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 Simultaneous polymerization, doping and solubilization of heterocyclic polymers, solutions and cast articles

Details
Inventors: Frommer, Jane E.; Elsenbaumer, Ronald L.;
Assignee: Allied Corporation (Morris Township, Morris County, NJ)
Primary Examiner:
Assistant Examiner:
Attorney, Agent or Firm:

Polymer solutions are formed by reacting an aromatic heterocyclic such as thiophene, substituted thiophenes or oligomers of either with an acceptor doping agent (Lewis Acid) such as arsenic pentafluoride in the presence of certain solvents such as arsenic trifluoride. Articles such as air-stable conductive poly(3-methylthiophene) are cast from such solutions.

DETAILED DESCRIPTION OF THE INVENTION The solvent used in the present invention is preferably arsenic trifluoride, but it may also be other metal or non-metal halides having a liquid phase under atomospheric pressure for at least one temperature between about -150.
degree.
C.
and about +100.
degree.
C.
, with preferably a liquid point at atmospheric pressure for at least one temperature between about -100.
degree.
C.
and about +30.
degree.
C.
Such solvents include especially phosphorus trifluoride, phosphorus pentafluoride, phosphorus trichloride, phosphorus oxytrichloride, titanium tetrachloride, boron trifluoride, boron trichloride, boron tribromide, antimony pentachloride, antimony trichloride, arsenic trichloride and arsenic tribromide, in addition to arsenic trifluoride.
The solvent may also be chloroalkane liquid in the above temperature range and volatile (to the extent of at least 7 kPa vapor pressure at 100.
degree.
C.
or below).
Preferred chloroalkanes include dichloromethane.
The monomers used to form the polymer solute include, especially, five-member monoheterocyclic aromatics of the formula: ##STR1## wherein X is S, O, Se, NH, NR', PH or PR'; R.
sub.
1 is H alkyl, --OR, --SR or aryl; R.
sub.
2 is H, alkyl, --OR, --SR or aryl; R is alkyl or aryl; and R' is alkyl or aryl.
Exemplary of these preferred monomers are thiophene, 3-methylthiophene, 3,4-dimethylthiophene, 3-phenylthiophene, selenophene, pyrrole, N-methylpyrrole, 3-methylpyrrole, 3-phenylthiophene, 3-methylthiothiophene, and furans.
Other monomers useful include benzothiophene, dibenzothiophene and other, similar fused ring structures and substituted forms thereof knowm to form conductive polymers when acceptor-doped (see O.
K.
Kim, J.
Polym.
Sci.
, Polym.
Letters Ed.
, Vol.
20, pp.
663-66 (1982); G.
Tourillon et al.
, J.
Electroanal.
Chem.
, Vol.
135, pp.
173-178 (1982), the disclosures of which are incorporated by reference for such polymers).
Also included as suitable monomers are dibenzofuran, dibenzothiophene, phenazine, carbazole, pyridine, quinazoline, thiazole, thianthrene, thianaphthene and quinoxaline



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