CN116120674A - Flame-retardant wear-resistant chlorinated polyethylene rubber composition and preparation method thereof - Google Patents
Flame-retardant wear-resistant chlorinated polyethylene rubber composition and preparation method thereof Download PDFInfo
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- 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 compounds containing halogen
- C08L23/286—Chlorinated polyethylene
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- 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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention discloses a flame-retardant wear-resistant chlorinated polyethylene rubber composition and a preparation method thereof, belonging to the technical field of chlorinated polyethylene rubber compositions, wherein the flame-retardant wear-resistant chlorinated polyethylene rubber composition comprises the following components in parts by weight: 100-105 parts of chlorinated polyethylene powder, 10-12 parts of ultrafine colloid particles, 5-8 parts of white carbon black, 5-7 parts of dioctyl phthalate, 5-6 parts of composite vulcanizing agent, 3-5 parts of antimonous oxide, 3-4 parts of calcium stearate, 2-3 parts of octamethyl cyclotetrasiloxane, 1-2 parts of methyl methacrylate, 1-1.5 parts of paraffin wax, 1-1.2 parts of tricalcium phosphate and 0.5-1 part of stearic acid; the flame-retardant wear-resistant chlorinated polyethylene rubber composition prepared by the invention has good elasticity and compression resistance, high electrical insulation property, high tearing strength, good flex crack resistance, ozone resistance, weather resistance, flame retardance and wear resistance, and is not easy to agglomerate during mixing.
Description
Technical Field
The invention relates to the technical field of chlorinated polyethylene rubber compositions, in particular to a flame-retardant wear-resistant chlorinated polyethylene rubber composition and a preparation method thereof.
Background
The chlorinated polyethylene rubber is random chloride prepared by the chlorine substitution reaction of polyethylene, has the characteristics of excellent ozone resistance, weather resistance, chemical resistance, oil resistance, flame retardance and the like, has good mechanical properties such as flexibility resistance, wear resistance and the like, is commonly used for preparing chemical resistant rubber rolls, wires, model products and other industrial products, but has poor elasticity and compression resistance and lower electrical insulation, and limits the application range of the chlorinated polyethylene rubber.
In order to solve the above problems, the most commonly used method is to vulcanize chlorinated polyethylene rubber, to which nanofiller is added and blended with other rubber, but vulcanization reduces the tear strength and flex crack resistance of the chlorinated polyethylene rubber; the added nano filler is easy to agglomerate during mixing, and the addition of the nano filler can also influence the ozone resistance and weather resistance of the chlorinated polyethylene rubber; blending with other rubbers can affect the flame retardancy and abrasion resistance of chlorinated polyethylene rubbers.
Chinese patent CN102850676B discloses a chlorinated polyethylene rubber composite material for a food conveyor belt, which is prepared from the following raw materials in parts by weight: 80-120 parts of chlorinated polyethylene rubber, 5-15 parts of magnesium oxide, 15-30 parts of white carbon black, 0.5-3 parts of silane coupling agent, 10-50 parts of superfine calcium carbonate, 1-5 parts of titanium dioxide, 10-20 parts of plasticizer, 5-15 parts of white oil, 2-10 parts of organic peroxide vulcanizing agent, 1.5-3.0 parts of vulcanizing aid and 1-10 parts of rubber and plastic deodorant; the prepared chlorinated polyethylene rubber composite material has high tensile strength and elongation at break, but poor elasticity and compression resistance.
Chinese patent CN114479295B discloses a chlorinated polyethylene rubber and a preparation method thereof, the chlorinated polyethylene rubber is prepared from the following raw materials in parts by weight: 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 octamethyl cyclotetrasiloxane, 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 prepared chlorinated polyethylene rubber has high tensile strength and elongation at break and good compression resistance, but has poor tearing strength and flex crack resistance.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a flame-retardant wear-resistant chlorinated polyethylene rubber composition and a preparation method thereof, and the prepared flame-retardant wear-resistant chlorinated polyethylene rubber composition has good elasticity and compression resistance, high electrical insulation property, high tear strength, good flex crack resistance, ozone resistance, weather resistance, flame retardance and wear resistance, and is not easy to agglomerate during mixing.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the flame-retardant wear-resistant chlorinated polyethylene rubber composition comprises the following components in parts by weight: 100-105 parts of chlorinated polyethylene powder, 10-12 parts of ultrafine colloid particles, 5-8 parts of white carbon black, 5-7 parts of dioctyl phthalate, 5-6 parts of composite vulcanizing agent, 3-5 parts of antimonous oxide, 3-4 parts of calcium stearate, 2-3 parts of octamethyl cyclotetrasiloxane, 1-2 parts of methyl methacrylate, 1-1.5 parts of paraffin wax, 1-1.2 parts of tricalcium phosphate and 0.5-1 part of stearic acid;
the chlorine content of the chlorinated polyethylene powder is 40-42%;
the preparation method of the ultrafine colloidal particles comprises the following steps: mixing kaolin and expanded perlite powder according to a weight ratio of 10:1-2, performing ball milling, controlling a ball-material ratio during ball milling to be 18-20:1, rotating at 300-320rpm for 40-45min, obtaining mixed powder after ball milling, adding the mixed powder into deionized water with a weight ratio of 7-8 times that of the mixed powder, performing ultrasonic vibration, controlling the frequency of ultrasonic vibration to be 30-40kHz, controlling the time to be 15-20min, and obtaining mixed powder suspension aqueous solution after ultrasonic vibration; adding sodium alginate into deionized water of which the weight is 28-30 times that of the sodium alginate, performing ultrasonic oscillation, controlling the frequency of the ultrasonic oscillation to be 30-40kHz and the time to be 10-12min, and obtaining sodium alginate aqueous solution after the ultrasonic oscillation is finished; adding the mixed powder suspension aqueous solution into a reaction kettle, controlling the temperature of the reaction kettle to 40-45 ℃, starting stirring, controlling the stirring speed to 60-80rpm, dripping sodium alginate aqueous solution into the reaction kettle, controlling the dripping speed of the sodium alginate aqueous solution to 30-35g/min, continuously stirring for 10-12min after dripping, adding citric acid, continuously stirring for 10-12min, adding glutaraldehyde, continuously stirring for 25-30min, performing ultraviolet irradiation, controlling the ultraviolet wavelength during ultraviolet irradiation to 200-230nm for 1.5-2h, adding methanol after ultraviolet irradiation is finished, continuously stirring for 15-20min, filtering, and drying filter residues at 110-120 ℃ to obtain ultrafine colloid particles;
in the preparation of the ultrafine colloidal particles, the weight ratio of the mixed powder suspension aqueous solution to the sodium alginate aqueous solution to the citric acid to the glutaraldehyde to the methanol is 100-105:500-520:4-6:1-1.5:500-550;
the preparation method of the composite vulcanizing agent comprises the following steps: mixing nano calcium carbonate, triethyl citrate and sodium dodecyl sulfate, performing ball milling, controlling the ball-material ratio during ball milling to be 15-18:1, the rotating speed to be 300-320rpm, adding zinc methacrylate and sodium hexametaphosphate after ball milling for 20-25min, continuing ball milling for 20-25min to obtain ball grinding materials, and mixing the ball grinding materials with tert-butyl hydroperoxide to obtain a compound vulcanizing agent;
in the preparation of the composite vulcanizing agent, the weight ratio of nano calcium carbonate to triethyl citrate to sodium dodecyl sulfate to zinc methacrylate to sodium hexametaphosphate to t-butyl hydroperoxide is 10-12:0.5-1:0.3-0.5:20-24:4-6:100-105;
in the preparation of the composite vulcanizing agent, the particle size of the nano calcium carbonate is 50-100nm.
The preparation method of the flame-retardant wear-resistant chlorinated polyethylene rubber composition comprises the steps of mixing chlorinated polyethylene powder, ultrafine colloid particles, white carbon black, dioctyl phthalate, antimonous oxide, calcium stearate, octamethyl cyclotetrasiloxane, methyl methacrylate, paraffin, tricalcium phosphate and stearic acid, adding the mixture into a mixer, stirring for 15-20min at 300-320rpm, adding the mixture into the mixer for primary mixing, controlling the pressure during primary mixing to be 2-2.5MPa, controlling the temperature to be 80-85 ℃ for 15-20min, then uniformly increasing the temperature to be 110-115 ℃ within 20-25min, uniformly increasing the pressure to be 10-11MPa, performing secondary mixing, controlling the time during secondary mixing to be 80-90min, and obtaining a mixed material after the secondary mixing is finished; adding a composite vulcanizing agent into the mixed materials, stirring for 4-6min at 300-320rpm, vulcanizing, controlling the pressure at 5-6MPa during vulcanization and the temperature at 140-150 ℃, and obtaining the flame-retardant wear-resistant chlorinated polyethylene rubber composition after vulcanization.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, the elasticity can be improved by adding the ultrafine colloid particles into the flame-retardant wear-resistant chlorinated polyethylene rubber composition, the tensile strength of the flame-retardant wear-resistant chlorinated polyethylene rubber composition is 26.1-26.6MPa, and the elongation at break is 554-567%;
(2) According to the invention, the compression resistance can be improved by adding the ultrafine colloid particles into the flame-retardant wear-resistant chlorinated polyethylene rubber composition, and the compression set of the flame-retardant wear-resistant chlorinated polyethylene rubber composition is 3.6-4.1%;
(3) The invention can improve the electrical insulation property by adding the composite vulcanizing agent into the flame-retardant wear-resistant chlorinated polyethylene rubber composition, and the volume resistivity of the flame-retardant wear-resistant chlorinated polyethylene rubber composition is 3.23 multiplied by 10 16 -3.31×10 16 Ω·cm；
(4) The invention can improve the tearing strength by adding the composite vulcanizing agent into the flame-retardant wear-resistant chlorinated polyethylene rubber composition, and the tearing strength of the flame-retardant wear-resistant chlorinated polyethylene rubber composition is 64.7-65.2kN/m;
(5) According to the invention, the flex crack resistance can be improved by adding the composite vulcanizing agent into the flame-retardant wear-resistant chlorinated polyethylene rubber composition, and the flame-retardant wear-resistant chlorinated polyethylene rubber composition has no crack after 4 ten thousands of flex cracks are resisted;
(6) According to the invention, the ozone resistance can be improved by adding the composite vulcanizing agent into the flame-retardant wear-resistant chlorinated polyethylene rubber composition, and the flame-retardant wear-resistant chlorinated polyethylene rubber composition disclosed by the invention is free from fracture after being subjected to ozone resistance of 500pphm multiplied by 20% multiplied by 168 hours;
(7) According to the invention, the composite vulcanizing agent is added into the flame-retardant wear-resistant chlorinated polyethylene rubber composition, so that the flame retardance is improved, and the oxygen index of the flame-retardant wear-resistant chlorinated polyethylene rubber composition is 42-45;
(8) The wear-resistant performance can be improved by adding the ultrafine colloidal particles into the flame-retardant wear-resistant chlorinated polyethylene rubber composition, and the wear-resistant performance of the flame-retardant wear-resistant chlorinated polyethylene rubber composition is 0.24-0.28cm 3 ；
(9) According to the invention, the weather resistance can be improved by adding the composite vulcanizing agent into the flame-retardant wear-resistant chlorinated polyethylene rubber composition, the flame-retardant wear-resistant chlorinated polyethylene rubber composition is placed at the temperature of minus 30 ℃ for 10d, placed at the temperature of 40 ℃ for 10d, and continuously irradiated for 10d under a 500W xenon lamp, wherein the tensile strength is 25.7-26.4MPa, the elongation at break is 550-564%, the compression set is 3.8-4.3%, and the tearing strength is 64.4-65.0kN/m;
(10) According to the invention, the nano calcium carbonate and the tert-butyl hydroperoxide are prepared into the composite vulcanizing agent, so that agglomeration in mixing can be avoided.
Detailed Description
Specific embodiments of the present invention will now be described in order to provide a clearer understanding of the technical features, objects and effects of the present invention.
Example 1
The flame-retardant wear-resistant chlorinated polyethylene rubber composition comprises the following components in parts by weight: 100 parts of chlorinated polyethylene powder, 10 parts of ultrafine colloid particles, 5 parts of white carbon black, 5 parts of dioctyl phthalate, 5 parts of composite vulcanizing agent, 3 parts of antimonous oxide, 3 parts of calcium stearate, 2 parts of octamethyl cyclotetrasiloxane, 1 part of methyl methacrylate, 1 part of paraffin, 1 part of tricalcium phosphate and 0.5 part of stearic acid;
the chlorine content of the chlorinated polyethylene powder is 40%;
the preparation method of the ultrafine colloidal particles comprises the following steps: mixing kaolin and expanded perlite powder according to a weight ratio of 10:1, performing ball milling, controlling a ball-material ratio during ball milling to be 18:1, controlling a rotating speed to be 300rpm and a time to be 40 minutes, obtaining mixed powder after ball milling, adding the mixed powder into deionized water with a weight ratio of 7 times that of the mixed powder, performing ultrasonic vibration, controlling the frequency of ultrasonic vibration to be 30kHz and the time to be 15 minutes, and obtaining mixed powder suspension aqueous solution after ultrasonic vibration; adding sodium alginate into deionized water of which the weight is 28 times that of the sodium alginate, carrying out ultrasonic oscillation, controlling the frequency of the ultrasonic oscillation to be 30kHz and the time to be 10 minutes, and obtaining sodium alginate aqueous solution after the ultrasonic oscillation is finished; adding the mixed powder suspension aqueous solution into a reaction kettle, controlling the temperature of the reaction kettle to 40 ℃, starting stirring, controlling the stirring speed to 60rpm, dripping sodium alginate aqueous solution into the reaction kettle, controlling the dripping speed of the sodium alginate aqueous solution to 30g/min, continuing stirring for 10min after dripping, adding citric acid, continuing stirring for 10min, adding glutaraldehyde, continuing stirring for 25min, then performing ultraviolet irradiation, controlling the ultraviolet wavelength during ultraviolet irradiation to be 200nm, controlling the time to be 1.5h, adding methanol after ultraviolet irradiation is finished, continuing stirring for 15min, filtering, and drying filter residues at 110 ℃ to obtain ultrafine colloid particles;
the weight ratio of the mixed powder suspension aqueous solution to the sodium alginate aqueous solution to the citric acid to the glutaraldehyde to the methanol is 100:500:4:1:500;
the preparation method of the composite vulcanizing agent comprises the following steps: mixing nano calcium carbonate, triethyl citrate and sodium dodecyl sulfate, performing ball milling, controlling the ball-material ratio during ball milling to be 15:1, the rotating speed to be 300rpm, adding zinc methacrylate and sodium hexametaphosphate after ball milling for 20min, continuing ball milling for 20min to obtain ball grinding materials, and mixing the ball grinding materials with tert-butyl hydroperoxide to obtain the composite vulcanizing agent;
the weight ratio of the nano calcium carbonate to the triethyl citrate to the sodium dodecyl sulfate to the zinc methacrylate to the sodium hexametaphosphate to the tert-butyl hydroperoxide is 10:0.5:0.3:20:4:100;
the particle size of the nano calcium carbonate is 50nm.
A preparation method of a flame-retardant wear-resistant chlorinated polyethylene rubber composition specifically comprises the following steps: mixing chlorinated polyethylene powder, ultrafine colloid particles, white carbon black, dioctyl phthalate, antimonous oxide, calcium stearate, octamethyl cyclotetrasiloxane, methyl methacrylate, paraffin, tricalcium phosphate and stearic acid, adding into a mixer, stirring for 15min at 300rpm, adding into a mixer for primary mixing, controlling the pressure at 2MPa during primary mixing at 80 ℃ for 15min, then uniformly increasing the temperature to 110 ℃ within 20min, uniformly increasing the pressure to 10MPa, performing secondary mixing, controlling the time at 80min during secondary mixing, and obtaining a mixed material after the secondary mixing is finished; and adding a composite vulcanizing agent into the mixed materials, stirring for 4min at 300rpm, vulcanizing, controlling the pressure at 5MPa and the temperature at 140 ℃ during vulcanization, and obtaining the flame-retardant wear-resistant chlorinated polyethylene rubber composition after vulcanization.
This example shows no agglomeration during kneading.
Example 2
The flame-retardant wear-resistant chlorinated polyethylene rubber composition comprises the following components in parts by weight: 102 parts of chlorinated polyethylene powder, 11 parts of ultrafine colloidal particles, 6 parts of white carbon black, 6 parts of dioctyl phthalate, 5.5 parts of composite vulcanizing agent, 4 parts of antimonous oxide, 3.5 parts of calcium stearate, 2.5 parts of octamethyl cyclotetrasiloxane, 1.5 parts of methyl methacrylate, 1.2 parts of paraffin, 1.1 parts of tricalcium phosphate and 0.8 part of stearic acid;
the chlorine content of the chlorinated polyethylene powder is 41%;
the preparation method of the ultrafine colloidal particles comprises the following steps: mixing kaolin and expanded perlite powder according to a weight ratio of 10:1.5, performing ball milling, controlling a ball-material ratio during ball milling to be 19:1, rotating at 310rpm for 42min, obtaining mixed powder after ball milling, adding the mixed powder into deionized water with a weight ratio of 7.5 times that of the mixed powder, performing ultrasonic vibration, controlling the frequency of ultrasonic vibration to be 35kHz, and obtaining mixed powder turbid aqueous solution after ultrasonic vibration; adding sodium alginate into 29 times of deionized water in parts by weight, performing ultrasonic oscillation, controlling the frequency of the ultrasonic oscillation to be 35kHz and the time to be 11 minutes, and obtaining sodium alginate aqueous solution after the ultrasonic oscillation is finished; adding the mixed powder suspension aqueous solution into a reaction kettle, controlling the temperature of the reaction kettle to 42 ℃, starting stirring, controlling the stirring speed to 70rpm, dripping sodium alginate aqueous solution into the reaction kettle, controlling the dripping speed of the sodium alginate aqueous solution to 32g/min, continuing stirring for 11min after dripping, adding citric acid, continuing stirring for 11min, adding glutaraldehyde, continuing stirring for 28min, then performing ultraviolet irradiation, controlling the ultraviolet wavelength during ultraviolet irradiation to be 210nm, controlling the time to be 1.8h, adding methanol after ultraviolet irradiation, continuing stirring for 18min, filtering, and drying filter residues at 115 ℃ to obtain ultrafine colloid particles;
the weight ratio of the mixed powder suspension aqueous solution to the sodium alginate aqueous solution to the citric acid to the glutaraldehyde to the methanol is 102:510:5:1.2:520;
the preparation method of the composite vulcanizing agent comprises the following steps: mixing nano calcium carbonate, triethyl citrate and sodium dodecyl sulfate, performing ball milling, controlling the ball-material ratio during ball milling to be 16:1, the rotating speed to be 310rpm, adding zinc methacrylate and sodium hexametaphosphate after ball milling for 22min, continuing ball milling for 22min to obtain ball grinding materials, and mixing the ball grinding materials with tert-butyl hydroperoxide to obtain the composite vulcanizing agent;
the weight ratio of the nano calcium carbonate to the triethyl citrate to the sodium dodecyl sulfate to the zinc methacrylate to the sodium hexametaphosphate to the tert-butyl hydroperoxide is 11:0.8:0.4:22:5:102;
the particle size of the nano calcium carbonate is 80nm.
A preparation method of a flame-retardant wear-resistant chlorinated polyethylene rubber composition specifically comprises the following steps: mixing chlorinated polyethylene powder, ultrafine colloid particles, white carbon black, dioctyl phthalate, antimonous oxide, calcium stearate, octamethyl cyclotetrasiloxane, methyl methacrylate, paraffin, tricalcium phosphate and stearic acid, adding into a mixer, stirring for 18min at 310rpm, adding into a mixer for primary mixing, controlling the pressure at 2.2MPa during primary mixing at 82 ℃ for 18min, then uniformly increasing the temperature to 112 ℃ within 22min, uniformly increasing the pressure to 10.5MPa, performing secondary mixing, controlling the time at 85min during secondary mixing, and obtaining a mixed material after the secondary mixing is finished; and adding a composite vulcanizing agent into the mixed mixture, stirring for 5min at 310rpm, vulcanizing, controlling the pressure at 5.5MPa and the temperature at 145 ℃ during vulcanization, and obtaining the flame-retardant wear-resistant chlorinated polyethylene rubber composition after vulcanization.
This example shows no agglomeration during kneading.
Example 3
The flame-retardant wear-resistant chlorinated polyethylene rubber composition comprises the following components in parts by weight: 105 parts of chlorinated polyethylene powder, 12 parts of ultrafine colloid particles, 8 parts of white carbon black, 7 parts of dioctyl phthalate, 6 parts of composite vulcanizing agent, 5 parts of antimonous oxide, 4 parts of calcium stearate, 3 parts of octamethyl cyclotetrasiloxane, 2 parts of methyl methacrylate, 1.5 parts of paraffin, 1.2 parts of tricalcium phosphate and 1 part of stearic acid;
the chlorine content of the chlorinated polyethylene powder is 42%;
the preparation method of the ultrafine colloidal particles comprises the following steps: mixing kaolin and expanded perlite powder according to a weight ratio of 10:2, performing ball milling, controlling a ball-material ratio during ball milling to be 20:1, controlling a rotating speed to be 320rpm and a time to be 45min, obtaining mixed powder after ball milling, adding the mixed powder into 8 times of deionized water according to weight parts, performing ultrasonic vibration, controlling the frequency of ultrasonic vibration to be 40kHz and the time to be 20min, and obtaining mixed powder suspension aqueous solution after ultrasonic vibration; adding sodium alginate into 30 times of deionized water in parts by weight, performing ultrasonic oscillation, controlling the frequency of the ultrasonic oscillation to be 40kHz and the time to be 12 minutes, and obtaining sodium alginate aqueous solution after the ultrasonic oscillation is finished; adding the mixed powder suspension aqueous solution into a reaction kettle, controlling the temperature of the reaction kettle to 45 ℃, starting stirring, controlling the stirring speed to 80rpm, dripping sodium alginate aqueous solution into the reaction kettle, controlling the dripping speed of the sodium alginate aqueous solution to 35g/min, continuing stirring for 12min after dripping, adding citric acid, continuing stirring for 12min, adding glutaraldehyde, continuing stirring for 30min, then performing ultraviolet irradiation, controlling the ultraviolet wavelength during ultraviolet irradiation to 230nm, controlling the time to 2h, adding methanol after ultraviolet irradiation is finished, continuing stirring for 20min, filtering, and drying filter residues at 120 ℃ to obtain ultrafine colloid particles;
the weight ratio of the mixed powder suspension aqueous solution to the sodium alginate aqueous solution to the citric acid to the glutaraldehyde to the methanol is 105:520:6:1.5:550;
the preparation method of the composite vulcanizing agent comprises the following steps: mixing nano calcium carbonate, triethyl citrate and sodium dodecyl sulfate, performing ball milling, controlling the ball-material ratio during ball milling to be 18:1, controlling the rotating speed to be 320rpm, adding zinc methacrylate and sodium hexametaphosphate after ball milling for 25min, continuing ball milling for 25min to obtain ball grinding materials, and mixing the ball grinding materials with tert-butyl hydroperoxide to obtain the composite vulcanizing agent;
the weight ratio of the nano calcium carbonate to the triethyl citrate to the sodium dodecyl sulfate to the zinc methacrylate to the sodium hexametaphosphate to the tert-butyl hydroperoxide is 12:1:0.5:24:6:105;
the particle size of the nano calcium carbonate is 100nm.
A preparation method of a flame-retardant wear-resistant chlorinated polyethylene rubber composition specifically comprises the following steps: mixing chlorinated polyethylene powder, ultrafine colloid particles, white carbon black, dioctyl phthalate, antimonous oxide, calcium stearate, octamethyl cyclotetrasiloxane, methyl methacrylate, paraffin, tricalcium phosphate and stearic acid, adding into a mixer, stirring for 20min at 320rpm, adding into a mixer for primary mixing, controlling the pressure at 2.5MPa during primary mixing at 85 ℃ for 20min, then uniformly increasing the temperature to 115 ℃ within 25min, uniformly increasing the pressure to 11MPa, performing secondary mixing, controlling the time at 90min during secondary mixing, and obtaining a mixed material after the secondary mixing is finished; and adding a composite vulcanizing agent into the mixed materials, stirring for 6min at 320rpm, vulcanizing, controlling the pressure during vulcanization to be 6MPa and the temperature to be 150 ℃, and obtaining the flame-retardant wear-resistant chlorinated polyethylene rubber composition after vulcanization.
This example shows no agglomeration during kneading.
Comparative example 1
The composition and the preparation method of the flame-retardant wear-resistant chlorinated polyethylene rubber composition described in the example 2 are adopted, and the difference is that: the same amount of kaolin is used to replace ultrafine colloidal particles in the composition and preparation method of the flame-retardant wear-resistant chlorinated polyethylene rubber composition.
The comparative example did not show agglomeration during mixing.
Comparative example 2
The composition and the preparation method of the flame-retardant wear-resistant chlorinated polyethylene rubber composition are adopted in the embodiment 2, and the difference is that: the mixture of nano calcium carbonate and tertiary butyl hydroperoxide is used for replacing the compound vulcanizing agent in the composition of the flame-retardant wear-resistant chlorinated polyethylene rubber composition, wherein the weight ratio of the nano calcium carbonate to the tertiary butyl hydroperoxide is 11:102.
This comparative example showed agglomeration during kneading.
Test example 1
The flame retardant and abrasion resistant chlorinated polyethylene rubber compositions prepared in examples 1 to 3 and comparative examples 1 to 2 were tested for tensile strength, elongation at break, compression set, volume resistivity, tear strength, flex crack resistance, ozone resistance, oxygen index, and abrasion resistance, and the test results were as follows:
from the above results, it can be seen that by adding the ultrafine colloidal particles into the flame-retardant wear-resistant chlorinated polyethylene rubber composition, the ultrafine colloidal particles have good compatibility with polyvinyl chloride, and can bond the polyvinyl chloride particles, thereby improving the tensile strength, elongation at break, compression set and wear resistance; by using the composite vulcanizing agent in the flame-retardant wear-resistant chlorinated polyethylene rubber composition, the tertiary butyl hydroperoxide and the nano calcium carbonate subjected to surface treatment are combined, the combined tertiary butyl hydroperoxide can realize the vulcanization of polyvinyl chloride, the influence on the tearing strength and the flex crack resistance is reduced, the nano calcium carbonate subjected to surface treatment can further improve the tearing strength, the flex crack resistance, the ozone resistance and the oxygen index, the volume resistivity is reduced, and meanwhile, the agglomeration of the nano calcium carbonate in the mixing process can be avoided after the tertiary butyl hydroperoxide and the nano calcium carbonate subjected to surface treatment are combined.
Test example 2
The flame retardant and abrasion resistant chlorinated polyethylene rubber compositions prepared in examples 1 to 3 and comparative examples 1 to 2 were left to stand at-30℃for 10d, left to stand at 40℃for 10d, and then subjected to continuous irradiation under 500W xenon lamp for 10d, and then tested for tensile strength, elongation at break, compression set, and tear strength, with the following test results:
from the above results, it can be seen that the nano calcium carbonate surface-treated in the composite vulcanizing agent can promote the vulcanization of the polyvinyl chloride rubber by the tert-butyl hydroperoxide by using the composite vulcanizing agent in the flame-retardant wear-resistant chlorinated polyethylene rubber composition, thereby improving the weather resistance.
The percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The flame-retardant wear-resistant chlorinated polyethylene rubber composition is characterized by comprising the following components in parts by weight: 100-105 parts of chlorinated polyethylene powder, 10-12 parts of ultrafine colloid particles, 5-8 parts of white carbon black, 5-7 parts of dioctyl phthalate, 5-6 parts of composite vulcanizing agent, 3-5 parts of antimonous oxide, 3-4 parts of calcium stearate, 2-3 parts of octamethyl cyclotetrasiloxane, 1-2 parts of methyl methacrylate, 1-1.5 parts of paraffin wax, 1-1.2 parts of tricalcium phosphate and 0.5-1 part of stearic acid;
the preparation method of the ultrafine colloidal particles comprises the following steps: mixing kaolin and expanded perlite powder, performing ball milling to obtain mixed powder, adding the mixed powder into deionized water, performing ultrasonic vibration, and obtaining mixed powder suspension aqueous solution after the ultrasonic vibration is finished; adding sodium alginate into deionized water, performing ultrasonic oscillation, and obtaining sodium alginate aqueous solution after the ultrasonic oscillation is finished; adding the mixed powder suspension aqueous solution into a reaction kettle, controlling the temperature of the reaction kettle to 40-45 ℃, stirring, dripping sodium alginate aqueous solution into the reaction kettle, controlling the dripping speed of the sodium alginate aqueous solution to be 30-35g/min, continuing stirring after dripping, adding citric acid, continuing stirring, adding glutaraldehyde, continuing stirring, carrying out ultraviolet irradiation, adding methanol after ultraviolet irradiation, continuing stirring, filtering, and drying filter residues to obtain ultrafine colloid particles;
the preparation method of the composite vulcanizing agent comprises the following steps: mixing nano calcium carbonate, triethyl citrate and sodium dodecyl sulfate, performing ball milling, adding zinc methacrylate and sodium hexametaphosphate, performing ball milling continuously to obtain ball grinding materials, and mixing the ball grinding materials with tert-butyl hydroperoxide to obtain the composite vulcanizing agent.
2. The flame retardant and abrasion resistant chlorinated polyethylene rubber composition according to claim 1, wherein the chlorinated polyethylene powder has a chlorine content of 40-42%.
3. The flame-retardant wear-resistant chlorinated polyethylene rubber composition according to claim 1, wherein in the preparation of the ultrafine colloidal particles, the weight ratio of the mixed powder in the mixed powder suspension aqueous solution to deionized water is 1:7-8; the weight ratio of sodium alginate to deionized water in the sodium alginate aqueous solution is 1:28-30.
4. The flame-retardant and wear-resistant chlorinated polyethylene rubber composition according to claim 1, wherein in the preparation of the ultrafine colloidal particles, the weight ratio of the mixed powder suspension aqueous solution, the sodium alginate aqueous solution, the citric acid, the glutaraldehyde and the methanol is 100-105:300-320:4-6:1-1.5:500-550.
5. The flame-retardant and wear-resistant chlorinated polyethylene rubber composition according to claim 1, wherein the composite vulcanizing agent is prepared by mixing 10-12:0.5-1:0.3-0.5:20-24:4-6:100-105 of nano calcium carbonate, triethyl citrate, sodium dodecyl sulfate, zinc methacrylate, sodium hexametaphosphate and tert-butyl hydroperoxide.
6. The flame-retardant and wear-resistant chlorinated polyethylene rubber composition according to claim 1, wherein the particle size of the nano calcium carbonate is 50-100nm in the preparation of the composite vulcanizing agent.
7. A preparation method of a flame-retardant wear-resistant chlorinated polyethylene rubber composition according to claim 1, which is characterized in that chlorinated polyethylene powder, ultrafine colloid particles, white carbon black, dioctyl phthalate, antimony trioxide, calcium stearate, octamethyl cyclotetrasiloxane, methyl methacrylate, paraffin, tricalcium phosphate and stearic acid are mixed and then added into a mixer, stirred, then added into the mixer for primary mixing, the pressure during primary mixing is controlled to be 2-2.5MPa, the temperature is 80-85 ℃ for 15-20min, then the temperature is uniformly increased to be 110-115 ℃ within 20-25min, the pressure is uniformly increased to be 10-11MPa, secondary mixing is performed, the time during secondary mixing is controlled to be 80-90min, and a mixed material is obtained after the secondary mixing is finished; and adding a composite vulcanizing agent into the mixed mixture, stirring, and vulcanizing to obtain the flame-retardant wear-resistant chlorinated polyethylene rubber composition after vulcanization.
8. The method for producing a flame retardant and abrasion resistant chlorinated polyethylene rubber composition according to claim 7, wherein the pressure at the time of vulcanization is 5 to 6MPa and the temperature is 140 to 150 ℃.
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