CN111875760B - UV-cured fluorescent material with temperature-sensitive light transmittance and preparation method and application thereof - Google Patents

UV-cured fluorescent material with temperature-sensitive light transmittance and preparation method and application thereof Download PDF

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CN111875760B
CN111875760B CN202010096440.7A CN202010096440A CN111875760B CN 111875760 B CN111875760 B CN 111875760B CN 202010096440 A CN202010096440 A CN 202010096440A CN 111875760 B CN111875760 B CN 111875760B
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fluorescent
light transmittance
fluorescent material
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CN111875760A (en
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杨雄发
刘江玲
焦晓皎
程飞
吴于飞
范云鑫
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Hangzhou Normal University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/022—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations
    • C08F299/024—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations the unsaturation being in acrylic or methacrylic groups
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract

The invention relates to a high-molecular fluorescent material, and provides a fluorescent material with temperature-sensitive UV curing light transmittance and a preparation method and application thereof in order to overcome the defects of the fluorescent high-molecular material, wherein the fluorescent material with temperature-sensitive UV curing light transmittance is within the visible light range of 400-800nm, the light transmittance at 5 ℃ is 4-78%, the light transmittance at 25 ℃ is 75.0-98%, and the fluorescence intensity at 317nm is 3.3 multiplied by 10 6 cps‑8.0×10 6 cps, hardness of 4B-2B, and tensile strength of 0.5MPa-3.0 MPa. The fluorescent material is simple and convenient to prepare, rich and cheap in raw materials, convenient to industrialize, free of doping of luminescent fluorescent materials such as carbon quantum dots, rare earth metal ions or organic dyes, non-toxic, free of the problems that the color of the fluorescent material is difficult to regulate and control, poor dispersion stability in an elastomer and the like, and applied to the fields of temperature-sensitive optical devices, anti-counterfeiting, fluorescent probes, fluorescent coatings and the like.

Description

UV-cured fluorescent material with temperature-sensitive light transmittance and preparation method and application thereof
Technical Field
The invention relates to a high-molecular fluorescent material, in particular to a UV-cured fluorescent material with temperature-sensitive light transmittance and a preparation method and application thereof.
Background
The application range of the fluorescent material is wide, and the fluorescent material can be roughly divided into a fluorescent dye material, a fluorescent detection material, a fluorescent tracer material, a fluorescent development material, a fluorescent electronic device and the like [ Zhizhixi, Wang seal, Turkey, Yangmeng, Dinglian Zhan, SchoGo, the preparation of a waterborne polyurethane fluorescent material and the fluorescence property thereof, functional polymer science report, 2014, 27 (4): 426-431]. Compared with fluorescent micromolecules, the chromophore of the fluorescent macromolecule is combined in the macromolecule by a chemical bond and is not easy to fall off, the chromophore is uniformly distributed, the content is stable, the luminous performance and the photoconductive performance are good [ Zhou Di, Zhu Xiulin, Hulihua, Zangjun, Guanhai Yuan, the research progress of fluorescent macromolecule materials, chemical engineers, 2007, 39-4], the peculiar film forming property and the processing property of the macromolecule are achieved, the chromophore has unique photophysical and photochemical properties, and the chromophore is used as a novel functional material and widely applied to the aspects of photoconductive resin, fluorescent probe technology, fluorescent chemical sensors, nonlinear optical devices, agricultural production, scientific research and the like. [ Sunqi, Queenli, Liuyang, Chengxing, Wangpojun, Liuxuolong, Zhangbo, Zhenghui, Liulimna, preparation and performance of near-infrared polyvinyl alcohol fluorescent polymer material, application chemistry, 2018, 35 (1): 53-59; chenyun, shoya, van li juan, mechanism and method for regulating fluorescence color of conjugated polymer material, chemical progress, 2014, 26 (11): 1801-1810].
At present, the synthesis of fluorescent polymer materials is mainly realized through polymerization and copolymerization of fluorescent monomers and physical or chemical bonding of small molecular fluorescent substances and a polymer matrix, and fluorescent groups in the polymer are mostly rigid and planar structures containing aromatic rings or heterocyclic rings and conjugated double bonds. [ Zhou Di, Ju Xiu Lin, Hu Li Hua, Zai Jun you, guan Hai Yuan, fluorescent polymer materials progress, chemical Engineer, 2007, 39-41] in addition, rare earth elements due to excellent optical properties, the incorporation of rare earth elements into polymers can also make polymer materials have fluorescent properties [ Zhou Di, Ju Lin, Hu Li Hua, Zai Jun you, guan Hai Yuan, fluorescent polymer materials progress, chemical Engineer, 2007, 39-41], the fluorescent substances used are mainly rare earth ions and their complexes, organic small molecular substances, but their fluorescence emission wavelengths are all short, and the dissolution and recombination effects with polymer substrates are also poor, the recombination process is complicated, the types of the involved polymer substrates are also few, mainly poly (arylene ether nitrile), polymethyl methacrylate, acrylamides and the like. Therefore, the development of new fluorescent polymer materials with more varieties, especially near-infrared fluorescent polymer materials, has wider application prospect. [ Sunqi, Queenli, Liuyang, Chengxing, Wangpojun, Liuxuolong, Zhangbo, Zhenghui, Liulimna, preparation and performance of near-infrared polyvinyl alcohol fluorescent polymer material, application chemistry, 2018, 35 (1): 53-59; chenyun, Shaoya, Naringian and a mechanism and a method for regulating the fluorescence color of a conjugated polymer material, and chemical progress, 2014, 26 (11): 1801-1810 Sulqi takes PVA, a water-soluble near-infrared squaraine dye with excellent fluorescence characteristics and a novel water-soluble graphene with outstanding thermal stability and mechanical property as raw materials, and the composite is carried out through physical and chemical actions to design and synthesize the squaraine/polyvinyl alcohol binary and squaraine/graphene/polyvinyl alcohol ternary composite near-infrared fluorescent polymer material. [ Sunqi, Queenli, Liuyang, Chengxing, Wangpojun, Liuxuolong, Zhangbo, Zhenghui, Liulimna, preparation and performance of near-infrared polyvinyl alcohol fluorescent polymer material, application chemistry, 2018, 35 (1): 53-59]
The organic silicon polymer material has the advantages of good temperature resistance, weather resistance, good flexibility, easy processing and the like, so that fluorescent materials based on the organic silicon polymer also attract wide attention of people. The Chinese patent application 201910570244.6 discloses a coating with both noctilucent and fluorescent properties, which is obtained by mixing a carbon dot fluorescent material, an organic long afterglow luminescent material, an organic silicon modified polyurethane emulsion, a pigment, a filler and an auxiliary agent. Chinese patent ZL200910187422.3 discloses a light conversion flexible polymer material and application thereof, and specifically relates to an elastomer material obtained by mixing and heating and curing silicone rubber, a diluent, a fluorescent material (aluminate, silicate, silicon nitride and sulfur oxide fluorescent material), an auxiliary agent and the like. The Chinese patent ZL201210332383.3 discloses a fluorescent material, which is obtained by carrying out hydrosilylation reaction on an ordered mesoporous organic silicon material, a modified silicon nanocrystal and siloxane. The traditional organic silicon fluorescent elastomer is prepared by doping luminescent fluorescent materials such as carbon quantum dots, rare earth metal ions or organic dyes into the elastomer, but the doped fluorescent materials have certain toxicity, the color of the fluorescent materials is difficult to control, and the dispersion stability in the elastomer is poor, so that the application of the fluorescent materials in the field of biological medical treatment is limited. The Chinese patent application 201810434130.4 discloses a preparation method of an organic silicon fluorescent elastomer, which is to grind a fluorescent material obtained by reacting polysilsesquioxane with an organic conjugated fluorescent material, uniformly disperse the ground fluorescent material into the organic silicon elastomer, and then cure and mold the ground fluorescent material to obtain the organic silicon fluorescent elastomer. The method still has the problems of high cost of fluorescent materials, poor dispersibility in organic silicon polymers and the like.
Disclosure of Invention
In order to solve the defects of the fluorescent high polymer material, the application provides the fluorescent material with the UV-cured light transmittance and the temperature sensitivity, and the preparation method and the application thereof.
The invention is realized by the following technical scheme: the UV-cured fluorescent material with the temperature-sensitive light transmittance has the light transmittance of 4-78% at 5 ℃ and the fluorescence intensity of 3.3 multiplied by 10 at 317nm at 25 ℃ within the visible light range of 400-800nm 6 cps-8.0×10 6 cps, hardness of 4B-2B, and tensile strength of 0.5MPa-3.0 MPa.
The 317nm is a place where the highest peak value of fluorescence excited by ultraviolet light appears, and the pencil hardness of the fluorescent material is only 4B-2B, which indicates that the hardness of the material is lower.
The preparation method of the UV-cured fluorescent material with the temperature-sensitive light transmittance comprises the following steps:
(1) obtaining a fluorescent hyperbranched organic silicon polymer containing hydroxyl groups by reacting a compound with hydroxyl groups at two ends and alkoxy siloxane under the action of a catalyst;
the method comprises the following specific steps: reacting a compound with two ends being hydroxyl groups with alkoxy silane under the action of a catalyst at 90-180 ℃ for 2-12 h, and then evaporating unreacted raw materials under reduced pressure at 90-180 ℃/130mmHg to obtain a fluorescent hyperbranched organic silicon polymer containing hydroxyl groups;
the compound with two ends being hydroxyl is selected from one or more of dihydric alcohol, polyether glycol and polysiloxane with two ends being hydroxyl-terminated,
the alkoxy silane is selected from one or more of methyl trimethoxy silane, methyl triethoxy silane, vinyl trimethoxy silane, vinyl triethoxy silane, phenyl trimethoxy silane, phenyl triethoxy silane, gamma-aminopropyl trimethoxy silane, gamma-aminopropyl triethoxy silane, ethyl trimethoxy silane, ethyl triethoxy silane, mercaptopropyl trimethoxy silane and mercaptopropyl triethoxy silane, the molar ratio of the compound with hydroxyl at two ends to the alkoxy silane is 1.55-2.5: 1, and preferably, the molar ratio of the compound with hydroxyl at two ends to the alkoxy silane is 1.6: 1-2.0: 1.
Preferably, the dihydric alcohol is one or more selected from ethylene glycol, diethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, neopentyl glycol, triethylene glycol and tetraethylene glycol; more preferably, the dihydric alcohol is one or more selected from ethylene glycol, 1, 2-propylene glycol, 1, 4-butanediol and neopentyl glycol.
Preferably, the polyether glycol is selected from polytetramethylene ether glycol with the average molecular weight of 100-5000 or the structural formula of HO (C) 2 H 4 O) x (C 3 H 6 O) y OH, ethylene oxide and propylene oxide copolymer with hydroxyl groups at two ends, wherein x/(x + y) is more than or equal to 0 and less than or equal to 1.0, x is more than or equal to 10 and less than or equal to 80, and x is an integer; the polyether is prepared by taking ethylene oxide and propylene oxide as raw materials, and the polyether glycol is one of main raw materials for preparing polyurethane.
The catalyst is selected from one or a mixture of more of sulfuric acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid and acidic macroporous cation exchange resin, and the usage amount of the catalyst is 0-10 wt% of the total mass of the raw materials (the total mass of the compound with hydroxyl groups at two ends and the alkoxy siloxane) in the step (1). Preferably, the acidic catalyst is one or a mixture of more of trifluoromethanesulfonic acid, p-toluenesulfonic acid and acidic macroporous cation exchange resin, and the usage amount of the catalyst is 0-5 wt% of the total mass of the raw materials in the step (1).
(2) Polyether glycol or hydroxyl-terminated polysiloxane, diisocyanate and the fluorescent hyperbranched organic silicon polymer containing hydroxyl obtained in the step (1) react in a solvent under the catalysis of diisobutyl tin laurate to obtain isocyanate-terminated hyperbranched polyurethane, and then the isocyanate-terminated hyperbranched polyurethane reacts with hydroxyl acrylate to obtain a hyperbranched organic silicon modified polyurethane-acrylate fluorescent polymer;
the method comprises the following specific steps: reacting polyether glycol or hydroxyl terminated polysiloxane which is subjected to moisture removal at a reduced pressure of 100-130 ℃/130mmHg for 0.5-2 h, diisocyanate and the fluorescent hyperbranched organic silicon polymer containing hydroxyl obtained in the step (1) in a reaction solvent at a temperature of 30-90 ℃ for 1-8 h under the catalysis of diisobutyl tin laurate, then dropwise adding hydroxyl acrylate, reacting at a temperature of 30-90 ℃ for 0.5-12 h, and removing the solvent at a reduced pressure of 100-170 ℃/130mmHg until no fraction is produced in 5min to obtain the acrylate terminated hyperbranched organic silicon modified polyurethane-acrylate fluorescent polymer;
preferably, the polyether glycol is selected from polytetramethylene ether glycol with the average molecular weight of 100-5000 or the structural formula of HO (C) 2 H 4 O) x (C 3 H 6 O) y OH, ethylene oxide and propylene oxide copolymer with hydroxyl groups at two ends, wherein x/(x + y) is more than or equal to 0 and less than or equal to 1.0, x is more than or equal to 10 and less than or equal to 80, and x is an integer; the polyether is prepared by taking ethylene oxide and propylene oxide as raw materials, and the polyether glycol is one of main raw materials for preparing polyurethane.
Preferably, the hydroxyl-terminated polysiloxane is a polysiloxane terminated with two terminal hydroxyl groups and has the structural formula HO [ (CH) 3 ) 2 SiO] m [CH 3 C 6 H 5 SiO] n [CH 3 CH 2 CH 2 CF 3 SiO] P OH, wherein m, n and p are integers, and m is 8 to 100, n is 0 to 40,p is 0-18, n + p)/(m + n + p) is not less than 0 and not more than 0.9, p/(m + n + p) is not less than 0 and not more than 0.2. The addition of the hydroxyl-terminated polysiloxane enables the polyurethane chain segment to have an organic silicon component, and can improve the flexibility and the high and low temperature resistance.
The molar ratio of the polyether glycol or the hydroxyl-terminated polysiloxane to the diisocyanate is 1: 1.05-2.5, and the using amount of the fluorescent hyperbranched organic silicon polymer containing the hydroxyl is 0.5-15% of the total mass of the polyether glycol or the hydroxyl-terminated polysiloxane and the diisocyanate. Preferably, in the polyether glycol or hydroxyl-terminated polysiloxane, the diisocyanate and the fluorescent hyperbranched organic silicon polymer containing hydroxyl, the polyether glycol or hydroxyl-terminated polysiloxane and the diisocyanate are used according to the molar ratio of 1: 1.1-2.0, and the fluorescent hyperbranched organic silicon polymer containing hydroxyl is 1-10% of the total mass of the polyether glycol or hydroxyl-terminated polysiloxane and the diisocyanate.
The diisocyanate is selected from one or more of 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate isomer mixture (TDI), diphenylmethane diisocyanate (MDI), 1, 6-Hexamethylene Diisocyanate (HDI) and isophorone diisocyanate (IPDI).
Preferably, the reaction solvent is one or a mixture of several of toluene, tetrahydrofuran, acetone, dichloroethane and petroleum ether, and the use amount of the reaction solvent is 0.5 to 3 times of the mass of the raw materials (polyether glycol or hydroxyl-terminated polysiloxane, diisocyanate and the total mass of the fluorescent hyperbranched organosilicon polymer containing hydroxyl groups obtained in the step (1)) in the step (2); more preferably, the amount of the reaction solvent used is 1 to 2 times the mass of the reaction raw material in the step (2).
The using amount of the diisobutyl tin laurate is 0.01 to 1 percent of the mass of the raw materials (the total mass of the polyether glycol or the hydroxyl-terminated polysiloxane, the diisocyanate and the fluorescent hyperbranched organosilicon polymer containing the hydroxyl group obtained in the step (1)) in the step (2), and preferably, the using amount is 0.05 to 0.5 percent of the mass of the raw materials in the step (2). The diisobutyl tin laurate acts as a catalyst for catalyzing the reaction of the polyurethane group and the hydroxyl group.
The hydroxyl acrylic ester is selected from one or more of hydroxyethyl methacrylate, hydroxypropyl methacrylate, 4-hydroxyphenyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate and 4-hydroxybutyl acrylate. The amount of the hydroxy acrylate used is equal to the number of moles of isocyanate groups remaining in the polyurethane when the hydroxy acrylate is not added, in terms of the number of moles of hydroxy acrylate hydroxyl groups.
(3) And uniformly mixing the obtained acrylate-terminated hyperbranched organic silicon modified polyurethane-acrylate fluorescent polymer with a UV initiator in proportion, defoaming in vacuum for 10-30 min, and curing by UV for 10-180 s to obtain the fluorescent material with temperature-sensitive light transmittance.
The UV initiator is selected from benzoin, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, diphenylethanone, alpha-dimethoxy-alpha-phenylacetophenone, alpha-diethoxyacetophenone, alpha-hydroxyalkylphenone, alpha-aminoalkylphenone, aroylphosphine oxide, bis-benzoylphenylphosphine oxide, benzophenone, 2, 4-dihydroxybenzophenone, Michler's ketone; one or more of thiopropoxy thioxanthone and isopropyl thioxanthone, and the using amount of the thiopropoxy thioxanthone and the isopropyl thioxanthone is 1-12% of the mass of the hyperbranched organic silicon modified polyurethane-acrylate fluorescent polymer terminated by acrylate. Preferably, the UV initiator is one or more selected from benzoin, benzoin dimethyl ether, benzoin ethyl ether, diphenylethanone, alpha-dimethoxy-alpha-phenylacetophenone, alpha-diethoxyacetophenone, aroylphosphine oxide, bis-benzoylphenylphosphine oxide, benzophenone and 2, 4-dihydroxy benzophenone, and the using amount of the UV initiator is 3-9% of the mass of the acrylate-terminated hyperbranched organosilicon-modified polyurethane-acrylate fluorescent polymer.
Preferably, the UV light source is selected from one of 365nm, 405nm and 385nm, and the power of the UV lamp is 300-.
The method comprises the following steps of reacting a compound with two ends of hydroxyl with alkoxy siloxane to obtain a fluorescent hyperbranched organic silicon polymer containing the hydroxyl; the obtained organic silicon hyperbranched polymer has hydroxyl, double bond or nitrogen atom, and the organic silicon hyperbranched polymer has fluorescence due to the interaction of the hydroxyl, the double bond or the nitrogen atom.
Then polyether glycol or hydroxyl-terminated polysiloxane, diisocyanate and fluorescent hyperbranched organic silicon polymer containing hydroxyl are reacted to obtain isocyanate-terminated hyperbranched polyurethane, and then the isocyanate-terminated hyperbranched polyurethane is reacted with hydroxyl acrylate to obtain hyperbranched organic silicon modified polyurethane-acrylate fluorescent polymer; because the obtained organosilicon hyperbranched polymer has hydroxyl, the organosilicon hyperbranched polymer can participate in polycondensation to obtain polyurethane in the step, and finally obtain the acrylate-terminated polyurethane, so that the acrylate-terminated polyurethane product has fluorescence. The resultant acrylate-terminated polyurethane can be UV-cured under the initiation of a UV photoinitiator because the terminal is an acrylate.
And finally, carrying out UV curing on the obtained hyperbranched organic silicon modified polyurethane-acrylate and a UV initiator to obtain the high-molecular fluorescent material. The fluorescent material with the temperature-sensitive UV curing light transmittance can be applied to the fields of temperature-sensitive optical devices, anti-counterfeiting, fluorescent probes and fluorescent coatings because fluorescent materials such as luminescent carbon quantum dots, rare earth metal ions or organic dyes do not need to be doped, and the fluorescent material is non-toxic, does not have the problems that the color of the fluorescent material is difficult to regulate and control, and the dispersion stability in an elastomer is poor.
Compared with the prior art, the invention has the beneficial effects that:
(1) the preparation is simple and convenient, the raw materials are rich and cheap, and the industrialization is convenient;
(2) fluorescent materials such as luminescent carbon quantum dots, rare earth metal ions or organic dyes do not need to be doped, and the preparation method is nontoxic, and does not have the problems that the color of the fluorescent materials is difficult to control, the dispersion stability in the elastomer is poor and the like.
Drawings
FIG. 1 is a graph showing the change in light transmittance caused by the change in the amount of the product obtained in step (1) in example 1
FIG. 2 is a graph showing the change in fluorescence intensity according to the change in the amount of the product obtained in step (1) in example 1
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The starting materials used in the examples are either commercially available or prepared by conventional methods.
In an embodiment, the UV light source is selected from 365nm and the UV lamp power is 1000 w/h.
The analytical test methods of the examples are as follows:
nuclear magnetic resonance: deuterated chloroform (CDCl) 3 ) As solvent, hydrogen spectra were determined at room temperature using a Brucker Advance-400NMR Nuclear magnetic resonance apparatus (Brucker, Germany) ((R)) 1 H-NMR)。
Fourier infrared (FT-IR): the method comprises the steps of using a Nicolet700 type Fourier transform infrared spectrometer (provided with an ATR accessory) of Nicolet company in America, directly placing a sample in the ATR accessory of the infrared spectrometer during testing, and testing at 4000-700 cm -1 Fourier ir spectrum within the range.
And (3) testing light transmittance: an Evolution 300 type ultraviolet-visible spectrophotometer of the United states Thermo Fisher company tests the light transmittance of the polymer, the test wavelength range is 300-800 nm, and the sample thickness is 10 mm;
fluorescence spectrum test: the fluorescence spectrum at 300-500nm was measured using a Fluorolog-3 fluorometer (Horiba Jobin Yvon, USA).
Tensile strength test: the experimental equipment is a UH6503D microcomputer controlled electronic tension-compression cycle reciprocating testing machine produced by Yoghong measurement and control technology (Shanghai) Limited company, the stretching speed is 2mm/min, each film is measured for 5 times, and the average value is taken.
Pencil hardness: the measurement is carried out according to GB/T6739-2006 determination of paint film hardness by the pencil method for color paint and varnish.
Example 1
(1) Adding 54.8g of neopentyl glycol and 50.25g of vinyltrimethoxysilane into a clean 250mL three-neck flask, adding 1.05g of trifluoromethanesulfonic acid, heating to 120 ℃, reacting for 4 hours, removing low molecules for 2 hours at 120 ℃/130mmHg under reduced pressure, and then cooling to room temperature to obtain 72.46g of colorless transparent liquid, namely the fluorescent hyperbranched organosilicon polymer containing hydroxyl.
(2) 200g of polytetramethylene ether glycol with the average molecular weight of 2000 and 66.687g of IPDI (isophorone diisocyanate), which are dehydrated by 120 ℃/130mmHg under reduced pressure for 1h, 40g of the fluorescent hyperbranched organosilicon polymer containing hydroxyl obtained in the step (1), 306g of tetrahydrofuran are uniformly mixed, 0.181g of dibutyltin dilaurate is added, after the mixture reacts for 6h at the temperature of 40 ℃, 54.855g of hydroxypropyl methacrylate is added, the reaction continues for 8h at the temperature of 40 ℃, and the tetrahydrofuran is removed by 80 ℃/130mmHg under reduced pressure to obtain 361.542g of the acrylate-terminated hyperbranched organosilicon-modified polyurethane-acrylate fluorescent polymer.
(3) And (3) taking 20g of the acrylate-terminated hyperbranched organosilicon-modified polyurethane-acrylate fluorescent polymer obtained in the step (2), adding 1g of benzoin and 0.5g of benzoin dimethyl ether, uniformly mixing, defoaming in vacuum at 130mmHg/30 ℃ for 20min, and carrying out UV curing for 60s to obtain the hyperbranched organosilicon-modified polyurethane-acrylate fluorescent material, namely the UV-cured fluorescent material 1 with temperature-sensitive light transmittance.
Fluorescent material 1 with UV curing light transmittance and temperature sensitivity has the fluorescence intensity of 6.6 multiplied by 10 at 317nm 6 cps, pencil hardness 4B, light transmittance of 22.5% at 5 ℃ and 93.1% at 25 ℃.
Test example 1
The change in the amount of the product of step (1) in step (2) according to the preparation procedure of example 1 resulted in a change in the transmittance as shown in FIG. 1 and in the fluorescence intensity as shown in FIG. 2.
The preferable fluorescent hyperbranched organic silicon polymer containing hydroxyl is 1-10% of the total mass of polyether glycol or hydroxyl-terminated polysiloxane and diisocyanate, and the results of light transmittance at 5 ℃ and light transmittance at 25 ℃ show that the material is an opaque material at lower temperature, and when the temperature reaches 25 ℃, the material has higher light transmittance, which shows that the light transmittance of the obtained material changes along with the change of the temperature, and the material is a temperature-sensitive material. The fluorescence intensity is enhanced along with the increase of the using amount of the hyperbranched organosilicon modified polyurethane-acrylate fluorescent material.
Meanwhile, fluorescent materials such as luminescent carbon quantum dots, rare earth metal ions or organic dyes do not need to be doped, and the preparation method is non-toxic, does not have the problems that the color of the fluorescent materials is difficult to regulate and control, and the dispersion stability of the carbon quantum dots, the rare earth metal ions or the organic dyes in the elastomer is poor.
Example 2
(1) 39.190g of ethylene glycol and 74.919g of gamma-aminopropyltriethoxysilane are added into a clean 250mL three-neck flask, 11.41g of acidic cation exchange resin is added, the mixture is heated to 160 ℃ for reaction for 12 hours and then cooled to room temperature, low molecules are removed at 160 ℃/130mmHg for 2 hours under reduced pressure after the acidic cation exchange resin is removed by filtration, and then the temperature is cooled to room temperature, so that 67.022g of colorless transparent liquid, namely the fluorescent hyperbranched organosilicon polymer containing hydroxyl is obtained.
(2) 100g of HO (C) with an average molecular weight of 1000 and with water removed by 110 ℃/130mmHg under reduced pressure for 1.5h 2 H 4 O) 22 OH, 52.248g of TDI, 15.225g of fluorescent hyperbranched organic silicon polymer containing hydroxyl obtained in the step (1) and 502.4g of toluene are uniformly mixed, 1.011g of dibutyltin dilaurate is added, after reaction for 6 hours at 60 ℃, 34.767g of hydroxypropyl acrylate is added, reaction is continued for 4 hours at 60 ℃, and after toluene is removed at 100 ℃/130mmHg under reduced pressure, 202.24g of acrylate-terminated hyperbranched organic silicon modified polyurethane-acrylate fluorescent polymer is obtained.
(3) And (3) taking 20g of the acrylate-terminated hyperbranched organosilicon-modified polyurethane-acrylate fluorescent polymer obtained in the step (2), adding 1g of benzoin and 0.5g of benzoin dimethyl ether, uniformly mixing, defoaming in vacuum at 130mmHg/30 ℃ for 20min, and carrying out UV curing for 80s to obtain the hyperbranched organosilicon-modified polyurethane-acrylate fluorescent material, namely the UV-cured fluorescent material 2 with temperature-sensitive light transmittance.
Fluorescent material 2 with UV curing light transmittance and temperature sensitivity has the fluorescence intensity of 6.6 multiplied by 10 at 317nm 6 cps, pencil hardness 3B, 4.5% transmittance at 5 ℃ and 94.2% transmittance at 25 ℃.
Example 3
(1) 142.63g of diethylene glycol and 67.22g of phenyltrimethoxysilane are added into a clean 250mL three-neck flask, the mixture is heated to 100 ℃ and reacts for 12 hours, low molecules are removed for 4 hours under the reduced pressure of 100 ℃/130mmHg, and then the temperature is reduced to room temperature, so that 177.26g of colorless transparent liquid, namely the fluorescent hyperbranched organosilicon polymer containing hydroxyl is obtained.
(2) 120g of a copolymer HO (C) of ethylene oxide and propylene oxide with two hydroxyl groups at the two ends and an average molecular weight of 1200, which is dehydrated for 2 hours under the reduced pressure of 100 ℃/130mmHg 2 H 4 O) 20 (C 3 H 6 O) 5 OH and 50.052g MDI, and 1.70g of the hydroxyl group-containing fluorescent SuperSpeed in step (1)After the branched organic silicon polymer and 85.9g of petroleum ether are uniformly mixed, 0.017g of dibutyltin dilaurate is added, after the reaction is carried out at 80 ℃ for 3h, 59.487g of 4-hydroxyphenyl methacrylate is added, the reaction is continued at 80 ℃ for 4h, and after the petroleum ether is removed at the reduced pressure of 120 ℃/130mmHg, 290.726g of hyperbranched organic silicon modified polyurethane-acrylate fluorescent polymer with end capped acrylate is obtained.
(3) And (3) taking 20g of the acrylate-terminated hyperbranched organosilicon-modified polyurethane-acrylate fluorescent polymer obtained in the step (2), adding 0.5g of alpha-aminoalkylbenzophenone and 0.5g of aroylphosphine oxide, uniformly mixing, defoaming in vacuum at 130mmHg/30 ℃ for 20min, and carrying out UV curing for 120s to obtain the hyperbranched organosilicon-modified polyurethane-acrylate fluorescent material, namely the UV-cured fluorescent material 3 with temperature-sensitive light transmittance.
Fluorescent material 3 with UV curing light transmittance and temperature sensitivity has the fluorescent intensity of 7.27 multiplied by 10 at 317nm 6 cps, pencil hardness 3B, transmittance 57.5% at 5 ℃ and transmittance 92.8% at 25 ℃.
Example 4
(1) 91.635g of triethylene glycol, 50.251g of vinyltrimethoxysilane and 1.5g of p-toluenesulfonic acid are added into a clean 250mL three-neck flask, the mixture is heated to 100 ℃ to react for 12 hours, low molecules are removed for 4 hours under the reduced pressure of 130 ℃/130mmHg, and then the temperature is reduced to room temperature to obtain 177.26g of colorless transparent liquid, namely the fluorescent hyperbranched organosilicon polymer containing hydroxyl.
(2) 350g of ethylene oxide polymer HO (C) with hydroxyl groups at two ends and average molecular weight of 3500, which is decompressed at 130 ℃/130mmHg to remove water for 0.5h 2 H 4 O) 80 And (2) uniformly mixing OH, 33.639g HDI and 19.182g of the hydroxyl-containing fluorescent hyperbranched organosilicon polymer obtained in the step (1) and 403g of acetone, adding 1.611g of dibutyltin dilaurate, reacting at 30 ℃ for 8h, adding 19.079g of hydroxyethyl acrylate, continuing to react at 30 ℃ for 6h, and removing the acetone at 90 ℃/130mmHg under reduced pressure to obtain 421.9g of acrylate-terminated hyperbranched organosilicon-modified polyurethane-acrylate fluorescent polymer.
(3) And (3) taking 20g of the acrylate-terminated hyperbranched organosilicon-modified polyurethane-acrylate fluorescent polymer obtained in the step (2), adding 0.5g of 2, 4-dihydroxy benzophenone and 0.5g of Michler's ketone, uniformly mixing, defoaming in vacuum at 130mmHg/30 ℃ for 20min, and carrying out UV curing for 180s to obtain the hyperbranched organosilicon-modified polyurethane-acrylate fluorescent material, namely the UV-cured fluorescent material 4 with temperature-sensitive light transmittance.
Fluorescent material 4 with UV curing light transmittance and temperature sensitivity has the fluorescence intensity of 6.2 multiplied by 10 at 317nm 6 cps, pencil hardness 4B, light transmittance of 17.1% at 5 ℃ and 94.8% at 25 ℃.
Example 5
(1) 105.348g of tetraethylene glycol, 46.206g of methyltrimethoxysilane and 0.2g of concentrated sulfuric acid are added into a clean 250mL three-neck flask, heated to 180 ℃, reacted for 6h, the low molecules are removed for 6h under reduced pressure of 180 ℃/130mmHg, and then the temperature is reduced to room temperature, thus obtaining 118.969g of colorless transparent liquid, namely the fluorescent hyperbranched organosilicon polymer containing hydroxyl.
(2) Firstly, 50g of HO [ (CH) with hydroxyl groups at two ends and average molecular weight of 500 is removed by reducing the pressure for 2 hours at 120 ℃/130mmHg 3 ) 2 SiO] 6 And (2) uniformly mixing OH, 33.639g HDI, 6.691g of the hydroxyl-containing fluorescent hyperbranched organosilicon polymer obtained in the step (1) and 271g of acetone, adding 0.0181g of dibutyltin dilaurate, reacting at 40 ℃ for 8h, adding 25.532g of hydroxypropyl acrylate, continuing to react at 60 ℃ for 4h, and removing the acetone at 90 ℃/130mmHg under reduced pressure to obtain 115.862g of acrylate-terminated hyperbranched organosilicon-modified polyurethane-acrylate fluorescent polymer.
(3) And (3) taking 20g of the acrylate-terminated hyperbranched organosilicon-modified polyurethane-acrylate fluorescent polymer obtained in the step (2), adding 0.5g of alpha-aminoalkylbenzophenone and 0.5g of aroylphosphine oxide, uniformly mixing, defoaming in vacuum at 130mmHg/30 ℃ for 20min, and carrying out UV curing for 40s to obtain the hyperbranched organosilicon-modified polyurethane-acrylate fluorescent material, namely the UV-cured fluorescent material 5 with temperature-sensitive light transmittance.
Fluorescent material 5 with UV curing light transmittance and temperature sensitivity has the fluorescence intensity of 7.5 multiplied by 10 at 317nm 6 cps, pencil hardness 3B, transmittance of 78.2% at 5 ℃ and 85.0% at 25 ℃.
Example 6
(1) 105.348g of tetraethylene glycol, 46.206g of methyltrimethoxysilane and 0.2g of concentrated sulfuric acid are added into a clean 250mL three-neck flask, heated to 180 ℃, reacted for 6h, the low molecules are removed for 6h under reduced pressure of 180 ℃/130mmHg, and then the temperature is reduced to room temperature, thus obtaining 118.969g of colorless transparent liquid, namely the fluorescent hyperbranched organosilicon polymer containing hydroxyl.
(2) Firstly, reducing the pressure to 110 ℃/130mmHg to remove water for 1h, and then obtaining the HO [ (CH) with 640g of hydroxyl groups at two ends and average molecular weight of 6400 3 ) 2 SiO] 32 [CH 3 C 6 H 5 SiO] 16 [CH 3 CH 2 CH 2 CF 3 SiO] 12 And (2) uniformly mixing OH, 33.639g HDI, 6.691g of the hydroxyl-containing fluorescent hyperbranched organosilicon polymer obtained in the step (1) and 271g of acetone, adding 0.0181g of dibutyltin dilaurate, reacting at 40 ℃ for 8h, adding 25.532g of hydroxypropyl acrylate, continuing to react at 60 ℃ for 4h, and removing the acetone at 90 ℃/130mmHg under reduced pressure to obtain 115.862g of acrylate-terminated hyperbranched organosilicon-modified polyurethane-acrylate fluorescent polymer.
(3) And (3) taking 20g of the acrylate-terminated hyperbranched organosilicon-modified polyurethane-acrylate fluorescent polymer obtained in the step (2), adding 0.5g of bis-benzoyl phenyl phosphine oxide and 0.5g of thiopropoxy thioxanthone, uniformly mixing, defoaming in vacuum at 130mmHg/30 ℃ for 20min, and carrying out UV curing for 40s to obtain the hyperbranched organosilicon-modified polyurethane-acrylate fluorescent material, namely the UV-cured fluorescent material 6 with temperature-sensitive light transmittance.
Fluorescent material 6 with UV curing light transmittance and temperature sensitivity has the fluorescent intensity of 3.3 multiplied by 10 at 317nm 6 cps, pencil hardness 4B, light transmittance 48.2% at 5 ℃ and 74.5% at 25 ℃.

Claims (10)

1. The preparation method of the UV-cured fluorescent material with the temperature-sensitive light transmittance is characterized in that the fluorescent material with the temperature-sensitive light transmittance has the light transmittance of 4-78% at 5 ℃, the light transmittance of 75.0-98% at 25 ℃ and the fluorescence intensity of 3.3 multiplied by 10 at 317nm in the visible light range of 400-800nm 6 cps-8.0×10 6 cps and 4B-2B hardness;
the preparation method comprises the following steps:
(1) obtaining a fluorescent hyperbranched organic silicon polymer containing hydroxyl groups by reacting a compound with hydroxyl groups at two ends and alkoxy siloxane under the action of a catalyst;
(2) polyether glycol or hydroxyl-terminated polysiloxane, diisocyanate and the fluorescent hyperbranched organic silicon polymer containing hydroxyl obtained in the step (1) react in a solvent under the action of dibutyltin dilaurate to obtain isocyanate-terminated hyperbranched polyurethane, and then react with hydroxyl acrylate to obtain hyperbranched organic silicon modified polyurethane-acrylate fluorescent polymer;
(3) uniformly mixing the obtained hyperbranched organic silicon modified polyurethane-acrylate with a UV initiator in proportion, defoaming for 10-30 min in vacuum, and curing for 10-180 s by UV to obtain a fluorescent material with temperature-sensitive light transmittance;
in the step (1), the compound with two hydroxyl ends is selected from one or more of dihydric alcohol and polysiloxane with two hydroxyl end caps.
2. The method for preparing a fluorescent material with UV curing light transmittance and temperature sensitivity according to claim 1, wherein the diol is polyether diol.
3. The method for preparing a fluorescent material with UV curing transmittance temperature sensitivity according to claim 1 or 2, wherein the alkoxysilane in the step (1) is one or more selected from methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane, and the molar ratio of the compound with hydroxyl groups at both ends to the alkoxysilane is 1.55-2.5: 1.
4. the preparation method of the UV-cured fluorescent material with the light transmittance and the temperature sensitivity according to claim 1, wherein the catalyst in the step (1) is one or a mixture of sulfuric acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid and acidic macroporous cation exchange resin, and the usage amount of the catalyst is 0-10 wt% of the total mass of the raw materials.
5. The method for preparing a fluorescent material with UV curing light transmittance and temperature sensitivity according to claim 1, wherein in the step (2), the polyether glycol or the hydroxyl terminated polysiloxane and the diisocyanate are used according to a molar ratio of 1:1.05-1:2.5, and the fluorescent hyperbranched organic silicon polymer containing hydroxyl is used in an amount of 0.5-15% of the total mass of the polyether glycol or the hydroxyl terminated polysiloxane and the diisocyanate.
6. The method for preparing a UV-curable fluorescent material with temperature-sensitive transmittance according to claim 1, wherein the hydroxy acrylate in step (2) is one or more selected from hydroxyethyl methacrylate, hydroxypropyl methacrylate, 4-hydroxyphenyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate and 4-hydroxybutyl acrylate.
7. The method for preparing a fluorescent material with UV curing light transmittance and temperature sensitivity according to claim 1, wherein the amount of dibutyltin dilaurate in the step (2) is 0.01-1% of the mass of the reaction raw materials in the step (2).
8. The method for preparing a UV-curable fluorescent material with temperature-sensitive light transmittance according to claim 1, wherein in the step (3), the UV initiator is selected from one or more of benzoin, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, diphenylethanone, alpha-dimethoxy-alpha-phenylacetophenone, alpha-diethoxyacetophenone, alpha-hydroxyalkylphenone, alpha-aminoalkylbenzophenone, aroylphosphine oxide, bis-benzoylphenylphosphine oxide, benzophenone, 2, 4-dihydroxybenzophenone, Michler's ketone, thiopropoxy thioxanthone and isopropyl thioxanthone, and is used in an amount of 1-12% of the mass of the hyperbranched organosilicon-modified polyurethane-acrylate fluorescent polymer.
9. The method as claimed in claim 1, wherein the UV light source in step (3) is one of 365nm, 405nm and 385nm, and the power of the UV lamp is 300-.
10. An application of the UV-cured fluorescent material with the temperature-sensitive light transmittance obtained by the preparation method of any one of claims 1 to 9 in the fields of temperature-sensitive optical devices, anti-counterfeiting, fluorescent probes and fluorescent coatings.
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