CN105482098B - The azo polyarylether liquid crystal material of a kind of side chain with Oligoanilines and preparation method thereof - Google Patents
The azo polyarylether liquid crystal material of a kind of side chain with Oligoanilines and preparation method thereof Download PDFInfo
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- CN105482098B CN105482098B CN201610046499.9A CN201610046499A CN105482098B CN 105482098 B CN105482098 B CN 105482098B CN 201610046499 A CN201610046499 A CN 201610046499A CN 105482098 B CN105482098 B CN 105482098B
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- LYQWYZKZARZMFR-QNEJGDQOSA-N O=C(C(CC=C1)C=C1/N=N/c1cccc(C(Nc(cc2)ccc2F)=O)c1)Nc(cc1)ccc1F Chemical compound O=C(C(CC=C1)C=C1/N=N/c1cccc(C(Nc(cc2)ccc2F)=O)c1)Nc(cc1)ccc1F LYQWYZKZARZMFR-QNEJGDQOSA-N 0.000 description 1
- WJTWWDSQTHZQTF-UHFFFAOYSA-N O=C(c(c(F)ccc1)c1F)Nc(cc1)ccc1Nc1ccccc1 Chemical compound O=C(c(c(F)ccc1)c1F)Nc(cc1)ccc1Nc1ccccc1 WJTWWDSQTHZQTF-UHFFFAOYSA-N 0.000 description 1
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
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- C08G2650/50—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing nitrogen, e.g. polyetheramines or Jeffamines(r)
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Abstract
There is the preparation method of the azo polyarylether liquid crystal material of Oligoanilines the invention discloses a kind of side chain, belong to functional high polymer material field.The present invention is respectively synthesized double fluorine monomer M2 that azo group is carried on double fluorine monomer M1 and main chain of the side chain with Oligoanilines by acylation reaction first, then by double fluorine monomer M1, double fluorine monomer M2 and bisphenol-A with 1:1:2 ratio, which carries out the obtained side chain of ternary nucleophilic polycondensation, has the azo polyarylether liquid crystal material of Oligoanilines.The azo polyarylether liquid crystal material that the side chain that the method provided by the present invention is synthesized has Oligoanilines has good electro-chemical activity, photo-isomerisable, dissolubility and heat endurance, and lysotropic liquid crystal can be produced in the organic solvent such as N dimethylacetylamides and dimethyl sulfoxide.The material is in biology sensor, optical element, has good application potential in terms of electromagnetic material.
Description
Technical field
The invention belongs to functional high polymer material field, and in particular to a kind of side chain carries the azo polyarylether of Oligoanilines
Liquid crystal material and preparation method thereof.
Background technology
With the continuous progress of science and technology, high-performance, multi-functional macromolecular material are got in fields such as space flight, traffic, national defence
More to obtain attention and the demand of people.Polyarylether is a kind of temperature classification very high thermoplastic, its temperature in use scope
It is relatively wide, and fatigue durability, hydrolytic resistance, anti-flammability are good, and creep resistant is wear-resisting, and in machinery, the high frontier such as Aero-Space is obtained
Extensive use is arrived.
In conducting polymer, polyaniline is because possessing inexpensive, good environmental stability, being readily synthesized, aoxidize also
Ortho states is adjustable, soda acid adulterates and the advantage of dedoping process simple possible, so being set in electromagnetic shielding material, electrochromic display
Had broad application prospects in terms of standby, electroluminescent cell and biology sensor.Lack however, polyaniline molecule structure is present
Fall into, and molten fusibleness and machinability are poor, and this greatly hinders the understanding and its practical application to Conducting Mechanism of Polyaniline.Tool
The aniline oligomer for having the electrical properties closely similar with polyaniline and having regular molecular structure and good solubility is recognized
To be the suitable substitute of polyaniline, but it lacks good stability and mechanical performance.Now feasible method is to pass
Machinable polymer of system obtains a series of new functional polymer materials with aniline oligomer by covalent bond, so may be used
Polyaniline and insulating polymer are blended into cohesion and the phase that obtained conducting polymer occurs to avoid passing through physical mixing processes
Separation.
In recent years with the optical active polymer of azo chromophore in optical element, optical transition and digit optical storage etc.
Aspect has obtained extensive concern.Between the transisomer that azobenzene group is stablized in unstable cis-isomer and relatively
Reversible photoisomerization conversion is the core property of its research.High isomerization efficiency, molecular shape and photoinduced nematic it is larger
Change makes azobenzene especially make researcher interested compared to other chromophores.
The domestic and international patent on the high molecular polymer in molecular chain structure simultaneously containing Oligoanilines and azo group
It is few with document.Chinese patent (101985495A) prepares side chain by the method for ternary polymerization and contains Tetraaniline chain
Section, main chain contains the polyarylether high molecule material of azo group, wherein 10<m<100,16<n<160, synthetic polymer has bright
Aobvious electroactive and good heat endurance, the favorable solubility in common organic solvents, machinability is strong.
[J.Mater.Chem., 2011,21 such as Xiaoteng Jia：18317-18324] pass through the side of Low-temperature Solution Polycondensation
Method has synthesized the azopolyamide containing Tetraaniline on side chain.Synthesizing polyamides show high glass transition temperature,
Good thermodynamic stability and reversible electrochemical properties, and with high contrast, low conversion time and appropriateness
The electrochromism feature such as coloration efficiency.Synthesizing polyamides show to induce the high stability of order for illumination, in diffraction efficiency
The change for the refractive index that the change of upper electrochemistry induction occurs with the change along with aniline oligomer segment redox state
Change consistent.Synthetic polymer structure is as follows：
Double fluorine acyls with double flutolanils of the side chain with aniline dimer segment and main chain belt azo group are not found also at present
Amine carries out the document report that ternary polymerization prepares polyarylether with bisphenol-A.We are respectively synthesized out side chain by acylation reaction
Double fluorine monomers of double fluorine monomers and main chain belt azo group with aniline dimer segment, then by two kinds of double fluorine monomers and bis-phenol
A is with 1:1:2 ratio carries out ternary nucleophilic condensation polymerization and obtains azo polyarylether of the side chain with Oligoanilines.
The content of the invention
The technical problems to be solved by the invention are to provide the azo polyarylether liquid crystal material that a kind of side chain carries Oligoanilines
Material and preparation method thereof, the liquid crystal material that the side chain of the liquid crystal material carries aniline dimer and is prepared by the method for the present invention has
There is electroactive and azobenzene polymer the optical Response similar to polyaniline.
The present invention provides institute in the azo polyarylether liquid crystal material that a kind of side chain carries Oligoanilines, its structural formula such as (I)
Show：
Wherein n is positive integer.
The present invention also provides the preparation method of azo polyarylether liquid crystal material of the above-mentioned side chain with Oligoanilines, and it is wrapped
Include following steps：
(1) double fluorine monomer M1s of the side chain with Oligoanilines synthesis：It is 1.5~3 by mol ratio：1 triethylamine and N- benzene
Base p-phenylenediamine is added in dichloromethane solvent, and stir to obtain solution one, the 4-aminodiphenylamine concentration in solution one
For 0.02~0.05g/mL；Molal quantity is dissolved in two for 2, the 6- difluoro benzoyl chlorides of above-mentioned 1~1.5 times of 4-aminodiphenylamine
Solution two is obtained in chloromethanes, wherein 2,6- difluorobenzoyl cl concns are 0.03~0.06g/mL；Dropwise will be molten under condition of ice bath
Liquid two is all added drop-wise in solution one dropwise, and nitrogen is protected and quickly stirred, and reacts at room temperature 4~6h, and suction filtration simultaneously uses second respectively
Ether and distillation water washing, the solid recrystallize with dichloromethane that last suction filtration is obtained fully are dried to obtain solid i.e. in baking oven
The double fluorine monomer M1 with Oligoanilines that are side chain, its structural formula is as shown in (II)；
(2) double fluorine monomer M2 of main chain belt azo group synthesis：Azo m-phthaloyl chloride is dissolved in dichloromethane
Solution three is obtained, the wherein concentration of azo m-phthaloyl chloride is 0.03~0.06g/mL；It is respectively between above-mentioned azo by molal quantity
The para-fluoroaniline and 1.5~2.1 times of triethylamine that 2~2.1 times of phthalyl chloride are added in dichloromethane solvent, are stirred
Solution four is obtained, wherein para-fluoroaniline concentration is 0.03~0.05g/mL；Solution three is all added dropwise in solution four and fast
Speed stirring, reacts at room temperature more than 5h, and suction filtration is simultaneously washed with distilled water and dichloromethane respectively, is fully dried to obtain in baking oven solid
Body is double fluorine monomer M2 of main chain belt azo group, and its structural formula is such as shown in (III)；
(3) synthesis of azo polyarylether liquid crystal material of the side chain with Oligoanilines：By double fluorine monomer M1, double fluorine monomer M2
With bisphenol-A according to mol ratio 1：1：2 ratio is dissolved in organic solvent, while adding 1~1.2 that molal quantity is double fluorine monomer M1
Times potassium carbonate and volume be the organic solvent volume 30~40% toluene, be passed through nitrogen and quickly stirring obtain reaction it is molten
Liquid, is warming up to 130~140 DEG C and reacts 3~5h to be removed water by azeotropic distillation, then proceed to be warming up to 180 DEG C that first is evaporated off
Benzene, continues to react more than 8h, reaction, which is finished, to be poured the mixture into precipitation, suction filtration, distilled water in distilled water and repeatedly wash, and is finally taken out
Filter obtained solid fully to dry in baking oven, dried solid again with methanol is extracted to extract close to colourless, in baking oven
The interior solid that is fully dried to obtain is the azo polyarylether liquid crystal material that side chain carries Oligoanilines, and its structural formula is such as shown in (I).
The present invention can also make further specific requirement or restriction to above-mentioned preparation method：
Specifically, the dichloromethane used in step (1) is the dichloromethane Jing Guo drying process, the drying process
Dichloromethane by by dichloromethane be heated to reflux with calcium hydride 7~8h of stirring and distill obtain.
Specifically, the total concentration in reaction solution of the double fluorine monomer M1, double fluorine monomer M2 and bisphenol-A in step (3)
For 0.2~0.3g/mL.Reaction solution includes double fluorine monomer M1, double fluorine monomer M2, bisphenol-A, potassium carbonate, organic solvent and toluene.
Specifically, organic solvent most preferably DMA or dimethyl sulfoxide (DMSO) in step (3).
Specifically, solution two is all added dropwise to the time used in solution one for 30~60min in step (1).
Specifically, solution three is all added dropwise to the time used in solution four for 10~30min in step (2).
Specifically, the specific requirement fully dry in baking oven described in step (1), (2) and (3) is：Dried in vacuum
More than 24h is dried in case at a temperature of 75~85 DEG C.
The azo polyarylether liquid crystal material of side chain prepared by the present invention with Oligoanilines has the electricity similar to polyaniline
The optical Response of activity and azobenzene polymer, at the same its also have favorable solubility, good thermal stability, mechanical strength higher and
A variety of elite clone characteristics such as machinability is strong, it will have great in terms of sensor, electromagnetic material, optical element
Application potential.
Brief description of the drawings
Fig. 1：The double fluorine monomer M1 synthesized in the present invention mass spectrogram；
Fig. 2：The double fluorine monomer M1 synthesized in the present invention infrared spectrum；
Fig. 3:The double fluorine monomer M2 synthesized in the present invention mass spectrogram；
Fig. 4：The double fluorine monomer M2 synthesized in the present invention infrared spectrum；
Fig. 5：The infrared spectrum of the azo polyarylether liquid crystal material synthesized in the present invention；
Fig. 6：The cyclic voltammetry curve figure of the azo polyarylether liquid crystal material synthesized in the present invention；
Fig. 7：The ultraviolet spectra curve of the azo polyarylether liquid crystal material synthesized in the present invention；
Fig. 8：The thermogravimetric curve of the azo polyarylether liquid crystal material synthesized in the present invention；
Fig. 9：The liquid crystal phase figure of the azo polyarylether liquid crystal material synthesized in the present invention.
Embodiment
Below by specific embodiment and the invention will be further described with reference to accompanying drawing, following examples are descriptive
, it is not limited, it is impossible to once limit protection scope of the present invention.
Method used in the present invention, unless otherwise required, is conventional method, reagent used in the present invention, such as
Without particular provisions, commercially available prod is.
Embodiment 1
A kind of preparation of azo polyarylether liquid crystal material of the side chain with Oligoanilines：
(1) 7.36g (40mmol) 4-aminodiphenylamines and 10mL (72mmol) triethylamine are dissolved in the two of 150mL dryings
In chloromethane alkane solvents, stir to obtain solution one, and the concentration of wherein 4-aminodiphenylamine is about 0.04g/mL；By 7.06g
(40mmol) 2,6- difluoro benzoyl chlorides, which are dissolved in 120mL dichloromethane, obtains solution two, and the concentration of 2,6- difluoro benzoyl chlorides is about
For 0.06g/mL, solution two is all instilled in solution one dropwise under the conditions of ice bath (0~5 DEG C), nitrogen is led to while dropwise addition
Protect and quickly stir, completion of dropping in 30min；After dripping, the lower room temperature of nitrogen protection continues to react 6h, and then suction filtration is used in combination
Ether and distillation water washing 3 times (can be washed for ether once, distill washing twice), what suction filtration was obtained after last time washing consolidates
Body recrystallize with dichloromethane 2 times, finally dries 24h at 80 DEG C of vacuum drying oven, obtains beige crystals 8.6g, as side chain
Double fluorine monomer M1 with Oligoanilines, yield is 60%.
(2) 3.07g (10mmol) azo m-phthaloyl chloride is dissolved in 50mL dichloromethane and obtains solution three, wherein azo
The concentration of m-phthaloyl chloride is about 0.06g/mL；2.22g (20mmol) para-fluoroaniline and 3mL (21mmol) triethylamine are dissolved in
In 60mL dichloromethane, stir to obtain solution four, and wherein para-fluoroaniline concentration is about 0.03g/mL；Solution three is whole dropwise
It is added in solution four, completion of dropping in 20min, generates a kind of pale yellow solution, continues to react 5h afterwards at room temperature, suction filtration is simultaneously
3 times (can be washed once for the alkane of dichloro four, distill washing twice) is washed with distilled water and dichloromethane, last time is obtained after washing
The solid arrived obtains light yellow solid 4.4g in 80 DEG C or so dry 24h of vacuum drying oven, and as main chain is double with azo group
Fluorine monomer M2, yield is 83%.
(3) by the double fluorine monomer M1 of 1.62g (5mmol), the double fluorine monomer M2 of 2.28g (5mmol) and 2.28g (10mmol) bis-phenol
A is dissolved in 20mL dimethyl sulfoxide solvents, and adds 1.7g (12mmol) potassium carbonate and 8mL toluene, is passed through nitrogen and is quickly stirred
Reaction solution is mixed to obtain, wherein double fluorine monomer M1, double fluorine monomer M2 and the bisphenol-A total concentration in reaction solution are about 0.22g/
ML, is warming up to 140 DEG C of reaction 3h to be removed water by azeotropic distillation, then proceedes to be warming up to 180 DEG C, be evaporated off after toluene, continue anti-
8h is answered, mixture pours into 500mL distilled water thing precipitation to be polymerized after completion of the reaction, suction filtration, distillation water washing is multiple, final suction filtration
Obtained solid is in 80 DEG C or so dry 24h of vacuum drying oven, and solid again with methanol extracting 30h or so is close to extract after drying
It is colourless, afterwards in 80 DEG C or so dry 24h of vacuum drying oven, brown solid 5g is obtained, as azo of the side chain with Oligoanilines gathers
Aryl oxide, yield is 81%.
Fig. 1,2 are shown in the step of embodiment 1 (1) carries out acyl by 2,6- difluoro benzoyl chlorides and 4-aminodiphenylamine
Change the mass spectrum and infrared spectrum for double fluorine monomer M1 that reaction is obtained.In mass spectrogram shown in Fig. 1, at mass-to-charge ratio 325.1152,
It is respectively the molecular ion hydrogenation peak of subject monomers at 347.0972 and at 363.0736, adds sodium peak and add potassium peak, illustrates successfully
Double fluorine monomer M1 are synthesized.In infrared spectrum shown in Fig. 2, wave number 3411cm-1And 3380cm-1Locate the vibration absorption peak for N-H,
3285cm-1Locate as the stretching vibration peak of N-H in amide structure, 3091cm-1And 3047cm-1Locate to shake for the flexible of the C-H on phenyl ring
Dynamic peak, 1623cm-1Locate as the stretching vibration peak of C=O in amide structure, 1589cm-1、1508cm-1、1458cm-1Locate as on phenyl ring
C=C stretching vibration peak, 1400cm-1Locate as the stretching vibration peak of C-N in amide structure, 1313cm-1Locate as in aniline structure
C-N stretching vibration peak, 1279cm-1Locate the stretching vibration peak for C-F, 790cm-1、756cm-1、693cm-1Locate as C-H on phenyl ring
Flexural vibrations absworption peak.
By azo m-phthaloyl chloride and para-fluoroaniline be acylated instead in the step of Fig. 3,4 show embodiment 1 (2)
The mass spectrum and infrared spectrum for the double fluorine monomer M2 that should be obtained.In mass spectrogram shown in Fig. 3, at mass-to-charge ratio 457.1491,
It is respectively the molecular ion hydrogenation peak plus sodium peak of subject monomers at 479.1311, at 495.1051 and adds potassium peak, illustrates successfully to close
Into double fluorine monomer M2.In infrared spectrum shown in Fig. 4,3268cm-1Locate as the stretching vibration absworption peak of N-H in amide structure,
3066cm-1Locate as the stretching vibration peak of C-H on phenyl ring, 1647cm-1Locate as the stretching vibration peak of C=O in amide structure,
1607cm-1、1577cm-1、1506cm-1Locate as the stretching vibration peak of C=C on phenyl ring, 1473cm-1Locate the stretching vibration for N=N
Peak, 1406cm-1Locate as the stretching vibration peak of C-N in amide structure, 1209cm-1Locate the stretching vibration peak for C-F, 817cm-1、
717cm-1、681cm-1Locate as the flexural vibrations absworption peak of C-H on phenyl ring.
Fig. 5 is shown in the step of embodiment 1 (3) by two kinds of double fluorine monomer M1, M2 and bisphenol-A with 1：1：2 mol ratio
The infrared spectrum for the azo polyarylether liquid crystal material that example ternary polymerization is obtained.In the infrared spectrum, 3383cm-1Locate stretching for N-H
Contracting vibration peak, 3257cm-1Locate as the stretching vibration peak of N-H in amide structure, 3056cm-1Locate as the stretching vibration of C-H on phenyl ring
Peak, 2976cm-1Locate as the stretching vibration peak of C-H in methyl, 1643cm-1Locate as the stretching vibration peak of N-H in amide structure,
1597cm-1、1506cm-1、1441cm-1Locate as the stretching vibration peak of C=C on phenyl ring, 1473cm-1Locate the stretching vibration for N=N
Peak, 1401cm-1Locate as the stretching vibration peak of C-N in amide structure, 1310cm-1Locate as the stretching vibration of C-N in aniline structure
Peak, 1230cm-1Locate as aryl oxide key Ar-O-Ar stretching vibration absworption peak, 817cm-1、742cm-1、691cm-1Locate as C- on phenyl ring
H flexural vibrations absworption peak.
Fig. 6 show the azo polyarylether liquid crystal material for having Oligoanilines according to the side chain of the method synthesis in embodiment 1
The cyclic voltammetry curve of material.The curve shows that polymer has a pair of redox peaks at 476mV/499mV, because polymer side
It is aniline dimer on chain, therefore it is poly- to only exist the correspondence of the redox peaks at full reduction-state and oxidized state, 476mV/499mV
Conversion of the compound between full reduction-state and oxidized state.
It is illustrated in figure 7 the azo polyarylether liquid crystal that there are Oligoanilines according to the side chain of the method synthesis in embodiment 1
The ultraviolet spectra curve of material.With the growth of ultra violet lamp time, absorbance of the polymer solution at wavelength 300nm by
It is decrescence small, correspondence trans-azobenzene group and the π-π * transition for being conjugated benzene ring system；And the absorbance at 416nm gradually increases
Greatly, the n- π * transition of correspondence cis-azobenzene group.The cis-trans isomerization process of azobenzene group is basic after ultraviolet lighting 12min
Stabilization is reached, hereafter curve is without significant change.
It is illustrated in figure 8 the azo polyarylether liquid crystal that there are Oligoanilines according to the side chain of the method synthesis in embodiment 1
The thermogravimetric curve of material.The curve is shown：Start slow thermal decomposition in 140 DEG C or so azo polyarylethers；Temperature reaches 290 DEG C
Thermal decomposition is accelerated, the decomposition of correspondence polymer segment.Temperature of the polymer at weightlessness 5%, 10% and 50% is respectively 280
DEG C, 345 DEG C, 759 DEG C, the polymer weightlessness 53% at 800 DEG C, thus illustrate synthesis side chain have Oligoanilines azo gather
Aryl oxide liquid crystal material has good heat endurance.
Fig. 9 show the azo polyarylether liquid crystal material for having Oligoanilines according to the side chain of the method synthesis in embodiment 1
The liquid crystal phase figure of material.Under cross-polarization light irradiation, synthesis azo polyarylether is showed in DMA solution
Go out lysotropic liquid crystal performance, form the bar-shaped texture of anisotropy.
Table 1 below show the azo polyarylether liquid crystal for having Oligoanilines according to the side chain of the method synthesis in embodiment 1
Dissolving implementations of the material in different solvents.It is measured by taking 0.2g polymer to add in 10mL solvents, temperature of the measurement
At 20 DEG C.Test result illustrates polymer favorable solubility in the larger solvent of polarity.
Table 1：The side chain that the present invention is synthesized has dissolubility of the azo polyarylether of Oligoanilines in different solvents
Note：1:Acetone is acetone, and methanol is methanol, CH2Cl2For dichloromethane, THF is tetrahydrofuran, DMAc
For DMA, NMP is 1-METHYLPYRROLIDONE.2:+ represent solvable ,+- represents to be partly dissolved ,-represent insoluble
Solution.
After testing, there is the side chain synthesized in embodiment 1 the number-average molecular weight Mn of the azo polyarylether of Oligoanilines to be
20094, molecular weight distribution (Mw/Mn) is 1.98.
Embodiment 2
A kind of preparation of azo polyarylether liquid crystal material of the side chain with Oligoanilines：
(1) 7.36g (40mmol) 4-aminodiphenylamines and 8.3mL (60mmol) triethylamine are dissolved in 100mL dryings
In dichloromethane solvent, stir to obtain solution one, and the concentration of wherein 4-aminodiphenylamine is about 0.05g/mL；By 10.6g
(60mmol) 2,6- difluoro benzoyl chlorides, which are dissolved in 200mL dichloromethane, obtains solution two, and the concentration of 2,6- difluoro benzoyl chlorides is about
For 0.05g/mL, solution two is all instilled in solution one dropwise under the conditions of ice bath (0~5 DEG C), nitrogen is led to while dropwise addition
Protect and quickly stir, completion of dropping in 45min；After dripping, the lower room temperature of nitrogen protection continues to react 5h, and then suction filtration is used in combination
Ether and distillation water washing 3 times (can be washed for ether once, distill washing twice), what suction filtration was obtained after last time washing consolidates
Body recrystallize with dichloromethane 2 times, finally dries 24h at 80 DEG C of vacuum drying oven, obtains beige crystals 8.7g, as side chain
Double fluorine monomer M1 with Oligoanilines, yield is 62%.
(2) 3.07g (10mmol) azo m-phthaloyl chloride is dissolved in 75mL dichloromethane and obtains solution three, wherein azo
The concentration of m-phthaloyl chloride is about 0.04g/mL；By 2.33g (21mmol) para-fluoroaniline and 2.14mL (15mmol) triethylamine
It is dissolved in 45mL dichloromethane, stir to obtain solution four, and wherein para-fluoroaniline concentration is about 0.05g/mL；By solution three all
It is added dropwise in solution four, completion of dropping in 10min, generates a kind of pale yellow solution, continues to react 6h afterwards at room temperature, take out
Filter and washed with distilled water and dichloromethane 3 times (can be washed once for the alkane of dichloro four, distill washing twice), last time is washed
The solid obtained afterwards obtains light yellow solid 4.3g in 80 DEG C or so dry 24h of vacuum drying oven, and as main chain carries azo group
Double fluorine monomer M2, yield is 82%.
(3) by the double fluorine monomer M1 of 1.62g (5mmol), the double fluorine monomer M2 of 2.28g (5mmol) and 2.28g (10mmol) bis-phenol
A is dissolved in 20mL DMA solvent, and adds 1.7g (12mmol) potassium carbonate and 8mL toluene, is passed through nitrogen
And reaction solution is quickly stirred to obtain, wherein double fluorine monomer M1, double fluorine monomer M2 and the bisphenol-A total concentration in reaction solution are about
For 0.22g/mL, 130 DEG C of reaction 5h are warming up to be removed water by azeotropic distillation, then proceedes to be warming up to 180 DEG C, toluene is evaporated off
Afterwards, continue to react 9h, mixture pours into 500mL distilled water thing precipitation to be polymerized after completion of the reaction, suction filtration, distillation water washing is more
Secondary, the solid that final suction filtration is obtained is in 80 DEG C or so dry 24h of vacuum drying oven, solid again with methanol extracting 30h or so after drying
To extract close to colourless, afterwards in 80 DEG C or so dry 24h of vacuum drying oven, brown solid 5.05g, as side chain band benzene are obtained
The azo polyarylether of amine segment, yield is 82%.
Embodiment 3
(1) 7.36g (40mmol) 4-aminodiphenylamines and 16.7mL (120mmol) triethylamine are dissolved in into 340mL to dry
Dichloromethane solvent in, stir to obtain solution one, and the concentration of wherein 4-aminodiphenylamine is about 0.02g/mL；Will
8.47g (48mmol) 2,6- difluoro benzoyl chlorides are dissolved in 270mL dichloromethane obtaining solution two, 2,6- difluoro benzoyl chlorides it is dense
Degree is about 0.03g/mL, all instills in solution one solution two dropwise under the conditions of ice bath (0~5 DEG C), leads to while dropwise addition
Nitrogen is protected and quickly stirred, completion of dropping in 60min；After dripping, the lower room temperature of nitrogen protection continues to react 6h, then suction filtration
And with ether and distilling water washing 3 times (can be washed for ether once, distill washing twice), suction filtration is obtained after last time is washed
Solid recrystallize with dichloromethane 2 times, finally dry 24h at 80 DEG C of vacuum drying oven, obtain beige crystals 8.6g, be
Side chain carries double fluorine monomer M1 of Oligoanilines, and yield is 60%.
(2) 3.07g (10mmol) azo m-phthaloyl chloride is dissolved in 100mL dichloromethane and obtains solution three, wherein occasionally
The concentration of nitrogen m-phthaloyl chloride is about 0.03g/mL；By 2.22g (20mmol) para-fluoroaniline and 2.6mL (18mmol) triethylamine
It is dissolved in 55mL dichloromethane, stir to obtain solution four, and wherein para-fluoroaniline concentration is about 0.04g/mL；By solution three all
It is added dropwise in solution four, completion of dropping in 30min, generates a kind of pale yellow solution, continues to react 5h afterwards at room temperature, take out
Filter and washed with distilled water and dichloromethane 3 times (can be washed once for the alkane of dichloro four, distill washing twice), last time is washed
The solid obtained afterwards obtains light yellow solid 4.6g in 80 DEG C or so dry 24h of vacuum drying oven, and as main chain carries azo group
Double fluorine monomer M2, yield is 85%.
(3) by the double fluorine monomer M1 of 1.62g (5mmol), the double fluorine monomer M2 of 2.28g (5mmol) and 2.28g (10mmol) bis-phenol
A is dissolved in 15mL dimethyl sulfoxide solvents, and adds 2.1g (14mmol) potassium carbonate and 4.5mL toluene, is passed through nitrogen and quick
Reaction solution is stirred to obtain, wherein double fluorine monomer M1, double fluorine monomer M2 and the bisphenol-A total concentration in reaction solution are about
0.3g/mL, is warming up to 135 DEG C of reaction 4h to be removed water by azeotropic distillation, then proceedes to be warming up to 180 DEG C, be evaporated off after toluene, after
Continuous to react 9h, mixture pours into 500mL distilled water thing precipitation to be polymerized after completion of the reaction, and suction filtration, distillation water washing is multiple, finally
The solid that suction filtration is obtained is in 80 DEG C or so dry 24h of vacuum drying oven, and solid again with methanol extracts 30h or so to extract after drying
Close to colourless, afterwards in 80 DEG C or so dry 24h of vacuum drying oven, brown solid 5.1g is obtained, as side chain is with Oligoanilines
Azo polyarylether, yield is 83%.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
Within principle, any modifications, equivalent substitutions and improvements made etc. should be included within the scope of the present invention.
Claims (8)
1. a kind of side chain carries the azo polyarylether liquid crystal material of Oligoanilines, it is characterised in that with the structure as shown in (I)
Formula, wherein n are positive integer,
2. a kind of preparation method of azo polyarylether liquid crystal material of side chain as claimed in claim 1 with Oligoanilines, it is special
Levy and be, comprise the following steps：
(1) double fluorine monomer M1s of the side chain with Oligoanilines synthesis：It is 1.5~3 by mol ratio：1 triethylamine and N- phenyl pair
Phenylenediamine is added in dichloromethane solvent, and stir to obtain solution one, and 4-aminodiphenylamine concentration is in solution one
0.02~0.05g/mL；Molal quantity is dissolved in dichloro for 2, the 6- difluoro benzoyl chlorides of above-mentioned 1~1.5 times of 4-aminodiphenylamine
Solution two is obtained in methane, wherein 2,6- difluorobenzoyl cl concns are 0.03~0.06g/mL；Dropwise by solution under condition of ice bath
Two are all added drop-wise in solution one dropwise, and nitrogen is protected and quickly stirred, and react at room temperature 4~6h, and suction filtration simultaneously uses ether respectively
With distillation water washing, the solid recrystallize with dichloromethane that last suction filtration is obtained, in baking oven being fully dried to obtain solid is
Double fluorine monomer M1s of the side chain with Oligoanilines, its structural formula is such as shown in (II)；
(2) double fluorine monomer M2 of main chain belt azo group synthesis：Azo m-phthaloyl chloride is dissolved in dichloromethane and obtains molten
Liquid three, the wherein concentration of azo m-phthaloyl chloride are 0.03~0.06g/mL；It is respectively above-mentioned azo isophthalic two by molal quantity
The para-fluoroaniline and 1.5~2.1 times of triethylamine that 2~2.1 times of formyl chloride are added in dichloromethane solvent, stir molten
Liquid four, wherein para-fluoroaniline concentration are 0.03~0.05g/mL；Solution three is all added dropwise in solution four and quickly stirred
Mix, react at room temperature more than 5h, suction filtration is simultaneously washed with distilled water and dichloromethane respectively, and solid is fully dried to obtain i.e. in baking oven
For double fluorine monomer M2 of main chain belt azo group, its structural formula is such as shown in (III)；
(3) synthesis of azo polyarylether liquid crystal material of the side chain with Oligoanilines：By double fluorine monomer M1, double fluorine monomer M2 and double
Phenol A is according to mol ratio 1：1：2 ratio is dissolved in organic solvent, while adding 1~1.2 times that molal quantity is double fluorine monomer M1
Potassium carbonate and volume are the toluene of the organic solvent volume 30~40%, be passed through nitrogen and quickly stirring obtain reaction solution,
It is warming up to 130~140 DEG C and reacts 3~5h to be removed water by azeotropic distillation, then proceedes to be warming up to 180 DEG C so that toluene is evaporated off,
Continue to react more than 8h, reaction, which is finished, to be poured the mixture into precipitation, suction filtration, distilled water in distilled water and repeatedly wash, last suction filtration
Obtained solid is fully dried in baking oven, and dried solid again with methanol is extracted to extract close to colourless, in baking oven
It is the azo polyarylether liquid crystal material that side chain carries Oligoanilines to be fully dried to obtain solid, and its structural formula is such as shown in (I)；
3. a kind of preparation method of azo polyarylether liquid crystal material of the side chain according to claim 2 with Oligoanilines,
Characterized in that, the dichloromethane used in step (1) is the dichloromethane Jing Guo drying process, the two of the drying process
Chloromethanes is obtained by the way that dichloromethane to be heated to reflux 7~8h of stirring with calcium hydride and distill.
4. a kind of preparation method of azo polyarylether liquid crystal material of the side chain according to claim 2 with Oligoanilines,
Characterized in that, double fluorine monomer M1, the total concentration of double fluorine monomer M2 and bisphenol-A in reaction solution in step (3) for 0.2~
0.3g/mL。
5. a kind of preparation method of azo polyarylether liquid crystal material of the side chain according to claim 2 with Oligoanilines,
Characterized in that, the organic solvent in step (3) is DMA or dimethyl sulfoxide (DMSO).
6. a kind of side chain according to any one of claim 2 to 5 carries the azo polyarylether liquid crystal material of Oligoanilines
Preparation method, it is characterised in that in step (1) solution two be all added dropwise to the time used in solution one for 30~
60min。
7. a kind of side chain according to any one of claim 2 to 5 carries the azo polyarylether liquid crystal material of Oligoanilines
Preparation method, it is characterised in that in step (2) solution three be all added dropwise to the time used in solution four for 10~
30min。
8. a kind of side chain according to any one of claim 2 to 5 carries the azo polyarylether liquid crystal material of Oligoanilines
Preparation method, it is characterised in that the specific requirement fully dry in baking oven described in step (1), (2) and (3) is：True
More than 24h is dried in empty baking oven at a temperature of 75~85 DEG C.
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Non-Patent Citations (3)
| Title |
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| Fabrication of electrochemically responsive surface relief diffraction gratings based on a multifunctional polyamide containing oligoaniline and azo groups;Xiaoteng Jia et al.;《J. Mater. Chem.》;20111014;第21卷;18317-18324 * |
| Novel Electroactive Poly(arylene ether sulfone) Copolymers Containing Pendant Oligoaniline Groups: Synthesis and Properties;DANMING CHAO et al.;《Journal of Polymer Science Part A: Polymer Chemistry》;20111231;第49卷;1605-1614 * |
| Synthesis and properties of novel electroactive poly(amic acid) and polyimide copolymers bearing pendant oligoaniline groups;Xiaoteng Jia et al.;《Polymer Chemistry》;20110412;第2卷;1300-1306 * |
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