Oligomeric binaphthalene compound and thermoplastic resin

Abstract

The present invention relates to oligomeric binaphthalene compounds of formula (I) which are suitable as monomers for the preparation of thermoplastic resins, such as polycarbonate resins, which have beneficial optical and mechanical properties and can be used in the production of optical devices. # imgabs 0 # wherein X1 and X2 are independently selected from the group consisting of hydrogen,-Alk1-OH,-CH2-A2-CH2-OH,-Alk2-C (O) ORx,-CH2-A2-C (O) ORx, and-C (O)-A2-C (O) ORx wherein Rx is selected from the group consisting of hydrogen, phenyl, benzyl, and C1-C4-alkyl; y1 and Y2 are independently selected from the group consisting of-CH2-,-CHArY-, and-CH (CH2ArY)-; a1 is, for example, a single bond,-CH2-,-CHArA-CH (CH2ArA)-,-C (CH2ArA) 2-, a moiety of formula (A), a monocyclic or polycyclic arylene group having 6 to 26 carbon atoms as ring members, or a monocyclic or polycyclic heteroarylene group having a total of 5 to 26 atoms as ring members, or the moiety-Y1-A1-Y2-in formula (I) may be-CH2-or-CHArY-, n is 1, 2 or 3; m, p, q and r are independently 0, 1 or 2; r1, R2, R3 and R4 are independently selected from the group consisting of halogen, C2-C3-alkynyl, CN, R, OR, CHsR '3-s, NR2, C (O) R and CH = CHR ", R1, R2, R3 or R4 may be the same or different if more than one R1, R2, R3 or R4 is present, where s is 0, 1 or 2 at each occurrence.

Description

Technical Field

[0001] The present invention relates to oligomeric binaphthyl compounds which are suitable as monomers for preparing thermoplastic resins, such as polycarbonate resins, which have beneficial optical and mechanical properties and are useful in the production of optical devices. Background Art

[0002] Optical devices, such as optical lenses, made of optical resins instead of optical glass are advantageous in that they can be mass-produced by injection molding. Today, optical resins, particularly transparent polycarbonate resins, are often used to produce camera lenses. In this regard, resins with a higher refractive index are very desirable because they allow the size and weight of the final product to be reduced. Generally, when an optical material with a higher refractive index is used, a lens element with the same refractive power can be realized with a surface having a smaller curvature, thereby reducing the amount of aberrations generated on the surface. As a result, the number of lenses can be reduced to reduce the decentering sensitivity of the lens and / or to reduce the thickness of the lens, thereby achieving lightweighting.

[0003] US 9,360,593 describes polycarbonate resins having repeating units derived from binaphthyl monomers of the following formula (A):

[0004]

[0005] wherein Y is a C1-C4-alkanediyl group, in particular 1,2-ethylenediyl. Polycarbonate resins are said to have beneficial optical properties in terms of high refractive index, low Abbe number, high transparency, low birefringence and a glass transition temperature suitable for injection molding.

[0006] Copolycarbonates of monomers of formula (A) and 10,10-bis(4-hydroxyphenyl)anthrone monomers and their use in preparing optical lenses are described in US 2016 / 0319069.

[0007] WO2019 / 043060 describes a thermoplastic resin for producing an optical material, wherein the thermoplastic resin comprises a polymeric compound of formula (B)

[0008]

[0009] in

[0010] X is, for example, C2-C4-alkanediyl;

[0011] R and R' are the same or different and are selected from an optionally substituted monocyclic or polycyclic aryl group having 6 to 36 carbon atoms and an optionally substituted monocyclic or polycyclic heteroaryl group having a total of 5 to 36 atoms.

[0012] However, as observed by the inventors of the present application, despite having a variety of advantages, binaphthyl derived monomers (e.g., monomers of formulas A and B above) also have the disadvantage that when used as monomers in the production of thermoplastic resins (e.g., the production of polyesters and polycarbonates), they form a large number of undesirable cyclic oligomers. These cyclic oligomers may exacerbate the increase in molecular weight and / or deteriorate the product properties of the resin, such as reducing mechanical strength, reducing glass transition temperature and / or optical properties. Unfortunately, these cyclic components are difficult to remove from the resin in an effective manner. In order to reduce the formation of such cyclic compounds, it is usually necessary to polymerize the binaphthyl-containing monomers with a relatively large amount of comonomers.

[0013] Without being bound by theory, it is speculated that the reason for the increased formation of cyclic compounds when using these monomers is related to their flexible linking units (see the -Y-OH and -X-OH parts in Formulas A and B) and the close spatial proximity of the 1- and 1'-positions of the naphthyl residues to which these linking groups are attached. Summary of the invention

[0014] The present inventors have now discovered that these problems can be alleviated by compounds of formula (I) described below. The use of compounds of formula (I) as monomers to produce thermoplastic resins, particularly polycarbonates, will produce resins with reduced undesirable cyclic oligomer content and / or higher molecular weight and higher refractive index, thereby having improved optical properties and / or improved mechanical properties.

[0015] Therefore, a first aspect of the present invention relates to the use of a compound of formula (I) or a mixture thereof as a monomer for the production of thermoplastic resins, in particular for the production of polyesters, in particular for the production of polycarbonates.

[0016]

[0017] in

[0018] X 1 and X 2 are independently selected from hydrogen, -Alk 1 -OH, -CH2-A 2 -CH2-OH, -Alk 2 -C(O)OR x 、-CH2-A 2 -C(O)OR x and -C(O)-A 2 -C(O)OR x , where R x is selected from hydrogen, phenyl, benzyl and C1-C4-alkyl;

[0019] Y 1 and Y 2Independently selected from -CH2-, -CHAr Y - and -CH(CH2Ar Y )-;

[0020] A 1 Selected from single bond, -CH2-, -CHAr A -、-CH(CH2Ar A )-、-C(CH2Ar A )2-, moieties of formula (A), monocyclic or polycyclic arylene groups having 6 to 26 carbon atoms as ring members and monocyclic or polycyclic heteroarylene groups having a total of 5 to 26 atoms as ring members, wherein 1, 2, 3 or 4 of these ring member atoms of the heteroarylene group are selected from nitrogen, sulfur and oxygen, and the remaining atoms of these ring member atoms of the heteroarylene group are carbon atoms, wherein the monocyclic or polycyclic arylene groups and the monocyclic or polycyclic heteroarylene groups are unsubstituted or carry 1, 2, 3 or 4 R Ar Group,

[0021]

[0022] in

[0023] Q represents a single bond, O, C=O, CH2, S or SO2;

[0024] R 5a , R 5b are independently selected from hydrogen, fluorine, CN, R, OR, CH k R'3-k, NR2, C(O)R and C(O)NH2, wherein k is 0, 1 or 2; and

[0025] * indicates the same as Y 1 or Y 2 The connection point;

[0026] Alternatively, the moiety -Y in formula (I) 1 -A 1 -Y 2 - can be -CH2- or -CHAr Y -,

[0027] n is 1, 2 or 3;

[0028] R 1 , R 2 , R 3 and R 4 independently selected from halogen, C2-C3-alkynyl, CN, R, OR, CH s R' 3-s , NR2, C(O)R and CH=CHR", if more than one R 1 , R2 , R 3 or R 4 If exists, then R 1 , R 2 , R 3 or R 4 can be the same or different, where s is 0, 1, or 2 each time it occurs;

[0029] m, p, q and r are independently 0, 1 or 2;

[0030] A 2 Selected from phenylene, naphthylene and biphenylylene;

[0031] Alk 1 is C2-C4-alkanediyl;

[0032] Alk 2 is C1-C4-alkanediyl;

[0033] Ar Y and Ar A is chosen from monocyclic or polycyclic aryl radicals having 6 to 26 carbon atoms as ring atoms and monocyclic or polycyclic heteroaryl radicals having a total of 5 to 26 atoms as ring members, wherein 1, 2, 3 or 4 of these ring member atoms of the heteroaryl radical are chosen from nitrogen, sulfur and oxygen, and the remaining atoms of these ring member atoms of the heteroaryl radical are carbon atoms, wherein Ar Y and Ar A Unsubstituted or replaced by 1, 2 or 3 R Ar group substitution;

[0034] R Ar Selected from R, OR, CH t R' 3-t , NR2 and CH=CHR", where if more than one R is present on the same (hetero)aryl or (hetero)arylene group Ar , then R Ar can be the same or different, where t is 0, 1, or 2 each time it occurs;

[0035] R is selected from C1-C4-alkyl, phenyl, naphthyl, phenanthrenyl and triphenylenyl, wherein phenyl, naphthyl, phenanthrenyl and triphenylenyl are unsubstituted or substituted by 1, 2, 3 or 4 identical or different R'" groups;

[0036] R' is selected from phenyl, naphthyl, phenanthrenyl and triphenylene, wherein phenyl, naphthyl, phenanthrenyl and triphenylene are unsubstituted or substituted with 1, 2, 3 or 4 identical or different R'" groups;

[0037] R" is selected from hydrogen, methyl, phenyl and naphthyl, wherein phenyl and naphthyl are unsubstituted or substituted with 1, 2, 3 or 4 identical or different R'" groups;

[0038] R'" is selected from phenyl, OCH3, CH3, N(CH3)2 and C(O)CH3.

[0039] The compounds of formula (I) are novel, except those compounds of formula (I) wherein X 1 and X 2 are all hydrogen or -CH2CH2-OH, Y 1 and Y 2 Both are CH2, and A 1 is a single bond or CH2; and except for those compounds of formula (I) below, wherein n is 1, X 1 and X 2 All are hydrogen, Y 1 and Y 2 are all CH2, m, p, q and r are all 0, and A 11,2-phenylene, 1,3-phenylene, 1,6-pyrenylene, 4,4'-biphenylene, 2,6-pyridinylene, 4,4"-terphenylene, 2,5-[1,3,4]-thiadiazolylene, 2,5-[1,3,4]-oxadiazolylene, 2,5 -thienediyl-bis(4,1-phenylenemethylene), 9,9-diethyl-2,7-9H-fluorenylene, 10-methyl-3,7-phenothiazinylene or 10-ethyl-3,7-phenothiazinylene. These compounds are known from ARAbreu et al., Terahedron 2010, 66(3), 743-749; SC Jha et al., Synthetic Communications 2003, 33(6), 1005-1009; F. De Jong et al., Journal of the Chemical Society, Chemical Communications 1975, 14, 551-553; EP Kyba et al., Journal of Organic Chemistry 1977, 42(26), 4173-4184; DE 2414188A1; ARAbreu et al., Journal of Molecular Catalysis A; Chemical 2010, 325(1-2), 91-97; G. Gao et al., European Journal of Organic Chemistry 2011, 2011(26), 5039-5046; DE2539324A1; JP 2015129266 A; H. Egami et al., Journal of the American Chemical Society 2018, 140(8), 2785-2788; F. Peixoto et al., Current Organic Synthesis 2014, 11(2), 301-309; A. R. A. Breu et al., Chemistry Letters 2013, 42(1), 37-39; GWGokel et al., Journal of the Chemical Society, Chemical Communications 1975, (11), 444-446; K. Takaishi et al., Journal of the American Chemical Society 2020, 142(4), 1774-1779; HK Matsui et al., Bulletin of the Chemical Society of Japan 2000,73(4),991-997; K.Ogura, Tetrahedron Letters 1999,40(51),9065-9068; P.Rajakumar et al., Supramolecular Chemistry 2009,21(8),674-680; R.Kanagalatha et al., Asian Journal of Chemistry 2015,27(12),4373-4378; R.Sebastian et al., Journal of HeterocyclicChemistry 2016, 53(3), 993-996; A. Thirunarayanan et al., RSC Advances 2014, 4(45), 23433-23439; and P. Rajakumar et al., Tetrahedron 2001, 57(48), 9749-9754. .

[0040] Therefore, the second aspect relates to novel compounds of formula (I). In other words, the second aspect relates to compounds of formula (I), except for those compounds of formula (I) wherein X 1 , X 2 , Y 1 , Y 2 and Ar 1 The combination is as follows:

[0041] X 1 and X 2 are all hydrogen or -CH2CH2-OH, Y 1 and Y 2 Both are CH2, and A 1 is a single bond or CH2;

[0042] and except for those compounds of formula (I) wherein n, m, p, q, r, X 1 , X 2 , Y 1 , Y 2 and Ar 1The combination is as follows:

[0043] n is 1, X 1 and X 2 All are hydrogen, Y 1 and Y 2 are all CH2, m, p, q and r are all 0, and A 1 It is 1,2-phenylene, 1,3-phenylene, 1,6-pyrenylene, 4,4'-biphenylene, 2,6-pyridylene, 4,4"-m-terphenylene, 2,5-[1,3,4]-thiadiazolylene, 2,5-[1,3,4]-oxadiazolyl, 2,5-thiophenediyl-bis(4,1-phenylenemethylene), 9,9-diethyl-2,7-9H-fluorenyl, 10-methyl-3,7-phenothiazinyl or 10-ethyl-3,7-phenothiazinyl.

[0044] The third aspect relates to a thermoplastic resin comprising a polymerized unit of a compound of formula (I), that is, a thermoplastic resin comprising a structural unit represented by the following formula (III);

[0045]

[0046] in

[0047] # indicates the connection point with the adjacent structural unit;

[0048] And where X 1a and X 2a Derived from X in formula (I) 1 or X 2 , if X 1 or X 2 is hydrogen, by replacing the hydrogen with a single bond, or if X 1 or X 2 is not hydrogen, then by replacing X 1 or X 2 -OH or -OR x The group is replaced by an oxo (-O-) unit, and wherein X 1 , X 2 , Y 1 , Y 2 , A 1 , R 1 , R 2 , R 3 , R 4 , n, m, p, q and r are as defined above.

[0049] The invention also relates to an optical device made of a thermoplastic resin as defined above, in particular of a polyester and in particular of a polycarbonate. DETAILED DESCRIPTION

[0050] Due to the restricted rotation along the bond between the naphthalene units, the compounds of formula (I) may have axial chirality, and thus the compounds of formula (I) may be arranged in at least 2 (n+1) The invention can be present in the form of one of the three stereoisomers, or in the form of any mixture of these stereoisomers, wherein n is a variable given in formula (I). Specific examples of these mixtures are those belonging to at least 2 n The invention relates to the pure stereoisomers of the compounds of formula (I) and to any mixtures of stereoisomers, including racemic and non-racemic mixtures of the two stereoisomers, which together constitute an enantiomeric pair.

[0051] For the purposes of the present invention, the term "C1-C4-alkanediyl" may also be referred to alternatively as "alkylene having 1, 2, 3 or 4 carbon atoms" and refers to a divalent saturated aliphatic hydrocarbon radical having 1, 2, 3 or 4 carbon atoms. Examples of C1-C4-alkanediyl are in particular methylene (CH2), straight-chain alkanediyl such as 1,2-ethanediyl (CH2CH2), 1,3-propylenediyl (CH2CH2CH2) and 1,4-butanediyl (CH2CH2CH2CH2), but also branched alkanediyl such as 1-methyl-1,2-ethanediyl, 1-methyl-1,2-propylenediyl, 2-methyl-1,2-propylenediyl, 2-methyl-1,3-propylenediyl and 1,3-butanediyl.

[0052] For the purposes of the present invention, the term "monocyclic aryl" refers to a monovalent aromatic monocyclic radical, such as in particular phenyl.

[0053] For the purposes of the present invention, the term "monocyclic heteroaryl" refers to a monovalent heteroaromatic monocyclic radical, i.e. a heteroaromatic monocyclic ring which is linked to the rest of the molecule by a single covalent bond, wherein the ring member atoms are part of a conjugated π-electron system, wherein the heteroaromatic monocyclic ring has 5 or 6 ring atoms, which include 1, 2, 3 or 4 nitrogen atoms or 1 oxygen atom and 0, 1, 2 or 3 nitrogen atoms or 1 sulfur atom and 0, 1, 2 or 3 nitrogen atoms as heteroring members, wherein the remaining ring atoms are carbon atoms. Examples include furyl (=furanyl), pyrrolyl (=1H-pyrrolyl), thienyl (=thiophenyl), imidazolyl (=1H-imidazolyl), pyrazolyl (=1H-pyrazolyl), 1,2,3-triazolyl, 1,2,4-triazolyl, tetrazolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, 1,3,4-oxadiazolyl, 1,3,4-thiadiazolyl, pyridyl (=pyridinyl), pyrazinyl, pyridazinyl, pyrimidinyl and triazinyl.

[0054] For the purposes of the present invention, the term "monocyclic or polycyclic aromatic group" refers to a monovalent aromatic monocyclic radical as defined herein, or to a monovalent aromatic polycyclic radical, i.e. a polycyclic aromatic hydrocarbon linked to the rest of the molecule by a single covalent bond, wherein the polycyclic aromatic hydrocarbon is

[0055] (i) aromatic polycyclic hydrocarbons, i.e. fully unsaturated polycyclic hydrocarbon radicals in which each carbon atom is part of a conjugated π-electron system,

[0056] (ii) a polycyclic hydrocarbon having at least one benzene ring fused to a saturated or unsaturated 4- to 10-membered monocyclic or bicyclic hydrocarbon ring,

[0057] (iii) Polycyclic hydrocarbons having at least two benzene rings which are linked to each other by covalent bonds or are directly fused to each other and / or to a saturated or unsaturated 4- to 10-membered monocyclic or bicyclic hydrocarbon ring.

[0058] Monocyclic or polycyclic aryl has 6 to 26, typically 6 to 24, for example 6, 9, 10, 12, 13, 14, 16, 17, 18, 19, 20, 22 or 24 carbon atoms as ring atoms, in particular 6 to 20 carbon atoms, in particular 6, 10, 12, 13, 14, 16, 17 or 18 carbon atoms. Polycyclic aryl usually has 10 to 26, in particular 10 to 20, in particular 10, 12, 13, 14, 16, 17 or 18 carbon atoms as ring atoms.

[0059] In this context, polycyclic aromatic radicals with 2, 3 or 4 benzene rings linked to one another by single bonds include, for example, biphenyl and terphenylyl. Polycyclic aromatic radicals with 2, 3 or 4 benzene rings directly fused to one another include, for example, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, triphenylene, Polycyclic aromatic radicals with 2, 3 or 4 benzene rings fused to a saturated or unsaturated 4- to 10-membered monocyclic or bicyclic hydrocarbon ring include, for example, 9H-fluorenyl, biphenylenyl, tetraphenylenyl, acenaphthenyl (1,2-dihydroacenaphthenyl), acenaphthylenyl, 9,10-dihydroanthracene-1- 1,2,3,4-tetrahydrophenanthrenyl, 5,6,7,8-tetrahydrophenanthrenyl, cyclopenta[fg]acenaphthenyl, phenalenyl, fluoranthenyl, benzo[k]fluoranthenyl, perylenyl, 9,10-dihydro-9,10[1',2']-benzanthryl, dibenzo[a,e][8]annulenyl, 9,9'-spiro[9H-fluorenyl]yl and spiro[1H-cyclobuta[de]naphthyl-1,9'-[9H]fluorenyl]yl.

[0060] Monocyclic or polycyclic aromatic groups include, by way of example, phenyl, naphthyl, 9H-fluorenyl, phenanthrenyl, anthracenyl, pyrenyl, 1,2-dihydroacenaphthenyl, 1,2,3,4-dihydrophenanthrenyl, 1,2,3,4-tetrahydrophenanthrenyl, 5,6,7,8-tetrahydrophenanthrenyl, 1,2-dihydroacenaphthenyl, 1,2-dihydroacenaphthenyl, 1,2,3,4-dihydrophenanthren ... yl), phenanthrenylphenyl, anthracenylphenyl, pyrenylphenyl, 9H-fluorenylphenyl, di(naphthyl)phenyl, naphthylenebiphenyl, tri(phenyl)phenyl, tetra(phenyl)phenyl, pentaphenyl(phenyl), phenylnaphthyl, binaphthyl, phenanthrenylnaphthyl, pyrenylnaphthyl, phenylanthracenyl, biphenylanthracenyl, naphthylanthracenyl, phenanthrenylanthracenyl, dibenzo[a,e][8]annulyl, 9,10-dihydro-9,10[1',2']benzanthryl, 9,9'-spirobi-9H-fluorenyl and spiro[1H-cyclobut[de]naphthalene-1,9'-[9H]fluorenyl]yl.

[0061] For the purposes of the present invention, the term "monocyclic or polycyclic heteroaryl" refers to a monovalent heteroaromatic monocyclic radical as defined herein, or to a monovalent heteroaromatic polycyclic radical, i.e. a polycyclic heteroarene linked to the rest of the molecule by a single covalent bond, wherein

[0062] (i) a polycyclic heteroaromatic hydrocarbon having a heteroaromatic monocyclic ring as defined above and at least one, for example 1, 2, 3, 4 or 5, further aromatic rings selected from phenyl and a heteroaromatic monocyclic ring as defined above, wherein the aromatic rings of the polycyclic heteroaromatic hydrocarbon are linked to each other by covalent bonds and / or are directly fused to each other and / or to a saturated or unsaturated 4- to 10-membered monocyclic or bicyclic hydrocarbon ring, or

[0063] (ii) polycyclic heteroaromatic hydrocarbons carrying at least one saturated or partially or completely unsaturated 5-, 6-, 7- or 8-membered heterocyclic ring carrying 1, 2 or 3 heteroatoms selected from oxygen, sulfur and nitrogen as ring atoms, for example 2H-pyran, 4H-pyran, thiopyran, 1,4-dihydropyridine, 4H-1,4-oxazine, 4H-1,4-thiazine, 1,4-dioxin, oxepin, thiophene, dioxin, dithiophene, dithiophene, dioxocin ... dioxocine), dithiocine, and at least one, for example 1, 2, 3, 4 or 5, aromatic rings selected from phenyl and heteroaromatic monocyclic rings as defined above, wherein at least one aromatic ring is directly fused to a saturated or partially unsaturated 5- to 8-membered heterocyclic ring, and wherein the aromatic rings of the polycyclic heteroaromatic hydrocarbons are linked to each other by covalent bonds or are directly fused to each other and / or to a saturated or unsaturated 4- to 10-membered monocyclic or bicyclic hydrocarbon ring.

[0064] Monocyclic or polycyclic heteroaryl groups have 5 to 26, usually 5 to 24, in particular 5 to 20 ring atoms, including 1, 2, 3 or 4 atoms selected from nitrogen atoms, sulfur atoms and oxygen atoms, wherein the remaining atoms in the ring atoms are carbon atoms. Polycyclic heteroaryl groups usually have 9 to 26, usually 9 to 24, in particular 9 to 20 ring atoms, including 1, 2, 3 or 4 atoms selected from nitrogen atoms, sulfur atoms and oxygen atoms, wherein the remaining atoms in the ring atoms are carbon atoms.

[0065] Examples of polycyclic heteroaryl groups include, but are not limited to, benzofuranyl, benzothienyl, dibenzofuranyl (=dibenzo[b,d]furanyl), dibenzothienyl (=dibenzo[b,d]thienyl), naphthofuranyl, naphthothienyl, furano[3,2-b]furanyl, furano[2,3-b]furanyl, furano[3,4-b]furanyl, thieno[3,2-b]thienyl, thieno[2,3-b]thienyl, thieno[3,4-b]thienyl, oxanthrenyl, thianthrenyl, indolyl (=1H-indolyl), isoindolyl (=2H-isoindolyl), carbazolyl, indolizinyl, yl), benzopyrazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, benzo[c,d]indolyl, 1H-benzo[g]indolyl, quinolyl, isoquinolyl, acridinyl, phenazinyl, quinazolinyl, quinoxalinyl, phenoxazinyl, phenothiazinyl, benzo[b][1,5]naphthyridinyl, cinnolinyl, 1,5-naphthyridinyl, 1,8-naphthyridinyl, phenylpyrrolyl, naphthylpyrrolyl, dipyridyl, phenylpyridinyl, naphthylpyridinyl, pyrido[4,3-b]indolyl, pyrido[3,2-b]indolyl, pyrido[3,2-g]quinolyl, pyrido[2,3-b][1,8]naphthyridinyl, pyrrolo[3,2-b]pyridinyl, pteridinyl, purinyl, 9H- xanthene, 9H-thioxanthenyl, 2H-chromenyl, 2H-thiochromenyl, phenanthridinyl, phenanthrolinyl, benzo[1,2-b:4,3-b']bifuranyl, benzo[1,2-b:6,5-b']bifuranyl, benzo[1,2-b:5,4-b']bifuranyl, benzo[1,2-b:4,5-b']bifuranyl, naphthofuranoyl pyranyl, benzo[b]naphtho[1,2-d]furanyl, benzo[b]naphtho[2,3-d]furanyl, benzo[b]naphtho[2,1-d]furanyl, tribenzo[b,d,f]oxepinyl, dibenzo[b,d]thienyl, naphtho[1,2-b]thienyl, naphtho[2,3-b]thienyl, naphtho[2,1-b]thien ... benzo[b]naphtho[1,2-d]thienyl, benzo[b]naphtho[2,3-d]thienyl, benzo[b]naphtho[2,1-d]thienyl, 6H-dibenzo[b,d]thiopyranyl, 5H,9H-[1]benzothiopyrano[5,4,3-c,d,e][2]benzothiopyranyl, 5H,10H-[1]benzothiopyrano[5,4, 3-c,d,e][2]benzothiopyranyl, benzo[1,2-b:4,3-b']bithienyl, benzo[1,2-b:6,5-b']bithienyl, benzo[1,2-b:5,4-b']bithienyl, benzo[1,2-b:4,5-b']bithienyl, 1,4-benzodithiinyl, naphtho[1,2-b][1,4]dithianyl, naphtho[2,3-b][1,4]dithianyl, thianthrenyl, benzo[a]thianthrenyl, benzo[b]thianthrenyl, dibenzo[a,c]thianthrenyl, dibenzo[a,h]thianthrenyl, dibenzo[a,i]thianthrenyl, dibenzo[a,j]thianthrenyl, dibenzo[b,i]thianthrenyl, 2H-naphtho[1,8-b,c]thienyl, 5H-phenanthrene 1,4-Dibenzo[b,d]thiophene, 1,2-Dibenzo[b,f]thiophene, 1,6-Dibenzo[b,d]thiophene, 1,2-Dibenzo[b,f]thiophene, 1,2-Dibenzo[b,d]thiophene, 1,2-Dibenzo[d,f][1,3]dithiophene, 1,2-Dibenzo[b,d,f]thiophene, 1,2-Dibenzo[3,4-c, d]thieno[2,3,4-j,k][2]benzothiepinyl, dinaphtho[1,8-bc:1',8'-f,g][1,5]dithiocinyl, furano[3,2-g]quinolyl, furano[2,3-g]quinolyl, furano[2,3-g]quinoxalinyl, benzo[g]chromenyl, thieno[3,2-f [1]benzothiophenyl, thieno[2,3-f][1]benzothiophenyl, thieno[3,2-g]quinolyl, thieno[2,3-g]quinolyl, thieno[2,3-g]quinoxalinyl, benzo[g]thiochromenyl, pyrrolo[3,2,1-h,i]indolyl, benzo[g]quinoxalinyl, benzo[f]quinoxalinyl and benzo[h]isoquinolyl. ,

[0066] For the purposes of the present invention, the term "monocyclic arylene" refers to a divalent aromatic monocyclic radical, such as, in particular, phenylene.

[0067] For the purposes of the present invention, the term "monocyclic heteroarylene" refers to a divalent heteroaromatic monocyclic radical, i.e. a heteroaromatic monocyclic ring which is connected to two remaining parts of the molecule by two single covalent bonds, wherein the ring member atoms are part of a conjugated π-electron system, wherein the heteroaromatic monocyclic ring has 5 or 6 ring atoms, which include 1, 2, 3 or 4 nitrogen atoms or 1 oxygen atom and 0, 1, 2 or 3 nitrogen atoms or 1 sulfur atom and 0, 1, 2 or 3 nitrogen atoms as heteroring members, wherein the remaining ring atoms are carbon atoms. Examples include furylene (= furanylene), pyrrolylene (= 1H-pyrrolylene), thienylene (= thiophenylene), imidazolylene (= 1H-imidazolylene), pyrazolylene (= 1H-pyrazolylene), 1,2,3-triazolylene, 1,2,4-triazolylene, tetrazolylene, oxazolylene , thiazolylene, isoxazolylene, isothiazolylene, 1,3,4-oxadiazolylene, 1,3,4-thiadiazolylene, pyridylene (= pyridinylene), pyrazinylene, pyridazinylene, pyrimidinylene and triazinylene.

[0068] For the purposes of the present invention, the term "monocyclic or polycyclic arylene" refers to a divalent aromatic monocyclic radical or a divalent aromatic polycyclic radical as defined herein, i.e. a polycyclic aromatic hydrocarbon linked to two other parts of the molecule by two single covalent bonds, wherein the polycyclic aromatic hydrocarbon is

[0069] (i) aromatic polycyclic hydrocarbons, i.e. fully unsaturated polycyclic hydrocarbon radicals in which each carbon atom is part of a conjugated π-electron system,

[0070] (ii) a polycyclic hydrocarbon having at least one benzene ring fused to a saturated or unsaturated 4- to 10-membered monocyclic or bicyclic hydrocarbon ring,

[0071] (iii) Polycyclic hydrocarbons having at least two benzene rings which are linked to each other by covalent bonds or are directly fused to each other and / or to a saturated or unsaturated 4- to 10-membered monocyclic or bicyclic hydrocarbon ring.

[0072] Monocyclic or polycyclic arylene has 6 to 26, typically 6 to 24, for example 6, 9, 10, 12, 13, 14, 16, 17, 18, 19, 20, 22 or 24 carbon atoms as ring atoms, in particular 6 to 20, in particular 6, 10, 12, 13, 14, 16, 17 or 18 carbon atoms. Polycyclic arylene usually has 10 to 26, in particular 10 to 20, in particular 10, 12, 13, 14, 16, 17 or 18 carbon atoms as ring atoms.

[0073] In this context, polycyclic arylene groups having 2, 3 or 4 benzene rings linked to one another by single bonds include, for example, biphenylene and terphenylene. Polycyclic arylene groups having 2, 3 or 4 benzene rings directly fused to one another include, for example, naphthylene, anthracenylene, phenanthrenylene, pyrenylene, triphenylen ... Chrysenylene and benzo[c]phenanthrenylene. Polycyclic arylene groups with 2, 3 or 4 benzene rings fused to a saturated or unsaturated 4- to 10-membered monocyclic or bicyclic hydrocarbon ring include, for example, 9H-fluorenylene, biphenylenylene, tetraphenylenylene, acenaphthenylene (1,2-dihydroacenaphthenylene), acenaphthylenylene, 9,10-dihydroanthracen-1-ylene, 1,2,3,4-tetrahydrophenanthrenylene, 5,6,7,8-tetrahydrophenanthrenylene, cyclopent[fg]acenaphthylenylene, phenanthrenylene phenalenylene, fluoranthenylene, benzo[k]fluoranthenylene, perylenylene, 9,10-dihydro-9,10[1',2']-benzenoanthracenylene, annulenylene, 9,9'-spirobi[9H-fluoren]ylene, and spiro[1H-cyclobuta[de]naphthalene-1,9'-[9H]fluoren]ylene.

[0074] The monocyclic or polycyclic arylene group includes, for example, phenylene, naphthylene, 9H-fluorenylene, phenanthrenylene, anthracenylene, pyrenylene, 1,2-dihydro-1H-indenyl, 1,2,3,4-dihydro-1H-phenanthrenyl, 1,2,3,4-dihydro-2 ... enylene), perylene, biphenylene, terphenylene, naphthylphenylene, phenanthrylphenylene, anthracenylphenylene, pyrenylphenylene, 9H-fluorenylphenylene, di(naphthylen)phenylene, naphthylbiphenylene, tri(phenyl)phenylene, tetra(phenyl)phenylene, pentaphenyl(phenylene), phenylnaphthylene, binaphthylene, phenanthrylnaphthylene, pyrenylnaphthylene, phenylanthracenylene, biphenylanthracenylene phenylanthracenylene), naphthalenylanthracenylene, phenanthrylanthracenylene, dibenzo[a,e][8]annulenylene, 9,10-dihydro-9,10[1',2']benzanthrylene, 9,9'-spirobi-9H-fluorenylene and spiro[1H-cyclobut[de]naphthalene-1,9'-[9H]fluorenyl]ylene.

[0075] For the purposes of the present invention, the term "monocyclic or polycyclic heteroarylene" refers to a divalent heteroaromatic monocyclic radical as defined herein, or to a divalent heteroaromatic polycyclic radical, i.e. a polycyclic heteroarene linked to two other parts of the molecule by two single covalent bonds, wherein

[0076] (i) a polycyclic heteroaromatic hydrocarbon having a heteroaromatic monocyclic ring as defined above and at least one, for example 1, 2, 3, 4 or 5, further aromatic rings selected from phenyl and a heteroaromatic monocyclic ring as defined above, wherein the aromatic rings of the polycyclic heteroaromatic hydrocarbon are linked to each other by covalent bonds and / or are directly fused to each other and / or to a saturated or unsaturated 4- to 10-membered monocyclic or bicyclic hydrocarbon ring, or

[0077] (ii) polycyclic heteroaromatic hydrocarbons carrying at least one saturated or partially or completely unsaturated 5-, 6-, 7- or 8-membered heterocyclic ring carrying 1, 2 or 3 heteroatoms selected from oxygen, sulfur and nitrogen as ring atoms, for example 2H-pyran, 4H-pyran, thiopyran, 1,4-dihydropyridine, 4H-1,4-oxazine, 4H-1,4-thiazine, 1,4-dioxin, oxepin, thiophene, dioxin, dithiophene, dithiophene, dioxocin ... dioxocine), dithiocine, and at least one, for example 1, 2, 3, 4 or 5, aromatic rings selected from phenyl and heteroaromatic monocyclic rings as defined above, wherein at least one aromatic ring is directly fused to a saturated or partially unsaturated 5- to 8-membered heterocyclic ring, and wherein the aromatic rings of the polycyclic heteroaromatic hydrocarbons are linked to each other by covalent bonds or are directly fused to each other and / or to a saturated or unsaturated 4- to 10-membered monocyclic or bicyclic hydrocarbon ring.

[0078] The monocyclic or polycyclic heteroarylene group has 5 to 26, usually 5 to 24, especially 5 to 20 ring atoms, including 1, 2, 3 or 4 atoms selected from nitrogen atoms, sulfur atoms and oxygen atoms, wherein the remaining atoms in the ring atoms are carbon atoms. The polycyclic heteroaryl group usually has 9 to 26, usually 9 to 24, especially 9 to 20 ring atoms, including 1, 2, 3 or 4 atoms selected from nitrogen atoms, sulfur atoms and oxygen atoms, wherein the remaining atoms in the ring atoms are carbon atoms.

[0079] Examples of polycyclic heteroarylene groups include, but are not limited to, benzofurylene, benzothienylene, dibenzofuranylene (= dibenzo[b,d]furanylene), dibenzothienylene (= dibenzo[b,d]thienylene), naphthofurylene, naphthiothienylene, furanylene, furo[3,2-b]furanylene, furo[2,3-b]furanylene, furo[3,4-b]furanylene, thieno[3,2-b]thienylene, thieno[2,3-b]thienylene, thieno[3,4-b]thienylene, oxanthrenylene ), thianthrenylene, indolylene (=1H-indolylene), isoindolylene (=2H-isoindolylene), carbazolylene, indolizinylene, benzopyrazolylene, benzimidazolylene, benzoxazolylene, benzothiazolylene, benzo[c,d]indolylene (=1H-indolylene), isoindolylene (=2H-isoindolylene), carbazolylene, indolizinylene, benzopyrazolylene, benzimidazolylene, benzoxazolylene, benzothiazolylene, benzo[c,d]indolylene (=2H-isoindolylene), ndolylene), 1H-benzo[g]indolylene, quinolinylene, isoquinolinylene, acridinylene, phenazinylene, quinazolinylene, quinoxalinylene, phenoxazinylene, phenthiazinylene, benzo[b][1,5]naphthyridinylene,5]naphthyridinylene), cinnolinylene, 1,5-naphthyridinylene, 1,8-naphthyridinylene, phenylpyrrolylene, naphthylpyrrolylene, dipyridylene, phenylpyridylene, naphthylpyridylene, pyrido[4,3-b]indolyl pyrido[4,3-b]indolylene, pyrido[3,2-b]indolylene, pyrido[3,2-g]quinolinylene, pyrido[2,3-b][1,8]naphthyridinylene, pyrrolo[3,2-b]pyridinylene, pteridinylene, purylene, 9-pyridinylene H-xanthenylene, 9H-thioxanthenylene, 2H-chromenylene, 2H-thiochromenylene, phenanthridinylene, phenanthrolinylene, benzo[1,2-b:4,3-b']difuranylene, benzo[1,2-b:6,5-b']difuranylene, benzo[1,2-b:6,5-b']difuranylene, benzo[1,2 -b:5,4-b']difuranylene, benzo[1,2-b:4,5-b']difuranylene, naphthofuranylene, benzo[b]naphtho[1,2-d]furanylene, benzo[b]naphtho[2,3 ...1-d] furanyl (benzo[b]naphtho[2,1-d]furanylene), tribenzo[b,d,f]oxepinylene, dibenzo[b,d]thienylene, naphtho[1,2-b]thienylene, naphtho[2,3-b]thienylene, naphtho[2,3-b]thienylene, naphtho[2,1-b]thienylene, benzo[b]naphtho[2,1-d]furanylene, tribenzo[b,d,f]oxepinylene, dibenzo[b,d]thienylene, naphtho[1,2-b]thienylene, naphtho[2,3-b]thienylene, naphtho[2,1-b]thienylene, b]naphtho[1,2-d]thienylene, benzo[b]naphtho[2,3-d]thienylene, benzo[b]naphtho[2,3-d]thienylene, benzo[b]naphtho[2,1-d]thienylene, 6H-dibenzo[b,d]thiopyranylene, 5H,9H-[1]benzothiopyranylene[5,4,3-c,d,e][2]benzothiopyranylene, 5H,10H-[1]benzothiopyranylene[5,4,3-c,d,e][2]benzothiopyranylene, benzo[1,2-b:4,3-b']bithienylene, benzo[1,2-b:6,5 -b']bisthienyl, benzo[1,2-b:5,4-b']bisthienyl, benzo[1,2-b:4,5-b']bisthienyl, 1,4-benzodithienyl, naphtho[1,2-b][1,4]dithienyl, naphtho[2,3-b][1,4]dithienyl, thianthrenyl, benzo[a]thianthrenyl, benzo[b]thianthrenyl, dibenzo[a,c]thianthrenyl, dibenzo[a,h]thianthrenyl, dibenzo[a,i]thianthrenyl, dibenzo[a,j]thianthrenyl, dibenzo[b,i]thianthrenyl, 2H-naphtho[1,8-b,c]thienyl, 5H-phenanthro[4,5-b,c,d]thianthrenyl ]thiopyranyl, 10,11-dihydrodibenzo[b,f]thiepinylene, 6,7-dihydrodibenzo[b,d]thiepinylene, dibenzo[b,f]thiepinylene, dibenzo[b,d]thiepinylene, 6H-dibenzo[d,f][1,3]dithiepinylene, tribenzo[b,d,f]thiepinylene, benzothieno[3,4-c,d]thieno[2,3,4-j,k][2]benzothiepinylene, dinaphtho[1,8-bc:1',8'-f,g][1,5]dithiocinylene, furano[3,2-g]quinolyl, furano[2,3-g]quinolyl, furano[2,3-g]quinoxalinyl, benzo[g]chromenyl, thieno[3,2-f][1]benzothieno[2,3-f][1]benzothieno[3,2-g]quinolyl, thieno[2,3-g]quinolyl, thieno[2,3-g]quinoxalinyl, benzo[g]thiochromenyl, pyrrolo[3,2,1-h,i]indolyl, benzo[g]quinoxalinyl, benzo[f]quinoxalinyl and benzo[h]isoquinolyl.

[0080] For the purposes of the present invention, the suffix "-ylene" indicates that, according to the practice in the art, the corresponding hetero(aromatic) moiety is in diradical form. Thus, the suffix "-ylene" (e.g., in phenylene or 1,4-phenylene) is used herein synonymously with the suffix "-diyl" (e.g., in phendiyl or phen-1,4-diyl).

[0081] In the context of the present invention, a "structural unit" refers to a structural element that is repeatedly present in the polymer backbone of a thermoplastic resin. Therefore, the terms "structural unit" and "repeating unit" are used synonymously.

[0082] For the purposes of the present invention, the term "optical device" refers to a device that is transparent to visible light and manipulates light beams, particularly by refraction. Optical devices include, but are not limited to, prisms, lenses, optical films, and combinations thereof, particularly lenses for cameras and lenses for glasses.

[0083] The statements made below with regard to preferred embodiments of the variables (substituents) of the compounds of the formula (I) and of the structural elements of the formula (II) are valid both individually and preferably in combination with one another.

[0084] With regard to the compounds of the formula (I) and the structural units of the formula (II) and, where applicable, with regard to the use according to the invention, the statements made below regarding preferred embodiments of the variables are valid both individually and preferably in combination with one another.

[0085] In formula (I) and also in formula (II), the variable X 1 , X 2 , Y 1 , Y 2 , R 1 , R 2 , R 3 , R 4 , A 1 , n, m, p, q and r alone or preferably in any combination preferably have the following meanings:

[0086] Preferred variables X in formula (I) are1 and X 2 are independently selected from hydrogen, -Alk 1 -OH, -CH2-A 2 -CH2-OH, -Alk 2 -C(O)OR x and -CH2-A 2 -C(O)OR x , and accordingly preferred are those variables X in formula (II) 1a and X 2a Independently selected from -Alk 1 -O-, -CH2-A 2 -CH2-O-、-Alk 2 -C(O)O- and -CH2-A 2 -C(O)O-, where Alk 1 , -Alk 2 , A 2 and R x has the meanings defined herein, particularly the preferred meanings.

[0087] In a preferred embodiment of group (1), the variable X in formula (I) 1 and X 2 Independently selected from -Alk 1 -OH and -CH2-A 2 -CH2-OH and correspondingly the variable X in formula (II) 1a and X 2a Independently selected from -Alk 1 -O- and -CH2-A 2 -CH2-O-, where Alk 1 Preferably it is a straight-chain C2-C4-alkanediyl group, for example 1,2-ethanediyl (CH2-CH2), 1,3-propylenediyl or 1,4-butanediyl, and in particular 1,2-ethanediyl, and A 2 Preferably, it is selected from 1,4-phenylene, 1,3-phenylene, 2,6-naphthylene, 1,4-naphthylene, 1,5-naphthylene and 4,4'-biphenylene. In this context, preference is also given to the variable X in formula (I) 1 and X 2 or the variable X in formula (II) 1a and X 2a Same as each other.

[0088] Therefore, in a particularly preferred subgroup (1.1) of embodiments, the variable X in formula (I) 1 and X 2is selected from 2-hydroxyethyl (i.e. 2-(HO)-ethyl), hydroxymethyl-phenyl-methyl (i.e. HO-methyl-phenyl-methyl), hydroxymethyl-naphthyl-methyl and hydroxymethyl-biphenyl-methyl, in particular selected from 2-hydroxyethyl, 4-(hydroxymethyl)phenyl)methyl, (3-(hydroxymethyl)phenyl)methyl, (4-(hydroxymethyl)-1-naphthyl)methyl, (5-(hydroxymethyl)-1-naphthyl)methyl, (6-(hydroxymethyl)-2-naphthyl)methyl and 4'-(hydroxymethyl)-1,1'-biphenyl-4-methyl, and in particular selected from 2-hydroxyethyl, 4-(hydroxymethyl)phenyl)methyl and (3-(hydroxymethyl)phenyl)methyl. Accordingly, in this particularly preferred embodiment of group (1.1), the variable X in formula (II) 1a and X 2a Selected from 2(-O)-ethyl, -O-methyl-phenyl-methyl and -O-methyl-naphthyl-methyl, in particular selected from 2(-O)-ethyl, (4(-O-methyl)phenyl)methyl, (3(-O-methyl)phenyl)methyl, (4(-O-methyl)-1-naphthyl)methyl, (5(-O-methyl)-1-naphthyl)methyl, (6(-O-methyl)-2-naphthyl)methyl and 4'(-O-methyl)-1,1'-biphenyl-4-methyl, and in particular selected from 2(-O)-ethyl, (4(-O-methyl)phenyl)methyl and (3(-O-methyl)phenyl)methyl, (4(-O-methyl)-1-naphthyl)methyl.

[0089] In a specific subset (1') of embodiments, the variable X in formula (I) 1 and X 2 have the same meaning, and similarly, the variable X in formula (II) 1a and X 2a has the same meaning as defined in the embodiments of groups (1) and (1.1).

[0090] In another group (2) of embodiments, the variable X in formula (I) and (II) is 1 and X 2 are hydrogen and correspondingly the variable X in formula (II) 1a and X 2a All are single bonds.

[0091] In a preferred embodiment of group (3), the variable X in formula (I) 1 and X 2 Independently selected from -Alk 2 -C(O)OR x and -CH2-A 2 -C(O)OR x And accordingly the variable X in formula (II) 1a and X 2aIndependently selected from -Alk 2 -C(O)O- and -CH2-A 2 -C(O)O-, where Alk 2 Preferably, the straight-chain C1-C4-alkanediyl radicals are present, for example methylene or 1,2-ethanediyl (CH2-CH2), and in particular methylene, A 2 is preferably selected from 1,4-phenylene, 1,3-phenylene, 2,6-naphthylene, 1,5-naphthylene and 1,4-naphthylene, and R x Preferably, it is hydrogen or C1-C4-alkyl, and in particular methyl. Also preferred in this context is the variable X 1 and X 2 or variable X 1a and X 2a Same as each other.

[0092] Therefore, in a particularly preferred subgroup (3.1) of embodiments, the variable X in formula (I) is 1 and X 2 is selected from methoxycarbonyl-methyl (i.e., CH3O-C(O)-methyl), methoxycarbonyl-phenyl-methyl (i.e., CH3O-C(O)-phenyl-methyl) and methoxycarbonyl-naphthyl-methyl, in particular selected from methoxycarbonyl-methyl, (4-(methoxycarbonyl)phenyl)methyl, (3-(methoxycarbonyl)phenyl)methyl, (4-(methoxycarbonyl)-1-naphthyl)methyl, (5-(methoxycarbonyl)-1-naphthyl)methyl and (6-(methoxycarbonyl)-2-naphthyl)methyl, and in particular selected from methoxycarbonyl-methyl, (4-(methoxycarbonyl)phenyl)methyl and (3-(methoxycarbonyl)phenyl)methyl. Accordingly, in this particularly preferred embodiment of group (3.1), the variable X in formula (II) 1a and X 2a is selected from -OC(O)-methyl, -OC(O)-phenyl-methyl and -OC(O)-naphthyl-methyl, in particular selected from -OC(O)-methyl, (4(-OC(O)-phenyl)methyl, (3(-OC(O)-phenyl)methyl, (4-(-OC(O)-)-1-naphthyl)methyl, (5-(-OC(O)-)-1-naphthyl)methyl and (6-(-OC(O)-)-2-naphthyl)methyl, and in particular selected from -OC(O)-methyl, (4(-OC(O)-phenyl)methyl and (3(-OC(O)-phenyl)methyl.

[0093] In a specific subset (3') of embodiments, the variable X in formula (I) 1 and X 2 have the same meaning, and similarly, the variable X in formula (II) 1a and X 2ahas the same meaning as defined in the embodiments of groups (3) and (3.1).

[0094] In a preferred embodiment of group (4), which is a combination of the embodiments of groups (1.1), (2) and (3.1), the variable X in formula (I) is 1 and X 2 selected from the group consisting of hydrogen, 2-hydroxyethyl, methoxycarbonyl-methyl, hydroxymethyl-phenyl-methyl, hydroxymethyl-naphthyl-methyl, hydroxymethyl-biphenyl-methyl, methoxycarbonyl-phenyl-methyl and methoxycarbonyl-naphthyl-methyl, in particular selected from the group consisting of hydrogen, 2-hydroxyethyl, methoxycarbonyl-methyl, (4-(hydroxymethyl)phenyl)methyl, (3-(hydroxymethyl)phenyl)methyl, (4-(hydroxymethyl)-1-naphthyl)methyl, (5-(hydroxymethyl)-1-naphthyl)methyl, (6-(hydroxymethyl)-2-naphthyl)methyl, 4'-(hydroxymethyl)-1,1'-biphenyl-4-methyl, (4-(methoxycarbonyl)phenyl)methyl, methyl, (4-(hydroxymethyl)phenyl)methyl, (3-(hydroxymethyl)phenyl)methyl, (4-(methoxycarbonyl)phenyl)methyl, (3-(methoxycarbonyl)phenyl)methyl, (4-(methoxycarbonyl)phenyl)methyl, (3-(methoxycarbonyl)phenyl)methyl, (4-(methoxycarbonyl)phenyl)methyl, (3-(methoxycarbonyl)phenyl)methyl, and (6-(methoxycarbonyl)-2-naphthyl)methyl, and in particular selected from hydrogen, 2-hydroxyethyl, (4-(hydroxymethyl)phenyl)methyl and (3-(hydroxymethyl)phenyl)methyl. Accordingly, in this preferred embodiment of group (4), the variable X in formula (II) is 1a and X 2aselected from the group consisting of a single bond, 2(-O)-ethyl, -OC(O)-methyl, -O-methyl-phenyl-methyl, -O-methyl-naphthyl-methyl, -OC(O)-phenyl-methyl and -OC(O)-naphthyl-methyl, in particular selected from the group consisting of a single bond, 2(-O)-ethyl, -OC(O)-methyl, (4(-O-methyl)phenyl)methyl, (3(-O-methyl)phenyl)methyl, (4(-O-methyl)-1-naphthyl)methyl, (5(-O-methyl)-1-naphthyl)methyl, (6(-O-methyl)-2-naphthyl)methyl, (4(-OC(O)-phenyl)methyl, (3-(-OC(O)-phenyl)methyl, methyl, (-O-(methyl)phenyl)methyl, (4-(-O-methyl)phenyl)methyl, (3-(-O-methyl)phenyl)methyl, 4-(-O-methyl)phenyl)methyl and (3-(-O-methyl)phenyl)methyl, and in particular selected from a single bond, 2(-O)-ethyl, (4-(-O-methyl)phenyl)methyl and (3-(-O-methyl)phenyl)methyl.

[0095] In a specific subset (4') of embodiments, the variable X in formula (I) 1 and X 2 have the same meaning, and similarly, the variable X in formula (II) 1a and X 2a have the same meanings, which are selected from the meanings defined in the embodiments of group (4).

[0096] Preferably, the variable A in formula (I) and (II) is 1 Selected from single bond, -CH2-, -CHAr A -、-CH(CH2Ar A )-、-C(CH2Ar A )2-, monocyclic or polycyclic arylene having 6 to 26 carbon atoms as ring members and monocyclic or polycyclic heteroarylene having 5 to 26 atoms as ring members, in particular selected from a single bond, -CH2-, -C(CH2Ar A )2-, monocyclic or polycyclic arylene having 6 to 26 carbon atoms as ring members and monocyclic or polycyclic heteroarylene having 5 to 26 atoms as ring members, wherein the monocyclic or polycyclic arylene and the monocyclic or polycyclic heteroarylene are unsubstituted or carry 1, 2, 3 or 4 R Ar Group; Ar A , a monocyclic or polycyclic arylene group, a monocyclic or polycyclic heteroarylene group, and R Ar has the meanings defined herein, especially the preferred meanings mentioned herein.

[0097] In the preferred embodiment of group (5), the variable A1 in formula (I) and (II) is selected from a single bond, -CH2-, -CHAr A -、-CH(CH2Ar A )- and -C(CH2Ar A )2-, preferably selected from a single bond, -CH2-, -CH(CH2Ar A )- and -C(CH2Ar A )2-, in particular selected from -CH2- and -C(CH2Ar A )2-, and specifically -C(CH2Ar A )2-, where Ar A has one of the meanings defined herein, in particular one of the meanings mentioned as being preferred, and in particular is selected from phenyl, naphth-1-yl, naphth-2-yl, fluoren-2-yl, fluoren-9-yl, phenanthrene-9-yl, dibenzo[b,d]thiophen-2-yl, dibenzo[b,d]thiophen-3-yl, dibenzo[b,d]thiophen-4-yl, dibenzo[b,d]furan-2-yl, dibenzo[b,d]furan-3-yl or dibenzo[b,d]furan-4-yl, thianthren-1-yl, thianthren-2-yl, oxanthren-1-yl, oxanthren-2-yl, 9H-xanthren-9-yl and 9H-thioxanthren-9-yl.

[0098] In a preferred embodiment of subgroup (5.1), the variable A1 in formula (I) and (II) is -C(CH2Ar A )2-, where Ar A is selected from the group consisting of phenyl, naphth-1-yl, naphth-2-yl and phenanthren-9-yl.

[0099] In the preferred embodiment of group (6), the variable A in formula (I) 1 from monocyclic or polycyclic arylene radicals having 6 to 26 carbon atoms as ring members and monocyclic or polycyclic heteroarylene radicals having 5 to 26 atoms as ring members, in particular monocyclic or polycyclic aryl radicals having 6 to 22 (especially 6 to 18) carbon atoms as ring members and monocyclic or polycyclic heteroaryl radicals having a total of 5 to 26 atoms as ring members, in particular polycyclic heteroaryl radicals having a total of 9 to 26 atoms as ring members, wherein 1, 2, 3 or 4 of these atoms are nitrogen, oxygen or sulfur atoms, and preferably 1, 2 or 3, for example 1 or 2 of these atoms are oxygen or sulfur atoms, and the remaining atoms of these atoms are carbon atoms, wherein the monocyclic or polycyclic aryl radicals and monocyclic or polycyclic heteroaryl radicals are unsubstituted or carry 1, 2, 3 or 4, in particular 1 or 2 R Ar Group, where R Arhas one of the meanings defined herein, in particular one of the meanings mentioned as being preferred.

[0100] In a more preferred embodiment of subgroup (6.1), A 1 selected from phenylene, naphthylene, 1,2-dihydroacenaphthenylene, biphenylene, 9H-fluorenylene, 11H-benzo[a]fluorenylene, 11H-benzo[b]fluorenylene, 7H-benzo[c]fluorenylene, anthracenylene, phenanthrenylene, benzo[c]phenanthrenylene, pyrenylene, phenylene, picenylene, triphenylene, furanylene, benzo[b]furanylene, dibenzo[b,d]furanylene, naphtho[1,2-b]furanylene, naphtho[2,3-b]furanylene, naphtho[2,1-b]furanylene, benzo[b]naphtho[1,2-d]furanylene, benzo[b]naphtho[2,3-d]furanylene, benzo[b]naphtho[2,1-d]furanylene, benzo[1,2-b:4,3-b']difuranylene, benzo[1,2-b:6,5-b']difuranylene, benzo[1,2-b:5,4-b']difuranylene , benzo[1,2-b:4,5-b']difuranyl, 9H-xanthylene, tribenzo[b,d,f]oxepinylene, dibenzo[1,4]dioxinyl, 2H-naphtho[1,8-d,e][1,3]dioxinyl, phenoxathiinylene, dinaphtho[2,3-b:2',3'-d]furanyl, oxanthrenyl, benzo[a]oxanthrenylene, benzo[b]oxanthrenylene, thiathrenyl thienylene, benzo[b]thienylene, dibenzo[b,d]thienylene, naphtho[1,2-b]thienylene, naphtho[2,3-b]thienylene, naphtho[2,1-b]thienylene, benzo[b]naphtho[1,2-d]thienylene, benzo[b]naphtho[2,3-d]thienylene, benzo[b]naphtho[2,1-d]thienylene, benzo[1,2-b:4,3-b']dithienylene, benzo[1,2-b:6,5-b']dithienylene, benzo[1,2-b:5,4-b']dithienylene, benzo[1,2-b:4,5 -b']bithienyl, 9H-thioxanthylene, 6H-dibenzo[b,d]thiopyranylene, 1,4-benzodithiinylene, naphtho[1,2-b][1,4]dithiinylene, naphtho[2,3-b][1,4]dithiinylene, thianthrenylene, benzo[a]thianthrenylene, benzo[b]thianthrenylene, dibenzo[a,c]thianthrenylene,c]thianthrenylene), dibenzo[a,h]thianthrenyl, dibenzo[a,i]thianthrenyl, dibenzo[a,j]thianthrenyl, dibenzo[b,i]thianthrenyl, 2H naphtho[1,8-b,c]thienylene, dibenzo[b,d]thiepinylene, dibenzo[b,d]thiepinylene, 5H-phenanthro[4,5-b,c,d]thiopyranyl, 5H phenanthro[4,5-b,c,d]thiopyranylene), tribenzo[b,d,f]thiopyranylene, 2,5-dihydronaphtho[1,8-b,c:4,5-b',c']bithienylene, 2,6-dihydronaphtho[1,8-b,c:5,4-b',c']dithienylene, tribenzo[a,c,i]thiopyranylene, benzo[b]naphtho[1,8-e,f][1,4]dithiopyranylene 1,2-b:5,4-b']bithienyl, wherein the aforementioned monocyclic or polycyclic aromatic and polycyclic heteroaromatic groups are unsubstituted or carry 1 or 2 R, Ar Group.

[0101] In a particularly preferred subgroup (6.2) of embodiments, A 1 is selected from phenylene, naphthylene, thienylene, furanylene, benzo[b]thienylene, benzo[b]furanylene, dibenzo[b,d]thienylene, dibenzo[b,d]furanylene, biphenylene, 9H-fluorenylene, xanthenylene, phenoxathinylene, thianthrenylene, 9H-oxanthrylene and 9H-thioanthrylene, wherein the aforementioned monocyclic or polycyclic aromatic groups and monocyclic and polycyclic heteroaromatic groups are unsubstituted or carry 1 or 2 R Ar Group.

[0102] In a particularly preferred subgroup (6.3) of embodiments, A 1is selected from the group consisting of phenylene, naphthylene, dibenzo[b,d]thienylene, biphenylene, 9H-fluorenylene, xanthenylene, phenoxathinylene, thianthrenylene, 9H-xanthenylene and 9H-thioanthenylene, and in particular selected from the group consisting of 1,4-phenylene, 1,2-phenylene, 1,3-phenylene, 2,3-naphthylene, 2,7-naphthylene, 2,6-naphthylene, 1,4-naphthylene, 1,5-naphthylene, 1,8-naphthylene, 4,6-dibenzo[b,d]thienylene, 2,8-dibenzo[b,d]thienylene, 3,7-dibenzo[b,d]thienylene, 3,3′-biphenylene, 4,4′-biphenylene, 9,9-9H- 2,7-9H-fluorenyl, 2,7-oxanthryl, 2,8-oxanthryl, 1,4-oxanthryl, 2,3-oxanthryl, 1,6-oxanthryl, 1,9-oxanthryl, 1,4-phenoxathinyl, 3,7-phenoxathinyl, 2,8-phenoxathinyl, 3,8-phenoxathinyl, 2,7-thianthrenyl, 2,8-thianthrenyl, 1,4-thianthrenyl, 2,3-thianthrenyl, 1,6-thianthrenyl, 1,9-thianthrenyl, 9,9-9H-oxanthryl and 9,9-9H-thioxanthryl, wherein the aforementioned monocyclic or polycyclic aromatic and polycyclic heteroaromatic groups are unsubstituted or carry 1 or 2 R Ar Group.

[0103] A preferred embodiment of group (6) is a subgroup (6') of compounds of formula (I), wherein A 1 The moiety comprises a phenylene ring, which may have one or two fused rings selected from a fused benzene ring and a fused 5- or 6-membered heteroaromatic ring. Among the embodiments of the compounds of group (6'), those wherein Y 1 and Y 2 The group is connected to A 1 These compounds are also referred to as embodiments of the para isomers of group (6'). Also preferred are embodiments of mixtures of the para isomers of the compounds of formula (I) of group (6') and the corresponding meta or ortho isomers. Among the embodiments of the compounds of group (6'), particularly preferred are compounds of formula (I) wherein A 1 is 1,4-phenylene and a mixture of one or two isomers thereof, wherein A 1 It is 1,2-phenylene or 1,3-phenylene.

[0104] In a particularly preferred subgroup (6.4) of embodiments, A 1selected from 1,4-phenylene, 1,2-phenylene, 1,3-phenylene, 2,3-naphthylene, 2,7-naphthylene, 2,6-naphthylene, 1,4-naphthylene, 1,5-naphthylene, 1,8-naphthylene, 4,6-dibenzo[b,d]thienylene, 2,8-dibenzo[b,d]thienylene, 3,3'-biphenylene, 4,4'-biphenylene, 9, 9-9H-fluorenyl, 2,7-9H-fluorenyl, 2,7-thianthrenyl, 2,8-thianthrenyl, 1,4-thianthrenyl, 2,3-thianthrenyl, 1,6-thianthrenyl, 1,9-thianthrenyl, 9,9-9H-xanthrenyl and 9,9-9H-thioxanthrenyl, wherein the aforementioned monocyclic or polycyclic aromatic and polycyclic heteroaromatic groups are unsubstituted or carry 1 or 2 R Ar groups, and in particular are unsubstituted.

[0105] Preferably, the variable Y in formula (I) and (II) is 1 and Y 2 Selected from -CH2-, -CHAr Y - and -CH(CH2Ar Y )-, where Ar Y has one of the meanings defined herein, in particular one of the meanings mentioned as preferred, and is specifically selected from phenyl, naphth-1-yl, naphth-2-yl, fluoren-2-yl, fluoren-9-yl, phenanthrene-9-yl, dibenzo[b,d]thiophen-2-yl, dibenzo[b,d]thiophen-3-yl, dibenzo[b,d]thiophen-4-yl, dibenzo[b,d]furan-2-yl, dibenzo[b,d]furan-3-yl or dibenzo[b,d]furan-4-yl, thianthren-1-yl, thianthren-2-yl, xanthren-1-yl, xanthren-2-yl, 9H-xanthren-9-yl and 9H-thioxanthren-9-yl, and more particularly selected from phenyl, naphth-1-yl, naphth-2-yl and phenanthrene-9-yl. In this context, particular preference is given to the variable Y 1 and Y 2 Same as each other.

[0106] In a specific group (7) of embodiments, the variable Y in formula (I) and (II) is 1 and Y 2 All are -CH2-.

[0107] In a particularly preferred subgroup (7') of group (7), variable A 1 It has one of the meanings given in the embodiments of group (6), preferably one of the meanings given in the embodiments of group (6.1), more preferably one of the meanings given in the embodiments of group (6.2), particularly one of the meanings given in the embodiments of group (6.3), and especially one of the meanings given in the embodiments of group (6.4).

[0108] In the alternative embodiment of group (8), -Y in formula (I) and (II) 1 -A 1 -Y 2 -Part is -CH2- or -CHAr Y -, where Ar Y has one of the meanings defined herein, in particular one of the meanings mentioned as being preferred.

[0109] In a preferred embodiment of subgroup (8.1), -Y in formula (I) and (II) 1 -A 1 -Y 2 The - part is -CH2-.

[0110] Preferably, the variable n in formula (I) and (II) is 1 or 2.

[0111] In a particular group (9) of embodiments, the variable n in formulas (I) and (II) is 1.

[0112] If present, the substituent R in formula (I) and (II) is 1 , R 2 , R 3 and R 4 has one of the meanings defined herein, in particular one of the meanings mentioned as being preferred. In the present context, it is preferred that, if present, R 1 , R 2 , R 3 and R 4 have the same meaning. It is also preferred that, if present, R 1 , R 2 , R 3 and R 4 are attached to the corresponding positions of their respective naphthyl units.

[0113] The variables m, p, q and r in formulae (I) and (II) are preferably 0, 1 or 2, more preferably 0 or 1, and in particular all have the same meaning.

[0114] In a particularly preferred embodiment of group (10), the variables m, p, q and r in formulae (I) and (II) are all zero.

[0115] Those skilled in the art will readily appreciate that in formula (I) and (II), X given in one or more embodiments of groups (1), (1.1) and (1') 1 and X 2A may have the same meaning as A in one of the embodiments according to groups (5) and (5.1) or in one of the embodiments according to groups (6), (6.1), (6.2), (6.3) and (6.4). 1 The meaning combination of Y in the embodiment according to group (7) 1 and Y 2 The meanings of are combined with the meanings of n in the embodiments according to group (9), and can also be combined with the meanings of m, p, q and r in the embodiments according to group (10). A person skilled in the art will also understand that in formulas (I) and (II), X given in the embodiments of group (2) 1 and X 2 The meaning may be the same as A according to one of the embodiments in groups (5) and (5.1) or according to one of the embodiments in groups (6), (6.1), (6.2), (6.3) and (6.4). 1 The meaning combination of Y in the embodiment according to group (7) 1 and Y 2 The meanings of are combined with the meanings of n in the embodiments according to group (9), and can also be combined with the meanings of m, p, q and r in the embodiments according to group (10). It will also be understood by those skilled in the art that in formula (I) and (II), X given in one or more embodiments of groups (3), (3.1) and (3') 1 and X 2 A may have the same meaning as A in one of the embodiments according to groups (5) and (5.1) or in one of the embodiments according to groups (6), (6.1), (6.2), (6.3) and (6.4). 1 The meaning combination of Y in the embodiment according to group (7) 1 and Y 2 The meanings of are combined with the meanings of n in the embodiment according to group (9), and can also be combined with the meanings of m, p, q and r in the embodiment according to group (10). A person skilled in the art will also understand that in formula (I) and (II), X given in one of the embodiments of groups (4) and (4') is 1 and X 2 A may have the same meaning as A in one of the embodiments according to groups (5) and (5.1) or in one of the embodiments according to groups (6), (6.1), (6.2), (6.3) and (6.4). 1 The meaning combination of Y in the embodiment according to group (7) 1 and Y 2 The meanings of are combined with the meaning of n in the embodiments according to group (9), and can also be combined with the meanings of m, p, q and r in the embodiments according to group (10).

[0116] In addition, it is also easy to understand for those skilled in the art that in formula (I) and (II), according to one or more embodiments of group (1), (1.1) and (1'), or an embodiment of group (2), or one or more embodiments of group (3), (3.1) and (3'), or one of groups (4) and (4'), X 1 and X 2 The meaning of can be the same as Y in one of the embodiments of groups (8) and (8.1) according to 1 -A 1 -Y 2 -, a combination of the meanings of n in the embodiments according to group (9), and a combination of the meanings of m, p, q and r in the embodiments according to group (10).

[0117] In addition and if not otherwise stated, the variable Ar Y ,Ar A ,Q,R 1 , R 2 , R 3 , R 4 , R 5a , R 5b , R Ar , R, R', R" and R'" alone or in combination with the above variables X 1 , X 1 , A 1 , A 2 ,n,m,p,q,r,R x , Alk 1 and Alk 2 The meanings and preferred meanings of are combined and have the following meanings.

[0118] Ar Y and Ar A are preferably selected independently of one another from monocyclic or polycyclic aryl radicals having 6 to 18 carbon atoms as ring member atoms and polycyclic heteroaryl radicals having a total of 9 to 6 atoms as ring member atoms, wherein 1 or 2 of these ring member atoms of the heteroaryl radical are sulfur or oxygen atoms and the remaining of these ring member atoms of the heteroaryl radical are carbon atoms, wherein the monocyclic or polycyclic aryl radicals and the polycyclic heteroaryl radicals are unsubstituted or carry 1 or 2 R Ar Group, where R Ar has one of the meanings defined herein, in particular one of the meanings mentioned as being preferred. Unsubstituted Ar is preferred here Y and Ar A Group.

[0119] More preferably, Ar Y and Ar AThe phenyl group is independently selected from phenyl, naphthyl such as naphthalen-1-yl or naphthalen-2-yl, fluorenyl such as fluoren-1-yl, fluoren-2-yl, fluoren-3-yl, fluoren-4-yl, fluoren-9-yl, 11H-benzo[a]fluorenyl such as 11H-benzo[a]fluoren-7-yl, 11H-benzo[b]fluorenyl such as 11H-benzo[b]fluoren-1-yl, 7H-benzo[c]fluorenyl such as 7H-benzo[c]fluoren-5-yl or 7H-benzo[c]fluoren-10-yl, phenanthrene, phenanthrenyl ... phenanthren-1-yl, phenanthren-2-yl, phenanthren-3-yl, phenanthren-4-yl or phenanthren-9-yl, biphenyl such as biphenyl-4-yl, biphenyl-3-yl or biphenyl-2-yl, benzo[c]phenanthrenyl such as benzo[c]phenanthren-1-yl, benzo[c]phenanthren-2-yl, benzo[c]phenanthren-3-yl, benzo[c]phenanthren-4-yl, benzo[c]phenanthren-5-yl or benzo[c]phenanthren-6-yl, pyrenyl such as pyrene-1-yl, pyrene-2-yl or pyrene-4-yl, Kiru -1-base, -2-base, -3-base, -4-base, -5-base or -6-yl, triphenylene such as triphenylene-1-yl or triphenylene-2-yl, benzo[b]thiophene such as benzo[b]thiophene-2-yl, benzo[b]thiophene-3-yl, benzo[b]thiophene-4-yl, benzo[b]thiophene-5-yl, benzo[b]thiophene-6-yl or benzo[b]thiophene-7-yl, dibenzo[b,d]thiophene such as dibenzo[b,d]thiophene-1-yl, dibenzo[b,d ...,d]thiophene-3-yl, benzo[b]thiophene-4-yl, benzo[b]thiophene-5-yl, benzo[b]thiophene-6-yl or benzo[b]thiophene-7-yl, dibenzo[b,d]thiophene such as dibenzo[b,d]thiophene-7-yl, dibenzo[b,d]thiophene Thiophene-2-yl, dibenzo[b,d]thiophen-3-yl or dibenzo[b,d]thiophen-4-yl, dibenzo[b,d]furanyl such as dibenzo[b,d]furan-1-yl, dibenzo[b,d]furan-2-yl, dibenzo[b,d]furan-3-yl or dibenzo[b,d]furan-4-yl, naphtho[1,2-b]thiophene such as naphtho[1,2-b]thiophen-5-yl, naphtho[2 ,3-b]thienyl such as naphtho[2,3-b]thien-3-yl, naphtho[2,3-b]thien-4-yl or naphtho[2,3-b]thien-9-yl, naphtho[2,1-b]thienyl such as naphtho[2,1-b]thien-2-yl or naphtho[2,1-b]thien-5-yl, thianthrenyl such as thianthren-1-yl or thianthren-2-yl, xanthrenyl such as xanthren-1-yl or xanthren-2-yl, phenanthrenyl Oxathinyl such as thiothian-1-yl, thiothian-2-yl, thiothian-3-yl or thiothian-4-yl, 9H-xanthyl such as 9H-xanthyl-1-yl, 9H-xanthyl-2-yl, 9H-xanthyl-3-yl or 9H-xanthyl-9-yl, and 9H-thioanthenyl such as 9H-thioanthen-1-yl, 9H-thioanthen-2-yl, 9H-thioanthen-3-yl or 9H-thioanthen-9-yl.

[0120] Even more preferably, Ar Y and Ar A independently selected from phenyl, naphthyl, fluorenyl, phenanthryl, dibenzo[b,d]furanyl, dibenzo[b,d]thienyl, thianthrenyl, xanthenyl, phenoxathinyl, 9H-xanthenyl and 9H-thioxanthenyl, such as phenyl, naphthalen-1-yl, naphthalen-2-yl, fluoren-2-yl, fluoren-3-yl, fluoren-9-yl, phenanthren-1-yl, phenanthren-2-yl, phenanthren-3-yl, phenanthren-4-yl, phenanthren-9-yl, dibenzo[b,d]thiophene-1-yl, dibenzo[b,d]thiophene-2-yl, dibenzo[b,d]thiophene-3-yl, dibenzo[b,d]thiophene-4-yl, dibenzo[b,d]thiophene-9-yl ] furan-1-yl, dibenzo[b,d] furan-2-yl, dibenzo[b,d] furan-3-yl or dibenzo[b,d] furan-4-yl, thianthren-1-yl, thianthren-2-yl, xanthene-1-yl, xanthene-2-yl, phenoxathin-1-yl, phenoxathin-2-yl, phenoxathin-3-yl, phenoxathin-4-yl, 9H-xanthene-1-yl, 9H-xanthene-2-yl, 9H-xanthene-3-yl, 9H-xanthene-9-yl, 9H-thioxanthene-1-yl, 9H-thioxanthene-2-yl, 9H-thioxanthene-3-yl and 9H-thioxanthene-9-yl.

[0121] Especially Ar Y and Ar A independently selected from phenyl, naphthalene-1-yl, naphthalene-2-yl, fluoren-2-yl, fluoren-9-yl, phenanthrene-9-yl, dibenzo[b,d]thiophene-2-yl, dibenzo[b,d]thiophene-3-yl, dibenzo[b,d]thiophene-4-yl, dibenzo[b,d]furan-2-yl, dibenzo[b,d]furan-3-yl or dibenzo[b,d]furan-4-yl, thianthren-1-yl, thianthren-2-yl, xanthene-1-yl, xanthene-2-yl, 9H-xanthene-9-yl and 9H-thioxanthene-9-yl.

[0122] Specifically, Ar Y and Ar A Independently selected from phenyl, naphth-1-yl, naphth-2-yl and phenanthren-9-yl.

[0123] Q is preferably selected from a single bond, S, O and SO2, in particular selected from a single bond, S and O, and specifically is a single bond.

[0124] R 1 , R 2 , R 3 and R 4 Preferably, independently of one another, they are selected from halogen, C2-C3-alkynyl, CN, R, OR and CH tR'3-t, and more preferably selected from fluorine, CN, R and OR, wherein t is 1 or 2, especially 2, and the variables R and R' each have one of the meanings defined herein, especially one of the preferred meanings. In particular, R 1 , R 2 , R 3 and R 4 The radicals are independently selected from fluorine, CN, methyl, methoxy, phenyl, naphthyl and phenanthryl, and in particular from fluorine, phenyl or naphthyl.

[0125] R 5a and R 5b Preferably, independently of one another, they are selected from hydrogen, fluorine, CN, R, OR and CH k R' 3-k , and is more preferably selected from hydrogen, fluorine, CN, R and OR, wherein k is 1 or 2, in particular 2, and the variables R and R' each have one of the meanings defined herein, in particular one of the preferred meanings. In particular, R 5a and R 5b The radicals are independently selected from hydrogen, fluorine, CN, methyl, methoxy, phenyl, naphthyl and phenanthrenyl, and in particular from hydrogen, fluorine, phenyl or naphthyl.

[0126] R Ar Preferably selected from R, OR and CH t R' 3-t , and more preferably selected from R and OR, wherein t is 1 or 2, especially 2, and the variables R and R' each have one of the meanings defined herein, especially one of the preferred meanings. In particular, R Ar The group is selected from methyl, methoxy, phenyl, naphthyl, phenanthryl and triphenylene, and is specifically phenyl, naphthyl or phenanthryl.

[0127] R is preferably selected from methyl, ethyl, phenyl, naphthyl, phenanthrenyl and triphenylene, which are unsubstituted or substituted by 1, 2 or 3 identical or different R'' groups, wherein R'' independently has one of the meanings defined herein for each occurrence, particularly one of the preferred meanings. More preferably, R is selected from phenyl, naphthyl and phenanthrenyl, which are unsubstituted.

[0128] R' is preferably selected from phenyl, naphthyl, phenanthrenyl and triphenylene, which are unsubstituted or substituted by 1, 2 or 3 identical or different R'' groups, wherein R'' independently has one of the meanings defined herein for each occurrence, particularly one of the preferred meanings. More preferably, R' is selected from phenyl, naphthyl and phenanthrenyl, which are unsubstituted.

[0129] R" is preferably selected from hydrogen, methyl, phenyl and naphthyl, wherein phenyl and naphthyl are unsubstituted or substituted by 1, 2 or 3 (especially 1 or 2) identical or different R"' groups, wherein R"' has independently at each occurrence one of the meanings defined herein, especially one of the preferred meanings. More preferably, R" is unsubstituted phenyl or unsubstituted naphthyl.

[0130] R''' is preferably selected from phenyl, OCH3 and CH3.

[0131] In the embodiments of the specific subgroup (7a) of groups (7), (9) and (10), wherein Y in formula (I) 1 and Y 2 The groups are all -CH2-, the variable n is 1, the variables m, p, q and r are all 0, and X 1 and X 2 The groups have the same meanings, the compound of formula (I) is the compound of formula (Ia),

[0132]

[0133] Where X represents the same X 1 and X 2 group, and wherein A 1 , X 1 and X 2 have the meanings defined herein, particularly the meanings mentioned as being preferred.

[0134] In the embodiment of this subgroup (7a) of groups (7), (9) and (10), the structural unit of formula (II) is a structural unit of formula (IIa),

[0135]

[0136] Where # represents the connection point with the adjacent structural unit, and X a Indicates the same X 1a and X 2a group, and wherein the variable A 1 , X 1a and X 2a have the meanings defined herein, particularly the meanings mentioned as being preferred.

[0137] Preferably, the X moiety in formula (Ia) and the X moiety in formula (IIa) a The moiety is as defined in one of the embodiments of group (1) and (1.1), one of the embodiments of group (2), or one of the embodiments of group (3) and (3.1). More preferably, the moiety X in formula (Ia) and the moiety X in formula (IIa) aThe moiety is as defined in the embodiments of group (1.1), group (2) or group (3.1). Thus, the moiety X in formula (Ia) is particularly selected from hydrogen, 2-hydroxyethyl (i.e., 2-(HO)-ethyl), 4-(hydroxymethyl)phenyl)methyl, (3-(hydroxymethyl)phenyl)methyl, (4-(hydroxymethyl)-1-naphthyl)methyl, (5-(hydroxymethyl)-1-naphthyl)methyl, (6-(hydroxymethyl)-2-naphthyl)methyl, 4'-(hydroxymethyl)-1,1'-biphenyl-4-methyl, methoxycarbonyl-methyl, (4-(methoxycarbonyl)phenyl)methyl, (3-(methoxycarbonyl)phenyl)methyl methyl, (4-(methoxycarbonyl)-1-naphthyl)methyl, (5-(methoxycarbonyl)-1-naphthyl)methyl and (6-(methoxycarbonyl)-2-naphthyl)methyl, in particular selected from hydrogen, 2-hydroxyethyl, methoxycarbonyl-methyl, (4-(hydroxymethyl)phenyl)methyl, (3-(hydroxymethyl)phenyl)methyl, (4-(methoxycarbonyl)phenyl)methyl and (3-(methoxycarbonyl)phenyl)methyl, and in particular selected from hydrogen, 2-hydroxyethyl, (4-(hydroxymethyl)phenyl)methyl and (3-(hydroxymethyl)phenyl)methyl. Thus, X in formula (IIa) is a The moiety is particularly selected from a single bond, 2(-O)-ethyl, (4(-O-methyl)phenyl)methyl, (3(-O-methyl)phenyl)methyl, (4(-O-methyl)-1-naphthyl)methyl, (5(-O-methyl)-1-naphthyl)methyl, (6(-O-methyl)-2-naphthyl)methyl, 4'(-O-methyl)-1,1'-biphenyl-4-methyl, -OC(O)-methyl, (4(-OC(O)-phenyl)methyl, (3(-OC(O)-phenyl)methyl, (4-(-OC(O)-)-1-naphthyl)methyl methyl, (-O-methyl)phenyl)methyl, (3-(-O-methyl)phenyl)methyl, (-O-methyl)phenyl)methyl, (4-(-O-methyl)phenyl)methyl, (3-(-O-methyl)phenyl)methyl, and particularly selected from a single bond, 2(-O)-ethyl, (4-(-O-methyl)phenyl)methyl and (3-(-O-methyl)phenyl)methyl.

[0138] Also preferred are compounds of formula (Ia) and structural units of formula (IIa) in which A 1The moiety X is as defined in one of the embodiments of groups (5) and (5.1) or in one of the embodiments of groups (6), (6.1), (6.2), (6.3) and (6.4). More preferably, the moiety X in formula (Ia) and formula (IIa) is as defined in one of the embodiments of group (5.1) or in one of the embodiments of group (6.4). Thus, the moiety X in formula (Ia) is particularly selected from bisphenylmethanediyl, bis(naphthalene-1-yl)methanediyl, bis(naphthalene-2-yl)methanediyl, bis(phenanthrene-9-yl)methanediyl, 1,4-phenylene, 1,2-phenylene, 1,3-phenylene, 2,3-naphthylene, 2,7-naphthylene, 2,6-naphthylene, 1,4-naphthylene, 1,5-naphthylene, 1,8-naphthylene, 4,6-dibenzo[ b,d]thienyl, 2,8-dibenzo[b,d]thienyl, 3,3′-biphenylene, 4,4′-biphenylene, 9,9-9H-fluorenylene, 2,7-9H-fluorenylene, 2,7-thianthrenylene, 2,8-thianthrenylene, 1,4-thianthrenylene, 2,3-thianthrenylene, 1,6-thianthrenylene, 1,9-thianthrenylene, 9,9-9H-xanthrenylene and 9,9-9H-thioxanthrenylene.

[0139] Examples of a specific subgroup (7a) are compounds of formula (Ia) and structural units of formula (IIa) in which the moiety X or X a Part and variable A 1 The combinations are defined in any row from 1 to 266 in Table A below, where X a In each case, it is derived from X in formula (Ia) by replacing the hydrogen with a single bond if X is hydrogen or by replacing the -OH or -OR x The radical is replaced by an oxo (—O—) unit, wherein X has one of the meanings defined herein, in particular one of the meanings mentioned herein as being preferred.

[0140] Table A

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147] Among the compounds of formula (Ia) listed in Table A, those compounds of formula (Ia) wherein the X moiety is 2-hydroxyethyl (i.e. 2-HO-ethyl) are particularly preferred, and thus those compounds wherein X is a The structural unit of formula (IIa) is partially 2(-O)-ethyl. In other words, the following compounds of formula (Ia) are particularly preferred:

[0148] -2,2'-[1,4-phenylenebis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxy)]bis(ethane-1-ol)

[0149] -2,2'-[1,2-phenylenebis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxy)]bis(ethane-1-ol)

[0150] -2,2'-[1,3-phenylenebis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxy)]bis(ethane-1-ol)

[0151] -2,2'-[[1,1'-biphenyl]-4,4'-diylbis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxy)]bis(ethane-1-ol)

[0152] -2,2'-[[1,1'-biphenyl]-3,3'-diylbis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxy)]bis(ethan-1-ol)

[0153] -2,2'-[naphthalene-2,3-diylbis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxy)]bis(ethan-1-ol)

[0154] -2,2'-[naphthalene-2,7-diylbis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxy)]bis(ethan-1-ol)

[0155] -2,2'-[naphthalene-2,6-diylbis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxy)]bis(ethan-1-ol)

[0156] -2,2'-[naphthalene-1,4-diylbis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxy)]bis(ethane-1-ol)

[0157] -2,2'-[naphthalene-1,5-diylbis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxy)]bis(ethane-1-ol)

[0158] -2,2'-[naphthalene-1,8-diylbis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxy)]bis(ethan-1-ol)

[0159] -2,2'-[dibenzo[b,d]thiophene-4,6-diylbis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxy)]bis(ethan-1-ol)

[0160] -2,2'-[dibenzo[b,d]thiophene-2,8-diylbis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxy)]bis(ethan-1-ol

[0161] -2,2'-[dibenzo[b,d]thiophene-3,7-diylbis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxy)]bis(ethan-1-ol

[0162] -2,2'-[thianthrene-2,7-diylbis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxy)]bis(ethan-1-ol)

[0163] -2,2'-[thianthrene-2,8-diylbis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxy)]bis(ethan-1-ol)

[0164] -2,2'-[thianthrene-1,4-diylbis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxy)]bis(ethan-1-ol)

[0165] -2,2'-[thianthrene-2,3-diylbis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxy)]bis(ethan-1-ol)

[0166] -2,2'-[thianthrene-1,6-diylbis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxy)]bis(ethan-1-ol)

[0167] -2,2'-[thianthrene-1,9-diylbis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxy)]bis(ethan-1-ol)

[0168] -2,2'-[9H-fluorene-9,9-diylbis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxy)]bis(ethan-1-ol)

[0169] -2,2'-[9H-xanthene-9,9-diylbis(methyleneoxy[1,1'-binaphthyl]-2',2-diyloxy)]bis(ethane-1-ol)

[0170] -2,2'-[9H-thioxanthene-9,9-diylbis(methyleneoxy[1,1'-binaphthyl]-2',2-diyloxy)]bis(ethan-1-ol)

[0171] -2,2'-[9H-fluorene-2,7-diylbis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxy)]bis(ethan-1-ol)

[0172] -2,2'-[{2,2-bis[(naphthalen-1-yl)methyl]propane-1,3-diyl}bis(oxy[1,1'-binaphthylene]-2',2-diyloxy)]di(ethane-1-ol)

[0173] Among the compounds of formula (Ia) listed in Table A, those compounds of formula (Ia) wherein the X moiety is (4-(hydroxymethyl)phenyl)methyl are particularly preferred, and thus those compounds of formula (Ia) wherein X is a The structural unit of formula (IIa) is partially (4(-O-methyl)phenyl)methyl. In other words, the following compounds of formula (Ia) are particularly preferred:

[0174] -[1,4-phenylenebis(methyleneoxy[1,1'-binaphthyl]-2',2-diyloxymethylene(diyloxymethylene)-4,1-phenylene)]dimethanol

[0175] -[1,3-phenylenebis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxymethylene-4,1-phenylene)]dimethanol

[0176] -[1,2-phenylenebis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxymethylene-4,1-phenylene)]dimethanol

[0177] -[[1,1'-biphenyl]-4,4'-diylbis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxymethylene-4,1-phenylene)] dimethanol

[0178] -[[1,1'-biphenyl]-3,3'-diylbis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxymethylene-4,1-phenylene)]dimethanol

[0179] -[Naphthalene-2,3-diylbis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxymethylene-4,1-phenylene)]dimethanol

[0180] -[Naphthalene-2,7-diylbis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxymethylene-4,1-phenylene)]dimethanol

[0181] -[Naphthalene-2,6-diylbis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxymethylene-4,1-phenylene)]dimethanol

[0182] -[Naphthalene-1,4-diylbis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxymethylene-4,1-phenylene)]dimethanol

[0183] -[1,5-naphthalene-bis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxymethylene-4,1-phenylene)]dimethanol

[0184] -[Naphthalene-1,8-diylbis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxymethylene-4,1-phenylene)]dimethanol

[0185] -[Dibenzo[b,d]thiophene-4,6-diylbis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxymethylene-4,1-phenylene)]dimethanol

[0186] -[Dibenzo[b,d]thiophene-2,8-diylbis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxymethylene-4,1-phenylene)]dimethanol

[0187] -[Dibenzo[b,d]thiophene-3,7-diylbis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxymethylene-4,1-phenylene)]dimethanol

[0188] -[Thianthrene-2,7-diylbis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxymethylene-4,1-phenylene)]dimethanol

[0189] -[Thianthrene-2,8-diylbis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxymethylene-4,1-phenylene)]dimethanol

[0190] -[Thianthrene-1,4-diylbis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxymethylene-4,1-phenylene)]dimethanol

[0191] -[Thianthrene-2,3-diylbis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxymethylene-4,1-phenylene)]dimethanol

[0192] -[Thianthrene-1,6-diylbis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxymethylene-4,1-phenylene)]dimethanol

[0193] -[Thianthrene-1,9-diylbis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxymethylene-4,1-phenylene)]dimethanol

[0194] -[9H-fluorene-9,9-diylbis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxymethylene-4,1-phenylene)]dimethanol

[0195] -[9H-fluorene-2,7-diylbis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxymethylene-4,1-phenylene)]dimethanol

[0196] -[9H-xanthene-9,9-diylbis(methyleneoxy[1,1'-binaphthyl]-2',2-diyloxymethylene-4,1-phenylene)]dimethanol

[0197] -[9H-thioxanthenyl-9,9-diylbis(methyleneoxy[1,1'-binaphthyl]-2',2-diyloxymethylene-4,1-phenylene)]dimethanol

[0198] In the embodiments of the specific subgroup (8.1a) of groups (8.1), (9) and (10), wherein -Y in formula (I) 1 -A 1 -Y 2 -group is -CH2-, variable n is 1, variables m, p, q and r are all 0, and X 1 and X 2 The groups have the same meanings, the compound of formula (I) is the compound of formula (Ib),

[0199]

[0200] Where X represents the same X 1 and X 2 group, and wherein X 1 and X 2 have the meanings defined herein, particularly the meanings mentioned as being preferred.

[0201] In the embodiments of this subgroup (8.1a) of groups (8.1), (9) and (10), the structural unit of formula (II) is a structural unit of formula (IIb),

[0202]

[0203] Where # represents the connection point with the adjacent structural unit, and X a Indicates the same X 1a and X 2a group, and where the variable X1a and X 2a have the meanings defined herein, particularly the meanings mentioned as being preferred.

[0204] Preferably, the X moiety in formula (Ib) and the X moiety in formula (IIb) a The moiety is defined as one of the embodiments of group (1) and (1.1), one of the embodiments of group (2), or one of the embodiments of group (3) and (3.1). More preferably, the moiety X in formula (Ib) and the moiety X in formula (IIb) a The moiety is as defined in the embodiments of group (1.1), group (2) or group (3.1). In particular, the moiety X in formula (Ib) and the moiety X in formula (IIb) a The moieties are as defined in the embodiments of group (1.1). Thus, the moieties X in formula (Ia) here are particularly selected from 2-hydroxyethyl (i.e. 2-(HO)-ethyl), 4-(hydroxymethyl)phenyl)methyl, (3-(hydroxymethyl)phenyl)methyl, (4-(hydroxymethyl)-1-naphthyl)methyl, (6-(hydroxymethyl)-2-naphthyl)methyl, 4'-(hydroxymethyl)-1,1'-biphenyl-4-methyl, and in particular two 2-hydroxyethyl groups.

[0205] Therefore, compounds of formula (Ib) in which both X moieties are 2-hydroxyethyl are particularly preferred. Likewise, compounds in which both X a Part of the structural unit of formula (IIb) is 2(—O)-ethyl. In other words, among the compounds of formula (Ib), the compound 2,2′-[methylenebis(oxy[1,1′-binaphthylene]-2′,2-diyloxy)]di(ethan-1-ol) is particularly preferred.

[0206] As defined herein wherein X is hydrogen and A 1 The compound of formula (Ia) which is a monocyclic or polycyclic (hetero)arylene moiety is preferably prepared by a method similar to that shown in the following reaction scheme 1, wherein Ar represents the monocyclic or polycyclic (hetero)arylene moiety.

[0207] Route 1:

[0208]

[0209] In the presence of a base (e.g., an oxo base, such as an alkaline carbonate such as potassium carbonate), 1,1'-bi-2-naphthol of formula (3) is reacted with a compound of formula (4), wherein Z is a suitable leaving group, such as chloro, bromo, iodo, tosylate or mesylate, to obtain compound (5), which is a compound of formula (Ia), wherein A 1 Ar is a monocyclic or polycyclic (hetero)arylene moiety.

[0210] Where X is hydrogen, A 1 In this paper, -CH(CH2Ar A )- or -C(CH2Ar A The compound of formula (Ia) containing the 2-part can be prepared, for example, by a method similar to that shown in the following Reaction Scheme 2.

[0211] Route 2:

[0212]

[0213] In the presence of a base (e.g. an oxygen-containing base such as an alkaline carbonate such as potassium carbonate), 1,1'-bi-2-naphthol of formula (3) is reacted with a compound of formula (6) wherein Z is a suitable leaving group such as a chloro, bromo, iodo, tosylate or mesylate group and wherein R a is hydrogen or -CH2Ar A The obtained compound (7) is a compound of formula (Ia), wherein A 1 -CH(CH2Ar A )- or -C(CH2Ar A )2- moiety and X is hydrogen. Suitable solvents for this reaction are polar aprotic organic solvents such as acetone.

[0214] Where X is hydrogen, A 1 is a single bond or -CH2-, and wherein m, p, q and r are all 0, n is 1, X 1 and X 2 are all hydrogen, and -Y 1 -A 1 -Y 2 Compounds of formula (I) wherein the -CH2- moiety is a -CH2-, ie compounds of formula (Ib) wherein X is hydrogen, can be prepared, for example, by a process analogous to that shown in Scheme 3 below.

[0215] Route 3:

[0216]

[0217] In the presence of a base (e.g. an oxygen-containing base such as an alkaline carbonate or alkaline hydride, in particular an alkaline hydride such as sodium hydride), 1,1'-bi-2-naphthol of formula (3) is reacted with a compound of formula (8), wherein Z is a suitable leaving group such as bromine, iodine, toluenesulfonate or mesylate group, in particular toluenesulfonate, and wherein T is a -CH2-, -CH2CH2- or -CH2CH2CH2- moiety, to give a compound of formula (9). The resulting compound (9) is a compound of formula (Ia) or (Ib), wherein the X group is hydrogen, and A in (Ia) is 1 is a single bond or a -CH2- moiety. Suitable solvents for the reaction are polar aprotic organic solvents such as dimethylformamide or others such as acetone if an alkali metal carbonate is used as base.

[0218] A compound of formula (Ia) or (Ib), wherein X is -Alk 1 -OH, -CH2-A 2 -CH2-OH, -Alk 2 -C(O)OR x or -CH2-A 2 -C(O)OR x , and A in formula (Ia) 1 Some are single bonds, Ar, -CH(CH2Ar A )-、-C(CH2Ar A )2- or -CH2-, wherein Ar is as defined above in Scheme 1, can be prepared, for example, from compounds of the above formula (5), (7) or (9) by a method similar to that shown in Scheme 4 below.

[0219] Route 4:

[0220]

[0221] In the presence of a base (e.g., an oxygen-containing base such as an alkaline carbonate), a compound of formula (5), (7) or (9) is reacted with a compound of formula (10), wherein Z is a suitable leaving group such as a chloro, bromo, iodo, tosylate or mesylate group, and L is -Alk 1 -OH, -CH2-A 2 -CH2-OH, -Alk 2 -C(O)OR x or -CH2-A 2 -C(O)OR x , to obtain compound (11), wherein V is -CH2-Ar-CH2, -CH2-CH(CH2Ar A )-CH2-、-CH2-C(CH2Ar A)2-CH2-, -CH2-, -CH2CH2- or -CH2CH2CH2- moieties, wherein Ar is as defined above in Scheme 1. Thus, if V is -CH2-, compound (11) is a compound (Ib) of the invention, wherein X has one of the meanings listed above for the L group, or is a compound (Ia), wherein the unit -Y 1 -A 1 -Y 2 - has one of the meanings given above for unit V which is different from -CH2-, and the X group has one of the meanings listed above for the L group. Suitable solvents for the reaction of Scheme 4 are polar aprotic organic solvents, for example dimethylformamide.

[0222] If the L group in the compound of formula (11) is hydroxyethyl, the conversion shown in Scheme 4 above is preferably carried out using 2-chloroethanol, or alternatively, ethylene carbonate or ethylene oxide, especially ethylene carbonate, instead of the compound of formula (10). This conversion using 2-chloroethanol, ethylene carbonate or ethylene oxide is carried out in the presence of a base, for example an oxygen-containing base, such as an alkaline carbonate such as potassium carbonate.

[0223] As a preferred alternative to the transformations shown in Schemes 2 to 4 above, compounds of formula (Ia) or (Ib) wherein X is hydrogen, -Alk 1 -OH, -CH2-A 2 -CH2-OH, -Alk 2 -C(O)OR x or -CH2-A 2 -C(O)OR x , especially hydrogen, -Alk 1 -OH or -Alk 2 -C(O)OR x , and A in formula (Ia) 1 Some are single bonds, -CH(CH2Ar A )-、-C(CH2Ar A )2- or -CH2-, can also be prepared, for example, by a 3 to 4 step process similar to that shown in the following Reaction Scheme 5.

[0224] Route 5:

[0225]

[0226] In step a) of the present method, only one of the two hydroxyl groups of 1,1'-bi-2-naphthol of formula (3) is protected by introducing a protecting group, which is preferably an arylmethyl group, such as, in particular, a benzyl group. The arylmethyl group, in particular a benzyl group, can be introduced by methods known in the art, for example, by reacting 1,1'-bi-2-naphthol (3) with typically 0.5 to 1.5 molar equivalents of benzyl bromide or benzyl chloride in the presence of a suitable base (e.g., an alkali metal carbonate, such as potassium carbonate, or an alkali metal hydride, such as sodium hydride). The monoprotected derivative of formula (12) is thus obtained, wherein PG is a suitable protecting group, such as benzyl. In the subsequent step b), the mono-protected 1,1'-bi-2-naphthol derivative (12) is reacted with a compound of formula (13) in the presence of a base (e.g. an oxygen-containing base such as an alkali metal carbonate, e.g. potassium carbonate, or an alkali metal hydride, e.g. sodium hydride), wherein Z is a suitable leaving group, e.g. a bromine, iodine, tosylate or mesylate group, and wherein V' is -CH2-CH(CH2Ar A )-CH2-、-CH2-C(CH2Ar A )2-CH2-, -CH2-, -CH2CH2- or -CH2CH2CH2- moieties to obtain a compound of formula (14). In the subsequent step c), compound (14) can be deprotected to the corresponding diol of formula (15) using established procedures, for example, if the protecting group to be removed is a benzyl group, it can be removed by catalytic hydrogenation. The resulting diol (15) is a compound of formula (Ia) or (Ib), wherein X is hydrogen, and A in formula (Ia) is 1 Some are single bonds, -CH(CH2Ar A )-、-C(CH2Ar A )2- or -CH2-. In optional step d), diol (15) is converted into the corresponding compound of formula (15'), which is also a compound of formula (Ia) or (Ib), but in which X is not hydrogen but Alk 1 -OH,-CH2-A 2 -CH2-OH, -Alk 2 -C(O)OR x or -CH2-A 2 -C(O)OR x , and especially -Alk 1 -OH or -Alk 2 -C(O)OR x or -CH2-A 2 -C(O)OR xObviously, the conversion of diol (15) to compound (15') can be accomplished, for example, in a manner analogous to the procedure described above in connection with Scheme 4, i.e. by reacting diol (15) with a compound of formula (10'), wherein Z has the same meaning as described for compound (10), and L' is -Alk 1 -OH, -CH2-A 2 -CH2-OH, -Alk 2 -C(O)OR x or -CH2-A 2 -C(O)OR x , especially -Alk 1 -OH or -Alk 2 -C(O)OR x This reaction sequence is particularly suitable for the production of compounds of formula (Ia) and (Ib) wherein X is hydrogen, -Alk 1 -OH or -Alk 2 -C(O)OR x , and A in formula (Ia) 1 Some are single bonds, -CH(CH2Ar A )-、-C(CH2Ar A )2- or -CH2-.

[0227] As another preferred alternative to the transformations shown in Schemes 2 to 4 above, compounds of formula (Ia) or (Ib) wherein X is -CH2-A 2 -CH2-OH or -CH2-A 2 -C(O)OR x , and A in formula (Ia) 1 Some are single bonds, -CH(CH2Ar A )-、-C(CH2Ar A )2- or -CH2-, especially a single bond, -CH(CH2Ar A )-、-C(CH2Ar A )2- or -CH2-, wherein Ar is as defined above in Scheme 1, can also be prepared, for example, by a 2-step process similar to that shown in Scheme 6 below.

[0228] Route 6:

[0229]

[0230] In step a) of the process, 1,1'-bi-2-naphthol of formula (3) is reacted with typically 0.5 to 1.5 molar equivalents of a compound of formula (10"), wherein Z is a suitable leaving group, such as chloro, bromo, iodo, tosylate or mesylate, and L" is -CH2-A in the presence of a base, such as an oxygen-containing base, such as an alkali metal carbonate, for example potassium carbonate. 2 -CH2-OH or -CH2-A 2 -C(O)OR x , to obtain compound (16). The suitable solvent for this reaction step is preferably selected from polar aprotic organic solvents, such as dimethylformamide. In step b), compound (16) is reacted with a compound of formula (13') in the presence of a base (e.g. an oxygen-containing base, such as an alkaline carbonate such as potassium carbonate), wherein Z is a suitable leaving group, such as a chloro, bromo, iodo, tosylate or mesylate group, and wherein V" is -CH2-Ar-CH2-, -CH2-CH(CH2Ar A )-CH2-、-CH2-C(CH2Ar A )2-CH2-, -CH2-, -CH2CH2- or -CH2CH2CH2- moieties, in particular CH2-CH(CH2Ar A )-CH2-、-CH2-C(CH2Ar A )2-CH2-, -CH2-, -CH2CH2- or -CH2CH2CH2- moieties. A suitable solvent for this reaction step is a polar aprotic organic solvent, such as acetone. The compound of formula (17) obtained by this reaction is the desired compound of formula (Ia) or (Ib), particularly characterized in that X is -CH2-A 2 -CH2-OH or -CH2-A 2 -C(O)OR x This reaction sequence is particularly suitable for the production of compounds of formula (Ia) and (Ib) wherein X is -CH2-A 2 -CH2-OH or -CH2-A 2 -C(O)OR x , and wherein A in formula (Ia) 1 Some are single bonds, -CH(CH2Ar A )-、-C(CH2Ar A )2- or -CH2-.

[0231] As an alternative to the transformations shown in Schemes 1 to 6 above, compounds of formula (Ia) or (Ib) wherein X is other than hydrogen may also be prepared, for example, by a 4-step process analogous to that shown in Scheme 7 below.

[0232] Route 7:

[0233]

[0234] In step a) of the present method, 1,1'-bi-2-naphthol of formula (3) is monoprotected by introducing a suitable protecting group PG', which is selected from hydroxy protecting groups established in the art, such as 2-tetrahydropyranyl, benzyl, diphenylmethyl, triphenylmethyl, allyl, propargyl or tert-butyloxycarbonyl (Boc), to obtain a compound of formula (18). For a person skilled in the art, it is obvious that the PG' group should be selected to be compatible with the subsequent reaction. For example, if in step d) the variable A in the compound of formula (20) is 1 is an Ar moiety, which is as defined above in Scheme 1, then PG' should preferably be different from benzyl. The introduction of the protecting group PG' in step a) and its removal in step c) (obtaining the alcohol of formula (19)) can be carried out in a manner analogous to corresponding procedures established in the art (see, for example, EP 0 915 073 B1; T. Song et al., Advanced Synthesis & Catalysis 2014, 356 (8), 1708-1718; C. Dong et al., Catalysis Science & Technology 2015, 5 (10), 4755-4759; L. Jin et al., Tetrahedron: Asymmetry 2008, 19 (16), 1947-1953; A. R. Abreu et al., Tetrahedron 2010, 66 (3), 743-749; Y. Wang et al., Journal of the American Chemical Society 2012, 134 (7), 3342-3345; H. Hocke et al., Tetrahedron 2003, 59 (5), 619-630; G. Ma et al., Angewandte Chemie, International Edition 2014, 53 (44), 11818-11821; M. Nuruzzaman et al., Synlett 2008, 2, 207-212; and SC Jha et al., Synthetic Organic Chemistry 2003, 33: 6, 1005-1009). For the introduction of the group L "' (which is -Alk 1 -OH, -CH2-A 2 -CH2-OH, -Alk 2 -C(O)OR x or -CH2-A 2 -C(O)OR xThe intermediate step b) of the method can be carried out, for example, in a manner similar to the reaction of the above-mentioned route 4. The final step d) gives the desired product of formula (20), wherein the V"' part is -CH2-Ar-CH2-, -CH2-CH(CH2Ar A )-CH2-、-CH2-C(CH2Ar A )2-CH2-, -CH2-, -CH2CH2- or -CH2CH2CH2- can be carried out, for example, in a manner similar to any one of the reactions in step b) in Schemes 1 to 3 and Schemes 5 and 6.

[0235] The above reactions according to routes 1 to 7, in particular routes 1 to 4, can also be used to prepare compounds of formula (I) in which the variable n is different from 1, i.e. 2 or 3, or to prepare mixtures of compounds of formula (I) which differ only in the value of the variable n. It is obvious to a person skilled in the art that by appropriately adjusting the reaction conditions of the above reactions of routes 1 to 7, in particular the reaction conditions of routes 1 to 3, these reactions can generally be directed to compounds of formula (I) in which n is 2 or 3. For example, this can be achieved by appropriately increasing the amount ratio of the compounds of formula (4), (6) and (8) to 1,1'-bi-2-naphthol (3) used in the reactions of routes 1 to 3.

[0236] The naphthyl part has a substituent R 1 , R 2 , R 3 and / or R 4 The compound of formula (I) can be prepared by reactions similar to those in the above routes 1 to 7, at least when R 1 and R 2 R 3 and R 4 For this purpose, the 1,1'-bi-2-naphthol (3) used in the reactions of Schemes 1 to 7 is replaced by a 1,1'-bi-2-naphthol derivative, which is correspondingly replaced by R 1 (=R 3 ) and optionally also with R 2 (=R 4 )replace.

[0237] The transformations shown in Schemes 1 to 7 can be accomplished by the above reactions in these schemes or by obvious variations of these reactions, or alternatively, by established procedures in preparative organic chemistry, or by combinations thereof.

[0238] Other compounds of formula (I) may be prepared by employing obvious variations and combinations of the above reactions and well-established methods of preparative organic chemistry.

[0239] The reaction mixture obtained in each step of the synthesis of the compound described in the above-mentioned reaction schemes 1, 2, 3, 4, 5, 6 and 7 is usually refined in a conventional manner, for example, by mixing with water, separating each phase and by washing, chromatography or crystallization purification crude product when appropriate. In some cases, the intermediate forms a form of colorless or light brown viscous oil, which does not contain volatiles or is purified at a reduced pressure and a moderately elevated temperature. If a solid intermediate is obtained, purification can be achieved by recrystallization or washing methods such as slurry washing.

[0240] The starting compounds used to prepare compounds of formula (I) in the syntheses shown in Schemes 1, 2, 3, 4, 5, 6 and 7 above are commercially available or can be prepared by methods known in the art.

[0241] As mentioned above, the compounds of the invention can be obtained in very high purity, which means that the obtained product does not contain significant amounts of organic impurities other than the compounds of formula (I) other than volatiles. Typically, the purity of the compound of formula (I) is at least 95%, in particular at least 98%, and in particular at least 99%, based on non-volatile organic matter, i.e. the product contains at most 5%, in particular at most 2% and in particular at most 1% of non-volatile impurities other than the compounds of formula (I).

[0242] The term "volatiles" refers to the 5 Non-volatile organic substances are therefore understood to mean compounds having a boiling point of more than 200° C. at standard pressure.

[0243] A particular benefit of the present invention is that compounds of formula (I) and solvates thereof are generally available in crystalline form. In crystalline form, compounds of formula (I) may exist in pure form or in the form of solvates with water or an organic solvent. Therefore, a specific aspect of the present invention relates to compounds of formula (I) that exist substantially in crystalline form. In particular, the present invention relates to crystalline forms in which compounds of formula (I) exist in the absence of solvents, and to crystalline solvates of compounds of formula (I) in which the crystals contain incorporated solvents.

[0244] A special benefit of the present invention is that the compound of formula (I) and its solvate can usually be easily crystallized from conventional organic solvents. This allows the compound of formula (I) to be effectively purified. Suitable organic solvents for crystallizing the compound of formula (I) or its solvate include, but are not limited to, aromatic hydrocarbons such as toluene or xylene, aliphatic ketones, particularly ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone or diethyl ketone with 3 to 6 carbon atoms, aliphatic and alicyclic ethers such as diethyl ether, dipropyl ether, methyl isobutyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, dioxane or tetrahydrofuran, aliphatic-aromatic ethers such as anisole, and aliphatic alcohols such as methanol, ethanol or isopropanol with 1 to 4 carbon atoms, and mixtures thereof. Before the crystallization step, filtering the dissolved crude preparation of the compound of formula (I) (e.g., by diatomaceous earth) may be beneficial to remove solid components that may be present in the crude preparation.

[0245] Furthermore, impurities, in particular color-forming impurities, which may be present in the crude preparation of the compound of formula (I) can be removed at any stage of the purification process, for example before a filtration step or a crystallization step, by standard procedures, for example treatment with an adsorbent, such as activated carbon.

[0246] Alternatively, compounds of formula (I) and solvates thereof can be obtained in purified form by adopting other simple and effective methods for purifying crude products of these compounds, such as, in particular, slurry washing of the crude solid obtained directly after conversion, to prepare compounds of formula (I). Slurry washing is usually carried out at ambient temperature or at elevated temperatures of generally about 30 to 90° C., in particular 40 to 80° C. Suitable organic solvents are in principle the same as those listed above for crystallization of compounds of formula (I), such as, in particular, the aromatic hydrocarbons, aliphatic ketones and aliphatic ethers mentioned, such as toluene, methyl ethyl ketone and methyl tert-butyl ether.

[0247] Therefore, the compounds of formula (I) for preparing thermoplastic polymers, particularly polycarbonates defined herein can be easily prepared and obtained in high yield and high purity. In particular, the compounds of formula (I) can be obtained in crystalline form, which allows effective purification to the degree required in the preparation of optical resins. In particular, these compounds can be obtained with a purity that provides high refractive index and low haze, which is particularly important for the use of optical resins used for preparing optical devices. In a word, the compounds of formula (I) are particularly useful as monomers in the preparation of optical resins.

[0248] The skilled person will readily appreciate that the formula (I) of the monomer used corresponds to the formula (II) of the structural unit included in the thermoplastic resin. Similarly, the formulas (Ia) and (Ib) of the monomer used correspond to the formulas (IIa) and (IIb) of the structural unit included in the thermoplastic resin, respectively.

[0249] The skilled artisan will also appreciate that the structural units of formula (II), (IIa) and (IIb) are repeating units within the polymer chain of the thermoplastic resin.

[0250] In addition to the structural units of formula (II), (IIa) and (IIb), the thermoplastic resin may also have structural units different therefrom. In a preferred embodiment, these other structural units are derived from aromatic monomers of formula (IV), thereby producing structural units of formula (V):

[0251] HO-R z -A 3 -R z -OH(IV)

[0252] #-OR z -A 3 -R z -O-#(V)

[0253] in

[0254] # indicates the connection point with the adjacent structural unit;

[0255] A 3 is a polycyclic group with at least two benzene rings, wherein the benzene rings may be connected via W and / or directly fused to each other and / or fused via a non-benzene carbon ring and / or fused via two non-benzene carbon rings connected via a linker L, wherein A 3 R is unsubstituted or substituted by 1, 2 or 3 R selected from halogen, C1-C6-alkyl, C5-C6-cycloalkylphenyl, naphthyl, 1,2-dihydroacenaphthenyl, phenanthrenyl, pyrenyl, triphenylene, benzo[b]furanyl, dibenzo[b,d]furanyl, benzo[b]thienyl, dibenzo[b,d]thienyl and thianthrenyl aa group substitution;

[0256] W is selected from a single bond, O, C=O, S, S(O), SO2, CH2, CH-Ar, CAr2, CH(CH3), C(CH3)2 and a group of formula (A')

[0257]

[0258] in

[0259] Q' represents a single bond, O, C=O or CH2;

[0260] R 7a , R 7b are independently selected from hydrogen, fluorine, CN, R, OR, CH v R' 3-v, NR2, C(O)R and C(O)NH2, wherein R and R' are as defined in claim 1, and v is 0, 1 or 2; and

[0261] * indicates the point of attachment to the benzene ring;

[0262] L is selected from a single bond, C1-C4-alkylene, C4-C7-cycloalkylene, C4-C7-cycloalkylene dimethylene, phenylene dimethylene, wherein L is unsubstituted or substituted by 1 or 2 R selected from C1-C4-alkyl, halogen, C1-C4-haloalkyl, C4-C7-cycloalkyl and phenyl L Group substitution,

[0263] Ar is selected from monocyclic or polycyclic aryl radicals having 6 to 26 carbon atoms as ring atoms and monocyclic or polycyclic heteroaryl radicals having a total of 5 to 26 atoms as ring members, wherein 1, 2, 3 or 4 of these ring member atoms of the heteroaryl radical are selected from nitrogen, sulfur and oxygen, and the remaining atoms of these ring member atoms of the heteroaryl radical are carbon atoms, wherein Ar is unsubstituted or replaced by 1, 2 or 3 R selected from halogen, phenyl and C1-C4-alkyl ab group substitution;

[0264] R z For single bond, Alk 3 、O-Alk 4 -、O-Alk 4 -[O-Alk 4 -] w - or O-Alk 5 -C(O)-, where O is bound to A 3 , and among them

[0265] w is an integer from 1 to 10;

[0266] Alk 3 is C1-C4-alkanediyl;

[0267] Alk 4 is C2-C4-alkanediyl; and

[0268] Alk 5 It is C1-C4-alkanediyl.

[0269] If R in formula (IV) z It's O-Alk 5 -C(O), esters of the monomers of the formula (IV), in particular C1-C4-alkyl esters, can be used instead.

[0270] In the context of formula (IV) and (V), A 3In particular, polycyclic radicals with two benzene or naphthalene rings, wherein the benzene rings are linked via W or fused via two non-benzene carbon rings linked via a linker L, wherein W is in particular selected from a single bond, S, S(O), SO2, C(CH3)2 and an A' group, and wherein L is a single bond or a C1-C4-alkylene group.

[0271] In the context of formulae (IV) and (V), R z Especially O-Alk 4 -, where Alk 4 In particular it is a straight-chain alkanediyl radical having 2 to 4 carbon atoms and in particular O-CH2CH2.

[0272] Among the monomers of formula (IV), monomers of general formulae (IV-1) to (IV-8) are preferred.

[0273]

[0274]

[0275] in

[0276] a and b are 0, 1, 2 or 3, in particular 0 or 1;

[0277] a' and b' are 0, 1, 2 or 3, in particular 0 or 1;

[0278] c and d are 0, 1, 2, 3, 4 or 5, in particular 0 or 1;

[0279] e and f are 0, 1, 2, 3, 4 or 5, in particular 0 or 1;

[0280] W' is S, S(O), SO2, O, a single bond, CH2, CH(CH3), C(CH3)2, in particular S, S(O), SO2 or C(CH3)2;

[0281] And where R z , R aa , R ab , R 7a , R 7b and L are as defined for formula (IV), and wherein R z In particular, it is selected from a single bond, CH2 and OCH2CH2.

[0282] Among the monomers of formula (IV), monomers of general formulae (IV-11) to (IV-22) are particularly preferred, wherein R z and R aa As defined herein, and R z In particular selected from a single bond, CH2 and O-CH2CH2, in particular O-CH2CH2:

[0283]

[0284]

[0285] Examples of compounds of formulae (IV-11) to (IV-22) are 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-isopropylphenyl)fluorene, 9,9-bis(4-hydroxy-3-tert-butylphenyl)fluorene, 9,9-bis(4-hydroxy-3-cyclohexylphenyl)fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (BPEF), 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-isopropylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butylphenyl)fluorene, 9,9-bis(6-hydroxy-2-naphthyl)fluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)fluorene (also known as 9,9-bis(6-(2-hydroxyethoxy)naphth-2-yl)fluorene (BNEF)) or 6,6′-(9-fluorenylidene)bis(2-naphthyloxyethanol) (NOLE), 10,10-bis(4-(2-hydroxyethoxy)phenyl)anthracen-9-one, 10,10-bis(4-(2-hydroxyethoxy)phenyl)anthracen-9-one, 4,4′-dihydroxytetraphenylmethane, 4,4′-di- (2-Hydroxyethoxy)-tetraphenylmethane, 3,3'-diphenyl-4,4'-dihydroxy-tetraphenylmethane, di-(6-hydroxy-2-naphthyl)-diphenylmethane, 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-diphenyl-phenyl]-1-methyl-ethyl]-2,6-diphenyl-phenoxy]ethanol, 2-[4-[1-[4-(2-hydroxyethoxy)-3-phenyl-phenyl]-1-methyl-ethyl]-2,6-diphenyl-phenoxy]ethanol, 9,9'-dihydroxymethyl-9,9'-difluorene, 2,2'-[1,1'-binaphthyl-2,2'-diylbis(oxy)]diethanol (also known as 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl or 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl (BNE)), 2,2'-bis(1-hydroxymethoxy)-1,1'-binaphthyl, 2,2'-bis(3-hydroxypropoxy)-1,1'-binaphthyl, 2,2'-bis(4-hydroxybutoxy)-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-6,6'-di(naphthalene-1-yl)-1,1'-binaphthyl, 2,2'-bis(2-hydroxymethoxy)-6,6'-diphenyl-1,1'-binaphthyl, 2,2'-bis(2-hydroxymethoxy)-6,6'-di(naphthalene-1-yl)-1,1'-binaphthyl, 2,2'-bis(2-hydroxypropoxy)-6,6'-diphenyl-1,1'-binaphthyl, 2,2'-bis(2-hydroxypropoxy)-6,6'-di(naphthalen-1-yl)-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-6,6'-di(naphthalen-2-yl)-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-6,6'-di(9-phenanthrenyl)-1,1'-binaphthyl, 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-di(naphthalen-1-yl)-phenyl]-1-methyl-ethyl]-2,6-di(naphthalen-1-yl) )-phenoxy]ethanol, 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-di(naphthalen-2-yl)-phenyl]-1-methyl-ethyl]-2,6-di(naphthalen-2-yl)-phenoxy]ethanol, 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-di(phenanthren-9-yl)-phenyl]-1-methylethyl]-2,6-di(phenanthren-9-yl)-phenoxy]ethanol, 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-di(1,2-dibenzo[b,d]thiophen-4-yl)-phenyl]-1-methyl-ethyl]- 2,6-bis(1,2-dibenzo[b,d]thiophen-4-yl)-phenoxy]ethanol, 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-di(thianthren-1-yl)-phenyl]-1-methyl-ethyl]-2,6-di(thianthren-1-yl)-phenoxy]ethanol, 2-[4-[4-(2-hydroxyethoxy)-3,5-di(naphthalen-1-yl)phenyl]sulfonyl-2,6-di(naphthalen-1-yl)-phenoxy]ethanol, 2-[4-[4-(2-hydroxyethoxy)-3,5-di(naphthalen-2-yl)phenyl]sulfonyl-2,6-di( 2-[4-[4-(2-hydroxyethoxy)-3,5-di(phenanthrene-9-yl)phenyl]sulfonyl-2,6-di(phenanthrene-9-yl)-phenoxy]ethanol, 2-[4-[4-(2-hydroxyethoxy)-3,5-di(thianthrene-1-yl)phenyl]sulfonyl-2,6-di(thianthrene-1-yl)phenoxy]ethanol and 2-[4-[4-(2-hydroxyethoxy)-3,5-di(dibenzo[b,d]thiophen-4-yl)phenyl]sulfonyl-2,6-dibenzo[b,d]thiophen-4-yl)phenoxy]ethanol, etc.

[0286] Among the monomers of the general formula (IV) or formulas (IV-1) to (IV-8), the monomers of formulas (IV-1), (IV-2), (IV-3) and (IV-8) are particularly preferred, and the monomers of formulas (IV-11), (IV-12), (IV-13), (IV-14), (IV-15), (IV-21) and (IV-22) are even more preferred, and 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl (BNE or BHBNA), ... 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)fluorene (BNEF), 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene (BPPEF), 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-di(phenanthrene-9-yl)-phenyl]-1-methylethyl]-2,6-di(phenanthrene-9-yl) ... -yl)-phenoxy]ethanol, 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-di(1,2-dibenzo[b,d]thiophen-4-yl)-phenyl]-1-methyl-ethyl]-2,6-di(1,2-dibenzo[b,d]thiophen-4-yl)-phenoxy]ethanol, 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-di(thianthren-1-yl)-phenyl]-1-methyl-ethyl]-2,6-di(thianthren-1-yl)-phenoxy]ethanol, 2-[4-[4 -(2-hydroxyethoxy)-3,5-di(phenanthrene-9-yl)phenyl]sulfonyl-2,6-di(phenanthrene-9-yl)-phenoxy]ethanol, 2-[4-[4-(2-hydroxyethoxy)-3,5-di(thianthren-1-yl)phenyl]sulfonyl-2,6-di(thianthren-1-yl)phenoxy]ethanol and 2-[4-[4-(2-hydroxyethoxy)-3,5-di(dibenzo[b,d]thien-4-yl)phenyl]sulfonyl-2,6-dibenzo[b,d]thien-4-yl)phenoxy]ethanol.

[0287] Therefore, among the structural units of formula (V) that may be included in the thermoplastic resin, structural units of general formulae (V-1) to (V-8) are preferred.

[0288]

[0289]

[0290] in

[0291] a and b are 0, 1, 2 or 3, in particular 0 or 1;

[0292] a' and b' are 0, 1, 2 or 3, in particular 0 or 1;

[0293] c and d are 0, 1, 2, 3, 4 or 5, in particular 0 or 1;

[0294] e and f are 0, 1, 2, 3, 4 or 5, in particular 0 or 1;

[0295] W' is S, S(O), SO2, O, a single bond, CH2, CH(CH3), C(CH3)2, in particular S, S(O), SO2 or C(CH3)2;

[0296] And where R z , R aa , R ab , R 7a , R 7b and L are as defined for formula (V), and wherein R z In particular, it is selected from a single bond, CH2 and OCH2CH2.

[0297] Particularly preferred are structural units of the general formulae (V-11) to (V-22) in which R z and R aa As defined herein, and wherein R z In particular selected from a single bond, CH2 and O-CH2CH2, and in particular O-CH2CH2:

[0298]

[0299]

[0300] Among the structural units of formulae (V-1) to (V-8), structural units of formulae (V-1), (V-2), (V-3) and (V-8) are particularly preferred. Among the structural units of formulae (V-11) to (V-22), structural units of formulae (V-11), (V-12), (V-13), (V-14), (V-15) (V-21) and (V-22) are particularly preferred, and structural units derived from 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl (BNE or BHBNA), 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl (DPBHBNA), 9, 9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (BPEF), 9,9-bis(6-(2-hydroxyethoxy)naphth-2-yl)fluorene (BNEF), 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene (BPPEF), 2-[4-[4-(2-hydroxyethoxy)-3,5-di(thianthren-1-yl)phenyl]sulfonyl-2,6-di(thianthren-1-yl)phenoxy]ethanol, 2-[4-[4-(2-hydroxyethoxy)-3,5 -bis(phenanthrene-9-yl)phenyl]sulfonyl-2,6-bis(phenanthrene-9-yl)-phenoxy]ethanol, 2-[4-[4-(2-hydroxyethoxy)-3,5-bis(dibenzo[b,d]thiophen-4-yl)phenyl]sulfonyl-2,6-dibenzo[b,d]thiophen-4-yl)phenoxy]ethanol, 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-bis(phenanthrene-9-yl)phenyl]-1-methylethyl]-2,6-bis(phenanthrene-9-yl)-phenoxy ]ethanol, 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-di(1,2-dibenzo[b,d]thiophen-4-yl)-phenyl]-1-methyl-ethyl]-2,6-di(1,2-dibenzo[b,d]thiophen-4-yl)-phenoxy]ethanol and 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-di(thianthren-1-yl)-phenyl]-1-methyl-ethyl]-2,6-di(thianthren-1-yl)-phenoxy]ethanol.

[0301] In a particularly preferred embodiment, the thermoplastic resin of the present invention comprises at least one structural unit of formula (IIa) or (IIb) and at least one structural unit selected from the group consisting of structural units of formula (V-11), structural units of formula (V-12), structural units of formula (V-13), structural units of formula (V-14), structural units of formula (V-15), structural units of formula (V-21) and structural units of formula (V-22). In this specific embodiment, it is preferred that the radical R in the structural units of formula (V-11), (V-12), (V-13), (V-14), (V-15), (V-21) and (V-22) zThose thermoplastic resins which are O-CH2CH2.

[0302] In the thermoplastic resin of this group of particularly preferred embodiments, the total molar ratio of the structural units of formula (IIa) or (IIb) to the total amount of the structural units of formula (II) and (V) is preferably in the range of 1-99 mol%, preferably in the range of 5-98 mol%, further preferably in the range of 10-97 mol%, and even further preferably in the range of 20-95 mol%.

[0303] Compounds of formula (IV), (IV-1), (IV-2), (IV-3), (IV-4), (IV-5), (IV-6), (IV-7), (IV-8), (IV-11), (IV-12), (IV-13), (IV-14), (IV-15), (IV-16), (IV-17), (IV-18), (IV-19), (IV-20), (IV-21) and (IV-22) are known or can be prepared by analogy to known methods.

[0304] For example, the compound of formula (IV-8) can be prepared by various synthesis methods, such as disclosed in Japanese Publication No. 2014-227387, Japanese Publication No. 2014-227388, Japanese Publication No. 2015-168658, and Japanese Publication No. 2015-187098. For example, 1,1'-binaphthol can be reacted with ethylene glycol monotoluenesulfonate (monotosylates); alternatively, 1,1'-binaphthol can be reacted with alkylene oxides, halogenated alkanols, or alkylene carbonates; alternatively, 1,1'-binaphthol can be reacted with ethylene carbonate (ethylene carbonates). Thus, a compound of formula (IV-8) is obtained, wherein R z -OH is O-Alk 2 - or O-Alk 2 -[O-Alk 2 -] p -.

[0305] For example, the compound of formula (IV-2) can be prepared by various synthesis methods, such as disclosed in Japanese Patent Publication No. 5442800 and Japanese Publication No. 2014-028806. Examples include:

[0306] (a) reacting fluorene with hydroxynaphthalene in the presence of hydrochloric acid gas and mercaptocarboxylic acid;

[0307] (b) reacting 9-fluorene with hydroxynaphthalene in the presence of an acid catalyst (and an alkyl mercaptan);

[0308] (c) reacting fluorene with hydroxynaphthalene in the presence of a hydrochloride salt and a thiol (e.g., mercaptocarboxylic acid);

[0309] (d) reacting fluorene with hydroxynaphthalene in the presence of sulfuric acid and a thiol (e.g., mercaptocarboxylic acid), and then crystallizing the product from a crystallization solvent consisting of a hydrocarbon and a polar solvent to form binaphthol fluorene; etc.

[0310] Thus, a compound of formula (IV-2) can be obtained, wherein R z It is a single bond.

[0311] The compound of formula (IV) (wherein R z O-Alk 2 - or O-Alk 2 -[O-Alk 2 -] p -) can be made from a compound of formula (IV) (wherein R z is a single bond) by reacting with an alkylene oxide or a halogenated alkanol. z is a single bond) and 9,9-bis(hydroxynaphthyl)-fluorene is reacted with an alkylene oxide or a haloalkanol to produce a compound of formula (IV-2) (wherein R z It's O-Alk 2 - or O-Alk 2 -[O-Alk 2 -] p -). For example, 9,9-bis[6-(2-hydroxyethoxy)naphthyl]fluorene can be prepared by reacting 9,9-bis[6-(2-hydroxynaphthyl]fluorene with 2-chloroethanol under alkaline conditions.

[0312] The monomers of formula (I) and likewise the comonomers of formula (IV) used for the production of thermoplastic resins may contain certain impurities resulting from their preparation, for example, hydroxyl compounds with OH groups instead of, for example, groups O-Alk 1 -OH, or it may contain the group O-Alk 1 -[O-Alk 1 ] o -Substituent O-Alk 1-, or if only one oligomer monomer with n=1, 2 or 3 replaces the oligomer mixture with different n values, in addition to the expected oligomers, undesired oligomers may also be contained. The total amount of these impurity compounds is preferably 5000 ppm or less, more preferably 3000 ppm or less, still more preferably 2000 ppm or less, and particularly preferably 1000 ppm or less. The total content of impurities in the monomers used to prepare the thermoplastic resin is preferably 4000 ppm or less, particularly 1500 ppm or less, and more preferably 1000 ppm or less. In particular, in the monomers represented by the dihydroxy compound represented by formula (I) as the main component, wherein the group X 1 or X 2 The total amount of dihydroxy compounds having at least one carbon number different from that of formula (I) is preferably 3000 ppm or less, more preferably 1500 ppm or less, still more preferably 1000 ppm or less, and particularly preferably 500 ppm or less. 1 or X 2 The total content of dihydroxy compounds in which at least one carbon number is different from that of formula (I) is further preferably 1000 ppm or less, and more preferably 500 ppm or less. Likewise, the amount of impurities in the comonomer of formula (IV) will be within the range given for the monomer of formula (I).

[0313] In this context, it should be noted again that mixtures of compounds of formula (I) with different values ​​for the variable n are also part of the invention. Such mixtures are just as well suited as the individual compounds of formula (I) for use as monomers for the production of thermoplastic resins having advantageous properties. Thus, for the production of the thermoplastic resins of the invention, it is possible to use monomers of formula (I) with n=1, monomers of formula (I) with n=2, monomers of formula (I) with n=3 or any mixtures of these compounds.

[0314] Suitable thermoplastic resins for the production of optical devices such as lenses are especially polycarbonates, polyester carbonates and polyesters. Preferred thermoplastic resins for the production of optical devices such as lenses are especially polycarbonates.

[0315] The polycarbonate is characterized in that it has structural units of at least one of formula (II), (IIa) and (IIb), respectively, optionally structural units derived from diol monomers other than monomer compounds of formula (I), such as structural units of formula (V),

[0316] #-OR z -A 3 -R z -O-#(V)

[0317] in

[0318] #、Rz and A 3 As defined above;

[0319] and structural units of formula (III-1) derived from carbonate-forming components:

[0320]

[0321] wherein each # represents the point of attachment to the adjacent structural unit, ie, O at the point of attachment to the structural unit of formula (II) and O at the point of attachment to the structural unit of formula (V), if present.

[0322] The polyester is characterized in that it has structural units of at least one of formula (II), (IIa) and (IIb), respectively, optionally structural units derived from diol monomers other than the monomer compound of formula (I), such as structural units of formula V. If X in formula (II), (IIa) and (IIb) 1a and X 2a Selected from single bond, -Alk 1 -O-- and -CH2-A 2 -CH2-O-, the polyester may have structural units derived from one or more dicarboxylic acids, for example, in the case of phthalic acid, the structure of formula (III-2), in the case of naphthoic acid, the structure of formula (III-3), in the case of oxalic acid, the structure of formula (III-4), and in the case of malonic acid, the structure of formula (III-5):

[0323]

[0324] In formulae (III-2) to (III-5), each variable # represents the point of connection to the adjacent structural unit, ie, O at the point of connection to the structural unit of formula (II) and O at the point of connection to the structural unit of formula (V), if present.

[0325] The polyester carbonate is characterized in that it has structural units of at least one of the formulae (II), (IIa) and (IIb), respectively, optionally structural units derived from diol monomers other than monomer compounds of the formula (I), for example structural units of the formula (V), structural units of the formula (III-1) derived from carbonate-forming components and structural units derived from dicarboxylic acids, for example, in the case of phthalic acid, it has the structure of the formula (III-2), in the case of naphthoic acid, it has the structure of the formula (III-3), in the case of oxalic acid, it has the structure of the formula (III-4) and in the case of malonic acid, it has the structure of the formula (III-5).

[0326] A specific group of embodiments relates to thermoplastic copolymer resins, in particular polycarbonates, polyester carbonates and polyesters, having structural units of formula (II) and one or more structural units of formula (V), i.e. resins, in particular polycarbonates, polyester carbonates and polyesters, which can be obtained by reacting at least one monomer of formula (I) with one or more monomers of formula (IV). In this case, the molar ratio of the monomer of formula (I) to the monomer of formula (IV) and the molar ratio of the structural units of formula (II) to the structural units of formula (V) is in the range of 1:99 to 99:1, in particular in the range of 20:80 to 98:2, in particular in the range of 30:70 to 97:3, or in the range of 10:90 to 99:1, in particular in the range of 15:85 to 98:2, 15:85 to 90:10, 15:85 to 80:20 or 15:85 to 70:30, more preferably in the range of 20: :3 or 27:73 to 90:1 , and in particular in the range of 30:70 to 80:20 or in the range of 35:65 to 70:30. Therefore, based on the total molar amount of the structural units of formula (II) and (V), the molar ratio of the structural units of formula (II) is generally 1 to 99 mol%, in particular 20 to 98 mol%, more preferably in the range of 30 to 97 mol% or in the range of 10 to 99 mol%, in particular in the range of 20 to 97 mol% or in the range of 27 to 97 mol%, even more preferably in the range of 27 to 90 mol%, and in particular in the range of 30 to 80 mol% or in the range of 35 to 70 mol%. Therefore, based on the total molar amount of the structural units of formula (II) and (V), the molar ratio of the structural units of formula (V) is generally 1 to 99 mol%, in particular 2 to 80 mol%, more preferably in the range of 3 to 70 mol% or in the range of 1 to 90 mol%, in particular in the range of 2 to 85 mol% or in the range of 3 to 80 mol%, even more preferably in the range of 10 to 73 mol%, and in particular in the range of 20 to 70 mol% or in the range of 30 to 65 mol%. The above molar ratio may be applied to the molar ratio of the structural unit of formula (II) to the total structural units of the thermoplastic copolymer resin.

[0327] A specific group of embodiments relates to thermoplastic copolymer resins, in particular polycarbonates, polyester carbonates and polyesters, which have both structural units of formula (II) and one or more structural units of formula (V-14) or (V-15), i.e. resins, in particular polycarbonates, polyester carbonates and polyesters, which can be obtained by reacting at least one monomer of formula (I) with one or more monomers of formula (IV-14) or (IV-15). In this case, the molar ratio of the monomer of formula (I) to the monomer of formula (IV-14) and (IV-15) and the molar ratio of the structural units of formula (II) to the structural units of formula (V-14) and (V-15) are in the range of 50:50 to 99:1, in particular in the range of 70:30 to 98:2, in particular in the range of 80:20 to 97:3. The above molar ratios may apply to the molar ratio of the structural units of formula (II) to the total structural units of the thermoplastic copolymer resin.

[0328] Another specific group of embodiments relates to thermoplastic copolymer resins, in particular polycarbonates, polyester carbonates and polyesters, which have both structural units of formula (II) and one or more structural units of formula (V-11), (V-12), (V-13), (V-21) or (V-22), i.e. resins, in particular polycarbonates, polyester carbonates and polyesters, which can be obtained by reacting at least one monomer of formula (I) with one or more monomers of formula (IV-11), (IV-12), (IV-13), (IV-21) or (IV-22). In this case, the molar ratio of the monomer of formula (I) to the monomer of formula (IV-11), (IV-12), (IV-13), (IV-21) and (I-22) and the molar ratio of the structural unit of formula (II) to the structural unit of formula (V-11), (V-12), (V-13), (V-21) and (V-22) are in the range of 10:90 to 90:10, 15:85 to 80:20, 20:80 to 70:30, 25:75 to 80:20, 30:70 to 90:10 or 30:70 to 80:20, in particular in the range of 35:65 to 75:25, 35:65 to 70:30, 40:60 to 85:15 or 40:60 to 80:20, and in particular in the range of 50:50 to 80:20. The above molar ratio may be applied to the molar ratio of the structural unit of formula (II) to the total structural units of the thermoplastic copolymer resin.

[0329] The thermoplastic copolymer resin of the present invention, such as polycarbonate resin, can include any one of a random copolymer structure, a block copolymer structure and an alternating copolymer structure. The thermoplastic resin of the present invention does not need to include all structural units (II) and one or more different structural units (V) in one identical polymer molecule. That is, the thermoplastic copolymer resin according to the present invention can be a blended resin, as long as the above-mentioned structures are each included in any one of a plurality of polymer molecules. For example, a thermoplastic resin including all of the above-mentioned structural units (II) and structural units (V) can be a copolymer including all of the structural units (II) and structural units (V), it can be a mixture of a homopolymer and a copolymer including at least one structural unit (II) and a homopolymer or a copolymer including at least one structural unit (V), or it can be a copolymer including at least one structural unit (II) and a first structural unit (V) and a blended resin of a copolymer including at least one structural unit (II) and at least one other structural unit (V) different from the first structural unit (V); etc.

[0330] Thermoplastic polycarbonates can be obtained by polycondensation of a diol component and a carbonate-forming component. Similarly, thermoplastic polyesters and polyester carbonates can be obtained by polycondensation of a diol component and a dicarboxylic acid or its ester-forming derivative and optionally a carbonate-forming component.

[0331] Specifically, the thermoplastic resin (polycarbonate resin) can be prepared by the following method.

[0332] The method for preparing a thermoplastic resin such as a polycarbonate resin of the present invention comprises a process of melt polycondensing a dihydroxy component corresponding to the above-mentioned structural unit with a carbonic acid diester. According to the present invention, the dihydroxy compound includes at least one dihydroxy compound represented by formula (I), in particular a dihydroxy compound represented by formula (Ia) or (Ib) as defined herein. In addition to the compound of formula (I), the dihydroxy compound may also include one or more dihydroxy compounds represented by formula (IV), preferably by formula (IV-1) to (IV-8), in particular by formula (IV-11) to (IV-22) and in particular by formula (IV-11), (IV-12), (IV-13), (IV-14), (IV-15), (IV-21) or (IV-22).

[0333] As is clear from the above, the polycarbonate resin can be formed by reacting a dihydroxy component with a carbonate precursor such as a carbonic acid diester, wherein the dihydroxy component includes at least one compound represented by formula (I), (Ia) and (Ib), respectively, or a combination of at least one compound represented by formula (I), (Ia) and (Ib), respectively, and at least one compound represented by formula (IV), (IV-1), (IV-2), (IV-3), (IV-4), (IV-5), (IV-6), (IV-7), (IV-8), (IV-11), (IV-12), (IV-13), (IV-14), (IV-15), (IV-16), (IV-17), (IV-18), (IV-19), (IV-20), (IV-21) or (IV-22). Specifically, the polycarbonate resin can be formed by a melt polycondensation method, wherein compounds represented by formula (I), (Ia) and (Ib), respectively, or a combination thereof with at least one compound represented by formula (IV), (IV-1), (IV-2), (IV-3), (IV-4), (IV-5), (IV-6), (IV-7), (IV-8), (IV-11), (IV-12), (IV-13), (IV-14), (IV-15), (IV-16), (IV-17), (IV-18), (IV-19), (IV-20), (IV-21) or (IV-22) are reacted with a carbonate precursor such as a carbonic acid diester in the presence of a basic compound catalyst, an ester exchange catalyst or a mixed catalyst thereof, or in the absence of a catalyst.

[0334] Thermoplastic resins (or polymers) other than polycarbonate resins, such as polyester carbonates and polyesters, are obtained by using dihydroxy compounds represented by formula (I), (Ia) and (Ib), respectively, or a combination thereof with at least one compound represented by formula (IV), (IV-1), (IV-2), (IV-3), (IV-4), (IV-5), (IV-6), (IV-7), (IV-8), (IV-11), (IV-12), (IV-13), (IV-14), (IV-15), (IV-16), (IV-17), (IV-18), (IV-19), (IV-20)(IV-21) or (IV-22) as a material (or monomer).

[0335] As mentioned previously, the monomers of formula (I) and likewise the comonomers of formula (IV) used to make the thermoplastic resin may contain impurities resulting from their preparation.

[0336] For example, monomers of formula (IV-1) and (IV-2) (where R z It's O-Alk 2 - or O-Alk2 -[O-Alk 2 -] p -) can include two of the R z are all dihydroxy compounds with single bonds, or R z One of them is a single bond instead of O-Alk 2 - or O-Alk 2 -[O-Alk 2 -] p -dihydroxy compounds.

[0337] In the monomers mainly composed of dihydroxy compounds represented by formula (IV-1) or (IV-2), the dihydroxy compounds represented by formula (IV-1) or (IV-2) (wherein at least one R z Different from O-Alk 4 - or O-Alk 4 -[O-Alk 4 -] w The total amount of dihydroxy compounds in which at least one of the values ​​of a and b or c and d is different from that of formula (IV-1) or (IV-2) is preferably 3000 ppm or less, more preferably 1500 ppm or less, still more preferably 1000 ppm or less, and particularly preferably 500 ppm or less. The total content of dihydroxy compounds in which at least one of the values ​​of a and b or c and d is different from that of formula (IV-1) or (IV-2) is also preferably 300 ppm or less, and more preferably 200 ppm or less.

[0338] The polycarbonate resin can be obtained by reacting a monomer compound of formula (I) with a carbonate precursor such as a carbonic acid diester, or can be obtained by reacting at least one monomer compound of formula (I), especially at least one monomer (I) mentioned herein as preferred and one or more monomer compounds of formula (IV), and especially a combination of monomer compounds of formula (IV-11), (IV-12), (IV-13), (IV-14), (IV-15), (IV-21), or (IV-22), etc. as a dihydroxy component with a carbonate precursor such as a carbonic acid diester.

[0339] However, during the polymerization process for making polycarbonate resins, some compounds of formula (I) and (IV) may be converted into impurities, wherein the terminal -X 1 , -X 2 or -R z One or both of the OH groups are replaced with a different group, such as a vinyl terminal group represented by -OCH=CH2. Since the amount of such impurities is usually small, the resulting polymer product can be used as a polycarbonate resin without purification process.

[0340] The thermoplastic resin of the present invention may also contain a small amount of impurities, for example, as an additional content of the thermoplastic resin composition or as a part of the polymer backbone of the thermoplastic resin. Examples of such impurities include phenols, unreacted carbonic acid diesters and monomers formed by the process for forming the thermoplastic resin. The total amount of impurities in the thermoplastic resin may be 5000ppm or less, or 2000ppm or less. The total amount of impurities in the thermoplastic resin is preferably 1000ppm or less, more preferably 500ppm or less, still more preferably 200ppm or less, and particularly preferably 100ppm or less.

[0341] The total amount of phenol as an impurity in the thermoplastic resin may be 3000 ppm or less or 2000 ppm or less. The total amount of phenol as an impurity is preferably 1000 ppm or less, more preferably 800 ppm or less, still more preferably 500 ppm or less, particularly preferably 300 ppm or less.

[0342] The total amount of carbonic acid diester as impurities in the thermoplastic resin is preferably 1000 ppm or less, more preferably 500 ppm or less, still more preferably 100 ppm or less, particularly preferably 50 ppm or less.

[0343] The total amount of unreacted monomers as impurities in the thermoplastic resin is preferably 3000 ppm or less, more preferably 2000 ppm or less, still more preferably 1000 ppm or less, particularly preferably 500 ppm or less.

[0344] The lower limit of the total amount of these impurities is not critical, but may be 0.1 ppm or 1.0 ppm.

[0345] The total amount of residual heavy metals such as palladium as impurities in the thermoplastic resin is preferably 50 ppm or less, more preferably 10 ppm or less. The amount of residual palladium can be reduced by standard methods, such as treatment with an adsorbent such as activated carbon.

[0346] The resin having the target properties can be formed by adjusting the amount of phenol and carbonic acid diester. The amount of phenol, carbonic acid diester and monomer can be appropriately adjusted by adjusting the polycondensation conditions, the working conditions of the equipment used for polymerization, and the extrusion molding conditions after the polycondensation process.

[0347] The weight average molecular weight (Mw) of the thermoplastic resin according to the present invention is preferably in the range of 5000 to 100000 Daltons, more preferably in the range of 10000 to 80000 Daltons or 20000 to 65000 Daltons, and particularly in the range of 10000 to 50000 Daltons or 20000 to 40000 Daltons by GPC (gel permeation chromatography). GPC measurements can be calibrated using polystyrene standards. The Mw of the thermoplastic resin of the present invention measured in this way is also expressed herein as "polystyrene conversion weight average molecular weight". The number average molecular weight (Mn) of the thermoplastic resin according to the present invention is preferably in the range of 3000 to 30000, more preferably 5000 to 25000, and particularly preferably in the range of 7000 to 20000. The viscosity average molecular weight (Mv) of the thermoplastic resin according to the present invention is preferably in the range of 8,000 to 28,000, more preferably 9,000 to 22,000, and still more preferably 10,000 to 18,000.

[0348] The value of the molecular weight distribution (Mw / Mn) of the thermoplastic resin according to the present invention is preferably from 1.5 to 9.0, more preferably from 1.8 to 7.0, still more preferably from 2.0 to 4.0.

[0349] When the thermoplastic resin has a weight average molecular weight (Mw) value within the above-mentioned suitable range, the molded article made of the thermoplastic resin has high strength. In addition, such a thermoplastic resin having a suitable Mw value is advantageous for molding due to its excellent fluidity.

[0350] Preferably, the thermoplastic resin contains 9% by weight or less, in particular 7% by weight or less, and in particular 5% by weight or less, such as 0.1 to 9% by weight, in particular 0.1 to 7% by weight, and in particular 0.1 to 5% by weight of low molecular weight compounds having a molecular weight of less than 1000, based on the total weight of the thermoplastic resin. If such low molecular weight compounds are present in the thermoplastic resin in an amount within the above range, the mechanical strength of the molded body made of such thermoplastic resin is generally increased, in particular compared to a molded body made of a thermoplastic resin having a higher amount of low molecular weight compounds. In addition, the thermoplastic resin according to the present embodiment contains 9% by weight or less, in particular 7% by weight or less, in particular 5% by weight of low molecular weight compounds having a molecular weight of less than 1000, and during a molding process (e.g., an injection molding process), the low molecular weight compounds are not easily precipitated or only slightly precipitated, which is also referred to as exudation. In contrast, the molding of thermoplastic resins having a higher amount of low molecular weight compounds may be accompanied by a greater degree of exudation. It is also preferred that the thermoplastic resin contains 0.1 wt % or more, particularly 0.3 wt % or more or 0.5 wt % or more, particularly 1.0 wt % or more (e.g. 0.5 to 9 wt %, particularly 1 to 9 wt % or 1 to 7 wt %, and particularly 1 to 5 wt %) of a low molecular weight compound having a molecular weight of less than 1000, based on the total weight of the thermoplastic resin.

[0351] The thermoplastic resin of the present invention, such as the above-mentioned polycarbonate resin, has a high refractive index (n D or d ), and is therefore suitable for optical lenses. The value of the refractive index referred to herein is a value for a film having a thickness of 0.1 mm, and can be measured by using an Abbe refractometer according to the method of JIS-K-7142. The refractive index of the thermoplastic resin of the present invention, in particular the polycarbonate resin of the present invention, at 23° C. and a wavelength of 589 nm, is generally 1.630 or higher, preferably 1.640 or higher, more preferably 1.650 or higher, still more preferably 1.660 or higher, particularly 1.665 or higher, 1.670 or higher, 1.675 or higher, or 1.680 or higher, and particularly preferably 1.685 or higher. For example, the refractive index of the copolycarbonate resin comprising structural unit (II) and structural unit (V) according to the present invention is preferably 1.640 to 1.730, preferably 1.650 to 1.730, and still more preferably 1.660 to 1.730.

[0352] The Abbe number (ν or νd) of the thermoplastic resin of the present invention, particularly the polycarbonate resin of the present invention, is preferably 24 or less, or 23 or less, more preferably 22 or less, or 21 or less, and still more preferably 20 or less, or 19 or less. The Abbe number can be calculated by the following formula based on the refractive index at wavelengths of 487 nm, 589 nm, and 656 nm at 23°C.

[0353] ν=(n D -1) / (n F -n C )

[0354] n D : Refractive index at wavelength 589nm

[0355] n C : Refractive index at wavelength 656nm

[0356] n F : Refractive index at wavelength 486nm

[0357] The glass transition temperature (Tg) of the thermoplastic resin of the present invention, particularly the polycarbonate resin of the present invention, is generally in the range of 90 to 185°C, preferably in the range of 90 to 180°C, more preferably in the range of 100 to 170°C or 110 to 170°C, and particularly in the range of 110 to 160°C, 120 to 165°C or 130 to 160°C, considering that the polycarbonate can be used for injection molding. In terms of molding fluidity and molding heat resistance, the lower limit of Tg is preferably 130°C, more preferably 135°C, and the upper limit of Tg is preferably 180°C, more preferably 170°C. The glass transition temperature (Tg) within the above-given range provides a significant range of usable temperatures and avoids the risk that the melting temperature of the resin may be too high, and thus the resin may be undesirably decomposed or colored. In addition, it allows the preparation of molds with high surface accuracy. The values ​​given for the glass transition temperature refer to values ​​measured by differential scanning calorimetry (DSC) according to the protocol of JIS K7121-1987 using a 10° C. / min heating program.

[0358] In the preferred embodiment of group (11), the absolute value of the orientation birefringence of the thermoplastic resin is preferably in the range of 0 to 1×10 -2 In the range of 0 to 5x10 -3 in the range of 0 to 2x10 -3 In the range of 0 to 1x10 -3 in the range of 0 to 0.4x10 -3 within the range.

[0359] The total light transmittance of an optical molded article such as an optical element produced by using the polycarbonate resin of the present invention is preferably 85% or higher, more preferably 87% or higher, and particularly preferably 88% or higher. The total light transmittance of preferably 85% or higher is as good as the total light transmittance provided by bisphenol A type polycarbonate resin and the like.

[0360] The thermoplastic resin of the present invention has high moisture resistance and heat resistance. Moisture resistance and heat resistance can be evaluated by carrying out a "PCT test" (pressure cooker test) on a molded body such as an optical element made using a thermoplastic resin, and then measuring the total light transmittance of the molded body after the PCT test. In the PCT test, first, a PC305S III manufactured by HIRAYA MA Corporation with a diameter of 50 mm and a thickness of 3 mm is kept for 20 hours, at 120°C, 0.2 MPa, and 100% RH for 20 hours. Then, the sample of the injection molded body is taken out from the device, and the total light transmittance is measured according to the method of JIS-K-7361-1 using a SE2000 type spectroscopic parallax measuring instrument manufactured by Nippon Denshoku Industries Co., Ltd.

[0361] The total light transmittance of the thermoplastic resin according to the present invention after the PCT test is 60% or more, preferably 70% or more, more preferably 75% or more, still more preferably 80% or more, and particularly preferably 85% or more. As long as the total light transmittance is 60% or more, the thermoplastic resin is considered to have higher moisture and heat resistance than conventional thermoplastic resins.

[0362] The b value indicating the hue of the thermoplastic resin according to the present invention is preferably 5 or less. The smaller the b value, the less yellowish the color is, and the better the hue is.

[0363] According to the present invention, the diol component used for preparing the polycarbonate or polyester may additionally include one or more diol monomers different from the monomer compound of formula (I), for example one or more monomers of formula (IV).

[0364] Suitable diol monomers other than the monomer compounds of the formula (I) are those monomers conventionally used for preparing polycarbonates, for example

[0365] - aliphatic diols, for example ethylene glycol, propylene glycol, butanediol, pentanediol and hexanediol;

[0366] - alicyclic diols such as tricyclo[5.2.1.02,6]decanedimethanol, cyclohexane-1,4-dimethanol, decalin-2,6-dimethanol, norbornane dimethanol, pentacyclopentadecanedimethanol, cyclopentane-1,3-dimethanol, spirodiol, 1,4:3,6-dianhydro-D-sorbitol, 1,4:3,6-dianhydro-D-mannitol and 1,4:3,6-dianhydro-L-iditol are also included in the examples of diols; and

[0367] - aromatic diols, in particular aromatic diols of the formula (IV), for example bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)ketone, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-tert-butylphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, ... )diphenylmethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, α,ω-bis[2-(p-hydroxyphenyl)ethyl]polydimethylsiloxane, α,ω-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane, 4,4'-[1,3-phenylenebis(1-methylethylidene)hydroxyphenyl]-1-phenylethane, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-tert-butylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-isopropylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-isopropylphenyl]fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethyl)phenyl)fluorene, 9,9-bis(4-(2-hydroxyethyl)-3-phenylphenyl)fluorene, 9,9-bis(6-hydroxy-2-naphthyl)fluorene, 9,9-bis(6-(2-hydroxyethyl)-2-naphthyl)fluorene, 10,10-bis(4-hydroxyphenyl)anthracen-9-one, 10,10-bis(4-(2-hydroxyethyl)phenyl)anthracen-9-one, 2-[4-[4-(2-hydroxyethoxy)-3,5-di(thianthren-1-yl)phenyl]sulfonyl-2,6-di(thianthren-1-yl)phenoxy]ethanol , 2-[4-[4-(2-hydroxyethoxy)-3,5-di(dibenzo[b,d]thiophen-4-yl)phenyl]sulfonyl-2,6-dibenzo[b,d]thiophen-4-yl)phenoxy]ethanol, 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-di(phenanthrene-9-yl)-phenyl]-1-methylethyl]-2,6-di(phenanthrene-9-yl)-phenoxy]ethanol and 2,2'-[1,1'-binaphthyl-2,2'-diylbis(oxy)]diethanol (also known as 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl or 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl (BNE)).

[0368] Preferably, in addition to the monomer of formula (I), the diol component also includes at least one monomer of formula (IV). In particular, the total amount of the monomers of formula (I) and (IV) contributes to the diol component by at least 90% by weight based on the total weight of the diol component, or by at least 90% by mole based on the total molar amount of the diol monomers of the diol component. In particular, in addition to the monomer of formula (I), the diol component also includes at least one monomer selected from the monomers of formulas (IV-11) to (IV-22). More particularly, in addition to the monomer of formula (I), the diol component also includes at least one monomer selected from the monomers of formulas (IV-11), (IV-12), (IV-13), (IV-14), (IV-15), (IV-21) and (IV-22). In particular, in addition to the monomer of formula (I), the diol component also includes a diol selected from 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 2-[4-[4-(2-hydroxyethoxy)-3,5-di(thianthren-1-yl)phenyl]sulfonyl-2,6-di(thianthren-1-yl)benzene At least one monomer selected from 2-[4-[4-(2-hydroxyethoxy)-3,5-di(dibenzo[b,d]thien-4-yl)phenyl]sulfonyl-2,6-dibenzo[b,d]thien-4-yl)phenoxy]ethanol, 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-di(phenanthrene-9-yl)-phenyl]-1-methylethyl]-2,6-di(phenanthrene-9-yl)-phenoxy]ethanol and 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene and combinations thereof.

[0369] Typically, the relative amount of the monomeric compounds of formula (I), based on the total weight of the diol component, is at least 1 wt.-%, preferably at least 10 wt.-%, or at least 30 wt.-%, in particular at least 15 wt.-%, or at least 20 wt.-%, in particular at least 25 wt.-%, or at least 30 wt.-%, preferably in the range of 1 to 99 wt.-%, or in the range of 10 to 98 wt.-%, in particular in the range of 20 to 98 wt.-%, or in the range of 25 to 98 wt.-%, or in the range of 30 to 98 wt.-%, or in the range of 30 to 97 wt.-%, in particular in the range of 15 to 96 wt.-%, or in the range of 20 to 95 wt.-%, or in the range of 30 to 95 wt.-%, or in the range of 30 to 93 wt.-%, but may also be up to 100 wt.-%.

[0370] Typically, the relative molar amount of the monomeric compound of formula (I), based on the total molar amount of the diol component, is at least 1 mol%, preferably at least 10 mol%, or at least 30 mol%, in particular at least 15 mol%, or at least 20 mol%, and in particular at least 25 mol%, or at least 30 mol%, preferably in the range of 1 to 99 mol%, or in the range of 10 to 98 mol%, or in the range of 20 to 98 mol%, or in the range of 25 to 98 mol%, in particular in the range of 15 to 96 mol%, or in the range of 20 to 95 mol%, or in the range of 30 to 95 mol%, or in the range of 30 to 93 mol%, in particular in the range of 20 to 90 mol%, or in the range of 25 to 90 mol%, or in the range of 30 to 90 mol%, or in the range of 32 to 90 mol%, or in the range of 35 to 90 mol%, but may also be up to 100 mol%.

[0371] Thus, the relative molar amount of the monomeric compound of formula (IV), based on the total molar amount of the diol component, will not exceed 99 mol % or 90 mol % or 70 mol %, in particular not exceed 85 mol % or 80 mol %, and in particular not exceed 75 mol % or 70 mol %, and is preferably in the range of 1 to 99 mol %, or in the range of 2 to 90 mol %, or in the range of 2 to 80 mol %, or in the range of 2 to 75 mol %, in particular in the range of 4 to 85 mol %, or in the range of 5 to 80 mol %, or in the range of 5 to 70 mol %, or in the range of 7 to 70 mol %, in particular in the range of 10 to 80 mol %, or in the range of 10 to 75 mol %, or in the range of 10 to 70 mol %, or in the range of 10 to 68 mol %, or in the range of 10 to 65 mol %, but may also be up to 99.9 mol %.

[0372] Typically, the total molar amount of monomers of formula (I) and monomers of formula (IV) is at least 80 mol%, particularly at least 90 mol%, particularly at least 95 mol%, or up to 100 mol%, based on the total molar amount of diol monomers in the diol component.

[0373] In addition to the monomer of formula (I) and the optional monomer of formula (IV), further preferred examples of aromatic dihydroxy compounds that can be used include, but are not limited to, bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, bisphenol Z, etc.

[0374] In order to adjust the molecular weight and melt viscosity, the monomers forming the thermoplastic polymer may also include monofunctional compounds, which are monofunctional alcohols in the case of polycarbonates and monofunctional alcohols or monofunctional carboxylic acids in the case of polyesters. Suitable monohydric alcohols are butanol, hexanol and octanol. Suitable monocarboxylic acids include, for example, benzoic acid, propionic acid and butyric acid. In order to increase the molecular weight and melt viscosity, the monomers forming the thermoplastic polymer may also include polyfunctional compounds, which are polyfunctional alcohols with three or more hydroxyl groups in the case of polycarbonates and polyfunctional alcohols with three or more hydroxyl groups or polyfunctional carboxylic acids with three or more carboxyl groups in the case of polyesters. Suitable polyfunctional alcohols are, for example, glycerol, trimethylolpropane, pentaerythritol and 1,3,5-trihydroxypentane. Suitable polyfunctional carboxylic acids with three or more carboxyl groups are, for example, trimellitic acid and pyromellitic acid. Based on the molar amount of the diol component, the total amount of these compounds is usually no more than 10 mol%.

[0375] Suitable carbonate forming monomers are those conventionally used as carbonate forming monomers in the preparation of polycarbonate, including, but not limited to, phosgene, diphosgene and carbonic acid diesters such as diethyl carbonate, diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate and dinaphthyl carbonate. Among them, diphenyl carbonate is particularly preferred. Relative to a total of 1 mole of dihydroxy compounds, the use ratio of carbonate forming monomers is generally 0.97 to 1.20 moles, more preferably 0.98 to 1.10 moles.

[0376] Suitable dicarboxylic acids include, but are not limited to

[0377] - aliphatic dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid;

[0378] - cycloaliphatic dicarboxylic acids, for example tricyclo[5.2.1.02,6]decanedicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, decalin-2,6-dicarboxylic acid and norbornanedicarboxylic acid; and

[0379] - aromatic dicarboxylic acids, for example phthalic acid, in particular phthalic acid, isophthalic acid, 2-methylterephthalic acid or terephthalic acid, and naphthalene dicarboxylic acids, in particular naphthalene-1,3-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-1,6-dicarboxylic acid, naphthalene-1,7-dicarboxylic acid, naphthalene-2,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, 2-[9-(carboxymethyl)fluoren-9-yl]acetic acid (formula DC1), 2-[9-(carboxymethyl)fluoren-9-yl]propionic acid (formula DC2), 2,2′-bis(carboxymethoxy)-1,1′-binaphthyl (formula DC3) and naphthalene-2,7-dicarboxylic acid.

[0380]

[0381] Suitable ester-forming derivatives of dicarboxylic acids include, but are not limited to, dialkyl esters, diphenyl esters, and ditolyl esters.

[0382] In the case of polyester, the ester-forming monomer is used in a proportion of usually 0.97 to 1.20 mol, more preferably 0.98 to 1.10 mol, relative to 1 mol of the total dihydroxy compound.

[0383] The polycarbonate of the present invention can be prepared by reacting a diol component including a monomer of formula (I) and optionally an additional diol monomer such as a monomer of formula (IV) with a carbonate-forming monomer by a preparation method similar to the preparation of known polycarbonates described in, for example, US 9,360,593, US2016 / 0319069 and US2017 / 0276837 (all of which are cited in their entirety).

[0384] The polyester of the present invention can be prepared by reacting a diol component including a monomer of formula (I) and optionally an additional diol monomer such as a monomer of formula (IV) with a dicarboxylic acid or an ester-forming derivative thereof by a preparation method similar to the preparation of known polyesters described in, for example, US2017 / 044311 and the documents cited therein (which are fully cited).

[0385] The polyester carbonates of the present invention can be prepared by reacting a diol component including a monomer of formula (I) and optionally an additional diol monomer such as a monomer of formula (IV), a carbonate-forming monomer and a dicarboxylic acid or an ester-forming derivative thereof by a preparation method similar to the preparation of polyester carbonates known in the art.

[0386] In the case of using carbonate-forming monomers or ester-forming derivatives of polycarboxylic acids, polycarbonates, polyesters and polyester carbonates are generally prepared by reacting monomers of the diol component with carbonate-forming monomers and / or ester-forming monomers, i.e., dicarboxylic acids or their ester-forming derivatives, in the presence of an esterification catalyst, particularly an ester exchange catalyst.

[0387] Suitable transesterification catalysts are basic compounds, which specifically include but are not limited to alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, etc. Similarly, suitable transesterification catalysts are acidic compounds, which specifically include but are not limited to Lewis acid compounds of polyvalent metals, including, for example, compounds of zinc, tin, titanium, zirconium, lead, etc.

[0388] Examples of suitable alkali metal compounds include alkali metal salts of organic acids such as acetic acid, stearic acid, benzoic acid or phenylphosphonic acid, alkali metal phenolates, alkali metal oxides, alkali metal carbonates, alkali metal borohydrides, alkali metal bicarbonates, alkali metal phosphates, alkali metal hydrogenphosphates, alkali metal hydroxides, alkali metal hydrides, alkali metal alkoxides and the like. Specific examples thereof include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium borophenoxide, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate and disodium phenyl phosphate; also include disodium salt, dipotassium salt, dicesium salt, dilithium salt of bisphenol A, sodium salt, potassium salt, cesium salt and lithium salt of phenol; and the like.

[0389] Examples of the alkaline earth metal compound include alkaline earth metal salts of organic acids such as acetic acid, stearic acid, benzoic acid or phenylphosphonic acid, alkaline earth metal phenolates, alkaline earth metal oxides, alkaline earth metal carbonates, alkali metal borohydrides, alkaline earth metal hydrogen carbonates, alkaline earth metal hydroxides, alkaline earth metal hydrides, alkaline earth metal alkoxides, etc. Specific examples thereof include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium hydrogen carbonate, calcium hydrogen carbonate, strontium hydrogen carbonate, barium hydrogen carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, magnesium phenylphosphate, etc.

[0390] Examples of nitrogen-containing compounds include quaternary ammonium hydroxides, salts thereof, amines, etc. Specific examples thereof include: quaternary ammonium hydroxides containing an alkyl group, an aryl group, etc., such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, etc.; tertiary amines, such as triphenylamine, dimethylbenzylamine, triphenylamine, etc.; secondary amines, such as diethylamine, dibutylamine, etc.; primary amines, such as propylamine, butylamine, etc.; imidazoles, such as 2-methylimidazole, 2-phenylimidazole, benzimidazole, etc.; bases or basic salts, such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, tetraphenylammonium tetraphenylborate, etc.

[0391] Preferred examples of transesterification catalysts include salts of polyvalent metals such as zinc, tin, titanium, zirconium, lead, etc., particularly chlorides, alkoxides, alkanoates, benzoates, acetylacetonates, etc. They can be used alone or in combination of two or more. Specific examples of such transesterification catalysts include zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin chloride (II), tin chloride (IV), tin acetate (II), tin acetate (IV), dibutyltin laurate, dibutyltin oxide, dibutyltin methoxide, zirconium acetylacetonate, zirconium oxyacetate, tetrabutoxy zirconium, lead acetate (II), lead acetate (IV), etc.

[0392] The ratio of the transesterification catalyst used is usually 10 to 1 mol of the total dihydroxy compound. -9 Up to 10 -3 mole, preferably 10 -7 Up to 10 -4 Moore.

[0393] Typically, polycarbonates, polyesters and polyester carbonates are prepared by melt polycondensation. In melt polycondensation, monomers are reacted in the absence of an additional inert solvent. While the reaction is being carried out, any by-products formed in the transesterification reaction are removed by heating the reaction mixture under ambient pressure or reduced pressure.

[0394] The melt polycondensation reaction preferably includes loading the monomer and the catalyst into the reactor, and subjecting the reaction mixture to the conditions in which the reaction between the monomers and the formation of by-products occur. It has been found that it is advantageous if the by-products stay for at least a period of time in the polycondensation reaction. However, in order to drive the polycondensation reaction to the product side, it is beneficial to remove at least a portion of the by-products formed during the polycondensation reaction or preferably at the end thereof. In order to allow the by-products to enter the reaction mixture, the pressure can be controlled by closing the reactor or by increasing or reducing the pressure. The reaction time of this step is more than 20 minutes and less than 240 minutes, preferably more than 40 minutes and less than 180 minutes, and particularly preferably more than 60 minutes and less than 150 minutes. In this step, when the by-products are removed by distillation soon after they are produced, the thermoplastic resin finally obtained has a low content of high molecular weight resin molecules. On the contrary, when the by-products are allowed to stay in the reactor for a certain period of time, the thermoplastic resin finally obtained has a high content of high molecular weight resin molecules.

[0395] The melt polycondensation reaction can be carried out in a continuous system or a batch system. The reactor that can be used for the reaction can be a vertical reactor, including anchor stirring blades, Stirring blades, spiral belt stirring blades, etc.; horizontal ones include paddle blades, grating blades, glasses blades, etc.; or extruder ones include screws. Considering the viscosity of the polymer product, it is preferred to use a reactor including a combination of these reactors.

[0396] According to the method for manufacturing thermoplastic resins such as polycarbonate resins, after the polymerization reaction is completed, the catalyst can be removed or deactivated to maintain thermal stability and hydrolytic stability. A preferred method for deactivating the catalyst is to add an acidic substance. Specific examples of acidic substances include esters, such as butyl benzoate, etc.; aromatic sulfonates, such as p-toluenesulfonic acid, etc.; aromatic sulfonates, such as butyl p-toluenesulfonate, hexyl p-toluenesulfonate, etc.; phosphoric acids, such as phosphorous acid, phosphoric acid, phosphonic acid, etc.; phosphites, such as triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, di-n-butyl phosphite, di-n-hexyl phosphite, dioctyl phosphite, mono-phosphite, etc. octyl ester, etc.; phosphate esters, such as triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, dibutyl phosphate, dioctyl phosphate, monooctyl phosphate, etc.; phosphonic acid, such as diphenylphosphonic acid, dioctylphosphonic acid, dibutylphosphonic acid, etc.; phosphonic acid esters, such as diethyl phenylphosphonate, etc.; phosphines, such as triphenylphosphine, bis(diphenylphosphino)ethane, etc.; boric acids, such as boric acid, phenylboric acid, etc.; aromatic sulfonates, such as tetrabutylphosphonium dodecylbenzenesulfonate, etc.; organic halides, such as chloride stearate, benzoyl chloride, chloride p-toluenesulfonate, etc.; alkyl sulfonic acids, such as dimethylsulfonic acid, etc.; organic halides, such as benzyl chloride, etc. The amount of these deactivators is usually 0.01 to 50 mol, preferably 0.3 to 20 mol relative to the catalyst. After the catalyst is deactivated, there may be a step of removing low-boiling compounds from the polymer by distillation. The distillation is preferably carried out under reduced pressure, for example, at a pressure of 0.1 to 1 mm Hg at a temperature of 200 to 350° C. For this step, a horizontal apparatus including a stirring blade having a high surface renewal ability, such as a paddle blade, a cascade blade, a spectacled blade, etc., or a thin film evaporator is preferably used.

[0397] Desirably, thermoplastic resins such as polycarbonate resins have very small amounts of foreign matter. Therefore, the molten product is preferably filtered to remove any solids from the melt. The mesh of the filter is preferably 5 μm or less, more preferably 1 μm or less. Preferably, the produced polymer is filtered through a polymer filter. The mesh of the polymer filter is preferably 100 μm or less, more preferably 30 μm or less. Needless to say, the step of sampling the resin pellets needs to be performed in a low dust environment. The dust environment is preferably Class 6 or less, more preferably Class 5 or less.

[0398] The thermoplastic resin can be molded by any conventional molding method used to manufacture optical elements. Suitable molding methods include, but are not limited to, injection molding, compression molding, casting, roll processing, extrusion molding, stretching, and the like.

[0399] Although the thermoplastic resin of the present invention can be molded as such, a resin composition containing at least one thermoplastic resin of the present invention and further containing at least one additive and / or other resin can also be molded. Suitable additives include antioxidants, processing stabilizers, light stabilizers, polymer metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, antibacterial agents, mold release agents, ultraviolet absorbers, plasticizers, compatibilizers, etc. Suitable other resins are, for example, other polycarbonate resins, polyester carbonate resins, polyester resins, polyamides, polyacetals, etc., which do not contain repeating units of formula (I).

[0400] Examples of antioxidants include, but are not limited to, triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane phaspiro[5.5]undecane), 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)benzofuran-2(3H)-one, 5,7-di-tert-butyl-3-(1,2-dimethylphenyl)benzofuran-2(3H)-one, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate and 3,9-bis{1,1-dimethyl- 2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4,8,10-tetraoxaspiro(5,5)undecane, etc. Among these examples, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)benzofuran-2(3H)-one and 5,7-di-tert-butyl-3-(1,2-dimethylphenyl)benzofuran-2(3H)-one are more preferred. The content of the antioxidant in the thermoplastic resin is preferably 0.001 to 0.3 parts by weight relative to 100 parts by weight of the thermoplastic resin.

[0401] Examples of the processing stabilizer include, but are not limited to, phosphorus-based processing stabilizers, sulfur-based processing stabilizers, etc. Examples of the phosphorus-based processing stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, esters thereof, and the like. Specific examples thereof include triphenyl phosphite, tris(nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2,6-di-tert-butylphenyl)phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphites, distearyl pentaerythritol diphosphites, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenylmonoorthoxenylphosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, dimethyl phenylphosphonate, diethyl phenylphosphonate, dipropyl phenylphosphonate, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, and the like. The content of the phosphorus-based processing stabilizer in the thermoplastic resin composition is preferably 0.001 to 0.2 parts by weight relative to 100 parts by weight of the thermoplastic resin.

[0402] Examples of sulfur-based processing stabilizers include, but are not limited to, pentaerythritol-tetrakis (3-lauryl thiopropionate), pentaerythritol-tetrakis (3-myristyl thiopropionate), pentaerythritol-tetrakis (3-stearyl thiopropionate), dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, etc. The content of the sulfur-based processing stabilizer in the thermoplastic resin composition is preferably 0.001 to 0.2 parts by weight relative to 100 parts by weight of the thermoplastic resin.

[0403] Preferred release agents contain at least 90% by weight of esters of alcohols and fatty acids. Specific examples of esters of alcohols and fatty acids include esters of monohydric alcohols and fatty acids, and partial or complete esters of polyhydric alcohols and fatty acids. Preferred examples of the esters of the above-mentioned alcohols and fatty acids include esters of monohydric alcohols with carbon numbers of 1 to 20 and esters of saturated fatty acids with carbon numbers of 10 to 30. Preferred examples of partial or complete esters of polyhydric alcohols and fatty acids include partial or complete esters of polyhydric alcohols with carbon numbers of 2 to 25 and saturated fatty acids with carbon numbers of 10 to 30. Specific examples of esters of monohydric alcohols and fatty acids include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, etc. Specific examples of partial or complete esters of polyols and fatty acids include stearic acid monoglyceride, stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, behenic acid monoglyceride, caprylic acid monoglyceride, lauric acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl alcohol stearate, complete or partial esters of dipentaerythritol, such as dipentaerythritol hexastearate, etc. The content of the release agent in the resin composition is preferably 0.005 to 2.0 parts by weight, more preferably 0.01 to 0.6 parts by weight, and even more preferably 0.02 to 0.5 parts by weight relative to 100 parts by weight of the thermoplastic resin.

[0404] Preferred ultraviolet absorbers are selected from benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, triazine ultraviolet absorbers, cyclic imine ultraviolet absorbers and cyanoacrylate ultraviolet absorbers. That is, the following ultraviolet absorbers can be used alone or in combination of two or more.

[0405] Examples of benzotriazole-based ultraviolet absorbers include 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2N-benzotriazol-2-yl)phenol)], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-octyloxyphenyl)benzotriazole, 2,2'-methylenebis(4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis(1,3-benzoxazine-4-one), 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidemethyl)-5-methylphenyl]benzotriazole, etc.

[0406] Examples of the benzophenone-based ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfinyloxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid hydrate, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 ',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodiumsulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, etc.

[0407] Examples of the triazine-based ultraviolet absorber include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-([(hexyl)oxy]-phenol, 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-([(octyl)oxy]-phenol, and the like.

[0408] Examples of the cyclic imidate-based ultraviolet absorbers include 2,2'-bis(3,1-benzoxazin-4-one), 2,2'-p-phenylenebis(3,1-benzoxazin-4-one), 2,2'-m-phenylenebis(3,1-benzoxazin-4-one), 2,2'-(4,4'-biphenylene)bis(3,1-benzoxazin-4-one), 2,2'-(2,6-naphthalene)bis(3, 1-benzoxazine-4-one), 2,2'-(1,5-naphthalene)bis(3,1-benzoxazine-4-one), 2,2'-(2-methyl-p-phenylene)bis(3,1-benzoxazine-4-one), 2,2'-(2-nitro-p-phenylene)bis(3,1-benzoxazine-4-one), 2,2'-(2-chloro-p-phenylene)bis(3,1-benzoxazine-4-one), etc.

[0409] Examples of the cyanoacrylate-based ultraviolet absorber include 1,3-bis-[(2′-cyano-3′,3′-diphenylacryloyl)oxy]-2,2-bis(((2-cyano-3,3-diphenylacryloyl)oxy)methyl)propane, 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene, and the like.

[0410] The content of the ultraviolet absorber in the resin composition is preferably 0.01 to 3.0 parts by weight, more preferably 0.02 to 1.0 parts by weight, and even more preferably 0.05 to 0.8 parts by weight relative to 100 parts by weight of the thermoplastic resin. The ultraviolet absorber contained in such a content range can provide sufficient weather resistance to the thermoplastic resin according to the application.

[0411] As described above, the thermoplastic polymer resins, particularly polycarbonate resins, comprising repeating units of formula (II), (IIa) and (IIb), respectively, as described herein, provide thermoplastic resins with high transparency and high refractive index, and are therefore suitable for use in the preparation of optical devices requiring high transparency and high refractive index. More precisely, the thermoplastic polycarbonate having structural units of formula (II), (IIa) and (IIb), respectively, is characterized by having a high refractive index, preferably at least 1.640, more preferably at least 1.660, and especially at least 1.670.

[0412] The contribution of the monomers of formula (I), (Ia) and (Ib) to the refractive index of a thermoplastic resin, in particular a polycarbonate resin, depends on the refractive index of the monomer and the relative amount of the monomer in the thermoplastic resin. Generally, the higher the refractive index of the monomer contained in the thermoplastic resin, the higher the refractive index of the resulting thermoplastic resin. In addition, the refractive index of a thermoplastic resin comprising a structural unit of formula (II) can be calculated from the refractive index of the monomer used to prepare the thermoplastic resin, from the refractive index of the monomer or from scratch, for example by using the computer software ACD / ChemSketch 2012 (AdvancedChemistry Development, Inc.).

[0413] In the case of a thermoplastic copolymer resin, the refractive index of the thermoplastic resin, particularly a polycarbonate resin, can be calculated from the refractive index of the homopolymer of each monomer forming the copolymer resin by the following so-called "Fox equation":

[0414] 1 / n D =x1 / n D1 +x2 / n D2 +....x n / n Dn ,

[0415] where n D is the refractive index of the copolymer, x1, x2....x n is the mass fraction of monomers 1, 2, ....n in the copolymer, n D1 、n D2 ....n Dn is the refractive index of a homopolymer synthesized from only one of the monomers 1, 2, ... n. In the case of polycarbonate, x1, x2, ....x n is the mass fraction of OH monomers 1, 2, ... n based on the total amount of OH monomers. Obviously, a higher refractive index of the homopolymer will result in a higher refractive index of the copolymer.

[0416] The refractive index of a thermoplastic resin can be measured directly or indirectly. For direct measurement, the refractive index n of the thermoplastic resin is measured at a wavelength of 589 nm using an Abbe refractometer and applying a 0.1 mm thermoplastic resin film according to JIS-K-7142. DIn the case of the refractive index of a homopolycarbonate of a compound of formula (I), the refractive index can also be determined indirectly. For this purpose, copolycarbonates of the individual monomers of formula (I) with 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene and diphenyl carbonate were prepared according to the protocol of Example 1 in column 48 of US Pat. No. 9,360,593, and the refractive index n of the copolycarbonate was measured at a wavelength of 589 nm according to the protocol of JIS-K-7142 using an Abbe refractometer and applying a 0.1 mm copolycarbonate film. D According to the refractive index n measured in this way D The refractive index of the homopolycarbonate of the corresponding monomer can be obtained by applying the Fox equation and the known refractive index of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (n D (589nm)=1.639).

[0417] The compounds of formula (I) can be obtained in a purity providing a low yellowness index YI as measured according to ASTM E313, which can also be important for the use in the preparation of optical resins.

[0418] More precisely, the compounds of formula (I) preferably have a yellowness index YI of not more than 100, more preferably not more than 50, even more preferably not more than 20, in particular not more than 10 or not more than 5, determined according to ASTM E313.

[0419] The thermoplastic resin according to the present invention has a high refractive index and a low Abbe number. The thermoplastic resin of the present invention can be used to manufacture a transparent conductive substrate that can be used for a liquid crystal display, an organic EL display, a solar cell, etc. In addition, the thermoplastic resin of the present invention can be used as a structural material for optical parts such as optical disks, liquid crystal panels, optical cards, optical sheets, optical fibers, connectors, evaporated plastic reflectors, displays, etc.; or as an optical device suitable for functional material applications.

[0420] Therefore, the thermoplastic resin of the present invention can be used to form molded articles such as optical devices. Optical devices include optical lenses and optical films. Specific examples of optical devices include lenses, films, mirrors, filters, prisms, etc. These optical devices can be formed by any manufacturing process, for example, by injection molding, compression molding, injection compression molding, extrusion molding or solution casting.

[0421] Due to excellent moldability and high heat resistance, the thermoplastic resin of the present invention is very suitable for manufacturing optical lenses that require injection molding. For molding, the thermoplastic resin of the present invention, such as polycarbonate resin, can be used as a mixture with other thermoplastic resins, such as different polycarbonate resins, polyester carbonate resins, polyester resins and other resins.

[0422] In addition, the thermoplastic resin of the present invention may be mixed with an additive for forming an optical device. As the additive for forming an optical device, the additives described above may be used. The additives may include antioxidants, processing stabilizers, light stabilizers, polymer metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, antibacterial agents, mold release agents, ultraviolet absorbers, plasticizers, and compatibilizers.

[0423] As is apparent from the above, another aspect of the invention relates to an optical device made of a thermoplastic resin as defined above, wherein the thermoplastic resin comprises structural units represented by formula (II) and optionally formula (V). With regard to the preferred meanings and preferred embodiments of the structural units of formulae (II) and (V), reference is made to the explanations given above.

[0424] Optical devices made of optical resins comprising repeating units of formula (II) and optional repeating units of formula (V) as defined herein are generally optical molded articles, such as optical lenses, such as automobile headlight lenses, Fresnel lenses, fθ lenses for laser printers, camera lenses, lenses for eyes, and projection lenses for rear-projection televisions, CD-ROM pickup lenses, and optical disks, optical elements for image display media, optical films, film substrates, filters or prisms, liquid crystal panels, optical cards, optical sheets, optical fibers, optical connectors, deposition (eposition) plastic reflectors, etc. Optical lenses and optical films are particularly preferred herein. Optical resins comprising repeating units of formula (II) and optional repeating units of formula (V) can also be used to manufacture transparent conductive substrates that can be used for optical devices, which are suitable for use as structural elements or functional elements of transparent conductive substrates for liquid crystal displays, organic EL displays, solar cells, etc.

[0425] The optical lens manufactured by the thermoplastic resin according to the present invention has a high refractive index, a low Abbe number and a low birefringence, and has high moisture resistance and heat resistance. Therefore, the optical lens can be used in the field of conventionally using expensive glass lenses with high refractive index, such as for telescopes, binoculars, TV projectors, etc. Preferably, the optical lens is used in the form of an aspheric lens. Only one aspheric lens can make the spherical aberration substantially zero. Therefore, it is not necessary to use multiple spherical lenses to eliminate spherical aberration. Therefore, the weight and manufacturing cost of the device including spherical aberration are reduced. Among various types of optical lenses, aspheric lenses are particularly useful as camera lenses. The present invention easily provides an aspheric lens with a high refractive index and a low birefringence level that is technically difficult to manufacture by processing glass.

[0426] The optical lens of the present invention may be formed, for example, by injection molding, compression molding, injection compression molding or casting of a resin comprising a repeating unit of formula (II) and optionally a repeating unit of formula (V) as defined herein.

[0427] The optical lens of the present invention is characterized in that the optical distortion is very small. The optical lens including conventional optical resins has large optical distortion. Although it is not impossible to reduce the value of optical distortion by molding conditions, the condition width is very small, making molding extremely difficult. Since the resin having the repeating unit of formula (II) as defined herein and the optional repeating unit of formula (V) has extremely small optical distortion caused by resin orientation and small molding distortion, it is possible to obtain an excellent optical element without strictly setting the molding conditions.

[0428] In order to manufacture the optical lens of the present invention by injection molding, it is preferred that the lens is molded at a cylinder temperature of 260°C to 320°C and a mold temperature of 100°C to 140°C.

[0429] The optical lens of the present invention is advantageously used as an aspherical lens as required. Since a single aspherical lens can be used to substantially eliminate spherical aberration, it is not necessary to use a combination of spherical lenses to eliminate spherical aberration, thereby reducing weight and manufacturing costs. Therefore, among optical lenses, the aspherical lens can be particularly used as a camera lens.

[0430] Since the resins having the repeating units of formula (II) and optionally the repeating units of formula (V) as defined herein have high moldability, they are particularly useful as materials for optical lenses that are thin, small in size, and have a complex shape. As lens size, the thickness of the central portion of the lens is 0.05 to 3.0 mm, preferably 0.05 to 2.0 mm, and more preferably 0.1 to 2.0 mm. The diameter of the lens is 1.0 to 20.0 mm, preferably 1.0 to 10.0 mm, and more preferably 3.0 to 10.0 mm. A meniscus lens is preferred, which is convex on one side and concave on the other side.

[0431] The surface of the optical lens of the present invention may have a coating, such as an antireflection layer or a hard coating, as required. The antireflection layer may be a single layer or a multilayer, and may be composed of an organic material or an inorganic material, but is preferably composed of an inorganic material. Examples of inorganic materials include oxides and fluorides, such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, magnesium oxide, and magnesium fluoride.

[0432] The optical lens of the present invention can be formed by any method such as metal forming, cutting, polishing, laser processing, electrical discharge machining or edge grinding. Metal forming is preferred.

[0433] The optical film manufactured using the thermoplastic resin according to the present invention has high transparency and heat resistance, and can therefore be preferably used for liquid crystal substrate films, optical memory cards, etc. Needless to say, in order to prevent foreign matter from being incorporated into the optical film as much as possible, molding needs to be performed in a low dust environment. The dust environment is preferably below level 6, more preferably below level 5.

[0434] The following examples serve to further illustrate the present invention.

[0435] 1. abbreviation:

[0436] mp: melting point

[0437] eq.: molar equivalent

[0438] DMF: dimethylformamide

[0439] HCl: hydrochloric acid

[0440] K2CO3: Potassium carbonate

[0441] KI: Potassium iodide

[0442] KOH: Potassium Hydroxide

[0443] MTBE: Methyl tert-butyl ether

[0444] NaCl: Sodium Chloride

[0445] Na2SO4: Sodium sulfate

[0446] NaHCO3: Sodium bicarbonate

[0447] NH4Cl: Ammonium chloride

[0448] THF: Tetrahydrofuran

[0449] TLC: Thin layer chromatography

[0450] n D : Refractive index

[0451] ν: Abbe number

[0452] Mw: molecular weight

[0453] Tg: Glass transition temperature

[0454] CLWC: Low molecular weight compound content

[0455] GPC: Gel Permeation Chromatography

[0456] BPEF: 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluoride

[0457] BNEF: 9,9-bis[6-(2-hydroxyethoxy)naphthalen-2-yl]fluorene

[0458] BNE: 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl

[0459] DPC: diphenyl carbonate

[0460] 2. Preparation of monomers of formula (I)

[0461] 2.1 Analysis related to the monomer of formula (I):

[0462] The results were measured at 23 °C using an 80 MHz NMR spectrometer (Magritek Spinsolve 80). 1 H-NMR spectra. Unless otherwise stated, the solvent was CDCl3.

[0463] The melting points of the compounds were determined by Büchi Melting Point B-545.

[0464] 2.2 Preparation Example:

[0465] Example 1a: 2',2"-[1,4-phenylenebis(methyleneoxy)]bis([1,1'-binaphthyl]-2-ol) (DBNABHP) (a compound of formula (Ia) wherein X = hydrogen and A 1 =1,4-phenylene; Compound 1 of Table A)

[0466]

[0467] To a mixture of racemic 1,1'-bi-2-naphthol (111 g, 388 mmol, 2.05 eq.) and K2CO3 (152 g, 1.10 mol, 5.8 eq.) in acetone (1.20 kg) was added dropwise a solution of 1,4-bis(bromomethyl)benzene (50.0 g, 189 mmol, 1.0 eq.) in acetone (1.00 kg) at 60° C. The reaction mixture was stirred at 60° C. until TLC control (cyclohexane / ethyl acetate 2:1) showed complete conversion.

[0468] The reaction was quenched by adding water (1.00 kg), and acetone was removed under reduced pressure. Dichloromethane (500 g) was added to the residue, and the aqueous phase was acidified by adding 10% hydrochloric acid (pH=4-5). The phases were separated, and the organic phase was subsequently washed with water (200 g), then with saturated NaCl aqueous solution (200 g), and Na was used SO Drying, and the solvent was completely removed under reduced pressure.

[0469] The crude product was recrystallized from toluene twice and washed with pentane to give the title compound as a white solid (52.0 g, 77.1 mmol, yield: 41%, chemical purity: 99.3%).

[0470] mp=170-200℃.

[0471] 1 H NMR (80MHz. CDCl3): δ=8.11-7.71(m, 8H), 7.53-6.93(m, 16H), 6.83(s, 4H), 4.98(s, 4H), 4.87(s, 2H)ppm.

[0472] Example 1b: 2',2"-[1,4-phenylenebis(methyleneoxy)]bis([1,1'-binaphthyl]-2-ol) (DBNABHP) (a compound of formula (Ia) wherein X = hydrogen and A 1 =1,4-phenylene; Compound 1 of Table A)

[0473]

[0474] To a mixture of racemic 1,1'-bi-2-naphthol (288 g, 1.01 mol, 2.2 eq.), K2CO3 (139 g, 1.01 mol, 2.2 eq.) and KI (15.2 g, 91.4 mmol, 0.2 eq.) in acetone (1.6 kg) was added dropwise a solution of p-α,α'-dichloroxylene (80.0 g, 457 mmol, 1.0 eq.) in acetone (400 g) over 8 hours at 60° C. The reaction mixture was stirred at 60° C. until TLC control (cyclohexane / ethyl acetate 2:1) showed complete conversion (about 18 hours).

[0475] After complete conversion, 2L acetone is removed under reduced pressure. Then, water (1kg) and toluene (1kg) are added to the reaction mixture, and the remaining acetone is removed under reduced pressure. The residue is acidified by adding 10% hydrochloric acid (pH=4-5). Each phase is separated at 60 ℃, and the aqueous phase is extracted with toluene (500g). The combined organic phase is washed with water (500g), dried with Na2SO4, and the solution is concentrated to a residual mass of 1kg. The mixture is cooled to room temperature and stirred for about 2 hours. The suspension is diluted with toluene (300μ), the crystals formed are filtered out and washed with pentane to obtain a crude product, which is a light yellow solid. The crude product is recrystallized twice from toluene to obtain the title compound, which is a white solid (184g, 273mmol, yield: 60%, chemical purity: 99.3%).

[0476] mp=170-200℃.

[0477] 1 H NMR (80MHz, CDCl3): δ=8.11-7.71 (m, 8H), 7.53-6.93 (m, 16H), 6.83 (s, 4H), 4.98

[0478] (s, 4H), 4.87 (s, 2H) ppm.

[0479] Example 2a: 2,2′-[1,4-phenylenebis(methyleneoxy[1,1′-binaphthylene]-2′,2-diyloxy)] Di(ethane-1-ol) (DBHBNABHP) (a compound of formula (Ia) wherein X = 2-hydroxyethyl and A 1 =1,4-phenylene; Table A Compound 25)

[0480]

[0481] To a solution of bis(2′-hydroxy-1,1′-binaphthyl)bis(hydroxymethyl)benzene (34.0 g, 50.4 mmol, 1.0 eq.) in DMF (280 g) was added K2CO3 (27.9 g, 202 mol, 4.0 eq.) and the reaction was heated to 50°C for 30 min. 2-Chloroethanol (16.2 g, 202 mmol, 4.0 eq.) was added at 50°C and the reaction was heated to 130°C until TLC (cyclohexane / ethyl acetate 1:1) showed complete conversion.

[0482] The reaction was cooled to below 100°C, then water (750 g) was added, and the mixture was extracted with dichloromethane at room temperature. The organic phase was dried over Na2SO4, and the solvent was completely removed under reduced pressure to give the title compound as a white solid (35.0 g, 45.9 mmol, yield: 91%, chemical purity: 97.8%).

[0483] 1 H NMR (80 MHz, CDCl a ): δ=8.07-7.72(m, 8H), 7.49-6.99(m, 16H), 6.62(s, 4H), 4.89(m c , 4H), 4.16-3.91 (m, 4H), 3.62-3.32 (m, 4H), 1.95 (app.dt, J=6.6, 2.1Hz, 2H)ppm.

[0484] Example 2b: 2,2′-[1,4-phenylenebis(methyleneoxy[1,1′-binaphthylene]-2′,2-diyloxy)] Di(ethane-1-ol) (DBHBNABHP) (a compound of formula (Ia) wherein X = 2-hydroxyethyl and A 1 =1,4-phenylene; Table A Compound 25)

[0485]

[0486] A mixture of bis(2′-hydroxy-1,1′-binaphthyl)bishydroxymethylbenzene (5.0 g, 7.4 mmol, 1.0 eq.), K2CO3 (1.0 g, 7.4 mmol, 1.0 eq.) and KI (0.25 g, 1.5 mmol, 0.2 eq.) in toluene (30 g) was heated to 100° C. A solution of ethylene carbonate (16.2 g, 202 mmol, 4.0 eq.) in toluene (10 g) was added dropwise and the reaction was heated to reflux until TLC (cyclohexane / ethyl acetate 1:1) showed complete conversion.

[0487] The reaction was cooled to 70°C, water (10 g) was then added, and the mixture was stirred for 30 minutes. The aqueous phase was removed, and a 10% aqueous solution of citric acid (10 g) was then added. The mixture was stirred again for 30 minutes, the aqueous phase was removed, and a 15% aqueous solution of NaOH (10 g) was added. The mixture was stirred again for 1 hour, and the aqueous phase was removed. Water (10 g) was added, the mixture was stirred again for 30 minutes, and the phases were separated. The organic phase was dried over Na2SO4, and the solvent was completely removed under reduced pressure to obtain the title compound as a pale yellow solid (5.1 g, 6.7 mmol, yield: 90%, chemical purity: 93.1%). The compound can be further purified by repeated crystallization from toluene or isobutanol to obtain the product as a white solid with a chemical purity of >95%.

[0488] 1 H NMR (80MHz, CDCl3): δ=8.07-7.72(m, 8H), 7.49-6.99(m, 16H), 6.62(s, 4H), 4.89(m c , 4H), 4.16-3.91 (m, 4H), 3.62-3.32 (m, 4H), 1.95 (app.dt, J=6.6, 2.1Hz, 2H)ppm.

[0489] Example 2c: 2,2′-[1,4-phenylenebis(methyleneoxy[1,1′-binaphthylene]-2′,2-diyloxy)] Di(ethane-1-ol) (DBHBNABHP) (a compound of formula (Ia) wherein X = 2-hydroxyethyl and A 1 =1,4-phenylene; Table A Compound 25)

[0490]

[0491] A mixture of bis(2′-hydroxy-1,1′-binaphthyl)bishydroxymethylbenzene (10 g, 14.8 mmol, 1.0 eq.), K2CO3 (1.0 g, 7.4 mmol, 0.5 eq.) in toluene (30 g) and DMF (2.5 g) was heated to 100° C. A solution of ethylene carbonate (2.74 g, 31.1 mmol, 2.1 eq.) in toluene (10 g) was added dropwise, and the reaction mixture was heated to reflux until TLC (cyclohexane / ethyl acetate 1:1) showed complete conversion.

[0492] The reaction was cooled to 70°C, methanol (5g) was then added, and the mixture was stirred at reflux for 2 hours. Then, water (20g) was added, and the mixture was stirred for 30 minutes. The aqueous phase was removed. Activated carbon (200mg) was added to the organic phase and stirred for 30 minutes. The activated carbon was removed by filtration with diatomaceous earth at 60°C. The filtrate was concentrated under reduced pressure to remove methanol and then cooled to room temperature. The crystalline product was separated by filtration, washed with n-pentane, and dried to obtain the title compound DBHBNABHP as white crystals (9.2g; 12mmol) with a chemical purity of 98.1%.

[0493] mp=120-150℃

[0494] 1 H NMR (80MHz, CDCl3): δ = 8.07-7.72 (m, 8H), 7.49-6.99 (m, 16H), 6.62 (s, 4H), 4.89m c ,4H), 4.16-3.91(m, 4H), 3.62-3.32(m, 4H), 1.95(app.dt, J=6.6, 2.1Hz, 2H)ppm.

[0495] Example 3: [1,4-phenylenebis(methyleneoxy[1,1′-binaphthyl]-2′,2-diyloxymethylene- 4,1-phenylene)] dimethanol (DMOBBNABHP) (a compound of formula (Ia) wherein X = (4-(hydroxymethyl)phenyl)methyl and A 1 =1,4-phenylene; Compound 73 of Table A)

[0496]

[0497] To a mixture of DBNABHP (70.0 g, 104 mmol, 1.0 eq.), K2CO3 (29.4 g, 213 mmol, 2.05 eq.) and KI (1.72 g, 10.4 mmol, 0.1 eq.) in acetone (450 g) was added 4-chloromethylbenzyl alcohol (33.3 g, 213 mmol, 2.05 eq.). The mixture was heated to reflux until TLC control (cyclohexane / ethyl acetate 1:1) showed complete conversion. The reaction mixture was filtered through celite at 40°C to remove inorganic salts, and then the solvent was completely removed under reduced pressure.

[0498] The crude product was recrystallized from a mixture of toluene (200 g) and ethyl acetate (10 g) with activated carbon (2.5 g, Norit DXUltra), followed by slurry washing in MTBE to afford the title compound as a white solid (84.4 g, 92.2 mmol, yield: 89%, chemical purity: 96.9%).

[0499] mD=92-98℃.

[0500] 1 H NMR (80MHz, CDCl3, ppm): δ=8.02-7.77(m, 8H), 7.48-7.11(m, 16H), 7.08-6.75(m, 8H), 6.65(s, 4H), 4.95(s, 4H), 4.90(s, 4H), 4.48(s, 4H)ppm.

[0501] 1H NMR (80MHz, DMSO-d6, ppm): δ=8.18-7.81(m, 8H), 7.74-6.82(m, 24H), 6.74(s, 4 H), 5.05 (s, 4H), 5.04 (s, 4H), 5.04 (t, J = 4.7Hz, 2H), 4.37 (d, J = 4.7Hz, 4H) ppm.

[0502] Example 4: Bis(2′-hydroxy-1,1′-binaphthyl)bis(hydroxymethyl)-2,6-naphthalene (DBNABHN) (compound of formula (Ia), Where X = hydrogen and A 1 =2,6-naphthylene; Compound 6 of Table A)

[0503]

[0504] To a mixture of racemic 1,1'-bi-2-naphthol (39.2 g, 137 mmol, 2.2 eq.), K2CO3 (18.9 g, 137 mmol, 2.2 eq.) and KI (2.06 g, 12.4 mmol, 0.2 eq.) in acetone (330 g) was added dropwise a solution of 2,6-di(chloromethyl)naphthalene (14.0 g, 62.2 mmol, 1.0 eq.) in acetone (160 g) at 60° C. The reaction mixture was stirred at 60° C. until TLC control (cyclohexane / ethyl acetate 2:1) showed complete conversion.

[0505] Water (140g) and toluene (140g) are added to the reaction mixture, and acetone is removed under reduced pressure. The residue is acidified by adding 10% hydrochloric acid (pH=4-5). Each phase is separated at 60°C, and the aqueous phase is extracted with toluene (40g). The combined organic phase is washed with water (70g), dried with Na2SO4, and the solution is concentrated to a residual mass of 90g. The mixture is cooled to room temperature and stirred for about 2 hours. The crystals formed are filtered out and washed with pentane to obtain the title compound, which is a white solid (30.0g, 41.4mmol, yield: 67%, chemical purity: 91.5%). The compound can be further purified by repeated crystallization from toluene to obtain a product with a chemical purity of >95%.

[0506] 1 H NMR (80MHz, CDCl3): δ=8.07-7.71(m, 8H), 7.55-6.89(m, 22H), 5.26-4.89(m, 6H)ppm.

[0507] Example 5: 2,2′-[1,4-naphthylenebis(methyleneoxy[1,1′-binaphthylene]-2′,2-diyloxy)] Di(ethane-1-ol)(DBHBNA14BHN)(a compound of formula (Ia) wherein X = 2-hydroxyethyl and A 1 =1,4-naphthylene; Table A Compound 31)

[0508] Example 5a: 2-[2-Hydroxy-(1,1′-binaphthyl)-2′-oxy]-ethan-1-ol (building block block)1)

[0509]

[0510] A mixture of racemic 1,1'-bi-2-naphthol (200 g, 692 mmol, 1.0 eq.) and KCO (110 g, 795 mmol, 1.15 eq.) in methyl ethyl ketone (MEK) (930 g) was heated to reflux for 60 minutes. Then, a solution of 2-bromoethanol (112 g, 899 mmol, 1.3 eq.) in MEK (200 mL) was slowly added, and the reaction mixture was stirred at reflux for about 7 hours.

[0511] The reaction mixture is cooled to room temperature, and toluene (1000ml) and water (400ml) are then added. The mixture is acidified with aqueous HCl solution. The phases are separated, and the aqueous phase is extracted with toluene. The combined organic phase is washed with water and brine. The organic phase is concentrated under reduced pressure (150mbar) until all MEK is removed by distillation. The mixture is cooled to room temperature. The crystals formed are filtered out to obtain the title compound as a white solid (80.0g, 242mmol, yield: 35%, chemical purity: 83.75%). The slurry is repeatedly washed with THF to obtain the desired product with a chemical purity > 99%.

[0512] 1 H NMR (80MHz, CDCl3): δ=8.16-7.75(m, 4H), 7.56-6.96(m, 8H), 5.05(br s, 1H), 4.23-4.03(m, 2H), 3.71-3.44(m, 2H), 1.52(br s, 1H)ppm.

[0513] Example 5b: 1,4-di(bromomethyl)naphthalene (structural unit 2)

[0514] Example 5b.1: 1,4-Naphthalene-dimethanol

[0515]

[0516] To a mixture of lithium aluminum hydride (12 g, 316 mmol, 3.4 eq.) in THF (350 g) was added 1,4-naphthalenedicarboxylic acid (20 g, 92.5 mmol, 1 eq.) portionwise and the mixture was heated to reflux for 16 h until TLC (cyclohexane / ethyl acetate 1:1) showed complete conversion.

[0517] The mixture is cooled to room temperature, and 25g water is carefully added. The pH value is adjusted to 1.5 by adding 10% (w / w) HCl aqueous solution. Ethyl acetate (200g) and salt solution (50g) are added. Each phase is separated, and the aqueous phase is extracted with ethyl acetate (100g). The organic phase merged is washed with water (50mL), saturated NaHCO aqueous solution (2x 50mL) and saturated NH4Cl aqueous solution (50mL). With organic phase Na2SO4 drying and concentrating under reduced pressure, obtain title compound (14.3g, 76.0mmol, productive rate: 82%), is white solid.

[0518] 1 H NMR (80MHz, DMSO-d6): δ=8.25-7.94(m, 2H), 7.69-7.36(m, 4H), 5.36-5.16(m, 2H), 5.03-4.85(m, 4H)ppm.

[0519] Example 5b.2: 1,4-di(bromomethyl)naphthalene

[0520]

[0521] 1,4-Naphthalenedimethanol (14 g, 74 mmol, 1 eq.) obtained in Example 5b.1 above was dissolved in THF (250 g) at 0° C. Then, phosphorus tribromide (44.3 g; 163 mmol; 2.2 eq.) was added and the mixture was stirred at room temperature for 24 hours until TLC (cyclohexane / ethyl acetate 1:1) showed complete conversion.

[0522] Saturated NaHSO3 aqueous solution (100mL) was slowly added to the mixture. Dichloromethane (400mL) and water (220mL) were added to the mixture. Each phase was separated, and the aqueous phase was extracted with dichloromethane (100mL). The combined organic phase was washed with brine and water. The organic phase was concentrated under reduced pressure. Methanol (100g) was added to the remaining residue, and the mixture was stirred at room temperature for 2 hours. The title compound 1,4-di(bromomethyl)naphthalene was collected by filtration as a white solid (19.5g, 62.1mmol, yield: 83%).

[0523] 1 H NMR (80MHz, DMSO-d6): δ=8.45-8.07(m, 2H), 7.90-7.48(m, 4H), 5.21(s, 4H)ppm.

[0524] Example 5c: 2,2′-[1,4-naphthylenebis(methyleneoxy[1,1′-binaphthylene]-2′,2-diyloxy ) ] Di(ethane-1-ol)(DBHBNA14BHN)(a compound of formula (Ia) wherein X = 2-hydroxyethyl and A 1 =1,4-naphthylene; Table A Compound 31)

[0525]

[0526] 2-[2-Hydroxy-(1,1′-binaphthyl)-2′-oxy]-ethan-1-ol (36.3 g, 110 mmol, 2.1 eq., obtained in Example 5a) was dissolved in acetone (300 g). K2CO3 (15.2 g, 110 mmol, 2.1 eq.) was added and the mixture was heated to 60-70°C. Then a solution of 1,4-di(bromomethyl)naphthalene (16.4 g, 52.3 mmol, 1 eq., obtained in Example 5b) in acetone (120 g) was added dropwise. The mixture was stirred at reflux for 1 day until TLC (cyclohexane / ethyl acetate 1:1) showed complete conversion.

[0527] Water (300 g) and toluene (300 g) were added to the mixture. The resulting mixture was concentrated under reduced pressure to remove acetone, and then acidified by adding HCl aqueous solution (16% w / w). The aqueous phase was separated and extracted with dichloromethane. The combined organic phase was concentrated under reduced pressure to a thick suspension, and then stirred at room temperature for 18 hours. The solid product was collected by filtration. The crude product was dissolved in dichloromethane. The resulting solution was washed with water, dried with Na2SO4 and concentrated under reduced pressure to dryness to obtain the title compound as a white solid (30.0 g, 36.9 mmol, yield: 67%) with a chemical purity of 99.7%.

[0528] 1 H NMR (80MHz, CDCl3): δ = 8.05-7.67 (m, 8H), 7.62-6.74 (m, 22H), 5.28 (mc, 4H), 4.07-3.77 (m, 4H), 3.59-3.21 (m, 4H), 2.05 (t, J = 5.9Hz, 2H) ppm.

[0529] Example 6: 2,2′-[1,2-phenylenebis(methyleneoxy[1,1′-binaphthylene]-2′,2-diyloxy)] Di(ethane-1-ol) (DBHBNAOBHP) (a compound of formula (Ia) wherein X = 2-hydroxyethyl and A 1 =1,2-phenylene; Table A Compound 26)

[0530]

[0531] 2-[2-Hydroxy-(1,1′-binaphthyl)-2′-oxy]-ethan-1-ol (50 g, 151.3 mmol, 2.1 eq., obtained in Example 5a) was dissolved in acetone (450 g). K2CO3 (20.9 g, 151.3 mmol, 2.1 eq.) was added and the mixture was heated to 60-70°C. Then, a solution of 1,2-bis(bromomethyl)benzene (19 g, 72 mmol, 1 eq.) in acetone (180 g) was added dropwise. The mixture was stirred at reflux for 18 hours until TLC (cyclohexane / ethyl acetate 2:1) showed complete conversion.

[0532] Water (450 g) and toluene (450 g) were added to the mixture. The mixture was concentrated under reduced pressure to remove acetone and then acidified by adding HCl aqueous solution (16% w / w). The aqueous phase was separated and extracted with toluene (225 g). The combined organic phase was washed with water (225 g), dried over Na2SO4 and concentrated to dryness under reduced pressure. N-pentane was added to the residue and the mixture was stirred at room temperature for 1 hour. The solid was collected by filtration and dried under vacuum at 40°C to obtain the title compound (42.5 g, 55.7 mmol, yield: 74%) with a chemical purity of 96.7%.

[0533] 1 H NMR (80MHz, CDCl3): δ = 8.06-7.65 (m, 8H), 7.53-6.52 (m, 20H), 4.88-4.34 (m, 4H), 4.17-3.79 (m, 4H), 3.62-3.24 (m, 4H), 2.16-1.49 (m, 2H) ppm.

[0534] Example 7: 2,2′-[1,3-phenylenebis(methyleneoxy[1,1′-binaphthylene]-2′,2-diyloxy)] Di(ethane-1-ol) (DBHBNAMBHP) (a compound of formula (Ia) wherein X = 2-hydroxyethyl and A 1 =1,3-phenylene; Table A Compound 27)

[0535]

[0536] 2-[2-Hydroxy-(1,1′-binaphthyl)-2′-oxy]-ethan-1-ol (17.4 g, 52.7 mmol, 2.1 eq., obtained in Example 5a) was dissolved in acetone (150 g). K2CO3 (7.3 g, 52.7 mmol, 2.1 eq.) was added and the mixture was heated to 60-70°C. A solution of 1,3-bis(bromomethyl)benzene (6.6 g, 25 mmol, 1 eq.) in acetone (60 g) was then added dropwise. The mixture was stirred at reflux for 18 hours until TLC (cyclohexane / ethyl acetate 2:1) showed complete conversion.

[0537] Water (150 g) and toluene (150 g) were added to the mixture. The mixture was concentrated under reduced pressure to remove acetone and then acidified by adding aqueous HCl (16% w / w). The aqueous phase was separated and extracted with toluene (75 g) at 60° C. The combined organic phase was washed with water (75 g), dried over Na2SO4 and concentrated to dryness under reduced pressure. The residue was recrystallized twice from MTBE and dried in vacuo at 40° C. to give the title compound (13.4 g, 17.5 mmol, yield: 66%, chemical purity: 97.8%) as a white solid.

[0538] 1H NMR (80MHz, CDCl3): δ=8.05-7.69(m, 8H), 7.52-6.96(m, 16H), 6.94-6.22(m, 4H), 4.76(m c , 4H), 4.19-3.83 (m, 4H), 3.64-3.27 (m, 4H), 1.95 (app.dt, J=6.5, 3.0Hz, 2H)ppm.

[0539] Example 8a: Dimethyl-2,2'-[1,4-phenylenebis(methyleneoxy[1,1'-binaphthyl]-2',2-dimethyl methyloxy)] di(acetate) (a compound of formula (Ia) wherein X = methoxycarbonylmethyl and A 1 =1,4-phenylene; Table A Compound 49)

[0540]

[0541] A mixture of 2,2′-[1,4-phenylenebis(methyleneoxy)]bis([1,1′-binaphthyl]-2-ol (147 g, 218 mmol, 1.0 eq., obtained in Example 1), KCO (90 g, 654 mmol, 3 eq.) and acetone (1500 g) was heated to 50° C. Methyl bromoacetate (100 g, 654 mmol, 3 eq.) was added dropwise and the reaction mixture was heated to reflux for about 12 hours until TLC (cyclohexane / ethyl acetate 2:1) showed complete conversion.

[0542] The reaction mixture was concentrated under reduced pressure to remove most of acetone. Then, water (500g) and ethyl acetate (1000g) were added and the mixture was stirred for 30 minutes. The aqueous phase was separated and extracted with ethyl acetate (250g). The organic phase merged was washed with salt water (500g), and Na was used SO4 was dried, and was concentrated under reduced pressure to dryness to obtain a crude product. N-pentane was added, and slurries were stirred at room temperature for 1 hour. The crystal formed was filtered out, and the required product was obtained in a quantitative yield, which was a pale solid.

[0543] 1 H NMR (80MHz, CDCl3): δ=8.03-7.72(m, 8H), 7.48-7.02(m, 16H), 6.75(s, 4H), 4.97(s, 4H), 4.44(s, 4H), 3.52(s, 6H)ppm.

[0544] Example 8b: 2,2'-[1,4-phenylenebis(methyleneoxy[1,1'-binaphthylene]-2',2-diyloxy)] Di(acetic acid)

[0545]

[0546] A mixture of dimethyl-2,2'-[1,4-phenylenebis(methyleneoxy[1,1'-binaphthyl]-2',2-diyloxy)]di(acetate) (178.4 g, 218 mmol, 1.0 eq., obtained in Example 8a), KOH (133.3 g; 871.6 mmol, 4 eq.), ethanol (424 g) and water (106 g) was heated to reflux for 2 hours. After complete conversion, the mixture was cooled to room temperature and acidified by adding dilute aqueous HCl. Water was decanted from the solid formed. Toluene (400 g) was added to the solid, and the mixture was heated to reflux for 30 minutes. The solid was filtered out, and the filtrate was concentrated under reduced pressure to obtain a crude product. The crude product was first purified by stirring it in a pentane / MTBE mixture (9:1) for 2 h and then stirring it under reflux in MTBE to give the title compound (84.2 g, 106 mmol, yield: 49%, chemical purity: 99.1%) as a white solid.

[0547] 1 H NMR (80MHz, CDCl3): δ=9.88 (br s, 2H, OH), 8.07-7.53 (m, 8H), 7.48-6.89 (m, 16H), 6.59 (d, J=3.9Hz, 4H), 5.03-4.49 (m, 4H), 4.45-4.02 (m, 4H)ppm.

[0548] 2.3 Refractive index n of the monomer of formula (I) D :

[0549] Table B below lists the refractive indices of some monomers of formula (I) calculated using the software ACD / ChemSketch 2012 (Advanced Chemistry Development, Inc.). The individual monomers in Table B are identified by their names and entry numbers in Table A. Furthermore, quantum chemical calculations for all monomers included in Table B confirm that they do not absorb or absorb only to a negligible extent in the visible range and are therefore essentially colorless.

[0550] Table B

[0551]

[0552]

[0553]

[0554]

[0555] 3. Preparation of thermoplastic resin from monomers of formula (I)

[0556] 3.1 Analysis related to resins prepared from monomers of formula (I):

[0557] Refractive index (n D ):

[0558] The refractive index was measured using a disc-shaped test piece made of a polycarbonate resin and having a thickness of 3 mm as a test piece according to JIS B 7071-2: 2018. The measurement was performed at 23°C using the following refractive index measuring device.

[0559] Refractive index measurement device:

[0560] KPR-3000, manufactured by Shimadzu Corporation

[0561] Abbe number (ν):

[0562] The same disc-shaped test piece with a thickness of 3 mm as the test piece used in the refractive index measurement was used. The refractive index value was measured at 23° C. and wavelengths of 486 nm, 589 nm, and 656 nm using the following refractive index measuring device. Then, the Abbe number was calculated using the following formula.

[0563] Refractive index measurement device:

[0564] KPR-3000, manufactured by Shimadzu Corporation

[0565] ν=(nD-1) / (nF-nC)

[0566] nD: refractive index at wavelength 589nm

[0567] nC: refractive index at a wavelength of 656nm

[0568] nF: refractive index at a wavelength of 486nm

[0569] Glass transition temperature (Tg):

[0570] The glass transition temperature is measured by differential scanning calorimetry (DSC) using a heating program of 10° C. / min in accordance with JIS K7121-1987.

[0571] Differential Scanning Calorimetry Apparatus:

[0572] X-DSC7000, manufactured by Hitachi High-Tech Science Corporation

[0573] Molecular weight

[0574] The molecular weight distribution of the resin molecules, in particular the weight average molecular weight (Mw) value of the resin was measured by gel permeation chromatography (GPC) and calculated by standard polystyrene conversion method. The following apparatus, column and measurement conditions were used:

[0575] GPC apparatus: HLC-8420GPC (from Tosoh Corporation);

[0576] Columns: three TSKgel SuperHM-M (from Tosoh Corporation),

[0577] A guard column SuperHM-M (from Tosoh Corporation),

[0578] a TSKgel SuperH-RC (from Tosoh Corporation);

[0579] Detection device: RI detection

[0580] Standard polystyrene: PstQuick C as a standard polystyrene kit (from Tosoh Corporation);

[0581] Eluent: tetrahydrofuran;

[0582] Eluent flow rate: 0.6 ml / min;

[0583] Column temperature: 40℃.

[0584] The number average molecular weight (Mn) value is calculated using a method similar to the method for measuring the above-mentioned Mw value. The weight average molecular weight (Mw) and number average molecular weight (Mn) of polystyrene conversion are calculated using a pre-made polystyrene standard curve. Specifically, a standard polystyrene with a known molecular weight ("PStQuick C" from Tosoh Corporation) is used to make a standard curve. In addition, based on the measured data of standard polystyrene, the elution time and molecular weight value of each peak are plotted, and three-dimensional approximation is performed to obtain a calibration curve. The values ​​of Mw and Mn are calculated based on the following calculation formula:

[0585] Mw=Σ(Wi x Mi)÷Σ(Wi)

[0586] Mn=Σ(Ni x Mi)÷Σ(Wi)

[0587] In the calculation formula, "i" represents the "i"th dividing point, "Wi" represents the molecular weight (g) of the polymer at the "i"th dividing point, "Ni" represents the number of polymer molecules at the "i"th dividing point, and "Mi" represents the molecular mass at the "i"th dividing point. Molecular mass (M) represents the molecular mass value of polystyrene at the corresponding elution time in the calibration curve.

[0588] Content of low molecular weight compounds (CLWC)

[0589] The content of low molecular weight compounds indicates the area ratio of compounds having an Mw value of less than 1000 in GPC analysis. Therefore, the content of low molecular weight compounds is determined according to the following formula:

[0590]

[0591] GPC analysis of low molecular weight compounds is performed as described above for measuring the molecular weight of thermoplastic resins.

[0592] Birefringence

[0593] The value of Δn (birefringence) was determined as follows: a cast film having a thickness of 0.1 mm was cut into squares having a side of 5.0 cm, and then both ends of the film were clamped with chucks (distance between chucks: 3.0 cm), stretched 1.5 times at a temperature of Tg+20° C. of the polycarbonate resin, and then the phase difference (Re) at 589 nm was measured using an ellipsometer M-220 (JASCO Co., Ltd., Japan), and then calculated according to the following formula:

[0594] Δn=Re / d

[0595] Δn: Orientation birefringence

[0596] Re: Phase difference

[0597] D: Thickness

[0598] The standards for birefringence (Δn) are shown in the following table.

[0599]

[0600]

[0601] 3.2 Thermoplastic resin preparation example:

[0602] 3.2.1 Polycarbonate resin

[0603] Embodiment 9 (E9):

[0604] 21.6375 g (0.0493 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF), 4.4587 g (0.0055 mol) of 2,2'-[1,4-phenylenebis(methyleneoxy[1,1'-binaphthyl]-2',2-diyloxy)]di(ethane-1-ol) (DBHBNABHP) obtained in Example 2, 12.0983 g (0.0565 mol) of diphenyl carbonate (DPC) and 0.4606 × 10 -4 g(0.5483×10 -6 mol) of sodium bicarbonate as a raw material was placed in a 300 ml reactor with a stirrer and a distillation apparatus. The reactor was filled with nitrogen and the internal pressure was set to 101.3 kPa.

[0605] The reactor was immersed in an oil bath heated to 200°C, and then the transesterification reaction was started. The reaction mixture was stirred 5 minutes after the reaction started. After 20 minutes, the pressure of the reaction mixture dropped from 101.3 kPa to 26.66 kPa in 10 minutes. While the pressure was reduced, the reaction mixture was heated to 210°C. Then it was further heated to 220°C 60 minutes after the reaction started. Starting from 80 minutes after the reaction started, the pressure of the reaction mixture was reduced to 20.00 kPa, and the reaction mixture was heated to 240°C in 10 minutes. Then the pressure of the reaction mixture was reduced to 0 kPa and maintained for 30 minutes.

[0606] Nitrogen was introduced into the reactor, and the pressure of the reaction mixture was restored to 101.3 kPa, finally obtaining a polycarbonate resin.

[0607] The obtained polycarbonate resin had a refractive index of 1.647, an Abbe number of 22.31, and a Tg of 144°C; and a polystyrene-equivalent weight average molecular weight of 34,459. The molar ratios of the diol monomers used are listed in Table D, and the properties of the obtained resins are summarized in Table E.

[0608] Embodiment 10 (E10):

[0609] The polycarbonate resin was prepared according to the same method as used in Example 9, except that 10.4972 g of DBHBNABHP (0.0138 mol), 14.0818 g of BPEF (0.0321 mol), 10.0725 g of DPC (0.047 mol) and 0.7707×10 -4 g of NaHCO3 (0.9175×10 -6 The molar ratios of the monomers used are listed in Table D, and the properties of the resulting resins are summarized in Table E.

[0610] Embodiment 11 (E11):

[0611] The polycarbonate resin was prepared according to the same method as used in Example 9, except that 16.7174 g of DBHBNABHP (0.0219 mol), 6.4222 g of BPEF (0.0146 mol), 7.9897 g of DPC (0.0373 mol) and 0.6143×10 -4 g of NaHCO3 (0.7312×10 -6 The molar ratios of the monomers used are listed in Table D, and the properties of the resulting resins are summarized in Table E.

[0612] Examples 12 to 20, 23 to 27 and 29 to 33 (E12 to E20, E23 to E27 and E29 to E33)

[0613] The polycarbonate resins of these examples were produced according to the same method used in Example 9, with the only difference being that the amounts and types of monomers and catalysts given in Tables C1-C4 were used. The molar ratios of the monomers used in each example are listed in Table D, and the properties of the resulting resins are summarized in Table E.

[0614] 3.2.2 Polyester carbonate resin

[0615] Embodiment 21 (E21):

[0616] 13.7869 g (0.0181 mol) of 2,2'-[1,4-phenylenebis(methyleneoxy[1,1'-binaphthyl]-2',2-diyloxy)]di(ethane-1-ol) (DBHBNABHP), 16.2236 g (0.301 mol) of 9,9-bis[6-(2-hydroxyethoxy)2-naphthyl]fluorene (NOLE), 9.5057 g (0.0181 mol) of 6,6'- Diphenyl-2,2'bis(2-hydroxyethoxy)-1,1'-binaphthyl (DPBN), 21.8162 g (0.0542 mol) of 2,2'-[(1,1'-binaphthyl-2,2'-diyl)bis(oxy)]diacetic acid (BINOL-DC), 3.0558 g (0.0143 mol) of diphenyl carbonate (DPC) and catalyst tri(2,4-pentanedione)aluminum(III) (0.4701×10 -2 g, 0.1449×10 -3 mol, also referred to herein as Al(acac)3) and diethyl (4-methylbenzyl)phosphonate (0.5882×10 -2 g, 0.2428×10 -3 mol) as a raw material, was placed in a 300 ml reactor equipped with a stirrer and a distillation device. The reactor was filled with nitrogen and the internal pressure was set to 101.3 kPa.

[0617] The reactor was immersed in an oil bath heated to 200°C, and then the transesterification reaction was started. The reaction mixture was stirred 5 minutes after the reaction started. After 20 minutes, the pressure of the reaction mixture was reduced from 101.3 kPa to 93.33 kPa in 10 minutes. Starting from 10 minutes after the decompression was completed, the reaction mixture was heated to 240°C for 40 minutes. Then, the pressure of the reaction mixture was further reduced to 40.00 kPa in 20 minutes.

[0618] Nitrogen was introduced into the reactor and the pressure of the reaction mixture was restored to normal pressure. Then, the steam trap was replaced with a new one and the reaction conditions were set to 240°C and 300 Torr. The reaction mixture was heated to 250°C and then the pressure of the reaction mixture was reduced to 0 kPa over 60 minutes and maintained at that level for 30 minutes.

[0619] Nitrogen was introduced into the reactor, and the pressure of the reaction mixture was restored to 101.3 kPa, thereby finally obtaining a polyester carbonate resin.

[0620] The polyester carbonate resin obtained had a refractive index of 1.690, an Abbe number of 17.80, and a Tg of 160°C; and a polystyrene-equivalent weight average molecular weight of 36,654. The molar ratios of the monomers used are listed in Table D, and the properties of the obtained resins are summarized in Table E.

[0621] Embodiment 28 (E28):

[0622] Polyester carbonate resins were produced according to the same method as used in Example 21, except that the amounts and types of monomers and catalysts used were as shown in Tables C1-C4. The molar ratios of the monomers used are listed in Table D, and the properties of the resulting resins are summarized in Table E.

[0623] 3.2.3 Polyester resin

[0624] Embodiment 22 (E22):

[0625] 3.5226 g (0.0046 mol) of 2,2'-[1,4-phenylenebis(methyleneoxy[1,1'-binaphthyl]-2',2-diyloxy)]di(ethane-1-ol) (DBHBNABHP), 2.4287 g (0.0046 mol) of 6,6'-diphenyl-2,2'bis(2-hydroxyethoxy)-1,1'-binaphthyl (DPBN), 1.0031 g (0.0162 mol) of ethylene glycol (EG), 4.6451 g (0.0115 mol) of 2,2'-[(1,1'-binaphthyl-2,2'-diyl)bis(oxy)]diacetic acid (BINOL-DC), 0.1267 × 10- 2 g(0.5170×10 -5 mol) of manganese(II) acetate tetrahydrate and 0.1251×10 -2 g(0.7100×10 -5 1 mol) of calcium acetate monohydrate was used as a raw material and placed in a 50 ml reactor equipped with a stirrer and a distillation device. The reactor was filled with nitrogen.

[0626] The reactor was immersed in an oil bath heated to 100°C and the transesterification reaction was started. Stirring of the reaction mixture began 5 minutes after the start of the reaction. 120 minutes after the start of the reaction, the reaction mixture was heated to 230°C and maintained at this level for 290 minutes.

[0627] Then, 0.1498×10 -2 g(1.5283×10 -5 mol) of phosphoric acid and 0.4092×10 -2 g(3.9144×10 - 5 mol) of germanium dioxide was added to the reaction mixture to start the polycondensation reaction. Then, the reaction mixture was heated to 270° C., and the pressure of the reaction mixture was reduced to 0 kPa within 90 minutes and maintained at this level for 120 minutes.

[0628] Nitrogen gas was introduced into the reactor, and the pressure of the reaction mixture was restored to 101.3 kPa to obtain a polyester resin.

[0629] The obtained polyester resin had a refractive index of 1.690, an Abbe number of 17.60, and a Tg of 148°C; and a polystyrene-equivalent weight average molecular weight of 34,544. The molar ratios of the monomers used are listed in Table D, and the properties of the obtained resins are summarized in Table E.

[0630] 3.2.4 Comparative example of polycarbonate resin

[0631] Comparative Example 1 (CE1):

[0632] The polycarbonate resin was prepared according to the same method as used in Example 9, except that 10.2444 g of BNEF (0.019 mol), 19.4593 g of BPEF (0.0444 mol), 13.9877 g of DPC (0.0653 mol) and 0.3838×10 -4 g of NaHCO3 (0.4568×10 -6 The molar ratios of the monomers used are listed in Table D, and the properties of the resulting resins are summarized in Table E.

[0633] Comparative Example 2 (CE2):

[0634] The polycarbonate resin was prepared according to the same method as used in Example 9, except that 15.2611 g of BNE (0.0408 mol), 11.9149 g of BPEF (0.0272 mol), 14.9882 g of DPC (0.07 mol) and 0.4981×10 -4 g NaHCO3(0.593×10 -6 The molar ratios of the monomers used are listed in Table D, and the properties of the resulting resins are summarized in Table E.

[0635] Comparative Example 3 (CE3):

[0636] The polycarbonate resin was prepared according to the same method as used in Example 9, except that 16.2901 g of BNE (0.0435 mol), 4.7694 g of BPEF (0.0109 mol), 11.8826 g of DPC (0.0555 mol) and 0.4568×10 -4 g NaHCO3(0.5438×10 -6 The molar ratios of the monomers used are listed in Table D, and the properties of the resulting resins are summarized in Table E.

[0637] Tables C1 to C4 below summarize the amounts of monomers and catalysts used to prepare the thermoplastic resins of Examples E9 to E33 and CE1 to CE3. The molar ratios of the monomers used in each example are listed in Table D, and the properties of the resulting resins are summarized in Table E.

[0638] Table C1: Amounts of monomers used in Examples 9 to 33 and CE1 to CE3 (grams of base)

[0639] Table C2: Amounts of monomers used in Examples 9 to 33 and CE1 to CE3 (molar base)

[0640] Table C3: Amount of catalyst used in Examples 9 to 33 and CE1 to CE3 (grams of base)

[0641] Table C4: Amounts of catalyst used in Examples 9 to 33 and CE1 to CE3 (molar base)

[0642] Table D: Molar ratios of monomers used in Examples 9 to 33 and CE1 to CE3

[0643] Table E: Properties of Thermoplastic Resins E9 to E33 and CE1 to CE3

[0644]

[0645]

[0646]

[0647]

[0648]

[0649]

[0650]

[0651]

Claims

1. Use of a compound of formula (I) or a mixture thereof as a monomer for producing a thermoplastic resin in X 1 and X 2 are independently selected from hydrogen, -Alk 1 -OH, -CH2-A 2 -CH2-OH, -Alk 2 -C(O)OR x 、-CH2-A 2 -C(O)OR x and-C(O)-A 2 -C(O)OR x , where R x is selected from hydrogen, phenyl, benzyl and C1-C4-alkyl; Y 1 and Y 2 Independently selected from -CH2-, -CHAr Y - and -CH(CH2Ar Y )-; A 1 Selected from single bond, -CH2-, -CHAr A -、-CH(CH2Ar A )-、-C(CH2Ar A )2-, moieties of formula (A), monocyclic or polycyclic arylene groups having 6 to 26 carbon atoms as ring members and monocyclic or polycyclic heteroarylene groups having a total of 5 to 26 atoms as ring members, wherein 1, 2, 3 or 4 of these ring member atoms of the heteroarylene group are selected from nitrogen, sulfur and oxygen, and the remaining atoms of these ring member atoms of the heteroarylene group are carbon atoms, wherein the monocyclic or polycyclic arylene groups and the monocyclic or polycyclic heteroarylene groups are unsubstituted or carry 1, 2, 3 or 4 R Ar Group, in Q represents a single bond, O, C=O, CH2, S or SO2; R 5a , R 5b are independently selected from hydrogen, fluorine, CN, R, OR, CH k R' 3-k , NR2, C(O)R and C(O)NH2, wherein k is 0, 1 or 2; and * indicates the same as Y 1 or Y 2 The connection point; Alternatively, -Y in formula (I) 1 -A 1 -Y 2 The - part can be -CH2- or -CHAr Y -, n is 1, 2 or 3; R 1 , R 2 , R 3 and R 4 independently selected from halogen, C2-C3-alkynyl, CN, R, OR, CH s R' 3-s , NR2, C(O)R and CH=CHR", if there are more than one R 1 , R 2 , R 3 or R 4 , then R 1 , R 2 , R 3 or R 4 can be the same or different, where s is 0, 1, or 2 each time it occurs; m, p, q and r are independently 0, 1 or 2; A 2 is selected from phenylene, naphthylene and biphenylene; Alk 1 is C2-C4-alkanediyl; Alk 2 is C1-C4-alkanediyl; Ar Y and Ar A is chosen from monocyclic or polycyclic aryl radicals having 6 to 26 carbon atoms as ring atoms and monocyclic or polycyclic heteroaryl radicals having a total of 5 to 26 atoms as ring members, wherein 1, 2, 3 or 4 of these ring member atoms of the heteroaryl radical are chosen from nitrogen, sulfur and oxygen, and the remaining atoms of these ring member atoms of the heteroaryl radical are carbon atoms, wherein Ar Y and Ar A Unsubstituted or replaced by 1, 2 or 3 R Ar Group substitution; R Ar Selected from R, OR, CH t R' 3-t , NR2 and CH=CHR", where if there is more than one R on the same (hetero)aryl or (hetero)arylene Ar , then R Ar can be the same or different, where t is 0, 1, or 2 each time it occurs; R is selected from C1-C4-alkyl, phenyl, naphthyl, phenanthrenyl and triphenylene, wherein phenyl, naphthyl, phenanthrenyl and triphenylene are unsubstituted or substituted by 1, 2, 3 or 4 identical or different R'" groups; R' is selected from phenyl, naphthyl, phenanthrenyl and triphenylene, wherein phenyl, naphthyl, phenanthrenyl and triphenylene are unsubstituted or substituted with 1, 2, 3 or 4 identical or different R'" groups; R" is selected from hydrogen, methyl, phenyl and naphthyl, wherein phenyl and naphthyl are unsubstituted or substituted with 1, 2, 3 or 4 identical or different R'" groups; R'" is selected from phenyl, OCH3, CH3, N(CH3)2 and C(O)CH3.

2. A compound of formula (I) in X 1 and X 2 are independently selected from hydrogen, -Alk 1 -OH, -CH2-A 2 -CH2-OH, -Alk 2 -C(O)OR x 、-CH2-A 2 -C(O)OR x and-C(O)-A 2 -C(O)OR x , where R x is selected from hydrogen, phenyl, benzyl and C1-C4-alkyl; Y 1 and Y 2 Independently selected from -CH2-, -CHAr Y - and CH(CH2Ar Y )-; A 1 Selected from single bond, -CH2-, -CHAr A -、-CH(CH2Ar A )-、-C(CH2Ar A )2-, moieties of formula (A), monocyclic or polycyclic arylene groups having 6 to 26 carbon atoms as ring members and monocyclic or polycyclic heteroarylene groups having a total of 5 to 26 atoms as ring members, wherein 1, 2, 3 or 4 of these ring member atoms of the heteroarylene group are selected from nitrogen, sulfur and oxygen, and the remaining atoms of these ring member atoms of the heteroarylene group are carbon atoms, wherein the monocyclic or polycyclic arylene groups and the monocyclic or polycyclic heteroarylene groups are unsubstituted or carry 1, 2, 3 or 4 R Ar Group, in Q represents a single bond, O, C=O, CH2, S or SO2; and R 5a , R 5b are independently selected from hydrogen, fluorine, CN, R, OR, CH k R' 3-k , NR2, C(O)R and C(O)NH2, wherein k is 0, 1 or 2; and * indicates the same as Y 1 or Y 2 The connection point; Alternatively, -Y in Formula I 1 -A 1 -Y 2 The - part can be -CH2- or -CHAr Y -, n is 1, 2 or 3; R 1 , R 2 , R 3 and R 4 are independently selected from hydrogen, halogen, C2-C3-alkynyl, CN, R, OR, CH s R' 3-s , NR2, C(O)R and CH=CHR", if there are more than one R 1 , R 2 , R 3 or R 4 , then R 1 , R 2 , R 3 or R 4 can be the same or different, where s is 0, 1, or 2 each time it occurs; m, p, q and r are independently 0, 1 or 2; A 2 is selected from phenylene, naphthylene and biphenylene; Alk 1 is C2-C4-alkanediyl; Alk 2 is C1-C4-alkanediyl; Ar Y and Ar A is chosen from monocyclic or polycyclic aryl radicals having 6 to 26 carbon atoms as ring atoms and monocyclic or polycyclic heteroaryl radicals having a total of 5 to 26 atoms as ring members, wherein 1, 2, 3 or 4 of these ring member atoms of the heteroaryl radical are chosen from nitrogen, sulfur and oxygen, and the remaining atoms of these ring member atoms of the heteroaryl radical are carbon atoms, wherein Ar Y and Ar A Unsubstituted or replaced by 1, 2 or 3 R Ar Group substitution; R Ar Selected from R, OR, CH t R' 3-t , NR2 and CH=CHR", where if there is more than one R on the same (hetero)aryl or (hetero)arylene Ar , then R Ar can be the same or different, where t is 0, 1, or 2 each time it occurs; R is selected from C1-C4-alkyl, phenyl, naphthyl, phenanthrenyl and triphenylene, wherein phenyl, naphthyl, phenanthrenyl and triphenylene are unsubstituted or substituted by 1, 2, 3 or 4 identical or different R'" groups; R' is selected from phenyl, naphthyl, phenanthrenyl and triphenylene, wherein phenyl, naphthyl, phenanthrenyl and triphenylene are unsubstituted or substituted with 1, 2, 3 or 4 identical or different R'" groups; R" is selected from hydrogen, methyl, phenyl and naphthyl, wherein phenyl and naphthyl are unsubstituted or substituted with 1, 2, 3 or 4 identical or different R'" groups; R'" is selected from phenyl, OCH3, CH3, N(CH3)2 and C(O)CH3; The compound of formula (I) does not include the following compound of formula (I), wherein X 1 and X 2 are all hydrogen or -CH2CH2-OH, Y 1 and Y 2 Both are CH2, and A 1 is a single bond or CH2; and except for the following compounds of formula (I), wherein n is 1, X 1 and X 2 All are hydrogen, Y 1 and Y 2 are all CH2, m, p, q and r are all 0, and A 1 It is 1,2-phenylene, 1,3-phenylene, 1,6-pyrenylene, 4,4'-biphenylene, 2,6-pyridylene, 4,4"-m-terphenylene, 2,5-[1,3,4]-thiadiazolylene, 2,5-[1,3,4]-oxadiazolylene, 2,5-thienyl-bis(4,1-phenylenemethylene), 9,9-diethyl-2,7-9H-fluorenylene, 10-methyl-3,7-phenothiazinylene or 10-ethyl-3,7-phenothiazinylene.

3. The use according to claim 1 or the compound according to claim 2, wherein X 1 and X 2 Selected from -Alk 1 -OH and -CH2-A 2 -CH2-OH.

4. The use according to claim 1 or the compound according to claim 2, wherein X 1 and X 2 All are hydrogen.

5. The use according to claim 1 or the compound according to claim 2, wherein X 1 and X 2 Selected from -Alk 2 -C(O)OR x and -CH2-A 2 -C(O)OR x .

6. The use according to claim 1 or the compound according to claim 2, wherein X 1 and X 2 from the group consisting of hydrogen, 2-hydroxyethyl, methoxycarbonyl-methyl, hydroxymethyl-phenyl-methyl, hydroxymethyl-naphthyl-methyl, hydroxymethyl-biphenyl-methyl, methoxycarbonyl-phenyl-methyl and methoxycarbonyl-naphthyl-methyl, in particular from the group consisting of hydrogen, 2-hydroxyethyl, methoxycarbonyl-methyl, (4-(hydroxymethyl)phenyl)methyl, (3-(hydroxymethyl)phenyl)methyl, (4-(hydroxymethyl)-1-naphthyl)methyl, (6-(hydroxymethyl)-2-naphthyl)methyl, 4'-(hydroxymethyl)-1,1'-biphenyl-4-methyl, (4-(methoxycarbonyl)phenyl)methyl, (3-(methoxycarbonyl)phenyl)methyl, (4-(methoxycarbonyl)-1-naphthyl)methyl and (6-(methoxycarbonyl)-2-naphthyl)methyl.

7. The use or compound according to any one of the preceding claims, wherein X 1 and X 2 Have the same meaning.

8. The use or compound according to any one of the preceding claims, wherein Y 1 and Y 2 All are -CH2-.

9. The use or compound according to any one of the preceding claims, wherein A 1 A moiety selected from the group consisting of: a moiety of formula (A), a monocyclic or polycyclic arylene group and a monocyclic or polycyclic heteroarylene group, wherein the monocyclic or polycyclic arylene group and the monocyclic or polycyclic heteroarylene group are unsubstituted or carry 1, 2, 3 or 4 R Ar Group.

10. The use or compound according to any one of the preceding claims, wherein A 1 selected from phenylene, naphthylene, 1,2-dihydroacenaphthenylene, biphenylene, 9H-fluorenylene, 11H-benzo[a]fluorenylene, 11H-benzo[b]fluorenylene, 7H-benzo[c]fluorenylene, anthracenylene, phenanthrenylene, benzo[c]phenanthrenylene, pyrenylene, phenylene, pyrrolylene, triphenylene, furanylene, benzo[b]furanylene, dibenzo[b,d]furanylene, naphtho[1,2-b]furanylene, naphtho[2,3-b]furanylene, naphtho[2,1-b]furanylene, benzo[b]naphtho[1,2-d]furanylene, benzo[b]naphtho[2,3-d]furanylene, benzo[ b] naphtho[2,1-d]furanyl, benzo[1,2-b:4,3-b']bifuranyl, benzo[1,2-b:6,5-b']bifuranyl, benzo[1,2-b:5,4-b']bifuranyl, benzo[1,2-b:4,5-b']bifuranyl, 9H-xanthenyl, tribenzo[b,d,f]oxanthyl heptyl, dibenzo[1,4]dioxinyl, 2H-naphtho[1,8-d,e][1,3]dioxinyl, phenoxathiinyl, dinaphtho[2,3-b:2',3'-d]furanyl, xanthenyl, benzo[a]xanthenyl, benzo[b]xanthenyl, thienyl, benzo[b]thienyl, dibenzo[b,d] ]thienyl, naphtho[1,2-b]thienylene, naphtho[2,3-b]thienylene, naphtho[2,1-b]thienylene, benzo[b]naphtho[1,2-d]thienylene, benzo[b]naphtho[2,3-d]thienylene, benzo[b]naphtho[2,1-d]thienylene, benzo[1,2-b:4,3-b']bithienylene , benzo[1,2-b:6,5-b']bithienyl, benzo[1,2-b:5,4-b']bithienyl, benzo[1,2-b:4,5-b']bithienyl, 9H-thioxanthenyl, 6H-dibenzo[b,d]thiopyranyl, 1,4-benzodithiinyl, naphtho[1,2-b][1,4]dithiinyl, naphtho[2,3-b][1,4]dithiinyl, 9H-10-thio-anthracenyl, thianthrenyl, benzo[a]thianthrenyl, benzo[b]thianthrenyl, dibenzo[a,c]thianthrenyl, dibenzo[a,h]thianthrenyl, dibenzo[a,i]thianthrenyl, dibenzo[a,j]thianthrenyl, dibenzo[b,i]thianthrenyl, thianthrenyl 2H-naphtho[1,8-b,c]thienyl, dibenzo[b,d]thienyl, dibenzo[b,f]thienyl, 5H-phenanthro[4,5-b,c,d]thiopyranyl, tribenzo[b,d,f]thienyl, 2,5-dihydronaphtho[1,8-b,c:4,5-b',c']bithienyl, 2,6-dihydronaphtho[1,8-b,c:4,5-b',c']bithienyl 1,8-b,c:5,4-b',c']bithienyl, tribenzo[a,c,i]thianthrenyl, benzo[b]naphtho[1,8-e,f][1,4]bithienyl, dinaphtho[2,3-b:2',3'-d]thienyl, 5H-phenanthro[1,10-b,c]thienyl, 7H-phenanthro[1,10-c,b]thienyl, dibenzo[d,d']benzo[1,2-b:4,5-b']bithienyl and dibenzo[d,d']benzo[1,2-b:5,4-b']bithienyl.

11. The use or compound according to claim 10, wherein A 1 is selected from the group consisting of phenylene, naphthylene, dibenzo[b,d]thienylene, biphenylene, 9H-fluorenylene, thianthrenylene, 9H-xanthrenylene and 9H-thioxanthrenylene, in particular selected from the group consisting of 1,4-phenylene, 1,2-phenylene, 1,3-phenylene, 2,3-naphthylene, 2,7-naphthylene, 2,6-naphthylene, 1,4-naphthylene, 1,5-naphthylene, 1,8-naphthylene, 4,6-dibenzo[b,d]thienylene, 2, 8-dibenzo[b,d]thienylene, 3,7-dibenzo[b,d]thienylene, 3,3'-biphenylene, 4,4'-biphenylene, 9,9-9H-fluorenylene, 2,7-9H-fluorenylene, 2,7-thianthrenylene, 2,8-thianthrenylene, 1,4-thianthrenylene, 2,3-thianthrenylene, 1,6-thianthrenylene, 1,9-thianthrenylene, 9,9-9H-xanthrenylene and 9,9-9H-thioxanthrenylene.

12. The use or compound according to any one of claims 1 to 8, wherein A 1 Selected from single bond, -CH2-, -CHAr A -、-CH(CH2Ar A )- and -C(CH2Ar A )2-, and especially -C(CH2Ar A )2-.

13. The use or compound according to any one of claims 1 to 7, wherein -Y in formula (I) 1 -A 1 -Y 2 - is -CH2- or -CHAr Y -, especially -CH2-.

14. The use or compound according to any one of the preceding claims, wherein R 1 , R 2 , R 3 and R 4 Have the same meaning.

15. The use or compound according to any one of the preceding claims, wherein m, p, q and r are all 0.

16. The use or compound according to any one of claims 1 to 12, 14 and 15, wherein formula (I) is represented by formula (Ia), wherein X is defined as X in any one of claims 1 to 6 1 and X 2 The definition is the same as:

17. The use or compound according to claim 16, wherein X and A 1 is defined as a row in Table A: Table A:

18. The use or compound according to claim 13, wherein in formula (I), said -Y 1 -A 1 -Y 2 - part is -CH2-, X 1 and X 2 All are 2-hydroxyethyl, m, p, q and r are all 0 and n is 1.

19. A thermoplastic resin comprising a structural unit represented by the following formula (II): in # indicates the connection point with the adjacent structural unit; And where X 1a and X 2a Derived from X in formula (I) 1 or X 2 , if X 1 or X 2 is hydrogen, replace the hydrogen with a single bond, or if X 1 or X 2 If it is not hydrogen, then replace X with an oxo (-O-) unit 1 or X 2 -OH or -OR x group, and wherein X 1 , X 2 , Y 1 , Y 2 , A 1 , R 1 , R 2 , R 3 , R 4 , n, m, p, q and r are defined as in any one of claims 1 and 3 to 15.

20. The thermoplastic resin according to claim 19, which is a thermoplastic resin of formula (IIa), wherein X a The definition of X in claim 19 1a and X 2a The definition is the same as:

21. The thermoplastic resin according to any one of claims 19 or 20, wherein the structural unit of formula (II) is linked to one of the structures represented by the following formulae (III-1) to (III-5), and in the structural unit of formula (II), X 1a and X 2a Selected from single bond, -Alk 1 -O- and -CH2-A 2 -CH2-O-, in # indicates the connection point with the adjacent structural unit.

22. The thermoplastic resin according to any one of claims 19 to 21, which is selected from copolycarbonate resins, copolyestercarbonate resins and copolyester resins, wherein the thermoplastic resin includes a structural unit of formula (V) in addition to the structural unit represented by formula (II), #-O-R z -A 3 -R z -O-#-(V) in # indicates the connection point with the adjacent structural unit; A 3 is a polycyclic group with at least two benzene rings, wherein the benzene rings may be connected via W and / or directly fused to each other and / or fused via a non-benzene carbon ring and / or fused via two non-benzene carbon rings connected via a linker L, wherein A 3 R is unsubstituted or substituted by 1, 2 or 3 R selected from halogen, C1-C6-alkyl, C5-C6-cycloalkyl, phenyl, naphthyl, 1,2-dihydroacenaphthenyl, phenanthrenyl, pyrenyl, triphenylene, benzo[b]furanyl, dibenzo[b,d]furanyl, benzo[b]thienyl, dibenzo[b,d]thienyl and thianthrenyl aa Group substitution; W is selected from a single bond, O, C=O, S, S(O), SO2, CH2, CH-Ar, CAr2, CH(CH3), C(CH3)2 and a group of formula (A') in Q' represents a single bond, O, C=O or CH2; R 7a , R 7b are independently selected from hydrogen, fluorine, CN, R, OR, CH v R' 3-v , NR2, C(O)R and C(O)NH2, wherein R and R' are as defined in claim 1, and v is 0, 1 or 2; and * indicates the point of attachment to the benzene ring; L is selected from a single bond, C1-C4-alkylene, C4-C7-cycloalkylene, C4-C7-cycloalkylene dimethylene, phenylene dimethylene, wherein L is unsubstituted or substituted by 1 or 2 R selected from C1-C4-alkyl, halogen, C1-C4-haloalkyl, C4-C7-cycloalkyl and phenyl L Group substitution, Ar is selected from monocyclic or polycyclic aryl radicals having 6 to 26 carbon atoms as ring atoms and monocyclic or polycyclic heteroaryl radicals having a total of 5 to 26 atoms as ring members, wherein 1, 2, 3 or 4 of these ring member atoms of the heteroaryl radical are selected from nitrogen, sulfur and oxygen, and the remaining atoms of these ring member atoms of the heteroaryl radical are carbon atoms, wherein Ar is unsubstituted or replaced by 1, 2 or 3 R selected from halogen, phenyl and C1-C4-alkyl ab Group substitution; R z For single bond, Alk 3 、O-Alk 4 -、O-Alk 4 -[O-Alk 4 -] w - or O-Alk 5 -C(O)-, where O is bound to A 3 , and among them w is an integer from 1 to 10; Alk 3 is C1-C4-alkanediyl; Alk 4 is C2-C4-alkanediyl; and Alk 5 It is C1-C4-alkanediyl.

23. The thermoplastic resin according to claim 22, wherein the structural unit of formula V is represented by one of the following formulas V-1 to V-8: wherein a and b are 0, 1, 2 or 3, in particular 0 or 1; a' and b' are 0, 1, 2 or 3, in particular 0 or 1; c and d are 0, 1, 2, 3, 4 or 5, especially 0 or 1; e and f are 0, 1, 2, 3, 4 or 5, especially 0 or 1; W' is S, S(O), SO2, O, a single bond, CH2, CH(CH3), C(CH3)2, in particular S, S(O), SO2 or C(CH3)2; And where R z , R aa , R ab , R 7a , R 7b and L are as defined in formula (V).

24. The thermoplastic resin according to any one of claims 22 or 23, wherein the molar ratio of the structural unit of formula (II) is 1 mol% to 99 mol%, preferably 30 mol% to 98 mol%, based on the total molar amount of the structural units of formula (II) and (V), and wherein the molar ratio of the structural unit of formula (V) is 1 mol% to 99 mol%, preferably 2 mol% to 70 mol%, based on the total molar amount of the structural units of formula (II) and (V).

25. The thermoplastic resin according to any one of claims 19 to 24, which has a refractive index of 1.630 or more.

26. The thermoplastic resin according to any one of claims 19 to 25, which has an Abbe number of 24 or less.

27. The thermoplastic resin according to any one of claims 19 to 26, which has a glass transition temperature (Tg) of 90°C to 185°C.

28. The thermoplastic resin according to any one of claims 19 to 27, having a weight average molecular weight of 10,000 to 50,000 relative to a polystyrene standard as measured by gel permeation chromatography.

29. The thermoplastic resin according to any one of claims 19 to 28, comprising 7% by weight or less of a low molecular weight compound having a molecular weight of less than 1000, based on the total weight of the thermoplastic resin. 30 . The thermoplastic resin according to claim 19 , comprising 1% by weight or more of a low molecular weight compound having a molecular weight of less than 1000, based on the total weight of the thermoplastic resin.

31. The thermoplastic resin according to any one of claims 19 to 30, wherein the thermoplastic resin is polycarbonate, polyester carbonate or polyester.

32. An optical device made of the thermoplastic resin according to any one of claims 19 to 31.

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