CN114479295A - Chlorinated polyethylene rubber and preparation method thereof - Google Patents
Chlorinated polyethylene rubber and preparation method thereof Download PDFInfo
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- CN114479295A CN114479295A CN202210320991.6A CN202210320991A CN114479295A CN 114479295 A CN114479295 A CN 114479295A CN 202210320991 A CN202210320991 A CN 202210320991A CN 114479295 A CN114479295 A CN 114479295A
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- chlorinated polyethylene
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- 229920006235 chlorinated polyethylene elastomer Polymers 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 45
- 239000000203 mixture Substances 0.000 claims abstract description 43
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 239000002245 particle Substances 0.000 claims abstract description 28
- 239000004709 Chlorinated polyethylene Substances 0.000 claims abstract description 27
- 239000002131 composite material Substances 0.000 claims abstract description 27
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 26
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001506 calcium phosphate Substances 0.000 claims abstract description 13
- 239000003822 epoxy resin Substances 0.000 claims abstract description 13
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 13
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims abstract description 13
- 229940078499 tricalcium phosphate Drugs 0.000 claims abstract description 13
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims abstract description 13
- 235000019731 tricalcium phosphate Nutrition 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 67
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 52
- 238000002156 mixing Methods 0.000 claims description 30
- 238000000227 grinding Methods 0.000 claims description 26
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 26
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 20
- 229910044991 metal oxide Inorganic materials 0.000 claims description 20
- 150000004706 metal oxides Chemical class 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 229920001971 elastomer Polymers 0.000 claims description 17
- 239000005060 rubber Substances 0.000 claims description 16
- 230000002378 acidificating effect Effects 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 235000019441 ethanol Nutrition 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 239000006229 carbon black Substances 0.000 claims description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 11
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 239000000395 magnesium oxide Substances 0.000 claims description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 11
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- -1 aluminum silicon chloride Chemical compound 0.000 claims description 10
- 239000000919 ceramic Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 10
- 229940074439 potassium sodium tartrate Drugs 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 3
- 230000006835 compression Effects 0.000 abstract description 12
- 238000007906 compression Methods 0.000 abstract description 12
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 12
- 238000001704 evaporation Methods 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 239000003063 flame retardant Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 239000004636 vulcanized rubber 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
- 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
- 239000004698 Polyethylene Substances 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
- 150000001336 alkenes 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
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 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
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005604 random copolymer Polymers 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
- C08L23/286—Chlorinated polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/164—Aluminum halide, e.g. aluminium chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/325—Calcium, strontium or barium phosphate
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a chlorinated polyethylene rubber and a preparation method thereof, belonging to the field of compositions of high molecular compounds, wherein the chlorinated polyethylene rubber comprises the following components in parts by mass: 80-120 parts of chlorinated polyethylene powder, 8-12 parts of vinyl acetate, 20-30 parts of composite reinforcing particles, 1.8-2.2 parts of octamethylcyclotetrasiloxane, 2.5-3.5 parts of di-n-butyl phthalate, 4-6 parts of vulcanizing agent, 1.8-2.2 parts of tricalcium phosphate and 1.8-2.2 parts of epoxy resin. The chlorinated polyethylene rubber prepared by the invention has high tensile strength, and the tensile strength is 27.8-28.2 Mpa; the elongation at break is high and is 561-; good compression resistance, and compression set rate of 3.2-3.4%.
Description
Technical Field
The invention relates to a chlorinated polyethylene rubber and a preparation method thereof, belonging to the field of compositions of high molecular compounds.
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. They can be classified into general-purpose (modified) Chlorinated Polyethylene (CPE) and chlorinated polyethylene rubber (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.
Chlorinated polyethylene rubber (CM) is a product with the fastest increase of the use amount in synthetic rubber, is popular in the market due to heat resistance, oil resistance, cold resistance and flame retardant property, and can be applied to products such as automobile parts, acid/oil resistant rubber tubes, wires and cables, sponges, sealing elements, waterproof coiled materials, flame retardant rubber and the like.
The chlorinated polyethylene rubber needs to be vulcanized to improve the performance, has the characteristics of no stickiness, no easy breakage and the like after vulcanization, forms a spatial three-dimensional structure in raw rubber after vulcanization, and has higher elasticity, heat resistance, tensile strength, insolubility in an organic solvent and the like.
CN103880989A discloses a modified chlorinated polyethylene, a preparation method thereof, a chlorinated polyethylene vulcanized rubber and a preparation method thereof, which can make the prepared chlorinated polyethylene vulcanized rubber obtain better mechanical properties, wherein the highest tensile strength in the scheme can reach 26.5Mpa, but the elongation at break is only 323.5%, and when the tensile strength is 16.2Mpa, the elongation at break can reach 656.7%, so that the elongation at break is decreased instead with the increase of the tensile strength, and the tensile strength and the elongation at break of the material cannot be simultaneously increased, thereby limiting the application thereof.
CN108410075A discloses a new chlorinated polyethylene rubber composite material, and more particularly relates to a new chlorinated polyethylene rubber composite material for preparing sealing strips and a preparation method thereof.
In summary, the prior art has the following problems: the tensile strength and the elongation at break of the chlorinated polyethylene rubber cannot be improved simultaneously after the chlorinated polyethylene rubber is vulcanized.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects in the prior art, and the chlorinated polyethylene rubber is finally prepared by preparing the reinforcing particles and the vulcanizing agent, so that the tensile strength and the elongation at break of the chlorinated polyethylene rubber can be simultaneously improved.
In order to solve the technical problems, the invention adopts the following technical scheme:
the chlorinated polyethylene rubber comprises the following raw materials in parts by mass: 80-120 parts of chlorinated polyethylene powder, 8-12 parts of vinyl acetate, 20-30 parts of composite reinforcing particles, 1.8-2.2 parts of octamethylcyclotetrasiloxane, 2.5-3.5 parts of di-n-butyl phthalate, 4-6 parts of vulcanizing agent, 1.8-2.2 parts of tricalcium phosphate and 1.8-2.2 parts of epoxy resin.
The following is a further improvement of the above technical solution:
the chlorine content of the chlorinated polyethylene powder is 40-45%;
the preparation method of the composite reinforcing particles comprises the following steps:
heating acidic silica sol to 80-90 ℃, adding an aluminum chloride aqueous solution, keeping the temperature and stirring for 220min, adjusting the pH value to 4.3-4.7 to obtain aluminum silicon chloride sol for later use, roasting light calcium carbonate at the temperature of 380-450 ℃ for 150min, cooling and mixing with the aluminum silicon chloride sol, stirring at the temperature of 45-55 ℃ for 110-130min, heating at the constant temperature of 85-95 ℃ for 250min to obtain an initial mixture, putting the initial mixture into a grinder, adding grinding media anhydrous ethanol and ceramic grinding balls with the diameter of 0.4-0.6mm, grinding at the temperature of 100-150r/min for 100-150min, then adding carbon black, grinding at the temperature of 200-280r/min for 60-120min, discharging, and evaporating ethanol at the temperature of 60-80 ℃ to obtain composite reinforcing particles;
the mass ratio of the acidic silica sol to the aluminum chloride aqueous solution is 45-55: 1;
the mass concentration of the acidic silica sol is 25-35%;
the mass concentration of the aluminum chloride aqueous solution is 14-16%;
the mass ratio of the light calcium carbonate to the aluminum silicon chloride sol is 1: 28-32;
the mass ratio of the absolute ethyl alcohol to the primary mixture is 4.5-5.5: 2;
the mass ratio of the ceramic grinding balls with the diameter of 0.4-0.6mm to the primary mixture is 9-11: 1;
the mass ratio of the carbon black to the primary mixture is 3: 3.5-4.5.
The preparation method of the vulcanizing agent comprises the following steps:
mixing zinc oxide powder, magnesium oxide powder and absolute ethyl alcohol to obtain an ethanol solution of metal oxide, adding potassium sodium tartrate, stirring to uniformly disperse the ethanol solution, adjusting the pH to 8.3-8.7, heating to 70-80 ℃, keeping the temperature for 45-60min, filtering, washing and drying to obtain modified metal oxide mixture powder, mixing the modified metal oxide mixture powder with concentrated sulfuric acid, stirring to uniformly disperse, heating to 110-130 ℃, keeping the temperature for 50-70min, filtering, washing and drying to obtain a vulcanizing agent;
the mass ratio of the zinc oxide powder to the magnesium oxide powder to the absolute ethyl alcohol is 0.8-1.2:3.5-4.5: 45-55;
the mass ratio of the potassium sodium tartrate to the absolute ethyl alcohol is 1: 9-11;
the mass ratio of the modified metal oxide mixture powder to the concentrated sulfuric acid is 1: 9-11.
The preparation method of the chlorinated polyethylene rubber comprises the following steps:
mixing chlorinated polyethylene powder, vinyl acetate, composite reinforcing particles, octamethylcyclotetrasiloxane, di-n-butyl phthalate, a vulcanizing agent, tricalcium phosphate and epoxy resin, keeping the pressure at 1.0-1.2Mpa and the temperature at 75-85 ℃ for mixing for 18-22min, then increasing the pressure to 11-13Mpa within 25-35min, keeping the temperature at 95-105 ℃ for mixing for 90-110min to obtain a rubber material, extruding the rubber material, keeping the temperature at 280-320 ℃ for 25-35s, and cooling to obtain the chlorinated polyethylene rubber.
Compared with the prior art, the invention has the following beneficial effects:
the chlorinated polyethylene rubber prepared by the method has high tensile strength, and the tensile strength is 27.8-28.2 Mpa;
the chlorinated polyethylene rubber prepared by the invention has high elongation at break, and the elongation at break is 561-;
the chlorinated polyethylene rubber prepared by the invention has high tearing strength which is 62.9-63.8 kN/m;
the chlorinated polyethylene rubber prepared by the method has high hardness, and the Shore hardness is 77-78 degrees;
the chlorinated polyethylene rubber prepared by the invention has good compression resistance and compression set rate of 3.2-3.4% (GB/T7759.1-2015).
Detailed Description
Example 1 chlorinated polyethylene rubber and preparation method thereof
The chlorinated polyethylene rubber comprises the following raw materials in parts by mass: 100 parts of chlorinated polyethylene powder, 10 parts of vinyl acetate, 25 parts of composite reinforcing particles, 2 parts of octamethylcyclotetrasiloxane, 3 parts of di-n-butyl phthalate, 5 parts of vulcanizing agent, 2 parts of tricalcium phosphate and 2 parts of epoxy resin;
the chlorine content of the chlorinated polyethylene powder is 42%.
The preparation method of the composite reinforcing particles comprises the following steps:
heating acidic silica sol to 85 ℃, adding an aluminum chloride aqueous solution, keeping the temperature, stirring for 200min, adjusting the pH value to 4.5 to obtain aluminum chloride silica sol for later use, roasting light calcium carbonate at 400 ℃ for 120min, cooling, mixing with the aluminum chloride silica sol, stirring for 120min at 50 ℃, heating at 90 ℃ for 240min at constant temperature, losing all free water of the aluminum chloride silica sol to obtain a primary mixture, putting the primary mixture into a grinder, adding grinding media anhydrous ethanol and 0.5mm ceramic grinding balls, grinding for 120min at 120r/min, adding carbon black, grinding for 90min at 240r/min, discharging, and evaporating ethanol at 70 ℃ to obtain composite reinforcing particles;
the mass ratio of the acidic silica sol to the aluminum chloride aqueous solution is 50: 1;
the mass concentration of the acidic silica sol is 30 percent;
the mass concentration of the aluminum chloride aqueous solution is 15%;
the mass ratio of the light calcium carbonate to the aluminum silicon chloride sol is 1: 30;
the mass ratio of the absolute ethyl alcohol to the primary mixture is 5: 2;
the mass ratio of the ceramic grinding balls with the diameter of 0.5mm to the primary mixture is 10: 1;
the mass ratio of the carbon black to the primary mixture is 3:4.
The preparation method of the vulcanizing agent comprises the following steps:
mixing zinc oxide powder, magnesium oxide powder and absolute ethyl alcohol to obtain an ethanol solution of metal oxide, adding potassium sodium tartrate, stirring to uniformly disperse the ethanol solution, adjusting the pH to 8.5, heating to 75 ℃ and keeping the temperature for 50min, filtering, washing and drying to obtain modified metal oxide mixture powder, mixing the modified metal oxide mixture powder with concentrated sulfuric acid, stirring to uniformly disperse, heating to 120 ℃ and keeping the temperature for 60min, filtering, washing and drying to obtain a vulcanizing agent;
the mass ratio of the zinc oxide powder to the magnesium oxide powder to the absolute ethyl alcohol is 1:4: 50;
the mass ratio of the potassium sodium tartrate to the absolute ethyl alcohol is 1: 10;
the mass ratio of the modified metal oxide mixture powder to concentrated sulfuric acid is 1: 10.
The preparation method of the chlorinated polyethylene rubber comprises the following steps:
mixing chlorinated polyethylene powder, vinyl acetate, composite reinforcing particles, octamethylcyclotetrasiloxane, di-n-butyl phthalate, a vulcanizing agent, tricalcium phosphate and epoxy resin, putting into an internal mixer, keeping the pressure at 1.1Mpa and the temperature at 80 ℃ for mixing for 20min, then increasing the pressure to 12Mpa within 30min, keeping the temperature at 100 ℃ for mixing for 100min to obtain a rubber material, extruding the rubber material by an extruder according to needs, keeping the temperature at 300 ℃ for 30s, further vulcanizing the surface, cooling and packaging to obtain the chlorinated polyethylene rubber.
The chlorinated polyethylene rubber prepared in the example 1 has high tensile strength, and the tensile strength is 28.2 MPa;
the chlorinated polyethylene rubber prepared in example 1 has high elongation at break, and the elongation at break is 573%;
the chlorinated polyethylene rubber prepared in the example 1 has high tear strength, and the tear strength is 63.8 kN/m;
the chlorinated polyethylene rubber prepared in example 1 has high hardness, and the Shore hardness is 78 degrees;
the chlorinated polyethylene rubber prepared in example 1 has good compression resistance and a compression set of 3.2% (GB/T7759.1-2015).
Example 2 chlorinated polyethylene rubber and preparation method thereof
The chlorinated polyethylene rubber comprises the following raw materials in parts by mass: 80 parts of chlorinated polyethylene powder, 8 parts of vinyl acetate, 20 parts of composite reinforcing particles, 1.8 parts of octamethylcyclotetrasiloxane, 2.5 parts of di-n-butyl phthalate, 4 parts of vulcanizing agent, 1.8 parts of tricalcium phosphate and 1.8 parts of epoxy resin;
the chlorine content of the chlorinated polyethylene powder is 40%.
The preparation method of the composite reinforcing particles comprises the following steps:
heating acidic silica sol to 80 ℃, adding an aluminum chloride aqueous solution, keeping the temperature, stirring for 220min, adjusting the pH value to 4.3 to obtain aluminum chloride silica sol for later use, roasting light calcium carbonate at 380 ℃ for 150min, cooling, mixing with the aluminum chloride silica sol, stirring for 130min at 45 ℃, heating at 85 ℃ for 250min at constant temperature, wherein free water of the aluminum chloride silica sol is completely lost to obtain a primary mixture, putting the primary mixture into a grinder, adding grinding media anhydrous ethanol and 0.4mm ceramic grinding balls, grinding for 150min at 100r/min, adding carbon black, grinding for 120min at 200r/min, discharging, and evaporating ethanol at 60 ℃ to obtain composite reinforcing particles;
the mass ratio of the acidic silica sol to the aluminum chloride aqueous solution is 45: 1;
the mass concentration of the acidic silica sol is 25%;
the mass concentration of the aluminum chloride aqueous solution is 14%;
the mass ratio of the light calcium carbonate to the aluminum silicon chloride sol is 1: 28;
the mass ratio of the absolute ethyl alcohol to the primary mixture is 4.5: 2;
the mass ratio of the ceramic grinding balls with the diameter of 0.4mm to the primary mixture is 9: 1;
the mass ratio of the carbon black to the primary mixture is 3: 3.5.
The preparation method of the vulcanizing agent comprises the following steps:
mixing zinc oxide powder, magnesium oxide powder and absolute ethyl alcohol to obtain an ethanol solution of metal oxide, adding potassium sodium tartrate, stirring to uniformly disperse the ethanol solution, adjusting the pH to 8.3, heating to 70 ℃ and keeping for 60min, filtering, washing and drying to obtain modified metal oxide mixture powder, mixing the modified metal oxide mixture powder with concentrated sulfuric acid, stirring to uniformly disperse, heating to 110 ℃ and keeping for 70min, filtering, washing and drying to obtain a vulcanizing agent;
the mass ratio of the zinc oxide powder to the magnesium oxide powder to the absolute ethyl alcohol is 0.8:3.5: 45;
the mass ratio of the potassium sodium tartrate to the absolute ethyl alcohol is 1: 9;
the mass ratio of the modified metal oxide mixture powder to concentrated sulfuric acid is 1: 9.
The preparation method of the chlorinated polyethylene rubber comprises the following steps:
mixing chlorinated polyethylene powder, vinyl acetate, composite reinforcing particles, octamethylcyclotetrasiloxane, di-n-butyl phthalate, a vulcanizing agent, tricalcium phosphate and epoxy resin, putting into an internal mixer, keeping the pressure at 1.0Mpa and the temperature at 85 ℃ for mixing for 18min, then increasing the pressure to 11Mpa within 25min, keeping the temperature at 95 ℃ for mixing for 110min to obtain a rubber material, extruding the rubber material by an extruder according to needs, keeping the temperature at 280 ℃ for 35s, further vulcanizing the surface, cooling and packaging to obtain the chlorinated polyethylene rubber.
The chlorinated polyethylene rubber prepared in the embodiment 2 has high tensile strength, and the tensile strength is 28.1 MPa;
the chlorinated polyethylene rubber prepared in example 2 has high elongation at break, and the elongation at break is 561%;
the chlorinated polyethylene rubber prepared in the example 2 has high tear strength, and the tear strength is 62.9 kN/m;
the chlorinated polyethylene rubber prepared in the example 2 has high hardness, and the Shore hardness is 77 degrees;
the chlorinated polyethylene rubber prepared in example 2 has good compression resistance and a compression set of 3.3% (GB/T7759.1-2015).
Example 3 chlorinated polyethylene rubber and preparation method thereof
The chlorinated polyethylene rubber comprises the following raw materials in parts by mass: 120 parts of chlorinated polyethylene powder, 12 parts of vinyl acetate, 30 parts of composite reinforcing particles, 2.2 parts of octamethylcyclotetrasiloxane, 3.5 parts of di-n-butyl phthalate, 6 parts of vulcanizing agent, 2.2 parts of tricalcium phosphate and 2.2 parts of epoxy resin;
the chlorine content of the chlorinated polyethylene powder is 45%.
The preparation method of the composite reinforcing particles comprises the following steps:
heating acidic silica sol to 90 ℃, adding an aluminum chloride aqueous solution, keeping the temperature, stirring for 180min, adjusting the pH value to 4.7 to obtain aluminum chloride silica sol for later use, roasting light calcium carbonate at 450 ℃ for 100min, cooling, mixing with the aluminum chloride silica sol, stirring for 110min at 55 ℃, heating at 95 ℃ for 230min at constant temperature, wherein free water of the aluminum chloride silica sol is completely lost to obtain a primary mixture, putting the primary mixture into a grinder, adding grinding media anhydrous ethanol and 0.6mm ceramic grinding balls, grinding at 150r/min for 100min, adding carbon black, grinding at 280r/min for 60min, discharging, and evaporating ethanol at 80 ℃ to obtain composite reinforcing particles;
the mass ratio of the acidic silica sol to the aluminum chloride aqueous solution is 55: 1;
the mass concentration of the acidic silica sol is 35 percent;
the mass concentration of the aluminum chloride aqueous solution is 16%;
the mass ratio of the light calcium carbonate to the aluminum silicon chloride sol is 1: 32;
the mass ratio of the absolute ethyl alcohol to the primary mixture is 5.5: 2;
the mass ratio of the ceramic grinding balls with the diameter of 0.6mm to the primary mixture is 11: 1;
the mass ratio of the carbon black to the primary mixture is 3: 4.5.
The preparation method of the vulcanizing agent comprises the following steps:
mixing zinc oxide powder, magnesium oxide powder and absolute ethyl alcohol to obtain an ethanol solution of metal oxide, adding potassium sodium tartrate, stirring to uniformly disperse the ethanol solution, adjusting the pH to 8.7, heating to 80 ℃ and keeping for 45min, filtering, washing and drying to obtain modified metal oxide mixture powder, mixing the modified metal oxide mixture powder with concentrated sulfuric acid, stirring to uniformly disperse, heating to 130 ℃ and keeping for 50min, filtering, washing and drying to obtain a vulcanizing agent;
the mass ratio of the zinc oxide powder to the magnesium oxide powder to the absolute ethyl alcohol is 1.2:4.5: 55;
the mass ratio of the potassium sodium tartrate to the absolute ethyl alcohol is 1: 11;
the mass ratio of the modified metal oxide mixture powder to concentrated sulfuric acid is 1: 11.
The preparation method of the chlorinated polyethylene rubber comprises the following steps:
mixing chlorinated polyethylene powder, vinyl acetate, composite reinforcing particles, octamethylcyclotetrasiloxane, di-n-butyl phthalate, a vulcanizing agent, tricalcium phosphate and epoxy resin, putting into an internal mixer, keeping the pressure at 1.2Mpa and the temperature at 75 ℃ for mixing for 22min, then increasing the pressure to 13Mpa within 35min, keeping the temperature at 105 ℃ for mixing for 90min to obtain a rubber material, extruding the rubber material by an extruder according to needs, keeping the temperature at 320 ℃ for 25s, further vulcanizing the surface, cooling and packaging to obtain the chlorinated polyethylene rubber.
The chlorinated polyethylene rubber prepared in example 3 has high tensile strength, and the tensile strength is 27.8 MPa;
the chlorinated polyethylene rubber prepared in example 3 has high elongation at break, which is 566%;
the chlorinated polyethylene rubber prepared in example 3 has high tear strength, and the tear strength is 63.2 kN/m;
the chlorinated polyethylene rubber prepared in example 3 has high hardness, and the shore hardness is 78 degrees;
the chlorinated polyethylene rubber prepared in example 3 has good compression resistance and a compression set of 3.4% (GB/T7759.1-2015).
Comparative example 1
On the basis of the example 1, carbon black particles are used in the raw materials to replace composite reinforcing particles, and the rest steps are the same, so that chlorinated polyethylene rubber is prepared;
the chlorinated polyethylene rubber comprises the following raw materials in parts by mass: 100 parts of chlorinated polyethylene powder, 10 parts of vinyl acetate, 25 parts of carbon black particles, 2 parts of octamethylcyclotetrasiloxane, 3 parts of di-n-butyl phthalate, 5 parts of vulcanizing agent, 2 parts of tricalcium phosphate and 2 parts of epoxy resin.
The tensile strength of the chlorinated polyethylene rubber prepared in the comparative example 1 is 23.9 Mpa;
the elongation at break of the chlorinated polyethylene rubber prepared in comparative example 1 was 542%;
the chlorinated polyethylene rubber prepared in comparative example 1 had a tear strength of 59.2 kN/m;
the shore hardness of the chlorinated polyethylene rubber prepared in comparative example 1 is 72 degrees;
the chlorinated polyethylene rubber prepared in comparative example 1 had a compression set of 4.5% (GB/T7759).
Comparative example 2
On the basis of the example 1, a mixture is formed by using a combined vulcanizing agent instead of a vulcanizing agent in the raw materials, and the rest steps are the same, so that chlorinated polyethylene rubber is prepared;
the combined vulcanizing agent consists of zinc oxide powder and magnesium oxide powder in a mass ratio of 1: 4;
the chlorinated polyethylene rubber comprises the following raw materials in parts by mass: 100 parts of chlorinated polyethylene powder, 10 parts of vinyl acetate, 25 parts of composite reinforcing particles, 2 parts of octamethylcyclotetrasiloxane, 3 parts of di-n-butyl phthalate, 5 parts of combined vulcanizing agent, 2 parts of tricalcium phosphate and 2 parts of epoxy resin.
The tensile strength of the chlorinated polyethylene rubber prepared in the comparative example 2 is 25.3 Mpa;
the elongation at break of the chlorinated polyethylene rubber prepared in comparative example 2 was 487%;
the chlorinated polyethylene rubber prepared in comparative example 2 had a tear strength of 61.2 kN/m;
the shore hardness of the chlorinated polyethylene rubber prepared in comparative example 2 is 74 degrees;
the chlorinated polyethylene rubber prepared in comparative example 2 had a compression set of 3.6% (GB/T7759).
Claims (7)
1. The chlorinated polyethylene rubber is characterized by comprising the following raw materials in parts by mass: 80-120 parts of chlorinated polyethylene powder, 8-12 parts of vinyl acetate, 20-30 parts of composite reinforcing particles, 1.8-2.2 parts of octamethylcyclotetrasiloxane, 2.5-3.5 parts of di-n-butyl phthalate, 4-6 parts of vulcanizing agent, 1.8-2.2 parts of tricalcium phosphate and 1.8-2.2 parts of epoxy resin;
the preparation method of the composite reinforcing particles comprises the steps of roasting light calcium carbonate at the temperature of 380-450 ℃ for 150-one, mixing and stirring the light calcium carbonate with aluminum silicon chloride sol for 110-one 130-one after cooling, heating at the constant temperature of 85-95 ℃ for 230-one 250-one to obtain a primary mixture, grinding the primary mixture, adding a grinding medium absolute ethyl alcohol and a ceramic grinding ball with the diameter of 0.4-0.6mm, grinding at the temperature of 100-one 150r/min for 150-one, then adding carbon black, grinding at the temperature of 200-one 280r/min for 60-120min, discharging and drying to obtain the composite reinforcing particles;
the preparation method of the vulcanizing agent comprises the steps of mixing zinc oxide powder, magnesium oxide powder and absolute ethyl alcohol to obtain an ethanol solution of metal oxide, adding potassium sodium tartrate, stirring to uniformly disperse the ethanol solution, adjusting the pH value to 8.3-8.7, heating to 70-80 ℃, keeping for 45-60min, filtering, washing and drying to obtain modified metal oxide mixture powder, mixing the modified metal oxide mixture powder with concentrated sulfuric acid, stirring to uniformly disperse, heating to 110-130 ℃, keeping for 50-70min, filtering, washing and drying to obtain the vulcanizing agent.
2. A chlorinated polyethylene rubber according to claim 1, characterized in that:
the chlorine content of the chlorinated polyethylene powder in the raw material of the chlorinated polyethylene rubber is 40-45%.
3. A chlorinated polyethylene rubber according to claim 1, characterized in that:
in the preparation method of the composite reinforcing particle, the preparation method of the aluminum silicon chloride sol comprises the steps of heating the acidic silica sol to 80-90 ℃, adding an aluminum chloride aqueous solution, keeping the temperature, stirring for 180-fold for 220min, and adjusting the pH value to 4.3-4.7 to obtain the aluminum silicon chloride sol.
4. A chlorinated polyethylene rubber according to claim 3, wherein:
in the preparation method of the aluminum chloride silica sol, the mass ratio of the acidic silica sol to the aluminum chloride aqueous solution is 45-55:1, the mass concentration of the acidic silica sol is 25-35%, and the mass concentration of the aluminum chloride aqueous solution is 14-16%.
5. A chlorinated polyethylene rubber according to claim 1, characterized in that:
in the preparation method of the composite reinforcing particles, the mass ratio of the light calcium carbonate to the aluminum chloride silica sol is 1:28-32, the mass ratio of the absolute ethyl alcohol to the primary mixture is 4.5-5.5:2, the mass ratio of the ceramic grinding balls with the diameter of 0.4-0.6mm to the primary mixture is 9-11:1, and the mass ratio of the carbon black to the primary mixture is 3: 3.5-4.5.
6. A chlorinated polyethylene rubber according to claim 1, characterized in that:
in the preparation method of the vulcanizing agent, the mass ratio of the zinc oxide powder to the magnesium oxide powder to the absolute ethyl alcohol is 0.8-1.2:3.5-4.5:45-55, the mass ratio of the potassium sodium tartrate to the absolute ethyl alcohol is 1:9-11, and the mass ratio of the modified metal oxide mixture powder to the concentrated sulfuric acid is 1: 9-11.
7. A process for producing a chlorinated polyethylene rubber according to claim 1, characterized in that:
mixing chlorinated polyethylene powder, vinyl acetate, composite reinforcing particles, octamethylcyclotetrasiloxane, di-n-butyl phthalate, a vulcanizing agent, tricalcium phosphate and epoxy resin, keeping the pressure at 1.0-1.2Mpa and the temperature at 75-85 ℃ for mixing for 18-22min, then increasing the pressure to 11-13Mpa within 25-35min, keeping the temperature at 95-105 ℃ for mixing for 90-110min to obtain a rubber material, extruding the rubber material, keeping the temperature at 280-320 ℃ for 25-35s, and cooling to obtain the chlorinated polyethylene rubber.
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| CN116120674A (en) * | 2023-04-14 | 2023-05-16 | 潍坊硕邑化学有限公司 | Flame-retardant wear-resistant chlorinated polyethylene rubber composition and preparation method thereof |
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Denomination of invention: A chlorinated polyethylene rubber and its preparation method Effective date of registration: 20230301 Granted publication date: 20220617 Pledgee: Postal Savings Bank of China Limited by Share Ltd. Weifang branch Pledgor: WEIFANG POLYGRAND CHEMICAL CO.,LTD. Registration number: Y2023980033789 |