CN106192038B - The preparation method of blue light luminous fiber - Google Patents

Abstract

The present invention relates to a kind of preparation methods of blue light luminous fiber, include the following steps：（1）By 0.1~0.5 parts by weight triphenyl sulphur hexafluoro antimonate photoinitiator and 5~10 parts by weight SrAl₂O₄：Eu²⁺, Dy³⁺Luminescent material, the mixing of 20~40 parts by weight fibre-forming polymer base materials, are granulated using dual-screw pelletizer, obtain spinning noctilucence master batch；（2）By step（1）Melt spinning after obtained spinning noctilucence master batch predrying obtains the blue light luminous fiber.The luminous fiber that the present invention obtains absorbs visible light 10 minutes, sustainable in the dark state to shine 10 hours or more；Light emission luminance reaches as high as 1.5 ~ 3cd/m²；430 ~ 450nm the blue lights sent out are one kind of three primary colours, and the luminous fiber of any type secondary color can be prepared with one or two kinds of compounding in red luminous fiber and green luminous fiber, can expand the application field of luminous fiber.

Description

Preparation method of blue light luminous fiber

technical field

The invention relates to a preparation method of a blue luminous fiber, in particular to a preparation method of a blue luminous fiber capable of emitting 430-450nm blue light in the dark, and belongs to the technical field of functional textile material manufacturing.

Background technique

Rare earth strontium aluminate luminous fiber is a new type of environmentally friendly and energy-saving fiber. It is mainly made of rare earth materials as illuminants through special spinning technology. It is widely used because of its good luminous performance in the dark or at night. However, the wavelength of the emitted light is between 520 and 540nm, and the spectrum is distributed in the yellow-green light region, so the monotonous emission color has become a major problem in application. At present, the main raw materials of the existing blue luminous fibers are metal sulfides and silicate luminescent substances, and the initial afterglow brightness is lower than that of aluminate system luminescent materials. Studies have shown that the traditional green luminous fiber and red luminous fiber with SrAl ₂ O ₄ : Eu ²⁺ and Dy ³⁺ as luminescent materials have been developed, but so far there has been no report using SrAl ₂ O ₄ : Eu ²⁺ , Dy ³⁺ is a luminescent substance to prepare a luminous fiber that can emit blue light.

Therefore, looking for a long-wave (SrAl ₂ O ₄ emitting yellow-green light: Eu ²⁺ , Dy ³⁺ luminous fiber) to short-wave (SrAl ₂ O ₄ emitting blue light: Eu ²⁺ , Dy ³⁺ luminous fiber) Fiber) down-conversion materials have important research value and practical significance. Among them, triphenyliodine hexafluoroantimonate photoinitiator is a photosensitive material with excellent photoconversion performance, which can absorb radiation energy and trigger electron transition, which can realize SrAl ₂ O ₄ : Eu ²⁺ , Dy ³⁺ The purpose of glow-in-the-dark fibers is to glow blue in the dark.

Contents of the invention

The object of the present invention is to overcome the deficiencies in the prior art, and provide a preparation method of blue luminous fiber. The obtained luminous fiber can emit blue light with a wavelength of 430-450nm.

According to the technical solution provided by the present invention, the preparation method of the blue luminous fiber is characterized in that it includes the following steps:

(1) 0.1-0.5 parts by weight of triphenylsulfur hexafluoroantimonate photoinitiator, 5-10 parts by weight of SrAl ₂ O ₄ : Eu ^{2 +} , Dy ³⁺ luminescent material, 20-40 parts by weight of fiber-forming polymerization Mix the material base material and granulate it with a twin-screw granulator to obtain a luminous masterbatch for spinning; the structural formula of the triphenylsulfur hexafluoroantimonate photoinitiator is:

;

(2) Pre-drying the luminous masterbatch for spinning obtained in step (1) and then melt-spinning to obtain the blue luminous fiber.

In a specific embodiment, the triphenylsulfur hexafluoroantimonate photoinitiator is prepared by the following steps: 10-15 parts by weight of potassium iodate, 16-20 parts by weight of benzene, 23-27 parts by weight of acetic anhydride Mix with 5-10 parts by weight of solvent, lower the obtained reaction solution to -5-10°C, slowly add 10-15 parts by weight of concentrated sulfuric acid and react for 2-4 hours, then stir at room temperature for 46-48 hours and then add hexafluoro Potassium antimonate aqueous solution and potassium hexafluoroantimonate aqueous solution are obtained by mixing 10 to 15 parts by weight of potassium hexafluoroantimonate and 50 to 55 parts by weight of water; the above reaction solution is suction filtered, washed and recrystallized to obtain diphenyl iodide White crystal of hexafluoroantimonate; add 20-25 parts by weight of phenylene sulfide and 6-10 parts by weight of catalyst to 5-10 parts by weight of diphenyl iodine hexafluoroantimonate white crystal, and fill the reaction vessel with nitrogen And raise the temperature to 100~120°C to react for 2~4 hours, and after natural cooling, the precipitate was obtained, and after suction filtration, washing and recrystallization, white crystals of triphenylsulfur hexafluoroantimonate were obtained.

In a specific embodiment, the specific steps of using a twin-screw granulator in the step (1) are as follows: pre-drying the fiber-forming polymer substrate at 100-120°C for 20-24 hours, and then mixing with triphenylsulfide Hexafluoroantimonate photoinitiator and SrAl ₂ O ₄ : Eu ²⁺ , Dy ³⁺ luminescent material are mixed, and granulated by a twin-screw granulator to obtain luminous masterbatch for spinning.

In a specific embodiment, polyester, polypropylene or polyamide chips are used as the fiber-forming polymer substrate.

In a specific embodiment, the solvent is anhydrous acetonitrile.

In a specific embodiment, the catalyst uses anhydrous copper acetate.

The present invention has the following advantages: the luminous fiber obtained by the present invention absorbs visible light for 10 minutes, and can continue to emit light for more than 10 hours in a dark state; the maximum luminous brightness can reach 1.5~3cd/m ² ; the emitted 430~450nm blue light is trichromatic One, compounding with one or both of red luminous fiber and green luminous fiber can prepare any kind of multi-color luminous fiber, which can expand the application field of luminous fiber.

Description of drawings

Figure 1-1 is a scanning electron micrograph of the triphenylsulfur hexafluoroantimonate photoinitiator prepared in the present invention.

Figures 1-2 are scanning electron micrographs of the blue luminous fiber prepared in the present invention.

1-3 are scanning electron micrographs of the SrAl ₂ O ₄ : Eu ²⁺ , Dy ³⁺ luminescent material prepared in the present invention.

Fig. 2 is a fluorescence spectrum diagram of the blue-emitting luminous fiber prepared in the present invention.

Fig. 3 is a schematic diagram of photoinitiation of the blue-emitting luminous fiber prepared in the present invention.

Detailed ways

The present invention will be further described below in conjunction with specific examples.

Triphenylsulfur hexafluoroantimonate has the characteristics of high photoinitiation activity and high temperature resistance stability, and can trigger rare earth strontium aluminate luminous fibers to produce blue light by blending. The triggering principle is that the molecules of triphenylsulfur hexafluoroantimonate contain substances of the conjugated polymer system, which can absorb light energy and jump to the excited state, and the molecules in the excited state can transfer excess energy to the molecules of the fluorescent substance ; Due to the specific electronic configuration of rare earth ions, they can accept energy transitions from the conjugated polymer system to the excited state, and emit the characteristic fluorescence of each ion when the electrons return from the excited state to the ground state. The triphenylsulfur hexafluoroantimonate with a conjugated system acts as an "antenna" as an energy donor, and its emission spectrum should have a good overlap with the absorption spectrum of the acceptor (rare earth ion). Electrons can migrate in the whole conjugated system, therefore, the blue shift of the emission spectrum of SrAl ₂ O ₄ : Eu ²⁺ , Dy ³⁺ luminous fiber can be realized through energy transfer. As shown in Fig. 2, it is the fluorescence spectrum diagram of the blue-emitting luminous fiber prepared by the present invention; the abscissa is the wavelength, and the unit is nm; the ordinate is the relative intensity, and the unit is count · s ^-1 .

As shown in Figure 3, it is the photoinitiation schematic diagram of the blue-emitting luminous fiber prepared by the present invention: triphenylsulfur hexafluoroantimonate conjugated polymer donor (S) to SrAl ₂ O ₄ : Eu ²⁺ , The energy transfer of the Dy ³⁺ luminescent material acceptor (A) results in a blue shift of the fluorescence emission.

Embodiment 1: a kind of preparation method of blue light luminous fiber, comprises the following steps:

(1) To prepare triphenylsulfur hexafluoroantimonate photoinitiator, the following steps are adopted: 10 parts by weight of potassium iodate, 16 parts by weight of benzene, 23 parts by weight of acetic anhydride and 5 parts by weight of anhydrous acetonitrile are mixed to obtain The reaction solution was lowered to -5°C, slowly added 10 parts by weight of concentrated sulfuric acid and reacted for 2 hours, then stirred at room temperature for 46 hours and then added an aqueous solution of potassium hexafluoroantimonate, which was composed of 10 parts by weight of hexafluoroantimonic acid Potassium and 50 parts by weight of water are mixed; the above reaction solution is filtered, washed and recrystallized to obtain white crystals of diphenyl iodine hexafluoroantimonate; Add 20 parts by weight of phenylene sulfide and 6 parts by weight of anhydrous copper acetate, fill the reaction vessel with nitrogen and raise the temperature to 100°C for 2 hours. After natural cooling, a precipitate is obtained. After suction filtration, washing and recrystallization, triphenyl White crystals of sulfur hexafluoroantimonate;

(2) After pre-drying 20 parts by weight of the fiber-forming polymer substrate at 100 ° C for 20 h, with 0.1 parts by weight of triphenylsulfur hexafluoroantimonate photoinitiator and 5 parts by weight of SrAl ₂ O ₄ : Eu ²⁺ , Dy ³⁺ luminescent materials are mixed and granulated by a twin-screw granulator to obtain luminous masterbatch for spinning; the fiber-forming polymer substrate is made of polyester, polypropylene or polyamide slices;

(3) Pre-drying the luminous masterbatch for spinning obtained in step (2) and then melt-spinning to obtain the blue luminous fiber.

Embodiment 2: a kind of preparation method of blue light luminous fiber, comprises the following steps:

(1) To prepare triphenylsulfur hexafluoroantimonate photoinitiator, the following steps are adopted: 13 parts by weight of potassium iodate, 18 parts by weight of benzene, 25 parts by weight of acetic anhydride and 7 parts by weight of anhydrous acetonitrile are mixed to obtain The reaction solution was lowered to -7°C, 13 parts by weight of concentrated sulfuric acid was slowly added and reacted for 3 hours, and after stirring at room temperature for 47 hours, an aqueous solution of potassium hexafluoroantimonate was added, and the aqueous solution of potassium hexafluoroantimonate was composed of 13 parts by weight of Potassium and 53 parts by weight of water are mixed; the above reaction solution is filtered, washed and recrystallized to obtain white crystals of diphenyl iodine hexafluoroantimonate; Add 23 parts by weight of phenylene sulfide and 8 parts by weight of anhydrous copper acetate, fill the reaction vessel with nitrogen and raise the temperature to 110°C for 3 hours. After natural cooling, a precipitate is obtained. After suction filtration, washing and recrystallization, triphenyl White crystals of sulfur hexafluoroantimonate;

(2) After pre-drying 30 parts by weight of the fiber-forming polymer substrate at 110°C for 22 hours, with 0.3 parts by weight of triphenylsulfur hexafluoroantimonate photoinitiator and 7 parts by weight of SrAl ₂ O ₄ :Eu ²⁺ , Dy ³⁺ luminescent materials are mixed and granulated by a twin-screw granulator to obtain luminous masterbatch for spinning; the fiber-forming polymer substrate is made of polyester, polypropylene or polyamide slices;

(3) Pre-drying the luminous masterbatch for spinning obtained in step (2) and then melt-spinning to obtain the blue luminous fiber.

Embodiment 3: A kind of preparation method of blue light luminous fiber, comprises the following steps:

(1) To prepare triphenylsulfur hexafluoroantimonate photoinitiator, the following steps are adopted: 15 parts by weight of potassium iodate, 20 parts by weight of benzene, 27 parts by weight of acetic anhydride and 10 parts by weight of anhydrous acetonitrile are mixed to obtain The reaction solution was lowered to -10°C, 15 parts by weight of concentrated sulfuric acid was slowly added and reacted for 4 hours, and then stirred at room temperature for 48 hours, and then an aqueous solution of potassium hexafluoroantimonate was added, which was composed of 15 parts by weight of hexafluoroantimonic acid Potassium and 55 parts by weight of water are mixed; the above reaction solution is filtered, washed and recrystallized to obtain white crystals of diphenyl iodine hexafluoroantimonate; Add 25 parts by weight of phenylene sulfide and 10 parts by weight of anhydrous copper acetate, fill the reaction vessel with nitrogen and raise the temperature to 120°C for 4 hours of reaction. After natural cooling, a precipitate is obtained. After suction filtration, washing and recrystallization, triphenyl White crystals of sulfur hexafluoroantimonate;

(2) After pre-drying 40 parts by weight of the fiber-forming polymer substrate at 120 ° C for 24 h, with 0.5 parts by weight of triphenylsulfur hexafluoroantimonate photoinitiator and 10 parts by weight of SrAl ₂ O ₄ : Eu ²⁺ , Dy ³⁺ luminescent materials are mixed and granulated by a twin-screw granulator to obtain luminous masterbatch for spinning; the fiber-forming polymer substrate is made of polyester, polypropylene or polyamide slices;

(3) Pre-drying the luminous masterbatch for spinning obtained in step (2) and then melt-spinning to obtain the blue luminous fiber.

As shown in Figure 1-1, Figure 1-2, and Figure 1-3, they are respectively the triphenylsulfur hexafluoroantimonate photoinitiator prepared by the present invention, blue luminous fiber and SrAl ₂ O ₄ :Eu ²⁺ , SEM image of Dy ³⁺ luminescent material.

Claims (5)

1. a preparation method of blue light luminous fiber, is characterized in that, comprises the following steps: (1) 0.1-0.5 parts by weight of triphenylsulfur hexafluoroantimonate photoinitiator, 5-10 parts by weight of SrAl ₂ O ₄ : Eu ²⁺ , Dy ³⁺ luminescent material, 20-40 parts by weight of fiber-forming polymerization Mix the material base material, use the twin-screw granulator to granulate, and obtain the luminous masterbatch for spinning; (2) Pre-drying the luminous masterbatch for spinning obtained in step (1) and then melt-spinning to obtain the blue luminous fiber; The triphenylsulfur hexafluoroantimonate photoinitiator is prepared by the following steps: 10-15 parts by weight of potassium iodate, 16-20 parts by weight of benzene, 23-27 parts by weight of acetic anhydride and 5-10 parts by weight of solvent Mix, lower the obtained reaction solution to -5~-10°C, slowly add 10~15 parts by weight of concentrated sulfuric acid and react for 2~4 hours, then stir at room temperature for 46~48 hours, then add potassium hexafluoroantimonate aqueous solution, hexafluoro The aqueous solution of potassium antimonate is obtained by mixing 10-15 parts by weight of potassium hexafluoroantimonate and 50-55 parts by weight of water; the above reaction solution is filtered, washed and recrystallized to obtain white crystals of diphenyl iodine hexafluoroantimonate ; Add 20-25 parts by weight of phenylene sulfide and 6-10 parts by weight of catalyst to 5-10 parts by weight of diphenyliodine hexafluoroantimonate white crystals, fill the reaction vessel with nitrogen and raise the temperature to 100-120°C After reacting for 2-4 hours, the precipitate was obtained after natural cooling, and after suction filtration, washing and recrystallization, white crystals of triphenylsulfur hexafluoroantimonate were obtained. 2. The preparation method of blue light-in-the-dark fiber according to claim 1, characterized in that: the specific step of using a twin-screw granulator in the step (1) is to granulate the fiber-forming polymer substrate at 100- After pre-drying at 120°C for 20-24 hours, it is mixed with triphenylsulfur hexafluoroantimonate photoinitiator and SrAl ₂ O ₄ : Eu ²⁺ , Dy ³⁺ luminescent material, and granulated by twin-screw granulator to obtain spinning Luminous masterbatch for silk. 3. The preparation method of blue luminous fiber according to claim 1 or 2, characterized in that: polyester, polypropylene or polyamide chips are used as the fiber-forming polymer substrate. 4. The preparation method of blue luminous fiber according to claim 1, characterized in that: the solvent is anhydrous acetonitrile. 5. The preparation method of blue luminous fiber according to claim 1, characterized in that: the catalyst is anhydrous copper acetate.