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CN-122011255-A - Imidazole salt functionalized resin material, preparation method and application thereof, and method for carbonylation of epoxy compound

CN122011255ACN 122011255 ACN122011255 ACN 122011255ACN-122011255-A

Abstract

The invention relates to the field of high polymer materials, in particular to an imidazole salt functional resin material, a preparation method and application of the imidazole salt functional resin material and a method for carbonylating an epoxy compound. The resin material has a structure represented by the following formula (1): In the above-mentioned formula (1), The resin material is a polystyrene resin matrix, L is an alkylene chain, the carbon number of the main chain is more than 3, R 1 is a C1-C10 alkylene chain, R 2 is selected from hydroxyl, carboxyl, amino or hydrogen, X ‑ is an anion, and the number ratio of the styrene structural units to L in the polystyrene resin matrix is 1. The imidazole salt functionalized resin material has high catalytic activity and good thermal stability.

Inventors

  • YU FENGPING
  • GE JUNWEI
  • ZHOU JIPENG
  • JIN MING
  • HE WENJUN

Assignees

  • 中国石油化工股份有限公司
  • 中石化（上海）石油化工研究院有限公司

Dates

Publication Date
20260512
Application Date
20241111

Claims (11)

  1. 1. An imidazole salt functionalized resin material, characterized in that the resin material has a structure represented by the following formula (1): In the above-mentioned formula (1), Is a polystyrene resin matrix, L is an alkylene chain with the carbon number of a main chain being more than 3, R 1 is a C1-C10 alkylene chain, R 2 is selected from hydroxyl, carboxyl, amino or hydrogen, and X - is an anion; in the resin material, the ratio of the number of the styrene structural units to the number of L in the polystyrene resin matrix is 1.
  2. 2. The resin material according to claim 1, wherein the polystyrene-based resin matrix includes a styrene structural unit and a comonomer structural unit therein; Preferably, the proportion of comonomer structural units in the polystyrene resin matrix is not more than 50wt%, preferably 0.1-50wt%; more preferably, the comonomer is selected from at least one of a dibasic alkenylbenzene, a polybasic alkenylbenzene, and a polybasic unsaturated acid ester compound.
  3. 3. The resin material according to claim 1 or 2, wherein, Wherein L is an alkylene chain having 4 to 8 carbon atoms in the main chain, and/or The R 1 is a C1-C5 alkylene chain, and/or R 2 is selected from hydroxy, carboxy or amino, and/or X - is a halide and/or an organic acid ion, preferably a halide.
  4. 4. The preparation method of the imidazole salt functionalized resin material is characterized by comprising the following steps of: 1) Carrying out copolymerization reaction on halogenated alkyl styrene and a comonomer in the presence of an initiator and a first solvent to obtain a resin material; 2) The resin material and the nitrogen alkyl imidazole and/or nitrogen (substituted alkyl) imidazole are subjected to contact reaction under the condition of a second solvent to obtain an intermediate material; 3) The intermediate material is subjected to an ion exchange treatment of halogen ions and/or organic acid ions.
  5. 5. The preparation method according to claim 4, wherein, The haloalkylstyrene is bromoalkylstyrene, preferably bromoC 3-C6 alkylstyrene, and/or The comonomer is selected from di-alkenyl benzene and/or poly-unsaturated acid ester compound, preferably di-alkenyl benzene and/or poly-alkenyl benzene, and/or The initiator is at least one selected from benzoyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile, lauroyl peroxide and cumene hydroperoxide, and/or The first solvent is an aqueous solution containing a dispersant, preferably gelatin; the second solvent is at least one selected from acetonitrile, tetrahydrofuran, N-dimethylformamide and N, N-dimethylacetamide.
  6. 6. The production method according to claim 5, wherein the conditions of the copolymerization reaction include: The weight content of the halogenated alkylstyrene is 50wt% to 95wt%, preferably 60wt% to 90wt%, the weight content of the comonomer is 2wt% to 49.9wt%, preferably 8wt% to 39.5wt%, the weight content of the initiator is 0.1wt% to 3wt%, preferably 0.5wt% to 2.0wt%, and/or based on the total weight of the copolymerization system The polymerization reaction temperature is 60-100 ℃, and/or the time is 6-24 hours, preferably, the copolymerization reaction is firstly carried out for 1-3 hours at 65-75 ℃, then is carried out for 2-6 hours at 80-90 ℃, and finally is carried out for 3-6 hours at 95-105 ℃.
  7. 7. The production method according to any one of claims 4 to 6, wherein the conditions of the contact reaction include: At a temperature of 50-180 ℃, preferably 60-120 ℃, and/or For 10-36h, and/or The mass ratio of the imidazole compound to the resin material is 1 (1-4), preferably 1 (1-3).
  8. 8. An imidazole salt functional resin material prepared by the preparation method of any one of claims 4-7.
  9. 9. Use of the imidazolium-functionalized resin material according to any one of claims 1 to 3 and/or the imidazolium-functionalized resin material according to claim 8 as a catalyst in an epoxide carbonylation reaction.
  10. 10. A process for the carbonylation of an epoxy compound, which comprises contacting the epoxy compound with a carbonylation reagent in the presence of a catalyst which is the imidazolium-functional resin material according to any one of claims 1 to 3 and/or the imidazolium-functional resin material according to claim 8, preferably, The epoxy-containing compound has the following general formula: Wherein R 1 -R 4 is each independently selected from one of hydrogen, C 1 -C 6 alkyl and C 6 -C 10 aryl, preferably R 1 -R 4 is each independently selected from hydrogen, methyl, ethyl, propyl, butyl and phenyl. And/or The carbonylation reagent is selected from carbon dioxide and/or carbon disulphide, preferably carbon dioxide.
  11. 11. The method of claim 10, wherein, The contact is in countercurrent contact, and/or The contacting is performed in a bubbling bed reactor, and/or The imidazole salt functionalized resin material is provided with at least three beds in the reactor, and/or Along the flow direction of epoxide, the average grain diameter of imidazole salt functional resin material filled in the reactor is gradually increased layer by layer, and the increasing amplitude is 0.1-0.5 mm/layer; And/or The conditions of the contacting include: at a temperature of 40-180 ℃, preferably 80-130 ℃, and/or The carbonylation reagent provides a pressure of from 0.1 to 10.0MPa, preferably from 1.0 to 4.0MPa, and/or The liquid space velocity of the reaction is 0.05-10.0h -1 , preferably 0.1-5.0h -1 .

Description

Imidazole salt functionalized resin material, preparation method and application thereof, and method for carbonylation of epoxy compound Technical Field The invention relates to the field of high polymer materials, in particular to an imidazole salt functional resin material, a preparation method and application of the imidazole salt functional resin material and a method for carbonylating an epoxy compound. Background The new energy industry is an emerging industry with national emphasis on development, and meanwhile, the development of new energy vehicles makes the application of power batteries more and more important. The demand for alkylene carbonate solvents such as ethylene carbonate and propylene carbonate as an important component of power cell electrolytes has increased year by year. In addition, alkylene carbonates are also of great use in the printing, polymer manufacturing, textile and other industries. Currently, the mainstream production method of alkylene carbonate is to prepare alkylene oxide and carbon dioxide under the action of a homogeneous catalysis system. The homogeneous system has the problems of difficult separation of the catalyst, catalyst residue and high cost of solid-liquid waste treatment. Thus, there is a higher demand for the green and economical production process of alkylene carbonate. Compared with a homogeneous catalysis system, the heterogeneous catalysis system has no problems of difficult separation of catalyst products, catalyst residues and the like. Heterogeneous catalytic systems currently developed include oxides, MOFs, carbon materials, ionic liquids, and the like. Such as MgO-Al 2O3 metal compound, difunctional porous metal organic framework material UiO-67-IL, imidazole type ionic liquid catalyst loaded on chitosan, hydroxyl imidazole type ionic liquid loaded on ion exchange resin, zinc halide catalyst loaded on ion exchange resin, etc. Wherein the ion exchange resin supported catalyst is more studied. Zhang et al reported an ion exchange resin supported hydroxyimidazole ionic liquid PS-HEIMBR (CATALYSIS TODAY 2009,148,361-367) that had high particle size requirements for the catalyst particles when used in an epoxy/CO 2 system. When the catalyst particles are 100 mu m, after the reaction is carried out for 4 hours at 120 ℃ and 2.5MPa, the conversion rate of propylene oxide and the selectivity of propylene carbonate can reach 99 percent, and the catalyst has higher catalytic efficiency. However, the 1mm catalyst particles, which have not been ground, are capable of converting only 87% of the propylene oxide under the same conditions. And bromine ethanol is adopted in the preparation of the catalyst, so that the production cost of the catalyst is increased, and the catalyst is not beneficial to industrial application. CN105503608a discloses a halogen type composite hydroxyimidazole resin catalyst, and nano materials such as carbon nanotubes and hydroxyhalides are added during the preparation of the catalyst to improve the material performance. After the ethylene oxide is treated for 3 hours at 120 ℃ and 2.0MPa under the action of the catalyst, the conversion rate of the ethylene oxide can reach 98.6 percent, and the selectivity of the ethylene carbonate can reach 99.7 percent. However, the nano material, the hydroxyl halide and other reagents adopted in the preparation process also increase the production cost of the catalyst, and the catalyst has poor repeated performance, and the performance can be reduced after 5 times of repeated use. Xia et al in Appl. Catal A2005,279:125-129 report a system with zinc halide-loaded chitosan as the main catalyst and 1-butyl-3-methylimidazolium bromide as the co-catalyst. After propylene oxide and CO 2 react for 1 hour at 110 ℃ and 1.5MPa, the selectivity of propylene carbonate can reach more than 99 percent, and the yield can reach 95 percent. After the technological parameters are adjusted, the highest yield of propylene carbonate can reach 97 percent. However, the stability and strength of the catalytic system are insufficient, and after the catalytic system is repeatedly used for 5 times, the yield of propylene carbonate is reduced from 95% to 87%, which is not beneficial to industrial scale-up production. Thus, although heterogeneous catalytic systems, including ion exchange resin catalysts, have many advantages, there are still some disadvantages in how to improve the usability of the catalyst, and research and development of a heterogeneous catalytic system with high thermal stability is still a hot spot for the research of catalysts for the reaction of epoxy compounds with carbon dioxide. Disclosure of Invention The invention aims to overcome the defects of incomplete imidazole salt functionalization and insufficient stability of a resin material in the prior art, and provides an imidazole salt functionalized resin material, a preparation method and application of the imidazole salt functionalized resin material and