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Variable stiffness self-healing material containing metal-mercapto coordination bond and its preparation and application

A self-healing material and variable stiffness technology, applied in additive processing, adhesives, etc., can solve the problems of water vapor sensitivity, complicated synthesis steps, limited practical application fields, etc., and achieve simple steps, excellent flexibility, and good self-healing performance. Effect

Active Publication Date: 2022-07-12
NANJING UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] At present, self-healing materials based on coordination bonds have the following disadvantages: (1) The synthesis steps are relatively cumbersome, requiring multi-step synthesis to introduce ligand-hole units into the long chain of the polymer, and then add metal ions to complete the coordination form a cross-linked network
(2) Metal-hydroxyl (Science 2010,328,216.; Adv.Mater.2014,26,3415.; Chem.Sci.2016,7,2736.) or metal-amine (Nat .Mater.2015,14,1210.; Macromolecules 2016,49,6310.; Polym.Chem.2018,9,3543.) The coordination structure is used as the cross-linking point, which is sensitive to water vapor, which greatly limits the practical application field

Method used

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  • Variable stiffness self-healing material containing metal-mercapto coordination bond and its preparation and application
  • Variable stiffness self-healing material containing metal-mercapto coordination bond and its preparation and application
  • Variable stiffness self-healing material containing metal-mercapto coordination bond and its preparation and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0069] A variable stiffness self-healing material containing a metal-mercapto coordination bond and a preparation method thereof:

[0070] 50.00g of pentaerythritol tetra-3-mercaptopropionate was added to the flask, then 100mL of dichloromethane was added as a solvent, the reaction temperature was controlled to 25°C, the stirring speed was 100r / min, and the reaction was carried out for 30min to obtain a compound solution with a terminal mercapto group;

[0071] 8.28g of triethylamine was added to the above-mentioned mercapto-terminated compound solution, and the reaction temperature was controlled at 25°C and the stirring speed was 200r / min under sealed conditions, and the reaction was carried out for 4h;

[0072] Add 0.30g of pentaerythritol triacrylate to the above mixing system, control the reaction temperature under sealed conditions at 25°C, stir at 200r / min, and react for 6h;

[0073] Preparation of metal zinc salt solution: take 13.79g of zinc chloride, add 15mL of meth...

Embodiment 2

[0078] A variable stiffness self-healing material containing a metal-mercapto coordination bond and a preparation method thereof:

[0079] 80.00g of trimethylolpropane tris(2-mercaptoacetate) and 19.83g of mercapto-terminated liquid polysulfide resin with a relative molecular mass of 1000 were added to the flask, and then 100mL of dichloromethane was added as a solvent, and the reaction temperature was controlled at 25°C, The stirring speed was 150r / min, and the reaction was carried out for 30min to obtain the compound solution of the terminal mercapto group;

[0080] 20.00 g of triethanolamine was added to the above-mentioned mercapto-terminated compound solution, and the reaction temperature was controlled to be 25° C. and the stirring speed was 250 r / min under sealed conditions, and the reaction was carried out for 4 hours;

[0081] 30.00g of pentaerythritol triacrylate was added to the above mixed system, and the reaction temperature was controlled to be 25°C under sealed ...

Embodiment 3

[0088] 20.00g of 2,7-naphthyldithiol and 4.16g of mercapto-terminated liquid polysulfide resin with a relative molecular mass of 4000 were added to the flask, and then 100mL of tetrahydrofuran was added as a solvent. , to obtain the compound solution of the terminal thiol group;

[0089] 2.84g of N,N-dimethylbenzylamine was added to the above-mentioned mercapto-terminated compound solution, and the reaction temperature was controlled at 25°C and the stirring speed was 250r / min under sealed conditions, and the reaction was carried out for 4h;

[0090] To the above mixed system, 7.72 g of triphenylmethane triisocyanate was added, and the reaction temperature was controlled to be 25° C. under sealed conditions, and the stirring speed was 300 r / min, and the reaction was carried out for 6 hours;

[0091] Preparation of metal zinc salt solution: take 7.12g of zinc sulfate, add 10mL of methanol as a solvent, and carry out ultrasonic treatment for 1h at 25°C and ultrasonic power of 90...

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Abstract

The invention relates to a variable-stiffness self-repairing material containing a metal-mercapto coordination bond, which is composed of a mercapto-terminated small molecule compound, a mercapto-terminated liquid polysulfide resin, a crosslinking agent, a zinc salt, other metal salts, an alkaline regulator and a solvent composition. The material structure contains a large number of metal-mercapto coordination bonds. The good thermodynamic stability of the coordination bonds ensures that the material has greater rigidity and mechanical strength; Repair performance; the high temperature sensitivity of the coordination bond ensures the variable stiffness of the material under a wide temperature range; the insensitivity of the coordination bond to water ensures the environmental stability of the material; at the same time, the material has a transparent It has the characteristics of high performance and adjustable refractive index. The variable-stiffness self-healing material containing metal-mercapto coordination bonds of the present invention can be applied to the fields of sealants, self-healing coatings, temperature-sensitive variable-stiffness self-repairing engineering materials, additive manufacturing, composite materials, optically transparent adhesives and the like.

Description

technical field [0001] The invention belongs to the field of novel materials, relates to a self-healing material containing a coordination bond, a preparation method and application thereof, and in particular relates to a variable stiffness self-repairing material containing a metal-mercapto coordination bond, and a preparation method and application thereof. Background technique [0002] Self-healing materials are a new class of smart materials that can imitate living organisms to repair themselves when they are physically damaged by the environment or mechanical fatigue. Such materials are of great significance for extending the service life of materials and improving the stability of materials, and have gradually become one of the research hotspots, showing great development prospects and application values ​​in industries such as aerospace, shipbuilding, construction, and automobiles. . [0003] Self-healing materials can be divided into two categories: external aid typ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08G83/00C08L87/00B33Y70/00C09J187/00
CPCC08G83/008C08L87/00B33Y70/00C09J187/00
Inventor 李承辉李文王洪芹高文通
Owner NANJING UNIV
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