CN117511250A - Photochromic dye microsphere and preparation method thereof - Google Patents
Photochromic dye microsphere and preparation method thereof Download PDFInfo
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- CN117511250A CN117511250A CN202311405165.2A CN202311405165A CN117511250A CN 117511250 A CN117511250 A CN 117511250A CN 202311405165 A CN202311405165 A CN 202311405165A CN 117511250 A CN117511250 A CN 117511250A
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- photochromic dye
- microsphere
- photochromic
- dye
- amino resin
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- 239000004005 microsphere Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 229920003180 amino resin Polymers 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 8
- -1 anti-counterfeiting Substances 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000004753 textile Substances 0.000 claims abstract description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 30
- 239000011259 mixed solution Substances 0.000 claims description 17
- 229920000877 Melamine resin Polymers 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003995 emulsifying agent Substances 0.000 claims description 6
- 239000011241 protective layer Substances 0.000 claims description 6
- VCMLCMCXCRBSQO-UHFFFAOYSA-N 3h-benzo[f]chromene Chemical compound C1=CC=CC2=C(C=CCO3)C3=CC=C21 VCMLCMCXCRBSQO-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 230000001804 emulsifying effect Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical class C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 125000005907 alkyl ester group Chemical group 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- 229920005906 polyester polyol Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920000193 polymethacrylate Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims 1
- 239000011248 coating agent Substances 0.000 claims 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 12
- 239000007764 o/w emulsion Substances 0.000 abstract description 10
- 238000005562 fading Methods 0.000 abstract description 4
- 239000003973 paint Substances 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 230000032683 aging Effects 0.000 abstract 1
- 239000002775 capsule Substances 0.000 abstract 1
- 238000002845 discoloration Methods 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 7
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- 239000011162 core material Substances 0.000 description 4
- 239000003094 microcapsule Substances 0.000 description 4
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- IJFPVINAQGWBRJ-UHFFFAOYSA-N Diisooctyl phthalate Chemical compound CC(C)CCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCC(C)C IJFPVINAQGWBRJ-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical group C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical class 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000007771 core particle Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical class CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- UACSZOWTRIJIFU-UHFFFAOYSA-N hydroxymethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCO UACSZOWTRIJIFU-UHFFFAOYSA-N 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0004—Coated particulate pigments or dyes
- C09B67/0008—Coated particulate pigments or dyes with organic coatings
- C09B67/0013—Coated particulate pigments or dyes with organic coatings with polymeric coatings
-
- 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
-
- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention discloses a photochromic dye microsphere and a preparation method thereof, belonging to the technical field of high polymer materials. The preparation method of the photochromic dye microsphere specifically comprises the following steps: the photochromic dye is dissolved in an auxiliary agent, a polymer monomer and a catalyst, and is emulsified with a surfactant aqueous solution to form an oil-in-water emulsion, the oil-in-water emulsion is catalyzed to form the photochromic solid particles, and the surfaces of the particles are coated with amino resin to form the photochromic dye microspheres. The method is simple to operate, the yield exceeds 90%, and the formed capsule microspheres have uniform particle size and smooth surface; the formed photochromic microsphere polymer core can prevent dye leakage, provide good microenvironment for the photochromic dye, accelerate the discoloration and fading speed of the photochromic dye, and further improve the mechanical strength of the microsphere by the amino resin, so that the ageing resistance of the photochromic dye microsphere is improved, and the photochromic microsphere can be widely applied to the application fields of daily chemicals, textiles, anti-counterfeiting, paint and the like.
Description
Technical Field
The invention relates to a photochromic dye microsphere and a preparation method thereof, belonging to the technical field of high polymer materials.
Background
Photochromism refers to the reversible transformation process of certain substances between two states of different colors upon excitation by light. Organic photochromic materials, such as spiropyrans, naphthopyrans, spirooxazines, azobenzene, fulgides and the like, have been widely used in the fields of lenses, plastic products, coatings, textiles, inks and the like. However, most photochromic materials have problems of poor fatigue resistance and stability, and are easily oxidized and degraded.
In order to improve the utilization rate of the photochromic dye, an in-situ polymerization or emulsion polymerization method is adopted to encapsulate the photochromic dye molecules in the polymer particles, so that the excellent color-changing performance is maintained, the influence of external environments (acid, alkali, air, metal ions and the like) on the core material can be avoided, the weather resistance of the core material is improved, and the application is greatly facilitated.
At present, a common method for encapsulating photochromic dye is a microcapsule method, which is to dissolve the photochromic dye in an organic solvent, and then wrap polyurethane, polyurea, melamine ester, polyaniline and natural polymers such as chitosan, sodium alginate and other shell materials on the surface of liquid drops through emulsion polymerization. However, the microcapsules obtained by the conventional method are generally poor in mechanical strength, the core material is easy to leak, and the encapsulation rate of the product is low. The photochromic dye molecules and the polymer generally have certain compatibility, and if the photochromic dye and the polymer are directly melted, emulsified and polymerized to form polymeric particles containing the photochromic dye, and then the amino resin with higher mechanical strength is wrapped on the surfaces of the polymeric particles, the defects of the photochromic microcapsules can be avoided. Photochromic dye microspheres are critical in polymer selection, and need to have good transparency, stable chemical properties, a certain degree of toughness, and sufficient mechanical strength.
Therefore, screening of suitable polymeric materials and development of suitable polymeric encapsulation processes are particularly important for enhancing the properties of photochromic dye microspheres.
Disclosure of Invention
Aiming at the defects and shortcomings in the prior art, the invention provides a photochromic dye microsphere and a preparation method thereof in order to improve the application field and weather resistance of the photochromic dye; the method comprises the steps of melting photochromic dye, an auxiliary agent and a polymer monomer, preparing photochromic dye particles through emulsion polymerization, and forming an amino resin protective layer on the surface; the prepared photochromic dye microsphere has the advantages of high color change and fading speed, small particle size, good weather resistance and wide application field.
A first object of the present invention is to provide a method for preparing photochromic dye microspheres, comprising the steps of:
(1) Adding the photochromic dye into the auxiliary agent, stirring and dissolving, adding the polymer monomer and the catalyst, and stirring at 20-35 ℃ to prepare a mixed solution;
(2) Preparing an emulsifier aqueous solution with the concentration of 3-15 wt%;
(3) Adding the aqueous solution of the emulsifier in the step (2) into the mixed solution obtained in the step (1), emulsifying and dispersing, then heating to 60-100 ℃, stirring and reacting for 1-3 hours, adding the amino resin prepolymer into the mixed solution, regulating the pH value to 3-6 by using an acid aqueous solution with the mass fraction of 5-20%, continuously stirring for 30 min-2 hours to form microsphere suspension, and then carrying out suction filtration, washing and drying to obtain the photochromic dye microsphere.
In one embodiment of the invention, the photochromic material of step (1) is one or more of a spirooxazine, spiropyran, naphthopyran, azobenzene, fulgide compound.
In one embodiment of the invention, the auxiliary agent in the step (1) is one or more of C6-C18 long-chain fatty alcohol, C6-C18 long-chain alkyl ester and aromatic ester compounds.
In one embodiment of the present invention, the polymer monomer in the step (1) is one or more of acrylic acid esters, methacrylic acid esters, isocyanates, and polyalcohol compounds.
In one embodiment of the present invention, the catalyst in the step (1) is one or more of organotin, azodiisobutyronitrile, potassium persulfate, polyamine, bismuth carboxylate, phosphoric acid, organic sulfonic acid, phthalic anhydride, and dibenzoyl peroxide.
In one embodiment of the present invention, the emulsifier in the step (2) is one or more of alkylphenol ethoxylates, span80, tween80, PVA, SMA, EMA, gum arabic, gelatin, SDS, sodium dodecyl benzene sulfonate, and sodium dodecyl sulfonate.
In one embodiment of the present invention, the amino resin prepolymer in step (3) is a transparent solution formed by mixing urea, melamine or melamine and formaldehyde in a molar ratio of 1:2.5.
In one embodiment of the present invention, the acid in step (3) is one or more of acetic acid, citric acid, sulfuric acid, phosphoric acid, hydrochloric acid, and potassium bicarbonate.
In one embodiment of the present invention, the photochromic dye in the step (1) is added in an amount of 0.5 to 5wt% of the total mass of the mixed solution; the addition amount of the auxiliary agent is 10-50wt% of the total mass of the mixed solution; the addition amount of the polymer monomer is 20-90 wt% of the total mass of the mixed solution; the catalyst is used in an amount of 0.5 to 3wt% based on the mass of the polymer monomer.
In one embodiment of the present invention, the volume ratio of the mixed solution in the step (3) to the aqueous emulsifier solution is 1:1-1:5.
In one embodiment of the present invention, the mass ratio of the amino resin prepolymer to the mixed solution in the step (3) is 1:2 to 1:5.
It is a second object of the present invention to provide a photochromic dye microsphere prepared by the above method.
In one embodiment of the present invention, the photochromic dye microsphere is comprised of a core of photochromic dye, an auxiliary agent and a polymer, and an amino resin protective layer.
In one embodiment of the present invention, the polymer is one or more of polyacrylate, polymethacrylate, polyurethane, polyester polyol, polyether polyol.
In one embodiment of the present invention, the amino resin protective layer is urea, melamine, or a resin obtained by polycondensation of melamine and formaldehyde.
The third object of the invention is to provide an application of the photochromic dye microsphere in the fields of daily chemicals, textiles, anti-counterfeiting and paint.
The invention has the beneficial effects that:
(1) In the preparation process of the photochromic dye microsphere, the photochromic dye molecules are directly packaged in the polymer particles, and then the amino resin is used for forming a protective layer, so that the formed photochromic microsphere polymer core particles (in solid state) can prevent the dye from leaking, simultaneously provide good microenvironment for the photochromic dye, accelerate the changing and fading speed of the photochromic dye, and the amino resin can further improve the mechanical strength of the microsphere, so that the weather resistance of the photochromic dye can be improved, the product has excellent color changing performance, and the preparation process is simple, high in encapsulation rate and suitable for mass production;
(2) The photochromic microcapsule of the invention has uniform particle size, smooth surface and small particle size, and can be widely used in the fields of daily chemicals, textiles, anti-counterfeiting and paint.
Drawings
FIG. 1 is a microscopic image of an oil-in-water emulsion prepared in example 1 of the present invention;
FIG. 2 is a scan of photochromic dye microspheres prepared in example 1 of the present invention;
FIG. 3 is a schematic diagram showing the results of photochromic dye microspheres prepared in example 1 of the present invention.
Detailed Description
The invention will be further illustrated with reference to specific examples, which are to be understood as illustrative only and are not intended to limit the scope of the invention.
Example 1
The preparation method of the photochromic dye microsphere specifically comprises the following steps:
(1) Adding 3 parts of naphthopyran into 37 parts of tetradecanol, adding 30 parts of isophorone diisocyanate, 30 parts of polyethylene glycol (PEG 600) and 0.25 part of dibutyltin dilaurate, and stirring at 30 ℃ for dissolution to obtain a mixed solution;
(2) Adding the mixed solution obtained in the step (1) into 5wt% of sodium dodecyl benzene sulfonate aqueous solution according to the volume ratio of 1:3, and shearing and emulsifying at 10000rpm/min for 5min to obtain an oil-in-water emulsion;
(3) Heating the oil-in-water emulsion obtained in the step (2) to 80 ℃, stirring for 2 hours, adding 20 parts of prepolymer of melamine and formaldehyde into the emulsion, regulating the pH value to 4.5 by adopting a citric acid aqueous solution with the mass fraction of 10%, continuing to react for 1 hour, and after the reaction is finished, performing suction filtration, washing and drying at 70 ℃ for 12 hours to obtain the photochromic dye microspheres.
A microscopic image of the oil-in-water emulsion prepared in this example is shown in fig. 1; the formed photochromic dye/polyurethane microsphere scanning electron microscope image is shown in figure 2; FIG. 3 is a schematic structural diagram of a color-changing dye microsphere.
Example 2
The only difference from example 1 is that the prepolymer of melamine and formaldehyde in step (3) is replaced by a urea formaldehyde prepolymer, the other parameters and conditions being the same as in example 1.
Example 3
The difference from example 1 is only that isophorone diisocyanate in step (1) is replaced with dicyclohexylmethane diisocyanate, and other parameters and conditions are the same as in example 1.
Example 4
The difference from example 1 is only that the polyethylene glycol (PEG 600) in step (1) was replaced with polycarbonate diol (molecular weight 2000), and other parameters and conditions were the same as those of example 1.
Example 5
The preparation method of the photochromic dye microsphere specifically comprises the following steps:
(1) 1.5 parts of naphthopyran, 20 parts of isooctyl phthalate, 20 parts of hydroxypropyl methacrylate, 20 parts of hydroxymethyl methacrylate, 20 parts of butyl methacrylate and 0.3 part of azobisisobutyronitrile are mixed, stirred and dissolved at 30 ℃ to obtain a mixed solution;
(2) Adding the mixed solution obtained in the step (1) into 10wt% PVA water solution according to the volume ratio of 1:3, and shearing and emulsifying at 10000rpm/min for 5min to obtain oil-in-water emulsion;
(3) Heating the oil-in-water emulsion obtained in the step (2) to 90 ℃, stirring for 2 hours, adding 20 parts of prepolymer of melamine and formaldehyde into the emulsion, regulating the pH value to 4.5 by adopting 10% citric acid aqueous solution, continuing to react for 1 hour, filtering, washing, and drying at 70 ℃ for 12 hours to obtain the photochromic dye microspheres.
Example 6
The only difference from example 5 is that 20 parts of butyl methacrylate was replaced with 10 parts of isophorone diisocyanate and 10 parts of polyethylene glycol (PEG 600), and the other parameters and conditions were the same as in example 1.
Comparative example 1
The only difference from example 1 is that no prepolymer of melamine and formaldehyde was added and the pH was not adjusted, the other parameters and conditions being the same as in example 1.
Comparative example 2
The only difference from example 1 is that the prepolymer of melamine and formaldehyde is exchanged for a prepolymer of hydroxymethyl cellulose and formaldehyde.
Comparative example 3
The preparation method of the photochromic dye microsphere specifically comprises the following steps:
(1) Adding 3 parts of naphthopyran into 37 parts of tetradecanol, adding 50 parts of styrene and 0.25 part of azodiisobutyronitrile, and stirring at 30 ℃ for dissolution to obtain a mixed solution;
(2) Adding the mixed solution obtained in the step (1) into 5wt% of sodium dodecyl benzene sulfonate aqueous solution according to the volume ratio of 1:3, and shearing and emulsifying at 10000rpm/min for 5min to obtain an oil-in-water emulsion;
(3) Heating the oil-in-water emulsion obtained in the step (2) to 80 ℃, stirring for 2 hours, adding 20 parts of prepolymer of melamine and formaldehyde into the emulsion, adjusting the pH value to 4.5 by adopting 10% citric acid aqueous solution, continuing to react for 1 hour, filtering, washing, and drying at 70 ℃ for 12 hours to obtain the photochromic dye microspheres.
Result measurement
Various performance indexes of the photochromic dye microspheres prepared in the examples and the comparative examples are measured, and specific results are shown in the following table 1:
TABLE 1 various performance indicators of the photochromic dye microspheres
| Sample of | Yield% | Particle size μm | Fading effect |
| Example 1 | 93 | 3-6 | Excellent (excellent) |
| Example 2 | 94 | 3-7 | Excellent (excellent) |
| Example 3 | 89 | 4-9 | Good grade (good) |
| Example 4 | 88 | 2-6 | Excellent (excellent) |
| Example 5 | 92 | 4-8 | Excellent (excellent) |
| Example 6 | 90 | 5-10 | Good grade (good) |
| Comparative example 1 | 82 | 2-6 | Good grade (good) |
| Comparative example 2 | 83 | 10-15 | In general |
| Comparative example 3 | 76 | 12-28 | Difference of difference |
The above examples are not intended to limit the scope of the invention nor the order of execution of the steps described. The present invention is obviously modified by a person skilled in the art in combination with the prior common general knowledge, and falls within the scope of protection defined by the claims of the present invention.
Claims (10)
1. A method of preparing photochromic dye microspheres, the method comprising the steps of:
(1) Adding the photochromic dye into the auxiliary agent, stirring and dissolving, adding the polymer monomer and the catalyst, and stirring at 20-35 ℃ to prepare a mixed solution;
(2) Preparing an emulsifier aqueous solution with the concentration of 3-15 wt%;
(3) Adding the aqueous solution of the emulsifier in the step (2) into the mixed solution obtained in the step (1), emulsifying and dispersing, then heating to 60-100 ℃, stirring and reacting for 1-3 hours, adding the amino resin prepolymer into the mixed solution, regulating the pH value to 3-6 by using an acid aqueous solution with the mass fraction of 5-20%, continuously stirring for 30 min-2 hours to form microsphere suspension, and then carrying out suction filtration, washing and drying to obtain the photochromic dye microsphere.
2. The method of claim 1, wherein the photochromic material of step (1) is one or more of a spirooxazine, spiropyran, naphthopyran, azobenzene, fulgide compound.
3. The method of claim 1, wherein the auxiliary agent in the step (1) is one or more of a C6-C18 long-chain fatty alcohol, a C6-C18 long-chain alkyl ester, and an aromatic ester compound.
4. The method of claim 1, wherein the polymer monomer in step (1) is one or more of acrylates, methacrylates, isocyanates, and polyol compounds.
5. The method according to claim 1, wherein the catalyst in the step (1) is one or more of organotin, azobisisobutyronitrile, potassium persulfate, polyamine, bismuth carboxylate, phosphoric acid, organic sulfonic acid, phthalic anhydride, dibenzoyl peroxide compounds.
6. Photochromic dye microspheres prepared by the process according to any one of claims 1 to 5.
7. The photochromic dye microsphere of claim 6 wherein the photochromic dye microsphere is comprised of a core of photochromic dye, an auxiliary agent and a polymer, and an amino resin protective layer.
8. The photochromic dye microsphere according to claim 7, wherein the polymer is one or more of polyacrylate, polymethacrylate, polyurethane, polyester polyol, polyether polyol.
9. The photochromic dye microsphere according to claim 7, wherein the amino resin protective layer is urea, melamine or a resin formed by polycondensation of melamine and formaldehyde.
10. The photochromic dye microsphere is applied to the fields of daily chemicals, textiles, anti-counterfeiting and coating.
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