CN103755741B - 一种含dopo的双酚a-单苯并噁嗪及其制备方法 - Google Patents
一种含dopo的双酚a-单苯并噁嗪及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种含DOPO的双酚A-单苯并噁嗪及其制备方法,其中含DOPO的双酚A-单苯并噁嗪的结构式为:
Description
一、技术领域
本发明涉及的是一种有机高分子材料,具体地说是以双酚A-双苯并噁嗪为原料,制备一种含DOPO的双酚A-单苯并噁嗪的新型苯并噁嗪。
二、背景技术
苯并噁嗪树脂是在传统酚醛树脂的基础上发展起来的一种新型热固性酚醛树脂,一般由酚、胺和多聚甲醛合成而得,是氧、氮原子构成的六元杂环体系,最初是由Holly和Cope在研究Mannich反应中发现。苯并噁嗪树脂不仅具有传统酚醛树脂的优点,还具有合成工艺简单、来源广泛、成本低廉,开环固化不需催化剂且无小分子放出,制品的空隙率低几乎无收缩等优异性能。因此,苯并噁嗪树脂制备具有重要意义,在航空航天、电子、汽车等工业领域的应用受到越来越广泛的重视,具有广阔的应用前景。
但是由于其自身分子结构的一些特点,致使苯并噁嗪树脂有一定的缺点,如缺少含耐热基团,从而使得树脂的高温性能受到了影响,在一定程度上阻碍了苯并噁嗪树脂的应用和发展。
为改善苯并噁嗪树脂的性能,主要采用以下几种方法:利用分子的特点,采用不同的酚源或胺源,合成出不同结构的苯并噁嗪树脂;通过无机纳米粒子改性,引入适当的第二组分,使其均匀地分散在苯并噁嗪树脂基体中,达到改善树脂耐热性能的目的;共混或共聚改性,将其他热固性树脂预聚体或热塑性的树脂与苯并噁嗪共混,改善苯并噁嗪树脂的性能;制备新型的苯并噁嗪树脂。
三、发明内容
本发明旨在提供一种含DOPO的双酚A-单苯并噁嗪及其制备方法,所要解决的技术问题是通过分子设计优化苯并噁嗪单体的结构,以提高苯并噁嗪树脂的耐热性能。
9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)是一种新型阻燃剂中间体,具有活泼的P-H键,易于与双键等发生加成反应,可以作为有机合成原料,制备新的、具有特殊性能的化合物。DOPO及其衍生物合成的阻燃剂具有无卤、无烟、无毒,不迁移,阻燃性能持久等优点,可用于线性聚酯、聚酰胺、环氧树脂、聚氨酯等多种高分子材料阻燃处理。
本发明以DOPO和双酚A-双苯并噁嗪进行反应,合成的含DOPO的双酚A-单苯并噁嗪一方面既保持了苯并噁嗪中原有的优良特性,另一方面,引入含磷基团又提高了树脂的耐热特性。
本发明含DOPO的双酚A-单苯并噁嗪的结构式为:
本发明含DOPO的双酚A-单苯并噁嗪的制备方法如下:
将10-15g双酚A-双苯并噁嗪和100-200g有机溶剂加入反应器中,搅拌0.5-1小时后向反应器中加入5-9gDOPO,在氮气保护下于40-70℃搅拌反应3-5小时,反应结束后用去离子水洗涤,过滤收集沉淀物,于80℃真空干燥后得到目标产物。
本发明反应过程如下:
所述有机溶剂选自四氢呋喃、氯仿或二氧六烷。
与已有技术相比,本发明的有益效果体现在:
1、本发明通过分子设计制备得到含DOPO的双酚A-单苯并噁嗪,该单体制备的苯并噁嗪树脂既继承了双酚A结构的优良性能,又引入了含磷基团,提高了树脂的耐热性能。
2、本发明制备过程使用的原料及溶剂都比较环保,没有使用对环境污染大的材料,合成的树脂也容易处理,且溶剂可以重复使用,是一种环境友好型材料。
3、本发明制备工艺简单,易于实现工业化生产,成本低廉,收率超过90%。
四、附图说明
图1是双酚A-双苯并噁嗪(曲线a)和本发明含DOPO的双酚A-单苯并噁嗪(曲线b)的红外对比分析图。图1中945cm-1,930cm-1处是苯并噁嗪中噁嗪环的特征吸收峰,1115cm-1处为C-N-C不对称伸缩振动特征峰,1230cm-1处是C-O-C不对称伸缩振动特征峰,1497cm-1为苯环上1,2,4-三取代的吸收峰,1600cm-1,1602cm-1为苯环的骨架振动吸收峰,2965cm-1是苯环上碳氢伸缩振动吸收峰,3405cm-1为生成的酚羟基吸收峰。从图1中可以看出,苯并噁嗪中噁嗪环的特征吸收峰发生了迁移,且峰的强度降低。1200cm-1为P=O的特征吸收峰,可能与迁移后的C-O-C不对称伸缩振动特征峰重合,故其峰的强度并未发生明显的降低。综上可知,得到了目标产物。
图2是双酚A-双苯并噁嗪(曲线a)和本发明含DOPO的双酚A-单苯并噁嗪(曲线b)的TG对比分析图。从图2可以看出,双酚A-双苯并噁嗪从312℃开始分解,在373℃分解速度达到最快,在800℃时的残碳率为30.19%。含DOPO的双酚A-单苯并噁嗪从343.9℃开始分解,在459℃分解速度达到最快,在800℃时的残碳率为39.6%。通过对比可以知道,加入DOPO后的苯并噁嗪树脂的起始分解温度将近提高了32℃,最大分解速率提高了将近80℃,残碳率提高了将近9.4%,从而使材料整体的耐热性能有了很好的提高和改善。
五、具体实施方式
实施例1:
在室温条件下,向装有机械搅拌、氮气保护和回流冷凝的250mL圆底烧瓶中加入13.86g(0.3mol)的双酚A-双苯并噁嗪和100ml有机溶剂THF,搅拌0.5小时后,加入6.48g(0.3mol)的DOPO,升温至50℃回流反应4h,反应结束后将反应得到的产物用去离子水洗涤三次,沉淀过滤,得到沉淀物,旋蒸除去溶剂,再于80℃真空干燥,得到18.1g的产品,收率89%。
实施例2:
在室温条件下,向装有机械搅拌、氮气保护和回流冷凝的250mL圆底烧瓶中加入9.24g的双酚A-双苯并噁嗪和100ml有机溶剂三氯甲烷,搅拌1小时后,加入4.32g的DOPO,升温至50℃回流反应4h后结束。将反应得到的产物用去离子水洗涤三次,沉淀过滤,得到沉淀物,旋蒸除去溶剂,再于80℃真空干燥,得到11.6g的产品,收率86%。
实施例3:
在室温条件下,向装有机械搅拌、氮气保护和回流冷凝的250mL圆底烧瓶中加入9.24g的双酚A-双苯并噁嗪和100ml有机溶剂二氧六烷,搅拌1小时后,加入4.32g的DOPO,升温至45℃反应4h后结束。将反应得到的产物用去离子水洗涤三次,沉淀过滤,得到沉淀物,减压旋蒸除去溶剂,再于80℃真空干燥,得到10.8g的产品,收率80%。
Claims (1)
1.一种含DOPO的双酚A-单苯并噁嗪的制备方法,其特征在于按以下步骤操作:
将10-15g双酚A-双苯并噁嗪和有机溶剂加入反应器中,搅拌0.5-1小时后向反应器中加入5-9gDOPO,在氮气保护下于40-70℃搅拌反应3-5小时,反应结束后用去离子水洗涤,过滤收集沉淀物,于80℃真空干燥后得到目标产物;所述有机溶剂选自四氢呋喃、氯仿或二氧六烷;
目标产物的结构式为:
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CN102558233A (zh) * | 2010-12-17 | 2012-07-11 | 萧介夫 | 自苯并恶嗪衍生的磷系双酚、其环氧树脂半固化物、其环氧树脂固化物及其制造方法 |
CN103013111A (zh) * | 2012-09-12 | 2013-04-03 | 常州大学 | 一种含氮磷阻燃剂的制备方法 |
CN103012484A (zh) * | 2012-12-24 | 2013-04-03 | 清华大学深圳研究生院 | 一种含磷苯并恶嗪树脂、制备方法与应用 |
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CN102558233A (zh) * | 2010-12-17 | 2012-07-11 | 萧介夫 | 自苯并恶嗪衍生的磷系双酚、其环氧树脂半固化物、其环氧树脂固化物及其制造方法 |
CN103013111A (zh) * | 2012-09-12 | 2013-04-03 | 常州大学 | 一种含氮磷阻燃剂的制备方法 |
CN103012484A (zh) * | 2012-12-24 | 2013-04-03 | 清华大学深圳研究生院 | 一种含磷苯并恶嗪树脂、制备方法与应用 |
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