本文主要研究内容
作者孟志欣(2019)在《基于离子液体Pickering乳液微反应器用于催化合成氰醇》一文中研究指出:氰醇是有机合成中用途广泛的中间体,可以进一步合成β-氨基醇、α-羟基羧酸、α-氨基腈和α-羟基酯,同时它也是一些重要商业化合物的组成成分。传统氰醇工艺通常采用Lewis酸、Lewis碱等作为催化剂。但是上述工艺存在催化剂用量大、产物选择性低、大量使用有机溶剂、反应条件严苛等问题,不符合绿色化学的要求。离子液体(IL)既可以作为绿色溶剂又可以用作催化剂,反应条件温和,被广泛应用于催化反应体系中。但若直接将其用在间歇式反应体系中,离子液催化剂用量大,难于从反应体系中分离回收。为解决上述问题,一般将均相催化剂离子液固定到载体上,形成固体多相催化剂,填充到固定床中实现连续流动催化反应。然而,这种方法需要对离子液结构单元进行多步改性,会破坏离子液内部结构,同时催化剂活性位点包埋在载体内,难以与反应物充分接触。此外离子液介质粘度大,无法达到工业规模化生产时高速机械搅拌的要求。针对上述问题,本论文提出一种新方法,将乳滴固定床连续流动催化反应的概念拓展到IL/O型的Pickering体系中。采用两种IL(一种作为催化剂,另一种作为溶剂),构建了新型IL/O型的Pickering乳液固定床连续流动反应体系。该体系不会影响IL催化剂单元结构,便于调控催化剂用量。此外,乳滴内的[bmim]BF4介质作为离子“海”通过静电引力防止催化剂的流失,可实现催化剂高效利用。将IL乳液微反应器填充到固定床中,实现了[bmim]Cl在连续流动体系中高效催化合成氰醇。与间歇式反应相比,催化效率提高了2-3倍,连续反应100小时后转化率仍保持在95%,没有明显降低,表现出优异的稳定性。通过理论计算,预测了反应物分子在液滴中的扩散-反应过程,研究了液滴尺寸和催化效率的关系,实验进一步证实液滴在最佳尺寸范围内催化效率最高。由于上述反应体系中,单一IL催化剂难以获得高选择性的手性氰醇,因此基于IL/O型的Pickering乳液体系,构建了多种催化剂协同作用的一锅串联体系。在双金属钛配合物催化剂和有机碱的共同作用下,生成低选择性的氰醇対映体,然后利用生物催化剂CALB酶动力学拆分,(S)-氰醇対映体重新生成反应物,循环往复,从而获得手性产物。由于多种均相催化剂彼此之间会抑制活性,为了进一步提高手性选择性,受生物细胞启发,构建了多级空间微纳反应器。利用三维树枝状介孔SiO2作为催化剂载体(纳米反应器)组装在基于IL的Pickering乳液内部(微米反应器),实现了在微纳多级空间中,多种催化剂高效串联反应的类细胞体系。与直接将催化剂放入间歇式反应体系相比较,催化效率提高了12倍。
Abstract
qing chun shi you ji ge cheng zhong yong tu an fan de zhong jian ti ,ke yi jin yi bu ge cheng β-an ji chun 、α-qiang ji suo suan 、α-an ji jing he α-qiang ji zhi ,tong shi ta ye shi yi xie chong yao shang ye hua ge wu de zu cheng cheng fen 。chuan tong qing chun gong yi tong chang cai yong Lewissuan 、Lewisjian deng zuo wei cui hua ji 。dan shi shang shu gong yi cun zai cui hua ji yong liang da 、chan wu shua ze xing di 、da liang shi yong you ji rong ji 、fan ying tiao jian yan ke deng wen ti ,bu fu ge lu se hua xue de yao qiu 。li zi ye ti (IL)ji ke yi zuo wei lu se rong ji you ke yi yong zuo cui hua ji ,fan ying tiao jian wen he ,bei an fan ying yong yu cui hua fan ying ti ji zhong 。dan re zhi jie jiang ji yong zai jian xie shi fan ying ti ji zhong ,li zi ye cui hua ji yong liang da ,nan yu cong fan ying ti ji zhong fen li hui shou 。wei jie jue shang shu wen ti ,yi ban jiang jun xiang cui hua ji li zi ye gu ding dao zai ti shang ,xing cheng gu ti duo xiang cui hua ji ,tian chong dao gu ding chuang zhong shi xian lian xu liu dong cui hua fan ying 。ran er ,zhe chong fang fa xu yao dui li zi ye jie gou chan yuan jin hang duo bu gai xing ,hui po huai li zi ye nei bu jie gou ,tong shi cui hua ji huo xing wei dian bao mai zai zai ti nei ,nan yi yu fan ying wu chong fen jie chu 。ci wai li zi ye jie zhi nian du da ,mo fa da dao gong ye gui mo hua sheng chan shi gao su ji xie jiao ban de yao qiu 。zhen dui shang shu wen ti ,ben lun wen di chu yi chong xin fang fa ,jiang ru di gu ding chuang lian xu liu dong cui hua fan ying de gai nian ta zhan dao IL/Oxing de Pickeringti ji zhong 。cai yong liang chong IL(yi chong zuo wei cui hua ji ,ling yi chong zuo wei rong ji ),gou jian le xin xing IL/Oxing de Pickeringru ye gu ding chuang lian xu liu dong fan ying ti ji 。gai ti ji bu hui ying xiang ILcui hua ji chan yuan jie gou ,bian yu diao kong cui hua ji yong liang 。ci wai ,ru di nei de [bmim]BF4jie zhi zuo wei li zi “hai ”tong guo jing dian yin li fang zhi cui hua ji de liu shi ,ke shi xian cui hua ji gao xiao li yong 。jiang ILru ye wei fan ying qi tian chong dao gu ding chuang zhong ,shi xian le [bmim]Clzai lian xu liu dong ti ji zhong gao xiao cui hua ge cheng qing chun 。yu jian xie shi fan ying xiang bi ,cui hua xiao lv di gao le 2-3bei ,lian xu fan ying 100xiao shi hou zhuai hua lv reng bao chi zai 95%,mei you ming xian jiang di ,biao xian chu you yi de wen ding xing 。tong guo li lun ji suan ,yu ce le fan ying wu fen zi zai ye di zhong de kuo san -fan ying guo cheng ,yan jiu le ye di che cun he cui hua xiao lv de guan ji ,shi yan jin yi bu zheng shi ye di zai zui jia che cun fan wei nei cui hua xiao lv zui gao 。you yu shang shu fan ying ti ji zhong ,chan yi ILcui hua ji nan yi huo de gao shua ze xing de shou xing qing chun ,yin ci ji yu IL/Oxing de Pickeringru ye ti ji ,gou jian le duo chong cui hua ji xie tong zuo yong de yi guo chuan lian ti ji 。zai shuang jin shu tai pei ge wu cui hua ji he you ji jian de gong tong zuo yong xia ,sheng cheng di shua ze xing de qing chun dui ying ti ,ran hou li yong sheng wu cui hua ji CALBmei dong li xue ca fen ,(S)-qing chun dui ying ti chong xin sheng cheng fan ying wu ,xun huan wang fu ,cong er huo de shou xing chan wu 。you yu duo chong jun xiang cui hua ji bi ci zhi jian hui yi zhi huo xing ,wei le jin yi bu di gao shou xing shua ze xing ,shou sheng wu xi bao qi fa ,gou jian le duo ji kong jian wei na fan ying qi 。li yong san wei shu zhi zhuang jie kong SiO2zuo wei cui hua ji zai ti (na mi fan ying qi )zu zhuang zai ji yu ILde Pickeringru ye nei bu (wei mi fan ying qi ),shi xian le zai wei na duo ji kong jian zhong ,duo chong cui hua ji gao xiao chuan lian fan ying de lei xi bao ti ji 。yu zhi jie jiang cui hua ji fang ru jian xie shi fan ying ti ji xiang bi jiao ,cui hua xiao lv di gao le 12bei 。
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论文作者分别是来自山西大学的孟志欣,发表于刊物山西大学2019-11-12论文,是一篇关于氰醇论文,离子液体论文,乳液论文,微反应器论文,串联反应论文,山西大学2019-11-12论文的文章。本文可供学术参考使用,各位学者可以免费参考阅读下载,文章观点不代表本站观点,资料来自山西大学2019-11-12论文网站,若本站收录的文献无意侵犯了您的著作版权,请联系我们删除。