US3896184A - Polymers of benzanthracene as active matrix materials - Google Patents

Polymers of benzanthracene as active matrix materials Download PDF

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Publication number
US3896184A
US3896184A US374163A US37416373A US3896184A US 3896184 A US3896184 A US 3896184A US 374163 A US374163 A US 374163A US 37416373 A US37416373 A US 37416373A US 3896184 A US3896184 A US 3896184A
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US
United States
Prior art keywords
benzanthracene
vinyl
group
polycyclic
active matrix
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US374163A
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English (en)
Inventor
John Alf Bergfjord
Richard William Radler
Richard Phillip Millonzi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xerox Corp
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Xerox Corp
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Filing date
Publication date
Application filed by Xerox Corp filed Critical Xerox Corp
Priority to US374163A priority Critical patent/US3896184A/en
Priority to CA194,535A priority patent/CA1023390A/en
Priority to JP7073174A priority patent/JPS546554B2/ja
Priority to IT24471/74A priority patent/IT1015439B/it
Priority to GB2804874A priority patent/GB1470459A/en
Priority to DE2430755A priority patent/DE2430755C3/de
Priority to FR7422482A priority patent/FR2235104B1/fr
Priority to NL7408736A priority patent/NL7408736A/xx
Priority to US05/511,133 priority patent/US4022956A/en
Application granted granted Critical
Publication of US3896184A publication Critical patent/US3896184A/en
Priority to JP11605178A priority patent/JPS54108891A/ja
Priority to JP11605278A priority patent/JPS54105551A/ja
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
    • C07C1/34—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen reacting phosphines with aldehydes or ketones, e.g. Wittig reaction
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/043—Photoconductive layers characterised by having two or more layers or characterised by their composite structure
    • G03G5/0436—Photoconductive layers characterised by having two or more layers or characterised by their composite structure combining organic and inorganic layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
    • G03G5/0528—Macromolecular bonding materials
    • G03G5/0532—Macromolecular bonding materials obtained by reactions only involving carbon-to-carbon unsatured bonds
    • G03G5/0535—Polyolefins; Polystyrenes; Waxes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/07—Polymeric photoconductive materials
    • G03G5/071—Polymeric photoconductive materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/40—Ortho- or ortho- and peri-condensed systems containing four condensed rings
    • C07C2603/42—Ortho- or ortho- and peri-condensed systems containing four condensed rings containing only six-membered rings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S585/00—Chemistry of hydrocarbon compounds
    • Y10S585/929—Special chemical considerations
    • Y10S585/93—Process including synthesis of nonhydrocarbon intermediate
    • Y10S585/931—Metal-, Si-, B-, or P-containing, e.g. Grignard

Definitions

  • ABSTRACT Vinyl polycyclic aromatics, particularly polycyclics having three or more nuclei and their polymers utilizable as active matrix material for xerographic purposes are obtained in high yield by initial conversion of the polycyclic reactant to the aldehyde in the presence of a haloalkyl ether as a formulating agent in the presence of a Friedl-Crafts type catalyst.
  • the aldehyde intermediate is then coverted to the vinyl monomer by using a Wittig-type reaction and, thereafter. polymerized, as desired, by the use of a cationic mechanism.
  • the formation and development of images on photoconductive materials by electrostatic means is well known.
  • the best known of the commercial processes utilizes a latent electrostatic image on an imaging surface by first uniformly electrostatically charging the surface in the dark and then exposing the electrostatically charged surface to a light and shadow image.
  • the light-struck areas of the imaging layer are thus made conductive and the electrostatic charge selectively dissipated in these areas.
  • the latent positive electrostatic image remaining is made visible by development with a finely divided colored electroscopic material known as toner". This material is preferentially attracted to those areas on the image-bearing surface which have retained an electrostatic charge.
  • the image is permanently affixed to the photoconductor or transferred to some other suitable material such as paper.
  • Photoconductor layers useful for xerographic purposes 1 may be homogeneous layers of a single material such as vitreous selenium or (2) may be composite layers containing a photoconductor and another material.
  • One type of composite layer used in xerography is illustrated by US. Pat. No. 3,121,006 to Middleton and Reynolds, which describes a number of binder layers containing finely-divided particles of a photoconductive inorganic compound such as zinc oxide, dispersed in an electrically insulating organic resin binder.
  • the binder comprises a material which is incapable of transporting the injected charge carriers generated by the photoconductor particles for any significant distance.
  • the photoconductor particles must be in substantially continuous particle-to-particle contact throughout the layer to permit sufficient charge dissipation in the lightstruck areas.
  • the uniform dispersion of photoconductor particles describes in Middleton et 21]., therefore, represents a high volume concentration (i.e. up to about 50 percent or more by volume) of photoconductive particles.
  • Another form of composite photosensitive layer which has also been considered by the prior art includes a layer of photoconductive material which is covered with a relatively thick plastic layer and coated on a supporting substrate.
  • lt is a further object to obtain new polymeric derivatives for use as active matrix components for xerographic purposes.
  • Such material is obtained in excellent yield by contacting a corresponding polycyclic reactant represented by the formula with at least a molar amount of a haloalkyl ether of the formula R (Ii) CH-OA a lower alkyl (Ex. a S-methyl-1,2-benzanthracene), a lower alkoxy or a phenyl substituted 1,2- benzanthracene;
  • a in the above formulating agent is individually defined as an alkyl group such as an alkyl group of 1-8 carbon atoms and preferably a lower alkyl group of 1-8 carbon atoms such as methyl, isopropyl, or octyl;
  • the molar ratio of formylating agent (Formula lI)-to-polycyclic reactant (formula I) can vary from about 1.0-1.5 to l; a satisfactory catalytic amount of SnCl and/or TiCl for instance, is found to be in equimolar amount with respect to the haloalkyl ether formylating agent.
  • This reaction step is usefully carried out, for instance, in methylene chloride at a temperature within the range of about -i 5 to 40C, and preferably at about 0 -25C, to obtain a decomposible intermediate product which.
  • reaction solvent can be a chlorinated hydrocarbon such as methylene chloride or tetrahydrofurane.
  • the temperature of the reaction mixture usefully varies from about 50 to 75C, depending upon the solvent used, and about -500 ppm of initiator is found sufficient to effect the reaction.
  • the product is then conveniently recovered by precipitation with methanol and purified in the usual manner.
  • a controlled admixture of reactants containing up to 10% by weight of a second monomer such as a vinyl ether (ex. isobutylvinylether) or an acrylate is conveniently reacted at a temperature of about -50 to 20C and in the presence of a reaction solvent and catalyst of the types indicated above.
  • a second monomer such as a vinyl ether (ex. isobutylvinylether) or an acrylate
  • Suitable vinyl polycyclic aromatic monomers obtainable and usable in accordance with the present invention are reported, for instance, in Table l with respect to formula l-lV and some polymers exemplified in Table ll.
  • EXAMPLE I (C-l) About. 1 mole of commercially obtained and chromatographically purified l,2 benzanthracene is dissolved in methylene chloride at about 0C and admixed with about an equimolar amount of SnCl 0.12 mole of a, a-dichloromethyl ether is then added slowly with continuous stirring for about 2 hours, the mixture being maintained at ambient temperature at least until HCl is no longer evolved. The resulting aldehyde intermediate product is then hydrolyzed and recovered. 0.5 Mole of the aldehye is then contacted with exact equimolar amounts of Triphenylphosphine at about 0C for 1 hour to obtain the vinyl monomeric product. This product is recovered and identified as IO-Vinyl-benzanthracene. The compound is reported in Table l as C-l.
  • EXAMPLE lll (C-l) The reaction of Example I is repeated with the exception that TiCl is utilized a catalyst to obtain the alde- EXAMPLE V (P-] hyde'
  • the resulting vinyl intefrmediatc product 0.01 Mole of the 10- vinylbenzanthracene obtained lated, found to be identical with the product of Examin Example I is dissolved in ethyl ether and the P and reported as Table I belowmixed with about 500 ppm of BF; with constant stirring EXAMPLE W (05) 5 at a temperature of about 0C for about 3 hours.
  • Example I The resulting homopolymer is separated out and purified m
  • the reaction of Example I IS repeated with the cxccpthe usual way, and Coded as in Table I] below tion that the polycyclic aromatic reactant is l-methyl-2.3-benzochrysene.
  • the resulting 4-vinyl in- EXAMPLE VI (P'2) termediate product is isolated and reported as (-5 in It)
  • the polymerization reaction of Example V is re- Table I below.
  • Example V A process for producing a vinyl substitued aromatic polycyclic compound of the formula
  • the vinyl monomer identified as C-S .(Example lV) comprising contacting a corresponding reactant resch reacted as in Example .V but with an equivalent sented by the formula: amount of SbCl asan initiator to obtain the polymeric material identified as P-3 and reported in Table ll be- O low, I I 10 with at least a-molar amount of a haloalkyl ether of the 5 EXAMPLE VIII (CP-l) formula
  • Example V is repeated but with the addition of about 0.001 mole of isobutylvinyl ether to the 10- vinyl benzanthracene (C-l reactant and the reaction allowed to i5 proceed for about 6 hours at C.
  • ap- 40 Q M CH plied overcoat layers varying from 10a to about 30p. of polyvinyl pyrene having a numerical average molecular and then contacting the aldehyde intermediate with a weight of about 10,000
  • the pyrene utilized is Commer reactive amount of a phosphme compound represented cially obtained, purified and polymerized by acylation by the formulae (ref. Vollman, Beeker, Corell and Streech; Justus Lie- (Y)3 p CH2 (YEP (-1 h1g5 Annalen Der Chemie: Vol. 531 (1937).
  • the respective plates are thin corona charged at 900 Whch defined as a P y or lkyl group; volt, exposed to a monochromic light source at 4000 A to OPtam the cprrespondmg vmyl Substltuted P at a flux of 2 X 10 photons/cm /sec. and tested for. Cych? Compoumlelectrical properties.* The results are reported in Table A Process of clam ⁇ 1 Wherem the catalyst Sncl4- m below 3. The process of claim 1 wherein Q is an asymmetric *P.
  • Q is a 1,2- sflmple (JV/dild-I EOW/IL) benzanthracene group.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Photoreceptors In Electrophotography (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
US374163A 1973-06-27 1973-06-27 Polymers of benzanthracene as active matrix materials Expired - Lifetime US3896184A (en)

Priority Applications (11)

Application Number Priority Date Filing Date Title
US374163A US3896184A (en) 1973-06-27 1973-06-27 Polymers of benzanthracene as active matrix materials
CA194,535A CA1023390A (en) 1973-06-27 1974-03-08 Polymers of benzanthracene as active matrix materials
JP7073174A JPS546554B2 (enrdf_load_stackoverflow) 1973-06-27 1974-06-20
IT24471/74A IT1015439B (it) 1973-06-27 1974-06-25 Composti policiclici aromatici e procedimento per la loro produzio ne e il loro impiego in tecniche xerografiche
GB2804874A GB1470459A (en) 1973-06-27 1974-06-25 Producing vinyl substituted polycyclic aromatic compounds
DE2430755A DE2430755C3 (de) 1973-06-27 1974-06-26 Elektrophotographisches Aufzeichnungsmaterial
FR7422482A FR2235104B1 (enrdf_load_stackoverflow) 1973-06-27 1974-06-27
NL7408736A NL7408736A (enrdf_load_stackoverflow) 1973-06-27 1974-06-27
US05/511,133 US4022956A (en) 1973-06-27 1974-10-02 Polymers of benzanthracene as active matrix materials
JP11605178A JPS54108891A (en) 1973-06-27 1978-09-22 Preparation of viny sabstituted polycyclic aromatic compound polymer
JP11605278A JPS54105551A (en) 1973-06-27 1978-09-22 Imaging element

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US374163A US3896184A (en) 1973-06-27 1973-06-27 Polymers of benzanthracene as active matrix materials

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US05/511,133 Division US4022956A (en) 1973-06-27 1974-10-02 Polymers of benzanthracene as active matrix materials

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US (1) US3896184A (enrdf_load_stackoverflow)
JP (3) JPS546554B2 (enrdf_load_stackoverflow)
CA (1) CA1023390A (enrdf_load_stackoverflow)
DE (1) DE2430755C3 (enrdf_load_stackoverflow)
FR (1) FR2235104B1 (enrdf_load_stackoverflow)
GB (1) GB1470459A (enrdf_load_stackoverflow)
IT (1) IT1015439B (enrdf_load_stackoverflow)
NL (1) NL7408736A (enrdf_load_stackoverflow)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4719286A (en) * 1985-03-14 1988-01-12 Northrop Corporation Class of conductive polymers
US4835081A (en) * 1986-07-03 1989-05-30 Xerox Corporation Photoresponsive imaging members with electron transport overcoatings
CN102712558A (zh) * 2009-11-05 2012-10-03 出光兴产株式会社 含杂环的非对称性芳香族化合物、有机薄膜晶体管用化合物、以及使用它的有机薄膜晶体管

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2496867A (en) * 1948-05-13 1950-02-07 Gen Electric 3-vinylpyrene and method of preparing the same
US3041166A (en) * 1958-02-12 1962-06-26 Xerox Corp Xerographic plate and method
US3121007A (en) * 1958-02-12 1964-02-11 Xerox Corp Photo-active member for xerography
US3121006A (en) * 1957-06-26 1964-02-11 Xerox Corp Photo-active member for xerography

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2496867A (en) * 1948-05-13 1950-02-07 Gen Electric 3-vinylpyrene and method of preparing the same
US3121006A (en) * 1957-06-26 1964-02-11 Xerox Corp Photo-active member for xerography
US3041166A (en) * 1958-02-12 1962-06-26 Xerox Corp Xerographic plate and method
US3121007A (en) * 1958-02-12 1964-02-11 Xerox Corp Photo-active member for xerography

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4719286A (en) * 1985-03-14 1988-01-12 Northrop Corporation Class of conductive polymers
US4835081A (en) * 1986-07-03 1989-05-30 Xerox Corporation Photoresponsive imaging members with electron transport overcoatings
CN102712558A (zh) * 2009-11-05 2012-10-03 出光兴产株式会社 含杂环的非对称性芳香族化合物、有机薄膜晶体管用化合物、以及使用它的有机薄膜晶体管
US8766243B2 (en) 2009-11-05 2014-07-01 Idemitsu Kosan Co., Ltd. Heterocycle-containing asymmetric aromatic compound, compound for organic thin film transistor, and organic thin film transistor using the same
CN102712558B (zh) * 2009-11-05 2014-11-19 出光兴产株式会社 含杂环的非对称性芳香族化合物、有机薄膜晶体管用化合物、以及使用它的有机薄膜晶体管

Also Published As

Publication number Publication date
FR2235104A1 (enrdf_load_stackoverflow) 1975-01-24
DE2430755A1 (de) 1975-01-23
DE2430755B2 (de) 1978-07-27
FR2235104B1 (enrdf_load_stackoverflow) 1977-03-11
JPS5036452A (enrdf_load_stackoverflow) 1975-04-05
GB1470459A (en) 1977-04-14
CA1023390A (en) 1977-12-27
JPS54108891A (en) 1979-08-25
IT1015439B (it) 1977-05-10
NL7408736A (enrdf_load_stackoverflow) 1974-12-31
DE2430755C3 (de) 1979-04-12
JPS546554B2 (enrdf_load_stackoverflow) 1979-03-29
JPS54105551A (en) 1979-08-18

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