CN110791011A - 150 ℃ irradiation crosslinking low-smoke halogen-free flame-retardant elastomer cable material and preparation method thereof - Google Patents

150 ℃ irradiation crosslinking low-smoke halogen-free flame-retardant elastomer cable material and preparation method thereof Download PDF

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Publication number
CN110791011A
CN110791011A CN201911091770.0A CN201911091770A CN110791011A CN 110791011 A CN110791011 A CN 110791011A CN 201911091770 A CN201911091770 A CN 201911091770A CN 110791011 A CN110791011 A CN 110791011A
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parts
cable material
flame
retardant
antioxidant
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Chinese (zh)
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曾伟
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Nantong Linger Rubber And Plastic Products Co Ltd
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Nantong Linger Rubber And Plastic Products Co Ltd
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Priority to CN201911091770.0A priority Critical patent/CN110791011A/en
Publication of CN110791011A publication Critical patent/CN110791011A/en
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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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
    • 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
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
    • 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
    • C08L2312/00—Crosslinking
    • C08L2312/06—Crosslinking by radiation

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a 150 ℃ irradiation crosslinking low-smoke halogen-free flame-retardant elastomer cable material and a preparation method thereof, wherein the cable material is prepared from the following components: 10-40 parts of ethylene-vinyl acetate rubber (EVM); 10-40 parts of ethylene propylene diene monomer EPDM; 5-20 parts of polyolefin resin; 0-20 parts of a plasticizing system; 20-40 parts of a flame-retardant system; 20-40 parts of a smoke abatement system; 1-8 parts of a flame-retardant synergistic system; 0.5-3 parts of an anti-aging system; 0.2-3 parts of a lubricating system; 0.2-1 part of an anti-ultraviolet system; 0.5-3 parts of a crosslinking sensitization system. After irradiation crosslinking, the wire and cable prepared from the cable material disclosed by the invention have higher physical and mechanical properties, excellent electrical insulation performance, chemical medium resistance, flame retardance and heat resistance, and can meet the requirement of a cable with a long-term working temperature of 150 ℃. The irradiation dose of the cable material is 10-20 Mrad.

Description

150 ℃ irradiation crosslinking low-smoke halogen-free flame-retardant elastomer cable material and preparation method thereof
Technical Field
The invention discloses a 150 ℃ irradiation crosslinking low-smoke halogen-free flame-retardant elastomer cable material and a preparation method thereof.
Background
With the rapid development of the world economy and the great progress of modern industrial technology, the wire and cable industry faces more opportunities and challenges, and german industry 4.0 and china manufacture 2025 both put more stringent requirements on the cable industry. The 150 ℃ irradiation crosslinking low-smoke halogen-free flame-retardant elastomer cable material has wide market application in the industries of new energy automobiles, high-temperature electrical appliances and the like, and in the prior art, in order to achieve the effect of low smoke, a large amount of hydroxides such as aluminum hydroxide ATH and magnesium hydroxide MTH are added, so that the mechanical property is degraded due to the large amount of filling.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the existing cable material, the invention provides a 150 ℃ irradiation crosslinking low-smoke halogen-free flame-retardant elastomer cable material which has excellent heat resistance (the temperature resistance level is 150 ℃), flame retardance, mechanical property, electrical property and small thermal deformation, and overcomes the problems of high temperature resistance, environmental protection, mechanical property and the like of the traditional cable material.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme:
the ethylene-vinyl acetate rubber EVM has high temperature resistance (the long-term temperature resistance level is 150 ℃), excellent oil resistance and flame retardance (the oxygen index LOI is more than 30 percent), and good char forming property and low smoke density during combustion, and ethylene propylene diene monomer EPDM (ethylene propylene diene monomer) with good compatibility with the EVM is matched to make up the defects of low temperature resistance, moisture resistance and processability of the EVM; and the use of hydroxide can be greatly reduced by the matching of the efficient flame-retardant system and the flame-retardant plasticizer, so that the physical property reduction caused by a large amount of filling is avoided.
(III) advantageous effects
Compared with the prior art, the invention provides a 150 ℃ irradiation crosslinking low-smoke halogen-free flame-retardant elastomer cable material, which has the following beneficial effects:
the 150 ℃ irradiation crosslinking low-smoke halogen-free flame-retardant elastomer cable material has good flame retardant property, mechanical property, electrical property, temperature resistance and weather resistance.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples.
Embodiment 1 the invention provides a 150 ℃ irradiation crosslinking low-smoke halogen-free flame-retardant elastomer cable material, which comprises the following raw materials in parts by weight:
components The weight portions of
EVM 500HV 30
EPDM IP-4725P 13
LLDPE 10
Phosphorus-nitrogen ternary composite flame retardant FR705 20
Activated aluminum hydroxide 20
Nano montmorillonite 2
Antioxidant DLTDP 0.5
Antioxidant 300 1
Copper resistant agent 1024 0.1
Oxidized polyethylene wax 1
EBS 0.2
UV326 0.1
UV770 0.1
Sensitizer DPS 2
The cable material irradiation dose of this example was 12 Mrad.
Embodiment 2 provides a 150 ℃ irradiation crosslinking low-smoke halogen-free flame-retardant elastomer cable material, which comprises the following raw materials in parts by weight:
components The weight portions of
EVM 500HV 28
EPDM IP-4760P 12
LLDPE 13
Diethyl methyleneAluminium phosphonate 10
MCA 10
Active magnesium hydroxide 20
Nano montmorillonite 2
Antioxidant DSTP 0.5
Antioxidant 300 1
Copper resistant agent 1024 0.1
Oxidized polyethylene wax 1
Erucamide 0.2
UV326 0.1
UV622 0.1
Sensitizer TMPTMA 2
The cable material irradiation dose of this example was 15 Mrad.
Embodiment 3 the invention provides a 150 ℃ irradiation crosslinking low-smoke halogen-free flame-retardant elastomer cable material, which comprises the following raw materials in parts by weight:
components The weight portions of
EVM 700HV 25
EPDM 3092PM 15
LLDPE 10
RDP 8
Cyclic phosphoric acid esters 5
MPP 10
Activated aluminum hydroxide 20
Nano montmorillonite 2
Antioxidant DSTP 0.5
Antioxidant 300 1
Copper resistant agent 1024 0.1
Oxidized polyethylene wax 1
EBS 0.2
UV328 0.1
UV770 0.1
Sensitizer TMPTMA 2
The cable material irradiation dose of this example was 15 Mrad.
Embodiment 4 the invention provides a 150 ℃ irradiation crosslinking low-smoke halogen-free flame-retardant elastomer cable material, which comprises the following raw materials in parts by weight:
components The weight portions of
EVM 500HV 25
EPDM IP-4725P 10
LLDPE 18
Aluminum hypophosphite 8
MCA 12
Active magnesium hydroxide 20
Nano montmorillonite 2
Antioxidant DSTP 0.5
Antioxidant 300 1
Copper resistant agent 1024 0.1
Oxidized polyethylene wax 1
EBS 0.2
UV328 0.1
UV770 0.1
Sensitizer DPS 2
The cable material irradiation dose of this example was 12 Mrad.
Preparing the 150 ℃ irradiation crosslinking low-smoke halogen-free flame-retardant elastomer cable material according to the formula of the embodiment 1-4 by the following method:
(a) putting various materials into a high-speed mixer according to the formula proportion, setting the rotating speed to be 100 rpm-800 rpm, preferably 200 rpm-500 rpm, and mixing for 5 min-15 min. And (b) pouring the mixed materials into a double-screw extruder for melting, mixing, extruding, granulating, dehydrating and drying. The temperature of each zone of the machine body of the double-screw extruder is as follows: a first barrel area: 160 ± 5 ℃, barrel two zone: 170 +/-5 ℃, three sections of a machine barrel: 180 + -5 ℃, four zones of the machine barrel: 190 ± 5 ℃, five zones of the machine barrel: 200 plus or minus 5 ℃, six zones of a machine barrel: 200 plus or minus 5 ℃, seventh zone of machine barrel: 200 +/-5 ℃, eight zones of a machine barrel: 200 plus or minus 5 ℃, nine zones of a machine barrel: 200 +/-5 ℃, die: 200 +/-5 ℃, head: 200 +/-5 ℃.
The performance test data of the 150 ℃ irradiation crosslinking low-smoke halogen-free flame-retardant elastomer cable material prepared in the embodiments 1-4 after tabletting and irradiation crosslinking treatment are shown in the following table:
serial number Performance of Unit of Example 1 Example 2 Example 3 Example 4
1 Tensile strength MPa 13.7 11.6 12.3 14.2
2 Elongation at break % 316 350 335 324
3 Oxygen index % 33 31 31 32
4 Flame retardant rating FT-1 FT-1 FT-1 FT-1
5 Heat aging at 180 deg.C for 168H
5.1 Retention rate of tensile Strength % 116 126 102 108
5.2 Retention of elongation at break % 87 82 92 90
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, but any modifications or equivalent variations made according to the technical spirit of the present invention are within the scope of the present invention as claimed.

Claims (13)

1. The 150 ℃ irradiation crosslinking low-smoke halogen-free flame-retardant elastomer cable material is characterized in that: the cable material mainly comprises the following raw materials in parts by weight: 10-40 parts of ethylene-vinyl acetate rubber (EVM); 10-40 parts of ethylene propylene diene monomer EPDM; 5-20 parts of polyolefin resin; 0-20 parts of a plasticizing system; 10-40 parts of a flame-retardant system; 10-40 parts of a smoke abatement system; 1-8 parts of a flame-retardant synergistic system; 0.5-3 parts of an anti-aging system; 0.2-3 parts of a lubricating system; 0.2-1 part of an anti-ultraviolet system; 0.5-3 parts of a crosslinking sensitization system.
2. The ethylene-vinyl acetate rubber of claim 1 is EVM with VA content greater than 40%, preferably Levaprene EVM500HV, EVM700HV with VA content 50%, 70%.
3. The ethylene propylene diene monomer EPDM of claim 1 being an ethylene-propylene-nonconjugated diene terpolymer, preferably a particulate EPDM rubber with the third monomer ENB, preferably Nordel IP-4725P, IP-4760P, IP-4770P; triple-well EPT 3072PM, 3092 PM.
4. The polyolefin resin of claim 1 is at least one of homo-polypropylene PP-H, random co-polypropylene PP-R, block co-polypropylene PP-B, high density polyethylene HDPE, low density polyethylene LDPE, linear low density polyethylene LLDPE.
5. The plasticizing system of claim 1 being: high flash point naphthenic oil, polyester plasticizer, phosphate ester plasticizer, preferably polyphosphate ester such as RDP and BDP which can realize both plasticization and flame retardance.
6. The flame retardant system of claim 1 being: at least one of phenoxy polyphosphazene, cyclic phosphate, phosphorus-nitrogen ternary composite flame retardant FR705, inorganic aluminum hypophosphite, diethyl aluminum hypophosphite, melamine polyphosphate and melamine cyanurate.
7. The smoke abatement system of claim 1, being: at least one of activated aluminum hydroxide ATH and activated magnesium hydroxide MTH, preferably organosilicon-treated activated magnesium hydroxide MTH.
8. The flame retardant synergistic system of claim 1 is: nano montmorillonite, silicone, white carbon black and zinc borate, and preferably at least one of nano montmorillonite and zinc borate.
9. The anti-aging system of claim 1, being: antioxidant 1098, antioxidant 1076, antioxidant 1010, antioxidant 168, antioxidant 300, antioxidant DLTDP, antioxidant DSTP, and copper resistant agent 1024.
10. The lubricating system of claim 1 being: oxidized polyethylene wax, polypropylene wax, stearic acid, calcium stearate, stearamide, ethylene bis stearamide EBS, erucamide, oleamide and silicone.
11. The ultraviolet resistant linear system of claim 1: at least one of UV531, UV326, UV328, UV329, UV622, UV770, and UV 944.
12. The crosslinking sensitization system of claim 1: ethylene glycol dimethacrylate EGDMA, triallyl cyanurate TAC, trimethylolpropane trimethacrylate TMPTMA, pentaerythritol triacrylate PETA, dipropargyl succinate DPS, preferably at least one of TMPTMA and DPS.
13. The preparation method of the 150 ℃ irradiation crosslinking low-smoke halogen-free flame retardant elastomer cable material according to any one of claims 1 to 11, characterized by comprising the following steps: the method comprises the following steps: putting various materials into a high-speed mixer according to a formula proportion, setting the rotating speed of 100-800 rpm, preferably 200-500 rpm, and mixing for 5-15 min, (b) pouring the mixed materials into a double-screw extruder for melting and mixing, extruding and granulating, and dehydrating and drying; the temperature of each zone of the machine body of the double-screw extruder is as follows: a first barrel area: 160 ± 5 ℃, barrel two zone: 170 +/-5 ℃, three sections of a machine barrel: 180 + -5 ℃, four zones of the machine barrel: 190 ± 5 ℃, five zones of the machine barrel: 200 plus or minus 5 ℃, six zones of a machine barrel: 200 plus or minus 5 ℃, seventh zone of machine barrel: 200 +/-5 ℃, eight zones of a machine barrel: 200 plus or minus 5 ℃, nine zones of a machine barrel: 200 +/-5 ℃, die: 200 +/-5 ℃, head: 200 +/-5 ℃.
CN201911091770.0A 2019-11-11 2019-11-11 150 ℃ irradiation crosslinking low-smoke halogen-free flame-retardant elastomer cable material and preparation method thereof Withdrawn CN110791011A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111303484A (en) * 2020-04-01 2020-06-19 吉林大学 Irradiation-sensitized halogen-free flame retardant, preparation method and application in wires and cables
CN111662526A (en) * 2020-06-24 2020-09-15 苏州通优新材料科技有限公司 Halogen-free flame-retardant sheath material for thin cables with thickness of 0.13 square millimeter and below, and preparation method and application thereof
CN111662499A (en) * 2020-05-13 2020-09-15 扬州市好年华高分子材料有限公司 Low-heat-release low-smoke halogen-free flame-retardant polyolefin cable material and preparation method thereof
CN111690199A (en) * 2020-05-13 2020-09-22 扬州市好年华高分子材料有限公司 Ultraviolet light crosslinking low-smoke halogen-free flame-retardant polyolefin cable material and preparation method thereof
CN113896979A (en) * 2021-11-02 2022-01-07 苏州铂玛新材料有限公司 High-flame-retardant low-temperature-resistant thermoplastic low-smoke halogen-free flame-retardant composition and preparation method and application thereof
CN115028919A (en) * 2022-04-27 2022-09-09 深圳市欧龙优新材料科技有限公司 High-flexibility high-flame-retardance elastomer cable material resistant to high temperature of 150 ℃, preparation method and application thereof

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111303484A (en) * 2020-04-01 2020-06-19 吉林大学 Irradiation-sensitized halogen-free flame retardant, preparation method and application in wires and cables
CN111303484B (en) * 2020-04-01 2021-06-01 吉林大学 Irradiation-sensitized halogen-free flame retardant, preparation method and application in wires and cables
CN111662499A (en) * 2020-05-13 2020-09-15 扬州市好年华高分子材料有限公司 Low-heat-release low-smoke halogen-free flame-retardant polyolefin cable material and preparation method thereof
CN111690199A (en) * 2020-05-13 2020-09-22 扬州市好年华高分子材料有限公司 Ultraviolet light crosslinking low-smoke halogen-free flame-retardant polyolefin cable material and preparation method thereof
CN111662526A (en) * 2020-06-24 2020-09-15 苏州通优新材料科技有限公司 Halogen-free flame-retardant sheath material for thin cables with thickness of 0.13 square millimeter and below, and preparation method and application thereof
CN111662526B (en) * 2020-06-24 2021-11-19 苏州通优新材料科技有限公司 Halogen-free flame-retardant sheath material for thin cables with thickness of 0.13 square millimeter and below, and preparation method and application thereof
CN113896979A (en) * 2021-11-02 2022-01-07 苏州铂玛新材料有限公司 High-flame-retardant low-temperature-resistant thermoplastic low-smoke halogen-free flame-retardant composition and preparation method and application thereof
CN115028919A (en) * 2022-04-27 2022-09-09 深圳市欧龙优新材料科技有限公司 High-flexibility high-flame-retardance elastomer cable material resistant to high temperature of 150 ℃, preparation method and application thereof

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