Liquid crystalline (meth)acrylate compounds, composition and method

A liquid crystalline compound within the scope of the general formula:

• ##STR30## wherein R.sub.1 is a group of the general formula
• -A'-, -A'-R.sup.0.sub.1 -R'-, -A'-R.sup.0.sub.1 -R'-R.sup.0.sub.2 -R"-
• or a steroidal moiety, wherein
• each A', R' and R" independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 6 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to 30 carbon atoms, a substituted or unsubstituted alkylene moiety having up to 20 carbon atoms
• each R.sup.0.sub.1 and R.sup.0.sub.2 independently is a covalent bond, OCO, N.dbd.N, CH.dbd.N, C.dbd.C, CO, O(CO)O, O, S, SO.sub.2, OCS, CH.sub.2 --O, CH.sub.2 --S, ##STR31## each L.sub.1 and L.sub.2 independently is a hydrogen, alkyl having 1 to 20 carbon atoms, alkylene having 2 to 20 carbon atoms or CN
• R.sub.3 is a covalent bond or halogen 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.sub.4 is hydrogen, a substituted or an unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, or aryl having 6 to 20 carbon atoms,
• M is a mesogenic group comprising two rings and of the general formula
• -A.sup.2 -Z, -A.sup.2 -R.sup.0.sub.1 -R.sup.2 -Z, -A.sup.2 -R.sup.0.sub.1 -R.sup.2 -R.sup.0.sub.2 -R.sup.3 -Z
• or a steroidal moiety, wherein
• each A.sup.2 independently is a substituted or unsubstituted cycloalkylene moiety having up to 30 carbon atoms
• each R.sup.2 independently is a substituted or unsubstituted aromatic moiety having up to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having up to 24 carbon atoms
• each R.sup.3 independently is a substituted or unsubstituted aromatic moiety having up to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having up to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having up to 30 carbon atoms, a substituted or unsubstituted alkylene moiety having up to 20 carbon atoms
• each R.sup.0.sub.1 and R.sup.0.sub.2 independently is a covalent bond, OCO, N.dbd.N, CH.dbd.N, C.dbd.C, CO, O(CO)O, O, S, SO.sub.2, OCS, CH.sub.2 --O, CH.sub.2 --S, ##STR32## each L.sub.1 and L.sub.2 independently is a hydrogen, alkyl having 1 to 20 carbon atoms, alkylene having 2 to 20 carbon atoms or CN
• Z is a hydrogen, halogen, CN, --OR, COOR, NO.sub.2, a halogen substituted or unsubstituted alkylene or alkenyl having 1 to 20 carbon atoms, a halogen substituted or unsubstituted oxyalkylene or oxyalkenyl having up to 20 carbon atoms, a halogen substituted or unsubstituted thioalkylene or thioalkenyl having up to 20 carbon atoms, a halogen substituted or unsubstituted carboxyalkylene or alkanoylenoxy having up to 20 carbon atoms,
• X is a covalent bond, CO, NHCO, OCO
• n is an integer from 1 to 10, said liquid crystalline compound being in a mesomorphic state.

A dental composition comprising a liquid crystalline compound within the scope of the general formula ##STR37## wherein R.sub.1 is a group of the general formula

• -A'-, -A'-R.sup.0.sub.1 -R'-, -A'-R.sup.0.sub.1 -R'-R.sup.0.sub.2 -R"-
• or a steroidal moiety, wherein
• each A.sup.1, B.sup.1 and C.sup.1 independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 6 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 R.sup.0.sub.1 and R.sup.0.sub.2 independently is a covalent bond, OCO, N.dbd.N, CH.dbd.N, C.dbd.C, CO, O(CO)O, O, S, SO.sub.2, OCS, CH.sub.2 --O, CH.sub.2 --S, ##STR38## each L, and L.sub.2 independently is hydrogen, alkyl having 1 to 20 carbon atoms, alkylene having 2 to 20 carbon atoms or CN
• R.sub.3 is a covalent bond, alkyl having 1 to 20 carbon atoms, halogen substituted or unsubstituted alkylene having 2 to 20 carbon atoms, oxyalkylene having 1 to 20 carbon atoms, thioalkylene having 2 to 20 carbon atoms or a carboxyalkylene having 2 to 20 carbon atoms
• R.sub.4 is hydrogen, a substituted or an unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, or aryl having 6 to 20 carbon atoms,
• M is a mesogenic group comprising two rings and of the general formula
• -A.sup.2 -Z, -A.sup.2 -R.sup.0.sub.1 -R.sup.2 -Z, -A.sup.2 -R.sup.0.sub.1 -R.sup.2 -R.sup.0.sub.2 -R.sup.3 -Z
• or a steroidal moiety, wherein
• each A.sup.2 independently is a substituted or unsubstituted aromatic moiety having up to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having up to 24 carbon atoms
• each R.sup.2 and R.sup.3 independently is a substituted or unsubstituted aromatic moiety having up to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having up to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having up to 30 carbon atoms
• each R.sup.0.sub.1 and R.sup.0.sub.2 independently is a covalent bond, OCO, N.dbd.N, CH.dbd.N, C.dbd.C, CO, O(CO)O, O, S, SO.sub.2, OCS, CH.sub.2 --O, CH.sub.2 --S, ##STR39## each L.sub.1 and L.sub.2 independently is a hydrogen, alkyl having 1 to 20 carbon atoms, alkylene having 1 to 20 carbon atoms or CN
• Z is hydrogen, halogen, CN, --OR, COOR, NO.sub.2, alkyl having 1 to 20 carbon atoms, halogen substituted or unsubstituted alkylene or alkylidene having up to 20 carbon atoms, a halogen substituted or unsubstituted oxyalkylene or oxyalkylidene having up to 20 carbon atoms, a halogen substituted or unsubstituted thioalkylene or thioalkylidene having up to 20 carbon atoms, a halogen substituted or unsubstituted carboxyalkylene or alkanoylenoxy having 2 to 20 carbon atoms,
• X is a covalent bond, CO, NHCO, OCO
• n is an integer from 1 to 10, said liquid crystalline compound being in a mesomorphic state.

A method of using a dental composition, comprising providing a dental composition comprising a liquid crystalline compound within the scope of the general formula:

• ##STR40## wherein R.sub.1 is a group of the general formula
• -A'-, -A'-R.sup.0.sub.1 -R'-, -A'-R.sup.0.sub.1 -R'-R.sup.0.sub.2 -R"-
• or a steroidal moiety, wherein
• each A', R' and R" independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 6 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having up to 30 carbon atoms, a substituted or unsubstituted alkylene moiety having up to 20 carbon atoms
• each R.sup.0.sub.1 and R.sup.0.sub.2 independently is a covalent bond, OCO, N.dbd.N, CH.dbd.N, C.dbd.C, CO, O(CO)O, O, S, SO.sub.2, OCS, CH.sub.2 --O, CH.sub.2 --S, ##STR41## each L.sub.1 and L.sub.2 independently is hydrogen, alkyl having 1 to 20 carbon atoms, alkylene having 2 to 20 carbon atoms or CN
• R.sub.3 is a covalent bond, alkyl having 1 to 20 carbon atoms, halogen substituted or unsubstituted alkylene having 2 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.sub.4 is hydrogen, a substituted or an unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, or aryl having 6 to 20 carbon atoms,
• M is a mesogenic group comprising two rings and of the general formula
• -A.sup.2 -Z, -A.sup.2 -R.sup.0.sub.1 -R.sup.2 -Z, -A.sup.2 -R.sup.0.sub.1 -R.sup.2 -R.sup.0.sub.2 -R.sup.3 -Z
• or a steroidal moiety, wherein
• each A.sup.2 independently is a substituted or unsubstituted aromatic moiety having up to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having up to 24 carbon atoms
• each R.sup.2 and R.sup.3 independently is a substituted or unsubstituted aromatic moiety having up to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having up to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having up to 30 carbon atoms
• each R.sup.0.sub.1 and R.sup.0.sub.2 independently is a covalent bond, OCO, N.dbd.N, CH.dbd.N, C.dbd.C, CO, O(CO)O, O, S, SO.sub.2, OCS, CH.sub.2 --O, CH.sub.2 --S, ##STR42## each L.sub.1 and L.sub.2 independently is a hydrogen, a alkylene having up to 20 carbon atoms or CN
• Z is a hydrogen, halogen, CN, --OR, COOR, NO.sub.2, alkyl having 1 to 20 carbon atoms, halogen substituted or unsubstituted alkylene or alkenyl having 2 to 20 carbon atoms, a halogen substituted or unsubstituted oxyalkylene or oxyalkenyl having up to 20 carbon atoms, a halogen substituted or unsubstituted thioalkylene or thioalkenyl having up to 20 carbon atoms, a halogen substituted or unsubstituted carboxyalkylene or alkanoylenoxy having 2 to 20 carbon atoms,
• X is a covalent bond, CO, NHCO, OCO
• n is an integer from 1 to 10, said liquid crystalline compound being in a mesomorphic state,
• and polymerizing said compound to form polymeric material.

A method of using a dental composition, comprising providing a dental composition comprising a liquid crystalline compound within the scope of the general formula:

• ##STR43## wherein R.sub.1 is a group of the general formula
• -A'-, -A'-R.sup.0.sub.1 -R'-, -A'-R.sup.0.sub.1 -R'-R.sup.0.sub.2 -R"-
• or a steroidal moiety, selected of the group of cholesteryl compounds,
• wherein
• each A', R' and R" independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 6 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to 30 carbon atoms, a substituted or unsubstituted alkylene moiety having up to 20 carbon atoms
• each R.sup.0.sub.1 and R.sup.0.sub.2 independently is a covalent bond, OCO, N.dbd.N, CH.dbd.N, C.dbd.C, CO, O(CO)O, O, S, SO.sub.2, OCS, CH.sub.2 --O, CH.sub.2 --S, ##STR44## each L.sub.1 and L.sub.2 independently is a hydrogen, alkyl having 1 to 20 carbon atoms, alkylene having 2 to 20 carbon atoms or CN
• R.sub.3 is a covalent bond or halogen substituted or unsubstituted alkylene having 2 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.sub.4 is hydrogen, halogen substituted or an unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, or aryl having 6 to 20 carbon atoms,
• M is a mesogenic group comprising two rings and of the general formula
• -A.sup.2 -Z, -A.sup.2 -R.sup.0.sub.1 -R.sup.2 -Z, -A.sup.2 -R.sup.0.sub.1 -R.sup.2 -R.sup.0.sub.2 -R.sup.3 -Z
• or a steroidal moiety, wherein
• each A.sup.2 independently is a substituted or unsubstituted cycloalkylene moiety having up to 30 carbon atoms
• each R.sup.2 independently is a substituted or unsubstituted aromatic moiety having up to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having up to 24 carbon atoms
• each R.sup.3 independently is a substituted or unsubstituted aromatic moiety having up to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having up to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having up to 30 carbon atoms, a substituted or unsubstituted alkulene moiety having up to 20 carbon atoms
• each R.sup.0.sub.1 and R.sup.0.sub.2 independently is a covalent bond, OCO, N.dbd.N, CH.dbd.N, C.dbd.C, CO, O(CO)O, O, S, SO.sub.2, OCS, CH.sub.2 --O, CH.sub.2 --S, ##STR45## each L.sub.1 and L.sub.2 independently is a hydrogen, a alkylene having 1 to 20 carbon atoms or CN
• Z is a hydrogen, halogen, CN, --OR, COOR, NO.sub.2, alkyl having 1 to 20 carbon atoms, halogen substituted or unsubstituted alkylene or alkenyl having up to 20 carbon atoms, a halogen substituted or unsubstituted oxyalkylene or oxyalkenyl having up to 20 carbon atoms, a halogen substituted or unsubstituted thioalkylene or thioalkenyl having up to 20 carbon atoms, a halogen substituted or unsubstituted carboxyalkylene or alkanoylenoxy having 2 to 20 carbon atoms,
• X is a covalent bond, CO, NHCO, OCO
• n is an integer from 1 to 10, said liquid crystalline compound being in a mesomorphic state,
• and polymerizing said compound.

A liquid crystalline compound within the scope of the general formula:

• ##STR46## wherein R.sub.1 is a group of the general formula
• -R'.sub.10 -, -R'.sub.10 -Z.sub.1 -R'.sub.11 -, -R'.sub.10 -Z.sub.1 -R'.sub.11 -Z.sub.2 -R'.sub.12 -
• or a steroidal moiety, wherein
• each R'.sub.10, R'.sub.11 and R'.sub.12 independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 6 to 24 carbon atoms
• each Z.sub.1 and Z.sub.2 independently is a covalent bond, OCO, N.dbd.N, CH.dbd.N, C.dbd.C, CO, O(CO)O, O, S, SO.sub.2, OCS, CH.sub.2 --O, CH.sub.2 --S, ##STR47## each L.sub.1 and L.sub.2 independently is hydrogen, alkyl having 1 to 20 carbon atoms, alkylene having 2 to 20 carbon atoms or CN
• R.sub.3 is a covalent bond, alkyl having 1 to 20 carbon atoms, halogen substituted or unsubstituted alkylene having 2 to 20 carbon atoms, oxyalkylene having 1 to 20 carbon atoms, thioalkylene having 1 to 20 carbon atoms or a carboxyalkylene having 2 to 20 carbon atoms
• R.sup.4 is hydrogen, a substituted or an unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, or aryl having 6 to 20 carbon atoms,
• M is a mesogenic group comprising two rings and of the general formula
• -R'.sub.10 -, -R'.sub.10 -Z.sub.1 -R'.sub.11 -, -R'.sub.10 -Z.sub.1 -R'.sub.11 -Z.sub.2 -R'.sub.12-Z
• or a steroidal moiety, wherein
• each R'.sub.10, R'.sub.11 and R'.sub.12 independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 6 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to 30 carbon atoms
• each Z.sub.1 and Z.sub.2 independently is a covalent bond, OCO, N.dbd.N, CH.dbd.N, C.dbd.C, CO, O(CO)O, O, S, SO.sub.2, OCS, CH.sub.2 --O, CH.sub.2 --S, ##STR48## each L.sub.1 and L.sub.2 independently is a hydrogen, alkylene having up to 20 carbon atoms or CN
• Z is hydrogen, halogen, CN, --OR, COOR, NO.sub.2, halogen substituted or unsubstituted alkylene or alkenyl having up to 20 carbon atoms, a halogen substituted or unsubstituted oxyalkylene or oxyalkenyl having up to 20 carbon atoms, a halogen substituted or unsubstituted thioalkylene or thioalkenyl having up to 20 carbon atoms, a halogen substituted or unsubstituted carboxyalkylene or alkanoylenoxy having 2 to 20 carbon atoms,
• X is a covalent bond, CO, NHCO, OCO
• n is an integer from 1 to 10, said liquid crystalline compound being in a mesomorphic state.

A liquid crystalline compound within the scope of the general formula:

• ##STR49## wherein R.sub.1 is a group of the general formula
• -R.sub.10 -, -R.sub.10 -Z.sub.1 -R.sub.11 -, -R.sub.10 -Z.sub.1 -R.sub.11 -Z.sub.2 -R.sub.12 -
• or a steroidal moiety, wherein
• each R.sub.10, R.sub.11, and R.sub.12 independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 6 to 24 carbon atoms
• each Z.sub.1 and Z.sub.2 independently is a covalent bond, OCO, N.dbd.N, CH.dbd.N, C.dbd.C, CO, O(CO)O, O, S, SO.sub.2, OCS, CH.sub.2 --O, CH.sub.2 --S, ##STR50## each L.sub.1 and L.sub.2 independently is hydrogen, alkylene having up to 20 carbon atoms or CN
• R.sub.3 is a covalent bond or a halogen substituted or unsubstituted alkylene having up to 20 carbon atoms, oxyalkylene having up to 20 carbon atoms, thioalkylene having up to 20 carbon atoms or a carboxyalkylene having 2 to 20 carbon atoms
• R.sub.4 is hydrogen, halogen substituted or an unsubstituted alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, or aryl having 6 to 20 carbon atoms,
• M is a mesogenic group comprising two rings and of the general formula
• -R'.sub.10 -Z, -R'.sub.10 -Z.sub.1 -R'.sub.11 -Z, -R'.sub.10 -Z.sub.1 -R'.sub.11 -Z.sub.2 -R'.sub.12 -Z
• or a steroidal moiety, wherein
• each R'.sub.10, R'.sub.11 and R'.sub.12 independently is a substituted or unsubstituted aromatic moiety having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaromatic moiety having 6 to 24 carbon atoms or a substituted or unsubstituted cycloalkylene moiety having 5 to 30 carbon atoms
• each Z.sub.1 and Z.sub.2 independently is a covalent bond, OCO, N.dbd.N, CH.dbd.N, C.dbd.C, CO, O(CO)O, O, S, SO.sub.2, OCS, CH.sub.2 --O, CH.sub.2 --S, ##STR51## each L.sub.1 and L.sub.2 independently is a hydrogen, a alkylene having up to 20 carbon atoms or CN
• Z is a hydrogen, halogen, CN, --OR, COOR, NO.sub.2, halogen substituted or unsubstituted alkylene or alkenyl having up to 20 carbon atoms, a halogen substituted or unsubstituted oxyalkylene or oxyalkenyl having up to 20 carbon atoms, a halogen substituted or unsubstituted thioalkylene or thioalkenyl having up to 20 carbon atoms, a halogen substituted or unsubstituted carboxyalkylene or alkanoylenoxy having 2 to 20 carbon atoms,
• X is a covalent bond, CO, NHCO, OCO
• n is an integer from 1 to 10, said liquid crystalline compound being in a mesomorphic state.