780
Chem. Mater. 1992,4, 780-788 polymer films that were simply soaked and shaken in water, as above. The second set were not coated with 1 but were exposed to 10 Mrad of yrays and then treated with water. The last control set was coated with 1 before exposure to water. Stability of Hydrogel Grafts. Grafts of 1 were treated with 80% acetic acid, 0.1 N NaOH, THF, methanol, ethanol, hexane, and deionized water. During each treatment the samples were sonicated and agitated. The solutions were inspected visually to check for suspended hydrogel. In addition, the solutions were monitored by 31PN M R spectroscopy to monitor for the presence of any dissolved polymer 1.
-8.4 ppm. Elem. Anal. Calcd C, 42.40% H, 7.83%;N, 4.94%. Found: C, 41.28%; H, 7.85%; N, 4.96%. M,,, = 2 X lo6. Preparation of [NP(HNCH&], (2). Polymer 2 was prepared
by previously described methods.26 The characterization data were consistent with previous preparations of this polymer: 31P NMR +6.1 ppm(s); M, = 1 X lo6. Coating and Irradiation of Samples. Clean polymer film samples were dipped into 10% aqueous or methanolic solutions of 1 for 1 min and were then removed and allowed to dry. Each f i i was dipped a minium of five times. The multicoated films were dried for 24 h and were then d e d in an evacuated container. Sampleswere degassed and sealed under vacuum in freeze-dryer bottles. The samples were then irradiated with @'Co y-radiation at a dose rate of 0.222 Mrad/h for 0, 1, 5, or 10 Mrad. After irradiation, the films were soaked in and regularly shaken in deionized water for 5 days and were then soaked and shaken in ethanol for 1 day. Three sets of controls were prepared. The first set was the pure
Acknowledgment. This work was supported by the National Institutes of Health, through the National Heart, Lung, and Blood Institute (Grant No. HL 11418) and by the Johnson and Johnson COSAT program. Registry No. PTFE, 9002-84-0; Water, 7732-18-5.
Polyphosphazenes Bearing Polymerizable Pyrrole, Thiophene, and Furan Side Groups: Synthesis and Chemical Oxidation Harry R. Allcock* and Jeffrey A. Dodge Department of Chemistry, Pennsylvania State University, University Park, Pennsylvania 16802
Leon S. Van Dyke and Charles R. Martin* Department of Chemistry, Colorado State University, Fort Collins, Colorado 80521 Received April 2, 1992 The synthesis and chemical oxidation of linear poly(organophosphazenes) that bear polymerizable, heterocyclic side groups are described. The polymers were prepared for use as precursors to electronically conductive materials. The polymers have the general structure [NP(OR),],, where R is -CHzCCHSCHCH, , -CH&H2CCHSCHCH, -CH&HZCSCHCHCH, -CHzCHZCHzNCHCHCHCH, -CH,CCHOCHCH, -(CH2)11NCHCHCHCH, or -(CH2CH20)2CHzCH2NCHCHCHCH, and [NP(NHR),],, where R is -CHzCHzCHzNCHCHCHCHor -CH2CHzCCHSCHCH. The cyclic trimer [NP(OCH2CCHSCHCH),I3 was synthesized as a model compound and as a possible precursor to cyclomatrix conductive materials. Molecular structural Characterization for the linear high polymers was achieved by the use of 'H, 13C,and 31PNMR spectroscopy, gel permeation chromatography, and elemental microanalysis. The glass transition temperatures of the polymers were determined using differential scanning calorimetric analysis and were found to be in the range -48 to +1 "C. Chemical oxidation of the materials was carried out in solution using Fe(C104)3or FeC13. The resultant dark, insoluble powders were compressed into pellets, and their electronic conductivities were measured. All the materials were found to be semiconductive with conductivities in the range 4 X lO-lO-5 X S cm-'. The results of attempted electrochemical oxidation and chemical oxidation using iodine are also described.
. . . - b
i
i
. . .
Introduction In recent years, a growing interest has been evident in the development of electronically conductive organic Such materials are technologically important because they offer the prospect of combining electronic conductivity with other useful properties such as toughness, flexibility, or ease of fabrication into devices. Among
the most intensively studied conductive polymers are poly(pyrrole), poly(thiophene), and their derivatives. Research efforts in numerous laboratories are concentrated on improving the tractability of these material^.^ Poly(organophosphazenes) comprise a broad class of inorganic-organic polymers of general structure [NP&],.4 The possibility that electronic conductivity might be induced in polyphosphazenes has been considered in earlier
(1) Handbook of Conductive Polymers; Skotheim, T. A., Ed.; Marcel Dekker: New York, 1986. (2) (a) MacDiarmid, A. G.; Chiang, J. C.; Richter, A. F.; Epstein, A. J. Synth. Met. 1987, 18, 285. (b) Kanatzidis, M. G. Chem. Eng. News 1990, 68 (49), 36.
(3) Processable Electronically Conductiue Polymers; Skotheim, T. A,, Ed.; Marcel Dekker: New York, 1991. (4) Allcock, H. R. Phosphorus-Nitrogen Compounds: Cyclic, Linear, and High Polymeric System; Academic Press: New York, 1972.
0897-475619212804-0780$03.00/0 0 1992 American Chemical Society
Chem. Mater., Vol. 4, No. 4, 1992 781
Polyphosphazene Bearing Polymerizable Side Groups
p 0
0
&
0
3
2
1
p
Chart I
4
Js HN
8
I
+ P =I N - f n
Scheme I
Scheme I1
7 -NaCI
X = N, S o r 0
work. However, attempts to generate conduction within the phosphorus-nitrogen backbone have not yet been su~cessful.~Therefore, we and others have adopted an alternative 'outrigger" approach in which the polymer backbone serves 88 a platform for the attachment of electroactive side group^.^ For example, tetracyanoquinodimethane units have been attached 88 side groups to quaternized phosphazene polymers to provide materials that are inherent semiconductors.' Polyphosphazenea that contain phthalocyanine6and pyrrole9 side groups have also been synthesized, and these polymers yield semiconductive materials following doping. In this paper, we describe the synthesis and chemical oxidation of poly(organophosphazenes) that bear pyrrole, (5) Allcock, H. R. Chem. Eng. News 1985, 63 (ll),22. (6) Inorganic and Organometallic Polymers; Zeldin, M., Wynne, K. J., Allcock, H. R., Eds.;American Chemical Society: Washington DC, 1988. (7) Allcock, H. R.;Levin, M. L.; Austin, P. E. Inorg. Chem. 1986,25, 2281. (8) Allcock, H.R.;Neenan, T. X. Macromolecules 1986, 19, 1495. (9) Haddon, R. C.; Stein, S. M.; Chicheater-Hicks,S. V.; Marshall, J. H.; Kaplan, M. L.; Hellman, M. Y. Mater. Res. Bull. 1987,22, 117.
thiophene, or furan side groups. The objective was to prepare tractable, well characterized, high polymers that could be used as precursors to electronically conductive materials (Scheme I). Variations in the molecular structure of the side groups were explored, and these included changes in the type of heterocycle and the length and type of spacer group linking the heterocyclic unit to the polymer backbone. Conductivity measurements of the oxidized materials were taken from compressed pellets using both two- and four-point probe methods. In the following discussion, the synthesis and characterization of compounds 1-10 is described first. The various oxidation experiments using these materials are then described together with a discussion of the conductivity measurements and materials characterization. The relationship between the conductivity of the oxidized materials and the structure of the side groups is also addressed.
Results and Discussion Synthesis of Polymers 1-7. The overall synthetic m pathway to single-substituentpolymers 1-7 is s in Scheme 11,and the corresponding molecular structures
Allcock et al.
782 Chem. Mater., Vol. 4, No. 4, 1992 Table I. Characterization Data for [NP(OR),], and [NP(NHR)2]. EA
_.
. [NP(OCH2CCHSCHCH)21n . [NP(OCH2CH2CCHSCHCH)2In
1.2 x 106
2.0 x 106
-29
9.8 x 104
8.5 x lob
-37
[NP(OCH2CH2CH2NCHCHCHCH)2]n (3)
8.9 x 104
3.2 X lo6
-35
comDound
(1)
(2)
M.9
MU.
T., 'C
C H N
c1 C H N
c1 C H N
c1 7.6 x
[NP(OCH2CCHOCHCH),In (4)
104
1.9 x 106
-44
C H N
c1
4.4 x 104
[NP((OCH2CH2),NCHCHCHCH),1. (5)
1.9 x 106
-48
C H N
.
c1
4.5 x 104
[NP(O(CH2)11NCHCHCHCH)~ln (6)
1.7 X lo6
-36
C H N
c1 6.7 X lo5
[NP(OCH2CH2CSCHCHCH)21. (7)
.
[NP(NHCH2CH2CCHSCHCH)zln (8)
1.4 X 106
-41
C H N
c1
2.9 X lo6
3.2
X
lo6
1
C H N
c1 [NP(NHCH2CH2CH2NCHCHCHCH)2ln (9)
1.3 X lo6
4.1 X lo6
-8
C H N
c1
calcd
found
44.28 3.69 5.17 0 48.16 4.68 4.68 0 57.34 6.83 14.33 0 50.21 4.18 5.86 0 54.42 7.26 9.52 0 69.63 10.06 8.12 0. 48.16 4.68 4.68 0 48.48 5.39 14.14 0 57.75 7.56 24.05 0
43.91 3.64 4.93 0.05 47.88 4.81 4.84 0.24 57.64 6.65 14.64 0.03 52.33 4.14 5.82 0.05 54.48 7.28 9.42 0.04 68.98 10.11 7.49 ~~ and poly(phen y l a c e t ~ l e n e ) . ~This ~?~~ behavior has been attributed to the formation of a charge-transfer complex between the iodine and the polymer. The mechanism for the resultant conductivity is still a subject for debate.23*n The highest reported conductivity for a polyphosphazene is lo4 S cm-' for iodine-doped poly[bis(4-(dimethylamino)phenoxy)p h o ~ p h a z e n e ] . ~It~ was reported that the conductivity level was stable in the presence of iodine, but the effect of dynamic vacuum on the conductivity of the material was not mentioned.
Control Polymers.
Poly[bis(trifluoroethoxy)phos-
phazene], [NP(OCH2CF3)2]n,10b was used as a control for the oxidation experiments. The formation of a conductive material from this polymer would imply that the conduction is the result of oxidation of the phosphorus-nitrogen backbone. The trifluoroethoxy side groups should be inert to the oxidation conditions used in this work. If the compound could not be oxidized, then any electronic conductivity in oxidized materials 1-10 must be due to the side groups and not the polymer backbone. Several attempts were made to oxidize [NP(OCH2CF3),],. Potential sweep experiments conducted in a variety of solvents (such as MeCN, PhCN, and PhN02) with 0.2 M n-Bu4NBF4supporting electrolyte revealed no oxidation currents up to a potential of +3.0 V. Only currents associated with solvent breakdown were detected. This polymer proved to be impervious to chemical oxidation as well. Attempted oxidation using Fe(C104)3, FeC13, and Iz resulted in no detectable interaction and the polymer could be reisolated unchanged. Therefore, the phosphorus-nitrogen backbone in [NP(OCH2CF3)2]nappears to be resistant to oxidation under the conditions used in this work and any conductivity in 1-10 is most likely a contribution from the heterocyclic side groups. Compound 7 was also prepared for use as a control polymer; it has a structure more closely related to the heterocyclic polymers used in this work. Polymer 7 was designed 80 that although oxidation and cross-linkingcould take place through the open 5-position on the thiophene ring, polymerization could not occur to yield a conjugated heterocyclic polymer. Only nonconductive thiophene dimers should result from oxidation. It is known that reaction at the open 3 and 4 positions does not occur readily, and even if it did, this would yield nonconjugated, and therefore nonconductive, materials. Thus, any conductivity detected in 7 following oxidation would probably be a contribution from the polymer backbone. Polymer 7 was oxidized chemically in benzonitrile using Fe(C104)3as described below. Following anion exchange and drying, the conductivity was found to be
