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WO2023065430A1 - 一种导电炭黑高效分散的高压电缆半导电屏蔽料及制备方法 - Google Patents

一种导电炭黑高效分散的高压电缆半导电屏蔽料及制备方法 Download PDF

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WO2023065430A1
WO2023065430A1 PCT/CN2021/130245 CN2021130245W WO2023065430A1 WO 2023065430 A1 WO2023065430 A1 WO 2023065430A1 CN 2021130245 W CN2021130245 W CN 2021130245W WO 2023065430 A1 WO2023065430 A1 WO 2023065430A1
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carbon black
conductive carbon
conductive
parts
shielding material
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PCT/CN2021/130245
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English (en)
French (fr)
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章彬
徐曙
陈潇
伍国兴
侯帅
傅明利
黎小林
贾利川
惠宝军
朱闻博
冯宾
张逸凡
展云鹏
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深圳供电局有限公司
南方电网科学研究院有限责任公司
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Publication of WO2023065430A1 publication Critical patent/WO2023065430A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08L39/06—Homopolymers or copolymers of N-vinyl-pyrrolidones

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  • the invention relates to the technical field of semi-conductive shielding materials for high-voltage cables, in particular to a semi-conductive shielding material for high-voltage cables in which conductive carbon black is efficiently dispersed and a preparation method thereof.
  • the semi-conductive shielding layer plays the role of uniform electric field distribution in the insulating layer, eliminating the air gap at the interface between the conductor and the insulating layer, improving the initial corona discharge of the cable and the resistance to free discharge of the cable, and its quality directly affects the safety of high-voltage cables and stability.
  • the material for the semi-conductive shielding layer is mainly prepared by melt blending and compounding polymer matrix resin, conductive carbon black and processing aids.
  • conductive carbon black determines the electrical properties, mechanical properties and surface finish of high-voltage shielding materials. Due to the large surface area, surface energy and irregular branched chain structure of conductive carbon black, it is easy to form agglomerates in the matrix resin, resulting in a sharp decline in the conductivity and surface finish of the semi-conductive shielding material.
  • the current methods for the dispersion of conductive carbon black are mainly based on the physical coating of surfactants, which have weak interfacial force with conductive carbon black and cannot achieve a good dispersion effect of conductive carbon black. Therefore, the use of a dispersant that has a good interface with conductive carbon black is the key to solving the dispersion of conductive carbon black.
  • the present invention provides a high-voltage cable semi-conductive shielding material and a preparation method that enables the conductive carbon black to be evenly dispersed in the matrix resin, and the surface smoothness of the semi-conductive shielding material is high, and the conductive carbon black is efficiently dispersed.
  • a high-voltage cable semi-conductive shielding material with highly efficient dispersion of conductive carbon black comprising the following components in parts by weight: 55-65 parts of matrix resin, 28-35 parts of conductive carbon black, 0.5-2.5 parts of dispersant and 4-4 parts of functional additives 7 parts; the dispersant is polyvinylpyrrolidone.
  • the functional auxiliary agent includes in parts by weight: 1-2 parts of coupling agent, 0.5-1 part of antioxidant, 1-2 parts of lubricant; the antioxidant is antioxidant 1010 and antioxidant 168 or more Can be mixed in any proportion.
  • the matrix resin is ethylene butyl acrylate resin.
  • the lubricant is formed by mixing one or two of zinc stearate and polyethylene wax in any proportion.
  • crosslinking agent is a peroxide initiator, preferably di-tert-butyl cumene peroxide.
  • a method for preparing a high-voltage cable semi-conductive shielding material with high-efficiency dispersion of conductive carbon black comprising the following steps:
  • Step 1 Weigh each raw material component, stir and mix the dispersant, coupling agent and conductive carbon black to obtain a pretreated conductive carbon black;
  • Step 2 Add ethylene butyl acrylate resin, antioxidant, lubricant to the conductive carbon black pretreatment and continue to stir and mix;
  • Step 3 using a twin-screw extruder to melt and extrude the mixture obtained in step 2 to granulate;
  • Step 4 Heat the pellets obtained in Step 3 to temperature T, mix them with a cross-linking agent, and keep warm for t time to obtain the required high-voltage cable semi-conductive shielding material.
  • the heating temperature T in step 4 is 60-65°C.
  • the heat preservation time in step 4 is 8-12 hours.
  • the present invention adopts polyvinylpyrrolidone as a dispersant, overcomes that the semi-conductive shielding material of high-voltage cables filled with common conductive carbon black is easy to reunite, the conductivity and processability of the semi-conductive shielding material deteriorate, and the surface of the semi-conductive shielding material of high-voltage cables is not smooth. Smooth, with many raised spots;
  • the antioxidant 1010 and the antioxidant 168 are compounded and used together, and the antioxidant 168 plays the main role in the processing process, and the antioxidant 1010 plays the main role in the material aging process.
  • the additive reaction and synergistic reaction of the two antioxidants can achieve a better antioxidant effect and prolong the service life of the semi-conductive shielding material.
  • ethylene butyl acrylate is selected as the matrix resin, which has better thermal stability than the commonly used EVA resin.
  • Fig. 1 is the performance graph of the surface smoothness of the high-voltage cable semi-conductive shielding material obtained in Example 1 and Comparative Example.
  • a high-voltage cable semi-conductive shielding material with highly efficient dispersion of conductive carbon black comprising the following components in parts by weight: 55-65 parts of matrix resin, 28-35 parts of conductive carbon black, 0.5-2.5 parts of dispersant and 4-4 parts of functional additives 7 parts; the dispersant is polyvinylpyrrolidone.
  • the functional additives include: 1-2 parts of coupling agent, 0.5-1 part of antioxidant, and 1-2 parts of lubricant; the antioxidant is composed of antioxidant 1010 and antioxidant 168 mixed in any proportion.
  • the matrix resin is ethylene butyl acrylate resin, the melt index at 190°C and 2.16kg is 8-10g/min, and the breaking strength is >12Mpa.
  • the lubricant is formed by mixing one or two of zinc stearate and polyethylene wax in any proportion.
  • the crosslinking agent is a peroxide initiator, preferably bis-tert-butylperoxycumene.
  • Conductive carbon black is any one of VXC72 and VXC500 produced by American Cabot.
  • a method for preparing a high-voltage cable semi-conductive shielding material with high-efficiency dispersion of conductive carbon black comprising the following steps:
  • Step 1 Weigh each raw material component, stir and mix the dispersant, coupling agent and conductive carbon black to obtain a pretreated conductive carbon black;
  • Step 2 Add ethylene butyl acrylate resin, antioxidant, lubricant to the conductive carbon black pretreatment and continue to stir and mix;
  • Step 3 using a twin-screw extruder to melt and extrude the mixture obtained in step 2 to granulate;
  • Step 4 Put the pellets obtained in Step 3 into the heater and heat to 60-65°C, mix with the cross-linking agent, and then continue to keep warm in the heater for 8-12 hours, so that the premix can fully absorb the cross-linking agent, The required high-voltage cable semi-conductive shielding material can be obtained.
  • the conductive carbon black can be pretreated. After the conductive carbon black and ethylene glycol are ultrasonically mixed, the obtained suspension is heated and stirred at 150°C for 7h; The pretreated conductive carbon black was obtained by washing with distilled water three times and vacuum drying at 60°C. Wherein the mass ratio of conductive carbon black to ethylene glycol is 2-5:50.
  • the conductive carbon black after well treatment can be uniformly and stably dispersed in the matrix resin, which improves the stability of the shielding material.
  • a high-voltage cable semi-conductive shielding material with highly efficient dispersion of conductive carbon black comprising the following components in parts by weight: 58.5 parts of ethylene butyl acrylate resin EBA, 35 parts of conductive carbon black, 2 parts of dispersant, 1 part of crosslinking agent, lubricating 1 part of anti-oxidant, 0.5 part of antioxidant, 2 parts of coupling agent; dispersant is polyvinylpyrrolidone.
  • EBA resin at 190°C and 2.16kg, the melt index is 8.7g/min, and the breaking strength is >12Mpa.
  • the DBP absorption value of conductive carbon black is 148ml/100g; coupling agent is silane coupling agent KH550; antioxidant is the mixture of antioxidant 1010 and antioxidant 168, the mass ratio of antioxidant 1010 and antioxidant 168
  • the lubricant is a mixture of zinc stearate and pentaerythritol, and the mass ratio of zinc stearate and pentaerythritol is 1:1.
  • Step 1 Weigh each component according to the proportion, put the dispersant, coupling agent and conductive carbon black into the mixer for stirring and mixing to obtain the conductive carbon black pretreatment;
  • Step 2 adding ethylene butyl acrylate resin, antioxidant and lubricant to the conductive carbon black pretreatment obtained in step 1 and continuing to stir and mix;
  • Step 3 adding the mixture into a twin-screw extruder for melt extrusion granulation
  • Step 4 Put the obtained pellets into a heater and heat them to 60-65°C, then quickly mix them with the cross-linking agent evenly, and continue to place them in the heater for 8-12 hours, so that the premix can fully absorb the cross-linking agent. Finally, the required high-voltage cable semi-conductive shielding material is obtained.
  • a high-voltage cable semi-conductive shielding material with highly efficient dispersion of conductive carbon black comprising the following components in parts by weight: 59.5 parts of ethylene butyl acrylate resin EBA, 35 parts of conductive carbon black, 1 part of dispersant, 1 part of crosslinking agent, lubricating 1 part of anti-oxidant, 0.5 part of antioxidant, 2 parts of coupling agent; dispersant is polyvinylpyrrolidone.
  • EBA resin at 190°C and 2.16kg, the melt index is 8.7g/min, and the breaking strength is >12Mpa.
  • the DBP absorption value of conductive carbon black is 148ml/100g; coupling agent is silane coupling agent KH550; antioxidant is the mixture of antioxidant 1010 and antioxidant 168, the mass ratio of antioxidant 1010 and antioxidant 168
  • the lubricant is a mixture of zinc stearate and pentaerythritol, and the mass ratio of zinc stearate and pentaerythritol is 1:1.
  • the preparation method is as in Example 1.
  • a high-voltage cable semi-conductive shielding material with highly efficient dispersion of conductive carbon black comprising the following components in parts by weight: 60 parts of ethylene butyl acrylate resin EBA, 35 parts of conductive carbon black, 0.5 parts of dispersant, 1 part of crosslinking agent, lubricating 1 part of anti-oxidant, 0.5 part of antioxidant, 2 parts of coupling agent; dispersant is polyvinylpyrrolidone.
  • EBA resin at 190°C and 2.16kg, the melt index is 8.7g/min, and the breaking strength is >12Mpa.
  • the DBP absorption value of conductive carbon black is 148ml/100g; coupling agent is silane coupling agent KH550; antioxidant is the mixture of antioxidant 1010 and antioxidant 168, the mass ratio of antioxidant 1010 and antioxidant 168
  • the lubricant is a mixture of zinc stearate and pentaerythritol, and the mass ratio of zinc stearate and pentaerythritol is 1:1.
  • the preparation method is as in Example 1.
  • the semi-conductive shielding material for high-voltage cables includes the following components by weight: 58.5 parts of ethylene butyl acrylate resin EBA, 35 parts of conductive carbon black, 2 parts of dispersant, 1 part of crosslinking agent, 1 part of lubricant, and 0.5 parts of antioxidant 2 parts, 2 parts of coupling agent; dispersant is ethylene bis stearic acid amide.
  • EBA resin at 190°C and 2.16kg, the melt index is 8.7g/min, and the breaking strength is >12Mpa.
  • the DBP absorption value of conductive carbon black is 148ml/100g; coupling agent is silane coupling agent KH550; antioxidant is the mixture of antioxidant 1010 and antioxidant 168, the mass ratio of antioxidant 1010 and antioxidant 168
  • the lubricant is a mixture of zinc stearate and pentaerythritol, and the mass ratio of zinc stearate and pentaerythritol is 1:1.
  • the preparation method is as in Example 1.
  • the semi-conductive shielding material for high-voltage cables includes the following components by weight: 58.5 parts of ethylene butyl acrylate resin EBA, 35 parts of conductive carbon black, 2 parts of dispersant, 1 part of crosslinking agent, 1 part of lubricant, and 0.5 parts of antioxidant part, 2 parts of coupling agent; dispersant is pentaerythritol stearate.
  • EBA resin at 190°C and 2.16kg, the melt index is 8.7g/min, and the breaking strength is >12Mpa.
  • the DBP absorption value of conductive carbon black is 148ml/100g; coupling agent is silane coupling agent KH550; antioxidant is the mixture of antioxidant 1010 and antioxidant 168, the mass ratio of antioxidant 1010 and antioxidant 168
  • the lubricant is a mixture of zinc stearate and pentaerythritol, and the mass ratio of zinc stearate and pentaerythritol is 1:1.
  • the preparation method is as in Example 1.
  • Semi-conductive shielding material for high-voltage cables including the following components by weight: 58.5 parts of ethylene butyl acrylate resin EBA, 35 parts of conductive carbon black, 1 part of crosslinking agent, 1 part of lubricant, 0.5 parts of antioxidant, coupling agent 2 servings.
  • EBA resin at 190°C and 2.16kg, the melt index is 8.7g/min, and the breaking strength is >12Mpa.
  • the DBP absorption value of conductive carbon black is 148ml/100g; coupling agent is silane coupling agent KH550; antioxidant is the mixture of antioxidant 1010 and antioxidant 168, the mass ratio of antioxidant 1010 and antioxidant 168
  • the lubricant is a mixture of zinc stearate and pentaerythritol, and the mass ratio of zinc stearate and pentaerythritol is 1:1.
  • the preparation method is as in Example 1.
  • Fig. 1 is the surface smoothness performance diagram of the high-voltage cable semi-conductive shielding material obtained in Example 1 and Comparative Example 1. It can be seen from the figure that the surface of the high-voltage cable semi-conductive shielding material obtained in Example 1 is smooth. The surface of the high-voltage cable semi-conductive shielding material obtained in Comparative Example 1 has obvious raised points, and the size is larger, and the surface is not smooth.
  • dispersants are derivatives of fatty acids, one end is a polar part, the other end is a non-polar part, and its main function is to disperse. It can improve the dispersibility of the solid rubber formula, facilitate the mixing of compounding ingredients, reduce the mixing time, and have a positive impact on subsequent processing.
  • the dispersant also has unique wetting characteristics, which can promote the rapid mixing and dispersion of carbon black and other fillers, improve the internal and external lubricity of the compound, improve the processing performance and the surface finish of the product.
  • the conductive carbon black has better dispersion performance, and the obtained high-voltage cable semi-conductive shielding material has better mechanical and electrical properties, and has a higher surface finish and fewer burrs or protrusions.
  • a dispersant is added to the shielding material during processing to increase the fluidity of the rubber material, so that the surrounding conductive carbon black is protected by non-polar groups, and the refined conductive carbon black particles are fully wetted and encapsulated by rubber. stabilized without agglomeration.
  • the invention realizes the smooth surface of the semi-conductive shielding material and uniform dispersion of the conductive carbon black in the matrix resin through the selection of the matrix resin, the dispersant and the antioxidant and the synergistic effect of the dosage ratio of each component. And the obtained semi-conductive shielding material has excellent mechanical properties and electrical properties.

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Abstract

本发明公开了一种导电炭黑高效分散的高压电缆半导电屏蔽料及制备方法，按照重量份包括以下组分：基体树脂55～65份、导电炭黑28～35份、分散剂0.5～2.5份和功能助剂4～7份；分散剂为聚乙烯吡咯烷酮；本发明通过基体树脂、分散剂、抗氧剂三者种类的选择和各组分剂量配比的协同效应，实现了半导电屏蔽料表面光滑、导电炭黑均匀分散于基体树脂中，并且得到的半导电屏蔽料具有优异的机械性能和电性能。

Description

一种导电炭黑高效分散的高压电缆半导电屏蔽料及制备方法 技术领域
本发明涉及高压电缆半导电屏蔽料技术领域，具体涉及一种导电炭黑高效分散的高压电缆半导电屏蔽料及制备方法。
背景技术
半导电屏蔽层起着均匀绝缘层内电场分布、消除导体与绝缘层交界面气隙、提高电缆起始电晕放电和电缆耐游离放电性能的作用，其品质直接影响着高压电缆的使用安全性和稳定性。
半导电屏蔽层用材料主要是由高分子基体树脂、导电炭黑及加工助剂通过熔融共混复合制备而成。导电炭黑作为高压屏蔽料关键组分，决定着高压屏蔽料的电性能、力学性能和表面光洁度。导电炭黑由于极大的表面积、表面能及不规则的枝链状结构，极易在基体树脂中形成团聚体，从而导致半导电屏蔽料的导电性和表面光洁度急剧下降。目前导电炭黑分散性的方法主要基于表面活性剂的物理包覆，与导电炭黑界面作用力弱，无法实现导电炭黑良好的分散效果的作用。因此使用与导电炭黑具有良好界面作用的分散剂是解决导电炭黑分散的关键。
发明内容
本发明针对现有技术中存在的问题提供一种使导电炭黑均匀分散于基体树脂中，半导电屏蔽料的表面光洁度高的导电炭黑高效分散的高压电缆半导电屏蔽料及制备方法。
本发明采用的技术方案是：
一种导电炭黑高效分散的高压电缆半导电屏蔽料，按照重量份包括以下组分：基体树脂55～65份、导电炭黑28～35份、分散剂0.5～2.5份和功能助剂4～7份；分散剂为聚乙烯吡咯烷酮。
进一步的，所述功能助剂按照重量份包括：偶联剂1～2份、抗氧剂0.5～1份、润滑剂1～2份；抗氧剂为抗氧剂1010和抗氧剂168以任意比例混合构成。
进一步的，所述基体树脂为乙烯丙烯酸丁酯树脂。
进一步的，所述润滑剂为硬脂酸锌和聚乙烯腊中的一种或两种以任意比例混合构成。
进一步的，所述交联剂为过氧化物类引发剂，优选为双叔丁基过氧化异丙基苯。
导电炭黑高效分散的高压电缆半导电屏蔽料的制备方法，包括以下步骤：
步骤1：称取各原料组分，将分散剂、偶联剂和导电炭黑搅拌混合，得到导电炭黑预处理物；
步骤2：在导电炭黑预处理物中加入乙烯丙烯酸丁酯树脂、抗氧剂、润滑剂继续搅拌混 合；
步骤3：将步骤2得到的混合料，采用双螺杆挤出机熔融挤出造粒；
步骤4：将步骤3得到的粒料加热至T温度，与交联剂混合，然后保温t时间后即可得到所需高压电缆半导电屏蔽料。
进一步的，所述步骤4中加热温度T为60～65℃。
进一步的，所述步骤4中保温时间为8～12h。
本发明的有益效果是：
(1)本发明采用聚乙烯吡咯烷酮作为分散剂，克服了将普通导电炭黑填充高压电缆半导电屏蔽料容易团聚，半导电屏蔽料的导电性能和加工性能劣化，高压电缆半导电屏蔽料表面不光滑，凸起点多的问题；
(2)本发明将抗氧剂1010和抗氧剂168一起复配使用，在加工过程中主要为抗氧剂168起主要作用，在材料老化过程中抗氧剂1010起主要作用。两种抗氧剂的加和反应和协同反应能够起到更好的抗氧化效果，使得半导电屏蔽料使用寿命延长。
(3)本发明屏蔽料中选择乙烯丙烯酸丁酯作为基体树脂，与常用的EVA树脂相比热稳定性更优异。
附图说明
图1为实施例1和对比例得到的高压电缆半导电屏蔽料的表面光滑度性能图。
具体实施方式
下面结合附图和具体实施例对本发明做进一步说明。
一种导电炭黑高效分散的高压电缆半导电屏蔽料，按照重量份包括以下组分：基体树脂55～65份、导电炭黑28～35份、分散剂0.5～2.5份和功能助剂4～7份；分散剂为聚乙烯吡咯烷酮。
功能助剂按照重量份包括：偶联剂1～2份、抗氧剂0.5～1份、润滑剂1～2份；抗氧剂为抗氧剂1010和抗氧剂168以任意比例混合构成。基体树脂为乙烯丙烯酸丁酯树脂，在190℃和2.16kg下的熔融指数8～10g/min，断裂强度>12Mpa。润滑剂为硬脂酸锌和聚乙烯腊中的一种或两种以任意比例混合构成。交联剂为过氧化物类引发剂，优选为双叔丁基过氧化异丙基苯。导电炭黑为美国卡博特产的VXC72、VXC500中的任一种。
导电炭黑高效分散的高压电缆半导电屏蔽料的制备方法，包括以下步骤：
步骤1：称取各原料组分，将分散剂、偶联剂和导电炭黑搅拌混合，得到导电炭黑预处理物；
步骤2：在导电炭黑预处理物中加入乙烯丙烯酸丁酯树脂、抗氧剂、润滑剂继续搅拌混 合；
步骤3：将步骤2得到的混合料，采用双螺杆挤出机熔融挤出造粒；
步骤4：将步骤3得到的粒料放入加热器中加热至60～65℃，与交联剂混合，然后继续在加热器中保温8～12h，使预混料对交联剂充分吸收，即可得到所需高压电缆半导电屏蔽料。
为了进一步提高导电炭黑的分散性，可以对导电炭黑进行预处理，将导电炭黑、乙二醇超声混合后，将得到的悬浮液在150℃加热搅拌7h；过滤，用无水乙醇和蒸馏水分别进行洗涤3次，经60℃真空干燥即可得到预处理导电炭黑。其中导电炭黑和乙二醇的质量比为2～5:50。井处理后的导电炭黑可以均匀和稳定的分散在基体树脂中，提高了屏蔽料的稳定性。
实施例1
一种导电炭黑高效分散的高压电缆半导电屏蔽料，按照重量份包括以下组分：乙烯丙烯酸丁酯树脂EBA 58.5份、导电炭黑35份、分散剂2份、交联剂1份、润滑剂1份、抗氧剂0.5份、偶联剂2份；分散剂为聚乙烯吡咯烷酮。
EBA树脂，在190℃和2.16kg下的熔融指数8.7g/min，断裂强度>12Mpa。导电炭黑的DBP吸收值为148ml/100g；偶联剂为硅烷偶联剂KH550；抗氧剂为抗氧剂1010和抗氧剂168的混合物，抗氧剂1010和抗氧剂168的质量比为2:1；润滑剂为硬脂酸锌和季戊四醇构成的混合物，硬脂酸锌和季戊四醇的质量比为1:1。
按照以下方法制备导电炭黑高效分散的高压电缆半导电屏蔽料，
步骤1：按照配比称取各组分，将分散剂、偶联剂和导电炭黑放入混合器中进行搅拌混合得到导电炭黑预处理物；
步骤2：将步骤1得到的导电炭黑预处理物中加入乙烯丙烯酸丁酯树脂、抗氧剂和润滑剂并继续搅拌混合；
步骤3：将混合料加入到双螺杆挤出机中进行熔融挤出造粒；
步骤4：将得到的粒料放入加热器中加热至60～65℃，随后与交联剂快速混合均匀，继续在加热器中放置8～12h，使预混料对交联剂充分吸收，最后得到所需高压电缆半导电屏蔽料。
实施例2
一种导电炭黑高效分散的高压电缆半导电屏蔽料，按照重量份包括以下组分：乙烯丙烯酸丁酯树脂EBA 59.5份、导电炭黑35份、分散剂1份、交联剂1份、润滑剂1份、抗氧剂0.5份、偶联剂2份；分散剂为聚乙烯吡咯烷酮。
EBA树脂，在190℃和2.16kg下的熔融指数8.7g/min，断裂强度>12Mpa。导电炭黑的DBP吸收值为148ml/100g；偶联剂为硅烷偶联剂KH550；抗氧剂为抗氧剂1010和抗氧剂 168的混合物，抗氧剂1010和抗氧剂168的质量比为2:1；润滑剂为硬脂酸锌和季戊四醇构成的混合物，硬脂酸锌和季戊四醇的质量比为1:1。
制备方法如实施例1。
实施例3
一种导电炭黑高效分散的高压电缆半导电屏蔽料，按照重量份包括以下组分：乙烯丙烯酸丁酯树脂EBA 60份、导电炭黑35份、分散剂0.5份、交联剂1份、润滑剂1份、抗氧剂0.5份、偶联剂2份；分散剂为聚乙烯吡咯烷酮。
EBA树脂，在190℃和2.16kg下的熔融指数8.7g/min，断裂强度>12Mpa。导电炭黑的DBP吸收值为148ml/100g；偶联剂为硅烷偶联剂KH550；抗氧剂为抗氧剂1010和抗氧剂168的混合物，抗氧剂1010和抗氧剂168的质量比为2:1；润滑剂为硬脂酸锌和季戊四醇构成的混合物，硬脂酸锌和季戊四醇的质量比为1:1。
制备方法如实施例1。
为了说明本发明有益效果设置对比例。
对比例1
高压电缆半导电屏蔽料，按照重量份包括以下组分：乙烯丙烯酸丁酯树脂EBA 58.5份、导电炭黑35份、分散剂2份、交联剂1份、润滑剂1份、抗氧剂0.5份、偶联剂2份；分散剂为乙撑双硬脂酸酰胺。
EBA树脂，在190℃和2.16kg下的熔融指数8.7g/min，断裂强度>12Mpa。导电炭黑的DBP吸收值为148ml/100g；偶联剂为硅烷偶联剂KH550；抗氧剂为抗氧剂1010和抗氧剂168的混合物，抗氧剂1010和抗氧剂168的质量比为2:1；润滑剂为硬脂酸锌和季戊四醇构成的混合物，硬脂酸锌和季戊四醇的质量比为1:1。
制备方法如实施例1。
对比例2
高压电缆半导电屏蔽料，按照重量份包括以下组分：乙烯丙烯酸丁酯树脂EBA 58.5份、导电炭黑35份、分散剂2份、交联剂1份、润滑剂1份、抗氧剂0.5份、偶联剂2份；分散剂为季戊四醇硬脂酸脂。
EBA树脂，在190℃和2.16kg下的熔融指数8.7g/min，断裂强度>12Mpa。导电炭黑的DBP吸收值为148ml/100g；偶联剂为硅烷偶联剂KH550；抗氧剂为抗氧剂1010和抗氧剂168的混合物，抗氧剂1010和抗氧剂168的质量比为2:1；润滑剂为硬脂酸锌和季戊四醇构成的混合物，硬脂酸锌和季戊四醇的质量比为1:1。
制备方法如实施例1。
对比例3
高压电缆半导电屏蔽料，按照重量份包括以下组分：乙烯丙烯酸丁酯树脂EBA 58.5份、导电炭黑35份、交联剂1份、润滑剂1份、抗氧剂0.5份、偶联剂2份。
EBA树脂，在190℃和2.16kg下的熔融指数8.7g/min，断裂强度>12Mpa。导电炭黑的DBP吸收值为148ml/100g；偶联剂为硅烷偶联剂KH550；抗氧剂为抗氧剂1010和抗氧剂168的混合物，抗氧剂1010和抗氧剂168的质量比为2:1；润滑剂为硬脂酸锌和季戊四醇构成的混合物，硬脂酸锌和季戊四醇的质量比为1:1。
制备方法如实施例1。
图1为实施例1和对比例1得到的高压电缆半导电屏蔽料的表面光滑度性能图。从图中可以看出，实施例1得到的高压电缆半导电屏蔽料的表面光滑。对比例1得到的高压电缆半导电屏蔽料的表面具有明显的凸起点，且尺寸更大，表面不光滑。
对实施例和对比例得到的高压电缆半导电屏蔽料进行物理机械性能及电性能测试，结果如表1所示。
表1.高压电缆半导电屏蔽料的物理机械性能及电性能
Figure PCTCN2021130245-appb-000001
从表1可以看出，分散剂PVP含量为1份时，屏蔽料的力学性能和电性能最优。这是因为在更低PVP含量时，难以充分抑制导电炭黑的团聚；而在更高含量时，其自身绝缘性能又影响屏蔽料的电性能。此外，从对比例1-3看出，相比于乙撑双硬脂酸酰胺和季戊四醇硬脂酸脂，PVP具有更加的分散效果，这是因为PVP分子链与导电炭黑表面含氧官能团形成氢键，具有更好的键合作用，减少或削弱导电炭黑之间的团聚作用。
分散剂绝大多数都是脂肪酸的衍生物，一端为极性部分，另一端为非极性部分，其主要功能为分散。能改善固体胶料配方的分散度，有利于配合剂的混入，减少混合时间，并对随后加工有正面影响。分散剂还具有独特的浸润特性，它可以促进炭黑等填料的快速混入及分散，提高胶料的内、外部润滑性，改善加工性能和制品的表面光洁度。采用聚乙烯吡咯烷酮作为分散剂，导电炭黑分散性能更为优异，得到的高压电缆半导电屏蔽料的力学性能和电学性能更为优异，并且表面光洁度更高，毛刺或突起物更少。屏蔽料在加工过程中加入分散剂，使胶料流动性增大，从而导电炭黑周围被非极性基团保护起来，细化后的导电炭黑粒子被橡胶充分润湿与包封后，稳定下来而不再附聚。
本发明通过基体树脂、分散剂、抗氧剂三者种类的选择和各组分剂量配比的协同效应，实现了半导电屏蔽料表面光滑、导电炭黑均匀分散于基体树脂中。并且得到的半导电屏蔽料具有优异的机械性能和电性能。

Claims (8)

  1. 一种导电炭黑高效分散的高压电缆半导电屏蔽料，其特征在于，按照重量份包括以下组分：基体树脂55～65份、导电炭黑28～35份、分散剂0.5～2.5份和功能助剂4～7份；分散剂为聚乙烯吡咯烷酮。
  2. 根据权利要求1所述的一种导电炭黑高效分散的高压电缆半导电屏蔽料，其特征在于，所述功能助剂按照重量份包括：偶联剂1～2份、抗氧剂0.5～1份、润滑剂1～2份；抗氧剂为抗氧剂1010和抗氧剂168以任意比例混合构成。
  3. 根据权利要求1所述的一种导电炭黑高效分散的高压电缆半导电屏蔽料，其特征在于，所述基体树脂为乙烯丙烯酸丁酯树脂。
  4. 根据权利要求2所述的一种导电炭黑高效分散的高压电缆半导电屏蔽料，其特征在于，所述润滑剂为硬脂酸锌和聚乙烯腊中的一种或两种以任意比例混合构成。
  5. 根据权利要求2所述的一种导电炭黑高效分散的高压电缆半导电屏蔽料，其特征在于，所述交联剂为过氧化物类引发剂，优选为双叔丁基过氧化异丙基苯。
  6. 如权利要求2所述导电炭黑高效分散的高压电缆半导电屏蔽料的制备方法，其特征在于，包括以下步骤：
    步骤1：称取各原料组分，将分散剂、偶联剂和导电炭黑搅拌混合，得到导电炭黑预处理物；
    步骤2：在导电炭黑预处理物中加入乙烯丙烯酸丁酯树脂、抗氧剂、润滑剂继续搅拌混合；
    步骤3：将步骤2得到的混合料，采用双螺杆挤出机熔融挤出造粒；
    步骤4：将步骤3得到的粒料加热至T温度，与交联剂混合，然后保温t时间后即可得到所需高压电缆半导电屏蔽料。
  7. 根据权利要求6所述导电炭黑高效分散的高压电缆半导电屏蔽料的制备方法，其特征在于，所述步骤4中加热温度T为60～65℃。
  8. 根据权利要求6所述的导电炭黑高效分散的高压电缆半导电屏蔽料的制备方法，其特征在于，所述步骤4中保温时间为8～12h。
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