CN103159796B - 酰基氧膦化合物的制备方法 - Google Patents
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Abstract
本发明涉及辐射聚合固化新材料技术领域，特别涉及一类为通式(I)所示的酰基膦(氧)化合物的化学制备新工艺，其核心特点是以合适的三氯甲基取代的芳烃化合物的格氏型试剂与相应的(取代)卤化磷缩合得到关键的磷‑碳键。本申请披露的工艺以其化学反应技术的新颖性，成本经济竞争力以及环境友好性与文献已知工艺路线相比具有显著的优势。
Description
【技术领域】
本发明涉及辐射聚合固化新材料技术领域，特别涉及一类为通式(I)所示的酰基膦(氧)化合物的化学制备新工艺，其核心特点是以合适的三氯甲基取代的芳烃化合物的(原位制备的)格氏型试剂与相应的(取代)卤化磷缩合得到关键的磷-碳键。本申请披露的工艺以其化学反应技术的新颖性，成本经济竞争力以及环境友好性与文献已知工艺路线相比具有显著的优势。
【背景技术】
在辐射(紫外光或可见光或电子束或X-射线)固化领域，单和双膦酰型芳香酮化合物是具有重要工业应用价值的含烯不饱和体系自由基光聚合起始引发剂，已经成功商业化的代表性产品例如(二苯膦氧基)(均三甲苯基)甲酮[商品名TPO]，乙基苯基(2，4，6-三甲基苯甲酰基)磷酸酯(商品名TPO-L)，以及(苯膦氧基)双(均三甲苯基甲酮)[商品名BAPO]。
关于膦酰型化合物及其结构衍生物的制备方法，文献已有较多披露，典型的例如专利CN101830931，CN101200475A，CN1823077A，CN1659175A和WO2006056541A1。这些技术路线可以经由其关键起始原料清晰地加以区分为两类：
其一是以芳基酸或其相应的酰氯为关键起始原料，经由其与烷氧基膦的Arbuzov反应或与碱金属磷化合物(例如Na3P，Li3P等)的缩合或取代反应制备；
其二是以芳基醛为关键起始原料，经由其与合适的形式为Ar2P(O)H的氧化膦先进行羰基加成反应制得相应的羟基膦氧中间体，然后用过渡金属催化氧化羰基化该中间体制备。
这些文献已披露工艺的突出问题是存在一种或多种下述弊端：反应过程释放大量盐酸酸气和二氧化硫，释放大量污染大气且对臭氧层有显著破坏作用的氯代烷烃，使用高度空气敏感的易燃易爆性碱金属，使用重金属类过渡金属催化剂等。这些工艺环保风险巨大，同时不可避免地导致较高的经济成本。因此，研究和开发新的导向此类化合物的化学合成方法学，具有突出的经济和社会价值。
【发明内容】
本项申请现已首次发现以形式为ArCCl3的芳基三氯甲烷为关键起始原料的酰基膦(氧)化合物的化学制备新工艺。该工艺的核心特点是以合适的原位制备的芳基三氯甲烷的格氏型试剂ArCCl2MgCl与相应的(取代)卤化磷或三卤化磷缩合生成关键的磷-碳键。本申请披露的工艺简单易行，反应过程不排放任何对大气臭氧层有破坏作用的卤代烃，也不使用任何易燃易爆性活泼金属或具有环境污染风险的重金属试剂。
本项申请披露的工艺适用于下述通式(I)所示的酰基膦(氧)化合物：
在通式(I)中，n取值1或2或3；m取值0或1；X是氧或硫，或X是无原子。R1，R2，和R3分别独立地是氢，卤素，碳原子数为1-24(标记为C1-C24，下同)的含有一或多个取代基的支链或直链，含有或不含有C3-C12环系结构的烷基，或是一个C2-C24的含有一或多个取代基的支链或直链，含有或不含有C3-C12环系结构的烯基，或是一个碳原子数为C6-C24的未取代或被取代1-4次的芳基(苯基，萘基，蒽基，或联苯基)或杂芳基。R1，R2，和R3的链段彼此独立地可以被1-6个非连续的氧原子，氮原子，硅原子，或硫原子间断。R1，R2，和R3任意二者之间也可以形成一个环结构。R1，R2，和R3的链段与苯环之间彼此独立地也可以被一个氧，氮，硅，或硫原子插入。
R1，R2，和R3取代的芳基优选的例子是下述结构：
当n取值为2或3时，其两个芳环的满足上述定义的R1，R2，和R3取代基彼此独立地可以相同或不同。
R4是碳原子数为C1-C24的含有一或多个取代基的支链或直链，含有或不含有C3-C12环系结构的烷基，或是一个C2-C24的含有一或多个取代基的支链或直链，含有或不含有C3-C12环系结构的烯基。
R5是氢，OH，碳原子数为C1-C24的含有一或多个取代基的支链或直链，含有或不含有C3-C12环系结构的烷基或满足这样条件的烷氧基或烷巯基或硅烷基，碳原子数为C6-C24的未取代或被取代1-4次的芳基(苯基，萘基，蒽基，或联苯基)或杂芳基或满足这样条件的酚氧基或硫酚基。R5的链段可以被1-6个非连续的氧原子，氮原子，硅原子，硫原子，双键，或三键间断。
通式(I)化合物的新工艺反应通式如下：n当量的三氯甲基取代芳烃前体A和金属M反应原位得到中间体B，B常常无需分离直接和卤代膦C缩合消除MClY后得到结构D所示的膦烷。D和合适的氧化剂作用后水解即可得到五价膦目标化合物(I)。优选的卤代膦C是PCl3(当n＝3，m＝0，Y是氯时)。
M是Mg，Zn，In，Ca，Fe等金属，优选Mg。溶剂是四氢呋喃，N，N-二甲基甲酰胺，六甲基磷酰胺，脂肪或芳香烃，或上述溶剂的混合物，优选四氢呋喃。Y是卤素，优选Cl或Br。氧化剂是过氧化氢，氧气，空气，烷基过氧化物，过氧化酸，或硫(S8)等。
起始原料A可以由R1，R2，和R3取代的芳烃和四氯化碳在路易斯酸(例如AlCl3)催化下进行Friedel-Crafts烷基化反应方便地制备(参见实施例一)。
与上述反应技术相关的，本项申请同时披露适合于制备R1，R2，和R3取代的芳香醛化合物E的新方法：即三氯甲基取代芳烃前体A和金属M反应原位得到中间体B后加水分解即可制备芳醛E。M是Mg，Zn，In，Ca，Fe等金属，优选Mg。溶剂是四氢呋喃，N，N-二甲基甲酰胺，六甲基甲酰胺，脂肪或芳香烃，或上述溶剂的混合物，优选四氢呋喃。
与已知文献方法相比，本发明披露的工艺从原材料成本，反应操作简单性，反应条件的温和程度，以及环境友好性等方面考量均具有显著的优势和经济竞争力。
【具体实施方式】
下面结合具体实施例进一步说明本工艺流程。
实施例一：
第一步：1，3，5-三甲基-2-三氯甲基-苯的合成：室温下在一个反应瓶中混合1.82升四氯化碳和2.5千克无水AlCl3，有效机械搅拌下于一小时内滴加1.5千克均三甲苯(即1，3，5-三甲基苯)，反应体系立即呈现深红色并释放出盐酸气体(注意吸收酸气)，加毕在45摄氏度继续搅拌2小时，反应液徐徐倾倒入等体积1N冰盐酸里，分离有机相，用等体积二氯甲烷萃取2次，合并有机相，无水硫酸钠干燥，过滤，浓缩，油状残液减压蒸馏得到无色1，3，5-三甲基-2-三氯甲基-苯液体，收率约95％。
核磁共振数据：1H-NMR(CDCl3，500MHz)：6.88(s，2H)，2.74(s，6H)，2.25ppm(s，3H)；13C-NMR(CDCl3，125MHz)：139.1，138.1，136.7，132.5，98.3，25.6，20.5ppm。
第二步：在氮气保护下将74克1，3，5-三甲基-2-三氯甲基-苯和500毫升干燥的THF混合，加入9克酸活化的镁屑，维持反应温度在20摄氏度均匀搅拌直至镁屑几乎消失，滴加68克新鲜蒸馏的二苯基氯化膦在200毫升干燥THF中的溶液，滴毕反应体系在室温下搅拌2小时后升温回流反应过夜。反应体系冷却至室温后，脱除大部分溶剂，残余物倒入1升水中，用稀盐酸调节pH在3-4之间，在有效搅拌下加入90克30％过氧化氢溶液。水相用400毫升二氯甲烷萃取三次，合并有机相，硫酸镁干燥，过滤，减压蒸除溶剂，残余物用异丙醚结晶得到87克淡黄色目标化合物纯品。
实施例二：
在氮气保护下将68克1，3，5-三甲基-2-三氯甲基-苯和500毫升干燥的THF混合，加入8.5克酸活化的镁屑，维持反应温度在20摄氏度均匀搅拌直至镁屑几乎消失，然后滴加25克新鲜蒸馏的苯基二氯化膦在100毫升干燥THF中的溶液，滴毕反应体系在室温下搅拌4小时后升温回流反应过夜。反应体系冷却至室温后，脱除大部分溶剂，残余物倒入1升水中，用稀盐酸调节pH在3-4之间，在有效搅拌下加入42克30％过氧化氢溶液。水相用400毫升二氯甲烷萃取三次，合并有机相，硫酸镁干燥，过滤，减压蒸除溶剂，残余物用乙酸乙酯/己烷混合液为淋洗剂在硅胶柱色谱上洗脱得到49克黄色目标化合物纯品。
实施例三：
在氮气保护下将43克1，3，5-三甲基-2-三氯甲基-苯和350毫升干燥的THF混合，加入5.6克酸活化的镁屑，维持反应温度在20摄氏度均匀搅拌直至镁屑几乎消失，然后将反应液缓缓倒入饱和氯化铵溶液中，调节水相pH值至10左右，在氮气下搅拌过夜，用乙酸乙酯萃取水相三次，合并有机相，硫酸镁干燥，过滤，减压蒸除溶剂后残余物减压蒸馏得到22克无色油状液体纯品。
Claims (4)
1.通式(I)所示的酰基膦氧化合物的制备工艺：
在通式(I)中，n取值1或2或3；m取值0；X是氧；
R1，R2，和R3分别独立地是氢或甲基；
当n取值为2或3时，其两个芳环的满足上述定义的R1，R2，和R3取代基彼此独立地可以相同或不同；
R5是氢或苯基；
通式(I)化合物的工艺反应通式如下：n当量的三氯甲基取代芳烃前体A和金属M反应原位得到中间体B，B无需分离直接和卤代膦C缩合消除MClY后得到结构D所示的膦烷；D和合适的氧化剂作用后水解即可得到五价膦目标化合物(I)；
M选自Mg，Zn，In，Ca，Fe中的一种，溶剂是四氢呋喃，N，N-二甲基甲酰胺，六甲基磷酰眩，脂肪或芳香烃，或上述溶剂的混合物；Y是卤素；氧化剂选自过氧化氢，氧气，空气，烷基过氧化物，过氧化酸，或硫中的一种，所述硫为S8；
2.根据权利要求1所述的制备工艺，其特征在于，M为Mg；溶剂为四氢呋喃或N，N-二甲基甲酰胺；Y是Cl或Br。
3.结构E所示的芳香醛化合物的制备工艺：将一个三氯甲基取代芳烃前体A和金属M反应原位得到中间体B后加水分解即可制备芳醛E；M选自Mg，Zn，In，Ca，Fe中的一种；溶剂是四氢呋喃，N，N-二甲基甲酰胺，脂肪或芳香烃，或上述溶剂的混合物，
其中，R1，R2，和R3分别独立地是氢或甲基。
4.根据权利要求3所述的制备工艺，其特征在于，M为Mg；溶剂为四氢呋喃。
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| CN101830931A (zh) * | 2010-04-01 | 2010-09-15 | 天津久日化学工业有限公司 | 2,4,6-三甲基苯甲酰基-二苯基氧化膦及其衍生物的制备方法 |
| CN102875598A (zh) * | 2011-07-11 | 2013-01-16 | 陈婷 | (二苯膦氧基)(均三甲苯基)甲酮和(苯膦氧基)双(均三甲苯基甲酮)的制备方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101830931A (zh) * | 2010-04-01 | 2010-09-15 | 天津久日化学工业有限公司 | 2,4,6-三甲基苯甲酰基-二苯基氧化膦及其衍生物的制备方法 |
| CN102875598A (zh) * | 2011-07-11 | 2013-01-16 | 陈婷 | (二苯膦氧基)(均三甲苯基)甲酮和(苯膦氧基)双(均三甲苯基甲酮)的制备方法 |
Non-Patent Citations (1)
| Title |
|---|
| Formation of organic indoor air pollutants by UV-curing chemistry;T. Salthammer，et al.;《Journal of Photochemistry and Photobiology A: Chemistry》;20021231;第152卷;1-9 * |
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