CN106977919A - A kind of poly- p-phenylenediamine powder of high Seebeck coefficients and its preparation - Google Patents
A kind of poly- p-phenylenediamine powder of high Seebeck coefficients and its preparation Download PDFInfo
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- CN106977919A CN106977919A CN201610033622.3A CN201610033622A CN106977919A CN 106977919 A CN106977919 A CN 106977919A CN 201610033622 A CN201610033622 A CN 201610033622A CN 106977919 A CN106977919 A CN 106977919A
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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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
Abstract
The present invention relates to a kind of poly- p-phenylenediamine powder of high Seebeck coefficients and preparation method thereof, described poly- p-phenylenediamine powder includes poly- p-phenylenediamine matrix, and admixture in poly- p-phenylenediamine matrix to improve Seebeck coefficient organic acids；Poly- p-phenylenediamine raw powder's production technology comprises the following steps：(1) p-phenylenediamine monomer is added into stirring in solvent and forms emulsion, added organic acid and initiator, continue stirring reaction, obtain reaction product；(2) by after reaction product washing and drying, cold pressing plate obtains purpose product.Compared with prior art, the present invention has the advantages that Seebeck coefficients are high, preparation is simple, is easy to industry amplification.
Description
Technical field
The present invention relates to a kind of poly- p-phenylenediamine powder and its preparation, more particularly, to a kind of high Seebeck coefficients
Poly- p-phenylenediamine powder and its preparation.
Background technology
Into 21 century, environment becomes increasingly conspicuous with energy problem, and this thermoelectric conversion technology of cogeneration makes because of it
With scope is wide, clean and safe, the close attention for meeting environmental requirement and obtaining countries in the world.Thermoelectric material is a kind of
New energy semiconductor functional material, the material can be realized by solid interior carrier transport electric energy and heat energy it
Between mutual conversion.The electric organ or refrigerator being made up of thermoelectric material take up space, and small, quality is small, noiseless fortune
Row, clean and safe, so thermoelectric material can be widely used in microelectronics technology and daily life.
Thermoelectric material is that carrier moving realizes the function that heat energy is mutually changed with electric energy inside a kind of utilization semiconductor
Material, thermoelectric generation technology due to small volume, it is without friction, noiseless, pollution-free, without abrasion, without motion
Part, it is non-maintaining, pollution-free the features such as, the unique advantage having in terms of heat energy utilization.Thermo-electric device can profit
Electric energy is contamination-freely produced with various heats, such as solar energy, industrial waste heat, CPU dissipate and human body thermoelectric.
I.e. simply by the presence of the temperature difference, it is possible to export energy, this effective utilization to resource can produce far-reaching influence.At present
Had a wide range of applications in fields such as industrial afterheat power generation, space flight, microelectronics and refrigeration.Current thermoelectricity research field
Key issue be find high performance thermoelectric material.Conversion efficiency of thermoelectric is by thermoelectric figure of merit (ZT=α2σ T/ κ, wherein
α, σ and κ are respectively Seebeck coefficients, electrical conductivity and the thermal conductivity of material, and T is absolute temperature) determine.Cause
This, high conversion efficiency requires high α and σ, and low κ.But because these three parameters interdepend, such as
α can be reduced while improving κ by improving σ, and ZT values are difficult to improve.Improving the approach of conducting material thermoelectricity performance has doping, material
Expect low-dimensional and Material cladding.Although traditional inorganic thermoelectric material shows of a relatively high thermoelectricity capability, still
Because its prices of raw materials is expensive, the shortcomings of there is heavy metal pollution and complicated processing technology has had a strong impact on it
Large-scale application.Current Organic thermoelectric material have lower thermal conductivity, light weight, it is inexpensive, be readily synthesized and can solution
Machine-shaping, can large area get more and more people's extensive concerning the advantages of prepare flexible device.
The micro thermoelectric device that Organic thermoelectric material is made is very wide in the refrigeration and power generation applications of room temperature annex, for example
Using thermoelectric material electricity refrigeration characteristic, can be applied to portable refrigerator, integrated circuit refrigeration, microprocessor refrigeration,
In terms of infrared detector；Can be remote or portable wireless biography using the characteristic of thermoelectric material thermo-electric generation
Sensor is powered；In such applications, efficiency is not most important Consideration, and quality, size and flexibility may
As important factor, and the intrinsic advantage of these exactly organic thermoelectricity.Because polymer has flexibility, construct
Thermo-electric device can be integrated into special topological structure to meet most solid the need for so that heat absorption
Area is maximized, so as to improve actual conversion efficiency.The Organic thermoelectric material studied now mainly includes polyaniline
(PANI), the conduction such as polypyrrole (PPy), polythiophene (PTH), poly- 3,4- ethylenedioxy thiophenes (PEDOT)
Macromolecule and its composite.Research now concerning Organic thermoelectric material is more, but the organic material report of n-type
Road is still less.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of high Seebeck
The conductive poly- p-phenylenediamine powder of the n-type of coefficient and its preparation.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of poly- p-phenylenediamine powder of high Seebeck coefficients, including poly- p-phenylenediamine matrix, and fill poly-
The organic acid to improve Seebeck coefficients in p-phenylenediamine matrix.
In described poly- p-phenylenediamine powder, the mass content ratio of poly- p-phenylenediamine matrix and organic acid is 1：
(0~1.5).
Described organic acid is sulfosalicylic acid (SSA), camphorsulfonic acid (CSA) or p-methyl benzenesulfonic acid (TSA).
Described poly- p-phenylenediamine powder is n-type conducting polymer powder.
A kind of poly- p-phenylenediamine raw powder's production technology of high Seebeck coefficients, comprises the following steps：
(1) p-phenylenediamine monomer (pPD) is added into stirring in solvent and forms the emulsion of Cappuccino shape, then added
Enter organic acid and initiator, continue stirring reaction, obtain reaction product；
(2) by after reaction product washing and drying, cold pressing plate obtains purpose product.
Solvent described in step (1) is deionized water.
The ammonium persulfate aqueous solution that initiator described in step (1) is 0.2~2.2mol/L of concentration, p-phenylenediamine
The addition of monomer, organic acid and initiator meets p-phenylenediamine monomer, organic acid and ammonium persulfate (APS)
The ratio between addition is 1mmol：(0~1.5) g：(1~11) mmol.
The temperature of stirring reaction is room temperature in step (1), and the reaction time is 15~30h.
The process conditions of washing are in step (2)：Reaction product is inserted in deionized water and absolute ethyl alcohol successively
Cleaning is neutral to pH；
Dry process conditions are：Reaction product after washing is dried in vacuo 8~16h at 60~80 DEG C.
Cold pressing plate is that reaction product is cold-pressed into 1~2mm of thickness with diameter 12mm mould in step (2)
Block.
The present invention has prepared the organic acid doped of the n-type conduction of huge Seebeck coefficients using situ aggregation method
PpPD (poly- p-phenylenediamine) powder, because p-phenylenediamine cation has hydrophilic and lipophilic group simultaneously,
P-phenylenediamine cation can form spherical micella in aqueous, add oxidant APS (ammonium persulfate)
Afterwards, because APS is water miscible, it is impossible to enter inside micella, so the oxidative polymerization of p-phenylenediamine
It can only be carried out on the interface of micella/water.This means micella can be counted as the nano junction of self assembly PpPD- acid
" soft template " of structure.When acid concentration is moderate, micella stretches along one-dimensional square, forms nanofiber, due to poly-
The hydrophobic effect of p-phenylenediamine, while there is interchain stronger π-π to interact and hydrogen bond action, therefore, receives
Rice fiber can mutually be merged and extended to three-dimensional, and last self assembly is nano-lamellar structure.Again due to being doped into
Organic acid, the anion of organic acid is on PpPD doped with two kinds of influences, and one is electrostatic interaction, volume is larger
Anion migration velocity it is slow, the impeding effect that is diffused with to proton, this influence will cause doping rate reduce from
And Seebeck coefficients are increased considerably；Second of influence is that large volume of anion can hinder the curling of chain to twine
Around etc., it is favourable to forming regular chain structure, so this influence will cause electrical conductivity and Seebeck coefficients
All it increased, and the thermoelectricity capability for improving polymer to a certain extent.
Compared with prior art, the present invention has advantages below：
(1) Seebeck coefficients are very high：The PpPD that the present invention is used is due to big conjugated structure, conjugation
Degree is even above PANI, and conjugated polymer electrical conductivity is low in the state of going doping or be low-doped, but can obtain
Higher Seebeck coefficients.And poly- p-phenylenediamine has unique mechanism of doping effect, its process of adulterating includes two
Aspect, one is diffusion of the Bronsted acid to doping position, and two are carried out on doping position in doping reaction, i.e. soda acid
And reaction.The neutralization reaction of acid and alkali, speed ratio is very fast, thus diffusion process is to influence the key factor of doping rate.
Higher proton concentration diffusivity is stronger, is conducive to doping reaction and improves doping rate, but forms highly doped state
Afterwards, the imine nitrogen atom in poly- p-phenylenediamine chain is substantially by proton saturation, and doping rate is not further added by.If dopant acid
Concentration it is smaller, not only doping rate is low, and the driving force of its diffusion is also weak, be unfavorable for doping, therefore electricity
Conductance is relatively low.Low doping rate then causes the localization of polaron, and the formation of localized state is to improving Seebeck coefficients
Be it is favourable, thus Seebeck coefficients increase.Present invention selection organic acid SSA or CSA doping, these have
Machine acid molecule in both contain non-polar group, polar group is contained again, not only make doped poly- p-phenylenediamine have compared with
High electrical conductivity, and substantially improve the dissolubility of doped poly- p-phenylenediamine in organic solvent, and due to
Large volume of organic acid counter ion inserts poly- p-phenylenediamine interchain, reduces the aggtegation of poly- p-phenylenediamine chain,
The orientations of poly- p-phenylenediamine chain, thus strand arranged regular are more beneficial for, conjugacy is improved, its electric conductivity
It will can increase.The secondary doping of the poly- p-phenylenediamine of anion of organic acid has two kinds of influences, and one is electrostatic interaction,
The migration velocity of the larger anion of volume is slow, the effect of impeding that is diffused with to proton, and this influence will cause doping
So as to cause, electrical conductivity declines and Seebeck coefficients increase for rate reduction；Second of influence is large volume of anion
The curling of chain can be hindered to wind etc., be that favourable, regular chain structure is simultaneously favourable to forming regular chain structure
In the raising of electrical conductivity and Seebeck coefficients.So this influence will cause electrical conductivity and Seebeck coefficients to have
Increased.
(2) it is conductive for n-type conduction：The preparation of the poly- p-phenylenediamine powder of the present invention, which is mainly, there occurs oxidation also
Original doping, and because poly- p-phenylenediamine has compared with strong reducing property in itself, ammonium persulfate has oxidation as initiator
Property, but be consumed in reaction, and APS is in aqueous, can isolate ammonium ion, and it is same to have also. more
Originality.Simultaneously as the reproducibility of poly- p-phenylenediamine is more than the oxidisability of remaining initiator, so in preparation process
Main reaction be redox reaction, the Seebeck coefficients of last obtained poly- p-phenylenediamine powder are negative value, i.e.,
It is conductive for n-type.
(3) preparation is simple：Preparation technology in the present invention is simple to operate, and reacting treatment time is short,
Each reaction raw materials are cheap, are particularly suitable for the industrial production of scale.
Brief description of the drawings
Fig. 1 is the organic acid of poly- p-phenylenediamine powder produced by the present invention and the graph of a relation of Seebeck coefficients；
Fig. 2 is initiator different in the present invention and gathering to benzene obtained by the addition ratio of p-phenylenediamine monomer
The Seebeck coefficients and the graph of a relation of electrical conductivity of diamines powder；
Fig. 3 is transmission electron microscope (TEM) shape appearance figure of the poly- p-phenylenediamine powder of the present invention.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
A kind of conductive poly- p-phenylenediamine powder of the n-type of high Seebeck coefficients, is prepared from by following steps：
10mmol p-phenylenediamine (pPD) monomer is added into stirring in 50mL deionized waters and forms similar Cappuccino
The emulsion of (Cappuccino), then adds organic acid SSA 0.5g, separately takes 10mmol ammonium persulfates (APS)
In the emulsion for being dissolved in 50mL deionized waters and being prepared before being added with the speed often dripped for two seconds, mixing is obtained molten
Liquid.Mixed solution is persistently stirred 24 hours at room temperature, there is black precipitate generation at cup bottom.Generation product is spent
Alternately repeatedly washing, to neutrality, is put into 70 DEG C of insulations drying in 8 hours in vacuum drying oven for ionized water and absolute ethyl alcohol,
Obtain black powder, the poly- p-phenylenediamine powder of the n-type conduction of as high Seebeck coefficients.Obtained is gathered
P-phenylenediamine powder is detected that as shown in Figure 1, the Seebeck coefficients of the polymer powder of the present embodiment are
-3691μV·K-1。
Embodiment 2
In addition to the organic acid of addition is SSA 1.0g, remaining is identical with the preparation method of embodiment 1.Finally
The Seebeck coefficients of obtained polymer powder are -1498 μ VK-1, as shown in Figure 1.
Embodiment 3
In addition to the organic acid of addition is SSA 1.5g, remaining is identical with the preparation method of embodiment 1.Finally
The Seebeck coefficients of obtained polymer powder are -1415 μ VK-1, as shown in Figure 1.
Embodiment 4
In addition to the organic acid of addition is CSA 0.5g, remaining is identical with the preparation method of embodiment 1.Finally
The Seebeck coefficients of obtained polymer powder are -2192 μ VK-1, as shown in Figure 1.
Embodiment 5
In addition to the organic acid of addition is CSA 1.0g, remaining is identical with the preparation method of embodiment 1.Finally
The Seebeck coefficients of obtained polymer powder are -1775 μ VK-1, as shown in Figure 1.
Embodiment 6
In addition to the organic acid of addition is CSA 1.5g, remaining is identical with the preparation method of embodiment 1.Finally
The Seebeck coefficients of obtained polymer powder are -1171 μ VK-1, as shown in Figure 1.
Embodiment 1-1
Compared with the preparation method described in embodiment 1, in addition to no addition organic acid, remaining all same.Through inspection
After survey, the Seebeck coefficient values of last obtained polymer powder are -1232 μ VK-1。
Comprehensive analysis comparative example 1 and embodiment 1-1 are understood, after addition is organic acid doped, obtained polymer
The Seebeck coefficient values of powder are remarkably reinforced.
Embodiment 7
A kind of conductive poly- p-phenylenediamine powder of the n-type of high Seebeck coefficients, is prepared from by following steps：
10mmol p-phenylenediamine (pPD) monomer is added into stirring in 50mL deionized waters and forms similar Cappuccino
Emulsion.Separately take what 30mmol ammonium persulfates (APS) were dissolved in 50mL deionized waters and often dripped with two seconds
In the emulsion that speed is prepared before adding.Mixed solution is persistently stirred 24 hours at room temperature, and there is black precipitate at cup bottom
Generation.Product deionized water and absolute ethyl alcohol will be generated, and alternately repeatedly washing, to neutrality, is put into vacuum drying oven
70 DEG C of insulations drying in 8 hours, obtains black powder, as poly- p-phenylenediamine powder.After after testing, it is known that, its
Seebeck coefficient values are -8359 μ VK-1。
Embodiment 8
The present embodiment is compared with preparation method described in embodiment 7, except the addition of ammonium persulfate is 50mmol
Outside, remaining all same.The Seebeck coefficient values of last obtained polymer powder are -11965 μ VK-1, such as scheme
Shown in 2.
Embodiment 9
The present embodiment is compared with preparation method described in embodiment 7, except the addition of ammonium persulfate is 70mmol
Outside, remaining all same.The Seebeck coefficient values of last obtained polymer powder are -13400 μ VK-1, such as scheme
Shown in 2.
Embodiment 10
The present embodiment is compared with preparation method described in embodiment 7, except the addition of ammonium persulfate is 90mmol
Outside, remaining all same.The Seebeck coefficient values of last obtained polymer powder are -6566 μ VK-1, such as Fig. 2
It is shown.
Embodiment 11
The present embodiment is compared with preparation method described in embodiment 7, except the addition of ammonium persulfate is 110mmol
Outside, remaining all same.The thermoelectricity Seebeck values of last obtained polymer powder are -4708 μ VK-1, such as Fig. 2
It is shown.
Fig. 3 is the transmission of above-described embodiment 1 and the poly- p-phenylenediamine polymer powder obtained by embodiment 7~11
Electron microscope (TEM) shape appearance figure, wherein, Fig. 3 (a)~Fig. 3 (f) represents embodiment 1, implementation respectively
Example 7, embodiment 8, embodiment 9, embodiment 10, embodiment 11, it can be seen that polymer is micro-
Structure is seen by nano-lamellar structure, is changed into tubular structure, centre is final to become by tubulose and bar-shaped mixed process
Into club shaped structure.
Embodiment 12
A kind of conductive poly- p-phenylenediamine powder of the n-type of high Seebeck coefficients, is prepared from by following steps：
10mmol p-phenylenediamine (pPD) monomer is added into stirring in 50mL deionized waters and forms similar Cappuccino
The emulsion of (Cappuccino), then adds organic acid SSA 0.2g, separately takes 10mmol ammonium persulfates (APS)
In the emulsion for being dissolved in 50mL deionized waters and being prepared before being added with the speed often dripped for two seconds, mixing is obtained molten
Liquid.Mixed solution is persistently stirred 30 hours at room temperature, there is black precipitate generation at cup bottom.Generation product is spent
Alternately repeatedly washing, to neutrality, is put into 60 DEG C of insulations drying in 16 hours in vacuum drying oven for ionized water and absolute ethyl alcohol,
Black powder is obtained, reaction product is cold-pressed into thickness 2mm block with diameter 12mm mould, that is, obtained
Purpose product.After after testing, obtained poly- p-phenylenediamine powder Seebeck coefficient values are -2491 μ VK-1。
Embodiment 13
A kind of conductive poly- p-phenylenediamine powder of the n-type of high Seebeck coefficients, is prepared from by following steps：
10mmol p-phenylenediamine (pPD) monomer is added into stirring in 50mL deionized waters and forms similar Cappuccino
The emulsion of (Cappuccino), then adds organic acid SSA 0.2g, separately takes 10mmol ammonium persulfates (APS)
In the emulsion for being dissolved in 50mL deionized waters and being prepared before being added with the speed often dripped for two seconds, mixing is obtained molten
Liquid.Mixed solution is persistently stirred 30 hours at room temperature, there is black precipitate generation at cup bottom.Generation product is spent
Alternately repeatedly washing, to neutrality, is put into 60 DEG C of insulations drying in 16 hours in vacuum drying oven for ionized water and absolute ethyl alcohol,
Black powder is obtained, reaction product is cold-pressed into thickness 1mm block with diameter 12mm mould, that is, obtained
Purpose product.After after testing, obtained poly- p-phenylenediamine powder Seebeck coefficient values are -2251 μ VK-1。
Embodiment 14
A kind of conductive poly- p-phenylenediamine powder of the n-type of high Seebeck coefficients, is prepared from by following steps：
10mmol p-phenylenediamine (pPD) monomer is added into stirring in 50mL deionized waters and forms similar Cappuccino
The emulsion of (Cappuccino), then adds organic acid SSA 0.8g, separately takes 40mmol ammonium persulfates (APS)
In the emulsion for being dissolved in 50mL deionized waters and being prepared before being added with the speed often dripped for two seconds, mixing is obtained molten
Liquid.Mixed solution is persistently stirred 26 hours at room temperature, there is black precipitate generation at cup bottom.Generation product is spent
Alternately repeatedly washing, to neutrality, is put into 80 DEG C of insulations drying in 10 hours in vacuum drying oven for ionized water and absolute ethyl alcohol,
Black powder is obtained, reaction product is cold-pressed into thickness 1.5mm block with diameter 12mm mould, produced
To purpose product.After after testing, obtained poly- p-phenylenediamine powder Seebeck coefficient values are -9481 μ VK-1,
The mass content ratio of poly- p-phenylenediamine matrix and organic acid is 1:0.7.
Embodiment 15
A kind of conductive poly- p-phenylenediamine powder of the n-type of high Seebeck coefficients, is prepared from by following steps：
10mmol p-phenylenediamine (pPD) monomer is added into stirring in 50mL deionized waters and forms similar Cappuccino
The emulsion of (Cappuccino), then adds organic acid CSA 0.8g, separately takes 80mmol ammonium persulfates (APS)
In the emulsion for being dissolved in 50mL deionized waters and being prepared before being added with the speed often dripped for two seconds, mixing is obtained molten
Liquid.Mixed solution is persistently stirred 15 hours at room temperature, there is black precipitate generation at cup bottom.Generation product is spent
Alternately repeatedly washing, to neutrality, is put into 80 DEG C of insulations drying in 10 hours in vacuum drying oven for ionized water and absolute ethyl alcohol,
Black powder is obtained, reaction product is cold-pressed into thickness 1.5mm block with diameter 12mm mould, produced
To purpose product.After after testing, obtained poly- p-phenylenediamine powder Seebeck coefficient values are -8678 μ VK-1。
Embodiment 16
A kind of conductive poly- p-phenylenediamine powder of the n-type of high Seebeck coefficients, is prepared from by following steps：
10mmol p-phenylenediamine (pPD) monomer is added into stirring in 50mL deionized waters and forms similar Cappuccino
The emulsion of (Cappuccino), then adds organic acid CSA 1.2g, separately takes 60mmol ammonium persulfates (APS)
In the emulsion for being dissolved in 50mL deionized waters and being prepared before being added with the speed often dripped for two seconds, mixing is obtained molten
Liquid.Mixed solution is persistently stirred 20 hours at room temperature, there is black precipitate generation at cup bottom.Generation product is spent
Alternately repeatedly washing, to neutrality, is put into 70 DEG C of insulations drying in 10 hours in vacuum drying oven for ionized water and absolute ethyl alcohol,
Black powder is obtained, reaction product is cold-pressed into thickness 1.5mm block with diameter 12mm mould, produced
To purpose product.After after testing, obtained poly- p-phenylenediamine powder Seebeck coefficient values are -7491 μ VK-1。
Embodiment 17
A kind of conductive poly- p-phenylenediamine powder of the n-type of high Seebeck coefficients, is prepared from by following steps：
10mmol p-phenylenediamine (pPD) monomer is added into stirring in 50mL deionized waters and forms similar Cappuccino
The emulsion of (Cappuccino), then adds organic acid TSA 1.2g, separately takes 60mmol ammonium persulfates (APS)
In the emulsion for being dissolved in 50mL deionized waters and being prepared before being added with the speed often dripped for two seconds, mixing is obtained molten
Liquid.Mixed solution is persistently stirred 20 hours at room temperature, there is black precipitate generation at cup bottom.Generation product is spent
Alternately repeatedly washing, to neutrality, is put into 70 DEG C of insulations drying in 10 hours in vacuum drying oven for ionized water and absolute ethyl alcohol,
Black powder is obtained, reaction product is cold-pressed into thickness 1.5mm block with diameter 12mm mould, produced
To purpose product.After after testing, obtained poly- p-phenylenediamine powder Seebeck coefficient values are -8291 μ VK-1,
In poly- p-phenylenediamine powder, the mass content ratio of poly- p-phenylenediamine matrix and organic acid is 1:1.5.
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using hair
It is bright.Person skilled in the art obviously easily can make various modifications to these embodiments, and herein
The General Principle of explanation is applied in other embodiment without passing through performing creative labour.Therefore, the present invention is not limited
In above-described embodiment, those skilled in the art are according to the announcement of the present invention, and do not depart from that scope made changes
Entering and change all should be within protection scope of the present invention.
Claims (10)
1. a kind of poly- p-phenylenediamine powder of high Seebeck coefficients, it is characterised in that including poly- p-phenylenediamine base
Body, and admixture in poly- p-phenylenediamine matrix to improve Seebeck coefficient organic acids.
2. a kind of poly- p-phenylenediamine powder of high Seebeck coefficients according to claim 1, its feature exists
In in described poly- p-phenylenediamine powder, the mass content ratio of poly- p-phenylenediamine matrix and organic acid is 1：
(0~1.5).
3. a kind of poly- p-phenylenediamine powder of high Seebeck coefficients according to claim 1, its feature exists
In described organic acid is sulfosalicylic acid, camphorsulfonic acid or p-methyl benzenesulfonic acid.
4. a kind of poly- p-phenylenediamine powder of high Seebeck coefficients according to claim 1, its feature exists
In described poly- p-phenylenediamine powder is n-type conducting polymer powder.
5. the poly- p-phenylenediamine raw powder's production technology of the high Seebeck coefficients as described in Claims 1 to 4 is any,
It is characterised in that it includes following steps：
(1) p-phenylenediamine monomer is added into stirring in solvent and forms emulsion, added organic acid and initiator, hold
Continuous stirring reaction, obtains reaction product；
(2) by after reaction product washing and drying, cold pressing plate obtains purpose product.
6. a kind of poly- p-phenylenediamine raw powder's production technology of high Seebeck coefficients according to claim 5,
Characterized in that, the solvent described in step (1) is deionized water.
7. a kind of poly- p-phenylenediamine raw powder's production technology of high Seebeck coefficients according to claim 5,
Characterized in that, the ammonium persulfate aqueous solution that the initiator described in step (1) is 0.2~2.2mol/L of concentration,
The addition of p-phenylenediamine monomer, organic acid and initiator meets p-phenylenediamine monomer, organic acid and ammonium persulfate
The ratio between addition is 1mmol：(0~1.5) g：(1~11) mmol.
8. a kind of poly- p-phenylenediamine raw powder's production technology of high Seebeck coefficients according to claim 5,
Characterized in that, the temperature of stirring reaction is room temperature in step (1), the reaction time is 15~30h.
9. a kind of poly- p-phenylenediamine raw powder's production technology of high Seebeck coefficients according to claim 5,
Characterized in that, the process conditions of washing are in step (2)：Reaction product is inserted into deionized water and nothing successively
It is neutrality to be cleaned in water-ethanol to pH；
Dry process conditions are：Reaction product after washing is dried in vacuo 8~16h at 60~80 DEG C.
10. a kind of poly- p-phenylenediamine raw powder's production technology of high Seebeck coefficients according to claim 5,
Characterized in that, cold pressing plate is that reaction product is cold-pressed into thickness with diameter 12mm mould in step (2)
1~2mm block.
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| CN115414877A (en) * | 2022-08-01 | 2022-12-02 | 浙江理工大学 | Method for preparing phase change energy storage microcapsule based on poly-p-phenylenediamine stabilized Pickering emulsion |
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| CN101020749A (en) * | 2007-02-13 | 2007-08-22 | 同济大学 | High temperature reflux oxidation process for preparing poly-o-phenylenediamine |
| CN103137848A (en) * | 2013-02-06 | 2013-06-05 | 中国科学院上海硅酸盐研究所 | Method for obtaining high-performance polyaniline base thermoelectric materials |
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2016
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101020749A (en) * | 2007-02-13 | 2007-08-22 | 同济大学 | High temperature reflux oxidation process for preparing poly-o-phenylenediamine |
| CN103137848A (en) * | 2013-02-06 | 2013-06-05 | 中国科学院上海硅酸盐研究所 | Method for obtaining high-performance polyaniline base thermoelectric materials |
Non-Patent Citations (3)
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| FANGZHUAN LIU ET AL: "Optimization of thermoelectric figure of merit in poly(p-phenylenediamine)/exfoliated graphene nanosheets composites", 《RSC ADVANCES》 * |
| HU YAN ET AL: "Stretched polyaniline films doped by 10-camphorsulfonic acid: anisotropy and improvement of thermoelectric properties", 《MACROMOLECULAR MATERIALS AND ENGINEERING》 * |
| 李凤元 等: "聚3,4-乙烯二氧噻吩及其复合热电材料性能研究", 《新型工业化》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115414877A (en) * | 2022-08-01 | 2022-12-02 | 浙江理工大学 | Method for preparing phase change energy storage microcapsule based on poly-p-phenylenediamine stabilized Pickering emulsion |
| CN115414877B (en) * | 2022-08-01 | 2024-01-05 | 浙江理工大学 | Method for preparing phase-change energy-storage microcapsule based on p-phenylenediamine stable Pickering emulsion |
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| CN106977919B (en) | 2019-02-01 |
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