CN106432332B - 一种含磷氮丙烯酸酯及其共聚物核壳粒子的制备方法 - Google Patents
一种含磷氮丙烯酸酯及其共聚物核壳粒子的制备方法 Download PDFInfo
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Abstract
本发明公开了的一种含磷氮丙烯酸酯及其共聚物核壳粒子的制备方法。本发明中以苯基磷酰二氯、丙烯酸羟乙酯和二乙胺为原料，三乙胺为缚酸剂，在四氢呋喃中0‑5℃下反应得到含磷氮丙烯酸酯，合成方法简单，成本低；该含磷氮丙烯酸酯可以与其他丙烯酸酯类单体进行自由基共聚合。本发明采用核壳乳液聚合法制备了含磷氮丙烯酸酯的核壳粒子，具有结构、组成可调的优点，在不改变核壳冲击改性剂的结构前提下，粒子本身具有一定的阻燃性，有望被用于阻燃材料的增韧。
Description
技术领域
本发明涉及一种含磷氮丙烯酸酯及其共聚物核壳粒子的制备方法，属于高分子化学及聚合物技术的技术领域。
背景技术
近年来，随着环保及安全防护意识的不断提高，无卤阻燃剂已成为阻燃领域的开发热点。然而无卤阻燃剂存在阻燃效率低和阻燃后材料力学性能不佳等缺点， 解决“提高阻燃性与保持力学性能”之间的矛盾已成为重要课题。将“结构改性与功能改性相结合”，是解决这一问题的新途径。具有核壳结构的丙烯酸酯共聚物粒子是许多高分子材料的冲击改性剂，但是，尚未见对此类核壳冲击改性剂粒子的阻燃功能化报道。本发明的主要内容是将阻燃元素与核壳冲击改性剂结构相结合，制备新型阻燃功能化的冲击改性剂。
含磷丙烯酸酯可以通过自由基共聚合用于制备本质含磷的树脂、涂料、粘合剂等，也可以与其他阻燃单体共聚制备聚合型阻燃剂。中国专利200910116317.0公布了双官能团的含磷丙烯酸酯（1），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，超支化结构有利于提高涂层的韧性。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（2）的制备方法，该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ZL201110128125.9公开了一种含磷氮丙烯酸酯单体（3），该单体被用于制备聚丙烯酸酯乳液，减少了阻燃剂的使用量。中国专利ZL201410096997.5和ZL201410096979.7分别公布了含磷丙烯酸酯（4，5）与含硅丙烯酸酯等共聚制备聚合型阻燃剂，可用于聚苯乙烯等材料的阻燃改性。暂时未见用于制备核壳冲击改性剂的报道。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。
本发明的特点是将含磷氮丙烯酸酯作为共聚单体，引入核壳冲击改性剂结构中，对冲击改性剂进行阻燃功能化。本发明中的含磷氮丙烯酸酯合成方法简单，成本低，适合工业生产，与其他丙烯酸酯类单体可以通过自由基共聚。采用核壳乳液聚合法制备核壳粒子，具有结构、组成可调的优点；本发明的核壳粒子体现了 “结构改性与功能改性相结合”的设计思想，在不改变核壳冲击改性剂的结构前提下，粒子本身具有一定的阻燃性，有望被用于阻燃材料的增韧。
发明内容
本发明目的是提供一种含磷氮丙烯酸酯及其共聚物核壳粒子的制备方法。
本发明中的含磷氮丙烯酸酯，其结构特征如式（I）所示：
（I）。
本发明中含磷氮丙烯酸酯，其制备方法的特征在于：
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)等摩尔的丙烯酸羟乙酯（HEA），在0-5℃下反应2-4小时后，滴加与苯基磷酰二氯(PDCP)等摩尔的二乙胺，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，即为含磷氮丙烯酸酯单体；反应式如式（II）：
（II）。
本发明中含磷氮丙烯酸酯的共聚物核壳粒子的制备方法，其配方和过程如下：
先将80g蒸馏水、0.4g碳酸氢钠（NaHCO3）和乳化剂2.5g十二烷基硫酸钠（SDS）、1.5gOP-10，加入到250ml的四口烧瓶中，待其溶解后加入引发剂过硫酸钾（KPS）0.1g，升温至60℃，加入30%-50%的内核单体（含磷氮丙烯酸酯与丙烯酸丁酯的质量比为1:4至4:1的单体混合物），升温至70-75℃引发聚合后滴加剩余的内核单体（含磷氮丙烯酸酯与丙烯酸丁酯的质量比为1:4至4:1的单体混合物），反应1-3小时后；补加0.1gKPS，滴加壳层单体（甲基丙烯酸甲酯），反应温度75-80℃，滴加完毕后反应2-6小时，得到聚合物核壳乳液；其中，内核单体与壳层单体质量比为5:5至7:3；总单体与蒸馏水的质量比为4:6至6:4。 此乳液经破乳后，过滤，洗涤，干燥，即得到共聚物核壳粒子。
本发明的益处在于：采用核壳乳液聚合法制备了含磷氮丙烯酸酯的核壳粒子，具有结构、组成可调的优点，在不改变核壳冲击改性剂的结构前提下，粒子本身具有一定的阻燃性，有望被用于阻燃材料的增韧。
附图说明
图1 实施例1中含磷氮丙烯酸酯的核磁氢谱。
图2 实施例1中含磷氮丙烯酸酯的红外光谱。
图3 实施例2和实施例3中共聚物核壳粒子粒径分布曲线。
图4 实施例2和实施例3中共聚物核壳粒子的燃烧释热曲线。
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丙烯酸酯及其共聚物核壳粒子的制备方法，以及该粒子的热分解和燃烧释热性能。
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)80mL加入配有搅拌器的三口烧瓶中并降温至-5-0℃，滴加丙烯酸羟乙酯（HEA）11.6g (0.1mol)，在0-5℃下反应3小时后，滴加二乙胺(DEA)7.3g (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粗产品；产品用乙酸乙酯为流动相，通过中性硅胶柱层析提纯，去除乙酸乙酯后得到浅黄色粘稠液体即为含磷氮丙烯酸酯。
实施例2
先将80ml蒸馏水加入到带有电动搅拌器、温度计、回流冷凝管的250ml的四口烧瓶中，随后开启搅拌装置，加入0.4gNaHCO3、2.5gSDS和1.5gOP-10使其缓慢搅拌。待其溶解后加入0.1gKPS开始升温，温度升至60℃左右后加入20g 内核单体（含磷氮丙烯酸酯15g和丙烯酸丁酯10g的混合物），升温至70-75℃，引发聚合后滴加剩余的内核单体36g （含磷氮丙烯酸酯10g和丙烯酸丁酯26g的混合物），反应2小时后，补加0.1gKPS，滴加壳层单体甲基丙烯酸甲酯21g，继续反应3小时。乳液经破乳后，得到粒径在0.05~0.16微米范围的共聚物核壳粒子。
实施例3
先将80ml蒸馏水加入到带有电动搅拌器、温度计、回流冷凝管的250ml的四口烧瓶中，随后开启搅拌装置，加入0.4gNaHCO3、2.5gSDS和1.5gOP-10使其缓慢搅拌。待其溶解后加入0.1gKPS开始升温，温度升至60℃左右后加入20g 内核单体（含磷氮丙烯酸酯16g和丙烯酸丁酯4g的混合物），升温至70-75℃，引发聚合后滴加剩余的内核单体30g （含磷氮丙烯酸酯24g和丙烯酸丁酯6g的混合物），反应2小时后，补加0.1gKPS，滴加壳层单体甲基丙烯酸甲酯25g，继续反应3小时。乳液经破乳后，得到粒径0.05~0.23微米共聚物核壳粒子。
Claims (5)
1.共聚物核壳粒子，其特征在于：以式(I)所示的含磷氮丙烯酸酯和丙烯酸丁酯为内核单体，以甲基丙烯酸甲酯为壳层单体，通过核壳乳液聚合反应制备；
2.根据权利要求1所述的共聚物核壳粒子的制备方法，其特征在于按照如下方法制备：
先将80g蒸馏水、0.4g碳酸氢钠和乳化剂2.5g十二烷基硫酸钠、1.5gOP-10，加入到250ml的四口烧瓶中，待其溶解后加入引发剂过硫酸钾0.1g，升温至60℃，加入30％-50％的内核单体，升温至70-75℃引发聚合后滴加剩余的内核单体，反应1-3小时后；补加0.1gKPS，滴加壳层单体，反应温度75-80℃，滴加完毕后反应2-6小时，得到聚合物核壳乳液；此乳液经破乳后，过滤，洗涤，干燥，得到共聚物核壳粒子。
3.根据权利要求1或2所述的共聚物核壳粒子，其特征在于所述的内核单体中含磷氮丙烯酸酯与丙烯酸丁酯的质量比为1:4至4:1。
4.根据权利要求1或2所述的共聚物核壳粒子，其特征在于内核单体与壳层单体质量比为5:5至7:3。
5.根据权利要求2所述的共聚物核壳粒子的制备方法，其特征在于总单体与蒸馏水的质量比为4:6至6:4。
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