CN115232391B - Foaming ethylene-tetrafluoroethylene copolymer cable material and preparation method thereof - Google Patents

Foaming ethylene-tetrafluoroethylene copolymer cable material and preparation method thereof Download PDF

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CN115232391B
CN115232391B CN202210931493.5A CN202210931493A CN115232391B CN 115232391 B CN115232391 B CN 115232391B CN 202210931493 A CN202210931493 A CN 202210931493A CN 115232391 B CN115232391 B CN 115232391B
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tetrafluoroethylene copolymer
cable material
etfe
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CN115232391A (en
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林伟男
洪喜军
范明波
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Panheng Guangzhou Technology Co ltd
Guangzhou Jingxin High Polymer Technology Co ltd
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Panheng Guangzhou Technology Co ltd
Guangzhou Jingxin High Polymer Technology Co ltd
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    • 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
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide
    • 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
    • C08J9/0028—Use of organic additives containing nitrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/18—Protection against damage caused by wear, mechanical force or pressure; Sheaths; Armouring
    • 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
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • 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
    • C08J2207/00—Foams characterised by their intended use
    • C08J2207/06—Electrical wire insulation
    • 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
    • C08J2323/02—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
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A30/00—Adapting or protecting infrastructure or their operation
    • Y02A30/14—Extreme weather resilient electric power supply systems, e.g. strengthening power lines or underground power cables

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
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  • Spectroscopy & Molecular Physics (AREA)
  • Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

The invention relates to the technical field of cable material preparation, and particularly discloses a foaming ethylene-tetrafluoroethylene copolymer cable material and a preparation method thereof. The foaming ethylene-tetrafluoroethylene copolymer cable material comprises the following raw materials in parts by weight: 90-100 parts of ETFE; 0.5 to 1.5 portions of chemical foaming agent; 0.1 to 0.5 part of foaming auxiliary agent; 1-2 parts of nucleating agent; 0.1-0.5 part of lubricant; 1-5 parts of cross-linking agent. According to the ethylene-tetrafluoroethylene copolymer cable material, the foaming agent is added into the ETFE to foam the ETFE material, so that small air holes are formed in the ethylene-tetrafluoroethylene copolymer cable material, dielectric loss of the ETFE material can be reduced, accuracy and speed of signal transmission can be effectively improved, and further information transmission is better and faster. Meanwhile, the foamed ethylene-tetrafluoroethylene copolymer cable material also has excellent tensile strength and elongation at break after irradiation.

Description

Foaming ethylene-tetrafluoroethylene copolymer cable material and preparation method thereof
Technical Field
The invention relates to the technical field of cable material preparation, in particular to a foaming ethylene-tetrafluoroethylene copolymer cable material and a preparation method thereof.
Background
Ethylene-tetrafluoroethylene copolymer (ETFE) is widely applied to the field of high-temperature high-frequency wires and cables, and has good high-temperature resistance, radiation resistance, excellent mechanical properties and other properties. The fiber can be generally used for a long time at 150 ℃, and can improve the temperature resistance level after irradiation crosslinking because of low density, so that the fiber can be used for a long time to raise the use temperature to 200 ℃, and is often used in the field of signal transmission cables for military, aerospace and aviation.
However, the dielectric loss is greatly increased due to the three-bit network structure formed after the cross-linking, so that the signal transmission is reduced. However, with the development of 5G, higher requirements are put on the performance of signal transmission, and higher requirements are put on signal transmission in the military field.
The ETFE material is foamed, and small air holes can be formed in the ETFE material, so that dielectric loss of the ETFE material can be reduced, accuracy and speed of signal transmission are greatly improved, and further information transmission is better and faster. Therefore, the foaming ethylene-tetrafluoroethylene copolymer cable material has important application value.
However, the inventor further found in the study that the cable prepared from the foamed ethylene-tetrafluoroethylene copolymer cable material has poor mechanical properties such as tensile strength, elongation at break and the like after irradiation; therefore, how to improve the tensile strength and the breaking elongation of the foaming ethylene-tetrafluoroethylene copolymer cable material after irradiation is a technical problem which needs to be further solved by the invention.
Disclosure of Invention
In order to overcome at least one technical problem existing in the prior art, the invention firstly provides a foaming ethylene-tetrafluoroethylene copolymer cable material.
The invention firstly provides a foaming ethylene-tetrafluoroethylene copolymer cable material which comprises the following raw materials in parts by weight:
90-100 parts of ETFE; 0.5 to 1.5 portions of chemical foaming agent; 0.1 to 0.5 part of foaming auxiliary agent; 1-2 parts of nucleating agent; 0.1-0.5 part of lubricant; 1-5 parts of cross-linking agent.
Preferably, the foamed ethylene-tetrafluoroethylene copolymer cable material comprises the following raw materials in parts by weight:
93-98 parts of ETFE; 0.5 to 1 part of chemical foaming agent; 0.1 to 0.3 part of foaming auxiliary agent; 1 to 1.5 portions of nucleating agent; 0.2-0.5 part of lubricant; 1-3 parts of cross-linking agent.
Preferably, the ETFE is selected from ETFE having a melting point of less than 240 ℃.
Preferably, the ETFE is selected from ETFE with a melting point of 220-235 ℃.
The inventor finds that the selection of the ETFE material has important influence on the tensile strength and the elongation at break of the foamed ethylene-tetrafluoroethylene copolymer cable material prepared after foaming after irradiation; the inventor surprisingly found in the research process that when ETFE is selected from the ETFE with the melting point less than 240 ℃, the tensile strength and the elongation at break of the prepared ethylene-tetrafluoroethylene copolymer cable material are obviously higher than those of the prepared ethylene-tetrafluoroethylene copolymer cable material with the ETFE with the melting point greater than 240 ℃ after the ethylene-tetrafluoroethylene copolymer cable material is irradiated.
Preferably, the chemical blowing agent is selected from azodicarbonamide.
Preferably, the crosslinking agent is at least one selected from trifunctional acrylate and trifunctional allyl ester.
The inventor finds that the tensile strength and the elongation at break of the prepared foaming ethylene-tetrafluoroethylene copolymer cable material after irradiation can be improved by adding the cross-linking agent in the process of foaming the ethylene-tetrafluoroethylene copolymer cable material.
Further preferably, the crosslinking agent is selected from one or more of trimethylolpropane trimethacrylate (TMPTMA), trimethylolpropane triacrylate (TMPTA), triallyl cyanurate (TAC) and triallyl isocyanurate (TAIC).
Further preferably, the crosslinking agent is selected from the group consisting of trimethylolpropane trimethacrylate in combination with triallyl cyanurate.
The inventors have further found in the study that the addition of the crosslinking agent can improve the tensile strength and the elongation at break of the prepared foamed ethylene-tetrafluoroethylene copolymer cable material after irradiation. However, the different crosslinking agents are different in the degree of improvement of the tensile strength and the elongation at break of the expanded ethylene-tetrafluoroethylene copolymer cable material prepared by taking ETFE with the melting point of less than 240 ℃ as a raw material after irradiation. The inventors have surprisingly found in a number of studies that: the ethylene-tetrafluoroethylene copolymer cable material is prepared by taking ETFE with the melting point less than 240 ℃ as a raw material and adding a cross-linking agent consisting of trimethylolpropane trimethacrylate and triallyl cyanurate, and the tensile strength and the elongation at break after irradiation are greatly higher than those of the ethylene-tetrafluoroethylene copolymer cable material prepared by adopting other cross-linking agents or cross-linking agent combinations.
Still more preferably, the weight ratio of trimethylolpropane trimethacrylate to triallyl cyanurate is 1:3-5.
Most preferably, the weight ratio of trimethylolpropane trimethacrylate to triallyl cyanurate is 1:4.
Preferably, the foaming aid is selected from the group consisting of Mg 2 O 3 ，Sb 2 O 3 ，Al 2 O 3 ，ZnO，Fe 2 O 3 One or a combination of more than one of the above.
Preferably, the nucleating agent is selected from PTFE micropowder and/or Si 2 O 3 Micro powder.
Preferably, the lubricant is one or more of fluorowax, paraffin wax or microcrystalline wax.
Preferably, the foaming ethylene-tetrafluoroethylene copolymer cable material also comprises 0.1-1 part of antioxidant.
Preferably, the foaming ethylene-tetrafluoroethylene copolymer cable material also comprises 0.2-0.5 part of antioxidant.
Further preferably, the antioxidant comprises a primary antioxidant and a secondary antioxidant.
Still more preferably, the weight ratio of the primary antioxidant to the secondary antioxidant is 1-3:1.
Most preferably, the weight ratio of the primary antioxidant to the secondary antioxidant is 2:1.
Preferably, the main antioxidant is selected from one or more of pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (1010), triethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ] (245) or n-stearyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (1076).
Preferably, the auxiliary antioxidant is selected from one or more of phosphite esters or thioesters.
Most preferably, the secondary antioxidant is selected from pentaerythritol tetrakis (3-laurylthiopropionate).
The invention also provides a preparation method of the foaming ethylene-tetrafluoroethylene copolymer cable material, which comprises the following steps:
uniformly mixing ETFE, a chemical foaming agent, a foaming auxiliary agent, a nucleating agent, a lubricant and a crosslinking agent to obtain a mixture; then the mixture is melted and extruded by an extruder, and the foaming ethylene-tetrafluoroethylene copolymer cable material is obtained; or alternatively, the first and second heat exchangers may be,
uniformly mixing ETFE, a chemical foaming agent, a foaming auxiliary agent, a nucleating agent, a lubricant, a crosslinking agent and an antioxidant to obtain a raw material mixture; and then the raw material mixture is melted and extruded by an extruder, and the foaming ethylene-tetrafluoroethylene copolymer cable material is obtained.
The invention also provides a preparation method of the foaming ethylene-tetrafluoroethylene copolymer cable material, which comprises the following steps:
(1) Dividing the cross-linking agent into two parts, and uniformly mixing the first part of cross-linking agent with ETFE to obtain a first mixture;
(2) Uniformly mixing a chemical foaming agent and a foaming auxiliary agent with the first mixture to obtain a second mixture;
(3) Uniformly mixing the lubricant, the second part of cross-linking agent and the second mixture to obtain a raw material mixture;
(4) And (3) carrying out melt extrusion on the raw material mixture by an extruder to obtain the foamed ethylene-tetrafluoroethylene copolymer cable material.
Preferably, the weight of the first part of crosslinking agent is 1/3 to 1/2 of the total weight of the total crosslinking agent.
Preferably, an antioxidant is also added in step (2).
The inventor further discovers in the research that the adding mode of the cross-linking agent in the process of preparing the foaming ethylene-tetrafluoroethylene copolymer cable material has important influence on the tensile strength and the elongation at break of the prepared foaming ethylene-tetrafluoroethylene copolymer cable material after irradiation. The inventors have surprisingly found in the study that: in the process of preparing the foamed ethylene-tetrafluoroethylene copolymer cable material, the cross-linking agent is added twice according to the mode of the invention (namely, a part of cross-linking agent is firstly mixed with ETFE, then materials such as a chemical foaming agent and the like are added, and finally the rest cross-linking agent is added), so that the tensile strength and the elongation at break of the irradiated foamed ethylene-tetrafluoroethylene copolymer cable material are greatly higher than those of the foamed ethylene-tetrafluoroethylene copolymer cable material prepared by adding the cross-linking agent once, and are also greatly higher than those of the foamed ethylene-tetrafluoroethylene copolymer cable material prepared by adding the cross-linking agent twice in other modes.
The beneficial effects are that: the invention provides a brand new foaming ethylene-tetrafluoroethylene copolymer cable material; the foaming ethylene-tetrafluoroethylene copolymer cable material foams the ETFE material by adding the foaming agent into the ETFE, so that small pores are formed in the foaming ethylene-tetrafluoroethylene copolymer cable material, the dielectric loss of the ETFE material can be reduced, the accuracy and the speed of signal transmission can be effectively improved, and the information transmission can be better and faster improved. Meanwhile, the foamed ethylene-tetrafluoroethylene copolymer cable material also has excellent tensile strength and elongation at break after irradiation.
Detailed Description
The present invention is further explained below with reference to specific examples, but the examples do not limit the scope of the present invention. In the following examples, ETFE with melting point less than 240 ℃ is selected from ETFE with brand name of EP 620; ETFE selection product with the melting point higher than 240 ℃ is ETFE with the brand number HT-2202HS of the American Komu brand; the remaining unexplained starting materials are all available materials that can be purchased by one skilled in the art through conventional purchasing routes.
Example 1 preparation of a foamed ethylene-tetrafluoroethylene copolymer cable material
The raw materials comprise the following components in parts by weight: 95 parts of ETFE; 0.8 parts of chemical foaming agent; 0.2 part of foaming auxiliary agent; 1.5 parts of nucleating agent; 0.3 parts of lubricant; 2 parts of a cross-linking agent; 0.2 parts of a main antioxidant; 0.1 part of auxiliary antioxidant.
ETFE with the brand of HT-2202HS is selected as the ETFE; the chemical foaming agent is azodicarbonamide; the foaming auxiliary agent is Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the PTFE micropowder is selected as the nucleating agent; the said processThe lubricant is paraffin; the main antioxidant is antioxidant 245; the auxiliary antioxidant is antioxidant 412S; the cross-linking agent is triallyl cyanurate.
The preparation method comprises the following steps:
(1) Putting ETFE, a chemical foaming agent, a foaming auxiliary agent, a nucleating agent, a primary antioxidant and an auxiliary antioxidant into a stirrer, and uniformly stirring to obtain a first mixture;
(2) Adding a lubricant and a crosslinking agent, and continuously stirring uniformly to obtain a raw material mixture;
(3) And (3) putting the raw material mixture into an extruder, and carrying out melt extrusion at the melting point temperature of ETFE to obtain the foamed ethylene-tetrafluoroethylene copolymer cable material.
Example 2 preparation of a foamed ethylene-tetrafluoroethylene copolymer cable material
The raw materials comprise the following components in parts by weight: 95 parts of ETFE; 0.8 parts of chemical foaming agent; 0.2 part of foaming auxiliary agent; 1.5 parts of nucleating agent; 0.3 parts of lubricant; 2 parts of a cross-linking agent; 0.2 parts of a main antioxidant; 0.1 part of auxiliary antioxidant.
The ETFE is selected from ETFE with the brand number of EP 620; the chemical foaming agent is azodicarbonamide; the foaming auxiliary agent is Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the PTFE micropowder is selected as the nucleating agent; the lubricant is paraffin; the main antioxidant is antioxidant 245; the auxiliary antioxidant is antioxidant 412S; the cross-linking agent is triallyl cyanurate.
The preparation method comprises the following steps:
(1) Putting ETFE, a chemical foaming agent, a foaming auxiliary agent, a nucleating agent, a primary antioxidant and an auxiliary antioxidant into a stirrer, and uniformly stirring to obtain a first mixture;
(2) Adding a lubricant and a crosslinking agent, and continuously stirring uniformly to obtain a raw material mixture;
(3) And (3) putting the raw material mixture into an extruder, and carrying out melt extrusion at the melting point temperature of ETFE to obtain the foamed ethylene-tetrafluoroethylene copolymer cable material.
Example 3 preparation of a foamed ethylene-tetrafluoroethylene copolymer cable material
The raw materials comprise the following components in parts by weight: 95 parts of ETFE; 0.8 parts of chemical foaming agent; 0.2 part of foaming auxiliary agent; 1.5 parts of nucleating agent; 0.3 parts of lubricant; 2 parts of a cross-linking agent; 0.2 parts of a main antioxidant; 0.1 part of auxiliary antioxidant.
The ETFE is selected from ETFE with the brand number of EP 620; the chemical foaming agent is azodicarbonamide; the foaming auxiliary agent is Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the PTFE micropowder is selected as the nucleating agent; the lubricant is paraffin; the main antioxidant is antioxidant 245; the auxiliary antioxidant is antioxidant 412S; the cross-linking agent is trimethylolpropane trimethacrylate.
The preparation method comprises the following steps:
(1) Putting ETFE, a chemical foaming agent, a foaming auxiliary agent, a nucleating agent, a primary antioxidant and an auxiliary antioxidant into a stirrer, and uniformly stirring to obtain a first mixture;
(2) Adding a lubricant and a crosslinking agent, and continuously stirring uniformly to obtain a raw material mixture;
(3) And (3) putting the raw material mixture into an extruder, and carrying out melt extrusion at the melting point temperature of ETFE to obtain the foamed ethylene-tetrafluoroethylene copolymer cable material.
Example 4 preparation of a foamed ethylene-tetrafluoroethylene copolymer cable material
The raw materials comprise the following components in parts by weight: 95 parts of ETFE; 0.8 parts of chemical foaming agent; 0.2 part of foaming auxiliary agent; 1.5 parts of nucleating agent; 0.3 parts of lubricant; 2 parts of a cross-linking agent; 0.2 parts of a main antioxidant; 0.1 part of auxiliary antioxidant.
The ETFE is selected from ETFE with the brand number of EP 620; the chemical foaming agent is azodicarbonamide; the foaming auxiliary agent is Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the PTFE micropowder is selected as the nucleating agent; the lubricant is paraffin; the main antioxidant is antioxidant 245; the auxiliary antioxidant is antioxidant 412S; the cross-linking agent consists of trimethylolpropane trimethacrylate and triallyl cyanurate in the weight ratio of 1:4.
The preparation method comprises the following steps:
(1) Putting ETFE, a chemical foaming agent, a foaming auxiliary agent, a nucleating agent, a primary antioxidant and an auxiliary antioxidant into a stirrer, and uniformly stirring to obtain a first mixture;
(2) Adding a lubricant and a crosslinking agent, and continuously stirring uniformly to obtain a raw material mixture;
(3) And (3) putting the raw material mixture into an extruder, and carrying out melt extrusion at the melting point temperature of ETFE to obtain the foamed ethylene-tetrafluoroethylene copolymer cable material.
Example 5 preparation of a foamed ethylene-tetrafluoroethylene copolymer cable material
The raw materials comprise the following components in parts by weight: 95 parts of ETFE; 0.8 parts of chemical foaming agent; 0.2 part of foaming auxiliary agent; 1.5 parts of nucleating agent; 0.3 parts of lubricant; 2 parts of a cross-linking agent; 0.2 parts of a main antioxidant; 0.1 part of auxiliary antioxidant.
The ETFE is selected from ETFE with the brand number of EP 620; the chemical foaming agent is azodicarbonamide; the foaming auxiliary agent is Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the PTFE micropowder is selected as the nucleating agent; the lubricant is paraffin; the main antioxidant is antioxidant 245; the auxiliary antioxidant is antioxidant 412S; the cross-linking agent consists of trimethylolpropane trimethacrylate and triallyl cyanurate in the weight ratio of 1:4.
The preparation method comprises the following steps:
(1) Putting ETFE and a cross-linking agent into a stirrer to be uniformly stirred to obtain a first mixture;
(2) Then adding a chemical foaming agent, a foaming auxiliary agent, a nucleating agent, a primary antioxidant and an auxiliary antioxidant, and continuously and uniformly stirring to obtain a second mixture;
(3) Adding a lubricant, and continuously stirring uniformly to obtain a raw material mixture;
(4) And (3) putting the raw material mixture into an extruder, and carrying out melt extrusion at the melting point temperature of ETFE to obtain the foamed ethylene-tetrafluoroethylene copolymer cable material.
Example 6 preparation of a foamed ethylene-tetrafluoroethylene copolymer cable material
The raw materials comprise the following components in parts by weight: 95 parts of ETFE; 0.8 parts of chemical foaming agent; 0.2 part of foaming auxiliary agent; 1.5 parts of nucleating agent; 0.3 parts of lubricant; 2 parts of a cross-linking agent; 0.2 parts of a main antioxidant; 0.1 part of auxiliary antioxidant.
The ETFE is selected from ETFE with the brand number of EP 620; the chemical foaming agent is azodicarbonamide; the foaming auxiliary agent is Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the PTFE micropowder is selected as the nucleating agent; the lubricant is paraffin; the main antioxidant is antioxidant 245; the auxiliary antioxidant is antioxidant 412S; the cross-linking agent consists of trimethylolpropane trimethacrylate and triallyl cyanurate in the weight ratio of 1:4.
The preparation method comprises the following steps:
(1) Putting ETFE, a chemical foaming agent, a foaming auxiliary agent, a nucleating agent, a main antioxidant, an auxiliary antioxidant and 1/3 of a crosslinking agent into a stirrer, and uniformly stirring to obtain a first mixture;
(2) Adding the lubricant and the rest of the crosslinking agent, and continuously stirring uniformly to obtain a raw material mixture;
(3) And (3) putting the raw material mixture into an extruder, and carrying out melt extrusion at the melting point temperature of ETFE to obtain the foamed ethylene-tetrafluoroethylene copolymer cable material.
Example 7 preparation of a foamed ethylene-tetrafluoroethylene copolymer cable material
The raw materials comprise the following components in parts by weight: 95 parts of ETFE; 0.8 parts of chemical foaming agent; 0.2 part of foaming auxiliary agent; 1.5 parts of nucleating agent; 0.3 parts of lubricant; 2 parts of a cross-linking agent; 0.2 parts of a main antioxidant; 0.1 part of auxiliary antioxidant.
The ETFE is selected from ETFE with the brand number of EP 620; the chemical foaming agent is azodicarbonamide; the foaming auxiliary agent is Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the PTFE micropowder is selected as the nucleating agent; the lubricant is paraffin; the main antioxidant is antioxidant 245; the auxiliary antioxidant is antioxidant 412S; the cross-linking agent consists of trimethylolpropane trimethacrylate and triallyl cyanurate in the weight ratio of 1:4.
The preparation method comprises the following steps:
(1) Putting 1/3 of the cross-linking agent and ETFE into a stirrer to be uniformly stirred to obtain a first mixture;
(2) Then adding a chemical foaming agent, a foaming auxiliary agent, a nucleating agent, a primary antioxidant and an auxiliary antioxidant, and continuously and uniformly stirring to obtain a second mixture;
(3) Adding a lubricant and the rest of the crosslinking agent, and continuously stirring uniformly to obtain a raw material mixture;
(4) And (3) putting the raw material mixture into an extruder, and carrying out melt extrusion at the melting point temperature of ETFE to obtain the foamed ethylene-tetrafluoroethylene copolymer cable material.
Example 8 preparation of a foamed ethylene-tetrafluoroethylene copolymer cable material
The raw materials comprise the following components in parts by weight: 90 parts of ETFE; 0.5 part of chemical foaming agent; 0.1 part of foaming auxiliary agent; 1 part of nucleating agent; 0.5 parts of lubricant; 1 part of cross-linking agent; 0.3 parts of a main antioxidant; 0.2 parts of auxiliary antioxidant.
The ETFE is selected from ETFE with the brand number of EP 620; the chemical foaming agent is azodicarbonamide; the foaming auxiliary agent is Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the PTFE micropowder is selected as the nucleating agent; the lubricant is paraffin; the main antioxidant is antioxidant 245; the auxiliary antioxidant is antioxidant 412S; the cross-linking agent consists of trimethylolpropane trimethacrylate and triallyl cyanurate in the weight ratio of 1:5.
The preparation method comprises the following steps:
(1) Putting 1/2 of the cross-linking agent and ETFE into a stirrer to be uniformly stirred to obtain a first mixture;
(2) Then adding a chemical foaming agent, a foaming auxiliary agent, a nucleating agent, a primary antioxidant and an auxiliary antioxidant, and continuously and uniformly stirring to obtain a second mixture;
(3) Adding a lubricant and the rest of the crosslinking agent, and continuously stirring uniformly to obtain a raw material mixture;
(4) And (3) putting the raw material mixture into an extruder, and carrying out melt extrusion at the melting point temperature of ETFE to obtain the foamed ethylene-tetrafluoroethylene copolymer cable material.
Example 9 preparation of a foamed ethylene-tetrafluoroethylene copolymer cable material
The raw materials comprise the following components in parts by weight: 100 parts of ETFE; 1.5 parts of chemical foaming agent; 0.5 part of foaming auxiliary agent; 2 parts of nucleating agent; 0.1 parts of lubricant; 3 parts of cross-linking agent.
The ETFE is selected from ETFE with the brand number of EP 620; the chemical foaming agent is azodicarbonamide; the foaming auxiliary agent is Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the PTFE micropowder is selected as the nucleating agent; the lubricant is paraffin; the cross-linking agent consists of trimethylolpropane trimethacrylate and triallyl cyanurate in the weight ratio of 1:3.
The preparation method comprises the following steps:
(1) Putting 1/3 of the cross-linking agent and ETFE into a stirrer to be uniformly stirred to obtain a first mixture;
(2) Then adding a chemical foaming agent, a foaming auxiliary agent and a nucleating agent, and continuously and uniformly stirring to obtain a second mixture;
(3) Adding a lubricant and the rest of the crosslinking agent, and continuously stirring to obtain a raw material mixture;
(4) And (3) putting the raw material mixture into an extruder, and carrying out melt extrusion at the melting point temperature of ETFE to obtain the foamed ethylene-tetrafluoroethylene copolymer cable material.
The foamed ethylene-tetrafluoroethylene copolymer cable materials prepared in examples 1 to 9 were respectively taken, the foamed ethylene-tetrafluoroethylene copolymer cable materials and the conductors were extruded into a wire shape by using an extruder, the foamed ethylene-tetrafluoroethylene copolymer cable materials formed an insulating layer covering the conductors, and were irradiated on an electron irradiation instrument at an irradiation dose of 15Mrad. Testing the tensile strength and elongation at break of the foamed ethylene-tetrafluoroethylene copolymer cable material after irradiation (testing with reference to ASTM D638); the test results are shown in Table 1.
Table 1.
Material Tensile Strength Elongation at break
Example 1 expanded ethylene-tetrafluoroethylene copolymer Cable Material 28Mpa 80％
Example 2 expanded ethylene tetrafluoroethylene copolymer Cable Material 37Mpa 115％
Example 3 expanded ethylene tetrafluoroethylene copolymer Cable Material 35Mpa 109％
Example 4 expanded ethylene tetrafluoroethylene copolymer Cable Material 41Mpa 136％
Example 5 expanded ethylene-tetrafluoroethylene copolymer Cable Material 38Mpa 127％
Example 6 expanded ethylene-tetrafluoroethylene copolymer Cable Material 40Mpa 132％
Example 7 expanded ethylene tetrafluoroethylene copolymer Cable Material 55Mpa 173％
Example 8 expanded ethylene-tetrafluoroethylene copolymer Cable Material 49Mpa 158％
Example 9 expanded ethylene-tetrafluoroethylene copolymer Cable Material 53Mpa 164％
As can be seen from the experimental data in Table 1, the tensile strength and the elongation at break of the cable material of the foamed ethylene-tetrafluoroethylene copolymer prepared in example 1 after irradiation are not ideal and need to be improved. The tensile strength and the elongation at break of the foamed ethylene-tetrafluoroethylene copolymer cable material prepared in the embodiment 2 after irradiation are obviously improved compared with those of the embodiment 1; whereas example 1 differs from example 2 in the choice of ETFE material; this illustrates: the selection of the ETFE material has important influence on the tensile strength and the elongation at break of the foamed ethylene-tetrafluoroethylene copolymer cable material prepared after foaming after irradiation; when ETFE with the melting point smaller than 240 ℃ is selected as the ETFE, the tensile strength and the elongation at break of the prepared ethylene-tetrafluoroethylene copolymer cable material are obviously higher than those of the prepared ethylene-tetrafluoroethylene copolymer cable material with the ETFE with the melting point larger than 240 ℃ after irradiation.
As can be seen from the experimental data in table 1, the tensile strength and the elongation at break of the foamed ethylene-tetrafluoroethylene copolymer cable material prepared in example 4 after irradiation are further significantly improved compared with those of examples 2 and 3; example 4 differs from examples 2 and 3 in the choice of cross-linking agent; the cross-linking agent in example 2 is triallyl cyanurate, the cross-linking agent in example 3 is trimethylol propane trimethacrylate, and the cross-linking agent in example 4 is a cross-linking agent composed of trimethylol propane trimethacrylate and triallyl cyanurate. This illustrates: the different crosslinking agents have different degrees of improvement of tensile strength and elongation at break after irradiation for the foamed ethylene-tetrafluoroethylene copolymer cable material prepared by taking ETFE with the melting point of less than 240 ℃ as a raw material. The ethylene-tetrafluoroethylene copolymer cable material is prepared by taking ETFE with the melting point less than 240 ℃ as a raw material and adding a cross-linking agent consisting of trimethylolpropane trimethacrylate and triallyl cyanurate, and the tensile strength and the elongation at break of the ethylene-tetrafluoroethylene copolymer cable material after irradiation are greatly higher than those of the ethylene-tetrafluoroethylene copolymer cable material prepared by only adopting the trimethylolpropane trimethacrylate as the cross-linking agent or only adopting the triallyl cyanurate as the cross-linking agent. It also shows that the ETFE with the melting point less than 240 ℃ is taken as a raw material, and the crosslinking agent consisting of trimethylolpropane trimethacrylate and triallyl cyanurate is added to synergistically improve the tensile strength and the elongation at break of the prepared foaming ethylene-tetrafluoroethylene copolymer cable material after irradiation.
From the experimental data in table 1, it can be seen that the tensile strength and the elongation at break of the foamed ethylene-tetrafluoroethylene copolymer cable material prepared in example 7 after irradiation are further greatly improved compared with those of examples 4 to 6; whereas example 7 differs from examples 4 to 6 in the manner of adding the crosslinking agent during the preparation of the foamed ethylene-tetrafluoroethylene copolymer cable material. This illustrates: in the process of preparing the foaming ethylene-tetrafluoroethylene copolymer cable material, the addition mode of the cross-linking agent has important influence on the tensile strength and the elongation at break of the prepared foaming ethylene-tetrafluoroethylene copolymer cable material after irradiation. According to the invention, a part of cross-linking agent is mixed with ETFE, then materials such as a chemical foaming agent and the like are added, and finally the cross-linking agent is added twice in a mode of adding the rest of cross-linking agent, so that the tensile strength and the elongation at break of the prepared foamed ethylene-tetrafluoroethylene copolymer cable material after irradiation are greatly higher than those of the foamed ethylene-tetrafluoroethylene copolymer cable material prepared by adding the cross-linking agent once, and meanwhile, the tensile strength and the elongation at break of the prepared foamed ethylene-tetrafluoroethylene copolymer cable material are also greatly higher than those of the foamed ethylene-tetrafluoroethylene copolymer cable material prepared by adding the cross-linking agent twice in other modes.

Claims (6)

1. The foaming ethylene-tetrafluoroethylene copolymer cable material is characterized by comprising the following raw materials in parts by weight:
90-100 parts of ETFE; 0.5 to 1.5 portions of chemical foaming agent; 0.1 to 0.5 part of foaming auxiliary agent; 1-2 parts of nucleating agent; 0.1-0.5 part of lubricant; 1-5 parts of cross-linking agent;
the ETFE is selected from ETFE with a melting point of less than 240 ℃;
the cross-linking agent is selected from the combination of trimethylolpropane trimethacrylate and triallyl cyanurate;
the preparation method of the foamed ethylene-tetrafluoroethylene copolymer cable material comprises the following steps:
(1) Dividing the cross-linking agent into two parts, and uniformly mixing the first part of cross-linking agent with ETFE to obtain a first mixture;
(2) Uniformly mixing a chemical foaming agent and a foaming auxiliary agent with the first mixture to obtain a second mixture;
(3) Uniformly mixing the lubricant, the second part of cross-linking agent and the second mixture to obtain a raw material mixture;
(4) Melt-extruding the raw material mixture through an extruder to obtain the foamed ethylene-tetrafluoroethylene copolymer cable material;
wherein the weight of the first part of cross-linking agent accounts for 1/3-1/2 of the total weight of the total cross-linking agent.
2. The foamed ethylene-tetrafluoroethylene copolymer cable material according to claim 1, comprising the following raw materials in parts by weight:
93-98 parts of ETFE; 0.5 to 1 part of chemical foaming agent; 0.1 to 0.3 part of foaming auxiliary agent; 1 to 1.5 portions of nucleating agent; 0.2-0.5 part of lubricant; 1-3 parts of cross-linking agent.
3. The foamed ethylene-tetrafluoroethylene copolymer cable material according to claim 1, wherein the chemical blowing agent is selected from azodicarbonamide.
4. The foamed ethylene-tetrafluoroethylene copolymer cable material according to claim 1, wherein the crosslinking agent is at least one selected from trifunctional acrylate and trifunctional allyl ester.
5. The foamed ethylene-tetrafluoroethylene copolymer cable material according to claim 1, wherein the weight ratio of trimethylolpropane trimethacrylate to triallyl cyanurate is 1:3-5.
6. The foamed ethylene-tetrafluoroethylene copolymer cable material according to claim 5, wherein the weight ratio of trimethylolpropane trimethacrylate to triallyl cyanurate is 1:4.
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