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CN-118084835-B - Method for preparing 2, 5-dimethyl furandicarboxylate by oxidizing and esterifying 2, 5-furandimethanol with cobalt zinc carbon-based material

CN118084835BCN 118084835 BCN118084835 BCN 118084835BCN-118084835-B

Abstract

The invention provides a method for synthesizing 2, 5-dimethyl furandicarboxylate by oxidizing and esterifying 2, 5-furandimethanol by using a cobalt-zinc-based carbon material, belonging to the technical field of catalytic synthesis. The method takes 2, 5-furan dimethanol as a raw material, takes molecular oxygen as an oxidant, takes cobalt zinc carbon-based material as a heterogeneous catalyst, and prepares the 2, 5-furan dimethyl ester through a high-efficiency liquid phase one-step oxidation esterification reaction in a methanol solvent. The cobalt-zinc base material is prepared by mixing a certain amount of cobalt salt, zinc salt and organic nitrogen-containing compound ligand to obtain a precursor, and calcining for 0.5-24h in an inert atmosphere at 500-1100 ℃. The oxidation and esterification method provided by the invention is mild and efficient, and the catalyst is cheap and easy to obtain, so that the method has strong practicability and application scene.

Inventors

  • ZHAO CHEN
  • SHEN XIAOYU
  • TIAN JINGQING
  • MA BING

Assignees

  • 华东师范大学

Dates

Publication Date
20260505
Application Date
20240407

Claims (5)

  1. 1. The method for preparing the dimethyl 2, 5-furandicarboxylate by oxidizing and esterifying the 2, 5-furandimethanol by cobalt zinc carbon-based materials specifically comprises the following steps: The first step is to prepare cobalt zinc based material catalyst: Mixing cobalt nitrate, zinc nitrate and a nitrogen-containing organic ligand, adding the mixture into a solvent, stirring the mixture for 0.5 to 8 hours at a temperature of between 25 and 150 ℃, cooling the mixture to room temperature, removing the solvent by rotary evaporation, and cooling the mixture after the mixture is subjected to heat treatment for 0.5 to 24 hours in an inert atmosphere at a temperature of between 500 and 1100 ℃ to obtain a cobalt-zinc-carbon-based catalyst; the second step is to prepare 2, 5-dimethyl furandicarboxylate: Adding 2, 5-furandimethanol, cobalt zinc carbon-based catalyst and methanol into a reactor, introducing molecular oxygen as an oxygen source, sealing the reactor, setting the reaction temperature and stirring; The nitrogen-containing organic ligand in the catalyst preparation step is one or more of polyaniline, dicyandiamide, melamine, aniline, benzylamine, o-phenylenediamine, triazole, pyrrole, pyridine, quinoline, purine, 1, 10-phenanthroline and 2-methylimidazole; in the catalyst preparation step, the inert atmosphere is one or more than one of nitrogen, argon and helium.
  2. 2. The method according to claim 1, wherein in the catalyst preparation step, the molar ratio of cobalt nitrate to zinc nitrate is 1:0.5-1:10, the total molar ratio of cobalt nitrate to nitrogen-containing organic ligand is 1:1-1:40, and the solvent is 10-120 times of the total mass of the nitrogen-containing organic ligand.
  3. 3. The process according to claim 1, wherein in the step of preparing dimethyl-2, 5-furandicarboxylate, molecular oxygen is derived from air, oxygen or an oxygen-containing gas, and the partial pressure of oxygen is 0.02 to 2MPa.
  4. 4. The method according to claim 1, wherein in the step of preparing the dimethyl 2, 5-furandicarboxylate, the reaction temperature is 25-120 ℃, and the stirring reaction time is 0.5-72h.
  5. 5. The method according to claim 1, wherein the methanol is 2-200 times of the mass of 2, 5-furandimethanol, and the cobalt zinc-based material catalyst is 0.01-1 times of the mass of the raw material 2, 5-furandimethanol.

Description

Method for preparing 2, 5-dimethyl furandicarboxylate by oxidizing and esterifying 2, 5-furandimethanol with cobalt zinc carbon-based material Technical Field The application relates to the technical field of catalytic synthesis, and relates to a method for preparing dimethyl 2, 5-furandicarboxylate by oxidizing and esterifying 2, 5-furandimethanol with cobalt zinc carbon-based materials. Background Green renewable bio-based raw materials are attracting attention as a replacement for traditional fossil-based resources. 2, 5-furandicarboxylic acid is used as one of 12 bio-based chemical substances with high added value, can be used for synthesizing various fine chemical products, and has huge market potential as an important monomer of corrosion-resistant plastics. Dimethyl 2, 5-furandicarboxylate is an important derivative of 2, 5-furandicarboxylic acid and can be used in the production of bio-based polyester polyethylene furandicarboxylate (PEF). The PEF is a novel recyclable engineering plastic, has the melting temperature, young modulus, glass transition temperature, tensile strength and other aspects similar to those of common plastic polyethylene terephthalate (PET), has biodegradability, meets the development requirements of green chemistry and green industry, and has huge application potential. Compared with 2, 5-furandicarboxylic acid, the 2, 5-furandicarboxylic acid dimethyl ester is easy to produce and prepare due to good solubility and stability, and can effectively avoid decarboxylation reaction at high temperature, so that the product yield is improved, and the 2, 5-furandicarboxylic acid dimethyl ester has extremely high application value. At present, the 2, 5-dimethyl furandicarboxylate is mainly produced by taking 5-hydroxymethyl furfural (HMF) as a raw material, but the HMF has strong hygroscopicity and is extremely unstable under alkaline conditions, so that the industrial production of the 2, 5-dimethyl furandicarboxylate is limited. 2, 5-furandimethanol has a similar structure to HMF and is more stable under alkaline conditions than HMF. Therefore, the development of a new method for preparing the 2, 5-dimethyl furandicarboxylate by using the 2, 5-dimethyl furanate as the raw material through oxidative esterification, which is environment-friendly, low-cost and efficient, has important significance. According to the invention, molecular oxygen is used as an oxygen source, cobalt zinc carbon-based material is used as a catalyst, 2, 5-furandimethanol is efficiently oxidized and esterified into 2, 5-furandicarboxylic acid dimethyl ester by a one-step method, the reaction condition is mild, the method is safe and environment-friendly, and the heterogeneous catalyst is simple to separate from the product. Disclosure of Invention The invention aims to provide a novel method for preparing 2, 5-dimethyl furandicarboxylate by oxidizing and esterifying 2, 5-dimethyl furanate. The method is a novel method for oxidizing and esterifying 2, 5-furandimethanol into 2, 5-furandicarboxylic acid dimethyl ester in methanol solution by taking cobalt zinc carbon-based material as a catalyst and molecular oxygen as an oxygen source. In order to achieve the above purpose, the invention adopts the following technical scheme: a method for synthesizing 2, 5-dimethyl furandicarboxylate by catalyzing 2, 5-furandimethanol with cobalt zinc carbon-based material uses cobalt zinc-based material as catalyst to oxidize 2, 5-furandimethanol into 2, 5-dimethyl furandicarboxylate. The method specifically comprises the following steps: (1) Preparation of cobalt zinc carbon-based material catalyst Mixing cobalt nitrate, zinc nitrate and a nitrogen-containing organic ligand, adding the mixture into a solvent, stirring the mixture for 0.5 to 8 hours at a temperature of between 25 and 150 ℃, cooling the mixture to room temperature, removing the solvent by rotary evaporation, and cooling the mixture after the mixture is subjected to heat treatment for 0.5 to 24 hours in an inert atmosphere at a temperature of between 500 and 1100 ℃ to obtain the cobalt-zinc-carbon-based catalyst. (2) Preparation of dimethyl 2, 5-furandicarboxylate 2, 5-Furan dimethanol, cobalt zinc carbon-based catalyst and methanol are put into a reactor, wherein the dosage of the methanol is 2-200 times of the mass of the 2, 5-furan dimethanol, the dosage of the cobalt zinc-based catalyst is 0.01-2 times of the mass of the raw material 2, 5-furan dimethanol, molecular oxygen is introduced as an oxygen source, the reactor is closed, and stirring is carried out after the reaction temperature is set. The mol ratio of the cobalt nitrate to the zinc nitrate in the step (1) is 1:0.5-1:10, the total mol ratio of the cobalt nitrate to the nitrogen-containing organic ligand is 1:1-1:40, and the solvent dosage is 10-120 times of the total mass of the nitrogen-containing organic ligand. The nitrogen-containing organic ligand in the step (1) is one or more of polyaniline, d