Note: Descriptions are shown in the official language in which they were submitted.
ELECTROAC~IV~ POLYMERS
BACKGR0UND OE' THE INVENTION
This invention relates to electroactive organic poly-
meric materials. More specifically, this invention relates to
incorporating electroactiva~ing agents known in the art as
dopants.
~ ecently, research has been conducted into organic
polymeric materials in order to modify their room temperature
electrical conductivity by reacting them with electron donor or
acceptor molecules. The electron donor or acceptor molecules,
generally known in the art as n- and p-type dopants respective-
ly, can transform the organic polymeric materials so that these
modified organic polymeric materials exhibit semiconducting and
metallic room temperature electrical conductivity. Polyacety-
lene is an example of an organic polymeric ma~erial whose room
temperature electrical conductivity can be modiied over
several orders of magnitude above i-ts insulator state, by the
incorporation of ~opant molecules, A. J. Heeger et al, U.~.
patent 4,222,903. Other examples of organic polymeric mater-
ials whose room temperature electrical conductivi-ty can be
enhanced by several orders oE magnitude over their insulator
state by means of incorporation of dopant molecules are poly-p-
phenylene, polypyrrole, poly-1,6 heptadiyne, and polyphenylene
vinylene. However, all of the above recited examples are of
organic polymeric materials which are completely insoluble or
infusable and hence are completely intractable.
Other examples of organic polymers whose room temp-
erature electrical conductivity can be modified with the aid of
dopants are polyphenylene sulEide and poly-m-phenylene. How-
ever, -the above recited ma-terials -though being trac-table in
their original virgin state, undergo irreversible chemistry
when reacted with dopants which modi:Ey their room temperature
electrical conductivity. This irreversible chemistry imparts
upon these dopan-t
- la -
,r
01
--2--
modified organic polymeric materials a state of intract~
ability. Upon removal of the doping agents, these mate-
05 rials do not revert to the chemical structure which they
oriyinally exhibited prior to being modified by the
dopants. The inorganic material polysulfur nitride is
also considered a polymeric conduc-tor. As with the pre-
viously recited polymeric materials, polysulfur nitride is
also completely intractable.
For use in a wide variety of electronic device
applications, it is highly desirable to have available
organic polymeric electrically conducting materials having
a preselected room temperature conductivity which can be
varied over a broad range~ This range should preferably
extend from the insulator state of the unmodified organic
polymeric material through the semiconducting regime and
extending into the highly conducting metallic state~ It
is also desirable that these organic polyme~ic electric-
ally conducting materials should be tractable and hence
processable so that use~ul articles of any desired shape
and size can be fabricated. Tractable organic polymers
are those which can be readily shaped, formed, molded,
pressed, cast, etc., into desired articles from the liquid
state, i.e. either from the melt, fluid glassy state, or
from solution after the completion of the polymerization
reaction of the organic polymeric material.
SUMMARY OF THE lNv~NlION
I have invented an electroactive polymeric mate-
rial comprising a dopant modified organic polymer whose
room temperature electrical conductivity is controlled in
a highly selective and reversible manner. Electroactive
polymer is defined as a polymer having a conductivity
which has been modified with electron acceptor or donor
dopants to be greater than the conductivity of the virgin
state of the polymer. The electroactive organic polymeric
material is fabricated from a virgin polymer, which in
itself is completely tractable and processable and which
exhibits excellent mechanical and thermal properties as
well as being highly stable to oxidative degradation, by
3~
-- 3 --
modi~ying the polymer with a concluctivity modifier, i.e. elec-
tron donor dopants or electron acceptor dopants. l'he electro-
active org~nic polymeric material is comprised of recurring
units of a fused nitrogen-containing unsa-turated heterocyclic
ring system and a conductivity modifier. More specifically,
the electroactive polymer i5 a charged, either posi-tive or
negative, polymer backbone incorporating charge-compensating
ionic dopants, i.e. ions oE opposite charge to the charge o-f
the polymer backbone~ The recurring units are diradicals. ~he
diradicals are directly linked to one another, or may be con-
nected to one another via connecting units. A connec~ing unit
i5 defined as any a-tom or group of atoms which can link the
hereinabove diradicals together into a polymer chain.
Thus in its broadest aspect this invention provides a
tractable electroactive polymer comprising a linear charged
polymer backbone and charge compensating ionic dopant~s) asso-
ciated therewith wherein said linear polymer backbone is
capable of undergoing reversible oxidation or reversible reduc-
tion, or both, to form said linear charged polymer backbone,
said linear polymer backbone comprising diradical repeat units
selected from the following group: (a) fused nitrogen-con-
taining unsaturated heterocyclic ring systems, (b) fused nitro-
gen-containing unsaturated heterocyclic ring systems inter-
spersed with connecting units' and tc) mixtures of (a) and
(b)-
Preferably, in these polymers in the fused ni-trogen-
containing ring systems not more than two nitrogen atoms are
joined sequentially.
Further, it is preferred that in these polymers in
the nitrogen-containing ring system the atoms at the ring
.~,. ~,
, ~
- 3a ~
fusion points are other than nitrogen.
An n-~ype electroactive organic polymer is obtained
by reacting the virgin polymer with reducing or electron donor
dopants. Electron donor dopants induce n-type conductivity in
the polymer by donating an electron to the polymer and reducing
same to a polyanion and the dopant is oxidized to a cation.
Similarly, a p-type electroactive oryanic polymer is obtained
by reacting the virgin polymer with oxidizing electron acceptor
dopants. Electron acceptor dopants induce p-type conductivity
in the polymer by oxidizing the polymer to a polycation and the
dopant is reduced to an anion. The desired value of the room
temperature electrical conductivity of the dopant modified
electroactive organic polymer is preselected by controlling the
level of incorporation of the dopants into the virgin polymer.
Alternatively, the desired value of the roo~ temperature elec-
trical conductivity of the dopant modified electroactive
organic polymer is preselected by controlling the length of the
reaction time between the virgin polymer and dopants. Further-
more, the highly selective and reversible modification oE the
room temperature electrical conductivity of the virgin polymer
can proceed by either chemical or electrochemical means. The
highly selective and reversible modification of the electrical
conductivity oE the dopant containing organic
polymeric material togethcr with the tractability and processability of t~le
virgin polymer is highly desirable in that the fabrication of useful articles
and devices such as primary and secondary batteries, photovoltaic devices,
Schottky type devices can be accomplished. Furthermore, the materials
described in this invention can be utilized as active components in such
devices and articles as electrochromic displays and photolithographic
processes.
DET~ILED Dr:SCl~PTION O~ Tll~ INVE~TIO~
Electroactive organic polymers are fabricated from the modification
of tractable and processable virgin polymers consisting of recurring units
of fused nitrogen-containing ~msaturated, heterocyclic ring system by suit-
able conductivity modifiers. The polymers are composed of repeating diradical
units derived from fused six-member nitrogen-containing ring systems wherein
each ring contains no more than three nitrogens bonded sequentially. A
diraclical is defined as a molecule that has two unsatisfied positions
available for linking into the polymer chain. Optionally, the diradicals are
separated in the po]ymer chain by connecting units.
The fused rings contain from one through six nitrogen atoms. The
nitrogen atoms are distributed between the fused rings with three or fewer
nitrogens bonded sequentially in a ring. Suitable examples of single nitrogen
fused ring systems are any of the diradicals of quinoline and isoquinoline.
Suitable examples of two-nitrogen fused ring systems are any of the diradicals
of cinnoline; quinazoline; quinoxaline; 2-phenyl-quinoxaline; phthalazine;
1,5-naphthyridine; 1,6-naphthyridine; 1,7-naphthyridine; 1,8-naphthyridine;
- 2,6-naphthyridine; copyrine; and the like. Suitable examples of three-nitrogen
fused ring systems are any of the diradicals of 1,2,4-benzotriazine; pyrido-
[3,2-d] pyrimidine; pyrido[4,3-d] pyrimidine; pyrido[3,4-d] pyrimidine;
pyrido[2,3-d] pyrimidine; pyrido[2,3-b] pyrazin~; pyrido[3,4-b] pyridazine;
pyrido[2,3-d] pyr:idazine; pyrido[3,4-d] pyridazine; and the like. Suitable
examples of four-nitrogerl fused ring systems are any of the diradicals of
pyridazino[4,5-d] pyridaz:ine; pyr:imido~5,~-d] pyrimi-line, pteri-
dine;pyri~i.do[~,5~d] pyridazine, pyrimido[4,5-d] pyrimidine;
pyrazino[2,3~b~pyrazine; pyrazino[2,3-d] pyridazine; pyrida-
æinoC4,5-d3 pyridazine:pyri.mido[~,5-c] pyridazine: p~razino[2,3-
c] pyridazine; pyridoC3,2-d]-as-triazine; pyrido[2,3-e]-as-tri-
azine' and the like. Suita~le exampl.es of five-nitrogen fused
ring systems are any of the diradicals of pyrimido [~,5-e3-as-
triazine; pyrimido~5,~-d3-as-triazinei and the like. Suitable
examples of six-nitrogen fused ring systems are any of the di-
radical.s of as-triazino[6,5-d]-as-triazine and the like. A11
the previously mentioned fused nitrogen ring systems are known
and disclosed in The Ring Index, second edition, and Supplements
I, II and III; Patterson et al, American Chemical Society. The
molecules are synthesized into polymers by methods known in the
art such as treatment with Zncl2 or ~eCl3 and an alkyliodide, or
by dichlorination followed by reaction with appropriately disub-
stituted molecules such as: disodium sulfide, disodium salt of
ethylene glycol, and the like. The diradicals can be modified
with substi-tuents which modify the polymer properti.es such as
electron donating or withdrawing groups by methods known in the
art.
Suitable compounds in which one or more of the nitro-
gens are saturated with hydrogen or by bonding in the fused
ring or in the ionic form, include any diradical of quinolinium;
pyridazino[l,2-a] pyridazine; 2H-pyrido[1,2-a] pyrazine;
pyrido[1,2-a] pyrimdine-5-ium; pyrimido[1,2-a] pyrimidine-5-ium;
and 2H-pyrazino[1,2-a~-pyrazine. The compounds are known and
disclosed in The Ring Index and Supplements I, II and III. The
polymers are fabricated by methods known in the art.
For example, an electroactive polymer can be fabri-
cated with recurring units of positional diradicals of quino-
line, substituted quinoline, isoquinoline, substituted isoquin-
-~ oline and mixtures thereof. The diradicals
can be linked at the 2,4; 2,5; 2,6; 2,7; 2,8; 3,5; 3,6; 3,7; 3,8; 4,6; 4,7;
4,8; 5,7; 5,8; and 6,8 positionsJ but connections at the 2,6 and 3,6
positions in the polymer are preferred. The quinoline ring system is
numbered as follows:
~3~
The isoquinoline ring system is numbered as follows:
Nl ~ i~J
For example, the 296 diradical of quinoline has the formula:
,~
A preferred diradical of quinoline or isoquinoline is substituted in the
4 position. Preferably, the diradical is substituted with a phenyl group.
The diradicals can be separated by one or more connecting units.
Preferred connecting units are bi-phenyl, -CH=CH-, and -C - C-. The
connecting units can be the same or different between adjacent diradicals
in the polymer chain.
The polymer can be a homopolymer of the diradicals of quinoline,
isoquinoline and the substituted deriva-tives thereof or a copolymer of the
diradicals. A homopolymer is defined as a polymer fabricated comprising
- 6 -
the same recurring diraclical. A copolymer is defined as a
polymer comprising different cliradicals. In addition, the
polymer is a copolymer if the same or diEferent recurring di-
radicals are interspersed with connecting units.
The polymer is rendered elec-troactive by incorpor-
ating into the viryin polymer a conductivity modifier. More
specifically, the polymer is rendered electroactive b~ adding
electrons to (reducing) or removing electrons Erom (oxidizing)
the virgin polymer backbone. This can be accomplished by in-
'0 corporating into the virgin polymer a conductivity modifier
which is either an electron donor. dopant or an electron
acceptor dopant. An electron donor dopant donates an electron
to the polymer, the polymer becoming reduced to a polyanion and
the dopant becoming oxidized to a cation. An electron acceptor
dopant rernoves an elec-tron from the polymer, the polymer be-
coming oxidized to a polycation and the dopan-t becoming reduced
to an anion. ~lternatively, the polymer can be rendered elec-
troactive by electrochemical oxidation or reduction. In this
case an electron is removed ~rom or added to the polymer from
an electrode, and charge compensatiny anions or cations,
respectively, are incorporated into the polymer from t'ne
supporting electrolyte solution.
In both cases the resulting electroactive polyme~
consists of a charged polymer backbone incorporating charge-
compensa-ting ionic dopants. ~ suitable positively charged
compensating dopant can be a cation such as the alkali metal
ions, alkali earth me-tal ions, group III metal ions and organic
cations such as
R4i_N+ RXi-+ ~ , and ~ ~N_p~3i
~here RXi is a straight or branched chain alkyl of Cl-C6
groups. Mixtures oE these charge compensa-ting dopants can be
employed. These ionic dopants produce n-type conduc-tivity when
associated with a reduced or negatively charged polymer poly-
anion.
f~
A suitable negatively charged compensating dopant,
l.e. anionic dopants, can be an anion such as the halogen ions,
other ions such as AsF4-, and preferably ions such as AsF6~,
C104 ~ PF6 , S03CF3 , ~F4 , N03-, POF4-, CN-, SiF5-, SbC16-,
Sb~6-, HSO~ , organic anions ions such as CE-I3C02-, (acetate),
C6~sC02-, (benzoate), CH3C6H4S03-, (tosylate) and the like.
Mixtures of the charge compensating dopants can be employed.
These ionic dopants produce a p-type conductivity when asso-
ciated with an oxidized or positively charged polymer poly-
cation.
The dopant modified electroactive polymer has a
charge opposite to the conductivity modifier, i.e. ionic
dopant. I'he charges on the dopant modified electroactive poly-
mer and the ionic dopant balance so that the dopant modified
electroactive polymer is an electrically neutral system. The
association of -the virgin polymer with electron donor dopants
produces an electroactive polymer which exhibits n-type conduc-
tivity. More specifically, reduction of the virgin polymer and
the incorporation of cationic charge compensating dopants pro-
duces a polymer which exhibits n-type conductivi-ty. The asso-
ciation of the virgin polymer with electron acceptor dopants
produces an electroactive polymer with p-type conductivity.
More specifically, oxidation of the polymer and incorporation
of anionic charge compensating dopants produces a polymer with
p-type conductivity.
The electroactive polymers of th0 invention have the
following Eormula:
(+Sd)
(+S)
R t-X ) a ( R ) c ( Y ) b } (Md)
rl
,. .
where a is either 0 or ], b is either 0 or 1; c is either 0 or
1, n is an integer between 2 anc1 20,000; d is an integer
between 1 and 40,000; s is an integer 1, 2, or 3: R i5 a fused
nitrogen-containing unsaturated diradical-heterocyclic ring
system; R' is the same as R or a differen-t ~used unsaturated
heterocyclic ring system; X is a connec-ting unit comprising of
a single atom, or a group o atoms; Y is a connecting unit
wl~ich is identical to or different from ~; and M is a ch~rge-
compensating ionic dopant of opposite electrical charge to the
charge oE the polymer backbone wherein the polymer backbone is
capable of undergoing reversible oxidation or a reversible
reduction, or both, to form said charged polymer backbone.
Preferahly in these polymers in the fused
nitrogen-containing ring systems the atoms at the ring fusion
points are other than nitrogen.
The repeat units form the polyanion or polycation of
the electroactive polymer.
The diradical R group is a substituted or unsubstitu-
ted fused six-member nitrogen-containing rings. The diradicals
contain from one to six nitrogens distributed between the ~used
six~member rings wherein each ring contains no more -than 3
nitrogens bonded sequentially. Suitable R groups are the di-
radicals of molecules recited previously which contain from one
to six nitrogens. Preferred two ni-trogen fused ring systems
would be composed of substituted or unsubstituted diradicals of
quinoxaline.
More specifically, R and R' are unsubstituted or
substituted quinolinic and isoquinolinic diradical or mixtures
of diradicals which are linked -to one another either directly
or via the connecting units X and Y by forming bridges.
" ~
- ~a -
Preferahly the bridges are Eormed at the 2,6 and 3,6 posi-
tions~
The connecting units X and Y can be selected from the
group COmprl slng:
-0-; -S-; -CH=CH- -C--C-
~i ~~ S,~
CH-C~ ~ ; ~ C-C _ ~ ;_ ~ ;
~ _ cRv=c ~ , and -cRVii= cRvli
:,'
01
-10-
wherein RV, Rvi and R~ii are H or methyl and mixtures
oS thereof. Blphenyl, vinyl and acetylene connecting groups
are preerred connecting units.
The size of n determines the physical properties
o the electroactive pol~mer. Preferably, n is rom lO to
lO,000 when c is zero. Most preferably, n is from 50 to
5,000 when c is zero. Tractable films are formed with
electroactive polymer whose n exceeds 50. A preferred
molecular weight is lO,000 or above.
The enhancement in conductivity of the electro-
active polymer above the conductivity of polymer in the
virgin state is determined by d. The conductivity is
increased and adjusted by increasing d. For example, the
virgin homopolymer of 2,Ç-~4-phenylquinoline) has a con-
ductivity of about lO~l5 ohms~l cm~l. Incorporating about
20 weight percent of a charge compensating ionic dopant
such as Na~ in the electroactive polymer increases the
conductivity to about 102 ohms l cm l. Preferred electro-
active polymers are doped polymers that have conductiv-
ities greater than about lxlO-l0 ohm l cm l r most
preferably greater than lx10-4 ohm~l cm~l. Conductivities
in the range of semiconductors can be achieved when d is
from about lO to about lO00. Greater concentrations of
the charge compensating ionic dopant M increase the
conductivity to the metallic conductivity regime. The
charge compensating cationic or anionic dopant M is
selected from the previously recited dopants and the likeO
M remains the same for all the following preferred poly-
mers.
The R and R' groups are the same or different.
When a is l, b and c are zero, R' and Y drop out and the
polymer has the following formula:
(+ Sd)
~R-~X) ~ (Md)(+S)
01
when a, b, and c are zerot R', X, Y drop out and the poly-
mer has the formula-
~5 ~
(~Sd)
~ER~n ( ~ ( ~ S )
A preferred R or R' is selected from the group
consisting of the diradicals of quinoline, substituted
quinoline, isoquinoline and substituted isoquinoline. A
preferred diradical is a 2,6 substituted quinoline of the
formula:
Riii Riv
"~
wherein Rii, Riii and RiV are substituent groups selected
from H; hydroxy; carboxy; amino; alkyl 1 to 4 carbon
atoms; alkoxy 1 to 4 carbon atoms; an alkylthio of 1 to 4
carbon atoms; a cycloaliphatic group of 5 or 6 carbon
atoms; an alkenyl group of 2 to 4 carbon atoms; an aryl
group of 6 to 10 carbon atoms; an aryl group of 6 to 10
carbon atoms substituted by 1 to 3 alkyl groups of 1 to 4
carbon ~toms, alkenyl groups of 2 to 4 carbon atoms,
alkynyl groups o~ 2 to 4 carbon atoms, alkoxy groups of 1
3 to 4 carbon atoms, 1 to 3 cyano groups, 1 to 3 halogen
atoms r dialkyl amino groups of 1 to 4 carbon atoms t an
alkylthiol of 1 to 4 carbon atoms; or a 5~ or 6-member
nitrogen containing unsaturated heterocyclic group. The
nitrogen atom~ in the above polymers can be quaternized by
-~ 35 reaction with quaternizing agents, e.g. dimethyl sulfateu
The term "alkyl" refers to both straight- and
branched-chain alkyl groups~ Suitable examples are
methyl, ethyl, propyl, isopropyl, butyl t i-butyl, s-butyl,
and t-butyl.
JLf~i~.3~
~1
-12-
The term "alkoxy" refers to the group R ~
wherein Rl is alkyl. Suitable examples are methoxy,
ethoxy, propoxy, isopropoxy, butoxy, i-butoxy, s-butoxy,
and t-butoxy.
The term "alkylthio" refers to such examples as
methylthio, ethylthio, propylthio, isopropylthio, butyl-
thio, i butylthio, t-butylthio, and s-butylthio.
Suitable examples of cycloaliphatic are cyclo-
pentyl, cyclohexyl, 3-methylcyclopentyl~ and the like.
~ he term "alkenyl" refers ~o unsaturated alkyl
groups having a double bond [e.gO~ CH3CH=C~(CH2)2] and
includes both straight- and branched-chain alkenyl groups
such as ethenyl~ but-3-enyl, prope~yl, and the like.
The term "aryl" refers ~o an aromatic hydrocar-
bon radical such as phenyl, naphthyl, and the like. Suit-
able examples of an aryl substituted with an alkyl are 2-
tolyl, mesityl, 3-isopropylphenyl and the like. Suitable
examples of an aryl substituted with an alkenyl are 3-
styryl, 4~ propenylphenyl, and the like, Suitable aryl
groups substituted with an alkoxy are l-methoxy-2 naph~
thyl, 3-n-butoxyphenyl, and the like. Suitable aryl
groups ~ubstituted with a cyano group are 4 cyanophenyl,
4-cyano-1-naphthyl, and the like. Suitable examples of an
aryl with a halogen are 4-fluorophenyl, 3-chloro-4-bromo-
l-naphthyl, and the like. Suitable examples of an aryl
substituted with a dialkyl amino are 3-dimethylamino-
phenyl, 6-diethylamino-2-naphthyl, and the like. Suitable
examples of an aryl substituted by an alkylthio are 4
butylthiophenyl, 3-methylthio-2-naphthyl, and the likeO
Suitable examples of 5- or 6-member nitrogen containing
heterocyclic groups are 3-pyrrolyl, 4-pridyl, and the
like.
Preferred polymers of 2,6 substituted quinoline
occur when Rii and RiV are H. A preferred polymer is
obtained when Rll and RlV are H and Rlll is phenyl, i.e.
poly 2,6-(4-phenylquinoline).
~.3'~
01
-13-
~Sd)
0S -' ~ /
~ / (Md)
1~ Another preferred group of polymers are obtained
when Riii is phenyl and Rii and RiV are selected from the
group of ~ubstituents previously recited.
Still another preferred polymer is fabricated
from 2,6-(4-phenylquinoline~ diradicals wherein a CH3+
lS moiety is directly linked to the nitrogen of the quinoline
diradical, i.e. quaternized.
~ (~Sd)
~
~J/ (~d)
/ CH3 ~ll
Another preferred polymer is fabricated of 2,6-(4-
(4'pyridyl)quinoline) and/or its quaternized analog~ When
R and Rl are the same and are the 2,6 quinolinic diradical
unit, the recurring repeat unit of the dopant modified
electroactive polymer is:
(iSd)
~ ~1~ T x ~ d)
Rlll RlV ~,
wherein Rll, Rlll, and Rl~ are substituents selected from
the groups recited above and X and Y are the connecting
units pre~iously rec.ited. M is a previously recited con-
ductivity modifierO
A preferred poly~er has the formula
3 ~ (ISd)
~ ~ _ O ~ ~ (Md )
wherein Rii and RiV are H, Riii is phenyl a, b and C are
1, X is O diradical and Y is a Phenyl diradical.
_ Another preferred polymer has the formula
~ Sd)
~ (Md~j
wherein Rii and RiV are H, Riii is phenyl, a and c are l,
b is zero, and X is a biphenyl diradicalD
Another preferred polymer has the ormula:
( I Sd )
COOH COOH
( ) ( i S )
~ N ( ~
wherein Rii and Ri~ are H, Riii.is -COOH, a is 0, b and c
are l, and Y is a biphenyl diradical.
Another preferred polymer has the formula:
-14-
s
,. ,~., . ~,
(+Sd)
~ r~ n(Md)(_S)
wherein R , R and R v are H, a is 0, b and c are 1 and Y is
biphenyl diradical.
Another preEerred polymer has the formula:
CH3 CH3 (+Sd)
(+S)
,~'~`11,~ (~1 ~ (Md)
wherein R and R are H, R is -CH3, a is 0, b and c
are 1 and Y is
_~z_~
and Z is a connecting unit selected from the connec~ing units for
X and Y.
Another preferred polymer has the formula
0l (+Sd)
(+S)
~' ~ ~ ~ _ n
wherein Rii and R are H, R is -0~, a and c are 1, b is zero, and
xiS ~
Another preferred polymer is obtained when R and R' are
substituted quinoline diradicals wherein R i and R
- 15 -
01
-16-
are H, a is 1, b is 1, c is 1, X is -CRVil=CRvii- and Y is
-CRVii=C~-. The polymer has the formula:
Riii - ~Sd)
Riii Rvii ~ ( d)
~ R~ii n
Still another preferred polymer is when Riii is phenyl and
RVii is H,
When R or R' are substituted isoquinoline dira-
dical, a preferred diradical has the formulaO
~'0 X~ }~vi~i
wherein RViii~ RiX, and Rx are selected from the same
substituent groups as Rii t Riii, and RiV. Similar poly-
mers to the previously recited preferred quinoline poly-
mers are also preferred for isoquinolineO
A preferred electroactive poly(phenyl quin-
oxaline) polymer has the formula:
_ -
~N N~ Sd) (~S~
_ ~ N ~ N ~ O ~ ( d)n
where R and R' are phenyl quinoxaline, a is C, b and c are
1 and Y is - ~ o ~ _ .
~0
Polymer Fabricatlon
The .starting ma~erial for preparing the electroactive
polymers of this invention are polymers and copolymers com-
prisiny recurring units of fused nitrogen containing unsatur-
ated heterocyclic ring system. Preferably the recurring units
are quinolin~ or isoquinoline or subs-tituted quinoline or
isoqulnoline. These polymers and copolymers are well Xnown
ma~erials having been synthesized in a variety of ways. For
example, quinoline, isoquinoline, or substituted derivatives
thereof can be converted into polymers by treatmen~ wi-th zinc
chloride or by -treatmen-t with FeC13 and an alkyliodide,
Rabinovich et al, Dokl. Akad. Nauk SSSR 1971, 199(4), 835-7 and
Smirnov et al, Vysokomol Soedin Ser B 1971, 13(6), 395-6,
respectively. The method is also suitable to polymerize the
o-ther diradicals previously recited.
Other polymers are made by a synthetic route
involving the reaction of ~he dichloro or dibromo derivatives
of fused nitrogen containing unsaturated heterocyclic units
with magnesium in ether followed by contacting with a nickel
salt. The dihalo derivatives having halogens in essentially
all possible combinations are known. This route provides a
method of prepaxing polyquinolines or polyisoquinolines having
bridges through any two of ~he seven possible points o~ attach
ment.
The dihalo compounds are also useiul in forming
copolymers with other interconnecting groups. For example
reactions with sodium sul~ide gives a sulfur atom between each
nitrogen heterocycle. Reaction with dihydroxy or disodium
salts of dihydroxy compounds give ether-type copolymers.
~ .~
-17-
~ nother me~hoc1 of makincJ the polymeric starting
material is by a syn-thesis involving the Einal reaction of an
appropria~e diketone wi~h an appropriate aminodiacyl-~enzene in
the presence of a base or an acid catalys-t as discussed in
Korshak et al, Vysokomol, Soedin., Ser B9(3), 171~2(1967);
Shopov, I, Vysokomol.Soedin., Ser B 1969, 11(4) 248; Garapon, J
et al, Macromolecules 1977, 10(3) 627-32; Stille, J.K et al,
Polym. Prepr., Am Chem. Soc., Div. Polym. Chem 1976, 17(1),
41-45; Stille, J.K. Pure Appl. Chem. 1978, 50(4), 273-280;
Baker, G. L. et al Macromolecules 1979, 12(3), 369 73; and
Beever, W. H. et al Macromolecules 1979, 12 (6), 1033-8.
Still another method of prepariny polyquinolines
useful as starting materials for the compounds of this inven-
tion is by the condensation polymeri~ation of appropriate di-
(aminophenyl) compounds with appxopriate di(alpha,gamma-
diketo)compounds, see V. Korshak et al, Vysokomol Soedin, Ser
B9(3), 171, (1967). The resulting polymers have structures of
formula - -
C~I3 CH3
~Z1~
where zl is 0 or OEI2CH2.
The di(aminophenyl) compounds may contain a variety
of substituents but mus-t have an unsubstituted position or-tho
to the amino group. Typical compounds include 4,4'-diaminobi-
phenyl, 3,3'-diaminobiphenyl, 2,4'-diaminobiphenyl, 2,2'3,3'-
tetramethyl-4,4'-diaminobiphenyl, di(4-aminophenyl) methane,
di(4-aminophenyl) ether, 1,2-di(4-aminophenyl) ethane, 1,2-di-
(4-aminophenyl) ethylene, and the like.
., ~.
-18-
" ~
The di(alpha,gam~na-diketo) compounds compris~ those
compounds wherein the diketones are joined at the alpha-
position through various connecting groups. These compounds
have the s-tructure:
O O O O
.. .. ,~ "
CH3 - c-c~I2 - ~-z--C~C~12--~-CE13 1
wher~in Z is a connectiny group. Typical connec-ting groups
include the X and Y connecting groups having 2 or more atoms,
French Pat. 1,468,677 and J. Polym. Sci. Part C, #16 Part 8,
4653 (196~).
The preferred method for making the polyquinoline
polymeric starting material is in accordance with the proce-
dures outlined by W. H. Beever, et al., Journal of Polymer
Science: Polymer Symposium 65, pp. 41-53 1978; S. 0. Norris,
et al., Macromolecules, Vol. 9, No. 3, May-June, 1976, pp.
496-505, J. Pharm. Sci. 57 784 (1968), and J. ~eterocycle Chem.
_ 107 (1974).
Tractable Polymer Fabrication
Subsequen-t to polymerization, articles such as
fibers, ribbons, or free-standing films are cast from solution.
The solution is Eormed by dissolving the desired polymer in a
solvent which consists of sulfuric acid, formic acid, or a
mixture of P20s and m-cresol. The solution temperature is from
about 25C to about 200C and preferably at about 140CI most
preferably 100C. The polymers are coagulated into solid
shapes such as fibers, ribbons, or free-standing films in a
basic coagulation bath. For ~ree-s-tanding films, the polymers
are fabricated from solutions containing about 2 to 25~ polymer
dissolved in the solvent. At concentrations which exceed 10~,
the cast films take on an anisotropic morphology. The aniso-
r~
tropic property enhances the cc>ncluctivity in the anisotropicdirection. ~n amlne, for example triethylamine, dissolved in a
protonic solven-t such as ~120 and preferably ethyl alcohol
comprises -the coagulation bath. The bath ls maintained at a
lower temperature ~han the dissolu~ion temperature of -the poly-
mer in the solvent. ~sually room -temperature i8 selected as
-the operating temperature of the coagulation bath. The fabri
cated articles are dried. Elevated temperatures, usually 60C,
and reduced pressure accelerated the drying process. Drying is
0 continued until no further weight loss is observed.
Polymer Conductivity Modification
AEter fabrication of the desired articles from the
polyfused heterocyclic quinolinic polymers by means of the
procedure described above, the articles are rendered electro-
active by, for example, chemical or electrochemical procedures.
The articles can be rendered electroactive in an atmosphere
which is inert with respect to the polymer and dopant, by
contacting them with suitable conductivity modifiers, i~e.
dopants. An inert atmosphere is defined as an atmosphere which
does not react with the polymer, the dopant, or the electro-
active polymer. For example, the atmosphere can be argon,
helium, and nitrogen and the like. The doping can also be
carried out in an i.nert liquid medium such as tetrahydroEuran,
acetonitrile and the like. The dopants can be oxidizing or
electron accepting molecules, or reducing molecu]es, or
reducing or electron donating molecules. Both types of dopants
may be in the form of gases or vapors, pure liquids or liquid
solutions. Preferably, oxygen and water moisture are excluded
during and after the doping process because the conductive
polymers tend to degrade, i.e. lose conduc-tivity, when exposed
thereto.
.~y . ~
-20-
For example, the polymer can be contacted with alkali
naphthalides or alkali anthracenic1es such as sodium naphtha-
lide, potassium naphthalide, or sodium anthracenide in a tetra-
hydrofuran solution. The conductivity modifier concentration
can be from about 0.001 to about 1 molar and preferably from
about 0.01 to about 0.5 molar in the THF or o-ther suitable
solven~. ~lternative doping methods are taught in U.S. patent
4,~04,216.
I~ is unclear at -the present time exactly ho~ the
electron donor or acceptor dopants are incorporated into the
polymer. However, the incorporation of the dopants into the
polymer can be observed by a color change in the polymer as
well as an enhanced conductivity. For example, a virgin poly-
mer film having a yellow or orange
- 20a -
2L -
co:lor, changes to a blue or black color with a metallic luster
~lpon doping ~nd the rneasured conductivity increases by ~any
orders of magnitude.
Alternatively, the polyquinoline pol~mers can be
oxidized or reduced to their conductive forms using electro-
chemical techniques. In this method, herein reEerred to as
electrochemical doping, the poly~er is immersed in a suitable
electrolyte solution and used as one electrode of an electro-
chemical cell. Upon passing an electric current through such a
cel] the polymer becomes reduced (or oxidized, depending upon
the direction of current flow) and charge compensating cations
(or anions) Erom the supporting electrolyte become incorporated
into the polymer, This doping also proceeds with the character-
istic color change described above. Thusl the polymer can be
electrochemically doped wlth whatever appropriately charged ion
is present in the electrolyte solution. Electrolyte solutions
are comprised of a salt dissolved in a solvent. Suitable sol-
vents are acetonitrile, tetrahydrofuran, 2-methyl-tetrahydro-
Euran, propylene carbonate, dimethyl-~ormamide, dimethyl-
sulfoxide and the like. Suitable cations are Li+, Na~~, K+,
(CH3)4N~, (C2Hs)4N+ and (C4Hg)~N+. Suitable anions are Cl-,
Br-, C104-, BF4-, and PF6-. The extent of doping can be easily
controlled by adjusting the amount of charge electrochemically
injected into the polymer, either by controlling the magnitude
of the current used (galvanostatic charging) or by controlling
the potential of the polymer electrode with respec-t to a refer-
ence electrode (potentiostatic charging).
The above--described electrochemical doping process is
completely reversible. The polymer can be "undoped" and re-
turned to its original, neutral, non-conducting state simply by
applying a current opposite in sign to that used for the doping
process, Upon complete undoping the color of the polymer
reverts back to its original color. Thus, Eor example, a
re~uced~ conducting polyquinoline polymer can be reoxidized
completely to its neutral, non-conducting form, and the charge-
71 ~D,i ~
- 22 -
compensating cations incorporated during the electrochemical
reduction process are expellecl from the article during electro-
chemical re-oxidation.
Having described the methods o~ Eabrication and the
basic polyfused heterocyclic systems, the following examples
are intended -to be illustrative of the invention and not meant
to limit the scope thereof. Modification which would be
obvious to one of ordinary skill in the art are contemplated to
be within the scope of -the invention.
EXAMPLES
Example la
Preparation oE 2-methyl-2-(4-nitrophenyl)-1,3-dioxolane
P-Nitroacetophenone (1.65g, 10 m mol), ethylene
glycol (5 ml, 89 m mol), triethyl or-thoforma-te (2.96 g,
20 m mol), and p-toluenesulfonic acid (0.086 g, 0.5 m mol) were
combined in methylene chloride (4 ml). The solution was heated
with an oil bat'n (50-70C, 6 hrs), cooled to room -temperature,
and poured into excess 10% sodium hydroxide solution. The
phases were separated and the aqueous phase was extracted twice
with methylene chloride. The combined organic phase was washed
three times with water and dried with anhydrous sodiu~ sul-
phate. Evaporation of the solvent left a light yellow product
(1.78 g) with mp. 69-71C, (lit. 73-75C, see
J. Pharm. Sci. _, 784 (1968)).
Example lb
Preparation of
5-(2-Methyl-1,3-dioxolan-2yl)-3-phenyl-2,1-benzisoxazole
Phenylacetonitrile (0.84 g, 7.2 m mol) and 2-methyl-
2-(4-nitrophenyl)-1,3-dioxolane (mp. 69-71C) (].50 g,
7.2 m mol) were added to a room temperature solution of sodium
hydroxide (1.44 g, 36 m mol) in methanol (8 ml). A slight
exotherm was noted and stirring was continued Eor 16 hrs. The
mixture was filtered and the collected solid washed several
times with water and once with cold methanol to yield a yellow
powder (1.60 g) with mp. 137C (lit~ mp. 137-138C, see
J. Heterocyclic Chem. 11, 107 (1974)).
01
23-
Example lc
Preparation of
05 2-Amino-5-(2-methyl-1,3-dioxolan-2-yl) benzophenone
5-(2-Methyl-1,3-dioxolan-2yl)~3-phenyl-2,1-ben-
zisoxazole (1.50 9, 5.3 m mol), triethyl amine (0.3 ml)
and 5~ palladium on carbon (0.15 g) were combined ln dry
tetrahydrofuran (13 ml). The apparatus wa flushed with
nitrogen and then hydrogen. A static hydrogen atmosphere
was maintained (1 atm.) and the progress of the reaction
followed by gas chromatography. The starting material and
product have re~ention times of 11.15 and 11.33 min.
respectively. When conversion was complete, the mixture
was filtered through a pad o Celite to yield a clear
yellow solution. Evaporation of the solution yielded a
yellow solid ~1.35 g) of mp. 108-111C.
Example ld
Preparation of
5-Acetyl-2-aminobenzophenone
2-Amino-5-(2-methyl-1,3-dioxolan-2-yl) benzo-
phenone (1.0 g, 3.54 m mol) was dissolved in 30 ml
absolute ethanol. To this was added lM perchloric acid
(14 ml). The resulting mixture was stirred at room tem-
perature for 18 hrs. The mixture was made basic with 3N
sodium hydroxide solution and then extracted with several
portions of methylene chloride. The combined methylene
chloride extracts were washed with water, dried with anhy-
drous sodium sulfate, and evaporated to yield a yellow
30 product (0.79 g) of mp. 158-161C. A portion of the
product was recrystallized from a mixture of methylene
chloride and hexane to yield material of mp. 158-162C.
Example le
Preparation of
Poly 2,6-(4-phenylquinoline)
A solution was prepared from phosphorous pent-
oxide (1.07 g, 7.5 m mol) and reshly distilled m-cresol
(2.5 ml) by heating at 140C for 2.5 hrs. under nitrogen.
The solution was cooled to room temperature and 5-acetyl-
2-aminobenzophenone (0.30 g, 1.28 m mol) and m-cresol
(1.3 ml) were added. The solution was heated to, and
.
* Trade Mark
~'
malntained at 120C for 48 ~Irs. T~l~ h~t so~ution was poured ~,7ith stirring
into a mixture of 95% ethano] (60 ml) and triethylanline (6 ~ll) to yield a
fibrous yel]ow solid whicll was ~clshecl t~ice ~itll ~thanol in a Waring blender.
It was then extracted with ethanol (19 hrs) in a Soxlet apparatus and dried
to give an orange product (0.26 g, 1.28 m mol).
Examp:le 2
Preparation of Films of Poly 2,6-(4-phenylquinoline) Films
A solution was prepared from phosphorous pentoxide (0.8 g, 5.6 m
mol) and distilled m-cresol (2.5 ml) by heating at 110-120C under Argon.
The solution was cooled to room temperature and poly 2,6-(4-phenylquinoline)
(0.051 g, 0.25 m mol) added. The mixture was heated to 140C to yield a
viscous deep red solution. Free-standing films were prepared by spreading
a few drops of this solution on a heated glass plate and quenching in a bath
of triethylamine (10%) and ethanol (90%). The clear yellow films were
pressed between la~ers of filter paper and dried in a vacuum oven.
Example 3
Doping of Poly 2,6-(4-phenylquinoline)
The transparent, yellow film prepared in Example 2 was placed
in a jar, in a dry box with a dry argon atmosphere. After 30 minutes, a
dimethoxyethane solution of sodium naphthalide was poured into the jar.
The film reacted immediately, changing to a dark color; green blue in
transmitted light and purple-green ~:ith metallic sheen in reflected light.
Upon exposure to air, the dark color disappears instantly, and the polymer
resumes its original appearance.
Example 4
Conductivity ~leasurement of Poly 2,6-(4-phenylquinoline)
The procedure of example 3 was followed except the Eilm was first
wet with tetrahydrofuran (THF) and then treated with O.l~f sodium naphthalide,
dissolved in THF. Upon addition of the sodium naphthalide, the polymeric film
* Trade Mark
- 24 -
.~
turned deep blue with a metallic luster. The surface of
the film was rinsed with THF. l'he conductivity of the
doped film (2.54 x 10-3 cm thick) was measured using a 4-
point probe apparatus of the Signature Co. The 4 points
of the apparatus form a single line. A DC voltage (VE) is
applied across the outermost two points, and the voltage
(Vl) of the current is measured across the inner two
points. From these values a conduc~ivity is calculated as
follows:
VE = 0.1 volts VI = 0.06 volts (measured)
R = 1074 (VE/VI) = 1790 ohms/square
rho = Rxt = 1730 x 2.54 x 10-3 = 4.55 ohm centimeters
sigma = l/rho = 0.22 ohm~l centimeter~
where:
VE = impressed voltage
t = film thickness
VI = measured voltage
R = resistance of the surface-
rho = resistivity of the article
sigma ~ conductivity
1074 = instrument and unit conversion factor
The washed, but undoped polymer, was not conduc-
tive, but actually was an insulator having a conductivity
of 10 15 ohms 1 centimeter 1 as measured on the same appa-
ratus, (See J. Polym. Sci. Poly. Symp., 65, 41 (1978).
This same value (10-15) was measured on the doped film
after turning yellow upon exposure to air.
The infrared spectra of the original undoped
film and the air-exposed doped film were the same. The-
infrared o the dark, sodium naphthalide doped film was
opaque with no absorption between 4000 and 600 cm 1, indi-
cating metallic behavior. This experiment show$ that the
doped polyquinoline films are surprisingly good electrical
conductors.
-25-
~:,
f~ ~- JL
~1
-~6
Example 5
Conductivity Measurement of Poly 2,6-(4-phenylquinoline)
Films were also doped as in Example 4 but with
potassium naphthalide and after these films had been kept
for 6 days in a vacuum dry box at a pressure less than
10-6 mm Hg, the following conductivity value was obtained:
VE = 36 mv ~I = 55 mv t = 2.54 x 10-3 cm
rho = 1.78 ohm cm. sigma = 0O56 ohm~l cm~
Values of this magnitude show the doped polymer to be
electroactive in that it is a conductor of electricity.
Example 6a
1~ Preparation of bis-4-Nitrophenylether
l-Fluoro-4-nitrobenzene (20.0 g, 0.142 mol),
4-nitrophenol (19.7 g, 0.142 mol), and potassium fluoride
(28.3 g, 0:486 mol) were combined in 75 ml dimethylsulf-
oxide and heated to reflux for 0.5 hrs, The mixture was
cooled and left at room temperature overnightO
The precipitate was collected and washed with
water, It was dissolved in warm toluene, separated from a
water layer and dried with magnesium sulfate~ Concentra~
tion and cooling yielded 28u8 g of product (mp 144-146C~
in two crops.
Example 6b
Preparation of
5,5'-Oxybis-(3 phenyl-2,1-benzisoxazole)
Phenylacetonitrile (17.72 g, 0.151 mol) and bis-
4-nitrophenylether (19.52 g, 0.075 mol) were added to a
room temperature solution of sodium hydroxide (30.01 g,
0.75 mol) in methanol (150 ml) and heated at reflux for 9
hrs. The reaction mixture was cooled to room temperature
and diluted with 50 ml of 50% methanol in water and then
cooled in an ice bath. The precipitate was collected and
3 washed with cold methanol. This solid was dissolved in
warm toluene, dried with magnesium sulfate, concentrated,
and cooled to yield 7.55 g. Recrystallization from warm
toluene gave S.l9 g of product mp 208-209Co A second,
unidentified material, mp 158 165C, was also isolated.
~0
p~
01 -27-
Example 6c
Preparation of
05 4,4~-Diamino-3,3'-dibenzoyldiphenylether
5,5'-Oxybis-(3-phenyl-2,1-benzisoxazole)
(4,92 9r 12.~ m mol) and triethylamine (1.35 ml) were
combined in tetrahydrofuran (50 ml) under a nitrogen atmo-
sphere. Palladium on carbon (5%, 0.41 g) was added and
then hydrogen was slowly passed through the system for 15
hours. The mixture was filtered through Celite and eva-
porated to a yellow oil which was crystallized from a
mixture of toluene and hexane ( io to 1) to yield 4.33 g
~87~) of the desired product. This was further purified
by recrystallization from methanol to yield 2.43 g with mp
154-155C.
Example 6d
Preparation of a Quinoline Copolymer rom
4,4'-Diamino-3,3'-dibenzoyldiphenyl
ether and p-Diacetylbenzene
A solution was prepared from phosphorous pent-
oxide (5.6 g, 39.4 m mol) and freshly distilled m-cresol
(20 ml) by heating to 140C. A portion of this solution
(7.6 ml) was used to dissolve 4,4'-diamino-3,3'-dibenzoyl-
diphenyl ether~(0.5005 g, 1.225 m mol) and p-diacetylben~
zene (0.1987 g, 1.225 m mol). The solution was maintained
at 110-120C for 48 hrs. The mixture was cooled and
poured into a mixture of triethylamine (10 ml) and 95%
ethanol (100 ml) to yield a white fibrous product. The
product was dissolved in chloroform (15 ml) and precipita-
ted with ethanol. This was repeated to finally yield 0.10
g of whitet fibrous polymer. A film was prepared by dis-
solving 25.7 mg in 0.52 g of the above phosphorous pent-
oxide-m-cresol solution at 60C, placing a few drops on a
warm glass plate, and spreading ~ith a warm blade. After
quenching in a g0% ethanol - 10% triethyl amine bath, a
free-standing film was obtainedO This polymer has the
structure:
~3
~1 _
--28--
Example 7
Doping and Conductivity Measurement
of the Polymer of Example 6
Films of the polymer of Example 6d were kept in
a dry box for 2 weeks at less than 10 ppm water and oxy-
lS gen. Thereater the films were doped with sodium naph-
thalide as described in Example 3. Upon doping, the films
turned a deep metallic blue in color. Conductivity
measurements gave:
VE, = 4~5 mV rho = 40.9~ ohm cm.
VI = 0.3 mV sigma = 0.024 ohm 1 cm~
R ~ 16110 ohms per square
Example 8a
Preparation of
5~Bromo-3-phenyl-2,1-benzisoxazole
Phenylacetonitrile (8.1 g, 69 m mol) was added
to a room temperature solution of potassium hydroxide
(85~) (74 g, 1.1 mol) in methanol (150 ml). To this was
added 4-bromo l-nitrobenzene (12~7 g, 63 m mol~ suspended
in methanol ~130 ml). An exotherm was noted and the reac-
tion was maintained at 50C for 5 hrs. After cooling to
room temperature, water (400 ml) was added. ~he precipi-
tate was collected and washed with waterO The crude prod-
uct (13.15 gj was crystallized from hot methanol (200 ml)
to yield yellow needles (9~52 g, mp 113-116C).
Example 8b
Preparation of
2-Amino-S-bromobenzophenone
S~Bromo-3-phenyl-2,1-benzisoxaæole (7.5 g, 28.6
m mol), water (14.6 ml), and zinc dust (9.3 g, 143 m mol)
were combined. Acetic acid (8.6 ml, 143 m mol) was added
and the mixture was stirred and heated at 80C for
-- 29 -
90 minutes. ~Eter coolin~ to room temperature, both the liquid
and solid ~ortion of the reaction were extracted with methylene
chloride. The combined me-thylene chLoride solutions was washed
once with sodium hydroxide solution (10~) and several times
with water~ Drying (sodium sulfate) and evaporation yielded
the desired product (7.42 ~) of mp. 92-102C.
EX~MPLE 8c
Preparation o-f
4,4'-Diamino-3,3'-dibenzoylbiphenyl
4-Bromo-2-aminobenzophenone (0~55 g, 2.0 m mol) was
dissolved in dry and deoxygenated dimethylformamide (10 ml) in
an inert atmosphere box. To this was adcled in portions
bis(l,5-cyclooctadiene)nickel (0) (0.55 g, 2.0 m mol). The
reaction was moved from the inert atmosp'here box to a vacuum-
argon manifold using standard Schlenk-wave techniques. The
reaction was heated at 50-55~C for 4 hrs. and left at room
temperature overnight. ~he mixture was poured into 200 ml of
water which was made sli~htly basic with sodium hydroxide. The
water was extracted several times with e-thyl acetate which
after drying with sodium sulfate and evaporation gave a dark
brown liquid (0.48 g). Recrystallization from hexane yielded
100 mg of yellow hrown solid mp 180-185C.
Example 8d
Preparation of a Polymer from
4,4'-Diamino-3,3' dibenzoylbiphenyl
and 4,4'-diacetylbiphenyl
4,4'-Diamino-3,3'-dibenzoylbiphenyl (80.0 mg,
0.204 m mol) and ~,4'-diacetylbiphenyl (48.6 mg, 0.204 m mol)
were combined in a solution prepared from phosphorous pen-toxide
(0.348 g, 2.45 m mol) and freshly distilled m-cresol (1.2 ml)
and heated at 120-130C for 46 hrs. T'he ho-t reaction mixture
was poured with stirring into a mixture of triethylamine (6 ml)
and 95% ethanol (60 ml). I'he fibrous red precipitate was
stirred in the basic bath until i-ts color changed to yellow.
It was washed with water and dried at 80C to yield 120 mg of
yellow powder
.~
I~ ~'~' I'J
- ~o
mp > 320C. E'ilms of this material were prepared by dissolving
50 mg at 120C, in m-cresol (0.75 m:L) containing phosphorous
pentoxide (0.2 g). A few drops o:E this solution were spread on
a glass plate and quenched in a bath of triethylamine (10%) and
ethanol (90%) to yield a free-standing yellow film. This co-
polymer has the structure: ~ _
ThereaEter, the polymer was rendered conductive in
accordance with the procedure outlined in Example 3. The con-
ductivity was measured in accordance with the procedures out-
lined in Example 4. The conductivity of the doped polymer was
0.024 ohm~l cm~l.
Example 9
Preparation of
Poly 2,6-(4-(4'chlorophenyl)quinoline)
This polymer was prepared by essentially the same
process as described in Example l, except that 4-chlorophenyl
acetonitrile was used in place of phenylacetonitrile. Analysis
of the polymer gave the following results. Calculated for
(ClsHgNCl):C, 75.80%; H, 3.39%, N, 5.89%, Cl, 14.92%. E`ound:
C, 76.81%; H, 3.64~; N, 5.86%, the remainder being Cl. The
polymer has the structure:
r
~J
n
.~
~ :31 ~
Thereafter, the polymer was rendered concluctive in accordance
with the procedure outlined in Example 3. The conduc-tivity was
measured in accordance with the procedures outlined in
Example 4. The conductivity of the doped polymer was
0.02 ohm-l cm-l.
Example 10
Electrochemically Doping Quinoline Polymers
A 5-inch platinum wire was coated with a thin film of
the polymer of Example 1, by dipping the wire into a 5~ solu-
tion of the polymer in a m-cresol/P20s mixture. The film-
coated wire was neutrali~ed by dipping into a 10% triethylamine
- 90~ ethanol solution and dried in a vacuum oven at 60C.
The polymer coa-ted wire was connected to an
~.G. and G. Princeton Applied Research Apparatus comprising a
Universal programmer and a Potentiostat/Galvanostat, with
recorder. The polymer coa-ted end of the wire was then immersed
into a 0.1 M solution o-f lithium tetrafluoroborate in
acetonitrile. A potential, varying from 0 to -3.0 volts
vs. SCE was applied to the platinum wire. The output current
was essentially nil until the potential reached abou-t -1.5
volts at that point the cathodic current increased rapidly and
peaked at -2.25 volts. Upon reversal of t'ne potential sweep,
an anodic current was observed which peeked at -1.5 volts.
When the initial -1.5 volt potential was applied, the polymer
adhering to the wire turned from a pale yellow to a dark
metallic color, which color disappeared upon raising the
voltage to more than -1.5 volts.
This behavior indicates an initial resistance to
passage of curren-t followed by a rapid uptake of electrons
resulting in a charged electroactive polymer con-taining li-thium
iOIlS as the charge compensating dopant. In effect the polymer
was made electroactive by the application of a potential of
about -2 volts in the presence of an electrolyte solution
capable of providing a charge compensa-ting dopant.
Example 11
Electrochemically Doping Quinoline Polymers
The same experiment as Example 10 was carried out except that the
lithium tetrafluoroborate was replaced by tetrabutyl ammonium bromide.
Essentially the same results were obtained as in Exarnple 10. In this case
the polymer coated wire was alternately charged and discharged without any
loss in activity. The metallic color came and went as the polymer was charged
and discharged.
This experiment indicates that the charged electroactive polymer
can be used as an electron source. One useful application is as the anode
of a battery. It also shows that the electroactive polymer is able to
incorporate into its structure organic charge compensating ionic dopants.
Example 12
Electrochemically Doping oE a Poly(phenyl-quinoxaline)
A 5-inch platinum wire was coated with a thin film of a polymer
of the structure
~ N ~ ~
by dipping the wire into a 5% solution of the polymer in an m-cresol/P2/05
mixture. The virgin polymer was purchased through the Aldrich Chemical Co.
and is a product of Scientific Polymer Product, Inc., 6265 Dean Parkway,
Ontario, ~ew York Catalogue ~330 lot 101. The polymer is 100% solids in
m-cresol. The film-coated wire was neutralized by dipping into a 10% triethyl-
amine - 90% ethanol solution and dried in a vacuum oven at 60C.
The polymer coated wire was connnected to an E.G. and G. Princeton
Applied Research Apparatus comprising a Universal programmer and a Potentiostat/
Galvanostat, with recorder. The polymer coated end of the wire was then
- 32 -
-33-
immersecl into a 0.L M solution of lithium tetrafluoroborate in
acetonitrile. A potential, varylng Erom 0 to -3.0 volts
vs. SCE was applie~ to the platinum wire. The output current
was essentially nil until the potential reached about -1.5
volts. At that point the cathodic current increased rapidly
and peaked at -2.0 volts. Upon reversal of the potential
sweep, an anodic current was observed which peaked at -1.25
volts. When the initial -1.5 vol-t po-tential was applied, the
polymer adhering to the wire turned from a pale yellow to a
dark metallic co.or, which color disappeared upon raising the
voltage to more than -1.5 volts.
This behavior indicates an initial resistance to
passage of current followed by a rapid uptake of electrons
resulting in a charged polymer con-taining lith~lum ions as the
charge compensating dopant. In effect the polymer was made
electroactive by the application of a po-tential of about -2
volts in the presance of an electrolyte capable of providing
charge compen 5 ating ionic dopants.
Example 13a
Preparation of
4-Acetyl-2-(4'-methoxy)benzoyl Aniline Mono~er
38.2 g of NaOH was dissolved in metanol (200 ml) in a
l-liter 3-neck flask provided with a mechanical stirrer, reflux
condenser, N2 inlet and a heating mantle. 28014 g (0.19 mol)
of p-methoxyphenyl-acetonitrile was added followed by 40 g
(0.191 moles) of p-nitro-aceto-phenone ethylene glycol ketol.
The reaction was stirred mechanically under reflux for 22
hours.
The produc-t was Eiltered off, washed with water and
recrystallized from methanol.
The product had the formula:
~ N
~0
LI ~
OCH3
~llZ()~
Analysis calculated for C181ll704N
Calc Fnd.
% C 69.~4 68.16%
H 5.50 5.41
N 4.50 4.26
Example 13b
llydrogenation of the product of Example 13a
17.12 g (0.055 mol) of the product of Example 13a was dissolved
in 150 ml of tetrahydrofuran and 4 ml of triethylamine in a 500 ml 3-neck
flask provided with a gas inlet tube, reflux condenser, thermometer and a
magnetic stirrer. 1.2 g of 5% Pd/carbon catalyst was added.
The flask was flushed with nitrogen and then coImected to a slow
stream of hydrogen.
The reaction was stirred magnetically at room temperature for
9 hours.
Thin layer chromatography indicated complete reaction.
The reaction was flushed with nitrogen, and the catalyst filtered
off through celite.
The filtrate was evaporated to an oily residue, 19.3 g.
The product had the formula:
~NH2
\~
0
OCH~
Example 13c
Hydrolysis of the product of Example 13b
19.1 g of the product of Example 13b was dissolved in 60 ml of
tetrahydrofuran and 30 ml of water
- 34 -
~z~
in a 250 ml round bottom flask. The pH of the solution
was adjusted to approximately 3 with conc. HCl and the
reaction allowed to stand at room temperature for approxi-
mately 18 hours.
Thin layer chromatoyraphy showed complete hydro-
lysis.
The reaction mixture was poured into 300 ml of
saturated Na2CO3 solution and extracted three times with
an equal volume of methylene chloride.
The combined methylene chloride solution was
washed with water, dried and evaporated to give 14.5 g of
yellow residue.
The product was recrystallized from methylene-
chloride hexane m.p. 119-123C.
The product had the formula:
,~" NH 2
0
0 ~3
OCH3
Analysis calculated for C16H15O3N
Calc. Fnd.
% C71.36 71.33%
% H 5.61 5.69
% N 5.20 5,78
Example 13d
Preparation of
Poly [2,6-(4-p-methoxyphenyl)quinoline]
The catalyst solution was prepared by dissolving
9.44 g (66.5 mmoles) of P2OS (weighed in a dry box) in 24
ml of m-cresol (Aldrich gold label) in a 50 ml 3~neck
round bottom flask fitted with a mechanical stirrer,
reflux condenser and an N2 inlet.
-35-
,'d '
,h
~ ~'P~q~
The catalyst solution was mechanically stirred
and heated in an oil bath at 105C, under an N2 blanket,
until the solution became homogeneous (approximately
2-1/2 hours). 3 g (11~16 mmoles) of the monomer of
Example 13c was added followed by 10 ml of m-cresol. The
temperature of the oil bath was increased to 120 and the
polymerization reac~ion run of this temperature for
48 hours~ The color of the solution changed from gold to
deep red and the solution became more viscous.
The polymerization solution was poured slowly
into 500 ml of a 10% solution of triethylamine in ethanol
and stirred at room temperature overnight. On neutraliza-
tion the polymer formed a spindle.
The polymer was collected by filtration, washed
with ethanol and extracted with ethanol in a Soxhlet
extractor overnight.
Following the extraction, it was filtered and
dried in vacuo at 70C to give 2.3 g (88.5%) of dry
polymer.
The polymer had the formula:
~r~_
Analysis:
Calc.*Fnd.
% C 82.38 78.52
H 4.75 4.40
N 6.01 5.52
[nj = .83 dl/g (measured in H2SO4).
Thereafter, the polymer was rendered conductive
in accordance with the procedures for Example 3 using 0.5
molar solution of sodi~m anthracenide-in T~F instead of
~!; based on C16Hll NO as the repeating unit.
--36--
4~
01
-37-
sodium naphthalide. The conductivity was measured in
accordance with Example 4~ The polymer had a conductivity
05 of 205 ohm~I cm 1~
Example 14
Preparation of --
Poly[2,6-(1-Methyl-4-phenyl)quinolinium]metasulfate
Poly 2,6-(4-phenylquinoline) coated platinum
wires were placed in a 50 ml round bottom flask and
covered with 10 ml of Dimethyl sulfate (Aldrich~. The
flask was fitted with a reflux condenser and a drying tube
inside a hood. The reaction was allowed to stand at room
temperature overnight and then heated at reflux for
6 hours.
After cooling, dimethyl sulfate solution was
de~anted off and the wires quenched with approximately 30
ml of a 10% solution of triethylamine in ethanol~ Follow-
ing neutralization the w~res were thoroughly washed with
ethanol and dried in vacuo at 80C~
The polymer had the formula:
25~ 3
C~3S3l
30CH3 n
The polymer was rendered conductive in accord-
ance with Example 3. However, the dopan~ was 0.5 molar
sodium anthracenide in THF. The conductivity of the
polymer was 0075 ohm 1 cm 1 as measured in acco~dance with
Example 4.
nl
-38-
Example 15
05 _ Electrochemical Doping of
Poly[2,6~ methyl-4-phenyl)quinolinium]
A 5~inch platinum wire was coated with a thin
film of poly 2,6-(4-phenylquinoline) as in Example 10.
The polymer was then quaternized as in Example 14.
The resulting polymer coated wire was connected
to the apparatus described in Example 10 and immersed into
a 0.1 M solution of tetraethylammonium tetrafluoroborate
in acetonitrile. A linear potential sweep varying from
-O.5 to -1.3 volts vs. SCE was applied to the platinum
lS wire. The output current was essentially nil until the
potential reached about -OJ8 volts~ at which point the
cathodic current increased rapidly, peaking at -1.1 volts.
Upon reversal of the potential sweep, an anodic current
was observed, peaking at -0.8 volts.
2~ This behavior indicates an initial resistance to
current flow followed by a rapid uptake of electrons to
~orm a reduced polymer. In effect the polymer was made
electroactive by the application of a potential of about
-l.l volts vs. SCE in the presence of an electrolyte
solution.
Example 16
Electrochemical Doping of Copolymer From
4~41-Diamino-3,3'-dibenzoyldiphenylether
and p-diacetylbenzene
A 5-inch platinum wire was coated with a thin
film of the polymer of Example 6d by dipping the wire into
a 5% solution of the poly~er in a m-cresol/P205 mixture.
The film-coated wire was neutralized by dipping into a lO~
triethylamine - 9o% ethanol solution and dried in a vacuum
oven at 60C.
The polymer coated wire was connected to the
apparatus described in Example 10 and immersed into a 0.1
M solution of tetraethylammonium tetrafluoroborate in
acetonitrile A linear potential sweep, varying from 0 to
-2.5 volts vs, SCE was applied to the platinum wire The
output current was essentially nil until the potential
~39 -
reached a~out -1.7 volts. At that point the cathodic current
increased rapidly to a maxim-lm at -2.2 volts and exhibited a
doub]e wave with a peak separation of 200 mV. Upon reversal of
the potentlal sweep an anodic current, also ex'nibiting a double
wave, was observed at -1.8 volts. When the initial -1.1 volt
potential was applied, the polymer adhering to the wire changed
Erom a nearly colorless transparent appearance to a dark,
metallic color. This color disappeared upon raising the
voltage to greater than 1.5 volts.
This behavior indicates an initial resistance to
current flow followed by a rapid uptake of electrons resulting
in a charged polymer containing tetraethylammonium ion as the
charge compensa-ting ionic dopant. In effect the polymer was
made electroactive by the application of a potential o-f about
-2.2 volts V5. SCE in the presence of an electrolyte solution
capahle of providing charge compensating ionic dopants.
Example 17
Electrochemical Doping oE Copolymer from
4,~'-Diamino-3,3'-dibenzoylbiphenyl
and 4,A' diacetyl~iphenyl
A 5-inch platinum wire was rotated with a thin film
of the polymer of Example ~d by dipping the wire into a 5%
solution of the polymer in m-cresol/P2Os mixture. The ~ilm-
coated wire was neutralized by dippin~ into a 10~ triethyl-
amine-90~ e-thanol solution and dried in a vacuum oven at 60~C.
The polymer coated wire was connected to the appar-
atus described in Example 10 and immersed into a 0.1 M solution
of tetraethylammonium tetraEluoroborate in acetonitrile. A
linear potential sweep, varying from 0 to -2.5 volts vs. SCE
was applied to the platinum wire. The output current was
essentiall~ nil until the poten-tial reached a valve of -1.7
volts. At that point the cathodic current increased rapidly,
peaking at -2.0 volts. Upon reversal of the po-tential sweep,
an anodic current was observed, peaking at -1.6 volts when
the initial
.~
01
-40-
-1.7 volt potential was applied, the polymer adhering to
the wire turned from pale yellow to a dark, metallic
- color. This color disappeared upon raising the voltage to
greater than -1.4 volts.
This behavior indicates an initial resistance to
current flow followed by a rapid uptake of electrons
resulting in a charged polymer containing tetraethylammo-
nium ion as the charge compensating ionic dopant. In
effect the polymer was made electroactive by the applica-
tion of a potential of about -2.0 volts vs. SCE in the
presence of an electrolyte solution capable of providing
charge compensating ionic dopants.
Example 18
Electrochemical Doping of
Poly 2,6-(4-(4'-chlorophenyl)quinoline)
A 5-inch platinum wire was coated with a thin
2~ film of the polymer of Example 9 by dipping the wire into
a 5% solution of the polymer in a m cresol/P205 mixture.
Thé film-coated wire was ne1~tralized by dipping into a 10%
triethylamine-90% ethanol solution and dried in a vacuum
oven at 60C.
The polymer-coated wire was connected to the
apparatus described in Example lO and immersed into a
0~1 M solution of tetrabutylammonium bromide in aceto-
nitrile. A linear potential sweep, varying from 0 to -203
volts vs. SCE was applied to the platinum wire. The out-
put current was essentially nil until the potential
reached about -1.5 volts. At that point the cathodic
current increased rapidly, peaking at -l.~ voltsO Upon
reversal of the potential sweep an anodic current was
observed, peaking at 1,3 volts. When the initial
-1.5 volt potential was applied, the polymer adhering to
the wire turned to a dark metallic color. Thls color
disappeared upon raising the voltage to greater than
-1.2 volts.
This behavior indicates an initial resistance to
current flow followed by a rapid uptake of electrons
~3
~1
-41-
resulting in a charged polymer containing tetraethylammo-
0 nium ion as the charge compensating ionic dopant. In
effect the polymer was made electroactive by the applica-
tion of a potential of about -1.8 volts vs. SCE in the
presence of an electrolyte solution capable of providing
charge compensating ionic dopants.
Example 19
Electrochemical Doping of
Poly 2,6-(4-(4'-methoxyphenyl)quinoline)
A 5~inch platinum wire was coated with a thin
film of the polymer of Example 13d by dipping the wire
into a 5% solution of the polymer in a m-cresol/P205 mix-
ture. The film-coated wire was neutralized by dipping
into a 10% triethylamine-9o% ethanol solution and dried in
a vacuum oven at 60C.
The polymer coated wire was connected to the
appara~us described in Example 10 and immersed into a
0.1 M solution of tet~abutylammonium bromide in aceto-
nitrile. A linear potential sweep, varying from 0 to -2.3
volts vs. SCE was applied to the platinum wire. The out-
put current was essentially nil until the potential
reached about -1~5 volts. At that point the cathodic
current increased rapidly, peaking at -2.1 volts. Upon
reversal o the potential sweep an anodic current was
observed, peaking at -1.5 volts. When the ini~ial
-1.5-volt potential was applied, the polymer adhering to
the wire turned to a dark metallic color. This color
disappeared upon raising the voltage to greater than
-1~3 volts~
l'his behavior indicates an initial resistance to
current flow followed by a rapid uptake of electrons
resulting.in a charged pol~mer containing tetraethylammo-
nium ion as the charge compensating ionic dopant. In
effect the polymer was made electroactive by the applica-
tion of a potential of about -2.1 volts vs. SCE in the
presence of an electrolyte solution capable of providing
charge compensating ionic dopants.
. .
Example 20
Doplng and Conductivity Measurement of Poly 2,6-(4-phenylquinoline)
The polymer poly 2,6-(4-phenylquinoline) was doped and rendered
electroactive and the conductivity thereof was determined in accordance
with Examples 3 and 4. However, the conductivity modifier was 0.5 molar
sodium anthracenide in TIIF. The conductivity of the electroactive polymer
was 20 ohm 1 cm 1.
Example 21
Doping and Conductivity Measurement of Poly 2,6-(4-(4'-chloro-
phenyl)quinoline)
The polymer of Example 9 was doped and rendered electroactive and
the conductivity thereof was determined in accordance with Examples 3 and 4.
However, the conductivity modifier was 0.5 molar sodium anthracenide in THF.
The conductivity of the electroactive polymer was 1.25 ohm cm
Example 22
Doping and Conductivity Measurement of Poly 2,6-(4-phenylquinoline)
The polymer poly 2,6-(4-phenylquinoline) was doped and rendered
electroactive and the conductivity thereof was determined in accordance with
Examples 3 and 4. However, the conductivity modifier was 0.1 molar sodium
anthracenide in THF. The conductivity of the electroactive polymer was
15 h -1 -1
Example 23
Doping and Conductivity Measurement of Poly 2,6-(4-phenylquinoline)
The polymer poly 2,6-(4-phenylquinoline) was doped and rendered
electroactive and the conductivity thereof was determined in accordance
with Examples 3 and 4. However, the conductivity modifier was 0.01 molar
sodium anthracenide in THF. The conductivity of the electroactive polymer
was 15 ohm 1 cm 1.
- 42 -
Example 24
Doping ancl Conductivity Measurement of Poly 2 9 6-(4-phenylquinoline)
Tl~e polymer poly 2,6-(4-phenylquinoline) was doped and rendered
electroactive and the conductivity thereof was determined in accordance
with Examples 3 and 4. However, the concluctivity modifier was 0.005 molar
sodium anthracenide in THE. The conductivity of the electroactive polymer
was 2.75 ohm cm
-42a-
71~
