CN115975465B - Preparation method of water-based EVA (ethylene-vinyl acetate copolymer) surface treating agent - Google Patents
Preparation method of water-based EVA (ethylene-vinyl acetate copolymer) surface treating agent Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 title claims description 75
- 239000003795 chemical substances by application Substances 0.000 title claims description 33
- 239000005038 ethylene vinyl acetate Substances 0.000 title description 69
- 239000012756 surface treatment agent Substances 0.000 claims abstract description 28
- 229920001577 copolymer Polymers 0.000 claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 23
- -1 amide compound Chemical class 0.000 claims abstract description 21
- 239000004094 surface-active agent Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000007789 sealing Methods 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 14
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 9
- 125000003172 aldehyde group Chemical group 0.000 claims description 9
- 229940015043 glyoxal Drugs 0.000 claims description 9
- 150000001299 aldehydes Chemical class 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 7
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims description 6
- 125000003368 amide group Chemical group 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- WSMYVTOQOOLQHP-UHFFFAOYSA-N Malondialdehyde Chemical compound O=CCC=O WSMYVTOQOOLQHP-UHFFFAOYSA-N 0.000 claims description 3
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 3
- 229940118019 malondialdehyde Drugs 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims description 3
- NISQVXMPIWWGOO-UHFFFAOYSA-N 4,5-dihydro-1h-imidazole;dihydrochloride Chemical compound Cl.Cl.C1CN=CN1 NISQVXMPIWWGOO-UHFFFAOYSA-N 0.000 claims description 2
- 229920001744 Polyaldehyde Polymers 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- ZKIAYSOOCAKOJR-UHFFFAOYSA-M lithium;2-phenylethenesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 ZKIAYSOOCAKOJR-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 238000010526 radical polymerization reaction Methods 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 7
- 230000036541 health Effects 0.000 abstract description 4
- 239000003431 cross linking reagent Substances 0.000 abstract 3
- 238000007037 hydroformylation reaction Methods 0.000 abstract 3
- 239000000243 solution Substances 0.000 description 58
- 239000007864 aqueous solution Substances 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 230000001070 adhesive effect Effects 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000004381 surface treatment Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 239000010410 layer Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 5
- 238000001694 spray drying Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 3
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to a preparation method of a water-based EVA surface treatment agent, which comprises the steps of preparing a water-soluble amide compound, wherein the water-soluble amide compound and a multi-hydroformylation monomer cross-linking agent are adopted as a compatibility main body; adding a surface active compound to form a copolymer containing the surface active compound when preparing the water-soluble amide compound, dissolving the copolymer with water as a solvent, and mixing a multi-hydroformylation monomer crosslinking agent to form the high-solid-content reactive water-based EVA surface treatment agent; or after preparing the water-soluble amide compound, dissolving the water as a solvent, mixing the multi-hydroformylation monomer cross-linking agent, and adding the surface active compound to form the high-solid-content reactive water-based EVA surface treatment agent. Has the advantages of simple preparation, low cost, only water volatilization in the operation process and no threat to human health.
Description
Technical Field
The invention relates to a preparation method of a water-based EVA surface treatment agent.
Background
The foamed EVA (ethylene-vinyl acetate copolymer) material is widely applied in the shoe industry due to excellent performances of good elasticity, strong air permeability, light weight, low cost and the like, and the EVA material has low surface energy, and shoe-making glue (such as chloroprene rubber adhesive, polyurethane adhesive, chlorinated polypropylene and the like) has strong polarity, so that the EVA material surface is difficult to wet, the problem of insufficient adhesion and the like is caused, and therefore, the EVA shoe material surface needs to be roughened, treated by a treating agent and the like in the bonding process to improve the bonding strength. Zhang Yongqing it is reported that toluene solution is adopted to dissolve styrene-butadiene rubber [ Programmes of the university of Programmes per se (Nature science edition) 2000, 21 (4) 432-434], free radical is adopted to initiate methyl methacrylate and acrylic acid to graft styrene-butadiene rubber, and a polymerization solution system is adopted as EVA treating agent, so that a good treatment effect is obtained, but the process is complex, a large amount of toluene is adopted as solvent, toluene is extremely volatile and can be harmful to human health after long-term use, and a toluene treatment device is required.
The existing commercial chloride EVA surface treatment agents of MORTON and DUPONT also adopt toluene as a solvent, so that the cost is high, and the problems of toluene volatilization and the like are serious. CN103756233a discloses a preparation method of a water-based EVA surface treating agent, which adopts toluene and ethyl acetate to dissolve chlorinated polypropylene, free radical initiates methyl methacrylate and acrylic acid to graft modified chlorinated polypropylene, and through reduced pressure distillation, 50% -80% of solvent is removed, the PH value is adjusted to 6.5-8.5, deionized water and polyvinylpyrrolidone are added to form the preparation method of the water-based EVA surface treating agent, the preparation process is complex, and meanwhile, the EVA surface treating agent still contains 20% -50% of mixed solvent of toluene and ethyl acetate, which is harmful to human health after long-term use. CN112428716a discloses a novel foam shaft printing method, which comprises 30-35g of diethylenetriamine, 15-18g of ammonium chloride, 5-7g of propylene glycol, 25-30g of dicyandiamide, 20-25g of ethylene glycol, 4-5g of epichlorohydrin, 5-7g of glacial acetic acid and the balance of water, and is used for EVA surface treatment.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of a water-based EVA surface treatment agent, which is simple to prepare, low in cost, and free from threatening to human health, and only water volatilizes in the operation process.
The invention discloses a preparation method of a water-based EVA surface treatment agent, which comprises the following steps:
a. preparing a water-soluble amide compound: dissolving 20-60 parts by mass of acrylamide monomer in 100 parts by mass of solvent, sealing and preserving heat at 40-80 ℃ for 0.2-1 hour to enable the acrylamide monomer to be completely dissolved to form a first solution, and cooling to 25-60 ℃; adding glycidyl methacrylate accounting for 1-10% of the monomer amount compared with the acrylamide monomer into the first solution to form a second solution; adding 0.1-2 parts by mass of an initiator into the second solution to form a third solution, sealing and heating to 60-90 ℃, preserving heat for 0.5-1.5 hours, and removing all solvents to obtain an acrylamide-glycidyl methacrylate copolymer;
b. dissolving the copolymer and water according to the mass ratio of 20-60:100, adding a multi-component aldehyde monomer to form a fourth solution, wherein the quantity ratio of aldehyde groups in the added multi-component aldehyde monomer to amide groups in the water-soluble amide compound is 0.5-1:2;
c. adding a surface active compound and the water-soluble amide compound into the fourth solution according to the mass ratio of 0-35:100, preferably the mass ratio of 20-40:100, wherein the added surface active compound is a high molecular surface active compound, including but not limited to polyvinylpyrrolidone and polyvinyl alcohol, preferably polyvinylpyrrolidone; obtaining the water-based EVA surface treating agent.
The invention discloses a preparation method of a water-based EVA surface treatment agent, which comprises the following steps:
a. preparing a water-soluble amide compound: dissolving 20-60 parts by mass of acrylamide monomer in 100 parts by mass of solvent, sealing and preserving heat at 40-80 ℃ for 0.2-1 hour to enable the acrylamide monomer to be completely dissolved to form a first solution, and cooling to 25-60 ℃; adding glycidyl methacrylate with the monomer quantity accounting for 1-10% compared with the acrylamide monomer and a surface active compound with the monomer quantity accounting for 2-14% compared with the acrylamide monomer into the first solution to form a second solution; adding 0.1-2 parts by mass of an initiator into the second solution to form a third solution, sealing and heating to 60-90 ℃, preserving heat for 0.5-1.5 hours, and removing all solvents to obtain an acrylamide-glycidyl methacrylate-surface active compound copolymer;
the added surface active compound is a small molecular surface active compound, has surface activity after polymerization, and comprises 2-acrylamide-2-methylpropanesulfonic acid and sodium salt thereof, namely, lithium styrene sulfonate and methacryloyloxyethyl trimethyl ammonium chloride, and is preferably 2-acrylamide-2-methylpropanesulfonic acid;
b. dissolving the copolymer and water according to the mass ratio of 20-60:100, adding a multi-component aldehyde monomer to form a fourth solution, wherein the quantity ratio of aldehyde groups in the added multi-component aldehyde monomer to amide groups in the water-soluble amide compound is 0.5-1:2; obtaining the water-based EVA surface treating agent.
In the preparation of the aqueous EVA surface treatment agent, the polyaldehyde monomer used in the invention is a monomer containing at least two aldehyde groups, including but not limited to malondialdehyde and glyoxal, and preferably glyoxal.
In the preparation of the water-soluble amide compound, the solvent is one or more of ethanol, toluene and tetrahydrofuran, and is preferably ethanol.
In the preparation of the water-soluble amide compound, the initiator is a substance capable of generating free radical polymerization active center, and the initiator can be commercially available products including but not limited to azodiisobutyronitrile, 2 '-azacyclo (2-imidazoline) dihydrochloride and 2,2' -azodiisobutylamidine dihydrochloride, and preferably azodiisobutyronitrile.
In the preparation of the water-soluble amide compound, the acrylamide monomer used in the invention comprises one or more of acrylamide, methacrylamide and N-methylol acrylamide, and preferably acrylamide.
The invention has the following positive effects:
1) Aiming at the problem of volatilization of an organic solvent, the water-based EVA surface treating agent prepared by the invention adopts water as the solvent of the EVA surface treating agent, and the components except the water participate in film formation and cannot volatilize; meanwhile, the finished product surface treating agent adopts water as a solvent, so that volatilization treatment of an organic solvent is avoided, the surface treating agent is used for surface treatment of EVA shoe materials, and the surface treating cost is reduced on the basis of not reducing the bonding performance;
2) According to the invention, the acrylamide monomer and the glycidyl methacrylate are copolymerized in a certain amount and proportion, so that the copolymer has good water solubility, and meanwhile, a certain amount of glycidyl methacrylate structure is arranged in the main chain, so that good activity is provided for a film-forming treatment layer; when the EVA surface treating agent is used for the operation, the EVA surface treating agent is coated on the clean surface to be bonded of the shoe material, and the heat preservation stimulates the nitrogen atoms of the amide groups and the aldehyde groups to generate nucleophilic addition reaction, so that the film forming and curing are completed in the whole treatment operation process, the treatment effect is good, the polarity of the treated surface is improved, and the bonding strength and reliability are improved. The acrylamide monomer and glycidyl methacrylate with a certain amount of proportion can be completely dissolved in water by copolymerization, water can be used as a solvent, a large amount of volatilization problems of organic solvents such as toluene, xylene and ethyl acetate in the operation process of a conventional treating agent can be effectively solved, and the use cost of the treating agent is reduced. The surface active compound is added on the basis, so that the polarity level of the EVA surface treatment agent after film formation can be adjusted in a large range, different adhesive glues are adapted, the polarity level of the EVA surface treatment agent can be adjusted according to the requirements by adding the surface active substance, the leveling property of the EVA surface treatment agent can be effectively improved, the covering integrity is improved, the operation reliability is enhanced, and as the surface active substances have good surface activity and can be effectively dissolved in water no matter the small molecular weight or the high molecular weight, the EVA surface treatment agent adopts a lower cost and safer scheme, the problem of volatilization of harmful organic solvents is solved, the adhesive operation environment of EVA shoe materials is improved, and the product competitiveness is improved;
3) The defect of grafting modification of an organic solvent body reported in the prior art is overcome, a finished product surface treating agent directly adopts a water-soluble reaction monomer, water is directly adopted as a solvent to be matched with a crosslinking component, a high-solid-content aqueous solution system is formed, full coverage can be formed on the EVA surface through single coating, the crosslinking of amide groups and aldehyde groups is promoted by heat, a stable low-shrinkage transition film layer is formed, the polarity of the EVA surface, particularly the water-based shoe adhesive is effectively improved, and the bonding strength between the EVA surface treating agent and the shoe adhesive is enhanced; in addition, different water-soluble surface active compounds can be added according to the properties of the shoe glue, so that the polarity of the EVA treating agent can be adjusted in a large range, and the shoe glue with different brands can be adapted. Only water volatilizes in construction, the operation environment is more friendly to operators, solvents such as toluene, ethyl acetate, N-methyl pyrrolidone and the like do not volatilize, an organic gas recovery processing system of the operation environment can be simplified, and the operation safety and the production cost are greatly improved.
Description of the embodiments
Example 1, preparation method of aqueous EVA surface treatment agent
Dissolving 40g of acrylamide in 80g of absolute ethyl alcohol at room temperature, sealing and preserving heat at 60 ℃ for 30min to completely dissolve the acrylamide to form a first solution, and cooling to 30 ℃; adding 2.4g of glycidyl methacrylate to the first solution to form a second solution; dissolving 0.45g of azodiisobutyronitrile in 5g of ethanol, adding the solution into the second solution to form a third solution, sealing and heating to 80 ℃ for 1 hour, and performing spray drying to obtain an acrylamide-glycidyl methacrylate copolymer; taking 20g of the copolymer, stirring and dissolving the copolymer in 40g of deionized water at 50 ℃, and cooling the mixture to room temperature to obtain an aqueous solution; 20g of glyoxal aqueous solution with the mass content of 40% is added into the aqueous solution to form the aqueous EVA surface treating agent.
In the embodiment, the EVA surface treatment agent is coated on the cleaned EVA surface (part of the process needs to polish and coarsen the EVA surface), and the EVA surface treatment agent is dried at 70-75 ℃ for 5min to form a stable and uniform crosslinked transparent polymer film layer, so that the binding force of the film layer and the strong-polarity shoe adhesive can be effectively improved.
Example 2 preparation method of aqueous EVA surface treatment agent
Dissolving 20g of acrylamide and 24g of methacrylamide in 90g of absolute ethanol at room temperature, sealing and preserving heat at 60 ℃ for 30min to completely dissolve the acrylamide and the methacrylamide to form a first solution, and cooling to 30 ℃; adding 2.4g of glycidyl methacrylate to the first solution to form a second solution; dissolving 0.5g of azodiisobutyronitrile in 5g of ethanol, adding the solution into the second solution to form a third solution, sealing and heating to 80 ℃ for 1 hour, and performing spray drying to obtain an acrylamide-glycidyl methacrylate copolymer; taking 22g of the copolymer, stirring and dissolving the copolymer in 50g of deionized water at 50 ℃, and cooling the mixture to room temperature to obtain an aqueous solution; 20g of glyoxal aqueous solution with the mass content of 40% is added into the aqueous solution to form the aqueous EVA surface treating agent.
In the present invention, no surface active compound was added in each of examples 1 to 2.
Example 3 preparation method of aqueous EVA surface treatment agent
Dissolving 40g of acrylamide in 80g of absolute ethyl alcohol at room temperature, sealing and preserving heat at 60 ℃ for 30min to completely dissolve the acrylamide to form a first solution, and cooling to 30 ℃; 5g of 2-acrylamido-2-methylpropanesulfonic acid is dissolved in 15g of water to form a solution, and the solution is added to the first solution to form a second solution; adding 2.4g of glycidyl methacrylate to the second solution to form a third solution; dissolving 0.45g of azodiisobutyronitrile in 5g of ethanol, adding the solution into the third solution to form a fourth solution, sealing and heating to 80 ℃ for 1 hour, carrying out spray drying to obtain acrylamide-glycidyl methacrylate-2-acrylamide-2-methylpropanesulfonic acid copolymer, taking 21g of the copolymer, stirring and dissolving the copolymer in 45g of deionized water at 50 ℃, and cooling to room temperature to obtain an aqueous solution; 20g of glyoxal aqueous solution with the mass content of 40% is added into the aqueous solution to form the aqueous EVA surface treating agent.
In the embodiment 3, 5g of 2-acrylamide-2-methylpropanesulfonic acid is added into the first solution, the solution is adjusted to have stronger polarity, different shoe adhesives are adapted after film formation, and the added 2-acrylamide-2-methylpropanesulfonic acid can be copolymerized with acrylamide, so that the film formation property is more uniform. If 5g of poly (2-acrylamido-2-methylpropanesulfonic acid) is added, 10g of deionized water is added, wherein the poly (2-acrylamido-2-methylpropanesulfonic acid) is a high molecular compound, so that the surface activity of the copolymer is stronger, and the film forming leveling property is better.
Example 4 preparation method of an aqueous EVA surface treatment agent
Dissolving 40g of acrylamide in 80g of absolute ethyl alcohol at room temperature, sealing and preserving heat at 60 ℃ for 30min to completely dissolve the acrylamide to form a first solution, and cooling to 30 ℃; adding 2.4g of glycidyl methacrylate to the first solution to form a second solution; dissolving 0.45g of azodiisobutyronitrile in 5g of ethanol, adding the solution into the second solution to form a third solution, sealing and heating to 80 ℃ for 1 hour, and performing spray drying to obtain an acrylamide-glycidyl methacrylate copolymer; taking 20g of the copolymer, heating to 50 ℃, stirring and dissolving the copolymer in 40g of deionized water at 50 ℃, and cooling to room temperature to obtain an aqueous solution; adding 20g of glyoxal water solution with the mass content of 40% into the aqueous solution to form EVA surface treatment solution, dissolving 5g of polyvinylpyrrolidone into 15g of water, and then adding the EVA surface treatment solution to form the aqueous EVA surface treatment agent.
In this example 4, polyvinylpyrrolidone, a nonionic surface active polymer compound, was used.
Example 5 preparation method of an aqueous EVA surface treatment agent
Dissolving 40g of acrylamide in 80g of absolute ethyl alcohol at room temperature, sealing and preserving heat at 60 ℃ for 30min to completely dissolve the acrylamide to form a first solution, and cooling to 30 ℃; adding 7.5g of an aqueous solution of 80% mass content of methacryloyloxyethyl trimethyl ammonium chloride to the first solution to form a second solution; adding 2.4g of glycidyl methacrylate to the second solution to form a third solution; dissolving 0.5g of azodiisobutyronitrile in 5g of ethanol, adding the solution into the third solution to form a fourth solution, sealing and heating the solution to 80 ℃ for 1 hour, carrying out spray drying to obtain acrylamide-glycidyl methacrylate-methacryloyloxyethyl trimethyl ammonium chloride copolymer, taking 25g of the copolymer, stirring and dissolving the copolymer in 50g of deionized water at 50 ℃, and cooling the solution to room temperature to obtain an aqueous solution; 20g of glyoxal aqueous solution with the mass content of 40% is added into the aqueous solution to form the aqueous EVA surface treating agent.
In the invention, in the above examples 1 to 5, the solvent used for preparing the water-soluble amide compound is completely removed after the preparation, the solvent of the EVA surface treating agent is water, and the components except water participate in the surface treatment to form a film, so that the film cannot volatilize; meanwhile, as the finished product surface treating agent adopts water as a solvent, the surface treating agent can not cause danger to human bodies after volatilizing, and an organic gas recovery device is not needed in the EVA surface treatment operation environment.
According to the invention, the peel strength test of the water-based EVA surface treatment agent for the surface treatment of EVA materials: the aqueous EVA surface treatment agents obtained in examples 1 to 5 above were used for surface treatment of EVA materials: the EVA material is a mould pressing foaming EVA sheet with the thickness of 20mm and the hardness of 55-65, the surface of the EVA material to be treated is cleaned by adopting an aqueous cleaning agent, then cleaned by clean water, and dried; brushing the water-based EVA surface treating agent on the surface of a cleaned EVA material, drying at 70 ℃ for 5min to form a stable and uniform polymer film layer, vacuum drying at 75 ℃ for 10min to form the surface treated by the EVA treating agent, brushing water-based polyurethane shoe adhesive, and drying at 65 ℃ for 5min to form an activated adhesive layer. Bonding was performed under a pressure of 0.5MPa, and after 72 hours, peel strength was measured according to GB/T532-2008, and the results showed that the bonding strength of example 1 was 12N/cm, the bonding strength of example 2 was 9N/cm, the bonding strength of example 3 was 21N/cm, the bonding strength of example 4 was 15N/cm, the bonding strength of example 5 was 18N/cm, and the bonding strength of the EVA surface treatment agent without coating was only 6N/cm, which indicated that the bonding strength of the EVA surface treatment agent of the present invention could be improved. The highest bonding strength of the embodiment 3 is mainly because the addition of the 2-acrylamide-2-methylpropanesulfonic acid can promote the crosslinking reaction, improve the film forming quality and obtain a good EVA surface treatment effect; the EVA adhesive property is obviously improved in comparison with the example 1 and the example 2 which are not treated by the treating agent; compared with the examples 1 and 2, the examples 4 and 5 have better bonding effect, mainly because the surface active compound is further added, the polarity regulation and control are sufficient, the leveling property on the EVA surface is higher, the integrity of the film layer is high, polar groups are added, and in addition, the acting force of epoxy in glycidyl methacrylate and amino (ring opening can occur with epoxy) and other polar groups in the aqueous polyurethane shoe adhesive has better bonding effect.
Claims (4)
1. The preparation method of the water-based EVA surface treating agent comprises the following steps:
a. preparing a water-soluble amide compound: dissolving 20-60 parts by mass of acrylamide monomer in 100 parts by mass of solvent, sealing and preserving heat at 40-80 ℃ for 0.2-1 hour to enable the acrylamide monomer to be completely dissolved to form a first solution, and cooling to 25-60 ℃; adding glycidyl methacrylate accounting for 1-10% of the monomer amount compared with the acrylamide monomer into the first solution to form a second solution; adding 0.1-2 parts by mass of an initiator into the second solution to form a third solution, sealing and heating to 60-90 ℃, preserving heat for 0.5-1.5 hours, and removing the solvent to obtain an acrylamide-glycidyl methacrylate copolymer;
the acrylamide monomer comprises at least one of acrylamide, methacrylamide and N-methylol acrylamide;
b. dissolving the copolymer and water according to the mass ratio of 20-60:100, adding a multi-component aldehyde monomer to form a fourth solution, wherein the quantity ratio of aldehyde groups in the added multi-component aldehyde monomer to amide groups in the water-soluble amide compound is 0.5-1:2;
the multi-aldehyde monomer is a monomer containing at least two aldehyde groups and comprises at least one of malondialdehyde and glyoxal;
c. adding a surface active compound and the water-soluble amide compound into the fourth solution according to the mass ratio of 0-35:100, wherein the added surface active compound is a high molecular surface active compound and comprises at least one of polyvinylpyrrolidone and polyvinyl alcohol; obtaining the water-based EVA surface treating agent.
2. The preparation method of the water-based EVA surface treating agent comprises the following steps:
a. preparing a water-soluble amide compound: dissolving 20-60 parts by mass of acrylamide monomer in 100 parts by mass of solvent, sealing and preserving heat at 40-80 ℃ for 0.2-1 hour to enable the acrylamide monomer to be completely dissolved to form a first solution, and cooling to 25-60 ℃; adding glycidyl methacrylate with the monomer quantity accounting for 1-10% compared with the acrylamide monomer and a surface active compound with the monomer quantity accounting for 2-14% compared with the acrylamide monomer into the first solution to form a second solution; adding 0.1-2 parts by mass of an initiator into the second solution to form a third solution, sealing and heating to 60-90 ℃, preserving heat for 0.5-1.5 hours, and removing the solvent to obtain an acrylamide-glycidyl methacrylate-surface active compound copolymer;
the acrylamide monomer comprises at least one of acrylamide, methacrylamide and N-methylol acrylamide;
the added surface active compound is a micromolecular surface active compound and comprises at least one of 2-acrylamide-2-methylpropanesulfonic acid and sodium salt thereof, lithium styrenesulfonate and methacryloyloxyethyl trimethyl ammonium chloride;
b. dissolving the copolymer and water according to the mass ratio of 20-60:100, adding a multi-component aldehyde monomer to form a fourth solution, wherein the quantity ratio of aldehyde groups in the added multi-component aldehyde monomer to amide groups in the water-soluble amide compound is 0.5-1:2; obtaining an aqueous EVA surface treatment agent;
the polyaldehyde monomer is a monomer containing at least two aldehyde groups and comprises at least one of malondialdehyde and glyoxal.
3. The method for producing an aqueous EVA surface treatment agent according to claim 1 or 2, wherein the solvent is one or a mixture of more than one of ethanol, toluene, and tetrahydrofuran.
4. The method for preparing an aqueous EVA surface treatment agent according to claim 1 or 2, wherein the initiator is a substance that can generate a radical polymerization active center, and includes at least one of azobisisobutyronitrile, 2 '-aza (2-imidazoline) dihydrochloride, and 2,2' -azobisisobutylaminidine dihydrochloride.
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| CN114829497A (en) * | 2019-12-27 | 2022-07-29 | 株式会社可乐丽 | Thermoplastic elastomer composition, vibration-proof material, gear, and composite molded body |
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| CN114829497A (en) * | 2019-12-27 | 2022-07-29 | 株式会社可乐丽 | Thermoplastic elastomer composition, vibration-proof material, gear, and composite molded body |
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Denomination of invention: Preparation method of a water-based EVA surface treatment agent Effective date of registration: 20231117 Granted publication date: 20230919 Pledgee: Bank of China Limited Jieyang branch Pledgor: GUANGDONG STICK SHOES Co.,Ltd. Registration number: Y2023980066231 |
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Denomination of invention: Preparation method of water-based EVA surface treatment agent Granted publication date: 20230919 Pledgee: Bank of China Limited Jieyang branch Pledgor: GUANGDONG STICK SHOES Co.,Ltd. Registration number: Y2024980026852 |