Patent Application
20160222293
The invention relates to mesogenic compounds of formula I
wherein R11, R12, CG1, MG1 and Sp1 have the meaning given herein below, to the use of mesogenic compounds of formula I in liquid crystal media and particular to flexoelectric liquid crystal devices comprising a liquid crystal medium according to the present invention.
Liquid Crystal Displays (LCDs) are widely used to display information. LCDs are used for direct view displays, as well as for projection type displays. The electro-optical mode which is employed for most displays still is the twisted nematic (TN)-mode with its various modifications. Besides this mode, the super twisted nematic (STN)-mode and more recently the optically compensated bend (OCB)-mode and the electrically controlled birefringence (ECB)-mode with their various modifications, as e. g. the vertically aligned nematic (VAN), the patterned ITO vertically aligned nematic (PVA)-, the polymer stabilized vertically aligned nematic (PSVA)-mode and the multi domain vertically aligned nematic (MVA)-mode, as well as others, have been increasingly used. All these modes use an electrical field, which is substantially perpendicular to the substrates, respectively to the liquid crystal layer. Besides these modes there are also electro-optical modes employing an electrical field substantially parallel to the substrates, respectively the liquid crystal layer, like e.g. the In Plane Switching (short IPS) mode (as disclosed e.g. in DE 40 00 451 and EP 0 588 568) and the Fringe Field Switching (FFS) mode. Especially the latter mentioned electro-optical modes, which have good viewing angle properties and improved response times, are increasingly used for LCDs for modern desktop monitors and even for displays for TV and for multimedia applications and thus are competing with the TN-LCDs.
Further to these displays, new display modes using cholesteric liquid crystals having a relatively short cholesteric pitch have been proposed for use in displays exploiting the so called “flexo-electric” effect. The term “liquid crystal”, “mesomorphic compound” or “mesogenic compound” (also shortly referred to as “mesogen”) means a compound that under suitable conditions of temperature, pressure and concentration can exist as a mesophase (nematic, smectic, etc.) or in particular as a LC phase. Non-amphiphilic mesogenic compounds comprise for example one or more calamitic, banana-shaped or discotic mesogenic groups.
Flexoelectric liquid crystal materials are known in prior art. The flexoelectric effect is described inter alia by Chandrasekhar, “Liquid Crystals”, 2nd edition, Cambridge University Press (1992) and P. G. deGennes et al., “The Physics of Liquid Crystals”, 2nd edition, Oxford Science Publications (1995).
In these displays the cholesteric liquid crystals are oriented in the “uniformly lying helix” arrangement (ULH), which also give this display mode its name. For this purpose, a chiral substance which is mixed with a nematic material induces a helical twist transforming the material into a chiral nematic material, which is equivalent to a cholesteric material. The term “chiral” in general is used to describe an object that is non-superimposable on its mirror image. “Achiral” (non-chiral) objects are objects that are identical to their mirror image. The terms chiral nematic and cholesteric are used synonymously in this application, unless explicitly stated otherwise. The pitch induced by the chiral substance (P0) is in a first approximation inversely proportional to the concentration (c) of the chiral material used. The constant of proportionality of this relation is called the helical twisting power (HTP) of the chiral substance and defined by equation (1)
HTP≡1/(c·P0) (1)
wherein
c is the concentration of the chiral compound.
The uniform lying helix texture is realized using a chiral nematic liquid crystal with a short pitch, typically in the range from 0.2 μm to 1 μm, preferably of 1.0 μm or less, in particular of 0.5 μm or less, which is unidirectional aligned with its helical axis parallel to the substrates, e. g. glass plates, of a liquid crystal cell. In this configuration the helical axis of the chiral nematic liquid crystal is equivalent to the optical axis of a birefringent plate.
If an electrical field is applied to this configuration normal to the helical axis the optical axis is rotated in the plane of the cell, similar as the director of a ferroelectric liquid crystal rotate as in a surface stabilized ferroelectric liquid crystal display. The flexoelectric effect is characterized by fast response times typically ranging from 6 μs to 100 μs. It further features excellent grey scale capability.
The field induces a splay bend structure in the director which is accommodated by a tilt in the optical axis. The angle of the rotation of the axis is in first approximation directly and linearly proportional to the strength of the electrical field. The optical effect is best seen when the liquid crystal cell is placed between crossed polarizers with the optical axis in the unpowered state at an angle of 22.5° to the absorption axis of one of the polarizers. This angle of 22.5° is also the ideal angle of rotation of the electric field, as thus, by the inversion the electrical field, the optical axis is rotated by 45° and by appropriate selection of the relative orientations of the preferred direction of the axis of the helix, the absorption axis of the polarizer and the direction of the electric field, the optical axis can be switched from parallel to one polarizer to the center angle between both polarizers. The optimum contrast is then achieved when the total angle of the switching of the optical axis is 45°. In that case the arrangement can be used as a switchable quarter wave plate, provided the optical retardation, i. e. the product of the effective birefringence of the liquid crystal and the cell gap, is selected to be the quarter of the wave length. In this context the wavelength referred to is 550 nm, the wavelength for which the sensitivity of the human eye is highest, unless explicitly stated otherwise.
The angle of rotation of the optical axis (φ) is given in good approximation by formula (2)
tan φ=ēP0E/(2πK) (2)
wherein
This angle of rotation is half the switching angle in a flexoelectric switching element.
The response time (τ) of this electro-optical effect is given in good approximation by formula (3)
τ=[P0/(2π)]2·γ/K (3)
wherein
There is a critical field (Ec) to unwind the helix, which can be obtained from equation (4)
E
c=(π2/P0)·[k22/(∈0·Δ∈)]1/2 (4)
wherein
In this mode, however several problems still have to be resolved, which are, amongst others, difficulties in obtaining the required uniform orientation, an unfavourably high voltage required for addressing, which is incompatible with common driving electronics, a not really dark “off state”, which deteriorates the contrast, and, last not least, a pronounced hysteresis in the electro-optical characteristics.
A relatively new display mode, the so-called uniformly standing helix (USH) mode, may be considered as an alternative mode to succeed the IPS, as it can show improved black levels, even compared to other display mode providing wide viewing angles (e.g. IPS, VA etc.).
For the USH mode, like for the ULH mode, flexoelectric switching has been proposed, using bimesogenic liquid crystal materials. Bimesogenic compounds are known in general from prior art (cf. also Hori, K., Iimuro, M., Nakao, A., Toriumi, H., J. Mol. Struc. 2004, 699, 23-29). The term “bimesogenic compound” relates to compounds comprising two mesogenic groups in the molecule. Just like normal mesogens they can form many mesophases, depending on their structure. In particular compounds of formula I induce a second nematic phase, when added to a nematic liquid crystal medium.
The term “mesogenic group” means in this context, a group with the ability to induce liquid crystal (LC) phase behaviour. The compounds comprising mesogenic groups do not necessarily have to exhibit an LC phase themselves. It is also possible that they show LC phase behaviour only in mixtures with other compounds. For the sake of simplicity, the term “liquid crystal” is used hereinafter for both mesogenic and LC materials.
However, due to the unfavourably high driving voltage required, to the relatively narrow phase range of the chiral nematic materials and to their irreversible switching properties, materials from prior art are not compatible for the use with current LCD driving schemes.
For displays of the USH and ULH mode, new liquid crystalline media with improved properties are required. Especially the birefringence (Δn) should be optimized for the optical mode. The birefringence Δn herein is defined in equation (5)
Δn=ne−no (5)
wherein ne is the extraordinary refractive index and no is the ordinary refractive index, and the average refractive index nav, is given by the following equation (6).
n
av.=[(2no2+ne2)/3]1/2 (6)
The extraordinary refractive index ne and the ordinary refractive index no can be measured using an Abbé refractometer. Δn can then be calculated from equation (5).
Furthermore, for displays utilizing the USH or ULH mode the optical retardation d*Δn (effective) of the liquid crystal media should preferably be such that the equation (7)
sin2(π·d·Δn/λ)=1 (7)
wherein
is satisfied. The allowance of deviation for the right hand side of equation (7) is +/−3%.
The wave length of light generally referred to in this application is 550 nm, unless explicitly specified otherwise.
The cell gap of the cells preferably is in the range from 1 μm to 20 μm, in particular within the range from 2.0 μm to 10 μm.
For the ULH/USH mode, the dielectric anisotropy (Δ∈) should be as small as possible, to prevent unwinding of the helix upon application of the addressing voltage. Preferably Δ∈ should be slightly higher than 0 and very preferably be 0.1 or more, but preferably 10 or less, more preferably 7 or less and most preferably 5 or less. In the present application the term “dielectrically positive” is used for compounds or components with Δ∈>3.0, “dielectrically neutral” with −1.5≦Δ∈≦3.0 and “dielectrically negative” with Δ∈<−1.5. Δ∈ is determined at a frequency of 1 kHz and at 20° C. The dielectric anisotropy of the respective compound is determined from the results of a solution of 10% of the respective individual compound in a nematic host mixture. In case the solubility of the respective compound in the host medium is less than 10% its concentration is reduced by a factor of 2 until the resultant medium is stable enough at least to allow the determination of its properties. Preferably the concentration is kept at least at 5%, however, in order to keep the significance of the results a high as possible. The capacitance of the test mixtures are determined both in a cell with homeotropic and with homogeneous alignment. The cell gap of both types of cells is approximately 20 μm. The voltage applied is a rectangular wave with a frequency of 1 kHz and a root mean square value typically of 0.5 V to 1.0 V, however, it is always selected to be below the capacitive threshold of the respective test mixture.
Δ∈ is defined as (∈∥−∈⊥), whereas ∈av. is (∈∥+2∈⊥)/3. The dielectric permittivity of the compounds is determined from the change of the respective values of a host medium upon addition of the compounds of interest. The values are extrapolated to a concentration of the compounds of interest of 100%. A typical host mixture is disclosed in H. J. Coles et al., J. Appl. Phys. 2006, 99, 034104 and has the composition given in the table.
Besides the above mentioned parameters, the media have to exhibit a suitably wide range of the nematic phase, a rather small rotational viscosity and an at least moderately high specific resistivity.
Similar liquid crystal compositions with short cholesteric pitch for flexoelectric devices are known from EP 0 971 016, GB 2 356 629 and Coles, H. J., Musgrave, B., Coles, M. J., and Willmott, J., J. Mater. Chem., 11, p. 2709-2716 (2001). EP 0 971 016 reports on mesogenic estradiols, which, as such, have a high flexoelectric coefficient. GB 2 356 629 suggests the use of bimesogenic compounds in flexoelectric devices. The flexoelectric effect herein has been investigated in pure cholesteric liquid crystal compounds and in mixtures of homologous compounds only so far. Most of these compounds were used in binary mixtures consisting of a chiral additive and a nematic liquid crystal material being either a simple, conventional monomesogenic material or a bimesogenic one. These materials do have several drawbacks for practical applications, like insufficiently wide temperature ranges of the chiral nematic—or cholesteric phase, too small flexoelectric ratios, small angles of rotation.
Symmetrical dimeric compounds showing liquid crystalline behaviour are disclosed in Joo-Hoon Park et al. “Liquid Crystalline Properties of Dimers Having o-, m- and p-Positional Molecular structures”, Bill. Korean Chem. Soc., 2012, Vol. 33, No. 5, pp. 1647-1652.
One aim of the invention was to provide improved flexoelectric devices that exhibit high switching angles and fast response times. Another aim was to provide liquid crystal materials with advantageous properties, in particular for use in flexoelectric displays that enable good uniform alignment over the entire area of the display cell without the use of a mechanical shearing process, good contrast, high switching angles and fast response times also at low temperatures. The liquid crystal mixtures and preferably also the single compounds should exhibit low melting points, broad chiral nematic phase ranges, short temperature independent pitch lengths and high flexoelectric coefficients. Other aims of the present invention are immediately evident to the person skilled in the art from the following detailed description.
The inventors have found out that the above aims can be surprisingly achieved by providing mesogenic compounds according to the present invention. These compounds, when used in chiral nematic liquid crystal mixtures, lead to low melting points, broad chiral nematic phases. In particular, they exhibit relatively high values of the elastic constant k11, low values of the bend elastic constant k33 and high values of the flexoelectric coefficient.
Thus, the present invention relates to mesogenic compounds of formula I
wherein
In a preferred embodiment
Preferably in formula I
wherein one or more H atoms in —(CH2)n— may independently of each other optionally be replaced by F or CH3 and/or one or more non-adjacent —CH2— groups may be replaced by —O—.
Some preferred embodiments of the mixtures according to the invention are indicated below.
Preferred compounds of formula I are compounds in which
-A11-(Z1-A12)k- II
wherein
Especially preferred are compounds of formula I wherein the mesogenic group MG1 comprises one, two or three six-membered rings, preferably two or three six-membered rings.
A smaller group of preferred mesogenic groups MG1 of formula II is listed below. For reasons of simplicity, Phe in these groups is 1,4-phenylene or alkyl-1,4-phenylene, PheL is a 1,4-phenylene group which is substituted by 1 to 4 groups L, with L being preferably F, Cl, CN, OH, NO2 or an optionally fluorinated alkoxy or alkanoyl group with 1 to 7 C atoms, very preferably F, Cl, CN, OH, NO2, CH3, C2H5, OCH3, OC2H5, COCH3, COC2H5, COOCH3, COOC2H5, CF3, OCF3, OCHF2, OC2F5, in particular F, Cl, CN, CH3, C2H5, OCH3, COCH3 and OCF3, most preferably F, Cl, CH3, OCH3 and COCH3 and Cyc is 1,4-cyclohexylene. This list comprises the subformulae shown below as well as their mirror images
-Phe-Z-Phe- II-1
-Phe-Z-Cyc- II-2
-Cyc-Z-Cyc- II-3
-Phe-Z-PheL- II-4
-PheL-Z-Phe- II-5
-PheL-Z-Cyc- II-6
-PheL-Z-PheL- II-7
-Phe-Z-Phe-Z-Phe- II-8
-Phe-Z-Phe-Z-Cyc- II-9
-Phe-Z-Cyc-Z-Phe- II-10
-Cyc-Z-Phe-Z-Cyc- II-11
-Phe-Z-Cyc-Z-Cyc- II-12
-Cyc-Z-Cyc-Z-Cyc- II-13
-Phe-Z-Phe-Z-PheL- II-14
-Phe-Z-PheL-Z-Phe- II-15
-PheL-Z-Phe-Z-Phe- II-16
-PheL-Z-Phe-Z-PheL- II-17
-PheL-Z-PheL-Z-Phe- II-18
-PheL-Z-PheL-Z-PheL- II-19
-Phe-Z-PheL-Z-Cyc- II-20
-Phe-Z-Cyc-Z-PheL- II-21
-Cyc-Z-Phe-Z-PheL- II-22
-PheL-Z-Cyc-Z-PheL- II-23
-PheL-Z-PheL-Z-Cyc- II-24
-PheL-Z-Cyc-Z-Cyc- II-25
-Cyc-Z-PheL-Z-Cyc- II-26
wherein preferably
Particularly preferred are the sub-formulae II-1, II-4, II-5, II-7, II-8, II-14, II-15, II-16, II-17, II-18 and II-19 and most preferred is the sub-formula II-1.
In these preferred groups Z in each case independently has one of the meanings of Z1 as given under formula I. Preferably one of Z is —COO—, —OCO—, —CH2—O—, —O—CH2—, —CF2—O— or —O—CF2—, more preferably —COO—, —O—CH2— or —CF2—O—, and the others preferably are a single bond.
Very preferably the mesogenic group MG′ is selected from the following group of formulae IIa to IIo and their mirror images
wherein
L is in each occurrence independently of each other R, F or Cl, preferably R or F,
r is in each occurrence independently of each other 0, 1, 2 or 3, preferably 0, 1 or 2.
The group
in these preferred formulae is very preferably denoting
furthermore
wherein
L is in each occurrence independently of each other R, F or Cl,
R is alkyl having 1 to 5 C-atoms, preferably n-alkyl, more preferably methyl or ethyl.
Particularly preferred are the sub-formulae IIa, IIb and IIc.
Preferred are compounds of formula I wherein the mesogenic group MG1 comprises one, two or three six-membered rings, preferably two or three six-membered rings. Preferably MG1 comprises one, two or three six-membered rings, preferably two or three six-membered rings.
Preferred are compounds of formula I wherein the cyclic group CG1 and is a five-, six- or seven-membered ring or an annellated ring-system comprising at least one of such rings, preferably a six-membered ring.
Preferred are compounds of formula I wherein the cyclic group CG1 and is a five-, six- or seven-membered ring or an annellated ring-system comprising at least one of such rings, preferably a six-membered ring.
Especially preferred are compounds of formula I wherein the cyclic group CG1 and is selected from the following group of formulae IIa′ to IIh′ and the mirror images of formulae IIb′, IIe′ and IIf′
In one preferred embodiment of the present invention are compounds of formula I, wherein the cyclic group CG1 and is selected from the group of formulae IIa′ to IIc′ and their mirror images and R12 is H, CH3 or CF3, preferably H.
Preferably R11 and R12 in formula I are selected of H, F, Cl, CN, NO2, OCH3, COCH3, COC2H5, COOCH3, COOC2H5, CF3, C2F5, OCF3, OCHF2, and OC2F5, in particular of H, F, Cl, CN, OCH3 and OCF3, especially of H, F, CN and OCF3.
In case of compounds with a non-polar group, R11 and R12 are preferably alkyl with up to 15 C atoms or alkoxy with 1 to 15 C atoms.
If R11 or R12 is an alkyl or alkoxy radical, i.e. where the terminal CH2 group is replaced by —O—, this may be straight-chain or branched. It is preferably straight-chain, has 2, 3, 4, 5, 6, 7 or 8 carbon atoms and accordingly is preferably ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy or octoxy, furthermore methyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy or tetradecoxy, for example.
Oxaalkyl, i.e. where one CH2 group is replaced by —O—, is preferably straight-chain 2-oxapropyl (=methoxymethyl), 2-(=ethoxymethyl) or 3-oxabutyl (=2-methoxyethyl), 2-, 3- or 4-oxapentyl, 2-, 3-, 4- or 5-oxahexyl, 2-, 3-, 4-, 5- or 6-oxaheptyl, 2-, 3-, 4-, 5-, 6- or 7-oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl or 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-oxadecyl, for example.
In case of a compounds with a terminal polar group, R11 and R12 are selected from CN, NO2, halogen, OCH3, OCN, SCN, CORx, COORx or a mono- oligo- or polyfluorinated alkyl or alkoxy group with 1 to 4 C atoms. Rx is optionally fluorinated alkyl with 1 to 4, preferably 1 to 3 C atoms. Halogen is preferably F or Cl, more preferably F.
Especially preferably R11 and R12 in formula I are selected of H, F, Cl, CN, NO2, OCH3, COCH3, COC2H5, COOCH3, COOC2H5, CF3, C2F5, OCF3, OCHF2, and OC2F5, in particular of H, F, Cl, CN, OCH3 and OCF3, especially of H, F, CN and OCF3.
In addition, compounds of formula I containing an achiral branched group R11 and/or R12 may occasionally be of importance, for example, due to a reduction in the tendency towards crystallisation. Branched groups of this type generally do not contain more than one chain branch. Preferred achiral branched groups are isopropyl, isobutyl (=methylpropyl), isopentyl (=3-methylbutyl), isopropoxy, 2-methyl-propoxy and 3-methylbutoxy.
The spacer group Sp1 is preferably a linear or branched alkylene group having 1, 3 or 5 to 40 C atoms, in particular 1, 3 or 5 to 25 C atoms, very preferably 1, 3 or 5 to 15 C atoms, and most preferably 5 to 15 C atoms, in which, in addition, one or more non-adjacent and non-terminal CH2 groups may be replaced by —O—, —S—, —NH—, —N(CH3)—, —CO—, —O—CO—, —S—CO—, —O—COO—, —CO—S—, —CO—O—, —CH(halogen)-, —CH(CN)—, —CH═CH— or —C≡C—.
“Terminal” CH2 groups are those bound to the respective linking group “X11” and/or “X11” or directly to the mesogenic group MG1 and/or to the cyclic group CG1. Accordingly, “non-terminal” CH2 groups are not bound to the respective linking group “X11” and/or “X12” or directly to the respective group MG1 and/or CG1.
Typical spacer groups are for example —(CH2)o—, —(CH2CH2O)p—CH2CH2—, with o being an integer from 5 to 40, in particular from 5 to 25, very preferably from 5 to 15, and p being an integer from 1 to 8, in particular 1, 2, 3 or 4.
Preferred spacer groups are pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, diethyleneoxyethylene, dimethyleneoxybutylene, pentenylene, heptenylene, nonenylene and undecenylene, for example.
Especially preferred are inventive compounds of formula I wherein Sp is denoting alkylene with 5 to 15 C atoms. Straight-chain alkylene groups are especially preferred.
Preferred are spacer groups, which are straight-chain alkylene with odd numbers of C atoms, preferably a having 5, 7, 9, 11, 13 or 15 C atoms, very preferred are straight-chain alkylene spacers having 7, 9, and 11 C atoms.
In another embodiment of the present invention the spacer groups are straight-chain alkylenes with even numbers of C atoms, preferably having 6, 8, 10, 12 and 14 C atoms. This embodiment is particularly preferred if one of X11 and X12 consists of one atom, i.e. is —S— or —O—, or of three atoms, e.g. is —S—CO—, —S—CO—S— or —S—CS—S—, and the other does not consist of one or three C atoms.
In a preferred embodiment of the present invention the inventive compounds of formula I comprise Sp1 is denoting complete deuterated alkylene with 5 to 15 C atoms. Very preferred are deuterated straight-chain alkylene groups. Most preferred are partially deuterated straight-chain alkylene groups.
One preferred embodiment of the present invention are compounds of formula I wherein the mesogenic groups R11-MG1-X11— and R12—CG1-X12— are identical to one another.
Another preferred embodiment of the present invention are compounds of formula I wherein R11-MG1-X11 and R12—CG1-X12— in formula I are different from each other.
Preferred compounds of formula I are selected from the group of compounds of formulae IA to IG, preferably of formulae IA and/or ID, most preferably of formula ID,
wherein
LG1 is —X11—Spd1-X12—,
and
the other parameters have the respective meanings given above including the preferred meanings,
preferably at least one of the 1,3-phenylene rings is substituted by an alkyl group R and/or an alkoxy group (R—O) and/or by one or more F or Cl-atoms, preferably by one alkyl group and/or one or more F atoms and all of the 1,4-phenylene rings are optionally further substituted by one or more F or Cl-atoms, preferably at most by one CI or by one or two F-atoms each, and
Particularly preferred compounds of formula IA are selected from the group of compounds of formulae IA-1 to IA-3
wherein the parameters have the respective meanings given above including the preferred meanings and preferably
LG1 is —OC—O—(CH2)n—O—CO—.
Particularly preferred compounds of formula IB are selected from the group of compounds of formulae IB-1 to IB-3
wherein the parameters have the respective meanings given above including the preferred meanings and preferably
LG1 is —OC—O—(CH2)n—O—CO—.
Particularly preferred compounds of formula IC are selected from the group of compounds of formulae IC-1 and IC-2
wherein the parameters have the respective meanings given above including the preferred meanings and preferably
LG1 is —OC—O—(CH2)n—O—CO—.
Compounds of formula ID are very much preferred. And of these particularly preferred compounds are selected from the group of compounds of formulae ID-1 and ID-2
wherein the parameters have the respective meanings given above including the preferred meanings and preferably
LG′ is —OC—O—(CH2)n—O—CO—.
Particularly preferred compounds of formula IF are selected from the group of compounds of formulae IF-1 and IF-2
wherein the parameters have the respective meanings given above including the preferred meanings.
Particularly preferred compounds of formula IG are selected from the group of compounds of formulae IGF-1 and IG-2
wherein the parameters have the respective meanings given above including the preferred meanings.
Particularly preferred compounds are selected from the group of formulae given above, which bear 0, 2, 4 or 5 F atoms in lateral positions.
In a preferred embodiment of the present invention R11 is OCF3 or CN, preferably CN, and R12 is OCF3, F or CN, preferably also CN.
The compounds of formula I can be synthesized according to or in analogy to methods which are known per se and which are described in standard works of organic chemistry such as, for example, Houben-Weyl, Methoden der organischen Chemie, Thieme-Verlag, Stuttgart. A preferred method of preparation can be taken from the following synthesis schemes.
The compounds of formula I are preferably accessible according to the following general reaction schemes.
wherein n is an integer from 3 to 15.
a) DCC, DMAP, DCM
All phenylene moieties shown in this scheme and in the following schemes may independently of each other be optionally bearing one, two or three, preferably by no or one, F— or Cl—, preferably F—, atom.
An exemplary reaction scheme for the preparation of such a fluorinated compound is shown in the following scheme.
wherein n is as defined under Scheme I.
a) Pd(PPh3)Cl2, THF, NaCO3, H2O
b) DCC, DMAP, DCM,
c) DCC, DMAP, DCM
wherein n is as defined under Scheme I.
a) Pd(PPh3)2CL2, Na2CO3, H2O, THF
b) Pd(PPh3)2CL2, Na2CO3, H2O, THF
c) BBr3, DCM, 0° C.
d) DCC, DMAP, DCM
e) TFAA, DCM,
wherein n is as defined under Scheme I.
a) Pd(PPh3)2Cl2, Na2CO3, H2O, THF
b) BBr3, DCM
c) K2CO3, MEK, 80° C.
d) K2CO3, MEK, 80° C.
wherein n is as defined under Scheme I.
a) Pd(PPh3)Cl2, CuI, N(C2H5)3, THF
b) Pd(PPh3)Cl2, CuI, N(C2H5)3, THF
c) Pd/C, [H2], THF
d) Pd(PPh3)Cl2, Na2CO3, H2O, THF
Another object of the invention is the use of mesogenic compounds of formula I in liquid crystalline media.
The invention thus relates to a liquid-crystalline medium which comprises at least one compound of the formula I.
Some further preferred embodiments of the mixtures according to the invention are indicated below.
The media according to the invention preferably comprise one, two, three, four or more, preferably one, two or three, compounds of the formula I.
The amount of compounds of formula I in the liquid crystalline medium is preferably from 1 to 50%, in particular from 5 to 40%, very preferably 10 to 30% by weight of the total mixture.
In a preferred embodiment the liquid crystalline medium according to the present invention comprises additionally one or more compounds of formula III, like those or similar to those known from GB 2 356 629.
R31-MG31-X31-Sp3-X32-MG32-R32 III
wherein
The mesogenic groups MG31 and MG32 are preferably selected of formula II.
Especially preferred are compounds of formula III wherein R31-MG31-X31— and R32-MG32-X32— are identical.
Another preferred embodiment of the present invention relates to compounds of formula III wherein R31-MG31-X31— and R32-MG32-X32— are different.
Especially preferred are compounds of formula III wherein the mesogenic groups MG31 and MG32 comprise one, two or three six-membered rings very preferably are the mesogenic groups selected from formula II as listed below.
For MG31 and MG32 in formula III are particularly preferred are the subformulae II-1, II-4, II-5, II-8, II-15 and II-19. In these preferred groups Z in each case independently has one of the meanings of Z1 as given in formula II. Preferably Z is —COO—, —OCO—, —CH2CH2—, —C≡C— or a single bond.
Very preferably the mesogenic groups MG31 and MG32 are selected from the formulae IIa to IIo and their mirror images.
In case of compounds with a non-polar group, R31 and R32 are preferably alkyl with up to 15 C atoms or alkoxy with 2 to 15 C atoms.
If R31 or R32 is an alkyl or alkoxy radical, i.e. where the terminal CH2 group is replaced by —O—, this may be straight-chain or branched. It is preferably straight-chain, has 2, 3, 4, 5, 6, 7 or 8 carbon atoms and accordingly is preferably ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, or octoxy, furthermore methyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy or tetradecoxy, for example.
Oxaalkyl, i.e. where one CH2 group is replaced by —O—, is preferably straight-chain 2-oxapropyl (=methoxymethyl), 2-(=ethoxymethyl) or 3-oxabutyl (=2-methoxyethyl), 2-, 3-, or 4-oxapentyl, 2-, 3-, 4-, or 5-oxahexyl, 2-, 3-, 4-, 5-, or 6-oxaheptyl, 2-, 3-, 4-, 5-, 6- or 7-oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl or 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-oxadecyl, for example.
In case of a compounds with a terminal polar group, R31 and R32 are selected from CN, NO2, halogen, OCH3, OCN, SCN, CORx, COORx or a mono- oligo- or polyfluorinated alkyl or alkoxy group with 1 to 4 C atoms. Rx is optionally fluorinated alkyl with 1 to 4, preferably 1 to 3 C atoms. Halogen is preferably F or Cl, more preferably F.
Especially preferably R31 and R32 in formula III are selected of F, Cl, CN, NO2, OCH3, COCH3, COC2H5, COOCH3, COOC2H5, CF3, C2F5, OCF3, OCHF2, and OC2F5, in particular of F, Cl, CN, OCH3 and OCF3.
As for the spacer group Spa in formula III all groups can be used that are known for this purpose to the skilled in the art. The spacer group Sp is preferably a linear or branched alkylene group having 5 to 40 C atoms, in particular 5 to 25 C atoms, very preferably 5 to 15 C atoms, in which, in addition, one or more non-adjacent CH2 groups may be replaced by —O—, —S—, —NH—, —N(CH3)—, —CO—, —O—CO—, —S—CO—, —O—COO—, —CO—S—, —CO—O—, —CH(halogen)-, —CH(CN)—, —CH═CH— or —C≡C—.
Typical spacer groups for formula III are for example —(CH2)o—, —(CH2CH2O)p—CH2CH2—, —CH2CH2—S—CH2CH2— or —CH2CH2—NH—CH2CH2—, with o being an integer from 5 to 40, in particular from 5 to 25, very preferably from 5 to 15, and p being an integer from 1 to 8, in particular 1, 2, 3 or 4.
Preferred spacer groups are pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, diethyleneoxyethylene, dimethyleneoxybutylene, pentenylene, heptenylene, nonenylene and undecenylene, for example.
Especially preferred are inventive compounds of formula III wherein Spa is denoting alkylene with 5 to 15 C atoms. Straight-chain alkylene groups are especially preferred.
In another preferred embodiment of the invention the chiral compounds of formula III comprise at least one spacer group Sp1 that is a chiral group of the formula IV.
X31 and X32 in formula III denote preferably —O—, —CO—, —COO—, —OCO—, —O—CO—O— or a single bond. Particularly preferred are the following compounds selected from formulae III-1 to III-4:
wherein R31, R32 have the meaning given under formula III, Z31 and Z31-I are defined as Z31 and Z32 and Z32-I are respectively the reverse groups of Z31 and Z32-I in formula III and o and r are independently at each occurrence as defined above, including the preferred meanings of these groups and wherein L is in each occurrence independently of each other preferably F, Cl, CN, OH, NO2 or an optionally fluorinated alkyl, alkoxy or alkanoyl group with 1 to 7 C atoms, very preferably F, Cl, CN, OH, NO2, CH3, C2H5, OCH3, OC2H5, COCH3, COC2H5, COOCH3, COOC2H5, CF3, OCF3, OCHF2, OC2F5, in particular F, Cl, CN, CH3, C2H5, OCH3, COCH3 and OCF3, most preferably F, Cl, CH3, OCH3 and COCH3 and from which compounds of formula I are excluded.
Particularly preferred mixtures according to the invention comprise one or more compounds of the formulae III-1a to III-1e and III-3a to III-3b.
wherein the parameters are as defined above.
In a preferred embodiment of the invention the liquid crystalline medium is consisting of 2 to 25, preferably 3 to 15 compounds of formula III.
The amount of compounds of formula III in the liquid crystalline medium is preferably from 10 to 95%, in particular from 15 to 90%, very preferably 20 to 85% by weight of the total mixture.
Preferably, the proportion of compounds of the formulae III-1a and/or III-1 b and/or III-1c and/or III-1e and or III-3a and/or III-3b in the medium as a whole is preferably at least 70% by weight.
Particularly preferred media according to the invention comprise at least one or more chiral dopants which themselves do not necessarily have to show a liquid crystalline phase and give good uniform alignment themselves.
Especially preferred are chiral dopants selected from formula IV
including the respective (S,S) enantiomer,
wherein E and F are each independently 1,4-phenylene or trans-1,4-cyclo-hexylene, v is 0 or 1, Z° is —COO—, —OCO—, —CH2CH2— or a single bond, and R is alkyl, alkoxy or alkanoyl with 1 to 12 C atoms.
The compounds of formula IV and their synthesis are described in WO 98/00428. Especially preferred is the compound CD-1, as shown in table D below. The compounds of formula V and their synthesis are described in GB 2,328,207.
Especially preferred are chiral dopants with a high helical twisting power (HTP), in particular those disclosed in WO 98/00428.
Further typically used chiral dopants are e.g. the commercially available R/S-5011, CD-1, R/S-811 and CB-15 (from Merck KGaA, Darmstadt, Germany).
The above mentioned chiral compounds R/S-5011 and CD-1 and the compounds of formula IV and V exhibit a very high helical twisting power (HTP), and are therefore particularly useful for the purpose of the present invention.
The liquid crystalline medium preferably comprises preferably 1 to 5, in particular 1 to 3, very preferably 1 or 2 chiral dopants, preferably selected from the above formula IV, in particular CD-1, and/or formula V and/or R-5011 or S-5011, very preferably the chiral compound is R-5011, S-5011 or CD-1.
The amount of chiral compounds in the liquid crystalline medium is preferably from 1 to 20%, in particular from 1 to 15%, very preferably 1 to 10% by weight of the total mixture.
Further preferred are liquid crystalline media comprising one or more additives selected from the following formula VI
wherein
R5 is alkyl, alkoxy, alkenyl or alkenyloxy with up to 12 C atoms,
is
L1 through L4 are each independently H or F,
Z2 is —COO—, —CH2CH2— or a single bond,
m is 1 or 2
Particularly preferred compounds of formula VI are selected from the following formulae
wherein, R has one of the meanings of R5 above and L1, L2 and L3 have the above meanings.
The liquid crystalline medium preferably comprises preferably 1 to 5, in particular 1 to 3, very preferably 1 or 2, preferably selected from the above formulae VIa to VIf, very preferably from formulae VIf.
The amount of suitable additives of formula VI in the liquid crystalline medium is preferably from 1 to 20%, in particular from 1 to 15%, very preferably 1 to 10% by weight of the total mixture.
The liquid crystal media according to the present invention may contain further additives in usual concentrations. The total concentration of these further constituents is in the range of 0.1% to 10%, preferably 0.1% to 6%, based on the total mixture. The concentrations of the individual compounds used each are preferably in the range of 0.1% to 3%. The concentration of these and of similar additives is not taken into consideration for the values and ranges of the concentrations of the liquid crystal components and compounds of the liquid crystal media in this application. This also holds for the concentration of the dichroic dyes used in the mixtures, which are not counted when the concentrations of the compounds respectively the components of the host medium are specified. The concentration of the respective additives is always given relative to the final doped mixture.
The liquid crystal media according to the present invention consists of several compounds, preferably of 3 to 30, more preferably of 4 to 20 and most preferably of 4 to 16 compounds. These compounds are mixed in conventional way. As a rule, the required amount of the compound used in the smaller amount is dissolved in the compound used in the greater amount. In case the temperature is above the clearing point of the compound used in the higher concentration, it is particularly easy to observe completion of the process of dissolution. It is, however, also possible to prepare the media by other conventional ways, e.g. using so called pre-mixtures, which can be e.g. homologous or eutectic mixtures of compounds or using so called multi-bottle-systems, the constituents of which are ready to use mixtures themselves.
Particularly preferred mixture concepts are indicated below: (the acronyms used are explained in Table A).
The mixtures according to the invention preferably comprise
F-PGI-O9O-GP-F preferably in concentrations of >1%, in particular 1-20%, based on the mixture as a whole,
The mesogenic compounds of formula I and the liquid crystalline media comprising them can be used in liquid crystal displays, such as STN, TN, AMD-TN, temperature compensation, guest-host, phase change or surface stabilized or polymer stabilized cholesteric texture (SSCT, PSCT) displays, in particular in flexoelectric devices, in active and passive optical elements like polarizers, compensators, reflectors, alignment layers, colour filters or holographic elements, in adhesives, synthetic resins with anisotropic mechanical properties, cosmetics, diagnostics, liquid crystal pigments, for decorative and security applications, in nonlinear optics, optical information storage or as chiral dopants.
The compounds of formula I and the mixtures obtainable thereof are particularly useful for flexoelectric liquid crystal display. Thus, another object of the present invention is a flexoelectric display comprising one or more compounds of formula I or comprising a liquid crystal medium comprising one or more compounds of formula I.
The inventive mesogenic compounds of formula I and the mixtures thereof can be aligned in their cholesteric phase into different states of orientation by methods that are known to the expert, such as surface treatment or electric fields. For example, they can be aligned into the planar (Grandjean) state, into the focal conic state or into the homeotropic state. Inventive compounds of formula I comprising polar groups with a strong dipole moment can further be subjected to flexoelectric switching, and can thus be used in electro-optical switches or liquid crystal displays.
The switching between different states of orientation according to a preferred embodiment of the present invention is exemplarily described below in detail for a sample of an inventive compound of formula I.
According to this preferred embodiment, the sample is placed into a cell comprising two plane-parallel glass plates coated with electrode layers, e.g. ITO layers, and aligned in its cholesteric phase into a planar state wherein the axis of the cholesteric helix is oriented normal to the cell walls. This state is also known as Grandjean state, and the texture of the sample, which is observable e.g. in a polarization microscope, as Grandjean texture. Planar alignment can be achieved e.g. by surface treatment of the cell walls, for example by rubbing and/or coating with an alignment layer such as polyimide.
A Grandjean state with a high quality of alignment and only few defects can further be achieved by heating the sample to the isotropic phase, subsequently cooling to the chiral nematic phase at a temperature close to the chiral nematic-isotropic phase transition, and rubbing the cell.
In the planar state, the sample shows selective reflection of incident light, with the central wavelength of reflection depending on the helical pitch and the mean refractive index of the material.
When an electric field is applied to the electrodes, for example with a frequency from 10 Hz to 1 kHz, and an amplitude of up to 12 Vrms/□m, the sample is being switched into a homeotropic state where the helix is unwound and the molecules are oriented parallel to the field, i.e. normal to the plane of the electrodes. In the homeotropic state, the sample is transmissive when viewed in normal daylight, and appears black when being put between crossed polarizers.
Upon reduction or removal of the electric field in the homeotropic state, the sample adopts a focal conic texture, where the molecules exhibit a helically twisted structure with the helical axis being oriented perpendicular to the field, i.e. parallel to the plane of the electrodes. A focal conic state can also be achieved by applying only a weak electric field to a sample in its planar state. In the focal conic state the sample is scattering when viewed in normal daylight and appears bright between crossed polarizers.
A sample of an inventive compound in the different states of orientation exhibits different transmission of light. Therefore, the respective state of orientation, as well as its quality of alignment, can be controlled by measuring the light transmission of the sample depending on the strength of the applied electric field. Thereby it is also possible to determine the electric field strength required to achieve specific states of orientation and transitions between these different states.
In a sample of an inventive compound of formula I, the above described focal conic state consists of many disordered birefringent small domains. By applying an electric field greater than the field for nucleation of the focal conic texture, preferably with additional shearing of the cell, a uniformly aligned texture is achieved where the helical axis is parallel to the plane of the electrodes in large, well-aligned areas. In accordance with the literature on state of the art chiral nematic materials, such as P. Rudquist et al., Liq. Cryst. 23 (4), 503 (1997), this texture is also called uniformly-lying helix (ULH) texture. This texture is required to characterize the flexoelectric properties of the inventive compound.
The sequence of textures typically observed in a sample of an inventive compound of formula I on a rubbed polyimide substrate upon increasing or decreasing electric field is given below:
Starting from the ULH texture, the inventive flexoelectric compounds and mixtures can be subjected to flexoelectric switching by application of an electric field. This causes rotation of the optic axis of the material in the plane of the cell substrates, which leads to a change in transmission when placing the material between crossed polarizers. The flexoelectric switching of inventive materials is further described in detail in the introduction above and in the examples.
It is also possible to obtain the ULH texture, starting from the focal conic texture, by applying an electric field with a high frequency, of for example 10 kHz, to the sample whilst cooling slowly from the isotropic phase into the cholesteric phase and shearing the cell. The field frequency may differ for different compounds.
The mesogenic compounds of formula I are particularly useful in flexoelectric liquid crystal displays as they can easily be aligned into macroscopically uniform orientation, and lead to high values of the elastic constant k11 and a high flexoelectric coefficient e in the liquid crystal medium.
The liquid crystal medium preferably exhibits a k11<1×10−10 N, preferably <2×10−11 N, and a flexoelectric coefficient e>1×10−11 C/m, preferably >1×10−10 C/m.
Apart from the use in flexoelectric devices, the inventive bimesogenic compounds as well as mixtures thereof are also suitable for other types of displays and other optical and electro-optical applications, such as optical compensation or polarizing films, colour filters, reflective cholesterics, optical rotatory power and optical information storage.
A further aspect of the present invention relates to a display cell wherein the cell walls exhibit hybrid alignment conditions. The term “hybrid alignment” or orientation of a liquid crystal or mesogenic material in a display cell or between two substrates means that the mesogenic groups adjacent to the first cell wall or on the first substrate exhibit homeotropic orientation and the mesogenic groups adjacent to the second cell wall or on the second substrate exhibit planar orientation.
The term “homeotropic alignment” or orientation of a liquid crystal or mesogenic material in a display cell or on a substrate means that the mesogenic groups in the liquid crystal or mesogenic material are oriented substantially perpendicular to the plane of the cell or substrate, respectively.
The term “planar alignment” or orientation of a liquid crystal or mesogenic material in a display cell or on a substrate means that the mesogenic groups in the liquid crystal or mesogenic material are oriented substantially parallel to the plane of the cell or substrate, respectively.
A flexoelectric display according to a preferred embodiment of the present invention comprises two plane parallel substrates, preferably glass plates covered with a transparent conductive layer such as indium tin oxide (ITO) on their inner surfaces, and a flexoelectric liquid crystalline medium provided between the substrates, characterized in that one of the inner substrate surfaces exhibits homeotropic alignment conditions and the opposite inner substrate surface exhibits planar alignment conditions for the liquid crystalline medium.
Planar alignment can be achieved e.g. by means of an alignment layer, for example a layer of rubbed polyimide or sputtered SiOx, that is applied on top of the substrate.
Alternatively it is possible to directly rub the substrate, i.e. without applying an additional alignment layer. For example, rubbing can be achieved by means of a rubbing cloth, such as a velvet cloth, or with a flat bar coated with a rubbing cloth. In a preferred embodiment of the present invention rubbing is achieved by means of a at least one rubbing roller, like e.g. a fast spinning roller that is brushing across the substrate, or by putting the substrate between at least two rollers, wherein in each case at least one of the rollers is optionally covered with a rubbing cloth. In another preferred embodiment of the present invention rubbing is achieved by wrapping the substrate at least partially at a defined angle around a roller that is preferably coated with a rubbing cloth.
Homeotropic alignment can be achieved e.g. by means of an alignment layer coated on top of the substrate. Suitable aligning agents used on glass substrates are for example alkyltrichlorosilane or lecithine, whereas for plastic substrate thin layers of lecithine, silica or high tilt polyimide orientation films as aligning agents may be used. In a preferred embodiment of the invention silica coated plastic film is used as a substrate.
Further suitable methods to achieve planar or homeotropic alignment are described for example in J. Cognard, Mol. Cryst. Liq. Cryst. 78, Supplement 1, 1-77 (1981).
By using a display cell with hybrid alignment conditions, a very high switching angle of flexoelectric switching, fast response times and a good contrast can be achieved.
The flexoelectric display according to present invention may also comprise plastic substrates instead of glass substrates. Plastic film substrates are particularly suitable for rubbing treatment by rubbing rollers as described above.
Another object of the present invention is that compounds of formula I, when added to a nematic liquid crystalline mixture, produce a phase below the nematic.
Accordingly, the mesogenic compounds of formula I according to the present invention allow the second nematic phase to be induced in nematic mixtures that do not show evidence of this phase normally. Furthermore, varying the amounts of compounds of formula I allow the phase behaviour of the second nematic to be tailored to the required temperature.
Examples for this are given and the mixtures obtainable thereof are particularly useful for flexoelectric liquid crystal display. Thus, another object of the present invention is liquid crystal media comprising one or more compounds of formula I exhibiting a second nematic phase.
Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The following examples are, therefore, to be construed as merely illustrative and not limitative of the remainder of the disclosure in any way whatsoever.
Unless the context clearly indicates otherwise, as used herein plural forms of the terms herein are to be construed as including the singular form and vice versa.
Throughout the description and claims of this specification, the words “comprise” and “contain” and variations of the words, for example “comprising” and “comprises”, mean “including but not limited to”, and are not intended to (and do not) exclude other components.
Throughout the present application it is to be understood that the angles of the bonds at a C atom being bound to three adjacent atoms, e.g. in a C═C or C═O double bond or e.g. in a benzene ring, are 120° and that the angles of the bonds at a C atom being bound to two adjacent atoms, e.g. in a C≡C or in a C≡N triple bond or in an allylic position C═C═C are 180°, unless these angles are otherwise restricted, e.g. like being part of small rings, like 3-, 5- or 5-atomic rings, notwithstanding that in some instances in some structural formulae these angles are not represented exactly.
It will be appreciated that variations to the foregoing embodiments of the invention can be made while still falling within the scope of the invention. Each feature disclosed in this specification, unless stated otherwise, may be replaced by alternative features serving the same, equivalent or similar purpose. Thus, unless stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.
All of the features disclosed in this specification may be combined in any combination, except combinations where at least some of such features and/or steps are mutually exclusive. In particular, the preferred features of the invention are applicable to all aspects of the invention and may be used in any combination. Likewise, features described in non-essential combinations may be used separately (not in combination).
The total concentration of all compounds in the media according to this application is 100%.
In the foregoing and in the following examples, unless otherwise indicated, all temperatures are set forth uncorrected in degrees Celsius and all parts and percentages are by weight.
The following abbreviations are used to illustrate the liquid crystalline phase behaviour of the compounds: K=crystalline; N=nematic; N2=second nematic; S or Sm=smectic; Ch=cholesteric; I=isotropic; Tg=glass transition. The numbers between the symbols indicate the phase transition temperatures in ° C.
In the present application and especially in the following examples, the structures of the liquid crystal compounds are represented by abbreviations, which are also called “acronyms”. The transformation of the abbreviations into the corresponding structures is straight forward according to the following three tables A to C.
All groups CnH2n+1, CmH2m+1, and ClH2l−1 are preferably straight chain alkyl groups with n, m and I C-atoms, respectively, all groups CnH2n, CmH2m and ClH2lare preferably (CH2)n, (CH2)m and (CH2)l, respectively and —CH═CH— preferably is trans-respectively E vinylene.
Table A lists the symbols used for the ring elements, table B those for the linking groups and table C those for the symbols for the left hand and the right hand end groups of the molecules.
Table D lists exemplary molecular structures together with their respective codes.
wherein n and m each are integers and three points “ . . . ” indicate a space for other symbols of this table.
Preferably the liquid crystalline media according to the present invention comprise, besides the compound(s) of formula I one or more compounds selected from the group of compounds of the formulae of the following table.
Step 1.1
Pimelic acid, 11.8 g (74 mmol) is added to a round bottom flask and dissolved in Dichloromethane (100 ml) with stirring. Trifluoroacetic anhydride, 10.3 ml (74 mmol) is added slowly over a period of 5 minutes keeping the temperature constant at 20° C. The reaction mixture is stirred for 1 hour before adding a solution of 3,4-difluorophenol, 4.8 g (37 mmol) in Toluene (25 ml). The reaction mixture is stirred for 16 h at ambient temperature (herein about 20° C. unless explicitly stated otherwise) before diluting with Dichloromethane (100 ml). Brine is added and the resulting organic and aqueous layers are separated and the aqueous layer is extracted twice with 50 ml Dichloromethane each time. The combined organic material is washed with water twice, then dried over magnesium sulphate, filtered and concentrated in vacuo to afford the crude product. Purification by column chromatography through flash silica gel, eluting with petroleum ether/ethyl acetate solvent mixture gives a white solid.
Step 1.2
Sodium Carbonate, 16.5 g (0.156 mol) is dissolved in water (76 ml) and added to a 250 ml round bottom flask with stirring. 4-Bromophenol, 13.4 g (0.077 mol) is added into the flask along with Dioxane (152 ml). The flask is evacuated and refilled with nitrogen. 3,4-difluorophenylboronic acid, 14.7 g (0.093 mol) is added to the reaction flask, followed by palladium(dppf)dichloride, 1.9 g (2.38 mmol). The reaction mixture is heated to under vigorous reflux for 16 h. After allowing to cool down to ambient temperature the reaction mixture is diluted with water (150 ml) and acidified with dilute HCl (25 ml). After 5 minutes of stirring the organic and aqueous layers are separated and the aqueous layer extracted three times with 100 ml ethyl acetate each time. The combined organic material is washed with brine and then with water until the pH value of the aqueous wash is 6. The material is dried over anhydrous sodium sulphate, filtered and concentrated in vacuo to afford the crude product. Purification by column chromatography through flash silica gel, eluting with petroleum ether/ethyl acetate solvent mixture (ratio 5:1) gives a white solid.
Step 1.3
The product from the first step (Step 1.1), 3.7 g (16.6 mmol) is added to a round bottom flask together with Dichloromethane (50 ml). Trifluoroacetic anhydride, 1.9 ml (13.6 mmol) is added slowly over a period of 5 minutes keeping the temperature constant at 20° C. The reaction mixture is stirred for 1 hour at 25° C. In a second reaction flask, the product from the second step (Step 1.2), 2.8 g (13.6 mmol) is dissolved in Dichloromethane (50 ml). The mixture of the monoester/TFAA is added drop wise into the second reaction flask over a period of 30 minutes without cooling and is then stirred at ambient temperature for 16 h. The reaction mixture is diluted with Dichloromethane and then Brine is added and the resulting layers are separated and the aqueous layer is extracted twice with 50 ml Dichloromethane each time. The combined organic material is washed with water twice, then dried over magnesium sulphate, filtered and concentrated in vacuo to afford the crude product. Purification by column chromatography through flash silica gel, eluting with petroleum ether/Dichloromethane solvent mixture (3:7) followed by re-crystallisation from petroleum ether/Dichloromethane mixture affords the final product.
Phase sequence: K 74.8 I; T*(N,I)=69.0° C.; e/K=2.16 C·m−1·N−1=2.16 V−1. The e/K has been measured in mixture M-1 as specified below.
Remark: T*(N,I) and e/K extrapolated from 10% in host mixture H-0 with 2% of R-5011.
Step 2.1
4-Cyanophenol (8.3 g, 69 mmol) is dissolved in a stirred solution of Dichloromethane (75 ml) together with Undecandioic acid (15 g, 15.7 mmol) and Dimethyl aminopyridine (0.24 g, 1.9 mmol). After cooling to a temperature of 5° C. in Ice/water, a solution of Dicyclohexyl-carbodiimide (3.2 g, 15.6 mmol) in Dichloromethane (25 ml) is added drop wise. The reaction is stirred for 16 h and then allowed to warm up to room temperature. The reaction mixture is filtered in vacuo and the filtrate is concentrated to afford the crude product. Purification is carried out by column chromatography through silica gel, eluting with ethyl acetate/petroleum ether mixture (gradient elution from 2% to 20% ethyl acetate). A white powder is obtained and used without further purification.
Step 2.2
4-Fluorophenylboronic acid (35.0 g, 0.25 mol) and 4-bromo-3-fluorophenol (46.8 g, 0.245 mol) are charged to a 3-neck 2 litre round-bottomed flask and dissolved in 1,4-dioxane (1000 ml). The catalyst, Pd(dppf)Cl2, (2.0 g, 2.5 mmol) is added, followed by the addition of 2 molar sodium carbonate solution (250 ml). The solution is vigorously stirred for 16 h at a temperature of 80° C. under a nitrogen atmosphere.
The reaction mixture is cooled, then neutralised by addition of dilute Hydrochloric acid (HCl). Then the layers are separated. The organic material is washed first with brine (100 ml) and then water (150 ml). The aqueous phase is back extracted with ethyl acetate (30 ml) three times each and all the organic material combined, dried over magnesium sulphate, filtered and concentrated in vacuo. Purification is carried out by column chromatography through silica gel, eluting with Dichloromethane/petroleum ether mixture (gradient elution from 10% to 50% Dichloromethane). Final purification is afforded by re-crystallisation from petroleum ether/Dichloromethane (3:1 ratio) at a temperature of 5°. A white solid is obtained.
Step 2.3
The product from the previous step (Step 2.2) (4.0 g, 13 mmol) is added to a reaction flask with Dichloromethane (25 ml) and trifluoroacetic anhydride (1.9 ml, 13.8 mmol). After filling under inert atmosphere, the reaction mixture is stirred for 2 hours at ambient temperature. Into a separate flask 2′-4-difluorobiphenol (3.1 g, 15 mmol) is added followed by Dichloromethane (25 ml), under stirring. The content of the first flask is slowly added into the second flask, then stirred for a further 2 hours at ambient temperature. The reaction mixture is poured into water, and after separating the resulting layers, the organic phase is washed with sodium hydrogen carbonate solution (30 ml) and water (30 ml). The organic phase is dried over anhydrous sodium sulphate, filtered and concentrated in vacuo to yield the crude product as a yellow liquid. Purification is carried out by column chromatography through silica gel, eluting with dichloromethane/petroleum ether mixture. A white solid is obtained, which is re-crystallised from acetonitrile to yield the final pure product.
Phase sequence: K 82.4 (N 36) I; T*(N,I)=72.5° C.; e/K=2.07 V−1.
Remark: T*(N,I) and e/K extrapolated from 10% in host mixture H-0 with 2% of R-5011.
Step 3.1
In a 3-necked round bottom flask methyl 5-hexynoate (15.5 g, 122.86 mmol), 4-bromo-3-fluoroiodobenzene (36.97 g, 122.86 mmol), diisopropylamine (45 ml) and THF (225 ml) are placed under nitrogen. The flask is evacuated and refilled with nitrogen gas. The flask is then treated in an ultrasonic bath for 30 minutes to degas the reaction mixture, a procedure shortly referred to as “ultasonication” or shortly “sonication” in this application. Pd(Ph3P)2Cl2 (0.33 g) and CuI (0.165 g) are added to the mixture in one portion under stirring. The mixture was then is heated to a temperature of 30° C. for 20 minutes and then to 40° C. for 1 hour. The mixture is cooled and the solids are filtered off and washed thoroughly with ethyl acetate (100 ml). The filtrate is concentrated under reduced pressure. A dark coloured solid is obtained that is dissolved in Dichloromethane and purified by column chromatography through silica gel, eluted with petroleum ether/Dichloromethane. The appropriate fractions are combined and the solvent evaporated to obtain the product.
Step 3.2
The H-Cube hydrogenation apparatus is installed with a new Platinum/Carbon catalyst and set to flow rate 10 ml/min, 20 bars and 40° C. The product from the previous step (Step 3.1) (6.5 g, 21.7 mmol) is dissolved in Tetrahydrofuran (200 ml) and fed through the H-cube. GCMS shows complete hydrogenation, yielding the product, which is used for the next step without additional purification.
Step 3.3
The product from the previous step (Step 3.2), (10.9 g, 36.1 mmol) is added into a round bottom flask with 3,4-difluorobenzeneboronic acid (5.6 g, 36.1 mmol). Dioxan (250 ml) and Water (150 ml) are added to the reaction mixture and the whole mixture is stirred whilst the flask is flushed with nitrogen. Potassium phosphate (30.6 g, 144 mmol) is added followed by the catalyst Pd(dppf)Cl2 (0.53 g, 0.72 mmol). The reaction mixture is heated to 90° C. for 16 h under with vigorous stirring. The mixture is cooled to ambient temperature, the layers are separated and the organic material is washed twice with water (100 ml twice) before being concentrated in vacuo. The dark crude product is dissolved in Dichloromethane and purified by flash column chromatography on a silica column, eluted with petroleum ether/Dichloromethane solution (1:1 mixture) to yield the product.
Step 3.4
The product from the previous step (Step 3.3), (5.5 g, 16.4 mmol) and sodium hydroxide (1.26 g, 31.5 mmol) are added into a flask. Water (25 ml) and ethanol (25 ml) are subsequently added under stirring. Then the reaction mixture is heated to a temperature of 100° C. for 2 hours. The reaction mixture is cooled, reduced in volume by half under reduced pressure and acidified by drop wise addition of Hydrochloric acid (HCl). The acidified liquid is cooled in an ice bath and allowed to crystallise, the solids are filtered off in vacuo and washed well with water. Final purification is performed by re-crystallisation from ethanol/water mixture yields the pure product.
Step 3.5
The product from the previous step (Step 3.4), (5.0 g, 15.6 mmol) and 4-cyanohydroxyphenyl (1.6 g, 13.0 mmol) are added to a reaction flask and dissolved in Dichloromethane (95 ml) under stirring. The flask is flushed with nitrogen before Dimethylaminopyridine (0.24 g, 1.95 mmol) is added.
The reaction flask is cooled in an ice bath to a temperature of 5° C. Then a solution of Dicyclhexylcarbodiimide (3.2 g, 15.6 mmol) in Dichloromethane (30 ml) is added slowly. The ice bath is removed and the reaction mixture stirred for a further 18 hours. The reaction mixture is filtered in vacuo and the filter pad washed well with Dichloromethane (150 ml) before concentrating the filtrate to give the crude product. Purification is performed on a Biotage SP4 automated column chromatography instrument using a 100 g SNAP column and gradient elution of Ethyl acetate in Petroleum ether (2% up to 20% ethyl acetate concentration). The appropriate fractions were combined to give the final pure product.
Phase sequence: K 61.5 I; T*(N,I)=69.9° C.; e/K=2.51 V−1.
Remarks: T*(N,I) and e/K extrapolated from 10% in host mixture H-0 with 2% of R-5011, phases X and Y to be determined.
The following compounds of formula I are prepared analogously.
Phase sequence: K 102.5 I; T*(N,I)=63° C.; e/K=2.65 V−1.
(Remark: T*(N,I) and e/K extrapolated from 10% in host mixture H-0 with 2% of R-5011.)
Phase sequence: K 89 I; T*(N,I)=66.0° C.; e/K=2.46 V−1.
Phase sequence: K 87.4 I; T*(N,I)=72.5° C.; e/K=2.32 V−1.
Phase sequence: K 70 I; T*(N,I)=66.0° C.; e/K=2.32 V−1.
Phase sequence: K 59 I; T*(N,I)=63.1° C.; e/K=2.45 V−1.
Phase sequence: K 45.8 I; T*(N,I)=60.5° C.; e/K=2.14 V−1.
Phase sequence: K 83 I; T*(N,I)=69.1° C.; e/K=1.84 V−1.
Phase sequence: K 47 I; T*(N,I)=63.0° C.; e/K=1.93 V−1.
Phase sequence: K 72 I; T*(N,I)=72.7° C.; e/K=2.41 V-1.
Phase sequence: K 91 (N 85) I; T*(N,I)=77.0° C.; e/K=2.24 V−1.
Phase sequence: K 64 I; T*(N,I)=68.3° C.; e/K=2.09 V−1.
Phase sequence: K 53 I; T*(N,I)=69.0° C.; e/K=1.95 V−1.
Phase sequence: K 95 I; T*(N,I)=75.6° C.; e/K=1.90 V−1.
Phase sequence: K 64 I; T*(N,I)=73.5° C.; e/K=2.23 V−1.
Phase sequence: K 113 N 166 I; T*(N,I)=82.5° C.; e/K=1.82 V−1.
Phase sequence: K 104 N 169 I; T*(N,I)=84.0° C.; e/K=1.60 V-1.
Phase sequence: K 133 I; T*(N,I)=76.7° C.; e/K=1.85 V−1.
The materials in the above table generally showed increased performance in the screening mixtures, as compared to known, more conventional bimesogenic compounds as e.g. those shown in the table below.
Typically a 5.6 μm thick cell, having an anti-parallel rubbed PI alignment layer, is filled on a hotplate at a temperature at which the flexoelectric mixture in the isotropic phase.
After the cell has been filled phase transitions, including clearing point, are measured using a Differential Scanning calorimeter (DSC) and verified by optical inspection. For optical phase transition measurements, a Mettler FP90 hot-stage controller connected to a FP82 hot-stage is used to control the temperature of the cell. The temperature is increased from ambient temperature at a rate of 5 degrees C. per minute, until the onset of the isotropic phase is observed. The texture change is observed through crossed polarizers using an Olympus BX51 microscope and the respective temperature noted.
Wires are then attached to the ITO electrodes of the cell using indium metal. The cell is secured in a Linkam THMS600 hot-stage connected to a Linkam TMS93 hot-stage controller. The hot-stage is secured to a rotation stage in an Olympus BX51 microscope.
The cell is heated until the liquid crystal is completely isotropic. The cell is then cooled under an applied electric field until the sample is completely nematic. The driving waveform is supplied by a Tektronix AFG3021B arbitrary function generator, which is sent through a Newtons4th LPA400 power amplifier before being applied to the cell. The cell response is monitored with a Thorlabs PDA55 photodiode. Both input waveforms and optical response are measured using a Tektronix TDS 2024B digital oscilloscope.
In order to measure the flexoelastic response of the material, the change in the size of the tilt of the optical axis is measured as a function of increasing voltage. This is achieved by using the equation:
wherein φ is the tilt in the optic axis from the original position (i.e. when E=0), E is the applied field, K is the elastic constant (average of K1 and K3) and e is the flexoelectric coefficient (where e=e1+e3). The applied field is monitored using a HP 34401A multi-meter. The tilt angle is measured using the aforementioned microscope and oscilloscope. The undisturbed cholesteric pitch, P0, is measured using an Ocean Optics USB4000 spectrometer attached to a computer. The selective reflection band is obtained and the pitch determined from the spectral data.
The mixtures shown in the following examples are well suitable for use in USH-displays. To that end an appropriate concentration of the chiral dopant or dopants used has to be applied in order to achieve a cholesteric pitch of 200 nm or less.
The host mixture H-0 is prepared and investigated.
2% of the chiral dopant R-5011 are added to the mixture H-0 leading to the mixture H-1, which is investigated for its properties.
The mixture H-1 may be used for the ULH-mode. It has a clearing point of 82° C. and a lower transition temperature [T(N2,N)] of 33° C. It has a cholesteric pitch of 291 nm at 0.9T(N,I). The e/K of this mixture is 1.80 Cm−1N−1 at 0.9T(N,I).
2% of the chiral dopant R-5011 and 10% of the compound of synthesis example 1 are added to the mixture H-0 leading to the mixture M-1.1, which is investigated for its properties.
This mixture (M-1) is prepared and investigated. It is well suitable for the ULH-mode. It has a cholesteric pitch of 301 nm at 35° C. The e/K of this mixture is 2.16 Cm−1N−1 at a temperature of 35° C.
This mixture (M-2) is prepared and investigated. It is well suitable for the ULH-mode. It has a cholesteric pitch of 301 nm at 34.5° C.
The e/K of this mixture is 2.07 Cm−1N−1 at a temperature of 34.5° C.
This mixture (M-3) is prepared and investigated. It is well suitable for the ULH-mode. It has a cholesteric pitch of 319 nm at 35° C. The e/K of this mixture is 2.29 V−1 at a temperature of 35° C.
| Number | Date | Country | Kind |
|---|---|---|---|
| 13004454.8 | Sep 2013 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2014/002224 | 8/13/2014 | WO | 00 |
