CN109251435A - A kind of chromogen bonded polymer conductive bead and preparation method thereof - Google Patents
A kind of chromogen bonded polymer conductive bead and preparation method thereof Download PDFInfo
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- CN109251435A CN109251435A CN201811109215.1A CN201811109215A CN109251435A CN 109251435 A CN109251435 A CN 109251435A CN 201811109215 A CN201811109215 A CN 201811109215A CN 109251435 A CN109251435 A CN 109251435A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
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- 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
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- 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
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
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- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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Abstract
The invention discloses a kind of chromogen bonded polymer conductive beads and preparation method thereof.The preparation method includes: the preparation of 1) conducting polymer seed liquor；2) the controllable swelling pretreatment of the confinement of polymer beads；3) synthesis of chromogen bonded polymer conductive bead.The present invention can realize that the surface layer confinement of polymer beads is controllably swollen by the controllable swelling pretreatment technique of confinement of polymer beads, the synthesis technology factor controlling for passing through chromogen bonded polymer conductive bead again can synthesize to obtain the colorful conductive polymer beads of a series of different electric conductivities and different colours.Conducting polymer is good with polymer beads compatibility, lower conducting polymer content can assign the preferable conductive effect of polymer beads and colour, the internal structure for not destroying polymer beads simultaneously still maintains the foam characteristics of polymer beads for foamable polymer beads.
Description
Technical field
The invention belongs to chromogen bonded polymer conductive bead fields, more particularly, to a kind of chromogen bonded polymer conductive bead
And preparation method thereof.
Background technique
Polymer beads such as polystyrene, polymethyl methacrylate, expandable polystyrene (EPS) and expandable poly- methyl-prop
E pioic acid methyl ester etc. is widely used in the fields such as building materials, packaging, decoration and craftwork.Common polymer beads are white, but
Chromogen bonded polymer bead is needed in some application fields.Therefore a large amount of research reports in relation to chromogen bonded polymer bead have been derived
Road.The Chinese invention patent application of Publication No. CN 102875713A disclose a kind of colored expandable polystyrene resin with
And organic dyestuff is added to styrene monomer by the method that one-step method prepares colored expandable polystyrene resin, the patent application
In, colored expandable polystyrene resin is prepared using suspension polymerization one-step method, in addition, in order to inhibit colored expandability polyphenyl
Vinyl electrostatic generates, and the patent is using antistatic agent coating processes, by colored expandable polystyrene resin particles
It is put into mixing machine, then, adds surface coating agent and antistatic agent, after mixing evenly, obtaining has the coloured silk for inhibiting electrostatic
Color expandable polystyrene resin.It is resistance to that the Chinese invention patent application of Publication No. CN102719031A discloses high intensity of colour height
Fastness colour Expandable polystyrene resin bead and preparation method thereof is shone, organic pigment color is made using dispersion grinding technics
Slurry, obtains the monomer containing high intensity of colour organic pigment by the phase transition of mill base, and finally initiation monomer polymerization, which obtains colour, to send out
Property polystyrene resin bead.The Chinese invention patent application of Publication No. CN101633709A discloses in-situ suspension polymerization one
The colorful polystyrene particle preparation method of footwork synthesis carries out in-situ modification to inorganic pigment first and obtains hydrophobic inorganic powder
Body recycles in-situ suspension polymerization method to synthesize colorful polystyrene particle.The Chinese invention of Publication No. CN105061915A is special
Benefit application discloses a kind of high thermal stability antistatic poly styrene composite material and preparation method thereof, and this application will include polyphenyl
Ethylene, acrylonitrile-butadiene-styrene copolymer, conductive auxiliary agent, heat stabilizer, compatilizer and to help additive to be placed in high speed mixed
Conjunction machine premixes refining, is subsequently placed in double screw extruder after screw rod shearing, abundant melting mixing, after being squeezed out, being granulated
To aspherical high thermal stability antistatic poly styrene composite material.
Above-mentioned to have been reported, the first kind is to introduce organic dyestuff using suspension polymerisation, and still, organic dyestuff has been soluble in
Solvent, inflammable and be exposed to the sun and can decompose, therefore, organic dyestuff weatherability is poor, poor solvent resistance, light fastness difference and inflammable, sternly
Ghost image rings the performance of colored expandable polystyrene bead.Second class is inorganic pigment, needs to carry out hydrophobic change to inorganic pigment
Property processing, be re-introduced into suspension polymerization system, the introducing of inorganic pigment can reduce mechanical property to a certain extent.Third class is
Using melt blending technique, needing to add multiple additives and auxiliary agent, complex process, the conductive auxiliary agent of addition is inorganic matter, with
Polymer compatibility is poor, only can be only achieved the effect for inhibiting electrostatic when conductive auxiliary agent additive amount is very big, while can drop significantly
The mechanical property of low polymer.
In addition, polymer beads friction can generate accumulation of static electricity, and there are potential fire hazard, especially expandable polymer
Bead has frothing function because containing low boiling point organic foaming agent, however these low boiling point organic foaming agents are highly combustible.?
Expandable polymer beads can discharge foaming agent in the links such as storage, logistics and foaming, if there are electrostatic products in these links
The tired fire that will cause to be difficult to be aware brings harm and loss to the person and property, therefore, inhibits the quiet of polymer beads
Electrical phenomena is also very important.
Conducting polymer such as polyaniline and polypyrrole have special electricity, optical property, can have conduction after doped
Property and chemical property, itself present green, blackish green or black color, in addition, electrochromism is the weight of conducting polymer
Want one of characteristic.Because the raw material that it has is easy to get, synthesis technology is simple, chemistry and environmental stability good the features such as due to obtained it is wide
General research and application is typically used as electrode material, selective membrane material, antistatic and electromagnetic shielding material, conductive fiber, prevents
Rotten material etc..Due to its chain rigidity and interchain strong interaction, keeps its solubility very poor, there is preferable solvent resistance.
In conclusion existing reported patent and documents and materials not while having resolved colored and inhibition electrostatic dual function
The problem of, and existing report is all made of inorganic pigment and organic pigment, not simultaneously using the intrinsic color of conducting polymer
It solves the color of polymer beads and inhibits the relevant report of electrostatic.
Summary of the invention
The present invention is directed to draw while meeting chromogen bonded polymer bead demand, the electrostatic of polymer beads is inhibited to generate
The generation of conductive polymer fibers is led, and inhibits the diauxic growth of nanofiber, conductive polymer fibers is more advantageous to and constructs
Conducting fibrous web.
To achieve the goals above, the first aspect of the present invention provides a kind of preparation side of chromogen bonded polymer conductive bead
Method, the preparation method include:
1) preparation of conducting polymer seed liquor
Conducting polymer is dissolved in dimethyl sulfoxide, preparation obtains conducting polymer seed liquor；
2) the controllable swelling pretreatment of the confinement of polymer beads
It disperses polymer beads in the in the mixed solvent of good solvent and poor solvent, then is pre-processed through being separated by solid-liquid separation
Polymer beads；
3) synthesis of chromogen bonded polymer conductive bead
The monomer of conducting polymer described in the first acidic aqueous solution, step 1) is added into reaction vessel, step 1) obtains
To conducting polymer seed liquor, the obtained pretreatment polymer beads of step 2), stirring adsorbed, adds initiator
Solution carries out polymerization reaction, after being filtered, washed after reaction, obtains chromogen bonded polymer conductive bead；The initiator solution
For the mixture of oxidant and the second acidic aqueous solution.
According to the present invention, conducting polymer seed liquor is added in the synthetic system of chromogen bonded polymer conductive bead, it can
To guide the generation of conductive polymer fibers, while inhibiting the diauxic growth of nanofiber, keeps conductive polymer fibers more advantageous
In constructing conducting fibrous web.
According to the present invention, be using the reason of forming mixed solvent by good solvent and poor solvent: good solvent with it is bad
Solvent has intersolubility, and good solvent can be effectively prevent to bond because solvability too good general's polymer beads swelling is excessive, realized
The confinement of polymer beads is controllably swollen, while reducing the dosage of good solvent, in addition, mixed solvent is recyclable.
According to the present invention, conducting polymer dissolve in dimethyl sulfoxide formed true solution, the seed true solution can with it is water-soluble
Liquid dissolves each other, and can be dispersed in whole system, in step (3), carries out adsorption treatment and makes the poly- of the controllable swelling pretreatment of confinement
It closes object bead and seed solution comes into full contact with absorption.
As a preferred embodiment of the present invention,
In step 2), relative to the mixed solvent of 20~100mL good solvent and poor solvent, the dosage of polymer beads is
5~80g；
In step 3), relative to the monomer of conducting polymer described in 1~20mmol step 1), the dosage of other each components
Are as follows: 0.1~2mL of conducting polymer seed liquor that first 10~100mL of acidic aqueous solution, step 1) obtain, oxidant 1~
20mmol, second 10~60mL of acidic aqueous solution；
Wherein, the concentration of the first acidic aqueous solution is 0.1~4mol/L, the concentration of conducting polymer seed liquor is 0.1~
5mg/mL, the concentration of the second acidic aqueous solution are 0.1~4mol/L.
As a preferred embodiment of the present invention, the concentration of the first acidic aqueous solution is 0.1~2mol/L, conducting polymer
The concentration of seed liquor is 0.1~2mg/mL, and the concentration of the second acidic aqueous solution is 0.1~2mol/L.
As a preferred embodiment of the present invention, first acidic aqueous solution is identical as the second acidic aqueous solution, more excellent
Selection of land, first acidic aqueous solution and the second acidic aqueous solution concentration and dosage are all the same.
According to the present invention, the conducting polymer that those skilled in the art routinely use can be selected in the conducting polymer, makees
For the preferred embodiment of the present invention, the conducting polymer is polyaniline or polypyrrole.
As a preferred embodiment of the present invention, the polymer beads be selected from polystyrene, polymethyl methacrylate,
Poly- (styrene methyl methacrylate), expandable poly- (styrene methyl methacrylate), expandable polystyrene (EPS) and can
Foam at least one of polymethyl methacrylate bead.
As a preferred embodiment of the present invention, the partial size of the polymer beads is 0.1~2mm.
As a preferred embodiment of the present invention, the good solvent be selected from chloroform, methylene chloride, limonene, toluene,
Dimethylbenzene, ethylbenzene, benzene, methyl ethyl ketone, ethyl acetate, carbon tetrachloride, n-butyl acetate, tetrahydrofuran and N,N-dimethylformamide
At least one of.
As a preferred embodiment of the present invention, the poor solvent be selected from methanol, ethyl alcohol, propyl alcohol, butanol, isopropanol and
At least one of normal heptane.
As a preferred embodiment of the present invention, in the mixed solvent good solvent and poor solvent volume ratio are 1:1~15, should
Ratio can guarantee that bead is inadherent simultaneously, control processed material surface Swelling Capacity.
As a preferred embodiment of the present invention, in step 3), first acidic aqueous solution and the second acidic aqueous solution
It is each independently selected from hydrochloric acid solution, sulfuric acid solution, phosphate aqueous solution, high chloro acid solution, camphorsulfonic acid aqueous solution, benzene sulfonic acid
Aqueous solution, dodecyl benzene sulfonic acid aqueous solution, p-methyl benzenesulfonic acid aqueous solution, p styrene sulfonic acid aqueous solution, naphthalene sulfonic acids aqueous solution,
At least one of aqueous solution of salicylic acid, aqueous tartaric acid solution and phenyl-phosphonic acid aqueous solution.
As a preferred embodiment of the present invention, in step (3), the oxidant is ammonium persulfate, potassium peroxydisulfate or three
Iron chloride.
As a preferred embodiment of the present invention,
In step 2), the dispersion is realized by mechanical stirring, and the churned mechanically time is 0.5~20min, revolving speed
For 10~100rpm；
In step 3), the speed of stirring is 50~200rpm, and the time of absorption is 5~30min, and the time of polymerization reaction is
0.5~4h, the temperature of polymerization reaction are -5~25 DEG C.
The second aspect of the present invention provides the chromogen bonded polymer conductive bead as made from above-mentioned preparation method.
Beneficial effects of the present invention:
Present invention process is simple, and solvent can be recycled, and industrial can amplify.Using conducting polymer self color and lead
Electrical characteristics, the synchronous two fold problem for solving to inhibit electrostatic and colored demand.
The present invention carries out confinement to polymer beads by good solvent/poor solvent mixed liquor and is controllably swollen, with conduction
The solution of polymer is seed liquor, then in-situ polymerization occurs in polymer beads confinement layer by the monomer of conducting polymer, is obtained
The polymer beads coated to conductive polymer fibers.The present invention can pass through the controllable swelling pretreatment work of confinement of polymer beads
Skill realizes that the surface layer confinement of polymer beads is controllably swollen, then passes through the synthesis technology factor control of chromogen bonded polymer conductive bead
System can synthesize to obtain the chromogen bonded polymer conductive bead of a series of different electric conductivities and different colours.Conducting polymer and poly-
Conjunction object bead compatibility is good, and lower conducting polymer content can assign the preferable conductive effect of polymer beads and colour,
The internal structure for not destroying polymer beads simultaneously still maintains the hair of polymer beads for foamable polymer beads
Steep characteristic.
Other features and advantages of the present invention will then part of the detailed description can be specified.
Detailed description of the invention
Fig. 1 shows the conducting performance test for the chromogen bonded polymer conductive bead that synthetic method provided by the present invention obtains
Equipment therefor；
Fig. 2 shows a kind of expandable polystyrene (EPS) beads of the invention used；
Fig. 3 shows a kind of chromogen bonded polymer conductive bead that synthetic method provided by the present invention obtains；
Fig. 4 shows synthetic method provided by the present invention and obtains a kind of surface scan electricity of chromogen bonded polymer conductive bead
Sub- microscope photograph.
Specific embodiment
The preferred embodiment of the present invention is described in more detail below.Although the following describe preferred implementations of the invention
Mode, however, it is to be appreciated that may be realized in various forms the present invention without that should be limited by the embodiments set forth herein.Phase
Instead, these embodiments are provided so that the present invention is more thorough and complete, and can be by the scope of the present invention completely
It is communicated to those skilled in the art.
In the embodiment of the present invention, the temperature of polymerization reaction is -5~25 DEG C.
Embodiment 1
1) preparation of conducting polymer seed liquor
Polyaniline is dissolved in preparation 0.5mg/mL polyaniline seed liquor in dimethyl sulfoxide.
2) the controllable swelling pretreatment of the confinement of polymer beads
Weigh chloroform/ethyl alcohol mixed solvent (three that polystyrene bead 15g is scattered in 25mL polystyrene bead
The volume ratio of chloromethanes and ethyl alcohol is 1:4) in, mechanical stirring 1min, revolving speed 40rpm, separation of solid and liquid obtain pretreatment polyphenyl
Ethylene bead.
3) synthesis of chromogen bonded polymer conductive bead
0.5mol/L aqueous hydrochloric acid solution 20mL, 3mmol aniline monomer and 0.5mg/mL polyaniline kind are added into reaction flask
Then sub- liquid 0.5mL pretreatment polystyrene bead 15g obtained in step 2) is added in above-mentioned system, is kept stirring speed
60rpm is spent, 6min is adsorbed, is added dropwise into above-mentioned system and is made of 3mmol ammonium persulfate and 0.5mol/L aqueous hydrochloric acid solution 20mL
Initiator solution, polymerization reaction 1h after strainer filtering water washing, obtains colorful polystyrene conductive bead.
Embodiment 2
1) preparation of conducting polymer seed liquor
Polypyrrole is dissolved in preparation 1mg/mL polypyrrole seed liquor in dimethyl sulfoxide.
2) the controllable swelling pretreatment of the confinement of polymer beads
Weigh polymethyl methacrylate bead 20g be scattered in the methylene chloride of 30mL polymethyl methacrylate bead/
In the mixed solvent (volume ratio of methylene chloride and methanol is 1:6) of methanol, mechanical stirring 2min, revolving speed 50rpm, solid-liquid point
From obtain pretreatment polymethyl methacrylate bead.
3) synthesis of chromogen bonded polymer conductive bead
0.8mol/L phosphate aqueous solution 25mL, 5mmol pyrrole monomer and 1mg/mL polypyrrole seed are added into reaction flask
Then liquid 1mL pretreatment polymethyl methacrylate bead 20g obtained in step 2) is added in above-mentioned system, keeps stirring
Speed 80rpm is mixed, 12min is adsorbed, is added dropwise into above-mentioned system by 5mmol potassium peroxydisulfate and 0.8mol/L phosphate aqueous solution 25mL
The initiator solution of composition, polymerization reaction 1.5h after strainer filtering water washing, obtain colored polymethyl methacrylate conductive bead
Grain.
Embodiment 3
1) preparation of conducting polymer seed liquor
Polyaniline is dissolved in preparation 1.2mg/mL polyaniline seed liquor in dimethyl sulfoxide.
2) the controllable swelling pretreatment of the confinement of polymer beads
Weigh toluene/propyl alcohol mixed solvent (first that expandable polystyrene (EPS) bead 25g is scattered in 40mL polymer beads
The volume ratio of the propyl alcohol of benzene is 1:8) in, mechanical stirring 4min, revolving speed 60rpm, separation of solid and liquid obtain pre-processing expandable poly-
Styrene beads.
3) synthesis of chromogen bonded polymer conductive bead
1mol/L high chloro acid solution 30mL, 8mmol aniline monomer and 1.2mg/mL polyaniline kind are added into reaction flask
Then sub- liquid 1mL pretreatment expandable polystyrene (EPS) bead 25g obtained in step 2) is added in above-mentioned system, keeps stirring
Speed 90rpm is mixed, 15min is adsorbed, is added dropwise into above-mentioned system by 8mmol ammonium persulfate and 1mol/L high chloro acid solution 30mL
The initiator solution of composition, polymerization reaction 2h after strainer filtering water washing, obtain colored expandable polystyrene (EPS) conductive bead.
Embodiment 4
1) preparation of conducting polymer seed liquor
Polypyrrole is dissolved in preparation 1mg/mL polypyrrole seed liquor in dimethyl sulfoxide.
2) the controllable swelling pretreatment of the confinement of polymer beads
It weighs poly- (styrene methyl methacrylate) bead 30g and is scattered in the tetrahydrofuran of 50mL polymer beads/different
In the mixed solvent (volume ratio of tetrahydrofuran and isopropanol is 1:10) of propyl alcohol, mechanical stirring 6min, revolving speed 65rpm, Gu
Isolated poly- (styrene methyl methacrylate) bead of pretreatment of liquid.
3) synthesis of chromogen bonded polymer conductive bead
1mol/L benzene sulfonic acid aqueous solution 40mL, 10mmol pyrrole monomer and 1mg/mL polypyrrole seed are added into reaction flask
Then above-mentioned body is added in poly- (styrene methyl methacrylate) the bead 30g of pretreatment obtained in step 2) by liquid 1.5mL
In system, it is kept stirring speed 100rpm, adsorbs 18min, is added dropwise into above-mentioned system by 10mmol ferric trichloride and 1mol/L benzene
The initiator solution of sulfonic acid aqueous solution 30mL composition, polymerization reaction 2.5h after strainer filtering water washing, obtain colored poly- (benzene second
Alkene-methyl methacrylate) conductive bead.
Embodiment 5
1) preparation of conducting polymer seed liquor
Polyaniline is dissolved in preparation 1.5mg/mL polyaniline seed liquor in dimethyl sulfoxide.
2) the controllable swelling pretreatment of the confinement of polymer beads
Weigh carbon tetrachloride/positive heptan that expandable polymethyl methacrylate bead 50g is scattered in 65mL polymer beads
In the mixed solvent (volume ratio of the normal heptane of carbon tetrachloride is 1:12) of alkane, mechanical stirring 10min, revolving speed 75rpm, solid-liquid
The isolated expandable polymethyl methacrylate bead of pretreatment.
3) synthesis of chromogen bonded polymer conductive bead
1.5mol/L salicylic acid solution 60mL, 12mmol aniline monomer and 1.5mg/mL polyaniline kind are added into reaction flask
Then above-mentioned system is added in the expandable polymethyl methacrylate bead 50g of pretreatment obtained in step 2) by sub- liquid 1mL
In, it is kept stirring speed 120rpm, adsorbs 25min, is added dropwise into above-mentioned system by 12mmol ammonium persulfate and 1.5mol/L water
The initiator solution of poplar aqueous acid 40mL composition, polymerization reaction 3.5h after strainer filtering water washing, are obtained colored expandable poly-
Methyl methacrylate conductive bead.
Fig. 1 shows the conducting performance test for the chromogen bonded polymer conductive bead that synthetic method provided by the present invention obtains
Equipment therefor.The chromogen bonded polymer conductive bead of synthesis is put into the container in left side and is filled, be inserted into electric grade, opens digital display
Multimeter note can show reading, the as sheet resistance of chromogen bonded polymer conductive bead.
Fig. 2 shows a kind of expandable polystyrene (EPS) beads of the invention used.The bead is spheric profile, average grain diameter
About 1mm, sheet resistance are more than 1014Ohm.
Fig. 3 shows a kind of chromogen bonded polymer conductive bead that synthetic method provided by the present invention obtains.It can from picture
To find out that chromogen bonded polymer conductive bead is the spherical design of rule, average grain diameter about 1mm, and have it is uniform blackish green, this
It is the self color from electrically conductive polyaniline.The surface resistance testing instrument provided by Fig. 1 is it is found that the chromogen bonded polymer is conductive
The sheet resistance of bead is 962 ohm, illustrates that it measures conducting polymer with preferable electric conductivity, and by component separation
Content of the component in chromogen bonded polymer conductive bead is about 0.17%.In addition, the color and electric conductivity of polymer beads are all
Controllable, it is conductive by the chromogen bonded polymer of other colors such as the available light green color of process adjustments, green, blackish green, black
Bead.
Fig. 4 shows synthetic method provided by the present invention and obtains a kind of surface scan electricity of chromogen bonded polymer conductive bead
Sub- microscope photograph.As can be seen from the figure the surface of chromogen bonded polymer conductive bead is gathered by the conduction of many diameters about 90nm
The conductive network that fibres are constructed is closed, therefore assigns the preferable electric conductivity of polymer beads, in addition, in conducting polymer dosage
Under the same conditions, it is easy overlap joint between conductive polymer nanometer fiber and forms conductive network, more than conductive polymer nanometer particle
Conductive network easy to form, it is with the obvious advantage.
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes are obvious for the those of ordinary skill in art field.
Claims (10)
1. a kind of preparation method of chromogen bonded polymer conductive bead, which is characterized in that the preparation method includes:
1) preparation of conducting polymer seed liquor
Conducting polymer is dissolved in dimethyl sulfoxide, preparation obtains conducting polymer seed liquor；
2) the controllable swelling pretreatment of the confinement of polymer beads
It disperses polymer beads in the in the mixed solvent of good solvent and poor solvent, then is separated by solid-liquid separation and obtains pretreatment polymerization
Object bead；
3) synthesis of chromogen bonded polymer conductive bead
The monomer of conducting polymer described in the first acidic aqueous solution, step 1) is added into reaction vessel, step 1) obtains
The pretreatment polymer beads that conducting polymer seed liquor, step 2) obtain, stirring, are adsorbed, add initiator solution
Polymerization reaction is carried out, after being filtered, washed after reaction, obtains chromogen bonded polymer conductive bead；The initiator solution is oxygen
The mixture of agent and the second acidic aqueous solution.
2. preparation method according to claim 1, wherein
In step 2), relative to the mixed solvent of 20~100mL good solvent and poor solvent, the dosage of polymer beads is 5~
80g；
In step 3), relative to the monomer of conducting polymer described in 1~20mmol step 1), the dosage of other each components are as follows:
0.1~2mL of conducting polymer seed liquor that first 10~100mL of acidic aqueous solution, step 1) obtain, 1~20mmol of oxidant,
Second 10~60mL of acidic aqueous solution；
Wherein, the concentration of the first acidic aqueous solution is 0.1~4mol/L, and the concentration of conducting polymer seed liquor is 0.1~5mg/
ML, the concentration of the second acidic aqueous solution are 0.1~4mol/L.
3. preparation method according to claim 1, wherein the conducting polymer is polyaniline or polypyrrole.
4. preparation method according to claim 1, wherein the polymer beads are selected from polystyrene, polymethyl
Sour methyl esters, poly- (styrene methyl methacrylate), expandable poly- (styrene methyl methacrylate), expandable polyphenyl second
At least one of alkene and expandable polymethyl methacrylate bead.
5. the preparation method according to claim 4, wherein the partial size of the polymer beads is 0.1~2mm.
6. preparation method according to claim 1, wherein
The good solvent is selected from chloroform, methylene chloride, limonene, toluene, dimethylbenzene, ethylbenzene, benzene, methyl ethyl ketone, acetic acid second
At least one of ester, carbon tetrachloride, n-butyl acetate, tetrahydrofuran and N,N-dimethylformamide；
The poor solvent is selected from at least one of methanol, ethyl alcohol, propyl alcohol, butanol, isopropanol and normal heptane；
In the mixed solvent good solvent and poor solvent volume ratio are 1:1~15.
7. preparation method according to claim 1, wherein in step 3), first acidic aqueous solution and the second acidity
Aqueous solution be each independently selected from hydrochloric acid solution, sulfuric acid solution, phosphate aqueous solution, high chloro acid solution, camphorsulfonic acid aqueous solution,
Benzene sulfonic acid aqueous solution, dodecyl benzene sulfonic acid aqueous solution, p-methyl benzenesulfonic acid aqueous solution, p styrene sulfonic acid aqueous solution, naphthalene sulfonic acids
At least one of aqueous solution, aqueous solution of salicylic acid, aqueous tartaric acid solution and phenyl-phosphonic acid aqueous solution.
8. preparation method according to claim 1, wherein in step (3), the oxidant is ammonium persulfate, persulfuric acid
Potassium or ferric trichloride.
9. preparation method according to claim 1, wherein
In step 2), the dispersion is realized by mechanical stirring, and the churned mechanically time is 0.5~20min, revolving speed 10
~100rpm；
In step 3), the speed of stirring is 50~200rpm, and the time of absorption is 5~30min, and the time of polymerization reaction is 0.5
~4h, the temperature of polymerization reaction are -5~25 DEG C.
10. chromogen bonded polymer conductive bead made from the preparation method as described in any one of claim 1-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811109215.1A CN109251435B (en) | 2018-09-21 | 2018-09-21 | Colored polymer conductive bead and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811109215.1A CN109251435B (en) | 2018-09-21 | 2018-09-21 | Colored polymer conductive bead and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109251435A true CN109251435A (en) | 2019-01-22 |
| CN109251435B CN109251435B (en) | 2021-05-28 |
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