CN106398109B - 一种环三磷腈固化酚醛树脂的制备方法 - Google Patents

一种环三磷腈固化酚醛树脂的制备方法 Download PDF

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CN106398109B
CN106398109B CN201610870502.9A CN201610870502A CN106398109B CN 106398109 B CN106398109 B CN 106398109B CN 201610870502 A CN201610870502 A CN 201610870502A CN 106398109 B CN106398109 B CN 106398109B
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程文喜
苗蔚
郑红娟
夏绍灵
彭进
林浩伟
宋伟强
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Abstract

一种环三磷腈固化酚醛树脂的制备方法，其特征是：将热塑性酚醛树脂、六氯环三磷腈、氢氧化物和吸水剂按照重量比100：1~30：1~15：1~30混合均匀得到混合物1，混合物1再和填充剂按照重量比100：0~200混合均匀得到混合物2，混合物2在150~200℃下固化10~30分钟后即得环三磷腈固化的酚醛树脂。在高温下，六氯环三磷腈的P‑Cl键与热塑性酚醛树脂的酚羟基在碱存在下反应形成P‑O‑C交联键，从而固化改性酚醛树脂。

Description

一种环三磷腈固化酚醛树脂的制备方法
技术领域
本发明属于高分子材料制备领域，具体说是涉及一种环三磷腈固化酚醛树脂的制备方法。
背景技术
六氯环三磷腈，是生产聚磷腈和环磷腈的主要原料，分子中含有磷氮单双键交替排列的无机杂环结构。由于六氯环三磷腈的磷氯键的活泼性，可以使氯很容易被亲核试剂，如烷基、烷氧基、酚基、胺基、芳胺基等取代，制得一系列磷腈化合物。由于六元环的稳定性，使其具有耐酸碱以及耐高温特性。如果将其引入树脂结构中，将会进一步提高材料的耐热、耐温性以及机械强度。
专利200910086788中以六氯环三磷腈和苯胺为原料制备六苯胺基六氯环三磷腈，制得的六苯胺基六氯环三磷腈与邻甲酚醛环氧树脂、硅微粉、固化促进剂、硅烷偶联剂、润滑剂、增韧剂和硬脂酸各原料混合后，经混炼，粉碎，消磁后制得用于大规模和超大规模集成电路封装用的无卤阻燃环氧树脂组合物。印染助剂，2010，2（4）：25-28中分别制得甲氧基取代和乙氧基取代六氯环三磷腈丙烯酸酯衍生物，将2种烷氧基取代六氯环三磷腈丙烯酸酯经乳液共聚，获得的聚合物乳液应用于棉织物的阻燃整理，棉织物的阻燃性能得到提高。
目前，还未有环三磷腈固化酚醛树脂的报道。
发明内容
本发明的目的正是针对上述现有技术中所存在的不足之处而提供一种环三磷腈固化酚醛树脂的制备方法。
本发明以热塑性酚醛树脂为树脂基体，将其与六氯环三磷腈、氢氧化物混合后在高温下反应，高温下热塑性酚醛树脂的酚羟基与氢氧化物生成酚氧负离子，然后酚氧负离子与六氯环三磷腈的P-Cl键反应形成P-O-C键，从而获得环三磷腈固化的酚醛树脂。
本发明的目的可通过下述技术措施来实现：
本发明的一种环三磷腈固化酚醛树脂的制备方法方法包括下述步骤：
将热塑性酚醛树脂、六氯环三磷腈、氢氧化物和吸水剂按重量比100：1~30：1~15：1~30混合均匀得到混合物1，混合物1再和填充剂按重量比100：0~200混合均匀得到混合物2，混合物2在150~200℃下固化10~30分钟后即得到环三磷腈固化的酚醛树脂。
本发明中所述的氢氧化物为氢氧化钠、氢氧化钾、氢氧化钡中的任意一种或者几种。
本发明中所述的吸水剂为半水石膏、无水氯化钙、无水硫酸铜、枯矾中的任意一种或者几种。
本发明中所述的填充剂为粘土、膨润土、滑石粉、碳酸钙、白炭黑、铁粉、铝粉、铜粉、银粉、刚玉、碳化硅、金刚石、氮化硼中的任意一种或者几种。
本发明的有益效果如下：
酚醛树脂使用六氯环三磷腈作为固化剂，没有使用乌洛托品进行固化，复合材料中不含游离醛；
六氯环三磷腈耐热性高，所含的P-Cl键，能在氢氧化物的作用下与酚醛树脂的酚羟基反应降低酚羟基的含量，提高复合材料的性能；
使用吸水剂吸收反应放出的水分，间接促进P-Cl键与酚羟基的反应，降低酚醛树脂的气孔率。
具体实施方式
本发明以下将结合实施例作进一步详述。有必要在此指出的是以下实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，该领域的技术熟练人员可以根据上述本发明内容对本发明作出一些非本质的改进和调整。
实施例1.将热塑性酚醛树脂、六氯环三磷腈、氢氧化钠和半水石膏按重量比100：20：8：15混合均匀得到混合物1，混合物1在180℃下热压30min后即得到环三磷腈固化酚醛树脂。该树脂在水、乙醇和甲苯中不溶解，最大失重速率温度高于550℃。
实施例2.将热塑性酚醛树脂、六氯环三磷腈、氢氧化钾和半水石膏按重量比100：15：12：15混合均匀得到混合物1，混合物1再和滑石粉按重量比100：30混合均匀得到混合物2，混合物2在150℃下热压30min后即得到环三磷腈固化酚醛树脂。该树脂在水、乙醇和甲苯中不溶解，最大失重速率温度高于550℃。
实施例3.将热塑性酚醛树脂、六氯环三磷腈、氢氧化钾和半水石膏按重量比100：10：8：10混合均匀得到混合物1，混合物1再和碳酸钙按重量比100：50混合均匀得到混合物2，混合物2在150℃下热压30min后即得到环三磷腈固化酚醛树脂。该树脂在水、乙醇和甲苯中不溶解，最大失重速率温度高于550℃。
将热塑性酚醛树脂、六氯环三磷腈、氢氧化钠和无水氯化钙按重量比100：10：15：8混合均匀得到混合物1，混合物1再和铁粉、刚玉按重量比100：50：100混合均匀得到混合物2，混合物2在200℃下热压30min后即得到环三磷腈固化酚醛树脂。该树脂在水、乙醇和甲苯中不溶解，最大失重速率温度高于550℃。

Claims (4)

1.一种环三磷腈固化酚醛树脂的制备方法，其特征在于：所述方法包括下述步骤：将热塑性酚醛树脂、六氯环三磷腈、氢氧化物和吸水剂按重量比100：1~30：1~15：1~30混合均匀得到混合物1，混合物1再和填充剂按重量比100：0~200混合均匀得到混合物2，混合物2在150~200℃下固化10~30分钟后即得到环三磷腈固化的酚醛树脂。
2.根据权利要求1所述的方法，其特征在于：所述的氢氧化物为氢氧化钠、氢氧化钾、氢氧化钡中的任意一种或者几种。
3.根据权利要求1所述的方法，其特征在于：所述的吸水剂为半水石膏、无水氯化钙、无水硫酸铜、枯矾中的任意一种或者几种。
4.根据权利要求1所述的方法，其特征在于：所述的填充剂为粘土、膨润土、滑石粉、碳酸钙、白炭黑、铁粉、铝粉、铜粉、银粉、刚玉、碳化硅、金刚石、氮化硼中的任意一种或者几种。
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