CN104674368A - Organic rare earth europium luminescent nylon and preparation method thereof - Google Patents

Organic rare earth europium luminescent nylon and preparation method thereof Download PDF

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CN104674368A
CN104674368A CN201510045052.5A CN201510045052A CN104674368A CN 104674368 A CN104674368 A CN 104674368A CN 201510045052 A CN201510045052 A CN 201510045052A CN 104674368 A CN104674368 A CN 104674368A
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phen
preparation
europium
dmpphen
luminescent material
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CN104674368B (en
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顾玲
袁欢欢
顾昕
提云崇
徐国华
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Huzhou xinbeilian Network Technology Co.,Ltd.
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NANTONG HUALUN CHEMICAL FIBER CO Ltd
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Abstract

The invention discloses organic rare earth europium luminescent nylon and a preparation method thereof. The rare earth europium complex Eu(TTA)3DmPPhen luminescent material close to nanoscale is prepared by firstly preparing a phenanthroline neutral ligand and carrying out coordination on the phenanthroline neutral ligand and rare earth Eu (III) in combination with alpha-thenoyltrifluoroacetone and adopting a method of firstly carrying out titration under atmospheric pressure and secondly carrying out reaction under high pressure. The material emits strong pure red light at 615nm in a 10-5mol/L CH2Cl2 solution. The luminescent fiber is prepared by adopting the complex as a luminescent material and carrying out compound melt spinning on the complex and PA6 (polyamide 6). When the content of the rare earth luminescent material in the fiber is 0.08%, the fiber emits stronger pure red light in a 10-5mol/L DMF (dimethyl formamide) solution and the luminescent position is still at 615nm. The luminescent fiber has the advantages of high colour purity and better spinnability.

Description

Luminous polyamide fibre of Europium and preparation method thereof
Technical field
The invention belongs to luminescent material and textile science field, particularly luminous polyamide fibre of a kind of Europium and preparation method thereof.
Background technology
Rare earth element is arranged in periodic table of elements group of the lanthanides, and because its outer electronic structure is identical, and internal layer 4f energy level is more close, and rare earth element shows a lot of unique physics and chemical property, so be used widely in optical, electrical, magnetic field.The fluorescent emission of general rare earth ion mainly comes from the f-f electron transition of 4f electronic shell, 5S 2and 5P 6electronics generally can shield 4f electron institute, and therefore the light radiation transition impact of matrix on 4f electronic shell is less.This shielding action exactly can make rare earth ion produce sharp band transmitting and longer fluorescence lifetime.
The molar extinction coefficient that usual most of trivalent rare earth ions is less, makes the fluorescence intensity of himself also not bery strong, when its fluorescence intensity can be strengthened after organic ligand and rare-earth ion coordination, and effect that Here it is " antenna ".There is several obvious advantage as luminescent substance in rare earth compounding: (a) luminous efficiency is high: the most high-luminous-efficiency of organic molecule is 25% in theory, and rare earth compounding theory can reach 100%;
B () photochromic purity is high: the luminescence of rare earth compounding is produced by the f-f transition of central ion, and its spectral bands is very narrow, emission spectrum half peak breadth (<10nm); C () modified ligand does not affect glow color: the emission spectrum of rare earth compounding is different from the emission spectrum of general transient metal complex, the character such as the migration of general workability, solubility, charge migration and carrier in order to improve complex, often will carry out modification to meet above-mentioned requirements to part.These advantages have been widely used in the field such as phosphor, fluorescent lamp, laser dye, electroluminescent material of color monitor.
Eu (III) complex has obtained researcher as the photic or red electroluminescent phosphor material that a class is excellent and paid close attention to.A key point of research Eu (III) complex is design and optimization to part, and affected the required voltage of the luminous efficiency of complex, stability and device by the change of part, therefore the performance of change to material of part has far-reaching influence.A Rare Earth Europium Complex luminescent material Eu (L) prepared by document (Noto M, Irie K, Era M.Chem.Lett, 2011,320) 3phen solid fluorescence efficiency is 50%.Cavity transmission group triphenylamine introduced by document (Sun M, Xin H, Wang, et al.Chem.Commun, 2003,702) on neutral ligand, that regulate electronics with transmission that is hole, prepared luminescent material Eu (DBM) 3(TPIP) obtain good fluorescent effect, the device brightness of assembling is up to 1305cd/m 2, maximum fluorescence productive rate is 1.44lm/W.Document (Ling Q.D, Cai Q.J, Huang W et al.Mater Chem, 2004,14,2741-2746) prepare side chain type macromolecule rare-earth europium luminescent material, the hole transport character of carbazole is utilized to be polymerized with emitting complexes, but this kind of material is with side chain, and during polymerization, molecular weight difficulty controls, and is difficult to directly to carry out spinning and prepares luminescent fibre.
The preparation of luminescent fibre is generally be doped in high polymer by luminescent material, makes luminescent fibre through spinning.Its method is roughly divided into: solution-polymerized SBR, melt spinning, face coat etc.Solution-polymerized SBR requires that luminescent material can be dissolved in solvent, and melt spinning requires that fluorescent material is stablized, and heating not easily decomposition, resistance to oxidation etc., show that coating then requires that luminescent material and fiber surface have good affinity.
Have relevant report to the exploitation of luminescent fibre in recent years, some seminars utilize electrostatic spinning technique to prepare some rear-earth-doped polymer nanofiber and inorganic nano-fibers.The people such as Luo Jun have prepared the doping of series of rare earth long persistence luminescent silicate material and have carried out electrostatic spinning (China Patent Publication No.: CN103938297A in the fibre, application number: 201410174370.7), this fluorescent fiber, through visible ray or UV-irradiation 1-10 minute, can be launched blue at 470nm place.Fiber prepared by this kind of luminescent material has the effect of extinction energy storage, has long-persistence luminous feature; General prepared inorganic silicate luminescent material increasing particle size, is doped to spinnability in fiber poor, and in false proof and electroluminescent etc. existing defects.The people (X.M.Sui, C.L.Shao, Y.C.Liu et al.Appl.Phys.Lett., 2005,87,113-115) such as Sui X.M. have prepared ZnO/PVA composite fibre, can launch white light.Eu (BA) in document (H.Zhang, H.W.Song, B.Dong et al.J.Phy.Chem, 2008,112,9155-9162) 3(TPPO) 2be entrained in PVP (Poly Vinyl Pyrrolidone, polyvinylpyrrolidone) and carry out composite spinning, prepared that bleach-resistant ability is strong, the composite nano fiber of stable luminescence; Because the level-density parameter situation of part and Eu (III) ion is not fine, cause the luminous intensity of complex not to be very high.Chinese patent CN101381901A, application number: 200810042269.0, has prepared a series of organic molecule fluorescent chemicals and has been doped in polypropylene and carries out melt spinning, prepared the polypropylene luminescent fibre of good, the different glow color of luminescent properties; This kind of fiber prepared with pure organic molecule, oxidative resistance, excitation, luminous efficiency and luminous intensity are poor.
Summary of the invention
Provide hereinafter about brief overview of the present invention, to provide about the basic comprehension in some of the present invention.Should be appreciated that this general introduction is not summarize about exhaustive of the present invention.It is not that intention determines key of the present invention or pith, and nor is it intended to limit the scope of the present invention.Its object is only provide some concept in simplified form, in this, as the preorder in greater detail discussed after a while.
The object of the embodiment of the present invention is the defect for above-mentioned prior art, provides a kind of preparation method under UV-irradiation or electroluminescent condition with the luminous polyamide fibre of efficient, that luminous intensity is high Europium.
To achieve these goals, the technical scheme that the present invention takes is:
A preparation method for the luminous polyamide fibre of Europium, comprises the following steps:
(1) prepare Europium complex luminescent material, its chemical formula is C 24h 16euN 4sF 3o 2, molecular formula is Eu (TTA) 3dmPPhen, wherein TTA is: α-thiophene trifluoro formyl acetone, and DmPPhen is: 2,3-dimethyl pyrazine is [1,10] Phen also, and structural formula is:
(2) machine Rare Earth Europium Complex luminescent material and PA6 (Polyamide 6, polycaprolactam) are cut into slices carry out blended, then obtain luminous polyamide fibre through melt spinning.
The present invention reoffers the luminous polyamide fibre of a kind of Europium, prepares according to above-mentioned preparation method.
Compared with prior art, the invention has the beneficial effects as follows:
1) triplet and Eu (III) ion is prepared 5d 0the part DmPPhen that energy level effectively mates, makes the luminous efficiency of prepared Rare Earth Europium Complex, luminous intensity effectively improves, and heat endurance, the oxidative resistance of complex strengthen.The raising of luminous intensity and efficiency effectively can reduce the addition of complex, breaks end, around roller, improves spinnability when reducing spinning.
2) the complex grain diameter adopting synthesis under normal pressure obtained is larger, the present invention adopts after the complete part of normal pressure titration, again solution is proceeded to autoclave insulation reaction, utilize solvent heat can prepare complex close to nanoscale, can reduce when cutting into slices carry out composite spinning with PA6 and break end, around problems such as rollers.
3) the present invention adopts and first prepares luminescent material master batch and cut into slices with PA6 after drying and carry out composite spinning, luminescent material can be made to be dispersed in uniformly in polymeric system, produce Fluorescence-quenching under preventing high concentration.
4) the present invention passes through melt spinning method, through setting specific process conditions, continuablely carry out POY (pre-oriented yarn) and UDY (non-oriented silk) spinning, obtained fiber thickness evenly, powerful suitable Europium luminescent fibre.
5) the present invention is by preparing organic rare-earth ligand luminescent material, obtains the new way of the luminescent fibre that preparation luminous intensity is good, good dispersion, chemical stability are high, fiber number is even, brute force is suitable.Important application can be had in the field such as false proof, clothes, seabed operation, molecular probe, biochip, communication, solar cell.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is organic RE europium complex Eu (TTA) 3the synthetic route chart of DmPPhen;
Fig. 2 is Rare Earth Europium Complex Eu (TTA) prepared by the inventive method 3the infrared spectrum of DmPPhen and part DmPPhen, wherein a is Eu (TTA) 3dmPPhen, b are DmPPhen;
Fig. 3 is Rare Earth Europium Complex Eu (TTA) prepared by the inventive method 3the nuclear magnetic spectrogram of DmPPhen;
Fig. 4 is Rare Earth Europium Complex Eu (TTA) prepared by the inventive method 3dmPPhen is 10 in concentration -5the CH of mol/L 2cl 2fluorescent exciting spectrogram in solution;
Fig. 5 is Rare Earth Europium Complex Eu (TTA) prepared by the inventive method 3dmPPhen's is 10 in concentration -5the CH of mol/L 2cl 2fluorescence emission spectrogram in solution;
Fig. 6 is Rare Earth Europium Complex Eu (TTA) prepared by the inventive method 3the composite fibre of DmPPhen and PA6, when content is 0.08% to rare earth luminescent material in the fibre, concentration is 10 -5fluorescent exciting spectrogram in DMF (Dimethyl Formamide, the DMF) solution of mol/L;
Fig. 7 is Rare Earth Europium Complex Eu (TTA) prepared by the inventive method 3the composite fibre of DmPPhen and PA6, when content is 0.08% to rare earth luminescent material in the fibre, concentration is 10 -5fluorescence emission spectrogram in the DMF solution of mol/L.
Wherein:
Abscissa Wavenumbers in Fig. 2 represents wave number;
In Fig. 4, Fig. 5, Fig. 6 and Fig. 7, abscissa Wavelength represents wavelength, and ordinate Intensity represents intensity.
Detailed description of the invention
For making the object of the embodiment of the present invention, technical scheme and advantage clearly, below in conjunction with the accompanying drawing in the embodiment of the present invention, technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is the present invention's part embodiment, instead of whole embodiments.The element described in an accompanying drawing of the present invention or a kind of embodiment and feature can combine with the element shown in one or more other accompanying drawing or embodiment and feature.It should be noted that for purposes of clarity, accompanying drawing and eliminate expression and the description of unrelated to the invention, parts known to persons of ordinary skill in the art and process in illustrating.Based on the embodiment in the present invention, those of ordinary skill in the art, not paying the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
The invention provides the preparation method of the luminous polyamide fibre of a kind of Europium, comprise the following steps:
(1) prepare Europium complex luminescent material, its chemical formula is C 24h 16euN 4sF 3o 2, molecular formula is Eu (TTA) 3dmPPhen, wherein TTA is: α-thiophene trifluoro formyl acetone, and DmPPhen is: 2,3-dimethyl pyrazine is [1,10] Phen also, and structural formula is:
The construction unit of complex is as follows:
(2) machine Rare Earth Europium Complex luminescent material and PA6 (Polyamide 6, polycaprolactam) are cut into slices carry out blended, then obtain luminous polyamide fibre through melt spinning.
Particularly, the preparation method of Europium complex luminescent material, comprises the following steps:
(1) preparation of part 2,3-dimethyl pyrazine also [1,10] Phen:
A, 1,10-Phen and potassium bromide are put into flask, at-8 DEG C to-12 DEG C, drip volume ratio is the concentrated sulfuric acid of 3:1-2 and the mixed acid solution of red fuming nitric acid (RFNA), at-8 DEG C to-12 DEG C, react 0.5-1.5h, is heated to 75-95 DEG C of reaction 130-150min; In reactant liquor instillation ice cube, rapid stirring, adjust pH to 6-7 with NaOH, obtain neutralization solution, with neutralization solution described in solvent extraction, decompression distillation obtains yellow product 5,6-diketone-1,10-Phen;
Every 1g 1,10-Phen correspondence adds 0.4-1g potassium bromide;
The mixed acid solution that every 1g1,10-Phen correspondence adds is 20-30ml;
The solvent of described extraction is carrene or chloroform;
B, by 5,6-diketone-1,10-Phen, hydroxylamine hydrochloride and BaCO 310-13h is reacted, distillation, the watery hydrochloric acid washing of solid 0.2-0.3mol/L, suction filtration in the ethanol of 70-80 DEG C, with the first mixed liquor washing several, then vacuumize, vacuum is 0.09MPa, and baking temperature is 60-90 DEG C; Drying time is 5-12h; Obtain light yellow product 5,6-dioxime-1,10-Phen;
Described 5,6-diketone-1,10-Phens, hydroxylamine hydrochloride and BaCO 3mass ratio be 1:0.7-2:0.7-2;
Every 0.84g5,6-diketone-1,10-Phen correspondence adds 40-60ml ethanol, and the reaction time is 10-13h;
Described first mixed liquor is ethanol and ether or methyl alcohol and ether, and the ethanol in described first mixed liquor or the volume ratio of methyl alcohol and ether are 1:2-6;
The first mixed liquor that every 0.84g5,6-diketone-1,10-Phen correspondence adds is 15-30ml;
C, 5,6-dioxime-1,10-Phen is put into absolute ethyl alcohol, obtain alcoholic solution, be heated to 70-80 DEG C under inert gas shielding, getting sodium hydrosulfite, to be dissolved in content be in the ammonia spirit of 3%-5%, obtain the second mixed liquor, the second mixed liquor is added in above-mentioned alcoholic solution; Add the second mixed liquor with first time equivalent after 15-45min, and react 1.5-2h at 75-85 DEG C; Be cooled to normal temperature, suction filtration, with distilled water washing several, then wash for several times with ethanol or acetone, vacuumize, vacuum is 0.09MPa, and baking temperature is 60-90 DEG C, and drying time is 4-10h; Obtain golden yellow 5,6-diamines-1,10-Phen;
Every 1mmol 5,6-dioxime-1,10-Phen correspondence puts into 5-10ml ethanol;
The mol ratio of described 5,6-dioxime-1,10-Phens and sodium hydrosulfite is 1:3-5;
It is in the ammonia spirit of 3%-5% that every 1mmol sodium hydrosulfite is dissolved in 0.6-1ml mass percent concentration;
Every 1mmol 5,6-dioxime-1,10-Phen correspondence adds second mixed liquor of 2.5-4.5ml;
D, 5,6-diamines-1,10-Phen and 3,4-diacetyl are reacted 10-13h, decompression distillation at normal temperatures, the mixed liquor of solids with methanol and water washs, vacuumize, and vacuum is 0.09MPa, and baking temperature is 60-90 DEG C, and drying time is 5-12h; Obtain white powder 2,3-dimethyl pyrazine also [1,10] Phen;
The mass ratio of described 5,6-diamines-1,10-Phens and 3,4-diacetyl is 1.5-3:1;
The volume ratio of described methyl alcohol and water is 1:8-12;
The cumulative volume that every 1g5,6-diamines-1,10-Phen correspondence adds methyl alcohol and water is 8-12ml.
(2) organic RE europium complex Eu (TTA) 3the preparation of DmPPhen luminescent material:
By Eu 2o 3with concentrated hydrochloric acid mixing, Eu 2o 3be 1:1-10 with the mass ratio of concentrated hydrochloric acid, evaporate to dryness on electric jacket, is then mixed with ethanolic solution; Get a certain amount of Phen neutral ligand DmPPhen and put into flask, drip and the equimolar EuCl of Phen neutral ligand DmPPhen at 55-60 DEG C 3ethanolic solution, stir 40-80 minute; The ethanolic solution of the HTTA of dropping Phen neutral ligand DmPPhen, 3 times of molar weights, adjust pH to 6-7 with triethylamine, proceed to autoclave, design temperature is 120-160 DEG C, and pressure is less than 10MPa, insulation reaction 5-10h; Pressure is greater than 0.1MPa, decompression distillation, and solid is separated out in cooling, suction filtration, alcohol wash several, washed several times with water, vacuumize, and vacuum is 0.09MPa, and baking temperature is 60-90 DEG C, and drying time is 8-12h; Obtain nano level blush powder.
The preparation process of the luminous polyamide fibre of Europium of the present invention is divided into two parts and completes, and first prepares rare-earth europium luminescent material, is then prepared into Masterbatch, then to cut into slices melt spinning with PA6.Obtain can launching the luminous polyamide fibre of Europium of pure ruddiness under UV-irradiation.
Specifically comprise the following steps:
(1) Europium complex luminescent material is fully mixed with PA6 master batch, adopt screw extruder to prepare Masterbatch, vacuumize, make its moisture content be less than 20ppm; Europium complex luminescent material accounts for the 0.3%-30% of Masterbatch gross mass.The described Masterbatch prepared adopts vacuumize, and its vacuum < 0.095MPa, dry temperature are 100-140 DEG C, the dry time is 10-16h.
(2) PA6 slices synthesis method is carried out drying to vacuum drum; Dry temperature is 120-180 DEG C, and vacuum is less than 0.095MPa, and drying time is 10-16h.
(3) Masterbatch and dried PA6 are cut into slices and carry out Homogeneous phase mixing by a certain percentage, the weight ratio that described Masterbatch and PA6 cut into slices is 1:20-100, makes organic RE europium complex Eu (TTA) 3the content of DmPPhen is 0.05-5%; Under specific spinning process condition, through screw rod melt extruded, filtration, static mixing, spray silk, slow cooling, drawing-off and package, prepare recombination luminescence fiber;
The present invention, by preparation Phen neutral ligand, makes its triplet and rare earth Eu 3+energy level match, thus make that prepared new complexes has efficiently under UV-irradiation or electroluminescent condition, luminous intensity is high, launch pure ruddiness, Heat stability is good, Europium complex luminescent material that grain diameter is little.
The present invention by adopting melt spinning method, prepare luminous intensity high, launch pure ruddiness, the luminous polyamide fibre of good spinnability.Under UV-irradiation, luminous polyamide fibre launches pure ruddiness at 615nm place.
The present invention reoffers the luminous polyamide fibre of a kind of Europium, prepares according to above-mentioned preparation method.
The present invention has prepared a kind of Phen neutral ligand and has carried out coordination in conjunction with α-thiophene trifluoro formyl acetone and rare earth Eu (III), adopt first normal pressure titration, the method for rear reaction under high pressure prepares the Rare Earth Europium Complex Eu (TTA) close to nanoscale 3dmPPhen luminescent material.This material is 10 in concentration -5the CH of mol/L 2cl 2in solution, 615nm place launches very strong pure ruddiness.Adopt this complex to carry out composite molten spinning as luminescent material and polycaprolactam (PA6) and prepare luminescent fibre.When content is 0.08% to rare earth luminescent material in the fibre, be 10 in concentration -5launch stronger pure ruddiness in the DMF solution of mol/L, luminous position is still 615nm place.This luminescent fibre is that a kind of excitation is high, the good luminescent fibre of spinnability.
Efficient, color prepared by the present invention pure, good stability, particle diameter be nano level organic RE luminescent material be applied to preparation efficiently, the luminescent fibre of good spinnability has practical significance.
Orgnic RE complex Eu (TTA) of the present invention 3recombination luminescence fiber prepared by DmPPhen and PA6, this fiber is nontoxic, without radiocontamination, can have important application in fields such as false proof, lighting clothes, seabed operation, molecular probe, the biochip of high-grade goods, communication, solar cells after processing.
Luminescent fibre prepared by the embodiment of the present invention, Europium luminescent material used is Eu (TTA) 3dmPPhen, macromolecular material is PA6.
Below by specific embodiment, the present invention is described further.
Embodiment 1
Rare Earth Europium Complex Eu (TTA) 3the preparation process of DmPPhen is as follows:
The synthesis of 1,10-Phendione (compound 1): weighing 1g 1,10-Phen and 0.6g potassium bromide add in two mouthfuls of flasks of 100mL respectively, puts into cryosel bath flask and is cooled to-10 DEG C.Measuring the 16mL concentrated sulfuric acid pours in the beaker of 200mL, then measures 8ml red fuming nitric acid (RFNA) with graduated cylinder.Under cryosel bath condition, slowly in beaker, drip red fuming nitric acid (RFNA) with dropper, drip and stir with glass bar, drip about about 30min consuming time, smolder if drip too fast meeting.Acid solution prepares rear beginning and slowly drips in flask, under dropping process remains on-10 DEG C of condition of ice bath, approximately drips about 0.5h.Then then temperature programming is to 85 DEG C for ice bath reaction 1h, and insulation reaction 130min, is cooled to normal temperature after reaction terminates.Ice bath put into by the beaker separately getting a 500ml, in beaker, then drop into the ice cube frozen in advance, and reacted solution is slowly added drop-wise on ice cube, drips and exerts oneself to stir.Take about 30g NaOH wiring solution-forming, neutralization reaction liquid, have ice in N-process in moment maintenance system, and firmly stir, about about 1h neutralizes complete, neutralization to about pH value 6-7, stir three minutes constant to pH value.Use CH 2cl 2extraction neutralization solution, anhydrous magnesium sulfate drying extract, then distillation extraction liquid, obtains yellow powder, and then obtain needle-like yellow product 0.942g with ethyl alcohol recrystallization, productive rate is: 94.2%, m.p=251-252 DEG C, 1h NMR (400MHz, CDCl 3): δ 9.14 (d, J=4.6Hz, 2H), 8.52 (d, J=7.9Hz, 2H), 7.61 (dd, J=7.7,4.7Hz, 2H) .IR (KBr): 3062,1685,1577,1562,1461,1413,1317,1294,1207,1116,1010,925,808cm -1.
The synthesis of 1,10-Phen-5,6-dioxime (compound 2): add the dried hydroxylamine hydrochloride of 0.84g compound 1,1.18g brium carbonate and 1.2g in 100mL single port flask, then add 60ml absolute ethyl alcohol.Start heat temperature raising, be warming up to backflow and continue reaction 12h, stop reaction, reaction unit is made into distilling apparatus and carries out decompression distillation.Get the concentrated hydrochloric acid 4.16mL of 12mol/L, be made into the watery hydrochloric acid of 0.25mol/L, the hydrochloric acid measuring 20mL preparation is poured in flask, carries out suction filtration after stirring at normal temperature 30min.The mixed liquor 20ml of filter cake methyl alcohol and ether 1:5 washs three then vacuum dryings, and vacuum is 0.09MPa, and baking temperature is 65 DEG C; Drying time is 10h; Finally obtain product as light yellow solid 0.76g, productive rate 90.4%, m.p=235-236 DEG C.
5; 6-diamines-1; the preparation of 10-Phen (compound 3): by 6mmol 5; 6-dioxime-1,10-Phen puts into 40ml absolute ethyl alcohol, obtains alcoholic solution; 75 DEG C are heated under inert gas shielding; getting 25mmol sodium hydrosulfite, to be dissolved in 20ml content be in the ammonia spirit of 5%, obtains the second mixed liquor, added in above-mentioned alcoholic solution by 20ml second mixed liquor fast.Add same above-mentioned 20ml second mixed liquor when seeing that yellow solid matter is separated out after 45min, and react 2h at 80 DEG C.Be cooled to normal temperature, suction filtration, wash 3 times with distilled water, then wash 3 times with ethanol, vacuumize, vacuum is 0.09MPa, and baking temperature is 65 DEG C; Drying time is 5h; Obtain bright yellow solid product, productive rate 76.0%, m.p>350 DEG C, 1h NMR (400MHz, DMSO): δ 8.76 (m, 2H), 8.60 (m, 2H), 7.58 (m, 2H), 5.31 (s, 4H) .IR (KBr): 3371,3263,2594,1654,1608,1566,1483,1460,1433,1410,1349,1303,1280,1123,1074,1006,799,650,624,478.
The synthesis of 2,3-dimethyl pyrazine also [2,3-f] [1,10] ferrosin (DmPPhen): weigh 0.52g compound 3 and add in the flask of 150ml, add 75mL absolute ethyl alcohol.Measure 0.21g 3,4-diacetyl and be made into 10mL ethanolic solution, under normal temperature, in there-necked flask, slowly drip 3,4-diacetyl, drip and terminate rear continuation normal-temperature reaction, stop after reaction 12h.Then decompression evaporates solvent, and solid product is poured in the solution of 11ml (methyl alcohol: water=1:10) and washed, and then filters, and filter cake is admixed silica gel and carried out post separation after drying; First use benzinum: ethyl acetate=3:1 crosses post, then tune up polarity ethyl acetate: methyl alcohol=5:1.Eluent decompression evaporates, and solid is recrystallized again, dried in vacuo overnight at 75 DEG C, final product as white needles 0.47g, and productive rate is: 64.4%, m.p=281-282 DEG C, 1h NMR (400MHz, CDCl3): δ 9.49 (t, J=27.1Hz, 2H), 9.36 (m, 2H), 7.81 (dd, J=7.9,4.4Hz, 2H), 2.87 (s, 6H) .IR (KBr): 3417,1573,1513,1463,1421,1388,1342,1253,1213,1177,1121,1074,1010,979,816,744,713,693,637,572,445.
Complex Eu (TTA) 3the synthesis of DmPPhen: add 0.67g α-thiophene trifluoro formyl acetone in there-necked flask, 20ml absolute ethyl alcohol, stir and be heated to 60 DEG C.The ethanolic solution of the Europium chloride that slow dropping prepares.Then drip the ethanolic solution of NaOH, regulate PH to 6-7, neutralization terminates rear insulation reaction 1h.Weighing 0.26g DmPPhen is dissolved in 20ml absolute ethyl alcohol, slowly drops in flask, drips after terminating, and picks solution point to filter paper observes under uviol lamp launch very strong ruddiness with glass bar.Adjust ph is 6-7, then proceeds to autoclave, design temperature 140 DEG C, and pressure is set to 1MPa, insulation reaction 6h, and reaction terminates rear solvent concentration and separates out to about 15ml adularescent solid.Carry out suction filtration after being cooled to room temperature, filter cake first uses absolute ethanol washing 3 times, then spends deionized water three times.Then use ethyl alcohol recrystallization, 70 DEG C of vacuumize 8h, obtain blush powder 0.79g.Productive rate: 71.3%.m.p＝279-281℃。
The infrared spectrum of complex is as Fig. 1: the characteristic absorption peak ν of part α-thiophene trifluoro formyl acetone (HTTA) c=O(1656cm -1) after coordination, move to 1625cm -1place.HTTA part, respectively at 1305cm after coordination -1and 1142cm -1there is ν in place as (CF3)and ν s (CF3)characteristic absorption peak.And ν c=C(thiphene ring) and ν c-Hthe characteristic absorption peak of (thiphene ring) is respectively at 1353cm -1and 1061cm -1place occurs.ν c-Scharacteristic peak appear at 722cm -1, these absolutely prove α-thiophene trifluoro formyl acetone coordination success.For the stretching vibration red shift of DmPPhen part its C=N after coordination to 1478cm -1.561cm in addition -1one absworption peak at place is the absworption peak of N-Eu, and these results confirm that coordination occurs DmPPhen.The nuclear magnetic data of complex: 1hNMR (400MHz, CDCl 3): δ 11.66 (s, 2H), 11.39 (s, 2H), 10.2 (s, 2H), 6.99 (d, J=4.4Hz, 3H), 6.51 (s, 3H), 6.05 (d, J=75.2Hz, 3H), 3.25 – 2.64 (m, TTA-3H, CH 3-6H).Be theoretical value: Anal.calcd.C:44.58 (44.66) in elementary analysis bracket, H:2.17 (2.25), N:5.10 (5.21).
Fig. 4 is complex is 10 in concentration -5the CH of mol/L 2cl 2fluorescent exciting spectrogram in solution, complex presents wider bands of a spectrum between 260nm-420nm, and maximum excitation wavelength is 373nm.
Fig. 5 is complex is 10 in concentration -5the CH of mol/L 2cl 2fluorescent exciting spectrogram in solution is from emission spectrum, and complex has occurred Eu at 590nm (orange red photochromic), 615nm (pure ruddiness) and 651nm place 3+characteristic emission peak, and half peak breadth is narrower.Wherein the emission peak at 590nm and 615nm place is europium (III) respectively 5d 0→ 7f 1transition and 5d 0→ 7f 2transition.The spike that 615nm place is very strong is far longer than the peak at other two places, illustrates that complex has very strong monochromaticjty.Find out from the intensity of fluorescence spectra emission light, show very outstanding " working in coordination with " effect after DmPPhen part and Eu (III) coordination, have very strong spike at 615nm place, illustrate that made complex is a kind of well red illuminating material.
The preparation of ultraviolet irradiation luminous PA6 fiber, its process is as follows:
Fully mixed with PA6 master batch by the nanoscale luminescent material of above-mentioned preparation, employing double screw extruder prepares the Masterbatch containing organic rare-earth ligand 5%, and vacuum 105 DEG C of dry 12h make its moisture content be less than 20ppm.
PA6 slices synthesis method is carried out drying to vacuum drum, and design temperature is 150 DEG C, and vacuum is 0.095MPa, drying time 12h.
Dried material feeds single screw extrusion machine with the Masterbatch with rare earth luminescent material simultaneously, and the feed quantity of Masterbatch controls make rare earth luminescent material account for 0.08% of whole inventory.Screw rod is through variable frequency regulating speed control melt outlet pressure.
Material after Screw Extrusion makes melt mixed even through static mixer, is then assigned to spinning manifold, and setting spinning body temperature is 275 DEG C.Blend melt carries out spray silk through spinnerets.
Lateral blowing cooling forming, setting lateral blowing humidity 75%, wind speed 0.40-0.45m/s.High-speed winding is carried out again, the luminous polyamide fibre of obtained POY after oil nozzle oils.
Fig. 6 is rare earth luminescent material when content is 0.08% in the fibre, is 10 in concentration -5fluorescent exciting spectrogram in the DMF solution of mol/L.Composite fibre presents wider bands of a spectrum between 263-375nm, and maximum excitation wavelength is 342nm.
Fig. 7 is rare earth luminescent material when content is 0.08% in the fibre, is 10 in concentration -5fluorescence emission spectrogram in the DMF solution of mol/L.The fluorescence emission spectrum major embodiment of composite fibre is the characteristic emission (590nm (orange red light) and 615nm (pure ruddiness)) of Eu (III).The position of emission peak does not change in composite fibre, and still in narrow emission, the composite fibre prepared by explanation has very high excitation.
Embodiment 2
The present embodiment is only described the preparation of the luminescent fibre under the luminescent material of different content and different spinning process condition, and the preparation method of its luminescent material is with embodiment 1, and the preparation process of luminescent fibre is as follows:
Fully mixed with PA6 master batch by the nanoscale luminescent material of above-mentioned preparation, employing double screw extruder prepares the Masterbatch containing organic rare-earth ligand 5%, and vacuum 120 DEG C of dry 10h make its moisture content be less than 20ppm.
PA6 slices synthesis method is carried out drying to vacuum drum, and design temperature is 120 DEG C, and vacuum is 0.095MPa, drying time 16h.
Dried material feeds single screw extrusion machine with the Masterbatch with rare earth luminescent material simultaneously, and the feed quantity of Masterbatch controls make rare earth luminescent material account for 0.08% of whole inventory.Screw rod is through variable frequency regulating speed control melt outlet pressure.
Material after Screw Extrusion makes melt mixed even through static mixer, is then assigned to spinning manifold, and setting spinning body temperature is 280 DEG C.Blend melt carries out spray silk through spinnerets.
Lateral blowing cooling forming, setting lateral blowing humidity 75%, wind speed 0.40-0.45m/s.High-speed winding is carried out again, the luminous polyamide fibre of obtained POY after oil nozzle oils.
Embodiment 3
The preparation method of the luminous polyamide fibre of Europium:
Specifically comprise the following steps:
The preparation of Europium complex luminescent material:
(1) preparation of part 2,3-dimethyl pyrazine also [1,10] Phen:
A, be that 1, the 10-Phen of 1:1 and potassium bromide put into flask by mass ratio, at-8 DEG C, drip volume ratio is the concentrated sulfuric acid of 3:1 and the mixed acid solution of red fuming nitric acid (RFNA), and the mixed acid solution that every 1g 1,10-Phen correspondence adds is 25ml; At-8 DEG C, react 1.5h, be heated to 90 DEG C of reaction 130min; In reactant liquor instillation ice cube, rapid stirring, adjust pH to 6-7 with NaOH, obtain mixed solution, with mixed solution described in chloroform extraction, decompression distillation obtains yellow product 5,6-diketone-1,10-Phen;
B, be 5,6-diketone-1, the 10-Phens of 1:2:1, hydroxylamine hydrochloride and BaCO by mass ratio 3in the ethanol of 79 DEG C, react 13h, it is 40ml that every 0.84g 5,6-diketone-1,10-Phen correspondence adds ethanol; Distillation, the watery hydrochloric acid washing of solid 15ml, 0.2mol/L, suction filtration, with the first mixed liquor washing several, described first mixed liquor is ethanol and ether, and the ethanol in described first mixed liquor and the volume ratio of ether are 1:6; The first mixed liquor that every 0.84g 5,6-diketone-1,10-Phen correspondence adds is 15ml; Vacuumize again, vacuum is 0.09MPa, and baking temperature is 75 DEG C; Drying time is 8h; Obtain light yellow product 5,6-dioxime-1,10-Phen;
C, 5,6-dioxime-1,10-Phen is put into absolute ethyl alcohol, every 1mmol 5,6-dioxime-1,10-Phen correspondence puts into 10ml ethanol; Obtain alcoholic solution, be heated to 80 DEG C under inert gas shielding, it is in the ammonia spirit of 3% that the sodium hydrosulfite getting 5,6-dioxime-1,10-Phen, 5 times of molar weights is dissolved in content, obtains the second mixed liquor, is added by the second mixed liquor in above-mentioned alcoholic solution; Add the second mixed liquor with first time equivalent after 30min, and react 2h at 79 DEG C; Be cooled to normal temperature, suction filtration, with distilled water washing several, then wash for several times with acetone, vacuumize, vacuum is 0.09MPa, and baking temperature is 75 DEG C, and drying time is 6h; Obtain golden yellow 5,6-diamines-1,10-Phen;
Every 1mmol sodium hydrosulfite is dissolved in the ammonia spirit that 0.75ml mass percent concentration is 3%; Every 1mmol 5,6-dioxime-1,10-Phen correspondence adds second mixed liquor of 3ml;
D, be 5 of 3:1 by mass ratio, 6-diamines-1,10-Phen and 3,4-diacetyl react 13h, decompression distillation at normal temperatures, the mixed liquor of solids with methanol and water washs, the volume ratio of methyl alcohol and water is 1:8, vacuumize, and vacuum is 0.09MPa, baking temperature is 75 DEG C, and drying time is 10h; Obtain white powder 2,3-dimethyl pyrazine also [1,10] Phen;
Every 1g 5,6-diamines-1,10-Phen correspondence adds the cumulative volume 11ml of methyl alcohol and water.
Organic RE europium complex Eu (TTA) 3the preparation of DmPPhen luminescent material:
Be the Eu of 1:10 by mass ratio 2o 3with concentrated hydrochloric acid mixing, evaporate to dryness on electric jacket, is then mixed with ethanolic solution; Get a certain amount of Phen neutral ligand DmPPhen and put into flask, drip and the equimolar EuCl of Phen neutral ligand DmPPhen at 60 DEG C 3ethanolic solution, stir 40 minutes; The ethanolic solution of the HTTA of dropping Phen neutral ligand DmPPhen, 3 times of molar weights, adjust pH to 6-7 with triethylamine, proceed to autoclave, at 120 DEG C, pressure is set to 2MPa, insulation reaction 10h; Decompression distillation, solid is separated out in cooling, suction filtration, and for several times, washed several times with water, vacuumize 8h at 80 DEG C, obtains nano level blush powder to alcohol wash.
Europium complex luminescent material is fully mixed with PA6 master batch, adopts screw extruder to prepare Masterbatch, vacuumize, make its moisture content be less than 20ppm; Europium complex luminescent material accounts for 10% of Masterbatch gross mass.The vacuum < 0.095MPa adopted after preparing Masterbatch, dry temperature are 115 DEG C, the dry time is 10h.
Masterbatch and dried PA6 are cut into slices and carry out Homogeneous phase mixing by a certain percentage, the weight ratio that described Masterbatch and PA6 cut into slices is 1:20, makes organic RE europium complex Eu (TTA) 3the content of DmPPhen is 0.5%; Under specific spinning process condition, squeeze melt extruded, filtration, static mixing through screw rod, be then assigned to spinning manifold, setting spinning body temperature 280 DEG C; Blend melt carries out spray silk through spinnerets.Lateral blowing cooling forming, setting lateral blowing humidity 70%, wind speed 0.40m/s; Low-speed rolling is carried out again around, the luminous polyamide fibre of obtained POY after oil nozzle oils.
Last it is noted that above embodiment is only in order to illustrate technical scheme of the present invention, be not intended to limit; Although with reference to previous embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that: it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein portion of techniques feature; And these amendments or replacement, do not make the essence of appropriate technical solution depart from the spirit and scope of various embodiments of the present invention technical scheme.

Claims (10)

1. a preparation method for the luminous polyamide fibre of Europium, is characterized in that, comprise the following steps:
(1) prepare Europium complex luminescent material, its chemical formula is C 24h 16euN 4sF 3o 2, molecular formula is Eu (TTA) 3dmPPhen, wherein TTA is: α-thiophene trifluoro formyl acetone, and DmPPhen is: 2,3-dimethyl pyrazine is [1,10] Phen also, and structural formula is:
(2) machine Rare Earth Europium Complex luminescent material and PA6 (Polyamide 6, polycaprolactam) are cut into slices carry out blended, then obtain luminous polyamide fibre through melt spinning.
2. the preparation method of the luminous polyamide fibre of Europium according to claim 1, is characterized in that, comprise the following steps:
(1) preparation of part 2,3-dimethyl pyrazine also [1,10] Phen:
A, 1,10-Phen and potassium bromide are put into flask, at-8 DEG C to-12 DEG C, drip volume ratio is the concentrated sulfuric acid of 3:1-2 and the mixed acid solution of red fuming nitric acid (RFNA), at-8 DEG C to-12 DEG C, react 0.5-1.5h, is heated to 75-95 DEG C of reaction 130-150min; In reactant liquor instillation ice cube, rapid stirring, adjust pH to 6-7 with NaOH, obtain neutralization solution, with neutralization solution described in solvent extraction, decompression distillation obtains yellow product 5,6-diketone-1,10-Phen;
B, by 5,6-diketone-1,10-Phen, hydroxylamine hydrochloride and BaCO 310-13h is reacted, distillation, the watery hydrochloric acid washing of solid 0.2-0.3mol/L, suction filtration in the ethanol of 70-80 DEG C, with the first mixed liquor washing several, then vacuumize, obtain light yellow product 5,6-dioxime-1,10-Phen;
C, 5,6-dioxime-1,10-Phen is put into absolute ethyl alcohol, obtain alcoholic solution, be heated to 70-80 DEG C under inert gas shielding, getting sodium hydrosulfite, to be dissolved in content be in the ammonia spirit of 3%-5%, obtain the second mixed liquor, the second mixed liquor is added in above-mentioned alcoholic solution; Add the second mixed liquor with first time equivalent after 15-45min, and react 1.5-2h at 75-85 DEG C; Be cooled to normal temperature, suction filtration, with distilled water washing several, then wash for several times with ethanol or acetone, vacuumize, obtain golden yellow 5,6-diamines-1,10-Phen;
D, 5,6-diamines-1,10-Phen and 3,4-diacetyl are reacted 10-13h, decompression distillation at normal temperatures, the mixed liquor of solids with methanol and water washs, vacuumize, obtains white powder 2,3-dimethyl pyrazine also [1,10] Phen;
(2) organic RE europium complex Eu (TTA) 3the preparation of DmPPhen luminescent material:
By Eu 2o 3with concentrated hydrochloric acid mixing, evaporate to dryness on electric jacket, is then mixed with ethanolic solution; Get a certain amount of Phen neutral ligand DmPPhen and put into flask, drip and the equimolar EuCl of Phen neutral ligand DmPPhen at 55-60 DEG C 3ethanolic solution, stir 40-80 minute; The ethanolic solution of the HTTA of dropping Phen neutral ligand DmPPhen, 3 times of molar weights, adjusts pH to 6-7 with triethylamine, proceeds to autoclave, insulation reaction 5-10h; Decompression distillation, solid is separated out in cooling, suction filtration, and for several times, washed several times with water, vacuumize, obtains nano level blush powder to alcohol wash.
3. the preparation method of the luminous polyamide fibre of Europium according to claim 2, is characterized in that:
In described step a:
Every 1g 1,10-Phen correspondence adds 0.4-1g potassium bromide;
The mixed acid solution that every 1g 1,10-Phen correspondence adds is 20-30ml;
The solvent of described extraction is carrene or chloroform;
In described step b:
Described 5,6-diketone-1,10-Phens, hydroxylamine hydrochloride and BaCO 3mass ratio be 1:0.7-2:0.7-2;
Every 0.84g 5,6-diketone-1,10-Phen correspondence adds 40-60ml ethanol synthesis 8-13h;
Described first mixed liquor is ethanol and ether or methyl alcohol and ether, and the ethanol in described first mixed liquor or the volume ratio of methyl alcohol and ether are 1:2-8;
The first mixed liquor that every 0.84g 5,6-diketone-1,10-Phen correspondence adds is 15-30ml;
In described step c:
Every 1mmol 5,6-dioxime-1,10-Phen correspondence puts into 5-10ml ethanol;
The mol ratio of described 5,6-dioxime-1,10-Phens and sodium hydrosulfite is 1:3-5;
It is in the ammonia spirit of 3%-5% that every 1mmol sodium hydrosulfite is dissolved in 0.6-1ml mass percent concentration;
Every 1mmol 5,6-dioxime-1,10-Phen correspondence adds second mixed liquor of 2.5-4.5ml;
In described steps d:
The mass ratio of described 5,6-diamines-1,10-Phens and 3,4-diacetyl is 1.5-3:1;
The volume ratio of described methyl alcohol and water is 1:8-12;
The cumulative volume that every 1g5,6-diamines-1,10-Phen correspondence adds methyl alcohol and water is 8-12ml;
In described step (2):
Described Eu 2o 3be 1:1-10 with the mass ratio of concentrated hydrochloric acid.
4. the preparation method of the luminous polyamide fibre of Europium according to claim 3, is characterized in that:
In described step b, c d and step (2): the vacuum used is 0.09MPa, and baking temperature is 60-90 DEG C; Drying time in described step b is 5-12h;
Drying time in described step c is 4-10h;
Drying time in described steps d is 5-12h;
Drying time in described step (2) is 5-12h;
Described autoclave insulation reaction temperature is 120-160 DEG C, and pressure is less than 10MPa.
5. the preparation method of the luminous polyamide fibre of the Europium according to any one of claim 1-4, is characterized in that: specifically comprise the following steps:
(1) Europium complex luminescent material is fully mixed with PA6 master batch, adopt screw extruder to prepare Masterbatch, vacuumize, make its moisture content be less than 20ppm;
(2) PA6 slices synthesis method is carried out drying to vacuum drum;
(3) Masterbatch and dried PA6 are cut into slices carry out Homogeneous phase mixing by a certain percentage, make organic RE europium complex Eu (TTA) 3the content of DmPPhen is 0.05-5%; Under specific spinning process condition, through screw rod melt extruded, filtration, static mixing, spray silk, slow cooling, drawing-off and package, prepare recombination luminescence fiber.
6. the preparation method of the luminous polyamide fibre of Europium according to claim 5, is characterized in that:
Described Europium complex luminescent material accounts for the 0.3%-30% of Masterbatch gross mass.
7. the preparation method of the luminous polyamide fibre of Europium according to claim 5, is characterized in that:
The weight ratio that described Masterbatch and PA6 cut into slices is 1:20-100.
8. the preparation method of the luminous polyamide fibre of Europium according to claim 5, is characterized in that: described in prepare Masterbatch after the vacuum < 0.095MPa, the dry temperature that adopt be 100-140 DEG C, the dry time is 10-16h.
9. the preparation method of the luminous polyamide fibre of Europium according to claim 5, is characterized in that:
It is 120-180 DEG C that described PA6 section carries out dry temperature at vacuum drum, and vacuum is less than 0.095MPa, and drying time is 10-16h.
10. the luminous polyamide fibre of Europium, is characterized in that: prepare according to the preparation method described in any one of claim 1-9.
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