CN110437379A - 一种紫外光交联耐刮擦耐低温无卤阻燃绝缘料及其制备方法 - Google Patents
一种紫外光交联耐刮擦耐低温无卤阻燃绝缘料及其制备方法 Download PDFInfo
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Abstract
本发明提供了一种紫外光交联耐刮擦耐低温无卤阻燃绝缘料及其制备方法,涉及电缆绝缘料生产技术领域。本发明采用特定参数的三元乙丙橡胶、煅烧陶土作为基体材料,与硬脂酸、微细滑石粉、甲基丙烯酸锌、碳纳米管混合,并配有抗氧剂、阻燃剂以及光引发剂制备的绝缘料适用于电缆后具有优异的耐刮擦性能、耐低温性好、阻燃性能好、低烟无毒、使用寿命长、不易老化、绝缘性能好的特点。
Description
技术领域
本发明涉及电缆绝缘料生产技术领域,尤其是涉及一种紫外光交联耐刮擦耐低温无卤阻燃绝缘料及其制备方法。
背景技术
电力电缆的表面需要覆盖电缆料,电缆料是构成高压、特高压输变电设备和网路的技术核心与关键,其性能的高低与稳定直接关系到了整个输电网络的电压等级与安全。
电线电缆常因在传输电能中自身发热或外部火灾而引起燃烧。为了改善电线电缆的阻燃性,最初添加含有卤素的阻燃剂,此类电线电缆在燃烧过程中释放出大量的烟雾和卤化氢气体,燃烧时发烟量大,产生大量有害气体。目前,越来越多的高层建筑、大型商场、医院、车站、体育场等公共场合已经大量使用无卤低烟阻燃电缆。目前,市场上的PVC电缆料存在着不耐高温,不耐老化,并且其耐低温性能较差,低温冲击脆化温度在-15℃~-20℃,在低温环境中,电缆料所制成的电缆外护套容易变碎,更易损坏,远远达不到实际运行要求。而且电线电缆在生产、运输及使用的过程中,不可避免的相互产生摩擦或者受到硬物的摩擦,而产生摩擦刮白等现象,对线材的外观产生很大的影响。为了解决上述问题,必须研制一种耐刮擦、耐低温、无卤阻燃用于电缆的绝缘料。
发明内容
本发明目的在于提供一种紫外光交联耐刮擦耐低温无卤阻燃绝缘料及其制备方法,该材料用于电缆后,具有耐低温性能突出、耐刮擦性能优异、阻燃性能良好、低烟无毒、使用寿命长、不易老化的特点。
为实现上述目的,本发明采用的技术方案如下:
一种紫外光交联耐刮擦耐低温无卤阻燃绝缘料,由以下重量份的原料组成:三元乙丙橡胶100-200份、煅烧陶土10-20份、木质素25-50份、硬脂酸1-5份、抗氧剂0.01-1份、微细滑石粉0.5-1.5份、光引发剂0.5-2份、阻燃剂10-20份、甲基丙烯酸锌2-10份、碳纳米管0.1-1份。
进一步,所述的光引发剂由以下重量份数的原料组成:纳米二氧化硅1-1.5份、二氯硫杂蒽酮2-3份、γ-氨丙基三乙氧基硅烷0.1-0.5份、十六烷基三甲基溴化铵0.5-1份。
进一步,所述的抗氧化剂由以下重量份数的原料组成:石榴籽25-30份、2,2-二(2-羟基-5-叔丁基苯基)乙酸2-5份、抗氧剂168 1-3份。
进一步,所述的阻燃剂由以下重量份数的原料组成:片状纳米氢氧化镁1-5份、水滑石2-4份、硼酸锌1-3份、丁香油酚0.5-1份、有机蒙脱土1-2份、氧化镧0.1-0.5份。
进一步,所述的木质素和煅烧陶土的重量比为2.5:1。
进一步,所述的紫外光交联耐刮擦耐低温无卤阻燃绝缘料制备方法,具体操作为:按重量份数,将三元乙丙橡胶、煅烧陶土、硬脂酸、微细滑石粉、阻燃剂以及甲基丙烯酸锌投入温度为130-140℃的密炼机中,待其完全熔融后,再加入光引发剂,抗氧剂、碳纳米管控制温度在140-150℃,进行混炼10-20min,密炼完成后进入双螺杆挤出机,经过挤出造粒冷却后得到A料;然后将A料经过紫外光辐照仪器辐照交联即得;所述的紫外光辐照仪器波长200-400nm、光强400-2000mW·cm-2,辐照时间5-7s。
本发明具有以下有益效果:
1、本发明采用特定参数的三元乙丙橡胶、煅烧陶土作为基体材料,与硬脂酸、微细滑石粉、甲基丙烯酸锌、碳纳米管混合,并配有抗氧剂、阻燃剂以及光引发剂制备的绝缘料适用于电缆后,具有优异的耐刮擦性能、耐低温性好、阻燃性能好、低烟无毒、使用寿命长、不易老化、绝缘性能好的特点。
2、在本发明的技术方案中,加入了煅烧陶土作为了无机填料,与木质素配合形成的木质素/陶土复合物能够明显的提高本发明绝缘料的物理机械性能。木质素与陶土都有一定的补强能力,且木质素与陶土作为复合填料使用时表现出了较强的协效补强作用,由于木质素对陶土的表面修饰,改善了煅烧陶土在三元乙丙橡胶中的分散性能,加之由于木质素可以和三元乙丙橡胶之间形成氢键,可以起到很好的增塑作用,大大的提高了本发明制备的绝缘料的断裂伸长率和拉伸强度。经测定,本发明的绝缘料断裂伸长率可以达到505.6%、拉伸强度达到18MPa。但是当木质素/煅烧陶土重量比大于2.5时,木质素用量过大,则会使得生成的木质素/煅烧陶土在在三元乙丙橡胶中的分散性,增加团聚现象的发生率,进而导致拉伸强度与拉断伸长率下降;当木质素/陶土重量比小于2.5时,煅烧陶土用量过大,则陶土颗粒分散不均匀且部分固体颗粒裸露在外面,且煅烧陶土在三元乙丙橡胶基体中分散不均匀,也同样导致拉伸强度与拉断伸长率下降。
3、与现有加入氢氧化镁作为阻燃剂相比,本发明以片状纳米氢氧化镁为主,再配以协效阻燃剂:水滑石、硼酸锌、丁香油酚、有机蒙脱土、氧化镧制备成本发明的阻燃剂,具有阻燃性能好、低烟无毒的特点。
传统的氢氧化镁分散性差、团聚严重,分解过程会产生对人有害的气体。则片状纳米氢氧化镁分散性好、分解温度高、分解过程中不产生任何有毒气体、热稳定性好、无毒、无烟及抑烟等优点,而且本发明阻燃剂中还加入了有机蒙脱土、氧化镧、丁香油酚和水滑石;有机蒙脱土除了自身能释放出层间结晶水吸热,其多层结构对阻隔空气能起到一定的作用外,还能增加炭层连贯性,降低热释放速率,具有良好的协效阻燃作用;加入的氧化镧一方面由于熔点较高,可以有效地提高绝缘料的高温稳定性,有效减缓制备的绝缘料的降解速率,减少分解产物数量,配合片状纳米氢氧化镁达到增效阻燃的作用,另一方面,改善片状纳米氢氧化镁在绝缘料中的分散性能,使其分布更加均匀;加入的丁香油酚存在于多种植物中,具有低毒和“绿色”等特点,由于其分子中含有酚羟基可以在燃烧时捕获火焰区的自由基从而抑制气相燃烧,同时磷腈结构在燃烧过程中生成聚偏磷酸,可催化片状纳米氢氧化镁脱水形成氧化物隔层隔绝氧气和可燃气体的交换以抑制燃烧,具有良好的协效阻燃作用。经测定,本发明制备的绝缘料烟密度(无焰)可以达到50,烟密度(有焰)可以达到1。
除了上面所描述的目的、特征和优点之外,本发明还有其它的目的、特征和优点。下面将对本发明作进一步详细的说明。
具体实施方式
以下对本发明的实施例进行详细说明,但是本发明可以根据权利要求限定和覆盖的多种不同方式实施。
实施例1
一种紫外光交联耐刮擦耐低温无卤阻燃绝缘料,由以下重量份的原料组成:三元乙丙橡胶100份、煅烧陶土10份、木质素25份、硬脂酸1份、抗氧剂0.01份、微细滑石粉0.5份、光引发剂0.5份、阻燃剂10份、甲基丙烯酸锌2份、碳纳米管0.1份;所述的光引发剂由以下重量份数的原料组成:纳米二氧化硅1份、二氯硫杂蒽酮2份、γ-氨丙基三乙氧基硅烷0.1份、十六烷基三甲基溴化铵0.5份;所述的抗氧化剂由以下重量份数的原料组成:石榴籽25份、2,2-二(2-羟基-5-叔丁基苯基)乙酸2份、抗氧剂168 1份;所述的阻燃剂由以下重量份数的原料组成:片状纳米氢氧化镁1份、水滑石2份、硼酸锌1份、丁香油酚0,5份、有机蒙脱土1份、氧化镧0.1份。
所述的紫外光交联耐刮擦耐低温无卤阻燃绝缘料制备方法,具体操作为:按重量份数,将三元乙丙橡胶、煅烧陶土、硬脂酸、微细滑石粉、阻燃剂以及甲基丙烯酸锌投入温度为130℃的密炼机中,待其完全熔融后,再加入光引发剂,抗氧剂、碳纳米管控制温度在140℃,进行混炼10min,密炼完成后进入双螺杆挤出机,经过挤出造粒冷却后得到A料;然后将A料经过紫外光辐照仪器辐照交联即得;所述的紫外光辐照仪器波长200-400nm、光强400-2000mW·cm-2,辐照时间5s。
实施例2
一种紫外光交联耐刮擦耐低温无卤阻燃绝缘料,由以下重量份的原料组成:三元乙丙橡胶200份、煅烧陶土20份、木质素50份、硬脂酸5份、抗氧剂1份、微细滑石粉1.5份、光引发剂2份、阻燃剂20份、甲基丙烯酸锌10份、碳纳米管1份;所述的光引发剂由以下重量份数的原料组成:纳米二氧化硅1.5份、二氯硫杂蒽酮3份、γ-氨丙基三乙氧基硅烷0.5份、十六烷基三甲基溴化铵1份;所述的抗氧化剂由以下重量份数的原料组成:石榴籽30份、2,2-二(2-羟基-5-叔丁基苯基)乙酸5份、抗氧剂168 3份;所述的阻燃剂由以下重量份数的原料组成:片状纳米氢氧化镁5份、水滑石4份、硼酸锌3份、丁香油酚1份、有机蒙脱土2份、氧化镧0.5份。
所述的紫外光交联耐刮擦耐低温无卤阻燃绝缘料制备方法,具体操作为:按重量份数,将三元乙丙橡胶、煅烧陶土、硬脂酸、微细滑石粉、阻燃剂以及甲基丙烯酸锌投入温度为140℃的密炼机中,待其完全熔融后,再加入光引发剂,抗氧剂、碳纳米管控制温度在150℃,进行混炼20min,密炼完成后进入双螺杆挤出机,经过挤出造粒冷却后得到A料;然后将A料经过紫外光辐照仪器辐照交联即得;所述的紫外光辐照仪器波长200-400nm、光强400-2000mW·cm-2,辐照时间7s。
实施例3
一种紫外光交联耐刮擦耐低温无卤阻燃绝缘料,由以下重量份的原料组成:三元乙丙橡胶150份、煅烧陶土15份、木质素37.5份、硬脂酸3.5份、抗氧剂0.08份、微细滑石粉1份、光引发剂0.12份、阻燃剂15份、甲基丙烯酸锌7份、碳纳米管0.7份;所述的光引发剂由以下重量份数的原料组成:纳米二氧化硅1.3份、二氯硫杂蒽酮2.5份、γ-氨丙基三乙氧基硅烷0.3份、十六烷基三甲基溴化铵0.8份;所述的抗氧化剂由以下重量份数的原料组成:石榴籽27.5份、2,2-二(2-羟基-5-叔丁基苯基)乙酸3.5份、抗氧剂168 2份;所述的阻燃剂由以下重量份数的原料组成:片状纳米氢氧化镁3份、水滑石3份、硼酸锌2份、丁香油酚0.6份、有机蒙脱土1.5份、氧化镧0.3份。
所述的紫外光交联耐刮擦耐低温无卤阻燃绝缘料制备方法,具体操作为:按重量份数,将三元乙丙橡胶、煅烧陶土、硬脂酸、微细滑石粉、阻燃剂以及甲基丙烯酸锌投入温度为135℃的密炼机中,待其完全熔融后,再加入光引发剂,抗氧剂、碳纳米管控制温度在145℃,进行混炼15min,密炼完成后进入双螺杆挤出机,经过挤出造粒冷却后得到A料;然后将A料经过紫外光辐照仪器辐照交联即得;所述的紫外光辐照仪器波长200-400nm、光强400-2000mW·cm-2,辐照时间6s。
试验例
本发明制备的紫外光交联耐刮擦耐低温无卤阻燃绝缘料性能测试
1、拉伸强度按GB/T 1040-2006测试,标准要求:≥10.0。
2、20℃时体积电阻率按GB/T 1410-2006测试,标准要求:≥150。
3、断裂伸长率按GB/T 1040-2006,标准要求:≥1.0×1011。
4、冲击脆化性能(试验温度-50℃),标准要求:通过。
5、烟密度(无焰)标准要求:≤350有焰:标准要求:≤100。
6:按GB/T 32129—2015中5.4进行测试,老化条件为135℃×168h。
具体测试结果见表1
实施例1 | 实施例2 | 实施例3 | |
拉伸强度/MPa | 16.5 | 17.9 | 18 |
20℃时体积电阻率/Ω·m | 5.9×10<sup>12</sup> | 5.5×10<sup>12</sup> | 6.1×10<sup>12</sup> |
断裂伸长率/% | 489.5 | 474.6 | 505.6 |
冲击脆化性能 | 通过 | 通过 | 通过 |
烟密度(无焰) | 70 | 65 | 50 |
烟密度(有焰) | 3 | 3 | 1 |
老化温度℃ | 135 | 135 | 135 |
由表1可知,本发明制备的紫外光交联耐刮擦耐低温无卤阻燃绝缘料具有耐低温性好、阻燃性能好、低烟无毒、不易老化、绝缘性能好等特点。
以上所述仅为本发明的优选实施例而已,并不用于限制本发明,对于本领域的技术人员来说,本发明可以有各种更改和变化。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (4)
1.一种紫外光交联耐刮擦耐低温无卤阻燃绝缘料,其特征在于,由以下重量份的原料组成:三元乙丙橡胶100-200份、煅烧陶土10-20份、木质素25-50份、硬脂酸1-5份、抗氧剂0.01-1份、微细滑石粉0.5-1.5份、光引发剂0.5-2份、阻燃剂10-20份、甲基丙烯酸锌2-10份、碳纳米管0.1-1份;
所述的光引发剂由以下重量份数的原料组成:纳米二氧化硅1-1.5份、二氯硫杂蒽酮2-3份、γ-氨丙基三乙氧基硅烷0.1-0.5份、十六烷基三甲基溴化铵0.5-1份;
所述的抗氧化剂由以下重量份数的原料组成:石榴籽25-30份、2,2-二(2-羟基-5-叔丁基苯基)乙酸2-5份、抗氧剂168 1-3份;
所述的阻燃剂由以下重量份数的原料组成:片状纳米氢氧化镁1-5份、水滑石2-4份、硼酸锌1-3份、丁香油酚0.5-1份、有机蒙脱土1-2份、氧化镧0.1-0.5份。
2.根据权利要求1所述的一种紫外光交联耐刮擦耐低温无卤阻燃绝缘料制备方法,其特征在于,具体操作为:按重量份数,将三元乙丙橡胶、煅烧陶土、硬脂酸、微细滑石粉、阻燃剂以及甲基丙烯酸锌投入温度为130-140℃的密炼机中,待其完全熔融后,再加入光引发剂,抗氧剂、碳纳米管控制温度在140-150℃,进行混炼10-20min,密炼完成后进入双螺杆挤出机,经过挤出造粒冷却后得到A料;然后将A料经过紫外光辐照仪器辐照交联即得;所述的紫外光辐照仪器波长200-400nm、光强400-2000mW·cm-2,辐照时间5-7s。
3.根据权利要求1所述的一种紫外光交联耐刮擦耐低温无卤阻燃绝缘料,其特征在于,所述的木质素和煅烧陶土的重量比为2.5:1。
4.根据权利要求1所述的一种紫外光交联耐刮擦耐低温无卤阻燃绝缘料的用途,用于获得绝缘层或护套层或电缆制品。
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CN110951002A (zh) * | 2019-12-11 | 2020-04-03 | 威海金合思化工有限公司 | 一种高流动性增韧剂及其在工程塑料加工中的应用 |
CN110951002B (zh) * | 2019-12-11 | 2022-04-01 | 威海金合思化工有限公司 | 一种高流动性增韧剂及其在工程塑料加工中的应用 |
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