CN105968549A - EVA (ethylene-vinyl acetate) copolymer and preparation method thereof - Google Patents
EVA (ethylene-vinyl acetate) copolymer and preparation method thereof Download PDFInfo
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- CN105968549A CN105968549A CN201610355998.6A CN201610355998A CN105968549A CN 105968549 A CN105968549 A CN 105968549A CN 201610355998 A CN201610355998 A CN 201610355998A CN 105968549 A CN105968549 A CN 105968549A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses an EVA (ethylene-vinyl acetate) copolymer and a preparation method thereof. The EVA copolymer comprises the following components in percentage by weight: 50-70% of EVA particle, 10-30% of phenolic resin, 10-50% of methyl acrylate, 1-10% of ammonia water, 5-20% of cellulose, 5-20% of calcium carbonate, 5-20% of magnesium carbonate, 0-3.8% of color paste, 3-9% of emulsifier, 0-0.5% of coupling agent, 0.5-5% of accelerator, 1-5% of preservative and 20-40% of deionized water. The EVA copolymer has the advantages of high melting tension and extremely low probability for gel or fisheye formation. Thus, the obtained crosslinked EVA copolymer can be used as a raw material for shoe soles and wires.
Description
Technical field
The invention belongs to field of fine chemical, particularly to a kind of EVA copolymer and preparation method thereof.
Background technology
In order to form stable and excellent foams, the EVA copolymer resin used in foams should
This has optimum melted tension force and melt index (MI).In EVA resin, there is higher acetic acid
The resin of vinyl acetate (VA) content usually obtains the froth pulp of telescopic in height.But, VA contains
Measure the highest, it is thus achieved that the difficulty of the product with high melted tension force or low MI is the highest.Contain to reduce
There is the MI of the EVA copolymer resin of high VA content and increase melted tension force simultaneously, multiple place can be attempted
Reason method.At EVA copolymer resin in the case of foams, for examining in terms of economic benefit
Consider, more preferably utilize organic peroxide to reduce the MI of EVA copolymer resin by crosslinking, and not
It is to reduce EVA altogether by crosslinking with radiation or the crosslinking that utilizes the copolymerization with the monomer with double bond to carry out
The MI of copolymer resin.But, when being applied to film or electric wire, utilize organic peroxide to carry out directly
Crosslinking has some shortcomings.
Wherein at Chinese invention patent, Authorization Notice No. is to provide in CN 102382353 B, closes
In EVA material application in road cone produces, but the raw material of sole and electric wire can not be made.And
A kind of ameliorative EVA, tool is provided in Chinese invention patent, Application No. 201410336944.6
There is the advantage with high temperature resistant, corrosion-resistant and nonhazardous, but the former material of sole and electric wire can not be made
Material.
Summary of the invention
It is an object of the invention to provide a kind of EVA copolymer and preparation method thereof, prepared by the present invention
EVA copolymer has high melted tension force and the gel of extremely low probability or the EVA copolymer of flake formation.
The EVA copolymer of the crosslinking so obtained can be used as the raw material of sole and electric wire.
The present invention can be achieved through the following technical solutions:
The invention discloses a kind of EVA copolymer, the following component including by weight percentage: EVA
Particle 50～70%, phenolic resin 10～30%, acrylic acid methyl ester. 10～50%, ammonia 1～10%,
Cellulose 5～20%, calcium carbonate 5～20%, magnesium carbonate 5～20%, mill base 0～3.8%, emulsifying agent 3～
9%, coupling agent 0～0.5%, accelerator 0.5～5%, preservative 1～5%, deionized water 20～40%,
The EVA copolymer of preparation can be made to have by coupling agent and accelerator in the present invention the strongest
Degree, is not limited to acrylic acid methyl ester., it is also possible to include other esters of acrylic acids the most in the present invention.
Described a kind of EVA copolymer, the following component including by weight percentage: EVA particle
60～70%, phenolic resin 20～30%, acrylic acid methyl ester. 10～40%, ammonia 1～8%, cellulose
5～10%, calcium carbonate 5～15%, magnesium carbonate 5～15%, mill base 1～3.8%, emulsifying agent 3～6%, even
Connection agent 0.1～0.5%, accelerator 0.5～3%, preservative 1～4%, deionized water 20～40%.
Described a kind of EVA copolymer, the following component including by weight percentage: EVA particle
65%, phenolic resin 25%, acrylic acid methyl ester. 30%, ammonia 5%, cellulose 5%, calcium carbonate 10%,
Magnesium carbonate 10%, mill base 1.7%, emulsifying agent 4%, coupling agent 0.3%, accelerator 2%, preservative 2%,
Deionized water 30%, this programme, as optimal scheme, can make the EVA copolymer of preparation have height
The EVA copolymer that melted tension force and the gel of extremely low probability or flake are formed, and have and preferably tear
Resistance to spalling and hot strength, and there is more preferable storage characteristics.
Described emulsifying agent is made up of anion emulsifier and nonionic emulsifier, described anion emulsifier
For at least one in sodium lauryl sulphate, dodecylbenzene sodium sulfonate, described nonionic emulsifier
For alkylphenol polyoxyethylene, reasonable emulsifying effectiveness can be reached.
Described coupling agent is silane coupler, and silane coupler can be KH171, KH550 etc., described
Accelerator is environmental protection accelerator, and described preservative is antifungus agent BCM.
Described environmental protection accelerator is zinc diisobutyldithiocarbamate and dibutyl dithio amino first
The combination of acid zinc, the ratio of combination is 1:1.5, makes the EVA copolymer of preparation have the performance of environmental protection,
And the ratio of the combination of environmental protection accelerator is 1:1.5, EVA copolymer can be made to have good speed
Dryness energy.
Described emulsifying agent is sodium lauryl sulphate, dodecylbenzene sodium sulfonate and alkylphenol-polyethenoxy
Ether mixes, and mixed proportion is 1:1:1.5, and EVA copolymer can be made the most stable.Described
Cellulose, calcium carbonate, the particle size range of magnesium carbonate are 500 mesh～1250 mesh, by different-grain diameter
Cellulose, calcium carbonate and magnesium carbonate, can make the EVA copolymer of preparation have more preferably exquisiteness,
Concrete particle diameter is cellulose 1250 mesh, calcium carbonate 500 mesh, and magnesium carbonate 1250 mesh can reach
In EVA copolymer, the gap of particle is less.
The other one side of the present invention, the preparation method of a kind of EVA copolymer, comprise the steps:
Successively by EVA particle, phenolic resin, in acrylic acid methyl ester. and emulsifying agent addition deionized water also
Carry out blended melting and obtain the first mixture；
Cellulose, calcium carbonate, magnesium carbonate and mill base are added in the first mixture and stir and be mixed to get
Second mixture.
Ammonia and preservative are sequentially added in the second mixture and stir and be mixed to get the 3rd mixture；
Coupling agent and accelerator are added in the 3rd mixture and stirs and be mixed to get EVA copolymer, its
In, stirring condition is, is stirred under the vacuum condition of 1000～1500 rpms.
One EVA copolymer of the present invention, has a following beneficial effect:
The first, the formula of the present invention is by being added with coupling agent and accelerator, can make the EVA of preparation
Copolymer has high melted tension force and the gel of extremely low probability or the EVA copolymer of flake formation, so
The EVA copolymer of the crosslinking obtained can be used as the raw material of sole and electric wire；
The second, inventive formulation is by being added with cellulose, can make EVA copolymer surface more
Moist；
3rd, the silane coupler in the present invention and accelerator, can make to prepare the face of EVA copolymer
Color keeps more longlasting, not fugitive color.
Detailed description of the invention
In order to make those skilled in the art be more fully understood that technical scheme, below in conjunction with reality
Execute example product of the present invention is described in further detail.
Embodiment 1
Embodiment 1 is a kind of EVA copolymer, the following component including by weight percentage: EVA grain
Son 50, phenolic resin 10, acrylic acid methyl ester. 10, ammonia 1, cellulose 5, calcium carbonate 5, carbonic acid
Magnesium 5, emulsifying agent 3, accelerator 0.5, preservative 1, deionized water 20, in an embodiment by even
Connection agent and accelerator, can make the EVA copolymer of preparation have the solidifying of high melted tension force and extremely low probability
The EVA copolymer that glue or flake are formed, and by being added with cellulose, EVA copolymer can be made
Surface is the finest and the smoothest, further by being added with phenolic resin and acrylic acid methyl ester., can make preparation
EVA copolymer there is more preferable stability and intensity, and then EVA copolymer has high melted tension force
The EVA copolymer formed with gel or the flake of extremely low probability.The EVA copolymerization of the crosslinking so obtained
Thing can be used as the raw material of sole and electric wire, and the silane coupler in the present invention and accelerator,
The color preparing EVA copolymer can be made to keep more longlasting, not fugitive color.
Embodiment 2
Embodiment 2 is a kind of EVA copolymer, EVA particle 70, phenolic resin 30, acrylic acid first
Ester 50, ammonia 10, cellulose 20, calcium carbonate 20, magnesium carbonate 20, mill base 3.8, emulsifying agent 9,
Coupling agent 0.5, accelerator 5, preservative 5, deionized water 40, passes through coupling agent in an embodiment
And accelerator, can make the EVA copolymer of preparation have high melted tension force and the gel of extremely low probability or
The EVA copolymer that flake is formed, and by being added with cellulose, EVA copolymer surface can be made
More fine and smooth, further by being added with phenolic resin and acrylic acid methyl ester., the EVA of preparation can be made
Copolymer has more preferable stability and intensity, and then EVA copolymer has high melted tension force and extremely low
The EVA copolymer that the gel of probability or flake are formed.The EVA copolymer of the crosslinking so obtained can
It is used as the raw material of sole and electric wire, and the silane coupler in the present invention and accelerator, permissible
The color preparing EVA copolymer is made to keep more longlasting, not fugitive color.
Embodiment 3
Embodiment 3 is a kind of EVA copolymer, the following component including by weight percentage: EVA grain
Son 60, phenolic resin 20, acrylic acid methyl ester. 10, ammonia 1, cellulose 5, calcium carbonate 5, carbonic acid
Magnesium 5, mill base 1, emulsifying agent 3, coupling agent 0.1, accelerator 0.5, preservative 1, deionized water
20, in an embodiment by coupling agent and accelerator, the EVA copolymer of preparation can be made to have Gao Rong
Melt tension force and the gel of extremely low probability or the EVA copolymer of flake formation, and by being added with fiber
Element, can make EVA copolymer surface the finest and the smoothest, further by being added with phenolic resin and third
E pioic acid methyl ester, can make the EVA copolymer of preparation have more preferable stability and intensity, and then EVA
Copolymer has high melted tension force and the gel of extremely low probability or the EVA copolymer of flake formation.So
The EVA copolymer of the crosslinking obtained can be used as the raw material of sole and electric wire, and in the present invention
Silane coupler and accelerator, the color that can make to prepare EVA copolymer keeps more longlasting, is difficult to
Fade.
Embodiment 4
Embodiment 4 is a kind of EVA copolymer, the following component including by weight percentage: EVA grain
Son 70, phenolic resin 30, acrylic acid methyl ester. 40, ammonia 8, cellulose 10, calcium carbonate 15, carbon
Acid magnesium 15, mill base 3.8, emulsifying agent 6, coupling agent 0.5, accelerator 3, preservative 4, deionization
Water 40, in an embodiment by coupling agent and accelerator, can make the EVA copolymer of preparation have height
The EVA copolymer that melted tension force and the gel of extremely low probability or flake are formed, and by being added with fibre
Dimension element, EVA copolymer surface can be made the finest and the smoothest, further by be added with phenolic resin and
Acrylic acid methyl ester., can make the EVA copolymer of preparation have more preferable stability and intensity, and then EVA
Copolymer has high melted tension force and the gel of extremely low probability or the EVA copolymer of flake formation.So
The EVA copolymer of the crosslinking obtained can be used as the raw material of sole and electric wire, and in the present invention
Silane coupler and accelerator, the color that can make to prepare EVA copolymer keeps more longlasting, is difficult to
Fade.
Embodiment 5
Embodiment 5 is a kind of EVA copolymer, EVA particle 65, phenolic resin 25, acrylic acid first
Ester 30, ammonia 5, cellulose 5, calcium carbonate 10, magnesium carbonate 10, mill base 1.7, emulsifying agent 4, even
Connection agent 0.3, accelerator 2, preservative 2, deionized water 30, in an embodiment by coupling agent and
Accelerator, can make the EVA copolymer of preparation have high melted tension force and the gel of extremely low probability or fish
The EVA copolymer that eye-shaped becomes, and by being added with cellulose, EVA copolymer surface can be made more
The exquisiteness added, further by being added with phenolic resin and acrylic acid methyl ester., can make the EVA of preparation
Copolymer has more preferable stability and intensity, and then EVA copolymer has high melted tension force and extremely low
The EVA copolymer that the gel of probability or flake are formed.The EVA copolymer of the crosslinking so obtained can
It is used as the raw material of sole and electric wire, and the silane coupler in the present invention and accelerator, permissible
Making the color preparing EVA copolymer keep more longlasting, not fugitive color, emulsifying agent is by anion emulsifier
Forming with nonionic emulsifier, anion emulsifier is sodium lauryl sulphate, DBSA
At least one in sodium, nonionic emulsifier is alkylphenol polyoxyethylene, can reach reasonable
Emulsifying effectiveness, coupling agent is silane coupler, and silane coupler can be KH171, KH550 etc.,
Accelerator is environmental protection accelerator, and preservative is antifungus agent BCM, and further, environmental protection accelerator is two different
Zinc dibutyl dithiocarbamate and the combination of zinc dibutyl dithiocarbamate, the ratio of combination is
1:1.5, makes the EVA copolymer of preparation have a performance of environmental protection, and the combination of environmental protection accelerator
Ratio is 1:1.5, and EVA copolymer can be made to have good rapid-curing cutback performance, further preferably, breast
Agent is that sodium lauryl sulphate, dodecylbenzene sodium sulfonate and alkylphenol polyoxyethylene mix,
Mixed proportion is 1:1:1.5, can reach more preferable emulsifying effectiveness, and can make the EVA of preparation
Copolymer is the most stable, described cellulose, calcium carbonate, the particle size range of magnesium carbonate be 500 mesh～
1250 mesh, by the cellulose of different-grain diameter, calcium carbonate and magnesium carbonate, can make the EVA of preparation altogether
Polymers has more preferably exquisiteness, specially cellulose 1250 mesh, calcium carbonate 500 mesh, magnesium carbonate
1250 mesh, can reach the gap of particle in EVA copolymer less.
The EVA copolymer the most just prepared with the formula of the present invention is carried out with EVA copolymer on the market
Contrasting as follows, the ambient temperature (room temperature) of test sample thickness 1mm test is identical, and concrete data are such as
Shown in table 1；
Table 1
| Effect | The EVA copolymer of the present invention | The EVA copolymer of market |
| Melted tension force | High | Low |
| Parch the time | 60s | 160s |
| Tearing strength | 10MPa | 6MPa |
| Hot strength | 20MPa | 15MPa |
| Fade test | Fade in the middle part of 48 hours highly basic | 12 hours highly basic fade |
| Surface flatness | Excellent | Difference |
Come as can be seen from Table I, the product of the present invention, there is high melted tension force and extremely low probability
The EVA copolymer that gel or flake are formed, and there is higher tearing strength and hot strength, with
And be not easy to fade, and surface has good smoothness.
The another side of the present invention, the preparation method of a kind of EVA copolymer: comprise the following steps:
Step S1: successively by EVA particle, phenolic resin, acrylic acid methyl ester. and emulsifying agent add go from
In sub-water and carry out blended melting and obtain the first mixture.
Step S2: cellulose, calcium carbonate, magnesium carbonate and mill base are added in the first mixture and stirs
It is mixed to get the second mixture.
Step S3: ammonia and preservative are sequentially added in the second mixture and stir and be mixed to get the 3rd
Mixture, wherein, stirring condition is, carries out under the vacuum condition of 1000～1500 rpms
Stirring；
Step S4: coupling agent and accelerator are added in the 3rd mixture and stirring is mixed to get EVA altogether
Polymers.
The above, only presently preferred embodiments of the present invention, not the present invention is made any form
On restriction；The those of ordinary skill of all industry all can by specification and the above and real swimmingly
Execute the present invention；But, all those skilled in the art are without departing from technical solution of the present invention scope
In, available disclosed above technology contents and make a little change, modify and being equal to of developing
Change, is the Equivalent embodiments of the present invention；Meanwhile, all substantial technological according to the present invention to more than
The change of any equivalent variations that embodiment is made, modify and differentiation etc., all still fall within the skill of the present invention
Within the protection domain of art scheme.
Claims (9)
1. an EVA copolymer, it is characterised in that include following group by weight percentage
Point: EVA particle 50～70%, phenolic resin 10～30%, acrylic acid methyl ester. 10～50%,
Ammonia 1～10%, cellulose 5～20%, calcium carbonate 5～20%, magnesium carbonate 5～20%, mill base
0～3.8%, emulsifying agent 3～9%, coupling agent 0～0.5%, accelerator 0.5～5%, preservative
1～5%, deionized water 20～40%.
EVA copolymer the most according to claim 1, it is characterised in that: include by weight
The following component of percentages: EVA particle 60～70%, phenolic resin 20～30%, propylene
Acid methyl ester 10～40%, ammonia 1～8%, cellulose 5～10%, calcium carbonate 5～15%, carbonic acid
Magnesium 5～15%, mill base 1～3.8%, emulsifying agent 3～6%, coupling agent 0.1～0.5%, promote
Agent 0.5～3%, preservative 1～4%, deionized water 20～40%.
EVA copolymer the most according to claim 1, it is characterised in that: include by weight
The following component of percentages: EVA particle 65%, phenolic resin 25%, acrylic acid methyl ester. 30%,
Ammonia 5%, cellulose 5%, calcium carbonate 10%, magnesium carbonate 10%, mill base 1.7%, emulsifying agent
4%, coupling agent 0.3%, accelerator 2%, preservative 2%, deionized water 30%.
EVA copolymer the most according to claim 1, it is characterised in that: described emulsifying agent
Being made up of anion emulsifier and nonionic emulsifier, described anion emulsifier is dodecyl
At least one in sodium sulfate, dodecylbenzene sodium sulfonate, described nonionic emulsifier is alkyl
Phenol polyethenoxy ether.
EVA copolymer the most according to claim 1, it is characterised in that: described coupling agent
For silane coupler, described accelerator is environmental protection accelerator, and described preservative is antifungus agent BCM.
EVA copolymer the most according to claim 5, it is characterised in that: described environmental protection promotees
Enter the group that agent is zinc diisobutyldithiocarbamate and zinc dibutyl dithiocarbamate
Closing, the ratio of combination is 1:1.5.
EVA copolymer the most according to claim 4, it is characterised in that: described cellulose,
Calcium carbonate, the particle size range of magnesium carbonate are 500 mesh～1250 mesh.
8. a preparation method for EVA copolymer as described in any one in claim 1～7,
It is characterized in that, comprise the steps:
Successively by EVA particle, phenolic resin, acrylic acid methyl ester. and emulsifying agent add deionization
In water and carry out blended melting and obtain the first mixture；
Cellulose, calcium carbonate, magnesium carbonate and mill base are added in the first mixture and stirs mixing
Obtain the second mixture；
Ammonia and preservative are sequentially added in the second mixture and stir and be mixed to get the 3rd mixing
Thing；
Coupling agent and accelerator are added in the 3rd mixture and stirs and be mixed to get EVA copolymer.
The preparation method of EVA copolymer the most according to claim 8, it is characterised in that
Described coupling agent and accelerator are added in the 3rd mixture and stirring is mixed to get EVA copolymerization
In the step of thing, stirring condition is, enters under the vacuum condition of 1000～1500 rpms
Row stirring.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610355998.6A CN105968549A (en) | 2016-05-25 | 2016-05-25 | EVA (ethylene-vinyl acetate) copolymer and preparation method thereof |
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| CN201610355998.6A CN105968549A (en) | 2016-05-25 | 2016-05-25 | EVA (ethylene-vinyl acetate) copolymer and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN114752138A (en) * | 2022-03-29 | 2022-07-15 | 山西玄云科技有限公司 | Environment-friendly light EVA plastic particle and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102876241B (en) * | 2012-09-20 | 2013-10-02 | 吴江市天源塑胶有限公司 | Adhesive for wrapping paper material |
-
2016
- 2016-05-25 CN CN201610355998.6A patent/CN105968549A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102876241B (en) * | 2012-09-20 | 2013-10-02 | 吴江市天源塑胶有限公司 | Adhesive for wrapping paper material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN114752138A (en) * | 2022-03-29 | 2022-07-15 | 山西玄云科技有限公司 | Environment-friendly light EVA plastic particle and preparation method thereof |
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Address after: Nansha District Fengze road Guangzhou city Guangdong province 511458 No. 106 X1301-B437 Applicant after: Guangzhou poly injection General Technology Research Institute Co Ltd Address before: Nansha District Fengze road Guangzhou city Guangdong province 511458 No. 106 X1301-B437 Applicant before: GUANGZHOU JUZHU PATENT RESEARCH AND DEVELOPMENT CO., LTD. |
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Application publication date: 20160928 |