Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
  • G02F1/13363—Birefringent elements, e.g. for optical compensation
  • G02F1/133634—Birefringent elements, e.g. for optical compensation the refractive index Nz perpendicular to the element surface being different from in-plane refractive indices Nx and Ny, e.g. biaxial or with normal optical axis
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F12/02—Monomers containing only one unsaturated aliphatic radical
  • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/02—Alkylation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/18—Introducing halogen atoms or halogen-containing groups
  • C08F8/20—Halogenation
  • C08F8/22—Halogenation by reaction with free halogens
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/30—Polarising elements
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/30—Polarising elements
  • G02B5/3016—Polarising elements involving passive liquid crystal elements
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/30—Polarising elements
  • G02B5/3083—Birefringent or phase retarding elements
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
  • C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
  • C08J2325/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1343—Electrodes
  • G02F1/134309—Electrodes characterised by their geometrical arrangement
  • G02F1/134363—Electrodes characterised by their geometrical arrangement for applying an electric field parallel to the substrate, i.e. in-plane switching [IPS]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31855—Of addition polymer from unsaturated monomers

Definitions

• the invention relates to optical compensation films with positive birefringence greater than 0.002 throughout the wavelength range of 400 nm ⁇ ⁇ ⁇ 800 nm for use in optical devices such as liquid crystal display (“LCD”) devices, optical switches and waveguides where a controlled light management is desirable. More particularly, the optical compensation films are for use in an in-plane switching LCD (“IPS-LCD").
• LCD liquid crystal display
• IPS-LCD in-plane switching LCD
• LCDs are used as display screens in many common applications including digital clocks, microwaves, laptop computers, calculators and other electronic devices. LCDs offer advantages over luminescent display technologies such as cathode ray tubes (CRTs) because they are lighter, thinner and require less voltage and power to operate.
• CRTs cathode ray tubes
• LCD screens have good picture quality and contrast when viewed directly, i.e. at an angle that is perpendicular, or normal, to the plane of the screen.
• picture quality and contrast decline as the viewing angle increases.
• Image degradation occurs because the LC cell is birefringent and splits the entering light beam into two light beams (ordinary and extraordinary) that propagate through the LC cell in different directions and different speeds.
• the ordinary and extraordinary rays move in different planes, at different speeds and have different indices of refraction (n 0 and n e , respectively).
• the ordinary ray travels in a direction parallel to the direction of the liquid crystals, while the extraordinary ray travels in a direction perpendular to the direction of the liquid crystals.
• IPS-LCDs have molecules that are aligned in-plane
• light moving through the LC parallel to the plane of molecules plane of the has a higher index of refraction than light moving in the direction perpendicular to the molecules.
• light passing through the IPS LC cell has the relationship ny » n ⁇ , or n e » n 0 .
• light moving parallel to the LC molecules in the x or y directions on a Cartesian plane has a higher index of refraction than light moving perpendicular to the LC molecules in the z direction.
• Birefringence, ⁇ n measures the difference between the indices of refraction of the ordinary and extraordinary rays:
• US Patent Application No. 2005/0200792 Al discloses an in-plane switching liquid crystal display comprising a negative biaxial retardation film and a positive C-plate as a viewing angle compensation film.
• US Patent Application No. 2005/0140900 Al discloses an IPS-LCD comprising a positive A-plate and a positive C-plate. No chemical composition of the positive C-plate is disclosed.
• US Patent Application No. 2005/0270458 Al discloses a multilayer optical compensation film comprising optically anisotropic first and second layers, wherein the second layer includes amorphous polymer with a glass transition temperature above 16O 0 C, and the indices of refraction satisfy the relations
• US Patent No. 5,189,538 discloses a liquid crystal display comprising a film having light transmission properties that includes a uniaxially stretched polymer film with positive intrinsic birefringence.
• US Patent Application No. 2005/0122456 discloses an optical film with a substrate without a vertical alignment layer and a homeotropic alignment liquid crystal film layer formed on the substrate.
• the homeotropic alignment liquid crystal film layer comprises a homeotropically aligned liquid crystal polymer
• optical compensation film having a large positive birefringence value without being subject to expensive processes such as stretching, photo irradiation, and heat treatment.
• the optical compensation film should be stable at ambient conditions, optically transparent, have low color, and be easy to apply onto a substrate.
• R 1 , R 2 , and R3 are each independently hydrogen atoms, alkyl groups, substituted alkyl groups, or halogens;
• Ar-BES is an optically anisotropic subunit (OASU) that is attached directly to the polymer backbone via at least one covalent bond, wherein Ar is an aromatic ring structure, BES represents at least one birefringence enhancing substituent; and wherein the Ar-BES is oriented perpendicular to the polymer backbone, and the higher the perpendicularity of the Ar-BES, the larger the value of the positive birefringence of the polymer film.
• the polymer film is a homopolymer.
• the compensation film is capable of forming an out-of-plane anisotropic alignment upon solvent evaporation without being subject to heat treatment, photo irradiation, or stretching and has a positive birefringence greater than 0.002, greater than 0.005, or greater than 0.01 throughout the wavelength range of 400 nm ⁇ ⁇ ⁇ 800 nm.
• the compensation film is removed from the substrate upon drying to yield a free-standing film, which may be uniaxially or biaxially stretched. The free-standing film may be attached to a substrate by lamination with or without stretching.
• the polymer composition is soluble in a solvent such as toluene, methyl isobutyl ketone, cyclopentanone, and a mixture thereof.
• BES is nitro- or bromo-.
• the compensation film is used in a liquid crystal display device including an in-plane switching liquid crystal display device. The liquid crystal display device may be used as a screen for a television or computer.
• the degree of substitution of the BES may be controlled. In another embodiment, degree of substitution of the BES is greater than 0.5. In yet another embodiment, BES is nitro-, bromo-, iodo-, cyano- or phenyl-. Preferably, BES is nitro- or bromo-. In one embodiment, the aromatic ring is benzene, biphenyl, naphthalene, anthracene, phenanthrene, naphthacene, pentacene, or triphenyl. Preferably, the aromatic ring is benzene.
• BES is nitro- or bromo- and the aromatic ring is benzene, biphenyl, naphthalene, anthracene, phenanthrene, naphthacene, pentacene, ortriphenyl.
• the polymer film is poly(nitrostyrene).
• the poly(nitrostyrene) may have a positive birefringence greater than 0.007 throughout the wavelength range of 400 nm ⁇ ⁇ ⁇ 800 nm.
• the poly(nitrostyrene) may have a degree of substitution greater than 0.7 for the nitro group.
• the poly(nitrostyrene) may have a degree of substitution greater than 0.5 or greater than 0.7 for the nitro group.
• the polymer film may have BES that have some para-mtxo groups or that have mostly para-mtxo groups.
• poly(nitrostyrene) has mostly para -nitro groups and a degree of substitution greater than 0.5 or greater than 0.7 for the nitro group.
• R 1 , R 2 , R 3 ,R 4 , R 5 , and R 7 are each independently hydrogen atoms, alkyl groups, substituted alkyl groups, or halogens; wherein R 6 is a hydrogen atom, alkyl, substituted alkyl, halogen, ester, amide, ketone, ether, cyano, phenyl, epoxy, urethane, urea or optically anisotropic subunit (OASU) attached directly to the backbone of the residue of an ethylenically unsaturated monomer; wherein Ar-BES is an optically anisotropic subunit (OASU) that is attached directly to the copolymer backbone via at least one covalent bond.
• OASU optically anisotropic subunit
• the copolymer's at least one ethylenically unsaturated monomer is styrene, vinyl biphenyl, methyl methacrylate, butyl acrylate, acrylic acid, methacrylic acid, acrylonitrile, 2-ethylhexyl acrylate, or 4-t-butylstyrene.
• the at least one monomer of the copolymer includes styrene.
• the compensation film is capable of forming an out-of-plane anisotropic alignment upon solvent evaporation without being subject to heat treatment, photo irradiation, or stretching and has a positive birefringence greater than 0.002 or greater than 0.005 or greater than 0.01 throughout the wavelength range of 400 nm ⁇ ⁇ ⁇ 800 nm.
• the compensation film is removed from the substrate upon drying to yield a free-standing film, which may be uniaxially or biaxially stretched. The free-standing film may be attached to a substrate by lamination with or without stretching.
• the polymer composition is soluble in a solvent such as toluene, methyl isobutyl ketone, cyclopentanone, and a mixture thereof.
• BES is nitro- or bromo-.
• the compensation film is used in a liquid crystal display device including an in-plane switching liquid crystal display device. The liquid crystal display device may be used as a screen for a television or computer.
• the degree of substitution of the BES may be controlled. In one embodiment, the degree of substitution of the BES is greater than 0.5.
• BES may be nitro- bromo-, iodo-, cyano- or phenyl-, and is preferably nitro- or bromo-.
• the aromatic ring may be benzene, biphenyl, naphthalene, anthracene, phenanthrene, naphthacene, pentacene, or triphenyl but is preferably benzene.
• the polymer is poly(nitrostyrene-co-styrene).
• the poly(nitrostyrene-co-styrene) may have a degree of substitution for the nitro group that is greater than 0.5 or greater than 0.7.
• Some BES may be para-nitro groups, or nearly all BES may be/? ⁇ ra-nitro groups.
• poly(nitrostyrene-co-styrene) has nearly all BES as para-nitro groups a degree of substitution greater than 0.5 or greater than 0.7 for the nitro group.
• the polymer is poly(bromostyrene-co-styrene).
• the poly(bromostyrene-co-styrene) may have a degree of substitution for the bromo group that is greater than 0.5 or greater than 0.7.
• Some BES may be para-bromo groups, or nearly all BES may be/? ⁇ ra-bromo groups.
• poly(bromostyrene-co-styrene) has nearly all BES as para-bromo groups and a degree of substitution greater than 0.5 or 0.7 for the bromo group. 4. DESCRIPTION OF THE DRAWINGS
• Figure 1 is a depiction of several OASUs and the frameworks for calculating the buttressing factor for these OASUs.
• Figures Ia and Ib depict the OASU of polystyrene
• Figures Ic-Id depict the disk OASU of, poly(2 -vinyl naphthalene).
• Figures Ie-If depict the disk OASU of poly(l -vinyl naphthalene).
• Figures Ig-Ih depict the disk OASU of poly(vinylpyrene).
• Figure Ii depicts the mesogen OASU, of poly[2,5-bis(p- alkoxyphenyl)styrene] .
• Figure 2 is a depiction of the framework for calculating the buttressing factor for polystyrene.
• Figure 3(a) is a side view depiction of a buttressed rod-like mesogen-jacketed polymer chain.
• Figure 3(b) is an end view depiction of a buttressed rod- like mesogen- jacketed polymer chain.
• Figure 5 is a depiction of the stages of solvent evaporation during solution casting.
• Figure 8 is a depiction of the framework for calculating the buttressing factor for poly(vinylpyrene).
• the optical compensation films of the invention may be aligned anisotropically such that the net optical axis of a rod- like OASU (in the rod- direction) is out-of-plane (where out-of-plane includes but is not limited to optical axes that are perpendicular to the plane), and the net optical axis of a disk-like or Ar-BES OASU (in the disk normal direction) is in-plane (where in-plane includes but is not limited to optical axes that are parallel to the plane).
• the optical compensation films of the invention may be used as part of a liquid crystal display (LCD) device, particularly an in-plane switching (IPS) LCD.
• the LCD may be used in electronic devices with display screens including, but not limited to, televisions, computers, cell phone, clocks, microwaves and calculators.
• the polymer film with high positive birefringence has a moiety containing a light stable OASU in the polymer backbone.
• the OASU may be attached directly to the polymer backbone through one covalent bond so the moiety has the general formula:
• R 1 , R 2 , and R 3 are each independently hydrogen atoms, alkyl groups, substituted alkyl groups, or halogens, and OASU is an optically anisotropic sub-unit.
• the OASU may also be attached directly to the polymer backbone through two independent covalent bonds so the moiety has the general formula:
• the polymer film may be a homopolymer or a copolymer.
• the copolymer may have one or more moieties containing an OASU attached directly to the polymer backbone through at least one covalent bond.
• the description of the invention applies to any OASU-containing homopolymer or copolymer with any combination of moieties.
• the term "polymer" refers to homopolymers and copolymers.
• the OASU may be disk-like, rod like (mesogen), or aromatic rings (Ar) substituted with birefringence enhancing substituents (BES).
• the OASU is oriented perpendicular to the polymer backbone, and the value of the positive birefringence of the polymer film increases with increasing perpendicularity of the OASUs.
• the polymer solutions may advantageously form an out-of-plane anisotropic alignment upon solvent evaporation and solution film casting without being subject to heat treatment, photo irradiation, or a stretching process (although one or a combination of these processes may be used to further entrance birefringence).
• the resulting buttressed polymer films are stable at ambient conditions, have high positive birefringence and may be inexpensive to produce.
• Positive birefringence is defined as n z >(n x +n y )/2, wherein n x and n y represent in-plan refractive indexes, and n z represents the thickness-direction refractive index of the film.
• each polymer and the optical compensation films made therefrom each has positive birefringence greater than 0.002 throughout the wavelength range of 400 nm ⁇ ⁇ ⁇ 800 nm without being subject to heat treatment, photo irradiation, or stretching. However, in certain embodiments these processes may be used to further enhance positive birefringence.
• the compensation films may have birefringence greater than 0.005, 0.01, 0.02 or 0.03 throughout the wavelength range of 400 nm ⁇ ⁇ ⁇ 800 nm.
• Birefringence ( ⁇ n) may be measured by determining the birefringence of a film over a wavelength range of about 300 nm to about 800 nm at different increments.
• birefringence of a film may be measured at 633 nm as is customary in the art.
• Reference to ⁇ n at 633 nm is customary because birefringence at wavelengths ⁇ 633 nm is generally higher than birefringence at 633 nm, and birefringence at wavelengths > 633 nm is generally the same as or slightly lower than birefringence at 633nm.
• birefringence at 633 nm is understood in the art as indicating that birefringence throughout 300 nm ⁇ ⁇ ⁇ 800 nm is greater than or approximately the same as the birefringence at 633 nm.
• the OASU is a disk.
• the disk may be attached directly to the polymer backbone through one covalent bond so the moiety has the general formula:
• R 1 , R 2 , and R 3 are each independently hydrogen atoms, alkyl groups, substituted alkyl groups, or halogens.
• the disk may also be attached directly to the polymer backbone through two independent covalent bonds.
• the covalent bond may be a carbon-carbon or carbon-nitrogen bond.
• disks may be attached to the polymer backbone via a carbon or nitrogen atoms, such as the carbon atom on a benzene ring or the nitrogen atom on an imide or lactam.
• the disk-containing polymer has a positive birefringence greater than 0.002 throughout the wavelength range of 400 nm ⁇ ⁇ ⁇ 800 nm without being subject to heat treatment, photo irradiation, or stretching.
• the polymer film may be a homopolymer or copolymer with one or more moieties containing a disk attached directly to the polymer backbone through at least one covalent bond.
• the copolymer may have a moiety with the general structure in the polymer backbone:
• R 1 , R 2 , R 3 ,R 4 , R 5 , and R 7 are each independently hydrogen atoms, alkyl groups, substituted alkyl groups, or halogens; wherein R 6 is a hydrogen atom, alkyl group, substituted alkyl group, halogen, ester, amide, ketone, ether, cyano, phenyl, epoxy, urethane, urea, or optically anisotropic subunit (OASU) attached directly to the backbone of a residue of an ethylenically unsaturated monomer.
• R 6 is a different disk.
• R 6 is a benzene ring. The disk may also be attached to a copolymer backbone by two covalent bonds.
• the disk is usually a size greater than a benzene ring.
• the disk is usually bulky.
• the disk group has a fused ring structure.
• the "fused ring" structure may be understood to have two or more individual rings that are connected by sharing at least one of their sides.
• Each individual ring in the fused ring may be substituted or unsubstituted and is preferably a six- or f ⁇ ve-membered ring, which may be all-carbon or heterocyclic.
• Individual rings in a fused ring may be aromatic or aliphatic.
• Preferred individual rings in a fused ring include, but are not limited to, aromatic rings and substituted aromatic rings, lactam ring and rings based on aromatic imide such as phthalimide and substituted phthalimide.
• the disk group is stable at ambient conditions and thus suitable for use in an optical compensation film for an LCD.
• polymer compositions comprising moieties with disk groups may be prepared by polymerization of a disk-containing monomer having a vinyl group attached directly to either a carbon or a nitrogen atom on the fused ring.
• Such disk-containing monomers with polymerizable vinyl groups include, but are not limited to, the following compounds:
• Polymerization may be carried out by a method known in the art such as bulk, solution, emulsion, or suspension polymerization.
• the reaction may be free radical, cationic, anionic, zwitterionic, Ziegler-Natta, or atom transfer radical type of polymerization.
• Emulsion polymerization is a preferred method of polymerization when a particularly high molecular weight is desirable. A high molecular weight polymer may lead to better film quality and higher positive birefringence.
• the disk-containing polymers may be soluble in, for example, toluene, methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), cyclopentanone, N 5 N- dimethylformamide, or mixtures thereof.
• Preferred solvents are toluene and MIBK.
• the OASU is an aromatic ring (Ar) substituted with birefringence enhancing substituents (BES).
• BES could also be substituents on disk or mesogen OASUs.
• the Ar-BES may also be a fused aromatic ring substituted with BES.
• the Ar-BES may be attached directly to the polymer backbone through one covalent bond so the moiety has the general formula:
• R 1 , R 2 , and R 3 are each independently hydrogen atoms, alkyl groups, substituted alkyl groups, or halogens.
• the Ar-BES may also be attached directly to the polymer backbone through two independent covalent bonds.
• the degree of substitution of the aromatic ring with BES is at least 0.1, but it may also be higher.
• the covalent bond may be a carbon-carbon or carbon-nitrogen bond.
• the Ar-BES containing polymer has a positive birefringence greater than 0.002 throughout the wavelength range of 400 nm ⁇ ⁇ ⁇ 800 nm without being subject to heat treatment, photo irradiation, or stretching.
• the polymer film may be a homopolymer or copolymer with one or more moieties containing an Ar-BES attached directly to the polymer backbone through one covalent bond.
• the copolymer may have a moiety with the general structure in the polymer backbone:
• R 1 , R 2 , R 3 ,R 4 , R 5 , and R 7 are each independently hydrogen atoms, alkyl groups, substituted alkyl groups, or halogens; wherein R 6 is a hydrogen atom, alkyl group, substituted alkyl group, halogen, ester, amide, ketone, ether, cyano, phenyl, epoxy, urethane, urea, or optically anisotropic subunit (OASU) attached directly to the backbone of the residue of an ethylenically unsaturated monomer.
• R 6 is a different Ar- BES.
• R 6 is a benzene ring.
• the degree of substitution (DS) of BES on the aromatic ring refers to the average number of BES on one aromatic ring in a polymer composition.
• DS 1 when, on average, each aromatic ring is substituted with one BES.
• DS may also be greater than 1 when, on average, each aromatic ring is substituted with more than one BES.
• DS is preferably greater than 0.3, more preferably greater than 0.5, and most preferably greater than 0.7.
• the DS of BES is directly related to the polymer's birefringence.
• ⁇ n may be manipulated by varying the DS.
• the solubility of the polymer can also dependent on the DS and be optimized accordingly.
• the DS can be readily manipulated by one of ordinary skill in the art, for example, by adjusting the starting amounts of BES.
• the Ar-BES-containing polymer is a poly(vinylaromatic), i.e. a polymer resulting from polymerization of the vinyl group on an aromatic ring.
• the poly(vinylaromatic) also has at least one BES.
• Poly(vinylaromatic) with BES advantageously exhibits exceptionally high birefringence values, is soluble in a variety of organic solvents, and may be used to prepare an optical compensation film by solution casting onto a substrate.
• the solubility and birefringence of poly( vinyl aromatics) of the invention can be controlled by incorporating certain BESs and by adjusting their degree of substitutions (DSs) of the aromatic rings of the polymers.
• an LCD device typically contains multi-layers of materials having different solubility in a variety of solvents and a layer can only be coated with a polymer solution that does not dissolve this specific layer.
• the ability to control the solubility and birefringence of a polymer allows the optical film of the present invention to be cast on a specific layer (or substrate) for LCD fabrication to achieve the desirable order of the layers in the device.
• aromatic groups include, but are not limited to, benzene, biphenyl, naphthalene, anthracene, phenanthrene, naphthacene, pyrene, pentacene, triphenyl, and the like.
• the aromatic ring is benzene, biphenyl or naphthalene.
• the aromatic ring is benzene.
• BES is a group that in general is bulky and/or capable of increasing the polarizability of the disk groups' aromatic ring on poly( vinyl aromatic).
• a polymer may contain different BES groups on different aromatic rings within the same polymer molecule or different BES groups on the same aromatic ring.
• BES include, but are not limited to, NO 2 , Br, I, CN, and phenyl.
• BES substituents are NO 2 , Br, I, and CN.
• BES is NO 2 or Br.
• BES may be attached to an aromatic ring such as benzene at any available position including the positions that are para, ortho or meta to the ethylene moiety.
• a polymer composition may also have BESs that are in different positions on different aromatic rings.
• the BES is para to the ethylene moiety.
• BES may also be mostly at the para position with some BES at the ortho and/or meta positions.
• polymer compositions of BES- substituted aromatic polymers include, but are not limited to, poly(nitrostyrene), poly(bromostyrene), substituted poly(nitrostyrene), substituted poly(bromostyrene), copolymers of nitrostyrene or bromostyrene, and copolymer of substituted nitrostyrene or bromostyrene.
• the polymer composition is poly(nitrostyrene), poly(bromostyrene), a copolymer thereof, or a mixture thereof.
• preferred polymers include poly(4-nitrostyrene), poly(4-nitrostyrene-co-styrene), poly(4- bromotyrene) and poly(4-bromostyrene-co-styrene).
• preferred polymers are prepared from 4-nitro- or 4-bromostyrene monomers, the nitro or bromo groups, respectively, will always be at the para position.
• poly(nitrostyrene) may be prepared by nitration of polystyrene in the presence of a mixed acid of HNO3 and H 2 SO 4 as disclosed in Philippides, A., et al, Polymer (1993), 34(16), 3509-13; Fernandez, M. J., et al, Polymer Degradation and Stability (1998), 60(2-3), 257-263; Cowie, J. M. G., et al, European Polymer Journal (1992), 28(2), 145-8; and Al-Najjar, Mohammed M, et al., Polymer Engineering and Science (1996), 36(16), 2083-2087.
• Nitration of polystyrene can be carried out in the presence of an organic solvent such as nitrobenzene, 1 ,2-dichloroethane, 3- nitrotoluene, carbon tetrachloride, chloroform, methylene chloride, carbon disulfide, N 5 N- dimethylformamide, N,N-dimethylacetamide, N-methylpyrolidone, or a mixture thereof.
• organic solvents are nitrobenzene and a 3:1 mixture of nitrobenzene and 1 ,2- dichloroethane.
• Poly(nitrostyrene) can also be prepared by polymerization of nitrostyrene monomer as disclosed in Philippides, A. et al., Polymer (1994), 35(8), 1759-63; and Jonquieres, A. et al., Polymer Bulletin (Berlin), (1994), 33(4), 389-95.
• Trifluoroacetic anhydride and trifluoroacetic acid may be used with nitric acid as the nitration agent.
• Inorganic nitrate salts such as NH4NO3, NaNO 3 , KNO3, and AgNO 3 may also be used with trifluoroacetic anhydride as the nitration agent as disclosed in Grivello, J. V., J. Org. Chem. (1981), 46, 3056-3060.
• poly(bromostyrene) may be prepared by bromination of polystyrene in the presence of bromine and a Lewis acid catalyst such as AlCl 3 , FeCl 3 , AlBr 3 , FeBr 3 , SbCl 5 , ZrCl 4 , Sb 2 O 3 , and the like, as disclosed in U.S. Patent Nos. 5,677,390 and 5,532,322, which are incorporated by reference in their entirety. It may also be prepared by reaction of polystyrene with n-butyllithium-TMEDA complex followed by bromine quenching as disclosed in Farrall, M. J. and Frechet, M.
• poly(bromostyrene) may also be prepared by polymerization of bromostyrene monomer as described in Farrall, M. J. and Frechet, M. J., Macromolecules, Vol. 12; p. 426, (1979).
• copolymers of bromostyrene may also be prepared as described previously for poly(nitrostyrene).
• the poly(bromostyrene) polymers prepared in this invention are soluble in toluene as well as in cyclopentanone even with high degrees of substitution. This is particularly useful for coating a TAC substrate since toluene will not have a detrimental effect on the TAC film.
• Polymer compositions comprising moieties with Ar-BES may also be prepared by copolymerization of an Ar-BES-containing monomer with one or more ethylenically unsaturated monomers.
• ethylenically unsaturated monomers that may be used to copolymerize with disk-containing monomers include, but are not limited to, one or more of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, isoprene, octyl acrylate, octyl methacrylate, iso-octyl acrylate, iso-octyl methacrylate, trim
• Polymerization may be carried out by a method known in the art such as bulk, solution, emulsion, or suspension polymerization.
• the reaction may be free radical, cationic, anionic, zwitterionic, Ziegler-Natta, or atom transfer radical type of polymerization.
• Emulsion polymerization is a preferred method of polymerization when a particularly high polymer molecular weight is desirable. A high molecular weight polymer may lead to better film quality and higher positive birefringence.
• Solution film casting may be done with Ar-BES containing polymer, a polymer solution comprising a blend of Ar-BES -containing polymer with other polymers, or a copolymer of Ar-BES containing monomer with other monomers, the latter two being advantageous because they may improve film quality and lower cost.
• Polymer solutions may further contain other ingredients such as other polymers or additives.
• R 1 , R 2 , and R 3 are each independently hydrogen atoms, alkyl groups, substituted alkyl groups, or halogens.
• the mesogen may also be attached directly to the polymer backbone through two independent covalent bonds.
• the covalent bond may be a carbon-carbon or carbon-nitrogen bond.
• the mesogen is attached to the polymer backbone preferably at the gravity center of the mesogen or a nearby position, but may also be attached at an end or off-center position.
• the mesogen-containing polymer has a positive birefringence greater than 0.002 throughout the wavelength range of 400 nm ⁇ ⁇ ⁇ 800 nm without being subject to heat treatment, photo irradiation, or stretching.
• the mesogen-containing polymer film may be made by solution casting and may form an out-of- plane anisotropic alignment upon solvent evaporation.
• the positive birefringence is greater than 0.005, greater than 0.01, greater than 0.02 or greater than 0.03 throughout the wavelength range of 400 nm ⁇ ⁇ ⁇ 800 nm.
• the mesogen-containing polymers in the present invention are commonly referred to as mesogen jacketed polymers (MJPs).
• MJPs according to the invention include conventional mesogen-jacketed liquid crystalline polymers (MJLCPs) as well as polymers that are jacketed by a non- liquid crystalline rod-like group.
• mesogen-jacked polymers have no or very short spacers between the polymer backbones and the rod-like mesogenic units. See Zhao, Y. F., et al. Macromolecules, 2006, 39, p. 948. Thus, MJPs have a strong interaction between the main chains and the bulky side groups. As a result, unlike the conventional side- chain LCPs whose backbones usually take a random-coil chain conformation, MJPs are somewhat rigid and exhibit some characteristics of main-chain LCPs.
• MJPs having no spacers between the backbones and the rod- like mesogenic side groups are capable of forming out-of-plane anisotropically aligned films without being subject to either heat treatment or photo irradiation.
• An embodiment of the invention includes preparing such films by solution casting. Upon solvent evaporation at an ambient temperature, the resulting films exhibit exceptionally high positive birefringence. MJPs of the invention are soluble in a variety of organic solvents.
• Mesogens of the invention may have the general formula:
• a 1 , A 2 , and A 3 are independently either aromatic or cycloaliphatic rings.
• the rings may be all carbons or heterocyclic and may be unsubstituted or mono- or poly-substituted with halogen, cyano or nitro, or alkyl, alkoxy, or alkanoyl groups having 1 to 8 carbon atoms.
• Z 1 , Z 2 , and Z 3 are each independently -COO-, -OOC— , -CO-, -CONH-, -NHCO-
• R 1 and R 2 are each independently halogen, cyano, or nitro groups, or alkyl, alkoxy, or alkanoyl groups having 1 to 25 carbon atoms, or has one of the meanings given for — (Z 2 - A 3 ).
• m is 0, 1, or 2; n is 1 or 2.
• n is 1 or 2;
• a 2 is 1 ,4-phenylene; and the mesogen is attached to the polymer backbone through A 2 . More preferably, m is 2; n is 2; A 2 is 1 ,4-phenylene; and the mesogen is attached to the polymer backbone through A 2 .
• Representatives and illustrative examples of preferred polymer moieties with mesogens having m is 1 or 2, n is 1 or 2, A 2 is 1 ,4-phenylene, and the mesogen is attached to the polymer backbone through A 2 include, but are not limited to:
• MJPs of the invention may be prepared by polymerization of a mesogen monomer having a vinyl group attached to one of its rings, preferably an aromatic ring such as benzene.
• the polymerization may be carried out by a method known in the art such as bulk, solution, emulsion, or suspension polymerization.
• the reaction may be free radical, cationic, anionic, zwitterionic, Ziegler-Natta, or atom transfer radical type of polymerization. See Zhou, Q. F., et al. Macromolecules, 1987, 20, p.233; Zhang, D., et al, Macromolecules, 1999, 32, p.
• Polymers with these moieties have a positive birefringence greater than about 0.02 throughout the wavelength range of 400 nm ⁇ ⁇ ⁇ 800 nm.
• MJPs of the present invention may also be prepared by copolymerization of a mesogen monomer having one vinyl group with one or more ethylenically unsaturated monomers.
• ethylenically unsaturated monomers that may be used for copolymerization with mesogen-containing monomers include, but are not limited to, one or more of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, isoprene, octyl acrylate, octyl methacrylate, iso-octyl acrylate, iso-octyl acrylate, iso-oct
• Solution film casting may be done with MJPs, a polymer solution comprising a blend of MJPs with other polymers, or a copolymer of MJPs, the latter two being advantageous because they may improve film quality and lower cost.
• Polymer solutions may further contain other ingredients such as other polymers or additives.
• MJPs of the invention are soluble in toluene, methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), cyclopentanone, N,N-dimethylformamide or a mixture thereof depending on the structures of the mesogens.
• Preferred solvents are toluene and MIBK.
• Optical films can be cast onto a substrate from the resulting polymer solutions by a method known in the art such as, for example, spin coating, as described above.
• the OASU is attached directly to the polymer backbone through two independent covalent bonds so the moiety has the general formula:
• R 1 , R 2 , and R 3 are each independently hydrogen atoms, alkyl groups, substituted alkyl groups, or halogens, and OASU is an optically anisotropic sub-unit.
• Another example embodiment of the invention includes a method for controlling the birefringence of an optical compensation film by selecting a polymer that adheres to parameters that have been discovered to enhance birefringence as disclosed herein.
• Birefringence of a polymer film with positive birefringence may be controlled by controlling the orientation of optically anisotropic subunits (OASUs), which are the molecular units that give a compensation film its birefringent properties.
• OASUs optically anisotropic subunits
• birefringence may be controlled by selecting a polymer with substituents that exhibit the buttressing effect, defined as:
• R and D values may be understood by reference to an exemplary polymer, polystyrene, which is explained in Figures 1-2 and the following example.
• D is the distance between the attaching points of two OASUs to the polymer backbone when the polymer is in the extended chain conformation, as depicted in exemplary Figure Ia.
• D is the straight line distance between the attaching points of neighboring OASUs rather than the entire distance along the polymer backbone between the attaching points.
• D may be calculated by drawing a framework around an OASU-containing moiety and using known bond lengths and bond angles.
• FIG. 1 shows the point on the polymer backbone at which the OASU of reference (the benzene ring) will be attached.
• Figure 2b shows a segment of the polymer backbone in the extended chain conformation. For polystyrene, this represents two single carbon-carbon bonds, each having a bond length of 0.154 nm and a bond angle of 109.5°.
• D is approximately 2.51 A.
• Other examples of D calculations are depicted in Figures Ic, Ie, Ig, 3a-c and 4a-c and by Examples 23 and 24.
• R measures the size of an OASU in the direction perpendicular to its rigid bond to the polymer backbone.
• the OASU is drawn to scale in the plane of the paper according to its actual bond lengths and bond angles.
• R is measured by drawing lines flanking the OASU that are parallel to the covalent spacer bond and parallel to each other and determining the distance between the two outer lines using bond lengths and bond angles. That value is added to the van der waals radii of the left-most and right-most atoms of the OASU. This sum will be the value of R.
• This calculation is illustrated for the exemplary polymer polystyrene in Figure 2d-f.
• Figure 2d shows the covalent bond from a carbon atom of the polymer backbone to the attaching atom of the OASU. In the case of polystyrene, the attaching atom is also carbon.
• Figure 2e shows the structure of benzene attached to the polymer backbone and its known bond lengths and bond angles. All carbon- carbon bond lengths of the benzene ring are 0.14 nm, all bond angles of the benzene ring are 120°, and all carbon-hydrogen bond lengths of the benzene ring are 0.11 nm.
• Figure 2f shows the benzene ring with parallel vertical lines drawn at intervals such that calculating the distances of segments of the OASU is possible for each interval.
• bonds 1, 2, 3 and 4 each have an angle of 30° with respect to the horizontal length of the benzene OASU, and thus each segment has a length calculated by bond length x cos30°, and R is the sum of these segment lengths plus the van der waals radii of the hydrogen atoms, which are each 0.12 nm.
• R may be calculated by:
• this calculation may also be performed as:
• the R calculation will be the same as for styrene because the BES at the 4-position does not contribute to the dimension (R) of the Ar-BES and is thus not included in the calculation of R.
• the van der waals radii of the oxygen atoms in Figure Ii are the rightmost and left-most distances to be included in the R calculation.
• the buttressing effect also causes the polymer backbone to have an overall linear shape (i.e., viewed from a distance) over a long distance.
• the buttressed polymer is rigidly fixed in the corkscrew-like conformation with OASUs extending above and below at angles that are approximately perpendicular to the overall linear direction of the buttressed polymer chain, as shown in Figure 3.
• the butressing factor for an OASU is greater than about 2.5.
• the OASU is Ar-BES and the butressing factor may be at least about 2.6.
• the buttressing factor for an OASU is at least about 2.7.
• the OASU is a disk or a mesogen and the butressing factor may be at least about 2.7.
• High birefringence ⁇ n achieved through selecting a polymer with the buttressing effect is also desirable because it allows the thickness of the compensation film to be thinner since film birefringence and thickness vary inversely.
• the retardation value of an optical compensation film is defined as d x ⁇ n, wherein d is the thickness of the film.
• d is the thickness of the film.
• the retardation value of the optical compensation film may preferably be 50 nm to 400 nm.
• ⁇ n 0ASU is less than zero for disk-like OASUs because their optical axis is perpendicular to the plane of the OASU disk so n 0 0 O A A S S U U ⁇ ⁇ n e OASU T iee
• ⁇ is in the range from 0° to 90°, and O OASU is thus in the range from -0.5 to 1. Therefore, O OASU may be positive, negative, or zero.
• ⁇ n ⁇ n 0ASU x o OASU .
• the invention pertains to positive C plates.
• the rod-like OASU requires a positive order parameter (O OASU >0)
• the disk-like OASU requires a negative order parameter
• O is always negative or zero. Therefore, in the case of non-zero O , the sign of ⁇ n is determined by the sign of ⁇ n .
• O preferably has a large absolute value, which requires a sufficiently large segment size or a sufficiently long persistent length.
• birefringence may be controlled by selecting a polymer with OASUs that satisfy the equation:
• ⁇ n ⁇ n 0ASU x O u s x 0 s > 0
• rod-like OASUs For a rod-like OASU, ⁇ n 0ASU >0 and 0 s ⁇ 0. Thus, positive C-plates require negative O u s . O u s is negative when the rods are perpendicular to the segment direction.
• rod-like OASUs are selected such that the distance between the two attaching points of the neighboring OASUs is shorter than the length of the rod the so that they exhibit the buttressing effect. If the rod-like OASUs are selected according to these parameters, then the rods can no longer rotate freely. Instead, some conformation with rod direction parallel to the main chain direction will be forbidden due to steric hindrance. Further, the main polymer chain will be substantially rigid and linear over a long distance.
• OASU may be attached to the main chain from any position as long as buttressing effect is present.
• OASUs according to the buttressing effect parameters allows birefringence to be manipulated because it generates and enhances the non-zero segment parameter, O u s .
• the buttressing effect will make some of the OASU's conformations forbidden and thus leads to the preferred orientation of the OASU.
• the buttressing effect is the basic reason for the negative OASU order parameter within a segment O u s .
• the bigger buttressing factor will have a stronger buttressing effect and make O u s more negative for rod-like model and more positive for disk-like model.
• An advantage of the invention is that compensation films with high birefringence may be obtained by a simple solution casting process without any other post- processing such as stretching, photopolymerization, etc.
• Solution casting without postprocessing may significantly reduce the cost of film fabrication and help eliminate errors caused by the complexity of post-processing.
• post-casting processing such as uniaxially or biaxially stretching or photopolymerization, may be used to further enhance the compensation film's high positive birefringence.
• the order parameter of a polymer segment, O is mainly determined by the conditions of solution casting, such as temperature, evaporation rate, and concentration.
• a variety of solvents may be used for solution casting the optical compensation films of the invention including, but not limited to, chloroform, dichloromethane, dichloroethane, benzene, chlorobenzene, xylene, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, pyridine, dimethylsulfoxide, acetonitrile, cyclohexanone, methyl amyl ketone, ethyl acetate, ethylene glycol monobutyl ether, and the like.
• Preferred solvents include toluene, methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), and cyclopentanone.
• Optical films may be cast onto a substrate from polymer solutions by a method known in the art such as, for example, spin coating, spray coating, roll coating, curtain coating, or dip coating.
• Substrates are known in the art, and include TAC (triacetylcellulose), polyester, polyvinyl alcohol, cellulose ester, polycarbonate, polyacrylate, polyolefm, polyurethane, polystyrene, glass, and other materials commonly used in an LCD device.
• solvent evaporation generally follows a free relaxation model.
• the order parameter of the polymer segments is zero.
• the system fluctuates between the collapsed ball shape and round ball shape.
• the polymer's glass transition temperature is lower than the environment temperature so that polymer chains relax fast enough to compete with the collapse.
• Vf may be determined by many factors including, but not limited to, evaporation rate of the solvent, environmental temperature, solubility of the polymer in the solvent and the chemical structure of the polymer, which affects relaxation.
• the evaporation rate is preferably slow enough to ensure that the ball shape collapses but fast enough to ensure that the relaxation rate is slower at more dilute concentrations.
• evaporation rate may be adjusted by adjusting environmental temperature and pressure.
• the relaxation rate depends on the chemical structure of polymer and the film casting temperature. Polymers with rigid segments may freeze easily at the environmental temperature.
• the polymer was then dissolved in fresh THF and reprecipitated by dropwise addition into rapidly stirring methanol. After collection by filtration and drying, the resulting polymer was found to have MW of 127,000 g/mol and a Tg of 139 0 C.
• a film cast from cyclopentanone (Cp) showed a positive birefringence of 0.0040 at 633 nm.
• Example 3 Preparation of Polv(2-vinylnaphthalene) by solution polymerization
• 2-Vinylnaphthalene (2.0Ig), azo-bis(isobuytronitrile) (AIBN, 1.5mg) and benzene (0.98g) were charged to a 50 mL round bottom flask containing a Teflon-coated magnetic stirbar.
• the reaction mixture was degassed by bubbling dry argon gas through the stirring reaction mixture for 15 minutes.
• the vessel contents were then kept under a positive pressure of argon and immersed into an oil bath maintained at 60 0 C for 19 hours.
• the contents of the vessel were diluted with 25 mL of benzene after cooling the reaction mixture to room temperature.
• the resulting solution was slowly poured into 500 mL of rapidly stirring methanol, causing the resulting polymer to precipitate.
• the precipitated polymer was collected by filtration and dried by pulling air through the material on a filter pad.
• the polymer was then dissolved in tetrahydrofuran and reprecipitated by dropwise addition into rapidly stirring methanol. After collection by filtration and drying, the resulting polymer was found to have MW of 251,000 g/mol and a Tg of 148°C.
• a film cast from cyclopentanone showed a positive birefringence of 0.0073 at 633 nm.
• Example 4 Preparation of Polv(2-vinylnaphthalene) by emulsion polymerization
• 2-Vinylnaphthalene (2.00 g), sodium dodecyl sulfate (0.40 g), and water (18.0g) were charged to a 125ml round bottom flask containing a Teflon-coated magnetic stirbar.
• the contents of the vessel were degassed by bubbling dry argon gas through the stirring reaction mixture for 30 minutes.
• the vessel contents were then kept under a positive pressure of argon and immersed into an oil bath maintained at 80 0 C. After 30 minutes at 80 0 C, the vessel was then charged with potassium persulfate solution (32 mg in 1 mL of water).
• GBL ⁇ -butyrolactone
• copolymers were prepared by charging various mole ratios of styrene (S) with either N-vinyl phthalimide (VPI) or N-vinyl- 4,5-dichlorophthalimide (VDCPI), Films were then cast from NMP and their birefringence measured as listed in the table below. It should be noted, however, the mole ratios of the resulting polymers could vary due to low yields (about 30%).
• Example 8 Preparation of Poly(nitrostyrene) by Nitration of Styrene
• Polystyrene (5.0 g) was stirred and dissolved in a solvent mixture of nitrobenzene (90 g) and 1 ,2-dichloroethane (30 g) in a three-neck round-bottom flask equipped with a mechanical stirrer.
• the mixture was allowed to react at room temperature under nitrogen for a total of 22 hours.
• the resulting yellow mixture was poured into diluted sodium hydroxide in water and organic layer separated, which was subsequently precipitated into methanol to give a solid mass.
• the solid was dissolved in N ,N- dimethylformamide (DMF) and re-precipitated into methanol.
• the resulting heterogeneous mixture was stirred for two hours, filtered, washed repeatedly with methanol, and dried under vacuum to give a slightly yellowish fibrous powder. The yield was generally >95%.
• Example 9 The Property Relationship of Poly(nitrostyrenes) Having Various Degrees of
• a copolymer was prepared by nitration of poly(styrene-co-acrylonitrile) (75% styrene, MW 165K; Aldrich) using the same method as in Example 8 with an equivalent ratio of nitro/styrene, 3/1.
• the resulting polymer had Tg of 151 0 C, % N 5.84 (DS 0.62) (excluding CN group), and was soluble in cyclopentanone (Cp).
• a film was cast from Cp and showed a positive birefringence of 0.0089 at 633 nm.
• Example 11 Preparation of Polyfbromostyrene) by Bromomination of Styrene
• Polystyrene (5.0 g) (Mw 280, 000; Aldrich) was stirred and dissolved in 1,2- dichloroethane (100 g) in a three-neck round-bottom flask equipped with a mechanical stirrer.
• AICI3 0.1 g
• bromine 15.4 g
• the resulting red mixture was precipitated into methanol, filtered, and washed repeatedly with methanol to give a slightly yellowish fibrous powder (7.2 g).
• the product was soluble in toluene or Cp and has a Tg of 134 0 C, 34% of Br (DS 0.78).
• a film was cast from toluene and measured to have ⁇ n +0.0069 @ 633nm.
• a copolymer was prepared by bromination of poly(styrene-co-acrylonitrile) (75% styrene, MW 165K; Aldrich) using the same method as in Example 11 with an equivalent ratio of Br/styrene, 2/1.
• the resulting polymer had Tg of 141 0 C, 26 % Br (DS 0.65), and was soluble in MIBK.
• a film cast from MIBK showed a positive birefringence of 0.0024 at 633 nm.
• Example 13 Preparation of Poly(bromo-nitrostyrene) by Bromination of Polyfnitrosytrene) [0104]
• a poly(bromo-nitrostyrene) was prepared by bromination of a poly(nitrostyrene) having DS 0.47 prepared as in Example 7.
• poly(nitrostyrene) (3.0 g), AICI3 (0.1 g), and bromine (4.62 g) (Br/styrene 2/1) were used.
• the mixture was allowed to react for 5 hours to give a slightly yellowish powder (2.5 g); Tg 139 0 C; soluble in MIBK or cyclopentanone; film cast from MIBK having ⁇ n +0.0054 @ 633 nm.
• Example 15 Nitration of Poly(2-vinylnaphthalene) [0106]
• a nitro-substituted polymer was prepared by nitration of poly(2-vinylnaphthalene) (Mw 251 K; Tg 148 0 C) using the same method as in Example 8 with an equivalent ratio of nitro/styrene, 2/1.
• the reaction was carried out by charging poly(2-vinylnaphthalene) (0.25 g), nitrobenzene (4.5 g), 1 ,2-dichloroethane (1.5 g), HNO 3 (0.29 g), and H 2 SO 4 (0.34 g) to a 50 ml flask equipped with a magnetic stirrer.
• the mixture was allowed to react for 22 hours to give a powder (0.33 g).
• the resulting polymer had Tg of 199 0 C and % N 2.17 (DS 0.31) and was soluble in cyclopentanone.
• a film cast from Cp showed a positive birefringence of 0.0088 at 633 nm.
• Nitration The above product after alkylation (1.5 g) was stirred and dissolved in nitrobenzene (25 g). To the mixture was added a mixed acid of HNO3 (2.6 g) and H 2 SO 4 (2.6 g) dropwise in a period of 30 minutes. The mixture was allowed to react at room temperature for 24 hours. After the reaction, the yellow mixture was washed with dilute NaOH in water. The organic layer was separated and precipitated into methanol, filtered, and then dissolved in DMF. The resulting polymer solution was re -precipitated into methanol, filtered, washed repeatedly with methanol, and dried under vacuum to give a yellowish fibrous powder (1.77 g). The product was soluble in MIBK and has a Tg of 171 0 C. A film was cast from MIBK and measured to have ⁇ n 0.0086 @ 633nm.
• the mixture was allowed to react at room temperature under nitrogen for a total of 20
• Example 21 Preparation of Polv(4-vinylbiphenvD by bulk polymerization
• 4-Vinylbiphenyl (1.38g) was charged to a Schlenk tube.
• the tube was stoppered, evacuated by pulling vacuum, and then filled with argon gas.
• the tube was evacuated and then refilled with argon four more times. While under a positive pressure of argon, the tube was immersed into an oil bath maintained at 130 0 C for 1.5 hours. After cooling to room temperature, the solid plug of material was dissolved in tetrahydrofuran (THF).
• THF tetrahydrofuran
• the solution was added in a dropwise manner into 50OmL of rapidly stirring methanol, causing the polymer to precipitate.
• the contents of the vessel were diluted with 25 mL of DMAc after cooling the reaction mixture to room temperature.
• the resulting solution was slowly poured into 50OmL of rapidly stirring methanol, causing the resulting polymer to precipitate.
• the precipitated polymer was collected by filtration and dried by pulling air through the material on a filter pad.
• the polymer was then dissolved in fresh DMAc and reprecipitated by dropwise addition into rapidly stirring methanol. After collection by filtration and drying, the resulting polymer was found to have MW of 842,000 g/mol and a Tg of 184°C .
• a film cast from cyclopentanone showed a positive birefringence of 0.0103 at 633 nm.
• Tg and positive birefringence are not directly proportional.
• Example 24 Synthesis of Various Mesogen- Jacketed Polymers
• the following mesogen-jacketed polymers were made by charging the vinyl mesogen monomers, benzoyl peroxide (BPO, 0.1-0.3% mole of monomers) and toluene or chlorobenzene to a polymerization tube containing a Teflon-coated magnetic stirbar.
• BPO benzoyl peroxide
• the reaction mixture was degassed by bubbling argon through for 15 minutes.
• the tube was then sealed and immersed into an oil bath maintained at 8O 0 C for one day. After cooling the reaction mixture to room temperature, it was slowly poured into rapidly stirring methanol, causing the resulting polymer to precipitate.
• the precipitated polymer was collected by filtration and dried in a vacuum oven.
• the buttressing factor B was calculated for a naphthalene ring OASU.
• the attaching atom of the OASU is the 2- position carbon atom on the naphthalene ring. All of the carbon-carbon bond lengths of the naphthalene ring are 0.14nm, all bond angles of the naphthalene ring are 120°, and all carbon- hydrogen bond lengths of the naphthalene ring are 0.1 lnm as shown in Figure 7b.
• a BES at the 4-position of benzene ring enhanced the birefringence of polystyrene without changing its buttressing effect.
• Polystyrene was substituted at the 4-position with the following BES: Cl, Br, I, CN, NO 2 , and phenyl.
• Each BES-substituted polystyrene had the same buttressing factor (R/D value) as unsubstituted polystyrene but exhibited enhanced birefringence.
• R/D value buttressing factor
• Using the highly polarizable and polar NO 2 group enhanced the birefringence of BES-substituted polystyrene to as high as 0.0209.
• the buttressing factor was calculated for the mesogen OASU depicted above.
• the mesogen OASU has the same backbone structure as polystyrene (PS) and thus D is calculated the same as for PS, yielding 0.25 nm.
• the attaching atom of the OASU is a carbon atom on the middle benzene ring of the mesogen OASU. All of the carbon-carbon bond lengths of the benzene rings are 0.14nm, all bond angles of the benzene rings are 120°, the carbon-carbon bond between two benzene rings is 0.15 nm, and all carbon-oxygen bond lengths of the mesogen are 0.14nm shown in Figure 9.
• the length between carbon 1 and carbon 4 of the benzene rings (depicted as lines 2, 4 and 6 in Figure 9) is 0.28 nm. Although the three benzene rings don't lie in the same plane because the OASU may twist on its axis, the benzene rings maintain a linear alignment. When the two oxygen atoms are connected by a straight line as shown in Figure 9, the 1-, 4- carbon atoms of all three benzene rings lie on that line. When parallel lines are drawn through the center of each atom of the OASU, the bond angles of bonds 1, 3, 5 and 7 and lines 2, 4 and 6 with respect to the horizontal length of the OASU as shown in Figure 9 are all 30°. The left-most and right-most atoms are oxygen atoms and have van der waals radii of 0.15nm. The Ri and R 2 alkyl groups are not included in the calculation of R because their bonds are flexible. Thus, R is calculated by:
• This R/D value is bigger than PS and thus lead to stronger buttressing effect and higher positive birefringence as compared to PS.
• this mesogen OASU has a bigger ⁇ n 0ASU than PS, which enhanced the final ⁇ n.
• the solution cast this mesogen jacket polymer film (with Ri as -OCH 2 CH 2 OCH 3 , and R 2 as -CH 2 CH(CH 3 )CH 2 CH 3 ) showed a positive birefringence of 0.0082 at 633nm.
• N-Vinyl-4-tert-butylphthalimide (2.Og), chlorobenzene (6.Og), and benzoyl peroxide (2.1mg) were charged to a Schlenk tube containing a Teflon-coated magnetic stirbar.
• the tube was stoppered and degassed through the sidearm by three freeze-pump-thaw cycles. While under a positive pressure of argon, the reaction tube was immersed into an oil bath maintained at 85°C for 3 hours with constant stirring.
• the resulting viscous solution was diluted with 1OmL of tetrahydrofuran (THF) and added in a dropwise manner into 500 mL of rapidly stirring methanol, causing the polymer to precipitate.
• THF tetrahydrofuran
• the precipitated polymer was collected by filtration and dried by pulling air through the material on a filter pad.
• the polymer was reprecipitated twice more from fresh THF solution by dropwise addition into methanol.
• the resulting polymer was found to be soluble in MIBK and toluene and had a Tg of 215 0 C and a weight average molecular weight (Mw): 643, 000.
• Mw weight average molecular weight
• Example 30 UV Spectra of Various Mesogen- Jacketed Polymers
• the following table is a collection of the absorption maximum ( ⁇ max) and the birefringence ( ⁇ n) measured at the wavelength of 633 nm for each polymer.
• the first five polymers (PC6, PC8, PClO, PC12, PCt) are poly ⁇ 2,5-bis[(4-alkyloxyphenyl)-l,3,4- oxadiazole]styrene ⁇ with the following chemical structure:
• Sample XCt is poly ⁇ 3,5-bis[(4-ter-butylphenyl)-l,3,4-oxadiazole]styrene ⁇ with the following chemical structure:
• UV- Visible Spectrophotomer (UV-2450) from Shimadzu (Japan) was used to obtain UV spectrum of the above polymers, shown in Figure X.
• ⁇ max is the wavelength of the absorption maximum.
• ⁇ n (633) was measured with Prism Coupler (Model 2010) from Mitricon Corp.

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