KR20170082915A - Method for preparing modified ethylene vinyl acetate resin and modified ethylene vinyl acetate resin - Google Patents
Method for preparing modified ethylene vinyl acetate resin and modified ethylene vinyl acetate resin Download PDFInfo
- Publication number
- KR20170082915A KR20170082915A KR1020160002231A KR20160002231A KR20170082915A KR 20170082915 A KR20170082915 A KR 20170082915A KR 1020160002231 A KR1020160002231 A KR 1020160002231A KR 20160002231 A KR20160002231 A KR 20160002231A KR 20170082915 A KR20170082915 A KR 20170082915A
- Authority
- KR
- South Korea
- Prior art keywords
- vinyl acetate
- ethylene vinyl
- acetate resin
- modified ethylene
- carbodiimide
- Prior art date
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Classifications
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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
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
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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
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
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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
- C08F263/00—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00
- C08F263/02—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00 on to polymers of vinyl esters with monocarboxylic acids
- C08F263/04—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00 on to polymers of vinyl esters with monocarboxylic acids on to polymers of vinyl acetate
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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
- C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
- C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C08L31/04—Homopolymers or copolymers of vinyl acetate
Abstract
The present invention relates to a process for producing a modified ethylene vinyl acetate resin and a modified ethylene vinyl acetate resin. More specifically, the method for producing the modified ethylene vinyl acetate resin includes the steps of: mixing ethylene vinyl acetate and a carbodiimide compound; And extruding the mixture. The modified ethylene vinyl acetate resin thus produced is excellent in hydrolysis resistance and weather resistance.
Description
The present invention relates to a method for producing a modified ethylene vinyl acetate resin excellent in hydrolysis resistance and a modified ethylene vinyl acetate resin.
Ethylene Vinyl Acetate is a copolymer of ethylene and vinyl acetate and has a wide range of applications from hard materials to flexible materials such as hot melt adhesives depending on the content of vinyl acetate. It has a lower crystallinity than polyethylene, low temperature characteristics and impact resistance This is an excellent feature.
Ethylene vinyl acetate has a thermoplastic polymer or rubber character and is excellent in electrical insulation and dielectric strength and is excellent in transparency, barrier property, adhesive property, and UV characteristic. Therefore, it can be used as a tube, a packaging material, Tapes, adhesives, various sheets, and the like. In recent years, the protective film for photoelectric devices such as solar cells has been widely used.
However, ethylene vinyl acetate has problems such as acetic acid being produced by hydrolysis of vinyl acetate, resulting in deterioration of physical properties, odor, color change, etc., and oxidation is caused by oxygen in an air atmosphere . Therefore, there is still a need for research to improve the properties such as hydrolysis resistance and weather resistance of ethylene vinyl acetate.
The present invention provides a process for producing a modified ethylene vinyl acetate resin excellent in hydrolysis resistance and a modified ethylene vinyl acetate resin.
The present invention relates to a process for producing ethylene vinyl acetate by mixing ethylene vinyl acetate and a carbodiimide compound; And extruding the mixture. The present invention also provides a method for producing a modified ethylene vinyl acetate resin.
The present invention also relates to a copolymer comprising a main chain comprising repeating units of ethylene vinyl acetate; And a branch grafted to the main chain and comprising a carbodiimide group.
The method for producing a modified ethylene vinyl acetate resin and the modified ethylene vinyl acetate resin according to a specific embodiment of the present invention will now be described in more detail.
According to one embodiment of the present invention, there is provided a method for producing a polyvinylidene fluoride resin, comprising: mixing ethylene vinyl acetate and a carbodiimide compound; And a step of extruding the mixture, to obtain a modified ethylene vinyl acetate resin.
The present inventors have recognized that ethylene vinyl acetate widely used in various fields such as packaging materials, films, adhesives and the like has limitations such as hydrolysis, oxidation and deterioration of physical properties depending on the external environment, and the hydrolysis resistance of ethylene vinyl acetate , Weatherability, and so on. Thus, it has been confirmed through experiments that ethylene vinyl acetate and a carbodiimide compound are mixed and extruded to produce a modified ethylene vinyl acetate resin having improved hydrolysis resistance and low acetic acid production by hydrolysis And completed the invention.
Specifically, when a mixture of ethylene vinyl acetate and a carbodiimide compound is extruded as in the above-described method for producing a modified ethylene vinyl acetate resin, an ethylene vinyl acetate resin in which carbodiimide groups are grafted to a polymer main chain is produced . The modified ethylene vinyl acetate resin in which the carbodiimide group is grafted reacts with water naturally contacted in polymerization and processing and acetic acid inevitably produced by hydrolysis of the polymer itself to form a nonreactive urea, Hydrolysis is not performed well because of the structural characteristics that are converted into the structure, which can minimize the generation of acetic acid by hydrolysis which is known as the limit of ethylene vinyl acetate.
Herein, the carbodiimide compound means a compound containing a carbodiimide group. Any compound having a carbodiimide group may be used without limitation, and preferably a carbodiimide compound containing a carbodiimide group and an olefinic unsaturated double bond Compounds may be used.
Further, as the carbodiimide compound, one compound containing a carbodiimide group or a mixture of two or more different compounds may be used. Preferably, carbodiimidoethyl methacrylate (Carbodiimidoethyl Methacrylate) can be used.
The carbodiimide compound may be added in an amount of about 0.01 to 10 parts by weight, preferably about 0.1 to 1 part by weight based on 100 parts by weight of ethylene and vinyl acetate.
In addition, the step of extruding the mixture of ethylene vinyl acetate and carbodiimide compound may include heating to about 100 to 220 캜, preferably about 150 to 200 캜, in the presence of organic peroxide . As described above, a mixture of ethylene vinyl acetate and a carbodiimide compound can be heated and melted after being heated to a temperature within the above range, and then extruded. The organic peroxide can form a peroxyl radical to form a carbodiimide group in the polymer main chain You can play the role of rafting.
The organic peroxide is not particularly limited as long as it can initiate the radical polymerization of the vinyl group, and specific examples thereof include at least one selected from the group consisting of organic peroxides, hydroperoxides and azo compounds. More specifically, t-butyl cumyl peroxide, di-t-butyl peroxide, di-cumyl peroxide, 2,5-dimethyl-2,5-di (t- butylperoxy) Dialkyl peroxides such as 2,5-di (t-butylperoxy) -3-hexyne; Hydroperoxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethyl-2,5-di (hydroperoxy) hexane, and t-butyl hydroperoxide; Diacyl peroxides such as bis-3,3,5-trimethylhexanoyl peroxide, octanoyl peroxide, benzoyl peroxide, o-methylbenzoyl peroxide and 2,4-dichlorobenzoyl peroxide; butyl peroxy isobutyrate, t-butyl peroxyacetate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, t-butyl peroxyoctoate, t- Butyl peroxybenzoate, di-t-butylperoxy phthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl- (Benzoyl peroxy) -3-hexyne; And ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; Azo compounds such as lauryl peroxide, azobisisobutyronitrile, and azobis (2,4-dimethylvaleronitrile) can be used.
In addition, the step of extruding the mixture of ethylene vinyl acetate and carbodiimide compound may include irradiating an electron beam of about 1 to 25 kGy, preferably about 2 to 10 kGy. As described above, the mixture of ethylene vinyl acetate and carbodiimide compound can be extruded after irradiating and melting by irradiating an electron beam having an irradiation dose in the above-mentioned range. In this case, the step of irradiating the electron beam is a step of heating in the presence of the above- It can be done separately or together.
On the other hand, according to another embodiment of the present invention, there is provided a resin composition comprising a main chain comprising repeating units of ethylene vinyl acetate; And a branch grafted to the main chain and containing a carbodiimide group.
In this case, the branch containing the carbodiimide group is grafted to the main chain. This means that the branch containing the carbodiimide group is not copolymerized with the original structure of the polymer but is grafted to the main chain by post modification, A radical generated by using an organic peroxide or an electron beam is reacted with a radical of an unsaturated double bond to form a branch containing a carbodiimide group in a main chain containing a repeating unit of ethylene vinyl acetate Followed by grafting.
Such modified ethylene vinyl acetate resin not only has inherent properties of ethylene vinyl acetate resin but also reacts with water naturally contacted in the polymerization and processing step and acetic acid inevitably produced by hydrolysis of the polymer itself, since the hydrolysis phenomenon of the ethylene vinyl acetate resin itself which occurs when exposed to moisture can be minimized, it is possible to provide a bag for a solar cell module applied to an aqueous phase The present invention is also applicable to a sealing material which is applied to ash glass for a bathroom, or the like, which is likely to be exposed to moisture.
The modified ethylene vinyl acetate resin may be prepared by polymerizing ethylene, vinyl acetate, and carbodiimide compounds at a high pressure according to the production method of one embodiment. The modified ethylene vinyl acetate resin thus prepared is an ethylene vinyl acetate resin grafted with a carbodiimide group, which has an improved hydrolysis resistance and is characterized in that the amount of acetic acid produced by hydrolysis is small.
According to the method for producing a modified ethylene vinyl acetate resin of the present invention, a carbodiimide group is grafted to provide a modified ethylene vinyl acetate resin having improved hydrolysis resistance.
The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.
Example : Preparation of Modified Ethylene Vinyl Acetate Resin
99.45 parts by weight of an ethylene vinyl acetate copolymer having a vinyl acetate content of 26 to 30 wt% and an MFR of 23 to 27 g / 10 min under a load of 2.16 kg at 190 DEG C, 0.5 part by weight of carbodiimide methacrylate, 0.05 part by weight of bis (t-butylperoxy) -2,5-dimethylhexane (Luperox®101) was subjected to grafting reaction extrusion at 200 ° C. using a twin-screw extruder to prepare a master batch of denatured ethylene vinyl acetate resin Respectively.
Claims (6)
And extruding the mixture. ≪ RTI ID = 0.0 > 11. < / RTI >
Wherein the ethylene vinyl acetate and the carbodiimide compound are mixed at 0.01 to 10 parts by weight.
Wherein the extruding comprises heating to 100-220 占 폚 in the presence of organic peroxide.
Wherein the step of extruding comprises irradiating an electron beam of 1 to 25 kGy.
Wherein the modified ethylene vinyl acetate resin is produced according to the production method of any one of claims 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020160002231A KR20170082915A (en) | 2016-01-07 | 2016-01-07 | Method for preparing modified ethylene vinyl acetate resin and modified ethylene vinyl acetate resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020160002231A KR20170082915A (en) | 2016-01-07 | 2016-01-07 | Method for preparing modified ethylene vinyl acetate resin and modified ethylene vinyl acetate resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20170082915A true KR20170082915A (en) | 2017-07-17 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020160002231A KR20170082915A (en) | 2016-01-07 | 2016-01-07 | Method for preparing modified ethylene vinyl acetate resin and modified ethylene vinyl acetate resin |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR20170082915A (en) |
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2016
- 2016-01-07 KR KR1020160002231A patent/KR20170082915A/en unknown
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