CN106750640A - 一种高耐磨的丁腈橡胶复合电缆料及其制备方法 - Google Patents
一种高耐磨的丁腈橡胶复合电缆料及其制备方法 Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 18
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 13
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 10
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- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical class C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
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- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
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- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
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- KOVKEDGZABFDPF-UHFFFAOYSA-N n-(triethoxysilylmethyl)aniline Chemical compound CCO[Si](OCC)(OCC)CNC1=CC=CC=C1 KOVKEDGZABFDPF-UHFFFAOYSA-N 0.000 description 1
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
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- QQVIHTHCMHWDBS-UHFFFAOYSA-N perisophthalic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
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- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
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Abstract
本发明提供一种高耐磨的丁腈橡胶复合电缆料，由下列重量份数的组分制成：丁腈橡胶100份，促进剂4～5份，抗氧剂2～2.5份，阻燃剂8～13份，填料10～15份，偶联剂1.5～2份，增塑剂5～10份，硫化剂1～1.5份，防老剂2.5～3份，改性复合氧化锆6～8份，氧化锌4份，硬脂酸2份。本发明还提供了该丁腈橡胶复合电缆料的制备方法。本发明提供的丁腈橡胶复合电缆料的耐磨性能非常强。
Description
技术领域
本发明涉及一种电缆料，特别是涉及一种高耐磨的丁腈橡胶复合电缆料及其制备方法。
背景技术
丁腈橡胶由丁二烯和丙烯腈聚合而成，按用途分通用丁腈橡胶和特种丁腈橡胶。丁腈橡胶具有以下特性：
1、具有优异的耐油性和耐溶剂性，丙烯腈含量越高，其耐油性越好
2、物理机械性能一般
3、耐热性能较好
4、耐水性较好，透气性较小
5、能和其他橡胶或塑料混合使用，改进橡皮的性能。
丁腈橡胶可单独或与聚氯乙烯塑料混合做耐油电绝缘护套，如电机引出线、油矿用电缆、船用电缆护套等。
例如，公开号为CN103524809A、公开日为2014.01.22、申请人为安徽文峰电子科技集团有限公司的中国专利申请公开了“一种具备优良力学性能的改性丁腈橡胶电缆料”，该电缆料包含以下重量份的原料：丁腈橡胶(LG6250)30-34，氟橡胶4-7，氯丁橡胶(CR121)20-24，聚异丁烯4-5，茂金属线性低密度聚乙烯12-15，N339炭黑12-15，N660炭黑14-18，纳米碳酸钙14-17，硫酸钡粉10-12，滑石粉3-4，苯甲酸1-2，间苯二甲酸酯5-8，白炭黑25-35，硫磺2-3，氧化镁2-3，苯胺甲基三乙氧基硅烷2-3，防焦剂CTP1-2，促进剂CZ1-2，助剂4-5；该电缆料结合了丁腈橡胶、氟橡胶、氯丁橡胶以及茂金属线性低密度聚乙烯等原料的优点，提升了传统丁腈橡胶电缆料的性能，使其具备优良的力学性能，具有高强度、高韧性、抗拉伸等特性，能够满足特定场合的使用要求，且对环境和人体无危害，应用前景广阔。然而，该改性丁腈橡胶电缆料仍然存在耐磨性能较差的缺陷，使用时容易受到磨损。
发明内容
本发明要解决的技术问题是提供一种高耐磨的丁腈橡胶复合电缆料，其耐磨性能非常强。
为解决上述技术问题，本发明的技术方案是：
一种高耐磨的丁腈橡胶复合电缆料，由下列重量份数的组分制成：丁腈橡胶100份，促进剂4～5份，抗氧剂2～2.5份，阻燃剂8～13份，填料10～15份，偶联剂1.5～2份，增塑剂5～10份，硫化剂1～1.5份，防老剂2.5～3份，改性复合氧化锆6～8份，氧化锌4份，硬脂酸2份。
优选地，本发明所述促进剂为促进剂M。
优选地，本发明所述抗氧剂为抗氧剂1068。
优选地，本发明所述阻燃剂为三氧化二锑。
优选地，本发明所述填料为白炭黑。
优选地，本发明所述偶联剂为偶联剂A151。
优选地，本发明所述增塑剂为己二酸二辛酯。
优选地，本发明所述硫化剂为硫磺。
优选地，本发明所述防老剂为防老剂ODA。
本发明要解决的另一技术问题是提供上述高耐磨的丁腈橡胶复合电缆料的制备方法。
为解决上述技术问题，技术方案是：
一种高耐磨的丁腈橡胶复合电缆料的制备方法，包括下列步骤：
(1)将六水合硝酸铈加入到三水合硝酸锆中，搅拌至混合均匀后加入柠檬酸，搅拌30分钟加热至60℃，继续搅拌5小时后静置1小时，置于烘箱中烘干，转入高温炉中升温至900℃后煅烧5小时，研磨后过100目筛得到复合氧化锆，其中，六水合硝酸铈、三水合硝酸锆、柠檬酸的摩尔比为1:8:3；
(2)将复合氧化锆均匀地铺展于培养皿内，将培养皿放入等离子处理器中，抽真空至9Pa后用氧气洗气3次，通入氧气至压力达到25Pa后打开射频电源，调节功率至100W后等离子处理5分钟后取出，烘干后得到预处理复合氧化锆；
(3)将全氟壬烯氧基苯磺酸钠加入20倍重量的去离子水中，搅拌均匀后得到改性溶液，将改性溶液用针筒注射器均匀地喷洒于预处理复合氧化锆上，然后置于粉碎机中搅拌5分钟，100℃下真空烘干，研磨后过100目筛得到改性复合氧化锆，其中，全氟壬烯氧基苯磺酸钠的重量为预处理氧化锆重量的1％；
(4)按重量份数称取各组分，将丁腈橡胶、增塑剂加入密炼机中，塑炼至密炼机温度达到135℃时出料得到胶料一，待胶料一冷却至室温后再送入密炼机中，并加入其他组分，混炼20分钟后出料得到胶料二，将胶料二冷却至室温后送入开炼机中开炼，薄通7次后得到高耐磨的丁腈橡胶复合电缆料。
与现有技术相比，本发明具有以下有益效果：
氧化锆是锆的主要氧化物，硬度极高，耐磨性优异，不过氧化锆的韧性一般，热稳定性也不太好，所以本发明使用六水合硝酸铈与三水合硝酸锆进行复合制得了掺杂有氧化铈的复合氧化锆，氧化铈有效改善了氧化锆的韧性和热稳定性，不过复合氧化锆呈亲水性、活性较低，与丁腈橡胶之间的相容性不佳，因而本发明先使用等离子处理器对复合氧化锆进行等离子处理，在其表面产生了很多活性基团得到预处理氧化锆，然后通过全氟壬烯氧基苯磺酸钠(简称OBS)对预处理氧化锆进行表面改性处理得到改性复合氧化锆，OBS是一种氟表面活性剂，与预处理氧化锆表面的活性基团产生了化学反应，从而在预处理氧化锆表面形成了有机包覆，将其表面的亲水性变成了疏水性，进而改善了其与丁腈橡胶之间的相容性，与丁腈橡胶混合后改性复合氧化锆可充分发挥其耐磨性能，从而大幅提高电缆料的耐磨性能；此外，氧化锆的耐火性很强，因此改性复合氧化锆能与电缆料中的阻燃剂形成协同增效，从而进一步提高电缆料的阻燃性能。
具体实施方式
下面将结合具体实施例来详细说明本发明，在此本发明的示意性实施例以及说明用来解释本发明，但并不作为对本发明的限定。
实施例1
高耐磨的丁腈橡胶复合电缆料，由下列重量份数的组分制成：丁腈橡胶100份，促进剂M 4份，抗氧剂1068 2.5份，三氧化二锑12份，白炭黑11份，偶联剂A151 1.3份，己二酸二辛酯8份，硫磺1.1份，防老剂ODA 2.5份，改性复合氧化锆8份，氧化锌4份，硬脂酸2份。
该丁腈橡胶复合电缆料的制备方法包括下列步骤：
(1)将六水合硝酸铈加入到三水合硝酸锆中，搅拌至混合均匀后加入柠檬酸，搅拌30分钟加热至60℃，继续搅拌5小时后静置1小时，置于烘箱中烘干，转入高温炉中升温至900℃后煅烧5小时，研磨后过100目筛得到复合氧化锆，其中，六水合硝酸铈、三水合硝酸锆、柠檬酸的摩尔比为1:8:3；
(2)将复合氧化锆均匀地铺展于培养皿内，将培养皿放入等离子处理器中，抽真空至9Pa后用氧气洗气3次，通入氧气至压力达到25Pa后打开射频电源，调节功率至100W后等离子处理5分钟后取出，烘干后得到预处理复合氧化锆；
(3)将全氟壬烯氧基苯磺酸钠加入20倍重量的去离子水中，搅拌均匀后得到改性溶液，将改性溶液用针筒注射器均匀地喷洒于预处理复合氧化锆上，然后置于粉碎机中搅拌5分钟，100℃下真空烘干，研磨后过100目筛得到改性复合氧化锆，其中，全氟壬烯氧基苯磺酸钠的重量为预处理氧化锆重量的1％；
(4)按重量份数称取各组分，将丁腈橡胶、己二酸二辛酯加入密炼机中，塑炼至密炼机温度达到135℃时出料得到胶料一，待胶料一冷却至室温后再送入密炼机中，并加入其他组分，混炼20分钟后出料得到胶料二，将胶料二冷却至室温后送入开炼机中开炼，薄通7次后得到高耐磨的丁腈橡胶复合电缆料。
实施例2
高耐磨的丁腈橡胶复合电缆料，由下列重量份数的组分制成：丁腈橡胶100份，促进剂M 4.4份，抗氧剂1068 2.3份，三氧化二锑10份，白炭黑13份，偶联剂A151 1.5份，己二酸二辛酯10份，硫磺1.3份，防老剂ODA 2.7份，改性复合氧化锆7份，氧化锌4份，硬脂酸2份。
该丁腈橡胶复合电缆料的制备方法与实施例1相同。
实施例3
高耐磨的丁腈橡胶复合电缆料，由下列重量份数的组分制成：丁腈橡胶100份，促进剂M 4.2份，抗氧剂1068 2.1份，三氧化二锑8份，白炭黑15份，偶联剂A151 1.1份，己二酸二辛酯6份，硫磺1.5份，防老剂ODA 2.9份，改性复合氧化锆7.5份，氧化锌4份，硬脂酸2份。
该丁腈橡胶复合电缆料的制备方法与实施例1相同。
实施例4
高耐磨的丁腈橡胶复合电缆料，由下列重量份数的组分制成：丁腈橡胶100份，促进剂M 4.8份，抗氧剂1068 2.4份，三氧化二锑13份，白炭黑10份，偶联剂A151 1.8份，己二酸二辛酯9份，硫磺1.4份，防老剂ODA 3份，改性复合氧化锆6份，氧化锌4份，硬脂酸2份。
该丁腈橡胶复合电缆料的制备方法与实施例1相同。
实施例5
高耐磨的丁腈橡胶复合电缆料，由下列重量份数的组分制成：丁腈橡胶100份，促进剂M 4.5份，抗氧剂1068 2.2份，三氧化二锑11份，白炭黑12份，偶联剂A151 2份，己二酸二辛酯5份，硫磺1.2份，防老剂ODA 2.8份，改性复合氧化锆6.5份，氧化锌4份，硬脂酸2份。
该丁腈橡胶复合电缆料的制备方法与实施例1相同。
实施例6
高耐磨的丁腈橡胶复合电缆料，由下列重量份数的组分制成：丁腈橡胶100份，促进剂M 5份，抗氧剂1068 2份，三氧化二锑9份，白炭黑14份，偶联剂A151 1.6份，己二酸二辛酯7份，硫磺1份，防老剂ODA 2.6份，改性复合氧化锆6.4份，氧化锌4份，硬脂酸2份。
该丁腈橡胶复合电缆料的制备方法与实施例1相同。
对实施例1-6以及对比例的耐磨性能进行测试，其中，对比例为公开号为CN103524809A的中国专利申请，耐磨性能使用磨损试验机测试出各待测物的质量磨损率，该数值越小表示耐磨性能越强。测试结果见下表：
由上表可看出，实施例1-6的质量磨损率均低于对比例很多，表示具有非常强的耐磨性能。
上述实施例仅例示性说明本发明的原理及其功效，而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下，对上述实施例进行修饰或改变。因此，举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利要求所涵盖。
Claims (10)
1.一种高耐磨的丁腈橡胶复合电缆料，其特征在于，由下列重量份数的组分制成：丁腈橡胶100份，促进剂4～5份，抗氧剂2～2.5份，阻燃剂8～13份，填料10～15份，偶联剂1.5～2份，增塑剂5～10份，硫化剂1～1.5份，防老剂2.5～3份，改性复合氧化锆6～8份，氧化锌4份，硬脂酸2份。
2.根据权利要求1所述的一种高耐磨的丁腈橡胶复合电缆料，其特征在于：所述促进剂为促进剂M。
3.根据权利要求2所述的一种高耐磨的丁腈橡胶复合电缆料，其特征在于：所述抗氧剂为抗氧剂1068。
4.根据权利要求3所述的一种高耐磨的丁腈橡胶复合电缆料，其特征在于：所述阻燃剂为三氧化二锑。
5.根据权利要求4所述的一种高耐磨的丁腈橡胶复合电缆料，其特征在于：所述填料为白炭黑。
6.根据权利要求5所述的一种高耐磨的丁腈橡胶复合电缆料，其特征在于：所述偶联剂为偶联剂A151。
7.根据权利要求6所述的一种高耐磨的丁腈橡胶复合电缆料，其特征在于：所述增塑剂为己二酸二辛酯。
8.根据权利要求7所述的一种高耐磨的丁腈橡胶复合电缆料，其特征在于：所述硫化剂为硫磺。
9.根据权利要求8所述的一种高耐磨的丁腈橡胶复合电缆料，其特征在于：所述防老剂为防老剂ODA。
10.根据权利要求1～9任意一项所述的一种高耐磨的丁腈橡胶复合电缆料的制备方法，其特征在于，包括下列步骤：
(1)将六水合硝酸铈加入到三水合硝酸锆中，搅拌至混合均匀后加入柠檬酸，搅拌30分钟加热至60℃，继续搅拌5小时后静置1小时，置于烘箱中烘干，转入高温炉中升温至900℃后煅烧5小时，研磨后过100目筛得到复合氧化锆，其中，六水合硝酸铈、三水合硝酸锆、柠檬酸的摩尔比为1:8:3；
(2)将复合氧化锆均匀地铺展于培养皿内，将培养皿放入等离子处理器中，抽真空至9Pa后用氧气洗气3次，通入氧气至压力达到25Pa后打开射频电源，调节功率至100W后等离子处理5分钟后取出，烘干后得到预处理复合氧化锆；
(3)将全氟壬烯氧基苯磺酸钠加入20倍重量的去离子水中，搅拌均匀后得到改性溶液，将改性溶液用针筒注射器均匀地喷洒于预处理复合氧化锆上，然后置于粉碎机中搅拌5分钟，100℃下真空烘干，研磨后过100目筛得到改性复合氧化锆，其中，全氟壬烯氧基苯磺酸钠的重量为预处理氧化锆重量的1％；
(4)按重量份数称取各组分，将丁腈橡胶、增塑剂加入密炼机中，塑炼至密炼机温度达到135℃时出料得到胶料一，待胶料一冷却至室温后再送入密炼机中，并加入其他组分，混炼20分钟后出料得到胶料二，将胶料二冷却至室温后送入开炼机中开炼，薄通7次后得到高耐磨的丁腈橡胶复合电缆料。
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