CN101462072A - Solid supported type metal schiff base catalyst and preparation method thereof - Google Patents
Solid supported type metal schiff base catalyst and preparation method thereof Download PDFInfo
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- CN101462072A CN101462072A CNA2008100493253A CN200810049325A CN101462072A CN 101462072 A CN101462072 A CN 101462072A CN A2008100493253 A CNA2008100493253 A CN A2008100493253A CN 200810049325 A CN200810049325 A CN 200810049325A CN 101462072 A CN101462072 A CN 101462072A
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Abstract
The invention discloses Schiff base ligand compounds with a structural formula shown in a formula (I). In the formula, R1 is a hydrogen atom, a chlorine atom or a tert-butyl group; and R2 is the hydrogen atom, the chlorine atom or the tert-butyl group. The invention also discloses an immobilized catalyst which is prepared from the Schiff base ligand compounds and is used for series catalysis of oxygenated hydrocarbons by molecular oxygen. The immobilized catalyst for catalyzing the oxygenated hydrocarbons by the molecular oxygen has large immobilization amount of metal ions and high catalytic activity, and can be used for industrialized production. A method of the invention is easy to obtain raw materials, has simple preparation technology, and is easy for mass production.
Description
Technical field
The invention belongs to the Coordinative Chemistry field, the solid-carrying type schiff base catalyst and the Preparation of catalysts method that are specifically related to a kind of schiff bases ligand compound and prepare by this ligand compound.
Background technology
With green oxidation agent molecule oxygen is oxygen source, and metal complex is a catalyst, and it is important front edge problems that the scientific worker studies that the oxidizing hydrocarbons compound of high conversion, high selectivity is used for obtaining a series of Fine Organic Chemical product.The refreshing horse of country's " eight or five " key project-Chinese Group Co.,Ltd produces 6.5 ten thousand tons nylon salt project per year, in the process of producing cyclohexane by adding hydrogen in benzene, the joint product cyclohexene still has a large amount of more than needed except that personal, is that the higher spin-off of raw material production added value has important practical significance with the cyclohexene therefore.At present, the added value high product that is obtained by cyclohexene oxide mainly contains 7-oxa-bicyclo[4.1.0, cyclonene, cyclohexenol, cyclohexanediol etc.Wherein the purposes of 7-oxa-bicyclo[4.1.0 is extremely extensive, it is the very important organic synthesis intermediate of a class, epoxy radicals on its molecular structure is very active, can generate a series of derivatives with reaction such as ammonia, amine, alcohol, phenol, carboxylic acid, as being that raw material can synthesize with it: benzhexol hydrochloride, agricultural chemicals plictran, propargite, Merlon, catechol etc.; Cyclonene also is very important a kind of industrial chemicals in the organic synthesis, is widely used in medicine and the agricultural chemicals, as is used for synthetic steroid, cyclohexenone analog herbicide etc.
But compare with the oxidation reaction of other type, the selective oxidation of cyclohexene is difficult problem, especially use molecular oxygen to be oxygen source, product after the oxidation is complicated, this mainly is because cyclohexene has two active sites that oxidation reaction all easily takes place, promptly two keys and α-H, when the oxidation position occurs on two keys, generate 7-oxa-bicyclo[4.1.0, cyclohexanone, cyclohexanediol, hexandial, adipic acid etc., if the oxidation position occurs on the allylic, then generate cyclonene, cyclohexenol, 2-cyclohexene hydrogen peroxide etc.Therefore, be raw material with the cyclohexene, molecular oxygen is an oxygen source, explores the cyclohexene oxide catalyst of high activity, high selectivity, to obtain the higher back converted products of added value, not only has wide prospect in industrial application, also has important academic theory significance.
Although molecular oxygen is very stable, but there are many enzymes that molecular oxygen can be activated in nature under temperate condition, people are as inspiration, synthesized a large amount of metalloporphyrins and porphyrin-like compound and simulated the activated centre of these enzymes, as various metalloporphyrins, metal phthalocyanine, metal schiff bases complex compound, Bipyridine metal complexes, o-phenanthroline metal complex, 8 hydroxy quinazine metal complex compounds, β--diketone metalloid complex compound etc.But the above-mentioned homogeneous catalyst that all belongs to, homogeneous catalyst has the shortcoming that is difficult to separate recovery from product, and therefore, the imitative enzyme catalyst of preparation solid-carrying type is a present industrial problem that needs to be resolved hurrily.
When the solid-carrying type catalyst of preparation activate molecular oxygen, method commonly used at present is exactly a surface-modification method, these class methods are common in carries out modification to the Zeolite support surface, after functional group certain in the carrier surface grafting, this functional group is linked to each other with homogeneous catalyst with coordinate bond or covalent bond, thereby reach the immobilized purpose of homogeneous catalyst.With organic compound the modification of zeolite molecular sieve inner surface early there is research, the most frequently used organic matter is silane and alkyl silane or alkoxy silane, they can consequently be grafted on the surface of zeolite with the surface hydroxyl reaction of zeolite, by subsequent treatment, obtain a stable silica superficial layer at last such as hydrolysis.This method can effectively overcome the loss of homogeneous phase complex because of it and the carrier of adaptation larger aperture demonstrates application promise in clinical practice.Pass through to mesopore molecular sieve HMS and MCM-41 finishing, with alkene epoxidation homogeneous catalyst MoO as people such as Yang Hengquan
2(acac)
2Immobilized in ethylenediamine base and pentanedione functional mesoporous molecular sieve duct, prepared novel, easily reclaim, reusable alkene epoxidation heterogeneous catalyst, and this catalyst is used for the cyclohexene catalytic epoxidation, the result shows, compares with the catalyst that direct absorption method is immobilized, and it is strong that this catalyst has immobilized ability, the catalytic activity height, it is few that metal is separated out, and advantage such as can be repeatedly used, not only with homogeneous catalyst MoO
2(acac)
2Quite, and selectivity reach 80%.(Yang Hengquan, Zhang Gaoyong, Hong Xinlin, Deng. ethylenediamine base and 2, the immobilized molybdenum of 4-pentanedione functional mesoporous molecular sieve (VI): novel cyclohexene ring oxidation catalyst [J]. chemical journal, 2003,61 (11): 1786-1791.) Vinhado introduces propyl imidazole, sulphenyl, oxypropyl trimethyl ammonium respectively and introduces sulphenyl simultaneously and propyl imidazole (SiO on the silica gel surface
3 -Or oxypropyl trimethyl ammonium and propyl imidazole (SiN (IPG))
+(IPG)) two modification groups, with different ferriporphyrins, the load of manganoporphyrin derivative on it, the oxidation reaction that is used for the epoxidation and the cyclohexane of catalysis cyclo-octene, it is better that discovery has the catalyst activity of sulphenyl, illustrates that the electronic effect of sulphenyl and the strong polarity microenvironment that silica-gel carrier provides have promoted the heterolytic fission of O-O key.(F á bio.S.Vinhado, P.R.Martins, A.P.Masson, et al.Supported iron (III) porphyrins pentafluorophenyl-derivatives ascatalysts in epoxidation reactions by H2O2:the role of the silica-support andsulfonatophenyl residues in the activation of the peroxidic bond[J] .J.Mol.Catal.A:Chemical, 2002,188 (1-2): 141-151.) behind above-mentioned support modification, use the coordinate bond key solid-carrying type catalyst even, having occurred some recently again uses covalent bonds the complex key to be connected in report on the carrier of modification, as Rong-Min Wang etc., after the silica gel amination with modification, direct and aldehyde reaction forms the Schiff aar ligand, then with metallic ion coordination, make the heterogeneous catalysis (Fig. 1-17) that the covalent bond key connects, this catalyst molecular oxygen oxidation alkene, do not add co-conducer, and make chain alkene mainly obtain epoxides, solved and do not added co-conducer for many years, just be difficult to use molecular oxygen oxidation mainly to obtain the difficult problem of epoxides.(H.X.Feng, R.M.Wang, Y.F.He, et al.Preparation and catalysis of porous silicasupported metal Schiff-base complex[J] .J.Mol.Catal.A:Chemical, 2000,159:25-29.) Ren Tong etc. reported synthetic cobalt Schiff base metal complexes on the mesopore molecular sieve MCM 1 that 3 one aminopropyl triethoxysilanes are modified, find that this catalyst can be in the presence of isobutylaldehyde, with the molecular oxygen is oxidant, highly selective catalysis cyclohexene and cinnamic epoxidation under the temperate condition, and can be repeatedly used.(appoint and lead to, Yan Liang, Zhang Hanpeng waits the preparation of .MCM one 41 immobilized Co schiff bases complexes and the research [J] of catalyzing expoxidation of olefines thereof. Journal of Molecular Catalysis, 2003,17 (4): 310-312.)
Use covalent bond key key connection with on the immobilized carrier after modification of homogeneous catalyst, at present common have two kinds of methods, and a kind of is the intramolecular bond connection, and another kind is the intermolecular linkage connection.The intramolecular bond connection is meant that the carrier of functionalization (being generally amination) and the material (mostly being salicylide and derivative thereof) that contains carbonyl generate schiff bases in the molecule, and then a kind of method of carrying out coordination with metal, or the carrier of functionalization and homogeneous phase metal salicylide complex (or metal and salicylide) are reflected at when generating in the molecule schiff bases and metal-complexing, adopt this method to prepare the heterogeneous catalysis that the covalent bond key connects as V.D.Chaube and partners thereof, they use 3-amine propyl-triethoxysilicane with Woelm Alumina (mesoporous alumina) functionalization earlier, complex condensation and the coordination that itself and metal ion and salicylide are formed again, form the solid-carrying type catalyst that the covalent bond key connects in the molecule, the result shows, this solid-carrying type catalyst is all higher than corresponding homogeneous catalyst activity and selectivity, after using three times, active and selectivity does not have much variations.(V.D.Chaube, S.Shylesh, A.P.Singh.Synthesis, characterization and catalytic activity of Mn (III)-andCo (II)-salen complexes immobilized mesoporous alumina[J] .J.Mol.Catal.A:Chemical, 2005,241:79-87.) Boyapati Manoranjan Choudary and partners thereof adopt the also heterogeneous catalysis that synthesizes the intramolecular bond connection of success of two kinds of methods simultaneously, first method be earlier with 3-trimethoxy silicon propyl group ethylenediamine with carrier H
+-K10 kaolinite or pure silicon MCM-41 functionalization become schiff bases with the salicylidene symphysis again, form complex with the manganese ion coordination afterwards.Second method is to become schiff bases with 3-trimethoxy silicon propyl group ethylenediamine with the salicylidene symphysis earlier, forms complex with the manganese ion coordination again, and is afterwards that complex is immobilized at carrier H
+On-K10 kaolinite or the pure silicon MCM-41.Catalyst and ion-exchange that these two kinds of methods make compare, and the result shows that covalent bond key connection can prevent the loss of homogeneous phase complex preferably.(Boyapati?Manoranjan?Choudary，Mannepalli?LakshmiKantam，Balagam?Bharathi，et?al.Epoxidations?of?olefins?catalysed?by?newMn(II)salen?immobilized?mesoporous?materials[J].J.Mol.Catal.A：Chemical，2000，159：417-421.)
The intermolecular linkage connection is meant that earlier schiff bases (or the corresponding little molecule) prepared in reaction with the carrier and the functionalization of functionalization (being generally amination) goes out intermolecular schiff bases, and then a kind of method of carrying out coordination with metal.Adopt this method to prepare the heterogeneous catalysis that the covalent bond key connects as Geon-Joong Kim and Dae-Woon Park; at first with the MCM-41 and 2 of functionalization; 6-diformyl phenol or 2; 6-diformyl-4-tert-butyl phenol condensation, more respectively with (1S, 2S)-(+)-(1; 2)-DACH and salicylaldehyde derivatives reaction; generate the schiff bases part that intermolecular covalent bond key connects,, form complex again with the cobalt ions coordination.(G.J.Kim, D.W.Park.The catalytic activity of new chiral salen complexesimmobilized on MCM-41 in the asymmetric hydrolysis of epoxides to diols[J] .Catalysis Today, 2000,63:537-547.) V.Ayala etc. also synthesizes such catalyst, at first salicylide and the 3-isocyanate group propyl-triethoxysilicane with functionalization reacts, again with above-mentioned product and carrier reaction, thereby it is salicylaldehyde derivatives is immobilized on carrier, then close the derivatives reaction of salicylide respectively with cyclohexanediamine, get solid-carrying type schiff bases part, with metallic ion coordination, can form the complex that intermolecular covalent bond key connects again.(V.Ayala，A.Corma，M.Iglesiasc，et?al.MesoporousMCM-41-heterogenised(salen)Mn?and?Cu?complexes?as?effective?catalysts?foroxidation?of?sulfides?to?sulfoxides?Isolation?of?a?stable?supported?Mn(V)＝Ocomplex，responsible?of?the?catalytic?activity[J].J.Mol.Catal.A：Chemical，2004，221：201-208.)
In sum, the catalyst of covalent bond key connection preparation can prevent the loss of homogeneous phase complex preferably, and the intermolecular linkage connection is more complicated than molecule internal key connection, and the raw material of use also is difficult to obtain.When adopting the intramolecular bond connection in addition in the document carrier supported quantity of metal ion is had only 0.5-0.9%.
Summary of the invention
The objective of the invention is to overcome above shortcomings in the prior art, provide a kind of raw material to be easy to get, synthetic convenient, active high, to solid-carrying type schiff base catalyst of the big a kind of catalytic molecular oxygen oxidizing hydrocarbons of the supported quantity of metal ion and preparation method thereof.
The objective of the invention is to be achieved through the following technical solutions:
A kind of schiff bases ligand compound, its structural formula is suc as formula shown in (I):
R1 is hydrogen atom, chlorine atom or the tert-butyl group in the formula; R2 is hydrogen atom, chlorine atom or the tert-butyl group.
Schiff bases ligand compound of the present invention, R1 is preferably hydrogen atom in the formula, and R2 is preferably hydrogen atom.
By the solid-carrying type schiff base catalyst of schiff bases ligand compound preparation of the present invention, its structural formula is suc as formula shown in (II):
M is Mn, Co or Mo in the formula; R1 is hydrogen atom, chlorine atom or the tert-butyl group; R2 is hydrogen atom, chlorine atom or the tert-butyl group.
The preparation method of the solid-carrying type schiff base catalyst shown in the formula (II): the schiff bases ligand compound shown in the formula (I) is dissolved in the organic solvent, metal acetate salt is dispersed in the organic solvent after with small amount of ethanol solution, wherein the mol ratio of metal acetate salt and schiff bases ligand compound is 0.7～1.5:1, adding mole again in organic solvent is the o-phenylenediamine of 0.7～1.5 times of amount of schiff bases ligand compound, behind backflow 3～5h, add LiClH2O again with schiff bases ligand compound equimolar amounts, back flow reaction 0.5～1h, cooling, filter, 50～120 ℃ of vacuum drying get the solid-carrying type catalyst of catalytic molecular oxygen oxidizing hydrocarbons.
Described organic solvent is carrene, dichloroethanes, carbon tetrachloride, chloroform, dichloroethylene, n-butanol, isobutanol, benzene or toluene, is preferably carrene.Described metal acetate salt is Mn (OAc)
24H
2O, Co (OAc)
24H
2O or Cu (OAc)
24H
2O.
Another kind of solid-carrying type schiff base catalyst by schiff bases ligand compound preparation of the present invention, its structural formula is suc as formula shown in (III):
M is Mo in the formula; R1 is hydrogen atom, chlorine atom or the tert-butyl group; R2 is hydrogen atom, chlorine atom or the tert-butyl group.
The preparation method of the solid-carrying type schiff base catalyst shown in the formula (III), it is characterized in that: the schiff bases ligand compound shown in the formula (I) is dispersed in the mixed organic solvents, add little molecular metal complex, the mol ratio of its medium and small molecular metal complex and schiff bases ligand compound is 0.7～1.5:1, add 2-3 and drip triethylamine, behind the 3～5h that refluxes, cooling, suction filtration, 50～120 ℃ of vacuum drying; Dried product exhibited is put into apparatus,Soxhlet's, is that the dichloromethane-ethanol system extracting of 95:5～85:15 is colourless to filtrate with volume ratio, the solid-carrying type catalyst of catalytic molecular oxygen oxidizing hydrocarbons.
Described mixed organic solvents is that volume ratio is the dichloromethane-ethanol system of 1:3～3:1.Described little molecular metal complex is MoO
2(acac)
2
The present invention adopts covalent bond key connection to prepare heterogeneous catalysis, by the carrier MCM-41-NH after the ammonification
2Obtain the schiff bases ligand compound, obtain the solid-carrying type catalyst of serial catalytic molecular oxygen oxidizing hydrocarbons then by the schiff bases ligand compound.The solid-carrying type catalyst of catalytic molecular oxygen oxidizing hydrocarbons of the present invention is big to the supported quantity of metal ion, and the catalytic activity height can be used for suitability for industrialized production.Method raw material of the present invention is easy to get, and preparation technology is simple, is easy to large-scale production.Catalyst of the present invention to the catalytic oxidation performance result of cyclohexene shown in table 1, table 2, table 3.
The performance of table 1 catalyst molecular oxygen oxidation cyclohexene
The comparison of table 2 catalyst turn over number
The repeat performance of table 3 catalyst
Description of drawings
Fig. 1 MoO
2(acac)
2Infrared spectrum;
The infrared spectrum of Fig. 2 schiff bases ligand i-1;
The infrared spectrum of Fig. 3 schiff bases ligand i-2;
The infrared spectrum of Fig. 4 catalyst I I-1;
The infrared spectrum of Fig. 5 catalyst I I-5;
The infrared spectrum of Fig. 6 catalyst I I-6;
The infrared spectrum of Fig. 7 catalyst I II-1;
The uv drs spectrum of Fig. 8 schiff bases ligand i-1;
The uv drs spectrum of Fig. 9 schiff bases ligand i-2;
The uv drs spectrum of Figure 10 catalyst I I-1 (a), II-5 (b) and II-6 (c);
The uv drs spectrum of Figure 11 catalyst I II-1;
The thermogravimetric analysis of Figure 12 schiff bases ligand i-1 and I-2;
The thermogravimetric analysis of Figure 13 catalyst I I-1 (a), II-5 (b) and II-6 (c);
The thermogravimetric analysis of Figure 14 catalyst I II-1.
The specific embodiment
Below in conjunction with embodiment the present invention is specified, but the present invention is not limited thereto.
In the ethanolic solution of 30ml, the carrier MCM-41-NH after the adding 1g amination
2, the back that stirs adds the salicylide of 1.67mmol and the NaOH of 1.67mmol, adds hot reflux 6h under stirring, and cooling is filtered, and 60 ℃ of vacuum drying get glassy yellow compound schiff bases ligand compound I-1, and the content that elementary analysis records N is 2.1%.
Embodiment 2
In the ethanolic solution of 30ml, the carrier MCM-41-NH after the adding 1g amination
2, the back that stirs adds 3 of 1.67mmol, and the NaOH of 5-dichloro-salicylaldehyde and 1.67mmol adds hot reflux 6h under stirring, and cooling is filtered, and 60 ℃ of vacuum drying get glassy yellow compound schiff bases ligand compound I-2, and the content that elementary analysis records N is 1.5%.
Embodiment 3
Repeat the method for embodiment 1, different is to change above-mentioned salicylide into 3, the 5-di-tert-butyl salicylaldehyde, and all the other are constant, can obtain orange-yellow compound schiff bases ligand compound I-3, and the content that elementary analysis records N is 1.8%.
Embodiment 4
Repeat the method for embodiment 1, different is to change above-mentioned salicylide into the 5-chloro-salicylic aldehyde, and all the other are constant, can obtain orange-yellow compound schiff bases ligand compound I-4, and the content that elementary analysis records N is 1.9%.
Embodiment 5
I-1 is dispersed in the 30ml dichloromethane solution with 0.75mmol schiff bases ligand compound, adds to contain 0.75mmol Mn (OAc)
24H
2The 5ml ethanolic solution of O adds the o-phenylenediamine of 0.75mmol again, behind the backflow 4h, adds the LiClH of 0.75mmol again
2There are back flow reaction 1h down in O, air, and cooling is filtered, and 60 ℃ of vacuum drying get the solid-carrying type catalyst I I-1 of catalytic molecular oxygen oxidizing hydrocarbons.
Embodiment 6
I-1 is dispersed in the 30ml dichloroethane solution with 0.75mmol schiff bases ligand compound, adds to contain 1.5mmol Cu (OAc)
24H
2The 5ml ethanolic solution of O adds the o-phenylenediamine of 1.5mmol again, behind the backflow 5h, adds the LiClH of 1.5mmol again
2There are back flow reaction 0.5h down in O, air, and cooling is filtered, and 60 ℃ of vacuum drying get the solid-carrying type catalyst I I-2 of catalytic molecular oxygen oxidizing hydrocarbons.
Embodiment 7
I-1 is dispersed in the 40ml carbon tetrachloride solution with 1.5mmol schiff bases ligand compound, adds to contain 0.75mmol Co (OAc)
24H
2The 10ml ethanolic solution of O adds the o-phenylenediamine of 0.75mmol again, behind the backflow 3h, adds the LiClH of 0.75mmol again
2There are back flow reaction 0.8h down in O, air, and cooling is filtered, and 60 ℃ of vacuum drying get the solid-carrying type catalyst I I-3 of catalytic molecular oxygen oxidizing hydrocarbons.
Embodiment 8
1.5mmol schiff bases ligand compound I-1 is dispersed in the 40ml dichloroethylene solution, adds and contain 0.8mmol Mn (OAc)
24H
2The 5ml ethanolic solution of O adds the o-phenylenediamine of 1.5mmol again, return 4h after, add the LiClH of 1.5mmol again
2There are back flow reaction 0.9h down in O, air, and cooling is filtered, and 60 ℃ of vacuum drying get the solid-carrying type catalyst I I-4 of catalytic molecular oxygen oxidizing hydrocarbons.
Embodiment 8
Repeat the method for embodiment 5, different is to replace schiff bases ligand compound I-1 with schiff bases ligand compound I-2, replaces carrene with dichloroethylene, obtains the solid-carrying type catalyst I I-5 of catalytic molecular oxygen oxidizing hydrocarbons.
Embodiment 9
Repeat the method for embodiment 7, different is to replace schiff bases ligand compound I-1 with schiff bases ligand compound I-2, replaces dichloroethanes with n-butanol, obtains the solid-carrying type catalyst I I-6 of catalytic molecular oxygen oxidizing hydrocarbons.
Repeat the method for embodiment 6, different is to replace schiff bases ligand compound I-1 with schiff bases ligand compound I-2, replaces dichloroethanes with toluene, obtains the solid-carrying type catalyst I I-7 of catalytic molecular oxygen oxidizing hydrocarbons.
Embodiment 11
Repeat the method for embodiment 7, different is to replace schiff bases ligand compound I-1 with schiff bases ligand compound I-3, replaces dichloroethanes with toluene, obtains the solid-carrying type catalyst I I-8 of catalytic molecular oxygen oxidizing hydrocarbons.
Embodiment 12
A certain amount of molybdenum trioxide and a certain amount of acetylacetone,2,4-pentanedione are added the hot reflux certain hour together, the gained mixture contains a little unreacted molybdenum trioxide, mixture is promptly filtered while hot and under agitation pour into the filtrate of heat in the benzinum, there is yellow powder to separate out immediately, mixture is placed in the ice bath freezing, then orange-yellow powder is leached, wash 2-3 time with acetone solvent, air drying gets orange-yellow powder molybdenum and closes acetylacetone,2,4-pentanedione (MoO
2(acac)
2) product 7.5g (molecular weight 326.24), yield 65.8%.
The schiff bases ligand compound I-1 of 2mmol is dispersed in the mixed solution of 15ml carrene and 15ml ethanol, adds and contain 2mmol MoO
2(acac)
2The 15ml ethanolic solution, heating, add 2 triethylamines, behind the backflow 4h, cooling, suction filtration, 60 ℃ of vacuum drying, dried product is put into apparatus,Soxhlet's, is that the dichloromethane-ethanol solution extracting of 95:5 is colourless to filtrate with volume ratio, the solid-carrying type catalyst I II-1 of catalytic molecular oxygen oxidizing hydrocarbons.
Embodiment 13
The method that repeats embodiment 12 prepares molybdenum and closes acetylacetone,2,4-pentanedione.
The schiff bases ligand compound I-2 of 1.5mmol is dispersed in the mixed solution of 5ml carrene and 15ml ethanol, adds and contain 1mmol MoO
2(acac)
2The 10ml ethanolic solution, heating, add 2 triethylamines, behind the backflow 3h, cooling, suction filtration, 50 ℃ of vacuum drying, dried product is put into apparatus,Soxhlet's, is that the dichloromethane-ethanol solution extracting of 90:10 is colourless to filtrate with volume ratio, the solid-carrying type catalyst I II-2 of catalytic molecular oxygen oxidizing hydrocarbons.
Embodiment 14
The method that repeats embodiment 12 prepares molybdenum and closes acetylacetone,2,4-pentanedione.
The schiff bases ligand compound I-3 of 1.4mmol is dispersed in the mixed solution of 10ml carrene and 15ml ethanol, adds and contain 2mmol MoO
2(acac)
2The 15ml ethanolic solution, heating, add 2 triethylamines, behind the backflow 5h, cooling, suction filtration, 55 ℃ of vacuum drying, dried product is put into apparatus,Soxhlet's, is that the dichloromethane-ethanol solution extracting of 85:15 is colourless to filtrate with volume ratio, the solid-carrying type catalyst I II-3 of catalytic molecular oxygen oxidizing hydrocarbons.
Embodiment 15
The method that repeats embodiment 12 prepares molybdenum and closes acetylacetone,2,4-pentanedione.
The schiff bases ligand compound I-4 of 2.5mmol is dispersed in the mixed solution of 15ml carrene and 10ml ethanol, adds and contain 2mmol MoO
2(acac)
2The 15ml ethanolic solution, heating, add 2 triethylamines, behind the backflow 4.5h, cooling, suction filtration, 58 ℃ of vacuum drying, dried product is put into apparatus,Soxhlet's, is that the dichloromethane-ethanol system extracting of 92:8 is colourless to filtrate with volume ratio, the solid-carrying type catalyst I II-4 of catalytic molecular oxygen oxidizing hydrocarbons.
Embodiment 16 (can leave out)
Repeat the method for embodiment 12, different is to replace schiff bases ligand compound I with schiff bases ligand compound IV.
Structural characterization
1. infrared spectrum analysis
Molybdenum closes the infrared spectrogram of acetylacetone,2,4-pentanedione and sees Fig. 1.
As seen from Figure 1,2926cm
-1(w) be the stretching vibration peak of saturated ν (C-H); 1588cm
-1(S) be the stretching vibration peak of ν (C=C) and ν (C=O); 1516cm
-1(S) be the stretching vibration peak of ν (C=O) and ν (C=C); 1413cm
-1(W) and 1361cm
-1(S) be the flexural vibrations of saturated C-H; 1266cm
-1(m) be ν (C-CH
3) and the stretching vibration peak of ν (C=C); 1183cm
-1(W) be δ (C-H) and δ (C-CH
3Flexural vibrations; 907cm
-1(S) be the stretching vibration peak of ν (Mo=0).By above analysis as can be known, the product that is synthesized is object MoO
2(acac)
2
The infrared spectrogram of schiff bases ligand i-1 is seen Fig. 2.
As seen from Figure 2,3457.51cm
-1(m) be the stretching vibration peak of Si-OH, 2978.18cm
-1(w) be the stretching vibration peak of C-H.1647.99cm
-1(m) be the stretching vibration peak of C=N imine linkage.1535.99cm
-1(w) and 1482.86cm
-1(w) be the skeletal vibration absworption peak of phenyl ring.1082.41cm
-1(s), 797.58cm
-1(m) and 462.31cm
-1(s) be the stretching vibration peak of Si-O.By above analysis as can be known, the functional group-NH on the carrier
2With salicylide the condensation dehydration having taken place, has generated our target product schiff bases ligand i-1.
The infrared spectrogram of schiff bases ligand i-2 is seen Fig. 3.
As seen from Figure 3,3611.29cm
-1(m) be the stretching vibration peak of Si-OH, 2965.92cm
-1(w) be the stretching vibration peak of C-H.1653.11cm
-1(m) be the stretching vibration peak of C=N imine linkage.1509.74cm
-1(w) and 1458.34cm
-1(w) be the skeletal vibration absworption peak of phenyl ring.1080.40cm
-1(s), 797.28cm
-1(m) and 461.68cm
-1(s) be the stretching vibration peak of Si-O.665.61cm
-1(w) be the C-Cl stretching vibration peak.By above analysis as can be known, the functional group-NH on the carrier
2With salicylide the condensation dehydration having taken place, has generated our target product schiff bases ligand i-2.
The infrared spectrum of catalyst I I-1 is seen Fig. 4.
As seen from Figure 4,3635.96cm
-1(m) be the stretching vibration peak of Si-OH, 1625.28cm
-1(m) be the stretching vibration peak of C=N imine linkage; Compare (1647.99cm with the stretching vibration peak of C=N imine linkage among the ligand i I-1
-1(m)) taken place to move 1563.98cm
-1(w) and 1425.65cm
-1(w) be the skeletal vibration absworption peak of phenyl ring, 1082.41cm
-1(s), 797.25cm
-1(m) and 466.88cm
-1(s) be the stretching vibration peak of Si-O.By above analysis as can be known, metal ion and ligand i-1 carry out coordination and make some characteristic peaks of catalyst I I-1 compare with part to have taken place to move.
The infrared spectrum of catalyst I I-5 is seen Fig. 5.
As seen from Figure 5,3473.89cm
-1(m) be the stretching vibration peak of Si-OH, 165040cm
-1(m) be the stretching vibration peak of C=N imine linkage; Stretching vibration peak (1653.11cm with C=N imine linkage among the ligand i I-2
-1(m)) compare 1564.90cm has taken place to move
-1(w) and 1423.07cm
-1(w) be the skeletal vibration absworption peak of phenyl ring, 1082.41cm
-1(s), 795.03cm
-1(m) and 464.36cm
-1(s) be the stretching vibration peak of Si-O.662.33cm
-1(w) be the stretching vibration peak of C-Cl key.By above analysis as can be known, metal ion and ligand i-2 carry out coordination and make some characteristic peaks of catalyst I I-5 compare with part to have taken place to move.
The infrared spectrum of catalyst I I-6 is seen Fig. 6.
As seen from Figure 6,3455.80cm
-1(m) be the stretching vibration peak of Si-OH, 1617.71cm
-1(m) be the stretching vibration peak of C=N imine linkage; Stretching vibration peak (1653.11cm with C=N imine linkage in the ligand i-2
-1(m)) compare 1565.63cm has taken place to move
-1(w) and 1420.91cm
-1(m) be the skeletal vibration absworption peak of phenyl ring, 1078.32cm
-1(s), 793.61cm
-1(m) and 463.92cm
-1(s) be the stretching vibration peak of Si-O.669.68cm
-1(w) be the stretching vibration peak of C-Cl key.By above analysis as can be known, metal ion and ligand i-2 carry out coordination and make some characteristic peaks of catalyst I I-6 compare with part to have taken place to move.
(molybdenum closes acetylacetone,2,4-pentanedione-NH to catalyst I II-1
2-MCM-salicylide) infrared spectrum is seen Fig. 7.
As seen from Figure 7,3460.26cm
-1(m) be the stretching vibration peak of Si-OH, 1645.80cm
-1(m) be the stretching vibration peak of C=N imine linkage; Stretching vibration peak (1647.99cm with C=N imine linkage in the ligand i-1
-1(m)) compare 1549.43cm has taken place to move
-1(w) and 1474.69cm
-1(m) be the skeletal vibration absworption peak of phenyl ring, 1082.66cm
-1(s), 798.25cm
-1(m) and 463.17cm
-1(s) be the stretching vibration peak of Si-O.901.68cm
-1(m) be the stretching vibration peak of ν Mo=0, close the stretching vibration peak 907cm of Mo=0 in the acetylacetone,2,4-pentanedione with the homogeneous phase molybdenum
-1(S) compare and taken place to move.By above analysis as can be known, the homogeneous phase molybdenum closes acetylacetone,2,4-pentanedione and ligand i-1 and carries out coordination and make some characteristic peaks of catalyst V compare with part to have taken place to move.
2. uv drs spectrum analysis
The uv drs spectrogram of schiff bases ligand i-1 is seen Fig. 8.
As shown in Figure 8, be π-π on the phenyl ring at the 265nm place
*Electron transition absworption peak (B band), 415nm is n-on the C=N imine linkage〉π
*The electron transition absworption peak, when with metal-complexing after, this summit is moved to the high-energy direction.
The uv drs spectrogram of schiff bases ligand i-2 is seen Fig. 9.
As shown in Figure 9, be π-π on the phenyl ring at the 281nm place
*Electron transition absworption peak (B band), 417nm is n-on the C=N imine linkage〉π
*The electron transition absworption peak, same ligand i-1 is compared, because-the electrophilic effect of Cl, make characteristic peak mobile a little to the high-energy direction.
The uv drs spectrogram of catalyst I I is seen Figure 10.
As shown in Figure 10, catalyst I I-1, II-5 and II-6 respectively the absworption peak at 257nm, 254nm and 256nm place be π-π on the phenyl ring
*Electron transition absworption peak (B band), the absworption peak at 470nm, 442nm and 477nm place is n-on the C=N imine linkage〉π
*The electron transition absworption peak is compared with ligand i, because the coordination of N on metal ion and the C=N imine linkage makes this peak move to the high-energy direction.IV compares with complex, because the adding of o-phenylenediamine makes this peak increase to the amplitude that the high-energy direction moves.
(molybdenum closes acetylacetone,2,4-pentanedione-NH to catalyst I II-1
2-MCM-salicylide) uv drs spectrogram is seen Figure 11.
As shown in Figure 11, be π-π on the phenyl ring at the 254nm place
*Electron transition absworption peak (B band), 427nm is n-on the C=N imine linkage〉π
*The electron transition absworption peak, same ligand i-1C=N imine linkage absworption peak 415nm compares, because the coordination of N on metal ion and the C=N imine linkage makes this peak move to the high-energy direction.
3. thermogravimetric analysis
In order further to understand the thermally-stabilised situation of obtained catalyst, in the air stream of 20ml/min, 10 ℃/min of heating rate, 0-800 ℃ of intensification scope, we carry out the thermogravimetric test to prepared part and corresponding composition catalyst thereof, and concrete outcome is as follows.
Schiff bases ligand i-1 (MCM-41-NH
2-salicylide) and schiff bases ligand i-2
(MCM-41-NH
2-3,5-dichloro-salicylaldehyde) Figure 12 is seen in thermogravimetric analysis.
As shown in Figure 12, schiff bases ligand i-1 (MCM-41-NH
2-salicylide) decomposition temperature scope occurs two characteristic exotherm decomposition peaks from 221 ℃ to 560 ℃ respectively at 348.15 ℃ and 469.10 ℃, and this decomposition peak with polymer binding part is consistent
[3]Schiff bases ligand i I (MCM-41-NH
2-3,5-dichloro-salicylaldehyde) decomposition temperature scope occurs two characteristic exotherm decomposition peaks respectively at 335 ℃ and 504 ℃, with schiff bases ligand i-2 (MCM-41-NH from 209 ℃ to 586 ℃
2-salicylide) compare, its decomposition temperature scope broadens, and this is because the electrophilic effect of chlorine causes.
Catalyst I I-1 (Mn-NH
2-MCM-salicylide-o-phenylenediamine), II-5 (Mn-NH
2-MCM-3,5-dichloro-salicylaldehyde-o-phenylenediamine) and II-6Co-NH
2-MCM-3,5-dichloro-salicylaldehyde-o-phenylenediamine) Figure 13 is seen in thermogravimetric analysis.
As shown in Figure 13, catalyst I I-1 (Mn-NH
2-MCM-salicylide-o-phenylenediamine) decomposition temperature scope occurs 1 characteristic exotherm decomposition peak and an acromion from 183 ℃ to 504 ℃ at 310 ℃.Catalyst I I-5 (Mn-NH
2-MCM-3,5-dichloro-salicylaldehyde-o-phenylenediamine) decomposition temperature scope is from 162 ℃ to 510 ℃, 1 characteristic exotherm decomposition peak appears at 307 ℃, comparing the decomposition temperature scope with composition catalyst I-1 broadens, characteristic peak is mobile a little to low temperature, and the electrophilic effect of this explanation chlorine reduces the heat endurance of corresponding composition catalyst.Catalyst I I-6 (Co-NH
2-MCM-3,5-dichloro-salicylaldehyde-o-phenylenediamine) decomposition temperature scope occurs 1 characteristic exotherm decomposition peak from 175 ℃ to 690 ℃ at 328 ℃.With composition catalyst II-5 (Mn-NH
2-MCM-3,5-dichloro-salicylaldehyde-o-phenylenediamine) compare the decomposition temperature scope and characteristic peak all moves to high temperature, this explanation cobalt complex catalyst I I-6 is than the heat endurance height of manganese complex catalyst I I-5.
(molybdenum closes acetylacetone,2,4-pentanedione-NH to catalyst I II-1
2-MCM-salicylide) Figure 14 is seen in thermogravimetric analysis.
As shown in Figure 14, (molybdenum closes acetylacetone,2,4-pentanedione-NH to catalyst I II-1
2-MCM-salicylide) decomposition temperature scope occurs 3 characteristic exotherm decomposition peaks from 190 ℃ to 564 ℃ respectively at 248 ℃, 399 ℃, 475 ℃.The peak that may subside for the skeleton of molecular sieve MCM, 564 ℃ of later endothermic decomposition peaks.
4. elementary analysis
In order to understand the composition situation of obtained catalyst, we carry out the elementary analysis test to prepared catalyst, and concrete outcome is as shown in table 4 below.
The elementary analysis of table 4 complex
By table as can be seen, do not add among 2 kinds of catalyst complexes III-1 of o-phenylenediamine, the mol ratio of theoretical C/H is 10, but the practical measurement value is 9.45 and 6.58, all little than theoretical value, amino among the carrier MCM-41 of this explanation functionalization, some and salicylide condensation, some does not have and the salicylide condensation.Add among 3 kinds of catalyst I I-1, II-5, the II-6 of o-phenylenediamine, the mol ratio of theoretical C/H is 5.33, but the practical measurement value is 8.02,8.96 and 8.42, and is all big than theoretical value.
5. the mensuration of metal ion content
In order to determine the loading condition of metal ion on carrier, we use ICP that the content of metal ion is measured, and the result is as shown in table 2 below.
As can be seen from Table 5, do not add among 2 kinds of composition catalyst III-1 of o-phenylenediamine, the content of metal ion is respectively 1.5% and 8.0%, that is to say that the molybdenum match catalyst is bigger than the content of metal ion in the manganese complex catalyst, the content height of little molecular complex than the complex metal ion that directly uses metal ion to make used in this explanation.Add among 3 kinds of composition catalyst II-1, II-5, the II-6 of o-phenylenediamine, the content of metal ion is respectively 12%, 6.0% and 8.6%, by more as can be seen, the complex that uses chloride salicylide to make is lower than the content of the complex metal ion that uses not chloride salicylide to make, the content height of the complex metal ion that the complex ratio use manganese ion that uses cobalt ions to make makes.
The mensuration of table 5 metal ion content
Catalyst is to the catalytic oxidation performance and the repeat performance experiment of cyclohexene
Under the normal pressure, in aforementioned catalyst test apparatus, add 0.1g catalyst, 2ml cyclohexene, 20ml acetonitrile, with a certain amount of TBHP, control TBHP: cyclohexene=2%, bubbling feed a certain amount of oxygen, and oxygen speed is 5ml/min, 50 ℃ of control bath temperatures, reaction is 8 hours under the magnetic agitation, sample analysis, and the product data are quantitative by normalization method.Different catalysts to the catalytic oxidation performance result of cyclohexene shown in table 1, table 2, table 3.Wherein contrast groups I adopts Mn-MCM-NH
2-salicylide is as catalyst, and contrast groups II adopts molybdenum to close acetylacetone,2,4-pentanedione as catalyst.
Claims (11)
1. schiff bases ligand compound, its structural formula is suc as formula shown in (I):
R1 is hydrogen atom, chlorine atom or the tert-butyl group in the formula;
R2 is hydrogen atom, chlorine atom or the tert-butyl group.
2. schiff bases ligand compound according to claim 1 is characterized in that: R1 is a hydrogen atom, and R2 is a hydrogen atom.
3. solid-carrying type schiff base catalyst by claim 1 or the preparation of 2 described schiff bases ligand compounds, its structural formula is suc as formula shown in (II):
M is Mn, Co or Cu in the formula;
R1 is hydrogen atom, chlorine atom or the tert-butyl group;
R2 is hydrogen atom, chlorine atom or the tert-butyl group.
4. the preparation method of solid-carrying type schiff base catalyst as claimed in claim 3, it is characterized in that: the schiff bases ligand compound shown in the formula (I) is added in the organic solvent, mix with the ethanolic solution of dissolving little metal acetate, wherein the mol ratio of metal acetate salt and schiff bases ligand compound is 0.7～1.5:1, adding mole again in above-mentioned mixed liquor is the o-phenylenediamine of 0.7～1.5 times of amount of schiff bases ligand compound, reflux behind 3～5h, add LiClH again with schiff bases ligand compound equimolar amounts
2O, back flow reaction 0.5～1h, cooling is filtered, and 50～120 ℃ of vacuum drying get the solid-carrying type catalyst of catalytic molecular oxygen oxidizing hydrocarbons.
5. the preparation method of solid-carrying type schiff base catalyst according to claim 4 is characterized in that: described organic solvent is carrene, dichloroethanes, carbon tetrachloride, chloroform, dichloroethylene, n-butanol, isobutanol, benzene or toluene.
6. the preparation method of solid-carrying type schiff base catalyst according to claim 4 is characterized in that: described organic solvent is a carrene.
7. the preparation method of solid-carrying type schiff base catalyst according to claim 4 is characterized in that: described metal acetate salt is Mn (OAc)
24
H2O, Co (OAc)
24H
2O or Cu (OAc)
24H
2O.
8. solid-carrying type schiff base catalyst by claim 1 or the preparation of 2 described schiff bases ligand compounds, its structural formula is suc as formula shown in (III):
M is Mo in the formula;
R1 is hydrogen atom, chlorine atom or the tert-butyl group;
R2 is hydrogen atom, chlorine atom or the tert-butyl group.
9. the preparation method of solid-carrying type schiff base catalyst as claimed in claim 8, it is characterized in that: the schiff bases ligand compound shown in the formula (I) is dispersed in the mixed organic solvents, add little molecular metal complex, the mol ratio of its medium and small molecular metal complex and schiff bases ligand compound is 0.7～1.5:1, add 2-3 and drip triethylamine, behind the 3～5h that refluxes, cooling, suction filtration, 50～120 ℃ of vacuum drying; Dried product exhibited is put into apparatus,Soxhlet's, is that the dichloromethane-ethanol system extracting of 95:5～85:15 is colourless to filtrate with volume ratio, the solid-carrying type catalyst of catalytic molecular oxygen oxidizing hydrocarbons.
10. the preparation method of solid-carrying type schiff base catalyst according to claim 9 is characterized in that: described mixed organic solvents is that volume ratio is 1: 3～3: 1 a dichloromethane-ethanol system.
11. the preparation method of solid-carrying type schiff base catalyst according to claim 8 is characterized in that: described little molecular metal complex is MoO
2(acac)
2
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| CN102276422A (en) * | 2011-06-27 | 2011-12-14 | 湖南科技大学 | Method for catalyzing benzene and hydrogen peroxide to synthesize phenol by using Cu-loading Schiff base |
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| CN102276422A (en) * | 2011-06-27 | 2011-12-14 | 湖南科技大学 | Method for catalyzing benzene and hydrogen peroxide to synthesize phenol by using Cu-loading Schiff base |
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