LIQUID CRYSTAL COMPOUNDS

Abstract

The invention relates to novel polymerizable liquid crystals of formula (I), to LCP mixtures comprising these compounds and to their uses for optical and electro-optical devices:

##STR00001##

Claims

1. A compound of formula (I) ##STR00036## wherein A and B each independently from each other represents an unsubstituted or substituted carbocyclic or heterocyclic aromatic group selected from a monocyclic ring of five or six atoms, two adjacent monocyclic rings of five or six atoms, a bicyclic ring system of eight, nine or ten atoms, or a tricyclic ring system of thirteen or fourteen atoms; SP.sub.1, SP.sub.2 and SP.sub.3 each independently from each other represents a substituted or unsubstituted, straight-chain or branched C.sub.1-C.sub.18 alkylene group, in which one, two, three or four more CH.sub.2, CH or C groups are unreplaced or replaced by groups selected from the group consisting of CH?CH, C?C, O, S, NRCO, COO, OOC, CONR, OCOO, OCONR with the proviso that the spacer group does not contain two adjacent heteroatoms; X.sub.1, X.sub.2, X.sub.3 and X.sub.4 each independently from each other is selected from the group consisting of O, S, NR, CO, COO, OOC, CONR, OCOO, OCONR and a single bond; R is selected from the group consisting of hydrogen, a C.sub.1-C.sub.18alkyl group; BP.sub.1 and BP.sub.2 each independently from each other represents a polymerizable group, A.sub.1, A.sub.2, A.sub.3 and A.sub.4 each independently from each other are selected from the group consisting of hydrogen, OR, COOR, OCOR, CONR, OCOOR, OCONR and a C.sub.1-C.sub.18 alkyl group, wherein R is selected from the group consisting of hydrogen, an unsubstituted or substituted carbocyclic or heterocyclic aromatic group selected from a monocyclic ring of five or six atoms, two adjacent monocyclic rings of five or six atoms, a bicyclic ring system of eight, nine or ten atoms, or a tricyclic ring system of thirteen or fourteen atoms; a substituted or unsubstituted, straight-chain or branched C.sub.1-18 alkyl group, in which one, two, three or four more CH.sub.2, CH or C groups are unreplaced or replaced by groups selected from the group consisting of CH?CH, C?C, O, S, NRCO, COO, OOC, CONR, OCOO, OCONR with the proviso that the spacer group does not contain two adjacent heteroatoms, wherein R is selected from the group consisting of hydrogen, a C.sub.1-C.sub.18 alkyl group.

2. A compound according to claim 1, in which BP.sub.1 and BP.sub.2 each independently from each other are selected from the group consisting of CH.sub.2?C(Ph)-, CH.sub.2?CWCOO, CH.sub.2?CHCOO-Ph-, CH.sub.2?CWCONH, CH.sub.2?CHO, CH.sub.2?CHOOC, Ph-CH?CH, CH.sub.2?CH-Ph-, CH.sub.2?CH-Ph-O, R.sup.3-Ph-CH?CHCOO, R.sup.3OOCCH?CH-Ph-O and 2-W-epoxyethyl, in which W represents hydrogen, chloride, phenyl or a C.sub.1-C.sub.6alkyl, and R.sup.3 represents a C.sub.1-C.sub.6alkyl with the proviso that when R.sup.3 is attached to an aryl group it may also represent hydrogen or a C.sub.1-C.sub.6alkoxy.

3. A compound according to claim 1, in which SP.sub.1, SP.sub.2 and SP.sub.3 each independently from each other represents a substituted or unsubstituted, straight-chain or branched C.sub.1-C.sub.12 alkylene group, in which one, two, three or four more CH.sub.2, CH or C groups are unreplaced or replaced by groups selected from the group consisting of CH?CH, C?C, O, S, NRCO, COO, OOC, CONR, OCOO, OCONR with the proviso that the spacer group does not contain two adjacent heteroatoms.

4. A compound according to claim 1, in which the group X.sub.1, X.sub.2, X.sub.3 and X.sub.4 each independently from each other are selected from the group consisting of O, COO, OOC, OCOO, and a single bond.

5. A compound according to claim 1, in which the groups A.sub.1 and A.sub.2 each independently from each other are preferably selected from the group consisting of hydrogen, OR, COOR, and OCOR wherein R is selected from the group consisting of C.sub.1-C.sub.18 alkyl and; furan, benzene, especially phenylene; pyridine, triazine, pyrimidine, naphthalene, phenanthrene, biphenylene or tetralin group, which are unsubstituted or substituted;

6. A LCP mixture comprising the compound of formula (I).

7. A LCP network comprising a compound according to claim 1.

8. A method of forming a LCP network comprising forming a LCP layer comprising a compound of formula (I) according to claim 1, and polymerising the LCP layer.

9. A method of manufacturing an optical or an electro-optical device comprising using a compound according to claim 1.

10. An optical or electro-optical device including a compound according to claim 1.

11. A LCP network comprising a mixture according to claim 6 in polymerised form.

12. A method of forming a LCP network comprising forming a LCP layer comprising a LCP mixture according to claim 6, and polymerising the LCP layer.

13. A method of manufacturing an optical or an electro-optical device comprising using a mixture according to claim 6.

14. An optical or electro-optical device including a mixture according to claim 6.

15. An optical or electro-optical device including a network according to claim 7.

Description

EXAMPLES

[0107] Definitions used in the examples: [0108] .sup.1H NMR: .sup.1H nuclear magnetic resonance spectroscopy [0109] DMSO-d.sub.6: dimethylsulfoxid deuterated [0110] 300 MHz: 300 MegaHertz [0111] m: multiplet, d: doublet, dd: doublet doublet, t: triplet, s: singulet [0112] DMF: dimethylformamide [0113] HCl: hydrochloric acid [0114] CH.sub.2Cl.sub.2: dichloromethane [0115] THF: tetrahydrofuran [0116] NMP: N-Methyl-2-pyrrolidon [0117] Cul: Copper iodide [0118] MgSO.sub.4: magnesium sulfate

[0119] In the following examples, the thermotropic phases are abbreviated as follow: [0120] T.sub.(CrN): transition temperature from crystal phase to nematic phase [0121] T.sub.(NI): transition temperature from nematic phase to isotropic phase

Example 1: Preparation of propyl 5-[2-[6-(3-prop-2-enovloxypropoxy)-2-naphthyl]ethynyl]-2-[6-[4-[2-[6-(3-prop-2-enoyloxypropoxy)-2-naphthyl]ethynyl]-2-propoxycarbonyl-phenoxy]hexoxy]benzoate, Compound 1

[0122] ##STR00004##

Preparation of 3-[(6-ethynyl-2-naphthyl)oxy]propan-1-ol, Compound 2

[0123] ##STR00005##

[0124] A mixture of 20 g (85.81 mmol) of 6-bromo-2-naphthol, 15.41 g (111.55 mmol) of potassium carbonate, 1.7 g (10.29 mmol) of potassium iodide and 12.16 g (128.7 mmol) of 3-chloropropanol in 50 ml of NMP is heated at 80? C. for 18 h. The solution is then cooled down and poured into 400 ml of water/HCl solution. The obtained precipitate is filtered off and washed two times with 200 ml of water. The residue was further purified by flash column chromatography over silica gel using a 1:1 mixture of hexane/ethylacetate to give 22.47 g. After recrystallization from heptane/ethylacetate (10:1), 18.6 g of compound 2 was obtained as an off-white solid

Preparation of 3-[[6-(2-trimethylsilylethynyl)-2-naphthyl]oxy]propan-1-ol, Compound 3

[0125] ##STR00006##

[0126] Bis(Triphenylphosphine)palladium (II) chloride (2.1 g, 2.99 mmol), Cul (799 mg, 4.195 mmol), and compound 2 are placed, in 83.4 ml of triethylamine. The mixture is stirred at 25? C. for 15 minutes, and (trimethylsilyl)acetylene (11.77 g, 119.8 mmol) is added. After stirring the suspension at 80? C. for 2 h, a solution of HCl is dropwise added. The mixture is stirred for 30 min, then filtered off through hyflosilica and washed three times with 100 ml of ethylacetate. The solution is extracted with ethylacetate. The combined organic layers are washed with 5 ml of water and dried with MgSO.sub.4. After concentration of the solvent under vacuum, the residue is purified by flash chromatography over silica gel using a 1:1 mixture of hexane/ethylacetate to give 13.41 g of compound 3.

Preparation of 3-[(6-ethynyl-2-naphthyl)oxy]propan-1-ol, Compound 4

[0127] ##STR00007##

[0128] 12.4 g (89.79 mmol) of potassium carbonate is added to in several portions to a solution of compound 3 in 135 ml of methanol. After stirring 1 h at room temperature, the reaction mixture is filtered off over Hyflo/silica that is then washed 3 times with 25 ml of methanol. The solution is then poured onto a solution of HCl in water and then extracted with ethylactetate. The combined organic layers are dried over MgSO.sub.4. After concentration under vacuum 10.84 g of compound 4 as a yellowish solid is obtained.

Preparation of propyl 5-iodo-2-[6-(4-iodo-2-propoxycarbonyl-phenoxy)hexoxy]benzoate, Compound 5

[0129] ##STR00008##

[0130] A mixture of 9.24 g (30.18 mmol) of propyl 2-hydroxy-5-iodo-benzoate, 5.42 g (39.24 mmol) of potassium carbonate, 601 mg (3.62 mmol) of potassium iodide and 3.68 g (15.09 mmol) of 1,6-dibromobutane in 35 ml of DMF is heated at 80? C. for 5 h. The solution is then cooled down and poured onto 400 ml of water/HCl solution. The obtained precipitate is filtered off and washed two times with 50 ml of water. A purification by recrystallization in acetonitrile give 9.44 g of compound 5 as an off-white solid.

Preparation of propyl 5-[2-[6-(3-hydroxypropoxy)-2-naphthyl]ethynyl]-2-[6-[4-[2-[6-(3-hydroxypropoxy)-2-naphthyl]ethynyl]-2-propoxycarbonyl-phenoxy]hexoxy]benzoate, Compound 6

[0131] ##STR00009##

[0132] Bis(Triphenylphosphine)palladium (II) chloride (202 mg, 0.288 mmol), Cul (109 mg, 0.576 mmol), and propyl 5-iodo-2-[6-(4-iodo-2-propoxycarbonyl-phenoxy)hexoxy]benzoate (4 g, 5.765 mmol), 8.02 ml of triethylamine (57.65 mmol) are placed in 40 ml of DMF. The mixture was stirred at 25? C. for 15 minutes, and 3-[(6-ethynyl-2-naphthyl)oxy]propan-1-ol (2.87 g, 12.68 mmol) is added. After stirring the suspension at room temperature for 8 h, a solution of HCl is added and the mixture is stirred for 30 min. The reaction mixture is then filtered off through Hyflo/silica and washed 3 times with 100 ml of ethylacetate. The solution is extracted with ethylacetate. The combined organic layers are washed with water and dried over MgSO.sub.4. After concentration of the solvent under vacuum, the residue is purified by flash chromatography over silica gel using a 1:1 mixture of hexane/ethylacetate to give 4.33 g of compound 6.

Preparation of propyl 5-[2-[6-(3-prop-2-enoyloxypropoxy)-2-naphthyl]ethynyl]-2-[6-[4-[2-[6-(3-prop-2-enoyloxypropoxy)-2-naphthyl]ethynyl]-2-propoxycarbonyl-phenoxy]hexoxy]benzoate, Compound 1

[0133] To 4.33 g (4.859 mmol) of compound 6 in 45 mL of THF and 2.65 g (26.24 mmol) of triethylamine is added 4-dimethyl aminopyridine (118.7 mg, 0.97 mmol). This solution is cooled down to 0? C. and acryloyldichloride (2.2 g, 24.29 mmol) is added dropwise. The solution is then warmed to room temperature and let it stir for 18 hours. The residue is purified by flash chromatography over silica gel using a 1:1 mixture of hexane/ethylacetate to give 1.2 g of an off-white solid compound 1.

[0134] .sup.1H NMR (400 MHz, DMSO-d6) ?: 8.08 (s, 2H), 7.82 (m, 6H), 7.80 (dd, 2H), 7.55 (dd, 2H), 7.37 (d, 2H), 7.19 (m, 4H), 6.35 (dd, 2H), 6.19 (m, 2H), 5.95 (dd, 2H), 4.32 (t, 4H), 4.20 (q, 8H), 4.10 (t, 4H), 2.16 (qt, 4H), 1.70 (m, 8H), 1.52 (m, 4H), 0.96 (t, 6H).

[0135] Liquid crystal phase Transition: Compound 1 was observed with a polarizing microscope under cross polarizers to determine its phase transition temperature. As a result, when the temperature increased, the crystalline phase changed into a nematic phase at 105.8? C. (T.sub.(CrN)) and the isotropic phase appeared to be at 125.7? C. (T.sub.(NI)).

Example 2: Preparation of propyl 5-[2-[6-(6-prop-2-enoyloxyhexoxy)-2-naphthyl]ethynyl]-2-[6-[4-[2-[6-(6-prop-2-enoyloxyhexoxy)-2-naphthyl]ethynyl]phenoxy]hexoxy]benzoate, Compound 7

[0136] ##STR00010##

Preparation of 6-[(6-bromo-2-naphthyl)oxy]hexan-1-ol, Compound 8a

[0137] ##STR00011##

[0138] The compound 8a is prepared according to the process described in example 1 for compound 2 with the proviso that 3-chloropropanol is replaced by 3-bromohexanol.

Preparation of 6-[[6-(2-trimethylsilylethynyl)-2-naphthyl]oxy]hexan-1-ol, Compound 8b

[0139] ##STR00012##

[0140] The compound 8b is prepared according to the process described in example 1 for compound 3 with the proviso that compound 2 is replaced by compound 8a.

Preparation of 6-[(6-ethynyl-2-naphthyl)oxy]hexan-1-ol, Compound 9

[0141] ##STR00013##

[0142] The compound 9 is prepared according to the process described in example 1 for compound 4 with the proviso that compound 3 is replaced by compound 8b.

Preparation of 1-(6-chlorohexoxy)-4-iodo-benzene, Compound 10

[0143] ##STR00014##

[0144] To a solution of 4-iodophenol (25 g, 113.6 mmol) in 250 ml of THF, 6-chlorohexanol (19.4 g, 142 mmol) and triphenylphospine (37.25 g, 142 mmol) are added. The mixture is cooled down to 0? C. and diisopropyl azodicarboxylate (28.72 g, 142 mmol) in 250 ml of THF is added dropwise. After the addition, the reaction is cooled down to room temperature and stirred for 18 h. The solution is then concentrated under vacuum and the residue is purified by flash chromatography over silica gel using a 1:4 mixture of hexane/ethylacetate to give 35.4 g of an off-white solid compound 10.

Preparation of propyl 5-iodo-2-[6-(4-iodophenoxy)hexoxy]benzoate, Compound 11

[0145] ##STR00015##

[0146] To a mixture of 12.05 g (39.37 mmol) of propyl 2-hydroxy-5-iodo-benzoate, 7.07 g (51.18 mmol) of potassium carbonate, 784 mg (4.73 mmol) of potassium iodide and in 40 ml of DMF is added dropwise 20 g (50.06 mmol) of 1-(6-chlorohexoxy)-4-iodo-benzene in 50 ml of DMF. After heating at 80? C. for 18 h, the solution is then cooled down and poured into 400 mL of water/HCl solution. The obtained precipitate is filtered off and purified by flash chromatography over silica gel using a 9:1 mixture of hexane/ethylacetate to give 23.3 g of a yellowish solid compound 11.

Preparation propyl 5-[2-[6-(6-hydroxyhexoxy)-2-naphthyl]ethynyl]-2-[6-[4-[2-[6-(6-hydroxyhexoxy)-2-naphthyl]ethynyl]phenoxy]hexoxy]benzoate, Compound 12

[0147] ##STR00016##

[0148] The compound 12 is prepared according to the process described in example 1 for compound 6 with the proviso that compound 5 is replaced by compound 11.

Preparation of propyl 5-[2-[6-(6-prop-2-enoyloxyhexoxy)-2-naphthyl]ethynyl]-2-[6-[4-[2-[6-(6-prop-2-enoyloxyhexoxy)-2-naphthyl]ethynyl]phenoxy]hexoxy]benzoate, Compound 7

[0149] The compound 7 is prepared according to the process described in example 1 for compound 1 with the proviso that compound 6 is replaced by the compound 12.

[0150] .sup.1H NMR (400 MHz, THF-d8) ?: 7.91 (dd, 3H), 7.70 (m, 4H), 7.60 (dd, 1H), 7.55-7.40 (m, 4H), 7.20 (m, 1H), 7.16-7.08 (m, 4H), 6.91 (d, 1H), 6.33 (dd, 2H), 6.11 (dd, 2H), 5.77 (dd, 2H), 4.22 (t, 2H), 4.11 (m, 10H), 4.02 (t, 2H), 1.9-1.4 (m, 26H), 1.03 (t, 3H).

[0151] Liquid crystal phase transition: T.sub.(CrN): 83.3? C., T.sub.(NI) 146.3? C.

Example 3: Preparation of methyl 2-[6-[2-methoxycarbonyl-4-[2-[6-(11-prop-2-enoyloxyundecoxy)-2-naphthyl]ethynyl]phenoxy]hexoxy]-5-[2-[6-(11-prop-2-enoyloxyundecoxy)-2-naphthyl]ethynyl]benzoate, Compound 14

[0152] ##STR00017##

Preparation of 11-[(6-bromo-2-naphthyl)oxy]undecan-1-ol, Compound 15

[0153] ##STR00018##

[0154] The compound 15 is prepared according to the process described in example 1 for compound 2 with the proviso that 3-chloropropanol is replaced by 11-bromoundecanol.

Preparation of 11-[[6-(2-trimethylsilylethynyl)-2-naphthyl]oxy]undecan-1-ol, Compound 16

[0155] ##STR00019##

[0156] The compound 16 is prepared according to the process described in example 1 for compound 3 with the proviso that compound 2 is replaced by compound 15.

Preparation of 11-[(6-ethynyl-2-naphthyl)oxy]undecan-1-ol, Compound 17

[0157] ##STR00020##

[0158] The compound 17 is prepared according to the process described in example 1 for compound 4 with the proviso that compound 3 is replaced by compound 16.

Preparation of methyl 5-iodo-2-[6-(4-iodo-2-methoxycarbonyl-phenoxy)hexoxy]benzoate, Compound 18

[0159] ##STR00021##

[0160] The compound 18 is prepared according to the process described in example 1 for compound 5 with the proviso that propyl 2-hydroxy-5-iodo-benzoate is replaced by methyl 2-hydroxy-5-iodo-benzoate.

Preparation of methyl 5-[2-[6-(11-hydroxyundecoxy)-2-naphthyl]ethynyl]-2-[6-[4-[2-[6-(11-hydroxyundecoxy)-2-naphthyl]ethynyl]-2-methoxycarbonyl-phenoxy]hexoxy]benzoate, Compound 19

[0161] ##STR00022##

[0162] The compound 19 is prepared according to the process described in example 1 for compound 6 with the proviso that compound 5 is replaced by compound 18.

Preparation of methyl 2-[6-[2-methoxycarbonyl-4-[2-[6-(11-prop-2-enoyloxyundecoxy)-2-naphthyl]ethynyl]phenoxy]hexoxy]-5-[2-[6-(11-prop-2-enoyloxyundecoxy)-2-naphthyl]ethynyl]benzoate, Compound 14

[0163] The compound 14 is prepared according to the process described in example 1 for compound 1 with the proviso that compound 6 is replaced by compound 19.

[0164] .sup.1H NMR (400 MHz, THF-d8) ?: 7.94 (d, 2H), 7.90 (d, 2H), 7.70 (dd, 4H), 7.60 (dd, 2H), 7.47 (dd, 2H), 7.13 (m, 6H), 6.32 (dd, 2H), 6.10 (dd, 2H), 5.78 (dd, 2H), 4.10 (m, 12H), 3.82 (s, 6H), 1.9-1.75 (m, 8H), 1.75-1.35 (m, 18H).

[0165] Liquid crystal phase transition: T.sub.(CrN): 110.6? C., T.sub.(NI): 120.8? C.

Example 4: Preparation of propyl 5-[2-[6-(5-prop-2-enoyloxypentoxy)-2-naphthyl]ethynyl]-2-[6-[4-[2-[6-(5-prop-2-enoyloxypentoxy)-2-naphthyl]ethynyl]-2-propoxycarbonyl-phenoxy]hexoxy]benzoate, Compound 20

[0166] ##STR00023##

Preparation of 5-[(6-bromo-2-naphthyl)oxy]pentan-1-ol, Compound 21

[0167] ##STR00024##

[0168] The compound 21 is prepared according to the process described in example 1 for compound 2 with the proviso that 3-chloropropanol is replaced by 5-bromopentanol.

Preparation of 5-[[6-(2-trimethylsilylethynyl)-2-naphthyl]oxy]pentan-1-ol, Compound 22

[0169] ##STR00025##

[0170] The compound 22 is prepared according to the process described in example 1 for compound 3 with the proviso that compound 2 is replaced by compound 21.

Preparation of 5-[(6-ethynyl-2-naphthyl)oxy]pentan-1-ol, Compound 23

[0171] ##STR00026##

[0172] The compound 23 is prepared according to the process described in example 1 for compound 4 with the proviso that compound 3 is replaced by compound 22.

Preparation of propyl 5-[2-[6-(5-hydroxypentoxy)-2-naphthyl]ethynyl]-2-[6-[4-[2-[6-(5-hydroxypentoxy)-2-naphthyl]ethynyl]-2-propoxycarbonyl-phenoxy]hexoxy]benzoate, Compound 24

[0173] ##STR00027##

[0174] The compound 24 is prepared according to the process described in example 1 for compound 6 with the proviso that compound 4 is replaced by compound 23.

Preparation of propyl 5-[2-[6-(5-prop-2-enoyloxypentoxy)-2-naphthyl]ethynyl]-2-[6-[4-[2-[6-(5-prop-2-enoyloxypentoxy)-2-naphthyl]ethynyl]-2-propoxycarbonyl-phenoxy]hexoxy]benzoate, Compound 20

[0175] The compound 20 is prepared according to the process described in example 1 for compound 1 with the proviso that compound 6 is replaced by compound 24.

[0176] .sup.1H NMR (400 MHz, DMSO-d6) ?: 8.07 (s, 2H), 7.80 (m, 6H), 7.71 (dd, 2H), 7.53 (dd, 2H), 7.34 (d, 2H), 7.20 (m, 4H), 6.32 (dd, 2H), 6.18 (m, 2H), 5.93 (dd, 2H), 4.14 (m, 16H), 1.73 (m, 16H), 1.52 (m, 8H), 0.96 (t, 6H) Liquid crystal phase transition: T.sub.(CrN): 123? C., T.sub.(NI) 126.9? C.

Example 5: Preparation propyl 5-[2-[6-(6-prop-2-enoyloxyhexoxy)-2-naphthyl]ethynyl]-2-[6-[4-[2-[5-(6-prop-2-enoyloxyhexoxy)-2-naphthyl]ethynyl]-2-propoxycarbonyl-phenoxy]hexoxy]benzoate, Compound 25

[0177] ##STR00028##

Preparation of propyl 5-[2-[6-(6-hydroxyhexoxy)-2-naphthyl]ethynyl]-2-[6-[4-[2-[6-(6-hydroxyhexoxy)-2-naphthyl]ethynyl]-2-propoxycarbonyl-phenoxy]hexoxy]benzoate, Compound 26

[0178] ##STR00029##

[0179] The compound 26 is prepared according to the process described in example 1 for compound 6 with the proviso that compound 4 is replaced by compound 9.

Preparation propyl 5-[2-[6-(6-prop-2-enoyloxyhexoxy)-2-naphthyl]ethynyl]-2-[6-[4-[2-[5-(6-prop-2-enoyloxyhexoxy)-2-naphthyl]ethynyl]-2-propoxycarbonyl-phenoxy]hexoxy]benzoate, Compound 25

[0180] The compound 25 is prepared according to the process described in example 1 for compound 1 with the proviso that compound 6 is replaced by compound 26.

[0181] .sup.1H NMR (400 MHz, DMSO-d6) ?: 8.07 (s, 2H), 7.80 (m, 6H), 7.71 (dd, 2H), 7.53 (dd, 2H), 7.34 (d, 2H), 7.20 (m, 4H), 6.32 (dd, 2H), 6.18 (m, 2H), 5.93 (dd, 2H), 4.13 (m, 16H), 1.73 (m, 16H), 1.50 (m, 12H), 0.96 (t, 6H) Liquid crystal phase transition: T.sub.(CrN): 103.5? C., T.sub.(NI): 117? C.

Example 6: Preparation of propyl 5-[2-[6-(6-prop-2-enoyloxyhexoxy)-2-naphthyl]ethynyl]-2-[4-[4-[2-[6-(6-prop-2-enoyloxyhexoxy)-2-naphthyl]ethynyl]phenoxy]butoxy]benzoate, Compound 30

[0182] ##STR00030##

Preparation of propyl 5-iodo-2-[4-(4-iodophenoxy)butoxy]benzoate, Compound 31

[0183] ##STR00031##

[0184] The compound 31 is prepared according to the process described in example 2 for compound 11 with the proviso that 1-(6-chlorohexoxy)-4-iodo-benzene is replaced by 1-(6-chlorobutoxy)-4-iodo-benzene.

Preparation of propyl 5-[2-[6-(6-hydroxyhexoxy)-2-naphthyl]ethynyl]-2-[4-[4-[2-[6-(6-hydroxyhexoxy)-2-naphthyl]ethynyl]phenoxy]butoxy]benzoate, Compound 32

[0185] ##STR00032##

[0186] The compound 32 is prepared according to the process described in example 2 for compound 12 with the proviso that compound 11 is replaced by compound 31.

Preparation of propyl 5-[2-[6-(6-prop-2-enoyloxyhexoxy)-2-naphthyl]ethynyl]-2-[4-[4-[2-[6-(6-prop-2-enoyloxyhexoxy)-2-naphthyl]ethynyl]phenoxy]butoxy]benzoate, Compound 30

[0187] The compound 30 is prepared according to the process described in example 1 for compound 1 with the proviso that compound 6 is replaced by compound 31.

[0188] .sup.1H NMR (400 MHz, DMSO-d6) ?: 8.05 (s, 2H), 7.82 (m, 4H), 7.72 (dd, 2H), 7.52 (m, 4H), 7.34 (s, 2H), 7.21 (m, 3H), 7.00 (d, 2H), 6.32 (dd, 2H), 6.17 (m, 2H), 5.92 (dd, 2H), 4.14 (m, 14H), 1.92 (m, 4H), 1.79-1.60 (m, 10H), 1.44 (m, 5H), 0.96 (t, 6H) Liquid crystal phase transition: T.sub.(CrN): 85.1? C., T.sub.(NI): 158.3? C.

Example 7: Preparation of ethyl 2-[6-[2-ethoxycarbonyl-4-[2-[6-(3-prop-2-enoyloxypropoxy)-2-naphthyl]ethynyl]phenoxy]hexoxy]-5-[2-[6-(3-prop-2-enoyloxypropoxy)-2-naphthyl]ethynyl]benzoate, Compound 33

[0189] ##STR00033##

Preparation of ethyl 2-[6-(2-ethoxycarbonyl-4-iodo-phenoxy)hexoxy]-5-iodo-benzoate, Compound 34

[0190] ##STR00034##

[0191] The compound 34 is prepared according to the process described in example 1 for compound 5 with the proviso that propyl 2-hydroxy-5-iodo-benzoate is replaced by ethyl 2-hydroxy-5-iodo-benzoate.

Preparation of ethyl 2-[6-[2-ethoxycarbonyl-4-[2-[6-(3-hydroxypropoxy)-2-naphthyl]ethynyl]phenoxy]hexoxy]-5-[2-[6-(3-hydroxypropoxy)-2-naphthyl]ethynyl]benzoate, Compound 35

[0192] ##STR00035##

[0193] The compound 35 is prepared according to the process described in example 1 for compound 6 with the proviso that compound 5 is replaced by compound 34.

Preparation of ethyl 2-[6-[2-ethoxycarbonyl-4-[2-[6-(3-prop-2-enoyloxypropoxy)-2-naphthyl]ethynyl]phenoxy]hexoxy]-5-[2-[6-(3-prop-2-enoyloxypropoxy)-2-naphthyl]ethynyl]benzoate Compound 33

[0194] The compound 33 is prepared according to the process described in example 1 for compound 1 with the proviso that compound 6 is replaced by compound 35.

[0195] .sup.1H NMR (400 MHz, DMSO-d6) ?: 8.07 (s, 2H), 7.82 (m, 6H), 7.70 (dd, 2H), 7.54 (dd, 2H), 7.37 (d, 2H), 7.20 (m, 4H), 6.36 (dd, 2H), 6.19 (m, 2H), 5.95 (dd, 2H), 4.25 (m, 12H), 4.09 (t, 4H), 2.16 (qt, 4H), 1.76 (m, 4H), 1.53 (m, 4H), 1.30 (t, 6H) Liquid crystal phase transition: T.sub.(CrN): 123.5? C., T.sub.(NI): 143? C.

Example 8: Preparation of an Orientation Layer Using Photoalignment Materials

[0196] A glass substrate is spin-coated with a Photoalignment Composition (3% solid content of a photoaligning material in cyclopentanone as described in patent publication WO2012/085048: photoactive polymer materials use as orienting layer for liquid crystals).

[0197] The film is dried at 180? C. for 10 min and the resulting film thickness is about 100 nm. Then, the film is exposed to aligning light, which is collimated and linearly polarized UV (LPUV) light (280-320 nm) with 250 mJ/cm.sup.2. The plane of polarization is 0? with regard to a reference edge on the substrate.

Example 9: Preparation of Compound 1 Film

[0198] A 14.0 w % solution is prepared by mixing the 13.552 w % compound 1, 0.140 w % of 2,6-di-tert-butyl-4-methylphenol, 0.280 w % of Irgacure? 369, (Irgacure? 369, having the chemical structure of 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1), 0.028 w % of BYK? 378 (solvent-free silicone levelling agent) in cyclopentanone and stirred thoroughly till the solid is completely dissolved at room temperature. The above polymer solution was spin-coated onto a glass plate with the orientation layer of Example 8 to form a liquid crystal film.

[0199] This film is dried at 108? C. for 1 min 30 onto a temperature controlled hot plate. The sample is cooled down to room temperature and then photo-polymerised by irradiation with UV light using a Mercury lamp for approximately 2 min at room temperature, 20-25? C. under N.sub.2 atmosphere to fix the orientation state of the liquid crystal.

[0200] The resulting film of example 9 exhibited a very well oriented nematic mesophase at room temperature.

Example 10: Preparation of Compound 25 Film

[0201] A 15.0 w % solution is prepared by mixing the 14.775 w % compound 25, 0.075 w % of 2,6-di-tert-butyl-4-methylphenol, 0.150 w % of Irgacure? 369 in cyclohexanone and stirred thoroughly till the solid is completely dissolved at room temperature. The above polymer solution was spin-coated onto a glass plate with the orientation layer of Example 8 to form a liquid crystal film. This film is dried at 110? C. for 5 min onto a temperature controlled hot plate. The sample is cooled down to room temperature, 20-25? C. and then photo-polymerised by irradiation with UV light using a Mercury lamp for approximately 2 min at room temperature under N.sub.2 atmosphere to fix the orientation state of the liquid crystal.

[0202] The resulting film of example 10 exhibited a very well oriented nematic mesophase at room temperature.

Example 11: Preparation of Compound 4 Film

[0203] A 7.5 w % solution is prepared by mixing the 7.3875 w % compound 4, 0.0375 w % of 2,6-di-tert-butyl-4-methylphenol, 0.075 w % of Irgacure? 369 in cyclohexanone and stirred thoroughly till the solid is completely dissolved at room temperature. The above polymer solution was spin-coated onto a glass plate with the orientation layer of Example 8 to form a liquid crystal film. This film is dried at 120? C. for 5 min onto a temperature controlled hot plate. The sample is cooled down to room temperature and then photo-polymerised by irradiation with UV light using a Mercury lamp for approximately 2 min at room temperature under N.sub.2 atmosphere to fix the orientation state of the liquid crystal.

[0204] The resulting film of example 11 exhibited an oriented nematic mesophase with a medium quality of alignment at room temperature.

Example 12: Preparation of Compound 7 Film

[0205] A 15 w % solution is prepared by mixing the 14.370 w % compound 7, 0.300 w % of 2,6-di-tert-butyl-4-methylphenol, 0.300 w % of Irgacure? 369 in cyclopentanone/3-dioxolane 60/40 and stirred thoroughly till the solid is completely dissolved at room temperature. The above polymer solution was spin-coated onto a glass plate with the orientation layer of Example 8 to form a liquid crystal film. This film is dried at 130? C. for 5 min onto a temperature controlled hot plate. The sample is cooled down to room temperature and then photo-polymerised by irradiation with UV light using a Mercury lamp for approximately 2 min at room temperature, 20-25? C. under N.sub.2 atmosphere to fix the orientation state of the liquid crystal.

[0206] The resulting film of example 12 exhibited a very well oriented nematic mesophase at room temperature.

Example 13: Preparation of Compound 20 Film

[0207] A 15 w % solution is prepared by mixing the 14.520 w % compound 20, 0.150 w % of 2,6-di-tert-butyl-4-methylphenol, 0.300 w % of Irgacure? 369 and 0.030 wt % of BYK @ 378 in cyclopentanone and stirred thoroughly till the solid is completely dissolved at room temperature. The above polymer solution was spin-coated onto a glass plate with the orientation layer of Example 8 to form a liquid crystal film. This film is dried at 108? C. for 1 min 30 onto a temperature controlled hot plate. The sample is cooled down to room temperature and then photo-polymerised by irradiation with UV light using a Mercury lamp for approximately 2 min at room temperature, 20-25? C. under N.sub.2 atmosphere to fix the orientation state of the liquid crystal.

[0208] The resulting film of example 13 exhibited a very well oriented nematic mesophase at room temperature.

Example 14: Preparation of Compound 30 Film

[0209] A 15 w % solution is prepared by mixing the 14.520 w % compound 30, 0.150 w % of 2,6-di-tert-butyl-4-methylphenol, 0.300 w % of Irgacure? 369 and 0.030 wt % of Tego Flow 0.300 in cyclopentanone and stirred thoroughly till the solid is completely dissolved at room temperature. The above polymer solution was spin-coated onto a glass plate with the orientation layer of Example 8 to form a liquid crystal film. This film is dried at 148? C. for 5 min onto a temperature controlled hot plate. The sample is cooled down to room temperature and then photo-polymerised by irradiation with UV light using a Mercury lamp for approximately 2 min at room temperature, 20-25? C. under N.sub.2 atmosphere to fix the orientation state of the liquid crystal.

[0210] The resulting film of example 14 exhibited a very well oriented nematic mesophase at room temperature.

Example 15

[0211] The retardation at 550 nm of the sample described in example 9, example 10, example 11, example 12, example 14 are measured with an Ellipsometer. The thicknesses of the samples are measured by a contact stylus profilometer. The birefringence (?n) was obtained from the determined retardation and thickness values according to the formula (?n=Retardation/Thickness). The values are listed in Table 1.

TABLE-US-00001 TABLE 1 Thickness Retardation at Example (nm) 550 nm ?n 9 (compound 1) 1170 ? 30 450.9 0.39 ? 0.01 10 (compound 25) 780 ? 30 238.7 0.31 ? 0.01 11 (compound 14) 220 ? 20 70.8 0.32 ? 0.02 12 (compound 7) 1320 ? 30 472.5 0.36 ? 0.01 14 (compound 30) 1050 ? 30 362.1 0.35 ? 0.01

[0212] The films of Example 9, 10, 11, 12, 14 have high birefringence in the range from 0.31 to 0.39. These new LCPs could be used for preparing phase retarder optical films as Quarter-Waveplate (QWP) and Half-Waveplate (HWP). A retarder transmits light and modifies its polarization state and is widely used in various display application or in security elements.

[0213] The particularly high birefringence of these new LCPs leads to a significant thickness reduction of the retarder's films.

[0214] As an example, Table 2 shows the required thickness to get a quarter waveplate (14) retarder (QWP) and Half-Waveplate (12) retarder (HWP) at 550 nm with the compounds 1, 25, 14, 7, 30 used in respectively example 9, 10, 11, 12 and 14.

TABLE-US-00002 TABLE 2 Required Thickness for Required Thickness for QWP at 550 nm HWP at 550 nm Example (nm) (nm) 9 353 706 10 444 888 11 430 860 12 382 764 14 393 786