Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
  • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
  • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
  • H01B1/124—Intrinsically conductive polymers
  • H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
  • B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/06—Polyethene
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
  • D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
  • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
  • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
  • H01B1/124—Intrinsically conductive polymers
  • H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/0088—Blends of polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
  • B29K2995/0003—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular electrical or magnetic properties, e.g. piezoelectric
  • B29K2995/0005—Conductive

Definitions

• This invention relates generally to conducting polymers, to ordered conjugated polymer precursors to conducting polymers, and to methods for making the same. More particularly, it relates to polymer blends and/or composites which contain conjugated polymers together with nonconjugated carrier polymers so as to provide shaped articles such as fibers, tapes, rods and films which can be rendered conductive and which also exhibit excellent mechanical and optical properties.
• Conjugated polymers and conducting polymers based on them were discovered in the late 1970s. They offer unigue optical properties and the possibility of combining the important electronic and optical properties of semiconductors and metals with the attractive mechanical properties and processing advantages of polymers. However, the initial conjugated polymer systems were insoluble, intractable, and non elting (and thus not readily processable into oriented structures) with relatively poor mechanical properties.
• the poly(3-alkylthiophene) derivatives (P3ATs) of polythiophene are soluble and meltable with alkyl chains of sufficient length, and the P3ATs have been processed into films and fibers.
• P3ATs poly(3-alkylthiophene) derivatives
• the P3ATs have been processed into films and fibers. See, e.g., Hotta, S., et al., Macromolecules. 2.0:212 (1987); Nowak, M. , et al. , Macromolecules. .12:2917 (1989); Eisenbaumer, R.L. , et al., Synth. Met.. £6.:267 (1988).
• the mechanical properties (modulus and tensile strength) of fibers and films, etc., of the P3ATs are modest and limit their use.
• conjugated systems based on poly(phenylenevinylene) (“PPV") and alkoxy derivatives of PPV have been synthesized via the "precursor polymer" route.
• PPV poly(phenylenevinylene)
• alkoxy derivatives of PPV have been synthesized via the "precursor polymer” route. See, for example, U.S. Patent Nos. 3,401,152 and 3,706,677 to Wessling et al.; Gagnon et al., Am. Chem. Soc. Polym. Prepr. 25:284 (1984); Momii et al., Chem. Lett. !_'.1201-4 (1988); and Yamada et al., JCS Chem. Commun. 19 . :1448-9 (1987).
• a saturated precursor polymer is synthesized.
• the precursor polymer is soluble and can be processed into the desired final shape.
• the precursor polymer is thermally or chemically converted into the conjugated polymer during or after the forming into desired final shape.
• Tensile drawing can be carried out during the -conversion.
• significant. chain extension and chain alignment of the resulting conjugated polymers can be achieved.
• the precursor polymer route may offer advantages, the multi-step synthesis is complex, makes the resultant materials relatively expensive, and limits their utility.
• nonconjugated polymers such as polyolefins, for example, ultra-high molecular weight (“UHMW”) polyethylene (“PE”) can be chain extended and chain-aligned by first dissolving the polymer in an appropriate solvent at an elevated temperature, then
• -25 threshold for example, typically about 16% v/v for approximately spherical particles
• shaped, articles such as fibers, tapes, rods, and films which retain the desirable properties of conjugated/conductive polymers are fabricated from a mixture of nonconjugated "carrier” polymer; for example, from ultra-high molecular weight polyethylene (UHMW PE) and a conjugated polymer or conjugated polymer precursor.
• carrier polymer for example, from ultra-high molecular weight polyethylene (UHMW PE) and a conjugated polymer or conjugated polymer precursor.
• UHMW PE ultra-high molecular weight polyethylene
• the solution can be made of a quantity of a polymeric precursor or conjugated polymer which may be converted either chemically or thermally to a desired conjugated polymer (as in the case of PPV and its derivatives) .
• a mechanically coherent, shaped structure is then prepared, e.g., in the form of a fiber, tape, film, or the like; this structure is comprised of the carrier polymer and either the conjugated polymer or the precursor.
• the blend fibers, tapes, films, or the like are then subjected to distortion such as tensile drawing to yield the desired shaped articles.
• composite articles fabricated through this processing route have excellent mechanical properties, i.e., with respect to tensile strength, elongation at break, and the like, and can be made electrically conductive as well. If desired, the composite articles may also be fabricated so as to retain color, or display other attractive optical characteristics.
• conjugated polymer shaped articles can be formed by the process of
• the physical distorting is carried out anisotropically so as to yield an oriented structure in the carrier polymer and in the conjugated polymer.
• the orientation of the conjugated polymer leads to anisotropic absorption and photoluminescence properties for the shaped article.
• the distorting is carried out by drawing, particularly to very high draw ratios (greater than 10 and often up to as much as 30 or 100 or more) .
• this invention provides the conjugated polymer products which this process makes possible and conductive polymer products which result from doping the conjugated polymer with ions.
• Figure 1 illustrates the chemical structure of the poly(3-alkylthiophenes) as discussed in Example 1.
• FIG. 2 schematically illustrates the synthesis of poly(2,5-dimethoxy-p-phenylenevinylene) (PDMPV) as described in Example 10.
• Figure 3 schematically illustrates two routes for the synthesis of poly(2-methoxy-5(2'-ethylhexyloxy)- p-phenylenevinylene) (MEH-PPV) as described in Example 15.
• Figure 4 is a graph showing anisotropic absorption for an oriented film at a draw ratio of about 50 of PE/MEH-PPV for polarization both parallel to (solid) and perpendicular to (dashed) the draw axis and for a spin-cast film (dot-dashed) , all at 8OK.
• the scattering loss from a UHMW-PE film of comparable thickness and draw ratio is shown (dotted) for comparison) .
• Figure 5 is a graph showing anisotropic absorption for a nonoriented free-standing film of PE/MEH-PPV (dashed) , absorption parallel to draw axis of the oriented film of PE/MEH-PPV (solid) , and anisotropic absorption of the spin-cast film (dot-dashed) all at 8OK.
• the inset compares absorption parallel to draw axis of the oriented film at 80K (solid) and at 300K (dashed) .
• Figure 6 is a graph depicting anisotropy in the 80K photo-luminescence spectrum, from an oriented film of PE/MEH-PPV for parallel pumping; the upper solid curve is photo-luminescence spectrum parallel to draw axis; the lower solid curve is photo-luminescence spectrum perpendicular to draw axis; the dotted curve is photo- luminescence spectrum perpendicular to draw axis scaled (times 30) for clarity.
• the insert shows the dependence of photo-luminescence spectrum on the polarization angle relative to the chain axis (the solid curve is a fit to COS 2 ⁇ ) .
• Figure 7 shows the anisotropic electro- absorption (electric field modulated absorption) of a film of oriented PE/MEH-PPV having a 6% volume fraction Of MEH-PPV.
• the method of the present invention involves five steps: (a) the dissolution of the appropriate carrier polymer and either a soluble conjugated polymer or a soluble precursor to a conjugated polymer in a suitable carrier solvent; (b) the preparation of a shaped article from the polymer solution by forming; (c) the gelling of the polymer solution either before or after it is formed into the shaped article; (d) the physically distorting of the shaped article through tensile drawing or like process to chain-extend or chain-align the carrier polymer, and to chain-extend and chain-align the conjugated polymer as well; and (e) the removing of the solvent before, during, or after the physical distorting step.
• step c the gelling of step c can be arrived at as part of step b and solvent removal can accompany the gelling or distorting so as to give a three or four step process.
• a precursor for example, in the route to PPV and its derivatives
• the tensile drawing or distorting can be carried out at a temperature selected to. serve to convert the precursor polymer to the conjugated polymer.
• the articles formed by the present process typically fibers, rods tapes, or films of the otherwise colorless and insulating carrier polymer—can be rendered electrically conductive by doping, exhibit excellent mechanical properties, and may or may not be colored or display other optical characteristics.
• a "shaped article” as used herein is intended to mean a mechanically coherent object having a defined form, for example, a fiber, rod, film, or tape.
• the inventiveness of the present process lies in the ability to form shaped articles (by means of solution processing) of polymers such as polyolefins for example ultra high and molecular weight polyethlene which are electrically conductive and exhibit excellent mechanical properties over the full range indicated in Table 1. They also can exhibit anisotropic absorption and emission spectra.
• a “conjugated” polymer as used herein means a polymer having a 7r-electron network which allows for electron transfer substantially throughout its molecular structure. Conjugated polymers are typically highly colored because of the strong absorption associated with the ⁇ - ⁇ * transition; the color, if any, will depend on the specific polymer, for the energy of the ⁇ - ⁇ * transition is determined by the polymer structure.
• substantially nonconducting as used herein to describe the carrier polymer is meant a conductivity ⁇ of less than about 10 S/cm and preferably less than IO "9 S/cm.
• the conductivity ⁇ of the composite materials provided and described herein is given as-the conductivity after doping, i.e., during or after preparation of the composite as described herein, the material is rendered conductive by either p-type (oxidative) or n-type (reductive) doping using standard dopants and techniques.
• a "precursor" polymer as used herein is a partly saturated polymer which can be converted to a final conjugated polymer by thermal treatment or by chemical treatment, or both.
• the precursor polymer is soluble in common solvents, whereas the converted conjugated polymer is either not soluble in such solvents or much less soluble than the precursor polymer.
• a polymer "composite” or “blend” as used herein means a structural mixture of two or more polymeric materials which may or may not be covalently bound to one another.
• An "oriented" material as used herein is intended to mean a polymeric structure in which individual polymeric chains are substantially linear and parallel.
• the criteria for the selection of the carrier polymer are as follows.
• the polymer is preferably a substantially nonconducting, flexible-chain polymer which allows for the formation of mechanically coherent structures (fibers, films, rods, tapes, etc.) at low concentrations, and which is stable with respect to the solvent used in processing.
• Low concentrations of carrier polymer are preferred in order to minimize processing difficulties, i.e., excessively high viscosity or the formation of gross inhomogeneities; however, the concentration of the carrier should be high enough to allow for formation of coherent structures.
• Preferred carrier polymers are high molecular weight (weight averaged molecular weight greater than about 50,000, more preferably greater than about 100,000 such as greater than about 500,000) flexible-chain polymers, such as polyethylene, isotactic polypropylene, polyethylene oxide, polystyrene, poly(aerylonitrile) , polyketones, polyesters, polyamides, and the like, and particularly preferred carrier polymers are polyethylene and polypropylene.
• these macromolecular materials enable the formation of coherent structures from a wide variety of liquids, including water, acids, and numerous polar and nonpolar organic solvents. Structures manufactured using these carrier polymers have sufficient mechanical strength at polymer concentrations in the carrier solvent as low as 1%, even as low as 0.1%, by volume, to enable the subsequent processing into the desired_shaped article.
• Mechanically coherent structures can also be prepared from lower molecular weight flexible chain polymers, but generally, higher concentrations of these carrier polymers are required. " Higher concentrations may have an undesirable effect on the drawability and properties of the final products.
• carrier polymer is made primarily on the basis of compatibility of the final conducting polymer and its reactants, as well as with the solvent or solvents used.
• blending of polar conducting polymers generally requires carrier structures that are capable of codissolving with or absorbing polar reactants. So, too, the conjugated polymer and carrier polymer are often soluble in one another. Examples of such coherent structures are those comprised of poly(vinyl alcohol), poly(ethylene oxide), etc., and suitable liquids.
• nonpolar carrier structures are selected, such as those containing polyethylene, polypropylene, poly(butadiene) , and the like.
• carrier polymer may be used to form the carrier solution and ultimately become a part of the final composite; i.e., mixtures of two or more carrier polymers may be incorporated into the initial carrier solution.
• the carrier solvent is one in which the carrier polymer is substantially soluble and one which will not interfere with the subsequent admixture with the conjugated polymer, gelation and formation into the first body.
• organic solvents are used. These can include halohydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride, aromatic hydrocarbons such as xylene, benzene, toluene, other hydrocarbons such as decaline, and the like. Mixed solvents can be used, as well. Depending upon the nature of the carrier polymer, polar solvents such as water, acetone, acids and the like may be suitable. These are merely a representative exemplication and the solvent can be selected broadly from materials meeting the criteria set forth above.
• the conjugated polymers used herein include the wide range of conjugated polymers known in the art. These include, for example, poly(2-methoxy,5-(2'-ethyl- hexyloxy)-p-phenylenevinylene) or "MEH-PPV", P3ATs, poly(3-alkylthiophenes) (where alkyl is from 6 to 16 carbons), such as poly(2,5-dimethoxy-p-phenylene vinylene)-"PDMPV", and poly(2 ,5-thienylenevinylene) ; poly(phenylenevinylene) or "PPV” and alkoxy derivatives thereof; and polyanilines.
• conjugated polymers known in the art. These include, for example, poly(2-methoxy,5-(2'-ethyl- hexyloxy)-p-phenylenevinylene) or "MEH-PPV", P3ATs, poly(3-alkylthiophenes) (where
• a polymeric precursor which may be converted to the desired conjugated polymer is used.
• the precursor must, as above, be soluble in the solvent. It will typically be readily converted to the ultimately desired polymer via either thermal or chemical means. If such is the case, the thermal or chemical treatment may take place either before, during, or after gelation.
• soluble precursor polymers include those described by Wessling et al. in U.S. Patent Nos. 3,401,152 and 3,706,677, cited supra (i.e., as precursors to PPV) as well as those described by Gagnon et al., Momii et al., and Yamada et al. , all cited supra. _
• the initial concentration of the carrier in the solution polymer generally is selected above 0.1% by weight, and preferably above about 0.2% or 0.75% by weight, basis solvent and more preferably from about 0.1% by weight to about 50% by weight. More preferably, the concentration of the carrier polymer in the initial solution is from about 0.1% by weight to about 25% by volume.
• the final composite is one in which the conjugated polymer represents at least about 0.1 wt.% of the total polymer in the composite, more preferably from about 0.2 wt.% to about 90 wt.%, most preferably from about 0.5 wt.% to about 50 wt.%. In some settings it is desired to provide a final composite in which the conjugated (conducting) polymer represents at least about 5% of the total composite, preferably at least about 10% and more preferably at least about 20%
• the concentration of conjugated polymer (or precursor) in the carrier solution should be set to provide this relationship with the carrier polymer.
• the carrier solution is formed into a selected shape, e.g., a fiber, tape, _rod, film or the like, by extrusion or by any other suitable method.
• Gels can be formed from the carrier solution in various ways, e.g., through chemical crosslinking of the macromolecules in solution, swelling of crosslinked macromolecules, thermoreversible gelation, and coagulation of polymer solutions.
• the two latter types of gel formation are preferred, although under certain experimental conditions, chemically crosslinked gels may be preferred.
• Thermoreversible gelation refers to the physical transformation of polymer solution to polymer gel upon lowering the temperature of a homogeneous polymer solution (although in exceptional cases a temperature elevation may be required) .
• This mode of polymer gelation requires the preparation of a homogeneous solution of the selected carrier polymer in an appropriate solvent according to standard techniques known to those skilled in the art.
• the polymer solution is cast or extruded into a fiber, rod, or film form, and the temperature is lowered to below the gelation temperature of the polymer in order to form coherent gels.
• This procedure is well known and is commercially employed, e.g., for the formation of gels of high molecular weight polyethylene in decalin, paraffin oil, oligomeric polyolefins, xylene, etc., as a precursor for high-strength polyolefin fibers and films.
• Coagulation of a polymer solution involves contacting the solution with a nonsolvent for the dissolved polymer, thus causing the polymer to precipitate. This process is well known, and is commercially employed, for example, in the formation of rayon fibers and films, in the spinning of high-performance aramid fibers, etc.
• the gelation step can be carried out before, during, or after the "Forming Step". Solvent is removed from the carrier solution during the gelation step or thereafter. Solvent can also be removed during the distorting step. In many cases solvent is removed in several stages, during and after gelatio ..
• dry spinning can be employed.
• the solvent is removed by evaporation, leading to the desired carrier structure formation.
• thermoreversible gels are generally substantially greater than melt processed materials. (P. Smith and P.J. Lemstra, Colloid and Polym. Sci., 258:891 (1980).
• the large draw ratios possible with certain thermoreversible gels are also advantageous if composite materials may be prepared with materials limited in their drawability due to low molecular weights.
• conducting polymers not only do the mechanical properties- improve, but, more importantly, the electrical conductivity and optical properties also often display both anisotropy and drastic enhancement upon tensile drawing.
• the carrier/conjugate formed articles are typically subjected to substantial deformation such as a draw ratio (final length:initial length) of at least about 1:1 and preferably at least 10:1 and more preferably at least 20:1.
• a draw ratio final length:initial length
• This drawing has the effect of physically orienting not only the carrier molecules but also the molecules of conjugated polymers. This leads to advantages such as anisotropic optical and electrical properties, for the carrier/conjugate composites as a whole.
• the polymer composite materials can be rendered conductive by doping during or after fabrication into the shaped articles.
• acceptor doping the backbone of the acceptor-doped polymer is pxidized, thereby introducing positive charges into the polymer chain.
• donor doping the polymer is reduced, so that negative charges are introduced into the polymer chain. It is these mobile positive or negative charges which are externally introduced into the polymer chains that are responsible for the electrical conductivity of the doped polymers.
• the materials prepared according to the aforementioned method are thus shaped polymer blends or composites, i.e., fibers, rods, films, tapes, or the like, which are electrically conductive and which display superior mechanical properties. More specifically, the composites provided herein can have an electrical conductivity ⁇ of at least about 10 —7 S/cm and can in some cases have an electrical conductivity ⁇ of at least about 0.75 S/cm and a Young's modulus E of at least about
• This process can provide materials in which the product of ⁇ and E is at least about 0.3 (GPa) (S/cm) or even at least about 1 0 (GPA) (S/cm) or even at least about 5 (GPa) (S/cm) .
• linear density (linear density) of the samples was measured by weighing 100 to 200 mm of the fibers.
• the cross- sectional areas . of the fibers were determined from a knowledge of the linear density in combination with knowledge of the
• a four- probe technique for conductivity measurement was used to measure the conductivity o ⁇ _the materials herein. The four contacts were made on the surface of the sample fibers in a linear array. The testing probe was placed into a evacuable chamber from which ambient atmosphere was removed and into which iodine vapors were introduced. The vapor pressure of iodine at room temperature was 0.34 mm Hg. A current (1) was passed through the outermost probes and the voltage drop measured across the innermost probes. The voltage measurement was carried out by means of a high-impedance voltmeter and is considered to be essentially a zero current measurement.
• the contact resistance between the innermost probes and the sample is minute, since the current flow through the voltmeter is minute.
• Ohmic contacts were carried out using conductive carbon paint contacts (SPI, Inc., West Chester, PA) in which platinum electrodes were attached to the samples by means of finely divided graphite in .isopropyl alcohol.
• Example 1 The poly(3-alkythiophenes) were prepared by direct oxidation of the appropriate 3-alkylthiophene by FeCl 3 (J.-E. Osterholm et al., Svnth. Met.. 28:C435 (1989)).
• Figure 1 shows the chemical structure of the poly(3-alkylthiophenes) .
• a 100%-by-weight film of poly(3-octylthiophene) was cast onto glass from a 3 wt.' solution in chloroform (Fisher Scientific) .
• the films were dried under nitrogen and lifted from the substrate by soaking in methanol (Fisher Scientific) .
• Appropriate samples were cut from the dried films and subsequently drawn to their maximum draw ratio (L+ ⁇ L/L) at a variety of temperatures on the Instron Tensile Tester equipped with an oven capable of maintaining such temperatures.
• Example 2 A 100%-by-weight film of poly(3-dodecylthio- phene) (PDDT) was cast onto glass from a 3 wt.% solution in chloroform (Fisher Scientific) . The films were dried under nitrogen and lifted from the substrate by soaking in methanol (Fisher Scientific) . A 100%-by-weight poly(3-octylthiophene) (POT) fiber was produced by wet spinning into acetone (Fisher Scientific) according to standard procedures. The fibers and films of PDDT were cut to appropriate sizes and drawn to various draw ratios at 100°C in air. The fibers and films of the POT and PDDT have a lustrous greenish appearance on reflection and are red in transmission. The mechanical properties of the drawn polymers are listed below:
• Example 3 The poly(3-dodecylthiophene) samples of Example 2 were drawn, in air, at 100°C to various draw ratios.
• the poly(3- ⁇ ctylthiophene) samples of Example 2 were drawn, in air, at 105°C to various draw ratios.
• the drawn poly(3-octylthiophene) samples were then doped at room temperature in iodine vapor and measured using a 4-probe device.
• the poly(3-dodecylthiophene) samples were doped at.40°C in ' 1.74 wt.% solution of 488 mg N0SbF g (Alfa Chemicals) in 27.51 g acetonitrile (Aldrich) .
• the conductivities of the films or ibers reached constant values of:
• the composite fiber was of 68 denier, and dark red-brown in color.
• the polyoctylthiophene content of this composite fiber was 75% by weight.
• the mechanical properties of the composite fiber were determined to be as follows for various draw ratios, with the samples being drawn at ' 105ANCC in air.
• Example 5 The polyoctylthiophene/polyethylene composite fiber of Example 4 was dried and drawn, in air, at 105°C to various draw ratios. The drawn samples were then doped at room temperature in iodine vapor using a 4- probe device. The conductivities of the composite fibers reached constant values of:
• Example 6 Decalin (decahydronaphthalene, Aldrich) ; 9.7 g was mixed, at room temperature, with 200 mg of polydodecylthiophene in a 50 ml test tube. This stirred mixture was blanketed with nitrogen gas and heated to 104°C, at which time 200 mg of ultra-high molecular weight polyethylene (Hostalen GUR 415, Hoechst) was added. Subsequently, the mixture was heated to a temperature of 115°C, at which point stirring was stopped, and the temperature was raised further to 150°C for 1 hour. A viscous orange liquid was obtained. The solution was cooled, and the red orange gel was transferred to a laboratory-scale spinning apparatus. A polyethylene/ polydodecythiophene gel fiber was spun according to standard procedures, and subsequently drawn at 105°C in air.
• Hostalen GUR 415 ultra-high molecular weight polyethylene
• the composite fiber was of 600 denier, and dark red-brown in color.
• the polydodecylthiophene content of this composite fiber was 50% by weight.
• the polydodecylthiophene/polyethylene composite fiber of Example 6 was drawn, in air, at 105°C.
• the drawn samples were doped at 40°C in -1.75 wt. % solution of 488 mg N0SbF 6 (Alfa Chemicals) in 27.5 g acetonitrile (Aldrich) .
• the doped samples were removed from the doping solution, washed 3 times in dry acetonitrile, and then air dried.
• the conductivities were measured using a 4-point probe device.
• the conductivities of the composite fibers reached constant values of:
• Example 8 A series of polyoctylthiophene - (POT)/polyethylene composite fibers were prepared such that the total polymer concentration in the gel was maintained at 1.5% by weight. All composite fiber samples were drawn to various draw ratios at 105°C in air. A comparison of the moduli from composite fibers in Q Example 8 combined with data from Example 2 shows the drastically improved mechanical properties of the composite fibers.
• POT polyoctylthiophene -
• the composite fibers were of the following
• Example 9 The polyoctylthiophene/polyethylene composite fibers of Example 8 were dried and drawn, in air, at 105°C to various draw ratios. The samples were then doped at room temperature in iodine vapor to constant measured potentials using a 4-point probe device. The conductivities of the composite " fibers reached constant values of:
• the synthesis of the precursor polymer was carried out essentially according to the procedure described in the literature (T. Momii et al., Chem. Lett.. 1201 (1987); S. Tokito et al.. Polymer, to be published 1991) as shown in Figure 2.
• the polymerization was carried out by mixing equal volumes of 0.4 M aqueous monomer and 0.4 M aqueous NaOH at 0-l0°C for 1 hour. After 5 minutes reaction, the mixture formed a transparent gel.
• Purified precursor polymer (PDMPV, 50 mg) was dissolved in a mixture of 3_ml xylene and 0.5 ml chloroform. The solution of precursor polymer was mixed at 60°C with 62 mg of ultra-high molecular weight polyethylene (Hostalen GUR 412, Hoechst) in a 20 ml test tube. This mixture was heated at a temperature of 130°C for 30 minutes with stirring, and then cooled to ambient temperature. The resultant composite gel was yellow. Composite filaments of polyethylene and PPMPV were spun at 130°C using laboratory scale equipment. The as-spun filament was wound onto a bobbin and dried in a vacuum oven overnight.
• Ultra-high molecular weight polyethylene Hostalen GUR 412, Hoechst
• the drawn fibers were heated to convert precursor polymer to PMPV at 110°C for 10 hours under nitrogen gas containing a small amount of the vapor of hydrochloric acid (the nitrogen gas was first passed over HC1 at room temperature) .
• the acid catalyst plays an important role in the conversion reaction (see T. Momii et al. , Chem. Lett. , 1201 (1987)). After 10 hours of heating, the highly oriented composite fibers which contained 60 wt% of PE and 40 wt% of PDMPV, were obtained.
• the composite fibers were red with a shiny metallic luster.
• Mechanical properties of the composite fiber are listed below. These values are comparable to the values of highly oriented polyethylene fiber. (P. Smith and P.J. Lemstra, J. Mat. Sci.. 15.:505 (1980)) and are characteristic of high-performance polymers (see Table 1).
• Example 11 The composite fibers (40 wt%, PDMPV) of Example 10 were doped with iodine by exposing the fibers to iodine vapor at room temperature.
• the conductivities of the doped composite fibers were measured by the conventional 4-probe method. The conductivities are listed below:
• Example 10(B) The composite fibers prepared in Example 10(B) were drawn and converted simultaneously. Nitrogen gas containing a small amount of hydrochloric acid vapor was introduced into the tube furnace during heating and drawing.
• Example 13 The composite fibers (40 wt%, PDMPV) of Example 11 were doped with iodine by exposing the fibers to iodine vapor at room temperature.
• the conductivities of the doped composite fibers were measured by the conventional 4-probe method. The conductivities are listed below:
• Example 14 The composite filaments with different concentrations of precursor.polymer were prepared according to Example 10(B). The composite filaments were drawn and converted by using the same system as described in Example 12.
• the mechanical properties and conductivities of the composite fibers are listed below:
• Example 15 This example involves the preparation and testing of a highly drawn polymer composite made up of 99% ultra-high molecular weight polyethylene and 1% conjugated polymer, poly(2-methoxy,5-(2'ethyl-hexyloxy)- p-phenylenevinylene) "MEH-PPV". It follows the preparative scheme shown in Figure 3.
• the conjugated polymer is highly colored (bright red-orange) .
• UV ⁇ CHC1 3 UV ⁇ CHC1 3 ) 365.
• the precursor polymer was converted (step e of the Scheme) to the conjugated MEH-PPV by heating to reflux (approx. 214°C) in 1,2,4-trichlorobenzene solvent.
• the product was identical with the material obtained in Scheme 1 of Figure 3.
• the spectra were measured with a 0.3 meter single grating monochrometer, and a mechanically chopped tungsten-halogen light source (resolution at the exit slits was 1.0 nm) ; light was detected by a photomultiplier tube (Hamamatsu R372) , and the output was sent to a lock-in amplifier.
• the samples were mounted on sapphire substrates which were fit into a copper sample holder and mounted on the cold finger of a vacuum cryostat.
• a dichroic sheet polarizer (MG 03 FPG 005) was inserted (on a driven rotational stage) just before the sample.
• the index is dominated by that of PE so that the reflection losses were limited to a few percent even for relatively thick samples with moderate optical density.
• the absorption coefficients, parallel and perpendicular to draw axis were accurately determined after correcting for the background with a blank substrate.
• PL photo-luminescence
• the sample was excited by a polarized, mechanically chopped (400Hz) Ar - ion laser (Coherent model 70) beam tuned to 457.9 nm.
• the polarizer was placed at the entrance slit of the monochrometer. All PL spectra were corrected by replacing the sample with an NBS referenced lamp. Absorption spectra were monitored before and after • luminescence runs to insure against optical damage.
• Figure 5 compares absorption coefficients of a nonoriented free-standing film of PE/MEH-PPV, of the 0 oriented film of PE/MEH-PPV parallel to draw axis, and of the spin-cast film (all at 8OK) .
• the spectrum obtained from the nonoriented blend is intermediate between that of the spin-cast film and the oriented blend; it shows the red shift, the sharper absorption onset, the reduced _ total band-width and the emergence of vibronic structure.
• the MEH-PPV spectra are, in every way, consistent with a significant enhancement of microscopic order.
• the inset to Figure 5 compares the absorption parallel to draw of an oriented free standing film of PE/MEH-PPV at 8OK with that at 30OK. As the temperature
• Figure 6 demonstrates the anisotropy in the 8OK emission spectrum, L( ⁇ ) of an oriented free standing film of PE/MEH-PPV for parallel pumping.
• the inset displays the polarization dependence of L( ⁇ ) measured at the zero- phono line (2.091 eV) .
• the residual scattering sets a lower limit on this anisotropy of L( ⁇ ) parallel/L( ⁇ ) perpendicular greater than .60 with the preferred direction parallel to the draw axis.
• the L( ⁇ ) measured perpendicular shows relatively less spectral weight in the zero-phono line, consistent with a higher degree of disorder in the residual nonoriented material.
• Decalin decahydronaphthalene, Aldrich
• 9.7 g was mixed, at room temperature, with 200 mg of polydodecylthiophene in a 50 ml test tube.
• This stirred mixture was blanketed with nitrogen gas and heated to 104°C, at which time 200 mg of ultra-high molecular weight polyethylene (Hostalen GUR 415, Hoechst) was added.
• Hostalen GUR 415 ultra-high molecular weight polyethylene
• the mixture was heated to a temperature of 115°C, at which point stirring was stopped, and the temperature was raised further to 150°C for 1 hour. A viscous orange liquid was obtained.
• the solution was cooled, and the red-orange gel was transferred to a laboratory-scale spinning apparatus.
• a polyethylene/polydodecylthiophene gel fiber was spun according to standard procedures at 105°C in air.
• This material is drawn in accord with the invention and exhibits the orientation properties observed in Example 16.
• Example 18 The materials of Examples 15 - 17 are nonconducting. They are doped at 40°C in a 1.75%wt. solution of NOSbF g or in iodine vapor (as representative methods) and found to be conductive.
• FIG. 7 shows the anisotropic electroabsorption (electric field modulated absorption) of a film an oriented MEH-PPV/PE film containing a volume fraction of 6% MEH-PPV. At this concentration, direct optical absorption experiments are not possible for the optical density is too high. The electroabsorption was used, therefore, to characterize the orientation and alignment.
• the film was prepared and then tensile drawn as described in the case of the 1% sample (Example 16).
• the spectra- shown in Figure 7 were obtained with a film drawn to 10 times its original length (draw ratio of 10) .
• was taken with the electric field parallel to the draw direction; the spectrum denoted by - 1 was taken with the electric field perpendicular to the draw direction.

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