CN108435251B - Preparation method and application of separable emulsion catalyst - Google Patents
Preparation method and application of separable emulsion catalyst Download PDFInfo
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- CN108435251B CN108435251B CN201810224470.4A CN201810224470A CN108435251B CN 108435251 B CN108435251 B CN 108435251B CN 201810224470 A CN201810224470 A CN 201810224470A CN 108435251 B CN108435251 B CN 108435251B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- 239000000839 emulsion Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 claims abstract description 23
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 23
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 14
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 14
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 229920001400 block copolymer Polymers 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 40
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 32
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 32
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 25
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 claims description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 8
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- LFVZDICBSAOLCN-UHFFFAOYSA-N oxolane triethoxysilane Chemical compound O1CCCC1.C(C)O[SiH](OCC)OCC LFVZDICBSAOLCN-UHFFFAOYSA-N 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- RCNRJBWHLARWRP-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane;platinum Chemical compound [Pt].C=C[Si](C)(C)O[Si](C)(C)C=C RCNRJBWHLARWRP-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 150000001450 anions Chemical group 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 abstract description 8
- 230000001590 oxidative effect Effects 0.000 abstract description 6
- 239000004094 surface-active agent Substances 0.000 abstract description 4
- 229920001577 copolymer Polymers 0.000 abstract description 3
- 238000002444 silanisation Methods 0.000 abstract 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 12
- 235000019445 benzyl alcohol Nutrition 0.000 description 7
- -1 cationic quaternary ammonium salt Chemical class 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 7
- VAJVDSVGBWFCLW-UHFFFAOYSA-N 3-Phenyl-1-propanol Chemical compound OCCCC1=CC=CC=C1 VAJVDSVGBWFCLW-UHFFFAOYSA-N 0.000 description 6
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 4
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 4
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000009881 electrostatic interaction Effects 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
Classifications
-
- 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
- B01J31/068—Polyalkylene glycols
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- 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
-
- B01J35/27—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
- C07C45/294—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups with hydrogen peroxide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
A preparation method and application of a separable emulsion catalyst, belongs to the technical field of emulsion catalysts, and can solve the problem of the prior H2O2The problem that the catalyst and the surfactant in an emulsion catalytic oxidation system which is an oxidant are difficult to recover is solved, and the preparation method comprises the following steps: the polyethylene oxide/polypropylene oxide block copolymer with the HLB value of 14-40 and the molecular weight of 2000-20000 is modified by silanization end group; the segmented copolymer of polyethylene oxide and polypropylene oxide modified by silanization reacts with phosphotungstic heteropoly acid salt to obtain the separable emulsion catalyst of the invention. The catalyst of the invention shows good catalytic activity in emulsion catalytic oxidation reaction.
Description
Technical Field
The invention belongs to the technical field of emulsion catalysts, and particularly relates to a preparation method and application of a separable emulsion catalyst.
Background
The oxidation of alcoholic organics is one of the important reactions in the organic chemical industry. The traditional oxidation process mainly adopts oxidants such as chromate, hypochlorite, permanganate and the like to realize the oxidation of the organic substrate, but the oxidants have high price, poor selectivity and heavy existenceMetal pollution and the like. H2O2The green oxidant is widely noticed in recent years, but the green oxidant cannot be completely dissolved with aliphatic alcohol and aromatic alcohol, and an emulsion catalytic system is needed to effectively carry out the reaction. The conventional emulsion catalytic system consists of an organic phase, a water phase, a surfactant and a catalyst, and has the problems of difficult demulsification after the reaction is finished and difficult separation and recovery of the surfactant and the catalyst.
At present, H2O2The emulsion catalytic oxidation system using the oxidant mainly adopts cationic quaternary ammonium salt/heteropoly acid salt as the catalyst. Namely, through electrostatic interaction, organic quaternary ammonium cations and heteropoly acid anions are paired to form an interface catalytic system in which heteropoly acid anions play a catalytic role and organic quaternary ammonium cations play a surface active role. The catalytic system has the following problems: the electrostatic interaction is weaker, and the heteropoly acid anions are easy to lose; a plurality of organic quaternary ammonium cations wrap the heteropoly acid catalytic center, so that the catalytic performance is reduced; organic quaternary ammonium cations and heteropoly acid anions are difficult to recover.
Disclosure of Invention
The invention aims at the existing H2O2The preparation method of the emulsion catalyst based on the PEO/PPO block copolymer-phosphotungstic heteropoly acid salt which is combined by covalent bonds and the application of the emulsion catalyst in alcohol oxidation reaction are provided for solving the problem that the catalyst and the surfactant in an emulsion catalytic oxidation system of an oxidant are difficult to recover.
The invention adopts the following technical scheme:
a preparation method of an isolatable emulsion catalyst comprises the following steps:
firstly, mixing 10mmol of polyethylene oxide (PEO)/polypropylene oxide (PPO) block copolymer and 10-50mmol of allyl bromide in 100mL of tetrahydrofuran, reacting at room temperature for 24-48h, and then distilling under reduced pressure to remove tetrahydrofuran and unreacted allyl bromide; then adding 50-100mL of triethoxysilane tetrahydrofuran solution with concentration of 0.2mol/L, reacting for 24h at 30-50 ℃ in the presence of 10-100ppm of platinum catalyst to obtain a product A, cooling and standing for later use;
and secondly, adding 2-5mmol of phosphotungstic heteropoly acid salt into the product A obtained in the first step, dropwise adding 4-15mmol of hydrochloric acid, reacting at room temperature for 24 hours, carrying out reduced pressure distillation, washing with cyclohexane, acetone and acetonitrile in sequence, and carrying out vacuum drying to obtain the separable emulsion catalyst.
The polyethylene oxide (PEO)/polypropylene oxide (PPO) block copolymer has a PEO-PPO-PEO structure, an HLB value of 14-40 and a molecular weight of 2000-20000.
The platinum catalyst is any one of chloroplatinic acid or 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0).
The anion part of the phosphotungstic heteropoly acid salt is [ PW11O39]7-。
The separable emulsion catalyst is applied to emulsion catalytic oxidation reaction and comprises the following processes:
adding alcohol and water into a closed reaction kettle, wherein the molar ratio of the alcohol to the water is 1:5-1: 20; then H is put in2O2Is added into the reaction system, H2O2The mole number is 1.2 times of that of the alcoholic hydroxyl; adding separable emulsion catalyst with the mass of 0.1-5% of the total mass of the reactants, stirring, reacting at 40-60 ℃ for 4-24h to obtain mixed emulsion containing catalytic oxidation products, heating the emulsion to 60-90 ℃, standing at constant temperature for 2-24h to break emulsion, separating out the catalyst, washing with acetone, and drying to obtain the final product which can be directly used for the next reaction.
The alcohol is any one of aliphatic alcohol or aromatic alcohol.
The phosphotungstic heteropoly acid salt plays a role of a catalytic center, the polyethylene oxide/polypropylene oxide segmented copolymer plays a role of emulsification and separation, and the polyethylene oxide/polypropylene oxide segmented copolymer are connected through a silicon-oxygen bond to obtain the separable emulsion catalyst. The catalyst shows good catalytic activity in emulsion catalytic oxidation reaction.
The invention has the following beneficial effects:
1. the PEO/PPO block copolymer and phosphotungstic heteropoly acid are bonded together through silicon-oxygen covalent bonds to form the novel emulsion catalyst. Phosphotungstic acid hetero compound in the catalystThe inorganic portion of the polyacid provides the catalytic oxidation function; the PEO/PPO organic part provides surface activity and temperature-sensitive characteristics, so that the catalyst not only has a stable emulsion effect, but also can realize emulsion breaking by changing the temperature, and can be separated and recycled. In addition, the organic part and the inorganic part of the catalyst are combined through a silica covalent bond, so that the problem that the heteropoly acid in a cationic quaternary ammonium salt/heteropoly acid salt system is easy to run off is solved. The catalyst can be used for H2O2The emulsion catalytic oxidation process of the existing alcohol organic matters also has application potential in the catalytic oxidation process of other organic substrates.
2. The separable emulsion catalyst provided by the invention is formed by combining a PEO/PPO block copolymer and phosphotungstic heteropoly acid salt through a silicon-oxygen covalent bond, and H is used as the active ingredient2O2The alcohol organic matter emulsion catalytic oxidation system which is an oxidant can play the roles of an emulsifier and a catalyst at the same time, has the temperature-sensitive characteristic, and can realize emulsion breaking and catalyst separation and recovery by changing the temperature.
Detailed Description
Example 1
Dissolving 10mmol of PEO-PPO-PEO triblock polymer with the molecular weight of 4200 and the HLB value of 14 into 100mL of tetrahydrofuran, adding 10mmol of allyl bromide, mixing, and reacting at room temperature for 24 h; distilling under reduced pressure to remove tetrahydrofuran and unreacted allyl bromide; then 50mL of a triethoxysilane tetrahydrofuran solution with a concentration of 0.2mol/L is added; adding 10ppm chloroplatinic acid as a catalyst, reacting at 50 ℃ for 24h, cooling and standing. And then adding 2mmol of phosphotungstic heteropoly acid salt, dropwise adding 4mmol of hydrochloric acid, reacting at room temperature for 24 hours, carrying out reduced pressure distillation, washing with cyclohexane, acetone and acetonitrile in sequence, and carrying out vacuum drying to obtain the emulsion catalyst.
Adding 50mmol of benzyl alcohol and 250mmol of water into a 50mL closed reaction kettle; 60mmol of H are subsequently added2O2Into the above reaction system; then adding an emulsion catalyst accounting for 0.1 percent of the total mass of the reactants, stirring, and reacting at the temperature of 50 ℃ for 24 hours. And (3) heating the emulsion to 60 ℃, standing for 24 hours at constant temperature to realize demulsification. Analyzing the material composition in the organic phase and the water phase to obtain the catalyst to the p-tolueneThe conversion of alcohol was 35.4%; the selectivity to benzaldehyde was 99.0%. Collecting the precipitate, washing with acetone, and drying to obtain recovered catalyst with conversion rate of 35.1% to benzyl alcohol under the same reaction conditions; the selectivity to benzaldehyde was 98.5%.
Example 2
Dissolving 10mmol of PEO-PPO-PEO triblock polymer with molecular weight of 8900 and HLB value of 30 into tetrahydrofuran, adding 50mmol of allyl bromide, mixing, and reacting at room temperature for 48 h; distilling under reduced pressure to remove tetrahydrofuran and unreacted allyl bromide; then 100mL of a triethoxysilane tetrahydrofuran solution with a concentration of 0.2mol/L is added; adding 100ppm 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0) as a catalyst, reacting at 30 ℃ for 24 hours, cooling and standing. And then adding 5mmol of phosphotungstic heteropoly acid salt, dropwise adding 15mmol of hydrochloric acid, reacting at room temperature for 24 hours, carrying out reduced pressure distillation, washing with cyclohexane, acetone and acetonitrile in sequence, and carrying out vacuum drying to obtain the emulsion catalyst.
Adding 50mmol of benzyl alcohol and 1000mmol of water into a 50mL closed reaction kettle; then 60mmol of H were added2O2Into the above reaction system; then adding an emulsion catalyst accounting for 5 percent of the total mass of the reactants, stirring, and reacting at the temperature of 60 ℃ for 4 hours. And (3) heating the emulsion to 90 ℃, and standing for 24 hours at constant temperature to realize demulsification. Analyzing the composition of the organic phase and the aqueous phase to obtain the catalyst with the conversion rate of the benzyl alcohol of 42.1 percent; the selectivity to benzaldehyde was 99.2%. Collecting the precipitate, washing with acetone, and drying to obtain recovered catalyst with conversion rate of p-benzyl alcohol of 43.3% under the same reaction condition; the selectivity to benzaldehyde was 99.0%.
Example 3
Dissolving 10mmol of PEO-PPO-PEO triblock polymer with the molecular weight of 20000 and the HLB value of 40 into tetrahydrofuran, adding 50mmol of allyl bromide, mixing, and reacting at room temperature for 48 h; distilling under reduced pressure to remove tetrahydrofuran and unreacted allyl bromide; then 100mL of a triethoxysilane tetrahydrofuran solution with a concentration of 0.2mol/L is added; adding 100ppm 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0) as a catalyst, reacting at 50 ℃ for 24 hours, cooling and standing. And then adding 5mmol of phosphotungstic heteropoly acid salt, dropwise adding 15mmol of hydrochloric acid, reacting at room temperature for 24 hours, carrying out reduced pressure distillation, washing with cyclohexane, acetone and acetonitrile in sequence, and carrying out vacuum drying to obtain the emulsion catalyst.
Adding 50mmol of benzyl alcohol and 500mmol of water into a 50mL closed reaction kettle; then 60mmol of H were added2O2Into the above reaction system; then adding an emulsion catalyst accounting for 5 percent of the total mass of the reactants, and stirring at the reaction temperature of 40 ℃ for 24 hours. And (3) heating the emulsion to 90 ℃, and standing for 24 hours at constant temperature to realize demulsification. Analyzing the composition of the organic phase and the aqueous phase to obtain that the conversion rate of the catalyst to the benzyl alcohol is 48.3 percent; the selectivity to benzaldehyde was 98.5%. Collecting the precipitate, washing with acetone, and drying to obtain recovered catalyst with conversion rate of 48.0% to benzyl alcohol under the same reaction condition; the selectivity to benzaldehyde was 99.0%.
Example 4
Dissolving 10mmol of PEO-PPO-PEO triblock polymer with molecular weight of 2000 and HLB value of 16 into tetrahydrofuran, adding 20mmol of allyl bromide, mixing, and reacting at room temperature for 32 h; distilling under reduced pressure to remove tetrahydrofuran and unreacted allyl bromide; then 100mL of a triethoxysilane tetrahydrofuran solution with a concentration of 0.2mol/L is added; adding 50ppm 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0) as a catalyst, reacting at 30 ℃ for 24 hours, cooling and standing. And then adding 4mmol of phosphotungstic heteropoly acid salt, dropwise adding 4mmol of hydrochloric acid, reacting at room temperature for 24 hours, carrying out reduced pressure distillation, washing with cyclohexane, acetone and acetonitrile in sequence, and carrying out vacuum drying to obtain the emulsion catalyst.
Adding 50mmol of cyclohexanol and 1000mmol of water into a 50mL closed reaction kettle; then 60mmol of H were added2O2Into the above reaction system; then adding an emulsion catalyst accounting for 2 percent of the total mass of the reactants, and stirring at the reaction temperature of 60 ℃ for 24 hours. And (3) heating the emulsion to 75 ℃, and standing for 2 hours at constant temperature to realize demulsification. Analyzing the material composition of the organic phase and the aqueous phase to obtain that the conversion rate of the catalyst to cyclohexanol is 86.5%; the selectivity to cyclohexanone was 99.6%. Collecting the precipitate, washing with acetone, and drying to obtain recovered catalyst with cyclohexanol converting rate of 78.0% under the same reaction condition; selectivity to cyclohexanoneThe content was 99.6%.
Example 5
Dissolving 10mmol of PEO-PPO-PEO triblock polymer with the molecular weight of 13000 and the HLB value of 25 into tetrahydrofuran, adding 10mmol of allyl bromide, mixing, and reacting at room temperature for 32 h; distilling under reduced pressure to remove tetrahydrofuran and unreacted allyl bromide; then 50mL of a triethoxysilane tetrahydrofuran solution with a concentration of 0.2mol/L is added; adding 100ppm 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0) as a catalyst, reacting at 40 ℃ for 24 hours, cooling and standing. And then adding 5mmol of phosphotungstic heteropoly acid salt, dropwise adding 10mmol of hydrochloric acid, reacting at room temperature for 24 hours, carrying out reduced pressure distillation, washing with cyclohexane, acetone and acetonitrile in sequence, and carrying out vacuum drying to obtain the emulsion catalyst.
Adding 50mmol of n-octanol and 1000mmol of water into a 50mL closed reaction kettle; then 60mmol of H were added2O2Into the above reaction system; then adding an emulsion catalyst accounting for 3 percent of the total mass of the reactants, stirring, and reacting at the temperature of 60 ℃ for 24 hours. And (3) heating the emulsion to 80 ℃, and standing for 12 hours at constant temperature to realize demulsification. Analyzing the composition of substances in an organic phase and a water phase to obtain the catalyst with the conversion rate to n-octanol of 47.5 percent; the selectivity to n-octanal is 77.0%. Collecting the precipitate, washing with acetone, and drying to obtain recovered catalyst with n-octanol conversion rate of 48.1% under the same reaction conditions; the selectivity to n-octanal was 75.5%.
Example 6
Dissolving 10mmol of PEO-PPO-PEO triblock polymer with the molecular weight of 14600 and the HLB value of 30 into tetrahydrofuran, adding 10mmol of allyl bromide, mixing, and reacting at room temperature for 32 h; distilling under reduced pressure to remove tetrahydrofuran and unreacted allyl bromide; then adding 80mL of a triethoxysilane tetrahydrofuran solution with the concentration of 0.2 mol/L; adding 100ppm 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0) as a catalyst, reacting at 40 ℃ for 24 hours, cooling and standing. And then adding 5mmol of phosphotungstic heteropoly acid salt, dropwise adding 10mmol of hydrochloric acid, reacting at room temperature for 24 hours, carrying out reduced pressure distillation, washing with cyclohexane, acetone and acetonitrile in sequence, and carrying out vacuum drying to obtain the emulsion catalyst.
50mmol of 3-phenylpropanol and 1000mmol of water are added to 50mL of closed reaction kettle; then 60mmol of H were added2O2Into the above reaction system; then adding an emulsion catalyst accounting for 1 percent of the total mass of the reactants, stirring, and reacting at the temperature of 60 ℃ for 18 hours. And (3) heating the emulsion to 80 ℃, and standing for 12 hours at constant temperature to realize demulsification. Analyzing the composition of substances in the organic phase and the aqueous phase to obtain the catalyst with the conversion rate of the 3-phenylpropanol of 65.2 percent; the selectivity to propiophenone was 85.0%. Collecting the precipitate, washing with acetone, and drying to obtain recovered catalyst with conversion rate of 3-phenylpropanol of 58.2% under the same reaction condition; the selectivity to propiophenone was 85.5%.
Claims (4)
1. A preparation method of an isolatable emulsion catalyst is characterized in that: the method comprises the following steps:
firstly, mixing 10mmol of polyethylene oxide/polypropylene oxide block copolymer and 10-50mmol of allyl bromide in 100mL of tetrahydrofuran, reacting at room temperature for 24-48h, and then distilling under reduced pressure to remove tetrahydrofuran and unreacted allyl bromide; then adding 50-100mL of triethoxysilane tetrahydrofuran solution with concentration of 0.2mol/L, reacting for 24h at 30-50 ℃ in the presence of 10-100ppm of platinum catalyst to obtain a product A, cooling and standing for later use;
secondly, adding 2-5mmol of phosphotungstic heteropoly acid salt into the product A obtained in the first step, dropwise adding 4-15mmol of hydrochloric acid, reacting at room temperature for 24h, carrying out reduced pressure distillation, washing with cyclohexane, acetone and acetonitrile in sequence, and carrying out vacuum drying to obtain a separable emulsion catalyst;
the polyethylene oxide/polypropylene oxide block copolymer has a PEO-PPO-PEO structure, the HLB value is 14-40, and the molecular weight is 2000-20000;
the anion part of the phosphotungstic heteropoly acid salt is [ PW11O39]7-。
2. The method for preparing an emulsion catalyst capable of being separated according to claim 1, wherein: the platinum catalyst is chloroplatinic acid or 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0).
3. The use of the isolatable emulsion catalyst prepared by the preparation method of claim 1 in an emulsion catalytic oxidation reaction, wherein: the method comprises the following steps:
adding alcohol and water into a closed reaction kettle, wherein the molar ratio of the alcohol to the water is 1:5-1: 20; then H is put in2O2Is added into the reaction system, H2O2The mole number is 1.2 times of that of the alcoholic hydroxyl; adding separable emulsion catalyst with the mass of 0.1-5% of the total mass of the reactants, stirring, reacting at 40-60 ℃ for 4-24h to obtain mixed emulsion containing catalytic oxidation products, heating the emulsion to 60-90 ℃, standing at constant temperature for 2-24h to break emulsion, separating out the catalyst, washing with acetone, and drying to obtain the final product which can be directly used for the next reaction.
4. The use of an isolatable emulsion catalyst according to claim 3 in an emulsion catalyzed oxidation reaction, wherein: the alcohol is aliphatic alcohol or aromatic alcohol.
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