Search

CN-122006812-A - Temperature response type CP-metalloporphyrin dynamic interpenetrating composition, preparation method and application thereof

CN122006812ACN 122006812 ACN122006812 ACN 122006812ACN-122006812-A

Abstract

The application relates to the technical field of catalysts, in particular to a temperature response type CP-metalloporphyrin dynamic interpenetrating composition, a preparation method and application thereof. The temperature-responsive CP-metalloporphyrin dynamic interpenetrating composition specifically comprises modified metalloporphyrin and a temperature-responsive coordination polymer, wherein the mass ratio of the modified metalloporphyrin to the temperature-responsive coordination polymer is 1 (10-20). The temperature response type CP-metalloporphyrin dynamic interpenetrating composition catalyst provided by the application realizes the synergistic improvement of high catalytic conversion efficiency and selectivity, quick and convenient recovery, low metal loss and long cycle life, and the comprehensive performance is obviously superior to that of the traditional metalloporphyrin supported catalyst.

Inventors

  • HE ZEYU

Assignees

  • 元嘉生物科技(衢州)有限公司

Dates

Publication Date
20260512
Application Date
20260121

Claims (10)

  1. 1. The temperature-responsive CP-metalloporphyrin dynamic interpenetrating composition is characterized by specifically comprising modified metalloporphyrin and temperature-responsive coordination polymer, wherein the mass ratio of the modified metalloporphyrin to the temperature-responsive coordination polymer is 1 (10-20).
  2. 2. The temperature-responsive CP-metalloporphyrin dynamic interpenetrating composition according to claim 1, wherein said preparation method of modified metalloporphyrin comprises the following steps: The synthesis of TPP-Oet comprises dissolving TPP in chloroform, adding ethyl 4-hydroxybenzoate and AlCl 3 , refluxing, steaming to remove part of solvent, purifying by silica gel column chromatography, collecting target component, steaming, and drying to obtain TPP-OEt; The metal coordination reaction is to dissolve TPP-OEt in chloroform, add methanol solution of metal salt of corresponding metal in excessive metalloporphyrin, reflux-cool, filter, wash with methanol, and vacuum dry to obtain modified metalloporphyrin.
  3. 3. The temperature-responsive CP-metalloporphyrin dynamic interpenetrating composition according to claim 1, wherein the metal in said modified metalloporphyrin is any one or more of Fe, al, co, zn.
  4. 4. The temperature-responsive CP-metalloporphyrin dynamic interpenetrating composition according to claim 1, wherein the metal salt of the corresponding metal in the metalloporphyrin is any one or more of FeCl 3 ·6H 2 O、AlCl 3 、CoCl 2 ·6H 2 O or ZnCl 2 .
  5. 5. The temperature-responsive CP-metalloporphyrin dynamic interpenetrating composition according to claim 1, wherein the preparation method of the temperature-responsive coordination polymer comprises the following steps: The preparation method of NIPAM-PDA comprises dissolving PDA in DMF, adding NIPAM, DCC, DMAP, stirring at room temperature, filtering, concentrating the filtrate by rotary evaporation to 1/3-1/2 of the original volume, precipitating the crude product with diethyl ether, and vacuum drying to obtain NIPAM-PDA; The preparation of the temperature response coordination polymer comprises the steps of dissolving Zn (NO 3 ) 2 ·6H 2 O and NIPAM-PDA) in DMF, performing ultrasonic dispersion, transferring to a hydrothermal kettle, reacting for 20-28h at 110-130 ℃, naturally cooling to room temperature, filtering, washing with DMF, and performing vacuum drying to obtain the temperature response coordination polymer powder.
  6. 6. The temperature-responsive CP-metalloporphyrin dynamic interpenetrating composition according to claim 5, wherein the molar ratio of zinc ion in Zn (NO 3 ) 2 ·6H 2 O) to the NIPAM-PDA is 1 (1.8-2.2).
  7. 7. A method for preparing the temperature-responsive CP-metalloporphyrin dynamic interpenetrating composition according to any one of claims 1 to 6, which is characterized by comprising the steps of mixing the modified metalloporphyrin and the temperature-responsive coordination polymer according to a mass ratio of 1 (10 to 20), adding 40 to 60mL of toluene, heating to 45 to 55 ℃ and stirring for 1.5 to 2.5 hours, removing the toluene by rotary evaporation, and drying in vacuum for 4 to 6 hours to obtain the final composition.
  8. 8. Use of a temperature-responsive CP-metalloporphyrin dynamic interpenetrating composition according to any one of claims 1 to 6 as a catalyst in hydrocarbon selective oxidation, alcohol oxidation, phenol oxidation, nitro compound reduction, unsaturated bond oxidation reduction, copolymerization of alkylene oxide with carbon dioxide.
  9. 9. The use according to claim 8, characterized in that the ratio of mass of the temperature-responsive CP-metalloporphyrin dynamic interpenetrating composition to the molar amount of the substrate is comprised between 0.005 and 0.015g/mmol.
  10. 10. The use according to claim 8, wherein in the copolymerization of alkylene oxide with carbon dioxide, the alkylene oxide is propylene oxide or ethylene oxide, the reaction conditions are a pressure of 2-4MPa, a temperature of 60-80 ℃, the product is a polycarbonate-polyether polyol with a molecular weight of 2000-4000 Da; optionally, in the copolymerization reaction of alkylene oxide and carbon dioxide, the initiator is any one or more of dihydric alcohol, dibasic acid and polyhydric alcohol.

Description

Temperature response type CP-metalloporphyrin dynamic interpenetrating composition, preparation method and application thereof Technical Field The application relates to the technical field of catalysts, in particular to a temperature response type CP-metalloporphyrin dynamic interpenetrating composition, a preparation method and application thereof. Background The metalloporphyrin catalyst has a unique electronic structure, and shows excellent catalytic activity in selective oxidation-reduction reactions such as hydrocarbon oxidation, alcohol oxidation and the like, so that the metalloporphyrin catalyst is one of research hot spots in the field of catalysis. In order to solve the problems that the homogeneous metalloporphyrin catalyst is difficult to separate and recycle and the metal components are easy to lose, the heterogeneous modification scheme (such as metalloporphyrin-carbon nanotube supported catalyst) that metalloporphyrin is supported on carriers such as carbon nanotubes and molecular sieves is commonly adopted in the prior art. However, the existing supported metalloporphyrin catalyst has two outstanding defects that firstly, the utilization rate of active sites is low, the catalytic performance is limited, metalloporphyrin is easy to agglomerate on the surface of a carrier or is wrapped by a carrier pore canal, so that the exposure of the active sites is insufficient, the catalytic conversion rate and the product selectivity are low, the expected effect can be achieved only by prolonging the reaction time, secondly, the recovery efficiency is low, the circulation stability is poor, the recovery process is combined with repeated washing by means of centrifugal separation, the operation is tedious and takes a long time, meanwhile, the active components of metalloporphyrin are easy to fall off in the washing and centrifugal process, the catalyst is low in recycling times and high in metal loss rate, and the industrial application cost is remarkably increased. In addition, in the copolymerization reaction of propylene oxide/ethylene oxide and carbon dioxide, the existing catalyst has the problems of low catalytic efficiency, high addition amount and high recovery difficulty, and can not meet the requirements of low cost and high activity in industrial production. Therefore, developing a metalloporphyrin-based catalyst capable of synchronously solving the defects of insufficient exposure of active sites, complicated recovery and serious metal loss becomes a technical problem to be solved in the field. Disclosure of Invention The application provides a temperature response type CP-metalloporphyrin dynamic interpenetrating composition, a preparation method and application thereof. The temperature-responsive CP-metalloporphyrin (Fe, al, co, zn) dynamic interpenetrating composition catalyst provided by the application realizes the synergistic promotion of high catalytic conversion efficiency and selectivity, quick and convenient recovery, low metal loss and long cycle life, can efficiently catalyze the copolymerization reaction of propylene oxide/ethylene oxide and carbon dioxide to generate polycarbonate-polyether polyol with the molecular weight of 2000-4000Da, and has the advantages of low addition amount and high activity of the recyclability and copolymerization reaction of oxidation reaction, and the comprehensive performance is obviously superior to that of the traditional metalloporphyrin supported catalyst. In a first aspect, the application provides a temperature-responsive CP-metalloporphyrin dynamic interpenetrating composition, which adopts the following technical scheme: The temperature-responsive CP-metalloporphyrin dynamic interpenetrating composition specifically comprises modified metalloporphyrin and temperature-responsive coordination polymer, wherein the mass ratio of the modified metalloporphyrin to the temperature-responsive coordination polymer is 1 (10-20). The application realizes the convenience of high activity and heterogeneous recovery of homogeneous catalysis through a 'temperature response type dynamic interpenetrating structure', wherein in a catalysis stage (45-55 ℃) a CP pore canal expands, metalloporphyrin and CP form dynamic coordination interpenetrating, active sites are fully exposed in a monodispersed form (the size is 5-10nm without agglomeration), the problem of 'active site encapsulation/agglomeration' of the traditional heterogeneous catalyst is solved, and in a recovery stage (20-30 ℃) the CP pore canal contracts, coordination bonds are reversibly dissociated, the catalyst is quickly precipitated, and the defect of 'difficult separation and metal loss' of the traditional homogeneous catalyst is avoided. Compared with the traditional metalloporphyrin supported catalyst (such as CoTPP/CNT of comparative example 1), the temperature-responsive CP-metalloporphyrin dynamic interpenetrating composition provided by the application has outstanding physical advantages