CN103601629A - 对位或间位官能团化芳香酮类化合物、其制备方法及其光聚合引发剂 - Google Patents

对位或间位官能团化芳香酮类化合物、其制备方法及其光聚合引发剂 Download PDF

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CN103601629A
CN103601629A CN201310511618.XA CN201310511618A CN103601629A CN 103601629 A CN103601629 A CN 103601629A CN 201310511618 A CN201310511618 A CN 201310511618A CN 103601629 A CN103601629 A CN 103601629A
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张永波
王衍超
王亚朋
宋怀海
王智刚
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Shenzhen Youwei Technology Holding Co., Ltd.
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Abstract

本发明公开如结构通式Ⅱ所示的对位或间位取代模式的多官能团芳香酮类化合物、其制备方法、以及以该类化合物作为含烯键不饱和体系自由基聚合的光引发剂。

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对位或间位官能团化芳香酮类化合物、其制备方法及其光聚合引发剂
本申请是发明名称为“对位或间位官能团化芳香酮类化合物、其制备方法及其光聚合引发剂”的中国发明专利申请201010543143.9的分案申请，其申请日是2010年11月12日。
【技术领域】
本发明涉及光引发剂技术领域，特别涉及一些对位或间位取代模式的多官能团化芳香酮类化合物、它们的制备方法，以及以该类化合物为有效成分的含烯键不饱和化合物体系的光聚合引发剂。
【背景技术】
在紫外光（UV）辐射固化材料中，已知一些羟基酮和双芳基酮类化合物可以用作含烯键不饱和化合物体系的自由基光聚合引发剂。例如，下面列出的羟基酮型化合物Darocur1173和Irgacure184，以及双芳基酮类化合物二苯甲酮（BP）和4-苯基二苯甲酮（PBZ）均是已经工业化的成功典范。
Figure BDA0000401914220000011
然而这些光引发剂在工作时普遍产生致癌化合物苯以及包含苯甲醛，丙酮，和环己酮在内的一系列挥发性有害有机化合物（Volatile OrganicCompounds,简称VOCs），由此，造成的环境和健康污染已经成为本领域日益引起关注的问题。已经有相当多的专利文献报道新的化合物，致力于解决这些问题，例如：中国专利CN1288123C，CN1529588A，CN1914560A，CN100548955C，CN100523007C，CN1832912A，和CN1942424A；美国专利US2006/0270748A1，2010/0104979A1，US2005/0239971A1，和US4739052等。其中有代表性的化合物例如下列的Irgacure127和A-C。值得强调的是，这些化合物在光活性官能团和芳环取代基结构的本质结构关系上均呈现对位取代模式。这种模式是由芳环上Friedel-Crafts酰基化反应的特征决定的。
Figure BDA0000401914220000021
这些文献反映出该领域的一个强有力的发展趋势是研发新一代环保和健康友好型的产品，特别是要竭力减轻或消除上述传统市售光引发剂在实际应用时所体现出来的缺陷，包括光解碎片导致致癌性化合物苯/芳烃污染，VOCs释放，以及散发不良气味等。然而，从现实应用的角度考量，新一代光引发剂替代产品的研发不仅要致力于解决上述挑战性问题，提供综合性能优化的新化合物，同时必须尽可能使这些新化合物在经济成本上也要具有相当的竞争力。
【发明内容】
本发明的目的是提出一些新的对位或间位取代模式的多官能团芳香酮类化合物、其制备方法、以及以该类化合物为有效成分的含烯键不饱和化合物体系的自由基光聚合引发剂。
本发明提出的对位或间位取代模式的多官能团化芳香酮类化合物具有以下的结构通式I-III：
Figure BDA0000401914220000031
本发明提出上述多官能团化芳香酮类化合物的制备方法，该方法包括下列步骤：
对于通式I-II的化合物而言，利用双联二苯甲烷结构D和取代2-苯基苯酚E为芳环母核G可调控性地衍生制备一系列新的羟基酮或双芳基酮化合物；
Figure BDA0000401914220000032
对于通式III的化合物而言，反应序列起始于间位氯甲基取代的羟基酮砌块F。一些羟基酮化合物（例如Darocur1173）在路易斯酸和甲醛作用下进行芳环的Friedel-Crafts烷基化反应可以方便地得到间位取代的氯代苄结构的羟基酮砌块F；
Figure BDA0000401914220000033
上述反应是个极为重要的发现，因为自F起始将可以立即制备一系列间位取代的新型单或多官能团羟基酮型化合物，而这些化合物是传统取代芳环上的Friedel-Crafts酰基化反应技术所无法制备的。
本发明还提出以上述多官能团芳香酮类化合物为有效成分的含烯键不饱和化合物体系的自由基光聚合引发剂。
与现有技术相比，本发明特别关注利用价廉易得的工业原材料来作为起点突破口制备新的对位或间位取代模式的多官能团型芳香酮化合物，并将该化合物应用于光引发剂用途，着力解决传统光引发剂VOCs污染问题的同时力求其经济性，以降低成本。
【具体实施方式】
本发明提出的对位或间位取代模式的多官能团化芳香酮类化合物具有以下的结构通式I-III：
Figure BDA0000401914220000041
其中：
R1的具体结构任选如下两种形式之一：
Figure BDA0000401914220000051
R2，R3和R4彼此独立的是一个碳原子数为1-12的支链或直链，含有或不含有环系结构的烷基，或是一个碳原子数为6-12的取代或未取代芳基；R2，R3和R4基团结构彼此独立的也可被1-4个氧原子，氮原子，硅原子，或硫原子间断；R3和R4基团也可形成一个环状结构；R5是氢，R，SiR2R’或SiR3；R6，R7，或R8彼此独立的是氢或R；这里R，R’，R6，R7，或R8的定义彼此独立的与R2，R3和R4相同；
n取值为1-6之间的整数，优选1-4；X是O，S，N，NH，或NR；A是一个n元联结结构；当n取值1时，A-X是OH，OR，SR，NHR，NR2，或季胺盐阳离子形式（R3N+，或R2R’N+）；当n取值大于1时，A-X是N，NR，或季胺盐阳离子形式（RN+，R’RN+，或R2N+）；或A-X-(H)n相应地是一个多元醇，硫醇，酚，羧酸，或胺；
当A-X-(H)n是一个多元醇，硫醇，或酚时，这些多元醇，硫醇，或酚优选如下结构：
Figure BDA0000401914220000052
当A-X-(H)n是一个多元羧酸时，这些多元羧酸优选如下结构：
Figure BDA0000401914220000061
当A-X-(H)n是一个多元胺时，这些多元胺优选如下结构：
Figure BDA0000401914220000062
本发明提出上述多官能团芳香酮类化合物的制备方法，包括下列步骤：
对于通式I-II的化合物而言，利用双联二苯甲烷结构D和取代2-苯基苯酚E为芳环母核G可调控性地衍生制备一系列新的羟基酮或双芳基酮化合物；
对于通式III的化合物而言，反应序列起始于间位氯甲基取代的羟基酮砌块F。一些羟基酮化合物（例如Darocur1173）在路易斯酸和甲醛作用下进行芳环的Friedel-Crafts烷基化反应可以方便地得到间位取代的氯代苄结构F；
Figure BDA0000401914220000072
最后，利用氯代苄结构F制备一系列间位取代的新型单或多官能团羟基酮型化合物。代表性的反应方程式如下。
Figure BDA0000401914220000073
上述方程式中基团R代表通式III中的A-X结构。
对通式为I-II的化合物而言，左侧方框内的起始芳环母核原料G[包括1，4-二苄基苯和R2基保护的2-苯基苯酚]均是已知的化合物，其相关的制备文献依次分别是：Synthetic Communication,1995,25,2029;Journal of theAmerican Chemical Society,2002,124,9458（R2=CH3）。这些芳环母核G和一些酰基给体H在路易斯酸型试剂（常用的如无水氯化铝，氯化铁，氯化锌，或稀土三氟甲基磺酸盐）作用下进行傅瑞德-克拉夫茨酰基化反应得到相应的酰基化产物芳香酮。对于I-II中的一部分化合物而言（即R1取第二种结构通式），酰基化产物即是目标产物，而对于I-II中的另一部分的化合物而言（即R1取第一种结构通式），酰基化产物需要经历卤化（氯化或溴化）反应和碱解反应得到目标产物-----官能团化芳香酮化合物。
Figure BDA0000401914220000081
对于通式为III的目标化合物而言，反应序列起始于间位氯甲基取代的羟基酮砌块F，经由对其氯原子的亲核取代反应和/或对其羟基的衍生化反应即可组装一系列通式III化合物。
Figure BDA0000401914220000091
作为上述通式I表示的化合物的优选结构，可以列举出以下的化合物：
Figure BDA0000401914220000101
作为上述通式II表示的化合物的优选结构，可以列举出以下的化合物：
作为上述通式III表示的化合物的优选结构，当n=1时，可以列举出以下的化合物：
Figure BDA0000401914220000121
作为上述通式III表示的化合物的优选结构，当n>1时，可以列举出以下的化合物：
Figure BDA0000401914220000131
本发明提出的多官能团芳香酮类化合物可用做烯不饱和化合物或含有烯不饱和化合物的混合物的自由基光聚合作用的光引发剂。以下是用做光引发剂的具体制备和应用实例：
实施例一：
Figure BDA0000401914220000141
在氮气保护下，将8.4克1，4-二苄基苯和11.9克异丁酰氯置于400毫升新鲜蒸馏的二氯乙烷中，搅拌下分批徐徐加入15.6克无水三氯化铝粉末。在室温下反应过夜，反应液倒入1升2N盐酸溶液中，分出有机相，水相用300毫升二氯乙烷萃取，合并有机相，饱和食盐水和水各洗涤2次，浓缩残余物在硅胶柱色谱上以己烷/乙酸乙酯为淋洗剂洗脱得到酰基化中间体10.2克。将此中间体溶解于300毫升二氯乙烷中，滴加入10.4克溴素，用薄层色谱法跟踪反应进程。原料消失后旋干溶剂，残余固体在300毫升2N氢氧化钠水溶液中碱解得到目标化合物。粗品在硅胶柱色谱上以己烷/乙酸乙酯为淋洗剂洗脱纯化得到5.3克羟基酮产品。
核磁共振氢谱1H NMR(CDCl3,ppm单位):
7.99-7.94(m,5H),7.33-7.21(m,6H),4.09(s,4H),4.00(s,2H),3.39(s,1H),1.62(s,18H);
核磁共振碳谱13C NMR(CDCl3,ppm单位):
204.0,146.7,145.4,140.3,131.9,130.3,130.1,130.0,129.7,129.3,129.0,128.9,127.2,75.3,41.7,41.5,28.5;
实施例二：
Figure BDA0000401914220000142
第一步：氮气保护下，将5.2克1，4-二苄基苯和6.8克苯甲酰氯置于350毫升新鲜蒸馏的二氯乙烷中，搅拌下分批徐徐加入6.5克无水三氯化铝粉末。在室温下反应6小时，反应液倒入两倍体积的2N盐酸溶液中，分出有机相，水相用300毫升二氯乙烷萃取，合并有机相，饱和食盐水和水各洗涤2次，浓缩残余物在硅胶柱色谱上以己烷/乙酸乙酯为淋洗剂洗脱得到双苯甲酰化中间体5.7克。该中间体的波谱表征数据如下：
核磁共振氢谱1H NMR(CDCl3,ppm单位):
7.80-7.18(m,12H),4.04(s,4H);
核磁共振碳谱13C NMR(CDCl3,ppm单位):
189.2,129.1,133.1,133.0,130.9,128.6,125.1,124.1,123.4,123.0,122.9,122.1,122.0,121.9,121.6,121.4,121.2,120.7,120.3,119.5,118.4,34.9;
第二步：氮气保护下，将1.7克苯甲酰氯和1.8克无水三氯化铝粉末置于200毫升新鲜蒸馏的二氯乙烷中，搅拌半小时后，将上述5.7克中间体分批加入，混合物在室温下反应2小时，反应液倒入两倍体积的2N盐酸溶液中，分出有机相，水相用等体积二氯乙烷萃取2次，合并有机相，饱和食盐水和水各洗涤2次，浓缩残余物在硅胶柱色谱上以己烷/乙酸乙酯为淋洗剂洗脱得到目标化合物3.3克。
碳/氢元素分析：
理论值：碳，86.29%；氢，5.30；
实测值：碳，86.63%；氢，5.62；
实施例三：
Figure BDA0000401914220000151
在氮气保护下，将4.3克双异丁酰基中间体化合物（制备步骤与下列实施例四相同）1,1’-（6-甲氧基联苯基-3,4’-双基）双（2-甲基丙烷-1-酮）溶解于80毫升的干燥二氯甲烷和10毫升四氯化碳混合溶剂中,缓慢滴加4.2克的溴素,室温下搅拌反应至薄层色谱跟踪监测反应完成,减压脱除溶剂（用碱液吸收副产的溴化氢），残余物和100毫升2N的氢氧化钠溶液混合，搅拌反应过夜。反应液倒入两倍体积水中，分离有机相，水相用100毫升二氯甲烷萃取一次，合并有机相，饱和食盐水洗涤，硫酸镁充分干燥，过滤浓缩得到的粗产物在硅胶柱色谱上以己烷/乙酸乙酯为淋洗剂洗脱得到3.6克微黄色目标产物，收率77%。
核磁共振氢谱1H NMR(CDCl3,ppm单位):
8.13-8.09(m,4H),7.63(d,2H,J=8.4Hz),7.05(d,1H,J=9.0Hz),4.17(s,1H),4.16(s,1H),1.68(s,6H),1.65(s,6H);
核磁共振碳谱13C NMR(CDCl3,ppm单位):
204.0,202.4,160.2,142.2,133.0,132.3,129.6,129.5,129.2,126.1,110.6,77.4,76.0,55.8,28.6,28.1;
实施例四：
Figure BDA0000401914220000161
第一步：氮气保护下，将11克无水三氯化铝悬浮在50毫升的干燥二氯甲烷中,缓慢滴加12克的苯甲酰氯,溶液变澄清,然后缓慢将16克2-苯基苯甲醚原料在60毫升二氯甲烷中的溶液缓慢加入上述混合液。室温搅拌2小时后反应完全,然后将反应液倒入冷的两倍体积1N稀盐酸溶液中搅拌至澄清,分离有机相，硫酸镁充分干燥，过滤浓缩得到的单酰基化中间体不需纯化直接用于一步反应。
第二步：在氮气保护下，另将12克无水三氯化铝悬浮在50毫升的干燥二硫化碳中,缓慢滴加13克的苯甲酰氯,溶液变澄清,然后缓慢将上述单酰基化中间体的二硫化碳溶液（50毫升）缓慢加入,混合物在45-55摄氏度搅拌5小时后反应完全。将反应液倒入冷的两倍体积1N稀盐酸溶液中搅拌至澄清,分离有机相，硫酸镁充分干燥，过滤浓缩得到的粗产物在硅胶柱色谱上以己烷/乙酸乙酯为淋洗剂洗脱得到目标产品，微黄色蜡状固体，两步总收率72%。
核磁共振氢谱1H NMR(CDCl3,ppm单位):
7.91-7.72(m,8H),7.67-7.45(m,8H),7.09(d,1H),3.92(s,3H);
核磁共振碳谱13C NMR(CDCl3,ppm单位):
196.3,195.4,160.1,141.8,138.1,137.8,136.4,133.1,132.5,132.1,130.4,130.0,129.8,129.5,128.3,110.7,55.9;
实施例五：
Figure BDA0000401914220000171
第一步：在氮气保护下，将5克2-羟基-2-甲基-1苯基丙烷-1-酮，100毫升干燥的氯仿，和24克无水三氯化铝粉末混合。冷却到4摄氏度时慢慢加入4.5g多聚甲醛，用导管将反应过程中放出的HCl气体导入2N NaOH碱液中吸收，室温搅拌反应12小时，加水淬灭反应，出现大量不溶物，加入2N HCl溶液使其溶解，静置分液，收取下层，上层用乙酸乙酯萃取3次，合并有机层，加无水硫酸钠干燥，旋干溶剂，以乙酸乙酯和正己烷（体积比1:15）为洗脱液在硅胶柱色谱上分离得到黄色油状中间体化合物1-（3-（氯甲基）苯基）-2-羟基-2-甲基丙烷-1-酮，产率33%。
第二步：在氮气保护下，混合25克1-（3-（氯甲基）苯基）-2-羟基-2-甲基丙烷-1-酮，300毫升水和9.4克氢氧化钠，反应液在回流反应12小时，冷却至室温，用400毫升乙酸乙酯萃取3次，无水硫酸钠干燥，旋蒸回收溶剂，以乙酸乙酯和正己烷（体积比1:5）为洗脱液在硅胶柱色谱上分离得到黄色油状产物，产率38%。
核磁共振氢谱1H NMR(CDCl3,ppm单位):
7.89(s,1H),7.82(d,1H,J=7.8Hz),7.39(d,1H,J=7.5Hz),7.29(dd,J=7.8Hz,J=7.5Hz,1H),4.52(s,3H),4.17(s,1H),1.47(s,6H);
核磁共振碳谱13C NMR(CDCl3,ppm单位):
204.9,141.3,134.2,131.2,128.6,128.3,127.9,76.8,64.0,28.1;
实施例六：
Figure BDA0000401914220000181
在氮气保护下，将0.84克1-（3-（氯甲基）苯基）-2-羟基-2-甲基丙烷-1-酮，100毫升水，0.84克苄胺，和2.0克碳酸氢钠混合，反应体系回流12小时，冷却至室温，用200毫升乙酸乙酯萃取3次，无水硫酸钠干燥，旋蒸回收溶剂，以乙酸乙酯和正己烷（体积比1:4）为洗脱液在硅胶柱色谱上分离得到淡黄色油状产物，产率80%。
核磁共振氢谱1H NMR(CDCl3,ppm单位):
8.12(s,2H),7.91(d,2H,J=7.7Hz),7.59(d,2H,J=7.6Hz),7.46-7.22(m,7H),4.22(s,2H),3.64(s,4H),3.61(s,2H),1.64(s,12H);
核磁共振碳谱13C NMR(CDCl3,ppm单位):
204.8,139.9,138.9,133.9,133.2,130.0,128.8,128.5,128.4,128.3,127.2,76.5,58.2,57.7,28.5;
实施例七：
Figure BDA0000401914220000182
在氮气保护下，将13克1-（3-（氯甲基）苯基）-2-羟基-2-甲基丙烷-1-酮和250毫升水，1.5毫升乙醇胺，5.2克碳酸氢钠，在95摄氏度回流反应12小时。反应体系冷却至室温，加400毫升乙酸乙酯萃取3次，无水硫酸钠干燥，旋蒸除去溶剂，以乙酸乙酯和正己烷（体积比1:3）为洗脱液在硅胶柱色谱上分离得到黄色油状产物，产率90%。
核磁共振氢谱1H NMR(CDCl3,ppm单位):
8.04(s,2H),7.87(d,2H,J=7.8Hz),7.47(d,2H,J=7.5Hz),7.36(dd,2H,J=7.8Hz,J=7.5Hz),4.30(s,2H),3.65(s,4H),3.56(t,2H,J=5.4Hz),2.65(s,1H),2.64(t,2H,J=5.4Hz),1.56(s,12H);
核磁共振碳谱13C NMR(CDCl3,ppm单位):
204.5,139.1,134.1,133.0,130.1,128.5,128.3,76.6,58.9,58.1,55.2,28.2;
实施例八：
伴随实施例五中第二步所示反应条件下实验过程，同时可以分离得到51%收率的本实施例八所示结构的目标化合物。
核磁共振氢谱1H NMR(CDCl3,ppm单位):
8.01(s,2H),7.93(d,2H,J=7.8Hz),7.52(d,2H,J=7.5Hz),7.38(dd,J=7.8Hz,J=7.5Hz,2H),4.58(s,4H),4.22(s,2H),1.55(s,12H);
核磁共振碳谱13C NMR(CDCl3,ppm单位):
204.6,138.4,134.2,132.0,129.1,128.9,128.5,76.7,71.8,28.3;
应用实施例：
丙烯酸酯样品体系按下列配方制作（以重量百分比计）：
双酚A环氧丙烯酸酯（Ebecryl605）：30%；氨基丙烯酸酯（Ebecryl7100）：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%；光引发剂：4%。将上述配制混合物喷涂于卡纸板上形成约20微米的涂层，2支80瓦中亚汞灯为光源，变速传送带试验。以指甲反复压刻刮擦不产生印迹为光聚合固化完成的判据。残余气味测试以5个人分别独立地评价气味级别，评估的标准以数字标示如下：0级：没有气味；1级：非常轻微的气味；2级：轻微的气味；3级：明显的气味；4级：强烈的气味；5级：非常强烈的气味。
按代表性实施例合成的6个化合物给出的结果如下：
Figure BDA0000401914220000201
实验结果表明本发明制备的这些光引发剂具有良好的固化性能和低气味特征。
需要强调的是，上述列举的化合物仅是一些优选的示例性结构，不应被视为是限定性结构。本发明申请所涵盖的化合物范围应以权利要求书记载为准。

Claims (6)

1.一种多官能团芳香酮类化合物，具有以下结构通式II： 
Figure FDA0000401914210000011
其中： 
R1的具体结构为： 
R2，R3和R4是彼此独立的是一个碳原子数为1-12的支链或直链，含有或不含有环系结构的烷基，或是一个碳原子数为6-12的未取代芳基；R2，R3和R4基团结构彼此独立的也可被1-4个氧原子，氮原子，硅原子，或硫原子间断；R3和R4基团之间也可以形成一个环状结构；R5是氢，R，SiR2R’或SiR3；R6，R7，或R8彼此独立的是氢或R；这里R，R’，R6，R7，或R8的定义是彼此独立的与R2，R3和R4相同。 
2.化合物，结构如下： 
Figure FDA0000401914210000021
3.权利要求1中通式为II的芳香酮类化合物的制备方法，其特征在于，该方法利用取代2-苯基苯酚E为芳环母核G，将这些芳环母核G和一些酰基给体H在路易斯酸型试剂作用下进行傅瑞德-克拉夫茨酰基化得到相应的酰基化产物芳香酮： 
Figure FDA0000401914210000022
对于通式II中的R1取第二种结构通式的情况，酰基化产物即是目标产物----官能团化芳香酮化合物；而对于II中的R1取第一种结构通 式的情况，酰基化产物需要经历卤化反应和碱解反应得到目标产物----官能团化芳香酮化合物。 
4.根据权利要求3所述的方法，其特征在于，所述的芳环母核原料G包括R2基保护的2-苯基苯酚。 
5.根据权利要求3所述的方法，其特征在于，所述卤化选自氯化或溴化。 
6.一种光聚合引发剂，其特征在于，该光聚合引发剂包括权利要求1中所述的通式II的多官能团芳香酮类化合物： 
Figure FDA0000401914210000031
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