CN104674368B - Luminous polyamide fibre of Europium and preparation method thereof - Google Patents
Luminous polyamide fibre of Europium and preparation method thereof Download PDFInfo
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Abstract
The invention discloses luminous polyamide fibre of a kind of Europium and preparation method thereof, a kind of Phen neutral ligand is prepared first and is coordinated with rare earth Eu (III) (europium) with reference to α thiophene trifluoro formyl acetones, titrated using first normal pressure, the method for rear reaction under high pressure prepares the Rare Earth Europium Complex Eu (TTA) close to nanoscale3DmPPhen luminescent materials.The material is 10 in concentration‑5The CH of mol/L2Cl2Launch very strong pure feux rouges in solution, at 615nm.Composite molten spinning is carried out as luminescent material and polycaprolactam (PA6, Polyamide 6) using this complex and prepares luminescent fibre.It is 10 in concentration when content is 0.08% to rare earth luminescent material in the fibre‑5Launch stronger pure feux rouges in the DMF solution of mol/L, luminous position still for 615nm at.The luminescent fibre has that excitation is high, the preferable advantage of spinnability.
Description
Technical field
The invention belongs to luminescent material and textile science field, more particularly to a kind of Europium lights polyamide fibre and its system
Preparation Method.
Background technology
Rare earth element is located at group of the lanthanides in the periodic table of elements, because its outer electronic structure is identical, and internal layer 4f energy level ratios
More close, rare earth element shows the physics and chemical property of many uniquenesses, so being used widely in light, electricity, magnetic field.
The fluorescent emission of general rare earth ion mostlys come from the f-f electron transitions of 4f electronic shell, 5S2And 5P6Electronics typically can be 4f electricity
Son is shielded, therefore light radiation transition influence of the matrix on 4f electronic shell is smaller.This shielding action can exactly make rare earth from
Son produces sharp with transmitting and fluorescence lifetime more long.
Usual most of less molar extinction coefficients of trivalent rare earth ionses, make the fluorescence intensity and not bery by force of its own,
When its fluorescence intensity can be strengthened after organic ligand and rare-earth ion coordination, here it is " antenna " effect.Rare earth compounding is used as hair
There are several clear advantages in stimulative substance：A () luminous efficiency is high：The highest luminous efficiency of organic molecule is 25% in theory, and
Rare earth compounding is theoretical up to 100%；
B () light excitation is high：The luminous of rare earth compounding is produced by the f-f transition of central ion, its spectral bands
It is very narrow, emission spectrum half peak breadth (<10nm)；C () modified ligand does not influence glow color：The emission spectrum of rare earth compounding is not
The emission spectrum of general transient metal complex is same as, typically in order to improve workability, solubility, the charge migration of complex
And the property such as the migration of carrier, often part is modified to meet above-mentioned requirements.These advantages have been widely used
The fields such as phosphor, fluorescent lamp, laser dye, electroluminescent material in color monitor.
It is of interest that Eu (III) complexs have obtained researcher as the excellent photic or red electroluminescent phosphor material of a class.Grind
A key point for studying carefully Eu (III) complex is the design and optimization to part, and the hair of complex is influenceed by the change of part
The required voltage of light efficiency, stability and device, therefore the change of part has far-reaching influence to the performance of material.Document
(Noto M, Irie K, Era M.Chem.Lett, 2011,320) is prepared for Rare Earth Europium Complex luminescent material Eu (L)3Phen solid fluorescences efficiency is 50%.Document (Sun M, Xin H, Wang, et al.Chem.Commun, 2003,702) is in
Property part on introduce cavity transmission group triphenylamine and adjust electronics and hole transmission, prepared luminescent material Eu
(DBM)3(TPIP) good fluorescent effect is obtained, the device brightness of assembling is up to 1305cd/m2, maximum fluorescence yield is
1.44lm/W.Document (Ling Q.D, Cai Q.J, Huang W et al.Mater Chem, 2004,14,2741-2746) is made
For side chain type macromolecule rare-earth europium luminescent material, the hole transporting property using carbazole is polymerized with emitting complexes, but
This kind of material carries side chain, and molecular weight difficult control during polymerization, it is difficult to directly carrying out spinning prepares luminescent fibre.
The preparation of luminescent fibre is usually that luminescent material is doped in high polymer, and luminescent fibre is made through spinning.Its
Method is roughly divided into：Solution-polymerized SBR, melt spinning, face coat etc..Solution-polymerized SBR requirement luminescent material can be dissolved in solvent, melted
Melt spinning requirement fluorescent material stabilization, heating is not easily decomposed, resistance to oxidation etc., and shows coating and then require luminescent material and fiber table
There is good affinity in face.
In recent years to the existing relevant report of exploitation of luminescent fibre, some seminars are prepared for one using electrostatic spinning technique
A little rear-earth-doped polymer nanofibers and inorganic nano-fiber.Luo Jun et al. is prepared for series of rare earth silicate long-afterglow
Luminescent material doping carries out electrostatic spinning (China Patent Publication No. in the fibre：CN103938297A, application number：
201410174370.7), this fluorescent fiber can launch indigo plant through visible ray or ultraviolet light 1-10 minutes at 470nm.This
Fiber prepared by class luminescent material has the effect of extinction energy storage, with long-persistence luminous feature；General prepared inorganic silicon
Salt luminescent material increasing particle size, spinnability is poor in being doped to fiber, and exists at aspects such as false proof and electroluminescent scarce
Fall into.Sui X.M. et al. (X.M.Sui, C.L.Shao, Y.C.Liu et al.Appl.Phys.Lett., 2005,87,113-
115) ZnO/PVA composite fibres are prepared for, white light can be launched.Document (H.Zhang, H.W.Song, B.Dong et
Al.J.Phy.Chem, 2008,112,9155-9162) it is middle Eu (BA)3(TPPO)2It is entrained in PVP (Poly Vinyl
Pyrrolidone, polyvinylpyrrolidone) in carry out composite spinning, be prepared for that bleach-resistant ability is strong, the compound of stable luminescence is received
Rice fiber；With the level-density parameter situation of Eu (III) ion it is not fine due to part, the luminous intensity of caused complex is not
It is very high.Chinese patent CN101381901A, application number：200810042269.0, it is prepared for a series of organic molecules Fluoresceinated
Compound carries out melt spinning in being doped to polypropylene, prepares the luminous fibre of polypropylene of good, the different glow colors of luminescent properties
Dimension；This kind of fiber prepared with pure organic molecule, oxidative resistance, excitation, luminous efficiency and luminous intensity are poor.
The content of the invention
It is given below on brief overview of the invention, to provide the basic reason on certain aspects of the invention
Solution.It should be appreciated that this general introduction is not on exhaustive general introduction of the invention.It is not intended to determine key of the invention
Or pith, nor is it intended to limit the scope of the present invention.Its purpose only provides some concepts in simplified form, with
This is used as the preamble in greater detail discussed after a while.
The purpose of the embodiment of the present invention is directed to the defect of above-mentioned prior art, there is provided one kind is in ultraviolet light or electroluminescent
Under the conditions of there is the preparation method of the luminous polyamide fibre of efficient, luminous intensity Europium high.
To achieve these goals, the present invention is adopted the technical scheme that：
A kind of preparation method of the luminous polyamide fibre of Europium, comprises the following steps：
(1) Europium complex luminescent material is prepared, its chemical formula is C24H16EuN4SF3O2, molecular formula is Eu
(TTA)3DmPPhen, wherein TTA are：α-thiophene trifluoro formyl acetone, DmPPhen are：Simultaneously [1,10] are adjacent for 2,3- dimethyl pyrazines
Phenanthroline, structural formula is：
(2) machine Rare Earth Europium Complex luminescent material and PA6 (Polyamide 6, polycaprolactam) sections are blended,
Luminous polyamide fibre is obtained through melt spinning again.
The present invention provides a kind of Europium luminous polyamide fibre again, is prepared according to above-mentioned preparation method.
Compared with prior art, the beneficial effects of the invention are as follows：
1) triplet is prepared with Eu (III) ion5D0The part DmPPhen that energy level is effectively matched, makes prepared
The luminous efficiency of Rare Earth Europium Complex, luminous intensity are effectively improved, the heat endurance of complex, oxidative resistance enhancing.It is luminous strong
Raisings of degree and efficiency can effectively reduce the addition of complex, broken end when reducing spinning, around roller, raising spinnability.
2) larger using complex grain diameter obtained in synthesis under normal pressure, the present invention is used after normal pressure has titrated part,
Solution is transferred to autoclave insulation reaction again, the complex close to nanoscale can be prepared using solvent heat, cut into slices with PA6
Broken end can be reduced when carrying out composite spinning, around roller the problems such as.
3) present invention carries out composite spinning with PA6 sections after drying again using luminescent material master batch is first prepared, and can make
Luminescent material is uniformly dispersed in polymeric system, prevents from producing Fluorescence-quenching under high concentration.
4) present invention is set specific process conditions by melt spinning method, can continuously carry out POY (preorientations
Silk) and UDY (non-oriented silk) spinning, the Europium luminescent fibre that fiber thickness is uniform, strength is appropriate is obtained.
5) present invention obtains preparation luminous intensity good, dispersed by preparing organic rare-earth ligand luminescent material
Good, the luminescent fibre that chemical stability is high, fiber number is uniform, strength is appropriate new way.Can false proof, clothes, seabed operation, point
The fields such as sub- probe, biochip, communication, solar cell have important application.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
The accompanying drawing to be used needed for having technology description is briefly described, and drawings in the following description are only some realities of the invention
Example is applied, for those of ordinary skill in the art, without having to pay creative labor, can also be attached according to these
Figure obtains other 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 method3The INFRARED SPECTRUM of DmPPhen and part DmPPhen
Figure, wherein a is Eu (TTA)3DmPPhen, b are DmPPhen；
Fig. 3 is Rare Earth Europium Complex Eu (TTA) prepared by the inventive method3The nuclear magnetic spectrogram of DmPPhen；
Fig. 4 is Rare Earth Europium Complex Eu (TTA) prepared by the inventive method3DmPPhen is 10 in concentration-5Mol/L's
CH2Cl2Fluorescent exciting spectrogram in solution；
Fig. 5 is Rare Earth Europium Complex Eu (TTA) prepared by the inventive method3DmPPhen is 10 in concentration-5Mol/L's
CH2Cl2Fluorescence emission spectrogram of compound in solution；
Fig. 6 is Rare Earth Europium Complex Eu (TTA) prepared by the inventive method3The composite fibre of DmPPhen and PA6, when dilute
Native luminescent material in the fibre content be 0.08% when, concentration is 10-5DMF (the Dimethyl Formamide, N, N- of mol/L
Dimethylformamide) fluorescent exciting spectrogram in solution；
Fig. 7 is Rare Earth Europium Complex Eu (TTA) prepared by the inventive method3The composite fibre of DmPPhen and PA6, when dilute
Native luminescent material in the fibre content be 0.08% when, concentration is 10-5Fluorescence emission spectrogram of compound in the DMF solution of mol/L.
Wherein：
Abscissa Wavenumbers in Fig. 2 represents wave number；
Abscissa Wavelength represents wavelength in Fig. 4, Fig. 5, Fig. 6 and Fig. 7, and ordinate Intensity represents intensity.
Specific embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention
In accompanying drawing, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is
A part of embodiment of the present invention, rather than whole embodiments.Described in an accompanying drawing of the invention or a kind of implementation method
Element and the element that can be shown in one or more other accompanying drawings or implementation method of feature and feature be combined.Should
Note, for purposes of clarity, eliminated in accompanying drawing and explanation unrelated to the invention, known to persons of ordinary skill in the art
Part and the expression and description for the treatment of.Based on the embodiment in the present invention, those of ordinary skill in the art are not paying creation
Property work under the premise of the every other embodiment that is obtained, belong to the scope of protection of the invention.
The present invention provides a kind of preparation method of the luminous polyamide fibre of Europium, comprises the following steps：
(1) Europium complex luminescent material is prepared, its chemical formula is C24H16EuN4SF3O2, molecular formula is Eu
(TTA)3DmPPhen, wherein TTA are：α-thiophene trifluoro formyl acetone, DmPPhen are：Simultaneously [1,10] are adjacent for 2,3- dimethyl pyrazines
Phenanthroline, structural formula is：
The construction unit of complex is as follows：
(2) machine Rare Earth Europium Complex luminescent material and PA6 (Polyamide 6, polycaprolactam) sections are blended,
Luminous polyamide fibre is obtained through melt spinning again.
Specifically, the preparation method of Europium complex luminescent material, comprises the following steps：
(1) preparation of part 2,3- dimethyl pyrazines simultaneously [1,10] Phen：
A, 1,10- Phens and KBr are put into flask, it is 3 that volume ratio is added dropwise at -8 DEG C to -12 DEG C:1-2's
The mixed acid solution of the concentrated sulfuric acid and concentrated nitric acid, 0.5-1.5h is reacted at -8 DEG C to -12 DEG C, is heated to 75-95 DEG C of reaction 130-
150min；Reaction solution is instilled in ice cube, quick stirring, and pH to 6-7 is adjusted with NaOH, obtains neutralizing solution, with described in solvent extraction
Solution is neutralized, vacuum distillation obtains yellow product 5,6- diketone -1,10- Phens；
0.4-1g KBrs are added per 1g 1,10- Phens correspondence；
The mixed acid solution added per 1g1,10- Phens correspondence is 20-30ml；
The solvent of the extraction is dichloromethane or chloroform；
B, by 5,6- diketone -1,10- Phens, hydroxylamine hydrochloride and BaCO310- is reacted in 70-80 DEG C of ethanol
13h, distillation, solid is washed with the watery hydrochloric acid of 0.2-0.3mol/L, and suction filtration is washed for several times with the first mixed liquor, then is vacuum dried,
Vacuum is 0.09MPa, and drying temperature is 60-90 DEG C；Drying time is 5-12h；Light yellow product 5,6- dioxime -1 is obtained,
10- Phens；
5,6- diketone -1,10- the Phens, hydroxylamine hydrochloride and BaCO3Mass ratio be 1:0.7-2:0.7-2；
40-60ml ethanol is added per 0.84g5,6- diketone -1,10- Phens correspondence, the reaction time is 10-13h；
First mixed liquor is ethanol and ether or methyl alcohol and ether, the ethanol or methyl alcohol in first mixed liquor with
The volume ratio of ether is 1:2-6；
The first mixed liquor added per 0.84g5,6- diketone -1,10- Phens correspondence is 15-30ml；
C, by 5,6- dioxime -1,10- Phens are put into absolute ethyl alcohol, obtain alcoholic solution, under inert gas shielding heat
To 70-80 DEG C, take sodium hydrosulfite and be dissolved in the ammonia spirit that content is 3%-5%, obtain the second mixed liquor, the second mixed liquor is added
In entering above-mentioned alcoholic solution；The second mixed liquor with first time equivalent is added after 15-45min, and 1.5- is reacted at 75-85 DEG C
2h；Normal temperature is cooled to, suction filtration with distillation water washing for several times, then is washed for several times, vacuum drying with ethanol or acetone, and vacuum is
0.09MPa, drying temperature is 60-90 DEG C, and drying time is 4-10h；Obtain golden yellow 5,6- diamines -1,10- Phens；
5-10ml ethanol is correspondingly placed into per 1mmol 5,6- dioxime -1,10- Phens；
5,6- dioximes -1,10- the Phens are 1 with the mol ratio of sodium hydrosulfite：3-5；
It is dissolved in per 1mmol sodium hydrosulfites in the ammonia spirit that 0.6-1ml mass percent concentrations are 3%-5%；
Second mixed liquor of 2.5-4.5ml is added per 1mmol 5,6- dioxime -1,10- Phens correspondence；
D, by 5,6- diamines -1,10- Phens and 3,4- diacetyl react 10-13h at normal temperatures, vacuum distillation, Gu
Body is washed with methyl alcohol with the mixed liquor of water, vacuum drying, and vacuum is 0.09MPa, and drying temperature is 60-90 DEG C, drying time
It is 5-12h；Obtain white powder 2,3- dimethyl pyrazines simultaneously [1,10] Phen；
The mass ratio of the 5,6- diamines -1,10- Phens and 3,4- diacetyl is 1.5-3：1；
The methyl alcohol is 1 with the volume ratio of water:8-12；
It is 8-12ml with the cumulative volume of water that methyl alcohol is added per 1g5,6- diamines -1,10- Phens correspondence.
(2) organic RE europium complex Eu (TTA)3The preparation of DmPPhen luminescent materials：
By Eu2O3With concentrated hydrochloric acid mixing, Eu2O3It is 1 with the mass ratio of concentrated hydrochloric acid:1-10, is evaporated on electric jacket, then
It is configured to ethanol solution；Take a certain amount of Phen neutral ligand DmPPhen to be put into flask, be added dropwise at 55-60 DEG C and neighbour
The equimolar EuCl of phenanthroline neutral ligand DmPPhen3Ethanol solution, stir 40-80 minutes；Phen neutrality is added dropwise to match somebody with somebody
The ethanol solution of body DmPPhen, the HTTA of 3 times of moles, pH to 6-7 is adjusted with triethylamine, is transferred to autoclave, and design temperature is
120-160 DEG C, pressure is less than 10MPa, insulation reaction 5-10h；Pressure is more than 0.1MPa, and vacuum distillation, cooling separates out solid, takes out
Filter, alcohol is washed for several times, washed several times with water, vacuum drying, and vacuum is 0.09MPa, and drying 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 invention is divided into two parts completion, rare-earth europium is prepared first and is lighted
Material, is then prepared into Masterbatch, then is cut into slices melt spinning with PA6.Obtain that having for pure feux rouges can be launched under ultraviolet light
Machine rare-earth europium lights polyamide fibre.
Specifically include following steps：
(1) Europium complex luminescent material is sufficiently mixed with PA6 master batches, is prepared using screw extruder
Go out Masterbatch, be vacuum dried, its moisture content is less than 20ppm；Europium complex luminescent material accounts for Masterbatch gross mass
0.3%-30%.Using vacuum drying, its vacuum ＜ 0.095MPa, dry temperature are the Masterbatch prepared
100-140 DEG C, the dry time be 10-16h.
(2) PA6 slices synthesis methods are dried to vacuum drum；Dry temperature is 120-180 DEG C, and vacuum is less than
0.095MPa, drying time is 10-16h.
(3) Masterbatch is uniformly mixed by a certain percentage with dried PA6 sections, the Masterbatch is cut with PA6
The weight ratio of piece is 1:20-100, makes organic RE europium complex Eu (TTA)3The content of DmPPhen is 0.05-5%；Specific
Under spinning process condition, through screw rod melt extruded, filtering, static mixing, spinneret, slow cooling, drawing-off and package, compound hair is prepared
Fiber optics；
The present invention makes its triplet and rare earth Eu by preparing a Phen neutral ligand3+Energy level phase
Match somebody with somebody so that prepared new complexes ultraviolet light or it is electroluminescent under the conditions of have efficient, luminous intensity it is high,
Launch pure feux rouges, the Europium complex luminescent material that heat endurance is good, grain diameter is small.
The present invention prepares that luminous intensity is high, launch pure by using melt spinning method
Luminous polyamide fibre.Under ultraviolet light, luminous polyamide fibre launches pure feux rouges at 615nm.
The present invention provides a kind of Europium luminous polyamide fibre again, is prepared according to above-mentioned preparation method.
The present invention is prepared for a kind of Phen neutral ligand and combines α-thiophene trifluoro formyl acetone and rare earth Eu (III)
It is coordinated, is titrated using first normal pressure, the method for rear reaction under high pressure is prepared the Rare Earth Europium Complex Eu close to nanoscale
(TTA)3DmPPhen luminescent materials.The material is 10 in concentration-5The CH of mol/L2Cl2Launch very strong in solution, at 615nm
Pure feux rouges.Using this complex as luminescent material and polycaprolactam (PA6) carry out composite molten spinning prepare it is luminous
Fiber.It is 10 in concentration when content is 0.08% to rare earth luminescent material in the fibre-5Launch in the DMF solution of mol/L compared with
Strong pure feux rouges, luminous position still for 615nm at.The luminescent fibre is that a kind of excitation is high, the preferable luminescent fibre of spinnability.
The present invention prepare it is efficient, color is pure, good stability, particle diameter be nano level organic RE light material
Material is applied to prepare the efficient, luminescent fibre of good spinnability has practical significance.
Orgnic RE complex Eu (TTA) of the invention3Recombination luminescence fiber prepared by DmPPhen and PA6, the fiber
It is nontoxic, without radiocontamination, it is processed after can be in the false proof of high-grade goods, lighting clothes, seabed operation, molecular probe, life
The fields such as thing chip, communication, solar cell have important application.
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- Phen -5,6- diketone (compound 1)：1g 1,10- Phens and 0.6g are weighed respectively
KBr is added in two mouthfuls of flasks of 100mL, flask is put into ice salt bath and is cooled to -10 DEG C.The 16mL concentrated sulfuric acids are measured to pour into
In the beaker of 200mL, then 8ml concentrated nitric acids are measured with graduated cylinder.It is slowly dense toward being added dropwise in beaker with dropper under the conditions of the ice salt bath
Nitric acid, is added dropwise while being stirred with glass bar, about time-consuming 30min of dropwise addition or so, if dropwise addition is too fast can smolder.Acid solution is prepared
After start slowly to be added dropwise toward flask, dropwise addition process is maintained under -10 DEG C of condition of ice bath, and 0.5h or so is about added dropwise.Then ice
, to 85 DEG C, insulation reaction 130min, reaction is cooled to normal temperature after terminating for bath reaction 1h and then temperature programming.Separately take a 500ml's
Beaker is put into ice bath, the ice cube for then having frozen in advance toward input in beaker, and reacted solution is slowly added drop-wise on ice cube,
Drip while stirring of exerting oneself.Weigh 30g or so NaOH wiring solution-formings, neutralization reaction liquid, moment holding system in N-process
Inside have ice, and firmly stir, about 1h or so is neutralized and finished, neutralize to pH value 6-7 or so, stirring three minutes to pH value not
Become.Use CH2Cl2Extraction neutralizes solution, and anhydrous magnesium sulfate dries extract, and then distillation extraction liquid, obtains yellow powder, then
Needle-like yellow product 0.942g is obtained with ethyl alcohol recrystallization, yield is：94.2%, m.p=251-252 DEG C,1H NMR
(400MHz,CDCl3):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- dioximes (compound 2)：0.84g chemical combination is added toward 100mL single-necked flasks
Thing 1,1.18g barium carbonates and the dried hydroxylamine hydrochlorides of 1.2g, are subsequently adding 60ml absolute ethyl alcohols.Intensification is begun to warm up, is heated up
Continue to react 12h to backflow, stop reaction, reaction unit is made into distilling apparatus carries out vacuum distillation.Take the dense salt of 12mol/L
Sour 4.16mL, is made into the watery hydrochloric acid of 0.25mol/L, and the hydrochloric acid for measuring 20mL preparations is poured into flask, and stirring at normal temperature 30min is laggard
Row suction filtration.Filter cake methyl alcohol and ether 1:5 mixed liquor 20ml washs three times and then vacuum drying, and vacuum is 0.09MPa, does
Dry temperature is 65 DEG C；Drying time is 10h；Finally obtain product as light yellow solid 0.76g, yield 90.4%, m.p=235-236
℃。
The preparation of 5,6- diamines -1,10- Phens (compound 3)：By 6mmol 5,6- dioxime -1,10- Phens
40ml absolute ethyl alcohols are put into, obtain being heated to 75 DEG C under alcoholic solution, inert gas shielding, taken 25mmol sodium hydrosulfites and be dissolved in 20ml and contain
Measure in the ammonia spirit for 5%, obtain the second mixed liquor, quickly by the mixed liquors of the 20ml second above-mentioned alcoholic solution of addition.45min
The same mixed liquors of above-mentioned 20ml second are added when seeing that yellow solid matter is separated out afterwards, and 2h is reacted at 80 DEG C.It is cooled to often
Temperature, suction filtration with distillation water washing 3 times, then wash 3 times, vacuum drying with ethanol, and vacuum is 0.09MPa, and drying temperature is 65
℃；Drying time is 5h；Obtain bright yellow solid product, yield 76.0%, m.p>350℃,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 pyrazines simultaneously [2,3-f] [1,10] ferrosin (DmPPhen)：0.52g compounds 3 are weighed to add
Enter in the flask of 150ml, add 75mL absolute ethyl alcohols.0.21g 3 is measured, 4- diacetyl is made into 10mL ethanol solutions, under normal temperature
3,4- diacetyl is slowly added dropwise toward there-necked flask, normal-temperature reaction is continued after completion of dropwise addition, stopped after reaction 12h.Then depressurize
Solvent is evaporated, solid product pours into 11ml (methyl alcohol：Water=1:10) washed in solution, then filtered, filter cake is dried
Admixing silica gel after dry carried out post separation；First use petroleum ether：Ethyl acetate=3:1 crosses post, then tunes up polarity ethyl acetate：First
Alcohol=5:1.Eluent decompression is evaporated, and solid is recrystallized again, dried in vacuum overnight at 75 DEG C, final to obtain product as white needles
0.47g, yield is：64.4%, m.p=281-282 DEG C,1H NMR(400MHz,CDCl3):δ 9.49 (t, J=27.1Hz,
2H), (s, the 6H) .IR (KBr) of 9.36 (m, 2H), 7.81 (dd, J=7.9,4.4Hz, 2H), 2.87:3417,1573,1513,
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：0.67g α-thiophene trifluoro formyl acetone is added toward there-necked flask,
20ml absolute ethyl alcohols, are stirred and heated to 60 DEG C.It is slowly added dropwise the ethanol solution of the Europium chloride for preparing.Then it is added dropwise NaOH's
Ethanol solution, adjusts PH to 6-7, and neutralization terminates rear insulation reaction 1h.Weigh 0.26g DmPPhen and be dissolved in 20ml absolute ethyl alcohols
In, slowly drop in flask, after completion of dropwise addition, pick solution point with glass bar and observe transmitting under uviol lamp to filter paper
Go out very strong feux rouges.Regulation pH value is 6-7, is then transferred to autoclave, 140 DEG C of design temperature, and pressure is set to 1MPa, insulation
Reaction 6h, reaction terminates rear solvent concentration has white solid to separate out to 15ml or so.Suction filtration, filter cake elder generation are carried out after being cooled to room temperature
With absolute ethanol washing 3 times, then it is washed with deionized three times.Then ethyl alcohol recrystallization, 70 DEG C of vacuum drying 8h is used to obtain micro- red
Color powder 0.79g.Yield：71.3%.M.p=279-281 DEG C.
The infrared spectrum of complex such as Fig. 1：The characteristic absorption peak ν of part α-thiophene trifluoro formyl acetone (HTTA)C=O
(1656cm-1) 1625cm is moved to after coordination-1Place.HTTA parts, respectively in 1305cm after coordination-1And 1142cm-1Place goes out
Existing νas(CF3)And νS(CF3)Characteristic absorption peak.And νC=C(thiphene ring) and νC-HThe characteristic absorption peak of (thiphene ring) exists respectively
1353cm-1And 1061cm-1Place occurs.νC-SCharacteristic peak appear in 722cm-1, these absolutely prove α-thiophene trifluoro formyl third
Ketone is coordinated successfully.For DmPPhen parts after coordination the stretching vibration red shift of its C=N to 1478cm-1.In addition
561cm-1One absworption peak at place is the absworption peak of N-Eu, and these results confirm that DmPPhen is coordinated.The nuclear-magnetism number of complex
According to：1HNMR(400MHz,CDCl3):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, CH3-6H).In elementary analysis bracket
It is theoretical value：Anal.calcd.C:44.58(44.66),H:2.17(2.25),N:5.10(5.21).
Fig. 4 is that complex is 10 in concentration-5The CH of mol/L2Cl2Fluorescent exciting spectrogram in solution, complex exists
Bands of a spectrum wider, a length of 373nm of optimum excitation wave are presented between 260nm-420nm.
Fig. 5 is that complex is 10 in concentration-5The CH of mol/L2Cl2Fluorescent exciting spectrogram in solution from emission spectrum,
Complex occurs in that Eu at 590nm (orange red photochromic), 615nm (pure feux rouges) and 651nm3+Characteristic emission peak, and half-peak breadth
Degree is narrower.Emission peak at wherein 590nm and 615nm is respectively europium (III)5D0→7F1Transition and5D0→7F2Transition.615nm
The very strong spike in place is far longer than other peaks at two, illustrates that complex has very strong monochromaticjty.From fluorescence spectra emission light
Intensity finds out that DmPPhen parts show very outstanding " collaboration " effect after being coordinated with Eu (III), there is very strong at 615nm
Spike, illustrate that made complex is a kind of good red illuminating material.
The preparation of ultraviolet irradiation luminous PA6 fibers, its process is as follows：
The nanoscale luminescent material of above-mentioned preparation and PA6 master batches are sufficiently mixed, are prepared using double screw extruder
Go out the Masterbatch containing organic rare-earth ligand 5%, 105 DEG C of vacuum dries 12h makes its moisture content be less than 20ppm.
PA6 slices synthesis methods are dried to vacuum drum, design temperature is 150 DEG C, and vacuum is 0.095MPa, dried
Time 12h.
Dried material feeds single screw extrusion machine simultaneously with the Masterbatch with rare earth luminescent material, and Masterbatch is fed
Enter amount control in make rare earth luminescent material account for whole inventory 0.08%.Screw rod is through variable frequency regulating speed control melt outlet pressure.
Material after Screw Extrusion makes melt mixed uniform through static mixer, is then dispensed for spinning manifold, and setting is spun
Silk spin manifold temperature is 275 DEG C.Blend melt carries out spinneret through spinneret.
Cross air blasting cooling shaping, setting cross air blasting humidity 75%, wind speed 0.40-0.45m/s.Carried out after being oiled through oil nozzle again
High-speed winding, is obtained the luminous polyamide fibres of POY.
Fig. 6 be rare earth luminescent material in the fibre content be 0.08% when, concentration be 10-5In the DMF solution of mol/L
Fluorescent exciting spectrogram.Composite fibre is presented bands of a spectrum wider, a length of 342nm of optimum excitation wave between 263-375nm.
Fig. 7 be rare earth luminescent material in the fibre content be 0.08% when, concentration be 10-5In the DMF solution of mol/L
Fluorescence emission spectrogram of compound.The fluorescence emission spectrum of composite fibre is mainly reflected in the characteristic emission (590nm (orange light) of Eu (III)
With 615nm (pure feux rouges)).The position of emission peak does not change in composite fibre, and is still in narrow emission, explanation
Prepared composite fibre has excitation very high.
Embodiment 2
The preparation of the luminescent fibre under luminescent material and different spinning process conditions of the present embodiment only to different content is entered
Row explanation, the preparation method of its luminescent material is with embodiment 1, and the preparation process of luminescent fibre is as follows：
The nanoscale luminescent material of above-mentioned preparation and PA6 master batches are sufficiently mixed, are prepared using double screw extruder
Go out the Masterbatch containing organic rare-earth ligand 5%, 120 DEG C of vacuum dries 10h makes its moisture content be less than 20ppm.
PA6 slices synthesis methods are dried to vacuum drum, design temperature is 120 DEG C, and vacuum is 0.095MPa, dried
Time 16h.
Dried material feeds single screw extrusion machine simultaneously with the Masterbatch with rare earth luminescent material, and Masterbatch is fed
Enter amount control in make rare earth luminescent material account for whole inventory 0.08%.Screw rod is through variable frequency regulating speed control melt outlet pressure.
Material after Screw Extrusion makes melt mixed uniform through static mixer, is then dispensed for spinning manifold, and setting is spun
Silk spin manifold temperature is 280 DEG C.Blend melt carries out spinneret through spinneret.
Cross air blasting cooling shaping, setting cross air blasting humidity 75%, wind speed 0.40-0.45m/s.Carried out after being oiled through oil nozzle again
High-speed winding, is obtained the luminous polyamide fibres of POY.
Embodiment 3
The preparation method of the luminous polyamide fibre of Europium：
Specifically include following steps：
The preparation of Europium complex luminescent material：
(1) preparation of part 2,3- dimethyl pyrazines simultaneously [1,10] Phen：
A, by mass ratio be 1:11,10- Phens and KBr is put into flask, and it is 3 that volume ratio is added dropwise at -8 DEG C:
1 concentrated sulfuric acid and the mixed acid solution of concentrated nitric acid, per 1g 1, the mixed acid solution that 10- Phens correspondence is added is 25ml；At -8 DEG C
Lower reaction 1.5h, is heated to 90 DEG C of reaction 130min；Reaction solution is instilled in ice cube, quick stirring, and pH to 6-7 is adjusted with NaOH, is obtained
To mixed solution, with mixed solution described in chloroform extraction, vacuum distillation obtains yellow product 5,6- diketone -1,10- neighbour's Féraud
Quinoline；
B, by mass ratio be 1:2:1 5,6- diketone -1,10- Phens, hydroxylamine hydrochloride and BaCO3In 79 DEG C of ethanol
Middle reaction 13h, per 0.84g 5,6- diketone -1, it is 40ml that 10- Phens correspondence adds ethanol；Distillation, solid 15ml,
The watery hydrochloric acid washing of 0.2mol/L, suction filtration is washed for several times with the first mixed liquor, and first mixed liquor is ethanol and ether, institute
The ethanol and the volume ratio of ether stated in the first mixed liquor are 1:6；Add per 0.84g 5,6- diketone -1,10- Phens correspondence
The first mixed liquor for entering is 15ml；It is vacuum dried again, vacuum is 0.09MPa, drying temperature is 75 DEG C；Drying time is 8h；
Obtain light yellow product 5,6- dioxime -1,10- Phens；
C, by 5,6- dioxime -1,10- Phens are put into absolute ethyl alcohol, per 1mmol 5,6- dioxime -1,10- Phens
It is correspondingly placed into 10ml ethanol；Obtain being heated to 80 DEG C under alcoholic solution, inert gas shielding, take 5,6- dioxime -1,10- Phens
The sodium hydrosulfite of 5 times of moles is dissolved in the ammonia spirit that content is 3%, obtains the second mixed liquor, and the second mixed liquor is added
In stating alcoholic solution；The second mixed liquor with first time equivalent is added after 30min, and 2h is reacted at 79 DEG C；Normal temperature is cooled to, is taken out
Filter, with distillation water washing for several times, then is washed for several times, vacuum drying with acetone, and vacuum is 0.09MPa, and drying temperature is 75 DEG C,
Drying time is 6h；Obtain golden yellow 5,6- diamines -1,10- Phens；
The ammonia spirit that 0.75ml mass percent concentrations are 3% is dissolved in per 1mmol sodium hydrosulfites；Per 1mmol 5,6- bis-
Oxime -1,10- Phens correspondence adds second mixed liquor of 3ml；
D, by mass ratio be 3：15,6- diamines -1,10- Phens and 3,4- diacetyl react 13h at normal temperatures, subtract
Pressure distillation, solid is washed with methyl alcohol with the mixed liquor of water, and methyl alcohol is 1 with the volume ratio of water:8, it is vacuum dried, vacuum is
0.09MPa, drying temperature is 75 DEG C, and drying time is 10h；Obtain white powder 2,3- dimethyl pyrazines simultaneously [1,10] neighbour Féraud
Quinoline；
The cumulative volume 11ml of methyl alcohol and water is added per 1g 5,6- diamines -1,10- Phens correspondence.
Organic RE europium complex Eu (TTA)3The preparation of DmPPhen luminescent materials：
It is 1 by mass ratio:10 Eu2O3With concentrated hydrochloric acid mixing, it is evaporated on electric jacket, is then configured to ethanol solution；Take
A certain amount of Phen neutral ligand DmPPhen is put into flask, is added dropwise and Phen neutral ligand DmPPhen at 60 DEG C
Equimolar EuCl3Ethanol solution, stir 40 minutes；Phen neutral ligand DmPPhen, 3 times of moles is added dropwise
The ethanol solution of HTTA, pH to 6-7 is adjusted with triethylamine, is transferred to autoclave, and at 120 DEG C, pressure is set to 2MPa, insulation reaction 10h；
Vacuum distillation, cooling separates out solid, and suction filtration, alcohol is washed for several times, and washed several times with water is vacuum dried 8h at 80 DEG C, obtains nano level micro-
Red powder.
Europium complex luminescent material is sufficiently mixed with PA6 master batches, is prepared using screw extruder
Masterbatch, vacuum drying makes its moisture content be less than 20ppm；Europium complex luminescent material accounts for Masterbatch gross mass
10%.The vacuum ＜ 0.095MPa, the dry temperature that are used after Masterbatch are prepared for 115 DEG C, dry time are 10h.
Masterbatch is uniformly mixed by a certain percentage with dried PA6 sections, the Masterbatch is cut into slices with PA6
Weight ratio is 1:20, make organic RE europium complex Eu (TTA)3The content of DmPPhen is 0.5%；In specific spinning technique bar
Under part, melt extruded, filtering, static mixing are squeezed through screw rod, be then dispensed for spinning manifold, set 280 DEG C of spinning body temperature；
Blend melt carries out spinneret through spinneret.Cross air blasting cooling shaping, setting cross air blasting humidity 70%, wind speed 0.40m/s；Again through oil
Mouth carries out low-speed rolling around the prepared luminous polyamide fibres of POY after oiling.
Finally it should be noted that：The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
The present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those within the art that：It still may be used
Modified with to the technical scheme described in foregoing embodiments, or equivalent is carried out to which part technical characteristic；
And these modification or replace, do not make appropriate technical solution essence depart from various embodiments of the present invention technical scheme spirit and
Scope.
Claims (9)
1. the preparation method of the luminous polyamide fibre of a kind of Europium, it is characterised in that comprise the following steps：
(1) Europium complex luminescent material is prepared：
1) preparation of part 2,3- dimethyl pyrazines simultaneously [1,10] Phen：
A, 1,10- Phens and KBr are put into flask, it is 3 that volume ratio is added dropwise at -8 DEG C to -12 DEG C:The dense sulphur of 1-2
Acid and the mixed acid solution of concentrated nitric acid, 0.5-1.5h is reacted at -8 DEG C to -12 DEG C, is heated to 75-95 DEG C of reaction 130-150min；
Reaction solution is instilled in ice cube, quick stirring, and pH to 6-7 is adjusted with NaOH, obtains neutralizing solution, molten with being neutralized described in solvent extraction
Liquid, vacuum distillation obtains yellow product 5,6- diketone -1,10- Phens；
B, by 5,6- diketone -1,10- Phens, hydroxylamine hydrochloride and BaCO310-13h is reacted in 70-80 DEG C of ethanol, is steamed
Evaporate, solid is washed with the watery hydrochloric acid of 0.2-0.3mol/L, suction filtration, washed for several times with the first mixed liquor, then be vacuum dried, obtain shallow
Yellow product 5,6- dioxime -1,10- Phens；
C, by 5,6- dioxime -1,10- Phens are put into absolute ethyl alcohol, obtain being heated to 70- under alcoholic solution, inert gas shielding
80 DEG C, take sodium hydrosulfite and be dissolved in the ammonia spirit that mass percent concentration is 3%-5%, obtain the second mixed liquor, second is mixed
Conjunction liquid is added in above-mentioned alcoholic solution；The second mixed liquor with first time equivalent is added after 15-45min, and is reacted at 75-85 DEG C
1.5-2h；Normal temperature is cooled to, suction filtration with distillation water washing for several times, then is washed for several times with ethanol or acetone, and vacuum drying is obtained
Golden yellow 5,6- diamines -1,10- Phens；
D, by 5,6- diamines -1,10- Phens and 3,4- diacetyl react 10-13h at normal temperatures, and vacuum distillation, solid is used
The mixed liquor of methyl alcohol and water is washed, vacuum drying, obtains white powder 2,3- dimethyl pyrazines simultaneously [1,10] Phen；
2) organic RE europium complex Eu (TTA)3The preparation of DmPPhen luminescent materials：
By Eu2O3With concentrated hydrochloric acid mixing, it is evaporated on electric jacket, is then configured to ethanol solution；Take a certain amount of Phen neutral
Part DmPPhen is put into flask, is added dropwise and the equimolar EuCl of Phen neutral ligand DmPPhen at 55-60 DEG C3's
Ethanol solution, stirs 40-80 minutes；Phen neutral ligand DmPPhen, the ethanol solution of the HTTA of 3 times of moles is added dropwise,
PH to 6-7 is adjusted with triethylamine, autoclave, insulation reaction 5-10h is transferred to；Vacuum distillation, cooling separates out solid, and suction filtration, alcohol washes number
Secondary, washed several times with water, vacuum drying obtains nano level blush powder；
(2) Europium complex luminescent material and PA6 (Polyamide 6, polycaprolactam) sections are blended,
Luminous polyamide fibre is obtained through melt spinning again；
The chemical formula of the Europium complex luminescent material is C24H16EuN4SF3O2, molecular formula is Eu (TTA)3DmPPhen, wherein TTA are：α-thiophene trifluoro formyl acetone, DmPPhen are：2,3- dimethyl pyrazines simultaneously [1,10] neighbour Féraud
Quinoline, structural formula is：
2. the preparation method of the luminous polyamide fibre of Europium according to claim 1, it is characterised in that：
In the step a：
0.4-1g KBrs are added per 1g 1,10- Phens correspondence；
The mixed acid solution added per 1g 1,10- Phens correspondence is 20-30ml；
The solvent of the extraction is dichloromethane or chloroform；
In the step b：
5,6- diketone -1,10- the Phens, hydroxylamine hydrochloride and BaCO3Mass ratio be 1:0.7-2:0.7-2；
40-60ml ethanol synthesis 8-13h is added per 0.84g 5,6- diketone -1,10- Phens correspondence；
First mixed liquor is ethanol and ether or methyl alcohol and ether, ethanol or methyl alcohol and ether in first mixed liquor
Volume ratio be 1:2-8；
The first mixed liquor added per 0.84g 5,6- diketone -1,10- Phens correspondence is 15-30ml；
In the step c：
5-10ml ethanol is correspondingly placed into per 1mmol 5,6- dioxime -1,10- Phens；
5,6- dioximes -1,10- the Phens are 1 with the mol ratio of sodium hydrosulfite:3-5；
It is dissolved in per 1mmol sodium hydrosulfites in the ammonia spirit that 0.6-1ml mass percent concentrations are 3%-5%；
Second mixed liquor of 2.5-4.5ml is added per 1mmol 5,6- dioxime -1,10- Phens correspondence；
In the step d：
The mass ratio of the 5,6- diamines -1,10- Phens and 3,4- diacetyl is 1.5-3:1；
The methyl alcohol is 1 with the volume ratio of water:8-12；
It is 8-12ml with the cumulative volume of water that methyl alcohol is added per 1g5,6- diamines -1,10- Phens correspondence；
The step 2) in：
The Eu2O3It is 1 with the mass ratio of concentrated hydrochloric acid:1-10.
3. the preparation method of the luminous polyamide fibre of Europium according to claim 2, it is characterised in that：
Step b, c, d and step 2) in：The vacuum for being used is 0.09MPa, and drying temperature is 60-90 DEG C；
Drying time in the step b is 5-12h；
Drying time in the step c is 4-10h；
Drying time in the step d is 5-12h；
The step 2) in drying time be 5-12h；
The autoclave insulation reaction temperature is 120-160 DEG C, and pressure is less than 10MPa.
4. the preparation method of the luminous polyamide fibre of Europium according to claim any one of 1-3, it is characterised in that：It is described
Step (2) is comprised the following steps：
1) Europium complex luminescent material is sufficiently mixed with PA6 master batches, is prepared using screw extruder outstanding
Master batch, vacuum drying makes its moisture content be less than 20ppm；
2) PA6 slices synthesis methods are dried to vacuum drum；
3) Masterbatch is uniformly mixed by a certain percentage with dried PA6 sections, is made organic RE europium complex Eu
(TTA)3The content of DmPPhen is 0.05-5%；Under spinning process condition, through screw rod melt extruded, filtering, static mixing,
Spinneret, slow cooling, drawing-off and package, prepare recombination luminescence fiber.
5. the preparation method of the luminous polyamide fibre of Europium according to claim 4, it is characterised in that：
The Europium complex luminescent material accounts for the 0.3%-30% of Masterbatch gross mass.
6. the preparation method of the luminous polyamide fibre of Europium according to claim 4, it is characterised in that：
The Masterbatch is 1 with the weight ratio of PA6 sections:20-100.
7. the preparation method of the luminous polyamide fibre of Europium according to claim 4, it is characterised in that：It is described to prepare remarkably
Vacuum ＜ 0.095MPa, the dry temperature used after master batch are for 100-140 DEG C, dry time are 10-16h.
8. the preparation method of the luminous polyamide fibre of Europium according to claim 4, it is characterised in that：
The PA6 sections are 120-180 DEG C in the temperature that vacuum drum is dried, and vacuum is less than 0.095MPa, when drying
Between be 10-16h.
9. the luminous polyamide fibre of a kind of Europium, it is characterised in that：According to the preparation method system described in claim any one of 1-8
It is standby to obtain.
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