CN101982483A - Bis-azo type polyarylether copolymers, preparation method and application in aspect of optical storage - Google Patents
Bis-azo type polyarylether copolymers, preparation method and application in aspect of optical storage Download PDFInfo
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Abstract
The invention relates to a series of bis-azo type polyarylether copolymers, a preparation method of the series of the copolymers and an application thereof in the aspect of optical storage. The copolymers are homopolymers or random copolymers prepared by taking one of 4,4'-difluorobenzophenone, 4,4'-difluorotriphenyldione and 4,4'-dichlorodiphenyl sulfone, bis-azo difluoride monomer and hexafluobisphenol A as raw materials and carrying out nucleophilic polycondensation. The prepared polymers have high thermal stability and excellent film forming property. Thin films of the type of the azo polymers can rapidly form surface relief gratings which have good thermal stability and can be erased and written in a reversible manner under the irradiation of 355nm interference laser, and lead the polymers to show anisotropy and have the double refraction property under the irradiation of 532nm polarized light, and the double refraction property produced by induction can utilize the circularly polarized light to carry out convenient erasure. The properties represented by the type of the polymers can lead the polymers to be widely applied in the field of the reversible optical storage as optical response materials.
Description
Technical field
The invention belongs to field of polymer material preparing technology, be specifically related to the preparation method and the application aspect optical storage thereof of a series of tetrazo type polyarylether analog copolymers, this series copolymer.
Background technology
The azobenzene polymer material has huge application potential at aspects such as optical information storage, photoelectricity communications, and the azobenzene polymer material of exploitation novel type has important significance for theories and using value.Polyarylether polymer occupies extremely important position owing to have temperature classification height, radiation hardness, shock resistance and excellent comprehensive performance such as corrosion-resistant in the thermoplastic polymer field.Functional azo group is introduced in the polyarylether, realized the polyarylether functionalization and improve the over-all properties of polymkeric substance light responsive material, become the new research direction in this field.The present invention is incorporated into azo group the polyarylether system from molecular designing, has synthesized tetrazo type polyarylether copolymer, studies its photoinduction double refraction and the behavior of photoinduction surface relief grating and in the application of optical storage field.
Summary of the invention
In recent years, the photoinduction double refraction of azobenzene polymer uniqueness and the behavior of photoinduction surface relief grating become the focus of people's research.Azo group is incorporated in the polyarylether system of high thermal stability, helps improving the storage stability of material.The present invention has at first prepared a kind of novel disazo pair of fluorine monomer that contain, thereby improves the density of azo in polymkeric substance, and this contains disazo pair of fluorine monomer structural formula and is:
Purpose of the present invention is by the two fluorine monomers and 4 of novel tetrazo recited above, 4 '-difluoro triphen diketone (or 4,4 '-difluoro benzophenone, 4,4 '-dichlorobenzene sulfone) and the hexafluoro bisphenol-a copolymerization, synthesized a series of tetrazo type polyarylether copolymers, and the application of the type material aspect optical storage is provided.
The preparation process of the two fluorine monomers of tetrazo of the present invention is:
1, the sulfonation fluorine ketone of sodium-salt form is mixed with chlorsulfonic acid slowly is warming up to 80～120 ℃, under this temperature, reacted 4～10 hours.Then mixing solutions is poured in the frozen water, used in the sodium bicarbonate and a large amount of acid, divide extraction product three times with the 500mL methylene dichloride then, revolve steaming except that after desolvating and obtain white solid, both must contain the fluorine ketone of SULPHURYL CHLORIDE after the drying;
2, under the nitrogen protection; in the three-necked bottle that fills the 200mL methylene dichloride, add 4-hydroxyl-4 '-(itrile group) nitrogen benzide, triethylamine successively; the dichloromethane solution that under agitation will contain the fluorine ketone of SULPHURYL CHLORIDE slowly is added drop-wise in the instant liquid; dripping off the back continues to stir 2-12 hour; along with reaction carry out separate out a large amount of orange red crystal in the system, be the two fluorine monomers of tetrazo.
The mol ratio of the sulfonation fluorine ketone of sodium-salt form and chlorsulfonic acid is 1: 6～10 in above-mentioned reaction.The mol ratio that contains fluorine ketone, 4-hydroxyl-4 '-(itrile group) nitrogen benzide and the triethylamine of SULPHURYL CHLORIDE is 1: 2～4: 2～4, and the solid content of the two fluorine monomers of product tetrazo is 8%～10% in the 200mL methylene dichloride.
Structural formula by the two fluorine monomer institutes of tetrazo synthetic tetrazo type polyarylether copolymer is as follows:
0＜X≤1 wherein; N is 1～150 integer, the expression polymerization degree; The viscosity of polymkeric substance is 0.1～1.0, and number-average molecular weight (Mn) is 2000～100000, and dispersity (Mw/Mn) is 1.1～3;
Tetrazo type polyarylether copolymer preparation method of the present invention is described below:
With the two fluorine monomers of tetrazo, two fluorine or two chlorine monomer and biphenol monomer is raw material, and said pair of fluorine monomer is 4,4 '-difluoro benzophenone and 4, and 4 '-difluoro triphen diketone, two chlorine monomers are 4,4 '-dichloro diphenyl sulfone, biphenol monomer are hexafluoro bisphenol-a; With the Anhydrous potassium carbonate is salt forming agent, with N, N-N,N-DIMETHYLACETAMIDE (DMAc), tetramethylene sulfone TMS or dimethyl sulfoxide (DMSO) (DMSO) are reaction solvent, serve as the band aqua with toluene, benzene or dimethylbenzene, make tetrazo type polyarylether class homopolymer and random copolymers through nucleophilic polycondensation.Prepared polymkeric substance has higher thermostability and good film-forming properties, is the polyarylether class light responsive material that the novel side chain of a class contains the tetrazo group.
Detailed process is as follows:
(mix monomer is meant the two fluorine monomers and 4 of tetrazo with mix monomer, the monomeric mixing of 4 '-dichloro diphenyl sulfone, the two fluorine monomers and 4 of tetrazo, the monomeric mixing of 4 '-difluoro benzophenone, or the two fluorine monomers and 4 of tetrazo, the monomeric mixing of 4 '-difluoro triphen diketone), biphenol monomer and Anhydrous potassium carbonate mix, wherein the mole ratio of the total mole number of mix monomer and biphenol monomer is 1～1.01: 1, add organic solvent and band water solvent, be heated to band water temp (110～140 ℃) under the nitrogen protection, with the system complete drying, temperature of reaction is controlled at 150～160 ℃ then, continue reaction 4～24 hours, obtain multipolymer; Then product is poured in the deionized water, filtered through pulverizing, and use the deionized water repetitive scrubbing, remove and desolvate and inorganic salt, obtain tetrazo type polyarylether copolymer after the drying in baking oven, productive rate is 85～95%.
By changing the molar ratio of the two fluorine monomer consumptions of tetrazo in the mix monomer, can obtain the different polyarylether copolymer of tetrazo group content, the ratio that the two fluorine monomers of tetrazo account for the mix monomer total mole number is A%, 0%＜A%≤100%.
The mole number of salt forming agent consumption is 1～1.30 times of biphenol monomer consumption mole number in the reaction, organic solvent volume (mL) is 2.3mL～4mL: 1mg with mix monomer, biphenol monomer quality and ratio (mg), and the biphenol monomer of every 0.01mol uses 10～20ml band aqua.
Employed organic solution is N,N-dimethylacetamide (DMAc), tetramethylene sulfone TMS or dimethyl sulfoxide (DMSO) (DMSO).The band aqua is toluene, benzene or dimethylbenzene.
After tested, resulting tetrazo type polyarylether copolymer dissolves in chloroform, tetrahydrofuran (THF) (THF), N, dinethylformamide (DMF), N-Methyl pyrrolidone (NMP), pimelinketone and tetramethylene sulfone organic solvents such as (TMS).And utilize nuclear-magnetism, means of testing such as infrared to confirm its structure, in addition, can calculate the copolymerization content of the two fluorine monomers of tetrazo in the polymkeric substance by nuclear magnetic spectrogram.
The structural formula of the tetrazo type polyarylether copolymer of each embodiment preparation is as follows:
0＜X≤1 wherein; N is 1～150 integer, the expression polymerization degree; Viscosity is 0.1～1.0, and number-average molecular weight (Mn) is 2000～100000, and dispersity (Mw/Mn) is 1.1～3.
Above-mentioned polymkeric substance can be used as light responsive material and is used widely in reversible optical storage field.
With this series copolymer by weight the ratio of mark 5～15% be dissolved in the pimelinketone, after 0.8 micron filtering head filters, be spun on substrate (can be glass, quartz, ito glass or the metal etc.) surface.By freeze-day with constant temperature after progressively being warming up to 120 ℃ 12 hours, remove residual solvent then, obtain the polymeric film of homogeneous transparent, thickness can be controlled by regulator solution concentration and spin speed.Resulting polymeric film is exposed under the laser of interference of 355 nanometers, can forms the reversible erasable surface relief grating of good thermal stability fast, can use in fields such as holographic optical storages.Polymeric film is induced down at 532 nanometer Nd:YAG polarization lasers, and polymeric film presents stable photoinduction double refraction behavior, and can original position after the double refraction signal is wiped by circle light write once more can be used in reversible optical storage field.
Tetrazo type polyarylether copolymer film preparation surface relief grating process is as follows: this polymeric film is exposed under the 355 nanometer lasers irradiation of interference, can in holographic optical storage and patterned surface field potential application be arranged at the surface relief grating of film surface formation rule.Cycle can be controlled by the angle of controlling two beam interferometer light, and modulation depth can realize that (concrete principle is referring to Appl Phys Lett 1995,66 such as A.Natansohn, 136-138.) by light application time and laser intensity.
The photic research process of double refraction behavior of inducing of tetrazo type polyarylether copolymer film is as follows: this series polymer film is induced down at 532nm Nd:YAG polarization laser, azo group in the polymkeric substance can be by cis-trans isomerization motion repeatedly, finally arrange along the vertical direction of polarized light polarization direction, cause polymeric film to be anisotropic, produce the double refraction signal.And after the unlatching of circle light, azo chromophore evenly is orientated on each polarization direction of polarized light, causes polymeric film to be isotropy, and the double refraction signal is wiped free of, and finishes writing according to this and erase process of information.When the polarized light of 532nm once more during the irradiated polymer film, the double refraction signal can be by writing once more.By that analogy, we can repeat writing and wiping of signal.In reversible optical storage field potential application (concrete principle referring to: Chem.Rev.2002 such as A.Natansohn, 102,4139.) is arranged.
Description of drawings
Fig. 1: the proton magnetic spectrum figure of the two fluorine monomers of tetrazo;
The infrared spectrum of the tetrazo type polyarylether among Fig. 2: the embodiment 2;
The ultra-violet absorption spectrum of the DMF solution of the tetrazo type polyarylether among Fig. 3: the embodiment 2;
The nuclear magnetic spectrogram of the tetrazo type polyarylether among Fig. 4: the embodiment 2;
Fig. 5: the formed surface relief grating atomic force microscope of the tetrazo type polyarylether 3a figure among the embodiment 2-1: (A) be two-dimension picture; (B) be tri-dimensional picture; (C) be the profile analysis picture.
Fig. 6: the atomic force microscope figure after the formed surface relief grating thermal treatment of tetrazo type polyarylether 3a among the embodiment 2-1: (A) be two-dimension picture; (B) be tri-dimensional picture; (C) be the profile analysis picture.
Fig. 7: the tetrazo type polyarylether 3a among the embodiment 2-1 repeatedly writes and wipes curve.The A point is write light and is opened, and the B point is write light and closed, and C null circle light (erase signal) is opened.
Figure 1 shows that the proton magnetic spectrum figure of the two fluorine of tetrazo, the ownership of monomeric each hydrogen is all well belonged to as shown in Figure 1, proves that institute's synthetic compound is a target product.
Figure 2 shows that the tetrazo type polyarylether 3a among the embodiment 2, the infrared spectrum of 3b, 3c, wherein 1247 wave number places are the charateristic avsorption band of phenylate key (Ar-O-Ar); 1374 wave number places are sulphonate (Ar-SO
3-Ar) charateristic avsorption band; 2228 wave number places are cyano group (charateristic avsorption band CN).
Figure 3 shows that the tetrazo type polyarylether 3a among the embodiment 2, the nuclear magnetic spectrogram of 3b, 3c, the ownership of each hydrogen is all well belonged to as shown in Figure 3 in the polymkeric substance.
Figure 4 shows that tetrazo type polyarylether 3a, 3b, the 3c ultra-violet absorption spectrum in DMF solution among the embodiment 2, wherein in the characteristic absorbance that is absorbed as main polymer chain of 293 nanometers; The absorption peak of 350 nanometers is the charateristic avsorption band of the two key transconfigurations of azo group nitrogen nitrogen.
Figure 5 shows that the formed surface relief grating atomic force microscope of tetrazo type polyarylether 3a picture among the embodiment 2-1: (A) be two-dimension picture; (B) be tri-dimensional picture; (C) be the profile analysis picture.Can find out clearly that by figure polymer surfaces is the sinusoidal wave pattern of rule, by profile analysis figure as can be seen, this grating cycle is that 898 nanometers, the fluctuating degree of depth are 238 nanometers.
Figure 6 shows that the atomic force microscope picture after 220 ℃ of thermal treatments in 90 minutes of the formed surface relief grating of tetrazo type polyarylether 3a among the embodiment 2-1: (A) be two-dimension picture; (B) be tri-dimensional picture; (C) be the profile analysis picture.The grating fluctuating degree of depth that can be found out polymer surfaces by figure clearly obviously reduces, but pattern is still high-visible, and by profile analysis figure as can be seen, this grating cycle is that 898 nanometers, the fluctuating degree of depth are 6 nanometers.
Fig. 7 repeatedly writes and wipes curve for tetrazo type polyarylether 3a's among the embodiment 2-1.The A point is write light and is opened, and the B point is write light and closed, and C null circle light (erase signal) is opened.We can find that the erasable reversible repeatability of signal is fine, and as seen tangible fatigue phenomenon does not appear in this storage medium, and the potential using value is arranged in reversible optical storage.
Embodiment
Embodiment 1:
The chlorsulfonic acid of 25mL is slowly joined in the there-necked flask of the 100mL that fills 12.67 gram anhydrous sodium salt form sulfonation fluorine ketone.Under agitation, system slowly is heated to 100 ℃, and kept this thermotonus 4 hours, then mixing solutions is poured in the frozen water, with in the sodium bicarbonate and a large amount of acid, divide extraction product three times with the 500mL methylene dichloride then, revolve steaming except that after desolvating and obtain white solid, both got the fluorine ketone that 10 grams contain SULPHURYL CHLORIDE after the drying.
Under the nitrogen protection; in the three-necked bottle that fills the 200mL methylene dichloride, add 6.69 gram 4-hydroxyl-4 '-(itrile group) nitrogen benzides, 4.3mL triethylamine successively; the 50mL dichloromethane solution that under agitation 6.23 grams is contained SULPHURYL CHLORIDE fluorine ketone slowly is added drop-wise in the instant liquid; dripping off the back continues to stir 2 hours; along with reaction carry out separate out a large amount of orange red crystal in the system, be the two fluorine monomers of tetrazo and be about 10.6 grams.
Through the two fluorine monomer fusing points of DSC test gained tetrazo: 205 ℃, 7 ℃ of melting ranges are by mass spectrometric measurement two fluorine monomer C of gained tetrazo as can be known
39H
22F
2N
6O
7S
2Molecular ion peak be m/z=790.1 (M
++ H), conform to theoretical molecular 789; Infrared spectrum has occurred respectively-CN and Ar-SO at 2231,1196 wave number places
3Reaction has taken place in charateristic avsorption band proof SULPHURYL CHLORIDE and the phenol of-Ar, has generated the sulfonic acid ester bond.More than all signs proved that all our institute's synthetic monomer is a target product.
Embodiment 2:
Embodiment 2-1:
With two fluorine monomers of the tetrazo of 0.7888g (0.001mol) and 2.9007g (0.009mol) 4, the hexafluoro bisphenol-a of 4 '-difluoro triphen diketone and 3.3623g (0.01mol) joins in the three-necked bottle, adds the K of 1.4504g (0.013mol)
2CO
3, 25ml DMAc and 20ml toluene are heated with stirring under nitrogen protection and reflux 125～130 ℃, remove the water in the system, with the toluene of emitting behind the system finish-drying in the system, temperature of reaction are controlled at 150～160 ℃, react 24 hours.After reaction is finished, pour in the water polymers soln into precipitation and separate out polymkeric substance, use the deionized water repetitive scrubbing through pulverizing, remove and desolvate and inorganic salt, obtain polymkeric substance 6.5 gram, structural formula shown in A-3a, Ubbelohde viscometer (N, the N N,N-DIMETHYLACETAMIDE) recording viscosities il iv is 0.48 (dL/g), and GPC tests to such an extent that number-average molecular weight (Mn) is 4.3 * 10
4, dispersity is Mw/Mn=1.65, and the polymerization degree of emergencing copolymer is about 65, these show that we have higher molecular weight by institute's synthetic polymkeric substance.
Embodiment 2-2:
With two fluorine monomers of the tetrazo of 1.5775g (0.002mol) and 2.5784g (0.008mol) 4, the hexafluoro bisphenol-a of 4 '-difluoro triphen diketone and 3.3623g (0.01mol) joins in the three-necked bottle, adds the K of 1.4504g (0.013mol)
2CO
3, 25ml DMAc and 20ml toluene are heated with stirring under nitrogen protection and reflux 125～130 ℃, remove the water in the system, with the toluene of emitting behind the system finish-drying in the system, temperature of reaction are controlled at 150～160 ℃, react 24 hours.After reaction is finished, pour in the water polymers soln into precipitation and separate out polymkeric substance, use the deionized water repetitive scrubbing through pulverizing, except that desolvating and inorganic salt.Obtain 7.1 gram polymkeric substance, structural formula is shown in A-3b, and it is 0.38 (dL/g) that Ubbelohde viscometer (N, N N,N-DIMETHYLACETAMIDE) records viscosities il iv.
Embodiment 2-3:
With two fluorine monomers of the tetrazo of 2.3663g (0.003mol) and 2.2561g (0.007mol) 4, the hexafluoro bisphenol-a of 4 '-difluoro triphen diketone and 3.3623g (0.01mol) joins in the three-necked bottle, adds the K of 1.4504g (0.013mol)
2CO
3, 25ml DMAc and 20ml toluene are heated with stirring under nitrogen protection and reflux 125～130 ℃, remove the water in the system, with the toluene of emitting behind the system finish-drying in the system, temperature of reaction are controlled at 150～160 ℃, react 24 hours.After reaction is finished, pour in the water polymers soln into precipitation and separate out polymkeric substance, use the deionized water repetitive scrubbing through pulverizing, except that desolvating and inorganic salt.Obtain 7.4 gram polymkeric substance, structural formula is shown in A-3c, and it is 0.50 (dL/g) that Ubbelohde viscometer (N, N N,N-DIMETHYLACETAMIDE) records viscosities il iv.
Embodiment 3:
With two fluorine monomers of the tetrazo of 3.9436g (0.005mol) and 1.0905g (0.005mol) 4, the hexafluoro bisphenol-a of 4 '-difluoro benzophenone and 3.3623g (0.01mol) joins in the three-necked bottle, adds the K of 1.4504g (0.013mol)
2CO
3, 30ml DMAc and 25ml toluene are heated with stirring under nitrogen protection and reflux 125～130 ℃, remove the water in the system, with the toluene of emitting behind the system finish-drying in the system, temperature of reaction are controlled at 150～160 ℃, react 24 hours.After reaction is finished, pour in the water polymers soln into precipitation and separate out polymkeric substance, use the deionized water repetitive scrubbing through pulverizing, except that desolvating and inorganic salt.Obtain 7.8 gram polymkeric substance, structural formula is shown in B, and it is 0.40 (d L/g) that Ubbelohde viscometer (N, N N,N-DIMETHYLACETAMIDE) records viscosities il iv
Embodiment 4:
With two fluorine monomers of the tetrazo of 3.9436g (0.005mol) and 1.4358g (0.005mol) 4, the hexafluoro bisphenol-a of 4 '-dichloro diphenyl sulfone and 3.3623g (0.01mol) joins in the three-necked bottle, adds the K of 1.4504g (0.013mol)
2CO
3, 30ml DMAc and 25ml toluene are heated with stirring under nitrogen protection and reflux 125～130 ℃, remove the water in the system, with the toluene of emitting behind the system finish-drying in the system, temperature of reaction are controlled at 150～160 ℃, react 24 hours.After reaction is finished, pour in the water polymers soln into precipitation and separate out polymkeric substance, use the deionized water repetitive scrubbing through pulverizing, except that desolvating and inorganic salt.Obtain 7.9 gram polymkeric substance, structural formula is shown in C, and it is 0.43 (d L/g) that Ubbelohde viscometer (N, N N,N-DIMETHYLACETAMIDE) records viscosities il iv.
Embodiment 5:
The hexafluoro bisphenol-a of two fluorine monomers of the tetrazo of 3.9436g (0.005mol) and 1.6812g (0.005mol) is joined in the three-necked bottle, add the K of 0.7252g (0.0065mol)
2CO
3, 20ml DMAc and 15ml toluene are heated with stirring to backflow 125-130 ℃ under nitrogen protection, remove the water in the system, with the toluene of emitting behind the system finish-drying in the system, temperature of reaction are controlled at 150-160 ℃, react 24 hours.After reaction is finished, pour in the water polymers soln into precipitation and separate out polymkeric substance, use the deionized water repetitive scrubbing through pulverizing, except that desolvating and inorganic salt.Obtain 5.2 gram polymkeric substance, structural formula is shown in D, and it is 0.40 (d L/g) that Ubbelohde viscometer (N, N N,N-DIMETHYLACETAMIDE) records viscosities il iv.
Embodiment 6:
Resulting polymkeric substance 3a, 3b, 3c among embodiment 2-1, embodiment 2-2, the embodiment 2-3 are dissolved in (weight fraction 10%) in the pimelinketone solution respectively, solution filters through 0.8 micron filtering head, filtrate drips on glass basic surface, get uniform film through the refiner spin coating, thickness is about 1 micron, progressively is warming up to after 120 ℃ freeze-day with constant temperature and removes residual solvent in 12 hours.
Polymeric film is exposed under the laser radiation of 355 nanometers of interference, the two-beam angle is 22 °, shine 30 seconds can formation rule surface relief grating.Wherein the cycle of 3a is 898 nanometers, and the fluctuating degree of depth is 238 nanometers; The cycle of 3b is 898 nanometers, and the fluctuating degree of depth is 258 nanometers; The cycle of 3c is 898 nanometers, and the fluctuating degree of depth is 283 nanometers.Resulting grating all can carry out light by the single beam uniform irradiation to be wiped, and can write grating once more.With 3a is that example is carried out the research that heat is wiped behavior to it, after 90 minutes, the atomic power test is carried out on its surface 220 ℃ of thermal treatments, finds that the cycle of grating still is 898 nanometers, and the fluctuating degree of depth obviously is reduced to 6 nanometers.
Embodiment 7:
Resulting polymkeric substance 3a film among the embodiment 2-1 is exposed under the laser radiation of 355 nanometers of interference, the two-beam angle is set to 22 °, shine 15 seconds can formation rule surface relief grating.Its cycle is 898 nanometers, and the fluctuating degree of depth is 160 nanometers.
Embodiment 8:
Resulting polymkeric substance 3a film among the embodiment 2-1 is exposed under the laser radiation of 355 nanometers of interference, the two-beam angle is set to 40 °, and irradiation time is 15 seconds.The cycle of formed surface relief grating is 527 nanometers, and the fluctuating degree of depth is 102 nanometers.
Embodiment 9:
Resulting polymkeric substance 3a film among the embodiment 2-1 is induced down at 532nm Nd:YAG polarization laser, and the azo group in the polymkeric substance can be arranged along the vertical direction of polarized light polarization direction, causes polymeric film to be anisotropic, produces the double refraction signal.And after the unlatching of circle light, azo chromophore is evenly distributed on each polarization direction of polarized light, causes polymeric film to be isotropy, and the double refraction signal is wiped free of, and shows as writing and wiping of a signal.When the polarized light of 532nm once more during the irradiated polymer film, the double refraction signal can be by writing once more.By that analogy, we can repeat writing and wiping of signal.
Claims (8)
1. tetrazo type polyarylether copolymer, its structural formula is as follows:
Wherein, 0＜X≤1 is 1～150 integer, the expression polymerization degree; The viscosity of polymkeric substance is 0.1～1.0, and number-average molecular weight Mn is 2000～100000, and dispersity Mw/Mn is 1.1～3.
2. the preparation method of the described tetrazo type of claim 1 polyarylether copolymer, it is characterized in that: with mix monomer, biphenol monomer and Anhydrous potassium carbonate mix, mix monomer is meant the two fluorine monomers and 4 of tetrazo, the monomeric mixing of 4 '-dichloro diphenyl sulfone, the two fluorine monomers and 4 of tetrazo, the monomeric mixing of 4 '-difluoro benzophenone, or the two fluorine monomers and 4 of tetrazo, the monomeric mixing of 4 '-difluoro triphen diketone, the total mole number of mix monomer and the mole ratio of biphenol monomer are 1～1.01: 1, add organic solvent and band water solvent, be heated to 110～140 ℃ under the nitrogen protection, with the system complete drying, temperature of reaction is controlled at 150～160 ℃ then, continue reaction 4～24 hours, obtain multipolymer; Product is poured in the deionized water again, filtered through pulverizing, and use the deionized water repetitive scrubbing, remove and desolvate and inorganic salt, obtain tetrazo type polyarylether copolymer after the drying in baking oven, productive rate is 85～95%; Wherein the structural formula of the two fluorine monomers of tetrazo is as follows,
3. the preparation method of tetrazo type polyarylether copolymer as claimed in claim 2, it is characterized in that: the mole number of salt forming agent consumption is 1～1.30 times of biphenol monomer consumption mole number, the volume of consumption of organic solvent and mix monomer, biphenol monomer quality and ratio be 2.3mL～4mL: 1mg, the biphenol monomer of every 0.01mol uses 10～20ml band aqua.
4. the preparation method of tetrazo type polyarylether copolymer as claimed in claim 2 is characterized in that: organic solution is N,N-dimethylacetamide DMAc, tetramethylene sulfone TMS or dimethyl sulfoxide (DMSO) DMSO.
5. the preparation method of tetrazo type polyarylether copolymer as claimed in claim 2 is characterized in that: the band aqua is toluene, benzene or dimethylbenzene.
6. the application of the described tetrazo type of claim 1 polyarylether copolymer in reversible optical storage field.
7. the application of the described tetrazo type of claim 1 polyarylether copolymer in the holographic optical field of storage.
8. the described tetrazo type of claim 1 polyarylether copolymer is in the patterned surface Application for Field.
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| JP2013079367A (en) * | 2011-09-20 | 2013-05-02 | Toray Ind Inc | Aromatic sulfonate ester derivative, polymer containing sulfonate ester group, polyelectrolyte material using the same, polyelectrolyte molding using the same, electrolytic film with catalyst layer and polymer electrolyte fuel cell |
| CN103625153A (en) * | 2012-08-23 | 2014-03-12 | 中国人民银行印制科学技术研究所 | Optical storage anti-fake element, manufacturing method, application and optical elements applied to manufacturing process |
| CN104371132A (en) * | 2014-03-20 | 2015-02-25 | 南开大学 | Fixing method of surface relief gratings (SRGs) on azo polymer film |
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| US5173381A (en) * | 1991-08-05 | 1992-12-22 | Queen's University | Azo polymers for reversible optical storage |
| CN101486791A (en) * | 2009-02-13 | 2009-07-22 | 吉林大学 | Polyarylether copolymer with side chain containing azo group, as well as preparation and use thereof |
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2010
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5173381A (en) * | 1991-08-05 | 1992-12-22 | Queen's University | Azo polymers for reversible optical storage |
| CN101486791A (en) * | 2009-02-13 | 2009-07-22 | 吉林大学 | Polyarylether copolymer with side chain containing azo group, as well as preparation and use thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013079367A (en) * | 2011-09-20 | 2013-05-02 | Toray Ind Inc | Aromatic sulfonate ester derivative, polymer containing sulfonate ester group, polyelectrolyte material using the same, polyelectrolyte molding using the same, electrolytic film with catalyst layer and polymer electrolyte fuel cell |
| CN103625153A (en) * | 2012-08-23 | 2014-03-12 | 中国人民银行印制科学技术研究所 | Optical storage anti-fake element, manufacturing method, application and optical elements applied to manufacturing process |
| CN103625153B (en) * | 2012-08-23 | 2015-09-09 | 中国人民银行印制科学技术研究所 | Optical storage Security element, manufacture method, application and the optical element for the manufacture of process |
| CN104371132A (en) * | 2014-03-20 | 2015-02-25 | 南开大学 | Fixing method of surface relief gratings (SRGs) on azo polymer film |
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