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A kind of cross-linked metal supramolecular copolymer self-healing coating material and preparation method thereof

A coating material and supramolecular technology, applied in the coating and other directions, can solve the problems of difficult to meet practical requirements and low hardness of coating materials, and achieve the effect of solving multiple repairs, high repair rate and high hardness

Active Publication Date: 2016-04-06
GUANGZHOU GUANZHI NEW MATERIAL TECH +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The prepared partially cross-linked metal supramolecular copolymer coating has a low-temperature (100°C) self-healing function after damage, although the reversibility of its metal-ligand interaction has no significant effect on the self-healing process, but only Copolymers with a low glass transition temperature can repair wide scratches in a short time, and the hardness of the prepared coating material is too small to meet practical requirements

Method used

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  • A kind of cross-linked metal supramolecular copolymer self-healing coating material and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] (1) RAFT aggregation. A mixed monomer of 20.28g lauryl methacrylate and 2.07g styrene and 3.65g methacrylate-6-(2,2':6',2"-terpyridine-4'-oxyl) hexyl mono After dissolving the body with 4.00ml of toluene, add it to a 50ml reactor, start stirring, and after 30 minutes of purging oxygen with nitrogen, add 1.15ml of toluene containing 0.1425g of isobutyronitrile dithiobenzoate and 0.0265g of azobisisobutyronitrile Solution. Reacted in an oil bath at 70° C. for 18 hours. Discharged, and the polymer product was purified by precipitation with 250 ml of cold ethanol, and the polymer was obtained after drying.

[0032] Through nuclear magnetic detection, the obtained polymer parameters are: 1HNMR (CDCl3, δppm): 0.82-2.02 (185H), 3.94-4.28 (14H), 6.45-7.09 (8H), 7.40 (1H), 7.88 (1H), 8.04 ( 1H), 8.64-8.72(2H); the NMR data prove that the product obtained is polylauryl methacrylate-styrene-methacrylic acid-6-(2,2':6',2"-terpyridine-4 '-oxygen) hexyl ester terpolymer. The nuclea...

Embodiment 2

[0039] (1) RAFT aggregation. Mixed monomers of 15.07g of 2-ethylhexyl acrylate and 5.03g of ethyl methacrylate and 5.85g of methacrylic acid-8-(2,2':6',2"-terpyridine-4'- Oxygen) octyl ester monomer was dissolved in 12.00ml benzene and added to a 50ml reactor, started to stir, and after 5 minutes of blowing nitrogen to drive oxygen, add 0.2295g cumyl dithiobenzoate and 0.1145g diphenyl peroxide Formyl in 2.50ml of benzene solution. Reacted in an oil bath at 80°C for 16 hours. Discharged, the polymer product was purified by precipitation with 200ml of cold water, and dried for later use.

[0040] (2) Polymer crosslinking. Pour 10ml of acetone solution containing 0.1880g of polymer into a 25ml single-neck bottle with a magnetic stirrer, add 2ml of aqueous solution containing 0.0160g of ferrous sulfate heptahydrate under stirring, mix well and cast the sol directly on the glass mold In the process, the solvent is evaporated by vacuuming, and a cross-linked metal supramolecular ...

Embodiment 3

[0043] (1) RAFT aggregation. A mixed monomer of 15.56g lauryl acrylate and 7.78g methyl methacrylate and 3.89g methacrylate-12-(2,2':6',2"-terpyridine-4'-oxyl) lauryl After dissolving the monomer with 8.00ml of ethyl acetate, add it to a 50ml reactor, start stirring, blow nitrogen to drive oxygen for 10 minutes, then add 0.1276g of dithiobenzoic acid-2-(ethoxycarbonyl) isopropyl ester and 0.0360 2.00ml ethyl acetate solution of g dicyclohexyl peroxydicarbonate.Reacted in an oil bath at 50°C for 12 hours.Discharging, the polymer product was precipitated and purified with 275ml of cold water, dried for subsequent use.

[0044] (2) Polymer crosslinking. Pour 10ml of tetrahydrofuran solution containing 0.1548g of polymer into a 25ml single-neck bottle with a magnetic stirrer, add 2ml of aqueous solution containing 0.0093g of anhydrous cobalt chloride under stirring, mix well and cast the sol directly on a glass mold In the process, the solvent is evaporated by vacuuming, and a c...

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Abstract

The invention discloses a crosslinked metal supramolecular copolymer self-repairing coating material and a preparation method thereof. The self-repairing coating material comprises the following components in percentage by mass: 40-85% of soft monomer, 5-25% of hard monomer, 5-20% of tpy derivative containing monomer, 0.2-1.8% of dithioester derivative chain transfer agent, 0.1-0.3% of organic free radical initiator and 2-12% of iron element (II) salt as crosslinking agent, wherein the weight ratio of the dithioester derivative to the organic free radical initiator is 2 / 1-6 / 1. According to the invention, when micro-cracks are generated on the material due to an external force in use, iron element (II)-terpyridine structures are aggregated together with each other to form an ion cluster, and the ion cluster is not melted and is easy to be moved to a damaged area to repair a cracked surface so as to prevent further extension of the cracks during heating, thereby achieve self-repairing of the coating. The coating has the characteristics of simple preparation, strong repairing capability, short repairing time, capability of realizing multiple times of self-repairing, relatively high hardness and the like.

Description

technical field [0001] The invention relates to a self-repairing coating material, in particular to a cross-linked metal supramolecular copolymer self-repairing coating material and its preparation technology. Background technique [0002] Coating is a mixture of various substances with polymer materials as the main body and organic solvents, water or air as the dispersion medium. Polymer materials are the main film-formers that form the coating film and determine the properties of the coating film. In recent years, with the continuous development of the national economy, especially the development of the automobile industry, shipbuilding industry, leather industry, construction industry, bridge industry and home decoration industry, organic polymer coatings such as anti-reflective coatings, anti-corrosion coatings, antibacterial coatings and natural Repair coatings, etc., as new functional polymer coating materials to protect, decorate and beautify the surface of objects, ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08J3/24C08F220/18C08F212/08C08F220/34C08F220/14C08F220/48C09D133/08
Inventor 龙志云彭晓宏欧阳洁彭清李俊梅
Owner GUANGZHOU GUANZHI NEW MATERIAL TECH
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