CN105504172A - Preparation process of modified chlorinated polyethylene for rubber plastic material - Google Patents
Preparation process of modified chlorinated polyethylene for rubber plastic material Download PDFInfo
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- CN105504172A CN105504172A CN201510979608.8A CN201510979608A CN105504172A CN 105504172 A CN105504172 A CN 105504172A CN 201510979608 A CN201510979608 A CN 201510979608A CN 105504172 A CN105504172 A CN 105504172A
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- chlorinated polyethylene
- modified chlorinated
- rubber
- plastics material
- preparation technology
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- 239000004709 Chlorinated polyethylene Substances 0.000 title claims abstract description 106
- 229920003023 plastic Polymers 0.000 title claims abstract description 40
- 239000004033 plastic Substances 0.000 title claims abstract description 40
- 239000000463 material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229920001971 elastomer Polymers 0.000 title abstract description 18
- 239000005060 rubber Substances 0.000 title abstract description 18
- 206010042674 Swelling Diseases 0.000 claims abstract description 29
- 230000008961 swelling Effects 0.000 claims abstract description 29
- 239000000047 product Substances 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000012043 crude product Substances 0.000 claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 238000012986 modification Methods 0.000 claims abstract description 10
- 230000004048 modification Effects 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000000746 purification Methods 0.000 claims abstract description 5
- 238000005516 engineering process Methods 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 5
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 108010010803 Gelatin Proteins 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 2
- 229960001866 silicon dioxide Drugs 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 abstract description 3
- 229910001873 dinitrogen Inorganic materials 0.000 abstract 1
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 239000013536 elastomeric material Substances 0.000 description 9
- 239000004800 polyvinyl chloride Substances 0.000 description 8
- 229920000915 polyvinyl chloride Polymers 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- -1 polyethylene Polymers 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 239000004609 Impact Modifier Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000002688 persistence Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 101100161875 Arabidopsis thaliana ACR2 gene Proteins 0.000 description 1
- 101100495264 Arabidopsis thaliana CDC25 gene Proteins 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 101100380266 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) ARR2 gene Proteins 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 101150004068 acrB gene Proteins 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
- C08F255/023—On to modified polymers, e.g. chlorinated polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
Abstract
The invention provides a preparation process of modified chlorinated polyethylene for a rubber plastic material and belongs to the technical field of chlorinated polyethylene for the rubber plastic material. Universal chlorinated polyethylene is grafted and modified, and modified chlorinated polyethylene is obtained. The preparation process comprises steps as follows: A, swelling treatment: universal chlorinated polyethylene, an initiator, a grafting monomer, a swelling agent and deionized water are added to a reactor in a proportion for swelling treatment; B, dispersing treatment: deionized water and a dispersing agent are added to a product obtained after swelling treatment in the step A in a stirring state for dispersing treatment, nitrogen gas is introduced into the mixture, the mixture is heated for a reaction, and a modified chlorinated polyethylene crude product is obtained; C, purification treatment: the modified chlorinated polyethylene crude product obtained in the step B is extracted, the extracted product is dried to reach a constant weight, and modified chlorinated polyethylene is obtained. The modified chlorinated polyethylene obtained through grafting and modification is added to a plastic rubber material, and the performance of the plastic rubber material is greatly improved.
Description
Technical field
The invention belongs to the technical field of rubber-plastics material chlorinatedpolyethylene, be specifically related to a kind of preparation technology of the modified chlorinated polyethylene for rubber-plastics material, obtain modified chlorinated polyethylene by chlorinated polyethylene grafting modification, be applied to rubber-plastics material and add the comprehensive use properties problem in man-hour to improve chlorinatedpolyethylene.
Background technology
Chlorinatedpolyethylene (ChlorinatedPolyethylene) be polyethylene through liquid chlorine chlorination obtained chlorine-containing polymer, its molecular structure can regard ethene, vinylchlorid, 1 as, the ternary atactic copolymer of 2-Ethylene Dichloride, it is nonpoisonous and tasteless white or micro-yellow powder.By the difference of chlorinity, plasticity CPE (chlorinity 15%), elasticity CPE (16%-20%), elastomerics CPE (25%-50%), hard CPE (51%-60%) and snappiness CPE can be divided into.The chlorinity of commodity CPE is generally at 30%-40%, and its performance is similar to rubber; If chlorinity is lower than 30%, its performance is close to polyethylene; If chlorinity is higher than 40%, its performance is close to polyvinyl chloride.
Universal (mould and change) chlorinatedpolyethylene (CPE) and rubber-type chlorinated polyethylene (CM) can be divided into according to its chlorinity and distribution, residual crystallinity and other features.The former is rubber-plastics material properties-correcting agent, is used for resistance alkene or the toughening modifying of the plastics such as PVC, ABS; The latter is elastomerics, how uses as rubber, or with other rubber blendings, be one of the glue kind of most development prospect in Halogen class rubber.
Owing to having accessed containing cl radical without unsaturated link(age) in chlorinatedpolyethylene molecular structure, and chlorine atom is along Polyethylene Chain random distribution, therefore product has stable chemical structure, there are excellent weather-proof, resistance to ozone, chemical resistance corrosion and ageing-resistant performance, good consistency, toughness, oil-proofness, flame retardant resistance, tint permanence and electrical insulating property etc., and price is low, be at half than rubber raw materials.In the goods such as electric wire, acidproof/oil resisting rubber hose, waterproof roll, fire retarding conveying band, V band, auto parts machinery, sealing member, sponge, there is applications well prospect.
2014, the aggregated capacity of China CPE was more than 1,200,000 tons/year, and actual demand amount only about 700,000 tons, substantially exceed the demand of market reality, more than 90% is the anti-impact modifier being used as hard PVC material, for elastomeric material less than 10%.Current technical bottleneck be its be difficult to meet not only as plastics anti-impact modifier but also can use as elastomeric material.CPE, as rubber-plastics material, have the features such as cheap, weather resistance good, processibility is good, but also there is following subject matter in it in the application:
1, for plastics, time, CPE promotes that plasticizing function is not obvious, also needs to add the processing that auxiliary auxiliary agent could realize plastics.
2, for low temperature situation plastics, the shock proof persistence of prolonged cold of CPE is worse than acrylic ester impact-resisting and hits properties-correcting agent.
3, for rubber item, the sulfidation of CPE is bad, the smooth phase short (even the CPE of rubber-type, processing technology is bad in production of articles).
4, the cross-linked rubber resistance to low temperature of CPE is not good enough, and temperature limit of brittleness is higher.
5, processibility when CPE and other rubber share is poor.
Therefore research and develop graft modification chlorinatedpolyethylene, need the remaining crystallization destroying CPE, to make up the unfavorable factor of chlorine atom skewness on CPE main chain, improve the comprehensive use properties of CPE, also make it the characteristic with elastomeric material.The top grade of CPE, high performance research and development and application will be its leap property progress as rubber-plastics material field and the update of novel material.
Summary of the invention
The present invention is the problems such as the promotion plasticizing function that solution universal chlorinatedpolyethylene industrial applications of the prior art exists is poor, low-temperature impact resistance persistence difference, especially universal CPE is as the not good problem of elastomeric material performance, provide a kind of preparation technology of the universal modified chlorinated polyethylene for rubber-plastics material, there is the advantages such as good processability, curability is good, mechanical property is good.
The present invention is the technical scheme realizing the employing of its object:
For a preparation technology for the modified chlorinated polyethylene of rubber-plastics material, by universal chlorinatedpolyethylene is carried out graft modification, obtain modified chlorinated polyethylene, comprise the following steps:
A, swelling treatment: universal chlorinatedpolyethylene and initiator, grafted monomer, swelling agent and deionized water are joined in reactor in proportion and carries out swelling treatment;
B, dispersion treatment: under whipped state, add deionized water to the product obtained after steps A swelling treatment and dispersion agent carries out dispersion treatment, then pass into nitrogen wherein, temperature reaction, obtain modified chlorinated polyethylene crude product;
C, purification process: the modified chlorinated polyethylene crude product obtained by step B carries out extracting, then the product after extracting is dried to constant weight, obtains modified chlorinated polyethylene.
Universal chlorinatedpolyethylene and initiator, grafted monomer, swelling agent and distilled water to be joined in proportion in reactor swelling treatment 0.5-2.5h under the condition of 50-80 DEG C.
In steps A, the weight ratio of universal chlorinatedpolyethylene and initiator, grafted monomer, swelling agent and deionized water is (10-40): (0.03-0.5): (2-10): (5-20): 100.
Described initiator is benzoyl peroxide or dicumyl peroxide.
Described grafted monomer is selected from the one in maleic anhydride, vinylformic acid (ester), vinylbenzene, organic amine.
Described swelling agent is selected from the one in toluene, dimethylbenzene, ethyl acetate, solvent oil.
Described dispersion agent is selected from the one in gelatin, polyvinyl alcohol, silicon-dioxide, light calcium carbonate.
After passing into nitrogen in step B, be warming up to 55-90 DEG C, reaction 1-4h, reacts complete suction filtration while hot, and uses hot wash product, obtain modified chlorinated polyethylene crude product.
Be that solvent is placed in Soxhlet extractor extracting 0.5-2h with acetone during the extracting of modified chlorinated polyethylene crude product.
The invention has the beneficial effects as follows: the modified chlorinated polyethylene obtained by graft modification of the present invention is applied in plastics, not only increase prolonged cold shock resistance and the processing characteristics of plastic material, also improve its resistance to low temperature for elastomeric material, temperature limit of brittleness and sulfuration processing characteristics.And it can be used as the starting material of rubber-plastics material, its consumption, compared with unmodified chlorinatedpolyethylene, has the characteristics such as consumption is few, good physical performance.Meanwhile, universal chlorinatedpolyethylene is carried out modification by the present invention, not only makes the performance of plastic material products be improved largely, and is applied in elastomeric material, and its service performance very good too, substantially increases the performance of Rubber.
The present invention is by modified for universal chlorinated polyethylene grafting, and its comprehensive use properties promotes greatly, has great society and economic implications.On the one hand, modified CPE is used for plastic material, and its consumption reduces, and product properties promotes, and PVC product user synthetic prescription cost reduces, and has larger promoter action for the industry restructuring of China CPE industry.On the other hand, it is for elastomeric material, and the various synthetic rubbers such as alternative natural rubber and neoprene, butylbenzene, suitable fourth, improve the added value of chlorinatedpolyethylene product self greatly.
Embodiment
The present invention solves CPE in prior art to be applied to the technical problem existed in rubber-plastics material, especially the problem that universal chlorinatedpolyethylene application of rubber materials'use characteristic is not good, provide a kind of preparation technology of the modified chlorinated polyethylene for rubber-plastics material, good processability, mechanical property are good, consistency is good.
One, embodiment 1.
Grafting is carried out, wherein chlorinatedpolyethylene 200g, maleic anhydride 35g, dicumyl peroxide 1.2g, ethyl acetate 100mL, deionized water 1000mL after chlorinatedpolyethylene ethyl acetate is swelling.
A, swelling treatment: universal chlorinatedpolyethylene and dicumyl peroxide, maleic anhydride, ethyl acetate and deionized water are joined in reactor in proportion, agitator, prolong, thermometer, separating funnel is furnished with, universal chlorinatedpolyethylene abundant swelling 2h when stirring under 60 DEG C of conditions in this reactor;
B, dispersion treatment: under whipped state, add deionized water to the product obtained after steps A swelling treatment and dispersion agent carries out dispersion treatment, then nitrogen is passed into wherein, be warming up to 90 DEG C and carry out reaction 3h, react complete suction filtration while hot, during suction filtration first with precipitation agent by product precipitate and separate, then use hot wash product, obtain modified chlorinated polyethylene crude product; Consider in experiment that the later stage carries out extracting with acetone, the acetone that precipitation agent is selected of inertial thinking, but find that the graft product particle be precipitated out is little especially, relatively thickness, easily blocks filter paper when suction filtration, causes being separated unsuccessfully, precipitated with ethanol unintentionally afterwards, found that with alcohol settling product grain out comparatively large, more easily separate, thus ethanol selected by precipitation agent.
C, purification process: the modified chlorinated polyethylene crude product filter paper obtained by step B is wrapped and put into apparatus,Soxhlet's, carries out extracting 1h, then the product after extracting is dried to constant weight, obtain the modified chlorinated polyethylene after purifying with acetone.
Find in experimentation: the consumption of swelling agent is more, the particle of products therefrom is less, and dispersion effect is better, and reactant contact area can be made like this to increase.
Embodiment 2
Grafting is carried out, wherein chlorinatedpolyethylene 250g, maleic anhydride 40g, benzoyl peroxide 1.5g, dimethylbenzene 120mL, water 1000mL after chlorinatedpolyethylene dimethylbenzene is swelling in water.
A, swelling treatment: universal chlorinatedpolyethylene and benzoyl peroxide, maleic anhydride, dimethylbenzene and deionized water are joined in reactor in proportion, agitator, prolong, thermometer, separating funnel is furnished with, universal chlorinatedpolyethylene abundant swelling 1.5h when stirring under 80 DEG C of conditions in this reactor;
B, dispersion treatment: under whipped state, add deionized water to the product obtained after steps A swelling treatment and dispersion agent carries out dispersion treatment, then nitrogen is passed into wherein, be warming up to 90 DEG C of reaction 3h, after reaction terminates, carry out separatory, dimethylbenzene is separated, add precipitation agent by product precipitate and separate, and use hot wash product, obtain modified chlorinated polyethylene crude product;
C, purification process: the modified chlorinated polyethylene crude product filter paper obtained by step B is wrapped and put into apparatus,Soxhlet's, carries out extracting 0.5h, then the product after extracting is dried to constant weight, obtain the modified chlorinated polyethylene after purifying with acetone.
Comparative example 1
Polyvinyl chloride resin 100 parts, processing aid ACR2 part, rare earth complex heat stabilizer 4.5 parts, titanium dioxide 5 parts, 20 parts, calcium carbonate, add modified chlorinated polyethylene of the present invention (CPE) 6 parts respectively, unmodified chlorinatedpolyethylene 9 parts, the 5min that plasticates in 170 ~ 175 DEG C of two roller mills after grinding evenly is respectively in blocks, then at 180 ~ 185 DEG C of vulcanizing press compacting growth 150mm, wide 100mm, the test piece of thick 4mm, and carry out sample preparation by standard GB/T1040-2006 " plastic tensile performance test methods " and the tensile strength of difference test sample, elongation at break and simply supported beam notched Izod impact strength, or above-mentioned print is tested its weathering stability in ultraviolet light and aging proofing box, or uniform for above-mentioned grinding compound is got its rheologic behavio(u)r of contrast test on Plus-EC type Brabender rheometer in right amount respectively, result is as shown in the table:
Table 1: the stretching of sample and breach performance test contrast experiment
Table 2: the weather resistance contrast experiment of the test piece whiteness of test sample (after the QUV ultra violet lamp)
Table 3: different ingredients is along the rheologic behavio(u)r contrast experiment of batching
Comparative example 2
According to the following formulation, unmodified chlorinatedpolyethylene and modified chlorinatedpolyethylene are applied in rubber-plastics material, 5-10min that 140 ~ 160 DEG C of two roller mills are plasticated is in blocks, first test the vulcanization curve of test piece, then it is 165 DEG C at cure conditions, pressure 8MPa, curing time is 10min tabletted, tests the performance of rubber-plastics material respectively.
As can be seen here, application range of products of the present invention is wider, not only can be used for PVC modification, can be used for elastomeric material again, and comprehensive use properties is more superior, is mainly manifested in:
(1) for PVC plastic material, product of the present invention has that consumption is few, shock resistance is excellent, and has the advantages such as promote the function of PVC plastic and goods weather resistance is good.
(2) for elastomeric material, the performance of modification CPE sizing material is much better than unmodified CPE properties of rubber, is mainly manifested in the aspects such as tensile strength, stress at definite elongation and temperature limit of brittleness.In addition, its vulcanization curve shows, modification CPE is more suitable for the production for extensive rubber item.
Claims (9)
1., for a preparation technology for the modified chlorinated polyethylene of rubber-plastics material, by universal chlorinatedpolyethylene is carried out graft modification, obtain modified chlorinated polyethylene, it is characterized in that: comprise the following steps:
A, swelling treatment: universal chlorinatedpolyethylene and initiator, grafted monomer, swelling agent and deionized water are joined in reactor in proportion and carries out swelling treatment;
B, dispersion treatment: under whipped state, add deionized water to the product obtained after steps A swelling treatment and dispersion agent carries out dispersion treatment, then pass into nitrogen wherein, temperature reaction, obtain modified chlorinated polyethylene crude product;
C, purification process: the modified chlorinated polyethylene crude product obtained by step B carries out extracting, then the product after extracting is dried to constant weight, obtains modified chlorinated polyethylene.
2. the preparation technology of a kind of modified chlorinated polyethylene for rubber-plastics material according to claim 1, is characterized in that: universal chlorinatedpolyethylene and initiator, grafted monomer, swelling agent and distilled water to be joined in proportion in reactor swelling treatment 0.5-2.5h under the condition of 50-80 DEG C.
3. the preparation technology of a kind of modified chlorinated polyethylene for rubber-plastics material according to claim 1, is characterized in that: in steps A, the weight ratio of universal chlorinatedpolyethylene and initiator, grafted monomer, swelling agent and deionized water is (10-40): (0.03-0.5): (2-10): (5-20): 100.
4. the preparation technology of a kind of modified chlorinated polyethylene for rubber-plastics material according to claim 1, is characterized in that: described initiator is benzoyl peroxide or dicumyl peroxide.
5. the preparation technology of a kind of modified chlorinated polyethylene for rubber-plastics material according to claim 1, is characterized in that: described grafted monomer is selected from the one in maleic anhydride, vinylformic acid (ester), vinylbenzene, organic amine.
6. the preparation technology of a kind of modified chlorinated polyethylene for rubber-plastics material according to claim 1, is characterized in that: described swelling agent is selected from the one in toluene, dimethylbenzene, ethyl acetate, solvent oil.
7. the preparation technology of a kind of modified chlorinated polyethylene for rubber-plastics material according to claim 1, is characterized in that: described dispersion agent is selected from the one in gelatin, polyvinyl alcohol, silicon-dioxide, light calcium carbonate.
8. the preparation technology of a kind of modified chlorinated polyethylene for rubber-plastics material according to claim 1, is characterized in that: after passing into nitrogen in step B, is warming up to 55-90 DEG C, reaction 1-4h, react complete suction filtration while hot, and use hot wash product, obtain modified chlorinated polyethylene crude product.
9. the preparation technology of a kind of modified chlorinated polyethylene for rubber-plastics material according to claim 1, is characterized in that: be that solvent is placed in Soxhlet extractor extracting 0.5-2h with acetone during the extracting of modified chlorinated polyethylene crude product.
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| CN110283412B (en) * | 2019-06-25 | 2021-04-13 | 潍坊亚星化学股份有限公司 | Blending modified chlorinated polyvinyl chloride material and preparation method thereof |
| CN112375326A (en) * | 2021-01-12 | 2021-02-19 | 潍坊硕邑化学有限公司 | Preparation method of chlorinated polyethylene with high elongation at break |
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| CN114316494B (en) * | 2021-12-30 | 2024-01-26 | 镇江市华银仪表电器有限公司 | High-strength heat-resistant rubber wire and preparation method thereof |
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