CN111269266B - 含氰基芳醚磷腈型无卤阻燃剂、制备方法及辐照交联电缆绝缘材料中的应用 - Google Patents
含氰基芳醚磷腈型无卤阻燃剂、制备方法及辐照交联电缆绝缘材料中的应用 Download PDFInfo
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Abstract
本发明提供了一种含氰基芳醚磷腈型无卤阻燃剂、制备方法及在辐照交联电线电缆中的应用。制备方法是以六氯环三磷腈为原料，采用一步法进行亲核取代反应，制备的含氰基芳醚磷腈型无卤阻燃剂中的磷、氮含量以及阻燃性能均有显著提高。将含氰基芳醚磷腈型无卤阻燃剂、无机氢氧化物以及聚乙烯复合可获得无卤阻燃复合材料，复合材料经高能电子束辐照后，复合材料内部形成了交联网络，有效提高了复合材料的力学性能及抗老化性能。本发明的无卤阻燃剂有效解决了传统阻燃电缆由于过多添加无机填料导致材料力学性能较差、易老化等问题。
Description
技术领域
本发明属于阻燃材料领域，具体涉及一种含氰基芳醚磷腈型无卤阻燃剂、制备方法及在辐照交联电线电缆绝缘材料中的应用。
背景技术
聚乙烯是结晶热塑性树脂，聚乙烯可采用一般热塑性材料的成型方法加工。用途十分广泛，可用来制造薄膜、管道、单丝、电线电缆、日用品等。然而聚乙烯阻燃性能较差，易燃烧，极限氧指数(LOI)仅为17.3，遇火燃烧时发热量高、燃烧速度快、并伴有发烟、滴落等现象,限制了它在许多领域的应用。通过向聚乙烯中添加阻燃剂可提高其阻燃性能,市售电缆属于经过添加阻燃剂改性后的聚乙烯电缆材料。目前大规模工业应用聚乙烯阻燃剂主要为卤系阻燃剂,其中包括十溴联苯醚、四溴邻苯二甲酸酐、六氯环戊二烯等,添加到聚乙烯材料中可以起到优异的阻燃效果。但是,卤系阻燃体系在燃烧时会产生大量有毒气体,对环境及人身安全产生巨大威胁。近年来,随着对低毒、环境友好型阻燃剂需求的进一步扩大,越来越多国家已经限制了卤系阻燃剂的开发及应用。无卤型阻燃剂的开发和研制势在必行,且市场前景应用十分广阔。
目前大部分阻燃电缆是通过掺杂无机填料的方式达到阻燃效果，无机氢氧化物具有价格低廉，阻燃效果好的优点，但要想达到较好的阻燃效果，需要掺入大量无机阻燃剂，由于无机填料与基体复合性较差，导致复合材料力学性能较差，因此，改善无机填料在基体中的分散性是十分必要的。
目前磷系阻燃剂和氮系阻燃剂是比较常见的阻燃剂。磷系阻燃剂阻燃机理主要依托于磷元素在燃烧时生成聚偏磷酸，具有较强的化学稳定性，其存在会起到物理保护与隔离氧气的作用。同时聚偏磷酸具有较强的脱水性，可以有助于复合材料碳层的形成，因此对于磷系阻燃剂而言，其阻燃机理主要是依靠固相阻燃机理。
与磷系阻燃机理相似，氮系阻燃剂机理主要依托于氮元素的存在。只不过当氮元素在燃烧过程中会生成氮气以及氮的氧化物等气体，这将会稀释燃烧物上方氧气的含量，从而降低氧气浓度，达到阻燃的效果。因此，对于氮系阻燃剂而言，其阻燃机理主要是依靠气相阻燃。因此合成具有磷、氮元素的无卤阻燃剂是阻燃材料领域亟需解决的技术问题。
发明内容
为解决上述问题，本发明提供了一种含氰基芳醚磷腈型无卤阻燃剂，是以六氯环三磷腈为原料，采用一步亲核取代反应制备方法获得的，其是由高含量磷、氮构成的协同体系,具有较好的阻燃性能,其分子链端含有大量极性氰基基团，可以与无机填料形成强的相互作用，并会与金属离子形成络合物，因此对无机阻燃剂有着极好的粘结性，最终较好地与无机粒子复合，从而提升复合材料体系的均一性、力学性能及阻燃性能。将含氰基芳醚磷腈型无卤阻燃剂、无机氢氧化物以及聚乙烯进行复合，再通过高能电子束辐照交联方法提高了电缆绝缘材料的力学性能、使用温度、寿命和阻燃性能。
本发明提供的技术方案如下：
1.一种含氰基芳醚磷腈型无卤阻燃剂，为结构式1所示的化合物：
结构式1。
2.一种含氰基芳醚磷腈型无卤阻燃剂的制备方法，包括如下步骤：
(1)按照摩尔比48～72:1的比例称取4-羟基苯甲腈和六氯环三磷腈，将4-羟基苯甲腈和丙酮溶液混合，在室温条件下搅拌至4-羟基苯甲腈完全溶解后加入催化剂，在氮气气氛下加热回流4～12h获得4-羟基苯甲腈溶液，加热温度为50～100℃；
(2)将六氯环三磷腈溶于丙酮溶液中获得六氯环三磷腈溶液，将六氯环三磷腈溶液加入步骤(1)获得的4-羟基苯甲腈溶液，反应6～10h后获得白色沉淀物；
(3)将步骤(2)获得的白色沉淀物分别用去离子水和丙酮重复洗涤3～6次后，获得白色粉末状产物，再将白色粉末状产物在60～120℃干燥5～12h,获得含氰基芳醚磷腈型无卤阻燃剂；
优选地，步骤(1)所述催化剂为碳酸钾；
优选地，步骤(1)所述的加热温度为50～80℃。
3.含氰基芳醚磷腈型无卤阻燃剂在聚乙烯复合阻燃电缆绝缘材料的应用，所述应用的具体方法如下：
(1)按照重量份数计算，将含氰基芳醚磷腈型无卤阻燃剂100～10份、聚乙烯100～10份、增韧剂40～4份和无机复配阻燃填料100～10份混合加入双辊开炼机中熔融塑化后，再放入热压机中模压成型，获得了含氰基芳醚磷腈型无卤阻燃剂型聚乙烯复合电缆绝缘材料；
(2)将步骤(1)获得的含氰基芳醚磷腈型无卤阻燃剂型聚乙烯复合电缆绝缘材料进行高能电子束辐照交联，辐照剂量为100～300kGy，获得聚乙烯复合阻燃电缆绝缘材料；
优选地，步骤(1)所述的聚乙烯为高密度聚乙烯、低密度聚乙烯、线型低密度聚乙烯中的任一一种；
优选地，步骤(1)所述的增韧剂为乙烯一醋酸乙烯共聚物、甲基丙烯酸甲酯一丁二烯一苯乙烯共聚物或三元乙丙胶的任一一种；
优选地，步骤(1)所述的无机复配阻燃填料为氢氧化镁、氢氧化铝按一定比例混合获得的。
附图说明
图1为实施例1制备的含氰基芳醚磷腈型无卤阻燃剂傅里叶变换红外光谱图；
图2为实施例1制备的含氰基芳醚磷腈型无卤阻燃剂核磁共振氢谱图；
图3为实施例1获得的含氰基芳醚磷腈型无卤阻燃剂型聚乙烯复合电缆绝缘材料经高能电子束分别辐照100kGy、130kGy、160kGy和190kGy后的凝胶含量；
图4为实施例1获得的含氰基芳醚磷腈型无卤阻燃剂型聚乙烯复合电缆绝缘材料经高能电子束分别辐照100kGy、130kGy、160kGy和190kGy后的力学性能；
图5为实施例1获得的含氰基芳醚磷腈型无卤阻燃剂型聚乙烯复合电缆绝缘材料经高能电子束分别辐照100kGy、130kGy、160kGy和190kGy后的极限氧指数。
具体实施方式
下面结合实施例及附图对本发明作进一步详细的描述，但本发明的实施方式不限于此。
实施例1
含氰基芳醚磷腈型无卤阻燃剂的制备：
(1)将4-羟基苯甲腈0.144mol和200mL丙酮溶液混合，在室温条件下搅拌至4-羟基苯甲腈完全溶解后加入K2CO3粉末0.16mol，在N2气氛下加热回流4h获得4-羟基苯甲腈溶液，加热温度为50℃；
(2)称取六氯环三磷腈0.02mol溶于20mL丙酮溶液中获得六氯环三磷腈溶液，将六氯环三磷腈溶液加入步骤(1)所述的4-羟基苯甲腈溶液，反应6h后获得白色沉淀物；
(3)将步骤(2)获得的白色沉淀物分别用去离子水和丙酮重复洗涤3-6次后，获得白色粉末状产物，然后在真空烘箱中80℃干燥12h,获得一种含氰基芳醚磷腈型无卤阻燃剂HPCTP-CN，产率约为88.00％，利用傅里叶变换红外光谱对含氰基芳醚磷腈型无卤阻燃剂进行了结构分析，如图1所示：1205cm-1处为P＝N的特征吸收峰，939、1016和1105cm-1处为P-O-C的特征吸收峰，2227cm-1为CN的特征吸收峰，1400-1600cm-1为苯环的特征吸收峰；将含氰基芳醚磷腈型无卤阻燃剂溶于氘代氯仿中进行核磁共振氢谱测试，测试结果如图2所示：在化学位移为7.28处的氘代氯仿的特征峰，以及7.11、7.13、7.60和7.625处苯环上的特征峰。
聚乙烯复合阻燃电缆绝缘材料的制备：
(1)按照重量份数计算，将含氰基芳醚磷腈型无卤阻燃剂10份、高密度聚乙烯100份、乙烯一醋酸乙烯共聚物增韧剂40份和无机复配阻燃填料90份(按照质量比，氢氧化镁：氢氧化铝为1:1)混合加入双辊开炼机中熔融塑化后，再放入热压机中模压成型，获得了含氰基芳醚磷腈型无卤阻燃剂型聚乙烯复合电缆绝缘材料，其料凝胶含量、力学性能和极限氧指数指数分别详见表2和图3、图4和图5；
(2)将步骤(1)获得的含氰基芳醚磷腈型无卤阻燃剂型聚乙烯复合电缆绝缘材料进行高能电子束辐照交联，分别进行剂量为100kGy、130kGy、160kGy和190kGy的辐照，获得四种交联后的含氰基芳醚磷腈型无卤阻燃剂型聚乙烯复合电缆绝缘材料，四种交联后的无卤阻燃剂型聚乙烯复合电缆料凝胶含量、力学性能以及极限氧指数分别详见表2、图3、图4和图5所示。
实施例2
含氰基芳醚磷腈型无卤阻燃剂的制备：
(1)将4-羟基苯甲腈0.216mol和250mL丙酮溶液混合，在室温条件下搅拌至4-羟基苯甲腈完全溶解后加入K2CO3粉末0.32mol，在N2气氛下加热回流8h获得4-羟基苯甲腈溶液，加热温度为80℃；
(2)称取六氯环三磷腈0.03mol溶于30mL丙酮溶液中获得六氯环三磷腈溶液，将六氯环三磷腈溶液逐滴加入步骤(1)所述的4-羟基苯甲腈溶液，反应8h后获得白色沉淀物；
(3)将步骤(2)获得的白色沉淀物分别用去离子水和丙酮重复洗涤3-6次后，获得白色粉末状产物，然后在真空烘箱中60℃干燥10h,获得一种含氰基芳醚磷腈型无卤阻燃剂HPCTP-CN，产率约为86.00％。
含氰基芳醚磷腈型无卤阻燃剂型聚乙烯复合电缆绝缘材料的制备：
(1)按照重量份数计算，将含氰基芳醚磷腈型无卤阻燃剂20份、高密度聚乙烯80份、乙烯一醋酸乙烯共聚物增韧剂30份和无机复配阻燃填料60份(按照质量比，氢氧化镁：氢氧化铝为1:1)混合加入双辊开炼机中熔融塑化后，再放入热压机中模压成型，获得了含氰基芳醚磷腈型无卤阻燃剂型聚乙烯复合电缆绝缘材料；
(2)将步骤(1)获得的无卤阻燃剂型聚乙烯复合电缆绝缘材料进行高能电子束辐照交联，分别进行剂量为100kGy、130kGy、160kGy和190kGy的辐照，获得四种交联后的含氰基芳醚磷腈型无卤阻燃剂型聚乙烯复合电缆绝缘材料。
实施例3
含氰基芳醚磷腈型无卤阻燃剂的制备：
(1)将4-羟基苯甲腈0.288mol和250mL丙酮溶液混合，在室温条件下搅拌至4-羟基苯甲腈完全溶解后加入K2CO3粉末0.48mol，在N2气氛下加热回流10h获得4-羟基苯甲腈溶液，加热温度为100℃；
(2)称取六氯环三磷腈0.06mol溶于20mL丙酮溶液中获得六氯环三磷腈溶液，将六氯环三磷腈溶液逐滴加入步骤(1)所述的4-羟基苯甲腈溶液，反应10h后获得白色沉淀物；
(3)将步骤(2)获得的白色沉淀物分别用去离子水和丙酮重复洗涤3-6次后，获得白色粉末状产物，然后在真空烘箱中120℃干燥5h,获得一种含氰基芳醚磷腈型无卤阻燃剂HPCTP-CN，产率约为84.69％。
聚乙烯复合阻燃电缆绝缘材料的制备：
(1)按照重量份数计算，将含氰基芳醚磷腈型无卤阻燃剂20份、高密度聚乙烯70份、乙烯一醋酸乙烯共聚物增韧剂30份和无机复配阻燃填料80份(按照质量比，氢氧化镁：氢氧化铝为1:1)混合加入双辊开炼机中熔融塑化后，再放入热压机中模压成型，获得了含氰基芳醚磷腈型无卤阻燃剂型聚乙烯复合电缆绝缘材料；
(2)将步骤(1)获得的无卤阻燃剂型聚乙烯复合电缆绝缘材料进行高能电子束辐照交联，分别进行剂量为100kGy、130kGy、160kGy和190kGy的辐照，获得四种交联后的含氰基芳醚磷腈型无卤阻燃剂型聚乙烯复合电缆绝缘材料。
对比1聚乙烯复合阻燃电缆绝缘材料(不含氰基芳醚磷腈型无卤阻燃剂)的制备：
(1)按照重量份数计算，将含高密度聚乙烯100份、乙烯一醋酸乙烯共聚物增韧剂40份和无机复配阻燃填料100份(按照质量比，氢氧化镁：氢氧化铝为1:1)混合加入双辊开炼机中熔融塑化后，再放入热压机中模压成型，获得了含氰基芳醚磷腈型无卤阻燃剂型聚乙烯复合电缆绝缘材料；
(2)将步骤(1)获得的含氰基芳醚磷腈型无卤阻燃剂型聚乙烯复合电缆绝缘材料进行高能电子束辐照交联，分别进行剂量为100kGy、130kGy、160kGy和190kGy的辐照，获得四种交联后的含氰基芳醚磷腈型无卤阻燃剂型聚乙烯复合电缆绝缘材料，其凝胶含量、最大拉伸应力和极限氧指数详见表1。
表1交联后的聚乙烯复合阻燃电缆绝缘材料(不含氰基芳醚磷腈型无卤阻燃剂)的性能
表2交联后的聚乙烯复合阻燃电缆绝缘材料(含氰基芳醚磷腈型无卤阻燃剂)的性能
Claims (7)
1.一种含氰基芳醚磷腈型无卤阻燃剂在聚乙烯复合阻燃电缆绝缘材料的应用，其特征在于：所述应用的具体方法如下：
(1)按照重量份数计算，将含氰基芳醚磷腈型无卤阻燃剂100～10份、聚乙烯100～10份、增韧剂40～4份和无机复配阻燃填料100～10份混合加入双辊开炼机中熔融塑化后，再放入热压机中模压成型，获得了含氰基芳醚磷腈型无卤阻燃剂型聚乙烯复合电缆绝缘材料；
(2)将步骤(1)获得的含氰基芳醚磷腈型无卤阻燃剂型聚乙烯复合电缆绝缘材料进行高能电子束辐照交联，辐照剂量为100～300kGy，获得交联聚乙烯复合阻燃电缆绝缘材料；
步骤(1)所述的含氰基芳醚磷腈型无卤阻燃剂，为结构式1所示的化合物：
2.根据权利要求1所述的一种含氰基芳醚磷腈型无卤阻燃剂在聚乙烯复合阻燃电缆绝缘材料的应用，其特征在于：步骤(1)所述的含氰基芳醚磷腈型无卤阻燃剂的制备方法包括如下步骤：
(1)按照摩尔比24～36:5的比例称取4-羟基苯甲腈和六氯环三磷腈，将4-羟基苯甲腈和丙酮溶液混合，在室温条件下搅拌至4-羟基苯甲腈完全溶解后加入催化剂，在氮气气氛下加热回流4～12h获得4-羟基苯甲腈溶液，加热温度为50～100℃；
(2)将六氯环三磷腈溶于丙酮溶液中获得六氯环三磷腈溶液，将六氯环三磷腈溶液加入步骤(1)获得的4-羟基苯甲腈溶液，反应6～10h后获得白色沉淀物；
(3)将步骤(2)获得的白色沉淀物分别用去离子水和丙酮重复洗涤3～6次后，获得白色粉末状产物，再将白色粉末状产物在60～120℃干燥5～12h,获得含氰基芳醚磷腈型无卤阻燃剂。
3.根据权利要求2所述一种含氰基芳醚磷腈型无卤阻燃剂在聚乙烯复合阻燃电缆绝缘材料的应用，其特征在于：步骤(1)所述催化剂为碳酸钾。
4.根据权利要求2所述一种含氰基芳醚磷腈型无卤阻燃剂在聚乙烯复合阻燃电缆绝缘材料的应用，其特征在于：步骤(1)所述加热温度为50～80℃。
5.根据权利要求1所述的含氰基芳醚磷腈型无卤阻燃剂在聚乙烯复合阻燃电缆绝缘材料的应用，其特征在于：步骤(1)所述的聚乙烯为高密度聚乙烯、低密度聚乙烯、线型低密度聚乙烯中的任一一种。
6.根据权利要求1所述的含氰基芳醚磷腈型无卤阻燃剂在聚乙烯复合阻燃电缆绝缘材料的应用，其特征在于：步骤(1)所述的增韧剂为乙烯—醋酸乙烯共聚物、甲基丙烯酸甲酯—丁二烯—苯乙烯共聚物或三元乙丙胶的任一一种。
7.根据权利要求1所述的含氰基芳醚磷腈型无卤阻燃剂在聚乙烯复合阻燃电缆绝缘材料的应用，其特征在于：步骤(1)所述的无机复配阻燃填料为氢氧化镁、氢氧化铝按一定比例混合获得的。
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