CN111995747B - 一种聚酰胺用反应型阻燃剂的制备方法及其应用 - Google Patents
一种聚酰胺用反应型阻燃剂的制备方法及其应用 Download PDFInfo
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Abstract
本发明涉及到一种聚酰胺用反应型阻燃剂的制备方法及其应用。该方法包括下述步骤：将一定量的DOPO‑HQ与相应比例的缚酸剂投入三口烧瓶中，加入溶剂溶解，在50~140摄氏度的条件下滴加一定量氯乙酸酯，反应4~24小时后旋蒸除去溶剂与未反应的氯乙酸酯，加入DOPO‑HQ 2.5倍摩尔质量氢氧化钠的乙醇溶液将得到的中间体的酯键水解后加入盐酸调节pH=1，过滤，二次水洗涤3次，烘干即可得上述聚酰胺用反应型阻燃剂。产物产率为52～68%。
Description
技术领域
本发明属于一种聚酰胺用反应型阻燃剂的制备技术领域，具体涉及一种聚酰胺用反应型阻燃剂及其制备方法及其在聚酰胺中的应用。
背景技术
聚酰胺纤维具有断裂强度高、耐磨好、密度低、吸湿高、染色好等优点，在高端服饰、军警用品和工业丝等领域具有不可替代的地位。然而作为化学纤维主要品种的聚酰胺纤维却难以达到理想的阻燃效果，这是由于：通常需要添加高含量的阻燃剂才能达到满足要求的阻燃性能，而酰胺键较活泼，在高约260-320℃的纺丝温度时，易与阻燃剂发生化学反应、致分子链降解。因此阻燃改性易导致聚酰胺可纺性及其纤维物理机械性能恶化，所以阻燃聚酰胺纤维制备技术要求高、控制难度大，目前国内外对阻燃聚酰胺研发大多集中于树脂领域，未见阻燃聚酰胺纤维商品化产品成功开发的实例。
10-(2,5-二羟基苯基)-10-氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO-HQ)是一种磷杂菲类反应型阻燃剂，常用作覆铜板、半导体封装等高端环氧树脂的阻燃剂和固化剂，具有添加量低、阻燃效果好、不影响材料力学性能等优点。不仅如此，DOPO-HQ在聚氨酯、聚乳酸等其它聚合物中也展示出其优异的阻燃性能。然而，将DOPO-HQ引入聚酰胺时却存在明显的问题：将其作为添加型阻燃剂加入时会明显恶化聚酰胺的力学性能；酚羟基活性较低，不能作为共聚结构引入聚酰胺主链中。
发明内容
本发明的目的是针对现有技术存在的问题，首先提供一种聚酰胺用反应型阻燃剂。
本发明的另一目的是提供一种上述反应型阻燃剂的制备方法。
本发明提供的一种聚酰胺用反应型阻燃剂，其特征在于该聚酰胺用阻燃剂的结构如下：
本发明提供的上述聚酰胺用反应型阻燃剂的制备方法，其特征在于该方法的工艺步骤和条件如下：
将一定量的DOPO-HQ与相应比例的缚酸剂投入三口烧瓶中，加入溶剂溶解，在50～140摄氏度的条件下滴加一定量氯乙酸酯，反应4～24小时后旋蒸除去溶剂与未反应的氯乙酸酯，加入DOPO-HQ 2.5倍摩尔质量氢氧化钠的乙醇溶液将得到的中间体的酯键水解后加入盐酸调节pH＝1，过滤，二次水洗涤3次，烘干即可得上述聚酰胺用反应型阻燃剂。
以上方法中所用的缚酸剂为三乙胺、碳酸钠、碳酸钾或吡啶中的一种或多种。
以上方法中所用的溶剂为乙醇、乙二醇乙醚、1,4-二氧六环、甲苯、乙腈或丙酮中的一种或多种。
以上方法中所用的氯乙酸酯为氯乙酸甲酯、氯乙酸乙酯或氯乙酸丙酯中的任一种。
以上方法中所用的DOPO-HQ与氯乙酸酯的摩尔比为1：2～5。
本发明与现有技术相比，具有以下有益效果：
1、本发明提供的阻燃剂解决了DOPO-HQ不能用于聚酰胺阻燃的问题。
2、添加了本发明阻燃剂的聚酰胺纤维具有阻燃性能好、力学性能优异、可纺性强等优点。
3、本发明提供的阻燃剂是一种反应型阻燃剂，不含卤素，符合环保要求。
4、本发明提供的制备方法简单，易于控制，便于推广使用。
附图说明
图1为本发明实施2所制备的聚酰胺用反应型阻燃剂的核磁共振氢谱图。
具体实施方式
下面通过实施例对本发明作进一步说明。值得指出的是，给出的实施例不能理解为对本发明保护范围的限制，该领域的技术人员根据本发明的内容对本发明作出的一些非本质的改进和调整仍应属于本发明保护范围。
实施例1
将0.4mol的DOPO-HQ、0.8mol的三乙胺与足量的甲苯加入三口烧瓶中，升温至110℃，待DOPO-HQ完全溶解后滴加1mol的氯乙酸丙酯，1小时滴加完毕后保温反应8小时，旋蒸除去溶剂与多余的氯乙酸丙酯。加入含有1mol氢氧化钠的乙醇溶液，搅拌水解2小时后滴入盐酸调节pH＝1，过滤，使用二次水洗涤三次，烘干即得上述阻燃剂，产率84％。
实施例2
将0.4mol的DOPO-HQ、0.4mol的碳酸钾与足量的乙腈加入三口烧瓶中，升温至90℃，待DOPO-HQ完全溶解后滴加2mol的氯乙酸甲酯，2小时滴加完毕后保温反应14小时，旋蒸除去溶剂与多余的氯乙酸甲酯。加入含有1mol氢氧化钠的乙醇溶液，搅拌水解2小时后滴入盐酸调节pH＝1，过滤，使用二次水洗涤三次，烘干即得上述阻燃剂，产率89％。
图1为本发明实施2所制备的聚酰胺用反应型阻燃剂的核磁共振氢谱图。图中，4.0～5.0ppm的峰归属于氯乙酸酯中亚甲基的H，6.5～8.5ppm处为DOPO-HQ中芳香环上的C-H，13ppm左右为COOH的吸收峰，以上结果证明了上述阻燃剂的成功制备。
实施例3
将0.4mol的DOPO-HQ、0.4mol的碳酸钠与足量的乙二醇乙醚加入三口烧瓶中，升温至140℃，待DOPO-HQ完全溶解后滴加1.5mol的氯乙酸乙酯，1.5小时滴加完毕后保温反应4小时，旋蒸除去溶剂与多余的氯乙酸乙酯。加入含有1mol氢氧化钠的乙醇溶液，搅拌水解2小时后滴入盐酸调节pH＝1，过滤，使用二次水洗涤三次，烘干即得上述阻燃剂，产率72％。
实施例4
将0.4mol的DOPO-HQ、0.8mol的吡啶与足量的丙酮加入三口烧瓶中，升温至50℃，待DOPO-HQ完全溶解后滴加1.2mol的氯乙酸乙酯，1小时滴加完毕后保温反应23小时，旋蒸除去溶剂与多余的氯乙酸乙酯。加入含有1mol氢氧化钠的乙醇溶液，搅拌水解2小时后滴入盐酸调节pH＝1，过滤，使用二次水洗涤三次，烘干即得上述阻燃剂，产率88％。
实施例5
将0.4mol的DOPO-HQ、0.8mol的三乙胺与足量的乙醇加入三口烧瓶中，升温至80℃，待DOPO-HQ完全溶解后滴加1.8mol的氯乙酸甲酯，2小时滴加完毕后保温反应16小时，旋蒸除去溶剂与多余的氯乙酸甲酯。加入含有1mol氢氧化钠的乙醇溶液，搅拌水解2小时后滴入盐酸调节pH＝1，过滤，使用二次水洗涤三次，烘干即得上述阻燃剂，产率74％。
应用例1
将实施例2的阻燃剂和己二胺以1:1.5的摩尔比混合，再加入占体系总质量30wt％的去离子水作为反应溶剂，氮气保护时进行升温和搅拌，搅拌转速为50r/min；温度升至200℃后保持压力为1.5MPa，保温保压1h；0.5h内将压力降至常压，将搅拌转速降至30r/min，抽真空至-0.05MPa保持0.5h；停止搅拌，静置10～15min，氮气保护时出料制得阻燃剂盐。
按重量份数计，将97份己二酸己二胺盐和3份阻燃剂盐混合后，加入适量的己二酸，使得体系中端氨基与端羧基的摩尔比为1:1.01，再加入占体系总质量60％的去离子水，氮气保护时进行升温和搅拌，搅拌转速为200r/min；温度升至210℃后保持压力在1.85MPa，保温保压1h；将搅拌转速降至100r/min，2h内将压力降至常压；将搅拌速度降至50r/min，抽真空至0.08MPa保持1h；停止搅拌，静置10～15min，氮气保护时出料制得阻燃聚酰胺66，极限氧指数为28％。
应用例2
将实施例2的阻燃剂和戊二酸等摩尔比混合，再加入占体系总质量30wt％的去离子水作为反应溶剂，氮气保护时进行升温和搅拌，搅拌转速为50r/min；温度升至200℃后保持压力为1.5MPa，保温保压1h；0.5h内将压力降至常压，将搅拌转速降至30r/min，抽真空至-0.07MPa保持1h；停止搅拌，静置10～15min，氮气保护时出料制得阻燃剂盐。
按重量份数计，将95份己内酰胺和5份阻燃剂盐混合后，加入适量的己二胺，使得体系中端氨基与端羧基的摩尔比为1.1:1，再加入占体系总质量5％的去离子水，氮气保护时进行升温和搅拌，搅拌转速为100r/min；温度升至200℃后保持压力为0.6MPa，保温保压1h；0.5h内将压力降至常压；将搅拌转速降至50r/min，通氮气反应3h；抽真空至-0.05MPa保持1.5h；停止搅拌，静置10～15min，氮气保护时出料制得阻燃聚酰胺6，极限氧指数为29％。
Claims (7)
1.一种聚酰胺用反应型阻燃剂，其特征在于该聚酰胺用阻燃剂的结构如下：
2.根据权利要求1所述的聚酰胺用反应型阻燃剂的制备方法，其特征在于，该方法的工艺步骤和条件如下：
将DOPO-HQ与缚酸剂投入容器中，加入溶剂溶解，在50～140℃的条件下滴加氯乙酸酯，反应4～24小时后旋蒸除去溶剂与未反应的氯乙酸酯，加入相对于DOPO-HQ 2.5倍摩尔量的氢氧化钠的乙醇溶液，将得到的中间体的酯键水解后加入盐酸调节pH＝1，过滤，二次水洗涤3次，烘干即可得上述聚酰胺用反应型阻燃剂。
3.根据权利要求2所述的聚酰胺用反应型阻燃剂的制备方法，其特征在于，缚酸剂为三乙胺、碳酸钠、碳酸钾或吡啶中的一种或多种。
4.根据权利要求2所述的聚酰胺用反应型阻燃剂的制备方法，其特征在于，溶剂为乙醇、乙二醇乙醚、1,4-二氧六环、甲苯、乙腈或丙酮中的一种或多种。
5.根据权利要求2所述的聚酰胺用反应型阻燃剂的制备方法，其特征在于，氯乙酸酯为氯乙酸甲酯、氯乙酸乙酯或氯乙酸丙酯中的任一种。
6.根据权利要求2所述的聚酰胺用反应型阻燃剂的制备方法，其特征在于，DOPO-HQ与氯乙酸酯的摩尔比为1：2～5。
7.采用权利要求1所述的阻燃剂在制备聚酰胺中的应用。
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