CN105175585A - Method for preparing chlorinated polyethylene in acid medium - Google Patents
Method for preparing chlorinated polyethylene in acid medium Download PDFInfo
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- CN105175585A CN105175585A CN201510664364.4A CN201510664364A CN105175585A CN 105175585 A CN105175585 A CN 105175585A CN 201510664364 A CN201510664364 A CN 201510664364A CN 105175585 A CN105175585 A CN 105175585A
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- chlorinatedpolyethylene
- hydrochloric acid
- polyethylene
- depickling
- acidic medium
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Abstract
The invention discloses a method for preparing chlorinated polyethylene in an acid medium. Polyethylene is broken and sieved firstly, and polyethylene particles with the grain diameter of 40-120 meshes are obtained. The polyethylene particles are placed in hydrochloric acid added with emulgator, dispersant and initiator, under the stirring action, the polyethylene particles are suspended and heated for temperature rise, chlorine is introduced, and a chlorination reaction is conducted under certain pressure conditions. After the reaction is completed, chlorine left in a reaction still is replaced with air. Chlorinated polyethylene is subjected to preliminary washing deacidification, secondary deacidification, neutralization, dewatering and drying, and then chlorinated polyethylene with the chloride mass fraction of 65% can be prepared. An HCl water solution obtained after preliminary deacidification of chlorinated polyethylene is recycled, redundant hydrochloric acid is refined, and a hydrochloric acid product with the hydrochloric acid concentration of 20% is obtained. Chlorinated polyethylene produced through the process can be applied to the industries such as adhesives used for PVC bonding, fire retardant and anticorrosive paint.
Description
Technical field
The present invention relates to a kind of method preparing chlorinatedpolyethylene in acidic medium.
Background technology
Chlorinatedpolyolefins, as chlorinatedpolyethylene, chlorinated polyvinyl chloride, clorafin, Chlorinated Polypropylene III, ethylene chloride-ethylene acetate copolymer, chlorinated rubber etc. have nontoxic, water-fast, acidproof, easy film forming, the transparency advantage such as good, nonflammable, be widely used in fields such as protective system, anti-flaming dope and chlorinated rubber surrogates.Wherein chloride massfraction be 63 ~ 67% high chlorinatedpolyolefins be mainly used in the substitute of chlorinated rubber.
At present, the preparation method of chlorinatedpolyolefins mainly contains three major types: chlorination by solid state method, solvent chlorination process, aqueous suspension chlorination method.Owing to being subject to the restriction of the contact gear ratio area of polyolefine and chlorine molecule, thus there is heat-transfer capability difference in chlorination by solid state method, product chlorination is uneven, and the problem such as product coking and can not extensively adopting.Chloride solution produces chlorinatedpolyolefins, although product chlorination is even, superior performance, consumes the fluorochlorohydrocarbon classes such as a large amount of tetracol phenixin in producing.And this kind of material can cause damage to ozonosphere, therefore, solvent chlorination process is eliminated.Aqueous suspension chlorination method adopts clean process water, deionized water or distilled water as medium, is one eco-friendly processing method comparatively speaking.
In recent years, aqueous suspension chlorination method has become the prevailing technology producing chlorinatedpolyolefins both at home and abroad.But aqueous suspension chlorination method technique exists that acid waste water concentration is low, generation is large, process need neutralize with a large amount of alkali, and processing cost is high; Produce a small amount of milk in chlorination process, easily run off in deacidification, cause the shortcoming that product yield is low.
Summary of the invention
In order to overcome when existing aqueous suspension chlorination method prepares the hydrochloric acid N-process consumption energy consumption of by-product in chlorinatedpolyolefins and the problem that cannot recycle, the hydrochloric acid that the invention provides a kind of by-product prepares the method for chlorinatedpolyethylene as medium.The method synthesis technique is simple, and benefit is obvious, and while being the chlorinatedpolyolefins of 65% producing chloride massfraction, by-product goes out the hydrochloric acid that concentration is 20%, thus improves the economic benefit of chlorinatedpolyolefins production technique.
The method should producing chlorinatedpolyethylene in acidic medium is:
First polyethylene sieves through fragmentation, obtain particle diameter at 40 ~ 120 object polyethylene particles, then polymer raw material polyethylene particle is put in the reactor with emulsifying agent 400 ~ 600g, dispersion agent 400 ~ 600g and initiator 800 ~ 1000g, hydrochloric acid soln 1500kg, the concentration of hydrochloric acid is 10% ~ 12%, under stirring, polyethylene particles is made to be suspended state, be heated to 60 ~ 120 DEG C, thereafter pass into 380 ~ 400kg chlorine, under pressure is 0.4 ~ 0.45Mpa condition, carry out chlorination reaction 24 hours; After reaction terminates, with chlorine remaining in air displacement reactor; Chlorinatedpolyethylene, after initial water wash depickling, secondary depickling, neutralization, dehydration and drying, can obtain the chlorinatedpolyethylene that chloride massfraction is 65%; HCl solution after the preliminary depickling of chlorinatedpolyethylene, recycle, the concentration obtaining hydrochloric acid after unnecessary salt acid treating is the hydrochloric acid product of 20%.
In aforesaid method, described emulsifying agent is the one in polyoxyethylene nonylphenol ether, alkyl phenolic group Soxylat A 25-7, Viscotrol C-Soxylat A 25-7, pyrrolidone, C12-C14 alkanoic acid di-alcohol.
In aforesaid method, described dispersion agent is the one in the mixture of 18-alkyl dimethyl benzyl ammonium chloride, 14-alkyl dimethyl benzyl ammonium chloride, alkyl trimethyl ammonium chloride, polyoxyethylene and polyoxypropylene, alkyl front three methyl sulfate amine, Cocoalkyl front three ammonium chloride.
In aforesaid method, described initiator is the one in dilauroyl peroxide, benzoyl peroxide, Diisopropyl azodicarboxylate.
In aforesaid method, the hydrochloric acid reclaimed after described chlorinatedpolyethylene depickling uses as the acidic medium in described reactor.
The chlorinatedpolyethylene that the present invention produces fully will dissolve in the organic solvent such as toluene, dimethylbenzene, without obvious suspended substance and throw out.
The present invention adopts the hydrochloric acid of preliminary depickling as medium in the production process of chlorinatedpolyolefins, except there is the same advantage of aqueous suspension chlorination method, also have the following advantages: one is adopt sour phase suspension method, the hydrochloric acid that concentration is 20% can be reclaimed, there is recycle be worth, realize utilization of waste material, decrease acid waste water generation.
Two be utilize preliminary depickling to produce hydrochloric acid as acidic medium, recycle, acid waste water generation can be decreased equally.
Above two make acid waste water generation have to reduce largely, thus decrease the quantity of alkali consumption of wastewater treatment, reduce the cost of wastewater treatment.
Three is that sour phase suspension method does not produce milk in chlorination process, and the hydrochloric acid filtered out is limpid, and therefore product yield is high.
The chlorinatedpolyethylene that the present invention produces, the raw material being suitable as the industries such as fire retardant, protective system and tackiness agent uses.
Accompanying drawing explanation
Fig. 1 provides model to be the polyethylene nucleus magnetic hydrogen spectrum (deuterated orthodichlorobenzene) of 1I2A by Beijing Yanshan Petrochemical Company.
Fig. 2 is the nucleus magnetic hydrogen spectrum (deuterochloroform) providing model 1I2A polyethylene to prepare chlorinatedpolyethylene by Beijing Yanshan Petrochemical Company.
Fig. 3 provides model to be the polyethylene nucleus magnetic hydrogen spectrum (deuterated orthodichlorobenzene) of 1I20A by Beijing Yanshan Petrochemical Company
Fig. 4 is the nucleus magnetic hydrogen spectrum (deuterochloroform) providing model 1I20A polyethylene to prepare chlorinatedpolyethylene by Beijing Yanshan Petrochemical Company.
Embodiment
Embodiment 1
First polyethylene 1I2A sieves through fragmentation, obtain particle diameter at 40 ~ 120 object polyethylene particles, then put into by polymer raw material polyethylene particle in the reactor with emulsifying agent 400g, dispersion agent 400g, initiator 800g, hydrochloric acid soln 1500kg, the concentration of hydrochloric acid is 10%; Under stirring, make polyethylene particles be suspended state, be heated to 60 ~ 120 DEG C, pass into 390kg chlorine thereafter, under pressure is 0.4 ~ 0.45Mpa condition, carry out chlorination reaction 24 hours; After reaction terminates, with chlorine remaining in air displacement reactor; Chlorinatedpolyethylene, after initial water wash depickling, secondary depickling, neutralization, dehydration and drying, can obtain the chlorinatedpolyethylene that chloride massfraction is 65%; HCl solution after the preliminary depickling of chlorinatedpolyethylene, recycle, the concentration obtaining hydrochloric acid after unnecessary salt acid treating is the hydrochloric acid product of 20%.
Embodiment 2
First polyethylene 1I2A sieves through fragmentation, obtain particle diameter at 40 ~ 120 object polyethylene particles, then polymer raw material polyethylene particle is put into there is emulsifying agent 500g, dispersion agent 500g, initiator 900g, hydrochloric acid soln be in the reactor of 1500kg, the concentration of hydrochloric acid is 11%, under stirring, make polyethylene particles be suspended state, be heated to 60 ~ 120 DEG C, thereafter pass into 390kg chlorine, under pressure is 0.4 ~ 0.45Mpa condition, carry out chlorination reaction 12 hours; After reaction terminates, with chlorine remaining in air displacement reactor; Chlorinatedpolyethylene, after initial water wash depickling, secondary depickling, neutralization, dehydration and drying, can obtain the chlorinatedpolyethylene that chloride massfraction is 65%; HCl solution after the preliminary depickling of chlorinatedpolyethylene, recycle, the concentration obtaining hydrochloric acid after unnecessary salt acid treating is the hydrochloric acid product of 20%.
Embodiment 3
First polyethylene 1I2A sieves through fragmentation, obtain particle diameter at 40 ~ 120 object polyethylene particles, then polymer raw material polyethylene particle is put into there is emulsifier 600 g, dispersion agent 600g, initiator 1000g, hydrochloric acid soln be in the reactor of 1500kg, the concentration of hydrochloric acid is 12%, under stirring, make polyethylene particles be suspended state, be heated to 60 ~ 120 DEG C, thereafter pass into 390kg chlorine, under pressure is 0.4 ~ 0.45Mpa condition, carry out chlorination reaction 16 hours; After reaction terminates, with chlorine remaining in air displacement reactor; Chlorinatedpolyethylene, after initial water wash depickling, secondary depickling, neutralization, dehydration and drying, can obtain the chlorinatedpolyethylene that chloride massfraction is 65%; HCl solution after the preliminary depickling of chlorinatedpolyethylene, recycle, the concentration obtaining hydrochloric acid after unnecessary salt acid treating is the hydrochloric acid product of 20%.
Embodiment 4
First polyethylene 1I2A sieves through fragmentation, obtain particle diameter at 40 ~ 120 object polyethylene particles, then polymer raw material polyethylene particle is put into and there is emulsifying agent 550g, dispersion agent 550g, initiator 950g, hydrochloric acid soln is in the reactor of 1500kg, and the concentration of hydrochloric acid is 10%, under stirring, polyethylene particles is made to be suspended state, be heated to 60 ~ 120 DEG C, pass into 390kg chlorine thereafter, under pressure is 0.4 ~ 0.45Mpa condition, carry out chlorination reaction 20 hours; After reaction terminates, with chlorine remaining in air displacement reactor; Chlorinatedpolyethylene, after initial water wash depickling, secondary depickling, neutralization, dehydration and drying, can obtain the chlorinatedpolyethylene that chloride massfraction is 65%; HCl solution after the preliminary depickling of chlorinatedpolyethylene, recycle, the concentration obtaining hydrochloric acid after unnecessary salt acid treating is the hydrochloric acid product of 20%.
The emulsifying agent that above four embodiments drop into, dispersion agent, initiator are different, select the polyethylene of Fig. 1 ~ 4 model all not affect production process and the product yield of chlorinatedpolyolefins, and it is comparatively ripe for describing the technical program, is easy to production operation.
Claims (5)
1. in acidic medium, produce a method for chlorinatedpolyethylene, the method is characterized in that following steps:
First polyethylene sieves through fragmentation, obtain particle diameter at 40 ~ 120 object polyethylene particles, then polymer raw material polyethylene particle is put in the reactor with emulsifying agent 400 ~ 600g, dispersion agent 400 ~ 600g and initiator 800 ~ 1000g, hydrochloric acid soln 1500kg, the concentration of hydrochloric acid is 10% ~ 12%, under stirring, polyethylene particles is made to be suspended state, be heated to 60 ~ 120 DEG C, thereafter pass into 380 ~ 400kg chlorine, under pressure is 0.4 ~ 0.45Mpa condition, carry out chlorination reaction 24 hours; After reaction terminates, with chlorine remaining in air displacement reactor; Chlorinatedpolyethylene, after initial water wash depickling, secondary depickling, neutralization, dehydration and drying, can obtain the chlorinatedpolyethylene that chloride massfraction is 65%; HCl solution after the preliminary depickling of chlorinatedpolyethylene, recycle, the concentration obtaining hydrochloric acid after unnecessary salt acid treating is the hydrochloric acid product of 20%.
2. method of producing chlorinatedpolyethylene in acidic medium according to claim 1, is characterized in that described emulsifying agent is the one in polyoxyethylene nonylphenol ether, alkyl phenolic group Soxylat A 25-7, Viscotrol C-Soxylat A 25-7, pyrrolidone, C12-C14 alkanoic acid di-alcohol.
3. method of producing chlorinatedpolyethylene in acidic medium according to claim 1, is characterized in that described dispersion agent is the one in the mixture of 18-alkyl dimethyl benzyl ammonium chloride, 14-alkyl dimethyl benzyl ammonium chloride, alkyl trimethyl ammonium chloride, polyoxyethylene and polyoxypropylene, alkyl front three methyl sulfate amine, Cocoalkyl front three ammonium chloride.
4. method of producing chlorinatedpolyethylene in acidic medium according to claim 1, is characterized in that described initiator is the one in dilauroyl peroxide, benzoyl peroxide, Diisopropyl azodicarboxylate.
5. method of producing chlorinatedpolyethylene in acidic medium according to claim 1, the hydrochloric acid reclaimed after it is characterized in that described chlorinatedpolyethylene depickling uses as the acidic medium in described reactor.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105602131A (en) * | 2015-12-24 | 2016-05-25 | 深圳爱易瑞科技有限公司 | Novel chlorinated polyethylene and preparation method thereof |
| CN107266614A (en) * | 2017-08-08 | 2017-10-20 | 杭州新元化工技术开发有限公司 | A kind of super high molecular weight haloflex and preparation method thereof, device and application |
| CN108102011A (en) * | 2018-02-28 | 2018-06-01 | 中国天辰工程有限公司 | A kind of aftertreatment technology and device of high polymer chlorination reaction |
| CN108912252A (en) * | 2018-06-12 | 2018-11-30 | 梁格 | A kind of In The Production Technology of Chlorinated Polyethylene |
| CN109879990A (en) * | 2019-01-24 | 2019-06-14 | 潍坊硕邑化学有限公司 | A kind of method that the sour phase suspension of clean and environmental protection prepares chlorinated polypropylene |
| CN111995701A (en) * | 2020-09-09 | 2020-11-27 | 安徽华纳化学工业有限公司 | Preparation method of chlorinated polyethylene |
| CN112079945A (en) * | 2020-09-09 | 2020-12-15 | 安徽华纳化学工业有限公司 | Chlorinated polyethylene manufacturing process |
| CN114591453A (en) * | 2022-01-26 | 2022-06-07 | 山东奥星新材料股份有限公司 | Clean production method of chlorinated polyethylene |
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| CN1230550A (en) * | 1998-03-30 | 1999-10-06 | 上海华明高技术（集团）有限公司 | Aqueous-phase suspending polyethylene chlorinating process and high-chlorinated polyethylene produced using the same |
| CN101463104A (en) * | 2008-12-27 | 2009-06-24 | 潍坊亚星集团有限公司 | Method for producing high chlorinated polyethylene |
| CN101698687A (en) * | 2009-11-06 | 2010-04-28 | 潍坊亚星集团有限公司 | Method for preparing high-rigidity chlorinated polyethylene |
| CN102260361A (en) * | 2011-06-03 | 2011-11-30 | 杭州新元化工技术开发有限公司 | Preparation method of chlorinated polyethylene |
| CN103755845A (en) * | 2014-01-11 | 2014-04-30 | 潍坊亚星集团有限公司 | Clean production method of chlorinated polyethylene |
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2015
- 2015-10-14 CN CN201510664364.4A patent/CN105175585A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1230550A (en) * | 1998-03-30 | 1999-10-06 | 上海华明高技术（集团）有限公司 | Aqueous-phase suspending polyethylene chlorinating process and high-chlorinated polyethylene produced using the same |
| CN101463104A (en) * | 2008-12-27 | 2009-06-24 | 潍坊亚星集团有限公司 | Method for producing high chlorinated polyethylene |
| CN101698687A (en) * | 2009-11-06 | 2010-04-28 | 潍坊亚星集团有限公司 | Method for preparing high-rigidity chlorinated polyethylene |
| CN102260361A (en) * | 2011-06-03 | 2011-11-30 | 杭州新元化工技术开发有限公司 | Preparation method of chlorinated polyethylene |
| CN103755845A (en) * | 2014-01-11 | 2014-04-30 | 潍坊亚星集团有限公司 | Clean production method of chlorinated polyethylene |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105602131A (en) * | 2015-12-24 | 2016-05-25 | 深圳爱易瑞科技有限公司 | Novel chlorinated polyethylene and preparation method thereof |
| CN107266614A (en) * | 2017-08-08 | 2017-10-20 | 杭州新元化工技术开发有限公司 | A kind of super high molecular weight haloflex and preparation method thereof, device and application |
| CN108102011A (en) * | 2018-02-28 | 2018-06-01 | 中国天辰工程有限公司 | A kind of aftertreatment technology and device of high polymer chlorination reaction |
| CN108912252A (en) * | 2018-06-12 | 2018-11-30 | 梁格 | A kind of In The Production Technology of Chlorinated Polyethylene |
| CN109879990A (en) * | 2019-01-24 | 2019-06-14 | 潍坊硕邑化学有限公司 | A kind of method that the sour phase suspension of clean and environmental protection prepares chlorinated polypropylene |
| CN111995701A (en) * | 2020-09-09 | 2020-11-27 | 安徽华纳化学工业有限公司 | Preparation method of chlorinated polyethylene |
| CN112079945A (en) * | 2020-09-09 | 2020-12-15 | 安徽华纳化学工业有限公司 | Chlorinated polyethylene manufacturing process |
| CN114591453A (en) * | 2022-01-26 | 2022-06-07 | 山东奥星新材料股份有限公司 | Clean production method of chlorinated polyethylene |
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Application publication date: 20151223 |