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Intrinsic self-repairing and recyclable polythiourea polymer, and preparation method and application thereof

A technology of polymer and polythiourea, which is applied in the field of intrinsic self-healing and recyclable polythiourea polymer and its preparation, can solve the problems of unfavorable popularization and application, reduce thermal reversible reaction, and high thermal reversible temperature, and achieve Enhanced use stability, wide thermal reversible temperature range, and low thermal reversible temperature

Active Publication Date: 2019-12-10
SUN YAT SEN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, there are still the following deficiencies, for example: the thermal reversibility temperature of the general carbamate bond is relatively high, and even a high content of toxic catalyst is required; on the other hand, in order to reduce the temperature of the thermal reversible reaction, the reversible bond molecular The introduction of special electronegative (such as oxime bond) and large steric hindrance (such as tert-butyl) groups usually requires the synthesis of specific monomers, which limits the use of commercial conventional monomers, which is not conducive to the use of ordinary polyurethane and popularization and application in polyurea

Method used

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  • Intrinsic self-repairing and recyclable polythiourea polymer, and preparation method and application thereof
  • Intrinsic self-repairing and recyclable polythiourea polymer, and preparation method and application thereof
  • Intrinsic self-repairing and recyclable polythiourea polymer, and preparation method and application thereof

Examples

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Effect test

Embodiment 1

[0075] This embodiment provides a polythiourea polymer (referred to as cross-linked polythiourea, the same below), and its preparation process is as follows.

[0076] Under nitrogen atmosphere, add 5.0 parts of p-phenylene diisothiocyanate into a 250mL three-necked flask with mechanical stirring, add 100.0 parts of DMF solvent, heat up to 50°C to dissolve p-phenylene diisothiocyanate, Add 1.1 parts of N,N'-diethylethylenediamine and 1.9 parts of 1,2-bis(2-aminoethoxy)ethane, react at 50°C for 16 hours, add 0.1 parts of pentaethylenehexamine to continue the reaction for 8 hours , poured into the mold and continued to cure at 60°C for 16 hours to obtain cross-linked polythiourea. After the material was scratched or broken, the fractured surface was repaired in the air at 35-120°C for 0.5-24 hours, and then it could be repaired . The polymer can recover part of its mechanical strength by crushing-hot pressing or degrading-casting to make a new sample. The results of tensile tes...

Embodiment 2

[0078] This embodiment provides a polythiourea polymer, the preparation process of which is as follows.

[0079] Under nitrogen atmosphere, add 5.0 parts of p-phenylene diisothiocyanate into a 250mL three-necked flask with mechanical stirring, add 100.0 parts of DMF solvent, heat up to 50°C to dissolve p-phenylene diisothiocyanate, Add 1.1 parts of N,N'-diethylethylenediamine and 2.9 parts of diethylene glycol bis(3-aminopropyl) ether, react at 50°C for 16 hours, add 0.1 parts of pentaethylenehexamine to continue the reaction for 8 hours, and pour Continue curing in the mold at 60°C for 16 hours to obtain cross-linked polythiourea. After the material is scratched or fractured, the fractured surface is repaired in air at 35-120°C for 0.5-24 hours, and then it can be repaired. The polymer can recover part of its mechanical strength by crushing-hot pressing or degrading-casting to make a new sample. The results of tensile tests before and after repair or recycling of polymer mat...

Embodiment 3

[0081] This embodiment provides a polythiourea polymer, the preparation process of which is as follows.

[0082] Under nitrogen atmosphere, add 5.0 parts of p-phenylene diisothiocyanate into a 250mL three-necked flask with mechanical stirring, add 100.0 parts of DMF solvent, heat up to 50°C to dissolve p-phenylene diisothiocyanate, Add 1.1 parts of N,N'-diethylethylenediamine and 3.0 parts of polyetheramine PEA230 (the number average molecular weight is 230), react at 50°C for 16 hours, add 0.1 parts of pentaethylenehexamine to continue the reaction for 8 hours, and pour into the mold Continue to cure at 60°C for 16 hours to obtain cross-linked polythiourea. After the material is scratched or fractured, the fractured surface can be repaired by contacting it in the air at 35-120°C for 0.5-24 hours. The polymer can recover part of its mechanical strength by crushing-hot pressing or degrading-casting to make a new sample. The results of tensile tests before and after repair or r...

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Abstract

The invention relates to an intrinsic self-repairing and recyclable polythiourea polymer, and a preparation method and an application thereof. The polythiourea polymer is composed of the following components in parts by weight: 1.9 to 24.5 parts of a diamine monomer, 3.7 to 5.9 parts of a diisothiocyanate monomer and 0.07 to 2.2 parts of an amine monomer crosslinking agent; the functionality of the amine monomer crosslinking agent is greater than 2. The polythiourea polymer provided by the invention contains a characteristic dynamic reversible thiourea bond unit, and endows the polythiourea polymer material with thermotropic reversible self-repairing and solid crushing or solvent degradation recoquite properties, so that the use stability of the material is enhanced, and the service life of the material is prolonged. The preparation method provided by the invention is simple in process, the thermal reversible temperature range of thiourea bonds is wide (35-120 DEG C), and no additionalcatalyst is needed.

Description

technical field [0001] The invention belongs to the technical field of intelligent polymer materials, and in particular relates to an intrinsic self-repairing and recyclable polythiourea polymer and its preparation method and application. Background technique [0002] Polymer materials, metal materials, and inorganic materials are listed as the three pillars in the material structure, and have broad application prospects. However, during the processing and use of polymer materials, internal microcracks and local damage often lead to performance degradation, shorten their service life, and even cause safety hazards. Self-healing polymer materials imitate the principle of biological injury healing and heal themselves through certain mechanisms. They are the most promising polymer smart materials to solve such key problems. [0003] Self-healing polymer materials include intrinsic self-healing and exogenous self-healing. The foreign aid self-repair system repairs by implantin...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08G18/76C08G18/32C08G18/50C08G18/60C08G18/65C08G18/66
CPCC08G18/3228C08G18/3234C08G18/5024C08G18/603C08G18/6529C08G18/6685C08G18/7614
Inventor 张泽平李艳梅容敏智章明秋
Owner SUN YAT SEN UNIV
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