CN103923311A - Carbazole-containing side chain type polyether sulfone, and preparation method and applications - Google Patents
Carbazole-containing side chain type polyether sulfone, and preparation method and applications Download PDFInfo
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Abstract
The invention relates to a carbazole-containing side chain type polyether sulfone as well as a preparation method and applications, and particularly relates to a carbazole functional group-containing side chain type polyether sulfone polymer, a preparation method and applications in an information storage device as an organic functional film, belonging to the technical field of an electro-storage new material. In addition, a typical storage device (ITO glass/polymer functional film/Al electrode) with a three-layer structure is prepared, so that the optimization on performances of the device can be realized, a polyether sulfone information storage material which is excellent in thermal property (5% thermal weight loss temperature of 378DEG C), low in energy consumption (low switching voltage of 2.5V), accurate in information reading (current ratio ON/OFF is more than 10<5>, and good repeated current reading parallelism), and long in information storage time (storage time is longer than 3*10<5>), has the write once read many (WORM) storage characteristic, and is stable in storage performance can be obtained, and the application field of the polyether sulfone material can be extended.
Description
Technical field
The invention belongs to electricity and cause storage new material technology field, be specifically related to a kind of polyether sulphone base polymer, preparation method and application in information recording device as organic functions film thereof of the side chain type that contains carbazole functional group.
Background technology
Along with the fast development of scientific and technological progress, particularly IT industry, to us, work, live and be with great facility in recent years, also let us has enjoyed the welfare that scientific and technological progress brings to the full.When sharply developing, digital communication technology also make the demand of storing device increase rapidly, also storing device is had higher requirement: memory device need to have higher storage density, simply portable, more excellent stability, energy-conserving and environment-protective, preparation technology is easy.
Traditional storage medium, the demand that can not meet industry development gradually for various reasons, whole world researcher is making great efforts to seek its substitute, for following information storage.In recent years, there is the storage medium of various new to be in the news, comprised chalcogenide materials, nitride material, some oxide materials etc.
Due to the raw material of organic compound be easy to get, cheap, synthetic simple, the storage medium based on organic compound has obtained the extensive concern in worldwide at present.This class storing device has typical sandwich structure, two electrode sandwich one deck organic compound thin film, electric current by test component is with the memory property of executing alive change curve and study device, and it utilizes the electric bi-stable conversion of organic molecule under the effect of electric field to realize the storage of information.What an electrode of general device was used is ito glass, and organic compound film is coated on ITO substrate by spin coating (polymkeric substance) or vacuum evaporation (organic molecule), and top electrode is metal electrode (vacuum evaporation mostly is Al).Than organic molecule, the purification of polymer materials is easy, calorifics excellent mechanical, masking are simple, good snappiness, complete processing are easy, there is good superiority, so the storage medium based on polymkeric substance has attracted more investigator's sight, and there is the multiple material with memory property successfully to be developed by researcher both domestic and external.Wherein in Chinese patent " CN101280054A " and " CN101182374A ", introduced respectively the correlative study of the memory material of polymer of conjugated polymers based on complex of iridium and ferrocene conductive polymers.But much need in addition the problem of solution badly in the process of exploitation memory material of polymer, chemical stability storage good not, device such as material is unstable, Ultrahigh is explained complicated, the performance optimization difficulty of device, switch current ratio is large not etc., and researchers also solve the above problem facing by various trials.
Polyether sulphone material is as a kind of special engineering plastics of excellent performance, possess outstanding mechanical property, good thermostability, excellent solvent resistance and acid-proof alkaline etc., in fields such as fuel cell, aerospace, separatory membranes, obtain a wide range of applications.And carbazole group possesses good cavity transmission ability, its excellent photoelectric properties make it at photoelectric field, be widely used.
Summary of the invention
The technical problem that the present invention mainly solves is that the polyether sulphone polymer materials that contains carbazole group has been synthesized in design, and uses this polymkeric substance to prepare memory device as functional membrane, by the chemical modification to grafted monomer, has realized the optimization to device performance.In the present invention, will contain several grafted monomer of carbazole group, by covalent linkage, be grafted on the side chain of special engineering plastics polyether sulphone of excellent performance respectively.This synthetic polymkeric substance contains carbazole functional group, has the performance of good photoelectricity aspect, can realize the application aspect electric field of storage.This polymkeric substance possesses high thermostability (thermal weight loss temperature is high) simultaneously, good solubility property, and the good advantages such as film-forming properties, can prepare polymer functional film by spin coating.Application as synthetic polymer, utilize it to prepare the memory device (ito glass/polymer functional film/Al electrode) typically with three-decker, and by the simple chemically modified to the grafted monomer that contains carbazole group, realized the optimization to device performance, obtained a kind of thermal property excellent (5% 378 ℃ of thermal weight loss temperature), energy consumption low (switching voltage is low ,～2.5V), information reads accurately (current ratio ON/OFF>10
5, repeatedly reading current collimation is good), long (shelf time >3 * 10 of information shelf time
5s), there is the stable poly (ether ketone ketone) information storage material of memory property that write-once repeatedly reads storage characteristics (Write-Once-Read-Many, WORM), expanded the Application Areas of poly (ether ketone ketone) material.
The present invention is using the side chain type polyether sulphone polymkeric substance that contains carbazole functional group as electric storage medium, prepare corresponding electrical storage device, the technique of preparation aspect that has related to the synthetic and device of material, and by the chemically modified of polymer lateral chain has been realized to the optimization to the memory property of device, improved the stability of device.
The polyether sulphone that contains carbazole side group of the present invention, its structure is as follows:
Wherein, R in above formula
1, R
2hydrogen atom or nitro.If R
1, R
2be all hydrogen atom, that corresponding is polymkeric substance Cz-PES1; If R
1, R
2one of them be hydrogen atom another be nitro, corresponding polymkeric substance is Cz-PES2; If R
1, R
2be nitro, corresponding polymkeric substance is Cz-PES3.
The preparation method of the side chain type polyether sulphone Cz-PES1 that contains carbazole of the present invention, its step is as follows:
(1) with 4-methoxyphenyl hydroquinone and 4,4-dichloro diphenyl sulfone is synthon, salt of wormwood is salt forming agent, three's mol ratio is 1:1～1.05:1.05～1.1, then the tetramethylene sulfone and the 1～5mL toluene that add 10～30mL, 120～140 ℃ of reaction 2～4h, emit toluene, be warming up to 210～220 ℃ of reaction 4～7h, discharging, in distilled water, is filtered, pulverize, use distilled water and ethanol respectively to wash several times, obtain anisole side group polyether ethersulfone after oven dry, 4-methoxyphenyl hydroquinone's consumption is 2～3g; 3.0g anisole side group polyether ethersulfone is joined in the pyridine hydrochloride of 80～100g new system, 160～180 ℃ of reaction 4～6h, are cooled to 130～140 ℃, and product is poured in frozen water, filter again, and vacuum drying, obtains the polyether ethersulfone that hydroxybenzene side group replaces;
(2) carbazole, 1, mol ratio 1:8～13:0.05～0.3 of 4-dibromobutane, Tetrabutyl amonium bromide, then adding 30～50mL toluene and 10～20mL, massfraction is the 50%KOH aqueous solution, 60～100 ℃ of reaction 10～15h, and the consumption of carbazole is 3～4 grams; Separatory, remove organic solvent, solid is used column chromatography to purify, and obtains grafted monomer Cz-1.
(3) polyether ethersulfone hydroxybenzene side group being replaced dissolves with DMF, adds grafted monomer Cz-1 and salt of wormwood, 80～100 ℃ of reaction 24～36h, product discharging, in distilled water, is filtered, washing, vacuum drying, obtains the side chain type polyether sulphone polymkeric substance Cz-PES1 that contains carbazole; The mol ratio of polyether ethersulfone, grafted monomer Cz-1 and salt of wormwood that wherein, hydroxybenzene side group replaces is 1.0:1.2～3.0:3.0～5.0.
The preparation method of the side chain type polyether sulphone Cz-PES2 that contains carbazole of the present invention, its step is as follows:
(1) Cz-1 is dissolved with 1,2-ethylene dichloride, be cooled to 5～15 ℃, keep this temperature, dropwise add concentrated nitric acid (massfraction is 65～68%), reaction 1～3h; Separatory, remove organic solvent, solid is used column chromatography to purify, and obtains grafted monomer Cz-2; Wherein the mol ratio of Cz-1 and concentrated nitric acid is 1.0:1.0～2.0;
(2) polyether ethersulfone hydroxybenzene side group being replaced dissolves with DMF, adds grafted monomer Cz-2 and salt of wormwood, 80～100 ℃ of reaction 24～36h, product discharging, in distilled water, is filtered, washing, vacuum drying, obtains the side chain type polyether sulphone polymkeric substance Cz-PES2 that contains carbazole; The mol ratio of polyether ethersulfone, grafted monomer Cz-2 and salt of wormwood that wherein, hydroxybenzene side group replaces is 1.0:1.2～3.0:3.0～5.0.
The preparation method of the side chain type polyether sulphone Cz-PES3 that contains carbazole of the present invention, its step is as follows:
(1) Cz-1 is dissolved with 1,2-ethylene dichloride, be cooled to 5～15 ℃, keep this temperature, dropwise add nitrosonitric acid (massfraction is 95～98%) and 1,2-ethylene dichloride mixed solution (volume ratio 1.0:0.5～2.0), reaction 1～3h, 40～60 ℃ of reaction 3～6h; Cooling, filters, and solid is used column chromatography to purify, and obtains grafted monomer Cz-3; Wherein the molar ratio of Cz-1 and nitrosonitric acid is 1.0:20.0～40.0.
(2) polyether ethersulfone hydroxybenzene side group being replaced dissolves with DMF, adds grafted monomer Cz-3 and salt of wormwood, 80～100 ℃ of reaction 24～36h, product discharging, in distilled water, is filtered, washing, vacuum drying, obtains the side chain type polyether sulphone polymkeric substance Cz-PES3 that contains carbazole; The mol ratio of polyether ethersulfone, grafted monomer Cz-3 and salt of wormwood that wherein, hydroxybenzene side group replaces is 1.0:1.2～3.0:3.0～5.0.
Synthetic three kinds of polymer reaction equations of side chain type polyether sulphone that contain carbazole below:
As the application of the polyether sulphone polymkeric substance that contains Process of A Side-chain Azo of the present invention, take it as functional membrane raw material, prepared the device for information storage.
Take polymkeric substance Cz-PES1, Cz-PES2 or Cz-PES3 as the preparation process of storage media device as follows:
Ito glass is cut out; and use reserved two the bar shaped ITO electrode parts (electrode width is 0.2mm) of ITO protection ink protection; uv irradiating makes ink crosslinked; be cross-linked rear use Zn/HCl and carried out etching; ito glass after etching makes water, acetone, Virahol supersound washing; do not have the ITO of ink protection to be etched away, thus only on glass remaining two wide be the ITO strip electrode of 0.2mm.Ito glass after cleaning is put in vacuum drying oven, dries stand-by.
Use dry DMF to dissolve polymkeric substance Cz-PES1, Cz-PES2 or Cz-PES3, being mixed with concentration is 5～15mg/mL polymers soln, use sol evenning machine that polymers soln is spun on after etching on ITO electrode and glass substrate, dry in vacuum drying oven, remaining organic solvent is removed, obtained being coated with the ITO substrate of polymkeric substance Cz-PES1, Cz-PES2 or Cz-PES3 functional membrane.Above-mentioned substrate is placed in vacuum deposition apparatus, uses the mask plate that width is 0.2mm, evaporation discrete and vertical with ITO electrode Al top electrode each other above polymer functional film, thus prepare information recording device.Use semiconductor parameter instrument, test be take electric current that polymkeric substance Cz-PES1, Cz-PES2 or Cz-PES3 be storage medium stores device with executing alive change curve.
Accompanying drawing explanation
The infrared spectrum of the synthetic side chain type polyether sulphone that contains carbazole in Fig. 1: embodiment 1,2,3.
TGA and the DTG curve of the synthetic side chain type polyether sulphone that contains carbazole in Fig. 2: embodiment 1,2,3.
Fig. 3: the surface sweeping Electronic Speculum section photo (a) of memory device, structural representation (b), device pictorial diagram (c).
The electric current of the memory device of Fig. 4: embodiment 4 preparations is with executing alive change curve.
The electric current of the memory device of Fig. 5: embodiment 5 preparations is with executing alive change curve.
The electric current of the memory device of Fig. 6: embodiment 6 preparations is with executing alive change curve.
The data read stability curve of the memory device of Fig. 7: embodiment 6 preparations.
Fig. 1 has provided the infrared absorption spectra of carbazole lateral chain type polyether sulphone synthetic in embodiment 1,2,3, as we know from the figure, and at 3000cm
-1near absorption peak is the vibration absorption peak of the hydrocarbon key of alkyl, and 1517cm
-1vibration absorption peak for nitro.This peak not in Cz-PES1, and occurred this peak in Cz-PES2 and Cz-PES3, and the peak in Cz-PES3 is obviously better than Cz-PES2, proved the structural difference of three kinds of polymkeric substance.
Fig. 2 has provided TGA and the DTG curve of the side chain type polyether sulphone that contains carbazole synthetic in embodiment 1,2,3.By scheming us, can know that synthetic carbazole lateral group polyarylether sulfone has good thermal stability.Under nitrogen atmosphere, 5% thermal weight loss of polymkeric substance is all higher than 368 ℃, illustrated that the thermal property of material is excellent, and good thermal property is conducive to improve the stability of the device of preparation, and the joule heating of avoiding producing in the use procedure of device causes the decomposition of material.
Fig. 3 has provided the structural representation of memory device.On the ito glass surface that surface is clean, by spin coating, prepared one layer of polymeric film, then utilize the Al top electrode that vacuum evaporation instrument is 100nm in its surface vacuum evaporation a layer thickness, obtained the test component (ITO/ polymeric film/Al) of a sandwich structure.
Fig. 4 has provided test component electric current in embodiment 4 with executing alive change curve.As we know from the figure, it is less that device starts electric current most, in low electricity, leads state, and after voltage reaches 3.0V, electric current starts obvious increase, and when voltage reaches 5.0V, it is maximum that electric current reaches, and device has reached high electricity and led state.In scanning process afterwards, device still keeps higher conductive capability, belongs to the memory device of WORM type, but has the shortcoming that conductive state sudden change is not obvious, current ratio is little, easily produces certain information and misreads, and storage effect is bad.
Fig. 5 has provided test component electric current in embodiment 5 with executing alive change curve.As we know from the figure, it is less that device starts electric current most, in low electricity, leads state, and after voltage reaches 1.8V, electric current starts increase rapidly, and when voltage reaches 3.0V, device has reached high electricity and led state.In scanning process afterwards, device still keeps higher conductive capability, belongs to the memory device of WORM type, suddenly change comparatively obvious, but smaller (ON/OFF～10 of electric current
2), storage effect is better.Hence one can see that by modify a nitro on carbazole, makes the performance of device obtain certain improvement.
Fig. 6 has provided test component electric current in embodiment 6 with executing alive change curve.As we know from the figure, it is less that device starts electric current most, in low electricity, leads state, and when voltage reaches 2.5V, electric current increases suddenly, and device has reached rapidly high electricity and led state.In scanning process afterwards, device still keeps higher conductive capability, meets the characteristic that write-once repeatedly reads, and belongs to the memory device of WORM type, suddenly change obvious especially, but the large (ON/OFF>10 of current ratio
5), storage effect is best.Hence one can see that modifies two nitros by symmetrical on carbazole group, makes the performance of device obtain improvement, and the sudden change of electric bi-stable is obvious, current ratio is large, has illustrated that chemically modified is a kind of effective means of improving the memory property of memory device.
Fig. 7 has provided the beta stability line (reading voltage is 2.5V) that reads time dependent beta stability line (reading voltage is 2.5V) and change with reading times of the memory device in the embodiment 6 with good memory property.From curve as shown in the figure, we can know, within the test duration of device (3.5 * 10
5s), and in limited reading times (470 times), have good information hold capacity, current value collimation is good, and the information that guaranteed reads read false rate low in process.Illustrated chemical modification by step by step final obtain based on Cz-PES3, as the device of storage media, there is good memory property.
Embodiment
Embodiment 1:
The synthetic method of Cz-PES1 provided by the invention, can realize by following reactions steps:
(1) by 4-methoxyphenyl hydroquinone (2.1623g; 0.0100mol); 4,4 '-dichloro diphenyl sulfone (2.8716g, 0.0100mol); salt of wormwood (1.4501g; 0.0105mol), tetramethylene sulfone (15mL), toluene (5mL) joins and is equipped with in agitator, water-and-oil separator, prolong 50mL there-necked flask; the lower 140 ℃ of reaction 3h of nitrogen protection, 210 ℃ of reaction 6h.Discharging, in distilled water, is filtered, and pulverizes, and uses distilled water and ethanol respectively to wash several times, obtains intermediate product anisole side group polyether ethersulfone (MPPES), 4.75g after oven dry.By intermediate product MPPES3.00g; the pyridine hydrochloride of 100g new system (slowly splashes into 80ml concentrated hydrochloric acid in 70ml pyridine; after dropwising; water in system is steamed; after cooling, obtain snowy white pyridine hydrochloride) join in the there-necked flask of 250mL; under the protection of nitrogen, 170 ℃ reaction 6h to system be homogeneous phase.Cool the temperature to 140 ℃, discharging, in a large amount of frozen water, is filtered, and vacuum drying obtains polyether ethersulfone (HPPES) 2.81g that intermediate product hydroxybenzene side group replaces.
(2) by carbazole 4.0g (23.9mmol), toluene 40mL, 1; 4-dibromobutane 30mL (247.0mmol); Tetrabutyl amonium bromide 0.7g (2.17mmol), massfraction 50%KOH aqueous solution 20mL adds in the 100mL there-necked flask of nitrogen protection, 80 ℃ of reaction 12h.Separatory, except desolventizing, solid is used column chromatography purification (200～300 order silica gel are as stationary phase, and methylene dichloride and sherwood oil volume ratio 1:6 mixed solvent are as moving phase), obtains white solid Cz-15.39g.
(3) HPPES of 0.2g is used the dry DMF of 6mL dissolve, add Cz-1 and the 0.25g K of 0.72mmol
2cO
3, the lower 100 ℃ of reaction 36h of nitrogen protection.Discharging, in distilled water, is filtered, washing, and vacuum drying, obtains Cz-PES1.
Embodiment 2:
The synthetic method of Cz-PES2 provided by the invention, can realize by following reactions steps:
(1) Cz-10.8g (2.6mmol) is used to 1 of 10mL, 2-ethylene dichloride dissolves, be cooled to 10 ℃, keep this temperature, in above-mentioned solution, dropwise add 0.3mL concentrated nitric acid (massfraction 65-68%), dropwise rear continuation and keep 10 ℃ of reaction 1h, separatory, removes organic solvent, and (200～300 order silica gel are as stationary phase to use column chromatography purification, trichloromethane and sherwood oil volume ratio 2:1 mixed solvent are as moving phase), obtain faint yellow solid Cz-20.81g.
(2) HPPES of 0.2g is used the dry DMF of 6mL dissolve, add Cz-2 and the 0.25g K of 0.72mmol
2cO
3, the lower 100 ℃ of reaction 36h of nitrogen protection.Discharging, in distilled water, is filtered, washing, and vacuum drying, obtains Cz-PES2.
Embodiment 3:
The synthetic method of Cz-PES3 provided by the invention, can realize by following reactions steps:
(1) Cz-10.8g (2.6mmol) is used to 1 of 10mL, 2-ethylene dichloride dissolves, be cooled to 10 ℃, keep this temperature, in above-mentioned solution, dropwise add 2mL nitrosonitric acid (massfraction 95-98%) and 1 of 2mL, 2-ethylene dichloride mixing solutions, dropwises rear continuation and keeps 10 ℃ of reaction 1h, is warming up to 45 ℃ of reaction 4h.Filter, after solid drying, use column chromatography purification (200～300 order silica gel are as stationary phase, and trichloromethane and sherwood oil volume ratio 3:1 mixed solvent are as moving phase), obtain yellow solid Cz-30.66g.
(2) HPPES of 0.2g is used the dry DMF of 6mL dissolve, add Cz-3 and the 0.25g K of 0.72mmol
2cO
3, the lower 100 ℃ of reaction 36h of nitrogen protection.Discharging, in distilled water, is filtered, washing, and vacuum drying, obtains Cz-PES3.
Embodiment 4:
(1) ITO being reduced is the rectangular shape of 2.0cm * 1.5cm, uses ITO protection ink to protect two reserved ITO strip electrodes (reserved width is 0.2mm), and ultra violet lamp 12h makes ink crosslinked.After being cross-linked, ITO small pieces are packed in beaker, (do are both usage ratio how many as etching agent to add Zn powder and concentrated hydrochloric acid?), ITO is carried out to etching 15s.By the good ito glass of etching, (width of remaining two ITO strip electrodes is 0.2mm; the ITO of all the other not protected ink protections is etched away) use respectively distilled water, acetone, Virahol respectively to clean twice in ultrasonic cleaner; each 15min, vacuum drying is stand-by.
(2) will contain Cz-PES1 and use dry DMF to dissolve, and be mixed with the polymers soln of 10mg/mL, and use organic filter of 0.22 μ m to filter this solution.Polymers soln is spun on to ito glass surface by sol evenning machine, and control rotating speed is 2000r/min, spin coating 30s, and vacuum drying, stand-by.Wherein the thickness of polymer layer is 65nm.
(3) ITO that scribbles polymkeric substance of drying is placed in to vacuum evaporation plating machine, (that uses 0.2mm can obtain the aluminium electrode that width is 0.2mm to use the mask plate that width is 0.2mm, the contact area of its ITO electrode of each test point obtaining like this and aluminium electrode is 0.2 * 0.2mm), the Al top electrode of evaporation one deck 100nm, has obtained the memory device for testing.Device is carried out on semiconductor parameter instrument to test current with executing alive change curve.
Embodiment 5:
(1) will contain Cz-PES2 and use dry DMF to dissolve, and be mixed with the polymers soln of 10mg/mL, and use organic filter of 0.22 μ m to filter this solution.Polymers soln is spun on to ito glass surface by sol evenning machine, and control rotating speed is 2000r/min, spin coating 30s, and vacuum drying, stand-by.Wherein, the thickness of polymer layer is 71nm.
(2) ITO that scribbles polymkeric substance of drying is placed in to vacuum evaporation plating machine, uses the mask plate that width is 0.2mm, the Al top electrode of evaporation one deck 100nm, has obtained the memory device for testing.Device is carried out on semiconductor parameter instrument to test current with executing alive change curve.
Embodiment 6:
(1) will contain Cz-PES3 and use dry DMF to dissolve, and be mixed with the polymers soln of 10mg/mL, and use organic filter of 0.22 μ m to filter this solution.Polymers soln is spun on to ito glass surface by sol evenning machine, and control rotating speed is 2000r/min, spin coating 30s, and vacuum drying, stand-by.Wherein, the thickness of polymer layer is 62nm.
(2) ITO that scribbles polymkeric substance of drying is placed in to vacuum evaporation plating machine, uses the mask plate that width is 0.2mm, the Al top electrode of evaporation one deck 100nm, has obtained the memory device for testing.Device is carried out on semiconductor parameter instrument to test current with executing alive change curve, and it is stored to stability in time and with the stability study of reading times.
Claims (7)
1. a polyether sulphone that contains carbazole side group, its structural formula is as follows:
Wherein, R
1, R
2for H or NO
2.
2. the preparation method of the polyether sulphone that contains carbazole side group claimed in claim 1, its step is as follows:
(1) with 4-methoxyphenyl hydroquinone and 4,4-dichloro diphenyl sulfone is synthon, salt of wormwood is salt forming agent, three's mol ratio is 1:1～1.05:1.05～1.1, then the tetramethylene sulfone and the 1～5mL toluene that add 10～30mL, 120～140 ℃ of reaction 2～4h, emit toluene, be warming up to 210～220 ℃ of reaction 4～7h, discharging, in distilled water, is filtered, pulverize, use distilled water and ethanol respectively to wash several times, obtain anisole side group polyether ethersulfone after oven dry, 4-methoxyphenyl hydroquinone's consumption is 2～3g; 3.0g anisole side group polyether ethersulfone is joined in the pyridine hydrochloride of 80～100g new system, 160～180 ℃ of reaction 4～6h, are cooled to 130～140 ℃ again, by product discharging in frozen water, filter, vacuum drying, obtains the polyether ethersulfone that hydroxybenzene side group replaces;
(2) carbazole, 1, mol ratio 1:8～13:0.05～0.3 of 4-dibromobutane, Tetrabutyl amonium bromide, then adding 30～50mL toluene and 10～20mL, massfraction is the 50%KOH aqueous solution, 60～100 ℃ of reaction 10～15h, and the consumption of carbazole is 3～4 grams; Separatory, remove organic solvent, solid is used column chromatography to purify, and obtains grafted monomer Cz-1;
(3) polyether ethersulfone hydroxybenzene side group being replaced dissolves with DMF, adds grafted monomer Cz-1 and salt of wormwood, 80～100 ℃ of reaction 24～36h, product discharging, in distilled water, is filtered, washing, vacuum drying, obtains the side chain type polyether sulphone polymkeric substance Cz-PES1 that contains carbazole, R
1, R
2it is all hydrogen atom; The mol ratio of polyether ethersulfone, grafted monomer Cz-1 and salt of wormwood that hydroxybenzene side group replaces is 1.0:1.2～3.0:3.0～5.0.
3. the preparation method of the polyether sulphone that contains carbazole side group claimed in claim 1, its step is as follows:
(1) 1,2-ethylene dichloride for the preparation-obtained grafted monomer Cz-1Cz-1 of claim 2 is dissolved, be cooled to 5～15 ℃, keep this temperature, dropwise adding massfraction is 65～68 % concentrated nitric acid, reaction 1～3h; Separatory, remove organic solvent, solid is used column chromatography to purify, and obtains grafted monomer Cz-2; Wherein the mol ratio of Cz-1 and concentrated nitric acid is 1.0:1.0～2.0;
(2) the polyether ethersulfone preparation-obtained hydroxybenzene side group of claim 2 being replaced dissolves with DMF, add grafted monomer Cz-2 and salt of wormwood, 80～100 ℃ of reaction 24～36h, product discharging is in distilled water, filter washing, vacuum drying, obtain the side chain type polyether sulphone polymkeric substance Cz-PES2 that contains carbazole, R
1, R
2in one be hydrogen atom, another is nitro; The mol ratio of polyether ethersulfone, grafted monomer Cz-2 and salt of wormwood that hydroxybenzene side group replaces is 1.0:1.2～3.0:3.0～5.0.
4. the preparation method of the polyether sulphone that contains carbazole side group claimed in claim 1, its step is as follows:
(1) by the preparation-obtained Cz-1 of claim 2 with 1,2-ethylene dichloride dissolves, be cooled to 5～15 ℃, keep this temperature, dropwise add massfraction be 95～98% nitrosonitric acid and 1,2-ethylene dichloride mixed solution, both volume ratio 1.0:0.5～2.0, reaction 1～3h, 40～60 ℃ of reaction 3～6h; Cooling, filters, and solid is used column chromatography to purify, and obtains grafted monomer Cz-3; Wherein the molar ratio of Cz-1 and nitrosonitric acid is 1.0:20.0～40.0;
(2) the polyether ethersulfone preparation-obtained hydroxybenzene side group of claim 2 being replaced dissolves with DMF, add grafted monomer Cz-3 and salt of wormwood, 80～100 ℃ of reaction 24～36h, product discharging is in distilled water, filter washing, vacuum drying, obtain the side chain type polyether sulphone polymkeric substance Cz-PES3 that contains carbazole, R
1, R
2be nitro; The mol ratio of polyether ethersulfone, grafted monomer Cz-3 and salt of wormwood that hydroxybenzene side group replaces is 1.0:1.2～3.0:3.0～5.0.
5. the application of the polyether sulphone that contains carbazole side group claimed in claim 1 in information recording device.
6. the application of the polyether sulphone that contains carbazole side group as claimed in claim 5 in information recording device, is characterized in that: as organic functions film.
7. the application of the polyether sulphone that contains carbazole side group as claimed in claim 6 in information recording device, is characterized in that:
(1) ito glass is cut out, and use two reserved bar shaped ITO electrode parts of ITO protection ink protection, uv irradiating makes ink crosslinked, be cross-linked rear use Zn/HCl and carried out etching, ito glass after etching makes water, acetone, Virahol supersound washing, do not have the ITO of ink protection to be etched away, thereby only at remaining two ITO strip electrodes on glass;
(2) use dry DMF to dissolve polymkeric substance Cz-PES1, Cz-PES2 or Cz-PES3, being mixed with concentration is 5～15mg/mL polymers soln, polymers soln is spun on ITO electrode and glass substrate, dry in vacuum drying oven, remaining organic solvent is removed, obtained being coated with the ITO substrate of polymkeric substance Cz-PES1, Cz-PES2 or Cz-PES3 functional membrane;
(3) above-mentioned substrate is placed in vacuum deposition apparatus, uses mask plate, evaporation discrete and vertical with ITO electrode Al top electrode each other above polymer functional film, thus prepare information recording device.
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