CN116102817A - High-light-transmittance halogen-free flame-retardant polyolefin sheath material and preparation method thereof - Google Patents

High-light-transmittance halogen-free flame-retardant polyolefin sheath material and preparation method thereof Download PDF

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CN116102817A
CN116102817A CN202310250115.5A CN202310250115A CN116102817A CN 116102817 A CN116102817 A CN 116102817A CN 202310250115 A CN202310250115 A CN 202310250115A CN 116102817 A CN116102817 A CN 116102817A
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halogen
free flame
retardant polyolefin
sheath material
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CN116102817B (en
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孙凯
洪森林
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Shanghai Kaibo Cable Special Material Co ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0846Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853Vinylacetate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2217Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224Magnesium hydroxide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2227Oxides; Hydroxides of metals of aluminium
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/20Applications use in electrical or conductive gadgets
    • C08L2203/202Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A30/00Adapting or protecting infrastructure or their operation
    • Y02A30/14Extreme weather resilient electric power supply systems, e.g. strengthening power lines or underground power cables

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Abstract

The invention discloses a high-light-transmission halogen-free flame-retardant polyolefin sheath material and a preparation method thereof, wherein the sheath material comprises the following raw materials in parts by weight: 9-14 parts of polyethylene resin, 20-25 parts of ethylene-vinyl acetate copolymer, 10-15 parts of ethylene-octene copolymer, 5-10 parts of compatilizer, 1-2 parts of carbon black master batch, 90-100 parts of flame retardant, 3-5 parts of smoke suppressant, 3-8 parts of shell forming agent, 0.3-0.7 part of antioxidant, 2-3 parts of lubricant and 0.5-2 parts of organopolysiloxane coupling agent. The high-light-transmittance thermoplastic low-smoke halogen-free flame-retardant polyolefin material prepared by the invention has the advantages of environmental protection performance, heat resistance, cold resistance, cracking resistance and flame retardance, overcomes the defects of the existing material, can meet the severe condition that the light transmittance of a large-outer-diameter (d is more than 70 mm) power cable is more than or equal to 60 percent, and can also keep good mechanical performance and processing performance.

Description

High-light-transmittance halogen-free flame-retardant polyolefin sheath material and preparation method thereof
Technical Field
The invention relates to the technical field of cable materials, in particular to a high-light-transmittance halogen-free flame-retardant polyolefin sheath material and a preparation method thereof.
Background
The halogen-free low-smoke characteristic and the non-dripping characteristic of the cable are particularly important in occasions with high requirements on the flame retardant characteristic of the cable, such as subways, high-rise buildings, markets, theaters, power stations, chemical factories, urban squares and the like. When a fire disaster happens, the cable is often an important pushing handle for flame propagation, the flame is slow in flame delay speed, the cable is not dripped when being burnt, the smoke quantity is small, the visibility is high, the release quantity of harmful gas is small, the time from the development of the fire disaster to the bombing is delayed to a great extent, and more time is left for personnel escape and fire fighting. There are also rare reports on halogen-free cable material products with high light transmittance, low smoke and few dripping substances, and research on the halogen-free cable material products with high light transmittance and few dripping substances is a key problem in the development of low smoke halogen-free materials in the current market.
Disclosure of Invention
In order to solve the problems, the invention provides a high-light-transmission halogen-free flame-retardant polyolefin sheath material and a preparation method thereof, and the prepared high-light-transmission thermoplastic low-smoke halogen-free flame-retardant polyolefin material has the advantages of environmental protection performance, heat resistance, cold resistance, cracking resistance and flame retardance.
The invention adopts the following technical scheme:
the high-light-transmittance halogen-free flame-retardant polyolefin sheath material is prepared from the following raw materials in parts by weight:
9-14 parts of polyethylene resin;
20-25 parts of ethylene-vinyl acetate copolymer;
10-15 parts of ethylene-octene copolymer;
5-10 parts of compatilizer;
1-2 parts of carbon black master batch;
90-100 parts of flame retardant;
3-5 parts of smoke suppressant;
3-8 parts of a shell forming agent;
0.3-0.7 part of antioxidant;
2-3 parts of a lubricant;
0.5-2 parts of organopolysiloxane coupling agent.
The polyethylene resin has a melt index of (0.8-1) g/10min at 190℃and 2.16 kg.
The ethylene-octene copolymer has a melt index of (0.9-1.1) g/10min at 190℃and 2.16 kg.
The ethylene-vinyl acetate copolymer has a melt index of (4-5.5) g/10min at 190℃and a pressure of 2.16 kg.
The compatilizer is one or a mixture of two of ethylene-octene copolymer grafted maleic anhydride and ethylene copolymer grafted maleic anhydride.
Preferably, the ethylene-octene copolymer grafted maleic anhydride has a melt index (0.15-0.45) g/10min at 190 ℃ and 2.16 kg; the melt index of the ethylene copolymer grafted maleic anhydride at 190 ℃ and 2.16kg is (0.3-0.9) g/10min.
The carbon black master batch is a mixture of carbon black and a resin carrier, wherein the content of the carbon black is 50-60wt% based on the mass of the carbon black master batch; the resin carrier is a polyethylene resin having a melt index of (18-25) g/10min at 190 ℃ and 2.16 kg.
The flame retardant is one or a mixture of two of magnesium hydroxide and aluminum hydroxide.
The smoke suppressant is any one or a mixture of two of zinc borate and nano attapulgite.
The shell forming agent is any one or a mixture of two of modified nano montmorillonite, silica micropowder and white carbon black.
The modified nano montmorillonite is obtained by mixing hexadecyl long-chain alkane and montmorillonite, wherein the mass ratio of hexadecyl long-chain alkane to montmorillonite is (0.5-1.5): 1.
the antioxidant comprises the following components in percentage by mass: 1: (0.2-0.5) dilauryl thiodipropionate, polyhydric hindered phenol and phenyl tri (2, 4-di-tert-butyl) phosphite.
The polyhydric hindered phenol is selected from one or two of AT-10 and AT-76.
The organopolysiloxane coupling agent has a kinematic viscosity of 5.0-6.0Cst at 25 ℃.
The invention also provides a preparation method of the high-light-transmittance halogen-free flame-retardant polyolefin sheath material, which comprises the following steps:
s1, putting the raw material components weighed according to the weight of the formula into an internal mixer for kneading to obtain a mixture;
and S2, extruding, granulating and molding the uniformly mixed mixture through a single screw extruder to obtain the high-light-transmittance halogen-free flame-retardant polyolefin sheath material.
The kneading temperature in the step S1 is 180-190 ℃.
The extrusion temperature in the step S2 is 120-145 ℃.
The invention also provides application of the high-light-transmittance halogen-free flame-retardant polyolefin sheath material in preparation of the power cable sheath.
Compared with the prior art, the technical scheme of the invention has the following advantages:
the high-light-transmittance thermoplastic low-smoke halogen-free flame-retardant polyolefin material prepared by the invention has the advantages of environmental protection performance, heat resistance, cold resistance, cracking resistance and flame retardance, overcomes the defects of the existing material, can meet the severe condition that the light transmittance of a large-outer-diameter (d is more than 70 mm) power cable is more than or equal to 60 percent, and can also keep good mechanical performance and processing performance. In addition, the preparation process is simple, the equipment investment is small, the efficiency is high, and the cost is low.
Detailed Description
This invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the invention to those skilled in the art. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
the embodiment provides a high-light-transmission halogen-free flame-retardant polyolefin sheath material, which comprises the following components in parts by weight:
Figure BDA0004127603910000041
wherein the compatilizer is ethylene-octene copolymer grafted maleic anhydride and ethylene copolymer grafted maleic anhydride, and the mass ratio of the compatilizer to the ethylene-octene copolymer grafted maleic anhydride is 1:1, a mixture of two or more of the above-mentioned materials; the carbon black master batch is prepared from carbon black and a resin carrier according to a mass ratio of 1:1, wherein the resin carrier is polyethylene resin; the smoke suppressant is zinc borate; the shell forming agent is modified nano montmorillonite, the modified nano montmorillonite is obtained by mixing hexadecyl long-chain alkane and montmorillonite, wherein the mass ratio of hexadecyl long-chain alkane to montmorillonite is 0.5:1, a step of; the antioxidant comprises the following components in percentage by mass: 1:0.2 of dilauryl thiodipropionate, a polyhydric hindered phenol and tri (2, 4-di-tert-butyl) phenyl phosphite, wherein the polyhydric hindered phenol is AT-10.
The preparation method comprises the following steps:
s1, putting the raw material components weighed according to the weight of the formula into an internal mixer for kneading, and controlling the kneading temperature to be 180-190 ℃ to obtain a mixture;
s2, extruding, granulating and molding the uniformly mixed mixture through a single screw extruder, and controlling the extrusion temperature to be 120-145 ℃ to obtain the high-light-transmittance halogen-free flame-retardant polyolefin sheath material.
Example 2:
the embodiment provides a high-light-transmission halogen-free flame-retardant polyolefin sheath material, which comprises the following components in parts by weight:
Figure BDA0004127603910000051
wherein, the compatilizer is ethylene-octene copolymer grafted maleic anhydride; the shell forming agent is silicon micropowder and white carbon black according to the mass ratio of 1:1, a mixture of two or more of the above-mentioned materials; the carbon black master batch is prepared from carbon black and a resin carrier according to a mass ratio of 1:2, a mixture of two or more of the above-mentioned materials; the smoke suppressant is nano attapulgite; the shell forming agent is silicon micropowder and white carbon black according to the mass ratio of 1:1, a mixture of two or more of the above-mentioned materials; the antioxidant comprises the following components in percentage by mass: 1:0.5 dilauryl thiodipropionate, a polyhydric hindered phenol, and phenyl tri (2, 4-di-tert-butyl) phosphite, wherein the polyhydric hindered phenol is AT-76. The preparation method comprises the following steps:
s1, putting the raw material components weighed according to the weight of the formula into an internal mixer for kneading, and controlling the kneading temperature to be 180-190 ℃ to obtain a mixture;
s2, extruding, granulating and molding the uniformly mixed mixture through a single screw extruder, and controlling the extrusion temperature to be 120-145 ℃ to obtain the high-light-transmittance halogen-free flame-retardant polyolefin sheath material.
Example 3:
the embodiment provides a high-light-transmission halogen-free flame-retardant polyolefin sheath material, which comprises the following components in parts by weight:
Figure BDA0004127603910000061
wherein the compatilizer is ethylene-octene copolymer grafted maleic anhydride and ethylene copolymer grafted maleic anhydride, and the mass ratio of the compatilizer to the ethylene-octene copolymer grafted maleic anhydride is 1:1, a mixture of two or more of the above-mentioned materials; the carbon black master batch is prepared from carbon black and a resin carrier according to a mass ratio of 2:1, a mixture of two or more of the above-mentioned materials; the smoke suppressant is prepared from zinc borate and nano attapulgite according to a mass ratio of 1:1, a mixture of two or more of the above-mentioned materials; the shell forming agent is modified nano montmorillonite and white carbon black according to the mass ratio of 1:1, wherein the modified nano montmorillonite is obtained by mixing sixteen long-chain alkane and montmorillonite, and the mass ratio of the sixteen long-chain alkane to the montmorillonite is 1.5:1, a step of; the antioxidant comprises the following components in percentage by mass: 1:0.4 of dilauryl thiodipropionate, polyhydric hindered phenol and tri (2, 4-di-tert-butyl) phenyl phosphite, wherein the polyhydric hindered phenol comprises AT-10 and AT-76 according to the mass ratio of 1: 1.
The preparation method comprises the following steps:
s1, putting the raw material components weighed according to the weight of the formula into an internal mixer for kneading, and controlling the kneading temperature to be 180-190 ℃ to obtain a mixture;
s2, extruding, granulating and molding the uniformly mixed mixture through a single screw extruder, and controlling the extrusion temperature to be 120-145 ℃ to obtain the high-light-transmittance halogen-free flame-retardant polyolefin sheath material.
Comparative example 1:
in this comparative example, no smoke suppressant was used as compared with example 1, and the rest of the components were the same as in example 1, and the kneading and extrusion granulation process was the same as in example 1.
Comparative example 2:
in this comparative example, as compared with example 1, no shell-forming agent was used, and the rest of the components were the same as in example 1, and the kneading and extrusion granulation process was the same as in example 1.
Comparative example 3:
in this comparative example, as compared with example 1, no shell forming agent and smoke suppressant were used, and the rest of the components were the same as in example 1, and the kneading and extrusion granulation process was the same as in example 1.
Performance test:
the cable materials prepared according to the proportions in examples 1 to 3 and comparative examples 1 to 3 were subjected to performance tests according to the relevant standards, respectively, and the relevant performance results of the prepared cable materials are shown in Table 1.
TABLE 1 Performance test results of the cable materials prepared in examples 1-3 and comparative examples 1-3
Figure BDA0004127603910000071
Figure BDA0004127603910000081
As is evident from table 1, the smoke density of the cable sheath material and the light transmittance of the cable are greatly affected by the shell forming agent and the smoke suppressant. Under the condition that a shell forming agent and/or a smoke suppressant are not added, the flameless smoke density and the flame smoke density of the sheath material are both greatly increased, and the light transmittance is greatly reduced.
In conclusion, the high-light-transmittance thermoplastic low-smoke halogen-free flame-retardant polyolefin material prepared by the method has the advantages of taking the environmental protection performance, the heat resistance performance, the cold resistance performance, the cracking resistance performance and the flame retardance into consideration, overcoming the defects of the existing material, meeting the severe condition that the light transmittance of a large-outer-diameter (d is more than 70 mm) power cable is more than or equal to 60 percent, keeping good mechanical property and processing performance, effectively overcoming various defects in the prior art, along with simple preparation process, small equipment investment, high efficiency, low cost and high industrial utilization value.
The invention is applicable to the prior art where nothing is said.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While obvious variations or modifications are contemplated as falling within the scope of the present invention.

Claims (10)

1. The high-light-transmittance halogen-free flame-retardant polyolefin sheath material is characterized by being prepared from the following raw materials in parts by weight:
9-14 parts of polyethylene resin;
20-25 parts of ethylene-vinyl acetate copolymer;
10-15 parts of ethylene-octene copolymer;
5-10 parts of compatilizer;
1-2 parts of carbon black master batch;
90-100 parts of flame retardant;
3-5 parts of smoke suppressant;
3-8 parts of a shell forming agent;
0.3-0.7 part of antioxidant;
2-3 parts of a lubricant;
0.5-2 parts of organopolysiloxane coupling agent.
2. The high light transmission halogen-free flame retardant polyolefin sheathing compound of claim 1, wherein the polyethylene resin has a melt index of (0.8-1) g/10min at 190 ℃ and 2.16 kg; the ethylene-octene copolymer has a melt index (0.9-1.1) g/10min at 190 ℃ and 2.16 kg; the ethylene-vinyl acetate copolymer has a melt index of (4-5.5) g/10min at 190℃and a pressure of 2.16 kg.
3. The high light transmission halogen-free flame retardant polyolefin sheath material according to claim 1, wherein the compatibilizer is one or a mixture of two of ethylene-octene copolymer grafted maleic anhydride and ethylene copolymer grafted maleic anhydride.
4. The high light transmission halogen-free flame retardant polyolefin sheathing compound of claim 3, wherein the ethylene-octene copolymer grafted maleic anhydride has a melt index of (0.15-0.45) g/10min at 190 ℃ and 2.16 kg; the melt index of the ethylene copolymer grafted maleic anhydride at 190 ℃ and 2.16kg is (0.3-0.9) g/10min.
5. The high light transmission halogen-free flame retardant polyolefin sheath material according to claim 1, wherein the carbon black masterbatch is a mixture of carbon black and a resin carrier, wherein the carbon black content is 50-60wt% based on the mass of the carbon black masterbatch; the resin carrier is a polyethylene resin having a melt index of (18-25) g/10min at 190 ℃ and 2.16 kg.
6. The high light-transmitting halogen-free flame retardant polyolefin sheath material according to claim 1, wherein the flame retardant is one or a mixture of two of magnesium hydroxide and aluminum hydroxide; the smoke suppressant is any one or a mixture of two of zinc borate and nano attapulgite; the shell forming agent is any one or a mixture of two of modified nano montmorillonite, silica micropowder and white carbon black; the antioxidant comprises the following components in percentage by mass: 1: (0.2-0.5) dilauryl thiodipropionate, polyhydric hindered phenol and phenyl tri (2, 4-di-tert-butyl) phosphite.
7. The high-light-transmittance halogen-free flame-retardant polyolefin sheath material according to claim 6, wherein the modified nano montmorillonite is obtained by mixing sixteen long-chain alkane and montmorillonite, wherein the mass ratio of the sixteen long-chain alkane to the montmorillonite is (0.5-1.5): 1, a step of;
the polyhydric hindered phenol is selected from one or two of AT-10 and AT-76.
8. The high light transmission halogen-free flame retardant polyolefin sheath material according to claim 1, wherein the organopolysiloxane coupling agent has a kinematic viscosity of 5.0-6.0Cst at 25 ℃.
9. A method for preparing the high light transmission halogen-free flame retardant polyolefin sheath material according to any one of claims 1-8, comprising the following steps:
s1, putting the raw material components weighed according to the weight of the formula into an internal mixer for kneading to obtain a mixture;
and S2, extruding, granulating and molding the uniformly mixed mixture through a single screw extruder to obtain the high-light-transmittance halogen-free flame-retardant polyolefin sheath material.
10. The method according to claim 9, wherein the kneading temperature in the step S1 is 180 to 190 ℃; the extrusion temperature in the step S2 is 120-145 ℃.
CN202310250115.5A 2023-03-15 2023-03-15 High-light-transmittance halogen-free flame-retardant polyolefin sheath material and preparation method thereof Active CN116102817B (en)

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Publication number Priority date Publication date Assignee Title
CN1927928A (en) * 2006-09-01 2007-03-14 西北师范大学 Paligorskite-linear low density polyethylene composite flame-proof material
CN102304237A (en) * 2011-07-22 2012-01-04 西北师范大学 Halogen-free smoke inhibition fire retardant
CN103804808A (en) * 2014-01-23 2014-05-21 安徽华源电缆集团有限公司 High-strength smoke-inhibiting high-temperature-resisting cable sheath material
CN108059761A (en) * 2017-12-11 2018-05-22 上海至正道化高分子材料股份有限公司 A kind of 125 DEG C of cross-linking radiation photovoltaic cable flame-retardant sheath materials and preparation method thereof
CN108164798A (en) * 2016-12-07 2018-06-15 上海凯波特种电缆料厂有限公司 A kind of thermoplastic low-smoke halide-free fireproof composite polyolefine material of low-smoke and preparation method thereof
CN112210157A (en) * 2020-09-29 2021-01-12 上海凯波电缆特材股份有限公司 Halogen-free flame-retardant polyolefin sheath material and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1927928A (en) * 2006-09-01 2007-03-14 西北师范大学 Paligorskite-linear low density polyethylene composite flame-proof material
CN102304237A (en) * 2011-07-22 2012-01-04 西北师范大学 Halogen-free smoke inhibition fire retardant
CN103804808A (en) * 2014-01-23 2014-05-21 安徽华源电缆集团有限公司 High-strength smoke-inhibiting high-temperature-resisting cable sheath material
CN108164798A (en) * 2016-12-07 2018-06-15 上海凯波特种电缆料厂有限公司 A kind of thermoplastic low-smoke halide-free fireproof composite polyolefine material of low-smoke and preparation method thereof
CN108059761A (en) * 2017-12-11 2018-05-22 上海至正道化高分子材料股份有限公司 A kind of 125 DEG C of cross-linking radiation photovoltaic cable flame-retardant sheath materials and preparation method thereof
CN112210157A (en) * 2020-09-29 2021-01-12 上海凯波电缆特材股份有限公司 Halogen-free flame-retardant polyolefin sheath material and preparation method thereof

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