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CN-122011416-A - Organosilicon supermolecular elastomer based on crown ether host-guest effect crosslinking and preparation method thereof

CN122011416ACN 122011416 ACN122011416 ACN 122011416ACN-122011416-A

Abstract

A preparation method of a high-stretchability organosilicon supermolecular elastomer comprises the steps of forming a quasimetane structure by a host-guest effect of aldehyde group modified crown ether and a secondary ammonium salt, and introducing the quasimetane structure into a polydimethylsiloxane prepolymer. The invention provides a crown ether supermolecular polymer network which has excellent performance, easy synthesis and mild synthesis condition, and the main guest action of crown ether and secondary ammonium salt enables the supermolecular polymer network to have good dynamic property. The toughening agent is added into the organic silicon elastomer, so that the elastomer has better mechanical property and energy dissipation, and the maximum elongation and the ductility of the elastomer are greatly enhanced without sacrificing the mechanical strength.

Inventors

  • XU XINGDONG
  • ZHANG JINGJING
  • ZHANG JUNYING
  • FENG SHENGYU

Assignees

  • 山东大学

Dates

Publication Date
20260512
Application Date
20260228

Claims (9)

  1. 1. A preparation method of a high-stretchability organosilicon supermolecular elastomer is characterized in that aldehyde group modified crown ether and secondary ammonium salt form a quasiplane structure through a host-guest effect, and the quasiplane structure is introduced into a polydimethylsiloxane prepolymer to prepare the organosilicon supermolecular elastomer.
  2. 2. The method for preparing a high-stretchability silicone supermolecular elastomer as claimed in claim 1, comprising the steps of: (1) Respectively dispersing the benzo-24-crown-8 modified by aldehyde groups and the secondary ammonium salt modified by aldehyde groups in tetrahydrofuran, mixing and then carrying out ultrasonic treatment to obtain quasimethine; (2) The elastomer is prepared by any one of the following modes: Mode one: Adding the quasimethine into tetrahydrofuran dispersion liquid of the aminopropyl end-capped polydimethylsiloxane to obtain a mixed liquid A, slowly adding tetrahydrofuran dispersion liquid of 5'- (4-formylphenyl) -2',4',6' -trimethyl- [1,1':3',1 '-terphenyl ] -4,4' -dicarboxaldehyde (FTTD) into the mixed liquid A, uniformly mixing under the protection of inert gas, reacting, defoaming after the reaction is finished, pouring into a mould, and drying to obtain a polysiloxane elastomer A; mode two: Adding the pseudo-rotaxane into tetrahydrofuran dispersion liquid of aminopropyl end-capped polydimethylsiloxane, uniformly mixing, adding tetrahydrofuran dispersion liquid of isophorone diisocyanate, reacting to obtain reaction liquid B, slowly adding tetrahydrofuran dispersion liquid of 5'- (4-formylphenyl) -2',4',6' -trimethyl- [1,1':3',1 '-terphenyl ] -4,4' -dicarboxaldehyde into the reaction liquid B, uniformly mixing under the protection of inert gas, reacting, defoaming after the reaction is finished, pouring into a mould, and drying to obtain polysiloxane elastomer B; mode three: The preparation method comprises the steps of adding pseudo-rotaxane into tetrahydrofuran dispersion liquid of aminopropyl-terminated polydimethylsiloxane, uniformly mixing, adding tetrahydrofuran dispersion liquid of isophorone diisocyanate, reacting overnight to obtain reaction liquid C, respectively adding dithiodiphenylamine and tetrahydrofuran dispersion liquid of 5'- (4-formylphenyl) -2',4',6' -trimethyl- [1,1':3',1 '-terphenyl ] -4,4' -dicarboxaldehyde (FTTD) into the reaction liquid C slowly, uniformly mixing and reacting under the protection of inert gas, defoaming after the reaction is finished, pouring into a mold, and drying to obtain polysiloxane elastomer C.
  3. 3. The method for preparing a high-stretchability silicone supermolecular elastomer as claimed in claim 2, wherein the molar ratio of benzo-24-crown-8 to aldehyde group modified secondary ammonium salt in step (1) is 1:1.
  4. 4. The process for preparing a high-elongation silicone supermolecular elastomer according to claim 2, wherein in the first step (2), the molecular weight of the aminopropyl-terminated polydimethylsiloxane is 1000 to 20000, and the molar ratio of the aminopropyl-terminated polydimethylsiloxane to 5'- (4-formylphenyl) -2',4',6' -trimethyl- [1,1':3',1 '-terphenyl ] -4,4' -dicarboxaldehyde to the pseudorotaxane is 150 (99 to 80): 1 to 20.
  5. 5. The method for producing a high-stretchability silicone supermolecular elastomer as claimed in claim 2, wherein in the second mode (2), the molecular weight of the aminopropyl-terminated polydimethylsiloxane is 1000 to 20000, and the molar ratio of the aminopropyl-terminated polydimethylsiloxane, isophorone diisocyanate, 5'- (4-formylphenyl) -2',4',6' -trimethyl- [1,1':3',1 '-terphenyl ] -4,4' -dicarboxaldehyde (FTTD) to the quasimethine is 300:150 (99 to 90): 1 to 10.
  6. 6. The method for producing a high-stretchability silicone supermolecular elastomer as claimed in claim 2, wherein in the third mode (2), the molecular weight of the aminopropyl-terminated polydimethylsiloxane is 1000 to 20000, and the molar ratio of the aminopropyl-terminated polydimethylsiloxane, dithiodiphenylamine, isophorone diisocyanate, 5'- (4-formylphenyl) -2',4',6' -trimethyl- [1,1':3',1'' -terphenyl ] -4,4'' -dicarboxaldehyde (FTTD) to the pseudorotaxane is (297 to 270): (3 to 30): 150 (99 to 90): 1 to 10).
  7. 7. The method for preparing a high-stretchability silicone supermolecular elastomer as claimed in claim 2, wherein dibutyltin dilaurate is used as the catalyst in the reaction process of step (2).
  8. 8. An organosilicon supermolecular elastomer, characterized in that it is prepared by the process according to any one of claims 2 to 7.
  9. 9. Use of the silicone supermolecular elastomer of claim 8 as a toughening agent.

Description

Organosilicon supermolecular elastomer based on crown ether host-guest effect crosslinking and preparation method thereof Technical Field The invention belongs to the technical field of supermolecular materials, and relates to an organosilicon supermolecular elastomer based on crown ether host-guest effect crosslinking, a preparation method and application thereof. Background The polysiloxane elastomer is a high molecular polymer with a main chain containing a repeated structure of siloxane bonds. The material has excellent high and low temperature resistance, biocompatibility, chemical stability and electrical insulation, so that the material has irreplaceable functions in the fields of flexible electronics, biomedical devices, soft robots and the like. The Stanford university Bao Zhena subject group prepares a stretch-resistant elastomer material based on hydrogen bonds with different strength, two isocyanates are introduced into a PDMS system, the elongation at break of the material reaches 1200%, fauvre et al synthesizes an organosilicon elastomer with self-repairing performance containing self-associated bisamide groups through the Aza-Michael addition reaction of N, N' -methylenebisacrylamide and low molecular weight end group (3 amino propyl) polydimethylsiloxane, and Gao et al prepares a self-repairing performance, recoverable and firm elastomer based on the dynamic decimal hydrogen bond structure of carbohydrazine ester and simultaneously combines with a soft Polydimethylsiloxane (PDMS) chain. However, the existing organosilicon elastomer still has the problem that the strength and toughness are difficult to balance, so that the material generally has the defects of low toughness, poor mechanical property, unrepairable property and the like. These drawbacks severely limit their development in advanced applications requiring long life, sustainability or dynamic adaptation. Disclosure of Invention The invention provides a novel high-tensile organosilicon supermolecular elastomer and a preparation method thereof, aiming at the problems that the traditional covalent crosslinking organosilicon elastomer has lower elongation at break, and the single non-covalent crosslinking organosilicon elastomer has poor physical properties and the like. In order to achieve the above purpose, the invention is realized by adopting the following technical scheme: A preparation method of a high-stretchability organosilicon supermolecular elastomer comprises the steps of forming a quasimetane structure by a host-guest effect of aldehyde group modified crown ether and a secondary ammonium salt, and introducing the quasimetane structure into a polydimethylsiloxane prepolymer. The preparation method of the high-stretchability organosilicon supermolecular elastomer comprises the following preparation steps: (1) Respectively dispersing the benzo-24-crown-8 modified by aldehyde group and the secondary ammonium salt modified by aldehyde group in tetrahydrofuran, mixing and then carrying out ultrasonic treatment to obtain the quasimethide. (2) The elastomer is prepared by any one of the following modes: Mode one: The preparation method comprises the steps of adding the quasimethine into tetrahydrofuran dispersion liquid of aminopropyl terminated polydimethylsiloxane to obtain a mixed liquid A, slowly adding tetrahydrofuran dispersion liquid of 5'- (4-formylphenyl) -2',4',6' -trimethyl- [1,1':3',1 '-terphenyl ] -4,4' -dicarboxaldehyde (FTTD) into the mixed liquid A, uniformly mixing under the protection of inert gas, reacting, defoaming after the reaction is finished, pouring into a mould, and drying to obtain the polysiloxane elastomer A. Mode two: the preparation method comprises the steps of adding quasi-rotaxane into tetrahydrofuran dispersion liquid of aminopropyl-terminated polydimethylsiloxane, uniformly mixing, adding tetrahydrofuran dispersion liquid of isophorone diisocyanate, reacting to obtain reaction liquid B, slowly adding tetrahydrofuran dispersion liquid of 5'- (4-formylphenyl) -2',4',6' -trimethyl- [1,1':3',1 '-terphenyl ] -4,4' -dicarboxaldehyde into the reaction liquid B, uniformly mixing under the protection of inert gas, reacting, defoaming after the reaction is finished, pouring into a mould, and drying to obtain the polysiloxane elastomer B. Mode three: The preparation method comprises the steps of adding pseudo-rotaxane into tetrahydrofuran dispersion liquid of aminopropyl-terminated polydimethylsiloxane, uniformly mixing, adding tetrahydrofuran dispersion liquid of isophorone diisocyanate, reacting overnight to obtain reaction liquid C, respectively adding dithiodiphenylamine and tetrahydrofuran dispersion liquid of 5'- (4-formylphenyl) -2',4',6' -trimethyl- [1,1':3',1 '-terphenyl ] -4,4' -dicarboxaldehyde (FTTD) into the reaction liquid C slowly, uniformly mixing and reacting under the protection of inert gas, defoaming after the reaction is finished, pouring into a mold, and drying to obtain polysiloxan