CA1272342A - Polymer materials having liquid-crystalline phases - Google Patents
Polymer materials having liquid-crystalline phasesInfo
- Publication number
- CA1272342A CA1272342A CA000519143A CA519143A CA1272342A CA 1272342 A CA1272342 A CA 1272342A CA 000519143 A CA000519143 A CA 000519143A CA 519143 A CA519143 A CA 519143A CA 1272342 A CA1272342 A CA 1272342A
- Authority
- CA
- Canada
- Prior art keywords
- groups
- alkyl
- formula
- group
- polymer materials
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
- C09K19/3833—Polymers with mesogenic groups in the side chain
Abstract
Abstract Polymer materials exhibiting liquid-crystalline phases contain laterally bonded mesogenic groups of the formula Ia and/or Ib:
Ia Ib in which A, Ao, R1, R2, Sp, Z, Zo, m and n have the meanings stated in Patent Claim 1.
Processes for the preparation of polymer materials of this type comprise the polymerization and/or grafting of suitable monomers.
The polymer materials according to the invention are used as substrates in the electronics industry for fibre and film technology, for modulating laser beams and for optical data storage.
Ia Ib in which A, Ao, R1, R2, Sp, Z, Zo, m and n have the meanings stated in Patent Claim 1.
Processes for the preparation of polymer materials of this type comprise the polymerization and/or grafting of suitable monomers.
The polymer materials according to the invention are used as substrates in the electronics industry for fibre and film technology, for modulating laser beams and for optical data storage.
Description
Merck Patent Gesellscha~t mit beschrankter Haftung 6100 ~ a r m s t a d t Polymer mater;aLs having liquid-crystalline phases S The invention relates to polymer materials which have liquid-crystalline phases and the noesogenic groups of which ~re bonde~ laterally to the polymer backbone.
A nu~ber of liqu;d-crystalLine side-chain polymers are already known. Thus~ for example, German Of~enlegungs-schr;ft 2,944,591 and European Patent Specification 0,060,335 describe organopolysiloxanes, and German Offenlegungs-schrift 2~831,909 and Springer and Weigelt, Makromol.
Chem. 184 (1983) 14~9, describe polymethacryLates posses-sing mesogenic side groups.
The common feature of these kno~n side-chain poly-mers is that their mesogenic groups are bonded to the polymer backbone, if appropriate via a spacer, at the 4-position in the direction of the longitudinal molecular axis~ and hence analogously to the customary wing groups~
Such polymer materiaLs frequently have nematic phases at temperatures aboYe 100C. In many cases, such materials also exhibit crystalline behaviour, associated with ~he lack of mesomorphic properties.
The object of the present invention was to find polymer materials ~hich have licluid-crystalline phases and which possess the disadvantages described only to a slight extent, if at aLlO
To date~ only comparatively small lateral sub-stituents have besn considered to be compatible with the occurrence of liquid-crystalline properties (cf. Gray in:
The Molecular Physics of Liquid Crystals (editors G.R.
Luckhurst and G.W. Gray), London-New York-San Francisco 1979, page 1). The fact that it has now been found that pclymer materials in which the mesogenic groups are bonded laterally to the polymer backbone possess surprisingly wide mesophase ranges, a birefringence wh;ch can be varied ~ithin ~ide limi~s and a positive as well 3S negative dia-magnetic anisotropy is therefore all the more surprising.
~7~
They may furthermore be readily processed to articles of any shape with anisotropic properties, and have high chemical stability.
The invent;on relates ~o polymer mater;als which have l;qu;d-crystalline phases and the mesogenic groups of ~hich are bonded to the polymer backbone laterally, that is to say not terminally via a ring group or bridging group of t~e mesogenic un;t. Such mesogenic groups corre-spond to the formula Ia and/or Ib Sp Ia Rl ~A- ( Z-A ) ~Z -1 A- Z ~ nWA-R~
Sp Rl~(A-Z) -A-(Z~A)n-R2 Ib ~herein R1 and R2 are alkyl hav;ng 1-15 C atoms, ;n wh;ch furthermore one or t~o non-adjacent CH2 groups can be r~placed with -0-, -C0-, -0-C0-, -C0-9-and/or -CH=CH-, or one of the radicals R1 and R2 may furthermore be H, F, Cl, ar, NCS, N02~ CN or R -A-Z~
R3 is alkyl having 1-15 C atoms, in which further-more one or two non-adjacent CH~ groups can be replaced with -0 , -C0-, -0-C0-, -C0-0- and/or -CH=CH-, or is H, F, Cl, ~r, NCS or CN, Sp ;s a covalent bond or a radical of the formula _Q~_W1_~2_~2_ Q1 and Q2 independently of one another are each a chem;cal bond and/or an alkylene group having 2 to 25 C atoms, in wh;ch furthermore one or more non-adjacent CH2 groups can be replaced with -0-, -S-or -N(C1-C6-alkyl)-, ~1 and w2 independently of one another are each a chemical bond and/or a functional grouping from the group Gonsist;ng of -0 , -S-, -S0-, -S02 , -N(C1-C6-alkyl)-, -C0-, -C0-0~, -0-C0-, -0-C0-0-, -C0-S-, -S-C0-, -C0-NH~C1-C6-alkyl)-~ ~NH(C1-C6-alkyl)-C0~ -3 C0-NH(C1-C6-alkyl)- or -~H~C1~C6-alkyl)-C0-0 and Cl-C~-alkyl, A in each case is a 1,4-cyclohexylene group, in which furthermore one or t~o non-adjacen~ CU2 groups can be replaced with -0- and/or -S-, and/or which can be sub~tituted in the 1-position by C1-C4-alkyl, F, CL, 8r, rF3 or CN, or is a pi~eridine-1,4 diyl or 1~4-bicyclo~2.?.2~octylene group or a 1,4-phenylene group wh;ch is unsubsti-tuted or substituted by one or t~o f and/or Cl atoms and/or CH3 groups and/or CN groups and in which furthermore one or more CH groups can be replaced ~ith N~
A-Sp- is a rad;cal of the formula (1) or (2) Sp ~; .
_ ~ (1) ~ (2) wherein furthermore one or t~o non-adjacent CH2 groups can be replaced ~ith -0- and/or -S-, and/or a -CHz-CH group can be replaced with -N=C- or -CH=C- and/or which can be substituted in the Z0 1-position by C1-C4-alkyl, F, Cl~ ~r, CF3 or CN, or is a radical of the formula ~3) J
~p (3) wherein q is 0 to 2 and wherein furthermore one or more CH groups can be replaced with N, and/or Z5 which can furthermore be substituted by one or two F and/or Cl atoms and/or CH3 groups and/or C~
groups, or is a radical (4), (5) or (6) ~p Sp S~ >--~ ~
~ (4) ~ ~ (5) ~N N- (6) . , '~.
3~
n and m are each 0 to 3, Z in each case is -C0-0-, -0-C0 ~ CH2CH2-, -CHCN-CH2 , ~CH2-CHCN-, -CH=CH-, -OCM2-, -CH20-, -CH~N-, -N=CH-, ~N0=N-, -N=N0- or a single bond, and ~-Sp is -CH2CHSp-, -CSpCN-CH2-, -CHCN-CHSp-, -CSp=CH-~ -CHSp-0- or -CSp-N-, ~it~ the proviso that m ~ n ;s 0 to 3.
AboYe and belo~, R1, R2, R3, A, A~ , n, Sp, Q1, QZ, ~ 2, z and Z have the stclted meanings, unless expressly stated otherw;se.
The compounds of the formula Ia/b accordingly comprise co~pounds having two rings, of the partial for-mulae Iaa to Iba, where;n (Sp-) is a spac~r ~hich Possesses the stated meanings and is bonded to the above r;ng group or bridging group:
R1-Atsp-)-z-A-R2 Iaa R -A (Sp-)-A-R Iab R1-A-Z(Sp-)-A~R2 Iba, csmpounds possess;ng three r;ngs, of the partial formulae lac to Ibg:
R1-A(Sp~)-A-z-A-R2 Iac R1 A A(S ) Z A R2 Iad R1-A-A 7-~~Sp-)-R2 Iae 25 R1-A(Sp-)-Z-A-Z-A-R2 laf R1_A_~_A(Sp-)-Z-A-R2 Iag R3-A-z-A($p_)-z-A-~2 Iah R3-A-Z-A-Z-A~tSp-)-R~ Iai R3-Ao(5p_)-A-~-A-R2 Iaj 30 R3-A-Qo(sp~-z-A-R2 Iak R3_A-A-Z-A(SP-)-R2 Ial ~1_A~(sp_~-A-A-R2 Iam R1-A-A(Sp-)-A-R~ I an R1-A-A-Z(Sp-)-A-R2 Ibc 35 R1-A-Z~Sp-)-A-z-R2 Ibd ~3_A_Z(sp-)-A-z-A-~2 Ibe R3_A_z_A~z(Sp-)-A-R2 Ibf R3_A-A-Z(Sp-)-A-R2 Ibg, compounds possessing four rings, of the partial ^3~
formuLae lao to Ib R3_Ao(sp-)-z-A-z-A-z-A-R3 lao R3-A-Z-Ao(Sp-)-Z~A-Z-A R3 Iap R3-h(Sp-)-A-Z-A-A-R3 laq S R3-A A(Sp-)-z-A_A_R3 Iar R3-Ao(sp-)-z-A-A-A-R3 Ia~
R3-A-Z-Ao(Sp-)-A-A-R3 Iat R3-A-Z-A-A~(sp-)-A-R3 lau R3-A-z-A-A Ao~Sp-~-R3 Iav 10 R1-A(Sp-)-A-z-A-5_A_R3 Iaw R1-A-Ao(Sp-)-Z-A-Z-A-R3 Iax R1_A-A-Z-Ao(Sp-)-Z-A-K3 Iay ~1_A_A_z_A_z_A(5p~)~R3 Iaz ~3_Aotsp-)-z-h-A-z-A-R2 Iaaa 15 R3-A-Z-Ao(sp-)-A-z-A-R2 Iaab R3-A-Z-A-Ao(Sp-)-Z-A-R2 Iaac R3_A-Z-A-A-Z-A(Sp-)-R2 Iaad R1_Ao(sp-)-A-A-A-R3 Iaae R -A-A (Sp-)-A-A-R Iaaf 20 R1-A-A-Ao(sp-)-A-~3 Iaag R1-A-A-A-Ao(Sp-)-R3 Iaah R1 Ao(sp-)-A-A-z-A-R3 Iaai R1-A-A(sp-)-A-z-A-R3 Iaaj R1-A-A-Ao~sp-)-~-A-k3 Iaak Z5 R1-A-A-A-Z-Ao(Sp-)-R3 Iaal R1_Ao~sp-)-A-2-A-A-R3 I aam R1-A-Ao(sp-)-z-A-A-R3 Iaan R 1 _ A-A - ~ - A ( S p- ) - A-R3 Iaao R1_A_A_z_A_A~(sp-)-R3 Iaap 30 R3-Ao(Sp-)-A-A-Z-A-R2 Iaaq R3-A-Ao(sp-)-~-z-A-R2 Iaar R3-A-A-Ao~sp-)-z-A-R2 Iaas R3_A-A-A-Z-A(Sp-)-R2 Iaat R3-A-zo(sp-)-A-z-A-z-A-R3 Ibh 3 5 R 3 - A - X - A ~Z(Sp-) A-Z- A - R 3 I b i R3_A-A-z(Sp-) A-A-R3 Ibj R3-A-z0(sp-~-A-A-A-R3 Ibk R -A-A-Z (Sp-)-A-Z-A-R Ibl R1_A-A-Z-A-zo(sp-)-A~R3 Ibm 7 ~
R3-A-Z~(Sp-)-A-A-Z-A-R2 Ibn R3 A-z-A-A-ZSSp-3-~-R2 Ibo R1_A_A_A_zO~Sp_~_A_R3 Ibp R1-A-A-~(~p-)-A-A-~3 Ib~
5 R3-A~A-A-Zo~sp~) A R3 Ibr, and compounds possessing five rings, of the part;al for-mulae Iaau to Ib~
R3-AotSp-)-Z-A-A-Z-A-Z-A-R3 Iaau R3-A-Z-Ao(sp-)-A-Z-A-Z-A R3 Iaav 10 R -A-Z-A-A (sp~ -A-Z-A-R3 Iaa~
R3-A-Z-A-A-Z Ao(Sp-)-Z-A-R3 Iaax R3-A-Z-A-A-Z-A-Z-A~tSp-)~R3 Iaay R3-A(Sp-)-A-A-h-A-R3 Ia~z R3-A~Ao(sp-)-A-A-~-R3 Iaba 15 R3-A-A-Ao(Sp-)-A-A-R3 Iabb R3-~o(sp-)-A-A-z-A-A-R3 Iabc R3 A Ao(sp-)-A-z-A-A-R3 Iabd R -A-A-A (Sp-)-Z-A-A-R Iabe R3_~_A_A-Z-A(Sp-) A-R3 Iabf
A nu~ber of liqu;d-crystalLine side-chain polymers are already known. Thus~ for example, German Of~enlegungs-schr;ft 2,944,591 and European Patent Specification 0,060,335 describe organopolysiloxanes, and German Offenlegungs-schrift 2~831,909 and Springer and Weigelt, Makromol.
Chem. 184 (1983) 14~9, describe polymethacryLates posses-sing mesogenic side groups.
The common feature of these kno~n side-chain poly-mers is that their mesogenic groups are bonded to the polymer backbone, if appropriate via a spacer, at the 4-position in the direction of the longitudinal molecular axis~ and hence analogously to the customary wing groups~
Such polymer materiaLs frequently have nematic phases at temperatures aboYe 100C. In many cases, such materials also exhibit crystalline behaviour, associated with ~he lack of mesomorphic properties.
The object of the present invention was to find polymer materials ~hich have licluid-crystalline phases and which possess the disadvantages described only to a slight extent, if at aLlO
To date~ only comparatively small lateral sub-stituents have besn considered to be compatible with the occurrence of liquid-crystalline properties (cf. Gray in:
The Molecular Physics of Liquid Crystals (editors G.R.
Luckhurst and G.W. Gray), London-New York-San Francisco 1979, page 1). The fact that it has now been found that pclymer materials in which the mesogenic groups are bonded laterally to the polymer backbone possess surprisingly wide mesophase ranges, a birefringence wh;ch can be varied ~ithin ~ide limi~s and a positive as well 3S negative dia-magnetic anisotropy is therefore all the more surprising.
~7~
They may furthermore be readily processed to articles of any shape with anisotropic properties, and have high chemical stability.
The invent;on relates ~o polymer mater;als which have l;qu;d-crystalline phases and the mesogenic groups of ~hich are bonded to the polymer backbone laterally, that is to say not terminally via a ring group or bridging group of t~e mesogenic un;t. Such mesogenic groups corre-spond to the formula Ia and/or Ib Sp Ia Rl ~A- ( Z-A ) ~Z -1 A- Z ~ nWA-R~
Sp Rl~(A-Z) -A-(Z~A)n-R2 Ib ~herein R1 and R2 are alkyl hav;ng 1-15 C atoms, ;n wh;ch furthermore one or t~o non-adjacent CH2 groups can be r~placed with -0-, -C0-, -0-C0-, -C0-9-and/or -CH=CH-, or one of the radicals R1 and R2 may furthermore be H, F, Cl, ar, NCS, N02~ CN or R -A-Z~
R3 is alkyl having 1-15 C atoms, in which further-more one or two non-adjacent CH~ groups can be replaced with -0 , -C0-, -0-C0-, -C0-0- and/or -CH=CH-, or is H, F, Cl, ~r, NCS or CN, Sp ;s a covalent bond or a radical of the formula _Q~_W1_~2_~2_ Q1 and Q2 independently of one another are each a chem;cal bond and/or an alkylene group having 2 to 25 C atoms, in wh;ch furthermore one or more non-adjacent CH2 groups can be replaced with -0-, -S-or -N(C1-C6-alkyl)-, ~1 and w2 independently of one another are each a chemical bond and/or a functional grouping from the group Gonsist;ng of -0 , -S-, -S0-, -S02 , -N(C1-C6-alkyl)-, -C0-, -C0-0~, -0-C0-, -0-C0-0-, -C0-S-, -S-C0-, -C0-NH~C1-C6-alkyl)-~ ~NH(C1-C6-alkyl)-C0~ -3 C0-NH(C1-C6-alkyl)- or -~H~C1~C6-alkyl)-C0-0 and Cl-C~-alkyl, A in each case is a 1,4-cyclohexylene group, in which furthermore one or t~o non-adjacen~ CU2 groups can be replaced with -0- and/or -S-, and/or which can be sub~tituted in the 1-position by C1-C4-alkyl, F, CL, 8r, rF3 or CN, or is a pi~eridine-1,4 diyl or 1~4-bicyclo~2.?.2~octylene group or a 1,4-phenylene group wh;ch is unsubsti-tuted or substituted by one or t~o f and/or Cl atoms and/or CH3 groups and/or CN groups and in which furthermore one or more CH groups can be replaced ~ith N~
A-Sp- is a rad;cal of the formula (1) or (2) Sp ~; .
_ ~ (1) ~ (2) wherein furthermore one or t~o non-adjacent CH2 groups can be replaced ~ith -0- and/or -S-, and/or a -CHz-CH group can be replaced with -N=C- or -CH=C- and/or which can be substituted in the Z0 1-position by C1-C4-alkyl, F, Cl~ ~r, CF3 or CN, or is a radical of the formula ~3) J
~p (3) wherein q is 0 to 2 and wherein furthermore one or more CH groups can be replaced with N, and/or Z5 which can furthermore be substituted by one or two F and/or Cl atoms and/or CH3 groups and/or C~
groups, or is a radical (4), (5) or (6) ~p Sp S~ >--~ ~
~ (4) ~ ~ (5) ~N N- (6) . , '~.
3~
n and m are each 0 to 3, Z in each case is -C0-0-, -0-C0 ~ CH2CH2-, -CHCN-CH2 , ~CH2-CHCN-, -CH=CH-, -OCM2-, -CH20-, -CH~N-, -N=CH-, ~N0=N-, -N=N0- or a single bond, and ~-Sp is -CH2CHSp-, -CSpCN-CH2-, -CHCN-CHSp-, -CSp=CH-~ -CHSp-0- or -CSp-N-, ~it~ the proviso that m ~ n ;s 0 to 3.
AboYe and belo~, R1, R2, R3, A, A~ , n, Sp, Q1, QZ, ~ 2, z and Z have the stclted meanings, unless expressly stated otherw;se.
The compounds of the formula Ia/b accordingly comprise co~pounds having two rings, of the partial for-mulae Iaa to Iba, where;n (Sp-) is a spac~r ~hich Possesses the stated meanings and is bonded to the above r;ng group or bridging group:
R1-Atsp-)-z-A-R2 Iaa R -A (Sp-)-A-R Iab R1-A-Z(Sp-)-A~R2 Iba, csmpounds possess;ng three r;ngs, of the partial formulae lac to Ibg:
R1-A(Sp~)-A-z-A-R2 Iac R1 A A(S ) Z A R2 Iad R1-A-A 7-~~Sp-)-R2 Iae 25 R1-A(Sp-)-Z-A-Z-A-R2 laf R1_A_~_A(Sp-)-Z-A-R2 Iag R3-A-z-A($p_)-z-A-~2 Iah R3-A-Z-A-Z-A~tSp-)-R~ Iai R3-Ao(5p_)-A-~-A-R2 Iaj 30 R3-A-Qo(sp~-z-A-R2 Iak R3_A-A-Z-A(SP-)-R2 Ial ~1_A~(sp_~-A-A-R2 Iam R1-A-A(Sp-)-A-R~ I an R1-A-A-Z(Sp-)-A-R2 Ibc 35 R1-A-Z~Sp-)-A-z-R2 Ibd ~3_A_Z(sp-)-A-z-A-~2 Ibe R3_A_z_A~z(Sp-)-A-R2 Ibf R3_A-A-Z(Sp-)-A-R2 Ibg, compounds possessing four rings, of the partial ^3~
formuLae lao to Ib R3_Ao(sp-)-z-A-z-A-z-A-R3 lao R3-A-Z-Ao(Sp-)-Z~A-Z-A R3 Iap R3-h(Sp-)-A-Z-A-A-R3 laq S R3-A A(Sp-)-z-A_A_R3 Iar R3-Ao(sp-)-z-A-A-A-R3 Ia~
R3-A-Z-Ao(Sp-)-A-A-R3 Iat R3-A-Z-A-A~(sp-)-A-R3 lau R3-A-z-A-A Ao~Sp-~-R3 Iav 10 R1-A(Sp-)-A-z-A-5_A_R3 Iaw R1-A-Ao(Sp-)-Z-A-Z-A-R3 Iax R1_A-A-Z-Ao(Sp-)-Z-A-K3 Iay ~1_A_A_z_A_z_A(5p~)~R3 Iaz ~3_Aotsp-)-z-h-A-z-A-R2 Iaaa 15 R3-A-Z-Ao(sp-)-A-z-A-R2 Iaab R3-A-Z-A-Ao(Sp-)-Z-A-R2 Iaac R3_A-Z-A-A-Z-A(Sp-)-R2 Iaad R1_Ao(sp-)-A-A-A-R3 Iaae R -A-A (Sp-)-A-A-R Iaaf 20 R1-A-A-Ao(sp-)-A-~3 Iaag R1-A-A-A-Ao(Sp-)-R3 Iaah R1 Ao(sp-)-A-A-z-A-R3 Iaai R1-A-A(sp-)-A-z-A-R3 Iaaj R1-A-A-Ao~sp-)-~-A-k3 Iaak Z5 R1-A-A-A-Z-Ao(Sp-)-R3 Iaal R1_Ao~sp-)-A-2-A-A-R3 I aam R1-A-Ao(sp-)-z-A-A-R3 Iaan R 1 _ A-A - ~ - A ( S p- ) - A-R3 Iaao R1_A_A_z_A_A~(sp-)-R3 Iaap 30 R3-Ao(Sp-)-A-A-Z-A-R2 Iaaq R3-A-Ao(sp-)-~-z-A-R2 Iaar R3-A-A-Ao~sp-)-z-A-R2 Iaas R3_A-A-A-Z-A(Sp-)-R2 Iaat R3-A-zo(sp-)-A-z-A-z-A-R3 Ibh 3 5 R 3 - A - X - A ~Z(Sp-) A-Z- A - R 3 I b i R3_A-A-z(Sp-) A-A-R3 Ibj R3-A-z0(sp-~-A-A-A-R3 Ibk R -A-A-Z (Sp-)-A-Z-A-R Ibl R1_A-A-Z-A-zo(sp-)-A~R3 Ibm 7 ~
R3-A-Z~(Sp-)-A-A-Z-A-R2 Ibn R3 A-z-A-A-ZSSp-3-~-R2 Ibo R1_A_A_A_zO~Sp_~_A_R3 Ibp R1-A-A-~(~p-)-A-A-~3 Ib~
5 R3-A~A-A-Zo~sp~) A R3 Ibr, and compounds possessing five rings, of the part;al for-mulae Iaau to Ib~
R3-AotSp-)-Z-A-A-Z-A-Z-A-R3 Iaau R3-A-Z-Ao(sp-)-A-Z-A-Z-A R3 Iaav 10 R -A-Z-A-A (sp~ -A-Z-A-R3 Iaa~
R3-A-Z-A-A-Z Ao(Sp-)-Z-A-R3 Iaax R3-A-Z-A-A-Z-A-Z-A~tSp-)~R3 Iaay R3-A(Sp-)-A-A-h-A-R3 Ia~z R3-A~Ao(sp-)-A-A-~-R3 Iaba 15 R3-A-A-Ao(Sp-)-A-A-R3 Iabb R3-~o(sp-)-A-A-z-A-A-R3 Iabc R3 A Ao(sp-)-A-z-A-A-R3 Iabd R -A-A-A (Sp-)-Z-A-A-R Iabe R3_~_A_A-Z-A(Sp-) A-R3 Iabf
2~ R3-A-A-A-Z-A-Ao(SP-)-R3 Iabg R3-A-Zo(Sp-)-A-A-Z-A~Z-A-R3 Ibs R3-A-Z-A~A-Zo(Sp-)-A-Z-A-R3 Ibt R3-A-Z-A-A-Z-A-~otSp-)-A-R3 Ibu R3-A-A-A-~o(Sp-)-A-A-R3 Ibv.
In the compounds of the formulae above and belo~, R1, R~ and R3 are preferably alkyl, but ~ay also be alkoxy.
Other preferred compounds of the for~ulae above and below ar~ those ;n which one of ~he radicals R1, R2 and R3 is CN, F or SCN.
A and A independently of one another are each preferably 1~4-cyclohexyl~ne, 1,4-phenylene, 1,3-di~xan-2,5-diyl or pyr;din~-2,5-diyl.
Sp is preferably a radical -Q~ a2-~l2- Q1 and Q independently of one another aré each preferably alkylene having 2 to 15 C ato~s. W1 and ~Z independently of one another are ~ach pref~rably -0-, -S-, -0-C0~
-CO-0- or -CO-NH-~ n and 0 independently of one another are each 0 or 1, and in par~icular n ~ ~ is 0 to 2.
~L~7~-3~ 3 The radicals Z independently of one another are each preferably single bonds and are also preferably -CO-O-, O-CO- or -CH2CH2- groups. Z-Sp is preferably CH~-CHSp-, -CSp=CH- or CHSp-O-.
R , R2, R3, A, A, Sp Q1 Q2 w1 w2 ~ o and n ~ay be identical; however, they are preferably in-dependent of one another and d;fferent.
~re R1, R2 and/or R3 are alkyl radicaLs and/or alko~y radicals, they may be straight-chain or branched.
Preferably, they are straight-chain~ have 2, 3, 4, 5, 6 or 7 C atoms and are accordingly preferably ethyl, propyl, butyl, pentyl, hexyl, heptyl, ethoxy, propo~y, butoxy, pentyloxy, hexylo~y or heptyloxy, or methyL, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, octyloxy, nonyloxy, decyloxy, undecyloxy, do-decyloxy, ~ridecyloxy or tetradecyloxy.
Oxaalkyl is preferably straight-chain 2-oxapropyl (= methoxymethyl), 2- t= ethoxymethyl) or 3-oxabutyl (= 2-methoxyethyl), 2-, 3- or 4-oxapentyl, 2-, 3-, 4- or S-oxa-hexyl, 2-, 3-, 4-, 5- or 6-oxaheptyl, 2-, 3-, 4-, S-, 6-or 7-oxaoctyl, 2-, 3-, 4-, S-, 6-~ 7- or 8-oxanonyl or 2-, 3 , 4-, 5-, 6-, 7-, ~- or 9 oxadecyl.
Where R1, R2 and/or R3 are alkyl radicals in which a CH2 group is replaced with -CH=CH-, ~hese radi-cals can be straight-chain or branched. They are pref-erably straight-chain and have 2 to 10 C atoms. Accord-ingly, they are, in particular, vinyl, prop-1-enyl, prop-2-enyl, but-1-enyl, but-2-enyl, but-3-enyl, pent-1-enyl, pen~-2-enyl, pent-3-enyl, pent-4-enyl, hex-1-enyl, hex-2-enyl, hex-3-enyl, hex-4-enyl, hex-5-enyl, hept-1-enyl, hept-Z-enyl, hept-3-enyl, hept-4-enyl, hept-5-enyl, hept-6-enyl, oct 1-enyl, oct-2-enyl, oct 3-enyl, oct-4-enyl, oct-S-enyl, oct-6-enyl, oct-7-enyl, non-1-enyl, non-2-enyl~ non-3-enyl, non-4-enyl, non-5-enyl, non-6-enyl, non-7-enyl, non-8-enyl, dec-1-enyl, dec-2-enyl, dec-3-enyl, dec-4-enyl, dec-S-enyl, dec-6-enyl, dec-7-enyl, dec-8-enyl or dec-9-enyl~
~ ecause they possess better solubility in the customary liquid-crystalline base ~aterials, compounds of the formulae I having branched wing groups R1, R2 and/or R3 may sometimes be important; however, they are particularly important as chiral dopants when they are optically active~ Smectic compounds of this type are suitable components for ferroelectr;c materials, for chi-ral t;lted smectic phases and as components ~f nematic liquid-crystalline phasas, in particular for avoiding reverse t~ist~
Branched groùps of this type contain, as a rule~
no ~nore than one cha;n branch. Preferred branched radicals R1, R2 and/or R3 are isopropyl, 7-butyl (= 1-methyl-propyl), ;sobutyl (= 2-methylpropyl), 2-methylbutyl, iso-penty( 5= 3-methylbutyl~, 2-~ethylpentyl, 3-methylpentyl, 2-ethylhe~yl, Z-propylpentyl, isopropo)ty, 2-methylpr 2-methylbutoxy, 3-methylbutoxy, 3-methylpentyloxy, 3-methylpentyloxy, 2-ethylhexyloxy, 1~methylhexyloxy and 1-methylheptyloxy.
The for1ulae Ia and Ib embrace both the racemates of these ~ompounds and the optical antipodes and their ZO mixtures.
Preferred co~pounds among those of the for~ula Ia/b and Iaa to Ibv are those ;n ~hich at least one of the radicals present has th~ stated pre~erred mean;ngs.
Compounds corresponding to the mesogenis radicals Z5 of the formula Ia or Ib and in which the valence through which the spacer Sp is bonded is saturated with hydrogen or a radical -Q1-H or ~ H are known liquid crystals and are described in, for exa~ple~ German Patent Applications P 33 15 295, P 33 46 175, P 34 01 320, P 34 01 321, 3G P 24 04 116 and P 34 11 571; in German Offenlegungs-schriften 2,167,252, 2,2S7,588, 2,429,093, 2,547,737, 2~b41,724, Z,944,905, 2,951,099, 3,140,868 and 3,228,350, and in ~uropean Published Specification~ 0,014,885~
OyO84,194, 0,104,011, 0~111,695, 0,122,3a9 and 0,126~883.
M~sogenic groups which are suitable for la~eral bonding to poly~ers preferably possess the basic struc~
tures a to an, in which Phe is 1,4-phenylene, Cyc is trans-1,4-cyclohexylene, Dio is 2,5-dioxan-1,3-diyl and F'ym ;s pyri0;d;ne-2,5-diyl, and R1 and R2 have the meanings given in formula Ia/b:
a R1 Phe~he-R~
b R1-Phe Cyc R
c R1 -Cyc -Cyc: ~R
d Rl~Phe-Phe-Ph~-R~
e Rl~cyciPhe Phe~R2 f Rl-C~c-Phe Cy~
g RL-Cyc~Phe-Phe-Cyc~R2 h Rl PheiC~2C~2-Phe R2 i R -Cyc-CH2C~2-Cyc-R2 10 j R~-Phe-Cyc~OE12C~ Phe-R2 k Rl-Cyc~C~2C~2~Phe Phe-~2 1 Rl Phe CH2Ca2 Ph~ P 2 m R -Cyc C~(CN)-C~-Cyc-R
n Rl-Ph~-COO-Phe-R
lS o Rl-Cyc-COO-Phe-R~
p Rl-Cyc-COO-Phe-Phe~R2 ~ Rl-Cyc-Phe-COO-Phe R~
r Rl~Cyc-Phe OCO-Cyc~R2 . s Rl Phe-Cyc~COO Phe R~
2 O t Rl ~-Phe-Cyc~OCO-Phe-R2 u Rl~Phe-Cyc-COO-Cyc-~R2 v Rl~Phe-Phe-COO-Phe-Phe R2 w Rl-Cyc~COO-Phe Phe~R2 ~c Rl-Phe~Phe-COO-Phe R2 y Rl-Cyc-COO-Phe-COO Phe~R2 z Rl-Phe-~20 Phe-R2 aa Rl-Phe-Phe C~20-PheR2 ab Rl~Cyc~Phe-C~O-Phe-R2 ac Rl~Phe~Cyc-C~20~Phe~R2 ad Rl-Di~-Phe~-R~
ae ~l-Dio-Cyc_R2 af Rl Cyc-Dio-Phe-R2 ag R ~Dio~Cyc-Phe R
ah Rl~D.io-Phe-COO-Phe-R2 ai ~1 Dio~Cyc-COO-Phe-R2 ~:7~3~
a j Rl-Pym ~ Phe E~.~
ak Rl-Cyc-Pym Pne-R2 al Rl-Pym~Phe-COO~Phe~R2 am Rl-P~n~-Ph~C~20-Phe-R;~
an Rl-~Pym-Phe~OCO~Phe~R2 The spacer Sp can be bonded either to one of the ring grou~s Phe, Cyc, Dio or Pym or to a bridging group -CH20 , -CH2CH~- or -CH(CN)-CH2-.
The invention furthermore relates to a process for the preparation of polymer materials according to Clai~s 1 and 2.
Thus, compounds of the formula II
Y-M II
~herein M is a mesogenic group of the formula ~a/b and Y
is a functional group capable of poly~erization or of being grafted, can be polymerized, provided that Y is an alkyl-ene group ~hich has 2 eo s carbon atoms and is present in the ~- or (~ position. Y can be bonded to the spacer Sp directlY t-~1-W1-Q2-W2-Y) or via a functional group _Q1_w1_Q1_w2_y).
Particularly prefPrred groups are -O-, -CO-O-, -CO-NH- and -S-, in part;cular -O- and -CO-O-.
The poly~er materials according to the invention 2û can be prepared from compounds of the formula II, wherein r iS an alkylene group which has 2 to 5 C atoms and is pre-sentin the ~- or (~-1)-position also by copolymerization with other olefinically unsaturated monomers. Examples of suitable comonomers are C1-C20-alkyl esters of acrylic and/or methacrylic acid~ styrene, ~-methylstyrene, 4-~ethylstyrene, acrylonitrile, methacrylonitrile and methylene~alonates.
The polymerization is carried out in a manner kno~n per se, by reaction of radiant energy, heat energy electrical energy and by the reac~ion of ~ree radical or ionic catalystsp as described ;n, for example, Odian~ -Princ;ples of Polymerization, McGraw-Hill~ New York~ 1970.
.
In the compounds of the formulae above and belo~, R1, R~ and R3 are preferably alkyl, but ~ay also be alkoxy.
Other preferred compounds of the for~ulae above and below ar~ those ;n which one of ~he radicals R1, R2 and R3 is CN, F or SCN.
A and A independently of one another are each preferably 1~4-cyclohexyl~ne, 1,4-phenylene, 1,3-di~xan-2,5-diyl or pyr;din~-2,5-diyl.
Sp is preferably a radical -Q~ a2-~l2- Q1 and Q independently of one another aré each preferably alkylene having 2 to 15 C ato~s. W1 and ~Z independently of one another are ~ach pref~rably -0-, -S-, -0-C0~
-CO-0- or -CO-NH-~ n and 0 independently of one another are each 0 or 1, and in par~icular n ~ ~ is 0 to 2.
~L~7~-3~ 3 The radicals Z independently of one another are each preferably single bonds and are also preferably -CO-O-, O-CO- or -CH2CH2- groups. Z-Sp is preferably CH~-CHSp-, -CSp=CH- or CHSp-O-.
R , R2, R3, A, A, Sp Q1 Q2 w1 w2 ~ o and n ~ay be identical; however, they are preferably in-dependent of one another and d;fferent.
~re R1, R2 and/or R3 are alkyl radicaLs and/or alko~y radicals, they may be straight-chain or branched.
Preferably, they are straight-chain~ have 2, 3, 4, 5, 6 or 7 C atoms and are accordingly preferably ethyl, propyl, butyl, pentyl, hexyl, heptyl, ethoxy, propo~y, butoxy, pentyloxy, hexylo~y or heptyloxy, or methyL, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, octyloxy, nonyloxy, decyloxy, undecyloxy, do-decyloxy, ~ridecyloxy or tetradecyloxy.
Oxaalkyl is preferably straight-chain 2-oxapropyl (= methoxymethyl), 2- t= ethoxymethyl) or 3-oxabutyl (= 2-methoxyethyl), 2-, 3- or 4-oxapentyl, 2-, 3-, 4- or S-oxa-hexyl, 2-, 3-, 4-, 5- or 6-oxaheptyl, 2-, 3-, 4-, S-, 6-or 7-oxaoctyl, 2-, 3-, 4-, S-, 6-~ 7- or 8-oxanonyl or 2-, 3 , 4-, 5-, 6-, 7-, ~- or 9 oxadecyl.
Where R1, R2 and/or R3 are alkyl radicals in which a CH2 group is replaced with -CH=CH-, ~hese radi-cals can be straight-chain or branched. They are pref-erably straight-chain and have 2 to 10 C atoms. Accord-ingly, they are, in particular, vinyl, prop-1-enyl, prop-2-enyl, but-1-enyl, but-2-enyl, but-3-enyl, pent-1-enyl, pen~-2-enyl, pent-3-enyl, pent-4-enyl, hex-1-enyl, hex-2-enyl, hex-3-enyl, hex-4-enyl, hex-5-enyl, hept-1-enyl, hept-Z-enyl, hept-3-enyl, hept-4-enyl, hept-5-enyl, hept-6-enyl, oct 1-enyl, oct-2-enyl, oct 3-enyl, oct-4-enyl, oct-S-enyl, oct-6-enyl, oct-7-enyl, non-1-enyl, non-2-enyl~ non-3-enyl, non-4-enyl, non-5-enyl, non-6-enyl, non-7-enyl, non-8-enyl, dec-1-enyl, dec-2-enyl, dec-3-enyl, dec-4-enyl, dec-S-enyl, dec-6-enyl, dec-7-enyl, dec-8-enyl or dec-9-enyl~
~ ecause they possess better solubility in the customary liquid-crystalline base ~aterials, compounds of the formulae I having branched wing groups R1, R2 and/or R3 may sometimes be important; however, they are particularly important as chiral dopants when they are optically active~ Smectic compounds of this type are suitable components for ferroelectr;c materials, for chi-ral t;lted smectic phases and as components ~f nematic liquid-crystalline phasas, in particular for avoiding reverse t~ist~
Branched groùps of this type contain, as a rule~
no ~nore than one cha;n branch. Preferred branched radicals R1, R2 and/or R3 are isopropyl, 7-butyl (= 1-methyl-propyl), ;sobutyl (= 2-methylpropyl), 2-methylbutyl, iso-penty( 5= 3-methylbutyl~, 2-~ethylpentyl, 3-methylpentyl, 2-ethylhe~yl, Z-propylpentyl, isopropo)ty, 2-methylpr 2-methylbutoxy, 3-methylbutoxy, 3-methylpentyloxy, 3-methylpentyloxy, 2-ethylhexyloxy, 1~methylhexyloxy and 1-methylheptyloxy.
The for1ulae Ia and Ib embrace both the racemates of these ~ompounds and the optical antipodes and their ZO mixtures.
Preferred co~pounds among those of the for~ula Ia/b and Iaa to Ibv are those ;n ~hich at least one of the radicals present has th~ stated pre~erred mean;ngs.
Compounds corresponding to the mesogenis radicals Z5 of the formula Ia or Ib and in which the valence through which the spacer Sp is bonded is saturated with hydrogen or a radical -Q1-H or ~ H are known liquid crystals and are described in, for exa~ple~ German Patent Applications P 33 15 295, P 33 46 175, P 34 01 320, P 34 01 321, 3G P 24 04 116 and P 34 11 571; in German Offenlegungs-schriften 2,167,252, 2,2S7,588, 2,429,093, 2,547,737, 2~b41,724, Z,944,905, 2,951,099, 3,140,868 and 3,228,350, and in ~uropean Published Specification~ 0,014,885~
OyO84,194, 0,104,011, 0~111,695, 0,122,3a9 and 0,126~883.
M~sogenic groups which are suitable for la~eral bonding to poly~ers preferably possess the basic struc~
tures a to an, in which Phe is 1,4-phenylene, Cyc is trans-1,4-cyclohexylene, Dio is 2,5-dioxan-1,3-diyl and F'ym ;s pyri0;d;ne-2,5-diyl, and R1 and R2 have the meanings given in formula Ia/b:
a R1 Phe~he-R~
b R1-Phe Cyc R
c R1 -Cyc -Cyc: ~R
d Rl~Phe-Phe-Ph~-R~
e Rl~cyciPhe Phe~R2 f Rl-C~c-Phe Cy~
g RL-Cyc~Phe-Phe-Cyc~R2 h Rl PheiC~2C~2-Phe R2 i R -Cyc-CH2C~2-Cyc-R2 10 j R~-Phe-Cyc~OE12C~ Phe-R2 k Rl-Cyc~C~2C~2~Phe Phe-~2 1 Rl Phe CH2Ca2 Ph~ P 2 m R -Cyc C~(CN)-C~-Cyc-R
n Rl-Ph~-COO-Phe-R
lS o Rl-Cyc-COO-Phe-R~
p Rl-Cyc-COO-Phe-Phe~R2 ~ Rl-Cyc-Phe-COO-Phe R~
r Rl~Cyc-Phe OCO-Cyc~R2 . s Rl Phe-Cyc~COO Phe R~
2 O t Rl ~-Phe-Cyc~OCO-Phe-R2 u Rl~Phe-Cyc-COO-Cyc-~R2 v Rl~Phe-Phe-COO-Phe-Phe R2 w Rl-Cyc~COO-Phe Phe~R2 ~c Rl-Phe~Phe-COO-Phe R2 y Rl-Cyc-COO-Phe-COO Phe~R2 z Rl-Phe-~20 Phe-R2 aa Rl-Phe-Phe C~20-PheR2 ab Rl~Cyc~Phe-C~O-Phe-R2 ac Rl~Phe~Cyc-C~20~Phe~R2 ad Rl-Di~-Phe~-R~
ae ~l-Dio-Cyc_R2 af Rl Cyc-Dio-Phe-R2 ag R ~Dio~Cyc-Phe R
ah Rl~D.io-Phe-COO-Phe-R2 ai ~1 Dio~Cyc-COO-Phe-R2 ~:7~3~
a j Rl-Pym ~ Phe E~.~
ak Rl-Cyc-Pym Pne-R2 al Rl-Pym~Phe-COO~Phe~R2 am Rl-P~n~-Ph~C~20-Phe-R;~
an Rl-~Pym-Phe~OCO~Phe~R2 The spacer Sp can be bonded either to one of the ring grou~s Phe, Cyc, Dio or Pym or to a bridging group -CH20 , -CH2CH~- or -CH(CN)-CH2-.
The invention furthermore relates to a process for the preparation of polymer materials according to Clai~s 1 and 2.
Thus, compounds of the formula II
Y-M II
~herein M is a mesogenic group of the formula ~a/b and Y
is a functional group capable of poly~erization or of being grafted, can be polymerized, provided that Y is an alkyl-ene group ~hich has 2 eo s carbon atoms and is present in the ~- or (~ position. Y can be bonded to the spacer Sp directlY t-~1-W1-Q2-W2-Y) or via a functional group _Q1_w1_Q1_w2_y).
Particularly prefPrred groups are -O-, -CO-O-, -CO-NH- and -S-, in part;cular -O- and -CO-O-.
The poly~er materials according to the invention 2û can be prepared from compounds of the formula II, wherein r iS an alkylene group which has 2 to 5 C atoms and is pre-sentin the ~- or (~-1)-position also by copolymerization with other olefinically unsaturated monomers. Examples of suitable comonomers are C1-C20-alkyl esters of acrylic and/or methacrylic acid~ styrene, ~-methylstyrene, 4-~ethylstyrene, acrylonitrile, methacrylonitrile and methylene~alonates.
The polymerization is carried out in a manner kno~n per se, by reaction of radiant energy, heat energy electrical energy and by the reac~ion of ~ree radical or ionic catalystsp as described ;n, for example, Odian~ -Princ;ples of Polymerization, McGraw-Hill~ New York~ 1970.
.
3~
Suitable sources of radiant energy are UV radiation, laser beams, X-ray beams and radioactive radiationu Electrical energy can b~ generated, for example, by el~ctrolysis pro cesses. E~amples of ~he free radic3l catalysts are potas-S sium persulphate, diben~oyl peroxide, azobisisobutyro-nitriLe, di-tert-butyl peroxide and cyclohexanone peroxide.
Ion;c catalysts are organic alkali metal compounds, such as phenyll~ithiu0 anJ naphthalenesodium, and Lewis acids, such as ~F3, AlCl3, SnCl4 and TiCl4, or metal complexes in the form of aluminium or titanium compounds. The monomers can be polymerized in solution, suspen~ion or emulsion or as suchc ~ here Y is a hydroxyl, amino, mercapto, epoxide or carboxyl group or one of their reactive derivatives, the compounds of the formula II can be grafted onto a polymeric backbone~ Here~ Y is particularly pre~erably OH, NH2, coaH or a reactive derivative, in particular OH
or a reactive derivative of the carbaxyl group. This grafting reaction can be carried out by methods ~hich are known per se~ such as, for example, esterification~ amid-ationf transesterification~ transamidation, acstalization or etherification, ~h;ch are described in the literature Cfor example, in standard works such as Houben-~eyl, Methoden der Organischen Chemie (Methods of Organic Chemistry), ~eorg~Thieme-YerLag, Stuttgart, or C.M. Paleos et al~, J. Polym. Sci~ Polym. Chem. 19 (1981~ 1427].
A preferred grafting reaction is the reaction of monomers carrying mesogenic groups o~ the formula I a/b with organopolysiloxanes. For this purpose, linear or cyclic organohydropolysiloxanes are react~d, as described in~ for example, European Patent Specification 0,ObO,335, with ethylenically unsaturated, mesogenic monomers of the ~ormula II (Y is an alkylene group which has 2 to 5 C atoms and is present in ~he ~- or (~ position), in about equi-molar amounts, based on the amount of siloxane-hydrogen, in the presence of a catalyst which promotes the addition of silane hydrogen at alipha~ic multiple bonds.
Sui~able polymeric backbones are in principle all polymers the chains of which possess a certain degree 1~ 7~
of flexibility. These may be linear, branched or cyclic polymer chainsO The degree of polymerization is usually at least 10, preferably 20-100. ~owever, oligomers, in particular cyclic oligomers, having 3 ~o 15~ in particular
Suitable sources of radiant energy are UV radiation, laser beams, X-ray beams and radioactive radiationu Electrical energy can b~ generated, for example, by el~ctrolysis pro cesses. E~amples of ~he free radic3l catalysts are potas-S sium persulphate, diben~oyl peroxide, azobisisobutyro-nitriLe, di-tert-butyl peroxide and cyclohexanone peroxide.
Ion;c catalysts are organic alkali metal compounds, such as phenyll~ithiu0 anJ naphthalenesodium, and Lewis acids, such as ~F3, AlCl3, SnCl4 and TiCl4, or metal complexes in the form of aluminium or titanium compounds. The monomers can be polymerized in solution, suspen~ion or emulsion or as suchc ~ here Y is a hydroxyl, amino, mercapto, epoxide or carboxyl group or one of their reactive derivatives, the compounds of the formula II can be grafted onto a polymeric backbone~ Here~ Y is particularly pre~erably OH, NH2, coaH or a reactive derivative, in particular OH
or a reactive derivative of the carbaxyl group. This grafting reaction can be carried out by methods ~hich are known per se~ such as, for example, esterification~ amid-ationf transesterification~ transamidation, acstalization or etherification, ~h;ch are described in the literature Cfor example, in standard works such as Houben-~eyl, Methoden der Organischen Chemie (Methods of Organic Chemistry), ~eorg~Thieme-YerLag, Stuttgart, or C.M. Paleos et al~, J. Polym. Sci~ Polym. Chem. 19 (1981~ 1427].
A preferred grafting reaction is the reaction of monomers carrying mesogenic groups o~ the formula I a/b with organopolysiloxanes. For this purpose, linear or cyclic organohydropolysiloxanes are react~d, as described in~ for example, European Patent Specification 0,ObO,335, with ethylenically unsaturated, mesogenic monomers of the ~ormula II (Y is an alkylene group which has 2 to 5 C atoms and is present in ~he ~- or (~ position), in about equi-molar amounts, based on the amount of siloxane-hydrogen, in the presence of a catalyst which promotes the addition of silane hydrogen at alipha~ic multiple bonds.
Sui~able polymeric backbones are in principle all polymers the chains of which possess a certain degree 1~ 7~
of flexibility. These may be linear, branched or cyclic polymer chainsO The degree of polymerization is usually at least 10, preferably 20-100. ~owever, oligomers, in particular cyclic oligomers, having 3 ~o 15~ in particular
4 to 7, monomer units are also suitable.
Polymers having C-C main chains, in particular polyacrylates, polymethacrylates, poly-~-haloacrylates, poly-~-cya~noacrylates, polyacrylamides, polyacrylonitriles and polymethylenemalonates, are preferred. Polymers having heteroatoms in their ~ain chain, for ~xample polyethers, polyesters, polyamides, polyimides or polyurethanes, or in particul3r polysiloxanes, are also preferredu Other particularly suitable polymeric backbones are liquid-crystalline main-chain polymers, as described by, for exampl~, R.W. Len2 in L.L. Chapoy (editor), Recent Advances in Liquid Crystalline Polymers, London ~ New York, 1985, page 3.
Compounds of the formula II which possess appro-priate terminal functional groups can be prepared by methods known per se, as described in the literature, tfor example in the standard works such as Houben-Veyl, Methoden der Organischen Chem;e (Me~hods of Organic Chemistry), ~eorg-Thieme-Yerlag, Stuttgart), the prepara-tion being carr;ed out under react;on cond;t;ons which are fam;l;ar, and suitable for the stated reactions.
Variants ~hich are known per se but not mentioned here can also be used.
Preferred starting materials are compounds of the formu(a III a/b, xl~
RlA- I Z-A )m~Z ~ ( A-Z )n-R2 I I I a x1,2 Rl (A-z)m-Ao~(z-A)n-R~ IIIb h i A A A1 R1 R2 z, z, m and n have the meanings given formula Ia/b and x1 is a carboxyl groups or one of its reactive derivatives, or an epoxide~ halogen, haloalkyl, ~i~7~
sulphonate or isocyanate group~ and x2 ;5 an amino, alcohol or ~hiol group or a halo-gen atomO
To prepare compounds of the formula Ia/b, compounds of the formula IlIa/b containing a functional group X1 can be subjected to esterification, etherifica~ion, a~ida-tion or a transition metal-catalysed coupling reaction with a co~pound which contains a functional grouP x2 and is suitable as a spacer~ The corresponding reaction of compounds of the formula IIla/b which contain functional groups x2 w;th compounds which contain functional groups x1 and are suitable as spacers is also suitable.
Other compounds which are preferred for the pre-paration of compounds of the formula Ia/b are compounds of ~he formulae IV and/or V
Sp-H
Ri~ Z) -A~ 2 IV X2~l_A_(Z-A)n-R2 V
wherein A, A, R1, R2, Sp, Z, Z, m and n have the meanings given for formula lalb, and X1 and x2 have the meanings given for for~ula IiIatb.
Compounds of the formula IV containing a functional group X1 can be subjected to esterification, etherifica-~ion, a~.dation or a transition metal-catalysed csupling reaction with compounds of the formula V containing a functional group of the formula X2. The corresponding react;on of compounds of the formula IV which contain the functional groups x2 ~ith compounds of the formula V
which contain funct;onal groups X1 is also suitable.
Other preferred compounds for the preparation of compounds of the formula Ia~b are compounds of the formulae VI and/or VII, Sp-~ 0~
~l - ( A ~ ) m A-C~; O}~ VI Rl - ( A- z ) m~A~ ~2 - ( A- z ) n; R V I I
wherein A, R~ R~, Sp, Z, m and n have the mean;ngs given for formula Iatb.
Alcohols of the formula Yl can be reacted ~;th compounds of the formula V which co~tain a functional group X1 having the meaning given for formula IIIa/b to give polymerizab~e compounds of the forlnula II ~hich are suitable for the preparation of the polymer materials according to the invention.
Alcohols of the ~ormula VII can be reacted with compounds which contain functional groups X1 and are suit-able as s~acers, to give prepolymers of the formula II.
Some of the compounds of the formulae IIIa/b, IV, V, VI and VII which are suitable for the preparation of in~ermediates which can be polymerized to give materials according to the invention, of the formula Ia/b, are known, but th~ majority are new. They are prepared by ~ethods known per se, as described in the ~iterature (for example in standard ~orks such as Houben-Weyl~ Methoden der Organischen Chemie ~Methods of Orsanic Chemistry), Georg-Thieme-Verlag, Stuttgart), the preparation being carried out under reaction conditions which are familiar, and suitable, for the stated reactions. Variants which are known per se but not men~ioned here may also be used.
Thsy are used for the preparation of the liquid-crystalline polymer materials according to the inv@ntion.
The processes stated for the preparation of IIIa/b to YII are known per se (for example from standard works such as Houben-Weyl, Methoden der Org. Chemie (Methods cf Organic Chemistry3, Georg-Thieme-Verlag, Stuttgart).
Usually, ~he reaction conditions kno~n for the stated reactions are maintained. However, variants ~hich are known per se but not mentiorled here may also be used.
In particular, the processes stated for the preparation of the parent substance which is not provided with a poly-mer;zable 5ide chain and is described by the formulae a to an can be used.
Some of the low moLecular weight compounds of the formula II have broad mesophase ranges. However, com-pounds of the formula II ~hich do not exhibit any meso-ph~ses are also suitable for the preparation of the poly-mer mater;als according to the invention.
The preparation of the homopolymers or copolymers from the polymerizabLe compounds of the forrnula II or their polymerizable derivatives is preferably carried out by free radical polymeri~ation~ The reaction is started, for example, by means of UV irradiatiQn or free radical formers. The monomers can be polymerized in solution or as such.
CopoLymer materials exhibiting liquid-crystalline phases a~cording to the inventirJn are obtained by copoly-merization of the polymerizable co~pounds of the formula 10 II or their polymerizable derivatives with mono~ers ~hich carry no mesogenic radicals, which carry other mesogenic radicals (for e~ample disc-like: German Pat~nt Specifica-tion 3,430,482~, ~hich carry chiral radicals (far example German Offenlegungsschrift 2,a31~909~ or which carry dye radicals (German Qffenlegungsschrift 3,211~400).
Starting from a monomer mixture having the concen-tration X1, copolymerization with such monomers leads to a copolymer in which the monomer is incorporated ;n a concentrat;on X1 only when the copolymerization parameters of the monsmer components are of comparable orders of mag-nitude. This is particularly important when it is desired to prepare a copolymer of a part;cular composition ~ithout difficulties, for exa~ple without taking into account the reaction kinetics. Hence, preferably chosen monomer com-ponen~s are those wh;ch haYe comparable copolymerizationparameters, for e~a~ple alkyl acrylates or alkyl meth-arrylates, which differ pr;marily by virtue of the SUD-stituents in the alkyl chain.
Copoly~erization with monomers which do not carry any mesogenic radical generally leads to a reduction in the glass transition temperature and in the clear point.
8y a suitable choice of the spacer, it is often possible to bring the mesophase range into ~he temperature range s~it able for the particular intended use.
Suitable monom~rs possessing a chiral radical are ;n principle all compounds of this type which possess asym ~etric C ato~s. Mowever, compounds of the formula II or their polymerizable derivatives~ in which M is a mesogenic group of the formula la or Ib, wherein one of the radicals R1, R2 and/or R3 is an alkyl group in which one CH2 group is replac~d with -CHCH3-, are preferably empLoyed.
Finally, a large number of further possible vari-a~ions arise from the fact that the compounds according to the invention combine liquid crystalline properties with typical polymer properties, such as the ability to form layers, f;lms and fibres, easy deformabil;ty, etc. These properties can be modified in a manner known per se, by copolymerization or mixing ~ith other components, by vari-ation of the molecular weights, by adding a very wide var-iety of inorganic or organic additives and metals, and by many other treatments fam;liar to the skilled worker in the f;eld of polymers.
The polymer materials according to the invention can be used as starting materials for the production of organic glasses having aniso~ropic properties which can be modified over wide ranges.
Applications of this type occur, for example, in the sector comprising light collectors and solar collec-tors or in connection with organic phototropic glasses.Furthermore, an important area of application has opened up in the field of optical memory.
Other possible applications are being opened up in the field of magnetic memories~ The materials according to the invention are also particularly suitable as a ma-trix for substances having non-linear optical properties, for the production of "non-linear" optical components.
The polymer materials according to the invention ar~ also suitable for amplitude modulation and/or frequency modulat;on of laser beams~
The examples ~hich follow serve to illustrate ~he invention, G denoting glass state, C denoting crystalline, N denoting nematic and I denoting isotropic (phase tran-sition temperatures in degrees Kelvin in each case)~
Example 1 a) 2~ Hydroxyundecyl)-hydroquinone obtained fro~
Z-~10-carboxydecyl)~hydroquinone (prepared from p-benzo-quinone and methyl undec-10-enoate by using d;borane and then carrying out hydrolysis) by reduction ~ith lithium ~;~7~3~ ~
alu~inium hydride is esterified ~Jith methacrylic acid to give 1 (11-methacryloyloxyundecyl)-hydroquinorle.
34.8 9 of the above co~pound are dissolved in 500 ml of d;chloromethane. 20 9 of triethylamine are S added, after ~hich 34.1 9 of 4-methoxybenzoyl chloride are introduced slowly at 0C. When the addition is complete, stirring is continued for 1 hour at room temperature, after which the~mixture is washed with ~ater and freed from the sol~ent under reduced pressure. The bis~(4-~ethoxyphenyl) ester ot 2-(11-methacryloylo~yundecyl)-hydroquinone is obtained. In the supercoc,led state, the monomer exhibits a meta-stable ~onotropic ne~atic phase: C (336) N 2~6 I.
b) The bis(4-methoxyphenyl) ester of 2-(11-methacry-loyloxyundecyl)-hydrociuinone ob~ained according to Example 1a is polymerized in an approx;mately 1 molar solution in benzene, in the presence of 1 mol % of azobisisobutyro-nitr;le at 60C. The resulting polymer exhib;ts a stable l;qu;d-crystall;ne phase: G 312 N 337 I~
Exa~ple 2 a) 2-(11-Methacryloyloxyundecyl)-hydroquinone is ester;fied with 4-hexyloxybenzoyl chloride~ analogously to the procedure descr;bed ;r Example 1a.
In the supercooled state~ the resulting bis(4-hexyloxyphenyl) ester of 2~ methacryloyloxyundecyL)-hydroquinone has a monotropic metastable nematic phase:C (322) N 319 I.
b) ~he bis(4-hexyloxyphenyl) ester of 2-(11 methacry-loyloxyundecyl)-hydroquinone obta;ned ;n Example Za is poly-mer;zed in solution in benzene, analogously to the pro-cedure described in Example 2. A polymer which exhibits 3stable liquid-crystalline phase is obtained: ~ 282 N 335 I.
Example 3 a) 2-(9-Carboxynonanoyl)-4-butylphenol obtained from 4-heptylphenol, sebacic anhydride and aluminium chloride by known processes is reduced to 2-(10-hydroxydecyl)-4-heptylph~nol ~ith lithium aluminium hydride/aluminium chloride.
b) 2-(10 Hydroxydecyl)-4-heptylphenol (0.1 mol) pre-pared according to Example 3a is reacted~ ~ith methacryloyl chloride (Oo1 moL) in 300 ml of pyridine at 5C to give 2-(10-methacryloyloxydecyl)-4-heptylphenol 9 c) 0.1 moL of the phenol 3b obtained above, in 250 ml of d;chloromethane, and 0.1 mol of triethylamine are trea-ted ~;th 0.1 mol of 4-propoxyben~oyl chloride at 0-5C.
The m;xture is stirred for 2 hours at this te~perature, after which it is washed neutral with ice ~ater, dried over sodium sulfate and evaporated dowrl. 2-(10-Methacryl-oyl-oxydecyl)-4 haptylphenyl 4-propoxytenzoate remains in the form of an oil.
d) A solu~ion of 0.05 mol of 2-(1C-methacryloyloxy-decyl~-4-heptylphenyl 4-propoxybenzoate in 100 ml of tol-uene is heated at 90C for 10 hours, after the addition of 0.5 9 of azobisisobutyronitrile. The polymer separates out as a gel on cool;ng. After the add;t;on of ethanol, the f;lterable amorphous product which exhibits a nematic liquid-crystall;ne phase ;s obta;ned~
Example 4 a) 2-(10-Methacryloyloxydecyl)-4-heptylphenol ~0.2 mol) obta;ned according to 3b ;s d;ssolved in 5~0 ml of dichloromethane and 0.1 mol of triethylamine. 0.1 mol of trans-4-propylcyclohexanecarbonyl chloride is added drop-wise at +5C and the mixture is kep~ at this ~emperature for a further 30 minutes and then stirred for 1 hour at Z5 room temperature. It is washed neutral with water, dried, and freed from the solvent under reduced pressure and under mild cond;t;ons. Oily 2-(10-methacryloylo~ydecyl)-4-heptyl-phenyl 4-propylcyclohexanecarboxylate remains.
b~ A mixture of 0.1 mol of 2-(10-methacryloyloxydecyl)-4-heptyLphenyl 4-propylcyclohexanecarboxylate, O.OOS mol of azob;sis~butyronitr;le and 400 ml o~ benzene is heated under reflux for 8 hoursO The st;ll hot polymer is then prec;pitated by stirring the m;xture ;nto 1 litre of methanol~ The polymer possesses liqu;d-crystall;ne properties.
Exa~ple S
a) 27.7 9 of 2-(3-cyano-4-fluorophenyl)-S-pentyl-1,3-dioxane (obtainable from 3-cyano-4-fluorobenzaldehyde and 2-pen~yl-1~3-propanediol) ;n 380 ml of d;oxane are aclded 7~ 3~
dropwise, in the course of 2 hours, to a boiling suspen-sion of 4~0 9 of lithium aluminium hydride in 300 ml of the same solvent. ~hen the addition is complete, heating is continued for a further hour and decomposition is then S effected with water. The solu~ion is ~filtered off from the precipitated hydroxide and evaporated do~n under re-duced pressure. Z-53-Aminometllyl-4-flllorophenyl)-5 pentyl-1,~-dioxane is obtained.
b) A mixture of 14.0 9 of 2 (3-aminomethyl-4-fluoro-phenyl)-S-pentyl-1,3-dioxane and 11.7 ~ of ethoxycarbonyl-octanoyl chloride in 250 ml of pyridine is stirred for 3 hours at room temperature~ It is then poured onto 2 litres of ice wzter~ and the precipitaeed 2-(3-(8-ethoxycarbonyl-octanoylamidomethyl)-4-fluorophenyl)-5-pentyl-1,3-dioxane is filtered off under suction~
c) 0.1 mol of the above amido ester Sb is introduced in portions into a boiling suspension of 7.5 9 of lithium aluminium hydride in 400 ml of tetrahydrofuran. Heating for 1 hour, decomposing with ~ater and working up as de-scribed in 5a) give 2-S3-(9-hydroxynonylaminomethyl)-4-f luorophenyl)-5-pentyl-1,3-dioxane~
d) 15 9 of an acrylic acid/acrylate poly~er conta;n-ing free carboxyl groups are converted to the acid chlor-ide with 10 9 of thionyl chloride in a custo~ary manner.
The residue obtained af~er remov;ng excess thionyl chlor-ide is suspended in pyridine, and the suspension is stir-red overnight ~ith 5 9 of 2-(3-(9-hydroxynonylaminomethyl)-4-fluorophenyl)-S-pentyl-1,3-dioxane. Filtration and washing with water give a polymer material which exhibits liquid-crystalline properties.
~xample 6 a~ 15 9 of trans-4-(4-(4-pentylcyclohexyl)-phenyl)-ethylbenzene in 50 ml of glacial acetic acid are slowly added dropwise, at -35C, to a m;xture of 50 9 of fuming nitric acid and 50 9 of acetic anhydride. Stirring is cont;nued for a further 2 hours at this temperaeure, af~er which the mixture is poured onto 1 litre of ;ce water, the pale yellow precipitate ;s f;ltered off and the resulting mixtures of the mononitro-4 (4-(4-pentylcyclohexyl)-phenyl-~L ~ 72 ~3 ~ r ~
ethylbenzenes are dried.
b) The nitro compound obtained above is hydrogenated in a customary manner in ethanolic solutiorl over palladium/
activated carbon.
0.1 ~ol of amino-4-t4-(4-pentylcyclohexyl)-phenyl-ethylbenzene prepared in this manner is heated for 6 hours at 90-95C with 0.1 ~ol of dimethyl brassylate in 300 ml of toluen~, with removal of the resulting methanol by dis-tillation~ When the reaction is complete, the product is freed fro~ the solvent under reduced pressure. (12-Methoxy-carbonyldodecanoyla~ino)-4-(4-(4-pentylcyclohexyl)-phenyl)-ethylbenzene is obtained.
c) 0.25 mol of the amidoester 6b is reduced with 0.5 mol of LiAlH~ as described in Example 5c to give (13 hydroxydodecylamino)-4-(4-(4-pentylcyclohexyl)-phenyl)-ethylben~ene, and then grafted, in the manner described under 5d, onto a copolymer containing carboxyl groups. A
polymer material exhibiting a liquid-crystalline phase is obtained.
Exampl~ 7 a) 21.0 g of 5-butoxysalicylic acid, 22.2 9 of 5-heptylpyri~idine-Z-carbonyl chloride and 20~0 9 of tri-ethylamine in 500 ~l of dichloromethane are subjected to an esterification reaction for 2 hours at +5C.
b) 2-Carboxy-4-butoxyphenyl 5-heptylpyrimidine-2-carboxylate obtained according to 7a (0.1 mol) is conver-ted to the acid chloride ~ith 15.0 g of thionyl chloride in a customary manner. The crude product obtained after excess thionyl chloride has been removed by distillation is taken up in 450 ml of dichloromethane, 20~0 9 of tri-ethylamine are added and a solution o~ 0.1 mol of 2 (2-(2~hydroxyethoxy) ethoxy)-ethyl acrylate is then intro-duced slo~ly. The ~ixture is stirred at room temperature for 1 hour and then washed with water, dried over sodium sulfate and freed from ~he solvent under reduced pressure.
2-(2-(2-(2-Acryloyloxyethoxy)-ethoxy)-ethoxycarbonyl)-4-butoxyphenyl 5-heptylpyrimidine-2-carboxylate is obtained.
c) 0.1 mol of the e~ter 7b into which an acryloyl group has been introduced, in 120 ml ot benzene~ ;s heated ~7~3~
under reflux for 6 hours, after the addition of 2.5 9 of azobisisobutyronitrile. After the mixture has b~en cooled, an equal volume of methanol is added. A polymer ~hich exhib;ts a liquid-crystalline phase is ;solated by fil-tration.Example ~
a) 1-(4'-Pentylbiphenyl~4-yl)-2-~4-propylcyclohexyl)-etheneO o~tainable from 4-propylcyclohexanecarbo~aldehyde and 4'-triphenylphosphono-4-pentylbipher1yl broMide by a Wittig reaction, is hydroborated with diborane in a ~us-tomary manner and onverted to 1-(4-propylcyclohexyl)-2-~4'-pentylbiphenyl-4-yl)-ethanol ~ith alkaline hydrogen pero~ide.
b) 0.1 mol of 1-(4-propylcyclohexyl~2-(4'-pentyLbi-phenyl-4-yl)-ethanol is stirred w;th 0.1 mol of sodium hy-dr;de in 350 ml of toluene at room temperature until evolu-tion of hydrogen is complete. 0.1 mol of allyl 9-bromo-pelargonate (obtained from allyl bromide and 9-bromo-pelargonic acid in dimethylformamide using potassium car-bonate) is then added, and the mixture ;s kept at 60C for3 hours. After ~ool;ng, the mixture is washed with water and dried over sodiu~ sulfate, and the solvent is removed under reduced pressure to give allyl 9-(1-(4-propylcyclo-hexyl)-Z-(4'-pentylbiphenyl-4-yl~-etho~y)-pelargonate.
2S c) 10 9 of the allyl ester Bb in Z00 ml of xylene are kept at 90~C for 3 hours, 200 mg of azobisisobutyronitrile being added. The polymer obtained on cooling is isolated by fil~ration. It exhibits liquid-crystalline properties above the glass transition te~perature.
Example 9 a) A mix~ure of OD1 mol of 4~heptylbenzene, 0.1 mol of sebacic anhydride and 0.2 ~ol of aluminium chloride in 400 ml of carbon disulfide is heated under reflu~ for ~
hours~ The reaction mi~ture is hydrolysed by add;ng 200 ml of 10% hydrochloric acid. The residue obtained after the organic phase has been separated off and the solvent re-moved by distillation is 4~sebacoyl-heptylbenzene.
b) 0.1 mol of 4-sebacoyl-heptylbenzene, 0.1 mol of sodium borohydride and 300 ml of methanol are stirred for
Polymers having C-C main chains, in particular polyacrylates, polymethacrylates, poly-~-haloacrylates, poly-~-cya~noacrylates, polyacrylamides, polyacrylonitriles and polymethylenemalonates, are preferred. Polymers having heteroatoms in their ~ain chain, for ~xample polyethers, polyesters, polyamides, polyimides or polyurethanes, or in particul3r polysiloxanes, are also preferredu Other particularly suitable polymeric backbones are liquid-crystalline main-chain polymers, as described by, for exampl~, R.W. Len2 in L.L. Chapoy (editor), Recent Advances in Liquid Crystalline Polymers, London ~ New York, 1985, page 3.
Compounds of the formula II which possess appro-priate terminal functional groups can be prepared by methods known per se, as described in the literature, tfor example in the standard works such as Houben-Veyl, Methoden der Organischen Chem;e (Me~hods of Organic Chemistry), ~eorg-Thieme-Yerlag, Stuttgart), the prepara-tion being carr;ed out under react;on cond;t;ons which are fam;l;ar, and suitable for the stated reactions.
Variants ~hich are known per se but not mentioned here can also be used.
Preferred starting materials are compounds of the formu(a III a/b, xl~
RlA- I Z-A )m~Z ~ ( A-Z )n-R2 I I I a x1,2 Rl (A-z)m-Ao~(z-A)n-R~ IIIb h i A A A1 R1 R2 z, z, m and n have the meanings given formula Ia/b and x1 is a carboxyl groups or one of its reactive derivatives, or an epoxide~ halogen, haloalkyl, ~i~7~
sulphonate or isocyanate group~ and x2 ;5 an amino, alcohol or ~hiol group or a halo-gen atomO
To prepare compounds of the formula Ia/b, compounds of the formula IlIa/b containing a functional group X1 can be subjected to esterification, etherifica~ion, a~ida-tion or a transition metal-catalysed coupling reaction with a co~pound which contains a functional grouP x2 and is suitable as a spacer~ The corresponding reaction of compounds of the formula IIla/b which contain functional groups x2 w;th compounds which contain functional groups x1 and are suitable as spacers is also suitable.
Other compounds which are preferred for the pre-paration of compounds of the formula Ia/b are compounds of ~he formulae IV and/or V
Sp-H
Ri~ Z) -A~ 2 IV X2~l_A_(Z-A)n-R2 V
wherein A, A, R1, R2, Sp, Z, Z, m and n have the meanings given for formula lalb, and X1 and x2 have the meanings given for for~ula IiIatb.
Compounds of the formula IV containing a functional group X1 can be subjected to esterification, etherifica-~ion, a~.dation or a transition metal-catalysed csupling reaction with compounds of the formula V containing a functional group of the formula X2. The corresponding react;on of compounds of the formula IV which contain the functional groups x2 ~ith compounds of the formula V
which contain funct;onal groups X1 is also suitable.
Other preferred compounds for the preparation of compounds of the formula Ia~b are compounds of the formulae VI and/or VII, Sp-~ 0~
~l - ( A ~ ) m A-C~; O}~ VI Rl - ( A- z ) m~A~ ~2 - ( A- z ) n; R V I I
wherein A, R~ R~, Sp, Z, m and n have the mean;ngs given for formula Iatb.
Alcohols of the formula Yl can be reacted ~;th compounds of the formula V which co~tain a functional group X1 having the meaning given for formula IIIa/b to give polymerizab~e compounds of the forlnula II ~hich are suitable for the preparation of the polymer materials according to the invention.
Alcohols of the ~ormula VII can be reacted with compounds which contain functional groups X1 and are suit-able as s~acers, to give prepolymers of the formula II.
Some of the compounds of the formulae IIIa/b, IV, V, VI and VII which are suitable for the preparation of in~ermediates which can be polymerized to give materials according to the invention, of the formula Ia/b, are known, but th~ majority are new. They are prepared by ~ethods known per se, as described in the ~iterature (for example in standard ~orks such as Houben-Weyl~ Methoden der Organischen Chemie ~Methods of Orsanic Chemistry), Georg-Thieme-Verlag, Stuttgart), the preparation being carried out under reaction conditions which are familiar, and suitable, for the stated reactions. Variants which are known per se but not men~ioned here may also be used.
Thsy are used for the preparation of the liquid-crystalline polymer materials according to the inv@ntion.
The processes stated for the preparation of IIIa/b to YII are known per se (for example from standard works such as Houben-Weyl, Methoden der Org. Chemie (Methods cf Organic Chemistry3, Georg-Thieme-Verlag, Stuttgart).
Usually, ~he reaction conditions kno~n for the stated reactions are maintained. However, variants ~hich are known per se but not mentiorled here may also be used.
In particular, the processes stated for the preparation of the parent substance which is not provided with a poly-mer;zable 5ide chain and is described by the formulae a to an can be used.
Some of the low moLecular weight compounds of the formula II have broad mesophase ranges. However, com-pounds of the formula II ~hich do not exhibit any meso-ph~ses are also suitable for the preparation of the poly-mer mater;als according to the invention.
The preparation of the homopolymers or copolymers from the polymerizabLe compounds of the forrnula II or their polymerizable derivatives is preferably carried out by free radical polymeri~ation~ The reaction is started, for example, by means of UV irradiatiQn or free radical formers. The monomers can be polymerized in solution or as such.
CopoLymer materials exhibiting liquid-crystalline phases a~cording to the inventirJn are obtained by copoly-merization of the polymerizable co~pounds of the formula 10 II or their polymerizable derivatives with mono~ers ~hich carry no mesogenic radicals, which carry other mesogenic radicals (for e~ample disc-like: German Pat~nt Specifica-tion 3,430,482~, ~hich carry chiral radicals (far example German Offenlegungsschrift 2,a31~909~ or which carry dye radicals (German Qffenlegungsschrift 3,211~400).
Starting from a monomer mixture having the concen-tration X1, copolymerization with such monomers leads to a copolymer in which the monomer is incorporated ;n a concentrat;on X1 only when the copolymerization parameters of the monsmer components are of comparable orders of mag-nitude. This is particularly important when it is desired to prepare a copolymer of a part;cular composition ~ithout difficulties, for exa~ple without taking into account the reaction kinetics. Hence, preferably chosen monomer com-ponen~s are those wh;ch haYe comparable copolymerizationparameters, for e~a~ple alkyl acrylates or alkyl meth-arrylates, which differ pr;marily by virtue of the SUD-stituents in the alkyl chain.
Copoly~erization with monomers which do not carry any mesogenic radical generally leads to a reduction in the glass transition temperature and in the clear point.
8y a suitable choice of the spacer, it is often possible to bring the mesophase range into ~he temperature range s~it able for the particular intended use.
Suitable monom~rs possessing a chiral radical are ;n principle all compounds of this type which possess asym ~etric C ato~s. Mowever, compounds of the formula II or their polymerizable derivatives~ in which M is a mesogenic group of the formula la or Ib, wherein one of the radicals R1, R2 and/or R3 is an alkyl group in which one CH2 group is replac~d with -CHCH3-, are preferably empLoyed.
Finally, a large number of further possible vari-a~ions arise from the fact that the compounds according to the invention combine liquid crystalline properties with typical polymer properties, such as the ability to form layers, f;lms and fibres, easy deformabil;ty, etc. These properties can be modified in a manner known per se, by copolymerization or mixing ~ith other components, by vari-ation of the molecular weights, by adding a very wide var-iety of inorganic or organic additives and metals, and by many other treatments fam;liar to the skilled worker in the f;eld of polymers.
The polymer materials according to the invention can be used as starting materials for the production of organic glasses having aniso~ropic properties which can be modified over wide ranges.
Applications of this type occur, for example, in the sector comprising light collectors and solar collec-tors or in connection with organic phototropic glasses.Furthermore, an important area of application has opened up in the field of optical memory.
Other possible applications are being opened up in the field of magnetic memories~ The materials according to the invention are also particularly suitable as a ma-trix for substances having non-linear optical properties, for the production of "non-linear" optical components.
The polymer materials according to the invention ar~ also suitable for amplitude modulation and/or frequency modulat;on of laser beams~
The examples ~hich follow serve to illustrate ~he invention, G denoting glass state, C denoting crystalline, N denoting nematic and I denoting isotropic (phase tran-sition temperatures in degrees Kelvin in each case)~
Example 1 a) 2~ Hydroxyundecyl)-hydroquinone obtained fro~
Z-~10-carboxydecyl)~hydroquinone (prepared from p-benzo-quinone and methyl undec-10-enoate by using d;borane and then carrying out hydrolysis) by reduction ~ith lithium ~;~7~3~ ~
alu~inium hydride is esterified ~Jith methacrylic acid to give 1 (11-methacryloyloxyundecyl)-hydroquinorle.
34.8 9 of the above co~pound are dissolved in 500 ml of d;chloromethane. 20 9 of triethylamine are S added, after ~hich 34.1 9 of 4-methoxybenzoyl chloride are introduced slowly at 0C. When the addition is complete, stirring is continued for 1 hour at room temperature, after which the~mixture is washed with ~ater and freed from the sol~ent under reduced pressure. The bis~(4-~ethoxyphenyl) ester ot 2-(11-methacryloylo~yundecyl)-hydroquinone is obtained. In the supercoc,led state, the monomer exhibits a meta-stable ~onotropic ne~atic phase: C (336) N 2~6 I.
b) The bis(4-methoxyphenyl) ester of 2-(11-methacry-loyloxyundecyl)-hydrociuinone ob~ained according to Example 1a is polymerized in an approx;mately 1 molar solution in benzene, in the presence of 1 mol % of azobisisobutyro-nitr;le at 60C. The resulting polymer exhib;ts a stable l;qu;d-crystall;ne phase: G 312 N 337 I~
Exa~ple 2 a) 2-(11-Methacryloyloxyundecyl)-hydroquinone is ester;fied with 4-hexyloxybenzoyl chloride~ analogously to the procedure descr;bed ;r Example 1a.
In the supercooled state~ the resulting bis(4-hexyloxyphenyl) ester of 2~ methacryloyloxyundecyL)-hydroquinone has a monotropic metastable nematic phase:C (322) N 319 I.
b) ~he bis(4-hexyloxyphenyl) ester of 2-(11 methacry-loyloxyundecyl)-hydroquinone obta;ned ;n Example Za is poly-mer;zed in solution in benzene, analogously to the pro-cedure described in Example 2. A polymer which exhibits 3stable liquid-crystalline phase is obtained: ~ 282 N 335 I.
Example 3 a) 2-(9-Carboxynonanoyl)-4-butylphenol obtained from 4-heptylphenol, sebacic anhydride and aluminium chloride by known processes is reduced to 2-(10-hydroxydecyl)-4-heptylph~nol ~ith lithium aluminium hydride/aluminium chloride.
b) 2-(10 Hydroxydecyl)-4-heptylphenol (0.1 mol) pre-pared according to Example 3a is reacted~ ~ith methacryloyl chloride (Oo1 moL) in 300 ml of pyridine at 5C to give 2-(10-methacryloyloxydecyl)-4-heptylphenol 9 c) 0.1 moL of the phenol 3b obtained above, in 250 ml of d;chloromethane, and 0.1 mol of triethylamine are trea-ted ~;th 0.1 mol of 4-propoxyben~oyl chloride at 0-5C.
The m;xture is stirred for 2 hours at this te~perature, after which it is washed neutral with ice ~ater, dried over sodium sulfate and evaporated dowrl. 2-(10-Methacryl-oyl-oxydecyl)-4 haptylphenyl 4-propoxytenzoate remains in the form of an oil.
d) A solu~ion of 0.05 mol of 2-(1C-methacryloyloxy-decyl~-4-heptylphenyl 4-propoxybenzoate in 100 ml of tol-uene is heated at 90C for 10 hours, after the addition of 0.5 9 of azobisisobutyronitrile. The polymer separates out as a gel on cool;ng. After the add;t;on of ethanol, the f;lterable amorphous product which exhibits a nematic liquid-crystall;ne phase ;s obta;ned~
Example 4 a) 2-(10-Methacryloyloxydecyl)-4-heptylphenol ~0.2 mol) obta;ned according to 3b ;s d;ssolved in 5~0 ml of dichloromethane and 0.1 mol of triethylamine. 0.1 mol of trans-4-propylcyclohexanecarbonyl chloride is added drop-wise at +5C and the mixture is kep~ at this ~emperature for a further 30 minutes and then stirred for 1 hour at Z5 room temperature. It is washed neutral with water, dried, and freed from the solvent under reduced pressure and under mild cond;t;ons. Oily 2-(10-methacryloylo~ydecyl)-4-heptyl-phenyl 4-propylcyclohexanecarboxylate remains.
b~ A mixture of 0.1 mol of 2-(10-methacryloyloxydecyl)-4-heptyLphenyl 4-propylcyclohexanecarboxylate, O.OOS mol of azob;sis~butyronitr;le and 400 ml o~ benzene is heated under reflux for 8 hoursO The st;ll hot polymer is then prec;pitated by stirring the m;xture ;nto 1 litre of methanol~ The polymer possesses liqu;d-crystall;ne properties.
Exa~ple S
a) 27.7 9 of 2-(3-cyano-4-fluorophenyl)-S-pentyl-1,3-dioxane (obtainable from 3-cyano-4-fluorobenzaldehyde and 2-pen~yl-1~3-propanediol) ;n 380 ml of d;oxane are aclded 7~ 3~
dropwise, in the course of 2 hours, to a boiling suspen-sion of 4~0 9 of lithium aluminium hydride in 300 ml of the same solvent. ~hen the addition is complete, heating is continued for a further hour and decomposition is then S effected with water. The solu~ion is ~filtered off from the precipitated hydroxide and evaporated do~n under re-duced pressure. Z-53-Aminometllyl-4-flllorophenyl)-5 pentyl-1,~-dioxane is obtained.
b) A mixture of 14.0 9 of 2 (3-aminomethyl-4-fluoro-phenyl)-S-pentyl-1,3-dioxane and 11.7 ~ of ethoxycarbonyl-octanoyl chloride in 250 ml of pyridine is stirred for 3 hours at room temperature~ It is then poured onto 2 litres of ice wzter~ and the precipitaeed 2-(3-(8-ethoxycarbonyl-octanoylamidomethyl)-4-fluorophenyl)-5-pentyl-1,3-dioxane is filtered off under suction~
c) 0.1 mol of the above amido ester Sb is introduced in portions into a boiling suspension of 7.5 9 of lithium aluminium hydride in 400 ml of tetrahydrofuran. Heating for 1 hour, decomposing with ~ater and working up as de-scribed in 5a) give 2-S3-(9-hydroxynonylaminomethyl)-4-f luorophenyl)-5-pentyl-1,3-dioxane~
d) 15 9 of an acrylic acid/acrylate poly~er conta;n-ing free carboxyl groups are converted to the acid chlor-ide with 10 9 of thionyl chloride in a custo~ary manner.
The residue obtained af~er remov;ng excess thionyl chlor-ide is suspended in pyridine, and the suspension is stir-red overnight ~ith 5 9 of 2-(3-(9-hydroxynonylaminomethyl)-4-fluorophenyl)-S-pentyl-1,3-dioxane. Filtration and washing with water give a polymer material which exhibits liquid-crystalline properties.
~xample 6 a~ 15 9 of trans-4-(4-(4-pentylcyclohexyl)-phenyl)-ethylbenzene in 50 ml of glacial acetic acid are slowly added dropwise, at -35C, to a m;xture of 50 9 of fuming nitric acid and 50 9 of acetic anhydride. Stirring is cont;nued for a further 2 hours at this temperaeure, af~er which the mixture is poured onto 1 litre of ;ce water, the pale yellow precipitate ;s f;ltered off and the resulting mixtures of the mononitro-4 (4-(4-pentylcyclohexyl)-phenyl-~L ~ 72 ~3 ~ r ~
ethylbenzenes are dried.
b) The nitro compound obtained above is hydrogenated in a customary manner in ethanolic solutiorl over palladium/
activated carbon.
0.1 ~ol of amino-4-t4-(4-pentylcyclohexyl)-phenyl-ethylbenzene prepared in this manner is heated for 6 hours at 90-95C with 0.1 ~ol of dimethyl brassylate in 300 ml of toluen~, with removal of the resulting methanol by dis-tillation~ When the reaction is complete, the product is freed fro~ the solvent under reduced pressure. (12-Methoxy-carbonyldodecanoyla~ino)-4-(4-(4-pentylcyclohexyl)-phenyl)-ethylbenzene is obtained.
c) 0.25 mol of the amidoester 6b is reduced with 0.5 mol of LiAlH~ as described in Example 5c to give (13 hydroxydodecylamino)-4-(4-(4-pentylcyclohexyl)-phenyl)-ethylben~ene, and then grafted, in the manner described under 5d, onto a copolymer containing carboxyl groups. A
polymer material exhibiting a liquid-crystalline phase is obtained.
Exampl~ 7 a) 21.0 g of 5-butoxysalicylic acid, 22.2 9 of 5-heptylpyri~idine-Z-carbonyl chloride and 20~0 9 of tri-ethylamine in 500 ~l of dichloromethane are subjected to an esterification reaction for 2 hours at +5C.
b) 2-Carboxy-4-butoxyphenyl 5-heptylpyrimidine-2-carboxylate obtained according to 7a (0.1 mol) is conver-ted to the acid chloride ~ith 15.0 g of thionyl chloride in a customary manner. The crude product obtained after excess thionyl chloride has been removed by distillation is taken up in 450 ml of dichloromethane, 20~0 9 of tri-ethylamine are added and a solution o~ 0.1 mol of 2 (2-(2~hydroxyethoxy) ethoxy)-ethyl acrylate is then intro-duced slo~ly. The ~ixture is stirred at room temperature for 1 hour and then washed with water, dried over sodium sulfate and freed from ~he solvent under reduced pressure.
2-(2-(2-(2-Acryloyloxyethoxy)-ethoxy)-ethoxycarbonyl)-4-butoxyphenyl 5-heptylpyrimidine-2-carboxylate is obtained.
c) 0.1 mol of the e~ter 7b into which an acryloyl group has been introduced, in 120 ml ot benzene~ ;s heated ~7~3~
under reflux for 6 hours, after the addition of 2.5 9 of azobisisobutyronitrile. After the mixture has b~en cooled, an equal volume of methanol is added. A polymer ~hich exhib;ts a liquid-crystalline phase is ;solated by fil-tration.Example ~
a) 1-(4'-Pentylbiphenyl~4-yl)-2-~4-propylcyclohexyl)-etheneO o~tainable from 4-propylcyclohexanecarbo~aldehyde and 4'-triphenylphosphono-4-pentylbipher1yl broMide by a Wittig reaction, is hydroborated with diborane in a ~us-tomary manner and onverted to 1-(4-propylcyclohexyl)-2-~4'-pentylbiphenyl-4-yl)-ethanol ~ith alkaline hydrogen pero~ide.
b) 0.1 mol of 1-(4-propylcyclohexyl~2-(4'-pentyLbi-phenyl-4-yl)-ethanol is stirred w;th 0.1 mol of sodium hy-dr;de in 350 ml of toluene at room temperature until evolu-tion of hydrogen is complete. 0.1 mol of allyl 9-bromo-pelargonate (obtained from allyl bromide and 9-bromo-pelargonic acid in dimethylformamide using potassium car-bonate) is then added, and the mixture ;s kept at 60C for3 hours. After ~ool;ng, the mixture is washed with water and dried over sodiu~ sulfate, and the solvent is removed under reduced pressure to give allyl 9-(1-(4-propylcyclo-hexyl)-Z-(4'-pentylbiphenyl-4-yl~-etho~y)-pelargonate.
2S c) 10 9 of the allyl ester Bb in Z00 ml of xylene are kept at 90~C for 3 hours, 200 mg of azobisisobutyronitrile being added. The polymer obtained on cooling is isolated by fil~ration. It exhibits liquid-crystalline properties above the glass transition te~perature.
Example 9 a) A mix~ure of OD1 mol of 4~heptylbenzene, 0.1 mol of sebacic anhydride and 0.2 ~ol of aluminium chloride in 400 ml of carbon disulfide is heated under reflu~ for ~
hours~ The reaction mi~ture is hydrolysed by add;ng 200 ml of 10% hydrochloric acid. The residue obtained after the organic phase has been separated off and the solvent re-moved by distillation is 4~sebacoyl-heptylbenzene.
b) 0.1 mol of 4-sebacoyl-heptylbenzene, 0.1 mol of sodium borohydride and 300 ml of methanol are stirred for
5 hours at 0 to +5C. The mixture is then evaporated to dryness under reduced pressure, the residue is taken up in water, and the product, 10-(4-heptylphenyl)-lO-hydroxy-decanoic acid, is precipitated by adding dilute hydro-chloric acid.c) The corresponding methyl ester is prepared from 0.2 mol of the acid 9b described abave in a customary man-ner by heating in ~ethanol with the addition of sulfuric acid.
63.2 9 of methyl 10-(4-heptylphenyl~-10-hydroxy-decaroat~ are converted to the sodium alcoholate with 10 9 of a 50% sodium hydride/liquid paraffin dispersion in 500 ml of dimethyl sulfoxide. When the evolution of hydro-gen is complete, a sr,lution of 69.6 9 of 4-(4-mesyloxy-cyclohexyl)-butylcyclohexane (prepared from ~he corre-sponding cyclohexanol with mesyl chloride/triethylamine in dichloromethane) in 120 ml of dimethyl sulfoxide is added dropwise as 20C. Stirring is continued for a further 2 hours at 50C, and the mixture is poured onto 2 litres of ice water and extracted with dichloromethane. The residue obtained after removal of the solvent is chromatographed over silica gel, using chloroform as the eluant. Methyl 10-(4-t4-butylcyclohexyl)-cyclohexyloxy)-10-(4-heptyl-~henyl)-decanoate is isolated.
ZS d) 0.1 mol of the decanoa~e obtained in 9c is hydro-lysed by boiling for 4 hours in a mixture of 300 ml of m~thanol, 100 ml of water and 25 9 of potassium hydroxide.
The reaction mixture obtained is acidified by adding semi-concentrated hydrochloric acid. The precipitate is fil-tered off and dried at elevated temperature. To convert;t to the acid chloride, the crude acid prepared as des-cribed above is heated under reflux for 3 hours in the same amount by we;ght of th;onyl chlor;de. Volatile components are removed under reduced pressure, and 10 (4~(4-butyl-cyclohe~yl)-cyclohexyloxy)-10-(4-heptylphenyl)~decanoyl chloride is ;solated ;n this manner.
e) 15 9 of a hydroxylated po~yacrylate in 5 9 of acid chloride 9d in 200 ml of pyridine are stirred for 24 hours at room temperature, after the addition of 1 9 of 4-dimethylaminopyridine.
The mixture is filtered, and the residue is washed with water and dried. The polymer prepared in this manner exhibits a liquid-crystalline phase.
63.2 9 of methyl 10-(4-heptylphenyl~-10-hydroxy-decaroat~ are converted to the sodium alcoholate with 10 9 of a 50% sodium hydride/liquid paraffin dispersion in 500 ml of dimethyl sulfoxide. When the evolution of hydro-gen is complete, a sr,lution of 69.6 9 of 4-(4-mesyloxy-cyclohexyl)-butylcyclohexane (prepared from ~he corre-sponding cyclohexanol with mesyl chloride/triethylamine in dichloromethane) in 120 ml of dimethyl sulfoxide is added dropwise as 20C. Stirring is continued for a further 2 hours at 50C, and the mixture is poured onto 2 litres of ice water and extracted with dichloromethane. The residue obtained after removal of the solvent is chromatographed over silica gel, using chloroform as the eluant. Methyl 10-(4-t4-butylcyclohexyl)-cyclohexyloxy)-10-(4-heptyl-~henyl)-decanoate is isolated.
ZS d) 0.1 mol of the decanoa~e obtained in 9c is hydro-lysed by boiling for 4 hours in a mixture of 300 ml of m~thanol, 100 ml of water and 25 9 of potassium hydroxide.
The reaction mixture obtained is acidified by adding semi-concentrated hydrochloric acid. The precipitate is fil-tered off and dried at elevated temperature. To convert;t to the acid chloride, the crude acid prepared as des-cribed above is heated under reflux for 3 hours in the same amount by we;ght of th;onyl chlor;de. Volatile components are removed under reduced pressure, and 10 (4~(4-butyl-cyclohe~yl)-cyclohexyloxy)-10-(4-heptylphenyl)~decanoyl chloride is ;solated ;n this manner.
e) 15 9 of a hydroxylated po~yacrylate in 5 9 of acid chloride 9d in 200 ml of pyridine are stirred for 24 hours at room temperature, after the addition of 1 9 of 4-dimethylaminopyridine.
The mixture is filtered, and the residue is washed with water and dried. The polymer prepared in this manner exhibits a liquid-crystalline phase.
Claims (6)
1. Polymer materials which have Liquid-crystalline phases and the mesogenic groups of which are bonded lat-erally to the polymer backbone.
2. Polymer materials having liquid-crystalline phases, according to claim 1, characterized in that the mesogenic groups correspond to the formula Ia and/or Ib Ia Ib wherein R1 and R2 are alkyl having 1-15 C atoms, in which furthermore one or two non-adjacent CH2 groups can be replaced with -O-, -CO , -O-CO, -CO-O-and/or -CH=CH-, or one of the radicals R1 and R2 may furthermore be H, F, Cl, Br, NCS, N02, CH or R3-A-Z, R3 is alkyl having 1-15 C atoms, in which further-more one or two non-adjacent CH2 groups can be replaced with -O-, -CO-, -O-CO-, -CO-0- and/or -CH=CH-, or is H, F, Cl, Br, NCS or CN, Sp is a covalent bond or a radical of the formula -Q1-W1-Q2-W2-, Q1 and Q2 independently of one another are each a chemical bond and/or an alkylene group having 2 to 25 C atoms, in which furthermore one or more non-adjacent CH2 groups can be replaced with -0-, -S-or -N(C1-C6-alkyl)-, W1 and W2 independently of one another are each a chemical bond and/or a functional grouping from the group consisting of -0-, -S-, -SO-, -S02-, -N(C1-C6-alkyl)-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CO-S-, -S-CO-, -CO-NH(C1-C6-alkyl)-, -NH(C1-C6-alkyl)-CO, -O-CO-NH(C1-C6-alkyl)- or -NH(C1-C6-alkyl)-CO-O and C1-C6-alkyl, A in each case is a 1,4 cyclohexylene group, in which furthermore one or two non-adjacent CH2 groups can be replaced with -O- and/or -S-, and/or which can be substituted in the 1-position by C1-C4-alkyl, F, Cl, Br, CF3 or CN, or is a piper-idine-1,4-diyl or 1,4-bicyclo[2.2.2]octylene group or a 1,4-phenylene group which is unsubsti-tuted or substituted by one or two F and/or Cl atoms and/or CH3 groups and/or CN groups and in which furthermore one or more CH groups can be replaced with N, Ao-Sp- is a radical of the formula (1) or (2) (1) (2) wherein furthermore one or two non-adjacent CH2 groups can be replaced with -0- and/or -S-, and/or a -CH2-CH group can be replaced with -N=C- or -CH=C- and/or which can be substituted in the 1-position by C1-C4-alkyl, F, Cl, Br, CF3 or CN, or is a radical of the formula (3) (3) wherein q is 0 to 2 and wherein furthermore one or more CH groups can be replaced with N, and/or which can furthermore be substituted by one or two F and/or Cl atoms and/or CH3 groups and/or CN
groups, or is a radical (4), (5) or (6) (4) (5) (6) n and m are each 0 to 3, Z in each case is -CO-O , -O-CO-, -CH2CH2-, -CHCN-CH2-, -CH2-CHCN-, -CH=CH-, -OCH2-, -CH2O-, -CH=N-, -N=CH-, -NO=N-, -N=NO- or a single bond, and Zo-Sp is -CH2CHSp-, -CSpCN-CH2-, -CHCN-CHSp-, -CSp=CH-, -CHSp-0- or -CSp=N-with the proviso that m + n is 0 to 3.
groups, or is a radical (4), (5) or (6) (4) (5) (6) n and m are each 0 to 3, Z in each case is -CO-O , -O-CO-, -CH2CH2-, -CHCN-CH2-, -CH2-CHCN-, -CH=CH-, -OCH2-, -CH2O-, -CH=N-, -N=CH-, -NO=N-, -N=NO- or a single bond, and Zo-Sp is -CH2CHSp-, -CSpCN-CH2-, -CHCN-CHSp-, -CSp=CH-, -CHSp-0- or -CSp=N-with the proviso that m + n is 0 to 3.
3. Process for the preparation of polymer materials according to Claims 1 and 2, characterized in that com-pounds of the formula II
Y-M II
wherein M is a mesogenic group of the formula Ia/b and Y is a functional group capable of polymerization or of being grafted, are polymerized~ ~here Y
is an alkylene group which has 2 to 5 C atoms and is located in the .omega.- or (.omega.-1)-position, or grafted onto polymers, where Y is a hydroxyl, amino, mercapto, epoxide or carboxyl group or one of its reactive derivatives.
Y-M II
wherein M is a mesogenic group of the formula Ia/b and Y is a functional group capable of polymerization or of being grafted, are polymerized~ ~here Y
is an alkylene group which has 2 to 5 C atoms and is located in the .omega.- or (.omega.-1)-position, or grafted onto polymers, where Y is a hydroxyl, amino, mercapto, epoxide or carboxyl group or one of its reactive derivatives.
4. Use of polymer materials according to Claims 1 and 2 as organic substrates in electronics, for fibre and film technology.
5. Use of polymer materials according to Claims 1 and 2 for amplitude modulation and/or frequency modulation of laser beams.
6. Use of polymer materials according to Claims 1 and 2 for optical data storage.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3534646.9 | 1985-09-28 | ||
| DE19853534646 DE3534646A1 (en) | 1985-09-28 | 1985-09-28 | LIQUID CRYSTALLINE PHASED POLYMER MATERIALS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1272342A true CA1272342A (en) | 1990-07-31 |
Family
ID=6282205
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000519143A Expired - Fee Related CA1272342A (en) | 1985-09-28 | 1986-09-26 | Polymer materials having liquid-crystalline phases |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0220463B1 (en) |
| JP (1) | JPS6274987A (en) |
| KR (1) | KR870003180A (en) |
| AT (1) | ATE71131T1 (en) |
| CA (1) | CA1272342A (en) |
| DE (2) | DE3534646A1 (en) |
| FI (1) | FI863893A (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3770889D1 (en) * | 1986-07-30 | 1991-07-25 | De Beers Ind Diamond | MANUFACTURE OF CUBIC BORNITRIDE. |
| KR920701195A (en) * | 1989-12-08 | 1992-08-11 | 위르겐 호이만·라인하르트 슈틀러 | Phenyldioxane |
| ES2067848T3 (en) * | 1990-09-24 | 1995-04-01 | Akzo Nobel Nv | INFRARED SENSITIVE LIQUID CRYSTAL POLYESTERS, SUITABLE FOR USE IN OPTICAL DATA STORAGE, PROCEDURES FOR THE PREPARATION OF THE SAME, AND APPARATUS CONTAINING AN INFRARED SENSITIVE LIQUID CRYSTAL POLYESTER. |
| DE4209681A1 (en) * | 1992-03-25 | 1993-09-30 | Merck Patent Gmbh | Electro-optical arrangement |
| GB2267501A (en) * | 1992-06-05 | 1993-12-08 | Secr Defence | Liquid crystal polymers |
| GB2283976B (en) * | 1992-06-05 | 1997-01-22 | Secr Defence | Liquid crystal polymers |
| US7785488B2 (en) | 2005-12-08 | 2010-08-31 | Chisso Corporation | Lateral oxirane compound and polymer thereof |
| US7919648B2 (en) | 2005-12-08 | 2011-04-05 | Chisso Corporation | Lateral α-substituted acrylate compound and polymer thereof |
| US9120883B2 (en) | 2011-04-18 | 2015-09-01 | Dic Corporation | Polymerizable compound having lateral substituent in terminal ring structure |
| JP6102423B2 (en) * | 2013-03-29 | 2017-03-29 | Dic株式会社 | Polymerizable compound and optical element |
| JP2020100600A (en) * | 2018-12-25 | 2020-07-02 | Dic株式会社 | Polymerizable stabilizer and liquid crystal composition using the same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3430482C1 (en) * | 1984-08-18 | 1991-07-18 | Merck Patent Gmbh, 6100 Darmstadt | Polymer compositions comprising liquid-crystalline phases |
| US4603187A (en) * | 1985-03-11 | 1986-07-29 | Celanese Corporation | Polyacetylenic compositions |
-
1985
- 1985-09-28 DE DE19853534646 patent/DE3534646A1/en not_active Withdrawn
-
1986
- 1986-09-17 EP EP86112830A patent/EP0220463B1/en not_active Expired - Lifetime
- 1986-09-17 AT AT86112830T patent/ATE71131T1/en not_active IP Right Cessation
- 1986-09-17 DE DE8686112830T patent/DE3683241D1/en not_active Expired - Fee Related
- 1986-09-26 CA CA000519143A patent/CA1272342A/en not_active Expired - Fee Related
- 1986-09-26 FI FI863893A patent/FI863893A/en not_active Application Discontinuation
- 1986-09-26 JP JP61226361A patent/JPS6274987A/en active Pending
- 1986-09-27 KR KR860008119A patent/KR870003180A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| FI863893A0 (en) | 1986-09-26 |
| JPS6274987A (en) | 1987-04-06 |
| DE3683241D1 (en) | 1992-02-13 |
| EP0220463B1 (en) | 1992-01-02 |
| EP0220463A2 (en) | 1987-05-06 |
| DE3534646A1 (en) | 1987-04-02 |
| ATE71131T1 (en) | 1992-01-15 |
| EP0220463A3 (en) | 1989-05-24 |
| FI863893A (en) | 1987-03-29 |
| KR870003180A (en) | 1987-04-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1187802B1 (en) | Liquid crystal compounds | |
| EP0700981B1 (en) | Photopolymerisable liquid crystals | |
| US4631328A (en) | Polymers containing mesogenic groups and dye radicals in the side chains | |
| US5567349A (en) | Photo cross-linkable liquid crystals | |
| US6613245B1 (en) | Crosslinkable liquid crystalline compounds | |
| EP0755918B1 (en) | Photocrosslinkable liquid crystalline 1,2-phenylene derivatives | |
| CA1272342A (en) | Polymer materials having liquid-crystalline phases | |
| KR20200053554A (en) | Compound, liquid crystal composition thereof and optoelectronic display device | |
| US4614619A (en) | Liquid crystalline materials useful to prepare polymeric films | |
| US4925589A (en) | Amide side-chain polymers | |
| JPH04227611A (en) | Polymerizable nematic monomer composition | |
| US5707544A (en) | Chromophore-containing photo cross-linkable liquid crystals | |
| US4211666A (en) | Liquid crystal compounds | |
| US5851427A (en) | Photocross-linkable naphthyl derivatives | |
| US20110240917A1 (en) | Blue phase liquid crystal composition | |
| GB2199826A (en) | Alkyl phenyl ester liquid crystal compounds | |
| GB2162515A (en) | Liquid crystal esters | |
| US5164111A (en) | Polymerizable liquid-crystal material and polymers exhibiting liquid-crystal phases | |
| US5190689A (en) | Polymer materials having liquid-crystalline phases | |
| US4683078A (en) | Dihalogeno-aromatic compound | |
| KR101737990B1 (en) | Asymmetric bifunctional bent-core reactive mesogens and method for preparing the same | |
| EP1470105B1 (en) | Liquid crystal compounds | |
| US4293698A (en) | Compound for controlling dielectric constant of liquid crystal | |
| JPH10168076A (en) | Liquid crystal compound having negative permittivity anisotropic value, liquid crystal composition containing the liquid crystal compound and liquid crystal display element using the composition | |
| EP0272301B1 (en) | Polymerizable liquid crystal materials and polymers displaying liquid crystal phases |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |