WO2000078843A1 - Processus pour isoler des fractions polymeres - Google Patents

Processus pour isoler des fractions polymeres Download PDF

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Publication number
WO2000078843A1
WO2000078843A1 PCT/GB2000/002310 GB0002310W WO0078843A1 WO 2000078843 A1 WO2000078843 A1 WO 2000078843A1 GB 0002310 W GB0002310 W GB 0002310W WO 0078843 A1 WO0078843 A1 WO 0078843A1
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Prior art keywords
polymer
molecular weight
fraction
solution
formula
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PCT/GB2000/002310
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English (en)
Inventor
Joanne Victoria Allen
Beverley Anne Brown
Stephen William Leeming
John Dylan Morgan
Janos Veres
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Avecia Limited
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Priority claimed from GBGB9726810.6A external-priority patent/GB9726810D0/en
Priority claimed from GBGB9914163.2A external-priority patent/GB9914163D0/en
Priority claimed from GBGB9914164.0A external-priority patent/GB9914164D0/en
Application filed by Avecia Limited filed Critical Avecia Limited
Priority to JP2001505597A priority Critical patent/JP4890706B2/ja
Priority to AU58332/00A priority patent/AU5833200A/en
Priority to EP00944096A priority patent/EP1196476A1/fr
Priority to US09/979,841 priority patent/US6653510B1/en
Publication of WO2000078843A1 publication Critical patent/WO2000078843A1/fr

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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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/026—Wholly aromatic polyamines
    • 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
    • G03G5/075—Polymeric photoconductive materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G5/076—Polymeric photoconductive materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds having a photoconductive moiety in the polymer backbone
    • G03G5/0763—Polymeric photoconductive materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds having a photoconductive moiety in the polymer backbone comprising arylamine moiety
    • G03G5/0764—Polymeric photoconductive materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds having a photoconductive moiety in the polymer backbone comprising arylamine moiety triarylamine
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00

Definitions

  • the present invention relates to certain polymeric materials, and compositions containing them which are charge transport materials.
  • the invention also relates to processes for making these polymers and their use in devices such as electroreprographic devices and electroluminescent devices.
  • Electroreprography is any process in which an image is reproduced by means of electricity and incident radiation, usually electromagnetic radiation, more usually visible light. Electroreprography includes the technology of electrophotography which encompasses photocopying and laser printing technologies. Typically, in both a photocopier and a laser printer, a photo-conductive member is first charged in the dark (e.g. by applying a high voltage via a Corona discharge). Then a latent electrostatic image in charge is produced by partial exposure of the charged photo-conductive member (e.g. a drum or belt) to radiation (e.g. light). The radiation neutralises the charge in the exposed regions.
  • the charged photo-conductive member e.g. a drum or belt
  • radiation e.g. light
  • the light source can either be reflected light from an illuminated image (photocopying) or from a laser which scans the photo-conductive member usually under instruction from a computer (laser printing). Once a latent image has been produced in charge, it is developed with toner, the toner is transferred onto a substrate (e.g. paper) and then fixed thereto (e.g. by heat) so that a visible image is obtained.
  • a substrate e.g. paper
  • the photo-conductive member typically comprises a photo-conductor (e.g. an organic photo-conductor ["OPC"]) which must perform two different functions: generate a charge on exposure to the incident radiation; and transport the photo-generated charge to the surface.
  • OPC organic photo-conductor
  • the unexposed regions of the photo-conductive member will retain their charge and form the latent image. It is usual to use different materials for each of these two processes and develop materials which are separately optimised for their ability to generate photo-induced charge (charge generating materials or "CGMs”) or their ability to transport charge (charge transport materials or "CTMs").
  • the photo-conductor can be constructed as a single layer or from a plurality of layers, for example from at least one charge generating layer (“CGL”) comprising the CGM and at least one separate charge transport layer (“CTL”) comprising the CTM.
  • CGL charge generating layer
  • CTL separate charge transport layer
  • An ideal photoconductor would be one where the material charges rapidly to a high value in the dark, retains the charge in the dark (i.e. exhibits no dark decay) and shows rapid total discharge on exposure to low-intensity illumination.
  • the time taken for the charge-discharge cycle of a photo-conductor limits the maximum speed at which the latent image can be generated.
  • Photo-conductive materials with improved electrical properties may allow faster printing and copying and/or higher quality copies and/or longer component life. The applicant has discovered means to improve the charge transport properties of certain polymers based on triaryl amine repeat unit(s).
  • PCT/GB98/03685 is a co-pending patent application which describes novel CTM polymers of repeat unit of Formula D
  • a process which comprises isolating, from a polymer comprising repeating units which are individually of Formula X
  • Ar 1 & Ar 2 are bivalent aromatic groups
  • a Arr 3 ° is a monovalent aromatic group
  • the units of Formula X may be the same or different, a molecular weight fraction which is a charge transport material.
  • Y, Ar 1 , Ar 2 and Ar 3 are as previously defined; and the units X may be the same or different, a molecular weight fraction of improved charge transport properties.
  • Ar 1 Ar 2 and Ar 3 preferably comprise benzenoid rings which are optionally fused with other, preferably benzenoid, rings and/or substituted.
  • the polymer may be a block copolymer comprising such repeat units.
  • Trivalent repeat units of Formula D may be included to permit a degree of chain branching if desired.
  • the molecular weight fraction produced by the process according to the present invention may be of Formula 1 :
  • a and B are chain terminating groups, for example, hydrogen, chlorine, bromine or iodine, or other leaving groups used in a polymerisation process by which the polymer is made, or end capping groups, and m is the average number of X units per molecule of the fraction.
  • m is suitably 4 to 50, preferably 4 to 30, more preferably 4 to 25 for example 4 to 15 and especially 5 to 13 or 6 to 14. Generally it is desired that m is at least 5 in all of the above ranges.
  • the polydispersity of the fraction is suitably 1.1 to 4, preferably 1.1 to 3 and more preferably 1.2 to 2.5.
  • the fraction is substantially free from molecules having 3 or fewer or 50 or more repeat units.
  • the aryl groups may be mono- or poly-cyclic and the rings are preferably benzene rings substituted with, for example, one or more C 1-4rj -alkyl groups in order to increase their solubility in for example tetrahydrofuran (THF) for processing purposes.
  • They may have fused ring groups, naphthyl groups or covalently linked benzene rings for example biphenyl residues but are preferably benzene rings which are each substituted with alkyl groups providing a total of one to eight aliphatic carbon atoms per benzene ring.
  • the groups A and B are inert to coupling with further molecules of the polymer so as to reduce the likelihood of further growth of molecules to undesired sizes. Thus it is preferred that they should not be halide atoms.
  • Molecular weight fractions produced by the present invention may be isolated from polymers prepared without the addition of a separate end capping reagent to control the molecular weight of the polymer.
  • Isolation of the molecular weight fraction may be by filtration technologies, chromatographic techniques, osmotic methods, and/or solid extraction using a suitable solvent, for example Soxhlet extraction.
  • the process comprises a step of partially precipitating from a solution of the polymer in a suitable solvent, a molecular weight fraction thereof. It may be separated by dissolving the polymer in the solvent, precipitating a least soluble (highest molecular weight) fraction and then recovering a fraction of greater solubility having good CTM properties, for example in electrophotographic applications, from the remaining solution.
  • the least soluble fraction may be usable as a CTM in non-electrophotographic applications.
  • Suitable solvents are dichloro- and trichloro-ethane, dichloro- and thchloro-ethylene, dichlorobenzene, toluene, dioxane and, more preferably, THF. It will be appreciated that it is not necessary to use any other isolation procedure in conjunction with this preferred form of the invention.
  • (c) more conveniently, differential precipitation, that is, by the addition of a precipitant to a solution of the polymer and collecting successive fractions at increasing concentrations of the precipitant, in which a precipitant is suitably a liquid which is miscible with the solvent but in which the polymer is sparingly soluble.
  • the precipitant may be selected from n-octane, heptane, n-hexane, cyclohexane, methylpentane, n-butanol, n-propanol, 2-propanol, ethanol, methanol, acetone, mixed alkanes such as petroleum ether (pet ether) with boiling range 60-80°C, methyl-t-butyl ether (MTBE), high boiling mixed alkanes such as those available under the trade name Isopar (e.g. Isopar G with a boiling point of about 160°C); and/or mixtures thereof.
  • mixed alkanes such as petroleum ether (pet ether) with boiling range 60-80°C, methyl-t-butyl ether (MTBE), high boiling mixed alkanes such as those available under the trade name Isopar (e.g. Isopar G with a boiling point of about 160°C); and/or mixtures thereof.
  • the chosen precipitant has a boiling point (at ambient conditions) preferably from about 50°C to about 200°C, more preferably from about 60°C to about 170°C. It is preferably a lower alcohol, for example a C ⁇ -alkanol, such as ethanol or propanol or, more preferably, methanol, or a lower alkane or cycloalkane, preferably a C 4 . 10 -alkane or cycloalkane, or acetone. An especially preferred precipitant is methanol.
  • the molecular weight fraction collected by the isolating means preferably has an average number of repeat units ('m' number) of from about 4 to about 15, more preferably from about 5 to about 13.
  • the isolated molecular weight fraction preferably has a much narrower molecular weight distribution than the crude polymer.
  • the polymerisation may be performed in the presence of a controlling means to control molecular weight of the polymeric material during polymerisation (and before isolation) to provide a polymer suitable for use as a charge transport material, more preferably which is electroreprographically effective, most preferably with an average number of repeat units 'm' of between about 4 and about 25.
  • the means for controlling MW may be any of those described in co-pending British patent Application No 9914164.1 (the priority of which is claimed for this application) and/or those described in co-pending application PCT/GB98/03685.
  • the isolation means may be used to isolate a fraction having further improved properties as a charge transport material.
  • the isolation means may be used to convert crude polymer which is not especially fit for this purpose into an effective charge transport material.
  • the polymeric materials of the present invention are preferably obtained by polymerisation controlled by addition of at least one end capping reagent in an amount sufficient to reduce substantially further growth of the polymer chain.
  • the end capped polymers of the invention can be produced more cheaply and with a better control over their resultant properties (such as their molecular weight and polydispersity) due to the end capping.
  • the chemical nature of the end cap can be selected to control aspects of the polymerisation and hence properties of the resultant polymer. For example carrier mobility, polymer compatibility, electronic configuration [e.g. frontier orbital (FO) energy levels] and/or solubility may be affected by substitution (if used) and/or molecular weight (e.g. mobility can be shown to increase with polymer molecular weight).
  • the polymers of the invention are substantially free of chlorine, more preferably substantially free of chloro, bromp and iodo, containing species.
  • Polymers of the present invention preferably have a weight average molecular weight (M w ) from about 1000 to about 13000 daltons.
  • a suitable terminal group such as hydrogen or another substituent which is inert to coupling under the conditions of polymerisation, eg an akyl or aryl group, can be selected to control aspects of the polymerisation and
  • Ar 1 , Ar 2 and Ar 3 are each an optionally substituted aromatic group which may be a mononuclear aromatic group or a polynuclear aromatic group.
  • a mononuclear aromatic group has only one aromatic ring, for example phenyl or phenylene.
  • a polynuclear aromatic group has two or more aromatic rings which may be fused (for example napthyl or naphthylene), individually covalently linked (for example biphenyl) and/or a combination of both fused and individually linked aromatic rings.
  • each Ar 1 , Ar 2 and Ar 3 is an aromatic group which is substantially conjugated over substantially the whole group.
  • Polymers of the present invention may be made by a polymerisation process which is controlled to limit further growth of the polymer chain. If the end capping reagent is generated in situ in excess (e.g. at the step when it is desired to terminate polymerisation) further growth of the polymer chain (and/or polymer network if the polymer is branched and/or cross-linked) can be substantially inhibited (e.g. substantially quenched).
  • the end capper adds terminal group(s) to the polymer chain which are substantially incapable under the conditions of polymerisation of undergoing coupling (e.g. with other polymer precursor and/or other parts on the polymer chain).
  • the terminal group(s) end cap the polymer chain and act to substantially reduce the possibility of (preferably stop) further polymerisation by blocking sites at which the polymer chain could otherwise grow under the conditions of the polymerisation.
  • sites at which the polymer chain could otherwise grow under the conditions of the polymerisation Preferably in the polymers of the present invention from about 60% to substantially all of the polymerisation sites are blocked by at least one terminal substituent. More preferably (in one option) substantially all such sites are blocked. In another more preferable option from about 60% to about 90% of these sites are blocked.
  • polymer fractions of the present invention which may further distinguish them from known polymers, are that they can, if desired: comprise terminal group(s) other than a group selected from H, halo, hydroxy, glycidyl ether, acrylate ester, methacrylate ester, ethenyl, ethynyl, vinylbenzoxyl, maleimide, nadimide, triflurovinyl ether, a cyclobutene, a group forming part of a cyclobutene group, and trialkylsiloxy; and/or be other than copolymer(s) which consist of triarylamine repeat unit(s) and C 4-7 alicyclic repeat unit(s) optionally containing heteroatom(s); and/or be substantially undoped; and/or substantially polydisperse and/or other than of formula: wherein n is from 7 to 11.
  • Polymer fractions of the invention preferably comprise at least 4, and more preferably at least 6, repeat units of Formulae X or 1 or Formulae 2 or 3, hereinafter.
  • Preferred polymer fractions of the present invention comprise molecules represented by Formula 2:
  • Ar 1 , Ar 2 , Ar 3 & Y represent, independently in each case, those atom(s) and/or group(s) as described herein; n represents an integer from 3 to about 500;
  • R 1 & R 2 represent, independently, a terminal group as described herein.
  • Ar 1 , Ar 2 , and Ar 3 are preferably, each independently, optionally substituted aromatic groups, more preferably having optionally substituted heterocyclic and/or benzenoid rings.
  • the optionally substituted aromatic groups Ar 1 and Ar 2 are, or form part of, bivalent C 6 ⁇ 0 -hydrocarbyl groups, preferably phenylene and/or naphthylene groups. Any substituents are preferably C 1-15 -alkyl groups.
  • Polymeric material of the present invention may comprise molecules represented by Formula 3
  • R ⁇ R 5 & R 6 represent, independently in each case, optionally substituted C 1-15 alkyl groups and/or one or more other substituents.
  • the terminal groups (which may be attached to the repeat units of Formula X, denoted by A & B in Formula 1 and denoted by R & R 2 in Formulae 2 and 3 are preferably unreactive groups, that is are substantially incapable of undergoing chain extension or cross-linking under the conditions of polymerisation. They are more preferably independently selected from hydrogen or C M0 -hydrocarbyl groups, preferably selected from C ⁇ o-alkyl, C 6 . 36 -aryl and C 7 . 36 -aralkyl groups, any of which may optionally be substituted. Especially preferred terminal groups comprise C 6 . 36 -aryl groups optionally substituted with at least one C 1-4 -alkyl, C lJ( -alkoxy, or amino group (itself optionally
  • the terminal group may be selected from phenyl, optionally substituted with at least one methyl, 2-methylprop-2-yl, methoxy, ethoxy, trifluoromethyl and/or diethylamino group.
  • the novel polymer fractions of the present invention are of use as CTMs in electroreprographic devices. However such polymers may have many other uses which may rely on the same, similar and/or different properties to those required for electroreprography.
  • the polymers of the present invention may be generally relevant for use in (and/or in combination with) any application and/or device which requires the use of polymeric conductors, polymeric photo-conductors, organic photo-conductors (OPCs), electroluminescent (EL) materials, polymeric materials which exhibit substantial conjugation over the polymer and/or polymeric semiconductors.
  • Preferred polymeric semiconductors have hole mobilities greater than 0.01 cm 2 /volt.sec. This minimum mobility is either that of the pure polymeric material, or of an admixture of the polymeric material with one or more other polymeric or monomeric materials having different electrical and/or physical properties.
  • the polymers of the present invention also exhibit some or all of the following other useful properties: high carrier mobility, compatibility with binders, improved solubility, high durability and/or high resistivity undoped.
  • the polymers of the invention may be used in at least one of the devices and/or for at least one of the applications described in co-pending PCT application GB98/03685.
  • polymeric CTMs of the invention when optimised for use with organic light emitting materials (OLEMs) preferably may have a higher molecular weight and/or different mobilities than are optimal for electroreprography.
  • OLEMs organic light emitting materials
  • compositions and/or specific polymers used for each application may be different.
  • an electroreprographic polymeric CTM is compatible with the binder polymers (such as polycarbonates) used to make a CTL.
  • a polymeric CTM for use in an OLEM may be formulated without many other (or even no other) ingredients to make a film of substantially pure CTM.
  • each of these CTM polymers may require different physical properties.
  • M n number average molecular weights quoted in the Examples herein were determined by gel permeation chromatography (Waters 150CV) calibrated against polystyrene standards. Samples were run in tetrahydofuran (hereinafter "THF") using two "Polymer Labs. Mixed D” gel columns at a rate of 1 ml/min. A value for M n was determined from the GPC spectrum, and from the M n value, an approximate average degree of polymerisation ( ⁇ m as defined herein) was calculated by subtracting the mass of the terminal groups and dividing by the molecular weight of the repeat unit.
  • THF tetrahydofuran
  • Titanyloxy phthalocyanine (TiOPc) type IV (15.0 g) was dispersed into a 5 % w/w solution of polyvinyl butyral (PVB) in n-butyl acetate (75.0 g) using a high shear mixer. A further quantity of n-butyl acetate (20.0 g) was added to the dispersion to reduce its viscosity. The resulting slurry was charged to an Eiger Mini 50 Motormill (supplied by Eiger Torrance Ltd.) containing a charge (34 ml) of 0.6 to 0.8 mm zirconia beads. The mill was operated at 3,000 rpm for 50 minutes.
  • Eiger Mini 50 Motormill supplied by Eiger Torrance Ltd.
  • PVB solution (25.0 g, 5 % w/w in n-butyl acetate) was added to the millbase and milling was continued for a further 10 minutes.
  • the millbase was discharged into a receiving vessel and PVB solution (61.5 g) was added to the mill and circulated for 5 minutes.
  • the solution was then discharged into the millbase which was stirred throughout to prevent pigment agglomeration and n-butyl acetate (349.0 g) was flushed through the bead mill and out into the stirred dispersion to yield a CGL coating formulation of PVB (1.48 %), TiOPc (2.75 %) and n-butyl acetate (95.77 %).
  • the dispersion was coated onto aluminised Melinex film using a K#2 bar and K Control coater model 202 (supplied by RK Print-Coat Industries Ltd.). The coating was dried for 5 minutes at 100°C to produce a CGL which was approximately 0.4 ⁇ m thick.
  • CTL Charge Transport Layer
  • a formulation comprising a CTM of the invention was prepared using an amount of a CTM and (optionally) another CTM as specified in the Examples. If not otherwise specified herein 0.5 g of CTM was used (equivalent to 25 % CTM in the CTL) in the following preparation.
  • the polymeric CTM and polycarbonate resin 1.5 g of the PCZ available commercially from Esprit Chemical Co. under the trade designation TS 2020
  • TS 2020 toluene
  • a semi-transparent metal electrode was applied to the top of a section of the film by vacuum deposition.
  • the CTL thickness was measured using an Elcometer E 300 device.
  • the electrodes were connected to a power supply and a digitising oscilloscope.
  • the time of flight (TOF) technique is a transient photoconductivity experiment well known to those skilled in the art.
  • a field was applied across the sample via the electrodes and a sheet of charge carriers (holes) was photogenerated at one side of the film.
  • the charge carriers drifted through the film under the influence of the field creating a current which was detected using a current amplifier connected to the oscilloscope.
  • the current was observed to decrease and the transit-time across the film could thereby be determined from the transit waveform.
  • the measurement was repeated with a range of different applied voltages.
  • a number of electrophotographic photoreceptors were prepared as in the TOF technique described herein.
  • a photoreceptor test piece of approximately 5 x 10 cm was cut out from the coated aluminised Melinex.
  • the test piece was then fixed to a bare aluminium drum (used as the substrate for an OPC), 30 mm in diameter. Two small areas of coating were removed from the edge of the test piece using a suitable solvent.
  • the test piece was then electrically connected to the drum using a suitable conductive paint.
  • the drum was then mounted in a QEA PDT 2000 device (available commercially from Quality Engineering Associates Inc. Burlington MA 01803 USA) and was grounded via the contact in the QEA instrument.
  • the QEA PDT 2000 was fitted with a 780 nm band pass filter.
  • a track with a consistent -800 V charge of at least 10 mm length was selected using the charge scanner. Once the track had been selected the PIDC was measured in the known manner.
  • the energy required to discharge the photoreceptor to 1/8th of its original potential i.e. from -800 V to -100 V (E 7/8 )and the residual potential on the photoreceptor after the highest energy exposure ( ⁇ 3 ⁇ Jcm "2 ) (Vr) were recorded. Low values for E 7/8 and V r are desirable in a photoreceptor as they indicate efficient discharge of the device on exposure to light.
  • Photoreceptors with CTMs of the invention and various CTL binders OPC devices can be prepared in a similar manner to the method described above using different CGLs, binders and/or additives in combination with other CTMs and CGMs, for example as described in co-pending application PCT/GB98/03685 (e.g. in the tables thereof).
  • a reaction flask 500 mL, 5 neck was flame dried under nitrogen.
  • Nickel(ll) chloride (0.14 g, 1.05 mmol
  • zinc powder (8.9 g, 136.1 mmol)
  • 2,2'-dipyridyl (0.25 g, 1.58 mmol)
  • triphenylphosphine (2.76 g, 10.5 mmol)
  • N, /V-dimethylacetamide anhydrous, 100 mL
  • the temperature was then raised to 80 °C and b/s(4-chlorophenyl)-2,4-dimethylphenylamine (15.0 g, 43.8 mmol) was added to the reaction flask. Heating was continued at 80 °C for 6 hours, after which time the reaction was deemed complete.
  • the reaction mixture was allowed to cool to room temperature and added to a stirring mixture of water (400 mL) and dichloromethane (400 mL). With stirring HCI (cone, 50 mL) was added dropwise to destroy the excess zinc. The resulting mixture effervesced.
  • the organic extract was collected and the aqueous phase was further extracted with dichloromethane, with warming, to aid dissolution of some retained product.
  • the dichloromethane phase was filtered, the organic extracts combined and concentrated under reduced pressure to yield a yellow gum.
  • the resulting gum was dissolved in THF (400 mL) and precipitated from ethanol (600 mL). The resulting precipitate was collected by vacuum filtration.
  • the solid was dissolved in fresh DCM (200 mL) and washed with Na 2 CO 3 (1 M, 200 mL).
  • the organic extract was collected, concentrated under reduced pressure and purified by column chromatography (silica gel), eluting with a 750 mL mixture of dichloromethane and hexane (in a respective volume ratio of 3 to 1 ).
  • a reaction flask 250 mL, 5 neck equipped with overhead stirrer, thermometer and nitrogen line was flame dried under nitrogen.
  • Nickel(ll) chloride 0.097 g, 0. 75 mmol
  • zinc powder 5.9 g, 90.4 mmol
  • 2,2'-dipyridyl 0.18 g, 1.13 mmol
  • triphenylphosphine 3.93 g, 15 mmol
  • N, -dimethylacetamide anhydrous, 75 mL
  • Solid 2A was dissolved in THF (50 mL) and precipitated from methanol (700 mL).
  • a reaction vessel (1 litre, 5-neck) was equipped with an overhead stirrer, a nitrogen line and was flame dried under nitrogen.
  • Nickel(ll) chloride 0.5 g
  • zinc powder 30.4 g
  • 2,2'-dipyridyl 0.9 g
  • triphenylphosphine 9.9 g
  • anhydrous N,N- dimethylacetamide 300 ml
  • the catalyst solution was warmed to 80 °C and then the bis(N-4-chlorophenyl)-2,4-dimethylphenylamine (50.0 g) was added to the catalyst solution.
  • the 1-chloro-3-methylbenzene (9.2 g) was added over 30 mins via a syringe pump. The reaction was maintained at temperature and stirred for 4.5 hours, after which time more of the 1-chloro-3-methylbenzene (9.2 g) was added. The resulting mixture was stirred for a further 14 hours, to ensure the polymer was completely end capped.
  • the reaction mixture was allowed to cool to room temperature and DCM (100 mL) was added. This mixture was poured into stirring water (300 mL) and hydrochloric acid (10 M, 100 mL) was added dropwise. The resulting mixture effervesced. The organic layer was removed and washed sequentially with sodium hydrogen carbonate solution and several times with distilled water.
  • Example 4.1 to 4.3 illustrates that successive molecular weight fractions isolated from a crude polymeric CTM exhibit higher mobility than the crude polymer (Example 3). Thus polymers isolated by selective precipitation exhibit improved properties as CTM.
  • a reaction flask (1 L, 5-neck) equipped with overhead stirrer, condenser, thermometer and nitrogen line was flame dried under nitrogen.
  • Nickel(ll) chloride (0.79 g, 6.1 mmol
  • zinc powder 48.8 g, 747 mmol
  • 2,2'-dipyridyl (1.44 g, 9.22 mmol)
  • triphenylphosphine 9.52 g, 58.4 mmol
  • N,N-dimethylacetamide anhydrous, 620 mL
  • Solid 5A isolated in Part A was fractionated to obtain fractions of narrower Mw distribution.
  • Solid 5A (50.0 g) was dissolved in THF (200 mL) and methanol added dropwise in a process of fractional precipitation. Methanol was added dropwise (see Table 4 for quantities) until the solution maintained a cloudy appearance. After each methanol addition, the solution mixture was allowed to settle then the top liquor layer was decanted off and further methanol added to repeat the process. The bottom cloudy layer was treated with excess methanol (100 mL) to encourage precipitation of the product. Each precipitate was collected by vacuum filtration.
  • Fractions 1/1 and /1/2 were recombined and fractionated from THF and acetone. Thus, the fractions were dissolved in THF (200 mL) and the fractionation process repeated as described earlier (see Table 5).
  • a reaction flask fitted with overhead stirrer, condenser, thermometer and nitrogen line was flame dried under nitrogen.
  • Nickel (II) chloride (0.06 g, 0.6 mmol
  • zinc 5.0 g, 75.0 mmol
  • 2,2'-dipyridyl (0.14 g, 0.9 mmol
  • triphenylphosphine 1.6 g, 6.0 mmol
  • ⁇ /, ⁇ /-dimethylacetamide 90 cm 3
  • the catalyst was warmed to 74°C and bis(4-chlorophenyl)-2,4-dimethylphenylamine (8.35g, 25.0 mmol) and 1-chloro-3-methyl- benzene (1.6 g, 12.5 mmol) were added to the reaction mixture.
  • the reaction mixture was maintained at this temperature for 6 hours, after which time further 1-chloro-3- methylbenzene (0.3g, 20% of original charge) was added.
  • the reaction mixture was maintained at 74°C for a further 16 hours to ensure the polymer was completely end capped.
  • the reaction mass was allowed to cool to room temperature and dichloromethane (100 cm 3 ) added and the reaction mixture filtered.
  • a polymeric material comprising at least one repeat unit, the or each (if more than one) repeat unit consisting substantially of a moiety of Formula D:
  • Y represents, independently if in different repeat units, N, P, S, As and/or Se preferably N;
  • Ar 1 and Ar 2 which may be the same or different, represent, independently if in different repeat units, a multivalent (preferably bivalent) aromatic group (preferably mononuclear but optionally polynuclear) optionally substituted by at least one optionally substituted C lJl0 -carbyl-derived groups and/or at least one other optional substituent
  • Ar 3 represents, independently if in different repeat units, a mono or multivalent (preferably bivalent) aromatic group (preferably mononuclear but optionally polynuclear) optionally substituted by at least one: optionally substituted C ⁇ o-carbyl-derived group and/or at least one other optional substituent, characterised in that, after polymerisation, the polymeric material is treated by a isolation means to isolate a molecular weight fraction which is effective as a charge transport material.
  • Ar 1 , Ar 2 , Ar 3 and Y 1 represent, independently in each case, those group(s) and/or atom(s) as claimed in claim 1; n represents an integer from 3 to about 500;
  • R 1 & R 2 represent, independently, a terminal group as described herein;
  • R 3 represents H or a terminal group which is inert to coupling under polymerisation conditions, such as alkyl or aryl.
  • a polymeric material as in any preceding clause which comprises a substance represented by the following formula:
  • R 1 , R 2 & n represent, independently if in different repeat units, those groups or values described herein, R 3 only being present when the ring to which it is attached is not itself attached to another repeat unit;
  • R 3 represents H or a terminal group which is inert to coupling under polymerisation conditions, such as alkyl or aryl;
  • a & b represent, independently in each case, 0 or an integer from 1 to 4;
  • c represents, independently in each case, 0 or an integer from 1 to d (where d is 6 minus the valence of the aromatic group), preferably 0 to 5;
  • n represents an integer from 4 to about 200; and
  • R 4 , R 5 & R 6 represent, independently in each case, optionally substituted C-,. 15 -alkyl and/or at least one optional substituent.
  • terminal group(s) comprise, independently if in different repeat units, at least one optionally substituted C ⁇ - 40 -hydrocarbyl group each of which is substantially incapable of undergoing chain extension or cross-linking under the conditions of polymerisation.
  • terminal group(s) comprise, independently if in different repeat units, at least one group selected from C 1-30 -alkyl, C 6 . 36 -aryl and C 7 . 36 -aralkyl each of which is substantially incapable of undergoing chain extension or cross-linking under the conditions of polymerisation.
  • a composition comprising an inert diluent, optionally substantially electroreprographically inert, and, optionally in a substantially pure form, at least one polymeric material as claimed in any preceding claim.
  • composition as in clause 10, in which the diluent is selected from at least one of polyamide, polyurethane, polyether, polyester, epoxy resin, polyketone, polycarbonate, polysulfone, vinyl polymer, polystyrene, polyacrylamide, copolymers thereof and mixtures thereof.
  • a composition as in clause 10 or 11 which has a T g which is within about 50°C of the T g of the diluent resin.
  • composition as in clause 13 which comprises the at least one polymeric material in a total amount from about 10% to about 75% by total mass of the composition.
  • composition comprising at least one polymeric material as in any of clauses 10 to 15, the composition being substantially as described herein and/or exhibiting the properties described herein, with reference to any of the Examples and/or Tables herein.
  • a device and/or a component for a device comprising at least one polymeric material as in any of clauses 1 to 9 and/or composition as in any of clauses 10 to 16.
  • a method for making a charge transport layer comprising coating a substrate with a composition as in any of clauses 10 to 16, and/or at least one polymeric material as in any of clauses 1 to 9 optionally in at least one layer.
  • a method of making a device and/or component as in any of clauses 17 to 21 comprising the step of forming on a substrate at least one charge transport layer (CTL) which comprises a composition as in any of clauses 10 to 16, and/or at least one polymeric material as in any of clauses 1 to 9.
  • CTL charge transport layer
  • compositions as in any of clauses 10 to 16, and/or at least one polymeric material as in any of clauses 1 to 9, in a device and/or component as in any of clauses 17 to 21 for the purpose of transporting charge and/or improving electroreprographic and/or electroluminescent performance.
  • ion exchange optionally by derivatisation of a suitable salt on the central atom of the polymer repeat unit and then passing the salt through the ion-exchange column.
  • ion-exchange column optionally by derivatisation of a suitable salt on the central atom of the polymer repeat unit and then passing the salt through the ion-exchange column.
  • the solvent is selected from: n-octane, heptane, n-hexane, cyclohexane, methylpentane, n-butanol, n-propanol, 2-propanol, ethanol, methanol, acetone, a mixed alkane petroleum ether with boiling range 60-80°C, methyl tertiary-butyl ether, a

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Abstract

L'invention concerne un procédé pour isoler à partir d'un polymère comprenant des unités répétitives possédant chacune la formule X, (formule X) dans laquelle Y est P ou N, Ar1 et Ar2 sont des groupes aromatiques bivalents, Ar3 est un groupe aromatique monovalent et les unités de formule (X) peuvent être identiques ou différents, un fraction à poids moléculaire qui convient tout particulièrement comme une substance de transport de charges.
PCT/GB2000/002310 1997-12-19 2000-06-14 Processus pour isoler des fractions polymeres WO2000078843A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2001505597A JP4890706B2 (ja) 1999-06-18 2000-06-14 ポリマーフラクションの分離方法
AU58332/00A AU5833200A (en) 1999-06-18 2000-06-14 Process for the isolation of polymer fractions
EP00944096A EP1196476A1 (fr) 1999-06-18 2000-06-14 Processus pour isoler des fractions polymeres
US09/979,841 US6653510B1 (en) 1999-06-18 2000-06-14 Process for the isolation of polymer fractions

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
GBGB9726810.6A GB9726810D0 (en) 1997-12-19 1997-12-19 Compounds composition & use
PCT/GB1998/003685 WO1999032537A1 (fr) 1997-12-19 1998-12-16 MATERIAU POLYMERE CONTENANT N, P, S, As OU Se ET COMPOSITION DE MATERIAU DE TRANSFERT DE CHARGE
GB9914163.2 1999-06-18
GBGB9914163.2A GB9914163D0 (en) 1999-06-18 1999-06-18 Polymers, Compositions and uses
GBGB9914164.0A GB9914164D0 (en) 1999-06-18 1999-06-18 Polymers,compositions and uses
GB9914164.0 1999-06-18

Publications (1)

Publication Number Publication Date
WO2000078843A1 true WO2000078843A1 (fr) 2000-12-28

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1394617A2 (fr) * 2002-08-30 2004-03-03 Canon Kabushiki Kaisha Photoconducteur électrophotographique organique, appareil électrophotographique et cartouche de traitement
WO2004056937A1 (fr) * 2002-12-20 2004-07-08 Avecia Limited Dispositifs electroniques
DE112006003179T5 (de) 2006-01-21 2009-01-15 Merck Patent Gmbh Elektronische Kurzkanalvorrichtung umfassend eine organische Halbleiterformulierung
US7718734B2 (en) 2002-12-20 2010-05-18 Merck Patent Gmbh Organic semiconducting materials
EP2204861A1 (fr) 2001-12-19 2010-07-07 Merck Patent GmbH Dispositifs électroniques
US7985810B2 (en) 2005-12-02 2011-07-26 Sumitomo Chemical Company, Limited Polymer compound and polymer light emitting device using the same
EP3858886A4 (fr) * 2018-09-28 2022-08-03 Sumitomo Chemical Company, Limited Procédé de production d'un composé polymère

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Publication number Priority date Publication date Assignee Title
US4714779A (en) * 1980-11-20 1987-12-22 Xerox Corporation Aromatic aryl amine polymers
US4937165A (en) * 1989-04-03 1990-06-26 Xerox Corporation Photoconductive imaging members with N,N-bis(biarylyl)aniline charge transport polymers
WO1999032537A1 (fr) * 1997-12-19 1999-07-01 Avecia Limited MATERIAU POLYMERE CONTENANT N, P, S, As OU Se ET COMPOSITION DE MATERIAU DE TRANSFERT DE CHARGE

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4714779A (en) * 1980-11-20 1987-12-22 Xerox Corporation Aromatic aryl amine polymers
US4937165A (en) * 1989-04-03 1990-06-26 Xerox Corporation Photoconductive imaging members with N,N-bis(biarylyl)aniline charge transport polymers
WO1999032537A1 (fr) * 1997-12-19 1999-07-01 Avecia Limited MATERIAU POLYMERE CONTENANT N, P, S, As OU Se ET COMPOSITION DE MATERIAU DE TRANSFERT DE CHARGE

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2204861A1 (fr) 2001-12-19 2010-07-07 Merck Patent GmbH Dispositifs électroniques
EP2207217A1 (fr) 2001-12-19 2010-07-14 Merck Patent GmbH Dispositifs électroniques
EP1394617A2 (fr) * 2002-08-30 2004-03-03 Canon Kabushiki Kaisha Photoconducteur électrophotographique organique, appareil électrophotographique et cartouche de traitement
EP1394617A3 (fr) * 2002-08-30 2005-01-05 Canon Kabushiki Kaisha Photoconducteur électrophotographique organique, appareil électrophotographique et cartouche de traitement
US6994941B2 (en) 2002-08-30 2006-02-07 Canon Kabushiki Kaisha Electrophotographic photosensitive member, process cartridge and electrophotographic apparatus
WO2004056937A1 (fr) * 2002-12-20 2004-07-08 Avecia Limited Dispositifs electroniques
US7718734B2 (en) 2002-12-20 2010-05-18 Merck Patent Gmbh Organic semiconducting materials
US7985810B2 (en) 2005-12-02 2011-07-26 Sumitomo Chemical Company, Limited Polymer compound and polymer light emitting device using the same
DE112006003179T5 (de) 2006-01-21 2009-01-15 Merck Patent Gmbh Elektronische Kurzkanalvorrichtung umfassend eine organische Halbleiterformulierung
EP3858886A4 (fr) * 2018-09-28 2022-08-03 Sumitomo Chemical Company, Limited Procédé de production d'un composé polymère

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