CN105504172B - Preparation process of modified chlorinated polyethylene for rubber and plastic material - Google Patents
Preparation process of modified chlorinated polyethylene for rubber and plastic material Download PDFInfo
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- CN105504172B CN105504172B CN201510979608.8A CN201510979608A CN105504172B CN 105504172 B CN105504172 B CN 105504172B CN 201510979608 A CN201510979608 A CN 201510979608A CN 105504172 B CN105504172 B CN 105504172B
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- chlorinated polyethylene
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- 239000004709 Chlorinated polyethylene Substances 0.000 title claims abstract description 124
- 229920001971 elastomer Polymers 0.000 title claims abstract description 49
- 239000005060 rubber Substances 0.000 title claims abstract description 48
- 239000000463 material Substances 0.000 title claims abstract description 46
- 229920003023 plastic Polymers 0.000 title claims abstract description 37
- 239000004033 plastic Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000047 product Substances 0.000 claims abstract description 51
- 206010042674 Swelling Diseases 0.000 claims abstract description 26
- 230000008961 swelling Effects 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 239000006185 dispersion Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000012043 crude product Substances 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 239000002270 dispersing agent Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 238000012986 modification Methods 0.000 claims abstract description 6
- 230000004048 modification Effects 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000000746 purification Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 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 group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 239000012716 precipitator Substances 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
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 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
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims 1
- 239000005995 Aluminium silicate Substances 0.000 claims 1
- 235000012211 aluminium silicate Nutrition 0.000 claims 1
- 239000006229 carbon black Substances 0.000 claims 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims 1
- 239000000395 magnesium oxide Substances 0.000 claims 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
- 229920000915 polyvinyl chloride Polymers 0.000 description 8
- 239000004800 polyvinyl chloride Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000004073 vulcanization Methods 0.000 description 6
- 239000004609 Impact Modifier Substances 0.000 description 4
- -1 Polyethylene Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 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 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 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
- 229920006235 chlorinated polyethylene elastomer Polymers 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000000136 cloud-point extraction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UKDOTCFNLHHKOF-FGRDZWBJSA-N (z)-1-chloroprop-1-ene;(z)-1,2-dichloroethene Chemical group C\C=C/Cl.Cl\C=C/Cl UKDOTCFNLHHKOF-FGRDZWBJSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 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
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 150000002148 esters Chemical class 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
- 239000007788 liquid Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229920005604 random copolymer Polymers 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
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 230000035882 stress Effects 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
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000004636 vulcanized rubber 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
A preparation process of modified chlorinated polyethylene for rubber and plastic materials belongs to the technical field of chlorinated polyethylene for rubber and plastic materials, and the modified chlorinated polyethylene is obtained by carrying out graft modification on general chlorinated polyethylene, and comprises the following steps: A. swelling treatment: adding general chlorinated polyethylene, an initiator, a grafting monomer, a swelling agent and deionized water into a reactor in proportion for swelling treatment; B. and (3) dispersion treatment: adding deionized water and a dispersing agent into the product obtained after the swelling treatment in the step A under the stirring state for dispersion treatment, then introducing nitrogen into the product, and heating for reaction to obtain a crude product of the modified chlorinated polyethylene; C. and (3) purification treatment: and D, extracting the crude product of the modified chlorinated polyethylene obtained in the step B, and drying the extracted product to constant weight to obtain the modified chlorinated polyethylene. The modified chlorinated polyethylene obtained by the graft modification of the invention is applied to rubber and plastic materials, and the performance of the rubber and plastic materials is greatly improved.
Description
Technical Field
The invention belongs to the technical field of chlorinated polyethylene for rubber and plastic materials, and particularly relates to a preparation process of modified chlorinated polyethylene for rubber and plastic materials.
Background
Chlorinated Polyethylene (Chlorinated Polyethylene) is a chlorine-containing polymer prepared by liquid chlorine chlorination of Polyethylene, and the molecular structure of the Chlorinated Polyethylene can be regarded as a ternary random copolymer of ethylene, vinyl chloride and 1, 2-dichloroethylene, and the Chlorinated Polyethylene is nontoxic and tasteless white or yellowish powder. According to the difference of chlorine content, the CPEs can be divided into plastic CPE (chlorine content 15%), elastic CPE (16% -20%), elastic CPE (25% -50%), hard CPE (51% -60%) and high-elasticity CPE. The chlorine content of the commercial CPE is generally 30% -40%, and the performance of the commercial CPE is similar to that of rubber; if the chlorine content is less than 30%, the performance is close to that of polyethylene; if the chlorine content is higher than 40%, the properties are close to those of polyvinyl chloride.
They can be classified into general-purpose (modified) Chlorinated Polyethylene (CPE) and rubber-type chlorinated polyethylene (CM) according to their chlorine content and distribution, residual crystallinity and other characteristics. The former is a rubber-plastic material modifier and is mainly used for olefin blocking or toughening modification of PVC, ABS and other plastic products; the latter is an elastomer, and is often used as a rubber, or is used in combination with other rubbers, and is one of the most promising types of rubbers containing halogen.
The chlorinated polyethylene has no unsaturated bond in the molecular structure, is grafted with chlorine-containing groups, and the chlorine atoms are randomly distributed along the polyethylene chain, so that the product has a stable chemical structure, has excellent weather resistance, ozone resistance, chemical corrosion resistance, aging resistance, good compatibility, toughness, oil resistance, flame retardance, colorability, electrical insulation and the like, and is low in price and half lower than that of a rubber raw material. The flame-retardant rubber belt has good application prospect in products such as wires and cables, acid/oil-resistant rubber pipes, waterproof coiled materials, flame-retardant conveying belts, V belts, automobile accessories, sealing elements, sponges and the like.
In 2014, the total yield of CPE in China exceeds 120 ten thousand tons per year, the actual demand is only about 70 ten thousand tons, which greatly exceeds the actual demand of the market, more than 90 percent of CPE is used as an impact modifier of a hard PVC material, and the total yield is less than 10 percent when CPE is used for a rubber material. The technical bottleneck at present is that the rubber material is difficult to meet the requirements of serving as an impact modifier of plastic products and serving as a rubber material. The CPE serving as a rubber and plastic material has the characteristics of low price, good weather resistance, good processability and the like, but has the following main problems in application:
1. when the CPE is used for plastics, the CPE has an unobvious plasticizing promoting function, and auxiliary additives are added to realize the processing and production of plastic products.
2. When the impact modifier is used for plastic products in low-temperature occasions, the durability of the long-term low-temperature impact resistance of CPE is inferior to that of an acrylate impact modifier.
3. For rubber articles, the vulcanization behavior of the CPE is poor and the plateau time is short (even for rubber-type CPEs, the processability during the production of the articles is poor).
4. The low-temperature resistance of the vulcanized rubber of CPE is not good enough, and the brittleness temperature is higher.
5. CPE is poor in processability when used in combination with other rubbers.
Therefore, in the development of the graft modified chlorinated polyethylene, the residual crystal of the CPE needs to be damaged to make up the adverse factor of uneven distribution of chlorine atoms on the main chain of the CPE, improve the comprehensive use performance of the CPE and ensure that the CPE has the characteristics of a rubber material. The development and application of CPE with high grade and high performance are absolutely a leap forward and new generation of the CPE as a rubber and plastic material field.
Disclosure of Invention
The invention provides a preparation process of universal modified chlorinated polyethylene for rubber and plastic materials, aiming at solving the problems of poor plasticizing promotion function, poor low-temperature impact resistance durability and the like in the industrial application of the universal chlorinated polyethylene in the prior art, in particular the problem of poor performance of the universal CPE as a rubber material, and the preparation process has the advantages of good processing performance, good vulcanization performance, good mechanical property and the like.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a preparation process of modified chlorinated polyethylene for rubber and plastic materials is characterized in that general chlorinated polyethylene is subjected to graft modification to obtain the modified chlorinated polyethylene, and the preparation process comprises the following steps:
A. swelling treatment: adding general chlorinated polyethylene, an initiator, a grafting monomer, a swelling agent and deionized water into a reactor in proportion for swelling treatment;
B. and (3) dispersion treatment: adding deionized water and a dispersing agent into the product obtained after the swelling treatment in the step A under the stirring state for dispersion treatment, then introducing nitrogen into the product, and heating for reaction to obtain a crude product of the modified chlorinated polyethylene;
C. and (3) purification treatment: and D, extracting the crude product of the modified chlorinated polyethylene obtained in the step B, and drying the extracted product to constant weight to obtain the modified chlorinated polyethylene.
Adding general chlorinated polyethylene, an initiator, a grafting monomer, a swelling agent and distilled water into a reactor in proportion, and swelling for 0.5-2.5h at the temperature of 50-80 ℃.
The weight ratio of the universal chlorinated polyethylene to the initiator, the grafting monomer, the swelling agent and the deionized water in the step A is (10-40): (0.03-0.5): (2-10): (5-20): 100.
the initiator is benzoyl peroxide or dicumyl peroxide.
The grafting monomer is one selected from maleic anhydride, acrylic acid (ester), styrene and organic amine.
The swelling agent is selected from one of toluene, xylene, ethyl acetate and solvent oil.
The dispersing agent is selected from one of gelatin, polyvinyl alcohol, silicon dioxide and light calcium carbonate.
And B, introducing nitrogen into the product in the step B, heating the product to 55-90 ℃, reacting for 1-4h, performing suction filtration when the reaction is finished, and washing the product with hot water to obtain a crude modified chlorinated polyethylene product.
During the extraction of the crude product of the modified chlorinated polyethylene, acetone is taken as a solvent and is put into a Soxhlet extractor for extraction for 0.5 to 2 hours.
The invention has the beneficial effects that: the modified chlorinated polyethylene obtained by the graft modification is applied to plastics, so that the long-term low-temperature impact resistance and the processability of plastic materials are improved, and the low-temperature resistance, the brittleness temperature and the vulcanization processability of rubber materials are improved. Compared with unmodified chlorinated polyethylene, the dosage of the modified chlorinated polyethylene is less, and the physical properties are good. Meanwhile, the general chlorinated polyethylene is modified, so that the performance of the plastic material product is greatly improved, and the application characteristics of the plastic material product are also very good when the general chlorinated polyethylene is applied to a rubber material, so that the performance of the rubber material product is greatly improved.
After the general chlorinated polyethylene is grafted and modified, the comprehensive use performance of the general chlorinated polyethylene is greatly improved, and the general chlorinated polyethylene grafted and modified chlorinated polyethylene has great social and economic significance. On one hand, the modified CPE is used for plastic materials, the consumption is reduced, the product performance is improved, the comprehensive formula cost of PVC product users is reduced, and the method has a great promotion effect on the adjustment of industrial structures in the CPE industry in China. On the other hand, the chlorinated polyethylene can be used for rubber materials, can replace natural rubber and various synthetic rubbers such as chloroprene, butylbenzene and butadiene, and greatly improves the added value of the chlorinated polyethylene product.
Detailed Description
The invention provides a preparation process of modified chlorinated polyethylene for rubber and plastic materials, aiming at solving the technical problems existing in the application of CPE to rubber and plastic materials in the prior art, in particular to the problem of poor use characteristics of general chlorinated polyethylene applied rubber materials, and the preparation process has the advantages of good processing performance, good mechanical properties and good compatibility.
First, example 1.
The chlorinated polyethylene is swelled by ethyl acetate and grafted, wherein 200g of the chlorinated polyethylene, 35g of maleic anhydride, 1.2g of dicumyl peroxide, 100m L g of ethyl acetate and 1000m L g of deionized water.
A. Swelling treatment: adding the universal chlorinated polyethylene, dicumyl peroxide, maleic anhydride, ethyl acetate and deionized water into a reactor in proportion, wherein the reactor is provided with a stirrer, a condenser pipe, a thermometer and a separating funnel, and the universal chlorinated polyethylene fully swells for 2 hours when stirred at the temperature of 60 ℃;
B. and (3) dispersion treatment: adding deionized water and a dispersing agent into the product obtained after the swelling treatment in the step A under the stirring state for dispersion treatment, then introducing nitrogen into the product, heating to 90 ℃ for reaction for 3 hours, carrying out suction filtration while the reaction is hot, precipitating and separating the product by using a precipitator during suction filtration, and then washing the product by using hot water to obtain a crude modified chlorinated polyethylene product; in the experiment, the later extraction is carried out by using acetone, the precipitator is selected from acetone by inertial thinking, but the precipitated grafting product particles are very small and viscous, the filter paper is easy to block during suction filtration, so that the separation fails, and the product particles precipitated by using ethanol are larger and easier to separate after the precipitation is carried out by using ethanol unintentionally, so that the precipitator is selected from ethanol.
C. And (3) purification treatment: and D, wrapping the crude modified chlorinated polyethylene product obtained in the step B with filter paper, putting the wrapped crude modified chlorinated polyethylene product into a Soxhlet extractor, extracting the wrapped crude modified chlorinated polyethylene product with acetone for 1 hour, and drying the extracted product to constant weight to obtain purified modified chlorinated polyethylene.
The experimental process shows that: the larger the amount of the swelling agent, the smaller the particles of the resulting product, and the better the dispersion effect, which can increase the contact area of the reactants.
Example 2
The chlorinated polyethylene is grafted after swelling in water by using xylene, wherein 250g of the chlorinated polyethylene, 40g of maleic anhydride, 1.5g of benzoyl peroxide, 120m of the xylene L and 1000m of the water L are used.
A. Swelling treatment: adding the universal chlorinated polyethylene, benzoyl peroxide, maleic anhydride, xylene and deionized water into a reactor in proportion, wherein the reactor is provided with a stirrer, a condenser pipe, a thermometer and a separating funnel, and the universal chlorinated polyethylene fully swells for 1.5 hours when stirred at the temperature of 80 ℃;
B. and (3) dispersion treatment: adding deionized water and a dispersing agent into the product obtained after the swelling treatment in the step A under the stirring state for dispersing treatment, then introducing nitrogen into the product, heating the mixture to 90 ℃ for reaction for 3 hours, separating liquid after the reaction is finished, separating xylene, adding a precipitating agent to precipitate and separate the product, and washing the product with hot water to obtain a crude product of the modified chlorinated polyethylene;
C. and (3) purification treatment: and D, wrapping the crude modified chlorinated polyethylene product obtained in the step B with filter paper, putting the wrapped crude modified chlorinated polyethylene product into a Soxhlet extractor, extracting the wrapped crude modified chlorinated polyethylene product with acetone for 0.5h, and drying the extracted product to constant weight to obtain purified modified chlorinated polyethylene.
Comparative example 1
100 parts of PVC resin, 2 parts of processing aid ACR, 4.5 parts of rare earth composite heat stabilizer, 5 parts of titanium dioxide and 20 parts of calcium carbonate are respectively added with 6 parts of modified Chlorinated Polyethylene (CPE) and 9 parts of unmodified chlorinated polyethylene, the mixture is milled uniformly and then plasticated on a double-roll mill at 170-175 ℃ for 5min to form sheets, then the sheets are pressed into test pieces with the length of 150mm, the width of 100mm and the thickness of 4mm by a flat vulcanizing machine at 180-185 ℃, samples are prepared according to the standard GB/T1040-2006 Plastic tensile property test method, and the tensile strength, the elongation at break and the notch impact strength of a simply supported beam are respectively tested; or testing the sample wafer in an ultraviolet light aging test box for weather resistance stability; or respectively taking a proper amount of the uniformly ground mixture, and carrying out comparative test on the rheological properties of the uniformly ground mixture on a Brabender rheometer model Plus-EC, wherein the results are shown in the following table:
table 1: comparative test for tensile and notch performance test of sample
Table 2: weather resistance comparison experiment of test piece (whiteness of test piece after QUV ultraviolet lamp irradiation)
Table 3: rheological property comparison experiment of different formula ingredients
Comparative example 2
According to the following formula, unmodified chlorinated polyethylene and modified chlorinated polyethylene are applied to a rubber plastic material, plasticating is carried out on a double-roller open mill at 140-160 ℃ for 5-10min to form a sheet, the vulcanization curve of a test piece is firstly tested, then the sheet is pressed into the sheet under the vulcanization condition of 165 ℃, the pressure of 8MPa and the vulcanization time of 10min, and the performances of the rubber plastic material are respectively tested.
Therefore, the product has wider application range, can be used for modifying PVC and rubber materials, and has more excellent comprehensive use performance which is mainly shown in that:
(1) the product of the invention is used for PVC plastic materials, has the advantages of small dosage, excellent shock resistance, promotion of PVC plasticization, good weather resistance of products and the like.
(2) The modified CPE rubber material is used for rubber materials, and the performance of the modified CPE rubber material is far better than that of the unmodified CPE rubber material, and mainly shows the aspects of tensile strength, stress at definite elongation, brittle temperature and the like. In addition, the cure curve indicates that the modified CPE is more suitable for use in the production of large-scale rubber articles.
Claims (6)
1. A preparation process of modified chlorinated polyethylene for rubber and plastic materials is characterized in that the general chlorinated polyethylene is subjected to graft modification to obtain the modified chlorinated polyethylene, and the preparation process comprises the following steps: the formula of the rubber plastic material is as follows: n33035 parts, white carbon black 25 parts, kaolin 25 parts, DOP 15 parts, DCP 5 parts, TAIC 3 parts, magnesium oxide 5 parts, modified CPE100 parts, the modified CPE is prepared by the following method, including the following steps:
A. swelling treatment: adding general chlorinated polyethylene, an initiator, a grafting monomer, a swelling agent and deionized water into a reactor in proportion for swelling treatment; the grafting monomer is maleic anhydride;
B. and (3) dispersion treatment: adding deionized water and a dispersing agent into the product obtained after the swelling treatment in the step A under the stirring state for dispersion treatment, then introducing nitrogen into the product, and heating for reaction to obtain a crude product of the modified chlorinated polyethylene;
C. and (3) purification treatment: extracting the crude product of the modified chlorinated polyethylene obtained in the step B, and then drying the extracted product to constant weight to obtain modified chlorinated polyethylene;
the weight ratio of the universal chlorinated polyethylene to the initiator, the grafting monomer, the swelling agent and the deionized water in the step A is (10-40): (0.03-0.5): (2-10): (5-20): 100, respectively;
and B, introducing nitrogen into the mixture obtained in the step B, heating the mixture to 55-90 ℃, reacting for 1-4 hours, carrying out suction filtration while the reaction is hot, precipitating and separating the product by using a precipitator during suction filtration, and then washing the product by using hot water to obtain a crude modified chlorinated polyethylene product, wherein the precipitator is ethanol.
2. The preparation process of the modified chlorinated polyethylene for rubber and plastic materials as claimed in claim 1, wherein the modified chlorinated polyethylene comprises the following steps: adding general chlorinated polyethylene, an initiator, a grafting monomer, a swelling agent and deionized water into a reactor in proportion, and swelling for 0.5-2.5h at 50-80 ℃.
3. The preparation process of the modified chlorinated polyethylene for rubber and plastic materials as claimed in claim 1, wherein the modified chlorinated polyethylene comprises the following steps: the initiator is benzoyl peroxide or dicumyl peroxide.
4. The preparation process of the modified chlorinated polyethylene for rubber and plastic materials as claimed in claim 1, wherein the modified chlorinated polyethylene comprises the following steps: the swelling agent is selected from one of toluene, xylene, ethyl acetate and solvent oil.
5. The preparation process of the modified chlorinated polyethylene for rubber and plastic materials as claimed in claim 1, wherein the modified chlorinated polyethylene comprises the following steps: the dispersing agent is selected from one of gelatin, polyvinyl alcohol, silicon dioxide and light calcium carbonate.
6. The preparation process of the modified chlorinated polyethylene for rubber and plastic materials as claimed in claim 1, wherein the modified chlorinated polyethylene comprises the following steps: during the extraction of the crude product of the modified chlorinated polyethylene, acetone is taken as a solvent and is put into a Soxhlet extractor for extraction for 0.5 to 2 hours.
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| CN107474192A (en) * | 2017-10-12 | 2017-12-15 | 沈阳化大高分子材料研发中心有限公司 | The production method of unsaturated acid anhydride Suspension Graft chlorinated polyethylene rubber |
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| CN112375326B (en) * | 2021-01-12 | 2021-03-16 | 潍坊硕邑化学有限公司 | Preparation method of chlorinated polyethylene with high elongation at break |
| CN112708028B (en) * | 2021-03-26 | 2021-06-29 | 山东昌泰高分子材料股份有限公司 | Impact modifier ACM resin and preparation process thereof |
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