CN106167505A - 一种含硅笼状硫代磷酸酯阻燃剂及其制备方法 - Google Patents
一种含硅笼状硫代磷酸酯阻燃剂及其制备方法 Download PDFInfo
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Abstract
本发明所公开的一种含硅笼状硫代磷酸酯阻燃剂，其结构如式Ⅰ所示。本发明还公开了该阻燃剂的制备方法，包括将1‑硫代‑4‑羟甲基‑1‑磷杂‑2,6,7‑三氧杂双环[2,2,2]‑辛烷加溶剂二氯甲烷溶解，再加入缚酸剂三乙胺和二甲基二氯硅烷，通入氮气，升温至40℃恒温反应19~24h，停止反应，降至室温，抽滤，水洗，得到白色产物，将产物在80~100℃恒温干燥8~12h即获得所述一种含硅笼状硫代磷酸酯阻燃剂。该阻燃剂具有热稳定好、成炭性好、与基体相容性好等特点；分子结构中的磷、硅、硫等元素可以起到协同作用，有望应用于聚氨酯、环氧树脂、聚丙烯等常见的聚合物材料。
Description
技术领域
本发明属于阻燃剂领域，涉及一种含硅笼状硫代磷酸酯阻燃剂的结构及其制备方法。
背景技术
近年来，开发新型无卤阻燃剂成为了众多科研人员的研究热点之一。阻燃剂按阻燃元素可分为磷系、氮系和硅系等，但各自体系阻燃剂的缺点抑制了其发展，因此制备多元素协同阻燃剂已成为目前无卤阻燃的发展方向之一。磷系阻燃剂是无卤化阻燃剂的主体，硅系阻燃剂是后起之秀。磷/硅二元协同阻燃剂已受到了广大学者的青睐，硅系阻燃剂具有无卤、低毒、低烟等特点，而且硅元素的引入可在聚合物表面形成硅化合物层，从而降低高温下磷炭层的氧化以提高磷的阻燃效率。现已有较多专利公开了多种磷/硅二元协同阻燃剂的制备方法（例如CN105198926A，CN104211880A，CN104725667A等等）。
含硫的阻燃材料在热分解时的成炭量远高于理论值，具有阻燃作用，因研究较少而尚未成体系，同样关于磷/硫二元协同阻燃的报道也较少。SPEPA分子结构中同时含有磷、硫两种阻燃元素和活泼性的羟基，以致其在阻燃剂的分子结构设计中存在优先选择性。将磷、硫、硅等多种阻燃元素设计在同一分子结构中，通过元素之间的协同互补作用，可大大提高单一元素的利用率。
本发明的特点是将磷、硅、硫三种元素设计在同一分子结构中，具有协同阻燃作用，可以改善有机磷阻燃剂存在的迁移性问题，且其热稳定性好，成炭性好，有很好的发展和应用前景。
发明内容
本发明的目的是提供一种含硅笼状硫代磷酸酯阻燃剂的结构及其制备方法。
本发明的技术方案是：
一种含硅笼状硫代磷酸酯阻燃剂，该阻燃剂的结构式如下：
。
所述的含硅的笼状硫代磷酸酯阻燃剂的制备方法步骤如下：
将1-硫代-4-羟甲基-1-磷杂-2,6,7-三氧杂双环[2,2,2]-辛烷（SPEPA）与二甲基二氯硅烷按摩尔比2:1~1.2在溶剂二氯甲烷中溶解（每摩尔SPEPA的溶剂用量为600~800ml），以三乙胺为缚酸剂（三乙胺与SPEPA的摩尔比为1~1.1:1），通入氮气，升温至40℃恒温反应19~24h，停止反应，降至室温，抽滤，水洗，得到白色产物，将产物在80~100℃恒温干燥8~12h即获得所述一种含硅笼状硫代磷酸酯阻燃剂。
本发明的效果和益处是：采用简单的合成工艺法制备出了磷、硅、硫三元一体的阻燃剂，且产物为白色粉末状固体，有望适用于多种聚合物基材中。
本发明方法制备得到的含硅笼状硫代磷酸酯阻燃剂中含有四个刚性环状结构，热稳定性好；成炭性好，在700℃时，残炭率高达60%。
附图说明
图1是实施例1含硅笼状硫代磷酸酯阻燃剂的FTIR谱图。
图2是实施例1含硅笼状硫代磷酸酯阻燃剂的1H-NMR谱图。
图3是实施例1含硅笼状硫代磷酸酯阻燃剂的31P-NMR谱图。
图4是实施例1含硅笼状硫代磷酸酯阻燃剂氮气氛围下的热失重曲线图。
具体实施方式
以下结合技术方案给出实施例以对本发明作进一步说明。
实施例1
在装有机械搅拌、回流冷凝管（尾端与装有无水氯化钙干燥管和氯化氢吸收液相连）的250ml四口烧瓶中加入0.05molSPEPA、40ml二氯甲烷和0.019mol缚酸剂三乙胺，氮气保护下，于38℃用恒压滴液漏斗向烧瓶中缓慢滴加3.0ml二甲基二氯硅烷，滴加完毕后，保持40±2℃回流20h至无氯化氢产生，停止反应，冷却抽滤后水洗，抽滤，在100℃烘箱中干燥8h，得到白色粉末状产物含硅笼状硫代磷酸酯阻燃剂，产率为85%。
实施例2
在装有机械搅拌、回流冷凝管（尾端与装有无水氯化钙干燥管和氯化氢吸收液相连）的250ml四口烧瓶中加入0.05molSPEPA、40ml二氯甲烷和0.018mol缚酸剂三乙胺，氮气保护下，于40℃用恒压滴液漏斗向烧瓶中缓慢滴加3.0ml二甲基二氯硅烷，滴加完毕后，保持40±2℃回流21h至无氯化氢产生，停止反应，冷却抽滤后水洗，抽滤，在80℃烘箱中干燥8h，得到白色粉末状产物含硅笼状硫代磷酸酯阻燃剂，产率为83%。
实施例3
在装有机械搅拌、回流冷凝管（尾端与装有无水氯化钙干燥管和氯化氢吸收液相连）的250ml四口烧瓶中加入0.05molSPEPA、40ml二氯甲烷和0.018mol缚酸剂三乙胺，氮气保护下，于40℃用恒压滴液漏斗向烧瓶中缓慢滴加3.2ml二甲基二氯硅烷，滴加完毕后，保持40±2℃回流22.5h至无氯化氢产生，停止反应，冷却抽滤后水洗，抽滤，在100℃烘箱中干燥9h，得到白色粉末状产物含硅笼状硫代磷酸酯阻燃剂，产率为87%。
实施例4
在装有机械搅拌、回流冷凝管（尾端与装有无水氯化钙干燥管和氯化氢吸收液相连）的250ml四口烧瓶中加入0.1molSPEPA、60ml二氯甲烷和0.036mol缚酸剂三乙胺，氮气保护下，于39℃用恒压滴液漏斗向烧瓶中缓慢滴加6.0ml二甲基二氯硅烷，滴加完毕后，保持40±2℃回流21h至无氯化氢产生，停止反应，冷却抽滤后水洗，抽滤，在100℃烘箱中干燥10h，得到白色粉末状产物含硅笼状硫代磷酸酯阻燃剂，产率为90%。
实施例5
在装有机械搅拌、回流冷凝管（尾端与装有无水氯化钙干燥管和氯化氢吸收液相连）的250ml四口烧瓶中加入0.1molSPEPA、60ml二氯甲烷和0.034mol缚酸剂三乙胺，氮气保护下，于40℃用恒压滴液漏斗向烧瓶中缓慢滴加6.0ml二甲基二氯硅烷，滴加完毕后，保持40±2℃回流23h至无氯化氢产生，停止反应，冷却抽滤后水洗，抽滤，在100℃烘箱中干燥12h，得到白色粉末状产物含硅笼状硫代磷酸酯阻燃剂，产率为97%。
实施例6
以水为发泡剂，通过大量实验确定阻燃聚氨酯泡沫配方如表1所示，按表中配方采用一步法发泡工艺：将聚醚多元醇、胺催化剂、二甲基硅油、锡催化剂、水、丙三醇、正戊烷、实施例1中的含硅笼状硫代磷酸酯于同一容器中高速搅拌至混合均匀。于室温，将多次甲基多苯基多异氰酸酯(PAPI)加入以上混合料中继续搅拌20s左右，迅速倒入模具中自由发泡，模具在室温放置1h后放入烘箱，于80℃下熟化24h，开模取出泡体，即得到了阻燃聚氨酯泡沫塑料。对阻燃聚氨酯泡沫塑料进行表观密度（参照GB/T 6343-2009标准测定）和氧指数（参照GB8624-1997标准测定）测试，结果如表2所示。
表1阻燃聚氨酯泡沫配方
表2 含硅笼状硫代磷酸酯阻燃聚氨酯的阻燃效果
结果表明，上述合成的阻燃剂与硬质聚氨酯体系相容性较好，随着阻燃剂添加含量的增加，氧指数呈现先增大后降低的趋势，当添加份数为40份时，氧指数最高，可达26.9%。
Claims (2)
1.一种含硅笼状硫代磷酸酯阻燃剂及其制备方法，其特征在于该磷酸酯阻燃剂的结构式如下：
。
2.根据权利要求书1所述的含硅的笼状硫代磷酸酯阻燃剂的制备方法，其特征在于包括如下步骤：
将1-硫代-4-羟甲基-1-磷杂-2,6,7-三氧杂双环[2,2,2]-辛烷（SPEPA）与二甲基二氯硅烷按摩尔比2:1~1.2在溶剂二氯甲烷中溶解（每摩尔SPEPA的溶剂用量为600~800ml），以三乙胺为缚酸剂（三乙胺与SPEPA的摩尔比为1~1.1:1），通入氮气，升温至40℃恒温反应19~24h，停止反应，降至室温，抽滤，水洗，得到白色产物，将产物在80~100℃恒温干燥8~12h即获得所述一种含硅笼状硫代磷酸酯阻燃剂。
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