WO1997014674A1 - Liquid crystalline (meth)acrylate compounds, composition and method - Google Patents

Liquid crystalline (meth)acrylate compounds, composition and method Download PDF

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Publication number
WO1997014674A1
WO1997014674A1 PCT/US1996/016436 US9616436W WO9714674A1 WO 1997014674 A1 WO1997014674 A1 WO 1997014674A1 US 9616436 W US9616436 W US 9616436W WO 9714674 A1 WO9714674 A1 WO 9714674A1
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Prior art keywords
carbon atoms
substituted
unsubstituted
moiety
independently
Prior art date
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PCT/US1996/016436
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French (fr)
Inventor
Joachem E. Klee
Holger Frey
Dirk Holter
Rolf Mulhaupt
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Dentsply International Inc.
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Publication date
Application filed by Dentsply International Inc. filed Critical Dentsply International Inc.
Priority to JP51590897A priority Critical patent/JP2001509128A/en
Priority to DE69618661T priority patent/DE69618661T2/en
Priority to EP96936465A priority patent/EP0861230B1/en
Publication of WO1997014674A1 publication Critical patent/WO1997014674A1/en

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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C07C69/708Ethers
    • C07C69/712Ethers the hydroxy group of the ester being etherified with a hydroxy compound having the hydroxy group bound to a carbon atom of a six-membered aromatic ring
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00Preparations for dentistry
    • A61K6/20Protective coatings for natural or artificial teeth, e.g. sealings, dye coatings or varnish
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00Preparations for dentistry
    • A61K6/30Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00Preparations for dentistry
    • A61K6/50Preparations specially adapted for dental root treatment
    • A61K6/54Filling; Sealing
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00Preparations for dentistry
    • A61K6/80Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/884Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
    • A61K6/887Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00Preparations for dentistry
    • A61K6/80Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/884Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
    • A61K6/891Compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • A61K6/893Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00Carboxylic acid nitriles
    • C07C255/49Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/54Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and etherified hydroxy groups bound to the carbon skeleton
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06Polymers provided for in subclass C08G
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06Polymers provided for in subclass C08G
    • C08F290/061Polyesters; Polycarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06Polymers provided for in subclass C08G
    • C08F290/064Polymers containing more than one epoxy group per molecule
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/83Chemically modified polymers
    • C08G18/834Chemically modified polymers by compounds containing a thiol group
    • C08G18/835Unsaturated polymers modified by compounds containing a thiol group
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02Polycondensates containing more than one epoxy group per molecule
    • C08G59/10Polycondensates containing more than one epoxy group per molecule of polyamines with epihalohydrins or precursors thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02Polycondensates containing more than one epoxy group per molecule
    • C08G59/12Polycondensates containing more than one epoxy group per molecule of polycarboxylic acids with epihalohydrins or precursors thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14Polycondensates modified by chemical after-treatment
    • C08G59/1433Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C08G59/1461Unsaturated monoacids
    • C08G59/1466Acrylic or methacrylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14Polycondensates modified by chemical after-treatment
    • C08G59/1494Polycondensates modified by chemical after-treatment followed by a further chemical treatment thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4292Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with monocarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/52Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06Unsaturated polyesters
    • C08L67/07Unsaturated polyesters having terminal carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00Liquid crystal materials
    • C09K19/04Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06Non-steroidal liquid crystal compounds
    • C09K19/08Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
    • C09K19/2007Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
    • C09K19/2021Compounds containing at least one asymmetric carbon atom
    • C09K19/2028Compounds containing at least one asymmetric carbon atom containing additionally a linking group other than -COO- or -OCO-, e.g. -CH2-CH2-, -CH=CH-, -C=C-; containing at least one additional carbon atom in the chain containing -COO- or -OCO- groups, e.g. -COO-CH*-CH3
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00Liquid crystal materials
    • C09K19/04Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06Non-steroidal liquid crystal compounds
    • C09K19/08Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001Cyclohexane rings
    • C09K19/3066Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers
    • C09K19/3068Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers chain containing -COO- or -OCO- groups
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2270/00Compositions for creating interpenetrating networks
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00Liquid crystal materials
    • C09K19/04Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K2019/0444Liquid 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
    • C09K2019/0448Liquid 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

Definitions

  • the invention relates to liquid crystalline (meth)acrylates
  • electrooptical application such as in liquid-crystal displays.
  • invention provides (meth)acrylate compounds which are liquid below
  • compositions for treating natural teeth such as
  • the invention provides dental cement
  • compositions and methods of using them for binding hard tooth compositions and methods of using them for binding hard tooth
  • the cement compositions include
  • compositions of the invention are useful as dental
  • compositions of the invention are cements, liners, bases and restoratives.
  • compositions include less reactive diluent than prior art compositions.
  • terephthaloyl ester moiety are disclosed by G.G.Barclay, C.K. Ober,
  • a diacrylate (wherein R is H) and a dimethacrylate (wherein R is CH 3 ) having the formula IV which comprises a biphenylhydroxy moiety is disclosed by H. Litt Morton, Wha-Tzong Whang, Kung-Ti Yen, Xue-Jun Qian, in J. Polym. Sci., Part A,: Polym. Chem. 31 (1993) 183, Morton H. Lift US 89-369205.
  • Acetylene terminated aromatic ester having the formula V are described by E. P. Douglas, Polymer Prep. 34 (1993) 702.
  • Methacrylates having the formula VI with a ridged rod-like moiety are disclosed in T. Shindo, T. Uryu, Liquid Crystals 15 (1993) 239).
  • liquid crystalline mono- or difunctional molecules have melting temperatures and liquid crystalline behavior at temperatures above 50°C (Table 1 below, page 25). An application of these molecules in the liquid crystalline phase require temperatures over their melting temperature (50 to 170°C). An application at room temperature is only possible in the solid state or in solution.
  • monomers which are liquid at room temperature and which show liquid crystalline behavior at least between 20 and 40°C. These liquid crystalline monomers are useful in dentistry, medicine, microelectronics and optoelectronics.
  • R T is a group of the general formula
  • each L 1 and L 2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN
  • R 3 is a covalent bond or a substituted or unsubstituted alkylene having 1 to 20 carbon atoms, oxyalkylene having 1 to 20 carbon atoms, thioalkylene having 1 to 20 carbon atoms or a carboxyalkylene having 1 to 20 carbon atoms
  • R 4 is hydrogen, a substituted or an unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, or aryl rest having 6 to 20 carbon atoms,
  • M is a mesogenic group of the general formula -A-Z, -A-Y B-Z, -A-Y B-Y 2 -C-Z or a steroidal moiety, preferably selected of the group of cholesteryl compounds, wherein each A, B and C independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 2 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to
  • each L and L 2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN
  • Z is a hydrogen, halogen, CN, -OR, COOR, NO 2 , a halogen substituted or unsubstituted alkylene or alkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted oxyalkylene or oxyalkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted thioalkylene or thioalkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted carboxyalkylene or alkanoylenoxy having 1 to 20 carbon atoms,
  • X is a covalent bond, CO, NHCO, OCO n is an integer from 1 to 10.
  • Figure 1 is a graph of the thermomechanical properties of a
  • the invention provides a polymerizable compound within the scope of the general formula:
  • each L-, and L 2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN,
  • R 3 is a covalent bond or a substituted or unsubstituted alkylene having 1 to 20 carbon atoms, oxyalkylene having 1 to 20 carbon atoms, thioalkylene having 1 to 20 carbon atoms or a carboxyalkylene having 1 to 20 carbon atoms,
  • R 4 is hydrogen, a substituted or an unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, or aryl rest having 6 to 20 carbon atoms,
  • each L and L 2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN,
  • Z is a hydrogen, halogen, CN, -OR, COOR, NO 2 , a halogen substituted or unsubstituted alkylene or alkylidene having 1 to 20 carbon atoms, a halogen substituted or unsubstituted oxyalkylene or oxyalkylidene having 1 to 20 carbon atoms, a halogen substituted or unsubstituted thioalkylene or thioalkylidene having 1 to 20 carbon atoms, a halogen substituted or unsubstituted carboxyalkylene or alkanoylenoxy having
  • X is a covalent bond, CO, NHCO, OCO and n is an integer from 1 to
  • liquid crystalline (meth)acrylates within the scope of general formula 1 which have at least two polymerizable double bonds and at least two rigid rod-like moieties R and M
  • each Li and L 2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN R 3 is a covalent bond or a substituted or unsubstituted alkylene having 1 to 20 carbon atoms, oxyalkylene having 1 to 20 carbon atoms, thioalkylene having 1 to 20 carbon atoms or a carboxyalkylene having 1 to 20 carbon atoms
  • R 4 is hydrogen, a substituted or an unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, or aryl rest having 6 to 20 carbon atoms,
  • M is a mesogenic group of the general formula
  • each A, B and C independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 2 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to 30 carbon atoms
  • each LT and L 2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN
  • Z is a hydrogen, halogen, CN, -OR, COOR, NO 2 , a halogen substituted or unsubstituted alkylene or alkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted oxyalkylene or oxyalkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted thioalkylene or thioalkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted carboxyalkylene or alkanoylenoxy having 1 to 20 carbon atoms,
  • X is a covalent bond, CO, NHCO, OCO n is an integer from 1 to 10.
  • liquid crystalline (meth)acrylates have structures A and B.
  • a macromonomer within the scope of general formula 5 is formed by reaction of a 2,3-epoxypropyl (meth)acrylate compound within the scope of general formula 4, a diphenol compound within the scope of general formula 3 and a diepoxide compound within the scope of general formula 2 as follows.
  • R 2 is a group of the general formula
  • each L T and L 2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN
  • R 4 is hydrogen, a substituted or an unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, or aryl rest having 6 to 20 carbon atoms,
  • R T is a substituted or unsubstituted aryl having from 6 to 24 carbon atoms and/or a substituted or unsubstituted cycloalkyl having from 5 to 12 carbon atoms.
  • R ⁇ is
  • R 5 is hydrogen, alkyl having from 1 to 12 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, aryl having from 6 to 18 carbon atoms and
  • Y is substituted or unsubstituted alkylene having from 1 to 5 carbon atoms, O, CO, OCO, S, SO 2 and, n is an integer from 1 to 10. Preferably n is 1, 2, or 3.
  • R 3 is a covalent bond or a substituted or unsubstituted alkylene having 1 to 20 carbon atoms, oxyalkylene having 1 to 20 carbon atoms, thioalkylene having 1 to 20 carbon atoms or a carboxyalkylene having 1 to 20 carbon atoms
  • M is a mesogenic group of the general formula
  • each A, B and C independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 2 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to 30 carbon atoms
  • each L T and L 2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN
  • Z is a hydrogen, halogen, CN, -OR, COOR, NO 2 , a halogen substituted or unsubstituted alkylene or alkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted oxyalkylene or oxyalkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted thioalkylene or thioalkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted carboxyalkylene or alkanoylenoxy having 1 to 20 carbon atoms,
  • esterification, etherification and urethane formation of the di(meth)acrylate hydroxyl groups is carried out in solutions.
  • solvents for the esterification were used tetrahydrofurane, dioxane, CH 2 CI 2 , DMF or others, or polymerizable monomers such as triethyleneglycol bismethacrylate, diethyleneglycol bismethacrylate, dioxolan bismethacrylate, vinyl-, vinylene- or vinylidene-, acrylate- or methacrylate substituted spiroorthoesters and 2,2-bis[p- (acryloxyethoxy) phenyl] propane.
  • liquid crystalline di(meth)acrylate within the scope of structural formula 9 is synthesized in the following manner: 2,3- epoxy propoxy methacrylate and 4,4 ' -dihydroxy biphenyl are mixed and reacted for 15 hours at 115°C to form a methacrylate terminated macromonomer having hydroxyl groups.
  • the macromonomer hydroxyl groups are then esterified by mixing at O 97/14674 PC17US96/16436
  • compositions of the invention are formulated as one, two or more components, UV curable, visible light curable, self cure, and/or dual cure product or combinations of these.
  • the composition of a preferred embodiment of the invention includes polymerizable carboxylic acid monomer, an optional filler and/or diluent, a cationic elutable glass or other source of polyvalent cations, and a polymerization catalyst system.
  • Fillers which are suited for use in compositions of the invention are organic and/or inorganic particles, for example inorganic glasses such as are used in glass ionomer cements.
  • Exemplary of such fillers are those of U.S. Patent 4,814,362 which is incorporated herein by reference in its entirety.
  • Preferred fillers are glasses formed from or including, barium, calcium, strontium, lanthanum, tantalum, and/or tungsten silicates and aluminates and/or aluminosilicates, silica, including submicron silica, quartz, and/or ceramics for example, calcium hydroxy apatite.
  • reactive cations especially those of calcium, strontium and aluminium, and anions especially fluoride ions; are eluted from the fillers.
  • the fillers used in the invention preferably are reduced in particle size and are preferably silanated before they are incorporated into such compositions.
  • Preferred levels of filler are from about 20% to about 85% based on the total weight of the composition, with from about 40% to about 85% being more preferable and about 50-80% being most preferred. If a more finely particulated filler is used, amounts of filler may be decreased due to the relative increase in surface area which attends the smaller sizes of particles.
  • Preferred particle size distributions are from 0.02 to 50 microns, more preferably 0.1 to 10 microns, and most preferably 1 to 6 microns.
  • compositions of the present invention may be achieved using standard compounding techniques. For example, liquids, photoinitiator(s), and accelerator(s) are blended first, and fillers are added incrementally thereafter.
  • a photosafe room illumination i.e., one that does not contain substantial amounts of wavelengths of electromagnetic radiation that would activate the photoinitiating system is used to avoid initiating polymerization of the composition prematurely.
  • the compounds of the present invention also have medical applications such as in self adhesive bone cements. However, they are most preferred to use in dental treatment by application to a tooth or a number of teeth in vivo, in the mouth of a live patient by a dentist or dental practitioner.
  • the application of the compositions of the invention is preferably
  • ingredients such as curing catalysts, initiators, accelerators, diluents
  • composition is applied as a cement using
  • Inlays preferably are polymers, or
  • inlays are machined from metal such as titanium or gold
  • polymer compositions for example by CAD-CAM procedures.
  • appliances are bonded to teeth using cement compositions of the
  • Such cement compositions join metal or ceramic to tooth by
  • a preferred composition of the invention includes a two-part
  • One part includes an initiator.
  • the second part comprises filled and the co-initiator.
  • the two parts are spatuled to form a cement
  • the cement includes a visible light and/or a
  • luting cement compositions have low
  • compositions of the present invention may be prepared of such high
  • compositions of the invention are mechanically
  • a preferred dental treatment in accordance with the invention is
  • the dental filling composition includes finely divided filler.
  • composition is applied to a tooth as a filling material
  • component pit and fissure sealant which includes at least one
  • the invention are an especially valuable means of reducing caries by
  • the invention are preferably applied with or without prior acid etching or
  • compositions of the invention are preferably included in compositions of the
  • Fluoride is eluted to reduce the incidence of caries in tooth
  • compositions of the invention include two or more
  • the polymerizable monomer is preferably liquid at 23 ' C,
  • composition with amounts ranging from about 1 to about 99.98%
  • compositions of the invention include an adhesion
  • promoter for example a phosphorus-containing adhesion promoter
  • the phosphorus derivative may be any halogen atoms covalently or otherwise bonded directly to a phosphorus atom.
  • the phosphorus derivative may be any halogen atoms covalently or otherwise bonded directly to a phosphorus atom.
  • phosphorus-containing adhesion promoters comprise polymerizable
  • phosphorus materials having ethylenic unsaturation include, among others, organic esters of one or more acids of phosphorus
  • organic portion of the ester contains at least one polymerizable
  • the organic portion of the ester may
  • alkenyl alkenoxy, cycloalkenyl, aralkenyl, or alkenaryl
  • the organic portion preferably may have from 2 to 40 carbon atoms.
  • atoms i.e., atoms other than carbon, and can be unsubstituted or
  • phosphoric acid groups such as hydroxyethyl methacrylate
  • dimethacrylate phosphate dimethacrylate phosphate.
  • Other suitable polymerizable phosphorus acid esters are disclosed, for example, in U.S. Pat. No. 4,499,251 to
  • the preferred compounds are those polyethylenically unsaturated
  • R is an organic radical having a valency of n +1; and R may be
  • unsubstituted and may comprise an aliphatic radical, or a
  • R 1 is a hydrogen atom, alkyl having from 1 to 3 carbon atoms,
  • n is an integer of at least 1.
  • n is an integer of 2 or
  • pentaerythritol trimethacrylate monophosphate dipentaerythritol pentaacrylate monophosphate
  • dipentaerythritol pentaacrylate monophosphate dipentaerythritol
  • acid compound may comprise from about 0.25 to about 99.998% by
  • phosphorus acid compound would comprise from about 2 to about
  • compositions of the invention include a catalyst
  • the catalyst may comprise, for example,
  • an organic peroxide type initiator such as dibenzoyl
  • an actinic light sensitive initiator such as ultraviolet light-
  • benzophenones benzoin methyl ether, isopropoxybenzoin, benzoin
  • alpha-diketones such as camphoroquinone
  • the preferred initiators are the visible light sensitive initiators.
  • the catalyst generally is employed in the range of
  • the catalyst is used within the range of from 0.01 to about
  • compositions which include an accelerator system
  • the amine or amine salt may be
  • composition whereas the sulfinic acid or salt thereof is present in an
  • amine or amine salt is in the range of 0.001 to about 10% by weight of
  • the polymerizable composition and the sulfinic acid or a sulfinic acid
  • salt is in the range from about 0.01 to about 5 percent by weight of the
  • the amine or amine salt is in an amount from about 0.1-8 percent by
  • this invention desirably is a secondary or tertiary amine rather than a
  • Suitable amines include
  • Primers and adhesives of the invention may be filled to such an
  • composition of the invention comprises by weight about 5-20%
  • Example 1 To 5.00 g liquid crystalline di(meth)acrylate of Example 1 are added and 0,05 g JRAGCURE 651 (Ciba - Geigy). Using a curing unit (Dentsply De Trey) the mixture is polymerized by irradiation with visible light during 40 seconds. The degree of polymerization is about 85 %. The obtained material shows a volume shrinkage of 2.4 percent.
  • the thermo-mechanical properties are shown in Figure 1 wherein E' (storage modulus) is 2.8 • 10 9 Ps (25°C), E" (loss modulus) is 2.9 • 10 8 Pa (25°C) and tan ⁇ (E'VE') is 0.22.
  • Table 1 shows the Melting Points (°C) of LC-Monomers II - VI and the glass transition temperatures of Examples 1 and 2.
  • the powder and liquid are mixed in a 1 :1 ratio by volume to form a

Abstract

Liquid crystalline (meth)acrylates of the invention include at least three rigid rod-like moieties. One of these moieties is comprised between the (meth)acrylate rests and further two moieties are bonded as side chains. The liquid crystalline (meth)acrylates polymerizable using redox initiators and/or photo intiators. The (meth)acrylates of the invention polymerize quantitative and with very low volume shrinkage of less than 2.5 percent. The invention provides a polymerizable compound within the scope of general formula (I). These compounds are used in dental compositions and methods of use thereof.

Description

Liquid crystalline (meth)acrylate Compounds , Composiϋon and Method
This is a continuation-in-part of U.S. Patent Application Serial
No. 08/543,950 filed October 17, 1995 (Case 1865).
The invention relates to liquid crystalline (meth)acrylates
suitable for dental and medical applications, as well as for optical,
electrooptical application such as in liquid-crystal displays. The
invention provides (meth)acrylate compounds which are liquid below
50 ' C, and are useful in compositions for treating natural teeth, such as
dental restorative, cement, adhesive, primer, sealant and root canal
filling compositions. The invention provides dental cement
compositions and methods of using them for binding hard tooth
material, metal and ceramic. The cement compositions include
polymerizable ethylenically unsaturated monomers. The cements
have superior adhesion to tooth without separately acid etching dentin
or enamel. Compositions of the invention are useful as dental
cements, liners, bases and restoratives. Compositions of the invention
include less reactive diluent than prior art compositions. Compositions
of the invention polymerize to form polymeric material having low or no
residual monomer, preferably less than 1 percent residual monomer. A series of acrylate, methacrylate or vinyl terminated
compounds comprising a mesogenic or rigid rod-like moiety including
(meth) acrylate terminated oligomers I and II with a mesogenic
terephthaloyl ester moiety are disclosed by G.G.Barclay, C.K. Ober,
Prog. Polym. Sci. 18 (1993) 899; D. J. Broer, G. N. Mol, Polym. Engng.
Sci. 31 (1991) 625; R. A. M. Hikmet, J. Lub, J. A. Higgins, Polymer 34
(1993) 1736.
Figure imgf000004_0001
Figure imgf000004_0002
p-Hydroxy benzoic ester moieties incorporated into vinyl terminated compounds III are disclosed by D. J. Broer, J. Lub, G. N. Mol, Macromol. 26 (1993) 1244.
Figure imgf000004_0003
A diacrylate (wherein R is H) and a dimethacrylate (wherein R is CH3) having the formula IV which comprises a biphenylhydroxy moiety is disclosed by H. Litt Morton, Wha-Tzong Whang, Kung-Ti Yen, Xue-Jun Qian, in J. Polym. Sci., Part A,: Polym. Chem. 31 (1993) 183, Morton H. Lift US 89-369205.
Figure imgf000005_0001
Acetylene terminated aromatic ester having the formula V are described by E. P. Douglas, Polymer Prep. 34 (1993) 702.
Figure imgf000005_0002
Methacrylates having the formula VI with a ridged rod-like moiety are disclosed in T. Shindo, T. Uryu, Liquid Crystals 15 (1993) 239).
Figure imgf000005_0003
Figure imgf000005_0004
A vinyl terminated bishydroxy benzoate having formula VII which comprises spacers and exhibits relatively low phase transition temperatures only on cooling (n=11: i65n62sA47sB31 k) and relatively narrow liquid crystalline phases, are disclosed by H. Anderson, F. Sahlen, and U.W. Gedde, A. Hult, in Macromol. Symp. (1994) 339.
Mixtures of (meth)acrylates comprising liquid crystalline monomers, dimethacrylates (2,2-Bis-[p-(2-hydroxy-3- methacryloyloxypropoxy)-phenyl]-propane) and di(meth) acrylates comprising liquid crystalline monomers are described in EP 0379058.
However, the known liquid crystalline mono- or difunctional molecules have melting temperatures and liquid crystalline behavior at temperatures above 50°C (Table 1 below, page 25). An application of these molecules in the liquid crystalline phase require temperatures over their melting temperature (50 to 170°C). An application at room temperature is only possible in the solid state or in solution.
In accordance with the invention monomers are provided which are liquid at room temperature and which show liquid crystalline behavior at least between 20 and 40°C. These liquid crystalline monomers are useful in dentistry, medicine, microelectronics and optoelectronics.
It is an object of the invention to provide a polymerizable compound within the scope of the general formula:
R4 O-X-R3-M R4
I I I
CH2=C-C-O-[-CH2-CH-CH2-O-R1-O-]n-CH2-CH-CH2-O-C-C=CH2
II I II
O M-R3-X-O o
wherein
RT is a group of the general formula
-A-, -A-Y^B-, -A-YrB-Y2-C or a steroidal moiety, preferably selected of the group of cholesteryl compounds, wherein each A, B and C independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 2 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to 30 carbon atoms, a substituted or unsubstituted alkylene moiety having 2 to 20 carbon atoms each YT and Y2 independently is a covalent bond, OCO, N=N, CH=N, C=C, CO, O(CO)O, O, S, SO2, OCS, CH2-O, CH2-S,
—C≡C— —
Figure imgf000007_0001
each L1 and L2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN
R3 is a covalent bond or a substituted or unsubstituted alkylene having 1 to 20 carbon atoms, oxyalkylene having 1 to 20 carbon atoms, thioalkylene having 1 to 20 carbon atoms or a carboxyalkylene having 1 to 20 carbon atoms
R4 is hydrogen, a substituted or an unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, or aryl rest having 6 to 20 carbon atoms,
M is a mesogenic group of the general formula -A-Z, -A-Y B-Z, -A-Y B-Y2-C-Z or a steroidal moiety, preferably selected of the group of cholesteryl compounds, wherein each A, B and C independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 2 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to
30 carbon atoms each YT and Y2 independently is a covalent bond, OCO, N=N,
CH=N, C=C, CO, O(CO)O, O, S, SO2, OCS, CH2-O, CH2-S, —C≡C— —
Figure imgf000008_0001
each L and L2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN
Z is a hydrogen, halogen, CN, -OR, COOR, NO2, a halogen substituted or unsubstituted alkylene or alkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted oxyalkylene or oxyalkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted thioalkylene or thioalkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted carboxyalkylene or alkanoylenoxy having 1 to 20 carbon atoms,
X is a covalent bond, CO, NHCO, OCO n is an integer from 1 to 10.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a graph of the thermomechanical properties of a
composition in accordance with the invention.
BRIEF DESCRIPTION OF THE INVENTION
The invention provides a polymerizable compound within the scope of the general formula:
R4 O-X-R3-M R4
CH2=C-C-O-[-CH2-CH-CH2-O-RrO-]n-CH2-CH-CH2-O-C-C=CH2
II I II
O M-R3-X-O O wherein R, is a group of the general formula -A-, -A-Y B-, -A-Y B-Y2- C-, or a steroidal moiety, preferably selected of the group of cholesteryl compounds, wherein each A, B and C independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 2 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to 30 carbon atoms, a substituted or unsubstituted alkylene moiety having 2 to 20 carbon atoms, each Y^ and Y2 independently is a covalent bond, OCO, N=N, CH=N, C=C, CO, O, S, SO2, O(CO)O, OCS, CH2-O, CH2-S,
Li L, L- O
I I I II
— C≡C — — C=C — — C=C-C02- — C=C— C- — N=N — I I I j
L2 L2 L2 Q
each L-, and L2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN,
Altematively, R, is expressed as a group of the general formula -R-I0-, -R-to-Z-i-Rn-,
Figure imgf000009_0001
or a steroidal moiety, preferably selected from the group of cholesteryl compounds, wherein each R10, R-n and R12 independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 2 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to 30 carbon atoms, a substituted or unsubstituted alkylene moiety having 2 to 20 carbon atoms, each Y1 and Y2 independently is a covalent bond, OCO, N=N, CH=N, C=C, CO, O, S, SO2, O(CO)O, OCS, CH2-O, CH2-S,
Li L, L, O
I I I II
— C≡C — — C=C — — C=C-C02- — C=C-C- — ==N — I I I j
L2 L2 L2 Q each LT and L2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN,
R3 is a covalent bond or a substituted or unsubstituted alkylene having 1 to 20 carbon atoms, oxyalkylene having 1 to 20 carbon atoms, thioalkylene having 1 to 20 carbon atoms or a carboxyalkylene having 1 to 20 carbon atoms,
R4 is hydrogen, a substituted or an unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, or aryl rest having 6 to 20 carbon atoms,
M is a mesogenic group of the general formula -A-Z, -A-YrB-Z, -A-Y B-Y2-C-Z, or a steroidal moiety, preferably selected of the group of cholesteryl compounds, wherein each A, B and C independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 2 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to 30 carbon atoms, each Y, and Y2 independently is a covalent bond, OCO, N=N, CH=N, C=C, CO, O, S, SO2, O(CO)O, OCS, CH2-O, CH2-S, i T L, O
I I I II
— C≡C — — C=C— — C=C-C02- — C=C-C- — N=N — I I I j
L∑ L2 L2 Q
Alternatively, M is expressed as a mesogenic group of the general formula -R10-2, -R^^-R^-Z, -R10-YrRιrZ 2-Ri3-. or a steroidal moiety, preferably selected of the group of cholesteryl compounds, wherein each R10, Rn and R12 independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 2 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to 30 carbon atoms, each Z and Z2 independently is a covalent bond, OCO, N=N, CH=N, C=C, CO, O, S, SO2, O(CO)O, OCS, CH2-O, CH2-S,
L, L, L, O
I I I II
— C≡C — — C=C— — C=C-C02- — C=C-C- — N=N — I I I
L2 L2 L2 Q
each L and L2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN,
Z is a hydrogen, halogen, CN, -OR, COOR, NO2, a halogen substituted or unsubstituted alkylene or alkylidene having 1 to 20 carbon atoms, a halogen substituted or unsubstituted oxyalkylene or oxyalkylidene having 1 to 20 carbon atoms, a halogen substituted or unsubstituted thioalkylene or thioalkylidene having 1 to 20 carbon atoms, a halogen substituted or unsubstituted carboxyalkylene or alkanoylenoxy having
1 to 20 carbon atoms,
X is a covalent bond, CO, NHCO, OCO and n is an integer from 1 to
10.
DESCRIPTION OF THE INVENTION
Preparation of liquid crystalline (meth)acrylates
In accordance with the invention are prepared liquid crystalline (meth)acrylates within the scope of general formula 1 which have at least two polymerizable double bonds and at least two rigid rod-like moieties R and M
Figure imgf000012_0001
General formula 1 is alternatively written as general formula 1A as follows:
R4 O-X-R3-M R4
I I I
CH2=C-C-O-[-CH2-CH-CH2-O-R1-O-]n-CH2-CH-CH2-O-C-C=CH2
II I II
O M-R3-X-O O
In formula 1 and 1A R, is a group of the general formula
-A-, -A-Y B-, -A-YrB-Y2-C- or a steroidal moiety, preferably selected of the group of cholesteryl compounds, wherein each A, B and C independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 2 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to 30 carbon atoms, a substituted or unsubstituted alkylene moiety having 2 to 20 carbon atoms each YT and Y2 independently is a covalent bond, OCO, N=N, CH=N, C=C, CO, O(CO)O, O, S, SO2, OCS, CH2-O, CH2-S,
Figure imgf000012_0002
each Li and L2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN R3 is a covalent bond or a substituted or unsubstituted alkylene having 1 to 20 carbon atoms, oxyalkylene having 1 to 20 carbon atoms, thioalkylene having 1 to 20 carbon atoms or a carboxyalkylene having 1 to 20 carbon atoms
R4 is hydrogen, a substituted or an unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, or aryl rest having 6 to 20 carbon atoms,
M is a mesogenic group of the general formula
-A-Z, -A-YrB-Z, -A-Y B-Y2-C-Z or a steroidal moiety, preferably selected of the group of cholesteryl compounds, wherein each A, B and C independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 2 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to 30 carbon atoms each YT and Y2 independently is a covalent bond, OCO, N=N, CH=N, C=C, CO, O(CO)O, O, S, SO2, OCS, CH2-O, CH2-S,
i-1 L, LI O
I I I II
— C≡≡C — — C=C— — C=C-C02- — C=C-C- — N=N—
I I I j
L2 L2 L2 Q
each LT and L2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN
Z is a hydrogen, halogen, CN, -OR, COOR, NO2, a halogen substituted or unsubstituted alkylene or alkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted oxyalkylene or oxyalkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted thioalkylene or thioalkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted carboxyalkylene or alkanoylenoxy having 1 to 20 carbon atoms,
X is a covalent bond, CO, NHCO, OCO n is an integer from 1 to 10.
Compounds with the scope of general formulas A and B are within the scope of general formula 1 and 1A.
Preferably liquid crystalline (meth)acrylates have structures A and B.
Figure imgf000014_0001
Figure imgf000015_0001
B.
A macromonomer within the scope of general formula 5 is formed by reaction of a 2,3-epoxypropyl (meth)acrylate compound within the scope of general formula 4, a diphenol compound within the scope of general formula 3 and a diepoxide compound within the scope of general formula 2 as follows.
Figure imgf000015_0002
In general formulas 2 through 5 R2 is a group of the general formula
-A-, -A-Y1-B-, -A-YrB-Y2-C- or a steroidal moiety, preferably selected of the group of cholesteryl compounds, wherein each A, B and C independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 2 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to 30 carbon atoms, a substituted or unsubstituted alkylene moiety having 2 to 20 carbon atoms each Y1 and Y2 independently is a covalent bond, OCO, N=N, CH=N, C=C, CO, O(CO)O, O, S, SO2, OCS, CH2-O, CH2-S,
— C≡C — —
Figure imgf000016_0001
each LT and L2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN
R4 is hydrogen, a substituted or an unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, or aryl rest having 6 to 20 carbon atoms,
RT is a substituted or unsubstituted aryl having from 6 to 24 carbon atoms and/or a substituted or unsubstituted cycloalkyl having from 5 to 12 carbon atoms. Preferably R^ is
Figure imgf000016_0002
wherein R5 is hydrogen, alkyl having from 1 to 12 carbon atoms, cycloalkyl having from 5 to 12 carbon atoms, aryl having from 6 to 18 carbon atoms and
Y is substituted or unsubstituted alkylene having from 1 to 5 carbon atoms, O, CO, OCO, S, SO2 and, n is an integer from 1 to 10. Preferably n is 1, 2, or 3.
The reaction of epoxide di(meth)acrylates compounds within the scope of general formula 5 with organic acids within the scope of general formula 6 or derivatives thereof, with isocyanates within the scope of general formula 7 or alcohols 8 within the scope of general formula leads to modified di(meth)acrylates having ester moieties, urethane linkages or ether moieties 1 and 1A within the scope of general formula.
O II M-R3-C-OH 6
M-R3— NCO 7
M-R3-OH 8
In the general formulas 6, 7 and 8 are
R3 is a covalent bond or a substituted or unsubstituted alkylene having 1 to 20 carbon atoms, oxyalkylene having 1 to 20 carbon atoms, thioalkylene having 1 to 20 carbon atoms or a carboxyalkylene having 1 to 20 carbon atoms
M is a mesogenic group of the general formula
-A-Z, -A-YrB-Z, -A-YrB-Y2-C-Z or a steroidal moiety, preferably selected of the group of cholesteryl compounds, wherein each A, B and C independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 2 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to 30 carbon atoms each YT and Y2 independently is a covalent bond, OCO, N=N, CH=N, C=C, CO, O(CO)O, O, S, SO2, OCS, CH2-O, CH2-S,
Figure imgf000018_0001
each LT and L2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN
Z is a hydrogen, halogen, CN, -OR, COOR, NO2, a halogen substituted or unsubstituted alkylene or alkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted oxyalkylene or oxyalkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted thioalkylene or thioalkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted carboxyalkylene or alkanoylenoxy having 1 to 20 carbon atoms,
The esterification, etherification and urethane formation of the di(meth)acrylate hydroxyl groups is carried out in solutions. As solvents for the esterification were used tetrahydrofurane, dioxane, CH2CI2, DMF or others, or polymerizable monomers such as triethyleneglycol bismethacrylate, diethyleneglycol bismethacrylate, dioxolan bismethacrylate, vinyl-, vinylene- or vinylidene-, acrylate- or methacrylate substituted spiroorthoesters and 2,2-bis[p- (acryloxyethoxy) phenyl] propane.
For example a liquid crystalline di(meth)acrylate within the scope of structural formula 9 is synthesized in the following manner: 2,3- epoxy propoxy methacrylate and 4,4'-dihydroxy biphenyl are mixed and reacted for 15 hours at 115°C to form a methacrylate terminated macromonomer having hydroxyl groups. The macromonomer hydroxyl groups are then esterified by mixing at O 97/14674 PC17US96/16436
23 ' C with 4'-cyano-biphenyl 4-oxy-vale c carboxylic acid and dicyclohexylcarbodiimid and than for further 24 hours at 23°C to form a compound of the structural formula:
Figure imgf000019_0001
The compositions of the invention are formulated as one, two or more components, UV curable, visible light curable, self cure, and/or dual cure product or combinations of these. The composition of a preferred embodiment of the invention includes polymerizable carboxylic acid monomer, an optional filler and/or diluent, a cationic elutable glass or other source of polyvalent cations, and a polymerization catalyst system.
Fillers which are suited for use in compositions of the invention are organic and/or inorganic particles, for example inorganic glasses such as are used in glass ionomer cements. Exemplary of such fillers are those of U.S. Patent 4,814,362 which is incorporated herein by reference in its entirety. Preferred fillers are glasses formed from or including, barium, calcium, strontium, lanthanum, tantalum, and/or tungsten silicates and aluminates and/or aluminosilicates, silica, including submicron silica, quartz, and/or ceramics for example, calcium hydroxy apatite. In a preferred embodiment of the invention reactive cations, especially those of calcium, strontium and aluminium, and anions especially fluoride ions; are eluted from the fillers. The fillers used in the invention preferably are reduced in particle size and are preferably silanated before they are incorporated into such compositions. Preferred levels of filler are from about 20% to about 85% based on the total weight of the composition, with from about 40% to about 85% being more preferable and about 50-80% being most preferred. If a more finely particulated filler is used, amounts of filler may be decreased due to the relative increase in surface area which attends the smaller sizes of particles. Preferred particle size distributions are from 0.02 to 50 microns, more preferably 0.1 to 10 microns, and most preferably 1 to 6 microns.
Mixing the compositions of the present invention may be achieved using standard compounding techniques. For example, liquids, photoinitiator(s), and accelerator(s) are blended first, and fillers are added incrementally thereafter. When blending light sensitive compositions, however, a photosafe room illumination, i.e., one that does not contain substantial amounts of wavelengths of electromagnetic radiation that would activate the photoinitiating system is used to avoid initiating polymerization of the composition prematurely.
The compounds of the present invention also have medical applications such as in self adhesive bone cements. However, they are most preferred to use in dental treatment by application to a tooth or a number of teeth in vivo, in the mouth of a live patient by a dentist or dental practitioner. The application of the compositions of the invention is preferably
as a polymerizable dental composition applied to tooth. In a preferred
embodiment of the invention a dental cement composition includes a
compound within the scope of general formula 1 , and other
ingredients, such as curing catalysts, initiators, accelerators, diluents
and/or adjuvants. The composition is applied as a cement using
conventional techniques and preferably cured with application of
visible light in a conventional manner. Cements in accordance with the
invention are self adhesive to dentin and enamel. These cements are
used in bonding dentin to structures, for example, to bond a ceramic
inlay to a prepared cavity of a tooth. Inlays preferably are polymers, or
ceramics which are cast or built-up from porcelain frits and fired.
Alternatively, inlays are machined from metal such as titanium or gold
or performed polymeric composite or homogeneous monolithic
polymer compositions, for example by CAD-CAM procedures. In
accordance with a preferred embodiment of the invention metal or
ceramic superstructures for crowns, and bridges and/or orthodontic
appliances are bonded to teeth using cement compositions of the
invention. Such cement compositions join metal or ceramic to tooth by
application of the cement composition by bringing them into contact
until the cement hardens.
A preferred composition of the invention includes a two-part
system. One part includes an initiator. The second part comprises filled and the co-initiator. The two parts are spatuled to form a cement
prior to placement on tooth. The placement is by standard
technique(s). Preferably the cement includes a visible light and/or a
self-curing redox polymerization initiator system. In a preferred embodiment of the invention luting cement compositions have low
viscosity and film thicknesses less than about 25 μm to bond close
fitting appliances to prepared teeth. In one embodiment luting cement
compositions of the present invention may be prepared of such high
viscosity and consistency that they form adhesive "glue" Iines of
thicknesses up to several hundred microns to lute less close fitting
restorations, for example inlays prepared using present state-of-the-art
CAD-CAM devices. Compositions of the invention are mechanically
strong, abrasion resistant, and are esthetically suitable and serve as
the sole structural element to retain inlay, crowns and bridges or other
appliances to tooth structure.
A preferred dental treatment in accordance with the invention is
the application of dental filling compositions which include an initiator
and at least one compound within the scope of general formula 1.
Preferably the dental filling composition includes finely divided filler.
Preferably the composition is applied to a tooth as a filling material
using conventional techniques as a one-component material and is
cured with application of visible light in conventional manner. In a preferred embodiment of the invention a one or two
component pit and fissure sealant which includes at least one
compound within the scope of general formula 1 is applied to anatomic
defects and/or the exterior of teeth. The sealant limits the ability of
caries-forming bacteria to colonize the pits, fissures and other surfaces
of the teeth. Pit and fissure sealant compositions in accordance with
the invention are an especially valuable means of reducing caries by
filling and eliminating enamel defects. The pit and fissure sealants of
the invention are preferably applied with or without prior acid etching or
the use of rubber dam to teeth. In one embodiment fluoride eluting
compounds and glasses are preferably included in compositions of the
invention. Fluoride is eluted to reduce the incidence of caries in tooth
substance adjacent the compositions of the invention
Preferred compositions of the invention include two or more
ethylenically unsaturated materials are included in compositions of the
invention. The polymerizable monomer is preferably liquid at 23 ' C,
and comprises from about 0.5 to about 99.998% by weight of the
composition, with amounts ranging from about 1 to about 99.98%
being preferred, and amounts ranging from about 1.5 to about 99.8%
being more preferred.
Preferred compositions of the invention include an adhesion
promoter for example a phosphorus-containing adhesion promoter
which is free from any halogen atoms covalently or otherwise bonded directly to a phosphorus atom. The phosphorus derivative may be
polymerizable or non-polymerizable, however the preferred
phosphorus-containing adhesion promoters comprise polymerizable
phosphorus materials having ethylenic unsaturation and include, among others, organic esters of one or more acids of phosphorus
(hereinafter referred to as phosphorus acid esters), wherein the
organic portion of the ester contains at least one polymerizable
ethylenically unsaturated group. The organic portion of the ester may
be alkenyl, alkenoxy, cycloalkenyl, aralkenyl, or alkenaryl, and
preferably may have from 2 to 40 carbon atoms. The organic portion
may be straight chain, branched, or cyclic, can contain skeletal hetero
atoms, i.e., atoms other than carbon, and can be unsubstituted or
substituted with moieties which do not interfere with the free radical
polymerization of the phosphorus acid esters.
Examples of saturated and unsaturated phosphorus acid esters
which may be used include, but are not limited to, monomers
containing phosphoric acid groups such as hydroxyethyl methacrylate
monophosphate, 2,2,'-bis( alpha -methacryloxy- beta
hydroxypropoxyphenyl) propane diphosphonate (BIS-GMA
diphosphonate), BIS-GMA diphosphate, dibutyl phosphite, di-2-
ethylhexyl phosphite, di-2-ethylhexyl phosphate, glyceryl-2-phosphate,
glycerylphosphoric acid, methacryloxyethyl phosphate, and glyceryl
dimethacrylate phosphate. Other suitable polymerizable phosphorus acid esters are disclosed, for example, in U.S. Pat. No. 4,499,251 to
Omura et al, U.S. Pat. No. 4,222,780 to Shibantani et al, U.S. Pat. No.
4,235,633 to Tomioka, U.S. Pat. No. 4,259,117 to Yamauchi et al, U.S.
Pat. No, 4,368,043 to Yamauchi et al. Of the polymerizable
phosphorus acid compounds disclosed in the above patents and
application, each of which is incorporated herein by reference, the preferred compounds are those polyethylenically unsaturated
monophosphates of the formula:
R1 O
I II
(CH=C-CO-O)nR-O-P-OH
I
OH
and salts thereof, in which
R is an organic radical having a valency of n +1; and R may be
interrupted by one or more oxygen atoms and may be substituted or
unsubstituted, and may comprise an aliphatic radical, or a
cycloaliphatic radical, or an aryl radical;
R1 is a hydrogen atom, alkyl having from 1 to 3 carbon atoms,
halogen or -C=N, and
n is an integer of at least 1. Preferably n is an integer of 2 or
more, and more preferably from 3 to 6. Examples of the preferred
compounds include pentaerythritol triacrylate monophosphate,
pentaerythritol trimethacrylate monophosphate, dipentaerythritol pentaacrylate monophosphate, and dipentaerythritol
pentamethacrylate monophosphate. When included the phosphorus
acid compound may comprise from about 0.25 to about 99.998% by
weight of the adhesive composition, with amounts ranging from about
1 to about 50% being preferred. In a more preferred embodiment the
phosphorus acid compound would comprise from about 2 to about
29.8% by weight of the composition.
Preferred compositions of the invention include a catalyst
component which may comprise any free radical initiators normally
used in conjunction with polymerizable ethylenically unsaturated
materials, although those which will initiate polymerization at room
temperature are more preferred. Thus, the catalyst may comprise, for
example, an organic peroxide type initiator such as dibenzoyl
peroxide, dilauroyl peroxide, acetyl peroxide, t-butyl peroxybenzoate,
cumene hydroperoxide and the like. In a preferred aspect, the catalyst
comprises an actinic light sensitive initiator, such as ultraviolet light-
sensitive initiators or visible light sensitive initiators. As examples of
suitable ultraviolet light-sensitive initiators there may be mentioned the
monoketals of an aromatic 1 ,2-diketone, benzophenones, substituted
benzophenones, benzoin methyl ether, isopropoxybenzoin, benzoin
phenyl ether or benzoin isobutyl ether. Among the suitable visible light
sensitive initiators, alpha-diketones, such as camphoroquinone, are
particularly preferred. The preferred initiators are the visible light sensitive initiators. The catalyst generally is employed in the range of
from about 0.001 to about 10% of the composition. In a preferred
embodiment the catalyst is used within the range of from 0.01 to about
5%. In a still further preferred embodiment, from about 0.1 to about 2%
by weight of catalyst is employed.
In a preferred embodiment of the invention, polymerizable
compositions are provided which include an accelerator system
comprising (1) an amine or amine salt and/or (2) a sulfmic acid or salt
thereof and/or (3) a metal salt or organo metal compound. In a
preferred embodiment both the amine or amine salt and the sulfinic
acid or salt thereof are present. The amine or amine salt may be
present in an amount from 0 to about 20% by weight of the
composition, whereas the sulfinic acid or salt thereof is present in an
amount of from about 0 to about 10%, the combined amount being
from about 0.001 to about 20 percent. In a preferred embodiment, the
amine or amine salt is in the range of 0.001 to about 10% by weight of
the polymerizable composition, and the sulfinic acid or a sulfinic acid
salt is in the range from about 0.01 to about 5 percent by weight of the
polymerizable composition, the combined weight being in the range
from about 0.01-15% by weight. In a still more preferred embodiment,
the amine or amine salt is in an amount from about 0.1-8 percent by
weight of the polymerizable composition and the sulfinic acid or salt
thereof is in an amount from 0.1-2 percent by weight of the polymerizable composition, the combined amount ranging from about
0.2 to 10 percent by weight of the polymerizable composition.
The amine or amine salt employed in a preferred embodiment of
this invention desirably is a secondary or tertiary amine rather than a
primary amine, since the use of a secondary or tertiary amine leads to
significantly accelerated curing. Examples of suitable amines include
N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N-methyl-N-beta-
hydroxyethylaniline.
Primers and adhesives of the invention may be filled to such an
extent that they would serve not only as primers and adhesives, but
also as pit and fissure sealants and dental filling composites. A primer,
composition of the invention comprises by weight about 5-20%
PENTA, 0-61% hydroxyethyl methacrylate, 0.1% butylated
hydroxytoluene.
All of the percentages recited herein are by weight based on
the weight of the entire composition unless otherwise stated.
Example 1
Synthesis of 4.4'-Bis-(2-hydroxy-3-methacrvlovlpropoxv biDhenvl
60.00 g (0.422 mol) 2,3-Epoxypropoxy methacrylate, 0.40 g 2,6-Di- tert.-butyl-cresol, 39.3 g (0.211 mol) 4,4'-Dihydroxybiphenyl and 250 ml 1-Methoxy-2-propanol are heated until a homogeneous clear liquid is formed. After adding 0.30 g 1 ,8-Diaza-bicyclo-[5.4.0]-undec-7-ene the mixture were kept for 15 hours at 115 °C. Then the mixture is concentrated and dropped into petrolether and cooled onto 0 °C. The separated solid is filtered and washed with petrolether and dried. The crude product is recrystallized from 200 ml ethanol dissolved in a small amount DMSO and filtered over AI2O3 (act. Il/lll, app. 500 g) using acidic ethyl ester/petrol ether. After removing the solvents 14 g of pure 4,4'-Bis-(2-hydroxy-3-methacryloylpropoxy)-biphenyl is obtained. 1H NMR: 7.6/7.05 (Ar), 6.1/5.7 (CH2=C-), 5.45 (OH), 4.3, 4.1 (CH, CH2OCO), 4.0 (CH2OAr), 1.9 (CH3).
13C NMR: 166.3 (CO), 157.4/132.3/127.1/114.7 (Ar), 135.6 (C=), 125.8 (CH2=), 69.0 (CH2O), 66.6 (CH), 65.5 (CH2OCO), 17.8 (CH3).
Esterification of 4.4'-bis-r2-hvdroxy-3-methacryloylDropoxy -biphenyl with 4'-Cyano-biphenyl-4-oxyvaleric carboxylic acid
6,50 g (22 mmol) 4'-Cyano-biphenyl-4-oxyvalerian carboxylic acid, 4,71 g (10 mmol) 4,4'-bis-(2-hydroxy-3-methacryloylpropoxy)-biphenyl and 0,25 g dimethylamino pyridine were dissolved in 85 ml CH2CI2/DMF (vol.-ratio 9:8). To the mixture were added 5,00 g (24,2 mmol) dicyclohexyl carbodiimid. Then the mixture were stirred for 24 hours at room temperature. After this time the precipitated solid was filtered off. To the filtrate were added 0,1 g BHT and the solvent was removed by vacuum distillation. The viscose residue was dissolved in 100 ml CH2CI2 and cooled to 0 °C. The precipitating solid was removed and the filtrate was washed twice with 50 ml 1n HCl, 50 ml 1 n NaHCO3 solution and with 150 ml water and filtered over silica. Furthermore, the solution was dried over NaSO4 and the solvent was removed to obtain 5.5 g of 4,4'-bis-(2-hydroxy-3-methacryloylpropoxy)-biphenyl esterified with 4'-Cyano-biphenyl-4-oxyvaleric carboxylic acid.
Application Example 1 To 5.00 g liquid crystalline di(meth)acrylate of Example 1 are added and 0,05 g JRAGCURE 651 (Ciba - Geigy). Using a curing unit (Dentsply De Trey) the mixture is polymerized by irradiation with visible light during 40 seconds. The degree of polymerization is about 85 %. The obtained material shows a volume shrinkage of 2.4 percent. The thermo-mechanical properties are shown in Figure 1 wherein E' (storage modulus) is 2.8 • 109 Ps (25°C), E" (loss modulus) is 2.9 • 108 Pa (25°C) and tan δ (E'VE') is 0.22.
Comparative Example 1
To 7.000 g of (2,2-Bis-[p-(2-hydroxy-3-methacryloyloxypropoxy)- phenylj-propane) and 3.000 g of triethyleneglycol dimethacrylate were added 0,050 g N,N-di-(β-hydroxyethyl)-p-toluidine and 0.050 g champhorquinone. Using a curing unit (Dentsply De Trey) the mixture was polymerized by irradiation with visible light during 40 seconds. The degree of polymerization is about 65 %. The obtained material shows a volume shrinkage of 6.5 percent.
Synthesis of 4.4'-bis-(2-hvdroxy-3-methacryloylpropoxvVbiphenvl as described in example 1
Esterification of 4.4'-bis-(2-hydroxy-3-methacrvlovlDropoxv -biphenvl with 4'-Cyano- biphenyl-4-oxyundecane carboxylic acid
11.39 g (30 mmol) 4'-Cyano-biphenyl-4-oxyundecane carboxylic acid,
6.59 g (14 mmol) 4,4'-bis-(2-hydroxy-3-methacryloylpropoxy)-biphenyl and 0.32 g (2,6 mol) dimethylamino pyridine were dissolved in 160 ml CH2CI2/DMF (having a volume ratio 5:3). To the mixture were added
6.60 g (32 mmol) dicyclohexyl carbodiimid. Then the mixture were stirred for 27 hours at room temperature. After this time the precipi¬ tated solid was filtered off. To the filtrate were added 0.15 g BHT and the solvent was removed by vacuum distillation. The viscose residue was dissolved in 250 ml CH2CI2 and cooled to 0 °C. The precipitating solid was removed and the filtrate was washed twice with 150 ml with 1n HCl, 150 ml 1n NaHCO3 solution and with 75 ml water and filtered over silica. Furthermore, the solution is dried over NaSO4 and the solvent is removed.
Yield: 6.9 g
Table 1 shows the Melting Points (°C) of LC-Monomers II - VI and the glass transition temperatures of Examples 1 and 2.
LC-Monomer R / X Melting point (βC)
II H 108
II CH3 86
III - 52
IV 84
V Cl 157
V OCH3 154
V CH3 169
VI H 87-89
VI CH3 98-99
Example 1 18*
Example 2 6**
* At 18 ' C the glassy product of Example 1 becomes a liquid and from 18 to 67.5 ' C remains in the nematic phase.
**At 6 * C the glassy product of Example 2 becomes a liquid and from 6 to 59.5 X remains in the nematic phase.
EXAMPLE 3 SELF-CURING, TWO COMPONENT, POWDER AND LIQUID CEMENT
0.92 grams of the dried product prepared as described in Example 2 and 0.08 grams of triethyleneglycol dimethacrylate are dissolved in one another to form a liquid. 1.0 grams of this liquid is added to 2.0 grams of the strontium aluminofluorosilicate containing powder. The consistency of the mixture is suitable for use as a luting or crown and bridge or orthodontic cement or as a filling material. Polymerization is induced by the redox polymerization system of benzoyl peroxide, ascorbyl palmitate and copper acetyl acetonate. The powder and liquid compositions are as follows:
PERCENT POWDER BY WEIGHT
Strontium fluoroaluminosilicate cement 98.83
(Glass) Benzoyl peroxide 1.00 ascorbyl palmitate 0.15 copper acetyl acetonate 0.02
LIQUID
Product of example 2 92.00
Triethylene glycol dimethacrylate 8.00
The powder and liquid are mixed in a 1 :1 ratio by volume to form a
cement. This cement is adhesive to dentin and enamel without further
treatment except cleansing with pumice.
Example 4
Esterification of (2,2-Bis-[p-(2-hydroxy-3-methacryloyloxypropoxy)- phenylj-propane) with 11-[4'(trans-4-propyl-cyclohexyl)-phenoxy]- undecane carboxylic acid 1.50g (3.73 mmol) 11-[4'(trans-4-propyl-cyclohexyl)-phenoxy]- undecane carboxylic acid. 0.87 g (1.69mmol) (2.2-Bis-[p-(2-hydroxy-3- methacryloyloxypropoxy)-phenyl]-propane) and 0.05 g dimethylamino pyridine were dissolved in 20 ml CH2CI2. To the mixture were added 0.85 g (4.10 mmol) dicyclohexyl carbodiimid at 0 * C. Then the mixture stirred for 24 hours at room temperature. After this time the precipitated solid was filtered off. To the filtrate were added 0.05 g BHT and the solvent was removed by vacuum distillation. The viscose residue was washed with pentane and filtered over aluminum oxide. The separation of the disubstituted product from mono-substituted impurities occurs by column chromatography(silica, CHCI3). After evaporation of the solvent was obtained a highly viscous, slightly yellow liquid crystalline substance. The liquid crystalline dimethacrylate exhibits a glass transition temperature of Tg -10 °C. It shows a liquid crystalline behavior between -10 and 19 °C (smectic phase). The yield is 0.77 g.
13C-NMR: 14.4 (CH2-C_H3). 18.3 (C=C-C_H3). 20.1 (C_H2-CH3). 24.9-37.0 (aliphatic CH2 and cyclohexyl). 29.5 (C-C_H3). 39.8 (CH2-cyclohexyl). 43.7 (£-CH3). 62.9 (COO-CH2). 66.3 (Ph-O£H2). 69.4 (CH-O). 114.2- 135.8 (aromatic carbons). 126.2 (=CH2). 135.8 (=C). 157.2-157.5 (aromatic carbons). 166.9 (=C(C_O2)-). 173.1 ((CH2)4-C_O2-).
Figure imgf000034_0001
It should be understood that while the present invention has been described in considerable detail with respect to certain specific embodiments thereof, it should not be considered limited to such embodiments but may be used in other ways without departure from the spirit of the invention and the scope of the appended claims.

Claims

What we claim is
1. A compound within the scope of the general formula:
R4 O-X-R3-M R4
I I I
CH2=C-C-O-[-CH2-CH-CH2-O-R1-O-]n-CH2-CH-CH2-O-C-C=CH2
II I II
O M-R3-X-O O
wherein
Ri is a group of the general formula
-A-, -A-YT-B-, _A-YrB-Y2-C- or a steroidal moiety, preferably selected of the group of cholesteryl compounds, wherein each A, B and C independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 2 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to 30 carbon atoms, a substituted or unsubstituted alkylene moiety having 2 to 20 carbon atoms each YT and Y2 independently is a covalent bond, OCO, N=N, CH=N, C=C, CO, O(CO)O, O, S, SO2, OCS, CH2-O, CH2-S,
Li LT L, O
I I I I!
— C≡C— — C=C — — C=C-C02- — C=C-C- — N=N —
I I 1
L2 LL2, L, Λ
each LT and L2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN R3 is a covalent bond or a substituted or unsubstituted alkylene having 1 to 20 carbon atoms, oxyalkylene having 1 to 20 carbon atoms, thioalkylene having 1 to 20 carbon atoms or a carboxyalkylene having 1 to 20 carbon atoms
R4 is hydrogen, a substituted or an unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, or aryl rest having 6 to 20 carbon atoms,
M is a mesogenic group of the general formula
-A-Z, -A-YT-B-Z, -A-YrB-Y2-C-Z or a steroidal moiety, preferably selected of the group of cholesteryl compounds, wherein each A, B and C independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 2 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to 30 carbon atoms each YT and Y2 independently is a covalent bond, OCO, N=N, CH=N, C=C, CO, O(CO)O, O, S, SO2, OCS, CH2-O, CH2-S,
Figure imgf000036_0001
each LT and L2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN
Z is a hydrogen, halogen, CN, -OR, COOR, NO2, a halogen substituted or unsubstituted alkylene or alkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted oxyalkylene or oxyalkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted thioalkylene or thioalkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted carboxyalkylene or alkanoylenoxy having 1 to 20 carbon atoms,
X is a covalent bond, CO, NHCO, OCO n is an integer from 1 to 10.
2. A compound within the scope of the general formula:
R4 O-X-R3-M R4
I I I
CH2=C-C-O-[-CH2-CH-CH2-O-Rτ-O-]n-CH2-CH-CH2-O-C-C=CH2
II I II
O M-R3-X-O O
wherein
R is a group of the general formula
-A-, -A-YT-B-, -A-Yτ-B-Y2-C or a steroidal moiety, preferably selected of the group of cholesteryl compounds, wherein each A, B and C independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 2 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to 30 carbon atoms, a substituted or unsubstituted alkylene moiety having 2 to 20 carbon atoms each YT and Y2 independently is a covalent bond, OCO, N=N, CH=N, C=C, CO, O(CO)O, O, S, SO2, OCS, CH2-O, CH2-S,
LT L, L, 0
I I I II
—C≡C— — C=C— — C=C-C02- — C=C-C- — N=N —
I I I j
L2 L2 L2 Q
each LT and L2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN
R3 is a covalent bond or a substituted or unsubstituted alkylene having 1 to 20 carbon atoms, oxyalkylene having 1 to 20 carbon atoms, thioalkylene having 1 to 20 carbon atoms or a carboxyalkylene having 1 to 20 carbon atoms
R4 is hydrogen, a substituted or an unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, or aryl rest having 6 to 20 carbon atoms,
M is a mesogenic group of the general formula -A-Z, -A-YT-B-Z, -A-Y,-B-Y2-C-Z or a steroidal moiety, preferably selected of the group of cholesteryl compounds, wherein each A, B and C independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 2 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to 30 carbon atoms each YT and Y2 independently is a covalent bond, OCO, N=N, CH=N, C=C, CO, O(CO)O, O, S, SO2, OCS, CH2-O, CH2-S,
—C≡C—
Figure imgf000038_0001
each LT and L2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN Z is a hydrogen, halogen, CN, -OR, COOR, NO2, a halogen substituted or unsubstituted alkylene or alkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted oxyalkylene or oxyalkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted thioalkylene or thioalkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted carboxyalkylene or alkanoylenoxy having 1 to 20 carbon atoms,
X is a covalent bond, CO, NHCO, OCO n is an integer from 1 to 10.
3. Liquid crystalline (meth)acrylates of claim 1 or 2 wherein the liquid crystalline (meth)acrylate is within the scope of formula:
Figure imgf000039_0001
4. The composition of claim 1 or 2 wherein said compound is made by etherification, esterification or formation of urethane linkages of at least a portion of the -OH groups of a macromonomer having at least two terminal double bonds and having at least an aromatic or cycloaliphatic moiety, and said compound polymerizes with a shrinkage of less than 2.5 percent by volume and a conversion of double bonds of more than 80 percent.
5. The compound of claim 1 or 2 wherein said compound is made by etherification, esterification or formation of urethane linkages of at least a portion of the -OH groups of a macromonomer having at least two terminal double bonds and having at least an aromatic or cycloaliphatic moiety, and said compound polymerizes with a shrinkage of less than 2.5 percent by volume and a conversion of double bonds of more than 80 %.
6. The compound of claim 1 or 2 characterized in that RT, R2, R3 and R4 each independently is derived from liquid a crystalline alcohol, mercaptane, carboxylic acid, isocyanate or derivative thereof.
7. The compound of claim 1 or 2 wherein said compound has a melting point below 20 °C.
8. The compound of claim 1 in a composition comprising at least one low molecular weight compound within the scope of the general formula
Figure imgf000040_0001
wherein QT is a mesogenic group of the general formula
-A-Z, -A-YT-B-Z, -A-YrB-Y2-C-Z or a steroidal moiety, preferably selected of the group of cholesteryl compounds, wherein each A, B and C independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 2 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to 30 carbon atoms each YT and Y2 independently is a covalent bond, OCO, N=N, CH=N, C=C, CO, O(CO)O, O, S, SO2, OCS, CH2-O, CH2-S,
— C≡C — — C=C— — C=C-C02- — C=C-C- — N=N —
I I I
L2 L2 L2 Q each LT and L2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN
Z is a hydrogen, halogen, CN, -OR, COOR, NO2, a halogen substituted or unsubstituted alkylene or alkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted oxyalkylene or oxyalkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted thioalkylene or thioalkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted carboxyalkylene or alkanoylenoxy having 1 to 20 carbon atoms,
Q2 is a covalent bond or a substituted or unsubstituted alkylene having 1 to 20 carbon atoms, oxyalkylene having 1 to 20 carbon atoms, thioalkylene having 1 to 20 carbon atoms or a carboxyalkylene having 1 to 20 carbon atoms,
Q3 is hydrogen, -OCH3, -OH, -Cl, -Br, -COOH, -NCO, or Si(C2H5O)3.
9. The compound of Claim 1 in a composition comprising at least 25 percent by volume volatile organic solvent.
10. The compound of claim 1 in a dental cement comprising at least 20 percent by volume filler.
11. The compound of claim 1 wherein R and R2 each independently is an aryl having from 6 to 24 carbon atoms, a halogen substituted aryl having 6 to 24 carbon atoms or a cycloalkylene moiety having 5 to 12 carbon atoms.
12. The compound of claim 1 or 2 wherein said compound is within the general formula:
Figure imgf000042_0001
wherein
R3 is a covalent bond or a substituted or unsubstituted alkylene having 1 to 20 carbon atoms, oxyalkylene having 1 to 20 carbon atoms, thioalkylene having 1 to 20 carbon atoms or a carboxyalkylene having 1 to 20 carbon atoms
R4 is hydrogen, a substituted or an unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, or aryl rest having 6 to 20 carbon atoms,
Z is a hydrogen, halogen, CN, -OR, COOR, NO2, a halogen substituted or unsubstituted alkylene or alkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted oxyalkylene or oxyalkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted thioalkylene or thioalkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted carboxyalkylene or alkanoylenoxy having 1 to 20 carbon atoms,
X is a covalent bond, CO, NHCO, OCO.
13. The compound of claim 1 wherein said liquid crystalline (meth)acrylates have a melting point below 20 " C.
14. The compound of claim 1 further comprising a low molecular weight compound which is liquid at 23 ° C and is within the general formula
M-R3-X wherein
R3 is a covalent bond or a substituted or unsubstituted alkylene having 1 to 20 carbon atoms, oxyalkylene having 1 to 20 carbon atoms, thioalkylene having 1 to 20 carbon atoms or a carboxyalkylene having 1 to 20 carbon atoms
M is a mesogenic group of the general formula
-A-Z, -A-YT-B-Z, -A-YT-B-Y2-C-Z or a steroidal moiety, preferably selected of the group of cholesteryl compounds, wherein each A, B and C independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 2 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to 30 carbon atoms each YT and Y2 independently is a covalent bond, OCO, N=N, CH=N, C=C, CO, O(CO)O, O, S, SO2, OCS, CH2-O, CH2-S,
LT LT L, O
I I I II
— C≡C— — C=C— — C=C-C02- — C=C-C- — N=N — I I I j
L2 L2 L2 Q
each LT and L2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN
Z is a hydrogen, halogen, CN, -OR, COOR, NO2, a halogen substituted or unsubstituted alkylene or alkylidene having 1 to 20 carbon atoms, a halogen substituted or unsubstituted oxyalkylene or oxyalkylidene having 1 to 20 carbon atoms, a halogen substituted or unsubstituted thioalkylene or thioalkylidene having 1 to 20 carbon atoms, a halogen substituted or unsubstituted carboxyalkylene or alkanoylenoxy having 1 to 20 carbon atoms.
15. A dental composition comprising a compound within the scope of the general formula
R4 O-X-R3-M R4
I I I
CH2=C-C-O-[-CH2-CH-CH2-O-Rτ-O-]n-CH2-CH-CH2-O-C-C=CH2
II I II
O M-R3-X-O O
wherein
R is a group of the general formula
-A-, -A-Y1-B-, -A-Yτ-B-Y2-C- or a steroidal moiety, preferably selected of the group of cholesteryl compounds, wherein each A, B and C independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 2 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to 30 carbon atoms, a substituted or unsubstituted alkylene moiety having 2 to 20 carbon atoms each YT and Y2 independently is a covalent bond, OCO, N=N, CH=N, C=C, CO, O(CO)O, O, S, SO2, OCS, CH2-O, CH2-S, Li L, LT O
I I I II
—C≡C— — C=C— — C=C-C02- — C=C-C- — N=N—
I I I
L2 L2 L2 Q
each LT and L2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN
R3 is a covalent bond or a substituted or unsubstituted alkylene having 1 to 20 carbon atoms, oxyalkylene having 1 to 20 carbon atoms, thioalkylene having 1 to 20 carbon atoms or a carboxyalkylene having 1 to 20 carbon atoms
R4 is hydrogen, a substituted or an unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, or aryl rest having 6 to 20 carbon atoms,
M is a mesogenic group of the general formula
-A-Z, -A-YT-B-Z, -A-YT-B-Y2-C-Z or a steroidal moiety, preferably selected of the group of cholesteryl compounds, wherein each A, B and C independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 2 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to 30 carbon atoms each YT and Y2 independently is a covalent bond, OCO, N=N, CH=N, C=C, CO, O(CO)O, O, S, SO2, OCS, CH2-O, CH2-S,
L LT L, O
I I I II
—C≡C— — C=C— — C=C-C02- — C=C-C- — N=N—
I I I I
L2 L2 L2 Q
each LT and L2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN Z is a hydrogen, halogen, CN, -OR, COOR, NO2, a halogen substituted or unsubstituted alkylene or alkylidene having 1 to 20 carbon atoms, a halogen substituted or unsubstituted oxyalkylene or oxyalkylidene having 1 to 20 carbon atoms, a halogen substituted or unsubstituted thioalkylene or thioalkylidene having 1 to 20 carbon atoms, a halogen substituted or unsubstituted carboxyalkylene or alkanoylenoxy having 1 to 20 carbon atoms,
X is a covalent bond, CO, NHCO, OCO n is an integer from 1 to 10.
16. The composition of claim 17 wherein each R, and R2 independently is an aryl having 6 to 24 carbon atoms, halogen substituted aryl having 6 to 24 carbon atoms or cycloalkylene moiety having 5 to 12 carbon atoms.
17. A dental composition comprising a compound within the scope of the general formula
R4 0-X-R3-M R4
CH2=C-C-O-[-CH2-CH-CH2-O-Rτ-O-]n-CH2-CH-CH2-O-C-C=CH2
II I II
O M-R3-X-O O
wherein
R is a group of the general formula
_A-, -A-Y1-B-, -A-YrB-Y2-C- or a steroidal moiety, preferably selected of the group of cholesteryl compounds, wherein each A, B and C independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 2 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to 30 carbon atoms, a substituted or unsubstituted alkylene moiety having 2 to 20 carbon atoms each YT and Y2 independently is a covalent bond, OCO, N=N, CH=N, C=C, CO, O(CO)O, O, S, SO2, OCS, CH2-O, CH 2-S,
LT LT L, O
I I : : ι
—C≡C— — C=C— — C=C-C02- — C = C-C- — N=N —
L 1 2 L1 2 L-2 Q I
each LT and L2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN
R3 is a covalent bond or a substituted or unsubstituted alkylene having 1 to 20 carbon atoms, oxyalkylene having 1 to 20 carbon atoms, thioalkylene having 1 to 20 carbon atoms or a carboxyalkylene having 1 to 20 carbon atoms
R4 is hydrogen, a substituted or an unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, or aryl rest having 6 to 20 carbon atoms,
M is a mesogenic group of the general formula
-A-Z, -A-YT-B-Z, -A-Yτ-B-Y2-C-Z or a steroidal moiety, preferably selected of the group of cholesteryl compounds, wherein each A, B and C independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 2 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to 30 carbon atoms each YT and Y2 independently is a covalent bond, OCO, N=N, CH=N, C=C, CO, O(CO)O, O, S, SO2, OCS, CH2-O, CH2-S,
LT LT LT 0
I I I II
— C≡C — — C=C — — C=C-C02- — C=C-C- — N=IM —
I I I i
L2 L2 L2 Q
each L and L2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN
Z is a hydrogen, halogen, CN, -OR, COOR, NO2, a halogen substituted or unsubstituted alkylene or alkylidene having 1 to 20 carbon atoms, a halogen substituted or unsubstituted oxyalkylene or oxyalkylidene having 1 to 20 carbon atoms, a halogen substituted or unsubstituted thioalkylene or thioalkylidene having 1 to 20 carbon atoms, a halogen substituted or unsubstituted carboxyalkylene or alkanoylenoxy having 1 to 20 carbon atoms,
X is a covalent bond, CO, NHCO, OCO n is an integer from 1 to 10.
18. The composition of claim 15 or 17 wherein said composition comprises at least 50 percent by weight of filler particles.
19. The composition of claim 15 or 17 further comprising a polymerization initiator.
20. The composition of claim 15 or 17 further comprising a photoinitiator.
21. The composition of claim 15 or 17 wherein said composition is an adhesive, primer cement, pit and fissure sealant or restorative,.
22. A method of using a dental composition, comprising providing a dental composition comprising a compound within the scope of the general formula:
Figure imgf000049_0001
CH2=C-C-O-[-CH2-CH-CH2-O-Rτ-O-]n-CH2-CH-CH2-O-C-C=CH2
II
M-R3-X-O O
wherein
RT is a group of the general formula
-A-, -A-Y1-B-, -A-Yτ-B-Y2-C- or a steroidal moiety, preferably selected of the group of cholesteryl compounds, wherein each A, B and C independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 2 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to 30 carbon atoms, a substituted or unsubstituted alkylene moiety having 2 to 20 carbon atoms each YT and Y2 independently is a covalent bond, OCO, N=N, CH=N, C=C, CO, O(CO)O, O, S, SO2, OCS, CH2-O, CH2-S,
LT LT I, 0
I I I I I
—C≡C— — C=C— — C=C-C02- — C=C-C- — N==N—
I I I j
L2 L2 L2 Q
each LT and L2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN
R3 is a covalent bond or a substituted or unsubstituted alkylene having 1 to 20 carbon atoms, oxyalkylene having 1 to 20 carbon atoms, thioalkylene having 1 to 20 carbon atoms or a carboxyalkylene having 1 to 20 carbon atoms R4 is hydrogen, a substituted or an unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, or aryl rest having 6 to 20 carbon atoms,
M is a mesogenic group of the general formula
-A-Z, -A-YT-B-Z, -A-Yτ-B-Y2-C-Z or a steroidal moiety, preferably selected of the group of cholesteryl compounds, wherein each A, B and C independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 2 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to 30 carbon atoms each YT and Y2 independently is a covalent bond, OCO, N=N, CH=N, C=C, CO, O(CO)O, O, S, SO2, OCS, CH2-O, CH2-S,
LT LT LT O
I I I II
—C≡C— — C=C— — C=C-C02- — C=C-C- — N=N—
I I I I
L2 L2 L2 Q
each LT and L2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN
Z is a hydrogen, halogen, CN, -OR, COOR, NO2, a halogen substituted or unsubstituted alkylene or alkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted oxyalkylene or oxyalkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted thioalkylene or thioalkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted carboxyalkylene or alkanoylenoxy having 1 to 20 carbon atoms,
X is a covalent bond, CO, NHCO, OCO n is an integer from 1 to 10.
23. A method of using a dental composition, comprising providing a dental composition comprising a compound within the scope of the general formula:
R4 O-X-R3-M R4
I I I
CH2=C-C-O-[-CH2-CH-CH2-O-Rτ-O-]n-CH2-CH-CH2-O-C-C=CH2
II I II
O M-R3-X-O O
wherein
RT is a group of the general formula
-A-, -A-Y1-B-, -A-Yτ-B-Y2-C- or a steroidal moiety, preferably selected of the group of cholesteryl compounds, wherein each A, B and C independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 2 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to 30 carbon atoms, a substituted or unsubstituted alkylene moiety having 2 to 20 carbon atoms each YT and Y2 independently is a covalent bond, OCO, N=N, CH=N, C=C, CO, O(CO)O, O, S, SO2, OCS, CH2-O, CH2-S,
LT LT LT 0
I I I II
— C≡C— — C=C— — C=C-C02- — C=C-C- — N= —
I I I j
L2 L2 L2 Q
each LT and L2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN R3 is a covalent bond or a substituted or unsubstituted alkylene having 1 to 20 carbon atoms, oxyalkylene having 1 to 20 carbon atoms, thioalkylene having 1 to 20 carbon atoms or a carboxyalkylene having 1 to 20 carbon atoms R4 is hydrogen, a substituted or an unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, or aryl rest having 6 to 20 carbon atoms,
M is a mesogenic group of the general formula -A-Z, -A-YT-B-Z, -A-Y B-Y2-C-Z or a steroidal moiety, preferably selected of the group of cholesteryl compounds, wherein each A, B and C independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 2 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to 30 carbon atoms each YT and Y2 independently is a covalent bond, OCO, N=N, CH=N, C=C, CO, O(CO)O, O, S, SO2, OCS, CH2-O, CH2-S,
LT LT LT 0
I I I II
—C≡C— — C=C— — C=C-C02- — C=C-C- — N==N—
I I I j
L2 L2 L2 Q
each LT and L2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN
Z is a hydrogen, halogen, CN, -OR, COOR, NO2, a halogen substituted or unsubstituted alkylene or alkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted oxyalkylene or oxyalkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted thioalkylene or thioalkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted carboxyalkylene or alkanoylenoxy having 1 to 20 carbon atoms,
X is a covalent bond, CO, NHCO, OCO n is an integer from 1 to 10.
24. The method of claim 22 or 23 wherein said composition further comprises at least 30 percent by weight of filler particles.
25. The method of claim 22 or 23 wherein said composition further comprises at least 30 percent by weight of a volatile organic solvent.
26. The compound of claim 1 wherein at least one of RT and R2 is a cholesterol derivative.
27. The method of claim 22 or 23 further comprising adhering said composition to a natural tooth.
28. The compound of claim 1 in a composition adhered to a natural tooth in a patient's mouth.
29. The method of claim 1 further comprising applying said composition to a natural tooth.
30. A compound within the scope of the general formula:
R4 O-X-R3-M R4
I I I
CH2=C-C-O-[-CH2-CH-CH2-O-Rτ-O-]n-CH2-CH-CH2-O-C-C=CH2
II I II
O M-R,-X-O O
wherein
RT is a group of the general formula
-RTO-, -R O-ZT-R-I -I - 10-Z1- 11-Z2-R12- or a steroidal moiety, preferably selected of the group of cholesteryl compounds, wherein each R10, R and Rτ2 independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 2 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to 30 carbon atoms, a substituted or unsubstituted alkylene moiety having 2 to 20 carbon atoms each ZT and Z2 independently is a covalent bond, OCO, N=N, CH=N, C=C, CO, O(CO)O, O, S, SO2, OCS, CH2-O, CH2-S,
LT LT Lt O
I I I II
— C≡C — — C=C— — C=C-C02- — C=C-C- — =N —
I I I |
L2 L2 L2 Q
each LT and L2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN
R3 is a covalent bond or a substituted or unsubstituted alkylene having 1 to 20 carbon atoms, oxyalkylene having 1 to 20 carbon atoms, thioalkylene having 1 to 20 carbon atoms or a carboxyalkylene having 1 to 20 carbon atoms
R4 is hydrogen, a substituted or an unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, or aryl rest having 6 to 20 carbon atoms,
M is a mesogenic group of the general formula -R10-Z, -R10-Zτ-Rτ -Z, -Rτo-Z -Rι -Z2-R 2-Z- or a steroidal moiety, preferably selected of the group of cholesteryl compounds, wherein each Rι0, RU and Rτ2 independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 2 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to 30 carbon atoms each Z and Z2 independently is a covalent bond, OCO, N=N, CH=N, C=C, CO, O(CO)O, O, S, SO2, OCS, CH2-O, CH2-S, L, O
I II
—C≡C— — C=C— -c=c-co2- -c=c-c- — N=N-
I I ' I 2 2 L2 π
each L, and L2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN
Z is a hydrogen, halogen, CN, -OR, COOR, NO2, a halogen substituted or unsubstituted alkylene or alkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted oxyalkylene or oxyalkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted thioalkylene or thioalkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted carboxyalkylene or alkanoylenoxy having 1 to 20 carbon atoms,
X is a covalent bond, CO, NHCO, OCO n is an integer from 1 to 10.
31. A compound within the scope of the general formula:
R4 O-X-R3-M R4
I I I
CH2=C-C-O-[-CH2-CH-CH2-O-Rτ-O-]π-CH2-CH-CH2-O-C-C=CH2
II I II
O M-R3-X-O O
wherein
RT is a group of the general formula
-Rio-. -Rιo"Zι-Rιι-. -Rιo"ZrR-ιrZ-2"Ri2" or a steroidal moiety, preferably selected of the group of cholesteryl compounds, wherein each R10, Rn and R12 independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 2 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to 30 carbon atoms, a substituted or unsubstituted alkylene moiety having 2 to 20 carbon atoms each ∑ and Z2 independently is a covalent bond, OCO, N=N, CH=N, C=C, CO, O(CO)O, O, S, SO2, OCS, CH2-O, CH2-S,
—C≡C— —
Figure imgf000057_0001
each LT and L2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN
R3 is a covalent bond or a substituted or unsubstituted alkylene having 1 to 20 carbon atoms, oxyalkylene having 1 to 20 carbon atoms, thioalkylene having 1 to 20 carbon atoms or a carboxyalkylene having 1 to 20 carbon atoms
R4 is hydrogen, a substituted or an unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, or aryl rest having 6 to 20 carbon atoms,
M is a mesogenic group of the general formula
-RTO-Z, -R10-Zτ-Rιτ-Z, -Rτ0-Zτ-Rττ-Z2-R12-Z- or a steroidal moiety, preferably selected of the group of cholesteryl compounds, wherein each R10, RT T and R12 independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 2 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to 30 carbon atoms each ZT and Z2 independently is a covalent bond, OCO, N=N, CH=N, C=C, CO, O(CO)O, O, S, SO2, OCS, CH2-O, CH2-S,
Figure imgf000058_0001
each LT and L2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN
Z is a hydrogen, halogen, CN, -OR, COOR, NO2, a halogen substituted or unsubstituted alkylene or alkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted oxyalkylene or oxyalkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted thioalkylene or thioalkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted carboxyalkylene or alkanoylenoxy having 1 to 20 carbon atoms,
X is a covalent bond, CO, NHCO, OCO n is an integer from 1 to 10.
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DE69618661T2 (en) 2002-09-26
US6339114B1 (en) 2002-01-15
EP0861230B1 (en) 2002-01-02
EP0861230A1 (en) 1998-09-02
CA2229379A1 (en) 1997-04-24
US5998499A (en) 1999-12-07
JP2001509128A (en) 2001-07-10

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