WO2005035632A1 - Polysiloxanes hyperramifies a fonctionnalite carbazolyle, composition de silicone et diode electroluminescente organique - Google Patents

Polysiloxanes hyperramifies a fonctionnalite carbazolyle, composition de silicone et diode electroluminescente organique Download PDF

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WO2005035632A1
WO2005035632A1 PCT/US2004/020942 US2004020942W WO2005035632A1 WO 2005035632 A1 WO2005035632 A1 WO 2005035632A1 US 2004020942 W US2004020942 W US 2004020942W WO 2005035632 A1 WO2005035632 A1 WO 2005035632A1
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carbazolyl
transport layer
mol
polysiloxane
hyperbranched polysiloxane
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PCT/US2004/020942
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Paul Schalk
Shihe Xu
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Dow Corning Corporation
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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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
    • H10K85/146—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE poly N-vinylcarbazol; Derivatives thereof
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/151—Copolymers
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
    • H10K85/324—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising aluminium, e.g. Alq3
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom

Definitions

  • the present invention relates to carbazolyl-functional hyperbranched polysiloxanes and more particularly to carbazolyl-functional hyperbranched polysiloxanes containing N- carbazolylalkyl groups.
  • the present invention also relates to a silicone composition containing a carbazolyl-functional hyperbranched polysiloxane, a cured carbazolyl-functional polysiloxane prepared by curing the silicone composition, and an organic light-emitting diode
  • U.S. Patent No. 6,284,906 Bl to Paulasaari et al. discloses methods for the preparation of hyperbranched siloxane polymers by anionic polymerization of a cyclotrisiloxane having the functional group Si-OH.
  • Morikawa et al. (Macromolecules, 1991, 24(12), 3469-3474) describe the synthesis of highly branched polysiloxane starburst polymers starting from tris[(phenyldimethylsiloxy) dimethylsiloxy]methylsilane and bis[( ⁇ enyldimethylsiloxy)methylsiloxy]dimethylsilanol as the initiator core (GO-Ph) and the building block, respectively.
  • Muzafarov et al. (Polym. Sci., Ser. A, 1999, 41, 283) report the synthesis of a hyperbranched polysiloxane from triethoxysilanol via a rapid, ammonia-catalyzed condensation process.
  • the present invention is directed to a first carbazolyl-functional hyperbranched polysiloxane prepared by a method comprising reacting (a) a hyperbranched polysiloxane having a formula selected from:
  • the present invention is also directed to a second carbazolyl-functional hyperbranched polysiloxane prepared by the preceding method, wherein the mole ratio of the N-alkenyl carbazole to the silicon-bonded hydrogen atoms in the hyperbranched polysiloxane (a) is from 0.8:1 to 1:1 and further comprising reacting hyperbranched polysiloxane (a) with
  • R 3 or -H is a divalent organic group
  • X is a hydrolysable group
  • r is 0, 1, or 2
  • the mole ratio of the alkenyl silane (e) to the silicon-bonded hydrogen atoms in the hyperbranched polysiloxane (a) is from 0.01:1 to 0.15:1.
  • the present invention is also directed to a silicone composition comprising the second carbazolyl-functional hyperbranched polysiloxane and an organic solvent.
  • the present invention is also directed to a cured carbazolyl-functional polysiloxane prepared by curing the silicone composition.
  • the instant invention is further directed to an organic light-emitting diode comprising: a substrate having a first opposing surface and a second opposing surface; a first electrode layer overlying the first opposing surface; a light-emitting element overlying the first electrode layer, the light emitting element comprising a hole-transport layer and an electron-transport layer, wherein the hole-transport layer and the electron-transport layer lie directly on one another, and one of the hole-transport layer and the electron- transport layer comprises the first carbazolyl-functional hyperbranched polysiloxane; and a second electrode layer overlying the light-emitting element.
  • the instant invention is still further directed to an organic light-emitting diode comprising: a substrate having a first opposing surface and a second opposing surface; a first electrode layer overlying the first opposing surface; a light-emitting element overlying the first electrode layer, the light emitting element comprising a hole-transport layer and an electron-transport layer, wherein the hole-transport layer and the electron-transport layer lie directly on one another, and one of the hole-transport layer and the electron- transport layer comprises a cured carbazolyl-functional polysiloxane prepared by curing the silicone composition of the present invention; and a second electrode layer overlying the light-emitting element.
  • the carbazolyl-functional hyperbranched polysiloxanes of the present invention exhibit electroluminescence, emitting light when subjected to an applied voltage.
  • the hyperbranched polysiloxanes containing hydrolysable groups can be cured to produce durable cross-linked polysiloxanes.
  • the carbazolyl-functional hyperbranched polysiloxanes can be doped with small amounts of fluorescent dyes to enhance the electroluminescent efficiency and control the color output of the carbazolyl-functional hyperbranched polysiloxane or cured carbazolyl-functional polysiloxane.
  • the silicone composition of the present invention can be conveniently formulated as a one-part composition. Moreover, the silicone composition has good shelf-stability in the absence of moisture. Importantly, the composition can be applied to a substrate by conventional high-speed methods such as spin coating, printing, and spraying. Also, the silicone composition can be readily cured by exposure to moisture at mild to moderate temperatures.
  • the cured carbazolyl-functional polysiloxane prepared by curing the silicone composition of the present invention exhibits electroluminescence. Moreover, the cured polysiloxane has good primerless adhesion to a variety of substrates. The cured polysiloxane also exhibits excellent durability, chemical resistance, and flexibility at low temperatures.
  • the cured polysiloxane exhibits high transparency, typically at least 95% transmittance at a thickness of 100 nm, in the visible region of the electromagnetic spectrum.
  • the polysiloxane is substantially free of acidic or basic components, which are detrimental to the electrode and light-emitting layers in OLED devices.
  • the OLED of the present invention exhibits good resistance to abrasion, organic solvents, moisture, and oxygen. Moreover, the OLED exhibits high quantum efficiency and photostability.
  • the OLED is useful as a discrete light-emitting device or as the active element of light-emitting arrays or displays, such as flat panel displays.
  • OLED displays are useful in a number of devices, including watches, telephones, lap-top computers, pagers, cellular phones, digital video cameras, DVD players, and calculators.
  • Figure 1 shows a cross-sectional view of a first embodiment of an OLED according to the present invention.
  • Figure 2 shows a cross-sectional view of a second embodiment of an OLED according to the present invention.
  • Figure 3 shows a cross-sectional view of a third embodiment of an OLED according to the present invention.
  • Figure 4 shows a cross-sectional view of a fourth embodiment of an OLED according to the present invention.
  • the "mol%" of a siloxane unit in a hyperbranched polysiloxane is defined as the ratio of the number of moles of the siloxane unit to the total number of moles of siloxane units in the hyperbranched polysiloxane, multiplied by 100.
  • hydrocarbyl free of aliphatic unsaturation means the group is free of aliphatic carbon- carbon double bonds and aliphatic carbon-carbon triple bonds.
  • N- carbazolyl refers to a group having the formula:
  • a first carbazolyl-functional hyperbranched polysiloxane is prepared by a method comprising reacting (a) a hyperbranched polysiloxane having a formula selected from:
  • Hyperbranched polysiloxane (a)(i) has the formula
  • Rl is Ci to Ci 0 hydrocarbyl free of aliphatic unsaturation or -H
  • R 3 is C ⁇ to C IQ hydrocarbyl free of aliphatic unsaturation
  • R 4 is R 3 , -H, or -(CH2)q-Cz, wherein Cz is N-carbazolyl and q is an integer from 2 to 10
  • R is R 3 or-H
  • v is from 5 to 30 mol%
  • w is form 10 to 40 mol%
  • x is from 0 to 60 mol%
  • y is from 0 to 60 mol%
  • the sum x+y is from 10 to 60 mol%.
  • the hydrocarbyl groups represented by R and R 3 are free of aliphatic unsaturation and typically have from 1 to 10 carbon atoms, alternatively from 1 to 6 carbon atoms.
  • Acyclic hydrocarbyl groups containing at least 3 carbon atoms can have a branched or unbranched structure.
  • hydrocarbyl groups include, but are not limited to, alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1- dimethylethyl, pentyl, 1-methylbutyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 1,2- dimethylpropyl, 2,2-dimethylpropyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl; cycloalkyl, such as cyclopentyl, cyclohexyl, and methylcyclohexyl; aryl, such as phenyl and naphthyl
  • Cz wherein Cz is N-carbazolyl and q is an integer from 2 to 10, include, but are not limited to, groups having the formulae: -CH2-CH2-CZ, -(CH2)3-Cz, -(CH2)4-Cz, -(CH2)6 _ Cz, and -
  • the subscript v typically has a value of from 5 to 30 mol%, alternatively from 10 to 25 mol%; the subscript w typically has a value of from 10 to 40 mol%, alternatively from 20 to 30 mol%; the subscript x typically has a value of from 0 to 60 mol%, alternatively from 0 to 50 mol%; the subscript y typically has a value of from 0 to 60 mol%, alternatively from 0 to 50 mol%; and the sum x+y typically has a value of from 10 to 60 mol%; alternatively from 20 to 50 mol%.
  • Hyperbranched polysiloxane (a)(i) typically has a number-average molecular weight of from 500 to 1,000,000, alternatively from 1,000 to 100,000, alternatively from 1,000 to 50,000, where the molecular weight is determined by gel permeation chromatography employing a low angle laser light scattering detector.
  • hyperbranched polysiloxane (a)(i) examples include, but are not limited to, polysiloxanes having the following average formulae:
  • Rl is Ci to CJO hydrocarbyl free of aliphatic unsaturation or -H
  • R 3 is C ⁇ to Ci Q hydrocarbyl free of aliphatic unsaturation
  • R 4 is R 3 , -H, or -(CH2)q-Cz, wherein Cz is N-carbazolyl and q is an integer from 2 to 10
  • R is R 3 or -H
  • V is from 0 to 40 mol%
  • w' is from 0 to 40 mol%
  • x' is form 0 to 60 mol%
  • y' is from 0 to 60 mol%
  • z is from 10 to 60 mol%
  • the sum x'+y' is
  • Rl, R 3 , R 4 , and R ⁇ are as defined and exemplified above for hyperbranched polysiloxane (a)(i).
  • the subscript v' typically has a value of from 0 to 40 mol%, alternatively from 5 to 25 mol%; the subscript w' typically has a value of from 0 to 40 mol%, alternatively from 0 to 10 mol%; the subscript x' typically has a value of from 0 to 60 mol%, alternatively from 0 to 50 mol%; the subscript y' typically has a value of from 0 to 60 mol%, alternatively from 0 to 50 mol%; the subscript z typically has a value of from 10 to 60 mol%, alternatively from 20 to 50 mol%; and the sum x'+y' typically has a value of from 10 to 60 mol%; alternatively from 20 to 50 mol%.
  • Hyperbranched polysiloxane (a)(ii) typically has a number-average molecular weight of from 500 to 1,000,000, alternatively from 1,000 to 100,000, alternatively from 1,000 to 50,000, where the molecular weight is determined by gel permeation chromatography employing a low angle laser light scattering detector.
  • Examples of hyperbranched polysiloxane (a)(ii) include, but are not limited to, polysiloxanes having the following average formulae:
  • Hyperbranched polysiloxanes (a)(i) and (a)(ii) can be prepared by a method comprising the steps of: (A) reacting a difunctional silane having the formula RlHSiX ⁇ with a polyfunctional silane selected from at least one trifunctional silane having the formula RlSiX 3 and at least one tetrafunctional silane having the formula X 4 SiX 3 in the presence of a Lewis acid catalyst and, optionally, an organic solvent, to produce a hyperbranched polysiloxane having a formula selected from
  • R is C to CJQ hydrocarbyl free of aliphatic unsaturation or -H
  • step (B) reacting the hyperbranched polysiloxane produced in step (A) with an endblocking agent selected from at least one silane having the formula R 3 2R 4 Si ⁇ 5, at least one disiloxane having the formula (R 3 2R SiO)2, at least one disilazane having the formula (R 3 2R->Si)2NH, and a mixture comprising at least two of the preceding agents, in the presence of water and an effective amount of a water-miscible organic solvent, wherein R 3 is Cj to C ⁇ Q hydrocarbyl free of aliphatic unsaturation; R 4 is R 3 , H, or -(CH2)q-Cz, wherein Cz is N-carbazolyl and q is an integer from 2 to 10; R ⁇ is R 3 or -H; and X ⁇ is a hydrolysable group or -OH.
  • an endblocking agent selected from at least one silane having the formula R 3 2R 4 Si ⁇ 5, at least one disiloxane having
  • RlHSiX ⁇ is reacted with a polyfunctional silane selected from at least one trifunctional silane having the formula R SiX 2 3 and at least one tetrafunctional silane having the formula
  • Rl is C to CJQ hydrocarbyl free of aliphatic unsaturation or -H
  • X 4 is X 3 or -OH; a is from 5 to 50 mol%; b is from 0.1 to 25 mol%; c is from 5 to 50 mol%; d is from 5 to 70 mol%; a' is from 5 to 50 mol%; b' is from 0.1 to 25 mol%; c' is from 0.01 to 50 mol%; e is from 5 to 50 mol%; f is from 5
  • the difunctional silane is at least one silane having the formula RlHSiX ⁇ wherein R! is Ci to CJO hydrocarbyl free of aliphatic unsaturation or-H, and ⁇ l is -CI, -Br, -I, -
  • R 2 is Ci to Cg hydrocarbyl free of aliphatic unsaturation or halogen-substituted hydrocarbyl free of aliphatic unsaturation and Y is a divalent organic group.
  • the hydrocarbyl groups represented by R! are as described and exemplified above for hyperbranched polysiloxane (a)(i).
  • the hydrocarbyl and halogen-substituted hydrocarbyl groups represented by R 2 are both free of aliphatic unsaturation and typically have from 1 to 8 carbon atoms, alternatively from 3 to 6 carbon atoms.
  • Acyclic hydrocarbyl and halogen- substituted hydrocarbyl groups containing at least 3 carbon atoms can have a branched or unbranched structure.
  • hydrocarbyl groups represented by R 2 include, but are not limited to, unbranched and branched alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 1- ethylpropyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, hexyl, heptyl, and octyl; cycloalkyl, such as cyclopentyl, cyclohexyl, and methylcyclohexyl; phenyl; alkaryl, such as tolyl and xylyl; and aralkyl, such as benzyl and phenethyl.
  • unbranched and branched alkyl such as methyl, ethyl, propyl, 1-methyle
  • halogen-substituted hydrocarbyl groups represented by R ⁇ include, but are not limited to, 3,3,3-trifluoropropyl, 3- chloropropyl, chlorophenyl, and dichlorophenyl.
  • the divalent organic groups represented by Y typically have from 1 to 8 carbon atoms, alternatively from 2 to 6 carbon atoms. In addition to carbon and hydrogen, the divalent organic groups may contain other atoms such as nitrogen, oxygen, and halogen.
  • hydrocarbylene such as methylene, propylene, and phenylene
  • halogen-substituted hydrocarbylene such as chloroethylene and fluoroethylene
  • alkyleneoxyalkylene such as - CH2OCH2CH2CH2-, -CH 2 CH 2 OCH CH -, -CH 2 CH 2 OCH(CH3)CH 2 -, and
  • difunctional silanes include, but are not limited to, dichloromethylsilane, dichlorosilane, dichloroethylsilane, dichlorophenylsilane, allyldichlorosilane, diiodosilane, and diisopropoxymethylsilane.
  • the difunctional silane can be a single silane or a mixture comprising two or more different silanes, each having the formula RlHSiX ⁇ , wherein Rl and ⁇ l are as described and exemplified above. Methods of preparing difunctional silanes are well known in the art; many of these silanes are commercially available.
  • the polyfunctional silane is selected from at least one trifunctional silane having the formula RlSiX 2 3 and at least one tetrafunctional silane having the formula X 4 SiX 3 3 , wherein Rl, X 2 , X 3 and X 4 are as described and exemplified above.
  • trifunctional silanes include, but are not limited to, triisopropoxymethylsilane, triisopropoxyvinylsilane, tri-t-butoxymethylsilane, tri-t- butoxyvinylsilane, triacetoxymethylsilane, triisopropoxysilane, and trichlorosilane.
  • the trifunctional silane can be a single silane or a mixture comprising two or more different silanes each having the formula RlSiX 2 3, wherein R and X 2 are as defined and exemplified above.
  • Methods of preparing trifunctional silanes are well known in the art; many of these silanes are commercially available.
  • tetrafunctional silanes include, but are not limited to, tri-t- butoxysilanol, tetraisopropoxysilane, tetra-t-butoxysilane, tetrachlorosilane, tetraiodosilane, diacetoxy-di-t-butoxysilane, and tetrakis(methoxypropoxy)silane.
  • the tetrafunctional silane can be a single silane or a mixture comprising two or more different silanes each having the formula X SiX 3, wherein X 3 and X 4 are as described and exemplified above.
  • Methods of preparing tetrafunctional silanes are well known in the art; many of these silanes are commercially available.
  • the Lewis acid catalyst is at least one Lewis acid catalyst capable of promoting a condensation reaction between the silicon-bonded groups X* in the difunctional silane and the silicon-bonded groups X 2 , or X 3 and X 4 in the polyfunctional silane .
  • Lewis acid catalysts include, but are not limited to, catalysts having the following formulae: AICI3, FeCl3, BCI3, and ZnCl2.
  • the Lewis acid catalyst can be a single Lewis acid catalyst or a mixture comprising two or more different Lewis acid catalysts.
  • the organic solvent can be any aprotic or dipolar aprotic organic solvent that does not react with the difunctional silane, the polyfunctional silane, or the hyperbranched polysiloxane produced under the conditions of the present method, and is miscible with the difunctional silane, the polyfunctional silane, and the hyperbranched polysiloxane.
  • organic solvents include, but are not limited to, saturated aliphatic hydrocarbons such as n-pentane, hexane, n-heptane, isooctane and dodecane; cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; cyclic ethers such as tetrahydrofuran (THF) and dioxane; ketones such as methyl isobutyl ketone (MIBK); halogenated alkanes such as trichloroethane; and halogenated aromatic hydrocarbons such as bromobenzene and chlorobenzene.
  • saturated aliphatic hydrocarbons such as n-pentane, hexane, n-heptane, isooctane and dodecane
  • the organic solvent can be a single organic solvent or a mixture comprising two or more different organic solvents, each as defined above.
  • the reaction can be carried out in any standard reactor suitable for reacting halosilanes with alkoxysilanes or acyloxysilanes. Suitable reactors include glass and Teflon- lined glass reactors. Preferably, the reactor is equipped with a means of agitation, such as stirring.
  • the reaction can be carried out at atmospheric, subatmospheric, or supraatmospheric pressure. Also, preferably, the reaction is carried out in an inert atmosphere, such as nitrogen or argon, in the absence of moisture.
  • the difunctional silane, polyfunctional silane, Lewis acid catalyst, and organic solvent can be combined in any order.
  • the Lewis acid catalyst is added to a mixture comprising the difunctional silane, polyfunctional silane, and, optionally, organic solvent.
  • the reaction is typically carried out at a temperature of from room temperature ( ⁇ 23 °C) to 150 °C, alternatively from 40 tolOO °C.
  • the reaction is initially conducted at room temperature and then at an elevated temperature. When the temperature is less than room temperature, the rate of reaction is typically very slow. When the temperature is greater than 150 °C, volatile components may be lost from the reaction mixture.
  • the reaction is typically carried out for a period of time sufficient to achieve a constant viscosity of the reaction mixture. The reaction time depends on several factors, such as the structures of the difunctional silane, polyfunctional silane, and Lewis acid, and the temperature. The time of reaction is typically from 2 to 48 h at a temperature of from room temperature to 150 °C. The optimum reaction time can be readily determined by routine experimentation using the methods set forth in the Examples section below.
  • the mole ratio of the difunctional silane to the polyfunctional silane is typically from 0.8:1 to 1.2:1, alternatively from 0.9:1 to 1.1:1.
  • the mole ratio of the difunctional silane to the polyfunctional silane is less than 0.8:1 or greater than 1.2:1, the hyperbranched polysiloxane has a lower molecular weight.
  • the concentration of the Lewis acid catalyst is sufficient to catalyze the condensation reaction of the difunctional silane with the polyfunctional silane.
  • concentration of the Lewis acid catalyst is from 0.1 to 3% (w/w), alternatively from 0.5 to 1%
  • the concentration of the organic solvent is typically from 0 to 50% (w/w), based on the total weight of the reaction mixture.
  • the hyperbranched polysiloxane (I or II) can be separated from volatile solvent and/or by-products by conventional methods of evaporation.
  • the reaction mixture can be heated under reduced pressure, or heated and purged with an inert gas, such as nitrogen.
  • the resulting product can be used without further purification in step (B) of the present method, described below.
  • step (A) The hyperbranched polysiloxane produced in step (A) is reacted with an endblocking agent selected from at least one silane having the formula R 2R 4 SiX ⁇ , at least one disiloxane having the formula (R 3 2R 4 SiO)2, at least one disilazane having the formula
  • R 3 2R ⁇ Si)2NH and a mixture comprising at least two of the preceding agents, in the presence of water and an effective amount of a water-miscible organic solvent, wherein R is Ci to Ci o hydrocarbyl free of aliphatic unsaturation; R 4 is R 3 , H, or -(CH2)q-Cz, wherein
  • Cz is N-carbazolyl and q is an integer from 2 to 10; R ⁇ is R 3 or -H; and X ⁇ is a hydrolysable group or -OH.
  • the endblocking agent is selected from at least one silane having the formula R 3 2R 4 Si ⁇ 5, a t ⁇ eas t one disiloxane having the formula (R 2R 4 SiO)2, at least one disilazane having the formula (R ⁇ R ⁇ Si ⁇ NH, and a mixture comprising at least two of the preceding agents, wherein R 3 , R 4 , and R ⁇ are as described and exemplified above for the hyperbranched polysiloxane (a)(i), and X ⁇ is a hydrolysable group or -OH.
  • hydrolysable group means the silicon-bonded group X ⁇ can react with water to form a silicon-bonded -OH (silanol) group.
  • R 2 is Cj to Cg hydrocarbyl free of aliphatic unsaturation or halogen-substituted hydrocarbyl free of aliphatic unsaturation and Y is a divalent organic group, as described and exemplified above.
  • Examples of silanes having the formula R 3 2R 4 Si ⁇ 5, wherein R 3 and R 4 are as defined and exemplified above, and X ⁇ is a hydrolysable group or -OH include, but are not limited to, chlorodimethylsilane, chlorotrimethylsilane, chloromethylphenylsilane, triethylsilanol, triphenylsilanol, allylchlorosilane, and acetoxydimethylsilane.
  • the silane can be a single silane or a mixture comprising two or more different silanes, each having the formula R 3 2R 4 Si ⁇ 5, wherein R 3 , R 4 , and X ⁇ are as defined and exemplified above.
  • silanes are well known in the art; many of these silanes are commercially available.
  • the silane having the formula R 3 2R 4 Si ⁇ 5, wherein R 4 is -(CH 2 )q-
  • disiloxanes having the formula (R 3 2R SiO)2, wherein R 3 and R 4 are as described and exemplified above include, but are not limited to, 1,1,3,3- tetramethyldisiloxane, 1,1,3,3 -tetraethyldisiloxane, 1 ,3 -dimethyl- 1 ,3 -diphenyldisiloxane, hexamethyldisiloxane, and pentamethyldisiloxane.
  • the disiloxane can be a single disiloxane or a mixture comprising two or more different disiloxanes, each having the formula (R 3 2R 4 SiO)2, wherein R 3 and R 4 are as described and exemplified above.
  • disiloxanes are well known in the art; many of these disiloxanes are commercially available.
  • disilazanes having the formula (R 3 2 R ⁇ Si) 2 NH include, but are not limited to, hexamethyldisilazane, tetramethyldisilazane, and pentamethyldisilazane.
  • the disilazane can be a single disilazane or a mixture comprising two or more different disilazanes, each having the formula (R 3 2 R ⁇ Si) 2 NH wherein R 3 and R ⁇ are as described and exemplified above.
  • Methods of preparing disilazanes are well known in the art; many of these disilazanes are commercially available.
  • the endblocking agent can be a single endblocking agent selected from the silane, disiloxane, and disilazane, described above, or a mixture comprising at least two of the agents.
  • water-miscible organic solvent means the organic solvent is substantially miscible with water or completely miscible (i.e., miscible in all proportions) with water.
  • solubility of the water-miscible orgamc solvent in water is typically at least 90 g/100 g of water at 25 °C.
  • water-miscible organic solvents include, but are not limited to, monohydric alcohols such as methanol, ethanol, 1-propanol, and 2-propanol; dihydric alcohols such as ethylene glycol and propylene glycol; polyhydric alcohols such as glycerol and pentaerythritiol; and dipolar aproptic solvents such as N,N- dimethylformamide, tetrahydrofuran, dimethyl sulfoxide, and acetonitrile.
  • the water- miscible organic solvent can be a single water-miscible organic solvent or a mixture comprising two or more different water-miscible organic solvents, each as defined above.
  • the reaction mixture can further comprise a condensation catalyst.
  • hydrolysable group that does not react with water to form an acid means the hydrolysable group does not react with water in the absence of a catalyst at any temperature from room temperature to 100 °C within several minutes, for example thirty minutes, to form an acid.
  • the condensation catalyst can be any condensation catalyst typically used to promote condensation of silicon-bonded hydroxy (silanol) groups to form Si-O-Si linkages.
  • condensation catalysts include, but are not limited to, tin(II) and tin(IV) compounds such as tin dilaurate, tin dioctoate, and tetrabutyl tin; and titanium compounds such as titanium tetrabutoxide.
  • the concentration of the condensation catalyst is typically from 0.1 to 10% (w/w), alternatively from 0.5 to 5% (w/w), alternatively from 1 to 3% (w/w), based on the total weight of the hyperbranched polysiloxane (I or II).
  • the reaction can be carried out in any standard reactor suitable for reacting halosilanes with disiloxanes or disilazanes in the presence of water.
  • Suitable reactors include glass and Teflon-lined glass reactors.
  • the reactor is equipped with a means of agitation, such as stirring.
  • the reaction can be carried out at atmospheric, subatmospheric, or supraatmospheric pressure.
  • the reaction is carried out in an inert atmosphere, such as nitrogen or argon.
  • water is added slowly to a mixture comprising the hyperbranched polysiloxane (I or II), the endblocking agent, and the water-miscible organic solvent.
  • the reaction is typically carried out at a temperature of from 0 to 100 °C, alternatively from room temperature ( ⁇ 23 °C) to 80 °C. When the temperature is less than 0 °C, the rate of reaction is typically very slow. When the temperature is greater than 100 °C, the Si-H groups in the hyperbranched polysiloxane may be converted into silanol groups (Si- OH).
  • the reaction is typically carried out for a period of time sufficient to complete the condensation reaction between the hyperbranched polysiloxane (I or II) and the endblocking agent.
  • complete the condensation reaction means the hyperbranched polysiloxane product does not contain silicon-bonded groups X , X 2 , X 3 , or X 4 , as determined by NMR.
  • the reaction time depends on several factors, such as the structures of the hyperbranched polysiloxane (I or II) and the endblocking agent, and the temperature.
  • the time of reaction is typically from 2 to 48 h at a temperature of from 0 to 100 °C. The optimum reaction time can be readily determined by routine experimentation using the methods set forth in the Examples section below.
  • the mole ratio of the endblocking agent to the silicon-bonded groups X 2 in the hyperbranched polysiloxane (I) is typically from 1:1 to 2:1, alternatively from 1.1:1 to 1.5:1.
  • the mole ratio of the endblocking agent to the silicon-bonded groups X 3 in the hyperbranched polysiloxane (II) is typically from 1:1 to 2:1, alternatively from 1.1:1 to 1.5:1.
  • the concentration of water in the reaction mixture depends on the nature of ⁇ l , X 2 ,
  • the concentration of water is typically from 0.5 to 10% (w/w), alternatively from 1 to 3% (w/w), based on the total weight of the reaction mixture.
  • the endblocking agent has the formula R 2 R 4 Si ⁇ 5, wherein ⁇ 5 is -OH, only a trace amount, for example, 100 ppm, of water is required in the reaction mixture.
  • the water-miscible organic solvent is present in an effective amount in the reaction mixture.
  • the term "effective amount” means the concentration of the water- miscible solvent is such that the hyperbranched polysiloxane (I or II) and the endblocking agent are soluble in the reaction mixture containing the water-miscible organic solvent.
  • the concentration of the water-miscible organic solvent is typically from about 50 to 99% (w/w), alternatively from 50 to 90% (w/w), alternatively from 60 to 80% (w/w), based on the total weight of the reaction mixture.
  • the effective amount of the water-miscible organic solvent can be determined by routine experimentation using the methods in the Examples below.
  • Hyperbranched polysiloxane (a)(i) or (a)(ii) can be recovered from the reaction mixture by filtering the mixture to remove any Lewis acid catalyst introduced into the reaction mixture from the hyperbranched polysiloxane (I or II), and then evaporating the volatile solvent and/or by-products.
  • Conventional methods of evaporation can be used.
  • the mixture can be heated under reduced pressure, or heated and purged with an inert gas, such as nitrogen.
  • Hydrosilylation catalyst (c) can be any of the well-known hydrosilylation catalysts comprising a platinum group metal (i.e., platinum, rhodium, ruthenium, palladium, osmium and iridium) or a compound containing a platinum group metal.
  • a platinum group metal i.e., platinum, rhodium, ruthenium, palladium, osmium and iridium
  • the platinum group metal is platinum, based on its high activity in hydrosilylation reactions.
  • Preferred hydrosilylation catalysts include the complexes of chloroplatinic acid and certain vinyl-containing organosiloxanes disclosed by Willing in U.S. Pat. No. 3,419,593, which is hereby incorporated by reference.
  • a preferred catalyst of this type is the reaction product of chloroplatinic acid and l,3-diethenyl-l,l,3,3-tetramethyldisiloxane.
  • Organic solvent (d) is at least one organic solvent.
  • the organic solvent can be any aprotic or dipolar aprotic organic solvent that does not react with hyperbranched polysiloxane
  • organic solvents include, but are not limited to, saturated aliphatic hydrocarbons such as n-pentane, hexane, n-heptane, isooctane and dodecane; cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; cyclic ethers such as tetrahydrofuran (THF) and dioxane; ketones such as methyl isobutyl ketone (MIBK); halogenated alkanes such as trichloroethane; and halogenated aromatic hydrocarbons such as bromobenzene and chlorobenzene.
  • Organic solvent (d) can be a single organic solvent or a mixture comprising two or more different organic solvents, each as defined above.
  • N-alkenyl carbazole (b) can be a single N-alkenyl carbazole or a mixture comprising two or more different N-alkenyl carbazoles, each having the formula wherein Cz and q are as defined and exemplified above.
  • Hydrosilylation catalyst (c) can be any of the well-known hydrosilylation catalysts comprising a platinum group metal (i.e., platinum, rhodium, ruthenium, palladium, osmium and iridium) or a compound containing a platinum group metal.
  • a platinum group metal i.e., platinum, rhodium, ruthenium, palladium, osmium and iridium
  • the platinum group metal is platinum, based on its high activity in hydrosilylation reactions.
  • Preferred hydrosilylation catalysts include the complexes of chloroplatinic acid and certain vinyl-containing organosiloxanes disclosed by Willing in U.S. Pat. No. 3,419,593, which is hereby incorporated by reference.
  • a preferred catalyst of this type is the reaction product of chloroplatinic acid and l,3-diethenyl-l,l,3,3-tetramethyldisiloxane.
  • Organic solvent (d) is at least one organic solvent.
  • the organic solvent can be any aprotic or dipolar aprotic organic solvent that does not react with hyperbranched polysiloxane
  • organic solvents include, but are not limited to, saturated aliphatic hydrocarbons such as n-pentane, hexane, n-heptane, isooctane and dodecane; cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; cyclic ethers such as tetrahydrofuran (THF) and dioxane; ketones such as methyl isobutyl ketone (MIBK); halogenated alkanes such as trichloroethane; and halogenated aromatic hydrocarbons such as bromobenzene and chlorobenzene.
  • Organic solvent (d) can be a single organic solvent or a mixture comprising two or more different organic solvents, each as defined above.
  • the reaction can be carried out in any standard reactor suitable for hydrosilylation reactions. Suitable reactors include glass and Teflon-lined glass reactors. Preferably, the reactor is equipped with a means of agitation, such as stirring. Also, preferably, the reaction is carried out in an inert atmosphere, such as nitrogen or argon, in the absence of moisture.
  • Hyperbranched polysiloxane (a), N-alkenyl carbazole, hydrosilylation catalyst, and organic solvent can be combined in any order. Typically, N-alkenyl carbazole (b) is added to hyperbranched polysiloxane (a), and, optionally organic solvent (d) before the introduction of hydrosilylation catalyst (c).
  • hydrosilylation catalyst (c) is added to the mixture of (a), (b), and (d).
  • organic solvent (d) is not present, the mixture of (a) and (b) is heated to a temperature sufficient to form a homogeneous mixture, for example 60 °C, and hydrosilylation catalyst (c) is added to the mixture.
  • the reaction is typically carried out at a temperature of from 0 to 140 °C, alternatively from room temperature (-23 °C) to 140 °C. When the temperature is less than 0 °C, the rate of reaction is typically very slow.
  • the reaction time depends on several factors, such as the structures of the hyperbranched polysiloxane (a) and N-alkenyl carbazole, and the temperature.
  • the time of reaction is typically from 2 to 48 h at a temperature of from 0 to 140 °C.
  • the optimum reaction time can be determined by routine experimentation using the methods set forth in the Examples section below.
  • the mole ratio of N-alkenyl carbazole (b) to silicon-bonded hydrogen atoms in hyperbranched polysiloxane (a) is typically from 0.8:1 to 1.5:1, alternatively from 1:1 to 1.5:1, alternatively from 1:1 to 1.2:1.
  • the concentration of hydrosilylation catalyst (c) is sufficient to catalyze the addition reaction of hyperbranched polysiloxane (a) with N-alkenyl carbazole (b).
  • the concentration of hydrosilylation catalyst (c) is sufficient to provide from 0.1 to 1000 ppm of a platinum group metal, alternatively from 1 to 500 ppm of a platinum group metal, alternatively from 5 to 150 ppm of a platinum group metal, based on the combined weight of hyperbranched polysiloxane (a) and N-alkenyl carbazole (b). The rate of reaction is very slow below 0.1 ppm of platinum group metal.
  • the concentration of organic solvent (d) is typically from 0 to 60% (w/w), alternatively from 30 to 60% (w/w), alternatively from 40 to 50% (w/w), based on the total weight of the reaction mixture.
  • the first carbazolyl-functional hyperbranched polysiloxane can be recovered from the reaction mixture by adding sufficient quantity of an alcohol to effect precipitation of the polysiloxane and then filtering the reaction mixture to obtain the polysiloxane.
  • the alcohol typically has from 1 to 6 carbon atoms, alternatively from 1 to 3 carbon atoms.
  • the alcohol can have a linear, branched, or cyclic structure.
  • the hydroxy group in the alcohol may be attached to a primary, secondary, or tertiary aliphatic carbon atom.
  • alcohols include, but are not limited to, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl- 1-butanol, 1-pentanol, and cyclohexanol.
  • the first carbazolyl-function hyperbranched polysiloxane typically has a number- average molecular weight of from 1,500 to 1,000,000, alternatively from 1,500 to 100,000, alternatively from 1,500 to 50,000, where the molecular weight is determined by gel permeation chromatography employing a low angle laser light scattering detector.
  • a second carbazolyl-functional hyperbranched polysiloxane is prepared by a method comprising reacting (a) a hyperbranched polysiloxane having a formula selected from: and (ii) (RlHSi ⁇ 2/2)v'(R 1 Si ⁇ 3/2) w R 3 2R 4 SiO 1 /2) x R 3 2R 5 SiO ⁇ /2) y .(SiO 4 /2) z (IV)
  • R6 is a divalent organic group
  • X ⁇ is a hydrolysable group
  • Cz is N-carbazolyl
  • Hyperbranched polysiloxanes (a)(i) and (a)(ii), alkenyl carbazole (b), hydrosilylation catalyst (c), and organic solvent (d) are as described and exemplified above in the method of preparing the first carbazolyl-functional hyperbranched polysiloxane.
  • Alkenyl silane (e) is at least one alkenyl silane having a formula selected from X 7 3_ and r are as defined and exemplified above, and X 7 is a hydrolysable group as defined and exemplified above for ⁇ 5 in the method of preparing hyperbranched polysiloxanes (a)(i) and (a)(ii).
  • Alkenyl silane (e) can be a single alkenyl silane or a mixture comprising two or more different alkenyl silanes, each having a formula selected from X 7 3_ r R r Si-R6-
  • alkenyl silanes can be prepared by direct syntheses, Grignard reactions, addition of organosilicon hydrides to alkenes or alkynes, condensation of chloroolefins with organosilicon hydrides, and dehydrohalogenation of haloalkylsilanes. These and other methods are described by W. Noll in Chemistry and Technology of Silicones, Academic Press:New York, 1968.
  • the reaction for preparing the second carbazolyl-functional hyperbranched polysiloxane can be carried out in the manner described above for preparing the first carbazolyl-functional hyperbranched polysiloxane, except the mole ratio of the N-alkenyl carbazole (b) to the silicon-bonded hydrogen atoms in the hyperbranched polysiloxane (a) is typically from 0.8:1 to 1:1, alternatively from 0.95:1 to 1:1 and the reaction mixture further comprises alkenyl silane (e), wherein the mole ratio of alkenyl silane (e) to the silicon bonded hydrogen atoms in hyperbranched polysiloxane (a) is typically from 0.01:1 to 0.15:1, alternatively from 0.05:1 to 0.1:1.
  • the second carbazolyl-functional hyperbranched polysiloxane can be recovered from the reaction mixture as described above for the first carbazolyl-functional hyperbranched polysiloxane.
  • the second carbazolyl-function hyperbranched polysiloxane typically has a number- average molecular weight of from 1,500 to 1,000,000, alternatively from 1,500 to 100,000, alternatively from 1,500 to 50,000, where the molecular weight is determined by gel permeation chromatography employing a low angle laser light scattering detector.
  • a silicone composition according to the present invention comprises (A) the second carbazolyl-functional hyperbranched polysiloxane, and (B) an organic solvent.
  • Component (B) is at least one organic solvent.
  • organic solvents include, but are not limited to, saturated aliphatic hydrocarbons such as n-pentane, hexane, n- heptane, isooctane and dodecane; cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; cyclic ethers such as tetrahydrofuran (THF) and dioxane; ketones such as methyl isobutyl ketone (MIBK); halogenated alkanes such as trichloroethane; and halogenated aromatic hydrocarbons such as bromobenzene and chlorobenzene.
  • Component (B) can be a single organic solvent or a mixture comprising two or more different organic solvents, each as defined above.
  • the concentration of the organic solvent is typically from 70 to 99% (w/w), alternatively from 85 to 99% (w/w), based on the total weight of the silicone composition.
  • the silicone composition can further comprise at least one condensation catalyst.
  • the condensation catalyst can be any condensation catalyst typically used to promote condensation of silicon-bonded hydroxy (silanol) groups to form Si-O-Si linkages. Examples of condensation catalysts include, but are not limited to, tin(II) and tin(IV) compounds such as tin dilaurate, tin dioctoate, and tetrabutyl tin; and titanium compounds such as titanium tetrabutoxide.
  • the concentration of the condensation catalyst is typically from 0.1 to 10% (w/w), alternatively from 0.5 to 5% (w/w), alternatively from 1 to 3% (w/w), based on the total weight of component (A).
  • the silicone composition of the instant invention is typically prepared by combining components (A) and (B) and any optional ingredients in the stated proportions at ambient temperature.
  • Mixing can be accomplished by any of the techniques known in the art such as milling, blending, and stirring, either in a batch or continuous process.
  • the particular device is determined by the viscosity of the components and the viscosity of the final silicone composition.
  • a cured carbazolyl-functional polysiloxane according to the present invention is prepared by curing the silicone composition, described above.
  • the silicone composition can be cured by exposing the composition to moisture at moderate temperature. Cure can be accelerated by application of heat and/or exposure to high humidity. The rate of cure depends on a number of factors, including temperature, humidity, structure of the carbazolyl- functional linear polysiloxane, and nature of the hydrolysable groups.
  • the silicone composition can be cured by exposing the composition to a relative humidity of about 30% at a temperature of from about room temperature (23 °C) to about 150 °C, for period from 0.5 to 72 h.
  • a first organic light-emitting diode comprises : a substrate having a first opposing surface and a second opposing surface; a first electrode layer overlying the first opposing surface; a light-emitting element overlying the first electrode layer, the light emitting element comprising a hole-transport layer and an electron-transport layer, wherein the hole-transport layer and the electron-transport layer lie directly on one another, and one of the hole-transport layer and the electron- transport layer comprises the first carbazolyl-functional hyperbranched polysiloxane; and a second electrode layer overlying the light-emitting element.
  • a second organic light-emitting diode comprises: a substrate having a first opposing surface and a second opposing surface; a first electrode layer overlying the first opposing surface; a light-emitting element overlying the first electrode layer, the light emitting element comprising a hole-transport layer and an electron-transport layer, wherein the hole-transport layer and the electron-transport layer lie directly on one another, and one of the hole-transport layer and the electron- transport layer comprises a cured carbazolyl-functional polysiloxane prepared by curing the silicone composition of the present invention; and a second electrode layer overlying the light-emitting element.
  • the term "overlying" used in reference to the position of the first electrode layer, light-emitting element, and second electrode layer relative to the designated component means the particular layer either lies directly on the component or lies above the component with one or more intermediary layers there between, provided the OLED is oriented with the substrate below the first electrode layer as shown in Figures 1-4.
  • the term “overlying” used in reference to the position of the first electrode layer relative to the first opposing surface of the substrate in the OLED means the first electrode layer either lies directly on the surface or is separated from the surface by one or more intermediate layers.
  • the substrate can be a rigid or flexible material having two opposing surfaces. Further, the substrate can be transparent or nontransparent to light in the visible region of the electromagnetic spectrum.
  • the term “transparent” means the particular component (e.g., substrate or electrode layer) has a percent transmittance of at least 30%, alternatively at least 60%, alternatively at least 80%, for light in the visible region ( ⁇ 4O0 to -700 nm) of the electromagnetic spectrum. Also, as used herein, the term “nontransparent” means the component has a percent transmittance less than 30% for light in the visible region of the electromagnetic spectrum.
  • substrates include, but are not limited to, semiconductor materials such as silicon, silicon having a surface layer of silicon dioxide, and gallium arsenide; quartz; fused quartz; aluminum oxide; ceramics; glass; metal foils; polyolefins such as polyethylene, polypropylene, polystyrene, and polyethyleneterephthalate; fluorocarbon polymers such as polytetrafluoroethylene and polyvinylfluoride; polyamides such as Nylon; polyimides; polyesters such as poly(methyl methacrylate); epoxy resins; polyethers; polycarbonates; polysulfones; and polyether sulfones.
  • the first electrode layer can function as an anode or cathode in the OLED.
  • the first electrode layer may be transparent or nontransparent to visible light.
  • the anode is typically selected from a high work-function (> 4 eV) metal, alloy, or metal oxide such as indium oxide, tin oxide, zinc oxide, indium tin oxide (ITO), indium zinc oxide, aluminum-doped zinc oxide, nickel, and gold.
  • the cathode can be a low work-function ( ⁇ 4 eV) metal such as Ca, Mg, and Al; a high work-function (> 4 eV) metal, alloy, or metal oxide, as described above; or an alloy of a low- work function metal and at least one other metal having a high or low work-function, such as Mg-Al, Ag-Mg, Al-Li, In-Mg, and Al-Ca.
  • Methods of depositing anode and cathode layers in the fabrication of OLEDs, such as evaporation, co-evaporation, DC magnetron sputtering ,or RF sputtering, are well known in the art.
  • the light-emitting element comprises a hole-transport layer and an electron- transport layer wherein the hole-transport layer and the electron-transport layer lie directly on one another, and one of the hole-transport layer and the electron-transport layer comprises the first carbazolyl-functional hyperbranched polysiloxane or a cured carbazolyl-functional polysiloxane prepared by curing the silicone composition of the invention.
  • the orientation of the light-emitting element depends on the relative positions of the anode and cathode in the OLED.
  • the hole-transport layer is located between the anode and the electron-transport layer and the electron-transport layer is located between the hole-transport layer and the cathode.
  • the thickness of the hole-transport layer is typically from 20 to 100 nm, alternatively from 30 to 50 nm.
  • the thickness of the electron-transport layer is typically from 20 to 100 nm, alternatively from 30 to 50 nm.
  • the first carbazolyl-functional hyperbranched polysiloxane and the silicone composition used to prepare the cured carbazolyl-functional polysiloxane can be applied to the first electrode layer, the hole-transport layer, or the electron-transport layer, depending on the configuration of the OLED, using conventional methods such as spin-coating, dipping, spraying, brushing, and printing.
  • the first carbazolyl-functional hyperbranched polysiloxane can also be dissolved in an organic solvent prior to application, where the organic solvent is as described above for the silicone composition of the invention.
  • the electron-transport layer can be any low molecular weight organic compound or organic polymer typically used as an electron-transport, electron- injection/electron-transport, or light-emitting material in OLED devices.
  • Low molecular weight organic compounds suitable for use as the electron-transport layer are well known in the art, as exemplified in U.S. Patent No. 5,952,778; U.S. Patent No. 4,539,507; U.S. Patent No. 4,356,429; U.S. Patent No.
  • low molecular weight compounds include, but are not limited to, aromatic compounds, such as anthracene, naphthalene, phenanthrene, pyrene, chrysene, and perylene; butadienes such as 1,4-diphenylbutadiene and tetraphenylbutadiene; coumarins; acridine; stilbenes such as trans-stilbene; and chelated oxinoid compounds, such as tris(8- hydroxyquinolato)aluminum(III), Alq3-
  • aromatic compounds such as anthracene, naphthalene, phenanthrene, pyrene, chrysene, and perylene
  • butadienes such as 1,4-diphenylbutadiene and tetraphenylbutadiene
  • coumarins such as acridine
  • stilbenes such as trans-stilbene
  • chelated oxinoid compounds such as tris(8-
  • Organic polymers suitable for use as the electron-transport layer are well known in the art, as exemplified in U.S. Patent No. 5,952,778; U.S. Patent No. 5,247,190; U.S. Patent No. 5,807,627; U.S. Patent No. 6,048,573; and U.S. Patent No. 6,255,774.
  • organic polymers include, but are not limited to, poly(phenylene vinylene)s, such as poly(l,4 phenylene vinylene); poly-(2,5-dialkoxy-l,4 phenylene vinylene)s, such as poly(2-methoxy- 5-(2-ethylhexyloxy)-l ,4-phenylenevinylene) (MEHPPV), poly(2-methoxy-5-(2- methylpentyloxy)- 1 ,4-phenylenevinylene), poly(2-methoxy-5-pentyloxy- 1 ,4- phenylenevinylene), and poly(2-methoxy-5-dodecyloxy-l,4-phenylenevinylene); poly(2,5- dialkyl-1,4 phenylene vinylene)s; poly(phenylene); poly(2,5-dialkyl-l,4 phenylene)s; poly(p- phenylene); poly(thiophene)s, such as
  • the hole-transport layer can be any organic compound typically used as a hole-transport, hole-injection, or hole-injection/hole-transport material in OLED devices.
  • Organic compounds suitable for use as the hole-transport layer are well known in the art, as exemplified in U.S. Patent No. 4, 720,432; U.S. Patent No. 5,593,788; U.S. Patent No. 5,969,474; U.S. Patent No. 4,539,507; U/.S. Patent no.
  • organic compounds include, but are not limited to, aromatic tertiary amines, such as monoarylamines, diarylamines, triarylamines, and tetraaryldiamines; hydrazones; carbazoles; triazoles; imidazoles; oxadiazoles having an amino group; polythiophenes, such as poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate), which is sold under the name Baytron® P by H.C. Starck Inc.; and porphyrinic compounds, such as phthalocyanines and metal-containing phthalocyanines.
  • the organic compounds can be applied by conventional thin-film preparation techniques including vacuum evaporation and sublimation.
  • the electron-transport layer or the hole-transport layer in the light-emitting layer in the light-emitting element can further comprise a fluorescent dye. Fluorescent dyes suitable for use in OLED devices are well known in the art, as illustrated in U.S. Patent No. 4,769,292.
  • fluorescent dyes include, but are not limited to, coumarins; dicyanomethylenepyrans, such as 4-(dicyanomethylene)-2-methyl-6-(p- dimethylaminostyryl)4H-pyran; dicyanomethylenethiopyrans; polymethine; oxabenzanthracene; xanthene; pyrylium and thiapyrylium; cabostyril; and perylene fluorescent dyes.
  • dicyanomethylenepyrans such as 4-(dicyanomethylene)-2-methyl-6-(p- dimethylaminostyryl)4H-pyran
  • dicyanomethylenethiopyrans polymethine
  • oxabenzanthracene xanthene
  • pyrylium and thiapyrylium cabostyril
  • perylene fluorescent dyes include, but are not limited to, coumarins; dicyanomethylenepyrans, such as 4-(dicyanomethylene)
  • the second electrode layer can function either as an anode or cathode in the OLED.
  • the second electrode layer may be transparent or nontransparent to light in the visible region. Examples of anode and cathode materials and methods for their formation are as described above for the first electrode layer.
  • the OLED of the present invention can further comprise a hole-injection layer interposed between the anode and the hole-transport layer, and/or an electron-injection layer interposed between the cathode and the electron-transport layer.
  • the hole-injection layer typically has a thickness of from 5 to 20 nm, alternatively from 7 to 10 nm. Examples of materials suitable for use as the hole-injection layer include, but are not limited to, copper phthalocyanine.
  • the electron-injection layer typically has a thickness of from 0.5 to 5 nm, alternatively from 1 to 3 nm.
  • Examples of materials suitable for use as the electron-injection layer include, but are not limited to, alkali metal fluorides, such as lithium, fluoride and cesium fluoride; and alkali metal carboxylates, such as lithium acetate and cesium acetate.
  • alkali metal fluorides such as lithium, fluoride and cesium fluoride
  • alkali metal carboxylates such as lithium acetate and cesium acetate.
  • the hole-injection layer and the hole-injection layer can be formed by conventional techniques, thermal evaporation.
  • a first embodiment of an OLED according to the present invention comprises a substrate 100 having a first opposing surface 100A and a second opposing surface 100B, a first electrode layer 102 on the first opposing surface 100A, wherein the first electrode layer 102 is an anode, a light-emitting element 104 overlying the first electrode layer 102, wherein the light-emitting element 104 comprises a hole-transport layer 106 and an electron-transport layer 108 lying directly on the hole-transport layer 106, wherein the hole-transport layer 106 comprises a carbazolyl-functional hyperbranched polysiloxane or a cured carbazolyl-functional polysiloxane, and a second electrode layer 110 overlying the light-emitting element 104, wherein the second electrode layer 110 is a cathode.
  • a second embodiment of an OLED comprises a substrate 200 having a first opposing surface 2O0A and a second opposing surface 200B, a first electrode layer 202 on the first opposing surface 200A, wherein the first electrode layer 202 is an anode, a light-emitting element 204 overlying the first electrode layer 202, wherein the light-emitting element 204 comprises a hole-transport layer 206 and an electron-transport layer 208 lying directly on the hole-transport layer 206, wherein the electron-transport layer 208 comprises a carbazolyl-functional hyperbranched polysiloxane or a cured carbazolyl-functional polysiloxane, and a second electrode layer 210 overlying the light-emitting element 204, wherein the second electrode layer 210 is a cathode.
  • a third embodiment of an OLED according to the present invention comprises a substrate 300 having a first opposing surface 3O0A and a second opposing surface 300B, a first electrode layer 302 on the first opposing surface 300A, wherein the first electrode layer 302 is a cathode, a light-emitting element 304 overlying the first electrode layer 302, wherein the light-emitting element 304 comprises an electron- transport layer 308 and a hole-transport layer 306 lying directly on the electron-transport layer 306, wherein the hole-transport layer 306 comprises a carbazolyl-functional hyperbranched polysiloxane or a cured carbazolyl-functional polysiloxane, and a second electrode layer 310 overlying the light-emitting element 304, wherein the second electrode layer 310 is an anode.
  • a fourth embodiment of an OLED according to the present invention comprises a substrate 400 having a first opposing surface 4O0A and a second opposing surface 400B, a first electrode layer 402 on the first opposing surface 400A, wherein the first electrode layer 402 is a cathode, a light-emitting element 404 overlying the first electrode layer 402, wherein the light-emitting element 404 comprises an electron- transport layer 408 and a hole-transport layer 406 lying directly on the electron-transport layer 408, wherein the electron-transport layer 408 comprises a carbazolyl-functional hyperbranched polysiloxane or a cured carbazolyl-functional polysiloxane, and a second electrode layer 410 overlying the light-emitting element 404, wherein the second electrode layer 410 is an anode.
  • the carbazolyl-functional hyperbranched polysiloxanes of the present invention exhibit electroluminescence, emitting light when subjected to an applied voltage.
  • the hyperbranched polysiloxanes containing hydrolysable groups can be cured to produce durable cross-linked polysiloxanes.
  • the carbazolyl-functional hyperbranched polysiloxanes can be doped with small amounts of fluorescent dyes to enhance the electroluminescent efficiency and control the color output of the carbazolyl-functional hyperbranched polysiloxane or cured carbazolyl-functional polysiloxane.
  • the silicone composition of the present invention can be conveniently formulated as a one-part composition. Moreover, the silicone composition has good shelf-stability in the absence of moisture. Importantly, the composition can be applied to a substrate by conventional high-speed methods such as spin coating, printing, and spraying. Also, the silicone composition can be readily cured by exposure to moisture at mild to moderate temperatures.
  • the cured carbazolyl-functional polysiloxane prepared by curing the silicone composition of the present invention exhibits electroluminescence. Moreover, the cured polysiloxane has good primerless adhesion to a variety of substrates. The cured polysiloxane also exhibits excellent durability, chemical resistance, and flexibility at low temperatures.
  • the cured polysiloxane exhibits high transparency, typically at least 95% transmittance at a thickness of 100 nm, in the visible region of the electromagnetic spectrum.
  • the polysiloxane is substantially free of acidic or basic components, which are detrimental to the electrode and light-emitting layers in OLED devices.
  • the OLED of the present invention exhibits good resistance to abrasion, organic solvents, moisture, and oxygen. Moreover, the OLED exhibits high quantum efficiency and photostability.
  • the OLED is useful as a discrete light-emitting device or as the active element of light-emitting arrays or displays, such as flat panel displays.
  • OLED displays are useful in a number of devices, including watches, telephones, lap-top computers, pagers, cellular phones, digital video cameras, DVD players, and calculators.
  • Infrared spectra of hyperbranched polysiloxanes were recorded on a Perkin Elmer Instruments 1600 FT-IR spectrometer. An aliquot of a reaction mixture containing the polysiloxane was dissolved in THF or toluene to achieve a concentration of approximately 10%. A drop of the solution was applied to aNaCl window and the solvent was evaporated under a stream of dry nitrogen to form a thin film of the polysiloxane.
  • M n and M w Number-average and weight-average molecular weights (M n and M w ) of hyperbranched polysiloxanes were determined by gel permeation chromatography (GPC) using a PLgel (Polymer Laboratories, Inc.) 5- ⁇ m column at room temperature ( ⁇ 23 °C), a THF mobile phase at 1 mL/min, and a refractive index detector. Polystyrene standards were used for linear regression calibrations.
  • ITO-coated glass slides (Thin Film Technology, Inc., Buellton, CA) having a surface resistance of 10 ⁇ /square were cut into 25 -mm square substrates.
  • the substrates were immersed in an ultrasonic bath containing a solution consisting of 1% Alconox powdered cleaner (Alconox, Inc.) in water for 10 min and then rinsed with deionized water.
  • Alconox powdered cleaner Alconox, Inc.
  • the substrates were then immersed sequentially in the each of the following solvents with ultrasonic agitation for 10 min in each solvent: isopropyl alcohol, n-hexane, and toluene.
  • the glass substrates were then dried under a stream of dry nitrogen. Deposition of Alq3 and SiO in OLEDs
  • Alq 3 and silicon monoxide (SiO) were deposited by thermal evaporation using a BOC Edwards Auto 306 high vacuum deposition system equipped with a crystal balance film thickness monitor.
  • the substrate was placed in a rotary sample holder positioned above the source and covered with the appropriate mask.
  • the source was prepared by placing a sample of the organic compound or SiO in an aluminum oxide crucible. The crucible was then positioned in a tungsten wire spiral. The pressure in the vacuum chamber was reduced to
  • the substrate was allowed to outgas for at least 30 minutes at this pressure.
  • the organic or SiO film was deposited by heating the source via the tungsten filament while rotating the sample holder. The deposition rate (0.1 to 0.3 nm per second) and the thickness of the film were monitored during the deposition process.
  • the source was prepared by placing the metal in an aluminum oxide crucible and positioning the crucible in a tungsten wire spiral, or by placing the metal directly in a tungsten basket. When multiple layers of different metals were required, the appropriate sources were placed in a turret that could be rotated for deposition of each metal. The deposition rate (0.1 to 0.3 nm per second) and the thickness of the film were monitored during the deposition process.
  • a portion (3 g) of the resulting viscous fluid, 2.5 g of chlorodimethylsilane, and 10 ml of tetrahydrofuran (THF) were combined in a glass vial. Water (0.5 g) was added to the mixture and the vial was sealed with a cap and kept at room temperature overnight. Most of the THF was evaporated by directing a stream of air across the surface of the mixture to produce a hyperbranched polysiloxane as a viscous fluid.
  • the FTIR spectrum of the polysiloxane showed an Si-H absorption at 2138.6 cm-* with a shoulder at 2184 cm -1 , and a strong absorption at 901 cm "1 .
  • the resulting hyperbranched polysiloxane had a number-average molecular weight and a weight-average molecular weight of 3719 and 9034, respectively.
  • N-Allylcarbazole (2.0 g), 10 mL of anhydrous toluene, and 0.5 g of the hyperbranched polysiloxane of Example 1 were combined in a dry flask.
  • To the mixture was added 0.01 g of a solution consisting of 0.31% of l,3-divinyl-l,l,3,3-tetramethyldisiloxane and 0.19% of a platinum(IV) complex of l,3-divinyl-l,l,3,3-tetramethyldisiloxane in 2- propanol.
  • the flask - was purged with dry nitrogen and sealed with a septum.
  • the mixture was heated at 110 °C for 2 h, and then an aliquot was withdrawn for FTIR analysis.
  • the FTIR spectrum confirmed the absence of an Si-H absorption.
  • the product was extracted with anhydrous 2-propanol three times and then dried in a vacuum oven ( ⁇ 133 Pa) at 70 °C overnight to give a carbazolyl-fiinctional hyperbranched polysiloxane.
  • N-Allylcarbazole (8.0 g) and 2.0 g of the hyperbranched polysiloxane of Example 2 were combined in a dry flask.
  • To the mixture was added 0.025 g of a solution consisting of 0.31% of l,3-divinyl-l,l,3,3-tetramethyldisiloxane and 0.19% of a platinum(IV) complex of l,3-divinyl-l,l ,3,3-tetramethyldisiloxane in dry toluene.
  • the flask was purged with dry nitrogen sealed with a septum, and then heated in an oil bath at 130 °C for 4 h.
  • the material in the flask was dissolved in 3 mL of toluene. Residual N-allylcarbazole was extracted with electronic grade hexane (20 mL). The product was dissolved in a minimal amount of electronic grade toluene and the carbazolyl- functional hyperbranched polysiloxane was precipitated by addition of electronic grade 2- propanol. The dissolution precipitation process was repeated two times.
  • OLEDs were fabricated as follows: Silicon monoxide (100 nm) was thermally deposited along a first edge of a pre-cleaned ITO-coated glass substrate (25 mm x 25 mm) through a mask having a rectangular aperture (6 mm x 25 mm). A strip of 3M Scotch brand tape (5mm x 25mm) was applied along a second edge of the substrate, perpendicular to the SiO deposit.
  • a solution consisting of 1.5% of the carbazolyl-functional hyperbranched polysiloxane of Example 3 in toluene was spin-coated (3,000 rpm, 20 s) over the ITO surface using a CHEMAT Technology Model KW-4A spin-coater to form a hole- transport layer having a thickness of 40 nm.
  • the composite was heated in an oven under nitrogen at 80 °C for 30 min and then allowed to cool to room temperature.
  • Tris(8- hydroxyquinolato)aluminum (III), Alq 3 was thermally deposited on the hole-transport layer to form an electron-transport layer (30 nm).
  • the strip of tape was removed from the substrate to expose the anode (ITO) and four cathodes were formed by depositing aluminum (100 nm) on the electron-transport layer and SiO deposit through a mask having four rectangular apertures (3 mm x 16 mm). Each of the four OLEDs emitted a cyan color light having peak intensity at 505 nm at a turn-on voltage of about 8.5 V.

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Abstract

L'invention concerne des polysiloxanes hyperramifiés à fonctionnalité carbazolyle qui contiennent des groupes N-carbazolylalkyle, une composition de silicone contenant un polysiloxane hyperramifié à fonctionnalité carbazolyle, un polysiloxane traité à fonctionnalité carbazolyle obtenu par le traitement de la composition de silicone et une diode électroluminescente organique (OLED) contenant un polysiloxane hyperramifié à fonctionnalité carbazolyle ou un polysiloxane traité à fonctionnalité carbazolyle.
PCT/US2004/020942 2003-09-11 2004-06-29 Polysiloxanes hyperramifies a fonctionnalite carbazolyle, composition de silicone et diode electroluminescente organique WO2005035632A1 (fr)

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Publication number Priority date Publication date Assignee Title
GB2454366A (en) * 2007-11-01 2009-05-06 Univ Cranfield Electrochemical mediators
US10287398B2 (en) 2014-12-30 2019-05-14 Momentive Performance Materials Inc. Siloxane coordination polymers
US10294332B2 (en) 2014-12-30 2019-05-21 Momentive Performance Materials Inc. Functionalized siloxane materials

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DE3541161A1 (de) * 1985-11-21 1987-05-27 Basf Ag Carbazolsubstituierte polysiloxane und deren verwendung
DE3617996A1 (de) * 1986-05-28 1987-12-03 Basf Ag Feste, fotoleitfaehige schichten und diese enthaltende elektrofotographische aufzeichnungsmaterialien
US4933053A (en) * 1987-02-05 1990-06-12 Ciba-Geigy Corporation Carbazole-containing, electrically conductive polysiloxanes
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DE3541161A1 (de) * 1985-11-21 1987-05-27 Basf Ag Carbazolsubstituierte polysiloxane und deren verwendung
DE3617996A1 (de) * 1986-05-28 1987-12-03 Basf Ag Feste, fotoleitfaehige schichten und diese enthaltende elektrofotographische aufzeichnungsmaterialien
US4933053A (en) * 1987-02-05 1990-06-12 Ciba-Geigy Corporation Carbazole-containing, electrically conductive polysiloxanes
JPH06256520A (ja) * 1993-03-05 1994-09-13 Shin Etsu Chem Co Ltd 導電性重合体及びその製造方法

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2454366A (en) * 2007-11-01 2009-05-06 Univ Cranfield Electrochemical mediators
GB2454366B (en) * 2007-11-01 2012-01-04 Univ Cranfield Polydisperse hyperbranched polymers with redox mediator moieties and their uses
US10287398B2 (en) 2014-12-30 2019-05-14 Momentive Performance Materials Inc. Siloxane coordination polymers
US10294332B2 (en) 2014-12-30 2019-05-21 Momentive Performance Materials Inc. Functionalized siloxane materials

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