CN104624233B - Immobilized Pd (II) catalyst of the three-dimensional ordered mesoporous organosilicon of ethylenediamine functionalization - Google Patents
Immobilized Pd (II) catalyst of the three-dimensional ordered mesoporous organosilicon of ethylenediamine functionalization Download PDFInfo
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Abstract
The invention discloses a kind of immobilized Pd (II) catalyst of three-dimensional ordered mesoporous organosilicon of ethylenediamine functionalization, the preparation method of the Pd (II) catalyst is：Ethylenediamine bridged silane and phenyl bridged silane are carried out copolycondensation under Action of Surfactant first, ethylenediamine functionalization three-dimensional ordered mesoporous organosilicon material is obtained；Then immobilized Pd (II) catalyst of the three-dimensional ordered mesoporous organosilicon that Pd (II) is immobilized on obtaining ethylenediamine functionalization on ethylenediamine functionalization three-dimensional ordered mesoporous organosilicon material；Immobilized Pd (II) catalyst of three-dimensional ordered mesoporous organosilicon of the ethylenediamine functionalization of the present invention solve homogeneous Pd (II) catalyst cannot recycle, heavy metal ion and organic solvent to environment the problems such as, there is orderly three-dimensional hexagonal mesoporous structure, higher specific surface area, its are demonstrated by higher catalysis activity in the reaction of water phase Suzuki.
Description
Technical field
The present invention relates to the body Preparation Method of catalyst, and in particular to a kind of three-dimensional ordered mesoporous of ethylenediamine functionalization are organic
Silicon immobilized Pd (II) catalyst.
Background technology
In fine chemistry industry and pharmaceutical synthesis chemical field, the C-C coupling reaction of metal organic catalysis is to construct carbon-carbon bond
The halogenated aryl hydrocarbon of one of maximally effective instrument, wherein palladium chtalyst is formation C in organic synthesiss with the Suzuki reactions of end alkynessp-
CspOne of most important reaction of key, constructing for the structure occupy very important status in organic synthesis field.At present, palladium is urged
The type reaction system of the Suzuki reactions of change includes the homogeneous organic metal palladium catalyst of classics, such as Pd (OAc)2With heterogeneous
Metal palladium catalyst, such as Pd/C etc..Although and homogeneous catalyst activity is higher, can not reuse, this not only increases reaction
Cost, and heavy metal pollution is produced to environment.Although metal palladium catalyst can overcome the shortcoming of homogeneous catalyst,
Reaction system usually needs to add organometallic ligand, such as triphenylphosphine to be unfavorable for product separation and purification, and environment is caused
Organic Pollution.Additionally, both classical reaction systems are typically necessary organic solvent, and the organic solvent for using is to environment
Pollution can also be produced.
As countless biochemistry organic reactions occur in aqueous medium by enzyme catalyst, so as to produce to life system
Important impact.The solvent that water is safest, harmless, be easy to get, therefore, with water replace organic solvent carry out organic synthesiss into
One of focus for current Green Chemistry research.If designing the efficient catalytic for realizing cleaning organic reaction in aqueous medium
Agent, its meaning are very far-reaching.In recent years, many organic reactions focused in aqueous medium are due to its deliquescent restriction, most
It is to adopt homogeneous catalyst, although its effect is preferable, but their prospects for commercial application is restricted, and is primarily due to them very
Hardly possible is separated from reaction system, and recycling is also relatively difficult, so that production cost increases, and environment is produced heavy metal-polluted
Dye.Homogeneous organo-metallic catalyst is immobilized on carrier, although disadvantages described above can be overcome, but due to catalytic active site dispersion
Spend the change of not high and chemical environment so as to which catalytic efficiency reduces.In order to reach and corresponding homogeneous catalyst catalytic efficiency
Suitable catalyst, immobilized after organo-metallic catalyst both must must retain the chemical environment of original catalytic active site, and living
Want high degree of dispersion in property position.
Meso pore silicon oxide material has big surface area, pore volume, uniform aperture due to which, catalytic field have than
Wide application.Particularly chemist have developed a kind of mesopore silicon oxide material of caged three-dimensional open-framework in recent years
Material, because which has the aperture of adjustable inlet port, therefore be considered as having than traditional two-dimensional channel meso pore silicon oxide material more
Effectively adsorb and mass transport process.Three-dimensional ordered mesoporous organosilicon (PMO) material not only have above, and due to which
Organic group has been introduced in skeleton, the hydrophobicity of carrier has been enhanced so that the catalyst activity position after immobilized has been easier and substrate
Contact, so that improve catalytic efficiency.Therefore, organic metal homogeneous catalyst is immobilized on functionalization three-dimensional ordered mesoporous organosilicon
On material, using advantages such as the larger specific surface area of material itself, regular pore structure, controllable aperture and hydrophobicitys, one
Aspect can realize being fully contacted for catalytic active site high degree of dispersion, substrate and active center, on the other hand can also realize being catalyzed
Recycling for agent, finally realizes organic reaction greenization.
Content of the invention
The purpose of the present invention is：There is provided a kind of immobilized Pd (II) of three-dimensional ordered mesoporous organosilicon of ethylenediamine functionalization to urge
The preparation method of agent, the immobilized Pd (II) of the three-dimensional ordered mesoporous organosilicon of the ethylenediamine functionalization obtained by the preparation method
Catalyst is to solve homogeneous Pd (II) catalyst and cannot recycle, heavy metal ion and organic solvent are to environment etc.
Problem.
The present invention technical solution be：First by ethylenediamine bridged silane with phenyl bridged silane in surfactant
Copolycondensation is carried out under effect, ethylenediamine functionalization three-dimensional ordered mesoporous organosilicon material is obtained；Then Pd (II) is immobilized on second
On two amino-functionalization three-dimensional ordered mesoporous organosilicon materials, the three-dimensional ordered mesoporous organosilicon for obtaining ethylenediamine functionalization is immobilized
Pd (II) catalyst；Which comprises the following steps that：
（1）Surfactant, alcohol and mixed in hydrochloric acid are made surfactant concentration for 3.8 ~ 4.2 mM, determining alcohol is
Aqueous solution of 0.32 ~ 0.5 M, HCl concentration for 0.11 ~ 0.15 M, 30～40oC mix homogeneously；Add double three ethoxies of 1,2-
Base silicon benzene, 50 ~ 80 min of pre-polymerization；Ethylenediamine base bridged silane is added, continues 22 ~ 28 h of reaction；And 95 ~ 105oC is aged
70~80 h；
（2）By step（1）Gained solid surfactant removed through extraction, neutralizing treatment are dried, obtain ethylenediamine functionalization
Three-dimensional ordered mesoporous organosilicon (DA-PMO)；
（3）DA-PMO is added in the alcoholic solution containing Pd (II) compound, 40 ~ 60oAfter C stirring 10-16 h,
Filter, wash, dry, obtain the organosilicon of three-dimensional ordered mesoporous immobilized Pd (II) heterogeneous catalysis.
Wherein, step（1）In, 1,2- double triethoxysilicane benzene are 5 with the mol ratio of ethylenediamine bridged silane:1~99:1；
Described surfactant is P123；Described ethylenediamine bridged silane for double [3- (trimethoxy silicon substrate) propyl group] ethylenediamines or
Double [3- (triethoxy silicon substrate) propyl group] ethylenediamines.
Wherein, step（2）In, extractant used is acid mixed alkoxide solution, and extraction temperature is 60 ~ 90oC, during extraction
Between be 30 ~ 50 h；The mass volume ratio of solid and extraction agent solution is 1g: 400~600 mL；Described alcohol is methanol, ethanol
Or propanol；Described acid is hydrochloric acid, sulphuric acid, and acid content in extraction agent solution is 0.2 ~ 0.4 mol/L；Washing alkali soluble used
Liquid is 0.1M ~ saturation NaHCO3, 0.1M ~ saturation Na2CO3Solution, 0.1M ~ saturation KHCO3Or 0.1M ~ saturation K2CO3Solution；20
~30oCThe mass volume ratio of 5 ~ 10 h of agitator treating, solid and aqueous slkali is 1g:1~8 mL.
Wherein, step（3）In, described Pd (II) compound is Pd (CH3CN)2Cl2、Pd(OAc)2Or PdCl2In one
Kind；
Described alcohol is methanol, ethanol or propanol；Pd (II) compound is 1g with the mass volume ratio of alcohol:80~150mL；
DA-PMO is 1 with the mass ratio of Pd (II) compound:0.05~0.20.
Wherein, step（3）In, Pd (II) heterogeneous catalysis that the organosilicon of the three-dimensional ordered mesoporous for obtaining is immobilized has
Orderly three-dimensional hexagonal mesoporous structure, specific surface area are 500 ~ 600 m2/ g, aperture be 4.0 ~ 6.0 nm, pore volume be 0.4 ~
0.8cm3The supported quantity of/g, Pd (II) is 0.2 ~ 2.5 wt%.
Wherein, step（3）In, immobilized Pd (II) the heterogeneous catalysis application of the organosilicon of the three-dimensional ordered mesoporous for obtaining
Suzuki reactions in Yu Shuixiang, Suzuki courses of reaction are represented using following formula：
.
The present invention has advantages below：
1st, the heterogeneous catalysis duct prepared by the present invention is unobstructed, with orderly three-dimensional hexagonal mesoporous structure, higher
Specific surface area, active sites are evenly distributed, and reactivity is high, overcomes deficiency of the prior art, can realize catalytic active site
Being uniformly distributed of point, substrate and active center are fully contacted, and can realize recycling for catalyst again, finally realize that green is urged
The target of change, and preparation method is simple, and low cost, with preferable application prospect.
2nd, present invention process is simple, the immobilized Pd (II) of the three-dimensional ordered mesoporous organosilicon of the ethylenediamine functionalization of preparation
Catalyst not only has efficient catalysis activity, improves response speed, and the catalyst is recyclable, makes production cost
Reduce, and reduce pollution of the heavy metal to environment.
3rd, catalyst of the invention is demonstrated by higher catalysis activity in the Suzuki reactions of water phase phenylboric acid and iodobenzene,
Efficiency of pcr product is 100% up to 93%, selectivity, and there is preferable catalytic efficiency still after reusing 4 times, reacts yield up to 87%.
Description of the drawings
Fig. 1 is little for three-dimensional ordered mesoporous organosilicon immobilized Pd (II) catalyst of 1 gained ethylenediamine functionalization of embodiment
Angle XRD figure；
Ns of the Fig. 2 for three-dimensional ordered mesoporous organosilicon immobilized Pd (II) catalyst of 2 gained ethylenediamine functionalization of embodiment2
Adsorption-desorption isothermal figure；
Fig. 3 is three-dimensional ordered mesoporous organosilicon immobilized Pd (II) catalyst of the ethylenediamine functionalization of 3 gained of embodiment
XPS schemes；
Fig. 4 is applied mechanically for three-dimensional ordered mesoporous organosilicon immobilized Pd (II) catalyst of 4 gained ethylenediamine functionalization of embodiment
Number of times and yield.
Specific embodiment
Present invention is further illustrated with reference to specific embodiment, these embodiments are not to be construed as to technology
The restriction of scheme.
Embodiment 1：Immobilized Pd (II) catalysis of ethylenediamine functionalization three-dimensional ordered mesoporous organosilicon is prepared according to following steps
Agent
（1）By surfactant, alcohol and mixed in hydrochloric acid make surfactant concentration for 3.8 mM, determining alcohol be 0.32M,
Aqueous solution of the HCl concentration for 0.11M, 30oC mix homogeneously；Add the double triethoxysilicane benzene of 1,2-, pre-polymerization 50min；Again plus
Enter ethylenediamine base bridged silane, continue 28 h of reaction；And 95oC is aged 80 h；Wherein, step（1）In, 1,2- double three ethoxies
Base silicon benzene is 5 with the mol ratio of ethylenediamine bridged silane:1；Described surfactant is P123；Described ethylenediamine bridging silicon
Alkane is double [3- (trimethoxy silicon substrate) propyl group] ethylenediamines；
（2）By step（1）Gained solid surfactant removed through extraction, neutralizing treatment are dried, obtain ethylenediamine functionalization
Three-dimensional ordered mesoporous organosilicon (DA-PMO)；Wherein, step（2）In, extractant used is acid mixed alkoxide solution, extracts temperature
Spend 60oC, extraction time are 50 h；The mass volume ratio of solid and extraction agent solution is 1g: 400 mL；Described alcohol is
Methanol；Described acid is hydrochloric acid, and acid content in extraction agent solution is 0.2mol/L；Washing aqueous slkali used is
0.1MNaHCO3；20oCThe mass volume ratio of 10 h of agitator treating, solid and aqueous slkali is 1g:1mL；
（3）DA-PMO is added in the alcoholic solution containing Pd (II) compound, 40oAfter C stirs 16 h, filter, wash
Wash, dry, obtain the organosilicon of three-dimensional ordered mesoporous immobilized Pd (II) heterogeneous catalysis；Wherein, step（3）In, described
Pd (II) compound be Pd (CH3CN)2Cl2；Described alcohol is methanol；Pd (II) compound with the mass volume ratio of alcohol is
1g:80mL；DA-PMO is 1 with the mass ratio of Pd (II) compound:0.05.
The little angle XRD figure of Pd (the II)-DA-PMO heterogeneous catalysis that embodiment 1 is obtained is as shown in figure 1, obtained urges
Agent has orderly three-dimensional hexagonal mesoporous structure.
Embodiment 2：Immobilized Pd (II) catalysis of ethylenediamine functionalization three-dimensional ordered mesoporous organosilicon is prepared according to following steps
Agent
（1）By surfactant, alcohol and mixed in hydrochloric acid make surfactant concentration for 4.0 mM, determining alcohol be 0.4 M,
HCl concentration is the aqueous solution of 0.12 M, 35oC mix homogeneously；Add the double triethoxysilicane benzene of 1,2-, pre-polymerization 65min；Again plus
Enter ethylenediamine base bridged silane, continue 25 h of reaction；And 100oC is aged 75h；Wherein, step（1）In, 1,2- double three ethoxies
Base silicon benzene is 30 with the mol ratio of ethylenediamine bridged silane:1；Described surfactant is P123；Described ethylenediamine bridging
Silane is double [3- (triethoxy silicon substrate) propyl group] ethylenediamines；
（2）By step（1）Gained solid surfactant removed through extraction, neutralizing treatment are dried, obtain ethylenediamine functionalization
Three-dimensional ordered mesoporous organosilicon (DA-PMO)；Wherein, step（2）In, extractant used is acid mixed alkoxide solution, extracts temperature
Spend 70oC, extraction time are 40h；The mass volume ratio of solid and extraction agent solution is 1g: 450 mL；Described alcohol second
Alcohol；Described acid is sulphuric acid, and acid content in extraction agent solution is 0.3 mol/L；Washing aqueous slkali used is 0.3MNa2CO3
Solution；25oThe mass volume ratio of 7 h of C agitator treatings, solid and aqueous slkali is 1g: 4 mL；
（3）DA-PMO is added in the alcoholic solution containing Pd (II) compound, 50oAfter C stirring 13h, filter, wash
Wash, dry, obtain the organosilicon of three-dimensional ordered mesoporous immobilized Pd (II) heterogeneous catalysis；Wherein, step（3）In, described
Pd (II) compound be Pd (OAc)2；Described alcohol is ethanol；Pd (II) compound is 1g with the mass volume ratio of alcohol:
100 mL；DA-PMO is 1 with the mass ratio of Pd (II) compound:0.1.
Pd (the II)-DA-PMO heterogeneous catalysis that embodiment 2 is obtained is from N2Adsorption/desorption isotherms (Fig. 2) understand, are somebody's turn to do
Catalyst has larger specific surface area and regular aperture, and the specific surface area for determining the catalyst by BET method is 580 m2/ g,
6.9 nm of aperture, 0.58 cm of pore volume3/g.
Embodiment 3：Immobilized Pd (II) catalysis of ethylenediamine functionalization three-dimensional ordered mesoporous organosilicon is prepared according to following steps
Agent
（1）It is 0.45 that surfactant, alcohol and mixed in hydrochloric acid are made surfactant concentration for 4.2 mM, determining alcohol
Aqueous solution of M, HCl concentration for 0.13M, 40oC mix homogeneously；Add the double triethoxysilicane benzene of 1,2-, pre-polymerization 50min；Again
Ethylenediamine base bridged silane is added, continues reaction 22h；And 105oC is aged 70h；Wherein, step（1）In, 1,2- double three second
Epoxide silicon benzene is 60 with the mol ratio of ethylenediamine bridged silane:1；Described surfactant is P123；Described ethylenediamine bridge
Connection silane is double [3- (trimethoxy silicon substrate) propyl group] ethylenediamines；
（2）By step（1）Gained solid surfactant removed through extraction, neutralizing treatment are dried, obtain ethylenediamine functionalization
Three-dimensional ordered mesoporous organosilicon (DA-PMO)；Wherein, step（2）In, extractant used is acid mixed alkoxide solution, extracts temperature
Spend 80oC, extraction time are 40h；The mass volume ratio of solid and extraction agent solution is 1g: 500 mL；Described alcohol is third
Alcohol；Described acid is hydrochloric acid, and acid content in extraction agent solution is 0.4 mol/L；Washing aqueous slkali used is saturation
KHCO3；30oCThe mass volume ratio of agitator treating 5h, solid and aqueous slkali is 1g:4.5mL；
（3）DA-PMO is added in the alcoholic solution containing Pd (II) compound, 60oAfter C stirs 10 h, filter,
Wash, dry, obtain the organosilicon of three-dimensional ordered mesoporous immobilized Pd (II) heterogeneous catalysis；Wherein, step（3）In, institute
Pd (II) compound that states is PdCl2；Described alcohol is propanol；Pd (II) compound is 1g with the mass volume ratio of alcohol:
120mL；DA-PMO is 1 with the mass ratio of Pd (II) compound:0.15.
The XPS of Pd (the II)-DA-PMO heterogeneous catalysis that embodiment 3 is obtained is schemed as shown in figure 3, can from figure
Go out, the Pd species in catalyst still+divalent exist.
Embodiment 4：Immobilized Pd (II) catalysis of ethylenediamine functionalization three-dimensional ordered mesoporous organosilicon is prepared according to following steps
Agent
（1）By surfactant, alcohol and mixed in hydrochloric acid make surfactant concentration for 4.0mM, determining alcohol be 0.5 M,
HCl concentration is the aqueous solution of 0.15 M, 35oC mix homogeneously；Add the double triethoxysilicane benzene of 1,2-, 80 min of pre-polymerization；Again
Ethylenediamine base bridged silane is added, continues 28 h of reaction；And 95oC is aged 70h；Wherein, step（1）In, 1,2- double three second
Epoxide silicon benzene is 99 with the mol ratio of ethylenediamine bridged silane:1；Described surfactant is P123；Described ethylenediamine bridge
Connection silane is double [3- (triethoxy silicon substrate) propyl group] ethylenediamines；
（2）By step（1）Gained solid surfactant removed through extraction, neutralizing treatment are dried, obtain ethylenediamine functionalization
Three-dimensional ordered mesoporous organosilicon (DA-PMO)；Wherein, step（2）In, extractant used is acid mixed alkoxide solution, extracts temperature
Spend 90oC, extraction time are 50 h；The mass volume ratio of solid and extraction agent solution is 1g: 600 mL；Described alcohol is
Ethanol；Described acid is sulphuric acid, and acid content in extraction agent solution is 0.4 mol/L；Washing aqueous slkali used is saturation
K2CO3Solution；20oThe mass volume ratio of 5 h of C agitator treatings, solid and aqueous slkali is 1g:8 mL；
（3）DA-PMO is added in the alcoholic solution containing Pd (II) compound, 60oAfter C stirs 16 h, filter,
Wash, dry, obtain the organosilicon of three-dimensional ordered mesoporous immobilized Pd (II) heterogeneous catalysis；Wherein, step（3）In, institute
Pd (II) compound that states is Pd (CH3CN)2Cl2；Described alcohol is ethanol；Pd (II) compound and the mass volume ratio of alcohol
For 1g:150 mL；DA-PMO is 1 with the mass ratio of Pd (II) compound:0.2.
Embodiment 5：By Pd (II) immobilized for the three-dimensional ordered mesoporous organosilicon of the ethylenediamine functionalization obtained by embodiment 4
Catalyst is reacted for water phase Suzuki, and detailed process is as follows：Add in 10 mL reaction bulbs and contain 0.0080 mmolPd
(II) catalyst and 1.0 mmol iodobenzenes, 1.2 mmol phenylboric acids, 2.0 mmol potassium carbonate, n-decane and 3.0 ml
Deionized water is added in 10 ml flasks, 80oC reacts 4 h；Reaction equation is：
；After reaction terminates, second is used
Acetoacetic ester extracts the Organic substance in reaction system, is carried out carrying out quantitative analyses, Activity Results such as table 1 to which with gas chromatogram；
Remaining heterogeneous catalysis ethyl acetate, deionized water wash 2～4 times, 60～80oIt is vacuum dried under C, carries out next
Secondary repeat to apply mechanically experiment, its catalysis activity is shown in Fig. 4, figure 4, it is seen that ethylenediamine functional ordered mesopore organosilicon is immobilized
After Pd (II) heterogeneous catalysis reuses 4 times, product still has preferably activity, and yield is 87%.
The catalysis activity table that table 1. Pd (II)-DA-PMO catalyst is reacted in water phase Suzuki
| Entry | R | Conv.(%) | Yield (%) |
| 1 | H | 93 | 93 |
| 2 | OCH3 | 87 | 87 |
| 3 | NO2 | 99 | 99 |
As can be seen from the table, prepared ethylenediamine functional ordered mesopore organosilicon immobilized Pd (II) catalysis
Agent shows higher activity in the reaction of water phase Suzuki.
Claims (6)
1. immobilized Pd (II) catalyst of the three-dimensional ordered mesoporous organosilicon of ethylenediamine functionalization, is characterized in that the Pd (II) is catalyzed
The preparation method of agent is：Ethylenediamine bridged silane and phenyl bridged silane are carried out cocondensation under Action of Surfactant first
Poly-, obtain ethylenediamine functionalization three-dimensional ordered mesoporous organosilicon material；Then Pd (II) is immobilized on ethylenediamine functionalization three-dimensional
On order mesoporous organosilicon material, immobilized Pd (II) catalyst of the three-dimensional ordered mesoporous organosilicon of ethylenediamine functionalization is obtained；
Which comprises the following steps that：
(1) by surfactant, alcohol and mixed in hydrochloric acid make surfactant concentration for 3.8～4.2mM, determining alcohol be 0.32～
0.50M, HCl concentration is the aqueous solution of 0.11～0.15M, in 30～40 DEG C of mix homogeneously；The double triethoxysilicane benzene of 1,2- are added,
50～80min of pre-polymerization；Ethylenediamine bridged silane is added, continues 22～28h of reaction；And 70～80h is aged at 95～105 DEG C；
(2) by surfactant removed through extraction for step (1) gained solid, neutralizing treatment is dried, obtains the three-dimensional of ethylenediamine functionalization
Order mesoporous organosilicon (DA-PMO)；
(3) DA-PMO is added in the alcoholic solution containing Pd (II) compound, after 40～60 DEG C of stirring 10-16h, filter,
Wash, dry, obtain the organosilicon of three-dimensional ordered mesoporous immobilized Pd (II) heterogeneous catalysis.
2. immobilized Pd (II) catalyst of the three-dimensional ordered mesoporous organosilicon of ethylenediamine functionalization according to claim 1,
It is characterized in that：In step (1), 1,2- double triethoxysilicane benzene are 5 with the mol ratio of ethylenediamine bridged silane:1～99:1；Described
Surfactant be P123；Described ethylenediamine bridged silane is double [3- (trimethoxy silicon substrate) propyl group] ethylenediamines or double
[3- (triethoxy silicon substrate) propyl group] ethylenediamine.
3. immobilized Pd (II) catalyst of the three-dimensional ordered mesoporous organosilicon of ethylenediamine functionalization according to claim 1,
It is characterized in that：In step (2), extractant used is acid mixed alkoxide solution, and at 60～90 DEG C, extraction time is extraction temperature
30～50h；The mass volume ratio of solid and extraction agent solution is 1g:400～600mL；Described alcohol is methanol, ethanol or third
Alcohol；Described acid is hydrochloric acid, sulphuric acid, and acid content in extraction agent solution is 0.2～0.4mol/L；Washing aqueous slkali used is
0.1M～saturation NaHCO3, 0.1M～saturation Na2CO3Solution, 0.1M～saturation KHCO3Or 0.1M～saturation K2CO3Solution；20
The mass volume ratio of～30 DEG C of 5～10h of agitator treating, solid and aqueous slkali is 1g:1～8mL.
4. immobilized Pd (II) catalyst of the three-dimensional ordered mesoporous organosilicon of ethylenediamine functionalization according to claim 1,
It is characterized in that：In step (3), described Pd (II) compound is Pd (CH3CN)2Cl2、Pd(OAc)2Or PdCl2In one kind；
Described alcohol is methanol, ethanol or propanol；Pd (II) compound is 1g with the mass volume ratio of alcohol:80～150mL；DA-
PMO is 1 with the mass ratio of Pd (II) compound:0.05～0.20.
5. immobilized Pd (II) catalyst of the three-dimensional ordered mesoporous organosilicon of ethylenediamine functionalization according to claim 1,
It is characterized in that：In step (3), Pd (II) heterogeneous catalysis that the organosilicon of the three-dimensional ordered mesoporous for obtaining is immobilized has in order
Three-dimensional hexagonal mesoporous structure, specific surface area be 500～600m2/ g, aperture are 4.0～6.0nm, and pore volume is 0.4～0.8cm3/
The supported quantity of g, Pd (II) is 0.2～2.5wt%.
6. immobilized Pd (II) catalyst of the three-dimensional ordered mesoporous organosilicon of ethylenediamine functionalization according to claim 1,
It is characterized in that：In step (3), Pd (II) heterogeneous catalysis that the organosilicon of the three-dimensional ordered mesoporous for obtaining is immobilized is applied to water
Suzuki reactions in phase, Suzuki courses of reaction are represented using following formula：
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5727137A (en) * | 1980-07-26 | 1982-02-13 | Sumitomo Electric Ind Ltd | Catalyst for water producing reaction |
| CN103408601A (en) * | 2013-07-23 | 2013-11-27 | 沈阳化工大学 | Heteronuclear bimetallic complexes having catalytic activity for the Suzuki reaction and preparation method thereof |
-
2015
- 2015-02-06 CN CN201510060969.2A patent/CN104624233B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5727137A (en) * | 1980-07-26 | 1982-02-13 | Sumitomo Electric Ind Ltd | Catalyst for water producing reaction |
| CN103408601A (en) * | 2013-07-23 | 2013-11-27 | 沈阳化工大学 | Heteronuclear bimetallic complexes having catalytic activity for the Suzuki reaction and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| Periodic mesoporous organosilica grafted palladium organometallic complex: efficient heterogeneous catalyst for water-medium organic reactions;Jianlin Huang，et al;《Applied Organometallic Chemistry》;20100824;第24卷;全文 * |
| 乙基桥联有序介孔有机硅负载Pd(II)有机金属催化剂用于水介质Barbier反应;杨旭石，等;《化学学报》;20101231;第68卷(第3期);全文 * |
| 功能化有序介孔硅材料的制备及其在绿色有机合成中的应用;朱凤霞;《中国博士学位论文全文数据库 工程科技I辑》;20111015;第10-11、49-52、59-60、63-64、66、85-86、100-103、105、111页 * |
| 有序介孔有机金属Pd(II)的制备及其催化水介质中Suzuki反应;朱凤霞，等;《催化学报》;20101231;第31卷(第11期);摘要，第1389页右栏第1.4部分 * |
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