CN107537565B - Amphoteric crosslinked polymer supported noble metal catalyst, preparation and alcohol oxidation method - Google Patents
Amphoteric crosslinked polymer supported noble metal catalyst, preparation and alcohol oxidation method Download PDFInfo
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Abstract
The invention discloses a noble metal nanoparticle catalyst loaded by an acid-base amphoteric crosslinked polymer, which is a compound obtained by coordinating the acid-base amphoteric crosslinked polymer with a noble metal salt methanol solution and then reducing the coordination compound by sodium borohydride; the acid-base amphoteric crosslinked polymer is a crosslinked copolymer of divinylbenzene, vinyl heterocyclic monomers and acrylic monomers. The catalyst has high catalytic efficiency, does not need any other reaction auxiliary agents such as oxidant or inorganic base except oxygen, and the like, has adjustable reaction conversion rate and selectivity, can be recycled by centrifugation or filtration after the reaction is finished, is green and environment-friendly, and better meets the requirements of sustainable development.
Description
Technical Field
The invention relates to the technical field of catalyst design, in particular to an acid-base amphoteric crosslinked polymer supported noble metal nanoparticle catalyst, a preparation method thereof and application of the acid-base amphoteric crosslinked polymer supported noble metal nanoparticle catalyst in selective oxidation reaction of alcohol.
Background
The catalytic oxidation of alcohol is an important functional group conversion reaction in organic synthesis, is widely applied to the manufacture of various intermediates and fine chemicals, and has important significance in scientific research and chemical production. However, conventional alcohol oxidation reactions require the use of stoichiometric amounts of inorganic oxidizing agents while using large amounts of organic solvents, which agents, while effectively oxidizing the alcohol to the desired product, also produce large amounts of harmful by-products. Oxygen widely exists in air and is low in price, oxygen is used as an oxidant, and a byproduct is only water, so that the oxygen is an ideal oxidant which is green and environment-friendly, and noble metal (platinum, gold, palladium and the like) nanoparticles are used as a catalyst to catalyze the oxidation reaction of alcohol in oxygen at present. However, when oxygen is used as the oxidizing agent, a large amount of an inorganic base is added as an auxiliary agent for increasing the conversion rate of the reaction. In addition, the controllability of the oxidation reaction of alcohol is poor, and aldehyde is easily oxidized into acid to generate ester. Therefore, in the present day that green chemistry is increasingly regarded as important, from the viewpoint of environmental protection and sustainable development, and from the viewpoint of improvement of economic benefits, development of a green efficient oxidation reaction system in which a conventional oxidation system is replaced with oxygen, no additional solvent is used, no additive such as an inorganic base is used, and an efficient catalyst which is controllable in selectivity, easy to operate in reaction, and easy to separate are urgently required.
The supported nanometer noble metal catalyst is a good choice, and the carrier of the supported nanometer noble metal catalyst mainly plays the following three roles: 1) the nano noble metal is stabilized and dispersed, and agglomeration is avoided; 2) the charge state and the morphology of the nano noble metal are influenced through the interaction with the nano noble metal; 3) the surrounding micro environment of the nano noble metal, such as acid-base property, hydrophilicity and hydrophobicity and the like, is modulated, and then the substrate conversion efficiency and the selectivity of a target product are influenced. Up to now, many carriers have been used to support nano noble metals, mainly including carbon materials, oxides, organic polymers, and the like.
However, the most widely studied inorganic carriers, such as carbon materials and oxide carriers, are inexpensive but limited in kind, and have a narrow adjustable range of properties such as acid-base property and lipophilic and hydrophilic property. The organic polymer carriers have various types and wide selectable ranges, such as acid-base property, hydrophilic-hydrophobic property, space cross-linking structure and the like. By finely adjusting the properties, the size of the nano noble metal and the surrounding microenvironment thereof can be effectively regulated and controlled, so that the catalytic conversion efficiency of the substrate and the selectivity of a target product are remarkably enhanced. However, at present, the preparation and catalytic application of the organic polymer supported nano noble metal catalyst are still rarely studied. The cross-linked polymer carrier can provide a space network structure, so that the noble metal nano particles can be well fixed while being easy to separate, and the loss of the noble metal nano particles is avoided to a great extent.
Aiming at the characteristics of selective oxidation reaction of alcohol, the invention designs and synthesizes the acid-base amphoteric crosslinked polymer supported nano noble metal catalyst, realizes higher catalytic efficiency and selectivity by catalyzing the oxidation of the alcohol by acid-base synergy, and the catalyst is easy to separate and can be recycled after the reaction is finished.
Disclosure of Invention
The invention provides a noble metal nanoparticle catalyst loaded with an acid-base amphoteric crosslinked polymer, which has high catalytic efficiency and is easy to recover.
The invention also provides a preparation method of the acid-base amphoteric crosslinked polymer supported noble metal nanoparticle catalyst, which is simple to operate, easy to control and suitable for industrial production.
The invention also provides an application method of the acid-base amphoteric crosslinked polymer supported noble metal nanoparticle catalyst in catalyzing aldol condensation reaction, and the catalyst in the method can be recycled and reused.
An acid-base amphoteric crosslinked polymer supported noble metal nanoparticle catalyst is a compound obtained by coordinating an acid-base amphoteric crosslinked polymer with a noble metal salt methanol solution and then reducing the coordination compound by sodium borohydride;
the acid-base amphoteric crosslinked polymer described in the present invention is a crosslinked copolymer of divinylbenzene, vinyl heterocyclic monomers and acrylic monomers, and can be synthesized by a method known in the art, for example, a method described in the literature (for example, according to the methods described in the literature, catalysis Communications,2011,11, 1212-1217.).
The divinylbenzene monomer is a compound shown in a structural formula (I) (DVB), and the nitrogen-containing vinyl heterocyclic monomer is a compound shown in a structural formula (II) (VI), (III) (VP) or (IV) (NVP):
in the formula (I), R1、R2、R3、R4And R5Identical or different, R1Is hydrogen, alkyl or vinyl with 1 to 4 carbon atoms, R2Is hydrogen, alkyl or vinyl with 1 to 4 carbon atoms, R3Is hydrogen, alkyl or vinyl with 1 to 4 carbon atoms, R4Is hydrogen, alkyl or vinyl with 1 to 4 carbon atoms, R5Is hydrogen, alkyl or vinyl with 1 to 4 carbon atoms, R1、R2、R3、R4And R5The same or different, and at least one is a vinyl group;
in the formula (II), R6Is hydrogen, alkyl or vinyl with 1 to 4 carbon atoms, R7Is hydrogen, alkyl or vinyl with 1 to 4 carbon atoms, R8Is hydrogen, alkyl or vinyl with 1 to 4 carbon atoms, R9Is hydrogen, alkyl or vinyl with 1 to 4 carbon atoms, R6、R7、R8And R9The same or different, and at least one is a vinyl group;
in the formula (III), R10Is hydrogen, alkyl or vinyl with 1 to 4 carbon atoms, R11Is hydrogen, alkyl or vinyl with 1 to 4 carbon atoms, R12Is hydrogen, alkyl or vinyl with 1 to 4 carbon atoms, R13Is hydrogen, alkyl or vinyl with 1 to 4 carbon atoms, R14Is hydrogen, alkyl or vinyl with 1 to 4 carbon atoms, R10、R11、R12、R13And R14The same or different, and at least one is a vinyl group;
in the formula (IV), R15Is hydrogen, alkyl or vinyl with 1 to 4 carbon atoms, R16Is hydrogen, alkyl or vinyl with 1 to 4 carbon atoms, R17Is hydrogen, alkyl or vinyl with 1 to 4 carbon atoms, R18Is hydrogen, alkyl or vinyl with 1 to 4 carbon atoms, R15、R16、R17And R18The same or different, and at least one is a vinyl group;
in the formula (V), R19Is hydrogen or methyl;
the molar ratio of the divinylbenzene monomer to the nitrogen-containing vinyl heterocyclic monomer to the acrylic monomer in the acid-base amphoteric crosslinked polymer is 1-10: 1: 0.1-10, preferably 3-5: 1: 1.
The noble metal salt solution is a methanol solution of gold trichloride, tetrachloroauric acid, chloroplatinic acid, sodium hexachloroplatinate or ammonium tetrachloropalladate;
the mass ratio of the noble metal salt to the polymer is 0.1-20: 100, preferably 5-20: 100.
The preparation method of the nitrogen-containing cross-linked polymer supported gold nanoparticle catalyst comprises the following steps: according to the mass ratio of the noble metal salt to the acid-base amphoteric crosslinked polymer, immersing the acid-base amphoteric crosslinked polymer into a methanol solution containing the noble metal salt, and violently stirring for 6-24 hours, immersing a solid obtained by the coordination reaction of noble metal ions and nitrogen in the acid-base amphoteric crosslinked polymer into a methanol solution of a reducing agent prepared according to the molar ratio of the noble metal salt to the reducing agent, and violently stirring for 2-12 hours to prepare the acid-base amphoteric crosslinked polymer supported noble metal nanoparticle catalyst.
The mass fraction of the noble metal nanoparticles in the catalyst is 0.5-20%, preferably 1-10%.
The size range of the noble metal nano particles is 0.5-12 nm, and preferably 2-8 nm.
A selective oxidation method of alcohol, the concrete scheme includes adding catalyst into liquid alcohol and making alcohol oxidation reaction under the condition of oxygen atmosphere.
The temperature of the oxidation reaction is 20-100 ℃, and the time of the oxidation reaction is 2-30 hours.
The alcohol is one of benzyl alcohol, o-methyl benzyl alcohol, m-methyl benzyl alcohol, p-methyl benzyl alcohol, o-ethyl benzyl alcohol, m-ethyl benzyl alcohol, p-ethyl benzyl alcohol, phenethyl alcohol, o-methyl phenethyl alcohol, m-methyl phenethyl alcohol, p-methyl phenethyl alcohol, o-ethyl phenethyl alcohol, m-ethyl phenethyl alcohol, p-ethyl phenethyl alcohol, o-tert-butyl benzyl alcohol, m-tert-butyl benzyl alcohol, p-tert-butyl benzyl alcohol, o-tert-butyl phenethyl alcohol, m-tert-butyl phenethyl alcohol, p-tert-butyl phenethyl alcohol, o-nitro benzyl alcohol, m-nitro benzyl alcohol, p-nitro benzyl alcohol, o-nitro phenethyl alcohol, m-nitro phenethyl alcohol, p-nitro phenethyl alcohol and 1-octanol.
The feeding molar ratio of the alcohol to the noble metal in the catalyst is 500-100000: 1.
The raw materials and reagents of the invention can adopt products sold in the market.
Compared with the prior art, the invention has the following remarkable progress:
the catalyst combines the characteristics of noble metal nanoparticles and acid-base amphoteric crosslinked polymers; the size of the noble metal nano particles is controllable; the catalyst has acidity and alkalinity due to the fact that the catalyst simultaneously has carboxyl and imidazole groups, and therefore acid-base synergistic reaction can be achieved; the acid-base amphoteric crosslinked polymer has a spatial network structure, noble metal ions can be fixed in a network while being reduced after being complexed with nitrogen in the acid-base amphoteric crosslinked polymer, and the loading amount and size of noble metal in the catalyst can be adjusted by adjusting the nitrogen content, the crosslinking degree and the dosage of noble metal salt; the acid-base amphoteric crosslinked polymer can only swell but not dissolve after loading noble metal nano particles, and can be recycled by simple filtration or centrifugation after the catalytic reaction is finished; meanwhile, the synthesis method disclosed by the invention does not use an additional solvent, is more simple and convenient, green and environment-friendly, safe and nontoxic, has a wide development space and a great market application value, and better meets the requirements of sustainable development.
The catalyst has high catalytic efficiency, does not need any other reaction auxiliary agents such as oxidant or inorganic base except oxygen, and the like, has adjustable reaction conversion rate and selectivity, and can be recycled by centrifugation or filtration separation after the reaction is finished.
Detailed Description
Example 1 preparation of acid-base amphoteric crosslinked Polymer Supported Nannoble Metal catalyst
In a three-necked flask, Divinylbenzene (DVB) (2.0g, 15mmol), Vinylimidazole (VI) (0.483g, 5mmol), Acrylic Acid (AA) (0.360g, 5mmol), azobisisobutyronitrile (0.07g) and ethyl acetate (30ml) were added under nitrogen. The reaction was carried out at 100 ℃ for 24 hours without stirring, and after the completion of the reaction, the solvent was dried to obtain 2.5g of a white powder which was a copolymer of divinylbenzene, vinylimidazole and acrylic acid (PDVB-VI-AA).
200mg of the above white powder was immersed in AuCl3And (20mg) in methanol solution (10mL), stirring vigorously for 16h, centrifuging, washing with methanol, adding into sodium borohydride (20mg) in methanol solution (10mL), stirring vigorously for 6h, centrifuging, and washing with methanol to obtain the nitrogen acid and alkali containing amphoteric crosslinked polymer supported nanogold catalyst, wherein the gold loading capacity is 2.6%, and the particle size is 3.5 +/-1.0 nm.
Examples 2 to 7
The method of example 1 was used to prepare acid-base amphoteric crosslinked polymer supported nano noble metal catalyst, except that the molar ratio of DVB to VI and AA and the amount of gold trichloride were changed in the synthesis of PDVB-VI, as shown in table 1:
examples 8 to 9
The acid-base amphoteric crosslinked polymer supported nano noble metal catalyst was prepared by the method of example 1, except that the type of nitrogen-containing vinyl heterocyclic monomer in the synthesized crosslinked polymer was changed, as shown in table 2:
examples 10 to 12
The acid-base amphoteric crosslinked polymer supported nano noble metal catalyst was prepared by the method of example 1, except that the noble metal salt used and the amount used for preparing the catalyst were changed, as shown in table 3: EXAMPLE 13 Selective Oxidation of alcohols
Benzyl alcohol (0.3g) and 54mg of the catalyst prepared in example 1 were charged with oxygen in a jacketed reaction vessel equipped with a stirring paddle, a thermometer and gas inlets and outlets, and after stirring well, the temperature of the reaction vessel was raised to 90 ℃ and the reaction was carried out for 16 hours at a stirring speed of 600 rotor/min. After the reaction, the catalyst was recovered by centrifugal separation, and the recovery rate of the catalyst was 97.6%. The reaction mixture was diluted with ethyl acetate and the ethyl acetate solution was analyzed using gas chromatography to give a benzyl alcohol conversion of 90.3%, product selectivity: 80.1 percent of benzaldehyde, 13.2 percent of benzoic acid and 6.7 percent of benzyl benzoate.
Examples 14 to 19
The selective oxidation of alcohols was carried out as in example 13, except that the catalysts prepared in examples 2 to 7 were used, respectively, and the reaction results are shown in Table 4:
examples 20 to 21
The selective oxidation of alcohols was carried out as in example 13, except that the catalysts prepared in examples 8 to 9 were used, respectively, and the reaction results are shown in Table 5:
examples 22 to 24
The selective oxidation of alcohols was carried out as in example 13, except that the catalysts prepared in examples 10 to 12 were used, respectively, and the reaction results are shown in Table 6:
TABLE 1
| Example number | Gold chloride dosage (mg) | DVB:VI:AA(mol) | Gold loading (%) | Particle size (nm) |
| 2 | 20 | 3:1:1 | 4.2 | 3.4±1.2 |
| 3 | 40 | 3:1:2 | 7.8 | 4.5±1.1 |
| 4 | 10 | 10:3:2 | 1.7 | 2.8±1.1 |
| 5 | 20 | 2:1:1 | 2.9 | 3.0±0.9 |
| 6 | 10 | 6:1:1 | 6.4 | 3.2±1.0 |
| 7 | 20 | 10:3:5 | 7.8 | 4.2±1.2 |
TABLE 2
TABLE 3
TABLE 4
TABLE 5
TABLE 6
Example 25
Selective oxidation of alcohol was carried out in accordance with the procedure in example 13, except that benzyl alcohol was replaced with n-octanol (0.27 g). The catalyst recovery rate is 96%, the conversion rate of the obtained benzyl alcohol is 60.3%, and the product selectivity is as follows: 30.2 percent of n-octyl aldehyde, 57.5 percent of n-caprylic acid and 12.3 percent of octyl caprylate.
Example 26
The alcohol was selectively oxidized according to the procedure of example 13, except that the reaction temperature was 60 ℃ and the reaction time was 24 hours. The catalyst recovery rate is 97%, the conversion rate of the benzyl alcohol is 85.7%, and the product selectivity is as follows: 78.2 percent of benzaldehyde, 16.8 percent of benzoic acid and 5.0 percent of benzyl benzoate.
Example 27
The alcohol was selectively oxidized according to the procedure of example 13, except that the reaction temperature was 100 ℃ and the reaction time was 12 hours. The catalyst recovery rate is 96.6%, the conversion rate of the benzyl alcohol is 92.6%, and the product selectivity is as follows: 82% of benzaldehyde, 10.7% of benzoic acid and 6.5% of benzyl benzoate.
Example 28
Selective oxidation of alcohol was carried out in accordance with the procedure of example 13, except that the catalyst obtained was recovered by using example 23. The conversion rate of the benzyl alcohol is 91%, and the product selectivity is as follows: 85.8% of benzaldehyde, 7.8% of benzoic acid and 6.8% of benzyl benzoate.
Claims (9)
1. The amphoteric crosslinked polymer supported noble metal catalyst is characterized in that: the acid-base amphoteric crosslinked polymer supported noble metal catalyst is a compound obtained by coordinating the acid-base amphoteric crosslinked polymer with a soluble noble metal salt solution and then reducing the coordination compound by sodium borohydride;
the acid-base amphoteric crosslinked polymer is a crosslinked copolymer of a divinyl benzene monomer, a nitrogen-containing vinyl heterocyclic monomer and an acrylic monomer;
wherein the divinylbenzene monomer is a compound shown in a structural formula (I), the nitrogen-containing vinyl heterocyclic monomer is one or more than one of compounds shown in structural formulas (II), (III) or (IV), and the acrylic monomer is a compound shown in a structural formula (V):
in the formula (I), R1Is hydrogen, alkyl or vinyl with 1 to 4 carbon atoms, R2Is hydrogen, alkyl or vinyl with 1 to 4 carbon atoms, R3Is hydrogen, alkyl or vinyl with 1 to 4 carbon atoms, R4Is hydrogen, alkyl or vinyl with 1 to 4 carbon atoms, R5Is hydrogen, alkyl or vinyl with 1 to 4 carbon atoms, R1、R2、R3、R4And R5Any 2 or more of them are the same or different, and at least one is a vinyl group;
in the formula (II), R6Is hydrogen, alkyl or vinyl with 1 to 4 carbon atoms, R7Is hydrogen, alkyl or vinyl with 1 to 4 carbon atoms, R8Is hydrogen, alkyl or vinyl with 1 to 4 carbon atoms, R9Is hydrogen, alkyl or vinyl with 1 to 4 carbon atoms, R6、R7、R8And R9Any 2 or more of them are the same or different, and at least one is a vinyl group;
in the formula (III), R10Is hydrogen, alkyl or vinyl with 1 to 4 carbon atoms, R11Is hydrogen, alkyl or vinyl with 1 to 4 carbon atoms, R12Is hydrogen, alkyl or vinyl with 1 to 4 carbon atoms, R13Is hydrogen, alkyl or vinyl with 1 to 4 carbon atoms, R14Is hydrogen, alkyl or vinyl with 1 to 4 carbon atoms, R10、R11、R12、R13And R14Any 2 or more of them are the same or different, and at least one is a vinyl group;
in the formula (IV), R15Is hydrogen, alkyl or vinyl with 1 to 4 carbon atoms, R16Is hydrogen, alkyl or vinyl with 1 to 4 carbon atoms, R17Is hydrogen, alkyl or vinyl with 1 to 4 carbon atoms, R18Is hydrogen, alkyl or vinyl with 1 to 4 carbon atoms, R15、R16、R17And R18Any 2 or more of them are the same or different, and at least one is a vinyl group;
in the formula (V), R19Is hydrogen or methyl.
2. The catalyst of claim 1, wherein: the molar ratio of the divinyl benzene monomer to the nitrogen-containing vinyl heterocyclic monomer to the acrylic monomer in the acid-base amphoteric crosslinked polymer is 1-10: 1: 0.1-10.
3. The catalyst of claim 1, wherein: the noble metal salt solution is methanol solution of one or more than two of gold trichloride, tetrachloroauric acid, chloroplatinic acid, sodium hexachloroplatinate or ammonium tetrachloropalladate.
4. The catalyst of claim 1, wherein: the mass ratio of the noble metal salt to the polymer is 0.1-20: 100.
5. A process for preparing a catalyst as claimed in any one of claims 1 to 4, comprising the steps of: according to the required mass ratio of the noble metal salt to the acid-base amphoteric crosslinked polymer of 0.1-20: 100, immersing the acid-base amphoteric crosslinked polymer into a methanol solution containing the noble metal salt, wherein the concentration of the methanol solution is 0.1-10 mg/mL, vigorously stirring the methanol solution for 6-24 hours, taking out a solid obtained by the coordination reaction of noble metal ions and nitrogen in the acid-base amphoteric crosslinked polymer, immersing the solid into a methanol solution of a reducing agent prepared according to the required molar ratio of the noble metal salt to the reducing agent, vigorously stirring the mixture for 2-12 hours, taking out the solid, and obtaining the acid-base amphoteric crosslinked polymer supported noble metal nanoparticle catalyst, wherein the particle size of the supported noble metal nanoparticles is 1-10 nm.
6. An alcohol oxidation method comprising adding a catalyst to a liquid alcohol to perform an alcohol oxidation reaction in an oxygen atmosphere, characterized in that: the catalyst is the amphoteric crosslinked polymer supported noble metal catalyst as described in any one of claims 1-5.
7. The alcohol oxidation process according to claim 6, wherein the temperature of the oxidation reaction is 20 to 100 ℃ and the time of the oxidation reaction is 2 to 30 hours.
8. The alcohol oxidation process according to claim 6, wherein said alcohol is one or more selected from the group consisting of benzyl alcohol, o-methyl benzyl alcohol, m-methyl benzyl alcohol, p-methyl benzyl alcohol, o-ethyl benzyl alcohol, m-ethyl benzyl alcohol, p-ethyl benzyl alcohol, phenethyl alcohol, o-methyl phenethyl alcohol, m-methyl phenethyl alcohol, p-methyl phenethyl alcohol, o-ethyl phenethyl alcohol, p-ethyl phenethyl alcohol, o-t-butyl benzyl alcohol, m-t-butyl benzyl alcohol, p-t-butyl benzyl alcohol, o-t-butyl phenethyl alcohol, m-t-butyl phenethyl alcohol, p-t-butyl phenethyl alcohol, o-nitrobenzyl alcohol, m-nitrobenzyl alcohol, p-nitrobenzyl alcohol, and 1-octanol.
9. The alcohol oxidation process of claim 6, wherein the molar ratio of alcohol to noble metal charge in the catalyst is from 500 to 100000: 1.
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| JP2007237116A (en) * | 2006-03-10 | 2007-09-20 | Japan Science & Technology Agency | Polymer supported gold cluster catalyst for oxidation reaction |
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| JP2007237116A (en) * | 2006-03-10 | 2007-09-20 | Japan Science & Technology Agency | Polymer supported gold cluster catalyst for oxidation reaction |
| CN101033268A (en) * | 2007-03-30 | 2007-09-12 | 北京科技大学 | Method of preparing polarity controllable polymer microsphere |
| CN101701054A (en) * | 2009-12-01 | 2010-05-05 | 福州大学 | Surface decorating method of porous polymer microspheres |
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