CN107903889B - Photochromic nano composite microsphere and application thereof - Google Patents

Photochromic nano composite microsphere and application thereof Download PDF

Info

Publication number
CN107903889B
CN107903889B CN201711113657.9A CN201711113657A CN107903889B CN 107903889 B CN107903889 B CN 107903889B CN 201711113657 A CN201711113657 A CN 201711113657A CN 107903889 B CN107903889 B CN 107903889B
Authority
CN
China
Prior art keywords
photochromic
spiropyran
zinc sulfide
compound
polyurethane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201711113657.9A
Other languages
Chinese (zh)
Other versions
CN107903889A (en
Inventor
王明华
乔振安
张鹤军
纪立军
范为正
张倩
司云凤
王志飞
刘洋
薛晓花
吴潇
郑永华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu Shike New Material Co ltd
Original Assignee
Jiangsu Shike New Material Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangsu Shike New Material Co ltd filed Critical Jiangsu Shike New Material Co ltd
Priority to CN201711113657.9A priority Critical patent/CN107903889B/en
Priority to PCT/CN2017/117714 priority patent/WO2019090920A1/en
Priority to EP17912346.8A priority patent/EP3508554B1/en
Publication of CN107903889A publication Critical patent/CN107903889A/en
Application granted granted Critical
Publication of CN107903889B publication Critical patent/CN107903889B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/29—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for multicolour effects
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C7/00—Optical parts
    • G02C7/10—Filters, e.g. for facilitating adaptation of the eyes to the dark; Sunglasses
    • G02C7/102—Photochromic filters
    • 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
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • 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

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Ophthalmology & Optometry (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • General Health & Medical Sciences (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Optical Filters (AREA)
  • Eyeglasses (AREA)

Abstract

A photochromic nanometer composite microsphere and its application, the photochromic composite microsphere is a three-layer composite core-shell structure, the inner core is a zinc sulfide mesoporous nanometer microsphere, the middle layer is a photochromic layer composed of spiropyran compounds, the outer shell is polyurethane; the composite microsphere has the outer diameter of 50-350nm, wherein the diameter of the zinc sulfide mesoporous nano microsphere is 30-250 nm, the thickness of the middle layer is 5-25 nm, and the thickness of the shell is 5-25 nm. The photochromic composite microsphere can be prepared into a photochromic coating or can be mixed into a resin optical material to prepare an optical photochromic material. The material can be changed from colorless to colored under the irradiation of ultraviolet rays, and can be quickly faded to colorless after the ultraviolet rays disappear, and the material has the advantages of strong fatigue resistance, good stability, high color changing speed and the like.

Description

Photochromic nano composite microsphere and application thereof
Technical Field
The invention belongs to the technical field of photochromism, and particularly relates to a photochromism nano composite microsphere used in an optical material and application thereof.
Background
Photochromic refers to a functional material which is a compound, under the action of light with certain wavelength and intensity, and the molecular structure of the material is changed along with the change of an absorption spectrum, so that the absorbance and the color of the material are changed, the change is generally reversible, and the material can automatically recover to the original state after the light is stopped, and the photochromic material is used as a new material in the field of optical material subdivision and has important application value in the technical fields of optical lenses, optical information storage, molecular switches, anti-counterfeiting identification and the like. The phenomenon of photochromism has been found by humans for over a hundred years. The first successful commercial application, starting in the 60's of the 20 th century, two materials scientists, amistod and Stooky, in the Corning studio of the united states, first prepared photochromic materials containing silver halide glasses, and then a great deal of research into their mechanisms and applications, and the development of new photochromic eyewear. However, due to its high cost and complex processing technology, it is not suitable for manufacturing large-area photochromic glass, and thus, its commercial application in the building field is limited. Then, the application center of gravity of photochromism is shifted to polymer-based materials with low price and light weight, and the photochromism compound is added into transparent resin to prepare the photochromic material which can be used for resin spectacle lenses and is applied to photochromic spectacles at home and abroad. Silver halide photochromic materials have been phased out because they are not suitable for use with resin lenses. The application of the organic photochromic compound on the resin lens at present mainly comprises the following types: spiroindoline naphthoxazines, naphthopyrans, fulgide photochromic compounds, and the like. Although important achievements are achieved in the aspect of practical application, the disadvantages of poor light stability, low photochromic response value, insufficient thermal stability and the like of the photochromic compound exist, such as: photochromic compounds are susceptible to the influences of pH value, oxidation, illumination intensity, temperature, matrix environment and the like to cause the deterioration of photochemical fatigue, and are degraded and deteriorated after repeated irradiation for many times to lose reversible photochromic performance, or the conditions of prolonged color change response time, reduced chromaticity, delayed fading recovery time and the like are caused.
The light stability, namely fatigue resistance, of the color-changing compound is one of the important problems of the color-changing compound in practical application. The research on photochromic mechanism shows that the main reason for fatigue is that the compound is photooxidation degraded during the photoisomerization reaction, and the fatigue phenomenon occurs. Therefore, antioxidant research has become a major approach for compounds to improve fatigue resistance. At present, the following methods are mainly utilized to improve the fatigue resistance: firstly, adding a light stabilizer or an antioxidant into a polymer medium containing a color-changing compound; secondly, directly keying antioxidant groups on compound molecules; thirdly, introducing an electricity-rich heteroaryl group into a side chain of a compound molecule; and fourthly, improving the fatigue resistance by adding a single-base peroxy quencher or adopting a spin-trapping agent. Therefore, researchers have improved performance by microencapsulating color-changing compounds, such as: patent ZL200810057392 discloses a preparation method of photochromic microcapsules, which can improve the acid and alkali resistance and fatigue resistance of photochromic materials and prolong the service life. The patent ZL201410195430.3 discloses a preparation method of a polyurethane-chitosan double-shell photochromic microcapsule, and double-layer coating can further improve the coating rate, fatigue resistance and the like of photochromic compounds. Therefore, the development of compounds and composite materials with good photochromic performance has become one of the research hotspots of photochromic materials in recent years, and particularly, the development of the photochromic materials with excellent fatigue resistance, good thermal stability and high spectral response value has higher popularization and application values.
In addition, photochromic properties are also often affected by the polymer molecules, other chemical aids in the matrix, the microstructure, the polymerization environment, etc., such as: the color-changing compound is greatly influenced by the ultraviolet absorbent in the polymer, and the color-changing compound is greatly limited by the excitation of ultraviolet spectrum to change color due to the absorption of ultraviolet rays by the ultraviolet absorbent in the polymer, so that the color-changing efficiency is low; meanwhile, the existence of diopter leads to the inconsistency of the edge thickness and the center thickness of the lens, in this case, if the method of adding the color-changing compound in the body is still adopted, the color depth chromatic aberration of different positions of the thickness of the lens can be caused. Therefore, some manufacturers in China use spin coating to produce color-changing lenses. The spin coating method is that after the substrate is made, the prepared color-changing solution is added into a groove of a spin coater, after the color-changing solution is fully mixed, the substrate is fixed on the spin coater to carry out centrifugal rotation movement, and the substrate is solidified to form a product with the color-changing effect.
Disclosure of Invention
The invention aims to provide a polyurethane/spiropyran/zinc sulfide composite multilayer photochromic material and application thereof. The material can be prepared into a photochromic coating or blended into a resin optical material to prepare an optical color-changing material. The material can be changed from colorless to colored under the irradiation of ultraviolet rays, and can be quickly faded to colorless after the ultraviolet rays disappear, and the material has the advantages of strong fatigue resistance, good stability, high color changing speed and the like.
In order to achieve the purpose, the invention provides the following technical scheme:
a photochromic nanometer composite microsphere is a three-layer composite core-shell structure, wherein the inner core is a zinc sulfide mesoporous nanometer microsphere, the middle layer is a photochromic layer formed by a spiropyran compound, and the outer shell is polyurethane; the composite microsphere has the outer diameter of 50-350nm, wherein the diameter of the zinc sulfide mesoporous nano microsphere is 30-250 nm, the thickness of the middle layer is 5-25 nm, and the thickness of the shell is 5-25 nm.
As described above, preferably, the zinc sulfide mesoporous nanospheres are monodisperse zinc sulfide mesoporous nanospheres composed of zinc sulfide nanocrystals, and the intermediate layer is formed by uniformly dispersing spiropyran compound nanoparticles on the surface or in the gaps of the zinc sulfide mesoporous nanospheres to form a nanocomposite mesoporous structure.
The photochromic nanocomposite microspheres as described above, preferably, the spiropyran-based compound is selected from a compound of formula (I), formula (II) or formula (III):
Figure BDA0001463890620000031
wherein R ═ C16H33
Figure BDA0001463890620000032
Wherein R ═ C16H33
Figure BDA0001463890620000033
Figure BDA0001463890620000041
Preferably, the polyurethane is prepared by polymerizing an isocyanate monomer compound containing two or more isocyanate groups and an alcohol compound.
The photochromic nanocomposite microspheres as described above, preferably, the isocyanate monomer compound is selected from the group consisting of: at least one of toluene diisocyanate, diphenylmethane-4, 4' -diisocyanate, 1.6-hexamethylene diisocyanate, m-xylylene diisocyanate, naphthalene-1.5-diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, and isophorone diisocyanate;
preferably, the alcohol compound is at least one of n-butanol, polytetrahydrofuran ether glycol, pentaerythritol, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, and trimethylolpropane.
The photochromic nanocomposite microsphere as described above is preferably prepared by the following method:
a. preparing spiropyran coated zinc sulfide nanospheres:
adding zinc nitrate into ethylene glycol, uniformly stirring, adding sulfur powder, heating to the temperature of 140 ℃ and 160 ℃, and reacting for 20-24 hours; cooling to 40-60 ℃, dropwise adding a mercaptoethanol stabilizer and stirring; adding a spiropyran compound, stirring vigorously for 20-40 minutes, cooling to room temperature, gradually layering and precipitating reaction liquid, filtering and collecting precipitate, washing, and drying to obtain spiropyran-coated zinc sulfide mesoporous nanospheres; wherein the mass ratio of the zinc nitrate, the sulfur powder, the mercaptoethanol and the ethylene glycol is (0.3-0.6) to (0.1-0.2) to (4-7) to (90-110), and the mass ratio of the zinc nitrate and the spiropyran compound is 1 to (0.5-1);
b. preparing polyurethane/spiropyran/zinc sulfide nano composite microspheres:
b, adding the spiropyran coated zinc sulfide mesoporous nanospheres and the isocyanate monomer compound prepared in the step a into a solvent, uniformly stirring, and then sequentially adding an alcohol compound and a dispersing agent; wherein the spiropyran-coated zinc sulfide mesoporous nanospheres, the isocyanate monomer compound, the alcohol compound, the dispersant and the solvent are in mass ratio as follows: (0.5-1.2) to (0.5-0.9) to (1.2-2.2) to 100; keeping the temperature at 15-25 ℃, and carrying out prepolymerization reaction for 45-60min under stirring to obtain a prepolymer solution; adding a chain extender and a catalyst into a prepolymer solution, heating the chain extender, the catalyst and an isocyanate monomer compound to the mass ratio of (6-15) to (0.1-0.3) to (9-11) to perform polymerization chain extension reaction for 10-15min under the stirring condition at the temperature of 45-90 ℃, generating a polyurethane coating precipitate, filtering, washing and drying the precipitate to obtain the photochromic nano composite microsphere with the polyurethane/spiropyran/zinc sulfide three-layer composite core-shell structure.
Preferably, the solvent is at least one of chloroform, acetone, propyl acetate, butyl acetate, ethyl acetate, dibutyl phthalate and petroleum ether, and the catalyst is dibutyltin dilaurate.
Preferably, the alcohol compound is a mixture of n-butanol and polytetrahydrofuran ether glycol, wherein the mass ratio of n-butanol to polytetrahydrofuran ether glycol is (1-3) to (9-11).
The photochromic nano composite microsphere as described above, preferably, the dispersant is at least one of tween 20, tween80, span 20, span 60 and span 80;
preferably, the chain extender is at least one of ethylene glycol, propylene glycol, ethylenediamine, propylenediamine and diethylamine;
preferably, the chain extender is a mixture of ethylene glycol and ethylenediamine, and the mass ratio of the ethylene glycol to the ethylenediamine is (2-3) to (0.6-1.5).
In another aspect, the present invention includes applying the photochromic nanocomposite microspheres as described above as a color-changing material to a color-changing coating layer or a color-changing optical material.
The spiropyran photochromic compound of the present invention may be any known spiropyran photochromic compound, preferably spiropyran photochromic compound (I), spiropyran photochromic compound (II), spiropyran photochromic compound (III), and the three compounds may be synthesized by, but not limited to, the following methods.
(1) Synthesis of spiropyran photochromic Compound (I):
I. adding 2, 3, 3-trimethylindole and iodohexadecane into a trichloromethane solvent with a reflux device, wherein the mass ratio of the 2, 3, 3-trimethylindole to the iodohexadecane to the trichloromethane is (25-35) to (80-110) to (350-400), heating and refluxing for 16-24 hours under normal pressure, evaporating to remove the solvent, adding anhydrous ether, namely, generating a large amount of light yellow solids, performing suction filtration, fully washing with ether, and performing vacuum drying to obtain hexadecane-2, 3, 3-trimethylindole (PS 01);
dispersing PS01 in water, wherein the mass ratio of water to iodohexadecane is (1-2) to 1, continuously stirring and dropwise adding 25-35% NaOH solution until the solid completely disappears, stopping dropwise adding until a yellowish oily viscous substance is generated on the liquid surface, clarifying the lower layer, extracting with diethyl ether, washing with water, filtering, and removing diethyl ether by rotary evaporation to obtain a yellowish transparent liquid 3, 3-dimethyl-1' -hexadecyl-2-methylindole (PS 02);
preparing an ethanol solution containing PS02 and an ethanol solution containing 4-hydroxy-1, 3-benzenedicarboxaldehyde respectively, wherein the mass ratio of PS02 to ethanol is (1-2) to (3-9), and the mass ratio of PS02 to 4-hydroxy-1, 3-benzenedicarboxaldehyde is (2-3) to 1, 4-hydroxy-1, 3-benzenedicarboxaldehyde to ethanol is (2-3) to (50-100); heating the 4-hydroxy-1, 3-benzene dicarbaldehyde ethanol solution in an oil bath at 45-78 ℃ under the protection of nitrogen until reflux, dropwise adding a newly prepared ethanol solution containing PS02 into the ethanol solution, wherein the reaction solution quickly becomes purple, continuously heating and refluxing for 5-6 hours, cooling the room temperature, pouring the reaction solution into ice, stirring to obtain a light purple emulsion, fully standing, evaporating water and ethanol, recrystallizing a sticky substance with methanol, and performing suction filtration and drying to obtain light purple solid powder, namely the alkyl spiropyran photochromic compound (I).
The specific reaction formula is as follows:
Figure BDA0001463890620000061
(2) synthesis of spiropyran photochromic Compound (II):
dissolving 2-hydroxy-1-naphthaldehyde in absolute ethyl alcohol according to the mass ratio of (0.8-1.2) to (15-30), heating to 45-78 ℃ under the protection of nitrogen, refluxing, dropwise adding an ethanol solution containing PS02 into the ethanol solution, wherein the mass ratio of the PS02 ethanol solution to the 2-hydroxy-1-naphthaldehyde is (2-3) to 1, wherein the mass ratio of the PS02 to the absolute ethyl alcohol is (1-2) to (3-9), continuously and stably refluxing for 8-10h, cooling to room temperature, concentrating a solvent to 40-50%, sealing and placing in an ice bath at 0-minus 5 ℃ for 10-20 h, separating out a large amount of white solids, performing suction filtration, performing column chromatography on a crude product (petroleum ether: ethyl acetate 1: 1), and performing vacuum drying to obtain an alkyl-naphthospiropyran photochromic compound (II), the specific reaction formula is as follows:
Figure BDA0001463890620000062
(3) synthesis of spiropyran photochromic Compound (III):
the first step is as follows: heating 4-hydroxy-6, 7-dimethoxy-1-phenyl-2-naphthoic acid, o-xylene and polyphosphoric acid to 160 ℃ at the mass ratio of (0.8-1.2) to (1.5-2.5) to (0.8-1.2) for reaction for 1-2H, pouring the reaction liquid into water for filtration, and performing vacuum drying to obtain 5-hydroxy-2, 3-dimethoxy-7H-benzo [ c ] fluorene-7-ketone;
the second step is that: reacting tetrahydrofuran with 5-hydroxy-2, 3-dimethoxy-7H-benzo [ c ]]Mixing fluorene-7-ketone in the weight ratio of 0.6-1 to 1, cooling to-10-20 deg.c, and dropping methyl magnesium chloride in the concentration of 3.0M, methyl magnesium chloride and 5-hydroxy-2, 3-dimethoxy-7H-benzo [ c ]]The mass ratio of the fluorene-7-ketone is (0.6-1.2) to (0.7-1.2), and the temperature is controlled not to exceed-10 ℃ in the dropping process. After the dropwise addition is finished, the temperature is kept between minus 10 ℃ and 15 ℃ for reaction for 90 minutes to 120 minutes, saturated ammonium chloride solution is added for quenching reaction, the mass ratio of ammonium chloride to methyl magnesium chloride is (1-3) to 1, liquid separation is carried out, an aqueous layer is extracted by ethyl acetate, organic layers are combined, and anhydrous Na is added2SO4Drying, vacuum evaporating solvent, and performing column chromatography to obtain 2, 3-dimethoxy-7-methyl-7H-benzo [ c ]]Fluorene-5, 7-diol;
the third step: 2, 3-dimethoxy-7-methyl-7H-benzo [ c ]]Fluorene-5, 7-diol, toluene, 1-di (4-methoxyphenyl) -2-propyn-1-ol and p-toluenesulfonic acid (TsOH) according to the mass ratio: mixing (0.7-1.0) to (4-6) to (0.6-1.0) to (0.1-0.3), heating to 65-95 deg.C for 10-16h, vacuum evaporating toluene, adding saturated sodium bicarbonate solution for quenching reaction, mixing sodium bicarbonate solution and p-toluene at a mass ratio of (0.3-0.6) to 1, separating, extracting with ethyl acetate in water layer, mixing organic layers, and adding anhydrous Na2SO4Drying, vacuum evaporating solvent, and column chromatography (petroleum ether: ethyl acetate 15: 1 elution) is carried out on the crude product to obtain the spiropyran photochromic compound (III).
The main reaction process is that 4-hydroxy-6, 7-dimethoxy-1-phenyl-2-naphthoic acid is cyclized under the acid condition to obtain an intermediate 5-hydroxy-2, 3-dimethoxy-7H-benzo [ c ] fluorene-7-ketone; and reacting with methyl Grignard reagent-magnesium chloride to obtain 2, 3-dimethoxy-7-methyl-7H-benzo [ c ] fluorene-5, 7-diol; then the spiropyran photochromic compound (III) is generated by the reaction of the spiropyran photochromic compound (III) and 1, 1-di (4-methoxyphenyl) -2-propyne-1-alcohol under the catalysis of p-toluenesulfonic acid, and the specific reaction formula is as follows:
Figure BDA0001463890620000071
Figure BDA0001463890620000081
the acid in the reaction is acetic acid, trifluoroacetic acid, phosphoric acid, sulfuric acid or polyphosphoric acid, preferably polyphosphoric acid.
The photochromic nano composite microsphere is a polyurethane/spiropyran/zinc sulfide three-layer composite core-shell structure, the inner core of the photochromic nano composite microsphere is a zinc sulfide mesoporous nano microsphere, and in the preferred technical scheme of the invention, the preparation route of the zinc sulfide mesoporous nano microsphere is as follows: condensing ethylene glycol at high temperature to produce acetaldehyde, providing a hydrogen atom, and using the acetaldehyde as a reducing agent to change S into S2-Followed by release of Zn from zinc nitrate hexahydrate2+And S2-Combining to form ZnS crystal nucleus which grows continuously based on a diffusion mechanism, so that initial particles of the reaction, namely zinc sulfide nanocrystals are gradually aggregated to form secondary particles, namely zinc sulfide nanospheres; when nucleation reaches a certain stage, mercaptoethanol plays an important role in the reaction process, on one hand, the mercaptoethanol effectively prevents the agglomeration of a large number of particles, on the other hand, the continuous growth of the particles is limited, and the nucleation of the nanocrystals is gradually stopped along with the reduction of the ion concentration, wherein the specific nucleation reaction equation is as follows:
HOCH2CH2OH→CH3CHO+H2O (1)
S+2CH3CHO→CH3CO-OCCH3+S2-+2H+(2)
Zn2++S2-→ZnS(s) (3)
the prepared zinc sulfide nano microsphere is formed in the nucleation process of zinc sulfide nano crystals, and is a monodisperse zinc sulfide mesoporous nanosphere consisting of a plurality of small nano crystals.
And the added spiropyran discoloring compound is uniformly dispersed on the surface and gaps of the zinc sulfide microspheres in a nanoparticle form. And finally, covering by using polyurethane as a shell to form the nano composite core-shell structure.
As shown in fig. 7, the photochromic nanocomposite microspheres are spherical in appearance, wherein the darker core is composed of a plurality of uniformly sized and monodisperse zinc sulfide nanospheres, the lighter colored outer layer is a spiropyran chromic compound, and the outer shell of polyurethane is a colorless transparent material, so that the photochromic nanocomposite microspheres cannot be displayed and distinguished in a transmission electron microscope photograph.
The invention has the beneficial effects that: the photochromic nano composite microsphere is a polyurethane/spiropyran/zinc sulfide three-layer composite core-shell structure, the spiropyran is positioned between a shell and a core as a photochromic compound, namely a middle layer, the three-dimensional space is in a nanoscale range, and the energy level change and the energy gap widening caused by the quantum size effect are realized. On one hand, the unique structure can ensure that the color-changing compound is protected by a polyurethane shell with relatively stable property, and the color-changing compound is prevented from being influenced by the external environment; on the other hand, due to the stable supporting effect of the core zinc sulfide nano mesoporous structure, the Van der Waals area of the color-changing molecules is enlarged, the conjugated system is enlarged, the space volume of the molecules is enlarged, and the gaps between the molecules are enlarged, so that the space for the molecules to generate isomerization reaction is greatly increased, the activity of the color-changing body is enhanced, the obstruction of conversion between the color-changing open ring body and the colorless closed ring body is reduced, the conversion time is shortened, the speed is accelerated, the spectral response becomes more sensitive, and the color-changing effect is good. In addition, under the illumination condition, the polyurethane shell can absorb part of light, part of incident ultraviolet rays are absorbed by the zinc sulfide core, and the light intensity irradiated on the surface of the spiropyran allochroic compound is lower than that directly irradiated on the surface of the spiropyran allochroic compound; meanwhile, the irradiation intensity and the irradiation retention time required for exciting the color change of the spiropyran are not influenced, and the residual ultraviolet rays are absorbed by the zinc sulfide inner core. Therefore, the oxidation resistance and fatigue resistance of the polyurethane/spiropyran/zinc sulfide nano composite microsphere are obviously enhanced.
The photochromic coating or optical material prepared from the photochromic nano composite microsphere can be changed into color from colorless under the irradiation of ultraviolet rays, and can be quickly faded into colorless after the ultraviolet rays disappear, so that the photochromic coating or optical material has the advantages of strong fatigue resistance, good stability, high color changing speed and the like.
Drawings
FIG. 1 is a normal environment absorption spectrum of the polyurethane/spiropyran/zinc sulfide nano-composite microsphere prepared in example 1.
FIG. 2 is a high-temperature environment absorption spectrum diagram of the polyurethane/spiropyran/zinc sulfide nanocomposite microsphere prepared in example 1.
FIG. 3 shows normal environmental absorption spectrum of the spiropyran-based photochromic compound (III).
FIG. 4 is a high-temperature environment absorption spectrum diagram of the spiropyran photochromic compound (III).
FIG. 5 is a normal environmental absorption spectrum of the polyurethane/spiropyran nanocomposite microsphere prepared in comparative example 2.
FIG. 6 is a high-temperature environment absorption spectrum of the polyurethane/spiropyran nanocomposite microsphere prepared in comparative example 2.
Fig. 7 is a transmission electron microscope photograph of the photochromic nanocomposite microsphere prepared in example 1.
FIG. 8 is an infrared spectrum of the photochromic nanocomposite microsphere prepared in example 1 with pure zinc sulfide, spiropyran compound III, and polyurethane.
Detailed Description
The invention is further illustrated by the following specific examples, which are not intended to limit the scope of the invention.
The spiropyran-based photochromic compounds in the following examples and comparative examples were prepared by the following methods:
(1) preparation of spiropyran photochromic Compound (I):
A. adding 29g of 2, 3, 3-trimethylindole and 95g of iodohexadecane into 400g of trichloromethane solvent, heating and refluxing for 20 hours under normal pressure, evaporating to remove the solvent, adding 70g of anhydrous ether, layering, performing suction filtration, fully washing with ether, and performing vacuum drying to obtain hexadecane-2, 3, 3-trimethylindole (PS 01); dispersing PS01 in 170g of water, stirring and dropwise adding 26% NaOH solution, stopping dropwise adding after the solid completely disappears, extracting with diethyl ether after layering, washing with water, filtering, and removing diethyl ether by rotary evaporation to obtain 3, 3-dimethyl-1' -hexadecyl-2-methylindole (PS 02);
B. heating 575g of ethanol solution of 4-hydroxy-1, 3-benzene dicarbaldehyde (25 g of ethanol in the solution) in an oil bath under the protection of nitrogen till refluxing, heating to 65 ℃, dropwise adding 63g of ethanol solution containing PS02 (18 g of ethanol in the solution), continuously heating and refluxing for 6 hours after the color changes to purple, cooling to room temperature, pouring the reaction solution into ice, stirring, obtaining light purple emulsion after the ice is completely melted, fully standing, evaporating to remove water and ethanol, recrystallizing the sticky substance with methanol, filtering and drying to obtain light purple solid powder, namely the alkyl spiropyran photochromic compound (I).
(2) Preparation of spiropyran photochromic compound (II):
heating 230g of ethanol solution (containing 10g of ethanol) containing 2-hydroxy-1-naphthaldehyde to 60 ℃ in an oil bath under the protection of nitrogen until reflux, dropwise adding 24g of ethanol solution (containing 5g of ethanol) of PS02, continuously refluxing for 9 hours, cooling to room temperature, evaporating to remove the solvent, concentrating to 40%, hermetically placing in an ice bath at the temperature of minus 2 ℃ for 15 hours, carrying out suction filtration, eluting a crude product by petroleum ether and ethyl acetate in a ratio of 1: 1, and carrying out vacuum drying to obtain the alkyl-naphthospiropyran photochromic compound (II)
(3) Preparation of spiropyran photochromic compound (III):
the first step is as follows: uniformly stirring and mixing 90g of 4-hydroxy-6, 7-dimethoxy-1-phenyl-2-naphthoic acid, 170g of o-xylene and 85g of polyphosphoric acid, heating to 145 ℃, reacting for 90 minutes, pouring the reaction liquid into water, filtering, and drying in vacuum to obtain 5-hydroxy-2, 3-dimethoxy-7H-benzo [ c ] fluorene-7-ketone;
the second step is that: taking 75g of tetrahydrofuran and 95g of 5-hydroxy-2, 3-dimethoxy-7H-benzo [ c ]]Mixing fluoren-7-one, cooling to-12 deg.C, adding dropwise methyl magnesium chloride 80g with concentration of 3.0M, reacting at-10 deg.C for 100 min, adding saturated ammonium chloride solution 150g, extracting water layer with ethyl acetate (170mL × 3), combining organic layers, and adding anhydrous Na2SO4Drying, vacuum evaporating solvent, and performing column chromatography to obtain 2, 3-dimethoxy-7-methyl-7H-benzo [ c ]]Fluorene-5, 7-diol;
the third step: 40g of 2, 3-dimethoxy-7-methyl-7H-benzo [ c ]]Fluorene-5, 7-diol250g of toluene, 42g of 1, 1-bis (4-methoxyphenyl) -2-propyn-1-ol and 9g of p-toluenesulfonic acid are stirred and mixed uniformly, heated to 75 ℃ for reaction for 15 hours, the toluene is evaporated under reduced pressure, 110g of saturated sodium bicarbonate solution is added for quenching reaction, an aqueous layer is extracted by ethyl acetate (90mL multiplied by 3), organic layers are combined, and anhydrous Na2SO4Drying, decompressing and distilling out the solvent, and carrying out column chromatography on the crude product to obtain the spiropyran photochromic compound (III).
Example 1: preparation of photochromic nano composite microspheres, photochromic coating liquid and photochromic lens
Preparing photochromic nano composite microspheres:
(1) adding 9.7g of zinc nitrate hexahydrate into 1600g of ethylene glycol, stirring uniformly, adding 1.6g of sublimed sulfur powder, heating to 150 ℃, keeping the temperature, reacting for 24 hours, cooling to 55 ℃, dropwise adding 85g of mercaptoethanol, and stirring; then adding 6.7g of spiropyran photochromic compound shown in the formula III, stirring vigorously for 30 minutes, continuously cooling to room temperature, filtering and washing the precipitate, and drying in a vacuum drying oven at 65 ℃ for 8 hours to obtain spiropyran-coated zinc sulfide nanospheres;
(2) adding 8g of spiropyran-coated zinc sulfide nanosphere, 8.2g of diphenylmethane-4, 4' -diisocyanate (MDI) into 1000g of butyl acetate solvent, stirring uniformly, then respectively adding 7g of mixed reactants (1.2g of n-butyl alcohol, 5.8g of polytetrahydrofuran ether glycol) and 18g of Tween80, keeping the temperature at 20 ℃, carrying out prepolymerization reaction at the rotating speed of 500r/min for 60min, adding 9.2g of chain extender (6 g of ethylene glycol and 3.2g of ethylenediamine) and 0.1g of catalyst dibutyltin Dilaurate (DBTL), heating to 60 ℃, carrying out polymerization chain extension reaction for 15min, stirring at the speed of 1200r/min, filtering, washing and drying solid substances to obtain the polyurethane/spiropyran/zinc sulfide nano composite microsphere. The yield was 75%.
(3) Observing the product prepared in the step (2) by using a JEM-2100 type transmission electron microscope, as shown in fig. 7, showing that the appearance is spherical, wherein the core with darker color is composed of a plurality of uniformly sized and monodisperse zinc sulfide nanospheres, the outer layer with light color is a shell formed by the spiropyran chromic compound and polyurethane, the core-shell structure composite microsphere formed by adsorbing the spiropyran chromic compound material and coating the spiropyran compound material by the zinc sulfide nanospheres with larger specific surface area and pore volume can be concluded as the polyurethane outer shell is a colorless transparent material, so that the core-shell structure composite microsphere cannot be displayed and distinguished in a transmission electron microscope picture.
(4) The product prepared in the step (2) is tested by Fourier transform infrared spectroscopy (FT-IR), and the spectrogram is compared with the infrared spectrogram of pure zinc sulfide, spiropyran discolor compound III and polyurethane. The results are detailed in FIG. 8, in which curve a is an infrared spectrum of zinc sulfide; b, the curve is a spiropyran compound III infrared spectrogram; the curve c is an infrared spectrogram of the polyurethane material; the d curve is the infrared spectrum of the photochromic nanocomposite microsphere prepared in example 1.
3421cm from curve a analysis-1The wider absorption peak is O-H stretching vibration peak, 1620cm-1The absorption peak is the bending vibration peak of H-O-H, which is the characteristic absorption peak of water and can be attributed to the water adsorption on the surface of ZnS powder at 900-4000cm-1There was substantially no absorption peak in the range, indicating that the ZnS powder has a good infrared transmittance.
From the analysis of the b curve in the figure, 3430cm-12960cm, which is a stretching vibration absorption peak of-OH-1Is represented by-CH3Absorption peak of telescopic vibration, 1640--1Vibration absorption peak ascribed to benzene ring, 1366cm-1is-CH3Flexural vibration absorption Peak, 960cm-1Is represented by-CH3Absorption peak of stretching vibration, 820cm-1Is the vibration absorption peak of ortho-disubstituted benzene ring.
As can be seen from the analysis of the curve c in the figure, the suction at 3251-3480The peak is a stretching vibration peak of polyurethane hydroxyl-OH; 2270cm-1The strong absorption peak is generated by the stretching vibration of the-NCO group, other groups do not generate absorption at the peak, and the peak is the characteristic absorption peak of the isocyanate.
From the d curve analysis in the figure, 3430cm-1Stretching vibration absorption peak at-OH, 2270cm-1The disappearance of the vibration absorption peak indicates the absence of-NCO groups because the MDI monomer is completely reacted and the isocyanate has reacted with the compound containing weak active hydrogen atoms to form carbamate, 1706cm-1The absorption peak at (a) represents the vibration absorption peak of-C ═ O in the polyurethane; 1460cm-1The absorption peak at is CH2Vibration absorption peak or CH of group (methylene)3Despite the wave number (1366 cm) absorbed by the spiropyran molecules-1) The inconsistency is probably caused by that after the spiropyran molecules are adsorbed to the ZnS nano particles, the absorption spectrum is shifted due to the interaction between different molecules; 1224cm-1The absorption peak at (A) is a vibration absorption peak of the ether bond-C-O-C-.
By comparison, the infrared spectrogram of the photochromic nanocomposite microsphere prepared in example 1 not only has the characteristic absorption peak of the spiropyran derivative, but also contains the characteristic absorption peak of polyurethane, which indicates that the photochromic nanocomposite microsphere prepared in example 1 is not a single zinc sulfide substance, and also contains the spiropyran derivative and the polyurethane substance.
(II) preparing a photochromic coating liquid:
1. preparing a polyurethane component A: 675g of 2, 3-dimercaptoethyl thiopropanethiol (BES) monomer, 120g of dichloromethane, 35g of polyurethane/spiropyran/zinc sulfide nano composite microspheres, 15g F420 wetting dispersant (product of Orner Polymer Co., Ltd., Fushan City), and 5g F300 leveling agent (product of Orner Polymer Co., Ltd., Fushan City) are added into a container, and the mixture is uniformly stirred at room temperature for 25min to obtain a component A;
2. preparing a polyurethane component B: adding 145g of m-xylylene diisocyanate curing agent, 4g of XPJ01F defoamer (product of Jiangsu Sail Xinyue defoamer Co., Ltd.), and 1g of DBTL catalyst into a container, and uniformly stirring for 5 minutes at room temperature to obtain a component B;
3. preparing a photochromic coating liquid: uniformly mixing the component A and the component B, and subpackaging in A, B containers, wherein the container A is 600g and is a first photochromic coating solution; 400g of container B, and 26g of methylene chloride was added to container B to obtain a second photochromic coating solution.
(III) preparing a photochromic lens:
soaking the polyurethane optical lens base material cleaned by NaOH into the first photochromic coating liquid for 3 minutes at room temperature, then slowly pulling the lens at the speed of 1.0mm/s, raising the speed to 1.3mm/s after 85 seconds, moving the lens into an oven, setting the temperature at 45 ℃, and baking for 80 minutes; and spraying the lens by using second photochromic liquid, and curing to obtain the spiropyran photochromic lens. Wherein the thickness of the coating was 45 μm.
Example 2:
preparing photochromic nano composite microspheres:
(1) adding 6.5g of zinc nitrate into 1600g of ethylene glycol, stirring uniformly, adding 1.7g of sublimed sulfur powder, heating to 150 ℃, reacting for 24 hours while keeping the temperature, cooling to 55 ℃, dropwise adding 70g of mercaptoethanol, and stirring; then adding 3.5g of spiropyran photochromic compound (I), stirring vigorously for 30 minutes, cooling to room temperature, filtering and washing the precipitate, and drying in a vacuum drying oven at 65 ℃ for 8 hours to obtain spiropyran coated zinc sulfide nanospheres;
(2) taking 5.5g of spiropyran-coated zinc sulfide nanospheres, adding 5g of MDI into 1000g of butyl acetate solvent, stirring uniformly, sequentially adding 5.5g of mixed reactants (1.0g of n-butyl alcohol, 4.5g of polytetrahydrofuran ether glycol) and 20g of Tween80, keeping the temperature at 25 ℃, carrying out prepolymerization reaction at the rotating speed of 500r/min for 50min, adding 6g of chain extenders (4.5 g of ethylene glycol, 1.5g of ethylenediamine) and 0.1g of DBTL, heating to 65 ℃ to carry out polymerization chain extension reaction for 15min, stirring at the speed of 1000r/min, filtering, washing and drying solid substances, thus obtaining the polyurethane/spiropyran/zinc sulfide nanocomposite microspheres. The yield was 74%.
The JEM-2100 type TEM photograph of the product is similar to that of FIG. 7.
(II) preparing a photochromic coating liquid:
1. preparing a polyurethane component A: adding 610g of 1, 2, 3-trithioethyl Thiopropane (TES) monomer, 100g of dichloromethane, 40g of polyurethane/spiropyran/zinc sulfide nano composite microspheres, 10g F420 wetting dispersant and 5g F320 flatting agent (product of Olympic polymer Co., Ltd., Fushan City) into a container, and uniformly stirring at room temperature for 20min to obtain a component A;
2. preparing a polyurethane component B: adding 150g of m-xylylene diisocyanate curing agent, 6g of XPJ01F defoaming agent and 3g of DBTL catalyst into a container, and uniformly stirring for 5 minutes at room temperature to obtain a component B;
3. preparing a photochromic coating liquid: uniformly mixing the component A and the component B, and subpackaging in A, B containers, wherein the container A is 600g and is a first photochromic coating solution; 324g of container B, and 20g of methylene chloride were added to the container B to obtain a second photochromic coating solution.
(III) preparing a photochromic lens:
soaking the hardened polyurethane optical lens base material into the first photochromic coating liquid for 3 minutes at room temperature, then slowly lifting the lens, wherein the lifting speed is 1.0mm/s, the speed is increased to 1.3mm/s after 85 seconds, moving the lens into an oven, setting the temperature at 45 ℃, and baking for 70 minutes; and spraying the lens by using second photochromic liquid, and curing to obtain the spiropyran photochromic lens. Wherein the coating thickness was 43 μm.
Example 3:
preparing photochromic nano composite microspheres:
(1) adding 11g of zinc nitrate hexahydrate into 1600g of ethylene glycol, uniformly stirring, adding 3g of sulfur powder, heating to 145 ℃, reacting for 24 hours while keeping the temperature, cooling to 50 ℃, dropwise adding 92g of mercaptoethanol, and stirring; adding 8g of spiropyran photochromic compound (I), stirring vigorously for 35 minutes, continuously cooling to room temperature, filtering and washing the precipitate, and drying in a vacuum drying oven at 60 ℃ for 9 hours to obtain spiropyran coated zinc sulfide nanospheres;
(2) adding 10g of spiropyran-coated zinc sulfide nanospheres, 10.8g of m-Xylylene Diisocyanate (XDI) into 1000g of butyl acetate solvent, stirring uniformly, sequentially adding 7.4g of mixed reactants (1.0g of n-butanol, 6.4g of polytetrahydrofuran ether glycol) and 16g of Tween80, keeping the temperature at 25 ℃, carrying out prepolymerization reaction at the rotating speed of 600r/min for 60min, adding 8g of chain extenders (5.5 g of ethylene glycol, 2.5g of ethylenediamine) and 0.2g of DBTL, heating to 60 ℃, carrying out polymerization chain extension reaction for 15min, stirring at the speed of 1300r/min, filtering, washing and drying solid substances to obtain the polyurethane/spiropyran/zinc sulfide nano composite microspheres. The yield was 73%.
The JEM-2100 type TEM photograph of the product is similar to that of FIG. 7.
(II) preparing a photochromic coating liquid:
1. preparing a polyurethane component A: adding 710g TES monomer, 130g dichloromethane, 50g polyurethane/spiropyran/zinc sulfide nano composite microspheres, 18g F420 wetting dispersant and 10g F320 flatting agent into a container, and uniformly stirring at room temperature for 25min to obtain a component A;
2. preparing a polyurethane component B: adding 140g of m-toluene diisocyanate curing agent, 6g of XPJ01F defoaming agent and 5g of DBTL catalyst into a container, and uniformly stirring for 5 minutes at room temperature to obtain a component B;
3. preparing a photochromic coating liquid: uniformly mixing the component A and the component B, and subpackaging in A, B containers, wherein the container A is 600g and is a first photochromic coating solution; 469g of B vessel, 30g of methylene chloride was added to the B vessel to obtain a second photochromic coating solution.
(III) preparing a photochromic lens:
soaking the acid-washed polyurethane optical lens base material into the first photochromic coating liquid for 3 minutes at room temperature, then slowly lifting the lens, wherein the lifting speed is 1.0mm/s, the speed is increased to 1.3mm/s after 90 seconds, moving the lens into a drying oven, setting the temperature at 45 ℃, and baking for 70 minutes; and immersing the lens into second photochromic coating liquid again, wherein the method is the same as that of the first immersion coating, and curing to obtain the spiropyran photochromic lens. Wherein the thickness of the coating was 45 μm.
Example 4:
preparing photochromic nano composite microspheres:
(1) adding 14g of zinc nitrate hexahydrate into 1600g of ethylene glycol, uniformly stirring, adding 2g of sublimed sulfur powder, heating to 150 ℃, reacting for 23 hours while keeping the temperature, cooling to 50 ℃, dropwise adding 100g of mercaptoethanol, and stirring; adding 12g of spiropyran photochromic compound (II), stirring vigorously for 35 minutes, continuing cooling to room temperature, filtering and washing the precipitate, and drying in a vacuum drying oven at 60 ℃ for 9 hours to obtain spiropyran coated zinc sulfide nanospheres;
(2) adding 12g of spiropyran-coated zinc sulfide nanosphere and 11.5g of XDI into 1000g of butyl acetate solvent, stirring uniformly, sequentially adding 8.5g of mixed reactants (1g of n-butyl alcohol, 7.5g of polytetrahydrofuran ether glycol), 20g of Tween80, keeping the temperature at 20 ℃, carrying out prepolymerization reaction at the rotation speed of 650r/min for 60min, adding 8g of chain extender (5.5 g of ethylene glycol, 2.5g of ethylenediamine) and 0.2g of DBTL, heating to 60 ℃ to carry out polymerization chain extension reaction for 15min, stirring at the speed of 1200r/min, filtering, washing and drying solid substances to obtain the polyurethane/spiropyran/zinc sulfide nano composite microsphere. The yield was 72%.
The JEM-2100 type TEM photograph of the product is similar to that of FIG. 7.
(II) preparing a photochromic coating liquid:
1. preparing a polyurethane component A: adding 750g of 2, 2' -dimercaptoethylsulfide (MES) monomer, 150g of dichloromethane, 50g of polyurethane/spiropyran/zinc sulfide nano composite microspheres, 20g F420 wetting dispersant and 10g F300 leveling agent into a container, and uniformly stirring at room temperature for 25min to obtain a component A;
2. preparing a polyurethane component B: adding 120g of methylcyclohexyl diisocyanate curing agent, 7g of XPJ01F defoaming agent and 6g of DBTL catalyst into a container, and uniformly stirring for 5 minutes at room temperature to obtain a component B;
3. preparing a photochromic coating liquid: uniformly mixing the component A and the component B, and subpackaging in A, B containers, wherein the container A is 600g and is a first photochromic coating solution; in vessel B513 g, 30g of methylene chloride was added to vessel B to obtain a second photochromic coating solution.
(III) preparing a photochromic lens:
soaking the hardened polyurethane optical lens base material into the first photochromic coating liquid for 3 minutes at room temperature, then slowly lifting the lens, wherein the lifting speed is 0.9mm/s, the speed is increased to 1.4mm/s after 95 seconds, moving the lens into an oven, setting the temperature at 50 ℃, and baking for 75 minutes; and then immersing the lens into second photochromic coating liquid, wherein the method is the same as the first immersion coating, and curing to obtain the spiropyran photochromic lens. Wherein the coating thickness was 44 μm.
Example 5:
preparing photochromic nano composite microspheres:
(1) adding 8g of zinc nitrate hexahydrate into 1600g of ethylene glycol, uniformly stirring, adding 2.5g of sublimed sulfur powder, heating to 150 ℃, reacting for 23 hours while keeping the temperature, cooling to 50 ℃, dropwise adding 82g of mercaptoethanol, and stirring; then adding 5.2g of spiropyran photochromic compound (III), stirring vigorously for 35 minutes, cooling to room temperature, filtering and washing the precipitate, and drying in a vacuum drying oven at 60 ℃ for 9 hours to obtain spiropyran coated zinc sulfide nanospheres;
(2) adding 6.6g of spiropyran-coated zinc sulfide nanosphere, 5.6g of Toluene Diisocyanate (TDI) into 1000g of butyl acetate solvent, stirring uniformly, sequentially adding 6.3g of mixed reactants (0.9g of n-butyl alcohol, 5.4g of polytetrahydrofuran ether glycol) and 14g of Tween80, keeping the temperature at 25 ℃, carrying out prepolymerization reaction at the rotating speed of 700r/min for 60min, adding 5.5g of chain extender (4.5 g of ethylene glycol and 1g of ethylenediamine) and 0.1g of DBTL, heating to 60 ℃ for carrying out polymerization chain extension reaction for 15min, stirring at the speed of 1500r/min, filtering, washing and drying solid substances to obtain the polyurethane/spiropyran/zinc sulfide nano composite microsphere. The yield was 74%.
The JEM-2100 type TEM photograph of the product is similar to that of FIG. 7.
(II) preparing a photochromic coating liquid:
1. preparing a polyurethane component A: adding 640g of BES monomer, 110g of dichloromethane, 25g of polyurethane/spiropyran/zinc sulfide nano composite microspheres, 17g F420 wetting dispersant and 5g F309 flatting agent into a container, and uniformly stirring at room temperature for 25min to obtain a component A;
2. preparing a polyurethane component B: adding 110g of m-xylylene diisocyanate curing agent, 9g of XPJ01F defoaming agent and 7g of DBTL catalyst into a container, and uniformly stirring for 5 minutes at room temperature to obtain a component B;
3. preparing a photochromic coating liquid: uniformly mixing the component A and the component B, and subpackaging in A, B containers, wherein the container A is 700g and is a first photochromic coating solution; in the B vessel 223g, 15g of methylene chloride was added to the B vessel to obtain a second photochromic coating solution.
(III) preparing a photochromic lens:
soaking the hardened polyurethane optical lens base material into the first photochromic coating liquid for 3 minutes at room temperature, then slowly lifting the lens, wherein the lifting speed is 1.1mm/s, the speed is increased to 1.34mm/s after 85 seconds, moving the lens into an oven, setting the temperature at 45 ℃, and baking for 70 minutes; and spraying the lens by using second photochromic liquid, and curing to obtain the spiropyran photochromic lens. Wherein the coating thickness was 43 μm.
Example 6:
preparing photochromic nano composite microspheres:
(1) adding 8g of zinc nitrate hexahydrate into 1600g of ethylene glycol, uniformly stirring, adding 2.7g of sublimed sulfur powder, heating to 150 ℃, reacting for 23 hours while keeping the temperature, cooling to 45 ℃, dropwise adding 80g of mercaptoethanol, and stirring; then adding 5.9g of spiropyran photochromic compound (II), stirring vigorously for 35 minutes, continuing to cool to room temperature, filtering and washing the precipitate, and drying in a vacuum drying oven at 60 ℃ for 9 hours to obtain spiropyran-coated zinc sulfide nanospheres;
(2) adding 7.2g of spiropyran-coated zinc sulfide nanosphere and 6.9g of TDI into 1000g of butyl acetate solvent, stirring uniformly, sequentially adding 6.5g of mixed reactants (1.5g of n-butyl alcohol, 5.0g of polytetrahydrofuran ether glycol) and 12g of Tween80, keeping the temperature at 25 ℃, carrying out prepolymerization reaction at the rotating speed of 500r/min for 60min, adding 7g of chain extender (5.5 g of ethylene glycol, 1.5g of ethylenediamine) and 0.1g of DBTL, heating to 70 ℃ to carry out polymerization chain extension reaction for 15min, stirring at the speed of 1500r/min, filtering solid substances, washing and drying to obtain the polyurethane/spiropyran/zinc sulfide nano composite microsphere. The yield was 73%.
The JEM-2100 type TEM photograph of the product is similar to that of FIG. 7.
(II) preparing a photochromic coating liquid:
1. preparing a polyurethane component A: adding 660g of MES monomer, 140g of dichloromethane, 30g of polyurethane/spiropyran/zinc sulfide nano composite microspheres, 16g F420 wetting dispersant and 5g F320 flatting agent into a container, and uniformly stirring at room temperature for 25min to obtain a component A;
2. preparing a polyurethane component B: adding 100g of diphenylmethane-4, 4' -diisocyanate curing agent, 8g of XPJ01F defoaming agent and 8g of DBTL catalyst into a container, and uniformly stirring for 5 minutes at room temperature to obtain a component B;
3. preparing a photochromic coating liquid: uniformly mixing the component A and the component B, and subpackaging in A, B containers, wherein the container A is 600g and is a first photochromic coating solution; 367g of container B, 17g of methylene chloride was added to container B to obtain a second photochromic coating solution.
(III) preparing a photochromic lens:
soaking the hardened polyurethane optical lens base material into the first photochromic coating liquid for 4 minutes at room temperature, then slowly pulling the lens at the speed of 0.9mm/s, raising the speed to 1.4mm/s after 80 seconds, moving the lens into a drying oven, setting the temperature at 60 ℃, and baking for 60 minutes; and then immersing the lens into second photochromic coating liquid, wherein the method is the same as the first immersion coating, and curing to obtain the spiropyran photochromic lens. Wherein the thickness of the coating was 45 μm.
Comparative example 1:
photochromic coating liquids and photochromic lenses were prepared using the same operating conditions as in the steps (two) and (three) of example 1, except that the polyurethane/spiropyran/zinc sulfide nanocomposite microspheres were replaced with the spiropyran photochromic compound (III) in the preparation of the photochromic coating liquids.
Comparative example 2:
(1) the same operation conditions as those of the steps (one) - (2) of the example 1 are adopted, except that the spiropyran photochromic compound (III) is used for replacing the spiropyran to coat the zinc sulfide nanospheres, and the polyurethane/spiropyran nano composite microspheres are obtained.
(2) And (2) preparing photochromic coating liquid and photochromic lenses by adopting the same operation conditions as the steps (II) and (III) of the example 1, wherein the polyurethane/spiropyran/zinc sulfide nano composite microspheres obtained in the step (1) are used for replacing the polyurethane/spiropyran/zinc sulfide nano composite microspheres in the process of preparing the photochromic coating liquid.
Example 7: the photochromic materials prepared in example 1 and comparative examples 1 to 2 were respectively subjected to oxidation resistance tests
Respectively carrying out absorption spectrum detection on the polyurethane/spiropyran/zinc sulfide nano composite microspheres prepared in the embodiment 1, the spiropyran photochromic compound (III) and the polyurethane/spiropyran nano composite microspheres prepared in the comparative example 2;
(1) a detection step: taking 5g of the materials, dissolving the materials in 9mL of tetrahydrofuran, subpackaging and pouring the materials into a plurality of glass beakers, respectively placing one marked part into a sunlight simulation box for irradiation detection, irradiating for 15min at normal temperature, wherein the distance between the solution and a light source is 16CM, the radiation quantity hv is 2Eg, recording the difference between the absorption spectra of the solution before irradiation and after irradiation, and the detection result is shown in figure 1, figure 3, figure 5 and a table I.
TABLE-absorption Spectrum Difference (Δ OD) of solution under Normal Environment
Figure BDA0001463890620000181
(2) A detection step: respectively putting 5g of the polyurethane/spiropyran/zinc sulfide nano composite microspheres prepared in the example 1, 5g of the spiropyran photochromic compound (III) and 5g of the polyurethane/spiropyran nano composite microspheres prepared in the comparative example 2 into three crucibles, transferring the crucibles into a muffle furnace, uniformly heating to 200 ℃, and standing at the temperature for 28 hours; and taking out the photochromic compounds, respectively dissolving the photochromic compounds in 9mL of tetrahydrofuran, subpackaging and pouring the mixture into a plurality of glass beakers, respectively placing one marked part into a sunlight simulation box for irradiation detection, irradiating for 15min at normal temperature, wherein the distance between the solution and a light source is 16CM, the radiation quantity hv is 2Eg, and recording the difference between the absorption spectra of the solution before and after irradiation, wherein the detection results are shown in figure 2, figure 4, figure 6 and table two.
TABLE II absorption Spectrum Difference (Δ OD) of solution at high temperature
Figure BDA0001463890620000182
(II) anti-aging tests were performed on the photochromic lenses prepared in examples 1 to 6 and comparative examples 1 to 2, respectively
The detection steps and the method are as follows: the photochromic lenses prepared in the examples 1-6 and the comparative examples 1-2 are respectively subjected to irradiation ageing resistance experiments, the experimental equipment adopts a ZN-P type ultraviolet light ageing test box of the tin-free aerospace engineering technology Limited company, the temperature is set to be 60 ℃, the irradiation intensity selects the extreme irradiation condition, after identification, the irradiation is respectively carried out for 15 minutes and 48 hours, the transmittance data before and after irradiation are recorded, and the detection results are shown in the third table.
Table three photochromic lens transmittance (%)
Figure BDA0001463890620000191
And (4) test conclusion: the absorption spectrum of a solution containing polyurethane/spiropyran/zinc sulfide nano composite microspheres is unchanged (no difference) in normal environment and high-temperature environment; the absorption spectrum of the photochromic solution prepared in the comparative example 1-2 is changed under normal environment and high temperature environment, the change value at 550nm reaches 0.9, and the change value at 750nm reaches 1; and (II) the transmittance data of the photochromic lens containing the polyurethane/spiropyran/zinc sulfide nano composite microsphere coating before and after irradiation has no difference, while the transmittance data of the photochromic lens prepared in the comparative example 1-2 before and after irradiation has a larger difference, and the change values respectively reach 15 and 16.
The fatigue resistance of the photochromic material is mostly reflected by the change of absorbance or transmittance after discoloration, so the fatigue resistance is measured by the change of the absorbance before and after irradiation and the change of the transmittance, and the following conclusion is obtained by comparing test data: the optical material containing the polyurethane/spiropyran/zinc sulfide nano composite microspheres has stronger fatigue resistance.
Example 8: photochromic response test was performed on the resin lenses prepared in examples 1 to 6 and comparative examples 1 to 2, respectively
Photochromic response value test
The detection steps and the method are as follows: the ratio between the light transmittance tV (0) of the tested sample in the faded state and the light transmittance tV (1) of the discolored state after different illumination times (1-15min), namely: the spectral response value is tV (0) ÷ tV (1) to determine the photochromic response value of the tested sample at different temperatures. After the radiation intensity of the solar simulator is attenuated by 25%, the sample is irradiated with medium illumination intensity, the temperature is set to be 23 ℃, and the detection result is shown in the fourth table.
TABLE IV conditions of photochromic response values of test samples
Figure BDA0001463890620000201
(II) photochromic spectral response time detection
The detection steps and the method are as follows: placing the photochromic lenses prepared in examples 1-6 and comparative examples 1-2 into a test box respectively, turning on a solar simulator light source, and recording the time required for the lenses to change from colorless to colored; after 10 minutes of irradiation, the simulated light source is turned off, the time required for the lens to return to the colorless state from the colored state is recorded, and the detection result is shown in table five.
TABLE V detection of spectral response time of samples
Figure BDA0001463890620000202
In summary, the following steps: the optical material and the lens containing the polyurethane/spiropyran/zinc sulfide nano composite microspheres manufactured by the invention have the advantages of short photochromic response time, high spectral response sensitivity and the like.

Claims (11)

1. The photochromic nano composite microsphere is characterized by being of a three-layer composite core-shell structure, wherein the inner core is a zinc sulfide mesoporous nano microsphere, the middle layer is a photochromic layer formed by a spiropyran compound, and the outer shell is polyurethane; the composite microsphere has the outer diameter of 50-350nm, wherein the diameter of the zinc sulfide mesoporous nano microsphere is 30-250 nm, the thickness of the middle layer is 5-25 nm, and the thickness of the shell is 5-25 nm.
2. The photochromic nanocomposite microsphere of claim 1, wherein the zinc sulfide mesoporous nanospheres are monodisperse zinc sulfide mesoporous nanospheres composed of zinc sulfide nanocrystals, and the intermediate layer is a nano composite mesoporous structure formed by uniformly dispersing the spiropyran-based compound nanoparticles on the surface or in the gaps of the zinc sulfide mesoporous nanospheres.
3. The photochromic nanocomposite microsphere of claim 1 or 2, wherein the spiropyran-based compound is selected from the group consisting of compounds of formula (I), formula (II) or formula (III):
Figure FDA0002296198530000011
wherein R ═ C16H33
Figure FDA0002296198530000012
Wherein R ═ C16H33
Figure FDA0002296198530000021
4. The photochromic nanocomposite microspheres of claim 1, wherein the polyurethane is polymerized from an isocyanate monomer compound containing two or more isocyanate groups and an alcohol compound.
5. The photochromic nanocomposite microspheres of claim 4, wherein the isocyanate monomer compound is selected from the group consisting of: at least one of toluene diisocyanate, diphenylmethane-4, 4' -diisocyanate, 1.6-hexamethylene diisocyanate, m-xylylene diisocyanate, naphthalene-1.5-diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, and isophorone diisocyanate;
the alcohol compound is at least one of n-butyl alcohol, polytetrahydrofuran ether glycol, pentaerythritol, ethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol and trimethylolpropane.
6. The photochromic nanocomposite microspheres of any one of claims 1-5, wherein the photochromic nanocomposite microspheres are prepared by a process comprising:
a. preparing spiropyran coated zinc sulfide nanospheres:
adding zinc nitrate into ethylene glycol, uniformly stirring, adding sulfur powder, heating to the temperature of 140 ℃ and 160 ℃, and reacting for 20-24 hours; cooling to 40-60 ℃, dropwise adding a mercaptoethanol stabilizer and stirring; adding a spiropyran compound, stirring vigorously for 20-40 minutes, cooling to room temperature, gradually layering and precipitating reaction liquid, filtering and collecting precipitate, washing, and drying to obtain spiropyran-coated zinc sulfide mesoporous nanospheres; wherein the mass ratio of the zinc nitrate, the sulfur powder, the mercaptoethanol and the ethylene glycol is (0.3-0.6) to (0.1-0.2) to (4-7) to (90-110), and the mass ratio of the zinc nitrate and the spiropyran compound is 1 to (0.5-1);
b. preparing polyurethane/spiropyran/zinc sulfide nano composite microspheres:
b, adding the spiropyran coated zinc sulfide mesoporous nanospheres and the isocyanate monomer compound prepared in the step a into a solvent, uniformly stirring, and then sequentially adding an alcohol compound and a dispersing agent; wherein the spiropyran-coated zinc sulfide mesoporous nanospheres, the isocyanate monomer compound, the alcohol compound, the dispersant and the solvent are in mass ratio as follows: (0.5-1.2) to (0.5-0.9) to (1.2-2.2) to 100; keeping the temperature at 15-25 ℃, and carrying out prepolymerization reaction for 45-60min under stirring to obtain a prepolymer solution; adding a chain extender and a catalyst into a prepolymer solution, heating the chain extender, the catalyst and an isocyanate monomer compound to the mass ratio of (6-15) to (0.1-0.3) to (9-11) to perform polymerization chain extension reaction for 10-15min under the stirring condition at the temperature of 45-90 ℃, generating a polyurethane coating precipitate, filtering, washing and drying the precipitate to obtain the photochromic nano composite microsphere with the polyurethane/spiropyran/zinc sulfide three-layer composite core-shell structure.
7. The photochromic nanocomposite microspheres of claim 6, wherein the solvent is at least one of chloroform, acetone, propyl acetate, butyl acetate, ethyl acetate, dibutyl phthalate, petroleum ether, and the catalyst is dibutyltin dilaurate.
8. The photochromic nanocomposite microspheres of claim 6, wherein the alcohol compound is a mixture of n-butanol and polytetrahydrofuran ether glycol, wherein the mass ratio of n-butanol to polytetrahydrofuran ether glycol is (1-3) to (9-11).
9. The photochromic nanocomposite microspheres of claim 7, wherein the dispersant is at least one of tween 20, tween80, span 20, span 60, span 80;
the chain extender is at least one of ethylene glycol, propylene glycol, ethylenediamine, propylenediamine and diethylamine.
10. The photochromic nanocomposite microspheres of claim 7, wherein the chain extender is a mixture of ethylene glycol and ethylene diamine in a mass ratio of (2-3) to (0.6-1.5).
11. Photochromic nanocomposite microspheres according to any one of claims 1 to 10 as a color shifting material for application in color shifting coatings or color shifting optical materials.
CN201711113657.9A 2017-11-10 2017-11-10 Photochromic nano composite microsphere and application thereof Active CN107903889B (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201711113657.9A CN107903889B (en) 2017-11-10 2017-11-10 Photochromic nano composite microsphere and application thereof
PCT/CN2017/117714 WO2019090920A1 (en) 2017-11-10 2017-12-21 Photochromic optical material and preparation method therefor
EP17912346.8A EP3508554B1 (en) 2017-11-10 2017-12-21 Photochromic optical material and preparation method therefor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711113657.9A CN107903889B (en) 2017-11-10 2017-11-10 Photochromic nano composite microsphere and application thereof

Publications (2)

Publication Number Publication Date
CN107903889A CN107903889A (en) 2018-04-13
CN107903889B true CN107903889B (en) 2020-04-17

Family

ID=61844897

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711113657.9A Active CN107903889B (en) 2017-11-10 2017-11-10 Photochromic nano composite microsphere and application thereof

Country Status (1)

Country Link
CN (1) CN107903889B (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109324425A (en) * 2018-09-27 2019-02-12 镇江奥视达光学有限公司 A kind of anti-blue light screening glass and preparation method thereof
CN109331754B (en) * 2018-09-28 2021-06-29 江苏视科新材料股份有限公司 Blue-light-proof nano composite microsphere, blue-light-proof optical resin material and preparation method thereof
CN109369939B (en) * 2018-09-28 2021-04-27 南京米兰达视光科学研究院有限公司 Blue light prevention/color change dual-function optical resin material and preparation method thereof
IT202000003134A1 (en) * 2020-02-17 2021-08-17 Intercos Italiana Transparent colored cosmetic ingredient for cosmetic products, possibly capable of automatically changing color when irradiated by ultraviolet light
CN113817425A (en) * 2021-07-01 2021-12-21 江苏双星彩塑新材料股份有限公司 Photochromic polyester release film and preparation method thereof
CN114029011B (en) * 2021-10-25 2023-07-25 江苏视科新材料股份有限公司 Preparation method of organic/inorganic nano composite microsphere optomaterial
CN114035342A (en) * 2021-10-25 2022-02-11 江苏视科新材料股份有限公司 Resin lens for correcting color vision
CN114031706B (en) * 2021-10-25 2023-04-07 江苏视科新材料股份有限公司 Blue color weakness correcting lens and preparation method thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103215029B (en) * 2013-03-21 2014-11-26 江苏华天通科技有限公司 Nanometer complex phase photochromic material and preparation method
CN103962076B (en) * 2014-04-28 2017-05-17 江南大学 Preparation method of polyurethane-chitosan double-hull photochromic microcapsules
CN104817528A (en) * 2015-02-17 2015-08-05 江苏视客光电新材料有限公司 Spiropyran photochromic compound and preparation method thereof
CN106701058A (en) * 2016-11-18 2017-05-24 陕西品达石化有限公司 Preparation method for polyurethane-photochromic microcapsule

Also Published As

Publication number Publication date
CN107903889A (en) 2018-04-13

Similar Documents

Publication Publication Date Title
CN107778510B (en) Spiropyran photochromic optical material and preparation method thereof
CN107903889B (en) Photochromic nano composite microsphere and application thereof
CN107722027B (en) Preparation method of spiropyran photochromic nano composite microspheres
CN107779072B (en) Photochromic coating liquid and application thereof
CN1329477C (en) Photochromic polymer compositions and articles thereof
CN107828268B (en) Spiropyran photochromic coating and preparation method thereof
CN107722028B (en) Photochromic optical material
CN109337558B (en) Blue-light-proof coating liquid, blue-light-proof coating optical material and preparation method thereof
Ribot et al. New Photochromic Hybrid Organic–Inorganic Materials Built from Well‐Defined Nano‐Building Blocks
EP1438368A1 (en) Photochromic polymerizable compositions
EP1966342B1 (en) Photochromic plastic object
CN113004170A (en) Covalent macrocyclic polymer based on column [5] arene and preparation and application thereof
EP3508554B1 (en) Photochromic optical material and preparation method therefor
CN109337559B (en) Blue light/color change prevention dual-function coating optical material and preparation method thereof
EP1287086B1 (en) Hybrid polymer material for photochromic coatings and optical articles and glazings coated therewith
CN110981892B (en) Covalent organic framework material with spiropyran molecular switch and preparation method and application thereof
JPH0695290A (en) Thin clay film and its production
CN116751579A (en) Photochromic nano composite microsphere and application thereof
CN115057986B (en) Photochromic TPU composition for military camouflage and preparation method thereof
EP3762143A1 (en) Compounds for coordinating with a metal, compositions containing such compounds, and methods of catalyzing reactions
CN104628928B (en) Photochromic fluorocarbon resin as well as preparation method and application thereof
CN116769345B (en) Blue light discoloration prevention coating liquid, optical filter and preparation method of optical filter
CN114539274B (en) Single-factor induced photochromic sensing material and preparation method and application thereof
KR100860264B1 (en) A reactive spironaphthoxazine compound, a photocromic polymethacrylic polymer coating composition containing the spironaphthoxazine compound, a photocromic polymethacrylic polymer grafted with the spironaphthoxazine, and a photochromic optical article comprising the same
CN116769461A (en) Preparation method of colorful color-changing material

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
CB02 Change of applicant information
CB02 Change of applicant information

Address after: 211600 No. 73, Lishi Avenue, Jinhu Economic Development Zone, Huaian, Jiangsu

Applicant after: New material Limited by Share Ltd of Jiangsu University of optic science

Address before: 211600 No. 73, Lishi Avenue, Jinhu Economic Development Zone, Huaian, Jiangsu

Applicant before: JIANGSU SHIKE NEW MATERIAL CO., LTD.

GR01 Patent grant
GR01 Patent grant