Polymerizable compound

Abstract

The present application relates to polymerizable compounds, methods and intermediates for their preparation, compositions containing them, polymers prepared from the compounds or compositions, and uses of the polymerizable compounds, compositions and polymers.

Description

Technical Field

[0001] This application relates to polymerizable compounds, methods and intermediates for their preparation, compositions containing the same, polymers prepared from the compound or composition, and uses of the polymerizable compound, composition, and polymer. Background Technology

[0002] Polymerizable compounds, compositions containing them, and polymer particles or polymer films prepared therefrom have been proposed in the prior art for a variety of applications, such as protective, decorative, or optoelectronic applications. These polymerizable compounds can be advantageously polymerized by in-situ polymerization, such as UV-photopolymerization.

[0003] However, polymerizable compounds known from the prior art often exhibit disadvantages such as difficulty in synthesis, low yield, slow or incomplete polymerization, low stability, or low absorption in the desired UV wavelength range for photopolymerization.

[0004] Therefore, the object of the present invention is to provide improved polymerizable compounds and compositions that do not have the disadvantages of materials known in the prior art and exhibit one or more advantages, such as ease of synthesis, high yield, rapid and complete polymerization, high stability, and high ultraviolet absorption. In particular, polymerizable compounds that can be efficiently polymerized at longer ultraviolet wavelengths >300 nm are needed, for example, as is frequently used in the manufacture of optoelectronic devices. Additionally, polymerizable compounds that exhibit good solubility in organic solvents and liquid crystal media are also required.

[0005] The inventors have discovered that these objectives can be achieved by providing polymerizable compounds as disclosed and claimed below. Summary of the Invention

[0006] This invention relates to compounds of formula I.

[0007] P-Sp-A 1 -(Z 1 -A 2 ) z -R b I

[0008] Each group, independently of the others and in the same or different manner each time it appears, has the following meaning:

[0009] R b Indicates P-Sp- or R,

[0010] R represents F, Cl, -CN, or a straight-chain, branched, or cyclic alkyl group having 1-25 carbon atoms, wherein one or more non-adjacent CH2- groups are optionally surrounded by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, CR0 =CR 00 -、-C≡C-、 The O- and / or S- atoms are replaced in a manner in which they are not directly connected to each other, and one or more H atoms are optionally replaced by F, Cl, or P-Sp-.

[0011] P represents a polymerizable group.

[0012] Sp represents a spacer group optionally substituted with P, or a single bond.

[0013] A 1 A 2 This refers to an alicyclic, heterocyclic, aromatic, or heteroaromatic group having 4-20 ring atoms, which is monocyclic or polycyclic and optionally substituted by one or more L, A, or P-Sp- groups.

[0014] Z 1 Represents -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -(CH2) n1 -, -CF2CH2-, -CH2CF2-, -(CF2) n1 -, -CH=CH-, -CF=CF-, -CH=CF-, -CF=CH-, -C≡C-, -CH=CH-CO-O-, -O-CO-CH=CH-, -CH2-CH2-CO-O-, -O-CO-CH2-CH2-, -CR 0 R 00 -or a single key,

[0015] R 0 R 00 It represents H or an alkyl group having 1-12 carbon atoms.

[0016] A represents an alkyl group having 2-12, preferably 2-8, carbon atoms, wherein one or more preferably uncapped CH2 groups are replaced by S such that the S atoms are not directly connected to each other; preferably a thioalkyl group having 1-7 carbon atoms, very preferably SCH3.

[0017] L represents F, Cl, -CN, P-Sp- or a straight-chain, branched or cyclic alkyl group having 1-25 C atoms, wherein one or more non-adjacent CH2- groups are optionally surrounded by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, CR 0 =CR 00 -、-C≡C-、 The O- and / or S- atoms are replaced in a manner in which they are not directly connected to each other, and one or more H atoms are optionally replaced by P-Sp-, F or Cl.

[0018] z represents 0, 1, 2, 3, or 4.

[0019] n1 represents 1, 2, 3, or 4.

[0020] The compound is characterized by containing at least one A group. 1 Or A 2 It is substituted by at least one group A.

[0021] The present invention further relates to methods for preparing compounds of formula I and novel intermediates used or obtained in these methods.

[0022] The present invention further relates to polymerizable compositions comprising one or more compounds of formula I.

[0023] The present invention further relates to polymers obtained by polymerizing a compound of formula I or a composition comprising thereto.

[0024] Furthermore, the present invention relates to compounds of formula I, compositions comprising thereof, or polymers obtained by polymerizing compounds of formula I or compositions comprising thereof for protective, decorative, or optoelectronic applications or for use in liquid crystal media.

[0025] The polymerizable compounds and compositions according to the present invention are preferably polymerized by photopolymerization, and very preferably by UV photopolymerization.

[0026] This invention further relates to compounds of formula II.

[0027] Pg-Sp-A 1 -(Z 1 -A 2 ) z -R b1 II

[0028] Where Pg is OH, H, or a protected or masked hydroxyl group, and R b1 For R or Pg-Sp-, and Sp, A 1 A 2 R, Z, and z have the meaning of Equation I or the meaning of the preferred context, and A 1 and A 2 At least one of them is replaced by at least one group A as defined in Formula I.

[0029] Furthermore, the present invention relates to the use of compounds of formula II as intermediates in the synthesis of polymerizable compounds (especially those of formula I).

[0030] Furthermore, the present invention relates to a method for synthesizing compounds of formula I or its subforms by esterifying or etherifying a compound of formula II (wherein Pg represents OH or a protected or masked hydroxyl group) using a corresponding acid, acid derivative or halogenated compound containing a polymerizable group P, optionally in the presence of a dehydrating agent. Invention Details

[0032] Compound I exhibits the following advantageous properties:

[0033] - Rapid polymerization, low amount of residual unreacted monomers.

[0034] - Good heat resistance stability

[0035] - Good solubility in organic solvents and liquid crystal media.

[0036] - Good low-temperature stability (LTS),

[0037] - Rapid and complete UV photopolymerization, especially at 300-380nm and particularly at longer UV wavelengths greater than 320nm.

[0038] Unless otherwise stated, compounds of formula I are preferably selected from achiral compounds.

[0039] Unless otherwise stated, the term “polymerizable compound” as used herein shall be understood to mean a polymerizable monomeric compound.

[0040] Unless otherwise stated, the term "non-polymerizable compound" as used herein shall be understood to mean that it does not contain functional groups suitable for polymerization under the conditions commonly applied to the polymerization of compounds of Formula I.

[0041] In the context This indicates the trans-1,4-cyclohexyl ring.

[0042] and represents 1,4-Phenylidene ring.

[0043] In groups In this system, the single bond shown between two ring atoms can be attached to any vacant position on the benzene ring.

[0044] If in formula I and its subforms, group R bR or L represents alkyl and / or alkoxy groups, which can be straight-chain or branched. They are preferably straight-chain, having 2, 3, 4, 5, 6 or 7 carbon atoms, and correspondingly preferably represent ethyl, propyl, butyl, pentyl, hexyl, heptyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy or heptoxy, and methyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, octyloxy, nonoxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy or tetradecyloxy.

[0045] If in formula I and its subforms, group R b R, L, or A represent alkyl groups, wherein one or more CH2 groups are replaced by S, and the group may be straight-chain or branched. It is preferably straight-chain, having 1, 2, 3, 4, 5, 6, or 7 C atoms, and correspondingly preferably represents thiomethyl, thioethyl, thiopropyl, thiobutyl, thiopentyl, thiohexyl, or thioheptyl.

[0046] Oxaalkyl preferably represents 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, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-oxadecyl.

[0047] If in formula I and its subforms, group R b R or L represents alkoxy or oxalyl, which may also contain one or more additional oxygen atoms, provided that the oxygen atoms are not directly connected to each other.

[0048] In another preferred embodiment, R b One or more of R or L selected from -S 1 -F, -OS 1 -F, -O-S1-O-S2, where S 1 C 1-12 -alkylene or C 2-12 - Idemenyl and S 2 For H, C 1-12 -alkyl or C 2-12 -Alkenyl, and very preferably selected from -OCH2OCH3, -O(CH2)2OCH3, -O(CH2)3OCH3, -O(CH2)4OCH3, -O(CH2)2F, -O(CH2)3F, -O(CH2)4F.

[0049] If in formula I and its subforms, group R b R or L represents an alkyl group, in which one of the CH2 groups has been replaced by -CH=CH-, and it can be straight-chain or branched. It is preferably straight-chain and has 2-10 carbon atoms. Accordingly, it specifically represents vinyl, prop-1- or -2-enyl, but-1-, -2- or -3-enyl, pent-1-, -2-, -3- or -4-enyl, hex-1-, -2-, -3-, -4- or -5-enyl, hep-1-, -2-, -3-, -4-, -5- or -6-enyl, oct-1-, -2-, -3-, -4-, -5-, -6- or -7-enyl, non-1-, -2-, -3-, -4-, -5-, -6-, -7- or -8-enyl, dec-1-, -2-, -3-, -4-, -5-, -6-, -7-, -8- or -9-enyl.

[0050] If in formula I and its subforms, group R b R or L represents an alkyl or alkenyl group that is at least monosubstituted with a halogen, preferably a straight chain, and the halogen is preferably F or Cl. In the case of polysubstituted groups, the halogen is preferably F. The resulting group also includes a perfluorinated group. In the case of monosubstituted groups, the fluorine or chlorine substituent can be at any desired position, but is preferably at the ω-position.

[0051] The halogen is preferably F or Cl, with F being the most preferred.

[0052] Group -CR 0 =CR 00 - Preferably -CH=CH-.

[0053] In formula I and its derivatives, aryl and heteroaryl A 1 and A 2 They can be monocyclic, meaning they may contain one ring (e.g., phenyl) or polycyclic, meaning they contain two or more rings, which may be fused (e.g., naphthyl) or covalently bonded (e.g., biphenyl), or contain a combination of fused rings and linking rings. Heteroaryl groups contain one or more heteroatoms, preferably selected from O, N, S, and Se.

[0054] If in formula I and its subforms, group A 1 Or A 2The designation represents a monocyclic or polycyclic aryl or heteroaryl group, preferably a monocyclic, bicyclic, or tricyclic aryl group having 6 to 25 carbon atoms and a monocyclic, bicyclic, or tricyclic heteroaryl group having 2 to 25 carbon atoms, optionally containing a fused ring and optionally being substituted. Furthermore, 5-membered, 6-membered, or 7-membered aryl and heteroaryl groups are preferred, wherein one or more additional CH groups can be replaced by N, S, or O such that the O atom and / or S atom are not directly connected to each other.

[0055] Preferred aryl groups include, for example, phenyl, biphenyl, terphenyl, [1,1':3',1”]-terphenyl-2'-yl, naphthalene, anthracene, binaphthalene, phenanthrene, 9,10-dihydro-phenanthrene, pyrene, dihydropyrene, Dinaphthyl benzo[a]benzene, tetraphenyl, pentaphenyl, benzo[a]pyrene, fluorene, indene, indo[a]fluorene, spiro[a]fluorene, etc.

[0056] Preferred heteroaryl groups are, for example, 5-membered rings, such as pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, tetrazolium, furan, thiophene, selenophene, oxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, 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-tetraazine, 1,2,3,4-tetraazine, 1,2,3,5-tetraazine, or fused groups such as indole, isoindole, indole Azine, Indazole, Benzimidazole, Benzitriazole, Purine, Naphthemidazole, Phenylenazole, Pyridinazole, Pyrazinazole, Quinoxaline, Benzooxazole, Naphthemidazole, Anthrazooxazole, Phenylenazole, Isoxazole, Benzothiazolazole, Benzofuran, Isobenzofuran, Dibenzofuran, Quinoline, Isoquinoline, Pteridine, Benzo-5,6-quinoline, Benzo-6,7-quinoline, Benzo- 7,8-quinoline, benzoisoquinoline, acridine, phenothiazine, phenothiazine, benzopyridinium, quinoxaline, phenothiazine, naphthidine, azacarbazole, benzocarbine, phenanthridine, phenanthroxaline, thieno[2,3b]thiophene, thieno[3,2b]thiophene, dithieno[2,3b]thiophene, isobenzo[2,3b]thiophene, dibenzo[2,3b]thiophene, benzo[2,3b]thiophene, benzo[2,3b]thiophene, di[2,3b]thiophene, isobenzo[2,3b]thiophene, dibenzo[2,3b]thiophene, ... or combinations thereof.

[0057] (Non-aromatic) alicyclic and heterocyclic groups can include saturated rings (i.e., those containing only single bonds) and partially unsaturated rings (i.e., those containing multiple bonds). The heterocycle contains one or more heteroatoms, preferably selected from Si, O, N, S, and Se.

[0058] The (non-aromatic) alicyclic and heterocyclic groups can be monocyclic, i.e., containing only one ring (e.g., cyclohexane), or polycyclic, i.e., containing multiple rings (e.g., decahydronaphthalene or bicyclooctane). Saturated groups are particularly preferred. Furthermore, mono-, bi-, or tricyclic groups having 5-25 ring atoms are preferred, optionally containing a fused ring which is optionally substituted. Also preferred are 5-, 6-, 7-, or 8-membered carbocyclic groups, wherein one or more C atoms may be substituted with Si and / or one or more CH groups may be substituted with N and / or one or more non-adjacent CH2 groups may be substituted with -O- and / or -S-.

[0059] Preferred alicyclic and heterocyclic groups are, for example, 5-membered groups, such as cyclopentane, tetrahydrofuran, tetrahydrothiophene, pyrrolidine; 6-membered groups, such as cyclohexane, silanecyclohexane, cyclohexene, tetrahydropyran, tetrahydrothioran, 1,3-dioxane, 1,3-dithiaran, piperidine; 7-membered groups, such as cycloheptane; and fused groups, such as tetrahydronaphthalene, decahydronaphthalene, indane, bicyclo[1.1.1]pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]heptane-2,6-diyl, octahydro-4,7-bridged methylene indane-2,5-diyl.

[0060] Further preferred are compounds comprising Formula I, wherein at least one group A is an aryl or heteroaryl group. 1 Or A 2 It is preferably selected from the preferred aryl and heteroaryl groups listed above, and at least one A group is a non-aromatic, alicyclic, or heterocyclic group. 1 Or A 2 It is preferably selected from the preferred alicyclic and heterocyclic groups listed above.

[0061] The aromatic, heteroaromatic, alicyclic, and heterocyclic groups mentioned in the context may also be substituted by one or more groups L, P-Sp-, or A.

[0062] Preferred substituents L are, for example, F, Cl, -CN, each having 1-25 C atoms in a straight-chain or branched alkyl, alkoxy, alkyl carbonyl, alkoxy carbonyl, alkyl carbonyloxy, or alkoxy carbonyloxy group, wherein one or more H atoms may optionally be replaced by F, Cl, or P-Sp-.

[0063] Particularly preferred substituents L include, for example, F, Cl, CN, CH3, C2H5, OCH3, OC2H5, COCH3, COC2H5, COOCH3, COOC2H5, CF3, OCF3, OCHF2, and OC2F5.

[0064] Preferred

[0065] L has one of the meanings mentioned above.

[0066] The polymerizable group P is a group suitable for polymerization reactions, such as free radical or ionic chain polymerization, addition polymerization or condensation polymerization, or suitable for reactions similar to polymers, such as addition or condensation onto the polymer backbone. Groups suitable for chain polymerization are particularly preferred, especially those containing C=C double bonds or -C≡C- triple bonds, and groups suitable for ring-opening polymerization, such as oxobutyl or epoxy groups.

[0067] The preferred group P is selected from CH2=CW 1 -CO-O-、CH2=CW 1 -CO-、 CH2=CW 2 -(O) k3 -、CW 1 =CH-CO-(O) k3 -、CW 1 =CH-CO-NH-, CH2=CW 1 -CO-NH-, CH3-CH=CH-O-,

[0068] (CH2=CH)2CH-OCO-, (CH2=CH-CH2)2CH-OCO-, (CH2=CH)2CH-O-, (CH2=CH-CH2)2N-, (CH2=CH-CH2)2N-CO-, HO-CW 2 W 3 -、HS-CW 2 W 3 -、HW 2 N-, HO-CW 2 W 3 -NH-, CH2=CW 1 -CO-NH-, CH2=CH-(COO) k1 -Phe-(O) k2 - CH2=CH-(CO) k1 -Phe-(O) k2 -, Phe-CH=CH-, HOOC-, OCN- and W 4 W 5 W 6 Si-, where W 1 It represents H, F, Cl, CN, CF3, phenyl or alkyl with 1-5 carbon atoms, especially H, F, Cl or CH3, W 2 and W 3 Each independently represents H or an alkyl group having 1-5 carbon atoms, particularly H, methyl, ethyl, or n-propyl, W 4 W 5 and W6 Each independently represents Cl, an oxaalkyl or oxacarbonylalkyl group having 1-5 carbon atoms, and W. 7 and W 8 Each of them independently represents H, Cl or an alkyl group having 1-5 C atoms, Phe represents 1,4-phenylene, which is optionally substituted with one or more groups L as defined above, which is not P-Sp-, k1, k2 and k3 each independently represent 0 or 1, k3 preferably represents 1, and k4 represents an integer from 1 to 10.

[0069] The highly preferred group P is selected from

[0070] CH2=CW 1 -CO-O-、CH2=CW 1 -CO-、 CH2=CW 2 -O-、CH2=CW 2 -、

[0071] CW 1 =CH-CO-(O) k3 -、CW 1 =CH-CO-NH-, CH2=CW 1 -CO-NH-、

[0072] (CH2=CH)2CH-OCO-, (CH2=CH-CH2)2CH-OCO-, (CH2=CH)2CH-O-,

[0073] (CH2=CH-CH2)2N-, (CH2=CH-CH2)2N-CO-, CH2=CW 1 -CO-NH-、

[0074] CH2=CH-(COO) k1 -Phe-(O) k2 - CH2=CH-(CO) k1 -Phe-(O) k2 - Phe-CH=CH- and W 4 W 5 W 6 Si-, where W 1 It represents H, F, Cl, CN, CF3, phenyl or alkyl with 1-5 carbon atoms, especially H, F, Cl or CH3, W 2 and W 3 Each independently represents H or an alkyl group having 1-5 carbon atoms, particularly H, methyl, ethyl, or n-propyl, W 4 W 5 and W6 Each independently represents Cl, an oxaalkyl or oxacarbonylalkyl group having 1-5 carbon atoms, and W. 7 and W 8 Each of them independently represents H, Cl or an alkyl group having 1-5 C atoms, Phe represents 1,4-phenylene, k1, k2 and k3 each independently represent 0 or 1, k3 preferably represents 1, and k4 represents an integer from 1 to 10.

[0075] The highly preferred group P is selected from CH2=CW. 1 -CO-O-, especially CH2=CH-CO-O-, CH2=C(CH3)-CO-O- and CH2=CF-CO-O-, as well as CH2=CH-O-, (CH2=CH)2CH-O-CO-, (CH2=CH)2CH-O-,

[0076] Other preferred polymerizable groups P are selected from vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetyl, and epoxy, more preferably acrylate and methacrylate, and most preferably methacrylate.

[0077] If the spacer group Sp is different from the single bond, its preferred formula is Sp"-X", such that each group P-Sp- conforms to the formula P-Sp"-X"-, where

[0078] "Sp" represents a straight-chain or branched alkylene group having 1-20, preferably 1-12, carbon atoms, optionally mono- or polysubstituted with F, Cl, Br, I, or CN, wherein, in addition, one or more non-adjacent CH2 groups may be independently substituted with -O-, -S-, -NH-, or -N(R) 0 )-、-Si(R 0 R 00 )-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -S-CO-, -CO-S-, -N(R 00 -CO-O-、-O-CO-N(R) 0 )-、-N(R 0 )-CO-N(R 00 -, -CH=CH-, or -C≡C- are replaced by O and / or S atoms that are not directly connected to each other.

[0079] X" means -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CO-N(R 0 )-、-N(R 0 )-CO-、-N(R 0 )-CO-N(R00 )-, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CF2CH2-, -CH2CF2-, -CF2CF2-, -CH=N-, -N=CH-, -N=N-, -CH=CR 0 -、-CY 2 =CY 3 -, -C≡C-, -CH=CH-CO-O-, -O-CO-CH=CH- or single bonds

[0080] R 0 and R 00 Each independently represents H or an alkyl group having 1-20 carbon atoms, and

[0081] Y 2 and Y 3 Each can be represented independently as H, F, Cl, or CN.

[0082] X" is preferably -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, or -CO-NR. 0 -、-NR 0 -CO-、-NR 0 -CO-NR 00 - or a single key.

[0083] Typical spacer groups Sp and -Sp"-X"- are, for example, -(CH2). p1 -、-(CH2) p1 -O-、-(CH2) p1 -O-CO-、-(CH2) p1 -CO-O-、-(CH2) p1 -O-CO-O-、-(CH2CH2O) q1 -CH2CH2-, -CH2CH2-S-CH2CH2-, -CH2CH2-NH-CH2CH2- or -(SiR) 0 R 00 -O) p1 - where p1 is an integer from 1 to 12, q1 is an integer from 1 to 3, and R 0 and R 00 It has the meanings mentioned above.

[0084] The particularly preferred groups Sp and -Sp"-X"- are -(CH2). p1 -、-(CH2) p1 -O-、-(CH2) p1 -O-CO-、-(CH2) p1-CO-O-、-(CH2) p1 -O-CO-O-, where p1 and q1 have the meanings mentioned above.

[0085] The particularly preferred group Sp" is, in each case, a straight-chain ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylenethioethylene, ethylene-N-methyliminoethylene, 1-methylalkylene, vinylene, propenylene, and butenylene.

[0086] In a preferred embodiment of the invention, the compounds of formula I and its subforms contain a spacer group Sp, which is replaced by one or more polymerizable groups P, such that the group Sp-P corresponds to Sp(P). s , s≥2 (branched polymerizable groups).

[0087] Preferred compounds of Formula I according to this preferred embodiment are those in which s is 2, i.e., compounds containing the group Sp(P)2. A highly preferred compound of Formula I according to this preferred embodiment contains a group selected from the following formulas:

[0088]

[0089] Where P is defined in Equation I.

[0090] Alkyl refers to a single-chain or straight-chain alkylene group with 1-12 carbon atoms, which is unsubstituted or mono- or polysubstituted with F, Cl, or CN, and one or more non-adjacent CH2 groups may be independently bonded to each other by -C(R). 0 )=C(R 0 )-、-C≡C-、-N(R 0 -, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-, -O-CO-O- are replaced by O and / or S atoms not being directly connected to each other, where R 0 Having the meanings indicated above,

[0091] aa and bb each independently represent 0, 1, 2, 3, 4, 5, or 6.

[0092] X has one of the meanings indicated by X", and is preferably O, CO, SO2, O-CO-, CO-O or a single bond.

[0093] The preferred spacer group Sp(P)2 is selected from formulas Sp1, Sp2 and Sp3.

[0094] The highly preferred spacer group Sp(P)2 is selected from the following formulas:

[0095]

[0096] In the compounds of formula I and its sub-formulas described in the context, P is preferably vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxobutyl, and epoxy, very preferably acrylate and methacrylate, and most preferably methacrylate.

[0097] Other preferred options are compounds of formula I and its sub-formulas as described in the context, wherein all polymerizable groups P present in the compound have the same meaning, and very preferably represent acrylate or methacrylate groups, most preferably methacrylate groups.

[0098] Other preferred options are compounds of formula I and its sub-formulas as described in the context, which contain one, two, three or four P-Sp groups, with two or three P-Sp groups being particularly preferred.

[0099] Other preferred options are compounds of formula I and its derivatives as described in the context, wherein R b It is P-Sp-.

[0100] Other preferred options are compounds of formula I and its sub-formulas as described in the context, where Sp represents a single bond or -(CH2). p1 -、-O-(CH2) p1 -、-O-CO-(CH2) p1 Or -CO-O-(CH2) p1 Where p1 is 2, 3, 4, 5, or 6, and if Sp is -O-(CH2). p1 -、-O-CO-(CH2) p1 Or -CO-O-(CH2) p1 Each of the O- atoms or CO- groups is attached to a benzene ring.

[0101] Other preferred options are compounds of formula I and its sub-formulas as described in the context, wherein at least one Sp group is a single bond.

[0102] Other preferred options are compounds of formula I and its sub-formulas as described in the context, wherein at least one Sp group differs from the single bond and is selected from -(CH2). p1 -、-O-(CH2) p1 -、-O-CO-(CH2) p1 Or -CO-O-(CH2) p1 Where p1 is 2, 3, 4, 5, or 6, and if Sp is -O-(CH2). p1 -、-O-CO-(CH2) p1Or -CO-O-(CH2) p1 Each of the O- atoms or CO- groups is attached to a benzene ring.

[0103] Highly preferred are compounds of formula I and its sub-formulas as described in the context, wherein at least one group Sp is different from the single bond and is selected from -(CH2)2-, -(CH2)3-, -(CH2)4-, -O-(CH2)2-, -O-(CH2)3-, -O-CO-(CH2)2- and -CO-O-(CH)2-, wherein the O atom or CO group is attached to the benzene ring.

[0104] In Formula I and its sub-formulas, A preferably represents a thioalkyl group having 1-7 carbon atoms, preferably straight-chain or branched, most preferably straight-chain, and preferably selected from -SCH3, -SC2H5 and -SC3H7, very preferably -SCH3 or -SC2H5, and most preferably -SCH3. Further preferably, A is selected from -CH2-S-CH3 or -CH2-S-C2H5.

[0105] Preferably, A in Formula I 1 and A 2 Selected from 1,4-phenylene, 1,3-phenylene, naphthalene-1,4-diyl, naphthalene-2,6-diyl, phenanthrene-2,7-diyl, 9,10-dihydro-phenanthrene-2,7-diyl, anthracene-2,7-diyl, fluorene-2,7-diyl, coumarin, and flavonoids, wherein, in addition, one or more CH groups in these groups can be replaced by N, cyclohexane-1,4-diyl, wherein, in addition, one or more non-adjacent CH2 groups can be replaced by O and / or S, 1,4-cyclohexane Alkenyl, bicyclo[1.1.1]pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]heptane-2,6-diyl, piperidine-1,4-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, indane-2,5-diyl or octahydro-4,7-bridged methylene indane-2,5-diyl, all of which are optionally substituted with one or more groups A, L or P-Sp-, and at least one of the groups A 1 Or A 2 Preferably, at least one aryl or heteroaryl group A 1 Or A 2 It is substituted by at least one group A.

[0106] Very preferably, in formula I, A 1 and A 2 Selected from benzene, naphthalene, phenanthrene, anthracene, dibenzofuran, or dibenzothiophene, all of which are optionally substituted with one or more groups A, L, or P-Sp-, and at least one of these groups A 1 Or A 2 It is substituted by at least one group A.

[0107] Preferably, z in Formula I is 0, 1 or 2, and very preferably 1 or 2.

[0108] Preferably, in formula I, -A 1 -(Z 1 -A 2 ) z - represents benzene, biphenylene, p-terphenylene (1,4-diphenylbenzene), m-terphenylene (1,3-diphenylbenzene), naphthalene, 2-phenyl-naphthalene, phenanthrene or anthracene, dibenzofuran or dibenzothiophene, all of which are optionally substituted with one or more groups A, L or P-Sp-, and at least monosubstituted with A.

[0109] Further preferred are compounds of formula I and its derivatives, which contain at least one group A. 1 Or A 2 It was not replaced by L or A.

[0110] Other preferred options are compounds of formula I and its derivatives as described in the context, wherein -A 1 -(ZA 2 ) z -Selected from the following formula:

[0111]

[0112] The single bond describes the groups P-Sp and R in Formula I. b The benzene ring is connected, and the benzene ring is optionally further substituted by one or more groups A, L or P-Sp as defined in Formula I, and at least one benzene ring is substituted by at least one group A, and preferably at least one benzene ring is not substituted with any substituent A or L.

[0113] Formulas A1, A2, and A5 are preferred, formulas A1 and A2 are more preferred, and formula A1 is the most preferred.

[0114] Preferred compounds of formula I are selected from the following sub-formulas:

[0115]

[0116]

[0117] Each of the groups, independently of each other and in the same or different manner each time it appears, has the following meaning:

[0118] A, P, Sp, R b It has one of the meanings given in Equation I or one of the preferred meanings given in the context.

[0119] L 11 To L 17It can be represented by L or A, preferably F, Cl, OCH3, OCF3, CN, P-Sp or A.

[0120] r1, r2, r3, r4 represent 0, 1, 2, 3, or 4, preferably 0, 1, or 2, and very preferably 0 or 1, wherein in equations I1, I2, and I5, r1 + r2 + r3 ≥ 1.

[0121] r5, r6, represent 0, 1, 2, or 3, preferably 0, 1, or 2, very preferably 0 or 1, wherein in equation I3, r5 + r6 ≥ 1 and in equations I4a and I4b, r4 + r5 + r6 ≥ 1.

[0122] r7 represents 1, 2, 3, or 4, with 1 or 2 being preferred and 1 being the most preferred.

[0123] The compound contains at least the L group. 11 To L 17 , which is A.

[0124] The preferred compounds are those of formulas I1, I2 and I5, the most preferred compounds are those of formulas I1 and I2, and the most preferred compounds are those of formula I1.

[0125] Further preferred are compounds of formula I12.

[0126]

[0127] Where P, Sp, R b ,L 11 ,L 12 ,L 13 r1, r2, and r3 have the meaning given in the context, r1 + r2 + r3 ≥ 1, and c is 0, 1, or 2, preferably 0 or 1.

[0128] Preferred sub-formulas of formula I12 include the preferred sub-formulas of formulas I1 and I2 as listed below.

[0129] Further preferred are compounds of formula I, I1-I6 and I12, wherein R b It represents P-Sp.

[0130] Further preferred are compounds of formulas I, I1-I6 and I12, wherein R b Unlike P-Sp, and preferably representing F, Cl, CN or a straight-chain, branched, or cyclic alkyl group having 1-25 C atoms, wherein one or more non-adjacent CH2- groups are optionally replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- in such a way that the O- and / or S- atoms are not directly connected to each other, and wherein one or more H atoms are each optionally replaced by F or Cl.

[0131] Further preferred are compounds of formulas I1, I2, and I5, wherein at least one of r1, r2, and r3 is 0; compounds of formula I3, wherein at least one of r4 and r5 is 0; compounds of formulas I4a and I4b, wherein at least one of r4, r5, and r6 is 0; and compounds of formula I12, wherein if c is 0, then one of r1 and r2 is 0, and if c is 1 or 2, then at least one of r1, r2, and r3 is 0.

[0132] The preferred compounds of formulas I, I1 to I6 and I12 are selected from the following sub-formulas:

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139] in

[0140] R,P,Sp,L 11-17 r1-r7 have one of the meanings given in Equation I or the preferred meanings given in the context.

[0141] L 18 ,L 19 and L 20 With L 11 One of the meanings given is

[0142] r8 can be 0, 1, or 2, preferably 0 or 1.

[0143] r9 can be 0, 1, 2, or 3, preferably 0, 1, or 2, and very preferably 0 or 1.

[0144] r10 is 1, 2, or 3, preferably 1 or 2, and very preferably 1.

[0145] Sp(P)2 represents a spacer group Sp, which is replaced by two polymerizable groups P at the same or different positions.

[0146] in

[0147] In equations I1A, I1C, and I1E, r1 + r2 ≥ 1.

[0148] In equations I1B, I1D, and I1F, r1 + r5 ≥ 1.

[0149] In equations I1G, I3A, and I3C, r5 + r6 ≥ 1.

[0150] In equations I2A, I2D, I2E, I5A, and I5C, r1 + r2 + r3 ≥ 1.

[0151] In equations I2B, I2C, I2F, I5B, and I5D, r1 + r3 + r5 ≥ 1.

[0152] In equation I2G, r3+r5+r6≥1,

[0153] In equations I4A, I4C, and I4E, r4 + r5 + r6 ≥ 1.

[0154] In equation I4D, r5 + r6 + r9 ≥ 1.

[0155] In equation I3B, r5 + r8 ≥ 1,

[0156] In equation I4B, r4 + r5 + r8 ≥ 1.

[0157] And the compound contains at least the L group 11 To L 20 , which represents A.

[0158] Further preferred compounds of formulas I and I12 are selected from the following sub-formulas.

[0159]

[0160]

[0161] in

[0162] R,P,Sp,Sp(P)2,L 11-16 r1-r6 have one of the meanings given in Equation I2D or the preferred meanings given by the context.

[0163] c is 0, 1, or 2.

[0164] In equations I12A, I12D, and I12E, r1 + r2 + r3 ≥ 1.

[0165] In equations I12B, I12C, and I12F, r1 + r3 + r5 ≥ 1.

[0166] In equation I12G, r3+r5+r6≥1,

[0167] The compound contains at least one L group. 11 To L 16 , which is A.

[0168] Preferably, in compounds of formulas I12A to I12G, if c is 0, then one of r1 and r2 is 0, and if c is 1 or 2, then at least one of r1, r2 and r3 is 0.

[0169] The compound of formula I12A is highly preferred.

[0170] Other preferred compounds of formulas I, I1 to I6, I12, I1A–I6C and I12A–I12G are selected from the following sub-formulas:

[0171]

[0172]

[0173]

[0174]

[0175]

[0176]

[0177]

[0178]

[0179]

[0180]

[0181]

[0182]

[0183]

[0184]

[0185]

[0186]

[0187]

[0188]

[0189]

[0190]

[0191]

[0192]

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203]

[0204]

[0205]

[0206]

[0207]

[0208]

[0209]

[0210]

[0211]

[0212]

[0213]

[0214]

[0215]

[0216]

[0217]

[0218]

[0219]

[0220]

[0221]

[0222]

[0223]

[0224] Wherein R, P, Sp, Sp(P)2, A and L have one of the meanings given in Formula I or the preferred meanings given in the context, L is preferably F, Cl or CN, A is preferably a thioalkyl group having 1-7 C atoms, preferably linear, more preferably -SCH3, -SC2H5 or -SC3H7, very preferably -SCH3, and even more preferably -CH2S-CH3 or -CH2-S-C2H5.

[0225] Especially preferred are compounds selected from formulas I1A-1 to I2G-4.

[0226] Other preferred compounds of formulas I, I1 to I6, I12, I1A–I5D, I12A–I12G, and I1A-1 to I6C-1 are selected from the following sub-formulas:

[0227]

[0228]

[0229]

[0230]

[0231]

[0232]

[0233]

[0234]

[0235]

[0236]

[0237]

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244]

[0245]

[0246]

[0247]

[0248]

[0249]

[0250]

[0251]

[0252]

[0253]

[0254]

[0255]

[0256]

[0257]

[0258]

[0259]

[0260]

[0261]

[0262]

[0263]

[0264]

[0265]

[0266]

[0267]

[0268]

[0269]

[0270]

[0271]

[0272]

[0273]

[0274]

[0275]

[0276]

[0277]

[0278]

[0279]

[0280]

[0281]

[0282]

[0283]

[0284]

[0285]

[0286]

[0287]

[0288]

[0289]

[0290]

[0291]

[0292]

[0293]

[0294]

[0295]

[0296]

[0297]

[0298]

[0299]

[0300]

[0301]

[0302]

[0303]

[0304]

[0305]

[0306]

[0307]

[0308]

[0309]

[0310]

[0311]

[0312]

[0313]

[0314]

[0315]

[0316]

[0317]

[0318]

[0319]

[0320]

[0321]

[0322]

[0323]

[0324]

[0325]

[0326]

[0327]

[0328]

[0329]

[0330]

[0331]

[0332]

[0333]

[0334]

[0335]

[0336]

[0337]

[0338]

[0339] Wherein A, L, R, P, Sp and Sp(P)2 have one of the meanings given in Formula I or the preferred meanings given in the context, and A is preferably a thioalkyl group having 1-7 C atoms, preferably a straight chain, more preferably -SCH3, -SC2H5 or -SC3H7, very preferably -SCH3, and even more preferably -CH2S-CH3 or -CH2-S-C2H5.

[0340] Highly preferred are compounds selected from formulas I1A-1-1 to I2D-30-4.

[0341] Preferred compounds are those of formulas I1A-1-1 to I1B-8-6, I1D-1-1 to I2C-15-4, I2E-1-1 to I5B-9-4 and I5D-1-1 to I5D-5-3.

[0342] Further preferred are compounds of formulas I1A-1-1 to I1A-7-3, I2A-1-1 to I2A-18-12, I5A-1-1 to I5A-19-3, and I6A-1-1 to I6B-2-1, wherein all Sp groups are single bonds. Further preferred are compounds of formulas I1A-1-1 to I1A-7-3, I2A-1-1 to I2A-18-2, I5A-1-1 to I5A-19-3, and I6A-1-1 to I6B-2-1, wherein one Sp group represents a single bond and the other Sp group is different from a single bond.

[0343] Further preferred are compounds of formulas I1B-1-1 to I1B-8-6, I1D-1-1 to I1G-3-1, I2B-1-1 to I2C-15-4, I2E-1-1 to I2G-4-1, I5B-1-1 to I5B-9-4, I5D-1-1 to I5D-5-3 and I6C-1-1, wherein all Sp groups are single bonds. Further preferred are compounds of formulas I1B-1-1 to I1B-8-6, I1D-1-1 to I1G-3-1, I2B-1-1 to I2C-15-4, I2E-1-1 to I2G-4-1, I5B-1-1 to I5B-9-4, I5D-1-1 to I5D-5-3 and I6C-1-1, wherein one or two of the Sp groups represent single bonds and other Sp groups are different from single bonds. Further preferred are compounds of formulas I1B-1-1 to I1B-8-6, I1D-1-1 to I1G-3-1, I2B-1-1 to I2C-15-4, I2E-1-1 to I2G-4-1, I5B-1-1 to I5B-9-4, I5D-1-1 to I5D-5-3 and I6C-1-1, wherein one or two of the Sp groups are different from the single bond and the other Sp groups represent the single bond.

[0344] Further preferred are compounds of formulas I1C-1-1 to I1C-13-3, I2D-1-1 to I2D-30-4, and I5C-1-1 to I5C-28-3, wherein the Sp group in the P-Sp group is a single bond. Further preferred are compounds of formulas I1C-1-1 to I1C-13-3, I2D-1-1 to I2D-30-4, and I5C-1-1 to I5C-28-3, wherein all Sp groups are different from single bonds.

[0345] Further preferred are compounds of formulas I1A-1-1 to I6C-1-1, wherein A represents a thioalkyl group having 1 to 7 C atoms, preferably linear, more preferably -SCH3, -SC2H5 or -SC3H7, most preferably -SCH3, and further preferably -CH2S-CH3 or -CH2-S-C2H5.

[0346] Further preferred are compounds of formulas I1A-1-1 to I6C-1-1, wherein L represents F, Cl, CN or OCH3, with F being very preferred.

[0347] Further preferred are compounds of formulas I1A-1-1 to I6C-1-1, wherein P represents an acrylate group or a methacrylate group, with a methacrylate group being very preferred.

[0348] Further preferred are compounds of formulas I1A-1-1 to I6C-1-1, wherein Sp, when different from a single bond, represents an alkylene group having 2-6 carbon atoms.

[0349] Further preferred are compounds of formulas I1A-1-1 to I6C-1-1, wherein all Sp groups represent single bonds, all P groups represent methacrylate groups, all A groups represent S-CH3, and all L groups represent F.

[0350] The preferred compounds of formulas I and II and their sub-formulas are selected from the following preferred embodiments, including any combination thereof:

[0351] -This compound contains a group A.

[0352] -This compound contains two or more A groups.

[0353] -This compound contains one or more A groups and one or more L groups.

[0354] - This compound contains two non-fused or fused, preferably non-fused, benzene rings.

[0355] - The compound contains three or more, preferably three or four, non-fused or fused benzene rings.

[0356] - This compound contains at least one benzene ring that is not substituted by A or L.

[0357] -A is a thioalkyl group having 1-7 carbon atoms, preferably a straight chain, more preferably -SCH3, -SC2H5 or -SC3H7, and very preferably -SCH3.

[0358] -A is either -CH2S-CH3 or -CH2-S-C2H5.

[0359] - This compound contains exactly one polymerizable group (represented by the group P).

[0360] - This compound contains exactly two polymerizable groups (represented by the group P).

[0361] - This compound contains exactly three polymerizable groups (represented by the group P).

[0362] - This compound contains exactly four polymerizable groups (represented by the group P).

[0363] -P is selected from acrylate, methacrylate, and oxetyl groups, with acrylate or methacrylate groups being most preferred.

[0364] -P represents a methacrylate group.

[0365] -Pg represents a hydroxyl group.

[0366] - Each of the Sp groups represents a single bond.

[0367] - At least one Sp group is different from a single bond.

[0368] - At least one Sp group is a single bond and at least one Sp group is different from a single bond.

[0369] -Sp, when different from a single bond, is selected from -(CH2). p2 -,-(CH2) p2 -O-,-(CH2) p2 -CO-O-,-(CH2) p2 -O-CO-, where p2 is 2, 3, 4, 5, or 6, and the O- atom or CO- group is attached to the benzene ring, respectively.

[0370] -Sp, when different from a single bond, is selected from -(CH2)2-, -(CH2)3-, -(CH2)4-, -O-(CH2)2-, -O-(CH2)3-, -O-CO-(CH2)2-, and -CO-O-(CH)2-, wherein the O atom or CO group is attached to the benzene ring.

[0371] -Sp represents a single bond or -(CH2). p2 -,-(CH2)p2 -O-,-(CH2) p2 -CO-O-,-(CH2) p2 -O-CO-, where p2 is 2, 3, 4, 5, or 6, and the O- atom or CO- group is attached to the benzene ring, respectively.

[0372] -Sp(P)2 is selected from sub-Sp1a-Sp3a,

[0373] -R b Indicates P-Sp-,

[0374] -R b Does not indicate or contain polymerizable groups.

[0375] -R b The symbol represents F, Cl, CN, or a straight-chain, branched, or cyclic alkyl group having 1-25 C atoms, wherein one or more non-adjacent CH2- groups are optionally replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- in such a way that the O- and / or S- atoms are not directly connected to each other, and one or more H atoms are each optionally replaced by F or Cl.

[0376] -R represents F, Cl, CN, or a straight-chain, branched, or cyclic alkyl group having 1-25 C atoms, wherein one or more non-adjacent CH2- groups are optionally replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- in such a way that the O- and / or S- atoms are not directly connected to each other, and one or more H atoms are each optionally replaced by F or Cl.

[0377] -Z 1 It is a single key.

[0378] -z can be 0, 1, 2, or 3, with 0 or 1 being the most preferred.

[0379] -L is selected from F, Cl, CN, and each has 1-6 C atoms in an alkyl, alkoxy, alkyl carbonyl, alkoxy carbonyl, alkyl carbonyloxy, or alkoxy carbonyl alkyl group, wherein one or more H atoms may optionally be replaced by F or Cl, preferably F, Cl, CN, or OCH3, and very preferably F.

[0380] Highly preferred compounds of Formula I and its sub-formulas are selected from the following sub-formulas:

[0381]

[0382]

[0383]

[0384]

[0385]

[0386]

[0387]

[0388]

[0389]

[0390]

[0391]

[0392] Further preferred are compounds of formulas I1A-1-1a to I2B-1-6b, wherein one, two or three methacrylate groups are replaced by acrylate groups.

[0393] Highly preferred compounds of formula II are those selected from sub-formulas I1 to I6, I12, I1A to I6C, I12A to I12G, I1A-1 to I6C-1 and I1A-1-1 to I6C-1-1 above, wherein each group P is replaced by a group Pg as defined in formula II, and those selected from sub-formulas I1A-1-1a to I2B-1-6b above, wherein each methacrylate group is replaced by a group Pg as defined in formula II.

[0394] Suitable protected hydroxyl groups Pg for compounds of formula II and its derivatives are known to those skilled in the art. Preferred protected groups for the hydroxyl group are alkyl, alkoxyalkyl, acyl, alkylsilyl, arylsilyl, and arylmethyl, especially 2-tetrahydropyranyl, methoxymethyl, methoxyethoxymethyl, acetyl, triisopropylsilyl, tert-butyl-dimethylsilyl, or benzyl.

[0395] The term "masked hydroxyl group" is understood to refer to any functionalized group that can be chemically converted into a hydroxyl group. Suitable masked hydroxyl groups Pg are known to those skilled in the art.

[0396] Compounds of Formula II are suitable as intermediates for the preparation of compounds of Formula I and its derivatives.

[0397] The present invention further relates to the use of compounds of formula II as intermediates in the preparation of compounds of formula I and its derivatives.

[0398] Compounds and intermediates of Formulas I and II and their sub-formulas can be prepared by methods similar to those known to those skilled in the art and described in standard works of organic chemistry, such as Houben-Weyl, Methods of Organic Chemistry, Thieme-Verlag, and Stuttgart.

[0399] For example, a compound of formula I can be synthesized by using a corresponding acid, acid derivative or halogenated compound containing a polymerizable group P, optionally in the presence of a dehydrating agent, to esterify or etherify an intermediate of formula II (where Pg represents OH, H or a protected or masked hydroxyl group).

[0400] For example, acrylates or methacrylates can be prepared by esterifying the corresponding alcohol with an acid derivative such as (meth)acryloyl chloride or (meth)acrylic anhydride in the presence of a base such as pyridine or triethylamine and 4-(N,N-dimethylamino)pyridine (DMAP). Alternatively, the ester can be prepared by esterifying an alcohol with (meth)acrylic acid in the presence of a dehydrating agent, such as dicyclohexylcarbodiimide (DCC), N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide (EDC), or N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride and DMAP, according to Steglich.

[0401] Further suitable and preferred general synthetic methods for the compounds of formulas I and II are shown in Scheme 1 below.

[0402] Option 1

[0403]

[0404]

[0405] Where Z represents H or -R-OH, Y represents boronic ester, boric acid, or halogen, and X represents... 1,2,3 Halogens are indicated, preferably Br or Cl, R 1 ,2,3,4 Pg indicates a substituent, and Pg indicates a protected group or H. m ≥ 0 and m = 0 indicates a single bond.

[0406] Compounds of formulas I and II or their subforms with different substitution patterns or different mesocrystalline groups can be prepared in a manner similar to scheme 1.

[0407] Further suitable methods are shown in the following embodiments.

[0408] Furthermore, the present invention relates to compositions comprising one or more compounds of formula I or a subset thereof. Another preferred embodiment relates to a composition comprising at least two polymerizable compounds, at least one of which is a compound of formula I or a subset thereof.

[0409] Furthermore, the present invention relates to polymers obtained by polymeric compounds of formula I or its sub-formulas, or compositions comprising them.

[0410] Suitable and preferred polymerization methods are, for example, thermal or photopolymerization, with photopolymerization being preferred, especially UV-induced photopolymerization, which can be achieved by exposing the polymerizable compound to UV radiation.

[0411] Optionally, one or more polymerization initiators are added to a compound of formula I or a composition comprising it. Suitable conditions for polymerization and suitable types and amounts of initiators are known to those skilled in the art and described in the literature. Suitable initiators for free radical polymerization include, for example, commercially available photoinitiators. or (Ciba AG). If a polymerization initiator is used, its proportion is preferably 0.001-5 wt%, particularly preferably 0.001-1 wt%.

[0412] The polymerizable compounds according to the invention are also suitable for polymerization without an initiator, which has considerable advantages, such as lower material costs, and in particular less contamination of the polymer or composition by possible residual initiator or its degradation products. Therefore, polymerization can also be carried out without the addition of an initiator. In a preferred embodiment, the polymerizable compounds or compositions according to the invention do not contain a polymerization initiator.

[0413] The polymerizable compounds or compositions according to the invention may also contain one or more stabilizers to prevent undesirable spontaneous polymerization of the compound, for example, during storage or transportation. Suitable types and amounts of stabilizers are known to those skilled in the art and described in the literature. Particularly preferred stabilizers are, for example, those derived from... Commercially available stabilizers for the Ciba AG series, such as 1076. If stabilizers are used, their proportion, based on the total amount of polymerizable compounds, is preferably 10-50,000 ppm, particularly preferably 50-5,000 ppm.

[0414] In a preferred embodiment, the polymerizable compound or composition according to the invention contains one or more chiral dopants, preferably at a concentration of 0.01-1 wt%, very preferably 0.05-0.5 wt%. Racemates of one or more chiral dopants may also be used.

[0415] The polymerizable compounds or compositions according to the present invention may additionally contain one or more other components or additives, preferably selected from, but not limited to: comonomers, chiral dopants, polymerization initiators, inhibitors, stabilizers, surfactants, wetting agents, lubricants, dispersants, hydrophobic agents, binders, flow improvers, defoamers, degassing agents, diluents, reactive diluents, auxiliaries, colorants, dyes, pigments, and nanoparticles.

[0416] Particularly preferred are compositions comprising one, two, or three polymerizable compounds of Formula I.

[0417] Furthermore, it is preferable that the polymerizable compound is selected only from polymerizable compounds of Formula I.

[0418] Furthermore, preferred are achiral compounds of Formula I, and compositions in which all components are selected solely from achiral compounds.

[0419] The following examples are intended to explain, but not limit, the invention. However, they illustrate preferred mixture concepts and preferred compounds to be used, their respective concentrations, and combinations thereof, as well as those preferred by those skilled in the art. Furthermore, these examples demonstrate which properties and combinations of properties are available.

[0420] Unless otherwise expressly stated, all temperature values ​​specified in this application are referenced in degrees Celsius (°C) and all percentages refer to weight percentages. The following abbreviations are used: Mp or mp = melting point (in °C), DCM = dichloromethane. Detailed Implementation

[0421] Example 1

[0422] Compound 1 was prepared as follows.

[0423]

[0424] 1.1 Synthesis of Bromide A

[0425]

[0426] 13.51 g (127.42 mmol) of Na₂CO₃ was dissolved in 100.0 mL of water and 56.74 mL of ethanol. A solution of 18.3 g (46.3 mmol) of 1-benzyloxy-2-bromo-4-iodobenzene and 10.36 g (45.41 mmol) of 4-benzyloxyphenylboronic acid in 220.8 mL of toluene and 1.921 g (1.662 mmol) of tetrakis(triphenylphosphine)-palladium(O) were added. The reaction mixture was refluxed for 14 hours and cooled to room temperature. Ethyl acetate (EE) was added, and the organic layer was separated. The aqueous layer was extracted several times with EE, and the combined organic layers were washed with saturated NaCl solution (salt water), filtered, dried over MgSO₄, and evaporated under vacuum. The reaction product was purified by column chromatography (heptane / EE 1:1) to give a light brown crystalline solid.

[0427] 1.2 Synthesis of Thiol B

[0428]

[0429] 7.00 g (15.72 mmol) of bromide A, N,N-diisopropylethylamine was dissolved in toluene (50 mL) and packed into an autoclave. 148.39 mg (0.16 mmol) of Pd₂dba₃ and 206.27 mg of Xanthphos were added, and 0.849 g (17.290 mmol) of methanethiol was transferred to the autoclave at <6 °C (this reagent requires special care when handling). The reaction mixture was stirred at 110–112 °C for 14 h, cooled to room temperature, and washed with NaOH⁻, Na₂CO₃⁻, and NaCl⁻ solutions. The organic layer was separated, dried over Na₂SO₄, and evaporated under vacuum. The reaction product was purified by column chromatography (toluene / EE 1:1) to obtain a white solid.

[0430] 1.3 Synthesis of Phenol C

[0431]

[0432] 4.00 g (9.70 mmol) of glycol C was dissolved in 160 mL of dichloromethane (DCM) and cooled to +3 °C. The mixture was stirred for 30 min, and 24.24 mL (24.24 mmol, 1 M in dichloromethane) of BBr3 was added dropwise while stirring at 3 °C for 30 min. The reaction was quenched by carefully pouring the mixture into 100 mL of ice water. The organic layer was separated, and the aqueous layer was extracted with DCM. The combined organic layers were washed with brine, dried over Na2SO4, filtered, and evaporated under vacuum. The product was purified by column chromatography (DCM / EE 4:1) to give a yellow oily product.

[0433] 1 H NMR(500MHz,DMSO-d6)δ9.79(s,1H),9.40(s,1H),7.44–7.35(m,2H),7.22(d ,J=2.2Hz,1H),7.17(dd,J=8.2,2.2Hz,1H),6.85–6.77(m,3H),2.42(s,3H).

[0434] 1.4 Synthesis of Compound 1

[0435] 100.00 mg (0.43 mmol) of glycol C was dissolved in 5 mL of DCM, 0.084 mL (0.990 mmol) of methacrylic acid was added, and the mixture was cooled to 0 °C. 0.160 g (1.033 mmol) of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide dissolved in 5 mL of DCM was added dropwise. The reaction mixture was stirred at room temperature for 14 hours and filtered directly through silica gel using DCM / EE 9:1. The product fractions were combined and, after evaporation, crystallized from heptane (5 mL) to give a white solid product.

[0436] Mp=76℃, MS(EI=368(M + )

[0437] 1 ¹H NMR (500MHz, chloroform-d) δ 7.63–7.56 (m, 2H), 7.45 (d, J = 2.1 Hz, 1H), 7.39 (dd, J = 8.2, 2.2 Hz, 1H), 7.25–7.16 (m, 3H), 6.44 (dt, J = 30.7, 1.1 Hz, 2H), 5.82 (dq, J = 9.9, 1.6 Hz, 2H), 2.51 (s, 3H), 2.13 (dt, J = 13.2, 1.2 Hz, 6H).

[0438] For a DCM solution with a concentration of 3 g / L, the absorption wavelength λ of compound 1 was measured to be 336 nm at an extinction coefficient E = 0.5.

[0439] Example 2-15

[0440] Compounds 2-15 were prepared by the method described in Example 1 or a similar method.

[0441]

[0442]

[0443]

[0444] Compound 2-15 exhibited UV absorption at wavelengths >300 nm.

[0445] Application Example A – Comparison of Physical Properties

[0446] Using the method described in Example 1, the absorption wavelength λ at an extinction coefficient E = 0.5 was determined for prior art compounds C1 and C2. This wavelength can be used to characterize the wavelength dependence of UV photopolymerization of the compounds.

[0447]

[0448] The melting point and UV absorption wavelength of compound 1 according to the present invention were compared with those of prior art compounds C1 and C2. The results are shown in Table 1.

[0449] Table 1 – Melting Point and UV Absorption

[0450] C1 C2 1 Melting point (°C) 152 105 76 The UV absorption wavelength λ (nm) at E = 0.5 320 329 336

[0451] As can be seen from Table 1, compound 1 according to the invention has the lowest melting point, which is particularly advantageous because it indicates that the monomer dissolves faster than C1 and C2, resulting in a shorter production cycle, and has high solubility in liquid crystal media.

[0452] As can also be seen from Table 1, compound 1 according to the invention has the longest absorption wavelength and is therefore particularly suitable for UV photopolymerization at longer wavelengths or for faster polymerization at shorter wavelengths.

[0453] Application Example B – UV Photopolymerization

[0454] Compounds 1, C1, and C2 were each dissolved in a nematic LC bulk mixture (MDA-10-1077, Merck KGaA) at a concentration of approximately 0.3 wt%, and subsequently filtered using a 320 nm long-pass filter and 100 mW / cm². 2 The light intensity is polymerized by exposure to UV radiation.

[0455] The amount of residual unreacted monomers in the LC bulk mixture after various UV exposure times was determined by HPLC. The results are shown in Table 2.

[0456] Table 2 – Residual monomer concentration (relative to initial amount)

[0457]

[0458] As can be seen from Table 2, monomer 1 according to the present invention exhibits the fastest polymerization and the lowest residual monomer content, and is therefore particularly suitable for polymerization at longer UV wavelengths.

Claims

1. Compounds of formulas I1A-1 to I1A-5 and I2A-1 to I2A-11, characterized in that... It is selected from the following subforms: Where A is -SCH3, -SC2H5 or -SC3H7; P is acrylate or methacrylate; Sp is a single bond; L is F, Cl, CN, alkyl, alkoxy, alkyl carbonyl, alkoxy carbonyl, alkyl carbonyloxy or alkoxy carbonyloxy, each having 1 to 6 C atoms.

2. The compound according to claim 1, characterized in that... It is selected from formulas I1A-1-1 to I1A-5-3 and formulas I2A-1-1 to I2A-11-2: Where A is -SCH3, -SC2H5 or -SC3H7; P is acrylate or methacrylate; Sp is a single bond; L is F, Cl, CN, alkyl, alkoxy, alkyl carbonyl, alkoxy carbonyl, alkyl carbonyloxy or alkoxy carbonyloxy, each having 1 to 6 C atoms.

3. The compound according to claim 1 or 2, characterized in that... It is selected from the following subforms: 。 4. A composition comprising one or more compounds as defined in any one of claims 1-3.

5. A polymer obtained by polymerizing a compound according to any one of claims 1-3 or a composition according to claim 4.

6. The polymer according to claim 5, wherein the polymerization is UV photopolymerization.

7. The compound according to any one of claims 1-3, The composition of claim 4, or the polymer of claim 5 or 6, for use in protective, decorative, or optoelectronic applications, or for use in liquid crystal media.

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