CN-122011455-A - Preparation method of bio-based repairable flexible conductive organic silicon film

Abstract

The invention discloses a preparation method of a bio-based repairable flexible conductive organic silicon film. The preparation method comprises the steps of reacting biological polyol PO3G (polytrimethylene ether glycol) with isophorone diisocyanate to obtain an isocyanate-terminated biological prepolymer, sequentially carrying out two-step chain extension by using a mixed chain extender of bis (3-aminopropyl) terminated Polydimethylsiloxane (PDMS), 4' - (hexafluoroisopropylidene) diphenol and isophthalhydrazide to construct a biological-based organic silicon matrix with repairable function, and finally compounding the biological-based organic silicon matrix with a multi-wall carbon nano tube to obtain the organic silicon film with flexibility, conductivity and self-repairing function. The material can be applied to the manufacture of flexible electronic and wearable equipment.

Inventors

• WANG WENPIN
• ZHANG XU
• LI ZHONGCHENG

Assignees

• 青岛科技大学

Dates

Publication Date

20260512

Application Date

20260323

Claims (2)

1. 1. The preparation method of the bio-based repairable flexible conductive organic silicon film is characterized by comprising the following steps of: ① Mixing 2-4 mmol bio-based polyol PO3G (polytrimethylene ether glycol with the number average molecular weight of 2000G/mol), 4-8 mmol isophorone diisocyanate and 10-15 mg dibutyl tin dilaurate, and reacting for 1-2 h at 60-75 ℃ under the protection of N 2 to obtain an isocyanate-terminated bio-based prepolymer; ② 1-2 mmol bis (3-aminopropyl) terminated poly (dimethylsiloxane) PDMS (with the number average molecular weight of 3000 g/mol) is dissolved in 6-18 mL N-N-dimethylacetamide, and is added into the bio-based prepolymer prepared by ① dropwise, the chain extension reaction is carried out continuously at 60-75 ℃ for 1-2 h, and the temperature is reduced to 50 ℃ to obtain isocyanate terminated bio-based organosilicon prepolymer solution; ③ Dissolving 0.5-1 mmol of 4,4' - (hexafluoroisopropylidene) diphenol and 0.5-1 mmol m-phthalhydrazide in 3-6 mL N-N-dimethylacetamide, dropwise adding the solution into the bio-based organosilicon prepolymer solution prepared by ②, continuously performing chain extension reaction at 50 ℃ for 12-24 h, and drying to obtain the bio-based repairable flexible organosilicon; ④ Dispersing 15-20 mg multi-wall carbon nano-tubes and 30-40 mg bio-based repairable flexible organic silicon prepared by ③ in 10-15 mL tetrahydrofuran, fully and uniformly mixing, and compounding to obtain a flexible bio-based repairable conductive organic silicon film; wherein the molar ratio of the bio-based polyol PO3G, isophorone diisocyanate, bis (3-aminopropyl) terminated poly (dimethylsiloxane) PDMS, 4' - (hexafluoroisopropylidene) diphenol and isophthalhydrazide is 4:8:2:1:1.
2. 2. Use of a bio-based repairable flexible conductive silicone membrane obtained by the method of claim 1 in the manufacture of a flexible wearable electronic product, wherein the bio-based repairable flexible conductive silicone membrane is tested by an electrochemical workstation and when a constant voltage of 3V is applied, the current through the membrane material is 10-11 mA.

Description

Preparation method of bio-based repairable flexible conductive organic silicon film Technical Field The invention relates to a preparation method of a bio-based repairable flexible conductive organic silicon film. Specifically, the organosilicon film takes polydimethylsiloxane and bio-based polyol as the basis of a double-soft-segment structure, and is prepared into a bio-based organosilicon matrix with repairable performance by introducing F-H bonds and constructing a synergistic mechanism of multi-level hydrogen bonds, and after being further doped with multi-wall carbon nano tubes, the flexible composite film with good conductivity and self-repairing function can be obtained. Technical Field Elastomer applications have expanded from the traditional field to the frontier technologies of flexible electronics, etc., which benefit from their flexibility, designability and versatility potential. As flexible electronics evolve, there is a pressing need for high performance elastomeric substrates. PDMS is an ideal substrate material due to excellent biocompatibility, flexibility and stability. But pure PDMS has poor strength and toughness due to nonpolar structure and weak intermolecular action, is easy to damage, and limits high-end application. Therefore, it is a great challenge to simultaneously increase the toughness and tear resistance of silicon-based elastomers. If the material has repairability and recyclability, the service life is prolonged and the energy consumption pollution is reduced. Thermoplastic polyurethane urea elastomers spontaneously form microphase separated structures due to the thermodynamic incompatibility of the hard segments and the soft segments. The hard segments are aggregated through hydrogen bonds to form hard domains, and the soft segments form soft domains, so that the material has excellent designability and mechanical adjustability. However, in Polydimethylsiloxane (PDMS) based polyurea elastomers, the incompatibility of the high polarity hard segments with the non-polar PDMS soft segments is too pronounced, which can lead to excessive microphase separation, compromising mechanical properties. In order to solve the problem, polyether is introduced as a transition phase, the polarity of the transition phase is between that of PDMS and that of the hard segment, and the interface compatibility of the hard segment and the soft segment can be effectively improved, so that the comprehensive mechanical property of the elastomer is obviously improved. The invention uses polysiloxane and bio-based polyol as double soft segments, builds a bio-based organic silicon matrix with repairable performance by introducing F-H bonds and constructing a synergistic mechanism of multi-level hydrogen bonds, and further prepares the flexible composite membrane with conductivity and repairable function successfully by doping multi-wall carbon nano tubes for functionalization. Disclosure of Invention The invention aims to provide a preparation method of a bio-based repairable flexible conductive organic silicon film, which aims to integrate the obtained organic silicon film into a whole with excellent flexibility, conductivity, self-repairing performance and recoverability, and meets the ideas of green, environment-friendly and sustainable development. In order to achieve the aim, the preparation method of the bio-based repairable flexible conductive organic silicon film adopts the following technical scheme that the organic silicon film has the comprehensive properties of flexibility, conductivity, repairable function and recoverability through molecular structure design and functional doping based on a double-soft-segment structure constructed by bio-based polyol and polysiloxane. The invention provides a preparation method of a bio-based repairable flexible conductive organic silicon film, which comprises the following steps: (1) Mixing 2-4 mmol bio-based polyol PO3G (polytrimethylene ether glycol with the number average molecular weight of 2000G/mol), 4-8 mmol isophorone diisocyanate and 10-15 mg dibutyl tin dilaurate, and reacting for 1-2 h at 60-75 ℃ under the protection of N 2 to obtain an isocyanate-terminated bio-based prepolymer; (2) 1-2 mmol bis (3-aminopropyl) terminated poly (dimethylsiloxane) PDMS (with the number average molecular weight of 3000 g/mol) is dissolved in 6-18 mL N-N-dimethylacetamide, and is added into the bio-based prepolymer prepared in the step (1) dropwise, the chain extension reaction is carried out continuously at 60-75 ℃ for 1-2 h, and the temperature is reduced to 50 ℃ to obtain isocyanate terminated bio-based organosilicon prepolymer solution; (3) Dissolving 0.5-1 mmol of 4,4' - (hexafluoroisopropylidene) diphenol and 0.5-1 mmol m-phthalhydrazide in 3-6 mL N-N-dimethylacetamide, dropwise adding the solution into the bio-based organosilicon prepolymer solution prepared in the step (2), continuously performing chain extension reaction at 50 ℃ for 12-24 h, and drying