CN1394881A - Industrial production method of chlorinated rubber by adopting water phase suspension method and its product - Google Patents
Industrial production method of chlorinated rubber by adopting water phase suspension method and its product Download PDFInfo
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- CN1394881A CN1394881A CN 01121783 CN01121783A CN1394881A CN 1394881 A CN1394881 A CN 1394881A CN 01121783 CN01121783 CN 01121783 CN 01121783 A CN01121783 A CN 01121783A CN 1394881 A CN1394881 A CN 1394881A
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- chlorinated rubber
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Abstract
The industrial production method for making chlorinated rubber by using natural emulsion as raw material and adopting aqueous phase suspension method is characterized by that in same reaction still the natural emulsion, emulsification promotor, dispersion insulator and activation initiator are added according to a certain proportion in turn, stirred in dilute hydrochloric acid liuqor whose concentration is less than 10% to make solution become into suspension state, and under the irradiation of UV ray the chlorine gas is introduced in two temp. stages to make chlorination reaction so as to obtain the white powdered chlorinated rubber with chlorine content of 60-70% and good solubility. It is a high-quality resin which can be extensively used in the fields of coating, printing ink, adhesive and printing industry.
Description
Technical field: the present invention relates to the macromolecule chemical industry field.Be a kind of under the aqueous-phase suspending state, carry out chlorination reaction, make the industrialized preparing process of chlorinated rubber and the chlorinated rubber finished product that makes with present method with natural emulsion.
Background technology: chlorinated rubber all carries out chlorination reaction with solvent method and produces.Because solvent method cost height, and some as the tetracol phenixin equal solvent to health of human body residual solvent and make defectives such as purposes is restricted in harmful and volatile matter contaminate environment and the product.
Bibliographical information is arranged both at home and abroad though the water method is produced chlorinated rubber, it is investigated that new data shows, domesticly still be in the research trial stage; Though there is 800 tons/year industrial production device in deer island factory of the electrochemical company of the external Japanese rising sun, production method of the present invention has very big difference, and (seeing China Chemical Information Center's " novelty assessment report " for details numbers: 2000-086) with it.
Summary of the invention: a kind of industrialized preparing process and product with method of chlorinated rubber by adopting water phase suspension, be with natural emulsion under the aqueous-phase suspending state, carry out chlorination reaction and make the industrialized preparing process of chlorinated rubber and the chlorinated rubber product that makes with this method, it is characterized in that with the natural emulsion being raw material, add emulsification promotor sequentially, disperse separant and activate initiator, in the diluted hydrochloric acid aqueous solution that is lower than 10% concentration, make solution be suspension milkiness state through stirring, under the irradiation of ultraviolet, divide two temperature sections to feed chlorine, in same reactor, finish chlorination reaction continuously, reaction is warming up to 140 ℃ after ending again, the molecular weight of degraded chlorinated rubber is with the product of preparation different viscosity, after chlorination reaction ends, again through the washing depickling, neutralization, dehydration, technological processs such as drying finally make chlorinity between 60-70%, the finely powdered that is white in color finished product.The used raw material of this method is the natural emulsion of emulsion form.It is emulsification promotor that this method at first adds with a kind of in the nonionogenic tenside in raw material, as polyoxyethylene nonylphenol ether, alkyl phenolic group Soxylat A 25-7, castor-oil plant ether, Viscotrol C-Soxylat A 25-7, C12-C14 alkanoic acid diethanolamine etc.; Add-on is the 0.5-3% of latex weight.Adding then with a kind of in the cats product serves as to disperse separant, as 18-alkyl dimethyl benzyl ammonium chloride, 14-alkyl dimethyl benzyl ammonium chloride, alkyl trimethyl ammonium chloride, sodium polyacrylate, sodium polymethacrylate, cocounut oil alkyl front three ammonium chloride, alkyl trimethyl sulfate methyl ammonium etc., its add-on also is the 0.5-3% of latex weight.Add superoxide again and do to activate initiator, as dilauroyl peroxide, Diisopropyl azodicarboxylate, dibenzoyl peroxide etc., add-on is the 1-5% of latex weight.Be invested in concentration and be lower than in 10% the diluted hydrochloric acid aqueous solution, in the reactor that band stirs, carry out chlorination reaction.The solution of this moment is aqueous-phase suspending emulsion form preferably.Under the irradiation of ultraviolet light, feed chlorine and carry out chlorination reaction.The power 500-3000W of UV-lamp, wavelength 260-360nm.Feed chlorine and divide two temperature sections to carry out chlorination reaction, the fs is to be lower than 30 ℃ normal temperature, and the amount that feeds chlorine should reach 70% of total feeding amount; When the subordinate phase top temperature is no more than 130 ℃, all the other chlorine are all fed, the total amount of feeding chlorine is with 3-5 times of natural emulsion weight.The aqueous solution is that concentration is no more than 10% dilute hydrochloric acid solution, and its weight is 10-20 times of natural emulsion.Each temperature section feeds the weight and the ratio of chlorine and is controlled by measure monitor the back as calculated.
After logical chlorine finished, insulation earlier 0.5-2 hour was driven remaining chlorine in the still away with uncontaminated air again, and is warming up to below 140 ℃, and with the molecular weight of degraded chlorinated rubber, purpose is the chlorinated rubber finished product that can prepare different viscosity according to user's requirement.Chlorinated rubber after the degraded, through washing depickling, neutralization, dehydration, the dried finished products finely powdered pressed powder that is white in color, its chlorinity is 60-70%.And can fully dissolve in organic solvents such as toluene, dimethylbenzene, solution is clear, no suspended substance and throw out.
Reaction whole process of the present invention is to finish under the aqueous-phase suspending state of same reactor, and surrounding environment is not polluted.And operation, adaptation scale production are lacked, are convenient to the reaction times, and cost is lower, can bring considerable economic.
Embodiment: following the invention will be further described by example.Described embodiment only is the physical record in the mass-producing trial production.Therefore, concerning the person skilled in art, make some very easily on this basis and change, but its essence does not exceed the scope that the present invention includes.Present embodiment is only made an explanation to the present invention obviously, and is not that the present invention is made restriction.
Embodiment:
In the glassed steel reaction vessels that 2000 liters of bands stir, drop into concentration of hydrochloric acid and be no more than 10% aqueous solution 1500kg, with natural emulsion 100kg, at first add nonionogenic tenside 500g then, the combination solution that adds cats product 500g again is after fully stirring, put in the glassed steel reaction vessels, add peroxide initiator 1000g at last, under the irradiation of ultraviolet light, temperature is controlled at below 30 ℃, feeds chlorine and reacts.When chlorine feeding amount reach should the feeding amount 70% the time, heat up and enter subordinate phase, before top temperature is no more than 90 ℃, feed remaining chlorine.The chlorine total amount that feeds is 360kg.After reaction finished, insulation earlier 1.5 hours was driven chlorine remaining in the still again, and is warming up to 140 ℃, the molecular weight of degraded chlorinated rubber.Through washing depickling, neutralization, dehydration, drying, promptly get the chlorinated rubber finished product again, the finished product are the white fine powder shape solid of chlorinity 65%.
Claims (9)
1, a kind of industrialized preparing process of method of chlorinated rubber by adopting water phase suspension and product, be with natural emulsion under the aqueous-phase suspending state, carry out chlorination reaction and make the industrialized preparing process of chlorinated rubber and the chlorinated rubber product that makes with this method, it is characterized in that with the natural emulsion being raw material, add emulsification promotor sequentially, disperse separant and activate initiator, in the diluted hydrochloric acid aqueous solution that is lower than 10% concentration, make solution be suspension milkiness state through stirring, under the irradiation of ultraviolet, divide two temperature sections to feed chlorine, in same reactor, finish chlorination reaction continuously, reaction is warming up to 140 ℃ after ending again, the molecular weight of degraded chlorinated rubber is with the product of preparation different viscosity, after chlorination reaction ends, again through the washing depickling, neutralization, dehydration, technological processs such as drying finally make chlorinity between 60-70%, the finely powdered that is white in color finished product.
2, the industrialized preparing process of method of chlorinated rubber by adopting water phase suspension according to claim 1 is characterized in that the used raw material of this method is the natural emulsion of emulsion form.
3, the industrialized preparing process of method of chlorinated rubber by adopting water phase suspension according to claim 1, the emulsification promotor that it is characterized in that this production method is nonionogenic tenside, as polyoxyethylene nonylphenol ether, alkyl phenolic group Soxylat A 25-7, Viscotrol C-Soxylat A 25-7, C12-C14 alkanoic acid diethanolamine etc.; Disperse separant to adopt cats product, as 18-alkyl dimethyl benzyl ammonium chloride, 14-alkyl dimethyl benzyl ammonium chloride, alkyl trimethyl ammonium chloride, cocounut oil alkyl front three ammonium chloride, alkyl trimethyl sulfate methyl ammonium etc., activating reaction initiator such as dilauroyl peroxide, Diisopropyl azodicarboxylate, dibenzoyl peroxide etc.
4, the industrialized preparing process of method of chlorinated rubber by adopting water phase suspension according to claim 1, it is characterized in that the emulsification promotor in this method, disperse the additional proportion and the sequencing of separant and activation initiator to be, the emulsification promotor that adds latex weight 0.5-3% successively to natural emulsion earlier, the dispersion separant that adds latex weight 0.5-3% again adds the activation initiator of latex weight 1-5% at last.
5, the industrialized preparing process of method of chlorinated rubber by adopting water phase suspension according to claim 1, the aqueous solution that it is characterized in that this method is that concentration is no more than 10% dilute hydrochloric acid solution, its weight is 10-20 times of latex weight, and each temperature section feeds the weight and the ratio of chlorine and controlled by measure monitor the back as calculated.
6, the industrialized preparing process of method of chlorinated rubber by adopting water phase suspension according to claim 1, the chlorination reaction that it is characterized in that this method is to feed chlorine in the glassed steel reaction vessels that band stirs and under the UV-lamp rayed to carry out chlorination reaction, the power of used UV-lamp is between 500-3000W, and wavelength is 260-360nm.
7, the industrialized preparing process of method of chlorinated rubber by adopting water phase suspension according to claim 1 is characterized in that this method feeds chlorine and divides two temperature sections to carry out chlorination reaction, and the fs, chlorine feeding amount was for feeding 70% of total amount below 30 ℃; When subordinate phase is no more than 130 ℃ in top temperature, feed remaining chlorine.
8, the industrialized preparing process of method of chlorinated rubber by adopting water phase suspension according to claim 7, it is characterized in that this method is after chlorination reaction finishes, insulation earlier 0.5-2 hour, drive remaining chlorine in the still away with uncontaminated air again, and be warming up to below 140 ℃, the molecular weight of degraded chlorinated rubber is with the chlorinated rubber finished product of preparation different viscosity.
9, the industrialized preparing process of method of chlorinated rubber by adopting water phase suspension according to claim 1 and product, chlorinated rubber after it is characterized in that degrading, through washing depickling, neutralization, dehydration, drying, the chlorinated rubber finished product chlorinity that makes is 60-70%, the finely powdered that is white in color solid.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 01121783 CN1394881A (en) | 2001-07-08 | 2001-07-08 | Industrial production method of chlorinated rubber by adopting water phase suspension method and its product |
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| CN 01121783 CN1394881A (en) | 2001-07-08 | 2001-07-08 | Industrial production method of chlorinated rubber by adopting water phase suspension method and its product |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102174126A (en) * | 2011-03-07 | 2011-09-07 | 福建师范大学 | Method for preparing chlorinated rubber by water phase photocatalysis |
| CN102351971A (en) * | 2011-07-19 | 2012-02-15 | 杭州新元化工技术开发有限公司 | Preparation method of chlorination butyl rubber |
| CN103159867A (en) * | 2011-12-15 | 2013-06-19 | 中国石油天然气股份有限公司 | Preparation method of flame-retardant powdered rubber |
| CN104341641A (en) * | 2014-08-27 | 2015-02-11 | 安徽同丰橡塑工业有限公司 | Manufacturing process of chlorinated rubber |
| CN104448452A (en) * | 2013-09-18 | 2015-03-25 | 中国石油天然气股份有限公司 | Preparation method of halogenated acylation low-smoke flame-retardant powder styrene butadiene rubber |
| CN104479054A (en) * | 2014-12-25 | 2015-04-01 | 芜湖融汇化工有限公司 | Chlorinated rubber and method for preparing chlorinated rubber from recovered desulfurized tire rubber |
| CN105418809A (en) * | 2016-01-05 | 2016-03-23 | 临沂奥星化工有限公司 | Preparation method of chlorinated rubber |
| CN108976320A (en) * | 2018-07-23 | 2018-12-11 | 宁波昊鑫裕隆新材料有限公司 | A kind of chlorinated rubber and preparation method and purposes of nanometer additive and polyoxyethylene sulfonic acid sodium modified synergic |
-
2001
- 2001-07-08 CN CN 01121783 patent/CN1394881A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102174126A (en) * | 2011-03-07 | 2011-09-07 | 福建师范大学 | Method for preparing chlorinated rubber by water phase photocatalysis |
| CN102174126B (en) * | 2011-03-07 | 2012-11-14 | 福建师范大学 | Method for preparing chlorinated rubber by water phase photocatalysis |
| CN102351971A (en) * | 2011-07-19 | 2012-02-15 | 杭州新元化工技术开发有限公司 | Preparation method of chlorination butyl rubber |
| CN102351971B (en) * | 2011-07-19 | 2013-05-22 | 杭州新元化工技术开发有限公司 | Preparation method of chlorination butyl rubber |
| CN103159867A (en) * | 2011-12-15 | 2013-06-19 | 中国石油天然气股份有限公司 | Preparation method of flame-retardant powdered rubber |
| CN103159867B (en) * | 2011-12-15 | 2014-12-24 | 中国石油天然气股份有限公司 | Preparation method of flame-retardant powdered rubber |
| CN104448452A (en) * | 2013-09-18 | 2015-03-25 | 中国石油天然气股份有限公司 | Preparation method of halogenated acylation low-smoke flame-retardant powder styrene butadiene rubber |
| CN104448452B (en) * | 2013-09-18 | 2016-07-13 | 中国石油天然气股份有限公司 | Preparation method of halogenated acylation low-smoke flame-retardant powder styrene butadiene rubber |
| CN104341641A (en) * | 2014-08-27 | 2015-02-11 | 安徽同丰橡塑工业有限公司 | Manufacturing process of chlorinated rubber |
| CN104479054A (en) * | 2014-12-25 | 2015-04-01 | 芜湖融汇化工有限公司 | Chlorinated rubber and method for preparing chlorinated rubber from recovered desulfurized tire rubber |
| CN105418809A (en) * | 2016-01-05 | 2016-03-23 | 临沂奥星化工有限公司 | Preparation method of chlorinated rubber |
| CN108976320A (en) * | 2018-07-23 | 2018-12-11 | 宁波昊鑫裕隆新材料有限公司 | A kind of chlorinated rubber and preparation method and purposes of nanometer additive and polyoxyethylene sulfonic acid sodium modified synergic |
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