Self-repairing polyurethane based on hydrogen bonds and dynamic disulfide bonds as well as preparation method and application of self-repairing polyurethane

A disulfide bond and polyurethane technology, which is applied in the field of polymer preparation, can solve the problems of polyurethane's difficult mechanical strength and self-repair cycle, and achieve multiple self-repair functions, low repair temperature, and novel preparation methods.

Active Publication Date: 2020-07-17
QINGDAO UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the inventors found that it is difficult for the current self-healing polyurethane to have high mechanical strength and self-healing cycles at room temperature.

Method used

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  • Self-repairing polyurethane based on hydrogen bonds and dynamic disulfide bonds as well as preparation method and application of self-repairing polyurethane
  • Self-repairing polyurethane based on hydrogen bonds and dynamic disulfide bonds as well as preparation method and application of self-repairing polyurethane
  • Self-repairing polyurethane based on hydrogen bonds and dynamic disulfide bonds as well as preparation method and application of self-repairing polyurethane

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Experimental program
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preparation example Construction

[0039] The present invention also provides a method for preparing polyurethane with self-repairing function, comprising:

[0040] Prepolymers containing isocyanate groups and dynamic disulfide bonds and polyamino (butylene itaconate-co-butylene succinate) (PU-BIS) are used as raw materials for polymerization reactions. After the reaction is complete, Cross-linking by mercapto-ene click reaction to form a thin film.

[0041] The self-healing performance and mechanical strength of the cross-linked film and the molar ratio of disulfide in the prepolymer and the polyamino(butylene itaconate-co-butylene succinate) (PU-BIS) The hydrogen bond content is related, so the present invention is preferred, (3,3-dithiodipropionic acid+dithiosalicylic acid):4,4-diaminodiphenyl disulfide=1:0.5~1;3 , 3-dithiodipropionic acid: dithiosalicylic acid = 0:1 ~ 1:0; low molecular weight unsaturated polyester: isophorone diisocyanate = 1: 0 ~ 0.9.

[0042] Existing studies have shown that compared w...

Embodiment 1

[0064] Put isophorone diisocyanate and PBIS-2000 with a molar ratio of 2:1 in a 250ml four-neck flask, use chloroform solution as a solvent, and dibutyltin dilaurate as a catalyst, the amount of which is the quality of PBIS-2000 0.05%, connected with spherical condenser, thermometer and stirrer, heated up to 70°C under nitrogen protection and stirred, and reacted for 3 hours. Then, slowly drop PBIS-2000 into the flask, the molar ratio of the added amount to isophorone diisocyanate is 1:1, and add the catalyst dibutyltin dilaurate, the added amount is 0.05% of the mass of PBIS-2000, Under nitrogen protection, the reaction was continued for 3 hours. The hydroxyl-terminated unsaturated polyurethane PU-BIS-2000 was obtained.

[0065] 3,3-dithiodipropionic acid, 4,4-diaminodiphenyl disulfide and isophorone diisocyanate with a molar ratio of 1:0.5:2 were placed in a 250ml four-neck flask, and the chloroform solution As a solvent, connect a spherical condenser, a thermometer and a ...

Embodiment 2

[0067]Put isophorone diisocyanate and PBIS-2000 with a molar ratio of 1:2 in a 250ml four-neck flask, use chloroform solution as a solvent, and dibutyltin dilaurate as a catalyst, the amount of which is the quality of PBIS-2000 0.05%, connected with spherical condenser, thermometer and stirrer, heated up to 70°C under nitrogen protection and stirred, and reacted for 3 hours. Then, slowly drop isophorone diisocyanate into the flask, the molar ratio of the amount added to PBIS-2000 is 1:1, and the catalyst dibutyltin dilaurate is added, the amount added is 0.05% of the mass of PBIS-2000, Under nitrogen protection, the reaction was continued for 3 hours. Next, slowly drop PBIS-1000 into the flask, the molar ratio of the amount added to PBIS-2000 is 1:1, and add the catalyst dibutyltin dilaurate, the amount added is 0.05% of the mass of PBIS-1000, under nitrogen Under protection, the reaction was continued for 3 hours. The hydroxyl-terminated unsaturated polyurethane PU-BIS-1000...

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Abstract

The invention belongs to the field of polymer preparation, and relates to self-repairing polyurethane based on hydrogen bonds and dynamic disulfide bonds as well as a preparation method and application of the self-repairing polyurethane. The preparation method comprises the steps: introducing a plurality of diisocyanates into unsaturated polyester with low molecular weight to form hydroxyl-terminated unsaturated polyurethane; grafting and introducing a prepolymer containing an isocyanate group and dynamic disulfide bonds to a terminal hydroxyl group of unsaturated polyurethane to form a polymer; carrying out sulfydryl-alkene click reaction on the polymer and a multi-sulfydryl compound to obtain the self-repairing polyurethane based on the dynamic disulfide bonds. The preparation method ofthe self-repairing polyurethane is novel; the plurality of diisocyanates are introduced into unsaturated polyester with low molecular weight, the number of intermolecular hydrogen bonds is increased,improvement of the self-repairing performance of polyurethane is facilitated, meanwhile, amido bonds generated through the reaction of carboxyl and isocyanate groups are used for endowing the polyurethane with the advantages of high mechanical strength and good toughness, and the polyurethane with great self-repairing capacity and mechanical strength is prepared.

Description

technical field [0001] The invention relates to a method for preparing polyurethane, in particular to a method for preparing self-healing polyurethane based on hydrogen bonds and dynamic disulfide bonds, and belongs to the field of polymer preparation. Background technique [0002] The information disclosed in this background section is only intended to increase the understanding of the general background of the present invention, and is not necessarily taken as an acknowledgment or any form of suggestion that the information constitutes the prior art already known to those skilled in the art. [0003] Polyester polyol is a kind of polymer prepared by polycondensation reaction of polycarboxylic acid and polyol. It is the most commonly used and most important synthetic raw material for polyurethane, because in the process of polyurethane synthesis, polyester polyol can provide polyurethane Flexible soft segment, which endows polyurethane with excellent performance. As the so...

Claims

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Application Information

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IPC IPC(8): C08J3/24C08J5/18C08G18/68C08G18/38C08G18/32C08L75/14C09D175/14
CPCC08J3/24C08J5/18C08G18/68C08G18/3863C08G18/3868C09D175/14C08J2375/14
Inventor 高传慧张静董亚洁刘月涛王传兴许军武玉民
Owner QINGDAO UNIV OF SCI & TECH
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