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Organic reversible thermochromic microcapsule with long service life and large color difference and preparation method thereof

A thermochromic and microcapsule technology, which is applied in the direction of microcapsule preparation, microsphere preparation, color-changing fluorescent materials, etc., can solve the problems of small color difference, poor light transmission, short service life, etc., and achieve safe use, long life, and color difference. big effect

Active Publication Date: 2015-09-02
林 士杰
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] Because the organic reversible thermochromic compound composed of electron donor dyes has bright colors, sensitive discoloration, and lower price than liquid crystal materials, it has been used in textile printing and dyeing, printing ink, anti-counterfeiting, temperature-indicating materials, and coatings. Its main disadvantage is that when the color changes, the solvent in it will change from solid to liquid or from liquid to solid, so it is easily affected by the environment. When encountering strong acid, it will lose the reversibility of discoloration. It will react with weakly acidic chromogenic agents, and will also lose the reversibility of discoloration, and may be dissolved in some organic solvents, so it is required to isolate the organic reversible thermochromic compound from the use environment, a method of isolating It is to use polymer materials to wrap organic reversible thermochromic materials to obtain microcapsules containing organic reversible thermochromic materials. This preparation process is also called microencapsulation. Organic reversible thermochromic compounds in microcapsules are called As the core material, the polymer material wrapped around the core material is called the wall material, which requires the wall material to be resistant to strong acids and alkalis and organic solvents, not easy to degrade, the wall material is transparent, and the light absorption rate is low, which can prevent discoloration of organic reversible thermochromic materials The impact of sharpness and vividness
[0004] There are many documents on the preparation of organic reversible thermochromic microcapsules, but there are not many types of wall materials. Chinese patent CN102477290 discloses a thermosensitive color-changing material microcapsule and its preparation method. The raw material of the wall material is melamine resin prepolymer. Chinese patent The wall material disclosed in CN102807853 is a wall covering system formed by styrene-maleic anhydride copolymer and urea-formaldehyde resin prepolymer. Although urea-formaldehyde resin honey and melamine resin have good sealing performance, their light transmittance is poor, resulting in urea-formaldehyde resin Organic reversible thermochromic material microcapsules made of resin and melamine resin as the wall material have small color difference when the color changes; due to the incompatibility of urea-formaldehyde resin or melamine resin with the thermochromic compound, the organic reversible thermal The color-changing microcapsules will quickly lose their color-changing properties after experiencing temperature changes, and their service life is short; in addition, whether it is urea-formaldehyde resin or melamine resin, formaldehyde may be released during use, and formaldehyde is a recognized carcinogen; other common The wall material has gelatin. Although the light transmission of gelatin is better than that of urea-formaldehyde resin and melamine resin, but limited by the nature of gelatin, its stability is poor and it is easy to degrade
Most of the existing organic reversible thermochromic compounds based on the electron gain and loss mechanism use bisphenol A as the chromogenic agent. Bisphenol A is an endocrine disruptor, and its accumulation in nature and the environment will cause serious environmental and ecological problems.

Method used

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  • Organic reversible thermochromic microcapsule with long service life and large color difference and preparation method thereof
  • Organic reversible thermochromic microcapsule with long service life and large color difference and preparation method thereof
  • Organic reversible thermochromic microcapsule with long service life and large color difference and preparation method thereof

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preparation example Construction

[0048] The method for preparing organic reversible thermochromic microcapsules with long color difference and large color difference includes the following steps:

[0049] a) adding an oil-soluble initiator to the monomer A or the mixture of monomer A and monomer C for prepolymerization,

[0050] b) Add organic reversible thermochromic compound after prepolymerization,

[0051] c) adding monomer B to disperse it into an oil-in-water emulsion in an aqueous solution containing a dispersant,

[0052] d) performing free radical polymerization, filtering, washing and drying to obtain organic reversible thermochromic microcapsules.

[0053] The initiator is preferably azobisisobutyronitrile, the amount of the initiator is preferably 0.5-2% by weight of the monomer A, the prepolymerization temperature is between 60°C and 70°C, and the prepolymerization time is 30 minutes.

[0054] Acrylate and / or methacrylate molecules contain carbon-carbon double bonds, and the groups connected to...

Embodiment 1

[0059] Example 1. Weigh 10.0 grams of refined methyl methacrylate (MMA) with an electronic balance in a three-necked flask, add 0.10 grams of initiator azobisisobutyronitrile (AIBN), and prepolymerize in a water bath at 65°C 30min, add 10.0 grams of organic reversible thermochromic compound, add 1.00 g of divinylbenzene (DVB), the proportion of organic reversible thermochromic compound is 3,3-bis(4-dimethylaminophenyl)- 6-dimethylaminophthalide: 4,4'-dihydroxydiphenyl sulfone: the proportioning ratio of 1-hexadecanol is 1:3:150, and the mixture is added with 200 grams of weight percentage and the concentration is 0.3% polyvinyl alcohol ( In the PVA) aqueous solution, use a high-shear emulsifier to shear and emulsify for 3 minutes, then raise the temperature to 75° C., continue the reaction for 3 hours, and then raise the temperature to 85° C. for 1 hour. The product is washed, filtered, and dried to obtain a microcapsule product powder.

Embodiment 2

[0060]Example 2, take 10.0 grams of refined methyl methacrylate (MMA) and 0.20 grams of methacrylic acid (MAA) with an electronic balance in a three-necked flask, add 0.10 grams of initiator azobisisobutyronitrile (AIBN) , pre-polymerized in a water bath at 65°C for 30 minutes, added 10.0 grams of thermochromic compound, added 1.50 grams of divinylbenzene, the organic reversible thermochromic compound ratio is 3,3-bis(4-dimethylamine Phenyl)-6-dimethylaminophthalide: 4,4'-dihydroxydiphenyl sulfone: the ratio of 1-hexadecanol is 1:3:150, the mixture is added to 200 grams by weight and the concentration is 0.3% Polyvinyl alcohol (PVA) aqueous solution was sheared and emulsified for 3 minutes using a high-shear emulsifier, then the temperature was raised to 75° C., the reaction was continued for 3 hours, and the temperature was raised to 85° C. for 1 hour. The product is washed, filtered, and dried to obtain a microcapsule product powder.

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Abstract

The invention discloses an organic reversible thermochromic microcapsule with long service life and large color difference and a preparation method thereof. A wall material of the organic reversible thermochromic microcapsule is prepared from the following raw materials in percentage by weight through polymerization: 30-95% of acrylate and / or methacrylate, 5-70% of a divinyl and / or polyvinyl monomer mixture, and 0-10% of an acrylic acid and / or methacrylic acid mixture, and a core material is composed of a colour former 3,3-di(4-dimethylaminophenyl)-6-dimethylamino phthalide, a color developing agent 4,4'-dihydroxydiphenylsulfone, and a solvent selected from 1-dodecanol, 1-tetradecanol, 1-hexadecanol and 1-octadecanol; and the preparation method is implemented through carrying out prepolymerization on monomers and carrying out suspension polymerization on the obtained product. The obtained organic reversible thermochromic microcapsule has the advantages of long service life and large color difference; the microcapsule does not release formaldehyde, and does not contain bisphenol A, so that the microcapsule is safer to use.

Description

technical field [0001] The invention relates to an organic reversible thermochromic microcapsule and a preparation method thereof, in particular to an organic reversible thermochromic microcapsule of an acrylate-based wall material and a preparation method thereof, and belongs to the field of fine chemicals. Background technique [0002] Organic reversible thermochromic material refers to a functional material that can change color when the temperature is higher or lower than a specific temperature, and has a memory function and can be used repeatedly. Organic reversible thermochromic materials based on the mechanism of electron gain and loss are generally composed of a chromogenic agent, a chromogenic agent, and a solvent. The chromogenic agent determines the color of the color-changing material system, and the color depth is mainly determined by the chromogenic agent. The effect of system discoloration temperature. [0003] Because the organic reversible thermochromic com...

Claims

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Application Information

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IPC IPC(8): C08F220/14C08F212/36C08F220/06C09K9/02B01J13/14
Inventor 郑立辉宋光森
Owner 林 士杰
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