CN101787172A

CN101787172A - Preparation method of EVA sole surface treating agent

Info

Publication number: CN101787172A
Application number: CN 201010122990
Authority: CN
Inventors: 聂秋林
Original assignee: Hangzhou Dianzi University
Current assignee: NANTONG GUANGTAI BIOCHEMICAL PRODUCT Co Ltd
Priority date: 2010-03-12
Filing date: 2010-03-12
Publication date: 2010-07-28
Anticipated expiration: 2030-03-12
Also published as: CN101787172B

Abstract

The invention relates to a preparation method of an EVA sole surface treating agent. The existing products contain a great deal of toluene and are toxic. The preparation method comprises the following steps: firstly, adding chloroprene rubber and chlorinated polyethylene in reaction solvent containing 120# solvent oil, ethyl acetate, butanone and acetone, stirring for complete dissolution, injecting nitrogen, adding methylmethacrylate and vinyl acetate, heating to 80-100 DEG C, adding benzoyl peroxide to perform polymerization reaction for 2-3 hours, adding acrylic acid, replenishing benzoyl peroxide, reacting for 1-2 hours, stopping injecting nitrogen, reducing the temperature to 30-50 DEG C, then adding 2,6-di-tert-butyl-p-cresol, stirring evenly, discharging to obtain graft copolymer; and mixing graft copolymer with diluting solvent in a weight ratio of 1:1.5-3, and stirring evenly to obtain the EVA sole surface treating agent. The EVA sole surface treating agent prepared by the method of the invention has good environmental performance, and the EVA sole processed by the treating agent has obvious adhesion promoting function.

Description

A kind of preparation method of EVA sole surface treating agent

Technical field

The invention belongs to technical field of chemistry, 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 surface treating agent 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 surface treatment agent before bonding, EVA to be carried out surface treatment on the shoe industry.The material surface treatment agent 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 is handled the bond effect that can rise well behind the EVA, but its unstable need temporarily preparation makes material surface flavescence influence attractive in appearance simultaneously easily.The butanone solution of EVA multipolymer is handled the bond effect that also can rise well behind the EVA, 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) [Huaqiao University's journal (natural science edition) 2000,21 (4) 432-434].The solvent that these EVA sole surface treating agents use all contains a large amount of toluene.Toluene is a kind of moderately toxic solvent, can accumulate in human body, and long-term contact can cause respiratory disease, sacred disease even leukemia etc., causes serious harm for the workers'health of producing and using.

Summary of the invention

The preparation method who the purpose of this invention is to provide a kind of EVA sole surface treating agent of environment-friendly type.

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 60～80 ℃; Treat that chloroprene rubber and chlorinatedpolyethylene dissolve the back fully and charge into nitrogen in reactor, add methyl methacrylate and vinyl acetate then, be warming up to 80～100 ℃ after, add benzoyl peroxide and carry out polyreaction; After the polyreaction 2～3 hours, add vinylformic acid and add benzoyl peroxide, the amount of adding benzoyl peroxide is 1/4～1/2 of the initial add-on of benzoyl peroxide; Continue reaction and close nitrogen after 1～2 hour, be cooled to 30～50 ℃, add 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:

Reaction solvent 800～1200

Chloroprene rubber 100

Chlorinatedpolyethylene 20～40

Methyl methacrylate 20～40

Vinyl acetate 20～40

Benzoyl peroxide 1.5～2.4

Vinylformic acid 5～10

2,6 one ditertbutylparacresols 1～2

Graft copolymer and diluting solvent are mixed by weight 1: 1.5～3, stir, obtain the EVA sole surface treating agent.

The component of described reaction solvent and the weight percent of each component are:

120 ^#Solvent oil 10～40%

Ethyl acetate 10～40%

Butanone 10～40%

Acetone 10～30%

Methylcarbonate 0～30%

The component of described diluting solvent and the weight percent of each component are:

Butanone 20～40%

Ethyl acetate 20～40%

Acetone 20～40%

Methylcarbonate 0～20%

The inventive method is carried out graft copolymerization by chloroprene rubber, chlorinatedpolyethylene, methyl methacrylate, vinyl acetate and vinylformic acid in the reaction solvent of environment-friendly type, and then with the diluting solvent of environment-friendly type multipolymer is diluted and to form, the EVA sole surface treating agent that makes does not contain triphen, hydrochloric ether and free formaldehyde, has the good characteristics of the feature of environmental protection.Simultaneously, the EVA sole has significant adhesion promotion effect after this treatment agent is handled.

Embodiment

Embodiment 1

(component is 120 with 800 gram reaction solvents ^#Solvent oil 10w%, ethyl acetate 40w%, butanone 30w%, acetone 10w% and methylcarbonate 10w%) add in the reactor that has stirring and reflux, drop into 100 gram chloroprene rubbers and 20 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 20 gram vinyl acetates, adding 1 gram benzoyl peroxide after being warming up to 80 ℃ carries out polyreaction.After the polyreaction 2 hours, add 5 gram vinylformic acid and 0.5 gram benzoyl peroxide, continue reaction and close nitrogen after 2 hours, be cooled to 30 ℃, add 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 (butanone 40w%, ethyl acetate 40w%, acetone 20w%), stir, obtain the EVA sole surface treating agent.

Embodiment 2

(component is 120 with 1200 gram reaction solvents ^#Solvent oil 40w%, ethyl acetate 20w%, butanone 10w% and acetone 30w%) add in the reactor that has stirring and reflux, drop into 100 gram chloroprene rubbers and 40 gram chlorinatedpolyethylenees then, stir, controlled temperature is 80 ℃.Treat that chloroprene rubber and chlorinatedpolyethylene dissolve the back fully and charge into nitrogen in reactor, add 40 gram methyl methacrylates and 30 gram vinyl acetates, adding 1.8 gram benzoyl peroxides after being warming up to 100 ℃ carries out polyreaction.After the polyreaction 3 hours, add 10 gram vinylformic acid and 0.6 gram benzoyl peroxide, continue reaction and close nitrogen after 1 hour, be cooled to 50 ℃, add 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 (butanone 35w%, ethyl acetate 35w%, acetone 20w% and methylcarbonate 10%), stir, obtain the EVA sole surface treating agent.

Embodiment 3

(component is 120 with 1000 gram reaction solvents ^#Solvent oil 20w%, ethyl acetate 10w%, butanone 40w%, acetone 20w% and methylcarbonate 10w%) add in the reactor that has stirring and reflux, drop into 100 gram chloroprene rubbers and 30 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 40 gram vinyl acetates, adding 1.4 gram benzoyl peroxides after being warming up to 90 ℃ carries out polyreaction.After the polyreaction 2.5 hours, add 8 gram vinylformic acid and 0.7 gram benzoyl peroxide, continue reaction and close nitrogen after 1.5 hours, be cooled to 40 ℃, add 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 (butanone 30w%, ethyl acetate 20w%, acetone 30w% and methylcarbonate 20%), stir, obtain the EVA sole surface treating agent.

Embodiment 4

(component is 120 with 1000 gram reaction solvents ^#Solvent oil 10w%, ethyl acetate 10w%, butanone 20w%, acetone 30w% and methylcarbonate 30w%) add in the reactor that has stirring and reflux, drop into 100 gram chloroprene rubbers and 25 gram chlorinatedpolyethylenees then, stir, controlled temperature is 65 ℃.Treat that chloroprene rubber and chlorinatedpolyethylene dissolve the back fully and charge into nitrogen in reactor, add 20 gram methyl methacrylates and 40 gram vinyl acetates, adding 1.6 gram benzoyl peroxides after being warming up to 85 ℃ carries out polyreaction.After the polyreaction 2.5 hours, add 6 gram vinylformic acid and 0.4 gram benzoyl peroxide, continue reaction and close nitrogen after 1.5 hours, be cooled to 35 ℃, add 1.5 grams, 2,6 one ditertbutylparacresols then, stir evenly the back discharging, obtain graft copolymer.

500 gram graft copolymers are mixed with 1250 gram diluting solvents (butanone 20w%, ethyl acetate 20w%, acetone 40w% and methylcarbonate 20%), stir, obtain the EVA sole surface treating agent.

Claims

1. the preparation method of an EVA sole surface treating agent 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 60～80 ℃; Treat that chloroprene rubber and chlorinatedpolyethylene dissolve the back fully and charge into nitrogen in reactor, add methyl methacrylate and vinyl acetate then, be warming up to 80～100 ℃ after, add benzoyl peroxide and carry out polyreaction; After the polyreaction 2～3 hours, add vinylformic acid and add benzoyl peroxide, the amount of adding benzoyl peroxide is 1/4～1/2 of the initial add-on of benzoyl peroxide; Continue reaction and close nitrogen after 1～2 hour, be cooled to 30～50 ℃, add 2,6 ditertiary butyl p cresol then, stir evenly the back discharging, obtain graft copolymer; More than the parts by weight that add of each material be: