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WO1994004592A1 - Polymeres photoconducteurs - Google Patents

Polymeres photoconducteurs Download PDF

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Publication number
WO1994004592A1
WO1994004592A1 PCT/US1993/007747 US9307747W WO9404592A1 WO 1994004592 A1 WO1994004592 A1 WO 1994004592A1 US 9307747 W US9307747 W US 9307747W WO 9404592 A1 WO9404592 A1 WO 9404592A1
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polymer
repeating unit
article
manufacture
sulfur
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Samson Jenekhe
Ashwini Agrawal
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Research Corp Technologies Inc
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Research Corp Technologies Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides

Definitions

  • the present invention relates to photoconductive polymers. More specifically, the invention relates to a series of polymers and copolymers in the polyquinoline and polyanthrazoline class which have electrical and optical characteristics well-suited for electronic, optoelectronic and photonic applications. The present invention is also directed to a method of solubilizing these polymers, and polyquinolines and polyanthrazolines in general, in a manner which facilitates processing of the same into configurations important for practical implementation.
  • Polymers, or macromolecules, are generally thought of as insulators for electrical purposes and have found widespread use accordingly.
  • advances in electronics, optoelectronics and photonics have created a practical need for polymers that exhibit electronic and optical properties suitable for use in commercially important devices, such as electrophotographic copying and facsimile machines, laser printers, light- emitting diodes, flexible displays, optical switches and waveguides.
  • polyacetylene which has been a particular object of scrutiny.
  • Polyacetylene can be prepared using Ziegler-type catalysts to form a freestanding insoluble flexible film and, when properly doped, can exhibit metallic-like conductivity.
  • the utility of polyacetylene is, however, limited for practical purposes: it is unstable, reacting with air and moisture to the detriment of its photoconductive character, and is intractable to a point where it cannot be readily processed into fibers , thin films etc. --that is, those configurations and geometries needed for most applications.
  • polythiophene Like polyacetylene however, polythiophene exhibits poor processability.
  • One technique to enhance polythiophene processability involves the incorporation of soluble side chains, usually very long ones, into the polymer. The inclusion of such side groups imparts sufficient solubility to the polythiophene to permit processing into the requisite shapes.
  • side groups while the addition of side groups in this manner aides the processing of polythiophene, it adversely affects the mechanical properties of that polymer and moreover causes a loss in thermal resistance by transforming the polymer into a low temperature material, i.e., one that has a glass transition temperature (T G ) slightly above room temperature. This loss of mechanical integrity and high temperature stability has made this side-chain approach less-than-desirable from a practical stand-point.
  • PVK polyvinyl carbazole
  • poly(2,6-(4-phenylquinoline)) known hereafter as "PPQ”
  • poly(2,2'-(biphenylene)-6,6'-bis(4-phenylquinoline)) known hereafter as "PBPQ”
  • PBPQ poly(2,2'-(p,p'- stilbene)-6,6'-bis(4-phenylquinoline)) known hereafter as PSPQ
  • PSPQ poly(2,2'-(1,4-phenylene)-6,6'-bis(4-phenylquinoline)
  • polyanthrazolines as represented, for example, by poly(2,7-(p,p'-biphenylene)-4,9-diphenyl-1,6-anthrazoline) known hereafter as "PBDA”; and poly(2,7-(1,4-phenylene)-4,9-diphenyl-1,6-anthrazoline) known hereafter as "PPDA”. All of the aforementioned polymers generally exhibit high thermal stability (> 550°C) and excellent mechanical properties.
  • these polymers are not easily processed into useable configurations, including fibers, thin films, free-standing objects and the like.
  • Part of the problem in this regard is that these types of polyquinolines and polyanthrazolines are not generally soluble in organic solvents. Indeed, many of these materials are not even soluble in strong acids, such as suifuric acid, methane sulfonic acid and trifluoromethane sulfonic acid. As solubility is an all-important factor in the ultimate ability to use these polymers in a practical sense, several attempts have been made to improve the same.
  • polyquinolines are not generally soluble in organic solvents, they are soluble at high concentrations in a solvent system consisting of di-m-cresylphosphate (DCP) dissolved in m-cresol, which system is commonly employed as the polymerization medium for these polymers.
  • DCP di-m-cresylphosphate
  • m-cresol m-cresol
  • the polyquinolines can be processed into thin films and fibers from DCP/m-cresol solutions, there are inherent problems with this solvent system which prevent it from becoming used on a large scale.
  • DCP is not generally available and is difficult to synthesize and purify.
  • solutions of polyquinolines in DCP/m-cresol are highly viscous even at low concentrations ( ⁇ 0.5 wt.
  • the present invention is directed to a polymer generally of the polyquinoline and polyanthrazoline class that exhibits improved electrical and optical properties than polymers known heretofore.
  • the polymer of the present invention manifests excellent heat resistance and moisture stability thus permitting its utilization in a variety of applications and environments.
  • the structure of the polymer of the present invention may be modified in a predetermined fashion to obtain desired physical, electrical and/or optical properties, such as having maximum optical absorption or photoconductivity in any desired region of the electromagnetic spectrum, including the visible and near infrared regions.
  • a polymer comprising a repeating unit of structure (I) or (II):
  • X 1 , X 4 , X 5 and X 8 are each independently nitrogen or CR 2 ;
  • X 2 , X 3 , X 6 and X 7 are each independently nitrogen or CR 2 when not forming a point of attachment for said repeating unit to adjacent repeating units and are carbon when forming said point of attachment, with the proviso that at least one but no more than two of X 1 , X 2 , X 3 and X 4 is nitrogen and at least one but no more than two of X 5 , X 6 , X 7 and X 8 is nitrogen;
  • R 1 is lower alkenylene, lower alkynylene or a bivalent radical having structure (i):
  • Ar is a nitrogen, oxygen or sulfur-containing heterocyclic moiety, a monocyclic or polycyclic aromatic moiety, any of which moieties may be
  • W 1 is lower alkylene, lower alkenylene or lower alkynylene
  • each R 2 is independently hydrogen, nitro, cyano, halogen or lower alkyl, lower alkoxy, lower alkaryl, aralkyl, aryl or a nitrogen, oxygen, or sulfur-containing heterocyclic moeity any of which may be unsubstituted or substituted with one or more halogen, lower alkyl, lower alkoxy or aryloxy groups;
  • the polymer of the present invention comprises an article of manufacture, such as a thin film, a fiber or a free-standing object, or is comprised in an article of manufacture such as an electronic device, an optoelectronic device or a photonic device. Examples in this last regard include conductors, photoconductors, waveguides, optical switches, light-emitting diodes, such as flexible display devices, electrophotographic and facsimile machines and laser printers.
  • the present invention is directed to a method of solubilizing a polymer of the present invention, as well as polyquinolines, polyanthrazolines and like polymers in general, that involves contact of the same with a complexing agent of a Lewis acid, a dialkyl phosphate, a diaryl phosphate or mixture thereof under conditions effective to cause said polymer to become substantially soluble in a solvent.
  • the present invention relates to a method for forming an article of manufacture which comprises the aforementioned method of solubilizing to obtain a solution containing the polymer; processing the solution into a desired configuration; and recovering the polymer from the solution under conditions effective to substantially maintain the polymer in the desired configuration.
  • Figure 1 is a depiction of an embodiment of the method of forming an article of manufacture in accordance with the practice of the present invention. The method depicted relates to the formation of a thin film supported on a frame.
  • Figure 2 is a graph comparing the optical absorption spectra of thin films formed from a known biphenylene-linked polyquinoline, PBQA (Curve 1) to those formed from three thiophene-linked polyquinoline polymers of the present invention, PBTPQ, PBTAPQ and PBTVPQ (Curves 2, 3 and 4).
  • Figure 3 is a graph comparing the optical absorption spectra of thin films formed from a known biphenylene-linked polyanthrazoline, PBDA (Curve 1) to those formed from three thiophene-linked polymers of the present invention, PBTDA, PBTADA and PBTVDA (Curves 2, 3 and 4).
  • Figure 4 is a graph comparing the optical absorption spectra of a thin film formed from a known single phenylene-linked polyquinoline, PPPQ (Curve 1) to a thin film formed from a single thiophene-linked polymer of the present invention, PTPQ (Curve 2).
  • Figure 5 is a graph comparing the optical absorption spectra of a thin film formed from a known single phenylene-linked polyanthrazoline, PPDA (Curve 1) to a thin film formed from a single thiophene-linked polymer of the present invention, PTDA (Curve 2).
  • Figure 6 is a graph comparing the solution optical absorption spectra, in 0.1 mole % DCP/m-cresol, of a known polyquinoline, PBPQ (Curve 1) and thiophene-linked polymers of the present invention, PBTPQ, PBTAPQ and PBTVPQ (Curves 2, 3 and 4).
  • Figure 7 is a graph comparing the solution optical absorption spectra, in 0.1 mole % DCP/m-cresol, of a known polyanthrazoline, PBDA (Curve 1) to thiophene- linked polymers of the present invention, PBTDA, PBTADA and PBTVDA (Curves 2, 3 and 4).
  • Figure 8 is a graph comparing the optical absorption spectra of thin films of four polymers of the present invention, PBTPQA (Curve 1), PBTPQA (Curve 2), PBTPQA-OCH 3 (Curve 3) and PBTPQA-F (Curve 4).
  • Figure 9 is a graph comparing the optical absorption spectra thin films of polymers of the present invention, PBTPQA-OCH 3 (Curve 1), PBTPQA-F (Curve 2) and PBTPQA (Curve 3).
  • Figure 10 is a graph comparing the solution optical absorption spectra, in 0.1 mo. % of DCP/m-cresol, of two random copolymers of the present invention, PBTPQ/ PBTPQA-OCH 3 (mole ratio 80:20) and PBTPQ/PBTPQA-F (mole ratio 80:20) Curves 1 and 2, respectively.
  • Figure 11 is a graph comparing the dispersion of the refractive index of thin films formed from two known polyquinolines, PBPQ and PPPQ, to two polymers of the present invention, PBAPQ and PSPQ.
  • Figure 12 is a graph comparing the dispersion of the refractive index of thin films from three known polyanthrazolines, PBDA, PSPQ and PPDA, to a polymer of the present invention, PBADA and PSDA.
  • the polymer of the present invention comprises a repeating unit of structure (I) or (II):
  • X 1 , X 4 , X 5 and X 8 are each independently nitrogen or CR 2 ;
  • X 2 , X 3 , X 6 and X 7 are each independently nitrogen or CR 2 when not forming a point of attachment for said repeating unit to adjacent repeating units and are carbon when forming a point of attachment, with the proviso that at least one but no more than two of X 1 , X 2 , X 3 and X 4 is nitrogen and at least one but no more than two of X 5 , X 6 , X 7 and X 8 is nitrogen;
  • R 1 is lower alkenylene, lower alkynylene or a bivalent radical having structure (i):
  • o is zero or 1
  • p is zero or 1
  • q is an integer from 1 to 10
  • Ar is a nitrogen, oxygen or sulfur containing heterocyclic moiety, a monocyclic or polycyclic aromatic moiety, any of which moieties may be unsubstituted or substituted with one or more lower alkyl, lower alkoxy, cyano, or nitro groups
  • W 1 is lower alkylene, lower alkenylene or lower alkynylene;
  • each R 2 is independently hydrogen, nitro, cyano, halogen or lower alkyl, lower alkoxy, lower alkaryl, aralkyl, aryl or a nitrogen, oxygen or sulfur-containing heterocyclic moiety any of which may be unsubstituted or substituted with one or more halogen, lower alkyl, lower alkoxy or aryloxy groups;
  • W is lower alkylene, lower alkenylene or lower alkynylene; and m is zero or 1, with the proviso that R 1 is other than phenylene, biphenylene or stilbene when said repeating unit has structure (I), where m is zero, and q is 1; and R 1 is other than phenylene or biphenyl ene when said repeating unit has structure (II) and q is 1.
  • the lower alkyl groups each contain up to 6 carbon atoms which may be in the normal or branched configuration, including methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, amyl, pentyl, hexyl and the like.
  • the preferred alkyl groups contain 1 to 3 carbon atoms; methyl is most preferred.
  • the lower alkoxy groups each contain up to 6 carbon atoms which may be in the normal or branched configuration, including, for example, methoxy, ethoxy, propoxy and the like.
  • the preferred alkoxy groups contain 1 to 3 carbon atoms; methoxy is most preferred.
  • the lower alkaryl groups each contain up to 16 carbon atoms, with each alkyl group thereof containing up to 6 carbon atoms, which may be in the normal or branched configuration, and with each aryl group thereof containing from 6 to 10 carbon atoms.
  • each alkyl group contains 1 to 3 carbon atoms and each aryl group contains 6 carbon atoms.
  • the aryl groups are aromatic rings containing from 6 to 14 carbon atoms.
  • An aryl group may be a single ring or a combination of multiple rings which may be ortho-fused or joined by one or more single bonds.
  • Examples of the aryl groups include phenyl, ⁇ -naphthyl, ß-naphthyl and biphenyl.
  • T ne aryloxy groups each contain from 6 to 10 carbon atoms.
  • each aryl group contains 6 carbon atoms.
  • the aralkyl groups each contain up to 16 carbon atoms, with each aryl group thereof containing from 6 to 10 carbon atoms and each alkyl group thereof containing up to 6 carbon atoms which may be in the normal or branched configuration.
  • each aryl group contains 6 carbon atoms and each alkyl group contains 1 to 3 carbon atoms.
  • the lower alkenylene groups are bivalent radicals of normal or branched alkenes of 2 to 6 carbon atoms.
  • the lower alkenylene groups may have one carbon-carbon double bond or multiple carbon-carbon double bonds present therein. In configurations having multiple carbon- carbon double bonds, it is preferred that the alkenylene group be in the normal configuration and that the double bonds alternate with carbon-carbon single bonds, i.e, that conjugated double bonds are present.
  • the lower alkenylene groups are bivalent radicals of normal alkenes of 2 to 4 carbon atoms wherein a hydrogen from each of the terminal carbon atoms has been removed.
  • Examples of preferred alkenylene groups include vinylene, 1-propenylene, 2-propenylene, butenylene, 2-butenylene and the like. Vinylene is most preferred.
  • the lower alkynylene groups are bivalent radicals of normal or branched alkynes of 2 to 6 carbon atoms.
  • the lower alkynylene groups may have one carbon-carbon triple bond or multiple carbon-carbon triple bonds. In configurations having multiple carbon-carbon triple bonds, it is preferred that the alkynylene group be in the normal configuration and that the triple bonds alternate with carbon-carbon single bonds.
  • the lower alkynylene groups are bivalent radicals of normal alkynes of 2 to 4 carbon atoms wherein a hydrogen from each of the terminal carbon atoms has been removed.
  • a preferred alkynylene group is ethynylene.
  • the phrase "monocyclic or polycyclic aromatic moiety" includes bivalent radicals formed from an aromatic moiety having up to 12 carbon atoms. It is preferred that the free valencies forming the bivalent aromatic moiety are at ring carbon atoms.
  • a monocyclic or polycyclic aromatic moiety contemplated by the present invention may thus be a monocyclic aromatic ring system, such as a phenylene, or an orthofused polycyclic aromatic ring system, such as a naphthalene, or a polycyclic aromatic ring system joined by one or more single bonds, such as a biphenylene.
  • nitrogen, oxygen or sulfur-containing heterocyclic moiety includes bivalent radicals formed from heterocyclic rings which include at least one sulfur, nitrogen or oxygen ring atom but which may also include one or several of such atoms.
  • the expression includes bivalent radicals of saturated and unsaturated heterocyclics, as well as heteroaromatic rings, which in the practice of the present invention are preferred. These groups contain 5 to 12 ring atoms in the moiety, which may be formed from a single heterocyclic ring or may be polycyclic, the latter being formed from ortho-fused ring systems or ring systems joined by one or more single bonds. It is preferred that the free valencies of the bivalent moiety are at ring atoms; preferably carbon ring atoms.
  • bivalent radicals in this regard include furylene, pyrrolylene, imidazolylene, pyrazolylene, pyridylene, pyrazinylene and the like.
  • Preferred bivalent radicals are sulfur-containing heterocyclic moi eties, such as thienylene, dithienylene, trithienylene etc; 2,5-thienylene is especially preferred.
  • Halogens include fluorine, chlorine, bromine, iodine and astatine. Flourine is preferred.
  • nitro and cyano groups are -NO 2 and -CN, respectively.
  • each Ar is the same.
  • either of X 2 or X 3 may form a first point of attachment for said repeating unit to a first adjacent repeating unit and either of X 6 or X 7 may form a second point of attachment for said repeating unit to a second adjacent repeating unit.
  • X 1 is nitrogen and X 4 is CR 2 ;
  • X 2 forms a first point of attachment to a first adjacent repeating unit and X 3 is CR 2 ;
  • X 5 is nitrogen and X 8 is CR 2 ;
  • X 6 forms a second point of attachment to a second adjacent repeating unit and
  • X 7 is CR 2 .
  • the R 2 associated with X 3 and the R 2 associated with X 7 are each hydrogen, and that the R 2 associated with X 4 is phenyl, and that the R 2 associated with X 8 is phenyl.
  • the repeating unit have structure (I). (This arrangement is referred to hereafter as the "most preferred first embodiment").
  • m is zero.
  • R 1 is an alkenylene having 2 to 4 carbon atoms.
  • PVPQ The preferred structure of the repeating unit for this configuration, denoted hereinafter as PVPQ, is shown below:
  • R 1 is an alkynylene having 2 to 4 carbon atoms.
  • PAPQ The preferred structure of the repeating unit for this configuration, denoted herein as PAPQ, is shown below:
  • R 1 has structure (i), o, p and q are each 1, W 1 is alkyenlene of 3 to 4 carbon atoms and each Ar is a bivalent radical of a monocyclic aromatic moiety.
  • W 1 is methylene and each Ar is a phenylene.
  • PDMPQ The structure of the repeating unit in a particularly preferred practice, denoted herein as PDMPQ, is shown below:
  • R 1 has structure (i), o, p and q are each 1; W 1 is alkynylene having 2 to 4 carbon atoms and each Ar is a bivalent radical of a monocyclic aromatic moiety. In a preferred practice, W 1 is ethynylene and each Ar is a phenylene.
  • PBAPQ The structure of the repeating unit in a particularly preferred practice, denoted herein as PBAPQ, is shown below:
  • PTPQ a particularly preferred structure of the repeating unit in this regard, denoted herein as PTPQ, is shown below:
  • the thienylene is substituted with one or more alkoxy groups of up to 4 carbon atoms.
  • a preferred alkoxy is methoxy.
  • a particularly preferred structure of the repeating unit in this regard is shown below:
  • R 1 has structure (i), o and p are zero, q is 2, and each Ar is a bivalent radical of a sulfur-containing heterocyclic moiety; preferably each Ar is a thienylene.
  • PBTPQ A particularly preferred structure of the repeating unit in this regard, denoted herein as PBTPQ, is shown below:
  • each thienylene is substituted with one or more alkoxy groups of up to 4 carbon atoms.
  • a preferred alkoxy is methoxy.
  • R 1 has structure (i) wherein o and p are each zero; q is 3 and each Ar is a bivalent radical of a sulfur-containing heterocyclic moiety; preferably each Ar is a thienylene.
  • a particularly preferred structure in this regard is shown below:
  • R 1 has structure (i), o, p and q are each 1, W 1 is an alkenylene of 2 to 4 carbon atoms, and each Ar is a bivalent radical of a sulfur-containing heterocyclic moiety.
  • W 1 is vinylene in the trans position and each Ar is a thienylene.
  • PBTVPQ A particularly preferred structure of the repeating unit in this regard, denoted herein as PBTVPQ, is shown below:
  • R 1 has structure (i), o, p and q are each 1, W 1 is an alkynylene of 2 to 4 carbon atoms, and each Ar is a bivalent radical of a sulfur-containing heterocyclic moiety.
  • W 1 is ethynylene and each Ar is a thienylene.
  • PBTAPQ A particularly preferred structure of the repeating unit in this regard, denoted hereinafter as PBTAPQ, is shown below:
  • X 1 is nitrogen
  • X 4 is CR 2
  • X 2 forms a first point of attachment to a first adjacent repeating unit and
  • X 3 is CR 2 ;
  • the R 2 associated with X 3 is hydrogen and the R 2 associated with X 4 is phenyl.
  • X 8 is nitrogen and X 5 is CR 2 ;
  • X 6 is CR 2 and
  • X 7 forms a second point of attachment to a second adjacent repeating unit.
  • the R 2 associated with X 5 is phenyl and the R 2 associated with X 6 is hydrogen. It is most preferred in this particular arrangement that the repeating unit have structure (II) (this arrangement is referred to hereafter as the "most preferred second embodiment").
  • R 1 is an alkenylene of 2 to 4 carbon atoms.
  • R 1 is vinylene in the trans position.
  • the structure of the repeating unit having this configuration, denoted herein as PVDA, is shown below:
  • R 1 is an alkynylene of 2 to 4 carbon atoms.
  • R 1 is ethynylene.
  • PADA The structure of the repeating unit having this configuration, denoted hereinafter as PADA, is shown below:
  • R 1 has structure (i), o, p and q are each 1, W 1 is an alkylene of up to 4 carbon atoms and each Ar is a bivalent radical of a monocyclic aromatic moiety.
  • W 1 is methylene and each Ar is a phenylene.
  • PDMDA PDMDA
  • R 1 has structure (i), o, p and q are each 1, W 1 is alkenylene of 2 to 4 carbon atoms and each Ar is a bivalent radical of a monocyclic aromatic moiety.
  • W 1 is vinylene in the trans position and each Ar is a phenylene.
  • PSDA A particularly preferred structure of the repeating unit in this regard, denoted herein as PSDA, is shown below:
  • R 1 has structure (i), o, p and q are each 1, W 1 is alkynylene of 2 to 4 carbon atoms and each Ar is a bivalent radical of a monocyclic aromatic moiety.
  • W 1 is ethynylene and each Ar is a phenylene.
  • PBADA A particularly preferred structure of the repeating unit in this regard, denoted herein as PBADA, is shown below:
  • R 1 has structure (i), o and p are each zero, q is 1 and Ar is a sulfur-containing heterocyclic moiety; preferably Ar is a thienylene.
  • PTDA particularly preferred structure of the repeating unit in this regard, denoted herein as PTDA, is shown below:
  • the thienylene is substituted with one or more alkoxy groups of up to 4 carbon atoms.
  • a preferred alkoxy is methoxy.
  • a particularly preferred structure of the repeating unit in this regard is shown below:
  • R 1 has structure (i), o and p are each zero, q is 2 and each Ar is a sulfur-containing heterocyclic moiety; preferably, each Ar is a thienylene.
  • PBTDA PBTDA
  • each thienylene is substituted with one or more alkoxy groups of up to 4 carbon atoms.
  • a preferred alkoxy is methoxy.
  • a particularly preferred structure of the repeating unit in this regard is shown below:
  • R 1 has structure (i), o and p are each zero; q is 3 and each Ar is a sulfur-containing heterocyclic moiety.
  • each Ar is a thienylene.
  • R 1 has structure (i), o, p and q are each 1, W 1 is alkenylene of 2 to 4 carbon atoms and each Ar is a bivalent radical of a sulfur-containing heterocyclic moiety.
  • W 1 is vinylene in the trans position and each Ar is a thienylene.
  • PBTVDA A particularly preferred structure of a repeating unit in this regard, denoted herein as PBTVDA, is shown below:
  • R 1 has structure (i), o, p and q are each 1, W 1 is alkynylene of 2 to 4 carbon atoms and each Ar is a bivalent radical of a sulfur-containing heterocyclic moiety.
  • W 1 is ethynylene and each Ar is a thienylene.
  • PBTADA PBTADA
  • the repeating unit has the structure hereinbefore referred to as the most preferred first embodiment; however, in this third embodiment, m is 1.
  • W is an alkynylene of 2 to 4 carbon atoms.
  • R 1 has structure (i), o and p are each zero, q is 2 and each Ar is a bivalent radical of a sulfur-containing heterocyclic moiety.
  • W is ethynylene and each Ar is a thienylene.
  • PBTPQA A particularly preferred structure of the repeating unit in this regard, denoted herein as PBTPQA, is shown below:
  • PBTPQA-F A particularly preferred structure of the repeating unit in this regard, denoted herein as PBTPQA-F, is shown below:
  • the phenyl associated with X 4 is substituted with one or more alkoxy groups of up to 4 carbon atoms and the phenyl associated with X 8 is substituted with one or more alkoxy groups of up to 4 carbon atoms.
  • the alkoxy groups are methoxy.
  • N is alkenylene of 2 to 4 carbon atoms.
  • R 1 has structure (i); o and p are each zero; q is 2 and each Ar is a bivalent radical of a sulfur-containing heterocyclic moiety.
  • N is vinylene in the trans position and each Ar is a thienylene.
  • the phenyl associated with X 4 is substituted with one or more halogens and the phenyl associated with X 8 is substituted with one or more halogens.
  • a particularly preferred structure of the repeating unit in this regard is shown below:
  • the phenyl associated with X 4 is substituted with one or more alkoxy groups of up to 4 carbon atoms and the phenyl associated with X 8 is substituted with one or more alkoxy groups of up to 4 carbon atoms.
  • the alkoxy groups are methoxy.
  • each Ar is a thienylene substituted with one or more alkoxy groups of up to 4 carbon atoms.
  • the alkoxy groups are methoxy.
  • R 1 has structure (i); o and p are each zero; q is 1 and Ar is a bivalent radical of a sulfur-containing heterocyclic moiety.
  • W is vinylene in the trans position and Ar is a thienylene.
  • W is vinylene in the trans position
  • R 1 has structure (i); o, p and q are each 1; W 1 is alkynylene of 2 to 4 carbon atoms, and each Ar is a bivalent radical of a sulfur-containing heterocyclic moiety.
  • W 1 is ethynylene and each Ar is a thienylene.
  • a particularly preferred structure of the repeating unit in this regard is shown below:
  • W is vinylene in the trans position
  • R 1 has structure (i); o, p, and q are each 1;
  • W 1 is alkenylene of 2 to 4 carbon atoms and each Ar is a bivalent radical of a sulfur-containing heterocyclic moiety.
  • W 1 is vinylene in the trans position and each Ar is a thienylene.
  • a particularly preferred structure of the repeating unit in this regard is shown below:
  • W is vinylene in the trans position
  • R 1 has structure (i); o and p are each zero; q is 3; and Ar is a bivalent radical of a sulfur- containing heterocyclic moiety.
  • Ar is a trithienylene.
  • the polymer of the present invention is a random or block copolymer containing at least one repeating unit contemplated by the present invention.
  • the random copolymer is formed from two or more of the repeating units contemplated by the invention.
  • the copolymer comprises a first repeating unit having structure (I) or (II) and a first R 1 and a second repeating unit having structure (I) or (II) and a second R 1 wherein said first R 1 is different from said second R 1 , with the remainder of the first repeating unit and the second repeating unit being otherwise the same.
  • the copolymer is formed by one or more repeating units contemplated by the present invention in combination with known repeating units, such as those which make up the polymers PPQ, PBPQ, PPPQ, PSPQ, PBDA and PPDA.
  • the first repeating unit of the random copolymer of the invention is the repeating unit from the polymer PBPQ and the second repeating unit is one contemplated by the present invention, e.g., PBAPQ, as hereinbefore defined.
  • PBPQ/PBAPQ The structure of this copolymer, denoted herein as PBPQ/PBAPQ, is shown below:
  • the first repeating unit is one contemplated by the present invention, e.g., PBAPQ, as hereinbefore defined, and the second repeating unit is from the poly mer PSPQ.
  • PBAPQ/PSPQ The structure of this second copolymer, denoted herein PBAPQ/PSPQ, is shown below:
  • the copolymer is formed of repeating units contemplated by the invention wherein the R 1 groups are the same but the remainder of the respective repeating units are different.
  • the copolymer comprises a first repeating unit having structure (I) or (II) and a first R 1 , and a second repeating unit having structure (I) or (II) and a second R 1 wherein said first R 1 and said second R 1 are the same, with the remainder of the first repeating unit and the second repeating unit otherwise having differences.
  • the copolymer of the present invention has as a first repeating unit, PBTPQA-F, as hereinbefore defined, and a second repeating unit of PBTPQ, also as hereinbefore defined.
  • PBTPQA-F first repeating unit
  • PBTPQ second repeating unit of PBTPQ
  • the copolymer has as a first repeating unit, PBTPQA-OCH 3 , as hereinbefore defined, and a second repeating unit of PBTPQ, also as hereinbefore defined.
  • PBTPQA-OCH 3 /PBTPQ The structure of this copolymer, denoted herein as PBTPQA-OCH 3 /PBTPQ, is shown below:
  • the present invention is directed to a random or block copolymer comprising repeating units from known homopolymers, such as those making up PPQ, PPPQ, PSPQ, PBDA, and PPDA.
  • a copolymer contemplated in this regard denoted PBPQ/PSPQ, is shown below:
  • the random and block copolymers of the present invention preferably comprise only two repeating units as hereinbefore described and exemplified.
  • the mole ratio of a first repeating unit to a second, different repeating unit in this regard is anywhere from about 0.5:95 to about 95:0.5.
  • Other mole ratios in this regard are about 90:10 to about 10:90; about 80:20 to about 20:80; about 70:30 to about 30:70; about 60:40 to about 40:60 and about 50:50.
  • the present invention relates to an article of manufacture comprising a poly mer or copolymer of the present invention, preferably those exemplified hereinabove.
  • articles of manufacture contemplated by this embodiment of the present invention include electronic, optoelectronic and photonic devices, such as filters, optical switches, wave guides, light-emitting diodes, especially flexible display devices and nonlinear optical devices.
  • Other applications for the polymers of the present invention include but are not limited to electrophotographic copying machines, facsimile machines, laser printers and the like. The details pertaining to the inclusion, incorporation and employment of the polymer or copolymer of the present invention into these and similar devices and applications will be readily understood and appreciated by those of skill in the art given the teachings herein.
  • the present invention is directed to a method of solubilizing a polymer of the present invention, as well as solubilizing polyquinolines and polyanthrazolines in general, in a solvent.
  • Especially preferred polyquinolines and polyanthrazolines in this last regard are those having a rigid-rod, nonconjugated structure.
  • polymer as used in regard to the methods of the present invention also includes copolymers as contemplated by the invention or as known heretofore for the class of polyquinolines and polyanthrazolines.
  • the method of solubilizing of the present invention entails contacting a polymer of the present invention, a polyquinoline, a polyanthrazoline, or mixtures thereof, with a complexing agent of a Lewis acid, a dialkyl phosphate or a diaryl phosphate under conditions effective to cause said polymer (or polymers) to become substantially soluble in said solvent.
  • Lewis acids useful in this regard include those formed from metal halides.
  • Preferred Lewis acids include FeCl 3 , SbF 5 , SbCl 5 , BF 3 .
  • Particularly preferred Lewis acids are A1Cl 3 and GaCl 3 .
  • Dialkyl phosphates include those of alkyls having up to 6 carbon atoms; examples include diethyl dithio-phosphate, bis( 2-ethylhexyl) hydrogen phosphate; diaryl phosphates include those of aryls having up to 10 ring carbon atoms. Diphenyl is preferred.
  • the solvent in which the polymer is solubilized is preferably organic, and is more preferably an aprotic organic solvent.
  • suitable solvents include nitroalkanes, such as nitromethane, nitroethane and 1-nitropropane.
  • Other solvents include nitrobenzene, dichloromethane, dichloroethane, acet ⁇ phene, phenol. Mixtures of these and like solvents may also be employed. Nitroalkanes are preferred.
  • the conditions effective in the practice of the method of solubilizing contemplated by the present invention generally include a presence of complexing agent in an amount of up to about 20% by weight based said solvent.
  • complexing agent is present in an amount of about 15% by weight based on said solvent, more preferably about 10% by weight based on said solvent, and even more preferably about 5% by weight based on said solvent.
  • the conditions effective in the practice of the method of solubilizing contemplated by the present invention further generally includes a presence of the polymer (or copolymers) to be solubilized in an amount of up to about 3% by weight based on complexing agent plus solvent.
  • the polymer is present in an amount of up to about 2%, more preferably about 1% by weight based on complexing agent plus solvent; still more preferably about 0.5 % by weight based on complexing agent plus solvent and yet even more preferably about 0.1% by weight based on complexing agent plus solvent.
  • Another aspect of the method of solubilizing contemplated by the present invention includes recovering the polymer (or polymers) from the solution thus formed.
  • the solvent is removed by techniques known in the art, e.g., evaporation, in an amount sufficient to obtain a remnant which contains the polymer.
  • the remnant is then contacted with a base, preferably one having greater basicity in this regard than the remnant from which the polymer is to be recovered, under conditions effective to obtain the polymer in substantially pure form.
  • Bases useful in this regard include Lewis bases, preferably those having one or more hydroxy groups. It is preferred that when the polymer has been solubilized using a Lewis acid as a complexing agent that the base be a Lewis base.
  • Lewis bases especially useful in the practice of this method include water, alkanols of up to six carbon atoms or mixtures thereof. A preferred alcohol is methanol. In a particularly preferred practice of this aspect of the invention, the remnant is washed first with either water or methanol followed by a wash with the other.
  • Other bases useful in this practice of the present invention includes alkylamines in combination with a Lewis base. Alkylamines in this regard are those having up to 6 carbon atoms. It is preferred that when the polymer has been stabilized using a dialkyl phosphate and/or a diaryl phosphate as a complexing agent, that the base be an alkylamine in combination with an
  • the alkylamine is triethylemine and the alkanol is ethanol.
  • the present invention is directed to a method of forming an article of manufacture which comprises solubilizing a polymer of the invention, as well as polyquinolines or polyanthrazolines in general, in accordance with the method of solubilizing previously described to obtain a solution containing the polymer.
  • the solution is then processed into a desired configuration and the polymer recovered from the solution under conditions effective to substantially maintain the polymer in the desired configuration.
  • the polymers of the present invention may be doped to enhance conductivity by techniques known in the art.
  • the polymers may be p-doped or n- doped.
  • the p-doping is with the polymers of the invention wherein R 1 has structure (i) and Ar is a bivalent radical of a nitrogen, oxygen or sulfur-containing heterocyclic moiety, especially a sulfur-containing moiety, and most especially a thienylene.
  • 4,4'-diacetyl-1,1'-biphenylene (methanol), 1,4- diacetylbenzene (benzene), and 4,4'-diacetyldiphenylmethane (toluene) were obtained commercially and purified by recrystallization. All other materials were used as obtained: dibenzyl phosphate (Aldrich); diethyl dithiophosphate (Aldrich); bis( 2-ethylhexyl) hydrogen phosphate (Aldrich); diphenyl phosphate (Aldrich);
  • the reaction was heated to reflux and to this solution was added dropwise a solution of 5 g (15.26 mmol) of hexamethylditin (99%) in 50 ml toluene (dry) over a period of 1.5 h.
  • the reaction mixture was refluxed for another 6 h and then cooled down to -5°C.
  • Light yellow crystals of the product were isolated by suction filtration and were washed with hexane.
  • the product was then continuously extracted through Whatman filter paper #42 with dioxane using a soxhlet apparatus until all of the product was dissolved and collected in the boiling flask.
  • PDMPQ Poly(2,2'-(4,4'-diphenylmethane)-6,6'-bis(4-phenylquinoline))
  • PDMPQ was synthesized using the procedure described in Example 4 using equimolar amounts (1.78 mmol each) of 3,3'-dibenzoylbenzidine (18) and diacetyldiphenylmethane as the two monomers. 15 g of diphenyl phosphate with 8 g of m-cresol was used as the reaction medium instead of DCP/m-cresol.
  • PBADA Poly(2,7-(p,p'-biphenylacetylene)-4,9-diphenyl-1,6-anthrazoline)
  • PSDA Poly(2,7-(p,p'-stilbene)-4,9-diphenyl-1,6-anthrazoline)
  • PDMDA Poly(2,7-(4,4'-diphenylmethane)-4,9-diphenyl-1,6-anthrazoline)
  • PBTPQ Poly(2,2'-(2,2'-bithiophenyl)-6,6'-bis(4-phenylquinoline))
  • PBTAPQ Poly(2,2'-(2-thienylethynyl-2-thienyl)-6,6'-bis(4-phenylquinoline)
  • PBTAPQ was synthesized and isolated according to the procedure described in Example 4 using equimolar amounts (1.27 mmol each) of 3,3'-dibenzoylbenzidine and 1,2-Bis(5-acetyl-2-thienyl)acetylene prepared according to the procedure described in Example 3 were mixed with 12 g DCP and 2 g m-cresol.
  • the PBTAPQ polymer obtained had the following characteristics: FT-IR (freestanding film, cm -1 ): 3059, 2969, 1740, 1590, 1544, 1489, 1465, 1359, 1304, 1243, 1149, 1069, 1030, 970, 874, 825, 768, 701, 585; Anal, calcd. for (C 40 H 22 N 2 S 2 ) n : C, 80.78; H, 3.73; N, 4.71. Found: C, 77.04; H, 4.12; N, 4.13. Intrinsic viscosity was not determined.
  • PBTVPQ Poly(2,2'-(2-thienylethenyl-2- thienyl)-6,6'-bis(4-phenylquinoline)
  • PBTVPQ Poly(2,2'-(2-thienylethenyl-2- thienyl)-6,6'-bis(4-phenylquinoline)
  • PBTVPQ was synthesized and isolated according to the procedure described in Example 4 using equimolar amounts (1.27 mmol each) of 3,3'-dibenzoylbenzidine and 1,2-Bis(5- acetyl-2-thienyl)ethylene prepared according to the procedure described in Example 1, as reactants which were mixed with 12 g DCP and 2 g m-cresol.
  • PTPQ Poly(2,2'-(2,5-thiophenyl)-6,6'-bis(4-phenylquinoline))
  • PBTDA Poly(2,7-(2,2'-bithiophenyl)-4,9-diphenyl-1,6-anthrazoline)
  • the reaction mixture was purged with argon for 15 min., and then the temperature was slowly raised in steps to 140°C under positive pressure of argon. The temperature was maintained for 48 h, during which time small amounts of m-cresol were added to facilitate efficient stirring of the reaction mixture whenever it became highly viscous.
  • the polymerization dope was slowly poured into the stirred solution of 55 mL of ethanol/500 mL of triethylamine (TEA). The precipitated polymer was then chopped in a blender and collected by suction filtration. The polymer was purified by continuously extracting it with 20% TEA/ethanol solution for 24-36 h and was dried in vacuum at 80°C.
  • Anal. Calcd. for (C 32 H 18 N 2 S 2 ) n C, 77.7; H, 3.67; N, 5.66. Found: C, 75.76; H, 3.59; N, 5.34.
  • PBTADA polymer was prepared using equimolar amounts of 2,5-dibenzoyl-1,4-phenylenediamine (0.5 g) and 1,2-bis(5-acetyl-2-thienyl) acetylene (0.4336 g), prepared according to the procedure described in Example 3 in di-m-cresyl phosphate (DCP) as the solvent medium instead of DPP. The same procedure as described in Example 13 was used for the polymerization.
  • DCP di-m-cresyl phosphate
  • Anal. Calcd. for (C 34 H 18 N 2 S 2 ) n C, 78.74; H, 3.50; N, 5.40. Found: C, 76.82; H, 4.03; N, 4.66.
  • PBTVDA was synthesized and isolated according to the procedure described in Example 13 using equimolar amounts (1.58 mmol each) of 2,5-dibenzoyl-l,4-phenylenediamine and 1,2-Bis(5-acetyl-2-thienyl)ethylene prepared according to the procedure described in Example 1, as reactants which were reacted in 12 g DCP and 2.5 g m-cresol.
  • PTDA Poly(2,7-(2,5-thiopheneyl)-4,9- diphenyl-1,6-anthrazoline)
  • [ ⁇ ] 22.6 dL/g (25°C, 0.1 mol% DCP/m- cresol); FT-IR (freestanding film, cm -1 ): 3057, 3029, 102960, 1586, 1574, 1540, 1488, 1457, 1357, 1234, 1182, 1068, 1004, 870, 827, 772, 743, 701, 590.
  • Compound 2 1,2-Bis(trifluoroacetamido)-3,3'-dibenzoyldiphenyl-1-1'-acetylene
  • the product was purified by continuously extracting it in dioxane using a soxhlet apparatus (with a double thickness thimble lined with Whatman # 42 filter paper) until all of the product was dissolved and recrystallized in the boiling flask.
  • the pure product was recovered by suction filtration, washed with hexane and methanol and dried in vacuum at 60°C for 24 h. Yield 7.5 g (84%).
  • the mixture was heated to reflux, and to it was added dropwise a solution of 14.6 g (24.2 mmol) of bis (tri-n-butyl stannyl) acetylene in 76.5 ml of dry toluene over a period of 2 h.
  • the reaction was refluxed for an addition 10 h during which time part of orangish-yellow product precipitated.
  • the product was isolated by suction filtration (crude yield 13.03 g, 80%).
  • the product was purified by continuously extracting it in toluene using soxhlet apparatus (with double thickness thimble lined with Whatman # 42 filter paper) until all of the product was dissolved and collected in the boiling flask.
  • the product was purified by continuously extracting it in dioxane using soxhlet apparatus (with double thickness thimble line with Whatman # 42 filter paper) until all of the product was dissolved and recrystallized in the boiling flask. Pure product was recovered by suction filtration and dried in vacuum at 60°C for 24 h. Yield was 6.3 g (80%).
  • reaction mixture was then heated to reflux, and to this mixture was added dropwise a solution of 11.6 g (19.2 mmol) of bis(tri-n-butylstannyl) acetylene in 60 ml toluene (dry) over a period of 2 h.
  • the reaction was refluxed for an additional 10 hrs after which it was cooled down to -5°C.
  • the yellow crystals of product were isolated by suction filtration followed by washing with hexane.
  • the crude product obtained (12.4 g) was dissolved in excess chloroform, filtered and then recrystallized from chloroform to give a yield of 7.6 g (61.1%).
  • PBTPQA Equimolar amounts (1.2 mmol each) of both 4,4'-diamino-3,3'-dibenzoyldiphenyl-1,1'-acetylene
  • the reaction was quenched by cooling it down to room temperature under argon and precipitating it in 500 ml of 10% triethylamine/ethanol mixture.
  • the precipitated polymer was then collected by suction filtration.
  • the polymer was purified by continuous extraction in soxhlet apparatus with 20% triethylamine/ethanol solution for 36 h and was dried in vacuum at 80°C for 24 h.
  • the polymer product was collected and purified as described in Example 31.
  • reaction was run at this temperature for 9 h and then at 110°C for 15 h followed by 135 - 140°C for addition 24 h under static argon. As the viscosity of the reaction mixture increased with time, additional m-cresol was added to the reaction mixture to facilitate efficient stirring. Thereafter the reaction was quenched, precipitated and purified as described in Example 31.
  • reaction was run at this temperature for 2 h and then at 100°C for 3 h followed by 130°C for additional 25 h under static argon. As the viscosity of the reaction mixture increased with time, additional m-cresol was added to the reaction mixture to facilitate efficient stirring. Thereafter the reaction was quenched, precipitated, and purified as described in Example 31.
  • Nitromethane being volatile, evaporated while the film was being spun, and a polymer-DPP complex was obtained as a result.
  • the coated substrate was removed and precipitated in 10% TEA/ethanol mixture and worked up as described in part (a), above.
  • the uniform, thin-film coatings thus obtained were dried in a vacuum at 60°C.
  • Polymers of the present invention were processed into freestanding films supported in frames as follows: A round hole (or any other desirable shape) of 1-in.
  • the clamped assembly with the circular cavity facing upward, was placed on a stand or a flat surface and was adjusted so as to level the glass plate in the horizontal plane.
  • This assembly with the polymer solution in the cavity, was carefully placed into the vacuum oven and the more volatile component of the solution system was allowed to be slowly evaporated (see Figure 1C).
  • Example 36(d) When a Lewis acid/nitroalkane solution, as described in Example 36(d), was used the cavity filling and the solvent evaporation were all carried out inside the glovebox to avoid premature regeneration of the polymer.
  • the remaining highly viscous solution or film of the complex was precipitated by immersing the assembly in a glass container filed with a nonsolvent system (see Figure 1C).
  • the precipitation was completed by carrying out the extraction for 1 - 2 days at either room temperature or 40 - 50°C, depending on the thickness of the film and the solvent system used.
  • a 10% solution of triethylamine in ethanol was used for the precipitation of phosphate complexes, while methanol followed by water was employed in the case of Lewis acid complexes formed when the solubilizing method of the present invention was used.
  • Intrinsic viscosity was measured using dilute solutions in the range of 0.05 - 0.02 g/dL in 0.1 mol % DCP/m-cresol at 25°C.
  • FT-IR Fourier Transform Infrared
  • the thickness of the polymer films coated on silica substrates, as formed in Example 37 was measured using Alfa step 200 (Tencor Instruments) with an accuracy of + 0.005 ⁇ m, and the thickness of the much thicker freestanding films, supported on the frames, as formed in Example 37, was measured using an electronic micrometer with an accuracy of + 1 ⁇ m.
  • Optical absorption spectra of polymer thin films were obtained from thin coatings of the polymers on fused silica substrate formed in accordance with Example 37 on a Perkin-Elmer UV/vis/NIR spectrophotometer (Model Lambda 9).
  • solution spectra of polymer as shown in Figures 6, 7, and 10, were obtained by using dilute solutions of polymers in 0.1 mol %
  • Optical losses were, estimated using two different methods: (1) Extrapolation from solution optical losses: the polymer solutions of various concentration (1-7 wt %) were prepared in 25 wt % DPP/m-cresol solvent system using the methodology described Example 36. The absorption spectra were recorded for all the polymer concentrations by placing the highly viscous solutions between two optically flat silica substrates while maintaining a constant optical path length of 125 urn using standard spacers. Optical losses for the pure polymer were then estimated by extrapolating the linear plot of absorbance versus polymer concentration to 100 wt % polymer. (2) Direct measurement in solid state: Freestanding polymer films of various thicknesses were prepared according to the technique described above. The absorption spectra were recorded for 3 - 4 films of different thicknesses, and the optical losses were calculated from the slope of the straight line obtained by plotting absorption losses versus the thickness of the films.
  • Refractive indexes of the films of polymers in the transparent region 500 - 3000 nm were obtained using the method described by Swanepoel, et al. J. Opt. Soc. Am. (1985), 2 , 1339, the contents of which are incorporated herein by reference.
  • Various physical and optical properties of known polymers, PPQ, PPPQ, PBPQ, PSPQ, PPDA and PBDA, and polymers and copolymers of the present invention are presented in Table 1, below:
  • the polymers of the present invention have high thermally stability, with thermal transitions (glass transition and melting point) occurring at temperature greater than 250°C.
  • the decomposition temperature as determined by thermogravimetric analysis of the polymers under nitrogen at 10°C/min. was found to be generally greater than 550°C.
  • the diphenylmethane linked nonconjugated polymers of the present invention were also found to be stable above 550°C; slightly lower thermal stability was exhibited by polymers containing bithienylacetylene or bithienylvinylene linkages.
  • the polymers with bithienylvinylene linkage (PBTVPQ and PBTVDA) showed an onset of decomposition at about 510°C, whereas the polymers with bithienylacetylene linkage (PBTAPQ and PBTADA) started decomposing at about 415°C.
  • polymers of the present invention having a repeating unit of structure (II), generally associated with the polyanthrazoline family of polymers, had a higher ⁇ max and a smaller Eg compared to their structure (I) counterparts.
  • optical absorption spectra of thin films of the thiophene linked polymers of select polymers of the present invention are shown in Figures 2-5, 8, and 9 in comparison to known polymers; important optical properties of these polymers are shown at Table 1 above.
  • replacement of biphenylene linkage with bithiophene linkage resulted in a significant red shift of the absorption spectra ( ⁇ max ) of the polymers.
  • the ⁇ max has increased by about 74 nm from PBPQ to PBTPQ.
  • a red shift of about 105 nm in ⁇ max can be observed in PBTDA compared to PBDA.
  • the linear refractive index, n o is an essential property of interest in optical materials in general and also a needed information for measuring or calculating the nonlinear optical properties of a material.
  • the refractive index of the indicated polymers in the transparent region of 500 - 3000 nm was measured.
  • the accuracy in the measured values of n o was + 5%.
  • the refractive index spectra of representative members of the polyquinolines II and the polyanthrazolines III are shown in Figures 11 and 12, respectively. The refractive indexes are quite high for organic polymers.
  • the index of refraction values are between 1.68 and 1.87 in the wavelength range 900 - 3000 nm.
  • the n o values increase to greater than 2.
  • a material figure of merit Re[X (3) ]/ ⁇ is usually to be maximized, wherein Re[X (3) ] is the real part of the third-order optical nonlinearity and ⁇ is the optical loss at the frequency of intended application of the materials.
  • Re[X (3) ] is the real part of the third-order optical nonlinearity
  • ⁇ is the optical loss at the frequency of intended application of the materials.
  • Polymer 800 nm 1200 nm 1500 nm 1900 nm
  • PBAPQ a 1.0 2.5 2.5 4.5 a Measured from thin films.

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Abstract

L'invention concerne des polymères présentant d'excellentes caractéristiques électroniques, optiques et mécaniques. L'invention concerne plus particulièrement des polymères de la classe des polyquinolines et des polyanthrazolines, qui sont utiles dans des applications électroniques, optoélectroniques et photoniques. L'invention concerne en outre un procédé de solubilisation des polymères selon l'invention et des polyquinolines et polyanthrazolines en général, ladite solubilisation se faisant au moyen d'un agent complexant d'un acide de Lewis, d'un phosphate de dialkyle, d'un phosphate de diaryle ou de mélanges de ceux-ci.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5807960A (en) * 1997-04-28 1998-09-15 Hitachi Chemical Co., Ltd. Alkyl phosphate catalyst for polyquinoline synthesis
US20120217482A1 (en) * 2008-12-18 2012-08-30 Polyera Corporation Semiconductor materials prepared from dithienylvinylene copolymers

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
A.A.K.AGRAWAL ET ALL.: "New Conjugated Polyanthrazolines Containing Thiophene Moieties in the Main Chain", MACROMOLECULES, vol. 24, 1991, EASTON US, pages 6806 - 6808 *
A.K.AGRAWAL ET ALL.: "Synthesis and processing of heterocyclic polymers as electronic, optoelectronic, and nonlinear optical materials. 2. New series of conjugated rigid-rod polyquinolines and polyanthrazolines", MACROMOLECULES, vol. 26, no. 26, March 1993 (1993-03-01), EASTON US, pages 895 - 905, XP000345462, DOI: doi:10.1021/ma00057a003 *
J.K.STILLE: "Reviews - Polyquinolines", MACROMOLECULES, vol. 14, 1981, EASTON US, pages 870 - 880 *
S.E.TUNNEY ET ALL.: "Conducting Polyquinolines", MACROMOLECULES, vol. 16, 1983, EASTON US, pages 1398 - 1399 *
S.E.TUNNEY ET ALL.: "Conducting Polyquinolines", MACROMOLECULES, vol. 20, 1987, EASTON US, pages 258 - 264 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5807960A (en) * 1997-04-28 1998-09-15 Hitachi Chemical Co., Ltd. Alkyl phosphate catalyst for polyquinoline synthesis
US20120217482A1 (en) * 2008-12-18 2012-08-30 Polyera Corporation Semiconductor materials prepared from dithienylvinylene copolymers
US9221944B2 (en) * 2008-12-18 2015-12-29 Basf Se Semiconductor materials prepared from dithienylvinylene copolymers
US9650461B2 (en) 2008-12-18 2017-05-16 Basf Se Semiconductor materials prepared from dithienylvinylene copolymers

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