CN111763232B - 一种含有反应基团的磷杂菲/次磷酸盐双基阻燃剂及其制备方法 - Google Patents
一种含有反应基团的磷杂菲/次磷酸盐双基阻燃剂及其制备方法 Download PDFInfo
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- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
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Abstract
本发明公开一种含有反应基团的磷杂菲/次磷酸盐双基阻燃剂及其制备方法,采用磷杂菲、次磷酸盐和双醛化合物小分子,合成出具有基团协同效应的阻燃剂,获得一种高热稳定性、高残炭的磷杂菲/次磷酸盐阻燃剂。该阻燃剂实现了磷杂菲和次磷酸盐在同一个分子单元内的结合,在凝聚相和气相中同时发挥作用,大大提高了阻燃效率。更关键的是,当使用制备的含硅的双醛化合物作为原料时可以向该阻燃剂中引入硅氧烷柔性链,提高了材料的机械性能。此外,该合成工艺易于操作,产物后处理简单;该阻燃剂改善了物理添加所产生的相容性差和小分子迁移的问题,可有效降低阻燃剂添加量,是一种无卤、高效的环保阻燃剂。
Description
技术领域
本发明涉及一种含有反应基团的磷杂菲/次磷酸盐双基阻燃剂及其制备方法,属于材料科学阻燃剂的合成技术领域。
背景技术
随着高分子材料在工农业生产和人们的衣食住行用等方面发挥的作用日益增加。然而大多数聚合物材料具有易燃、难自熄的特点,为社会安全带来隐患。因此,发展高性能的阻燃聚合物材料成为当前材料改性研究的热点。
近年来,次磷酸盐有很好的应用前景,该类阻燃剂的磷和金属含量高,且单分子内实现磷/金属协同作用,具有阻燃效率高、热稳定性好和烟密度较低等特点。9,10-二氢-9-氧杂-10-磷菲基-10-氧化物(DOPO)及其衍生物因其优异的阻燃机理而常被用于阻燃聚合物,它既可通过释放自由基在气相中发挥阻燃作用,又可通过炭化作用在凝聚相中发挥阻燃作用。硅氧烷作为一种阻燃基团主要在凝聚相发挥作用,同时作为一种柔性基团能够增强材料的韧性。
目前,多数研究都将几种阻燃剂通过物理共混的形式添加到聚合物中,但是往往会出现阻燃剂与基体相容性差、混合不均、小分子迁移等问题,导致阻燃效率大大降低,同时影响了材料的机械性能。因此本发明将磷杂菲、次磷酸盐和硅氧烷通过化学键结合在一个分子单元内,形成含有反应基团的磷杂菲/次磷酸盐双基阻燃剂,既解决了上述问题,又增强了三者的协同阻燃效应,提高了阻燃效率。
发明内容
本发明针对目前存在的问题,提供一种新型的、环境友好的、具有双基协同效应的含有反应基团的磷杂菲/次磷酸盐双基阻燃剂。该阻燃剂体系可将磷杂菲、次磷酸盐和硅氧烷结合在同一个分子单元内,是一种在凝聚相和气相中可同时发挥作用的具有协同效应的阻燃剂。
为解决以上技术问题,本发明采取的技术方案是:
一种含有反应基团的磷杂菲/次磷酸盐双基阻燃剂,其结构通式如下式所示:
其中Mn+为Al3+、Zn2+中的一种。
上述含有反应基团的磷杂菲/次磷酸盐双基阻燃剂的制备方法,包括如下步骤:将双醛化合物溶于第一溶剂中,加入质量浓度50%的次磷酸水溶液,升温至70~90℃,反应12~48h后,加入9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO),再反应4~24h,将金属化合物溶于去离子水中,在机械搅拌下于0.5~2h内滴加入反应液中,再反应8~24h,冷却至室温,抽滤,将滤出固体用蒸馏水洗涤至中性,烘干,得到目标产物——含有反应基团的磷杂菲/次磷酸盐双基阻燃剂。所述的金属化合物中的金属为Al3+、Zn2+中的一种。
反应过程如下:
其中,双醛化合物的制备方法如下:在室温下将对羟基苯甲醛充分溶解在第二溶剂中,加入缚酸剂,密封,充分搅拌15~30min;用注射器将二氯硅烷缓慢加入到溶液中,升温至40~70℃,反应3~20h,冷却至室温,抽滤,滤液除去溶剂后即得到,所述的二氯硅烷为中的一种。优选的,所述的对羟基苯甲醛和二氯硅烷的摩尔比为2:1~2.5:1,更优选择2:1~2.3:1;所述的缚酸剂与二氯硅烷的摩尔比为2:1~3:1;所述的缚酸剂为1,8-二氮杂二环[5.4.0]十一碳-7烯(DBU)、吡啶、金属钠、三乙胺中的一种;所述的第二溶剂为1,4-二氧六环、丙酮、二氯乙烷、二甲亚砜、四氢呋喃中的一种或多种组合。反应过程如下:
上述方案中,进一步的,所述的次磷酸与双醛化合物的摩尔比为1:1~1.6:1;所述的9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物与双醛化合物的摩尔比为1:1~2:1;所述的金属化合物与次磷酸的摩尔比为0.3:1~1:1。采用上述配比,可以提高产率,既能使金属的催化效应得到最大的发挥,又能保证提供稳定性和高的残炭量,使产物具有最好的阻燃性能。
进一步的,所述的第一溶剂为甲醇、乙醇、正丙醇、二甲苯、甲苯中的一种。
本发明的有益效果在于:
1.本发明的含有反应基团的磷杂菲/次磷酸盐双基阻燃剂将有次磷酸盐和磷杂菲通过化学键结合在同一分子单元内,形成基团协同效应,提高阻燃效率,在较低的添加量下就可以获得更好的阻燃效果;如仅将2wt.%的磷杂菲-对苯二羟甲基-次磷酸铝(DHA)阻燃剂添加到环氧树脂中,极限氧指数即可达到32.3%并通过UL94 V-0级。
2.本发明的含有反应基团的磷杂菲/次磷酸盐双基阻燃剂具有反应官能团,能够与环氧树脂和聚氨酯等聚合物基体发生反应,改善了与基体的相容性。
3.本发明的含有反应基团的磷杂菲/次磷酸盐双基阻燃剂引入硅氧烷柔性链,提高了材料的机械性能;如添加2wt.%~4wt.%的磷杂菲-甲基乙烯基硅氧烷-次磷酸铝(DHAMVS)就可使DDM固化的双酚A缩水甘油醚型环氧树脂的冲击强度提高30%~50%,且通过UL94 V-0级。
4.本发明的含有反应基团的磷杂菲/次磷酸盐双基阻燃剂结构中多种金属化合物可供选择,因此可以通过控制金属元素的种类和含量,来调控阻燃剂的热稳定性和阻燃性能,从而赋予该类阻燃剂适应不同材料的应用灵活性。
5.本发明的含有反应基团的磷杂菲/次磷酸盐双基阻燃剂的合成工艺简单,易于操作,无需在高温高压下反应,无需在惰性条件下反应,产物后处理简单,所得产物易于纯化,产率高。
附图说明
图1是本发明实施例1制备的DOPO-次磷酸铝-二苯基硅氧烷阻燃剂(DHADPS)的热失重谱图。
图2是本发明实施例2制备的DOPO-次磷酸铝-甲基乙烯基硅氧烷阻燃剂(DHAMVS)的13C核磁谱图。
图3是本发明实施例3制备的DOPO-次磷酸锌阻燃剂(DHZ)的红外谱图。
具体实施方式
实施例1
步骤一:在室温下向三口烧瓶中加入7.327g对羟基苯甲醛,机械搅拌下充分溶解在150ml四氢呋喃中,加入7.286g三乙胺,密封,充分搅拌15min。用注射器将7.357g二苯二氯硅烷缓慢加入到烧瓶中,升温至60℃,反应6h。冷却至室温,抽滤,滤液除去溶剂后,得到红褐色液体。
步骤二:将步骤一中的滤液溶于100ml正丙醇中,加入4.620g次磷酸(H2O 50%),升温至80℃,反应15h后,加入6.912g 9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物,再反应20h。将3.622g AlCl3·6H2O溶于去离子水中,在机械搅拌下0.5h内滴加入三口烧瓶中,再反应12h,冷却至室温,抽滤,将滤出固体用蒸馏水洗涤至中性,120℃烘干24h,得到白色固体,即为目标产物——含有反应基团的磷杂菲/次磷酸盐双基阻燃剂,收率88%。
实施例2
步骤一:在室温下向三口烧瓶中加入4.885g对羟基苯甲醛,机械搅拌下充分溶解在120ml丙酮中,加入7.308g 1,8-二氮杂二环[5.4.0]十一碳-7烯,密封,充分搅拌20min。用注射器将2.821g甲基乙烯基二氯硅烷缓慢加入到烧瓶中,升温至50℃,反应12h。冷却至室温,抽滤,滤液除去溶剂后,得到红褐色液体。
步骤二:将步骤一中的滤液溶于80ml乙醇中,加入2.904g次磷酸(H2O 50%),升温至75℃,反应8h后,加入6.480g 9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物,再反应16h。将2.413g AlCl3·6H2O溶于去离子水中,在机械搅拌下1h内滴加入三口烧瓶中,再反应10h,冷却至室温,抽滤,将滤出固体用蒸馏水洗涤至中性,120℃烘干24h,得到白色固体,即为目标产物——含有反应基团的磷杂菲/次磷酸盐双基阻燃剂,收率83%。
实施例3
将2.683g对苯二甲醛溶于120ml甲苯中,加入3.168g次磷酸(H2O50%),升温至85℃,反应20h后,加入5.184g 9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物,再反应12h。将1.363g ZnCl2溶于去离子水中,在机械搅拌下1.5h内滴加入三口烧瓶中,再反应15h,冷却至室温,抽滤,将滤出固体用蒸馏水洗涤至中性,120℃烘干24h,得到白色固体,即为目标产物——含有反应基团的磷杂菲/次磷酸盐双基阻燃剂,收率91%。
本发明获得一种高热稳定性、高残炭的阻燃剂。该阻燃剂可实现磷杂菲、次磷酸盐和硅氧烷在同一个分子单元内的结合,在凝聚相和气相中同时发挥作用,大大提高了阻燃效率。与此同时,该阻燃剂引入硅氧烷柔性链,提高了材料的机械性能。此外,该合成工艺易于操作,产物后处理简单;该阻燃剂改善了物理添加所产生的相容性差和小分子迁移的问题,可有效降低阻燃剂添加量,是一种无卤、高效的环保阻燃剂。
上述实施例用来解释说明本发明,而不是对本发明进行限制,在本发明的精神和权利要求的保护范围内,对本发明作出的任何修改和改变,都适用于本发明的保护范围。
Claims (8)
4.根据权利要求3所述的含有反应基团的磷杂菲/次磷酸盐双基阻燃剂的制备方法,其特征在于:所述的对羟基苯甲醛和二氯硅烷的摩尔比为2:1~2.5:1;所述的缚酸剂与二氯硅烷的摩尔比为2:1~3:1。
5.根据权利要求3所述的含有反应基团的磷杂菲/次磷酸盐双基阻燃剂的制备方法,其特征在于:所述的缚酸剂为1,8-二氮杂二环[5.4.0]十一碳-7烯(DBU)、吡啶、金属钠、三乙胺中的一种。
6.根据权利要求3所述的含有反应基团的磷杂菲/次磷酸盐双基阻燃剂的制备方法,其特征在于:所述的第二溶剂为1,4-二氧六环、丙酮、二氯乙烷、二甲亚砜、四氢呋喃中的一种或多种组合。
7.根据权利要求2所述的含有反应基团的磷杂菲/次磷酸盐双基阻燃剂的制备方法,其特征在于:所述的次磷酸与双醛化合物的摩尔比为1:1~1.6:1;所述的9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物与双醛化合物的摩尔比为1:1~2:1;所述的金属化合物与次磷酸的摩尔比为0.3:1~1:1。
8.根据权利要求2所述的含有反应基团的磷杂菲/次磷酸盐双基阻燃剂的制备方法,其特征在于:所述的第一溶剂为甲醇、乙醇、正丙醇、二甲苯、甲苯中的一种。
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10114783A (ja) * | 1996-10-14 | 1998-05-06 | Sanko Chem Co Ltd | 有機環状りん化合物及びその製造方法 |
EP1544227A1 (de) * | 2003-12-17 | 2005-06-22 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Verwendung hydroxylgruppenhaltiger Phosphinate als und zur Herstellung von Flammschutzmitteln, die sich zur Einbindung in Polymerharze eignen, damit hergestellte neue Phosphinate mit organisch polymerisierbaren Gruppen sowie flammgeschützte Polymerharze |
CN101830926A (zh) * | 2010-05-04 | 2010-09-15 | 云梦县江山新材料有限公司 | 二烷基次膦酸金属盐及其阻燃剂的合成工艺 |
CN106573945A (zh) * | 2014-03-17 | 2017-04-19 | 瑞士材料试验研究所 | 基于dopo的杂化阻燃剂 |
CN109762022A (zh) * | 2019-02-15 | 2019-05-17 | 北京工商大学 | 一种磷腈/次磷酸盐双基阻燃剂及其制备方法 |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10114783A (ja) * | 1996-10-14 | 1998-05-06 | Sanko Chem Co Ltd | 有機環状りん化合物及びその製造方法 |
EP1544227A1 (de) * | 2003-12-17 | 2005-06-22 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Verwendung hydroxylgruppenhaltiger Phosphinate als und zur Herstellung von Flammschutzmitteln, die sich zur Einbindung in Polymerharze eignen, damit hergestellte neue Phosphinate mit organisch polymerisierbaren Gruppen sowie flammgeschützte Polymerharze |
CN101830926A (zh) * | 2010-05-04 | 2010-09-15 | 云梦县江山新材料有限公司 | 二烷基次膦酸金属盐及其阻燃剂的合成工艺 |
CN106573945A (zh) * | 2014-03-17 | 2017-04-19 | 瑞士材料试验研究所 | 基于dopo的杂化阻燃剂 |
CN109762022A (zh) * | 2019-02-15 | 2019-05-17 | 北京工商大学 | 一种磷腈/次磷酸盐双基阻燃剂及其制备方法 |
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