CN103922903B - 用共轭聚合金属卟啉催化氧化烷烃和环烷烃的方法 - Google Patents

用共轭聚合金属卟啉催化氧化烷烃和环烷烃的方法 Download PDF

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CN103922903B
CN103922903B CN201410127724.2A CN201410127724A CN103922903B CN 103922903 B CN103922903 B CN 103922903B CN 201410127724 A CN201410127724 A CN 201410127724A CN 103922903 B CN103922903 B CN 103922903B
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metalloporphyrin
naphthenic hydrocarbon
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阳卫军
李永进
郭灿城
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Hunan University
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    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
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    • B01J31/1825Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/48Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02Compositional aspects of complexes used, e.g. polynuclearity
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    • C07C2601/14The ring being saturated

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Abstract

本发明公开了一种催化空气或氧气氧化烷烃和环烷烃的方法,是选用具有高孔隙度和比表面积的、以共轭炔基偶联聚合而成的固体金属卟啉作催化剂,在温和条件下对烷烃和环烷烃的碳氢键进行催化氧化,得到相应的醛酮酸等氧化产物。催化剂用量小,催化效果好。这种催化剂在反应体系中不溶解不分解,可以多次循环使用。催化氧化碳氢键的转化率高,并有很好的醇酮选择性。

Description

用共轭聚合金属卟啉催化氧化烷烃和环烷烃的方法
技术领域
本发明涉及在温和条件下选择性催化空气氧化烷烃和环烷烃的办法。
背景技术
烷烃氧化一般需要在高温高压条件下进行,选择性差。且由于碳链容易断裂,副反应多,易深度氧化,产物难分离,转化率低,收率不高。使用合适的催化剂降低反应温度和压强是减少烷烃氧化副反应、提高转化率和选择性的一个有效办法。单金属卟啉及其与金属盐的混合物能够有效地催化氧化烷烃和环烷烃中的碳氢键,选择性和收率均比较高,如专利US5077394公开了使用多卤代过渡金属卟啉催化空气对环己烷氧化的方法。CN1405131A公开金属卟啉催化空气氧化环己烷的方法中,使用μ-氧双金属卟啉和单金属卟啉或它们的固载物作主催化剂,过渡金属盐或氧化物为共催化剂催化空气对环己烷氧化。虽然这些金属卟啉类催化剂的催化效率高,但它们都是作为均相催化剂溶解在反应液中,由于金属卟啉在均相催化体系中会被分解,只能够一次性使用,成本高。所以研发出一种可重复使用的、催化效率高的、适用于烷烃和环烷烃氧化的新型催化剂,显得非常必要。
发明内容
本发明的目的是提供一种高选择性、高转化率和回收率,并可避免深度氧化产物生成,更容易分离的聚合金属卟啉催化剂及其使用方法,用于在非均相体系中催化空气氧化烷烃和环烷烃。催化过程中该催化剂用量少,催化反应温度低,并且催化剂结构稳定可以回收重复使用。
本发明采用下述技术方案实现的:通入l-50atm的空气或氧气条件下,反应温度度为25-170℃,采用通式为I的金属卟啉聚合物催化剂。该聚合物结构中金属卟啉单元的四臂分别通过具有超共轭效应的亚炔基或二亚炔基相互偶联,聚合物分子中金属卟啉单体的重复数目为4-20000,该聚合物不溶于有机溶剂,具有高度的热稳定性,孔隙度高,比表面积达100-2000m2/g。孔结构为介孔或微孔,孔径大于0.2nm。金属卟啉聚合物催化剂的用量为被氧化底物的0.001-0.5wt%。
其中,结构式I中的金属原子M1,M2可以是过渡金属原子或镧系金属原子;苯环上取代基R1,R2可以是氢,烃基,烷氧基,卤素,胺基,氨基,糖基。X1,X2可以是乙酸,乙酸丙酮,卤素。
当所使用金属卟啉聚合物的苯环上带有一个或多个卤素或烷基取代基时,反应对一级碳氧键氧化具有较好好的选择催化作用,碳氢化合物氧化产物中主要生成端碳醇和对应的酮、醛或酸。
当所使用金属卟啉聚合物催化剂结构中的M1,M2为Fe,Co,Mn时,反应对碳氢化合物二级碳氢键氧化具有很好的选择催化作用,碳氢化合物氧化产物中主要生成二级醇和对应的酮、醛或酸。
试验表明,这种金属卟啉聚合物作为催化剂对空气或氧气氧化烷烃环烷烃的反应具有良好的催化性能。由于共轭基团的偶联,使得金属卟啉单元的电子能够在大分子中流动,这大大加强了聚合物分子的催化活性。
该催化剂的反应温度低且反应时间短,有效的控制了烷烃环烷烃的深度氧化和过氧化物的进一步分解。由于其具有很好的化学稳定性和热稳定性,作为一种非均相催化剂,可以多次重复使用,有效的降低了使用成本。如在适宜条件下,对环己烷的催化氧化,环己烷转化率可达10%以上,环己醇和环己酮的收率大于95%。反应后的催化剂金属卟啉聚合物可以通过简单的离心作用分离出来并可反复使用,并且使用5次后仍保持很高的催化效率。
具体实施方式
本发明的应用范围包含但不仅限于如下的实施方式。
实施例1:
将20mg具有结构式I结构的金属卟啉聚合物,R1=R2=H,M1=M2=Mn,X1=X2=Cl,n=1,分子量为115000,比表面积为860m2/g,加入500ml环己烷中,通入8atm空气。在125℃下搅拌反应物2小时,环己烷转化率为18.1%,反应产物中环己醇和环己酮总收率92%。
实施例2:
将20mg具有结构式I结构的金属卟啉聚合物,R1=H,R2=CH3,M1=M2=Fe,X1=X2=Cl,n=2,分子量为53000,比表面积为750m2/g,加入500ml环己烷中,通入8atm空气。在100℃下搅拌反应物4小时,环己烷转化率为8.6%,反应产物中环己醇和环己酮总收率94%。
实施例3:
将20mg具有结构式I结构的金属卟啉聚合物,R1=R2=Cl,M1=Mn,M2=Fe,X1=X2=Cl,n=1,分子量为172000,比表面积为970m2/g,加入500ml环己烷中,通入l0atm空气。在130℃下搅拌反应物2小时,环己烷转化率为21.4%,反应产物中环己醇和环己酮总收率91%。
实施例4:
将15mg具有结构式I结构的金属卟啉聚合物,R1=R2=H,M1=Co,M2=Mn,X1=OAc,X2=Cl,n=1,分子量为180000,比表面积为870m2/g,加入500ml环己烷中,通入10atm氧气。在140℃下搅拌反应物2小时,环己烷转化率为24.5%,反应产物中环己醇和环己酮总收率88%。
实施例5:
将20mg具有结构式I结构的金属卟啉聚合物,R1=R2=Cl,M1=M2=Fe,X1=X2=Cl,n=2,分子量为81000,比表面积为910m2/g,加入500ml邻氯甲苯中,通入8atm空气。在120℃下搅拌反应物3小时,邻氯甲苯转化率为14.3%,反应产物中邻氯苯甲醛收率88%。
实施例6:
将30mg具有结构式I结构的金属卟啉聚合物,R1=Cl,R2=2,3,4,6-四乙酰葡萄糖基,M1=M2=Mn,n=1,分子量为103000,比表面积为920m2/g,加入500ml2-甲基丁烷中,通入10atm空气。在90℃下搅拌反应物4小时,反应主产物为3-甲基-1-丁基醇。
实施例7:
将25mg具有结构式I结构的金属卟啉聚合物,R1=R2=H,M1=M2=La,X1=Br,X2=乙酰丙酮基,n=1,分子量为85000,比表面积为850m2/g,加入500ml甲基环己烷中,通入3atm空气。在70℃下搅拌反应物10小时,反应产物为2-甲基环己醇和3-甲基环己醇。
实施例8:
将40mg具有结构式I结构的金属卟啉聚合物,R1=H,R2=Br,M1=M2=Nd,X1=X2=乙酰丙酮基,n=1,分子量为95000,比表面积为882m2/g,加入500m1甲基环己烷中,通入1atm氧气。在50℃下搅拌反应物12小时,反应效果同实施例7。
实施例9:
将实施例1中I的金属卟啉聚合物回收,回收率90%,取15mg回收催化剂加入到350ml的环己烷中,通入8atm空气。在125℃下搅拌反应物2小时,环己烷转化率为18.05%,反应产物中环己醇和环己酮总收率91%。同样反应条件下,重复使用4次后,环己烷转化率为15.2%,反应产物中环己醇和环己酮总收率90%。
实施例10:
将实施例6中I的金属卟啉聚合物回收,回收率85%,取25mg回收催化剂加入400ml2-甲基丁烷中,通入l0atm空气。在90℃下搅拌反应物4小时,反应效果同实施例6。

Claims (4)

1.一种以化学结构式如I所示的共轭微介孔聚合金属卟啉作为催化剂催化空气或氧气氧化烷烃和环烷烃制备相应的含氧化合物的方法,其特征在于:结构式I中的金属原子M1,M2为过渡金属原子或镧系金属原子;苯环上取代基R1,R2为氢,烃基,烷氧基,卤素,胺基,氨基,糖基;X1,X2为乙酸,乙酸丙酮,卤素;氧化条件为:通入l-50atm的空气或氧气,反应温度为25-170℃,金属卟啉聚合物催化剂的用量为被氧化底物的0.001-0.5wt%
2.根据权利要求1所述方法,其特征在于:催化剂为化学结构式如I所示的聚合金属卟啉;金属卟啉单体的四臂分别通过具有超共轭效应的亚炔基或二亚炔基相互偶联,聚合物分子中金属卟啉单体的重复数目为4-20000,该聚合物不溶于有机溶剂,分子中的电子流动性好,具有高度的热稳定性,孔隙度高,比表面积达100-2000m2/g,孔结构为微孔或介孔结构,且孔径大于0.2nm。
3.根据权利要求1或2所述的方法,其特征在于当所述的烷烃和环烷烃为伯碳连接的氢键时,选用的催化剂结构中的R1,R2为卤素或烷基。
4.根据权利要求1或2所述的方法,其特征在于当 所述的烷烃和环烷烃为仲碳连接的碳氢键时,选用的催化剂结构中的M1,M2为Fe,Co,Mn。
CN201410127724.2A 2014-04-01 2014-04-01 用共轭聚合金属卟啉催化氧化烷烃和环烷烃的方法 Expired - Fee Related CN103922903B (zh)

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CN108927219A (zh) * 2017-05-25 2018-12-04 湖南大学 绿色高效合成金属卟啉共轭聚合物并催化氧化环酮类制备内酯化合物
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CN101301627A (zh) * 2008-06-13 2008-11-12 大连理工大学 仿生催化氧气氧化噻吩类化合物的方法

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CN101301627A (zh) * 2008-06-13 2008-11-12 大连理工大学 仿生催化氧气氧化噻吩类化合物的方法

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