CN112225902B - 一种ddp聚磷酸酯阻燃剂及其制备方法 - Google Patents

一种ddp聚磷酸酯阻燃剂及其制备方法 Download PDF

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CN112225902B
CN112225902B CN202011151760.4A CN202011151760A CN112225902B CN 112225902 B CN112225902 B CN 112225902B CN 202011151760 A CN202011151760 A CN 202011151760A CN 112225902 B CN112225902 B CN 112225902B
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ddp
ethylene glycol
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宋晓峰
孙奇浩
张宝昌
魏君格
陈兴
沈月石
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Changchun University of Technology
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Abstract

本发明涉及一种新型聚磷酸酯阻燃剂的制备方法，利用9，10‑二氢‑10[2，3‑二（羟基羰基）丙基]‑10‑膦‑10‑氧化物（DDP）与乙二醇熔融酯化反应合成双羟乙基DDP，然后苯基磷酰二氯与双羟乙基DDP进行缩聚反应合成DDP的聚磷酸酯阻燃剂。本方法具有合成工艺简单，成本低的优点。

Description

一种DDP聚磷酸酯阻燃剂及其制备方法
技术领域
本发明属于阻燃剂领域，涉及一种DDP聚磷酸酯阻燃剂及其制备方法。
背景技术
高分子材料由于其具有良好的机械性能，易于加工成型，及其耐腐蚀等优点，目前其已广泛用。但是，由于高分子材料属于易燃材料，并且燃烧会伴随着熔滴现象，这将进一加剧大火势的蔓延，给人类生命和财产安全造成极大威胁。因此，提高高分子材料的火灾安全性对于保护人的生命，降低因高分材料火灾所带来的财产经济损失具有极其重要的意义。
传统的的高分子阻燃方式主要是在在材料加工成型的过程中加入阻燃剂，其中，卤素阻燃剂由于其价格便宜、高效而被广泛应用于高分子材料的阻燃改性。但由于其在燃烧过程中会有有毒气体和腐蚀性烟雾的排放而逐渐被限制应用。因此，无卤阻燃剂的研究已经成为当今阻燃领域的主流方向，其中，磷系阻燃剂作为一种无卤环保阻燃剂备受关注。磷系阻燃剂在热解时能够产生磷酸或多聚磷酸等酸性物质促使聚合物降解形成碳层，同时燃剂燃烧过程中能够产生含有PO•和PO2•等含磷自由基，能够与聚合物基体交联形成热稳定性良好的聚合物网络，从而起到阻燃的作用；具有高效，环保等优点。但是，目前使用的磷系阻燃剂多为小分子阻燃剂，在聚合物中易迁移。
发明内容
为了解决上述背景中提出的问题，本发明提供一种DDP聚磷酸酯阻燃剂及其制备方法，其结构含有磷，磷化合物可以PO•和PO2•等含磷自由基，促进成碳；同时聚磷酸酯阻燃剂还可以改善阻燃剂在聚合物中的迁移问题，改善其在聚合物中的分善性。因此，这种阻燃剂具有高效阻燃的效果。
本发明提供一种DDP聚磷酸酯阻燃剂，所述阻燃剂结构：
Figure 682836DEST_PATH_IMAGE001
本发明提供一种DDP聚磷酸酯阻燃剂的制备方法，所述制备路线如下：
Figure 12187DEST_PATH_IMAGE002
具体过程包括：
在氮气保护下，将DDP于乙二醇加入三口瓶中升温至一定温度下，熔融反应8-12小时，减压除去多余乙二醇得到淡黄色羟乙基DDP,然后在氮气保护下，将三乙胺(TEA)、羟乙基DDP、二氯甲烷加入三口烧瓶中，在一定温度下通过恒压滴液漏斗缓慢滴入二氯甲烷和苯基磷酰二氯，滴加完毕后升温反应一段时间。反应结束后，将得到的溶液抽滤除去三乙胺盐酸盐，滤液经水洗分液，油层用无水硫酸镁干燥减压蒸馏除去溶剂，即可得到含DDP聚磷酸酯阻燃剂。
附图说明
附图1 DDP聚磷酸酯的核磁谱图；
附图2 DDP聚磷酸酯的热曲线；
附图3 DDP聚磷酸酯PLLA复合材料的LOI测试数据。
具体实施方式
下面结合实施例对本发明进行详细说明。
DDPEG的熔融合成：将3g DDP阻燃剂和1.45g 乙二醇置于三口烧瓶中，然后将烧瓶置于油浴锅中，升温至180℃搅拌使反应物溶解。在此温度下继续反应12小时。反应结束后减压蒸出多余的乙二醇，得到淡黄色固体产物。
PDPEG的合成：向装有氯化钙干燥管和机械搅拌的100mL三口烧瓶中加入3gDDPEG，1.13g TEA和20mL二氯甲烷。在冰水浴和氮气保护下，将PPD 1.34g和二20m1氯甲烷混合液滴加到上述反应体系中。滴完后继续反应2h，然后升温至60℃继续反应24h。反应结束后过滤三乙胺盐酸盐副产物，滤液分别用10％的NaHCO3水溶液和饱和氯化钠水溶液洗涤，然后利用无水硫酸镁对其进行干燥处理，减压蒸馏，得到产物DPPEG。
阻燃复合材料的制备：将聚乳酸与合成的聚磷酸酯阻燃剂以不同比例在氯仿中进行共混，然后将混合液缓慢的倒入模具中，自然挥发溶剂。然后于60℃烘箱中真空干燥5天，制样，将不同共混比例的样条氧指数测定仪进行氧指数（LOI）测试，聚磷酸酯的加入聚乳酸中可使聚乳酸的LOI显著提高。测试结果如附图3所示。

Claims (2)

1.一种含DDP的聚磷酸酯阻燃剂，所述阻燃剂的结构特征为：
Figure FDA0003522169870000011
所述一种含DDP的聚磷酸酯阻燃剂的制备方法包括以下步骤：(1)DDP与乙二醇在氮气保护下接枝，DDP与乙二醇按照1:5的摩尔比进行投料，反应温度180℃，反应时间12h，反应结束，过量的乙二醇以减压蒸馏的方式除去；(2)乙二醇接枝的DDP与苯基磷酰二氯按照摩尔比1:1进行投料，二氯甲烷为溶剂，加入三乙胺作为缚酸剂，在60℃冷凝回流下，缩聚反应24h，反应结束，通过过滤、碱洗、水洗以及减压蒸馏除去溶剂得到最终产物。
2.如权利要求1所述的一种含DDP的聚磷酸酯阻燃剂的制备方法，其特征在于以下步骤：(1)DDP与乙二醇在氮气保护下接枝，DDP与乙二醇按照1:5的摩尔比进行投料，反应温度180℃，反应时间12h，反应结束，过量的乙二醇以减压蒸馏的方式除去；(2)乙二醇接枝的DDP与苯基磷酰二氯按照摩尔比1:1进行投料，二氯甲烷为溶剂，加入三乙胺作为缚酸剂，在60℃冷凝回流下，缩聚反应24h，反应结束，通过过滤、碱洗、水洗以及减压蒸馏除去溶剂得到最终产物。
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