CN111944246A - High-temperature-resistant oil-resistant high-flame-retardant environment-friendly foaming adhesive mixture - Google Patents

High-temperature-resistant oil-resistant high-flame-retardant environment-friendly foaming adhesive mixture Download PDF

Info

Publication number
CN111944246A
CN111944246A CN202010857838.8A CN202010857838A CN111944246A CN 111944246 A CN111944246 A CN 111944246A CN 202010857838 A CN202010857838 A CN 202010857838A CN 111944246 A CN111944246 A CN 111944246A
Authority
CN
China
Prior art keywords
parts
rubber
upper plug
mixture
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202010857838.8A
Other languages
Chinese (zh)
Inventor
吕荣福
古景根
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sichuan Yuanxing Rubber Co Ltd
Original Assignee
Sichuan Yuanxing Rubber Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sichuan Yuanxing Rubber Co Ltd filed Critical Sichuan Yuanxing Rubber Co Ltd
Priority to CN202010857838.8A priority Critical patent/CN111944246A/en
Publication of CN111944246A publication Critical patent/CN111944246A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/22—Expandable microspheres, e.g. Expancel®
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
    • C08J2323/28—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/16—Ethene-propene or ethene-propene-diene copolymers
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/328—Phosphates of heavy metals
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K3/02—Elements
    • C08K3/06—Sulfur
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The invention provides a high-temperature-resistant oil-resistant high-flame-retardant environment-friendly foam rubber mixture, belonging to the technical field of foam tires. The paint comprises the following components in parts by weight: 20-40 parts of ethylene-vinyl acetate copolymer, 0-50 parts of halogenated butyl rubber, 0-50 parts of polyisoprene rubber, 0-40 parts of ethylene propylene diene monomer, 0.2-1 part of LDPE, 3-5 parts of carbon black, 5-10 parts of zirconium hydrogen phosphate and an inorganic filler: 5-100 parts of zinc oxide, 2-5 parts of stearic acid, 1-1.5 parts of stearic acid, 2-4 parts of an anti-aging agent, 0.5-1 part of sulfur, 1-3 parts of TB710, 1-3 parts of an accelerator, 1-2 parts of a homogenizing agent and 3-5 parts of physical foaming microbeads EM. After the foaming agent is implemented, the foaming product can meet the American UL 94HB standard, and can meet the market use in the aspects of high temperature resistance and oil resistance compared with the existing market products.

Description

High-temperature-resistant oil-resistant high-flame-retardant environment-friendly foaming adhesive mixture
Technical Field
The invention belongs to the technical field of foaming tires, and particularly relates to a high-temperature-resistant oil-resistant high-flame-retardant environment-friendly foaming rubber mixture.
Background
Most of the foamed tires in the current market still do not pay attention to the environmental protection, flame retardant and safety performance, and the high temperature resistance and oil resistance of the foamed tires are poor (the shrinkage is serious), so that the produced products have serious deformation and short service life in the use process.
Most of tires in the current market cannot solve the problems that the foamed tire is too large in deformation after being used for a period of time, and the foamed material adopting similar components is too large in compression deformation in the using process and cannot meet the use requirements. The products on the market at present have no effective available design on flame retardance, oil resistance and high temperature resistance.
Disclosure of Invention
In order to solve the problem that products in the current market have no effective available design in flame retardance, oil resistance and high temperature resistance, the invention adopts the following technical scheme:
a high-flame-retardant environment-friendly foaming adhesive mixture resistant to high temperature and oil comprises the following components in parts by weight: 20-40 parts of ethylene-vinyl acetate copolymer (EVM), 0-50 parts of halogenated butyl rubber (BIIR), 0-50 parts of polyisoprene rubber (NR), 0-40 parts of Ethylene Propylene Diene Monomer (EPDM), 0.2-1 part of LDPE, 3-5 parts of carbon black, 5-10 parts of zirconium hydrogen phosphate and an inorganic filler: 5-100 parts of zinc oxide, 2-5 parts of stearic acid, 1-1.5 parts of stearic acid, 2-4 parts of an anti-aging agent, 0.5-1 part of sulfur, 1-3 parts of TB710, 1-3 parts of an accelerator, 1-2 parts of a homogenizing agent and 3-5 parts of physical foaming microbeads EM.
The more preferable technical scheme is that the high-flame-retardant environment-friendly foaming glue mixture with high temperature resistance and oil resistance comprises the following components in parts by weight: 20-30 parts of ethylene-vinyl acetate copolymer, 40-50 parts of halogenated butyl rubber, 40-50 parts of polyisoprene rubber, 20-40 parts of ethylene propylene diene monomer, 0.5-1 part of LDPE, 3-5 parts of carbon black, 5-10 parts of zirconium hydrogen phosphate and an inorganic filler: 5-100 parts of zinc oxide, 2-5 parts of stearic acid, 1-1.5 parts of stearic acid, 2-4 parts of an anti-aging agent, 0.5-1 part of sulfur, 1-3 parts of TB710, 1-3 parts of an accelerator, 1-2 parts of a homogenizing agent and 3-5 parts of physical foaming microbeads EM.
Further, the halogenated butyl rubber is chlorinated butyl rubber or brominated butyl rubber.
Further, the inorganic filler is a mixture of light calcium carbonate and diatomite.
Furthermore, the antioxidant is a mixture of any two or three of antioxidant AFS, antioxidant BHT and antioxidant SP.
Further, the accelerator is a mixture of any two or three of accelerator EM33, accelerator TS and accelerator D.
Further, the homogenizing agent is RH150 or AD 1401.
The invention also provides a preparation method of the high-temperature-resistant oil-resistant high-flame-retardant environment-friendly foam rubber mixture, which comprises the following steps:
starting an internal mixer, adding halogenated butyl rubber and ethylene propylene diene monomer rubber into an internal mixing chamber, then pressing an upper plug downwards, adding diatomite, pressing the upper plug downwards until the temperature rises to 120 ℃, then lifting the upper plug for purging, re-lifting the upper plug downwards until the temperature reaches 145 ℃, and discharging to obtain rubber A;
starting an internal mixer, adding polyisoprene rubber and an ethylene-vinyl acetate copolymer into an internal mixing chamber, then pressing down by using an upper plug, adding carbon black and calcium carbonate, pressing down by using the upper plug until the temperature rises to 110 ℃, then lifting the upper plug for purging, pressing down by using the upper plug again until the temperature reaches 135 ℃, and discharging to obtain rubber B;
starting an internal mixer, putting the rubber A and the rubber B into an internal mixing chamber, pressing down the upper plug for 20 seconds, adding zirconium hydrogen phosphate, zinc oxide, stearic acid, an anti-aging agent and a homogenizing agent, pressing down the upper plug until the temperature rises to 110 ℃, then lifting up the upper plug for purging, pressing down the upper plug again until the temperature reaches 145 ℃, discharging the upper plug, turning over the upper plug for about 150 seconds on a belt type open mill with a roller filled with cooling water, cooling to 90-95 ℃, closing the cooling water, adding LDPE, sulfur and an accelerator into the rubber material, continuing turning over for 120 seconds, opening the cooling water, adding physical foaming microbeads, turning over for 3 minutes, and discharging to obtain the required mixed rubber.
Compared with the prior art, the invention has the beneficial effects that:
the product produced by using the mixture of the invention has a dimensional change of 3-5% after aging cooling to normal temperature at 150 ℃ for 30 min. The foaming product can meet the US UL 94HB standard, and can be improved to meet the market use in the aspects of high temperature resistance and oil resistance compared with the existing market products. The environment protection can pass the requirement of European Union standard, and the flame retardance can reach the requirement of American standard.
Detailed Description
The present invention will be further described with reference to the following examples, which are intended to illustrate only some, but not all, of the embodiments of the present invention. Based on the embodiments of the present invention, other embodiments used by those skilled in the art without any creative effort belong to the protection scope of the present invention.
Example 1:
EVM: 20 parts, BIIR 2222: 40 parts, NR 5: 20 parts, EPDM 4045: 20 parts of LDPE: 0.5 part of carbon black: 5 parts of zirconium hydrogen phosphate: 10 parts of calcium carbonate: 30 parts of diatomite: 45 parts of zinc oxide: 2 parts and stearic acid: 1 part of an antioxidant AFS: 1.5 parts of an antioxidant BHT: 1.5 parts, sulfur: 0.5 part, 1.9 parts of TB710, an accelerator EM 33: 1.2 parts, accelerator TS: 0.8 part of homogenizing agent RH 150: 2 parts of physical foaming micro-beads EM: 4.5 parts.
Starting the internal mixer, starting at the rotation speed of 55RPM, putting BIIR and EPDM into the internal mixing chamber, pressing the upper plug for 20 seconds, adding diatomite, pressing the upper plug until the temperature rises to 120 ℃, then lifting the upper plug to purge (purge all powder falling on the upper plug into the internal mixing chamber), pressing the upper plug again until the temperature reaches 145 ℃, and discharging to obtain the glue A.
Starting the internal mixer, starting at the rotation speed of 55RPM, putting NR and EVM into the internal mixing chamber, then pressing the upper ram for 20 seconds, adding carbon black and calcium carbonate, pressing the upper ram until the temperature rises to 110 ℃, then lifting the upper ram to purge (purge all powder falling on the upper ram into the internal mixing chamber), pressing the upper ram again until the temperature reaches 135 ℃, and discharging to obtain the B rubber.
Starting an internal mixer, starting the internal mixer at the rotation speed of 55RPM, putting glue A and glue B into the internal mixing chamber, pressing down the upper ram for 20 seconds, adding zirconium hydrogen phosphate, zinc oxide, stearic acid, an anti-aging agent and a homogenizing agent, pressing down the upper ram until the temperature rises to 110 ℃, then lifting up the upper ram to purge (purge all powder falling on the upper ram into the internal mixing chamber), pressing down the upper ram again until the temperature reaches 145 ℃, discharging the upper ram, turning over the upper ram on a belt-type open mill with a roller filled with cooling water for about 150 seconds (see equipment), cooling to 90-95 ℃, closing the cooling water, adding LDPE, sulfur and the accelerator into the rubber material, continuing to turn over for 120 seconds, starting the cooling water, adding physical foaming microbeads, turning over for 3 minutes, and discharging to obtain the required mixed rubber.
When the sizing material prepared by the formula is tested by a thermal dynamic analyzer, the total amount of 15PAHS is only 7PPM (German AFPS GS 2019: 01PAK requires less than 50 PPM), and the sizing material meets the standard. The combustion test data of the SGS mechanism is 36mm/min (the U.S. UL 94-2013 requires less than 40 mm/min), and the standard is met. After aging and cooling to normal temperature at 150 ℃ for 30min, the size change is 3.37% (the OE manufacturer control standard is below 12%), and the standard is met. Thermal dynamic analysis DMA test, tan (heat generation common to evaluation materials) at 80 ℃ of 0.045(OE plant control standard below 0.10), meets the standard.
Example 2:
EVM: 30 parts, BIIR 2222: 50 parts, EPDM 4045: 20 parts of LDPE: 0.2 part of carbon black: 5 parts of zirconium hydrogen phosphate: 6 parts of calcium carbonate: 30 parts of diatomite: 45 parts of zinc oxide: 2 parts and stearic acid: 1 part of an antioxidant AFS: 2 parts of an antioxidant BHT: 1 part and sulfur: 0.5 part, 2.2 parts of TB710, an accelerator EM 33: 1.2 parts, accelerator TS: 1.0 part of homogenizing agent RH 150: 2.5 parts of physical foaming micro-bead EM: 5 parts of the raw materials.
The preparation method is the same as that of example 1, and the high-temperature-resistant oil-resistant high-flame-retardant environment-friendly foam rubber mixture is obtained.
When the sizing material prepared by the formula is tested by a thermal dynamic analyzer, the total amount of 15PAHS is only 7.3PPM (German AFPS GS 2019: 01PAK requires less than 50 PPM), and the sizing material meets the standard. The combustion test data of the SGS mechanism is 34mm/min (the U.S. UL 94-2013 requires less than 40 mm/min), and the standard is met. After aging and cooling to normal temperature at 150 ℃ for 30min, the size change is 3.22% (the OE manufacturer control standard is below 12%), and the standard is met. The thermal dynamic analysis DMA test, 80 ℃ tan (common for evaluating the heat generation of materials) is 0.053(OE factory control standard is below 0.10), meets the standard.
Example 3:
EVM: 30 parts, NR 5: 50 parts, EPDM 4045: 20 parts of LDPE: 1 part of carbon black: 5 parts of zirconium hydrogen phosphate: 10 parts of calcium carbonate: 30 parts of diatomite: 60 parts of zinc oxide: 3 parts of stearic acid: 0.8 part of an antioxidant AFS: 2 parts of an antioxidant BHT: 2 parts of sulfur: 1 part, 1.0 part of TB710, 1.0 part of accelerator EM 33: 1.2 parts, accelerator TS: 1.4 parts of homogenizing agent RH 150: 3 parts of physical foaming micro-beads EM: 3.5 parts.
The preparation method is the same as that of example 1, and the high-temperature-resistant oil-resistant high-flame-retardant environment-friendly foam rubber mixture is obtained.
When the sizing material prepared by the formula is tested by a thermal dynamic analyzer, the total amount of 15PAHS is only 8PPM (German AFPS GS 2019: 01PAK requires less than 50 PPM), and the sizing material meets the standard. The combustion test data of the SGS mechanism is 38mm/min (the U.S. UL 94-2013 requires less than 40 mm/min), and the standard is met. After aging and cooling to normal temperature at 150 ℃ for 30min, the size change is 4.52% (the OE manufacturer control standard is below 12%), and the standard is met. The thermal dynamic analysis DMA test shows that the temperature of 80 ℃ tan (commonly used for evaluating the heat generation of materials) is 0.066 (the OE factory control standard is below 0.10), and the standard is met.
Example 4:
EVM: 30 parts, NR 5: 40 parts, BIIR 2222: 40 parts of LDPE: 0.6 part of carbon black: 5 parts of zirconium hydrogen phosphate: 10 parts of calcium carbonate: 40 parts of diatomite: 60 parts of zinc oxide: 2.5 parts, stearic acid: 1 part of an antioxidant AFS: 2 parts of an antioxidant BHT: 1.5 parts, sulfur: 1 part, 1.0 part of TB710, 1.0 part of accelerator EM 33: 1.2 parts, accelerator TS: 1.4 parts of accelerator D: 1 part of homogenizing agent RH 150: 3 parts of physical foaming micro-beads EM: 3.5 parts.
The preparation method is the same as that of example 1, and the high-temperature-resistant oil-resistant high-flame-retardant environment-friendly foam rubber mixture is obtained.
When the sizing material prepared by the formula is tested by a thermal dynamic analyzer, the total amount of 15PAHS is only 7.8PPM (German AFPS GS 2019: 01PAK requires less than 50 PPM), and the sizing material meets the standard. The combustion test data of the SGS mechanism is 33mm/min (the U.S. UL 94-2013 requires less than 40 mm/min), and the standard is met. After aging and cooling to normal temperature at 150 ℃ for 30min, the size change is 3.95% (the OE manufacturer control standard is below 12%), and the standard is met. The thermal dynamic analysis DMA test, 80 ℃ tan (common for evaluating the heat generation of materials) at 0.057(OE plant control standard below 0.10), meets the standard.
Example 5:
EVM: 35 parts, NR 5: 45 parts, BIIR 2222: 30 parts and LDPE: 0.6 part of carbon black: 5 parts of zirconium hydrogen phosphate: 8 parts of calcium carbonate: 40 parts of diatomite: 55 parts and zinc oxide: 2.5 parts, stearic acid: 1 part of an antioxidant AFS: 2 parts of an antioxidant BHT: 1.5 parts of an anti-aging agent SP: 0.5 part, sulfur: 1 part, 1.0 part of TB710, 1.0 part of accelerator EM 33: 1.2 parts, accelerator TS: 1.4 parts of homogenizing agent RH 150: 2 parts of physical foaming micro-beads EM: 3.5 parts.
The preparation method is the same as that of example 1, and the high-temperature-resistant oil-resistant high-flame-retardant environment-friendly foam rubber mixture is obtained.
When the sizing material prepared by the formula is tested by a thermal dynamic analyzer, the total amount of 15PAHS is only 7.6PPM (German AFPS GS 2019: 01PAK requires less than 50 PPM), and the sizing material meets the standard. The combustion test data of the SGS mechanism is 33mm/min (the U.S. UL 94-2013 requires less than 40 mm/min), and the standard is met. After aging and cooling to normal temperature at 150 ℃ for 30min, the size change is 3.86% (the OE manufacturer control standard is below 12%), and the standard is met. The thermal dynamic analysis DMA test, 80 ℃ tan (commonly used to evaluate the heat generation of materials) is 0.073(OE plant control standard is below 0.10), meeting the standard.
The invention selects the ethylene-vinyl acetate copolymer (EVM), which is a novel environment-friendly material with the content of 40-45 percent different from the EVA raw material with the vinyl acetate. (similar to the synthesis of EVA, only part of the monomers come from plants, but not petroleum extracts), so that the produced product is more environment-friendly and has a certain flame retardant effect, and a certain amount of zirconium hydrogen phosphate is added as a flame retardant; physical hydrocarbon foaming micro-beads are selected as a main foaming agent, so that the production environment pollution caused by VOCS (volatile organic Compounds) caused by the use of a chemical foaming agent is avoided; the inorganic matter is selected to be large in quantity to fill and support the bearing capacity of the foaming body.
The physical hydrocarbon foaming micro-beads are 15-40 mu m substance aggregates which can be gasified and expanded under heating (rubber vulcanization temperature), and the micro-beads can be softened and expanded by about four times (specific multiplying power can be controlled according to the using amount, the vulcanization temperature and the time) to form a hollow sphere; when the micro beads are uniformly mixed in the rubber, the three-dimensional network state molecular distance after the rubber is vulcanized can be expanded, so that the foamed rubber product which can be compressed in a large proportion and has high resilience is formed.
After the conventional EVA and NR foamed products are subjected to high temperature, the thermal aging deformation is very serious, the deformation can reach 50 percent, and when a proper amount of halogenated butyl rubber or ethylene propylene diene monomer rubber (both belong to saturated rubber with a single main chain) is added, the thermal aging resistance and the oil resistance of the conventional EVA and NR foamed products can be in the required standard range.
Because the recovery capability of the foamed rubber product is greatly reduced after the foamed rubber product is compressed at a certain frequency at a high temperature, and an anti-aging agent with pollution property cannot be added in the formula to ensure the environmental protection characteristic of the product, a proper amount of LDPE (thermoplastic material) is added in the formula to improve the extrusion recovery property of the product.
After the foaming agent is implemented, the foaming product can meet the American UL 94HB standard, and can meet the market use in the aspects of high temperature resistance and oil resistance compared with the existing market products.
Although the invention has been described herein with reference to illustrative embodiments thereof, it should be understood that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure.

Claims (8)

1. The high-flame-retardant environment-friendly foaming adhesive mixture with high temperature resistance and oil resistance is characterized by comprising the following components in parts by weight: 20-40 parts of ethylene-vinyl acetate copolymer, 0-50 parts of halogenated butyl rubber, 0-50 parts of polyisoprene rubber, 0-40 parts of ethylene propylene diene monomer, 0.2-1 part of LDPE, 3-5 parts of carbon black, 5-10 parts of zirconium hydrogen phosphate and an inorganic filler: 5-100 parts of zinc oxide, 2-5 parts of stearic acid, 1-1.5 parts of stearic acid, 2-4 parts of an anti-aging agent, 0.5-1 part of sulfur, 1-3 parts of TB710, 1-3 parts of an accelerator, 1-2 parts of a homogenizing agent and 3-5 parts of physical foaming microbeads EM.
2. The high-temperature-resistant oil-resistant high-flame-retardant environment-friendly foaming adhesive mixture as claimed in claim 1, which is characterized by comprising the following components in parts by weight: 20-30 parts of ethylene-vinyl acetate copolymer, 40-50 parts of halogenated butyl rubber, 40-50 parts of polyisoprene rubber, 20-40 parts of ethylene propylene diene monomer, 0.5-1 part of LDPE, 3-5 parts of carbon black, 5-10 parts of zirconium hydrogen phosphate and an inorganic filler: 5-100 parts of zinc oxide, 2-5 parts of stearic acid, 1-1.5 parts of stearic acid, 2-4 parts of an anti-aging agent, 0.5-1 part of sulfur, 1-3 parts of TB710, 1-3 parts of an accelerator, 1-2 parts of a homogenizing agent and 3-5 parts of physical foaming microbeads EM.
3. The high flame retardant environmental friendly foam rubber mixture with high temperature and oil resistance as claimed in claim 1, wherein the halogenated butyl rubber is chlorinated butyl rubber or brominated butyl rubber.
4. The high flame retardant environmental friendly foaming glue mixture with high temperature and oil resistance as claimed in claim 1, wherein the inorganic filler is a mixture of light calcium carbonate and diatomite.
5. The high flame retardant environment friendly foam rubber mixture with high temperature and oil resistance as claimed in claim 1, wherein the antioxidant is a mixture of any two or three of antioxidant AFS, antioxidant BHT and antioxidant SP.
6. The high flame retardant environmental friendly foam rubber mixture with high temperature and oil resistance as claimed in claim 1, wherein the accelerator is a mixture of any two or three of accelerator EM33, accelerator TS and accelerator D.
7. The high flame retardant environmental friendly foaming glue mixture with high temperature and oil resistance as claimed in claim 1, wherein the homogenizing agent is RH150 or AD 1401.
8. The preparation method of the high flame-retardant environment-friendly foaming glue mixture with high temperature resistance and oil resistance as claimed in any one of claims 1 to 7 is characterized by comprising the following steps:
starting an internal mixer, adding halogenated butyl rubber and ethylene propylene diene monomer rubber into an internal mixing chamber, then pressing an upper plug downwards, adding diatomite, pressing the upper plug downwards until the temperature rises to 120 ℃, then lifting the upper plug for purging, re-lifting the upper plug downwards until the temperature reaches 145 ℃, and discharging to obtain rubber A;
starting an internal mixer, adding polyisoprene rubber and an ethylene-vinyl acetate copolymer into an internal mixing chamber, then pressing down by using an upper plug, adding carbon black and calcium carbonate, pressing down by using the upper plug until the temperature rises to 110 ℃, then lifting the upper plug for purging, pressing down by using the upper plug again until the temperature reaches 135 ℃, and discharging to obtain rubber B;
starting an internal mixer, putting the rubber A and the rubber B into an internal mixing chamber, pressing down the upper plug for 20 seconds, adding zirconium hydrogen phosphate, zinc oxide, stearic acid, an anti-aging agent and a homogenizing agent, pressing down the upper plug until the temperature rises to 110 ℃, then lifting up the upper plug for purging, pressing down the upper plug again until the temperature reaches 145 ℃, discharging the upper plug, turning over the upper plug for about 150 seconds on a belt type open mill with a roller filled with cooling water, cooling to 90-95 ℃, closing the cooling water, adding LDPE, sulfur and an accelerator into the rubber material, continuing turning over for 120 seconds, opening the cooling water, adding physical foaming microbeads, turning over for 3 minutes, and discharging to obtain the required mixed rubber.
CN202010857838.8A 2020-08-24 2020-08-24 High-temperature-resistant oil-resistant high-flame-retardant environment-friendly foaming adhesive mixture Pending CN111944246A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010857838.8A CN111944246A (en) 2020-08-24 2020-08-24 High-temperature-resistant oil-resistant high-flame-retardant environment-friendly foaming adhesive mixture

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010857838.8A CN111944246A (en) 2020-08-24 2020-08-24 High-temperature-resistant oil-resistant high-flame-retardant environment-friendly foaming adhesive mixture

Publications (1)

Publication Number Publication Date
CN111944246A true CN111944246A (en) 2020-11-17

Family

ID=73360341

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010857838.8A Pending CN111944246A (en) 2020-08-24 2020-08-24 High-temperature-resistant oil-resistant high-flame-retardant environment-friendly foaming adhesive mixture

Country Status (1)

Country Link
CN (1) CN111944246A (en)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101747543A (en) * 2009-12-09 2010-06-23 浙江仕峰实业有限公司 Styrene-butadiene copolymer chemical foaming composition containing polystyrene micro-blocks, preparation method and application method thereof
CN105330995A (en) * 2015-12-11 2016-02-17 重庆可益荧新材料有限公司 Environment-friendly flame-retardant foaming rubber and preparation method thereof
CN106009463A (en) * 2016-06-17 2016-10-12 广东锐铂耐特新材料有限公司 Synthetic rubber foam material and preparation method thereof
CN106046448A (en) * 2016-06-17 2016-10-26 广东锐铂耐特新材料有限公司 Synthetic rubber foam material and preparation method thereof
CN106317662A (en) * 2016-08-19 2017-01-11 许文谈 Ultra-light wear-resistant anti-skidding shoe sole and preparation method thereof
CN107141526A (en) * 2017-06-02 2017-09-08 四川远星橡胶有限责任公司 Improve the refining gluing method of the decentralization of elastomeric compound containing white carbon
CN107652528A (en) * 2017-10-25 2018-02-02 扬州动易运动用品有限公司 Halogen-free flame-retardant expanded EVM rubber and its manufacture method

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101747543A (en) * 2009-12-09 2010-06-23 浙江仕峰实业有限公司 Styrene-butadiene copolymer chemical foaming composition containing polystyrene micro-blocks, preparation method and application method thereof
CN105330995A (en) * 2015-12-11 2016-02-17 重庆可益荧新材料有限公司 Environment-friendly flame-retardant foaming rubber and preparation method thereof
CN106009463A (en) * 2016-06-17 2016-10-12 广东锐铂耐特新材料有限公司 Synthetic rubber foam material and preparation method thereof
CN106046448A (en) * 2016-06-17 2016-10-26 广东锐铂耐特新材料有限公司 Synthetic rubber foam material and preparation method thereof
CN106317662A (en) * 2016-08-19 2017-01-11 许文谈 Ultra-light wear-resistant anti-skidding shoe sole and preparation method thereof
CN107141526A (en) * 2017-06-02 2017-09-08 四川远星橡胶有限责任公司 Improve the refining gluing method of the decentralization of elastomeric compound containing white carbon
CN107652528A (en) * 2017-10-25 2018-02-02 扬州动易运动用品有限公司 Halogen-free flame-retardant expanded EVM rubber and its manufacture method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
橡胶工业原材料与装备简明手册编审委员会编著: "《橡胶工业原材料与装备简明手册 2016年版》", 30 November 2016, 北京理工大学出版社 *

Similar Documents

Publication Publication Date Title
US9260578B2 (en) Thermoplastic elastomer foaming material
CN102226016B (en) Nano-mesoporous molecular sieve synergistic intumescent flame-retardant rubber and preparation method thereof
CN101709120B (en) Rubber additive and ethylene propylene diene monomer containing same
CN103059374B (en) High-temperature-resistant silane-crosslinked flame-retardation insulating material for automobile wires and preparation method thereof
CN106065123B (en) A kind of cold-resistant insualtion resin composition and preparation method thereof
CN110746706B (en) Low-smoke halogen-free ethylene propylene diene monomer composition and preparation method thereof
CN109251464B (en) SEBS composite foam material
CN109265779B (en) Flame-retardant insulated cable material and preparation method thereof
CN105419038A (en) Composition for manufacturing compound rubber mat and preparation method of composition
CN112375306B (en) Rubber material for sealing rubber strip
CN112812450A (en) Low-smoke halogen-free flame-retardant insulating material for cables
CN111944246A (en) High-temperature-resistant oil-resistant high-flame-retardant environment-friendly foaming adhesive mixture
US3240727A (en) Process for preparing cellular bodies from mixes containing amorphous polypropylene and expanded materials obtained therefrom
CN111205567A (en) Preparation method of low-VOC EPDM environment-friendly flame-retardant automotive interior rubber material
CN107057199B (en) Low-smoke halogen-free flame-retardant sealing strip and preparation method thereof
CN104262875B (en) Intumescent flame-retardant cable material taking plant-based active carbon as synergist and preparation method thereof
CN117304614B (en) Rubber elastomer material for vehicle and preparation method thereof
CN102234358B (en) Star styrene-butadiene-styrene (SBS) copolymer for sealing strip as well as preparation and application thereof
CN107337859A (en) Oil-immersed pump electric power cable oil resistant EP rubbers sheath material and preparation method thereof
CN115181422B (en) Flame retardant based on polyimide foam material and preparation method and application thereof
CN110294911B (en) Low-compression permanent-deformation active chlorine type acrylate rubber and preparation method thereof
CN116178803A (en) High flame-retardant tire sidewall rubber composition, mixing method and high flame-retardant tire
CN111944241B (en) Environment-friendly flame-retardant thermoplastic elastomer and preparation method thereof
CN111925577A (en) Low-rolling-resistance high-grip-force environment-friendly tire tread rubber mixture
CN114806026B (en) Cold-shrinkable ethylene propylene rubber pipe material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20201117

RJ01 Rejection of invention patent application after publication