CN1410486A - Conductive polymer-sulfonated polymeric elastomer composite conductive rubber and its preparation method - Google Patents
Conductive polymer-sulfonated polymeric elastomer composite conductive rubber and its preparation method Download PDFInfo
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- CN1410486A CN1410486A CN 02138451 CN02138451A CN1410486A CN 1410486 A CN1410486 A CN 1410486A CN 02138451 CN02138451 CN 02138451 CN 02138451 A CN02138451 A CN 02138451A CN 1410486 A CN1410486 A CN 1410486A
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Abstract
An electrically conductive composite rubber is prepared through sulfonating the high-molecular elastomer with benzene ring or unsaturated double-bond and electrochemical doped with electrically conductive heterocycle polymer. Its advantages are high stability of electric conductivity and good elasticity.
Description
(1) technical field:
The present invention relates to class novel conductive rubber and preparation method thereof, it belongs to composite conducting rubber technology field.
(2) background technology:
Conductive rubber is at electronic sensor in recent years, the polymer display screen, and extensive application in the microelectronic component and potential demand have caused the extensive attention of people to its action oriented research.In order to adapt to the demand of different use occasions, also more and more higher to the over-all properties requirement of conductive rubber.Typical performance requriements is: 1. good and stable electroconductibility; 2. the not obvious decline of specific conductivity in deformation process; 3. conductive component has dispersiveness and consistency preferably in rubber.Along with microelectronic device constantly develops to miniaturization and functionalization, also require material to have good film-forming properties; Better dispersed, consistency between conductive component and the rubber; Stronger anisotropy or the like.
Use now maximum be the rubber that carbon black and metallic particles are filled.Their material cost is lower, and also can obtain certain specific conductivity after the blend, but because they are insoluble to any solvent and can only carry out simple mechanical blending in rubber substrate, be subjected to the influence of processing conditions bigger, be difficult to obtain dispersed well-proportioned intermingling material, constitute the weakness on the stress structure easily, make whole mechanical properties that bigger decline be arranged.At the particle on the material surface with extraneous friction or in the rubber telescopic process, come off easily, thereby cause the decline of the apparent specific conductivity of material monolithic.There is in the deformation process specific conductivity problem such as decline to a great extent in addition.
In recent years, along with the progress of organic conductive superpolymer functionalization and action oriented research, people begin to replace carbon black and metal and blend rubber with conductive polymers.Though conductive polymers is full organic materials, the overwhelming majority all cannot not be molten, insoluble pulverulent solids, and rigidity is big, poor in processability.Method commonly used also is and the rubber manufacturing machinery blend that its relative merits are identical with the blend situation of carbon black, metal powder.
Be widely studied at present, and dispersion effect the best way is a solution blended process.Its mechanism is as follows:
Conductive polymers only just possesses conductivity under the doping situation, and traditional doping agent is generally mineral acid, example hydrochloric acid, and sulfuric acid etc. are disadvantageous for improving the solvability of conductive polymers in organic solvent.Have the doping agent such as the camphorsulfonic acid of large volume or long-tail chain lipophilic group by adding, or material such as Sodium dodecylbenzene sulfonate make conductive polymerss such as polyaniline under dopant states by the good dissolubility of doping agent and be dissolved in organic solvent.Its similar is in graftomer, utilizes the processable of side chain or large volume side group to improve the solvability of stiff backbone.
Preparation process is as follows: conductive polymers monomer and the doping agent that has large volume or long-tail chain lipophilic group are dissolved in solvent, add a certain amount of oxygenant and make it polymerization, doping agent is attached in the conductive polymers in polymerization process.The washing of product solution with water is removed excessive oxidant, impurity such as doping agent.Be dissolved in a cresol after the vacuum-drying, the chlorobenzene equal solvent, miscible with rubber solutions again, the film forming of volatilizing at last.The dispersion effect of this method is better, and is limited but the solvability of conducting polymer improves, and can only be dissolved in some high boiling points, solvent that toxicity is big usually, as: a cresol, chlorobenzene etc. easily pollute environment.{ reference [1] G.R.Valenciano, A.E.Job, L.H.C.Manttoso, Polymer, 2000,41,4757-4760; [2] Thomas E.Olinga, Jerome Fraysse, Jean Pierre, Alain Dufresne, Adam Pron, Macromolecules, 2000,33,2107-2113}, it is characterized in that: 1. contain conductive polymer composition and rubber components, the content of conductive polymers is between 5wt%-40wt%.2. no chemical action power between conductive polymers and the rubber molecule belongs to physical blending.3. blend is isotropic.4. specific conductivity can descend significantly in the rubber drawing process.5. the doping agent of conductive polymers is a small molecules, goes easily to mix in environment for use, and specific conductivity is descended gradually.6. be phase-splitting between conductive polymers and the rubber molecule.
Accompanying drawing 1 is seen in the signal of internal structure state.
In addition, the nanoparticle dispersion method also is blend means relatively more commonly used.Make nano particle with microemulsion polymerization method.Be suspended in them among the rubber solutions and utilize ultrasonic dispersing, simultaneously heated volatile solvent film forming.It goes for multiple conducting polymer composite, but nanoparticle manufacturing cost height, and and ultra-sonic dispersion is not suitable for large-scale industry and makes, and is unfavorable for that industry promotes.{ reference [3] Hong-Quan Xie, Yong-Mei Ma, Journal of Applied Polymer Science, 2000,77,2156-2164}
Remain physical blending between its nano particle of Zhi Bei conductive rubber and the rubber molecule in this way, product is isotropic, specific conductivity can decline to a great extent in drawing process, and also can't avoid being gone to mix and problem that the electric conductivity that causes descends by the small molecules doping agent.
Though replace carbon black and metal and blend rubber can't really reach industrial application requirements with conductive polymers at present,, remain developing direction from now on because conduction high polymer itself has functionalization developing direction such as luminous, anticorrosion, electromagnetic shielding.With the organic macromolecular LED device is example, conducting polymer luminescent material such as Polythiophene, and polyanilines etc. have high brightness, reduce power consumption, controllable color, low cost and other advantages can do that luminescent layer or electronics-can lead/hole-layer material is obstructed.But because their indissolubles and fragility are big, all very inconvenient when using in processing, add some elastomeric components and make them have some snappinesies will to improve its scope of application greatly.But present method of modifying all is to be main means with physical blending, it is poor to exist consistency, makes trouble, and pollutes easily, electroconductibility is descended the degradation problem easily, is difficult to produce the film that not only has caoutchouc elasticity but also can keep the functional property of conducting polymer own.
(3) content of the present invention
The objective of the invention is: solve the defective that existing blending method is made conductive rubber, a kind of new preparation method is provided, produce the conductive rubber film of high-quality tens to 200 micron thickness with it, make it to have good electrical conductivity, elasticity, stability and anisotropy are expected to be applied in the polymer indicating meter, corrosion protection coating, aspects such as unilateral conduction material.
The principle of the invention is as follows:
Conductive polymers can be with electrochemical method at the anode surface polymerization film formation, and the macromole ionogen contains a large amount of negatively charged ion, the automatic anode enrichment of meeting under galvanic action after the disassociation in solution, the macromole ionogen will embed in the conduction high polymer equably when the polymerization velocity of conduction high polymer is suitable with the electrolytical translational speed of macromole, make it to become the doping attitude and have electroconductibility, both will form uniform complex body.
The object of the present invention is achieved like this:
But will contain sulfonation segmental elastomericss such as polystyrene, polysulfones or unsaturated double-bond and carry out all or part of sulfonation processing, make it to become the flexible polyelectrolyte that has anionic group, be made into a certain proportion of solution with the monomer of conductive polymers and carry out electrochemical polymerization, generate conductive rubber film at working electrode surface.The sulfonation elastomerics embeds in the middle of the conducting polymer in the mode of doping agent, and conducting polymer becomes homodisperse conductive component in rubber inside, carries out crosslinkedly simultaneously between the sulfonation segment, generates high-quality conductive rubber film.Below
With the situation among the embodiment 1 is example, further sets forth preparation process: see accompanying drawing 2.
Preparation method's of the present invention advantage is:
1. a lot of polymer elastomers, especially having the disconnected elastomerics with Grafting Structure of embedding contains than softish and the bigger disconnected or branched structure (as Hydrogenated SBS) of two kinds of embeddings of rigidity, in its stiff chain of sulfonation (as the polystyrene block in the Hydrogenated SBS), keep the disconnected or branched structure constant (as the hydrogenated butadiene polymer block in the Hydrogenated SBS) of its soft embedding, make it to become and promptly have the flexible doping agent that snappiness has a large amount of anionic groups again.In the electrochemical synthesis process, do not add the small molecules doping agent, both simplified preparation condition, guaranteed the stable of product electric conductivity owing to the macromole doping agent is difficult for mixing again.
2. because the macromole negatively charged ion has stronger repulsive interaction in solution, in the process of electrochemical synthesis, be difficult for forming independent gathering phase, so by it adulterated conductive polymers dispersed fine in rubber diaphragm, be difficult for forming structural thin spot, thereby keep the favorable mechanical performance.
3. conductive polymers links together by the doping effect between elastomer substrates, it belongs to the chemical action power between the zwitterion, both can not come off because of surface friction in conjunction with closely, have solved the common problem for preparing the easy decline of conductive rubber surface conductivity with blending method.
4. macromolecular elastomer needed usually through crosslinking Treatment before becoming spendable rubber, make its elastic deformation become recoverable process, in the present invention, combine with chemical action power between the conductive polymers of doping attitude and the sulfonated polymer elastomerics, and can derive from different elastomer molecules with sulfonation group that same conductive polymer molecules combines, like this conductive polymers just between the sulfonated polymer elastomer molecules, produce crosslinked action make it to become can life-time service conductive rubber.
5. because the macromole elastomerics is a form with doping agent combines with conductive polymers, it is identical that the electrochemical growth mechanism of conductive polymers and small molecules doping agent exist under the situation, still can keep the photoelectromagnetism and the antiseptic property of conducting polymer film itself preferably.
Product structure characteristic of the present invention is: 1. product is a black thin film, thickness between the 20-200 micron, one of them smooth surface and glossy.2. contain conductive polymer composition and rubber components, the content of conductive polymers is between 20wt%-50wt%.Between conductive polymers and the sulfonated polymer elastomerics with chemical action power close-coupled.4. the doping agent of conductive polymers is flexible macromole ionogen.5. the specific conductivity of composite membrane is anisotropic.6. being homogeneous phase between conductive polymers and the sulfonated polymer elastomerics distributes.
Accompanying drawing 3 is seen in the signal of internal structure state.
(4) description of drawings: Fig. 1: the internal structure view 2 after soluble conductive macromolecular and the rubber solutions blend: preparation process Fig. 3 of polypyrrole-Hydrogenated SBS sulfonated bodies composite conducting rubber diaphragm: the internal structure view 4 after conductive polymers and the electrochemical polymerization of sulfonated polymer elastomerics: preparation Fig. 5 of polyaniline (or polypyrrole)-sulfonation polyoxyethylene glycol/polystyrene block polymkeric substance compounded rubber film: the preparation of Polythiophene-sulfonated polybutadiene composite conducting rubber diaphragm
(5) specific implementation method of the present invention:
The rubber diaphragm for preparing in the following example is placed 100 days specific conductivity no changes at normal temperatures.Elongation at break is more than or equal to 130%.The preparation of example 1 polypyrrole-Hydrogenated SBS sulfonated bodies composite conducting rubber diaphragm
Hydrogenated polystyrene-polyhutadiene-polystyrene three inlay and break copolymers are dissolved in methylene dichloride and trichloromethane mixed solvent, be made into the concentration of 2wt%-10wt%, under 30 ℃, be added dropwise to chlorsulfonic acid-triethyl phosphate sulphonating agent (chlorsulfonic acid-triethyl phosphate sulphonating agent by chlorsulfonic acid and triethyl phosphate sulphur in 3: 1-1: 1 ratio is dissolved in the dichloromethane solvent to be made) of excessive 10%-100% (mol ratio), reacted 40 minutes, reacted solution poured in a large amount of ethylene dichloride be settled out product, with methylene dichloride washing precipitation product repeatedly, be made into the tetrahydrofuran solution of 1wt%-4wt% after the vacuum-drying, the pyrrole monomer that adds 0.3wt%-1wt% again, stir, with the stainless steel electrode is working electrode and counter electrode, the Ag/AgCl electrode is a reference electrode, the continuous current polymerase 10 is .5-4 hour under the current density of 0.05-0.2 milliampere(mA)/square centimeter, wash the conductive rubber film that is aggregated in working electrode surface with a small amount of tetrahydrofuran solvent, peel the conductive rubber film after the vacuum-drying.Film thickness is between the 20-150 micron.Membrane plane internal conductance rate σ
∥In the 0.1-2 Siemens/cm, vertical film planar conductivity
⊥10
-6-10
-5Siemens/cm, σ
∥: σ
⊥≈ 10
5, in the rubber diaphragm drawing process along the σ of draw direction
∥Can rise nearly 1 times, and σ
⊥Descend nearly 10 times, anisotropy further increases.Example 2 polyanilines (or polypyrrole)-sulfonation polyoxyethylene glycol/polystyrene block polymkeric substance composite conducting rubber diaphragm preparation
This routine reaction process is: see accompanying drawing 4.
Polyoxyethylene glycol/polystyrene block polymkeric substance is dissolved in the ethylene dichloride bonding solvent, be made into the concentration of 2wt%-10wt%, under 0 ℃, be added dropwise to chlorsulfonic acid-triethyl phosphate sulphonating agent of excessive 10%-100% (mol ratio), reacted 40 minutes, reacted solution poured in a large amount of tetrachloroethane be settled out product, with ethanol washing precipitation product repeatedly, be made into the aqueous solution of 1wt%-4wt% after the vacuum-drying.
1. with the aniline modification: the aniline that adds 0.5wt%-1wt%, with the stainless steel electrode is working electrode and counter electrode, the Ag/AgCl electrode is a reference electrode, the continuous current polymerase 10 is .5-2 hour under the current density of 0.05-0.1 milliampere(mA)/square centimeter, wash the conductive rubber film that is aggregated in working electrode surface with a small amount of tetrahydrofuran solvent, peel the conductive rubber film after the vacuum-drying.
2. with pyrroles's modification: sulfonated elastomer solution is neutralized with NaOH, be made into the aqueous solution of 1wt%-4wt%, the pyrroles who adds 0.5wt%-1wt%, with the stainless steel electrode is working electrode and counter electrode, the Ag/AgCl electrode is a reference electrode, the continuous current polymerase 10 is .5-2 hour under the current density of 0.05-0.1 milliampere(mA)/square centimeter, washs the conductive rubber film that is aggregated in working electrode surface with a small amount of tetrahydrofuran solvent, peels the conductive rubber film after the vacuum-drying.
Film thickness is between the 20-100 micron.Membrane plane internal conductance rate σ
∥In the 0.5-4 Siemens/cm, vertical film planar conductivity
⊥10
-6-10
-5Siemens/cm, σ
∥: σ
⊥≈ 10
5, in the rubber diaphragm drawing process along the σ of draw direction
∥Can rise nearly 2 times, and σ
⊥Descend nearly 10 times, anisotropy further increases.The preparation of example 3 Polythiophenes-sulfonated polybutadiene composite conducting rubber diaphragm
This routine reaction process is: see accompanying drawing 5.
Polyhutadiene is dissolved in methylene dichloride and trichloromethane mixed solvent; be made into the concentration of 2wt%-10wt%; under-5 ℃, be added dropwise to the chlorsulfonic acid-triethyl phosphate sulphonating agent that is equivalent to its pair key mole number 1/4-1/2; reacted 15 minutes; reacted solution poured in a large amount of methylene dichloride be settled out product; with ethanol washing precipitation product repeatedly; be made into the tetrahydrofuran solution of 1wt%-4wt% after the vacuum-drying; the thiophene monomer that adds 0.5wt%-1wt% again; stir; with the stainless steel electrode is working electrode and counter electrode; the Ag/AgCl electrode is a reference electrode; feed nitrogen in the reaction forward direction solution and remove oxygen; use nitrogen protection in the reaction more than the liquid level; the continuous current polymerase 10 is .5-3 hour under the current density of 0.05-0.1 milliampere(mA)/square centimeter, washs the conductive rubber film that is aggregated in working electrode surface with a small amount of tetrahydrofuran solvent, peels the conductive rubber film after the vacuum-drying.Film thickness is between the 30-200 micron.Membrane plane internal conductance rate σ
∥In the 0.05-0.3 Siemens/cm, vertical film planar conductivity
⊥10
-5-10
-4Siemens/cm, σ
∥: σ
⊥≈ 10
5, in the rubber diaphragm drawing process along the σ of draw direction
∥Can rise nearly 0.5 times, and σ
⊥Descend nearly 5 times, anisotropy further increases.
Purposes of the present invention is: on method traditional conductive rubber film manufacture process is reformed, with electricity The method of chemical doping has replaced simple blend, produces the conductive rubber film that a class has new capability. Lead Electrostatic force by positive and negative charge between electric polymer and the rubber is closely linked, and both compatibilities are good, conduction Property is good, good stability, and technology is simple, is applicable to that the high-quality thickness of large-scale production is little to 200 tens Conductive rubber film between the rice is applicable to and does pliable and tough organic polymer luminescent material, corrosion-inhibiting coating, electrical screen Cover material, its anisotropy excellence can be used as soft unilateal conduction material simultaneously.
Claims (4)
1. conductive polymers-sulfonated polymer elastomer composite conductive rubber, adopt the heterocyclic conductive polymers, solubility sulfonated polymer elastomerics is formed composite conducting rubber, it is characterized in that the doping agent of solubility sulfonated polymer elastomerics as conductive polymers, the heterocyclic conductive polymers is formed composite conducting rubber as the elastomeric linking agent of sulfonated polymer, the content of conductive polymers is between 20wt%-50wt%, between conductive polymers and the sulfonated polymer elastomerics with chemical action power close-coupled, conductive polymers and sulfonated polymer elastomerics are homogeneous phase and distribute, composite conducting rubber is black thin film, rubber diaphragm thickness is the 20-200 micron, the specific conductivity of conductive rubber film is anisotropic, membrane plane internal conductance rate σ
∥Be the 0.05-4 Siemens/cm, vertical film planar conductivity
⊥Be 10
-6-10
-4Siemens/cm, specific conductivity does not change in time under the normal temperature, and the elongation at break of composite conducting rubber is more than or equal to 130%.
2. conductive polymers according to claim 1-sulfonated polymer elastomer composite conductive rubber, its feature is that also the heterocyclic conductive polymers is polyaniline, polypyrrole, Polythiophene and derivative thereof, and solubility sulfonated polymer elastomerics is the macromolecular elastomer that contains aromatic ring and contain unsaturated double-bond.
3. the preparation method of conductive polymers-sulfonated polymer elastomer composite conductive rubber, with the stainless steel electrode is working electrode and counter electrode, use the pyrroles, aniline or thiophene and derivative thereof, contain the macromolecular elastomer of aromatic ring or unsaturated double-bond and the concentration that chloroparaffin is made into 2wt%-10wt%, drip chlorsulfonic acid-triethyl phosphate sulphonating agent down at-5 ℃-30 ℃, reacted 15-40 minute, pour reacted solution into a large amount of ethylene dichloride, be settled out product in methylene dichloride or the tetrachloroethane, with ethanol or washed with dichloromethane product, be made into the tetrahydrofuran (THF) or the aqueous solution of 1wt%-4wt% after the drying, the pyrroles who adds 0.3wt%-1wt% again, aniline or thiophene monomer, stir, the continuous current polymerase 10 is .5-4 hour under the current density of 0.05-0.2 milliampere(mA)/square centimeter, generate the composite conducting rubber diaphragm in the working electrode surface polymerization, film thickness is at the 20-200 micron, membrane plane internal conductance rate σ
∥Be the 0.05-4 Siemens/cm, vertical film planar conductivity
⊥Be 10
-6-10
-4Siemens/cm.
4. the preparation method of conductive polymers according to claim 3-sulfonated polymer elastomer composite conductive rubber, its feature are that also the described macromolecular elastomer that contains aromatic ring and unsaturated double-bond is hydrogenated polystyrene-polyhutadiene-polystyrene copolymer, polyoxyethylene glycol-polystyrene copolymer, polybutadiene polymers.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633964A (en) * | 2012-04-28 | 2012-08-15 | 南京信息工程大学 | Sulfonated SBS (styrene-butadiene-styrene) ionomer and application thereof |
| US9154058B2 (en) | 2008-08-15 | 2015-10-06 | Board Of Regents, The University Of Texas System | Nanofiber actuators and strain amplifiers |
| US9243351B2 (en) | 2009-05-27 | 2016-01-26 | Board Of Regents, The University Of Texas System | Fabrication of biscrolled fiber using carbon nanotube sheet |
| JP2017002226A (en) * | 2015-06-12 | 2017-01-05 | トヨタ紡織株式会社 | Composite film and method for producing the same |
| CN107917939A (en) * | 2017-11-27 | 2018-04-17 | 电子科技大学 | Electromagnetism chemical sensor based on conducting polymer and preparation method thereof |
-
2002
- 2002-10-17 CN CN 02138451 patent/CN1200045C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9154058B2 (en) | 2008-08-15 | 2015-10-06 | Board Of Regents, The University Of Texas System | Nanofiber actuators and strain amplifiers |
| US9243351B2 (en) | 2009-05-27 | 2016-01-26 | Board Of Regents, The University Of Texas System | Fabrication of biscrolled fiber using carbon nanotube sheet |
| US9502711B2 (en) | 2009-05-27 | 2016-11-22 | Board Of Regents, The University Of Texas System | Fabrication of biscrolled fiber using carbon nanotube sheet |
| CN102633964A (en) * | 2012-04-28 | 2012-08-15 | 南京信息工程大学 | Sulfonated SBS (styrene-butadiene-styrene) ionomer and application thereof |
| JP2017002226A (en) * | 2015-06-12 | 2017-01-05 | トヨタ紡織株式会社 | Composite film and method for producing the same |
| CN107917939A (en) * | 2017-11-27 | 2018-04-17 | 电子科技大学 | Electromagnetism chemical sensor based on conducting polymer and preparation method thereof |
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|---|---|
| CN1200045C (en) | 2005-05-04 |
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