CN103288838B - A kind of preparation method of double-core Asia phthalocyanines material - Google Patents
A kind of preparation method of double-core Asia phthalocyanines material Download PDFInfo
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- CN103288838B CN103288838B CN201310190913.XA CN201310190913A CN103288838B CN 103288838 B CN103288838 B CN 103288838B CN 201310190913 A CN201310190913 A CN 201310190913A CN 103288838 B CN103288838 B CN 103288838B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The preparation method that the invention discloses a kind of double-core Asia phthalocyanines material.This preparation method is specific as follows: with 4-nitrophthalonitrile for initiation material, solvent DMF make itself and bisphenol generation nucleophilic substitution to prepare four nitrile presomas, then utilize four nitriles of synthesis and phthalonitrile as reacting initial thing, in high boiling point aromatic solvent, it is obtained by reacting double-core subphthalocyanine compounds with Boron tribromide or boron chloride initial ring dimerization, finally the double-core Asia phthalocyanine prepared and Pyrogentisinic Acid's class material are dissolved in aromatic solvent, under the catalysis of pyridine, prepare double-core Asia phthalocyanines material, this preparation method is simple.Present invention also offers this double-core Asia phthalocyanines material as catalyst at Li/SOCl2Application in battery.
Description
Technical field
The present invention relates to cell art, particularly relate to the preparation method of a kind of double-core Asia phthalocyanines material and its as catalyst at Li/SOCl2Application in battery.
Background technology
Sub-phthalocyanine is the organic macrocycle compound with 14-pi-electron conjugated system being made up of three isoindoline unit, within 1972, first synthesized by A.Meller et al., and determined its molecular structure by Kietaibl method of X-ray diffraction after 2 years, may be considered the isomers of phthalocyanine in a broad sense.Due to bigger electron-conjugated system, sub-phthalocyanine has the character such as good heat stability, light stability, nonlinear optics.The synthesis of double-core Asia phthalocyanine is by Kobayashi reported first, and adopting adjacent pyromellitonitrile and phthalonitrile is raw material.Relative to monokaryon Asia phthalocyanine, it has bigger electron-conjugated system, so having more excellent character, its application is based primarily upon its good properties having in optics, in view of electro optic properties is physically having a lot of general character, it is possible to attempt making it as cell catalyst to Li/SOCl2The character of battery is improved.
Li/SOCl2 battery is a kind of battery that in practical application battery string, specific energy is the highest, and its specific energy is up to 590W h/kg and 1100W h/kg.As a kind of green high-efficient energy electrochmical power source, the advantage such as there is specific energy height, volume is little, discharge voltage is high and discharge platform is stable, it is widely used in commercial production, the every field such as Aero-Space and daily life.But, find that this battery has two aspects to compare distinct issues in actual applications, i.e. " voltage delay " and " security performance ".So, seriously constrain the extensive use of Li/SOCl2 battery.For the solution of these problems, concentrate on the advanced positive electrode of preparation, optimize electrolyte, reduce the aspects such as impedance Curve guide impeller technique；But it is long to there is the R&D cycle, apparatus and process requires height, and efficiency-cost ratio is relatively low waits deficiency.The market if it is desired that battery is more widely used, still needs to solve these problems further.Double-core subphthalocyanine compounds except the same with phthalocyanine compound have macro ring conjugated system structure, good give and connect nucleophobic performance, good heat stability and chemical stability except, also having the good characteristic of pi-conjugated system high degree of polarization, therefore double-core subphthalocyanine compounds is as Li/SOCl2Reserve cell catalyst has important researching value and is widely applied prospect.
Double-core subphthalocyanine compounds is as Li/SOCl2The application of cell catalyst not yet has been reported that at present.
Summary of the invention
The preparation method that it is an object of the present invention to provide a kind of double-core Asia phthalocyanines material, this preparation method is simple, it is a further object of the present invention to provide this double-core Asia phthalocyanines material as catalyst purposes in Li/SOCl2 battery.
The technical scheme that the present invention takes is: first passes through solvent method and prepares four nitrile presomas, then utilize four nitrile precursor power double-core Asia phthalocyanines of synthesis, be bonded mutually with the phenol type substances of para-position group finally by axial chemical modification method and prepare double-core Asia phthalocyanines material.
The preparation method of a kind of double-core Asia provided by the invention phthalocyanines material, specifically includes following steps:
(A) in an inert atmosphere, the bisphenol of the nitrophthalonitrile of 0.3-0.4g and 0.15-0.25g is dissolved in the DMF of 10-30ml, at 65-70 DEG C, reacts 3.5-4.5h, add catalyst K2CO3After, continue to react 3～4h at 65-70 DEG C, be cooled to room temperature, subsequently reactant mixture poured in mixture of ice and water, produce flocculent deposit, stand, sucking filtration, obtain thick product, obtain four nitrile presomas eventually through recrystallization；
(B) in an inert atmosphere, four nitrile presomas in the step (A) of the phthalonitrile of 0.2-1g and 0.3-1.7g are dissolved in 20-40ml high boiling solvent, add 0.15-0.6ml boron chloride or Boron tribromide reacts, reaction system stirs 0.5-1h at-15 DEG C～-5 DEG C, then in 0.5-1h, it is warming up to 170-190 DEG C and is incubated 5-7h, it is then cooled to room temperature, after solvent is distilled off, gained solid is scrubbed, obtain pink powder after drying, is double-core subphthalocyanine compounds；
(C) the double-core subphthalocyanine compounds obtained in 0.2-0.3g step (B) is joined in 3-10ml aromatic solvent with the methyl parahydroxybenzoate of 0.2-0.4g, hydroxy benzaldehyde or paranitrophenol, and instill 1-3 and drip pyridine and make catalyst, it is heated to reflux 10～20h, crude product is obtained after removing solvent, then use second alcohol and water that it is washed, filter, dry, obtain double-core Asia phthalocyanines material.
In the preparation method of the present invention, catalyst K in step (A)2CO32-4 times that consumption is bisphenol quality, inert atmosphere is nitrogen atmosphere or argon gas atmosphere.
In the preparation method of the present invention, in step (B), inert atmosphere is also nitrogen atmosphere or argon gas atmosphere.
In above-mentioned preparation method, the high boiling solvent added in step (B) is dichloro-benzenes, dimethylbenzene or naphthalene chloride.
In above-mentioned preparation method, in step (B), cleaning solvent is for being followed successively by petroleum ether, dichloromethane and methanol.
In above-mentioned preparation method, in step (B), drying mode is oven drying, and baking temperature is 60～70 DEG C, and drying time is 20～30h.
In above-mentioned preparation method, the aromatic solvent in step (C) is benzene, naphthalene, anthracene and derivant thereof.
Step according to method made above, its main technology path is as follows: with 4-nitrophthalonitrile for initiation material, makes itself and bisphenol generation nucleophilic substitution to prepare four nitrile presomas in solvent DMF.Then utilize four nitriles of synthesis and phthalonitrile as reacting initial thing, in high boiling point aromatic solvent, be obtained by reacting double-core subphthalocyanine compounds with Boron tribromide or boron chloride initial ring dimerization.Finally the double-core Asia phthalocyanine prepared and Pyrogentisinic Acid's class material are dissolved in aromatic solvent (being generally toluene), under the catalysis of pyridine, make phenol type substances that axial bromine atoms or the chlorine atom of double-core Asia phthalocyanine are carried out nucleophilic displacement of fluorine to prepare the double-core Asia phthalocyanines material of axial substituted, wherein R=-H ,-N02 ,-CHO ,-COOH ,-COOCH3.
Above reaction scheme can be summarized as follows:
The present invention also provides for the purposes of this double-core Asia phthalocyanines material, and this double-core Asia phthalocyanines material is at Li/SOCl2Battery system is tested, and has obvious catalytic effect.
The preparation method and its usage of the double-core Asia phthalocyanines material provided in the present invention, has a characteristic that
1, the preparation method of the double-core Asia phthalocyanines material provided in the present invention, simple, is very suitable for industrialized production.
2, the double-core Asia phthalocyanines material in the present invention is at Li/SOCl2In battery system, catalytic efficiency is high, and can make extend the discharge time of this battery, and discharge voltage improves.
3, the double-core Asia phthalocyanine catalyst in the present invention is environmental type, the less pollution to environment.
In the present invention, double-core Asia phthalocyanine catalyst preparation engineering is less costly, is beneficial to industrialized production.
Accompanying drawing explanation
Fig. 1 is Li/SOCl2The double-core Asia phthalocyanines materials different in the battery impact on discharge voltage and discharge time；
Fig. 2 is Li/SOCl2The double-core Asia phthalocyanines materials different in the battery impact on battery capacity；
Fig. 3 is the carbon positive pole (left figure) without sub-phthalocyanine catalyst and the carbon positive pole (right figure) adding double-core Asia phthalocyanine catalyst.
Detailed description of the invention
Embodiment 1
The synthesis of double-core Asia phthalocyanine
Under nitrogen protection, finely ground 4-nitrophthalonitrile 0.386g and bis-phenol 0.186g is dissolved in 15mLDMF, reacting by heating to 70 DEG C, constant temperature 3.5 hours, add catalyst K2CO30.552g, continues to react 3.5h at 70 DEG C, is finally cooled to room temperature, is poured in mixture of ice and water by reactant mixture subsequently, produce flocky precipitate, stand, sucking filtration, obtain thick product, obtain end product four nitrile presoma eventually through recrystallization.
Under nitrogen protection, being dissolved in by the four nitrile presoma 0.438g and phthalonitrile 0.521g prepared in the dry dichloro-benzenes of 20mL, add 0.29mLBBr3, reaction system stirs 0.5h under-10 DEG C of conditions, is then gradually heating to 180 DEG C at 0.5h and keeps 6h.After having reacted, room temperature to be cooled to, decompression is distilled off solvent, and gained solid utilizes petroleum ether, dichloromethane, methanol to wash.Products therefrom being put into 65 DEG C of dry 24h of vacuum drying oven, obtains aubergine powder, building-up process is as follows:
Embodiment 2
Double-core Asia phthalocyanine axial substituted thing (OHCPhO-BSubPc-OPh)2Preparation
The double-core Asia phthalocyanine 0.283g prepared and hydroxy benzaldehyde 0.305g (ratio is 1: 5) is joined in 5mL toluene, and instill 2-3 and drip pyridine and make catalyst, it is heated to reflux 16h, being cooled to room temperature, rotation is evaporated off solvent, obtains crude product, then use second alcohol and water that it is washed, filter, dry, obtain double-core Asia phthalocyanines material.Building-up process is as follows:
Embodiment 3
Double-core Asia phthalocyanine axial substituted thing [(NO2)PhO-BSubPc-OPh]2Preparation
Adopt the method in embodiment 2, use the double-core Asia phthalocyanine of preparation in 0.283g embodiment 1 and 0.348g paranitrophenol to prepare [(NO2)PhO-BSubPc-OPh]2Preparation process below figure:
Embodiment 4
Double-core Asia phthalocyanine axial substituted thing (HOOCPhO-BSubPc-OPh)2Preparation
Adopt the method in embodiment 2, use the double-core Asia phthalocyanine of preparation in 0.2772g embodiment 1 and 0.3314g that carboxylic phenol is prepared (HOOCPhO-BSubPc-OPh)2Preparation process below figure:
Embodiment 5
Double-core Asia phthalocyanine axial substituted thing (PhOCPhO-BSubPc-OPh)2Preparation
Adopt the method in embodiment 2, use the double-core Asia phthalocyanine of preparation in 0.2811g embodiment 1 and 0.2389g phenol to prepare (PhOCPhO-BSubPc-OPh)2Preparation process below figure:
Embodiment 6
Double-core Asia phthalocyanine axial substituted thing (H3COOCCPhO-BSubPc-OPh)2Preparation
Adopt the method in embodiment 2, use the double-core Asia phthalocyanine of preparation in 0.283g embodiment 1 and 0.380g methyl parahydroxybenzoate to prepare (H3COOCPhO-BSubPc-OPh)2Preparation process below figure:
Embodiment 7
The electrochemical properties test of double-core Asia phthalocyanines material carries out in simulated battery；Adopted electrochemical workstation is Zhengzhou Shi Ruisi instrument Science and Technology Ltd. RST5000 type electrochemical workstation, and operating platform is WindowsXP system.Anode is acetylene black and politef mixes the thin-film material rolling preparation by a certain percentage, and battery cathode is bright unoxidized lithium sheet, and barrier film is a kind of non-organic thing thin film made by glass fiber, and battery electrolyte is the LiAlCl of 1.47mol/L4/SOCl2Solution.Before test, carbon film, diaphragm cell housing and accessory battery be dry 4h at 70 DEG C all.During test, assemble under the dry atmosphere of RH < 1%, and to add the sub-phthalocyanine catalytic agent concentration configured be 2mg/1mL (about 4 × 10- 3Mol/L) battery electrolyte.Battery, under the steady temperature of 23 DEG C-25 DEG C, is discharged to 2V with permanent resistance 40 Ω and stops, and this time is denoted as battery discharge time t；Battery capacity C is then quantified by formula 1,
Wherein I is the average current of discharge process, can be tried to achieve by formula (2),
I=U/R----(2)
R=40 is substituted into formula (2) and with formula (1) simultaneous, battery capacity value can be obtained.
In the present invention, by adding different double-core Asia phthalocyanines materials, and contrast with blank sample, it has been found that different double-core Asia phthalocyanines materials is to Li/SOCl2The discharge time of battery and discharge voltage impact are different, as shown in Figure 1.Wherein, (OHCPhO-BSubPc-OPh)2Making extend discharge time maximum, original 403s increase to 547s, the percentage ratio 35.7% of increase, discharge voltage improves 0.04V relative to blank, increases to 3.04V, and battery capacity has also been correspondingly improved 35%；(HOOCPhO-BSubPc-OPh)2Making discharge voltage improve 0.10V, the amplitude of raising is maximum, but puts a time and battery capacity but consequently reduces, it is clear that this is not desirable catalyst；Add (H3COOCPhO-BSubPc-OPh)2After, battery discharge time extend 3.2%, 403s increase to 416s, discharge voltage increases to 3.05V, and corresponding battery capacity improves 1.2%；Add catalyst (PhOCPhO-BSubPc-OPh)2After, discharge time extends 113s, improves 28% relative to blank, and discharge voltage is increased to 3.05V by blank 3.00V, and the percentage ratio that corresponding battery capacity improves is 23.1%；[(NO2)CPhO-BSubPc-OPh]2Cell discharge voltage can be made to improve 0.08V, and the discharge time of battery extends to 462s, and relative to blank, the discharge time of battery and battery capacity all improve 14.6%.
By adding different double-core Asia phthalocyanines materials, and contrast with blank sample, it has been found that different double-core Asia phthalocyanines materials is to Li/SOCl2The battery capacity impact of battery is different, as shown in Figure 2.Wherein, (OHCPhO-BSubPc-OPh)2Battery capacity can be made to increase by 35%, and be maximum.
Embodiment 8
Assembling two batteries respectively, one adds 2mg double-core Asia phthalocyanine catalyst PhO-B (SubPc-OPh)2Another is as blank；After question response terminates, respectively the reacted carbon positive pole of two batteries is carried out electron-microscope scanning, as shown in Figure 3.Institute's employing instrument is HitachiTM3000 scanning electron microscope, and operating platform is WindowsXP system.By comparison it can be seen that define the film of densification on the carbon positive pole of catalyst-free owing to deposited the LiCl of substantial amounts of reaction generation, causing that in system, resistance increases, this is the major reason causing voltage delay；And in the battery adding catalyst, owing to the macro ring conjugated system of double-core Asia phthalocyanine has good electronic conduction ability so that carbon positive electrode surface structure is comparatively loose, be conducive to electrode reaction better to carry out.
Claims (7)
1. the preparation method of a double-core Asia phthalocyanines material, it is characterised in that comprise the following steps:
(A) in an inert atmosphere, the bisphenol of the nitrophthalonitrile of 0.3-0.4g and 0.15-0.25g is dissolved in the DMF of 10-30ml, at 65-70 DEG C, reacts 3.5-4.5h, add catalyst K2CO3After, continue to react 3-4h at 65-70 DEG C, be cooled to room temperature, subsequently reactant mixture poured in mixture of ice and water, produce flocculent deposit, stand, sucking filtration, obtain thick product, obtain four nitrile presomas eventually through recrystallization；
(B) in an inert atmosphere, four nitrile presomas in the step (A) of the phthalonitrile of 0.2-1g and 0.3-1.7g are dissolved in 20-40ml high boiling solvent, add 0.15-0.6ml boron chloride or Boron tribromide reacts, reaction system stirs 0.5-1h at-15 DEG C～-5 DEG C, then in 0.5-1h, it is warming up to 170-190 DEG C and is incubated 5-7h, it is then cooled to room temperature, after solvent is distilled off, gained solid is scrubbed, obtain pink powder after drying, it is double-core subphthalocyanine compounds, described high boiling solvent is dichloro-benzenes, dimethylbenzene or naphthalene chloride；
(C) the double-core subphthalocyanine compounds obtained in 0.2-0.3g step (B) is joined in 5-10ml aromatic solvent with the methyl parahydroxybenzoate of 0.2-0.4g, hydroxy benzaldehyde or paranitrophenol, and instill 1-3 and drip pyridine and make catalyst, it is heated to reflux 10-20h, crude product is obtained after removing solvent, then use second alcohol and water that it is washed, filter, dry, obtain product, be double-core Asia phthalocyanines material；
Concrete reaction scheme is as follows:
Wherein R is-COOCH3, aldehyde radical or nitro.
2. the preparation method of a kind of double-core Asia according to claim 1 phthalocyanines material, it is characterised in that catalyst K in described step (A)2CO32-4 times that consumption is bisphenol quality.
3. the preparation method of a kind of double-core Asia according to claim 1 phthalocyanines material, it is characterised in that described step (A) and the inert atmosphere in step (B) are nitrogen atmosphere or argon gas atmosphere.
4. the preparation method of a kind of double-core Asia according to claim 1 phthalocyanines material, it is characterised in that in described step (B), cleaning solvent is followed successively by petroleum ether, dichloromethane and methanol.
5. the preparation method of a kind of double-core Asia according to claim 1 phthalocyanines material, it is characterised in that in described step (B), drying mode is oven drying, and baking temperature is 60-70 DEG C, and drying time is 20-30h.
6. the preparation method of a kind of double-core Asia according to claim 1 phthalocyanines material, it is characterised in that the aromatic solvent in described step (C) is benzene, naphthalene, anthracene or derivatives thereof.
7. the purposes of the double-core Asia phthalocyanines material prepared by the method for claim 1, it is characterised in that: this double-core Asia phthalocyanines material is at Li/SOCl2Catalyst it is used as among battery system.
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