WO2015051581A1 - Insulating material for nuclear grade electric cables - Google Patents

Insulating material for nuclear grade electric cables Download PDF

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WO2015051581A1
WO2015051581A1 PCT/CN2013/090818 CN2013090818W WO2015051581A1 WO 2015051581 A1 WO2015051581 A1 WO 2015051581A1 CN 2013090818 W CN2013090818 W CN 2013090818W WO 2015051581 A1 WO2015051581 A1 WO 2015051581A1
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parts
nuclear
ethylene
insulation material
cable insulation
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Chinese (zh)
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倪昭华
赵成刚
尹沾松
谢世平
张冰莹
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长园集团股份有限公司
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Abstract

Provided is an insulating material for nuclear grade electric cables, consisting of the following components by weight: 30-60 parts of an ethylene-methyl methacrylate copolymer; 40-70 parts of a binary ethylene propylene rubber; 5-15 parts of an alkoxyl polydimethylsiloxane, 90-110 parts of a nano magnesium hydroxide; 5-10 parts of a boron nitride, 0.5-2 parts of an ultraviolet light absorber; and 4-12 parts of an antioxidant. The insulating material for nuclear grade electric cables according to the present invention has a working life of up to 60 years (at a temperature of 90°C), a resistance to doses of radiation of up to 2400 KGy, a high tensile strength and a great elongation at break, is capable of passing a vertical burning test for a single cable and thus meets the requirements of third generation nuclear power stations.

Description

一种核级电缆绝缘料  Nuclear grade cable insulation material
技术领域 Technical field
本发明涉及一种核电站使用的电缆。 背景技术  The invention relates to a cable for use in a nuclear power plant. Background technique
2012年 10月 24 曰， 国务院总理温家宝主持召开国务院常务会 议， 再次讨论并通过《核电安全规划（2011-2020 年）》 和 《核电中 长期发展规划（2011-2020年）》。 该次国务院常务会议称， 在建设节 奏上要 "合理把握"、 "稳步推进"， "稳妥恢复正常建设"， 在准入门 槛上， "新建核电机组必须符合三代安全标准"， "按照全球最高安全 要求新建核电项目。"  On October 24, 2012, Premier Wen Jiabao of the State Council presided over the State Council executive meeting to discuss and adopt the Nuclear Power Safety Plan (2011-2020) and the Medium- and Long-Term Development Plan for Nuclear Power (2011-2020). The State Council executive meeting said that in the construction of the rhythm to "reasonable grasp", "steadily advance", "steadily return to normal construction", on the entry barrier, "new nuclear power units must meet the three generations of safety standards", "according to the highest in the world Safety requirements for new nuclear power projects."
第三代核电站对电缆提出了明确的要求， 严酷环境下的电缆使 用寿命要达到 60年 （90 °C温度）， 辐射剂量要达到 2400KGy, 无卤 阻燃要通过单根电缆垂直燃烧试验。 目前第三代核电站严酷环境下 的电缆全部从国外进口， 虽然国内有部分生产厂家正在进行研制， 但是要实现工程应用还有很长的路要走。 发明内容  The third-generation nuclear power plant puts forward clear requirements for cables. The cable life in harsh environments should reach 60 years (90 °C temperature), the radiation dose should reach 2400KGy, and the halogen-free flame retardant should pass the single cable vertical burning test. At present, the cables under the harsh environment of the third-generation nuclear power plants are all imported from abroad. Although some domestic manufacturers are developing, there is still a long way to go to realize engineering applications. Summary of the invention
本发明要解决的技术问题在于： 提供一种核级电缆绝缘料， 其 使用寿命可达到 60年 （90 °C温度）， 耐辐射剂量达到 2400KGy, 拉 伸强度和断裂伸长率大， 能通过单根电缆垂直燃烧试验， 满足第三 代核电站要求。 The technical problem to be solved by the invention is: providing a nuclear grade cable insulation material, the service life of which can reach 60 years (90 ° C temperature), the radiation resistance dose reaches 2400 KGy, the tensile strength and the elongation at break are large, and can pass Single cable vertical burning test, meeting the third Nuclear power plant requirements.
为了解决上述技术问题， 本发明提出以下技术方案： 一种核级 电缆绝缘料， 由下列按照重量计的组分组成： 乙烯-甲基丙烯酸甲酯 共聚物 30-60份； 二元乙丙橡胶 40-70份； 烷氧基聚二甲基硅氧烷 5-15份； 纳米氢氧化镁 90 - 110份； 氮化硼 5 - 10份； 紫外线吸收 剂 0. 5 - 2份； 抗氧剂 4 - 12份。  In order to solve the above technical problems, the present invention proposes the following technical solutions: A nuclear grade cable insulation material consisting of the following components by weight: ethylene-methyl methacrylate copolymer 30-60 parts; ethylene propylene diene rubber 40-70 parts; alkoxy polydimethylsiloxane 5-15 parts; nanometer magnesium hydroxide 90-110 parts; boron nitride 5-10 parts; ultraviolet absorbers 0. 5 - 2 parts; antioxidant 4 - 12 copies.
上述技术方案的进一步限定在于： 所述的紫外线吸收剂为 1- ( V -羟基 , 5' -二特戊基苯基 ) 苯并三唑。  The above technical solution is further defined by the fact that the ultraviolet absorber is 1-(V-hydroxy, 5'-di-t-pentylphenyl)benzotriazole.
上述技术方案的进一步限定在于： 所述抗氧剂为四（β _ (3, 5- 二叔丁基 -4-羟基苯基）丙酸）季戊四醇酯与 4, A' -硫代双（6-叔丁基 -3-甲基苯酚)按照 1 : 1混配而成。  The above technical solution is further defined by: the antioxidant is tetrakis(β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid) pentaerythritol ester and 4, A'-thiobis (6) -tert-Butyl-3-methylphenol) was compounded according to 1:1.
上述技术方案的进一步限定在于： 该核级电缆绝缘料由下列按 照重量计的组分组成： 乙烯-甲基丙烯酸甲酯共聚物 30份、 二元乙 丙橡胶 70份、 烷氧基聚二甲基硅氧烷 5份、 纳米氢氧化镁 110份、 氮化硼 5份、 紫外线吸收剂 0. 5份、 抗氧剂 4份。  The above technical solution is further defined as follows: The nuclear grade cable insulation is composed of the following components by weight: 30 parts of ethylene-methyl methacrylate copolymer, 70 parts of ethylene propylene diene rubber, alkoxy polydimethylene 5 parts of siloxane, 110 parts of nanometer magnesium hydroxide, 5 parts of boron nitride, 0.5 parts of ultraviolet absorber, and 4 parts of antioxidant.
上述技术方案的进一步限定在于： 该核级电缆绝缘料由下列按 照重量计的组分组成： 乙烯-甲基丙烯酸甲酯共聚物 60份、 二元乙 丙橡胶 40份、 烷氧基聚二甲基硅氧烷 15份、 纳米氢氧化镁 90份、 氮化硼 10份、 紫外线吸收剂 2份、 抗氧剂 12份。  The above technical solution is further defined as follows: The nuclear grade cable insulation is composed of the following components by weight: 60 parts of ethylene-methyl methacrylate copolymer, 40 parts of ethylene propylene diene rubber, alkoxy polydimethylene 15 parts of siloxane, 90 parts of nano-magnesium hydroxide, 10 parts of boron nitride, 2 parts of ultraviolet absorber, and 12 parts of antioxidant.
上述技术方案的进一步限定在于： 该核级电缆绝缘料由下列按 照重量计的组分组成： 乙烯-甲基丙烯酸甲酯共聚物 45份、 二元乙 丙橡胶 55份、 烷氧基聚二甲基硅氧烷 10份、 纳米氢氧化镁 100份、 氮化硼 8份、 紫外线吸收剂 1份、 抗氧剂 8份。 The above technical solution is further defined as follows: The nuclear grade cable insulation is composed of the following components by weight: 45 parts of ethylene-methyl methacrylate copolymer, 55 parts of ethylene propylene diene rubber, alkoxy polydimethylene 10 parts of siloxane, 100 parts of nanometer magnesium hydroxide, 8 parts of boron nitride, 1 part of ultraviolet absorber, and 8 parts of antioxidant.
与现有技术相比， 本发明具有以下有益效果：  Compared with the prior art, the present invention has the following beneficial effects:
1、 二元乙丙橡胶的耐热老化性能非常优异， 与紫外线吸收剂、 抗氧剂共同使用， 能满足 90 °C温度下使用 60年的要求；  1. The ethylene propylene rubber has excellent heat aging resistance. It can be used together with UV absorbers and antioxidants to meet the requirements of 60 years at 90 °C.
2、氮化硼、紫外线吸收剂与抗氧剂具有抗辐射老化的协同效应， 能显著提高材料的耐辐射性能， 辐射剂量达到 2400KGy以后， 其断 裂伸长率大于 50%;  2. Boron nitride, ultraviolet absorber and antioxidant have the synergistic effect of anti-radiation aging, which can significantly improve the radiation resistance of the material. After the radiation dose reaches 2400KGy, the elongation at break is greater than 50%;
3、烷氧基聚二甲基硅氧烷与纳米氢氧化镁具有明显的协效阻燃 作用， 在拉伸强度和断裂伸长率满足要求的前提下， 能通过单根电 缆垂直燃烧试验。 具体实施方式  3. The alkoxy polydimethylsiloxane and the nanometer magnesium hydroxide have obvious synergistic flame retardant effect, and can pass the vertical burning test of a single cable under the premise that the tensile strength and the elongation at break satisfy the requirements. detailed description
本发明提出一种核级电缆绝缘料， 其由下列按照重量计的组分 组成： 乙烯-甲基丙烯酸甲酯共聚物 30-60份； 二元乙丙橡胶 40-70 份； 烷氧基聚二甲基硅氧烷 5-15份; 纳米氢氧化镁 90-110份； 氮 化硼 5-10份； 紫外线吸收剂 0. 5-2份； 抗氧剂 4-12份。  The invention provides a nuclear grade cable insulation material which is composed of the following components by weight: 30-60 parts of ethylene-methyl methacrylate copolymer; 40-70 parts of ethylene propylene diene rubber; alkoxy polymerization 5-15 parts of dimethylsiloxane; 90-110 parts of nanometer magnesium hydroxide; 5-10 parts of boron nitride; 0.5-2 parts of ultraviolet absorber; 4-12 parts of antioxidant.
所述的紫外线吸收剂为 2- (？^羟基^^ ^^二特戊基苯基） 苯 并三唑。  The ultraviolet absorber is 2-(?^hydroxy^^^^dipentylphenyl)benzotriazole.
所述的抗氧剂为四（β - (3, 5-二叔丁基 -4-羟基苯基）丙酸）季戊 四醇酯与 4, 4 -硫代双（6-叔丁基 -3-甲基苯酚)按照 1 : 1混配而成。  The antioxidant is tetrakis(β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid) pentaerythritol ester and 4,4-thiobis(6-tert-butyl-3-methyl) Phenol) is compounded according to 1:1.
上述核级电缆绝缘料的制备方法包括如下步驟：  The preparation method of the above nuclear grade cable insulation material comprises the following steps:
步驟 1 : 取乙烯-甲基丙烯酸甲酯共聚物 30-60份； 二元乙丙橡 胶 40-70份；烷氧基聚二甲基硅氧烷 5-15份； 纳米氢氧化镁 90-110 份； 氮化硼 5-10份； 紫外线吸收剂 0. 5-2份； 抗氧剂 4-12份； 步驟 2 : 通过密炼混炼造粒或者平行双螺杆挤出机混炼造粒， 得到塑料粒子。 Step 1: Take 30-60 parts of ethylene-methyl methacrylate copolymer; binary ethylene propylene rubber 40-2份份; alkoxy polydimethylsiloxane 5-15 parts; nanometer magnesium hydroxide 90-110 parts; boron nitride 5-10 parts; UV absorbers 0. 5-2 parts; 4-12 parts of the agent; Step 2: Mixing and granulating by a mixture kneading or a parallel twin-screw extruder to obtain plastic particles.
步驟 3: 通过单螺杆挤出机挤出成缆， 利用钴 60或者电子加速 器进行辐射交联， 辐射剂量为 100-200KGy。 制备实施例 1  Step 3: Extruding into a cable by a single-screw extruder, using a cobalt 60 or an electron accelerator for radiation crosslinking, and the radiation dose is 100-200 KGy. Preparation Example 1
取乙烯-甲基丙烯酸甲酯共聚物 30份、 二元乙丙橡胶 70份、 烷 氧基聚二甲基硅氧烷 5份、 纳米氢氧化镁 110份、 氮化硼 5份、 紫 外线吸收剂 0. 5份、 抗氧剂 4份。  30 parts of ethylene-methyl methacrylate copolymer, 70 parts of ethylene propylene diene rubber, 5 parts of alkoxy polydimethylsiloxane, 110 parts of nanometer magnesium hydroxide, 5 parts of boron nitride, ultraviolet absorber 0.5 parts, 4 parts of antioxidants.
通过密炼混炼造粒或者平行双螺杆挤出机混炼造粒， 得到塑料 粒子。  The granules are kneaded by a mixture kneading or a parallel twin-screw extruder to obtain plastic particles.
通过单螺杆挤出机挤出成缆， 利用钴 60或者电子加速器进行辐 射交联， 辐射剂量为 100-200KGy。 制备实施例 2  The cable was extruded by a single-screw extruder and subjected to radiation crosslinking using a cobalt 60 or an electron accelerator at a radiation dose of 100-200 KGy. Preparation Example 2
取乙烯-甲基丙烯酸甲酯共聚物 60份、 二元乙丙橡胶 40份、 烷 氧基聚二甲基硅氧烷 15份、 纳米氢氧化镁 90份、 氮化硼 10份、 紫 外线吸收剂 2份、 抗氧剂 12份。  60 parts of ethylene-methyl methacrylate copolymer, 40 parts of ethylene propylene diene rubber, 15 parts of alkoxy polydimethylsiloxane, 90 parts of nanometer magnesium hydroxide, 10 parts of boron nitride, ultraviolet absorber 2 parts, 12 parts of antioxidant.
通过密炼混炼造粒或者平行双螺杆挤出机混炼造粒， 得到塑料 粒子。 通过单螺杆挤出机挤出成缆， 利用钴 60或者电子加速器进行辐 射交联， 辐射剂量为 100-200KGy The plastic particles are obtained by kneading and granulating or mixing and granulating in a parallel twin-screw extruder. Extrusion into a cable by a single-screw extruder, radiation crosslinking using cobalt 60 or an electron accelerator, the radiation dose is 100-200KGy
制备实施例 3 取乙烯-甲基丙烯酸甲酯共聚物 45份、 二元乙丙橡胶 55份、 烷 氧基聚二甲基硅氧烷 10份、 纳米氢氧化镁 100份、 氮化硼 8份、 紫 外线吸收剂 1份、 抗氧剂 8份。 Preparation Example 3 45 parts of ethylene-methyl methacrylate copolymer, 55 parts of ethylene propylene diene rubber, 10 parts of alkoxy polydimethylsiloxane, 100 parts of nanometer magnesium hydroxide, and 8 parts of boron nitride 1 part of UV absorber and 8 parts of antioxidant.
通过密炼混炼造粒或者平行双螺杆挤出机混炼造粒， 得到塑料 粒子。  The granules are kneaded by a mixture kneading or a parallel twin-screw extruder to obtain plastic particles.
通过单螺杆挤出机挤出成缆， 利用钴 60或者电子加速器进行辐 射交联， 辐射剂量为 100-200KGy  Extrusion by a single screw extruder, radiation crosslinking using cobalt 60 or an electron accelerator, the radiation dose is 100-200KGy
材料性能如下表所示 Material properties are shown in the table below
项目 试 方法 要求 实施例 1 实施例 1 实施例 3 拉伸强度 GB/T1040 > 9MPa 12. 6 13. 8 13. 5 断裂伸长率 GB/T1040 > 250% 356 405 382 热老化 （ 150 °C  Project test method Requirements Example 1 Example 1 Example 3 Tensile strength GB/T1040 > 9MPa 12. 6 13. 8 13. 5 Elongation at break GB/T1040 > 250% 356 405 382 Heat aging ( 150 °C
GB/T1040- 2360h ) > 50% 73 86 79  GB/T1040-2360h) > 50% 73 86 79
2006  2006
—断裂伸长率  —Elongation at break
辐射老化（辐射剂 Radiation aging
量 2400kGy， 剂量 > 50% 61 75 66 率 10 kGy/h )
Figure imgf000007_0001
Amount 2400kGy, dose > 50% 61 75 66 rate 10 kGy / h )
Figure imgf000007_0001

Claims

权 利 要 求 书 claims
1、 一种核级电缆绝缘料， 由下列按照重量计的组分组成： 乙烯 -甲基丙烯酸甲酯共聚物 30-60份； 二元乙丙橡胶 40-70份； 烷氧 基聚二甲基硅氧烷 5-15 份； 纳米氢氧化镁 90 - 110份； 氮化硼 5 - 10份； 紫外线吸收剂 0. 5 - 2份； 抗氧剂 4 - 12份。 1. A nuclear-grade cable insulation material, consisting of the following components by weight: 30-60 parts of ethylene-methyl methacrylate copolymer; 40-70 parts of binary ethylene-propylene rubber; alkoxy polydimethyl 5-15 parts of base silicone; 90-110 parts of nano-magnesium hydroxide; 5-10 parts of boron nitride; 0.5-2 parts of ultraviolet absorber; 4-12 parts of antioxidant.
2、 根据权利要求 1所述的一种核级电缆绝缘料， 其特征在于： 所述的紫外线吸收剂为 2- ( 2 -羟基 , 5' -二特戊基苯基 ) 苯并三 坐。 2. A nuclear grade cable insulation material according to claim 1, characterized in that: the ultraviolet absorber is 2-(2-hydroxy, 5'-dipentylphenyl)benzotriazine.
3、 根据权利要求 1所述的一种核级电缆绝缘料， 其特征在于： 所述抗氧剂为四（β - (3, 5-二叔丁基 -4-羟基苯基）丙酸）季戊四醇酯 与 4, 4 -硫代双（6-叔丁基 -3-甲基苯酚)按照 1 : 1混配而成。 3. A nuclear-grade cable insulation material according to claim 1, characterized in that: the antioxidant is tetrakis(β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid) Pentaerythritol ester and 4,4-thiobis(6-tert-butyl-3-methylphenol) are mixed at a ratio of 1:1.
4、 根据权利要求 1所述的一种核级电缆绝缘料， 其特征在于： 该核级电缆绝缘料由下列按照重量计的组分组成： 乙烯 -甲基丙烯酸 甲酯共聚物 30份、 二元乙丙橡胶 70份、 烷氧基聚二甲基硅氧烷 5 份、 纳米氢氧化镁 110份、 氮化硼 5份、 紫外线吸收剂 0. 5份、 抗 氧剂 4份。 4. A nuclear-grade cable insulation material according to claim 1, characterized in that: the nuclear-grade cable insulation material consists of the following components by weight: 30 parts of ethylene-methyl methacrylate copolymer, 2 70 parts of ethylene propylene rubber, 5 parts of alkoxypolydimethylsiloxane, 110 parts of nano-magnesium hydroxide, 5 parts of boron nitride, 0.5 parts of ultraviolet absorber, and 4 parts of antioxidant.
5、 根据权利要求 1所述的一种核级电缆绝缘料， 其特征在于： 该核级电缆绝缘料由下列按照重量计的组分组成： 乙烯 -甲基丙烯酸 甲酯共聚物 60份、 二元乙丙橡胶 40份、 烷氧基聚二甲基硅氧烷 15 份、 纳米氢氧化镁 90份、 氮化硼 10份、 紫外线吸收剂 2份、 抗氧 剂 12份。 5. A nuclear grade cable insulation material according to claim 1, characterized in that: the nuclear grade cable insulation material consists of the following components by weight: 60 parts of ethylene-methyl methacrylate copolymer, 2 40 parts of ethylene propylene rubber, 15 parts of alkoxy polydimethylsiloxane, 90 parts of nano magnesium hydroxide, 10 parts of boron nitride, 2 parts of ultraviolet absorber, and 12 parts of antioxidant.
6、 根据权利要求 1所述的一种核级电缆绝缘料， 其特征在于： 该核级电缆绝缘料由下列按照重量计的组分组成： 乙烯 -甲基丙烯酸 甲酯共聚物 45份、 二元乙丙橡胶 55份、 烷氧基聚二甲基硅氧烷 1 0 份、 纳米氢氧化镁 1 00份、 氮化硼 8份、 紫外线吸收剂 1份、 抗氧 6. A nuclear grade cable insulation material according to claim 1, characterized in that: The nuclear-grade cable insulation material consists of the following components by weight: 45 parts of ethylene-methyl methacrylate copolymer, 55 parts of binary ethylene-propylene rubber, 10 parts of alkoxy polydimethylsiloxane, 100 parts of nano magnesium hydroxide, 8 parts of boron nitride, 1 part of ultraviolet absorber, antioxidant
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