CN106432553A - Modified polymer as well as preparation method and application thereof - Google Patents
Modified polymer as well as preparation method and application thereof Download PDFInfo
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- CN106432553A CN106432553A CN201610814899.XA CN201610814899A CN106432553A CN 106432553 A CN106432553 A CN 106432553A CN 201610814899 A CN201610814899 A CN 201610814899A CN 106432553 A CN106432553 A CN 106432553A
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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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Abstract
The invention discloses a modified polymer. A molecular main chain of the polymer has a low-polarity structure similar with EVA (Ethylene/Vinyl Acetate) resin; reactive polar groups including hydroxyl and carboxyl are introduced on a molecular side chain. Meanwhile, the invention discloses a preparation method of the modified polymer; in a preparation process, different types of acid anhydrides are selected through adjusting a saponification condition and an esterification condition, so that free adjustment of the polarity of the modified polymer can be realized. The invention further discloses an EVA shoe material treatment agent comprising the modified polymer; the selectivity of the treatment agent on a solvent is great and the treatment agent has universality on different shoe making materials; meanwhile, the treatment agent also has the advantages of good adhering effect, good anti-ageing and anti-hydrolysis performances, good compatibility and good permeability on materials and the like.
Description
Technical field
The present invention relates to a kind of polymer and preparation method and application, especially a kind of polymer-modified and its preparation side
Method and application.
Background technology
Shoemaking EVA (ethylene-vinyl acetate copolymer) material, because of the various property of shoes to be reached particularly sport shoess
Can require, usual ethylene component content is higher, and various resilience pliabilities more preferable polyolefin may need to be blended (as polyoctenamer
Deng), but due to add in material processing various lubricants, plasticizer, releasing agent, inorganic filler etc. is so that material list
Face polarity is very low, and current shoe industry commonly uses polyurethane adhesive, because the polarity of polyurethane adhesive is of a relatively high,
According to similar compatibility principle, such as directly in EVA surface coating, it is hardly formed effectively then (the shoemaking requirement meeting shoemaking requirement
Can only be surface-treated with simple chemical method, reach material damage when then peeling off afterwards rather than glue-line destroys or interfacial failure
Or peeling force is at least up to 3N/mm).
Current then scheme typically has following three kinds：
1st, first will be thick for material mill and clean clean surface, to remove the low polarity oils and fatss on surface and to increase the surface of material
Long-pending, then it is surface-treated with the sol solutionses of chlorinated polypropylene, make EVA material surface form the transition of one layer of chlorinated polypropylene
Layer.It is similar to the low polarity similarity of the structure of ethylene moiety and EVA in EVA using main chain in chlorinated polypropylene to be formed then, and
Highly polar and polyurethane using chlorine element in chlorinated polypropylene is formed then, thus realizing the effectively viscous of EVA and other footwear material
Close.
2nd, it is polymerized in EVA particle solution with methyl methacrylate, form the macromolecule of interpenetrating networks or a small amount of connecing
The polymeric mixed solution of branch, after this solution is diluted, as the surface conditioning agent of EVA.Using EVA in inorganic agent and footwear
In material, the similar compatibility of the similar compatibility of EVA and poly- methylpropionic acid methyl esters part and polyurethane adhesive forms and effectively connects
, similarly, this kind of inorganic agent is also required to first polish coarse by material surface and clean.
3rd, use the inorganic agent of ultra-violet curing type, first apply the acrylic monomerss of one layer of ultraviolet-curing in material surface
Class inorganic agent, then irradiate material surface with ultraviolet, make a part penetrate into the small molecule propernoic acid ester monomer solid of material internal
Chemical conversion polyacrylate, is formed effectively then using the similar compatibility of acrylate and polyurethane adhesive.
But, above 1st type deals with agent using chlorinated polypropylene, due to the depositing of chlorine element in chlorinated polypropylene
So that the anti-yellowing property of inorganic agent is very poor, because, in shoemaking, inorganic agent inevitably may be brushed to does not need glue
The position connecing, so this inorganic agent is only used in the very deep EVA material of some colors.The inorganic agent of above 2nd type,
Because EVA is difficult to dissolve in usual vehicle, it usually needs with benzene, toluene, halogenated hydrocarbon solvent, use process in shoemaking worker
In, these solvents inevitably cause to operator and atmospheric environment to damage and damage.Above 1st, the 2nd is two kinds of
Inorganic agent is all only applicable to some density of material, the relatively low foaming EVA material of hardness, or is only applicable to special ethylene-acetic acid
The EVA material of propane ratio.For injection EVA, the EVA of post forming or the polyolefinic material that lower polarity has been blended,
Cannot be formed and effectively then (village's material destruction can not be reached or peeling force does not reach 3N/mm), or be only used for glueing joint on shoes
Unessential position.The uv-curing type inorganic agent of above 3rd type, needs to use ultraviolet curing equipment in use
Or streamline, for small business, ozone row during needing to put into more funds and manpower, and ultra-vioket radiation, can be produced
Put and heat dissipation.Further, since the huge heat energy producing in irradiation process, the low material of a part of expansion density may be made
Produce shrink, modification and can not use.
Content of the invention
Based on this, it is an object of the invention to providing in a kind of molecular backbone in place of overcoming above-mentioned the deficiencies in the prior art
There is low polar structure akin with EVA resin, molecular side chain has can antipolarity group hydroxy and carboxyl modification
Polymer and preparation method thereof.
Another object of the present invention is to provide a kind of containing described polymer-modified EVA shoe material inorganic agent.
For achieving the above object, the technical scheme that the present invention takes is：A kind of polymer-modified, molecule of described polymer
Structural formula is as follows：
Wherein, n is the integer in the range of 150～500, and m is the integer in the range of 60～150, and p is in the range of 9～75
Integer, k is the integer in the range of 6～65, and m is more than p, and p is more than k.
Of the present invention polymer-modified, there is molecular structural formula as above, be can be seen that by its molecular structural formula, its
There is in molecular backbone low polar structure akin with EVA resin, molecular side chain introduces can antipolarity group hydroxy
And carboxyl；Not halogen-containing, anti-yellowing property is good；Meanwhile, by the different choice to m, n, p, k value in above-mentioned molecular structural formula,
Can obtain that there is the polymer-modified of opposed polarity.
Meanwhile, present invention also offers a kind of preparation method polymer-modified as mentioned above, methods described includes following
Step：
(1) EVA resin is dissolved in solvent, and it is anti-to add alkaline reagent to make EVA resin carry out saponification in the basic conditions
Should, saponification temperature is 60～95 DEG C, and the response time is 0.5～4 hour, makes the part hydrolysis of ester group in EVA resin be hydroxyl
Base, obtains partly-hydrolysed EVA resin；
(2) the partly-hydrolysed EVA resin obtaining in step (1) and anhydride are carried out esterification, esterification reaction temperature
For 65～90 DEG C, the response time is 4～7 hours, reaction terminate after at 55～80 DEG C ageing 60～90 hours so that original
The ester bond of special construction is implanted on EVA resin, obtains final product described polymer-modified.
Specific course of reaction is as follows：
Preferably, the solvent in described step (1) is the mixed of hexahydrotoluene and at least one of butanone, n-butyl acetate
Compound；The alkaline reagent adding in described step (1) is the mixed solution of NaOH and ethanol, and NaOH in described mixed solution
Concentration is 0.1～1mol/L.
Preferably, in EVA resin in described step (1), the weight/mass percentage composition of VAc is 15～30%；Described step (1)
The saponification rate of the partly-hydrolysed EVA resin of gained is 15～50%.The partly-hydrolysed EVA resin of gained in described step (1)
Saponification rate produces on the polarity of products obtained therefrom directly to be affected, and saponification rate difference is it is likely that cannot prepare of the present invention
Molecular structural formula polymer-modified, or increase side reaction generation, meanwhile, the different EVA resin of VAc content, optimal
Saponification rate is different, and the condition needed for optimal saponification rate that reach also differs, and present inventor, through substantial amounts of research, finds
EVA in the range of VAc content 15～30%, under above-mentioned solvent, alkalescence condition, reaction temperature and response time, saponification rate
May remain in the range of 15%～50%, make better performances, there is the polymer-modified of molecular structural formula as described above.
It is highly preferred that the content of VAc is 18% in described step (1) EVA resin；Solvent be hexahydrotoluene, butanone and
The mixture of n-butyl acetate；Alkaline reagent is the mixed solution of NaOH and ethanol, and in described mixed solution NaOH concentration
For 0.5mol/L；Saponification temperature is 80 DEG C, and the response time is 2 hours；The saponification rate of the partly-hydrolysed EVA resin of gained is
40%.In step (1), the solvent of saponification, alkalescence condition, reaction temperature and time have to pass to preparation method of the present invention
Important impact, present inventor finds through numerous studies, when the solvent of saponification, alkalescence condition, reaction temperature and
When time is as described above, can obtain there is the polymer-modified of molecular structural formula as described above, farthest by effecting reaction
Reduce the generation of side reaction.And, this under the conditions of the product that obtains there is good dissolubility, product transparency is high, 0 DEG C of storage
Deposit one week and still there is good mobility, g., jelly-like will not be become.
Preferably, the anhydride in described step (2) be maleic anhydride, HHPA, in methyl hexahydrophthalic anhydride at least one
Kind.The selection of anhydride to of the present invention polymer-modified prepare most important, by selecting different types of anhydride, and lead to
Overregulate esterification condition in saponification and step (2) in step (1), reach certain saponification rate and esterification yield, can be real
Now freely adjust polymer-modified polarity.
Preferably, the polymer-modified esterification yield obtaining in described step (2) is not less than 65%.It is similar with saponification rate,
The polymer-modified esterification yield that obtains in described step (2) polarity polymer-modified to gained equally produces direct shadow
Ring, esterification yield difference is it is likely that the polymer-modified of molecular structural formula of the present invention cannot be prepared, or increases secondary anti-
The generation answered, meanwhile, the different EVA resin of VAc content, optimal esterification yield is different, will reach the bar needed for optimal esterification yield
Part also differs, and present inventor, through substantial amounts of research, finds, when esterification yield is not less than 65%, can effecting reaction to obtain
To having the polymer-modified of molecular structural formula as described above, farthest reduce the generation of side reaction.
Preferably, the anhydride in described step (2) is methyl hexahydrophthalic anhydride, and esterification reaction temperature is 80 DEG C, the response time
For 6 hours, reaction was aged 72 hours after terminating at 70 DEG C.Esterification reaction temperature, time in step (2), Aging Temperature, time
On preparation method of the present invention, there is vital impact, present inventor finds through numerous studies, when esterification temperature
Degree, time, when Aging Temperature, time are as described above, the modification with molecular structural formula as described above can be obtained by effecting reaction
Polymer, farthest reduces the generation of side reaction, can obtain the optimal modified poly of esterification yield more than 90%, properties of product
Thing.
Present invention also offers the application in terms of the described polymer-modified EVA shoe material inorganic agent in preparation.
Meanwhile, the present invention provides a kind of EVA shoe material inorganic agent, and described EVA shoe material inorganic agent contains of the present invention changing
Property polymer.
Due to the polar group good with the adhesive for polyurethane compatibility and can be be increased on described polymer-modified side chain
The active group of the isocyanates reaction in polyurethane adhesive, and pass through in preparation process to saponification and enzymatic synthesis condition and acid
The control of acid anhydride, can freely adjust described polymer-modified polarity, therefore, by the described polymer-modified EVA preparing
Footwear material inorganic agent is good with the polyurethane adhesive compatibility, can also carry out glue chain with polyurethane adhesive and be connected, effectively improve poly-
The initial stage adhesion of urethane adhesive and ageing-resistant anti-hydrolytic performance, realize the universality to different footwear materials, to great majority
Shoemaking EVA material is respectively provided with good adhesion.
Preferably, described EVA shoe material inorganic agent also contains solvent, described polymer-modified in described EVA shoe material inorganic agent
In weight/mass percentage composition be 2～4%.
Preferably, with a certain proportion of solvent, described polymer-modified being diluted to containing polymer-modified mass percent is
2.5% solution, obtains final product described EVA shoe material inorganic agent.
Preferably, described solvent be n-butyl acetate, hexamethylene, hexahydrotoluene, at least one in butanone；More preferably
Ground, described solvent is n-butyl acetate, hexamethylene, hexahydrotoluene, in butanone at least two.Directly use in prior art
Commercialization EVA deals with agent, excessively relies on selected EVA resin, little to the alternative of footwear material, and the splicing being formed
Effect is limited, and introduces hydroxyl, carboxyl on the polymer-modified EVA shoe material inorganic agent preparing of the present invention, side chain, right
The alternative of solvent increases it is not necessary to using the larger benzene of toxicity, first benzene kind solvent, select solvent effect as described above good,
Safety and environmental protection, and considerably increase the alternative to footwear material for the described EVA shoe material inorganic agent, it is applicable to most of species
Shoemaking EVA material is 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 using method of described EVA shoe material inorganic agent, methods described is：Dipped with hairbrush or cotton
A small amount of inorganic agent, brushing needs cementing position in material, after being dried 2～3 minutes at 55～65 DEG C, can direct brushing adhesive
Bonded.
As the preferred implementation of the using method of EVA shoe material inorganic agent of the present invention, before use, can be at this
Invent addition firming agent in described EVA shoe material inorganic agent；As EVA shoe material inorganic agent of the present invention using method more excellent
Select embodiment, described firming agent is isocyanates, such as：Bayer FRE, HENSMAN F318, the use of firming agent used
Measure 5～10% for inorganic agent quality；Described firming agent feed postition is：It is directly added in inorganic agent after being weighed with measuring cup, stir
Mix 3～5 minutes.EVA shoe material inorganic agent of the present invention, can reinforce agent using it is also possible to polyurethane adhesive in
Firming agent reacts, thus improving the crystallization rate processing oxidant layer, thus effectively improving initial stage then effect, resistance to after improving then
Aging anti-hydrolytic performance.
With respect to prior art, beneficial effects of the present invention are：
The present invention passes through modified polymer, has low polar structure akin with EVA resin in molecular backbone, point
Introduce on sub- side chain can antipolarity group hydroxy and carboxyl, good with the polyurethane adhesive compatibility, can also and polyurethane
Isocyanates reaction in adhesive；Not halogen-containing, anti-yellowing property is good；Meanwhile, by adjusting saponification rate and esterification yield, select
Different types of anhydride, can achieve the polarity for the different freely adjustable polymer of EVA.By the polymer-modified system of the present invention
The standby EVA shoe material inorganic agent obtaining, to the alternative big of solvent it is not necessary to using the larger benzene of toxicity, first benzene kind solvent, pacify
Loopful is protected；To different footwear materials, there is universality, range is wide；Operating procedure is convenient, has then effect good, resistance to simultaneously
Aging anti-hydrolytic performance is good, to the affine good penetrability of material the advantages of.
Specific embodiment
For better illustrating 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 the polymer-modified preparation method of the present invention, described in the present embodiment polymer-modified using following
Method is prepared from：
(1) EVA resin is dissolved in solvent, and it is anti-to add alkaline reagent to make EVA resin carry out saponification in the basic conditions
Should, saponification temperature is 80 DEG C, and the response time is 2 hours, obtains partly-hydrolysed EVA resin；
Wherein, in EVA resin, VAc content is 18%；The solvent of saponification is hexahydrotoluene, butanone, the positive fourth of acetic acid
The mixed system of ester；Alkaline reagent is the mixed solution of NaOH and ethanol, and in described mixed solution, the concentration of NaOH is
0.5mol/L；The saponification rate of the partly-hydrolysed EVA resin of gained is 40%.
(2) the partly-hydrolysed EVA resin obtaining in step (1) and methyl hexahydrophthalic anhydride are carried out esterification, esterification
Reaction temperature is 80 DEG C, and the response time is 6 hours, and reaction is aged 72 hours after terminating at 70 DEG C, and obtaining final product esterification yield is 90%
Polymer-modified.
It is polymer-modified that a kind of preparation method described in the present embodiment prepares.
With the mixed solvent of a certain proportion of hexahydrotoluene and butanone, (mass ratio of hexahydrotoluene and butanone is 2:1)
By the present embodiment prepare polymer-modified be diluted to the solution being 2% containing polymer-modified mass percent, contained
There is described polymer-modified EVA shoe material inorganic agent.
Embodiment 2
A kind of embodiment of the polymer-modified preparation method of the present invention, described in the present embodiment polymer-modified using following
Method is prepared from：
(1) EVA resin is dissolved in solvent, and it is anti-to add alkaline reagent to make EVA resin carry out saponification in the basic conditions
Should, saponification temperature is 60 DEG C, and the response time is 4 hours, obtains partly-hydrolysed EVA resin；
Wherein, in EVA resin, VAc content is 15%；The solvent of saponification is hexahydrotoluene, butanone, the positive fourth of acetic acid
The mixed system of ester；Alkaline reagent is the mixed solution of NaOH and ethanol, and in described mixed solution, the concentration of NaOH is
0.1mol/L；The saponification rate of the partly-hydrolysed EVA resin of gained is 15%.
(2) the partly-hydrolysed EVA resin obtaining in step (1) and maleic anhydride are carried out esterification, esterification
Temperature is 65 DEG C, and the response time is 7 hours, and reaction is aged 90 hours after terminating at 80 DEG C, and obtaining final product esterification yield is 75% change
Property polymer.
It is polymer-modified that a kind of preparation method described in the present embodiment prepares.
Polymer-modified it is diluted to what the present embodiment prepared containing modification with a certain proportion of methyl cyclohexane alkane solvents
Polymer quality percentage ratio is 4% solution, obtains containing described polymer-modified EVA shoe material inorganic agent.
Embodiment 3
A kind of embodiment of the polymer-modified preparation method of the present invention, described in the present embodiment polymer-modified using following
Method is prepared from：
(1) EVA resin is dissolved in solvent, and it is anti-to add alkaline reagent to make EVA resin carry out saponification in the basic conditions
Should, saponification temperature is 95 DEG C, and the response time is 0.5 hour, obtains partly-hydrolysed EVA resin；
Wherein, in EVA resin, VAc content is 30%；The solvent of saponification is hexahydrotoluene, butanone, the positive fourth of acetic acid
The mixed system of ester；Alkaline reagent is the mixed solution of NaOH and ethanol, and in described mixed solution, the concentration of NaOH is 1mol/
L；The saponification rate of the partly-hydrolysed EVA resin of gained is 50%.
(2) the partly-hydrolysed EVA resin obtaining in step (1) and HHPA are carried out esterification, esterification
Temperature is 90 DEG C, and the response time is 4 hours, and reaction is aged 60 hours after terminating at 60 DEG C, and obtaining final product esterification yield is 65% change
Property polymer.
It is polymer-modified that a kind of preparation method described in the present embodiment prepares.
Polymer-modified it is diluted to what the present embodiment prepared containing polymer-modified with a certain proportion of butanone solvent
Mass percent is 3% solution, obtains containing described polymer-modified EVA shoe material inorganic agent.
Embodiment 4
A kind of embodiment of the polymer-modified preparation method of the present invention, described in the present embodiment polymer-modified using following
Method is prepared from：
(1) EVA resin is dissolved in solvent, and it is anti-to add alkaline reagent to make EVA resin carry out saponification in the basic conditions
Should, saponification temperature is 70 DEG C, and the response time is 1 hour, obtains partly-hydrolysed EVA resin；
Wherein, in EVA resin, VAc content is 20%；The solvent of saponification is hexahydrotoluene, butanone, the positive fourth of acetic acid
The mixed system of ester；Alkaline reagent is the mixed solution of NaOH and ethanol, and in described mixed solution, the concentration of NaOH is
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 obtaining in step (1) and methyl hexahydrophthalic anhydride and maleic anhydride
(methyl hexahydrophthalic anhydride is 2 with the mass ratio of maleic anhydride:1) carry out esterification, esterification reaction temperature is 70 DEG C, the response time
For 5 hours, reaction terminate after at 65 DEG C be aged 80 hours, obtain final product esterification yield be 85% polymer-modified.
It is polymer-modified that a kind of preparation method described in the present embodiment prepares.
Polymer-modified it is diluted to material containing modified poly with a certain proportion of hexamethylene by what the present embodiment prepared
Amount percentage ratio is 2.5% solution, obtains containing described polymer-modified EVA shoe material inorganic agent.
Embodiment 5
A kind of embodiment of the polymer-modified preparation method of the present invention, described in the present embodiment polymer-modified using following
Method is prepared from：
(1) EVA resin is dissolved in solvent, and it is anti-to add alkaline reagent to make EVA resin carry out saponification in the basic conditions
Should, saponification temperature is 90 DEG C, and the response time is 2 hours, obtains partly-hydrolysed EVA resin；
Wherein, in EVA resin, VAc content is 25%；The solvent of saponification is hexahydrotoluene, butanone, the positive fourth of acetic acid
The mixed system of ester；Alkaline reagent is the mixed solution of NaOH and ethanol, and in described mixed solution, the concentration of NaOH is
0.3mol/L；The saponification rate of the partly-hydrolysed EVA resin of gained is 35%.
(2) the partly-hydrolysed EVA resin obtaining in step (1) and special anhydride be maleic anhydride, HHPA, first
(maleic anhydride, HHPA, the mass ratio of methyl hexahydrophthalic anhydride are 1 to the mixture of base HHPA:2:1) carry out esterification anti-
Should, esterification reaction temperature is 85 DEG C, and the response time is 6.5 hours, and reaction is aged 65 hours after terminating at 55 DEG C, obtains final product esterification
Rate be 80% polymer-modified.
It is polymer-modified that a kind of preparation method described in the present embodiment prepares.
Polymer-modified it is diluted to what the present embodiment prepared containing modified poly with a certain proportion of n-butyl acetate
Amount of substance percentage ratio is 2% solution, obtains containing described polymer-modified EVA shoe material inorganic agent.
Embodiment 6
Preparation-obtained for embodiment 1～5 EVA shoe material inorganic agent is applied to Dongguan and contains one hundred lucky footwear industry (Dongguan
Surpassng Shoes Co., Ltd) two kinds of type body footwear material (big bottoms of PUMA brand JO-539, JO-522 of producing：MD EVA with
Rubber；Vamp：Screen cloth and synthesis skin), test, using the footwear material pulling force after EVA shoe material inorganic agent of the present invention and interface conditions, is drawn
Power is tested using universal tensile testing machine, and interface conditions are mainly tested by observational method, and will be logical in 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, carries out same application and test, and test result is as shown in table 1：
Table 1 pulling force and interface conditions test result
As can be seen from Table 1, compare with comparative example, the present invention preparation-obtained EVA shoe material inorganic agent is connect with footwear material
Effect and anti-hydrolytic performance is greatly enhanced.
Embodiment 7
Take the white EVA material of hardness 65A, the sand paper disc sharpener with 80 mesh is thick, remove the ash bits on surface, drip on surface respectively
Plus same amount of test group and matched group EVA shoe material inorganic agent, wherein test group adopts EVA shoe material prepared by the present invention to process
Agent, matched group adopts one of EVA shoe material inorganic agent generally adopting in prior art, and (in the application background technology, the 2nd kind then
EVA shoe material inorganic agent used in scheme), all added with orchil in test group and matched group EVA inorganic agent), measurement examination respectively
Test group and the depth of matched group EVA surface conditioning agent infiltration circle size and the infiltration of EVA material section inorganic agent, measurement data
As shown in table 2：
Table 2 EVA surface conditioning agent 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 preparing of the present invention on material
Permeability is substantially accelerated.
Last should be noted that above example is only in order to illustrate technical scheme rather than to present invention guarantor
The restriction of shield scope, although being explained in detail to the present invention with reference to preferred embodiment, those of ordinary skill in the art should
Understand, technical scheme can be modified or equivalent, without deviating from the essence of technical solution of the present invention
And scope.
Claims (10)
1. a kind of polymer-modified it is characterised in that described polymer molecular structural formula such as formula (1) shown in：
Wherein, n is the integer in the range of 150～500, and m is the integer in the range of 60～150, and p is the integer in the range of 9～75,
K is the integer in the range of 6～65, and m is more than p, and p is more than k.
2. a kind of preparation method polymer-modified as claimed in claim 1 is it is characterised in that methods described includes following step
Suddenly：
(1) EVA resin is dissolved in solvent, and adds alkaline reagent to make EVA resin carry out saponification, soap in the basic conditions
Change reaction temperature and be 60～95 DEG C, the response time is 0.5～4 hour, obtains partly-hydrolysed EVA resin；
(2) the partly-hydrolysed EVA resin obtaining in step (1) and anhydride are carried out esterification, esterification reaction temperature is 65
～90 DEG C, the response time is 4～7 hours, and reaction is aged 60～90 hours after terminating at 55～80 DEG C, obtains final product described modified poly-
Compound.
3. preparation method polymer-modified as claimed in claim 2 is it is characterised in that the solvent in described step (1) is first
At least one in butylcyclohexane, butanone, n-butyl acetate；The alkaline reagent adding in described step (1) is NaOH and ethanol
Mixed solution, and in described mixed solution NaOH concentration be 0.1～1mol/L.
4. preparation method polymer-modified as claimed in claim 2 is it is characterised in that in EVA resin in described step (1)
The weight/mass percentage composition of VAc is 15～30%；The saponification rate of the partly-hydrolysed EVA resin of described step (1) gained be 15～
50%.
5. polymer-modified preparation method as described in any one of claim 2～4 is it is characterised in that described step (1) EVA
In resin, the content of VAc is 18%；Solvent is the mixture of hexahydrotoluene, butanone and n-butyl acetate；Alkaline reagent is
In NaOH and the mixed solution of ethanol, and described mixed solution, the concentration of NaOH is 0.5mol/L；Saponification temperature is 80 DEG C,
Response time is 2 hours；The saponification rate of the partly-hydrolysed EVA resin of gained is 40%.
6. preparation method polymer-modified as claimed in claim 2 is it is characterised in that the anhydride in described step (2) is horse
Come anhydride, HHPA, at least one in methyl hexahydrophthalic anhydride.
7. polymer-modified preparation method as described in claim 2 or 6 is it is characterised in that the anhydride in described step (2) is
Methyl hexahydrophthalic anhydride, esterification reaction temperature is 80 DEG C, and the response time is 6 hours, and reaction is aged 72 hours after terminating at 70 DEG C.
8. a kind of EVA shoe material inorganic agent is it is characterised in that the modification that described EVA shoe material inorganic agent contains described in claim 1 gathers
Compound.
9. EVA shoe material inorganic agent as claimed in claim 8 is it is characterised in that described EVA shoe material inorganic agent also contains solvent,
Described polymer-modified weight/mass percentage composition in described EVA shoe material inorganic agent is 2～4%.
10. the application in a kind of polymer-modified as claimed in claim 1 EVA shoe material inorganic agent in preparation.
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| CN110316690A (en) * | 2019-06-11 | 2019-10-11 | 惠科股份有限公司 | Flexible device buffer layer and preparation method thereof and flexible device |
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