磷钨杂多酸盐催化氧化环己烯合成己二酸的研究
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摘要
本文采用我国有着充足供应的过氧化氢(H_2O_2)为氧化剂，开展环己烯“绿色”氧化合成己二酸的研究。主要开展了如下几方面工作：
1．针对烯烃—H_2O_2反应体系的特殊性，根据过渡金属催化氧化理论，进行了W(Ⅵ)价态催化剂分子水平上的结构设计。选用具有两亲性结构特点的季铵盐大阳离子，组装入具有特定W(Ⅵ)价态且有优良氧化活性和选择性的磷钨杂多酸根构成杂多酸季铵盐。用红外光谱法及元素分析法对设计、制备出的催化剂进行了表征。
2．对H_2O_2氧化环己烯合成己二酸反应中的催化剂进行了筛选，结果表明磷钨酸十六烷基吡啶铵在不加入任何助剂时，就可达到较好的催化效果；
3．将筛选出的催化剂用于催化H_2O_2氧化环己烯合成己二酸的反应，探讨了反应时间、反应温度、H_2O_2与环己烯摩尔比、催化剂加入量等对反应的影响。采用两次正交实验技术对反应条件进行优化，较适宜的反应条件为：反应时间5.5 h，反应温度90℃，n(H_2O_2)：，n(环己烯)=5.5：1(以0.045 mol环己烯计)，催化剂用量0.3 mmol。在该条件下实验重复性较好，己二酸的平均收率为73.88％，催化剂平均回收率为51.82％；
4．将回收催化剂用于H_2O_2氧化环己烯合成己二酸的反应，在使用五次后，己二酸收率为70.89％，催化活性没有降低。将反应前后的催化剂进行红外光谱分析，发现回收催化剂的IR谱图与Keggin结构[PW_(12)O_(40)]~(3-)的IR谱带的位置、形状及相对强度有很好的一致性。
本研究的工作特点在于：
1．用“绿色”氧化剂H_2O_2进行环己烯氧化合成己二酸，其还原产物为水，无毒、无有害物质，不会给环境带来新的污染，为“绿色”合成过程；
2．本文较系统的考察了不同的磷钨酸季铵盐的催化H_2O_2氧化环己烯的性能，且此类催化剂能够有大部分回收利用。
In this work, H_2O_2 with ample supply in China was used as oxidant in the synthesis of adipic acid from cyclohexene. And we mainly carried out the following aspects of research works:
1. Based on transition metal catalytic oxidation theory, the structure design in the molecule of W(VI) catalyst was carried out in allusion to the particularity of cycloalkene-H_2O_2 reaction system. The amphiphilic structure of quaternary ammonium ions was encased in the excellent oxidation activity and selectiveity of phospho-tungstic acid root that formed quaternary ammonium salts of heteropolyacids. These quaternary ammonium salts of heteropolyacids were characterized by IR and elemental analysis.
2. The filtering catalysts was used in the oxidation of cyclohexene to adipic acid. The result indicated that, in the absence of cocatalysts and acids, the catalytic activity have been very high if cation of quaternary ammonium phospho-tungstic acid was cetypyridine quaternary ammonium ions.
3. The filtering catalysts was used in synthesis of adipic acid reaction. The key factors influencing the oxidation were also studied, such as reaction time, reaction temperature, mole ratio between H_2O_2 and cyclohexene, the amount of catalysts. Orthognol technique was used twice to optimize the reaction conditions, optimal synthesis condition was detailed as: reaction time 5.5 h, reaction temperature 90 ℃, n (H_2O_2): n (C_6H_(10)) - 5.5:1 (based on 0.045 mol cyclohexene), amounts of catalyst was 0.3 mmol. On the condition, the repetition of experiment result were better, the average yield of adipic acid was 73.88%, the average recovery rate of catalyst was 51.82%.
4. The recovery catalyst was used in the oxidation of cyclohexene to adipic acid oxidized by H_2O_2. After catalysis cycle was quintic, catalysis activity didn't reduce. The new catalyst and the used catalyst were analysed by IR, and found IR spectra of recovery catalyst in accord with IR spectra of the Keggin structure of [PW_(12)O_(40)]~(3-).
The points of this work were listed as follows:
1. The green oxidant H_2O_2 is used in this work with the reductive production of H_2O. So there is no baneful materials to release and it can be ascribed to a kind of green progress.
2. A series of quaternary ammonium salts of phospho-tungstic acids catalysts were systematically studied in the oxidation of cyclohexene. And the catalysts could be mostly recovered and utilized.
1．针对烯烃—H_2O_2反应体系的特殊性，根据过渡金属催化氧化理论，进行了W(Ⅵ)价态催化剂分子水平上的结构设计。选用具有两亲性结构特点的季铵盐大阳离子，组装入具有特定W(Ⅵ)价态且有优良氧化活性和选择性的磷钨杂多酸根构成杂多酸季铵盐。用红外光谱法及元素分析法对设计、制备出的催化剂进行了表征。
2．对H_2O_2氧化环己烯合成己二酸反应中的催化剂进行了筛选，结果表明磷钨酸十六烷基吡啶铵在不加入任何助剂时，就可达到较好的催化效果；
3．将筛选出的催化剂用于催化H_2O_2氧化环己烯合成己二酸的反应，探讨了反应时间、反应温度、H_2O_2与环己烯摩尔比、催化剂加入量等对反应的影响。采用两次正交实验技术对反应条件进行优化，较适宜的反应条件为：反应时间5.5 h，反应温度90℃，n(H_2O_2)：，n(环己烯)=5.5：1(以0.045 mol环己烯计)，催化剂用量0.3 mmol。在该条件下实验重复性较好，己二酸的平均收率为73.88％，催化剂平均回收率为51.82％；
4．将回收催化剂用于H_2O_2氧化环己烯合成己二酸的反应，在使用五次后，己二酸收率为70.89％，催化活性没有降低。将反应前后的催化剂进行红外光谱分析，发现回收催化剂的IR谱图与Keggin结构[PW_(12)O_(40)]~(3-)的IR谱带的位置、形状及相对强度有很好的一致性。
本研究的工作特点在于：
1．用“绿色”氧化剂H_2O_2进行环己烯氧化合成己二酸，其还原产物为水，无毒、无有害物质，不会给环境带来新的污染，为“绿色”合成过程；
2．本文较系统的考察了不同的磷钨酸季铵盐的催化H_2O_2氧化环己烯的性能，且此类催化剂能够有大部分回收利用。
In this work, H_2O_2 with ample supply in China was used as oxidant in the synthesis of adipic acid from cyclohexene. And we mainly carried out the following aspects of research works:
1. Based on transition metal catalytic oxidation theory, the structure design in the molecule of W(VI) catalyst was carried out in allusion to the particularity of cycloalkene-H_2O_2 reaction system. The amphiphilic structure of quaternary ammonium ions was encased in the excellent oxidation activity and selectiveity of phospho-tungstic acid root that formed quaternary ammonium salts of heteropolyacids. These quaternary ammonium salts of heteropolyacids were characterized by IR and elemental analysis.
2. The filtering catalysts was used in the oxidation of cyclohexene to adipic acid. The result indicated that, in the absence of cocatalysts and acids, the catalytic activity have been very high if cation of quaternary ammonium phospho-tungstic acid was cetypyridine quaternary ammonium ions.
3. The filtering catalysts was used in synthesis of adipic acid reaction. The key factors influencing the oxidation were also studied, such as reaction time, reaction temperature, mole ratio between H_2O_2 and cyclohexene, the amount of catalysts. Orthognol technique was used twice to optimize the reaction conditions, optimal synthesis condition was detailed as: reaction time 5.5 h, reaction temperature 90 ℃, n (H_2O_2): n (C_6H_(10)) - 5.5:1 (based on 0.045 mol cyclohexene), amounts of catalyst was 0.3 mmol. On the condition, the repetition of experiment result were better, the average yield of adipic acid was 73.88%, the average recovery rate of catalyst was 51.82%.
4. The recovery catalyst was used in the oxidation of cyclohexene to adipic acid oxidized by H_2O_2. After catalysis cycle was quintic, catalysis activity didn't reduce. The new catalyst and the used catalyst were analysed by IR, and found IR spectra of recovery catalyst in accord with IR spectra of the Keggin structure of [PW_(12)O_(40)]~(3-).
The points of this work were listed as follows:
1. The green oxidant H_2O_2 is used in this work with the reductive production of H_2O. So there is no baneful materials to release and it can be ascribed to a kind of green progress.
2. A series of quaternary ammonium salts of phospho-tungstic acids catalysts were systematically studied in the oxidation of cyclohexene. And the catalysts could be mostly recovered and utilized.
引文
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