固载化氨基酚型席夫碱氧钒（Ⅳ）配合物的制备及其催化氧化性能的研究
发布时间：2018-07-31 19:45
【摘要】：在催化剂的作用下,以分子氧或空气为氧化剂实现醇类物质向羰基化合物的转变,这是备受关注的绿色化氧化过程。固载化席夫碱过渡金属配合物催化剂在催化分子氧氧化醇类物质的过程中具有优良的催化活性、选择性和良好的重复使用性能,可以有效地将醇类物质氧化为相应的醛或酮。本研究通过分子设计,以交联聚苯乙烯微球为载体,经过两步大分子反应,制备了键合有氨基酚型席夫碱配基的功能微球CPSAGAP,然后使之分别与硫酸氧钒、醋酸钴、硝酸铜、醋酸锰四种物质发生配位螯合反应,制备了多种表面固载有氨基酚型席夫碱配合物的固体催化剂微球,并将它们用于催化分子氧氧化环己醇和1-苯乙醇的反应中,探究了这些非均相催化剂的催化活性、选择性和催化氧化机理。本文的研究结果在绿色化的醇类物质催化氧化领域中,具有重要的科学意义与潜在的应用价值。使乙醛酸与氯甲基化交联聚苯乙烯(CMCPS)微球的氯甲基发生酯化反应,从而将醛基(GA)引入交联聚苯乙烯(CPS)微球表面,得到改性微球CPS-AG,再以间氨基苯酚(MAP)为试剂,与微球CPS-AG表面的醛基发生席夫碱反应,制得了表面键合有氨基酚型席夫碱配基的功能微球CPS-AGAP,考察了主要因素对制备功能微球的影响规律,优化了反应条件。最后使微球分别与硫酸氧钒、醋酸钴、硝酸铜、醋酸锰四种物质发生配位螯合反应,制得了四种表面固载有氨基酚型席夫碱过渡金属配合物的固体催化剂微球CPS-[VO(AGAP)_2]、CPS-[Co(AGAP)_2]和CPS-[Mn(AGAP)_2]、CPS-[Cu(AGAP)_2],采用红外光谱(FT-IR)、固体紫外(UV)及扫描电子显微镜(SEM)对催化剂微球进行了充分表征。经研究发现,溶剂的极性有利于乙醛酸与CMCPS微球之间的酯化反应,极性较强的N,N-二甲基乙酰胺为适宜的反应溶剂;90℃为适宜的反应温度。在适宜反应条件下,CMCPS微球的氯甲基转化率可以达到82%。所制得的固体催化剂微球CPS-[VO(AGAP)_2]、CPS-[Co(AGAP)_2]、CPS-[Mn(AGAP)_2]和CPS-[Cu(AGAP)_2],其表面金属物种的固载量分别达到0.78 mmol/g、0.75 mmol/g、0.71 mmol/g、0.69mmol/g。将四种固载有氨基酚型席夫碱过渡金属配合物微球用于环己醇和1-苯乙醇的分子氧催化氧化过程,考察了主要因素对环己醇和1-苯乙醇催化氧化的影响规律,探究了催化氧化的机理。实验结果表明,在环己醇环己醇和1-苯乙醇的催化反应中,四种催化剂微球均表现出一定的催化活性与优良的选择性。催化氧化反应具有高选择性,环己酮和苯乙酮为反应的唯一产物。四种催化剂微球的催化效果相比,催化效果顺序为CPS-[VO(AGAP)_2]CPS-[Co(AGAP)_2]CPS-[Mn(AGAP)_2]CPS-[Cu(AGAP)_2],催化剂微球CPS-[VO(AGAP)_2]的催化效果最佳。0.78 mmol催化剂微球CPS-[VO(AGAP)_2],在90℃下,反应30 h,催化剂微球CPS-[VO(AGAP)_2]可将环己醇高效的转化为环己酮,转化率达到64%。0.546 mmol催化剂微球CPS-[VO(AGAP)_2],在80℃下,反应28h,催化剂微球CPS-[VO(AGAP)_2]可将1-苯乙醇高效的转化为苯乙酮,转化率达到78%。氧钒催化剂CPS-[VO(AGAP)_2]之所以有高的催化活性,主要原因在于高价态钒原子对分子氧具有高亲和性,且具有高配位数。制备的非均相催化剂CPS-[VO(AGAP)_2]重复使用7次后,环己醇的转化率基本保持稳定在61%左右,1-苯乙醇的转化率基本保持稳定在73%左右。显然,固载化的催化剂CPS-[VO(AGAP)_2]具有良好的循环使用性能。
[Abstract]:Under the action of catalyst, the conversion of alcohols to carbonyl compounds is realized with molecular oxygen or air as oxidant. This is a highly concerned green oxidation process. The immobilized Schiff base transition metal complexes have excellent catalytic activity, selectivity and good repetition in the process of catalytic oxidation of alcohols by molecular oxygen. Using properties, the alcohols can be effectively oxidized to corresponding aldehydes or ketones. Through molecular design, a functional microsphere CPSAGAP bonded with aminophenol type Schiff base ligand was prepared through two steps of macromolecular reaction, and then it was made with vanadium sulfate, cobalt acetate, copper nitrate, and manganese acetate, four. A variety of solid catalyst microspheres containing aminophenol type Schiff base complexes have been prepared and used to catalyze the reaction of cyclohexanol and 1- phenolols. The catalytic activity, selectivity and catalytic oxidation mechanism of these heterogeneous catalysts are investigated. The results of this paper are in this paper. In the field of catalytic oxidation of green alcohols, it has important scientific significance and potential application value. The glyoxylic acid is esterified with chloromethyl methylation of chloromethylated polystyrene (CMCPS) microspheres, and aldehyde group (GA) is introduced into the surface of crosslinked polystyrene (CPS) microsphere, and the modified microsphere CPS-AG, and then interaminophenol (MAP), is obtained. A functional microsphere CPS-AGAP was prepared for the surface bonding of Schiff base with aminophenol type Schiff base on the surface of the microsphere CPS-AG. The effect of the main factors on the preparation of functional microspheres was investigated, and the reaction conditions were optimized. Finally, the microspheres were made with four substances, vanadium sulfate, cobalt acetate, copper nitrate, and manganese acetate, respectively. Four kinds of solid catalyst microspheres, CPS-[VO (AGAP) _2], CPS-[Co (AGAP) _2] and CPS-[Mn (AGAP) _2], CPS-[Cu (AGAP) _2], were prepared by the chelating reaction. The catalyst microspheres were fully characterized by infrared spectroscopy, solid UV and scanning electron microscopy. It is found that the polarity of the solvent is beneficial to the esterification between glyoxylic acid and CMCPS microspheres. The very strong N, N- two methyl acetamide is a suitable reaction solvent, and the suitable reaction temperature is 90 C. Under the suitable reaction conditions, the conversion rate of chloromethyl of CMCPS microspheres can reach to the solid catalyst microsphere CPS-[VO (AGAP) _2] produced by 82%.. CPS-[Co (AGAP) _2], CPS-[Mn (AGAP) _2] and CPS-[Cu (AGAP) _2], the solid load of the surface metal species reached 0.78 mmol/g, 0.75 mmol/g, 0.71 mmol/g. Four kinds of solid containing aminophenol type Schiff base transition metal complexes were used in the molecular oxygen catalytic oxidation process of cyclohexanol and ethyl alcohol. The main factors were investigated. The mechanism of catalytic oxidation of hexanol and 1- benzol was investigated. The experimental results showed that in the catalytic reaction of cyclohexanol cyclohexanol and 1- Benzol, the four catalyst microspheres showed a certain catalytic activity and excellent selectivity. The catalytic oxidation reaction had high selectivity, and cyclohexanone and acetophenone were reacted. The catalytic effect of the four catalyst microspheres is CPS-[VO (AGAP) _2]CPS-[Co (AGAP) _2]CPS-[Mn (AGAP) _2]CPS-[Cu (AGAP) _2], and the catalyst microsphere CPS-[VO (AGAP) _2] has the best catalytic effect. At 90, the reaction is 30. The conversion of hexanol to cyclohexanone, the conversion of 64%.0.546 mmol catalyst microsphere CPS-[VO (AGAP) _2], at 80 C, reaction 28h, the catalyst microsphere CPS-[VO (AGAP) _2] can convert 1- benzophenone into acetophenone, the conversion rate reaches the high catalytic activity of 78%. oxygen vanadium catalyst. The main reason is high price. The state vanadium atom has high affinity to molecular oxygen and has high coordination number. After repeated use of the heterogeneous catalyst CPS-[VO (AGAP) _2] for 7 times, the conversion rate of cyclohexanol is basically stable at about 61%, and the conversion rate of 1- benzene ethanol is basically around 73%. Obviously, the immobilized catalyst CPS-[VO (AGAP) _2] has a good cycle. Use performance.
【学位授予单位】：中北大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4;O643.36
本文编号：2156642
[Abstract]:Under the action of catalyst, the conversion of alcohols to carbonyl compounds is realized with molecular oxygen or air as oxidant. This is a highly concerned green oxidation process. The immobilized Schiff base transition metal complexes have excellent catalytic activity, selectivity and good repetition in the process of catalytic oxidation of alcohols by molecular oxygen. Using properties, the alcohols can be effectively oxidized to corresponding aldehydes or ketones. Through molecular design, a functional microsphere CPSAGAP bonded with aminophenol type Schiff base ligand was prepared through two steps of macromolecular reaction, and then it was made with vanadium sulfate, cobalt acetate, copper nitrate, and manganese acetate, four. A variety of solid catalyst microspheres containing aminophenol type Schiff base complexes have been prepared and used to catalyze the reaction of cyclohexanol and 1- phenolols. The catalytic activity, selectivity and catalytic oxidation mechanism of these heterogeneous catalysts are investigated. The results of this paper are in this paper. In the field of catalytic oxidation of green alcohols, it has important scientific significance and potential application value. The glyoxylic acid is esterified with chloromethyl methylation of chloromethylated polystyrene (CMCPS) microspheres, and aldehyde group (GA) is introduced into the surface of crosslinked polystyrene (CPS) microsphere, and the modified microsphere CPS-AG, and then interaminophenol (MAP), is obtained. A functional microsphere CPS-AGAP was prepared for the surface bonding of Schiff base with aminophenol type Schiff base on the surface of the microsphere CPS-AG. The effect of the main factors on the preparation of functional microspheres was investigated, and the reaction conditions were optimized. Finally, the microspheres were made with four substances, vanadium sulfate, cobalt acetate, copper nitrate, and manganese acetate, respectively. Four kinds of solid catalyst microspheres, CPS-[VO (AGAP) _2], CPS-[Co (AGAP) _2] and CPS-[Mn (AGAP) _2], CPS-[Cu (AGAP) _2], were prepared by the chelating reaction. The catalyst microspheres were fully characterized by infrared spectroscopy, solid UV and scanning electron microscopy. It is found that the polarity of the solvent is beneficial to the esterification between glyoxylic acid and CMCPS microspheres. The very strong N, N- two methyl acetamide is a suitable reaction solvent, and the suitable reaction temperature is 90 C. Under the suitable reaction conditions, the conversion rate of chloromethyl of CMCPS microspheres can reach to the solid catalyst microsphere CPS-[VO (AGAP) _2] produced by 82%.. CPS-[Co (AGAP) _2], CPS-[Mn (AGAP) _2] and CPS-[Cu (AGAP) _2], the solid load of the surface metal species reached 0.78 mmol/g, 0.75 mmol/g, 0.71 mmol/g. Four kinds of solid containing aminophenol type Schiff base transition metal complexes were used in the molecular oxygen catalytic oxidation process of cyclohexanol and ethyl alcohol. The main factors were investigated. The mechanism of catalytic oxidation of hexanol and 1- benzol was investigated. The experimental results showed that in the catalytic reaction of cyclohexanol cyclohexanol and 1- Benzol, the four catalyst microspheres showed a certain catalytic activity and excellent selectivity. The catalytic oxidation reaction had high selectivity, and cyclohexanone and acetophenone were reacted. The catalytic effect of the four catalyst microspheres is CPS-[VO (AGAP) _2]CPS-[Co (AGAP) _2]CPS-[Mn (AGAP) _2]CPS-[Cu (AGAP) _2], and the catalyst microsphere CPS-[VO (AGAP) _2] has the best catalytic effect. At 90, the reaction is 30. The conversion of hexanol to cyclohexanone, the conversion of 64%.0.546 mmol catalyst microsphere CPS-[VO (AGAP) _2], at 80 C, reaction 28h, the catalyst microsphere CPS-[VO (AGAP) _2] can convert 1- benzophenone into acetophenone, the conversion rate reaches the high catalytic activity of 78%. oxygen vanadium catalyst. The main reason is high price. The state vanadium atom has high affinity to molecular oxygen and has high coordination number. After repeated use of the heterogeneous catalyst CPS-[VO (AGAP) _2] for 7 times, the conversion rate of cyclohexanol is basically stable at about 61%, and the conversion rate of 1- benzene ethanol is basically around 73%. Obviously, the immobilized catalyst CPS-[VO (AGAP) _2] has a good cycle. Use performance.
【学位授予单位】：中北大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4;O643.36
【参考文献】
相关期刊论文 前10条
1 刘晓;王涛;张晨;宋宪根;宁丽丽;丁云杰;;Co(Ⅱ)-席夫碱配合物在水溶液中催化苯甲醇氧化制苯甲醛的研究[J];石油化工;2015年12期
2 汤金辉;王宏青;王榆元;江晓娇;李虹霖;蒋林;王爽;;2-羟基-1-萘甲醛缩2,6-二氨基吡啶钍的席夫碱配合物的合成及其抑菌活性的研究[J];应用化工;2014年01期
3 郝成君;谢辉;;高分子担载水杨醛半胱氨酸希夫碱铜配合物催化氧化环己烯研究[J];高分子通报;2010年02期
4 高宇;张月成;赵继全;;双氮席夫碱配体对甲基三氧化铼催化烯烃环氧化反应的影响[J];催化学报;2009年12期
5 方小牛;戴美珍;李晓红;匡仁云;;水杨醛双缩二氨基硫脲二丁基锡配合物的合成及杀菌活性研究[J];化学研究与应用;2009年05期
6 陈丽珍;安树茂;魏田玉;;分子筛固载希夫碱锰配合物催化环己烯环氧化[J];山西化工;2009年01期
7 王茂清;冯思思;朱苗力;;N,N,N-三(2-甲基苯并咪唑)胺氧钒配合物的合成、表征及光谱性质研究[J];化学工程师;2009年01期
8 刘宝生;王洪艳;纪红兵;;分子氧存在下镁铝水滑石负载高锰酸钾活化醇类液相氧化反应研究[J];高校化学工程学报;2008年04期
9 郝成君;赵晓军;;高分子担载苯丙氨酸希夫碱钴配合物催化氧化环己烯研究[J];平顶山工学院学报;2007年02期
10 段宗范,王荣民,何玉凤,谢云涛,王云普,夏春谷;高分子担载水杨醛希夫碱钴配合物催化分子氧氧化环己烯性能研究[J];分子催化;2005年05期
，本文编号：2156642
本文链接：https://www.wllwen.com/kejilunwen/huaxue/2156642.html
教材专著
