CN114539785A - 一种聚氨酯改性的橡胶复合材料、制备方法及其在避雷器复合外套中的应用 - Google Patents
一种聚氨酯改性的橡胶复合材料、制备方法及其在避雷器复合外套中的应用 Download PDFInfo
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Abstract
本发明提供一种聚氨酯改性的橡胶复合材料、制备方法及其在避雷器复合外套中的应用。所述聚氨酯改性的橡胶复合材料，包括A组份：甲基乙烯基硅橡胶100份、低密度聚乙烯15～30份、乙烯‑醋酸乙烯酯共聚物7～13份、白炭黑45～50份、聚二甲基硅氧烷8～12份、2,5‑二甲基‑2,5‑二(叔丁基过氧基)己烷2～3份、氢氧化铝100～120份、氧化锌3～4份、硬脂酸4～6份、硅烷偶联剂3～4份；B组份为聚氨酯预聚体：异佛尔酮二异氰酸酯39～40份、聚醚多元醇35～37份、二月桂酸二丁基锡0.01～0.02份、甲基丙烯酸‑2‑羟乙酯23～24份、偶氮二异丁腈0.04～0.06份。该聚氨酯改性的橡胶复合材料，在体积电阻率、外延起始分解温度、拉伸强度和断裂伸长率数据中表现出较好的绝缘性、耐候性和力学性能，适用于避雷器的复合外套。
Description
技术领域
本发明涉及一种聚氨酯改性的橡胶复合材料、制备方法及其在避雷器复合外套中的应用，属于硅橡胶制备技术领域。
背景技术
复合外套避雷器是由硅橡胶复合外套、环氧管、电阻片、内腔填充物和连接金具等组件构成的综合体。复合外套避雷器与瓷外套避雷器相比，具有体积小、重量轻、密封及耐污性能强、以及良好的防爆性能和耐候性等优点，因此复合外套避雷器已广泛应用于电力系统。
现在避雷器的复合外套材料往往因运行年久而出现硬化、脆化，甚至开裂等问题，严重影响复合外套避雷器绝缘性能和力学性能。目前对硅橡胶绝缘子改性的研究很多，主要的是通过硅橡胶共混物改性和添加补强填料改性这两种。共混物改性配合补强填料来改性硅橡胶对性能有很大的改善，如常用硅橡胶和低密度聚乙烯共混来提高了硅橡胶的电性能和力学性能，但此共混需要添加相容剂，相容剂的添加降低了硅橡胶的耐热性。因此，如何得到耐热性、电性能和力学性能良好的复合外套材料，是现阶段的主要研究方向。
发明内容
针对现有技术的不足，本发明的目的是提供一种聚氨酯改性的橡胶复合材料、制备方法及其在避雷器复合外套中的应用。
为了实现上述目的，本发明所采用的技术方案是：
一种聚氨酯改性的橡胶复合材料，包括A组份和B组份，所述A组份与B组份以重量份为300:0.5～14的比例进行混合；
所述A组份包括如下重量份的原料：甲基乙烯基硅橡胶100份、低密度聚乙烯15～30份、乙烯-醋酸乙烯酯共聚物7～13份、白炭黑45～50份、聚二甲基硅氧烷8～12份、2,5-二甲基-2,5-二(叔丁基过氧基)己烷2～3份、氢氧化铝100～120份、氧化锌3～4份、硬脂酸4～6份、硅烷偶联剂3～4份；
所述B组份为聚氨酯预聚体，包括如下重量份的原料：异佛尔酮二异氰酸酯39～40份、聚醚多元醇35～37份、二月桂酸二丁基锡0.01～0.02份、甲基丙烯酸-2-羟乙酯23～24份、偶氮二异丁腈0.04～0.06份。
所述白炭黑为气相法白炭黑。
所述甲基乙烯基硅橡胶的分子量为500000～700000；乙烯基的摩尔分数含量为0.08％。
所述低密度聚乙烯的分子量为100000～500000；密度为0.925g/cm3。
所述聚二甲基硅氧烷是羟基封端的聚二甲基硅氧烷，粘度为40cst。
所述聚醚多元醇为聚乙二醇、聚四氢呋喃或聚氧化丙烯二醇，分子量为1000～10000。
所述的聚氨酯改性的橡胶复合材料的制备方法，包括如下步骤：
(1)按原料组成称取各原料，备用；
(2)先将甲基乙烯基硅橡胶加入开炼机，然后将白炭黑、聚二甲基硅氧烷、硅烷偶联剂、氧化锌、硬脂酸混合均匀后加入到开炼机；混炼温度为125～130℃，混炼时间为8～10min，待塑化均匀后加入低密度聚乙烯、乙烯-醋酸乙烯酯共聚物，继续混炼5～7min，出片，得混炼胶，备用；
(3)在55～58℃下，将混炼胶与聚氨酯预聚体加入开炼机混炼5～7min，然后加入2,5-二甲基-2,5-二(叔丁基过氧基)己烷和氢氧化铝继续混炼8～10min，出片，备用；
(4)在平板硫化机上进行一段硫化，压力为9～10MPa、时间为8～10min、温度为170～175℃；一段硫化结束后继续在平板硫化机上进行二段硫化，硫化温度为180～185℃，时间为45～50min，即得聚氨酯改性的橡胶复合材料。
所述聚氨酯预聚体的制备方法包括如下步骤：
(1)按原料组成称取各原料，备用；
(2)将异佛尔酮二异氰酸酯与聚醚多元醇加入到烧瓶中，将烧瓶放入50～55℃的水浴中并搅拌，待聚醚多元醇溶解后，再加入二月桂酸二丁基锡，搅拌5～30min，得到浑浊的混合液C，备用；
(3)将偶氮二异丁腈加入到甲基丙烯酸-2-羟乙酯中配置成溶液D，备用；
(4)搅拌混合液C，使其维持在浑浊状态，再加入溶液D，继续搅拌20～60min，得聚氨酯预聚体。
所述的聚氨酯改性的橡胶复合材料在避雷器复合外套中的应用。
本发明有益效果：
本发明聚氨酯改性的橡胶复合材料是在硅橡胶与低密度聚乙烯共混的基础上加入少量的自制聚氨酯预聚体得到，使聚氨酯预聚体和硅橡胶形成互穿网络结构。与硅橡胶/低密度聚乙烯共混胶相比，添加了聚氨酯预聚体的共混胶，其相容性增加，耐热性和力学性能增大。
本发明以甲基乙烯基硅橡胶作为基胶；加入低密度聚乙烯与硅橡胶共混来提高复合外套避雷器的聚氨酯改性材料的力学性能；氢氧化铝作为阻燃剂；乙烯-醋酸乙烯酯共聚物作为低密度聚乙烯与硅橡胶共混的相容剂，提高相容性；加入白炭黑提高复合外套避雷器的聚氨酯改性材料的耐热性能、韧性、拉伸强度；羟基封端的聚二甲基硅氧烷作为结构控制剂，控制混炼胶与白炭黑之间的结构化作用，改善硅橡胶加工性能，延长胶料的存放时间；2,5-二甲基-2,5-二(叔丁基过氧基)己烷作为硫化剂，起交联作用；氧化锌作为补强剂；硬脂酸作为硫化促进剂；偶联剂作为表面改性剂，提高加工性能。
本发明原料组成中B组份以异佛尔酮二异氰酸酯、聚醚多元醇、甲基丙烯酸-2-羟乙酯作为反应物；二月桂酸二丁基锡作为催化剂，起催化作用；偶氮二异丁腈作为引发剂，引发聚合。B组份中的原料合成的为聚氨酯预聚体，将合成的聚氨酯预聚体与A组份的硅橡胶共混，使硅橡胶与聚氨酯预聚体形成互穿网络结构，以改善复合外套避雷器材料的耐热性能及力学性能。
本发明的聚氨酯改性的橡胶复合材料，在体积电阻率、外延起始分解温度、拉伸强度和断裂伸长率数据中表现出了较好的绝缘性、耐候性和力学性能，适合用于避雷器的复合外套。
具体实施方式
以下结合实施例对本发明的具体实施方式作进一步详细说明。如无特别说明，实施例中所涉及的仪器设备均为常规仪器设备；涉及试剂均为市售常规试剂；涉及试验方法为常规方法。
本实施例部分原料的性能如下：
甲基乙烯基硅橡胶C2H3[Si(CH3)2O]n[Si(CH3)(C2H3)O]mC2H3：分子量为500000～700000；乙烯基的摩尔分数含量0.08％。
低密度聚乙烯(C2H4)n：分子量为100000～500000；密度为0.925g/cm3；熔体流动速率2.16g/10min。
聚二甲基硅氧烷是羟基封端的聚二甲基硅氧烷：分子式HO-(C2H6OSi)n-H，粘度40cst。
实施例1聚氨酯预聚体的制备
一种聚氨酯预聚体的制备方法，包括如下步骤：
(1)按原料组成称取各原料：按重量份计，异佛尔酮二异氰酸酯39.96份、聚乙二醇-200036份、二月桂酸二丁基锡0.015份、甲基丙烯酸-2-羟乙酯23.40份、偶氮二异丁腈0.05份，备用；
(2)将异佛尔酮二异氰酸酯与聚乙二醇-2000加入到烧瓶中，烧瓶放入50～55℃的水浴中并搅拌，待聚乙二醇-2000溶解后，再加入二月桂酸二丁基锡，搅拌5min，得到浑浊的混合液C，备用；
(3)将偶氮二异丁腈加入到甲基丙烯酸-2-羟乙酯中配置成溶液D，备用；
(4)搅拌混合液C10min，使其维持在浑浊状态，再加入溶液D，继续搅拌30min，得聚氨酯预聚体。
实施例2聚氨酯改性的橡胶复合材料的制备
一种聚氨酯改性的橡胶复合材料，包括A组份和B组份，A组份与B组份以重量份为300:0.6的比例进行混合；所述B组份为聚氨酯预聚体，其原料组成及制备方法同实施例1。
所述A组份包括如下重量份的原料：甲基乙烯基硅橡胶(乙烯基的摩尔分数含量为0.08％)100份、低密度聚乙烯21份、乙烯-醋酸乙烯酯共聚物8份、气相法白炭黑45份、聚二甲基硅氧烷8份、2,5-二甲基-2,5-二(叔丁基过氧基)己烷2.5份、氢氧化铝100份、氧化锌3份、硬脂酸4.5份、硅烷偶联剂A-174 3.5份。
该聚氨酯改性的橡胶复合材料的制备方法，包括如下步骤：
(1)按原料组成称取各原料，备用；
(2)先将甲基乙烯基硅橡胶加入开炼机，然后将白炭黑、聚二甲基硅氧烷、硅烷偶联剂A-174、氧化锌、硬脂酸混合均匀后加入到开炼机；混炼温度为125℃，混炼时间为10min，待塑化均匀后加入低密度聚乙烯、乙烯-醋酸乙烯酯共聚物，继续混炼5min，出片，得混炼胶，备用；
(3)在56℃下，将混炼胶与聚氨酯预聚体加入开炼机混炼5min，然后加入2,5-二甲基-2,5-二(叔丁基过氧基)己烷和氢氧化铝，继续混炼10min，出片，备用；
(4)在平板硫化机上进行一段硫化，压力为10MPa、时间为10min、温度为175℃；一段硫化结束后继续在平板硫化机上进行二段硫化，硫化温度为185℃，时间为45min，即得聚氨酯改性的橡胶复合材料。
实施例3聚氨酯改性的橡胶复合材料的制备
一种聚氨酯改性的橡胶复合材料，包括A组份和B组份，A组份与B组份以重量份为300:1.4的比例进行混合；所述B组份为聚氨酯预聚体，其原料组成及制备方法同实施例1；所述A组份的原料组成及橡胶复合材料的制备方法同实施例2。
实施例4聚氨酯改性的橡胶复合材料的制备
一种聚氨酯改性的橡胶复合材料，包括A组份和B组份，A组份与B组份以重量份为300:4的比例进行混合；所述B组份为聚氨酯预聚体，其原料组成及制备方法同实施例1；所述A组份的原料组成及橡胶复合材料的制备方法同实施例2。
实施例5聚氨酯改性的橡胶复合材料的制备
一种聚氨酯改性的橡胶复合材料，包括A组份和B组份，A组份与B组份以重量份为300:14的比例进行混合；所述B组份为聚氨酯预聚体，其原料组成及制备方法同实施例1；所述A组份的原料组成及橡胶复合材料的制备方法同实施例2。
对比例 橡胶复合材料的制备
一种橡胶复合材料，其原料组成与实施例2相比，不含B组份聚氨酯预聚体，其他各组分与实施例2相同。
该橡胶复合材料的制备方法，包括如下步骤：
(1)按原料组成称取各原料，按重量份计，甲基乙烯基硅橡胶(乙烯基的摩尔分数含量为0.08％)100份、低密度聚乙烯21份、乙烯-醋酸乙烯酯共聚物8份、气相法白炭黑45份、聚二甲基硅氧烷8份、2,5-二甲基-2,5-二(叔丁基过氧基)己烷2.5份、氢氧化铝100份、氧化锌3份、硬脂酸4.5份、硅烷偶联剂A-174 3.5份，备用；
(2)先将甲基乙烯基硅橡胶加入开炼机，然后将白炭黑、聚二甲基硅氧烷、硅烷偶联剂A-174、氧化锌、硬脂酸混合均匀后加入到开炼机；混炼温度为125℃，混炼时间为10min，待塑化均匀后加入低密度聚乙烯、乙烯-醋酸乙烯酯共聚物，接着混炼10min，然后加入2,5-二甲基-2,5-二(叔丁基过氧基)己烷和氢氧化铝，继续混炼10min，出片，备用；
(3)在平板硫化机上进行一段硫化，压力为10MPa、时间为10min、温度为175℃；一段硫化结束后继续在平板硫化机上进行二段硫化，硫化温度为185℃，时间为45min，即得聚氨酯改性的橡胶复合材料。
本发明的产品性能分析
对实施例2-5及对比例所得样品进行性能测定，结果如表1所示。
1、拉伸性能：在电子万能实验机上以200mm/min的速度测定拉伸强度和断裂伸长率，实验温度为室温；
2、疏水性能：在接触角测量仪下进行接触角的测定，测定温度为室温；
3、电气性能：在高阻测试仪下进行体积电阻率的测定，测定温度为室温；
4、相容性：将待测样品拉伸断面进行喷金处理，用场发射扫描电子显微镜观察其断面形态；
5、耐热性：称取待测样品4-6mg，用综合热分析仪，于氮气气氛，升温速率为10℃/min，测试温度范围为室温至850℃下测试。
表1实施例2-5及对比例所得样品的性能测定结果
结合表1可以看出，除了实施例2-5的体积电阻率比对比例有所下降外，拉伸强度、断裂伸长率、外延起始热分解温度都比对比例的高。
实施例2-5的拉伸强度，断裂伸长率和外延起始热分解温度均大于对比例，说明实施例2-5采用聚氨酯预聚体改性后制得的复合材料的强度、韧性和耐热性均得到提高。其中，实施例3的拉伸强度、断裂伸长率均大于实施例2、实施例4和实施例5，综合来看实施例3采用聚氨酯预聚体改性制得的复合材料性能最佳，说明实施例3的聚氨酯预聚体的添加量与复合橡胶共混表现出更好的相容性，与硅橡胶形成了最佳互穿网络结构。
Claims (9)
1.一种聚氨酯改性的橡胶复合材料，其特征在于，包括A组份和B组份，所述A组份与B组份以重量份为300:0.5～14的比例进行混合；
所述A组份包括如下重量份的原料：甲基乙烯基硅橡胶100份、低密度聚乙烯15～30份、乙烯-醋酸乙烯酯共聚物7～13份、白炭黑45～50份、聚二甲基硅氧烷8～12份、2,5-二甲基-2,5-二(叔丁基过氧基)己烷2～3份、氢氧化铝100～120份、氧化锌3～4份、硬脂酸4～6份、硅烷偶联剂3～4份；
所述B组份为聚氨酯预聚体，包括如下重量份的原料：异佛尔酮二异氰酸酯39～40份、聚醚多元醇35～37份、二月桂酸二丁基锡0.01～0.02份、甲基丙烯酸-2-羟乙酯23～24份、偶氮二异丁腈0.04～0.06份。
2.如权利要求1所述的聚氨酯改性的橡胶复合材料，其特征在于，所述白炭黑为气相法白炭黑。
3.如权利要求1所述的聚氨酯改性的橡胶复合材料，其特征在于，所述甲基乙烯基硅橡胶的分子量为500000～700000；乙烯基的摩尔分数含量为0.08％。
4.如权利要求1所述的聚氨酯改性的橡胶复合材料，其特征在于，所述低密度聚乙烯的分子量为100000～500000；密度为0.925g/cm3。
5.如权利要求1所述的聚氨酯改性的橡胶复合材料，其特征在于，所述聚二甲基硅氧烷是羟基封端的聚二甲基硅氧烷，粘度为40cst。
6.如权利要求1所述的聚氨酯改性的橡胶复合材料，其特征在于，所述聚醚多元醇为聚乙二醇、聚四氢呋喃或聚氧化丙烯二醇，分子量为1000～10000。
7.如权利要求1所述的聚氨酯改性的橡胶复合材料的制备方法，其特征在于，包括如下步骤：
(1)按原料组成称取各原料，备用；
(2)先将甲基乙烯基硅橡胶加入开炼机，然后将白炭黑、聚二甲基硅氧烷、硅烷偶联剂、氧化锌、硬脂酸混合均匀后加入到开炼机；混炼温度为125～130℃，混炼时间为8～10min，待塑化均匀后加入低密度聚乙烯、乙烯-醋酸乙烯酯共聚物，继续混炼5～7min，出片，得混炼胶，备用；
(3)在55～58℃下，将混炼胶与聚氨酯预聚体加入开炼机混炼5～7min，然后加入2,5-二甲基-2,5-二(叔丁基过氧基)己烷和氢氧化铝继续混炼8～10min，出片，备用；
(4)在平板硫化机上进行一段硫化，压力为9～10MPa、时间为8～10min、温度为170～175℃；一段硫化结束后继续在平板硫化机上进行二段硫化，硫化温度为180～185℃，时间为45～50min，即得聚氨酯改性的橡胶复合材料。
8.如权利要求7所述的聚氨酯改性的橡胶复合材料的制备方法，其特征在于，所述聚氨酯预聚体的制备方法包括如下步骤：
(1)按原料组成称取各原料，备用；
(2)将异佛尔酮二异氰酸酯与聚醚多元醇加入到烧瓶中，将烧瓶放入50～55℃的水浴中并搅拌，待聚醚多元醇溶解后，再加入二月桂酸二丁基锡，搅拌5～30min，得到浑浊的混合液C，备用；
(3)将偶氮二异丁腈加入到甲基丙烯酸-2-羟乙酯中配置成溶液D，备用；
(4)搅拌混合液C，使其维持在浑浊状态，再加入溶液D，继续搅拌20～60min，得聚氨酯预聚体。
9.如权利要求1所述的聚氨酯改性的橡胶复合材料在避雷器复合外套中的应用。
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