CN110183492A - 一种含磷氮的阻燃环氧树脂固化剂及其制备方法 - Google Patents
一种含磷氮的阻燃环氧树脂固化剂及其制备方法 Download PDFInfo
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Abstract
本发明属于高分子材料技术领域，公开了一种含磷氮的阻燃型环氧树脂固化剂及其制备方法，所述含磷氮的阻燃环氧树脂固化剂是将甲醛和4‑氨基‑2,2,6,6‑四甲基哌啶在溶剂Ⅰ中，0～50℃下反应，生成含氮中间体；再将含氮中间体与DOPO在溶剂Ⅱ中，在80～120℃下反应，产物经自然冷却、旋蒸、真空干燥处理制得，其分子结构如式(1)所示：
Description
技术领域
本发明属于高分子材料技术领域，尤其涉及一种含磷氮的阻燃环氧树脂固化剂及其制备方法。
背景技术
环氧树脂是一类具有优异的粘结、防腐蚀、绝缘性、成型加工性、高强度等性能的热固性高分子材料，因而被大量应用在涂料、铸造、粘合剂、复合材料、半导体密封材料、电气设备的绝缘材料等领域。但是由于环氧树脂的易燃性使得环氧树脂的应用范围受到了极大的限制。因此，研究环氧树脂阻燃性能对于扩大其在电子电气、航空航天领域的应用有着重要的意义。
在环氧树脂复合材料的阻燃方面，卤系阻燃剂在较低的添加量下就可以达到优异的阻燃效果，但是卤系阻燃剂分解的过程中会释放出大量的有毒气体如卤化氢、二噁英等，更有甚者在燃烧的过程中还会释放出致癌气体如多溴代二苯呋喃等，不仅对人类的健康带来极大的威胁，还会造成严重的环境污染。因此，如何取代卤素，研制高效、低烟、低毒的无卤环保型阻燃剂及新型阻燃环氧树脂材料成为了国内外学者的研究热点。
发明内容
为了解决上述现有技术中存在的不足和缺点，本发明的首要目的在于提供一种含磷氮的阻燃环氧树脂固化剂。该固化剂含有磷、氮两种阻燃元素，既可以参与环氧树脂固化，同时，具有阻燃效率高和无卤、低烟、低毒等特点，符合当今人们保护生态环境的要求，这种阻燃固化剂在燃烧过程中大大减少了有毒气体和腐蚀性气体的产生。
本发明的另一目的在于提供上述含磷氮的阻燃环氧树脂固化剂的制备方法。
本发明的目的是通过以下技术方案实现：
一种含磷氮的阻燃环氧树脂固化剂，其特征在于，所述含磷氮的阻燃环氧树脂固化剂是将甲醛和4-氨基-2,2,6,6-四甲基哌啶在溶剂Ⅰ中，0～50℃下反应，生成含氮中间体；再将含氮中间体与DOPO在溶剂Ⅱ中，在80～120℃下反应，产物经自然冷却、旋蒸、真空干燥处理制得，其分子结构如式(1)所示：
优选地，所述的甲醛和4-氨基-2,2,6,6-四甲基哌啶的摩尔比为1：(1～1.3)。
优选地，所述的含氮中间体和DOPO的摩尔比为(1～1.3)：1。
优选地，所述的溶剂Ⅰ和溶剂Ⅱ均为乙醇、甲醇或二氯甲烷中的一种以上。
优选地，所述的4-氨基-2,2,6,6-四甲基哌啶的摩尔和溶剂Ⅰ的体积比为(0.01～0.03)mol：(10～20)ml。
优选地，所述的DOPO的摩尔和溶剂Ⅱ的体积比为(0.01～0.03)mol：(10～30)ml。
所述的含磷氮的阻燃环氧树脂固化剂的制备方法，包括如下具体步骤：
S1.将甲醛和4-氨基-2,2,6,6-四甲基哌啶在溶剂Ⅰ中，0～50℃下反应，生成含氮中间体；
S2.将步骤S1所得的含氮中间体与DOPO在溶剂Ⅱ中，80～120℃下反应，产物经自然冷却、旋蒸、真空干燥处理，得含磷氮的阻燃环氧树脂固化剂。
优选地，步骤S1中所述反应的时间为2～6h。
优选地，所述溶剂Ⅰ和溶剂Ⅱ均为乙醇、甲醇、二氯甲烷中的一种以上。
优选地，步骤S2中所述反应的时间为8～12h；所述干燥的温度为40～60℃。
本发明的过程用化学反应式表示为：
与现有技术相比，本发明具有以下有益效果：
1.本发明的含磷氮的环氧树脂阻燃固化剂，其兼具固化和阻燃性能，具有阻燃高效，绿色环保的特点。
2.本发明的含磷氮的环氧树脂阻燃固化剂常温下非常稳定，储存期长，且与环氧树脂有良好的相容性，用其固化环氧树脂，对固化物的力学性能影响较小，在作为环氧树脂固化剂的同时，由于磷、氮元素的加入很好的提高了固化物的阻燃性能。
3.本发明的制备方法简单，反应条件易于控制，转化率高，所得产品质量好，适宜推广和应用。
具体实施方式
下面结合具体实施例进一步说明本发明的内容，但不应理解为对本发明的限制。若未特别指明，实施例中所用的技术手段为本领域技术人员所熟知的常规手段。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
实施例1
1.称取0.8g(0.02mol)甲醛溶于20ml乙醇中，将其倒入装有回流冷凝管、温度计和磁子的100ml三口烧瓶中。再称取3.13g(0.02mol)4-氨基-2,2,6,6-四甲基哌啶溶于10ml乙醇中，在室温下用注射器滴加到三口烧瓶中，0.5h滴加完毕后，升温至50℃反应2h，生成含氮中间体；
2.将步骤S1所得的含氮中间体加入9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)4.32g(0.02mol)加入20ml乙醇完全溶解后加热至80℃反应8h，反应完毕后冷却至室温。在50℃下旋蒸，然后将其放入45℃真空干燥箱中24h，得到橘黄色固体，即为含磷氮的阻燃环氧树脂固化剂。
实施例2
与实施例1不同的在于：步骤2中加入DOPO4.32g(0.02mol)和20ml甲醇完全溶解后加热至80℃反应10h，反应完毕后冷却至室温。在50℃下旋蒸，然后将其放入50℃真空干燥箱中22h，得到橘黄色固体，即为含磷氮的阻燃环氧树脂固化剂。
实施例3
与实施例1不同的在于：步骤2中加入DOPO4.32g(0.01mol)和30ml二氯甲烷完全溶解后加热至100℃反应8h，反应完毕后冷却至室温。在50℃下旋蒸，然后将其放入55℃真空干燥箱中20h，得到橘黄色固体，即为含磷氮的阻燃环氧树脂固化剂。
实施例4
与实施例1不同的在于：步骤2中加入DOPO3.24g(0.015mol)和20ml甲醇完全溶解后加热至80℃反应8h，反应完毕后冷却至室温。在50℃下旋蒸，然后将其放入48℃真空干燥箱中23h，得到橘黄色固体，即为含磷氮的阻燃环氧树脂固化剂。
实施例5
与实施例1不同的在于：步骤2中加入DOPO3.24g(0.015mol)和20ml二氯甲烷完全溶解后加热至100℃反应8h，反应完毕后冷却至室温。在50℃下旋蒸，然后将其放入60℃真空干燥箱中18h，得到橘黄色固体，即为含磷氮的阻燃环氧树脂固化剂。
实施例6
与实施例1不同的在于：步骤2中加入DOPO3.24g(0.015mol)和20ml乙醇完全溶解后加热至120℃反应8h，反应完毕后冷却至室温。在60℃下旋蒸，然后将其放入40℃真空干燥箱中24h，得到橘黄色固体，即为含磷氮的阻燃环氧树脂固化剂。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合和简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
Claims (10)
1.一种含磷氮的阻燃环氧树脂固化剂，其特征在于，所述含磷氮的阻燃环氧树脂固化剂是将甲醛和4-氨基-2,2,6,6-四甲基哌啶在溶剂Ⅰ中，0～50℃下反应，生成含氮中间体；再将含氮中间体与DOPO在溶剂Ⅱ中，在80～120℃下反应，产物经自然冷却、旋蒸、真空干燥处理制得，其分子结构如式(1)所示：
2.根据权利要求1所述的含磷氮的阻燃环氧树脂固化剂，其特征在于，所述的甲醛和4-氨基-2,2,6,6-四甲基哌啶的摩尔比为1：(1～1.3)。
3.根据权利要求1所述的含磷氮的阻燃环氧树脂固化剂，其特征在于，所述的含氮中间体和DOPO的摩尔比为(1～1.3)：1。
4.根据权利要求1所述的含磷氮的阻燃环氧树脂固化剂，其特征在于，所述的溶剂Ⅰ和溶剂Ⅱ均为乙醇、甲醇或二氯甲烷中的一种以上。
5.根据权利要求1所述的含磷氮的阻燃环氧树脂固化剂，其特征在于，所述的4-氨基-2,2,6,6-四甲基哌啶的摩尔和溶剂Ⅰ的体积比为(0.01～0.03)mol：(10～20)ml。
6.根据权利要求1所述的含磷氮的阻燃环氧树脂固化剂，其特征在于，所述的DOPO的摩尔和溶剂Ⅱ的体积比为(0.01～0.03)mol：(10～30)ml。
7.根据权利要求1-6任一项所述的含磷氮的阻燃环氧树脂固化剂的制备方法，其特征在于，包括如下具体步骤：
S1.将甲醛和4-氨基-2,2,6,6-四甲基哌啶在溶剂Ⅰ中，0～50℃下反应，生成含氮中间体；
S2.将步骤S1所得的含氮中间体与DOPO在溶剂Ⅱ中，80～120℃下反应，产物经自然冷却、旋蒸、真空干燥处理，得含磷氮的阻燃环氧树脂固化剂。
8.根据权利要求7所述的含磷氮的阻燃环氧树脂固化剂的制备方法，其特征在于，步骤S1中所述反应的时间为2～6h。
9.根据权利要求7所述的含磷氮的阻燃环氧树脂固化剂的制备方法，其特征在于，所述溶剂Ⅰ和溶剂Ⅱ均为乙醇、甲醇、二氯甲烷中的一种以上。
10.根据权利要求7所述的含磷氮的阻燃环氧树脂固化剂的制备方法，其特征在于，步骤S2中所述反应的时间为8～12h；所述干燥的温度为40～60℃。
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