CN111875760A - A kind of UV curing light transmittance temperature sensitive fluorescent material and preparation method and application thereof - Google Patents

Abstract

The invention relates to a polymer fluorescent material. In order to solve the shortcomings of the fluorescent polymer material, the present application proposes a UV-curable light transmittance temperature-sensitive fluorescent material and a preparation method and application thereof. The light transmittance temperature-sensitive fluorescent material In the visible light range of 400‑800nm, the transmittance is 4%‑78% at 5℃, 75.0%‑98% at 25℃, and the fluorescence intensity at 317nm is 3.3×10 ⁶ cps‑8.0×10 ⁶ cps, Fluorescent material with hardness of 4B~2B and tensile strength of 0.5MPa‑3.0MPa. The fluorescent material is easy to prepare, has abundant raw materials and is cheap, is convenient for industrialization, and does not need to incorporate fluorescent materials such as luminescent carbon quantum dots, rare earth metal ions or organic dyes, is non-toxic, has no fluorescent material and is difficult to control in color, and can be used in elastomers. It is widely used in temperature-sensitive optical devices, anti-counterfeiting, fluorescent probes, fluorescent coatings and other fields.

Description

A kind of UV curing light transmittance temperature sensitive fluorescent material and preparation method and application thereof

technical field

The invention relates to a polymer fluorescent material, and specifically designs a UV-curable light transmittance temperature-sensitive fluorescent material and a preparation method and application thereof.

Background technique

The application range of fluorescent materials is relatively wide, which can be roughly divided into fluorescent dye materials, fluorescent detection materials, fluorescent tracer materials, fluorescent developing materials, fluorescent electronic devices, etc. [Xie Zhiqian, Wang Jiyin, Tao Can, Yang Mingdi, Huang Yiping, Xu Gewen , Preparation and Fluorescence Properties of Waterborne Polyurethane Fluorescent Materials, Journal of Functional Polymers, 2014, 27(4): 426-431]. Compared with small fluorescent molecules, the chromophore of fluorescent polymer is not easy to fall off in the polymer by chemical bond, the chromophore distribution is uniform, the content is stable, and the luminescence performance and photoconductive performance are good [Zhou Di, Zhu Xiulin, Hu Lihua, Zeng Xiaojun. , Guan Haiyuan, Research Progress of Fluorescent Polymer Materials, Chemical Engineer, 2007, 39-4], as well as the unique film-forming properties and easy processing of polymers, with unique photophysical and photochemical properties, as a new functional material, It has been widely used in photoconductive resin, fluorescent probe technology, fluorescent chemical sensor, nonlinear optical device, agricultural production and scientific research. [Sun Qi, Wang Liqiu, Liu Yang, Guo Chenxiao, Wang Pengjun, Liu Xuelong, Zhang Xiaobo, Zheng Lihui, Liu Liping, Preparation and Properties of Near-Infrared Polyvinyl Alcohol Fluorescent Polymer Materials, Applied Chemistry, 2018, 35(1): 53-59; Chen Yun, Shao Ya, Fan Lijuan, Regulation mechanism and method of fluorescent color of conjugated polymer materials, Progress in Chemistry, 2014, 26(11): 1801-1810].

At present, the synthesis of fluorescent polymer materials is mainly realized by the polymerization and copolymerization of fluorescent monomers, and the physical or chemical bonding of small molecular fluorescent substances to the polymer matrix. Rigid and planar structure with conjugated double bonds. [Di Zhou, Zhu Xiulin, Hu Lihua, Zeng Xiaojun, Guan Haiyuan, Research Progress of Fluorescent Polymer Materials, Chemical Engineer, 2007, 39-41] In addition, due to the excellent optical properties of rare earth elements, the incorporation of rare earth elements into polymers can also make high Molecular materials have fluorescent properties [Zhou Di, Zhu Xiulin, Hu Lihua, Zeng Xiaojun, Guan Haiyuan, Research Progress in Fluorescent Polymer Materials, Chemical Engineer, 2007, 39-41], the fluorescent substances used are mainly rare earth ions and their complexes, organic small Molecular substances, but most of their fluorescence emission wavelengths are short, and the dissolution and recombination effects with the polymer matrix are also poor, the composite process is complicated, and the types of polymer matrices involved are also less, mainly polyarylether nitrile, Polymethyl methacrylate and acrylamide, etc. Therefore, the development of new types of fluorescent polymer materials, especially near-infrared fluorescent polymer materials, will have wider application prospects. [Sun Qi, Wang Liqiu, Liu Yang, Guo Chenxiao, Wang Pengjun, Liu Xuelong, Zhang Xiaobo, Zheng Lihui, Liu Liping, Preparation and Properties of Near-Infrared Polyvinyl Alcohol Fluorescent Polymer Materials, Applied Chemistry, 2018, 35(1): 53-59; Chen Yun, Shao Ya, Fan Lijuan, Regulation mechanism and method of fluorescent color of conjugated polymer materials, Advances in Chemistry, 2014, 26(11): 1801-1810] Sun Qi et al. Acid cyanine dyes and a new type of water-soluble graphene with outstanding thermal stability and mechanical properties were used as raw materials. Through physical and chemical compounding, the design and synthesis of squaraine/polyvinyl alcohol dibasic and squaraine/polyvinyl alcohol were synthesized. Graphene/polyvinyl alcohol ternary composite near-infrared fluorescent polymer material. [Sun Qi, Wang Liqiu, Liu Yang, Guo Chenxiao, Wang Pengjun, Liu Xuelong, Zhang Xiaobo, Zheng Lihui, Liu Liping, Preparation and Properties of Near Infrared Polyvinyl Alcohol Fluorescent Polymer Materials, Applied Chemistry, 2018, 35(1): 53-59]

Silicone polymer materials have the advantages of good temperature and weather resistance, good flexibility, and easy processing. Therefore, fluorescent materials based on silicone polymers have also attracted widespread attention. Chinese invention application 201910570244.6 is mixed with carbon dot fluorescent material, organic long afterglow luminescent material, silicone modified polyurethane emulsion, pigments and fillers and additives, and discloses a coating with both luminous and fluorescent properties. Chinese invention patent ZL200910187422.3 discloses a light-converting flexible polymer material and its use, specifically combining silicone rubber, diluent and fluorescent material (aluminate, silicate, silicon nitride and sulfur oxide fluorescent material) , additives, etc. are mixed and then heated and cured to obtain an elastomer material. Chinese invention patent ZL201210332383.3 discloses a fluorescent material, which is obtained by hydrosilylation of ordered mesoporous organosilicon material and modified silicon nanocrystals with siloxane. Traditional silicone fluorescent elastomers are doped with fluorescent materials such as carbon quantum dots, rare earth metal ions or organic dyes. However, many of the doped fluorescent materials have certain toxicity, and the color of fluorescent materials is difficult to control. The poor dispersion stability in elastomers limits its application in the biomedical field. Chinese Invention Application 201810434130.4 discloses a method for preparing a type of silicone fluorescent elastomer, that is, the fluorescent material obtained by reacting polysilsesquioxane and organic conjugated fluorescent material is ground and uniformly dispersed in the silicone elastomer, and then cured. The silicone fluorescent elastomer is obtained by molding. This method still has problems such as expensive fluorescent material and poor dispersibility in silicone polymers.

SUMMARY OF THE INVENTION

In order to solve the above-mentioned shortcomings of fluorescent polymer materials, the present application proposes a UV-curable light transmittance temperature-sensitive fluorescent material and its preparation method and application. Incorporating luminescent carbon quantum dots, rare earth metal ions or organic dyes and other fluorescent materials, non-toxic, there is no problem of difficult to control the color of fluorescent materials, and poor dispersion stability in elastomers, used in temperature-sensitive optical devices, anti-counterfeiting, fluorescence Probes, fluorescent coatings, etc.

The invention is realized by the following technical solutions: a UV-curable light transmittance temperature-sensitive fluorescent material, the light transmittance temperature-sensitive fluorescent material is in the visible light range of 400-800 nm, and the light transmittance is 4% at 5°C -78%, the transmittance at 25°C is 75.0%-98%, the fluorescence intensity at 317nm is 3.3×10 ⁶ cps-8.0×10 ⁶ cps, the hardness is 4B～2B, and the tensile strength is 0.5MPa-3.0MPa.

The 317 nm is where the highest peak of ultraviolet-excited fluorescence appears, and the pencil hardness of the fluorescent material is only 4B-2B, indicating that this material has a low hardness.

A preparation method of a UV-curable light transmittance temperature-sensitive fluorescent material comprises the following steps:

(1) Under the action of a catalyst, a compound having hydroxyl groups at both ends and an alkoxysiloxane are used to obtain a fluorescent hyperbranched organosilicon polymer containing hydroxyl groups;

The specific steps are as follows: react the compound with hydroxyl groups at both ends and alkoxysilane under the action of a catalyst at 90-180 °C for 2-12 h, and then steam the unreacted raw materials under reduced pressure at 90-180 °C/130 mmHg to obtain Fluorescent hyperbranched silicone polymers containing hydroxyl groups;

The compound having hydroxyl groups at both ends is selected from one or more of diols, polyether diols, and polysiloxanes terminated by hydroxyl groups at both ends,

The alkoxysilane is selected from methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane Silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, mercaptopropyltrimethoxysilane, mercaptopropyl One or more of the triethoxysilanes, the molar ratio of the compound with hydroxyl groups at both ends and the alkoxysilane is 1.55-2.5:1, preferably, the dosage of the compound with hydroxyl groups at both ends and the alkoxysilane According to the molar ratio of 1.6:1-2.0:1.

Preferably, the dihydric alcohol is selected from ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, triethylene glycol, tetrakis One or more of ethylene glycol; more preferably, the glycol is selected from one or more of ethylene glycol, 1,2-propanediol, 1,4-butanediol, and neopentyl glycol.

Preferably, the polyether glycol is selected from polytetramethylene ether glycol with an average molecular weight of 100-5000 or a ring with a structural formula of HO(C ₂ H ₄ O) _x (C ₃ H ₆ O) _y OH and hydroxyl groups at both ends. Copolymer of ethylene oxide and propylene oxide, wherein 0≤x/(x+y)≤1.0, 10≤x≤80 and x is an integer; this is prepared from ethylene oxide and propylene oxide as raw materials Polyether and polyether glycol are one of the main raw materials for the preparation of polyurethane.

Described catalyst is selected from the mixture of one or more in sulfuric acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, acidic macroporous cation exchange resin, and the catalyst usage amount is step (1) raw material gross mass (both ends are 0-10 wt % of the total mass of the hydroxyl compound and the alkoxysiloxane). Preferably, the acidic catalyst is selected from one or more mixtures of trifluoromethanesulfonic acid, p-toluenesulfonic acid, and acidic macroporous cation exchange resin, and the catalyst usage amount is 0 to 5wt% of the total mass of the raw materials in step (1). .

(2) Polyether diol or hydroxyl terminated polysiloxane, diisocyanate and the fluorescent hyperbranched organosilicon polymer containing hydroxyl obtained in step (1) are in a solvent, and catalyzed by diisobutyl tin laurate The following reaction is performed to obtain an isocyanate-terminated hyperbranched polyurethane, which is then reacted with hydroxy acrylate to obtain a hyperbranched organosilicon modified polyurethane-acrylate fluorescent polymer;

The specific steps are: depressurizing 100～130℃/130mmHg and removing water for 0.5～2h, polyetherdiol or hydroxyl terminated polysiloxane, diisocyanate and the fluorescent hyperbranched organosilicon containing hydroxyl obtained in step (1) The polymer is in the reaction solvent, under the catalysis of diisobutyltin laurate, after reacting at 30℃～90℃ for 1～8h, then adding hydroxyacrylate dropwise, reacting at 30℃～90℃ for 0.5～12h, 100～ The solvent was removed under reduced pressure at 170°C/130mmHg until there was no distillate for 5 minutes to obtain an acrylate-terminated hyperbranched organosilicon-modified polyurethane-acrylate fluorescent polymer;

Preferably, the polyether glycol is selected from polytetramethylene ether glycol with an average molecular weight of 100-5000 or a ring with a structural formula of HO(C ₂ H ₄ O) _x (C ₃ H ₆ O) _y OH and hydroxyl groups at both ends. Copolymer of ethylene oxide and propylene oxide, wherein 0≤x/(x+y)≤1.0, 10≤x≤80 and x is an integer; this is prepared from ethylene oxide and propylene oxide as raw materials Polyether and polyether glycol are one of the main raw materials for the preparation of polyurethane.

Preferably, the hydroxyl-terminated polysiloxane is a polysiloxane terminated by hydroxyl groups at both ends, and the structural formula is 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 all integers, and m=8-100, n=0-40, p=0-18, 0≤(n+p)/(m+n+ p)≤0.9, 0≤p/(m+n+p)≤0.2. The addition of hydroxyl-terminated polysiloxane enables silicone components in the polyurethane segment to improve flexibility and high and low temperature resistance.

The molar ratio of the polyether glycol or hydroxyl-terminated polysiloxane to diisocyanate is 1:1.05-2.5, and the amount of the fluorescent hyperbranched organosilicon polymer containing hydroxyl groups is polyether glycol or hydroxyl-terminated polysiloxane. 0.5%-15% of the total mass of oxane and diisocyanate. Preferably, in polyether diol or hydroxyl terminated polysiloxane, diisocyanate and fluorescent hyperbranched organosilicon polymer containing hydroxyl groups, the amount of polyether diol or hydroxyl terminated polysiloxane and diisocyanate used is based on moles In a ratio of 1:1.1-2.0, the amount of the fluorescent hyperbranched organosilicon polymer containing hydroxyl groups is 1%-10% of the total mass of polyether diol or hydroxyl-terminated polysiloxane and diisocyanate.

The diisocyanate is selected from the group consisting of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate isomer mixture (TDI), diphenylmethane diisocyanate (MDI), 1,6-hexamethylene diisocyanate (HDI), One or more of isophorone diisocyanate (IPDI).

Preferably, the reaction solvent is selected from one or more mixtures of toluene, tetrahydrofuran, acetone, ethylene dichloride, and petroleum ether, and the usage amount is the quality of the reaction raw materials (polyether glycol or hydroxyl-terminated polysilicon) in step (2). Oxane, diisocyanate and the total mass of the fluorescent hyperbranched organosilicon polymer containing hydroxyl obtained in step (1)) 0.5-3 times; more preferably, the amount of reaction solvent used is 1-2 times the mass of the reaction raw materials in step (2). times.

The amount of diisobutyltin laurate used is the quality of the reaction raw materials in step (2) (polyether glycol or hydroxyl terminated polysiloxane, diisocyanate and the fluorescent hyperbranched organosilicon polymer containing hydroxyl groups obtained in step (1). 0.01%-1% of the total mass), preferably, the usage amount is 0.05-0.5% of the mass of the reaction raw materials in step (2). Tin diisobutyl laurate acts as a catalyst to catalyze the reaction between polyurethane groups and hydroxyl groups.

The hydroxy acrylate is selected from hydroxyethyl methacrylate, hydroxypropyl methacrylate, 4-hydroxyphenyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, and 4-hydroxybutyl acrylate. one or more. The amount of hydroxy acrylate used is equal to the number of moles of isocyanate groups remaining in the polyurethane when no hydroxy acrylate is added.

(3) The obtained acrylate-terminated hyperbranched organosilicon-modified polyurethane-acrylate fluorescent polymer and UV initiator are mixed uniformly in proportion, and after vacuum defoaming for 10 to 30 minutes, UV curing is performed for 10 to 180 s to obtain transparent Light-rate temperature-sensitive fluorescent material.

The UV initiator is selected from benzoin, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, diphenylethanone, α,α-dimethoxy-α-phenylacetophenone, α,α -diethoxyacetophenone, α-hydroxyalkylphenone, α-aminoalkylphenone, aroylphosphine oxide, bisbenzoylphenylphosphine oxide, benzophenone, 2,4-diphenone Hydroxybenzophenone, Michler's ketone; one or more of thiopropoxythioxanthone, isopropylthioxanthone, the usage amount is acrylate-terminated hyperbranched organosilicon modified polyurethane- 1-12% by mass of acrylic fluorescent polymer. Preferably, the UV initiator is selected from benzoin, benzoin dimethyl ether, benzoin ether, diphenyl ethyl ketone, α,α-dimethoxy-α-phenylacetophenone, α,α-diethoxybenzene One or more of ethyl ketone, aroyl phosphine oxide, bisbenzoyl phenyl phosphine oxide, benzophenone, 2,4-dihydroxybenzophenone, the usage amount is acrylate-terminated hyperbranched 3-9% by mass of silicone-modified polyurethane-acrylate fluorescent polymer.

Preferably, the UV light source is selected from one of 365nm, 405nm and 385nm, and the UV lamp power is 300-2000w/h.

In the present application, a compound having hydroxyl groups at both ends is reacted with an alkoxysiloxane to obtain a fluorescent hyperbranched organosilicon polymer containing hydroxyl groups; the obtained organosilicon hyperbranched polymer has hydroxyl groups, double bonds or nitrogen atoms, and they are The interaction makes the organosilicon hyperbranched polymer have fluorescence.

Then polyether diol or hydroxyl terminated polysiloxane, diisocyanate and fluorescent hyperbranched silicone polymer containing hydroxyl groups are reacted to obtain isocyanate terminated hyperbranched polyurethane, which is then reacted with hydroxy acrylate to obtain hyperbranched organic Silicon-modified polyurethane-acrylate fluorescent polymer; because the obtained organosilicon hyperbranched polymer has hydroxyl groups, it can participate in polycondensation to obtain polyurethane in this step, and finally obtain acrylate-terminated polyurethane, so that acrylate-terminated polyurethane can be obtained. Polyurethane products are fluorescent. The resulting acrylate-terminated polyurethane, because the termini is acrylate, can be UV-cured under the initiation of a UV photoinitiator.

Finally, the obtained hyperbranched organosilicon modified polyurethane-acrylate and UV initiator are UV-cured to obtain a polymer fluorescent material. Since there is no need to incorporate fluorescent materials such as luminescent carbon quantum dots, rare earth metal ions or organic dyes, it is non-toxic, and there are no problems such as difficult to control the color of fluorescent materials, and poor dispersion stability in elastomers. The rate-sensitive fluorescent material can be used in the fields of temperature-sensitive optical devices, anti-counterfeiting, fluorescent probes, and fluorescent coatings.

Compared with the prior art, the beneficial effects of the present invention are:

(1) The preparation is simple, the raw materials are abundant and cheap, and it is convenient for industrialization;

(2) There is no need to incorporate fluorescent materials such as luminescent carbon quantum dots, rare earth metal ions or organic dyes, non-toxic, and there are no problems such as difficult to control the color of fluorescent materials, and poor dispersion stability in elastomers.

Description of drawings

Fig. 1 is the change curve of light transmittance caused by the change in the amount of the product obtained in step (1) in Example 1

Fig. 2 is the change curve of the fluorescence intensity caused by the change in the amount of the product obtained in step (1) in Example 1

Detailed ways

The present invention will be described in further detail below through the examples, but the examples are not intended to limit the protection scope of the present invention. The raw materials used in the examples are all commercially available or prepared by conventional methods.

In the embodiment, the UV light source is selected from 365nm, and the UV lamp power is 1000w/h.

The analytical test method of the embodiment is as follows:

Nuclear Magnetic Resonance: Using deuterated chloroform (CDCl ₃ ) as a solvent, the hydrogen spectrum ( ¹ H-NMR) was measured at room temperature with a Brucker Advance-400 NMR nuclear magnetic resonance apparatus from Brucker, Germany.

Fourier Transform Infrared (FT-IR): Use the Nicolet 700 Fourier Transform Infrared Spectrometer (equipped with ATR accessory) from Nicolet Company, USA. When testing, place the sample directly in the ATR accessory of the infrared spectrometer, and test in the range of 4000～700cm ^-1 . Fourier transform infrared spectrum.

Light transmittance test: The Evolution 300 UV-Vis spectrophotometer of Thermo Fisher Company in the United States tests the light transmittance of the polymer, the test wavelength range is 300-800nm, and the sample thickness is 10mm;

Fluorescence Spectrum Test: Fluorolog-3 Fluorometer (Horiba Jobin Yvon Company, USA) was used to test the fluorescence spectrum at 300-500nm.

Tensile strength test: The experimental equipment is UH6503D microcomputer-controlled electronic tension-compression cyclic reciprocating testing machine produced by Youhong Measurement and Control Technology (Shanghai) Co., Ltd., the tensile speed is 2mm/min, and each film is measured 5 times, and the average value is taken.

Pencil hardness: measured according to GB/T 6739-2006 "Paint and Varnish Pencil Method Determination of Paint Film Hardness".

Example 1

(1) Add 54.8g of neopentyl glycol and 50.25g of vinyltrimethoxysilane into a clean 250mL three-necked flask, add 1.05g of trifluoromethanesulfonic acid, heat to 120°C for 4 hours, and then remove low molecular weight under reduced pressure at 120°C/130mmHg 2h, and then the temperature was lowered to room temperature to obtain 72.46 g of a colorless transparent liquid, that is, a fluorescent hyperbranched organosilicon polymer containing hydroxyl groups.

(2) 200g of polytetramethylene ether glycol with an average molecular weight of 2000 and 66.687g of IPDI, and 40g of the hydroxyl-containing fluorescent hyperbranched organosilicon obtained in step (1) were first polymerized by depressurizing 120°C/130mmHg for 1h to remove moisture After mixing 306g of tetrahydrofuran evenly, 0.181g of dibutyltin dilaurate was added, and after reacting at 40°C for 6h, 54.855g of hydroxypropyl methacrylate was added, and the reaction was continued at 40°C for 8h, and the tetrahydrofuran was removed under reduced pressure of 80°C/130mmHg. Afterwards, 361.542 g of an acrylate-terminated hyperbranched silicone-modified polyurethane-acrylate fluorescent polymer was obtained.

(3) Take 20 g of the acrylate-terminated hyperbranched organosilicon-modified polyurethane-acrylate fluorescent polymer obtained in (2), add 1 g of benzoin and 0.5 g of benzoin dimethyl ether, mix evenly, and degas at 130 mmHg/30°C in a vacuum After 20 minutes, UV curing was performed for 60 s to obtain a hyperbranched organosilicon modified polyurethane-acrylate fluorescent material, that is, a UV-cured light transmittance temperature-sensitive fluorescent material 1.

The UV-curable light transmittance temperature-sensitive fluorescent material 1 has a fluorescence intensity of 6.6×10 ⁶ cps at 317 nm, a pencil hardness of 4B, a light transmittance of 22.5% at 5°C, and a light transmittance of 93.1% at 25°C.

Test Example 1

According to the preparation steps in Example 1, the amount of the product in step (1) in step (2) changes, the resulting light transmittance change curve is shown in Figure 1, and the resulting fluorescence intensity change curve is shown in Figure 2.

Description as the preferred dosage of the fluorescent hyperbranched organosilicon polymer containing hydroxyl group is 1%-10% of the total mass of polyether diol or hydroxyl-terminated polysiloxane and diisocyanate, and the light transmittance at 5°C is the same as that at 25°C. The lower light transmittance results show that the material is opaque at lower temperature, and the material has higher light transmittance when the temperature reaches 25°C, indicating that the light transmittance of the obtained material changes with temperature. , which is a temperature-sensitive material. The fluorescence intensity increased with the increase of the amount of hyperbranched silicone-modified polyurethane-acrylate fluorescent material.

At the same time, the present invention does not need to incorporate fluorescent materials such as luminescent carbon quantum dots, rare earth metal ions or organic dyes, is non-toxic, has no fluorescent materials that are difficult to control in color, and does not contain carbon quantum dots, rare earth metal ions or organic dyes in the elastomer. Problems such as poor dispersion stability.

Example 2

(1) Add 39.190g of ethylene glycol and 74.919g of γ-aminopropyltriethoxysilane into a clean 250mL three-necked flask, add 11.41g of acidic cation exchange resin, heat to 160°C for 12 hours and then drop to room temperature, filter to remove acidic cations After the resin was exchanged, the low molecular weight was removed under reduced pressure at 160°C/130mmHg for 2h, and then the temperature was lowered to room temperature to obtain 67.022g of a colorless and transparent liquid, that is, a fluorescent hyperbranched organosilicon polymer containing hydroxyl groups.

(2) First, 100 g of HO(C ₂ H ₄ O) ₂₂ OH with an average molecular weight of 1000 and 52.248 g of TDI, and 15.225 g of the hydroxyl-containing fluorescence obtained in step (1), were decompressed at 110° C./130 mmHg for 1.5 h. Hyperbranched organosilicon polymer, 502.4g of toluene was mixed evenly, 1.011g of dibutyltin dilaurate was added, and after reacting at 60°C for 6h, 34.767g hydroxypropyl acrylate was added, and the reaction was continued at 60°C for 4h, and the pressure was reduced to 100°C / After removing toluene at 130 mmHg, 202.24 g of acrylate-terminated hyperbranched organosilicon-modified polyurethane-acrylate fluorescent polymer was obtained.

(3) Take 20 g of the acrylate-terminated hyperbranched organosilicon-modified polyurethane-acrylate fluorescent polymer obtained in (2), add 1 g of benzoin and 0.5 g of benzoin dimethyl ether, mix evenly, and degas at 130 mmHg/30°C in a vacuum After 20 min, UV curing was performed for 80 s to obtain a hyperbranched organosilicon-modified polyurethane-acrylate fluorescent material, that is, a UV-cured light transmittance temperature-sensitive fluorescent material 2.

The UV-curable light transmittance temperature-sensitive fluorescent material 2 has a fluorescence intensity of 6.6×10 ⁶ cps at 317 nm, a pencil hardness of 3B, a light transmittance of 4.5% at 5°C, and a light transmittance of 94.2% at 25°C.

Example 3

(1) 142.63g of diethylene glycol and 67.22g of phenyltrimethoxysilane were added to a clean 250mL three-necked flask, heated to 100°C and reacted for 12h, decompressed at 100°C/130mmHg for 4h, and then the temperature was lowered to room temperature 177.26 g of a colorless and transparent liquid, that is, a fluorescent hyperbranched organosilicon polymer containing hydroxyl groups, was obtained.

(2) First, 120 g of a copolymer of ethylene oxide and propylene oxide with an average molecular weight of 1200 and two hydroxyl groups at both ends, which was decompressed at 100° C./130 mmHg for 2 hours, was decompressed and removed HO(C ₂ H ₄ O) ₂₀ (C ₃ H ₆ ). O) ₅ OH and 50.052g MDI, and 1.70g of the fluorescent hyperbranched organosilicon polymer containing hydroxyl groups obtained in step (1), 85.9g of petroleum ether were mixed uniformly, 0.017g of dibutyltin dilaurate was added, and the reaction was carried out at 80°C After 3h, 59.487g of 4-hydroxyphenyl methacrylate was added, and the reaction was continued at 80°C for 4h, and the petroleum ether was removed under reduced pressure of 120°C/130mmHg to obtain 290.726g of acrylate-terminated hyperbranched organosilicon-modified polyurethane-acrylate. fluorescent polymers.

(3) Take 20 g of the acrylate-terminated hyperbranched organosilicon-modified polyurethane-acrylate fluorescent polymer obtained in (2), add 0.5 g of α-amino alkyl phenone, 0.5 g of aroyl phosphine oxide, and mix uniformly After vacuum defoaming at 130 mmHg/30 °C for 20 min, UV curing for 120 s, hyperbranched organosilicon modified polyurethane-acrylate fluorescent material was obtained, that is, UV curing light transmittance temperature sensitive fluorescent material 3.

The UV-curable light transmittance temperature-sensitive fluorescent material 3 has a fluorescence intensity of 7.27×10 ⁶ cps at 317 nm, a pencil hardness of 3B, a light transmittance of 57.5% at 5°C, and a light transmittance of 92.8% at 25°C.

Example 4

(1) 91.635g triethylene glycol, 50.251g vinyltrimethoxysilane and 1.5g p-toluenesulfonic acid were added to a clean 250mL three-necked flask, heated to 100°C for 12h, and then decompressed under reduced pressure at 130°C/130mmHg Molecules for 4 hours, and then the temperature was lowered to room temperature to obtain 177.26 g of a colorless and transparent liquid, that is, a fluorescent hyperbranched organosilicon polymer containing hydroxyl groups.

(2) First, 350 g of ethylene oxide polymer HO(C 2 H 4 O) 80 OH and 33.639 g of HDI, and 19.182 g of ethylene oxide polymer HO(C ₂ H ₄ O) ₈₀ OH and 33.639 g of HDI with an average molecular weight of 3500, which were decompressed at 130° C./130 mmHg for 0.5 h, were dehydrated. For the fluorescent hyperbranched organosilicon polymer containing hydroxyl groups obtained in step (1), after 403 g of acetone was mixed uniformly, 1.611 g of dibutyltin dilaurate was added, and after reacting at 30°C for 8 h, 19.079 g of hydroxyethyl acrylate was added, and the temperature was continued at 30 °C. The reaction was carried out at ℃ for 6 h, and the acetone was removed under reduced pressure of 90 ℃/130 mmHg to obtain 421.9 g of acrylate-terminated hyperbranched organosilicon-modified polyurethane-acrylate fluorescent polymer.

(3) Take 20 g of the acrylate-terminated hyperbranched organosilicon-modified polyurethane-acrylate fluorescent polymer obtained in (2), add 0.5 g of 2,4-dihydroxybenzophenone, and 0.5 g of Michler's ketone, and mix them evenly. After vacuum defoaming at 130 mmHg/30 °C for 20 min, UV curing was performed for 180 s to obtain a hyperbranched organosilicon modified polyurethane-acrylate fluorescent material, namely UV curing light transmittance temperature sensitive fluorescent material 4.

The UV-curable light transmittance temperature-sensitive fluorescent material 4 has a fluorescence intensity of 6.2×10 ⁶ cps at 317 nm, a pencil hardness of 4B, a light transmittance of 17.1% at 5°C, and a light transmittance of 94.8% at 25°C.

Example 5

(1) Add 105.348g of tetraethylene glycol, 46.206g of methyltrimethoxysilane and 0.2g of concentrated sulfuric acid into a clean 250mL three-necked flask, heat to 180°C and react for 6h, then reduce the pressure at 180°C/130mmHg under reduced pressure Molecules for 6 hours, and then the temperature was lowered to room temperature to obtain 118.969 g of a colorless and transparent liquid, that is, a fluorescent hyperbranched organosilicon polymer containing hydroxyl groups.

(2) First, 50g of HO[(CH ₃ ) ₂ SiO] ₆ OH and 33.639g of HDI with hydroxyl groups at both ends of the average molecular weight of 500 which were decompressed at 120° C./130mmHg for 2h, and 6.691g obtained in step (1) were prepared Fluorescent hyperbranched organosilicon polymer containing hydroxyl groups, after mixing 271g acetone evenly, add 0.0181g dibutyltin dilaurate, react at 40°C for 8h, add 25.532g hydroxypropyl acrylate, continue to react at 60°C for 4h, under reduced pressure After removing acetone at 90°C/130mmHg, 115.862 g of acrylate-terminated hyperbranched organosilicon-modified polyurethane-acrylate fluorescent polymer was obtained.

(3) Take 20 g of the acrylate-terminated hyperbranched organosilicon-modified polyurethane-acrylate fluorescent polymer obtained in (2), add 0.5 g of α-amino alkyl phenone, 0.5 g of aroyl phosphine oxide and mix uniformly, After vacuum defoaming at 130 mmHg/30 °C for 20 min, UV curing was performed for 40 s to obtain a hyperbranched organosilicon modified polyurethane-acrylate fluorescent material, that is, UV curing light transmittance temperature-sensitive fluorescent material 5.

The UV-curable light transmittance temperature-sensitive fluorescent material 5 has a fluorescence intensity of 7.5×10 ⁶ cps at 317 nm, a pencil hardness of 3B, a light transmittance of 78.2% at 5°C, and a light transmittance of 85.0% at 25°C.

Example 6

(1) Add 105.348g of tetraethylene glycol, 46.206g of methyltrimethoxysilane and 0.2g of concentrated sulfuric acid into a clean 250mL three-necked flask, heat to 180°C and react for 6h, then reduce the pressure at 180°C/130mmHg under reduced pressure Molecules for 6 hours, and then the temperature was lowered to room temperature to obtain 118.969 g of a colorless and transparent liquid, that is, a fluorescent hyperbranched organosilicon polymer containing hydroxyl groups.

(2) First, 640 g of HO[(CH ₃ ) ₂ SiO] ₃₂ [CH ₃ C ₆ H ₅ SiO] ₁₆ [CH ₃ CH ₂ with hydroxyl groups at both ends of the average molecular weight of 6400, which was decompressed at 110° C./130 mmHg for 1 hour and dehydrated for 1 h were removed CH ₂ CF ₃ SiO] ₁₂ OH and 33.639g HDI, and 6.691g of the hydroxyl-containing fluorescent hyperbranched organosilicon polymer obtained in step (1), after 271g of acetone were mixed uniformly, 0.0181g of dibutyltin dilaurate was added, and the mixture was heated at 40 After 8 hours of reaction at ℃, 25.532 g of hydroxypropyl acrylate was added, and the reaction was continued at 60 ℃ for 4 hours. After the acetone was removed under reduced pressure of 90 ℃/130 mmHg, 115.862 g of acrylate-terminated hyperbranched organosilicon-modified polyurethane-acrylate fluorescent polymer was obtained. .

(3) Take 20 g of the acrylate-terminated hyperbranched organosilicon-modified polyurethane-acrylate fluorescent polymer obtained in (2), add 0.5 g of bisbenzoylphenyl phosphine oxide, 0.5 g of thiopropoxythioxanthene After the ketones were mixed uniformly, they were vacuum degassed at 130 mmHg/30 °C for 20 min, and then UV cured for 40 s to obtain a hyperbranched organosilicon modified polyurethane-acrylate fluorescent material, that is, a UV cured light transmittance temperature sensitive fluorescent material 6.

The UV-curable light transmittance temperature-sensitive fluorescent material 6 has a fluorescence intensity of 3.3×10 ⁶ cps at 317 nm, a pencil hardness of 4B, a light transmittance of 48.2% at 5°C, and a light transmittance of 74.5% at 25°C.

Claims (10)

1. a UV curing light transmittance temperature-sensitive fluorescent material, is characterized in that, the light transmittance temperature-sensitive fluorescent material is in the visible light range of 400-800nm, and the light transmittance is 4%-78% during 5 ℃, The light transmittance at 25℃ is 75.0%-98%, the fluorescence intensity at 317nm is 3.3×10 ⁶ cps-8.0×10 ⁶ cps, and the hardness is 4B~2B. 2. a preparation method of the fluorescent material of UV curing light transmittance temperature-sensitive as claimed in claim 1, is characterized in that, described preparation method is the following steps: (1) A fluorescent hyperbranched organosilicon polymer containing hydroxyl groups is obtained by using a compound with hydroxyl groups at both ends and an alkoxysiloxane under the action of a catalyst; (2) Polyether diol or hydroxyl-terminated polysiloxane, diisocyanate and the fluorescent hyperbranched organosilicon polymer containing hydroxyl groups obtained in step (1) are catalyzed by diisobutyl tin laurate in a solvent. The following reaction is performed to obtain an isocyanate-terminated hyperbranched polyurethane, which is then reacted with hydroxy acrylate to obtain a hyperbranched organosilicon modified polyurethane-acrylate fluorescent polymer; (3) The obtained hyperbranched organosilicon modified polyurethane-acrylate and UV initiator are mixed uniformly in proportion, and after vacuum defoaming for 10~30min, and UV curing for 10~180s, the light transmittance temperature-sensitive fluorescent material can be obtained . 3 . The method for preparing a UV-curable light transmittance temperature-sensitive fluorescent material according to claim 2 , wherein the compound whose two ends are hydroxyl groups in step (1) is selected from the group consisting of diols, polyethers One or more of diols and polysiloxanes terminated by hydroxyl groups at both ends, and alkoxysilanes are selected from methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyl Triethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, ethyltrimethoxysilane, ethyl One or more of thiopropyltriethoxysilane, mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane, and the molar ratio of the compound with hydroxyl groups at both ends and alkoxysilane is 1.55-2.5: 1. 4 . The method for preparing a UV-curable light transmittance temperature-sensitive fluorescent material according to claim 2 , wherein the catalyst described in step (1) is selected from the group consisting of sulfuric acid, trifluoromethanesulfonic acid, and p-toluene. 5 . One or more mixtures of sulfonic acid and acidic macroporous cation exchange resin, and the amount of catalyst used is 0-10wt% of the total mass of the raw materials. 5 . The preparation method of a UV-curable light transmittance temperature-sensitive fluorescent material according to claim 2 , wherein in step (2), the amount of polyether diol or hydroxyl terminated polysiloxane and diisocyanate is used. 6 . According to the molar ratio of 1:1.05-1:2.5, the amount of fluorescent hyperbranched organosilicon polymer containing hydroxyl groups used is 0.5%-15% of the total mass of polyether diol or hydroxyl-terminated polysiloxane diisocyanate. 6 . The method for preparing a UV-curable light transmittance temperature-sensitive fluorescent material according to claim 2 , wherein the hydroxy acrylate in step (2) is selected from the group consisting of hydroxyethyl methacrylate, methyl methacrylate, and methyl methacrylate. 7 . One or more of hydroxypropyl acrylate, 4-hydroxyphenyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, and 4-hydroxybutyl acrylate. 7. The preparation method of a UV-curable light transmittance temperature-sensitive fluorescent material according to claim 2, wherein the amount of diisobutyltin laurate in step (2) is the quality of the reaction raw material in step (2). of 0.01%-1%. 8 . The method for preparing a UV-curable light transmittance temperature-sensitive fluorescent material according to claim 2 , wherein in step (3), the UV initiator is selected from the group consisting of benzoin, benzoin dimethyl ether, benzoin ether, benzoin Isopropyl ether, butyl benzoin, diphenylethanone, α,α-dimethoxy-α-phenylacetophenone, α,α-diethoxyacetophenone, α-hydroxyalkylphenone , α-aminoalkyl phenone, aroyl phosphine oxide, bisbenzoyl phenyl phosphine oxide, benzophenone, 2,4-dihydroxybenzophenone, Michler's ketone; thiopropoxy sulfur One or more of xanthone and isopropylthioxanthone are used in an amount of 1-12% of the mass of the acrylate-terminated hyperbranched organosilicon-modified polyurethane-acrylate fluorescent polymer. 9 . The method for preparing a UV-cured light transmittance temperature-sensitive fluorescent material according to claim 2 , wherein in step (3), the UV light source is one of 365 nm, 405 nm, and 385 nm, and the UV light power is 300- 2000w/h. 10. The application of the UV-curable light transmittance temperature-sensitive fluorescent material according to claim 1 in the fields of temperature-sensitive optical devices, anti-counterfeiting, fluorescent probes, and fluorescent coatings.

Images