Classifications

• • 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
  • 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
  • C08F24/00—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 a heterocyclic ring containing oxygen
• • 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
  • C08F26/00—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
  • C08F26/06—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
• • 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
  • C08F28/00—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 a bond to sulfur or by a heterocyclic ring containing sulfur
  • C08F28/06—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 a bond to sulfur or by a heterocyclic ring containing sulfur by a heterocyclic ring containing sulfur

Definitions

• R is a fused ring radical.
• .these copolymers are N-vinylindole-indole copolymer, N-vinylindole-N-methylindole copolymer, N-vinylindole-indene copolymer, N-vinylindole-coumarin copolymeryand N- vinylindole-maleic anhydride copolymer.
• This invention relates to a class of N-vinylindole copolymers and, more particularly, relates to their preparation and use as photoconductors in electrophotographic processes.
• R is selected from the group consisting of hydrogen and lower alkyl, wherein R is a fused ring radical, and wherein n is at least 1 and m+n is greater than 10.
• N-vinylindole monomers can be prepared according to the above-cited Polymer Letters references.
• N-vinylindole and N-Vinyl-Z-methylindole and 3-methylindole can be prepared in one step 3,554,741 Patented Jan. 12., 1971 by pressure vinylation at elevated temperatures under nitrogen in a solvent containing an alkaline catalyst.
• the vinylindole monomers were prepared from the corresponding indoles by the following procedure: The indole, g., was dissolved with 5 g. KOH in 250 m1. toluene in a one-liter stainless steel pressure reactor.
• the reactor was pressurized at ambient temperature to 200 p.s.i.g., with acetylene, 99.5% and diluted with 200 p.s.i.g. dry nitrogen.
• the temperature was slowly raised to 150"for the 2-, B-methylindoles and for indole and held constant for twenty-four hours.
• the extent of reaction was monitored on a pressure-temperature recorder.
• the crude mixture was washed with water and ether, the organic layer dried over Na S0 and fractionated through a glass helix-packed column under vacuum to give the monomers: N-vinylindole, B.P. 702 at 1 mm.; N-vinyl-2-methylindole, B.P. 105 at 2 mm.; and N-vinyl-3-methylindole, B.P. 94 at 1 mm.
• Indene coumarin, maleic anhydride, benzofuran, and benzothiophene are commercially available.
• the polymerization of the N-vinylindole, substituted and unsubstituted, and copolymers is carried out in solution under an inert atmosphere with a cationic catalyst, such as diethylaluminum chloride.
• a cationic catalyst such as diethylaluminum chloride.
• the copolymers are also prepared in vacuo with heat.
• a 1:1 molar ratio of each monomer is preferred in order to obtain a 50/50 copolymer. If desired, howev'e'f, other ratios may be used to obtain copolymers with different proportions of monomeric units.
• n is at least 1 and m+n is greater than 10.
• n is at least 1 and m+n is greater than 10.
• n is at least 1 and m+n is greater than 10.
• n is at least 1 and m+n is greater than 10.
• n is at least 1 and m+n is greater than 10.
• n is at least 1 and 111+ is greater than 10.
• n is at least 1 and m+n is greater than 10.
• n is at least 1 and m+n is greater than 10.
• FORMULA XXII wherein n is at least 1 and m-l-n is greater than 10.
• FORMULA XXIII wherein n is at least 1 and m -l-n is greater than 10.
• the compounds of the general formula are soluble in organic solvents, such as tetrahydrofuran, or any other solvent in which compounds are at least partially soluble.
• organic solvents such as tetrahydrofuran, or any other solvent in which compounds are at least partially soluble.
• solvents such as tetrahydrofuran, or any other solvent in which compounds are at least partially soluble.
• Such solutions are applied to substrates suitable for electrophotography and the solvent is then removed. Mixtures of solvents can also be used. If the polymer is essentially insoluble, it can be melted and applied to the substrate while in a liquid state.
• the substrate material may be any which satisfy the requirements of electrophotography such as metal, glass, paper, or plastic. Unless it is to be used in a device employing dual corona discharge, such as US. 2,922,883, the substrate should preferably have a conductivity greater than l0 ohmcmf Applications of the solutions of the polymers of the general formula to the substrate is in the usual manner, such as spraying, doctor blade, meniscus, etc., followed by drying.
• the polymers of the present invention absorb below the visible region of the electromagnetic spectrum, i.e. below 4000 A. Accordingly, their spectral sensitivity to the visible region may be improved by the addition of dyestulf sensitizers.
• activators or electron acceptors which increase the photoconductivity of the polymers of the present invention may also be applied with the polymers in preparing the photoconductive element. When added in a layer with the polymer, the activator or electron acceptor may be in molar amounts up to and beyond equivalent molar amounts of each monomeric unit in the copolymer. The only limitation on the amount of the activator or electron acceptor in the polymer layer is the dark conductivity.
• xerography One type of electrophotography process in which the polymers of the invention are useful is known as xerography.
• This process comprises the laying down of a uniform electrostatic charge on a photoconductive insulating layer comprising at least one of the polymers of the invention, exposing the electrostatic charge surface to a pattern of light to effect decay of the charge in the illuminated areas, and contacting the latent electrostatic image thus formed with colored electroscopic powder to render the image visible.
• a copy sheet is brought into contact with the developed image and transferred thereto and fixed thereon.
• the residual powder remaining on the photoconductive insulating element is removed by cleaning and the element is then ready for the preparation of the next copy or the next cycle.
• Example I -Five grame (0.035 mole) N-vinylindole and 4.1 g. (0.035 mole) indole were weighed into a heavy walled Pyrex polymerization tube. The mixture was de- Clrademark of Corning Glass Works.
• Example II -Five grams of N-vinylindole (0.035 mole) and 4.58 g. (0.035 mole) freshly distilled N-methylindole were weighed into a heavy walled Pyrex polymerization tube. The tube contents were degassed and sealed as in Example I, then heated in an oil bath at 150 C. for 24 hours. The light yellow viscous product, obtained upon cooling, was dissolved in benzene and precipitated in 800 ml. methyl alcohol. The white precipitate was re-dissolved and re-precipitated, then dried at C. for 16 hours giving 6.2 gm. (64.5% conversion) White powdery polymer (Formula II). The intrinsic viscosity in benzene was 0.24 and the melting point range was 220 to 230 C. Elemental analysis for (C H N indicated a 50/ 50 copolymer:
• Example III N-vinylindole, 14.3 g. (0.01 mole) and 13.1 g. (0.1 mole) freshly distilled N-methylindole were added to ml. dry benzene in a 250 m1. 3-necked polymerization flask equipped with stirrer, thermometer, condenser and nitrogen gas inlet tube. The mixture was heated to 50 C. in an oil bath, then 0.33 g. (0.002 mole) azobisisobutyronitrile catalyst was added. The temperature of the mixture was raised to 70 C. and the polymerization continued for 24 hours under a nitrogen blanket. The mixture was cooled, poured into ml. methyl alcohol to give a heavy white precipitate.
• the monomer mixture was degassed and sealed as in previous examples, then heated at C. for 96 hours and at 200 C. for an additional 20 hours.
• a clear viscous mass was obtained which was dissolved in hot tetrahydrofuran and precipitated as a white solid in 800 ml. methyl alcohol.
• the elemental analysis for (C H N) indicated 50/50 copolymer.
• Example V Five grams (0.035 mole) pure N-vinylindole and 5.1 g. (0.035 mole) coumarin were mixed intimately, then transferred to a heavy walled Pyrex glass polymerization tube. The mixture was degassed, sealed, then heated at 200 C. for 48 hours. The dark viscous mass obtained was twice dissolved in hot tetrahydrofuran and precipitated from cold methyl alcohol. A light tan solid polymer (Formula VIII) 4.5 g. (44.5% conversion) was obtained after drying 16 hours at 60 C.; M.P. 300 C. which had an intrinsic viscosity in tetrahydrofuran of 0.24. Elemental analysis for (C H NO Calculated (percent): C, 78.87; H, 5.23. Found (percent): C, 80.98, 8l.13; H, 5.78, 5.94.
• Example VI.-N-vinylindolc, 10.9 g. (0.077 mole) and maleic anhydride, 7.5 g. (0.076 mole) were added to 285 g. of methylene chloride in a 500 m1. 3-necked polymerization flask equipped with stirrer, thermometer, condenser, and nitrogen gas inlet tube. The mixture was heated to 40 C. in an oil bath. Then 0.09 g. (3.8 10 mole) of benzoyl peroxide catalyst was added. The polymerization was continued for 22 hours under a nitrogen blanket. The mixture was cooled, poured into 1000 ml. of hexane to give 11.9 g. (68% conversion) of a red colored solid precipitate. The polymer (Formula VII) had a softening range of 146-153 C.
• the elemental analysis for calculated on the basis of a 85/15 copolymer was as follows:
• Examples VlI-XII.-Photoconductive elements were prepared from the polymer of Examples I, II, IV, V, and VI by forming five separate solutions of 2,4,7-trinitro-9- flurorenone and each of the polymers, except for the polymer of Example VI, in a ratio of .7 mole of 2,4,7-trinitro-9-fluorenone to 1 monomeric unit of the copolymer using tetrahydrofuran as the solvent.
• the ratio of 2,4,7- trinitro-9-fiuorenone to the copolymer of Example VI was .62 to 1.
• the solutions were coated on five separate aluminum substrates with a doctor blade set on a 5 mil wet gap. After drying, the photoconductive layers had a thickness of 78 microns.
• the thus prepared photoconductive elements were tested for this photoconductive and electrophotographic properties on the electrometer described in US. Pat. S.N. 690,775, filed Dec. 15, 1967 and assigned to the same assignee. The results of tests are shown in the following
• W is the exposure time required to reach one-half of the original electrostatic surface potential applied to the photoconductive element.
• the compounds are not limited as photoconductors in the mode electrophotography known as xerography, but may be used in persistent electrophotographic methods such as that described in US. Pat. No. 2,845,348 or any other method where the photoconductor is exposed before charging.
• the compounds are also particularly well suited for other photoconductive applications.
• An electrophotographic process comprising the steps of forming an electrostatic charge pattern on a photoconductive element comprising a photoconductive polymer having the following structural formula:
• R L 1% Him L 11 wherein R is selected from the group consisting of hydrogen and lower alkyl, wherein R is a fused ring radical, and wherein n is at least 1 and m+n is greater than 10.
• R is selected from the group consisting of hydrogen and lower alkyl
• X is selected from the group consisting of O, S, CH and NR wherein R is selected from the group consisting of hydrogen and lower alkyl
• n is at least 1 and m+n is greater than 10.
• n is at least 1 and m+n is greater than 10.
• n is atleast 1 and m+n is greater than 10.
• n is at least 1 and m+n is greater than 10.
• n is at least 1 and m+n is greater than 10.
• n is at least 1 and m+n is greater than 10.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Photoreceptors In Electrophotography (AREA)

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Cited By (2)

• 1968
  • 1968-04-08 US US719663A patent/US3554741A/en not_active Expired - Lifetime
  • 1968-12-30 FR FR1602788D patent/FR1602788A/fr not_active Expired
• 1969
  • 1969-01-22 BE BE727249D patent/BE727249A/xx unknown
  • 1969-02-12 DE DE19691906831 patent/DE1906831A1/de active Pending
  • 1969-04-05 DE DE19691917747 patent/DE1917747A1/de active Pending
  • 1969-04-08 GB GB07993/69A patent/GB1264035A/en not_active Expired
  • 1969-04-08 GB GB07992/69A patent/GB1269385A/en not_active Expired

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