CN106519105A - Method for preparing photochromic microspheres through self-emulsifying method - Google Patents
Method for preparing photochromic microspheres through self-emulsifying method Download PDFInfo
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- CN106519105A CN106519105A CN201611015109.8A CN201611015109A CN106519105A CN 106519105 A CN106519105 A CN 106519105A CN 201611015109 A CN201611015109 A CN 201611015109A CN 106519105 A CN106519105 A CN 106519105A
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- microspheres
- photochromic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1416—Condensed systems
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1466—Heterocyclic containing nitrogen as the only heteroatom
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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention relates to the technical field of functional materials, in particular to a method for preparing photochromic microspheres through a self-emulsifying method. The method for preparing the photochromic microspheres through the self-emulsifying method includes the steps that spiropyrane is prepared; a premixed solution A is prepared; a premixed solution B is prepared; resin C and light pink dispersoid D are prepared; the dispersoid D is put in a flask and stirred for about 1 hour, then the room temperature is increased to 70 DEG C, heat preservation is performed for 1 hour, an initiator APS aqueous solution is slowly and dropwise added within 2 hours, heat preservation is performed for 1 hour after dropwise adding is finished, then the temperature is increased to 80 DEG C, after curing is performed for 1 hour, reaction is stopped, and flesh pink emulsion E is obtained; and the emulsion E is subjected to high-speed centrifugal separation, repeated cleaning is performed, a cleaned microsphere dispersed solution is frozen and dried, and the light pink photochromic microspheres are obtained. The average grain diameter of the microspheres is 249 nm, and the monodispersion is good; and the microspheres are good in photochromic property and also much higher than the solution of the microspheres in fatigue resistance. The fatigue resistance of the spiropyrane is effectively improved.
Description
Technical field
The present invention relates to technical field of function materials, and in particular to a kind of self-emulsification prepares the side of photochromic microsphere
Method.
Background technology
The characteristics of organic photochromic material has discoloration sensitive, bright in colour, spiro-pyrans are organic photochromic materials
One of earliest and widest system of middle research, it in addition to the photochromic effect with Rapid reversible, also with molten mutagens
Color, electrochromism, power mutagens color, acid-base discoloration etc. are acted on, can be in multiple necks such as chemical sensor, optical switch, information Store
Domain is used as intelligent response material.
However, spiro-pyrans are easily affected by environmental factorss and aoxidize deterioration, cause fatigue durability poor.Spiro-pyrans are wrapped in
In polymer microballoon, can both avoid the caused loss because of migration of small molecule photochromic material, can reduce again with extraneous oxygen,
The external environment such as soda acid directly contact and off-color material is damaged, so as to can further improve its discoloration the life-span.Polymer
Microsphere has larger surface area, controllable physical dimension, high load capability, good biocompatibility and surface modificability,
Show in many high-technology fields such as biomedical engineering, immunity inspection, electronics and information industry, high performance liquid chromatography, catalysis
Good application prospect is gone out.Organic photochromic material is wrapped in polymer microballoon, emulsion polymerization, precipitation can be adopted
The method such as polymerization and dispersin polymerization.During using emulsion polymerization, generally require to add substantial amounts of emulsifying agent, and the emulsifying agent meeting for remaining
The performance of emulsion is affected, while can also cause environmental pollution, its use range is limited；Although being not added with the soap-free emulsion of emulsifying agent
Polymerization be the drawbacks of can overcome emulsifying agent to bring, but polymerization rate is slow, solid content is relatively low.The great advantage of precipitation polymerization is
Any surfactant and stabilizer is not needed in the course of the polymerization process, but which has the disadvantage monomer, and consumption is relatively low, cause yield difficult
To improve, and off-color material can only be invested in microsphere by way of absorption or copolymerization.Dispersin polymerization can be regarded as one kind
Special precipitation polymerization, need to add dispersant and stabilizer that the polymer for generating suspends in media as well in system, generation
The dissolving situation of polymer particle diameter and photochromic material is affected by dispersant and stabilizer.
The content of the invention
It is contemplated that proposing a kind of method that self-emulsification prepares photochromic microsphere.
Technical program of the present invention lies in：
The method that self-emulsification prepares photochromic microsphere, including preparing spiro-pyrans；Also comprise the steps：
Methyl methacrylate, n-butyl acrylate, acrylic acid in mass ratio 3: 3: 2 is mixed, then respectively by positive 12
Mercaptan, initiator azodiisobutyronitrile are added in monomer solution by the consumption of account for monomer gross mass 4.0% and 0.8%, are obtained
Premixed liquid A；
After with methyl methacrylate dissolving spiro-pyrans, the friendship equivalent to methyl methacrylate quality 0.1% is added
Connection agent diacrylate -1,6- hexanediol esters obtain premixed liquid B after mixing；
A certain amount of solvent ethyl acetate is added in the 150mL four-hole boiling flasks equipped with thermometer, agitator and condensation reflux unit,
And after adding the premixed liquid A of 1/3 volume, stirring to be warming up to 70 DEG C, remaining premixed liquid, question response system is dripped in 3h
After stable, it is warming up to 80 DEG C and is incubated 3h.；When monomer conversion is basicly stable, less than 40 DEG C are cooled to, add TEA to carry out
Neutralization, is obtained resin C；Premixed liquid B is added in resin C, after mix homogeneously, is added water, is stirred 1h under 1000r/min, makes
Obtain pale pink dispersion D；
By dispersion D load the four-hole boiling flask with thermometer, agitator and condensation reflux unit in, after 1 h of stir about by
Room temperature rises to 70 DEG C, after insulation 1h, is slowly added dropwise initiator A PS aqueous solutions, is incubated 1 h, then rises after completion of dropping in 2h
To 80 DEG C, after ripening 1h, stopped reaction obtains meat powder color emulsion E to temperature；To emulsion E with being centrifuged at a high speed, the product of gained enters
Row is cleaned repeatedly, and the microsphere dispersion liquid for washing later is freezed and is dried, the photochromic microsphere of pale pink has been obtained.
The method have technical effect that：
The present invention is prepared for polyacrylate dispersion using self-emulsification, and the mean diameter of the emulsion is 249 nm, with preferable
Monodispersity；In addition to possessing good photochromic property, its fatigue resistance is also far above its solution to microsphere.The method energy
The fatigue resistance of spiro-pyrans is effectively improved, is expected to widen the application of spiro-pyrans in terms of intellectual material field.
Specific embodiment
The method that self-emulsification prepares photochromic microsphere, including preparing spiro-pyrans；Also comprise the steps：
Methyl methacrylate, n-butyl acrylate, acrylic acid in mass ratio 3: 3: 2 is mixed, then respectively by positive 12
Mercaptan, initiator azodiisobutyronitrile are added in monomer solution by the consumption of account for monomer gross mass 4.0% and 0.8%, are obtained
Premixed liquid A；
After with methyl methacrylate dissolving spiro-pyrans, the friendship equivalent to methyl methacrylate quality 0.1% is added
Connection agent diacrylate -1,6- hexanediol esters obtain premixed liquid B after mixing；
A certain amount of solvent ethyl acetate is added in the 150mL four-hole boiling flasks equipped with thermometer, agitator and condensation reflux unit,
And after adding the premixed liquid A of 1/3 volume, stirring to be warming up to 70 DEG C, remaining premixed liquid, question response system is dripped in 3h
After stable, it is warming up to 80 DEG C and is incubated 3h.；When monomer conversion is basicly stable, less than 40 DEG C are cooled to, add TEA to carry out
Neutralization, is obtained resin C；Premixed liquid B is added in resin C, after mix homogeneously, is added water, is stirred 1h under 1000r/min, makes
Obtain pale pink dispersion D；
By dispersion D load the four-hole boiling flask with thermometer, agitator and condensation reflux unit in, after 1 h of stir about by
Room temperature rises to 70 DEG C, after insulation 1h, is slowly added dropwise initiator A PS aqueous solutions, is incubated 1 h, then rises after completion of dropping in 2h
To 80 DEG C, after ripening 1h, stopped reaction obtains meat powder color emulsion E to temperature；To emulsion E with being centrifuged at a high speed, the product of gained enters
Row is cleaned repeatedly, and the microsphere dispersion liquid for washing later is freezed and is dried, the photochromic microsphere of pale pink has been obtained.
Claims (1)
1. the method that self-emulsification prepares photochromic microsphere, including preparing spiro-pyrans；It is characterized in that：Also include following step
Suddenly：
Methyl methacrylate, n-butyl acrylate, acrylic acid in mass ratio 3: 3: 2 is mixed, then respectively by positive 12
Mercaptan, initiator azodiisobutyronitrile are added in monomer solution by the consumption of account for monomer gross mass 4.0% and 0.8%, are obtained
Premixed liquid A；
After with methyl methacrylate dissolving spiro-pyrans, the cross-linking agent two equivalent to methyl methacrylate quality 0.1% is added
Acrylic acid -1,6- hexanediol esters, obtains premixed liquid B after mixing；
A certain amount of solvent ethyl acetate is added in the 150mL four-hole boiling flasks equipped with thermometer, agitator and condensation reflux unit,
And after adding the premixed liquid A of 1/3 volume, stirring to be warming up to 70 DEG C, remaining premixed liquid, question response system is dripped in 3h
After stable, it is warming up to 80 DEG C and is incubated 3h.；When monomer conversion is basicly stable, less than 40 DEG C are cooled to, add TEA to carry out
Neutralization, is obtained resin C；Premixed liquid B is added in resin C, after mix homogeneously, is added water, is stirred 1h under 1000r/min, makes
Obtain pale pink dispersion D；
By dispersion D load the four-hole boiling flask with thermometer, agitator and condensation reflux unit in, after 1 h of stir about by
Room temperature rises to 70 DEG C, after insulation 1h, is slowly added dropwise initiator A PS aqueous solutions, is incubated 1 h, then rises after completion of dropping in 2h
To 80 DEG C, after ripening 1h, stopped reaction obtains meat powder color emulsion E to temperature；To emulsion E with being centrifuged at a high speed, the product of gained enters
Row is cleaned repeatedly, and the microsphere dispersion liquid for washing later is freezed and is dried, the photochromic microsphere of pale pink has been obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611015109.8A CN106519105A (en) | 2016-11-18 | 2016-11-18 | Method for preparing photochromic microspheres through self-emulsifying method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611015109.8A CN106519105A (en) | 2016-11-18 | 2016-11-18 | Method for preparing photochromic microspheres through self-emulsifying method |
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| CN106519105A true CN106519105A (en) | 2017-03-22 |
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| CN201611015109.8A Pending CN106519105A (en) | 2016-11-18 | 2016-11-18 | Method for preparing photochromic microspheres through self-emulsifying method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106987244A (en) * | 2017-05-15 | 2017-07-28 | 电子科技大学 | A kind of composite electrochromic material and preparation method thereof |
| CN107779072A (en) * | 2017-11-10 | 2018-03-09 | 江苏视客新材料股份有限公司 | A kind of photochromic coating liquid and its application |
| CN114381177A (en) * | 2020-10-16 | 2022-04-22 | 广州盛色科技有限公司 | Preparation method of photochromic water-based acrylic coating |
-
2016
- 2016-11-18 CN CN201611015109.8A patent/CN106519105A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106987244A (en) * | 2017-05-15 | 2017-07-28 | 电子科技大学 | A kind of composite electrochromic material and preparation method thereof |
| CN106987244B (en) * | 2017-05-15 | 2019-05-14 | 电子科技大学 | A kind of composite electrochromic material and preparation method thereof |
| CN107779072A (en) * | 2017-11-10 | 2018-03-09 | 江苏视客新材料股份有限公司 | A kind of photochromic coating liquid and its application |
| CN107779072B (en) * | 2017-11-10 | 2020-08-25 | 江苏视科新材料股份有限公司 | Photochromic coating liquid and application thereof |
| CN114381177A (en) * | 2020-10-16 | 2022-04-22 | 广州盛色科技有限公司 | Preparation method of photochromic water-based acrylic coating |
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Application publication date: 20170322 |