CN101775111B - Method for preparing fully organic high-dielectric copolymers with side chains containing polyaniline chain segments - Google Patents
Method for preparing fully organic high-dielectric copolymers with side chains containing polyaniline chain segments Download PDFInfo
- Publication number
- CN101775111B CN101775111B CN2010101003884A CN201010100388A CN101775111B CN 101775111 B CN101775111 B CN 101775111B CN 2010101003884 A CN2010101003884 A CN 2010101003884A CN 201010100388 A CN201010100388 A CN 201010100388A CN 101775111 B CN101775111 B CN 101775111B
- Authority
- CN
- China
- Prior art keywords
- polyaniline
- copolymers
- dielectric
- sulfonic acid
- styrene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention provides a method for preparing a series of fully organic high-dielectric copolymer materials with side chains containing polyaniline chain segments, which is simple and has strong operability. A method for radical polymerization is used to solve the problem of separation existing between fillers and polymer substances and caused by a simple physical blending method, thereby improving the dielectric constants of the materials. Toluene is used as a reactive solvent, polyaniline mixed with phenylethylene and phenylethylene sulfoacid is used as a monomer for radical polymerization reaction, and then a series of copolymers containing different polyaniline mass fractions can be prepared through regulating the mass ratio of the polymerized monomer, thereby obtaining a series of copolymers with different dielectric constants. The obtained copolymers are configured into tetrahydrofuran solutions with the mass fractions of 10%-15%, and then copolymer films can be prepared by using a casting film-formation method. The copolymers obtained by the method have high dielectric constants and small density and is beneficial to the development of high-dielectric materials to small-size light materials.
Description
Technical field
The invention belongs to the high dielectric material technical field, be specifically related to a kind of side chain and contain fully organic high-dielectric copolymers material of polyaniline chain segments and preparation method thereof.
Background technology
High dielectric material is a kind of insulating material with broad prospect of application, because it has the performance of good store electrical energy and uniform electric field, thereby in electronics, motor and cable industry very important application is arranged all.Along with the develop rapidly of electronics, information and power industry, the active demand capacitor devices develops to the direction of high energy storage, miniaturization and less energy-consumption.For electrical condenser, in order to obtain the electrical condenser of small-sized lightness, high energy storage density, the then necessary employing dielectric substance that density is little, specific inductivity is high is as capacitor dielectric.Therefore, the novel high dielectric-constant dielectric material that has of development has great practical value and meaning.
High dielectric material is one of the most popular research topic of electronics, information and electromechanics trade always.Yet the high dielectric material of one-component is difficult to satisfy present industrial requirements.Though single stupalith has higher dielectric constant, but its processing temperature higher (generally above 1000 ℃), tooling cost is higher, and the more crisp bad mechanical property of material itself, and though but single polymkeric substance better mechanical property specific inductivity lower (being generally less than 10) can not satisfy the demands, thereby to design and develop novel polymer based composite high-dielectric material be pressing for of epoch.Though the method for simple physics blend has many good qualities, realize the mutual supplement with each other's advantages of single-phase component, inevitably there is problem such as be separated in snappiness etc. preferably.The chemical bond composite methods that we adopt is incorporated into conductive filler material on the side chain of polymkeric substance, can improve the problems such as reunion of filler preferably, thereby improve the specific inductivity of polymkeric substance, and this is a kind of very effective simple method.
Summary of the invention
The objective of the invention is polyaniline chain segments to be incorporated in the side chain of polymkeric substance, prepared the fully organic high-dielectric copolymers that a series of side chains contain polyaniline chain segments by the method for chemosynthesis.
We adopt the synthetic method of radical polymerization to solve the problem of phase separation that exists between filler that the simple physics blend method brings and the polymeric matrix, thereby have improved the specific inductivity of material.With toluene is solvent, the adulterated polyaniline of vinylbenzene and styrene sulfonic acid is the monomer of Raolical polymerizable, can prepare a series of multipolymers that contain the different polyaniline massfraction by the mass ratio of regulating polymerization single polymerization monomer, thereby obtain having a series of multipolymers of differing dielectric constant.This method is simple, and is simple to operate.
Side chain of the present invention contains the fully organic high-dielectric copolymers of polyaniline chain segments, and its structural formula is as follows:
Wherein, m, x, y are positive integer.
Its synthetic route is as follows:
Side chain contains the preparation method of the fully organic high-dielectric copolymers of polyaniline chain segments, and it comprises the steps:
A. with Sodium styrene sulfonate and the 0.84～6.68mL of 0.01～0.08mol, the aqueous hydrochloric acid of massfraction 37% joins in the water of 20～160mL and stirred 1～3 hour, add 0.01～0.08mol aniline monomer, in above-mentioned solution, drip the aqueous solution of the 20～160mL that contains 0.01～0.08mol ammonium persulphate under 0 ℃ of condition, dropwise the back and continue reaction 4～8h, reaction finishes direct suction filtration, filter cake washes with water till the neutrality, it is colourless to be washed till acetone with acetone again, 45～60 ℃ of drying 24～48h of vacuum (vacuum tightness is 0.1MPa) obtain the adulterated polyaniline of styrene sulfonic acid;
B. will be made into the toluene solution that concentration is 1.0～1.5g/mL after styrene monomer and the adulterated polyaniline mixing of styrene sulfonic acid, wherein, the massfraction that the adulterated polyaniline of styrene sulfonic acid accounts for styrene monomer and the adulterated polyaniline mixture of styrene sulfonic acid is 2～40%, ultra-sonic dispersion 15～30min, the Diisopropyl azodicarboxylate initiator that adds styrene monomer mole number 1.2%～3% again, behind argon gas deoxygenation 15～30min, 65～85 ℃ of polymerization 6～10h of oil bath remove solvent seasoning then and promptly obtain the fully organic high-dielectric copolymers that side chain contains polyaniline chain segments.
It is 10%～15% tetrahydrofuran solution that the multipolymer that obtains is configured to massfraction, to after the dissolving solution being inclined on the conductive glass of clean level fully, drying at room temperature promptly obtains copolymer film in 40～50 ℃ of drying 8～12h after 36～60 hours again.
Measure the thickness of co-polymer membrane earlier, coat the elargol electrode on the multipolymer surface then, and then carry out the test of specific inductivity.
The present invention contains the fully organic high-dielectric copolymers of polyaniline chain segments by the side chain of chemical polymerization method preparation, not only when low frequency 170Hz, has very high specific inductivity, when the adulterated polyaniline massfraction of styrene sulfonic acid in styrene monomer is 35%, specific inductivity is 3070, almost is about 1000 times of general polymer; And under higher frequency 1MHz, still has a high specific inductivity, the adulterated polyaniline massfraction of styrene sulfonic acid is 35% o'clock, specific inductivity is 220, and multipolymer has extraordinary solvability, as at tetrahydrofuran (THF), and N, N '-dimethyl formamide (DMF), N, N '-N,N-DIMETHYLACETAMIDE (DMAC) equal solvent is a kind of novel fully organic high-dielectric material.Preparation method's technology of the present invention is simple, can be handling strong.This invention has very high scientific value and practical value, has broad application prospects.
Description of drawings
Fig. 1: the infrared spectrum of the adulterated polyaniline of styrene sulfonic acid (a), multipolymer-20 (b) and multipolymer-35 (c); From the spectrogram we we have successfully synthesized target product as can be seen, the peak ownership at 3436 places be the vibration peak of N-H, 3232 ownership are=C-H
2Vibration peak, 2967,2925 be summed up as=vibration peak of C-H, 1571 and 1503 are respectively the vibration peak of the C=C of phenyl ring and quinone ring, 1149 is the vibration peak of S=O, this and wes' target product structure well meets.
Fig. 2: the uv atlas of the adulterated polyaniline of styrene sulfonic acid (a), multipolymer-20 (b) and multipolymer-35 (c); We see that the uv-absorbing of product and the uv-absorbing of polyaniline and polystyrene coincide the π-π on the phenyl ring in 250nm place peak position vinylbenzene and the polyaniline structure well from the spectrogram
*Transition of electron causes, 450 and the peak at 800nm place be that the proton transition of the polyaniline of doping attitude causes.
Fig. 3: (a) multipolymer-35, (b) multipolymer-30, (c) multipolymer-25 and (d) the film surface field emission scan electromicroscopic photograph of multipolymer 20.We can see that the surface of copolymer film is very smooth from figure, when the massfraction concentration of the adulterated polyaniline of styrene sulfonic acid reaches 35%, also do not observe significantly and are separated.Illustrate that we adopt the method for chemical bonding can very effectively avoid the generation that is separated.
Fig. 4 (a): the specific inductivity of multipolymer of the adulterated polyaniline of styrene sulfonic acid that contains different concns is at room temperature with the change curve of frequency.As shown in the figure, when the concentration of the adulterated polyaniline of styrene sulfonic acid was lower than 20%, specific inductivity increased slowly with the increase numerical value of concentration, increases slow that specific inductivity descends with frequency; When concentration is higher than 20%, specific inductivity with being changed significantly of frequency be reduced in 100～1000Hz scope, descend slowly afterwards; When the concentration of the adulterated polyaniline of styrene sulfonic acid near 30% the time, the increase that the specific inductivity of multipolymer is at full speed, specific inductivity reaches 2510 when 170Hz, when concentration reached 35%, it is maximum that the specific inductivity of multipolymer reaches, when 170Hz greater than 3000; When concentration was higher than 35%, specific inductivity reduced, and this is to have formed conductive network owing to being in contact with one another between the polyaniline chain segments, has reduced the charge storage ability, and specific inductivity reduces.
Fig. 4 (b): the specific inductivity loss of multipolymer of the adulterated polyaniline of styrene sulfonic acid that contains different concns is with the change curve of frequency.As shown in the figure, dielectric loss has an extreme value with the variation of frequency, corresponding the dipole alignment relaxation position of specific inductivity, and dielectric loss is with the reduction that is changed significantly of frequency afterwards.
Fig. 5: the massfraction of the adulterated polyaniline of styrene sulfonic acid is 35% o'clock, the specific inductivity correlation curve (a) of the co-polymer membrane that obtains with the method for chemical polymerization method and physical blending respectively, the stereoscan photograph on the surface of the film that the method for chemical polymerization obtains (b), the stereoscan photograph on the surface of the film that the method for physical blending obtains (c); As shown in the figure, the specific inductivity of scheming the method that we see our chemosynthesis from (a) is about 10 times of simple physics blend method under low frequency; (b) and (c) scheme us and also the surperficial electron microscope photo scanning of the film of two kinds of different methods preparations contrasted, therefrom we we have significantly improved the problem that is separated at the method for chemical bonding as can be seen.
Fig. 6: the specific inductivity of multipolymer under different frequency with the variation of the adulterated polyaniline concentration of styrene sulfonic acid.When the adulterated polyaniline concentration of styrene sulfonic acid was lower than 20%, specific inductivity increased slowly; When concentration continuation increase, specific inductivity rises significantly, and the seepage flow threshold value is approximately 30%, when concentration reaches 35%, and the specific inductivity maximum; When concentration continuation increase, specific inductivity reduces.
Embodiment
Synthesizing of the adulterated polyaniline of styrene sulfonic acid
Embodiment 1:
With the Sodium styrene sulfonate of 0.08mol and 6.68mL, massfraction is that 37% aqueous hydrochloric acid joins in the deionized water of 160mL, stir the aniline that adds 0.08mol after 1 hour, under 0 ℃ of condition, drip the aqueous solution of the 160mL that contains the 0.08mol ammonium persulphate, dropwising the back continues about reaction 4h, direct suction filtration after reaction finishes, it is neutral that filter cake washes with water to the aqueous solution, again with acetone wash 3 times colourless to acetone, 45 ℃ of dry 24h of vacuum (vacuum tightness is 0.1) obtain the adulterated polyaniline of exsiccant styrene sulfonic acid.
Preparation with high-k copolymer material
Embodiment 2:
The adulterated polyaniline of styrene sulfonic acid and vinylbenzene are accounted for total mass mark 0,5%, 7%, 10%, 15%, 20%, 25%, 30%, 35%, 38% the ratio of being respectively according to the adulterated polyaniline of styrene sulfonic acid carry out polyreaction, obtain the fully organic high-dielectric copolymers that a series of side chains contain polyaniline chain segments.
When being 20% with the massfraction when the adulterated polyaniline of styrene sulfonic acid is example, and being defined as the multipolymer that obtains is multipolymer-20, by that analogy.Its polyreaction is: adulterated polyaniline of 2.083g styrene sulfonic acid and 0.5208g styrene monomer join in the three-necked bottle of 50mL, the toluene solvant that adds 2mL again, add the 0.0492g Diisopropyl azodicarboxylate behind the ultrasonic 30min, behind the argon gas deoxygenation 30min, oil bath is reacted down about 6h for 85 ℃, and removing desolvates obtains the fully organic high-dielectric copolymers that side chain contains polyaniline chain segments.
Film preparation with high-k copolymer material
Embodiment 3:
The fully organic high-dielectric copolymers that the side chain that obtains is contained polyaniline chain segments is dissolved in the tetrahydrofuran (THF), be configured to the copolymer quality mark and be 10% solution, after treating that multipolymer dissolves fully, the solution of multipolymer is inclined on the conductive glass plate of clean level, after the drying at room temperature 48 hours, dry 12h under 45 ℃ of temperature condition obtains copolymer film again, and the stereoscan photograph on copolymer film surface as shown in Figure 3.
The test of high dielectric material
Embodiment 4:
At first use milscale to measure the thickness of co-polymer membrane, coat elargol on the surface of co-polymer membrane, measure area, test as electrode with conductive glass and elargol respectively, test frequency is 100Hz～1M Hz.
Claims (1)
1. a structural formula side chain as follows contains the preparation method of the fully organic high-dielectric copolymers of polyaniline chain segments, and it comprises the steps:
A. with Sodium styrene sulfonate and the 0.84～6.68mL of 0.01～0.08mol, the aqueous hydrochloric acid of massfraction 37% joins in the water of 20～160mL and stirred 1～3 hour, add 0.01～0.08mol aniline monomer, dripping ammonium persulphate content under 0 ℃ of condition in above-mentioned solution is the aqueous solution of 20～160mL ammonium persulphate of 0.01～0.08mol, dropwise the back and continue reaction 4～8h, reaction finishes direct suction filtration, filter cake washes with water till the neutrality, it is colourless to be washed till acetone with acetone again, 45～60 ℃ of drying 24～48h of vacuum obtain the adulterated polyaniline of styrene sulfonic acid;
B. be made into the toluene solution that concentration is 1.0～1.5g/mL after the polyaniline mixing with styrene monomer and styrene sulfonic acid doping; Wherein, The mass fraction that the polyaniline that styrene sulfonic acid mixes accounts for the polyaniline mixture of styrene monomer and styrene sulfonic acid doping is 2～40%; Ultrasonic dispersion 15～30min; The azodiisobutyronitrile initator that adds again styrene monomer molal quantity 1.2%～3%; Behind argon gas deoxygenation 15～30min; 65～85 ℃ of polymerization 6～10h of oil bath; Desolventizing is drying to obtain the fully organic high-dielectric copolymers that side chain contains polyaniline chain segments then
Wherein, m, x, y are positive integer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101003884A CN101775111B (en) | 2010-01-25 | 2010-01-25 | Method for preparing fully organic high-dielectric copolymers with side chains containing polyaniline chain segments |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101003884A CN101775111B (en) | 2010-01-25 | 2010-01-25 | Method for preparing fully organic high-dielectric copolymers with side chains containing polyaniline chain segments |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101775111A CN101775111A (en) | 2010-07-14 |
| CN101775111B true CN101775111B (en) | 2011-09-28 |
Family
ID=42511709
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101003884A Expired - Fee Related CN101775111B (en) | 2010-01-25 | 2010-01-25 | Method for preparing fully organic high-dielectric copolymers with side chains containing polyaniline chain segments |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101775111B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103755918B (en) * | 2014-01-09 | 2015-08-26 | 吉林大学 | Side chain type electroactive polyurea polymer, preparation method and the application in anticorrosion thereof |
| CN108503755A (en) * | 2017-12-26 | 2018-09-07 | 刘超 | A kind of manufacturing process of novel polymerizable polyaniline material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1243849A (en) * | 1999-07-12 | 2000-02-09 | 武汉工业大学 | nm-class composite polyphenylamine-Fe2O3 material and its preparing process |
| CN1958658A (en) * | 2006-11-21 | 2007-05-09 | 南京大学 | Method for preparing conductive, high molecular compound particles of polystyrene / polyaniline |
| CN101469285A (en) * | 2007-12-28 | 2009-07-01 | 西北工业大学 | Polyaniline nano-rod ER fluid |
-
2010
- 2010-01-25 CN CN2010101003884A patent/CN101775111B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1243849A (en) * | 1999-07-12 | 2000-02-09 | 武汉工业大学 | nm-class composite polyphenylamine-Fe2O3 material and its preparing process |
| CN1958658A (en) * | 2006-11-21 | 2007-05-09 | 南京大学 | Method for preparing conductive, high molecular compound particles of polystyrene / polyaniline |
| CN101469285A (en) * | 2007-12-28 | 2009-07-01 | 西北工业大学 | Polyaniline nano-rod ER fluid |
Non-Patent Citations (1)
| Title |
|---|
| 姚慧玲等.聚苯胺/聚（苯乙烯-苯乙烯磺酸钠）纳米核-壳结构聚合物的微乳液法合成及性能表征.《山东大学学报（理学版）》.2008,第43卷(第3期),26-29. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101775111A (en) | 2010-07-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhao et al. | Gel polymer electrolyte based on polymethyl methacrylate matrix composited with methacrylisobutyl-polyhedral oligomeric silsesquioxane by phase inversion method | |
| KR0162864B1 (en) | Process for preparing electrically conductive polypyrrole having excellent solubility | |
| Baik et al. | Solid polymer electrolytes containing poly (ethylene glycol) and renewable cardanol moieties for all-solid-state rechargeable lithium batteries | |
| JPWO2010095648A1 (en) | Composite conductive polymer composition, method for producing the same, solution containing the composition, and use of the composition | |
| Zuo et al. | Enhanced performance of a novel gel polymer electrolyte by dual plasticizers | |
| CN102746514B (en) | Hyper branched polysiloxane modified polyaniline (PANI) and preparation method thereof | |
| Ma et al. | Three-dimensional hierarchical walnut kernel shape conducting polymer as water soluble binder for lithium-ion battery | |
| WO2000057440A1 (en) | Electrolyte composition for electric double layer capacitor, solid polymer electrolyte, composition for polarizable electrode, polarizable electrode, and electric double layer capacitor | |
| Liu et al. | A novel polyacrylonitrile-based porous structure gel polymer electrolyte composited by incorporating polyhedral oligomeric silsesquioxane by phase inversion method | |
| CN101775111B (en) | Method for preparing fully organic high-dielectric copolymers with side chains containing polyaniline chain segments | |
| CN101996770B (en) | Copolymer gel electrolyte and preparation method thereof | |
| US10121971B2 (en) | Cellulose-polymer composites for solar cells | |
| CN110408025A (en) | Electrochromism/electricity storage bifunctional material and its preparation method and application | |
| Kamarulazam et al. | Stretchable, self-healable and highly conductive natural-rubber hydrogel electrolytes for supercapacitors: Advanced wearable technology | |
| CN109256556A (en) | A kind of starlike Cu/Cu of the cross of core-shell structure2O/CuO@Ppy composite material and preparation method and application | |
| Liu et al. | A hyperbranched disulfide polymer as cathode material for lithium-ion batteries | |
| CN1962726A (en) | Stellate reticulum solid or gel polymer electrolyte | |
| Zhang et al. | Study of EVOH based single ion polymer electrolyte: Composition and microstructure effects on the proton conductivity | |
| CN1454388A (en) | Electrolyte composition for electric double-layer capacitor, solid polymer electrolyte composition for polarizable electrode, polarizable electrode, and electric double-layer capacitor | |
| Liu et al. | UV-photopolymerized cellulose acetate-acrylate membranes for lithium-ion battery separator | |
| CN1821304A (en) | High dielectric constant composition and its preparing method and use | |
| CN115368499A (en) | Underwater high-viscosity solid ionic elastomer and preparation method thereof | |
| Bu et al. | Ultratough and Reversibly Stretchable Zwitterionic poly (ionic liquid) Copolymer Hydrogel with High Ionic Conductivity for High-Performance Flexible and Cold-Resistant Supercapacitor | |
| CN106749817B (en) | A kind of poly ion liquid antistatic agent and preparation method thereof | |
| WO2002010251A1 (en) | Method for making polypyrrole |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110928 Termination date: 20120125 |