CN103146327A - Method for preparing adhesive used for timber - Google Patents
Method for preparing adhesive used for timber Download PDFInfo
- Publication number
- CN103146327A CN103146327A CN2013101175757A CN201310117575A CN103146327A CN 103146327 A CN103146327 A CN 103146327A CN 2013101175757 A CN2013101175757 A CN 2013101175757A CN 201310117575 A CN201310117575 A CN 201310117575A CN 103146327 A CN103146327 A CN 103146327A
- Authority
- CN
- China
- Prior art keywords
- mass parts
- monomer
- preparation
- initiator
- emulsifying agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 53
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title abstract description 6
- 239000000178 monomer Substances 0.000 claims abstract description 94
- 239000003999 initiator Substances 0.000 claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 44
- -1 vinyl aromatic compound Chemical class 0.000 claims abstract description 44
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 24
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 14
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 13
- 239000002023 wood Substances 0.000 claims description 54
- 238000002360 preparation method Methods 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 238000004945 emulsification Methods 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 21
- 239000003002 pH adjusting agent Substances 0.000 claims description 20
- 238000006116 polymerization reaction Methods 0.000 claims description 20
- 150000001735 carboxylic acids Chemical class 0.000 claims description 12
- 229920001567 vinyl ester resin Polymers 0.000 claims description 12
- 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
- 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 6
- 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
- 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
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 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
- 150000001408 amides Chemical class 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
- 238000001149 thermolysis Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 18
- 239000002904 solvent Substances 0.000 abstract description 9
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract 3
- 150000001733 carboxylic acid esters Chemical class 0.000 abstract 1
- 230000003750 conditioning effect Effects 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 31
- 238000012360 testing method Methods 0.000 description 21
- 239000002994 raw material Substances 0.000 description 16
- 235000019256 formaldehyde Nutrition 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
- 238000012545 processing Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 235000010469 Glycine max Nutrition 0.000 description 8
- 229920001807 Urea-formaldehyde Polymers 0.000 description 8
- 239000003292 glue 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
- 238000003756 stirring Methods 0.000 description 6
- 238000010008 shearing Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000004160 Ammonium persulphate 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
- 239000000839 emulsion Substances 0.000 description 4
- 239000012528 membrane Substances 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
- 239000012467 final product Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 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
- 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
- 239000002131 composite material Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process 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
- 230000001846 repelling effect Effects 0.000 description 2
- 238000011160 research 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
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 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
- 230000036541 health Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 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
- 238000012827 research and development Methods 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
- 230000008961 swelling Effects 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides a method for preparing adhesive used for timber, which comprises the following steps: monomers, an emulsifying agent, an initiator and a pH conditioning agent are mixed with water, and emulsion polymerization is carried out to obtain the adhesive used for the timber; and the monomers include main monomers and functional monomers, the main monomers are one or more of vinyl unsaturated carboxylic acid ester and vinyl aromatic compound, and the functional monomers are one or more of unsaturated carboxylic acid and unsaturated carboxylic acid amide. The adhesive used for the timber prepared by the method disclosed by the invention does not contain methanol, and has excellent binding power and water-resistant performance and good solvent resistance.
Description
Technical field
The invention belongs to the sizing agent technical field, be specifically related to a kind of preparation method of adhesive for wood.
Background technology
It is mainly that wood-based plate manufacturing and woodwork are produced two large fields that China's wood working is used sizing agent, and along with the sustainable development of wood processing industry, the consumption of based Wood Adhesives is continuing expansion, and kind also is being on the increase.
The production of timber industry is mainly the glutinous agent of urea-formaldehyde glue with glue.The glutinous agent of urea-formaldehyde glue be urea with formaldehyde under acidity or basic catalyst effect, polycondensation becomes the initial stage urea-formaldehyde resin, and then under solidifying agent or promoter effect, form melt, insoluble urea-formaldehyde adhesive.Price is low, raw material is easy to get, bonding strength is high, make the advantages such as simple, easy to use because it has for the glutinous agent of urea-formaldehyde glue, in producing with sizing agent, wood working occupies larger proportion, become the main glue kind that China's timber is produced, wherein, the glutinous agent of urea-formaldehyde glue accounts in timber industry the wood-based plate glue consumption more than 90%.But, the glutinous agent of urea-formaldehyde glue is prepared from take formaldehyde as main raw material, this just makes and has formaldehyde in himself and goods thereof and discharge, the regulation if burst size of methanal is above standard, can cause damage to HUMAN HEALTH, so the hypotoxic adhesive for wood that the organizational strength research and development are integrated with the world market is significant.
Along with technician's continuous research, the sizing agent that does not contain formaldehyde is also arranged in the market, as rubber made from soybean cake.Rubber made from soybean cake is with 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, its applied research in the timber industry field is more and more paid attention to, but rubber made from soybean cake does not far reach the required performance of wood processing field aspect cohesive force and water repelling property, has limited its application in the based Wood Adhesives field.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of preparation method of adhesive for wood, and the prepared adhesive for wood of the present invention does not contain formaldehyde, has excellent cohesive force and water repelling property, and has good 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, 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.
Preferably, described preparation method is specially:
A) with the monomer of pH adjusting agent, the first mass parts, the initiator of the emulsifying agent of the first mass parts, the first mass parts mixes with the water of the first mass parts, reacts, and obtains reaction solution;
B) add the initiator of pre-emulsification material and the second mass parts in the described reaction solution, carry out letex polymerization, obtain adhesive for wood;
Described pre-emulsification material comprises the monomer of the second mass parts, the emulsifying agent of the second mass parts and the water of the second mass parts;
The monomer of described the 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 the 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 the 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 the 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 form.
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 thermolysis 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 is take vinyl esters of unsaturated carboxylic acids and/or aromatic ethylene compound as main monomer, be aided with a kind of and multiple as function monomer in vinyl unsaturated nitrile, unsaturated carboxylic acid and unsaturated carboxylic acid acid amides, avoid using formaldehyde to be raw material, and the method for employing letex polymerization, make the adhesive for wood for preparing have excellent water tolerance, cohesiveness, solvent resistance.
Result shows, the viscosity 〉=269mpas of the adhesive for wood that the present invention is prepared, remaining unsaturated volatile matter≤300ppm, particle diameter are 1.0～2.2 μ m, and total solid content is 40%～45%.And, having 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, 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.
At first the present invention mixes monomer, emulsifying agent, initiator, pH adjusting agent with water, carry out letex polymerization, obtains 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 is preferably one or more in methyl methacrylate, butyl acrylate, ethyl propenoate and Octyl acrylate, more preferably one or more in ethyl propenoate, butyl acrylate and Octyl acrylate; The mass ratio of described vinyl esters of unsaturated carboxylic acids and described monomer is preferably (40～70): 100, more preferably (50～60): 100;
Described aromatic ethenyl compound is preferably one or more in vinylbenzene and alpha-methyl styrene, more preferably vinylbenzene; The mass ratio of described aromatic ethenyl compound and described monomer is preferably (30～50): 100, 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, more preferably acrylic or methacrylic acid; The mass ratio of described unsaturated carboxylic acid and described monomer is preferably (0.1～5): 100, more preferably (1～3): 100;
Described unsaturated amides is preferably acrylamide or N hydroxymethyl acrylamide, more preferably N hydroxymethyl acrylamide; The mass ratio of described unsaturated carboxylic acid acid amides and described monomer is preferably (0.1～5): 100, 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, more preferably vinyl cyanide; The mass ratio of described vinyl unsaturated nitrile compounds and described monomer is preferably (0～10): 100, 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), 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 form.Wherein, described anionic emulsifier is preferably one or more in alkyl-sulphate, polyvinyl alcohol, Seconary Alkane Sulphonate Sodium compound and derivative thereof and (z)-9-octadecenic acid sylvite, more preferably one or more in sodium lauryl sulphate, polyvinyl alcohol, Seconary Alkane Sulphonate Sodium and octadecenoic acid potassium; Described nonionic emulsifying agent is preferably one or more in the alkylaryl Soxylat A 25-7, 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), 1:(2～5 more preferably).The present invention adopts the composite emulsifying system, selects the composite of anionic emulsifier and nonionic emulsifying agent, by adjusting the mass ratio of anionic emulsifier and nonionic emulsifying agent, makes sizing agent form nucleocapsid structure in system, has improved the performance of sizing agent.
The initiator that the present invention adds is water-soluble thermolysis type persulfate initiator, can reduce the pollution to environment, is preferably the persulphate compounds, more preferably Potassium Persulphate or ammonium persulphate.Described pH adjusting agent is Sodium phosphate dibasic.Described water is preferably deionized water.The present invention there is no particular restriction to the source of described monomer, emulsifying agent, initiator, pH adjusting agent, general commercially available getting final product.
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), 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.And the present invention there is no particular restriction to the feed way of above-mentioned raw materials, can once join above-mentioned raw materials in reactor, also can join in reactor in batches, in the present invention, preferably join described raw material in reactor in batches, carry out emulsion polymerization, concrete grammar is:
A) with the monomer of pH adjusting agent, the first mass parts, the initiator of the emulsifying agent of the first mass parts, the first mass parts mixes with the water of the first mass parts, reacts, and obtains reaction solution;
B) add the initiator of pre-emulsification material and the second mass parts in the described reaction solution, carry out letex polymerization, obtain adhesive for wood;
Described pre-emulsification material comprises the monomer of the second mass parts, the emulsifying agent of the second mass parts and the water of the second mass parts;
The present invention mixes 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 with the water of the first mass parts, wherein, the present invention there is no particular restriction to the mode of described mixing, in the present invention, preferably mixes as follows:
After polymeric kettle is vacuumized, add the monomer of pH adjusting agent, the first mass parts, the emulsifying agent of the first mass parts and the water of the first mass parts in described polymeric kettle, 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 ℃, more preferably 60～80 ℃; Add initiator to polymeric kettle, the time of reacting is preferably 0.5～2.5h, more preferably 1～2h.The monomer conversion of described reaction is preferably 60%～90%, and more preferably 70%～80%.
The present invention adopts ladder temperature control technique when carrying out letex polymerization, improved the stability of the sizing agent that letex polymerization obtains, and prevents that gel from producing, and improved 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 initiator of the emulsifying agent of the first mass parts, the first mass parts mixes with the water of the first mass parts, the above-mentioned raw materials material is heated to 50～90 ℃ of the required temperature of polyreaction, described step B) the keeping and improves by steps A of temperature of reaction of letex polymerization in), the polymerization reaction heat of reaction replenishes, and can reduce energy consumption.
concrete, adding the raw material of the first mass parts to polymeric kettle, the raw material of described the first mass parts comprises: pH adjusting agent, the monomer of the first mass parts, the water of the emulsifying agent of the first mass parts and 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, raw material to described the first mass parts heats, described Heating temperature is preferably 50～90 ℃, more preferably 60～80 ℃, when the raw material to described the first mass parts heats, add the initiator of the first mass parts in the reactor, when the transformation efficiency of the monomer of the first mass parts in polymeric kettle is 60%～90%, stopped heating.The reaction heat of the initiator for reaction of the raw material of the first mass parts and the first mass parts can be used for replenishing the required temperature of reaction of emulsion polymerization that the initiator of pre-emulsion and the second mass parts carries out.
After obtaining reaction solution, add the initiator of pre-emulsification material and the second mass parts in the described reaction solution, carry out letex polymerization.Wherein, described pre-emulsification material comprises the monomer of the second mass parts, the emulsifying agent of the second mass parts and the water of the second mass parts.
In the present invention, the monomer of the second mass parts is carried out pre-emulsification, obtain the pre-emulsification material.The present invention there is no particular restriction to described pre-emulsified mode, and pre-emulsification mode well known to those skilled in the art gets final product.Wherein, monomer is through abundant swelling after the 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 of the high polymerisation conversion of assurance, 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, carry out letex polymerization.Wherein, the temperature of described letex polymerization is preferably 80～100 ℃, more preferably 85～95 ℃.Measure the transformation efficiency of the monomer in polymeric kettle, when described monomer conversion＞99%, get final product stopped reaction, obtain end reaction liquid.
Wherein, the monomer of described the first mass parts is preferably (10～50) with the ratio of the consumption of the monomer of the second mass parts: (50～90), more preferably (20～40): (60～80); The emulsifying agent of described the first mass parts is preferably (10～50) with the ratio of the consumption of the emulsifying agent of the second mass parts: (50～90), more preferably (20～40): (60～80); The initiator of described the first mass parts is preferably (10～50) with the ratio of the consumption of the initiator of the second mass parts: (50～90), more preferably (20～40): (60～80); The water of described the first mass parts is preferably (10～50) with the ratio of the consumption of the water of the second mass parts: (50～90), 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 processing, regulates the pH value, can obtain adhesive for wood.
In the present invention, adopt degassed processing to remove whole unreacteds monomer completely.The present invention there is no particular restriction to the mode of described degassed processing, and the preferred mode that adopts pressurization to vacuumize is carried out degassed processing.After described degassed processing, measure the residual volume of unsaturated volatile matter in end reaction liquid, described residual volume is preferably≤300ppm, more preferably≤200ppm.Regulate the pH value of described end reaction liquid with ammoniacal liquor, can obtain adhesive for wood, the scope of described pH value is preferably 5.5～7.5, and more preferably 6～7.
The present invention is take vinyl esters of unsaturated carboxylic acids and/or aromatic ethylene compound as main monomer, be aided with a kind of and multiple as function monomer in vinyl unsaturated nitrile, unsaturated carboxylic acid and unsaturated carboxylic acid acid amides, avoid using formaldehyde to be raw material, and the method for employing letex polymerization, make the adhesive for wood for preparing have excellent water tolerance, cohesiveness and solvent resistance.
Result shows, the viscosity 〉=269mpas of the adhesive for wood that the present invention is prepared, remaining unsaturated volatile matter≤300ppm, particle diameter are 1.0～2.2 μ m, and total solid content is 40%～45%.And, having good physical strength, Formaldehyde emission rate is low.
In order further to understand the present invention, below in conjunction with embodiment, adhesive for wood provided by the invention is described, protection scope of the present invention is not limited by the following examples.
Embodiment 1
Add 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, 2.5g N hydroxymethyl acrylamide in the pre-emulsification still, stirred 20 minutes under 25 ℃ of conditions, stir, obtain the pre-emulsification material.
Add deionized water 20g, ammonium persulphate 0.7g in the initiator groove, be stirred to dissolving, obtain initiator solution.With 30% initiator solution as the first mass parts of described initiator solution quality, with 70% initiator solution as the second mass parts of described initiator solution quality.
After vacuumizing, polymeric kettle adds 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 in still, 0.1g Sodium phosphate dibasic, stirred 20 minutes under 25 ℃ of conditions, stir.
Chuck by reactor heats up with steam, when temperature reaches 80 ℃, stop steam and heat up, add the initiator solution of the first mass parts, then begin reaction, reacted 2 hours, when reacting when reaching 90% to transformation efficiency, slow continuous charging in the reactor, be that the pre-emulsification material of above-mentioned preparation, the initiator solution of the second mass parts are thrown into respectively in reactor, temperature is controlled at 90 ℃, after the reinforced end of the initiator of described pre-emulsification material and the second mass parts, temperature of reaction is maintained 95 ℃.When transformation efficiency reaches 99% when above, polymeric kettle is vacuumized, carry out degassed processing, remove the monomer of whole remnants, measure that in emulsion, remaining unsaturated volatile matter is 226ppm.PH value with ammoniacal liquor impregnation breast reaches 7.3, and product cools to 30 ℃, packs to tempering tank after filtering, obtains adhesive for wood.Measure total solid substance, viscosity, median size of described based Wood Adhesives etc., the results are shown in Table 1, table 1 is the prepared based Wood Adhesives physico-chemical property of embodiment 1～3.
The based Wood Adhesives of embodiment 1 preparation is carried out the water resistance test, and concrete grammar is as follows:
Be the steel test piece of 100mm * 25mm * 3mm with specification, the polishing of sand for surface paper, acetone is cleaned, and obtains shear test block;
the adhesive for wood of embodiment 1 preparation is coated on described shear test block, wherein, bond length is 15mm, self-vulcanizing 24h, place respectively 0h in the distilled water of 23 ℃ ± 2 ℃, 3h, 7h, 15h, 30h, after 48h, take out the test specimen room temperature and hang 24 hours, adopting respectively the Shanghai Shenlian Tester Factory model under the condition of 25 ℃ is the shearing resistance of the electronic tension tester mensuration test specimen of LD-50 type, wherein, 3 parallel samples of every group of data determination, average, the results are shown in Table 2, table 2 is the shearing resistance experimental result of the prepared adhesive for wood of embodiment 1.
The shearing resistance experimental result of the adhesive for wood that table 2 embodiment 1 is prepared
Be the steel test piece of 100mm * 25mm * 3mm with specification, the polishing of sand for surface paper, acetone is cleaned, and obtains shear test block;
Adhesive for wood in above-mentioned shearing test piece surface-coated embodiment 1 preparation, the glued membrane of preparation 0.2mm * 25mm * 60mm, self-vulcanizing 24h, after putting into the distilled water of 23 ℃ ± 2 ℃ and placing respectively 0h, 3h, 7h, 15h, 30h, 48h, take out the test specimen room temperature and hang 24 hours, the taking-up test specimen dries, and observes the glued membrane state.Experimental result sees Table 3, and table 3 is the water resistance test result of the adhesive for wood of embodiment 1 preparation.
The water resistance test result of the adhesive for wood of table 3 embodiment 1 preparation
Measuring respectively the shear test block immersion 30 hours scribble adhesive for wood and the strength retention of 48 hours is 99.6% and 95.9%.
Result shows, the adhesive for wood that embodiment 1 is prepared have a good water tolerance.
The based Wood Adhesives of embodiment 1 preparation is carried out the solvent resistance test, and concrete grammar is as follows:
Be the steel test piece of 100mm * 25mm * 3mm with specification, the polishing of sand for surface paper, acetone is cleaned, and obtains shear test block;
Adhesive for wood in above-mentioned shearing test piece surface-coated embodiment 1 preparation, the glued membrane of preparation 0.2mm * 25mm * 60mm, 120 ℃ solidified 30 minutes, after putting into No. 120 solvent oils and placing respectively 0h, 8h, 18h, 28h, 38h, 48h, take out the test specimen room temperature and hang 24 hours, observe the glued membrane surface and have or not bubble, wrinkling, obscission state, the results are shown in Table 4, table 4 is the solvent resistance test result of the sizing agent of embodiment 1 preparation.
The solvent resistance test result of the sizing agent of table 4 embodiment 1 preparation
As shown in Table 4, the product solvent resistance is superior, does not occur bubble, wrinkling, obscission in 48 hours.
Embodiment 2
Add 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 in the pre-emulsification still, stirred 20 minutes under 25 ℃ of conditions, stir, obtain the pre-emulsification material.
Add deionized water 20g, ammonium persulphate 0.6g in the initiator groove, be stirred to dissolving, obtain initiator solution.With 30% initiator solution as the first mass parts of described initiator solution quality, with 70% initiator solution as the second mass parts of described initiator solution quality.
After vacuumizing, polymeric kettle adds 80g deionized water, 0.2g Seconary Alkane Sulphonate Sodium, 0.5g polyoxyethylene nonylphenol ether, 15g butyl acrylate, 10g vinylbenzene, 0.5g methacrylic acid in still, 0.2g Sodium phosphate dibasic, stirred 20 minutes under 25 ℃ of conditions, stir.
chuck by reactor heats up with steam, when temperature reaches 90 ℃, stopping steam heating up, the initiator solution that adds the first mass parts, then begin reaction, reacted 2 hours, when reacting when reaching 90% to transformation efficiency, slow continuous charging in the reactor, it is the pre-emulsification material of above-mentioned preparation, the initiator solution of the second mass parts is thrown into respectively in reactor, temperature is controlled at 90 ℃, after the reinforced end of the initiator of described pre-emulsification material and the second mass parts, temperature of reaction is maintained 95 ℃. when transformation efficiency reaches 99% when above, polymeric kettle vacuumizes, carry out degassed processing, remove the monomer of whole remnants, in emulsion, remaining unsaturated volatile matter is 183ppm.PH value with ammoniacal liquor impregnation breast reaches 7.0, and product cools to 30 ℃, packs to tempering tank after filtering, obtains adhesive for wood.Measure total solid substance, viscosity, median size of described based Wood Adhesives etc., the results are shown in Table 1, table 1 is the prepared based Wood Adhesives physico-chemical property of embodiment 1～3.
Embodiment 3
Add 30g deionized water, 0.5g octadecenoic acid potassium, 0.9g alkylphenol polyoxyethylene, 42g Octyl acrylate, 31g vinylbenzene, 3g vinyl cyanide, 1.8g vinylformic acid, 0.8g N hydroxymethyl acrylamide in the pre-emulsification still, stirred 20 minutes under 25 ℃ of conditions, stir, obtain the pre-emulsification material.
Add deionized water 20g, ammonium persulphate 0.7g in the initiator groove, be stirred to dissolving, obtain initiator solution.With 30% initiator solution as the first mass parts of described initiator solution quality, with 70% initiator solution as the second mass parts of described initiator solution quality.
After vacuumizing, polymeric kettle adds 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 in still, stirred 20 minutes under 25 ℃ of conditions, stir.
Chuck by reactor heats up with steam, when temperature reaches 90 ℃, stop steam and heat up, add the initiator solution of the first mass parts, then begin reaction, reacted 2 hours, when reacting when reaching 90% to transformation efficiency, slow continuous charging in the reactor, be that the pre-emulsification material of above-mentioned preparation, the initiator solution of the second mass parts are thrown into respectively in reactor, temperature is controlled at 90 ℃, after the reinforced end of the initiator of described pre-emulsification material and the second mass parts, temperature of reaction is maintained 95 ℃.When transformation efficiency reaches 99% when above, polymeric kettle vacuumizes, and carries out degassed processing, removes the monomer of whole remnants, measures that in emulsion, remaining unsaturated volatile matter is 211ppm.PH value with ammoniacal liquor impregnation breast reaches 6.8, and product cools to 30 ℃, packs to tempering tank after filtering, obtains adhesive for wood.Measure total solid substance, viscosity, median size of described based Wood Adhesives etc., the results are shown in Table 1, table 1 is the prepared based Wood Adhesives physico-chemical property of embodiment 1～3.
The based Wood Adhesives physico-chemical property that table 1 embodiment 1～3 is prepared
Embodiment 4
Adhesive for wood take wood fibre as raw material with embodiment 1 preparation mixes, and makes density board, and described density board is carried out performance test, and result is referring to table 5, and table 5 is the performance perameter of the density board of the embodiment of the present invention 1 preparation.
Comparative Examples 1
Produce the Precondensed UreaFormaldehyde Resin latex take wood fibre as raw material with the great Xiang chemical industry of Linyi City company limited and mixes, make density board, described density board is carried out performance test, result is referring to table 5, and table 5 is the performance perameter of the density board for preparing of the embodiment of the present invention 1.
Comparative Examples 2
The rubber made from soybean cake of producing with Shanghai Honghan Chemical Technology Co., Ltd. take wood fibre as raw material mixes, and makes density board, and described density board is carried out performance test, and result is referring to table 5, and table 5 is the performance perameter of the density board of the embodiment of the present invention 1 preparation.
The performance perameter of the density board of table 5 embodiment of the present invention 1 and comparative example 1～2 preparation
As shown in Table 5, the prepared adhesive for wood of 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; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle 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 (10)
1. the preparation method of an adhesive for wood comprises 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.
2. preparation method according to claim 1, is characterized in that, described preparation method is specially:
A) with the monomer of pH adjusting agent, the first mass parts, the initiator of the emulsifying agent of the first mass parts, the first mass parts mixes with the water of the first mass parts, reacts, and obtains reaction solution;
B) add the initiator of pre-emulsification material and the second mass parts in the described reaction solution, carry out letex polymerization, obtain adhesive for wood;
Described pre-emulsification material comprises the monomer of the second mass parts, the emulsifying agent of the second mass parts and the water of the second mass parts;
The monomer of described the 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 the 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 the 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 the 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, is characterized in that, described function monomer also comprises vinyl unsaturated nitrile compounds.
4. preparation method according to claim 1 and 2, 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).
5. preparation method according to claim 3, is characterized in that,
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.
6. preparation method according to claim 3, is characterized in that,
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.
7. 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 form.
8. preparation method according to claim 7, 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.
9. preparation method according to claim 1 and 2, is characterized in that, described initiator is water-soluble thermolysis type persulphate.
10. preparation method according to claim 1 and 2, is characterized in that, described pH adjusting agent is Sodium phosphate dibasic.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310117575.7A CN103146327B (en) | 2013-04-07 | 2013-04-07 | A kind of preparation method of adhesive for wood |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310117575.7A CN103146327B (en) | 2013-04-07 | 2013-04-07 | A kind of preparation method of adhesive for wood |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103146327A true CN103146327A (en) | 2013-06-12 |
| CN103146327B CN103146327B (en) | 2016-01-06 |
Family
ID=48544659
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310117575.7A Expired - Fee Related CN103146327B (en) | 2013-04-07 | 2013-04-07 | A kind of preparation method of adhesive for wood |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103146327B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106010304A (en) * | 2016-06-22 | 2016-10-12 | 张育栋 | Adhesive suitable for wood and preparation method of adhesive |
| CN106634725A (en) * | 2016-12-17 | 2017-05-10 | 浦北县建业胶合板有限责任公司 | Water-based copolymer adhesive and preparation method thereof |
| CN107216831A (en) * | 2017-07-07 | 2017-09-29 | 泗县美佳化建有限责任公司 | A kind of aggretion type aqueous, environmental protective pencil glues core rubber and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1135512A (en) * | 1995-05-12 | 1996-11-13 | 四川联合大学 | Aqueous emulsion paper-plastic composite adhesive |
-
2013
- 2013-04-07 CN CN201310117575.7A patent/CN103146327B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1135512A (en) * | 1995-05-12 | 1996-11-13 | 四川联合大学 | Aqueous emulsion paper-plastic composite adhesive |
Non-Patent Citations (2)
| Title |
|---|
| 李欣闻等: "丙烯酸酯乳液胶粘剂的合成及其性能研究", 《中国胶粘剂》 * |
| 黎文部等: "四元共聚丙烯酸酯热熔压敏胶膜的合成研究", 《中国胶粘剂》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106010304A (en) * | 2016-06-22 | 2016-10-12 | 张育栋 | Adhesive suitable for wood and preparation method of adhesive |
| CN106634725A (en) * | 2016-12-17 | 2017-05-10 | 浦北县建业胶合板有限责任公司 | Water-based copolymer adhesive and preparation method thereof |
| CN107216831A (en) * | 2017-07-07 | 2017-09-29 | 泗县美佳化建有限责任公司 | A kind of aggretion type aqueous, environmental protective pencil glues core rubber and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103146327B (en) | 2016-01-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1141895A (en) | Copolymers for pressure-sensitive adhesives based on acrylic esters, vinyl acetate and ethylene | |
| CN102559108B (en) | Preparation method for water-fast starch adhesive with high initial adhesion | |
| CN102333799B (en) | Process for producing vinyl acetate/ethylene copolymers by means of emulsion polymerization | |
| CN100537619C (en) | Method for preparing carboxylic styrene butadiene latex for carpet back coating | |
| CN102533177B (en) | High water resistance emulsion polyacrylate pressure-sensitive adhesive and preparation method and application thereof | |
| CN102372813B (en) | A kind of low viscosity vinyl acetate-ethylene copolymerization emulsions and preparation method and use thereof | |
| CN102408853B (en) | Water-based body flame-resistant acrylate adhesive and preparation method thereof | |
| CN101864025B (en) | Preparation method of polyacrylate microgel emulsion and application thereof | |
| CN102010478B (en) | Acrylic ester emulsion and preparation method thereof | |
| CN104497201B (en) | Rosin derivative/polyacrylate hybrid miniemulsion pressure sensitive adhesive and preparation method thereof | |
| CN102911630A (en) | Rear cross-linking heatproof emulsion pressure-sensitive adhesive and method for producing same | |
| CN102433091B (en) | Laminated wood plate alignment adhesive-based adhesive and preparation method thereof | |
| CN1083085A (en) | Multi-component adhesive polymer | |
| CN102585112A (en) | Preparation method of modified soy protein-acrylic ester composite emulsion | |
| CN103146327B (en) | A kind of preparation method of adhesive for wood | |
| CN103275260B (en) | Preparation method of acrylic plastic-plastic composite latex | |
| CN101205696A (en) | Method for preparing core-shell soap-free surface sizing agent | |
| WO2013167537A1 (en) | Use of copolymers as tackifiers for adhesives | |
| CN103113530B (en) | Preparation method of PVC (Polyvinyl Chloride) covalent bonding nanoparticle alloy resin | |
| CN101812209B (en) | Method for preparing nanometer attapulgite/polyvinyl acetate composite emulsion | |
| CN102559103B (en) | Fine pasting glue and preparing process thereof | |
| CN102533182A (en) | Method for preparing starch-based water-resistant adhesive for corrugated board production | |
| CN106479407A (en) | A kind of paper-plastic stick adhesive and preparation method thereof | |
| CN103012692B (en) | Method for preparing soybean protein copolymer emulsion | |
| CN106833452A (en) | Aqueous environment protection cohesive force sealing compound high and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20160805 Address after: Nine sets of Changji Economic Development Zone of Jilin province highway 130500 Changchun city 8 kilometers Patentee after: Jilin province wonder Polytron Technologies Inc Address before: 130000 Jilin province Changchun Changji City, East Lake Economic Development Zone North line of 8 kilometers in Jilin province Royaum Decoration Material Co. Ltd. Patentee before: Wang Yikui Patentee before: Wang Hongwei |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160106 Termination date: 20190407 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |