WO2007120459A2 - Chiral diole compounds, liquid crystal compositions and polymer networks derived therefrom - Google Patents

Chiral diole compounds, liquid crystal compositions and polymer networks derived therefrom Download PDF

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WO2007120459A2
WO2007120459A2 PCT/US2007/008080 US2007008080W WO2007120459A2 WO 2007120459 A2 WO2007120459 A2 WO 2007120459A2 US 2007008080 W US2007008080 W US 2007008080W WO 2007120459 A2 WO2007120459 A2 WO 2007120459A2
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compound
group
substituted
phenyl
liquid crystal
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PCT/US2007/008080
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English (en)
French (fr)
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WO2007120459A3 (en
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Marc Goldfinger
Jose Manuel Rodriguez-Parada
Lee Silverman
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E. I. Du Pont De Nemours And Company
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Priority to JP2009503060A priority Critical patent/JP2009532363A/ja
Priority to EP07754582A priority patent/EP2001888A2/en
Publication of WO2007120459A2 publication Critical patent/WO2007120459A2/en
Publication of WO2007120459A3 publication Critical patent/WO2007120459A3/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/10—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/58—Dopants or charge transfer agents
    • C09K19/586—Optically active dopants; chiral dopants
    • C09K19/588—Heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
    • C09K19/3405—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a five-membered ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
    • C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
    • C09K19/3405—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a five-membered ring
    • C09K2019/3408—Five-membered ring with oxygen(s) in fused, bridged or spiro ring systems

Definitions

  • the present invention is related to the chemical synthesis of bis (meth)acrylate chiral compounds, liquid crystal compositions comprising the chiral compounds, and polymerization of the liquid crystal compositions to provide polymer networks with useful cholesteric optical properties.
  • Thermotropic liquid crystals are generally crystalline compounds with significant anisotropy in shape. That is, at the molecular level, they are characterized by a rod-like or disc like structure. When heated they typically melt in a stepwise manner, exhibiting one or more thermal transitions from a crystal to a final isotropic phase.
  • the intermediate phases known as mesophases, can include several types of smectic phases wherein the molecules are generally confined to layers; and a nematic phase wherein the molecules are aligned parallel to one another with no long range positional order.
  • the liquid crystal phase can be achieved in a heating cycle, or can be arrived at in cooling from an isotropic phase.
  • a comprehensive description of the structure of liquid crystals in general, and twisted nematic liquid crystals in particular is given in "The Physics of Liquid Crystals," P. G. de Gennes and J. Prost, Oxford University Press, 1995.
  • nematic phase is one wherein a chiral moiety is present, referred to as a twisted nematic or cholesteric phase.
  • the • molecules are parallel to each other as in the nematic phase, but the director of molecules (the average direction of the rodlike molecules) changes direction through the thickness of a layer to provide a helical packing of the nematic molecules.
  • the pitch of the helix is perpendicular to the long axes of the molecules.
  • This helical packing of anisotropic molecules leads to important and characteristic optical properties of twisted nematic phases including circular dichroism, a high degree of rotary power; and the selective reflection of light, including ultraviolet, visible, and near-IR light.
  • the sense of the helix can either be right- handed or left-handed, and the rotational sense is an important characteristic of the material.
  • the chiral moiety either may be present in the liquid crystalline molecule itself, for instance, as in a cholesteryl ester, or can be added to the nematic phase as a dopant, with induction of the cholesteric phase. This phenomenon is well documented, see e.g. H. Bassler, M.M. Labes, J. Chem. Phys., 52 p 631 (1970).
  • Crosslinking chiral monomers including bis (meth)acrylates with ether groups (-O-) linking a core chiral group to flexible spacers and polymerizable (meth)acrylates are disclosed in US
  • One embodiment of the invention is a compound of Formula (T):
  • R 1 and R 2 are each independently selected from the group: H, F, Cl and CH 3 ; nl and n2 are each independently integers 3 to 20; q and r are each independently integers 0, 1 or 2, with the proviso that q + r is >1 ; D is a divalent chiral radical selected from the group:
  • R 3 is a Cl to C6 straight or branched chain alkyl group
  • Another embodiment of the invention is a polymerizable liquid crystal composition comprising at least one compound of Formula (I).
  • Another embodiment of the invention is a polymer network derived from polymerization of the polymerizable liquid crystal composition comprising at least one compound of Formula (I).
  • the polymer network is useful as an optical element or as a pigment.
  • Another embodiment of the invention is a process for making the compounds as described by Formula (I).
  • twisted nematic phase twisted nematic phase
  • cholesteric phase chiral nematic
  • One embodiment of the invention is a compound of Formula (I):
  • R 1 and R 2 are each independently selected from the group: H, F, Cl and CH3; nl and n2 are each independently integers 3 to 20; q and r are each independently integers 0, 1 or 2, with the proviso that q + r is ⁇ l ; D is a divalent chiral radical selected from the group:
  • R 3 is a Cl to C6 straight or branched chain alkyl group
  • a C1-C6 group may be any one or more of Ci, C 2 , C 3 , C 4 , C 5 , or C 6 .
  • a preferred embodiment of the invention is a composition of Formula (I) wherein R 1 and R 2 are independently selected from H and CH 3 , and more preferably, R 1 and R 2 are H.
  • R 1 and R 2 are independently selected from H and CH 3 , and more preferably, R 1 and R 2 are H.
  • nl and n2 are, independently, integers 3 to 10.
  • D is selected from the group of Formulae (Dl), (D2) and (D3).
  • composition of Formula (I) wherein q and r is equal 1 is particularly preferred, and particularly preferred is a composition, wherein q and r is equal to 1 and B 1 and B 2 are R 4 -substituted-l ,4-phenyl.
  • compositions are wherein D is equal to (Dl) and B 1 and B 2 are R 4 -substituted-l ,4-phenyl, or 4,4'-biphenyl.
  • Other particularly favored compositions are wherein D is equal to (D2) and B 1 and B 2 are R 4 -substituted-l ,4- phenyl.
  • One embodiment of this invention is a process for providing the compound of Formula (I), which process may be distinguished from previous information concerning synthetic methods related to the preparation of similar types of compounds.
  • US 5,780,629 discloses in general terms materials including those of Formula (I), there is limited disclosure useful in relation to how to make the specific compounds of Formula (I) comprising ester moieties linking B 1 and B 2 to the spacer groups and the (meth)acrylate groups.
  • the available disclosure is directed essentially at the synthesis of compounds wherein ether (-O-) moieties link B 1 and B 2 to the spacer groups.
  • US 5,780,629 has limited useful disclosure in relation to providing the compound of Formula (I).
  • This invention thus provides, in the aforementioned embodiment, a process for preparing the compound of Formula (1) by: (a) providing a chiral organic diol, such as that from which the radical D is obtained; (b) reacting the chiral organic diol with one or more functionalized alkyl acids or acid halide(s) of the Formula (II):
  • X is Cl, Br or OH
  • X 1 is selected from the group: Cl, Br, I, -OMs (wherein Ms is methanesulfonyl), -OTs (wherein, Ts is toluenesulfonyl), and — OTf (wherein Tf is trifluoromethanesulfonyl); and n is an integer equal to 3 to 20; in a first reaction solvent at a first reaction temperature to provide one or more polyfunctionalized ester(s) and a first spent reaction mixture; (c) reacting the one or more polyfunctionalized ester(s) with a (meth)acrylate salt in the presence of a phase transfer catalyst, and a second reaction solvent at a second reaction temperature; to provide one or more poly (meth)acrylate ester(s) and a second spent reaction mixture.
  • the poly (meth)acrylate ester(s) may be alkyl and/or aryl ester(s).
  • the process step (b) further comprises the uses of a base, and when X is OH, further comprises the use of a carbodiimide dehydrating agent.
  • Step (c) preferably further comprises the use of one or more radical inhibitors.
  • a sufficient amount of the functionalized alkyl acid halide(s) preferably is about 1.8 to about 2.5 equivalents, and more preferably about 2.0 to 2.2 equivalents, based on the amount of the chiral organic diol.
  • the one or more functionalized alkyl acid halides(s) comprises two functionalized alkyl acid halide(s) in a molar ratio of about 0.05:1 to 1 :1, or two or more functionalized alkyl acid halide(s); and said step (b) provides a mixture of at least three polyfunctionalized alkyl ester(s).
  • This process, or derivations thereof using three or more polyfunctionalized alkyl acid halide(s) is a convenient and preferred process to provide complex mixtures of the compounds of the invention.
  • the first reaction solvent can be any solvent known in the art to be useful in performing acid halide condensations with alcohols, including alkyl ethers, such as THF, dioxane, dimethoxyethane; alkyl esters such as ethyl acetate and butyl acetate; hydrocarbons such as xylenes, and toluene; halogenated hydrocarbons such as 1,2-dichloroethane and dichloromethane.
  • alkyl ethers such as THF, dioxane, dimethoxyethane
  • alkyl esters such as ethyl acetate and butyl acetate
  • hydrocarbons such as xylenes, and toluene
  • halogenated hydrocarbons such as 1,2-dichloroethane and dichloromethane.
  • a preferred first reaction solvent is THF.
  • the (meth)acrylate salt useful in step (c) can be derived from neutralization of the corresponding (meth)acrylate acid including methacrylic acid, acrylic acid, 2-chloroacrylic acid, and 2-fIuoroacrylic acid.
  • the base used in the neutralization can be an alkali metal base, for instance, potassium carbonate and bicarbonate, sodium carbonate and bicarbonate; lithium carbonate and bicarbonate, and cesium carbonate and bicarbonate; to provide an alkali metal (meth)acrylate salt.
  • the base can be an alkali earth metal base, for instance, magnesium, calcium or barium carbonate; to provide an alkali earth metal (meth)acrylate salt.
  • the base also can be an amine base and particularly a hindered amine base such as a tertiary aliphatic, aromatic or heterocyclic amine as described above; to provide an ammonium (meth)acrylate salt.
  • Preferred (meth)acrylate salts for step (c) are selected from the group: potassium
  • (meth)acrylate, sodium (meth)acrylate, and ammonium (meth)acrylates selected from the group: triethylammonium, diisopropylethylamrnonium, and 2,6- dimethylpyridinium salts.
  • the (meth)acrylate salt can be provided from commercial sources; it can be prepared in a separate process step and used directly or purified by one or more methods known in the art such as washing, filtering, drying, recrystallizing, or precipitating the salt; or it can be made in situ by neutralization of a (meth)acrylate acid with a base.
  • a preferred embodiment of the invention is wherein the (meth)acrylate salt is provided by mixing (meth)acrylic acid and an alkali metal carbonate selected from the group: potassium hydrogen carbonate and potassium carbonate; in a molar ratio of about 1 : 1 to about 1 : 5, respectively, in said second reaction solvent.
  • the amount of (meth)acrylate salt to be used is about 2.0 about 10.0 equivalents per equivalent of the polyfunctiorialized alkyl ester(s).
  • the (meth)acrylate salt is an acrylate salt.
  • the phase transfer catalyst used in step (c) is a substance which, being at least partly present in or wetted by a first (usually organic) phase, promotes reaction between a reactant in the first phase and a reactant which it transfers to the first phase from a second phase, usually an aqueous or a solid phase. After reaction, the phase transfer catalyst is released for transferring further reactant.
  • the phase transfer catalyst is a quaternary ammonium or phosphonium salt preferably containing bulky organic groups, usually alkyl or aralkyl groups, to make it soluble in the organic phase. It is preferred that the phase catalyst is a tetraalkyl or aralkyl (e.g.
  • phase transfer catalyst in which the total number of carbon atoms attached to each nitrogen or phosphorus atom is at least 4. It is especially preferred that the number should be in the range of from 16 to 40.
  • Other substances suitable for use herein as the phase transfer catalyst include those reviewed by E. V. Dehmlow in Angewante Chernie, (International Edition), JJ3, 170 (1974).
  • quaternary ammonium salts are: cetyltrimethylammonium bromide, dicetyldimethylammonium chloride, octyltributylammonium bromide, trioctylmethylammonium chloride (available as AliquatTM 336), benzyldimethyllaurylammonium chloride, benzyltriethylammonium chloride, dilauryldimethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate and tetrabutylammonium iodide.
  • phase transfer catalysts examples include crown ethers and polyethylene glycol variants.
  • the phase transfer catalyst may be present in an amount ranging from 0.001 to 0.5 mole equivalents, and preferably 0.1-0.5 equivalents, of the polyfunctionalized alkyl ester(s).
  • a preferred phase transfer catalyst is selected from the group: tetrabutylammonium iodide, tetrabutylammonium bromide, and tetraheptyl ammonium bromide; and crown ethers selected from the group: 18- crown-6, CAS No.
  • the second reaction solvent can be any solvent known in the art to be useful in performing nucleophilic displacement of -X 1 with a (meth)acrylate salt.
  • a (meth)acrylate salt there is a preference for particular second reaction solvents that are aprotic in structure, and have a dipole moment of about 3.5 or less.
  • aprotic in structure we mean the solvents are devoid of active hydrogens such as hydroxyl or acid functionality. Solvents having these characteristics provide high rates of conversion of the polyfunctionalized alkyl ester(s) to product while maintaining a very low level of undesired ester cleavage products.
  • Preferred second reaction solvents include those selected from the group: alkyl ethers including tetrahydrofuran, dioxane and dimethoxyethane; ketones including acetone and 2- butanone; alkyl esters including butyl acetate and ethyl acetate; and acetonitrile.
  • the second reaction solvent may be the first spent reaction mixture.
  • the first reaction temperature and second reaction temperature are reaction temperatures that give a reasonable rate of reaction with a minimum of by-products.
  • the first reaction temperature generally is between — 30 0 C and about 50 0 C, and preferably about 0 0 C to about room temperature (RT 5 e.g. 25 0 C).
  • the second reaction temperature is generally about RT to about 120 0 C, and preferably about 50 0 C to about 100 0 C.
  • a base when used in step (b), it can include an inorganic base, for instance, alkali metal and alkali earth metal hydroxide, carbonate and bicarbonate; or an organic base such as an amine base that has at least two aliphatic groups, or that in which the N atom is in a cyclo aliphatic or aromatic ring, substituted in a manner that induces steric crowding around the N atom.
  • an organic base such as an amine base that has at least two aliphatic groups, or that in which the N atom is in a cyclo aliphatic or aromatic ring, substituted in a manner that induces steric crowding around the N atom.
  • the amine base will be of low water solubility and have a pK a of the conjugate acid of about 10.
  • it may be a heteroaromatic base such as pyridine or a substituted pyridine, for example 2,6-dimethylpyridine; or it may be a secondary amine, providing it is sufficiently sterically hindered:
  • An example of a suitable secondary amine is 2,2,6,6-tetramethyl-piperidine.
  • it is a tertiary amine of formula R 13 R 14 R 15 N wherein R 13 , R 14 and R 15 are independently Ci -10 alkyl groups or C 3-6 cycloalkyl groups.
  • the alkyl groups may be straight or branched chain.
  • Suitable tertiary amines of formula R 13 R 14 R 15 N are, for example, N,N- diisopropylethylamine, N,N-dimethylaniline, triethylamine, t-butyldimethylamine, N,N-diisopropylmethylamine, N,N-diisopropylisobutylamine, N,N-diisopropyl-2- ethylbutylamine, tri-n-butylamine.
  • amine bases selected from the group: triethylamine, diisopropylethylamine, tributylamine, pyridine, and 2,6- dimethylpyridine; and triethylamine is most preferred.
  • the base is preferably present in an amount of about 0.8 to about 5 equivalents per equivalent of the functionalized alkyl acid halide(s).
  • a by-product of the reaction is an amine salt such as an amine hydrochloride.
  • the amine salt is removed from the first spent reaction mixture by, for instance, filtering the reaction mixture. This is a convenient and preferred process wherein the second reaction solvent can include the first reaction solvent.
  • the one or more polyfunctionalized alkyl ester(s) provided by step (b) can be separated from the first spent reaction mixture by a variety of methods known in the art.
  • Preferred methods include any one or more of the steps: filtering the amine salt by-product; precipitating the reaction mixture into water and filtering; partitioning the reaction mixture with water and/or organic solvents; washing with reaction mixture with water; drying the reaction mixture with a drying agent; removal of solvent by evaporation; chromatography, crystallization and/or recrystallization of the one or more polyfunctionalized alkyl ester(s); and washing the crude product with one or more solvents which selectively remove byproducts without dissolving the one or more polyfunctionalized alkyl ester(s).
  • a carbodiimide dehydrating agent when used in step (b), can be any ⁇ diimide commonly used in coupling acids with alcohols and phenols.
  • a preferred carbodiimide for step (b) is dicyclohexylcarbodiimide.
  • a radical inhibitor when used in step (c), can be any radical inhibitor known to inhibit radical polymerization reactions of ( ⁇ neth)acrylate groups including 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methyIphenol, 2,6-di-tert- butyl-4-ethylphenol, 2-methyl-6-tert-butylphenol, 2,4,6-tri-tert-octylphenol, 2,4- dimethyl-6-tert-butylphenol, 2-tert-butyl-6-( ⁇ methylbenzyl)phenol, 2,4-di-tert- octylphenol, 2,6-di-tert-butyl-4-methoxyphenol, 2,6-di-tert-octyl-4-decoxyphenol, 2-tert-butyl-4-chlorophenol, 2,6-di-tert-butyl-4(N,N -dimemylarninomethyl- phenol), 2,2 -
  • the above list is not intended to be exhaustive; numerous classes of compounds that inhibit formation of radicals in organic materials are well known, and can be used in the practice of the present process.
  • the radical inhibitor can be a single compound, or a mixture of combination of such compounds.
  • the preferred radical inhibitors are hindered phenols selected from the group: 2,6-di-tert-butyl-4-methylphenol, phenothiazine, and tridecyl phosphate.
  • the process further comprises separating the one or more poly (meth)acrylate ester(s) provided by step (c) from the second spent reaction mixture.
  • This can be by a variety of methods known in the art including any one or more of the steps: filtering the second spent reaction mixture; precipitating the reaction mixture into water and filtering; partitioning the reaction mixture with water and/or organic solvents; washing the reaction mixture with water; drying the reaction mixture with a drying agent; removal of solvent by evaporation; chromatography, crystallization and/or recrystallization of the one or more poly (meth)acrylate ester(s); and washing the crude product with one or more solvents which selectively remove byproducts without dissolving the one or more polyfunctionalized alkyl ester(s).
  • compounds of Formula (I) wherein q and r are 1; and B 1 and B 2 are R 4 -substituted-l,4-phenyl radicals can be made from chiral diester diols (IIIa-d):
  • the diester diols (IIIa-d) are available by esterification of respective chiral diols: 1,4:3,6 dianhydro-D-sorbitol, CAS No. [652-67-5]; 1,4:3,6 dianhydro-D- mannitol, CAS No. [643-74-7]; 1,4:3,6 dia ⁇ hydro-L-iditol, CAS No. [24332-71- 6]; diethyl L-tartrate, CAS No. [87-91-2]. These chiral diols are available commercially from Aldrich Chemical Co.
  • the diester diols (IIIa-c) are readily prepared by heating the chiral diols with two or more equivalents of hydroxy acid in the presence of an acid catalyst with azeotropic removal of water.
  • Chiral diol (HId) can be made by esterification of diethyl L-tartrate with 4-benzyloxybenzoyl chloride in the presence of a base, followed by hydrogenation to cleave the benzyl protecting group.
  • compounds of Formula (I) wherein q is 1 and r is 0; and B 1 and B 2 are R 4 - substituted-l,4-phenyl radicals can be made from chiral ester diols (IVa-e):
  • ester diols (IVa-d) are available by mono-esterification of respective chiral diols.
  • US 6,468,444 discloses the synthesis of material of formula (IVd) wherein R 4 is H, the monoester of isomannitol, using an equivalent amount of 4-hydroxybenzoic acid and isomannitol in refluxing xylene in the presence of p-toluenesulfonic acid.
  • Chiral diol (IVe) can be made by selective mono-esterification of diethyl L-tartrate with 4-benzyloxybenzoyl chloride in the presence of a base, followed by hydrogenation to cleave the benzyl protecting group.
  • Another embodiment of the invention is a process for preparing the compounds of Formula (I) wherein q and/or r is equal to 2.
  • the process comprises (a) providing one or more polyol(s) selected from the group: Formulae (IIIa-d) and (IVa-e); and (b) reacting the polyol(s) with a sufficient amount of one or more (meth)acrylate aryl acids or acid halides of the Formula (Va-c):
  • step (b) includes a base and one or more radical inhibitors as described above; and when X is OH, further comprises a carbodiimide dehydrating agent.
  • the process is suitable for esterification of polyol(s) related to (IIIa-d) and (IVa-e) wherein the carboxylate group is derived from 6-hydroxy-2-napthalene carboxylic acid and 4'-hydroxy-4-biphenyl carboxylic acid, within the limits of the provisos disclosed for compounds of Formula (I).
  • Compounds of Formula (T) are useful in polymerizable liquid crystal compositions (i.e. mixtures), also of the invention.
  • Compounds of Formula (I) are useful as chiral dopants to induce chirality of a nematic phase to provide a twisted nematic phase.
  • Useful twisted nematic phases can be provided by mixing the chiral dopants at about 0.5 to about 30 wt % based on the total nematic mixture.
  • a wide variety of polymerizable and nonpolymerizable liquid crystals can be used in the polymerizable liquid crystal compositions of the invention including in those disclosed in Makromol. Chem. 190, 2255-2268 (1989); Macromolecules, 1988, 31, 5940; Makromol.
  • R 1 and R 2 are independently selected from the group: H, F, Cl and CH 3 ; nl and n2 are, independently, integers 3 to 20; m and p are, independently, integers 0 or 1; A is a divalent radical selected from the group:
  • R 5 - R 12 are independently selected from the group: H, Cl — C8 straight or branched chain alkyl, Cl — C8 straight or branched chain alkyloxy, F, Cl, phenyl,
  • X 2 is a divalent radical selected from the group: -O-, -(CBb) 2 C-, and -(CFa) 2 C-; and each B 3 and B 4 is a divalent radical independently selected from the group: R 4 -substituted-l,4-phenyl, wherein R 4 is H 5 -CH 3 or — OCH 3 ; 2,6-naphthyl; and 4,4"-biphenyl; with the proviso that when m + p is equal to 3 or 4, at least two of B 3 and B 4 are R 4 -substituted-l,4-phenyl.
  • a Cl-CS group may be any one or more of Ci, C 2 , C 3 , C 4 , C 5 , Ce, C 7 or C 8 .
  • Preferred polymerizable liquid crystal compositions of the invention have a twisted nematic phase below 120 0 C.
  • liquid crystal compositions of the invention are useful in preparing polymer networks that exhibit the fixed optical properties of twisted nematic polymer networks.
  • the polymer network of the invention is one or more polymerized layer(s) comprising a liquid crystal composition that include: polymerized films, coatings, castings and prints; including patterned, unpatterned, variable and nonvariable optical properties; that can be made by a wide variety of methods as disclosed, for instance, in US 4,637,896, 6,010,643 and 6,410,130, all hereby incorporated by reference.
  • one preferred method for making a polymer network comprises: providing a polymerizable twisted nematic mixture, in the form of a twisted nematic or isotropic phase, with a polymerization initiator, preferably a radical initiator; applying the twisted nematic mixture to one or more substrates, optionally the substrate(s) comprises an alignment layer, to provide a layer of the twisted nematic mixture; optionally treating the layer to provide a desired twisted nematic phase; and polymerizing the twisted nematic phase, preferably by exposing the twisted nematic phase to actinic radiation.
  • Actinic radiation includes heat, microwave radiation, UV and visible light, and electron beam and other radiation.
  • the liquid crystal compositions of various embodiments of the invention can include a radical initiator, and preferably the radical initiator is a photoinitiator useful in conducting photochemical polymerizations.
  • Photochemical polymerizations can include customary commercial photoinitiators including, for example, isobutyl benzoin ether, 2,4,6- trimethylbenzoyldiphenylphosphine oxide, and/or 1-hydroxycyclohexyl phenyl ketone. For curing by electron beams, such initiators are not required. Applying the twisted nematic mixture can be accomplished by any method that gives a uniform layer, or if desired, a patterned or non-uniform layer.
  • Coating including rod-coating, extrusion coating, gravure coating and spin-coating, spraying, printing, blading, knifing, or a combination of methods, can be used.
  • Substrates can be pre-coated with alignment layers: polymers that are applied to substrates and mechanically buffed with a rubbing clothe or optically aligned with polarized light.
  • Useful polyimide alignment layers are disclosed in US 6,887,455. Alignment of twisted nematic phases by coating of dilute liquid crystal mixtures is disclosed in US 6,410,130.
  • twisted nematic phases When the propagation direction of plane polarized or unpolarized light is along the helical axis of the twisted nematic layer, the wavelength of maximum reflection, ⁇ o, is governed by the equation ⁇ o — n a p, wherein n a is the average of n o and n e , and n o and n e are defined as the ordinary and extraordinary refractive indices respectively, of the twisted nematic phase measured in the propagation direction and p is the pitch of the helix (the distance the helix takes to repeat itself).
  • ⁇ o Light outside the vicinity of ⁇ o is essentially unaffected in transmission.
  • the twisted nematic phase exhibits selective reflection of the light such that approximately 50% of the light is reflected and approximately 50% of the light is transmitted, with both the reflected and transmitted beams being substantially circularly polarized.
  • a right handed helix reflects right handed circularly polarized light and transmits left handed circularly polarized light.
  • the pitch p can be tuned effectively by manipulating the amount of chiral dopant, the twisting power of the dopant and selection of the nematic materials.
  • the pitch is sensitive to temperature, unwinding or tightening with a change in temperature; to electric fields, dopants, and other environmental considerations.
  • manipulation of the pitch, and thus the wavelength of maximum reflection can be accomplished with a wide variety of tools.
  • the bandwidth ⁇ of the reflected wavelength band also can be manipulated as disclosed in US 5,506,704 and US 5,793,456.
  • the polymer networks of the invention can be made either flexible or brittle depending on crosslinking.
  • the brittle films can be flaked and the flakes used as pigments in a variety of inks or paints for use in cosmetics and automobile paint.
  • the films can be combined with other pigments or pigment layers, for instance black layers that act to enhance the brilliance of the reflected light.
  • the polymer networks of the invention are useful as optical elements or components of an optical element.
  • An optical element is any film, coating or shaped object that is used to modify the characteristics of light.
  • the modifications produced by optical elements include changes in the intensity of light through changes in transmission or reflectivity, changes in wavelength or wavelength distribution, changes in the state of polarization, changes in the direction of propagation of part or all of the light, or changes in the spatial distribution of intensity by, for example, focusing, collimating, or diffusing the light.
  • Examples of optical elements include linear polarizers, circular polarizers, lenses, mirrors, collimators, diffusers, reflectors and the like.
  • One specific example of an optical element is a layer of a cholesteric polymer network of the invention that reflects light within the vicinity of ⁇ o, employed in a window structure.
  • An optical element prepared from a polymer network as provided by this invention may be used as a component in a multilayer laminate, one form of which may be a laminated article.
  • the optical element may be provided in the form of a sheet that has a thickness of greater than about 10 mils (0.25 mm), or about 20 mils (0.50 mm) or greater, where the total thickness of all components from which the laminate is composed may be a thickness of about 30 mils (0.75 mm) or greater to ensure adequate penetration resistance commonly regarded as a feature of safety laminates.
  • Polymeric sheets useful for such purpose may be formed by any suitable process such as extrusion, calendaring, solution casting or injection molding.
  • a polymeric sheet to be used as an interlayer within a laminate may have a roughened surface to effectively allow most of the air to be removed from between the surfaces of the laminate during the lamination process. This may be accomplished, for example, by mechanically embossing the sheet after extrusion, as described above, or by melt fracture during extrusion of the sheet and the like. This rough surface is only temporary and particularly functions to facilitate deairing during laminating after which it is melted smooth from the elevated temperature and pressure associated with autoclaving and other lamination processes.
  • the film may be treated to enhance the adhesion to a coating or to a polymeric sheet or both.
  • This treatment may take any suitable form known such as adhesives, primers, such as silanes, flame treatments, plasma treatments, electron beam treatments, oxidation treatments, corona discharge treatments, chemical treatments, chromic acid treatments, hot air treatments, ozone treatments, ultraviolet light treatments, sand blast treatments, solvent treatments, and the like and combinations thereof.
  • a film suitable for use herein as an optical element may have a thickness of about 10 mils (0.25 mm) or less, or a thickness of between about 0.5 mils (0.012 millimeters (mm)), to about 10 mils (0.25 mm), or a thickness of about 1 mil (0.025mm) to about 5 mils (0.13mm).
  • a process to produce a multilayer laminate provides a polymeric sheet laminated to a polymeric film that is coated with the twisted nematic liquid crystal layer.
  • the polymeric sheet may be lightly bonded to the film with the twisted nematic liquid crystal through a nip roll bonding process.
  • the components may be heated to a temperature sufficient to promote temporary fusion bonding, i.e., to cause the surfaces of the polymeric sheet or the polymeric film to become tacky. Suitable temperatures are within the range of about 50 0 C to about 120 0 C, with the preferred surface temperatures reaching about 65°C.
  • the film with the twisted nematic liquid crystal is fed along with the polymeric sheet through nip rolls where the two layers are merged together under moderate pressure to form a weakly bonded laminate.
  • the bonding pressure will be within the range of about 10 psi (0.7 kg/sq cm), to about 75 psi (5.3 kg/sq cm), and is preferably within the range of about 25 psi (1.8 kg/sq cm), to about 30 psi (2.1 kg/sq cm).
  • the laminate is passed over a series of cooling rolls which ensure that the laminate taken up on a roll is not tacky.
  • Laminates made through this process will have sufficient strength to allow handling by laminators who may produce further laminated articles, such as glass laminates, which encapsulate this laminate.
  • a multi-layer laminate may also be formed by an autoclave processes wherein a glass sheet, an interlayer composed of a polymeric sheet, a polymeric film with the twisted nematic liquid crystal (either in the form of a coated layer or of a film), a second polymeric sheet, and a second glass sheet are laminated together under heat and pressure and a vacuum (for example, in the range of about 27-28 inches (689-711 mm) Hg), to remove air.
  • a multilayer laminate as provided by this invention may include additional layers, such as other polymeric sheets, other coated or uncoated polymeric films, half-wave plates and absorptive layer.
  • the additional layers may be glass or rigid transparent plastic sheets, such as, for example, polycarbonates, acrylics, polyacrylates, cyclic polyolefins, such as ethylene norbornene polymers, metallocene-catalyzed polystyrenes and the like and combinations thereof.
  • Metal or ceramic plates may also be suitable, if transparency is not required for the laminate.
  • glass is meant to include not only window glass, plate glass, silicate glass, sheet glass, and float glass,, but also includes colored glass, specialty glass which includes ingredients to control, for example, solar heating, coated glass with, for example, sputtered metals, such as silver or indium tin oxide, for solar control purposes and other specialty glasses.
  • specialty glass which includes ingredients to control, for example, solar heating
  • the type of glass to be selected for a particular laminate depends on the intended use.
  • An absorptive layer may also comprise part of a laminate as provided herein.
  • the absorptive layer may be in the form of a discrete film.
  • the absorptive layer may be in the form of a coating on one or more of the twisted nematic liquid crystal layers, the polymeric sheets, the polymeric films and the rigid sheets.
  • the absorptive layer may be incorporated into one or more of the twisted nematic liquid crystal layers, the polymeric sheets, the polymeric films and the rigid sheets.
  • the thermal transitions and phase assignments were made with differential scanning calorimetry and hotstage optical microscopy. Unless stated otherwise, phase behavior is reported for the first heating.
  • THF tetrahydrofuran
  • TEA triethylamine
  • RT room temperature. Unless noted otherwise, the phase behavior refers to the first heating cycle.
  • liquid crystal compounds of formula (VI) that are used in illustrating a chiral liquid crystal composition and polymer network of various embodiments the invention are described below.
  • 6-Hydroxy-naphthalene-2-carboxylic acid 56 g
  • isosorbide 20 g
  • p- toluenesulfonic acid 1 g
  • xylenes 250 mL
  • the reaction mixture was heated to reflux until 5 mL of water were collected in the trap ( ⁇ 24 hrs).
  • two additional charges of p-toluenesulfonic acid 1.0 g were added.
  • the xylenes were decanted and the solids were rinsed with hexanes.
  • This example illustrates an alternate synthetic route as applied to the synthesis of Compound 19, a chiral monomer of one embodiment of the invention.
  • 6-Hydroxy-naphtalene-2-carboxylic acid 56 g
  • isomannide 20 g
  • p- toluenesulfonic acid 1 g
  • xylenes 250 mL
  • the reaction mixture was heated to reflux until 5 mL of water were collected in the trap ( ⁇ 24 hrs).
  • two additional charges of p-toluenesulfonic acid 1.0 g
  • This example illustrates the method used to prepare a twisted nematic mixture wherein each compound was prepared separately.
  • This example illustrates the method used to prepare a twisted nematic mixture wherein each compound was prepared separately.
  • Mixture 2 was prepared in a similar manner as was described above for Mixture 1.
  • a polyethylene terephthalate film was hand rubbed with a Yoshikawa YA-20-R rubbing cloth.
  • Each of the formulae shown herein describes each and all of the separate, individual compounds that can be formed in that formula by (i) selection from within the prescribed range for one of the variable, substituents or numerical coefficents while all of the other variable radicals, substituents or numerical coefficents are held constant, and (ii) performing in turn the same selection from within the prescribed range for each of the other variable radicals, substituents or numerical coefficents with the others being held constant.
  • a plurality of compounds may be described by selecting more than one but less than all of the members of the group of radicals, substituents or numerical coefficents.
  • substituents or numerical coefficents is a subgroup containing (a) only one of the members of the group described by the range, or (b) more than one but less than all of the members of the group, the selected member(s) are selected by omitting those member(s) of the whole group that are not selected to form the subgroup.
  • variable radicals, substituents or numerical coefficents each of which variable radicals, substituents or numerical coefficents is defined by the members of the whole group, described by the range for that variable radical, substituent or numerical coefficient in the absence of the member(s) omitted to form the subgroup.
  • the range includes the endpoints thereof and all the individual integers and fractions within the range, and also includes each of the narrower ranges therein formed by all the various possible combinations of those endpoints and internal integers and fractions to form subgroups of the larger group of values to the same extent as if each of those narrower ranges was explicitly recited.
  • a range of numerical values is stated herein as being greater than a stated value, the range is nevertheless finite and is bounded on its upper end by a value that is operable within the context of the invention as described herein.
  • a range of numerical values is stated herein as being less than a stated value, the range is nevertheless bounded on its lower end by a non-zero value.
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JP2009532363A (ja) 2009-09-10

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