Oligomeric binaphthalene compound and thermoplastic resin

Abstract

The invention relates to the use of a compound of formula (I) or mixtures thereof, wherein the variables are as defined in the claims and the description, as monomers for producing thermoplastic resins selected from polyesters, polycarbonates and polyestercarbonates. The invention also relates to compounds (I) but excluding compounds wherein A1 and A2 are both unsubstituted 1, 4-phenylene, p and q are both 0, and X1 and X2 are both-CH2OH or-C (O) OH; and excluding the following compounds: wherein A1 and A2 are both unsubstituted 2, 3-quinolinylidene, p and q are both 0, and X1 and X2 are both-CH2OH. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to oligomeric binaphthalene compounds suitable as monomers for preparing thermoplastic resins such as polycarbonate resins, which have beneficial optical and mechanical properties and can be used for manufacturing optical devices. Background Art

[0002] Optical devices, such as optical lenses made of optical resin instead of optical glass, are advantageous in that they can be mass-produced by injection molding. Nowadays, optical resins, especially transparent polycarbonate resins, are often used in the production of camera lenses. In this regard, resins with a higher refractive index are highly desirable because they allow for a reduction in the size and weight of the final product. Generally, when using an optical material with a higher refractive index, a lens element with the same refractive power can be achieved with a surface having a smaller curvature, thereby reducing the amount of aberration generated on this surface. As a result, the number of lenses can be reduced to lower the decentration sensitivity of the lens and / or reduce the lens thickness, thus achieving weight reduction.

[0003] US 9,360,593 describes a polycarbonate resin having repeating units of a binaphthalene monomer derived from the following formula (A):

[0004]

[0005] wherein Y is a C1-C4-alkanediyl, especially 1,2-ethandiyl. It is alleged that the polycarbonate resin has 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] US2016 / 0319069 describes a copolycarbonate of a monomer of formula (A) and 10,10-bis(4-hydroxy-phenyl)anthrone monomer and its use in the preparation of optical lenses.

[0007] WO 2019 / 043060 describes a thermoplastic resin for manufacturing optical materials, wherein the thermoplastic resin comprises a polymeric compound of formula (B)

[0008]

[0009] wherein

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

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

[0012] However, as observed by the inventors of the present application, despite having various advantages, binaphthalene-derived monomers (such as the monomers of formulas A and B above) also have disadvantages, namely that when used as monomers in the manufacture of thermoplastic resins (such as the manufacture of polyesters and polycarbonates), they form a large amount of unwanted 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, lowering the glass transition temperature, and / or optical properties. Unfortunately, these cyclic components are difficult to remove from the resin in an effective manner. To reduce the formation of such cyclic compounds, it is generally necessary to polymerize the binaphthalene-containing monomer with a relatively large amount of comonomer.

[0013] Without being bound by theory, it is speculated that the reason for the increased formation of cyclic compounds when using these monomers is particularly related to their flexibility and generally short linking units (see the -Y-OH and -X-OH moieties in formulas A and B). Summary of the Invention

[0014] The present inventors have now found that these problems can be alleviated by the compounds of formula (I) below. Using the compounds of formula (I) as monomers to manufacture thermoplastic resins, especially polycarbonates, will result in a resin with a reduced content of unwanted cyclic oligomers and / or a higher molecular weight and a higher refractive index, thus having improved optical properties and / or improved mechanical properties.

[0015] Accordingly, 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 manufacturing a thermoplastic resin selected from polyesters, polycarbonates, and polyester carbonates, especially for manufacturing polycarbonates.

[0016]

[0017] wherein

[0018] X 1 and X 2 are independently selected from -CH2OH and -C(O)OR x ,

[0019] wherein R x is selected from hydrogen, phenyl, benzyl, and C1-C4-alkyl;

[0020] A 1 and A 2Independently selected from monocyclic or polycyclic arylenes having 6 to 18 carbon atoms as ring members and monocyclic or polycyclic heteroarylenes having a total of 5 to 18 atoms as ring members, wherein 1, 2, 3, or 4 of these ring member atoms of the heteroarylene are selected from nitrogen, sulfur, and oxygen, and the remaining atoms of these ring member atoms of the heteroarylene are carbon atoms, wherein the monocyclic or polycyclic arylene and the monocyclic or polycyclic heteroarylene are unsubstituted or carry 1, 2, 3, or 4 R Ar1 groups,

[0021] R 1 and R 2 are independently selected from halogen, C2-C3-alkynyl, CN, R, S(O) k R, NHR, OR, CH s R', 3-s NR2, C(O)R, and CH═CHR", provided that if p + q>1, then R 1 and R 2 can be the same or different, where s is 0, 1, or 2 each time it appears, and k is 0, 1, or 2 each time it appears;

[0022] p and q are independently 0, 1, or 2;

[0023] R is selected from C1-C4-alkyl and Q 1 groups;

[0024] Q 1 is selected from monocyclic or polycyclic aryls having 6 to 26 carbon atoms as ring members and monocyclic or polycyclic heteroaryls 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 are selected from nitrogen, sulfur, and oxygen, and the remaining atoms of these ring member atoms of the heteroaryl are carbon atoms, wherein the monocyclic or polycyclic aryl and the monocyclic or polycyclic heteroaryl are unsubstituted or carry 1, 2, 3, or 4 R''' groups;

[0025] R Ar1 is selected from R 11 S(O) k R 11 NHR 11 OR 11 CN, halogen, CH t R', 3-t NR 11 2 and CH═CHR", where, if there are more than one R Ar1 on the same heteroaryl or aryl or heteroarylene or arylene, then R Ar1 can be the same or different, where t is 0, 1, or 2 each time it appears, and k is 0, 1, or 2 each time it appears;

[0026] R 11selected from C1-C4-alkyl and Q 2 groups;

[0027] Q 2 selected from monocyclic or polycyclic aryl groups having 6 to 18 carbon atoms as ring members and monocyclic or polycyclic heteroaryl groups having a total of 5 to 18 atoms as ring members, where 1, 2, 3 or 4 of these ring member atoms of the heteroaryl group are selected from nitrogen, sulfur and oxygen, and the remaining atoms of these ring member atoms of the heteroaryl group are carbon atoms, where the monocyclic or polycyclic aryl group and the monocyclic or polycyclic heteroaryl group are unsubstituted or carry 1, 2, 3 or 4 R''' groups;

[0028] R' is selected from monocyclic or polycyclic aryl groups having 6 to 18 carbon atoms as ring members and monocyclic or polycyclic heteroaryl groups having a total of 5 to 18 atoms as ring members, where 1, 2, 3 or 4 of these ring member atoms of the heteroaryl group are selected from nitrogen, sulfur and oxygen, and the remaining atoms of these ring member atoms of the heteroaryl group are carbon atoms, where the monocyclic or polycyclic aryl group and the monocyclic or polycyclic heteroaryl group are unsubstituted or carry 1, 2, 3 or 4 R''' groups;

[0029] R” is selected from hydrogen, methyl, phenyl and naphthyl, where the phenyl and naphthyl are unsubstituted or substituted by 1, 2, 3 or 4 identical or different R'" groups;

[0030] R''' is selected from phenyl, halogen, OCH3, CH3, N(CH3)2 and C(O)CH3.

[0031] The compounds of formula (I) are new, but excluding those compounds of formula (I) in which A 1 and A 2 are both unsubstituted 1,4-phenylene, p and q are both 0, and X 1 and X 2 are both -CH2OH or C(O)OH, and further excluding those compounds of formula (I) in which A 1 and A 2 are both unsubstituted 2,3-quinolylene, p and q are both 0, and X 1 and X 2 are both -CH2OH.

[0032] These compounds are known from S.-I. Murahashi et al., Advanced Synthesis and Catalysis 346(2)(2004), 195-198 (https: / / doi.org / 10.1002 / adsc.200303190); G.S. Liou et al., J. Polym. Sci. Part A 31(13),(1993), 3265-72 (https: / / doi.org / 10.1002 / pola.1993.080311314); and P. Rajakumar et al., Bioorganic and Medicinal Chemistry Letters 19(13)(2009), 3466-3470 (https: / / doi.org / 10.1016 / j.bmcl.2009.05.019).

[0033] Accordingly, a second aspect relates to novel compounds of formula (I). In other words, the second aspect relates to compounds of formula (I), excluding the following compounds of formula (I): wherein A 1 and A 2 are both unsubstituted 1,4-phenylene, p and q are both 0, and X 1 and X 2 are both -CH2OH or -C(O)OH, and further excluding the following compounds of formula (I): wherein A 1 and A 2 are both unsubstituted 2,3-quinolylene, p and q are both 0, and X 1 and X 2 are both -CH2OH.

[0034] The use of a compound of formula (I) to prepare a thermoplastic polymer, namely a polycarbonate, polyester or polyester carbonate, will result in a thermoplastic polymer having polymerized units of the compound of formula (I), namely a thermoplastic resin comprising a structural unit represented by the following formula (II);

[0035]

[0036] wherein

[0037] # represents the point of attachment to an adjacent structural unit;

[0038] and wherein X 1a and X 2a are respectively derived from X 1 and X 2 , with the -OH or -OR of X 1 or X 2 replaced by an oxo (-O-) moietyx a group, namely X 1a and X 2a are each independently O or C(O)-O, and wherein A 1 、A 2 、R 1 、R 2 、p and q are as defined above.

[0039] Due to the beneficial properties conferred by the monomers of formula (I), the thermoplastic resins having repeating units of formula (II) described herein, especially polyesters, particularly polycarbonates, are particularly suitable for the manufacture of optical devices. Detailed Description

[0040] Due to the restricted rotation about the bonds between the naphthalene units, the compounds of formula (I) can have axial chirality, and thus the compounds of formula (I) can exist in the form of their (S)-enantiomers and (R)-enantiomers. Accordingly, the compounds of formula (I) can exist as a racemic mixture or as a non-racemic mixture, or as their pure (S)- and (R)-enantiomers, respectively. The present invention relates to racemic and non-racemic mixtures of the enantiomers of the compounds of formula (I), as well as their pure (S)- and (R)-enantiomers, insofar as these enantiomers exist.

[0041] For the purposes of the present invention, the term "C1-C4-alkanediyl" may alternatively be referred to as "C1-C4-alkylene" and refers to a divalent saturated aliphatic hydrocarbon group having 1, 2, 3 or 4 carbon atoms. Examples of C1-C4-alkanediyl are especially methylene (CH2), straight-chain alkanediyls such as 1,2-ethanediyl (CH2CH2), 1,3-propanediyl (CH2CH2CH2) and 1,4-butanediyl (CH2CH2CH2CH2), but may also be branched-chain alkanediyls such as 1-methyl-1,2-ethanediyl, 1-methyl-1,2-propanediyl, 2-methyl-1,2-propanediyl, 2-methyl-1,3-propanediyl and 1,3-butanediyl.

[0042] For the purposes of the present invention, the term "monocyclic aryl" refers to a monovalent aromatic monocyclic group, such as especially phenyl.

[0043] For the purposes of the present invention, the term "monocyclic heteroaryl" refers to a monovalent heteroaromatic monocyclic group, i.e., a heteroaromatic monocyclic ring that is connected to the remainder of the molecule by a single covalent bond, wherein the ring member atoms are part of a conjugated π - electron system, and 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 hetero - ring members, and 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.

[0044] For the purposes of the present invention, the term "monocyclic or polycyclic aryl" refers to a monovalent aromatic monocyclic group as defined herein, or to a monovalent aromatic polycyclic group, i.e., a polycyclic aromatic hydrocarbon that is connected to the remainder of the molecule by a single covalent bond, wherein the polycyclic aromatic hydrocarbon is

[0045] (i) a polycyclic aromatic hydrocarbon, i.e., a completely unsaturated polycyclic hydrocarbon, wherein each carbon atom is part of a conjugated π - electron system,

[0046] (ii) a polycyclic hydrocarbon that bears at least 1 benzene ring fused to a saturated or unsaturated 4 - to 10 - membered monocyclic or bicyclic hydrocarbon ring,

[0047] (iii) a polycyclic hydrocarbon that bears at least 2 benzene rings that are connected to each other by covalent bonds or directly fused to each other and / or fused to a saturated or unsaturated 4 - to 10 - membered monocyclic or bicyclic hydrocarbon ring.

[0048] The monocyclic or polycyclic aryl group has 6 to 26, for example 6, 9, 10, 12, 13, 14, 16, 17, 18, 19, 20, 22 or 24 carbon atoms as ring atoms, usually 6 to 22 carbon atoms, especially 6 to 18 carbon atoms, in particular 6 to 14 carbon atoms, especially 6, 10, 12, 13, 14, 16, 17 or 18 carbon atoms. The polycyclic aryl group usually has 9 to 26 carbon atoms as ring atoms, especially 10 to 18 carbon atoms, in particular 10 to 14 carbon atoms, for example 10, 12, 13, 14, 16, 17 or 18 carbon atoms as ring atoms.

[0049] In this context, polycyclic aryl groups having 2, 3 or 4 benzene rings connected to each other by single bonds include, for example, biphenylyl and terphenylyl. Polycyclic aryl groups having 2, 3 or 4 benzene rings directly fused to each other include, for example, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, triphenylenyl, chrysenyl and benzo[c]phenanthrenyl. Polycyclic aryl groups having a benzene ring fused with 2, 3 or 4 saturated or unsaturated 4- to 10-membered monocyclic or bicyclic hydrocarbon rings include, for example, 9H-fluorenyl, biphenylenyl, tetraphenylenyl, acenaphthenyl (1,2-dihydroacenaphthylenyl), acenaphthylenyl, 9,10-dihydroanthracen-1-yl, 1,2,3,4-tetrahydrophenanthrenyl, 5,6,7,8-tetrahydrophenanthrenyl, cyclopent[fg]acenaphthylenyl, phenalenyl, fluoranthenyl, benzo[k]fluoranthenyl, perylenyl, 9,10-dihydro-9,10[1',2']-benzenoanthracenyl, dibenzo[a,e][8]annulenyl, 9,9'-spirobi[9H-fluoren]yl and spiro[1H-cyclobuta[de]naphthalene-1,9'-[9H]fluoren]yl.

[0050] For example, monocyclic or polycyclic aryl groups include phenyl, naphthyl, 9H-fluorenyl, phenanthrenyl, anthracenyl, pyrenyl, a radical, a benz[c]phenanthryl group, an acenaphthylenyl group, an acenaphthenyl group, a 2,3-dihydro-1H-indenyl group, a 5,6,7,8-tetrahydronaphthalenyl group, a cyclopenta[fg]acenaphthylenyl group, a 2,3-dihydrophenalenyl group, a 9,10-dihydroanthracen-1-yl group, a 1,2,3,4-tetrahydrophenanthryl group, a 5,6,7,8-tetrahydrophenanthryl group, a fluoranthenyl group, a benzo[k]fluoranthenyl group, a biphenylenyl group, a triphenylene group, a tetraphenylene group, a 1,2-dihydroacenaphthenyl group, a dibenzo[a,e][8]annulenyl group, a perylenyl group, a biphenyl group, a terphenyl group, a naphthylenphenyl group, a phenanthrylphenyl group, an anthracenylphenyl group, a pyrenylphenyl group, a 9H-fluorenylphenyl group, a di(naphthylen)phenyl group, a naphthylenebiphenyl group, a tri(phenyl)phenyl group, a tetra(phenyl)phenyl group, a pentaphenyl(phenyl) group, a phenylnaphthyl group, a binaphthyl group, a phenanthrylnaphthyl group, a pyrenylnaphthyl group, a phenylanthracenyl group, a biphenylanthracenyl group, a naphthalenylanthracenyl group, a phenanthrylanthracenyl group, a dibenzo[a,e][8]annulenyl group, a 9,10-dihydro-9,10[1',2']benzanthracenyl group, a 9,9'-spirobi-9H-fluorenyl group, and a spiro[1H-cyclobuta[de]naphthalene-1,9'-[9H]fluorene] group.

[0051] For the purposes of the present invention, the term "monocyclic or polycyclic heteroaryl" refers to a monovalent heteroaromatic monocyclic group as defined herein, or to a monovalent heteroaromatic polycyclic group, i.e., a polycyclic hetarene attached to the remainder of the molecule by a single covalent bond, wherein

[0052] (i) the polycyclic hetarene bears a heteroaromatic monocyclic group as defined above and at least one other aromatic ring, such as 1, 2, 3, 4 or 5 aromatic rings selected from a phenyl group and heteroaromatic monocyclic groups as defined above, wherein the aromatic rings of the polycyclic hetarene are covalently linked to one another and / or directly fused to one another and / or fused to a saturated or unsaturated monocyclic or bicyclic hydrocarbon ring having 4 to 10 members, or

[0053] (ii) The polycyclic heteroarene has at least one saturated or partially or fully unsaturated 5-membered, 6-membered, 7-membered or 8-membered heterocyclic ring, which heterocyclic ring has 1, 2 or 3 heteroatoms selected from oxygen, sulfur and nitrogen as ring atoms, such as 2H-pyran, 4H-pyran, thiopyran, 1,4-dihydropyridin, 4H-1,4-oxazin, 4H-1,4-thiazin, 1,4-dioxin, oxepin, thiepin, dioxin, dithiin, dioxepin, dithiepin, dioxocine, dithiocine, and at least one, for example 1, 2, 3, 4 or 5, aromatic rings selected from phenyl and heteroaromatic monocyclics as defined above, wherein at least one aromatic ring is directly fused to the saturated or partially unsaturated 5- to 8-membered heterocyclic ring, and wherein the aromatic rings of the polycyclic heteroarene are linked to each other by covalent bonds or directly fused to each other and / or fused to a saturated or unsaturated 4- to 10-membered monocyclic or bicyclic hydrocarbon ring.

[0054] The monocyclic or polycyclic heteroaryl has 5 to 26, usually 5 to 22, especially 5 to 18, particularly 5 to 14 ring atoms, which include 1, 2, 3 or 4, especially 1 or 2 atoms selected from nitrogen atoms, sulfur atoms and oxygen atoms, and the remaining atoms among the ring atoms are carbon atoms. The polycyclic heteroaryl usually has 9 to 26, usually 9 to 20, especially 9 to 18, particularly 9 to 14 ring atoms, which include 1, 2, 3 or 4, especially 1 or 2 atoms selected from nitrogen atoms, sulfur atoms and oxygen atoms, and the remaining atoms among the ring atoms are carbon atoms.

[0055] Examples of polycyclic heteroaryls include, but are not limited to, benzofuryl, benzothienyl, dibenzofuranyl ( = dibenzo[b,d]furanyl), dibenzothienyl ( = dibenzo[b,d]thienyl), naphthofuryl, naphthothienyl, furo[3,2-b]furanyl, furo[2,3-b]furanyl, furo[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, benzopyrazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, benzo[c,d]indolyl, 1H-benzo[g]indolyl, quinolinyl, isoquinolinyl, acridinyl, phenazinyl, quinazolinyl, quinoxalinyl, phenoxazinyl, phenthiazinyl, benzo[b][1,5]naphthyridinyl, cinnolinyl, 1,5-naphthyridinyl, 1,8-naphthyridinyl, phenylpyrrolyl, naphthylpyrrolyl, dipyridyl, phenylpyridyl, naphthylpyridyl, pyrido[4,3-b]indolyl, pyrido[3,2-b]indolyl, pyrido[3,2-g]quinolinyl, pyrido[3,2-g]quinolinyl), pyrido[2,3-b][1,8]naphthyridinyl, pyrrolo[3,2-b]pyridinyl, pteridinyl, puryl, 9H-xanthenyl, 9H-thioxanthenyl, 2H-chromenyl, 2H-thiochromenyl, phenanthridinyl, phenanthrolinyl, benzo[1,2-b:4,3-b’]difuranyl, benzo[1,2-b:6,5-b’]bifuranyl, benzo[1,2-b:5,4-b’]bifuranyl, benzo[1,2-b:4,5-b’]bifuranyl, naphthofuranyl, 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]thienyl, 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']bisthienyl, benzo[1,2-b:6,5-b']bisthienyl, benzo[1,2-b:5,4-b']bisthienyl, benzo[1,2-b:4,5-b']bithienyl, 1,4-benzodithiinyl, naphtho[1,2-b][1,4]dithiinyl, naphtho[2,3-b][1,4]dithiinyl, 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]thiopyranyl, 10,11-dihydrodibenzo[b,f]thiepinyl, 6,7-dihydrodibenzo[b,d]thiepinyl, dibenzo[b,f]thiepinyl, dibenzo[b,d]thiepinyl, 6H-dibenzo[d,f][1,3]dithiepinyl, tribenzo[b,d,f]thiepinyl, benzothieno[3,4-c,d]thieno[2,3,4-j,k][2]benzothiepinyl, dinaphtho[1,8-bc:1',8'-f,g][1,5]dithiocinyl, furo[3,2-g]quinolinyl, furo[2,3-g]quinolinyl, furo[2,3-g]quinoxalinyl, benzo[g]chromenyl, thieno[3,2-f][1]benzothienyl, thieno[2,3-f][1]benzothienyl, thieno[3,2-g]quinolinyl, thieno[2,3-g]quinolinyl, thieno[2,3-g]quinoxalinyl, thieno[2,3-g]quinoxalinyl), benzo[g]thiochromenyl, pyrrolo[3,2,1-h,i]indolyl, benzo[g]quinoxalinyl, benzo[f]quinoxalinyl and benzo[h]isoquinolinyl.,

[0056] For the purposes of the present invention, the term "monocyclic arylene" refers to a divalent aromatic monocyclic group, such as especially phenylene.

[0057] For the purposes of the present invention, the term "monocyclic heteroarylene" refers to a divalent heteroaromatic monocyclic group, i.e. a heteroaromatic monocyclic ring which is connected to the two remaining parts of the molecule by two covalent single bonds, where the ring member atoms are part of a conjugated π-electron system, where 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 hetero ring members, and where 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.

[0058] For the purposes of the present invention, the term "monocyclic or polycyclic arylene" refers to a divalent aromatic monocyclic group or a divalent aromatic polycyclic group as defined herein, i.e., a polycyclic aromatic hydrocarbon that is linked to two remaining parts of the molecule by two covalent single bonds, wherein the polycyclic aromatic hydrocarbon is

[0059] (i) an aromatic polycyclic hydrocarbon, i.e., a fully unsaturated polycyclic hydrocarbon group in which each carbon atom is part of a conjugated π - electron system,

[0060] (ii) a polycyclic hydrocarbon that bears at least 1 benzene ring fused to a saturated or unsaturated 4 - to 10 - membered monocyclic or bicyclic hydrocarbon ring,

[0061] (iii) a polycyclic hydrocarbon that bears at least 2 benzene rings fused directly to one another and / or fused to a saturated or unsaturated 4 - to 10 - membered monocyclic or bicyclic hydrocarbon ring.

[0062] The monocyclic or polycyclic arylene has 6 to 18, such as 6, 9, 10, 12, 13, 14, 16, 17 or 18, carbon atoms as ring atoms, in particular 6 to 16 carbon atoms, especially 6 to 14 carbon atoms as ring atoms. The polycyclic arylene usually has 10 to 18 carbon atoms as ring atoms, in particular 10 to 16 carbon atoms, especially 10 to 14 carbon atoms, such as 10, 12, 13 or 14 carbon atoms.

[0063] In this context, polycyclic arylenes with 2 or 3 benzene rings fused directly to one another include, for example, naphthylene, anthracenylene, phenanthrenylene, pyrenylene, triphenylenylene, chrysenylene and benzo[c]phenanthrenylene. Polycyclic arylenes having 2 or 3 benzene rings fused to a saturated or unsaturated 4- to 10-membered monocyclic or bicyclic hydrocarbon ring include, for example, 9H-fluorenylene, biphenylenylene, acenaphthenylene (1,2-dihydroacenaphthylenylene), acenaphthylenylene, 9,10-dihydroanthracen-1-ylene, 1,2,3,4-tetrahydrophenanthrenylene, 5,6,7,8-tetrahydrophenanthrenylene, cyclopent[fg]acenaphthylenylene, phenalenylene, fluoranthenylene, benzo[k]fluoranthenylene, perylenylene, 9,10-dihydro-9,10[1',2']-benzenoanthracenylene, dibenzo[a,e][8]annulenylene, 9,9’-spirobi[9H-fluoren]ylene, and spiro[1H-cyclobuta[de]naphthalene-1,9'-[9H]fluoren]ylene.

[0064] For example, monocyclic or polycyclic arylenes include phenylene, naphthylene, 9H-fluorenylene, phenanthrenylene, anthrylene, pyrenylene, radical, phenanthrenylene, acenaphthylenylene, acenaphthenylene, 2,3-dihydro-1H-indenylene, 5,6,7,8-tetrahydro-naphthalenylene, cyclopenta[fg]acenaphthylenylene, 2,3-dihydrophenalenylene, 9,10-dihydroanthracen-1-yl, 1,2,3,4-tetrahydrophenanthryl, 5,6,7,8-tetrahydrophenanthryl, fluoranthenylene, biphenylylenyl, triphenylenylene, 1,2-dihydroacenaphthylenyl, dibenzo[a,e][8]annulenylene, naphthylenphenylene, phenanthrylphenylene, anthracenylphenylene, pyrenylphenylene, 9H-fluorenylphenylene, dibenzo[a,e][8]annulenylene, 9,10-dihydro-9,10[1',2']benzanthryl.

[0065] For the purposes of the present invention, the term "monocyclic or polycyclic heteroarylene" refers to a divalent heteroaromatic monocyclic group as defined herein, or to a divalent heteroaromatic polycyclic group, i.e., a polycyclic heteroarene that is attached to the two remaining parts of the molecule via two covalent single bonds, wherein

[0066] (i) the polycyclic heteroarene bears a heteroaromatic monocyclic group as defined above and at least one, for example 1, 2 or 3, other aromatic rings selected from phenyl and heteroaromatic monocyclic groups as defined above, wherein the aromatic rings of the polycyclic heteroarene are connected to each other by covalent bonds and / or are directly fused to each other and / or are fused to a saturated or unsaturated 4- to 10-membered monocyclic or bicyclic hydrocarbon ring, or

[0067] (ii) the polycyclic heteroarene bears at least one saturated or partially or fully unsaturated 5-membered, 6-membered, 7-membered or 8-membered heterocyclic ring that bears 1, 2 or 3 heteroatoms selected from oxygen, sulfur and nitrogen as ring atoms, such as 2H-pyran, 4H-pyran, thiopyran, 1,4-dihydropyridine, 4H-1,4-oxazine, 4H-1,4-thiazine, 1,4-dioxin, oxepin, thiepin, dioxin, dithiin, dioxepin, dithiepin, dioxocin, dithiocin, and at least one, for example 1, 2, 3, 4 or 5, aromatic rings selected from phenyl and heteroaromatic monocyclic groups 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 heteroarene are connected to each other by covalent bonds or are directly fused to each other and / or are fused to a saturated or unsaturated 4- to 10-membered monocyclic or bicyclic hydrocarbon ring.

[0068] The monocyclic or polycyclic heteroaryl group has 5 to 18, usually 5 to 16, especially 5 to 16 ring atoms, including 1, 2, 3 or 4, especially 1 or 2 atoms selected from nitrogen, sulfur and oxygen atoms, and the remaining atoms in the ring atoms are carbon atoms. The polycyclic heteroaryl group usually has 9 to 18, usually 9 to 16, especially 9 to 14 ring atoms, including 1, 2, 3 or 4, especially 1 or 2 atoms selected from nitrogen, sulfur and oxygen atoms, and the remaining atoms in the ring atoms are carbon atoms.

[0069] Examples of polycyclic heteroarylene include, but are not limited to, benzofurylene, benzothienylene, dibenzofuranylene (= dibenzo[b,d]furanylene), dibenzothienylene (= dibenzo[b,d]thienylene), naphthofurylene, naphthothienylene, 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 (= dibenzo[1,4]dioxinylene), thianthrenylene, indolylene (= 1H-indolylene), isoindolylene (= 2H-isoindolylene), carbazolylene, indolizinylene, benzopyrazolylene, benzimidazolylene, benzoxazolylene, benzothiazolylene, benzo[c,d]indolylene, 1H-benzo[g]indolylene, quinolinylene, isoquinolinylene, acridinylene, phenazinylene, quinazolinylene, quinoxalinylene, phenoxazinylene, phenthiazinylene, benzo[b][1,5]naphthyridinylene, cinnolinylene, 1,5-naphthyridinylene, 1,8-naphthyridinyl, phenylpyrrolylene, naphthylpyrrolylene, dipyridylene, phenylpyridylene, naphthylpyridylene, pyrido[4,3-b]indolylene, pyrido[3,2-b]indolyl, pyrido[3,2-g]quinolinylene, pyrido[2,3-b][1,8]naphthyridinylene, pyrrolo[3,2-b]pyridinylene, pteridinylene, purylene, 9H-xanthenylene, 9H-thioxanthenylene, 2H-chromenylene, 2H-thiochromenylene, phenanthridinylene, phenanthrolinylene, benzo[1,2-b:4,3-b’]difuranylene, benzo[1,2-b:6,5-b’]difuranyl, benzo[1,2-b:5,4-b’]difuranyl, benzo[1,2-b:4,5-b’]difuranyl, naphthofuranylene, benzo[b]naphtho[1,2-d]furanylene, benzo[b]naphtho[2,3-d]furanyl, benzo[b]naphtho[2,1-d]furanyl, tribenzo[b,d,f]oxepinylene, dibenzo[b,d]thienylene, naphtho[1,2-b]thienylene, naphtho[2,3-b]thienyl, naphtho[2,1-b]thienyl, benzo[b]naphtho[1,2-d]thienylene, 6H-dibenzo[b,d]thiopyranyl(6H-dibenzo[b,d]thiopyranylene), 5H,9H-[1]benzothiopyrano[5,4,3-c,d,e][2]benzothiopyranylene, 5H,10H-[1]benzothiopyrano[5,4,3-c,d,e][2]benzothiopyranyl, benzo[1,2-b:4,3-b']bisthienylene, benzo[1,2-b:6,5-b']bisthienylene, benzo[1,2-b:5,4-b']bisthienylene, benzo[1,2-b:4,5-b']bisthienylene, 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, dibenzo[a,h]thianthrenylene, 2H-naphtho[1,8-b,c]thienylene, 5H-phenanthro[4,5-b,c,d]thiopyranylene, 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, furo[3,2-g]quinolinylene, furo[2,3-g]quinolinylene, furo[2,3-g]quinoxalinylene,3-g]quinoxalinylene), benzo[g]chromenylene, thieno[3,2-f][1]benzothienylene, thieno[2,3-f][1]benzothienylene, thieno[3,2-g]quinolinylene, thieno[2,3-g]quinolinylene, thieno[2,3-g]quinoxalinylene, benzo[g]thiochromenylene, pyrrolo[3,2,1-h,i]indolylene, benzo[g]quinoxalinylene, benzo[f]quinoxalinylene and benzo[h]isoquinolinylene.,

[0070] For the purposes of the present invention, the suffix “-ylene” means that, according to the convention in the art, the corresponding heteroaromatic or aromatic moiety is in its diyl form. Thus, the suffix “-ylene” (e.g., in phenylene or 1,4-phenylene) is used synonymously herein with the suffix “-diyl” (e.g., in benzenediyl or benzene-1,4-diyl).

[0071] For the purposes of the present invention, a “structural unit” means a structural element that repeatedly occurs in the polymer backbone of a thermoplastic resin. Thus, the terms “structural unit” and “repeating unit” are used synonymously.

[0072] For the purposes of the present invention, an “optical device” means a device that is transparent to visible light and that manipulates a light beam, in particular by refraction. Optical devices include, but are not limited to, prisms, lenses, optical films and combinations thereof, in particular lenses for cameras and lenses for spectacles.

[0073] The following descriptions of preferred embodiments of the variables (substituents) of the compounds of formula (I) and the structural units of formula (II) are valid both individually and preferably in combination with each other.

[0074] The following descriptions of preferred embodiments of the variables are valid both individually and preferably in combination with each other with respect to the compounds of formula (I) and the structural units of formula (II) and, where applicable, with respect to the uses according to the invention.

[0075] In formula (I) and also in formula (II), the variable X 1 、X 2 、A 1 、A 2 、R 1 、R 2 、p and q, individually or preferably in any combination, have the following meanings:

[0076] Preferably, those variables X 1 and X 2 in formula (I) are independently selected from -CH2OH and -C(O)OR x , where R x is selected from hydrogen and C1-C4-alkyl, and correspondingly preferably those variables X 1a and X 2a in formula (II) are independently selected from -CH2O- and -C(O)O-.

[0077] In an embodiment of the preferred group (1), the variables X 1 and X 2 in formula (I) are both -CH2OH, and correspondingly the variables X 1a and X 2a in formula (II) are both -CH2O-.

[0078] In an embodiment of another group (2), the variables X 1 and X 2 in formulas (I) and (II) are independently -C(O)OR x , and correspondingly the variables X 1a and X 2a in formula (II) are both -C(O)O-, where R x is selected from the meanings defined herein for R x , especially selected from hydrogen, phenyl, benzyl and C1-C4-alkyl, preferably hydrogen and C1-C4-alkyl, more preferably hydrogen, methyl and ethyl, especially hydrogen and methyl.

[0079] In an embodiment of a specific subgroup (2'), the variables X 1 and X 2 in formula (I) have the same meaning, which is selected from the meanings defined for X 1 and X 2 in the embodiment of group (2).

[0080] In an embodiment of the preferred group (3), which is a combination of the embodiments of groups (1) and (2), the variables X 1 and X 2 in formula (I) are independently selected from -CH2OH and -C(O)OR x , where R xis hydrogen or a C1-C4-alkyl group, in particular independently selected from -CH2OH, -C(O)OH, -C(O)OCH3 and -C(O)OCH2CH3, and especially independently selected from -CH2OH, -C(O)OH and -C(O)OCH3. Accordingly, in embodiments of the preferred group (4), the variable X in formula (II) 1a and X 2a are independently selected from -CH2O- and -C(O)O-.

[0081] In embodiments of a particular subgroup (3'), the variables X in formula (I) 1 and X 2 have the same meaning, which is selected from the meanings defined herein for X 1 and X 2 and in particular the preferred meanings mentioned, especially the meanings defined in embodiments of group (3), and likewise, the variables X in formula (II) 1a and X 2a have the same meaning, which is selected from the meanings defined in embodiments of group (3).

[0082] In embodiments of the preferred group (4), the variables A in formulas (I) and (II) 1 and A 2 are independently selected from monocyclic or polycyclic arylene groups having 6 to 16, especially 6 to 14 carbon atoms as ring members and monocyclic or polycyclic heteroarylene groups having 9 to 16 atoms as ring members, where 1, 2, 3 or 4, especially 1 or 2, of these atoms are nitrogen, oxygen or sulfur atoms, especially 1 or 2 of these atoms are oxygen or sulfur atoms and the remaining atoms of these atoms are carbon atoms. In embodiments of the preferred group (4), the monocyclic or polycyclic arylene group and the monocyclic or polycyclic heteroarylene group are unsubstituted or carry 1, 2, 3 or 4, especially 1 or 2, R Ar1 groups, where R Ar1 has one of the meanings defined herein, especially one of the meanings mentioned as preferred herein.

[0083] In embodiments of the more preferred subgroup (4.1) of group (4), A 1 and A 2 are independently selected from phenylene, naphthylene, 1,2-dihydroacenaphthylene, biphenylene, 1,1'-oxydiphenylene, 1,1'-thiobiphenylene, 9H-fluorenylene, 11H-benzo[a]fluorenylene, 11H-benzo[b]fluorenylene, 7H-benzo[c]fluorenylene, anthrylene, phenanthrylene, benzo[c]phenanthrylene, pyrenylene, Base, picenylene, naphthotriarylene, furanylene, benzofuran-2-ylidene, dibenzofuran-2-ylidene, naphtho[1,2-b]furan-2-ylidene, naphtho[2,3-b]furan-2-ylidene, naphtho[2,1-b]furan-2-ylidene, benzo[b]naphtho[1,2-d]furan-2-ylidene, benzo[b]naphtho[2,3-d]furan-2-ylidene, benzo[b]naphtho[2,1-d]furan-2-ylidene, 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']difuranylene, 9H-xanthenylidene, tribenzo[b,d,f]oxepin-2-ylidene, dibenzo[1,4]dioxin-2-ylidene, 2H-naphtho[1,8-d,e][1,3]dioxin-2-ylidene, phenoxathiin-2-ylidene, dinaphtho[2,3-b:2',3'-d]furanylene, xanthenylidene, benzo[a]oxanthrenylene, benzo[b]oxanthrenylene, thienylene, benzothiophen-2-ylidene, dibenzothiophen-2-ylidene, naphtho[1,2-b]thiophen-2-ylidene, naphtho[2,3-b]thiophen-2-ylidene, naphtho[2,1-b]thiophen-2-ylidene, benzo[b]naphtho[1,2-d]thiophen-2-ylidene, benzo[b]naphtho[2,3-d]thiophen-2-ylidene, benzo[b]naphtho[2,1-d]thiophen-2-ylidene, 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']dithienylene, 9H-thioxanthenylidene, 6H-dibenzothiopyrylium-2-ylidene, 1,4-benzodithiin-2-ylidene, naphtho[1,2-b][1,4]dithiin-2-ylidene, naphtho[2,3-b][1,4]dithiin-2-ylidene, thianthren-2-ylidene, benzo[a]thianthrenylene, benzo[b]thianthrenylene, dibenzo[a,c]thianthrenylene, dibenzo[a,h]thianthrenylene, dibenzo[a,i]thianthrenylene, dibenzo[a,j]thianthrenylene, dibenzo[b,i]thianthrenylene, 2H-naphtho[1,8-b,c]thiophen-2-ylidene, dibenzo[b,d]thiepin-2-ylidene, dibenzo[b,f]thiepin-2-ylidene, 5H-phenanthro[4,5-b,c,d] Thienyl, tribenzo[b,d,f]thiepinylene, 2,5-dihydronaphtho[1,8-b,c:4,5-b',c']dithienylene, 2,6-dihydronaphtho[1,8-b,c:5,4-b',c']dithienylene, tribenzo[a,c,i]thianthrenylene, benzo[b]naphtho[1,8-e,f][1,4]dithiepinylene, dinaphtho[2,3-b:2',3'-d]thienylene, 5H-phenanthro[1,10-b,c]thienylene, 7H-phenanthro[1,10-c,b]thienylene, dibenzo[d,d']benzo[1,2-b:4,5-b']dithienylene and dibenzo[d,d']benzo[1,2-b:5,4-b']dithienylene, wherein the aforementioned monocyclic or polycyclic arylene and monocyclic or polycyclic heteroarylene are unsubstituted or carry 1 or 2 R Ar1 groups.

[0084] In an embodiment of subgroup (4.2) of the particularly preferred group (4), A 1 and A 2 are independently selected from phenylene, naphthylene, benzothienyl, benzofuryl, biphenylene, 9H-fluorenyl, xanthenyl, phenoxathiinyl, thianthrenyl, 9H-xanthenyl and 9H-thioxanthenyl, wherein the aforementioned monocyclic or polycyclic arylene and monocyclic and polycyclic heteroarylene are unsubstituted or carry 1 or 2 R Ar1 groups.

[0085] In an embodiment of subgroup (4.3) of the particularly preferred group (4), A 1 and A 2Independently selected from phenylene, naphthylene, biphenylene, benzofuran-2,1-diyl, dibenzofuran-2,1-diyl, benzothiophene-2,1-diyl, dibenzothiophene-2,1-diyl, 9H-fluorene-2,7-diyl and thianthrene-2,7-diyl, wherein phenylene, naphthylene, biphenylene, benzofuran-2,1-diyl, dibenzofuran-2,1-diyl, benzothiophene-2,1-diyl, dibenzothiophene-2,1-diyl, 9H-fluorene-2,7-diyl and thianthrene-2,7-diyl are unsubstituted or carry 1 or 2 R Ar groups.

[0086] In an embodiment of a particularly preferred subgroup (4.4) of group (4), A 1 and A 2 are independently selected from phenylene, naphthylene, biphenylene, benzofuran-2,1-diyl, dibenzofuran-2,1-diyl, benzothiophene-2,1-diyl, dibenzothiophene-2,1-diyl, 9H-fluorene-2,7-diyl and thianthrene-2,7-diyl, wherein phenylene, naphthylene, biphenylene, benzofuran-2,1-diyl, dibenzofuran-2,1-diyl, benzothiophene-2,1-diyl, dibenzothiophene-2,1-diyl, 9H-fluorene-2,7-diyl and thianthrene-2,7-diyl are unsubstituted or substituted by 1 Q 2 group.

[0087] An embodiment of a preferred subgroup (4.a) of group (4) relates to a compound of formula (I) wherein A 1 and A 2 moieties each comprise a phenylene ring which may carry one or two fused rings selected from fused benzene rings and fused 5- or 6-membered heteroaromatic rings. A 1 and A 2 moieties may be unsubstituted or carry 1 or 2 R Ar1 groups, where R Ar1 is especially a Q 2 group. Among the compounds of the embodiment of group (4.a), those are preferred in which the X 1 or X 2 group and the -O- atom are attached to the para-position of the phenylene ring of A 1 or A 2 . These compounds are also referred to as para-isomers of the embodiment of group (4.a). Among the compounds of the embodiment of group (4.a), the following compounds of formula (I) are particularly preferred: wherein A 1 and A 2 are both 1,4-phenylene or both 1,4-naphthylene or both 2,6-naphthylene, wherein 1,4-phenylene, 1,4-naphthylene and 2,6-naphthylene may be unsubstituted or carry 1 or 2 R Ar1 groups, where R Ar1 is especially a Q 2 group.

[0088] In an embodiment of a particularly preferred subgroup (4.5) of group (4), A 1 and A 2 are independently selected from 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 1,4-naphthylene, 1,2-naphthylene, 2,1-naphthylene, 2,6-naphthylene, 4,4'-biphenylene, 3,3'-biphenylene, 2,2'-biphenylene, 2,4-dibenzo[b,d]thiophene-2,6-diyl, 2,6-dibenzo[b,d]thiophene-2,6-diyl, 4,2-dibenzo[b,d]thiophene-2,6-diyl, 2,8-dibenzo[b,d]thiophene-2,6-diyl, 4,6-dibenzo[b,d]thiophene-2,6-diyl, 6,2-dibenzo[b,d]thiophene-2,6-diyl, 2,4-dibenzo[b,d]furan-2,6-diyl, 2,6-dibenzo[b,d]furan-2,6-diyl, 4,2-dibenzo[b,d]furan-2,6-diyl, 2,8-dibenzo[b,d]furan-2,6-diyl, 4,6-dibenzo[b,d]furan-2,6-diyl, 6,2-dibenzo[b,d]furan-2,6-diyl, 1,2-thianthren-1,2-diyl, 2,1-thianthren-1,2-diyl, 3,2-thianthren-1,2-diyl, 1,3-thianthren-1,2-diyl, 1,4-thianthren-1,2-diyl, 1,6-thianthren-1,2-diyl, 2,7-thianthren-1,2-diyl, 2,8-thianthren-1,2-diyl, 1,9-thianthren-1,2-diyl, 2,7-9H-fluorene-2,7-diyl, 9,2-9H-fluorene-2,7-diyl, 2,9-9H-fluorene-2,7-diyl, 2-(phenyl)-1,4-phenylene, 3-(phenyl)-1,4-phenylene, 2-(1-naphthyl)-1,4-phenylene, 3-(1-naphthyl)-1,4-phenylene, 2-(2-naphthyl)-1,4-phenylene, 3-(2-naphthyl)-1,4-phenylene, 2-(9-phenanthryl)-1,4-phenylene, 3-(9-phenanthryl)-1,4-phenylene, 2-(dibenzo[b,d]thiophen-4-yl)-1,4-phenylene, 3-(dibenzo[b,d]thiophen-4-yl)-1,4-phenylene, 2-(thianthren-1-yl)-1,4-phenylene, 3-(thianthren-1-yl)-1,4-phenylene, 2-phenyl-1,4-naphthylene, 2-(1-naphthyl)-1,4-naphthylene, 2-(2-naphthyl)-1,4-naphthylene, 2-(9-phenanthryl)-1,4-naphthylene, 2-(dibenzo[b,d])thiophen-4-yl)-1,4-naphthylene, 2-(thianthren-1-yl)-1,4-naphthylene, 8-phenyl-2,6-naphthylene, 8-(1-naphthyl)-2,6-naphthylene, 8-(2-naphthyl)-2,6-naphthylene, 8-(9-phenanthryl)-2,6-naphthylene, 8-(dibenzo[b,d]thiophen-4-yl)-2,6-naphthylene, and 8-(thianthren-1-yl)-2,6-naphthylene.

[0089] In an embodiment of the preferred group (4'), the variables A in formulas (I) and (II) 1 and A 2Independently selected from polycyclic arylenes having 10 to 16, in particular 10 to 14, carbon atoms as ring members and monocyclic or polycyclic heteroarylenes having 9 to 16 atoms as ring members, where 1, 2, 3 or 4, in particular 1 or 2, of these atoms are nitrogen, oxygen or sulfur atoms, in particular 1 or 2 of these atoms are oxygen or sulfur atoms, and the remaining atoms of these atoms are carbon atoms. In an embodiment of the preferred group (4), the polycyclic arylene and the monocyclic or polycyclic heteroarylene are unsubstituted or carry 1, 2, 3 or 4, in particular 1 or 2, R Ar1 groups, where R Ar1 has one of the meanings defined herein, in particular one of the preferred meanings mentioned herein.

[0090] In an embodiment of the more preferred subgroup (4.1') of group (4'), A 1 and A 2 are independently selected from naphthylene, 1,2-dihydroacenaphthylene, biphenylene, 1,1'-oxydiphenylene, 1,1'-thiodiphenylene, 9H-fluorenylene, 11H-benzo[a]fluorenylene, 11H-benzo[b]fluorenylene, 7H-benzo[c]fluorenylene, anthracene, phenanthrene, benzo[c]phenanthrene, pyrene, Groups, picenylene, triphenylene, furanylene, benzofuran-2-ylidene, dibenzofuran-4-ylidene, naphtho[1,2-b]furan-2-ylidene, naphtho[2,3-b]furan-2-ylidene, naphtho[2,1-b]furan-2-ylidene, benz[b]naphtho[1,2-d]furan-4-ylidene, benz[b]naphtho[2,3-d]furan-4-ylidene, benz[b]naphtho[2,1-d]furan-4-ylidene, benzo[1,2-b:4,3-b']difuranyl, benzo[1,2-b:6,5-b']difuranyl, benzo[1,2-b:5,4-b']difuranyl, benzo[1,2-b:4,5-b']difuranyl, 9H-xanthenyl, tribenzo[b,d,f]oxepin-5-ylidene, dibenzo[1,4]dioxin-6-ylidene, 2H-naphtho[1,8-d,e][1,3]dioxin-6-ylidene, phenoxathiin-4-ylidene, dinaphtho[2,3-b:2',3'-d]furan-4-ylidene, xanthen-9-ylidene, benzo[a]oxanthrenylene, benz[b]oxanthrenylene, thienylene, benzothiophen-2-ylidene, dibenzothiophene-4-ylidene, naphtho[1,2-b]thiophene-2-ylidene, naphtho[2,3-b]thiophene-2-ylidene, naphtho[2,1-b]thiophene-2-ylidene, benz[b]naphtho[1,2-d]thiophene-4-ylidene, benz[b]naphtho[2,3-d]thiophene-4-ylidene, benz[b]naphtho[2,1-d]thiophene-4-ylidene, benzo[1,2-b:4,3-b']dithienyl, benzo[1,2-b:6,5-b']dithienyl, benzo[1,2-b:5,4-b']dithienyl, benzo[1,2-b:4,5-b']dithienyl, 9H-thioxanthenyl, 6H-dibenz[b,d]thiopyranyl, 1,4-benzodithiin-6-ylidene, naphtho[1,2-b][1,4]dithiin-6-ylidene, naphtho[2,3-b][1,4]dithiin-6-ylidene, thianthren-4-ylidene, benzo[a]thianthren-4-ylidene, benz[b]thianthren-4-ylidene, dibenzo[a,c]thianthren-4-ylidene, dibenzo[a,h]thianthren-4-ylidene, dibenzo[a,i]thianthren-4-ylidene, dibenzo[a,j]thianthren-4-ylidene, dibenzo[b,i]thianthren-4-ylidene, 2H-naphtho[1,8-b,c]thiophene-2-ylidene, dibenz[b,d]thiepin-5-ylidene, dibenz[b,f]thiepin-5-ylidene, 5H-phenanthro[4,5-b,c,d]thiopyranyl, tribenzo[b,d,f]thiepin-5-ylidene, 2,5-dihydronaphtho[1,8-b,c:4,5-b',c']dithienylene, 2,6-dihydronaphtho[1,8-b,c:5,4-b',c']dithienylene), tribenzo[a,c,i]thianthrenylene, benzo[b]naphtho[1,8-e,f][1,4]dithiepinylene, dinaphtho[2,3-b:2',3'-d]thienylene, 5H-phenanthro[1,10-b,c]thienylene, 7H-phenanthro[1,10-c,b]thienylene, dibenzo[d,d']benzo[1,2-b:4,5-b']dithienylene and dibenzo[d,d']benzo[1,2-b:5,4-b']dithienylene, wherein the aforementioned monocyclic or polycyclic arylene and monocyclic or polycyclic heteroarylene are unsubstituted or carry 1 or 2 R, Ar1 groups.

[0091] In an embodiment of a particularly preferred subgroup (4.2') of group (4'), A 1 and A 2 are independently selected from naphthylene, benzo[b]thienylene, benzo[b]furanylene, biphenylene, 9H-fluorenylene, xanthenylene, phenoxathiinylene, thianthrenylene, 9H-xanthylene and 9H-thioxanthenylene, wherein the aforementioned monocyclic or polycyclic arylene and monocyclic and polycyclic heteroarylene are unsubstituted or carry 1 or 2 R Ar1 groups.

[0092] In an embodiment of a particularly preferred subgroup (4.3') of group (4'), A 1 and A 2 are independently selected from naphthylene, biphenylene, benzo[b]furanylene, dibenzo[b,d]furanylene, benzo[b]thienylene, dibenzo[b,d]thienylene, 9H-fluorenylene, thianthrenylene, wherein naphthylene, biphenylene, benzo[b]furanylene, dibenzo[b,d]furanylene, benzo[b]thienylene, dibenzo[b,d]thienylene, 9H-fluorenylene and thianthrenylene are unsubstituted or carry 1 or 2 R Ar groups.

[0093] In an embodiment of a particularly preferred subgroup (4.4') of group (4'), A 1 and A 2Independently selected from naphthylene, biphenylene, benzofuran-2-yl, dibenzofuran-2-yl, benzothiophene-2-yl, dibenzothiophene-2-yl, 9H-fluorene-2-yl, thianthren-2-yl, wherein naphthylene, biphenylene, benzofuran-2-yl, dibenzofuran-2-yl, benzothiophene-2-yl, dibenzothiophene-2-yl, 9H-fluorene-2-yl and thianthren-2-yl are unsubstituted or substituted with one Q 2 group.

[0094] An embodiment of a preferred subgroup (4.a') of group (4') relates to a compound of the following formula (I): wherein A 1 and A 2 moieties each comprise a phenylene ring which bears one or two fused rings selected from fused benzene rings and fused 5- or 6-membered heteroaromatic rings. A 1 and A 2 moieties may be unsubstituted or carry one or two R Ar1 groups, wherein R Ar1 is especially a Q 2 group. Among the compounds of the embodiment of subgroup (4.a'), preference is given to those in which the X 1 or X 2 group and the -O- atom are attached to the para-position of the phenylene ring of A 1 or A 2 . These compounds are also referred to as para-isomers of the embodiment of subgroup (4.a'). Among the compounds of the embodiment of subgroup (4.a'), particular preference is given to a compound of the following formula (I): wherein A 1 and A 2 are both 1,4-naphthylene or both 2,6-naphthylene, wherein 1,4-naphthylene and 2,6-naphthylene may be unsubstituted or carry one or two R Ar1 groups, wherein R Ar1 is especially a Q 2 group.

[0095] In an embodiment of a particularly preferred subgroup (4.5') of group (4'), A 1 and A 2Independently selected from 1,4-naphthylene, 1,2-naphthylene, 2,1-naphthylene, 2,6-naphthylene, 4,4'-biphenylene, 3,3'-biphenylene, 2,2'-biphenylene, 2,4-dibenzo[b,d]thiophene-2,6-diyl, 2,6-dibenzo[b,d]thiophene-2,6-diyl, 4,2-dibenzo[b,d]thiophene-2,6-diyl, 2,8-dibenzo[b,d]thiophene-2,6-diyl, 4,6-dibenzo[b,d]thiophene-2,6-diyl, 6,2-dibenzo[b,d]thiophene-2,6-diyl, 2,4-dibenzo[b,d]furan-2,6-diyl, 2,6-dibenzo[b,d]furan-2,6-diyl, 4,2-dibenzo[b,d]furan-2,6-diyl, 2,8-dibenzo[b,d]furan-2,6-diyl, 4,6-dibenzo[b,d]furan-2,6-diyl, 6,2-dibenzo[b,d]furan-2,6-diyl, 1,2-thianthren-2,1-diyl, 2,1-thianthren-2,1-diyl, 3,2-thianthren-2,1-diyl, 1,3-thianthren-2,1-diyl, 1,4-thianthren-2,1-diyl, 1,6-thianthren-2,1-diyl, 2,7-thianthren-2,1-diyl, 2,8-thianthren-2,1-diyl, 1,9-thianthren-2,1-diyl, 2,7-9H-fluorene-2,7-diyl, 9,2-9H-fluorene-2,7-diyl, 2,9-9H-fluorene-2,7-diyl, 2-(phenyl)-1,4-phenylene, 3-(phenyl)-1,4-phenylene, 2-(1-naphthyl)-1,4-naphthylene, 3-(1-naphthyl)-1,4-naphthylene, 2-(2-naphthyl)-1,4-naphthylene, 3-(2-naphthyl)-1,4-naphthylene, 2-(9-phenanthryl)-1,4-phenylene, 3-(9-phenanthryl)-1,4-phenylene, 2-(dibenzo[b,d]thiophen-4-yl)-1,4-phenylene, 3-(dibenzo[b,d]thiophen-4-yl)-1,4-phenylene, 2-(thianthren-1-yl)-1,4-phenylene, 3-(thianthren-1-yl)-1,4-phenylene, 2-phenyl-1,4-naphthylene, 2-(1-naphthyl)-1,4-naphthylene, 2-(2-naphthyl)-1,4-naphthylene, 2-(9-phenanthryl)-1,4-naphthylene, 2-(dibenzo[b,d]thiophen-4-yl)-1,4-naphthylene, 2-(thianthren-1-yl)-1,4-naphthylene, 8-phenyl-2,6-naphthylene, 8-(1-naphthyl)-2,6-naphthylene, 8-(2-naphthyl)-2,6-naphthylene, 8-(9-phenanthryl)-2,6-naphthylene, 8-(dibenzo[b,d]thiophen-4-yl)-2,6-naphthylene, and 8-(thianthren-1-yl)-2,6-naphthylene.

[0096] In an embodiment of a particular subgroup (4''), the variable A in formulas (I) and (II) 1 and A 2 have the same meaning and are selected from those defined herein for A 1 and A 2The meaning of the definition, in particular the preferred meanings mentioned, and in particular the meanings defined in the embodiments selected from the groups (4), (4.1), (4.2), (4.3), (4.4), (4.5), (4.a), (4’), (4.1’), (4.2’), (4.3’), (4.4’), (4.5’) and (4.a’).

[0097] In an embodiment of the preferred group (5), the variables R in formulas (I) and (II) 1 and R 2 (if present) are independently selected from halogen, C2-C3-alkynyl, CN, R, SR, OR and CH s R' 3-s , more preferably from fluorine, CN, R and OR, where s is 1 or 2, especially 2, and the variables R and R’ each have one of the meanings defined herein, in particular the preferred meanings.

[0098] In an embodiment of the particularly preferred subgroup (5.1), R 1 and R 2 (if present) are independently selected from fluorine, CN, methyl, methoxy and the Q 1 group. In particular, R 1 and R 2 (if present) are the Q 1 group.

[0099] In the context of an embodiment of subgroup (5.1) of group (5), the Q 1 group is a monocyclic or polycyclic aryl group having 6 to 14 carbon atoms as ring members and a monocyclic or polycyclic heteroaryl group having a total of 5 to 14 atoms as ring members, where 1 or 2 of these ring member atoms of the heteroaryl group are selected from nitrogen, sulfur and oxygen, and the remaining atoms of these ring member atoms of the heteroaryl group are carbon atoms. In particular, Q 1 is selected from phenyl, naphthyl (e.g. 1-naphthyl or 2-naphthyl), phenanthryl (e.g. 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl or 9-phenanthryl), thianthrenyl (e.g. 1-thianthrenyl or 2-thianthrenyl) and dibenzo[b,d]thiophenyl (e.g. dibenzo[b,d]thiophen-1-yl, dibenzo[b,d]thiophen-2-yl, dibenzo[b,d]thiophen-3-yl or dibenzo[b,d]thiophen-4-yl), and in particular from phenyl or naphthyl (e.g. 1-naphthyl or 2-naphthyl).

[0100] In a specific embodiment of group (5’), the variables R 1 and R 2 have the same meaning, which is selected from R 1 and R 2The meaning of the definitions, in particular the preferred meanings mentioned, and in particular the meanings defined in the embodiments selected from group (5) and (5.1).

[0101] Preferably, the variables p and q in formulas (I) and (II) have the same meaning, and are selected from 0, 1, and 2.

[0102] In the embodiments of the preferred group (6), the variables p and q in formulas (I) and (II) are both 0, that is, the binaphthyl moieties in formulas (I) and (II) carry neither substituent R 1 nor substituent R 2 .

[0103] In the embodiments of the preferred group (7), the variables p and q in formulas (I) and (II) are both 1, that is, the binaphthyl moieties in formulas (I) and (II) carry one substituent R 1 and one substituent R 2 . Further, in the embodiments of this group (7), the variables R 1 and R 2 preferably have the same meaning, which is selected from the meanings defined herein, in particular the preferred meanings mentioned, and preferably from the meanings defined in the embodiments of group (5), especially those defined in the embodiments of group (5.1). In the embodiments of group (7), R 1 and R 2 are especially Q 1 groups.

[0104] In the embodiments of the particularly preferred subgroup (7.1) of group (7), the two substituents R 1 and R 2 are respectively bonded to the corresponding positions of the respective naphthyl units, that is, if R 1 is, for example, bonded to position 5 of the binaphthyl moiety in formula (I) or (II), then R 2 is bonded to position 5' of this moiety. In the embodiments of group (7.1), R 1 and R 2 are especially Q 1 groups.

[0105] In the embodiments of the particularly preferred subgroup (7.2), the two substituents R 1 and R 2 are respectively bonded to positions 6 and 6' of the binaphthyl moiety in formula (I) or (II). In the embodiments of group (7.2), R 1 and R 2 are especially Q 1 groups.

[0106] In an embodiment of the preferred group (8), the variables p and q in formulas (I) and (II) are both 2, i.e., the binaphthyl moieties in formulas (I) and (II) carry two substituents R 1 and two substituents R 2 . Further, in an embodiment of this group (8), the variables R 1 and R 2 preferably have the same meaning, which is selected from the meanings defined herein, particularly those preferred meanings mentioned herein, and more preferably selected from the meanings defined in the embodiments of group (5), especially those defined in the embodiments of group (5.1). Further, in an embodiment of this group (8), the two substituents R 1 and R 2 are preferably attached at the corresponding positions of the respective naphthyl units, i.e., if the two substituents R 1 are attached, for example, at positions 3 and 6 of the binaphthyl moiety in formula (I) or (II), then the two substituents R 2 are attached at positions 3' and 6' of this moiety. In an embodiment of group (8), R 1 and R 2 are especially Q 1 groups.

[0107] Those skilled in the art will readily understand that in formulas (I) and (II), the meanings of X 1 and X 2 given in the embodiments of group (1) can be combined with the meanings of A 1 and A 1 in the embodiments according to one or more of groups (4), (4.1), (4.2), (4.3), (4.4), (4.5), (4.a), (4'), (4.1'), (4.2'), (4.3'), (4.4'), (4.5'), (4.a') and (4''), combined with the meanings of R 1 and R 2 in the embodiments according to one or more of groups (5), (5.1) and (5'), combined with the meanings of p and q in the embodiments according to group (6), one or more of groups (7), (7.1) and (7.2) or the embodiments of group (8). Those skilled in the art should also understand that in formulas (I) and (II), the meanings of X 1 and X 2 given in one of the embodiments of groups (2) and (2') can be combined with the meanings of A1 and A 1 in combination with the meanings of R in the embodiments according to one or more of groups (5), (5.1) and (5’) 1 and R 2 in combination with the meanings of p and q in the embodiments according to group (6), one or more of groups (7), (7.1) and (7.2) or the embodiment according to group (8). Those skilled in the art should also understand that in formulas (I) and (II), X given in one of the embodiments of groups (3) and (3’) 1 and X 2 can have meanings in combination with A in the embodiments according to one or more of groups (4), (4.1), (4.2), (4.3), (4.4), (4.5), (4.a), (4’), (4.1’), (4.2’), (4.3’), (4.4’), (4.5’), (4.a’) and (4’’) 1 and A 2 in combination with the meanings of R in the embodiments according to one or more of groups (5), (5.1) and (5’) 1 and R 1 in combination with the meanings of p and q in the embodiments according to group (6), one or more of groups (7), (7.1) and (7.2) or the embodiment according to group (8).

[0108] In the use according to the first aspect of the invention, and also for the compounds according to the second aspect of the invention, it is further preferred that the compound of formula (I) is not a compound of formula (I) as follows: wherein A 1 and A 2 are both unsubstituted 1,4-phenylene, and both p and q are 0.

[0109] For the first and second aspects of the invention, if A 1 and A 2 are both unsubstituted phenylene (such as 1,4-phenylene), then preferably both p and q are 1 or 2, especially 1.

[0110] For the first and second aspects of the invention, if A 1 and A 2 are both unsubstituted phenylene or phenylene substituted by 1, 2, 3 or 4 R Ar1 groups, then it is further preferred that both p and q are 1 or 2, especially 1.

[0111] In particular, for the first and second aspects of the invention, if A 1 and A 2If both are unsubstituted phenylene groups (such as 1,4-phenylene), then preferably both p and q are 1 or 2, especially 1, and R 1 and R 2 at least one of (especially R 1 and R 2 both) represents a Q group.

[0112] In particular, with respect to the first and second aspects of the present invention, if A 1 and A 2 are both unsubstituted phenylene groups or phenylene groups substituted with 1, 2, 3 or 4 R Ar1 groups, then preferably both p and q are 1 or 2, especially 1, and R 1 and R 2 at least one of (especially R 1 and R 2 both) represents a Q group.

[0113] In particular, with respect to the first and second aspects of the present invention, if A 1 and A 2 are both unsubstituted phenylene groups (such as 1,4-phenylene), then preferably both p and q are 1, and R 1 and R 2 both represent Q groups located at positions 6 and 6' of the binaphthyl moiety.

[0114] In particular, with respect to the first and second aspects of the present invention, if both p and q are 0, then preferably A 1 and A 2 are each independently selected from polycyclic arylene groups having 10 to 18 carbon atoms as ring members and monocyclic or polycyclic heteroarylene groups having a total of 5 to 18 atoms as ring members, wherein 1, 2, 3 or 4 of these ring member atoms of the heteroarylene are selected from nitrogen, sulfur and oxygen, and the remaining atoms of these ring member atoms of the heteroarylene are carbon atoms, and wherein the monocyclic or polycyclic arylene groups and monocyclic or polycyclic heteroarylene groups are unsubstituted or carry 1, 2, 3 or 4 R Ar1 groups. If both p and q are 0, then especially preferably A 1 and A 2 are each as disclosed in groups (4'), (4.1'), (4.2'), (4.3'), (4.4'), (4.5') and (4.a').

[0115] In addition and if not otherwise specified, the variables s, R Ar1 , Q 1 , Q 2 , R 11 , R, R', R” and R”' alone or preferably in combination with each other, and with the above variable X 1, X 1 , A 1 , A 2 , R 1 , R 2 The meanings and preferred meaning combinations of p and q have the following meanings.

[0116] The variable s is especially 2.

[0117] R Ar1 is preferably selected from R 11 , S(O) k R 11 , OR 11 , CH t R' 3-t , where t is 1 or 2, especially 2, and is more preferably selected from R 11 , SR 11 and OR 11 , and the variables R 11 and R' each have one of the meanings defined herein, especially the preferred meanings. In particular, R Ar1 groups are selected from methyl, methoxy, SR 11 and Q 2 groups. In particular, the R Ar1 group is the Q 2 group.

[0118] In this context, R 11 is preferably methyl or a Q 2 group.

[0119] In this context, Q 2 is preferably a monocyclic or polycyclic aryl group having 6 to 14 carbon atoms as ring members and a monocyclic or polycyclic heteroaryl group having a total of 5 to 14 atoms as ring members, wherein 1 or 2 of these ring member atoms of the heteroaryl group are selected from nitrogen, sulfur, and oxygen, and the remaining atoms of these ring member atoms of the heteroaryl group are carbon atoms. In particular, Q 2 is selected from phenyl, naphthyl (e.g., 1-naphthyl or 2-naphthyl), phenanthryl (e.g., 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, or 9-phenanthryl), thianthrenyl (e.g., 1-thianthrenyl or 2-thianthrenyl), and dibenzo[b,d]thiophenyl (e.g., dibenzo[b,d]thiophen-1-yl, dibenzo[b,d]thiophen-2-yl, dibenzo[b,d]thiophen-3-yl, or dibenzo[b,d]thiophen-4-yl), and is especially selected from phenyl or naphthyl (e.g., 1-naphthyl or 2-naphthyl).

[0120] R is preferably selected from methyl, ethyl, and a Q 1 group, where Q 1unsubstituted or substituted by one, two or three identical or different R''' groups, where each occurrence of R''' independently has one of the meanings defined herein, especially one of the preferred meanings. More preferably, R is Q as defined herein 1 group.

[0121] irrespective of whether it occurs or not, Q 1 is preferably a monocyclic or polycyclic aryl group having 6 to 14 carbon atoms as ring members and a monocyclic or polycyclic heteroaryl group having a total of 5 to 14 atoms as ring members, where 1 or 2 of these ring member atoms of the heteroaryl group are selected from nitrogen, sulfur and oxygen, and the remaining atoms of these ring member atoms of the heteroaryl group are carbon atoms. In particular, Q 1 is selected from phenyl, naphthyl (e.g., 1-naphthyl or 2-naphthyl), phenanthryl (e.g., 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl or 9-phenanthryl), thianthrenyl (e.g., 1-thianthrenyl or 2-thianthrenyl) and dibenzo[b,d]thiophenyl (e.g., dibenzo[b,d]thiophen-1-yl, dibenzo[b,d]thiophen-2-yl, dibenzo[b,d]thiophen-3-yl or dibenzo[b,d]thiophen-4-yl), and is especially selected from phenyl or naphthyl (e.g., 1-naphthyl or 2-naphthyl).

[0122] R' is preferably selected from phenyl, naphthyl, phenanthryl and triphenylene, which are unsubstituted or substituted by one, two or three identical or different R''' groups, where each occurrence of R''' independently has one of the meanings defined herein, especially one of the preferred meanings. More preferably, R' is selected from phenyl, naphthyl (e.g., 1-naphthyl or 2-naphthyl) and phenanthryl (e.g., 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl or 9-phenanthryl), which are unsubstituted.

[0123] R'' is preferably selected from hydrogen, methyl, phenyl and naphthyl, where the phenyl and naphthyl are unsubstituted or substituted by one, two or three, especially one or two identical or different R''' groups, where each occurrence of R''' independently has one of the meanings defined herein, especially one of the preferred meanings. More preferably, R'' is unsubstituted phenyl or unsubstituted naphthyl, such as 1-naphthyl or 2-naphthyl.

[0124] R''' is preferably selected from phenyl, OCH3 and CH3.

[0125] In an embodiment of a specific subgroup (6 / 7) of groups (6) and (7), the compound of formula (I) is a compound of formula (Ia). Formula (Ia) corresponds to the following formula (I): where the variables p and q are both 0 or both 1, X 1 and X 2 groups are represented by X groups having the same meaning, A 1 and A 2The group is represented by group A and has the same meaning, and R 0 is hydrogen or represents R having the same meaning 1 and R 2 groups:

[0126]

[0127] Therefore, in formula (Ia), the variable X represents the same X 1 and X 2 groups, A represents the same A 1 and A 2 groups, R 0 is H or R 1 / R 2 groups, especially H, fluorine or R groups, particularly H or Q 1 groups, and wherein X 1 、X 2 、Q 1 、A 1 and A 2 have the meanings defined herein, especially the meanings mentioned as preferred herein, namely those given in the embodiments of groups (3), (3’), (4), (4.1), (4.2), (4.3), (4.4), (4.5), (4’), (4.1’), (4.2’), (4.3’), (4.4’), (4.5’) and (5.1).

[0128] In the embodiments of this subgroup (6 / 7) of groups (6) and (7), the structural unit of formula (II) is the structural unit of formula (IIa),

[0129]

[0130] where # represents the connection point to the adjacent structural unit, wherein X a represents the same X 1a and X 2a groups, wherein A represents the same A 1 and A 2 groups, wherein R 0 is H, fluorine or an R group, especially H or Q 1 groups, and wherein the variable X 1a 、X 2a 、Q 1 、A 1 and A 2Has the meaning defined herein, in particular as preferably mentioned, namely those meanings given in the embodiments of groups (3), (3’), (4), (4.1), (4.2), (4.3), (4.4), (4.5), (4’), (4.1’), (4.2’), (4.3’), (4.4’), (4.5’) and (5.1).

[0131] Preferably, the X moiety in formula (Ia) and the X a moiety in formula (IIa) are defined as in the embodiments of group (1), the embodiments of group (2) or the embodiments of group (3). Thus, the X moiety in formula (Ia) herein is particularly selected from -CH2OH (i.e., hydroxymethyl) and -C(O)OR x , where R x is hydrogen or C1-C4-alkyl, particularly selected from -CH2OH, -C(O)OH, -C(O)OCH3 and -C(O)OCH2CH3, and specifically selected from -CH2OH, -C(O)OH and -C(O)OCH3. Thus, the X a moiety in formula (IIa) is selected from -CH2O- and -C(O)O-.

[0132] Also preferred are the compounds of formula (Ia) and the structural units of formula (IIa) below: wherein the A moiety is defined as in one of the embodiments of groups (4), (4.1), (4.2), (4.3) and (4.4), and wherein R 0 is hydrogen or has one of the meanings given for R 1 and R 2 respectively, and wherein R 0 is particularly hydrogen or has one of the meanings given in the embodiments of group (5.1). More preferably, the A moiety in formula (Ia) and formula (IIa) is defined as in the embodiments of group (4.5). In particular, the A moiety in formula (Ia) and formula (IIa) is defined as in the embodiments of group (4.5), and R 0 is particularly hydrogen or has one of the meanings given in the embodiments of group (5.1).

[0133] Thus, the A moiety in formula (Ia) and (IIa) herein is particularly selected from A 1 and A 2, which is independently selected from 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 1,4-naphthylene, 1,2-naphthylene, 2,1-naphthylene, 2,6-naphthylene, 4,4'-biphenylene, 3,3'-biphenylene, 2,2'-biphenylene, 2,4-dibenzo[b,d]thiophene-2,6-diyl, 2,6-dibenzo[b,d]thiophene-2,6-diyl, 4,2-dibenzo[b,d]thiophene-2,6-diyl, 2,8-dibenzo[b,d]thiophene-2,6-diyl, 4,6-dibenzo[b,d]thiophene-2,6-diyl, 6,2-dibenzo[b,d]thiophene-2,6-diyl, 2,4-dibenzo[b,d]furan-2,6-diyl, 2,6-dibenzo[b,d]furan-2,6-diyl, 4,2-dibenzo[b,d]furan-2,6-diyl, 2,8-dibenzo[b,d]furan-2,6-diyl, 4,6-dibenzo[b,d]furan-2,6-diyl, 6,2-dibenzo[b,d]furan-2,6-diyl, 1,2-thianthren-2,1-diyl, 2,1-thianthren-2,1-diyl, 3,2-thianthren-2,1-diyl, 1,3-thianthren-2,1-diyl, 1,4-thianthren-2,1-diyl, 1,6-thianthren-2,1-diyl, 2,7-thianthren-2,1-diyl, 2,8-thianthren-2,1-diyl, 1,9-thianthren-2,1-diyl, 2,7-9H-fluorene-2,7-diyl, 9,2-9H-fluorene-2,7-diyl, 2,9-9H-fluorene-2,7-diyl, 2-(phenyl)-1,4-phenylene, 3-(phenyl)-1,4-phenylene, 2-(1-naphthyl)-1,4-phenylene, 3-(1-naphthyl)-1,4-phenylene, 2-(2-naphthyl)-1,4-phenylene, 3-(2-naphthyl)-1,4-phenylene, 2-(9-phenanthryl)-1,4-phenylene, 3-(9-phenanthryl)-1,4-phenylene, 2-(dibenzo[b,d]thiophen-4-yl)-1,4-phenylene, 3-(dibenzo[b,d]thiophen-4-yl)-1,4-phenylene, 2-(thianthren-1-yl)-1,4-phenylene, 3-(thianthren-1-yl)-1,4-phenylene, 2-phenyl-1,4-naphthylene, 2-(1-naphthyl)-1,4-naphthylene, 2-(2-naphthyl)-1,4-naphthylene, 2-(9-phenanthryl)-1,4-naphthylene, 2-(dibenzo[b,d])thiophen-4-yl)-1,4-naphthylene, 2-(thianthren-1-yl)-1,4-naphthylene, 8-phenyl-2,6-naphthylene, 8-(1-naphthyl)-2,6-naphthylene, 8-(2-naphthyl)-2,6-naphthylene, 8-(9-phenanthryl)-2,6-naphthylene, 8-(dibenzo[b,d]thiophen-4-yl)-2,6-naphthylene and 8-(thianthren-1-yl)-2,6-naphthylene, and R 0 group is especially hydrogen or Q 1 , wherein Q 1is a monocyclic or polycyclic aryl group having 6 to 14 carbon atoms as ring members and a monocyclic or polycyclic heteroaryl group having a total of 5 to 14 atoms as ring members, wherein 1 or 2 of these ring member atoms of the heteroaryl group are selected from nitrogen, sulfur, and oxygen, and the remaining atoms of these ring member atoms of the heteroaryl group are carbon atoms, and wherein Q 1 is more preferably selected from phenyl, naphthyl (e.g., 1-naphthyl or 2-naphthyl), phenanthryl (e.g., 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, or 9-phenanthryl), thianthrenyl (e.g., 1-thianthrenyl or 2-thianthrenyl), and dibenzo[b,d]thiophenyl (e.g., dibenzo[b,d]thiophen-1-yl, dibenzo[b,d]thiophen-2-yl, dibenzo[b,d]thiophen-3-yl, or dibenzo[b,d]thiophen-4-yl), and particularly selected from phenyl or naphthyl (e.g., 1-naphthyl or 2-naphthyl).

[0134] Examples of a specific subgroup (6 / 7) are compounds of formula (Ia) and structural units of formula (IIa) below: wherein the X moiety or the X a moiety is combined with the A moiety as defined in any one of rows 1 to 243 in Table A below, wherein X a in each case is derived from X in formula (Ia) by replacing the -OH or -OR x group of X with an oxo (-O-) unit.

[0135] Table A:

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146] *) The linking position "n,m-" included in the name of part A should be understood as follows: the first one, namely n, represents the position of the carbon atom connected to X, and the second one, namely m, represents the position of the carbon atom connected to the O atom.

[0147] Among the compounds of formula (Ia) listed in Table A, the following compounds are particularly preferred:

[0148] {[1,1'-Binaphthalene]-2,2'-diylbis(oxy(oxy)-4,1-phenylene)}dimethanol

[0149] {[1,1'-Binaphthalene]-2,2'-diylbis(oxy-3,1-phenylene)}dimethanol

[0150] {[1,1'-Binaphthalene]-2,2'-diylbis(oxy-2,1-phenylene)}dimethanol

[0151] {[1,1'-Binaphthalene]-2,2'-diylbis(oxy naphthalene-4,1-diyl)]}dimethanol

[0152] {[1,1'-Binaphthalene]-2,2'-diylbis(oxy naphthalene-6,2-diyl)]}dimethanol

[0153] {[1,1'-Binaphthalene]-2,2'-diylbis(oxy naphthalene-1,2-diyl)]}dimethanol

[0154] {[1,1'-Binaphthalene]-2,2'-diylbis(oxy[1,1'-biphenyl]-4',4-diyl)}dimethanol

[0155] {[1,1'-Binaphthalene]-2,2'-diylbis(oxy[1,1'-biphenyl]-3',3-diyl)}dimethanol

[0156] {[1,1'-Binaphthalene]-2,2'-diylbis(oxy[1,1'-biphenyl]-2',2-diyl)]}dimethanol

[0157] {[1,1'-Binaphthalene]-2,2'-diylbis(oxy-9H-fluorenyl-7,2-diyl)}dimethanol

[0158] {[1,1'-Binaphthalene]-2,2'-diylbis(oxy-9H-fluorenyl-2,9-diyl)}dimethanol

[0159] {[1,1'-Binaphthalene]-2,2'-diylbis(oxy-9H-fluorenyl-9,2-diyl)}dimethanol

[0160] {[1,1'-Binaphthalene]-2,2'-diylbis(oxydibenzo[b,d]thiophene(oxydibenzo[b,d]thiene)-6,4-diyl)}dimethanol

[0161] {[1,1'-Binaphthalene]-2,2'-diylbis(oxydibenzo[b,d]thiophene-6,2-diyl)}dimethanol

[0162] {[1,1'-Binaphthalene]-2,2'-diylbis(oxydibenzo[b,d]thiophene-4,2-diyl)}dimethanol

[0163] {[1,1'-Binaphthalene]-2,2'-diylbis(oxydibenzo[b,d]thiophene-8,2-diyl)}dimethanol

[0164] {[1,1'-Binaphthalene]-2,2'-diylbis(oxydibenzo[b,d]thiophene-2,6-diyl)}dimethanol

[0165] {[1,1'-Binaphthalene]-2,2'-diylbis(oxydibenzo[b,d]thiophene-2,4-diyl)}dimethanol

[0166] {[1,1'-Binaphthalene]-2,2'-diylbis(oxydibenzofuran-6,4-diyl)}dimethanol

[0167] {[1,1'-Binaphthalene]-2,2'-diylbis(oxydibenzofuran-6,2-diyl)}dimethanol

[0168] {[1,1'-Binaphthalene]-2,2'-diylbis(oxydibenzofuran-4,2-diyl)}dimethanol

[0169] {[1,1'-Binaphthalene]-2,2'-diylbis(oxydibenzofuran-8,2-diyl)}dimethanol

[0170] {[1,1'-Binaphthalene]-2,2'-diylbis(oxydibenzofuran-2,6-diyl)}dimethanol

[0171] {[1,1'-Binaphthalene]-2,2'-diylbis(oxydibenzofuran-2,4-diyl)}dimethanol

[0172] {[1,1'-Binaphthalene]-2,2'-diylbis(oxythianthrene-9,1-diyl)}dimethanol

[0173] {[1,1'-Binaphthalene]-2,2'-diylbis(oxythianthrene-6,1-diyl)}dimethanol

[0174] {[1,1'-Binaphthalene]-2,2'-diylbis(oxythianthrene-1,2-diyl)]}dimethanol

[0175] {[1,1'-Binaphthalene]-2,2'-diylbis(oxythianthrene-1,3-diyl)]}dimethanol

[0176] {[1,1'-Binaphthalene]-2,2'-diylbis(oxythianthrene-7,2-diyl)]}dimethanol

[0177] {[1,1'-Binaphthalene]-2,2'-diylbis(oxythianthrene-8,2-diyl)]}dimethanol

[0178] {[1,1'-Binaphthalene]-2,2'-diylbis(oxythianthrene-2,1-diyl)]}dimethanol

[0179] {[1,1'-Binaphthalene]-2,2'-diylbis(oxythianthrene-3,2-diyl)]}dimethanol

[0180] 4,4'-{[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]}dibenzoic acid

[0181] 3,3'-{[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]}dibenzoic acid

[0182] 2,2'-{[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]}dibenzoic acid

[0183] 4,4'-[[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]di(naphthalene-1-carboxylic acid)

[0184] 6,6'-[[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]di(naphthalene-2-carboxylic acid)

[0185] 1,1'-[[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]di(naphthalene-2-carboxylic acid)

[0186] 7,7'-[[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]di(9H-fluoren-2-carboxylic acid)

[0187] 2,2'-[[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]di(9H-fluoren-9-carboxylic acid)

[0188] 9,9'-[[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]di(9H-fluoren-2-carboxylic acid)

[0189] 6,6'-[[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]}bis(dibenzo[b,d]thiophene-4-carboxylic acid)

[0190] 6,6'-[[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]}bis(dibenzo[b,d]thiophene-2-carboxylic acid)

[0191] 4,4'-[[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]}bis(dibenzo[b,d]thiophene-2-carboxylic acid)

[0192] 8,8'-{[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]}bis(dibenzo[b,d]thiophene-2-carboxylic acid)

[0193] 8,8'-[[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]}bis(dibenzo[b,d]thiophene-4-carboxylic acid)

[0194] 2,2'-[[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]}bis(dibenzo[b,d]thiophene-4-carboxylic acid)

[0195] 6,6'-[[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]}bis(dibenzo[b,d]furan-4-carboxylic acid)

[0196] 9,9'-[[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]}bis(thianthrene-1-carboxylic acid)

[0197] Dimethyl 4,4'-{[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]}dibenzoate

[0198] Dimethyl 2,2'-{[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]}dibenzoate

[0199] Dimethyl 4,4'-{[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]}bis(naphthalene-1-carboxylate)

[0200] Dimethyl 6,6'-{[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]}bis(naphthalene-2-carboxylate)

[0201] {(6,6'-Diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis(oxy-4,1-phenylene)]}dimethanol

[0202] {(6,6'-Diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis(oxy-2,1-phenylene)]}dimethanol

[0203] [(6,6'-Diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis(oxynaphthalene-4,1-diyl)]dimethanol

[0204] 4,4'-[(6,6'-Diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]dibenzoic acid

[0205] 2,2'-[(6,6'-Diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]dibenzoic acid

[0206] 4,4'-[(6,6'-Diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]bis(1-naphthoic acid)

[0207] Dimethyl 4,4'-[(6,6'-diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]dibenzoate

[0208] Dimethyl 2,2'-[(6,6'-diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]dibenzoate

[0209] Dimethyl 4,4'-[(6,6'-diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]bis(1-naphthoate)

[0210] {(6,6'-Bis(1-naphthyl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy-4,1-phenylene)}dimethanol

[0211] {(6,6'-Bis(1-naphthyl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy-2,1-phenylene)}dimethanol

[0212] [(6,6'-Bis(1-naphthyl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxynaphthalene-4,1-diyl)]dimethanol

[0213] 4,4'-{(6,6'-Bis(1-naphthyl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)}dibenzoic acid

[0214] 4,4'-[(6,6'-Bis(1-naphthyl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]bis(1-naphthoic acid)

[0215] Dimethyl 4,4'-{(6,6'-bis(1-naphthyl)-[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)}dibenzoate

[0216] Dimethyl 4,4'-[(bis(naphthalen-1-yl)-[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]bis(naphthalene-1-carboxylate)

[0217] {(6,6'-Bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy-4,1-phenylene)}dimethanol

[0218] [(Bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxynaphthalene-4,1-diyl)]dimethanol

[0219] 4,4'-{(6,6'-Bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)}dibenzoic acid

[0220] 4,4'-[(Bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]bis(naphthalene-1-carboxylic acid)

[0221] Dimethyl 4,4'-{(6,6'-bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)}dibenzoate

[0222] Dimethyl 4,4'-[(bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]bis(naphthalene-1-carboxylate)

[0223] {[6,6'-Di(phenanthren-9-yl)[1,1'-binaphthalene]-2,2'-diyl]bis(oxy-4,1-phenylene)}dimethanol

[0224] [(6,6'-Di(phenanthren-9-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxynaphthalene-4,1-diyl)]dimethanol

[0225] 4,4'-{[6,6'-Di(phenanthren-9-yl)[1,1'-binaphthalene]-2,2'-diyl]bis(oxy)}dibenzoic acid

[0226] 4,4'-[(6,6'-Di(phenanthren-9-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]bis(naphthalene-1-carboxylic acid)

[0227] Dimethyl 4,4'-{[6,6'-di(phenanthren-9-yl)[1,1'-binaphthalene]-2,2'-diyl]bis(oxy)}dibenzoate

[0228] Dimethyl 4,4'-[(di(phenanthren-9-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]bis(naphthalene-1-carboxylate)

[0229] {[6,6'-Bis(dibenzo[b,d]thiophen-4-yl)[1,1'-binaphthalene]-2,2'-diyl]bis(oxy-4,1-phenylene)}dimethanol

[0230] {[6,6'-Bis(dibenzo[b,d]thiophen-4-yl)[1,1'-binaphthalene]-2,2'-diyl]bis(oxynaphthalene-4,1-diyl)}dimethanol

[0231] 2,2'-{[6,6'-Bis(dibenzo[b,d]thiophen-4-yl)[1,1'-binaphthalene]-2,2'-diyl]bis(oxy)}dibenzoic acid

[0232] 4,4'-{[6,6'-Bis(dibenzo[b,d]thiophen-4-yl)[1,1'-binaphthalene]-2,2'-diyl]bis(oxy)}bis(naphthalene-1-carboxylic acid)

[0233] Dimethyl 4,4'-{[6,6'-Bis(dibenzo[b,d]thiophen-4-yl)[1,1'-binaphthalene]-2,2'-diyl]bis(oxy)}dibenzoate

[0234] Dimethyl 4,4'-{[6,6'-Bis(dibenzo[b,d]thiophen-4-yl)[1,1'-binaphthalene]-2,2'-diyl]bis(oxy)}bis(naphthalene-1-carboxylate)

[0235] {[6,6'-Di(thianthren-1-yl)[1,1'-binaphthalene]-2,2'-diyl]bis(oxy-4,1-phenylene)}dimethanol

[0236] {[6,6'-Di(thianthren-1-yl)[1,1'-binaphthalene]-2,2'-diyl]bis(oxynaphthalene-4,1-diyl)}dimethanol

[0237] 4,4-{[6,6'-Di(thianthren-1-yl)[1,1'-binaphthalene]-2,2'-diyl]bis(oxy)}dibenzoic acid

[0238] 4,4'-{[6,6'-Di(thianthren-1-yl)[1,1'-binaphthalene]-2,2'-diyl]bis(oxy)}bis(naphthalene-1-carboxylic acid)

[0239] Dimethyl 4,4'-{[6,6'-Di(thianthren-1-yl)[1,1'-binaphthalene]-2,2'-diyl]bis(oxy)}dibenzoate

[0240] Dimethyl 4,4'-{[6,6'-Di(thianthren-1-yl)[1,1'-binaphthalene]-2,2'-diyl]bis(oxy)}bis(naphthalene-1-carboxylate).

[0241] In an embodiment of a specific subgroup (6 / 7-1) of the group (6 / 7), the compound of formula (I) is a compound of formula (Ia.1). Formula (Ia.1) corresponds to the following formula (I): where the variables p and q are both 0 or both 1, X 1 and X 2 groups are represented by X groups having the same meaning, A 1 and A 2 groups are represented by an optionally substituted 1,4-phenylene, and Q 0 group is hydrogen or a Q 2 group, and R 0 group is hydrogen or represents R 1 and R 2 groups having the same meaning:

[0242]

[0243] Thus, in formula (Ia.1), the variable X represents the same X 1 and X 2 groups, and R 0 is H or an R 1 / R 2 group, H, especially fluorine or an R group, particularly H or a Q 1 group, and wherein Q 0 is hydrogen or a Q 2 group, and wherein X 1 , X 2 , Q 1 , Q 2 have the meanings defined herein, especially the preferred meanings mentioned herein.

[0244] In an embodiment of another specific subgroup (6 / 7-2) of the group (6 / 7), the compound of formula (I) is a compound of formula (Ia.2). Formula (Ia.2) corresponds to the following formula (I): where the variables p and q are both 0 or both 1, X 1 and X 2 groups are represented by X groups having the same meaning, A 1 and A 2 groups are represented by an optionally substituted 1,4-phenylene, and Q 0 group is hydrogen or a Q 2 group, and R 0 group is hydrogen or represents R 1 and R 2 groups:

[0245]

[0246] Thus, in formula (Ia.2), the variable X represents the same X 1 and X2 group, and R 0 is H or R 1 / R 2 group, H, especially fluorine or R group, particularly H or Q 1 group, and wherein Q 0 is hydrogen or Q 2 group, and wherein X 1 、X 2 、Q 1 、Q 2 have the meanings defined herein, especially the preferred meanings mentioned herein.

[0247] In an embodiment of a further specific subgroup (6 / 7-3) of group (6 / 7), the compound of formula (I) is a compound of formula (Ia.3). Formula (Ia.3) corresponds to the following formula (I): wherein the variables p and q are both 0 or both 1, X 1 and X 2 groups are represented by X groups having the same meaning, A 1 and A 2 groups are represented by optionally substituted 2,6-naphthylene, and Q 0 group is hydrogen or Q 2 group, and R 0 group is hydrogen or represents R 1 or R 2 group:

[0248]

[0249] Thus, in formula (Ia.3), the variable X represents the same X 1 and X 2 groups, and R 0 is H or R 1 / R 2 group, H, especially fluorine or R group, particularly H or Q 1 group, and wherein Q 0 is hydrogen or Q 2 group, and wherein X 1 、X 2 、Q 1 、Q 2 have the meanings defined herein, especially the preferred meanings mentioned herein.

[0250] In an embodiment of a specific subgroup (6 / 7-4) of group (6 / 7), the compound of formula (I) is a compound of formula (Ia.4). Formula (Ia.4) corresponds to the following formula (I): wherein the variables p and q are both 0 or both 1, X 1 and X 2The group is represented by the X group having the same meaning, A 1 and A 2 The group is represented by an optionally substituted 1,4-naphthylene group, and Q 0 The group is hydrogen or the Q 2 group, and R 0 The group is hydrogen or represents R having the same meaning 1 and R 2 group:

[0251]

[0252] Therefore, in formula (Ia.4), the variable X represents the same X 1 and X 2 group, and R 0 is H or R 1 / R 2 group, H, especially fluorine or R group, particularly H or Q 1 group, and wherein Q 0 is hydrogen or the Q 2 group, and wherein X 1 、X 2 、Q 1 、Q 2 has the meaning defined herein, especially the preferred meanings mentioned herein.

[0253] Preferably, the X moiety in formulas (Ia.1), (Ia.2), (Ia.3) and (Ia.4) is defined as in the embodiments of group (1), the embodiments of group (2) or the embodiments of group (3). Therefore, the X moiety in formula (Ia) herein is especially selected from -CH2OH (i.e., hydroxymethyl) and -C(O)OR x wherein R x is hydrogen or C1-C4-alkyl, especially selected from -CH2OH, -C(O)OH, -C(O)OCH3 and -C(O)OCH2CH3, and particularly selected from -CH2OH, -C(O)OH and -C(O)OCH3. Therefore, the X a moiety in formula (IIa) herein is selected from -CH2O- and -C(O)O-.

[0254] Also preferred are the compounds of formulas (Ia.1), (Ia.2), (Ia.3) and (Ia.4) and the structural unit of formula (IIb) below: wherein the R 0 group is defined as in one or more of the embodiments of groups (5), (5.1) and (5'). More preferably, the R 0The group is as defined in the embodiment of group (5.1). Thus, R in formula (Ib) and (IIb) here 0 The group is especially selected from fluorine, CN, methyl, methoxy and Q 1 group.

[0255] In the context of formulae (Ia.1), (Ia.2), (Ia.3) and (Ia.4), R 0 is especially hydrogen or Q 1 , where Q 1 is preferably a monocyclic or polycyclic aryl group having 6 to 14 carbon atoms as ring members and a monocyclic or polycyclic heteroaryl group having a total of 5 to 14 atoms as ring members, where 1 or 2 of these ring member atoms of the heteroaryl group are selected from nitrogen, sulfur and oxygen, and the remaining atoms of these ring member atoms of the heteroaryl group are carbon atoms. In particular, Q 1 is selected from phenyl, naphthyl (such as 1-naphthyl or 2-naphthyl), phenanthryl (such as 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl or 9-phenanthryl), thianthrenyl (such as 1-thianthrenyl or 2-thianthrenyl) and dibenzo[b,d]thiophenyl (such as dibenzo[b,d]thiophen-1-yl, dibenzo[b,d]thiophen-2-yl, dibenzo[b,d]thiophen-3-yl or dibenzo[b,d]thiophen-4-yl), and especially selected from phenyl or naphthyl (such as 1-naphthyl or 2-naphthyl).

[0256] In the context of formulae (Ia.1), (Ia.2), (Ia.3) and (Ia.4), Q 0 is especially hydrogen or Q 2 , where Q 2 is preferably a monocyclic or polycyclic aryl group having 6 to 14 carbon atoms as ring members and a monocyclic or polycyclic heteroaryl group having a total of 5 to 14 atoms as ring members, where 1 or 2 of these ring member atoms of the heteroaryl group are selected from nitrogen, sulfur and oxygen, and the remaining atoms of these ring member atoms of the heteroaryl group are carbon atoms. In particular, Q 2 is selected from phenyl, naphthyl (such as 1-naphthyl or 2-naphthyl), phenanthryl (such as 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl or 9-phenanthryl), thianthrenyl (such as 1-thianthrenyl or 2-thianthrenyl) and dibenzo[b,d]thiophenyl (such as dibenzo[b,d]thiophen-1-yl, dibenzo[b,d]thiophen-2-yl, dibenzo[b,d]thiophen-3-yl or dibenzo[b,d]thiophen-4-yl), and especially selected from phenyl or naphthyl (such as 1-naphthyl or 2-naphthyl).

[0257] Examples of the specific subgroups (6 / 7-1), (6 / 7-2), (6 / 7-3), and (6 / 7-4) are the compounds of the following formulas (Ia.1), (Ia.2), (Ia.3), and (Ia.4): wherein the X moiety, R 0 group, and Qgroup are defined as in any one of rows 1 to 504 in Table B below: 0

[0258] Table B:

[0259]

[0260]

[0261]

[0262]

[0263]

[0264]

[0265]

[0266]

[0267]

[0268]

[0269]

[0270]

[0271]

[0272]

[0273]

[0274]

[0275]

[0276]

[0277] Among the compounds of formulas (Ia.1), (Ia.2), (Ia.3), and (Ia.4) listed in Table B, the following compounds are particularly preferred:

[0278] [[1,1'-Binaphthalene]-2,2'-diylbis(oxy[1,1'-biphenyl]-2,5-diyl)]dimethanol

[0279] 6,6'-[[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]bis([1,1'-biphenyl]-3-carboxylic acid)

[0280] Dimethyl 6,6'-[[1,1'-binaphthalene]-2,2'-diylbis(oxy)]bis([1,1'-biphenyl]-3-carboxylate)

[0281] ([1,1'-Binaphthalene]-2,2'-diylbis{oxy[3-(naphthalen-1-yl)-4,1-phenylene]})dimethanol

[0282] 4,4'-[[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]bis[3-(naphthalen-1-yl)benzoic acid]

[0283] Dimethyl 4,4'-[[1,1'-binaphthalene]-2,2'-diylbis(oxy)]bis[3-(naphthalen-1-yl)benzoate]

[0284] ([1,1'-Binaphthalene]-2,2'-diylbis{oxy[3-(naphthalen-2-yl)-4,1-phenylene]})dimethanol

[0285] 4,4'-[[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]bis[3-(naphthalen-2-yl)benzoic acid]

[0286] Dimethyl 4,4'-[[1,1'-binaphthalene]-2,2'-diylbis(oxy)]bis[3-(naphthalen-2-yl)benzoate]

[0287] ([1,1'-Binaphthalene]-2,2'-diylbis{oxy[3-(phenanthren-9-yl)-4,1-phenylene]})dimethanol

[0288] 4,4'-[[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]bis[3-(phenanthren-9-yl)benzoic acid]

[0289] ([1,1'-Binaphthalene]-2,2'-diylbis{oxy[3-(dibenzo[b,d]thiophen-4-yl)-4,1-phenylene]})dimethanol

[0290] 4,4'-[[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]bis[3-(dibenzo[b,d]thiophen-4-yl)benzoic acid]

[0291] ([1,1'-Binaphthalene]-2,2'-diylbis{oxy[3-(thianthren-1-yl)-4,1-phenylene]})dimethanol

[0292] 4,4'-[[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]bis[3-(thianthren-1-yl)benzoic acid]

[0293] [[1,1'-Binaphthalene]-2,2'-diylbis(oxy[1,1'-biphenyl]-2,5-diyl)]dimethanol

[0294] 6,6'-[[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]bis([1,1'-biphenyl]-3-carboxylic acid)

[0295] Dimethyl 6,6'-[[1,1'-binaphthalene]-2,2'-diylbis(oxy)]bis([1,1'-biphenyl]-3-carboxylate)

[0296] ([1,1'-Binaphthalene]-2,2'-diylbis{oxy[3-(naphthalen-1-yl)-4,1-phenylene]})dimethanol

[0297] 4,4'-[[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]bis[3-(naphthalen-1-yl)benzoic acid]

[0298] ([1,1'-Binaphthalene]-2,2'-diylbis{oxy[3-(naphthalen-2-yl)-4,1-phenylene]})dimethanol

[0299] 4,4'-[[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]bis[3-(naphthalen-2-yl)benzoic acid]

[0300] ([1,1'-Binaphthalene]-2,2'-diylbis{oxy[3-(phenanthren-9-yl)-4,1-phenylene]})dimethanol

[0301] ([1,1'-Binaphthalene]-2,2'-diylbis{oxy[3-(dibenzo[b,d]thiophen-4-yl)-4,1-phenylene]})dimethanol

[0302] 4,4'-[[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]bis[3-(dibenzo[b,d]thiophen-4-yl)benzoic acid]

[0303] ([1,1'-Binaphthalene]-2,2'-diylbis{oxy[3-(thianthren-1-yl)-4,1-phenylene]})dimethanol

[0304] 4,4'-[[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]bis[3-(thianthren-1-yl)benzoic acid]

[0305] {[1,1'-Binaphthalene]-2,2'-diylbis[oxy(4-phenylnaphthalene-6,2-diyl)]}dimethanol

[0306] 6,6'-[[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]bis(4-phenylnaphthalene-2-carboxylic acid)

[0307] [[1,1'-Binaphthalene]-2,2'-diylbis(oxy[1,1'-binaphthalene]-7,3-diyl)]dimethanol

[0308] 7,7'-[[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]bis([1,1'-binaphthalene]-3-carboxylic acid)

[0309] [[1,1'-Binaphthalene]-2,2'-diylbis(oxy[1,2'-binaphthalene]-7,3-diyl)]dimethanol

[0310] ([1,1'-Binaphthalene]-2,2'-diylbis{oxy[4-(dibenzo[b,d]thiophen-4-yl)naphthalene-6,2-diyl]})dimethanol

[0311] ([1,1'-Binaphthalene]-2,2'-diylbis{oxy[4-(thianthren-1-yl)naphthalene-6,2-diyl]})dimethanol

[0312] {[1,1'-Binaphthalene]-2,2'-diylbis[oxy(3-phenylnaphthalene-4,1-diyl)]}dimethanol

[0313] 4,4'-[[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]bis(3-phenylnaphthalene-1-carboxylic acid)

[0314] Dimethyl 4,4'-[[1,1'-binaphthalene]-2,2'-diylbis(oxy)]bis(3-phenylnaphthalene-1-carboxylate)

[0315] [[1,1'-Binaphthalene]-2,2'-diylbis(oxy[1,2'-binaphthalene]-1',4'-diyl)]dimethanol

[0316] 1',1”-[[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]bis([1,2'-binaphthalene]-4'-carboxylic acid)

[0317] [[1,1'-Binaphthalene]-2,2'-diylbis(oxy[2,2'-binaphthalene]-1,4-diyl)]dimethanol

[0318] 1,1'-[[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]bis([2,2'-binaphthalene]-4-carboxylic acid)

[0319] Dimethyl 1,1'-[[1,1'-binaphthalene]-2,2'-diylbis(oxy)]bis([2,2'-binaphthalene]-4-carboxylate)

[0320] ([1,1'-Binaphthalene]-2,2'-diylbis{oxy[3-(phenanthren-9-yl)naphthalene-4,1-diyl]})dimethanol

[0321] ([1,1'-Binaphthalene]-2,2'-diylbis{oxy[3-(dibenzo[b,d]thiophen-4-yl)naphthalene-4,1-diyl]})dimethanol

[0322] ([1,1'-Binaphthalene]-2,2'-diylbis{oxy[3-(thianthren-1-yl)naphthalene-4,1-diyl]})dimethanol

[0323] [(6,6'-Diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis(oxy[1,1'-biphenyl]-2,5-diyl)]dimethanol

[0324] 6,6'-[(6,6'-Diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]bis([1,1'-biphenyl]-3-carboxylic acid)

[0325] Dimethyl 6,6'-[(6,6'-diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]bis([1,1'-biphenyl]-3-carboxylate

[0326] [(6,6'-Diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis{oxy[3-(naphthalen-1-yl)-4,1-phenylene]}]dimethanol

[0327] 4,4'-[(6,6'-Diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]bis[3-(naphthalen-1-yl)benzoic acid]

[0328] [(6,6'-Diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis{oxy[3-(naphthalen-2-yl)-4,1-phenylene]}]dimethanol

[0329] 4,4'-[(6,6'-Diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]bis[3-(naphthalen-2-yl)benzoic acid]

[0330] [(6,6'-Diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis{oxy[3-(dibenzo[b,d]thiophen-4-yl)-4,1-phenylene]}]dimethanol

[0331] [(6,6'-Diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis{oxy[3-(thianthren-1-yl)-4,1-phenylene]}]dimethanol

[0332] [(6,6'-Bis(naphthalen-1-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy[1,1'-biphenyl]-2,5-diyl)]dimethanol

[0333] [(6,6'-Bis(naphthalen-1-yl)[1,1'-binaphthalene]-2,2'-diyl)bis{oxy[3-(naphthalen-1-yl)-4,1-phenylene]}]dimethanol

[0334] 4,4'-[(6,6'-Bis(naphthalen-1-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]bis[3-(naphthalen-1-yl)benzoic acid]

[0335] Dimethyl 4,4'-[(6,6'-Bis(naphthalen-1-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]bis[3-(naphthalen-1-yl)benzoate]

[0336] [(6,6'-Bis(naphthalen-1-yl)[1,1'-binaphthalene]-2,2'-diyl)bis{oxy[3-(naphthalen-2-yl)-4,1-phenylene]}]dimethanol

[0337] 4,4'-[(6,6'-Bis(naphthalen-1-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]bis[3-(naphthalen-2-yl)benzoic acid]

[0338] [(6,6'-Bis(naphthalen-1-yl)[1,1'-binaphthalene]-2,2'-diyl)bis{oxy[3-(dibenzo[b,d]thiophen-4-yl)-4,1-phenylene]}]dimethanol

[0339] [(6,6'-Bis(naphthalen-1-yl)[1,1'-binaphthalene]-2,2'-diyl)bis{oxy[3-(thianthren-1-yl)-4,1-phenylene]}]dimethanol

[0340] [(6,6'-Bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy[1,1'-biphenyl]-2,5-diyl)]dimethanol

[0341] [(6,6'-Bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis{oxy[3-(naphthalen-1-yl)-4,1-phenylene]}]dimethanol

[0342] 4,4'-[(6,6'-Bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]bis[3-(naphthalen-1-yl)benzoic acid]

[0343] [(6,6'-Bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis{oxy[3-(naphthalen-2-yl)-4,1-phenylene]}]dimethanol

[0344] 4,4'-[(6,6'-Bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]bis[3-(naphthalen-2-yl)benzoic acid]

[0345] Dimethyl 4,4'-[(6,6'-Bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]bis[3-(naphthalen-2-yl)benzoate]

[0346] [(6,6'-Bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis{oxy[3-(dibenzo[b,d]thiophen-4-yl)-4,1-phenylene]}]dimethanol

[0347] [(6,6'-Bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis{oxy[3-(thianthren-1-yl)-4,1-phenylene]}]dimethanol

[0348] [(6,6'-Di(phenanthren-9-yl)[1,1'-binaphthalene]-2,2'-diyl)bis{oxy[3-(phenanthren-9-yl)-4,1-phenylene]}]dimethanol

[0349] [(6,6'-Bis(dibenzo[b,d]thiophen-4-yl)[1,1'-binaphthalene]-2,2'-diyl)bis{oxy[3-(dibenzo[b,d]thiophen-4-yl)-4,1-phenylene]}]dimethanol

[0350] [(6,6'-Di(thianthren-1-yl)[1,1'-binaphthalene]-2,2'-diyl)bis{oxy[3-(thianthren-1-yl)-4,1-phenylene]}]dimethanol

[0351] [(6,6'-Diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis(oxy[1,1'-biphenyl]-5,2-diyl)]dimethanol

[0352] 5,5'-[(6,6'-Diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]bis([1,1'-biphenyl]-2-carboxylic acid)

[0353] [(6,6'-Diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis{oxy[2-(naphthalen-1-yl)-4,1-phenylene]}]dimethanol

[0354] 4,4'-[(6,6'-Diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]bis[2-(naphthalen-1-yl)benzoic acid]

[0355] [(6,6'-Diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis{oxy[2-(naphthalen-2-yl)-4,1-phenylene]}]dimethanol

[0356] 4,4'-[(6,6'-Diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]bis[2-(naphthalen-2-yl)benzoic acid]

[0357] [(6,6'-Bis(naphthalen-1-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy[1,1'-biphenyl]-5,2-diyl)]dimethanol

[0358] [(6,6'-Bis(naphthalen-1-yl)[1,1'-binaphthalene]-2,2'-diyl)bis{oxy[2-(naphthalen-1-yl)-4,1-phenylene]}]dimethanol

[0359] 4,4'-[(6,6'-Bis(naphthalen-1-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]bis[2-(naphthalen-1-yl)benzoic acid]

[0360] Dimethyl 4,4'-[(6,6'-Bis(naphthalen-1-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]bis[2-(naphthalen-1-yl)benzoate]

[0361] [(6,6'-Bis(naphthalen-1-yl)[1,1'-binaphthalene]-2,2'-diyl)bis{oxy[2-(naphthalen-2-yl)-4,1-phenylene]}]dimethanol

[0362] [(6,6'-Bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy[1,1'-biphenyl]-5,2-diyl)]dimethanol

[0363] [(6,6'-Bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis{oxy[2-(naphthalen-1-yl)-4,1-phenylene]}]dimethanol

[0364] [(6,6'-Bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis{oxy[2-(naphthalen-2-yl)-4,1-phenylene]}]dimethanol

[0365] 4,4'-[(6,6'-Bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]bis[2-(naphthalen-2-yl)benzoic acid]

[0366] Dimethyl 4,4'-[(6,6'-bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]bis[2-(naphthalen-2-yl)benzoate]

[0367] [(6,6'-Di(phenanthren-9-yl)[1,1'-binaphthalene]-2,2'-diyl)bis{oxy[2-(phenanthren-9-yl)-4,1-phenylene]}]dimethanol

[0368] [(6,6'-Bis(dibenzo[b,d]thiophen-4-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy[1,1'-biphenyl]-5,2-diyl)]dimethanol

[0369] [(6,6'-Bis(dibenzo[b,d]thiophen-4-yl)[1,1'-binaphthalene]-2,2'-diyl)bis{oxy[2-(dibenzo[b,d]thiophen-4-yl)-4,1-phenylene]}]dimethanol

[0370] [(6,6'-Di(thianthren-1-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy[1,1'-biphenyl]-5,2-diyl)]dimethanol

[0371] [(6,6'-Di(thianthren-1-yl)[1,1'-binaphthalene]-2,2'-diyl)bis{oxy[2-(thianthren-1-yl)-4,1-phenylene]}]dimethanol

[0372] {(6,6'-Diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis[oxy(4-phenylnaphthalene-6,2-diyl)]}dimethanol

[0373] [(6,6'-Diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis(oxy[1,1'-binaphthalene]-7,3-diyl)]dimethanol

[0374] [(6,6'-Diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis(oxy[1,2'-binaphthalene]-7,3-diyl)]dimethanol

[0375] {(6,6'-Bis(naphthalen-1-yl)[1,1'-binaphthalene]-2,2'-diyl)bis[oxy(4-phenylnaphthalene-6,2-diyl)]}dimethanol

[0376] [(6,6'-Bis(naphthalen-1-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy[1,1'-binaphthalene]-7,3-diyl)]dimethanol

[0377] 7,7'-[(6,6'-Bis(naphthalen-1-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]bis([1,1'-binaphthalene]-3-carboxylic acid)

[0378] [(6,6'-Bis(naphthalen-1-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy[1,2'-binaphthalene]-7,3-diyl)]dimethanol

[0379] [(6,6'-Bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy[1,1'-binaphthalene]-7,3-diyl)]dimethanol

[0380] [(6,6'-Bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy[1,2'-binaphthalene]-7,3-diyl)]dimethanol

[0381] {(6,6'-Diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis[oxy(3-phenylnaphthalene-4,1-diyl)]}dimethanol

[0382] 4,4'-[(6,6'-Diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]bis(3-phenylnaphthalene-1-carboxylic acid)

[0383] Dimethyl 4,4'-[(6,6'-Diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]bis(3-phenylnaphthalene-1-carboxylic acid)

[0384] [(6,6'-Diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis(oxy[1,2'-binaphthalene]-1',4'-diyl)]dimethanol

[0385] [(6,6'-Diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis(oxy[2,2'-binaphthalene]-1,4-diyl)]dimethanol

[0386] {(6,6'-Bis(naphthalen-1-yl)[1,1'-binaphthalene]-2,2'-diyl)bis[oxy(3-phenylnaphthalene-4,1-diyl)]}dimethanol

[0387] [(6,6'-Bis(naphthalen-1-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy[1,2'-binaphthalene]-1',4'-diyl)]dimethanol

[0388] 1',1”-[(6,6'-bis(naphthalen-1-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]bis([1,2'-binaphthalene]-4'-carboxylic acid)

[0389] dimethyl 1',1”-[(6,6'-bis(naphthalen-1-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]bis([1,2'-binaphthalene]-4'-carboxylate)

[0390] [(6,6'-bis(naphthalen-1-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy[2,2'-binaphthalene]-1,4-diyl)]dimethanol

[0391] {(6,6'-bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis[oxy(3-phenylnaphthalene-4,1-diyl)]}dimethanol

[0392] [(6,6'-bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy[1,2'-binaphthalene]-1',4'-diyl)]dimethanol

[0393] [(6,6'-bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy[2,2'-binaphthalene]-1,4-diyl)]dimethanol

[0394] 1,1'-[(6,6'-bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]bis([2,2'-binaphthalene]-4-carboxylic acid)

[0395] dimethyl 1,1'-[(6,6'-bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]bis([2,2'-binaphthalene]-4-carboxylate)

[0396] [(6,6'-bis(dibenzo[b,d]thiophen-4-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy[2,2'-binaphthalene]-1,4-diyl)]dimethanol

[0397] [(6,6'-bis(dibenzo[b,d]thiophen-4-yl)[1,1'-binaphthalene]-2,2'-diyl)bis{oxy[3-(dibenzo[b,d]thiophen-4-yl)naphthalene-4,1-diyl]}]dimethanol

[0398] [(6,6'-di(thianthren-1-yl)[1,1'-binaphthalene]-2,2'-diyl)bis{oxy[3-(thianthren-1-yl)naphthalene-4,1-diyl]}]dimethanol.

[0399] Compounds of formula (I), where p = q = 0, can be prepared by the method shown in reaction scheme 1 below, where X and A each have one of the meanings defined above for X 1 and X 2 or A 1 and A 2 Specifically, X is -CH2OH or -C(O)OR x , where R x is usually C1-C4-alkyl, and A is a monocyclic or polycyclic heteroarylene or arylene.

[0400] Compounds of formula (I) can be prepared by methods known in the art, as shown in the following reaction scheme.

[0401] Scheme 1 shows the synthesis of compound (I), where X 1 and X 2 have the same meaning (hereinafter referred to as X), A 1 and A 2 have the same meaning (hereinafter referred to as A). Such compounds are hereinafter referred to as (I'). R 1 ' has the same meaning as R 1 , or is a precursor thereof, i.e., a substituent that can be converted into the desired R 1 group. Similarly, R2' has the same meaning as R 2 , or is a precursor thereof, i.e., a substituent that can be converted into the desired R 2 group. A' is A or a precursor thereof, which is a monocyclic or polycyclic arylene or heteroarylene A, but which bears a substituent that can be converted into the desired R Ar1 group. X' is -CHO, -CN or -C(O)OR x ', where R x ' is phenyl, benzyl or C1-C4-alkyl, more typically methyl.

[0402] Scheme 1

[0403]

[0404] In the presence of a base, such as an oxo base like an alkali metal carbonate or an alkali metal hydride, especially in the presence of an alkali metal carbonate such as potassium carbonate, the 1,1'-bi-2-naphthol compound of formula (1) is reacted with about 2 to 2.5 molar equivalents of the compound of formula (2) to give the compound of formula (Ia). A suitable solvent for this reaction is a polar aprotic organic solvent, such as dimethylformamide.

[0405] Compounds containing a fluorine leaving group (2) can be replaced with similar chlorine or bromine compounds (X’-A’-Cl or X’-A’-Br). However, fluorine is the most reactive, so fluorine is the preferred leaving group.

[0406] If R 1’ , R 2’ and A’ in compound (3) are respectively R 1 , R 2 and A, and X’ has the required meaning, namely -C(O)OR x’ , where R x’ has the meaning required by R x , then compound (3) corresponds to the required compound (I’), without further transformation.

[0407] Compound (3) in which X’ is -CHO can be converted to compound (I’) in which X is -CH2OH by reducing the formyl group with a suitable reducing agent (such as sodium borohydride).

[0408] Compound (I’) in which X is -CH2OH can alternatively be prepared from compound (3) in which X’ is -C(O)OR x’ (where R x’ is a C1-C4-alkyl group, especially methyl) by reducing the ester group with a suitable reducing agent (such as lithium aluminum hydride (LAH) or DIBAL-H (diisobutylaluminum hydride)).

[0409] Compound (I’) in which X is -C(O)OH can be prepared from compound (3) in which X’ is -C(O)OR x’ by hydrolysis, for example, under basic conditions.

[0410] Compound (I’) in which X is -C(O)OH can alternatively be prepared from compound (3) in which X’ is -CN by hydrolysis, for example, under basic conditions.

[0411] Compound (I’) in which X is -C(O)OR x can be prepared from compound (3) in which X’ is -C(O)OH by esterification using a well-established method, for example, first converting the diacid of formula (3) to the corresponding diacyl chloride, for example, by conversion with thionyl chloride, and then reacting with the corresponding alcohol R x -OH (such as methanol) under basic conditions. x

[0412] Compound (I’) in which X is -C(O)OR x can be prepared from compound (3) in which X’ is -CHO by oxidation to the corresponding diacid and then esterification with an alcohol according to a well-established method. By in the corresponding alcohol Rx in the presence of -OH (such as methanol), reacting a compound (3) in which X' is -CHO with an oxidizing agent (2KHSO5 . KHSO4 . K2SO4), and these two steps can be completed by a "one-pot method".

[0413] If R 1’ is an R 2’ precursor group, it can be converted into the desired R 1 and R 2 groups by methods well-known in the art. Just to give a few examples, if R 1 group and / or R 2 group is for example R, and R is a heteroaromatic ring or an aromatic ring Q 1 , then the latter can be introduced by a Suzuki reaction, and the Suzuki reaction is: where R 1’ and / or R 2’ is a halogen or a sulfonate group (such as trifluoromethanesulfonate or tosylate), especially a compound (3) where Br reacts with a suitable boronic acid derivative such as Q 1 -B(OH)2 or its ester or anhydride, under typical Suzuki conditions, for example Pd-catalyzed (more details of the Suzuki reaction are given in Route 2), and the reaction occurs. This reaction can be carried out before or after the conversion of X' to X (if necessary).

[0414] If for example R 1 and / or R 2 group is an alkenyl group -CH=CHR", then the latter can be introduced by a Heck reaction, and the Heck reaction is: where R 1’ and / or R 2’ is a halogen or a sulfonate group (such as trifluoromethanesulfonate or tosylate), especially a compound (3) where Br reacts with the corresponding alkene CH2=CHR", under typical Heck conditions, for example Pd-catalyzed, and the reaction occurs. This reaction can also be carried out before or after the conversion of X' to X (if necessary).

[0415] Similarly, if A' is a precursor of A, and the precursor is a monocyclic or polycyclic arylene or heteroarylene A, but it carries substituents that can be converted into the desired R Ar1 group, this conversion can be carried out by methods well-known in the art. Just to give a few examples, if A is a monocyclic or polycyclic arylene or heteroarylene A substituted by an R Ar1 group and R Ar1 is Q 2, then the latter can be introduced via the Suzuki reaction, which is as follows: wherein A' is a monocyclic or polycyclic arylene or heteroarylene ring A substituted with a halogen or sulfonate group (such as trifluoromethanesulfonate or tosylate), especially Br, of compound (3) and a suitable boronic acid derivative such as Q 2 -B(OH)2 or its ester or anhydride, under typical Suzuki conditions, e.g., Pd catalysis (more details of the Suzuki reaction are given in Route 2), reacts. This reaction can be carried out before or after the conversion of X' to X (if necessary).

[0416] If A is a monocyclic or polycyclic arylene or heteroarylene A substituted with an R Ar1 group and R Ar1 is -CH=CR”, then the latter can be introduced via the Heck reaction, which is as follows: wherein A' is a monocyclic or polycyclic arylene or heteroarylene ring A substituted with a halogen or sulfonate group (such as trifluoromethanesulfonate or tosylate), especially Br, of compound (3) and the corresponding alkene CH2=CHR”, under typical Heck reaction conditions, e.g., Pd catalysis, reacts. This reaction can also be carried out before or after the conversion of X' to X (if necessary).

[0417] The 1,1'-bi-2-naphthol compound (1) is commercially available or can be prepared by methods known in the art. By way of example only, Route 2 illustrates the bromination of 1,1'-bi-2-naphthol (1’) to 6,6’-dibromo-1,1'-bi-2-naphthol (1”), and the further conversion of the latter to 6,6’-heteroaryl- or 6,6’-aryl-substituted 1,1'-bi-2-naphthol (1”’).

[0418] Route 2

[0419]

[0420] In step i) of the process according to Route 2, 1,1'-bi-2-naphthol (1') is brominated to selectively produce 6,6'-dibromo-1,1'-bi-2-naphthol of formula (1"). Bromination can be simply achieved by mixing 1,1'-bi-2-naphthol (1') with a suitable brominating reagent in a polar aprotic solvent at low temperature, the polar aprotic solvent being inert to bromination. Suitable brominating agents are especially elemental bromine. Suitable polar aprotic solvents for step i) include aliphatic halogenated hydrocarbon compounds (such as dichloromethane or dichloroethane), esters (such as isopropyl acetate or ethyl acetate), and mixtures thereof. The suitable reaction temperature for the bromination reaction of 1,1'-bi-2-naphthol (1') with bromine is generally in the range of -100 to 10 °C, especially in the range of -100 to -30 °C, or alternatively, in the range of -10 to 10 °C. Further details can be found in Bunzen et al., J. Am. Chem. Soc., 2009, 131(10), 3621-3630. As an alternative, N-bromosuccinimide can be used as the brominating agent. In this case, the reaction temperature is generally higher than that for bromination with elemental bromine, for example, 0 to 50 °C. In addition to aliphatic halogenated hydrocarbons, suitable solvents can also include aliphatic ketones having 3 to 6 carbon atoms, such as acetone or methyl ethyl ketone, ethers having 4 to 6 carbon atoms, such as tetrahydrofuran, dioxane, diethyl ether, cyclopentyl methyl ether, and other solvents, such as acetonitrile, dimethylformamide, chloroform, dichloromethane, dichloroethane, and mixtures thereof with aliphatic halogenated hydrocarbons.

[0421] As another alternative, 6,6'-dibromo-1,1'-bi-2-naphthol of formula (1") can also be synthesized by copper(II)-catalyzed oxidative coupling of 6-bromo-2-naphthol, for example, according to the method described in H. Egami et al., J. Am. Chem. Soc. 2009, 13(17), 6082-83.

[0422] In step ii) of Route 2, in the presence of a transition metal catalyst, especially in the presence of a palladium catalyst, a compound of formula (1") is reacted with a heteroaryl or aryl boron compound of formula Q 1 -B(OH)2, where Q 1 is as defined above, or with Q 1-B(OH)2 esters or anhydrides, especially C1-C4-alkyl esters thereof, react. Usually, step ii) is carried out under Suzuki coupling conditions (see, for example, A. Suzuki et al., Chem. Rev. 1995, 95, 2457-2483; N. Zhe et al., J. Med. Chem. 2005, 48(5), 1569-1609; Young et al., J. Med. Chem. 2004, 47(6), 1547-1552; C. Slee et al., Bioorg. Med. Chem. Lett. 2001, 9, 3243-3253; T. Zhang et al., Tetrahedron Lett. 52(2011), 311-313; S. Bourrain et al., Synlett. 5(2004), 795-798; B. Li et al., Europ. J. Org. Chem. 20113932-3937). Suitable transition metal catalysts are especially palladium compounds carrying at least one palladium atom and at least one trisubstituted phosphine ligand. Examples of palladium catalysts are tetrakis(triphenylphosphine)palladium, tetrakis(tritolyphosphine)palladium and dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium(II) (PdCl2(dppf)). Usually, the palladium catalyst is prepared in situ from a suitable palladium precursor and a suitable phosphine ligand. Suitable palladium precursors are palladium compounds such as tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3) or palladium(II) acetate (Pd(OAc)2). Suitable phosphine ligands are especially tris(substituted)phosphines such as triarylphosphines, for example triphenylphosphine, tritolyphosphine or 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP), tricycloalkylphosphines, for example tri-n-butylphosphine, tris(tert-butyl)phosphine or tricyclohexylphosphine, or dicyclohexyl-(2',4',6'-triisopropyl-1,1'-biphenyl-2-yl)-phosphine (X-Phos). Usually, the reaction is carried out in the presence of a base, especially the above-mentioned oxygen-containing bases such as alkali metal alkoxides, alkali metal hydroxides, alkali metal carbonates or alkaline earth carbonates, for example sodium ethoxide, sodium tert-butoxide, lithium hydroxide, sodium carbonate or potassium carbonate; phosphate bases such as tripotassium phosphate. Usually, the reaction according to step ii) of route 2 is carried out in an organic solvent or a mixture thereof with water. If the reaction is carried out in a mixture of an organic solvent and water, the reaction mixture can be single-phase or two-phase. Suitable organic solvents include, but are not limited to, aromatic hydrocarbons (e.g., toluene, anisole or xylene), acyclic and cyclic ethers (e.g., methyl tert-butyl ether, diisopropyl ether, dioxane or tetrahydrofuran), and aliphatic alcohols having 1 to 4 carbon atoms (e.g., methanol, ethanol or isopropanol) and mixtures thereof. The reaction according to step ii) of route 2 is usually carried out at a temperature in the range of 50 to 150 °C.

[0423] Compound (2) is commercially available or can be prepared by methods known in the art. By way of example only, Route 3 illustrates the conversion of bromo-substituted (2’) to heteroaryl- or aryl-substituted (2”). This conversion can be carried out under the Suzuki conditions illustrated in Route 2.

[0424] Route 3

[0425]

[0426] wherein X 1 and X 2 and / or A 1 and A 2 Compound (I) having different meanings (hereinafter referred to as compound (I”)) can be prepared by the stepwise reaction of the two hydroxyl groups of compound (1), as shown in Route 4. However, the method according to Route 4 is particularly suitable for preparing compounds of formula (I) below: wherein p and q are each 0, 1 or 2, and the substituents R 1 and R 2 (if present) have the same meaning and are attached at the corresponding positions of their respective naphthyl units.

[0427] Route 4

[0428]

[0429] In reaction step i) of the method according to Route 4, the 1,1'-bi-2-naphthol compound (1) is reacted with about 0.7 to 1.1 molar equivalents of a compound of formula (2.1). Then, the monoetherified product of formula (4) is further etherified with about 1.0 to 1.5 molar equivalents of a compound of formula (2.2) to obtain compound (5). Both of these etherification steps can be carried out under reaction conditions substantially similar to those in Route 1 above ((1) and the reaction of (2) to (3)).

[0430] If R 1’ and R 2’ in compound (5) are respectively R 1 and R 2 , then compound (5) corresponds to the desired compound (I”), without further conversion. Otherwise, R 1’ and R 2’ are converted to the desired R 1 and R 2 groups, as described in Route 1 above.

[0431] If desired or appropriate, wherein A 1 and A 2Compounds of formula (I) that are the same or different biphenylene moieties can be prepared in two, three or four steps by methods similar to those shown in Reaction Scheme 5 below. The methods according to Scheme 5 and similar methods are particularly suitable for the preparation of the following compounds (I): wherein p and q are each 0, 1 or 2, and the substituents R 1 and R 2 (if present) have the same meaning and are attached at the corresponding positions of their respective naphthyl units. Reaction Scheme 5 illustrates the preparation of compounds (I) wherein A 1 is 3,4'-biphenylene and A 2 is 3,3'-biphenylene.

[0432] Scheme 5

[0433]

[0434] In the first reaction step of Scheme 5, 1,1'-bi-2-naphthol (1) is reacted with about 0.7 to 1.1 molar equivalents of the bromide of formula (6a). Then, in the second step, the mono-etherified product of formula (7) is further etherified with about 1.0 to 1.5 molar equivalents of the compound of formula (6b) to give the dibromide of formula (7). The first and second reaction steps can be carried out under reaction conditions substantially similar to those in Scheme 1 above. Then, the dibromide (7) is reacted with about 2 molar equivalents of the phenylboron compound of formula (8), similar to the coupling step described above in connection with Scheme 2, to give compound (9).

[0435] If R 1’ and R 2’ in compound (9) are respectively R 1 and R 2 , then compound (9) corresponds to the desired biphenyl compound (I) without further transformation. Otherwise, R 1’ and R 2’ are converted to the desired R 1 and R 2 groups as described above in Scheme 1.

[0436] Compounds of formula (9') that differ from compound (9) prepared in Scheme 5 above only in that A 1 and A 2 have the same meaning (e.g., 3,4'-biphenylene) can be prepared by a variant of the first step of Scheme 5, wherein 1,1'-bi-2-naphthol (1) is reacted with about 2 molar equivalents of the bromide of formula (6a), followed by the third reaction step of Scheme 5.

[0437] Compounds that differ from compound (9) prepared in Scheme 5 above only in that X 1 and X2 Compounds having different formula (9”) can be prepared using a variant of the method according to Route 5. Specifically, the compound (7) obtained in the first step of the method of Route 5 is reacted with about one molar equivalent of the compound (8'), which is the compound (8) with another X group, by a method similar to the third step. Then the intermediate product thus obtained is reacted with the compound (6b) according to the second step of Route 5. Finally, the obtained bromide is reacted with about one molar equivalent of the compound (8) by a method similar to step iii).

[0438] Including as A 1 and A 2 identical or different bi(het)arylene groups that are not biphenylene and in which the variables p, q, R 1 、R 2 、X 1 and X 2 have the meanings defined herein, the compounds of formula (I) can also be prepared generally in two, three or four steps by a method similar to that described in Reaction Route 5 above, provided that the bond between the two heteroarylene or arylene moieties of A 1 and A 2 is a C-C bond.

[0439] For easier understanding, the following route illustrates the reaction of Route 1 based on a more specific example.

[0440] Route 6 illustrates the reaction of Route 1 for the synthesis of the following compound (I): wherein p and q are 0, A 1 and A 2 are 1,4-phenylene substituted by the Q 2 group, X 1 and X 2 are CH2OH, and the starting material is the compound (2) that already carries the desired Q 2 substituent.

[0441] Route 6

[0442]

[0443] Route 7 illustrates the reaction of Route 1 for the synthesis of the following compound (I): wherein p and q are 0, A 1 and A 2 are 1,4-phenylene substituted by the Q 2 group, X 1 and X 2 are CH2OH, and the starting material is the compound (2) that carries the precursor (Br) of the desired Q 2 substituent. Q2 It is introduced after the reaction of the etherification step ((3”’) to (3 iv )), or after the formyl reduction (the reaction of (3”’) to (I”’)).

[0444] Route 7

[0445]

[0446] Route 8 illustrates the reaction of Route 1 for synthesizing the following compound (I): where p and q are 1, R 1 and R 2 is Q 1 , A 1 and A 2 is 1,4-phenylene substituted by the Q 2 group, X 1 and X 2 is CH2OH, the starting materials are compound (1”) and compound (2”), compound (1”) carries the precursor (Br) of the required Q 1 substituent, and compound (2”) already carries the required Q 2 substituent. Q 1 is introduced after the reaction of the etherification step ((3 v ) to (3 vII )) or after the formyl reduction (the reaction of (3 vi ) to (I iv )).

[0447] Route 8

[0448]

[0449] Optionally, Q 1 can be introduced after the reaction of the etherification step ((1”) to (1”’)), as shown in Route 2 above.

[0450] Route 9 illustrates the reaction of Route 1 for synthesizing compound (I 1 and Q 2 are the same (hereinafter referred to as Q). iv )).

[0451] Route 9

[0452]

[0453] The transformations shown in Routes 1 to 9 can be completed by the reactions in the above routes or by obvious variations of these reactions, or optionally, by established methods in organic chemistry or combinations thereof.

[0454] Other compounds of formula (I) can be prepared by obvious variations of the above reactions and in combination with established methods in organic chemistry.

[0455] The reaction mixtures obtained in the individual steps for the synthesis of the compounds described in Reaction Routes 1-9 above are generally worked up in a conventional manner, for example by mixing with water, separating the phases and, where appropriate, purifying the crude product by washing, treatment with an adsorbent (such as activated carbon) or chromatography or crystallization. In some cases, the intermediate forms in the form of a colorless or light brown viscous oil, which is free of volatiles or purified under reduced pressure and moderately elevated temperature. If a solid intermediate is obtained, purification can be achieved by recrystallization or washing methods such as slurry washing.

[0456] The starting compounds for the preparation of the compounds of formula (I) used in the syntheses shown in Routes 1-9 above are commercially available or can be prepared by methods known in the art.

[0457] As described above, the compounds of the present invention can be obtained in very high purity, which means that the product obtained contains no significant amount of organic impurities other than volatiles that are different from the compounds of formula (I). Generally, based on non-volatile organic matter, the purity of the compounds of formula (I) is at least 95%, especially at least 98%, and particularly at least 99%, i.e., the product contains at most 5%, especially at most 2% and particularly at most 1% of non-volatile impurities different from the compounds of formula (I).

[0458] It should be mentioned in this context that mixtures of different compounds of formula (I) are also available, since they can be used as monomer compositions for the preparation of useful thermoplastic resins (such as polycarbonate resins), said thermoplastic resins comprising different structural units of formula (II) derived from different monomers of formula (I). Accordingly, mixtures of different compounds of formula (I) and the corresponding thermoplastic resins comprising different structural units of formula (II) are also part of the present invention.

[0459] The term "volatile" means an organic compound having a boiling point below 200 °C at standard pressure (10 5 Pa). Thus, non-volatile organic matter should be understood to mean compounds having a boiling point above 200 °C at standard pressure.

[0460] A particular advantage of the present invention is that the compounds of formula (I) and their solvates can generally be obtained in crystalline form. In the crystalline form, the compounds of formula (I) can exist in pure form or as solvates with water or organic solvents. Accordingly, a specific aspect of the present invention relates to compounds of formula (I) which are substantially in crystalline form. In particular, the present invention relates to crystalline forms in which the compounds of formula (I) are present without solvent, and to crystalline solvates of the compounds of formula (I), wherein the crystals contain incorporated solvent.

[0461] A particular advantage of the present invention is that the compounds of formula (I) and their solvates can generally be readily crystallized from conventional organic solvents. This allows for the effective purification of the compounds of formula (I). Suitable organic solvents for crystallizing the compounds of formula (I) or their solvates include, but are not limited to, aromatic hydrocarbons (such as toluene or xylene), aliphatic ketones especially those having 3 to 6 carbon atoms (such as acetone, methyl ethyl ketone, methyl isopropyl ketone or diethyl ketone), aliphatic and cycloaliphatic 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), aliphatic alcohols having 1 to 4 carbon atoms (such as methanol, ethanol or isopropanol) and aliphatic esters (such as ethyl acetate) and mixtures thereof. It may be beneficial to filter the crude preparation of the dissolved compound of formula (I) (such as through diatomaceous earth) prior to the crystallization step in order to remove solid components which may be present in the crude preparation.

[0462] Furthermore, impurities which may be present in the crude preparation of the compound of formula (I), especially chromophoric impurities and heavy metals, can be removed at any stage of the purification process, for example prior to the filtration step or the crystallization step, by standard procedures, such as treatment with an adsorbent (such as activated carbon).

[0463] Alternatively, the compounds of formula (I) and their solvates can be obtained in purified form by employing other simple and effective methods for purifying crude products of these compounds, such as especially slurry washing of the crude solid obtained directly after the transformation to prepare the compounds of formula (I). The slurry washing is generally carried out at ambient temperature or at an elevated temperature of generally about 30 to 90 °C, especially 40 to 80 °C. Here, the suitable organic solvents are in principle the same as those listed above which are suitable for crystallizing the compounds of formula (I), such as especially the aromatic hydrocarbons, aliphatic ketones and aliphatic ethers mentioned, such as toluene, methyl ethyl ketone and methyl tert-butyl ether.

[0464] Thus, the compounds of formula (I) for preparing the thermoplastic polymers defined herein, especially polycarbonates, 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 extent required for the preparation of optical resins. In particular, these compounds can be obtained in a purity that provides a high refractive index and low haze, which is particularly important for use in optical resins used in the preparation of optical devices. In summary, the compounds of formula (I) can be used especially as monomers in the preparation of optical resins.

[0465] Those skilled in the art will readily understand that the formula (I) of the monomers used corresponds to the formula (II) of the structural units included in the thermoplastic resin. Similarly, the formula (Ia) of the monomers used corresponds respectively to the formula (IIa) of the structural units included in the thermoplastic resin. Obviously, the formulas (Ia.1), (Ia.2), (Ia.3) and (Ia.4) of the monomers used correspond respectively to the formulas (IIa.1), (IIa.2), (IIa.3) and (IIa.4) of the structural units included in the thermoplastic resin, where #, X, R 0 and Q 0 are as defined herein.

[0466]

[0467]

[0468] Those skilled in the art should also understand that the structural units of formulas (II), (IIa), (IIa.1), (IIa.2), (IIa.3) and (IIa.4) are respectively repeating units within the polymer chain of the thermoplastic resin. In addition to the respective structural units of formulas (II), (IIa), (IIa.1), (IIa.2), (IIa.3) and (IIa.4), the thermoplastic resin may also have structural units different from them. In a preferred embodiment, these other structural units are derived from aromatic monomers of formula (IV), thereby producing structural units of formula (V):

[0469] HO-R z -A 3 -R z -OH (IV)

[0470] #-O-R z -A 3 -R z -O-# (V)

[0471] where

[0472] # represents the connection point with the adjacent structural unit;

[0473] A 3is a polycyclic group with at least 2 benzene rings, where the benzene rings can be fused via W and / or directly to each other and / or via a non-benzene carbocyclic ring and / or via two non-benzene carbocyclic rings fused via a linking group L, where A 3 is unsubstituted or substituted by 1, 2 or 3 radicals selected from halogen, C1-C6-alkyl, C5-C6-cycloalkyl, phenyl, naphthyl, 1,2-dihydroacenaphthylenyl, phenanthrenyl, pyrenyl, triphenylenyl, benz[b]furanyl, dibenzo[b,d]furanyl, benz[b]thiophenyl, dibenzo[b,d]thiophenyl and thianthrenyl;

[0474] 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’)

[0475]

[0476] where

[0477] Q’ represents a single bond, O, C=O or CH2;

[0478] R 7a 、R 7b are independently of one another selected from hydrogen, fluorine, CN, R, OR, CH v R’ 3-v 、NR2, C(O)R and C(O)NH2, where R and R’ are as defined above, and v is 0, 1 or 2; and

[0479] * represents the point of attachment to the benzene ring;

[0480] L is selected from a single bond, C1-C4-alkylene, C4-C7-cycloalkylene, C4-C7-cycloalkylenedimethylene, phenylenedimethylene, where L is unsubstituted or substituted by 1 or 2 radicals R L selected from C1-C4-alkyl, halogen, C1-C4-haloalkyl, C4-C7-cycloalkyl and phenyl,

[0481] Ar is selected from monocyclic or polycyclic aryl groups having 6 to 26 carbon atoms as ring atoms and monocyclic or polycyclic heteroaryl groups having a total of 5 to 26 atoms as ring members, where 1, 2, 3 or 4 of these ring member atoms of the heteroaryl group are selected from nitrogen, sulfur and oxygen, and the remaining atoms of these ring member atoms of the heteroaryl group are carbon atoms, where Ar is unsubstituted or substituted by 1, 2 or 3 radicals R ab selected from halogen, phenyl and C1-C4-alkyl;

[0482] R z is a single bond, Alk 3 、O-Alk 4 -, O-Alk4 -[O-Alk 4 -] w - or O-Alk 5 -C(O)-, where O is bonded to A 3 , and where

[0483] w is an integer from 1 to 10;

[0484] Alk 3 is a C1-C4-alkanediyl;

[0485] Alk 4 is a C2-C4-alkanediyl; and

[0486] Alk 5 is a C1-C4-alkanediyl.

[0487] If R in formula (IV) z is O-Alk 5 -C(O), then esters of the monomers of formula (IV) can alternatively be used, especially C1-C4-alkyl esters.

[0488] In the context of formulas (IV) and (V), A 3 is in particular a polycyclic group having at least 2 benzene rings or naphthalene rings, where the benzene rings are linked by W or are fused via two non-benzene carbocyclic rings connected by a linking group L, where W is in particular selected from a single bond, S, S(O), SO2, C(CH3)2 and group A', and where L is a single bond or a C1-C4-alkylene.

[0489] In the context of formulas (IV) and (V), R z is in particular O-Alk 4 -, where Alk 4 is in particular a straight-chain alkanediyl having 2 to 4 carbon atoms, and in particular O-CH2CH2.

[0490] Among the monomers of formula (IV), monomers of general formulas (IV-1) to (IV-8) are preferred

[0491]

[0492]

[0493] where

[0494] a and b are 0, 1, 2 or 3, in particular 0 or 1;

[0495] a' and b' are 0, 1, 2 or 3, in particular 0 or 1;

[0496] c and d are 0, 1, 2, 3, 4 or 5, in particular 0 or 1;

[0497] e and f are 0, 1, 2, 3, 4 or 5, especially 0 or 1;

[0498] W’ is S, S(O), SO2, O, a single bond, CH2, CH(CH3), C(CH3)2, especially S, S(O), SO2 or C(CH3)2;

[0499] and wherein R z 、R aa 、R ab 、R 7a 、R 7b and L are as defined for formula (IV), and wherein R z is especially selected from a single bond, CH2 and OCH2CH2.

[0500] Among the monomers of formula (IV), monomers of general formulas (IV-11) to (IV-22) are particularly preferred, wherein R z and R aa are as defined herein, and R z is especially selected from a single bond, CH2 and O-CH2CH2, especially O-CH2CH2:

[0501]

[0502]

[0503] Examples of the compounds of formulas (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(4-(2-hydroxyethoxy)-3-cyclohexylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene (BPPEF), 9,9-bis(6-hydroxynaphthalen-2-yl)fluorene, 9,9-bis(6-(2-hydroxyethoxy)naphthalen-2-yl)fluorene (also known as 9,9-bis(6-(2-hydroxyethoxy)naphthalen-2-yl)fluorene (BNEF) or 6,6'-(9-fluorenylidene)bis(2-naphthyloxyethanol) (NOLE)), 10,10-bis(4-hydroxyphenyl)anthracen-9-one, 10,10-bis(4-(2-hydroxyethoxy)phenyl)anthracen-9-one, 4,4'-dihydroxytetraphenylmethane, 4,4'-bis-(2-hydroxyethoxy)-tetraphenylmethane, 3,3'-diphenyl-4,4'-dihydroxy-tetraphenylmethane, bis-(6-hydroxynaphthalen-2-yl)-diphenylmethane, 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-diphenylphenyl]-1-methyl-ethyl]-2,6-diphenylphenoxy]ethanol, 2-[4-[1-[4-(2-hydroxyethoxy)-3-phenylphenyl]-1-methyl-ethyl]-2,6-diphenylphenoxy]ethanol, 9,9'-bis(hydroxymethyl)-9,9'-bifluorene, 2,2'-[1,1'-binaphthalene-2,2'-diylbis(oxy)]diethanol (also known as 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene or 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene (BNE)), 2,2'-bis(1-hydroxyethoxy)-1,1'-binaphthalene, 2,2'-bis(3-hydroxypropoxy)-1,1'-binaphthalene, 2,2'-bis(4-hydroxybutoxy)-1,1'-binaphthalene, 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthalene, 2,2'-bis(2-hydroxyethoxy)-6,6'-bis(naphthalen-1-yl)-1,1'-binaphthalene, 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthalene, 2,2'-bis(2-hydroxyethoxy)-6,6'-bis(naphthalen-1-yl)-1,1'-binaphthalene, 2,2'-bis(2-hydroxypropoxy)-6,6'-diphenyl-1,1'-binaphthalene, 2,2'-bis(2-hydroxypropoxy)-6,6'-bis(naphthalen-1-yl)-1,1'-binaphthalene, 2,2'-bis(2-hydroxyethoxy)-6,6'-bis(naphthalen-2-yl)-1,1'-binaphthalene, 2,2'-bis(2-hydroxyethoxy)-6,6'-bis(9-phenanthryl)-1,1'-binaphthalene, 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-bis(naphthalen-1-yl)phenyl]-1-methylethyl]-2,6-bis(naphthalen-1-yl)phenoxy]ethanol, 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-bis(naphthalen-2-yl)phenyl]-1-methylethyl]-2,6-bis(naphthalen-2-yl)phenoxy]ethanol, 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-bis(phenanthren-9-yl)phenyl]-1-methylethyl]-2,6-bis(phenanthren-9-yl)phenoxy]ethanol, 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-bis(1,2-dibenzo[b,d]thiophen-4-yl)phenyl]-1-methylethyl]-2,6-bis(1,2-dibenzo[b,d]thiophen-4-yl)phenoxy]ethanol, 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-bis(thianthren-1-yl)phenyl]-1-methylethyl]-2,6-bis(thianthren-1-yl)phenoxy]ethanol, 2-[4-[4-(2-hydroxyethoxy)-3,5-bis(naphthalen-1-yl)phenyl]sulfonyl-2,6-bis(naphthalen-1-yl)phenoxy]ethanol, 2-[4-[4-(2-hydroxyethoxy)-3,5-bis(naphthalen-2-yl)phenyl]sulfonyl-2,6-bis(naphthalen-2-yl)phenoxy]ethanol, 2-[4-[4-(2-hydroxyethoxy)-3,5-bis(phenanthren-9-yl)phenyl]sulfonyl-2,6-bis(phenanthren-9-yl)phenoxy]ethanol, 2-[4-[4-(2-hydroxyethoxy)-3,5-bis(thianthren-1-yl)phenyl]sulfonyl-2,6-bis(thianthren-1-yl)phenoxy]ethanol, and 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, etc.,

[0504] Among the monomers of 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'-binaphthalene (BNE or BHBNA), 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthalene (DPBHBNA), 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (BPEF), 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-bis(phenanthren-9-yl)phenyl]-1-methylethyl]-2,6-bis(phenanthren-9-yl)phenoxy]ethanol, 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-bis(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-bis(thianthren-1-yl)phenyl]-1-methyl-ethyl]-2,6-bis(thianthren-1-yl)phenoxy]ethanol, 2-[4-[4-(2-hydroxyethoxy)-3,5-bis(phenanthren-9-yl)phenyl]sulfonyl-2,6-bis(phenanthren-9-yl)phenoxy]ethanol, 2-[4-[4-(2-hydroxyethoxy)-3,5-bis(thianthren-1-yl)phenyl]sulfonyl-2,6-bis(thianthren-1-yl)phenoxy]ethanol and 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 are particularly preferred.

[0505] Therefore, among the structural units of formula (V) that can be included in the thermoplastic resin, the structural units of general formulas (V-1) to (V-8) are preferred.

[0506]

[0507]

[0508] wherein

[0509] a and b are 0, 1, 2 or 3, especially 0 or 1;

[0510] a' and b' are 0, 1, 2 or 3, especially 0 or 1;

[0511] c and d are 0, 1, 2, 3, 4 or 5, especially 0 or 1;

[0512] e and f are 0, 1, 2, 3, 4 or 5, especially 0 or 1;

[0513] W’ is S, S(O), SO2, O, a single bond, CH2, CH(CH3), C(CH3)2, especially S, S(O), SO2 or C(CH3)2;

[0514] and wherein R z 、R aa 、R ab 、R 7a 、R 7b and L are as defined for formula (V), and wherein R z is especially selected from a single bond, CH2 and OCH2CH2.

[0515] Structural units of general formulas (V-11) to (V-22) are particularly preferred, wherein R z and R aa are as defined herein, and wherein R z is especially selected from a single bond, CH2 and O-CH2CH2, and especially O-CH2CH2:

[0516]

[0517]

[0518] Among the structural units of formulas (V-1) to (V-8), the structural units of formulas (V-1), (V-2), (V-3) and (V-8) are particularly preferred. Among the structural units of formulas (V-11) to (V-22), the structural units of formulas (V-11), (V-12), (V-13), (V-14), (V-15), (V-21) and (V-22) are particularly preferred, and the structural units derived from the following are particularly preferred: 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene (BNE or BHBNA), 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthalene (DPBHBNA), 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (BPEF), 9,9-bis(6-(2-hydroxyethoxy)naphthalen-2-yl)fluorene (BNEF), 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene (BPPEF), 2-[4-[4-(2-hydroxyethoxy)-3,5-bis(thianthren-1-yl)phenyl]sulfonyl-2,6-bis(thianthren-1-yl)phenoxy]ethanol, 2-[4-[4-(2-hydroxyethoxy)-3,5-bis(phenanthren-9-yl)phenyl]sulfonyl-2,6-bis(phenanthren-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(phenanthren-9-yl)phenyl]-1-methylethyl]-2,6-bis(phenanthren-9-yl)phenoxy]ethanol, 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-bis(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 and 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-bis(thianthren-1-yl)phenyl]-1-methyl-ethyl]-2,6-bis(thianthren-1-yl)phenoxy]ethanol.

[0519] In a particularly preferred set of embodiments, 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 following: the structural unit of formula (V-11), the structural unit of formula (V-12), the structural unit of formula (V-13), the structural unit of formula (V-14), the structural unit of formula (V-15), the structural unit of formula (V-21) and the structural unit of formula (V-22). In this specific set of embodiments, it is preferred that the group R in the structural units of formulas (V-11), (V-12), (V-13), (V-14), (V-15), (V-21) and (V-22)z Those thermoplastic resins where it is O-CH2CH2.

[0520] Among the thermoplastic resins of this group of particularly preferred embodiments, preferably, based on the total amount of the structural units of formula (II) and (V), the total molar ratio of the structural units of formula (IIa) or (IIb) is in the range of 1-99 mol%, in the range of 10-99 mol%, more preferably in the range of 15-97 mol%, and even more preferably in the range of 25-95 mol%.

[0521] The 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 analogous methods of known methods.

[0522] For example, the compound of formula (IV-8) can be prepared by various synthetic methods, for example, as disclosed in Japanese Laid-Open No. 2014-227387, Japanese Laid-Open No. 2014-227388, Japanese Laid-Open No. 2015-168658, Japanese Laid-Open No. 2015-187098. For example, 1,1'-binaphthol can be reacted with ethylene glycol monotosylates; alternatively, 1,1'-binaphthol can be reacted with alkylene oxides, haloalkanols or alkylene carbonates; alternatively, 1,1'-binaphthol can be reacted with ethylene carbonates. Thus, the compound of formula (IV-8) is obtained, where R z -OH is O-Alk 4 -OH or O-Alk 4 -[O-Alk 4 -] w -OH.

[0523] For example, the compound of formula (IV-2) can be prepared by various synthetic methods, for example, as disclosed in Japanese Patent Publication No. 5442800 and Japanese Laid-Open No. 2014-028806. Examples include:

[0524] (a) React fluorenes with hydroxy naphthalenes in the presence of hydrochloric acid gas and mercapto carboxylic acids; (b) React 9-fluorenes with hydroxy naphthalenes in the presence of an acid catalyst (and an alkyl mercaptan); (c) React fluorenes with hydroxy naphthalenes in the presence of hydrochloric acid and a mercaptan (e.g., mercapto carboxylic acid); (d) React fluorenes with hydroxy naphthalenes in the presence of sulfuric acid and a mercaptan (e.g., mercapto carboxylic acid), and then crystallize the product from a crystallization solvent composed of a hydrocarbon and a polar solvent to form bisnaphthol fluorene; etc. Thus, a compound of formula (IV-2) can be obtained, wherein R z is a single bond.

[0525] The compound of formula (IV) (wherein R z is O-Alk 4 - or O-Alk 4 -[O-Alk 4 -] w -) can be prepared from the compound of formula (IV) (wherein R z is a single bond) by reaction with an epoxide or a haloalkanol. For example, react 9,9-bis(hydroxy naphthalenyl)-fluorene of formula (IV-2) (wherein R z is a single bond) with an epoxide or a haloalkanol to produce a compound of formula (IV-2) (wherein R z is O-Alk 4 - or O-Alk 4 -[O-Alk 4 -] w -). For example, 9,9-bis[6-(2-hydroxyethoxy)naphthalenyl]fluorene can be prepared by reacting 9,9-bis[6-(2-hydroxynaphthyl]fluorene with 2-chloroethanol under basic conditions.

[0526] The monomers of formula (I) and (IV) for manufacturing a thermoplastic resin may contain certain impurities generated from their preparation. For example, the comonomer (IV) may contain a hydroxy compound that carries an OH group instead of, for example, the group O-Alk 4 -OH, or may contain the group O-Alk 4 -[O-Alk 4 w - instead of the group O-Alk 4 -. 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 for preparing a thermoplastic resin is preferably 4000 ppm or less, especially 1500 ppm or less, and more preferably 1000 ppm or less. In particular, in the monomer mainly composed of the dihydroxy compound represented by formula (IV), wherein the group R Z ​The total amount of the dihydroxy compounds in which at least one of the -OH has a carbon number different from that of the dihydroxy compound of the formula (IV) 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. Wherein the group R Z The total content of the dihydroxy compounds in which at least one of the -OH has a carbon number different from that of the dihydroxy compound of the formula (IV) is further preferably 1000 ppm or less, and more preferably 500 ppm or less. Similarly, the amount of impurities in the monomer of the formula (I) will be within the range given for the monomer of the formula (IV).

[0527] Suitable thermoplastic resins for preparing optical devices such as lenses are specifically polycarbonates, polyester carbonates, and polyesters. Preferred thermoplastic resins for preparing optical devices such as lenses are specifically polycarbonates.

[0528] The polycarbonate is characterized by structural units having at least one of the formulas (II), (IIa), and (IIb) respectively, and optionally structural units derived from a diol monomer different from the monomer compound of the formula (I), such as the structural unit of the formula (V),

[0529] #-O-R z -A 3 -R z -O-#(V)

[0530] wherein

[0531] #, R z and A 3 are as defined above;

[0532] and a structural unit of the formula (III-1) derived from a carbonate-forming component:

[0533]

[0534] where each # represents a connection point with an adjacent structural unit, that is, the O at the connection point connecting to the structural unit of the formula (II), and the O at the connection point connecting to the structural unit of the formula (V) (if present).

[0535] The polyester is characterized by structural units having at least one of the formulas (II), (IIa), and (IIb) respectively, and optionally structural units derived from a diol monomer different from the monomer compound of the formula (I), such as the structural unit of the formula V. If X in the formula (II) 1a and X 2a or X in the formulas (IIa) and (IIb) aIf it is selected from -CH2O-, the polyester may have structural units derived from one or more dicarboxylic acids, such as the structural unit of formula (III-2) in the case of phthalic acid, the structural unit of formula (III-3) in the case of naphthoic acid, the structural unit of formula (III-4) in the case of oxalic acid, and the structural unit of formula (III-5) in the case of malonic acid:

[0536]

[0537] In formulas (III-2) to (III-5), each variable # represents a connection point to an adjacent structural unit, that is, the O that is the connection point to the structural unit of formula (II), and the O that is the connection point to the structural unit of formula (V) (if present).

[0538] The structural characteristics of the polyester carbonate are characterized by having at least one of the structural units of formulas (II), (IIa), and (IIb), optionally structural units derived from a diol monomer different from the monomer compound of formula (I), such as the structural unit of formula (V), the structural unit of formula (III-1) derived from a carbonate-forming component, and structural units derived from a dicarboxylic acid, such as the structural unit of formula (III-2) in the case of phthalic acid, the structural unit of formula (III-3) in the case of naphthoic acid, the structural unit of formula (III-4) in the case of oxalic acid, and the structural unit of formula (III-5) in the case of malonic acid.

[0539] Embodiments of a particular group relate 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 similarly the molar ratio of the structural unit of formula (II) to the structural unit of formula (V) is in the range of 1:99 to 99:1, in particular in the range of 10:90 to 99:1, especially 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 97:3, more preferably in the range of 20:80 to 96:4, or in the range of 25:75 to 96:4, especially in the range of 27:73 to 96:4 or in the range of 27:73 to 99:1, even more preferably in the range of 27:73 to 90:10, and especially in the range of 30:70 to 80:20 or in the range of 35:65 to 70:30. Thus, based on the total molar amount of the structural units of formula (II) and (V), the molar ratio of the structural unit of formula (II) is usually 1 to 99 mol%, in particular 10 to 99 mol%, more preferably in the range of 15 to 97 mol% or in the range of 5 to 99 mol%, especially in the range of 10 to 97 mol% or in the range of 17 to 97 mol%, even more preferably in the range of 17 to 90 mol%, and especially in the range of 20 to 80 mol% or in the range of 25 to 70 mol%. Thus, based on the total molar amount of the structural units of formula (II) and (V), the molar ratio of the structural unit of formula (V) is usually 1 to 99 mol%, in particular 1 to 90 mol%, more preferably in the range of 3 to 85 mol% or in the range of 1 to 95 mol%, especially in the range of 3 to 90 mol% or in the range of 3 to 83 mol%, even more preferably in the range of 10 to 83 mol%, and especially in the range of 20 to 80 mol% or in the range of 30 to 75 mol%.

[0540] Embodiments of a particular group relate to thermoplastic copolymer resins, in particular polycarbonates, poly(ester carbonate)s, and polyesters, having structural units of formula (II) and one or more structural units of formula (V-14) or (V-15), i.e., resins, in particular polycarbonates, poly(ester carbonate)s, 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 monomers of formula (IV-14) and (IV-15) and similarly 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 from 50:50 to 99:1, in particular in the range from 70:30 to 98:2, especially in the range from 80:20 to 97:3.

[0541] Embodiments of another specific group relate to thermoplastic copolymer resins, especially polycarbonates, poly(ester carbonate)s, and polyesters, having 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, especially polycarbonates, poly(ester carbonate)s, 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 monomers of formula (IV-11), (IV-12), (IV-13), (IV-21), and (IV-22) and similarly the molar ratio of the structural units of formula (II) to the structural units of formula (V-11), (V-12), (V-13), (V-21), and (V-22) are in the range from 30:70 to 90:10, in particular in the range from 40:60 to 85:15, especially in the range from 50:50 to 80:20.

[0542] The thermoplastic copolymer resin of the present invention, such as a polycarbonate resin, may include any one of a random copolymer structure, a block copolymer structure, and an alternating copolymer structure. The thermoplastic resin according to the present invention does not need to include all of the structural units (II) and one or more different structural units (V) in the same polymer molecule. That is, the thermoplastic copolymer resin according to the present invention may be a blended resin as long as the above structures are included in any of the plurality of polymer molecules. For example, a thermoplastic resin including all of the above structural units (II) and structural unit (V) may be a copolymer including all of the structural units (II) and structural unit (V), it may 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 may be a blended resin of a copolymer including at least one structural unit (II) and a first structural unit (V) and 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.

[0543] Thermoplastic polycarbonates can be obtained by the polycondensation of a diol component and a carbonate-forming component. Similarly, thermoplastic polyesters and polyester carbonates can be obtained by the polycondensation of a diol component and a dicarboxylic acid or its ester-forming derivative and optionally a carbonate-forming component.

[0544] Specifically, the thermoplastic resin (polycarbonate resin) can be prepared by the following method.

[0545] The method for preparing the thermoplastic resin of the present invention, such as a polycarbonate resin, includes a process of melt polycondensing a dihydroxy component corresponding to the above structural unit with a dicarbonate. According to the present invention, the dihydroxy compound includes at least one dihydroxy compound represented by formula (I), especially a dihydroxy compound represented by formula (Ia) or (Ib) as defined herein. In addition to the compound of formula (I), the dihydroxy compound may further include one or more dihydroxy compounds represented by formula (IV), preferably formula (IV-1) to (IV-8), especially a dihydroxy compound represented by formula (IV-11) to (IV-22), particularly a dihydroxy compound represented by formula (IV-11), (IV-12), (IV-13), (IV-14), (IV-15), (IV-21), or (IV-22).

[0546] As is clear from the foregoing, polycarbonate resins can be formed by reacting a dihydroxy component with a carbonate precursor such as a carbonate diester, wherein the dihydroxy component includes at least one compound represented by formula (I), (Ia), and (Ib) respectively, or at least one compound represented by formula (I), (Ia), and (Ib) respectively and at least one combination of compounds 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, polycarbonate resins can be formed by melt polycondensation, wherein the 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 carbonate diester in the presence of a basic compound catalyst, a transesterification catalyst, or a mixed catalyst thereof, or under conditions without a catalyst.

[0547] Thermoplastic resins (or polymers) other than polycarbonate resins, such as polyester carbonates and polyesters, are obtained by using the 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 materials (or monomers).

[0548] As previously mentioned, the monomers of formula (I) used to manufacture thermoplastic resins and similarly the comonomers of formula (IV) can contain impurities resulting from their preparation.

[0549] For example, the monomers of formula (IV-1) and (IV-2) wherein R z is O-Alk 4 - or O-Alk4 -[O-Alk 4 -] w -) may include a dihydroxy compound in which two of the Rs z are both single bonds, or a dihydroxy compound in which one of the Rs z is a single bond instead of O-Alk 4 - or O-Alk 4 -[O-Alk 4 -] w -.

[0550] In a monomer mainly composed of a dihydroxy compound represented by formula (IV-1) or (IV-2), the total amount of such dihydroxy compounds of formula (IV-1) or (IV-2) (where at least one R z is different from O-Alk 4 - or O-Alk 4 -[O-Alk 4 -] w -) 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 formula (IV-1) or (IV-2) is also preferably 300 ppm or less, and more preferably 200 ppm or less.

[0551] 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), particularly at least one monomer (I) preferably mentioned herein, with a combination of one or more monomer compounds of formula (IV), particularly monomer compounds of formula (IV-11), (IV-12), (IV-13), (IV-14), (IV-15), (IV-21), or (IV-22), etc. as the dihydroxy component with a carbonate precursor such as a carbonic acid diester.

[0552] However, during the polymerization process for manufacturing the polycarbonate resin, some compounds of formula (I) and (IV) may be converted into impurities, in which one or both of the terminal R z OH groups are replaced with different groups, such as a vinyl terminal group represented by -OCH=CH2. Since the amount of such impurities is usually small, the formed polymer product can be used as a polycarbonate resin without a purification process.

[0553] 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 formed during the process of forming the thermoplastic resin, unreacted carbonic acid diesters, and monomers. The total amount of impurities in the thermoplastic resin may be 5000 ppm or less, or 2000 ppm or less. The total amount of impurities in the thermoplastic resin is preferably 1000 ppm or less, more preferably 500 ppm or less, still more preferably 200 ppm or less, and particularly preferably 100 ppm or less.

[0554] The total amount of phenols as impurities in the thermoplastic resin may be 3000 ppm or less or 2000 ppm or less. The total amount of phenols as impurities is preferably 1000 ppm or less, more preferably 800 ppm or less, still more preferably 500 ppm or less, and particularly preferably 300 ppm or less.

[0555] The total amount of carbonic acid diesters 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, and particularly preferably 50 ppm or less.

[0556] 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, and particularly preferably 500 ppm or less.

[0557] The lower limit of the total amount of these impurities is not important, but may be 0.1 ppm or 1.0 ppm.

[0558] 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.

[0559] By adjusting the amounts of phenols and carbonic acid diesters, a resin having target properties can be formed. The amounts of phenols, carbonic acid diesters, and monomers can be appropriately adjusted by adjusting the polycondensation conditions, the operating conditions of the apparatus used for polymerization, and the conditions of extrusion molding after the polycondensation process.

[0560] As measured by GPC (gel permeation chromatography), the weight average molecular weight (Mw) of the thermoplastic resin according to the present invention is preferably in the range of 5,000 to 100,000 daltons, more preferably in the range of 10,000 to 80,000 daltons, and particularly in the range of 10,000 to 50,000 daltons. GPC measurement can be calibrated by using polystyrene standards. The Mw of the thermoplastic resin according to the present invention measured in this way is also expressed herein as "weight average molecular weight based on polystyrene". The number average molecular weight (Mn) of the thermoplastic resin according to the present invention is preferably in the range of 3,000 to 30,000, more preferably 5,000 to 25,000, and particularly in the range of 7,000 to 20,000. 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 even more preferably 10,000 to 18,000.

[0561] The value of the molecular weight distribution (Mw / Mn) of the thermoplastic resin according to the present invention is preferably 1.5 to 9.0, more preferably 1.8 to 7.0, and even more preferably 2.0 to 4.0.

[0562] When the thermoplastic resin has a weight average molecular weight (Mw) value within the above 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.

[0563] Preferably, based on the total weight of the thermoplastic resin, the thermoplastic resin contains 9% by weight or less, especially 7% by weight or less, and particularly 5% by weight or less, for example 0.1 to 9% by weight, especially 0.1 to 7% by weight, and particularly 0.1 to 5% by weight of low molecular weight compounds having a molecular weight of less than 1,000. If such low molecular weight compounds are present in the thermoplastic resin in the above range, the mechanical strength of the molded body made of such a thermoplastic resin generally increases, especially 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 this embodiment contains 9% by weight or less, especially 7% by weight or less, and particularly 5% by weight of low molecular weight compounds having a molecular weight of less than 1,000, and during the molding process (such as an injection molding process), the low molecular weight compounds are not easily precipitated or only slightly precipitated (also referred to as bleed - out). In contrast, the molding of a thermoplastic resin having a higher amount of low molecular weight compounds may be accompanied by a greater degree of bleed - out.

[0564] The thermoplastic resin of the present invention, for example especially the above - mentioned polycarbonate resin, has a high refractive index (n D or n d), and thus is suitable for producing optical lenses. The refractive index values referred to in this article are the values for a film with a thickness of 0.1 mm, which can be measured using an Abbe refractometer according to the method of JIS-K-7142. The refractive index of the thermoplastic resin of the present invention, especially the polycarbonate resin of the present invention, at 23 °C and a wavelength of 589 nm, when the resin includes the structural unit (II), is generally 1.650 or more, preferably 1.660 or more, more preferably 1.670 or more, still more preferably 1.680 or more, especially 1.690 or more, for example 1.700 or more. For example, the refractive index of the copolycarbonate resin including the structural unit (II) and the structural unit (V) according to the present invention is preferably 1.660 to 1.800, preferably 1.670 to 1.800, still more preferably 1.680 to 1.800.

[0565] The Abbe number (ν) of the thermoplastic resin of the present invention, especially the polycarbonate resin of the present invention, is preferably 24 or less, more preferably 22 or less, still more preferably 20 or less. The Abbe number can be calculated by the following formula based on the refractive indices at wavelengths of 487 nm, 589 nm, and 656 nm at 23 °C.

[0566] ν=(n D -1) / (n F -n C )

[0567] n D : Refractive index at a wavelength of 589 nm

[0568] n C : Refractive index at a wavelength of 656 nm

[0569] n F : Refractive index at a wavelength of 486 nm

[0570] The glass transition temperature (Tg) of the thermoplastic resin of the present invention, especially the polycarbonate resin of the present invention, considering that polycarbonate can be used for injection molding, 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, especially in the range of 110 to 160 °C. 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 resin melting temperature may be too high, so that the resin will decompose or color undesirably. In addition, it allows the preparation of molded articles with high surface accuracy. The given value of the glass transition temperature refers to the value measured by differential scanning calorimetry (DSC) using a heating program of 10 °C / minute according to the method of JIS K7121-1987.

[0571] The absolute value of the orientation birefringence of the thermoplastic resin of the present invention, particularly the polycarbonate resin of the present invention, is preferably in the range of 0 to 1×10 -2 and more preferably in the range of 0 to 5×10 -3 and even more preferably in the range of 0 to 2×10 -3 and particularly in the range of 0 to 1×10 -3 and especially in the range of 0 to 0.4×10 -3 .

[0572] The total light transmittance of an optical molded article such as an optical element made by using the polycarbonate resin of the present invention is preferably 85% or more, more preferably 87% or more, and particularly preferably 88% or more. A total light transmittance of preferably 85% or more is as good as that provided by a bisphenol A type polycarbonate resin or the like.

[0573] The thermoplastic resin according to the present invention has high moisture and heat resistance. The moisture and heat resistance can be evaluated by the following method: perform a "PCT test" (autoclave test) on a molded article such as an optical element made of the thermoplastic resin, and then measure the total light transmittance of the molded article after the PCT test. In the PCT test, first, an injection molded article with a diameter of 50 mm and a thickness of 3 mm is held for 20 hours at 120 °C, 0.2 MPa, and 100% RH for 20 hours using PC305S III manufactured by HIRAYAMA Corporation. Then, the injection molded article sample is taken out of the apparatus, and the total light transmittance is measured according to the method of JIS-K-7361-1 using a SE2000 type spectro-parallax meter manufactured by Nippon Denshoku Industries Co., Ltd.

[0574] 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, it is considered that the thermoplastic resin has higher moisture and heat resistance than conventional thermoplastic resins.

[0575] The b value (representing hue) of the thermoplastic resin according to the present invention is preferably 5 or less. The smaller the b value, the less yellow the color, and the better the hue.

[0576] According to the present invention, the glycol component for preparing polycarbonate or polyester may additionally include one or more glycol monomers different from the monomer compounds of formula (I), such as one or more monomers of formula (IV).

[0577] Suitable diol monomers that are different from the monomer compounds of formula (I) are those that are conventionally used to prepare polycarbonates, such as

[0578] - aliphatic diols, such as ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, and hexylene glycol;

[0579] - cycloaliphatic diols, such as tricyclo[5.2.1.02,6]decane dimethanol, cyclohexane-1,4-dimethanol, naphthalane-2,6-dimethanol, norbornane dimethanol, pentacyclopentadecane-dimethanol, cyclopentane-1,3-dimethanol, spiroglycerol, 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

[0580] - Aromatic diols, especially aromatic diols of formula (IV), such as 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, bis(4-hydroxyphenyl)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)dihydroxyphenyl]-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-cyclohexylphenyl]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-hydroxynaphthalen-2-yl)fluorene, 9,9-bis(6-(2-hydroxyethyl)naphthalen-2-yl)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-bis(thianthren-1-yl)phenyl]sulfonyl-2,6-bis(thianthren-1-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(phenanthren-9-yl)phenyl]-1-methylethyl]-2,6-bis(phenanthren-9-yl)phenoxy]ethanol and 2,2'-[1,1'-binaphthalene-2,2'-diylbis(oxy)]diethanol (also known as 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene or 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene (BNE)).

[0581] Preferably, in addition to the monomer of formula (I), the diol component further comprises at least one monomer of formula (IV). In particular, the total amount of the monomers of formula (I) and (IV), based on the total weight of the diol component, accounts for at least 90% by weight of the diol component, or based on the total molar amount of the diol monomers of the diol component, accounts for at least 90% by mole of the diol component. In particular, in addition to the monomer of formula (I), the diol component further comprises at least one monomer selected from the monomers of formula (IV-11) to (IV-22). More particularly, in addition to the monomer of formula (I), the diol component further comprises at least one monomer selected from the monomers of formula (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 further comprises at least one monomer selected from the following: 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene, 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthalene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 2-[4-[4-(2-hydroxyethoxy)-3,5-bis(thianthren-1-yl)phenyl]sulfonyl-2,6-bis(thianthren-1-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(phenanthren-9-yl)phenyl]-1-methylethyl]-2,6-bis(phenanthren-9-yl)phenoxy]ethanol and 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene and combinations thereof.

[0582] Generally, based on the total weight of the diol component, the relative amount of the monomer compound of formula (I) is at least 1% by weight, preferably at least 10% by weight, or at least 25% by weight, in particular at least 15% by weight, or at least 20% by weight, especially at least 15% by weight, or at least 25% by weight, preferably in the range of 1 to 99% by weight, or in the range of 10 to 98% by weight, in particular in the range of 15 to 98% by weight, or in the range of 20 to 98% by weight, or in the range of 25 to 98% by weight, or in the range of 25 to 97% by weight, especially in the range of 10 to 96% by weight, or in the range of 15 to 95% by weight, or in the range of 25 to 95% by weight, or in the range of 25 to 93% by weight, but can also be up to 100% by weight.

[0583] Generally, based on the total molar amount of the diol component, the relative molar amount of the monomeric compound of formula (I) is at least 1 mol%, preferably at least 10 mol%, or at least 25 mol%, especially at least 15 mol%, or at least 20 mol%, particularly at least 15 mol%, or at least 25 mol%, preferably in the range of 1 to 99 mol%, or in the range of 10 to 98 mol%, or in the range of 15 to 98 mol%, or in the range of 20 to 98 mol%, especially in the range of 10 to 96 mol%, or in the range of 15 to 95 mol%, or in the range of 25 to 95 mol%, or in the range of 25 to 93 mol%, particularly in the range of 15 to 90 mol%, or 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%, but can also be up to 100 mol%.

[0584] Therefore, based on the total molar amount of the diol component, the relative molar amount of the monomeric compound of formula (IV) will not exceed 99 mol% or 90 mol% or 75 mol%, especially not exceed 85 mol% or 80 mol%, particularly not exceed 85 mol% or 75 mol%, and 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 85 mol%, or in the range of 3 to 75 mol%, especially in the range of 4 to 90 mol%, or in the range of 5 to 85 mol%, or in the range of 5 to 75 mol%, or in the range of 7 to 75 mol%, particularly in the range of 10 to 85 mol%, or 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%, but can also be up to 99.9 mol%.

[0585] Generally, based on the total molar amount of the diol monomers in the diol component, the total molar amount of the monomers of formula (I) and formula (IV) is at least 80 mol%, especially at least 90 mol%, particularly at least 95 mol%, or up to 100 mol%.

[0586] Examples of further preferred aromatic dihydroxy compounds that can be used in addition to the monomers of formula (I) and optionally the monomers of formula (IV) 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.

[0587] To adjust the molecular weight and melt viscosity, the monomers for forming the thermoplastic polymer may further 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. To increase the molecular weight and melt viscosity, the monomers for forming the thermoplastic polymer may further include polyfunctional compounds, which are polyfunctional alcohols having three or more hydroxyl groups in the case of polycarbonates and polyfunctional alcohols having three or more hydroxyl groups or polyfunctional carboxylic acids having 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 having 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 generally does not exceed 10 mol%.

[0588] Suitable carbonate-forming monomers are those conventionally used as carbonate-forming monomers in the preparation of polycarbonates, which include, but are 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. The usage ratio of the carbonate-forming monomer is generally 0.97 to 1.20 mol, more preferably 0.98 to 1.10 mol, relative to a total of 1 mol of the dihydroxy compound.

[0589] Suitable dicarboxylic acids include, but are not limited to

[0590] -aliphatic dicarboxylic acids, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid;

[0591] -alicyclic dicarboxylic acids, such as tricyclo[5.2.1.02,6]decane dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, decalin-2,6-dicarboxylic acid, and norbornane dicarboxylic acid; and

[0592] -aromatic dicarboxylic acids, such as phthalic acid, specifically o-phthalic acid, m-phthalic acid, 2-methyl terephthalic acid, or terephthalic acid, and naphthalenedicarboxylic acid, specifically 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'-binaphthalene (Formula DC3), and naphthalene-2,7-dicarboxylic acid.

[0593]

[0594]

[0595] Suitable ester-forming derivatives of dicarboxylic acids include, but are not limited to, dialkyl esters, diphenyl esters, and xylenyl esters.

[0596] In the case of polyesters, the usage ratio of the ester-forming monomers is generally 0.97 to 1.20 moles, more preferably 0.98 to 1.10 moles, relative to a total of 1 mole of the dihydroxy compound.

[0597] The polycarbonates of the present invention can be prepared by reacting a glycol component including monomers of formula (I) and optionally additional glycol monomers such as monomers of formula (IV) with a carbonate-forming monomer by a preparation method similar to the known polycarbonate preparation methods described in, for example, US 9,360,593, US2016 / 0319069, and US2017 / 0276837 (which are incorporated herein by reference in their entirety).

[0598] The polyesters of the present invention can be prepared by reacting a glycol component including monomers of formula (I) and optionally additional glycol monomers such as monomers of formula (IV) with a dicarboxylic acid or its ester-forming derivative by a preparation method similar to the known polyester preparation methods described in, for example, US2017 / 044311 and the documents cited therein (which are incorporated herein by reference in their entirety).

[0599] The polyester carbonates of the present invention can be prepared by reacting a glycol component including monomers of formula (I) and optionally additional glycol monomers such as monomers of formula (IV), a carbonate-forming monomer, and a dicarboxylic acid or its ester-forming derivative by a preparation method similar to the preparation of polyester carbonates known in the art.

[0600] In the case of using a carbonate-forming monomer or an ester-forming derivative of a polycarboxylic acid, polycarbonates, polyesters, and polyester carbonates are generally prepared by reacting the monomers of the glycol component with a carbonate-forming monomer and / or an ester-forming monomer, i.e., a dicarboxylic acid or its ester-forming derivative, in the presence of an esterification catalyst, especially a transesterification catalyst.

[0601] Suitable transesterification catalysts include 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 include acidic compounds, which specifically include, but are not limited to, Lewis acid compounds of polyvalent metals, including compounds of, for example, zinc, tin, titanium, zirconium, lead, etc.

[0602] Examples of suitable alkali metal compounds include alkali metal salts of organic acids such as acetic acid, stearic acid, benzoic acid or phenylphosphoric acid, alkali metal phenolates, alkali metal oxides, alkali metal carbonates, alkali metal borohydrides, alkali metal bicarbonates, alkali metal phosphates, alkali metal hydrogen phosphates, alkali metal hydroxides, alkali metal hydrides, alkali metal alkoxides, etc. 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 phenylphosphate; also include disodium, dipotassium, dicesium and dilithium salts of bisphenol A, sodium, potassium, cesium and lithium salts of phenol; and so on.

[0603] Examples of alkaline earth metal compounds include alkaline earth metal salts of organic acids such as acetic acid, stearic acid, benzoic acid or phenylphosphoric acid, alkaline earth metal phenolates, alkaline earth metal earth oxide, alkaline earth metal carbonates, alkali metal borohydrides, alkaline earth metal bicarbonates, 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 bicarbonate, calcium bicarbonate, strontium bicarbonate, barium bicarbonate, 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.

[0604] Examples of nitrogen-containing compounds include quaternary ammonium hydroxides, their salts, amines, etc. Specific examples thereof include quaternary ammonium hydroxides containing alkyl, aryl, 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.

[0605] Examples of preferred transesterification catalysts include salts of polyvalent metals such as zinc, tin, titanium, zirconium, lead, etc., especially 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(II) chloride, tin(IV) chloride, tin(II) acetate, tin(IV) acetate, dibutyltin dilaurate, dibutyltin oxide, dibutyltin methoxide, zirconium acetylacetonate, zirconium oxyacetate, tetrabutoxyzirconium, lead(II) acetate, lead(IV) acetate, etc.

[0606] The usage ratio of the transesterification catalyst is generally 10 -9 to 10 -3 moles, preferably 10 -7 to 10 -4 moles, relative to a total of 1 mole of the dihydroxy compound.

[0607] Generally, polycarbonates, polyesters, and polyester carbonates are prepared by melt polycondensation. In melt polycondensation, the monomers react in the absence of an additional inert solvent. While the reaction is proceeding, any by-products formed in the transesterification reaction are removed by heating the reaction mixture under ambient pressure or reduced pressure.

[0608] The melt polycondensation reaction preferably includes loading the monomers and the catalyst into a reactor and subjecting the reaction mixture to conditions under which the reaction between the monomers and the formation of by-products occur. It has been found that it is beneficial if the by-products remain in the polycondensation reaction for at least a certain period of time. However, in order to drive the polycondensation reaction towards the product side, it is beneficial to remove at least a part of the by-products formed during or preferably at the end of the polycondensation reaction. 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 decreasing the pressure. The reaction time for this step is more than 20 minutes and less than 240 minutes, preferably more than 40 minutes and less than 180 minutes, particularly preferably more than 60 minutes and less than 150 minutes. In this step, when the by-products are removed quickly by distillation after being produced, the finally obtained thermoplastic resin has a low content of high molecular weight resin molecules. On the contrary, when the by-products are allowed to remain in the reactor for a certain period of time, the finally obtained thermoplastic resin has a high content of high molecular weight resin molecules.

[0609] The melt polycondensation reaction can be carried out in a continuous system or a batch system. The reactors that can be used for the reaction can be vertical reactors, including anchor-type stirring blades, stirring blades, helical ribbon-type stirring blades, etc.; horizontal reactors, including paddle-type blades, grid-type blades, spectacle-type blades, etc.; or extruder-type reactors, including screws. Considering the viscosity of the polymerization product, it is preferred to use a reactor including a combination of these reactors.

[0610] According to a method for manufacturing a thermoplastic resin such as polycarbonate resin, after the polymerization reaction is completed, the catalyst can be removed or deactivated to maintain thermal stability and hydrolysis stability. A preferred method for deactivating the catalyst is to add an acidic substance. Specific examples of the acidic substance include esters such as butyl benzoate; aromatic sulfonates such as p-toluenesulfonic acid; aromatic sulfonic acid esters such as butyl p-toluenesulfonate, hexyl p-toluenesulfonate; phosphoric acids such as phosphorous acid, phosphoric acid, phosphonic acid; 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, monooctyl phosphite; phosphates such as triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, dibutyl phosphate, dioctyl phosphate, monooctyl phosphate; phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid, dibutylphosphonic acid; phosphonic acid esters such as diethyl phenylphosphonate; phosphines such as triphenylphosphine, bis(diphenylphosphino)ethane; boric acids such as boric acid, phenylboric acid; aromatic sulfonates such as tetrabutylphosphonium dodecylbenzenesulfonate; organic halides such as stearoyl chloride, benzoyl chloride, p-toluenesulfonyl chloride; alkyl sulfonic acids such as dimethylsulfonic acid; organic halides such as benzyl chloride. 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 mmHg and a temperature of 200 to 350 °C. For this step, a horizontal device including stirring blades with high surface renewal ability such as paddle blades, grid blades, spectacle blades, etc., or a thin-film evaporator is preferably used.

[0611] Desirably, a thermoplastic resin such as polycarbonate resin has a very small amount of foreign matter. Therefore, it is preferred to filter the molten product to remove any solids from the melt. The mesh size 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 size 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 carried out in a low-dust environment. The dust environment is preferably class 6 or less, more preferably class 5 or less.

[0612] The thermoplastic resin can be molded by any conventional molding method used for manufacturing optical elements. Suitable molding methods include, but are not limited to, injection molding, compression molding, casting, roll processing, extrusion molding, stretching, and the like.

[0613] Although the thermoplastic resin of the present invention can be molded as such, a resin composition can also be molded. The above resin composition contains at least one thermoplastic resin of the present invention and also contains at least one additive and / or other resin. Suitable additives include antioxidants, processing stabilizers, light stabilizers, polymerization metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, antibacterial agents, mold release agents, ultraviolet absorbers, plasticizers, compatibilizers, and the like. Suitable other resins are, for example, other polycarbonate resins, polyester carbonate resins, polyester resins, polyamides, polyacetals, etc. that do not contain the repeating unit of formula (I).

[0614] 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 - tetra[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, 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), diethyl 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate, 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. With respect to 100 parts by weight of the thermoplastic resin, the content of the antioxidant in the thermoplastic resin is preferably from 0.001 to 0.3 parts by weight.

[0615] Examples of processing stabilizers include, but are not limited to, phosphorus-based processing stabilizers, sulfur-based processing stabilizers, etc. Examples of phosphorus-based processing stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, their esters, etc. 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, tristearyl phosphite, diphenylmonoalkylphenyl phosphite (where the alkyl group can be decyl, octyl, isopropyl, etc.), monophenyl dialkylphenyl phosphite (where the alkyl group can be butyl, decyl, octyl, etc.), 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 diphosphite, distearylpentaerythritol diphosphite, 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'-biphenyldiphosphite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenyldiphosphite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenyldiphosphite, bis(2,4-di-tert-butylphenyl)-4-phenyl-benzenephosphite, bis(2,4-di-tert-butylphenyl)-3-phenyl-benzenephosphite, etc. Relative to 100 parts by weight of the thermoplastic resin, the content of the phosphorus-based processing stabilizer in the thermoplastic resin composition is preferably from 0.001 to 0.2 parts by weight.

[0616] Examples of sulfur-based processing stabilizers include, but are not limited to, pentaerythritol-tetrakis(3-laurylthiopropionate), pentaerythritol-tetrakis(3-myristylthiopropionate), pentaerythritol-tetrakis(3-stearylthiopropionate), dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, etc. Relative to 100 parts by weight of the thermoplastic resin, the content of the sulfur-based processing stabilizer in the thermoplastic resin composition is preferably from 0.001 to 0.2 parts by weight.

[0617] The preferred mold release agent contains at least 90% by weight of an ester of an alcohol and a fatty acid. Specific examples of the ester of an alcohol and a fatty acid include esters of a monohydric alcohol and a fatty acid, and partial or complete esters of a polyhydric alcohol and a fatty acid. Preferred examples of the above-mentioned ester of an alcohol and a fatty acid include esters of a monohydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. Preferred examples of the partial or complete ester of a polyhydric alcohol and a fatty acid include partial or complete esters of a polyhydric alcohol having 2 to 25 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. Specific examples of the ester of a monohydric alcohol and a fatty acid include stearyl stearate, palmitoyl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, etc. Specific examples of the partial or complete ester of a polyhydric alcohol and a fatty acid include glycerol monostearate, glyceryl monostearate, glyceryl distearate, glyceryl tristearate, sorbitan monostearate, glyceryl behenate, glyceryl caprylate, glyceryl laurate, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetraisononanoate, propylene glycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, complete or partial esters of dipentaerythritol, such as dipentaerythritol hexastearate, etc. With respect to 100 parts by weight of the thermoplastic resin, the content of the mold 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 still more preferably 0.02 to 0.5 parts by weight.

[0618] The preferred ultraviolet absorber is selected from benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, triazine ultraviolet absorbers, cyclic imidazoline ultraviolet absorbers, and cyanoacrylate ultraviolet absorbers. That is, the following ultraviolet absorbers can be used alone or in combination of two or more.

[0619] Examples of benzotriazole UV 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-(2H-benzotriazol-2-yl)phenol)], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-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-benzotriazolylphenyl), 2,2'-p-phenylenebis(1,3-benzoxazin-4-one), 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole, etc.

[0620] Examples of benzophenone UV absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 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-dodecyloxypbenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, etc.

[0621] Examples of triazine UV absorbers 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, etc.

[0622] Examples of the cyclic iminoester-based UV absorbers include 2,2'-bis(3,1-benzoxazin-4-one), 2,2'-p-phenylene bis(3,1-benzoxazin-4-one), 2,2'-m-phenylene bis(3,1-benzoxazin-4-one), 2,2'-(4,4'-biphenyl) bis(3,1-benzoxazin-4-one), 2,2'-(2,6-naphthalene) bis(3,1-benzoxazin-4-one), 2,2'-(1,5-naphthalene) bis(3,1-benzoxazin-4-one), 2,2'-(2-methyl-p-phenylene) bis(3,1-benzoxazin-4-one), 2,2'-(2-nitro-p-phenylene) bis(3,1-benzoxazin-4-one), 2,2'-(2-chloro-p-phenylene) bis(3,1-benzoxazin-4-one), etc.

[0623] Examples of the cyanoacrylate-based UV absorbers 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, etc.

[0624] Relative to 100 parts by weight of the thermoplastic resin, the content of the UV absorber in the resin composition is preferably from 0.01 to 3.0 parts by weight, more preferably from 0.02 to 1.0 parts by weight, and still more preferably from 0.05 to 0.8 parts by weight. The UV absorber contained in such a content range according to the use can provide sufficient weather resistance to the thermoplastic resin.

[0625] As described above, the thermoplastic polymer resins respectively including the repeating units of formula (II), (IIa) and (IIb) as described herein, especially polycarbonate resins, provide high transparency and high refractive index to the thermoplastic resin, and thus are suitable for preparing optical devices that require high transparency and high refractive index. More precisely, the thermoplastic polycarbonates respectively having the structural units of formula (II), (IIa) and (IIb) are characterized by having a high refractive index, and the refractive index is preferably at least 1.640, more preferably at least 1.660, especially at least 1.670.

[0626] The contribution of the monomers of formula (I), (Ia) and (Ib) to the refractive index of a thermoplastic resin, especially a polycarbonate resin, will depend 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 monomers used to prepare the thermoplastic resin, and the refractive index of the monomers used to prepare the thermoplastic resin can be measured by refractometer or determined ab initio, for example using the computer software ACD / ChemSketch 2012 (Advanced Chemistry Development, Inc.).

[0627] In the case of a thermoplastic copolymer resin, the refractive index of the thermoplastic resin, especially a polycarbonate resin, can be calculated from the refractive indices of the homopolymers of the individual monomers forming the copolymer resin by the following so-called "Fox equation":

[0628] 1 / n D = x1 / n D1 + x2 / n D2 +....x n / n Dn ,

[0629] where n D is the refractive index of the copolymer, x1, x2....x n are the mass fractions of monomers 1, 2....n in the copolymer, and n D1 , n D2 ....n Dn are the refractive indices of the homopolymers prepared from only one of monomers 1, 2...n individually. In the case of polycarbonate, x1, x2....x n are the mass fractions of OH monomers 1, 2...n based on the total amount of OH monomers. Obviously, the higher the refractive index of the homopolymer, the higher the refractive index of the copolymer will be.

[0630] The refractive index of a thermoplastic resin can be measured directly or indirectly. For direct measurement, according to the protocol of JIS-K-7142, 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 film of the thermoplastic resin. D。In the case of the refractive index of the homopolycarbonate of the compound of formula (I), the refractive index can also be determined indirectly. For this purpose, according to the procedure of Example 1 in column 48 of US 9,360,593, a copolycarbonate of each monomer of formula (I) with 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene and diphenyl carbonate was prepared, and according to the procedure of JIS-K-7142, using an Abbe refractometer and applying a 0.1 mm copolycarbonate film, the refractive index n of the copolycarbonate was measured at a wavelength of 589 nm D 。Based on the refractive index n thus measured D , the refractive index of the homopolycarbonate of the corresponding monomer can be calculated by applying the Fox equation and the known refractive index of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (n D (589 nm) = 1.639).

[0631] The compound of formula (I) can be obtained in a purity that provides a low yellowness index Y.I. as measured according to ASTM E313, which is also very important for use in the preparation of optical resins.

[0632] More precisely, the yellowness index Y.I. of the compound of formula (I) as measured according to ASTM E313 is preferably not more than 100, more preferably not more than 50, even more preferably not more than 20, especially not more than 10 or not more than 5.

[0633] 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 transparent conductive substrates that can be used in liquid crystal displays, organic EL displays, solar cells, etc. In addition, the thermoplastic resin of the present invention can be used as a structural material for optical components such as optical discs, liquid crystal panels, optical cards, optical sheets, optical fibers, connectors, evaporated plastic mirrors, displays, etc.; or as an optical device suitable for functional material applications.

[0634] Therefore, a molded article of an optical device, for example, can be formed using the thermoplastic resin of the present invention. 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.

[0635] Due to its 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 a 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.

[0636] In addition, the thermoplastic resin of the present invention can be mixed with additives for forming optical devices. As the additives for forming optical devices, the additives described above can be used. The additives may include antioxidants, processing stabilizers, light stabilizers, polymerization metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, antibacterial agents, mold release agents, ultraviolet absorbers, plasticizers, compatibilizers, and the like.

[0637] As is obvious from the above, another aspect of the present invention relates to an optical device made of the thermoplastic resin as defined above, wherein the thermoplastic resin includes structural units represented by formula (II) and optionally formula (V). Regarding the preferred meanings and preferred embodiments of the structural units of formula (II) and (V), reference is made to the descriptions given above.

[0638] Optical devices made of an optical resin including repeating units of formula (II) as defined herein and optionally repeating units of formula (V) are generally optical molded articles, such as optical lenses, such as automotive headlight lenses, Fresnel lenses, fθ lenses for laser printers, camera lenses, lenses for glasses, and projection lenses for rear projection TVs, CD-ROM pickup lenses, and optical elements for optical discs, image display media, optical films, film substrates, filters or prisms, liquid crystal panels, optical cards, optical sheets, optical fibers, optical connectors, deposited plastic mirrors, etc. Optical lenses and optical films are particularly preferred herein. The optical resin including repeating units of formula (II) and optionally repeating units of formula (V) can also be used to manufacture a transparent conductive substrate that can be used for optical devices and is suitable as a structural element or functional element of a transparent conductive substrate for liquid crystal displays, organic EL displays, solar cells, etc.

[0639] The optical lens made of 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 and heat resistance. Therefore, the optical lens can be used in fields where expensive glass lenses with a high refractive index are conventionally used, such as for telescopes, binoculars, and television projectors. Preferably, the optical lens is used in the form of an aspherical lens. Just one aspherical 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, aspherical lenses are particularly useful as camera lenses. The present invention easily provides an aspherical lens having a high refractive index and a low birefringence level, which is technically difficult to manufacture by processing glass.

[0640] The optical lens of the present invention can be formed by the following methods: for example, injection molding, compression molding, injection compression molding, or casting of a resin including repeating units of formula (II) as defined herein and optionally repeating units of formula (V).

[0641] The optical lens of the present invention is characterized in that the optical distortion is very small. An optical lens including a conventional optical resin has a large optical distortion. Although it is not impossible to reduce the optical distortion value 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 optionally the repeating unit of formula (V) has extremely small optical distortion caused by resin orientation and small molding distortion, excellent optical elements can be obtained without strictly setting molding conditions.

[0642] In order to manufacture the optical lens of the present invention by injection molding, preferably, the lens is molded at a barrel temperature of 260 °C to 320 °C and a mold temperature of 100 °C to 140 °C.

[0643] As needed, the optical lens of the present invention is advantageously used as an aspherical lens. Since spherical aberration can be substantially eliminated with a single aspherical lens, it is not necessary to use a combination of spherical lenses to eliminate spherical aberration, thereby reducing the weight and manufacturing cost. Therefore, among optical lenses, aspherical lenses are particularly useful as camera lenses.

[0644] Since the resin having the repeating unit of formula (II) as defined herein and optionally the repeating unit of formula (V) has high moldability, they are particularly useful as materials for thin optical lenses with small sizes and complex shapes. As the lens size, the thickness of the central part of the lens is 0.05 to 3.0 mm, preferably 0.05 to 2.0 mm, 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, more preferably 3.0 to 10.0 mm. A meniscus lens is preferred, which bulges on one side and is concave on the other side.

[0645] As needed, the surface of the optical lens of the present invention may have a coating, such as an antireflection layer or a hard coating. The antireflection layer may be single-layer or multi-layer, composed of an organic material or an inorganic material, but 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.

[0646] The optical lens of the present invention can be formed by any method such as metal molding, cutting, polishing, laser processing, electrical discharge machining, or edge grinding. Metal molding is preferred.

[0647] The optical film made of the thermoplastic resin according to the present invention has high transparency and heat resistance, and is therefore preferably applicable to liquid crystal substrate films, optical memory cards, etc. Needless to say, in order to avoid foreign matter incorporation into the optical film as much as possible, molding needs to be carried out in a low-dust environment. The dust environment is preferably below class 6, more preferably below class 5.

[0648] The following examples are used for further illustration of the present invention.

[0649] 1. Abbreviation:

[0650] m.p.: melting point

[0651] eq.: molar equivalent

[0652] MEK: 2-butanone (methyl ethyl ketone)

[0653] THF: tetrahydrofuran

[0654] TBME: tert-butyl methyl ether

[0655] MeOH: methanol

[0656] 2-Me-THF: 2-methyltetrahydrofuran

[0657] K2CO3: potassium carbonate

[0658] KI: potassium iodide

[0659] Na2CO3: sodium carbonate

[0660] NaHCO3: sodium bicarbonate

[0661] NaOH: sodium hydroxide

[0662] NaBH4: sodium borohydride

[0663] NH4Cl: ammonium chloride

[0664] Na2SO4: sodium sulfate

[0665] HCl: hydrochloric acid

[0666] 2KHSO5 . KHSO4 . K2SO4 (oxidizing agent)

[0667] TLC: thin layer chromatography

[0668] n D : refractive index

[0669] h: hour

[0670] 2. Preparation of the monomer of formula (I)

[0671] 2.1 Analysis related to the monomer of formula (I):

[0672] Measured at 23 °C using an 80 MHz NMR spectrometer (Magritek Spinsolve 80). 1 1H-NMR spectrum.

[0673] The melting point of the compound was determined using a Büchi Melting Point B-545.

[0674] 2.2 Preparation of starting materials

[0675] Example A: Synthesis of 6,6'-bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diol [D2NBNA]

[0676]

[0677] A mixture of 136.7 g (300 mmol) of 6,6'-dibromo-1,1'-bi-2-naphthol, 900 mL of toluene, 900 mL of ethanol, 2-naphthylboronic acid (108.35 g; 630 mmol), K3PO4 (140.1 g; 660 mmol), 312 g of water, and 365 mg of tris-(o-tolyl)phosphine [P(o-Tol)3] was heated to 60 °C, and 67 mg (0.1 mol%) of Pd(OCOCH3)2 (palladium(II) acetate) was carefully added. The mixture was heated to reflux for 2.5 h until TLC control (MeOH / H2O 3:1) showed complete conversion. The mixture was cooled to 70 °C. The aqueous phase was separated. The aqueous phase was extracted once with MEK (100 mL). The combined organic phases were washed successively with saturated aqueous Na2CO3 solution (400 mL), 125 mL of 2 M aqueous HCl, and brine (350 mL). The organic phase was treated with activated carbon at room temperature for 1 h, dried over Na2SO4 (40 g), and filtered through diatomaceous earth. The solvent was removed under reduced pressure, and the residue was dissolved in hot MEK (700 g). Then, 200 g of toluene was added, and the mixture was concentrated under reduced pressure to a mass of 240 g. Then, 120 g of toluene was added, and the mixture was concentrated under reduced pressure again to a mass of 240 g. 240 g of toluene was added, and the mixture was concentrated under reduced pressure to a mass of 440 g. The resulting mixture was cooled to room temperature and stirred overnight. The crystals formed were collected by filtration, washed with toluene and pentane, and dried at 60 °C to give 172 g of the title compound D2NBNA (UPLC chemical purity: 97.6%).

[0678] 1 1H NMR (80 MHz, CDCl3) δ = 7.7–7.6 (m, 2H) 7.6–7.0 (m, 12H), 7.0–6.5 (m, 10H), 4.53 (bs, 2H, OH) ppm;

[0679] m.p.[DSC] = 143.0 °C.

[0680] 2.3 Preparation examples:

[0681] Example 1: {[1,1'-Binaphthalene]-2,2'-diylbis(oxy-4,1-phenylene)}dimethanol (BNAD4PODMO) (Compound of formula (Ia), where X = -CH2OH, A = 1,4-phenylene; Compound 1 in Table A)

[0682] Step 1 : Synthesis of 4,4'-[[1,1'-binaphthalene]-2,2'-diylbis(oxy)]dibenzaldehyde (BNAD4PODA)

[0683]

[0684] 4,4'-[[1,1'-binaphthalene]-2,2'-diylbis(oxy)]dibenzaldehyde

[0685] A mixture of racemic 1,1'-bi-2-naphthol (144.61 g, 500 mmol, 1 eq.) and K2CO3 (172.76 g, 1.25 mmol, 2.5 eq) in N,N-dimethylformamide (530 mL) was stirred at 60 °C for 1 h. 4-Fluorobenzaldehyde (155.14 g, 1.25 mol, 2.5 eq) was added to the mixture, and the mixture was stirred under reflux for about 2 h until TLC control (cyclohexane / ethyl acetate 1:1) showed complete conversion. The mixture was cooled to room temperature. Then, the mixture was slowly added to a mixture of 200 mL of concentrated hydrochloric acid solution (37%) and 4 L of water. The resulting suspension was stirred for 1 h. The solid product was collected by filtration. The filter cake was washed three times with water (3 × 500 ml) and once with isopropanol (500 ml), and dried at 60 °C to obtain 247.6 g of the title compound (BNAD4PODA), which was used in the next step (step 2) without purification.

[0686] m.p.[DSC] = 235.9 °C

[0687] 1 1H NMR (80 MHz, CDCl3) δ = 9.77 (s, 2H), 8.11–7.73 (m, 4H), 7.73–7.08 (m, 12H), 6.81 (d, J = 8.6 Hz, 4H) ppm.

[0688] Step 2 : Synthesis of {[1,1'-binaphthalene]-2,2'-diylbis(oxy-4,1-phenylene)}dimethanol (BNAD4PODMO)

[0689]

[0690] {[1,1'-Binaphthalene]-2,2'-diylbis(oxy-4,1-phenylene)}dimethanol

[0691] To a mixture of BNAD4PODA (100.93 g, 200 mmol, 1.00 eq; obtained in Step 1) in THF (1000 g) was added NaBH4 (15.1 g, 400 mmol, 2.00 eq). The reaction mixture was stirred under reflux for 1 h until TLC control (MTBE) showed complete conversion. The reaction mixture was cooled to 0 °C (ice bath), and 10% (w / w) hydrochloric acid (ca. 100 ml) was carefully added to adjust the pH to < 3. The solvent was removed under reduced pressure. The remaining residue was dissolved in 2-MeTHF (350 ml) and water (250 ml). The aqueous phase was removed. The organic phase was washed successively with aqueous sodium hydroxide solution (1 M; 250 ml), 10% (w / w) hydrochloric acid (250 ml), saturated aqueous Na2CO3 solution (250 ml), and brine (250 ml). The organic phase was dried over Na2SO4 and treated with 5 g of activated carbon (Norit DX Ultra). The activated carbon and sodium sulfate were removed by filtration through diatomaceous earth, and the filtrate was concentrated under reduced pressure to give 103.6 g of a crude product. This material was dissolved in hot toluene (333 g). The mixture was cooled to 50 °C, seeded, and slowly cooled to room temperature. The solid was collected by filtration, washed with toluene (3 × 30 g) and n-pentane (200 ml), and dried at 60 °C to give the title compound as a white solid (83.9 g, chemical purity: 99.1%).

[0692] The material was again dissolved in 400 g of 2-MeTHF, washed with aqueous NaOH solution (10% w / w; 133 ml), and washed twice with brine (2 × 100 ml). The organic phase was dried over Na2SO4 and treated with 5 g of activated carbon (Norit DX Ultra). The activated carbon and sodium sulfate were removed by filtration through diatomaceous earth, and the filtrate was concentrated under reduced pressure to give 97.5 g of a crude product. This material was dissolved in hot toluene (273 g). The mixture was cooled to 50 °C, seeded, and slowly cooled to room temperature. The solid was collected by filtration, washed with toluene (3 × 30 g), and dried at 60 °C to give the title compound as a white solid (75.6 g, UPLC chemical purity: 99.34%).

[0693] m.p. [DSC] = 144.3 °C

[0694] 11H NMR (80 MHz, CDCl3) δ = 7.83 (d, J = 9.0 Hz, 4H), 7.52–7.07 (m, 8H), 7.02–6.82 (m, 4H), 6.79–6.47 (m, 4H), 4.43 (s, 4H) 2.45 (bs, 2H) ppm.

[0695] Example 2: {[1,1'-Binaphthalene]-2,2'-diylbis(oxynaphthalene-4,1-diyl)}dimethanol (BNAD4NODMO) (Compound of formula (Ia), where X = -CH2OH, A = 1,4-naphthylene, R = H; Compound 4 in Table A)

[0696] Step 1 : Synthesis of 4,4’-[[1,1’-Binaphthalene]-2,2’-diylbis(oxy)]bis(naphthalene-1-carbaldehyde) (BNAD4NODA)

[0697]

[0698] 4,4’-[[1,1’-Binaphthalene]-2,2’-diylbis(oxy)]bis(naphthalene-1-carbaldehyde)

[0699] A mixture of racemic 1,1’-bi-2-naphthol (98.3 g, 340 mmol, 1 eq.) and K2CO3 (117.5 g, 850 mmol, 2.5 eq) in dimethylformamide (360 mL) was stirred at 60 °C for 1 h. 4-Fluoronaphthaldehyde (141.7 g, 850 mol, 2.5 eq) was added to the mixture at 50 °C and stirred under reflux for about 2 h until TLC control (methanol / H2O 3:1) showed complete conversion. The mixture was cooled to 70 °C. Then, the mixture was slowly added to a mixture of 136 mL of concentrated hydrochloric acid solution (37%) and 3100 L of water. The resulting suspension was stirred for 3 h. The solid product was collected by filtration. The filter cake was washed three times with water (3 × 500 ml), three times with isopropanol (3 × 230 ml), and three times with methanol (3 × 230 ml), and dried at 60 °C for 2 days to obtain 208.4 g of the title compound (BNAD4PODA), which was used in the next step (step 2) without purification.

[0700] 1 1H NMR (80 MHz, CDCl3) δ = 10.13 (s, 2H), 9.3 (d, J = 8.08 Hz, 2H), 8.22–7.27 (m, 20H), 6.60 (d, J = 8.0 Hz, 2H) ppm.

[0701] Step 2 : Synthesis of {[1,1’-Binaphthalene]-2,2’-diylbis(oxynaphthalene-4,1-diyl)}dimethanol (BNAD4NODMO)

[0702]

[0703] {[1,1'-Binaphthalene]-2,2'-diylbis(oxynaphthalene-4,1-diyl)}dimethanol

[0704] NaBH4 (15.2 g, 402 mmol, 2.00 eq) was added portionwise to a mixture of BNAD4PODA (124.53 g, 200 mmol, 1.00 eq; obtained in Step 1) in 2-MeTHF (1000 g). The reaction mixture was stirred under reflux for 10 h. NaBH4 (15.2 g, 402 mmol, 2.00 eq) was added again and stirred for 1 h until TLC control (MTBE) showed complete conversion. The reaction mixture was cooled to room temperature and washed three times with water (3 × 250 ml). Note: The aqueous phase was quenched with 10% (w / w) hydrochloric acid and discarded. The organic phase was washed three times with saturated aqueous citric acid (10% w / w; 3 × 250 ml) and brine (250 ml). The organic phase was dried over Na2SO4 and treated with 5 g of activated carbon (Norit DX Ultra). The activated carbon and sodium sulfate were removed by filtration through diatomaceous earth. Toluene (240 g) was added to the filtrate and the mixture was concentrated under reduced pressure to 316 g (removing 2-MeTHF). Toluene (360 g) was added and the mixture was stirred at room temperature overnight. The crystals formed were collected by filtration, washed with toluene (3 × 30 g) and n-pentane (200 ml), and dried at 60 °C to give the title compound as an off-white solid (103.2 g, chemical purity: 96.7%).

[0705] The substance was dissolved in 500 g of THF and treated with 5 g of activated carbon (Norit DX Ultra) at 40 °C for 2 h. The activated carbon was removed by filtration through diatomaceous earth and toluene (200 g) was added to the filtrate. The mixture was then concentrated under reduced pressure to remove THF (residue: 234 g of the product dissolved in toluene). The residual solution was stirred at room temperature overnight. The crystals formed were collected by filtration, washed with toluene (3 × 30 g) and n-pentane (200 ml), and dried at 60 °C to give the title compound as a white solid (82.6 g, UPLC chemical purity: 97.7%).

[0706] The above recrystallization step was repeated to give the title compound as a white solid (73.6 g, UPLC chemical purity: 97.9%).

[0707] 1 H NMR (80 MHz, acetone-d6) δ = 7.82–7.32 (m, 8H), 7.26–6.50 (m, 14H), 6.34 (d, J = 7.8 Hz, 2H), 4.56 (d, J = 5.3 Hz, 4H), 3.78 (t, J = 5.5 Hz, 2H) ppm.

[0708] m.p. [DSC] = 201.3 °C

[0709] Example 3: [(6,6'-Bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy-4,1-phenylene)] dimethanol (D2NBNAD4PODMO) (Compound of formula (Ia), where X = -CH2OH, A = 1,4-phenylene, R = 2-naphthyl; Table A Compound 148)

[0710] Step 1 : 4,4'-[(6,6'-Bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]dibenzaldehyde (D2NBNAD4PODA)

[0711]

[0712] A mixture of D2NBNA (108.81 g, 200 mmol, 1 eq, obtained in Example A) and K2CO3 (69.1 g, 500 mmol, 1 eq) in N,N-dimethylformamide (200 g) was stirred at 60 °C for 1 h. 4-Fluorobenzaldehyde (62.1 g, 500 mol, 2.5 eq) was added to the mixture, and the mixture was stirred under reflux for about 36 h until TLC control (cyclohexane / ethyl acetate 1:1) showed complete conversion. The mixture was cooled to room temperature and then slowly added to a mixture of 80 mL of concentrated hydrochloric acid solution (37%) and 1.6 L of water. The resulting suspension was stirred for 1 h. The solid product was collected by filtration. The filter cake was washed with water (3 × 150 ml) and isopropanol (2 × 100 ml), and the filter cake was washed once with n-pentane (100 ml) and dried at 60 °C to obtain 150 g of the crude title compound D2NBNAD4PODA. This material was dissolved in THF (450 g). Then toluene (600 g) was added, and the mixture was concentrated under reduced pressure to a total mass of 700 g. The resulting suspension was stirred at room temperature for 1 h. The solid product was collected by filtration. The filter cake was washed with toluene (2 × 100 mL) and n-pentane (100 mL) and dried at 60 °C to obtain 95.8 g of the title compound D2NBNAD4PODA with a chemical purity (UPLC) > 98%.

[0713] 1 1H NMR (80 MHz, DMSO-d6) δ = 9.80 (s, 2H, CHO), 8.60–6.85 (m, 32H) ppm.

[0714] Step 2 : Synthesis of [(6,6'-bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy-4,1-phenylene)]dimethanol (D2NBNAD4PODMO) by reduction of D2NBNAD4PODA

[0715]

[0716] To a mixture of D2NBNAD4PODA (95.8 g, 125 mmol, 1.00 eq.; obtained in Step 1) and THF (640 g) was added portionwise NaBH4 (10 g, 264 mmol, 2.1 eq.) and 8.5 g of methanol. The reaction mixture was stirred under reflux for 2 h until TLC control (TBME) showed complete conversion. The reaction mixture was cooled to 0 °C (ice bath), and aqueous HCl solution (10 wt%) was carefully added (ca. 100 ml) to adjust the pH to < 3. 2-Me-THF (250 mL) and water (100 mL) were added to the mixture. The mixture was concentrated under reduced pressure to remove THF. Phase separation was carried out at 60 °C, and the organic phase was washed with aqueous sodium hydroxide solution (1 M; 200 mL), aqueous HCl solution (10 wt%, 200 mL), and brine (200 mL). The organic phase was dried over Na2SO4 and treated with 5 g of activated carbon (Norit DX Ultra). The activated carbon and Na2SO4 were removed by filtration through diatomaceous earth, and the filtrate was concentrated under reduced pressure. Then, toluene (500 g) was added, and the suspension was stirred at room temperature for 1 h. The solid was collected by filtration, washed with toluene (3 × 30 g) and n-pentane (200 mL), and dried at 60 °C to give 63.5 g of the title compound with a chemical purity of 98.9% D2NBNAD4PODMO .

[0717] 1 1H NMR (80 MHz, DMSO-d6) δ = 8.51 (s, 2H) 8.4–7.8 (m, 14H), 7.7–7.1 (m, 12H), 6.86 (d, J = 8.5 Hz, 4H), 5.19 (t, J = 5.6 Hz, 2H, OH), 4.83 (d, J = 5.6 Hz, 4H, CH2) ppm.

[0718] Example 4 : [(6,6'-Bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxynaphthalene-4,1-diyl)]dimethanol (D2NBNAD4NODMO); (compound of formula (Ia), X = -CH2OH, A = naphthalene-1,4-diyl, R = naphthalen-2-yl; compound 150 of Table A)

[0719] Step 1 : Synthesis of 4,4'-[(6,6'-bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxy)]bis(naphthalene-1-carbaldehyde) (D2NBNAD4NODA)

[0720]

[0721] A mixture of D2NBNA (98 g, 180 mmol, 1 eq., obtained in Example A) and K2CO3 (62.2 g, 450 mmol, 2.5 eq.) in dimethylformamide (280 mL) was stirred at 60 °C for 1 h. 4-Fluoronaphthaldehyde (80 g, 450 mol, 2.5 eq.) was added to the mixture at 50 °C, and the mixture was stirred under reflux for about 4 h until TLC control (cyclohexane / ethyl acetate 3:1) showed complete conversion. The mixture was cooled to 70 °C. Then, the mixture was slowly added to a mixture of 100 mL of concentrated hydrochloric acid solution (37%) and 2000 mL of water. The resulting suspension was stirred for 3 h. The solid product was collected by filtration. The filter cake was washed with water (3 × 250 ml), ethanol (2 × 200 ml) and pentane (200 mL), and dried at 60 °C to obtain 151.7 g of the crude title compound D2NBNAD4NODA. The crude product was recrystallized from THF (750 g) to obtain 95.5 g of the title compound D2NBNAD4NODA, which was used in Step 2 below.

[0722] Step 2 Synthesis of [(6,6'-bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(oxynaphthalene-4,1-diyl)]dimethanol (D2NBNAD4NODMO) by reduction of D2NBNAD4NODA

[0723]

[0724] To a mixture of D2NBNAD4NODA (95 g, 109.9 mmol, 1.00 eq.; obtained in Step 1) in 2-MeTHF (600 g) was added NaBH4 (8.7 g, 231 mmol, 2.1 eq.) portionwise. Methanol (7 g) was slowly added to the reaction mixture, and the mixture was stirred under reflux for 3 h. An additional amount of NaBH4 (2 g) was added, and the mixture was stirred under reflux for 2 h until TLC control (cyclohexane / ethyl acetate 1:1) showed complete conversion. The reaction mixture was cooled to 0 °C (ice bath), and aqueous HCl solution (10 wt%) was carefully added (ca. 100 mL) to adjust the pH to < 3. 2-Me-THF (500 mL) and water (200 mL) were added to the mixture. Phase separation was carried out, and the organic phase was concentrated under reduced pressure. The residue was dissolved in 2-MeTHF (800 mL) and water (200 mL). The organic phase was washed with aqueous NaOH solution (1 M; 200 mL), aqueous HCl solution (10 wt%, 200 mL), and brine (200 mL). The organic phase was dried over Na2SO4. Thereafter, Na2SO4 was removed by filtration through diatomaceous earth, and the filtrate was concentrated under reduced pressure. Then, toluene (300 g) was added, and the suspension was stirred at room temperature for 1 h. The solid was collected by filtration, washed with toluene (3 × 30 g) and n-pentane (200 mL), and dried at 60 °C to give the title compound as an off-white solid (73.7 g). This material was recrystallized from hot THF (1.7 L) and dried at 60 °C to give the title compound D2NBNAD4NODMO as a white solid (41 g) with a chemical purity of 99%.

[0725] 1 H NMR (80 MHz, DMSO-d6) δ = 8.33 (d, J = 10.4 Hz, 4H), 8.2–7.7 (m, 16H), 7.7–7.0 (m, 14H), 6.85 (d, J = 7.2 Hz, 2H), 5.19 (t, J = 5.2 Hz, 2H, OH), 4.82 (d, J = 5.2 Hz, 4H, CH2) ppm;

[0726] m.p. [DSC] = 232 °C.

[0727] Example 5: 4,4'-[[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]dibenzoic acid (BNAD4PODCA) (formula (Ia) compound, where X = -COOH, A = 1,4-phenylene, R = H; Compound 34 in Table A)

[0728] Step 1 : Synthesis of 4,4’-[[1,1’-Binaphthalene]-2,2’-diylbis(oxy)]dibenzonitrile (BNAD4PODCN):

[0729]

[0730] 4,4'-[[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]dibenzo-nitrile

[0731] A mixture of racemic -1,1'-bi - 2 - naphthol (101.23 g, 350 mmol, 1 eq) and K2CO3 (120.93 g, 1.25 mol, 2.5 eq) in N,N - dimethylformamide (350 mL) was stirred at 60 °C for 1 h. 4 - Fluorobenzonitrile (105.97 g, 1.25 mol, 2.5 eq) was added to the mixture, and the mixture was stirred under reflux for about 2 h until TLC control (methanol / H2O = 3:1) showed complete conversion. The mixture was cooled to room temperature. Then, the mixture was slowly added to a mixture of 20 mL of concentrated hydrochloric acid solution (37%) and 400 mL of water. The resulting suspension was stirred for 1 h. The solid product was collected by filtration. The filter cake was washed three times with water (3×250 ml) and once with isopropanol (250 mL) and dried at 60 °C to give 170 g of the title compound (BNAD4PODCN). The crude product was recrystallized from a THF / toluene mixture to give pure BNAD4PODCN (120.6 g) with a chemical purity of 97.8%.

[0732] 1 1H NMR (80 MHz, CDCl3) = δ 8.03 (dd, J = 8.1, 4.2 Hz, 4H), 7.78–7.17 (m, 12H), 6.88 (d, J = 6.78 Hz, 4H) ppm.

[0733] m.p. [DSC] = 215.3 °C

[0734] Step 2 : Synthesis of 4,4'-[[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]dibenzoic acid (BNAD4PODCA):

[0735]

[0736] 4,4'-[[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]dibenzoic acid

[0737] A mixture of BNAD4PODCN (10.0 g, 20.47 mmol; obtained in Step 1) in 38 g of ethanol and a solution of KOH (34.5 g) in water (75 mL) was stirred under reflux for 24 h until TLC control (methanol / H2O = 3:1, acidified with acetic acid) showed complete conversion. The reaction mixture was cooled to room temperature and part of the ethanol was distilled off. Then, the mixture was quenched with concentrated hydrochloric acid (37%) until pH = 1 was reached. The resulting suspension was stirred for 30 min. The solid product was collected by filtration. The filter cake was washed three times with water (3 × 25 mL), once with isopropanol (25 mL), and dried at 60 °C to give 10.75 g (99.74%) of the title compound (BNAD4PODCA) with a chemical purity of 94.4%.

[0738] 1 1H NMR (80 MHz, DMSO-d6) = δ 7.99 (t, J = 7.4 Hz, 4H), 7.69 (d, J = 7.69 Hz, 4H), 7.50–7.04 (m, 8H), 6.78 (d, J = 6.77 Hz, 4H) ppm.

[0739] m.p. [DSC] = 314.2 °C

[0740] Example 6: 4,4'-[[1,1'-Binaphthalene]-2,2'-diylbis(oxy)]dibenzoate (BNAD4PODCAMe) (Compound of formula (Ia), where X = -COOMe, A = 1,4-phenylene, R = H; Compound 67 in Table A)

[0741] Example 6a: Synthesis of BNAD4PODCAMe by oxidation of BNAD4PODA in methanol (see Example 1, Step 1)

[0742]

[0743] Dimethyl 4,4'-[[1,1'-binaphthalene]-2,2'-diylbis(oxy)]dibenzoate

[0744] A suspension of BNAD4PODA (68.6 g, 137.33 mmol; synthesized according to Step 1 of Example 1) and (83.6 g) in 690 g of methanol was stirred at 60 °C for 60 h until TLC control (cyclohexane / ethyl acetate = 3:1) showed complete reaction. The reaction mixture was cooled to room temperature, the solid was filtered off, and washed three times with methanol (3 × 50 mL). The solid was suspended in 500 mL of water and the suspension was stirred at room temperature for 1 h. Finally, the crude product BNAD4PODCAMe was collected by filtration. The filter cake was washed three times with water (3 × 50 mL), once with isopropanol (25 mL), and dried at 60 °C to give 11.93 g (16%) of the title compound BNAD4PODCAMe with a chemical purity of 96.2%.

[0745] 1 1H NMR (80 MHz, CDCl3) = δ 8.18–7.54 (m, 8H), 7.50–7.15 (m, 8H), 6.79 (d, J = 6.76 Hz, 4H), 3.93 (s, 6H, OCH3) ppm.

[0746] m.p. [DSC] = 225.4 °C

[0747] Example 6b: Synthesis of BNAD4PODCAMe by esterification of BNAD4PODCA (see Example 5):

[0748] A suspension of BNAD4PODCA (5.0 g, 9.3 mmol; synthesized according to Example 5) in 35 mL of thionyl chloride (SOCl2) was stirred under reflux for 4 h until the solid was completely dissolved. The excess thionyl chloride was completely removed under reduced pressure, and the resulting solid was dried in vacuo at 60 °C for 1 h. 40 mL of methanol was slowly added to the dried solid, and the resulting suspension was stirred under reflux for 6 h. The suspension was cooled to room temperature, and the crude product was collected by filtration. The filter cake was washed three times with methanol (3 × 10 mL) and dried in vacuo at 60 °C to give 4.83 g (93.9%) of the title compound BNAD4PODCAMe.

[0749] 1 1H NMR (80 MHz, CDCl3) = δ 8.18–7.54 (m, 8H), 7.50–7.15 (m, 8H), 6.79 (d, J = 6.76 Hz, 4H), 3.93 (s, 6H, OCH3) ppm.

[0750] 2.4 Refractive index n of the monomer of formula (I) D :[[-END]]

[0751] Table C below lists the refractive indices of some monomers of formula (I) calculated using software ACD / ChemSketch 2012 (Advanced Chemistry Development, Inc.). Each monomer in Table C is identified by its respective number in Tables A and B. In addition, quantum chemical calculations of all monomers included in Table C confirmed that they do not absorb or absorb only to a negligible extent in the visible range and are thus substantially colorless.

[0752] Table C

[0753]

[0754]

[0755]

[0756]

[0757]

[0758]

[0759]

[0760]

[0761]

[0762]

[0763]

[0764] 3. Preparation of polycarbonate resin from the monomer of formula (I)

[0765] 3.1 Analysis related to the resin prepared from the monomer of formula (I):

[0766] Refractive index (n D ):

[0767] The refractive index was measured using a test piece obtained by the general method for preparing homopolycarbonate described in Section 3.2 below. The measurement was carried out using a Rudolph Instruments J257 automatic refractometer at a temperature of 23 °C and a wavelength of 589 nm.

[0768] Abbe number (ν):

[0769] A sample with a thickness of about 3 mm, the same as the test piece used in the above refractive index measurement method, was used to determine the Abbe number. The refractive index values were measured using a Metricon 2010M prism coupler at 23 °C and wavelengths of 486 nm, 589 nm, and 656 nm. Then, the Abbe number was calculated using the following formula:

[0770] ν = (n D - 1) / (n F - n C )

[0771] n D : Refractive index at a wavelength of 589 nm

[0772] n C : Refractive index at a wavelength of 656 nm

[0773] n F : Refractive index at a wavelength of 486 nm

[0774] 3.2 Preparation examples of homopolycarbonate:

[0775] General method:

[0776] 1.0 mmol of the monomer of formula (I), 214 mg (1.0 eq.) of diphenyl carbonate, and 11 μl of 0.1 mM aqueous NaHCO3 solution were thoroughly mixed and then dried at 30 °C and 500 mbar for 30 minutes. Then, half of the mixture was transferred to a test tube (diameter: 10 mm, length: 80 mm) and heated in an oil bath at 180 °C to 200 °C for 3 hours under a gentle argon stream. A overhead stirrer with a rotation speed of about 35 rpm was used during mixing. Then, the heating was turned off and the formed polymer was slowly cooled to room temperature in the oil bath. The test tube was cut just above the polymer surface using a tube cutter, and the test tube part was tapped with a rubber hammer to take out the obtained test piece lens. The homopolycarbonate prepared by this method, the refractive index measured for it, and the Abbe number are listed in Table D below.

[0777] Table D

[0778]

Claims

1. Use of a compound of formula (I) as a monomer for producing a thermoplastic resin selected from the group consisting of polyesters, polycarbonates and polyester carbonates wherein X 1 and X 2 are independently selected from -CH2OH and -C(O)OR x , wherein R x is selected from hydrogen, phenyl, benzyl and C1-C4-alkyl; A 1 and A 2 are independently selected from monocyclic or polycyclic arylene having 6 to 18 carbon atoms as ring members and monocyclic or polycyclic heteroarylene having a total of 5 to 18 atoms as ring members, wherein 1, 2, 3 or 4 of these ring member atoms of the heteroarylene are selected from nitrogen, sulfur and oxygen, and the remaining atoms of these ring member atoms of the heteroarylene are carbon atoms, and wherein the monocyclic or polycyclic arylene and the monocyclic or polycyclic heteroarylene are unsubstituted or carry 1, 2, 3 or 4 R Ar1 groups; R 1 and R 2 are independently selected from halogen, C2-C3-alkynyl, CN, R, S(O) k R, NHR, OR, CH s R' 3-s , NR2, C(O)R and CH=CHR", provided that if p + q > 1, then R 1 and R 2 may be the same or different, where s is 0, 1 or 2 each occurrence, and k is 0, 1 or 2 each occurrence; p and q are independently 0, 1 or 2; R is selected from C1-C4-alkyl and Q 1 group; Q 1 selected from monocyclic or polycyclic aryl groups having 6 to 26 carbon atoms as ring members and monocyclic or polycyclic heteroaryl 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 heteroaryl group are selected from nitrogen, sulfur and oxygen, and the remaining atoms of these ring member atoms of the heteroaryl group are carbon atoms, wherein the monocyclic or polycyclic aryl group and the monocyclic or polycyclic heteroaryl group are unsubstituted or carry 1, 2, 3 or 4 R''' groups; R Ar1 Selected from R 11 、S(O) k R 11 、NHR 11 、OR 11 、CN, halogen, CH t R' 3-t 、NR 11 2 and CH=CHR", where, If there is more than one R on the same heteroaryl or aryl or heteroarylene or arylene Ar1 , then the R Ar1 s may be the same or different, where t is 0, 1 or 2 each time it appears, and k is 0, 1 or 2 each time it appears; R 11 selected from C1-C4-alkyl and Q 2 groups; Q 2 selected from monocyclic or polycyclic aryl groups having 6 to 18 carbon atoms as ring members and monocyclic or polycyclic heteroaryl groups having a total of 5 to 18 atoms as ring members, wherein 1, 2, 3 or 4 of these ring member atoms of the heteroaryl 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 aryl group and the monocyclic or polycyclic heteroaryl group are unsubstituted or carry 1, 2, 3 or 4 R''' groups; R' is selected from monocyclic or polycyclic aryl groups having 6 to 18 carbon atoms as ring members and monocyclic or polycyclic heteroaryl groups having a total of 5 to 18 atoms as ring members, wherein 1, 2, 3 or 4 of these ring member atoms of the heteroaryl 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 aryl group and the monocyclic or polycyclic heteroaryl group are unsubstituted or carry 1, 2, 3 or 4 R''' groups; R'' is selected from hydrogen, methyl, phenyl and naphthyl, wherein phenyl and naphthyl are unsubstituted or substituted by 1, 2, 3 or 4 identical or different R''' groups; R''' is selected from phenyl, halogen, OCH3, CH3, N(CH3)2 and C(O)CH3.

2. A compound of formula (I) wherein X 1 and X 2 are independently selected from -CH2OH and -C(O)OR x , wherein R x is selected from hydrogen, phenyl, benzyl and C1-C4-alkyl; A 1 and A 2 are independently selected from monocyclic or polycyclic arylenes having 6 to 18 carbon atoms as ring members and monocyclic or polycyclic heteroarylenes having a total of 5 to 18 atoms as ring members, where 1, 2, 3 or 4 of these ring member atoms of the heteroarylene are selected from nitrogen, sulfur and oxygen and the remaining atoms of these ring member atoms of the heteroarylene are carbon atoms, where the monocyclic or polycyclic arylene and the monocyclic or polycyclic heteroarylene are unsubstituted or carry 1, 2, 3 or 4 R Ar1 groups; R 1 and R 2 are independently selected from halogen, C2-C3-alkynyl, CN, R, S(O) k R, NHR, OR, CH s R' 3-s , NR2, C(O)R and CH=CHR", where if p + q > 1, then R 1 and R 2 may be the same or different, where s is 0, 1 or 2 each time it appears, and k is 0, 1 or 2 each time it appears; p and q are independently 0, 1 or 2; R is selected from C1-C4-alkyl and Q 1 group; Q 1 selected from monocyclic or polycyclic aryl groups having 6 to 26 carbon atoms as ring members and monocyclic or polycyclic heteroaryl 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 heteroaryl 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 aryl group and the monocyclic or polycyclic heteroaryl group are unsubstituted or carry 1, 2, 3 or 4 R''' groups; R Ar1 Selected from R 11 、S(O) k R 11 、NHR 11 、OR 11 、CN, halogen, CH t R' 3-t 、NR 11 2 and CH=CHR", where, If there are more than one R on the same heteroaryl or aryl or heteroarylene or arylene Ar1 , then the R Ar1 may be the same or different, where t is 0, 1 or 2 each time it appears, and k is 0, 1 or 2 each time it appears; R 11 selected from C1-C4-alkyl and Q 2 groups; Q 2 selected from monocyclic or polycyclic aryl groups having 6 to 18 carbon atoms as ring members and monocyclic or polycyclic heteroaryl groups having a total of 5 to 18 atoms as ring members, wherein 1, 2, 3 or 4 of these ring member atoms of the heteroaryl 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 aryl group and the monocyclic or polycyclic heteroaryl group are unsubstituted or carry 1, 2, 3 or 4 R''' groups; R' is selected from monocyclic or polycyclic aryl groups having 6 to 18 carbon atoms as ring members and monocyclic or polycyclic heteroaryl groups having a total of 5 to 18 atoms as ring members, wherein 1, 2, 3 or 4 of these ring member atoms of the heteroaryl 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 aryl group and the monocyclic or polycyclic heteroaryl group are unsubstituted or carry 1, 2, 3 or 4 R''' groups; R'' is selected from hydrogen, methyl, phenyl and naphthyl, wherein phenyl and naphthyl are unsubstituted or substituted by 1, 2, 3 or 4 identical or different R''' groups; R''' is selected from phenyl, halogen, OCH3, CH3, N(CH3)2 and C(O)CH3; Exclude the compounds of formula (I): wherein A 1 and A 2 are both unsubstituted 1,4-phenylene, p and q are both 0, and X 1 and X 2 are both -CH2OH or -C(O)OH; and further exclude the compounds of formula (I): wherein A 1 and A 2 are both unsubstituted 2,3-quinolyl, p and q are both 0, and X 1 and X 2 are both -CH2OH.

3. The use according to claim 1 or the compound according to claim 2, wherein X 1 and X 2 are both -CH2OH.

4. The use according to claim 1 or the compound according to claim 2, wherein X 1 and X 2 are each -C(O)OR x , where R x is selected from hydrogen, phenyl, benzyl and C1-C4-alkyl, especially from hydrogen, methyl and ethyl, particularly from hydrogen and methyl.

5. The use or compound according to any one of the preceding claims, wherein A 1 and A 2 are independently selected from monocyclic or polycyclic arylenes having 6 to 14 carbon atoms as ring members and monocyclic or polycyclic heteroarylenes having a total of 5 to 14 atoms as ring members, where 1 or 2 of these ring member atoms of the heteroarylene are selected from nitrogen, sulfur and oxygen, and the remaining atoms of these ring member atoms of the heteroarylene are carbon atoms, and wherein the monocyclic or polycyclic arylene and the monocyclic or polycyclic heteroarylene are unsubstituted or carry 1 or 2 R Ar1 groups.

6. The use or compound according to any one of the preceding claims, wherein A 1 and A 2 are independently selected from polycyclic arylene groups having 6 to 18 carbon atoms as ring members, wherein the polycyclic arylene group is unsubstituted or bears 1 or 2 R Ar1 groups.

7. Use or compound according to any one of claims 1 to 4, wherein A 1 and A 2 are independently selected from phenylene, naphthylene, 1,2-dihydroacenaphthylene, biphenylene, 1,1'-oxydiphenylene, 1,1'-thiobiphenylene, 9H-fluorene-9,9-diyl, 11H-benzo[a]fluorene-11,11-diyl, 11H-benzo[b]fluorene-11,11-diyl, 7H-benzo[c]fluorene-7,7-diyl, anthracene-9,10-diyl, phenanthrene-9,10-diyl, benzo[c]phenanthrene-5,12-diyl, pyrene-1,6-diyl, Base, methylene, trimethylene, furylidene, benzofuran-2-ylidene, dibenzofuran-2-ylidene, naphtho[1,2-b]furan-2-ylidene, naphtho[2,3-b]furan-2-ylidene, naphtho[2,1-b]furan-2-ylidene, benzonaphtho[1,2-d]furan-2-ylidene, benzonaphtho[2,3-d]furan-2-ylidene, benzonaphtho[2,1-d]furan-2-ylidene, benzo[1,2-b:4,3-b']bifurylidene, benzo[1,2-b:6,5-b']bifurylidene, benzo[1,2-b:5,4-b']bifurylidene, benzo[1,2-b:4,5-b']bifurylidene, 9H-xanthenylidene, tribenzo[b,d,f]oxepin-2-ylidene, xanthenylidene, 2H-naphtho[1,8-d,e][1,3]dioxin-2-ylidene, phenoxathiin-2-ylidene, dinaphtho[2,3-b:2',3'-d]furan-2-ylidene, xanthenylidene, benzo[a]xanthenylidene, benzo[b]xanthenylidene, thienylidene, benzothiophen-2-ylidene, dibenzothiophen-2-ylidene, naphtho[1,2-b]thiophen-2-ylidene, naphtho[2,3-b]thiophen-2-ylidene, naphtho[2,1-b]thiophen-2-ylidene, benzonaphtho[1,2-d]thiophen-2-ylidene, benzonaphtho[2,3-d]thiophen-2-ylidene, benzonaphtho[2,1-d]thiophen-2-ylidene, benzo[1,2-b:4,3-b']bithienylidene, benzo[1,2-b:6,5-b']bithienylidene, benzo[1,2-b:5,4-b']bithienylidene, benzo[1,2-b:4,5-b']bithienylidene, 9H-thioxanthenylidene, 6H-dibenzothiopyran-2-ylidene, 1,4-benzodithiin-2-ylidene, naphtho[1,2-b][1,4]dithiin-2-ylidene, naphtho[2,3-b][1,4]dithiin-2-ylidene, 9H-10-thiaxanthenylidene, thianthren-2-ylidene, benzo[a]thianthren-2-ylidene, benzo[b]thianthren-2-ylidene, dibenzo[a,c]thianthren-2-ylidene, dibenzo[a,h]thianthren-2-ylidene, dibenzo[a,i]thianthren-2-ylidene, dibenzo[a,j]thianthren-2-ylidene, dibenzo[b,i]thianthren-2-ylidene, 2H-naphtho[1,8-b,c]thiophen-2-ylidene, dibenzothiepin-2-ylidene, dibenzothiepin-4-ylidene, 5H-phenanthro[4,5-b,c,d]thiopyran-2-ylidene, tribenzo[b,d,f]thiepin-2-ylidene, 2,5-dihydronaphtho[1,8-b,c:4,5-b',c']bithiophene-2-ylidene, 2,6-dihydronaphtho[1,8-b,c:5,4-b',c']bithiophene-2-ylidene, tribenzo[a,c,i]thianthren-2-ylidene, benzonaphtho[1,8-e,f][1,4]dithiepin-2-ylidene, dinaphtho[2,3-b:2',3'-d]thiophen-2-ylidene, 5H-phenanthro[1,10-b,c]thiophen-2-ylidene, 7H-phenanthro[1,10-c,b]thiophen-2-ylidene, dibenzo[d,d']benzo[1,2-b:4,5-b']bithiophenyl and dibenzo[d,d']benzo[1,2-b:5,4-b']bithiophenyl, wherein the above groups are unsubstituted or carry one R, Ar1 group.

8. Use or compound according to claim 7, wherein A 1 and A 2 are independently selected from phenylene, naphthylene, biphenylene, benz[b]furanyl, dibenz[b,d]furanyl, benz[b]thienyl, dibenz[b,d]thienyl, 9H-fluorenyl and thianthrenyl, wherein phenylene, naphthylene, biphenylene, benz[b]furanyl, dibenz[b,d]furanyl, benz[b]thienyl, dibenz[b,d]thienyl, 9H-fluorenyl and thianthrenyl are unsubstituted or substituted with one Q 2 group, and the Q 2 group is particularly selected from phenyl, naphthyl, phenanthryl, thianthrenyl and dibenz[b,d]thienyl.

9. The use or compound according to claim 8, wherein A 1 and A 2 are independently selected from 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 1,4-naphthylene, 1,2-naphthylene, 2,1-naphthylene, 2,6-naphthylene, 4,4'-biphenylene, 3,3'-biphenylene, 2,2'-biphenylene, 2,4-dibenzo[b,d]thiophenylene, 2,6-dibenzo[b,d]thiophenylene, 4,2-dibenzo[b,d]thiophenylene, 2,8-dibenzo[b,d]thiophenylene, 4,6-dibenzo[b,d]thiophenylene, 6,2-dibenzo[b,d]thiophenylene, 2,4-dibenzo[b,d]furanylene, 2,6-dibenzo[b,d]furanylene, 4,2-dibenzo[b,d]furanylene, 2,8-dibenzo[b,d]furanylene, 4,6-dibenzo[b,d]furanylene, 6,2-dibenzo[b,d]furanylene, 1,2-thianthrenylene, 2,1-thianthrenylene, 3,2-thianthrenylene, 1,3-thianthrenylene, 1,4-thianthrenylene, 1,6-thianthrenylene, 2,7-thianthrenylene, 2,8-thianthrenylene, 1,9-thianthrenylene, 2,7-9H-fluorenylene, 9,2-9H-fluorenylene, 2,9-9H-fluorenylene, 2-(phenyl)-1,4-phenylene, 3-(phenyl)-1,4-phenylene, 2-(1-naphthyl)-1,4-phenylene, 3-(1-naphthyl)-1,4-phenylene, 2-(2-naphthyl)-1,4-phenylene, 3-(2-naphthyl)-1,4-phenylene, 2-(9-phenanthryl)-1,4-phenylene, 3-(9-phenanthryl)-1,4-phenylene, 2-(dibenzo[b,d]thiophen-4-yl)-1,4-phenylene, 3-(dibenzo[b,d]thiophen-4-yl)-1,4-phenylene, 2-(thianthren-1-yl)-1,4-phenylene, 3-(thianthren-1-yl)-1,4-phenylene, 2-phenyl-1,4-naphthylene, 2-(1-naphthyl)-1,4-naphthylene, 2-(2-naphthyl)-1,4-naphthylene, 2-(9-phenanthryl)-1,4-naphthylene, 2-(dibenzo[b,d])thiophen-4-yl)-1,4-naphthylene, 2-(thianthren-1-yl)-1,4-naphthylene, 8-phenyl-2,6-naphthylene, 8-(1-naphthyl)-2,6-naphthylene, 8-(2-naphthyl)-2,6-naphthylene, 8-(9-phenanthryl)-2,6-naphthylene, 8-(dibenzo[b,d]thiophen-4-yl)-2,6-naphthylene and 8-(thianthren-1-yl)-2,6-naphthylene.

10. Use or compound according to any one of the preceding claims, wherein A 1 and A 2 have the same meaning.

11. Use or compound according to any one of the preceding claims, wherein p and q are both 1, and wherein R 1 and R 2 are each attached at the 6- and 6'-positions of the binaphthyl moiety of formula (I), respectively.

12. The use or compound according to any one of the preceding claims, wherein R 1 and R 2 are independently selected from fluorine, CN, methyl, methoxy and the group Q 1 , and wherein R 1 and R 2 are especially the group Q 1 , said group Q 1 being a monocyclic or polycyclic aryl having 6 to 14 carbon atoms as ring members and a monocyclic or polycyclic heteroaryl having a total of 5 to 14 atoms as ring members, wherein 1 or 2 of these ring member atoms of the heteroaryl are selected from nitrogen, sulfur and oxygen, and the remaining atoms of these ring member atoms of the heteroaryl are carbon atoms, and wherein R 1 and R 2 are especially selected from phenyl, naphthyl, phenanthryl, thianthrenyl and dibenzo[b,d]thiophenyl.

13. The use or compound according to any one of the preceding claims, wherein R 1 and R 2 have the same meaning.

14. Use or compound according to any one of the preceding claims, wherein both p and q are 0.

15. Use or compound according to any one of the preceding claims, wherein formula (I) is represented by formula (Ia), where X, R 0 and A are defined as in a row of Table A: Table A: *) The linking positions "n,m-" included in the name of part A should be understood as follows: the first, i.e. n, represents the position of the carbon atom connected to X, and the second, i.e. m, represents the position of the carbon atom connected to the O atom.

16. The use or compound according to any one of the preceding claims, wherein formula (I) is represented by one of formulae (Ia.1), (Ia.2), (Ia.3) or (Ia.4), where X, R 0 and Q 0 are defined as a row in Table B: Table B:

Images