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WO2011032630A1 - Composés polymérisables et milieux à cristaux liquides - Google Patents

Composés polymérisables et milieux à cristaux liquides Download PDF

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Publication number
WO2011032630A1
WO2011032630A1 PCT/EP2010/005134 EP2010005134W WO2011032630A1 WO 2011032630 A1 WO2011032630 A1 WO 2011032630A1 EP 2010005134 W EP2010005134 W EP 2010005134W WO 2011032630 A1 WO2011032630 A1 WO 2011032630A1
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compounds
groups
group
diyl
atoms
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German (de)
English (en)
Inventor
Axel Jansen
Thorsten Kodek
Helmut Haensel
Erdal Durmaz
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Merck Patent GmbH
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Merck Patent GmbH
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
    • C09K19/3405—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a five-membered ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
    • C09K2019/0448—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
    • C09K2019/3422—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a six-membered ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
    • C09K2019/3422—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a six-membered ring
    • C09K2019/3425—Six-membered ring with oxygen(s) in fused, bridged or spiro ring systems

Definitions

  • the present invention relates to polymerizable compounds of formula I, a process for their preparation, their use as
  • Electro-optical display elements containing these LC media are preferably sugar derivatives.
  • the blue phase is usually observed at the transition from the nematic to the optically isotropic state.
  • liquid crystalline blue phase can be blue, as the name implies, but also colorless. Aim of previous efforts was the,
  • WO 2005/080529 A1 describes polymer-stabilized blue phases with mono- and multireactive monomers.
  • JP 2005 283 632 are derived from carbohydrates
  • Methyl Gluceth-20 (MG-20, Glucam E-20) is described. This is a methylglucoside with a total of about 20 ethyleneoxy units (ethylene glycol units), whereby the glycol units in the ring are also counted.
  • ethyleneoxy units ethylene glycol units
  • these materials are alkoxy polymers of non-uniform composition.
  • the general structure is roughly described by the following formula.
  • MG-20 Glucam E-20
  • the sum of the parameters a, b, c and d is then approximately 20, with the values for a, b, c and d differing from one another can. Since the composition of these materials is not uniform and is subject to variations, they are derived therefrom
  • the present invention has as an object, suitable
  • Monomers and corresponding polymers for the stabilization of blue To find phases are said to have the following effects on the
  • V op low operating voltage
  • the present invention aims to provide, in particular, improved reactive polymerizable compounds which are capable of stabilizing blue phases and which are suitable for producing LC materials having improved properties.
  • a first subject of the invention are thus compounds of the formula I,
  • a 1 , A 3 are each independently of one another:
  • trans-1, 4-cyclohexylene or cyclohexenylene in which also one or more non-adjacent CH 2 groups may be replaced by -O- and / or -S- and in which H may be substituted by F
  • b) 1, 4 Phenylene wherein one or two CH groups may be replaced by N and in which also one or more H atoms may be replaced by Br, Cl, F, CN, methyl, methoxy or a mono- or polyfluorinated methyl or methoxy group .
  • SF 5 CH 2 F, CHF 2l CF 3 , OCH 2 F, OCHF 2 or OCF 3 may be substituted
  • one or more CH groups can be replaced by N,
  • M is -O-, -S-, -CH 2 -, -CHY- or -CYY'-, and
  • Y and Y are Cl, F, CN, OCF 3 or CF 3 , each independently, same or different, a single bond, O, CH 2 , OC (O) CH 2 , -CH 2 O-,
  • x, y is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, where x + y 4, preferably equal to 0, 1 or 2, particularly preferably 0 or
  • P is a polymerizable group
  • Sp is a spacer group or a single bond, -Sp-P together additionally also a group R 1 , mean, wherein the number of polymerizable groups P is one or more.
  • the compounds of the formula I according to the invention do not comprise the sugar derivatives A and B disclosed in the publication JP 2005 283 632, not the methyl gfuceth-20-tetraacrylates, ie not the
  • the polymerizable group P is a group suitable for a
  • Polymerization reaction such as radical or ionic chain polymerization, polyaddition or polycondensation, or for a polymer-analogous reaction, for example, the addition or
  • Condensation to a polymer backbone is suitable.
  • H or alkyl having 1 to 5 C atoms each independently of one another denote H or alkyl having 1 to 5 C atoms, in particular H, methyl, ethyl or n-propyl
  • W 4 , W 5 and W 6 each independently of one another denote Cl
  • W 7 and W 8 are each independently H, Cl or alkyl of 1 to 5 carbon atoms
  • Phe is 1,4-phenylene, which is optionally defined with one or more radicals L as defined above, ki, k 2 and k
  • Each 3 is independently 0 or 1, k 3 is preferably 1.
  • CH 2 CH-COO-
  • CH 2 C (CH 3 ) -COO-
  • CH 2 CF-COO-
  • Very particularly preferred groups P are vinyloxy, acrylate,
  • the monomers according to the invention are suitable, depending on the number of polymerizable groups per molecule, for the formation of
  • Groups in particular the number 4 or 5.
  • spacer group (Engl. "Spacer” or “spacer group”), also referred to below as “Sp”, is known to the person skilled in the art and described in the literature, see, for example, Pure Appl. Chem. 73 (5), 888 (2001) and C. Tschierske, G. Pelzl, S. Diele, Angew. Chem. 2004, 16, 6340-6368. Unless otherwise indicated, the term “spacer” or “spacer” above and below denotes a flexible group which, in a polymerisable liquid-crystalline or mesogenic compound, bonds together the mesogenic group and the polymerizable group (s).
  • R and R are each independently H or alkyl of 1 to 12 C atoms, and
  • Y 2 and Y 3 are each independently H, F, Cl or CN.
  • X is preferably -O-, -S-CO-, -COO-, -OCO-, -O-COO-, -CO-NR 0 -, -NR ° -CO-, -NR ° -CO-NR ° - or a single bond.
  • Typical spacer groups Sp ' are, for example, - (CH 2 ) p i-, - (CH 2 CH 2 O) P 2, -CH 2 CH 2 -, -CH 2 CH 2 -S-CH 2 CH 2 -, -CH 2 CH 2 -NH-CH 2 CH 2 - or - (SiR 00 R 000 -O) p i-, wherein p 1 is an integer from 1 to 24, preferably 3, p 2 is an integer from 1 to 6, and R 00 and R 000 are those given above
  • Particularly preferred groups -X-Sp'- are - (CH 2) p -O- (CH 2) p -, -OCO- (CH 2) p1 -, -OCOO- (CH 2) p1 - wherein p1 as is defined above.
  • Ethylenoxyethylene methyleneoxybutylene, ethylenethioethylene, ethylene-N-methyl-iminoethylene, 1-alkylalkylene, ethenylene, propenylene and
  • Sp ' is an alkylene having 4 to 12 C atoms as defined above in the event that the group X is a
  • a 1 and A 3 can have different meanings if they occur several times for x or y> 1.
  • the groups -Sp-P are equal to one another.
  • the groups R 1 and R 2 independently of one another preferably represent a group P-Sp-, H, alkyl, alkoxy or an alkoxymethyl radical having 1-10 C atoms.
  • the compounds according to the invention are outstandingly suitable as polymerisable components in liquid-crystalline media.
  • the polymer fulfills in all respects the requirements in the task for the stabilization of liquid crystalline phases, in particular of blue phases. Compared to conventional systems becomes a clear
  • the compounds are also suitable in amounts of ⁇ 1% as a polymerisable component in mixtures for PSA-VA type displays (cf., JP 10-1036847 A, EP 1 170626 A2, US 686 107, US 7169449, US 2004/0191428, US Pat. US 2006/0066793) and for other PSA ('polymer sustained alignment') displays.
  • PSA-VA type displays cf., JP 10-1036847 A, EP 1 170626 A2, US 686 107, US 7169449, US 2004/0191428, US Pat. US 2006/0066793
  • PSA 'polymer sustained alignment'
  • Carbohydrates or also referred to as sugars substances are familiar to the person skilled in the art. These are oxidation products of polyhydric alcohols, ie
  • Particularly preferred type I compounds are derived from
  • Monosaccharides simple sugars with five (pentoses, eg xylose) or six carbon atoms (hexoses, eg glucose) from. This allows a ring closure. The balance of this reaction is usually on the side of the cyclic hemiacetals. The open-chain form is usually negligible in solution and solid.
  • the sugars can be present as a furanose (5-ring) or pyranose (6-ring). Furthermore, a new stereocenter is formed during ring closure. Depending on the position of the OH group, a distinction is made between alpha and beta anomers.
  • Enantiomeric forms e.g. The glucose is identified by the prefixes D and L. In nature, only D-glucose occurs.
  • L-glucose is only synthetically accessible.
  • D-glucose for example, exists almost exclusively in the pyranosefrom. D-glucose thus means below:
  • the wavy cusp at the anomeric center indicates that it is or can be a mixture of alpha and befa anomers. Detailed information on monosaccharides can be found in
  • Particularly preferred compounds according to the invention are derived, for example, from the following sugars.
  • the selection of the starting materials preferred for the synthesis of the compounds I according to the invention is not limited to natural occurring carbohydrates. Also synthetically accessible sugars, enantiomers, derivatives or compounds modified by chemical reactions are preferred starting materials for the
  • x and y are both 0, as shown in formula IA:
  • R 1 , R 2 , Sp, P, m and A 2 are as defined above.
  • radicals [P-Sp-] can be present and following at any of the existing positions of the H atoms, ie also directly next to R 1 or R 2 .
  • R 1 to R 5 assume the meanings given for R 1 , but R 1 "5 are preferably hydrogen, straight-chain or branched
  • X 1 to X 5 are defined as X above,
  • Sp 1 to Sp 5 are defined as Sp 'above, and
  • P 1 to P 5 are defined as P above.
  • IA1-IA19 compounds having a tetrahydropyran ring
  • IA1-IA10 compounds having more than two polymerizable groups are preferred.
  • the polyfunctionalized ring A 2 of formula I is particularly preferred with mesogenic radicals of the formula
  • radicals preferably have the following meanings:
  • Particularly preferred bridges Z 1 , Z 3 are, for example
  • one of the parameters x or y is equal to zero.
  • Preferred structures IB resulting therefrom are reproduced below in sub-formulas IB-1 to IB-5, wherein a planar notation is chosen. This is all possible stereoisomers (Enantiomers and diastereoisomers, see Zucker Weg Weg above) included. For the purposes of the present invention, preference is given to all possible stereoisomers which have been disclosed previously
  • R 1 5 is hydrogen, straight-chain or branched alkyl, alkenyl, alkoxy or alkoxymethyl having 1 to 12 carbon atoms; particularly
  • R 1 , A 1 , Z 1 , X 1 "5 , Sp “ 5 , P 1 "5 and x are as defined above.
  • Stereoisomers enantiomers and diastereoisomers resulting from the position of the substituents on the ring.
  • IC Sp 1 5 -P 1 "5 may be replaced one or more times by R 1" 5 .
  • R 1 5 here assume the meanings given for R 2 , but R 1 "5 is preferably hydrogen, straight-chain or branched alkyl, alkenyl, alkoxy or alkoxymethyl having 1 to 12 C atoms, particularly preferably hydrogen or alkoxy.
  • R 1 , R 2 , A 1 , A 2 , ZZ 2 , X 1 "5 , Sp 1" 5 , P 1'5 , x and y are as defined above.
  • Simple sugars can chain via a glycosidic bond through a condensation reaction to di- or polysaccharides.
  • Preferred compounds of the formula I are also derived from disaccharides (double sugars such as granulated sugar or milk sugar).
  • Particularly preferred compounds according to the invention are derived, for example, from maltose, cellobiose, isomaltose, isomaltulose,
  • Gentiobiose trehalose, sucrose, lactose, laminaribiose.
  • Sub-formula for particularly preferred compounds derived from maltose are particularly preferred.
  • Sub-formula for particularly preferred compounds derived from sucrose.
  • the hydroxy functions of the carbohydrates are decisively used, thereby -O- is given as part of the spacer -Sp ' -X-.
  • Such compounds are particularly preferred.
  • oo-bromoalkanoic acids 2.
  • ⁇ -Bromalkankladchloride 6 are used. These are derived from the carboxylic acids 2, for example, by reaction with thionyl chloride.
  • the sugar 1 is alkylated / allylated with allyl bromide (7) [A. Leydet et al., J. Med. Chem. 1997, 40, 350-356]. Allyl bromide (7) is a
  • Alkylating agents such as alkyl bromides or alkyl tosylates, are disclosed in U.S. Patent Nos. 3,846,066 and 5,402,866 Usually not reactive enough to react sufficiently well with free sugars.
  • Reaction sequence can be carried out analogously with other starting materials which are preferred in the context of this invention.
  • the perallylated compound 8 or analogs are also suitable.
  • OH groups of compounds such as compound 9 can of course also be converted into other suitable leaving groups.
  • bromides particular preference is also given to iodides, chlorides, tosylates, mesylates or triflates (in each case not shown).
  • W 1 R.
  • R is preferably H or CH a .
  • reaction media solvents such as dichloromethane, ether, ethyl acetate, toluene, etc.
  • sugar chemistry is first of all protective, in many cases even first of all OH groups (see also deoxygenation at the anomeric center Scheme 30).
  • glycosides e.g., alkyl glycosides such as compound 40
  • Alkyl glycosides are easily obtained by reacting the sugars with alcohols in the presence of acid. It is about a
  • R is preferably H or CKr
  • a protected spacer group are provided. This can be done in the sense of an acetalization with compounds 43 or in the form of an alkylation with compounds 36a. Here is also the possibility to attach other spacers than at the other positions. Thus, e.g. a group with different spacer length q1 be attached. q1 denotes an integer between 1 and 24, preferably between 1 and 12. After deprotection, esterification to the preferred acrylates may take place.
  • reaction sequence can be further simplified (see Scheme 13).
  • the spacer provided with a protective group can be introduced in the first step.
  • Scheme 13 Synthesis and reaction of a glycoside 44 with protected type 36 bromoalkanols exemplified by L - (+) - arabinose (35).
  • W 1 R.
  • R is preferably H or CH.
  • Particularly preferred reactants are therefore alkyl alcohols 55 and 55a, cyclohexyl alcohols 58, cyclohexylmethanols 60, phenols 62 and benzyl alcohols 64 (compare Scheme 16) but also carboxylic acids (not shown here).
  • Example B 1, 3-Glycolspacer by all-round allylation
  • the anomeric center can be protected as before as alkyl glycoside, or the desired spacer or precursor can be introduced directly (compounds 73, q1 is an integer between 1 and 24, preferably between 1 and 12).
  • compounds 73, q1 is an integer between 1 and 24, preferably between 1 and 12).
  • the secondary OH groups may be e.g. be esterified with bromoalkanoic acids.
  • the trityl protecting group in 75 is then removed and appropriate groups can be attached to the primary OH group. Again an esterification was chosen, this time with a ⁇ -bromoalkanoic acid 2a with a different chain length s1.
  • s1 is an integer between 1 and 24, preferably between 1 and 12.
  • the primary OH group is also a preferred position to other groups or R2- [A 3 -Z 3 ] y - to attach preferably alkyl radicals and mesogenic radicals.
  • the tetrabenzyl ether 80 can be used for this purpose. This is obtained from D - (+) - glucose (70). First, the C6-OH group is protected as trityl ether, then the benzylated other positions. After cleavage of the trityl group, 80 is obtained (see Scheme 20).
  • a functionalization takes place by alkylation of the primary OH group with alkyl halides (eg, the iodides 81), tosylates or triflates (see Examples in Scheme 21). Subsequently, the benzyl groups are split off and the remaining OH functions of compounds 83 can be converted accordingly.
  • alkyl halides eg, the iodides 81
  • tosylates or triflates see Examples in Scheme 21.
  • the structural part -OX 1 1 - thus corresponds for example to the group -X- in formula I or X 1 in the formulas IA to IC.
  • Another preferred reaction is the esterification of the C6-OH function with carboxylic acids 85 (see Scheme 22).
  • the C6 hydroxyl group can be converted to a good leaving group (e.g., a bromide or a tosylate).
  • a good leaving group e.g., a bromide or a tosylate.
  • Compounds such as 93 or 98 may then be further conjugated to nucleophiles (preferably with carbon nucleophiles, e.g., Grignard reagents 94 and O nucleophiles, e.g., derived from phenols 89 alcohols 99 or carboxylic acids 85)
  • Oxidation of 80 provides the aldehyde 102. This is a preferred substrate for I / I / Wg reactions (see Scheme 25) or addition reactions.
  • the mutually c / 's-OH groups at C4 and C5 can be selectively protected as the acetonide (compound 118).
  • the discrimination between the primary and the secondary OH group then succeeds again with the trityl protecting group.
  • the remaining OH group can be suitably derivatized.
  • the protecting groups can be split off to 121. This can also be done successively to install different spacers. This possibility is not shown here for the sake of simplicity.
  • a functionalization to polymerizable compounds 122 or 123 for example, by the methods listed above.
  • vicinal OH groups can be converted into epoxides. These can then be opened with nucleophiles.
  • a distinction between two secondary OH groups, and a further possibility for the formation of CC-linkages in the Sense an S N 2 reaction was shown.
  • An example is shown in Scheme 29.
  • the benzylidene acetal 124 formed from the methyl glycoside of D - (+) - glucose is converted into the epoxide 125.
  • This is then opened, for example, with Grignard reagents 126.
  • the OH groups in 127 can then be suitably functionalized after release.
  • Another preferred form of functionalization concerning the anomeric center is its fluorination.
  • fluorination for example, an even better compatibility with the often highly fluorinated LC materials can be achieved.
  • Glycosyl fluorides may also be selected from acetates, e.g. obtained by reaction with HF-pyridine complex (see Scheme 31)
  • the products of the alkylation with ⁇ -bromomethylacetates 137 can be saponified and acrylate groups can be attached, e.g. directly via the esterification with (2-hydroxyalkylene) acrylates 47.
  • Another object of the invention is thus generally a process for the preparation of compounds of formula I as defined for the compounds by derivatizing monosaccharides or disaccharides, in particular of the above-mentioned or illustrated saccharides and their derivatives.
  • Another object of the invention is the use of the
  • Preferred liquid-crystalline media are characterized in that, after stabilization of the blue phase by polymerization, they are at least in the range from 15 to 30 ° C., preferably from 10 to 40 ° C., more preferably from 0 to 50 ° C., very preferably from -10 to 60 ° C have a blue phase.
  • liquid-crystalline media which comprise a polymer of at least one monomer component of the formula I or which contain at least one unpolymerized monomer of the formula I, or both.
  • Particularly preferred media according to the invention are mentioned below:
  • the medium contains one or more monoreactive monomers or a polymer which is made up of one or more monoreactive monomers and optionally further monomers.
  • the proportion of monoreactive monomers is preferably 1 to 15%, more preferably 2 to 12%.
  • Preferred monoreactive monomers are those of the formula P given below, in which the individual groups particularly preferably adopt the preferred embodiments for formula P and only the radical R a is polymerizable.
  • the medium contains in addition to the aforementioned monoreactive
  • Monomers one or more cross-linking compounds, which are characterized by a plurality of reactive groups. These include the compounds of formula I.
  • the medium contains one or more di-reactive monomers or a polymer consisting of one or more double-reactive monomers
  • Monomers and optionally further monomers is constructed.
  • the proportion of di-reactive monomers is preferably 0 to 9%, more preferably 0 to 5%.
  • the di-reactive monomers are completely or partially replaced by the compounds of the formula I according to the invention having 3 or more reactive groups.
  • the sum of mono- and di-reactive monomers is preferably 3 to 7%, more preferably 6-14%.
  • the three or more (> 3) reactive monomers are preferably part or all of the compounds of formula I.
  • the ratio of monoreactive monomers to crosslinkers is preferably between 3: 1 and 1: 1. The ratio depends on the number of reactive groups of the crosslinkers involved. It is particularly preferred when using four-fold cross-linking crosslinkers between 3: 1 and 2.1, when using doubly reactive
  • Crosslinkers particularly preferably between 1, 5: 1 and 1: 1.
  • monoreactive monomers have a structure of the formula R a -Sp-P
  • P is a polymerizable group
  • Sp is a spacer group or a single bond
  • R a represents an organic radical having at least 3 C atoms.
  • the residue R a may be a so-called mesogenic residue, which usually bonds one or more rings to the leg, or a simple, usually chain-like, non-mesogenic residue.
  • Non-mesogenic radicals are preferably straight-chain or branched alkyl having 1 to 30 C atoms, in which also one or more non-adjacent CH 2 groups are each independently of one another
  • P and Sp correspond to the meanings given below for formula I * .
  • Preferred mesogenic monomers having one, two or more
  • R a and R b are each, independently of one another, P, P-Sp-, H, halogen, SF 5 ,
  • N0 2 a carbon group or hydrocarbon group, wherein at least one of R a and R b is or contains a group P or P-Sp-,
  • B 1 and B 2 are each independently an aromatic
  • heteroaromatic, alicyclic or heterocyclic group preferably having 4 to 25 ring atoms, which may also contain fused rings, and which may also be monosubstituted or polysubstituted by L,
  • P-Sp- H, OH, CH 2 OH, halogen, SF 5 , NO 2 , a carbon group or hydrocarbon group,
  • Z b is the same or different at each occurrence -O-, -S-, -CO-,
  • R ° and R 00 are each independently H or alkyl with 1 to 12 C
  • Particularly preferred compounds of the formula P are those in which optionally one or more of the radicals R a and R b are each, independently of one another, P, P-Sp-, H, F, Cl, Br, I, -CN,
  • 2,5-diyl where all of these groups may be unsubstituted or monosubstituted or polysubstituted by L, LP, P-Sp-, OH, CH 2 OH, F, Cl, Br, I, -CN, -NO 2 , -NCO , -NCS,
  • carbon group means a monovalent or polyvalent organic group containing at least one carbon atom, which either contains no further atoms (such as -CsC-), or optionally one or more further atoms such as N , O, S, P, Si, Se, As, Te or Ge (eg carbonyl, etc.).
  • hydrocarbon group means a carbon group which additionally contains one or more H atoms and optionally one or more heteroatoms such as, for example, N, O, S, P, Si, Se, As, Te or Ge.
  • Halogen means F, Cl, Br or I, preferably F or Cl.
  • a carbon or hydrocarbon group may be a saturated or unsaturated group. Unsaturated groups are, for example, aryl, alkenyl or alkynyl groups.
  • a carbon or hydrocarbon radical having more than 3 C atoms may be straight-chain, branched and / or cyclic, and may also have spiro-linkages or fused rings.
  • alkyl alkyl
  • aryl means an aromatic carbon group or a group derived therefrom.
  • heteroaryl means "aryl” as defined above containing one or more heteroatoms. Preferred carbon and hydrocarbon groups are
  • carbon and hydrocarbon groups are d- C 40 alkyl, C 2 -C 40 alkenyl, C 2 -C 40 alkynyl, C 3 -C 40 Al ⁇ y ⁇ , C 4 -C 40 alkyldienyl, C 4 -C 0 polyenyl , C 6 -C 40 aryl, C 6 -C 40 alkylaryl, C 6 -C 40 arylalkyl, C 6 -C 40 alkylaryloxy, C 6 -C 4 Q ArylaJkyJoxy, C 2 -C 4 o heteroaryl, C 4 -C Q Cycloalkyl, C 4 -C 40 cycloalkenyl, etc.
  • CC 22 alkyl Particularly preferred are CC 22 alkyl, C 2 -C 22 alkenyl, C 2 -C 22 alkynyl, C 3 -C 22 allyl, C 4 -C 22 alkyl dienyl, C 6 -C 12 aryl, C 6 -C 20 arylalkyl and C 2 -C 20 heteroaryl.
  • carbon and hydrocarbon groups are straight-chain, branched or cyclic alkyl radicals having 1 to 40,
  • R * is preferably H, halogen, a straight-chain, branched or cyclic alkyl chain having 1 to 25 C atoms, in which one or more nonadjacent C atoms are represented by -O-, -S-, -CO-, -CO- O-, -O-CO-, -O-CO- O- may be replaced, wherein also one or more H atoms may be replaced by fluorine, an optionally substituted aryl or aryloxy group having 6 to 40 carbon atoms, or an optionally substituted heteroaryl or Heteroaryloxy group having 2 to 40 carbon atoms.
  • Preferred alkoxy groups are, for example, methoxy, ethoxy, 2-methoxyethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, 2-methylbutoxy, n-pentoxy, n-hexoxy, n- Heptoxy, n-octoxy, n-nonoxy, n-decoxy, n-undecoxy, n-dodecoxy, etc.
  • alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, n-hexyl, cyclohexyl, 2- Ethylhexyl, n-heptyl,
  • Preferred alkenyl groups For example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyc octenyl, etc.
  • Preferred alkynyl groups are, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, octynyl, etc.
  • Preferred alkoxy groups are, for example, methoxy, ethoxy, 2-methoxyethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, 2-methylbutoxy, n-pentoxy, n-hexoxy, n- Heptoxy, n-octoxy, n-nonoxy, n-decoxy, n-undecoxy, n-dodecoxy, etc.
  • Preferred amino groups are, for example, dimethylamino,
  • Aryl and heteroaryl groups may be mononuclear or polynuclear, that is, they may have a ring (such as phenyl) or two or more rings which may also be fused (such as naphthyl) or covalently linked (such as eg biphenyl), or a combination of fused and linked rings.
  • Heteroaryl groups contain one or more heteroatoms, preferably selected from O, N, S and Se.
  • mono-, di- or trinuclear aryl groups having 6 to 25 carbon atoms and mono-, di- or trinuclear heteroaryl groups having 2 to 25 carbon atoms, which optionally contain fused rings and are optionally substituted.
  • mono-, di- or trinuclear heteroaryl groups having 2 to 25 carbon atoms, which optionally contain fused rings and are optionally substituted.
  • 5-, 6- or 7-membered aryl are especially preferred.
  • Heteroaryl groups wherein also one or more CH groups can be replaced by N, S or O so that O atoms and / or S atoms are not directly linked.
  • Preferred aryl groups are, for example, phenyl, biphenyl, terphenyl, [1, 1'3] terphenyl-2'-yl, naphthyl, anthracene, binaphthyl, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, tetracene, pentacene, benzopyrene, fluorene, Indene, indenofluorene, spirobifluorene, etc.
  • Preferred heteroaryl groups are for example 5-membered rings such as pyrrole, pyrazole, imidazole, 1, 2,3-triazole, 1, 2,4-triazole, tetrazole, furan, Tbiopben, Seienophen, OxazoJ, Jsoxazo ), 1,2-thiazole, 1,3-tiazole, 1,2,3-oxadiazole, 1, 2,4-oxadiazole, 1, 2,5-oxadiazole, 1, 3,4-oxadiazole, 1, 2, 3-thiadiazole, 1, 2,4-thiadiazole, 1, 2,5-thiadiazole, 1, 3,4-thiadiazole, 6-membered rings such as pyridine, pyridazine, pyrimidine, pyrazine, 1, 3,5-triazine, 1 , 2,4-triazine, 1, 2,3-triazine, 1, 2,4,5-tetrazine, 1, 2,3,4-tetrazine, 1, 2,3,5-t
  • heteroaryl groups can also be reacted with alkyl, alkoxy, thioalkyl, fluorine, fluoroalkyl or further aryl or
  • heteroaryl be substituted.
  • the (non-aromatic) alicyclic and heterocyclic groups include both saturated rings, ie those exclusively
  • Heterocyclic rings contain one or more heteroatoms, preferably selected from Si, O, N, S and Se.
  • the (non-aromatic) alicyclic and heterocyclic groups may be mononuclear, i. contain only one ring (e.g.
  • Cyclohexane or polynuclear, ie containing several rings (such as decahydronaphthalene or bicyclooctane). Particularly preferred are saturated groups. Also preferred are mono-, di- or trinuclear groups having 3 to 25 carbon atoms, which optionally contain fused rings and are optionally substituted. Also preferred are 5-, 6-, 7- or 8-membered carbocyclic groups in which also one or more carbon atoms may be replaced by Si and / or one or more CH groups may be replaced by N and / or one or more non-adjacent CH 2 groups may be replaced by -O- and / or -S-. Preferred alicyclic and heterocyclic groups are, for example, 5-membered groups such as cyclopentane, tetrahydrofuran,
  • Tetrahydrothiofuran pyrrolidine, 6-membered groups such as cyclohexane, cyclohexene, tetrahydropyran, tetrahydrothiopyran, 3-dioxane, 1,3-dithiane, piperidine, 7-membered groups such as cycloheptane, and fused groups such as tetrahydronaphthalene, decahydronaphthalene, indane,
  • Preferred substituents are, for example, solubility-promoting
  • Groups such as alkyl or alkoxy, electron-withdrawing groups such as fluorine,
  • Substituted silyl or aryl is preferably substituted by halogen, -CN, R ° -OR °, -CO-R 0 , -CO-OR 0 , -O-CO-R 0 or -O-CO-OR 0 substituted, wherein R ° has the meaning given above.
  • substituents L are, for example, F, Cl, CN, NO 2 , CH 3 , C 2 H 5 , OCH 3 , OC 2 H 5 , COCH 3 , COC 2 H 5 , COOCH 3 , COOC 2 H 5 , CF 3 , OCF 3 , OCHF 2 , OC 2 F 5 , furthermore phenyl.
  • the polymerizable group P is a group suitable for a
  • Polymerization reaction such as radical or ionic chain polymerization, polyaddition or polycondensation, or for a polymer-analogous reaction, for example, the addition or
  • Condensation to a polymer backbone is suitable.
  • Preferred groups P are defined as for formula I above.
  • Preferred spacer groups Sp are selected from the formula Sp'-X- as defined above for formula I.
  • P-Sp- is a radical having two or more polymerisable groups
  • -C (R 00 ) C (R 000 ) -, -C ⁇ C-, -N (R 00 ) -, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- may be replaced so that O- and / or S atoms are not directly linked to each other, and where also one or more H atoms may be replaced by F, Cl or CN, wherein R 00 and R 000 have the abovementioned meaning, aa and bb are each independently 0, 1, 2, 3, 4, 5 or 6, and
  • P 1 '5 are each independently one of those given for P.
  • the polymerisable compounds and RMs can be prepared analogously to those known to those skilled in the art and described in standard works of organic chemistry, such as in Houben-Weyl, Methods of Organic Chemistry, Thieme Verlag, Stuttgart. Other synthetic methods can be found in the documents cited above and below. In the simplest case, the synthesis of such RMs takes place for example by esterification or etherification of 2,6-dihydroxynaphthalene or 4,4'-di-ydroxybjpber> yJ with corresponding acids, acid derivatives or halogenated compounds containing a group P, such as (meth) acrylic acid chloride or
  • the non-polymerizable fraction preferably comprises compounds selected from Table A (see Example).
  • the blue-crystalline liquid-crystalline media according to the invention preferably have a positive dielectric anisotropy. They can be designed to have very high dielectric anisotropy combined with high optical anisotropies.
  • Preferred further compounds for the liquid-crystalline media according to the invention are selected from the compounds of the formula II and III:
  • asymmetric linkers eg, CF 2 O
  • asymmetric linkers may be oriented in both possible directions, X 1 F, Cl, CN, or
  • the liquid-crystalline media preferably contain between 20 and 40% by weight of compounds of the formula II.
  • the compounds of the formula III are preferably used, if present, with up to 20% by weight.
  • the remaining other compounds, if present, are selected from further compounds with high dielectric anisotropy, high optical anisotropy and preferably with a high clearing point.
  • Preferred compounds of the formula III are those of the formula IIIa or IIIb:
  • R is as defined for formula III.
  • the preparation of the FK media which can be used according to the invention is carried out in a conventional manner, for example by mixing one or more of the abovementioned compounds with one or more polymerizable compounds as defined above and, if appropriate, with further liquid-crystalline compounds and / or additives.
  • the abovementioned compounds with one or more polymerizable compounds as defined above and, if appropriate, with further liquid-crystalline compounds and / or additives.
  • FK media according to the invention may also contain compounds in which, for example, H, N, O, Cl, F have been replaced by the corresponding isotopes.
  • alkyl alkenyl, etc. are defined as follows:
  • alkyl embraces straight-chain and branched alkyl groups having 1-9 carbon atoms, in particular the straight-chain groups methyl, ethyl, propyl, butyl, pentyl, hexyl and heptyl. Groups of 2-5 carbon atoms are generally preferred.
  • alkenyl includes straight-chain and branched alkenyl groups having up to 9 carbon atoms, especially the straight-chain groups.
  • alkenyl groups are C 2 -C 7 -1E-alkenyl, C 4 -C 7 3E-alkenyl, C 5 -C 7 -alkenyl ) C 6 -C 7 -5-alkenyl and C 7 -6- Alkenyl, in particular C 2 -C 7 -1 E-alkenyl, C 4 -C 7 3E-alkenyl and C 5 -C 7 -4-alkenyl.
  • alkenyl groups examples are vinyl, 1E-propenyl, 1E-butenyl, 1E-pentenyl, 1E-hexenyl, 1E-heptenyl, 3-butenyl, 3E-pentenyl,
  • fluoroalkyl in this application includes straight-chain groups having at least one fluorine atom, preferably one
  • fluorine i. Fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl and 7-fluoroheptyl. Other positions of the fluorine are not excluded.
  • halogenated alkyl preferably includes mono- or polyfluorinated and / or chlorinated radicals. Perhalogenated radicals are included. Particularly preferred are fluorinated alkyl radicals,
  • alkylene includes straight-chain and branched
  • Alkanediyl groups having 1-12 carbon atoms in particular the
  • Pentylene Groups of 2-8 carbon atoms are generally preferred. Further combinations of the embodiments and variants of
  • K crystalline
  • N nematic
  • BP blue phase
  • Tg glass transition temperature
  • Example 1 5- (2-Methyl-acryloyloxy) valeric acid (3R, 4S, 5R) -4,5,6-tris [5- (2-methyl-acryloyloxy) -pentanoyloxy] -tetrahydropyran-3-yl ester
  • Washed sodium chloride solution The solution is dried with sodium sulfate and completely concentrated. The residue will be
  • 5-acryloyloxy-valeric acid (3R, 4S, 5R) -4,5,6-tris (5-acryloyloxy-pentanoyloxy) -tetrahydropyran-3-yl ester is synthesized as described below.
  • Example 4 2-Methacrylic acid (3R, 4S, 5S) -4,5,6-tris (2-methyl-acryloyloxy) -tetrahydropyran-3-yl ester
  • 2-methacrylic acid (3R, 4S, 5S) -4,5,6-tris (2-methyl-acryloyloxy) -tetrahydropyran-3-yl ester is synthesized as described below.
  • the compound of the invention is 2-methacrylic acid-3 - ⁇ (3S, 4R, 5R) -2,3,5-tris- [3- (2-methy (-acryloy (oxy) -propoxy] -tetrahydropyran-4-yloxy ⁇ -propyl ester synthesized as described below.
  • Example 1 Analogously to Example 1, the example compounds 6-9 are obtained from the corresponding sugars and reaction with bromovaleric acid and methacrylic acid.
  • the spectroscopic data correspond respectively to the structures.
  • R 220 has the phase sequence 82.5 N 97 I.
  • RM257 has the phase sequence K 66 N 127 I.
  • phase properties of the medium are determined in a test cell of about 10 micrometers thickness and an area of 2x2.5 cm.
  • the filling is achieved by capillary action at a temperature of 75 ° C.
  • the measurement is carried out under a polarizing microscope with hot stage at a temperature gradient of 1 ° C / min.
  • the polymerization of the media is carried out by irradiation with a UV lamp (Hönle, Bluepoint 2. 1, 365 nm interference filter) with an effective power of about 1.5 mW / cm 2 for 180 seconds.
  • a UV lamp Hönle, Bluepoint 2. 1, 365 nm interference filter
  • Polymerization initially occurs at a temperature in which the medium is in blue phase I (BP-I).
  • BP-I blue phase I
  • the polymerization takes place in several substeps, which gradually to a complete
  • the temperature range of the blue phase usually changes during the polymerization. Between each sub-step, therefore, the temperature is adjusted so that the medium is still present in the blue phase. In practice, this can be done so that after each irradiation process of about 5 s or longer, the sample is observed under the polarizing microscope. If the sample becomes darker, this indicates a transition to the isotropic phase.
  • the total irradiation time leading to the maximum stabilization is typically 180 seconds at the indicated irradiation power. Further polymerizations can be carried out after an optimized irradiation Temperature program are performed. Alternatively, the
  • Polymerization can also be carried out in a single irradiation step, especially if a wide blue phase is present even before the polymerization.
  • phase width of the blue phase is determined.
  • the electro-optical characterization is then carried out at different temperatures within and possibly outside this range.
  • test cells used are equipped on one side with interdigital electrodes on the cell surface.
  • the cell gap, the electrode gap and the electrode width are typically each
  • the test cells do not have an alignment layer. The cell is in between for electro-optical characterization
  • crossed polarizing filters wherein the longitudinal direction of the electrodes occupy an angle of 45 ° with the axes of the polarizing filter.
  • the measurement is carried out with a DMS301 (Autronic-Melchers) at right angles to the cell level, or by means of a high-sensitivity camera on the
  • the operating voltage at the cell electrodes is applied in the form of square-wave voltage with alternating sign (frequency 100 Hz) and variable amplitude as described below.
  • the transmission in the de-energized state is set as 0%. While the operating voltage is increased, the transmission is measured. Achieving the maximum value of about 100% intensity determines the characteristic magnitude of the operating voltage V100.
  • the characteristic voltage V 10 becomes 0% of maximum transmission determined.
  • Temperature range limited by and T 2 is referred to as a usable, flat temperature range (FB).
  • the width of this "flat area" (FB) is (T 2 -T r ) and is referred to as the width of the flat area (BFB) (engl, 'flat ranks').
  • the exact values of 1 ⁇ and T 2 are determined by the intersections of tangents to the flat curve section FB and the adjacent steep curve sections in the V 10 o temperature diagram.
  • the switching times are determined when switching on and off ( ⁇ ⁇ , ⁇ 0 »).
  • the switching time ⁇ 0 ⁇ is defined by the time to reach 90% intensity after applying a voltage of the level of Vi 0 o at the selected temperature.
  • the switching time is also determined at different temperatures in the region of the blue phase.
  • voltages at 50% transmission are characteristic hysteresis values and are referred to as ⁇ 5 ⁇ and AV 50 , respectively.
  • Examples 1 (for comparison), M2, M3 (for comparison), M4 The following polymerizable media are combined:
  • the media are characterized as described before polymerization. Then the RM components are polymerized by single irradiation (180 s) in the blue phase, and the resulting media are characterized again.
  • the inventive RM-1 polymer-stabilized media M2 and M4 show a significant reduction in the operating voltage (V 10 , Vi 0 o) and the hysteresis (AV 50 ) compared to the media M1 and M3 (without RM-1).
  • the mixtures M3 and M4 differ from the mixtures M1 and M2 by an increased proportion of chiral dopant, whereby M3 / 4 in contrast to M 1/2 invisible blue phases form (shift the wavelengths in the UV range).
  • M3 / 4 in contrast to M 1/2 invisible blue phases form (shift the wavelengths in the UV range).

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Abstract

L'invention concerne des composés polymérisables de formule (I), dans laquelle P, Sp, R1, R2, A1, A2, A3, Z1, Z3, V, m, n, o, x et y ont les significations données dans la revendication 1, ainsi que des milieux à cristaux liquides contenant au moins un composé de formule (I). Les composés sont de préférence des dérivés du sucre.
PCT/EP2010/005134 2009-09-18 2010-08-20 Composés polymérisables et milieux à cristaux liquides Ceased WO2011032630A1 (fr)

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