CN102887973B - Preparation method of white fluorescent powder containing europium terbium beryllium polymer - Google Patents

Abstract

The invention relates to a preparation method of white fluorescent powder containing europium terbium beryllium polymer. The method comprises the steps of: firstly, preparing red europium complex, green beryllium complex and blue beryllium complex; and carrying out polymerization reaction in a four-hole boiling flask, and washing, leaching, drying and grinding to prepare the white fluorescent powder containing the europium terbium beryllium polymer. According to the preparation method, the process is advanced, the data is accurate, the light emitting purity of the white fluorescent powder is good, and the luminous efficiency is high; chromaticity coordinates under 365nm of ultraviolet light excitation are that x is 0.3218 and y is 0.3332, and the preparation method is an ideal method for preparing the white fluorescent powder containing the europium terbium beryllium polymer.

Description

A kind of preparation method of the white emitting fluorescent powder containing europium terbium beryllium polymkeric substance

Technical field

The present invention relates to a kind of preparation method of the white emitting fluorescent powder containing europium terbium beryllium polymkeric substance, belong to the technical field of luminescent material preparation and application.

Background technology

White light LEDs because volume is little, energy-saving and environmental protection, long service life, luminous efficiency are high, in electronics, luminous field, be widely used, thus be called as the 4th generation lighting source.

At present, realize white light LEDs and mainly contain three kinds of approach: the one, with red-green-blue chip portfolio, emit white light, this method will have four electrodes, three driving voltages, structure is more complicated; The 2nd, with blue chip, excite gold-tinted fluorescent material, obtain white light, this fluorescent material lacks ruddiness composition, and colour temperature is on the low side, and color developing is poor; The 3rd, with ultraviolet chip, excite three primary colors fluorescent powder to obtain white light, this method more easily obtains the white light of solid colour, photochromicly can by the proportioning of fluorescent material, be determined to have high-color rendering, the photochromic and adjustable advantage of colour temperature; Although these methods can obtain white light, also there is the drawback that material selection is not enough and preparation method falls behind, cause white light LEDs not reach service requirements.

Summary of the invention

Goal of the invention

Object of the present invention is exactly the situation for background technology, selects europium, terbium, beryllium material, first prepares red, green, blue title complex, then carries out polymerization, makes white emitting fluorescent powder, to improve luminous intensity and the luminous efficiency of white emitting fluorescent powder.

Technical scheme

The chemical substance material using is: Europium trichloride, 2-thenoyltrifluoroacetone, terbium chloride, anthranilic acid, beryllium sulfate, 2-(2-hydroxy phenyl) benzothiazole, undecylenic acid, α-methacrylic acid, methyl methacrylate, Diisopropyl azodicarboxylate, sodium hydroxide, dehydrated alcohol, anhydrous methanol, dimethyl sulfoxide (DMSO), deionized water, nitrogen, it is as follows that it prepares consumption: with gram, milliliter, centimetre ³for measure unit

Europium trichloride EuCl ₃0.3664 g ± 0.0001 g

2-thenoyltrifluoroacetone C ₈h ₅f ₃o ₂s 0.4444 g ± 0.0001 g

Terbium chloride TbCl ₃0.3734 g ± 0.0001 g

Anthranilic acid C ₇h ₇nO ₂0.4114 g ± 0.0001 g

Undecylenic acid C ₁₁h ₂₀o ₂0.9214 g ± 0.0001 g

Beryllium sulfate BeSO ₄4H ₂o 0.1771 g ± 0.0001 g

2-(2-hydroxy phenyl) benzothiazole C ₁₃h ₉nOS 0.2273 g ± 0.0001 g

α-methacrylic acid C ₄h ₆o ₂0.0845 mL ± 0.0001 mL

Sodium hydroxide NaOH 2 g ± 0.0001 g

Diisopropyl azodicarboxylate C ₈h ₁₂n ₄0.0074 g ± 0.0001 g

Methyl methacrylate C ₅h ₈o ₂1.6 mL ± 0.1 mL

Dehydrated alcohol CH ₃cH ₂oH 1000 mL ± 1 mL

Anhydrous methanol CH ₃oH 500mL ± 1mL

Dimethyl sulfoxide (DMSO) C ₂h ₆oS 5 mL ± 0.1 mL

Deionized water H ₂o 200 mL ± 0.1 mL

Nitrogen N ₂10000 cm ³± 100 cm ³

Preparation method is as follows

(1) obtain solution

preparation Europium trichloride ethanolic soln

Take Europium trichloride 0.3664 g ± 0.0001 g, measure dehydrated alcohol 5 mL ± 0.1 mL, be placed in beaker, agitator stirs 5 min, becomes the Europium trichloride ethanolic soln of 0.2 mol/L;

preparation 2-thenoyltrifluoroacetone ethanolic soln

Take 2-thenoyltrifluoroacetone 0.4444 g ± 0.0001 g, measure dehydrated alcohol 10 mL ± 0.1 mL, be placed in beaker, agitator stirs 5 min, becomes the 2-thenoyltrifluoroacetone ethanolic soln of 0.2 mol/L;

preparation terbium chloride ethanolic soln

Take terbium chloride 0.3734 g ± 0.0001 g, measure dehydrated alcohol 5 mL ± 0.1 mL, be placed in beaker, agitator stirs 5 min, becomes the terbium chloride ethanolic soln of 0.2 mol/L;

preparation anthranilic acid ethanolic soln

Take anthranilic acid 0.4114 g ± 0.0001 g, measure dehydrated alcohol 15 mL ± 0.1 mL, be placed in beaker, agitator stirs 5 min, becomes the anthranilic acid ethanolic soln of 0.2 mol/L;

the preparation beryllium sulfate aqueous solution

Take beryllium sulfate 0.1771 g ± 0.0001 g, measure deionized water 5 mL ± 0.1 mL, be placed in beaker, agitator stirs 5 min, and ultrasonic vibrator vibrates 30 min, becomes the beryllium sulfate aqueous solution of 0.2 mol/L;

preparation 2-(2-hydroxy phenyl) benzothiazole methanol solution

Take 2-(2-hydroxy phenyl) benzothiazole 0.2273 g ± 0.0001g, measure anhydrous methanol 20 mL ± 0.1 mL, be placed in beaker, agitator stirs 5 min, ultrasonic vibrator vibrates 30 min, becomes 2-(2-hydroxy phenyl) the benzothiazole methanol solution of 0.05 mol/L;

preparation undecylenic acid ethanolic soln

Take undecylenic acid 0.9214 g ± 0.0001 g, measure dehydrated alcohol 25 mL ± 0.1 mL, be placed in beaker, agitator stirs 5 min, becomes the undecylenic acid ethanolic soln of 0.2 mol/L;

preparation sodium hydroxide ethanolic soln

Weighing sodium hydroxide 2 g ± 0.0001 g, measure dehydrated alcohol 50 mL ± 0.1 mL, are placed in beaker, and agitator stirs 5 min, becomes the sodium hydroxide ethanolic soln of 1 mol/L;

(2) prepare europium ruddiness title complex

Prepare europium ruddiness title complex and carry out in there-necked flask, in heating, stirring, dropping solution process, complete;

there-necked flask is placed on electric mantle, on there-necked flask top, inserts dropping funnel, agitator, pH meter;

measure undecylenic acid ethanolic soln 15 mL ± 0.1 mL and add in there-necked flask, opening electric heater heating, Heating temperature is 50oC ± 1oC, and stirs;

europium trichloride ethanolic soln 5 mL ± 0.1 mL are joined in dropping funnel, drip, rate of addition is 1 mL/min, and stir on dropping limit, limit, and the time is 5 min;

sodium hydroxide ethanolic soln 1 mL ± 0.1 mL is added in dropping funnel, drip, rate of addition is 1 mL/min, and stir on dropping limit, limit, and regulating pH value is 4.5-5.5, reaction times 30 min;

by 2-thenoyltrifluoroacetone ethanolic soln 10 mL ± 0.1 mL, add in dropping funnel, drip, rate of addition is 1 mL/min, and stir on dropping limit, limit, and regulating pH value is 6.5-7.0;

continue reaction 180 min, in heating, stirring, dropping solution process, chemical reaction will occur,

Reaction formula is as follows:

In formula: Eu (C ₈h ₅f ₃o ₂s) ₂(C ₁₁h ₁₉o ₂) ₃: europium ruddiness title complex, NaCl: sodium-chlor

stop heating, stir, make reaction soln be cooled to 25oC with bottle, and precipitation, reaction soln obtained;

suction filtration, is placed in the Büchner funnel on filter flask by reaction soln, with millipore filtration, carries out suction filtration, obtains product filter cake on filter membrane, and waste liquid is evacuated in filter flask;

washing, suction filtration, be placed in beaker by product filter cake, adds dehydrated alcohol 50 mL, and agitator treating 5 min, then carry out suction filtration with millipore filtration; Washing, suction filtration repeat 3 times, obtain product filter cake;

vacuum-drying, is placed in quartz container by product filter cake, is then placed in vacuum drying oven dry, drying temperature 60oC, and vacuum tightness-0.08 Mpa, time of drying 6, h, obtained after being dried: europium ruddiness title complex;

(3) prepare terbium green glow title complex

Prepare terbium green glow title complex and carry out in there-necked flask, in heating, stirring, dropping solution process, complete;

there-necked flask is placed on electric mantle, on there-necked flask top, inserts dropping funnel, agitator, pH meter;

measure undecylenic acid ethanolic soln 10 mL ± 0.1 mL, add in there-necked flask, opening electric heater heating, Heating temperature is 50oC ± 1oC, and stirs;

terbium chloride ethanolic soln 5 mL ± 0.1 mL are joined in dropping funnel, drip, rate of addition is 1 mL/min, and stir on dropping limit, limit, and the time is 5 min;

sodium hydroxide ethanolic soln 1 mL ± 0.1 mL is added in dropping funnel, drip, rate of addition is 1 mL/min, and stir on dropping limit, limit, and regulating pH value is 5.5-6.5, reaction times 30 min;

by anthranilic acid ethanolic soln 15 mL ± 0.1 mL, add in dropping funnel, drip, rate of addition is 1 mL/min, and stir on dropping limit, limit, and pH value is 6.5-7.0;

continue reaction 180 min, in heating, stirring, dropping solution process, chemical reaction will occur, reaction formula is as follows:

In formula: Tb (C ₇h ₆nO ₂) ₃(C ₁₁h ₂₀o ₂) ₂: terbium green glow title complex

stop heating, stir, make reaction soln be cooled to 25oC with bottle, and precipitation, reaction soln obtained;

suction filtration, is placed in the Büchner funnel on filter flask by reaction soln, with millipore filtration, carries out suction filtration, obtains product filter cake on filter membrane, and waste liquid is evacuated in filter flask;

washing, suction filtration, be placed in beaker by product filter cake, adds dehydrated alcohol 50 mL agitator treating 5 min, then with millipore filtration, carries out suction filtration; Washing, suction filtration repeat 3 times, obtain product filter cake;

vacuum-drying, is placed in quartz container by product filter cake, is then placed in vacuum drying oven dry, drying temperature 60oC, and vacuum tightness-0.08 Mpa, time of drying 6, h, obtained after being dried: terbium green glow title complex;

(4) prepare beryllium blue light title complex

Prepare beryllium blue light title complex and carry out in there-necked flask, in heating, stirring, dropping solution process, complete;

there-necked flask is placed on electric mantle, on there-necked flask top, inserts dropping funnel, agitator, pH meter;

measure 2-(2-hydroxy phenyl) benzothiazole methanol solution 20 mL ± 0.1 mL and add in there-necked flask, opening electric heater heating, Heating temperature is 50oC ± 1oC, and stirs;

the beryllium sulfate aqueous solution 5 mL ± 0.1 mL are joined in dropping funnel, drip, rate of addition is 1 mL/min, and stir on dropping limit, limit, and the time is 5 min;

by α-methacrylic acid 0.0845 mL ± 0.0001 mL, with micro-feeder, add in dropping funnel, drip, rate of addition is 0.01 mL/min, continues reaction times 10 min;

sodium hydroxide ethanolic soln 1 mL ± 0.1 mL is added in dropping funnel, and drip stirring, rate of addition is 1 mL/min, regulating pH value is 8-9, occurs yellow-green precipitate, continues reaction 180 min, in heating, stirring, dropping solution process, will there is chemical reaction, reaction formula is as follows:

In formula: Be (C ₁₃h ₈nOS) (C ₄h ₅o ₂): beryllium blue light title complex, Na ₂sO ₄: sodium sulfate

stop heating, stir, make reaction soln be cooled to 25oC with bottle, and precipitation, reaction soln obtained;

suction filtration, is placed in the Büchner funnel on filter flask by reaction soln, uses millipore filtration suction filtration, obtains product filter cake on filter membrane, and waste liquid is evacuated in filter flask;

washing, suction filtration, be placed in beaker by product filter cake, adds dehydrated alcohol 50 mL agitator treating 5 min, then with millipore filtration, carries out suction filtration; Washing, suction filtration repeat 3 times, obtain product filter cake;

vacuum-drying, is placed in quartz container by product filter cake, is then placed in vacuum drying oven dry, drying temperature 60oC, and vacuum tightness-0.08 Mpa, time of drying 6, h, obtained after being dried: beryllium blue light title complex;

(5) preparation is containing europium terbium beryllium polymer white light fluorescent material

Preparation is carried out in four-hole bottle, under heating, stirring, water-bath, water cycle condensation, nitrogen protection, completes;

four-hole boiling flask is placed on cleansing bath tub, and the water-bath water in cleansing bath tub will flood 4/5 of four-hole boiling flask volume, on four-hole boiling flask top by left-to-right nitrogen tube, dropping funnel, agitator, the water cycle prolong of inserting successively;

by chemicals quality, than 0.015:0.05:0.03, take respectively europium ruddiness title complex 0.1724 g ± 0.0001 g, terbium green glow title complex 0.0469 g ± 0.0001 g, beryllium blue light title complex 0.0064 g ± 0.0001 g;

Take initiator Diisopropyl azodicarboxylate 0.0074 g ± 0.0001 g;

Measure methyl methacrylate 1.6 mL ± 0.1 mL;

Measure dimethyl sulfoxide (DMSO) 5 mL ± 0.1 mL;

Above material is added in beaker, be then placed in ultrasonic vibrator, vibrating dispersion is dissolved 30 min, becomes clarification mixing solutions;

mixing solutions is added in four-hole boiling flask;

opening electric heater, makes temperature in cleansing bath tub and four-hole boiling flask be increased to 75oC ± 1 oC, and constant;

open nitrogen valve, to the defeated nitrogen of four-hole boiling flask, nitrogen input speed 25 cm ³/ min;

open water circulating condensing pipe, carries out water cycle condensation;

turn on agitator, stirs, churning time 1 h;

then stop inputting nitrogen, stop water cycle condensation, stop stirring, continue to react 48 h under heating 75oC ± 1oC state;

under heating, stirring, water cycle condensation, nitrogen protection, chemical reaction will occur, reaction formula is as follows:

In formula

: containing europium terbium beryllium polymer white light fluorescent material, n: the polymerization degree 230

after reaction, become polymers soln, polymers soln is poured in beaker, then add methyl alcohol 5 mL, generate cotton-shaped white precipitate, standing 1 h, precipitates it completely;

with scissors, throw out is shredded;

anhydrous methanol washing, filtration, be placed in beaker by the throw out shredding, and adds anhydrous methanol 50 mL, stirs, washs 5 min; Then with millipore filtration, filter; Washing, filtration repeat 3 times;

vacuum-drying, is placed in quartz container by the filter cake after washing and filtering, be then placed in vacuum drying oven and be dried, drying temperature 80oC, vacuum tightness-0.08 Mpa, time of drying 24 h; After dry, become white powder;

grind, sieve, by dried agate mortar, pestle grinding for white powder, then with 600 eye mesh screens, sieve, grind, sieve and repeatedly carry out, obtain end product: containing europium terbium beryllium polymer white light fluorescent material;

(6) detect, analyze, characterize

Pattern, color and luster, chemical physics performance, luminescent properties containing europium terbium beryllium polymer white light fluorescent material to preparation detect analysis;

with XRD-5000 X-ray diffractometer, carry out morphology analysis;

with Hitachi F-4500 spectrophotofluorometer, carry out fluorometric analysis;

Conclusion: be white powder containing europium terbium beryllium polymer white light fluorescent material, chromaticity coordinates is x=0.3218, y=0.3332 under 365 nm ultraviolet excitations, is positioned at white light area;

(7) product stores

To preparation containing europium terbium beryllium polymer white light fluorescent material be stored in brown transparent Glass Containers, airtight keeping in Dark Place, waterproof, sun-proof, anti-acid-alkali salt to corrode, storing temp 20oC, relative humidity≤10 %.

Beneficial effect

The present invention compares with background technology has obvious advance, first prepares europium ruddiness title complex, terbium green glow title complex, beryllium blue light title complex, then in four-hole boiling flask, carry out polyreaction, through washing, suction filtration, dry, grinding, make containing europium terbium beryllium polymer white light fluorescent material.This preparation method's technique is advanced, and informative data is accurate, and white emitting fluorescent powder luminance purity is good, and luminous efficiency is high, and chromaticity coordinates x=0.3218, y=0.3332 under 365 nm ultraviolet excitations are the methods that desirable preparation contains europium terbium beryllium polymer white light fluorescent material.

Accompanying drawing explanation

Fig. 1 is for preparation is containing the state graph of europium terbium beryllium polymer white light fluorescent material

Fig. 2 is for containing europium terbium beryllium polymer white light fluorescent material shape appearance figure

Fig. 3 is for containing europium terbium beryllium polymer white light fluorescent material chromaticity coordinates figure

Fig. 4 is for containing europium terbium beryllium polymer white light fluorescent phosphor spectrogram

Shown in figure, list of numerals is as follows:

1, electric controller, 2, display screen, 3, pilot lamp, 4, power switch, 5, Heating temperature modulator, 6, stir modulator, 7, cleansing bath tub, 8, water-bath water, 9, four-hole boiling flask, 10, nitrogen tube, 11, dropping funnel, 12, control valve, 13, agitator, 14, water cycle prolong, 15, water-in, 16, water outlet ，17, air outlet, 18, nitrogen valve, 19, nitrogengas cylinder, 20, nitrogen, 21, reaction soln.

Embodiment

Below in conjunction with accompanying drawing, the present invention will be further described:

Shown in Fig. 1, for preparation wants correct containing europium terbium beryllium polymer white light fluorescent material state graph ，Ge Bu position, proportioning, according to the order of sequence operation according to quantity.

The value of the chemical substance that preparation is used is to determine by the scope setting in advance, with gram, milliliter, centimetre ³for measure unit.

Preparation is carried out in four-hole boiling flask containing europium terbium beryllium polymer white light fluorescent material, under heating, stirring, water-bath, water cycle condensation, nitrogen protection, completes;

Electric controller 1 top is cleansing bath tub 7, in cleansing bath tub 7, is water-bath water 8, on cleansing bath tub 7 tops, is four-hole boiling flask 9, and water-bath water 8 will flood 4/5 of four-hole boiling flask volume; On four-hole boiling flask 9 tops by the left-to-right nitrogen tube 10 that is equipped with successively, dropping funnel 11 and control valve 12, agitator, water cycle prolong 14 and water-in 15, water outlet 16， air outlet 17; On the supervisory control desk of electric controller 1, be provided with display screen 2, pilot lamp 3, power switch 4, Heating temperature modulator 5, stir modulator 6; Left part at electric controller 1 is provided with nitrogengas cylinder 19, and nitrogengas cylinder 19 connects nitrogen valve 18, nitrogen tube 10; It in four-hole boiling flask 9, is reaction soln 21.

Shown in Fig. 2, for containing europium terbium beryllium polymer white light fluorescent material shape appearance figure, known in figure: containing europium terbium beryllium polymer white light fluorescent material, to be unformed shape, crosslinked shape pattern, particle diameter≤1 μ m.

Shown in Fig. 3, for containing europium terbium beryllium polymer white light fluorescent material chromaticity coordinates figure, known in figure: x=0.3218, y=0.3332, be positioned at white light area.

Shown in Fig. 4, for containing europium terbium beryllium polymer white light fluorescent phosphor spectrogram, known in figure: the emission peak containing europium terbium beryllium polymer white light fluorescent material is positioned at 427,488,543,590,613 and 652 nm places, wherein, be positioned at the transmitting that 427 nm places belong to beryllium title complex, belong to blue emission; Be arranged in 488,543 nm places and belong to respectively terbium coordination compound terbium ion ⁵d ₄- ⁷f ₆, ⁵d ₄- ⁷f ₅energy level transition, 543 strong nm places belong to green emission; Be positioned at 590,613 and 652 nm places and belong to respectively europium complex ⁵d ₀- ⁷f ₁, ⁵d ₀- ⁷f ₂, ⁵d ₀- ⁷f ₃energy level transition, 613 strong nm places belong to red emission.

Claims (2)

1. the preparation method containing the white emitting fluorescent powder of europium terbium beryllium polymkeric substance, it is characterized in that: the chemical substance material of use is: Europium trichloride, 2-thenoyltrifluoroacetone, terbium chloride, anthranilic acid, undecylenic acid, beryllium sulfate, 2-(2-hydroxy phenyl) benzothiazole, α-methacrylic acid, methyl methacrylate, Diisopropyl azodicarboxylate, sodium hydroxide, dehydrated alcohol, anhydrous methanol, dimethyl sulfoxide (DMSO), deionized water, nitrogen, it is as follows that it prepares consumption: with gram, milliliter, centimetre ³for measure unit

Europium trichloride EuCl ₃0.3664 g ± 0.0001 g

2-thenoyltrifluoroacetone C ₈h ₅f ₃o ₂s 0.4444 g ± 0.0001 g

Terbium chloride TbCl ₃0.3734 g ± 0.0001 g

Anthranilic acid C ₇h ₇nO ₂0.4114 g ± 0.0001 g

Undecylenic acid C ₁₁h ₂₀o ₂0.9214 g ± 0.0001 g

Beryllium sulfate BeSO ₄4H ₂o 0.1771 g ± 0.0001 g

2-(2-hydroxy phenyl) benzothiazole C ₁₃h ₉nOS 0.2273 g ± 0.0001 g

α-methacrylic acid C ₄h ₆o ₂0.0845 mL ± 0.0001 mL

Sodium hydroxide NaOH 2 g ± 0.0001 g

Diisopropyl azodicarboxylate C ₈h ₁₂n ₄0.0074 g ± 0.0001 g

Methyl methacrylate C ₅h ₈o ₂1.6 mL ± 0.1 mL

Dehydrated alcohol CH ₃cH ₂oH 1000 mL ± 1 mL

Anhydrous methanol CH ₃oH 500mL ± 1mL

Dimethyl sulfoxide (DMSO) C ₂h ₆oS 5 mL ± 0.1 mL

Nitrogen N ₂10000 cm ³± 100 cm ³

Deionized water H ₂o 200 mL ± 0.1 mL

Preparation method is as follows

(1) obtain solution

preparation Europium trichloride ethanolic soln

Take Europium trichloride 0.3664 g ± 0.0001 g, measure dehydrated alcohol 5 mL ± 0.1 mL, be placed in beaker, agitator stirs 5 min, becomes the Europium trichloride ethanolic soln of 0.2 mol/L;

preparation 2-thenoyltrifluoroacetone ethanolic soln

Take 2-thenoyltrifluoroacetone 0.4444 g ± 0.0001 g, measure dehydrated alcohol 10 mL ± 0.1 mL, be placed in beaker, agitator stirs 5 min, becomes the 2-thenoyltrifluoroacetone ethanolic soln of 0.2 mol/L;

preparation terbium chloride ethanolic soln

Take terbium chloride 0.3734 g ± 0.0001 g, measure dehydrated alcohol 5 mL ± 0.1 mL, be placed in beaker, agitator stirs 5 min, becomes the terbium chloride ethanolic soln of 0.2 mol/L;

preparation anthranilic acid ethanolic soln

Take anthranilic acid 0.4114 g ± 0.0001 g, measure dehydrated alcohol 15 mL ± 0.1 mL, be placed in beaker, agitator stirs 5 min, becomes the anthranilic acid ethanolic soln of 0.2 mol/L;

the preparation beryllium sulfate aqueous solution

Take beryllium sulfate 0.1771 g ± 0.0001 g, measure deionized water 5 mL ± 0.1 mL, be placed in beaker, agitator stirs 5 min, and ultrasonic vibrator vibrates 30 min, becomes the beryllium sulfate aqueous solution of 0.2 mol/L;

preparation 2-(2-hydroxy phenyl) benzothiazole methanol solution

Take 2-(2-hydroxy phenyl) benzothiazole 0.2273 g ± 0.0001g, measure anhydrous methanol 20 mL ± 0.1 mL, be placed in beaker, agitator stirs 5 min, ultrasonic vibrator vibrates 30 min, becomes 2-(2-hydroxy phenyl) the benzothiazole methanol solution of 0.05 mol/L;

preparation undecylenic acid ethanolic soln

Take undecylenic acid 0.9214 g ± 0.0001 g, measure dehydrated alcohol 25 mL ± 0.1 mL, be placed in beaker, agitator stirs 5 min, becomes the undecylenic acid ethanolic soln of 0.2 mol/L;

preparation sodium hydroxide ethanolic soln

Weighing sodium hydroxide 2 g ± 0.0001 g, measure dehydrated alcohol 50 mL ± 0.1 mL, are placed in beaker, and agitator stirs 5 min, becomes the sodium hydroxide ethanolic soln of 1 mol/L;

(2) prepare europium ruddiness title complex

Prepare europium ruddiness title complex and carry out in there-necked flask, in heating, stirring, dropping solution process, complete;

there-necked flask is placed on electric mantle, on there-necked flask top, inserts dropping funnel, agitator, pH meter;

measure undecylenic acid ethanolic soln 15 mL ± 0.1 mL and add in there-necked flask, opening electric heater heating, Heating temperature is 50oC ± 1oC, and stirs;

europium trichloride ethanolic soln 5 mL ± 0.1 mL are joined in dropping funnel, drip, rate of addition is 1 mL/min, and stir on dropping limit, limit, and the time is 5 min;

sodium hydroxide ethanolic soln 1 mL ± 0.1 mL is added in dropping funnel, drip, rate of addition is 1 mL/min, and stir on dropping limit, limit, and regulating pH value is 4.5-5.5, reaction times 30 min;

by 2-thenoyltrifluoroacetone ethanolic soln 10 mL ± 0.1 mL, add in dropping funnel, drip, rate of addition is 1 mL/min, and stir on dropping limit, limit, and regulating pH value is 6.5-7.0;

continue reaction 180 min, in heating, stirring, dropping solution process, chemical reaction will occur,

Reaction formula is as follows:

In formula: Eu (C ₈h ₅f ₃o ₂s) ₂(C ₁₁h ₁₉o ₂) ₃: europium ruddiness title complex, NaCl: sodium-chlor

stop heating, stir, make reaction soln be cooled to 25oC with bottle, and precipitation, reaction soln obtained;

suction filtration, is placed in the Büchner funnel on filter flask by reaction soln, with millipore filtration, carries out suction filtration, obtains product filter cake on filter membrane, and waste liquid is evacuated in filter flask;

washing, suction filtration, be placed in beaker by product filter cake, adds dehydrated alcohol 50 mL, and agitator treating 5 min, then carry out suction filtration with millipore filtration; Washing, suction filtration repeat 3 times, obtain product filter cake;

vacuum-drying, is placed in quartz container by product filter cake, is then placed in vacuum drying oven dry, drying temperature 60oC, and vacuum tightness-0.08 Mpa, time of drying 6, h, obtained after being dried: europium ruddiness title complex;

(3) prepare terbium green glow title complex

Prepare terbium green glow title complex and carry out in there-necked flask, in heating, stirring, dropping solution process, complete;

there-necked flask is placed on electric mantle, on there-necked flask top, inserts dropping funnel, agitator, pH meter;

measure undecylenic acid ethanolic soln 10 mL ± 0.1 mL, add in there-necked flask, opening electric heater heating, Heating temperature is 50oC ± 1oC, and stirs;

terbium chloride ethanolic soln 5 mL ± 0.1 mL are joined in dropping funnel, drip, rate of addition is 1 mL/min, and stir on dropping limit, limit, and the time is 5 min;

sodium hydroxide ethanolic soln 1 mL ± 0.1 mL is added in dropping funnel, drip, rate of addition is 1 mL/min, and stir on dropping limit, limit, and regulating pH value is 5.5-6.5, reaction times 30 min;

by anthranilic acid ethanolic soln 15 mL ± 0.1 mL, add in dropping funnel, drip, rate of addition is 1 mL/min, and stir on dropping limit, limit, and pH value is 6.5-7.0;

continue reaction 180 min, in heating, stirring, dropping solution process, chemical reaction will occur, reaction formula is as follows:

In formula: Tb (C ₇h ₆nO ₂) ₃(C ₁₁h ₂₀o ₂) ₂: terbium green glow title complex

stop heating, stir, make reaction soln be cooled to 25oC with bottle, and precipitation, reaction soln obtained;

suction filtration, is placed in the Büchner funnel on filter flask by reaction soln, with millipore filtration, carries out suction filtration, obtains product filter cake on filter membrane, and waste liquid is evacuated in filter flask;

washing, suction filtration, be placed in beaker by product filter cake, adds dehydrated alcohol 50 mL agitator treating 5 min, then with millipore filtration, carries out suction filtration; Washing, suction filtration repeat 3 times, obtain product filter cake;

vacuum-drying, is placed in quartz container by product filter cake, is then placed in vacuum drying oven dry, drying temperature 60oC, and vacuum tightness-0.08 Mpa, time of drying 6, h, obtained after being dried: terbium green glow title complex;

(4) prepare beryllium blue light title complex

Prepare beryllium blue light title complex and carry out in there-necked flask, in heating, stirring, dropping solution process, complete;

there-necked flask is placed on electric mantle, on there-necked flask top, inserts dropping funnel, agitator, pH meter;

measure 2-(2-hydroxy phenyl) benzothiazole methanol solution 20 mL ± 0.1 mL and add in there-necked flask, opening electric heater heating, Heating temperature is 50oC ± 1oC, and stirs;

the beryllium sulfate aqueous solution 5 mL ± 0.1 mL are joined in dropping funnel, drip, rate of addition is 1 mL/min, and stir on dropping limit, limit, and the time is 5 min;

by α-methacrylic acid 0.0845 mL ± 0.0001 mL, with micro-feeder, add in dropping funnel, drip, rate of addition is 0.01 mL/min, continues reaction times 10 min;

sodium hydroxide ethanolic soln 1 mL ± 0.1 mL is added in dropping funnel, and drip stirring, rate of addition is 1 mL/min, regulating pH value is 8-9, occurs yellow-green precipitate, continues reaction 180 min, in heating, stirring, dropping solution process, will there is chemical reaction, reaction formula is as follows:

In formula: Be (C ₁₃h ₈nOS) (C ₄h ₅o ₂): beryllium blue light title complex, Na ₂sO ₄: sodium sulfate

stop heating, stir, make reaction soln be cooled to 25oC with bottle, and precipitation, reaction soln obtained;

suction filtration, is placed in the Büchner funnel on filter flask by reaction soln, uses millipore filtration suction filtration, obtains product filter cake on filter membrane, and waste liquid is evacuated in filter flask;

washing, suction filtration, be placed in beaker by product filter cake, adds dehydrated alcohol 50 mL agitator treating 5 min, then with millipore filtration, carries out suction filtration; Washing, suction filtration repeat 3 times, obtain product filter cake;

vacuum-drying, is placed in quartz container by product filter cake, is then placed in vacuum drying oven dry, drying temperature 60oC, and vacuum tightness-0.08 Mpa, time of drying 6, h, obtained after being dried: beryllium blue light title complex;

(5) preparation is containing europium terbium beryllium polymer white light fluorescent material

Preparation is carried out in four-hole bottle, under heating, stirring, water-bath, water cycle condensation, nitrogen protection, completes;

four-hole boiling flask is placed on cleansing bath tub, and the water-bath water in cleansing bath tub will flood 4/5 of four-hole boiling flask volume, on four-hole boiling flask top by left-to-right nitrogen tube, dropping funnel, agitator, the water cycle prolong of inserting successively;

by chemicals quality, than 0.015:0.05:0.03, take respectively europium ruddiness title complex 0.1724 g ± 0.0001 g, terbium green glow title complex 0.0469 g ± 0.0001 g, beryllium blue light title complex 0.0064 g ± 0.0001 g;

Take initiator Diisopropyl azodicarboxylate 0.0074 g ± 0.0001 g;

Measure methyl methacrylate 1.6 mL ± 0.1 mL;

Measure dimethyl sulfoxide (DMSO) 5 mL ± 0.1 mL;

Above material is added in beaker, be then placed in ultrasonic vibrator, vibrating dispersion is dissolved 30 min, becomes clarification mixing solutions;

mixing solutions is added in four-hole boiling flask;

opening electric heater, makes temperature in cleansing bath tub and four-hole boiling flask be increased to 75oC ± 1 oC, and constant;

open nitrogen valve, to the defeated nitrogen of four-hole boiling flask, nitrogen input speed 25 cm ³/ min;

open water circulating condensing pipe, carries out water cycle condensation;

turn on agitator, stirs, churning time 1 h;

then stop inputting nitrogen, stop water cycle condensation, stop stirring, continue to react 48 h under heating 75oC ± 1oC state;

under heating, stirring, water cycle condensation, nitrogen protection, chemical reaction will occur, reaction formula is as follows:

In formula

: containing europium terbium beryllium polymer white light fluorescent material,

N: the polymerization degree 230

after reaction, become polymers soln, polymers soln is poured in beaker, then add methyl alcohol 5 mL, generate cotton-shaped white precipitate, standing 1 h, precipitates it completely;

with scissors, throw out is shredded;

anhydrous methanol washing, filtration, be placed in beaker by the throw out shredding, and adds anhydrous methanol 50 mL, stirs, washs 5 min; Then with millipore filtration, filter; Washing, filtration repeat 3 times;

vacuum-drying, is placed in quartz container by the filter cake after washing and filtering, be then placed in vacuum drying oven and be dried, drying temperature 80oC, vacuum tightness-0.08 Mpa, time of drying 24 h; After dry, become white powder;

grind, sieve, by dried agate mortar, pestle grinding for white powder, then with 600 eye mesh screens, sieve, grind, sieve and repeatedly carry out, obtain end product: containing europium terbium beryllium polymer white light fluorescent material;

(6) detect, analyze, characterize

Pattern, color and luster, chemical physics performance, luminescent properties containing europium terbium beryllium polymer white light fluorescent material to preparation detect analysis;

with XRD-5000 X-ray diffractometer, carry out morphology analysis;

with Hitachi F-4500 spectrophotofluorometer, carry out fluorometric analysis;

Conclusion: be white powder containing europium terbium beryllium polymer white light fluorescent material, chromaticity coordinates is x=0.3218, y=0.3332 under 365 nm ultraviolet excitations, is positioned at white light area;

(7) product stores

To preparation containing europium terbium beryllium polymer white light fluorescent material be stored in brown transparent Glass Containers, airtight keeping in Dark Place, waterproof, sun-proof, anti-acid-alkali salt to corrode, storing temp 20oC, relative humidity≤10 %.

2. a kind of preparation method containing europium terbium beryllium polymer white light fluorescent material according to claim 1, it is characterized in that: preparation is carried out in four-hole boiling flask containing europium terbium beryllium polymer white light fluorescent material, under heating, stirring, water-bath, water cycle condensation, nitrogen protection, completes;

The top of electric controller (1) is cleansing bath tub (7), in cleansing bath tub (7), is water-bath water (8), on cleansing bath tub (7) top, is four-hole boiling flask (9), and water-bath water (8) will flood 4/5 of four-hole boiling flask volume; On four-hole boiling flask (9) top by the left-to-right nitrogen tube (10) that is equipped with successively, dropping funnel (11) and control valve (12), agitator (13), water cycle prolong (14) and water-in (15), water outlet (16), air outlet (17); On the supervisory control desk of electric controller (1), be provided with display screen (2), pilot lamp (3), power switch (4), Heating temperature modulator (5), stir modulator (6); Left part at electric controller (1) is provided with nitrogengas cylinder (19), and nitrogengas cylinder (19) connects nitrogen valve (18), nitrogen tube (10); In four-hole boiling flask (9), be reaction soln (21).

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