CA2069291C - Polyaniline compositions having a surface/core dopant arrangement - Google Patents

Abstract

A electrically conductive polyaniline particle comprising a substituted or unsubstituted polyaniline doped with two or more dopants, at least one of said dopants predominating at or near the surface of said particles and at least one other dopant predominating at or near the core of said particle.

Description

fOLYANILTNE COMPOSITTONS HAVING;
~SLBt~~sr. ~ ~.Q,T~ DQ PB,i~N~ ; EME N T
~K.O~Q31L~~ OF THE INVENTION
1 . ~ ~,e ld Qf t a I~..v~tlt,.~ol1 This invention relates to novel electri~a'_Ly conductive polyaniline compositions. Another aspect of this invention relates to polyaniline articles, including films, fibers. coatings and the like formed from the polymer compositions of this invention.

2. p~s~riptj,9~ of the Prior Art There has recently been an increased interest in the electrochemistry and electrical phenomena of Polymeric systems. Recently, work has intensified with backbone polymers having extended conjugation in at least one backbone chain.
One conjugated polymer system currently under study is polyaniline. Kc~bayashi, et al., ,T_ ElectrQ~l. Chem~, "Electrochemical Reactions Concerned with Electrochromism of Polyaniline Film-i.oated Electrodes", LZ 281-291 (1984). describes various experiments in which spectro electro-chemical measurement of a polyaniline film coated electrode were made. French Patent Ne. 1,519,729; French Patent of l~ddition 94,536; U.K. Patent 1,216,549; "Direct Current Conductivity of Polyaniline Sulfate", M.
Doriomedoff, F. Rautiere - Cristofini, R. De Surville, M. Jozefowicz, L-T. Yu, and R. Huvet, sL
Chim,L Phvs. Phvsico~im. ~~~, 58, 1055 ( 1971) ~Continuous Curtent Conduc'_ivity of MacLOmolecular Materials", L-T. Yu, M. Jozefowicz. and R. fiuvet, Chim. Macramol, i, 469 (J.97U); "Polyaniline Based Filmogenic Organic-Conduc:.or Polymers", C. LaDarre and M. Jozefowicz, C.12. $~aa._~,~.. Ser. C, ~Q, 964 (1969); "Recently discovered Properties of Semiconducting Polymers", M. Jozefowicz, L-T. Yu, J.

-z-Perichon, and R. Buvet, ~T_~glym. Sci., Part C
1187 (1969); "Electrochemical Properties of Polyaniline Sulfates", F. Cristofini, R. De Surville, and M. Jozefowicz, C.R,_Acad. Ski., SPA. C, ~$, 1346 (1979); "Electrochemical Cells Using Protolytic Organic Semiconductors", R. De Surville, M.
Jozefowicz, L-T. Yu, J. Perichon, R. Buvet, Electrochem_. Acta., 1~, 1951 (1968); "Oligomers and Polymers Produced by Oxidation of Aromatic Amines", R. De Surville, M. Jozefowicz, and R. Buvet, Chem. (Paris) ~ 5 (1967); "Experimental Study of the Direct Current Conductivity of Macromolecular Compounds", L-T. Yu, M. 8orredon, M. Jozefowicz, G.
Helorgey, and R. Buvet, J. Polvm. Sci. Po .ym. Svmo., ~, 2931 (1967); "Conductivity and Chemical Properties of Oligorneric Polyaniline", M. Jozefowicz, L-T. Yu, G. Belorgey, and R. Buvet, J. o.vm. Sci.
PolytneSSumo. , .1~, 2943 ( 1967) ;, ~Products of the Catalytic Oxidation of Aromatic Amines". R. De Surville, M. Jozefowicz, and R. Buvet, Ann. Chim.
(Paris). ~. 149 (1967): "Conductivity and Chemical Composition of Maeromolecular Semiconductors", Rev.
Gea,. Electr., ~, 1014 (1966); "Relation Between the Chemical and Electrochemical Properties of Macromolecular Semiconductors~, M. Jozefowicz and L-T. Yu, Rev. Gea. Electr., ~ 100B (1966);
"Preparation, Chemical Properties, and Electrical Conductivity of Poly-N-Alkyl Anilines in the Solid State", D. Muller and M. Jozefowicz, Bull. Soc.
Che~°~ . Fr. 4087 (1972) .
U.S. Patent Nos. 3,963,496 and 4,025,463 describe oligomeric polyanilines and substituted polyanilines having not more than S aniline repeat units which are described as being soluble in certain organic solvents and which are described as being useful in the formation of semi-conductors compositions having bulk electrical conductivities up to about 7 x 10'3 S/cm and, surface resistivities of 4 x 107 ohm/square. European Patent No. 0017717 is an apparent improvement in the compositions of USP
Nos. 3,963,498 and 4,025,463 and states that the polyaniline can be formed into a latex composite through use of acetone solutions of the oligomers of polyaniline and a suitable binder polymer.
U.S. Patent No. 4,855,361 describes a conductive polymer blend which comprises mixing a Folyimide with a base-type polymer containing carbon nitrogen linkages, such as polyaniline, having a polyimide-like group covalently linked to the nitrogen atoms of the base-type polymer. The conductive polymer blend is formed by first reacting a base-type non-conductive polymer containing carbon-nitrogen linkages, such as polyaniline, with a carbonyl anhydride, such as 3,3',9,4'-benzophenone tetracarboxylic dianhydride to form a conductive polymer containing polyimide-like groups conveniently linked to the nitrogen atoms of the base-type polymer mixing such conductive polymer with non-conductive polyamide in a suitable solvent. removing the solvent, and forming a conductive continuous phase blend of the polyimide and the conductive polymer.
~5 U.S. Patent No. 4,798,685 describes the production of base-type conductive golymers, particularly from the family of conductive polyaniline, by reacting a base-group non-conductive polymer containing carbon-nitrogen linkages, e.g.
golyaniline,with an R+ donor compound, where R is an organic group. e.g. methyl iodide, and forming an electrically conductive polymer in which the R groups are covalently linked to the nitrogen atoms of the polymer.
U~S. patent No. 4,806,271 describes the production of base-type conductive polymers, particularly from the family of conductive polyaniline, by reacting a base-type non-conductive polymer containing carbon-nitrogen linkages e.g., polyaniline, with a cation donor compound, such as R2S04R, R'S02C1 or R"3SiCl, where R, R' and R" are alkyl or aryl, such as dimethyl sulfate or tosyl chloride, and forming an electrically conductive polymer in which the R groups of R2S04 and R'S02 groups of R'S02C1, or the R"3Si groups of R"3SiC1 are covalently linked to the nitrogen atoms of the Polymer.
U.S. Patent No. 4,822,638 describes a process for fabricating an electronic device on a non-conductive polymer substrate, particularly from the family of polyaniline, which comprises applying a covalent doping agent, such as an R+ donor compound, where R is an organic group, e.g., methyl iodide, to a preselected portion of a base-type non-conductive polymer substrate containing carbon-nitrogen linkages, and converting such preselected portion of the polymer substrate to an electrically conductive polymer portion, by covalent linkage of the R groups of such donor compound. to the nitrogen atoms of the non-conductive polymer substrate. Electronic devices, such as resistors, capacitors, inductors.
printed circuits and the like, can be provided by the invention process, in the form of light-weight polymers containing no metal,and which are stable and wherein the conductive portions are non-diffusing.
U.S. Patent No. 4,851,487 describes the ~ production of base-type conductive polymers, particularly from the family of conductive polyaniline, by reacting a base-type non-conductive polymer containing carbon-nitrogen linkages, e.g., polyaniline, with an anhydride such as R-S02-O-S02-R', R-CO-O-CO-R°, R-CO-O-S02R' or miztures thereof, where R and R' are alkyl or aryl, e.g., tosylic anhydride or benzophenone ~~~9291 tetracarboxylic dianhydride, and forming an electrically conductive polymer in which the S02R and COR groups are covalently linked to the nitrogen atortis of the conductive polymer and the anion of the conductive polymers is the S03R' or 02CR' group.
U.S. Patent No. 4,798,685 describes the production of base-type conductive polymers, particularly from the Family of conductive polyaniline, by reacting a base-type non-conductive Polymer containing carbon-nitrogen linkages, e.g., polyaniline, with an R+ donor compound, where R is an organic group, e.g., methyl iodide, and forming an electrically conductive polymer in which the R groups are covalently linked to the nitrogen atoms of the Polymer. ' PCT W089/01694 describes various of electrically conductive polyaniline doped with certain sulfonated dopants materials such as para-toluene-sulfonic acid. It is disclosed that these materials ase thermally stable and can be melt blended with other polymers to form blends.
This invention relates to particles of a polyaniline doped with two or more dopants where the dopant at or near the surface of said particles is different from the dopant at or near the core of said particles. As used herein, "at or near the surface of the particle" is all or a portion of the surface of said particles to a depth of about 50A or less, and "at or near the core of said particle" is all or a portion of the particle more than about 50A from the surface of the particle.
Several advantages flow from this invention.
Fox a:ample, through use of this invention, two or more dopants can be structured in the polyaniline particles to obtain better properties. For example, it is critically important to develop more thermally stable forms of polyaniline which are capable of being melt blended in matrix polymers with higher processing temperatures such as nylons and polycarbonates while at the same time providing a final blended composition having an acceptable level of electrical conductivity. WO 90/10297 published September 7, 1990 and WO 89/101694 published February 23, 1989 identify a broad range of organic acids and their salts as thermally stable dopants for polyaniline. However, some of the most thermally stable dopants such as aryl disulfonates and trisulfonates of benzene and naphthalene exhibit significantly lower conductivity as compared to the less thermally stable dopants such as aryl monosulfonates. Particles in which the polyaniline is doped with dopants structured in a skin/core arrangement (or more generally in a stratifiQd arrangement) can combine the high conductivity of one dopant (preferably in the core) with the high thermal stability of the other dopant (preferably in the skin) to provide a beneficial result.
~ variety of other desirable combinations of properties can b~ achieved through the skin/core or stratified polyaniline particles. For example, such particles can be used to enhance the dispersion ability of polyaniline particles doped in the core with desirable dopant in a matrix of polymers which is incompatible with the core dopant. This embodiment of the invention includes polyaniline particles doped predominantly in the skin or surface region of the particle with a dopant which has a more compatible surface energy with the intended matrix polymer or polymers of the blend but which may provide less electrical conductivity and which is doped - ~ _ 20~92~1 predominantly in the core region with a dopant which provides higher levels of electrical conductivity.
Other possible desirable features which can be incorporated via a surface dopant/core dopant combination is lessening the hygroscopic tendency of the more electrically conductive core dopant by using for eaample a fluorinated alkyl sulfonate as the skin dopant and more high conductive toluene sulfonic acid as the core dopant. Still other desirable features which may be incoporated via a surface dopant/core dopant combination is the lessening of the reactivity of the doped polyaniline with contacting metals or with other chemical substances by using a less reactive surface d'opant such as a polymeric sulfonats, and using a reactive dopant having a higher le~~el of electrical conductivity predominantly in the core of the particle. This arrangement and combination of dopants provides particles and substrates comprising conductive polyaniline with the combinations of desirable features imparted by both dopants whale minimizing or eliminating the undesirable of each if taken individually.
ga~~uTpT?nN OF THE P EFERRED EMBODIMENT
HRI QESCRIPTION OF THE DRAWINGS
The invention will be more fully understood and further advantages will become apparent when references is made to the following detailed description of the invention and the accompanying drawings in which:
Figure 1 is a graph of conductivity half life measured for a pellet of compressed polyaniline particles doped with tosylate anions. Measured half life at various temperatures (solid points) is used to project half life over a continuous range of temperature (solid lane).

Figure z is a graph of conductivity half life versus temperature for a pellet of compressed polyaniline particles doped with tosylate, and a combination of tasylate and dodecylbenzene sulfonate in a skin/core configuration, where in the latter case the tosylate dopant predominates at the care and the dodecylbenzene sulfonate dopant predominates at the skin.
Figure 3 is a graph of half-life versus temperature for polyaniline particles doped with tosylate, and a combination of tosylate and 1,5-n aphthalene disulfonate in a skin/core configuration, where in the latter case the tosylate dopant predominates at the core and the naphthalene disulfonate dopant predominates at the skin.
This invention is directed to particles of a polyaniline doped with two or more dopants such that the concentration of at least one dopant at or near the surface of said particles is higher than the concentration of at least one other dopant at or near said core of said particle. Particle size and shape ~ are not critical. Por a:ample, the particles can be of an irregular shape or can be of a regular or substantially regular shape. The particles can be r~gular flat shaped particles having relatively high aspect ratios or can be short block, spherical, oval or like shaped particles having relatively low aspect ratios. In any event, the shape of the particles will be dictated solely by the needs of the specific application. Particle size may also vary widely and is dependent on the particular application. In those applications Where relatively large particles are required i.e. 1 to 100 microns, large particles are used; conversely in those applications where ~~~~2J1 _ g _ relatively small particles are required i.e. less than about one micron, small particles are used. Although not ciritcal,usually particle.. size is from about 0.05 to about 50 microns. Preferred particles sizes are from about 0.02 to about 3 microns. In some polyaniline compositions particles may exist as aggregates composed of smaller primary particles. It is generally most preferred for the production of uniform blends of high conductivity that these a99regates be broken down to their primary particles during compounding. It is most preferred that the primary particles themselves be doped in a skin/core configuration and that the primary particles range in size from about 0.05 to 0.2 microns.
Polyanilines for use in the process of this invention may vary widely. Any form of substituted and unsubstituted polyaniline can be conveniently used in the practice of this invention. Illustrative of useful forms are those described in Green, A.G. and Woodhead, A.E., CRVII - Aniline-black and Allied Compounds, Part II", ,L~ Chem. Soc. , .~Q~, pp. 1117 (1912) and Kobayashi, et al., "Electrochemical Reactions... of Polyaniline Film-Coated Electrodes", J. Elect~ganal. Chem.. 177. pp. 281-91 (1984) and in Shacklette, L.W., et al. "Structure and Properties of Polyanilin$ as Modeled by Single-Crystal Oligomers", Ghem. Phvs.. $~,. pp. 3955 (1988), which are hereby incorporated by reference. Ezamples of unsubstituted and substituted polyaniline useful in this invention 0 are characterized by different ratios of phenylene amine and quinone imine backbone segments and include leucoemeraldine, protoemeraldine, emeraldine, nigraniline and pernigraniline.
In the preferred embodiments, polyanilines for use in the invention are polyaniline homopolymers and copolymers of the type derived from the polymerization of one or more unsubstituted and substituted anilines -of the Formula I:
F'~m~d~~.
wherein:
n is an integer from 0 to 5;
m is an integer from 0 to 5, with the proviso that the sum of n and m is equal to 5 and with the further groviso that at least one position on Lhe aniline ring, preferably at the para position, is substituted with a substituent which will allow coupling of the aniline units such halo, hydrozen or other leaving group;
Rl is the same or different at each occurrence and is selected from the group consisting of alkyl, deuterium, alkenyl, alkoay, cycloalkyl, cycloalkenyl, alkanoyl, alkylthio, arylozy, alkylthioalkyl, alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, aryl, alkylsulfinyl, arylozyalkyl, alkylsulfinylalkyl, alkoayalkyl, phosphoric acid.
alkylsulfonyl, arylthio, alkylsulfonylalkyl, boric acid, phosphoric acid, sulfinate salts, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, carboxylic acid, phosphoric acid, halo, hydroay, cyano, sulfinic acid, carboxylate salts, borate salts, phosphate salts, sulfonate salts, phosphinate salts, phosphonate ' salts, phosphoric acid, sulfonic acid, vitro, alkylsilane, or any of the foregoing aryl, aliphatic or cycloaliphatic groups substituted with one or more phosphoric acid, sulfonic acid, phosphoric acid, boric acid, carboxylate salt, borate salt, sulfonate salt, phosphinate salt, phosphonate salt, phosphate salt, phosphinic acid, carboxylic acid, halo, nitro, amino, alkylamino, dia.lkylamino, arylamino, diarylamino, alkylarylamino, cyano or epoxy moieties;
or any two Rl groups together or any R~ group together with any R2 group may form a substituted or unsubstituted alkylene, alkenylene or alkynylene chain completing a 3, 4, 5, 6, 7, 8, 9 or 10 membered aromatic, heteroaromatic, heteroalicyclic or alicyclic ring, which ring may optionally include one or more divalent nitrogen, sulfur, sulfinyl, ester, carbonyl, sulfonyl, or o$ygen atoms wherein permissible substituents are one or more phosphonic acid, sulfonic acid. phosphoric acid, boric acid, carboxylate salt. borate salt, sulfonate salt, phosphinate salts, phosphonate salt, phosphate salt, phosphinic acid, carboxylic acid, halo, vitro, amino, alkylamino, dialkylamino, arylamino, diaryiamino, alkylarylamino, cyano or epozy moieties ; or R1 is an aliphatic moiety having repeat units of the formula:
-(OCHZCH2)q~-CH3, -(~CH2CH(CH3))q0-CH3, -(CHZ)q CF3, -(CFZ)q-CF3 or -(CH2)q CH3 wherein q is a positive whole number; and RZ is selected from the group consisting of perrtaissibl~ Rl substituents or hydrogen.
Illustrative of the polyanilines useful in the pts~tice of this invention are those of the Formulas II to V:
l !!
3s ~.._J
(H)~

ar (w)~
( 11),~
"°
M t4 ""~, t ~'t9 n ~ ~'$,~ fl h ~~Z~n ~P
zo ~ whereinz n, m, R1 and R2 are as described above;
a and y are the same or different at each 206929.
_ 13 -occurrence and are integers equal to er greater than 0, with the proviso that the sum of x and y is greater than 0, preferably x is an integer equal to or greater than about 1 and/or the ratio of x to y is greater than or equal to about 0; and z is the same or different and is an integer equal to or greater than 1.
The following listing of substituted and unsubstituted anilines are illustrative of those which can be used to prepare polymers and copolymers useful in the practice this invention.
of 2-Cyclohexylaniline 2-Acetylaniline Aniline 2.5-Dimethylaniline o-Toluidine 2,3-Dimethylaniline 4-Propanoylaniline 2-(Methylamino)aniline 4-Benzylaniline 2-(Dimethylamino)aniline4-Aminoaniline 2-Methyl-9-methozy- 2-Methylthiomethylaniline carbonylaniline 4-(2,4-Dimethylphenyl) N-Ethylaniline aniline 4-Carbozyaniline 2-Ethylthioaniline N-Methyl aniline N-Methyl aniline 2,4-Dimethylaniline N-Propyl aniline N-Propyl-m-toluidine N-Hezyl aniline N-Methyl-a-cyanoaniline m-Toluidine 2,5-Dibutylaniline o-Ethylaniline 2,5-Dimethozyaniline m-Ethylaniline Tetrahydronaphthylamine o-Ethozyaniline o-Cyanoaniline m-Butylaniline 2-Methylthioaniline m-Hezylaniline 2,5-Dichloroaniline m-Octylaniline 3-(n-Butanesulfonic acid) 4-Bromoaniline aniline 2-Bromoaniline 3-Propozymethylaniline 3-Bromoaniline 2,4-Dimethozyaniline 3-Acetamidoaniline 4-Mercaptoaniline 4-Acetamidoaniline 4-Ethylthioaniline ~0~~2~1 5-Chloro-2-methoAy-aniline 3-Phenoxyaniline S-Chloro-2-ethoxy-aniline 4-Phencayaniline N-He8y1-m-Toluidine N-Octyl m-toluidine 4-Ph~enylthioaniline 4-Trimethylsilylaniline 3-Amino-9-methylcarbazole 3-Amino carbazole 9-Amino carbazole N-(p-Amino phenyl) aniline Illustrative of useful R1 groups are hydrogen, alkyl, such as methyl, ethyl, octyl, nonyl, tent-butyl, neopentyl, isopropyl, sec-butyl, dodecyl and the like, alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 1-heptenyl, 1-octenyl and the like; alkoay such as propoay, butoay, methoay, isopropoay, pentoxy, nonoay, ethyoay, octozy, and the likes cycloalkenyl such as cycloheaenyl, cyclopentenyl and the like: alkanoyl such as butanoyl, pentanoyl, octanoyl, ethanoyl, propanoyl and the like; amino; alkylamino, such as methylamino, ethylamino, butylamino and the like: dialkylamino, such as dimethylamino, methylethylamino and the like;
arylamino such as phenylamino, p-methylphenylamino and the like: diarylamino, such as diphenylamino, p-nitrophenyl-p'-methylphenylamino and the like;
alkylarylamino, such as 2-phenyl-4-methylamino and the like: alkylsulfinyl, alkylsulfonyl, alkylthio, arylthio, arylsulfinyl, and arylsulfonyl such as butylthio, neopentylthio, methylsulfinyl, benzylsulfinyl, phenylsulfinyl, propylthio, octylthio, nonylsulfonyl, octylsulfonyl, methylthio, lsoprapylthio, phenylsulfonyl, methylsulfonyl, nonylthio, phenylthio. ethylthio. benzyithio.
phenethylthio, sec-butylthio, naphthylthio and the like; alkozycarbonyl such as methoaycarbonyl, ethoaycarbonyl, butoaycarbonyl and the like;
cycloalkyl such as cyclohezyl, cyclopentyl, cyclo-octyl, cycloheptyl and the like; alkozyalkyl such as metho$y-methyl, ethozymethyl. butoaymethyl.

propoxyethyl, pentoxybutyl and the like; aryloxyalkyl and aryloxyaryl such as phenoxyphenyl, phenoxymethyl and the like; and various substituted alkyl and aryl groups such as 1-hydroxybutyl, 1-aminobutyl, 1-hydroxylpropyl, 1-hydroxypentyl, 1-hydroxyoctyl, 1-hydroxyethyl, ~-nitroethyl, trifluoromethyl, 3,4-epoxybutyl, cyanomethyl, 3-chloropropyl, 4-nitrophenyl, 3-cyanophenyl, and the like; acid and acid salts such as sulfonic acid, carboxylic acid and salts thereof; aliphatic or aryl groups substituted with an acid or salt thereof such as phosphoric acid, phosphinic acid, sulfonate salt, sulfinate salt, sulfonic acid, sulfinic acid, borate salt, phosphoric acid, boric acid, or carboaylic acid groups such as ethylsulfonic acid, propylsulfonic acid, 4-nitro benzene sulfonic acid, butyisulfonic acid, phenylsulfonic acid, and the like.
Also illustrative of useful R1 groups are divalent moieties derived from any two R1 groups or a R1 group with a R2 group such as moieties having from about 2 to about 7 repeat units of the formula:
-(CR3.CR3-CR3.CR3)_b or -(C(R3)2)a wherein R3 is the same or different at each occurrence and as hydrogen or alkyl, as for ezample -(CH2)~. -(CHZ)g-a -(CH-CH-CH-CH)-, -ICIiZ-CH(CH~)-CH2l- and -(CH2)5-. and groups comprised of such moieties which include one or more heteroatoma of oxygen, nitrogen, ester, sulfonyl, carbonyl, sulfinyl, and/or sulfur, such as -CH2SCH2--CH2NHCH2-. -SCH2NHCH2-, -O-CH2-CH20- -O-CH2-S-CHZ-, -CH2S(02)CH2-, -CH2S(0)CH2-. -OC(O)CH2CH2-, -CH2G(O)CH2- and -CH2-O-CH2- to form heterocyclic amino compounds such as tetrahydronaphthylamine, dihydrobenzopyrroleamine, benzofuranamine, dihydrobenzopyranamine, Cihydrobenzofuranamine, dihydrobenzoparaoxazineamine, dihydrobenzoparadiazineamine, dihydrobenzotriazoleamine, dihydro-benzothiazineamine,benzothiopyranamine, dihydro-benzoaazoleamine and the like. Exemplary of useful R3 groups are divalent alkenylene chains containing 1 to about 3 unsaturated bonds such as divalent 1,3-butadiene and like moieties which may also include one or more divalent oxygen, nitrogen, sulfinyl, sulfonyl, carbonyl, ester, and/or sulfur groups which form such compounds as benzodiazineamine, benzodiazoleamine, benzotriazepine-amine, benzimidazolylamine, benzisoxazoleamine, benzoaazolylamine, benzothiazineamine, benzoaazineamine, naphthaleneamine, benzopyranamine, benzothiazineamine, anthraceneamine, aminobenzothio-pyran,aminobenzodiazine, benzethiopyrone amine, amino-coumarin, benzthiopheneamine, benzothiodiazoleamine, and the like.
Exemplary of useful RZ groups are hydrogen and the above-referenced representative R1 groups described above such as alkyl as for example, methyl, ethyl, isopropyl, butyl, isobutyl, hezyl, octyl and the like; alkylsulfonyl such as methylsulfonyl, ethylsufonyl, propylsulfonyl and the like;
arylsulfonyl such as phenylsulfonyl, p-methyl phenylsulfonyl, naphthylsulfonyl and the like.
Preferred for use in the practice of this invention are polyanilines of the above Formulas II
to V in which:
n is an integer from 0 to about 2;
m is an integer from 2 to 4, with the proviso that the sum of n and m.is equal to 4;
Rl is aryl, alkyl or alkoay having from 1 to about 30 carbon atoms, cyano, halo, sulfonic acid, 2~~9~~1 carboxylic acid, boric acid, borate salt, phosphoric acid, phosphate salt, phosphoric acid, phosphonate salt, phasphinic acid, phosphinate salt, sulfinic acid, sulfinate salt, carboxylate salt, sulfonate salt, amino, alkylamino, dialkylamino, arylamino, hydroxy, diarylamino, alkylarylamino, or alkyl, ar;~l or alkoay substituted with phosphoric acid, phosphate salt, phosphoric acid, borate salt, sulfonate salt, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, carboaylate salt, hydroay, alkoay, phosphoric acid, boric acid, alkyl, phosphinic acid, phosphonate salt, phosphinate salts, carboxylic acid or sulfonic acid substituents;
R2 is the same or different at each occurrence and is a R1 substituent or hydrogen;
a is an integer equal to or greater than 1;
y is equal to or greater than 0, with the proviso that the ratio of a to y is greater than about 0.5; and z is an integer equal to or greater than about 5.
Particularly preferred for use in the practice of this invention are polyanilines of the above Formulas in which:
n is an integer from 0 to 1;
m is an integer from 3 to 4, with the proviso that the sum of n and m is equal to 4;
R1 is aryl, alkyl or alkoay having from 1 to about 20 carbon atoms, sulfonic acid, halo, carboxylic acid, amino, carboxylate salt, alkylamino, phosphonate salt, dialkylamino, arylamino, phosphoric acid, boric acid, phosphate salt, phosphoric acid, borate salt, diarylamino, alkylarylamino, or alkyl or aryl substituted with carboxylic acid, phosphoric acid, boric acid, phosphate salt, phosphoric acid, borate salt, sulfonate salt, amino. alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, ~ooo~~~.
_ 18 _ carboxylate salt, halo, phosphonate salt, or sulfonic acid substituents;
RZ is the same or different at each occurrence and is a R1 subsituent or hydrogen;
x is an integer equal to or greater than 2;
y is equal to or greater than 0, with the proviso that the ratio o~ x to y is greater than about 1; and z is an integer equal to or greater than about 5~
Amongst the particularly preferred embodiments, most preferred for use in the practice of this invention are polyanilines of the above Formulas III or V in which:
n is an integer from 0 to 1;
m is an integer from 3 to 4, with the proviso that the surn of n and m is equal to 4;
R1 is aryl, alkyl, alkozy, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, halo, sulfonic acid, sulfonate salt, carboxylic acid or carbozylate salt. ar alkyl or aryl substituted with one or more sulfonic acid, carbozylate salt.
amino, alkylamino, dialkylamino, arylamino, diarylamino, halo, alkylarylamino, sulfate salt, sulfonate salt, or carboxylic acid substituents, wherein the aromatic moieties include from 6 to about 21 carbon stoma and the aliphatic moieties include from 1 to about 15 carbon atoms;
RZ is hydrogen;
z is an integer equal to or greater than 2;
y is equal to or greater than l, with the proviso that the ratio of z to y is equal to or greater than about 2; and z is an integer equal to or greater than about 5.
In the most preferred embodiments of this invention, the polyaniline is derived from 19 - 20692~~.
unsubstituted aniline, alkoxy, alkyl, or sulfonic acid substituted aniline or copolymers thereof.
In general, the number of aniline repeat units is not critical and may vary widely. The greater the number of aniline repeat units the greater the viscosity and molecular weight of the polyaniline.
In those applications where a polyaniline of lower molecular weight and viscosity is required, such material may be used, and in those applications where a polyaniline of high molecular weight and viscosity is required, then such material can be used. The number of aniline repeat units is preferably at least about 10. The upper limit can vary widely depending on the desired viscosity and molecular weight. In the more preferred embodiments of the invention, the number of aniline repeat units is at least about 20, and in the particularly preferred embodiments. the number of repeat units is at least about 30. Amongst the particularly preferred embodiments, most preferred are those embodiments in which the number of repeat units is at least about 40.
Useful polyanilines can be prepared through use of chemical and electrochemical synthetic procedures. For example, one form of polyaniline can be prepared by treating aniline with ammonium persulfate (P1H4)ZS208 in excess 1M HC1. This powdared form of polyaniline is blue green in color.
After methanol washing and air drying this material exhibits a conductivity of 10 S/cm. This conductive form of polyaniline can be treated with ammonium hydroxide in ethanol to form a non-conductive form of polyaniline which is purple in color and which has a conductivity of less than 10'8 S/cm. Other chemical procedures for preparation of various chemical forms of polyaniline are described in detail in Green et al. described above.

~~~~~~1 Useful forms of oolyaniline can also be prepared electrochemically. For example, useful forms of polyaniline can be prepared by the electrochemical oxidation of aniline in aqueous fluoroboric acid electrolyte on a platinum foil anode.
Other chemical and electrochemical syntheses and transformations of the conductive form of polyaniline may be discovered and are presently contemplated as being useful. Moreover, additional forms or types of polyaniline may be elucidated in the future. Accordingly, no limitation to the syntheses, transformation, or structures herein described or postulated is intended beyond the limitations of the appended claims.
The polyaniline may be electrically neutral or electrically conductive polyaniline may be used.
Polyaniline is rendered electrically conductive by doping with a dopant solute. In general, such dopant solute is derived from a compound, which upon addition to the polyaniline. ionizes the polymer with co-committent formation of a dopant solute species to form a charge transfer complex with polyaniline, which complex has a conductivity equal to or greater than about 10-6ohm-1Cm-1 by the four-in-line probe method.
Dopants for use in the practice of this invention can vary widely and can be such materials which are known in the art for use in doping conjugated backbone polymers to form conductive or semi-conductive polymers, as for eaample, those described in detail in U.S. Patent Nos. 4,442,187 and 4,321,114 which are hereby incorporated by reference. Illustrative of useful dopant species are oxidizing dopants. Oxidizing dopants are well known in the conductive polymer art, and any of such known oxidizing dopants can be used.

2f~~9~91 Illustrative of useful oxidizing dopants are AsFS, Mo0C14, MoCls, PC15, POC13, PC13, A1C13, NO+
and NOZ'" salts (such as NOBF~, NOPF6, NOSbF6, NOAsF6, NOCH3C0z, N02BF4, N02PF5, NOZAsF6, N02SbF6, and N02CF3S02), HC104, HN03, HZSOg, benzoylperoaide, S03, Hr2, (FS03)Z, ZnCl2, FS03H, and Fe(III) salts (such as Fe(BF4)3, FeBr3, Fe(CH3S03)3. Fe(C104)3, FeCl3.
Fe(OTs)3, and Fe(CF3SO3)3 which give rise to doped polymers containing dopant solutes such as N03-, CH3S03-, A1C14-,BF4-, ZnCl4-, PC14-. PF6-, AsF6-, SbF6', CF3S03-, C104-. OTs-, S03'Z, C6HSC02-, CH3S03-, FS03', and FeClg°. Other useful oxidizing dopants include electrolyte salts such as LiCIO4,LiBF4, LiAsF6, NaPF6, BuqNC104, Bu,~NOTs, BuqNCF3S03, LiCF3S03, AgOTs, and the like. Preferred oxidizing dopants for use in the practice of this invention are oxidizing dopants selected from the group consisting of MoOCl4, MoClS, PC1S, POC13. and Fe (TII) salts such as Fe(C10~)3, FeCl3, FeBr3, and Fe(CF3SO3)3, and particularly preferred oxidizing dopants for use in the practice of this invention are dopants selected from the group consisting of MoOCl4.
MoClS, PC1S, POC13, FeBr3 and FeCl3. Amongst these particularly preferred embodiments, most preferred 2S oaldizing dopants are those embodiments in which the oxidizing dopant is FeCl3.
Illustrative of other dopants are inorganic oxidizing or non-oxidizing protonic acid dopants.
Such dopants include inorganic acid such as hydrofluoric acid, hydrochloric acid, hydroiodic acid, phosphoric acid, nitric acid, perchloric acid, boric acid, sulfuric acid and the like.
Illustrative of still other useful dopants are non-oxidizing protonic acids such as those of 3S containing anionic moieties of the formula:
R~(PO3°)r(POZ(R6)-)r(BO2°)r(so3-)r (C02-)r(POZ°)r PO(Rg) )(SO2 )r 209291.

and having one or more cationic moieties selected from the group consisting of:
M+s wherein:
R4 and R6 are the same or different at each occurrence and are organic radical or amino;
M is a species having a positive charge equal to s, provided that at least one of M+s is a proton or a moiety which can be transformed by radiation, heat, chemicals and the like into a proton under use conditions such as +NH4, +N(cH3)2H2, +N(C2HS~H3 and the like;
s is the same or different at each occurrence and is an integer equal to 1 to 8;
r is the same or different at each occurrence and is 0 or a positive integer equal to or greater than I, with the proviso that at least one of r is other than 0.
The R4 and R6 group may vary widely and can be a substituted or unsubstituted aliphatic radical such as alkyl, nitroalkyl, haloalkyl and the like, or a substituted or unsubstituted aromatic radical such as phenyl, helophenyl, nitrophenyl, anthracyl, naphthyl, phenanthryl and the like. RQ and R6 groups may also be s polymeric radical such as a polymer having reGUrring pendant phenyl groups in the polymeric backbone substituted with sulfonic acid and derivatives thereof such as salts, phosphoric acid and derivatives thereof such as salts, phosphoric acid and derivatives thereof such as salts. sulfinic acid and derivatives thereof such as salts, carboxylic acid and derivatives thereof such as salts, boric acid and derivatives thereof such as salts, or phosphoric acid and derivatives thereof such as salts; moieties such as sulfonated or phosphonated polystyrene, poly(a-methylstyrenN), poly(4-phenylstyrene), poly(2-vinyl naphthalene), polyvinyl benzoate), poly(benzyl methacrylate) and the like. In the particularly preferred embodiments of the invention, Rq and R6 are aromatic radical and in the most precerred embodiments R4 and R~ are substituted or unsubstituted phenyl or naphthyl. The nature of the M+n group may vary widely. For example, M+n may be be a non-metal ration such as Bu~N+, H+, NO+, NO2~, NH4~, +N(CH3)2H2, +N(C2H~)H3, and the like, or may be a metal ration such as Na+, Li+, Ag+, Ha+2, Co+3, A1+3, Fe+3 and the like.
Preferred for use in the practice of this invention are organic acid dopants, more preferably those having anionic moieties of the formulas:
R4(P03')r(P02')r(S02-)r{P02(R6)')r{S03)')r(C02-')r (PO(R6)")(B02')r and having a cationic moiety of the Formula:
M+s wherein at least one of the cationic moieties of the formula M+s is a proton or is a moiety which can be transformed into a proton under use conditions;
M+s is a cationic species having or positing charge s;
s is an integer equal to or greater than 1, preferably from 1 to about 8;
R4 and R6 are organic radicals or amino, and r is an integer equal to or greater than 1, preferably from 1 to about 8;
More preferred for use in the practice of this invention as dopants are acids or acid derivatives of ~~~~~~1 the formula:
Rq(POZ(R6)M)g(P03M')f(S03M)c(COZM)d(POZM2)t(SOZM)h S (PO(R6)M)i or S°aM~r, ~-R5~ ~
a~ ~~ ~ ~ C.P
(~~p3/r~~~5o3M ~ c.
wherein:
hi is H+. or other metal or non-metal cation with the proviso that at least one of M is H+ or a moiety which can be thermally or chemically transformed into a proton under use conditions, such as +NH4,+N(CH3)2H2, +N(C2H5)H3 and the like t is 0, 1, 2, 3 or 4;
h is l, 1, 2, 3 or 4;
i is 1, 1, 2, 3 or 4;
c is 0, 1. Z, 3 or 4;
d is 0, 1, 2, 3 or 4;
f is 0, 1, 2, 3 or 4;
g is 0, 1, 2, 3 or 4, with the proviso that at least one of c, d, f, g, h, i or t is other than 0;
a is 0, 1 or 2; and R4 and R5 are the same or different at each occurrence and are nitro, cyano, hydroay, halo, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, alkozy, or salt substituted or unsubstituted alkozy, aryl or alkyl having from 1 to 2~~~291 _ zs -about 30 carbon atoms wherein permissible substituents include sulfonate salt, perhaloalkyl, phenyl, alkoxy, halo, cyano, amino, haloalkyl, hydroxy, sulfonic acid, phosphoric acid phosphate salt, boric acid, sulfinate salt, phosphinate salt, sulfinic acid, borate salt, phosphinic acid, phosphonate salt, phosphonic acid, carboxylic acid, vitro, carboaylate salt and the like, or any two R4 or any two RS substituents together may form an alkenylene chain completing a fused-ring system which chain may be unsubstituted or substituted with one or more halo, phosphoric acid, hydroay, boric acid, vitro, cyano, amino, sulfinate salt, phosphinic acid, alkylamino, dialkylamino, ghosphinate salt, arylamino, diarylamino, alkylarylamino, sulfinic acid, phosphate salt. carbozylate salt, phosphonic acid, phosphonate salt, sulfonate salt, borate salt, sulfonic acid or carboaylic acid groups, or R4 or R5 is a moiety of the formula:
-(CH2)qCF3, -(CFZ)qCF3, -(CHZ)qCH3 -(OCH2CH2)qOCH3 or -(OCH2CH(CH3))qOCH3 wherein:
g is a positive whole number from 1 to about 10; and R~ is alkyl, aryl, aryiozy or alkoxy.
In the particularly preferred embodiment of this invention, useful dopants are acids andlor acid derivatives of the above formula:
R4(POZ(R6)M)g(PO~M2)f(SO3M)c(C02M)d(P02M2)t(SO2M)h (PO(R6)M)i or 2~ _ ~0~9291 S°~~~r, ~-Rs~ ~
Lpp~ ~'~3M~~~r ~~.~3m~~Lso~M ~
wherein:
c is 0, 1, z or 3;
d, t, f, g, h and i are the same or different at each occurrence and are with the proviso that at least one of c, d, t, f of g, i or h is other than 0;
a is 0, 1 or 2;
R~ and RS are the same or different are hydroay, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkyl aryl amino, substituted or unsubstituted phenyl or alkyl wherein permissible substituents are selected from the group consisting of alkyl, hydroay, amino, alkylamino, dialkylamine, arylamine, diarylamino, alkylarylamino, hydroay, phenyl, haloalkyl, perhaloalkyl, cyano, amino, vitro, alkoay, boric acid, borate salts, phosphonate, ~ phosphonic acid. carbozylate salts, sulfonate salts, phosphate salts, phosphinic acid, phosphinate salt, sulfonic acid, carboaylic acid, phosphoric acid, sulfinic acid or sulfinate salts or any two R6 substituents together may form an unsubstituted or substituted or alkenylene chain completing a naphthalene, anthracene or phenanthracene fused ring system wherein permissible substituents are as described above or RQ or RS is a moiety of the formula:
-(CH2)qCF3,-(CFZ)gCR3,-(CH2)qCH3, -(OCHZCH2)gOCH3 or -(OCH2CH(CH3))q OCH3 - ~~ - 2a~9291 wherein:
q is a positive whole number from 1 to about 10;
R6 is alkyl, alkoxy, arylosy or aryl; and M is H+, or other metal or non-metal cation, with the proviso that at least one of M is H+ or a moiety which can be thermally or chemically transformed into a proton under use conditions.
zn the most preferred embodiments of this invention, useful dopants are acids and/or acid derivaties of the formula:
RQ(P02(R6)M)g(P03M2)f(S03M)c(C02M)d Or ~~~a oa"'~~ ~. ~ _.
wherein:
c. d, e, f and g are the same or different and are 0. 1 or 2, with the proviso that at least one of c, d, f and g is not 0;
R4 and RS are the same or different at each occurrence and are alkyl, phenyl, amino, alkylamino, dialkylamino. arylamino, diarylamino, alkylarylamino, or alkyl substituted with one or more fluoro, sulfonic acid, sulfonate salt, alkozy, carbozylate salt, hydrozy, nitro, cyano, phosphinic acid, .- 28 -phosphonic acid phosphinate salt, phosphonate salt, amino or carboxylic acid groups, or phenyl substituted with one or more alkyl, alkoxy, fluoroalkyl, sulfonic acid, phosphinic acid, phosphonic acid, phosphinate salt, phosphonate salt, sulfonate salt, carboxylate, hydroxy, vitro, cyano, or carboxylic acid groups or any two R4 or R5 substituents together may form an alkylene or alkenylene chain completing a naphthalene, anthracene LO or phenanthracene fused system which may be substituted with one or more alkyl, alkoxy, fluoro, phosphinic acid, phosphinate salt, phosphonic acid, phosphonate salt, fluoroalkyl, sulfonic acid, sulfonate salt, carboaylic acid, carbo:ylate salt, hydroay, vitro, amino or cyano groups;
R6 is aryl, aryloay, alkyl or alkozy; and M is H+ or other metal or non-metal cation, with the proviso that at least one of M is H+ or is a moiety which can be thermally transformed into a proton under process condistions.
In the especially preferred embodiments of this invention, useful dopants are acids or acid derivaties of the formula:
Rq(S03M)c (OOZ1~I)d or C
~3r~~~

wherein:
c is i, 2 or 3;
d is l, Z or 2 with the proviso that at least one of c, d is not 0 a is 0, 1 or 2;
R4 and RS are the same or different at each occurrence and are hydroxy, dialkylamino, l0 diarylamino, alkylarylamino, amino, alkylamino, arylamino, alkyl, phenyl, alkyl substituted with one or more fluoro, sulfonic acid, sulfonate salt, alkoxy, dialkylamino, diarylamino, alkylarylamino, carboxylate salt, hydroxy, alkylamino, arylamino, 15 phosphonic acid, nitro, cyano, phosphinic acid, phosphinate salt, phosphonate, amino or carboxylic acid groups, or phenyl substituted with one or more alkyl, alkoxy, fluoroalkyl, dialkylamino, diarylamino, alkylarylamino, sulfonic acid, 2o alkylamino, arylamino, sulfonate salt, carboaylate salt, hydroxy, phosphinate acid, phosphinate salt, nitro, cyano, amino or carboxylic groups or any two R4 and RS substituents together may form an alkylene or alkenylene chain completing a naphthalene, anthracene or phenanthracene fused system which may be substituted with one or more alkyl, alkoay, fluoro, fluoroalkyi, sulfonic acid, sulfonate salt, carboxylic acid, phosphinic acid, phosphinate salts, carboxylate salt, hydroxy, nitro, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, or cyano groups;
M is Hø or other metal or non-metal cation or a moiety which can be thermally tranformed into a proton under process conditions.
In the process of the embodiment of this invention of choice, the dopant is a sulfonic acid or sulfonic acid derivative of the formula:

~~(~~~~~
_~o~
to wherein;
c is 1. 2 or 3;
a is 0, 1 or 2;
R5 is alkyl or alkyl substituted with one or 15 more fluoro groups, or any two RZ groups together may form an alkenylene chain completing a naphthalene fused ring system which may be substituted with one or more sulfonic acid, sulfonic salt group or a combination thereof; and 20 M is a proton, or other metal or non-metal can on, with the proviso that at least one of M is proton.
The following is a listing of dopants which are useful in the practice of the most preferred 2S embodiments of this invention for formation of the dopant solute.
1-anthracene sulfonic acid, 9-anthracene sulfonic acid, Z-phenanthracene sulfonic acid, 30 3-phenanthracene sulfonic acid, 9-phenanthracene sulfonic acid, N02CF3S03.
CF3S03H, perflouro octyl sulfonic acid 35 Perfluoro octyl carboxylic acid octylsulfonic acid.
dodecylsulfonic acid, 2~~~?~1 cetylsulfonic acid, roluenesulfonic acid (TsOH), Fe{OTs)3, Fe(CH3S03)3~

(FS03)', AgOTs, Me3Si0Ts, dodecylbenzene sulfonic acid, naphthalene sulfonic acid, benzene disulfonic acid, benzene sulfonic acid, 1,3-benzene disulfonic acid, 2,5-dihydroay-1,~-benzene disulfonic acid, camphor sulfinic acid naphthalene trisulfonic acid dodecylbenzene sulfonic acid, ethane sulfonic acid 1,5-naphthalene disulfonic acid, nickel phthalocyanine tetrasulfonic acid, phenyl phosphoric acid.

diphenyl ghasphinic acid phenyl phosphinic acid, 3-sulfopropyl acrylate.

3-sulfopropyl methacrylate, sulfamic acid, 5-sulfosalicyclic acid, trion (4,5-dihydroay-1,3-benzene disulfonic acid), vinyl sulfonic acid.
sulfanilic acid, 4-sulfophthalic acid, sulfoacetic acid, methyl phosphinic acid, phenylphosphonic acid.
3S methyl phosphoric acid, methyl orange, sulfonated polystyrene, sulfonated poly(2-vinyl naphthalene), naphthol yellow, naphthal blue black, 1,2-naphthoquinone-4-sulfonic acid, naphthylazoxine S, 1-octane sulfonic acid, t-butyl phosphoric acid, ethyl phosphoric acid, butyl phosphoric acid, 1,2-benzene disulfonic acid, 4-octylbenzene sulfonic acid, 2-mesitylene sulfonic acid, 2,6-naphthalene disulfonic acid, 2-naphthalene sulfonic acid, 1,3,6-naphthalene trisulfonic acid, 1,3,7-naphthalene trisulfonic acid, sulfonazo III acid, -biphenyl disulfonic acid, biphenyl sulfonic acid, 1.8-dihydroaynaphthalene-3-6-disulfonic acid, 3,6-dihydroaynaphthalene-2,7-disulfonic acid, 4,5-dihydroaynaphthalene-2,7-disulfanic acid, 6,7-dihydroay-2-naphthalene sulfonic acid, 1-naphthalene phosphoric acid, 1-naphthalene sulfonic acid, 1-naphthalene-5,7-dinitro-8-hydroay, 1-naphthalene-4-hydroxy sulfonic acid, 4-bromo benzene sulfonic acid, 4-hydro$y-5-isopropyl-2-methyl benzene sulfonic acid 3,4-diamino benzene sulfonic acid benzenephosphoric acid, 1,3.5-benzene trisulfonic acid, 2-methyl-5-isopropyl benzene sulfonic acid, 3,~-dinitro benzene sulfonic acid, 2-methoay benzene sulfonic acid, 1-naphthalene-5-hydroay sulfonic acid, 1-naphthalene-7-hydroxy sulfonic acid, 1-naphthalene-3-hydroxy sulfonic acid, 2-napthalene-1-hydroxy sulfonic acid, ~-phenylamino benzene sulfonic acid, 1,6-naphthalene disulfonic acid, 1,5-naphthalene disulfonic acid, 1,3-naphthalene-7-hydroxy disulfonic acid, and Me3SiOSO2CF3.
L'opants which are preferred for use at or near the core of the conductive polyaniline particles of this invention when the purpose is to achieve high conductivity include but or not limited to:
methane sulfonic acid, trifluoromethane sulfonic acid, P-toluene sulfonic acid, 4-hydroaybenzene sulfonic acid, benzene sulfonic acid, perchloric acid, sulfuric acid, and trifluoroacetic acid.
Dopants which are preferred for use in this invention at or near the outer surface layer of the polyaniline particles of this invention when the purpose is to achieve increased compatibility between the conductive polymer particles and a matrix polymer of lower surface energy and lesser polar character include those which contain one or more alkyl or fluoroalkyl substituents of length equal t~ or greater than about 2 carbon atoms, preferably equal to or greater than about 5 carbon atoms, more preferably equal to or greater than about 8 carbon atoms, and most preferably equal to or greater than 12 carbon atoms. Such dopants include but are not limited to:
octylsulfonic acid, perfluorooctylsulfonic acid, dodecylsulfonic acid, 3~ - ~O~i~~~l dodecylben2enesu.lfonic acid, dinonylnaphthalenesulfonic acid and dodecyldiphenyl ether disulfonic acid.
The latter is available from Dow Chemical Co. as DOWFAX 2AO.T~. Such dopants are also capable of lessening the hygroscopic nature of the polymer particles.
Dopants which are preferred for use at or near the outer surface layer or surface layers of the Particles of this invention when the purpose is to obtain more thermally stable compositions are organic sulfonic acids containing more than one sulfonic acid group including disulfonates such as 1,5-naphthalene sulfonic acid, 2,6-naphthalene sulfonic acid, dodecyldiphenyl ether disulfonic acid 1-naphthol-3,6-disulfonic acid, diphenylether-4,4'-disulfonic acid, diphenylsulfone-4,4'-disulfonic acid, and 2.5-dihydroay-1,4-benaene disulfonic acid.
Also preferred as thermally stable dopants for use at or near the outer surface of the particles of this invention are organic sulfonates including oligomer and polymeric sulfonates containing more than two sulfonic acid groups such as 1.3.6-naphthalene trisulfonic acid, polyvinyl sulfonic acid, sulfonated polystyrene, sulfonated poly(4-vinyl naphthalene), and the like.
The amount of dopant added to the polyaniline at or near the surface of the particle or at or near the core of the particle is not critical and may vary widely. In general, sufficient dopant is added to the polyaniline such that the conductivity of at least about 10-g ohm-lcm-1. The upper level of conductivity is not critical and will usually depend on the type of aniline polymer employed and the dopant. In general, the highest level of conductivity that can be obtained _ 35 _ is provided without unduly adversely affecting the environmental stability of the polyaniline. In the preferred embodiments of the invention, the amount of dopant employed is sufficient to provide a conductivity of at least about 10"6ohm"'lcm-1 and in the particularly preferred embodiments is sufficient to provide a conductivity of from about 10'4ohm°lcm'1 to about 10+3ohm°lcm°l. Amongst these particularly preferred embodiments, most preferred are those embodiments in which sufficient dopant is employed to provide a conductivity of at least about 10'3ohm°lcm'1 to about 10+3ohm'lcm'l, with amounts sufficient to provide a conductivity from about 100ohm'lcm'1 to about 10~3ohm"lcm"1 usually being the amounts of choice.
The region or portion of the particles doped by a particular dopant and the selected dopant are critical. In general, the area at or near the surface.
of the particle is predominantly doped with a dopant that is "compatible" with the environment or matrix in which the particles will be dispersed and/or the conditions under which said particles will be dispersed. As used herein "compatibility" refers to the eztent to which the dopant and the environment or matriz are misicible and include meeting one or more of the following criteria: closely matching the cohesive energies of the particle and the matrix;
obtaining low, chemical reactivity between the particle and the matrix or other medium with which the particle will come in contact; and maximizing dispersive polar or hydrogen bonding interactions which will lead to the facile dispersion of the particles in the matrix. Additionally, when two or more dopants are employed it is generally preferred that the dopant at or near the surface be the most thermally stable of the dopants. The region of the particle at or near the core of the particle is doped 2~~~2,~1.

with any kind of dopant, but is preferably doped with a dopant or mixture of dopants, which offers high conductivity and/or high thermal stability. The dopant within the core can be "incompatible" with the environment in which the particle is used or is adversely affected by such environment (reduction in beneficial properties) to any extent. As used herein, "incompatible" is the opposite to compatible and refers to having a mismatched surface energy or a chemical reactivity toward the matrix or the environment in which the particle is embedded. When more than two dopants are to be employed in a multilayer structure it is preferred that the dopant in the outer most layer be the most compatible with the matrix, the dopant in the neat outermost layer produce the most thermally stable doped polymer, and the dopant in the innermost layer offer high conductivity or other advantages in the use or synthesis of the conductive polymer particles of this invention.
This degree of structure provides for an increase in the effectiveness of the particles under use conditions. For example, highly dispersible high conductivity particles with high thermal stability are sought for dispersion in higher temperature thermoplastics, such as polyethylene terephthalate), polyethylene terephthalate glycol), nylon 6, nylon 66, polycarbonate, poly(phenylene oxide), and the lilts. When such blends are used, for example, to provide electromagnetric interference (EMI) shielding, a blend conductivity greater than about 0.1 S/cm is usually required and a blend conductivity of greater than 1.0 S/cm is preferred. Uniform distribution of particles is sought to prevent gaps in the shield.
Surfaces and corners in molded articles typically present difficulties for achieving sufficiently uniform distribution of particles. The present invention provides means for achieving the desired properties of the blend by providing conductive particles which by virtue of their multilayer structure preferably combine the requirements for compatibility, thermal stability, and high conductivity.
Similarly, the present invention provides a means of providing dispersible particles of a desirable size, geometry, and surface area. Such particles are generally produced by a nucleation and growth process within the reaction mixture. The size, shape, and surface area of such particles is known by those of skill in the art to be a function of reaction conditions especially including the chemical 1S composition of the dopant which is typically present during the synthesis of the polyaniline. The present invention allows for the optimal choice of dopant for this purpose since the other required characteristics, compatibility with the matriz and thermal stability, z0 can be added or enhanced in a post synthesis via a controlled exchange of dopant(s) in the surface regions of the particles. While we do not Wish to be bound by any theories. we postulate that the loss of conductivity from regions containing thermally unstable doped polyaniline compositions frequently occurs via outward diffusion and/or evaporation of the dopant. The use of a thermally stable dopant in an outer layer of the particle prevents or slows the loss of dopant from within the particle by limiting the 3,0 outward diffusion of such dopants of lower thermal stability. The particles may include various other optional ingridients. For example, salts containing dopant anions. plasticizers, or dispersion aids.
The particles of this invention can be 35 manufactured using modification of conventional chemical or electrochemical doping procedures such as those of U.S Patent 4,820,595 relating to polyaniline _ 3g _ which is hereby incorporated by reference. For example, particles of pcly~niline can be prepared by addition of an oxidant to solutions of the aniline monomer, The dopant anion incorporated in the poiyaniline may be derived from the oxidant (e. g.
FeCl4- from FeCl3) or it may be derived from an acid or salt which is also present in the solution (e. g., CH3(CSH4)S03- when tosylic acid is present) during addition of an oxidant such as ammonium persulfate.
Such conventional procedures produce doped conductive polyaniline particles and particle aggregates which are in general homogeneously doped with a dopant or mixture of dopants. In the present invention, such dopants or mixtures of dopants form the core of the conductive polyanilines particles. The outer layer or layers of the particles of this invention which contain dopant produced either during synthesis or after synthesis by dopant ezchange or by partial dopant removal and replacement. It is possible to achieve a stratified dopant configuration by using an excess of a different salt or acid during the latter stages of the polymerization reaction, tore preferred is to filter anc! wash the particles after the synthesis to remove any free salt or acid of the first Core dopant type or depending on the degree of washing to remove a surface layer of the core dopant from each particle. A dopant layer of different composition car.
be then achieved by washing or slurrying the polymer particles in a solution of the new dopant. Repeatedly washing with different dopants will produce multiple layers. It is preferred that primary particles rather than aggregates receive a core/shell dopant structure. It is preferred that the aqueous or nonaqueous solvent or solvent miature employed in the procedure act to swell the polyaniline particles. It is also preferred that the entire procedure act to swell the polymer particles. It is also preferred _ 39 _.
that the entire precedure from synthesis through to the formtion of a layered dopant structure be carried out while keeping the polyaniline particles wetted by a liquid which swells the polyaniline.
The electrically conductive polyaniline composition of this invention can be used for any purpose for which conductive polymers are useful. For example, the composition can be used to form electrically conductive articles for shielding purposes, anti-static purposes or adhesive. Eaamples of articles include conductive polymer housings for EMI Shielding of sensitive electronic equipment such as microprocessors, infrared, radio frequency and microwave absorbing shields, flexible electrically conducting connectors, conductive bearings, brushes and semiconducting photoconductor junctions, electrodes, capacitors, optically transparent or non-transparent corrosion-preventing coatings for corrodible materials such as steel, antistatic materials and optically transparent or non-transgarent coatings for packaging electronic components, antistatic carpet fibers, wanes for floors in computer rooms, antistatic finishes for CRT screens, aircraft, auto windows. electostatic dissipative packaging for electranics, and the like.
The particles of this invention are particularly suited for uae in the manufacture of emulsions, suspensions of the polyaniline, blends of the polyaniline with other polymers as for ezample, other conjugated backbone polymers, thermoplastic polymers such as polyamides, polycarbonates, polyesters, polylactones, polyolefins, polyacrylics; thermosetting resins such as phenolics and phenolic derivatives, alkyds. unsaturated polyester, epozies, melamines, amino resins and allylics; and miztures thereof. For eaample, blends of conductive polyaniline particles which are inherently highly polar may be made with a ~~~9~~~

polymer such as polyethylene terephthalate glycol) (PETG) or polycarbonate (PC) by combining a core dopant such as tosylate (CH3(C6H4)S03-), which offers hiah conductivity with a surface dopant such as dodecylbenzene sulfonate which offers increased compatibility with PETG or PC via the long-chain alkyl substituent tin the dopant anion.
The following specific examples are presented to more particularly illustrate the invention, and should not be construed as being limitations or. the scope and spirit of the inveNtion.
Polyaniline (PAni) (320G) doped with pare-toluene sulfonic acid (PTSA) (PAni-OTs) (approa. 8~ S) was filtered on a Huchner funnel and was placed into a bucket, and 3 liters of 1 M PTSA having a concentration of 1 mol/L were added and stirred for 1/2 hour. The material was again filtered on the Buchner funnel. Then the filtrate was combined with 3 liters of boiling water and the mixture was stirred with an agitator/miaer for 10 minutes, then filtered on the Huchner funnel. The filter cake had a sulfur content of about ~ ~ by weight. A solution of methanol (2.SL) containing 2 weight ~ of pare-dodecylbenxene sulfonic acid (DeSA) were added to the filter cake and stirred for 1/2 h. The mizture was then filtered again. The filtered material was dried in a fluid bed dryer at a maximum temperature of 80 °C.
The skin/core particles, (PAni-tosylate (OTs)-dodecylbenzene sulfonate (D8S)), and polyaniline tosylate (PAni-OTs) particles were combined with matrix polymers, polycaprolactone (PCL) and (PETG), into composites.

- ql -The relative proportions of the polyaniline components were varied ow er a range of samples from about 50% by weight polyaniline to about 5% by weight. Conductivity of compression molded samples of each blend were measured by a four-probe technique. A
plot of the logarithim of conductivity as a function of volume percent polyaniline gave an approximately "S" shaped curve in each case. Such characteristic "percolation" curves were analyzed to determine a "Percolation point" (the point of steepest rise in conductivity) specified by the volume percent loading of polyaniline at that point, and the saturation conductivity as evidenced by the conductivity observed for the highest loading level for polyaniline in the blend.
The results are set forth in the following Table II. In the Table, the conductivity of polyaniline is given in the first row and is that taken on a compressed pellet consisting of 100% polyaniline containing the specified dopant anion(s). The saturation conductivity given in the bottom row refers to the blend with PETG.
Doped PAni Particles (PAni-OTs) (PAni-OTs/DBS) A~ Conductivity of PAni 7.55 S/em 4.5 S/cm H. Percolation Point in PCL 8°~ 8°~s C. Percolation Point in PETG 20-25% 9.5%
D. Saturation Conductivity in PETG 5 z 10-'~ S/cm 2.5 S/cm ~~~9~'9~.
EXAMPLE Z
Polyaniline tosylate (PAni-OTs) was prepared from aniline, p-toluene sulfonic acid (PTSA), and ammonium persulfate solution by first combining the aniline and the acid, and then slowly adding the ammonium persulfate solution to the acid and aniline solution in approximately one hour. The solids which were formed were then filtered and washed successively twice with water (75°C), once with 5% solution of PTSA
(slurry for 1 to 2 hrs), and finally with a z%
solution of PTSA in methanol. After filtration, the solids were dried in a vacuum oven at 130°C until the temperature of the powdered solids reached 110°C. The water content of the solids was determined to be less than 3% by weight.
E~IF'~~
Polyanilinium tosylate coated by dodecylbenzene sulfonate (PAni OTs/DBS) was prepared as in Examgle 2 with the exception that dodecylbenzene sulfonic acid (DHSA) was substituted for the PTSA in the final methanol wash. By elemental analysis the resulting dried powder was found to contain approximately (by molar ratio) 70~ DTs and 30% DBS. Since exposure of PAni OTs to a concentrated solution of DBSA will cause the replacement of PTSA with DHSA via a process which requires the outward diffusion of PTSA and the inward diffusion of DBSA, the above process produced a polyaniline which was preferentially doped on the surface of each powder grain and/or primary particle with DHSA.

Polyaniline tosylate coated by naphthalene disulfonate was prepared by the procedure of Example 3 wherein naphthalene disulfonic acid (NDSA) was substituted far PTSA only in the final methanol wash and this wash was maintained at 75°C.

Polyaniline tosylate heavily exchanged with dodecylbenzene sulfonate (PAni-OTslDBS (heavy) and polyaniline tasylate heavily exchanged with naphthalene disulfonate (PAni-OTs/NDS (heavy)) where prepared in the manner of Example 2, with the exception that DBSA and NDSA were substituted far PTSA
in the final two washes, the first was being made at 75°C.
to The relative thermal stabilities of the various forms of polyaniline, described in Examples 2-5 above, were determined by the following procedure: The Powdered polyaniline was compressed into pellets with a diameter of 0.7 cm and a thickness of about 0.09 cm. The pellets were placed in an apparatus in which the given pellet was contacted by gold pins at four equally spaced points (90 degrees apart) near the circumference of the pellet. In this configuration a four-probe resistance measurement could be made which could be used to calculate the bulk conductivity of the pellet from the equation aØ215/(Rd), where ~ is conductivity in S/cm (or ohm'lcm-1), R is resistance in ohms, and d is pellet thickness in cm. The pellet was maintained in an atmosphere of flowing nitrogen and was held at various constant temperatures (130°C, 150°C, 170°C, 200°C, and 230°C) while the conductivity was observed to decay. In order to insure that all samples were thoroughly dry, the pellets were first held at 150°C for 16 hours before conductivity data were taken. All of the samples exhibited a decay in conductivity as an exponential function of time at a given temperature which could be described by the relation, o(t) - a°e-(t/z)a where Q(t) is the conductivity at a time, t; BO is the initial conductivity at time t . 0: 2 is an 2~?~1 - 49 _ experimentally determined characteristic decay time;
and a is an experimentally determined parameter for a given sample at each temperature. The value of a typically lay in a range from 0.77 to 1Ø With the help of this equation a charateristic half-life of the conductivity can be determined at each temperature from the value of ~ and a determined at that temperature according to the relation, tl/2 ' (ln2)1/a where In is the naperian logarithm and tl/2 is the time required for the conductivity to decrease by half (half life). Since the determination of T and a can be made from the functional form of the decay at early times, this method does not require that the conductivity be driven down to one half its original value at each temperature. As a result, this method allows the determination of the half lives at the five temperatures listed above on the same sample without unduly altering the thermal decay characteristics of the sample by heavily degrading the sample at each temperature. The following Table II summarizes the results obtained for the various polyaniline samples.
In the Table II, the abbreviations have the following meanings:
(a) "PAni-OTS" is polyaniline doped with tosylate as in Ezample 2.
(b) "PAni-OTS/DHS" is skin/core polyaniline particles doped with tosylate at the core and doped with dodecylbenzene sulfonate at the skin as in Example 3.
(c) "PAni-OTs/DHS (heavy)" is polyaniline heavily doped with dodecylbenzene sulfonate as in Example 5.
3~ (d) "PAni-OTS/NDS" is skin/core polyaniline particles doped with tosylate at the core and doped with naphthalene disulfonate at the skin as in Example 4.

(e) "PAni-OTs/NDS (heavy)" is polyaniline heavily doped with naphthalene disulfonic acid as in Example S.
able II
Conductivity Half Lives of Polyaniline Compositions Composition CTO tl/2(170°C) tl/2(200°C) tl/2(230°C) (S/cm) (h) (h) (h) PAni-OTs 5.4 20.6 1.8 0.15 PAni-OTs/DBS 6.2 20.0 1.5 0.21 PAni-OTs/DBS
(heavy) 0.9 10.1 1.3 0.23 PAni-OTs/NDS 6.4 54.3 4.1 0.34 PAni-OTs/NDS 1.0 98.6 15.8 1.4 (heavy) The conductivity given in the Table II, a . is that obtained at 150°C after drying 16 hours at 150°C. The conductivity half lives, tl/2, are those measured at 170°C, 200°C, and 230°C. The data are arranged in order of thermal stability at the highest temperature 230°C. The data fox the samples having a skin/core arrangement of different organic sulfonate dopant anions illustrate a synergy of desirable properties which goes beyond a simple average. The core and skin cosabination of PTSA and DBSA, respectively, (PAni OTa/DHS) results in a conductive polyaniline which combines the higher thermal stability of PAni/DHS with the high conductivity of PAni/OTs. hikewise, the PAni OTs/NDS sample combines the high conductivity of PAni/OTs with a significant improvement in the thermal stability stemming from its skin of the dopant, NDSA, even though this sample received only a light treatment with NDSA in the final wash. The sample PAni OTs/NDS (heavy) shows an even more substantial increase in thermal stability. Fox comparison with 2~69?~1 the results of Table II, a sample of polyaniline doped with hydrochloric acid was also tested. This sample was treated at temperatures below 100°C because it was to resistive to measure at temperatures above 100°C.
The initial conductivity offer drying at 90°C was 2.9 S/ctn.
Example 7 The data for the half lives taken as in Example 6 at 130°C, 150°C, 170°C, 200°C, 230°C was shown to follow an Arrhenius exponential as a function of temperature of the form, tl/2 ' t(1/2)°eEa/KT
where a is the base of the naperian logarithm and K is the Boltzmann constant. The activation energy, Ea, was determined from the slope of a plot of ln(tl/2] vs the inverse of absolute temperature in degrees Kelvin. The naperian logarithm of the prefactor, In((tl/2)0]~ was determined from the intercept at 1!T'0. These empirically determined parameters were then used to predict the thermal stability (i.e., the conductivity half life) over a range of temperature eatending from 50°C to about 280°C. The agreement between the predicted variation of half-life and data taken for PAni-OTs is shown in Figure 1 projected results are given in Figure 2 for PAni OTs, PAni-OTs/DBS and PAni-OTs/DBS (heavy). Figure 3 compares the projected results obtained for PAni-OTs, PAni-OTs/NDS and PAni-OTs/NDS (heavy). These figures illustrate that the thermal stability for the samples with a skin/core dopant arrangement is enhanced beyond a simple averaging of properties. These data were used to estimate an upper limit for processing termperature (Tp) and for continuous use temperature (Tu)~ Temperatures corresponding to maaimum processing times of 0.1 h and l.Oh Were calculated along with the temperatures where the continuous use 2(~~~?~~.
time was 5 years. 'table III below summarizes the results obtained for the various compositions which were tested.
TABLB III
Use Temperature and Processing Temperatures of Polyaniline Compositions Composition Tu Tp(lh) Tp (O.lh) (C) (C) (C) PAni-OTs 97 206 239 PAni-OTs/DBS 84 207 245 PAni-OTs/DBS (heavy) 68 203 246 PAni-OTs/NDS 112 217 249 PAni-OTs/NDS (heavy) 112 239 280 Table III indicates that the addition of DHSA or NDSA as a surface dopant on PAni-OTs raises the processing temperature in each case. As shown in Table Iv, the use temperature of PAni-OTs/DBS is found to be intermediate between that of PAni-OTs and PAni-OTs/DBS (heavy), and these is a small increase in the higher processing temperative for both (DHSA
treated) samples in comparison With PAni-OTs. The use temperatures of PAni-OTs/NDS and PAni-OTs/NDS (heavy) are found to be nearly equivalent, yet the processing temperatures for the sample with a heavy skin of P1DS
anions are much higher than these for the sample with lightly doped skin layer.

Claims (36)

1. An electrically conductive polyaniline particle comprising a substituted or unsubstituted polyanilire doped with two or more dopants, at least one of said dopants predominating at or near the surface of said particles and at least one other dopant predominating at or near the core of said particle.

2. They particle according to claim 1 wherein said polyaniline is a polyaniline homopolymer or copolymer of the type derived from polymerizing an aniline of the formula:

n is an integer from 0 to 5;
m is an integer from 0 to 5, with the proviso that the sum of n and m is 5;
R1 is phosphinic acid, phosphonic acid, sulfonic acid, boric acid, phosphoric acid, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, amino, sulfonate salt, borate salt, hydroxy, phosphonate salt, phosphinate salt, phosphate salt, sulfinic acid, nitro, sulfinate salt, carboxylic acid, halo, carboxylate salt, cyano, deuterium, or substituted or unsubstituted alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, alkanoyl, alkylthio, alkynyl, dialkylamino, arylamino.
diarylamino, alkylarylamino, aryloxy, hydrozy, alkylthioalkyl, alkylaryl, arylalkyl, aryloxy, amino, alkylthioalkyl, alkylaryl, arylalkyl, alkylsufinyl, alkoxyalkyl, alkylsulfonyl, aryl, arylthio, arylsulfinyl, alkoxycarbonyl, alkylsilane, or arylsulfonyl, wherein permissible substituents are one or more amino, phosphinate salt, alkylamino, dialkylamino, arylamino, diarylamino,phosphinic acid, alkylarylamino, phosphoric acid, sulfonic acid, boric acid, sulfinic acid, sulfinate salt, phosphoric acid, sulfonate salt, borate salt, carboxylate salt, phosphonate salt, phosphate salt, carboxylic acid, halo, nitro, hydroxy, cyano or epoxy moieties; or any two R3 substituents or any one R3 substituent and R2 substituent taken together may form substituted or unsubstitued alkylene, alkynylene or alkenylene chain completing a 3, 4, 5, 6, 7, 8, 9 or 10 membered aromatic, heteroalicyclic, heteroaromatic or alicyclic carbon ring, which ring may optionally include one or more divalent ester, carbonyl, nitrogen, sulfur, sulfinyl, sulfonyl or oxygen wherein permissible substituents are one or more amino, alkylamino, phosphinic acid, phosphinate salt, dialkylamino, arylamino, diarylamino, alkylarylamino, phosphoric acid, sulfonic acid, boric acid, sulfinic acid, sulfinate salt, phosphoric acid, sulfonate salt, borate salt, carboxylate salt, phosphonate salt, phosphate salt, carboxylic acid, halo, nitro, hydroxy, cyano or epoxy moieties, or R3 is an aliphatic moiety having repeat units of the formula:

(OCH2CH2q O-CH3, (OCH2CH(CH3))qO-CH3, (CH2)qCF3, (CF2)qCF3 or (CH2)q CH3 wherein q is a positive whole number; and R2 is the same or different at each occurrence and is R1 substituents or hydrogen.

3. The particle according to claim 2 wherein said homopolymer or copolymer is of the formulas II
to V:

wherein:
x and y are the same or different at each occurrence and are integers equal to or greater than 0, with the proviso that the sum or x and y are greater than 0;
z is an integer equal to or greater than about 1;
n is an integer from 0 to 3;
m is an integer from 1 to 4, with the proviso that the sum of n and m is 4;
R1 is the same or different at each occurrence and is alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, alkanoyl, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, alkylthio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl. alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, aryl, arythio, arylsulfinyl, alkoxycarbonyl, phosphinic acid, phosphonic acid, alkylsilyl, boric acid, arylsulfonyl, carboxylic acid, halo, hydroxy, phosphate salt, sulfonate salt, phosphonate salt, borate salt, phosphinate salt. carboxylate salt, nitro, cyano, sulfonic acid, phosphoric acid or aryl, alkyl or alkoxy substituted with one or more sulfonic acid, carboxylic acid, sulfinate salt, phosphoric acid, boric acid, sulfinic acid, halogen, nitro, cyano, epoxy, hydroxy, sulfonate salt, phosphate salt, phosphonate salt, phosphinic acid, phosphinate salt, carboxylate salt, phosphonic acid or borate salt substituents; or any two R1 groups or any one R1 group and R2, group together may form a substituted or unsubstituted alkylene or alkenylene chain completing a 3, 5, 5, 6, 7, 8, 9 or 10 membered heteroaromatic, heteroalicyclic, aromatic or alicyclic carbon ring, which chain may optionally include one or more divalent nitrogen, ester, carbonyl, sulfur, sulfinyl, sulfonyl or oxygen group wherein permissible substituents are one or more sulfonic acid, carboxylic acid, sulfinate salt, phosphoric acid, boric acid, sulfinic acid, halogen, nitro, cyano, epoxy, hydroxy, sulfonate salt, phosphate salt, phosphonate salts, phosphinic acid, phosphinate salt, carboxylate salts, phosphonic acid or borate salt substituents; and R2 is the same of different at each occurrence and is R1 substituents or hydrogen.

4. The particle according to claim 3 wherein m is from about 2 to about 4.

5. The particle according to claim 4 wherein m is from about 3 to about 4.

6. The particle according to claim 2 wherein said polyaniline is derived from substituted anilines.

7. The particle according to claim 2 wherein said polyaniline is derived from unsubstituted aniline.

8. The particle according to claim 6 wherein R1 is the same or different at each occurrence and is alkyl or alkoxy having from 1 to about 30 carbon atoms.

9. The particle according to claim 8 wherein R1 is the same or different at each occurrence and is alkyl having from 1 to about 20 carbon atoms or alkoxy having from 1 to about 20 carbons.

10. The particle according to claim 5 wherein, R1 is alkyl or substituted alkyl.

11. The particle according to claim 6 wherein said homopolymer or copolymer is of the Formulas II
to V wherein:
n is an integer from 0 to about 2;
m is an integer from 2 to 4, with the proviso that the sum of n and m is equal to 4;

R1 is aryl, alkyl or alkoxy having from 1 to about 30 carbon atoms, cyano, halo, sulfonic acid, carboxylic acid, boric acid, borate salt, phosphoric acid, phosphate salt, phosphoric acid, phosphonate salt, phosphinic acid, phosphinate salt, sulfinic acid, sulfinate salt, carboxylate salt, sulfonate salt, amino, alkylamino, dialkylamino, arylamino, hydroxy, diarylamino, alkylarylamino, or alkyl, aryl or alkoxy substituted with phosphoric acid, phosphate salt, phosphoric acid, borate salt, sulfonate salt, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, carboxylate salt, hydroxy, alkoxy, phosphonic acid, boric acid, alkyl, phosphinic acid, phosphonate salt, phosphinate salt, carboxylic acid or sulfonic acid substituents;
R2 is the same or different at each occurrence and is a R1 substituent or hydrogen;
x is an integer equal to or greater than 1;
y is equal to or greater than 0, with the proviso that the ratio of x to y is greater than about 0: and z is an integer equal to or greater than about 5.

12. The particle according to claim 11 wherein:
n is an integer from 0 to 1;
m is an integer from 3 to 4, with the proviso that the sum of n and m is equal to 4;
R1 is aryl, alkyl or alkoxy having from 1 to about 20 carbon atoms, sulfonic acid, halo, carboxylic acid, amino, carboxylate salt, alkylamino, phosphonate salt, dialkylamino, arylamino, phosphoric acid, boric acid, phosphate salt, phosphoric acid, borate salt, diarylamino, alkylyarylamino, or alkyl or aryl substituted with carboxylic acid, phosphoric acid, boric acid, phosphate salt, phosphoric acid, borate salt, sulfonate salt, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, carboaylate salt, halo, phosphonate salt, or sulfonic acid substituents;
R2 is the same or different at each occurrence and is a R1 subsit:uent or hydrogen;
x is an integer equal to or greater than 2;
y is equal to or greater than 0, with the proviso that the ratio of x to y is greater than about 0.5; and z is an integer equal to or greater than about 5.

13. The particle according to claim 12 wherein:
n is an integer from 0 to 1;
m is an integer from 3 to 4, with the proviso that the sum of n and m is equal to 4;
R1 is aryl, alkyl, alkoxy, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, halo, or sulfonic acid, sulfonate salt, carboxylic acid or carboxylate salt or alkyl or aryl substituted with one or more sulfonic acid, carboxylate salt, amino, alkylamino, dialkylamino. arylamino, diarylamino, halo, alkylarylamino. sulfate salt, sulfonate salt. or carboxylic acid substituents wherein aromatic moieties include from 6 to about 21 carbon atoms, and the aliphatic moieties are from 1 to about 15 carbon atoms;
R2 is hydrogen;
z is an integer equal to or greater than 2;
y is equal to or greater than 1, with the proviso that the ratio of x to y is equal to or greater than about 1; and z is an integer equal to or greater than about 5.

14. The particle according to claim 13 wherein:
n is 0 or 1;

m is 3 or 4, with the proviso that the sum of n and m is 4;
R1 is sulfonic acid, a hydrolyzable derivative of sulfonic acid, alkoxy or alkyl; and R2 is hydrogen, arylsulfonyl or alkylsulfonyl.

15. The particle according to claim 14 wherein:
n is 1;
m is 3;
R1 is sulfonic acid or a hydrolyzable derivative thereof; and R2 is hydrogen.

16. The particle according to claim 14 wherein:
n is 0;
m is 4; and R2 is hydrogen.

17. The particle according to claim 1 wherein said polyaniline is doped with one or more organic acid dopants or salts thereof having anionic moieties of the formula:

R4(PO3~)r(PO2~)r(PO2~)r(PO2(R6-)r(SO3)-t)r(CO2-)r (BO2~)r(PO(R6)-)r and having a cationic moiety of the Formula:

M+s wherein at least one of the cation moieties of the formula M+s is a proton or is a moiety which can be transformed into a proton under use conditions;
M+s is a cationic species having or positing charge s;
s is an integer equal to or greater than 1;
R4 and R6 are organic radicals or amino, and r is an integer equal to or greater than 1.

18. The particle according to claim 17 wherein said dopants are acids or acid derivatives of the formula:

R4(PO2(R6)M)g(PO3M2)f(SO3M)c(CO2M)d(PO2M2)t(SO2M)h (PO(R6))i or wherein:
M is H+, or other metal or non-metal cation with the proviso that at least one of M is H+ or a moiety which can be thermally or chemically transformed into a proton under use conditions, such as t is 0, 1, 2, 3 or 4;
i is 0, 1, 2, 3 or 4;
h is 0, 1, 2, 3 or 4;
c is 0, 1, 2, 3 or 4;
d is 0, 1, 2, 3 or 4;
f is 0, 1, 2, 3 or 4;
g is 0, 1, 2, 3 or 4 with the proviso that at least one of t, i, h, c, d, f or g is other than 0;
e is 0, 1, 2; and R4, R5 and R6 are the same or different at each occurrence and are nitro, cyano, hydroxy, halo, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, alkoxy, or salt substituted or unsubstituted alkoxy, aryl or alkyl having from 1 to about 30 carbon atoms wherein permissible substituents include sulfonate salt, perhaloalkyl, phenyl, alkoxy, halo, cyano, amino, haloalkyl, hydroxy, sulfonic acid, phosphoric acid phosphate salt, boric acid, sulfinate salt, phosphinate salt, sulfinic acid, borate salt, phosphinic acid, phosphonate salt, phosphoric acid, carboxylic acid, nitro, carboxylate salt and the like, or any two R4 or any two R5 substituents together may form an alkenylene chain completing a fused-ring system which chain may be unsubstituted or substituted with one or more halo, phosphoric acid, hydroxy, boric acid, nitro, cyano, amino, sulfinate salt, phosphinic acid, alkylamino, dialkylamino, phosphinate salt, arylamino, diarylamino, alkylarylamino, sulfinic acid, phosphate salt, carboxylate salt, phosphoric acid, phosphonate salt, sulfonate salt, borate salt, sulfonic acid or carboxylic acid groups, or R4 or R5 is a moiety of the formula:

-(CH2)qCF3, -(CF2)qCF3, -(CH2)qCH3 - (OCH2CH2)qOCH3 or - (OCH2CH(CH3))qOCH3 wherein:
q is a positive whole number from 1 to about 10;
and

19. The particle according to claim 18 wherein said dopants are acids, acid derivatives or a combination thereof of the above formula:

R4(PO2(R6)M)s(PO3M2)f(SO3M)c(CO2M)d(PO2M2)t(SO2M)h (PO(R6)M)i or wherein:
c is 0, 1, 2 or 3;
d, t, i, f, g and h are the same or different at each occurrence and are with the proviso that at least one of c, h, i, t, d, f or g is other than 0;
e is 0, 1 or 2;
R4 and R5 are the same or different are hydroxy, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, substituted or unsubstituted phenyl or alkyl wherein permissible substituents are selected from the group consisting of alkyl, hydroxy, amino, alkylamino, dialkylamine, arylamine, diarylamino, alkylarylamino, hydroxy, phenyl, haloalkyl, perhaloalkyl, cyano, amino, nitro, alkoxy, boric acid, borate salts, phosphonate, phosphoric acid, carboxylate salts, sulfonate salts, phosphate salts, phosphinic acid, phosphinate salt, sulfonic acid, carboxylic acid, phosphoric acid, sulfinic acid or sulfinate salts or any two R6 substituents together may form an unsubstituted or substituted or alkenylene chain completing a naphthalene, anthracene or phenanthracene fused ring system wherein permissible substituents are as described above or R4 or R5 is a moiety of the formula:

- (CH2)qCF3, -(CF2)qCR3, -(CH2)qCH3 , - (OCH2CH2)qOCH3 or -(OCH2CH(CH3))q OCH3 wherein:
q is a positive whole number from 1 to about 10;
R6 is alkyl, alkoxy, aryloxy or aryl; and M is H+, or other metal or non-metal cation, with the proviso that at least one of M is H+ or a moiety which can be thermally or chemically transformed into a proton under use conditions.

20. The particle according to claim 19 wherein said dopants are acids and/or acid derivatives of the formula:

R4g(PO2(R6)M)8(SO3M)c(CO2M)d or wherein:
c, d, e, and g are the same or different and are 0, 1 or 2 with the proviso that at least one of c, d, and g is not 0;

R4 and R5 are the same or different at each occurrence and are alkyl, phenyl, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, or alkyl substituted with one or more fluoro, sulfonic acid, sulfonate salt, alkoxy, carboxylate salt, hydroxy, nitro, cyano, phosphinic acid, phosphinate salt, amino or carboxylic acid groups, or phenyl substituted with one or more alkyl, alkoxy, fluoroalkyl, sulfonic acid, phosphinic acid, phosphinic salt, sulfonate salt, carboxylate, hydroxy, nitro, cyano, or carboxylic acid groups or any two R4 or R5 substituents together may form an alkylene or alkenylene chain completing a naphthalene, anthracene or phenanthracene fused system which may be substituted with one or more alkyl, alkoxy, fluoro, phosphinic acid, phosphinate salt, fluoroalkyl, sulfonic acid, sulfonate salt, carboxylic acid, carboxylate salt, hydroxy, nitro, amino or cyano groups;
R6 is aryl, aryloxy, alkyl or alkoxy; and M is H+ or other metal or non-metal cation, with the proviso that at least one of M is H+ or is a moiety which can be thermally transformed into a proton under process conditions.

21. The particle according to claim 20 wherein said dopants are acids acid derivatives or a combination thereof of the formula:
R4(SO3M)c (CO2M)d or wherein:
c is 1, 2 or 3;
d is 0, 1 or 2, with the proviso that at least one of c, or d is not 0;
e is 0, 1 or 2;
R4 and R5 are th same or different at each occurrence and are hydroxy, dialkylamino, diarylamino, alkylarylamino, amino, alkylamino, arylamino, alkyl, phenyl, alkyl substituted with one or more fluoro, sulfonic acid, sulfonate salt, alkoxy, dialkylamino, diarylamino, alkylarylamino, carboxylate salt, hydroxy, alkylamino, arylamino, phosphonic acid, nitro, cyano, phosphinic acid, phosphinate salt, phosphonate amino or carboxylic acid groups, or phenyl substituted with one or more alkyl, alkoxy, fluoroalkyl, dialkylamino, diarylamino, alkylarylamino, sulfonic acid, alkylamino, arylamino, sulfonate salt, carboxylate salt, hydroxy, phosphinate acid, phosphinate salt, nitro, cyano, amino or carboxylic groups or any two R4 and R5 substituents together may form an alkylene or alkenylene chain completing a naphthalene, anthracene or phenanthracene fused system which may be substituted with one or more alkyl, alkoxy, fluoro, fluoroalkyl, sulfonic acid, sulfonate salt, carboxylic acid, phosphinic acid, phosphinate salts, carboxylate salt, hydroxy, nitro, amino, alkylamino, dialkylamino, arylamino, diarylamino, alkylarylamino, or cyano groups; and M is H+ or other metal or non-metal cation or a moiety which is thermally tranformed into a proton under process conditions.

22. The particle according to claim 21 wherein said dopant is a sulfonic acid, sulfonic acid derivative or a combination thereof of the formula:
wherein;
c is 1, 2 or 3;
e is 0, 1 or 2;
R5 is alkyl or alkyl substituted with one or more fluoro, or any two R2 groups together may form an alkenylene chain completing a naphthalene faced system which may be substituted with one or more sulfonic acid or, sulfonic acid salt, fluoro or alkyl group; and M is a proton, or other metal or non-metal cation, with the proviso that at least one of M is proton.

23. The particle according to claim 21 wherein said polyaniline is unsubstituted polyaniline and at least one of said dopants predominating at the core of said particle is selected from group consisting of methane sulfonic acid, trifluoromethane sulfonic acid, p-toluene sulfonic acid, 4-hydroxybenzene sulfonic acid, benzene sulfonic acid, perchloric acid, sulfonic acid, and trifluoroacetic acid.

24. The particles according to claim 23 wherein at least one of said dopants predominating at the core of said particle is p-toluene sulfonic acid.

25. The particle according to claim 23 where at least one dopant predominating at or near the outer surface of said particle is selected from the goup consisiting of compatibility enhancing dopants that increase the compatibility between said particle and a matrix polymer of lower surface energy and lesser polar character and thermally stable dopants which form doped unsubstituted polyaniline which is thermally stable at a temperature of 200°C thermally stable.

26. The particle according to claim 25 wherein said compatibility enhancing dopants are selected from the group consisting of aliphatic acid or aliphatic acid having three or more carbon atoms wherein said aliphatic moiety includes three or more carbon atoms or aromatic acids substituted with one or more substituted alkyl having three or more carbon atoms or one or more alkyl substituted with one or more fluoro substitutents.

27. The particle according to claim 26 wherein the number of carbon atoms is equal to or greater than about 5.

28. The particle according to claim 27 wherein the number of carbon atoms is equal to or greater than about 8.

29. The particle according to claim 28 wherein the number of carbon atoms is equal to or greater than about 12.

30. The particle according to claim 27 wherein said compatibility enhancing dopants is selected from the group consiting of octylsulfonic acid, perfluorooctylsulfonic acid, dodecylsulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid and dodecyldiphenyl ether disulfonic acid.

31. The particle according to claim 25 wherein said thermally stable dopants are aromatic compositions having more than one sulfonic acid group.

32. The particle according to claim 31 wherein said thermally stable dopant is selected from the group consisting of 1,5-naphthalene sulfonic acid, 2,6-naphthalene sulfonic acid, 1-naphthol-3,6-disulfonic acid, diphenylether-4,4'-disulfonic acid, diphenylsulfone-4,4'-disulfonic acid, 1,3,6-naphthalene trisulfonic acid, and 2,5-dihydroxy-1,4-benzene disulfonic acid.

33. The particle according to claim 25 wherein said thermally stable dopant is selected from the group consisting of oligomers and polymeric sulfonates containing more than two sulfonic acid groups.

34. The particle according to claim 33 wherein said oligomers and polymeric sulfonates are selected from the group consisting of polyvinyl sulfonic acid, sulfonated polystyrene, sulfonated poly (vinyl naphthalene) and sulfonated phenolic resin.

35. An electrically conductive polyaniline particle of unsubstitured polyaniline wherein said particle is doped predominantly at or near the core with toluenesulfonic acid and is doped predominately at or near the surface with dodecylbenzene suflonic acid.

36. An electrically coductive polyaniline particle of unsubstituted polyaniline wherein said particle is doped predominantly at or near the core with toluene sulfonic acid and is doped predominantly at or near the surface with naphthalene disulfonic acid.