CN106188815B - 耐高温老化的交联乙烯-四氟乙烯共聚物材料 - Google Patents

耐高温老化的交联乙烯-四氟乙烯共聚物材料 Download PDF

Info

Publication number
CN106188815B
CN106188815B CN201610596142.8A CN201610596142A CN106188815B CN 106188815 B CN106188815 B CN 106188815B CN 201610596142 A CN201610596142 A CN 201610596142A CN 106188815 B CN106188815 B CN 106188815B
Authority
CN
China
Prior art keywords
butyl
tert
bis
tetrafluoroethylene copolymer
crosslinking agent
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.)
Active
Application number
CN201610596142.8A
Other languages
English (en)
Other versions
CN106188815A (zh
Inventor
史丛丛
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.)
Cgnpc Delta (jiangsu) Plastic Co Ltd
Original Assignee
Cgnpc Delta (jiangsu) Plastic 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 Cgnpc Delta (jiangsu) Plastic Co Ltd filed Critical Cgnpc Delta (jiangsu) Plastic Co Ltd
Priority to CN201610596142.8A priority Critical patent/CN106188815B/zh
Publication of CN106188815A publication Critical patent/CN106188815A/zh
Application granted granted Critical
Publication of CN106188815B publication Critical patent/CN106188815B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C08L23/0892—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms containing monomers with other atoms than carbon, hydrogen or oxygen atoms
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/246—Intercrosslinking of at least two polymers
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/28—Treatment by wave energy or particle radiation
    • 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
    • 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
    • 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
    • H01B3/443—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 vinylhalogenides or other halogenoethylenic compounds
    • H01B3/445—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 vinylhalogenides or other halogenoethylenic compounds from vinylfluorides or other fluoroethylenic compounds
    • 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
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • 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
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H01B7/292—Protection against damage caused by extremes of temperature or by flame using material resistant to heat
    • 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
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
    • 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
    • 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
    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • 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
    • C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
    • C08J2491/06—Waxes
    • 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
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • 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
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Organic Insulating Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

本发明一种耐高温老化的交联乙烯‑四氟乙烯共聚物材料，由以下质量份的组分组成：乙烯‑四氟乙烯共聚物、预聚物交联剂、N，N’‑双[β‑(3，5‑二叔丁基‑4‑羟基苯基)丙酰]肼、1,3,5‑三(3,5‑二叔丁基‑4‑羟基苄基)异氰尿酸、三氧化二锑、五氧化二锑、N,N'‑乙撑双硬脂酰胺、季戊四醇硬脂酸酯、白油；预聚物交联剂的重均分子量为600~3000，1,3,5‑三(3,5‑二叔丁基‑4‑羟基苄基)异氰尿酸与N，N’‑双[β‑(3，5‑二叔丁基‑4‑羟基苯基)丙酰]肼的重量份比例为3：0.9~1.2；1,3,5‑三(3,5‑二叔丁基‑4‑羟基苄基)异氰尿酸与N，N’‑双[β‑(3，5‑二叔丁基‑4‑羟基苯基)丙酰]肼的重量份比例为3：1。本发明稳定性非常好，加工的成品颜色非常白，经辐照后也不变色。

Description

耐高温老化的交联乙烯-四氟乙烯共聚物材料
技术领域
本发明涉及特种电线电缆材料，尤其涉及辐照交联乙烯-四氟乙烯共聚绝缘料。
背景技术
乙烯-四氟乙烯共聚物（ETFE）又称F40，透明结晶料，熔点为265～280℃，是最强韧和最轻的氟塑料。ETFE具有优良的介电性、绝缘性能和力学性能，耐辐照，耐开裂，耐老化，耐各种化学溶剂，耐高低温，长期工作温度在-65℃到150℃之间。ETFE树脂经辐照交联后，耐辐射性能，抗拉强度和抗老化性能大大提升，长期工作温度提高到200℃，被大量用于特种电缆绝缘料，如运输、航空、化学和核工厂、油井以及井下的各种线缆和通讯线的绝缘。辐照交联乙烯-四氟乙烯（XETFE）绝缘电线电缆是目前飞机安装线两大主要线种之一。目前X-ETFE绝缘料的技术掌握在国外少数几家著名的电线电缆生产厂家中，价格昂贵，供货周期长，遇到特殊时期对我国实行销售管控。目前的XETFE绝缘料生产过程中发烟量大，污染环境；交联剂易自聚，且对加工温度的要求苛刻，在加工过程中热稳定性差，易发黄，且辐照后颜色加深。因此如何克服上述技术问题，成为本领域技术人员努力的方向。
发明内容
本发明的目的是提供一种耐高温老化的交联乙烯-四氟乙烯共聚物材料，该耐高温老化的交联乙烯-四氟乙烯共聚物材料解决目前的XETFE绝缘料加工过程中发烟量高、交联剂易自聚、对加工温度要求较为苛刻的问题，填补国内空白；且本发明生产的电缆料经高温老化后，产品拉伸强度和断裂伸长率的保留率高，本发明所述的预聚物交联剂更适合高温使用的交联电缆料。
为达到上述发明目的，本发明采用的技术方案是：一种耐高温老化的交联乙烯-四氟乙烯共聚物材料，由以下质量份的组分组成：
乙烯-四氟乙烯共聚物（ETFE） 100份，
预聚物交联剂 0.3~8份，
N，N’-双[β- (3，5-二叔丁基-4-羟基苯基)丙酰]肼 0.1~1份，
1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰尿酸 0.5~3份，
三氧化二锑 1~5份，
五氧化二锑 1~3份，
N,N'-乙撑双硬脂酰胺 0.1~2份
季戊四醇硬脂酸酯 0.1~0.5份，
白油 0.1~3份；
所述预聚物交联剂化学结构式如下：
其中X为乙烯基、烯丙基、甲代烯丙基、炔丙基或以上几种的组合，n= 2~15；
所述预聚物交联剂的重均分子量为600~3000，所述1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰尿酸与N，N’-双[β- (3，5-二叔丁基-4-羟基苯基)丙酰]肼的重量份比例为3：0.9~1.2；
所述1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰尿酸与N，N’-双[β- (3，5-二叔丁基-4-羟基苯基)丙酰]肼的重量份比例为3：1。
上述技术方案进一步改进的技术方案如下：
1. 上述方案中，所述X为甲代烯丙基。
2. 上述方案中，所述1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰尿酸与N，N’-双[β- (3，5-二叔丁基-4-羟基苯基)丙酰]肼的重量份比例为3：1。
3. 上述方案中，所述预聚物交联剂的重均分子量为600~5000。
由于上述技术方案的运用，本发明与现有技术相比具有下列优点：
1. 本发明的耐高温老化的交联乙烯-四氟乙烯共聚物材料加工过程中发烟量低，还有一种非常好的性能，就是加工过程中预聚物交联剂热稳定性非常好，加工的成品颜色非常白，经辐照后也不变色；而用单体交联剂的产品，加工过程中发烟量非常大，交联剂不稳定，产品易发黄，辐照后颜色加深。
2. 本发明的耐高温老化的交联乙烯-四氟乙烯共聚物材料，其经高温老化后，所测拉伸强度和断裂伸长率的保留率，相对现有的采用单体交联剂的产品的拉伸强度和断裂伸长率保留率高，本发明所述的预聚物交联剂更适合高温使用的交联电缆料。
3. 本发明的耐高温老化的交联乙烯-四氟乙烯共聚物材料，1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰尿酸与N，N’-双[β- (3，5-二叔丁基-4-羟基苯基)丙酰]肼共同使用，比单独加入其中任何一种，抗氧效果都好。其中1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰尿酸与N，N’-双[β- (3，5-二叔丁基-4-羟基苯基)丙酰]肼的重量份比例为3：1协同作用抗氧效果最好。具体测试方法： 将加入不同种类和含量抗氧剂的绝缘料，压片（1mm），辐照交联后经250℃（辐照剂量12M），7h老化，观察外表颜色变化，结果见表1。三氧化二锑用于含氟的乙烯-四氟乙烯有很好的阻燃效果，并且可用于HF吸收剂，以防止HF浓度过大影响辐照过程中的交联效果，并提高电线的使用寿命。
具体实施方式
下面结合实施例对本发明作进一步描述：
实施例1~3：一种耐高温老化的交联乙烯-四氟乙烯共聚物材料，由以下质量份的组分组成：
乙烯-四氟乙烯共聚物 100份，
预聚物交联剂 0.3~8份，
N，N’-双[β- (3，5-二叔丁基-4-羟基苯基)丙酰]肼 0.1~1份，
1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰尿酸 0.5~3份，
三氧化二锑 1~5份，
五氧化二锑 1~3份，
N,N’-乙撑双硬脂酰胺 0.1~2份
季戊四醇硬脂酸酯 0.1~0.5份，
白油 0.1~3份；
所述预聚物交联剂化学结构式如下：
其中X为乙烯基、烯丙基、甲代烯丙基、炔丙基或以上几种的组合，n= 2~15；
所述预聚物交联剂的重均分子量为600~3000，所述1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰尿酸与N，N’-双[β- (3，5-二叔丁基-4-羟基苯基)丙酰]肼的重量份比例为3：0.9~1.2。
优选预聚物交联剂的重均分子量为1000~3000。
表1 抗氧剂种类对产品抗氧化性能的影响
所述耐高温老化的交联乙烯-四氟乙烯共聚物材料具体由以下重量份组分组成，如表2所示：
表2
一种用于上述耐高温老化的交联乙烯-四氟乙烯共聚物材料的制备方法，包括以下步骤：
第一步：将按配方重量计量的乙烯-四氟乙烯共聚物100份、N，N’-双[β- (3，5-二叔丁基-4-羟基苯基)丙酰]肼0.1~1份、1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰尿酸0.5~3份、三氧化二锑1~5份、五氧化二锑1~3份、预聚物交联剂0.3~8份、N,N'-乙撑双硬脂酰胺（EBS）0.1~2份、季戊四醇硬脂酸酯（PETS）0.1~0.5份、白油在高速混合机中均匀混合10min后取出；
第二步：将混合均匀的原料在加料口加入，在双螺杆挤出机中挤出造粒，熔融挤出温度为240~340℃；然后烘干并包装，获得耐高温老化的交联乙烯-四氟乙烯共聚物材料。
将所得电缆料经压片，辐照后，经300℃，7h老化，然后取出，室温冷却24h，测其拉伸强度和断裂伸长率保留率，与用TMAIC做交联剂的样品做对比。测试方法：GJB-773A2000, （50±5）mm/min，结果如表3。
表3
从表3中性能可以看出，采用本发明耐高温老化的交联乙烯-四氟乙烯共聚物材料，其测拉伸强度和断裂伸长率的保留率，相对于用单体交联剂的产品的拉伸强度和断裂伸长率的保留率高。其次，加工过程中发烟量低，还有一种非常好的性能，就是加工过程中预聚物交联剂热稳定性非常好，加工的成品颜色非常白，经辐照后也不变色，而用单体交联剂的产品，加工过程中，交联剂不稳定，产品易发黄，辐照后颜色加深。
上述实施例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。

Claims (1)

1.一种耐高温老化的交联乙烯-四氟乙烯共聚物材料，其特征在于：由以下质量份的组分组成：
乙烯-四氟乙烯共聚物（ETFE） 100份，
预聚物交联剂 0.3~8份，
N，N’-双[β- (3，5-二叔丁基-4-羟基苯基)丙酰]肼 0.1~1份，
1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰尿酸 0.3~3份，
三氧化二锑 1~5份，
五氧化二锑 1~3份，
N,N'-乙撑双硬脂酰胺 0.1~2份
季戊四醇硬脂酸酯 0.1~0.5份，
白油 0.1~3份；
所述预聚物交联剂化学结构式如下：
；
其中X为甲代烯丙基，n= 2~15；
所述预聚物交联剂的重均分子量为600~5000，所述1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰尿酸与N，N’-双[β- (3，5-二叔丁基-4-羟基苯基)丙酰]肼的重量份比例为3：1。
CN201610596142.8A 2015-02-05 2015-02-05 耐高温老化的交联乙烯-四氟乙烯共聚物材料 Active CN106188815B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610596142.8A CN106188815B (zh) 2015-02-05 2015-02-05 耐高温老化的交联乙烯-四氟乙烯共聚物材料

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201510059128.XA CN104629159B (zh) 2015-02-05 2015-02-05 交联乙烯‑四氟乙烯共聚物绝缘料
CN201610596142.8A CN106188815B (zh) 2015-02-05 2015-02-05 耐高温老化的交联乙烯-四氟乙烯共聚物材料

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CN201510059128.XA Division CN104629159B (zh) 2015-02-05 2015-02-05 交联乙烯‑四氟乙烯共聚物绝缘料

Publications (2)

Publication Number Publication Date
CN106188815A CN106188815A (zh) 2016-12-07
CN106188815B true CN106188815B (zh) 2018-11-27

Family

ID=53208426

Family Applications (3)

Application Number Title Priority Date Filing Date
CN201510059128.XA Active CN104629159B (zh) 2015-02-05 2015-02-05 交联乙烯‑四氟乙烯共聚物绝缘料
CN201610596142.8A Active CN106188815B (zh) 2015-02-05 2015-02-05 耐高温老化的交联乙烯-四氟乙烯共聚物材料
CN201610596143.2A Active CN106046525B (zh) 2015-02-05 2015-02-05 低发烟量乙烯-四氟乙烯共聚物材料

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CN201510059128.XA Active CN104629159B (zh) 2015-02-05 2015-02-05 交联乙烯‑四氟乙烯共聚物绝缘料

Family Applications After (1)

Application Number Title Priority Date Filing Date
CN201610596143.2A Active CN106046525B (zh) 2015-02-05 2015-02-05 低发烟量乙烯-四氟乙烯共聚物材料

Country Status (1)

Country Link
CN (3) CN104629159B (zh)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104629159B (zh) * 2015-02-05 2017-03-29 中广核三角洲（江苏）塑化有限公司 交联乙烯‑四氟乙烯共聚物绝缘料
JP6732803B2 (ja) * 2015-06-16 2020-07-29 ダウ グローバル テクノロジーズ エルエルシー ハイブリッドスコーチ遅延剤／硬化助剤
CN105061876A (zh) * 2015-08-06 2015-11-18 中广核三角洲（江苏）塑化有限公司 性能可调节的辐照交联乙烯-四氟乙烯共聚物绝缘料
CN108976346B (zh) * 2015-08-06 2021-06-04 中广核三角洲（江苏）塑化有限公司 高稳定性含氟聚合物
CN105949603A (zh) * 2016-07-11 2016-09-21 苏州泰尚新材料有限公司 一种抗氧化抗降解线缆外皮及其制备方法
CN106188796A (zh) * 2016-07-11 2016-12-07 芜湖航飞科技股份有限公司 航空用高温安装线绝缘料及其制备方法
JP7153563B2 (ja) * 2017-06-12 2022-10-14 Nok株式会社 フッ素ゴム組成物およびフッ素ゴムシール材
CN109337263B (zh) * 2018-10-08 2022-04-15 深圳市沃尔核材股份有限公司 可低温加工的辐照交联耐高温电缆附件及生产方法
CN109354757B (zh) * 2018-10-08 2023-12-12 深圳市沃尔核材股份有限公司 可低温加工的辐照交联耐高温线缆绝缘材料及生产方法
CN109294051B (zh) * 2018-10-08 2021-10-22 深圳市沃尔核材股份有限公司 一种可低温加工的辐照交联乙烯-四氟乙烯共聚物材料
CN114644790A (zh) * 2020-12-21 2022-06-21 中广核三角洲（江苏）塑化有限公司 辐照交联乙烯-四氟乙烯共聚物绝缘材料的制备工艺
CN114644789A (zh) * 2020-12-21 2022-06-21 中广核三角洲（江苏）塑化有限公司 改性辐照交联乙烯-四氟乙烯共聚物绝缘料

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5256748A (en) * 1990-07-02 1993-10-26 Autochem Precursors of polymers containing isocyanurate units
EP1452561A1 (en) * 2003-02-28 2004-09-01 Nichias Corporation Fluororubber molded article and method for producing the same
CN1743370A (zh) * 2004-09-02 2006-03-08 霓佳斯株式会社 氟橡胶组合物、橡胶材料和氟橡胶成型体的制造方法
CN1332988C (zh) * 2001-09-26 2007-08-22 霓佳斯株式会社 氟橡胶模塑产品及其生产方法
JP4345220B2 (ja) * 2000-10-16 2009-10-14 ユニマテック株式会社 含フッ素エラストマー組成物
CN104629159B (zh) * 2015-02-05 2017-03-29 中广核三角洲（江苏）塑化有限公司 交联乙烯‑四氟乙烯共聚物绝缘料

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0627158B2 (ja) * 1984-07-03 1994-04-13 日立電線株式会社 放射線照射架橋可能なふつ素樹脂組成物
JPH05271430A (ja) * 1992-03-27 1993-10-19 Nitto Denko Corp フッ素樹脂チューブ、その製造法およびその用途
JPH07278394A (ja) * 1994-04-11 1995-10-24 Asahi Glass Co Ltd 架橋可能な含フッ素樹脂組成物
JPH07292199A (ja) * 1994-04-28 1995-11-07 Asahi Glass Co Ltd フッ素系ポリマー組成物およびその架橋方法
CN100411061C (zh) * 2006-06-20 2008-08-13 广州凯恒特种电线电缆有限公司 辐照交联改性乙烯-四氟乙烯绝缘电线电缆及其制造方法
CN104151754B (zh) * 2014-08-15 2016-05-25 上海三爱富新材料股份有限公司 高流动性乙烯-四氟乙烯共聚物组合物及其制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5256748A (en) * 1990-07-02 1993-10-26 Autochem Precursors of polymers containing isocyanurate units
JP4345220B2 (ja) * 2000-10-16 2009-10-14 ユニマテック株式会社 含フッ素エラストマー組成物
CN1332988C (zh) * 2001-09-26 2007-08-22 霓佳斯株式会社 氟橡胶模塑产品及其生产方法
EP1452561A1 (en) * 2003-02-28 2004-09-01 Nichias Corporation Fluororubber molded article and method for producing the same
CN1743370A (zh) * 2004-09-02 2006-03-08 霓佳斯株式会社 氟橡胶组合物、橡胶材料和氟橡胶成型体的制造方法
CN104629159B (zh) * 2015-02-05 2017-03-29 中广核三角洲（江苏）塑化有限公司 交联乙烯‑四氟乙烯共聚物绝缘料

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
《电线用辐照交联乙烯-四氟乙烯共聚物绝缘料》;忻济民;《中国电工技术学会电线电缆专委会、中国电机工程学会电力电缆分专委会交联电缆专题研讨会（2002年会）论文集》;20021130;第1页至第11页 *

Also Published As

Publication number Publication date
CN104629159B (zh) 2017-03-29
CN106046525B (zh) 2018-07-20
CN106046525A (zh) 2016-10-26
CN104629159A (zh) 2015-05-20
CN106188815A (zh) 2016-12-07

Similar Documents

Publication Publication Date Title
CN106188815B (zh) 耐高温老化的交联乙烯-四氟乙烯共聚物材料
CN101633754B (zh) 耐油型硅烷自然交联低烟无卤阻燃聚烯烃电缆料及其制备方法
CA2775975C (en) Heat stabilized polymeric composition with epoxidized fatty acid ester plasticizer
CN103450598A (zh) 改性聚氯乙烯电缆料
CN106633341B (zh) 电梯电缆用硅烷交联低烟无卤阻燃聚烯烃弹性体料及制法
CN101157785A (zh) 一种电线电缆用辐照交联聚氯乙烯电缆料及其制备方法
CN101245169A (zh) 免水煮低烟无卤阻燃硅烷交联聚烯烃组合物及其制备方法
CN106543517A (zh) 一种聚烯烃电缆料及其制备方法
CN105524368B (zh) 一种机器人线缆专用聚氯乙烯护套材料及制备方法
CN105061876A (zh) 性能可调节的辐照交联乙烯-四氟乙烯共聚物绝缘料
CN102532755A (zh) 一种热收缩套管的配方及其加工工艺
CN106543607A (zh) 一种航天航空用交联氟塑料电缆料及其制备方法
CN104371219B (zh) 一种医用耐热耐老化复合塑料及其制备方法
CN103554639B (zh) 一种环保型无卤阻燃电线电缆的生产方法
CN105034186B (zh) 光伏线缆护套层材料的制备方法
CN108164798B (zh) 一种低发烟量的热塑性低烟无卤阻燃聚烯烃材料及其制备方法
CN109354757A (zh) 可低温加工的辐照交联耐高温线缆绝缘材料及生产方法
RU2473994C1 (ru) Способ получения фторполимерной радиационно-сшиваемой композиции
CN109337188B (zh) 一种辐照交联耐高温热缩套管及生产方法
JP2017224454A (ja) ケーブル
CN111100391A (zh) 一种耐候性电线电缆料及其生产工艺
CN101266845A (zh) 环保型聚氯乙烯电缆料及其制备方法
CN105482462A (zh) 一种耐高温低烟无卤电缆料及制备方法
CN109294051A (zh) 一种可低温加工的辐照交联乙烯-四氟乙烯共聚物材料
CN104829909A (zh) 一种耐高温强度高的硅烷交联聚乙烯电缆料及其制作方法

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant