Optically active device

Abstract

The present invention relates to a novel ophthalmic device comprising a polymerized compound containing a photoactive chromophore, and a composition and a special monomer compound particularly suitable for an ophthalmic device. The present invention also relates to a process for modifying the optical properties of said ophthalmic device or a precursor article for manufacturing said ophthalmic device.

Description

Technology Field

[0001] The present invention relates to a novel ophthalmic device comprising a polymerized compound containing a photoactive chromophore, and a composition and a special monomer compound particularly suitable for an ophthalmic device. The present invention also relates to a method for modifying the optical properties of said ophthalmic device or a precursor article for manufacturing said ophthalmic device. Background Technology

[0002] Cataract is a general term for an eye disease in which the lens of the eye, which is normally transparent, becomes cloudy, leading to loss of vision and, in extreme cases, blindness. It is a leading cause of blindness worldwide, affecting over 100 million people. The primary cause is age, and as the average age of the population increases, the number of cataracts is expected to continue to rise substantially in the future.

[0003] Effective treatment of cataracts is possible only through surgical intervention, which involves removing the eye's natural lens through a corneal incision and replacing it with an ophthalmic device often referred to as an "intraocular lens." During surgical preparation, the latest surgical techniques utilize eye mapping to achieve a refractive power as close as possible to the most suitable for each individual patient.

[0004] Although cataract surgery is one of the most widely used and safest surgical procedures, it is not without certain postoperative problems. It frequently occurs that the refractive power of the implanted intraocular lens (IOL) is insufficient to restore good vision. This problem can arise from irregular wound healing and positioning errors that prevent the ophthalmic device from having optimal optical properties, as well as from changes in the eye's geometric structure resulting from the surgery. Consequently, the patient will still require corrective devices, such as glasses, to see properly. In some cases, the refractive power of the created implanted device will be significantly different from the required power, necessitating additional surgery. This is particularly undesirable for older individuals, as the body's healing capacity decreases with age. Furthermore, there is a risk of developing endophthalmitis, an inflammation of the eye, which can lead to complete vision loss or, in severe cases, even eye loss.

[0005] Therefore, there is a need in the healthcare sector for optically active ophthalmic devices, particularly intraocular lenses, that allow for non-invasive adjustment of refractive power after lens implantation and thereby preferably further reduce the need for postoperative vision aids.

[0006] In this sense, some developments have already been made, as demonstrated by, for example, International Patent Publication WO 2007 / 033831, International Patent Publication WO 2009 / 074520, U.S. Patent No. 2010 / 0324165, International Patent Publication WO 2017 / 032442, International Patent Publication WO 2017 / 032443, International Patent Publication WO 2017 / 032444, International Patent Publication WO 2018 / 149850, International Patent Publication WO 2018 / 149852, International Patent Publication WO 2018 / 149853, EP3363791, International Patent Publication WO 2018 / 149855, International Patent Publication WO 2018 / 149856 or International Patent Publication WO 2018 / 149857.

[0007] The literature [M. Schraub et al, European Polymer Journal 51 (2014) 21-27] describes the photochemistry of 3-phenyl-coumarin containing polymethacrylate.

[0008] When a chromophore undergoes addition cyclication, both density and polarizability change. The refractive index is a function of density and polarizability according to the Lorentz-Lorenz equation (Equation 1), where M is the molar mass, and ρ is density, N It is the number density of the molecule, and α is the polarizability. The conversion of carbon-carbon double bonds to carbon-carbon single bonds results in a volume reduction of 22 cm³ / mol (Reference [Patel, MP et al., Biomaterials, 1987, 8, 53-56]).

[0009] [Equation 1]

[0010] This alone would lead to an increase in refractive index due to addition. However, by utilizing the nonlinear decrease in refractive index caused by the breakdown of the conjugated system, a large negative change in refractive index can be observed for a given chromophore, far exceeding the positive change in refractive index of the volume reduction.

[0011] However, large conjugated chromophores also exhibit large optical dispersion. Optical dispersion is the Abbe number, V, defined by Equation 2. D It is characterized by.

[0012] [Equation 2]

[0013] High optical dispersion is characterized by a low Abbe number and is disadvantageous in optical applications where more than one wavelength of light passes through materials such as ophthalmic devices, for example, lenses.

[0014] The literature [S. Helmstetter et al, J Polym Res, 2016, 23:249] describes copolymers as well as quinolinone-based crosslinked homopolymers that exhibit a refractive index at 589 nm in the range of 1.60 to 1.68 and an Abbe number of 19 to 25. It has been further reported that the higher the refractive index of the lens material, the thinner the intraocular lens becomes, but in most cases, this is accompanied by an increase in the glass transition temperature and a decrease in the Abbe number. Finding the optimal balance between a high refractive index, a low glass transition temperature, and a high Abbe number is a chemical challenge in polymer synthesis for IOL manufacturing, and the latest foldable but non-tunable hydrophobic IOLs have been reported to have a refractive index of 1.55 or less, a glass transition temperature of about 14 to 15°, and an Abbe number of 37 or less.

[0015] Since the publication of the literature [RB Setlow, Science, 1966, 153, 3734, 379-386], it has been known that the nucleobases thymine and uracil form dimers in response to ultraviolet light. Thymine, one of the nucleobases in DNA, photodimerizes via [2p + 2p]-addition cyclization when irradiated above 270 nm, and these dimers can be cleaved using UV below 249 nm. Because the dimerization of thymine leads to DNA damage, this effect has been extensively studied, and understanding this is important for preventing skin cancer. With 50 years of experimentation on these photochemical reactions, many scientists have attempted to apply this knowledge of the photochemistry of thymine and uracil for optical storage materials.

[0016] The literature [B. Lohse et al, Chem. Mater. 2006, 18, 4808-4816] reports new potential optical data storage media using 1,1'-(α,ω-alkandiyl)bis-uracil, 1,1'-(α,ω-alkandiyl)bis-[5-bromouracil], 1-(ω-bromoalkyl)uracil and 1-undecyluracil.

[0017] The literature [B. Lohse et al, Journal of Polymer Science: Part A: Polymer Chemistry 4401-4412] reports UV-photodimerization in uracil-substituted dendrimers for high-density data storage.

[0018] The literature [A. Theis et al, Macromolecules 2003, 36 (20), 7552-7559] describes kinetic studies on the photochemical behavior of polymeric mesoions and mesoionic copolymers from methacrylate monomers having liquid crystal properties.

[0019] International Patent Publication WO9924420 describes a pyrimidinone compound and a pharmaceutical composition containing the same.

[0020] DE10147238 describes a carrier-bound vinyl nucleus, and the preparation of a polymer thereof as an antiviral and anticancer agent.

[0021] EP0354179 describes thiouracil as a stabilizer for chloro-containing polymers.

[0022] PL108383 describes a silicate containing a uracil-derived moiety for chromatography.

[0023] U.S. Patent Application Publication No. 2013033975 describes a copolymer containing a 4-methyl substituted coumarin moiety as part of a medium for reversible recording.

[0024] U.S. Patent Application Publication No. 20170306121 describes a method for providing an electrically conductive polyaniline pattern by providing a uniform layer of a photocurable composition comprising a water-soluble reactive polymer on a substrate.

[0025] International Patent Publication WO2015003095 describes a sunless tanning composition comprising a uracil derivative.

[0026] However, there is still a need to provide alternative or improved ophthalmic devices, such as contact lenses or lenses implanted by the latest technology of cataract surgery methods, and there is still a need to provide specific compounds for the manufacture of ophthalmic devices implanted by the latest technology of cataract surgery methods, particularly the latest technology of micro-incision cataract surgery methods, such as intraocular lenses. Preferably, to meet the aforementioned needs, a high refractive index-change material with a high Abbe number is required.

[0027] Consequently, the object of the present application is to provide an alternative or improved ophthalmic device and a suitable compound for manufacturing such an ophthalmic device.

[0028] The object of the present application is also to provide a compound whose optical properties can be altered, preferably by a non-invasive technique.

[0029] A further objective of the present application is to provide a compound or an alternative compound having advantages over currently known compounds, preferably in a combination suitable for ophthalmic devices.

[0030] The advantages of a polymer or copolymer comprising a polymerized monomer of formula (I), formula (II), formula (III), or formula (VI) according to the present invention are shown in the experimental section. As well as ophthalmic devices comprising the polymer or copolymer containing the material according to the present invention, they preferably exhibit a significant change in polarization or refractive index after irradiation.

[0031] A further advantage of the polymer or copolymer comprising the polymerized monomer of formula (I), formula (II), formula (III), or formula (IV) according to the present invention is that these materials have a high Abbe number.

[0032] The advantage of a polymer or copolymer comprising a polymerized monomer of formula (I), formula (II), formula (III) or formula (VI) according to the present invention is excellent flexibility and a low glass transition temperature.

[0033] These characteristics enable greater flexibility in adjusting the polarization or refractive index of the optical device according to the present invention and ensure a high Abbe number. Based on the advantages of the polymer or copolymer of the present invention, an ophthalmic device comprising said material has inherently lower chromatic aberration.

[0034] The inventors have now discovered that the above objective can be achieved individually or in any combination by an ophthalmic device and a compound of the present invention.

[0035] The present invention relates to an ophthalmic device or a precursor article for manufacturing an ophthalmic device comprising at least one polymerized compound of formula (I), formula (II), formula (III) or formula (IV), and

[0036] , ,

[0037] , ,

[0038] In the above chemical formulas (I) to (IV),

[0039] R# is independently -[L]-R1 or R2 in each case, provided that at least one R# is -[L]-R1;

[0040] Y1 and Y0 are each independently O or S;

[0041] X is absent or C=O and;

[0042] R1 is a trialkoxysilyl group or a dialkoxyalkylsilyl group, wherein the alkyl and / or alkoxy group each independently has 1 to 6 C atoms and is linear or branched, or is a silyl group of formula (1), formula (2) or formula (3) or a polymerizable group of formula (4):

[0043]

[0044] In the above formulas (I) to (IV), alkyl means a linear or branched alkyl group having 1 to 6 C atoms independently in each case, and the asterisk "*" indicates a linkage to the linker [L] independently in each case;

[0045] X 11 In each case, is independently selected from the group consisting of O, S, O-SO2, SO2-O, C(=O), OC(=O), C(=O)O, S(C=O)S, and (C=O)S, and

[0046] R5, R6, and R7 are each independently selected from the group consisting of H, F, linear or branched alkyl groups having 1 to 20 C atoms that are not fluorinated or partially or fully fluorinated, and aryls having 6 to 14 C atoms, respectively.

[0047] c is independently 0 or 1 in each case;

[0048] [L] is independent of each case, -(C(R)2) o- , or -(C(R)2) p- X 8- (C(R)2) q- (X9) s- (C(R)2) r- (X 10 ) t -(C(R)2) u - and;

[0049] R is independently selected in each case from the group consisting of H, F, a linear or branched alkyl group having 1 to 4 C atoms, and a linear or branched partially or fully fluorinated alkyl group having 1 to 4 C atoms;

[0050] o is selected from the group consisting of 1 to 20, and

[0051] X8, X9 and X 10 is independently O, S, SO2, or NR0 in each case, and

[0052] s and t are 0 or 1, and

[0053] p and q are each independently selected from the group consisting of 1 to 10 in each case, and

[0054] r and u are independently selected from the group consisting of 0 to 10 in each case, -(C(R)2) p- X 8- (C(R)2) q- (X9) s- (C(R)2) r- (X 10) t -(C(R)2) u The total number of atoms for - is 20 or fewer, and

[0055] R0 is independently selected from the group consisting of a linear or branched alkyl group having 1 to 4 C atoms and a linear or branched partially or fully fluorinated alkyl group having 1 to 4 C atoms in each case;

[0056] R2 is, in each case independently of each other, an aryl group that can be substituted with one or more R', wherein the aryl group is H, a linear or branched alkyl group having 1 to 20 C atoms that is not halogenated or partially or completely halogenated, a linear or branched alkoxyalkyl group having 2 to 20 C atoms that is not halogenated or partially or completely halogenated, a cycloalkyl group having 3 to 7 C atoms, or a aryl group having 6 to 14 C atoms that is not halogenated or partially or completely halogenated;

[0057] R3 and R4 are, in each case independently, H, F, a linear or branched halogenated or partially or fully halogenated alkyl group having 1 to 20 C atoms, a cycloalkyl group having 3 to 7 C atoms, a halogenated or partially or fully halogenated aryl group having 6 to 14 C atoms, said aryl group that can be substituted with one or more R', or a heteroaryl group having 5 to 14 C atoms, said heteroaryl group that can be substituted with one or more R';

[0058] R' is independently selected in each case from the group consisting of F, SF5, CN, SO2CF3, a linear or branched alkyl group having 1 to 20 C atoms that is not halogenated or partially or fully halogenated, a cycloalkyl group having 3 to 6 C atoms that is not halogenated or partially or fully halogenated, a linear or branched alkoxy group having 1 to 20 C atoms that is not halogenated or partially or fully halogenated, and a linear or branched thioalkyl group having 1 to 20 C atoms that is not halogenated or partially or fully halogenated.

[0059] The present invention also relates to a method for forming an ophthalmic device or a precursor article for manufacturing an ophthalmic device as described above or preferably below, said method

[0060] - A step of providing a composition comprising at least one compound of Formula (I), Formula (II), Formula (III), or Formula (IV) described above or preferably below, and / or an oligomer or polymer derived from a compound of Formula (I), Formula (II), Formula (III), or Formula (V) described below or preferably below, having at least one reactive group left for polymerization, but having at least one reactive group left for polymerization, and optionally an additional monomer and / or crosslinking agent and / or UV absorber and / or radical initiator different from the compound of Formula (I), Formula (II), Formula (III), or Formula (IV);

[0061] - Subsequently includes the step of forming an ophthalmic device or a precursor article from the above composition.

[0062] The present invention also relates to a method for modifying the optical properties of an ophthalmic device or a precursor article for manufacturing an ophthalmic device as described above or preferably below, and

[0063] - A step of providing an ophthalmic device or precursor article in a manner as described above or preferably as described below, and

[0064] - Subsequently includes the step of exposing the ophthalmic device or precursor article to irradiation having a wavelength of 200 nm or more and 1500 nm or less.

[0065] The present invention also relates to an ophthalmic device or a precursor article for manufacturing an ophthalmic device that can be obtained by the above method of modifying optical properties, which is described above or preferably below.

[0066] The present invention also relates to an oligomer, polymer, or copolymer comprising at least one polymerizable compound of formula (I), formula (II), formula (III), or formula (IV), wherein all substituents R# as described above or preferably below contain a Si-containing group R1 to be polymerized, provided that silicates based on polymerizable compounds of formulas (I) and (IV) are excluded.

[0067] The present invention also relates to a composition for polymerization comprising at least one compound of formula (I), formula (II), formula (III), or formula (IV) as described above or preferably below, and / or an oligomer or polymer derived from the compound of formula (I), formula (II), formula (III), or formula (IV) as described above or preferably below and having at least one reactive group left for polymerization, and / or a crosslinking agent and / or a UV absorber and / or a radical initiator, and optionally an additional monomer different from the compound of formula (I), formula (II), formula (III), or formula (IV).

[0068] The present invention also relates to chemical formulas (I), (II), (III) and (IV), wherein

[0069] , ,

[0070] , ,

[0071] In the above chemical formulas (I) to (IV),

[0072] R# is independently -[L]-R1 or R2 in each case, provided that at least one R# is -[L]-R1;

[0073] Y1 and Y0 are each independently O or S;

[0074] X is absent or C=O and;

[0075] R1 is a trialkoxysilyl group or a dialkoxyalkylsilyl group, wherein the alkyl and / or alkoxy group is each independently a linear or branched group having 1 to 6 C atoms, or a silyl group of formula (1), formula (2), or formula (3), or a polymerizable group of formula (4);

[0076]

[0077] In the above chemical formulas (1) to (4), alkyl means, in each case independently, a linear or branched alkyl group having 1 to 6 C atoms, and the asterisk “*” indicates, in each case independently, a connection to the linker [L];

[0078] X 11 is selected from the group consisting of O, S, O-SO2, SO2-O, C(=O), OC(=O), C(=O)O, S(C=O)S, and (C=O)S.

[0079] R5, R6, and R7 are each independently selected from the group consisting of H, F, linear or branched alkyl groups having 1 to 20 C atoms that are not fluorinated or partially or fully fluorinated, and aryls having 6 to 14 C atoms, and

[0080] c is independently 0 or 1 in each case;

[0081] [L] is independent of each case, -(C(R)2) o - or -(C(R)2) p -X8-(C(R)2) q -(X9) s -(C(R)2) r -(X 10 ) t -(C(R)2) u - and;

[0082] R is independently selected in each case from the group consisting of H, F, a linear or branched alkyl group having 1 to 4 C atoms, and a linear or branched partially or fully fluorinated alkyl group having 1 to 4 C atoms;

[0083] o is selected from the group consisting of 1 to 20, and

[0084] X8, X9 and X 10 is independently O, S, SO2, or NR0 in each case, and

[0085] s and t are 0 or 1, and

[0086] p and q are each independently selected from the group consisting of 1 to 10, and

[0087] r and u are each independently selected from the group consisting of 0 to 10, -(C(R)2) p -X8-(C(R)2) q -(X9) s -(C(R)2) r -(X 10 )t -(C(R)2) u The total number of atoms for - is 20 or fewer, and

[0088] R0 is independently selected in each case from the group consisting of a linear or branched alkyl group having 1 to 4 C atoms and a linear or branched partially or fully fluorinated alkyl group having 1 to 4 C atoms;

[0089] R2 is, in each case independently of each other, an aryl group that can be substituted with one or more R's, wherein the aryl group is H, a linear or branched alkyl group having 1 to 20 C atoms that is not halogenated or partially or completely halogenated, a linear or branched alkoxyalkyl group having 2 to 20 C atoms that is not halogenated or partially or completely halogenated, a cycloalkyl group having 3 to 7 C atoms, or a aryl group having 6 to 14 C atoms that is not halogenated or partially or completely halogenated;

[0090] R3 and R4 are, in each case independently, H, F, a linear or branched halogenated or partially or fully halogenated alkyl group having 1 to 20 C atoms, a cycloalkyl group having 3 to 7 C atoms, a halogenated or partially or fully halogenated aryl group having 6 to 14 C atoms, said aryl group that can be substituted with one or more R', or a heteroaryl group having 5 to 14 C atoms, said heteroaryl group that can be substituted with one or more R';

[0091] R' is independently selected in each case from the group consisting of F, SF5, CN, SO2CF3, a linear or branched alkyl group having 1 to 20 C atoms that is not halogenated or partially or fully halogenated, a cycloalkyl group having 3 to 6 C atoms that is not halogenated or partially or fully halogenated, a linear or branched alkoxy group having 1 to 20 C atoms that is not halogenated or partially or fully halogenated, and a linear or branched thioalkyl group having 1 to 20 C atoms that is not halogenated or partially or fully halogenated.

[0092] However, in the case of a compound of formula (II) where R# in XR# is [L]-R1, X is absent and [L] is -(C(R)2) o - and, Y0-R# is S-R2, R2 is H, and c is 1;

[0093] However, in the case of a compound of formula (III) in which R# in Y0-R# is [L]-R1, R# in XR# is R2, R3 is F, R1 is a polymerizable group of formula (4), and R5, R6, and R7 are each independently selected from the group consisting of H, F, and linear or branched alkyl groups having 1 to 20 C atoms that are not fluorinated or partially or fully fluorinated;

[0094] However, in the case of a compound of formula (IV) in which R# in both Y1-R# and Y0-R# is [L]-R1, R1 is independently selected from the silyl group of formula (1), formula (2), or formula (3) or the polymerizable group of formula (4). Brief explanation of the drawing

[65535] FIG. 1 is a chart showing the change in refractive index with respect to Abbe number of Application Examples 1 to 36 compared with the application examples for the reference compound Ref-[1] of the prior art. Specific details for implementing the invention

[0095] The compound of formula (I), formula (II), formula (III), or formula (IV) as described above or preferably below may be used as a monomer for producing a blank that can be modified into a polymer, copolymer, or precursor article, such as a contact lens or eye implant, or specifically an ophthalmic device such as an ortholens, or may be used in the manufacture of an ophthalmic device as described above or preferably below.

[0096] All preferred embodiments of the compound of formula (I) and any monomer unit according to the present invention include all stereoisomers or racemic mixtures.

[0097] All preferred embodiments of the compound of formula (II) and any monomer unit according to the present invention include all stereoisomers or racemic mixtures.

[0098] All preferred embodiments of the compound of formula (III) and any monomer unit according to the present invention include all stereoisomers or racemic mixtures.

[0099] All preferred embodiments of the compound of formula (IV) and the compound of formula (IV) comprising any monomer unit according to the present invention include all stereoisomers or racemic mixtures.

[0100] Compounds of formulas (I), (II), (III), and (IV) provide several advantages over conventional materials for manufacturing ophthalmic devices or precursor articles for manufacturing ophthalmic devices as described above. Furthermore, the presence of sulfur atoms in Y0 and / or Y1 in oligomers, polymers, and copolymers comprising compounds of formulas (I), (II), (III), or (IV), or polymerized compounds of formulas (I), (II), (III), or (IV) has a significant effect on optical properties, as this is believed to lead to a larger polarization, a broader absorption range, and a higher molar absorption coefficient.

[0101] Accordingly, compounds of formulas (I), (II), (III), and (IV) as described above, in which at least one of Y0 and Y1 is S, are particularly desirable to be used as monomers for manufacturing blanks that can be modified into precursor articles, such as contact lenses or eye implants or, specifically, ophthalmic devices such as ortho-lenses, or can preferably be used in the manufacture of ophthalmic devices as described above or preferably below. In one embodiment of the present invention, it is preferable that Y0 is S and Y1 is O. In one embodiment of the present invention, it is preferable that Y0 is O and Y1 is S. In another embodiment of the present invention, it is preferable that Y0 and Y1 are S. In another embodiment of the present invention, it is preferable that Y0 and Y1 are O.

[0102] Accordingly, the present invention relates to an ophthalmic device as described above or a precursor article for manufacturing an ophthalmic device, wherein Y1 and Y0 are independently O or S, and at least one of Y1 and Y0 is S.

[0103] Polymers that fold at room temperature generally have a glass transition temperature (T) lower than room temperature (approximately 21°C). gIt represents ). At this temperature, the polymer can be easily deformed without causing physical damage to the polymer by inducing, for example, creep, stress, or fissures. In the case of the polymer of the guide lens, T below 15°C g It is desirable.

[0104] The polymer used in the manufacture of ophthalmic devices, preferably intraocular lenses, preferably has a relatively high refractive index, which makes it possible to manufacture ophthalmic devices, such as contact lenses or intraocular lenses, thinner. Preferably, the polymer used in ophthalmic devices, preferably intraocular lenses, will have a refractive index greater than about 1.49.

[0105] Polymers / copolymers used in the manufacture of ophthalmic devices, preferably intraocular lenses, preferably have a relatively high Abbe number. Preferably, polymers / copolymers used in ophthalmic devices, preferably intraocular lenses, will have an Abbe number greater than 35, and most preferably 37 or higher.

[0106] Where an asterisk ("*") is used in the description of the invention, unless specifically defined, it indicates a connection with an adjacent unit or group, or in the case of a polymer, a connection with an adjacent repeating unit or any other group.

[0107] Linear or branched alkyl groups having 1 to 10 C atoms are alkyl groups having 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 C atoms, e.g., methyl, ethyl, iso -profile, n -profile, iso -butyl, n -butyl, tert -butyl, n -pentyl, 1-, 2- or 3-methylbutyl, 1,1-, 1,2- or 2,2-dimethylpropyl, 1-ethylpropyl, n - Hexyl, n -Heptyl, n-Octyl, Ethylhexyl, n - Nonil or n - Represents a decyl. A linear or branched alkyl group having 1 to 20 C atoms is, for example, n -Undecil, n - Dodecyl, n -Tridecil, n -Tetradecil, n -Pentadecil, n -Hexadecil, n -Heptadecil, n -Octadecil, n - Nonadesil and n - Includes any alkyl group having 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20 C atoms, such as eicosyl, and all examples of linear or branched alkyl groups having 1 to 10 C atoms.

[0108] The term partially halogenated alkyl group indicates that at least one H atom of the alkyl group is substituted with F, Cl, Br, or I. Preferably, the alkyl group is partially fluorinated, which means that at least one H atom of the alkyl group is substituted with F. A preferred partially halogenated alkyl group is CH2CF3.

[0109] The term "fully halogenated alkyl group" indicates that all H atoms of the alkyl group are substituted with F, Cl, Br, and / or I. Preferably, the alkyl group is fully fluorinated, which means that all H atoms of the alkyl group are substituted with F. The preferred fully fluorinated alkyl group is trifluoromethyl or pentafluoroethyl.

[0110] The term halogenated or preferably fluorinated additionally corresponds to other groups such as halogenated cycloalkyl groups, halogenated alkoxy groups, or halogenated thioalkyl groups.

[0111] Cycloalkyl groups having 3 to 6 C atoms include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl, which may be partially or completely halogenated or fluorinated as described above. Preferably, the cycloalkyl group is cyclopropyl.

[0112] A linear or branched alkoxy group having 1 to 20 C atoms is an O-alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 C atoms, e.g., methoxy, ethoxy, iso -Propoxi, n -Propoxi, iso -Butoxy, n -Butoxy, tert -Butoxy, n -pentyloxy, 1-, 2- or 3-methylbutyloxy, 1,1-, 1,2- or 2,2-dimethylpropoxy, 1-ethylpropoxy, n -hexyloxy, n -Heptyloxy, n -Octyloxy, Ethylhexyloxy, n - Nonyloxy, n - Decyloxy, n -Undecyloxy, n - Dodecyloxy, n - Tridecyloxy, n - Tetradecyloxy, n -Pentadeciloxy, n -Hexadecyloxy, n -Heptadecyloxy, n - Octadecyloxy, n - Nonadeciloxy and n - Represents eicosyloxy, which may be partially or completely halogenated or, preferably, partially or completely fluorinated. The preferred completely fluorinated alkoxy group is trifluoromethoxy.

[0113] A linear or branched optionally partially or completely halogenated alkoxyalkyl group having 2 to 20 C atoms represents an alkyl group in which at least one H atom is substituted with an alkoxy group substituted with a halogen, such as F, Cl, or Br, where it is a partially halogenated alkoxyalkyl group. The alkoxyalkyl group described above has a total of 2 to 20 C atoms, preferably a total of 2 to 8 C atoms. Preferably, the linear or branched optionally partially or completely halogenated alkoxyalkyl group having 2 to 20 C atoms is optionally partially or completely fluorinated. Preferred examples include methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, pentoxymethyl, methoxyethane-2-yl, methoxypropane-3-yl, methoxybutane-4-yl, methoxypentane-5-yl, methoxyhexane-6-yl, ethoxyethane-2-yl, propoxyethane-2-yl, butoxyethane-2-yl, pentoxyethane-2-yl, ethoxypropane-3-yl, ethoxybutane-4-yl, ethoxypentane-5-yl, propoxypropane-3-yl, propoxybutane-4-yl, propoxypentane-5-yl, butoxypropane-3-yl, pentoxypropane-3-yl, butoxybutane-4-yl, trifluoromethoxymethyl, trifluoromethoxyethane-2-yl, trifluoromethoxypropane-3-yl, The preferred optionally fluorinated alkoxyalkyl groups are trifluoromethoxybutane-4-yl, trifluoromethoxypentane-5-yl, trifluoromethoxyhexane-6-yl, trifluoromethoxydifluoromethyl, and pentafluoroethoxydifluoromethyl. The preferred optionally fluorinated alkoxyalkyl groups are methoxymethyl, methoxyethane-2-yl, trifluoromethoxymethyl, and trifluoromethoxyethane-2-yl.

[0114] A linear or branched thioalkyl group having 1 to 20 C atoms is an S-alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 C atoms, e.g., thiomethyl, 1-thioethyl, 1-thio-iso-propyl, 1-thio-n -propyl, 1-thio-iso-butyl, 1-thio- n -butyl, 1-thio-tert-butyl, 1-thio- n -pentyl, 1-thio-1-, -2- or -3-methylbutyl, 1-thio-1,1-, -1,2- or -2,2-dimethylpropyl, 1-thio-1-ethylpropyl, 1-thio- n -hexyl, 1-thio- n -heptyl, 1-thio- n -octyl, 1-thio-ethylhexyl, 1-thio- n -nonil, 1-thio -n -decyl, 1-thio- n -undecyl, 1-thio- n -dodecyl, 1-thio- n -Tridecyl, 1-thio- n -Tetradecyl, 1-thio- n -Pentadecil, 1-thio- n -Hexadecyl, 1-thio- n -Heptadecyl, 1-thio- n -Octadecil, 1-thio- n -Nonadecyl and 1-thio- n - Represents eicosyl, which may be partially or completely halogenated or, preferably, partially or completely fluorinated. The preferred completely fluorinated thioether group is trifluoromethyl thioether.

[0115] Desirable alkyl and alkoxy radicals have 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 C atoms.

[0116] In the context of the present invention, an aryl group comprises 6 to 40 ring atoms, and in the context of the present invention, a heteroaryl group comprises 5 to 40 ring atoms including at least one heteroatom. The heteroatom is preferably selected from N, O, and / or S. An aryl group or a heteroaryl group is understood herein to mean a simple aromatic cycle, i.e., phenyl, or a simple heteroaromatic cycle, e.g., pyridinyl, pyrimidinyl, thiophenyl, etc., or a fused (cyclic) aryl or heteroaryl group, e.g., naphthyl, anthracenyl, phenanthrenyl, quinolinyl, or isoquinolinyl.

[0117] The aryl group or heteroaryl group is preferably benzene, naphthalene, anthracene, phenanthrene, pyrene, benzanthracene, chrysene, perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, triphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenoflurene, cis- or trans-indenocarbazole, cis- or trans-indolocarbazole, truxen, isotruxen, spirotruxen, spiroisotruxen, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, Isoquinoline, Acridine, Fenantridine, Benzo-5,6-quinoline, Benzo-6,7-quinoline, Benzo-7,8-quinoline, Phenothiazine, Fenoxazine, Pyrazol, Indazole, Imidazole, Benzimidazole, Naftimidazole, Fenantrimidazole, Pyridimidazole, Pyrazineimidazole, Quinoxalineimidazole, Oxazole, Benzoxazole, Naphtoxazole, Anthroxazole, Fenantroxazole, Isoxazole, 1,2-Thiaazole, 1,3-Thiaazole, Benzothiazole, Pyridazine, Hexazatriphenylene, Benzopyridazine, Pyrimidine, Benzopyrimidine, Quinoxazolin, 1,5-Diazanthracene, 2,7-Diazapyrene, 2,3-Diazapyrene, 1,6-Diazapyrene, 1,8-Diazapyrene, 4,5-Diazapyrene, 4,5,9,10-Tetraazaperylene, Pyrazine, Phenazine, Phenoxazine, Phenothiazine, Fluorubin, Naftiridine, Azacarbazole, Benzocarbolin, Phenanthroline, 1,2,3-Triazol, 1,2,4-Triazol, Benzotriazole, 1,2,3-Oxadiazole, 1,2,4-Oxadiazole, 1,2,5-Oxadiazole, 1,3,4-Oxadiazole, 1,2,3-Thiadiazol, 1,2,4-Thiadiazol, 1,2,5-Thiadiazol, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine,It is derived from indolizin and benzothiadiasol.

[0118] A polymerizable group is a group that can be polymerized or polymerized to form an oligomer or polymer.

[0119] Polymerization is a process of taking individual monomers and chain-linking them together to form longer units. These longer units are called polymers. Compounds of formula (I), formula (II), formula (III), or formula (IV), as described above and preferably below, are monomers suitable for manufacturing ophthalmic devices or precursor articles for manufacturing ophthalmic devices.

[0120] In the gist of the invention, the polymerizable group R1, once oligomerized or polymerized, becomes part of or forms the backbone of an oligomer, polymer, or copolymer comprising a polymerized compound of Formula (I), Formula (II), Formula (III), or Formula (IV). A suitable polymerizable group is defined as a trialkoxysilyl group or a diallkoxyalkylsilyl group, wherein the alkyl and / or alkoxy groups are each independently linear or branched having 1 to 6 C atoms, or are a silyl group of Formula (1), Formula (2), or Formula (3) or a polymerizable group of Formula (4).

[0121]

[0122] Here, alkyl means a linear or branched alkyl group having 1 to 6 C atoms independently in each case, and an asterisk "*" indicates a connection to the linker [L] independently in each case;

[0123] X 11 is selected from the group consisting of O, S, O-SO2, SO2-O, C(=O), OC(=O), C(=O)O, S(C=O)S, and (C=O)S.

[0124] R5, R6, and R7 are each independently selected from the group consisting of H, F, linear or branched alkyl groups having 1 to 20 C atoms that are not fluorinated or partially or fully fluorinated, and aryls having 6 to 14 C atoms.

[0125] c is 0 or 1.

[0126] A particularly desirable polymerizable group is described below. A particularly desirable polymerized group is described below.

[0127] An aryl having 6 to 14 C atoms is an aryl group preferably selected from the group consisting of phenyl, naphthyl or anthryl, particularly preferably phenyl.

[0128] The preferred compounds of formula (I) are compounds of formulas (Ia), (Ib), and (Ic), and

[0129] , ,

[0130] ,

[0131] In the above formula, R1, [L], R2, Y1, Y0, X, R3, and R4 have the meanings described above or, preferably, described below.

[0132] The preferred compounds of formula (II) are compounds of formulas (II-a), (II-b), and (II-c), and

[0133] , ,

[0134] ,

[0135] In the above formula, R1, [L], R2, Y1, Y0, X, R3, and R4 have the meanings described above or, preferably, described below.

[0136] The preferred compounds of formula (III) are compounds of formulas (III-a), (III-b), and (III-c), and

[0137] , , ,

[0138] In the above formula, R1, [L], R2, Y1, Y0, X, R3, and R4 have the meanings described above or, preferably, described below.

[0139] The preferred compounds of formula (IV) are compounds of formulas (IV-a), (IV-b), and (IV-c), and

[0140] , , ,

[0141] In the above formula, R1, [L], R2, Y1, Y0, X, R3, and R4 have the meanings described above or, preferably, described below.

[0142] In a preferred embodiment, the compound of Formula (I), Formula (II), Formula (III), or Formula (IV) acting as a monomer or compound according to the present invention for the manufacture of an ophthalmic device or a precursor article for the manufacture of an ophthalmic device as described above, or for the manufacture of an oligomer, polymer, or copolymer according to the present invention, contains only one substituent R# which is -[L]-R1, and the other substituent R# is R2, wherein [L], R1, and R2 have the meanings described above or preferably below.

[0143] The compounds of formula (I) that are particularly desirable are the compounds of formulas (Ia) and (Ib). The compounds of formula (I) that are very particularly desirable are the compounds of formula (Ia).

[0144] The compounds of formula (II) that are particularly desirable are the compounds of formulas (II-a) and (II-b). The compounds of formula (I) that are very particularly desirable are the compounds of formula (II-a).

[0145] Particularly desirable compounds of formula (III) are compounds of formulas (III-a) and (III-b).

[0146] Particularly desirable compounds of formula (IV) are compounds of formulas (IV-a) and (IV-b).

[0147] Accordingly, the present invention relates to an ophthalmic device or a precursor article for manufacturing an ophthalmic device as described above, wherein in a polymerized compound of formula (I), formula (II), formula (III), or formula (IV), only one substituent R# is -[L]-R1 and the other substituent R# is R2, where [L], R1, and R2 have the same meaning as described above or preferably as described below.

[0148] Accordingly, the present invention relates to an ophthalmic device or a precursor article for manufacturing an ophthalmic device as described above, comprising at least one compound of the formulas (Ia), (Ib), (Ic), (II-a), (II-b), (II-c), (III-a), (III-b), (III-c), (IV-a), (IV-b), or (IV-c) as described above, wherein R1, [L], R2, Y1, Y0, X, R3, and R4 have the meanings described above or preferably as described below.

[0149] Accordingly, the present invention relates to a compound of the formula (Ia), formula (Ib), formula (Ic), formula (II-a), formula (II-b), formula (II-c), formula (III-a), formula (III-b), formula (III-c), formula (IV-a), formula (IV-b), or formula (IV-c) as described above, wherein R1, [L], R2, Y1, Y0, X, R3, and R4 have the meanings described above or preferably as described below.

[0150] However, in the case of the compound of formula (II-b), X is absent and [L] is -(C(R)2) o- And, Y0-R# is S-R2, R2 is H, and c is 1;

[0151] However, in the case of a compound of formula (IIIa), R 3 is F, R1 is a polymerizable group of formula (4), and R5, R6, and R7 are each independently selected from the group consisting of H, F, or linear or branched alkyl groups having 1 to 20 C atoms that are not fluorinated or are partially or completely fluorinated;

[0152] However, in the case of the compound of formula (IV-c), R1 is independently selected from the silyl group of formula (1), formula (2), or formula (3) or the polymerizable group of formula (4).

[0153] In the compounds of formulas (I), (Ia), (Ib), (Ic), (II), (II-a), (II-b), (II-c), (III), (III-a), (III-b), (III-c), (IV), (IV-a), (IV-b), and (IV-c), X is absent or C=O.

[0154] In the compounds of formulas (Ib), (II-b), and (III-b), X is preferably absent or C=O.

[0155] In the compounds of formulas (I), (Ia), (Ib), (Ic), (II), (II-a), (II-b), (II-c), (III), (III-a), (III-b), (III-c), (IV), (IV-a), (IV-b), and (IV-c), X is particularly preferably absent.

[0156] Accordingly, the present invention further relates to an ophthalmic device or a precursor article for manufacturing an ophthalmic device comprising at least one polymerized compound of formula (I), formula (Ia), formula (Ib), formula (Ic), formula (II), formula (II-a), formula (II-b), formula (II-c), formula (III), formula (III-a), formula (III-b), formula (III-c), formula (IV), formula (IV-a), formula (IV-b), or formula (IV-c), wherein X is absent and Y0, Y1, [L], R1, R2, R3, and R4 have the meanings described above or preferably below.

[0157] As described above, in the ophthalmic device according to the present invention, the precursor article for manufacturing the ophthalmic device, the compound of formula (I), formula (Ia), formula (Ib), formula (Ic), formula (II), formula (II-a), formula (II-b), formula (II-c), formula (III), formula (III-a), formula (III-b), formula (III-c), formula (IV), formula (IV-a), formula (IV-b) or formula (IV-c) and any oligomer, polymer, or copolymer derived therefrom, the substituent R' is, in each case, independently F, SF5, CN, SO2CF3, a linear or branched alkyl group having 1 to 20 C atoms that is not halogenated or partially or completely halogenated, a cycloalkyl group having 3 to 6 C atoms that is not halogenated or partially or completely halogenated, and a linear or branched alkoxy group having 1 to 20 C atoms that is not halogenated or partially or completely halogenated. and is selected from linear or branched thioalkyl groups having 1 to 20 C atoms that are not halogenated or are partially or completely halogenated.

[0158] R' is, in each case independently preferably SF5, SO2CF3, a linear or branched alkyl group having 1 to 10 C atoms that is not halogenated or is partially or completely halogenated, or a linear or branched alkoxy group having 1 to 10 C atoms that is not halogenated and is partially or completely halogenated. R' is, in each case independently particularly preferably SO2CF3, SF5, methyl, ethyl, n -profile, n -butyl, n -pentyl, n - Hexyl, n -Heptyl, n-Octyl, trifluoromethyl, pentafluoroethyl, heptafluoropropyl, methoxy, ethoxy, propoxy, trifluoromethoxy, pentafluoroethoxy, thiomethyl, and thioethyl. R' is independently, in each case, very particularly preferably SF5, SO2CF3, methyl, n-pentyl, trifluoromethyl, or trifluoromethoxy.

[0159] In one embodiment of the present invention, the unhalogenated or partially or completely halogenated aryl group having 6 to 14 C atoms preferably has 2, 1 or 0 substituent(s) R', where R' has the meaning as described above or preferably as described above.

[0160] As described above, in the ophthalmic device, precursor article, compound of formula (I), formula (Ia), formula (Ib), formula (Ic), formula (II), formula (II-a), formula (II-b), formula (II-c), formula (III), formula (III-a), formula (III-b), formula (III-c), formula (IV), formula (IV-a), formula (IV-b) or formula (IV-c) according to the present invention, preferred compound of formula (I), formula (Ia), formula (Ib), formula (Ic), formula (II), formula (II-a), formula (II-b), formula (II-c), formula (III), formula (III-a), formula (III-b), formula (III-c), formula (IV), formula (IV-a), formula (IV-b) or formula (IV-c), and any oligomer, polymer or copolymer derived therefrom, R2 is, in each case, independently of H, linear or branched, non-halogenated or partially or having 1 to 20 C atoms A fully halogenated alkyl group, a linear or branched alkoxyalkyl group having 1 to 20 C atoms that is not halogenated or is partially or fully halogenated, a cycloalkyl group having 3 to 7 C atoms, or an aryl group having 6 to 14 C atoms that is not halogenated or is partially or fully halogenated and can be substituted with one or more R's, wherein R' has the meaning described or preferably as described above.

[0161] Preferably, where R2 is connected to the remainder of Formula (I), Formula (Ia), Formula (II), Formula (II-a), Formula (III), or Formula (III-a) through an N atom, R2 is H, a linear or branched alkyl group having 1 to 10 C atoms that is not halogenated or partially or completely halogenated, a linear or branched alkoxyalkyl group having 1 to 8 C atoms that is not halogenated or partially or completely halogenated, or a phenyl group having 1 or more R' that can be substituted, wherein R' has the meaning described or preferably as previously stated. Particularly preferably, R2 is H, a linear or branched alkyl group having 1 to 10 C atoms that is not halogenated or partially or completely halogenated, a linear or branched alkoxyalkyl group having 1 to 8 C atoms that is not halogenated or partially or completely halogenated. Very particularly preferably, R2 is H, methyl, ethyl, n -Profile, isoprofile, n -butyl, 1-methyl-butyl, 2,2,2-trifluoroethyl, trifluoromethoxyethyl, phenyl, or phenyl substituted with one or more of SF5, SO2CF3, methyl, ethyl, n-pentyl, trifluoromethyl, or trifluoromethoxy. Very particularly preferably, R2 is H or methyl.

[0162] Preferably, where R2 is connected to the remainder of Formula (I), Formula (Ib), Formula (II), Formula (II-b), Formula (III), or Formula (III-b) through Y0 or Y1 as described above or preferably as described above, R2 is a linear or branched unhalogenated or partially or fully halogenated alkyl group having 1 to 10 C atoms, or a linear or branched unhalogenated or partially or fully halogenated alkoxyalkyl group having 1 to 8 C atoms. Particularly preferably, R2 is a linear or branched non-halogenated alkyl group having 1 to 10 C atoms. Very particularly preferably, R2 is methyl or ethyl.

[0163] As described above, in the ophthalmic device according to the present invention, a precursor article for manufacturing an ophthalmic device, a compound of formula (I), formula (Ia), formula (Ib), formula (Ic), formula (II), formula (II-a), formula (II-b), formula (II-c), formula (III), formula (III-a), formula (III-b), formula (III-c), formula (IV), formula (IV-a), formula (IV-b) or formula (IV-c), and any oligomer, polymer, or copolymer derived therefrom, R3 is H, F, a linear or branched alkyl group having 1 to 20 C atoms that is not halogenated or partially or completely halogenated, a cycloalkyl group having 3 to 7 C atoms, an aryl group having 6 to 14 C atoms that is not halogenated or partially or completely halogenated and may be substituted with one or more R's, or having 5 to 14 C atoms that may be substituted with one or more R's. It is a heteroaryl group, where R' has the meaning described above or preferably as described above.

[0164] Preferably, R3 is H, F, a linear or branched alkyl group having 1 to 10 C atoms that is not halogenated or partially or completely halogenated, a phenyl group that is not halogenated or partially or completely halogenated and may be substituted with one or more R's, or a pyridyl group that may be substituted with one or more R's, wherein R' has the meaning as described above or preferably as described above. Particularly preferably, R3 is H, F, methyl, ethyl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, phenyl, or phenyl substituted with one or more of SF5, SO2CF3, methyl, ethyl, n-pentyl, trifluoromethyl, or trifluoromethoxy.

[0165] As described above, in the ophthalmic device according to the present invention, a precursor article for manufacturing an ophthalmic device, a compound of formula (I), formula (Ia), formula (Ib), formula (Ic), formula (II), formula (II-a), formula (II-b), formula (II-c), formula (III), formula (III-a), formula (III-b), formula (III-c), formula (IV), formula (IV-a), formula (IV-b) or formula (IV-c), and any oligomer, polymer, or copolymer derived therefrom, R4 is H, F, a linear or branched alkyl group having 1 to 20 C atoms that is not halogenated or partially or completely halogenated, a cycloalkyl group having 3 to 7 C atoms, a aryl group having 6 to 14 C atoms that is not halogenated or partially or completely halogenated and may be substituted with one or more R's, or a group having 5 to 14 C atoms that may be substituted with one or more R's. It is a heteroaryl group, where R' has the meaning described above or preferably as described above.

[0166] Preferably, R4 is H, a linear or branched alkyl group having 1 to 10 C atoms that is not halogenated or partially or fully halogenated, a phenyl group that is not halogenated or partially or fully halogenated and may be substituted with one or more R's, or a pyridyl group that may be substituted with one or more R's, wherein R' has the meaning described above or preferably as described above. Particularly preferably, R4 is H, methyl, n - It is propyl or phenyl.

[0167] According to the present invention, a compound of formula (I), formula (Ia), formula (Ib), formula (Ic), formula (II), formula (II-a), formula (II-b), formula (II-c), formula (III), formula (III-a), formula (III-b), formula (III-c), formula (IV), formula (IV-a), formula (IV-b) or formula (IV-c) having a substituent as described above, used as a monomer for manufacturing an ophthalmic device according to the present invention, has at least one polymerizable group as described above or preferably as described below, and has at least one linking element [L]. In a preferred embodiment of the present invention, a compound of formula (I), formula (Ia), formula (Ib), formula (II), formula (II-a), formula (II-b), formula (III), formula (III-a), formula (III-b), formula (IV), formula (IV-a) or formula (IV-b) having a substituent as described above or preferably as described below, used as a monomer for manufacturing an ophthalmic device according to the present invention, has only one polymerizable group as described above or preferably as described below, connected to one linking element [L].

[0168] According to the present invention, the connecting element [L] is independently -(C(R)2) in each caseo- or -(C(R)2) p- X 8- (C(R)2) q- (X9) s- (C(R)2) r- (X 10 ) t -(C(R)2) u Selected from the group consisting of -, where R is independently selected in each case from H, F, a linear or branched alkyl group having 1 to 4 C atoms or a linear or branched partially or fully fluorinated alkyl group having 1 to 4 C atoms, and o is selected from 1 to 20, and X8, X9 and X 10 is O, S, SO2, or NR0 in each case, s and t are independently 0 or 1 in each case, p and q are independently selected from 1 to 10 in each case, r and u are independently selected from 0 to 10 in each case, where, -(C(R)2) p- X 8- (C(R)2) q- (X9) s- (C(R)2) r- (X 10 ) t -(C(R)2) u - In the case of -, the total number of atoms is 20 or fewer C atoms. In NR0, R0 is, in each case independently, a linear or branched alkyl group having 1 to 4 C atoms and a linear or branched partially or completely fluorinated alkyl group having 1 to 4 C atoms. R0 is, in each case independently and preferably methyl, ethyl, or trifluoromethyl. R0 is, in each case independently and particularly preferably methyl.

[0169] According to the present invention, R is, in each case, independently H, F, a linear or branched alkyl group having 1 to 8 C atoms, or a linear or branched partially or completely fluorinated alkyl group having 1 to 4 C atoms.

[0170] R is particularly preferably independently H, F, methyl or ethyl or H and F in each case. R is very particularly preferably H.

[0171] In another preferred embodiment of the present invention, in a compound of formula (I), formula (Ia), formula (Ib), formula (Ic), formula (II), formula (II-a), formula (II-b), formula (II-c), formula (III), formula (III-a), formula (III-b), formula (III-c), formula (IV), formula (IV-a), formula (IV-b) and formula (IV-c) that acts as a monomer for the manufacture of an ophthalmic device or a precursor article of an ophthalmic device as described above, or for the manufacture of an oligomer, polymer, or copolymer according to the present invention, o is preferably 2, 3, 4, 5, 6, 9, 11, or 12. Preferably, o is 6, 9, 11, or 12. Particularly preferably, o is 6 or 12.

[0172] With respect to the compound according to the present invention, the same preferred meaning for o applies as described above.

[0173] In another preferred embodiment of the present invention, in a compound of formula (I), formula (Ia), formula (Ib), formula (Ic), formula (II), formula (II-a), formula (II-b), formula (II-c), formula (III), formula (III-a), formula (III-b), formula (III-c), formula (IV), formula (IV-a), formula (IV-b), and formula (IV-c) acting as a monomer for the manufacture of an ophthalmic device or a precursor article of an ophthalmic device as described above, or for the manufacture of an oligomer, polymer, or copolymer according to the present invention, or in a compound according to the present invention, s, t, X8, X9, X 10 , p, q, r, and u have the following desirable meanings:

[0174] Preferably, s is 1. Preferably, s is 0.

[0175] Preferably, t is 0 or 1.

[0176] Preferably, s and t are 0.

[0177] Preferably, X8, X9 and X 10 is O, S, or SO2. Particularly preferably, X8, X9, and X 10 is O. Particularly preferably, X8, X9, and X 10 is S. Particularly preferably, X8, X9, and X 10 It is SO2.

[0178] Preferably, p and q are each independently 1, 3, 3, 4, 5 or 6, particularly preferably 1 or 2, very particularly preferably 2.

[0179] Preferably, r and u are each independently 0, 1, 2 or 3, particularly preferably 0, 1 or 2, very particularly preferably 0.

[0180] -(CH2)-, -(CH2)2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -(CH2)9-, -(CH2) 10 -, -(CH2) 11 -, -(CH2) 12 -, -(CH2) 13 -, -(CH2) 14 -, -(CH2) 15 -, -(CH2) 16 -, -(CH2) 17 -, -(CH2) 18 -, -(CH2) 19 -, -(CH2) 20 -, -(CHCH3)-, -(CHCH3)2-, -(CHCH3)3-, -(CHCH3)4-, -(CHCH3)5-, -(CHCH3)6-, -(CHCH3)7-, -(CHCH3)8-, -(CHCH3)9-, -(CHCH3) 10 -, -(CHCH3) 11 -, -(CHCH3) 12 -, -(CHCH3) 13 -, -(CHCH3) 14 -, -(CHCH3) 15 -, -(CHCH3) 16 -, -(CHCH3) 17 -, -(CHCH3) 18 -, -(CHCH3) 19 -, -(CHCH3) 20 -, -(C(CH3)2)-, -(C(CH3)2)2-, -(C(CH3)2)3-, -(C(CH3)2)4-, -(C(CH3)2)5-, -(C(CH3)2)6-, -(C(CH3)2)7-, -(C(CH3)2)8-, -(C(CH3)2)9-, -(C(CH3)2) 10 -, -(C(CH3)2) 11 -, -(C(CH3)2) 12 -, -(C(CH3)2) 13 -, -(C(CH3)2) 14 -, -(C(CH3)2)15 -, -(C(CH3)2) 16 -, -(C(CH3)2) 17 -, -(C(CH3)2) 18 -, -(C(CH3)2) 19 -, -(C(CH3)2) 20 -, -(CHC2H5)-, -(CHC2H5)2-, -(CHC2H5)3-, -(CHC2H5)4-, -(CHC2H5)5-, -(CHC2H5)6-, -(CHC2H5)7-, -(CHC2H5)8-, -(CHC2H5)9-, -(CHC2H5) 10 -, -(CHC2H5) 11 -, -(CHC2H5) 12 -, -(CHC2H5) 13 -, -(CHC2H5) 14 -, -(CHC2H5) 15 -, -(CHC2H5) 16 -, -(CHC2H5) 17 -, -(CHC2H5) 18 -, -(CHC2H5) 19 -, -(CHC2H5) 20 -, -(CH2)-(CHCH3)-(CH2)-, -(CH2)-(CHCH3)-(CH2)2-, -(CH2)-(CHCH3)-(CH2)3-, -(CH2)-(CHCH3)-(CH2) 11 -, -(CH2)2-(CHCH3)-(CH2)-, -(CH2)3-(CHCH3)-(CH2)-, -(CH2) 11-(CHCH3)-(CH2)-, -(CH2)2-O-(CH2)2-, -(CH2)3-O-(CH2)3-, -(CH2)2-O-(CH2)2-O-(CH2)2-, -(CH2)3-O-(CH2)3-O-(CH2)3-, -(CH2)2-O-(CH2)2-O-(CH2)6-, -(CH2)6-O-(CH2)2-O-(CH2)2-, -(CH2)2-O-(CH2)2-O-(CH2)8-, -(CH2)8-O-(CH2)2-O-(CH2)2-, -(CH2)2-S-(CH2)2-, -(CH2)3-S-(CH2)3-, -(CH2)2-S-(CH2)2-S-(CH2)2-, -(CH2)3-S-(CH2)3-S-(CH2)3-, -(CH2)2-S-(CH2)2-S-(CH2)6-, -(CH2)6-S-(CH2)2-S-(CH2)2-, -(CH2)2-S-(CH2)2-S-(CH2)8-, -(CH2)8-S-(CH2)2-S-(CH2)2-, -(CH2)2-SO2-(CH2)2-, -(CH2)3-SO2-(CH2)2-SO2-(CH2)2-, -(CH2)3-SO2-(CH2)3-SO2-(CH2)3-, -(CH2)2-SO2-(CH2)2-SO2-(CH2)6- -(CH2)6-SO2-(CH2)2-SO2-(CH2)2-, -(CH2)2-SO2-(CH2)2-SO2-(CH2)8-, -(CH2)8-SO2-(CH2)2-SO2-(CH2)2-, -(CH2)-S-(CH2)2-O-(CH2)-, -(CH2)-SO2-(CH2)2-O-(CH2)-, -(CH2)-SO2-(CH2)2-S-(CH2)-, -(CH2)-O-(CH2)2-S-(CH2)2-O-(CH2)-, -(CH2)-S-(CH2)2-O-(CH2)2-S-(CH2)-, -(CH2)-SO2-(CH2)2-O-(CH2)2-SO2-(CH2)- -(CH2)-S-(CH2)2-S-(CH2)2-S-(CH2)-, -(CH2)-SO2-(CH2)2-SO2-(CH2)2-SO2-(CH2)-, -(CH2)-O-(CH2)2-SO2-(CH2)2-O-(CH2)-, -(CH2)2-(NCH3)-(CH2)2--(CH2)3-(NCH3)-(CH2)3-, -(CH2)2-(NCH3)-(CH2)2-(NCH3)-(CH2)2-, -(CH2)3-(NCH3)-(CH2)3-(NCH3)-(CH2)3-, -(CH2)2-(NCH3)-(CH2)2-(NCH3)-(CH2)6-, -(CH2)6-(NCH3)-(CH2)2-(NCH3)-(CH2)2-, -(CH2)2-(NCH3)-(CH2)2-(NCH3)-(CH2)8- and -(CH2)8-(NCH3)-(CH2)2-(NCH3)-(CH2)2-;

[0181] -(CF2)-(CH2)-, -(CH2)-(CF2)-, -(CH2)-(CF2)-(CH2)-, -(CH2)-(CF2)-(CH2)2-, -(CH2)-(CF2)-(CH2)3-, -(CH2)-(CF2)-(CH2)4-, -(CH2)-(CF2)-(CH2)5-, -(CH2)-(CF2)-(CH2)6-, -(CH2)-(CF2)-(CH2)7-, -(CH2)-(CF2)-(CH2)8-, -(CH2)-(CF2)-(CH2)9-, -(CH2)-(CF2)-(CH2) 10 -, -(CH2)2-(CF2)-(CH2)-, -(CH2)3-(CF2)-(CH2)-, -(CH2)4-(CF2)-(CH2)-, -(CH2)5-(CF2)-(CH2)-, -(CH2)6-(CF2)-(CH2)-, -(CH2)7-(CF2)-(CH2)-, -(CH2)8-(CF2)-(CH2)-, -(CH2)9-(CF2)-(CH2)-, -(CH2) 10-(CF2)-(CH2)-, -(CH2)2-(CF2)-(CH2)2-, -(CH2)3-(CF2)-(CH2)3-, -(CH2)4-(CF2)-(CH2)4-, -(CH2)5-(CF2)-(CH2)5-, -(CH2)2-(CF2)-(CH2)-, -(CH2)2-(CF2)-(CH2)3-, -(CH2)2-(CF2)-(CH2)4-, -(CH2)2-(CF2)-(CH2)5-, -(CH2)2-(CF2)-(CH2)6-, -(CH2)2-(CF2)-(CH2)7-, -(CH2)2-(CF2)-(CH2)8-, -(CH2)2-(CF2)-(CH2)9-, -(CH2)3-(CF2)-(CH2)-, -(CH2)3-(CF2)-(CH2)2-, -(CH2)3-(CF2)-(CH2)4-, -(CH2)3-(CF2)-(CH2)5-, -(CH2)3-(CF2)-(CH2)6-, -(CH2)3-(CF2)-(CH2)7-, -(CH2)3-(CF2)-(CH2)8-, -(CH2)4-(CF2)-(CH2)-, -(CH2)4-(CF2)-(CH2)2-, -(CH2)4-(CF2)-(CH2)3-, -(CH2)4-(CF2)-(CH2)5-, -(CH2)4-(CF2)-(CH2)6-, -(CH2)4-(CF2)-(CH2)7-, -(CH2)5-(CF2)-(CH2)-, -(CH2)5-(CF2)-(CH2)2-, -(CH2)5-(CF2)-(CH2)3-, -(CH2)5-(CF2)-(CH2)4-, -(CH2)5-(CF2)-(CH2)6-, -(CH2)6-(CF2)-(CH2)-, -(CH2)6-(CF2)-(CH2)2-, -(CH2)6-(CF2)-(CH2)3-, -(CH2)6-(CF2)-(CH2)4-, -(CH2)6-(CF2)-(CH2)5-,

[0182] -(CFH)-(CH2)-, -(CH2)-(CFH)-, -(CH2)-(CFH)-(CH2)-, -(CH2)-(CFH)-(CH2)2-, -(CH2)-(CFH)-(CH2)3-, -(CH2)-(CFH)-(CH2)4-, -(CH2)-(CFH)-(CH2)5-, -(CH2)-(CFH)-(CH2)6-, -(CH2)-(CFH)-(CH2)7-, -(CH2)-(CFH)-(CH2)8-, -(CH2)-(CFH)-(CH2)9-, -(CH2)-(CFH)-(CH2) 10 -, -(CH2)2-(CFH)-(CH2)-, -(CH2)3-(CFH)-(CH2)-, -(CH2)4-(CFH)-(CH2)-, -(CH2)5-(CFH)-(CH2)-, -(CH2)6-(CFH)-(CH2)-, -(CH2)7-(CFH)-(CH2)-, -(CH2)8-(CFH)-(CH2)-, -(CH2)9-(CFH)-(CH2)-, -(CH2) 10-(CFH)-(CH2)-, -(CH2)2-(CFH)-(CH2)2-, -(CH2)3-(CFH)-(CH2)3-, -(CH2)4-(CFH)-(CH2)4-, -(CH2)5-(CFH)-(CH2)5-, -(CH2)2-(CFH)-(CH2)-, -(CH2)2-(CFH)-(CH2)3-, -(CH2)2-(CFH)-(CH2)4-, -(CH2)2-(CFH)-(CH2)5-, -(CH2)2-(CFH)-(CH2)6-, -(CH2)2-(CFH)-(CH2)7-, -(CH2)2-(CFH)-(CH2)8-, -(CH2)2-(CFH)-(CH2)9-, -(CH2)3-(CFH)-(CH2)-, -(CH2)3-(CFH)-(CH2)2-, -(CH2)3-(CFH)-(CH2)4-, -(CH2)3-(CFH)-(CH2)5-, -(CH2)3-(CFH)-(CH2)6-, -(CH2)3-(CFH)-(CH2)7-, -(CH2)3-(CFH)-(CH2)8-, -(CH2)4-(CFH)-(CH2)-, -(CH2)4-(CFH)-(CH2)2-, -(CH2)4-(CFH)-(CH2)3-, -(CH2)4-(CFH)-(CH2)5-, -(CH2)4-(CFH)-(CH2)6-, -(CH2)4-(CFH)-(CH2)7-, -(CH2)5-(CFH)-(CH2)-, -(CH2)5-(CFH)-(CH2)2-, -(CH2)5-(CFH)-(CH2)3-, -(CH2)5-(CFH)-(CH2)4-, -(CH2)5-(CFH)-(CH2)6-, -(CH2)6-(CFH)-(CH2)-, -(CH2)6-(CFH)-(CH2)2-, -(CH2)6-(CFH)-(CH2)3-, -(CH2)6-(CFH)-(CH2)4-, -(CH2)6-(CFH)-(CH2)5-,

[0183] -(CF2)2-(CH2)-, -(CH2)-(CF2)2-, -(CH2)-(CF2)2-(CH2)-, -(CH2)-(CF2)2-(CH2)2-, -(CH2)-(CF2)2-(CH2)3-, -(CH2)-(CF2)2-(CH2)4-, -(CH2)-(CF2)2-(CH2)5-, -(CH2)-(CF2)2-(CH2)6-, -(CH2)-(CF2)2-(CH2)7-, -(CH2)-(CF2)2-(CH2)8-, -(CH2)-(CF2)2-(CH2)9-, -(CH2)2-(CF2)2-(CH2)-, -(CH2)3-(CF2)2-(CH2)-, -(CH2)4-(CF2)2-(CH2)-, -(CH2)5-(CF2)2-(CH2)-, -(CH2)6-(CF2)2-(CH2)-, -(CH2)7-(CF2)2-(CH2)-, -(CH2)8-(CF2)2-(CH2)-, -(CH2)9-(CF2)2-(CH2)-, -(CH2)2-(CF2)2-(CH2)2-, -(CH2)3-(CF2)2-(CH2)3-, -(CH2)4-(CF2)2-(CH2)4-, -(CH2)5-(CF2)2-(CH2)5-, -(CH2)2-(CF2)2-(CH2)-,-(CH2)2-(CF2)2-(CH2)3-, -(CH2)2-(CF2)2-(CH2)4-, -(CH2)2-(CF2)2-(CH2)5-, -(CH2)2-(CF2)2-(CH2)6-, -(CH2)2-(CF2)2-(CH2)7-, -(CH2)2-(CF2)2-(CH2)8-, -(CH2)3-(CF2)2-(CH2)-, -(CH2)3-(CF2)2-(CH2)2-, -(CH2)3-(CF2)2-(CH2)4-, -(CH2)3-(CF2)2-(CH2)5-, -(CH2)3-(CF2)2-(CH2)6-, -(CH2)3-(CF2)2-(CH2)7-, -(CH2)4-(CF2)2-(CH2)-, -(CH2)4-(CF2)2-(CH2)2-, -(CH2)4-(CF2)2-(CH2)3-, -(CH2)4-(CF2)2-(CH2)5-, -(CH2)4-(CF2)2-(CH2)6-, -(CH2)5-(CF2)2-(CH2)-, -(CH2)5-(CF2)2-(CH2)2-,-(CH2)5-(CF2)2-(CH2)3-, -(CH2)5-(CF2)2-(CH2)4-, -(CH2)6-(CF2)2-(CH2)-, -(CH2)6-(CF2)2-(CH2)2-, -(CH2)6-(CF2)2-(CH2)3-, -(CH2)6-(CF2)2-(CH2)4-,

[0184] -(CFH)2-(CH2)-, -(CH2)-(CFH)2-, -(CH2)-(CFH)2-(CH2)-, -(CH2)-(CFH)2-(CH2)2-, -(CH2)-(CFH)2-(CH2)3-, -(CH2)-(CFH)2-(CH2)4-, -(CH2)-(CFH)2-(CH2)5-, -(CH2)-(CFH)2-(CH2)6-, -(CH2)-(CFH)2-(CH2)7-, -(CH2)-(CFH)2-(CH2)8-, -(CH2)-(CFH)2-(CH2)9-, -(CH2)2-(CFH)2-(CH2)-, -(CH2)3-(CFH)2-(CH2)-, -(CH2)4-(CFH)2-(CH2)-, -(CH2)5-(CFH)2-(CH2)-, -(CH2)6-(CFH)2-(CH2)-, -(CH2)7-(CFH)2-(CH2)-, -(CH2)8-(CFH)2-(CH2)-, -(CH2)9-(CFH)2-(CH2)-, -(CH2)2-(CFH)2-(CH2)2-, -(CH2)3-(CFH)2-(CH2)3-, -(CH2)4-(CFH)2-(CH2)4-, -(CH2)5-(CFH)2-(CH2)5-, -(CH2)2-(CFH)2-(CH2)-,-(CH2)2-(CFH)2-(CH2)3-, -(CH2)2-(CFH)2-(CH2)4-, -(CH2)2-(CFH)2-(CH2)5-, -(CH2)2-(CFH)2-(CH2)6-, -(CH2)2-(CFH)2-(CH2)7-, -(CH2)2-(CFH)2-(CH2)8-, -(CH2)3-(CFH)2-(CH2)-, -(CH2)3-(CFH)2-(CH2)2-, -(CH2)3-(CFH)2-(CH2)4-, -(CH2)3-(CFH)2-(CH2)5-, -(CH2)3-(CFH)2-(CH2)6-, -(CH2)3-(CFH)2-(CH2)7-, -(CH2)4-(CFH)2-(CH2)-, -(CH2)4-(CFH)2-(CH2)2-, -(CH2)4-(CFH)2-(CH2)3-, -(CH2)4-(CFH)2-(CH2)5-, -(CH2)4-(CFH)2-(CH2)6-, -(CH2)5-(CFH)2-(CH2)-, -(CH2)5-(CFH)2-(CH2)2-,-(CH2)5-(CFH)2-(CH2)3-, -(CH2)5-(CFH)2-(CH2)4-, -(CH2)6-(CFH)2-(CH2)-, -(CH2)6-(CFH)2-(CH2)2-, -(CH2)6-(CFH)2-(CH2)3-, -(CH2)6-(CFH)2-(CH2)4-,

[0185] -(CF2)3-(CH2)-, -(CH2)-(CF2)3-, -(CH2)-(CF2)3-(CH2)-, -(CH2)-(CF2)3-(CH2)2-, -(CH2)-(CF2)3-(CH2)3-, -(CH2)-(CF2)3-(CH2)4-, -(CH2)-(CF2)3-(CH2)5-, -(CH2)-(CF2)3-(CH2)6-, -(CH2)-(CF2)3-(CH2)7-, -(CH2)-(CF2)3-(CH2)8-, -(CH2)2-(CF2)3-(CH2)-, -(CH2)3-(CF2)3-(CH2)-, -(CH2)4-(CF2)3-(CH2)-, -(CH2)5-(CF2)3-(CH2)-, -(CH2)6-(CF2)3-(CH2)-, -(CH2)7-(CF2)3-(CH2)-, -(CH2)8-(CF2)3-(CH2)-, -(CH2)2-(CF2)3-(CH2)2-, -(CH2)3-(CF2)3-(CH2)3-, -(CH2)4-(CF2)3-(CH2)4-, -(CH2)2-(CF2)3-(CH2)-,-(CH2)2-(CF2)3-(CH2)3-, -(CH2)2-(CF2)3-(CH2)4-, -(CH2)2-(CF2)3-(CH2)5-, -(CH2)2-(CF2)3-(CH2)6-, -(CH2)2-(CF2)3-(CH2)7-, -(CH2)3-(CF2)3-(CH2)-, -(CH2)3-(CF2)3-(CH2)2-, -(CH2)3-(CF2)3-(CH2)4-, -(CH2)3-(CF2)3-(CH2)5-, -(CH2)3-(CF2)3-(CH2)6-, -(CH2)4-(CF2)3-(CH2)-, -(CH2)4-(CF2)3-(CH2)2-, -(CH2)4-(CF2)3-(CH2)3-, -(CH2)4-(CF2)3-(CH2)5-, -(CH2)5-(CF2)3-(CH2)-, -(CH2)5-(CF2)3-(CH2)2-, -(CH2)5-(CF2)3-(CH2)3-, -(CH2)5-(CF2)3-(CH2)4-, (CH2)6-(CF2)3-(CH2)-, -(CH2)6-(CF2)3-(CH2)2-, -(CH2)6-(CF2)3-(CH2)3-, -(CF2)4-(CH2)-, -(CH2)-(CF2)4-,-(CH2)-(CF2)4-(CH2)-, -(CH2)-(CF2)4-(CH2)2-, -(CH2)-(CF2)4-(CH2)3-, -(CH2)-(CF2)4-(CH2)4-, -(CH2)-(CF2)4-(CH2)5-, -(CH2)-(CF2)4-(CH2)6-, -(CH2)-(CF2)4-(CH2)7-, -(CH2)-(CF2)4-(CH2)8-, -(CH2)-(CF2)4-(CH2)9-, -(CH2)-(CF2)4-(CH2), 10 -, -(CH2)2-(CF2)4-(CH2)-, -(CH2)3-(CF2)4-(CH2)-, -(CH2)4-(CF2)4-(CH2)-, -(CH2)5-(CF2)4-(CH2)-, -(CH2)6-(CF2)4-(CH2)-, -(CH2)7-(CF2)4-(CH2)-, -(CH2)2-(CF2)4-(CH2)2-, -(CH2)3-(CF2)4-(CH2)3-, -(CH2)4-(CF2)4-(CH2)4-, -(CH2)5-(CF2)4-(CH2)5-, -(CH2)2-(CF2)4-(CH2)3-, -(CH2)2-(CF2)4-(CH2)4-, -(CH2)2-(CF2)4-(CH2)5-, -(CH2)2-(CF2)4-(CH2)6-, -(CH2)3-(CF2)4-(CH2)2-, -(CH2)3-(CF2)4-(CH2)4-, -(CH2)4-(CF2)4-(CH2)2-, -(CH2)4-(CF2)4-(CH2)3-, -(CH2)5-(CF2)4-(CH2)2-, -(CH2)5-(CF2)4-(CH2)3-, -(CH2)6-(CF2)4-(CH2)2-,

[0186] -(CF2)5-(CH2)-, -(CH2)-(CF2)5-, -(CH2)-(CF2)5-(CH2)-, -(CH2)-(CF2)5-(CH2)2-, -(CH2)-(CF2)5-(CH2)3-, -(CH2)-(CF2)5-(CH2)4-, -(CH2)-(CF2)5-(CH2)5-, -(CH2)-(CF2)5-(CH2)6-, -(CH2)2-(CF2)5-(CH2)-, -(CH2)3-(CF2)5-(CH2)-, -(CH2)4-(CF2)5-(CH2)-, -(CH2)5-(CF2)5-(CH2)-, -(CH2)6-(CF2)5-(CH2)-, -(CH2)2-(CF2)5-(CH2)2-, -(CH2)3-(CF2)5-(CH2)3-, -(CH2)4-(CF2)5-(CH2)4-, -(CH2)2-(CF2)5-(CH2)3-, -(CH2)2-(CF2)5-(CH2)4-, -(CH2)2-(CF2)5-(CH2)5-, -(CH2)2-(CF2)5-(CH2)6-, -(CH2)3-(CF2)5-(CH2)2-, -(CH2)3-(CF2)5-(CH2)4-, -(CH2)4-(CF2)5-(CH2)2-, -(CH2)4-(CF2)5-(CH2)3-, -(CH2)5-(CF2)5-(CH2)2-,

[0187] -(CHCF3)-(CH2)-, -(CH2)-(CHCF3)-, -(CH2)-(CHCF3)-(CH2)-, -(CH2)-(CHCF3)-(CH2)2-, -(CH2)-(CHCF3)-(CH2)3-, -(CH2)-(CHCF3)-(CH2)4-, -(CH2)-(CHCF3)-(CH2)5-, -(CH2)-(CHCF3)-(CH2)6-, -(CH2)-(CHCF3)-(CH2)7-, -(CH2)-(CHCF3)-(CH2)8-, -(CH2)-(CHCF3)-(CH2)9-, -(CH2)-(CHCF3)-(CH2) 10-, -(CH2)2-(CHCF3)-(CH2)-, -(CH2)3-(CHCF3)-(CH2)-, -(CH2)4-(CHCF3)-(CH2)-, -(CH2)5-(CHCF3)-(CH2)-, -(CH2)6-(CHCF3)-(CH2)-, -(CH2)7-(CHCF3)-(CH2)-, -(CH2)8-(CHCF3)-(CH2)-, -(CH2)9-(CHCF3)-(CH2)-, -(CH2) 10 -(CHCF3)-(CH2)-, -(CH2)2-(CHCF3)-(CH2)2-, -(CH2)3-(CHCF3)-(CH2)3-, -(CH2)4-(CHCF3)-(CH2)4-, -(CH2)5-(CHCF3)-(CH2)5-, -(CH2)2-(CHCF3)-(CH2)3-, -(CH2)2-(CHCF3)-(CH2)4-, -(CH2)2-(CHCF3)-(CH2)5-, -(CH2)2-(CHCF3)-(CH2)6-, -(CH2)2-(CHCF3)-(CH2)7-, -(CH2)2-(CHCF3)-(CH2)8-, -(CH2)2-(CHCF3)-(CH2)9- -(CH2)3-(CHCF3)-(CH2)2-, -(CH2)3-(CHCF3)-(CH2)4-, -(CH2)3-(CHCF3)-(CH2)5-, -(CH2)3-(CHCF3)-(CH2)6-, -(CH2)3-(CHCF3)-(CH2)7-, -(CH2)3-(CHCF3)-(CH2)8-, -(CH2)4-(CHCF3)-(CH2)2-, -(CH2)4-(CHCF3)-(CH2)3-, -(CH2)4-(CHCF3)-(CH2)5-, -(CH2)4-(CHCF3)-(CH2)6-, -(CH2)4-(CHCF3)-(CH2)7-, -(CH2)5-(CHCF3)-(CH2)2- -(CH2)5-(CHCF3)-(CH2)3-, -(CH2)5-(CHCF3)-(CH2)4-, -(CH2)5-(CHCF3)-(CH2)6-, -(CH2)6-(CHCF3)-(CH2)2-, -(CH2)6-(CHCF3)-(CH2)3-, -(CH2)6-(CHCF3)-(CH2)4-, -(CH2)6-(CHCF3)-(CH2)5-

[0188] -(CHCF3)2-(CH2)-, -(CH2)-(CHCF3)2-, -(CH2)-(CHCF3)2-(CH2)-, -(CH2)-(CHCF3)2-(CH2)2-, -(CH2)-(CHCF3)2-(CH2)3-, -(CH2)-(CHCF3)2-(CH2)4-, -(CH2)-(CHCF3)2-(CH2)5-, -(CH2)-(CHCF3)2-(CH2)6-, -(CH2)-(CHCF3)2-(CH2)7-, -(CH2)-(CHCF3)2-(CH2)8-, -(CH2)-(CHCF3)2-(CH2)9-, -(CH2)2-(CHCF3)2-(CH2)- -(CH2)3-(CHCF3)2-(CH2)-, -(CH2)4-(CHCF3)2-(CH2)-, -(CH2)5-(CHCF3)2-(CH2)-, -(CH2)6-(CHCF3)2-(CH2)-, -(CH2)7-(CHCF3)2-(CH2)-, -(CH2)8-(CHCF3)2-(CH2)-, -(CH2)9-(CHCF3)2-(CH2)-, -(CH2)2-(CHCF3)2-(CH2)2-, -(CH2)3-(CHCF3)2-(CH2)3-, -(CH2)4-(CHCF3)2-(CH2)4-, -(CH2)5-(CHCF3)2-(CH2)5-, -(CH2)2-(CHCF3)2-(CH2)3- -(CH2)2-(CHCF3)2-(CH2)4-, -(CH2)2-(CHCF3)2-(CH2)5-, -(CH2)2-(CHCF3)2-(CH2)6-, -(CH2)2-(CHCF3)2-(CH2)7-, -(CH2)2-(CHCF3)2-(CH2)8-, -(CH2)3-(CHCF3)2-(CH2)2-, -(CH2)3-(CHCF3)2-(CH2)4-, -(CH2)3-(CHCF3)2-(CH2)5-, -(CH2)3-(CHCF3)2-(CH2)6-, -(CH2)3-(CHCF3)2-(CH2)7-, -(CH2)4-(CHCF3)2-(CH2)2- -(CH2)4-(CHCF3)2-(CH2)3-, -(CH2)4-(CHCF3)2-(CH2)5-, -(CH2)4-(CHCF3)2-(CH2)6-, -(CH2)5-(CHCF3)2-(CH2)2--(CH2)5-(CHCF3)2-(CH2)3-, -(CH2)5-(CHCF3)2-(CH2)4-, -(CH2)6-(CHCF3)2-(CH2)2-, -(CH2)6-(CHCF3)2-(CH2)3-, -(CH2)6-(CHCF3)2-(CH2)4-

[0189] -(CHCF3)3-(CH2)-, -(CH2)-(CHCF3)3-, -(CH2)-(CHCF3)3-(CH2)-, -(CH2)-(CHCF3)3-(CH2)2-, -(CH2)-(CHCF3)3-(CH2)3-, -(CH2)-(CHCF3)3-(CH2)4-, -(CH2)-(CHCF3)3-(CH2)5-, -(CH2)-(CHCF3)3-(CH2)6-, -(CH2)-(CHCF3)3-(CH2)7-, -(CH2)-(CHCF3)3-(CH2)8-, -(CH2)2-(CHCF3)3-(CH2)-, -(CH2)3-(CHCF3)3-(CH2)- -(CH2)4-(CHCF3)3-(CH2)-, -(CH2)5-(CHCF3)3-(CH2)-, -(CH2)6-(CHCF3)3-(CH2)-, -(CH2)7-(CHCF3)3-(CH2)-, -(CH2)8-(CHCF3)3-(CH2)-, -(CH2)2-(CHCF3)3-(CH2)2-, -(CH2)3-(CHCF3)3-(CH2)3-, -(CH2)4-(CHCF3)3-(CH2)4-, -(CH2)2-(CHCF3)3-(CH2)3-, -(CH2)2-(CHCF3)3-(CH2)4-, -(CH2)2-(CHCF3)3-(CH2)5- -(CH2)2-(CHCF3)3-(CH2)6-, -(CH2)2-(CHCF3)3-(CH2)7-, -(CH2)3-(CHCF3)3-(CH2)2-, -(CH2)3-(CHCF3)3-(CH2)4-, -(CH2)3-(CHCF3)3-(CH2)5-, -(CH2)3-(CHCF3)3-(CH2)6-, -(CH2)4-(CHCF3)3-(CH2)2-, -(CH2)4-(CHCF3)3-(CH2)3-, -(CH2)4-(CHCF3)3-(CH2)5-, -(CH2)5-(CHCF3)3-(CH2)2-, -(CH2)5-(CHCF3)3-(CH2)3- -(CH2)5-(CHCF3)3-(CH2)4-, -(CH2)6-(CHCF3)3-(CH2)2-, -(CH2)6-(CHCF3)3-(CH2)3-,

[0190] -(CHCF3)4-(CH2)-, -(CH2)-(CHCF3)4-, -(CH2)-(CHCF3)4-(CH2)-, -(CH2)-(CHCF3)4-(CH2)2-, -(CH2)-(CHCF3)4-(CH2)3-, -(CH2)-(CHCF3)4-(CH2)4-, -(CH2)-(CHCF3)4-(CH2)5-, -(CH2)-(CHCF3)4-(CH2)6-, -(CH2)-(CHCF3)4-(CH2)7-, -(CH2)-(CHCF3)4-(CH2)8-, -(CH2)-(CHCF3)4-(CH2)9-, -(CH2)-(CHCF3)4-(CH2) 10 -, -(CH2)2-(CHCF3)4-(CH2)-, -(CH2)3-(CHCF3)4-(CH2)-, -(CH2)4-(CHCF3)4-(CH2)-, -(CH2)5-(CHCF3)4-(CH2)-, -(CH2)6-(CHCF3)4-(CH2)-, -(CH2)7-(CHCF3)4-(CH2)-, -(CH2)2-(CHCF3)4-(CH2)2-, -(CH2)3-(CHCF3)4-(CH2)3-, -(CH2)4-(CHCF3)4-(CH2)4-, -(CH2)5-(CHCF3)4-(CH2)5-, -(CH2)2-(CHCF3)4-(CH2)3- -(CH2)2-(CHCF3)4-(CH2)4-, -(CH2)2-(CHCF3)4-(CH2)5-, -(CH2)2-(CHCF3)4-(CH2)6-, -(CH2)3-(CHCF3)4-(CH2)2-, -(CH2)3-(CHCF3)4-(CH2)4-, -(CH2)4-(CHCF3)4-(CH2)2-, -(CH2)4-(CHCF3)4-(CH2)3-, -(CH2)5-(CHCF3)4-(CH2)2-, -(CH2)5-(CHCF3)4-(CH2)3-, -(CH2)6-(CHCF3)4-(CH2)2-

[0191] -(CHCF3)5-(CH2)-, -(CH2)-(CHCF3)5-, -(CH2)-(CHCF3)5-(CH2)-, -(CH2)-(CHCF3)5-(CH2)2-, -(CH2)-(CHCF3)5-(CH2)3-, -(CH2)-(CHCF3)5-(CH2)4-, -(CH2)-(CHCF3)5-(CH2)5-, -(CH2)-(CHCF3)5-(CH2)6-, -(CH2)2-(CHCF3)5-(CH2)-, -(CH2)3-(CHCF3)5-(CH2)-, -(CH2)4-(CHCF3)5-(CH2)-, -(CH2)5-(CHCF3)5-(CH2)- -(CH2)6-(CHCF3)5-(CH2)-, -(CH2)2-(CHCF3)5-(CH2)2-, -(CH2)3-(CHCF3)5-(CH2)3-, -(CH2)4-(CHCF3)5-(CH2)4-, -(CH2)2-(CHCF3)5-(CH2)3-, -(CH2)2-(CHCF3)5-(CH2)4-, -(CH2)2-(CHCF3)5-(CH2)5-, -(CH2)2-(CHCF3)5-(CH2)6-, -(CH2)3-(CHCF3)5-(CH2)2-, -(CH2)3-(CHCF3)5-(CH2)4-, -(CH2)4-(CHCF3)5-(CH2)2- -(CH2)4-(CHCF3)5-(CH2)3-, -(CH2)5-(CHCF3)5-(CH2)2-,

[0192] -[C(CH3)CF3]-(CH2)-, -(CH2)-[C(CH3)CF3]-, -(CH2)-[C(CH3)CF3]-(CH2)-, -(CH2)-[C(CH3)CF3]-(CH2)2-, -(CH2)-[C(CH3)CF3]-(CH2)3-, -(CH2)-[C(CH3)CF3]-(CH2)4-, -(CH2)-[C(CH3)CF3]-(CH2)5-, -(CH2)-[C(CH3)CF3]-(CH2)6-, -(CH2)-[C(CH3)CF3]-(CH2)7-, -(CH2)-[C(CH3)CF3]-(CH2)8-, -(CH2)-[C(CH3)CF3]-(CH2)9-, -(CH2)-[C(CH3)CF3]-(CH2) 10-, -(CH2)2-[C(CH3)CF3]-(CH2)-, -(CH2)3-[C(CH3)CF3]-(CH2)-, -(CH2)4-[C(CH3)CF3]-(CH2)-, -(CH2)5-[C(CH3)CF3]-(CH2)-, -(CH2)6-[C(CH3)CF3]-(CH2)-, -(CH2)7-[C(CH3)CF3]-(CH2)-, -(CH2)8-[C(CH3)CF3]-(CH2)-, -(CH2)9-[C(CH3)CF3]-(CH2)-, -(CH2) 10-[C(CH3)CF3]-(CH2)-, -(CH2)2-[C(CH3)CF3]-(CH2)2-, -(CH2)3-[C(CH3)CF3]-(CH2)3-, -(CH2)4-[C(CH3)CF3]-(CH2)4-, -(CH2)5-[C(CH3)CF3]-(CH2)5-, -(CH2)2-[C(CH3)CF3]-(CH2)3-, -(CH2)2-[C(CH3)CF3]-(CH2)4-, -(CH2)2-[C(CH3)CF3]-(CH2)5-, -(CH2)2-[C(CH3)CF3]-(CH2)6-, -(CH2)2-[C(CH3)CF3]-(CH2)7-, -(CH2)2-[C(CH3)CF3]-(CH2)8-, -(CH2)2-[C(CH3)CF3]-(CH2)9-, -(CH2)3-[C(CH3)CF3]-(CH2)2-, -(CH2)3-[C(CH3)CF3]-(CH2)4-, -(CH2)3-[C(CH3)CF3]-(CH2)5-, -(CH2)3-[C(CH3)CF3]-(CH2)6-, -(CH2)3-[C(CH3)CF3]-(CH2)7-, -(CH2)3-[C(CH3)CF3]-(CH2)8-, -(CH2)4-[C(CH3)CF3]-(CH2)2-, -(CH2)4-[C(CH3)CF3]-(CH2)3-, -(CH2)4-[C(CH3)CF3]-(CH2)5-, -(CH2)4-[C(CH3)CF3]-(CH2)6-, -(CH2)4-[C(CH3)CF3]-(CH2)7-, -(CH2)5-[C(CH3)CF3]-(CH2)2-, -(CH2)5-[C(CH3)CF3]-(CH2)3-, -(CH2)5-[C(CH3)CF3]-(CH2)4-, -(CH2)5-[C(CH3)CF3]-(CH2)6-, -(CH2)6-[C(CH3)CF3]-(CH2)2-, -(CH2)6-[C(CH3)CF3]-(CH2)3-, -(CH2)6-[C(CH3)CF3]-(CH2)4-, -(CH2)6-[C(CH3)CF3]-(CH2)5-,

[0193] -[C(CH3)CF3]2-(CH2)-, -(CH2)-[C(CH3)CF3]2-, -(CH2)-[C(CH3)CF3]2-(CH2)-, -(CH2)-[C(CH3)CF3]2-(CH2)2-, -(CH2)-[C(CH3)CF3]2-(CH2)3-, -(CH2)-[C(CH3)CF3]2-(CH2)4-, -(CH2)-[C(CH3)CF3]2-(CH2)5-, -(CH2)-[C(CH3)CF3]2-(CH2)6-, -(CH2)-[C(CH3)CF3]2-(CH2)7-, -(CH2)-[C(CH3)CF3]2-(CH2)8-, -(CH2)-[C(CH3)CF3]2-(CH2)9-, -(CH2)2-[C(CH3)CF3]2-(CH2)-, -(CH2)3-[C(CH3)CF3]2-(CH2)-, -(CH2)4-[C(CH3)CF3]2-(CH2)-, -(CH2)5-[C(CH3)CF3]2-(CH2)-, -(CH2)6-[C(CH3)CF3]2-(CH2)-, -(CH2)7-[C(CH3)CF3]2-(CH2)-, -(CH2)8-[C(CH3)CF3]2-(CH2)-, -(CH2)9-[C(CH3)CF3]2-(CH2)-, -(CH2)2-[C(CH3)CF3]2-(CH2)2-, -(CH2)3-[C(CH3)CF3]2-(CH2)3-, -(CH2)4-[C(CH3)CF3]2-(CH2)4-, -(CH2)5-[C(CH3)CF3]2-(CH2)5-, -(CH2)2-[C(CH3)CF3]2-(CH2)3-, -(CH2)2-[C(CH3)CF3]2-(CH2)4-, -(CH2)2-[C(CH3)CF3]2-(CH2)5-, -(CH2)2-[C(CH3)CF3]2-(CH2)6-, -(CH2)2-[C(CH3)CF3]2-(CH2)7-, -(CH2)2-[C(CH3)CF3]2-(CH2)8-, -(CH2)3-[C(CH3)CF3]2-(CH2)2-, -(CH2)3-[C(CH3)CF3]2-(CH2)4-, -(CH2)3-[C(CH3)CF3]2-(CH2)5-, -(CH2)3-[C(CH3)CF3]2-(CH2)6-, -(CH2)3-[C(CH3)CF3]2-(CH2)7-,-(CH2)4-[C(CH3)CF3]2-(CH2)2-, -(CH2)4-[C(CH3)CF3]2-(CH2)3-, -(CH2)4-[C(CH3)CF3]2-(CH2)5-, -(CH2)4-[C(CH3)CF3]2-(CH2)6-, -(CH2)5-[C(CH3)CF3]2-(CH2)2-, -(CH2)5-[C(CH3)CF3]2-(CH2)3-, -(CH2)5-[C(CH3)CF3]2-(CH2)4-, -(CH2)6-[C(CH3)CF3]2-(CH2)2-, -(CH2)6-[C(CH3)CF3]2-(CH2)3-, -(CH2)6-[C(CH3)CF3]2-(CH2)4-,

[0194] -[C(CH3)CF3]3-(CH2)-, -(CH2)-[C(CH3)CF3]3-, -(CH2)-[C(CH3)CF3]3-(CH2)-, -(CH2)-[C(CH3)CF3]3-(CH2)2-, -(CH2)-[C(CH3)CF3]3-(CH2)3-, -(CH2)-[C(CH3)CF3]3-(CH2)4-, -(CH2)-[C(CH3)CF3]3-(CH2)5-, -(CH2)-[C(CH3)CF3]3-(CH2)6-, -(CH2)-[C(CH3)CF3]3-(CH2)7-, -(CH2)-[C(CH3)CF3]3-(CH2)8-, -(CH2)2-[C(CH3)CF3]3-(CH2)-, -(CH2)3-[C(CH3)CF3]3-(CH2)-, -(CH2)4-[C(CH3)CF3]3-(CH2)-, -(CH2)5-[C(CH3)CF3]3-(CH2)-, -(CH2)6-[C(CH3)CF3]3-(CH2)-, -(CH2)7-[C(CH3)CF3]3-(CH2)-, -(CH2)8-[C(CH3)CF3]3-(CH2)-, -(CH2)2-[C(CH3)CF3]3-(CH2)2-, -(CH2)3-[C(CH3)CF3]3-(CH2)3-, -(CH2)4-[C(CH3)CF3]3-(CH2)4-, -(CH2)2-[C(CH3)CF3]3-(CH2)3-, -(CH2)2-[C(CH3)CF3]3-(CH2)4-, -(CH2)2-[C(CH3)CF3]3-(CH2)5-, -(CH2)2-[C(CH3)CF3]3-(CH2)6-, -(CH2)2-[C(CH3)CF3]3-(CH2)7-, -(CH2)3-[C(CH3)CF3]3-(CH2)2-, -(CH2)3-[C(CH3)CF3]3-(CH2)4-, -(CH2)3-[C(CH3)CF3]3-(CH2)5-, -(CH2)3-[C(CH3)CF3]3-(CH2)6-, -(CH2)4-[C(CH3)CF3]3-(CH2)2-, -(CH2)4-[C(CH3)CF3]3-(CH2)3-, -(CH2)4-[C(CH3)CF3]3-(CH2)5-, -(CH2)5-[C(CH3)CF3]3-(CH2)2-, -(CH2)5-[C(CH3)CF3]3-(CH2)3-,-(CH2)5-[C(CH3)CF3]3-(CH2)4-, -(CH2)6-[C(CH3)CF3]3-(CH2)2-, -(CH2)6-[C(CH3)CF3]3-(CH2)3-,

[0195] -[C(CH3)CF3]4-(CH2)-, -(CH2)-[C(CH3)CF3]4-, -(CH2)-[C(CH3)CF3]4-(CH2)-, -(CH2)-[C(CH3)CF3]4-(CH2)2-, -(CH2)-[C(CH3)CF3]4-(CH2)3-, -(CH2)-[C(CH3)CF3]4-(CH2)4-, -(CH2)-[C(CH3)CF3]4-(CH2)5-, -(CH2)-[C(CH3)CF3]4-(CH2)6-, -(CH2)-[C(CH3)CF3]4-(CH2)7-, -(CH2)-[C(CH3)CF3]4-(CH2)8-, -(CH2)-[C(CH3)CF3]4-(CH2)9-, -(CH2)-[C(CH3)CF3]4-(CH2) 10-, -(CH2)2-[C(CH3)CF3]4-(CH2)-, -(CH2)3-[C(CH3)CF3]4-(CH2)-, -(CH2)4-[C(CH3)CF3]4-(CH2)-, -(CH2)5-[C(CH3)CF3]4-(CH2)-, -(CH2)6-[C(CH3)CF3]4-(CH2)-, -(CH2)7-[C(CH3)CF3]4-(CH2)-, -(CH2)2-[C(CH3)CF3]4-(CH2)2-, -(CH2)3-[C(CH3)CF3]4-(CH2)3-, -(CH2)4-[C(CH3)CF3]4-(CH2)4-, -(CH2)5-[C(CH3)CF3]4-(CH2)5-, -(CH2)2-[C(CH3)CF3]4-(CH2)3-, -(CH2)2-[C(CH3)CF3]4-(CH2)4-, -(CH2)2-[C(CH3)CF3]4-(CH2)5-, -(CH2)2-[C(CH3)CF3]4-(CH2)6-, -(CH2)3-[C(CH3)CF3]4-(CH2)2-, -(CH2)3-[C(CH3)CF3]4-(CH2)4-, -(CH2)4-[C(CH3)CF3]4-(CH2)2-, -(CH2)4-[C(CH3)CF3]4-(CH2)3-, -(CH2)5-[C(CH3)CF3]4-(CH2)2-, -(CH2)5-[C(CH3)CF3]4-(CH2)3-, -(CH2)6-[C(CH3)CF3]4-(CH2)2-,

[0196] -[C(CH3)CF3]5-(CH2)-, -(CH2)-[C(CH3)CF3]5-, -(CH2)-[C(CH3)CF3]5-(CH2)-, -(CH2)-[C(CH3)CF3]5-(CH2)2-, -(CH2)-[C(CH3)CF3]5-(CH2)3-, -(CH2)-[C(CH3)CF3]5-(CH2)4-, -(CH2)-[C(CH3)CF3]5-(CH2)5-, -(CH2)-[C(CH3)CF3]5-(CH2)6-, -(CH2)2-[C(CH3)CF3]5-(CH2)-, -(CH2)3-[C(CH3)CF3]5-(CH2)-, -(CH2)4-[C(CH3)CF3]5-(CH2)-, -(CH2)5-[C(CH3)CF3]5-(CH2)-, -(CH2)6-[C(CH3)CF3]5-(CH2)-, -(CH2)2-[C(CH3)CF3]5-(CH2)2-, -(CH2)3-[C(CH3)CF3]5-(CH2)3-, -(CH2)4-[C(CH3)CF3]5-(CH2)4-, -(CH2)2-[C(CH3)CF3]5-(CH2)3-, -(CH2)2-[C(CH3)CF3]5-(CH2)4-, -(CH2)2-[C(CH3)CF3]5-(CH2)5-, -(CH2)2-[C(CH3)CF3]5-(CH2)6-, -(CH2)3-[C(CH3)CF3]5-(CH2)2-, -(CH2)3-[C(CH3)CF3]5-(CH2)4-, -(CH2)4-[C(CH3)CF3]5-(CH2)2-, -(CH2)4-[C(CH3)CF3]5-(CH2)3-, -(CH2)5-[C(CH3)CF3]5-(CH2)2-,

[0197] -[CH(CH2CF3)]-(CH2)-, -(CH2)-[CH(CH2CF3)]-, -(CH2)-[CH(CH2CF3)]-(CH2)-, -(CH2)-[CH(CH2CF3)]-(CH2)2-, -(CH2)-[CH(CH2CF3)] -(CH2)3-, -(CH2)-[CH(CH2CF3)]-(CH2)4-, -(CH2)-[CH(CH2CF3)]-(CH2)5-, -(CH2)-[CH(CH2CF3)]-(CH2)6-, -(CH2)-[CH(CH2CF3)]-(CH2)7-, -(CH2)-[CH(CH2CF3)]-(CH2)8-, -(CH2)-[CH(CH2CF3)]-(CH2)9-, -(CH2)-[CH(CH2CF3)]-(CH2) 10 -, -(CH2)2-[CH(CH2CF3)]-(CH2)-, -(CH2)3-[CH(CH2CF3)]-(CH2)-, -(CH2)4-[CH(CH2CF3)]-(CH2)-, -(CH2)5-[CH(CH2CF3)]-(CH2)-, -(CH2)6-[CH(CH2CF3)]-(CH2)-, -(CH2)7-[CH(CH2CF3)]-(CH2)-, -(CH2)8-[CH(CH2CF3)]-(CH2)-, -(CH2)9-[CH(CH2CF3)]-(CH2)-, -(CH2) 10-[CH(CH2CF3)]-(CH2)-, -(CH2)2-[CH(CH2CF3)]-(CH2)2-, -(CH2)3-[CH(CH2CF3)]-(CH2)3-, -(CH2)4-[CH(CH2CF3)]-(CH2)4-, -(CH2)5-[CH(CH2CF3)]-(CH2)5-, -(CH2)2-[CH(CH2CF3)]-(CH2)3-, -(CH2)2-[CH(CH2CF3)]-(CH2)4-, -(CH2)2-[CH(CH2CF3)]-(CH2)5-, -(CH2)2-[CH(CH2CF3)]-(CH2)6-, -(CH2)2-[CH(CH2CF3)]-(CH2)7-, -(CH2)2-[CH(CH2CF3)]-(CH2)8-, -(CH2)2-[CH(CH2CF3)]-(CH2)9-, -(CH2)3-[CH(CH2CF3)]-(CH2)2-, -(CH2)3-[CH(CH2CF3)]-(CH2)4-, -(CH2)3-[CH(CH2CF3)]-(CH2)5-, -(CH2)3-[CH(CH2CF3)]-(CH2)6-, -(CH2)3-[CH(CH2CF3)]-(CH2)7-, -(CH2)3-[CH(CH2CF3)]-(CH2)8-, -(CH2)4-[CH(CH2CF3)]-(CH2)2-, -(CH2)4-[CH(CH2CF3)]-(CH2)3-, -(CH2)4-[CH(CH2CF3)]-(CH2)5-, -(CH2)4-[CH(CH2CF3)]-(CH2)6-, -(CH2)4-[CH(CH2CF3)]-(CH2)7-, -(CH2)5-[CH(CH2CF3)]-(CH2)2-, -(CH2)5-[CH(CH2CF3)]-(CH2)3-, -(CH2)5-[CH(CH2CF3)]-(CH2)4-, -(CH2)5-[CH(CH2CF3)]-(CH2)6-, -(CH2)6-[CH(CH2CF3)]-(CH2)2-, -(CH2)6-[CH(CH2CF3)]-(CH2)3-, -(CH2)6-[CH(CH2CF3)]-(CH2)4-, -(CH2)6-[CH(CH2CF3)]-(CH2)5-,

[0198] -[CH(CH2CF3)]2-(CH2)-, -(CH2)-[CH(CH2CF3)]2-, -(CH2)-[CH(CH2CF3)]2-(CH2)-, -(CH2)-[CH(CH2CF3)]2-(CH2)2-, -(CH2)-[CH(CH2CF3)]2-(CH2)3-, -(CH2)-[CH(CH2CF3)]2-(CH2)4-, -(CH2)-[CH(CH2CF3)]2-(CH2)5-, -(CH2)-[CH(CH2CF3)]2-(CH2)6-, -(CH2)-[CH(CH2CF3)]2-(CH2)7-, -(CH2)-[CH(CH2CF3)]2-(CH2)8-, -(CH2)-[CH(CH2CF3)]2-(CH2)9-, -(CH2)2-[CH(CH2CF3)]2-(CH2)-, -(CH2)3-[CH(CH2CF3)]2-(CH2)-, -(CH2)4-[CH(CH2CF3)]2-(CH2)-, -(CH2)5-[CH(CH2CF3)]2-(CH2)-, -(CH2)6-[CH(CH2CF3)]2-(CH2)-, -(CH2)7-[CH(CH2CF3)]2-(CH2)-, -(CH2)8-[CH(CH2CF3)]2-(CH2)-, -(CH2)9-[CH(CH2CF3)]2-(CH2)-, -(CH2)2-[CH(CH2CF3)]2-(CH2)2-, -(CH2)3-[CH(CH2CF3)]2-(CH2)3-, -(CH2)4-[CH(CH2CF3)]2-(CH2)4-, -(CH2)5-[CH(CH2CF3)]2-(CH2)5-, -(CH2)2-[CH(CH2CF3)]2-(CH2)3-, -(CH2)2-[CH(CH2CF3)]2-(CH2)4-, -(CH2)2-[CH(CH2CF3)]2-(CH2)5-, -(CH2)2-[CH(CH2CF3)]2-(CH2)6-, -(CH2)2-[CH(CH2CF3)]2-(CH2)7-, -(CH2)2-[CH(CH2CF3)]2-(CH2)8-, -(CH2)3-[CH(CH2CF3)]2-(CH2)2-, -(CH2)3-[CH(CH2CF3)]2-(CH2)4-, -(CH2)3-[CH(CH2CF3)]2-(CH2)5-, -(CH2)3-[CH(CH2CF3)]2-(CH2)6-,-(CH2)3-[CH(CH2CF3)]2-(CH2)7-, -(CH2)4-[CH(CH2CF3)]2-(CH2)2-, -(CH2)4-[CH(CH2CF3)]2-(CH2)3-, -(CH2)4-[CH(CH2CF3)]2-(CH2)5-, -(CH2)4-[CH(CH2CF3)]2-(CH2)6-, -(CH2)5-[CH(CH2CF3)]2-(CH2)2-, -(CH2)5-[CH(CH2CF3)]2-(CH2)3-, -(CH2)5-[CH(CH2CF3)]2-(CH2)4-, -(CH2)6-[CH(CH2CF3)]2-(CH2)2-, -(CH2)6-[CH(CH2CF3)]2-(CH2)3-, -(CH2)6-[CH(CH2CF3)]2-(CH2)4-,

[0199] -[CH(CH2CF3)]3-(CH2)-, -(CH2)-[CH(CH2CF3)]3-, -(CH2)-[CH(CH2CF3)]3-(CH2)-, -(CH2)-[CH(CH2CF3)]3-(CH2)2-, -(CH2)-[CH(CH2CF3)]3-(CH2)3-, -(CH2)-[CH(CH2CF3)]3-(CH2)4-, -(CH2)-[CH(CH2CF3)]3-(CH2)5-, -(CH2)-[CH(CH2CF3)]3-(CH2)6-, -(CH2)-[CH(CH2CF3)]3-(CH2)7-, -(CH2)-[CH(CH2CF3)]3-(CH2)8-, -(CH2)2-[CH(CH2CF3)]3-(CH2)-, -(CH2)3-[CH(CH2CF3)]3-(CH2)-, -(CH2)4-[CH(CH2CF3)]3-(CH2)-, -(CH2)5-[CH(CH2CF3)]3-(CH2)-, -(CH2)6-[CH(CH2CF3)]3-(CH2)-, -(CH2)7-[CH(CH2CF3)]3-(CH2)-, -(CH2)8-[CH(CH2CF3)]3-(CH2)-, -(CH2)2-[CH(CH2CF3)]3-(CH2)2-, -(CH2)3-[CH(CH2CF3)]3-(CH2)3-, -(CH2)4-[CH(CH2CF3)]3-(CH2)4-, -(CH2)2-[CH(CH2CF3)]3-(CH2)3-, -(CH2)2-[CH(CH2CF3)]3-(CH2)4-, -(CH2)2-[CH(CH2CF3)]3-(CH2)5-, -(CH2)2-[CH(CH2CF3)]3-(CH2)6-, -(CH2)2-[CH(CH2CF3)]3-(CH2)7-, -(CH2)3-[CH(CH2CF3)]3-(CH2)2-, -(CH2)3-[CH(CH2CF3)]3-(CH2)4-, -(CH2)3-[CH(CH2CF3)]3-(CH2)5-, -(CH2)3-[CH(CH2CF3)]3-(CH2)6-, -(CH2)4-[CH(CH2CF3)]3-(CH2)2-, -(CH2)4-[CH(CH2CF3)]3-(CH2)3-, -(CH2)4-[CH(CH2CF3)]3-(CH2)5-, -(CH2)5-[CH(CH2CF3)]3-(CH2)2-,-(CH2)5-[CH(CH2CF3)]3-(CH2)3-, -(CH2)5-[CH(CH2CF3)]3-(CH2)4-, -(CH2)6-[CH(CH2CF3)]3-(CH2)2-, -(CH2)6-[CH(CH2CF3)]3-(CH2)3-,

[0200] -[CH(CH2CF3)]4-(CH2)-, -(CH2)-[CH(CH2CF3)]4-, -(CH2)-[CH(CH2CF3)]4-(CH2)-, -(CH2)-[CH(CH2CF3)]4-(CH2)2-, -(CH2)-[CH(CH2CF3)]4-(CH2)3-, -(CH2)-[CH(CH2CF3)]4-(CH2)4-, -(CH2)-[CH(CH2CF3)]4-(CH2)5-, -(CH2)-[CH(CH2CF3)]4-(CH2)6-, -(CH2)-[CH(CH2CF3)]4-(CH2)7-, -(CH2)-[CH(CH2CF3)]4-(CH2)8-, -(CH2)-[CH(CH2CF3)]4-(CH2)9-, -(CH2)-[CH(CH2CF3)]4-(CH2) 10-, -(CH2)2-[CH(CH2CF3)]4-(CH2)-, -(CH2)3-[CH(CH2CF3)]4-(CH2)-, -(CH2)4-[CH(CH2CF3)]4-(CH2)-, -(CH2)5-[CH(CH2CF3)]4-(CH2)-, -(CH2)6-[CH(CH2CF3)]4-(CH2)-, -(CH2)7-[CH(CH2CF3)]4-(CH2)-, -(CH2)2-[CH(CH2CF3)]4-(CH2)2-, -(CH2)3-[CH(CH2CF3)]4-(CH2)3-, -(CH2)4-[CH(CH2CF3)]4-(CH2)4-, -(CH2)5-[CH(CH2CF3)]4-(CH2)5-, -(CH2)2-[CH(CH2CF3)]4-(CH2)3-, -(CH2)2-[CH(CH2CF3)]4-(CH2)4-, -(CH2)2-[CH(CH2CF3)]4-(CH2)5-, -(CH2)2-[CH(CH2CF3)]4-(CH2)6-, -(CH2)3-[CH(CH2CF3)]4-(CH2)2-, -(CH2)3-[CH(CH2CF3)]4-(CH2)4-, -(CH2)4-[CH(CH2CF3)]4-(CH2)2-, -(CH2)4-[CH(CH2CF3)]4-(CH2)3-, -(CH2)5-[CH(CH2CF3)]4-(CH2)2-, -(CH2)5-[CH(CH2CF3)]4-(CH2)3-, -(CH2)6-[CH(CH2CF3)]4-(CH2)2-,

[0201] -[CH(CH2CF3)]5-(CH2)-, -(CH2)-[CH(CH2CF3)5-, -(CH2)-[CH(CH2CF3)]5-(CH2)-, -(CH2)-[CH(CH2CF3)]5-(CH2)2-, -(CH2)-[CH(CH2CF3)]5-(CH2)3-, -(CH2)-[CH(CH2CF3)]5-(CH2)4-, -(CH2)-[CH(CH2CF3)]5-(CH2)5-, -(CH2)-[CH(CH2CF3)]5-(CH2)6-, -(CH2)2-[CH(CH2CF3)]5-(CH2)-, -(CH2)3-[CH(CH2CF3)]5-(CH2)-, -(CH2)4-[CH(CH2CF3)]5-(CH2)-, -(CH2)5-[CH(CH2CF3)]5-(CH2)-, -(CH2)6-[CH(CH2CF3)]5-(CH2)-, -(CH2)2-[CH(CH2CF3)]5-(CH2)2-, -(CH2)3-[CH(CH2CF3)]5-(CH2)3-, -(CH2)4-[CH(CH2CF3)]5-(CH2)4-, -(CH2)2-[CH(CH2CF3)]5-(CH2)3-, -(CH2)2-[CH(CH2CF3)]5-(CH2)4-, -(CH2)2-[CH(CH2CF3)]5-(CH2)5-, -(CH2)2-[CH(CH2CF3)]5-(CH2)6-, -(CH2)3-[CH(CH2CF3)]5-(CH2)2-, -(CH2)3-[CH(CH2CF3)]5-(CH2)4-, -(CH2)4-[CH(CH2CF3)]5-(CH2)2-, -(CH2)4-[CH(CH2CF3)]5-(CH2)3-, -(CH2)5-[CH(CH2CF3)]5-(CH2)2-,

[0202] -[C(CH3)(CH2CF3)]-(CH2)-, -(CH2)-[C(CH3)(CH2CF3)]-, -(CH2)-[C(CH3)(CH2CF3)]-(CH2)-, -(CH2)-[C(CH3)(CH2CF3)]-(CH2)2-, -(CH2)-[C(CH3)(CH2CF3)]-(CH2)3-, -(CH2)-[C(CH3)(CH2CF3)]-(CH2)4-, -(CH2)-[C(CH3)(CH2CF3)]-(CH2)5-, -(CH2)-[C(CH3)(CH2CF3)]-(CH2)6-, -(CH2)-[C(CH3)(CH2CF3)]-(CH2)7-, -(CH2)-[C(CH3)(CH2CF3)]-(CH2)8-, -(CH2)-[C(CH3)(CH2CF3)]-(CH2)9-, -(CH2)-[C(CH3)(CH2CF3)]-(CH2) 10 -, -(CH2)2-[C(CH3)(CH2CF3)]-(CH2)-, -(CH2)3-[C(CH3)(CH2CF3)]-(CH2)-, -(CH2)4-[C(CH3)(CH2CF3)]-(CH2)-, -(CH2)5-[C(CH3)(CH2CF3)]-(CH2)-, -(CH2)6-[C(CH3)(CH2CF3)]-(CH2)-, -(CH2)7-[C(CH3)(CH2CF3)]-(CH2)-, -(CH2)8-[C(CH3)(CH2CF3)]-(CH2)-, -(CH2)9-[C(CH3)(CH2CF3)]-(CH2)-, -(CH2) 10-[C(CH3)(CH2CF3)]-(CH2)-, -(CH2)2-[C(CH3)(CH2CF3)]-(CH2)2-, -(CH2)3-[C(CH3)(CH2CF3)]-(CH2)3-, -(CH2)4-[C(CH3)(CH2CF3)]-(CH2)4-, -(CH2)5-[C(CH3)(CH2CF3)]-(CH2)5-, -(CH2)2-[C(CH3)(CH2CF3)]-(CH2)3-, -(CH2)2-[C(CH3)(CH2CF3)]-(CH2)4-, -(CH2)2-[C(CH3)(CH2CF3)]-(CH2)5-, -(CH2)2-[C(CH3)(CH2CF3)]-(CH2)6-, -(CH2)2-[C(CH3)(CH2CF3)]-(CH2)7-, -(CH2)2-[C(CH3)(CH2CF3)]-(CH2)8-, -(CH2)2-[C(CH3)(CH2CF3)]-(CH2)9-, -(CH2)3-[C(CH3)(CH2CF3)]-(CH2)2-, -(CH2)3-[C(CH3)(CH2CF3)]-(CH2)4-, -(CH2)3-[C(CH3)(CH2CF3)]-(CH2)5-, -(CH2)3-[C(CH3)(CH2CF3)]-(CH2)6-, -(CH2)3-[C(CH3)(CH2CF3)]-(CH2)7-, -(CH2)3-[C(CH3)(CH2CF3)]-(CH2)8-, -(CH2)4-[C(CH3)(CH2CF3)]-(CH2)2-, -(CH2)4-[C(CH3)(CH2CF3)]-(CH2)3-, -(CH2)4-[C(CH3)(CH2CF3)]-(CH2)5-, -(CH2)4-[C(CH3)(CH2CF3)]-(CH2)6-, -(CH2)4-[C(CH3)(CH2CF3)]-(CH2)7-, -(CH2)5-[C(CH3)(CH2CF3)]-(CH2)2-, -(CH2)5-[C(CH3)(CH2CF3)]-(CH2)3-, -(CH2)5-[C(CH3)(CH2CF3)]-(CH2)4-, -(CH2)5-[C(CH3)(CH2CF3)]-(CH2)6-, -(CH2)6-[C(CH3)(CH2CF3)]-(CH2)2-, -(CH2)6-[C(CH3)(CH2CF3)]-(CH2)3-,-(CH2)6-[C(CH3)(CH2CF3)]-(CH2)4-, -(CH2)6-[C(CH3)(CH2CF3)]-(CH2)5-,

[0203] -[C(CH3)(CH2CF3)]2-(CH2)-, -(CH2)-[C(CH3)(CH2CF3)]2-, -(CH2)-[C(CH3)(CH2CF3)]2-(CH2)-, -(CH2)-[C(CH3)(CH2CF3)]2-(CH2)2-, -(CH2)-[C(CH3)(CH2CF3)]2-(CH2)3-, -(CH2)-[C(CH3)(CH2CF3)]2-(CH2)4-, -(CH2)-[C(CH3)(CH2CF3)]2-(CH2)5-, -(CH2)-[C(CH3)(CH2CF3)]2-(CH2)6-, -(CH2)-[C(CH3)(CH2CF3)]2-(CH2)7-, -(CH2)-[C(CH3)(CH2CF3)]2-(CH2)8-, -(CH2)-[C(CH3)(CH2CF3)]2-(CH2)9-, -(CH2)2-[C(CH3)(CH2CF3)]2-(CH2)-, -(CH2)3-[C(CH3)(CH2CF3)]2-(CH2)-, -(CH2)4-[C(CH3)(CH2CF3)]2-(CH2)-, -(CH2)5-[C(CH3)(CH2CF3)]2-(CH2)-, -(CH2)6-[C(CH3)(CH2CF3)]2-(CH2)-, -(CH2)7-[C(CH3)(CH2CF3)]2-(CH2)-, -(CH2)8-[C(CH3)(CH2CF3)]2-(CH2)-, -(CH2)9-[C(CH3)(CH2CF3)]2-(CH2)-, -(CH2)2-[C(CH3)(CH2CF3)]2-(CH2)2-, -(CH2)3-[C(CH3)(CH2CF3)]2-(CH2)3-, -(CH2)4-[C(CH3)(CH2CF3)]2-(CH2)4-, -(CH2)5-[C(CH3)(CH2CF3)]2-(CH2)5-, -(CH2)2-[C(CH3)(CH2CF3)]2-(CH2)3-, -(CH2)2-[C(CH3)(CH2CF3)]2-(CH2)4-, -(CH2)2-[C(CH3)(CH2CF3)]2-(CH2)5-, -(CH2)2-[C(CH3)(CH2CF3)]2-(CH2)6-, -(CH2)2-[C(CH3)(CH2CF3)]2-(CH2)7-, -(CH2)2-[C(CH3)(CH2CF3)]2-(CH2)8-,-(CH2)3-[C(CH3)(CH2CF3)]2-(CH2)2-, -(CH2)3-[C(CH3)(CH2CF3)]2-(CH2)4-, -(CH2)3-[C(CH3)(CH2CF3)]2-(CH2)5-, -(CH2)3-[C(CH3)(CH2CF3)]2-(CH2)6-, -(CH2)3-[C(CH3)(CH2CF3)]2-(CH2)7-, -(CH2)4-[C(CH3)(CH2CF3)]2-(CH2)2-, -(CH2)4-[C(CH3)(CH2CF3)]2-(CH2)3-, -(CH2)4-[C(CH3)(CH2CF3)]2-(CH2)5-, -(CH2)4-[C(CH3)(CH2CF3)]2-(CH2)6-, -(CH2)5-[C(CH3)(CH2CF3)]2-(CH2)2-, -(CH2)5-[C(CH3)(CH2CF3)]2-(CH2)3-, -(CH2)5-[C(CH3)(CH2CF3)]2-(CH2)4-, -(CH2)6-[C(CH3)(CH2CF3)]2-(CH2)2-, -(CH2)6-[C(CH3)(CH2CF3)]2-(CH2)3-, -(CH2)6-[C(CH3)(CH2CF3)]2-(CH2)4-,

[0204] -[C(CH3)(CH2CF3)]3-(CH2)-, -(CH2)-[C(CH3)(CH2CF3)]3-, -(CH2)- [C(CH3)(CH2CF3)]3-(CH2)-, -(CH2)-[C(CH3)(CH2CF3)]3-(CH2)2-, -(CH2)-[C(CH3)(CH2CF3)]3-(CH2)3-, -(CH2)-[C(CH3)(CH2CF3)]3-(CH2)4-, -(CH2)-[C(CH3)(CH2CF3)]3-(CH2)5-, -(CH2)-[C(CH3)(CH2CF3)]3-(CH2)6-, -(CH2)-[C(CH3)(CH2CF3)]3-(CH2)7-, -(CH2)-[C(CH3)(CH2CF3)]3-(CH2)8-, -(CH2)2-[C(CH3)(CH2CF3)]3-(CH2)-, -(CH2)3-[C(CH3)(CH2CF3)]3-(CH2)-, -(CH2)4-[C(CH3)(CH2CF3)]3-(CH2)-, -(CH2)5-[C(CH3)(CH2CF3)]3-(CH2)-, -(CH2)6-[C(CH3)(CH2CF3)]3-(CH2)-, -(CH2)7-[C(CH3)(CH2CF3)]3-(CH2)-, -(CH2)8-[C(CH3)(CH2CF3)]3-(CH2)-, -(CH2)2-[C(CH3)(CH2CF3)]3-(CH2)2-, -(CH2)3-[C(CH3)(CH2CF3)]3-(CH2)3-, -(CH2)4-[C(CH3)(CH2CF3)]3-(CH2)4-, -(CH2)2-[C(CH3)(CH2CF3)]3-(CH2)3-, -(CH2)2-[C(CH3)(CH2CF3)]3-(CH2)4-, -(CH2)2-[C(CH3)(CH2CF3)]3-(CH2)5-, -(CH2)2-[C(CH3)(CH2CF3)]3-(CH2)6-, -(CH2)2-[C(CH3)(CH2CF3)]3-(CH2)7-, -(CH2)3-[C(CH3)(CH2CF3)]3-(CH2)2-, -(CH2)3-[C(CH3)(CH2CF3)]3-(CH2)4-, -(CH2)3-[C(CH3)(CH2CF3)]3-(CH2)5-, -(CH2)3-[C(CH3)(CH2CF3)]3-(CH2)6-,-(CH2)4-[C(CH3)(CH2CF3)]3-(CH2)2-, -(CH2)4-[C(CH3)(CH2CF3)]3-(CH2)3-, -(CH2)4-[C(CH3)(CH2CF3)]3-(CH2)5-, -(CH2)5-[C(CH3)(CH2CF3)]3-(CH2)2-, -(CH2)5-[C(CH3)(CH2CF3)]3-(CH2)3-, -(CH2)5-[C(CH3)(CH2CF3)]3-(CH2)4-, -(CH2)6-[C(CH3)(CH2CF3)]3-(CH2)2-, -(CH2)6-[C(CH3)(CH2CF3)]3-(CH2)3-,

[0205] -[C(CH3)(CH2CF3)]4-(CH2)-, -(CH2)-[C(CH3)(CH2CF3)]4-, -(CH2)-[C(CH3)(CH2CF3)]4-(CH2)-, -(CH2)-[C(CH3)(CH2CF3)]4-(CH2)2-, -(CH2)-[C(CH3)(CH2CF3)]4-(CH2)3-, -(CH2)-[C(CH3)(CH2CF3)]4-(CH2)4-, -(CH2)-[C(CH3)(CH2CF3)]4-(CH2)5-, -(CH2)-[C(CH3)(CH2CF3)]4-(CH2)6-, -(CH2)-[C(CH3)(CH2CF3)]4-(CH2)7-, -(CH2)-[C(CH3)(CH2CF3)]4-(CH2)8-, -(CH2)-[C(CH3)(CH2CF3)]4-(CH2)9-, -(CH2)-[C(CH3)(CH2CF3)]4-(CH2) 10-, -(CH2)2-[C(CH3)(CH2CF3)]4-(CH2)-, -(CH2)3-[C(CH3)(CH2CF3)]4-(CH2)-, -(CH2)4-[C(CH3)(CH2CF3)]4-(CH2)-, -(CH2)5-[C(CH3)(CH2CF3)]4-(CH2)-, -(CH2)6-[C(CH3)(CH2CF3)]4-(CH2)-, -(CH2)7-[C(CH3)(CH2CF3)]4-(CH2)-, -(CH2)2-[C(CH3)(CH2CF3)]4-(CH2)2-, -(CH2)3-[C(CH3)(CH2CF3)]4-(CH2)3-, -(CH2)4-[C(CH3)(CH2CF3)]4-(CH2)4-, -(CH2)5-[C(CH3)(CH2CF3)]4-(CH2)5-, -(CH2)2-[C(CH3)(CH2CF3)]4-(CH2)3-, -(CH2)2-[C(CH3)(CH2CF3)]4-(CH2)4-, -(CH2)2-[C(CH3)(CH2CF3)]4-(CH2)5-, -(CH2)2-[C(CH3)(CH2CF3)]4-(CH2)6-, -(CH2)3-[C(CH3)(CH2CF3)]4-(CH2)2-, -(CH2)3-[C(CH3)(CH2CF3)]4-(CH2)4-, -(CH2)4-[C(CH3)(CH2CF3)]4-(CH2)2-, -(CH2)4-[C(CH3)(CH2CF3)]4-(CH2)3-, -(CH2)5-[C(CH3)(CH2CF3)]4-(CH2)2-, -(CH2)5-[C(CH3)(CH2CF3)]4-(CH2)3-, -(CH2)6-[C(CH3)(CH2CF3)]4-(CH2)2-,

[0206] -[C(CH3)(CH2CF3)]5-(CH2)-, -(CH2)-[C(CH3)(CH2CF3)]5-, -(CH2)-[C(CH3)(CH2CF3)]5-(CH2)-, -(CH2)-[C(CH3)(CH2CF3)]5-(CH2)2-, -(CH2)-[C(CH3)(CH2CF3)]5-(CH2)3-, -(CH2)-[C(CH3)(CH2CF3)]5-(CH2)4-, -(CH2)-[C(CH3)(CH2CF3)]5-(CH2)5-, -(CH2)-[C(CH3)(CH2CF3)]5-(CH2)6-, -(CH2)2-[C(CH3)(CH2CF3)]5-(CH2)-, -(CH2)3-[C(CH3)(CH2CF3)]5-(CH2)-, -(CH2)4-[C(CH3)(CH2CF3)]5-(CH2)-, -(CH2)5-[C(CH3)(CH2CF3)]5-(CH2)-, -(CH2)6-[C(CH3)(CH2CF3)]5-(CH2)-, -(CH2)2-[C(CH3)(CH2CF3)]5-(CH2)2-, -(CH2)3-[C(CH3)(CH2CF3)]5-(CH2)3-, -(CH2)4-[C(CH3)(CH2CF3)]5-(CH2)4-, -(CH2)2-[C(CH3)(CH2CF3)]5-(CH2)3-, -(CH2)2-[C(CH3)(CH2CF3)]5-(CH2)4-, -(CH2)2-[C(CH3)(CH2CF3)]5-(CH2)5-, -(CH2)2-[C(CH3)(CH2CF3)]5-(CH2)6-, -(CH2)3-[C(CH3)(CH2CF3)]5-(CH2)2-, -(CH2)3-[C(CH3)(CH2CF3)]5-(CH2)4-, -(CH2)4-[C(CH3)(CH2CF3)]5-(CH2)2-, -(CH2)4-[C(CH3)(CH2CF3)]5-(CH2)3-, -(CH2)5-[C(CH3)(CH2CF3)]5-(CH2)2-,

[0207] -(CH2)2-(CF2)-O-(CF2)-(CH2)2-, -(CH2)2-(CF2)-O-(CH2)-O-(CF2)-(CH2)2-, -(CH2)2-(CF2)-O-(CH2)2-O-(CF2)-(CH2)2,

[0208] -(CH2)-(CF2)-O-(CF2)-O-(CF2)-(CH2)-, -(CH2)2-(CF2)-O-(CF2)-O-(CF2)-(CH2)2-, -(CH2)3-(CF2)-O-(CF2)-O-(CF2)-(CH2)3-, -(CH2)4-(CF2)-O-(CF2)-O-(CF2)-(CH2)4-, -(CH2)-(CF2)-O-(CF2)-O-(CF2)-(CH2)2-, -(CH2)-(CF2)-O-(CF2)-O-(CF2)-(CH2)3-, -(CH2)-(CF2)-O-(CF2)-O-(CF2)-(CH2)4-, -(CH2)-(CF2)-O-(CF2)-O-(CF2)-(CH2)5-, -(CH2)-(CF2)-O-(CF2)-O-(CF2)-(CH2)6-, -(CH2)-(CF2)-O-(CF2)-O-(CF2)-(CH2)7-, -(CH2)2-(CF2)-O-(CF2)-O-(CF2)-(CH2)-, -(CH2)3-(CF2)-O-(CF2)-O-(CF2)-(CH2)-, -(CH2)4-(CF2)-O-(CF2)-O-(CF2)-(CH2)-, -(CH2)5-(CF2)-O-(CF2)-O-(CF2)-(CH2)-, -(CH2)6-(CF2)-O-(CF2)-O-(CF2)-(CH2)-, -(CH2)7-(CF2)-O-(CF2)-O-(CF2)-(CH2)-, -(CH2)2-(CF2)-O-(CF2)-O-(CF2)-(CH2)3-, -(CH2)2-(CF2)-O-(CF2)-O-(CF2)-(CH2)4-, -(CH2)2-(CF2)-O-(CF2)-O-(CF2)-(CH2)5-, -(CH2)2-(CF2)-O-(CF2)-O-(CF2)-(CH2)6-, -(CH2)3-(CF2)-O-(CF2)-O-(CF2)-(CH2)2-, -(CH2)4-(CF2)-O-(CF2)-O-(CF2)-(CH2)2-, -(CH2)5-(CF2)-O-(CF2)-O-(CF2)-(CH2)2-, -(CH2)6-(CF2)-O-(CF2)-O-(CF2)-(CH2)2-, -(CH2)3-(CF2)-O-(CF2)-O-(CF2)-(CH2)4-, -(CH2)4-(CF2)-O-(CF2)-O-(CF2)-(CH2)3-,-(CH2)3-(CF2)-O-(CF2)-O-(CF2)-(CH2)5-, -(CH2)5-(CF2)-O-(CF2)-O-(CF2)-(CH2)3-,

[0209] -(CH2)-(CF2)-O-(CF2)2-O-(CF2)-(CH2)-, -(CH2)2-(CF2)-O-(CF2)2-O-(CF2)-(CH2)2-, -(CH2)3-(CF2)-O-(CF2)2-O-(CF2)-(CH2)3-, -(CH2)4-(CF2)-O-(CF2)2-O-(CF2)-(CH2)4-, -(CH2)-(CF2)-O-(CF2)2-O-(CF2)-(CH2)2-, -(CH2)-(CF2)-O-(CF2)2-O-(CF2)-(CH2)3-, -(CH2)-(CF2)-O-(CF2)2-O-(CF2)-(CH2)4-, -(CH2)-(CF2)-O-(CF2)2-O-(CF2)-(CH2)5-, -(CH2)-(CF2)-O-(CF2)2-O-(CF2)-(CH2)6-, -(CH2)-(CF2)-O-(CF2)2-O-(CF2)-(CH2)7-, -(CH2)2-(CF2)-O-(CF2)2-O-(CF2)-(CH2)-, -(CH2)3-(CF2)-O-(CF2)2-O-(CF2)-(CH2)-, -(CH2)4-(CF2)-O-(CF2)2-O-(CF2)-(CH2)-, -(CH2)5-(CF2)-O-(CF2)2-O-(CF2)-(CH2)-, -(CH2)6-(CF2)-O-(CF2)2-O-(CF2)-(CH2)-, -(CH2)7-(CF2)-O-(CF2)2-O-(CF2)-(CH2)-, -(CH2)2-(CF2)-O-(CF2)2-O-(CF2)-(CH2)3-, -(CH2)2-(CF2)-O-(CF2)2-O-(CF2)-(CH2)4-, -(CH2)2-(CF2)-O-(CF2)2-O-(CF2)-(CH2)5-, -(CH2)2-(CF2)-O-(CF2)2-O-(CF2)-(CH2)6-, -(CH2)3-(CF2)-O-(CF2)2-O-(CF2)-(CH2)2-, -(CH2)4-(CF2)-O-(CF2)2-O-(CF2)-(CH2)2-, -(CH2)5-(CF2)-O-(CF2)2-O-(CF2)-(CH2)2-, -(CH2)6-(CF2)-O-(CF2)2-O-(CF2)-(CH2)2-, -(CH2)3-(CF2)-O-(CF2)2-O-(CF2)-(CH2)4-,-(CH2)4-(CF2)-O-(CF2)2-O-(CF2)-(CH2)3-, -(CH2)3-(CF2)-O-(CF2)2-O-(CF2)-(CH2)5-, -(CH2)5-(CF2)-O-(CF2)2-O-(CF2)-(CH2)3-,

[0210] -(CH2)-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)-, -(CH2)2-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)2-, -(CH2)3-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)3-, -(CH2)4-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)4-, -(CH2)-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)2-, -(CH2)-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)3-, -(CH2)-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)3-, -(CH2)-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)4-, -(CH2)-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)5-, -(CH2)-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)6-, -(CH2)-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)7-, -(CH2)2-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)-, -(CH2)3-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)-, -(CH2)4-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)-, -(CH2)5-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)-, -(CH2)6-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)-, -(CH2)7-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)-, -(CH2)2-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)3-, -(CH2)2-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)4-, -(CH2)2-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)5-, -(CH2)2-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)6-, -(CH2)3-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)2-, -(CH2)4-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)2-, -(CH2)5-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)2-,-(CH2)6-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)2-, -(CH2)3-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)4-, -(CH2)4-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)3-, -(CH2)3-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)5-, -(CH2)5-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)3-,

[0211] -(CH2)-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)-, -(CH2)2-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)2-, -(CH2)3-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)3-, -(CH2)4-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)4-, -(CH2)-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)2-, -(CH2)-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)3-, -(CH2)-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)4-, -(CH2)-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)5-, -(CH2)-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)6-, -(CH2)-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)7-, -(CH2)2-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)-, -(CH2)3-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)-, -(CH2)4-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)-, -(CH2)5-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)-, -(CH2)6-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)-, -(CH2)7-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)-, -(CH2)2-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)3-, -(CH2)2-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)4-, -(CH2)2-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)5-, -(CH2)2-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)6-, -(CH2)3-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)2-,-(CH2)4-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)2-, -(CH2)5-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)2-, -(CH2)6-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)2-, -(CH2)3-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)4-, -(CH2)4-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)3-, -(CH2)3-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)5-, -(CH2)5-(CF2)-O-(CF2)-O-(CF2)-O-(CF2)-(CH2)3-,

[0212] -(CH2)-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)-, -(CH2)2-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)2-, -(CH2)3-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)3-, -(CH2)4-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)4-, -(CH2)-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)2-, -(CH2)-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)3-, -(CH2)-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)4-, -(CH2)-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)5-, -(CH2)-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)6-, -(CH2)-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)7-, -(CH2)2-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)-, -(CH2)3-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)-, -(CH2)4-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)-, -(CH2)5-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)-, -(CH2)6-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)-, -(CH2)7-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)-, -(CH2)2-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)3-, -(CH2)2-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)4-, -(CH2)2-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)5-,-(CH2)2-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)6-, -(CH2)3-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)2-, -(CH2)4-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)2-, -(CH2)5-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)2-, -(CH2)6-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)2-, -(CH2)3-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)4-, -(CH2)4-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)3-, -(CH2)3-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)5-, -(CH2)5-(CF2)2-O-(CF2)2-O-(CF2)2-O-(CF2)2-(CH2)3-,

[0213] Desirable examples for [L] are -(CH2)2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)9-, -(CH2) 11 -, -(CH2) 12 -, -(CH2)2-(CHF)2-(CH2)2-, -(CH2)2-CHF-(CH2)3-, -(CF2)-(CH2)5-, -(CH2)5-(CF2)-, -(CH2)2-(CF2)-(CH2)2-, -(CH2)3-(CF2)2-(CH2)2-, -(CH2)2-(CF2)2-(CH2)3-, -(CH2)3-O-(CH2)2-O-(CH2)2-, -(CH2)2-O-(CH2)2-O-(CH2)2-, -(CH2)3-O-(CH2)2-S-(CH2)2-, -(CH2)2-SO2-(CH2)2-O-(CH2)2-.

[0214] Particularly desirable examples for [L] are -(CH2)2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)9-, -(CH2) 11-, -(CH2) 12 -, -(CH2)2-(CHF)2-(CH2)2-, -(CH2)2-CHF-(CH2)3-, -(CH2)2-(CF2)-(CH2)2-, -(CH2)2-O-(CH2)2-O-(CH2)2- is.

[0215] Compounds of formulas (I), (Ia), (Ib), (Ic), (II), (II-a), (II-b), (II-c), (III), (III-a), (III-b), (III-c), (IV), (IV-a), (IV-b), and (IV-c) having a polymerizable group as described above or preferably as described below, or having a substituent as described above or preferably as described below, are such that [L] is -(C(R)2 o- Corresponding to, where R and o have the meaning described or preferably as described above when the substrate is preferred according to the present invention.

[0216] Accordingly, the monomers of Formula (I), Formula (Ia), Formula (Ib), Formula (Ic), Formula (II), Formula (II-a), Formula (II-b), Formula (II-c), Formula (III), Formula (III-a), Formula (III-b), Formula (III-c), Formula (IV), Formula (IV-a), Formula (IV-b) and Formula (IV-c) for manufacturing an ophthalmic device or a precursor article for manufacturing an ophthalmic device as described above, having a polymerizable group as described above or preferably as described below, having a substituent as described above or preferably as described above, are such that [L] is -(C(R)2) o- Corresponding to, where R and o have the meaning described or preferably as described above when used as substrates. Such ophthalmic devices and precursor articles manufactured using these monomers are particularly preferred.

[0217] Accordingly, the present invention relates to polymerized compounds of formulas (I), (Ia), (Ib), (Ic), (II), (II-a), (II-b), (II-c), (III), (III-a), (III-b), (III-c), (IV), (IV-a), (IV-b), and (IV-c), wherein [L] is -(C(R)2) o- The invention relates to an ophthalmic device as described above or preferably as described above, wherein o is 1 to 20 and R has the meaning as described above.

[0218] Accordingly, the present invention relates to polymerized compounds of formulas (I), (Ia), (Ib), (Ic), (II), (II-a), (II-b), (II-c), (III), (III-a), (III-b), (III-c), (IV), (IV-a), (IV-b), and (IV-c), wherein [L] is -(C(R)2) o- And, o and R preferably have the meaning as described above, and relate to an ophthalmic device as described or preferably as described above.

[0219] In the substituent [L]-R1 in chemical formula (I), chemical formula (Ia), chemical formula (Ib), chemical formula (Ic), chemical formula (II), chemical formula (II-a), chemical formula (II-b), chemical formula (II-c), chemical formula (III), chemical formula (III-a), chemical formula (III-b), chemical formula (III-c), chemical formula (IV), chemical formula (IV-a), chemical formula (IV-b) or chemical formula (IV-c), [L] preferably has the meaning as described above, or preferably or particularly preferably, as described above, and R1 is preferably trimethoxysilyl, triethoxysilyl, dimethoxymethylsilyl, diethoxymethylsilyl or a polymerizable group according to chemical formula (4).

[0220] ,

[0221] In the above formula,

[0222] X 11 is selected from the group consisting of O, S, O-SO2, SO2-O, C(=O), OC(=O), C(=O)O, S(C=O)S, and (C=O)S.

[0223] R5, R6, and R7 are, in each case, independently of one another, H, F, a linear or branched alkyl group having 1 to 20 C atoms that is not fluorinated or is partially or fully fluorinated, or an aryl group having 6 to 14 C atoms, and

[0224] c is 0 or 1.

[0225] In another preferred embodiment of the present invention, in a compound of formula (I), formula (Ia), formula (Ib), formula (Ic), formula (II), formula (II-a), formula (II-b), formula (II-c), formula (III), formula (III-a), formula (III-b), formula (III-c), formula (IV), formula (IV-a), formula (IV-b), and formula (IV-c) which acts as a monomer for the manufacture of an ophthalmic device or a precursor article of an ophthalmic device as described above, or for the manufacture of an oligomer, polymer, or copolymer according to the present invention, c, X 11 , R5, R6, and R7 have the following desirable meanings:

[0226] Preferably, R6 and R7 are H. Preferably, c is 1.

[0227] Preferably, R5 is H, methyl, ethyl, or phenyl. Particularly preferably, R5 is H or methyl.

[0228] Preferably, X 11 is C(=O), OC(=O), or C(=O)O. Particularly preferably, X 11 is C(=O)O.

[0229] As a polymerizable group R1 according to the present invention, a preferred alkenyl group of formula (4) is therefore represented by any one of formulas (4-1), (4-2), (4-3), (4-4), (4-5), (4-6), (4-7), (4-8), (4-9), (4-10), (4-11) and (4-12):

[0230] , ,

[0231] , , ,

[0232] , , ,

[0233] , ,

[0234] , .

[0235] A particularly preferred alkenyl group of formula (4) as the polymerizable group R1 according to the present invention is represented by any one formula selected from the group consisting of formulas (4-1), (4-2), (4-3), (4-5), (4-6), (4-11) and (4-12) as described above:

[0236] The alkenyl group represented by chemical formula (4-1) is called methacrylate. The alkenyl group represented by chemical formula (4-2) is called acrylate.

[0237] The desirable R1 is preferably combined with the desirable R1 of the connecting element [L].

[0238] The substituent [L]-R1 in formulas (I), (Ia), (Ib), (Ic), (II), (II-a), (II-b), (II-c), (III), (III-a), (III-b), (III-c), (IV), (IV-a), (IV-b), and (IV-c) is therefore particularly preferably

[0239] -(CH2)2-R1, -(CH2)3-R1, -(CH2)4-R1, -(CH2)5-R1, -(CH2)6-R1, -(CH2)9-R1, -(CH2) 11 -R1, -(CH2) 12-R1, -(CH2)2-(CHF)2-(CH2)2-R1, -(CH2)2-CHF-(CH2)3-R1, -(CF2)-(CH2)5-R1, -(CH2)5-(CF2)-R1, -(CH2)2-(CF2)-(CH2)2-R1, -(CH2)3-(CF2)2-(CH2)2-R1, -(CH2)2-(CF2)2-(CH2)3-R1, -(CH2)3-O-(CH2)2-O-(CH2)2-R1, -(CH2)2-O-(CH2)2-O-(CH2)2-R1, -(CH2)3-O-(CH2)2-S-(CH2)2-R1, -(CH2)2-SO2-(CH2)2-O-(CH2)2-R1 It is selected from the group consisting of the alkenyls of formula (4-1), formula (4-2), formula (4-3), formula (4-4), formula (4-5), formula (4-6), formula (4-7), formula (4-8), formula (4-9), formula (4-10), formula (4-11), or formula (4-12).

[0240] Particularly preferably, the compounds of formulas (I), (Ia), (Ib), (Ic), (II), (II-a), (II-b), (II-c), (III), (III-a), (III-b), (III-c), (IV), (IV-a), (IV-b), and (IV-c) comprise the polymerizable group R1 represented by formulas (4-1), (4-2), (4-5), (4-6), (4-11), and (4-12).

[0241] Very particularly preferably, the compounds of formulas (I), (Ia), (Ib), (Ic), (II), (II-a), (II-b), (II-c), (III), (III-a), (III-b), (III-c), (IV), (IV-a), (IV-b), and (IV-c) comprise a polymerizable group R1 of methacrylate or acrylate origin represented by formulas (4-1) and (4-2).

[0242] Accordingly, the present invention also relates to an ophthalmic device or a precursor article for manufacturing an ophthalmic device comprising a polymerized compound of formula (I), formula (Ia), formula (Ib), formula (Ic), formula (II), formula (II-a), formula (II-b), formula (II-c), formula (III), formula (III-a), formula (III-b), formula (III-c), formula (IV), formula (IV-a), formula (IV-b) or formula (IV-c) as described above, preferably, wherein R1 is independently derived from an acrylic or methacrylic group in each case.

[0243] Accordingly, the present invention also relates to a compound of formula (I), formula (Ia), formula (Ib), formula (Ic), formula (II), formula (II-a), formula (II-b), formula (II-c), formula (III), formula (III-a), formula (III-b), formula (III-c), formula (IV), formula (IV-a), formula (IV-b) or formula (IV-c) as described above or preferably as described above, wherein R1 is an acrylic or methacrylic group independently in each case.

[0244] Examples of compounds / monomers of chemical formulas (I), (II), (III) and (IV) are the following compounds (A-001) to (A-080) as presented in Table 1.

[0245] [Table 1]

[0246]

[0247]

[0248]

[0249]

[0250]

[0251]

[0252]

[0253]

[0254]

[0255]

[0256] The compounds of Formula (I), Formula (Ia), Formula (Ib), Formula (Ic), Formula (II), Formula (II-a), Formula (II-b), Formula (II-c), Formula (III), Formula (III-a), Formula (III-b), Formula (III-c), Formula (IV), Formula (IV-a), Formula (IV-b), and Formula (IV-c) of the present application can be synthesized by methods well known to those skilled in the art. Preferably, all syntheses are carried out under an inert atmosphere using a dry solvent.

[0257] General reaction scheme 1 provides an overview of the synthesis of compounds of formulas (I), (II), (III) and / or (IV), and all additional reaction products that will be generated but can be easily separated, wherein all symbols and labels have the meanings as previously stated or are shown in the reaction scheme, and X is absent:

[0258]

[0259] General reaction scheme 2 provides an overview of the synthesis of compounds of formulas (I), (II), (III) and / or (IV), and any additional reaction products that may be generated but can be easily separated, wherein all symbols and labels have the meanings as described above or are shown in the reaction scheme, and X is absent:

[0260]

[0261] An exemplary reaction sequence is presented in Reaction Schematic 1 for compounds of formulas (II) and (IV) (where X is absent, R1 is methacrylate, and all additional symbols and labels have the meanings as previously described). However, the product can be easily separated by ordinary means in the art as further described below.

[0262] Reaction Schema 1:

[0263]

[0264] This reaction is a nucleophilic substitution.

[0265] An alternative exemplary reaction sequence is presented in Reaction Schema 2-1 for the compound of Formula (II) (wherein X is absent, Y1 is O, Y0 is S, R1 is methacrylate, and all symbols and labels have the meanings as previously described). However, the product can be easily separated by conventional means in the art as further described below.

[0266] Reaction Schema 2-1:

[0267]

[0268] The first type of reaction is nucleophilic substitution.

[0269] The second type of reaction is nucleophilic substitution.

[0270] An alternative exemplary reaction sequence is presented in Reaction Schematic 2-2 for compounds of formulas (I), (II) and (IV) (wherein X is absent, Y1 is S, Y0 is S, R1 is methacrylate, and all symbols and labels have the meanings as previously described). However, the product can be easily separated by conventional means in the art as further described below.

[0271] Reaction Schema 2-2:

[0272]

[0273] The first type of reaction is nucleophilic substitution.

[0274] The second type of reaction is nucleophilic substitution.

[0275] An alternative reaction sequence is presented in Reaction Schematic 3 for compounds of Formulas (II) and (IV) (wherein X is absent, Y1 is O, Y0 is S, R1 is methacrylate, and all symbols and labels have the meanings as previously described). However, the product can be easily separated by conventional means in the art as further described below.

[0276] Reaction Schema 3:

[0277]

[0278] This reaction is a nucleophilic substitution.

[0279] An alternative reaction sequence is presented in Reaction Schema 4 for the compound of Formula (II) (where X is absent, Y1 is S, Y0 is O or S, R1 is acrylate, and all symbols and labels have the same meaning as previously described).

[0280] Reaction Schema 4:

[0281]

[0282] This reaction is a thiolation reaction.

[0283] An exemplary reaction sequence for the compound of chemical formula (II) (wherein X is absent, Y1 is O, Y0 is S, R1 is methacrylate, and all symbols and labels have the meanings as previously described) is presented in reaction scheme 5, route (b). However, the product can be easily separated by conventional means in the art as further described below.

[0284] Reaction Schema 5:

[0285]

[0286] This reaction is a nucleophilic substitution.

[0287] An alternative exemplary reaction sequence is presented in Reaction Schematic 6. Here, the compound of formula (II) (where X is absent, R1 is methacrylate, and all symbols and labels have the meanings as previously described) is part of a mixture of compounds. However, the compounds in the mixture can be easily separated by ordinary means in the art, as further described below.

[0288] Reaction Schema 6:

[0289]

[0290] This reaction is a nucleophilic substitution.

[0291] An alternative exemplary reaction sequence is presented in Reaction Schematic 7. Here, the compound of formula (III) (where X is absent, R1 is methacrylate, and all symbols and labels have the meanings as previously described) is part of a mixture of compounds. However, the compounds of formula (III) can be easily separated from the mixture of compounds by ordinary means in the art, as further described below.

[0292] Reaction Schema 7:

[0293]

[0294] This reaction is a nucleophilic substitution.

[0295] An alternative exemplary reaction sequence is presented in Reaction Schematic 8. Here, the compound of formula (III) (where X is absent, R1 is methacrylate, and all symbols and labels have the meanings as previously described) is part of a mixture of compounds. However, the compounds of formula (III) can be easily separated from the mixture by ordinary means in the art, as further described below.

[0296] Reaction Schema 8:

[0297]

[0298] This reaction is a nucleophilic substitution.

[0299] An alternative exemplary reaction sequence is presented in Reaction Schematic 9. Here, the compound of Formula (II) (where X is absent, Y1 and Y0 are O, R1 is methacrylate, and all symbols and labels have the meanings as previously described) is part of a mixture of compounds of Formula (IV) (where Y1 and Y0 are O, R1 is methacrylate, and all symbols and labels have the meanings as previously described). However, the compounds can be easily separated from the mixture by ordinary means in the art, as further described below.

[0300] Reaction Schema 9:

[0301]

[0302] Precursor compounds as disclosed in any of reaction schemes 1 to 9 or general reaction schemes 1 and 2 are commercially available or accessible by known synthesis processes.

[0303] In the processes described in any of reaction schemes 1 to 9 or general reaction schemes 1 and 2, it is preferable that a purification step be performed after the reaction of the reactants to separate the final product of formula (I), formula (II), formula (III), or formula (IV) as described above from the byproduct or reaction product.

[0304] Suitable purification steps include the separation of easily volatile components by distillation or condensation, fractional crystallization, extraction with organic solvents, chromatography, or a combination of these methods. Each known separation method may be used or combined for this purpose.

[0305] As described above, the compounds / monomers of formulas (I), (Ia), (Ib), (Ic), (II), (II-a), (II-b), (II-c), (III), (III-a), (III-b), (III-c), (IV), (IV-a), (IV-b) and (IV-c) described above, or preferably described above, contain polymerizable groups and are intended as monomers for oligomerization or polymerization.

[0306] Accordingly, the present invention also relates to an oligomer, polymer, or copolymer comprising at least one polymerized compound of formula (I), formula (Ia), formula (Ib), formula (Ic), formula (II), formula (II-a), formula (II-b), formula (II-c), formula (III), formula (III-a), formula (III-b), formula (III-c), formula (IV), formula (IV-a), formula (IV-b), and formula (IV-c) as described above, provided that silicates based on polymerized compounds of formulas (I) and (IV) (wherein all substituents R# contain a polymerized Si-containing group R1) are excluded.

[0307] Accordingly, the present invention also relates to an oligomer, polymer, or copolymer comprising at least one polymerized compound of formula (I), formula (Ia), formula (Ib), formula (Ic), formula (II), formula (II-a), formula (II-b), formula (II-c), formula (III), formula (III-a), formula (III-b), formula (III-c), formula (IV), formula (IV-a), formula (IV-b) and formula (IV-c) as described above, provided that silicates comprising polymerized compounds of formulas (Ic) and (IV-c) are excluded.

[0308] The term “polymer” generally refers to a relatively high molecular weight molecule having a structure that essentially comprises a number of repeating units derived, either actually or conceptually, from a relatively low molecular weight molecule (PAC, 1996, 68, 2291). Unless otherwise noted in the specification, the term “polymer” includes homopolymers and copolymers. The term “oligomer” generally refers to a relatively medium molecular weight molecule having a structure that essentially comprises a number of small units derived, either actually or conceptually, from a relatively lower molecular weight molecule (PAC, 1996, 68, 2291). In a preferred sense according to the present invention, a polymer means a compound having 30 or more repeating units, and an oligomer means a compound having more than 1 and fewer than 30 repeating units.

[0309] In the above and below, in the formulas representing a polymer, oligomer, compound of formula (I), formula (Ia), formula (Ib), formula (Ic), formula (II), formula (II-a), formula (II-b), formula (II-c), formula (III), formula (III-a), formula (III-b), formula (III-c), formula (IV), formula (IV-a), formula (IV-b) or formula (IV-c), or a monomer unit or polymer formed from a compound of formula (I), formula (Ia), formula (Ib), formula (Ic), formula (II), formula (II-a), formula (II-b), formula (II-c), formula (III), formula (III-a), formula (III-b), formula (III-c), formula (IV), formula (IV-a), formula (IV-b) or formula (IV-c), an asterisk ("*") indicates a connection with an adjacent repeating unit of the polymer chain or oligomer chain or with a terminal end group.

[0310] The suitable end group is known to those skilled in the art and depends on the polymerization method used.

[0311] The terms “repeat unit” and “monomer unit” refer to a constituent repeat unit (CRU), which is a repetition of the smallest constituent unit that makes up a regular macromolecule, a regular oligomeric molecule, a regular block, or a regular chain (Reference [PAC, 1996, 68, 2291]).

[0312] Unless otherwise noted, the molecular weight is the number average molecular weight (M n ) or weight-average molecular weight (M W It is given as ), which is determined by gel permeation chromatography (GPC) on polystyrene standards in elution solvents such as tetrahydrofuran, trichloromethane (TCM, chloroform), chlorobenzene, or 1,2,4-trichlorobenzene. Unless otherwise noted, tetrahydrofuran is used as the solvent. The degree of polymerization (n) is given in the literature [JMG Cowie, Polymers: Chemistry & Physics of Modern Materials As stated in [ , Blackie, Glasgow, 1991], n = M n / M U It refers to the number-average degree of polymerization given by, and in the above formula, M U is the molecular weight of a single repeating unit.

[0313] In a polymer comprising a copolymer according to the present invention, the total number of repeating units (n) is preferably ≥ 30, very preferably ≥ 100, most preferably ≥ 200, and preferably 5000 or less, very preferably 3000 or less, most preferably 2000 or less, and includes any combination of the upper and lower limits of n mentioned above.

[0314] The polymer of the present invention or the polymer / copolymer as a material for an ophthalmic device according to the present invention comprises homopolymers, statistical copolymers, random copolymers, alternating copolymers, and block copolymers, and combinations of the aforementioned.

[0315] Throughout the description and claims of this specification, the words “comprising” and “containing” and variations thereof, e.g., “comprising” and “comprising”, mean that other components “comprising but not limited thereto” and are not intended to exclude (and do not exclude) other components.

[0316] Preferably, the polymerizable group R1 forms a regioregular, alternating, regiorandom, statistical, block or random homopolymer or copolymer backbone, or becomes part of a polymer backbone, and R1 has the meaning described or preferably as described above.

[0317] Preferably, such oligomers, polymers, or copolymers according to the present invention are constituent units M based on formula (I), formula (II), formula (III), or formula (IV). 0 Includes,

[0318] , ,

[0319] , ,

[0320] Herein, in each case, the polymerizable group R1 is polymerized to form a positionally regular, alternating, positionally irregular, statistical, block or random oligomer or polymer backbone, or to become part of a copolymer backbone, and all symbols and labels used in Formulas (I), (II), (III), and (IV) have the meanings described above or preferably as described above. Precautions regarding the polymer / copolymer of the present invention as described above should be taken into account with respect to the definitions of the symbols and labels.

[0321] Furthermore, the present invention comprises a constituent unit M based on the formula (I), formula (II), formula (III), or formula (IV) as described above, or preferably based on the formula (Ia), formula (Ib), formula (Ic), formula (II-a), formula (II-b), formula (II-c), formula (III-a), formula (III-b), formula (III-c), formula (IV-a), formula (IV-b), or formula (IV-c). 0 The invention relates to an ophthalmic device or a precursor article for manufacturing an ophthalmic device as described above or preferably below, comprising an oligomer, polymer, or copolymer including R1, wherein in each case R1 is polymerized to form a positionally regular, alternating, positionally irregular, statistical, block, or random oligomer or polymer backbone or to become part of a copolymer backbone.

[0322] Preferably, this polymerized group R1 is of formula (1-p), formula (2-p), formula (3-p) or formula (4-p), and

[0323] , the asterisk "*" in formulas (1-p) to (4-p) indicates a connection with an adjacent repeating unit of a polymer chain or oligomer chain or with a terminal end group, or the asterisk "**" in formulas (1-p) to (4-p) indicates a connection to the remainder of formula (I), formula (Ia), formula (Ib), formula (Ic), formula (II), formula (II-a), formula (II-b), formula (II-c), formula (III), formula (III-a), formula (III-b), formula (III-c), formula (IV), formula (IV-a), formula (IV-b) or formula (IV-c) as described above or preferably as described above, and R5, R6, R7, X 11 and c have the meanings described above or preferably as described above.

[0324] Furthermore, the present invention relates to an ophthalmic device or a precursor article for manufacturing an ophthalmic device as described above or preferably below, wherein the polymerized group R1 is of the formula (1-p), formula (2-p), formula (3-p), or formula (4-p) as described above.

[0325] Furthermore, the present invention relates to an oligomer, polymer, or copolymer as described above or preferably below, wherein the polymerized group R1 is of formula (1-p), formula (2-p), formula (3-p), or formula (4-p) as described above, provided that the polymerized group R1 of formula (1-p), formula (2-p), and formula (3-p) in the compounds of formula (Ic) and formula (IV-c) is excluded.

[0326] Particularly preferably, such oligomers, polymers, or copolymers according to the present invention, or polymers / copolymers as materials for ophthalmic devices according to the present invention, are of the formula (M 0 -Ia), chemical formula (M 0 -Ib), chemical formula (M 0 -Ic), chemical formula (M 0 -II-a), chemical formula (M 0 -II-b), chemical formula (M 0 -II-c), chemical formula (M 0 -III-a), chemical formula (M 0 -III-b), chemical formula (M 0 -III-c), chemical formula (M 0 -IV-a), chemical formula (M 0 -IV-b) or chemical formula (M 0 -IV-c) constituent unit M 0 Includes,

[0327]

[0328]

[0329]

[0330]

[0331] R2, [L], X, Y0, Y1, R3, R4, R5, R6, R7, 11 and c have the meanings described above or preferably as described above, and the asterisk "*" indicates, in each case, a connection with an adjacent repeating unit of the polymer chain or oligomer chain or with a terminal end group.

[0332] Furthermore, the present invention relates to an ophthalmic device or a precursor article for manufacturing an ophthalmic device as described above or preferably below, and a constituent unit M 0 is the chemical formula as described above (M 0 -Ia), chemical formula (M 0 -Ib), chemical formula (M 0 -Ic), chemical formula (M 0 -II-a), chemical formula (M 0 -II-b), chemical formula (M 0 -II-c), chemical formula (M 0 -III-a), chemical formula (M 0 -III-b), chemical formula (M 0 -III-c), chemical formula (M 0 -IV-a), chemical formula (M 0 -IV-b) or chemical formula (M 0 -IV-c) and the asterisk "*" indicates, in each case, the connection with an adjacent repeating unit of the polymer chain or oligomer chain or with a terminal end group.

[0333] Preferably, such oligomers, polymers, or copolymers according to the present invention, or polymers / copolymers as materials for ophthalmic devices according to the present invention, are composed of constituent units (M) as described above. 0 -Ia), chemical formula (M 0 -Ib), chemical formula (M 0 -Ic), chemical formula (M 0 -II-a), chemical formula (M 0-II-b), chemical formula (M 0 -II-c), chemical formula (M 0 -III-a), chemical formula (M 0 -III-b), chemical formula (M 0 -III-c), chemical formula (M 0 -IV-a), chemical formula (M 0 -IV-b) or chemical formula (M 0 Includes -IV-c), where

[0334] [L] is independently -(CH2)2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)9-, -(CH2) 11 -, -(CH2) 12 Selected from -, -(CH2)2-(CHF)2-(CH2)2-, -(CH2)2-CHF-(CH2)3-, -(CF2)-(CH2)5-, -(CH2)5-(CF2)-, -(CH2)2-(CF2)-(CH2)2-, -(CH2)3-(CF2)2-(CH2)2-, -(CH2)2-(CF2)2-(CH2)3-, -(CH2)3-O-(CH2)2-O-(CH2)2-, -(CH2)2-O-(CH2)2-O-(CH2)2-, -(CH2)3-O-(CH2)2-S-(CH2)2-, -(CH2)2-SO2-(CH2)2-O-(CH2)2-, preferably having the meaning as described above;

[0335] X is absent or CO, preferably having the meaning as described above;

[0336] Y0 and Y1 are O or S, preferably having the meaning as described above;

[0337] X 11 is selected from the group consisting of O, S, O-SO2, SO2-O, C(=O), OC(=O), C(=O)O, S(C=O)S, and (C=O)S, or preferably has the meaning as described above,

[0338] R6 and R7 are H;

[0339] R5 is H, methyl, ethyl, or phenyl, preferably having the meaning as described above;

[0340] c is 0 or 1, or preferably has the meaning as described above;

[0341] R2, R3 and R4 have the meanings described above or, preferably, as described above.

[0342] Preferably, such oligomers, polymers, or copolymers are included in the ophthalmic device or precursor article for manufacturing the ophthalmic device according to the present invention.

[0343] Particularly preferably, such oligomers, polymers, or copolymers according to the present invention, or polymers / copolymers as materials for ophthalmic devices according to the present invention, are composed of constituent units (M) as described above. 0 -Ia), chemical formula (M 0 -Ib), chemical formula (M 0 -Ic), chemical formula (M 0 -II-a), chemical formula (M 0 -II-b), chemical formula (M 0 -II-c), chemical formula (M 0 -III-a), chemical formula (M 0 -III-b), chemical formula (M 0 -III-c), chemical formula (M 0 -IV-a), chemical formula (M 0 -IV-b) or chemical formula (M 0 Includes -IV-c), where

[0344] [L] is independently -(CH2)2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)9-, -(CH2) 11 -, -(CH2) 12Selected from -, -(CH2)2-(CHF)2-(CH2)2-, -(CH2)2-CHF-(CH2)3-, -(CF2)-(CH2)5-, -(CH2)5-(CF2)-, -(CH2)2-(CF2)-(CH2)2-, -(CH2)3-(CF2)2-(CH2)2-, -(CH2)2-(CF2)2-(CH2)3-, -(CH2)3-O-(CH2)2-O-(CH2)2-, -(CH2)2-O-(CH2)2-O-(CH2)2-, -(CH2)3-O-(CH2)2-S-(CH2)2-, -(CH2)2-SO2-(CH2)2-O-(CH2)2-, preferably having the meaning as described above;

[0345] X is absent;

[0346] Y0 and Y1 are O or S, but at least one of Y0 and Y1 is S, preferably having the meaning as described above;

[0347] X 11 is selected from the group consisting of O, S, O-SO2, SO2-O, C(=O), OC(=O), C(=O)O, S(C=O)S, and (C=O)S, or preferably has the meaning as described above,

[0348] R6 and R7 are H;

[0349] R5 is H, methyl, ethyl, or phenyl, preferably having the meaning as described above;

[0350] c is 1 and;

[0351] R2, R3 and R4 have the meanings described above or, preferably, as described above.

[0352] Particularly preferably, such oligomers, polymers, or copolymers are included in the ophthalmic device or precursor article for manufacturing the ophthalmic device according to the present invention.

[0353] The copolymer is one or more polymerized compounds of formula (I), formula (Ia), formula (Ib), formula (Ic), formula (II), formula (II-a), formula (II-b), formula (II-c), formula (III), formula (III-a), formula (III-b), formula (III-c), formula (IV), formula (IV-a), formula (IV-b) or formula (IV-c) as described above or preferably as described above, or formula (M 0 -Ia), chemical formula (M 0 -Ib), chemical formula (M 0 -Ic), chemical formula (M 0 -II-a), chemical formula (M 0 -II-b), chemical formula (M 0 -II-c), chemical formula (M 0 -III-a), chemical formula (M 0 -III-b), chemical formula (M 0 -III-c), chemical formula (M 0 -IV-a), chemical formula (M 0 -IV-b) and / or chemical formula (M 0 One or more constituent units M of -IV-c) 0 , or one or more constituent units as described below (M 0 -001) or constituent unit (M 0 -080)(these may be identical or different) and one or more constituent units M 2 It may be an oligomer or polymer comprising (which may be identical or different from each other). One or more constituent units M 2 is constituent unit M 0 It is chemically different from. Preferably, the one or more constituent units M 2is styrene, ethoxyethyl methacrylate (EOEMA), methyl methacrylate (MMA), methyl acrylate, n-alkyl acrylate (n-alkyl group contains 2 to 20 C atoms), n-alkyl methacrylate (n-alkyl group contains 2 to 20 C atoms), i-alkyl acrylate (i-alkyl group contains 3 to 20 C atoms), i-alkyl methacrylate (i-alkyl group contains 3 to 20 C atoms), ethoxyethoxyethyl acrylate (EEEA), n -Hydroxyalkyl acrylate( n - The alkyl group contains 2 to 10 C atoms), n -Hydroxyalkyl methacrylate( n - The alkyl group comprises 2 to 10 C atoms), one or more selected from the group consisting of tetrahydrofuryl methacrylate (THFMA), glycidyl methacrylate (GMA), 16-hydroxyhexadecyl acrylate, 16-hydroxyhexadecyl methacrylate, 18-hydroxyoctadecyl acrylate, 18-hydroxyoctadecyl methacrylate, 2-phenoxyethyl acrylate (EGPEA), heptafluorobutyl acrylate, heptafluorobutyl methacrylate, hexafluorobutyl acrylate, hexafluorobutyl methacrylate, hexafluoroisopropyl acrylate, hexafluoroisopropyl methacrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate, pentafluoropropyl acrylate, pentafluoropropyl methacrylate, tetrafluoropropyl methacrylate, trifluoroethyl acrylate, and trifluoroethyl methacrylate. It is induced by the polymerization of monomers.

[0354] Accordingly, the present invention also comprises at least one polymerized compound of formula (I), formula (Ia), formula (Ib), formula (Ic), formula (II), formula (II-a), formula (II-b), formula (II-c), formula (III), formula (III-a), formula (III-b), formula (III-c), formula (IV), formula (IV-a), formula (IV-b) or formula (IV-c) as described above or preferably as described above, or formula (M 0 -Ia), chemical formula (M 0 -Ib), chemical formula (M 0 -Ic), chemical formula (M 0 -II-a), chemical formula (M 0 -II-b), chemical formula (M 0 -II-c), chemical formula (M 0 -III-a), chemical formula (M 0 -III-b), chemical formula (M 0 -III-c), chemical formula (M 0 -IV-a), chemical formula (M 0 -IV-b) and / or chemical formula (M 0 One or more constituent units M of -IV-c) 0 , or one or more constituent units as described below (M 0 -001) or constituent unit (M 0 In addition to -080), styrene, ethoxyethyl methacrylate (EOEMA), methyl methacrylate (MMA), methyl acrylate, n-alkyl acrylate (n-alkyl group contains 2 to 20 C atoms), n-alkyl methacrylate (n-alkyl group contains 2 to 20 C atoms), i-alkyl acrylate (i-alkyl group contains 3 to 20 C atoms), i-alkyl methacrylate (i-alkyl group contains 3 to 20 C atoms), ethoxyethoxyethyl acrylate (EEEA), n -Hydroxyalkyl acrylate( n- The alkyl group contains 2 to 10 C atoms), n -Hydroxyalkyl methacrylate( n - The alkyl group comprises 2 to 10 C atoms), at least one additional selected from the group consisting of tetrahydrofuryl methacrylate (THFMA), glycidyl methacrylate (GMA), 16-hydroxyhexadecyl acrylate, 16-hydroxyhexadecyl methacrylate, 18-hydroxyoctadecyl acrylate, 18-hydroxyoctadecyl methacrylate, 2-phenoxyethyl acrylate (EGPEA), heptafluorobutyl acrylate, heptafluorobutyl methacrylate, hexafluorobutyl acrylate, hexafluorobutyl methacrylate, hexafluoroisopropyl acrylate, hexafluoroisopropyl methacrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate, pentafluoropropyl acrylate, pentafluoropropyl methacrylate, tetrafluoropropyl methacrylate, trifluoroethyl acrylate, and trifluoroethyl methacrylate. The invention relates to an ophthalmic device or a precursor article for manufacturing an ophthalmic device, comprising a polymerized monomer, as described or preferably as described above.

[0355] Particularly preferably, at least one additional comonomer other than the crosslinking agent and / or UV absorber described below is 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl methacrylate, 5-hydroxypentyl acrylate, 8-methylnonyl methacrylate, n -Butyl acrylate, n - Selected from butyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, i-decyl methacrylate, i-decyl acrylate, or mixtures thereof.

[0356] Particularly preferably, such copolymer is included in an ophthalmic device according to the present invention or in a precursor article for manufacturing an ophthalmic device.

[0357] Alternatively, the oligomer or polymer according to the present invention, preferably the polymer, is as described above or preferably as described above (M 0 -Ia), chemical formula (M 0 -Ib), chemical formula (M 0 -Ic), chemical formula (M 0 -II-a), chemical formula (M 0 -II-b), chemical formula (M 0 -II-c), chemical formula (M 0 -III-a), chemical formula (M 0 -III-b), chemical formula (M 0 -III-c), chemical formula (M 0 -IV-a), chemical formula (M 0 -IV-b) or chemical formula (M 0 -IV-c), or a chemical formula as described below (M 0 -001) to chemical formula (M 0 One or more constituent units M of -080) 0 A homopolymer comprising, i.e., an oligomer or polymer, preferably a polymer, wherein all constituent units M in the above formula 0 is the same.

[0358] Exemplary homopolymerizable compounds based on compounds of formulas (I), (II), (III) and / or (IV) are the following compounds (P-001) to (P-080) as shown in Table 2.

[0359] [Table 2]

[0360]

[0361]

[0362]

[0363]

[0364]

[0365]

[0366]

[0367]

[0368]

[0369]

[0370]

[0371] The letter n provides the degree of polymerization as described above.

[0372] An exemplary constituent unit M based on compounds of chemical formulas (I), (II), (III) and / or (IV) 0 , or chemical formula (M 0 -Ia), chemical formula (M 0 -Ib), chemical formula (M 0 -Ic), chemical formula (M 0 -II-a), chemical formula (M 0 -II-b), chemical formula (M 0 -II-c), chemical formula (M 0 -III-a), chemical formula (M 0 -III-b), chemical formula (M 0 -III-c), chemical formula (M 0 -IV-a), chemical formula (M 0 -IV-b) and / or chemical formula (M 0 -IV-c) constituent unit M 0 is the following compound (M as shown in Table 2-1) 0 -001) to compound (M 0 -080) is.

[0373] [Table 2-1]

[0374]

[0375]

[0376]

[0377]

[0378]

[0379]

[0380]

[0381]

[0382]

[0383]

[0384]

[0385] Preferably, the copolymer according to the present invention as described above or preferably as described above comprises one or more constituent units M as described above with a molar ratio m1 together with substituents as described above or preferably as described above. 0 and one or more constituent units M of the molar ratio m2 2 It includes, and the ratio of m1 to m2 is 0.01 or greater and 100 or less.

[0386] Particularly preferably, such copolymer is included in an ophthalmic device according to the present invention or in a precursor article for manufacturing an ophthalmic device.

[0387] Preferably, the copolymer in the ophthalmic device or precursor material for the ophthalmic device according to the present invention as described above or preferably as described above, or the copolymer according to the present invention, has one or more constituent units M as described above, having a substituent as described above or preferably as described above. 0 It contains at a concentration of at least 12% to 96% by weight, preferably at least 20% to 75% by weight or at least 25% to 50% by weight.

[0388] Particularly preferably, such copolymer is included in an ophthalmic device or a precursor article for an ophthalmic device according to the present invention.

[0389] Accordingly, the present invention also relates to a polymerized compound of formula (I), formula (II), formula (III) or formula (IV), or formula (M 0 -Ia), chemical formula (M 0 -Ib), chemical formula (M 0 -Ic), chemical formula (M 0 -II-a), chemical formula (M 0 -II-b), chemical formula (M 0 -II-c), chemical formula (M 0 -III-a), chemical formula (M 0 -III-b), chemical formula (M 0 -III-c), chemical formula (M 0 -IV-a), chemical formula (M 0 -IV-b) or chemical formula (M 0 -IV-c) constituent unit M 0 The total amount of the photoactive chromophore, or the constituent unit (M 0 -001) or constituent unit (M 0 The invention relates to an ophthalmic device or a precursor article for an ophthalmic device as described or preferably above, wherein the total amount of -080) is at least 12 weight% to 96 weight%, preferably at least 20 weight% to 75 weight%, particularly preferably at least 25 weight% to 50 weight%.

[0390] The oligomer, polymer, or copolymer according to the present invention as described above or preferably as described above, preferably the polymer or polymer, may be crosslinked. Particularly preferably, such polymer or copolymer is included in an ophthalmic device or a precursor article for manufacturing an ophthalmic device according to the present invention.

[0391] The oligomers or polymers of the present invention may be produced by any suitable method. However, the oligomers, polymers, and copolymers of the present invention are preferably produced by radical polymerization, and the radical polymerization reaction is initiated by a suitable radical polymerization initiator. For the purposes of the present invention, the type of radical polymerization initiator is not particularly limited and may be any suitable radical-generating compound. Such compounds are well known to those skilled in the art. Suitable polymerization initiators may be selected from thermal initiators or photoinitiators, that is, compounds that generate radicals upon exposure to heat or irradiation using light of a suitable wavelength. Examples of suitable thermal polymerization initiators may be selected from the group of compounds containing one or more peroxide groups, i.e., compounds containing the group -OO-, and / or compounds containing one or more azo groups, i.e., compounds containing the group -N≡N-.

[0392] Suitable polymerization initiators comprising one or more peroxide groups may be selected from the group consisting of, for example, t-butyl(peroxy-2-ethyl-hexanoate), di-(tert-butylcyclohexyl)peroxydicarbonate and benzoyl peroxide.

[0393] Suitable polymerization initiators comprising one or more azo groups may be selected from the group consisting of, for example, 1,1'-azobis(cyclohexanecarbonitrile) and 2,2'azobis(cyclohexanecarbonitrile) (AIBN).

[0394] Examples of suitable photoinitiators are dimethylaminobenzoate / camporquinone, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO) or phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO).

[0395] When a photoinitiator is used as a polymerization initiator, it is preferable that the wavelength required to decompose the photoinitiator is different from the wavelength required to irradiate the compound of the present application to change the optical properties of the compound.

[0396] Preferably, the radical initiator is used in an amount of at least 0.0001 equivalents and no more than 0.1 equivalents of the main monomer. Such radical initiators may be thermal initiators, such as azobis(isobutyronitrile) (AIBN), or photochemical initiators such as dimethylaminobenzoate / camporquinone, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), or phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO).

[0397] The present invention also relates to a composition for polymerization.

[0398] Depending on the intended use, such compositions as described or preferably as described above may include additional different components. These additional components may include, for example, blue absorbers, UV absorbers, antioxidants, and crosslinking agents, or be selected from the group consisting thereof.

[0399] Crosslinking agents can also be referred to as crosslinking agents.

[0400] The present invention also comprises at least one compound of Formula (I), Formula (Ia), Formula (Ib), Formula (Ic), Formula (II), Formula (II-a), Formula (II-b), Formula (II-c), Formula (III), Formula (III-a), Formula (III-b), Formula (III-c), Formula (IV), Formula (IV-a), Formula (IV-b) or Formula (IV-c) as described or preferably as previously stated, or compounds (A-001) to (A-080), and / or an oligomer or polymer having at least one reactive group as previously stated or preferably as previously stated but left for polymerization, and / or a crosslinking agent, and / or a UV absorber, and / or a radical initiator, and optionally Formula (I), Formula (Ia), Formula (Ib), Formula (Ic), Formula (II), Formula (II-a), Formula (II-b), Formula (II-c), Formula (III), Formula (III-a), Formula (III-b), Formula (III-c), Formula (IV), Formula The invention relates to a composition for polymerization comprising additional monomers different from the compound of (IV-a), formula (IV-b) or formula (IV-c) or compounds (A-001) to (A-080).

[0401] A composition comprising at least one compound of formula (I), formula (Ia), formula (Ib), formula (Ic), formula (II), formula (II-a), formula (II-b), formula (II-c), formula (III), formula (III-a), formula (III-b), formula (III-c), formula (IV), formula (IV-a), formula (IV-b) or formula (IV-c) as described or preferably as described above, or compounds (A-001) to (A-080), and an oligomer or polymer according to the present invention as described above, is mainly used for the synthesis of block copolymers under the condition that the oligomer or polymer has at least one remaining reactive group capable of reacting with the monomer.

[0402] The composition may include or contain the essential or optional components mentioned above, or may be essentially composed of or composed of them. All compounds or components that may be used in the composition may be known and commercially available, or may be synthesized by known processes or as described herein.

[0403] The components of the composition according to the present invention are combined in an amount in which a photoactive chromophore of the polymerized formula (I), formula (Ia), formula (Ib), formula (Ic), formula (II), formula (II-a), formula (II-b), formula (II-c), formula (III), formula (III-a), formula (III-b), formula (III-c), formula (IV), formula (IV-a), formula (IV-b) or formula (IV-c) is included in an oligomer, polymer, or copolymer produced according to the present invention, at least 2% to 100% by weight, preferably 3% to 70% by weight, particularly preferably 4% to 51% by weight, and very particularly preferably 5% to 45% by weight.

[0404] The components of the composition according to the present invention are combined in an amount that constitutes the material of an ophthalmic device or a precursor article for manufacturing an ophthalmic device according to the present invention, wherein the photoactive chromophore of the polymerized formula (I), formula (Ia), formula (Ib), formula (Ic), formula (II), formula (II-a), formula (II-b), formula (II-c), formula (III), formula (III-a), formula (III-b), formula (III-c), formula (IV), formula (IV-a), formula (IV-b), or formula (IV-c) is included in the resulting oligomer, polymer, or copolymer, in an amount of at least 2% to 100% by weight, preferably 3% to 70% by weight, particularly preferably 4% to 51% by weight, and very particularly preferably 5% to 45% by weight.

[0405] Suitable blue absorbers are materials that exhibit absorption in the blue wavelength region of visible light. Likewise, blue absorbers that are acrylates or methacrylates and are available as additional monomers during polymerization are preferably selected. Suitable blue absorbers are known from the literature, for example, from International Patent Publication WO 2012 / 167124. A particularly preferred blue absorber is N-2-[3-(2'-methylphenylazo)-4-hydroxy-phenyl-ethyl]-ethylmethacrylamide. These can be added to the composition as described above so that the polymerized composition can also filter short-wavelength visible light in addition to UV light, thereby enabling better protection of the retina if the material is used in the production of ophthalmic products.

[0406] UV absorbers that can be used in the composition of the present invention are not particularly limited and can be easily selected from those generally known to those skilled in the art. Generally suitable UV absorbers are characterized by compounds comprising one or more unsaturated compounds, preferably selected from the group consisting of olefin groups, aryl groups, and heteroaryl groups; these groups may be present in any combination.

[0407] Suitable UV absorbers for use in the composition may be selected from those comprising groups selected from, for example, benzotriazole, benzophenone, and triazine. Suitable UV absorbers are disclosed, for example, in U.S. Patents No. 5,290,892; No. 5,331,073 and No. 5,693,095.

[0408] Suitable UV absorbers are 2-(3-(t-butyl)-4-hydroxy-5-(5-methoxy-2-benzotriazolyl)phenoxy)ethyl methacrylate, 3-(3-(t-butyl)-4-hydroxy-5-(5-methoxy-2-benzotriazolyl)phenoxy)propyl methacrylate, 3-(3-t-butyl-5-(5-chlorobenzotriazole-2-yl)-4-hydroxyphenyl)propyl methacrylate, 3-(3-(tert-butyl)-4-hydroxy-5-(5-methoxy-2H-benzo[d][1,2,3]triazole-2-yl)phenoxy)propyl methacrylate, 2-(2-hydroxy-5-vinylphenyl)-2H-benzotriazole, Allyl-2-hydroxybenzophenone, 2-allyl-6-(2 H -Benzotriazole-2-day)- p-Cresol, 4-methacryloxy-2-hydroxybenzophenone, 2-(2'-hydroxy-3'-metallyl-5'-methylphenyl)benzotriazole, 2-hydroxy-4-methacryloyloxybenzophenone, 4-acryloylethoxy-2-hydroxybenzophenone, 2-[3-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]ethyl methacrylate, 2-(2'-hydroxy-5'-methacrylamidophenyl)-5-methoxybenzotriazole, 2-(2'-hydroxy-5'-methacrylamidophenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-methacryloxypropylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methacryloylpropyl-3'-tert-butyl-phenyl)-5-methoxy-2H-benzotriazole, 2-(3-(tert-butyl)-4-hydroxy-5-(5-methoxy-2H-benzo[d][1,2,3]triazole-2-yl)phenoxy)ethyl methacrylate, 2-[3'-tert-butyl-2'-hydroxy-5'-(3''-methacryloyloxypropyl)phenyl]-5-chlorbenzotriazole, 2-{2'-hydroxy-3'-tert-butyl-5'-[3'-methacryloyloxypropoxy]phenyl}-5-methoxy-2H-benzotriazole, It is 2-[3'tert-butyl-5'-(3''-dimethylvinylsilylpropoxy)-2'-hydroxyphenyl]-5-methoxybenzotriazole, 2-(tert-butyl)-6-(5-chloro-2H-benzo[d][1,2,3]triazole-2-yl)-4-vinylphenol, 2-(2H-1,2,3-benzotriazole-2-yl)-4-methyl-6-(2-methylprop-2-enyl)phenol, 2-(3-acetyl-2-aminophenoxy)ethyl methacrylate, 2-(4-benzoyl-3-hydroxyphenoxy)ethyl acrylate, or a combination of these compounds.

[0409] A preferred UV absorber is 2-[3'-2'H-benzotriazole-2'-yl)-4'-hydroxyphenyl]ethyl methacrylate (BTPEM), 2-(3-(t-butyl)-4-hydroxy-5-(5-methoxy-2-benzotriazolyl)phenoxy)ethyl methacrylate, 3-(3-(t-butyl)-4-hydroxy-5-(5-methoxy-2-benzotriazolyl)phenoxy))propyl methacrylate, 3-(3-t-butyl-5-(5-chlorobenzotriazole-2-yl)-4-hydroxyphenyl)propyl methacrylate, which can be polymerized with monomers described or preferably as described above. It is selected from the group of 3-[3-(2H-1,2,3-benzotriazole-2-yl)-5-tert-butyl-4-hydroxyphenyl]propyl methacrylate.

[0410] The crosslinking agent is a monomer containing at least two polymerizable groups. The crosslinking agent preferably has two polymerizable groups. The crosslinking agent may optionally also contain a functional group capable of coordinating water, such as an OH or NH2 group. Compounds of formulas (Ic), (II-c), (III-c), and (IV-c) act as crosslinking agents.

[0411] A suitable crosslinking agent may be used to impart elastomeric properties to the composition and the ophthalmic device or precursor article produced with it. Typically, any suitable di- or tri-functional group monomer may be used as a crosslinking agent. Such monomers are generally well known to those skilled in the art.

[0412] A suitable crosslinking agent may be used to impart elastomeric properties to the composition and the ophthalmic device or precursor article produced with it. Typically, any suitable die- or tri-functional monomer may be used as a crosslinking agent. Such monomers are generally well known to those skilled in the art, and include para-divinylbenzene, allyl acrylate, ethylene glycol divinyl ether, divinyl sulfone, allyl methacrylate, N,N'-methylene-bis-acrylamide, ethylene glycol diacrylate, ethylene glycol dimethacrylate (EGDMA), N,N'-methylene-bis-methacrylamide, 1,3-propanediol diacrylate, 2,3-propanediol diacrylate, 1,4-butanediol diacrylate, 1,3-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,7-heptanediol diacrylate, 1,8-octanediol diacrylate, and 1,9-nonandiol. Diacrylate, 1,10-Decanediol Diacrylate, 1,11-Undecanediol Diacrylate, 1,12-Dodecanediol Diacrylate, 1,13-Tridecanediol Diacrylate, 1,14-Tetradecanediol Diacrylate, 1,15-Pentadecanediol Diacrylate, 1,16-Hexadecanediol Diacrylate, 1,17-Heptadecanediol Diacrylate, 1,18-Octadecanediol Diacrylate, 1,19-Nona-Decanediol Diacrylate, 1,20-Eicosandiol Diacrylate, 1,21-Heneicosandiol Diacrylate, 1,22-Docosandiol Diacrylate, 1,23-Tricosandiol diacrylate, 1,24-Tetracosandiol diacrylate, ethylene glycol dimethacrylate, N,N'-Dihydroxyethylene-bisacrylamide, thiodiethylene glycol diacrylate, 1,3-Propanediol dimethacrylate, 2,3-Propanediol dimethacrylate, 1,3-Butanediol dimethacrylate, 1,4-Butanediol dimethacrylate, 1,5-Pentanediol dimethacrylate,1,6-Hexanediol Dimethacrylate, 1,7-Heptanediol Dimethacrylate, 1,8-Octanediol Dimethacrylate, 1,9-Nonandiol Dimethacrylate, 1,10-Decanediol Dimethacrylate, 1,11-Undecanediol Dimethacrylate, 1,12-Dodecanediol Dimethacrylate, 1,13-Tridecanediol Dimethacrylate, 1,14-Tetradecanediol Dimethacrylate, 1,15-Pentadecanediol Dimethacrylate, 1,16-Hexa-Decanediol Dimethacrylate, 1,17-Hepta-Decanediol Dimethacrylate, 1,18-Octadecanediol Dimethacrylate, 1,19-Nonadecanediol dimethacrylate, 1,20-Eicosandiol dimethacrylate, 1,21-Heneicosandiol dimethacrylate, 1,22-Docosandiol dimethacrylate, 1,23-Tricosandiol dimethacrylate, 1,24-Tetracosandiol dimethacrylate, 2-(Acryloyloxy)ethyl methacrylate, 2-(Acryloyloxy)propyl methacrylate, 3-(Acryloyloxy)propyl methacrylate, 4-(Acryloyloxy)butyl methacrylate, 5-(Acryloyloxy)pentyl methacrylate, 6-(Acryloyloxy)hexyl methacrylate, 7-(Acryloyloxy)heptyl methacrylate, 8-(Acryloyloxy)octyl methacrylate, 9-(Acryloyloxy)nonyl methacrylate, 10-(Acryloyloxy)decyl methacrylate, 11-(Acryloyloxy)undecyl methacrylate, 12-(Acryloyloxy)dodecyl methacrylate, 13-(Acryloyloxy)tridecyl methacrylate, 14-(Acryloyloxy)tetradecyl methacrylate, 15-(Acryloyloxy)pentadecyl methacrylate, 16-(Acryloyloxy)hexadecyl methacrylate, 17-(Acryloyloxy)heptadecyl methacrylate, 18-(Acryloyloxy)octadecyl methacrylate, 19-(Acryloyloxy)nonadecyl methacrylate, 20-(acryloyloxy)-eicosanyl methacrylate, 21-(acryloyloxy)-heneicosanyl methacrylate, 22-(acryloyloxy)-docosanyl methacrylate,23-(acryloyloxy)-tricosanyl methacrylate, 24-(acryloyloxy)-tetracosanyl methacrylate, neopentyl glycol diacrylate, di(ethylene glycol) diacrylate, N,N'-hexamethylene-bisacrylamide, thiodiethylene glycol diacrylate, thiodiethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, diethylene glycol dimethacrylate, diallyl phthalate, trialyl cyanurate, glyceryl 1,3-dimethacrylate, N,N'-hexamethylenebismethacrylamide, tri(ethylene glycol) diacrylate, tri(ethylene glycol) dimethacrylate (e.g., M, n = 286), tetra(ethylene glycol) diacrylate, tetra(ethylene glycol) dimethacrylate, penta(ethylene glycol) diacrylate, penta(ethylene glycol) dimethacrylate, hexa(ethylene glycol) diacrylate, hexa(ethylene glycol) dimethacrylate, poly(ethylene glycol) diacrylate (e.g., M n = 250 to 750), poly(ethylene glycol) dimethacrylate (e.g., M n It can be selected from the group of = 250 to 750).

[0413] Preferred crosslinking agents are ethylene glycol dimethacrylate, 1,3-propanediol diacrylate, 2,3-propanediol diacrylate, 1,4-butanediol diacrylate, 1,3-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,7-heptanediol diacrylate, 1,8-octanediol diacrylate, 1,9-nonandiol diacrylate, 1,10-decanediol diacrylate, 1,11-undecanediol diacrylate, 1,12-dodecanediol diacrylate, 1,13-tridecanediol diacrylate, and 1,14-tetradecanediol. Diacrylate, 1,15-Pentadecandiol diacrylate, 1,16-Hexadecandiol diacrylate, 1,17-Heptadecandiol diacrylate, 1,18-Octadecandiol diacrylate, 1,19-Nonadecandiol diacrylate, 1,20-Eicosandiol diacrylate, 1,21-Heneicosandiol diacrylate, 1,22-Docosandiol diacrylate, 1,23-Tricosandiol diacrylate, 1,24-Tetracosandiol diacrylate, 1,3-Propanediol dimethacrylate, 2,3-Propanediol dimethacrylate, 1,3-Butanediol dimethacrylate, 1,4-Butanediol Dimethacrylate, 1,5-Pentanediol Dimethacrylate, 1,6-Hexanediol Dimethacrylate, 1,7-Heptanediol Dimethacrylate, 1,8-Octanediol Dimethacrylate, 1,9-Nonandiol Dimethacrylate, 1,10-Decanediol Dimethacrylate, 1,11-Undecanediol Dimethacrylate, 1,12-Dodecanediol Dimethacrylate, 1,13-Tridecanediol Dimethacrylate, 1,14-Tetradecanediol Dimethacrylate, 1,15-Pentadecanediol Dimethacrylate, 1,16-Hexadecanediol Dimethacrylate, 1,17-Heptadecandiol dimethacrylate, 1,18-Octadecandiol dimethacrylate, 1,19-Nonadecanediol dimethacrylate, 1,20-Eicosandiol dimethacrylate, 1,21-Heneicosandiol dimethacrylate, 1,22-Docosandiol dimethacrylate, 1,23-Tricosandiol dimethacrylate, 1,24-Tetracosandiol dimethacrylate, Glyceryl 1,3-Dimethacrylate, Diallyl phthalate, Polyethylene glycol diacrylate (e.g., M, n = 500 to 750), polyethylene glycol dimethacrylate (e.g., M n = 500 to 750), tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, pentaethylene glycol dimethacrylate, pentaethylene glycol diacrylate, hexaethylene glycol dimethacrylate, hexaethylene glycol diacrylate, glyceryl 1,3-dimethacrylate (GDMA), triethylene glycol dimethacrylate (M n = 286) or a combination of these compounds.

[0414] By using alkylene dimethacrylate as a crosslinking agent, the alkylene group is preferably linear and contains 2 to 18 C atoms, preferably 14 to 18 C atoms.

[0415] By using alkylene diacrylate as a crosslinking agent, the alkylene group is preferably linear and contains 2 to 18 C atoms, preferably 14 to 18 C atoms.

[0416] Particularly preferred crosslinking agents include alkylene dimethacrylates containing 14 to 18 C atoms, alkylene diacrylates containing 14 to 18 C atoms, and polyethylene glycol diacrylates (e.g., M n = 500 to 750), polyethylene glycol dimethacrylate (e.g., M n= 500 to 750), tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, pentaethylene glycol dimethacrylate, pentaethylene glycol diacrylate, hexaethylene glycol dimethacrylate and hexaethylene glycol diacrylate.

[0417] The components of the composition according to the present invention or the components of the composition for synthesizing a polymer / copolymer as a material for an ophthalmic device according to the present invention are combined in an amount in which a crosslinking agent is included in the oligomer, polymer, or copolymer produced according to the present invention in an amount of at least 1% to 10% by weight, preferably 3% to 8% by weight, particularly preferably 5% to 7% by weight.

[0418] Suitable antioxidants are phenyl acrylate derivatives having impaired phenol moiety. Preferred antioxidants are

[0419] am.

[0420] Compounds of formula (I), formula (Ia), formula (Ib), formula (Ic), formula (II), formula (II-a), formula (II-b), formula (II-c), formula (III), formula (III-a), formula (III-b), formula (III-c), formula (IV), formula (IV-a), formula (IV-b), or formula (IV-c) according to the present invention as described or preferably as described above, or compounds (A-001) to (A-080), and formula (M as described above or preferably as described above 0 -Ia), chemical formula (M 0 -Ib), chemical formula (M 0 -Ic), chemical formula (M 0 -II-a), chemical formula (M 0 -II-b), chemical formula (M 0 -II-c), chemical formula (M 0 -III-a), chemical formula (M 0-III-b), chemical formula (M 0 -III-c), chemical formula (M 0 -IV-a), chemical formula (M 0 -IV-b) or chemical formula (M 0 One or more constituent units M of -IV-c) 0 or one or more constituent units (M 0 -001) or constituent unit (M 0 The oligomers, polymers, or copolymers thereof, including -080, as described above or preferably as described above, are particularly suitable for use in optically active devices, such as ophthalmic devices as described above.

[0421] Compounds of formula (I), formula (Ia), formula (Ib), formula (Ic), formula (II), formula (II-a), formula (II-b), formula (II-c), formula (III), formula (III-a), formula (III-b), formula (III-c), formula (IV), formula (IV-a), formula (IV-b), or formula (IV-c) according to the present invention as described or preferably as described above, or compounds (A-001) to (A-080), and formula (M as described above or preferably as described above 0 -Ia), chemical formula (M 0 -Ib), chemical formula (M 0 -Ic), chemical formula (M 0 -II-a), chemical formula (M 0 -II-b), chemical formula (M 0 -II-c), chemical formula (M 0 -III-a), chemical formula (M 0 -III-b), chemical formula (M 0 -III-c), chemical formula (M 0 -IV-a), chemical formula (M 0 -IV-b) or chemical formula (M 0 One or more constituent units M of -IV-c) 0 or one or more constituent units (M0 -001) or constituent unit (M 0 The oligomers, polymers, or copolymers thereof, including or preferably as described above, comprising -080) are particularly sensitive to 2-photon or multiphoton absorption. Thus, ophthalmic devices and precursor articles for manufacturing ophthalmic devices are sensitive to 2-photon or multiphoton absorption.

[0422] The ophthalmic device according to the present invention, preferably a system for 2-photon or multiphoton irradiation of an intraocular lens preferably arranged within a patient's eye, is not limited. Several examples are described below.

[0423] Accordingly, the present invention also relates to a precursor article for manufacturing an ophthalmic device, said precursor article having the formula (M as described above or preferably as described above) 0 -Ia), chemical formula (M 0 -Ib), chemical formula (M 0 -Ic), chemical formula (M 0 -II-a), chemical formula (M 0 -II-b), chemical formula (M 0 -II-c), chemical formula (M 0 -III-a), chemical formula (M 0 -III-b), chemical formula (M 0 -III-c), chemical formula (M 0 -IV-a), chemical formula (M 0 -IV-b) or chemical formula (M 0 One or more constituent units M of -IV-c) 0 or one or more constituent units (M 0 -001) or constituent unit (M 0 It is a blank that can be modified into an optically active ophthalmic device comprising at least one oligomer, polymer, or copolymer as described above, or preferably as described above, including -080).

[0424] A preferred ophthalmic device is an optically active ophthalmic device. Examples of such ophthalmic devices or eye implants include lenses, artificial corneal implants, and corneal inlays or rings. More preferably, said ophthalmic device or eye implant is a lens article. Most preferably, said ophthalmic device is a lens. The type of lens is not limited and may include contact lenses or intraocular lenses. More preferably, said ophthalmic device is an intraocular lens, which may be, for example, a posterior chamber intraocular lens or an anterior chamber intraocular lens.

[0425] The blank of the present invention may be produced as one step in a manufacturing process used to produce an ophthalmic device as described above, preferably a contact lens or an intraocular lens. For example, without limitation, the manufacturing process may include steps of polymer synthesis, polymer sheet casting, blank cutting, optic lathe cutting, optic milling, haptic milling or attachment, polishing, solvent extraction, sterilization, and packaging, and the term polymer is used as described above or preferably as described above.

[0426] The ophthalmic device or precursor article for manufacturing the ophthalmic device according to the present invention, as described above or preferably as described above, is

[0427] - At least one compound of formula (I), formula (Ia), formula (Ib), formula (Ic), formula (II), formula (II-a), formula (II-b), formula (II-c), formula (III), formula (III-a), formula (III-b), formula (III-c), formula (IV), formula (IV-a), formula (IV-b) or formula (IV-c), or compounds (A-001) to (A-080) as described herein or preferably as described herein, and / or an oligomer or polymer having at least one reactive group as described herein or preferably as described herein but left for polymerization, and optionally formulas (I), formula (Ia), formula (Ib), formula (Ic), formula (II), formula (II-a), formula (II-b), formula (II-c), formula (III), formula (III-a), formula (III-b), formula (III-c), formula (IV), formula (a) a step of providing a composition comprising additional monomers and / or crosslinking agents and / or UV absorbers and / or radical initiators that are different from the compound of formula (IV-a), formula (IV-b) or formula (IV-c) or compounds (A-001) to (A-080); and

[0428] - Subsequently, it can be formed by a process including the step of forming an ophthalmic device or a precursor article of the above composition.

[0429] The guiding lens according to the present invention is considered to exhibit particularly advantageous characteristics in that it is sufficiently flexible to be rolled or folded, so that consequently, a much smaller incision is required for the lens to be inserted into the eye. This is considered to improve the treatment of the eye, particularly the time required for the eye to be treated.

[0430] The type of intraocular lens is not limited in any way. It may be, for example, a pseudo-phakic intraocular lens or a phakic intraocular lens. The former type usually replaces the eye's natural lens to replace a removed cataract lens. The latter type is used to supplement the existing lens and functions as a permanent corrective lens, which is implanted in the anterior or posterior chamber to correct the eye's refractive errors. It may include, for example, one or more optical components and one or more haptic components, one or more optical components acting as the lens, and one or more haptic components attached to one or more optical components to hold one or more optical components in place in the eye. The intraocular lens may be a one-piece or multi-piece design, depending on whether one or more optic components and one or more haptic components are formed from a single piece of material (one-piece design) or manufactured separately and then combined (multi-piece design). The intraocular lens is also designed in such a way that it allows the intraocular lens to be rolled or folded, for example, so that it is small enough to fit into the eye through an incision as small as possible, for example, of a length of 3 mm or less.

[0431] Additionally, the tragus lens according to the present invention allows for non-invasive adjustment of optical properties, particularly polarization or refractive power, after implantation of the lens in the eye, thereby reducing the need for postoperative visual aids or reducing or entirely avoiding follow-up surgery.

[0432] For changing the optical properties, particularly polarization or refractive power, of an ophthalmic device according to the present invention, e.g., an orthoscopic lens, it is exposed to irradiation having wavelengths greater than 200 nm and less than 1500 nm. The irradiation is not limited to single-photon, two-photon, or multiphoton processes.

[0433] Accordingly, the present invention also relates to a process for modifying the optical properties of an ophthalmic device or a precursor article for manufacturing an ophthalmic device as defined or preferably defined herein, and said process

[0434] - A step of providing an ophthalmic device as defined in the present specification or a precursor article for manufacturing an ophthalmic device; and

[0435] - Subsequently includes the step of exposing the ophthalmic device or the precursor article to irradiation having a wavelength of 200 nm or more and 1500 nm or less.

[0436] Preferably, the wavelength of the irradiation is 250 nm or 300 nm or greater, more preferably 350 nm or greater, even more preferably 400 nm or greater, even more preferably 450 nm or greater, and most preferably 500 nm or greater. Preferably, the wavelength of the irradiation is 1400 nm or 1300 nm or 1200 nm or 1100 nm or 1000 nm or less, more preferably 950 nm or 900 nm or less, even more preferably 850 nm or less, even more preferably 800 nm or less, and most preferably 750 nm or less.

[0437] Accordingly, the present invention also relates to an ophthalmic device or a precursor article for manufacturing an ophthalmic device that can be obtained by the aforementioned or preferably the aforementioned or the above-described irradiation process.

[0438] Alternatively, a change in refractive power may be described as a modification of the refractive index of the ophthalmic device as described or preferably as described. Alternatively, a change in refractive power may be described as a modification of the refractive index of the guiding lens as described or preferably as described. Due to irradiation into the focal volume, the resulting refractive optical structure is characterized by a change in the refractive index relative to the refractive index of most of the ophthalmic device or, alternatively, the refractive index of the unirradiated portion of the ophthalmic device. Due to irradiation into the focal volume, the resulting refractive optical structure is characterized by a change in the refractive index relative to the refractive index of most of the ophthalmic device or guiding lens or, alternatively, the refractive index of the unirradiated portion of the ophthalmic device or guiding lens. A change in polarization or refractive index may be used to form a desired patterned refractive structure in an optical ophthalmic device as described or preferably as described, and in a guiding lens as described or preferably as described.

[0439] Accordingly, the present invention also relates to an ophthalmic device having a refractive optical structure characterized by a change in the refractive index of most or alternatively the refractive index of the non-irradiated portion of the ophthalmic device, which is obtained by the aforementioned or preferably the aforementioned irradiation process and as described below.

[0440] It is desirable to provide a refractive structure that exhibits a change in refractive index with little or no scattering loss, in such a way that the ablation or removal of the ophthalmic device, preferably an intraocular lens, is not observed in the investigation area.

[0441] In such a process, the irradiated area of ​​the ophthalmic device described above, or preferably as described above, may take the form of a refractive structure filled with a two-dimensional or three-dimensional area or volume capable of providing spherical, non-spherical, toroidal, or cylindrical correction. In practice, any optical structure may be formed to generate power correction in both physical directions. Furthermore, the optical structure may be vertically stacked or recorded on a separate plane in the ophthalmic device described above, or preferably as described above, to function as a single lens element.

[0442] Accordingly, the present invention also relates to a method for locally adjusting the polarization and / or refractive power of an ophthalmic device according to the present invention, preferably an intraocular lens preferably arranged within a patient's eye. The present method is particularly related to the fabrication of an optical profile by adjusting the polarization through a two-photon or multiphoton process in a non-destructive manner. The two-photon or multiphoton process allows for a different optical profile compared to a single-photon process and can be advantageously used in the fabrication of an ophthalmic device according to the present invention including the optical profile.

[0443] The system used in the above two-photon or multiphoton process advantageously allows for postoperative and non-invasive adjustment of the optical properties / profile of an implanted intraocular lens (IOL) to eliminate visual defects such as refractive errors. Furthermore, when manufacturing an ophthalmic device according to the present invention, the system advantageously allows for the delicate fabrication of a refractive structure capable of providing, in particular, spherical, aspherical, toroidal, or cylindrical corrections, and / or to maintain the flexibility of the ophthalmic device once the fabrication of the ophthalmic device is completed. The polarization of the ophthalmic device is modified based on a two-photon (or generally multiphoton) process that allows for adjustment of the optical properties / profile of the ophthalmic device or adjustment of optical properties in different planes of the ophthalmic device. Furthermore, the modification of polarization based on a two-photon or multiphoton process improves the maintenance of the flexibility of the ophthalmic device when processed at wavelengths of 400 nm to 550 nm.

[0444] Accordingly, the present invention also relates to a process for adjusting the polarization of an ophthalmic device according to the present invention based on a two-photon or multiphoton absorption process, wherein the process is:

[0445] A step of providing the ophthalmic device described above, preferably as described above; and

[0446] The system includes the step of adjusting the polarity of the ophthalmic device through irradiation of the ophthalmic device, and

[0447] The above system is:

[0448] One or more irradiation sources of 2-photons or multiphotons, focused optically and irradiating the ophthalmic device with an irradiation beam of a first wavelength and / or a second wavelength different from the first wavelength,

[0449] A scanner coupled to one or more irradiation sources and configured to scan the irradiation beam across the ophthalmic device, and

[0450] An input unit coupled to one or more irradiation sources and a scanner, comprising an input unit configured to input data for treating the ophthalmic device by scanning the irradiation beam across the ophthalmic device based on input data, and

[0451] Based on the above treatment of the ophthalmic device, the first wavelength for locally reducing the polarization of the ophthalmic device is 551 nm to 800 nm, and based on the above treatment of the ophthalmic device, the second wavelength for locally increasing the polarization of the ophthalmic device is 400 nm to 550 nm, and as a result, the polymeric optical material of the ophthalmic device is changed to preferably have a significant difference in the UV / Vis spectrum with respect to the non-irradiated polymeric optical material of the ophthalmic device.

[0452] Ultraviolet-visible spectroscopy or ultraviolet-visible spectrophotometry (UV-Vis or UV / Vis) is known to those skilled in the art. It refers to absorption spectroscopy or reflection spectroscopy of a portion of the ultraviolet spectrum and an adjacent portion of the entire visible spectrum. Suitable UV / Vis spectrophotometers are commercially available. The choice of UV / Vis spectrophotometer is not important for comparing the UV / Vis spectrum of the initial ophthalmic device with the UV / Vis spectrum of the irradiated ophthalmic device manufactured according to the present invention. As long as the measurements of both are taken under similar conditions, the results can be compared as known to those skilled in the art. A suitable spectrophotometer is the Lambda 900 UV / Vis spectrophotometer from Perkin Elmer.

[0453] In this specification, polarization can be changed locally with very high precision.

[0454] Furthermore, the present invention relates to a method for correcting a patient's vision by modifying the refractive power of an intraocular lens within the patient's eye, wherein

[0455] A step to verify and measure the degree of the patient's vision correction;

[0456] A step of determining the type and location of a refractive structure recorded within the above-mentioned guide lens to correct the patient's vision; and

[0457] Subsequently, a step of exposing the guide lens to 2-photon or multiphoton irradiation having a wavelength of 551 nm to 800 nm to locally reduce the polarization of the guide lens, or

[0458] Subsequently, the method includes the step of exposing the guide lens to 2-photon or multiphoton irradiation having a wavelength of 400 nm to 550 nm to locally increase the polarization rate of the guide lens.

[0459] In this application, input data is any type of data used to generate a treatment plan defined as transforming ophthalmic requirements into control commands during the recording process of an ophthalmic device according to the present invention. During the recording process, an optical pattern is recorded by irradiation on the ophthalmic device.

[0460] The term "control command" refers to a command that directly controls the recording process, as previously described. A control command can, for example, control the movement of a scanner.

[0461] The term "scanner" as used in the specification is not part of the input unit according to the present invention. As described in the specification, the "scanner" is a component of a system used in a process for adjusting the polarization of an ophthalmic device according to the present invention that controls the movement of an irradiation beam.

[0462] Ophthalmic requirements refer to the desired optical profile that must be generated in an ophthalmic device through a system as described.

[0463] An optical profile is a required change defined by a surgeon based on the results of a patient's examination before or after the implantation of an ophthalmic device, preferably an intraocular lens, and is, for example but without limitation, a spherical total power change, a toric profile, an EDOF profile, or a 2-, 3-, or multifocal profile. Alternatively, an optical profile is an adjustment of the optical characteristics of the ophthalmic device.

[0464] The optical pattern is a necessary change in polarization that causes a change in refractive index in all voxels of an ophthalmic device.

[0465] The term "optic," as used herein as part of a system used in a process for adjusting the polarization of an ophthalmic device according to the present invention, includes all optical equipment necessary to control the spatial distribution of an irradiation source (focus) on the ophthalmic device. Critical variables of focus include lateral focus size (or beam waist) and focal length (or Rayleigh range). Optics include all elements along the optical beam path that determine focus, such as beam expanders, aperture diaphragms, shutters, and focusing optics, particularly microscope objective lenses or single aspherical lenses.

[0466] Multiphoton excitation is generated only near the focal point and preferably by the use of an ultrashort laser pulse. The average power is limited by a sample damage threshold, such as a threshold that is part of the input data as described above.

[0467] Criteria for the Selection and Optimization of System Variables:

[0468] One ultimate goal is to produce localized refractive index correction of the IOL after implantation, as prescribed by the physician, to improve the patient's vision. For refractive index correction surgery, an important criterion is the total treatment time required to achieve the desired result. It is generally recognized that this should not exceed a few minutes for such surgery to be considered feasible. Modern systems capable of localized refractive index correction do not involve the approach required to achieve a substantial number of treatment sessions in the case of IOL application.

[0469] Discussion of System Tradeoffs and Limitations:

[0470] In general, for ophthalmic devices or, specifically, for substantial high-performance systems capable of adjusting IOLs after implantation, their subcomponents must be treated as a system and are therefore recognized as needing to be jointly optimized where there are many interdependence trade-offs between the subcomponents. The subcomponents include a radiation source, optics, a scanner, and a treatment plan.

[0471] A key requirement for any system / parameter optimization is to maintain the system / parameters within safety limits for ophthalmic device materials in the case of treatment, or for the eye and materials including eye components (e.g., retina) in the case of treatment of an ophthalmic device that is an IOL. This requirement establishes the basis for the input data as described above. In particular, two major damage mechanisms for radiation from an irradiation source, preferably a pulsed laser source, can be distinguished as follows: single-pulse damage (dielectric breakdown and avalanche breakdown), and thermal damage (subsequent heating of the lens material and / or eye temperature in the case of repeated pulses for the same volume). For example: the average power of the pulsed irradiation source is related to heating and consequent potential damage to the lens material and / or eye. Therefore, while maintaining the average power of the irradiation source below the overheating threshold of the lens material and / or eye, pulse energy and pulse repetition rate have an inverse relationship, and the product of pulse energy and the number of pulses per second (= the reciprocal of the repetition rate) is equal to the average power.

[0472] Average power is defined as the pulse energy multiplied by the number of pulses per second and is characterized in watts (W).

[0473] The investigation is equivalent to the line flux density (W / cm²).

[0474] Radiant exposure is equivalent to fluence (J / cm²).

[0475] An overall objective is to minimize the treatment time for IOL adjustment after implantation. Theoretically, increasingly higher pulse energies can be applied with more frequent pulses (= higher repetition rates), but when the average power typically exceeds 1 watt, overheating begins, creating unsafe conditions for the IOL material and the retina. Therefore, to complete the treatment of the entire IOL volume within minutes while maintaining safe operating limits, a preferred radiation exposure dose can be defined. The preferred radiation exposure dose is ≤5 kJ / cm², particularly preferably <1 kJ / cm², and very particularly preferably <0.3 kJ / cm². This described radiation exposure dose is further applied to the process and method according to the present invention as described below.

[0476] If the treatment plan is too extensive and exceeds the laser safety limits regarding overheating, it is possible to stop the treatment to allow both the ophthalmic device material and tissues affected by the treatment to cool down. After cool-down, the locating system can compare the treated voxels of the ophthalmic device with the optical pattern and the treatment can be continued.

[0477] As described above, the process of adjusting the optical characteristics / profile of the ophthalmic device through the system and according to the requirements will be carried out according to the treatment plan described above. According to the treatment plan, for example, a profile for toric, spherical, multifocal, or EDOF (extended depth of focus) can be recorded into the ophthalmic device according to the present invention. An algorithm can be used to record a profile for, for example, toric, spherical, multifocal, or EDOF (extended depth of focus) profiles.

[0478] By combining information on the desired optical profile with input data, control commands for the irradiation source, optics, and scanner of the system as described above, and the desired optical pattern can be calculated. Additional input data is, for example, lens data such as laser energy required for a predetermined change in refractive index per voxel of the ophthalmic device material, and additional patient data such as the precise position and orientation of the ophthalmic device in the patient's eye, which is part of the treatment plan data.

[0479] Control commands may be updated and changed during the recording process by process input data, such as, for example, patient eye temperature data obtained by IR-temperature measurement, an irradiation beam obtained by, for example, OCT (optical coherence tomography), process positioning data of an ophthalmic device or eye, and / or refractive data obtained from Scheimpflug images.

[0480] In an additional embodiment of the input data, the input data includes lens data of the ophthalmic device, preferably the guiding lens, and / or treatment plan data related to a treatment plan for the treatment of the ophthalmic device. For example, the lens data may include data regarding one or more of the polarization degree and / or refractive index of the ophthalmic device as a function of the position of each volume or part of the ophthalmic device, shape, diopter, cylindrical and spherical, and / or individual aberrations in said dimensions. Accordingly, the polarization may be increased or decreased at a specific location or volume in one or more planes of the ophthalmic device depending on the current polarization (or refractive index) and the polarization (or refractive index) obtained through the treatment.

[0481] In some embodiments, the treatment plan calculation may generate a control command that gives rise to one or more of the treatment plan data comprising: scan strategy control command data for the scan of the irradiation beam of the first and / or second wavelength traversing the ophthalmic device (e.g., scan pattern and / or scan order and / or scan rate and / or scan duration of the scan pattern and / or scan duration of the scan order and / or pulse duration of the pulse of the irradiation beam of the first and / or second wavelength (e.g., nanosecond, picosecond, or femtosecond pulse) and / or irradiation beam profile of the irradiation beam of the first and / or second wavelength and / or radiation (photon) density and / or radiation intensity and / or radiation power and / or radiation wavelength); input data during the process, such as temperature data of the current and / or expected temperature of the ophthalmic device during the exposure; the refractive index / polarization of the ophthalmic device obtained based on the exposure, in particular the refractive index / polarization obtained with respect to the mapping of the refractive index / polarization obtained at a specific location / coordinate of the ophthalmic device Input data such as refractive index / polarization data, rhexis dimension data, and eye data regarding the shape and / or dimensions of the patient's eye, positioning data regarding the position and / or orientation of an ophthalmic device to the eye, and registration data regarding the identification of the patient and / or the patient's specific eye.

[0482] Preferably, the scan strategy control command data of the scan strategy is a scan pattern and / or scan rate and / or pulse duration and / or radiation intensity of the pulse as further described below.

[0483] The variables of the irradiation beam(s) may then be adjusted according to lens data and / or treatment plan data as defined herein, in order to precisely (locally) change the polarization / refractive index of the ophthalmic device, if desired.

[0484] Preferably, the variables of the irradiation beam(s) are adjusted according to lens data and / or treatment plan data as described above or, preferably, as described in this specification.

[0485] Those skilled in the art are well aware that optimal irradiation focus conditions are achieved when the depth of field (Rayleigh range) of the irradiation beam matches the desired thickness of the optical structure being recorded into the ophthalmic device.

[0486] Those skilled in the art are well aware that optimal irradiation focus conditions are achieved when the depth of field (Rayleigh range) of the irradiation beam is matched to the local thickness of the ophthalmic device.

[0487] In a further embodiment, lens data includes data regarding the radiation absorption characteristics of the ophthalmic device (e.g., absorption and / or light attenuation coefficients, which may vary depending on the wavelength of light), wherein the system is configured to adjust a first wavelength and / or a second wavelength for the ophthalmic device to locally change the polarization based on a multiphoton absorption process. For example, based on the material used in the ophthalmic device, a specific wavelength or wavelength range may be an input for precise local change of the polarization of the ophthalmic device.

[0488] As part of a system used in a process for adjusting the polarization of an ophthalmic device according to the present invention, one or more irradiation sources may include one or more pulsed lasers that can be used to generate nanosecond pulses, preferably picosecond pulses, and more preferably femtosecond pulses. Preferably, one irradiation source is used. Particularly preferably, one or more irradiation sources include one or more pulsed lasers used to generate femtosecond pulses. Particularly preferably, one pulsed laser used to generate femtosecond pulses is used as irradiation for the system according to the present invention or for the process and method according to the present invention.

[0489] In one embodiment, one or more irradiation sources each comprise a laser tunable to emit a laser beam having a first and a second wavelength. This may be particularly advantageous when a single laser can be used to (locally) increase or decrease the polarization / refractive index of an ophthalmic device or an orthotic lens as desired.

[0490] Different pulse laser types are suitable for the irradiation source within the system used in the process for adjusting the polarization of the ophthalmic device according to the present invention. Both MHz lasers and kHz lasers are suitable and have particular advantages. While the MHz laser system operates, for example, at low pulse energy, the focused laser spot can be maintained at a μm-size (<1 μm to several μm) and thus can be used, for example, for precise local refractive index correction in all three dimensions to create diffractive structures. A preferred MHz irradiation source is an 80 MHz laser having pulse energy in the range of 0.1 to 10 nJ.

[0491] On the other hand, kHz lasers typically operate at higher pulse energies of 0.1 to 10 μJ and therefore require larger spot sizes, for example, of 10 to 100 μm, to avoid damaging the lens material. However, a larger laser spot size implies a large depth of field (long Rayleigh range) that can be equal to or even exceed the thickness of the ophthalmic device material. In the case of such a long Rayleigh range, it may be impossible to change the refractive index layer by layer in the IOL, but it may be possible to change it uniformly only along a line around the focal point. A preferred kHz irradiation source is a laser with a repetition rate of 100 to 500 kHz.

[0492] The average power of the irradiation source, as described above or preferably as described above, is preferably 300 to 600 mW, more preferably 400 to 500 mW.

[0493] As part of a system used in a process for adjusting the polarization of an ophthalmic device according to the present invention, the irradiation source preferably comprises a tunable laser, such as a Ti:sapphire laser (e.g., Coherent’s Chameleon Ultra II, Santa Clara, California, USA), capable of providing a variable wavelength in the range of approximately 680-1080 nm. The system may also include an optical parametric oscillator (e.g., Coherent’s frequency doubling Chameleon Compact OPO-Vis, Santa Clara, California, USA).

[0494] As part of a system used in a process for adjusting the polarization of an ophthalmic device according to the present invention, an irradiation source particularly preferably comprises a femtosecond pump laser together with an optical parametric amplifier. The pump laser emits irradiation with an average power of more than 10 watts at 1030 nm in pulses of less than 350 fs having a repetition rate of 0.1 to 700 kHz. The radiation of the pump laser is directed to the optical parametric amplifier, and the pump laser output is frequency-doubled and optionally mixed to produce a final adjustable output in the wavelength range of 600 nm to 800 nm. A preferred repetition rate is 50 to 600 kHz. A particularly preferred repetition rate is 100 to 500 kHz.

[0495] As part of a system used in a process for adjusting the polarization of an ophthalmic device according to the present invention, an irradiation source comprises, particularly preferably, a femto-second pump laser of average power greater than 10 watts at 1030 nm emitting irradiation pulses of less than 350 fs at a repetition rate of 1 to 700 kHz together with an optical parametric amplifier. The radiation of the pump laser relates to an optical parametric amplifier having one or more second-harmonic stages and produces a final adjustable output in a wavelength range of 400 nm to 590 nm. A preferred repetition rate is 50 to 600 kHz. A particularly preferred repetition rate is 100 to 500 kHz.

[0496] The laser type described above, or preferably as described above, generates a collimated optical beam with a diameter of several millimeters, which subsequently relates to optics and scanners. The optical beam quality (characterized by the beam quality factor or beam propagation factor) is ideally 1.0 to 1.5, more ideally 1.0 to 1.3. According to DIN EN ISO 11146, the optical beam quality is given in M².

[0497] The first wavelength of the irradiation beam in the system used in the process for adjusting the polarization of the ophthalmic device according to the present invention is 551 nm to 800 nm, preferably 551 nm to 700 nm, to (locally) reduce the polarization (and consequently the refractive index) of the IOL.

[0498] The second wavelength of the irradiation beam in the system used in the process for adjusting the polarization of the ophthalmic device according to the present invention is 400 nm to 550 nm, preferably 500 nm to 550 nm, to (locally) increase the polarization (and consequently refractive index) of the IOL.

[0499] In this specification, polarization can be changed locally with very high precision.

[0500] Optic in a system used in a process for adjusting the polarization rate of an ophthalmic device according to the present invention:

[0501] The primary function of the optic is to focus an irradiation beam emitted from an irradiation source and controlled by a scanner onto an ophthalmic lens. The key considerations mentioned above are spot size and depth of focus to minimize treatment time while maintaining the limits given by material damage and laser safety requirements mentioned above as part of general input data. The most important characteristics of the optic are the numerical aperture (NA), along with the effective focal length (EFL) and the diameter of the irradiation beam at the entry aperture of the focusing optic. Additionally, all optical elements within the system used in the process for adjusting the polarization of the ophthalmic device according to the present invention must be selected for diffraction- or near-diffraction-limited characteristics so as not to substantially degrade the optical beam quality.

[0502] Since spot size determines the spatial resolution that can be obtained, different ophthalmic needs will require different spot sizes. Ideally, the spot size is 1 to 100 μm, more ideally 50 to 100 μm, to minimize treatment time while also keeping the possibility of material damage low.

[0503] Scanner in a system used in a process for adjusting the polarization rate of an ophthalmic device according to the present invention:

[0504] A scanner used within a system used in a process for adjusting the polarization of an ophthalmic device according to the present invention may include a galvano-scanner, a piezo-scanner, a rotary scanner, or an acousto-optic modulator, or it may be digital, such as a spatial light modulator, a digital micromirror device, or a stereolithography apparatus (SLA). Preferably, as part of the system of the present invention according to this specification, the scanner is selected from a galvano-scanner, a piezo-scanner, a rotary scanner, an acousto-optic modulator, a spatial light modulator, a digital micromirror device, or an SLA. A preferred galvano-scanner is a single pivot-point scanner.

[0505] Preferably, the scanner is configured to operate at a scan speed greater than 50 mm / s. This may allow the treatment time to be kept short. Generally, the treatment time should not exceed a few minutes, preferably less than 10 minutes, preferably less than 5 minutes, and particularly preferably less than 3 minutes per treatment session.

[0506] The treatment area may be limited to the volume and size of the ophthalmic device. Typically, the optic of the ophthalmic device or intraocular lens has a diameter of 5 mm to 7 mm and typically a thickness of 0.2 mm to 2.0 mm.

[0507] The optimal radiation exposure is <1 kJ / cm² and, more ideally, <0.3 kJ / cm² to keep the total radiation exposure low and the treatment time short while processing the entire volume of the ophthalmic device.

[0508] Particularly preferably, a random scan pattern or an interleaved scanning line is used to spread the irradiation energy of the irradiation beam.

[0509] Scanning can be performed in three ways. In a bottom-up scan, the laser can move from spot to spot with a specific dwell time on each spot ("bottom-up, between spots"). Alternatively, in a bottom-up scan, the laser can dwell on spots that overlap each other ("bottom-up, spot overlap"). Alternatively, the laser can move at a constant speed without dwelling on any spot ("passing at constant speed").

[0510] In one embodiment of the scan pattern, the IOL is scanned as the light source, as described above or preferably as described above, penetrates the pupil and emits light. The IOL contained within the capsular bag at the time of scanning is inserted first through an intracorneal incision using a conventional surgical procedure. In this embodiment, the entire volume of the IOL is scanned, and the scan is performed in a bottom-up manner (i.e., a portion of the IOL away from the cornea is scanned first), and in this manner, an optical profile is generated to avoid unnecessary changes in the refractive index in the optical path.

[0511] As previously mentioned, a key consideration when selecting a scanning program is to minimize localized heating of the ophthalmic device and / or the patient's eye; therefore, various variables are used in the scanning program. Taking into account anatomical features such as rupture and pupil size, as well as optical features such as numerical aperture and laser pulse characteristics, a laser program is generated at a specific scanning speed and sequence. In this embodiment, the relationship between the lens coordinate system and the eye coordinate system is automatically taken into account.

[0512] Variables for the scan program and / or treatment plan are preferably the first and second wavelengths, scan speed and sequence, positioning of the lens relative to the eye (e.g., in Cartesian coordinates), scan strategy, change in acquired refractive index (optical pattern), numerical aperture of the objective lens, rupture, pupil and / or optical diameter of the lens (approximately 6 mm in some examples), pulse duration of the laser beam (shape, intensity and xy positioning), laser safety when operating the laser, and centering for the positioning of the lens and the eye.

[0513] In one embodiment of a system used in a process for adjusting the polarization rate of an ophthalmic device according to the present invention, photons generated from a laser are preferably guided through a mirror (e.g., as Optic 1) to a beam expander that prepares a beam for, for example, a subsequent scanner and a focusing optical device. After passing through the beam expander, the photons are directed toward a scanner (e.g., a galvano-scanner or a piezo-scanner or a rotary scanner or an acousto-optic modulator or, in a digital sense, a spatial light modulator or a digital micromirror device or an SLA).

[0514] After passing through the scanner, the laser beam travels through other optics, such as a divider mirror. In this embodiment, the divider mirror splits the beam into a main imaging beam for ophthalmic device inspection and a beam for monitoring beam characteristics and positioning with feedback. After the divider mirror, the optical beam is focused to the ophthalmic device by an imaging group or a focusing optic. In one embodiment, the imaging group includes a microscope objective lens for obtaining a high numerical aperture (for μm-level spatial resolution) or a low-NA optic to allow higher pulse energies at the μJ level.

[0515] The system described above, or preferably as described above, may additionally include a microscope objective lens coupled to a scanner to focus the irradiation beam into the ophthalmic device by means of the microscope objective lens, wherein the numerical aperture of the microscope objective lens is 0.1 to 0.8, preferably 0.2 to 0.5, and more preferably 0.2 to 0.4. Providing a microscope objective lens having such a numerical aperture allows for high irradiation beam quality, particularly regarding focusing, and resolution characteristics of the beam used to process the guide lens.

[0516] The microscope objective lens includes a typical lens configuration that allows for the correction of, for example, chromatic aberration. The microscope objective lens is preferably connected to an eye interface system, typically a suction system, that holds the patient's eye in a fixed position, as further described below.

[0517] In an additional embodiment of the objective lens used within the system described above, the objective lens is an Olympus LUCPLFLN objective lens for focusing an irradiation beam to an ophthalmic device.

[0518] An alternative focusing optical device / imaging group is composed of a single aspherical lens having an effective focal length preferably from 50 to 150 mm and a numerical aperture preferably from 0.025 to 0.1.

[0519] The system described above, or preferably as described above, may further include a positioning system for determining the position of the focal point of the irradiation beam within the eye of the patient, the positioning system being coupled to a scanner, and the scanning by the scanner of the irradiation beam across the guide lens being based on the position of the focal point of the irradiation beam within the eye.

[0520] The positioning system may include a positioning system such as an optical coherence tomography system, a confocal microscope, or a Scheimpflug camera. The positioning system may be coupled to the scanner directly or indirectly. In some examples where a confocal microscope is used, the confocal microscope may be coupled directly to the scanner.

[0521] The positioning system described above is used to provide topographical data of the eye to a positioning system for determining the position of a laser focus based on the correlation between the eye and the guide lens.

[0522] In the case of confocal microscopes, a partially transparent mirror is used to allow video imaging.

[0523] The system described above, or preferably as described above, is further configured to determine the position and / or orientation of the guide lens with respect to the eye and the outlet of the irradiation beam, and the scanning of the irradiation beam across the guide lens by a scanner is based on the position and / or orientation of the guide lens with respect to the eye. This may be particularly advantageous because misalignment can be taken into account when processing the guide lens with the irradiation beam(s), since the position of the guide lens may not be centered with respect to the eye.

[0524] Regarding the position of the IOL, at least two coordinate systems can be considered in relation to the coordinate system of the eye and the coordinate system of the lens inside the eye, whereby the two may not be centered relative to each other.

[0525] Regarding the position of the IOL, at least two coordinate systems may be considered in relation to the x, y, z coordinates of the eye and the x, y, z coordinates of the lens inside the eye, whereby the two may not be centered relative to each other.

[0526] In one embodiment, the positioning system may generate input data. Such input data includes, for example, data regarding the lens position and / or orientation of the ophthalmic device with respect to the laser beam outlet within the eye, and / or mapping of the optical output of the eye and / or ophthalmic device. Such data is used to calculate the duration of the optical pattern or treatment.

[0527] Additionally, the positioning system is capable of generating input data during the recording process. Input data during this process includes, for example, data regarding the lens position and / or orientation of the ophthalmic device within the eye and relative to the laser beam outlet, and / or mapping of the optical output of the eye and / or ophthalmic device. This data is used for process modification of control commands used to generate optical patterns.

[0528] The system described above, or preferably as described above, may further include a temperature control unit coupled to one or both of (i) one or more irradiation sources and (ii) a scanner, wherein the temperature control unit is configured to determine the temperature of a portion of the ophthalmic device during the treatment of the ophthalmic device by the scan based on the irradiation beam characteristics of the irradiation beam and the ophthalmic device characteristics of the ophthalmic device, and the system is configured to control one or both of (i) one or more irradiation sources and (ii) a scanner based on the temperature determination. This may allow ensuring that the eye and / or the ophthalmic device may not be adversely affected based on treatment with the irradiation beam.

[0529] Additionally, the temperature control unit is preferably configured to predict the temperature during the treatment of the ophthalmic device, and the input data includes the predicted temperature. This may allow for taking precautionary measures to ensure that the eye and / or the ophthalmic device may not be adversely affected based on the treatment with the irradiation beam.

[0530] Alternatively, the temperature management unit is an infrared camera that logs the eye temperature and displays the correlation between the measured data and the standard data holding calibration data to calculate the actual eye temperature.

[0531] In another embodiment, the temperature dependence of the refractive index is used to control the temperature. In this example, the system includes a refractive power mapping device. Based on the deviation of the measured refractive power map and the progress of the recorded predicted refractive power map, the temperature of the lens can be calculated during the process.

[0532] In another embodiment, the temperature dependence of the emission spectrum is used for temperature control. In this example, the system includes a UV-Vis spectrophotometer. Based on the deviation of the measured emission peak wavelength and / or peak width, the temperature at the focal spot can be calculated during the process.

[0533] The system described above, or preferably as described above, may further include an eye interface system configured to maintain the patient's eye in a fixed position. The eye interface system may include a suction system to fix the position of the patient's eye during treatment.

[0534] The patient can be "docking" into the system while lying flat or standing upright.

[0535] The system described above, or preferably as described above, may further include a wireless or wired receiver and / or a transceiver for one or more of (i) transmitting a control command to one or more probe sources, (ii) transmitting a control command to a scanner, and (iii) inputting control command data required to generate an optical pattern into the scanner.

[0536] One or more irradiation sources and / or scanners may therefore be controlled remotely. Additionally or alternatively, data regarding one or both of lens data and treatment plan data may be stored outside the system and provided to the system if desired. In some embodiments, it may be desirable to provide a wired receiver or transceiver for controlling at least one irradiation source and / or scanner to reduce (or avoid) any delay when transmitting control signals to one or more irradiation sources and / or scanners.

[0537] In another embodiment, the receiver / transmitter transmits treatment plan data and lens data to a central computing unit that calculates optical patterns, and transmits this back to the receiver as input data to provide to the system.

[0538] The system described above, or preferably as described above, may additionally include a device for locally measuring the refractive power of the ophthalmic device during the treatment of the ophthalmic device. Adjustment of one or more of the irradiation source(s), scanner, and input data may thereby be performed during the treatment process.

[0539] The system described above, or preferably as described above, may additionally include a refractometer to locally measure the refractive index of the ophthalmic device during the treatment of the ophthalmic device. Adjustment of one or more of the irradiation source(s), scanner, and input data may thereby be performed during the treatment process.

[0540] Additional components of the photon-providing system are optionally a cover in which all equipment is mounted, a power unit that supplies sufficient energy to the system and all sub-systems, and sub-systems such as a suction system and / or a cooler.

[0541] In addition to the components mentioned above, a controller, firmware, and a graphical user interface (GUI), as well as a treatment algorithm, may be provided. To connect to the system, a connection may be established via other ports such as Bluetooth, Wi-Fi, or RS-232.

[0542] The present invention also relates to a method for locally adjusting the polarization of an ortho-lens according to the present invention arranged within a patient's eye, wherein the treatment plan data comprises one or more of the following:

[0543] Scan strategy control command data for a scan strategy for scanning the above-mentioned irradiation beam across a guide lens (e.g., scan pattern and / or scan order and / or scan speed and / or scan duration of the scan pattern and / or scan duration of the scan order and / or pulse duration of the pulse of the irradiation beam of the first and / or second wavelength and / or irradiation beam profile of the above-mentioned irradiation beam and / or radiation (photon) density and / or radiation intensity and / or radiation power and / or radiation wavelength),

[0544] Temperature data of the current and / or expected temperature of the guide lens during the above exposure,

[0545] Refractive index data of the refractive index of the guide lens acquired based on the above exposure, in particular regarding the mapping of the refractive index acquired to a specific position / coordinate of the guide lens,

[0546] Rupture dimension data of the rupture dimension,

[0547] Eye data regarding the shape and / or dimensions of the patient's eye,

[0548] Positioning data regarding the position and / or orientation of a guiding lens for the eye, and

[0549] Registration data regarding the identification of the patient and / or the patient's specific eye.

[0550] The present invention also relates to a method for locally adjusting the polarization of an ortho-lens according to the present invention arranged within a patient's eye, wherein the exposure of the ortho-lens to the irradiation beam comprises the exposure of a first volume of the ortho-lens before the exposure of a second volume of the ortho-lens, and the first volume is further away from the cornea of ​​the patient's eye than the second volume.

[0551] In the section mentioned above, the initial step of the method may be to provide the guide lens.

[0552] In an embodiment, exposure of the guide lens to the irradiation beam comprises exposing a first volume and / or plane and / or position of the guide lens before exposing a second volume and / or plane and / or position of the guide lens, wherein the first volume and / or plane and / or position is further from the cornea of ​​the patient's eye than the second volume and / or plane and / or position, and the volume and / or plane and / or position irradiated at a later time in the irradiation sequence may be closer to the cornea than the volume and / or plane and / or position irradiated at an earlier time. The volume may thus relate to one or more planes of the guide lens.

[0553] The present invention further relates to a method for correcting a patient's vision by modifying the refractive index of an guiding lens according to the present invention within the patient's eye, wherein

[0554] A step to verify and measure the degree of the patient's vision correction;

[0555] A step of determining the type and location of a refractive structure recorded within the above-mentioned guide lens to correct the patient's vision; and

[0556] Subsequently, the step of exposing the guide lens to 2-photon or multiphoton irradiation having a wavelength of 551 nm to 800 nm to locally reduce the polarization of the guide lens, and / or

[0557] Subsequently, to expose the guide lens to the above irradiation, preferably using a system and / or process as described above, the method includes the step of exposing the guide lens to a two-photon or multiphoton irradiation having a wavelength of 400 nm to 550 nm to locally increase the polarization rate of the guide lens.

[0558] As outlined above, a change in polarizability causes a change in refractive index.

[0559] It must be noted that variations of the embodiments described in this invention are included within the scope of this invention. Any feature disclosed in this invention may be exchanged for an alternative feature providing the same purpose or an equivalent or similar purpose, unless explicitly excluded. Accordingly, any feature disclosed in this invention should be regarded as an example of a general series or an equivalent or similar feature, unless otherwise stated.

[0560] All features of the present invention may be combined with one another in any manner, provided that specific features and / or steps are not excluded from one another. This applies particularly to the preferred features of the present invention. Equally, features of non-essential combinations may be used separately (and not combined).

[0561] Furthermore, it should be noted that many features, and in particular features of the preferred embodiments of the present invention, are original in themselves and should not be regarded merely as part of the embodiments of the present invention. In the case of such features, independent protection may be requested in addition to or as an alternative to any currently claimed invention.

[0562] The technical teachings disclosed together with the present invention are summarized and may be combined with other embodiments.

[0563] There is no doubt that many other substantial alternatives may occur to those skilled in the art. It will be understood that the present invention is not limited to the embodiments described and includes modifications that are obvious to those skilled in the art and fall within the scope of the claims appended herein.

[0564] Examples

[0565] The following examples are intended to demonstrate the benefits of the compound in a non-limiting manner.

[0566] Unless otherwise indicated, all syntheses are performed under an inert gas atmosphere using a dry (anhydrous) solvent. Solvents and reagents are purchased from commercial suppliers.

[0567] DCM is used to denote dichloromethane. DMF is used to denote dimethylformamide. EE or EtOAc is used to denote ethyl acetate. THF is used to denote tetrahydrofuran. RT stands for room temperature.

[0568] Copolymer properties can be investigated on blanks prepared by bulk polymerization of monomers. Comonomers, crosslinking agents, and initiators can therefore be purchased from commercial suppliers. All chemicals are available in the highest purity and can be used as received.

[0569] Synthesis of precursor substances:

[0570] Example 1:

[0571]

[0572] Thiourea (297 mg, 3.90 mmol, 1.50 eq.) is dissolved in ethanol (2.80 mL, 18.3 eq.), and a solution of 25 wt% sodium methoxide in methanol (1.12 mL, 4.89 mmol, 1.88 eq.) and ethyl benzoyl acetate (449 μL, 2.60 mmol, 1.00 eq.) are added. The solution is stirred overnight at room temperature. Water is added to the reaction mixture, and the mixture is neutralized using 1 M hydrochloric acid. The formed precipitate is filtered by suction and dried overnight in a vacuum drying oven. This synthesis yields 307.0 mg of 6-phenyl-2-sulfanylidene-1,2,3,4-tetrahydropyrimidine-4-one (57.8 mmol, 58% of the theoretical value).

[0573] 1 H NMR (500 MHz, DMSO) δ 12.52 (s, 1H), 12.46 (s, 1H), 7.73 - 7.67 (m, 2H), 7.59 - 7.52 (m, 1H), 7.52 - 7.46 (m, 2H), 6.08 (d, J = 1.9 ㎐, 1H).

[0574] Similarly, other derivatives are manufactured in the same way:

[0575]

[0576]

[0577] 1 H NMR (600 MHz, DMSO-d6) δ 11.25 (s, 1H), 11.15 (s, 1H), 7.61 (t, 1H), 7.53 (d, 2H), 7.35 (d, 2H), 7.26 (s, 1H).

[0578]

[0579] 1H NMR (600 MHz, DMSO-d6) δ 11.16 (s, 1H), 11.14 (s, 1H), 7.72 (d, 2H), 7.54 (t, 1H), 7.49 (d, 2H), 5.81 (s, 1H).

[0580]

[0581] 1 H NMR (500 MHz, DMSO-d6) δ 11.14 (s, 2H), 7.52 (s, 1H), 7.46 (d, 2H), 6.91 (d, 2H), 3.75 (s, 3H).

[0582]

[0583] 1 H NMR (500 MHz, DMSO-d6) δ 13.20 (s, 1H), 7.90 (s, 1H), 7.31 - 7.60 (m, 5H), 6.12 (s, 1H).

[0584] Example 2:

[0585]

[0586] 5-phenyl-2,4(1H,3H)-pyrimidinedione (1.00 g, 5.31 mmol, 1.00 eq.) is added to a stirred solution of phosphine desulfide (1.18 g, 5.31 mmol, 1.00 eq.) in diethylene glycol dimethyl ether (7.97 mL, 10.5 eq.). Subsequently, sodium bicarbonate (1.78 g, 21.24 mmol, 4.00 eq.) is added in portions. The reaction mixture is stirred overnight at 110°C. The reaction mixture is poured into cold water, the precipitate is filtered by suction, and washed with cold water. The crude product is dried overnight in a vacuum drying oven. This synthesis yields 976.1 mg of 2,3-dihydro-5-phenyl-2-thiooxo-4(1H)-pyrimidinone (4.78 mmol; 90% of the theoretical value).

[0587] 1H NMR (400 MHz, DMSO-d6) δ 6.12 (s, 1 H), 7.3-7.6 (m, 5H), 7.9 (s, 1H), 13.2 (s, 1H)

[0588] Example 3:

[0589]

[0590] 1-ethyl-5-methyl-1,2,3,4-tetrahydropyrimidine-2,4-dione (500.00 mg, 3.24 mmol, 1.00 eq.), 2,4-bis(pyridin-1-yum-1-yl)-2,4-disulfanylidene diphosphatiane-1,5-diide (370.19 mg, 0.97 mmol, 0.30 eq.), and dimethyl sulfone (1.62 g, 17.19 mmol, 5.3 eq.) were combined and heated to 175°C for 15 minutes. Then, water was added, and the mixture was heated to 100°C for 15 minutes. The suspension was filtered. The crude solid was purified by column chromatography (100% chloroform). This synthesis yields 170.00 mg of 1-ethyl-5-methyl-1,2,3,4-tetrahydropyrimidine-2,4-dithione (0.89 mmol; 27% of the theoretical value).

[0591] 1 H NMR (400 MHz, CDCl3) δ 10.98 (s, 1H), 7.12 (s, 1H), 4.24 (q, J = 7.2 Hz, 2H), 2.15 (s, 3H), 1.43 (t, J = 7.2 Hz, 3H).

[0592] Example 4:

[0593]

[0594] 60% sodium hydride (9.85 g, 246.29 mmol, 1.40 eq.) in mineral oil was dissolved in anhydrous 1,4-dioxane (234.93 mL, 15.46 eq.), and N , NEthyl thiourea (12.28 g, 117.87 mmol, 0.67 eq.) is added in portions. The suspension is stirred at 50°C for 30 minutes. After cooling the reaction mixture to room temperature, methyl 3,3-dimethoxypropionate (26.87 g, 175.92 mmol, 1.00 eq.) is added. The reaction mixture is refluxed overnight. Water and ethyl acetate are added to the reaction mixture, and the mixture is washed once with brine and twice with water. The combined aqueous layer is extracted twice with ethyl acetate. The combined organic layer is dried with MgSO4, filtered, and evaporated. Next, the crude product is distilled to yield 11.86 g of 1-ethyl-2-sulfanylidene-1,2,3,4-tetrahydropyrimidine-4-one (75.93 mmol, 64% of the theoretical value).

[0595] 1 H NMR (500 MHz, CDCl3) δ 9.75 (s, 1H), 7.28 (d, J = 7.9 Hz, 1H), 5.99 (dd, J = 7.9, 1.9 Hz, 1H), 4.25 (q, J = 7.2 Hz, 2H), 1.40 (t, J = 7.2 Hz, 3H).

[0596] 1 H NMR (500 MHz, CDCl3) δ 9.98 (s, 1H), 7.10 (dd, J = 7.8, 4.3 Hz, 1H), 5.99 (d, J = 7.6 Hz, 1H), 4.45 (q, J = 7.0 Hz, 2H), 1.32 (t, J = 7.0 Hz, 3H).

[0597] Similarly, other derivatives are manufactured in the same way:

[0598]

[0599] Example 5:

[0600]

[0601] 2-Thiouracil (525.42 mg, 4.10 mmol, 1.00 eq.), phenylbromic acid (1.00 g, 8.20 mmol, 2.00 eq.), Cu(OAc)2*H2O (818.5 mg, 4.10 mmol, 1.00 eq.), and TMEDA (1.24 mL, 8.20 mmol, 2.00 eq.) were dissolved in methanol (328 mL, 1.97 eq.) and water (82.0 mL, 1.11 eq.). The reaction mixture was stirred overnight at room temperature. The solvent was evaporated, and the crude product was purified by column chromatography (20% methanol / DCM).

[0602] This synthesis yields 31.52 mg of 1-phenyl-2-sulfanylidene-1,2,3,4-tetrahydropyrimidine-4-one (0.25 mmol, 6% of the theoretical value).

[0603] 1 H NMR (300 MHz, chloroform- d ) δ = 10.03 (s, 1 H), 7.53 (m, 3 H), 7.36 (d, J = 7.8 Hz, 1 H), 7.34 (m, 2 H), 6.07 (d, J = 7.8 Hz, 1 H).

[0604] Example 6:

[0605]

[0606] Potassium carbonate (1.00 eq.) is added to a solution of 6-bromohexyl methacrylate (1.00 eq.) and 2-thiothimine (1.50 eq.) in DMF (100 eq.). The mixture is stirred at room temperature for 18 hours. Subsequently, water is added to the reaction mixture, and the mixture is neutralized using 1 M hydrochloric acid. The aqueous layer is extracted twice with ethyl acetate, dried with magnesium sulfate, filtered, and evaporated under vacuum. The crude product is purified by column chromatography (50 to 100% EtOAc in cyclohexane). This synthesis yields 6-(thymine-1-yl)hexyl methacrylate and 6-[(5-methyl-6-oxo-1,6-dihydropyrimidine-2-yl)sulfanyl]hexyl 2-methylprop-2-enoate.

[0607] 1 H NMR (500 MHz, CDCl3) δ 8.95 (s, 1H), 6.96 (d, J = 1.5 Hz, 1H), 6.10 - 6.06 (m, 1H), 5.54 (p, J = 1.7 Hz, 1H), 4.12 (t, J = 6.7 Hz, 2H), 3.71 - 3.63 (m, 2H), 1.94 - 1.90 (m, 6H), 1.66 (p, J = 6.8 Hz, 4H), 1.41 - 1.27 (m, 8H).

[0608] Similarly, other derivatives are prepared in the same way ([%] represents yield).

[0609]

[0610]

[0611]

[0612]

[0613] 1 H NMR (500 MHz, DMSO) δ 12.45 (s, 1H), 5.91 (s, 1H), 4.30 (s, 1H), 3.37 (t, J= 6.6 ㎐, 2H), 3.32 (s, 2H), 3.09 (t, J = 7.3 ㎐, 2H), 2.38 (t, J = 7.5 ㎐, 2H), 1.68 - 1.56 (m, 3H), 1.43 - 1.33 (m, 2H), 1.24 (s, 8H), 0.88 (t, J = 7.4 ㎐, 3H).

[0614]

[0615] 1 H NMR (500 ㎒, DMSO) δ 12.50 (s, 1H), 7.82 (d, J = 6.5 ㎐, 1H), 6.03 (d, J = 6.4 ㎐, 2H), 3.38 (t, J = 6.5 ㎐, 2H), 3.06 (t, J = 7.2 ㎐, 2H), 1.66 - 1.57 (m, 2H), 1.45 - 1.37 (m, 2H), 1.34 - 1.24 (m, 4H).

[0616]

[0617] 1 H NMR (500 ㎒, CDCl3) δ 12.52 (s, 1H), 8.06 - 7.85 (m, 2H), 7.48 (dt, J = 5.3, 2.5 ㎐, 3H), 6.68 (s, 1H), 6.08 (s, 1H), 5.54 (t, J = 1.7 ㎐, 1H), 4.14 (t, J = 6.6 ㎐, 2H), 3.34 (t, J = 7.3 ㎐, 2H), 1.93 (s, 3H), 1.84 (p, J = 7.3 ㎐, 2H), 1.70 (p, J = 6.8 ㎐, 2H), 1.54 (dt, J = 15.0, 6.4 ㎐, 4H), 1.46 (q, J = 8.3 ㎐, 2H).

[0618]

[0619] 1 H NMR (500 MHz, CDCl3) δ 8.11 (d, J = 5.4 Hz, 1H), 6.80 (d, J = 5.4 Hz, 1H), 6.11 (s, 2H), 5.57 (s, 2H), 4.17 (td, J = 6.7, 2.2 Hz, 4H), 3.16 (dt, J = 15.9, 7.3 Hz, 4H), 1.96 (s, 6H), 1.84 - 1.67 (m, 8H), 1.57 - 1.39 (m, 8H).

[0620] Example 7:

[0621]

[0622] 6-(3-ethyl-2,6-dioxo-1,2,3,6-tetrahydropyrimidine-1-yl)hexyl 2-methylprop-2-enoate (1.00 eq.) is dissolved in anhydrous toluene (170 eq.), and Lawesson reagent (0.70 eq.) is added under argon. The resulting suspension is heated to 110°C for 2 hours while checking the conversion rate via TLC. The reaction mixture is cooled, added to an aqueous NH4Cl solution, and extracted three times with ethyl acetate. The combined organic phase is washed with an aqueous NaHCO3 solution and brine, and dried with Na2SO4. The crude product is purified by column chromatography on a silica phase using cyclohexane / ethyl acetate = 10% to 30% as the eluent. 6-(3-ethyl-2-oxo-6-sulfanilidene-1,2,3,6-tetrahydropyrimidine-1-yl)hexyl 2-methylprop-2-enoate (42%) is isolated as a yellow solid.

[0623] 1H NMR (500 MHz, CDCl3) δ 7.03 (s, 1H), 6.09 (t, J = 1.4 Hz, 1H), 5.54 (q, J = 1.7 Hz, 1H), 4.14 (t, J = 6.5 Hz, 2H), 3.90 (q, J = 7.3 Hz, 2H), 3.39 (t, J = 7.2 Hz, 2H), 2.23 (d, J = 1.1 Hz, 3H), 1.94 (t, J = 1.3 Hz, 3H), 1.76 (p, J = 7.3 Hz, 2H), 1.69 (p, J = 6.8 Hz, 2H), 1.53 - 1.37 (m, 7H).

[0624] Similarly, other derivatives are prepared in the same way ([%] represents yield).

[0625]

[0626]

[0627] 1 H NMR (500 MHz, CDCl3) δ 9.96 (s, 1H), 7.06 (s, 1H), 3.82 (q, J = 7.2 Hz, 2H), 2.12 (d, J = 1.0 Hz, 3H), 1.36 (t, J = 7.2 Hz, 3H).

[0628] Example 8:

[0629]

[0630] Potassium hydride (1 eq.) is added to a solution of 6-[(5-methyl-4-oxo-3H-pyrimidine-2-yl)sulfanyl]hexyl 2-methylprop-2-enoate (1.0 g) in dry dimethylformamide (10 ml). Subsequently, the mixture is heated to 50°C for 0.5 hours. Ethyl iodide (1.20 eq.) is added. The mixture is stirred at 60°C for 3 days. Subsequently, ammonium chloride (1.2 eq.) is added to the reaction mixture to neutralize it. The mixture is filtered and evaporated under vacuum. The crude product is purified by column chromatography (0 to 30% EtOAc in cyclohexane). This synthesis is 6-[(4-ethoxy-5-methylpyrimidine-2-yl)sulfanyl]hexyl 2-

[0631] It produces methylprop-2-enoate (31% of the theoretical value).

[0632] Similarly, other derivatives are manufactured in the same way:

[0633]

[0634]

[0635] 1 H NMR (500 MHz, CDCl3) δ 6.66 (s, 1H), 6.09 (t, J = 1.3 Hz, 1H), 5.54 (p, J = 1.6 Hz, 1H), 4.14 (t, J = 6.6 Hz, 2H), 3.16 (t, J = 7.3 Hz, 2H), 2.54 (s, 3H), 2.33 (s, 3H), 1.94 (t, J = 1.3 Hz, 3H), 1.70 (dq, J = 19.0, 7.1 Hz, 4H), 1.52 - 1.34 (m, 4H).

[0636] Example 9:

[0637]

[0638] Thionyl chloride (3.24 mL, 44.6 mmol, 5.00 eq.) was added to a suspension of 6-(oxane-2-yloxy)hexanoic acid (1.93 g, 8.92 mmol, 1.00 eq.) and THF (40.0 mL, 55.3 eq.). The mixture was stirred for 30 minutes. After adding toluene, the mixture was evaporated under vacuum. The residue was suspended in THF (40.0 mL, 55.3 eq.), and in THF (10 mL, 13.83 eq.) N,N - Add dropwise to a solution of diisopropylethylamine (4.55 mL, 26.76 mmol, 3.00 eq.) and thiouracil (1.71 g, 13.38 mmol, 1.50 eq.). Stir the reaction mixture overnight. Quench the reaction mixture with methanol and filter by suction. Neutralize the aqueous phase with 1 M HCl and extract twice with methyl THF. Dry the organic phase with magnesium sulfate, filter by suction, and evaporate under vacuum. Purify the crude product by column chromatography (0 to 100% EtOAc / cyclohexane). This synthesis yields 698.58 mg of 1-[6-(oxane-2-yloxy)hexanoyl]-2-sulfanilidene-1,2,3,4-tetrahydropyrimidine-4-one (2.14 mmol, 24% of the theoretical value).

[0639] Example 10:

[0640]

[0641] A solution of 1-[6-(oxane-2-yloxy)hexanoyl]-2-sulfanylidene-1,2,3,4-tetrahydropyrimidine-4-one (1.05 g, 3.22 mmol, 1 eq.) and p-toluenesulfonic acid (277.2 mg, 1.61 mmol, 0.5 eq.) in methanol (20.13 mL, 154.14 eq.) is stirred at 40°C for 1 hour. The solvent is evaporated under vacuum. Subsequently, the residue is extracted with water and methyl THF. The organic phase is washed with saturated sodium bicarbonate, dried with magnesium sulfate, filtered by suction, and evaporated under vacuum. This synthesis yields 780.17 mg of 1-(6-hydroxyhexanoyl)-2-sulfanylidene-1,2,3,4-tetrahydropyrimidin-4-one (3.22 mmol, 100% of the theoretical value).

[0642] Example 11:

[0643]

[0644] 2-[(11-hydroxyundecyl)sulfanyl]-1,2,3,4-tetrahydropyrimidine-4-one (3.40 g, 10.82 mmol, 1.00 eq.), triethylamine (6.00 mL, 43.28 mmol, 4.00 eq.), and 4-(dimethylamino)-pyridine (132.19 mg, 1.08 mmol, 0.10 eq.) are dissolved in DCM (52.14 mL, 75.47 eq.). Then, methacrylic anhydride (1.78 mL, 11.90 mmol, 1.10 eq.) is added, and the mixture is stirred at room temperature for 15.5 hours. The reaction mixture is quenched with methanol, and 1 M hydrochloric acid and water are added. The phases are separated, and the organic phase is washed twice with water and once with a saturated NaCl solution. The organic layer is dried with MgSO4, and the crude product is purified by column chromatography (0 to 30% EtOAc / cyclohexane). This synthesis yields 611.78 mg of 11-[(4-oxo-1,2,3,4-tetrahydropyrimidine-2-yl)sulfanyl]undecyl 2-methylprop-2-enoate (1.66 mmol, 15% of the theoretical value).

[0645] Similarly, other derivatives are manufactured in the same way:

[0646]

[0647]

[0648] 1 H NMR (500 MHz, CDCl3) δ 12.61 (s, 1H), 7.87 (d, J = 6.6 Hz, 1H), 6.24 (d, J = 6.6 Hz, 1H), 6.11 (t, J = 1.5 Hz, 1H), 5.57 (p, J = 1.6 Hz, 1H), 4.16 (t, J = 6.6 Hz, 2H), 3.21 (t, J = 7.3 Hz, 2H), 1.96 (t, J = 1.3 Hz, 3H), 1.76 (p,J = 6.7, 6.2 ㎐, 2H), 1.70 (q, J = 7.0 ㎐, 2H), 1.55 - 1.39 (m, 4H).

[0649]

[0650] 1 H NMR (500 ㎒, CDCl3) δ 12.25 (s, 1H), 6.14 - 6.07 (m, 1H), 6.03 (s, 1H), 5.54 (t, J = 1.7 ㎐, 1H), 4.13 (t, J = 6.7 ㎐, 2H), 3.17 (t, J = 7.3 ㎐, 2H), 2.46 (t, J = 7.5 ㎐, 2H), 1.94 (t, J = 1.3 ㎐, 3H), 1.81 - 1.62 (m, 6H), 1.49 - 1.21 (m, 14H), 0.95 (t, J = 7.4 ㎐, 3H).

[0651]

[0652] 1 H NMR (500 ㎒, CDCl3) δ 12.30 (s, 1H), 7.84 (d, J = 6.6 ㎐, 1H), 6.21 (d, J = 6.6 ㎐, 1H), 6.09 (d, J = 1.5 ㎐, 1H), 5.54 (p, J = 1.6 ㎐, 1H), 4.13 (t, J = 6.7 ㎐, 2H), 3.18 (t, J = 7.3 ㎐, 2H), 1.94 (t, J = 1.3 ㎐, 3H), 1.77 - 1.63 (m, 4H), 1.51 - 1.21 (m, 14H).

[0653]

[0654] 1H NMR (500 MHz, CDCl3) δ 11.66 (s, 1H), 7.70 (d, J = 1.3 Hz, 1H), 6.09 (s, 1H), 5.54 (t, J = 1.7 Hz, 1H), 4.13 (t, J = 6.7 Hz, 2H), 3.15 (t, J = 7.4 Hz, 2H), 2.03 (s, 3H), 1.94 (d, J = 1.5 Hz, 3H), 1.78 - 1.60 (m, 4H), 1.50 - 1.23 (m, 14H).

[0655] Example 12:

[0656]

[0657] Acryloyl chloride (419.77 μL, 5.148 mmol, 1.20 eq.) is added at 0°C to a solution of 1-(11-hydroxyundecyl)-1,2,3,4-tetrahydropyrimidine-2,4-dione-2-[(11-hydroxyundecyl)sulfanyl]-3,4-dihydropyrimidine-4-one (1.28 g, 4.29 mmol, 1.00 eq.) and triethylamine (2.38 mL, 17.16 mmol, 4.00 eq.) in THF (13.90 mL, 40.0 eq.). The reaction mixture is heated to room temperature within 18 hours. The reaction mixture is quenched with isopropanol and acidified to pH 2 using 1 M hydrochloric acid. The aqueous layer is extracted twice with methyl THF. The organic layer is dried with MgSO4 and the solvent is removed. The crude product is purified by column chromatography (0 to 50% EtOAc / cyclohexane). This synthesis yields 805.34 mg of 11-[(4-oxo-1,2,3,4-tetrahydropyrimidine-2-yl)sulfanyl]undecylprop-2-enoate (2.27 mmol, 53% of the theoretical value).

[0658] Example 13:

[0659]

[0660] 2-methylsulfanyl-3 in DMF (13.12 ml; 170.56 eq.) H Lithium hydride (28.54 mg; 3.41 mmol; 1.00 eq.) is added to a solution of -pyrimidine-4-one (500.00 mg; 3.41 mmol; 1.00 eq.). Then, the mixture is heated to 50°C while stirring. When the reaction stops bubbling, it is cooled to room temperature, and 6-bromohexyl methacrylate (1.02 g; 4.09 mmol; 1.20 eq.) is added. The mixture is stirred at 60°C for 18.5 hours. Then, a saturated aqueous ammonium chloride solution is added to the reaction mixture, the mixture is filtered by suction, and washed with THF. The mother lye is evaporated under vacuum. The crude product is purified by column chromatography (0 to 30% EtOAc in cyclohexane). This synthesis yields 347.0 mg of 6-[2-(methylsulfanyl)-6-oxo-1,6-dihydropyrimidine-1-yl]hexyl 2-methylprop-2-enoate (1.05 mmol, 31% of the theoretical value).

[0661] 1 H NMR (500 MHz, CDCl3) δ 7.73 (d, J = 6.4 Hz, 1H), 6.17 (d, J = 6.4 Hz, 1H), 6.09 (t, J = 1.4 Hz, 1H), 5.55 (p, J = 1.6 Hz, 1H), 4.14 (t, J = 6.6 Hz, 2H), 4.06-3.99 (m, 2H), 2.56 (s, 3H), 1.94 (t, J = 1.3 Hz, 3H), 1.76 (q, J = 7.6 Hz, 2H), 1.69 (q, J = 6.9 Hz, 2H), 1.50-1.37 (m, 4H).

[0662] Similarly, other derivatives are manufactured in the same way:

[0663]

[0664]

[0665] 1 H NMR (500 ㎒, CDCl3) δ 7.51 (d, J = 1.2 ㎐, 1H), 5.97 (dd, J = 1.7, 1.0 ㎐, 1H), 5.42 (s, 1H), 4.02 (t, J = 6.6 ㎐, 2H), 3.39 (s, 3H), 3.12 - 2.97 (m, 2H), 1.90 (d, J = 1.1 ㎐, 3H), 1.82 (s, 3H), 1.69 - 1.54 (m, 4H), 1.33 (m, 4H).

[0666]

[0667] 1 H NMR (500 ㎒, CDCl3) δ 8.05 - 7.88 (m, 2H), 7.53 - 7.35 (m, 3H), 6.68 (s, 1H), 6.11 (t, J = 1.3 ㎐, 1H), 5.56 (s, 1H), 4.17 (t, J = 6.6 ㎐, 2H), 3.57 (s, 3H), 3.35 (t, J = 7.3 ㎐, 2H), 1.96 (t, J = 1.3 ㎐, 3H), 1.87 (p, J = 7.4 ㎐, 2H), 1.73 (p, J = 6.8 ㎐, 2H), 1.61 - 1.54 (m, 2H), 1.52 - 1.44 (m, 2H).

[0668]

[0669] 1 H NMR (500 ㎒, CDCl3) δ 8.04 (dd, J = 6.8, 2.9 ㎐, 2H), 7.49 (p, J= 3.3 ㎐, 3H), 6.80 (s, 1H), 6.11 (s, 1H), 5.56 (s, 1H), 4.17 (t, J = 6.6 ㎐, 2H), 4.02 (s, 3H), 3.25 (t, J = 7.3 ㎐, 2H), 1.96 (s, 3H), 1.86 (p, J = 7.4 ㎐, 2H), 1.73 (p, J = 6.8 ㎐, 2H), 1.63 - 1.54 (m, 2H), 1.52 - 1.42 (m, 2H).

[0670]

[0671] 1 H NMR (500 ㎒, CDCl3) δ 8.02 - 7.92 (m, 2H), 7.53 - 7.41 (m, 3H), 6.66 (s, 1H), 6.11 (dd, J = 1.7, 1.0 ㎐, 1H), 5.56 (p, J = 1.6 ㎐, 1H), 4.17 (m, 4H), 3.34 (t, J = 7.3 ㎐, 2H), 1.95 (t, J = 1.3 ㎐, 3H), 1.87 (p, J = 7.4 ㎐, 2H), 1.79 - 1.69 (m, 2H), 1.61 - 1.54 (m, 2H), 1.49 (qd, J = 7.7, 7.1, 1.5 ㎐, 2H), 1.39 (t, J = 7.1 ㎐, 3H).

[0672]

[0673] 1 H NMR (500 ㎒, CDCl3) δ 7.08 (s, 1H), 6.09 (s, 1H), 5.54 (t, J = 1.8 ㎐, 1H), 4.13 (t, J = 6.6 ㎐, 2H), 3.87 (q, J = 7.2 ㎐, 2H), 3.24 (t, J= 7.3 ㎐, 2H), 2.01 (s, 3H), 1.94 (s, 3H), 1.70 (dp, J = 14.2, 7.0 ㎐, 4H), 1.45 (dq, J = 26.2, 7.7 ㎐, 4H), 1.35 (t, J = 7.2 ㎐, 3H).

[0674] 13 C NMR (126 ㎒, CDCl3) δ 177.8 (C arom S), 167.7 (CO2R), 154.7 (C2), 141.3 (C6), 136.7, 125.4, 112.1 (C5), 64.8, 45.8, 29.8, 28.7, 28.7, 28.6, 25.8, 18.5, 14.6, 14.2.

[0675]

[0676] 1 H NMR (500 ㎒, CDCl3) δ 7.26 (d, J = 1.9 ㎐, 1H), 6.09 (s, 1H), 5.54 (q, J = 1.7 ㎐, 1H), 4.41 (q, J = 7.2 ㎐, 2H), 4.14 (t, J = 6.6 ㎐, 2H), 3.32 (t, J = 7.2 ㎐, 2H), 2.07 (s, 3H), 1.94 (d, J = 1.8 ㎐, 3H), 1.71 (dp, J = 20.9, 7.0 ㎐, 4H), 1.47 (h, J = 9.4, 8.8 ㎐, 7H).

[0677] 13 C NMR (126 ㎒, CDCl3) δ 178.9 (C=S), 172.7 (C arom S), 167.7 (CO2R), 141.5 (C6), 136.6, 125.4, 118.0 (C5), 64.8, 52.3, 30.2, 28.6, 28.6, 28.4, 25.8, 18.5, 14.7, 13.8.

[0678]

[0679] 1 H NMR (500 MHz, CDCl3) δ 7.03 (s, 1H), 6.09 (t, J = 1.4 Hz, 1H), 5.54 (q, J = 1.7 Hz, 1H), 4.14 (t, J = 6.5 Hz, 2H), 3.90 (q, J = 7.3 Hz, 2H), 3.39 (t, J = 7.2 Hz, 2H), 2.23 (d, J = 1.1 Hz, 3H), 1.94 (t, J = 1.3 Hz, 3H), 1.76 (p, J = 7.3 Hz, 2H), 1.69 (p, J = 6.8 Hz, 2H), 1.53 - 1.37 (m, 7H).

[0680] 13 C NMR (126 MHz, CDCl3) δ 198.2 (C=S), 167.7 (CO2R), 156.6 (C arom S), 136.6, 134.4 (C6), 130.8 (C5), 125.4, 64.7, 48.8, 32.1, 28.6, 28.5, 28.4, 25.7, 19.4, 18.5, 14.6.

[0681] Application Examples:

[0682] Example 14 - General polymerization procedure for producing a bulk copolymer

[0683] To produce a bulk polymer blank, monomers are melted under vacuum, and additional components are added in respective amounts as shown in Table 3 below.

[0684] These monomers in the composition as shown in Table 3 below are thoroughly mixed under stirring using mild heating and degassed by three freeze-pump-thaw cycles. An appropriate amount (0.02 to 0.12 eq.) of radical initiator is added (e.g., 1,1'-(3,3,5-trimethylcyclohexylidene)bis[2-(1,1-dimethylethyl)peroxide [Luperox® 231] or 2-[(E)-2-(1-cyano-1-methylethyl)diazen-1-yl]-2-methylpropanenitrile).

[0685] polymerization:

[0686] Two glass plates are coated with polyethylene terephthalate sheets, and a 1 mm thick cell is created between the polyethylene terephthalate sheets using a silicone rubber gasket. The coated surfaces of the glass sheets are clipped together using a spring clip with a syringe needle placed between the gasket and the polyethylene terephthalate sheets. Subsequently, the cavity is filled with one of the formulations shown in Table 3 and manufactured as described above using an airtight syringe through the needle. Once the cavity is filled, the syringe needle is removed, the mold is sealed using a final clip, and the assembly is placed in an oven. The polymerization temperature is 60°C to 180°C, and individual polymerization conditions are selected for each initiator. After allowing the mold to cool to room temperature, the polymer plate is removed from the mold.

[0687] A change in refractive index is induced by irradiation at 275 to 340 nm. The refractive index (n) of the polymer film and blank at 589 nm is measured on the Schmidt+Haensch ATR-L before and after irradiation. Refractive index n D, 35℃ Measure before irradiation. The difference in refractive index before and after irradiation is Δn. Table 4 below shows the refractive index n D, 35℃ In addition, it shows the change in refractive index (Δn) after irradiation.

[0688] Ref-[1] is an example of a monomer included in the general disclosure of U.S. Patent Application Publication No. 2013033975 (e.g., page 6):

[0689] Ref-[1].

[0690] Table 3 Composition - The amounts of the components are provided in mol%, IDMA represents isodecyl methacrylate, PEG-DA represents poly(ethylene glycol) diacrylate, and HEMA represents hydroxyethyl methacrylate, A represents ethylene glycol dimethacrylate instead of PEG-DA, and B represents undecane dimethacrylate instead of PEG-DA, and C represents hydroxybutyl methacrylate instead of HEMA, and D represents hydroxybutyl acrylate instead of HEMA, and E represents hydroxyethyl acrylate instead of HEMA, and F represents butyl acrylate instead of IDMA, and G represents butyl methacrylate instead of IDMA, and the total amount of each selected radical initiator becomes 100 mol% initiator.

[0691]

[0692] Table 4 Polymer Properties (Refractive Index and Abbe Number) v 0) and change in refractive index after irradiation:

[0693]

[0694] The results of Application Examples 1 to 36 show a change in refractive index and a high Abbe number after irradiation.

[0695] The change in refractive index with respect to the Abbe number of Application Examples 1 to 36 is visualized in FIG. 1 in comparison with the application examples for the reference compound Ref-[1] of the prior art.

[0696] Figure 1 clearly shows the advantages of the described polymer compared to the reference example of the prior art.

Claims

Claim 1 An ophthalmic device comprising at least one polymerizable compound of formula (I), formula (II), formula (III) or formula (IV): In the above formulas (I) to (IV), R# is independently -[L]-R1 or R2 in each case, provided that at least one R# is -[L]-R1; Y1 and Y0 are independently O or S; X is absent or C=O; R1 is a trialkoxysilyl group or a dialkoxyalkylsilyl group, or a silyl group of formula (1), formula (2), or formula (3), or a polymerizable group of formula (4), wherein the alkyl and / or alkoxy group is independently having 1 to 6 C atoms and is linear or branched: In the above chemical formulas (1) to (4), alkyl means, in each case independently, a linear or branched alkyl group having 1 to 6 C atoms, and the asterisk "*" indicates, in each case independently, a linkage to the linker [L]; X 11 is independently selected in each case from the group consisting of O, S, O-SO2, SO2-O, C(=O), OC(=O), C(=O)O, S(C=O) and (C=O)S, and R5, R6 and R7 are independently selected in each case from the group consisting of H, F, linear or branched unfluorinated or partially or fully fluorinated alkyl groups having 1 to 20 C atoms, and aryls having 6 to 14 C atoms, and c is independently 0 or 1 in each case; [L] is independently in each case -(C(R)2) o- , or -(C(R)2) p- X 8- (C(R)2) q- (X9) s- (C(R)2) r- (X 10 ) t -(C(R)2) u - and;R is independently selected from the group consisting of H, F, a linear or branched alkyl group having 1 to 4 C atoms, and a linear or branched partially or fully fluorinated alkyl group having 1 to 4 C atoms in each case;o is selected from the group consisting of 1 to 20, and X8, X9, and X 10 is independently O, S, SO2, or NR0 in each case, s and t are 0 or 1, p and q are independently selected from the group consisting of 1 to 10 in each case, r and u are independently selected from the group consisting of 0 to 10 in each case, and -(C(R)2) p- X 8- (C(R)2) q- (X9) s- (C(R)2) r- (X 10 ) t -(C(R)2) u The total number of atoms for - is 20 or fewer, and R0 is selected from the group consisting of a linear or branched alkyl group having 1 to 4 C atoms and a linear or branched partially or completely fluorinated alkyl group having 1 to 4 C atoms, independently in each case; R2 is an aryl group that can be substituted with one or more R', wherein it is H, a linear or branched alkyl group having 1 to 20 C atoms that is not halogenated or partially or completely halogenated, a linear or branched alkoxyalkyl group having 2 to 20 C atoms that is not halogenated or partially or completely halogenated, a cycloalkyl group having 3 to 7 C atoms, or a linear or branched aryl group having 6 to 14 C atoms; and R3 and R4 are, independently in each case, H, F, a linear or branched alkyl group having 1 to 20 C atoms An alkyl group that is not halogenated or partially or completely halogenated, a cycloalkyl group having 3 to 7 C atoms, an aryl group that is not halogenated or partially or completely halogenated having 6 to 14 C atoms, said aryl group that can be substituted with one or more R's, or a heteroaryl group having 5 to 14 C atoms, said heteroaryl group that can be substituted with one or more R's;R' is independently selected in each case from the group consisting of F, SF5, CN, SO2CF3, a linear or branched alkyl group having 1 to 20 C atoms that is not halogenated or partially or fully halogenated, a cycloalkyl group having 3 to 6 C atoms that is not halogenated or partially or fully halogenated, a linear or branched alkoxy group having 1 to 20 C atoms that is not halogenated or partially or fully halogenated, and a linear or branched thioalkyl group having 1 to 20 C atoms that is not halogenated or partially or fully halogenated.; Claim 2 An ophthalmic device according to claim 1, wherein Y1 and Y0 are independently O or S, and at least one of Y1 and Y0 is S. Claim 3 An ophthalmic device according to claim 1, wherein in the compound of formula (I), formula (II), formula (III) or formula (IV) being polymerized, only one substituent R# is -[L]-R1 and the other substituent R# is R2, where [L], R1 and R2 have the meanings as indicated in claim 1. Claim 4 In paragraph 1, [L] is independently -(C(R)2) in each case o - and, an ophthalmic device having the meanings as indicated in paragraph 1. Claim 5 In claim 1, a constituent unit M based on formula (I), formula (II), formula (III), or formula (IV). 0 An ophthalmic device comprising an oligomer, polymer, or copolymer comprising, in each case of formula (I), formula (II), formula (III), or formula (IV), R1 is polymerized, and thus R1 forms a regioregular oligomer or polymer backbone, an alternating oligomer or polymer backbone, a regiorandom oligomer or polymer backbone, a statistical oligomer or polymer backbone, a block oligomer or polymer backbone, or a random oligomer or polymer backbone, or becomes part of a copolymer backbone. Claim 6 An ophthalmic device according to claim 5, wherein the polymerized group R1 is of formula (1-p), formula (2-p), formula (3-p) or formula (4-p): , , , . In the above formulas (1-p) to (4-p), the asterisk "*" in formulas (1-p) to (4-p) indicates a connection to an adjacent repeating unit within a polymer chain or oligomer chain or a connection to a terminal end group, and the asterisk "**" in formulas (1-p) to (4-p) indicates a connection to the remainder of formula (I), formula (II), formula (III), or formula (IV), and R5, R6, R7, X 11 and c have the meanings described in Paragraph 1. Claim 7 In paragraph 5, the above-mentioned constituent unit M 0 is the chemical formula (M 0 -Ia), chemical formula (M 0 -Ib), chemical formula (M 0 -Ic), chemical formula (M 0 -II-a), chemical formula (M 0 -II-b), chemical formula (M 0 -II-c), chemical formula (M 0 -III-a), chemical formula (M 0 -III-b), chemical formula (M 0 -III-c), chemical formula (M 0 -IV-a), chemical formula (M 0 -IV-b) or chemical formula (M 0 Ophthalmic device having -IV-c): , , , , , , , , , , , . The above chemical formula (M 0 -Ia) to (M 0 In -IV-c), R2, [L], X, Y0, Y1, R3, R4, R5, R6, R7, X 11 and c have the meanings described in paragraph 1, and the asterisk "*" indicates, in each case, a connection to an adjacent repeating unit within a polymer chain or oligomer chain or a connection to a terminal group. Claim 8 In claim 7, the at least one polymerizable compound of formula (I), formula (II), formula (III) or formula (IV), or formula (M 0 -Ia), chemical formula (M 0 -Ib), chemical formula (M 0 -Ic), chemical formula (M 0 -II-a), chemical formula (M 0 -II-b), chemical formula (M 0 -II-c), chemical formula (M 0 -III-a), chemical formula (M 0 -III-b), chemical formula (M 0 -III-c), chemical formula (M 0 -IV-a), chemical formula (M 0 -IV-b) or chemical formula (M 0 -IV-c) The above constituent unit M 0 In addition, styrene, ethoxyethyl methacrylate (EOEMA), methyl methacrylate (MMA), methyl acrylate, n-alkyl acrylate (wherein the n-alkyl group comprises 2 to 20 C atoms), n-alkyl methacrylate (wherein the n-alkyl group comprises 2 to 20 C atoms), i-alkyl acrylate (wherein the i-alkyl group comprises 3 to 20 C atoms), i-alkyl methacrylate (wherein the i-alkyl group comprises 3 to 20 C atoms), ethoxyethoxyethyl acrylate (EEEA), n -Hydroxyalkyl acrylate (the above) n - The alkyl group contains 2 to 10 C atoms), n -Hydroxyalkyl methacrylate (the above) n - The alkyl group comprises 2 to 10 C atoms), tetrahydrofuryl methacrylate (THFMA), glycidyl methacrylate (GMA), 16-hydroxyhexadecyl acrylate, 16-hydroxyhexadecyl methacrylate, 18-hydroxyoctadecyl acrylate, 18-hydroxyoctadecyl methacrylate, 2-phenoxyethyl acrylate (EGPEA), heptafluorobutyl acrylate, heptafluorobutyl methacrylate, hexafluorobutyl acrylate, hexafluorobutyl methacrylate, hexafluoroisopropyl acrylate, hexafluoroisopropyl methacrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate, pentafluoropropyl acrylate, pentafluoropropyl methacrylate, tetrafluoropropyl methacrylate, trifluoroethyl acrylate, trifluoroethyl methacrylate and An ophthalmic device comprising at least one additional polymerized monomer selected from the group consisting of ethylene glycol dimethacrylate. Claim 9 An ophthalmic device according to any one of claims 1 to 5, wherein the precursor article for manufacturing the ophthalmic device is a blank that can be modified into a contact lens, an eye implant, or an intraocular lens. Claim 10 A method for forming an ophthalmic device according to any one of claims 1 to 5, the method comprising: providing a composition comprising at least one compound of formula (I), formula (II), formula (III), or formula (IV) described in any one of claims 1 to 4 and / or an oligomer or polymer described in claim 5 having at least one reactive group left for polymerization, and optionally, additional monomers and / or crosslinking agents and / or UV absorbers and / or radical initiators different from the compound of formula (I), formula (II), formula (III), or formula (IV); and subsequently forming the ophthalmic device from said composition. Claim 11 A method for changing the optical properties of an ophthalmic device according to any one of claims 1 to 5, comprising: - providing an ophthalmic device according to any one of claims 1 to 5; and - subsequently exposing the ophthalmic device to irradiation having a wavelength of 200 nm or more and 1500 nm or less. Claim 12 An ophthalmic device obtainable by the method according to paragraph 11. Claim 13 A polymer comprising at least one polymerizable compound of formula (I), formula (II), formula (III) or formula (IV), wherein all substituents R# described in claim 1 contain a Si-containing group R1 to be polymerized, provided that silicates based on polymerizable compounds of formulas (I) and (IV) are excluded. Claim 14 In claim 13, in addition to the compound of formula (I), formula (II), formula (III) or formula (IV) polymerized above, styrene, ethoxyethyl methacrylate (EOEMA), methyl methacrylate (MMA), methyl acrylate, n-alkyl acrylate (wherein the n-alkyl group comprises 2 to 20 C atoms), n-alkyl methacrylate (wherein the n-alkyl group comprises 2 to 20 C atoms), i-alkyl acrylate (wherein the i-alkyl group comprises 3 to 20 C atoms), i-alkyl methacrylate (wherein the i-alkyl group comprises 3 to 20 C atoms), ethoxyethoxyethyl acrylate (EEEA), n -Hydroxyalkyl acrylate (the above) n - The alkyl group contains 2 to 10 C atoms), n -Hydroxyalkyl methacrylate (the above) n - The alkyl group comprises 2 to 10 C atoms), tetrahydrofuryl methacrylate (THFMA), glycidyl methacrylate (GMA), 16-hydroxyhexadecyl acrylate, 16-hydroxyhexadecyl methacrylate, 18-hydroxyoctadecyl acrylate, 18-hydroxyoctadecyl methacrylate, 2-phenoxyethyl acrylate (EGPEA), heptafluorobutyl acrylate, heptafluorobutyl methacrylate, hexafluorobutyl acrylate, hexafluorobutyl methacrylate, hexafluoroisopropyl acrylate, hexafluoroisopropyl methacrylate, octafluoropentyl acrylate, octafluoropentyl methacrylate, pentafluoropropyl acrylate, pentafluoropropyl methacrylate, tetrafluoropropyl methacrylate, trifluoroethyl acrylate, trifluoroethyl methacrylate and A polymer comprising at least one additional polymerized monomer selected from the group consisting of ethylene glycol dimethacrylate. Claim 15 A composition for polymerization comprising at least one compound of formula (I), formula (II), formula (III), or formula (IV) described in any one of claims 1 to 4, and / or a polymer according to claim 13 or 14 having at least one reactive group left for polymerization, and / or a crosslinking agent and / or a UV absorber and / or a radical initiator, and optionally an additional monomer different from the compound of formula (I), formula (II), formula (III), or formula (IV). Claim 16 Compounds of chemical formula (I), chemical formula (II), chemical formula (III) or chemical formula (IV): , , , . In the above formulas (I) to (IV), R# is independently -[L]-R1 or R2 in each case, provided that at least one R# is -[L]-R1; Y1 and Y0 are independently O or S; X is absent or C=O; R1 is a trialkoxysilyl group or a dialkoxyalkylsilyl group, or a silyl group of formula (1), formula (2), or formula (3), or a polymerizable group of formula (4), wherein the alkyl and / or alkoxy group is independently having 1 to 6 C atoms and is linear or branched: In the above chemical formulas (1) to (4), alkyl means, in each case independently, a linear or branched alkyl group having 1 to 6 C atoms, and the asterisk "*" indicates, in each case independently, a connection to the linker [L]; X 11 is selected from the group consisting of O, S, O-SO2, SO2-O, C(=O), OC(=O), C(=O)O, S(C=O) and (C=O)S, and R5, R6 and R7 are each independently selected from the group consisting of H, F, linear or branched unfluorinated or partially or fully fluorinated alkyl groups having 1 to 20 C atoms, and aryls having 6 to 14 C atoms, where c is each independently 0 or 1; [L] is each independently -(C(R)2) o - or -(C(R)2) p -X8-(C(R)2) q -(X9) s -(C(R)2) r -(X 10 ) t -(C(R)2) u - and; R is independently selected in each case from the group consisting of H, F, a linear or branched alkyl group having 1 to 4 C atoms, and a linear or branched partially or fully fluorinated alkyl group having 1 to 4 C atoms; o is selected from the group consisting of 1 to 20, and X8, X9, and X 10 is independently O, S, SO2, or NR0 in each case, s and t are 0 or 1, p and q are independently selected from the group consisting of 1 to 10 in each case, r and u are independently selected from the group consisting of 0 to 10 in each case, and -(C(R)2) p -X8-(C(R)2) q -(X9) s -(C(R)2) r -(X 10 ) t -(C(R)2) u The total number of atoms for - is 20 or fewer, and R0 is independently selected in each case from the group consisting of a linear or branched alkyl group having 1 to 4 C atoms and a linear or branched partially or completely fluorinated alkyl group having 1 to 4 C atoms; R2 is independently in each case H, a linear or branched non-halogenated or partially or completely halogenated alkyl group having 1 to 20 C atoms, a linear or branched non-halogenated or partially or completely halogenated alkoxyalkyl group having 2 to 20 C atoms, a cycloalkyl group having 3 to 7 C atoms, or a non-halogenated or partially or completely halogenated aryl group having 6 to 14 C atoms, said aryl group which can be substituted with one or more R'; R3 and R4 are independently in each case H, F, a linear or branched having 1 to 20 C atoms An alkyl group that is not halogenated or partially or completely halogenated, a cycloalkyl group having 3 to 7 C atoms, an aryl group that is not halogenated or partially or completely halogenated having 6 to 14 C atoms, said aryl group that can be substituted with one or more R's, or a heteroaryl group having 5 to 14 C atoms, said heteroaryl group that can be substituted with one or more R's;R' is independently selected in each case from the group consisting of F, SF5, CN, SO2CF3, a linear or branched alkyl group having 1 to 20 C atoms that is not halogenated or partially or fully halogenated, a cycloalkyl group having 3 to 6 C atoms that is not halogenated or partially or fully halogenated, a linear or branched alkoxy group having 1 to 20 C atoms that is not halogenated or partially or fully halogenated, and a linear or branched thioalkyl group having 1 to 20 C atoms that is not halogenated or partially or fully halogenated, provided that in the case of a compound of formula (II) in which R# in XR# is [L]-R1, X is absent and [L] is -(C(R)2; o - and Y0-R# is S-R2, R2 is H, and c is 1; provided that in the case of a compound of formula (III) in which R# in Y0-R# is [L]-R1, R# in XR# is R2, R3 is F, and R1 is a polymerizable group of formula (4), and R5, R6 and R7 are each independently selected from the group consisting of H, F, and linear or branched alkyl groups having 1 to 20 C atoms that are not fluorinated or partially or fully fluorinated; provided that in the case of a compound of formula (IV) in which R# in both Y1-R# and Y0-R# is [L]-R1, R1 is independently selected from a silyl group of formula (1), formula (2) or formula (3), and a polymerizable group of formula (4).

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