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CN-121975124-A - Modified silicone oil with aldehyde functional group and preparation method and application thereof

CN121975124ACN 121975124 ACN121975124 ACN 121975124ACN-121975124-A

Abstract

The invention discloses modified silicone oil with aldehyde functional groups, a preparation method and application thereof, and belongs to the technical field of organic silicon modified silicone oil, wherein the structural general formula of the modified silicone oil with the aldehyde functional groups is shown as I, and at least one of R 1 ,R 2 ,R 3 ,R 4 ,R 5 ,R 6 ,R 7 ,R 8 is an aldehyde group. The synthesis method comprises the steps of mixing olefin-containing siloxane, a metal catalyst, a ligand and a solvent in a synthesis gas system for reaction to obtain the modified silicone oil with aldehyde functional groups. The preparation process is simple, and the preparation of the novel modified aldehyde-containing silicone oil is attempted to be improved for the first time. The silicone oil can be subjected to a gel-coupling reaction with amine to form gel, has higher viscosity and hydrophobicity, and has a strong application prospect in the field of gel self-healing.

Inventors

  • XU LIWEN
  • TIAN SHUYUAN
  • SHI LIN
  • XU ZHENG
  • YANG XUEMIN
  • YE FEI
  • CAO JIAN

Assignees

  • 杭州师范大学

Dates

Publication Date
20260505
Application Date
20260121

Claims (10)

  1. 1. The modified silicone oil with aldehyde functional groups is characterized in that the structural formula of the modified silicone oil is shown as (I): In the formula (I), R 1 -R 10 is independently selected from a straight-chain or branched-chain alkyl group with 1-18 carbon atoms, an aryl group with 6-18 carbon atoms, an acyloxy group with 2-18 carbon atoms, an alkoxy group with 1-18 carbon atoms or an aldehyde group with 1-6 carbon atoms, and at least one of R 1 -R 8 is an aldehyde group; a, b is selected from any integer of 1-18, c ranges from 0 to 5000, and d ranges from 0 to 5000.
  2. 2. A method for preparing the novel modified silicone oil having an aldehyde functional group according to claim 1, comprising the steps of: Mixing olefin-containing siloxane shown in a formula (II), a metal catalyst, a ligand and a solvent, introducing synthesis gas to react to prepare a modified silicone oil crude product with aldehyde functional groups, and centrifuging and distilling under reduced pressure to remove the ligand, the catalyst and low-boiling substances to obtain the modified silicone oil with aldehyde functional groups shown in the formula (I); the synthetic route is as follows: R 11 -R 20 in the formula (II) is independently selected from a linear or branched alkyl group of 1-18 carbon atoms, an alkenyl group of 2-18 carbon atoms, an aryl group of 6-18 carbon atoms, an acyloxy group of 2-18 carbon atoms, an alkoxy group of 1-18 carbon atoms, and at least one of R 11 -R 20 is an alkenyl group.
  3. 3. The method according to claim 2, wherein the specific structure of the olefin-containing siloxane is any one of the following formulas (1) to (8): 。
  4. 4. The preparation method according to claim 2, wherein the metal catalyst is any one of rhodium acetylacetonate bis (ethylene) chloride, rhodium (1, 5-cyclooctadiene) chloride dimer, rhodium dicarbonyl acetylacetonate, and rhodium bis (1, 5-cyclooctadiene) tetrafluoroborate.
  5. 5. The method of claim 2, wherein the ligand is (a) or (b): 。
  6. 6. The method according to claim 2, wherein the solvent is one selected from tetrahydrofuran, toluene, 1, 4-dioxane, N-dimethylformamide, and nitrile compounds.
  7. 7. The method of claim 2, wherein the volume ratio of CO to H 2 in the synthesis gas is 1:1-5.
  8. 8. The process of claim 7 wherein the synthesis gas is at a pressure of 20 to 40 bar.
  9. 9. The preparation method according to claim 2, wherein the reaction temperature is 70-120 o C and the reaction time is 12-36h.
  10. 10. Use of the novel modified silicone oil having aldehyde functional groups according to claim 1 in synthetic gels.

Description

Modified silicone oil with aldehyde functional group and preparation method and application thereof Technical Field The invention belongs to the technical field of organic chemistry, and particularly relates to modified silicone oil with aldehyde functional groups, and a preparation method and application thereof. Background In the field of material science, silicone oil is widely used in a plurality of industries, including personal care products, textile treatment, electronic equipment packaging and the like, by virtue of unique physical and chemical characteristics, such as low surface tension, good thermal stability, chemical inertness, excellent lubricity and the like, of silicone oil as an organosilicon material with excellent performance. However, with rapid development of science and technology and continuous improvement of material performance requirements in various industries, the performance of the traditional silicone oil gradually exposes some limitations, such as easy aging, poor high temperature tolerance and other problems, and is difficult to meet increasingly complex and refined application requirements, which prompt scientific researchers to continuously explore and develop novel silicone oil materials so as to fill the blank of the prior art. In the application field of traditional silicone oil, especially in the field of gel self-healing, a few problems to be solved urgently exist. When the traditional silicone oil material is subjected to condensation reaction with an amino group, the condensation reaction is usually carried out with the aid of a catalyst, so that the reaction cost and the process complexity are increased, and additional impurities can be introduced to influence the performance of a final product. In addition, the traditional silicone oil has defects in the aspects of viscosity, hydrophobicity and the like after gel formation, and the use of the traditional silicone oil in gel self-healing applications with extremely high performance requirements is limited. For example, in some self-healing protective coatings for electronic devices, a gel material is required to have rapid formation, high viscosity to ensure the firmness of the coating and good hydrophobicity to prevent moisture erosion, but gels made of traditional silicone oils often have difficulty meeting these requirements at the same time, resulting in a small market share in these high-end application fields, and not fully exploiting their potential. Thus, there is a need for new modified silicone oils to overcome the above-mentioned drawbacks. Disclosure of Invention The first aim of the invention is to provide the modified silicone oil with aldehyde functional groups, which can be subjected to condensation reaction with amine groups under the condition of no catalyst to form gel instantly, has higher viscosity and hydrophobicity, and has strong application prospect in the field of self-healing of gel. In order to achieve the above purpose, the present invention adopts the following technical scheme: A novel modified silicone oil with aldehyde functional groups has a structural formula shown in (I): R1,R2,R3,R4,R5,R6,R7,R8,R9,R10 in formula (I) is independently selected from a linear or branched alkyl group of 1 to 18 carbon atoms, an aryl group of 6 to 18 carbon atoms, an acyloxy group of 2 to 18 carbon atoms, an alkoxy group of 1 to 18 carbon atoms, an aldehyde group of 1 to 6 carbon atoms, and at least one of R 1,R2,R3,R4,R5,R6,R7,R8 is an aldehyde group. Wherein a, b is selected from any integer of 1-18, c ranges from 0 to 5000, and d ranges from 0 to 5000. A second object of the present invention is to provide a method for preparing the above novel modified silicone oil having an aldehyde functional group, comprising the steps of: Mixing olefin-containing siloxane shown in a formula (II), a metal catalyst, a ligand and a solvent, introducing synthesis gas to react to prepare a modified silicone oil crude product with aldehyde functional groups, and centrifuging and distilling under reduced pressure to remove the ligand, the catalyst and low-boiling substances to obtain the modified silicone oil with aldehyde functional groups shown in the formula (I); the synthetic route is as follows: R11,R12,R13,R14,R15,R16R17,R18R19,R20 in formula (II) is independently selected from a linear or branched alkyl group of 1 to 18 carbon atoms, an alkenyl group of 2 to 18 carbon atoms, an aryl group of 6 to 18 carbon atoms, an acyloxy group of 2 to 18 carbon atoms, an alkoxy group of 1 to 18 carbon atoms, and at least one of R11,R12,R13,R14,R15,R16,R17,R18,R19,R20 is an alkenyl group. Preferably, the specific structure of the olefin-containing siloxane is any one of the following formulas (1) to (8). Preferably, the metal catalyst is any one of rhodium acetylacetonate bis (ethylene) chloride, rhodium (1, 5-cyclooctadiene) chloride dimer, rhodium dicarbonyl acetylacetonate, and rhodium bis (1, 5-cyclooctadiene) tetrafluoro