Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
20 1 1 1 89
THERMALLY STABLE FORMS OF
ELECTRICALLY CONDUCTIVE ~QLYANILINE
RELATED APPLICATIONS
BACKGRQUND OF THE INVENTION
1. Field of the Invention
This invention relates to thermally stable
electrically conductive substituted or unsubstituted
polyanilines, and to compositions comprising such
polyanilines and other non-electrically conductive
polymers. Another aspect of this invention relates to a
method of using such polyanilines and compositions to give
conducting polymer articles, including films, fibers and
coatings, and to fabricate such articles.
2. Prior Art
There has recently been an increased interest in
the electrochemistry and electrical phenomena of polymeric
systems. Recently, work has intensified with backbone
p°lymers having extended conjugation in at least one
backbone chain.
One conjugated polymer system currently under study
is polyaniline. Kobayashi, Tetsuhiko, et al.,
J. Electroanal. Chem., "Electrochemical Reactions
Concerned With Electrochromism of Polyaniline Film-Coated
Electrodes", 177 (1984) 281-291, describes various
experiments in which spectro electro-chemical measurement
of a polyaniline film coated electrode were made. French
Patent No. 1,519,729; French Patent of Addition 94,536;
U.K. Patent 1,216,549; "Direct Current Conductivity of
Polyaniline Sulfate", M. Donomedoff, F. Kautier -
Cristojini, R. De Surville, M. Jozefowicz, L-T. Yu, and
20111~J
-2-
R. Buvet, J. Chim. Phys. Phvsicohim. Brol, 68, 1055 {1971);
"Continuous Current Conductivity of Macro-molecular
Materials", L-T. Yu, M. Jozefowicz, and R. Buvet, Chim.
Macromol., ~, 469 (1970); "Polyaniline Based Filmogenic
Organic Conductive Polymers", D. LaBarre and
M. Jozefowicz, C. R. Read. Sci., Ser. C, ?~, 964 (1969);
"Recently Discovered Properties of Semiconducting
Polymers", M. Jozefowicz, L-T. Yu, J. Perichon, and
R. Buvet, ~I. Polym. Sci., Part C, ~, 1187 (1967);
~~Electrochemical Properties of Polyaniline Sulfates", F.
Cristojini, R. De Surville, and M. Jozefowicz, Cr. Read.
Sci., Ser. C, ?~$, 1346 (1979); "Electrochemical Cells
Using Protolytic Organic Semiconductors", R. De Surville,
M. Jozefowicz, L-T. Yu, J. Perichon, R. Buvet,
Electrochem. Ditn., ~, 1451 (1968); "Oligomers and
Polymers Produced by Oxidation of Aromatic Amines",
R. De Surville, M. Jozefowicz, and R. Buvet, Ann. Chern.
(Paris), ~ 5 {1967); "Experimental Study of the Direct
Current Conductivity of Macromolecular Compounds",
L-T. Yu, M. Borredon, N. Jozefowicz, G. Belorgey, and
R. Buvet, J. Polvm. Sci. Polyp"-~vmn., 16, 2931 (1967);
"Conductivity and Chemical Properties of Oligomeric
Polyaniline", M. Jozefowicz, L-T. Yu, G. Belorgey, and
R. Buvet, J. Polym. Sci.. Polym. Symp., 16, 2934 (1967);
"Products of the Catalytic Oxidation of Aromatic Amines",
R. De Surville, M. Jozefowicz, and R. Buvet, Amm. Chem.
(Paris), 2, 149 (1967); "Conductivity and Chemical
Composition of Macromolecular Semiconductors", Rev. Gen.
Electr., 75 1014 (1966); "Relation Between the Chemical and
Electrochemical Properties of Macromolecular
Semiconductors", M. Jozefowicz and L-T. Yu, Rev. Gen.
Electr., 75 1008 (1966); "Preparation, Chemical
Properties, and Electrical Conductivity of Poly-N-Alkyl
Anilines in the Solid State", 0. Muller and
M. Jozefowicz, Bull. Soc. Chem., Fr. 4087 {1972).
U.S. Patent Nos. 3,963,498 and 4,025,463 describe
oligomeric polyanilines and substituted polyanilines
having not more than 8 aniline repeat units which are
2~~1~89
-3-
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 U.S. Patent 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.
In the general field of conducting polymers, it was
heretofore neither demonstrated nor conceived that
thermally stable conductive polyanilines could be
prepared, and that compositions comprising such poly-
anilines and one or more thermoplastic polymers could be
fabricated into useful articles by melt blending
techniques. Thus. a need exists for thermally stable
electrically conductive polyanilines and for techniques to
facilitate the fabrication of shaped conductive
polyaniline articles, especially articles such as films,
sheets, fibers, prismatic objects and coatings.
SUMMARY OF THE INVENTION
One aspect of the present invention relates to a
thermally stable, electrically conductive doped
polyaniline comprised of an ionized polyaniline backbone
polymer and one or more dopant solute species selected
from the group consisting of:
R1(P03)r. Rl(P02)~~
Rl(P03H )r. R1 (S02)r.
R1(-So3)r. R1(COO )r and R1(Bo2H )r
wherein Rl is the same or different at each occurrence
and is a substituted or unsubstituted organic radical, and
r is a positive whole number equal to or greater than 1.
Another aspect of this invention is articles formed from
201118
-4-
this polyaniline. This invention also relates to a
composition comprising a matrix of one or more
thermoplastic polymers having one or more doped
polyanilines of this invention dispersed therein, and to
articles formed from this composition. This invention
also relates to a process for forming the compositions of
this invention by melt-blending one or more doped
polyaniline of this invention and one or more
thermoplastic polymers.
As used herein, "polyanilines" are homopolymers or
copolymers in which at least 50 mole % of the recurring
monomeric units are derived from unsubstituted or
substituted anilines of the formula:
NR2R4
~H~~a ~F3~n
wherein:
n is an integer from 0 to 4:
m is an integer from 1 to 5 with the proviso that
the sum of n and m is equal to 5;
RZ and R4 are the same or different and are R3
substituents, hydrogen or alkyl with the proviso that at
least one of R2 or R4 is hydrogen; and
R3 is the same or different at each occurrence and
is selected from the group consisting of deuterium, alkyl,
alkenyl, alkoxy, cycloalkyl, cycloalkenyl, alkanoyl,
alkythio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl,
amino, alkylamino, dialkylamino, aryl, alkylsulfinyl,
aryloxyalkyl, alkylsulfinylalkyl, alkoxyalkyl,
alkylsulfonyl, phosphonic acid, borate, carboxylate,
phosphonate, sulfonate, phosphinate, arylthio, sulfinate,
sulfinic acid, alkylsulfonylalkyl, arylsulfinyl,
alkoxycarbonyl, arylsulfonyl, carboxylic acid, halogen,
X011189
-5-
hydroxy, cyano, sulfonic acid, nitro, or alkylsilane; or
alkyl substituted with one or more sulfonic acid,
phosphoric acid, phosphonic acid, sulfinate, sulfinic
acid, borate, carboxylate, phosphonate, sulfonate,
phosphinate, boric acid, carboxylic acid, halo, nitro,
cyano or epoxy moieties; or any two R3 groups together
or an R3 group togetherr with any R4 or R2 group may
form an alkylene or alkenylene chain completing a 3, 4, 5,
6 or 7 membered aromatic or alicyclic ring, which ring may
optionally include one or more divalent nitrogen, sulfur,
sulfinyl, ester, carbonyl, sulfonyl, or oxygen atoms; or
R3 is an aliphatic moiety having repeat units of the
formula:
-(~CH2~-qCF3 , --ECF2-~-qCF3 . --~CH2 qCH3 .
-f OCHZCH2~--q0-CH3 , or ~OCH2CH(CH3 ) ~--q0-CH3
wherein q is a positive whole number; with the proviso
that said homopolymer or copolymer includes about 10 or
more recurring aniline moieties in the polymer backbone.
As used herein, an "organic radical" is polymeric or
other type of radical.
BRIEF DESCRIPTION OF DRAWINGS
In the drawings,
FIG 1 is a thermogravimetric analysis (TGA) spectrum
under argon of poly(aniline chloride) as prepared in
Example 1.
FIG 2 is a thermogravimetric analysis (TGA)
spectrum under argon of poly(aniline J.,S-naphthalene
disulfonate) as prepared in Example 2.
FIG 3 is a thermogravimetric analysis (TGA)
spectrum under argon of poly(aniline p-toluene sulfonate)
as prepared by redoping neutral polyaniline (Example 3).
2om~~
-6-
FIG 4 is a thermogravimetric analysis (TGA) spectrum
under argon of poly(aniline p-toluene sulfonate) as
prepared in Example 4.
FIG 5 is a thermogravimetricric analysis (TGA)
spectrum under argon of poly(aniline dodecyl-benzene
sulfonate) as prepared in Example 5.
FIG 6 is a thermogravimetric analysis (TGA) spectrum
under argon of poly(aniline 1, 3-benzene disulfonate) as
prepared in Example 6.
FIG 7 is a thermogravimetric analysis (TGA) spectrum
under argon of poly(aniline-sulfonate) as prepared in
Example 7.
FIG 8 is a graph showing percent weight loss as a
function of temperature for polyaniline doped with
chloride anions.
FIG 9 is a graph showing percent weight loss as a
function of temperature for polyaniline doped with
tosylate anions.
DETAILED DESCRIPTION OF THE INVENTION
The thermally stable electrically conductive
polyaniline of this invention comprises two essential
ingredients. One essential ingredient is a substituted or
unsubstituted polyaniline. In general, polyanilines for
use in the invention are homopolymers and copolymers
derived from the polymerization of unsubstituted and
substituted anilines of the Formula I:
NR2R4
3 5 '''
{H)~n ~~3)n
2011189
wherein:
n is an integer from 0 to 4;
m is an integer from 1 to 5 with the proviso that the
sum of n and m is equal to 5;
R2 and R4 are the same or different and are R3
substituents, hydrogen or alkyl; and
R3 is the same or different at each occurrence and
is selected from the group consisting of alkyl, deuterium,
alkenyl, alkoxy, cycloalkyl, cycloalkenyl, alkanoyl,
alkythio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl,
amino, alkylamino, dialkylamino, aryl, alkylsulfinyl,
aryloxyalkyl, alkylsulfinylalkyl, alkoxyalkyl, phosphoric
acid, alkylsulfonyl, arylthio, alkylsulfonylalkyl, boric
acid, phosphoric acid, sulfinate, arylsulfinyl,
alkoxycarbonyl, arylsulfonyl, carboxylic acid, phosphoric
acid, halogen, hydroxy, cyano, sulfinic acid, carboxylate,
borate, phosphate, sulfonate, phosphinate, phosphonate,
phosphoric acid, sulfonic acid, nitro, alkylsilane or
alkyl substituted with one or more phosphoric acid,
sulfonic acid, phosphoric acid, boric acid, carboxylate,
borate, sulfonate, phosphinate, phosphonate, phosphate
acid, phosphinic acid, carboxylic acid. halo, nitro,
cyano or epoxy moieties; or any two R3 groups together
or any R3 group together with any R1 or R2 group may
form an alkylene or alkenylene chain completing a 3, 4, 5,
6 or 7 membered aromatic or alicyclic ring, which ring may
optionally include one or more divalent nitrogen, sulfur,
sulfinyl, ester, carbonyl, sulfonyl, or oxygen atoms; or
R3 is a divalent organic moiety bonded to the same or a
different substituted or unsubstituted aniline moiety or
R3 is an aliphatic moiety having repeat ura.its of_ t_lue
formula:
-~OCH2CH2-~-q0-CH3 , --f OCH2CH ( CH3 )~q0-CH3 ,
3 5 -f CH2 q CF3 ,-fCF q CF3 or -f CHZ q CH3
wherein q is a positive whole number; with the proviso
that said homopolymer and copolymer includes about 10 or
2A11189
_8_
more recurring substituted or unsubstituted aniline
aromatic moieties in the polymer backbone.
Illustrative of the polyanilines useful in the
practice of this invention are those of the Formulas II to
v:
R
I2 (2 II
N N
~J y
z
~H)m
or
(I~)m ~H)m
R2
III
N N
z
~R3)n (R3)n
or
(H)m
R2
N IV
Z
~R3)n
or
~H)m R ~H)m
12
N N N V
'~'~' y -l z
~R3)n ~R3)n
~0~~~.89
-g_
wherein:
n, m,. R2, R3 and R4 are as described above;
y is an integer equal to or greater than 0;
x is an integer equal to or greater than about 1,
with the proviso that the io of x to y is greater than
rat
or equal to about 0.5; and
z, v and a are the same or different and are
integers equal to or greater than 1.
The following listing of substituted and
unsubstituted anilines are lustrative of those which can
il
be used to prepare polymers nd copolymers useful in
a
the practice of this invention.
2-Cyclohexylaniline 2-Acetylaniline
Aniline 2,5-Dimethylaniline
o-Toluidine 2,3-Dimethylaniline
4-Propanoylaniline N, N-Dimethylaniline
2-(Methylamino)aniline 4-Benzylaniline
2-(Dimethylamino)aniline 4-Aminoaniline
2-Methyl-4-methoxy- 2-Methylthiomethylaniline
carbonylaniline 4-(2,4-Dimethylphenyl)
aniline
4-Carboxyaniline 2-Ethylthioaniline
N-Methyl aniline N-Methyl 2,4-Dimethylaniline
N-Propyl aniline N-Propyl m-Toluidine
N-Hexyl aniline N-Methyl O-Cyanoaniline
m-Toluidine 2,5-Dibutylaniline
o-Ethylaniline 2,5-Dimethoxyaniline
m-Ethylaniline Tetrahydronaphthylamine
o-Ethoxyaniline o-Cyanoaniline
m-Butylaniline 2-Thiomethylaniline
m-Hexylaniline 2,5-Dichloroar~iline
m-Octylaniline 3-(n-Butanesulfonic acid)
4-Bromoaniline aniline
2-Bromoaniline 3-Propoxymethylaniline
3-Bromoaniline 2,4-Dimethoxyaniline
3-Acetamidoaniline 4-Mercaptoaniline
4-Acetamidoaniline 4-Ethylthioaniline
5 5-Chloro-2-methoxy-aniline 3-phenoxyaniline
~~1~~8
-10-
5-Chloro-2-ethoxy-aniline 4-phenoxyaniline
N-Hexyl-m=Toluidine N-Octyl m-Toluidine
4-phenylthioaniline 4-trimethylsilyaniline
3-amino-9-methylcarbazole 3-amino carbazole
4-amino carbazole N-(p-amino phenyl) aniline
Exemplary of useful R2 and R4 groups are
hydrogen, methyl, ethyl, isopropyl, butyl, isobutyl,
hexyl, octyl and the like.
IO Illustrative of useful R3 groups are hydrogen,
alkyl, such as methyl, ethyl, octyl, nonyl, tert-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; alkoxy such
as propoxy, butoxy, methoxy, isopropoxy, pentoxy, nonoxy,
ethyoxy, octoxy, and the like; cycloalkenyl such as
cyclohexenyl, cyclopentenyl and the like; alkanoyl such as
butanoyl, pentanoyl, octanoyl, ethanoyl, propanoyl and the
like; alkylsulfinyl, alkylsulfonyl, alkylthio,
arylsulfonyl, arylsulfonyl, and the like, such as
butylthio, neopentylthio, methylsulfinyl, benzylsulfinyl,
phenylsulfinyl, propylthio, octylthio, nonylsulfonyl,
octylsulfonyl, methylthio, isopropylthio, phenylsulfonyl,
methylsulfonyl, nonylthio, phenylthio, ethylthio,
benzylthio, phenethylthio, sec-butylthio, naphthylthio and
the like; alkoxycarbonyl such as methoxycarbonyl,
ethoaycarbonyl, butoxycarbonyl and the like; cycloalkyl
such as cyclohexyl, cyclopentyl, cyclo-octyl, cycloheptyl
and the like; alkoxyalkyl such as methoxy-methylene,
ethoxymethyl, butoxymethyl, propoxyethyl, pentoxybutyl
and the like; aryloxyalkyl and aryloxyaryl such as
phenoxyphenyl, phenoxymethylene and the like; and various
substituted alkyl and aryl groups such as 1-hydroxybutyl,
1-aminobutyl, 1-hydroxylpropyl, 1-hydroxypentyl,
1-hydroxyoctyl, 1-hydroxyethyl, 2-nitro-ethyl,
trifluoromethyl, 3,4-epoxy-butyl, cyanomethyl,
3-chloropropyl, 4-nitrophenyl, 3-cyanophenyl, and the
like; alkyl or aryl groups terminated with phosphonic
2on~g~
-11-
acid, phosphinic acid, sulfinate, sulfonic acid, sulfinic
acid, phosphoric acid, boric acid, or carboxylic acid
groups such as ethylsulfonic acid, propylsulfonic acid,
butylsulfonic acid, phenylsulfonic acid, and the
corresponding phosphoric acid, boric acid, sulfonic acid,
carboxylic acid, sulfinate, sulfinic acid, phosphonic
acid, and phosphinic acid.
Also illustrative of useful R3 groups are divalent
moieties derived from any two R3 groups or a R3 group
with an R1 or R2 group such as moieties of the formula:
-E-CR5=CRl-CR5=CRS~
-fC(R5)2 a
wherein a is an integer from about 3 to about 7, and b is
an integer from 1 to 2 and R5 is the same or different
at each occurrence and is hydrogen or alkyl, as for
example (CHZ)4'
(CH2)3-(CH=CH-CH=CH)-[-H2-CHCCH3)-
CH2-], (-(CCH3- and -(CH2)5, such moieties which
optionally include heteroatoms of oxygen, nitrogen, ester,
sulfonyl, carbonyl, sulfinyl, and/or sulfur such as
-CH2SCH2- -CH2NHCH2, -SCH2NHCH2-,
-O-CH2 S-CH2-, -CH2S(02)CH2-,
-CHZS(O)CH2-, -OC(O)CH2CH2, -CHZC(O)CH2 and
-CH2-O-CH2- to form heterocyclic amino compounds such
as tetrahydronaphthylamine, dihydrobenzopyrroleamine,
benzofuranamine, dihydrobenzopyranamine,
dihydrobenzofuranamine, dihydrobenzoparoxazineamine,
dihydrobenzopara-diazineamine, dihydrobenzotetrazoleamine,
dihydro-benzothiazineamine,
benzothiopyranamine, dihydro-benzoxazoleamine 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-
201119
-12-
amine, benzoimidazolylamine, benzoxazoleamine, benzo-
ixazoleamine, benzoxazolylamine, benzotriazineamine,
benzoxazineamine, naphthaleneamine, benzopyranamine,
benzothiazineamine, anthraceneamine, aminobenzothio-pyran,
aminobenzodiazine, benzethiopyrone, amino-coumarin,
benzothiophene, benzothiodiazoleamine, 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 3 to 5, with the proviso that
the sum of n and m is equal to 5;
R2 and Rl are the same or different at each
occurrence and are hydrogen, methyl or ethyl;
R3 is alkyl or alkoxy having from 1 to about 30
carbon atoms, cyano, halogen, or alkyl substituted with
phosphonic acid, phosphate, phosphoric acid, borate,
sulfonate, carboxylate, phosphonate, boric acid,
phosphinic acid, phosphinate, carboxylic acid or sulfonic
acid substituents;
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 1;
z is an integer equal to or greater than about 5;
a is an integer equal to or greater than about 3; and
v is an integer equal to or greater than about 10.
Particularly 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 2;
m is an integer from 3 to 5, with the proviso that
the sum of n and m is equal to 5;
R2 and R4 are the same or different at each
occurrence and are hydrogen or methyl;
R3 is alkyl or alkoxy having from 1 to about 20
carbon atoms, or alkyl substituted with carboxylic acid,
phosphonic acid, phosphate, phosphoric acid, borate,
~0111~9
-13-
sulfonate, carboxylate, phosphonate, or sulfonic acid
substituents;
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 2; z is
an integer equal to or greater than about 10; a is an
integer equal to or greater than about 5;
and
v is an integer equal to or greater than about 20.
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 4 to 5, with the proviso that
the sum of n and m is equal to 5;
R2.and R4 are hydrogen;
R3 is alkyl or alkoxy from 1 to about 15 carbon
atoms;
x 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 greater than about 2; and
a is an integer equal to or greater than about 6. In
the most preferred embodiments of this invention, the
polyaniline is derived from unsubstituted or alkyl
substituted aniline.
In general, the number of aniline repeat units is at
least about 10. In the 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.
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., "Aniline-
black and Allied Compounds, Part I", J. Chem. Soc., 101,
20 1 1 1 89
-14-
pp. 1117 (1912) and Kobayashi, et al., "Electrochemical
Reactions... of Polyaniline Film-Coated Electrodes",
J. Electroanal. Chem., 177, pp. 281-91 (1984). For example,
unsubstituted polyaniline, useful forms include
leucoemeraldine, proteomeraldine, emeraldine, nigraniline
and tolu-protoemeraldine forms.
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
(NH4)2S20a in excess 1M HC1. This powdered 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.
Useful forms of polyaniline 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 second essential ingredient of the thermally
stable polyaniline of this invention is a dopant solute.
The purpose of the dopant is to render polyaniline
electrically conductive. In general, such dopant solute
20 1 1 1 89
-15-
is derived from a compound, which upon addition to the
polyaniline, ionizes the polymer with co-committent
formation of a dopant solute species. Illustrative of
useful dopant species are those formed from ionization of
neutral ionic compounds, polymers or the like selected
from the group consisting of:
R1(P03)r, R1(P02)r, Rl(P03H )r
Rl(S02)r, R1(C00 )r and
Rl(BOZH )r
and having one or more cationic moieties selected from the
group consisting of:
M+n
wherein:
R1 is the same or different at each occurrence and is
a substituted or unsubstituted organic radical.
Preferably, the organic radical is selected from amino,
alkylamino, dialkylamino, arylamino, diarylamino or
alkylarylamino;
M is a species having a positive charge equal to n;
and
n and r are the same and are 1 to 8.
The R1 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, halophenyl, nitrophenyl, anthracyl, naphthyl,
phenanthryl and the like. R1 may also be a polymeric
radical such as a polymer having recurring pendant phenyl
groups in the polymeric backbone substituted with sulfonic
acid, phosphoric acid, phosphonate, phosphonic acid,
sulfinate, sulfinic acid, phosphate, carboxylate,
sulfonate, borate, phosphinate, carboxylic acid, boric
acid, or phosphonic acid moieties such as sulfonated or
phosphonated polystyrene, poly(2-methylstyrene), poly(4-
phenylstyrene), poly(a-vinyl naphthalene), polyvinyl
benzoate), poly(benzyl methaerylate) and the like. In the
particularly preferred embodiments of the invention, Rl
~~t ~~~
2D11189
-16-
is an aromatic radical and in the most preferred
embodiments R1 is 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 cation such as
Bu4N+, H+, NO+, N02, NH4 and the like,
or may be a metal cation such as Na+, Li+, Ag+,
Ba+2~ Co+3~ Al+3~ Fe+3 and the like.
The following is a listing of dopants which are
useful in the practice of this invention for formation of
the dopant solute.
1-anthracene sulfonic acid,
9-anthracene sulfonic acid,
2-phenanthracene sulfonic acid,
3-phenanthracene sulfonic acid,
9-phenanthracene sulfonic acid,
N02CF3S03,
CF3S03H,
perflouro octyl sulfonic acid
perfluoro octyl carboxylic acid
octylsulfonic acid,
dodecylsulfonic acid,
cetylsulfonic acid'
toluenesulfonic Acid (TsOH),
Fe (OT9) 3
Fe(CH3S03)3'
(FS03)2'
AgOTs'
Me3SiOTs,
dodecylbenzene sulfonic acid,
naphthalene sulfonic acid,
benzene disulfonic acid,
benzene sulfonic acid,
1,3-benzene disulfonic acid,
2,5-dihydroxy-1,4-benzene disulfonic acid,
camphor sulfinic acid
naphthalene trisulfonic acid
dodecylbenzene sulfonic acid'
~t~~~~~~
-17-
isethionic acid,
1,5-naphthalene disulfonic acid,
nickel phthalocyanine tetrasulfonic acid,
phenyl phosphonic acid,
polyvinyl sulfonic acid),
3-sulfopropyl acrylate,
3-sulfopropyl methacrylate,
sulfamic acid,
5-sulfosalicyclic acid,
tiron (4,5-dihydrogy-1,3-benzene disulfonic acid),
vinyl sulfonic acid,
sulfanilic acid,
4-sulfophthalic acid,
sulfoacetic acid,
methyl orange,
sulfonated polystyrene,
sulfonated poly(a-vinyl naphthalene),
naphthol yellow,
naphthol blue black,
1,2-naphthoquinone-4-sulfonic acid,
naphthylazoxine S,
1-octane sulfonic acid,
t-butyl phosphonic acid,
ethyl phosphonic acid,
butyl phosphonic 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-dihydroxynaphthalene-3-6-disulfonic acid,
3,6-dihydroxynaphthalene-2,7-disulfonic acid,
4,5-dihydroxynaphthalene-2,7-disulfonic acid,
~o~i~so
-18-
6,7-dihydroxy-2-naphthalene sulfonic acid,
1-naphthalene phosphoric acid,
1-naphthalene sulfonic acid,
1-naphthalene-5,7-dinitro-8-hydroxy,
1-naphthalene-4-hydroxy sulfonic acid,
4-bromo benzene sulfonic acid,
4-hydroxy-5-isopropyl-2-methyl benzene sulfonic acid
3,4-diamino benzene sulfonic acid
benzenphosphoric acid,
IO 1,3,5-benzene trisulfonic acid,
2-methyl-5-isopropyl benzene sulfonic acid,
3,4-dinitro benzene sulfonic acid,
2-methoxy benzene sulfonic acid,
1-naphthalene-5-hydroxy sulfonic acid,
1-naphthalene-7-hydroxy sulfonic acid,
1-naphthalene-3-hydroxy sulfonic acid,
2-napthalene-1-hydroxy sulfonic acid,
4-phenylamino benzene sulfonic acid,
1,6-naphthalene disulfonic acid,
1,5-naphthalene disulfonic acid,
1,3-naphthalene-7-hydroxy disulfonic acid, and
Me3SiOS02CF3.
In the preferred embodiments of the invention, useful
dopants are those
of the formula:
c
(1~102B) q (R6) a
i
Wherein:
M is a metal or non-metal cation;
c is 1, 2, 3 or 4;
d is 0, 1 or 2;
-19-
f is 0, 1 or 2;
g is 0, 1 or 2;
a is 0, 1 or 2; and
R6 is nitro, cyano, hydroxy, halogen, alkoxy,
phosphate, borate, carboxylate, substituted or
unsubstituted aryl or alkyl having from 1 to about 30
carbon atoms wherein permissible substituents include
perhaloalkyl, phenyl, alkoxy, halogen, cyano, haloalkyl,
hydroxy, sulfonic acid, phosphoric acid, boric acid,
sulfinate, sulfinic acid, carboxylic acid, nitro,
carboxylate and the like, or any two R6 substituents
together may form an alkenylene chain completing a
fused-ring system which chain may be unsubstituted or
substituted with one or more halogen, phosphoric acid,
hydroxy, boric acid, nitro, cyano, sulfinate, phosphoric
acid, sulfinic acid, phosphate, carboxylate, phosphonic
acid, phosphonate, sulfonate,borate, sulfonic acid or
carboxylic acid groups, or R6 is a moiety of the formula:
--ECH2 qCF3 ,--ECF2 qCF3 ,--ECH2 q CH3
--EOCH2CHZ~OCH3 or--~OCHZCH(CH3)~ OCH3
wherein:
q is a positive whole number from 1 to about 10; and
In the particularly preferred embodiment of this
invention useful dopants are those of the above formula
wherein:
c is 1, 2 or 3;
d is 0 or 1;
f is 0 or 1;
g is 0 or 1;
a is 0, 1 or 2; and
R6 is substituted or unsubstituted phenyl or alkyl
wherein permissible substituents are selected from the
group consisting of alkyl, halogen, hydroxy, phenyl,
haloalkyl, perhaloalkyl, cyano, vitro, alkoxy, boric acid,
borate, phosphonate, phosphonic acid, carboxylate,
sulfonate, phosphate, sulfonic acid, carboxylic acid,
2011189
-20-
phosphoric acid, sulfinic acid or sulfinate or any two
R6 substituents together may form an alkylene chain
completing a naphthalene, anthracene or phenanthracene
fused ring system or R5 is a moiety of the formula:
--EOCH2CH2-~-qOCH3 o r --EOCHZCH ( CH3 ) q OCH3
wherein:
q is a positive whole number from 1 to about 10; and
M is H+, NO+, N02, Fe(III), Pb(IV), Ce(IV),
A1(III), Sr(IV), Cr(VI), Mn(VII), Co(III), Au(III),
Os(VIII), Na(I), Li(I), K(I) or Bu4N(I).
In the particularly preferred embodiments of this
invention:
c is 1, 2 or 3;
d, f and g are 0;
a is 0, 1 or 2; and
R6 is alkyl, phenyl, alkyl substituted with one or
more fluoro, sulfonic acid, sulfonate, carboxylate,
hydroxy, nitro, cyano, or carboxylic acid groups, or
phenyl substituted with one or more alkyl, fluoroalkyl,
sulfonic acid, sulfonate, carboxylate, hydroxy, nitro,
cyano, or carboxylic groups; and
M is H+
The amount of dopant added to the polyaniline is not
critical and may vary widely. In general, sufficient
dopant is added to the polyaniline to at least form doped
polymer which is a semi-conductor which is a conductivity
of at least about 10 6 ohmlcml. The upper level of
conductivity is not critical and will usually depend on
the type of aniline polymer employed. In genera)_, the
highest level of conductivity obtained is provided without
unduly adversely affecting the environmental stability of
the polymer. In the preferred embodiments of the
invention the amount of dopant employed is sufficient to
provide a conductivity of at least about
10 4ohm lcm 1 and in the particularly preferred
embodiments is sufficient to provide a conductivity of
CA 02011189 2000-04-20
._
-21-
from about 10 'ohm lcm 1 to about
10+2ohm lcm 1. Amongst these particularly preferred
embodiments, most preferred are those embodiments in which
unsubstituted polyaniline is employed and in which
sufficient dopant is employed to provide a conductivity of
at least about 10 lohm lcm to about 10+2ohm lcm 1
with amounts sufficient to provide a conductivity from
about 100ohm lc:m 1 to about 10+2ohm lcm 1
usually being i:he amounts of choice.
IO The method of forming the thermally stable
electrically conductive polyaniline is not critical and
may vary widel~r. Suitable techniques are those described
in U.S. Patent Nos. 4,442,187 and 4,321,114. Such
processes include the direct chemical polymerization of
molecules of Formula 1 in the presence of chemical species
as LR1(S03)~2M~F1, LR1(OPO~ir)M+1~
[R1(H02)r]M , R1(B02H )M and/or
[R1(P03)r)M+2. Also such process include
electrochemical doping of neutral polyaniline as described
in U.S. Patent No. 4,321,114. Another process is
electrochemical polymerization of aniline and its
derivatives as described in Formula I in the presence of
[R1S03-]n M+n ;are described in Kobayashi,
Tetsuhiko, et .al., ~. Electroanal. Chem., "Electrochemical
Reactions Concerned with Electrochromism of Polyaniline
Film-Coated Electrodes", Z1, pp. 28-29 (1984). Yet
another process of forming the polyaniline of this
invention involves the exchange of non-thermally stable
dopants in pol;yaniline with a suitable dopant solute such
as R1(S03)r, Rl (OP02)r and/or R1
(OPOH-)r. For example, in this process polyaniline
can be doped by contacting same with a solution containing
excess of a compound which ionizes in solution into a
suitable dopant such as R1(S03+~ M+r~
R1(OPOi)rM+2r and Rl(OPOH )r.M
Another aspect of this invention relates to a
composition comprising one or more thermally stable doped
electrically conductive polyanilines of this invention,
20 1 1 1 89
-22-
and one or more thermoplastic, solution processible or
thermoset polymers. One advantage of this composition is
that because of the thermal stability of the polyanilines,
articles can be fabricated from these compositions using
conventional melt or heat processing techniques. Also,
composites of these polyanilines can be used at
temperatures much higher then heretofore available to
conductive polyanilines. The proportion of polyaniline to
thermoplastic or thermoset polymer is not critical and may
vary widely, depending on the uses of the composition.
For example, for those uses which require the composite
having higher conductivities, i.e., up to or greater than
about 100ohM lcm 1 the amount of electrically
conductive polyaniline will tend to be relatively high, as
for example up to and greater than about 10 weight
percent, based on the total weight of the composition.
Conversely, for those uses in which lower conductivities
are required, i.e., down to or less than about
10 6ohmlcm 1, the amount of electrically conductive
polyaniline will tend to be relatively low, down to or
less than about 5 weight percent based on the total weight
of the composition. In the preferred embodiments of the
invention, the amount of electrically conductive
polyaniline is from about 1 to about 60 weight percent
based on the total weight of the composition, and in the
particularly preferred embodiments of the invention the
amount of conductive polyaniline is from about 5 to about
40 weight percent on the aforementioned basis. Amongst
these particularly preferred embodiments most preferred
are those embodiments in which the composition comprises
from about 5 to about 35 weight percent of the
electrically conductive polyaniline based on the total
weight of the composition.
Thermoset polymers for use in the practice of this
invention may vary widely. Illustrative of such useful
thermoset polymers are alkyls derived from the
esterification of a polybasic acid such as phthalic acid
and a polyhydric alcohol such as glycol; allylics such as
-23-
those produced by polymerization of diallyl phthalate,
diallyl isophthalate, diallyl maleate, and diallyl
chlorendate; amino resins such as those produced by
addition reaction between formaldehyde and such compounds
as melamine, urea, aniline, ethylene urea, sulfonamide and
dicyandiamide; epoxies such as epoxy phenol novolak
resins, diglycidyl ethers of bisphenol A and
cycloaliphatic epoxies; phenolics such as resins derived
from reaction of substituted and unsubstituted phenols
IO such as cresol and phenol with an aldehyde such as
formaldehyde and acetaldehyde; polyesters; silicones; and
urethanes formed by reaction of a polyisocyanate such as
2,6-tolylene disocyanate, 2,4-tolylene disocyanate, 4,4,-
diphenylmethane disoeyanate, 1,6-hexamethylene disoryanate
and 4,4'-dieyclohexylmethane disocyanate with a polyol
such as polyether polyol (trimethylol propane,
1,2,6-heaanetriol, 2-methyl glycoside, pentaerythitol,
poly(1,4-tetramethylene ether) glycol, sorbitol and
sucrose), polyester polyols such as those prepared by
detect esterification of adipic acid, phthalic acid and
like carboxylic acids with an excess of difunctional
alcohols such as ethylene glycol, diethylene glycol,
propanediols and butanediols.
Thermoplastic polymers for use in the formulation of
the composition of this invention may vary widely.
Illustrative of such polymers are polyesters such as
poly(glycolic acid), polyethylene succinate),
polyethylene adipate), poly(tetramethylene adipate),
polyethylene azelate), polyethylene sebacate),
poly(decamethylene adipate), poly(decamethylene sebacate),
poly (a,a-dimethylpropiolactone), poly(pivaloyl fact«ne),
poly(para-hydroxybenzoate), polyethylene oxybenzoate),
polyethylene isophthalate), polyethylene terephthalate),
poly(decamethylene terephthalate), poly(hexamethylene
terephthalate), poly(1,4-cyclohexane dimethylene
terephthalate), polyethylene-1,5-naphthalate),
poly(ethylene-2,6-naphathalate), poly(1,4-cyclohexylidene
dimethylene-teraphthalate) and the like; polyamides such
2011189
-24-
as poly(4-aminobutyric acid) (nylon 4), poly(6-amino-
hexanoic acid) (nylon 6), poly(7-aminoheptanoic acid)
(nylon 7), poly(8-aminooctanoic acid) (nylon 8),
poly(9-aminononanoic acid) (nylon 9), poly(10-amino-
decanoic acid) (nylon 10), poly(11-aminoundecanoic acid)
(nylon 11), poly(12-aminododecanoic acid) (nylon 12), poly
(hexamethylene adipamide) (nylon 6,6), poly(heptamethylene
pimelamide) (nylon 7,7), poly(octamethylene suberamide)
(nylon 8,8), poly(hexamethylene sebacamide), (nylon 6,10),
poly(nonamethylene azelamide) (nylon 9,9), poly(deca-
methylene azelamide) (nylon 10,9), poly(decamethylene
sebacamide) (nylon 10,10), poly[bis(4-aminoeyclohexyl)-
methane-1,10-decanedicarboxamide] (Quiana)(trans),
poly(m-xylene adipamide), polyp-xylene sebacamide),
poly(2,2,2-trimethylhexamethylene terephthalamide),
poly(piperazine sebacamide), poly(metaphenylene
isophthalamide) (Nomex)* polyp-phenylene terephthalamide)
(Kevlarj, and the like; polycarbonates such as
poly[methane bis(4-phenyl)carbonate], poly[1,1-ethane
bis(4-phenyl)carbonate], poly[2,2-propane bis(4-
phenyl)carbonatel, poly[1,1-butane bis(4-phenyl)
carbonate], poly[1,1-(2-methyl propane)bis(4-phenyl)
carbonatel, poly[2,2-butane bis(4-phenyl)carbonate],
poly[2,2-pentane bis(4-phenyl)carbonate], poly[4,4-heptane
bis(4-phenyl)carbonate], poly [1,1-(1-phenyl-
ethane)bis(4-phenyl)carbonate], poly[diphenylmethane
bis(4-phenyl)carbonate], poly[1,1-cyclopentane bis(4-
phenyl)carbonatel, poly[1,1-cyclohexane bis(4-phenyl)
carbonate], poly[thio bis(4-phenyl)carbonate], poly
[2,2-propane bis-[4-(2-methyl phenyl)]carbonate], poly .
[2,2-propane bis-[4-(2-chlorophenyl)]carbonate],
poly [2,2-propane bis-[4-(2,6-dichlorophenyl))carbonate],
poly[2,2-propane bis-[4-(2,6-dibromophenyl)]carbonate],
poly[1,1-eyclohexane bis-[4-(2,6-dichloro phenyl)]-
carbonate], and the like; polymers derived from the
polymerization of a,s-unsaturated monomers such as
polyethylene, acrylonitrile/butadiene/styrene terpolymer,
polypropylene, poly(1-butene), poly(3-methyl-1-butene),
*Trademark
20 1 1 1 89
-25-
poly(1-pentene), poly(4-methyl-1-pentene), poly(1-hexene),
poly(5-methyl-1-hexene), poly(1-octadecene),
polyisobutylene, poly(isoprene), 1,2-poly(1,3-butadiene)
(iso), 1,2-poly(1,3-buta-diene) (syndio), polystyrene,
poly(a-methylstyrene), poly(2-methylstyrene), poly(4-
methylstyrene), poly(4-methoxystyrene), poly(4-
phenylstyrene), poly(3-phenyl-1-propene), poly(2-
chlorostyrene), poly(4-chlorostyrene), polyvinyl
fluoride), polyvinyl chloride), polyvinyl bromide),
poly(vinylidene fluoride), poly(vinylidene chloride),
poly(tetrafluoroethylene) (Teflon ), poly(chlorotri-
fluoroethylene), poly(vinylcyclopentane),
poly(vinylcyclohexane), poly (-vinylnaphthalene),
polyvinyl alcohol), polyvinyl methyl ether),
polyvinyl ethyl ether), polyvinyl propyl ether),
polyvinyl isopropyl ether), polyvinyl butyl ether),
polyvinyl isobutyl ether), polyvinyl sec.-butyl ether),
polyvinyl tert.-butyl ether), polyvinyl hexyl ether),
polyvinyl octyl ether), polyvinyl methyl ketone),
poly(methyl isopropenylketone), polyvinyl formate),
polyvinyl acetate), polyvinyl propionate), polyvinyl
chloroacetate), poly (vinyltrifluoroacetate), polyvinyl
benzoate), poly(2-vinylpyridine), poly(vinylpyrolidone),
polyvinyl-carbazole), poly(acrylic acid), poly(methyl
acrylate), poly(ethyl acrylate), poly(propyl acrylate),
poly(iso-propyl acrylate), poly(butyl acrylate),
poly(isobutyl acrylate), poly(sec.-butyl acrylate),
poly(tert.-butyl acrylate), poly(methaerylic acid),
poly(methyl methacrylate), poly(ethyl methacrylate),
poly(propyl methacrylate), poly(isopropyl methacrylate),
poly(butyl methacrylate), poly(isobutyl methacryJ_ate),
poly(sec.-butyl methacrylate), poly(tert.-vutyl
methacrylate), poly(2-ethylbutyl methacrylate), poly(hexyl
methacrylate), poly(octyl methacrylate), poly(dodecyl
methacrylate), poly(octadecyl methacrylate), poly(phenyl
methacrylate), poly(benzyl methacrylate), poly(cyclo-
hexyl methacrylate), poly(methyl chloroacrylate), poly-
aerylonitrile, polymethacrylonitrile, polyacrylamide,
*Trademark
w_ ~ 20 1 1 1 89
-26-
poly(N-isopropylacrylamide), and the like; polydienes such
as poly(1,3-butadiene) (cis), poly(1,3-butadiene)
(trans), poly(1,3-butadiene) (mixt.), poly(1,3-penta-
diene) (trans), poly(2-methyl-1,3-butadiene) (cis), poly
(2-methyl-1,3-butadiene) (trans), poly(2-methyl-1,3-
butadiene) (mixt.), poly(2-tert.-butyl-1,3-butadiene)
(cis), poly(2-chloro-1,3-butadiene) (trans), poly(2-
chloro-1,3-butadiene) (mixt.) and the like; polyoxides
such as poly(methylene oxide), polyethylene oxide),
poly(tetra-methylene oxide), polyethylene formal),
poly(tetra-methylene formal), polyacetaldehyde, poly
(propylene oxide), poly(hexene oxide), poly(octene oxide),
poly(trans-2-butene oxide), polystyrene oxide),
poly(3-methoxypropylene oxide), poly(3-butoxypropylene
oxide), poly(3-hexoxypropylene oxide), poly(3-phenoxy-
propylene oxide), poly(3-chloropropylene oxide), poly
[2,2-bis(chloromethyl)-trimethylene-3-oxide] (penton),
poly(2,6-dimethyl-1,4-phenylene oxide) (PPO), poly(2,6-
diphenyl-1,4-phenylene oxide) (Texax, P30), and the like;
polysulphides such as polypropylene sulphide), poly
(phenylene sulphide) and the like; polysulfones such as
poly[4,4'-isopropylidene diphenoxy di(4-phenylene)
sulphonel; noryl, and the like, and/or mixtures thereof.
The composition of this invention may include various
optional components such as plasticizers, blending aids,
colorants, flame-retardants and the like, or components
which either fill or form a substrate for the composition
to be cast from the melt or solution. These other
components may vary widely and may include any material
known for use in conventional polymer compositions.
Illustrative of such other components are such materials
as carbons, metal conductors, reinforcing fibers, inert
fillers, glass beads, clays, other conductive and
non-conductive polymers, conductive ceramics, super-
conductive ceramics, and the like.
The composition of this invention can be prepared
using conventional techniques as for example conventional
melt or solution blending techniques. For example, such
*Trademark
201~1~9
-27-
compositions can be formed by heating and mixing a mixture
of the various components to a temperature which is equal
to or greater than the melting point or flow point of at
least one of the polymer components to form a molten
intimate mixture to which optional components may be added
as desired. Thereafter the mixture can be formed into a
desired article through use of any conventional shape
forming technique. For example, the molten mixture can be
spread on a surface and allowed to cool forming free
standing films or films coating other substitutes. The
molten mixture can be extruded through a die to form films
or fibers, or injection molded into a suitable mold to
form molded parts having the shape of the mold. The
manner in which the molten mixture is formed is not
critical and conventional methods can be employed. For
example, the molten mixture can be formed through use
of conventional polymer and additive blending means, in
which the polymeric components are heated to a temperature
equal to or greater than the melting point of a least one
of the polymerrs, and below the degradation temperature of
each of the polymers. Ultrasonication can be used to
improve dispersion of the non-soluble phases. The desired
amount of the optional ingredients in a liquid or powdered
form is added to the melted polymers while at the same
time vigorosly agitating the melt as for example by
stirring or irradiating with ultrasound, or added prior to
melting and mixing.
In a solution process for the preparation of the
composition of this invention a solution of the desired
host polymer in a suitable solvent with a or without a
dopant solute is formed. The desired optional components
in the desired amounts may be dissolved or dispersed in
the solution. The dissolved and/or dispersed polymers can
be solidified into a desired shape by removal of the
solvent through use of conventional techniques. For
example, by removal of the solvent from a solution spread
on a surface films can be formed of any desired
thickness. By extruding the solution through a die,
2p~~.~~9
-28-
fibers and films can be made. Similarly, by removing the
solvent from the solution in a mold, shaped articles
conforming in shape to the mold can be prepared. If the
original solution did not include a suitable dopant, the
shaped article can be exposed to a suitable dopant to dope
the polyaniline. In the preferred embodiments of the
invention, however, doped polyaniline is used to form the
solution.
In the most preferred embodiment, the components of
IO the intimate mixture can be granulated, and the gran-
ulated components mined dry in a suitable mixer, as for
example using ultrasonication or a tumbler or a Branbury
Mixer, or the like, as uniformly as possible. Thereafter,
the composition is heated and further mixed in an extruder
when at least one of the polymers components is melted.
As described above, the fluid mixture is thereafter
ejected with cooling.
The order of mixing of the various components of the
intimate mixture may not be critical. Accordingly, the
order of addition of the polymers and other optional
components to be desired in more detail hereinbelow, to
form the initmate mizture can be varied as desired.
The electrically conductive polyaniline of the
invention, and the composition of this invention can be
used for any purpose for which conductive polymers are
useful. 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
electrical conducting connectors, conductive bearings,
brushes and semiconducting photoconductor iuncti«ns,
electrodes, capacitors, optically transparent or non-
transparent corrosion-preventing coatings for corrodible
materials such as steel, antistatic materials and
optically transparent or non-transparent coatings for
packaging electronic components, carpet fibers, waxes for
floors in computer rooms, antistatic finishes for CRT
- CA 02011189 2000-04-20
-29-
screens, aircraft, auto windows, electrostatice disapative
packaging for electronics, and the like.
The following specific examples are presented to more
particularly illustrate the invention, and should not be
construed as being limitations on the scope and spirit of
the invention.
TO preparation of Poly(aniline hydrogen chloride)
Aniline, (10 ml, O.llm); concentrated hydrochloric
acid, (33.76 ml., 0.35 m); thirty percent hydrogen
peroxide, (12.5 ml., 0.11 m); and ferrous sulfate
l5 heptahydrate (100 mg.) together in 400 ml. deionized
water. The reactants were cooled overnight without
stirring at 4°C.
The resulting finely precipitated solids were
filtered, washed twice with 100 ml. deionized water, then
20 air dried 16 hours. The conductivity of a pressed pellet
1 cm. in diameter was 10.2 S/cm as measured by a
four-point probe conductivity apparatus. Thermogravimetric
analysis (TGA) from 30 to 700°C under argon at a heating
rate of l.OaC/minute was performed using a Perkin-Elmer
25 TGS-2. Significant weight loss was noted beginning at
room temperature up to 125°C with a gecond major weight
loss step occurring at 175°C (See Fig. 1).
Preparation of Poly(aniline 1.5-Naphthalenedisulfonate)
A suspension of 50 ml. aniline (0.538 m) and 273 g.
1,5-naphthalenedisulfonic acid. tetrahydrate (0.758 ) in
2250 ml. deionized water was cooled to 1.4°C. A solution
of 163 g. ammonium persulfate (0.714 m) in 400 ml water
was added all at once.
20 1 1 1 89
-30
The reaction was slow to initiate, taking an hour
overall. It reached a maximum temperature of 24°C and a
maximum potential of 0.745 volts as measured using a
platinum electcode vs a Ag/AgCl reference electrode
connected to a Keithley~168 digital multimeter. As the
reaction neared completion, the potential fell to 0.5
volts. The color of the solution was blue/black; and
the solution was full of suspended solids. After stirring
for an additional 30 minutes, the reaction mixture was
filtered, and the filter cake washed 4 times with 200 ml
portions of water at 50°C.
The semi-dry cake was resuspended in one liter of
water containing 12 g. dissolved 1,5-naphthalenedi-
sulfonic acid, tetrahydrate. After stirring 30 minutes
the acid solution was filtered and the filter cake washed
2 times with 300 ml portions of water at 50°C and 5 times
with 200 ml portions of methanol at 20°C.
The solids were added to one liter of methanol
containing 11,5-naphthalenedisulfonic acid tetrahydrate
(12g) and stirred 30 minutes. After filtering, the
filter cake was washed 3 times with 200 ml portions of
methanol. The solids were dried in air overnight and
then under vacuum (0.1 mm Hg) 80°C at for three hours.
A pressed pellet of this dark blue-green powder
exhibited a conductivity of 0.21 S/cm. The TGA in argon
shows that weight loss begins at temperatures slightly
above 275°C. (See Fig. 2)
EXAMPLE 3
preparation of Poly(aniline p-toluene sulfonate>
Two separate solutions were prepared. Solution A
contains aniline (155 g, 1.67 m) and methanesulfonic
acid (241 g, 2.5 m) in 1.67 liters of deionized water.
Solution B contains ammonium persulfate (571 g 2.5 m)
dissolved in 1.67 liters of deionized water.
*Trademark
2011189
-31-
Solution B was added to solution A with stirring at a
rate sufficient to maintain the temperature of the
reaction mixture below 50°C. The suspension was stirred
overnight. The solids were collected by filtration and
were washed with 3.7 liters of water at 50°C. The solids
were resuspended in 6.2 liters of water. To the
suspension was added 300 ml. of concentrated ammonium
hydroxide was added with stirring to neutralize the
polymer. After 30 minutes the solids were collected by
filtration and washed with 3.7 liters of water at 50°C.
The neutral polymer was resuspended in 3.1 liters of water
containing 310 g of p-toluene-sulfonic acid. The re-doped
polymer slurry was stirred for three hours, filtered and
washed with 500 ml of methanol.
After drying under vacuum overnight at 80°C, the
powder was measured for conductivity as in Example 1,
which was found to be 0.25 S/cm. TGA in argon inicates
little weight loss occurs below 260°C. (See Fig. 3)
EXAMPLE 4
Aniline (50 ml, 0.5367 m) and p-toluene sulfonic
acid, (144 g., 0.758 m) were charged into a 4 liter beaker
containing 2250 ml deionized water at 30°C. The potential
of the reactants were monitored by immersion of a platinum
wire and a reference Ag/AgCl electrode. Ammonium
persulfate (123 g., 0.539 m) dissolved in 300 ml water was
added all at once. As the reaction progressed, the
temperature reached 46°C and the potential went as high as
0.74 volts.
Fifteen minutes after the reaction potential peaked
and fell, a further 40 g. of ammonium persulfate (0.175 m)
dissolved in 100 ml water was added dropwise at a rate
which maintained the reaction mixture at a steady
potential of 0.62 volts.
-32
The suspension was filtered and the filter cake
washed under suction with six times with 200 ml portions
of deionized water. The solids were then resuspended in
one liter of water containing 20 g. of p-toluene-
sulfonic acid and stirred at room temperature for one
hour. After filtration, the filter cake was again washed
under suction six times with 200 ml portions of 2% p-
toluenesulfonic and stirred for 30 minutes. This slurry
was filtered and the filter cake washed three times with
200 ml of acetone.
The solids were dried overnight at room temperature.
under vacuum, then two hours at 80'C under vacuum. Pellets
pressed from this dry powder and measured as in Example 1
had conductivities of at least 1.0 S/cm. The TGA of this
material, as run by the method in Example 1, shows that
major weight loss occurs only at temperatures above 225'C.
(See Fig. 4)
Aniline (1.7 g.) was added to 9.0 g. of decylbenzene-
sulfonic acid (1.5 equivalents based on aniline) dissolved
in 50 ml. of deionized water at room temperature. To this
creamy mixture was added 6.3 g. of ammonium persulfate
(1.5 equivalents based on aniline) all at once.
After 30 minutes a smooth blue/green suspension
formed. The solids were filtered, washed 3 times with 50
ml. portions of water, and then air dried. The solids
were tested for conductivity as in Example 1.
Conductivity of the pellet was 0.19 S/cm. A TGA of the
material run under the parameters of Example 1 shows that
major weight loss only begins at temperatures above 225~C.
(See Fig. 5)
~0~~~~9
-33
EXAMPLE 6
PrPgaration of Poly(aniline hydrogen sulfate' 1 3
benzenedisulfonatP,~
Aniline (50 g. 0.5365 m) and 1,3-benzenedisulfonic
acid disodium salt (95.1 g. 0.337 m) were charged into
2250 ml.) water in a 4L beaker at ambient temperature.
The reaction potential was monitored as in Example 2.
Ammonium persulfate (157 g. 0.688m) was added all at
once. The reaction had induction period of twenty
minutes. Once underway, the reaction proceeded quickly
0
(3-4 minutes). The temperature rose to a maximum of 46 C
and the potential peaked at 0.735 volts. The reactants
were stirred overnight at room temperature.
After filtration, the solids were resuspended in 1.3
liters of deionized water containing 5% sulfuric acid and
1.67% 1,3-benzenedisulfonic acid disodium salt and the
suspension stirred for 30 minutes. The solids were
collected by filtration and resuspended in one liter of
water containing 3% sulfuric acid and 1% 1,3- benzenedi-
sulfonic acid, disodium salt. After stirring for an hour,
this suspension in turn was filtered and the solids were
added to a liter of water containing 1% sulfuric acid and
0.5% 1,3-benzenedisulfonic acid, disodium salt. The
solids were stirred and then collected by filtration.
The solids were air dried overnight, then heated
0
under vacuum (0.1 mm Hg) at 80 C for two hours.
Conductivity of a pellet measured as described in Example
1 was 1.57 s/cm. The TGA shows that major weight loss
0
does not occur at temperature below 200 C. (S°e Fig. 6)
EXAMPLE 7
Pre»aration of Poly(aniline sulfamate~
Poly(aniline/hydrogen chloride) from Example 1 was
suspended in water and neutralized with an excess of
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ammonium hydroxide as in Example 3. The neutral poly-
aniline was washed with water and dried under vacuum.
Neutral polyaniline, (2g) Was added to 100 ml of
deionized water in a 600 ml beaker. Sulfamic acid 9.7 g.
0.1 m) was added with stirring. The contents were allowed
to mix overnight at room temperature. The solids were
then filtered, and washed as in Example 6 using the
following sulfamic acid solutions: a 5% aqueous sulfamic
acid solution, a 3% aqueous sulfamic acid solution, and a
1% aqueous sulfamic acid solution. The solids were then
washed with 2 X 50 ml portions of methanol, and dried
under vacuum at 80'C for 2 hours.
Conductivity of a pressed pellet was 0.835/cm. The
TGA shows that no major weight loss occurs below 200~C.
(See Fig. 7)
EXAMPLE $
Preparation of Thermally Stable Conductive Polyaniline
Containing p-Toluenesulfonate Anion as Dopant
To 0.05 mole of p-toluene sulfonic acid hydrate in
100 mL of water was added 0.05 mole of aniline. To this
solution at 0'C was then added 0.075 mole of ammonium
persulfate in 20 mL of water. After stirring for 20 min.,
the yellow solution was allowed to warm to room
temperature and stirring Was continued for another 16 hr.
The green precipitate Was filtered, washed twice with a
O.1M p-toluenesulfonic acid solution in water, three times
with water, then twice with methanol, then air dried.
Yield was 2.6g. A compacted-powder pellet, 10 12.7mm
diameter by lmm thick, exhibited a 4-probe conductivity of
0.7 s/cm (ohm-lcm 1). Elemental analysis gave
64.03%C, 5.42%H, 9.43%N, 7.44%S, and 12.02%O. Empirical
formula: C6H4N1 (OTs)0.27(HS04)0.07
(OTS=p-toluenesulfonic acid). Thermogravimetric analysis
0
(TGA) under argon shows only a 2% wt loss up to 300 C and
.. 201119
-35-
a 5% wt loss up to 400°C. Major weight loss begins at
425°C with 55% of the original weight remaining at 700°C.
~~paration of p-Toluenesulfonate Doped Polyaniline by
Treatment of the Emeraldine Base Form of polyaniline
with p-Toluenesulfonic Acid
IO To 50mL of a 1M p-toluenesulfonic acid solution in
water was added l.Og of the Emeraldine base form of
powdered polyaniline. The suspension was stirred for 1
hour at room temperature, filtered, washed twice with 1M
p-toluenesulfonic acid, twice with water (25mL), then
twice with methanol, and air dried. A compacted-powder
pellet 12.7mm dia. x 1 mm thick gave four-probe
conductivity of 0.5 s/m. TGA analysis on this material
showed similar weight loss behavior to that of material
prepared as in Example 8.
~gparation of ~-Toluenesulfonate Doped Polyaniline
~y Exchange of Dopant Ion in Polya~ilin~~ydr2~hloride
with p-Toluene Sulfonate Anion
To 50 mL of 1M p-toluene sulfonic acid solution in
water was added l.Og of polyaniline hydrochloride
(original conductivity of 5 S/cm). The suspension
was stirred for one day at room temperature, filtered and
the solid was washed with 1M toluene sulfonic acid
solution then water and air-dried. A compacted pellet
exhibited a 4-probe conductivity of 0.5 S/cm. TGA
analysis show similar weight loss behavior as that of
sample from Example 9.
..
-36
EXAMPLE 11
(A) Preparation of Polyaniline Chloride
Into a one liter erlenmeyer flask equipped with a
magnetic stirring bar was placed 750 mL of 1M HC1 and 29g
of distilled aniline. After the aniline dissolved, a
solution of 35.6g of ammonium persulfate in 80 mL of water
was added with cooling. After three hours at room
temperature, the dark solids were filtered, washed three
times with mL of 1M HC1, twice with 200 mL water, and once
with 200 mL of methanol. The solids were air dried to
give 13g of polyaniline chloride. A pressed pellet 7 mm
diameter by 1 mm thickness exhibited a 4-point probe
conductivity of 10.2 S/cm.
(B) Thermal Studies on Polyaniline Chloride
One gram of the above polyaniline chloride with a
conductivity of 10.2 S/cm was heated to 100°C under vacuum
for 2 hours. The sample lost 14% of its weight and its
conductivity (pressed pellet, 4-point probe) dropped to
0.7 s/cm.
Another 1 gram sample was heated to 200°C under
vacuum for 2 hours. This sample lost 24% of its weight
and its conductivity (pressed pellet, 4-point probe
dropped to 7 X 10 7 S/cm.
COMPARATIVE EXAMPLE I
Thermog~metric Analyses (TGA of
~y~niline Chloride and Polyaniline Tosylate
An experiment was carried out to compare the thermal
stability of the thermally stable polyaniline of this
invention and conventional doped polyaniline. The
polyaniline of this invention was doped with tosylate
anions and was prepared as described in EXAMPLE I. The
~~1118~
-37-
conventional polyaniline was doped with chloride anions
and was prepared as in Comparative Example I.
Samples of polyaniline chloride and polyaniline
tosylate were analyzed by TGA under argon to determine
their stability to weight loss (dopant loss). The results
of this experiment are set forth in Figs 1, 8 and 9. At a
10°C/min heating rate, the sample of polyaniline chloride
exhibited two weight-loss steps, one between room
temperature and 100°C (11% wt loss) and the other between
125°C and 300°C (dopant loss) (14% wt loss). (See Fig. 8)
Subjecting a sample of polyaniline tosylate to the same
analysis showed that it did not loose any weight up to
300 °C. (See Fig. 9)
20
30
