CN102358762B - Preparation technology of chlorinated maleic acid modified polyethylene material - Google Patents
Preparation technology of chlorinated maleic acid modified polyethylene material Download PDFInfo
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- CN102358762B CN102358762B CN 201110215698 CN201110215698A CN102358762B CN 102358762 B CN102358762 B CN 102358762B CN 201110215698 CN201110215698 CN 201110215698 CN 201110215698 A CN201110215698 A CN 201110215698A CN 102358762 B CN102358762 B CN 102358762B
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Abstract
The invention discloses a preparation technology of a chlorinated maleic acid modified polyethylene material. The technology comprises the steps of: first dispersing polyethylene in water with an emulsifier under stirring, and adding a peroxide initiator; introducing a certain amount of chlorine under a certain temperature, adding maleic acid and introducing chlorine again for a period of reaction, then raising the temperature for a continuous chlorination reaction; finally conducting washing and deacidification, neutralization, dehydration, injection moulding and granulation as well as drying, thus obtaining the chlorinated maleic acid modified polyethylene material. The technology of the invention undergoes in an enclosed container, i.e. the chlorination reaction occurs under an aqueous suspension state in a reaction vessel. By first introducing chlorine for reaction and then adding maleic acid and introducing chlorine for reaction, the invention successfully prepares a chlorinated maleic acid modified polyethylene material with chlorine content of about 25%-70%. The chlorinated maleic acid modified polyethylene prepared by the technology of the invention has excellent surface cohesiveness and compatibility with other polar materials.
Description
Technical field
The present invention relates to a kind of preparation technology of chlorinated maleic acid modified polyethylene material.
Background technology
The production method of chlorinatedpolyethylene mainly contains three kinds of solution method, suspension method and chlorination by solid state method.Solution method is the earliest method of producing chlorinatedpolyethylene, is researched and developed successfully in 1938 by Britain ICI chemical company.Solution method is under the certain pressure temperature, polyethylene is dissolved in the organic solvents such as halogenated alkane or chlorobenzene, add initiator, the logical chlorine that heats up reacts, after reaching needed cl content, reaction stops logical chlorine, in the material precipitation agent of falling people, reclaim solvent, can make the chlorinatedpolyethylene finished product through washing, neutralization, drying again.The solution method processing condition are gentle, and operating procedure is ripe, and the cl content of gained chlorinatedpolyethylene product is controlled, and chlorine distribution uniform in the product can be used for producing the chlorinatedpolyethylene product of high cl content and high-crystallinity.But from reaction solution, isolate chlorinatedpolyethylene, and it is comparatively complicated to remove residual dissolving agent process from chlorinatedpolyethylene, cost of equipment is high, the solvent that leaks does great damage to atmospheric ozone layer, along with coming into force of Montreal Protocol on Substances that Deplete the Ozone Layer, the technology of producing chlorinatedpolyolefins with solvent method progressively is eliminated.Solid phase method is to make chlorizating agent with the gas mixture of chlorine or chlorine and nitrogen solid polyethylene is carried out chlorination.The solvent-free pollution of solid phase method, but the problems such as homogeneity that chlorine distributes in the derivation of reaction heat and the chlorizate also are not well solved.Water phase suspension is succeeded in developing in nineteen sixty by German Hirst company, and after this Osaka, Japan Cao Da company, most of producer clear and electrician company, U.S. Dow chemical company and China also adopt the method to produce.Water phase suspension is that the polyethylene fine powder is distributed in the deionized water of suspending agent-containing, add swelling agent, tack reducing material, dispersion agent, initiator, defoamer, antistatic agent, under agitation pressurization passes into chlorine and carries out chlorination, after reaching needed cl content, carry out depickling, wash, add the alkali neutralization, take off waste liquid, hot wash, centrifuge dehydration, the dry chlorinatedpolyethylene finished product that gets.Water phase suspension has smooth operation, chlorine utilization is high, and the product aftertreatment is easy, and is lower to equipment requirements, and production cost is low, and good product quality is applicable to the advantage of scale operation.
Along with the continuous expansion of chlorinatedpolyethylene range of application, some special dimension has proposed Secretary to chlorinatedpolyethylene, as with the tack problem at polarity interface.Its chlorination homogeneity, consistency etc. are had higher requirement, and people adopt the methods such as grafting, blend that chlorinatedpolyethylene is carried out modification.The maleic anhydride modified polyethylene of chlorination is the important Chemicals of a class, it has stable chemical structure, good heat-resisting, ageing resistance, flame retardant resistance, winter hardiness, oil-proofness, weathering resistance, tint permanence, chemical proofing, ozone resistance, electrical insulating property, good consistency and processibility, thereby being widely used in the industries such as plastics, building materials, electric, medical, agriculture, rubber, paint, pigment, steamer, papermaking, weaving, packing and coating, market outlook are fabulous.Only have at present some about chlorinatedpolyethylene is carried out maleic anhydride modified report, as Yang Qibiao etc. with maleic anhydride to chlorinatedpolyethylene carried out functionalized grafting (Yang Qibiao, Yang Zishan. macromolecular material and engineering, 1994,3,134-137); And Tan Xiaohong etc. is with maleic anhydride modified chlorinatedpolyethylene, improved the chlorinatedpolyethylene surface cementability and with the consistency of the poly-platform thing of other polarity (Tan Xiaohong, Ceng Fan wash, Chen Yuguang. Chinese sizing agent, 1998,8 (6), 5-8).But the preparation method of the modified chlorinated polyethylene of these bibliographical informations carries out modification on the basis of chlorinatedpolyethylene, and therefore above processing step of two steps will be arranged at least, complicated process of preparation, cl content and contain the difficult control of maleic anhydride amount.
Summary of the invention
The invention provides a kind of preparation technology of chlorinated maleic acid modified polyethylene material, its objective is to solve the like product complicated process of preparation, cl content and contain the difficult control of maleic anhydride amount, the technical problem that production cost is higher.The objective of the invention is to realize by the following technical solutions.
A kind of preparation technology of chlorinated maleic acid modified polyethylene material, its key points in design is that the step of the method is as follows: sub polyethylene is dispersed in the reactor that contains emulsifying agent and water, stir lower, so that polyethylene is in suspended state, add initiator, at 60～70 ℃, pass into chlorine after, be warming up to 80～90 ℃, add toxilic acid, pass into again chlorine, behind the reaction 4h, be warming up to 115 ℃, continue reaction 1.5～2.0h, after reaction finishes, drive chlorine remaining in the reactor away with air, chlorizate is through the washing depickling, neutralization, dehydration, injection moulding granulation and drying treatment namely make chlorinated maleic acid modified polyethylene material.
Described emulsifying agent is the mixture of oxygen ethene-oxypropylene multipolymer and sodium polymethacrylate; Described emulsifying agent and poly part by weight are 1:100～6:100.
Described initiator is benzoyl peroxide; Described initiator and poly part by weight are 1:1000～10:1000.
What described modified poly ethylene was used is toxilic acid; Described toxilic acid and poly part by weight are 1:100～15:100.
Described chlorine and poly part by weight are: 32:1～55:1; Described water is clean process water, deionized water or distilled water after filtering, and described water and poly part by weight are 10:1～30:1.
The chlorinity of the described chlorinated maleic acid modified polyethylene material that makes is that part by weight is 25%～70%.
Described oxygen ethene-oxypropylene multipolymer and sodium polymethacrylate part by weight are 3:7～5:5.
The beneficial effect that the present invention has is: what modified poly ethylene was used is the toxilic acid aqueous solution, carries out in same reactor when chlorination reaction and toxilic acid modified-reaction, and technique is simple, convenient operation, and cost is lower, and little to the pollution of surrounding environment, cl content is controlled.The chlorination toxilic acid modified poly ethylene of this technique preparation has good surface adhesion and the consistency good with other polar material.
Embodiment
Embodiment 1:
The 2Kg sub polyethylene is dispersed in contains the 0.06Kg emulsifying agent, the emulsifying agent and the poly part by weight that contain oxygen ethene-oxypropylene multipolymer and sodium polymethacrylate are 3:7, and in the reactor of 36Kg water, under stirring, so that polyethylene is in suspended state, add the 0.014Kg initiator, at 70 ℃, after passing into chlorine 1.1Kg, be warming up to 90 ℃, add the 0.2Kg toxilic acid, pass into again 0.5Kg chlorine, behind the reaction 4h, be warming up to 115 ℃, continue reaction 1.0h.After reaction finishes, drive chlorine remaining in the reactor away with air, chlorizate namely makes approximately 25% chlorinated maleic acid modified polyethylene material of chlorinity through washing depickling, neutralization, dehydration, injection moulding granulation and drying treatment.
Embodiment 2:
The 2Kg sub polyethylene is dispersed in contains the 0.06Kg emulsifying agent, the emulsifying agent and the poly part by weight that contain oxygen ethene-oxypropylene multipolymer and sodium polymethacrylate are 3:7, and in the reactor of 36Kg water, under stirring, so that polyethylene is in suspended state, add the 0.014Kg initiator, at 70 ℃, after passing into chlorine 2Kg, be warming up to 90 ℃, add the 0.2Kg toxilic acid, pass into again 1.1Kg chlorine, behind the reaction 4h, be warming up to 115 ℃, continue reaction 1.0h.After reaction finishes, drive chlorine remaining in the reactor away with air, chlorizate namely makes approximately 55% chlorinated maleic acid modified polyethylene material of chlorinity through washing depickling, neutralization, dehydration, injection moulding granulation and drying treatment.
Embodiment 3:
The 2Kg sub polyethylene is dispersed in contains the 0.06Kg emulsifying agent, the emulsifying agent and the poly part by weight that contain oxygen ethene-oxypropylene multipolymer and sodium polymethacrylate are 3:7, and in the reactor of 36Kg water, under stirring, so that polyethylene is in suspended state, add the 0.014Kg initiator, at 70 ℃, after passing into chlorine 2.2Kg, be warming up to 90 ℃, add the 0.2Kg toxilic acid, pass into again 1.2Kg chlorine, behind the reaction 4h, be warming up to 115 ℃, continue reaction 1.5h.After reaction finishes, drive chlorine remaining in the reactor away with air, chlorizate namely makes approximately 60% chlorinated maleic acid modified polyethylene material of chlorinity through washing depickling, neutralization, dehydration, injection moulding granulation and drying treatment.
Embodiment 4:
The 2Kg sub polyethylene is dispersed in contains the 0.06Kg emulsifying agent, the emulsifying agent and the poly part by weight that contain oxygen ethene-oxypropylene multipolymer and sodium polymethacrylate are 3:7, and in the reactor of 36Kg water, under stirring, so that polyethylene is in suspended state, add the 0.014Kg initiator, at 70 ℃, after passing into chlorine 2.3Kg, be warming up to 90 ℃, add the 0.2Kg toxilic acid, pass into again 1.3Kg chlorine, behind the reaction 4h, be warming up to 115 ℃, continue reaction 2.0h.After reaction finishes, drive chlorine remaining in the reactor away with air, chlorizate namely makes approximately 65% chlorinated maleic acid modified polyethylene material of chlorinity through washing depickling, neutralization, dehydration, injection moulding granulation and drying treatment.
Embodiment 5:
The 2Kg sub polyethylene is dispersed in contains the 0.06Kg emulsifying agent, the emulsifying agent and the poly part by weight that contain oxygen ethene-oxypropylene multipolymer and sodium polymethacrylate are 5:5, and in the reactor of 36Kg water, under stirring, so that polyethylene is in suspended state, add the 0.014Kg initiator, at 70 ℃, after passing into chlorine 1.2Kg, be warming up to 90 ℃, add the 0.2Kg toxilic acid, pass into again 0.6Kg chlorine, behind the reaction 4h, be warming up to 115 ℃, continue reaction 1.0h.After reaction finishes, drive chlorine remaining in the reactor away with air, chlorizate namely makes approximately 28% chlorinated maleic acid modified polyethylene material of chlorinity through washing depickling, neutralization, dehydration, injection moulding granulation and drying treatment.
Embodiment 6:
The 2Kg sub polyethylene is dispersed in contains the 0.06Kg emulsifying agent, the emulsifying agent and the poly part by weight that contain oxygen ethene-oxypropylene multipolymer and sodium polymethacrylate are 5:5, and in the reactor of 36Kg water, under stirring, so that polyethylene is in suspended state, add the 0.014Kg initiator, at 70 ℃, after passing into chlorine 90Kg, be warming up to 90 ℃, add the 0.2Kg toxilic acid, pass into again 5Kg chlorine, behind the reaction 4h, be warming up to 115 ℃, continue reaction 1.0h.After reaction finishes, drive chlorine remaining in the reactor away with air, chlorizate namely makes approximately 59% chlorinated maleic acid modified polyethylene material of chlorinity through washing depickling, neutralization, dehydration, injection moulding granulation and drying treatment.
Embodiment 7:
The 2Kg sub polyethylene is dispersed in contains the 0.06Kg emulsifying agent, the emulsifying agent and the poly part by weight that contain oxygen ethene-oxypropylene multipolymer and sodium polymethacrylate are 5:5, and in the reactor of 36Kg water, under stirring, so that polyethylene is in suspended state, add the 0.014Kg initiator, at 70 ℃, after passing into chlorine 2Kg, be warming up to 90 ℃, add the 0.2Kg toxilic acid, pass into again 1.3Kg chlorine, behind the reaction 4h, be warming up to 115 ℃, continue reaction 1.5h.After reaction finishes, drive chlorine remaining in the reactor away with air, chlorizate namely makes approximately 66% chlorinated maleic acid modified polyethylene material of chlorinity through washing depickling, neutralization, dehydration, injection moulding granulation and drying treatment.
Embodiment 8:
The 2Kg sub polyethylene is dispersed in contains the 0.06Kg emulsifying agent, the emulsifying agent and the poly part by weight that contain oxygen ethene-oxypropylene multipolymer and sodium polymethacrylate are 5:5, and in the reactor of 36Kg water, under stirring, so that polyethylene is in suspended state, add the 0.014Kg initiator, at 70 ℃, after passing into chlorine 2.3Kg, be warming up to 90 ℃, add the 0.2Kg toxilic acid, pass into again 1.5Kg chlorine, behind the reaction 4h, be warming up to 115 ℃, continue reaction 2.0h.After reaction finishes, drive chlorine remaining in the reactor away with air, chlorizate namely makes approximately 70% chlorinated maleic acid modified polyethylene material of chlorinity through washing depickling, neutralization, dehydration, injection moulding granulation and drying treatment.
Initiator in above-described embodiment 1～enforcement 8 is benzoyl peroxide.
Claims (3)
1. the preparation technology of chlorinated maleic acid modified polyethylene material, this preparation technology is characterised in that sub polyethylene is dispersed in the reactor that contains emulsifying agent and water, emulsifying agent is the mixture of oxygen ethene-oxypropylene multipolymer and sodium polymethacrylate, described oxygen ethene-oxypropylene multipolymer and sodium polymethacrylate part by weight are 3:7～5:5, described emulsifying agent and poly part by weight are 1:100～6:100, stir lower, so that polyethylene is in suspended state, add initiator, described initiator is benzoyl peroxide, described initiator and poly part by weight are 1:1000～10:1000, at 60～70 ℃, after passing into chlorine, be warming up to 80～90 ℃, add toxilic acid, described toxilic acid and poly part by weight are 1:100～15:100, pass into again chlorine, described chlorine and poly part by weight are: 32:1～55:1, behind the reaction 4h, be warming up to 115 ℃, continue reaction 1.5～2.0h, after reaction finishes, drive chlorine remaining in the reactor away with air, chlorizate is through the washing depickling, neutralization, dehydration, injection moulding granulation and drying treatment namely make chlorinated maleic acid modified polyethylene material.
2. the preparation technology of chlorinated maleic acid modified polyethylene material according to claim 1 is characterized in that: described water is clean process water, deionized water or distilled water after filtering, and described water and poly part by weight are 10:1～30:1.
3. the preparation technology of chlorinated maleic acid modified polyethylene material according to claim 1, it is characterized in that: the chlorinity of the described chlorinated maleic acid modified polyethylene material that makes is that part by weight is 25%～70%.
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Non-Patent Citations (2)
| Title |
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| 氯化原位接枝反应制备酐基化HDPE;马衍青等;《现代塑料加工应用》;20091231;第21卷(第3期);第12-15页 * |
| 马衍青等.氯化原位接枝反应制备酐基化HDPE.《现代塑料加工应用》.2009,第21卷(第3期),第12-15页. |
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Address after: No. 7, Dajiang North Road, Jiangkou street, Fenghua District, Ningbo, Zhejiang Patentee after: Ningbo Haoxin Yulon New Material Co. Ltd. Address before: 315502 Zhejiang city of Ningbo province Fenghua Xikou after Ge Patentee before: Fenghua Yuron Chemical Industry Material Co., Ltd. |
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