Linear and cyclic polymers or oligomers having a photoreactive ethene group

Abstract

The invention is concerned with linear and cyclic polymers or oligomers having a photoreactive ethene group. The polymers are of the formula ##STR1## wherein M a , M b , M c are monomer units for homo- or copolymers; x, y, z are mole fractions of the copolymers, whereby in each case 0<x≦1; 0≦y≦1 and 0≦z<1; S a , S b are spacer units; Z a , Z b are molecular units which can undergo photochemical isomerization/dimerization; n is a magnitude of 4-100 000 and m is 0 or 1, The compounds are used as an orienting layer for liquid cyrstals.

We claim: 
     
       1. A polymer of formula I ##STR8## wherein M a , M b , M c  are monomer units for homo- or copolymers; x, y, z are mole fractions of the copolymers, whereby in each case 0<X≦1; 0≦y≦1 and 0≦z<1;   S a , S b  are independently of one another, methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,2-propylene, 1,3-butylene, cyclopentane-1,2-diyl, cyclopentane-1,3-diyl, cyclohexane-1,3-diyl, cyclohexane-1,4-diyl, piperidine-1,4-diyl, piperizine-1,4-diyl, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, ethyleneoxy, ethyleneoxycarbonyl, ethylenecarboxy, CONH-- or --CONR' in which R 1  is lower alkyl;   Z a , Z b  each independently are formula II ##STR9## wherein ring A 1  is 1,4-phenylene, which is unsubstituted or substituted with at least one of halogen, cyano and nitro, or pyridine-2,5-yl, pyrimidine-2-5-yl, 2,5-thiophenediyl, 2,5-furanylene, 1,4- or 2,6-naphthylene, in which a CH group can be replaced by nitrogen;   ring A,A 2  each individually are 1,4-phenylene, which is unsubstituted or substituted with at least one of halogen, cyano, and nitro, pyridine-2-5-yl, pyrimidine-2,5-yl, or 2,5-thiophenediyl, 2,5-furanylene, trans-1,4-cyclohexylene, trans-1,3-dioxane-2,5-yl or 1,4-piperidyl;   A 3  is --COO--, --CONH--, --CO--E--, 1,4-phenylene, which is unsubstituted or substituted with at least one of halogen, cyano and nitro, or pyridine-2,5-yl, pyrimidine-2-5-yl, 2,5-thiophenediyl, 2,5-furanylene, 1,4- or 2,6-naphthylene, in which a CH group can be replaced by nitrogen;   E is 1,4-phenylene, which is unsubstituted or substituted with at least one of halogen, cyano and nitro, or pyridine-2,5-yl, pyrimidine-2,5-yl, 2,5-thiophenediyl, 2,5-furanylene, 1,4- or 2,6-naphthylene, in which a CH group can be replaced by nitrogen;   Z,Z 1  each independently are a single covalent bond, --CH 2  CH 2  --, COO--, --OOC--, --OCH 2  --, CH 2  O--, --C.tbd.C--, --(CH 2 ) 4 , --O(CH 2 ) 3  --, --(CH 2 ) 3  O-- or the trans form of --OCH 2  CH═CH--, --CH═CHCH 2  O--, --(CH 2 ) 2  CH═CH-- or --CH═CH(CH 2 ) 2  --;   R 1  is hydrogen, halogen, cyano, nitro, NCS, alkyl with 1 to 12 carbon atoms, which is unsubstituted or substituted with fluorine and in which 1 or 2 non-adjacent --CH 2  -- groups can be replaced by oxygen, --COO--, --OOC--, --CO-- and in which a --CH 2  CH 2  -- group can be replaced by --CH═CH--;   n,p each independently are 0 or 1;   X,Y each independently are hydrogen, halogen, cyano, alkyl with 1 to 12 carbon atoms which is unsubstituted or substituted with fluorine and in which 1 or 2 non-adjacent --CH 2  -- groups can be replaced by oxygen, --COO--, --OOC--, --CO-- and/or --CH═CH--; with the proviso that A 3  is different from --COO--, when simultaneously n and p each are 0, A 1  is phenyl, R 1  is hydrogen or methoxy and S a  and, respectively S b  are a single bond;     n' is from 4-100 000 and   m is 0 or 1.   
     
     
       2. A polymer according to claim 1 of formula 1-A: ##STR10## wherein Ma, Sa, Za and n' have the significance given in claim 1. 
     
     
       3. A polymer according to of claim 1, wherein the isomerization/dimerization units Z a  and Z b  each independently are of formula ##STR11## wherein ring A 1  is 1,4-phenylene, which is unsubstituted or substituted with halogen, cyano and/or nitro, or pyrimidine-2,5-diyl, pyridine-2,5-diyl, 2,5-thiophenediyl, 2,5-furanylene, 1,4-naphthylene or 2,6-naphthylene; ring A 2  is 1,4-phenylene, which is unsubstituted or substituted with halogen, cyano and/or nitro, or pyrimidine-2,5-diyl, pyridine-2,5-diyl, 2,5-thiophenediyl, 2,5-furanylene, trans-1,4-cyclohexylene, trans-1,3-dioxane-2,5-diyl or 1,4-piperidyl;   ring A 4  is 1,4-phenylene, which is unsubstituted or substituted with halogen, cyano and/or nitro;   Z 1  is a single covalent bond, --CH 2  CH 2  --, --COO--, --OCH 2  --, --(CH 2 ) 4  --, --O(CH 2 ) 3  -- or --(CH 2 ) 3  O--;   R 1  is hydrogen, halogen, cyano, nitro, alkyl with 1 to 12 carbon atoms, which is optionally substituted with fluorine and in which optionally 1 or 2 non-adjacent --CH 2  -- groups can be replaced by oxygen or --COO-- and/or a --CH 2  CH 2  -- group can be replaced by --CH═CH--;   n is 0 or 1;   X is hydrogen or alkyl with 1 to 6 carbon atoms, which is optionally substituted with halogen;   Y is hydrogen, cyano, --COO-alkyl, alkyl with 1 to 6 carbon atoms, which is optionally substituted with fluorine; and   S a , S b  are spacer units; with the proviso that in formula II-A simultaneously n does not signify 0, A 1  does not signify phenyl, R 1  does not signify hydrogen or methoxy, X and Y do not signify hydrogen and S a  or S b  does not signify a single bond.     
     
     
       4. A polymer according to claim 1, wherein the isomerization/dimerization units Z a  and Z b  each independently are of formula ##STR12## wherein R 1  is hydrogen, halogen, cyano, nitro, alkyl or alkoxy with 1 to 6 carbon atoms, with the proviso that in formula IIa simultaneously R 1  does not signify hydrogen or methoxy and S a  or S b  does not signify a single bond. 
     
     
       5. A polymer according to claim 1 selected from the group consisting of: poly(methacryloyloxyethyl-3-(E)-[4-cyano-4'-biphenyl]acrylate;   poly(methacryloyloxyethyl-3(E)-[4-cyanophenyl]acrylate;   poly(methacryloyloxyethyl-3(E)-[4-chlorophenyl]acrylate);   poly(methacryloyloxyethyl-3(E)-[4-methoxyphenyl]acrylate);   poly(methacryloyloxyethyl-3(E)-[4-nitrophenyl]acrylate);   poly(3-methacryloylaminopropyl-(E)-3-[4-cyano-phenyl]acrylamide)   poly[1-[1-[(E)-3-(4-methoxy-phenyl)-acryloyl]piperidine-4-yloxycarbonyl]-1- methyl-ethylen]; and   poly(methacryloyloxyethyl-3-(E)-biphenylacrylate).   
     
     
       6. A polymer according to claim 5, poly(methacryloyloxyethyl-3-(E)-[4-cyano-4'-biphenyl]acrylate. .Iadd.   
     
     
       7.  A polymer according to formula 1-A ##STR13## wherein M a  is a monomer unit for a homopolymer; S a  is an alkylene chain with 1 to 10 carbon atoms, a cycloalkylene group with 3 to 8 carbon atoms in which optionally one or two methylene groups can be replaced by NH groups, or phenylene which can be substituted with lower alkyl, lower alkoxy, --CN, --NO 2 , halogen, carbonate, an ester group, an amide group, an ether group or a combination of said groups;   Z a  is of formula II ##STR14## wherein, ring A 1  1,4-phenylene, which is unsubstituted or substituted with at least one of halogen, cyano and nitro, or pyridine-2,5-yl, pyrimidine-2-5-yl, 2,5-thiophenediyl, 2,5-furanylene, 1,4- or 2,6-napthylene, in which a CH group can be replaced by nitrogen;   ring A,A 2  each individually are 1,4-phenylene, which is unsubstituted or substituted with at least one of halogen, cyano and nitro, pyridine-2-5-yl, pyrimidine-2,5-yl, or 2,5-thiophenediyl, 2,5-furanylene, trans-1,4-cyclohexylene, trans-1,3-dioxane-2,5-diyl or 1,4-piperidyl;   A 3  is --COO--, --CONH--, --CO--E--, 1,4-phenylene, which is unsubstituted or substituted with at least one of halogen, cyano and nitro, or pyridine-2,5-yl pyrimidine-2,5-yl, 2,5-thiophenediyl, 2,5-furanylene, 1,4- or 2,6-naphthylene, in which a CH group can be replaced by nitrogen;   E is 1,4-phenylene, which is unsubstituted or substituted with at least one of halogen, cyano and nitro, or pyridine-2,5-yl, pyrimidine-2,5-yl, 2,5-thiophenediyl, 2,5-furanylene, 1,4- or 2,6-naphthylene, in which a CH group can be replaced by nitrogen;   Z,Z 1  each independently are a single covalent bond, --CH 2  CH 2  --, --COO--, --OOC--, --OCH 2  --, --CH 2  O--, --C.tbd.C--, --(CH 2 ) 4  --, --O(CH 2 ) 3  --, --(CH 2 ) 3  O-- or the trans form of --OCH 2  CH═CH--, --CH═CHCH 2  O--, --(CH 2 ) 2  CH═CH-- or --CH═CH(CH 2 ) 2  --;   R 1  is hydrogen, halogen, cyano, nitro, NCS, alkyl with 1 to 12 carbon atoms, which is optionally substituted with fluorine and in which optionally 1 or 2 non-adjacent --CH 2  -- groups can be replaced by oxygen, --COO--, --OOC--, --CO-- and/or a --CH 2  CH 2  -- group can be replaced by --CH═CH--;   n,p each independently are 0 or 1;   X,Y each independently are hydrogen, halogen cyano, alkyl with 1 to 12 carbon atoms which is optionally substituted with fluorine and in which optionally 1 or 2 non-adjacent --CH 2  -- groups can be replaced by oxygen, --COO--, --OOC--, --CO-- and/or --CH═CH--, with the proviso that A 3  is different from --COO--, when simultaneously n and p each are 0, A 1  is phenyl, R 1  is hydrogen or methoxy and S a  is a single bond;     n' is from 4-100 000. .Iaddend..Iadd.8. A polymer of the formula of formula I ##STR15## wherein M a , M b , M c  are monomer units for homo- or copolymers;   x, y, z are mole fractions of the copolymers, whereby in each case O<x≦1; 0≦y≦1 and 0≦z<1;   S a , S b  are independently of one another, an alkylene chain with 1 to 10 carbon atoms, a cycloalkylene group with 3 to 8 carbon atoms in which optionally one or two methylene groups can be replaced by NH groups, or phenylene which can be substituted with lower alkyl, lower alkoxy, --CN, --NO 2  halogen, carbonate, an ester group, an amide group, an ether group or a combination of said groups;   Z a , Z b  each independently are of formula II-A, ##STR16## II-B, or ##STR17## II-C ##STR18## wherein ring A 1  is 1,4-phenylene, which is unsubstituted or substituted with halogen, cyano and/or nitro, or pyrimidine-2,5-diyl, pyridine-2,5-diyl, 2,5-thiophenediyl 2,5-furanylene, 1,4-naphthylene or 2,6-naphthylene;   ring A 2  is 1,4-phenylene, which is unsubstituted or substituted with halogen, cyano and/or nitro, or pyrimidine-2,5-diyl, pyridine-2,5-diyl, 2,5-thiophenediyl, 2,5-furanylene, trans-1,4-cyclohexylene, trans-1,3-dioxane-2,5-diyl or 1,4-piperidyl;   ring A 4  is 1,4-phenylene, which is unsubstituted or substituted with halogen, cyano and/or nitro;   Z 1  is a single covalent bond, --CH 2  CH 2  --, --COO--, --OCH 2  --, --(CH 2 ) 4  --, --O(CH 2 ) 3  -- or --(CH 2 ) 3  O--;   R 1  is hydrogen, halogen, cyano, nitro, alkyl with 1 to 12 carbon atoms, which is optionally substituted with fluorine and in which optionally 1 or 2 non-adjacent --CH 2  -- groups can be replaced by oxygen or --COO-- and/or a --CH 2  CH 2  -- group can be replaced by --CH═CH--;   n is 0 or 1;   X is hydrogen or alkyl with 1 to 6 carbon atoms which is optionally substituted with halogen;   Y is hydrogen, cyano, --COO-alkyl, alkyl with 1 to 6 carbon atoms, which is optionally substituted with fluorine; and with the proviso that in formula II-A simultaneously n does not signify 0, A 1  does not signify phenyl, R 1  does not signify hydrogen or methoxy, X and Y do not signify hydrogen and S a  or S b  does not signify a single bond;     n' is from 4-100 000; and   m is 0 or 1. .Iaddend.