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题名:
催化二氧化碳与环氧化合物制取环碳酸酯的研究
作者: 周亮
答辩日期: 2014-05-30
导师: 侯震山 ; 吾满江·艾力
专业: 有机化学
授予单位: 中国科学院大学
授予地点: 北京
学位: 博士
关键词: 二氧化碳 ; 环氧化合物 ; 环碳酸酯
摘要:

近年来,随着对碳污染的重视和碳化学的发展,二氧化碳作为碳资源的终态,由于储量丰富、无毒和惰性等特点受到越来越多化学工作者的重视。环碳酸酯是化学固定二氧化碳成功的范例之一。环碳酸酯被广泛用作精细化工中间体、非质子性极性溶剂、生物医药前体以及聚碳酸酯的原料。绿色化学是当今国际化学科学研究的前沿和热门领域,利用二氧化碳和环氧化合物通过偶联反应制备环碳酸酯是绿色化学的研究热点之一,受到人们广泛的关注。
本论文以二氧化碳的活化以及二氧化碳和环氧化合物为底物合成环碳酸酯为出发点,探讨了不同催化剂体系的反应过程和机理。
(1)设计合成碘化钾/分子筛MCM-41 体系催化的二氧化碳与环氧化合物环加成合成环碳酸酯的反应,分别探讨了催化剂中的碘化钾含量、催化剂用量、反应温度、时间、二氧化碳压力对反应的影响,筛选出了该催化剂对此反应的最优条件。研究表明当使用碘化钾/分子筛MCM-41 催化体系,在优化条件下,考察了催化剂的重复使用性,该催化剂易于分离,但重复使用能力一般。并在此基础上,将底物进行了扩展,考察了催化剂的普适性。
(2)考虑到碘化钾在分子筛MCM-41 的酸位影响下,容易氧化,所以其重复催化能力一般,在此基础上,设计合成了碘化钾/季戊四醇体系催化的二氧化碳与环氧化合物环加成合成环碳酸酯的反应,分别探讨了不同的碘化钾/季戊四醇摩尔比、催化剂用量、反应温度、时间、二氧化碳压力对反应的影响,并考察了催化剂的重复使用能力以及普适性情况。研究表明当使用碘化钾/季戊四醇催化体系,在优化的条件下,各种环氧化合物都可以生成较高收率的环碳酸酯;并且该催化剂易于分离,使用5 次催化性能只有略微下降。
(3)虽然碘化钾/季戊四醇体系催化效果较好,但长时间放置易吸潮,导致催化剂失活。我们将目标设定为其他易储存的多相催化剂上,设计合成膦酸锆固载腺嘌呤体系催化的二氧化碳与环氧化合物环加成合成环碳酸酯的反应,分别探讨了不同碳链的催化剂1a-e 的催化性能,筛选出最优催化剂1c,并做了相应的表征。紧接着又考察了该催化剂1c 的用量、反应温度、反应时间、二氧化碳压力对反应的影响,并研究了催化剂的重复使用能力以及普适性情况。实验表明当使用膦酸锆固载季铵盐催化体系,在优化条件下,使用6 次催化能力虽有下降,但还在期望值之内。并在此基础上,将底物进行了扩展,拓展了反应底物,研究
催化剂的普适性发现,完成反应的时间较长,但催化效果还是令人较为满意的。
(4)膦酸锆固载腺嘌呤催化体系,反应时间较长,不太符合高效催化剂的原则。我们进一步设计合成膦酸锆固载季铵盐体系催化的二氧化碳与环氧化合物环加成合成环碳酸酯的反应,分别探讨了不同碳链的催化剂1a-e 的催化能力,筛选出最优催化剂1d,并做了相应的表征。紧接着考察了该催化剂1d 的用量、反应温度、时间、二氧化碳压力对反应的影响,并研究了催化剂的重复使用能力以及底物普适性情况。实验表明当使用膦酸锆固载季铵盐催化体系,在优化条件下,循环使用7 次催化性略有下降,但还在期望值之内。并在此基础上,将底物进行了扩展,考察催化剂的普适性,虽然反应时间较长,但催化其他环氧烷烃还
是取得了较满意的结果,论文并且对膦酸锆固载季铵盐型催化剂催化二氧化碳与环氧化合物环加成合成环碳酸酯的反应机理进行了详细讨论。
(5)在膦酸锆固载季铵盐体系的基础上,设计合成膦酸锆固载丁基咪唑体系催化的二氧化碳与环氧化合物环加成合成环碳酸酯的反应,分别探讨了不同碳链的催化剂1a-e 的催化能力,筛选出最优催化剂1d,并做了相应的表征。紧接着又考察了该催化剂1d 的用量、反应温度、反应时间、二氧化碳压力对反应的影响,并研究了催化剂的重复使用能力以及普适性情况。实验表明当使用膦酸锆固载丁基咪唑催化体系,在优化条件下,使用5 次催化能力虽有下降,但还在期望值之内。并在此基础上,拓展了反应底物,研究催化剂的普适性发现,各种环氧化合物都可以生成较高收率的环碳酸酯。论文最后还提出了该催化剂催化二氧化碳与环氧化合物环加成合成环碳酸酯的反应机理。

英文摘要:

Carbon dioxide is the industrial waste product and the main components of the greenhouse gases. Research studies to convert CO2 into many useful products to reduce the carbon dioxide emission are increased over the past decades. Coupling of CO2 and epoxides to synthesis cyclic carbonates is one of the most promising methodologies in this area. Cyclic carbonates can be used as excellent aprotic polar solvents, precursors for producing polycarbonates, fine chemicals, and etc. From the study of activation of carbon dioxide and the Process and mechanism of the formation of cyclic carbonates via epoxides and carbon dioxide catalyzed by the catalysts were detailed documented. (1) The first section described that the low cost KI/MCM-41 catalyst could be easily prepared by the incipient wetness impregnation of MCM-41 with aqueous solution of KI. Several techniques were employed to confirm that KI was well-dispersed onto the surface of MCM-41. The formation of propylene carbonate was used as a test reaction for the activity of catalysts. The present study demonstrates that KI/MCM-41 (KI, 35 wt %) catalyst has given excellent catalytic activity to produce cyclic carbonates from CO2 and epoxides. In the consideration of the experimental results and previous reports, the mechanism of the cycloaddition of cyclic carbonates from epoxides and CO2 catalyzed by supported KI/MCM-41 catalyst was proposed. (2) The second section described a novel and mild method for the synthesis of cyclic carbonate using the KI/PER system free of solvent. The cheapness, easy availability of the reagents, short reaction time, and excellent yield of the products are the advantages that make this protocol a useful addition to the existing methodologies. (3) In third section, a convenient and simple way is presented to immobilize adenine onto zirconium phosphonates. This series of catalyst were prepared for the synthesis of cyclic carbonates from epoxides and carbon dioxide. Their porous and layered structure and surface morphology were characterized by nitrogen adsorption-desorption, XRD, SEM and TEM. The influence of the linkage lengths on the catalytic performance was also investigated. Typical optimized catalyst 1c, with a larger pore diameter, was found to be more catalytic active than the other catalysts. Moreover, the catalyst 1c was easily separated from the reaction systems and could be reused for several times without significant loss of catalytic activity. (4) Zirconium phosphonates-supported bromide quaternary ammonium salts are reported in the fourth section for the first time as recyclable and efficient catalysts for the synthesis of propylene carbonate from propylene oxide and carbon dioxide, which requires no additional organic solvents either for the reaction. This catalyst 1d also has given excellent catalytic activity in the synthesis of various carbonates. The catalyst 1d was easily recovered and could be reused at six times without much loss of activity. In addition, the reaction mechanism was discussed on the basis of the experimental results. (5) In fifth section, a series of zirconium phosphonates-supported 1-butylimidazole catalysts 1a-e could be easily prepared. Several techniques were employed to confirm that the low cost 1-butylimidazole was successfully grafted onto the zirconium phosphonates-supports. The formation of propylene carbonate was used as a test reaction for the activity of catalysts. The present study demonstrates that heterogeneous catalyst 1d has given excellent catalytic activity to produce cyclic carbonates from CO2 and epoxides. Furthermore, it could maintain high catalytic performance and stability without much loss in catalytic activity, even in the fifth reused time. In the consideration of the experimental results and previous reports, the mechanism of the cycloaddition of cyclic carbonates from epoxides and CO2 catalyzed by zirconium phosphonates-supported 1-butylimidazole catalysts was proposed.

内容类型: 学位论文
URI标识: http://ir.xjipc.cas.cn/handle/365002/3429
Appears in Collections:新疆维吾尔自治区精细化工工程技术研究中心_学位论文

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作者单位: 中国科学院新疆理化技术研究所

Recommended Citation:
周亮. 催化二氧化碳与环氧化合物制取环碳酸酯的研究[D]. 北京. 中国科学院大学. 2014-05-30.
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