CN103819896A - Synthetic method of cage type gamma-aminopropyl polyhedral oligomeric silsesquioxane and polyaniline compound - Google Patents
Synthetic method of cage type gamma-aminopropyl polyhedral oligomeric silsesquioxane and polyaniline compound Download PDFInfo
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- CN103819896A CN103819896A CN201210460742.3A CN201210460742A CN103819896A CN 103819896 A CN103819896 A CN 103819896A CN 201210460742 A CN201210460742 A CN 201210460742A CN 103819896 A CN103819896 A CN 103819896A
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- polyaniline
- aminopropyl
- silsesquioxane
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/549—Silicon-containing compounds containing silicon in a ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
Abstract
The invention discloses a synthetic method of cage type gamma-aminopropyl polyhedral oligomeric silsesquioxane (POSS-NH2 for short) and polyaniline compound. The synthetic method comprises the following steps: placing cage type amino polyhedral oligomeric silsesquioxane and polyaniline in a diacid aqueous solution to take reaction, and obtaining the polyaniline silsesquioxane compound with good electrochemical performance and good stability at high temperature. Through research, the polyaniline silsesquioxane compound has good electrochemical performance and good stability at high temperature. The synthetic method is simple in process, accessible in the raw materials, low in the cost and easy to popularize and apply.
Description
Technical field
The synthetic method that the present invention relates to poly-(γ-aminopropyl) silsesquioxane of a kind of cage modle eight and Polyaniline, belongs to new function material field.
Background technology
Organic and inorganic is considered to have most the material of application prospect in many aspects, and it combines the advantage of inorganic materials and organic materials, organic materials be beneficial to synthetic, snappiness, quality is light, corrosion-resistant etc.; Anti-oxidant, the intensity of inorganic materials is large, good in thermal property etc.In the more than ten years in past, cage modle oligomeric silsesquioxanes (Poss) is more and more subject to people's attention as an emerging inorganic materials.
Polyaniline is that people study one of more polymkeric substance.The different state of polyaniline has distinct colors, and the polyaniline of eigenstate presents brownish black, and the compound polyaniline of alkali presents black and blue color, and these two kinds of polyanilines all do not have electrochemical activity; Polyaniline after peracid is compound presents green, has electrochemical activity.This specific character of compound state polyaniline, make it aspect electronics and sensor, have extraordinary prospect, polyaniline is flexibly synthetic, unique oxidation-reduction quality and simple plyability, make polyaniline be widely used in nanotube, among nanofiber transistor and absorbing material.
Compound with polyaniline again after the present invention is compound with succinic acid by poly-(γ-aminopropyl) silsesquioxane (Poss) of cage modle eight, composite polyphenylene amine electrochemical activity is strengthened, thermodynamic stability increases.
Summary of the invention
The invention provides a kind of synthetic method of eight poly-(γ-aminopropyl) silsesquioxane-polyaniline composite materials of the cage modle with electrochemical activity and high-temperature stability, have that production technique is simple, cost is low, electrochemical activity is good, an advantage such as Heat stability is good under high temperature.
The present invention proposes the synthetic method of cage modle eight poly-(γ-aminopropyl) silsesquioxane-polyaniline composite materials with electrochemical activity and high-temperature stability, polyaniline is reacted with poly-(γ-aminopropyl) silsesquioxane of cage modle eight.Due to poly-(γ-aminopropyl) silsesquioxane of cage modle eight and compound after polyaniline constructional feature, make the polyaniline after compound there is the thermostability under good electrochemical activity and high temperature.
The invention has the advantages that:
(1) poly-(γ-aminopropyl) silsesquioxane of cage modle eight that the present invention uses has the feature of inorganic-organic concurrently, organic materials be beneficial to synthetic, snappiness, quality is light, corrosion-resistant etc.; Anti-oxidant, the intensity of inorganic materials is large, good in thermal property etc.
(2) the present invention has prepared the Polyaniline that is compounded with cage modle eight poly-(γ-aminopropyl) silsesquioxanes, compare with complex morphological Polyaniline in the past, it is good that mixture of the present invention has electrochemical activity, at high temperature comparatively stable feature.
(3) the present invention is compound with silsesquioxane and polyaniline, and poly-(γ-aminopropyl) silsesquioxane of cage modle eight is compound rapidly, and reaction conditions is comparatively gentle, and productive rate is higher, simple to operate.
Accompanying drawing explanation
The infrared spectrogram of Fig. 1 polyaniline-cage modle eight poly-(γ-aminopropyl) silsesquioxane mixtures.
The ultraviolet-visible spectrogram of Fig. 2 polyaniline-cage modle eight poly-(γ-aminopropyl) silsesquioxane mixtures.
The stereoscan photograph of Fig. 3 polyaniline-cage modle eight poly-(γ-aminopropyl) silsesquioxanes.
The cyclic voltammetry curve of Fig. 4 polyaniline-cage modle eight poly-(γ-aminopropyl) silsesquioxane mixtures.
The thermogravimetric curve of Fig. 5 polyaniline-cage modle eight poly-(γ-aminopropyl) silsesquioxane polymers.
The X-ray diffraction spectrogram of Fig. 6 polyaniline-cage modle eight poly-(γ-aminopropyl) silsesquioxane mixtures.
Embodiment
Embodiment 1
By KH-550, deionized water, acetonitrile, propyl alcohol, tetraethyl ammonium hydroxide was according to volume ratio 221: 90: 10: the ratio of 40: 5 adds in there-necked flask, and mechanical stirring is reacted 24 hours in the oil bath of 50 ℃.After reaction finishes, add the tetrahydrofuran (THF) of approximately 3 times of volumes, ice bath precipitation, filters to obtain white product, is placed in 40 ℃ of vacuum drying ovens and vacuumizes after dry and obtain primary amino silsesquioxane (Poss-NH
2).By Poss-NH
2hydrotropic solution be slowly added dropwise in the maleic acid aqueous solution, obtain mixture (POSS/COOH)
Get appropriate aniline and be dissolved in deionized water, magnetic agitation is dissolved it completely, takes the water-soluble ammonium persulfate aqueous solution that is configured to of ammonium persulphate at 1: 1 according to mol ratio.Add magnetic agitation in 0.5g aniline solution by containing solute 1.38g in the aqueous solution of 50ml mixture (POSS/COOH), and the aqueous solution of ammonium persulphate is added in system according to the 2 seconds speed of 1,4 ℃ of ice baths react 24 hours.After reaction finishes, wash with water, filter, until filtrate is colourless, be dried to obtain blackish green product.。
Embodiment 3
In reactor, add 50mL to contain the aqueous solution of mixture (POSS/COOH) 0.92g, other steps are identical with embodiment 2, prepare silsesquioxane-Polyaniline 2.
In reactor, add 50mL to contain the aqueous solution of mixture (POSS/COOH) 0.5g, other steps are identical with embodiment 2, prepare silsesquioxane-Polyaniline 3.
Embodiment 5
Fig. 4 is the cyclic voltammetry curve of each group of polymkeric substance, electrode is by polymkeric substance: graphite: polytetrafluoroethyl-ne aqueous solution mixes and mills according to the mass ratio of 10: 85: 5, be evenly coated on nickel foam bar 1cm high, make with the pressure compacting of 7mPa, measure its cyclic voltammetry curve, the dilute sulfuric acid aqueous solution that electrolytic solution is 1mol/L with three-electrode method.Can be found out by Fig. 4 a, the redox peak of the cyclic voltammetry curve of polymkeric substance is obvious, current-responsive is all higher than polyaniline in eigenstate, this is because the polyaniline after compound has had delocalized electron in quinone benzene-benzoquinones structure of eigenstate, form conjugated structure, this reduces the HOMO-LUMO energy gap of the polyaniline after compound, and transition of electron is easy, has caused the polyaniline after compound to have better Charge Storage characteristic and electrochemical activity than not compound polyaniline.It is the cyclic voltammetry curve of 25mv/v during to 100mv/s in current density that Fig. 4 b has provided the synthetic composite polyphenylene amine of pH=2.5, can see, curve shape is substantially constant, and current-responsive is along with the change of scanning speed becomes large greatly, this is the performance that material possesses satisfactory stability, its reason may be the satisfactory mechanical property due to POSS, makes polyaniline after the compound swelling compression in redox processes etc. receive restriction, and the decomposition of polyaniline is reduced.
Embodiment 6
The mensuration of the thermogravimetric curve of polyaniline-silsesquioxane mixture: the mixture of getting mixture 10mg left and right does thermogravimetric curve, relatively their thermostability.Fig. 5 is the thermogravimetric curve of polyaniline-silsesquioxane mixture, c.d is the correlation curve of Pan and Pan-Poss, as can be seen from the figure, not compound Pan has one to account for the decomposition peak that total mass 20% left side has near 260 ℃, this may be because a part of Ph-NH key of polyaniline is subject to thermal destruction, causes forming oligomer decomposes.Be compounded with Poss polyaniline afterwards and can see in the scope of 100～600 ℃, there is no obvious decomposition peak, be subject to thermal weight loss stable, in the time of 600 ℃, also only decompose 70% left and right, this is because Si-O key is also extremely stable under high-temperature condition, so have good resistance toheat through the compound polyaniline later of poss, this point has more obtained good embodiment from two curves of contrast a.b, along with increasing of Poss compounding quantity, material is more excellent in the stability of high temperature section, only decomposes the weight of 10% left and right in the time of 600 ℃.
Embodiment 7
The mensuration of polyaniline-silsesquioxane mixture electroconductibility: get in right amount and be placed in the PP plastics tubing that internal diameter is 1cm according to the ready-made mixture of example 2, compacting, two connects its resistance of multitester measuring, measures its resistivity according to ρ=Rs/l, and then is converted into specific conductivity S.Can see: the polyaniline after compound strengthens greatly than the polyaniline conductivity of eigenstate.In table 1.
The electric conductivity contrast of table 1 polyaniline-cage modle eight poly-(γ-aminopropyl) silsesquioxane mixtures.
Claims (3)
1. one kind has poly-(γ-aminopropyl) silsesquioxane of cage modle eight of electrochemical activity, high-temperature stability and the mixture of polyaniline, it is characterized in that take polyaniline as main body the hydridization superpolymer forming after poly-(γ-aminopropyl) silsesquioxane of cage modle eight reacts under the environment of succinic acid.
2. the preparation method of mixture described in a claim 1: get polyaniline 0.5g and be scattered in deionized water, add POSS-NH
20.65g, fully dissolves, and add maleic acid to system pH is 2.5 left and right magnetic agitation simultaneously, reacts 24 hours under room temperature, after reaction finishes, washes with water, filters, until filtrate is colourless, is dried to obtain blackish green product.
3. the formula of a mixture claimed in claim 1: polyaniline and POSS-NH
2be respectively 10: 13: 13 with the weight ratio of maleic acid; 10: 9.2: 9.2; 10: 5: 5; The mixture of poly-(γ-aminopropyl) silsesquioxane of synthetic cage modle eight and polyaniline under the condition of the claims 2.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356284A (en) * | 2014-11-04 | 2015-02-18 | 江南大学 | Epoxy functional group containing nano-reinforcer for hybrid polymer epoxy resin |
| CN104525260A (en) * | 2014-12-25 | 2015-04-22 | 江南大学 | Polymeric solid acid catalyst for esterification reaction and preparation method thereof |
| CN106751814A (en) * | 2016-12-09 | 2017-05-31 | 广东工业大学 | A kind of polyaniline silicon based composite material and preparation method and application |
| CN110256679A (en) * | 2019-05-27 | 2019-09-20 | 武汉华星光电半导体显示技术有限公司 | A kind of polyimides and preparation method thereof, electrochromic device |
| CN112143341A (en) * | 2020-10-14 | 2020-12-29 | 湖南科技大学 | Preparation method of secondary POSS-doped modified polyaniline anticorrosive coating |
-
2012
- 2012-11-16 CN CN201210460742.3A patent/CN103819896A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356284A (en) * | 2014-11-04 | 2015-02-18 | 江南大学 | Epoxy functional group containing nano-reinforcer for hybrid polymer epoxy resin |
| CN104525260A (en) * | 2014-12-25 | 2015-04-22 | 江南大学 | Polymeric solid acid catalyst for esterification reaction and preparation method thereof |
| CN106751814A (en) * | 2016-12-09 | 2017-05-31 | 广东工业大学 | A kind of polyaniline silicon based composite material and preparation method and application |
| CN110256679A (en) * | 2019-05-27 | 2019-09-20 | 武汉华星光电半导体显示技术有限公司 | A kind of polyimides and preparation method thereof, electrochromic device |
| WO2020237730A1 (en) * | 2019-05-27 | 2020-12-03 | 武汉华星光电半导体显示技术有限公司 | Polyimide, preparation method therefor, electrochromic component |
| CN112143341A (en) * | 2020-10-14 | 2020-12-29 | 湖南科技大学 | Preparation method of secondary POSS-doped modified polyaniline anticorrosive coating |
| CN112143341B (en) * | 2020-10-14 | 2022-04-01 | 湖南科技大学 | Preparation method of secondary POSS-doped modified polyaniline anticorrosive coating |
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Application publication date: 20140528 |