CN114456518A - High-elasticity polyvinyl chloride composite material and preparation method thereof - Google Patents
High-elasticity polyvinyl chloride composite material 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
- 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
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Abstract
The invention discloses a high-elasticity polyvinyl chloride composite material which comprises the following components in parts by weight: 8-15 parts of rubber type chlorinated polyethylene, 70-90 parts of polyvinyl chloride resin, 3-5 parts of heat stabilizer, 5-8 parts of plasticizer, 1-2 parts of polyethylene wax, 1.8-2.5 parts of processing aid, 5-12 parts of inorganic flame retardant, 3-5 parts of ultraviolet-resistant absorbent, 6-8 parts of modified polyacrylate rubber, 2.5-3.5 parts of modified triblock polyolefin copolymer SEBS material, 0.5-1.5 parts of antioxidant and 20-35 parts of inorganic filler. Wherein, the rubber type chlorinated polyethylene is matched with the polyvinyl chloride resin for use, so that the elasticity of the composite material can be obviously enhanced; the addition of the vulcanized modified polyacrylate rubber can effectively improve the connection performance between various inorganic raw materials and organic raw materials; a small amount of modified triblock polyolefin copolymer SEBS material can further improve the elasticity of the material.
Description
Technical Field
The invention relates to the technical field of polyvinyl chloride composite materials, in particular to a high-elasticity polyvinyl chloride composite material and a preparation method thereof.
Background
The polyvinyl chloride resin is a multi-component plastic, and different additives can be added according to different purposes, so that products can show different physical and mechanical properties according to different compositions, for example, the hardness of the products can be changed by adding plasticizers with different component amounts. The decorative material polyvinyl chloride anti-collision strip on the market is mainly used for decoration and processing of furniture and aluminum materials, is bright in material color and convenient to paste, can play a good role in protecting the safety of children and the old, and can improve the decorative attractive effect of the furniture. The product part is composed of ultra-soft polyvinyl chloride, the hardness of the soft polyvinyl chloride in the market is mainly adjusted by increasing the dosage of a plasticizer, and although the crashproof strips produced by the soft polyvinyl chloride have enough softness, the elasticity is poor and the special smell of plastics is accompanied, so the crashproof strips are not used better.
In order to improve the elasticity and environmental protection performance of the polyvinyl chloride material and enable the polyvinyl chloride material to better meet the requirements of household use, the invention provides a high-elasticity polyvinyl chloride composite material and a preparation method thereof.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a high-elasticity polyvinyl chloride composite material and a preparation method thereof.
The technical scheme of the invention is as follows:
a high-elasticity polyvinyl chloride composite material comprises the following components in parts by weight: 8-15 parts of rubber type chlorinated polyethylene, 70-90 parts of polyvinyl chloride resin, 3-5 parts of heat stabilizer, 5-8 parts of plasticizer, 1-2 parts of polyethylene wax, 1.8-2.5 parts of processing aid, 5-12 parts of inorganic flame retardant, 3-5 parts of ultraviolet-resistant absorbent, 6-8 parts of modified polyacrylate rubber, 2.5-3.5 parts of modified triblock polyolefin copolymer SEBS material, 0.5-1.5 parts of antioxidant and 20-35 parts of inorganic filler.
Preferably, the tensile strength of the rubber type chlorinated polyethylene is higher than 15Mpa, and the elongation at break is higher than 550%.
Preferably, the heat stabilizer is a calcium-zinc composite stabilizer; the plasticizer is cyclohexane 1, 2-diisononyl phthalate; the processing aid is a processing aid DR; the antioxidant is hindered phenol antioxidant; the inorganic filler is any one of calcium carbonate or kaolin.
Preferably, the inorganic flame retardant is a mixed flame retardant of aluminum hydroxide and antimony trioxide.
Preferably, in the inorganic flame retardant, the mass ratio of the aluminum hydroxide to the antimony trioxide is 100: (7-22).
Preferably, the modified polyacrylate rubber is vulcanized modified polyacrylate rubber.
The preparation method of the vulcanized modified polyacrylate rubber comprises the following steps: adding polyacrylate rubber raw rubber into a rubber open mill or an internal mixer, pressing partial reinforcing filler, adding stearic acid, an anti-aging agent, partial vulcanizing agent and a vulcanization accelerator, alternately adding the reinforcing filler and an operation aid, finally adding the rest vulcanizing agent, beating for 4-6 times to form triangular bags after all the aids are mixed into the rubber, discharging the sheets, and standing for 24 hours at room temperature to prepare polyacrylate rubber compound; and vulcanizing and crosslinking the rubber compound for 5-6h at the temperature of 160-170 ℃ to obtain the vulcanized modified polyacrylate rubber.
More preferably, the addition amounts of the reinforcing filler, the stearic acid, the anti-aging agent, the vulcanizing agent, the vulcanization accelerator and the operation auxiliary agent are respectively 8-15 parts, 1-2 parts, 0.5-0.8 part, 7-10 parts, 0.8-1.5 parts and 3-5 parts according to 100 parts of the polyacrylate rubber virgin rubber;
the reinforcing filler is carbon black, the anti-aging agent is diphenylamine anti-aging agent, the vulcanization accelerator is sodium stearate, the vulcanizing agent is sulfur, and the operation auxiliary agent is dimethyl silicone oil.
Preferably, the preparation method of the modified triblock polyolefin copolymer SEBS material comprises the following steps: oil-charging SEBS elastomer, namely stirring and mixing SEBS and white oil in a mass ratio of 1: 0.8-2 in a high-speed mixer for 3-5min, taking out, and standing for more than 24 hours to fully swell SEBS; mixing oil-filled SEBS and a modifier PP in a mass ratio of 1: 0.3-2, matching calcium carbonate in a mass ratio of 3-10% and hindered phenol antioxidant in a mass ratio of 0.1-0.5% in a high-speed mixer for 3-5min, adding the mixture into an internal mixer for melting and mixing after fully mixing uniformly, wherein the mixing temperature is 190 ℃ and 220 ℃, and the mixing time is 45-60 min; cooling and discharging the mixture in an internal mixing cavity; pulverizing with pulverizer to obtain granules with diameter of 3-5 mm.
A preparation method of a high-elasticity polyvinyl chloride composite material comprises the following steps: mixing rubber type chlorinated polyethylene, polyvinyl chloride resin, a heat stabilizer, polyethylene wax, a processing aid, an ultraviolet-resistant absorbent, modified polyacrylate rubber, a modified triblock polyolefin copolymer SEBS material and an antioxidant, stirring at the rotation speed of 100-200r/min at 90-120 ℃, stirring at the rotation speed of 400-500r/min, slowly adding a plasticizer, kneading and swelling until the mixed material is powdery, adding an inorganic flame retardant and an inorganic filler, continuously stirring until the mixed material is loose and powdery, and extruding, granulating and cooling by an extruder to obtain the modified polyvinyl chloride rubber.
The invention has the advantages that: the high-elasticity polyvinyl chloride composite material comprises the following components in parts by weight: 8-15 parts of rubber type chlorinated polyethylene, 70-90 parts of polyvinyl chloride resin, 3-5 parts of heat stabilizer, 5-8 parts of plasticizer, 1-2 parts of polyethylene wax, 1.8-2.5 parts of processing aid, 5-12 parts of inorganic flame retardant, 3-5 parts of ultraviolet-resistant absorbent, 6-8 parts of modified polyacrylate rubber, 2.5-3.5 parts of modified triblock polyolefin copolymer SEBS material, 0.5-1.5 parts of antioxidant and 20-35 parts of inorganic filler. Wherein, the rubber type chlorinated polyethylene is matched with the polyvinyl chloride resin for use, so that the elasticity of the composite material can be obviously enhanced; the addition of the vulcanized modified polyacrylate rubber can effectively improve the connection performance between various inorganic raw materials and organic raw materials; the elasticity of the material can be further improved by adding a small amount of the modified triblock polyolefin copolymer SEBS material.
Detailed Description
Example 1
A high-elasticity polyvinyl chloride composite material comprises the following components in parts by weight: 12 parts of rubber type chlorinated polyethylene, 85 parts of polyvinyl chloride resin, 4 parts of heat stabilizer, 7 parts of plasticizer, 1.8 parts of polyethylene wax, 2.2 parts of processing aid, 7 parts of inorganic flame retardant, 4 parts of ultraviolet-resistant absorbent, 6.5 parts of modified polyacrylate rubber, 2.8 parts of modified triblock polyolefin copolymer SEBS material, 0.8 part of antioxidant and 30 parts of inorganic filler.
The tensile strength of the rubber type chlorinated polyethylene is 16.2Mpa, and the elongation at break is 580%.
The heat stabilizer is a calcium-zinc composite stabilizer; the plasticizer is cyclohexane 1, 2-diisononyl phthalate; the processing aid is a processing aid DR; the antioxidant is hindered phenol antioxidant; the inorganic filler is calcium carbonate.
The inorganic flame retardant is a mixed flame retardant of aluminum hydroxide and antimony trioxide.
In the inorganic flame retardant, the mass ratio of the aluminum hydroxide to the antimony trioxide is 100: 18.
the modified polyacrylate rubber is vulcanized modified polyacrylate rubber.
The preparation method of the vulcanized modified polyacrylate rubber comprises the following steps: adding polyacrylate rubber raw rubber into a rubber open mill or an internal mixer, pressing partial reinforcing filler, adding stearic acid, an anti-aging agent, partial vulcanizing agent and a vulcanization accelerator, alternately adding the reinforcing filler and an operation aid, finally adding the rest vulcanizing agent, beating for 5 times to form a triangular bag after all the aids are mixed into the rubber, discharging the rubber, and standing for 24 hours at room temperature to prepare polyacrylate rubber mixed rubber; and vulcanizing and crosslinking the rubber compound for 5.5 hours at 165 ℃ to obtain the vulcanized modified polyacrylate rubber.
The polyacrylate rubber raw rubber comprises, by 100 parts, 10 parts of reinforcing filler, 1.5 parts of stearic acid, 8 parts of antioxidant, 1.2 parts of vulcanizing accelerator and 3.8 parts of operation aid;
the reinforcing filler is carbon black, the anti-aging agent is diphenylamine anti-aging agent, the vulcanization accelerator is sodium stearate, the vulcanizing agent is sulfur, and the operation auxiliary agent is dimethyl silicone oil.
The preparation method of the modified triblock polyolefin copolymer SEBS material comprises the following steps: oil-charging SEBS elastomer, namely stirring and mixing SEBS and white oil in a mass ratio of 1: 1.2 in a high-speed mixer for 4min, taking out, and standing for more than 24 hours to fully swell SEBS; mixing the oil-filled SEBS and the modifier PP in a mass ratio of 1: 0.8, mixing with 7% of calcium carbonate and 0.3% of hindered phenol antioxidant in a high-speed mixer for 4min, mixing uniformly, adding into an internal mixer for melting and mixing at 215 ℃, wherein the mixing time is 55 min; cooling and discharging the mixture in an internal mixing cavity; pulverizing with pulverizer to obtain granules with diameter of 3-5 mm.
A preparation method of a high-elasticity polyvinyl chloride composite material comprises the following steps: mixing rubber type chlorinated polyethylene, polyvinyl chloride resin, a heat stabilizer, polyethylene wax, a processing aid, an ultraviolet-resistant absorbent, modified polyacrylate rubber, a modified triblock polyolefin copolymer SEBS material and an antioxidant, stirring at the rotating speed of 150r/min for 1.5min at 105 ℃, stirring at the rotating speed of 480r/min, slowly adding a plasticizer, kneading and swelling until the mixed material is powdery, adding an inorganic flame retardant and an inorganic filler, continuously stirring until the mixed material is loose and powdery, extruding by an extruder for granulation, and cooling to obtain the modified polyvinyl chloride rubber.
Example 2
A high-elasticity polyvinyl chloride composite material comprises the following components in parts by weight: 15 parts of rubber type chlorinated polyethylene, 70 parts of polyvinyl chloride resin, 5 parts of heat stabilizer, 5 parts of plasticizer, 2 parts of polyethylene wax, 1.8 parts of processing aid, 12 parts of inorganic flame retardant, 3 parts of ultraviolet-resistant absorbent, 8 parts of modified polyacrylate rubber, 2.5 parts of modified triblock polyolefin copolymer SEBS material, 1.5 parts of antioxidant and 20 parts of inorganic filler.
The tensile strength of the rubber type chlorinated polyethylene is 15.5Mpa, and the elongation at break is 565%.
The heat stabilizer is a calcium-zinc composite stabilizer; the plasticizer is cyclohexane 1, 2-diisononyl phthalate; the processing aid is a processing aid DR; the antioxidant is hindered phenol antioxidant; the inorganic filler is kaolin.
The inorganic flame retardant is a mixed flame retardant of aluminum hydroxide and antimony trioxide.
In the inorganic flame retardant, the mass ratio of the aluminum hydroxide to the antimony trioxide is 100: 22.
the modified polyacrylate rubber is vulcanized modified polyacrylate rubber.
The preparation method of the vulcanized modified polyacrylate rubber comprises the following steps: adding polyacrylate rubber raw rubber into a rubber open mill or an internal mixer, pressing partial reinforcing filler, adding stearic acid, an anti-aging agent, partial vulcanizing agent and a vulcanization accelerator, alternately adding the reinforcing filler and an operation aid, finally adding the rest vulcanizing agent, beating for 4 times to form a triangular bag after all the aids are mixed into the rubber, discharging the rubber, and standing for 24 hours at room temperature to prepare polyacrylate rubber mixed rubber; and vulcanizing and crosslinking the rubber compound for 5 hours at the temperature of 170 ℃ to obtain the vulcanized modified polyacrylate rubber.
The polyacrylate rubber raw rubber comprises, by 100 parts, 15 parts of reinforcing filler, 1 part of stearic acid, 7 parts of antioxidant, 1.5 parts of vulcanizing agent, 0.8 part of vulcanizing accelerator and 3 parts of operation aid;
the reinforcing filler is carbon black, the anti-aging agent is diphenylamine anti-aging agent, the vulcanization accelerator is sodium stearate, the vulcanizing agent is sulfur, and the operation auxiliary agent is dimethyl silicone oil.
The preparation method of the modified triblock polyolefin copolymer SEBS material comprises the following steps: oil-charging SEBS elastomer, namely stirring and mixing SEBS and white oil in a mass ratio of 1: 2 in a high-speed mixer for 3min, taking out, and standing for more than 24 hours to fully swell SEBS; mixing oil-filled SEBS and a modifier PP in a mass ratio of 1: 2, calcium carbonate in a mass ratio of 3% and a hindered phenol antioxidant in a mass ratio of 0.5% in a high-speed mixer for 3min, adding the mixture into an internal mixer for melting and mixing at the mixing temperature of 220 ℃ for 45min after fully and uniformly mixing; cooling and discharging the mixture in an internal mixing cavity; pulverizing with pulverizer to obtain granules with diameter of 3-5 mm.
A preparation method of a high-elasticity polyvinyl chloride composite material comprises the following steps: mixing rubber type chlorinated polyethylene, polyvinyl chloride resin, a heat stabilizer, polyethylene wax, a processing aid, an ultraviolet-resistant absorbent, modified polyacrylate rubber, a modified triblock polyolefin copolymer SEBS material and an antioxidant, stirring at the rotating speed of 100r/min for 2min at 120 ℃, stirring at the rotating speed of 400r/min, slowly adding a plasticizer, kneading and swelling until the mixed material is powdery, adding an inorganic flame retardant and an inorganic filler, continuously stirring until the mixed material is loose and powdery, extruding by an extruder for granulation, and cooling to obtain the modified polyvinyl chloride rubber.
Example 3
A high-elasticity polyvinyl chloride composite material comprises the following components in parts by weight: 8 parts of rubber type chlorinated polyethylene, 90 parts of polyvinyl chloride resin, 3 parts of heat stabilizer, 8 parts of plasticizer, 1 part of polyethylene wax, 2.5 parts of processing aid, 5 parts of inorganic flame retardant, 5 parts of ultraviolet-resistant absorbent, 6 parts of modified polyacrylate rubber, 3.5 parts of modified triblock polyolefin copolymer SEBS material, 0.5 part of antioxidant and 35 parts of inorganic filler.
The tensile strength of the rubber type chlorinated polyethylene is higher than 17.6Mpa, and the elongation at break is higher than 595%.
The heat stabilizer is a calcium-zinc composite stabilizer; the plasticizer is cyclohexane 1, 2-diisononyl phthalate; the processing aid is a processing aid DR; the antioxidant is hindered phenol antioxidant; the inorganic filler is calcium carbonate.
The inorganic flame retardant is a mixed flame retardant of aluminum hydroxide and antimony trioxide.
In the inorganic flame retardant, the mass ratio of the aluminum hydroxide to the antimony trioxide is 100: 7.
the modified polyacrylate rubber is vulcanized modified polyacrylate rubber.
The preparation method of the vulcanized modified polyacrylate rubber comprises the following steps: adding polyacrylate rubber raw rubber into a rubber open mill or an internal mixer, pressing partial reinforcing filler, adding stearic acid, an anti-aging agent, partial vulcanizing agent and a vulcanization accelerator, alternately adding the reinforcing filler and an operation aid, finally adding the rest vulcanizing agent, beating a triangular bag for 6 times after all the aids are mixed into the rubber, discharging the rubber, and standing for 24 hours at room temperature to prepare polyacrylate rubber mixed rubber; and vulcanizing and crosslinking the rubber compound for 6 hours at 160 ℃ to obtain the vulcanized modified polyacrylate rubber.
The polyacrylate rubber raw rubber comprises, by 100 parts, 8 parts, 2 parts, 0.5 part, 10 parts, 0.8 part and 5 parts of reinforcing filler, stearic acid, an anti-aging agent, a vulcanizing agent, a vulcanization accelerator and a processing aid;
the reinforcing filler is carbon black, the anti-aging agent is diphenylamine anti-aging agent, the vulcanization accelerator is sodium stearate, the vulcanizing agent is sulfur, and the operation auxiliary agent is dimethyl silicone oil.
The preparation method of the modified triblock polyolefin copolymer SEBS material comprises the following steps: oil-charging SEBS elastomer, namely stirring and mixing SEBS and white oil in a mass ratio of 1: 0.8 in a high-speed mixer for 5min, taking out, and standing for more than 24 hours to fully swell SEBS; mixing oil-filled SEBS and a modifier PP in a mass ratio of 1: 0.3, mixing with 10% of calcium carbonate and 0.1% of hindered phenol antioxidant in a high-speed mixer for 5min, mixing uniformly, adding into an internal mixer for melt mixing at 190 ℃, and mixing for 60 min; cooling and discharging the mixture in an internal mixing cavity; pulverizing with pulverizer to obtain granules with diameter of 3-5 mm.
A preparation method of a high-elasticity polyvinyl chloride composite material comprises the following steps: mixing rubber type chlorinated polyethylene, polyvinyl chloride resin, a heat stabilizer, polyethylene wax, a processing aid, an ultraviolet-resistant absorbent, modified polyacrylate rubber, a modified triblock polyolefin copolymer SEBS material and an antioxidant, stirring at the rotation speed of 200r/min for 1min at 90 ℃, stirring at the rotation speed of 500r/min, slowly adding a plasticizer, kneading and swelling until the mixed material is powdery, adding an inorganic flame retardant and an inorganic filler, continuously stirring until the mixed material is loose and powdery, extruding by an extruder for granulation, and cooling to obtain the modified polyvinyl chloride rubber.
Example 4
A high-elasticity polyvinyl chloride composite material comprises the following components in parts by weight: 12 parts of rubber type chlorinated polyethylene, 90 parts of polyvinyl chloride resin, 3.5 parts of heat stabilizer, 8 parts of plasticizer, 1.2 parts of polyethylene wax, 2.5 parts of processing aid, 8.5 parts of inorganic flame retardant, 5 parts of ultraviolet-resistant absorbent, 6.8 parts of modified polyacrylate rubber, 3.5 parts of modified triblock polyolefin copolymer SEBS material, 0.7 part of antioxidant and 35 parts of inorganic filler.
The tensile strength of the rubber type chlorinated polyethylene is 16.2Mpa, and the elongation at break is higher than 570%.
The heat stabilizer is a calcium-zinc composite stabilizer; the plasticizer is cyclohexane 1, 2-diisononyl phthalate; the processing aid is a processing aid DR; the antioxidant is hindered phenol antioxidant; the inorganic filler is kaolin.
The inorganic flame retardant is a mixed flame retardant of aluminum hydroxide and antimony trioxide.
In the inorganic flame retardant, the mass ratio of the aluminum hydroxide to the antimony trioxide is 100: 17.
the modified polyacrylate rubber is vulcanized modified polyacrylate rubber.
The preparation method of the vulcanized modified polyacrylate rubber comprises the following steps: adding polyacrylate rubber raw rubber into a rubber open mill or an internal mixer, pressing partial reinforcing filler, adding stearic acid, an anti-aging agent, partial vulcanizing agent and a vulcanization accelerator, alternately adding the reinforcing filler and an operation aid, finally adding the rest vulcanizing agent, beating for 5 times to form a triangular bag after all the aids are mixed into the rubber, discharging the rubber, and standing for 24 hours at room temperature to prepare polyacrylate rubber mixed rubber; and vulcanizing and crosslinking the rubber compound for 5.5h at the temperature of 160-170 ℃ to obtain the vulcanized modified polyacrylate rubber.
The polyacrylate rubber raw rubber comprises 100 parts of reinforcing filler, 2 parts of stearic acid, an anti-aging agent, a vulcanizing agent, a vulcanization accelerator and a processing aid, wherein the addition amounts of the reinforcing filler, the stearic acid, the anti-aging agent, the vulcanizing agent, the vulcanization accelerator and the processing aid are respectively 12 parts, 2 parts, 0.6 part, 10 parts, 0.9 part and 5 parts;
the reinforcing filler is carbon black, the anti-aging agent is diphenylamine anti-aging agent, the vulcanization accelerator is sodium stearate, the vulcanizing agent is sulfur, and the operation auxiliary agent is dimethyl silicone oil.
The preparation method of the modified triblock polyolefin copolymer SEBS material comprises the following steps: oil-charging SEBS elastomer, namely stirring and mixing SEBS and white oil in a mass ratio of 1: 1.5 in a high-speed mixer for 5min, taking out, and standing for more than 24 hours to fully swell SEBS; mixing oil-filled SEBS and a modifier PP in a mass ratio of 1: 0.8, mixing with 10% of calcium carbonate and 0.2% of hindered phenol antioxidant in a high-speed mixer for 5min, mixing uniformly, adding into an internal mixer for melt mixing at 195 ℃, and mixing for 60 min; cooling and discharging the mixture in an internal mixing cavity; pulverizing with pulverizer to obtain granules with diameter of 3-5 mm.
A preparation method of a high-elasticity polyvinyl chloride composite material comprises the following steps: mixing rubber type chlorinated polyethylene, polyvinyl chloride resin, a heat stabilizer, polyethylene wax, a processing aid, an ultraviolet-resistant absorbent, modified polyacrylate rubber, a modified triblock polyolefin copolymer SEBS material and an antioxidant, stirring at the rotation speed of 200r/min at 110 ℃ for 1.5min, stirring at the rotation speed of 500r/min, slowly adding a plasticizer, kneading and swelling until the mixed material is powdery, adding an inorganic flame retardant and an inorganic filler, continuously stirring until the mixed material is loose and powdery, extruding by an extruder for granulation, and cooling to obtain the flame-retardant modified polyvinyl chloride rubber.
Example 5
A high-elasticity polyvinyl chloride composite material comprises the following components in parts by weight: 15 parts of rubber type chlorinated polyethylene, 75 parts of polyvinyl chloride resin, 3 parts of heat stabilizer, 7 parts of plasticizer, 2 parts of polyethylene wax, 1.9 parts of processing aid, 12 parts of inorganic flame retardant, 3.8 parts of ultraviolet-resistant absorbent, 6 parts of modified polyacrylate rubber, 2.8 parts of modified triblock polyolefin copolymer SEBS material, 0.5 part of antioxidant and 32 parts of inorganic filler.
The tensile strength of the rubber type chlorinated polyethylene is higher than 16.5Mpa, and the elongation at break is higher than 580%.
The heat stabilizer is a calcium-zinc composite stabilizer; the plasticizer is cyclohexane 1, 2-diisononyl phthalate; the processing aid is a processing aid DR; the antioxidant is hindered phenol antioxidant; the inorganic filler is calcium carbonate.
The inorganic flame retardant is a mixed flame retardant of aluminum hydroxide and antimony trioxide.
In the inorganic flame retardant, the mass ratio of the aluminum hydroxide to the antimony trioxide is 100: 13.
the modified polyacrylate rubber is vulcanized modified polyacrylate rubber.
The preparation method of the vulcanized modified polyacrylate rubber comprises the following steps: adding polyacrylate rubber raw rubber into a rubber open mill or an internal mixer, pressing partial reinforcing filler, adding stearic acid, an anti-aging agent, partial vulcanizing agent and a vulcanization accelerator, alternately adding the reinforcing filler and an operation aid, finally adding the rest vulcanizing agent, beating for 5 times to form a triangular bag after all the aids are mixed into the rubber, discharging the rubber, and standing for 24 hours at room temperature to prepare polyacrylate rubber mixed rubber; and vulcanizing and crosslinking the rubber compound for 5.5 hours at 165 ℃ to obtain the vulcanized modified polyacrylate rubber.
The polyacrylate rubber raw rubber comprises 100 parts of reinforcing filler, 2 parts of stearic acid, an anti-aging agent, a vulcanizing agent, a vulcanization accelerator and a processing aid, wherein the addition amounts of the reinforcing filler, the stearic acid, the anti-aging agent, the vulcanizing agent, the vulcanization accelerator and the processing aid are respectively 12 parts, 2 parts, 0.6 part, 10 parts, 1.3 parts and 5 parts;
the reinforcing filler is carbon black, the anti-aging agent is diphenylamine anti-aging agent, the vulcanization accelerator is sodium stearate, the vulcanizing agent is sulfur, and the operation auxiliary agent is dimethyl silicone oil.
The preparation method of the modified triblock polyolefin copolymer SEBS material comprises the following steps: oil-charging SEBS elastomer, namely stirring and mixing SEBS and white oil in a mass ratio of 1: 1.5 in a high-speed mixer for 3min, taking out, and standing for more than 24 hours to fully swell SEBS; mixing the oil-filled SEBS and the modifier PP in a mass ratio of 1: 0.8, matching with 5.8% of calcium carbonate and 0.1% of hindered phenol antioxidant in a high-speed mixer for 3.5min, adding the mixture into an internal mixer for melting and mixing at the mixing temperature of 205 ℃ for 55min after fully mixing uniformly; cooling and discharging the mixed material in an internal mixing cavity; pulverizing with pulverizer to obtain granules with diameter of 3-5 mm.
A preparation method of a high-elasticity polyvinyl chloride composite material comprises the following steps: mixing rubber type chlorinated polyethylene, polyvinyl chloride resin, a heat stabilizer, polyethylene wax, a processing aid, an ultraviolet-resistant absorbent, modified polyacrylate rubber, a modified triblock polyolefin copolymer SEBS material and an antioxidant, stirring at the rotating speed of 150r/min at 95 ℃ for 1.5min, stirring at the rotating speed of 450r/min, slowly adding a plasticizer, kneading and swelling until the mixed material is powdery, adding an inorganic flame retardant and an inorganic filler, continuously stirring until the mixed material is loose and powdery, extruding by an extruder for granulation, and cooling to obtain the flame-retardant modified polyvinyl chloride rubber.
Comparative example 1
The rubber type chlorinated polyethylene in example 1 was removed, and the rest of the compounding ratio and the preparation method were unchanged.
Comparative example 2
The modified polyacrylate rubber in example 1 was removed, and the remaining proportions and preparation methods were unchanged.
Comparative example 3
The modified polyacrylate rubber in example 1 was replaced with unmodified polyacrylate rubber, and the rest of the compounding ratio and the preparation method were unchanged.
Comparative example 4
The modified triblock polyolefin copolymer SEBS material in example 1 was removed, and the rest of the compounding ratio and the preparation method were unchanged.
Comparative example 5
The modified triblock polyolefin copolymer SEBS material in example 1 is replaced by the unmodified triblock polyolefin copolymer SEBS, and the rest proportion and the preparation method are not changed.
Comparative example 6
The modified polyacrylate rubber and the modified triblock polyolefin copolymer SEBS material in example 1 were removed simultaneously, and the remaining proportion and preparation method were unchanged.
The physical properties of the high-elasticity polyvinyl chloride composite materials prepared in the examples 1 to 5 and the comparative examples 1 to 6 are detected as follows, and the following detection results are obtained, wherein the detection method is referred to GB/T528-:
table 1: detecting the physical property of the high-elasticity polyvinyl chloride composite material;
remarking: 1. the compression deformation% is compression deformation at 30 ℃ for 24 h; 2. the recovery degree and the deformation degree are flat experiments at 30 ℃ for 1h, and the recovery degree is kept for 1 h; the deformation degree is 30 ℃ multiplied by 1h flat experiment, and the deformation degree is 24h when the flat experiment is parked.
The test data show that the polyvinyl chloride composite material has very good elasticity, and the three materials of the rubber type chlorinated polyethylene, the modified polyacrylate rubber and the modified triblock polyolefin copolymer SEBS have a synergistic effect mutually.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (9)
1. The high-elasticity polyvinyl chloride composite material is characterized by comprising the following components in parts by weight: 8-15 parts of rubber type chlorinated polyethylene, 70-90 parts of polyvinyl chloride resin, 3-5 parts of heat stabilizer, 5-8 parts of plasticizer, 1-2 parts of polyethylene wax, 1.8-2.5 parts of processing aid, 5-12 parts of inorganic flame retardant, 3-5 parts of ultraviolet-resistant absorbent, 6-8 parts of modified polyacrylate rubber, 2.5-3.5 parts of modified triblock polyolefin copolymer SEBS material, 0.5-1.5 parts of antioxidant and 20-35 parts of inorganic filler; the inorganic flame retardant is a mixed flame retardant of aluminum hydroxide and antimony trioxide.
2. The high resilience polyvinyl chloride composite material according to claim 1 wherein the rubber type chlorinated polyethylene has a tensile strength of greater than 15Mpa and an elongation at break of greater than 550%.
3. The high resilience polyvinyl chloride composite material according to claim 1, wherein the heat stabilizer is a calcium zinc composite stabilizer; the plasticizer is cyclohexane 1, 2-diisononyl phthalate; the processing aid is a processing aid DR; the antioxidant is hindered phenol antioxidant; the inorganic filler is any one of calcium carbonate or kaolin.
4. The high elastic polyvinyl chloride composite material according to claim 1, wherein the inorganic flame retardant comprises aluminum hydroxide and antimony trioxide in a mass ratio of 100: (7-22).
5. The high resilience polyvinyl chloride composite material of claim 1 wherein said modified polyacrylate rubber is a vulcanized modified polyacrylate rubber.
6. The high resilience polyvinyl chloride composite material according to claim 1, wherein said vulcanized modified polyacrylate rubber is prepared by a method comprising the steps of: adding polyacrylate rubber raw rubber into a rubber open mill or an internal mixer, pressing partial reinforcing filler, adding stearic acid, an anti-aging agent, partial vulcanizing agent and a vulcanization accelerator, alternately adding the reinforcing filler and an operation aid, finally adding the rest vulcanizing agent, beating for 4-6 times to form triangular bags after all the aids are mixed into the rubber, discharging the sheets, and standing for 24 hours at room temperature to prepare polyacrylate rubber compound; and vulcanizing and crosslinking the rubber compound for 5-6h at the temperature of 160-170 ℃ to obtain the vulcanized modified polyacrylate rubber.
7. The high elastic polyvinyl chloride composite material according to claim 1, wherein the reinforcing filler, stearic acid, anti-aging agent, vulcanizing agent, vulcanization accelerator and processing aid are added in amounts of 8 to 15 parts, 1 to 2 parts, 0.5 to 0.8 part, 7 to 10 parts, 0.8 to 1.5 parts and 3 to 5 parts, respectively, based on 100 parts of the polyacrylate rubber virgin rubber;
the reinforcing filler is carbon black, the anti-aging agent is diphenylamine anti-aging agent, the vulcanization accelerator is sodium stearate, the vulcanizing agent is sulfur, and the operation auxiliary agent is dimethyl silicone oil.
8. The high-elasticity polyvinyl chloride composite material as claimed in claim 1, wherein the preparation method of the modified triblock polyolefin copolymer SEBS material comprises the following steps: oil-charging SEBS elastomer, namely stirring and mixing SEBS and white oil in a mass ratio of 1: 0.8-2 in a high-speed mixer for 3-5min, taking out, and standing for more than 24 hours to fully swell SEBS; stirring the oil-filled SEBS and the modifier PP in a mass ratio of 1: 0.3-2, matching with 3-10% of calcium carbonate and 0.1-0.5% of hindered phenol antioxidant in a high-speed mixer for 3-5min, fully mixing uniformly, adding the mixture into an internal mixer for melting and mixing, wherein the mixing temperature is 190-; cooling and discharging the mixture in an internal mixing cavity; pulverizing with pulverizer to obtain granules with diameter of 3-5 mm.
9. The highly elastic polyvinyl chloride composite material according to claims 1 to 8, which is prepared by a process comprising the steps of: mixing rubber type chlorinated polyethylene, polyvinyl chloride resin, a heat stabilizer, polyethylene wax, a processing aid, an ultraviolet-resistant absorbent, modified polyacrylate rubber, a modified triblock polyolefin copolymer SEBS material and an antioxidant, stirring at the rotation speed of 100-200r/min at 90-120 ℃, stirring at the rotation speed of 400-500r/min, slowly adding a plasticizer, kneading and swelling until the mixed material is powdery, adding an inorganic flame retardant and an inorganic filler, continuously stirring until the mixed material is loose and powdery, and extruding, granulating and cooling by an extruder to obtain the modified polyvinyl chloride rubber.
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| US6063846A (en) * | 1997-05-30 | 2000-05-16 | Teknor Apex Company | Polyvinyl chloride compositions |
| CN1861678A (en) * | 2006-05-19 | 2006-11-15 | 北京化工大学 | Preparation process of easy processing cold resisting type polyacrylate rubber |
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| CN113402825A (en) * | 2021-07-03 | 2021-09-17 | 台州市天达源科技股份有限公司 | Preparation method of environment-friendly impact-resistant PVC (polyvinyl chloride) insulating material |
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| US6063846A (en) * | 1997-05-30 | 2000-05-16 | Teknor Apex Company | Polyvinyl chloride compositions |
| CN1861678A (en) * | 2006-05-19 | 2006-11-15 | 北京化工大学 | Preparation process of easy processing cold resisting type polyacrylate rubber |
| CN103849089A (en) * | 2014-03-10 | 2014-06-11 | 深圳市领亚电子有限公司 | Full-fogging-surface flexible cable composite material and preparation method thereof |
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