Liquid-crystalline polyorganosiloxanes containing (meth) acryloxy groups

• US 5,211,877 A
• Filed: 08/31/1989
• Issued: 05/18/1993
• Est. Priority Date: 09/08/1988
• Status: Expired due to Fees

• Current Assignee: Consortium Fur Elektrochemische Industrie GmbH
• Original Assignee: Consortium Fur Elektrochemische Industrie GmbH
• Inventors: Andrejewski, Dirk, Gohary, Magdi, Luckas, Hans-Joachim, Winkler, Rainer, Kreuzer, Franz-Heinrich
• Primary Examiner(s): Stoll, Robert L.
• Assistant Examiner(s): WU, SHEAN CHIU
• Application Number:
  US07/401,261
• Time in Patent Office: 1,356 Days
• Field of Search: 252/299.1, 252/299.6, 252/299.67, 252/299.7, 556/466, 556/478, 556/420, 556/421, 556/445, 556/450, 556/462, 528/15, 528/30, 528/31, 528/32, 528/33, 528/41, 528/26, 528/27, 528/28, 528/29
• US Class Current: 252/299.01
• CPC Class Codes: C08G 77/38 Polysiloxanes modified by chemical after-treatment C08G77/045 takes precedence
• CPC Class Codes: C09D 7/41 Organic pigments; Organic dyes
• CPC Class Codes: C09K 19/408 Polysiloxanes

Abstract

The present invention relates to liquid-crystalline compounds and to a process for preparing liquid-crystalline polyorganosiloxanes having methacryloxy and/or acryloxy groups by the reaction of organosiloxanes having hydrogen atoms bonded directly to silicon atoms and/or organosilanes which can be condensed to form organosiloxanes having hydrogen atoms bonded directly to silicon atoms, with alkenes and/or alkynes having mesogenic groups, which comprises reacting in a first step the organosiloxanes with an alkene and/or alkyne having at least one non-enolic hydroxyl group protected by a protective group, and in a second step the protective group is removed and the hydroxyl group which is now free is esterified with (meth)acrylic acid, esters, anhydrides and/or halides thereof and thereafter optionally condensing the organosilanes to organosiloxanes.

Claims

1. A process for preparing liquid-crystalline polyorganosiloxanes having more than 20 mol percent of crosslinkable methacryloxy and/or acryloxy groups per molecule which is obtained from the reaction of an organosilicon compound selected from the group consisting of an organopolysiloxane having hydrogen atoms bonded directly to silicon atoms, an organosilane having hydrogen atoms bonded directly to silicon atoms and which is capable of being condensed to form organosiloxanes and mixtures thereof, with a compound selected from the group consisting of alkenes, alkynes and mixtures thereof having mesogenic groups which comprises reacting the organosilicon compound in a first step with a compound selected from the group consisting of an alkene, alkyne and mixtures thereof having at least one-non-enolic hydroxyl group protected by a protective group, and in a second step removing the protective group and esterifying the free hydroxyl group with a compound selected from the group consisting of (meth)-acrylic acid, esters, anhydrides, halides thereof, and mixtures thereof with the proviso that if the organosilicon compound is an organosilane, then the organosilane is condensed to an organosiloxane.

2. The process of claim 1, wherein the organosiloxane having hydrogen atoms bonded directly to silicon atoms has units of the formula (I):

space="preserve" listing-type="equation">R.sub.p H.sub.q SiO.sub.(4-p-q)/2 (I)

where R is selected from the group consisting of C₁ to C₁₈ hydrocarbon radicals and substituted C₁ to C₁₈ hydrocarbon radicals;

p is an integer having a value of from 0 to 3, with an average value of 1.8 to 2.2;

q is an integer having a value of from 0 to 3, with an average value such that at least three hydrogen atoms are bonded directly to silicon atoms per molecule, and the sum of p and q is a maximum of 3.

3. The process of claim 1, wherein the organosilane having hydrogen atoms bonded directly to silicon atoms and is condensable to organosiloxanes is represented by formula (VI)

4. The process or claim 1, wherein the organosilicon compound is a mixture of an organosiloxane having hydrogen atoms bonded directly to silicon atoms with units of formula (I)

5. The process of claim 1, wherein the alkenes or alkynes having mesogenic groups are represented by formula (VII)

6. The process of claim 2, wherein the alkenes or alkynes having mesogenic groups are represented by formula (VII)

7. The process of claim 3, wherein the alkenes or alkynes, having mesogenic groups are represented by formula (VII),

8. The process of claim 4, wherein the alkenes or alkynes having mesogenic groups are represented by formula (VII)

9. The process of claim 1, wherein the alkenes have at least one non-enolic hydroxyl group protected by a protective group and have up to 30 carbon atoms, which in addition to carbon atoms and hydrogen atoms, may also contain oxygen atoms, which may interrupt the carbon chain in the form of an ether linkage.

10. The process of claim 2, wherein the alkenes have at least one non-enolic hydroxyl group protected by a protective group and have up to 30 carbon atoms, which in addition to carbon atoms and hydrogen atoms, may also contain oxygen atoms, which may interrupt the carbon chain in the form of an ether linkage or ester linkage.

11. The process of claim 3, wherein the alkenes have at least one non-enolic hydroxyl group protected by a protective group and have up to 30 carbon atoms, which in addition to carbon atoms and hydrogen atoms, may also contain oxygen atoms, which may interrupt the carbon chain in the form of an ether linkage or ester linkage.

12. The process of claim 4, wherein the alkenes have at least one non-enolic hydroxyl group protected by a protective group and have up to 30 carbon atoms, which in addition to carbon atoms and hydrogen atoms, may also contain oxygen atoms, which may interrupt the carbon chain in the form of an ether linkage or ester linkage.

13. The process of claim 5, wherein the alkenes have at least one non-enolic hydroxyl group protected by a protective group and have up to 30 carbon atoms, which in addition to carbon atoms and hydrogen atoms, may also contain oxygen atoms, which may interrupt the carbon chain in the form of an ether linkage or ester linkage.

14. The process of claim 6, wherein the alkenes have at least one non-enolic hydroxyl group protected by a protective group and have up to 30 carbon atoms, which in addition to carbon atoms and hydrogen atoms, may also contain oxygen atoms, which may interrupt the carbon chain in the form of an ether linkage or ester linkage.

15. The process of claim 7, wherein the alkenes have at least one non-enolic hydroxyl group protected by a protective group and have up to 30 carbon atoms, which in addition to carbon atoms and hydrogen atoms, may also contain oxygen atoms, which may interrupt the carbon chain in the form of an ether linkage or ester linkage.

16. A liquid-crystalline polyorganosiloxane having methacryloxy groups and/or acryloxy groups prepared in accordance with the process of claim 1.

17. A liquid-crystalline polyorganosiloxane having methacryloxy groups and/or acryloxy groups prepared in accordance with the process of claim 2.

18. A liquid-crystalline polyorganosiloxane having methacryloxy groups and/or acryloxy groups prepared in accordance with the process of claim 3.

19. A liquid-crystalline polyorganosiloxane having methacryloxy groups and/or acryloxy groups prepared in accordance with the process of claim 4.

20. A liquid-crystalline polyorganosiloxane having methacryloxy groups and/or acryloxy groups prepared in accordance with the process of claim 5.

21. A liquid-crystalline polyorganosiloxane having methacryloxy groups and/or acryloxy groups prepared in accordance with the process of claim 6.

22. A liquid-crystalline polyorganosiloxane having methacryloxy groups and/or acryloxy groups prepared in accordance with the process of claim 7.

23. A composition comprising the liquid crystalline polyorganosiloxane having methacryloxy groups and/or acryloxy groups prepared in accordance with the process of claim 1, wherein the composition contains a compound of the formula ##STR6## where A⁶ is selected from the group consisting of saturated alkyl, alkoxy or cycloalkyl radicals having from 1 to 16 carbon atoms, olefinically unsaturated alkyl, alkoxy or cycloalkyl radicals having from 1 to 16 carbon atoms, cholestane radicals, cholesteryl radicals, halogen atoms, hydrogen atoms, hydroxyl, nitrile, trialkylsiloxy groups in which the alkyl radicals of the trialkylsiloxy groups have from 1 to 8 carbon atoms and a radical of the formula CH₂ ═

CQ--COO--(R"")_u --;

Q represents a hydrogen atom or a methyl group;

R"" represents divalent radicals selected from the group consisting of --CH₂ --, --O--CH₂ --, --O--CH₂ --CH₂ -- and --O--CH₂ --CH₂ --CH₂ --;

u is an integer having a value of from 0 to 20;

l is 0 or 1;

X¹ and X² represent divalent radicals selected from the group consisting of --O--, --COO--, --CONH--, --CO--, --S--, --C≡

C--, --CH═

CH--, --CH═

N--, --N═

N-- and --N═

N(O)--;

A³ represents divalent radicals, selected from the group consisting of 1,4-phenylene and 1,4-cyclohexylene radicals, substituted arylenes having from 1 to 10 carbon atoms, substituted cycloalkylenes having from 1 to 10 carbon atoms and heteroarylenes having from 1 to 10 carbon atoms;

f, has a value of 1, and a and g each have a value of 0 or 1.

24. A composition comprising the liquid crystalline polyorganosiloxane having methacryloxy groups and/or acryloxy groups prepared in accordance with the process of claim 2, wherein the composition contains a compound of the formula ##STR7## where A⁶ is selected from the group consisting of saturated alkyl, alkoxy or cycloalkyl radicals having from 1 to 16 carbon atoms, olefinically unsaturated alkyl, alkoxy or cycloalkyl radicals having from 1 to 16 carbon atoms, cholestane radicals, cholesteryl radicals, halogen atoms, hydrogen atoms, hydroxyl, nitrile, trialkylsiloxy groups in which the alkyl radicals of the trialkylsiloxy groups have from 1 to 8 carbon atoms and a radical of the formula CH₂ ═

CQ--COO--(R"")_u --;

Q represents a hydrogen atom or a methyl group;

R"" represents divalent radicals selected from the group consisting of --CH₂ --, --O--CH₂ --, --O--CH₂ --CH₂ -- and --O--CH₂ --CH₂ --CH₂ --;

u is an integer having a value of from 0 to 20;

l is 0 or 1;

X¹ and X² represent divalent radicals selected from the group consisting of --O--, --COO--, --CONH--, --CO--, --S--, --C≡

C--, --CH═

CH--, --CH═

N--, --N═

-- and '"'"'N═

N(O)--;

A³ represents divalent radicals, selected from the group consisting of 1,4-phenylene and 1,4-cyclohexylene radicals, substituted arylenes having from 1 to 10 carbon atoms, substituted cycloalkylenes having from 1 to 10 carbon atoms and heteroarylenes having from 1 to 10 carbon atoms;

f, has a value of 1, and a and g each have a value of 0 or 1.

25. A composition comprising the liquid crystalline polyorganosiloxane having methacryloxy groups and/or acryloxy groups prepared in accordance with the process of claim 3, wherein the composition contains a compound of the formula ##STR8## where A⁶ is selected from the group consisting of saturated alkyl, alkoxy or cycloalkyl radicals having from 1 to 16 carbon atoms, olefinically unsaturated alkyl, alkoxy or cycloalkyl radicals having from 1 to 16 carbon atoms, cholestane radicals, cholesteryl radicals, halogen atoms, hydrogen atoms, hydroxyl, nitrile, trialkylsiloxy groups in which the alkyl radicals of the trialkylsiloxy groups have from 1 to 8 carbon atoms and a radical of the formula CH₂ ═

CQ--COO--(R"")_u --;

Q represents a hydrogen atom or a methyl group;

R"" represents divalent radicals selected from the group consisting of --CH₂ --, --O--CH₂ --, --O--CH₂ --CH₂ -- and --O--CH₂ --CH₂ --CH₂ --;

u is an integer having a value of from 0 to 20;

l is 0 or 1;

X¹ and X² represent divalent radicals selected from the group consisting of --O--, --COO--, --CONH-- , --CO--, --S--, --C≡

C--, --CH═

CH--, --CH═

N--, --N═

N-- and --N═

N(O)--;

A³ represents divalent radicals, selected from the group consisting of 1,4-phenylene and 1,4-cyclohexylene radicals, substituted arylenes having from 1 to 10 carbon atoms, substituted cycloalkylenes having from 1 to 10 carbon atoms and heteroarylenes having from 1 to 10 carbon atoms;

f, has a value of 1, and a and g each have a value of 0 or 1.

26. A composition comprising the liquid crystalline polyorganosiloxane having methacryloxy groups and/or acryloxy groups prepared in accordance with the process of claim 4, wherein the composition contains a compound of the formula ##STR9## where A⁶ is selected from the group consisting of saturated alkyl, alkoxy or cycloalkyl radicals having from 1 to 16 carbon atoms, olefinically unsaturated alkyl, alkoxy or cycloalkyl radicals having from 1 to 16 carbon atoms, cholestane radicals, cholesteryl radicals, halogen atoms, hydrogen atoms, hydroxyl, nitrile, trialkylsiloxy groups in which the alkyl radicals of the trialkylsiloxy groups have from 1 to 8 carbon atoms and a radical of the formula CH₂ ═

CQ--COO--(R"")_u --;

Q represents a hydrogen atom or a methyl group;

R"" represents divalent radicals selected from the group consisting of --CH₂ --, --O--CH₂ --, --O--CH₂ --CH₂ -- and --O--CH₂ --CH₂ --CH₂ --;

u is an integer having a value of from 0 to 20;

l is 0 or 1;

X¹ and X² represent divalent radicals selected from the group consisting of --O--, --COO--, --CONH-- , --CO--, --S--, --C≡

C--, --CH═

CH--, --CH═

N--, --N═

N-- and --N═

N(O)--;

A³ represents divalent radicals, selected from the group consisting of 1,4-phenylene and 1,4-cyclohexylene radicals substituted arylenes having from 1 to 10 carbon atoms, substituted cycloalkylenes having from 1 to 10 carbon atoms and heteroarylenes having from 1 to 10 carbon atoms;

f, has a value of 1, and a and g each have a value of 0 or 1.

27. A composition comprising the liquid crystalline polyorganosiloxane having methacryloxy groups and/or acryloxy groups prepared in accordance with the process of claim 5, wherein the composition contains a compound of the formula ##STR10## where A⁶ is selected from the group consisting of saturated alkyl, alkoxy or cycloalkyl radicals having from 1 to 16 carbon atoms, olefinically unsaturated alkyl, alkoxy or cycloalkyl radicals having from 1 to 16 carbon atoms, cholestane radicals, cholesteryl radicals, halogen atoms, hydrogen atoms, hydroxyl, nitrile, trialkylsiloxy groups in which the alkyl radicals of the trialkylsiloxy groups have from 1 to 8 carbon atoms and a radical of the formula CH₂ ═

CQ--COO--(R"")_u --;

Q represents a hydrogen atom or a methyl group;

R"" represents divalent radicals selected from the group consisting of --CH₂ --, --O--CH₂ --, --O--CH₂ --CH₂ -- and --O--CH₂ --CH₂ --CH₂ --;

u is an integer having a value of from 0 to 20;

l is 0 or 1;

X¹ and X² represent divalent radicals selected from the group consisting of --O--, --COO--, --CONH-- , --CO--, --S--, --C≡

C--, --CH═

CH--, --CH═

N--, --N═

N-- and --N═

N(O)--;

A³ represents divalent radicals, selected from the group consisting of 1,4-phenylene and 1,4-cyclohexylene radicals, substituted arylenes having from 1 to 10 carbon atoms, substituted cycloalkylenes having from 1 to 10 carbon atoms and heteroarylenes having from 1 to 10 carbon atoms;

f, has a value of 1, and a and g each have a value of 0 or 1.

28. A composition comprising the liquid crystalline polyorganosiloxane having methacryloxy groups and/or acryloxy groups prepared in accordance with the process of claim 6, wherein the composition contains a compound of the formula ##STR11## where A⁶ is selected from the group consisting of saturated alkyl, alkoxy or cycloalkyl radicals having from 1 to 16 carbon atoms, olefinically unsaturated alkyl, alkoxy or cycloalkyl radicals having from 1 to 16 carbon atoms, cholestane radicals, cholesteryl radicals, halogen atoms, hydrogen atoms, hydroxyl, nitrile, trialkylsiloxy groups in which the alkyl radicals of the trialkylsiloxy groups have from 1 to 8 carbon atoms and a radical of the formula CH₂ ═

CQ--COO--(R"")_u --;

Q represents a hydrogen atom or a methyl group;

R"" represents divalent radicals selected from the group consisting of --CH₂ --, --O--CH₂ --, --O--CH₂ --CH₂ -- and --O--CH₂ --CH₂ --CH₂ --;

u is an integer having a value of from 0 to 20;

l is 0 or 1;

X¹ and X² represent divalent radicals selected from the group consisting of --O--, --COO--, --CONH-- , --CO--, --S--, --C≡

C--, --CH═

CH--, --CH═

N--, --N═

N-- and --N═

N(O)--;

A³ represents divalent radicals, selected from the group consisting of 1,4-phenylene and 1,4-cyclohexylene radicals, substituted arylenes having from 1 to 10 carbon atoms, substituted cycloalkylenes having from 1 to 10 carbon atoms and heteroarylenes having from 1 to 10 carbon atoms;

f, has a value of 1, and a and g each have a value of 0 or 1.

29. A composition comprising the liquid crystalline polyorganosiloxane having methacryloxy groups and/or acryloxy groups prepared in accordance with the process of claim 7, wherein the composition contains a compound of the formula ##STR12## where A⁶ is selected from the group consisting of saturated alkyl, alkoxy or cycloalkyl radicals having from 1 to 16 carbon atoms, olefinically unsaturated alkyl, alkoxy or cycloalkyl radicals having from 1 to 16 carbon atoms, cholestane radicals, cholesteryl radicals, halogen atoms, hydrogen atoms, hydroxyl, nitrile, trialkylsiloxy groups in which the alkyl radicals of the trialkylsiloxy groups have from 1 to 8 carbon atoms and a radical of the formula CH₂ ═

CQ--COO--(R"")_u --;

Q represents a hydrogen atom or a methyl group;

R"" represents divalent radicals selected from the group consisting of --CH₂ --, --O--CH₂ --, --O--CH₂ --CH₂ -- and --O--CH₂ --CH₂ --CH₂ --;

u is an integer having a value of from 0 to 20;

l is 0 or 1;

X¹ and X² represent divalent radicals selected from the group consisting of --O--, --COO--, --CONH-- , --CO--, --S--, --C≡

C--, --CH═

CH--, --CH═

N--, --N═

N-- and --N═

N(O)--;

A³ represents divalent radicals, selected from the group consisting of 1,4-phenylene and 1,4-cyclohexylene radicals, substituted arylenes having from 1 to 10 carbon atoms, substituted cycloalkylenes having from 1 to 10 carbon atoms and heteroarylenes having 1 to 10 carbon atoms;

f, has a value of 1, and a and g each have a value of 0 or 1.