CN101475653A - Industrial production method of multicomponent copolymer chlorinated polyethylene by water phase grafting - Google Patents
Industrial production method of multicomponent copolymer chlorinated polyethylene by water phase grafting Download PDFInfo
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- CN101475653A CN101475653A CNA200910095625XA CN200910095625A CN101475653A CN 101475653 A CN101475653 A CN 101475653A CN A200910095625X A CNA200910095625X A CN A200910095625XA CN 200910095625 A CN200910095625 A CN 200910095625A CN 101475653 A CN101475653 A CN 101475653A
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Abstract
The invention relates to an industrialized production method for producing multielement copolymerization chlorinated polyethylene through water phase grafting. The method comprises the following steps: taking polyethylene powder as the raw material, and adding the raw material into an aqueous solution containing an emulsification promoter, a dispersion separation agent and an activation initiator; making the polyethylene powder be in a suspended state under the action of stirring, and linking up functional groups with the molecular chain of polyethylene before chlorine is introduced to have a chlorination reaction. The method comprises the following key points: the functional groups can be four functional groups, namely a carboxyl functional group, a hydroxyl functional group, an ester functional group and a carbonyl functional group, and the number of the grafted functional groups can be 15 to 25 percent of the weight of polyethylene; then a certain proportion of chlorine is respectively introduced through three temperature sections, and the chlorination reaction is carried out in the same glass lining reaction kettle so as to finally obtain the multielement copolymerization chlorinated polyethylene with the chlorine content of 70 to 80 percent; and the raw material of polyethylene has the molecular weight of 3,000 to 5,000. The method causes no pollution on the ambient surroundings, and has the short reaction time and convenient operation. The method is suitable for the large-scale production, and has lower cost and great economic benefits.
Description
Technical field
The present invention relates to the macromolecule chemical industry field, is under the aqueous-phase suspending state, makes multi-component copolymer chlorinatedpolyethylene industrialized preparing process after the grafting.
Background technology
Multi-component copolymer chlorinatedpolyethylene (HPHCPE) is mainly as coating, printing ink, fire retardant, high-grade caking agent etc.Its manufacture method, present known have chlorination by solid state method, solvent chlorination process and aqueous suspension chlorination method.Because solid-phase chlorination is that chlorine is directly fed polyethylene powders, the intermolecular specific surface area that is in contact with one another of its polyethylene and chlorine is limited, thus in scale operation, be difficult to realization, so industrially generally do not adopt.Usually industrially all carry out chlorination, but because of the production cost height, and some there are harm and contaminate environment as the tetracol phenixin equal solvent to the person, so also will progressively be eliminated with solvent method.In recent years, though Japanese and domestic indivedual enterprises are also in the exploration of carrying out making with water phase suspension the multi-component copolymer chlorinatedpolyethylene, but show according to looking into new data, domesticly still rest on the small test stage, do not see report (China Chemical Information Center's " novelty assessment report " numbering: 2001-008) that large-scale industrial production is arranged; External as Japan speciallys permit communique 93-18619, the technology that comprises the chlorinatedpolyethylene of multi-component copolymer chlorinatedpolyethylene in 93-222117 disclosed chlorinatedpolyethylene manufacture method, they for embodiment in employed reactor all below 100 liters, and long reaction time, technology is numerous and diverse.Therefore, be not suitable for large-scale industrial production.
Chinese patent mandate publication number CN1177875C, denomination of invention " is made the industrialized preparing process of terpolymer chlorinated polyethylene by adopting " behind the water-phase grafting, this part patent is put to implement to produce positive social benefit, and its not good enough part is to remain weak point with other resin cosolvencies and common molten scope.
Summary of the invention
For overcoming above-mentioned deficiency, the object of the invention provides a kind of multicomponent copolymer chlorinated polyethylene by water phase grafting industrialized preparing process, make polyethylene under the aqueous-phase suspending state, feed chlorine after the grafting and carry out chlorination reaction, the manufacturing chlorinity is higher, with better, the common molten wider multi-component copolymer chlorinatedpolyethylene of other resin cosolvencies.The industrialized preparing process of multi-component copolymer chlorinatedpolyethylene does not pollute surrounding enviroment.And the reaction times is short, is convenient to operation, adapts to scale production, and cost is lower.The objective of the invention is to realize by the following technical solutions.
A kind of multicomponent copolymer chlorinated polyethylene by water phase grafting industrialized preparing process, this method is raw material with the polyethylene powders, put in the aqueous solution that contains emulsification promotor, dispersion separant, activation initiator, under the effect of stirring, make polyethylene powders be suspended state, before feeding chlorine carries out chlorination reaction, on poly molecular chain, connect functional group earlier; Its technical essential is that described functional group is carboxyl, hydroxyl, ester group and four functional groups of carbonyl, and the quantity that connects functional group is 1～10% of polyethylene weight ratio; Divide three temperature sections to feed a certain proportion of chlorine respectively then, and in same glassed steel reaction vessels, carry out chlorination reaction, finally make chlorinity and be 60～75% multi-component copolymer chlorinatedpolyethylene; Raw materials used polyethylene, its molecular weight are between 3000～50000, and the granularity of powder was between 60～120 orders after fragmentation was sieved.
Described multicomponent copolymer chlorinated polyethylene by water phase grafting industrialized preparing process, the water that it is characterized in that the aqueous solution in the described reactor are the water purification of 20～40 times of polyethylene weight; Alleged water purification refers to filter back clean process water, deionized water, distilled water; The emulsification promotor that adds is 1.0～2.5% of material polyethylene weight; Dispersion agent is 2～6%; Activating initiator is 1.5～2.5%.Materials such as emulsification promotor that adds such as polyoxyethylene alkylphenol, polysorbate60, peregal 20, Viscotrol C-Soxylat A 25-7, polyoxyethylene Fatty Alcohol(C12-C14 and C12-C18); Disperse separant such as vinyl monomer multipolymer, sodium polymethacrylate, sodium polyacrylate, maleic acid anhydride-phenylethylene copolymer etc.; Initiator as activating reaction can be selected for use in superoxide, azo-based compound.The process that feeds chlorine in the airtight glassed steel reaction vessels that stirs to band divides three sections to carry out, first temperature section in the time of 80～90 ℃, and chlorine feeding amount must reach chlorine should feed 45～70% of total amount; When 90～110 ℃ of second temperature sections, chlorine feeding amount should reach 95% of total amount; The 3rd temperature section is the temperature a little more than 110 ℃, last 5% last chlorine is all fed finish; After logical chlorine finished, insulation earlier 0.5～2 hour was driven remaining chlorine in the still away with uncontaminated air then, cools to 70～80 ℃.After washing depickling, neutralization, dehydration, drying, promptly obtain described multi-component copolymer chlorinatedpolyethylene then.The total amount that feeds chlorine is 4～6 times of polyethylene raw material weight.Each temperature section feeds the weight and the ratio of chlorine and is controlled by measure monitor the back as calculated.
" syllogic " described in the present invention is to the in good time heat temperature raising of reaction mass in fact, reaches specified temperature, and controls a kind of working method of the feeding amount of chlorine simultaneously, finishes chlorination reaction continuously in same glassed steel reaction vessels; Do not need raw material is transferred to another reactor reaction; Whole time of chlorinating is 3～4 hours.
Multi-component copolymer chlorinatedpolyethylene of the present invention is a chlorinity up to 60～75% multi-component copolymer chlorinatedpolyethylene, and can in organic solvents such as toluene, dimethylbenzene, fully dissolve, good with other resin compatibilities, solution is limpid vitreous state, 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 enviroment are not polluted.And be that the reaction times is short, be convenient to operation, adapt to scale production, cost is lower, and economic benefit is considerable.
Embodiment
The invention will be further described by the following examples.For embodiment, be the example that actually operating is verified in mass-producing trial production.Therefore be easy to be grasped by those skilled in the art.Change as make some on basis of the present invention, its essence does not exceed the scope that the present invention includes.Therefore, described embodiment only makes an explanation to the present invention, is not that the present invention is made restriction.
Embodiment:
In the glassed steel reaction vessels that 2000 liters of bands stir, add water purification 1500Kg; Reach granularity 60～120 purpose hp-ldpe 70Kg behind the crushing screening, emulsification promotor 600g, dispersion separant 2Kg, activation initiator 600g.Under agitation be warmed up to 90～100 ℃ and be incubated 0.5～1 hour gradually, make and connect carboxyl, hydroxyl, ester group and carbonyl on the sub polyethylene subchain, when again temperature being reduced to 60 ℃, begin to feed chlorine.Reached before 88 ℃ in temperature, the feeding amount of chlorine must reach 60% of total feeding amount, continues to be warming up to 110 ℃ then, and the feeding amount of chlorine requires to reach 95%; 5% last chlorine must feed when 100～120 ℃ of temperature, and total feeding amount of chlorine is 330Kg, and the chlorination reaction whole process is 3 hours 20 minutes, and chlorination reaction finishes; Insulation is earlier driven remaining chlorine in the still away with uncontaminated air after 2 hours again, cools to 80 ℃.Material is washed depickling, neutralization, dehydration, drying, promptly obtain the white powder multi-component copolymer chlorinatedpolyethylene finished product of chlorinity 68%.
Claims (2)
1, a kind of multicomponent copolymer chlorinated polyethylene by water phase grafting industrialized preparing process, this method is raw material with the polyethylene powders, put in the aqueous solution that contains emulsification promotor, dispersion separant, activation initiator, under the effect of stirring, make polyethylene powders be suspended state, before feeding chlorine carries out chlorination reaction, on poly molecular chain, connect functional group earlier; It is characterized in that described functional group is carboxyl, hydroxyl, ester group and four functional groups of carbonyl, the quantity that connects functional group is 1～10% of polyethylene weight ratio; Divide three temperature sections to feed a certain proportion of chlorine respectively then, and in same glassed steel reaction vessels, carry out chlorination reaction, finally make chlorinity and be 60～75% multi-component copolymer chlorinatedpolyethylene; Raw materials used polyethylene, its molecular weight is between 3000～50000.
2, multicomponent copolymer chlorinated polyethylene by water phase grafting industrialized preparing process as claimed in claim 1, the water that it is characterized in that the aqueous solution in the described reactor are the water purification of 20～40 times of polyethylene weight; Alleged water purification refers to filter back clean process water, deionized water, distilled water; The emulsification promotor that adds is 1.0～2.5% of material polyethylene weight; Dispersion agent is 2～6%; Activating initiator is 1.5～2.5%.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA200910095625XA CN101475653A (en) | 2009-01-13 | 2009-01-13 | Industrial production method of multicomponent copolymer chlorinated polyethylene by water phase grafting |
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| CNA200910095625XA CN101475653A (en) | 2009-01-13 | 2009-01-13 | Industrial production method of multicomponent copolymer chlorinated polyethylene by water phase grafting |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102827329A (en) * | 2012-09-20 | 2012-12-19 | 山东瑞丰高分子材料股份有限公司 | High-tensile-strength impact modifier for PVC (polyvinyl chloride) and preparation technique thereof |
| CN110343216A (en) * | 2019-01-28 | 2019-10-18 | 浙江大学 | A method of the maleic anhydride modified polythene material of chlorination is prepared using composite initiation system |
-
2009
- 2009-01-13 CN CNA200910095625XA patent/CN101475653A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102827329A (en) * | 2012-09-20 | 2012-12-19 | 山东瑞丰高分子材料股份有限公司 | High-tensile-strength impact modifier for PVC (polyvinyl chloride) and preparation technique thereof |
| CN110343216A (en) * | 2019-01-28 | 2019-10-18 | 浙江大学 | A method of the maleic anhydride modified polythene material of chlorination is prepared using composite initiation system |
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Open date: 20090708 |