CN107814860A - 一种含磷氮硅的聚丙烯酸酯型阻燃剂及其制备方法 - Google Patents
一种含磷氮硅的聚丙烯酸酯型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磷氮硅的聚丙烯酸酯型阻燃剂,其重复单元结构如式I所示。本发明以苯基磷酰二氯、3‑氨基丙基三乙氧基硅烷和丙烯酸羟乙酯为主要原料合成了含磷氮硅的丙烯酸酯单体,并通过自由基聚合制备了一种含磷氮硅的聚丙烯酸酯型阻燃剂。该阻燃剂具有热稳定性好,成炭性好,抗迁移等特点,有望应用于聚苯乙烯等常见聚合物材料。
Description
技术领域
本发明属于阻燃剂领域,涉及一种含磷氮硅的聚丙烯酸酯型阻燃剂的结构及其制备方法。
背景技术
新阻燃剂的研发具有两个趋势:由小分子阻燃剂向齐聚物阻燃剂发展;由单一阻燃体系向多种阻燃元素“协同”阻燃体系发展。齐聚物阻燃剂具有材料相容性好、分解温度高、耐候性好、还可以改善某些基材的机械性能等优点。美国孟山都公司(US3014956)开发了分子量800左右齐聚磷酸酯;四川大学开展了聚磷(膦)酸酯的合成与应用研究(CN02113512.6;CN200510021217.1);中国专利CN200910012620.6和CN200810012458.3分别公开了含有DOPO侧链结构和PEPA侧链结构的聚磷酸酯阻燃剂及其制备方法。这些齐聚物是基于逐步缩聚工艺合成聚酯或聚酰胺类物质,被应用于PET、PA、PC等材料。磷-氮协同阻燃作用主要体现为膨胀型阻燃机理,可以提高阻燃剂在聚合物基体中的阻燃效率。含硅阻燃剂是近年来新兴起的一种环保型阻燃剂,硅系阻燃剂不仅可以改善材料的阻燃性能和抑烟性能,而且具有提高高分子材料的耐热性能等优点。中国专利CN201310155777.0公开了一种含磷-氮-硅的有机无机杂化阻燃剂,该阻燃剂的合成方法是:将含磷、含氮的硅氧烷通过溶胶凝胶法得到具有Si-O-Si交联结构的有机无机杂化分子。将三种阻燃元素有机地结合到一起,可以更有效的提高磷系阻燃的效率,该阻燃剂可用于PC、PP、PU等材料的阻燃改性。
含磷丙烯酸酯可以通过自由基均聚或共聚,用于制备本质含磷的树脂、涂料、粘合剂等,产物具有阻燃性,既可以单独使用,也可以作为阻燃剂改性其他材料。例如:中国专利CN200910116317.0公布了双官能团的含磷丙烯酸酯,并与三官能团的胺基化合物制备了具有超支化结构的阻燃涂层;中国专利201510810594.7公布了可用于自由基聚合的新型含磷丙烯酸酯单体,可作为反应型阻燃剂添加到聚合物材料中起到阻燃作用;中国专利CN201110128125.9公开了一种含磷氮丙烯酸酯单体,被用于制备聚丙烯酸酯乳液;中国专利CN201410096997.5和CN201410096779.7公开了由含磷丙烯酸酯为单体的聚合型磷-硅阻燃剂,其中含有少量苯乙烯链节,在聚烯烃中相容性较好。含磷丙烯酸酯的制备主要有两种方法:一种是由丙烯酰氯和环氧基或羟基反应得到,这种方法合成成本高,不适合工业化,如美国专利US5399733A和中国专利ZL201410096997.5和ZL201410096979.7;另一种是单羟基丙烯酸质与磷(膦)酰氯反应,由于磷(膦)酰氯价格低廉,广泛易得,更适合工业化,如中国专利ZL200910116317.0。
本发明的特点是将同时含磷氮硅元素的丙烯酸酯进行均聚或共聚得到聚丙烯酸酯型阻燃剂,这种阻燃剂可以通过磷氮协同阻燃作用和磷硅协同阻燃作用,提高原有磷系阻燃剂的阻燃效率,并能够克服小分子阻燃剂在聚烯烃中的相容性欠佳和热稳定性差等问题。
发明内容
本发明的目的是提供一种含磷氮硅的聚丙烯酸酯阻燃剂的结构及其制备方法。
本发明的技术方案是提供的阻燃剂,其特征在于有如式(I)所示的重复单元:
(I)。
本发明提供的一种含磷氮硅的聚丙烯酸酯阻燃剂的制备方法步骤如下:
首先,合成含磷氮硅的丙烯酸酯单体:将苯基磷酰二氯(PDCP)与三乙胺(TEA)按摩尔比1:2.2至1:3的比例以及溶剂四氢呋喃(THF)加入配有搅拌器的三口烧瓶中并降温至-5-0℃,滴加与苯基磷酰二氯(PDCP)等摩尔的3-氨基丙基三乙氧基硅烷(KH550),在0-5℃下反应2-4小时后,滴加与苯基磷酰二氯(PDCP)等摩尔的丙烯酸羟乙酯(HEA),在0-5℃下反应2-4小时后,升温至室温反应2-6小时,反应混合物经过滤去除三乙胺盐酸盐,得到的滤液去除溶剂和未反应的三乙胺后得到浅黄色粘稠液体,即为含磷氮硅的丙烯酸酯,反应式如式(II):
(II)。
然后,将含磷氮硅的丙烯酸酯中加入占单体总质量0.4-0.6%的自由基引发剂(BPO或AIBN),在60-90℃下进行本体聚合1-2小时后,在80℃下熟化10-20小时,得到淡黄色固体,粉碎后,用乙醇抽提去除未反应的单体,烘干,即得到含磷氮硅的聚丙烯酸酯型阻燃剂。
本发明的效果和益处是:采用自由基本体聚合的方法制得同时含磷氮硅的聚丙烯酸酯型阻燃剂,制备方法简单易行,成本低;该阻燃剂具有良好的热稳定性和分解成炭性,5%分解温度275℃,800℃下残炭含量达到35%,炭层结构稳定,并能显著降低材料燃烧热释放率。
附图说明
图1 实施例1中含磷氮硅丙烯酸酯的核磁氢谱。
图2 实施例1中含磷氮硅丙烯酸酯的红外光谱。
图3 实施例2中含磷氮硅的聚丙烯酸酯阻燃剂的热重曲线。
图4实施例3中添加30%含磷氮硅的聚丙烯酸酯阻燃剂的聚苯乙烯燃烧释热曲线。
具体实施方式
以下通过实施例进一步详细说明本发明含磷氮硅的聚丙烯酸酯阻燃剂制备方法,以及该阻燃剂在部分高分子材料中的应用情况。
实施例1
将苯基磷酰二氯(PDCP) 19.5g(0.1mol)与三乙胺(TEA)25.3g(0.25mol)以及溶剂四氢呋喃(THF)100mL加入配有搅拌器的三口烧瓶中并降温至-5-0℃,滴加3-氨基丙基三乙氧基硅烷(KH550)22.14(0.1mol),控制反应器内温度为0-5℃反应3小时后,滴加丙烯酸羟乙酯(HEA)11.6g (0.1mol),在0-5℃下反应2小时后,升温至室温反应4小时,反应混合物经过滤去除三乙胺盐酸盐,得到的滤液去除溶剂和未反应的三乙胺后得到浅黄色粘稠液体,即为含磷氮硅的丙烯酸酯单体。
实施例2
将10g含磷氮硅的丙烯酸酯中加入0.05g AIBN,在70℃下进行本体聚合1小时后,在80℃下熟化16小时,得到淡黄色固体,粉碎后,用乙醇抽提去除未反应的单体,烘干,即得到含磷氮硅的聚丙烯酸酯型阻燃剂。
实施例3
将15g 含磷氮硅的聚丙烯酸酯阻燃剂与35g 通用聚苯乙烯置于180℃、20rpm的密炼机中混合均匀后在微型注射剂中制样。测得该样品极限氧指数LOI达到26.2%;微型燃烧量热仪测得样品的燃烧热总释放29.6kJ/g,热释放率峰值373.2W/g,远低于通用聚苯乙烯的燃烧热总释放43.0 kJ/g,热释放率峰值896 W/g。
Claims (2)
1.一种含磷氮硅的聚丙烯酸酯阻燃剂,其分子结构特征在于阻燃剂具有如式(I)所示的重复单元:
(I)。
2.制备权利要求1中所述的一种含磷氮硅的聚丙烯酸酯阻燃剂的方法,其特征在于:
首先,合成含磷氮硅的丙烯酸酯单体:将苯基磷酰二氯(PDCP)与三乙胺(TEA)按摩尔比1:2.2至1:3的比例以及溶剂四氢呋喃(THF)加入配有搅拌器的三口烧瓶中并降温至-5-0℃,滴加与苯基磷酰二氯(PDCP)等摩尔的3-氨基丙基三乙氧基硅烷(KH550),在0-5℃下反应2-4小时后,滴加与苯基磷酰二氯(PDCP)等摩尔的丙烯酸羟乙酯(HEA),在0-5℃下反应2-4小时后,升温至室温反应2-6小时,反应混合物经过滤去除三乙胺盐酸盐,得到的滤液去除溶剂和未反应的三乙胺后得到浅黄色粘稠液体,即为含磷氮硅的丙烯酸酯,反应式如式(II):
(II);
然后,将含磷氮硅的丙烯酸酯中加入占单体总质量0.4-0.6%的自由基引发剂(BPO或AIBN),在60-90℃下进行本体聚合1-2小时后,在80℃下熟化10-20小时,得到淡黄色固体,粉碎后,用乙醇抽提去除未反应的单体,烘干,即得到含磷氮硅的聚丙烯酸酯型阻燃剂。
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103172770A (zh) * | 2011-12-20 | 2013-06-26 | 深圳市有为化学技术有限公司 | 经由芳酰环系衍生的多官能团或聚合型酰基膦氧化合物 |
CN103709717A (zh) * | 2013-12-17 | 2014-04-09 | 中山台光电子材料有限公司 | 乙烯苄基醚化-dopo化合物树脂组合物及制备和应用 |
CN103897104A (zh) * | 2014-03-04 | 2014-07-02 | 河北联合大学 | 一种含dopo侧基的聚合型磷-硅阻燃剂及其制备方法 |
CN103897105A (zh) * | 2014-03-04 | 2014-07-02 | 河北联合大学 | 一种含pepa侧基的聚合型磷-硅阻燃剂及其制备方法 |
-
2016
- 2016-09-12 CN CN201610814080.3A patent/CN107814860B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103172770A (zh) * | 2011-12-20 | 2013-06-26 | 深圳市有为化学技术有限公司 | 经由芳酰环系衍生的多官能团或聚合型酰基膦氧化合物 |
CN103709717A (zh) * | 2013-12-17 | 2014-04-09 | 中山台光电子材料有限公司 | 乙烯苄基醚化-dopo化合物树脂组合物及制备和应用 |
CN103897104A (zh) * | 2014-03-04 | 2014-07-02 | 河北联合大学 | 一种含dopo侧基的聚合型磷-硅阻燃剂及其制备方法 |
CN103897105A (zh) * | 2014-03-04 | 2014-07-02 | 河北联合大学 | 一种含pepa侧基的聚合型磷-硅阻燃剂及其制备方法 |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109776725A (zh) * | 2018-12-25 | 2019-05-21 | 昆明理工大学 | 一种含磷-氮乙烯基单体阻燃剂及其合成方法 |
CN111363397A (zh) * | 2018-12-25 | 2020-07-03 | 昆明理工大学 | 一种乙烯基磷酸酯阻燃剂及其制备方法 |
CN109776725B (zh) * | 2018-12-25 | 2020-11-24 | 昆明理工大学 | 一种含磷-氮乙烯基单体阻燃剂及其合成方法 |
CN110157042A (zh) * | 2019-04-28 | 2019-08-23 | 北京工商大学 | 新型表面处理剂、其制备方法及经其处理的纳米颗粒在阻燃聚氨酯泡沫中的应用 |
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CN113061217A (zh) * | 2021-05-13 | 2021-07-02 | 蒋春梅 | 一种用于聚乳酸的新型阻燃剂的制备方法 |
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