CN106432553B - A kind of EVA shoe material inorganic agent - Google Patents
A kind of EVA shoe material inorganic agent Download PDFInfo
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- CN106432553B CN106432553B CN201610814899.XA CN201610814899A CN106432553B CN 106432553 B CN106432553 B CN 106432553B CN 201610814899 A CN201610814899 A CN 201610814899A CN 106432553 B CN106432553 B CN 106432553B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2810/00—Chemical modification of a polymer
- C08F2810/50—Chemical modification of a polymer wherein the polymer is a copolymer and the modification is taking place only on one or more of the monomers present in minority
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2423/00—Presence of polyolefin
- C09J2423/04—Presence of homo or copolymers of ethene
- C09J2423/046—Presence of homo or copolymers of ethene in the substrate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2423/00—Presence of polyolefin
- C09J2423/04—Presence of homo or copolymers of ethene
- C09J2423/048—Presence of homo or copolymers of ethene in the pretreated surface to be joined
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- Chemical Kinetics & Catalysis (AREA)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of polymer-modified, there is the low polar structure close with EVA resin, being introduced on molecular side chain can antipolarity group hydroxy and carboxyl in the polymer molecule backbone.Meanwhile the invention discloses the polymer-modified preparation method, in preparation process, by adjusting Saponification Conditions and enzymatic synthesis condition, different types of acid anhydrides is selected, it can be achieved that polar freely being adjusted to polymer-modified.The invention also discloses a kind of comprising the polymer-modified EVA shoe material inorganic agent, the inorganic agent is big to the alternative of solvent, have many advantages, such as universality to different footwear materials, while having then that effect is good, ageing-resistant anti-hydrolytic performance is good, affine good penetrability to material.
Description
Technical field
The present invention relates to a kind of footwear material inorganic agent, especially a kind of EVA shoe material inorganic agent.
Background technology
Shoemaking EVA (ethylene-vinyl acetate copolymer) material, because of the various property of shoes to be reached especially sport footwear
It can require, usual ethylene component content is higher, and better polyolefin (such as polyoctenamer of various resilience flexibilities may need to be blended
Deng), and various lubricants, plasticizer, releasing agent, inorganic filler etc. due to being added in material processing so that material table
Face polarity is very low, and shoe industry generally uses polyurethane adhesive at present, since the polarity of polyurethane adhesive is relatively high,
According to similar compatibility principle, such as directly in EVA surface coatings, it is hardly formed effectively then (the shoemaking requirement for meeting shoemaking requirement
It can only be surface-treated with simple chemical method, reach material damage when then removing afterwards rather than glue-line destruction or interfacial failure
Or peeling force is at least up to 3N/mm).
Current then scheme generally has following three kinds：
1, material is first ground into thick and clean surface, to remove the low polarity grease on surface and increase the surface of material
Product, is then surface-treated with the sol solutions of chlorinated polypropylene, and EVA material surface is made to form the transition of one layer of chlorinated polypropylene
Layer.Low polarity similitude using main chain in chlorinated polypropylene similar to the structure of ethylene moiety in EVA is formed then, again with EVA
It is formed then using the highly polar and polyurethane of chlorine element in chlorinated polypropylene, to realize that EVA is glued with the effective of other shoes material
It closes.
2, it is polymerize in EVA particle solutions with methyl methacrylate, forms the macromolecule of interpenetrating networks or connecing on a small quantity
The polymeric mixed solution of branch, after which is diluted, the surface conditioning agent as EVA.Utilize EVA in inorganic agent and shoes
The similar compatibility of the similar compatibility of EVA and poly- methylpropionic acid methyl esters part and polyurethane adhesive, which is formed, in material effectively connects
It, similarly, this kind of inorganic agent is also required to first polish coarse by material surface and clean.
3, using the inorganic agent of ultra-violet curing type, the acrylic monomers of one layer of ultraviolet-curing is first applied in material surface
Class inorganic agent, then material surface is irradiated with ultraviolet light, so that a part is penetrated into the small molecule propernoic acid ester monomer solid of material internal
It is melted into polyacrylate, is formed effectively then using the similar compatibility of acrylate and polyurethane adhesive.
But above 1st type deals with agent using chlorinated polypropylene, since chlorine element is deposited in chlorinated polypropylene
So that the anti-yellowing property of inorganic agent is very poor, since in shoemaking, inorganic agent may inevitably be brushed to and not need glue
The position connect, so this inorganic agent is only used in the very deep EVA material of some colors.The inorganic agent of above 2nd type,
Since EVA is difficult to dissolve in usual vehicle, it usually needs with benzene, toluene, halogenated hydrocarbon solvent, process is used in shoemaking worker
In, these solvents are inevitably caused to damage and be damaged to operator and atmospheric environment.Above 1st, the 2nd is two kinds of
Inorganic agent is only applicable to some density of material, the lower foaming EVA material of hardness, or is only applicable to special ethylene-acetic acid
The EVA material of propane ratio.For projecting the EVA of EVA, post forming or the material of lower polar polyolefin being blended,
Can not be formed effectively then (cannot reach village's material destruction or 3N/mm is not achieved in peeling force), or be only used for being glued on shoes
Unessential position.The uv-curing type inorganic agent of above 3rd type needs to use ultraviolet curing equipment in use
Or assembly line needs to put into more funds and manpower, and will produce ozone row during ultraviolet irradiation for small business
It puts and heat dissipation.In addition, due to the huge thermal energy generated in irradiation process, the material that a part of expansion density may be made low
Generate shrink, modification and cannot use.
Invention content
Based on this, provided it is an object of the invention to overcome in place of above-mentioned the deficiencies in the prior art in a kind of molecular backbone
Have with the low polar structure close with EVA resin, on molecular side chain can antipolarity group hydroxy and carboxyl modification
Polymer and preparation method thereof.
Containing the polymer-modified EVA shoe material inorganic agent another object of the present invention is to provide a kind of.
To achieve the above object, the technical solution that the present invention takes is：A kind of polymer-modified, molecule of the polymer
Structural formula is as follows：
Wherein, n be 150~
Integer in 500 ranges, m are the integer in 60~150 ranges, and p is the integer in 9~75 ranges, and k is in 6~65 ranges
Integer, m are more than p, and p is more than k.
It is of the present invention polymer-modified, there is molecular structural formula as described above, can be seen that by its molecular structural formula,
There is the low polar structure close with EVA resin, being introduced on molecular side chain can antipolarity group hydroxy in molecular backbone
And carboxyl；It is halogen-free, anti-yellowing property is good；Meanwhile by selecting the different of m, n, p, k value in above-mentioned molecular structural formula,
It can obtain that there is the polymer-modified of opposed polarity.
Meanwhile the present invention also provides a kind of polymer-modified preparation method as described above, the method includes following
Step：
(1) EVA resin is dissolved in solvent, and alkaline reagent is added so that EVA resin is carried out saponification under alkaline condition anti-
It answers, saponification temperature is 60~95 DEG C, and the reaction time is 0.5~4 hour, and it is hydroxyl to make the part hydrolysis of ester group in EVA resin
Base obtains partly-hydrolysed EVA resin；
(2) the partly-hydrolysed EVA resin obtained in step (1) and acid anhydrides are subjected to esterification, esterification reaction temperature
It it is 65~90 DEG C, the reaction time is 4~7 hours, is aged 60~90 hours at 55~80 DEG C after reaction so that original
The ester bond of special construction is implanted into EVA resin to get described polymer-modified.
Specific reaction process is as follows：
Preferably, the solvent in the step (1) is the mixed of at least one of hexahydrotoluene and butanone, n-butyl acetate
Close object；The alkaline reagent being added in the step (1) is the mixed solution of NaOH and ethyl alcohol, and NaOH in the mixed solution
A concentration of 0.1~1mol/L.
Preferably, the mass percentage of VAc is 15~30% in EVA resin in the step (1)；The step (1)
The saponification rate of the partly-hydrolysed EVA resin of gained is 15~50%.The partly-hydrolysed EVA resin of gained in the step (1)
Saponification rate, which generates the polarity of products obtained therefrom, directly to be influenced, and saponification rate is different, it is likely that can not be prepared of the present invention
Molecular structural formula it is polymer-modified, or increase the generation of side reaction, meanwhile, the different EVA resin of VAc contents is best
Saponification rate is different, to reach the condition needed for best saponification rate and also differ, and present inventor has found by a large amount of research
EVA in 15~30% range of VAc contents, under above-mentioned solvent, alkaline condition, reaction temperature and reaction time, saponification rate
It may remain in 15%~50% range, better performances be made, with the polymer-modified of molecular structural formula as described above.
It is highly preferred that the content of VAc is 18% in step (1) EVA resin；Solvent be hexahydrotoluene, butanone and
The mixture of n-butyl acetate；Alkaline reagent be NaOH and ethyl alcohol mixed solution, and in the mixed solution NaOH concentration
For 0.5mol/L；Saponification temperature is 80 DEG C, and the reaction time is 2 hours；The saponification rate of the partly-hydrolysed EVA resin of gained is
40%.Solvent, alkaline condition, reaction temperature and the time of saponification have to pass preparation method of the present invention in step (1)
Important influence, present inventor by numerous studies find, when the solvent of saponification, alkaline condition, reaction temperature and
When time is as described above, can effecting reaction obtain that there is the polymer-modified of molecular structural formula as described above, to the greatest extent
Reduce the generation of side reaction.Moreover, the product obtained under the conditions of this has good dissolubility, product transparency is high, 0 DEG C of storage
Depositing one week still has good mobility, will not become g., jelly-like.
Preferably, the acid anhydrides in the step (2) is at least one in maleic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride
Kind.The selection of acid anhydrides to it is of the present invention it is polymer-modified prepare most important, by selecting different types of acid anhydrides, and lead to
Esterification condition in saponification and step (2) is overregulated in step (1), certain saponification rate and esterification yield are reached, it can be real
Now freely adjust polymer-modified polarity.
Preferably, the polymer-modified esterification yield obtained in the step (2) is not less than 65%.It is similar with saponification rate,
The polymer-modified esterification yield that is obtained in the step (2) polarity polymer-modified to gained equally generates direct shadow
It rings, esterification yield is different, it is likely that the polymer-modified of molecular structural formula of the present invention can not be prepared, or increase secondary anti-
The generation answered, meanwhile, the different EVA resin of VAc contents, best esterification yield is different, to reach the item needed for best esterification yield
Part also differs, and present inventor has found by a large amount of research when esterification yield is not less than 65%, can effecting reaction obtain
To with the polymer-modified of molecular structural formula as described above, the generation of side reaction is reduced to the greatest extent.
Preferably, the acid anhydrides in the step (2) is methyl hexahydrophthalic anhydride, and esterification reaction temperature is 80 DEG C, the reaction time
It is 6 hours, is aged 72 hours at 70 DEG C after reaction.Esterification reaction temperature, time in step (2), Aging Temperature, time
There is vital influence on preparation method of the present invention, present inventor has found by numerous studies, when esterification temperature
Degree, the time, when Aging Temperature, time are as described above, can effecting reaction obtain the modification with molecular structural formula as described above
Polymer reduces the generation of side reaction to the greatest extent, can get the best modified poly of 90% or more esterification yield, properties of product
Object.
The present invention also provides the polymer-modified applications in terms of preparing EVA shoe material inorganic agent.
Meanwhile the present invention provides a kind of EVA shoe material inorganic agent, the EVA shoe material inorganic agent contains of the present invention change
Property polymer.
Due to increasing the polar group good with adhesive for polyurethane compatibility on the polymer-modified side chain and can be with
In polyurethane adhesive isocyanates reaction active group, and by preparation process to saponification and enzymatic synthesis condition and acid
The control of acid anhydride can freely adjust the polymer-modified polarity, therefore, by the polymer-modified EVA being prepared
Footwear material inorganic agent is good with polyurethane adhesive compatibility, can also carry out glue chain link with polyurethane adhesive, effectively improve poly-
The initial stage adhesion and ageing-resistant anti-hydrolytic performance of urethane adhesive realize the universality to different footwear materials, to most of
Shoemaking EVA material all has good adhesion.
Preferably, the EVA shoe material inorganic agent also contains solvent, described polymer-modified in the EVA shoe material inorganic agent
In mass percentage be 2~4%.
Preferably, it is containing polymer-modified mass percent by polymer-modified be diluted to a certain proportion of solvent
2.5% solution is to get the EVA shoe material inorganic agent.
Preferably, the solvent is at least one of n-butyl acetate, hexamethylene, hexahydrotoluene, butanone；More preferably
Ground, the solvent are at least two in n-butyl acetate, hexamethylene, hexahydrotoluene, butanone.It is directly used in prior art
Commercialization EVA deals with agent, excessively relies on selected EVA resin, to the splicing that is small, and being formed of the alternative of footwear material
Effect is limited, and passes through the polymer-modified EVA shoe material inorganic agent being prepared of the present invention, and hydroxyl, carboxyl are introduced on side chain, right
The alternative of solvent increases, and need not use benzene, the first benzene kind solvent being more toxic, select solvent effect as described above good,
Safety and environmental protection, and the EVA shoe material inorganic agent is considerably increased to the alternative of footwear material, it is applicable to most of types
Shoemaking EVA material, it might even be possible to be used for other low polar materials, such as ethylene propylene diene rubber, butyl rubber, polyformaldehyde, part
Polypropylene material etc..
The invention also discloses the application method of the EVA shoe material inorganic agent, the method is：It is dipped with hairbrush or cotton
A small amount of inorganic agent is brushed and needs cementing position in material, can direct brushing adhesive after 2~3 minutes dry at 55~65 DEG C
It is bonded.
The preferred embodiment of application method as EVA shoe material inorganic agent of the present invention, before use, can be at this
It invents in the EVA shoe material inorganic agent and curing agent is added；Application method as EVA shoe material inorganic agent of the present invention it is more excellent
It is isocyanates to select embodiment, the curing agent, such as：Bayer FRE, HENSMAN F318, the use of curing agent used
Amount is the 5~10% of inorganic agent quality；The curing agent feed postition is：It is directly added into inorganic agent, stirs after being weighed with measuring cup
It mixes 3~5 minutes.EVA shoe material inorganic agent of the present invention, can add curing agent to use, can also in polyurethane adhesive
Curing agent reacts, resistance to after improving then to effectively improve initial stage then effect to improve the crystallization rate of processing oxidant layer
Aging anti-hydrolytic performance.
Compared with the existing technology, beneficial effects of the present invention are：
The present invention has the low polar structure close with EVA resin by modified polymer in molecular backbone, divide
Introduced on sub- side chain can antipolarity group hydroxy and carboxyl, it is good with polyurethane adhesive compatibility, can also and polyurethane
Isocyanates reaction in adhesive；It is halogen-free, anti-yellowing property is good；Meanwhile by adjusting saponification rate and esterification yield, selection
Different types of acid anhydrides is, it can be achieved that can freely adjust different EVA the polarity of polymer.By the polymer-modified system of the present invention
Standby obtained EVA shoe material inorganic agent, it is big to the alternative of solvent, benzene, the first benzene kind solvent being more toxic, peace need not be used
Loopful is protected；Have universality, use scope wide different footwear materials；Operating procedure is convenient, at the same have then effect it is good, resistance to
Aging anti-hydrolytic performance is good, to the affine good penetrability of material the advantages that.
Specific implementation mode
To better illustrate the object, technical solutions and advantages of the present invention, below in conjunction with specific embodiment to the present invention
It is described further.
Embodiment 1
A kind of embodiment of polymer-modified preparation method of the invention, it is polymer-modified using following described in the present embodiment
Method is prepared：
(1) EVA resin is dissolved in solvent, and alkaline reagent is added so that EVA resin is carried out saponification under alkaline condition anti-
It answers, saponification temperature is 80 DEG C, and the reaction time is 2 hours, obtains partly-hydrolysed EVA resin；
Wherein, VAc contents are 18% in EVA resin；The solvent of saponification is hexahydrotoluene, butanone, the positive fourth of acetic acid
The mixed system of ester；Alkaline reagent be NaOH and ethyl alcohol mixed solution, and in the mixed solution NaOH it is a concentration of
0.5mol/L；The saponification rate of the partly-hydrolysed EVA resin of gained is 40%.
(2) the partly-hydrolysed EVA resin obtained in step (1) and methyl hexahydrophthalic anhydride are subjected to esterification, esterification
Reaction temperature be 80 DEG C, the reaction time be 6 hours, be aged at 70 DEG C after reaction 72 hours to get esterification yield be 90%
It is polymer-modified.
A kind of preparation method described in the present embodiment is prepared polymer-modified.
With the mixed solvent of a certain proportion of hexahydrotoluene and butanone, (mass ratio of hexahydrotoluene and butanone is 2:1)
It is 2% solution by polymer-modified be diluted to containing polymer-modified mass percent that the present embodiment is prepared, is contained
There is the polymer-modified EVA shoe material inorganic agent.
Embodiment 2
A kind of embodiment of polymer-modified preparation method of the invention, it is polymer-modified using following described in the present embodiment
Method is prepared：
(1) EVA resin is dissolved in solvent, and alkaline reagent is added so that EVA resin is carried out saponification under alkaline condition anti-
It answers, saponification temperature is 60 DEG C, and the reaction time is 4 hours, obtains partly-hydrolysed EVA resin；
Wherein, VAc contents are 15% in EVA resin；The solvent of saponification is hexahydrotoluene, butanone, the positive fourth of acetic acid
The mixed system of ester；Alkaline reagent be NaOH and ethyl alcohol mixed solution, and in the mixed solution NaOH it is a concentration of
0.1mol/L；The saponification rate of the partly-hydrolysed EVA resin of gained is 15%.
(2) the partly-hydrolysed EVA resin obtained in step (1) and maleic anhydride are subjected to esterification, esterification
Temperature is 65 DEG C, and the reaction time is 7 hours, after reaction be aged at 80 DEG C 90 hours and changes for 75% to get esterification yield
Property polymer.
A kind of preparation method described in the present embodiment is prepared polymer-modified.
Polymer-modified be diluted to that the present embodiment is prepared is contained into modification with a certain proportion of methyl cyclohexane alkane solvents
The solution that polymer quality percentage is 4%, obtains containing the polymer-modified EVA shoe material inorganic agent.
Embodiment 3
A kind of embodiment of polymer-modified preparation method of the invention, it is polymer-modified using following described in the present embodiment
Method is prepared：
(1) EVA resin is dissolved in solvent, and alkaline reagent is added so that EVA resin is carried out saponification under alkaline condition anti-
It answers, saponification temperature is 95 DEG C, and the reaction time is 0.5 hour, obtains partly-hydrolysed EVA resin；
Wherein, VAc contents are 30% in EVA resin；The solvent of saponification is hexahydrotoluene, butanone, the positive fourth of acetic acid
The mixed system of ester；Alkaline reagent be NaOH and ethyl alcohol mixed solution, and in the mixed solution NaOH a concentration of 1mol/
L；The saponification rate of the partly-hydrolysed EVA resin of gained is 50%.
(2) the partly-hydrolysed EVA resin obtained in step (1) and hexahydrophthalic anhydride are subjected to esterification, esterification
Temperature is 90 DEG C, and the reaction time is 4 hours, after reaction be aged at 60 DEG C 60 hours and changes for 65% to get esterification yield
Property polymer.
A kind of preparation method described in the present embodiment is prepared polymer-modified.
It polymer-modified is diluted to what the present embodiment was prepared containing polymer-modified with a certain proportion of butanone solvent
The solution that mass percent is 3%, obtains containing the polymer-modified EVA shoe material inorganic agent.
Embodiment 4
A kind of embodiment of polymer-modified preparation method of the invention, it is polymer-modified using following described in the present embodiment
Method is prepared：
(1) EVA resin is dissolved in solvent, and alkaline reagent is added so that EVA resin is carried out saponification under alkaline condition anti-
It answers, saponification temperature is 70 DEG C, and the reaction time is 1 hour, obtains partly-hydrolysed EVA resin；
Wherein, VAc contents are 20% in EVA resin；The solvent of saponification is hexahydrotoluene, butanone, the positive fourth of acetic acid
The mixed system of ester；Alkaline reagent be NaOH and ethyl alcohol mixed solution, and in the mixed solution NaOH it is a concentration of
0.8mol/L；The saponification rate of the partly-hydrolysed EVA resin of gained is 30%.
(2) by the mixture of the partly-hydrolysed EVA resin and methyl hexahydrophthalic anhydride and maleic anhydride that are obtained in step (1)
(mass ratio of methyl hexahydrophthalic anhydride and maleic anhydride is 2:1) esterification is carried out, esterification reaction temperature is 70 DEG C, the reaction time
Be 5 hours, be aged at 65 DEG C after reaction 80 hours to get esterification yield be 85% it is polymer-modified.
A kind of preparation method described in the present embodiment is prepared polymer-modified.
With a certain proportion of hexamethylene polymer-modified substance containing modified poly is diluted to by what the present embodiment was prepared
The solution that percentage is 2.5% is measured, is obtained containing the polymer-modified EVA shoe material inorganic agent.
Embodiment 5
A kind of embodiment of polymer-modified preparation method of the invention, it is polymer-modified using following described in the present embodiment
Method is prepared：
(1) EVA resin is dissolved in solvent, and alkaline reagent is added so that EVA resin is carried out saponification under alkaline condition anti-
It answers, saponification temperature is 90 DEG C, and the reaction time is 2 hours, obtains partly-hydrolysed EVA resin；
Wherein, VAc contents are 25% in EVA resin；The solvent of saponification is hexahydrotoluene, butanone, the positive fourth of acetic acid
The mixed system of ester；Alkaline reagent be NaOH and ethyl alcohol mixed solution, and in the mixed solution NaOH it is a concentration of
0.3mol/L；The saponification rate of the partly-hydrolysed EVA resin of gained is 35%.
(2) it is maleic anhydride, hexahydrophthalic anhydride, first by the partly-hydrolysed EVA resin obtained in step (1) and special acid anhydrides
Base hexahydrophthalic anhydride mixture (maleic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride mass ratio be 1:2:1) it carries out being esterified anti-
It answers, esterification reaction temperature is 85 DEG C, and the reaction time is 6.5 hours, is aged 65 hours at 55 DEG C after reaction to get esterification
Rate be 80% it is polymer-modified.
A kind of preparation method described in the present embodiment is prepared polymer-modified.
It polymer-modified is diluted to what the present embodiment was prepared containing modified poly with a certain proportion of n-butyl acetate
The solution that amount of substance percentage is 2%, obtains containing the polymer-modified EVA shoe material inorganic agent.
Embodiment 6
The preparation-obtained EVA shoe material inorganic agent of Examples 1 to 5 is applied to Dongguan and contains one hundred lucky shoes industry (Dongguan
Surpassng Shoes Co., Ltd) production two kinds of type body footwear material (outsoles of PUMA brands JO-539, JO-522：MD EVA with
Rubber；Vamp：Screen cloth and synthesis skin), test is drawn using footwear material pulling force and interface conditions after EVA shoe material inorganic agent of the present invention
Power is tested using universal tensile testing machine, and interface conditions are mainly tested by observation, and will be led in the prior art
Frequently with one of EVA shoe material inorganic agent (in the application background technology the 2nd kind then EVA shoe material inorganic agent used in scheme) make
Comparative example similarly apply and test, and test result is as shown in table 1：
1 pulling force of table and interface conditions test result
It is compared as can be seen from Table 1 with comparative example, the preparation-obtained EVA shoe material inorganic agent of the present invention and footwear material connect
It effect and anti-hydrolytic performance is greatly enhanced.
Embodiment 7
The white EVA material for taking hardness 65A, it is thick with the sand paper disc sharpener of 80 mesh, the ash bits on surface are removed, are dripped respectively on surface
Add same amount of test group and control group EVA shoe material inorganic agent, wherein test group is using EVA shoe material processing prepared by the present invention
Agent, (the 2nd kind then in the application background technology using one of EVA shoe material inorganic agent of generally use in the prior art for control group
EVA shoe material inorganic agent used in scheme), added with orchil in test group and control group EVA inorganic agents), examination is measured respectively
Test group and control group EVA surface conditioning agents infiltration circle size and the depth of EVA material section inorganic agent infiltration, measurement data
As shown in table 2：
2 EVA surface conditioning agents of table infiltration circle size and the depth of EVA material section inorganic agent infiltration
As can be seen from Table 2, by the polymer-modified EVA shoe material inorganic agent being prepared of the present invention on material
Permeability is obviously accelerated.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than is protected to the present invention
The limitation of range is protected, although being explained in detail to the present invention with reference to preferred embodiment, those skilled in the art should
Understand, technical scheme of the present invention can be modified or replaced equivalently, without departing from the essence of technical solution of the present invention
And range.
Claims (7)
1. a kind of EVA shoe material inorganic agent, which is characterized in that the EVA shoe material inorganic agent contains the molecular structural formula as shown in formula (1)
It is polymer-modified：
Wherein, n is the integer in 150~500 ranges, and m is the integer in 60~150 ranges, and p is the integer in 9~75 ranges,
K is the integer in 6~65 ranges, and m is more than p, and p is more than k.
2. EVA shoe material inorganic agent as described in claim 1, which is characterized in that the polymer-modified preparation method include with
Lower step：
(1) EVA resin is dissolved in solvent, and alkaline reagent, which is added, makes EVA resin carry out saponification, soap under alkaline condition
It is 60~95 DEG C to change reaction temperature, and the reaction time is 0.5~4 hour, obtains partly-hydrolysed EVA resin；In the step (1)
The mass percentage of VAc is 15~30% in EVA resin；The saponification rate of partly-hydrolysed EVA resin obtained by the step (1)
It is 15~50%；
(2) the partly-hydrolysed EVA resin obtained in step (1) and acid anhydrides are subjected to esterification, esterification reaction temperature 65
~90 DEG C, the reaction time is 4~7 hours, is aged at 55~80 DEG C 60~90 hours and gathers to get the modification after reaction
Close object；The polymer-modified esterification yield obtained in the step (2) is not less than 65%.
3. EVA shoe material inorganic agent as claimed in claim 2, which is characterized in that the solvent in the step (1) is methyl cyclohexane
At least one of alkane, butanone, n-butyl acetate；The alkaline reagent being added in the step (1) is the mixing of NaOH and ethyl alcohol
Solution, and in the mixed solution NaOH a concentration of 0.1~1mol/L.
4. the EVA shoe material inorganic agent as described in Claims 2 or 3, which is characterized in that the matter of VAc in step (1) EVA resin
It is 18% to measure percentage composition；Solvent is the mixture of hexahydrotoluene, butanone and n-butyl acetate；Alkaline reagent is NaOH and second
The mixed solution of alcohol, and in the mixed solution NaOH a concentration of 0.5mol/L；Saponification temperature is 80 DEG C, the reaction time
It is 2 hours；The saponification rate of the partly-hydrolysed EVA resin of gained is 40%.
5. EVA shoe material inorganic agent as claimed in claim 2, which is characterized in that acid anhydrides in the step (2) be maleic anhydride,
At least one of hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride.
6. the EVA shoe material inorganic agent as described in claim 2 or 5, which is characterized in that the acid anhydrides in the step (2) is methyl six
Hydrogen phthalic anhydride, esterification reaction temperature are 80 DEG C, and the reaction time is 6 hours, is aged 72 hours at 70 DEG C after reaction.
7. EVA shoe material inorganic agent as described in claim 1, which is characterized in that the EVA shoe material inorganic agent also contains solvent, institute
It is 2~4% to state the polymer-modified mass percentage in the EVA shoe material inorganic agent.
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|---|---|---|---|---|
| CN1187498A (en) * | 1997-01-10 | 1998-07-15 | 中国石油化工总公司 | Ethylene-vinylacetate-vinyl alcohol-vinyl alcohol maleic monoester quaternary atactic copolymer and its preparing process |
| FR2827608A1 (en) * | 2001-07-17 | 2003-01-24 | Elf Antar France | Special olefin-alkenyl alkylate copolymers, such as ethylene-vinyl acetate copolymers with special side chains, used as multifunctional fuel additives to improve low temperature properties and sedimentation |
| CN102942649A (en) * | 2012-12-17 | 2013-02-27 | 中国林业科学研究院林产化学工业研究所 | Preparation method of ethylene-vinyl alcohol copolymer |
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| CN1187498A (en) * | 1997-01-10 | 1998-07-15 | 中国石油化工总公司 | Ethylene-vinylacetate-vinyl alcohol-vinyl alcohol maleic monoester quaternary atactic copolymer and its preparing process |
| FR2827608A1 (en) * | 2001-07-17 | 2003-01-24 | Elf Antar France | Special olefin-alkenyl alkylate copolymers, such as ethylene-vinyl acetate copolymers with special side chains, used as multifunctional fuel additives to improve low temperature properties and sedimentation |
| CN102942649A (en) * | 2012-12-17 | 2013-02-27 | 中国林业科学研究院林产化学工业研究所 | Preparation method of ethylene-vinyl alcohol copolymer |
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