrene one or more, be more preferably vinylbenzene; The mass ratio of described aromatic ethenyl compound and described monomer is preferably (30 ~ 50): 100, is more preferably (35 ~ 45): 100.
In the function monomer of described monomer, described unsaturated carboxylic acid is preferably vinylformic acid, methylene-succinic acid or methacrylic acid, is more preferably acrylic or methacrylic acid; The mass ratio of described unsaturated carboxylic acid and described monomer is preferably (0.1 ~ 5): 100, is more preferably (1 ~ 3): 100;
Described unsaturated amides is preferably acrylamide or N hydroxymethyl acrylamide, is more preferably N hydroxymethyl acrylamide; The mass ratio of described unsaturated carboxylic acid acid amides and described monomer is preferably (0.1 ~ 5): 100, is more preferably (1 ~ 3): 100.
In the present invention, described function monomer also comprises vinyl unsaturated nitrile compounds, and described vinyl unsaturated nitrile compounds is preferably vinyl cyanide or methacrylonitrile, is more preferably vinyl cyanide; The mass ratio of described vinyl unsaturated nitrile compounds and described monomer is preferably (0 ~ 10): 100, is more preferably (2 ~ 8): 100.
The mass ratio of main monomer of the present invention and function monomer is preferably (82 ~ 98.9): (1.1 ~ 18), are more preferably (85 ~ 90): (10 ~ 15).
In the present invention, described emulsifying agent is the compound emulsifying agent that anionic emulsifier and nonionic emulsifying agent are formed.Wherein, described anionic emulsifier be preferably in alkyl-sulphate, polyvinyl alcohol, Seconary Alkane Sulphonate Sodium compound and derivative thereof and (z)-9-octadecenic acid sylvite one or more, be more preferably in sodium lauryl sulphate, polyvinyl alcohol, Seconary Alkane Sulphonate Sodium and octadecenoic acid potassium one or more; Described nonionic emulsifying agent be preferably in alkylaryl Soxylat A 25-7 one or more, be more preferably polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether and alkylphenol polyoxyethylene.Wherein, the mass ratio of described anionic emulsifier and nonionic emulsifying agent is preferably 1:(1 ~ 6), be more preferably 1:(2 ~ 5).The present invention adopts composite emulsifying system, selects the composite of anionic emulsifier and nonionic emulsifying agent, by the mass ratio of adjustment anionic emulsifier and nonionic emulsifying agent, makes sizing agent form nucleocapsid structure in system, improves the performance of sizing agent.
The initiator that the present invention adds is water-soluble heat decomposition type persulfate initiator, can reduce the pollution to environment, is preferably persulphate compounds, is more preferably Potassium Persulphate or ammonium persulphate.Described pH adjusting agent is Sodium phosphate dibasic.Described water is preferably deionized water.The source of the present invention to described monomer, emulsifying agent, initiator, pH adjusting agent there is no particular restriction, generally commercially available.
In the present invention, the mass ratio of described monomer, emulsifying agent, initiator, pH adjusting agent and water is preferably 100:(0.3 ~ 7): (0.15 ~ 0.95): (0.1 ~ 0.5): (100 ~ 150), are more preferably 100:(1 ~ 5): (0.2 ~ 0.8): (0.2 ~ 0.3): (120 ~ 140).
The present invention mixes with water above-mentioned monomer, emulsifying agent, initiator, pH adjusting agent, and the place of carrying out letex polymerization there is no particular restriction, can be polymeric kettle.Further, the feed way of the present invention to above-mentioned raw materials there is no particular restriction, above-mentioned raw materials once can be joined in reactor, also can join in reactor in batches, in the present invention, preferably described raw material be joined in reactor in batches, carry out emulsion polymerization, concrete grammar is:
A) by the monomer of pH adjusting agent, the first mass parts, the emulsifying agent of the first mass parts, the initiator of the first mass parts mix with the water of the first mass parts, react, obtain reaction solution;
B) in described reaction solution, add the initiator of pre-emulsification material and the second mass parts, carry out letex polymerization, obtain adhesive for wood;
Described pre-emulsification material comprises the water of the monomer of the second mass parts, the emulsifying agent of the second mass parts and the second mass parts;
The emulsifying agent of the monomer of pH adjusting agent, the first mass parts, the first mass parts, the initiator of the first mass parts mix with the water of the first mass parts by the present invention, wherein, the mode of the present invention to described mixing there is no particular restriction, in the present invention, preferably mixes as follows:
After polymeric kettle is vacuumized, in described polymeric kettle, add the water of pH adjusting agent, the monomer of the first mass parts, the emulsifying agent of the first mass parts and the first mass parts, after described polymeric kettle heat temperature raising, add the initiator of the first mass parts, react, obtain reaction solution.Wherein, the temperature of described polymerization reaction kettle heat temperature raising is preferably 50 ~ 90 DEG C, is more preferably 60 ~ 80 DEG C; Add initiator to polymeric kettle, the time of carrying out reacting is preferably 0.5 ~ 2.5h, is more preferably 1 ~ 2h.The monomer conversion of described reaction is preferably 60% ~ 90%, is more preferably 70% ~ 80%.
The present invention, when carrying out letex polymerization, adopts ladder temperature control technique, improves the stability of the sizing agent that letex polymerization obtains, prevent gel from producing, improve the performance of sizing agent.The present invention adopts higher polymerization temperature, namely at the monomer to pH adjusting agent, the first mass parts, the emulsifying agent of the first mass parts, the initiator of the first mass parts mix with the water of the first mass parts, above-mentioned raw materials material is heated to the temperature 50 ~ 90 DEG C needed for polyreaction, described step B) in letex polymerization temperature of reaction maintenance and improve then by steps A) in reaction polymerization reaction heat supplement, can energy consumption be reduced.
Concrete, the raw material of the first mass parts is being added to polymeric kettle, the raw material of described first mass parts comprises: pH adjusting agent, the monomer of the first mass parts, the emulsifying agent of the first mass parts and the water of the first mass parts, described polymeric kettle is furnished with heat-exchange system, the temperature series adjustment of polymeric kettle and heat-exchange system is by the internal recycle water management in described heat-exchange system, the raw material of described first mass parts is heated, described Heating temperature is preferably 50 ~ 90 DEG C, be more preferably 60 ~ 80 DEG C, while the raw material of described first mass parts is heated, the initiator of the first mass parts is added in reactor, when the transformation efficiency of the monomer of the first mass parts in polymeric kettle is 60% ~ 90%, stop heating.The temperature of reaction needed for emulsion polymerization that the initiator that the reaction heat of the raw material of the first mass parts and the initiator for reaction of the first mass parts can be used for supplementary pre-emulsion and the second mass parts carries out.
After obtaining reaction solution, in described reaction solution, add the initiator of pre-emulsification material and the second mass parts, carry out letex polymerization.Wherein, described pre-emulsification material comprises the water of the monomer of the second mass parts, the emulsifying agent of the second mass parts and the second mass parts.
In the present invention, the monomer of the second mass parts is carried out pre-emulsification, obtain pre-emulsification material.The present invention there is no particular restriction to described pre-emulsified mode, pre-emulsification mode well known to those skilled in the art.Wherein, monomer is fully swelling after emulsifying agent pre-emulsification, adopts the mode of continuous charging to join in reaction solution the initiator of described pre-emulsification material and the second mass parts, under the condition ensureing high polymerisation conversion, is that monomer carries out uniform chainpropagation.
The initiator of described pre-emulsification material and the second mass parts is joined in reaction solution continuously, carries out letex polymerization.Wherein, the temperature of described letex polymerization is preferably 80 ~ 100 DEG C, is more preferably 85 ~ 95 DEG C.Measure the transformation efficiency of the monomer in polymeric kettle, as described monomer conversion > 99%, get final product stopped reaction, obtain end reaction liquid.
Wherein, the monomer of described first mass parts is preferably (10 ~ 50) with the ratio of the consumption of the monomer of the second mass parts: (50 ~ 90), are more preferably (20 ~ 40): (60 ~ 80); The emulsifying agent of described first mass parts is preferably (10 ~ 50) with the ratio of the consumption of the emulsifying agent of the second mass parts: (50 ~ 90), are more preferably (20 ~ 40): (60 ~ 80); The initiator of described first mass parts is preferably (10 ~ 50) with the ratio of the consumption of the initiator of the second mass parts: (50 ~ 90), are more preferably (20 ~ 40): (60 ~ 80); The water of described first mass parts is preferably (10 ~ 50) with the ratio of the consumption of the water of the second mass parts: (50 ~ 90), are more preferably (20 ~ 40): (60 ~ 80).
After stopped reaction, obtain end reaction liquid, described end reaction liquid is carried out aftertreatment, the concrete grammar of described aftertreatment is:
Described end reaction liquid is carried out degassed process, adjust ph, can adhesive for wood be obtained.
In the present invention, degassed process is adopted to remove whole unreacted monomers completely.The mode of the present invention to described degassed process there is no particular restriction, preferably adopts the mode vacuumized of pressurizeing to carry out degassed process.After described degassed process, measure the residual volume of unsaturated volatile matter in end reaction liquid, described residual volume is preferably≤300ppm, is more preferably≤200ppm.Regulate the pH value of described end reaction liquid with ammoniacal liquor, can adhesive for wood be obtained, described pH value range preferably from 5.5 ~ 7.5, be more preferably 6 ~ 7.
The present invention with vinyl esters of unsaturated carboxylic acids and/or aromatic ethylene compound for main monomer, be aided with one in vinyl unsaturated nitrile, unsaturated carboxylic acid and unsaturated carboxylic acid acid amides and multiple as function monomer, avoid using formaldehyde to be raw material, and adopt the method for letex polymerization, make the adhesive for wood prepared have excellent water tolerance, cohesiveness and solvent resistance.
Result shows, the viscosity >=269mpas of the adhesive for wood prepared by the present invention, remaining unsaturated volatile matter≤300ppm, and particle diameter is 1.0 ~ 2.2 μm, and total solid content is 40% ~ 45%.Further, have good physical strength, Formaldehyde emission rate is low.
In order to understand the present invention further, be described adhesive for wood provided by the invention below in conjunction with embodiment, protection scope of the present invention is not limited by the following examples.
Embodiment 1
30g deionized water, 0.3g sodium lauryl sulphate, 0.7g polyoxyethylene octylphenol ether, 32g ethyl propenoate, 18g butyl acrylate, 24g vinylbenzene, 0.5g vinylformic acid, the third 3.0g alkene nitrile, 2.5gN-n-methylolacrylamide is added in pre-emulsification still, stir 20 minutes under 25 DEG C of conditions, stir, obtain pre-emulsification material.
In initiator groove, add deionized water 20g, ammonium persulphate 0.7g, be stirred to dissolving, obtain initiator solution.Using 30% of described initiator solution quality as the initiator solution of the first mass parts, using 70% of described initiator solution quality as the initiator solution of the second mass parts.
In still, 80g deionized water, 0.2g sodium lauryl sulphate, 0.5g polyoxyethylene octylphenol ether, 8g ethyl propenoate, 9g butyl acrylate, 6g vinylbenzene, 0.5g vinylformic acid is added after polymeric kettle vacuumizes, 0.1g Sodium phosphate dibasic, stir 20 minutes under 25 DEG C of conditions, stir.
Heated up by the chuck steam of reactor, when temperature reaches 80 DEG C, stop steam heating up, add the initiator solution of the first mass parts, then reaction is started, react 2 hours, when reaction reaches 90% to transformation efficiency, slowly to continuous charging in reactor, namely the pre-emulsification material of above-mentioned preparation, the initiator solution of the second mass parts are thrown in reactor respectively, temperature controls at 90 DEG C, after the reinforced end of initiator of described pre-emulsification material and the second mass parts, temperature of reaction is maintained 95 DEG C.When transformation efficiency reaches more than 99%, vacuumized by polymeric kettle, carry out degassed process, remove the monomer of whole remnants, measuring remaining unsaturated volatile matter in emulsion is 226ppm.Reach 7.3 with the pH value of ammoniacal liquor impregnation breast, product cools to 30 DEG C, arrives tempering tank after filtering and packs, obtain adhesive for wood.Measure the total solid substance of described based Wood Adhesives, viscosity, median size etc., the results are shown in Table 1, the based Wood Adhesives physico-chemical property of table 1 prepared by embodiment 1 ~ 3.
Based Wood Adhesives embodiment 1 prepared carries out water resistance test, and concrete grammar is as follows:
Be the steel test piece of 100mm × 25mm × 3mm by specification, sand for surface paper is polished, and acetone is cleaned, and obtains shear test block;
Adhesive for wood prepared by embodiment 1 is coated on described shear test block, wherein, bond length is 15mm, self-vulcanizing 24h, 0h is placed respectively in the distilled water of 23 DEG C ± 2 DEG C, 3h, 7h, 15h, 30h, after 48h, take out test specimen room temperature and hang 24 hours, under the condition of 25 DEG C, adopt Shanghai Shenlian Tester Factory model to be that the electronic tension tester of LD-50 type measures the shearing resistance of test specimen respectively, wherein, often organize data determination 3 parallel samples, average, the results are shown in Table 2, the shearing resistance experimental result of the adhesive for wood of table 2 prepared by embodiment 1.
The shearing resistance experimental result of the adhesive for wood prepared by table 2 embodiment 1
Be the steel test piece of 100mm × 25mm × 3mm by specification, sand for surface paper is polished, and acetone is cleaned, and obtains shear test block;
At adhesive for wood prepared by above-mentioned shearing strip coating embodiment 1, the glued membrane of preparation 0.2mm × 25mm × 60mm, self-vulcanizing 24h, after the distilled water putting into 23 DEG C ± 2 DEG C places 0h, 3h, 7h, 15h, 30h, 48h respectively, take out test specimen room temperature and hang 24 hours, taking-up test specimen dries, and observes glued membrane state.Experimental result is in table 3, and table 3 is the water resistance test result of adhesive for wood prepared by embodiment 1.
The water resistance test result of adhesive for wood prepared by table 3 embodiment 1
Measuring the soak strength retention of 30 hours and 48 hours of the shear test block scribbling adhesive for wood is respectively 99.6% and 95.9%.
Result shows, the adhesive for wood prepared by embodiment 1 there is good water tolerance.
Based Wood Adhesives embodiment 1 prepared carries out solvent resistance test, and concrete grammar is as follows:
Be the steel test piece of 100mm × 25mm × 3mm by specification, sand for surface paper is polished, and acetone is cleaned, and obtains shear test block;
At adhesive for wood prepared by above-mentioned shearing strip coating embodiment 1, the glued membrane of preparation 0.2mm × 25mm × 60mm, 120 DEG C solidify 30 minutes, put into after No. 120 solvent oils place 0h, 8h, 18h, 28h, 38h, 48h respectively, take out test specimen room temperature and hang 24 hours, observing film surface has bubble-free, wrinkling, obscission state, the results are shown in Table 4, table 4 is the solvent resistance test result of sizing agent prepared by embodiment 1.
The solvent resistance test result of sizing agent prepared by table 4 embodiment 1
As shown in Table 4, product solvent resistance is superior, within 48 hours, does not occur bubble, wrinkling, obscission.
Embodiment 2
30g deionized water, 0.4g Seconary Alkane Sulphonate Sodium, 0.7g polyoxyethylene nonylphenol ether, 50g butyl acrylate, 25g vinylbenzene, 1.5g methacrylic acid, 1g acrylamide is added in pre-emulsification still, stir 20 minutes under 25 DEG C of conditions, stir, obtain pre-emulsification material.
In initiator groove, add deionized water 20g, ammonium persulphate 0.6g, be stirred to dissolving, obtain initiator solution.Using 30% of described initiator solution quality as the initiator solution of the first mass parts, using 70% of described initiator solution quality as the initiator solution of the second mass parts.
In still, 80g deionized water, 0.2g Seconary Alkane Sulphonate Sodium, 0.5g polyoxyethylene nonylphenol ether, 15g butyl acrylate, 10g vinylbenzene, 0.5g methacrylic acid is added after polymeric kettle vacuumizes, 0.2g Sodium phosphate dibasic, stir 20 minutes under 25 DEG C of conditions, stir.
Heated up by the chuck steam of reactor, when temperature reaches 90 DEG C, steam is stopped to heat up, add the initiator solution of the first mass parts, then reaction is started, react 2 hours, when reaction reaches 90% to transformation efficiency, slowly to continuous charging in reactor, the i.e. pre-emulsification material of above-mentioned preparation, the initiator solution of the second mass parts is thrown in reactor respectively, temperature controls at 90 DEG C, after the reinforced end of initiator of described pre-emulsification material and the second mass parts, temperature of reaction is maintained 95 DEG C. when transformation efficiency reaches more than 99%, polymeric kettle vacuumizes, carry out degassed process, remove the monomer of whole remnants, in emulsion, remaining unsaturated volatile matter is 183ppm.Reach 7.0 with the pH value of ammoniacal liquor impregnation breast, product cools to 30 DEG C, arrives tempering tank after filtering and packs, obtain adhesive for wood.Measure the total solid substance of described based Wood Adhesives, viscosity, median size etc., the results are shown in Table 1, the based Wood Adhesives physico-chemical property of table 1 prepared by embodiment 1 ~ 3.
Embodiment 3
30g deionized water, 0.5g octadecenoic acid potassium, 0.9g alkylphenol polyoxyethylene, 42g Octyl acrylate, 31g vinylbenzene, 3g vinyl cyanide, 1.8g vinylformic acid, 0.8gN-n-methylolacrylamide is added in pre-emulsification still, stir 20 minutes under 25 DEG C of conditions, stir, obtain pre-emulsification material.
In initiator groove, add deionized water 20g, ammonium persulphate 0.7g, be stirred to dissolving, obtain initiator solution.Using 30% of described initiator solution quality as the initiator solution of the first mass parts, using 70% of described initiator solution quality as the initiator solution of the second mass parts.
In still, 80g deionized water, 0.2g octadecenoic acid potassium, 0.6g alkylphenol polyoxyethylene, 15g Octyl acrylate, 9g vinylbenzene, 0.6g vinylformic acid, 0.3g polyvinyl alcohol, 0.2g Sodium phosphate dibasic is added after polymeric kettle vacuumizes, stir 20 minutes under 25 DEG C of conditions, stir.
Heated up by the chuck steam of reactor, when temperature reaches 90 DEG C, stop steam heating up, add the initiator solution of the first mass parts, then reaction is started, react 2 hours, when reaction reaches 90% to transformation efficiency, slowly to continuous charging in reactor, namely the pre-emulsification material of above-mentioned preparation, the initiator solution of the second mass parts are thrown in reactor respectively, temperature controls at 90 DEG C, after the reinforced end of initiator of described pre-emulsification material and the second mass parts, temperature of reaction is maintained 95 DEG C.When transformation efficiency reaches more than 99%, polymeric kettle vacuumizes, and carries out degassed process, removes the monomer of whole remnants, and measuring remaining unsaturated volatile matter in emulsion is 211ppm.Reach 6.8 with the pH value of ammoniacal liquor impregnation breast, product cools to 30 DEG C, arrives tempering tank after filtering and packs, obtain adhesive for wood.Measure the total solid substance of described based Wood Adhesives, viscosity, median size etc., the results are shown in Table 1, the based Wood Adhesives physico-chemical property of table 1 prepared by embodiment 1 ~ 3.
Based Wood Adhesives physico-chemical property prepared by table 1 embodiment 1 ~ 3
Embodiment 4
Be that raw material mixes with adhesive for wood prepared by embodiment 1 with wood fibre, make density board, carry out performance test to described density board, result is see table 5, and table 5 is the performance perameter of density board prepared by the embodiment of the present invention 1.
Comparative example 1
Be that raw material is produced Precondensed UreaFormaldehyde Resin latex with Linyi City Hao Xiang Chemical Co., Ltd. and mixed with wood fibre, make density board, carry out performance test to described density board, result is see table 5, and table 5 be the performance perameter of the density board of the embodiment of the present invention 1 preparation.
Comparative example 2
Be that raw material mixes with the rubber made from soybean cake that Shanghai Honghan Chemical Technology Co., Ltd. produces with wood fibre, make density board, carry out performance test to described density board, result is see table 5, and table 5 is the performance perameter of density board prepared by the embodiment of the present invention 1.
The performance perameter of density board prepared by table 5 embodiment of the present invention 1 and comparative example 1 ~ 2
As shown in Table 5, the adhesive for wood prepared by the present invention has good physical strength, and burst size of methanal is low.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (7)
1. a preparation method for adhesive for wood, comprises the following steps:
Monomer, emulsifying agent, initiator, pH adjusting agent are mixed with water, carries out letex polymerization, obtain adhesive for wood;
Described monomer comprises main monomer and function monomer, and described main monomer is vinyl esters of unsaturated carboxylic acids and aromatic ethenyl compound, and described function monomer is unsaturated carboxylic acid, unsaturated amides and vinyl unsaturated nitrile compounds;
Described vinyl esters of unsaturated carboxylic acids is one or more in butyl acrylate, ethyl propenoate and Octyl acrylate;
Described aromatic ethenyl compound is one or more in vinylbenzene and alpha-methyl styrene;
Described vinyl unsaturated nitrile compounds is vinyl cyanide or methacrylonitrile;
Described unsaturated carboxylic acid is vinylformic acid, methylene-succinic acid or methacrylic acid;
Described unsaturated amides is acrylamide or N hydroxymethyl acrylamide;
The mass ratio of described vinyl esters of unsaturated carboxylic acids and described monomer is (40 ~ 70): 100;
The mass ratio of described aromatic ethenyl compound and described monomer is (30 ~ 50): 100;
The mass ratio of described unsaturated carboxylic acid and described monomer is (0.1 ~ 5): 100;
The mass ratio of described unsaturated carboxylic acid acid amides and described monomer is (0.1 ~ 5): 100;
The mass ratio of described vinyl unsaturated nitrile compounds and described monomer is (0 ~ 10): 100;
The temperature of described emulsion reaction is 50 ~ 90 DEG C.
2. preparation method according to claim 1, is characterized in that, described preparation method is specially:
A) by the monomer of pH adjusting agent, the first mass parts, the emulsifying agent of the first mass parts, the initiator of the first mass parts mix with the water of the first mass parts, react, obtain reaction solution;
B) in described reaction solution, add the initiator of pre-emulsification material and the second mass parts, carry out letex polymerization, obtain adhesive for wood;
Described pre-emulsification material comprises the water of the monomer of the second mass parts, the emulsifying agent of the second mass parts and the second mass parts;
The monomer of described first mass parts is (10 ~ 50) with the ratio of the consumption of the monomer of the second mass parts: (50 ~ 90);
The emulsifying agent of described first mass parts is (10 ~ 50) with the ratio of the consumption of the emulsifying agent of the second mass parts: (50 ~ 90);
The initiator of described first mass parts is (10 ~ 50) with the ratio of the consumption of the initiator of the second mass parts: (50 ~ 90);
The water of described first mass parts is (10 ~ 50) with the ratio of the consumption of the water of the second mass parts: (50 ~ 90).
3. preparation method according to claim 1 and 2, it is characterized in that, the mass ratio of described monomer, emulsifying agent, initiator, pH adjusting agent and water is 100:(0.3 ~ 7): (0.15 ~ 0.95): (0.1 ~ 0.5): (100 ~ 150).
4. preparation method according to claim 1 and 2, is characterized in that, described emulsifying agent is the compound emulsifying agent that anionic emulsifier and nonionic emulsifying agent are formed.
5. preparation method according to claim 4, is characterized in that,
Described anionic emulsifier is one or more in alkyl-sulphate, polyvinyl alcohol, Seconary Alkane Sulphonate Sodium compound and derivative thereof and (z)-9-octadecenic acid sylvite;
Described nonionic emulsifying agent is one or more in alkylaryl Soxylat A 25-7 compounds.
6. preparation method according to claim 1 and 2, is characterized in that, described initiator is water-soluble heat decomposition type persulphate.
7. preparation method according to claim 1 and 2, is characterized in that, described pH adjusting agent is Sodium phosphate dibasic.
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| 丙烯酸酯乳液胶粘剂的合成及其性能研究;李欣闻等;《中国胶粘剂》;20080930;第17卷(第9期);第1-4页 * |
| 四元共聚丙烯酸酯热熔压敏胶膜的合成研究;黎文部等;《中国胶粘剂》;20060930;第15卷(第9期);第6-10页 * |
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