CN1042942C - Method of water phase suspension for making ethylene-fluoride-vinyl acetate copolymer - Google Patents
Method of water phase suspension for making ethylene-fluoride-vinyl acetate copolymer Download PDFInfo
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- CN1042942C CN1042942C CN93112539A CN93112539A CN1042942C CN 1042942 C CN1042942 C CN 1042942C CN 93112539 A CN93112539 A CN 93112539A CN 93112539 A CN93112539 A CN 93112539A CN 1042942 C CN1042942 C CN 1042942C
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Abstract
The present invention relates to a water phase suspension method for making chlorination EVA. In a reaction vessel with a jacket, EVA powder is suspended in water; dispersing agents, emulsifiers and initiating agents A and B are simultaneously added to the water; then, the temperature in the reaction vessel at normal pressure is gradually raised, and chlorine gas is led to the reaction vessel for chlorination; finally, chlorination is carried out in the range of the melting temperature of EVA resin; a constant temperature segment exists in the process of the whole chlorination reaction. Compared with the solution method, the present invention has the advantages of simple technological process, and convenient and easy product obtainment; the cost can be reduced by more than 10 %. The obtained uniform and homogeneous chlorination EVA is neutral without carbon tetrachloride; thus, the work environment is good and operators are free from the influence of toxic solvent. The chlorination EVA of the present invention is especially suitable for making connection materials of printing ink of food packaging bags, paint and adhesives.
Description
The present invention relates to the manufacture method of ethylene chloride-ethylene acetate copolymer (EVA), particularly relate to a kind of manufacture method of water phase suspension ethylene chloride-ethylene acetate copolymer.
In prior art, the chlorination of ethylene-vinyl acetate copolymer mainly is a solution method, as being that ethylene-vinyl acetate copolymer is dissolved in chlorinated aliphatic hydrocarbon such as tetracol phenixin, ethylene dichloride, trichloromethane or chlorination aromatic hydrocarbons such as the chlorobenzene solvent among EP163970 and day disclosure special permission communique 58-145704, under the certain reaction temperature and pressure, lead to chlorinated with chlorine.Reaction mass is condensed and boil off organic solvent, chopping, oven dry and get product.The production ratio of this method is easier to control, chlorine is evenly distributed in the chlorizate, but it is big that its weak point is a solvent-oil ratio, to from being 5～7% dilute solution, concentration isolate product, and solvent and the hydrogenchloride of driving away trace from product are relatively more difficult, and product color is poor, becomes the block inconvenience of using, production cost is higher, and solvent is quite big to human body harm.So the chlorination problem of ethylene-vinyl acetate copolymer is the problem that people thirst for solving always.
The objective of the invention is to replace the ethylene chloride-ethylene acetate copolymer manufacture method of solvent method with the simple water phase suspension of technical process, in order to reduce production costs, product separation conveniently is easy to get, and Working environment is preferably arranged, make operator not be subjected to the influence of noxious solvent.With method of the present invention obtain be chlorination uniformly, the unformed elastomerics of free from extraneous odour.
For realizing this purpose, the present invention be in the reactor of strap clamp cover the ethylene-vinyl acetate copolymer powder suspension at aqueous phase, add various auxiliary agents such as dispersion agent, emulsifying agent, initiator simultaneously, logical chlorine chlorination under certain temperature and pressure, product gets product after washing neutralization, centrifugation, extruding pelletizing, vacuum-drying.
The used dispersion agent of the present invention is a kind of in polyacrylate, poly-methyl acrylate, the polyvinyl alcohol, and the consumption of dispersion agent is 0.5～2% (weight) of ethylene-vinyl acetate copolymer powder.Suitable dispersion agent is selected and consumption can guarantee that chlorinated reaction mass do not lump.
The used emulsifying agent of the present invention is a nonionic emulsifier, a kind of as in alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether, polyoxyethylenated castor oil, polyhydric alcohol fatty acid ester, the polyethers, the consumption of emulsifying agent is 0.5～2% (weight) of ethylene-vinyl acetate copolymer powder.Suitable emulsifying agent is selected and consumption should make the foam of reaction too much unsuitable, prevents that the reactor top cover is stained with material and muriate prevented from caking.
The used composite initiator of the present invention is made up of initiator A and initiator B, initiator A is the azo-compound of the alkyl that has two C3～C4, two cyano group or has the organo-peroxide of two alkyl acyls at least or have the organo-peroxide of two aralkyl acyls at least, a kind of as in dilauroyl peroxide, dibenzoyl peroxide, didecanoyl peroxide, dioctanoyl peroxide, the Diisopropyl azodicarboxylate.Initiator B is to have the organo-peroxide of an alkyl carboxylates at least or have the organo-peroxide of a carboxylic acid aryloxyalkyl group ester at least or have the alkyl of two C5～C8, the azo-compound of two cyano group, as the mistake-2 thylhexoic acid tert-butyl ester, cross the pivalic tert-butyl ester, peroxy dicarbonate hexichol oxygen ethyl ester, peroxy dicarbonate di-isooctyl, di-isopropyl peroxydicarbonate, cross the neodecanoic acid tert-butyl ester, cross a kind of in neodecanoic acid tert-pentyl ester, the 2,2'-Azobis(2,4-dimethylvaleronitrile).The consumption of initiator is 0.1～2% (weight) of ethylene-vinyl acetate copolymer powder, and the proportioning of initiator A and initiator B is 1: (1～10)～(1～10): 1, and the best proportioning of initiator A and initiator B is 1: 4～4: 1.
Chlorination reaction is to carry out in normal-pressure reaction kettle, employing progressively is warmed up to 50～100 ℃ of also logical chlorine and carries out chlorination, carry out chlorination at last in ethylene-vinyl acetate copolymer melt temperature scope, it is 2～7 hours that constant temperature zone, reaction times are arranged in the entire reaction course.
Chlorination process is made up of the absorption and the substitution reaction of chlorine, controlling factor is the rate of diffusion of chlorine in ethylene-vinyl acetate copolymer, and temperature of reaction is very big to the chlorination reaction influence, temperature of reaction of the present invention is 50～100 ℃, so both keep certain chlorination speed, guaranteed the stable of reaction system again.
The used ethylene-vinyl acetate copolymer powder of the present invention is that the method with Chinese patent 85108354 makes, and the content of its vinyl acetate between to for plastic is 10～35% (weight), and MI is 3～50 grams/10 minutes.
Logical chlorine speed directly has influence on the chlorinity of product, and logical chlorine speed is too slow, has prolonged the reaction times; Logical chlorine speed is too fast, and very exothermic makes some some district heat scatter and disappear difficulty and cause caking, and chlorine consumption increase has simultaneously improved production cost.After chlorination reaction finishes, the product discharging after 35～50 ℃ that will cool.
Reaction mass is put in the washing and still, adds the alkali neutralization when earlier material being washed pH and reaching certain value again.Neutralization back material is delivered to and is extruded pelletizing through centrifuge dehydration, is lower than 0.5% at Vacuumdrier inner drying to moisture content at last, promptly gets required ethylene chloride-ethylene acetate copolymer product, and chlorinity is 15～30% (weight).
In the water phase suspension ethylene chloride-ethylene acetate copolymer manufacturing processed, exist comparatively serious etching problem, strong corrosive mediums such as the dried chlorine of equipment and tube contacts, wet chlorine, hydrochloric acid.All material there is special requirement at chlorination, washing all equipment that contact with reaction mass, work in-process of operation such as neutralization and other accessories, pipeline and valve etc.
In chlorination reaction process, chlorizate does not lump to cooperatively interact by many-sided conditions such as stirring state, dispersion system, initiator, temperature of reaction and logical chlorine speed and solves, and these all are the places of technical characterictic involved in the present invention.
Technical process of the present invention is simple, replace solution method with water phase suspension, make uniform ethylene chloride-ethylene acetate copolymer, it is easily separated not lump, product is neutral free from extraneous odour, and cost can descend more than 10% than solution method, does not contain tetracol phenixin, so Working environment is better, operator are not subjected to the influence of noxious solvent.The ethylene chloride-ethylene acetate copolymer that this external application the present invention makes is a particulate state, brings great convenience to the user in the use.So be specially adapted to make low-melting ink vehicle, coating and the tackiness agent of food pack printing-ink with the ethylene chloride-ethylene acetate copolymer of manufacturing of the present invention.
Illustrate the present invention with embodiment below, but and do not mean that restriction the present invention.
Embodiment 1:
In 10 liter glass-lined kettles, add 6.0 liter water, the poly-methyl olefin(e) acid sodium of 4.5 grams, 4.0 gram fatty alcohol-polyoxyethylene ether, 400 grams by 30 purpose ethylene-vinyl acetate copolymer powder (vinyl acetate between to for plastic 32%, MI 10 grams/10 minutes).In the time of 50 ℃, add initiator A dilauroyl peroxide and initiator B peroxy dicarbonate hexichol oxygen ethyl ester 2.0 grams, initiator A: initiator B=2: 1.And then feeding chlorine, insulation is 1 hour about 60 ℃, is warming up to about 80 ℃ to keep 2 hours again.Reaction finishes the back and feed pressurized air in still, logical cooling water temperature to 40 ℃ discharging in the chuck.After washing, neutralize, extrude pelletizing, vacuum-drying, obtain chlorinity and be 17.3% ethylene chloride-ethylene acetate copolymer.
Embodiment 2:
In 10 liter glass-lined kettles, add 6.5 liter water, 3.0 gram polyvinyl alcohol, 6.0 gram alkylphenol polyoxyethylene, 450 grams by 30 purpose ethylene-vinyl acetate copolymer powder (vinyl acetate between to for plastic 15%, MI 40 grams/10 minutes).In the time of 50 ℃, add initiator A dibenzoyl peroxide and initiator B 2,2'-Azobis(2,4-dimethylvaleronitrile) 4.5 grams, initiator A: initiator B=1: 4.Feed chlorine then, maintenance is 1 hour about 60 ℃, is warming up to keep stopping after 2 hours logical chlorine about 80 ℃.Reaction finishes the back and feed pressurized air in still, logical cooling water temperature to 40 ℃ discharging in the chuck.Through washing neutralization, centrifuge dehydration, to obtain chlorinity after extruding pelletizing and vacuum-drying be 25% ethylene chloride-ethylene acetate copolymer granular product.
Embodiment 3:
In 10 liter glass-lined kettles, add 6.0 liter water, 6.5 gram sodium polyacrylates, 2.25 gram alkylphenol polyoxyethylene and 450 grams by 30 purpose ethylene-vinyl acetate copolymer powder (vinyl acetate between to for plastic 28%, MI 20 grams/10 minutes).Warming while stirring adds initiator A Diisopropyl azodicarboxylate and initiator B and crosses the neodecanoic acid tert-butyl ester 2.5 grams, initiator A: initiator B=3: 1 in the time of 50 ℃.Feed chlorine then, maintenance is 1 hour about 60 ℃, is warmed up to about 70 ℃ to keep 1 hour, is warmed up to keep stopping after 2 hours logical chlorine about 80 ℃ again.Reaction finishes the back and feed pressurized air in still, logical cooling water temperature to 40 ℃ discharging in the chuck.Through washing neutralization, centrifugation, to obtain chlorinity after extruding pelletizing, vacuum-drying be 21% ethylene chloride-ethylene acetate copolymer finished product.
Embodiment 4:
Remove the initiator B pivalic tert-butyl ester, initiator A: initiator B=outside 1: 5, other conditions are all identical with embodiment 3.Obtain chlorinity and be 20% ethylene chloride-ethylene acetate copolymer product.
Embodiment 5:
Remove the initiator A dioctanoyl peroxide, initiator A: initiator B=outside 6: 1, other conditions are all identical with embodiment 1.Obtain chlorinity and be 21.5% ethylene chloride-ethylene acetate copolymer product.
Embodiment 6:
Remove the initiator A didecanoyl peroxide, initiator A: initiator B=outside 1: 8, other conditions are all identical with embodiment 2.Obtain chlorinity and be 21.5% ethylene chloride-ethylene acetate copolymer product.
Embodiment 7:
Remove the initiator B di-isopropyl peroxydicarbonate, initiator A: initiator B=outside 1: 1, other conditions are all identical with embodiment 3.Obtain chlorinity and be 23% ethylene chloride-ethylene acetate copolymer product.
Embodiment 8:
In 500 liter glass-lined kettles, add 325 liter water, 150 gram polyvinyl alcohol, 300 gram alkylphenol polyoxyethylene, 22.5 kilograms by 30 purpose ethylene-vinyl acetate copolymer powder (vinyl acetate between to for plastic 15%, MI 40 grams/10 minutes).In the time of 50 ℃, add initiator A dibenzoyl peroxide and initiator B 2,2'-Azobis(2,4-dimethylvaleronitrile) totally 225 grams, initiator A: initiator B=1: 2.Other conditions are all identical with embodiment 2, obtain chlorinity and be 24% ethylene chloride-ethylene acetate copolymer product.
Embodiment 9:
In 500 liter glass-lined kettles, add 300 liter water, 325 gram sodium polyacrylates, 112.5 gram alkylphenol polyoxyethylene, 22.5 kilograms by 30 purpose ethylene-vinyl acetate copolymer powder (vinyl acetate between to for plastic 28%, MI 20 grams/10 minutes).Warming while stirring adds initiator A Diisopropyl azodicarboxylate and initiator B and crosses the neodecanoic acid tert-butyl ester 125 grams, initiator A: initiator B=1.5: 1 in the time of 50 ℃.Other conditions are all identical with embodiment 3, obtain chlorinity and be 20% ethylene chloride-ethylene acetate copolymer product.
Claims (4)
1, a kind of manufacture method with the water phase suspension ethylene chloride-ethylene acetate copolymer, comprise the ethylene-vinyl acetate copolymer powder through chlorination reaction, the washing neutralization, centrifugation, extrude, vacuum-drying, it is characterized in that: chlorination reaction several steps in the following order carries out in aqueous media
1. in the reactor of strap clamp cover the ethylene-vinyl acetate copolymer powder suspension in water, the dispersion agent that adds 0.5～2% (weight) simultaneously, described dispersion agent is a polyacrylate, poly-methyl acrylate, a kind of in the polyvinyl alcohol, the nonionic emulsifier of～2% 0.5 (weight), described nonionic emulsifier is an alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether, polyoxyethylenated castor oil, polyhydric alcohol fatty acid ester, a kind of in the polyethers, the initiator A of～2% 0.1 (weight) and B, described initiator A is the alkyl that has two C3～C4, the azo-compound of two cyano group or have the organo-peroxide of two alkyl acyls at least or have the organo-peroxide of two aralkyl acyls at least, described initiator B is to have the organo-peroxide of an alkyl carboxylates at least or have the organo-peroxide of a carboxylic acid aryloxyalkyl group ester at least or have the alkyl of two C5～C8, the azo-compound of two cyano group, the proportioning of initiator A and initiator B is 1: (1～10)～(1～10): 1
2. progressively be warmed up to 50～100 ℃ then in normal-pressure reaction kettle, and logical chlorine carries out chlorination, carry out chlorination at last in ethylene-vinyl acetate copolymer melt temperature scope, the reaction times is 2～7 hours,
3. logical cooling water temperature to 35 in the reacting kettle jacketing～50 ℃ is emitted reaction mass,
4. reaction mass obtains the ethylene chloride-ethylene acetate copolymer product that chlorinity is 15～30% (weight) through washing, alkali neutralization, centrifugation, after extruding pelletizing, vacuum-drying.
2, according to the described ethylene chloride-ethylene acetate copolymer manufacture method of claim 1, it is characterized in that: initiator A is a kind of in dilauroyl peroxide, dibenzoyl peroxide, didecanoyl peroxide, dioctanoyl peroxide, the Diisopropyl azodicarboxylate, and initiator B was-2 thylhexoic acid tert-butyl esters, cross the pivalic tert-butyl ester, peroxy dicarbonate hexichol oxygen ethyl ester, peroxy dicarbonate di-isooctyl, di-isopropyl peroxydicarbonate, cross the neodecanoic acid tert-butyl ester, cross a kind of in neodecanoic acid tert-pentyl ester, the 2,2'-Azobis(2,4-dimethylvaleronitrile).
3, according to the described ethylene chloride-ethylene acetate copolymer manufacture method of claim 1, it is characterized in that: the proportioning of initiator A and initiator B is 1: 4～4: 1.
4, according to the described ethylene chloride-ethylene acetate copolymer manufacture method of claim 1, it is characterized in that: the vinyl acetate content of used ethylene-vinyl acetate copolymer powder is 10～35% (weight), and MI is 3～50 grams/10 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93112539A CN1042942C (en) | 1993-09-01 | 1993-09-01 | Method of water phase suspension for making ethylene-fluoride-vinyl acetate copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93112539A CN1042942C (en) | 1993-09-01 | 1993-09-01 | Method of water phase suspension for making ethylene-fluoride-vinyl acetate copolymer |
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| Publication Number | Publication Date |
|---|---|
| CN1099763A CN1099763A (en) | 1995-03-08 |
| CN1042942C true CN1042942C (en) | 1999-04-14 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN93112539A Expired - Fee Related CN1042942C (en) | 1993-09-01 | 1993-09-01 | Method of water phase suspension for making ethylene-fluoride-vinyl acetate copolymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104098731B (en) * | 2013-04-11 | 2017-05-24 | 中国石油化工集团公司 | Method for preparing ethylene-vinyl alcohol copolymer through composite initiation system |
| CN104250314B (en) * | 2014-02-25 | 2017-11-14 | 江苏煦和新材料有限公司 | Viscosity metallocene PE synthesis technique in the high chlorination of water phase suspension |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85105030A (en) * | 1985-06-29 | 1986-09-03 | 华南工学院 | The gas-solid chlorination of polyethylene aqueous phase |
| CN87107853A (en) * | 1986-11-18 | 1988-09-28 | 昭和电工株式会社 | The production method of ethylene chloride-propylene copolymers |
| JPH03197508A (en) * | 1989-12-26 | 1991-08-28 | Sanyo Kokusaku Pulp Co Ltd | Production of chlorinated eva |
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1993
- 1993-09-01 CN CN93112539A patent/CN1042942C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85105030A (en) * | 1985-06-29 | 1986-09-03 | 华南工学院 | The gas-solid chlorination of polyethylene aqueous phase |
| CN87107853A (en) * | 1986-11-18 | 1988-09-28 | 昭和电工株式会社 | The production method of ethylene chloride-propylene copolymers |
| JPH03197508A (en) * | 1989-12-26 | 1991-08-28 | Sanyo Kokusaku Pulp Co Ltd | Production of chlorinated eva |
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| CN1099763A (en) | 1995-03-08 |
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