CN101805431B - Preparation method of EVA sole bonding promoter - Google Patents
Preparation method of EVA sole bonding promoter Download PDFInfo
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- CN101805431B CN101805431B CN2010101229575A CN201010122957A CN101805431B CN 101805431 B CN101805431 B CN 101805431B CN 2010101229575 A CN2010101229575 A CN 2010101229575A CN 201010122957 A CN201010122957 A CN 201010122957A CN 101805431 B CN101805431 B CN 101805431B
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- eva sole
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Abstract
The invention relates to a preparation method of an EVA sole bonding promoter. The method comprises the following steps: firstly adding chloroprene rubber and chlorinated polyethylene into a reaction solvent (the components are toluene, ethyl acetate, butanone and acetone), stirring, filling nitrogen after full dissolution, adding methyl methacrylate and vinyl acetate, increasing the temperature to 75-90 DEG C, and then adding benzoyl peroxide for carrying out polymerization; carrying out the polymerization for 2-3 hours, adding acrylic acid, continuing the reaction for 1-2 hours, then closing the nitrogen, reducing the temperature to 30-50 DEG C, further adding terpene resin and 2,6-di-tert-butyl-p-cresol, uniformly stirring, discharging materials and obtaining a graft copolymer; and mixing the graft copolymer with a dilution solvent according to the weight ratio of 1: 1.5-3, uniformly stirring and obtaining the EVA sole bonding promoter. The EVA sole bonding promoter prepared by the method has good comprehensive performance and significant bonding promotion role for an EVA sole.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a kind of preparation method of surface treatment agent, specifically is a kind of preparation method who is used to improve the EVA sole bonding promoter of bond strength.
Background technology
Features such as along with developing rapidly of shoe industry, EVA (ethylene-vinyl acetate copolymer) foam material is light because of quality, attractive in appearance and low price and in a large number as material for sole of shoe, especially its material of the sole of sandy beach slippers is EVA.Because EVA is a kind of low-pole material, and the avidity that has between strong polar polychloroprene tackifier and the polyurethane adhesive is not strong, give the bonding difficulty of bringing of EVA material, in order to improve the bonding strength of EVA sole, generally all use adhesion promotor before bonding, EVA to be carried out surface treatment on the shoe industry.Adhesion promotor can be regarded as by a bridging agent between sticking material and the tackiness agent, and its effect one is a contamination of removing the adherend surface, greasy dirt and help processing aid; The 2nd, can change by surface polarity, activity and the roughness etc. of sticking material being formed the new upper layer of one deck by sticking material surface, make it to be complementary with employed tackiness agent, improve bonding strength.
The toluene solution of trichloroisocyanuric acid carries out the adhesion promotion effect that can rise well after the surface treatment as a kind of adhesion promotor to the EVA sole, but its unstable need temporarily preparation makes material surface flavescence influence attractive in appearance simultaneously easily.The butanone solution of EVA multipolymer carries out the adhesion promotion effect that also can rise well after the surface treatment as a kind of adhesion promotor to the EVA sole, but its easy at low temperatures gel is not suitable for using winter.Zhang Yongqing has developed a kind of EVA surface treatment agent of preparing with the graft copolymer solution of methyl methacrylate and vinylformic acid and styrene-butadiene rubber(SBR) and has been used to promote EVA sole bonding [Huaqiao University's journal (natural science edition) 2000,21 (4) 432-434].
Summary of the invention
Purpose of the present invention just provides a kind of preparation method who is used to promote the EVA sole bonding promoter of EVA sole bonding.
The concrete technical scheme of the inventive method is:
Reaction solvent is added in the reactor that has stirring and reflux, drop into chloroprene rubber and chlorinatedpolyethylene then, stir, controlled temperature is 50～70 ℃; Treat that chloroprene rubber and chlorinatedpolyethylene dissolve the back fully and charge into nitrogen in reactor, add methyl methacrylate and vinyl acetate, adding benzoyl peroxide after being warming up to 75～90 ℃ carries out polyreaction; After the polyreaction 2～3 hours, add vinylformic acid, continue reaction and close nitrogen after 1～2 hour, be cooled to 30～50 ℃, add terpine resin and 2,6 one ditertbutylparacresols then, stir evenly the back discharging, obtain graft copolymer.
More than the parts by weight that add of each material be:
With graft copolymer and diluting solvent is 1: 1.5～3 to mix by weight, stirs, and obtains the EVA sole bonding promoter.
The component of described reaction solvent and the weight percent of each component are:
The component of described diluting solvent and the weight percent of each component are:
In the EVA sole bonding promoter of the inventive method preparation, component chlorinated polyethylene rubber and vinyl acetate reactive monomer are good to EVA material affinity, and the solvent price of use is relatively low.Therefore the EVA sole bonding promoter good combination property of the inventive method preparation has significant adhesion promotion effect to the EVA sole.
Embodiment
Embodiment 1
1200 gram reaction solvents (component is toluene 50w%, ethyl acetate 10w%, butanone 20w%, acetone 20w%) are added in the reactor that has stirring and reflux, drop into 100 gram chloroprene rubbers and 30 gram chlorinatedpolyethylenees then, stir, controlled temperature is 50 ℃.Treat that chloroprene rubber and chlorinatedpolyethylene dissolve the back fully and charge into nitrogen in reactor, add 20 gram methyl methacrylates and 30 gram vinyl acetates, adding 1.2 gram benzoyl peroxides after being warming up to 75 ℃ carries out polyreaction.After the polyreaction 2 hours, add 5 gram vinylformic acid again, continue reaction and close nitrogen after 1 hour, be cooled to 30 ℃, add 5 gram terpine resins and 1 gram, 2,6 one ditertbutylparacresols then, stir evenly the back discharging, obtain graft copolymer.
500 gram graft copolymers are mixed with 750 gram diluting solvents (component is toluene 50w%, butanone 20w%, ethyl acetate 20w%, acetone 10w%), stir, obtain the EVA sole bonding promoter.
Embodiment 2
800 gram reaction solvents (component is toluene 30w%, ethyl acetate 30w%, butanone 10w%, acetone 30w%) are added in the reactor that has stirring and reflux, drop into 100 gram chloroprene rubbers and 50 gram chlorinatedpolyethylenees then, stir, controlled temperature is 70 ℃.Treat that chloroprene rubber and chlorinatedpolyethylene dissolve the back fully and charge into nitrogen in reactor, add 30 gram methyl methacrylates and 50 gram vinyl acetates, adding 2.4 gram benzoyl peroxides after being warming up to 90 ℃ carries out polyreaction.After the polyreaction 3 hours, add 10 gram vinylformic acid again, continue reaction and close nitrogen after 2 hours, be cooled to 50 ℃, add 10 gram terpine resins and 2 grams, 2,6 one ditertbutylparacresols then, stir evenly the back discharging, obtain graft copolymer.
500 gram graft copolymers are mixed with 1500 gram diluting solvents (component is toluene 20w%, butanone 40w%, ethyl acetate 30w% and acetone 10w%), stir, obtain the EVA sole bonding promoter.
Embodiment 3
1000 gram reaction solvents (component is toluene 40w%, ethyl acetate 10w%, butanone 40w%, acetone 10w%) are added in the reactor that has stirring and reflux, drop into 100 gram chloroprene rubbers and 40 gram chlorinatedpolyethylenees then, stir, controlled temperature is 60 ℃.Treat that chloroprene rubber and chlorinatedpolyethylene dissolve the back fully and charge into nitrogen in reactor, add 30 gram methyl methacrylates and 40 gram vinyl acetates, adding 1.8 gram benzoyl peroxides after being warming up to 85 ℃ carries out polyreaction.After the polyreaction 2.5 hours, add 8 gram vinylformic acid again, continue reaction and close nitrogen after 1.5 hours, be cooled to 40 ℃, add 8 gram terpine resins and 1.5 grams, 2,6 one ditertbutylparacresols then, stir evenly the back discharging, obtain graft copolymer.
500 gram graft copolymers are mixed with 1000 gram diluting solvents (component is toluene 20w%, butanone 30w%, ethyl acetate 10w%, acetone 20w% and methylcarbonate 20%), stir, obtain the EVA sole bonding promoter.
Embodiment 4
1000 gram reaction solvents (component is toluene 35w%, ethyl acetate 20w%, butanone 25w%, acetone 20w%) are added in the reactor that has stirring and reflux, drop into 100 gram chloroprene rubbers and 35 gram chlorinatedpolyethylenees then, stir, controlled temperature is 55 ℃.Treat that chloroprene rubber and chlorinatedpolyethylene dissolve the back fully and charge into nitrogen in reactor, add 40 gram methyl methacrylates and 35 gram vinyl acetates, adding 1.5 gram benzoyl peroxides after being warming up to 80 ℃ carries out polyreaction.After the polyreaction 2.5 hours, add 7 gram vinylformic acid again, continue reaction and close nitrogen after 1.5 hours, be cooled to 35 ℃, add 6 gram terpine resins and 1.8 grams, 2,6 one ditertbutylparacresols then, stir evenly the back discharging, obtain graft copolymer.
500 gram graft copolymers are mixed with 800 gram diluting solvents (component is toluene 30w%, butanone 30w%, ethyl acetate 10w%, acetone 15w% and methylcarbonate 15%), stir, obtain the EVA sole bonding promoter.
Claims (2)
1. the preparation method of an EVA sole bonding promoter is characterized in that this method specifically: with reaction solvent add have stir and the reactor of reflux in, drop into chloroprene rubber and chlorinatedpolyethylene then, stir, controlled temperature is 50～70 ℃; Treat that chloroprene rubber and chlorinatedpolyethylene dissolve the back fully and charge into nitrogen in reactor, add methyl methacrylate and vinyl acetate, adding benzoyl peroxide after being warming up to 75～90 ℃ carries out polyreaction; After the polyreaction 2～3 hours, add vinylformic acid, continue reaction and close nitrogen after 1～2 hour, be cooled to 30～50 ℃, add terpine resin and 2,6-ditertbutylparacresol then, stir evenly the back discharging, obtain graft copolymer;
More than the parts by weight that add of each material be:
Reaction solvent 800～1200
Chloroprene rubber 100
Chlorinatedpolyethylene 30～50
Methyl methacrylate 20～40
Vinyl acetate 30～50
Benzoyl peroxide 1.2～2.4
Vinylformic acid 5～10
Terpine resin 5～10
2,6-ditertbutylparacresol 1～2
The component of described reaction solvent and the weight percent of each component are:
With graft copolymer and diluting solvent is 1: 1.5～3 to mix by weight, stirs, and obtains the EVA sole bonding promoter.
2. the preparation method of a kind of EVA sole bonding promoter as claimed in claim 1 is characterized in that: the component of described diluting solvent and the weight percent of each component are:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101229575A CN101805431B (en) | 2010-03-12 | 2010-03-12 | Preparation method of EVA sole bonding promoter |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101229575A CN101805431B (en) | 2010-03-12 | 2010-03-12 | Preparation method of EVA sole bonding promoter |
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| CN101805431A CN101805431A (en) | 2010-08-18 |
| CN101805431B true CN101805431B (en) | 2011-10-05 |
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| CN2010101229575A Expired - Fee Related CN101805431B (en) | 2010-03-12 | 2010-03-12 | Preparation method of EVA sole bonding promoter |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102746472B (en) * | 2012-04-20 | 2015-03-25 | 苏州兴业材料科技股份有限公司 | Special modified polypropylene resin and preparation method thereof |
| CN109280131A (en) * | 2018-08-01 | 2019-01-29 | 江苏益帆高分子材料有限公司 | A kind of EVA/AA/MA graft copolymer and preparation method thereof |
| CN113402837A (en) * | 2021-06-02 | 2021-09-17 | 佛山市高明大都化工有限公司 | EVA (ethylene-vinyl acetate) treating agent and preparation method thereof |
| CN114246396A (en) * | 2021-12-29 | 2022-03-29 | 广州大草原鞋业有限公司 | Molding process of finished shoes |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3340224B2 (en) * | 1994-01-07 | 2002-11-05 | 電気化学工業株式会社 | Chloroprene rubber adhesive |
| JP3426481B2 (en) * | 1997-10-20 | 2003-07-14 | 電気化学工業株式会社 | Chloroprene rubber composition and adhesive using the same |
| US6835777B2 (en) * | 2002-11-19 | 2004-12-28 | Equistar Chemicals, E.P. | Adhesive compositions having improved performance |
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Owner name: NANTONG GUANGTAI BIOCHEMISTRY PRODUCT CO., LTD. Free format text: FORMER OWNER: HANGZHOU ELECTRONIC SCIENCE AND TECHNOLOGY UNIV Effective date: 20131021 |
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