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CN111662511A - High-resilience high-strength thermoplastic vulcanized elastomer material and preparation method thereof - Google Patents

High-resilience high-strength thermoplastic vulcanized elastomer material and preparation method thereof Download PDF

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Publication number
CN111662511A
CN111662511A CN202010599300.1A CN202010599300A CN111662511A CN 111662511 A CN111662511 A CN 111662511A CN 202010599300 A CN202010599300 A CN 202010599300A CN 111662511 A CN111662511 A CN 111662511A
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antioxidant
polypropylene
zone temperature
elastomer
thermoplastic
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Inventor
夏玉洁
曹春林
王江玉
吴章柱
黄慧
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Anhui Zhongding Rubber and Plastic Products Co Ltd
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Anhui Zhongding Rubber and Plastic Products Co Ltd
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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
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Ethene-propene or ethene-propene-diene copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/505—Screws
    • B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/02—Heterophasic composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer

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  • Mechanical Engineering (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a high-resilience high-strength thermoplastic vulcanized elastomer material and a preparation method thereof, wherein the high-resilience high-strength thermoplastic vulcanized elastomer material is prepared by blending and banburying raw materials of ethylene propylene diene monomer, polypropylene, a thermoplastic elastomer, processing oil, a vulcanization system, a processing aid and an anti-aging agent through a double-screw extruder; firstly, rubber, filler, oil and processing aids are fully sheared and mixed during banburying, then the mixture is dynamically crosslinked with polypropylene, and an elastomer is introduced at a proper time in the later stage of crosslinking to improve the overall compatibility of the material, so that the mechanical property and elasticity of the material are improved, the rubber and the plastic can form a uniform phase state in a short time, and the defect that the filler, the oil and various processing aids migrate to the plastic phase in a large amount is overcome. The thermoplastic vulcanized elastomer material prepared by the invention has good hardness, tensile strength, elongation at break, compression set, high resilience and high strength, has good physical and mechanical properties, and is suitable for being used as a raw material of products such as automobile sealing strips, wire harness sheaths and the like.

Description

High-resilience high-strength thermoplastic vulcanized elastomer material and preparation method thereof
Technical Field
The invention relates to the technical field of thermoplastic elastomer materials, in particular to a high-resilience high-strength thermoplastic vulcanized elastomer material and a preparation method thereof.
Background
The lightweight of the automobile is to reduce the preparation quality of the automobile as much as possible on the premise of ensuring the strength and the safety performance of the automobile, thereby improving the dynamic property of the automobile, reducing the fuel consumption and reducing the exhaust pollution. Experiments prove that if the weight of the whole automobile is reduced by 10%, the fuel efficiency can be improved by 6% -8%; the oil consumption per hundred kilometers of the vehicle can be reduced by 0.3-0.6 liter, the weight of the vehicle can be reduced by 1 percent, and the oil consumption can be reduced by 0.7 percent when the mass of the vehicle is reduced by 100 kilograms. The light weight of automobiles has become a trend of the development of automobiles in the world due to the need for environmental protection and energy conservation. US4311628/0272871a1 discloses a process for preparing thermoplastic vulcanizate, wherein the elastomer is ethylene propylene rubber, the resin is polypropylene, the vulcanization system is phenolic resin vulcanizing agent, stannous chloride dihydrate is vulcanization accelerator, and dynamic vulcanization technology is adopted to prepare the thermoplastic vulcanizate, but the vulcanized thermoplastic elastomer has poor rebound resilience and physical and mechanical properties, particularly hardness lower than 80shore a, and the products such as automobile sealing strips, wire harness sheaths and the like have better rebound resilience requirements for the thermoplastic vulcanizate.
Patent publication No. CN109320726A discloses a high-resilience thermoplastic elastomer and a preparation method thereof, wherein the preparation method comprises the following steps: dibasic acid, a cross-linking agent and dihydric alcohol are used as raw materials, a prepolymer is prepared through esterification or amidation reaction, then polyether dihydric alcohol, a catalyst and a heat stabilizer are added, and the high-resilience thermoplastic elastomer is prepared through ester exchange or amide exchange reaction. The high-resilience thermoplastic elastomer comprises a hard chain segment and a soft chain segment, wherein the hard chain segment is polyester and accounts for 10-90 wt% of the total amount of the elastomer, and the soft chain segment is polyether glycol/polyester and accounts for 10-90 wt% of the total amount of the elastomer. The invention improves the mechanical property of the elastomer by introducing a proper amount of chemical crosslinking points. The prepared product has the advantages of high breaking strength, elongation at break, rebound resilience and repeated processability, adjustable shore hardness, simple processing technology and high production efficiency, and makes up the defects of the product in the prior art.
Disclosure of Invention
In order to overcome the technical problems, the invention aims to provide a high-resilience high-strength thermoplastic vulcanized elastomer material and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
the invention provides a high-resilience high-strength thermoplastic vulcanized elastomer material which is prepared from the following raw materials in parts by weight: 80-120 parts of ethylene propylene diene monomer, 30-90 parts of polypropylene, 10-50 parts of thermoplastic elastomer, 10-80 parts of processing oil, 0.2-10 parts of a vulcanization system, 0.1-10 parts of a processing aid, 0.5-5 parts of an anti-aging agent and 20-50 parts of a filler;
the third monomer of the ethylene propylene diene monomer is ethylene norbornene, wherein the ethylene content is 40-70 wt%, and the third monomer content is 2-15 wt%;
the thermoplastic elastomer comprises one or a mixture of at least two of thermoplastic polyolefin elastomer, thermoplastic styrene elastomer and thermoplastic polyurethane elastomer.
As a further aspect of the present invention, the thermoplastic polyolefin elastomer has an ethylene content of less than 15% and a puncture force of not less than 300 lbf; the thermoplastic styrene-based elastomer has a hardness-softness ratio of 20/80 to 40/60 and a molecular weight of at least 20 ten thousand; the hard segment type of the thermoplastic polyurethane elastomer is MDI or H12MDI elastomer, wherein the relative molecular mass of the soft segment is not less than 2000.
As a further scheme of the invention, the polypropylene comprises one of homo-polypropylene and co-polypropylene or a mixture of at least two of homo-polypropylene and co-polypropylene, and the flexural modulus of the polypropylene is more than 1000 MPa; the polypropylene is high-melt-strength polypropylene, and the melt viscosity of the polypropylene is more than 1000Pas when the shearing force is 200Pa and the frequency is 10 HZ.
As a further scheme of the invention, the processing oil is paraffin oil, CA is less than or equal to 5, CN is less than or equal to 40, and CP is greater than or equal to 65; the kinematic viscosity of the processing oil at 100 ℃ is not less than 20mm2/s。
As a further scheme of the invention, the vulcanizing system is a phenolic resin vulcanizing system and is formed by mixing vulcanizing agent octyl phenolic resin and accelerator stannous chloride hydrate in a mass ratio of 3: 1.
As a further scheme of the invention, the processing aid is one or a mixture of at least two of a lubricant, a light stabilizer and a colorant; the lubricant is one or a mixture of at least two of zinc stearate, calcium stearate, PE wax and dimethyl silicone oil; the light stabilizer is one or a mixture of at least two of hindered amine and benzophenone; the colorant is one or a mixture of at least two of metal oxide, carbon black, metal sulfide and chromate.
As a further scheme of the invention, the anti-aging agent is formed by mixing a main antioxidant and an auxiliary antioxidant in a mass ratio of 1:3, wherein the main antioxidant is a hindered phenol antioxidant, and the auxiliary antioxidant is a phosphite antioxidant; the main antioxidant is one of antioxidant 1010, antioxidant 1076 and antioxidant 1790; the auxiliary antioxidant is one of antioxidant 168, antioxidant 618 and antioxidant P-EPQ.
As a further scheme of the invention, the filler is obtained by grafting the inorganic filler with whiteness of more than 85 through a coupling agent, and the coupling agent is formed by matching one or more than two of silane coupling agent, titanate coupling agent and zirconium coupling agent.
The invention also provides a preparation method of the high-resilience high-strength thermoplastic vulcanized elastomer material, which comprises the following steps:
feeding ethylene propylene diene monomer, polypropylene, processing oil, an anti-aging agent, a filler and a processing aid into a double-screw extruder through a weightlessness scale for blending; the screw rotation speed is 300 plus one/min, the screw length-diameter ratio is 55-64, the processing temperature is 160 plus one/min, the rubber, the filler, the oil product and the processing aid are fully sheared and mixed during banburying, then the rubber, the filler, the oil product and the processing aid are dynamically crosslinked with the polypropylene, the elastomer is introduced at the later stage of crosslinking, the position on the screw is located from the third section of cylinder body to the tenth section of cylinder body, and the side feeding position is located at the sixth section of cylinder body.
As a further scheme of the present invention, the processing temperature specifically is: the first zone temperature of the processing is 140 ℃, the second zone temperature is 180 ℃, the third zone temperature is 190 ℃, the fourth zone temperature is 200 ℃, the fifth zone temperature is 205 ℃, the sixth zone temperature is 210 ℃, the seventh zone temperature is 215 ℃, the eighth zone temperature is 220 ℃, the tenth zone temperature is 220 ℃, the eleventh zone temperature is 220 ℃, the twelfth zone temperature is 220 ℃ and the thirteenth zone temperature is 220 ℃.
The invention has the beneficial effects that:
the high-resilience high-strength thermoplastic vulcanized elastomer material is prepared by blending and banburying raw materials of ethylene propylene diene monomer, polypropylene, a thermoplastic elastomer, processing oil, a vulcanization system, a processing aid and an anti-aging agent by a double-screw extruder; rubber, filler, oil and processing aid are fully sheared and mixed during banburying, then are dynamically crosslinked with polypropylene, and the elastomer is introduced at a proper time in the later stage of crosslinking, so that the elastomer does not influence the island structure of TPV (thermoplastic vulcanizate), and can be connected into a rubber phase to improve the overall compatibility of the material, thereby improving the mechanical property and elasticity of the material, enabling the rubber and plastic to form a uniform phase in a short time, and avoiding the defect that the filler, the oil and various processing aids migrate to the plastic phase in a large amount. The thermoplastic vulcanized elastomer material prepared by the invention has good hardness, tensile strength, elongation at break, compression set, high resilience and high strength, has good physical and mechanical properties, and is suitable for being used as a raw material of products such as automobile sealing strips, wire harness sheaths and the like.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The names, designations and production companies of the raw materials of the high resilience and high strength thermoplastic vulcanizate of examples 1 to 4 are shown in the following table:
Figure BDA0002558063290000041
Figure BDA0002558063290000051
the weight parts of the raw materials of examples 1-4 are shown in the following table:
Figure BDA0002558063290000052
Figure BDA0002558063290000061
examples 1-4 high resilience high strength thermoplastic vulcanizate, preparation method comprising the steps of:
feeding ethylene propylene diene monomer, polypropylene, processing oil, an anti-aging agent, a filler and a processing aid into a double-screw extruder through a weightlessness scale for blending; the screw rotation speed is 300 plus one/min, the screw length-diameter ratio is 55-64, the processing temperature is 160 plus one/min, the rubber, the filler, the oil product and the processing aid are fully sheared and mixed during banburying, then the rubber, the filler, the oil product and the processing aid are dynamically crosslinked with the polypropylene, the elastomer is introduced at the later stage of crosslinking, the position on the screw is located from the third section of cylinder body to the tenth section of cylinder body, and the side feeding position is located at the sixth section of cylinder body. The processing temperature is specifically as follows: the first zone temperature of the processing is 140 ℃, the second zone temperature is 180 ℃, the third zone temperature is 190 ℃, the fourth zone temperature is 200 ℃, the fifth zone temperature is 205 ℃, the sixth zone temperature is 210 ℃, the seventh zone temperature is 215 ℃, the eighth zone temperature is 220 ℃, the tenth zone temperature is 220 ℃, the eleventh zone temperature is 220 ℃, the twelfth zone temperature is 220 ℃ and the thirteenth zone temperature is 220 ℃.
Example 5
The high-resilience high-strength thermoplastic vulcanized elastomer material is prepared from the following raw materials in parts by weight: 115 parts of ethylene propylene diene monomer, 76 parts of polypropylene, 38 parts of thermoplastic elastomer, 66 parts of processing oil, 6.5 parts of a vulcanization system, 7.5 parts of a processing aid, 2.5 parts of an anti-aging agent and 26 parts of a filler; the third monomer of the ethylene propylene diene monomer is ethylene norbornene, wherein the ethylene content is 56 wt%, and the third monomer content is 10 wt%.
Wherein the thermoplastic elastomer is formed by mixing a thermoplastic polyolefin elastomer and a thermoplastic styrene elastomer according to the mass ratio of 1: 1. The ethylene component of the thermoplastic polyolefin elastomer is less than 15 percent, and the puncture force is not less than 300 lbf; the thermoplastic styrene elastomer has a hardness-softness ratio of 20/80-40/60 and a molecular weight of at least 20 ten thousand; the hard segment type of the thermoplastic polyurethane elastomer is MDI or H12MDI elastomer, wherein the relative molecular mass of the soft segment is not less than 2000. The polypropylene is formed by mixing homo-polypropylene and co-polypropylene according to the mass ratio of 2:1, and the flexural modulus of the polypropylene is more than 1000 MPa; the polypropylene is high-melt-strength polypropylene, and the melt viscosity of the polypropylene is more than 1000Pas when the shearing force is 200Pa and the frequency is 10 HZ.
The processing oil is paraffin oil, CA is less than or equal to 5, CN is less than or equal to 40, and CP is more than or equal to 65; the kinematic viscosity of the processing oil at 100 ℃ is not less than 20mm2And s. The vulcanizing system is a phenolic resin vulcanizing system and is formed by mixing vulcanizing agent octyl phenolic resin and accelerator stannous chloride hydrate in a mass ratio of 3: 1.
The processing aid is formed by mixing a lubricant, a light stabilizer and a coloring agent according to the mass ratio of 2:1: 1; the lubricant is formed by mixing calcium stearate and PE wax according to the mass ratio of 2: 1; the light stabilizer is hindered amine; the colorant is a metal oxide.
The anti-aging agent is formed by mixing a main antioxidant and an auxiliary antioxidant in a mass ratio of 1:3, wherein the main antioxidant is a hindered phenol antioxidant, and the auxiliary antioxidant is a phosphite antioxidant; the main antioxidant is antioxidant 1010; the auxiliary antioxidant is antioxidant 168. The filler is obtained by grafting the inorganic filler with whiteness larger than 85 through a coupling agent, and the coupling agent is a silane coupling agent.
The preparation method of the thermoplastic vulcanized elastomer material with high resilience and high strength comprises the following steps:
feeding ethylene propylene diene monomer, polypropylene, processing oil, an anti-aging agent, a filler and a processing aid into a double-screw extruder through a weightlessness scale for blending; the screw rotating speed is 460rpm/min, the screw length-diameter ratio is 55-64, the processing temperature is 160-.
The processing temperature is specifically as follows: the first zone temperature of the processing is 140 ℃, the second zone temperature is 180 ℃, the third zone temperature is 190 ℃, the fourth zone temperature is 200 ℃, the fifth zone temperature is 205 ℃, the sixth zone temperature is 210 ℃, the seventh zone temperature is 215 ℃, the eighth zone temperature is 220 ℃, the tenth zone temperature is 220 ℃, the eleventh zone temperature is 220 ℃, the twelfth zone temperature is 220 ℃ and the thirteenth zone temperature is 220 ℃.
Example 6
The high-resilience high-strength thermoplastic vulcanized elastomer material is prepared from the following raw materials in parts by weight: 115 parts of ethylene propylene diene monomer, 76 parts of polypropylene, 45 parts of thermoplastic elastomer, 65 parts of processing oil, 8 parts of a vulcanization system, 4 parts of processing aid, 3 parts of anti-aging agent and 35 parts of filler; the third monomer of the ethylene propylene diene monomer is ethylene norbornene, wherein the ethylene content is 55 wt%, and the third monomer content is 12 wt%.
Wherein the thermoplastic elastomer is formed by mixing thermoplastic styrene elastomer and thermoplastic polyurethane elastomer according to the mass ratio of 1: 2. The ethylene component of the thermoplastic polyolefin elastomer is less than 15 percent, and the puncture force is not less than 300 lbf; the thermoplastic styrene elastomer has a hardness-softness ratio of 20/80-40/60 and a molecular weight of at least 20 ten thousand; the hard segment type of the thermoplastic polyurethane elastomer is MDI or H12MDI elastomer, wherein the relative molecular mass of the soft segment is not less than 2000. The polypropylene is formed by mixing homo-polypropylene and co-polypropylene according to the mass ratio of 2:1, and the flexural modulus of the polypropylene is more than 1000 MPa; the polypropylene is high-melt-strength polypropylene, and the melt viscosity of the polypropylene is more than 1000Pas when the shearing force is 200Pa and the frequency is 10 HZ.
The processing oil is paraffin oil, CA is less than or equal to 5, CN is less than or equal to 40, and CP is more than or equal to 65; the kinematic viscosity of the processing oil at 100 ℃ is not less than 20mm2And s. The vulcanizing system is a phenolic resin vulcanizing system and is formed by mixing vulcanizing agent octyl phenolic resin and accelerator stannous chloride hydrate in a mass ratio of 3: 1.
The processing aid is formed by mixing a lubricant, a light stabilizer and a coloring agent according to the mass ratio of 1:1: 1; the lubricant is formed by mixing zinc stearate and dimethyl silicone oil according to the mass ratio of 1: 1; the light stabilizer is benzophenone; the colorant is carbon black.
The anti-aging agent is formed by mixing a main antioxidant and an auxiliary antioxidant in a mass ratio of 1:3, wherein the main antioxidant is a hindered phenol antioxidant, and the auxiliary antioxidant is a phosphite antioxidant; the main antioxidant is antioxidant 1076; the auxiliary antioxidant is antioxidant 168. The filler is obtained by grafting the inorganic filler with whiteness larger than 85 through a coupling agent, and the coupling agent is a silane coupling agent.
The preparation method of the thermoplastic vulcanized elastomer material with high resilience and high strength comprises the following steps:
feeding ethylene propylene diene monomer, polypropylene, processing oil, an anti-aging agent, a filler and a processing aid into a double-screw extruder through a weightlessness scale for blending; the screw rotation speed is 350rpm/min, the screw length-diameter ratio is 55-64, the processing temperature is 160-.
The processing temperature is specifically as follows: the first zone temperature of the processing is 140 ℃, the second zone temperature is 180 ℃, the third zone temperature is 190 ℃, the fourth zone temperature is 200 ℃, the fifth zone temperature is 205 ℃, the sixth zone temperature is 210 ℃, the seventh zone temperature is 215 ℃, the eighth zone temperature is 220 ℃, the tenth zone temperature is 220 ℃, the eleventh zone temperature is 220 ℃, the twelfth zone temperature is 220 ℃ and the thirteenth zone temperature is 220 ℃.
Example 7
The high-resilience high-strength thermoplastic vulcanized elastomer material is prepared from the following raw materials in parts by weight: 112 parts of ethylene propylene diene monomer, 76 parts of polypropylene, 42 parts of thermoplastic elastomer, 25 parts of processing oil, 12 parts of a vulcanization system, 7 parts of processing aid, 4.5 parts of anti-aging agent and 36 parts of filler; the third monomer of the ethylene propylene diene monomer is ethylene norbornene, wherein the ethylene content is 62 wt%, and the third monomer content is 10 wt%.
Wherein the thermoplastic elastomer is formed by mixing a thermoplastic styrene elastomer and a thermoplastic polyurethane elastomer according to the mass ratio of 1: 2. The ethylene component of the thermoplastic polyolefin elastomer is less than 15 percent, and the puncture force is not less than 300 lbf; the thermoplastic styrene elastomer has a hardness-softness ratio of 20/80-40/60 and a molecular weight of at least 20 ten thousand; the hard segment type of the thermoplastic polyurethane elastomer is MDI or H12MDI elastomer, wherein the relative molecular mass of the soft segment is not less than 2000. The polypropylene is formed by mixing homo-polypropylene and co-polypropylene according to the mass ratio of 1:2, and the flexural modulus of the polypropylene is more than 1000 MPa; the polypropylene is high-melt-strength polypropylene, and the melt viscosity of the polypropylene is more than 1000Pas when the shearing force is 200Pa and the frequency is 10 HZ.
The processing oil is paraffin oil, CA is less than or equal to 5, CN is less than or equal to 40, and CP is more than or equal to 65; the kinematic viscosity of the processing oil at 100 ℃ is not less than 20mm2And s. The vulcanizing system is a phenolic resin vulcanizing system and is formed by mixing vulcanizing agent octyl phenolic resin and accelerator stannous chloride hydrate in a mass ratio of 3: 1.
The processing aid is formed by mixing a lubricant, a light stabilizer and a coloring agent according to the mass ratio of 1.5:1: 0.5; the lubricant is formed by mixing PE wax and dimethyl silicone oil according to the mass ratio of 1: 1; the light stabilizer is formed by mixing hindered amine and benzophenone according to the mass ratio of 1: 1; the colorant is chromate.
The anti-aging agent is formed by mixing a main antioxidant and an auxiliary antioxidant in a mass ratio of 1:3, wherein the main antioxidant is a hindered phenol antioxidant, and the auxiliary antioxidant is a phosphite antioxidant; the main antioxidant is antioxidant 1076; the auxiliary antioxidant is antioxidant P-EPQ. The filler is obtained by grafting the inorganic filler with whiteness larger than 85 through a coupling agent, and the coupling agent is a titanate coupling agent.
The preparation method of the thermoplastic vulcanized elastomer material with high resilience and high strength comprises the following steps:
feeding ethylene propylene diene monomer, polypropylene, processing oil, an anti-aging agent, a filler and a processing aid into a double-screw extruder through a weightlessness scale for blending; the screw rotation speed is 500rpm/min, the screw length-diameter ratio is 55-64, the processing temperature is 160-.
The processing temperature is specifically as follows: the first zone temperature of the processing is 140 ℃, the second zone temperature is 180 ℃, the third zone temperature is 190 ℃, the fourth zone temperature is 200 ℃, the fifth zone temperature is 205 ℃, the sixth zone temperature is 210 ℃, the seventh zone temperature is 215 ℃, the eighth zone temperature is 220 ℃, the tenth zone temperature is 220 ℃, the eleventh zone temperature is 220 ℃, the twelfth zone temperature is 220 ℃ and the thirteenth zone temperature is 220 ℃.
Example 8
The high-resilience high-strength thermoplastic vulcanized elastomer material is prepared from the following raw materials in parts by weight: 96 parts of ethylene propylene diene monomer, 78 parts of polypropylene, 42 parts of thermoplastic elastomer, 52 parts of processing oil, 7 parts of a vulcanization system, 8 parts of processing aid, 4.2 parts of anti-aging agent and 42 parts of filler; the third monomer of the ethylene propylene diene monomer is ethylene norbornene, wherein the ethylene content is 55 wt%, and the third monomer content is 10 wt%.
Wherein the thermoplastic elastomer is formed by mixing a thermoplastic polyolefin elastomer, a thermoplastic styrene elastomer and a thermoplastic polyurethane elastomer according to the mass ratio of 1:1: 1. The ethylene component of the thermoplastic polyolefin elastomer is less than 15 percent, and the puncture force is not less than 300 lbf; the thermoplastic styrene elastomer has a hardness-softness ratio of 20/80-40/60 and a molecular weight of at least 20 ten thousand; the hard segment type of the thermoplastic polyurethane elastomer is MDI or H12MDI elastomer, wherein the relative molecular mass of the soft segment is not less than 2000. The polypropylene is formed by mixing homo-polypropylene and co-polypropylene according to the mass ratio of 1:1, and the flexural modulus of the polypropylene is more than 1000 MPa; the polypropylene is high-melt-strength polypropylene, and the melt viscosity of the polypropylene is more than 1000Pas when the shearing force is 200Pa and the frequency is 10 HZ.
The processing oil is paraffin oil, CA is less than or equal to 5, CN is less than or equal to 40, and CP is more than or equal to 65; the kinematic viscosity of the processing oil at 100 ℃ is not less than 20mm2And s. The vulcanizing system is a phenolic resin vulcanizing system and is formed by mixing vulcanizing agent octyl phenolic resin and accelerator stannous chloride hydrate in a mass ratio of 3: 1.
The processing aid is formed by mixing a lubricant, a light stabilizer and a coloring agent according to the mass ratio of 1:1: 1; the lubricant is prepared by mixing zinc stearate, calcium stearate and dimethyl silicone oil according to the mass ratio of 1:1: 1; the light stabilizer is benzophenone; the colorant is chromate.
The anti-aging agent is formed by mixing a main antioxidant and an auxiliary antioxidant in a mass ratio of 1:3, wherein the main antioxidant is a hindered phenol antioxidant, and the auxiliary antioxidant is a phosphite antioxidant; the main antioxidant is antioxidant 1790; the secondary antioxidant is antioxidant 618. The filler is obtained by grafting the inorganic filler with whiteness larger than 85 through a coupling agent, and the coupling agent is a zirconium coupling agent.
The preparation method of the thermoplastic vulcanized elastomer material with high resilience and high strength comprises the following steps:
feeding ethylene propylene diene monomer, polypropylene, processing oil, an anti-aging agent, a filler and a processing aid into a double-screw extruder through a weightlessness scale for blending; the screw rotation speed is 480rpm/min, the screw length-diameter ratio is 55-64, the processing temperature is 160-. The processing temperature is specifically as follows: the first zone temperature of the processing is 140 ℃, the second zone temperature is 180 ℃, the third zone temperature is 190 ℃, the fourth zone temperature is 200 ℃, the fifth zone temperature is 205 ℃, the sixth zone temperature is 210 ℃, the seventh zone temperature is 215 ℃, the eighth zone temperature is 220 ℃, the tenth zone temperature is 220 ℃, the eleventh zone temperature is 220 ℃, the twelfth zone temperature is 220 ℃ and the thirteenth zone temperature is 220 ℃.
And (3) performance testing:
the measurements of hardness, tensile strength, elongation at break and compression set were carried out on the high resilience high strength thermoplastic vulcanizate of examples 1 to 8, and the specific results are given in the following table:
Figure BDA0002558063290000121
as can be seen from the above table, the thermoplastic vulcanized elastomer material prepared by the invention has good hardness, tensile strength, elongation at break, compression set, high resilience, high strength and good physical and mechanical properties, and is suitable for being used as a raw material of products such as automobile sealing strips, wire harness sheaths and the like.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.

Claims (10)

1. The high-resilience high-strength thermoplastic vulcanized elastomer material is characterized by being prepared from the following raw materials in parts by weight: 80-120 parts of ethylene propylene diene monomer, 30-90 parts of polypropylene, 10-50 parts of thermoplastic elastomer, 10-80 parts of processing oil, 0.2-10 parts of a vulcanization system, 0.1-10 parts of a processing aid, 0.5-5 parts of an anti-aging agent and 20-50 parts of a filler;
the third monomer of the ethylene propylene diene monomer is ethylene norbornene, wherein the ethylene content is 40-70 wt%, and the third monomer content is 2-15 wt%;
the thermoplastic elastomer comprises one or a mixture of at least two of thermoplastic polyolefin elastomer, thermoplastic styrene elastomer and thermoplastic polyurethane elastomer.
2. The high resilience and high strength thermoplastic vulcanizate according to claim 1, wherein the thermoplastic polyolefin elastomer has an ethylene content of less than 15% and a puncture force of not less than 300 lbf; the thermoplastic styrene-based elastomer has a hardness-softness ratio of 20/80 to 40/60 and a molecular weight of at least 20 ten thousand; the hard segment type of the thermoplastic polyurethane elastomer is MDI or H12MDI elastomer, wherein the relative molecular mass of the soft segment is not less than 2000.
3. The high resilience and high strength thermoplastic vulcanizate according to claim 1, wherein the polypropylene comprises one of homo polypropylene, co polypropylene or a mixture of at least two thereof, and the flexural modulus of the polypropylene is greater than 1000 MPa; the polypropylene is high-melt-strength polypropylene, and the melt viscosity of the polypropylene is more than 1000Pas when the shearing force is 200Pa and the frequency is 10 HZ.
4. The high-resilience high-strength thermoplastic vulcanizate according to claim 1, wherein the processing oil is paraffin oil, CA ≤ 5, CN ≤ 40, and CP ≥ 65; the kinematic viscosity of the processing oil at 100 ℃ is not less than 20mm2/s。
5. The high-resilience high-strength thermoplastic vulcanized elastomer material as claimed in claim 1, wherein the vulcanization system is a phenolic resin vulcanization system formed by mixing octyl phenolic resin serving as a vulcanizing agent and stannous chloride hydrate serving as a promoter in a mass ratio of 3: 1.
6. The high resilience and high strength thermoplastic vulcanizate according to claim 1, wherein the processing aid is one or a mixture of at least two of a lubricant, a light stabilizer, a colorant; the lubricant is one or a mixture of at least two of zinc stearate, calcium stearate, PE wax and dimethyl silicone oil; the light stabilizer is one or a mixture of at least two of hindered amine and benzophenone; the colorant is one or a mixture of at least two of metal oxide, carbon black, metal sulfide and chromate.
7. The high-resilience high-strength thermoplastic vulcanized elastomer material as claimed in claim 1, wherein the antioxidant is prepared by mixing a primary antioxidant and a secondary antioxidant in a mass ratio of 1:3, the primary antioxidant is a hindered phenol antioxidant, and the secondary antioxidant is a phosphite antioxidant; the main antioxidant is one of antioxidant 1010, antioxidant 1076 and antioxidant 1790; the auxiliary antioxidant is one of antioxidant 168, antioxidant 618 and antioxidant P-EPQ.
8. The high-resilience high-strength thermoplastic vulcanized elastomer material according to claim 1, wherein the filler is an inorganic filler with whiteness of more than 85, and is obtained by grafting treatment through a coupling agent, and the coupling agent is one or more of a silane coupling agent, a titanate coupling agent and a zirconium coupling agent.
9. A preparation method of a high-resilience high-strength thermoplastic vulcanized elastomer material is characterized by comprising the following steps:
feeding ethylene propylene diene monomer, polypropylene, processing oil, an anti-aging agent, a filler and a processing aid into a double-screw extruder through a weightlessness scale for blending; the screw rotation speed is 300 plus one/min, the screw length-diameter ratio is 55-64, the processing temperature is 160 plus one/min, the rubber, the filler, the oil product and the processing aid are fully sheared and mixed during banburying, then the rubber, the filler, the oil product and the processing aid are dynamically crosslinked with the polypropylene, the elastomer is introduced at the later stage of crosslinking, the position on the screw is located from the third section of cylinder body to the tenth section of cylinder body, and the side feeding position is located at the sixth section of cylinder body.
10. The process for the preparation of a high resilience and high strength thermoplastic vulcanizate according to claim 9, wherein the processing temperature is in particular: the first zone temperature of the processing is 140 ℃, the second zone temperature is 180 ℃, the third zone temperature is 190 ℃, the fourth zone temperature is 200 ℃, the fifth zone temperature is 205 ℃, the sixth zone temperature is 210 ℃, the seventh zone temperature is 215 ℃, the eighth zone temperature is 220 ℃, the tenth zone temperature is 220 ℃, the eleventh zone temperature is 220 ℃, the twelfth zone temperature is 220 ℃ and the thirteenth zone temperature is 220 ℃.
CN202010599300.1A 2020-06-28 2020-06-28 High-resilience high-strength thermoplastic vulcanized elastomer material and preparation method thereof Pending CN111662511A (en)

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CN101440182A (en) * 2007-11-19 2009-05-27 上海日之升新技术发展有限公司 Method for producing high quality dynamic vulcanization thermoplastic elastomer
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