TW200930743A - Process for preparation of regioregular conducting block copolymers - Google Patents

Abstract

The invention provides a method of preparing regioregular conducting block copolymers as well as the regioregular conducting block copolymers prepared thereby. The method includes combining a nickel (II) catalyst together with at least two monomer-metal complexes to provide the regioregular conducting block copolymer. Electronic devices may be made using the polymers prepared herein.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of preparing a positionally-regular conductive block copolymer having high positional selectivity. [Prior Art] Recently, attention has been paid to conductive polymers, which are due to their properties, electrical conductivity, and other valuable properties. Conductive Poly: = Used in electronic components for a variety of applications, such as transistors, diodes, triodes, and rectifiers. Irregular conductivity due to low purity often hampers the use of conductive polymers in such and other applications. There are several known synthetic methods for preparing conductive polymers such as polythiophenes. However, such known techniques often provide substituted polythiophenes having suboptimal positional rules. High position regular conductive polymers are expected because of the strong influence of monomer orientation on polymer conductivity. The high position of the regular conductive polymer allows improved package and optimized microstructure to improve charge carrier mobility. The lack of desirable mechanical and processing properties also hinders the use of conductive polymers in these and other applications. Improved Processability of Conductive Polymers Red-methods are modified by the synthesis of blocks (4). Block copolymers are attractive because they allow the designer to tailor the processability and mechanical properties of the block copolymer by carefully selecting the appropriate section of the & Therefore, there is still a need in the art for an improved method of synthesizing a regular-purity and high-position regular conductive block copolymer. There is also a need in the industry for a device having a high purity positionally oriented conductive block copolymer assembly to improve the ease of manufacture and operation. I35320.doc 200930743. [Summary of the Invention]

The present invention relates to a process for preparing a positionally oriented conductive segment copolymer and a positionally oriented conductive block copolymer prepared thereby. The method of preparing a positionally oriented conductive block copolymer disclosed herein employs an activated metal which directly inserts a metal atom into a halogen-aromatic or halogen-heteroaromatic carbon bond. Preferably, the metal is Rieke zinc (Zn*). If the polymerization is completed, for example, using nickel (II) or a platinum catalyst, a positionally regular conductive block copolymer can be obtained. The positionally-regular conductive block copolymer may be, for example, a block copolymer comprising two or more monomers having the same ring system (e.g., thiophene), or two or more having different ring systems ( For example, a block copolymer composed of monomers of thiophene and benzene). Preferably, the positionally-regular conductive block copolymer is, for example, a polythiophene block copolymer comprising unsubstituted phenanthrene, 3-substituted thiophene, 3,4-disubstituted thiophene, or a combination thereof, or includes poly A block copolymer of a thiophene block and another aromatic or heteroaromatic conductive polymer block. The present invention is also directed to a positionally constrained electrically conductive block copolymer having excellent electrical conductivity. The positional regular conductive block copolymer is characterized by its monomer composition, its positional regularity, and its physical properties, such as its molecular weight and number average knife amount, its degree of polymerization distribution, its electrical conductivity, and its preparation characteristics. Directly determine the purity, and other characteristics. The positionally regular electrically conductive block copolymer is also characterized by its method of preparation. The present invention is also directed to a positional regular guide 135320.doc 200930743 prepared by the method described herein. The positionally regular conductive block copolymer film may comprise a mu of a dopant. The invention also provides an electronic device' comprising circuitry constructed, for example, from a positionally-regular conductive block copolymer prepared by any of the methods described herein. The electronic device may be a thin film transistor, a field effect transistor, a radio frequency identification mark, a flat panel display, a photovoltaic device, an electroluminescence display device, a sensor device, an electrophotographic device, or an organic light emitting diode (〇led) . The present invention provides a method of preparing a positionally oriented conductive block copolymer comprising: a) combining a (11) catalyst with a first single Zhao metal complex to provide

位置 Positioning of a regular conductive block copolymer intermediate, wherein the first monomer-metal complex is prepared by a method comprising the steps of: first element-monomer and activated metal, Grignard Reagent (Grignard called coffee) or RZnX, R2ZnX, or ruler 321 ^ reagent combined, wherein the ruler (^ ^ 2) alkyl, lanthanide magnesium, manganese, lithium, sodium or potassium, and α, or plant · b) will The second monomer-metal complex is combined with the positionally-regular conductive block copolymer intermediate to provide a positionally-regular conductive block copolymer, wherein the second monomer-metal complex is comprised of the following steps The method comprises the steps of: combining a second dentate-monomer with an activated metal, a Grignard reagent, or a RZnX, R2ZnX, or R3ZnM reagent, wherein the ft (C2_Ci2) alkyl group, the μ system of magnesium, manganese, lithium, sodium Or potassium, and X is F, a, Br, or 1; wherein each dihalogen-monomer is independently an aromatic or heteroaromatic group substituted by two halogens, the halogens being the same or different And wherein if the dihalogen-monomers have the same ring system, at least one dentate-monomer is substituted And if the two bis-monomers all have the same ring system and are substituted, 135320.doc 200930743 then the substituents are different. In the examples, the recording (1) catalyst was used and the recording medium and the first monomer metal complex were combined in either order. In another embodiment, the (8) catalyst is added to the first monomer/metal complex t to provide a positional regular, f block copolymer intermediate. In another embodiment, a first monomeric metal disorder is added to the (η) catalyst to provide a positionally regular conductive block 'copolymer intermediate. In one embodiment, the aromatic or heteroaromatic group may be benzene, thiophene, benzoic acid, aniline, phenylene extended phenyl group, thiophene extended vinyl group, bis-extended thiophene extended ethylene Base, acetylene, anthracene, aryl, isothionaphthalene, p-phenylene sulfide, thieno[2,3_b], thieno[2,3&lt; thiophene, thieno[2,3-d] porphin , naphthalene, benzo[2,3]porphin, benzo[3,4](tetra),biphenyl, or conjugated phenyl] and wherein the aromatic or heteroaromatic group has from 0 to about 3 non-halogen Substituent. In another embodiment, the substituents of the above aromatic or heteroaryl (tetra) groups are each independently from about 1 to about 5 esters, hydrazines, nitriles, amine groups, aryl groups, heteroaryl groups, as desired. Or a heterocyclic group substituted with (Ci_C24)alkyl, (Ci C24)alkylthio, (CrC24)alkyldecyl, or (Ci_C24)alkoxy, and one or more alkyl-alkyl chains The carbon atoms may optionally be replaced by from about 1 to about 10 hydrazine, s. or NH groups. In another embodiment, the first dioxin monomer and the second dihalo monomer are each independently selected from the group consisting of: 2,5-difunctional thiophene, 2,5-di Halogen ratio, 2,5-di-business-bite, dihalobenzene, 2,% dihalo-3-substituted thiophene, 2,5-difunctional substituted pyrrole, 2, Hong dentate _ 135320.doc • 9- 200930743 3-Substituted furan, 1,3-difunctional-2-substituted benzene, bis-dentate-4-substituted benzene, 1,3-dihalo-5-substituted benzene, 1,3_two-tooth Substituted benzene, 1&gt;3_didentate-2,4-disubstituted benzene, M-dimorph-2,5-disubstituted benzene, bis-dentate-2,6-disubstituted benzene, 1,3 _Seconazole _4,5-disubstituted benzene, hydrazine, 3- dentate _ 4.6-disubstituted benzene, 1,3-difunctional 2,4,5-trisubstituted benzene, anthracene, 3·2 Phytosin _ • : / sense trisubstituted benzene ~ to - dimerin winter 乂 - trisubstituted benzene '^-difunctional - 2-substituted benzene, fluorene-dihalo-3-substituted benzene, M-dentate 5--5-substituted benzene, 1,4-dihalo-6-substituted benzene, 1,4-dentate-2,3-disubstituted benzene, L4-diindole halogen-2,5-disubstituted benzene, M -dihalo-2,6-disubstituted benzene, L4-dihalogen-3,5-disubstituted benzene, 1,4_dihalogen _3,6-disubstituted benzene, L4-diponectin- 3.5.6-trisubstituted benzene, 2,5·didentin-3,4-disubstituted thiophene, 2,5-didentate·3,4- Disubstituted 0-H, 2,5-dihalo-3,4-disubstituted*, and combinations thereof 0 In one embodiment, the first dihalogen-single system dibromohexyl sinter and second A dentate-single system of ethyl 5-(2-5-dibromophenant-3-yl)pentanoate. In another embodiment, the positionally regular conductive block copolymer comprises unsubstituted singly, 3-substituted porphin, 3,4-disubstituted finch, or a combination thereof. In another embodiment, the <positionally-preferred conductive block copolymer is a HT poly(3-substituted thiophene) block copolymer or HT poly(3,4-disubstituted porphin). In one embodiment, the HT poly(3-substituted thiophene) block copolymer is substituted with a plurality of linear (Ci-Ci2) alkyl groups and substituted with a plurality of linear (Cr C12) alkyl groups substituted with an ester group. . In another embodiment, the HT poly(3-substituted thiophene) block copolymer is substituted with a plurality of hexyl groups and substituted with a plurality of ethyl ester groups monosubstituted 135320.doc • 10·200930743. In one embodiment, the 'metal auxiliaries, bells, copper, rhodium, magnesium, about, chin, iron, erroneous, recorded, marital, or combinations thereof. In another embodiment, the metal is activated by zinc (Zn*). In another embodiment, the positional regular conductive block copolymer has a positionality of greater than about 87% or preferably at least about 92%, or more preferably at least about 97%. In one embodiment, the positionally-regular conductive block copolymer is substituted with a plurality of linear (C丨-C12) substituents and substituted with a plurality of linear (C1 _ C 2) alkyl groups substituted with an ester group. In another embodiment, the positionally-regular conductive block copolymer is substituted with a plurality of hexyl groups and substituted with a plurality of pentyl groups monosubstituted with ethyl ester groups. In another embodiment, the positionally regular conductive block copolymer has a weight average molecular weight of from about 5,000 to about 200,000, or preferably from about 40,000 to about 60,000 Å. In one embodiment, the positionally oriented conductive block is prepared. The copolymer polymerization degree distribution index is from about 1 to about 2.5, or preferably from about 1.2 to about 2.2. In another embodiment, 'nickel (II) catalyst or derived from Ni(dppe)Cl2, Ni(dPPP)Cl2, NKPPh^Bi.2, 1,5-cyclooctadiene bis(triphenyl)nickel , two gas (2,2'-dipyridine) nickel, tetrakis(triphenylphosphine) nickel, Ni〇, ν%,

NiC12, NiBr2, Nil2, NiAs, Ni(dmph)2, BaNiS, or a combination thereof 0 In another embodiment, 'using about 0.01 m〇l% to about 1 〇〇m〇l% of the catalyst (Η) catalyst' Or preferably from about 0.1 mol% to about 5 mol%' or more preferably from about 1 mol% to about 3 mol%. In another embodiment, about 1 m 〇 1 % 135320.doc 11 200930743 to about 100 mol % platinum catalyst, or preferably about (M mol % to about 5 mol %, or better about 0. 1 mol % to about 3 mol 0 / 〇. In one embodiment, the present invention provides a method of preparing a positionally regular HT poly(3-substituted thiophene) block copolymer, which comprises: a) contacting nickel (11) The medium is combined with a first thiophene-conjugate to provide a positionally regular HT poly(3-substituted thiophene) intermediate; b) a second thiophene-zinc complex with a positionally regular ht poly(3 _ substituted thiophene) The intermediates are combined to provide a positionally regular HT poly(3-substituted thiophene) block copolymer. In another embodiment, the nickel (ruthenium) catalyst is combined with the first thiophene-zinc complex in either order. In another embodiment, a nickel (H) catalyst is combined with a first thiophene-zinc complex to provide a positionally regular HT poly(3-substituted thiophene) intermediate. In one embodiment, the first thiophene-zinc complex and the nickel (π) catalyst are combined to provide a positionally regular fluorene (3-substituted thiophene) intermediate. In one embodiment, an electronic device comprising a circuit constructed using a positionally regular conductive block copolymer or a positionally regular condensed (3-substituted thiophene) block copolymer is provided. In another embodiment, the device is a thin film transistor, a field effect transistor, a radio frequency identification mark, a flat panel display, a photovoltaic device, an electroluminescent display device, a sensor device, and an electrophotographic device, or an organic light emitting device Polar body. In another embodiment, a positionally regular conductive block copolymer or a positionally regular fluorene (3-substituted thiophene) block copolymer is provided. In one embodiment, the coarse-position regular conductive segment copolymer or the coarse-position regular Ητ poly(3 _ substituted porphin) block copolymer has a positional regularity of at least about 87%, preferably greater than about 92%. More preferably, it is greater than about 95%. 135320.doc • 12· 200930743 In another embodiment, a conductive block copolymer is provided having a positional regularity of at least about 92%; a weight average molecular weight of from about 30,000 to about 70,000; and a conductance of about 10.5 to About 10.6 Siemens/cm ° [Embodiment] Definitions Certain terms used herein have the following meanings. All other terms and phrases used in the specification have the generic meaning as understood by those skilled in the art. These general meanings can be obtained by reference to technical dictionaries such as w Hawley's, 11th edition, Sax and

Lewis, Van Nostrand Reinhold, New York, N.Y., 1987 and 77^ MercA/ni/ex, 11th ed., Merck &amp; Co., 'Rahway N.J. 1989. The term &quot; and/or &quot; as used herein means any entry, any combination of terms, or all entries associated with this term. The singular forms &quot;&quot;&quot; &&quot;&quot;&quot;&quot;&quot;&quot;&quot;&quot; Thus, for example, reference to &quot;mixture&quot;&quot; includes a plurality of such formulations such that the formulation of Compound X includes various formulations of Compound X. The term &quot;about&quot; as used herein means to vary within 10% of the specified value, for example about 50% means to vary from 45% to 55%. For the range of integers, the word "about" may include an integer one or two greater than the integer. The term &quot;activated metal&quot; as used herein refers to metal powder, metal dust, or metal particles, which have Chemical, thermal, electrochemical, or ultrasonic activation. Usually &quot;activated metal&quot; is zero. The term &quot;activated zinc&quot; as used herein refers to zinc powder, repulsive dust, or zinc 135320. Doc 13 200930743 granules, which have been chemically, thermally, electrochemically, or ultrasonically activated. For example, the words can be added by adding a small amount of l2, a halogenated carbon compound, a halogenated hydrazine compound, or Hg (:l2). It is chemically activated. Electrochemical activation of zinc can be carried out by applying a positive voltage. Thermal activation can be carried out by heating the particles or zinc powder in a vacuum. Activation can also be carried out by ultrasonic waves. &quot;Alkyl&quot; means a branched, unbranched, or cyclic hydrocarbon having, for example, from 3 to 3 carbon atoms, and often from 1 to 12 carbon atoms. Examples include Not limited to) methyl, ethyl, propyl (n-propyl), 2-propyl (isopropyl), 1 butyl (n-butyl), 2-methyl-1-propyl (isobutyl), 2_ butyl (t-butyl), 2-methyl-2-propyl (t-butyl), i-pentyl (n-pentyl), 2-pentyl, 3-pentyl, 2-methyl -2-butyl, 3-methyl-2-butyl, 3-mercapto-1-butyl, 2-methyl-1-butyl, i-hexyl, 2-hexyl, 3-hexyl, 2- Methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 3-methyl-3-ethylpentyl, 2-methyl-3-pentyl, 2, 3-dimethyl-2-butyl, 3,3-didecyl-2-butyl, hexyl, octyl, decyl, dodecyl, and the like. The alkyl group may be unsubstituted or substituted. The alkyl group may also be partially or completely unsaturated, as desired. Thus, when referring to an alkyl group, it includes alkenyl and alkynyl groups. As exemplified and exemplified above, the alkyl group may be a monovalent hydrocarbon group, or it may be a divalent hydrocarbon group ( That is, an alkyl group. The term &quot;alkylthio&quot; as used herein refers to an alkyl-S- group, wherein the alkyl group is as defined herein. In one embodiment, the alkylthio group includes, for example, methyl sulfide. Base, Thio, n-propylthio, isopropylthio, n-butylthio, tert-butylthio, first butylthio, n-pentylthio, n-hexylthio, ι, 2· Dimethyl butylthio, and the like. The alkyl group in the alkylthio group may be unsubstituted or substituted. 135320.doc • 14- 200930743 The term &quot;alkylalkylalkyl&quot; as used herein refers to alkyl-SiH2 a - or a thiol-SiR2_ group, wherein the alkyl group is as defined herein, and each r is independently η or alkyl. Replacing the porphin with a burnt-based alkyl group by any of a variety of techniques known to those skilled in the art will generally be accomplished by coupling the porphin to the alkyl halide of the compound. Technology revealed in Aldrich

Handbook of Fine Chemicals, 2007-2008, Milwaukee, WI. The term &quot;alkoxy&quot; as used herein, refers to an alkyl-oxime group, wherein the leuco group is as defined herein. In one embodiment 'alkoxy includes, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, second butoxy, n-pentyl Oxy, hexyloxy, 1,2-didecylbutoxy, and the like. The alkyl group in the alkoxy group may be unsubstituted or substituted. The term &quot;aryl&quot; as used herein refers to an aromatic hydrocarbon radical derived by the removal of one hydrogen atom from a single carbon atom of the parent aromatic ring system. This group may be at the saturated or unsaturated carbon atom of the parent ring system. The aryl group may have 6 to 18 carbon atoms. The aryl group may have a single ring (e.g., phenyl) or a plurality of condensed (fused) rings wherein at least one of the rings is aromatic (e.g., naphthyl, dihydrophenanthrenyl, fluorenyl, or fluorenyl). Typically aryl groups include, but are not limited to, groups derived from benzene, naphthalene, anthracene, biphenyl, and the like. The aryl group may be unsubstituted or substituted as desired, as described above for the alkyl group. The term &quot;block copolymer&quot; as used herein refers to any polymer prepared by coupling a functional polyvalent polymer, such as an AB block copolymer. The block copolymer of certain embodiments may be an AB block copolymer wherein the a block is a first monomer and the B block is a second monomer, wherein the first and second monomers are each different. The block copolymer of some embodiments may also be an ABA block copolymer or an ABc embedded 135320.doc -15-200930743 segment copolymer, wherein the A block is the first monomer, and the B block is the second monomer. And wherein the C block is a third monomer, wherein the first, second and third monomers are each different. Further, the block copolymer of certain embodiments may be an Ab block copolymer, for example, wherein the A block is a polythiophene and the B block is another conductive polymer 'e such as poly(β pyrrole). The block copolymer of certain embodiments may also be a hydrazine block copolymer or an ABC block copolymer, wherein the a block is a polythiophene, wherein the B block is another conductive polymer, such as poly(pyrrole), and Wherein the C block is another conductive polymer such as poly(stupylamine). The term &quot;conductive polymer&quot; as used herein refers to a polymer that conducts electrical current. Usually, the conductive polymer is a polymer mainly containing sp2-hybridized carbon atoms in the main chain, and these carbon atoms may also be replaced by corresponding hetero atoms. In the simplest case, this means that double bonds and single bonds alternate in the main chain. &quot;Main&quot; means that the natural deficiencies that lead to conjugate blocking do not affect the term &quot;conductive polymer," its applicability. Further, if, for example, an arylamine unit and/or a certain heterocyclic ring (ie, conjugated via an N, hydrazine or S atom) and/or an organometallic complex (ie, conjugated via a metal atom) are present in the backbone, The term &quot;conductive&quot; is also used in the text of this application. In contrast, units such as simple alkyl bridges, (thio)ethers, esters, decylamines, or hydrazine amine linkages are defined as non-conductive segments. A partially conductive polymer is intended to mean a relatively long conductive portion of the main chain which is interrupted by a non-conductive portion or which has a relatively long conductive portion in the side chain but which is not electrically conductive. The term &quot;conductive polymer&quot; as used herein also refers to homopolymers, random copolymers, branched polymers, block copolymers, and the like. The term &quot;film, or &quot;film&quot;; means a self-propelled or free-standing film that exhibits mechanical stability and flexibility, and a coating or layer on the support substrate or between 135320.doc -16- 200930743. The term &quot; A reagent, which is a composition formed by the action of a leukotriene or an aryl dentate on a magnesium metal. The term "dentate" as used herein refers to fluorine, chlorine, ? Stinky, or an ionic group, a substituent, or a free radical. The term &quot;heteroaryl&quot; as used herein, is defined herein as a monocyclic, bicyclic, or tricyclic system which contains one, two or three aromatic rings and contains at least one nitrogen in the aromatic ring. Oxygen, or sulphur and which may be unsubstituted or substituted, for example, by one or more (and in particular 丨 to 3) substituents, as described above in the definition of "substituted". Heteroaryl Examples include, but are not limited to, down-reacting, 3H, aryl, 4H, pyridazinyl, acenaphthyl benzophenanyl, benzinium, lindenyl, (tetra), benzopyrene Tertyl, porphyrin, dibenzo[b,d]furanyl,furazanyl,furyl,imidazolyl,imidizolyi,isosyl,zino,(tetra),isobenzo吱味基, 异巧卜基基, 异噎琳基, 异嗟峻基异 峻 基 萘 萘 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Biazinyl, phenazinyl, phenazinyl, benzylthio, phenyl, pyridazinyl, fluorenyl, beta-pyranyl, pyridazinyl, benzylazolyl, pyridazinyl, Acridinyl, pyrimidinyl, Rupyl, quinazolinyl, quinolyl, quinoxalinyl, thiadiazolyl, thioxyl, thiazolyl, thienyl, triazolyl, tetrazolyl, and xanthene. In one embodiment The term &quot;heteroaryl&quot; denotes a monocyclic aromatic ring containing 5 or 6 ring atoms containing carbon atoms and deuterium, 2, 3 or 4 independently selected from non-peroxide oxygen, sulfur and N (z) a hetero atom in which it is vacant or is H' 〇, alkyl, aryl, or (CiC6)alkylaryl. In another 135320.doc •17· 200930743, the heteroaryl group represents from about 8 to A thick uf heterocyclic ring of about 1 ring atom, especially a phenyl derivative or a derivative obtained by condensing a propyl group, a trimethylene group or a tetramethylene divalent radical. The term "heterocyclic ring" or "heterocyclic group" as used in the basic text of 喃 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基Substituting a group as defined in the term &quot;substituted&quot; as needed. The heterocyclic ring may be a monocyclic, bicyclic or tricyclic ring containing - or a plurality of heteroatoms. Non-limiting examples of heterocyclic groups which may also contain an oxo (=0) beta heterocyclyl group attached to the ring include 1,3-dihydrobenzofuran, 1,3-dioxolane, 1,4-Dioxane, anthracene, 4_dithiane, pyran, 2_pyrazoline, 4-pyridolohydropyranyl, imidazolidinyl, imidazolinyl, dihydroindole Benzodihydropyranyl, iso-dihydroarsenyl, morpholine, hexahydropyrazine/hydropyridine, hexahydropyridyl, pyrazolidine, pyrazolidinyl, pyrazolinium pyrrolidine 'pyrroline, Quinine ring, and thiomorpholine. The term &quot;heterocycle&quot; also includes (for example, without limitation) monovalent free radicals of the heterocyclic ring described in the following literature. Paquette, Leo A., Principles of Modern Heterocyclic

Chemistry (W.A. Benjamin, New York, 1968), especially chapters i, 3, 4, 6, 7 and 9, The Chemistry of Heterocyclic Compounds, A Series of Monographs (John Wiley &amp; Sons »

New York, 1950 to present, especially Volumes 13, 14, 16, 19, and 28, and /. dm. C/ze/n·S〇c·i960, 52, 5566. In the present invention - an embodiment, &quot;heterocycle&quot; includes a "carbocycle" as defined herein, wherein one or more (e.g., 1, 2, 3 or 4) carbon atoms have been heteroatoms (e.g., hydrazine, N or S) Replacement The term &quot;high positionality&quot; as used herein refers to a compound or polymer having a positional regularity of at least about 85%, preferably at least about 87% of the positional regularity of 135320.doc • 18 · 200930743 More preferably, at least about 90% of the positionality, even better, at least about 92% of the positionality, preferably at least about 95% of the positionality, preferably at least about 97% of the positionality, or preferably At least about 99% of the positional regularity.

术语 The term &quot;HT poly(substituted thiophene) block copolymer" as used herein means in ht poly(3_substituted thiophene) block copolymer or ht poly(3,4-disubstituted thiophene) block copolymer Monomer head-to-tail orientation ^ The percentage of positional regularity exhibited in the HT poly (substituted phenotype) block copolymer can be determined by standard ι Η. The percentage of positional regularity can be improved by various techniques, including (for example) Soxhlet extraction, sedimentation, and recrystallization. The term &quot;metal catalyst&quot; as used herein refers to a polymerization catalyst for monomer-metal complexes. The term &quot;single A body-metal complex refers to a monomer moiety (eg, (iv)) attached to a metal atom (eg, zinc). The monomer-metal complex is typically a monomeric metal tooth complex complex (eg, porphin) Compound complex). The "dental" &quot; or dentate&quot; group can be fluorine, gas, desert or iodine. As used herein, the terms "better" and "preferably" are preferred embodiments of the present invention that provide advantages in some cases. However, other embodiments may be preferred in the same or other circumstances. </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> and one or more preferred embodiments are not intended to be used in the context of the present invention. As used herein, the term &quot;positional rules&quot;, phantom buckles, in which the monomers are substantially aligned in a head-to-tail orientation, are agglomerated, although a variety of conventional polymers have a full alpha·alpha coupling' The head _ takes a mixture of - tail, tail and tail orientation. 135320.doc 19 200930743

Therefore, the polymer for f does not have full positional regularity (previously referred to as positional specificity and stereospecificity), i.e., all of the head, tail, tail, or tail-tail orientation. Conventional polymers are also not completely random in position, ie each orientation is equal (25% head-tail and head-tail, 25% head_tail and head, 25% tail-tail and head-tail, 25% tail-tail And head _ head).

Head-to-tail and head-to-tail connections

R R

Head-to-tail and head-to-head connection

Tail-tail and head-to-head connection -20· 135320.doc 200930743

Tail-Tail and Head-Head Connections For further explanations and discussion of the term positional randomness and positional regularity (or positional selectivity), see U.S. Patent No. 5,756,053, which is incorporated herein by reference. The term "Rick Zinc (Zn*)" as used herein refers to an activated form of zinc prepared by the method described in U.S. Patent No. 5,756,653, the disclosure of which is incorporated herein by reference. The term &quot;room temperature&quot; as used herein refers to about 23 〇c. The term &quot;substitution&quot; as used herein is intended to mean one or more of the groups that are not used in the expression ''substitution'&quot; (e.g. 1, 2, 3, 4 or 5, in certain φ embodiments) 1 or 2 or 3 in other embodiments, and 1 or 2 in other embodiments) a hydrogen atom is replaced by a member selected from the group consisting of the organic or inorganic group, or a suitable organic or inorganic group known to those skilled in the art. The group substitution, provided that it does not exceed the constant value of the indicated atom 'and the substitution produces a stable compound. The suitable organic or inorganic group includes, for example, an alkyl group, an alkenyl 'alkynyl group, an alkoxy group, a dentate group, a halogen group. Alkyl, thiol, hydroxyalkyl, aryl, heteroaryl, heterocyclyl, cycloalkyl, aryl, alkoxycarbonyl, amine, alkylamino, dialkylamino, Methylthio, difluoroindenyl, decylamino, nitro, trifluoromethyl, dimethoxy, carboxy, carboxyalkyl, keto, thio, alkylthio, 135320.doc 21 200930743 a base group, a base group, a base group, and a cyano group. Further, the suitable group may include, for example, -X, - R, -CT, -OR, -SR, -S_, -NR2, -NR3, =NR, -CX3, -CN, -OCN, -SCN, -N=C=0, -NCS, -NO, -N02 , =N2, -N3, NC( = 0)R, -C( = 0)R, -C(=0)NRR -S(=0)2〇-, -S(=0)20H, -S( =0) 2R, -0S(=0)20R, '-S(=0)2NR, -S(=0)R, -0P(=0)02RR, -P(=0)02RR, -P(= 0)(C〇2, -P( = 0)(0H)2, -C( = 0)R, -C( = 0)x, -C(S)R, -C(0)0R, -c (0)cr, -C(S)OR, -C(0)SR, -C(S)SR, -C(0)NRR, O-C(S)NRR, -C(NR)NRR, each of which X is independently halogen (or &quot;halogen&quot; group): F, Cl, Br, or I, and each R is independently hydrazine, alkyl, aryl, heterocyclyl, protecting group or prodrug moiety It will be readily understood by those skilled in the art that when the substituent is a keto group (i.e., = oxime) or a thio group (i.e., =S) or the like, two hydrogen atoms on the substituted atom are replaced. The terms "stabilizing compound" and "stabilizing structure" are intended to mean that the compound or polymer is sufficiently strong to remain unchanged when separated from the reaction mixture to useful purity. The compounds and polymers of the invention are generally stable compounds. Intermediates and metals The compound may be somewhat unstable or may be an inseparable component of the process of the invention. - The term &quot;thiophene-zinc complex π as used herein refers to a thiophene moiety attached to a diatom atom. The thiophene-zinc complex is typically thiophene- Zinc halide complex. The "halide" or "halogen" group may be fluorine, gas, bromine or iodine. Of course, for any of the above groups containing one or more substituents, it is understood that the groups do not contain Any substitution or substitution pattern which is sterically impractical and/or synthetically infeasible. Furthermore, the compounds of the invention include all stereochemical isomers resulting from the substitution of such compounds by 135320.doc • 22 200930743. A method of preparing a positionally oriented conductive block copolymer and a positionally regular conductive block copolymer prepared thereby. The method of preparing a positionally regular conductive block copolymer disclosed herein employs an activated metal which directly inserts a metal atom into a halogen - Aromatic or halogen-heteroaromatic carbon bond. If the polymerization is carried out, for example, using a nickel (II) catalyst or a platinum catalyst, a positionally regular conductive block copolymer can be obtained. The copolymer may be, for example, a block copolymer comprising two or more monomers having the same ring system (e.g., thiophene), or two or more having different ring systems A block copolymer composed of a monomer such as thiophene and benzene. Preferably, the position-regular conductive block copolymer (for example) includes unsubstituted thiophene, 3-substituted thiophene, 3,4-disubstituted a thiophene block copolymer or a combination thereof, or a block copolymer comprising a polythiophene block and another aromatic or heteroaromatic conductive polymer block. The present invention is also directed to a position having excellent electrical conductivity properties. Regular conductive block copolymer. The positional regular conductive block copolymer is characterized by its monomer composition, its degree of positional regularity, and its physical properties, such as its molecular weight and number average molecular weight, its degree of polymerization distribution, Electrical conductivity, purity directly determined by its preparation characteristics, and other characteristics. The positional regular conductive block copolymer is also characterized by its method of preparation. The present invention also relates to a positionally regular conductive prepared by the method described herein. a block copolymer film. The positionally regular conductive block copolymer thin layer may include a dopant. 135320.doc • 23· 200930743 The present invention also provides an electronic device, A circuit comprising, for example, a positionally-regular conductive block copolymer prepared by any of the methods described herein. The electronic device can be a thin film transistor, a field effect transistor, a radio frequency identification tag, a flat panel display, a photovoltaic device An electroluminescent display device, a sensor device, and an electrophotographic device, or an organic light emitting diode (OLED). General Preparation Methods Various exemplary methods of preparing a positionally regular conductive block copolymer are provided herein. It is intended to describe the nature of such preparations and is not intended to limit the scope of the methods available. Certain compounds are useful as intermediates in the preparation of other compounds or polymers of the invention. A general scheme for preparing positionally regular conductive block copolymers is set forth in Scheme 1 below. In Scheme 1, the 'positional regular conductive block copolymer is prepared by the following steps: a) combining a nickel (11) catalyst with a first monomer-metal complex (organic metal I) to provide a position A regular conductive block copolymer intermediate wherein the first monomer-metal complex is prepared by a process comprising the steps of: And a first dentate-monomer and an activated metal, a Grignard reagent, or a RZnX, R2ZnX, or R3znM reagent, wherein the R is a (c2-C12) alkyl group, and the lanthanum is magnesium, manganese, lithium, sodium or potassium. And the lanthanide F, c; b) combining the second monomer-metal complex (organometallic ruthenium) with the positionally regular conductive block copolymer intermediate to provide a positionally regular conductive block copolymer, wherein the The dimonomer-metal complex is prepared by a process comprising the steps of: combining a second dihalogen-monomer with an activated metal, a Grignard reagent or an RZnX, R2ZnX, or R3ZnM reagent, wherein the alkyl group, the M system Magnesium, 135320.doc -24· 200930743 Manganese, lithium, sodium or potassium, and X is F, a, Br, or 1, wherein each dihalogen-monomer is independently substituted by two identical or different sulphur atoms. An aromatic or heteroaromatic group, and wherein if the dimeric-monomer has the same ring system, at least one dihalogen-monomer is substituted, and if the two dentate-monomers have the same ring system And all substituted, the substituents are different. The nickel (11) catalyst and the first monomer-metal complex are combined in either order. For example, a nickel (ruthenium) catalyst is combined with a first monomer-metal complex to provide a _ positionally regular conductive block copolymer intermediate. Alternatively, the first monomer oxime complex is combined with a ruthenium catalyst to provide a positionally regular conductive block copolymer intermediate. plan 1.

Wherein A, Β and 〇 each of molybdenum a E may be absent, or also &amp;, nitrogen, oxygen, phosphorus, antimony, or carbon; a |, nitrogen, oxygen, dish, sputum, or carbon, and in E not I35320. Doc -25· 200930743 When present, B and D form a bond; Χι and X2 are each independently halogen; m and n represent the number of monomer units present for the block copolymer to have a desired molecular weight;

Ri, R2, R3, R4, R5 and R6 are each independently absent or, if desired, from about 1 to about 5 esters, ketones, nitriles, amines, auxins, aryls, heteroaryls, or heterocycles. a substituent, a thiol group, a pyroline group, or an alkoxy group, and one or more carbon atoms of the alkyl chain in the alkyl group may be from about j to about 10 Ο, S, as desired. And/or NP group substitution, wherein P is a substituent or a gas protecting group as described above, and an M* system activating metal, a Grignard reagent, or a RZnX, R2ZnX4 R3ZnM reagent 'where &amp; (C2_Ci2) alkyl group , μ is magnesium, manganese, lithium, sodium or potassium, and X is F, C1, wherein the ring represents an aromatic structure, wherein the groups A, B, D and E have additional hydrogen atoms required to maintain the neutral ring structure. , the Ni(II) catalyst is any nickel (Π) catalyst that can achieve polymerization of the monomer-metal complex, and in one embodiment, the present invention provides a method for preparing a positionally-regular conductive block copolymer, It comprises: a) combining a nickel (II) catalyst with a first monomer-metal complex under conditions which provide living polymerization to provide a positionally regular conductive block copolymer intermediate, The first monomer-metal complex is prepared by a method comprising the steps of: combining a first dihalogen-monomer with an activated metal, a Grignard reagent, or an RZnX, R2ZnX or R3ZnM reagent, wherein the R system (CVC, 2) a base, μ system of magnesium, fierce, bell, nano or potassium, and X series F, Cl, Br or I; b) combined second monomer metal complex and positional regular conductive block copolymerization The intermediate is provided to provide a positional regular conductive block copolymer 135320.doc -26- 200930743 wherein the second monomer-metal complex is prepared by a method comprising the steps of: combining the second bis- _ Monomer and activated metal, Grignard reagent, or RZnX, R2ZnX or R3ZnM reagent, wherein the ruthenium (〇: 2 (: 12) alkyl, lanthanide magnesium, manganese, lithium, sodium or potassium, and X series F, Cl , Br or I, wherein each dihalogen-monomer is independently an aromatic or heteroaromatic group substituted by two identical or different halogen atoms, and wherein if the dihalogen monomer has the same ring system, then at least one The dentate-monomer is substituted, and if the two dimeric-monomers all have the same ring system and are substituted, then The substituents are different. In another embodiment, the method additionally comprises the use of a third monomer-metal complex which is the same as the first monomer-metal complex, to position the regular conductive block copolymer. The bond is extended. In another embodiment, the method additionally comprises extending the positionally regular conductive AB block copolymer chain to form a positionally regular conductive block copolymer. In one embodiment, the method additionally includes a chain extension step A positionally regular conductive ABC block copolymer is formed. In another embodiment, the positionally regular conductive AB block copolymer is a positionally regular polythiophene block copolymer. Various activating metals can be used to form the first monomer-metal complex and the second monomer-metal complex. Suitable activating metals can include, for example, zinc, indium, manganese, copper, and the like. Preferably, Rick (Zn*) is used. Typically, each monomer-metal complex formation temperature is at least about, preferably at least about 〇 ° C, and more preferably at least about 23. Hey. Typically, the monomer-metal complex is formed at a temperature of no more than about 100 ° C, preferably no more than about 60 ° C, and more preferably no more than about 4 ° C. 135320.doc • 27· 200930743 Typically, the formation of each monomer-metal complex is fully accomplished in at least about 5 minutes and is preferably fully completed in at least about 30 minutes. Typically, the reaction time is no more than about 24 hours, more preferably no more than about 8 hours, and even more preferably no more than about 1 hour. Preferred polymerization conditions for the first monomer-metal complex and the second monomer-metal complex to form a positionally-regular conductive block copolymer include, for example, an inert atmosphere (e.g., nitrogen, helium, or argon). Use and suitable temperature and time. ❹

The first monomer-metal complex is typically added to the metal catalyst to provide a positionally oriented conductive block copolymer intermediate. A metal catalyst may also be added to the first monomer-metal to provide a positionally regular conductive block copolymer intermediate. Usually the polymerization temperature is at least -78. . Preferably, it is at least (TC, and more preferably at least 23 C. Usually, the polymerization temperature does not exceed the boiling point of the solvent used, preferably does not exceed 60 ° C ' and more preferably does not exceed 4 〇 t. Usually the polymerization reaction is sufficient for at least 2 hours. It is completed, and preferably filled in at least J. Usually, the polymerization reaction does not exceed 72 hours, more preferably does not exceed 48 hours, and even more preferably does not exceed (four) hours. It can be used in the preparation of monomer/metal complexes. The polymerization is carried out in the same solvent as the solvent used. The entire reaction sequence can be carried out without isolating any of the intermediates. Suitable dioxins·monomers can include, for example, (d) di- ordinarily substituted or not taken: «C: C3°) a quaternary monomer or a dentate substituted or unsubstituted (c3-c3.)heteroaryl precursor. The aromatic or heteroaromatic monomer may be, for example, benzene, phenanthrene, cough, aniline, phenyl extended vinyl, thiophene extended vinyl, 135320.doc -28- 200930743 bis-thenylene-based extension Vinyl, —^^ acetylene oxime, exo-group, isothionaphthalene, benzophenone, porphin [2,3 吩, mouth 〜 ] ] ] ] 售 售 售 售 2 2 2 2 2 [2'3-d] 嗟Naphthalene, benzo[2,3] porphin, benzo[3,4] porphin, biphenyl, or hydrazino, and the like. The aromatic or heteroaromatic monomer may have from one to about three non-protein substituents. The substituents are each independently (C丨-C24)alkyl, optionally substituted with from about 1 to about 5 esters, ketones, nitriles, amines, aryl, heteroaryl, or heterocyclic groups, (C丨- C24) alkylthio, (C丨-C24)alkyldecyl, or (C^C^)alkoxy, and one of the alkyl chains in the alkyl group or

多个 Multiple carbon atoms may optionally be replaced by from about 1 to about 10 0, S or NH groups. Suitable dentate-monomers include, for example, 2,5-di-s-thiophene, 2,5-dihalo-pyrrole, 2,5-dihalo-furan, 1,3-dentary benzene, 2, 5-Bidentate-3-substituted thiophene, 2,5-dihalo-3-substituted pyrrole, 2,5-diiso-3-substituted furan, 1,3-difunctional-2-substituted benzene, L3 · Bismuth _4-substituted benzene, 込3-dihalo-5-substituted benzene, iota, dihalo _6_substituted benzene, L3-didentin_2, 4-substituted benzene, 1,3 - bis-2,5-disubstituted benzene, dentate, 2,6-disubstituted benzene, 1,3-biphenyl-4,5-disubstituted benzene, L3-dentate _4,6 _Disubstituted benzene, 1,3-dimorph-2,4,5-trisubstituted stupid, L3·dihalogen-2'4,6-disubstituted benzene, 1,3_dihalogen-2,5,6 -trisubstituted benzene, dihalo-2-substituted benzene, 1,4-difunctional-3-substituted benzene, 1,4-didentin-5-substituted benzene, fluorene dimer/6-substituted benzene, 1,4-dihalo-2,3-disubstituted benzene, fluorene dihalo-2'5-disubstituted benzene, U4-difunctional-2,6-disubstituted benzene, fluorene disaccharide·3, 5. Disubstituted benzene, 1,4-dimerin-3,6-disubstituted benzene, Μ_ dentate _3,5,6_trisubstituted benzene, 2,5-dii s 3,4- Disubstituted porphin, 2'5_di. _3'4· Los substituted pyrazole, 2,5-substituted furan tooth element _3,4- workers, or a combination thereof. 135320.doc • 19-200930743 In a preferred embodiment, the process for preparing a substituted HT polythiophene block copolymer is shown in Scheme 2 below. In Scheme 2, a positionally regular fluorene (3-substituted thiophene) block copolymer is prepared by a process comprising the steps of: combining a nickel (π) catalyst with a first thiophene·zinc complex to provide a position Regularly condensed (3-substituted thiophene) intermediates, b) combined second thiophene-zinc complexes with a positionally regular 1717 poly(3-substituted thiophene) intermediate to provide positional regular HT poly(3_substituted thiophene) The block copolymers combine the nickel (11) catalyst with the first thiophene-zinc complex in either order. For example, s, a nickel (II) catalyst is combined with a first thiophene-zinc complex to provide a positionally regular HT poly(3-substituted thiophene) intermediate, or the first thiophene-zinc complex is combined with nickel. The (π) catalysts combine to provide a positional regularity 111 poly(3_substituted thiophene) intermediate. Scenario 2.

R2

ZnX:

135320.doc ·30· 200930743 wherein 丨 and 2 are each independently halogen, and the heart and heart are each independently from about 1 to about 5 esters, ketones, nitriles, amines, halogens, aryls, An aryl group, or a heterocyclic group-substituted alkyl group, a sulfur-burning group, a pyridyl group, or an alkoxy group, and one or more carbon atoms of the thiol chain in the hospital base are optionally or 10 0, S, and/or NP group substitution, wherein p is the above substituent or nitrogen protecting group ' and its center and the ruler 2 are not simultaneously absent, and Zn* is a Rick zinc 'Ni(II) catalyst Any nickel (&quot;) catalyst that polymerizes the thiophene zinc complex is reached, and m is pregnant, wherein m and η are the number of monomer units present to provide the block copolymer with the desired molecular weight. In one embodiment, the invention provides a method of preparing a positionally regular fluorene (3. substituted thiophene) block copolymer comprising combining a nickel (II) catalyst with a first thiophene under conditions which provide living polymerization. -Zinc complex to provide a positionally regular fluorene (3-substituted thiophene) intermediate; b) combining a second thiophene-zinc complex with a positionally regular HT poly(3-substituted thiophene) intermediate to provide a positional rule a HT poly(3-substituted thiophene) block copolymer in which at least one monomer-metal complex is substituted 'and if the two monomer-metal complexes are substituted' then the substituents are not the same. In another embodiment, the method additionally comprises extending the positional regular Ητ poly(3_substituted OSE) block copolymer chain with a third thiophene-zinc complex as desired for the first thiophene-zinc complex. . In another embodiment, the method further comprises extending the positionally regular HT poly(3-substituted thiophene) AB block copolymer chain to form a positionally regular HT poly(3. substituted thiophene) fluorene block copolymer. In one embodiment, the method additionally includes a chain extension step to form a positionally regular HT poly(3-substituted thiophene) ABC block copolymer. 135320.doc •31 _ 200930743 The first and second thiophene-zinc complexes are prepared by the method described in U.S. Patent No. 5,756,653, the disclosure of which is incorporated herein by reference. The method comprises combining the first and second 2,5-di- quinone porphin with Rick ((iv) to provide the first and second thiophene-zinc complex. 2,5-di- _ The thiophene is dissolved in a suitable solvent, such as an ethereal solvent, such as tetrahydrofuran. The reaction flask can be cooled, followed by the introduction of activated zinc, preferably with the introduction of a Zn* (Zn*) reagent. The Zn* can be added to the reaction. The flask is stirred for a sufficient period of time to form a singular-synthesis complex by exchanging a zinc-based (Ζηχ) group with a quinone (halogen) group in the porphin. Formation of the thiophene-zinc complex Thereafter, a nickel (11) catalyst may be added to the reaction vessel containing the thiophene-zinc complex. The resulting mixture may be stirred for a sufficient time to form a polythiophene, which may typically be precipitated from the reaction mixture. After the zinc complex is formed, the thiophene-zinc complex can be added to the flask containing the nickel (II) catalyst. The reaction mixture can be substantially insoluble in the volume by transferring the polythiophene. The polythiophene is separated in a solvent. Other treatments may include filtration, washing with decyl alcohol, and at height Drying under vacuum can be carried out by, for example, a hydrocarbon solvent such as hexane by Soxhlet extraction. The formation of polythiophene can be carried out at any suitable effective temperature. In one embodiment, at about -100° The polymerization is carried out at a temperature of from c to about 150 ° C. In another embodiment, the polymerization is carried out at a temperature of from about -20 ° C to about 10 CTC, which may be the same solvent as that used in the preparation of the zinc phenanthrene complex. The polymerization is carried out in a polymerization process using a Ni(II) catalyst, which can be carried out at a temperature of about 〇. 〇 to the boiling point of the solvent used in the reaction step. Usually, Ni(II) catalyst is used as 135320.doc -32- 200930743 The polymerization step is carried out at a temperature of from about 〇 ° C to about 25 ° C. The activated metal activates a metal-based highly reactive metal having a large surface area and lacking a passivated surface oxide. For example, the activated metal may be a metal powder , metal dust, or metal particles. The activated metal can be activated by, for example, a chemical method, a thermal method, an electrochemical method, or an ultrasonic method, and the valence state of the activated metal is usually zero. Preferably, the activated metal is Rick metal, which is prepared by a method developed by Dr. Reuben D. Rieke, an inventor of the present invention. Rick process generally involves the reduction of tetrahydrofuran of an anhydrous metal halide (e.g., F, Cl, Br, or I) with an alkali metal. Suspensions. The metals used in the Rick process typically include, for example, potassium, sodium, and lithium. For example, Rick magnesium is prepared using potassium as a reducing agent, as described below:

MgCl2 + 2 K — Mg + 2 KC1 A variety of activated metals are prepared by this method, including, for example, Ming, Meng, Cu, Zinc, Lock, Hex, Zinc, Iron, Drill, Record, and Indium. In some cases, the reaction is carried out with a catalytic amount of electron carriers such as biphenyl or naphthalene. The activated metal is usually used in situ. Suitable activating metals include, for example, Ming, Meng, copper, zinc, town, about, titanium, iron, cobalt, nickel, indium, or combinations thereof. Preferably, the activated metal is a zinc chromite 2,5-di- sulphate. In a preferred embodiment, the dihalogen-single system is a bis-thiophene. 2,5-dihalo-thiophene can be 2,5-dinan-3-substituted thiophene, unsubstituted 2,5-dihalo-thiophene, or 2,5-didentin-3,4-disubstituted Thiophene bis-thiophene is usually 135320.doc •33- 200930743 is a monofluoro-, di-, _, or di-molybdenum phenanthrene which may be unsubstituted or substituted at the 3 and/or 4 positions. A combination of 2 5-difunctional thiophene, 2 5•dihalo-3-substituted thiophene and 2,5-difunctional _3,4-disubstituted thiophene can also be used. Suitable unsubstituted dihalothiophenes may include, for example, 2,5-difluorophene, 2.5-dithiophene, 2,5-dibromothiophene, 2,5-dithiophene, 2-fluoro-5-gas. Thiophene, 2-fluoro-5-bromothiophene, 2-fluoro-5-iodothiophene, 2-gas-5-fluorothiophene, 2·chloro-5-bromophene, 2-gas-5-fluorene, 2 -bromo-5-fluorophene, 2-bromo-5-phenethiophene, 2-bromo-5-iodothiophene, 2-iodo-5-fluorothiophene, 2-iodo-5-azone, and 2- Iodine-5-bromothiophene. The 2,5-dihaloquinones which are unsubstituted at the 3_ and/or 4' position may be used to prepare, for example, an unsubstituted polythiophene block and one or more substituted polythiophene blocks. Segment copolymer. For example, an unsubstituted polythiophene can be combined with a 3-substituted polythiophene block and/or a 3,4-disubstituted polythiophene block. Alternatively, the '3-substituted polythiophene can be combined with a 3,4-disubstituted polythiophene block. The dentate thiophenes listed above may be substituted at the 3 and/or 4 positions by the following groups: $ 1 to about 5 esters, ketones, nitriles, amines, aryls, heteroaryls or heterocycles as desired. Substituted ((:"(:24)alkyl, (C丨-C24)alkylthio, (Ci-C24)alkylcarboxyalkyl, or (C^C^)alkoxy, and in alkyl One or more carbon atoms of the alkyl chain may optionally be replaced by from about 1 to about 10 0, S or NH groups. Suitable 2,5-difunctional-3-substituted thiophenes may include, for example, 2,5- Difluoro-3-hexylthiophene, 2,5-dioxa-3-hexylthiophene, 2,5-dibromo-3-hexylthiophene, 2.5-diiodo-3-hexylthiophene, 2-fluoro-3-hexyl- 5-oxythiophene, 2-fluoro-3-hexyl-5-bromothiophene, 2-fluoro-3-hexyl-5-iodothiophene, 2-chloro-3-hexyl_5-fluorothia 135320.doc -34- 200930743 Phenyl, 2-chloro-3-hexyl-5-bromothiophene, 2-ox-3-hexyl-5-iodothiophene, 2-bromo-3-hexyl-5-fluoroseptene, 2-oxa-3-hexyl- 5- annole, 2-oxa-3-hexyl-5-iodothiophene, 2-iodo-3-hexyl-5-fluorothiophene, 2-iodo-3-hexyl-5-athiophene, 2-iodo-3 -hexyl-5-bromo&quot;cephene, ethyl 5-(2-5-difluorophenanthr-3-yl)pentanoate, 5-(2-5-dioxaphen-3-yl) Ethyl valerate, ethyl 5-(2-5-di-n-phen-3-yl)pentanoate, ethyl 5-(2-5-diiodothiophen-3-yl)pentanoate, 5- Ethyl (2-fluoro-5-athiophen-3-yl)pentanoate, ethyl 5-(2-fluoro-5-bromothin-3-yl)pentanoate, 5-(2-fluoro-5- Ethyl-3-yl)pentanoic acid, ethyl 5-(2-a-5-methanol-3-phenoxy)pentanoic acid, 5-(2-a-5-mothose-phenophene- 3-ethyl) ethyl valerate, ethyl 5-(2-indol-5-oxythiophen-3-yl)pentanoate, ethyl 5-(2·bromo-5-athiophen-3-yl)pentanoate , 5-(2-bromo-5-acanthen-3-yl)pentanoic acid ethyl ester, 5-(2- moth-5- gas porphin-3-yl) valeric acid ethyl ester, 5-(2- Ethyl iodo-5-bromothiophen-3-yl)pentanoate, and ethyl 5-(2_峨-5-fluorononin-3-yl)pentanoate. Preferably, 2,5-diphthoquinone_ 3_Substituted porphin 2-bromo-3-hexyl-5-mothole or 5-(2-di-5-峨嗟- _3_yl)pentanoic acid ethyl ester. Suitable 2,5-di-i The -3,4-disubstituted thiophene may include, for example, ethyl 5(2 5 -difluoro-3-hexylindol-3-yl)pentanoate, 5-(2-5-digas_3_hexylfluorene). Phenyl-3-yl)ethyl valerate, ethyl 5-(2-5-dibromo-3-hexylthiophen-3-yl)pentanoate, 5-(2-5-dimoth-3-hexyl porphin- 3-yl)ethyl valerate, 5-(2- 1-5-Gas·3_ hexyl sold phen-3-yl) Ethyl valerate, 5-(2-Fluoro-5-indol-3-hexyl porphin-3-yl) Ethyl valerate, 5-(2 -Ethylfluoro-3-hexyl-5-iodothiophen-3-yl)pentanoate, ethyl 5-(2-ethane-3-hexyl-5-fluoroindol-3-yl)pentanoate, 5-(2 - gas _3 · hexyl · 5 · desert phen-3-yl) bismuth citrate, 5-(2- gas-3-hexyl-5-breaking porphin-3-yl) valeric acid ethyl ester, 5 -(2-Bromo-5-gas-3-hexyl phenyl-3-yl) pentanoic acid ethyl ester, 5_(2_ 135320.doc -35- 200930743 -3-hexyl-5-ept-3-yl Ethyl valerate, ethyl 5-(2_hard_3_hexyl_5_ginophen-3-yl)pentanoate, 5-(2-indole-3-hexyl-5-bromo benzene-3- Ethyl valerate, and 5-(2-But-5-fluoro-3-hexyl septin-3-yl)pentanoic acid vinegar. Solvent The solvent used in these methods may be an aprotic organic solvent. One or more solvent compounds or mixtures can be used. Suitable solvents include etheric or polyether solvents. Examples of such solvents include diethyl ether, decyl-tert-butyl ether, tetrahydrofuran (THF), dioxane, diethylene glycol dimethyl ether, triethylene glycol dimethyl _, 1,2-dimethoxy group. Ethylene (DME or ethylene glycol dice), and the like. The solvent is usually a four-milk flavor. Polymerization Catalyst A variety of metal catalysts can be used in the polymerization of such methods. The metal catalyst may comprise an organometallic compound or a transition metal complex. For example, the metal catalyst can be a nickel, platinum, or palladium compound. Preferably, the metal catalyst is a ruthenium catalyst which provides a positionally selective polyporphin block copolymer. A catalyst Ni(II) catalyst for forming a positionally regular polythiophene block copolymer is used in an embodiment method. An effective amount of Ni(II) catalyst is used to effect the reaction using a sufficient amount of catalyst in less than about 5 days. This is usually in the range of about 0.01 to 10 mol% (m〇l%), however, any amount of nickel catalyst may be used, for example, 50 mol%, 100 m〇% or more. The amount of the oscillating monomer present in the end view is usually about 1 mol % nickel (II) catalyst to about 5 mol % nickel (II) catalyst, or preferably about 0.1 mol % recorded (II) Catalyst to about 3 mol% nickel (π) catalyst. Examples of suitable (Π) catalysts include, for example, Ni(PR3)2X2 (wherein R is 135320.doc -36·200930743 (C丨-c20) alkyl, (C6-C20) aryl' and X is a tooth And NiLX2 (wherein L is a suitable nickel (ruthenium) ligand and X is a halogen). Suitable nickel (π) ligands include hydrazine, 2-bis(diphenylphosphino)ethane, 1,3-diphenylphosphinopropane, [2,2-dimethyl-1,3-dioxol Cyclo-4,5-diyl)bis(methylene)]diphenylphosphine, bis(triphenylphosphine), and (2,2'-bipyridine) ligands. Other suitable Ni(II) catalysts include Ni(CN), 2, NiO, Ni(CN)5-3, Ni2Cl8·4, NiF2, NiCl2, NiBr2, Nil2, NiAs, Ni(dmph)2 (where dmph is two曱基乙二肟), BaNiS, [NiX(QAS)]+ (where X is halogen and QAS is As (o-C6H4AsPh2)3), [NiP(CH2CH2CH2AsMe2)3CN]+, [Ni(NCS)6]·4 , KNiX3 (where X is dentate), [Ni(NH3)6]+2, and [Ni(bipy)3]+2 (where bipy is a two-degree bite). Usually, the nickel catalyst also includes 1,2-bis(diphenylphosphino)ethane nickel (Π) vapor (Ni(dppe)Cl2), 1,3-diphenylphosphinopropane nickel (π) vapor. (Ni(dppp)Cl2), I,5·cyclooctadiene bis(triphenyl)nickel, dibromobis(triphenylphosphine)nickel, digas (2,2,-dipyridine)nickel, and four (triphenylphosphine) nickel (ruthenium). The general techniques and methods known to those skilled in the art can be used in the methods herein such as performing various standard procedures for polymerization and separation and purification of products. Properties of Polymer Structures and Conductive Polymers Generally, conductive polymers are organic polymers which, due to their conjugated backbone structure, exhibit high electrical conductivity (relative to the conductivity of conventional polymeric materials) under certain conditions. When the materials are doped, oxidized, or reduced, their performance as a hole or electron conductor is improved. After the low-oxidation (or reduction) of the conductive polymer, in the process commonly referred to as doping, the -electron (or added to the bottom end of the conduction band) is removed from the valence band to generate a radical cation 135320.doc • 37· 200930743 (or polaron). The formation of polarons acts in the separation domain of several monomer unit generating moieties. After further oxidation, another electron can be removed from the individual polymer segments thereby creating two independent polarons. Alternatively, unpaired electrons can be removed to produce a dication (or bipolar). In the applied electric field, both the polaron and the bipolaron are fluid and can move along the polymer chain by the delocalization of double bonds and single bonds. This change in oxidation state results in the formation of a new energy state called a bipolaron. Some of the residual electrons in the valence band are susceptible to these levels, allowing the polymer to act as a conductor. The degree of conjugation of this conjugated structure depends on the extent to which the polymer chain forms a planar configuration in the solid state. This is because the ring-ring common vehicle depends on the π_track overlap. If a particular ring is twisted off the plane, no overlap can occur and the common band structure can be interrupted. Some minor distortions are harmless because, for example, the degree of overlap between the porphin rings varies with the cosine of the dihedral angle between the rings. The properties of the conjugated polymer as an organic conductor may also depend on the morphology of the polymer in its solid state. Electronic properties may depend on the electrical connectivity between the polymer chains and the charge transport between the chains. The charge transport path can be along the polymer chain or between adjacent chains. Since the charged moiety has a dependency on the number of double bonds between the rings (ring planarity index), the planar main chain configuration promotes transport along the chain. This interchain electrical conduction mechanism may involve a stacking of planar polymer segments (referred to as π-stacking) or a chain* (four) hopping mechanism in which excitons or electrons may pass through space or other matrix to arrive or &quot;jump&quot; Close to the other chain of the leaving chain. Therefore, the method of ordering the polymer chain under the solid 4 can help to improve the 14 energy of the conductive polymer. It is known that the absorbance characteristics of the conductive polymer film Reflecting the enhanced re-stacking that occurs in the solid state. 135320.doc -38 - 200930743 In order to effectively use a co-polymer, it is advantageous to prepare the polymer by removing organic and ionic impurities from the polymerization medium. In particular, the presence of impurities (especially metal ions) in this material can have severely detrimental effects on the properties of the conductive polymer, including, for example, charge localization or trapping, exciton quenching, charge mobility reduction, Interface morphological effects such as phase separation, and oxidation or reduction of the polymer to atypical conductive states that may not be suitable for a particular application. There are several types of self-conjugated polymers that remove impurities. Most of these methods can be facilitated by the ability of the polymer to be dissolved in common organic and polar solvents. The positionally oriented conductive block copolymers are prepared by the methods described herein. Polymerization of other types of non-excimer polymers is described, for example, in Yokozawa et al., Po/ywer &gt;/〇Μ&quot; «α/, 36(2), 65 (2004). The materials are well known to those skilled in the art. For example, see Yang (Editor), The Chemistry of Nanostructured Materials * pp. 317-327 (&quot;Block Copolymers in Nanotechnology&quot;) (2003). The copolymer is also described (for example, Copo). /ywer·?, Overview awcf CWi/cfl/, Noshay and McGrath, Academic Press, 1977. For example, this article describes AB diblock copolymers (Chapter 5), ABA triblock copolymers (6th) And (-) AB-n-multiblock copolymers (Chapter 7), which form base block copolymer types in the present invention. Other block copolymers including, for example, polythiophene In (for example) the following documents: Francois et al, "ίΛ. Mei., 69, 463-466 (1995); Yang et al, 26, 1188-1190, (1993); Widawski et al, iWziwre, 369, 387-389 (1994); Jenekhe et al, 135320. Doc-39-200930743 279, 1903-1907 (1998); Wang et al., for example, ~C., 122, 6855-6861 (2000); Li et al., 32, 3034-3044 (1999); and Hempenius et al. , j 5〇c·, 120, 2798-2804 (1998). The derivative of the positionally regular conductive block copolymer may be a modified polymer such as poly(3-substituted thiophene) which retains the basic backbone structure of the base polymer but structurally modifies the base polymer. The derivative can be combined with the base polymer to form a family of related polymers. Derivatives ® retain the properties of the base polymer such as conductivity. Further, the positionally regular conductive block copolymer may comprise a conductive block having a conjugated structure that is doped or undoped, and one or more other non-conductive blocks. Non-conductive blocks can include various synthetic polymers including, for example, condensation polymers, addition polymers, and ring-opening polymers such as urethanes, polyamines, polyesters, polyethers, vinyl polymerizations. , aromatic polymers, aliphatic polymers, heteroatom polymers, decane, acrylate, methacrylate, phosphazene, decane, and the like. Inorganic and organic polymers can be used as the non-conductive portion. If desired, the positional regular conductive block copolymer can be blended with other components. These other components include, for example, inorganic glass and metals and other poly-[objects] such as inorganic polymers and organic polymers and the same type. (for example, two polythiophene types) or other conductive polymers of different types (for example, polythiophene and non-polythiophene). Block copolymers can be used as compatibilizers. Positionally regular poly(3-substituted porphin) block copolymers in a preferred embodiment 'position regular conductive block copolymer system position gauge 135320.doc 200930743 then poly(3-substituted thiophene) block copolymer . Materials having excellent π-conjugated, electrotransport, and solid state forms can be prepared by using position-specific chemical coupling methods that produce poly(s) having greater than 95% 2,5,-coupled alkyl substituents ( 3-substituted thiophene) block copolymer. Similar to the positional random poly(3-substituted thiophene) having a decyl group, an aryl group, and a decyl/aryl substituent, a positional regular poly(alkyl) group having an alkyl group, an aryl group, and an alkyl/aryl group 3-substituted thiophene) block copolymers are soluble in common organic solvents and by deposition methods (eg, spin coating, drop casting, dip coating, spray coating, and printing techniques (eg, inkjet printing, offset printing, and Transfer coating printing)) Enhanced workability when applied. Therefore, these materials have better processability in the large-area mode compared to the positionally random poly(3-substituted thiophene) block copolymers. In addition, due to their 2,5,-ring-ring coupling, uniformity 'Therefore it shows a clear π-common sign and a high extinction coefficient corresponding to the absorption of visible light by π-π* absorption in these materials. The quality of the absorption band structure is 'when the positional poly(3-substituted thiophene) block copolymer having a burnt group, an aryl group, or a aryl/aryl substituent is used in an organic electronic device, This structure is used and thus determines the efficiency and performance of the device. Another advantage of the positional regularity of poly(3-substituted thiophene) block copolymers is that they are self-assemblable and form highly ordered structures in the solid state. These structures tend to juxtapose the thiophene ring system via a π-stacking unit and allow for improved interchain charge transport via the bonding arrangement between the individual polymers, thereby enhancing the conductive properties compared to the positionally random polymer. Therefore, the morphological advantages of these materials can be understood. 135320.doc -41 · 200930743 As in the case of polybenzazole, it is shown that various poly(3.substituent) block copolymers having a pendant group, an aryl group, and an alkyl-aryl substituent are soluble in, for example, toluene. And common organic solvents such as xylene. These materials all share a common electron-band structure similar to polyphene, making it a P-type conductor suitable for use in electronic applications' but due to its solubility it is much easier than polythiophene. &amp; Processing &amp; Purification. These materials are made into oligomeric chains such as (3-alkylthiophene) n, (3-arylthiophene). Or (3_alkyl/arylthiophene)n, wherein the n-coefficient value is a repeating unit number of 2-10, or it is made into a polymer having η of 1 1-350 or higher, but such materials In terms of η, the most common value is η 50-200. Substituent effect Since the electronic properties of the conductive polymer are derived from the common band structure of the polymer backbone, any factor that increases or decreases the electron density in the main chain can directly affect the band gap and energy of the conductive polymer. Therefore, a substituent bonded to the main chain and containing an electron-withdrawing substituent can lower the electron density of the conjugated backbone and lower the HOMO of the polymer. The substituent bonded to the main chain and containing the electron-releasing functional group can have the opposite The nature of the substitution effect is known to those skilled in the art and is described in detail in the general text on organic chemistry (see, for example, March, J., Advanced Organic Chemistry, Second Edition 'John Wiley &amp; Sons, New- York, 1985, and references cited therein. In both cases, the magnitude of the polymer energy level depends on the specific functional group of the substituent, the length or nature of the functional group to the conjugated backbone linkage, and the polymer. The presence of other functional features. In the case of poly(3-alkylthiophene), it usually includes a hospital that can improve solubility. 135320.doc •42- 200930743 base substituent , which has an electron-releasing effect, thereby increasing the HOMO of the polymer relative to the polythiophene. For example, it has been shown that the fluorine substituent as a 3-substituent or a 4-substituent component of the polythiophene is adsorbed from the polythiophene homopolymer. The electrons thereby reduce the H〇M〇 of the conductive polymer. It can be seen that the alkoxy substituent at the 3-position can be used to reduce the band gap of the positionally regular poly(3-substituted thiophene). In each of these cases The manipulation of the 'energy level' is achieved by modifying the homopolymer backbone. In many cases, it is desirable to incorporate specific functional groups into the conductive polymer to impart specific properties. For example, the introduction of poly(3-hexyl) • The thiophene-based substituents to render the polymer soluble in common organic solvents. However, for applications where low HOMO is required, this electron-releasing functional group actually imparts an opposite effect to the desired electronic effect. The flexible synthesis method that balances and adjusts the electronic, optical, and physical properties of conductive polymers to provide materials that meet different performance requirements provides practical benefits for organic device development. The modified positionally regular conductive block copolymers disclosed in the disclosed methods can include various combinations of different block linkages including, for example, unsubstituted polythiophenes, 3-substituted polythiophenes, and 3,4 a disubstituted polyporphin. The substituents may be any of the groups listed in the definition of the substituents above. In one embodiment, the 'thiophene 3-substituted thiophene, wherein the substituent is an alkyl group, sulfur-burning a substituent, a methoxy group, or a methoxy group. The substituent may be substituted with other functional groups, such as, but not limited to, from about 1 to about 5 esters, ketones, nitriles, amines, hydroxyls, aryl groups, a heterocyclic group, and a heteroaryl group. One or more carbon atoms of an alkyl chain in an alkyl group, an alkylthio group, a pyrenylalkyl group or an alkoxy group are also 135,320.doc •43- 200930743 may be one or more Atomic substitutions, such as deuterium, s, Np groups (wherein a p-substituent or a nitrogen protecting group), or a combination thereof. Substituents which improve the solubility of the polybenzazole copolymer are generally preferred. Preferably, the substituents include those having at least about 5 or 6 carbon atoms. For example, hexyl, hexyloxy, hexylthio, and hexylmethylcarbazide. In one embodiment, the substituent directly bonded to the 3 position may preferably be a hetero atom such as sulfur, helium, oxygen, or a nitrogen atom. The heteroatoms can be substituted with other suitable bases, such as those described above in the definition of substitution. The hetero atom at the 3-position of the porphin can further enhance the conductivity of the polythiophene block copolymer by, for example, the following, such that the aromatic electrons of the porphin ring system can delocalize and/or cause the encapsulation of the polymer. Improvements can be made and the microstructure can be optimized to improve charge carrier mobility. In another aspect of the invention, one or more (e.g., 丨 to 〇, 丨 to 5 or 丨 to ^) methylene groups (which are optionally composed of one or more heteroatoms) may be used. Alternatively, the aryl, heteroaryl, or heterocyclyl substituent is separated from the thiophene ring (e.g., polyethylene or polyethylenimine, wherein the oxime comprises from about 2 to about 1 repeat units). The substituent at the 3-position of the thiophene monomer can improve the positional regularity of the product polythiophene block copolymer by providing a space volume to influence the chemical orientation of the polymerization reaction. - The terminal group on the product polythiophene block copolymer (the group at the 2 or 5-position of the thiophene at the end of the polymer) may be hydrogen or halogen. The terminal group of the polythiophene block copolymer may also be a pendant or functionalized alkyl group which can be obtained by terminating the polymerization reaction with an organometallic substance such as an organic-zinc reagent. The polythiophene block copolymer prepared by the methods described herein has an average weight of 135,320.doc • 44 - 200930743 and may have a molecular weight of from about 5,000 to about 2, preferably from about 2 to about 80,000. More preferably, it is about 4 Å, _ to about 6 Å, _, as determined by Gpc using a polystyrene standard stored in tetra-furan. The degree of polymerization distribution index (PDI) may range from about 丨 to about 25, or preferably from about 丨 to about 24, or more preferably from about 1.2 to about 2.2. The polythiophene block copolymer prepared by the process of the present invention typically has a positional regularity of at least about 87% without any purification after treatment. Simple purification techniques such as performing Soxhlet extraction with hexane can improve the positionality to greater than about 94%, preferably greater than about 95%, more preferably greater than about 97%, still more preferably greater than about 98%, or even More preferably greater than about 99 〇 / 〇. The crude polyphenanthrene block copolymer can be isolated after polymerization by precipitation in methanol and subsequent simple filtration of the precipitated polymer. The crude polythiophene block copolymer has excellent properties relative to the prior art crude product. The crude polythiophene block copolymer has a higher positional regularity than known preparation methods, which reduces the amount of purification work required to provide usable materials for electronic applications. The higher position regularity gives the polythiophene block copolymer a higher conductivity. The conductivity of the regular 3 _ substituted poly porphin at the time of the "hetero" can be about 1'000 Siemens/cm, +/- about 400 Siemens/cm. Positional randomness 3_substitution The polystimulus copolymer is typically conductive at about 5-1 〇 Siemens/cm. In addition, the undoped positional 3-substituted polythiophene block copolymer is a conductive polythiophene block copolymer which is electrically conductive and undoped at a position of from about 1 〇 to about 5 6 Siemens/cm (semiconductor range). Conductive at approximately 10.9 Siemens/cm. Doping In a preferred embodiment, the positionally oriented conductive block copolymer can be doped by oxidation in the manner of 135,320.doc 45.200930743 or in a reducing manner. The addition of dopants can result in a range extension of the conjugated π system in individual polymer molecules. There is no need to extend the range of the conjugated enthalpy system over the entire molecular range. The range of the π-conjugated system in a single molecule must be sufficiently extended such that the π-conjugated moiety in the individual molecule is adjacent to a portion of the π-conjugated moiety in the adjacent molecule after removal of the solvent. In the π-conjugated system, electrons are delocalized substantially within the entire π conjugate bond. These electrons are more loosely bonded and can be used in electrical conduction. When an electric field is applied, electrons can flow along individual molecules and can jump from one molecule to an adjacent molecule in a region where π conjugated portions of adjacent molecules overlap. It is also possible to electrochemically achieve doping by limiting the positionally-regular conductive block copolymer to the surface of the electrode in an electrochemical cell and placing it at an oxidation potential. A positionally-regular conductive block copolymer matrix can be introduced. The dopants include, for example, angstroms (Id, bromo(2), iron hydride, and various kundamates or salt salts. Other dopants may include, for example, various known rust salts, iodonium a salt, a borate, a toluenesulfonate, a triflate, and a sulfoximine. The positionally regular conductive block copolymer can be doped by, for example, the following method: dissolving the polymer Suitable organic solvents and dopants are added to the solution, followed by evaporation of the solvent. A variety of variations of this technique can be used and are well known to those skilled in the art. For example, see U.S. Patent No. 5, 〖98,丨53, which is incorporated herein by reference. In conductive film applications, the conductivity can be between about lxl 〇-ss/cm to about 104 s/cm, but more typically it is about s/s/ From cm to about 5 〇〇s/cm. In the polythiophene block copolymer system Regular poly(3_substituted thiophene) embedded 135320.doc -46· 200930743 segment copolymer (wherein the 3-substituent is an alkyl, aryl, or alkyl/aryl moiety and a* in the 3-substituent. Where the position has an oxygen substitution or in the case where the α or the position of the 3 substituent has a hetero atom), the desired characteristic of the (4) film is that its conductivity retains thousands of hours under normal use conditions and at higher temperatures and/or humidity. The following can meet the requirements of the device stress test. This is beneficial to stabilize the range of charge mobility and allows the characteristics to be adjusted by controlling the amount and type of dopants and to adjust the characteristics by adjusting the primary structure. There are many types of oxidizing agents that can be used to adjust the conductive properties as described above. By controlling the amount of dopants exposed to the polythiophene block copolymer, the resulting conductive ruthenium film can be controlled due to its high vapor pressure and in organic High solubility in the solvent, the halogen can be applied to the gas phase or in the solution. Compared with the material of the neutral state, the oxidation of the polythiophene block copolymer can greatly reduce the solubility of the material. The solution is applied to the device. Suitable dopants may also include, for example, ferric chloride, tri-gas gold, pentafluorination, metal hypochlorites, proton acids (eg, benzoic acid). And its derivatives, propionic acid, and other organic carboxylic acids and sulfonic acids), nitrosonium salts (such as NOPF6 or NOBF4), or organic oxidants (such as tetracyanate, di-cyanide), and high-valent iodine oxidants ( For example, iodonium benzene and diethyl ethoxy phenoxy epoxide block copolymers can also be oxidized by adding a polymer containing an acid or an oxidizing functional group such as poly(styrenesulfonic acid). The solvent to be used for the addition of the dopant is not particularly limited. One or more solvent compounds or mixtures may be used. An organic solvent may also be used. For example, _, an ester, and an alcohol may be used. Water may be used. A polar solvent can be used. Can be used 135320.doc •47· 200930743 aprotic solvent. A solvent having a molecular weight of less than 2 Å or less than 1 〇〇 g/m 〇 i can be used. Suitable solvents for the addition of dopants include, for example, dimethylformamide (DMF), dioxolane, methyl ethyl ketone, mibk, ethylene glycol diterpene (tetra) butyronitrile, cyclopentamidine, rings. _, bite, chloroform, nitromethane, 2-nitromethane, diethylene, tetraethylene, propylene carbonate, quinoline, cyclohexane, 1,4-dioxolane, dimethyl argan DMS 〇), nitrobenzene, gas benzene, and methyl-2-&quot; than bite _. ® Other Components In a preferred embodiment, the positionally-regular conductive block copolymer may also comprise or comprise a plurality of other suitable components, such as sensitizers, stabilizers, inhibitors, bond transfer agents, co-reacting monomers or A polymer, a surface active compound, a smoothing agent, a dispersing agent, a hydrophobic agent, a binder, a flow improver, a diluent colorant, a dye, a pigment, or a dopant. The optional components can be added to the polymer composition by dissolving the positionally regular e-block copolymer in a suitable organic solvent and adding the component to the solution, followed by evaporation of the solvent. . In certain embodiments of the invention, positionally oriented conductive block copolymers such as polythiophene block copolymers are readily useful as substantially pure polymers or doped polymers. Film In the preferred embodiment, the bit 4 regular conductive block copolymer may be in the form of a film. Highly conductive films of soluble positionally regular conductive block copolymers can be used in a variety of applications, including, for example, multiple types of diodes. In its neutral or undoped form, the soluble position regular conductive block copolymer 135320.doc -48· 200930743 provides the ability to be applied by the following techniques: spin casting, droplet casting screen printing, Inkjet, and standard printing techniques such as transfer coating or roll coating. Depending on the amount of dopant added, the conductivity can be adjusted from a neutral or semiconducting state to a highly conductive state, making the material specific for a given application. In general, the conductive film of the doped-site regular conductive block copolymer can be made to pass through the visible region for 3 months. This makes it suitable for transparent conductors. This combination of features makes it suitable for use in electronic devices such as diodes and light-emitting diodes. ° It has been shown in diodes and in luminescent diodes and solid-state illumination t-position regular conductive block copolymers (especially blended The hetero-position regular conductive block copolymer) is suitable for use as a positive charge carrier, also known as a hole injection layer. This depends on how easily it is oxidized and its stability in the mixed state. The properties of the conductive film were measured by evaluating its high conductivity value, good electronic properties, and high thermal stability. Conductivity is usually measured by the following method: σ = Ι / (4.53 VW), where the conductivity 〇 is measured by s / coffee, ❹ ❹ flow (10) P), electricity (V), and film thickness (cm). This value is usually measured by a standard four-point probe method in which a current flows between the two electrodes and is measured by another electrode. The thickness can be measured by different methods such as s belly and rim. The use of a soluble positional regular conductive block copolymer to construct a conductive layer or film provides several advantages in the polar body, such as ease of processing of materials and components during device fabrication. In a neutral or undoped form, the positionally oriented conductive block copolymer provides the ability to apply a poly(tetra) block copolymer layer using the following techniques: spin flooding, droplet washing, screen printing, spraying 135320.doc -49- 200930743 Ink, and standard printing techniques such as transfer coating or roll coating. These methods allow for in-situ gentle processing and precise control of the volume of conductive material applied. In general, methods for printable or printed electronic devices can be used. The lithography and nano silver engraving methods can be used. The use of positionally regular conductive block copolymers provides several advantages in this application. The most important of these advantages is the ability to adjust the conductivity of the device by controlling the morphology of the film, selecting the oxidant used, and the amount of oxidant used. When the materials are formed in a neutral or undoped state, the conductivity can be carefully adjusted by the amount of oxidation. Another key benefit of using such materials is the oxidation or &quot;doped&quot; conductivity stability of the positionally oriented conductive block copolymer compared to the use of other conductive polymers. The selective dissolution of such materials also permits the selective application and removal of films of such materials in the device. In addition, conductive polymers are described in The Encyclopedia of P〇丨ymer

And lei, pp. This reference also describes the blending and copolymerization of polymers, including the formation of block copolymers. High purity positionally regular conductive block copolymers prepared by the methods described herein can be used to form films. The crucible can be formed by using a conventionally-regulated conductive block copolymer solution dissolved in a solvent by standard methods known to those skilled in the art, such as spin coating, casting, dip coating, ink jet coating, and rods. Coating, roll coating, air knife coating, curtain coating, extrusion slot die coating, and the like. For example, 'for a method of preparing a film and an organic field-effect transistor, see U.S. Patent Nos. 5,892,244, 6,337,102, 7,049,631, 135,320, doc-50, 2009, 030, 743, 767, 767, 7,025, 277, 7, 053, 401, And 7, pp. 57,339, which is incorporated herein by reference. In one embodiment, the positionally regular conductive inlaid segment copolymer film can be formed by, for example, the following method: Langmuir-Blodgett forming a positionally regular conductive block copolymer precursor a film, and the positional regular conductive block copolymer front enthalpy is converted into a positionally regular conductive block copolymer. Similarly, a thin film can be formed by, for example, the following method: vapor deposition of a regular conductive block copolymer precursor, and conversion of a positionally regular conductive plate segment copolymer precursor to a positionally regular conductive block copolymer Things. In one embodiment, the positionally regular conductive block copolymer film can be formed by, for example, spin coating. The positionally regular conductive block copolymer solution is placed on the substrate and rotated at a high speed to spread the fluid by centrifugal force. The substrate continues to rotate as the fluid rotates out of the edge of the substrate until the desired film thickness is achieved. The solvent applied is generally volatile and simultaneously evaporates. In addition, the higher the angular velocity of rotation, the thinner the resulting film. The film thickness also depends on the solution concentration and solvent. In one embodiment, the positionally oriented conductive block copolymer film can be formed by, for example, casting. The molten position regular conductive block copolymer is introduced into the mold so that it can be solidified, cooled, and disassembled in the mold to provide a film. In an embodiment, the positional regular block copolymer thinner may be formed by, for example, dip coating, wherein the substrate is impregnated into a can containing a positionally regulated segment, and the substrate is removed from the can. Material and make it (four). The coated substrate is air dried or baked. 135320.doc • 51 · 200930743 In one embodiment, a positionally regular conductive block copolymer film can be formed by, for example, inkjet coating, wherein a positionally regular conductive block copolymer solution is self-piezoelectrically sprayed The ink is sprayed onto the substrate. The coated substrate can be air dried or baked. The tweezers can have a variety of thicknesses. Typical film systems range from about 1 μηη to about 丨mm. The film can include a colorant, a plasticizer, or a dopant. The positionally regular conductive block copolymer can be electrically conductive, especially when a dopant is included in the polymer matrix. The application of the positionally-regular conductive block copolymer is not particularly limited and may include optical, electronic, energy, biomaterials, semiconductors, electroluminescence, photovoltaic, LED, OLED, PLED, sensor, transistor , field effect transistors, batteries, flat panel displays, organic lighting, printed electronics, nonlinear optical materials, dimmable windows, RFID tags, fuel cells, triodes, rectifiers, and other applications. See, for example, Kraft et al., et al., 37, 402_428 (1998). See also Shinar, Orgam.c Zz. 丑 Spring Springer_ Verlag, (2004). A hole injection layer can be fabricated. A multilayer structure can be fabricated and a thin film device can be fabricated. Printable film. Patterning can be performed. Printing can be performed on consumer products. Small transistors can be fabricated. In a variety of applications, the compositions are formulated to provide good solution processing and film formation. Blends with other polymers including conductive polymers can be prepared. The nanowire morphology of the block copolymer can be developed in nanoscale manufacturing. The following is a brief description of an exemplary application of a positionally oriented electrically conductive block copolymer. 135320.doc -52- 200930743 Organic Light Emitting Diode In a preferred embodiment, a positionally oriented conductive segment copolymer prepared by the methods described herein can be used, for example, in an organic light emitting diode. For example, the positional regular polythiophene can be used in the fabrication of organic light emitting diodes (OLEDs). Organic light-emitting diodes (OLEDs) are used in electronic applications or as backlights for, for example, liquid crystal displays. Generally, organic light-emitting diode systems are fabricated using a multi-layer structure. The emissive layer is typically sandwiched between one or more electron transport layers and/or a hole transport layer. Electrons and holes as charge carriers are moved toward the emissive layer by application of a voltage and recombined therein to excite and illuminate the luminophore units contained in the emissive layer. The positionally oriented conductive block copolymer can be used in one or more charge transport layers and/or emissive layers depending on its electronic and/or optical properties. Furthermore, if the positionally regular conductive block copolymer itself exhibits electroluminescent properties or contains electroluminescent groups or compounds, its use in the emissive layer is particularly advantageous. In this case, luminescence can be achieved by injecting charge carriers only into the conductive polymer. The selection, characterization and processing of suitable monomers, oligomeric and polymeric compounds or materials for use in OLEDs are generally known to those skilled in the art (see, for example,

Meerholz, 31-34 (2000) and Alcala, 却 ρ/. 88, 7124-7128 (2000) and references cited therein). In another application, positionally regular conductive block copolymers (especially those exhibiting photoluminescence properties) can be used, for example, as light source materials for display devices. For example, European Patent Application Publication No. 〇 889 3 5 Said in a nickname or by C. Weder et al. 'Science, 279, 835-837 (1998). 135320.doc -53- 200930743 Field Effect Electron Crystal Hip In a preferred embodiment, the positionally oriented conductive block copolymer can also be used, for example, in field effect transistors (FETs). In a field effect transistor, the organic semiconductor material can be disposed as a thin film between the gate dielectric and the channel and the source electrode (see, for example, U.S. Patent No. 5,892,244, PCT Patent Application Publication No. WO 00/79617, U.S. Patent No. 5 998 8〇4). Preferred applications of such field effect transistors are, for example, integrated circuits, thin film electromorph (TFT) displays, and security applications due to the many advantages of such materials (e.g., fabrication of large surfaces at low cost). In safety applications, field effect transistors and other devices with semiconductor materials (such as transistors or diodes) can be used in radio frequency identification (RFID) tags or security tags to verify and prevent counterfeit voucher. Valuable documents may include, for example, banknotes, credit cards, identification (ID) certificates, passports, licenses, or any other product of economic value (such as stamps, tickets, shares, bonds, checks, and the like). First Placed Power In a preferred embodiment, the positionally oriented conductive block copolymer can also be used, for example, in photovoltaic cells. Photovoltaic cells are electrochemical devices that convert electromagnetic radiation into electrical energy. Although not limited by theory, the conversion of electromagnetic radiation to electrical energy can be achieved via a charge separation event that occurs after photon absorption. This results in the formation of an excited state called an exciton in a p-type semiconductor in direct contact with the n-type semiconductor. Typically the semiconductor domain is sandwiched between one or more of the active layers, at least one of which is sufficiently transparent to allow photons to pass. Photovoltaic cells can be used in rechargeable batteries or for running electronic devices. 135320.doc •54- 200930743 It offers many advantages for any electrical application powered by the distribution network, whether it is an alternative to a battery or a charge 2 device that supplies power to the recovery unit. Finally, it can also be used to supplement the electricity provided by the distribution network or to replace the electricity provided by the distribution network. Photovoltaic cells typically include at least four components, two of which are electrodes. The components are transparent first electrodes, such as indium tin oxide coated on plastic or glass, which acts as charge carriers. This component is typically a negative pole and allows ambient light to enter the device. The second electrode may be made of a metal such as calcium or aluminum. In some cases, the metal can be applied to a support surface such as plastic, glass, sapphire, gasification 26, quartz, or diamond. This second electrode can also carry current. There is a discrete layer or a mixture of p and η-type semiconductors, i.e., third and fourth components, between the electrodes. A p-type material can be referred to as a primary light-harvesting component or layer. This material absorbs photons of a specific energy and produces a state that causes electrons to enter an excited energy state, thereby leaving a positive charge or &quot;hole&quot; in the ground state level. This is called exciton formation. The excitons diffuse into the junction between the p-type and the η-type material, thereby generating charge separation or exciton separation. Electron and &quot;holes&quot; charge are introduced into the electrode via η-type and ρ-type materials, respectively. This causes current to flow out of the battery. In addition to the positionally-regular conductive block copolymer described herein, the Ρ-type semiconductor can also Containing a conjugated polymer comprising, for example, a mixture or blend of materials 'including the use of poly-phenylene vinylene (PPV) or poly(3-hexyl)thiophene (Ρ3ΗΤ). The η-type component can comprise Materials with strong electron affinity include, for example, carb〇n fuiierene, titanium dioxide, cadmium selenide, and polymers and small molecules that are specifically designed to exhibit budding behavior. 135320.doc -55- 200930743 The performance of photovoltaic cells can be determined by the efficiency of the 4 metering energy to the conversion of electrochemical energy, such as by quantum efficiency (the number of photons used effectively divided by the number of absorbed photons) and the peak output produced by the battery Power (by product

IppVpp is measured as 'the voltage at which the peak current is 1 叩 and the voltage at the peak power is v. Photoluminescent Device In a preferred embodiment, the &quot;positionally regular conductive block copolymer&quot; can also be used, for example, as a hole injection or hole transport layer in an organic or polymeric electroluminescent device. In the electro-luminescence domain + use of the positional regular lead segment copolymer can be known for: a number of desired characteristics, such as improved device luminosity, reduced threshold voltage, extended life, electronic blocking materials and components during device manufacturing The ease of processing, the ability to apply hole injection or hole transport layers in electroluminescent devices using spin-on, drop-injection, and other printing techniques, and the ability to fabricate flexible, more electroluminescent devices The ability to prepare low-weight electroluminescent devices and the ability to produce low-cost electroluminescent devices. Electroluminescent devices are devices that convert current into photon flux. This can be done when electrons and positive charges or &quot;holes&quot; meet in an electroluminescent material to produce an excited species or excitons that emit photons when decaying to the ground state. The device is an efficient way to generate light with low voltage and minimal radiant heat. These devices are currently available in a variety of consumer electronic devices. An example of an electroluminescent device includes four components. Two tie electrodes in these components. The first component can be a transparent negative electrode such as indium tin oxide coated on a plastic or glass substrate that acts as a charge carrier and allows photons to be emitted from the device 135320.doc - 56 - 200930743. The second electrode or positive electrode is typically composed of a low work function metal such as calcium or aluminum or both. In some cases, the metal can be applied to a support surface such as plastic, glass, sapphire, aluminum nitride, quartz or diamond. This second electrode introduces electrons into or into the device. An electroluminescent layer and a hole injection layer or a hole transport layer are present between the two electrodes. The second component is an electroluminescent layer material. The electroluminescent layer can comprise, for example, materials based on positionally regular conductive block copolymers, other conductive polymers, and organic-transition metal small molecule complexes. The materials are typically selected based on the efficiency with which the material emits photons as it decays to the ground state via fluorescence or phosphorescence and depending on the wavelength or color of the light emitted by the material through the transparent electrode. The fourth component is a hole injection or hole transport layer material. The hole injection or hole transport layer is capable of transferring a positive charge or &quot;hole&quot; from the transparent negative electrode to the electroluminescent layer to produce a conductive material that in turn causes the excitons to emit light. The hole injection or hole transport layer is typically a P-doped or oxidized conductive material, which is generally selected based on the ease with which a positive charge can be transferred to the electroluminescent layer and its overall efficiency. Organic and polymeric electroluminescent devices can take a variety of forms. If the electroluminescent layer comprises a small molecule which is usually vacuum deposited, it is generally referred to as an OLED (organic light-emitting diode p. If the electroluminescent layer comprises an electroluminescent polymer which is usually solution processed and deposited, then generally The device is referred to as a PLED (Polymer Light Emitting Diode). » Some electroluminescent layers may not fully conform to any of the above descriptions, such as a mixture of electroluminescent materials and solid electrolytes that form a light-emitting electrochemical cell. The layer can be designed to emit white light (ie, a balanced blend of primary colors) for white light applications or can be filtered to use 135320.doc -57- 200930743 for full color display applications. The electroluminescent layer can also be designed to Emit specific colors 'eg red, green and blue, which can be combined to produce a full chromatogram. Each light emitting diode (LED) can be combined to make a single color (single color) or full color (usually by combining red, Most colors produced by green and blue) flat panel display. It can be a passive matrix display with a hole injection or hole transport layer and electroluminescent layer between the two electrodes. Straight angle deposits a strip of negative electrode material onto the strip of positive electrode material, causing current to flow through a negative electrode and a positive electrode strip to cause illumination at the intersection of a single pixel in the display. It can also be an active matrix display 'electricity at each pixel The crystal controls whether individual pixels emit light and their brightness. The active matrix display can be either bottom emission (where light passes through or near the transistor circuit) or top emission (where the light exits in the opposite direction of the layer containing the transistor circuit). In a preferred embodiment, the positionally oriented conductive block copolymer can also be used, for example, in non-luminescent or non-photovoltaic diodes. Diodes are described, for example, in Ben G. Streetman, Siaie V. , 4th edition '1995 (see, for example, Chapters 5 and 6). This book describes, for example, the fabrication of junctions and diodes. In a diode type, the p_type material is compared to the n_type material. Examples of semiconductor junction type diodes include a normal p_n diode, a gold doped diode, a Zener diode, an avalanche diode, and a transient voltage suppression (TVS) diode. Body, light-emitting diode (LED), photodiode, Schottky diode, urgency diode, Esaki or tunnel diode, impatt diode, TRAPATT diode, BARITT diodes, and Gunn diodes. Other types 2 135320.doc -58- 200930743 Polar bodies include point contact diodes, vacuum or vacuum tube diodes, exhaust diodes and variable capacitance Or a variable anti-diode. Those skilled in the art can prepare non-luminescent and non-photovoltaic diodes. The non-luminescent and non-photovoltaic diodes can be fabricated by methods known in the art. The ρ-η junction can be fabricated by (1) providing a Ρ-type material, (11) providing a η-type material, and (iii) combining a p-type material and an n-type by methods known in the art. The materials are brought into contact with each other. The p-type material can be a positionally oriented conductive block copolymer as described herein. Similarly, additional steps can be provided to obtain additional P-type materials and combine them with the p_n junction to provide a Ρ_η·ρ sandwich-type structure. The positionally regular conductive block copolymers can additionally be used, for example, in liquid crystal and/or semiconductor materials, devices or applications. The high conductance of such polymers allows for improved conductivity and thus improved functionality of such applications and devices as compared to conventional synthesis. The positionally oriented conductive block copolymers described herein can also be used, for example, in anti-Q films, electrode materials in batteries, and the like. Thus, electronic devices comprising circuits constructed with the polymers described herein (e.g., the polymers prepared as described in Example 1) can also be used. The positionally regular conductive block copolymer can be, for example, a positionally random polypene, which can be used in electronic device applications where high conductivity is not required for positional regular polythiophenes. For example, the optical properties of positionally random polythiophenes are clearly dependent on the polycation and pH of the solution, which represents a significant difference between 435 nm and 516 nm in the maximum visible light absorption of each assembly. (See, for example, Myunghwan et al., /. Macrowo/. 5W., 38(12) 135320.doc • 59-200930743 1291 (2001)). This rare sensitivity of positionally random polythiophenes to polycations can have potential applications in sensor devices. It is to be understood that the description of the invention has been inferred Other elements and/or limitations may be required to practice the invention in light of the teachings of the invention. However, as such other elements and/or limitations may be readily determined by those skilled in the art after having regard to the present description of the present invention, and are not necessary for a complete understanding of the present invention, therefore no such elements are provided herein. And the discussion of restrictions. For example, the materials of the present invention can be incorporated into electronic devices, and as such electronic devices are known to those skilled in the art, they are not described in detail herein. Further, the compositions of the present invention can be summarized and embodied in various forms and applied to the final application not specifically set forth herein. For example, those skilled in the art will appreciate that the invention can be incorporated into an electronic device other than the electronic devices detailed herein. Other manufacturable devices (respecting the polymer properties of the invention) include, for example, monopolar transistors (eg, FETs, BJTs, and JFETs), heterojunction transistors (eg, HEM1^HBT), detectors (eg, PIN, MSM, HPT, focal plane array, cCD, and active pixel sensors), diodes (such as peltier and waste), optical devices (such as waveguides, external cavity lasers and resonators, WGM Ray) Shots, optical amplifiers, and tunable emitters), and quantum structures (such as quantum wires, quantum dots, and nanowires). Method of preparing a composition 135320.doc 200930743 ❹

The compositions described herein can be prepared by any of the techniques available in organic synthesis. Many of these techniques are well known in the art. However, a variety of known methods are detailed in the following literature: Compendium of Organic Synthetic Methods (John Wiley &amp; Sons, New York) Vol. 1, Ian T. Harrison and Shuyen Harrison (1971); Volume 2, Ian T. Harrison and Shuyen Harrison (1974); Vol. 3, Louis S. Hegedus and Leroy Wade (1977); Vol. 4, Leroy G. Wade Jr., (1980); Vol. 5, Leroy G. Wade Jr. (1984 And; Volume 6, Michael B. Smith; and March, J., Advanced Organic Chemistry, 3rd edition, John Wiley &amp; Sons, New York (1985); Comprehensive

Organic Synthesis. Selectivity, Strategy &amp; Efficiency in Modern Organic Chemistry, Vol. 9, Barry M. Trost, ed., Pergamon Press » New York (1993); Advanced Organic Chemistry, Part B: Reactions and Synthesis, 4th edition; Carey And Sundberg; Kluwer Academic/Plenum Publishers: New York (2001); Advanced Organic Chemistry, Reactions, Mechanisms, and Structure, 2nd Edition, March, McGraw Hill (1977); Protecting Groups in Organic Synthesis, 2nd Edition, Greene, TW and Wutz, PGM, John Wiley &amp; Sons, New York (1991); and Comprehensive Organic Transformations, 2nd Edition, Larock, RC, John Wiley &amp; Sons, New York (1999). EXAMPLES The following examples illustrate the above aspects of the invention. Those skilled in the art will readily appreciate that the techniques and reagents described in the examples illustrate various methods of practicing the invention 135320.doc-61 - 200930743. It should be understood that many variations can be made within the scope of the invention, while still remaining in the operating example, 4 #,, unless otherwise explicitly stated, even if the word "about" is not explicitly related to the value, quantity ^ ^ The forked target image appears, all numbers:, values and percentages (eg, regarding the amount of material, : and temperature, the quantity ratio, and other factors in the following sections of the specification) should be understood as if the preceding words "about" Repair #-. Accordingly, the numerical parameters set forth in the following specification and the appended claims are intended to be an approximation that may vary depending on the desired properties to be achieved by the present invention. In any event, and without attempting to limit the application of the principles of the patented equivalents, each numerical parameter should be interpreted at least in accordance with the number of reported effective digits and by using ordinary rounding techniques. Although the numerical ranges and parameters set forth in the broad scope of the invention are approximations, the listed values are reported as accurately as possible in the particular examples. However, any value inherently contains certain inevitable errors caused by the standard deviations present in their respective test measurements. In addition, when a range of numbers for each category is recited herein, it is intended to encompass any combination of such values, including the recited values. The reaction can usually be carried out on a double joint vacuum/argon or nitrogen system. If desired, the treatment of air sensitive materials can be carried out in a dry box under argon or nitrogen. The chemical reagents were primarily constructed from Aldrich Chemical Co., Ltd. (Milwaukee, WI) and were used in untreated form unless otherwise stated. EXAMPLE 1 Preparation of a Positionally Regular HT Poly(3-Substituted Thiophene) Block Copolymer 135320.doc • 62· 200930743 Organic Zinc I and II are based on the method described in U.S. Patent No. 5,756,653 (see, for example, No. 54, No. 15 -40 columns) Prepared using Rick (Zn*). A solution of 40 ml (mL) (20 mmol (mmol)) of organozinc 1 (0.5 mol (M) in tetrahydrofuran) was placed in a flask and stirred at room temperature under an inert atmosphere. To this solution was added 0.02 g (0.2 mol%) of Ni(dppe)Cl2 in one portion and the mixture was stirred for 5 minutes. 20 mL (10 mmol) of organic zinc 11 (0.5 Torr in tetrahydrofuran) was added and the mixture was stirred at room temperature overnight. The solution was poured into methanol and stirred for 20 minutes (min). The polymer precipitate was filtered through a Buchner funnel (Buchner &gt; funnel) and washed with methanol. The polymer was dried under high vacuum pressure and extracted with hexane for 24 hours in a Soxhlet Extractor to obtain 4.4 g of a polymer. The crude polymer was determined to have about 94:6 positional regularity by 1H NMR. The crude polymer contained about 70% 3-hexyl-thiophene and about 30% 3-ethylvalerate thiophene. This procedure is listed in scenario 3. Option 3.

135320.doc -63-

One of the advantages of the process for preparing polythiophene block copolymers described herein is that the formation of the porphin-zinc complex allows for polymerization to be carried out at temperatures lower than those of known methods. The polymerization of the thiophene-zinc complex is carried out smoothly at ambient temperature (e.g., about 8 〇c to about 2 5 C) without the need for heat or reflux conditions. A more significant advantage is that the method described herein produces a polymer having a greater degree of positional regularity (higher head-to-tail phenanthrene linkage percentage). In addition, less catalyst needs to be loaded, thereby reducing the cost of the program. EXAMPLE 2 Example Positioned Regular Conductive Block Copolymer Scheme 4 illustrates several possible blocks in a positionally regular conductive block copolymer that can be prepared by the methods described herein, wherein n is such that the positionally regular conductive is segmentally copolymerized The molecular weight of the substance may be from about 1 〇〇〇〇 to about 2 ,, &quot;Hex&quot; is a hexyl group but may be any of the alkyl groups described herein; &quot;Bn&quot; may be as described herein Substituted benzyl; "Ar&quot; is an aryl group as described herein; &quot;Het&quot; is a heteroaryl or heterocyclic ring as described herein; to about 2 Å; and the ulnar is described herein.

Het

R

135320.doc -64 - 200930743

All publications, patents, and patent documents are hereby incorporated by reference in their entirety herein in their entirety herein The invention has been described above with reference to specific embodiments and preferred embodiments and techniques. However, it should be understood that many changes and modifications can be made. At the same time, it remains in the spirit and scope of the present invention.

135320.doc -65 -

Claims (1)

200930743 X. Patent Application Range 1. A method for preparing a positionally regular conductive block copolymer comprising: a) combining a nickel (II) catalyst with a first monomer-metal complex to provide a positional rule w w a block copolymer intermediate, wherein the first monomer metal complex is prepared by a process comprising the steps of: combining a first dihalogen-monomer with an activated metal, a Grignard reagent, or Rznx, LUX Or R3ZnM reagent, wherein the pedigree (C2-C12) alkyl, μ is magnesium, manganese, lithium, sodium or potassium, and X is F, Cl, Br, or I; 'b) combined with the second monomer-metal And the positionally regular conductive block copolymer intermediate to provide the positional regular conductive block copolymer, wherein the second monomer-metal complex is prepared by a method comprising the steps of: Two kinds of bis-monomers and activated metal Grignard reagents, or RZnX, R2ZnX4R3ZnM reagents, wherein the ruler is (1)^^...alkyl, lanthanide magnesium, manganese, lithium, sodium or potassium, and the lanthanide F, lanthanum, Or each of the dentate-monomers is independently an aromatic or heteroaryl substituted by two dentants. a family group, wherein the dentates may be the same or different, and wherein if the dimeric monomers have the same ring system, at least one of the dihalogen monomers is substituted, and if the two If the monomers have the same ring system and are substituted, the substituents are not the same. 2. The method of claim 1, wherein a nickel catalyst is used and the nickel (ruthenium) catalyst and the monomer/metal complex are combined in either order. 3' The method of claim 2, wherein the nickel catalyst is added to the first bulk metal complex to provide a positionally regular conductive block copolymer intermediate. 135320.doc 200930743 4. The method of claim s, wherein the first monomer-metal complex is added to the §, (1) catalyst to provide a positionally regular conductive | segment of the copolymer intermediate. 5. The method of claim 1 , wherein the aromatic or heteroaromatic group is phenylthiophene, pyrrole, furan, aniline, phenyl extended vinyl, thiophene extended ethylene thiophene Dilute, B, D, aryl isothionaphthalene, p-phenylene sulfide, porphin [2,3-b] thiophene, thieno[2,3_C]thiophene, thieno[2,3-d] Thiophene, naphthalene, benzo[2,3]thiophene, benzo[3,4]thiophene, biphenylyl, or bithiophenyl, and wherein the aromatic or heteroaromatic group has from 0 to about 3 non-halogen Substituent. 6. The method of claim 5, wherein the oxime to about 3 substituents are each independently from about 1 to about 5 esters, ketones, nitriles, amines, aryls, heteroaryls, or heterocycles, as desired. Substituted ((^-(:24)alkyl, ((^-(:24)alkylthio, (c--C24)alkylcarboxyalkyl, or (Cl_C24) alkoxy), and the alkyl group One or more of the carbon atoms of the intermediate bond may be replaced by from about 1 to about 10 hydrazine, S or NH groups as desired. 7. The method of claim 1, wherein the first dihalogen monomer and The second dimeric-monomers are each independently selected from the group consisting of 2,5-dihalo-thiophene, 2,5-di-p-pyrrole, 2,5-di-furan, furo, 3 -dihalobenzene, 2,5-difunctional-3-substituted thiophene, 2,5-di- _3_substituted pyrrole, 2,5-didentin-3-substituted furan, 1,3-two letter Phen-2-substituted benzene, 1,3-dihalo-4-substituted benzene, 1,3-didentin-5-substituted benzene, iota, dihalo-6-substituted benzene, 1,3-dihalogen -2,4-disubstituted benzene, 1,3-dioxin- 135320.doc 200930743 2.5- Disubstituted benzene, 1,3-dipenin-2,6-disubstituted benzene, h3-dihalogen- 4.5- Disubstituted benzene, 1 3-substituted-4,6-prime stupid, 1,3-prime _ - 2.4.5- Trisubstituted benzene, 1,3-dioxin-2,4,6-trisubstituted benzene, 1,3-dihalogen-2,5,6-trisubstituted benzene, 1,4·dihalogen- 2-substituted benzene, fluorene-didentin-3-substituted benzene, 1,4-di-n-5-substituted benzene, 1,4-dentate-6-substituted benzene, M-dentate-2, 3-disubstituted benzene, 1,4-diterpenoid-2,5-disubstituted benzene, 1,4-dentate-2,6-disubstituted benzene, 1,4-difunctional-3,5- Disubstituted benzene, 1,4-dimorph-3,6-disubstituted benzene, 1,4-dihalogen-3,5,6-trisubstituted benzene, 2,5-difunctional-3,4-di Substituting thiophene, 2,5-didentin-3,4-disubstituted pyrrole, 2,5-didentin-3,4-disubstituted furan, and combinations thereof. 8. The method of claim 7, wherein the first dentate-single system 2,5-dibromo-3-hexylthiophene and the second dihalogen-single system 5_(2_5_dibromothiophene -3-yl) Ethyl valerate. 9. The method of claim 1 wherein the positional regular conductive block copolymer comprises unsubstituted thiophene, 3-substituted thiophene, 3,4-disubstituted thiophene or a combination thereof. 10. The method of claim 9, wherein the positional regular conductive block copolymer is a poly(3-substituted thiophene) block copolymer or an 11-butadiene (3,4 disubstituted thiophene) block copolymer. The method of claim 10, wherein the fluorene (3_substituted thiophene) block copolymer is substituted with a plurality of linear (C--Cl2) alkyl groups and substituted by a plurality of acetal-substituted direct bonds (Cl) -Cl2) Substituted by a burnt group. 12. The method of claim 11, wherein the homopolymer (3 substituted porphin) annihilation copolymer is subjected to a plurality of thiol groups which are monosubstituted by ethyl groups through a plurality of hexyl groups. 135320.doc 200930743 13. 14. 15. 16. ❺ If requested ϊ § 1 + +, 丄 method 'where the activated metal is Ming, Meng, copper, zinc, recorded, T, 'do, titanium, iron, cobalt, nickel, indium or a combination thereof. The method of claim 13, wherein the activated metal is rickel zinc (Zn*). The method of claim 1, wherein the positional regular conductive block copolymer has a positional regularity greater than about 87%. The method of claim 1, wherein the positional regular conductive block copolymer has a weight average molecular weight of from about 5,000 to about 200,000. The method of claim 1, wherein the prepared positional regular conductive block copolymer has a degree of polymerization index of from about 1 to about 25. 18. The method of claim i, wherein the nickel catalyst is derived from Nl (dppe) Cl2, Ni(dPPP)Cl2, Ni(PPh3)2Br2, 1,5·cyclooctadiene bis(diphenyl Recorded, two gas (2, 2, _ dioxin) nickel, tetrakis (triphenylphosphine), NiO NiF2, NiCh, NiBr2, Nil:, NiAs, Ni (dmph) 2, BaNiS or a combination thereof. 19. The method of claim 1, wherein about ιι mol is used. /. Up to about 5 mol% of nickel (ruthenium) catalyst. 20. A method of preparing a positionally regular HT poly(3-substituted thiophene) block copolymer comprising: a) combining a nickel (II) catalyst with a first thiophene-zinc complex to provide positional regularity HT a poly(3-substituted thiophene) intermediate; b) combining a second porphin-decomplex with the positional regular ht poly(3-substituted sinter) intermediate to provide the positional regular HT poly(3-substitution Stroke) block copolymer. 135320.doc 200930743 21. An electronic device comprising a circuit constructed from a positional regular conductive block copolymer prepared by the method of claim 1. 22. The electronic device of claim 21, wherein the device is a thin film transistor, a field effect transistor, a radio frequency identification tag, a flat panel display, a photovoltaic device, an electroluminescent display device, a sensor device, and an electrophotographic device or Organic light-emitting diodes. 23. A positionally regular conductive block copolymer prepared by the method of claim 1. 24. The positional regular conductive block copolymer of claim 23, wherein the coarse position regular conductive block copolymer has a degree of positional regularity of at least about 87%, preferably greater than about 92®/. More preferably, it is greater than about 95%. 25. A positionally regular conductive block copolymer having at least about 92. /〇 Positionality; about 30, 〇〇〇 to about 7 〇, the weight average molecular weight of 〇〇〇; and a conductivity of about ΙΟ·5 to about 10-6 Siemens/cm. 135320.doc 200930743 VII. Designated representative 囷: (1) The representative representative of the case is: (none) (2) The symbolic symbol of the representative figure is simple: 8. If there is a chemical formula in this case, please reveal the best display of the characteristics of the invention. Chemical formula: (none) 135320.doc