CN105732709A - 一种光引发剂2,4,6-三甲基苯甲酰二环己基氧膦,制备方法及其应用 - Google Patents
一种光引发剂2,4,6-三甲基苯甲酰二环己基氧膦,制备方法及其应用 Download PDFInfo
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Abstract
本发明涉及光引发剂2,4,6?三甲基苯甲酰二环己基氧膦的制备方法,在氩气保护下,二环己基氯化膦、金属钠、叔丁醇在甲苯溶剂中反应得到中间体Ⅰ;中间体Ⅰ与2,4,6?三甲基苯甲酰氯反应得到中间体Ⅱ;温度在30?35℃条件下,中间体Ⅱ与双氧水反应得到2,4,6?三甲基苯甲酰二环己基氧膦,液相纯度达到99.21%。该制备方法,操作简单,工艺先进,溶剂可回收利用,易于工业化生产。
Description
技术领域
本发明属于光引发剂领域,具体涉及一种光引发剂2,4,6-三甲基苯甲酰二环己基氧磷制备方法。
技术背景
酰基氧化膦类光引发剂与D-1173,I-184,D-2959等α-羟基酮类光引发剂相比具有如下优点:(1)它们的最大吸收波长在350-380nm,其光谱吸收延伸至可见光区;(2)酰基氧化膦能够穿透较深的涂层,这类光引发剂可以配制较高浓度,应用于厚涂层的固化;(3)酰基氧化膦的激发态寿命很短,因此不易被其他物质淬灭失活,可以应用在以苯乙烯为稀释单体的不饱和聚酯配方中;(4)酰基氧化膦分解速度快,产生的自由基量子效率高,光固化速度快,光照后不存在剩余引发剂,没有小分子化合物残存于固化体系中,所以不析出,不发生黄变现象,同时有利于防止老化过程中高聚物的降解;(5)酰基氧化膦挥发性低。正是酰基氧化膦类化合物具有上述许多优点而被广泛应用于光引发涂料(如粉末涂料、光纤涂料)、成像印刷板、光致刻蚀剂、UV固化粘合剂、浮雕印刷板等方面,因此研发新型酰基氧化膦类光引发剂十分必要。
发明内容
本发明的任务是提供一种工艺简单、收率高、成本低、污染小、产品质量好、适合工业化生产的2,4,6-三甲基苯甲酰二环己基氧膦制备方法。为解决上述技术问题,本发明的目的是这样实现:一种光引发剂2,4,6-三甲基苯甲酰二环己基氧膦,该化合物具有如下化学结构式:
本发明采用以下技术方案:
A:氩气保护下,向装有有机溶剂的反应器中加入有机溶剂,开启搅拌,再加入金属钠,升温至80-110℃保温半小时,再向反应釜中缓慢滴加二环己基氯化膦,控制反应液温度80-110℃,保温3-4h,控制反应釜内的温度80-110℃,再滴加叔丁醇,滴加完叔丁醇后,在80-110℃继续反应1.0-1.5h,含有中间体Ⅰ的、甲苯溶液,无需分离,直接用于中间体Ⅱ的制备;
该步骤中,二环己基氯化膦、叔丁醇、金属钠的物质的量之比为1:1-4:1-5。所述的有机溶剂为苯、甲苯或二甲苯中的任一种,优选甲苯,有机溶剂的重量为金属钠重量10-20倍;所述的优选反应温度为100-105℃。
B:将含有中间体Ⅰ的有机溶剂冷却到20-30℃,向反应器中缓慢滴加2,4,6-三甲基苯甲酰氯,滴加完后,控制反应液温度10-40℃(优选反应温度为20-30℃),反应约2.0-3.0h,得到含有中间体Ⅱ的有机溶液,无需分离,直接用于2,4,6-三甲基苯甲酰二环己基氧膦的制备;
C:将含有中间体Ⅱ的有机溶液温度降至室温,再滴加质量分数为30%的双氧水,滴加完后,控制反应釜内温在20-50℃反应1.0-2.0h(优选反应温度为30-35℃),反应完成后,向反应器中加入质量分数为10%的碳酸氢钠水溶液,在20-50℃下保温搅拌30min,静置,分层,有机相用纯化水洗涤三次,控制温度在70-80℃,减压蒸出甲苯,用石油醚纯结晶得得到联苯基四(2,4,6-三甲基苯甲酰基)氧化膦,反应方程式如下:
本发明的有益效果如下:
1、提供了2,4,6-三甲基苯甲酰二环己基氧膦的完整的制备方法。
2、制备的2,4,6-三甲基苯甲酰二环己基氧膦光解产生的苯甲酰自由基和膦酰自由基都能引发单体聚合,全部参加光聚合反应,该引发剂是能应用于有色体系和深层固化的新型酰基氧化膦光引发剂。
3、用该制备方法制得的2,4,6-三甲基苯甲酰二环己基氧膦,液相纯度高,可达99.21%。
具体实施方式
以下结合实施例对本发明作进一步说明,但本发明要求保护的范围并不局限于实施例表述的范围。
实施例1:
一种2,4,6-三甲基苯甲酰二环己基氧膦的制备方法,该方法由以下步骤组成:
中间体Ⅰ的制备
氩气保护下,在反应器中,加入甲苯100mL,开启搅拌,依次加金属钠2.3g(0.1mol),升温至100-105℃保温半小时,向反应釜中缓慢滴加二环己基氯化膦23.3g(0.10mol),约2h滴完,控制反应液温度100-105℃,保温3-4h。控制反应釜内的温度100-105℃,缓慢滴加叔丁醇7.4g(0.1mol),约0.5-1h滴完,滴加完叔丁醇后,在100-105℃继续反应1.0-1.5h,含有中间体Ⅰ的、甲苯溶液,无需分离,直接用于中间体Ⅱ的制备。
中间体Ⅱ的制备
将含有中间体Ⅰ的二甲苯溶液冷却到20-30℃,向反应器中缓慢滴加2,4,6-三甲基苯甲酰氯18.3g(0.1mol),约0.5-1h滴完,控制反应液温度30-35℃,滴加完成后,继续反应约2.0-3.0h,得到含有中间体Ⅱ的二甲苯溶液,无需分离,直接用于2,4,6-三甲基苯甲酰二环己基氧膦的制备。
2,4,6-三甲基苯甲酰二环己基氧膦的制备
将含有中间体Ⅱ的甲苯溶液温度降至室温,缓慢滴加30%的双氧水34.0g,约0.5h滴完,控制反应釜内温在30-35℃反应1.0-2.0h,反应完成后,向反应器中加入60g 10%的碳酸氢钠水溶液,在30-35℃下保温搅拌30min,静置,分层,有机相用纯化水洗涤三次,控制温度在70-80℃,减压蒸出甲苯,用石油醚纯结晶得纯品2,4,6-三甲基苯甲酰二环己基氧膦,收率79.5%。1HNMR(CDCl3,400MHz)δ:4.21(s,3H,Ar-H),2.46(s,6H,2CH3),2.27(s,3H,CH3),1.72-1.51(m,10H,CH2),1.45-1.38(m,12H,CH2).
实施例2:
将叔丁醇的量增大至14.8g(0.2mol)、钠的量增大至4.6g(0.2mol),其它同实例一,2,4,6-三甲基苯甲酰二环己基氧膦收率83.2%。
实施例3:
将叔丁醇的量增大至15.2g(0.3mol)、钠的量增大至6.9g(0.3mol),其它同实例一,2,4,6-三甲基苯甲酰二环己基氧膦收率88.7%。
实施例4:
将叔丁醇的量增大至29.6g(0.4mol)、钠的量增大至9.2g(0.4mol),其它同实例一,2,4,6-三甲基苯甲酰二环己基氧膦收率84.3%。
实施例5:
钠的量增大至11.5g(0.5mol),其它同实例一,2,4,6-三甲基苯甲酰二环己基氧膦收率82.4%。
实施例6:
将实施例所制得的光引发剂2,4,6-三甲基苯甲酰二环己基氧膦、市售的TPO(2,4,6-三甲基苯甲酰基二苯基氧化膦)分别以4%(质量比)比例加入丙烯酸环氧树酯样品体系(配方为:双酚A环氧丙烯酸酯30%;氨基丙烯酸酯8%;丙氧基化甘油三丙烯酸酯30%;己二醇二丙烯酸酯24%;聚硅氧烷丙烯酸酯0.5%;乙氧基季戊四醇四丙烯酸酯3.5%),均匀涂布在经过清洗、干燥的敷铜板上,用1kw高压汞灯辐照,使得液膜聚合固化,测定结果如下表1所示。
表1 本发明光引发剂对丙烯酸环氧树酯的阻燃效果
Claims (7)
1.一种光引发剂2,4,6-三甲基苯甲酰二环己基氧膦,其特征在于,其化学结构式如下:
2.一种光引发剂2,4,6-三甲基苯甲酰二环己基氧膦制备方法,其特征在于该制备方法包括以下步骤:
A:氩气保护下,向装有有机溶剂的反应器中加入有机溶剂,开启搅拌,再加入金属钠,升温至100-105℃保温半小时,再向反应釜中缓慢滴加二环己基氯化膦,控制反应液温度100-105℃,保温3-4h,控制反应釜内的温度100-105℃,再滴加叔丁醇,滴加完叔丁醇后,在100-105℃继续反应1.0-1.5h,含有中间体Ⅰ的、甲苯溶液,无需分离,直接用于中间体Ⅱ的制备;
B:将含有中间体Ⅰ的有机溶剂冷却到20-30℃,向反应器中缓慢滴加2,4,6-三甲基苯甲酰氯,滴加完后,控制反应液温度10-40℃,反应约2.0-3.0h,得到含有中间体Ⅱ的有机溶液,无需分离,直接用于2,4,6-三甲基苯甲酰二环己基氧膦的制备;
C:将含有中间体Ⅱ的有机溶液温度降至室温,再滴加质量分数为30%的双氧水,滴加完后,控制反应釜内温在20-50℃反应1.0-2.0h,反应完成后,向反应器中加入质量分数为10%的碳酸氢钠水溶液,在20-50℃下保温搅拌30min,静置,分层,有机相用纯化水洗涤三次,控制温度在70-80℃,减压蒸出甲苯,用石油醚纯结晶得得到联苯基四(2,4,6-三甲基苯甲酰基)氧化膦,反应方程式如下:
3.根据权利要求2所述的光引发剂2,4,6-三甲基苯甲酰二环己基氧膦制备方法,其特征在于:步骤A中,二环己基氯化膦、叔丁醇、金属钠的物质的量之比为1:1-4:1-5。
4.根据权利要求1所述的光引发剂2,4,6-三甲基苯甲酰二环己基氧膦制备方法,其特征在于:步骤A中,所述的有机溶剂为苯、甲苯或二甲苯中的任一种,优选甲苯,有机溶剂的重量为金属钠重量10-20倍;所述的优选反应温度为100-105℃。
5.根据权利要求1所述的光引发剂2,4,6-三甲基苯甲酰二环己基氧膦制备方法,其特征在于:步骤B中,所述的优选反应温度为20-30℃。
6.根据权利要求1所述的光引发剂2,4,6-三甲基苯甲酰二环己基氧膦制备方法,其特征在于:步骤C中,所述的优选反应温度为30-35℃。
7.根据权利要求1-6述的任意一项所述的光引发剂2,4,6-三甲基苯甲酰二环己基氧膦在丙烯酸环氧树脂中的应用。
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