CN109453809A - A kind of CS-Salen-Mn type composite catalyst and preparation method based on natural polymer chitosan - Google Patents
A kind of CS-Salen-Mn type composite catalyst and preparation method based on natural polymer chitosan Download PDFInfo
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- CN109453809A CN109453809A CN201811396123.6A CN201811396123A CN109453809A CN 109453809 A CN109453809 A CN 109453809A CN 201811396123 A CN201811396123 A CN 201811396123A CN 109453809 A CN109453809 A CN 109453809A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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Abstract
It is a kind of to utilize natural polymer chitosan (Chitosan, it is abbreviated as CS) aldehyde radical in surface rich amino and salicylide is condensed to form imine ligand, the composite catalyst to be formed and preparation method are coordinated with manganese acetate again, belong to chemical field, name are as follows: the structural formula of CS-Salen-Mn, CS-Salen-Mn type composite catalyst is as shown in Figure 1.Wherein, CS is as parent；Salicylide is ligand；Acetic acid is organic solvent: Mn (OAc)2·4H2As coordination center, Mn atom in CS-Salen-Mn and the N atom that imine ligand is formed in chitosan are connected directly O with coordinate bond.A kind of CS-Salen-Mn type composite catalyst based on natural polymer chitosan is prepared using being condensed and being coordinated Technology design.Composite catalyst CS-Salen-Mn preparation process of the invention is simple, and reaction specificity is good, high for aminomethyl phenyl sulfide oxidation reaction selectivity, can be recycled for multiple times and reaction process is pollution-free.
Description
Technical field
The invention belongs to chemical field, it is related to that a kind of CS-Salen-Mn type based on natural polymer chitosan is compound to urge
Agent and preparation method.
Background technique
Nineteen ninety, Jacobsan et al. have devised it is a kind of electronics in terms of and metal porphyrins
Salen-Mn complex with same characteristics, and this is used in catalytic oxidation, descendant constantly carries out on this basis
Innovation, and achieve certain progress.But for homogeneous Salen-Mn catalyst, although being difficult to substrate point in catalytic process
From being unfavorable for reusing, greatly limit its use.In addition, homogeneous Salen-Mn catalyst exists during the reaction
Dimerization deactivation phenomenom, therefore, more and more people's selection are immobilized to organic or inorganic carrier by homogeneous Salen-Mn catalyst
Upper obtained heterogeneous catalysis, to solve the problems, such as that Salen-Mn is not easily recycled as homogeneous catalyst.
Chitosan is the natural high molecular substance that chitin takes off that N- acetyl group obtains, and content in nature is only second to fibre
Dimension element occupies second, surface polyamino and hydroxyl.Biological functionality and compatibility, the blood compatibility of this natural polymer
The excellent performances such as property, safety, microbic resolvability are by all trades and professions extensive concern, in medicine, food, chemical industry, cosmetics, water
The application study of the numerous areas such as processing, METAL EXTRACTION and recycling, biochemistry and biomedical engineering achieves major progress.Although
In this way, it is still less about the research of chitosan and application report both at home and abroad at present, it is the report of catalyst carrier about chitosan
Road is with regard to less.The chemical engineering process of " green " is advocated using Ke Xunhuanliyong natural polymer solid and has substituted chemistry side
The macromolecule chain of method polymerization.Therefore, it is more next that the carrier that chitosan is used as homogeneous catalyst has obtained scientists
More concerns.
Currently, people mention by using homogeneous Salen-Mn catalyst is supported on the mode on mesoporous silicon carrier mostly
Its high specific surface area, thermal stability, catalytic activity and its reusability etc., thus realize homogeneous Salen-Mn heterogeneousization with
Oxidative function.However, the surface of mesoporous silicon composite has the hydroxyl of high concentration, there is stronger hydrophily, it is anti-in catalysis
It answers the easy strong adsorption of hydrophily product in the surface and duct of silica, causes catalyst tight during recycling
It inactivates again, also, mostly uses rear grafting or infusion process greatly, operating process is complicated, and experimental period is long.
Result of study shows the organic group being rich in using the characteristic and surface of natural polymer chitosan overlength segment
Largely influence the catalytic performance of material.It finds, after introducing organic group on material segment, is keeping after study
While raw material structure, and parent/hydrophobicity of chitosan chain can be improved, be conducive to the hydrothermal stability for improving material,
The regulation of its chain property is even carried out by the type and introduction volume that change organic group.Therefore, it is negative to prepare chitosan for design
The CS-Salen-Mn type composite catalyst of load is of great significance.Preparation process can guarantee the chain for having natural polymer chitosan
Section characteristic, moreover, active site significantly improves compared with homogeneous Salen-Mn, and the diffusion rate of reactant or product compared with
Height, so as to cause its higher catalytic activity.Therefore, we are prepared for one kind using dehydrating condensation and coordination polymerization Technology design
CS-Salen-Mn type composite catalyst based on natural polymer chitosan.
Summary of the invention
The technical problem to be solved by the present invention is to controllable using a kind of simple possible, environmentally protective and reaction condition is provided
Technology design is prepared for a kind of CS-Salen-Mn type composite catalyst based on natural polymer chitosan.
Product of the present invention is using CS as parent；Salicylide is ligand；Acetic acid is organic solvent；Mn(OAc)2·4H2O makees
For coordination center, a kind of CS-Salen-Mn type based on natural polymer chitosan is prepared using being condensed and being coordinated Technology design
Composite catalyst.
A kind of CS-Salen-Mn type composite catalyst with natural polymer chitosan structure that the present invention designs,
Name are as follows: the structural formula of CS-Salen-Mn, CS-Salen-Mn type composite catalyst is Fig. 1.
The preparation method of CS-Salen-Mn type composite catalyst based on natural polymer chitosan, by following steps and
Condition is completed:
(1) weighed 0.5 g CS is dissolved in the acetic acid diluted that 25 mL volume fractions are 1%, is placed in magnetic stirring apparatus, stirs
It mixes to chitosan and dissolves, 100 mL deionized waters are added and stir to colloidal state；
(2) it measures 0.565 mL salicylide to be dissolved in 20 mL dehydrated alcohols, this solution is added dropwise to described in step 1
In colloidal solution, solution turned yellow adjusts pH to neutrality.At this point, colloidal solution becomes cloudy, 12 h are persistently stirred；
After (3) 12 h, the turbid solution during step 2 is filtered, and after alternately being washed for several times with dehydrated alcohol and deionized water,
Obtain faint yellow solid；
(4) solid matter obtained in step 3 is dissolved in 150 mL dehydrated alcohols, and the magnetic force that this solution is placed on heating is stirred
It mixes in device and stirs, and temperature is heated to 80 DEG C, weigh 1.46 g Mn (OAc)2·4H2O is added in this solution, increases stirring
Dynamics keeps reactant evenly dispersed, sufficiently reacts 36 h；
It after (5) 36 h, weighs 0.252 g LiCl powder and is added in solution described in step 4, the reaction was continued 12 h, reaction terminates
It is filtered using suction filtration machine, and is alternately washed using dehydrated alcohol and deionized water afterwards, obtain brown solid substance；
(6) solid matter obtained after suction filtration is placed in a vacuum drying oven 80 DEG C to be dried overnight, it is multiple obtains brown powder solid
Close catalyst, final product indicates that x represents the mole ratio of manganese and salicylide with CS-Salen-Mn (x), by feed ratio it is found that
x=0.9、1.0、1.1、1.2。
The evaluation of CS-Salen-Mn catalytic effect --- it is tested with the reaction of aminomethyl phenyl sulfide oxidation for probe.
Test base stock used: aminomethyl phenyl thioether, 30% H2O2, acetonitrile.Testing composite catalyst used is CS-
Salen-Mn (x) (x=0.9,1.0,1.1,1.2), has rated the catalytic activity of different manganese content composite catalysts.
Composite material is put into 110 DEG C of 2 h of vacuum drying in a vacuum drying oven before catalysis test.
CS-Salen-Mn is catalyzed the reaction of aminomethyl phenyl sulfide oxidation in 25 mL, two mouthfuls of round-bottomed flasks with condenser pipe
Through row.By 5 mL acetonitriles, 118.6 μ L(1 mmol) aminomethyl phenyl thioether, 50 mg catalyst and 301 μ L(3 mmol) 30%
H2O2It is added sequentially in round-bottomed flask, is placed in magnetic stirring apparatus, 24 h are reacted under the conditions of 0 DEG C.Table 1 is different manganese contents
The conversion ratio and selectivity of the aminomethyl phenyl sulfide oxidation reaction of CS-Salen-Mn type composite catalyst catalysis.
Table 1
| Catalyst | Methyl phenyl sulfoxide yield % | Conversion ratio % | Selective % |
| Nothing | — | — | — |
| CS | 10.9 % | 45.3 % | 24.1 % |
| CS-Schiff | 25.2 % | 45. 1% | 55.9% |
| CS-Salen-Mn-0.9 | 41.7 % | 48. 9 % | 85.3% |
| CS-Salen-Mn-1.0 | 49.7% | 52.9% | 94.0% |
| CS-Salen-Mn-1.1 | 57.3% | 57.3% | 100% |
| CS-Salen-Mn-1.2 | 57.5% | 57.5% | 100% |
The target product of acquisition is analyzed, analysis condition: UV detector, ultraviolet wavelength with liquid chromatograph Agilent 1100
242 nm, 30 DEG C of column temperature, 100% methanol is mobile phase, 0.5 mLmin of flow velocity-1, efficient liquid phase phase chromatography p-methylphenyl
Thioether is qualitative, and the conversion ratio and selectivity of product of p-methylphenyl thioether are analyzed, and liquid data analysis method is using mark
Curve method.
The result of analytical table 1 is as it can be seen that composite catalyst CS-Salen-Mn is catalyzed aminomethyl phenyl sulfide oxidation reaction conversion ratio
Good, selectivity is high, and reaction process cleaning is suitable for industrialization promotion；In addition, in CS-Salen-Mn (1.1) composite material manganese it is negative
Carrying capacity is almost saturated, and catalysis reaction yield, which also has no, to be significantly improved, it is contemplated that economic cost problem, we finally determine
It the use of CS-Salen-Mn (1.1) is dreamboat composite catalyst.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of CS-Salen-Mn type composite catalyst.
Fig. 2 is a kind of FT-IR of CS-Salen-Mn type composite catalyst based on natural polymer chitosan of the invention
Spectrogram.
Specific embodiment:
(1) weighed 0.5 g CS is dissolved in the acetic acid diluted that 25 mL volume fractions are 1%, is placed in magnetic stirring apparatus, stirred
It is dissolved to chitosan, 100 mL deionized waters is added and stir to colloidal state；
(2) it measures 0.565 mL salicylide to be dissolved in 20 mL dehydrated alcohols, this solution is added dropwise to described in step 1
In colloidal solution, solution turned yellow adjusts pH to neutrality.At this point, colloidal solution becomes cloudy, 12 h are persistently stirred；
After (3) 12 h, the turbid solution during step 2 is filtered, and after alternately being washed for several times with dehydrated alcohol and deionized water,
Obtain faint yellow solid；
(4) solid matter obtained in step 3 is dissolved in 150 mL dehydrated alcohols, and the magnetic force that this solution is placed on heating is stirred
It mixes in device and stirs, and temperature is heated to 80 DEG C, weigh 1.46 g Mn (OAC)2·4H2O is added in this solution, increases stirring
Dynamics keeps reactant evenly dispersed, sufficiently reacts 36 h；
It after (5) 36 h, weighs 0.252 g LiCl powder and is added in solution described in step 4, the reaction was continued 12 h, reaction terminates
It is filtered using suction filtration machine, and is alternately washed using dehydrated alcohol and deionized water afterwards, obtain brown solid substance；
(6) solid matter obtained after suction filtration is placed in a vacuum drying oven 80 DEG C to be dried overnight, it is multiple obtains brown powder solid
Catalyst is closed, final product indicates that x represents the mole ratio of Mn ion and salicylide with CS-Salen-Mn (x), according to feeding intake
Than x=0.9,1.0,1.1,1.2.
Claims (2)
1. a kind of CS-Salen-Mn type composite catalyst based on natural polymer chitosan, name are as follows: CS-Salen-Mn,
The structural formula of CS-Salen-Mn type composite catalyst is shown in Fig. 1.
2. a kind of CS-Salen-Mn type composite catalyst based on natural polymer chitosan according to claim 1
Preparation method, completed by following steps and condition:
(1) weighed 0.5 g CS is dissolved in the acetic acid diluted that 25 mL volume fractions are 1%, is placed in magnetic stirring apparatus, stirs
It mixes to chitosan and dissolves, 100 mL deionized waters are added and stir to colloidal state；
(2) it measures 0.565 mL salicylide to be dissolved in 20 mL dehydrated alcohols, this solution is added dropwise to described in step 1
In colloidal solution, solution turned yellow adjusts pH to neutrality and persistently stirs 12 h at this point, colloidal solution becomes cloudy；
After (3) 12 h, the turbid solution during step 2 is filtered, and after alternately being washed for several times with dehydrated alcohol and deionized water,
Obtain faint yellow solid；
(4) solid matter obtained in step 3 is dissolved in 150 mL dehydrated alcohols, and the magnetic force that this solution is placed on heating is stirred
It mixes in device and stirs, and temperature is heated to 80 DEG C, weigh 1.46 g Mn (OAc)2·4H2O is added in this solution, increases stirring
Dynamics keeps reactant evenly dispersed, sufficiently reacts 36 h；
It after (5) 36 h, weighs 0.252 g LiCl powder and is added in solution described in step 4, the reaction was continued 12 h, reaction terminates
It is filtered using suction filtration machine, and is alternately washed using dehydrated alcohol and deionized water afterwards, obtain brown solid substance；
(6) solid matter obtained after suction filtration is placed in a vacuum drying oven 80 DEG C to be dried overnight, it is multiple obtains brown powder solid
Catalyst is closed, final product indicates that x represents the mole ratio of manganese and salicylide with CS-Salen-Mn (x), according to feed ratio, x=
0.9、1.0、1.1、1.2。
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| CN201811396123.6A CN109453809A (en) | 2018-11-22 | 2018-11-22 | A kind of CS-Salen-Mn type composite catalyst and preparation method based on natural polymer chitosan |
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| CN201811396123.6A CN109453809A (en) | 2018-11-22 | 2018-11-22 | A kind of CS-Salen-Mn type composite catalyst and preparation method based on natural polymer chitosan |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110420634A (en) * | 2019-06-27 | 2019-11-08 | 河南大学 | A kind of raising H2O-WOxThe method of@C catalytic activity and stability |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103143378A (en) * | 2013-03-04 | 2013-06-12 | 太原理工大学 | Preparation method of non-noble metal oxygen reduction electrocatalyst for cathode of fuel cell |
| CN104588100A (en) * | 2015-01-09 | 2015-05-06 | 福州大学 | Catalyst for catalyzing thioether oxidation as well as preparation method and application of catalyst |
| CN108030926A (en) * | 2017-12-15 | 2018-05-15 | 武汉工程大学 | A kind of Salen types manganese complex-Chitosan Composites with high SOD enzyme activity and preparation method thereof |
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2018
- 2018-11-22 CN CN201811396123.6A patent/CN109453809A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103143378A (en) * | 2013-03-04 | 2013-06-12 | 太原理工大学 | Preparation method of non-noble metal oxygen reduction electrocatalyst for cathode of fuel cell |
| CN104588100A (en) * | 2015-01-09 | 2015-05-06 | 福州大学 | Catalyst for catalyzing thioether oxidation as well as preparation method and application of catalyst |
| CN108030926A (en) * | 2017-12-15 | 2018-05-15 | 武汉工程大学 | A kind of Salen types manganese complex-Chitosan Composites with high SOD enzyme activity and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 何乐芹等: ""壳聚糖负载Salen-Mn(III)络合物的合成及其催化性能研究"", 《第一届全国化学工程与生物化工年会论文集》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110420634A (en) * | 2019-06-27 | 2019-11-08 | 河南大学 | A kind of raising H2O-WOxThe method of@C catalytic activity and stability |
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Application publication date: 20190312 |