Binaphthalene compound and thermoplastic resin

Abstract

The present invention relates to binaphthalene compounds of formula (I), which are suitable as monomers for the preparation of thermoplastic resins such as polycarbonate resins, which have beneficial optical and mechanical properties and can be used in the manufacture of optical devices. Wherein X1 and X2 are independently selected from-CH2OH and-C (O) ORx, wherein Rx is selected from hydrogen, phenyl, benzyl and C1-C4-alkyl; a1 and A2 are independently, for example, a monocyclic or polycyclic arylene group having 6 to 26 carbon atoms as ring members or a monocyclic or polycyclic heteroarylene group having a total of 5 to 26 atoms as ring members; r1 and R2 are independently selected from the group consisting of halogen, C2-C3-alkynyl, CN, R, OR, CHSR '3-s, NR2, C (O) R and CH = CHR "if p + qgt; r1 and R2 may be the same or different, where s is 0, 1 or 2 at each occurrence; p and q are independently 0, 1 or 2. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to 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 the surface. As a result, the number of lenses can be reduced to lower the decentration sensitivity of the lenses and / or reduce the lens thickness, thus achieving weight reduction.

[0003] US 9,360,593 describes a polycarbonate resin having a repeating unit 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 an optionally substituted monocyclic or polycyclic aryl group having 6 to 36 carbon atoms and an optionally substituted monocyclic or polycyclic heteroaryl group having a total of 5 to 36 atoms.

[0012] However, as observed by the inventors of the present application, despite having 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 undesirable cyclic oligomers. These cyclic oligomers may exacerbate the increase in molecular weight and / or deteriorate the product properties of the resin, such as reducing mechanical strength, reducing glass transition temperature, and / or optical properties. Unfortunately, these cyclic components are difficult to remove from the resin in an effective manner. To reduce the formation of such cyclic compounds, it is generally necessary to polymerize the binaphthalene-containing monomers with a relatively large amount of comonomers.

[0013] Without being bound by theory, it is speculated that the reason for the increased formation of cyclic compounds when using these monomers is 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 undesirable 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, especially for manufacturing, in particular for manufacturing, a polycarbonate,

[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 26 carbon atoms as ring members and monocyclic or polycyclic heteroarylenes having a total of 5 to 26 atoms as ring members, wherein 1, 2, 3 or 4 of these ring member atoms of the heteroarylene 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 Ar groups,

[0021] R 1 and R 2 are independently selected from halogen, C2-C3-alkynyl, CN, R, OR, CH s R' 3-s 、NR2, C(O)R and CH=CHR”, 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;

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

[0023] R Ar is selected from R, OR, CH t R' 3-t 、NR2 and CH=CHR”, where if there are more than one R Ar on the same heteroarylene or arylene, then R Ar can be the same or different, where t is 0, 1 or 2 each time it appears;

[0024] R is selected from C1-C4-alkyl, phenyl, naphthyl, phenanthryl and triphenylenyl, where phenyl, naphthyl, phenanthryl and triphenylenyl are unsubstituted or substituted by 1, 2, 3 or 4 identical or different R'" groups;

[0025] R' is selected from phenyl, naphthyl, phenanthryl and triphenylenyl, where phenyl, naphthyl, phenanthryl and triphenylenyl are unsubstituted or substituted by 1, 2, 3 or 4 identical or different R'" groups;

[0026] R” is selected from hydrogen, methyl, phenyl and naphthyl, where phenyl and naphthyl are unsubstituted or substituted by 1, 2, 3 or 4 identical or different R'" groups;

[0027] R'" is selected from phenyl, halogen, OCH3, CH3, N(CH3)2 and C(O)CH3.

[0028] The compounds of formula (I) are new, but excluding those compounds of formula (I) in which A 1 and A 2 are both unsubstituted phenylene groups, p and q are both 0, and X 1and X 2 are each -CH2OH or C(O)OR x , where R x is hydrogen, methyl or ethyl. These compounds are known from S. Florea et al., Revista de Chimie 2003, 54(12), 972 - 973; P. Rajakumar et al., Bioorganic & Medicinal Chemistry Letters 2007, 17(18), 5270 - 5273; P. Rajakumar et al., Tetrahedron 2007, 63(36), 8891 - 8901; and P. Rajakumar et al., Tetrahedron Letters (2005), 46(36), 6127 - 6130.

[0029] Accordingly, a second aspect relates to new compounds of formula (I). In other words, the second aspect relates to compounds of formula (I), excluding those compounds of formula (I) in which A 1 , A 2 , p, q, X 1 and X 2 are combined as follows:

[0030] A 1 and A 2 are each unsubstituted phenylene, p and q are each 0, X 1 and X 2 are each -CH2OH, C(O)OH, C(O)OCH3 or C(O)OCH2CH3.

[0031] A third aspect relates to a thermoplastic resin comprising a polymer unit of a compound of formula (I), i.e., a thermoplastic resin comprising a structural unit represented by the following formula (II);

[0032]

[0033] wherein

[0034] # represents a connection point to an adjacent structural unit;

[0035] and wherein X 1a and X 2a are respectively derived from X 1 and X 2 , with the -OH or -OR 1 or X 2 group of X x replaced by an oxo (-O-) moiety, and wherein X 1 , X 2 , A 1 , A2 and R 1 and R 2 The definitions of p and q are the same as those described above.

[0036] The present invention also relates to optical devices made of a thermoplastic resin as defined above, in particular made of a polyester and especially made of a polycarbonate. Detailed Description

[0037] Due to the restricted rotation around the bond 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. Therefore, the compounds of formula (I) can exist as a racemic mixture or as a non-racemic mixture, or respectively in the form of their pure (S)- and (R)-enantiomers. 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, provided that these enantiomers exist.

[0038] For the purposes of the present invention, the term "C1-C4-alkanediyl" can alternatively also be referred to as "C1-C4-alkylene" and means a divalent saturated aliphatic hydrocarbon radical 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 can also be branched 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.

[0039] For the purposes of the present invention, the term "monocyclic aryl" means a monovalent aromatic monocyclic group, for example especially phenyl.

[0040] 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 attached 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.

[0041] 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 attached to the remainder of the molecule by a single covalent bond, wherein the polycyclic aromatic hydrocarbon is

[0042] (i) a polycyclic aromatic hydrocarbon, i.e., a fully unsaturated polycyclic hydrocarbon, wherein each carbon atom is part of a conjugated π - electron system,

[0043] (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,

[0044] (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.

[0045] The monocyclic or polycyclic aryl group has 6 to 26, usually 6 to 24 carbon atoms, such as 6, 9, 10, 12, 13, 14, 16, 17, 18, 19, 20, 22 or 24 carbon atoms as ring atoms, especially 6 to 20 carbon atoms, particularly 6, 10, 12, 13, 14, 16, 17 or 18 carbon atoms. The polycyclic aryl group usually has 10 to 26 carbon atoms as ring atoms, especially 10 to 20 carbon atoms, particularly 10, 12, 13, 14, 16, 17 or 18 carbon atoms.

[0046] In this context, polycyclic aryl groups with 2, 3 or 4 benzene rings connected to each other by single bonds include, for example, biphenylyl and terphenylyl. Polycyclic aryl groups with 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 with 2, 3 or 4 fused 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.

[0047] For example, monocyclic or polycyclic aryl groups include phenyl, naphthyl, 9H-fluorenyl, phenanthrenyl, anthracenyl, pyrenyl, a radical, a benz[c]phenanthryl radical, an acenaphthylenyl radical, an acenaphthenyl radical, a 2,3-dihydro-1H-indenyl radical, a 5,6,7,8-tetrahydronaphthalenyl radical, a cyclopenta[fg]acenaphthylenyl radical, a 2,3-dihydrophenalenyl radical, a 9,10-dihydroanthracen-1-yl radical, a 1,2,3,4-tetrahydrophenanthryl radical, a 5,6,7,8-tetrahydrophenanthryl radical, a fluoranthenyl radical, a benzo[k]fluoranthenyl radical, a biphenylenyl radical, a triphenylene radical, a tetraphenylene radical, a 1,2-dihydroacenaphthenyl radical, a dibenzo[a,e][8]annulenyl radical, a perylenyl radical, a biphenyl radical, a terphenyl radical, a naphthylenephenyl radical, a phenanthrylphenyl radical, an anthracenylphenyl radical, a pyrenylphenyl radical, a 9H-fluorenylphenyl radical, a di(naphthylen)phenyl radical, a naphthylenebiphenyl radical, a tri(phenyl)phenyl radical, a tetra(phenyl)phenyl radical, a pentaphenyl(phenyl) radical, a phenylnaphthyl radical, a binaphthyl radical, a phenanthrylnaphthyl radical, a pyrenylnaphthyl radical, a phenylanthracenyl radical, a biphenylanthracenyl radical, a naphthalenylanthracenyl radical, a phenanthrylanthracenyl radical, a dibenzo[a,e][8]annulenyl radical, a 9,10-dihydro-9,10[1',2']benzanthracenyl radical, a 9,9'-spirobifluorenyl radical, and a spiro[1H-cyclobuta[de]naphthalene-1,9'-[9H]fluorene] radical.

[0048] 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 heteroarene attached to the remainder of the molecule by a single covalent bond, wherein

[0049] (i) the polycyclic heteroarene 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 phenyl and heteroaromatic monocyclic groups as defined above, wherein the aromatic rings of the polycyclic heteroarene are covalently linked to one another and / or directly fused to one another and / or fused to a saturated or unsaturated 4- to 10-membered monocyclic or bicyclic hydrocarbon ring, or

[0050] (ii) The polycyclic heteroarene has at least one saturated or partially or fully unsaturated 5-membered, 6-membered, 7-membered or 8-membered heterocycle, which heterocycle 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 the heteroaromatic monocycles as defined above, wherein at least one aromatic ring is directly fused to the saturated or partially unsaturated 5- to 8-membered heterocycle, and wherein the aromatic rings of the polycyclic heteroarene 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.

[0051] The monocyclic or polycyclic heteroaryl has 5 to 26, usually 5 to 24, especially 5 to 20 ring atoms, which include 1, 2, 3 or 4 atoms selected from nitrogen atoms, sulfur atoms and oxygen atoms, and the remaining atoms of the ring atoms are carbon atoms. The polycyclic heteroaryl usually has 9 to 26, usually 9 to 24, especially 9 to 20 ring atoms, which include 1, 2, 3 or 4 atoms selected from nitrogen atoms, sulfur atoms and oxygen atoms, and the remaining atoms of the ring atoms are carbon atoms.

[0052] 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’]difuranyl, benzo[1,2-b:5,4-b’]difuranyl, benzo[1,2-b:4,5-b’]difuranyl, 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.,

[0053] For the purposes of the present invention, the term "monocyclic arylene" refers to a divalent aromatic monocyclic group, such as, in particular, phenylene.

[0054] For the purposes of the present invention, the term "monocyclic heteroarylene" refers to a divalent heteroaromatic monocyclic group, i.e., a heteroaromatic monocyclic that 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 has 5 or 6 ring atoms, which includes 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, 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.

[0055] 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 connected to the two remaining parts of the molecule by two covalent single bonds, wherein the polycyclic aromatic hydrocarbon is

[0056] (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,

[0057] (ii) a polycyclic hydrocarbon having at least 1 benzene ring fused to a saturated or unsaturated 4 - to 10 - membered monocyclic or bicyclic hydrocarbon ring,

[0058] (iii) a polycyclic hydrocarbon having at least 2 benzene rings that are connected to each other by a covalent bond, an oxygen atom or a sulfur atom, or are directly fused to each other and / or fused to a saturated or unsaturated 4 - to 10 - membered monocyclic or bicyclic hydrocarbon ring.

[0059] The monocyclic or polycyclic arylene has 6 to 26 carbon atoms, usually 6 to 24 carbon atoms, for example 6, 9, 10, 12, 13, 14, 16, 17, 18, 19, 20, 22 or 24 carbon atoms as ring atoms, especially 6 to 20 carbon atoms, particularly 6, 10, 12, 13, 14, 16, 17 or 18 carbon atoms. The polycyclic arylene usually has 10 to 26 carbon atoms as ring atoms, especially 10 to 20 carbon atoms, particularly 10, 12, 13, 14, 16, 17 or 18 carbon atoms.

[0060] In this context, polycyclic arylenes having 2, 3 or 4 benzene rings connected to each other by a single bond or by an oxygen or sulfur atom include, for example, biphenylylene and terphenylylene, 1,1’ - oxydiphenylene and 1,1’ - thiodiphenylene. Polycyclic arylenes having 2, 3 or 4 benzene rings directly fused to each other include, for example, naphthylene, anthracenylene, phenanthrenylene, pyrenylene, triphenylenylene, chrysenylene and benzo[c]phenanthrenylene. Polycyclic arylene groups having 2, 3 or 4 benzene rings fused to a saturated or unsaturated 4- to 10-membered monocyclic or bicyclic hydrocarbon ring include, for example, 9H-fluorenylene, biphenylenylene, tetraphenylenylene, acenaphthenylene (1,2-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.

[0061] For example, monocyclic or polycyclic arylene groups include phenylene, naphthylene, 9H-fluorenylene, phenanthrylene, anthrylene, pyrenylene, a base, a benz[c]phenanthrenylene, an acenaphthylenylene, an acenaphthylene, a 2,3-dihydro-1H-indenylene, a 5,6,7,8-tetrahydro-naphthalenylene, a cyclopenta[fg]acenaphthylenylene, a 2,3-dihydrophenalenylene, a 9,10-dihydroanthracen-1-yl, a 1,2,3,4-tetrahydrophenanthryl, a 5,6,7,8-tetrahydrophenanthryl, a fluoranthenylene, a benzo[k]fluoranthenylene, a biphenylene, a triphenylene, a quaterphenylene, a 1,2-dihydroacenaphthyl, a dibenzo[a,e][8]annulenylene, a perylenylene, a biphenylenyl, a terphenylenyl, a naphthylenephenylene, a phenanthrylphenylene, an anthracenylphenylene, a pyrenylphenylene, a 9H-fluorenylphenylene, a di(naphthylen)phenylene, a naphthylenebiphenylene, a tri(phenyl)phenylene, a tetra(phenyl)phenylene, a pentaphenyl(phenylene), a phenylnaphthylene, a binaphthylene, a phenanthrylnaphthylene, a pyrenylnaphthylene, a phenylanthracenylene, a biphenylanthracenylene, a naphthalenylanthracenylene, a phenanthrylanthracenylene, a dibenzo[a,e][8]annulenylene, a 9,10-dihydro-9,10[1',2']benzanthryl, a 9,9'-spirobi-9H-fluorenylene, and a spiro[1H-cyclobuta[de]naphthalene-1,9'-[9H]fluorene]ylene.

[0062] 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 by two covalent single bonds, where

[0063] (i) the polycyclic heteroarene bears a heteroaromatic monocyclic ring as defined above and at least one, for example 1, 2, 3, 4 or 5, other aromatic rings selected from phenyl and heteroaromatic monocyclic rings as defined above, where the aromatic rings of the polycyclic heteroarene are linked to each other by covalent bonds and / or directly fused to each other and / or fused to a saturated or unsaturated 4- to 10-membered monocyclic or bicyclic hydrocarbon ring, or

[0064] (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 rings as defined above, where at least one aromatic ring is directly fused to a saturated or partially unsaturated 5- to 8-membered heterocyclic ring, and where 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.

[0065] The monocyclic or polycyclic heteroarylene has 5 to 26, usually 5 to 24, especially 5 to 20 ring atoms, which include 1, 2, 3 or 4 atoms selected from nitrogen atoms, sulfur atoms and oxygen atoms, where the remaining atoms of the ring atoms are carbon atoms. The polycyclic heteroaryl usually has 9 to 26, usually 9 to 24, especially 9 to 20 ring atoms, which include 1, 2, 3 or 4 atoms selected from nitrogen atoms, sulfur atoms and oxygen atoms, where the remaining atoms of the ring atoms are carbon atoms.

[0066] 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, benzo[b]naphtho[2,3-d]thienylene, benzo[b]naphtho[2,1-d] Thienyl, 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]benzothiopyranylene, 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, dibenzo[a,i]thianthrenylene, dibenzo[a,j]thianthrenylene, dibenzo[b,i]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, Tribenzo[b,d,f] tribenzo[b,d,f]thiepinylene, benzothieno[3,4-c,d]thieno[2,3,4-j,k][2]benzothiepinylene, dinaphtho[1,8-bc:1',8'-f,g][1,5]dithiocinylene, furo[3,2-g]quinolinylene, furo[2,3-g]quinolinylene, furo[2,3-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.,

[0067] For the purposes of the present invention, the suffix “-ylene” means that, in accordance with 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 herein synonymously with the suffix “-diyl” (e.g. in benzenediyl or benzene-1,4-diyl).

[0068] For the purposes of the present invention, a “structural unit” means a structural element that repeatedly occurs in the polymer main chain of a thermoplastic resin. Thus, the terms “structural unit” and “repeating unit” are used synonymously.

[0069] For the purposes of the present invention, an "optical device" means a device that is transparent to visible light and that manipulates light beams, 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 glasses.

[0070] The following statements regarding the 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 one another.

[0071] The following statements regarding the preferred embodiments of the variables, when referring to the compounds of formula (I) and the structural units of formula (II) and, where applicable, to the uses according to the invention, are valid both individually and preferably in combination with one another.

[0072] In formula (I) and also in formula (II), the variables X 1 、X 2 、A 1 、A 2 、R 1 、R 2 、p and q have the following meanings, either individually or preferably in any combination:

[0073] 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-.

[0074] 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-.

[0075] In an embodiment of another group (2), the variables X 1 and X 2 in formula (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 those defined herein for R xThe meaning of the definition, 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.

[0076] In an embodiment of a specific subgroup (2'), the variable X in formula (I) 1 and X 2 have the same meaning, which is selected from the meanings defined for X 1 and X 2 in the embodiments of group (2).

[0077] In an embodiment of the preferred group (3), which is a combination of the embodiments of groups (1) and (2), the variable X in formula (I) 1 and X 2 are independently selected from -CH2OH and -C(O)OR x , where R x is hydrogen or C1-C4-alkyl, especially independently selected from -CH2OH, -C(O)OH, -C(O)OCH3 and -C(O)OCH2CH3, and in particular independently selected from -CH2OH, -C(O)OH and -C(O)OCH3. Accordingly, in an embodiment of the preferred group (4), the variable X in formula (II) 1a and X 2a are independently selected from -CH2O- and -C(O)O-.

[0078] In an embodiment of a specific subgroup (3'), the variable 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 , especially those preferred meanings mentioned, especially selected from the meanings defined in the embodiments of group (3), and likewise, the variable X in formula (II) 1a and X 2a have the same meaning, which is selected from the meanings defined in the embodiments of group (3).

[0079] In an embodiment of the preferred group (4), the variables A 1 and A 2Independently selected from monocyclic or polycyclic arylene groups having 6 to 22, especially 6 to 18, carbon atoms as ring members and monocyclic or polycyclic heteroarylene groups having 9 to 26 atoms as ring members, where 1, 2, 3 or 4 of these atoms are nitrogen, oxygen or sulfur atoms, especially 1, 2 or 3 (e.g., 1 or 2) of these atoms are oxygen or sulfur atoms and the remaining atoms of these atoms are carbon atoms, where 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 Ar groups, where R Ar has one of the meanings defined herein, especially one of the preferred meanings mentioned herein.

[0080] In an embodiment of the more preferred subgroup (4.1), A 1 and A 2 are independently selected from phenylene, naphthylene, acenaphthylene-1,2-diyl, biphenylene, 1,1'-oxydiphenylene, 1,1'-thiodiphenylene, 9H-fluorenylene, 11H-benzo[a]fluorenylene, 11H-benzo[b]fluorenylene, 7H-benzo[c]fluorenylene, anthrylene, phenanthrylene, benzo[c]phenanthrylene, pyrenylene, Base, picenylene, triphenylene, furanylene, benz[b]furanylene, dibenz[b,d]furanylene, naphtho[1,2-b]furanylene, naphtho[2,3-b]furanylene, naphtho[2,1-b]furanylene, benz[b]naphtho[1,2-d]furanylene, benz[b]naphtho[2,3-d]furanylene, benz[b]naphtho[2,1-d]furanylene, benz[1,2-b:4,3-b']bifuranylene, benz[1,2-b:6,5-b']bifuranylene, benz[1,2-b:5,4-b']bifuranylene, benz[1,2-b:4,5-b']bifuranylene, 9H-xanthenyl, tribenzo[b,d,f]oxepinylene, dibenzo[1,4]dioxinylene, 2H-naphtho[1,8-d,e][1,3]dioxinylene, phenoxathiinylene, dinaphtho[2,3-b:2',3'-d]furanylene, xanthenyl, benzo[a]oxanthrenylene, benz[b]oxanthrenylene, thienylene, benz[b]thienylene, dibenz[b,d]thienylene, naphtho[1,2-b]thienylene, naphtho[2,3-b]thienylene, naphtho[2,1-b]thienylene, benz[b]naphtho[1,2-d]thienylene, benz[b]naphtho[2,3-d]thienylene, benz[b]naphtho[2,1-d]thienylene, benz[1,2-b:4,3-b']dithienylene, benz[1,2-b:6,5-b']dithienylene, benz[1,2-b:5,4-b']dithienylene, benz[1,2-b:4,5-b']dithienylene, 9H-thioxanthylene, 6H-dibenz[b,d]thiopyranyl, 1,4-benzodithiinylene, naphtho[1,2-b][1,4]dithiinylene, naphtho[2,3-b][1,4]dithiinylene, thianthrenylene, benzo[a]thianthrenylene, benz[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]thienylene, dibenz[b,d]thiepinylene, dibenz[b,f]thiepinylene, 5H-phenanthro[4,5-b,c,d] Thienyl, tribenzo[b,d,f]thiepinyl, 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 Ar groups.

[0081] In an embodiment of a particularly preferred subgroup (4.2), A 1 and A 2 are independently selected from phenylene, naphthylene, benzo[b]thienyl, benzo[b]furyl, 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 Ar groups.

[0082] In an embodiment of a particularly preferred subgroup (4.3), A 1 and A 2Independently selected from phenylene, naphthylene, dibenzo[b,d]thiophene-ylene, dibenzo[b,d]furan-ylene, biphenylene, 9H-fluorene-ylene, xanthene-ylene, phenoxathiin-ylene, thianthrene-ylene, and in particular selected from 1,4-phenylene, 1,2-phenylene, 1,3-phenylene, 1,4-naphthylene, 1,5-naphthylene, 2,7-naphthylene, 2,6-naphthylene, 2,3-naphthylene, 1,8-naphthylene, 1,7-naphthylene, 2,8-naphthylene, 1,6-naphthylene, 2,5-naphthylene, 2,4-naphthylene, 1,3-naphthylene, 2,1-naphthylene, 1,2-naphthylene, 2,8-dibenzo[b,d]thiophene-ylene, 4,6-dibenzo[b,d]thiophene-ylene, 2,9-dibenzo[b,d]thiophene-ylene, 1,2-dibenzo[b,d]thiophene-ylene, 2,4-dibenzo[b,d]thiophene-ylene, 3,6-dibenzo[b,d]thiophene-ylene, 4,8-dibenzo[b,d]thiophene-ylene, 2,6-dibenzo[b,d]thiophene-ylene, 3,2-dibenzo[b,d]thiophene-ylene, 3,8-dibenzo[b,d]thiophene-ylene, 1,6-dibenzo[b,d]thiophene-ylene, 1,4-dibenzo[b,d]thiophene-ylene, 3,4-dibenzo[b,d]thiophene-ylene, 4,2-dibenzo[b,d]thiophene-ylene, 2,8-dibenzo[b,d]furan-ylene, 4,6-dibenzo[b,d]furan-ylene, 2,9-dibenzo[b,d]furan-ylene, 1,2-dibenzo[b,d]furan-ylene, 2,4-dibenzo[b,d]furan-ylene, 3,6-dibenzo[b,d]furan-ylene, 4,8-dibenzo[b,d]furan-ylene, 2,6-dibenzo[b,d]furan-ylene, 3,2-dibenzo[b,d]furan-ylene, 3,8-dibenzo[b,d]furan-ylene, 1,6-dibenzo[b,d]furan-ylene, 1,4-dibenzo[b,d]furan-ylene, 3,4-dibenzo[b,d]furan-ylene, 4,2-dibenzo[b,d]furan-ylene, 4,4'-biphenylene, 3,4'-biphenylene, 3,3'-biphenylene, 4,3'-biphenylene, 2,2'-biphenylene, 4,2'-biphenylene, 3,2'-biphenylene, 2,4'-biphenylene, 2,3'-biphenylene, 9,9-9H-fluorene-ylene, 3,6-9H-fluorene-ylene, 1,6-9H-fluorene-ylene, 2,6-9H-fluorene-ylene, 4,6-9H-fluorene-ylene, 1,3-9H-fluorene-ylene, 4,3-9H-fluorene-ylene, 2,3-9H-fluorene-ylene, 3,8-9H-fluorene-ylene, 1,8-9H-fluorene-ylene, 2,8-9H-fluorene-ylene, 4,8-9H-fluorene-ylene, 3,1-9H-fluorene-ylene, 4,1-9H-fluorene-ylene, 2,1-9H-fluorene-ylene, 3,2-9H-fluorene-ylene, 1,2-9H-fluorene-ylene, 2,4-9H-fluorene-ylene, 4,7-9H-fluorene-ylene, 1,7-9H-fluorene-ylene, 2,7-fluorenylene, 3,7-fluorenylene, 3,5-fluorenylene, 4,5-fluorenylene, 2,5-fluorenylene, 1,5-fluorenylene, 1,4-fluorenylene, 2,4-fluorenylene, 3,4-fluorenylene, 2,7-xanthenyl, 2,8-xanthenyl, 1,4-xanthenyl, 2,3-xanthenyl, 1,6-xanthenyl, 1,9-xanthenyl, 1,4-phenoxathiinyl, 4,1-phenoxathiinyl, 3,7-phenoxathiinyl, 2,8-phenoxathiinyl, 3,8-phenoxathiinyl, 2,7-thianthrenyl, 2,8-thianthrenyl, 1,8-thianthrenyl, 1,7-thianthrenyl, 1,3-thianthrenyl, 2,3-thianthrenyl, 1,2-thianthrenyl, 2,1-thianthrenyl, 2,4-thianthrenyl, 1,4-thianthrenyl, 2,9-thianthrenyl, 1,9-thianthrenyl, 2,6-thianthrenyl and 1,6-thianthrenyl, wherein the aforementioned monocyclic or polycyclic aryl and polycyclic heteroaryl are unsubstituted or carry 1 or 2 Rs, Ar groups.

[0083] In an embodiment of a particularly preferred subgroup (4.4), A 1 and A 2Independently selected from phenylene, naphthylene, biphenylene, 9H-fluorene-9,9-diyl, dibenzo[b,d]thiophene-4,4-diyl, dibenzo[b,d]furan-4,4-diyl and thianthrene-2,2-diyl, such as 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 1,4-naphthylene, 1,5-naphthylene, 2,7-naphthylene, 2,6-naphthylene, 2,3-naphthylene, 1,8-naphthylene, 1,7-naphthylene, 2,8-naphthylene, 1,6-naphthylene, 2,5-naphthylene, 2,4-naphthylene, 1,3-naphthylene, 2,1-naphthylene, 1,2-naphthylene, 4,4'-biphenylene, 3,4'-biphenylene, 3,3'-biphenylene, 4,3'-biphenylene, 2,2'-biphenylene, 4,2'-biphenylene, 3,2'-biphenylene, 2,4'-biphenylene, 2,3'-biphenylene, 3,6-9H-fluorene-9,9-diyl, 1,6-9H-fluorene-9,9-diyl, 2,6-9H-fluorene-9,9-diyl, 4,6-9H-fluorene-9,9-diyl, 1,3-9H-fluorene-9,9-diyl, 4,3-9H-fluorene-9,9-diyl, 2,3-9H-fluorene-9,9-diyl, 3,8-9H-fluorene-9,9-diyl, 1,8-9H-fluorene-9,9-diyl, 2,8-9H-fluorene-9,9-diyl, 4,8-9H-fluorene-9,9-diyl, 3,1-9H-fluorene-9,9-diyl, 4,1-9H-fluorene-9,9-diyl, 2,1-9H-fluorene-9,9-diyl, 3,2-9H-fluorene-9,9-diyl, 1,2-9H-fluorene-9,9-diyl, 2,4-9H-fluorene-9,9-diyl, 4,7-9H-fluorene-9,9-diyl, 1,7-9H-fluorene-9,9-diyl, 2,7-9H-fluorene-9,9-diyl, 3,7-9H-fluorene-9,9-diyl, 3,5-9H-fluorene-9,9-diyl, 4,5-9H-fluorene-9,9-diyl, 2,5-9H-fluorene-9,9-diyl, 1,5-9H-fluorene-9,9-diyl, 1,4-9H-fluorene-9,9-diyl, 2,4-9H-fluorene-9,9-diyl, 3,4-9H-fluorene-9,9-diyl, 2,8-dibenzo[b,d]thiophene-4,4-diyl, 4,6-dibenzo[b,d]thiophene-4,4-diyl, 2,9-dibenzo[b,d]thiophene-4,4-diyl, 1,2-dibenzo[b,d]thiophene-4,4-diyl, 2,4-dibenzo[b,d]thiophene-4,4-diyl, 3,6-dibenzo[b,d]thiophene-4,4-diyl, 4,8-dibenzo[b,d]thiophene-4,4-diyl, 2,6-dibenzo[b,d]thiophene-4,4-diyl, 3,2-dibenzo[b,d]thiophene-4,4-diyl, 3,8-dibenzo[b,d]thiophene-4,4-diyl, 1,6-dibenzo[b,d]thiophene-4,4-diyl, 1,4-dibenzo[b,d]thiophene-4,4-diyl, 3,4-dibenzo[b,d]thiophene-4,4-diyl, 4,2-dibenzo[b,d]thiophene-4,4-diyl, 2,8-dibenzo[b,d]furan-4,4-diyl, 4,6-dibenzo[b,d]furan-4,4-diyl, 2,9-dibenzo[b,d]furan-4,4-diyl, 1,2-dibenzo[b,d]furan-4,4-diyl, 2,4-dibenzo[b,d]furan-4,4-diyl, 3,6-dibenzo[b,d]furan-4,4-diyl, 4,8-dibenzo[b,d]furan-4,4-diyl, 2,6-dibenzo[b,d]furan-4,4-diyl, 3,2-dibenzo[b,d]furan-4,4-diyl, 3,8-dibenzo[b,d]furan-4,4-diyl, 1,6-dibenzo[b,d]furan-4,4-diyl, 1,4-dibenzo[b,d]furan-4,4-diyl, 3,4-dibenzo[b,d]furan-4,4-diyl, 4,2-dibenzo[b,d]furan-4,4-diyl, 3,8-dibenzo[b,d]furanyl, 1,6-dibenzo[b,d]furanyl, 1,4-dibenzo[b,d]furanyl, 3,4-dibenzo[b,d]furanyl, 4,2-dibenzo[b,d]furanyl, 2,7-thianthrenyl, 2,8-thianthrenyl, 1,8-thianthrenyl, 1,7-thianthrenyl, 1,3-thianthrenyl, 2,3-thianthrenyl, 1,2-thianthrenyl, 2,1-thianthrenyl, 2,4-thianthrenyl, 1,4-thianthrenyl, 2,9-thianthrenyl, 1,9-thianthrenyl, 2,6-thianthrenyl or 1,6-thianthrenyl, and in particular selected from phenylene, naphthylene, biphenylene, dibenzo[b,d]thiophenyl and thianthrenyl, such as 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 1,4-naphthylene, 1,5-naphthylene, 2,7-naphthylene, 2,6-naphthylene, 2,4-naphthylene, 1,3-naphthylene, 2,3-naphthylene, 1,2-naphthylene, 2,1-naphthylene, 4,4'-biphenylene, 3,4'-biphenylene, 3,3'-biphenylene, 4,3'-biphenylene, 2,2'-biphenylene, 4,2'-biphenylene, 3,2'-biphenylene, 2,4'-biphenylene, 2,3'-biphenylene, 2,8-dibenzo[b,d]thiophenyl, 4,6-dibenzo[b,d]thiophenyl, 2,8-thianthrenyl or 1,9-thianthrenyl, wherein the aforementioned monocyclic or polycyclic aryl and polycyclic heteroaryl are unsubstituted or carry 1 or 2 R, Ar groups.

[0084] In an embodiment of a particular subgroup (4'), the variables A in formulas (I) and (II) 1 and A 2 have the same meaning, which is selected from the meanings defined herein for A 1 and A 2 and in particular the preferred meanings mentioned, and in particular from the meanings defined in the embodiments of groups (4), (4.1), (4.2), (4.3) and (4.4).

[0085] An embodiment of a preferred subgroup (4a) of group (4) relates to a compound of formula (I) wherein A 1 and A 2 each part includes a phenylene ring, which may carry one or two fused rings selected from fused benzene rings and fused 5- or 6-membered heteroaryl rings. Among the compounds of the embodiments of group (4a), the following compounds are preferred: wherein X 1 or X 2 group and -CH2- group are connected to A 1 or A 2At the para position of the phenylene ring. These compounds are also referred to as para isomers of the embodiments of group (4a). A mixture of the para isomers of the compounds of formula (I) of the embodiments of group (4a) with the corresponding meta or ortho isomers is also preferred. Among the compounds of the embodiments of group (4a), the following compounds of formula (I) are particularly preferred: wherein A 1 and A 2 are each 1,4-phenylene or each a mixture of 1,4-phenylene with one or two of its isomers, the isomers being 1,2-phenylene or 1,3-phenylene.

[0086] In a preferred embodiment of group (5), the variables R 1 and R 2 (if present) in formulas (I) and (II) are each independently selected from halogen, C2-C3-alkynyl, CN, R, 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, particularly the preferred meanings.

[0087] In a particularly preferred embodiment of subgroup (5.1), R 1 and R 2 (if present) are independently selected from fluorine, CN, methyl, methoxy, phenyl, naphthyl (e.g., 1-naphthyl or 2-naphthyl), and phenanthryl (e.g., 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, or 9-phenanthryl), and particularly from fluorine, phenyl, or naphthyl (e.g., 1-naphthyl or 2-naphthyl).

[0088] In a specific embodiment of group (5’), the variables R 1 and R 2 in formulas (I) and (II) have the same meaning, which is selected from the meanings defined for R 1 and R 2 herein, particularly the preferred meanings mentioned, and especially from the meanings defined in the embodiments of groups (5) and (5.1).

[0089] Preferably, the variables p and q in formulas (I) and (II) have the same meaning, which is selected from 0, 1, and 2.

[0090] In a preferred embodiment of group (6), the variables p and q in formulas (I) and (II) are both 0, i.e., the binaphthyl moieties in formulas (I) and (II) carry neither the substituent R 1 nor the substituent R 2 .

[0091] In an embodiment of the preferred group (7), the variables p and q in formulas (I) and (II) are both 1, i.e., the binaphthyl moiety in formulas (I) and (II) carries one substituent R 1 and one substituent R 2 . Further, in an embodiment of this group (7), the variable 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 preferably selected from the meanings defined in the embodiments of group (5), especially those defined in the embodiments of group (5.1).

[0092] In an embodiment of the particularly preferred subgroup (7.1) of group (7), the two substituents R 1 and R 2 are respectively attached to the corresponding positions of the respective naphthyl units, i.e., if R 1 is attached, for example, to position 5 of the binaphthyl moiety in formula (I) or (II), then R 2 is attached to position 5' of this moiety.

[0093] In an embodiment of the particularly preferred subgroup (7.2), the two substituents R 1 and R 2 are respectively attached to positions 6 and 6' of the binaphthyl moiety in formula (I) or (II).

[0094] 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 moiety in formulas (I) and (II) carries two substituents R 1 and two substituents R 2 . Further, in an embodiment of this group (8), the variable 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 to the corresponding positions of the respective naphthyl units, i.e., if the two substituents R 1 are attached, for example, to positions 3 and 6 of the binaphthyl moiety in formula (I) or (II), then the two substituents R 2 are attached to positions 3' and 6' of this moiety.

[0095] Those skilled in the art will readily understand that in formulas (I) and (II), X 1 and X 2The meaning of can be combined with A in the embodiments according to one or more of the groups (4), (4.1), (4.2), (4.3), (4.4) and (4'), 1 and A 2 The meaning of can be combined with A in the embodiments according to one or more of the groups (5), (5.1) and (5'), 1 and A 1 The meaning of can be combined with the meanings of p and q in the embodiments according to the group (6), one or more of the groups (7), (7.1) and (7.2) or the embodiment of the group (8). Those skilled in the art should also understand that in the formulas (I) and (II), X given in one of the embodiments of the groups (2) and (2') 1 and X 2 The meaning of can be combined with A in the embodiments according to one or more of the groups (4), (4.1), (4.2), (4.3), (4.4) and (4'), 1 and A 2 The meaning of can be combined with R in the embodiments according to one or more of the groups (5), (5.1) and (5'), 1 and R 2 The meaning of can be combined with the meanings of p and q in the embodiments according to the group (6), one or more of the groups (7), (7.1) and (7.2) or the embodiment of the group (8). Those skilled in the art should also understand that in the formulas (I) and (II), X given in one of the embodiments of the groups (3) and (3') 1 and X 2 The meaning of can be combined with A in the embodiments according to one or more of the groups (4), (4.1), (4.2), (4.3), (4.4) and (4'), 1 and A 2 The meaning of can be combined with R in the embodiments according to one or more of the groups (5), (5.1) and (5'), 1 and R 2 The meaning of can be combined with the meanings of p and q in the embodiments according to the group (6), one or more of the groups (7), (7.1) and (7.2) or the embodiment of the group (8).

[0096] In addition and unless otherwise stated, the variables R Ar , R, R', R'' and R''' alone or preferably in combination with each other, and with the above variables X 1 , X 2 , A 1 , A 2 , R 1 , R 2 , p and q have the following meanings in combination with their meanings and preferred meanings.

[0097] R Ar is preferably selected from R, OR and CH t R' 3-t , and more preferably selected from R and OR, where t is 1 or 2, especially 2, and the variables R and R' each have one of the meanings defined herein, especially one of the preferred meanings. In particular, R Ar groups are selected from methyl, methoxy, phenyl, naphthyl, phenanthryl and triphenylenyl, especially from phenyl, naphthyl (such as 1-naphthyl or 2-naphthyl) and phenanthryl (such as 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl or 9-phenanthryl).

[0098] R is preferably selected from methyl, ethyl, phenyl, naphthyl, phenanthryl and triphenylenyl, which is unsubstituted or substituted by 1, 2 or 3 identical or different R''' groups, where R''' independently has one of the meanings defined herein each time it appears, especially one of the preferred meanings. More preferably, R is selected from phenyl, naphthyl (such as 1-naphthyl or 2-naphthyl) and phenanthryl (such as 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl or 9-phenanthryl), which is unsubstituted.

[0099] R' is preferably selected from phenyl, naphthyl, phenanthryl and triphenylenyl, which is unsubstituted or substituted by 1, 2 or 3 identical or different R''' groups, where R''' independently has one of the meanings defined herein each time it appears, especially one of the preferred meanings. More preferably, R' is selected from phenyl, naphthyl (such as 1-naphthyl or 2-naphthyl) and phenanthryl (such as 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl or 9-phenanthryl), which is unsubstituted.

[0100] R'' is preferably selected from hydrogen, methyl, phenyl and naphthyl, where phenyl and naphthyl are unsubstituted or substituted by 1, 2 or 3, especially 1 or 2 identical or different R''' groups, where R''' independently has one of the meanings defined herein each time it appears, especially one of the preferred meanings. More preferably, R'' is unsubstituted phenyl or unsubstituted naphthyl, such as 1-naphthyl or 2-naphthyl.

[0101] R''' is preferably selected from phenyl, OCH3 and CH3.

[0102] In an embodiment of a specific subgroup (6a) of groups (6), (3') and (4'), where the variables p and q in formula (I) are both 0, X 1 and X 2 groups have the same meaning, and A 1 and A 2 groups have the same meaning, the compound of formula (I) is a compound of formula (Ia),

[0103]

[0104] wherein X represents the same X 1 and X 2 groups, wherein A represents the same A 1 and A 2 groups, and wherein X 1 、X 2 、A 1 and A 2 have the meanings defined herein, in particular the meanings mentioned as preferred herein

[0105] In an embodiment of this subgroup (6a) of groups (6), (3') and (4'), the structural unit of formula (II) is a structural unit of formula (IIa),

[0106]

[0107] where # represents the point of attachment 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, and wherein the variable X 1a 、X 2a 、A 1 and A 2 have the meanings defined herein, especially the meanings mentioned as preferred.

[0108] 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 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 specifically selected from -CH2OH, -C(O)OH and -C(O)OCH3. Thus, the X a moiety in formula (IIa) herein is selected from -CH2O- and -C(O)O-.

[0109] Compounds of formula (Ia) and structural units of formula (IIa) are also preferred, wherein the A moiety is defined as in one of the embodiments of groups (4), (4.1), (4.2), (4.3) and (4.4). More preferably, the A moiety in formula (Ia) and formula (IIa) is defined as in the embodiment of group (4.4). Thus, the A moiety in formula (Ia) and (IIa) herein is especially selected from 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 1,4-naphthylene, 1,5-naphthylene, 2,7-naphthylene, 2,6-naphthylene, 2,3-naphthylene, 1,8-naphthylene, 1,7-naphthylene, 2,8-naphthylene, 1,6-naphthylene, 2,5-naphthylene, 2,4-naphthylene, 1,3-naphthylene, 2,1-naphthylene, 1,2-naphthylene, 4,4'-biphenylene, 3,4'-biphenylene, 3,3'-biphenylene, 4,3'-biphenylene, 2,2'-biphenylene, 4,2'-biphenylene, 3,2'-biphenylene, 2,4'-biphenylene, 2,3'-biphenylene, 3,6-9H-fluorene-1,6-diyl, 1,6-9H-fluorene-1,6-diyl, 2,6-9H-fluorene-1,6-diyl, 4,6-9H-fluorene-1,6-diyl, 1,3-9H-fluorene-1,6-diyl, 4,3-9H-fluorene-1,6-diyl, 2,3-9H-fluorene-1,6-diyl, 3,8-9H-fluorene-1,6-diyl, 1,8-9H-fluorene-1,6-diyl, 2,8-9H-fluorene-1,6-diyl, 4,8-9H-fluorene-1,6-diyl, 3,1-9H-fluorene-1,6-diyl, 4,1-9H-fluorene-1,6-diyl, 2,1-9H-fluorene-1,6-diyl, 3,2-9H-fluorene-1,6-diyl, 1,2-9H-fluorene-1,6-diyl, 2,4-9H-fluorene-1,6-diyl, 4,7-9H-fluorene-1,6-diyl, 1,7-9H-fluorene-1,6-diyl, 2,7-9H-fluorene-1,6-diyl, 3,7-9H-fluorene-1,6-diyl, 3,5-9H-fluorene-1,6-diyl, 4,5-9H-fluorene-1,6-diyl, 2,5-9H-fluorene-1,6-diyl, 1,5-9H-fluorene-1,6-diyl, 1,4-9H-fluorene-1,6-diyl, 2,4-9H-fluorene-1,6-diyl, 3,4-9H-fluorene-1,6-diyl, 2,8-dibenzo[b,d]thiophene-2,8-diyl, 4,6-dibenzo[b,d]thiophene-2,8-diyl, 2,9-dibenzo[b,d]thiophene-2,8-diyl, 1,2-dibenzo[b,d]thiophene-2,8-diyl, 2,4-dibenzo[b,d]thiophene-2,8-diyl, 3,6-dibenzo[b,d]thiophene-2,8-diyl, 4,8-dibenzo[b,d]thiophene-2,8-diyl, 2,6-dibenzo[b,d]thiophene-2,8-diyl, 3,2-dibenzo[b,d]thiophene-2,8-diyl, 3,8-dibenzo[b,d]thiophene-2,8-diyl, 1,6-dibenzo[b,d]thiophene-2,8-diyl, 1,4-dibenzo[b,d]thiophene-2,8-diyl, 3,4-dibenzo[b,d]thiophene-2,8-diyl, 4,2-dibenzo[b,d]thiophene-2,8-diyl, 2,8-dibenzo[b,d]furan-2,8-diyl, 4,6-dibenzo[b,d]furan-2,8-diyl, 2,9-dibenzo[b,d]furan-2,8-diyl, 1,2-dibenzo[b,d]furan-2,8-diyl, 2,4-dibenzo[b,d]furan-2,8-diyl, 3,6-dibenzo[b,d]furanyl, 4,8-dibenzo[b,d]furanyl, 2,6-dibenzo[b,d]furanyl, 3,2-dibenzo[b,d]furanyl, 3,8-dibenzo[b,d]furanyl, 1,6-dibenzo[b,d]furanyl, 1,4-dibenzo[b,d]furanyl, 3,4-dibenzo[b,d]furanyl, 4,2-dibenzo[b,d]furanyl, 2,7-thianthrenyl, 2,8-thianthrenyl, 1,8-thianthrenyl, 1,7-thianthrenyl, 1,3-thianthrenyl, 2,3-thianthrenyl, 1,2-thianthrenyl, 2,1-thianthrenyl, 2,4-thianthrenyl, 1,4-thianthrenyl, 2,9-thianthrenyl, 1,9-thianthrenyl, 2,6-thianthrenyl, 1,6-thianthrenyl, wherein the aforementioned monocyclic or polycyclic aryl and polycyclic heteroaryl are unsubstituted or carry 1 or 2 R, Ar groups.

[0110] Examples of specific subgroup (6a) are compounds of formula (Ia) and structural units of formula (IIa), wherein the combination of the X moiety or the X a moiety with the A moiety is defined respectively in any one of rows 1 to 288 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.

[0111] Table A:

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

[0122]

[0123] *) The linking position "n,m-" contained in the name of part A should be understood as follows: the first one, i.e., n, represents the position of the carbon atom connected to X, and the second one, i.e., m, represents the position of the carbon atom connected to the group -CH2-.

[0124] Among the compounds of formula (Ia) listed in Table A, the following compounds of formula (Ia) are particularly preferred:

[0125] - [[1,1'-Binaphthalene]-2,2'-diylbis(oxymethylene-4,1-phenylene)]dimethanol

[0126] - [[1,1'-Binaphthalene]-2,2'-diylbis(oxymethylene-3,1-phenylene)]dimethanol

[0127] - [[1,1'-Binaphthalene]-2,2'-diylbis(oxymethylene-2,1-phenylene)]dimethanol

[0128] - [[1,1'-Binaphthalene]-2,2'-diylbis(oxymethylenenaphthalene-4,1-diyl)]dimethanol

[0129] - [[1,1'-Binaphthalene]-2,2'-diylbis(oxymethylenenaphthalene-5,1-diyl)]dimethanol

[0130] - [[1,1'-Binaphthalene]-2,2'-diylbis(oxymethylenenaphthalene-7,2-diyl)]dimethanol

[0131] - [[1,1'-Binaphthalene]-2,2'-diylbis(oxymethylenenaphthalene-6,2-diyl)]dimethanol

[0132] - [[1,1'-Binaphthalene]-2,2'-diylbis(oxymethylenenaphthalene-1,3-diyl)]dimethanol

[0133] - [[1,1'-Binaphthalene]-2,2'-diylbis(oxymethylenenaphthalene-3,1-diyl)]dimethanol

[0134] - [[1,1'-Binaphthalene]-2,2'-diylbis(oxymethylenenaphthalene-3,2-diyl)]dimethanol

[0135] - [[1,1'-Binaphthalene]-2,2'-diylbis(oxymethylenenaphthalene-2,1-diyl)]dimethanol

[0136] - [[1,1'-Binaphthalene]-2,2'-diylbis(oxymethylenenaphthalene-1,2-diyl)]dimethanol

[0137] -[[1,1'-Binaphthalene]-2,2'-diylbis(methylenoxy[1,1'-biphenyl]-4',4-diyl)]dimethanol

[0138] -[[1,1'-Binaphthalene]-2,2'-diylbis(methylenoxy[1,1'-biphenyl]-4',3-diyl)]dimethanol

[0139] -[[1,1'-Binaphthalene]-2,2'-diylbis(methylenoxy[1,1'-biphenyl]-3',3-diyl)]dimethanol

[0140] -[[1,1’-Binaphthalene]-2,2’-diylbis(methylenoxy[1,1'-biphenyl]-3,4'-diyl)]dimethanol

[0141] -[[1,1’-Binaphthalene]-2,2’-diylbis(methylenoxy[1,1'-biphenyl]-2',2-diyl)]dimethanol

[0142] -[[1,1’-Binaphthalene]-2,2’-diylbis(methylenoxy[1,1'-biphenyl]-2,4'-diyl)]dimethanol

[0143] -[[1,1’-Binaphthalene]-2,2’-diylbis(methylenoxy[1,1'-biphenyl]-2,3'-diyl)]dimethanol

[0144] -[[1,1’-Binaphthalene]-2,2’-diylbis(methylenoxydibenzo[b,d]thiophene(oxymethylenedibenzo[b,d]thiene)-8,2-diyl)]dimethanol

[0145] -[[1,1’-Binaphthalene]-2,2’-diylbis(methylenoxydibenzo[b,d]thiophene-6,4-diyl)]dimethanol

[0146] -[[1,1’-Binaphthalene]-2,2’-diylbis(methylenoxythianthrene(oxymethylenethianthrene)-8,2-diyl)]dimethanol

[0147] -[[1,1’-Binaphthalene]-2,2’-diylbis(methylenoxythianthrene-9,1-diyl)]dimethanol

[0148] -4,4'-[[1,1’-Binaphthalene]-2,2’-diylbis(methylenoxy)]dibenzoic acid

[0149] -3,3'-[[1,1’-Binaphthalene]-2,2’-diylbis(methylenoxy)]dibenzoic acid

[0150] -2,2'-[[1,1'-Binaphthalene]-2,2'-diylbis(methyleneoxy)]dibenzoic acid

[0151] -4,4'-[[1,1'-Binaphthalene]-2,2'-diylbis(methyleneoxy)]bis(naphthalene-1-carboxylic acid)

[0152] -5,5'-[[1,1'-Binaphthalene]-2,2'-diylbis(methyleneoxy)]bis(naphthalene-1-carboxylic acid)

[0153] -7,7'-[[1,1'-Binaphthalene]-2,2'-diylbis(methyleneoxy)]bis(naphthalene-2-carboxylic acid)

[0154] -6,6'-[[1,1'-Binaphthalene]-2,2'-diylbis(methyleneoxy)]bis(naphthalene-2-carboxylic acid)

[0155] -3,3'-[[1,1'-Binaphthalene]-2,2'-diylbis(methyleneoxy)]bis(naphthalene-2-carboxylic acid)

[0156] -2,2'-[[1,1'-Binaphthalene]-2,2'-diylbis(methyleneoxy)]bis(naphthalene-1-carboxylic acid)

[0157] -1,1'-[[1,1'-Binaphthalene]-2,2'-diylbis(methyleneoxy)]bis(naphthalene-2-carboxylic acid)

[0158] -4,4'-[[1,1'-Binaphthalene]-2,2'-diylbis(methyleneoxy)]bis(naphthalene-2-carboxylic acid)

[0159] -3,3'-[[1,1'-Binaphthalene]-2,2'-diylbis(methyleneoxy)]bis(naphthalene-1-carboxylic acid)

[0160] -4',4”-[[1,1'-Binaphthalene]-2,2'-diylbis(methyleneoxy)]bis([1,1'-biphenyl]-4-carboxylic acid)

[0161] -4',4”-[[1,1'-Binaphthalene]-2,2'-diylbis(methyleneoxy)]bis([1,1'-biphenyl]-3-carboxylic acid)

[0162] -3',3”-[[1,1'-Binaphthalene]-2,2'-diylbis(methyleneoxy)]bis([1,1'-biphenyl]-3-carboxylic acid)

[0163] -3',3”-[[1,1'-Binaphthalene]-2,2'-diylbis(methyleneoxy)]bis([1,1'-biphenyl]-4-carboxylic acid)

[0164] -8,8'-[[1,1'-Binaphthalene]-2,2'-diylbis(methyleneoxy)]bis(dibenzo[b,d]thiophene-2-carboxylic acid)

[0165] -6,6'-[[1,1'-Binaphthalene]-2,2'-diylbis(methyleneoxy)]bis(dibenzo[b,d]thiophene-4-carboxylic acid)

[0166] -8,8'-[[1,1'-Binaphthalene]-2,2'-diylbis(methyleneoxy)]bis(thianthrene-2-carboxylic acid)

[0167] -9,9'-[[1,1'-Binaphthalene]-2,2'-diylbis(methyleneoxy)]bis(thianthrene-1-carboxylic acid)

[0168] -Dimethyl 4,4'-[[1,1'-binaphthalene]-2,2'-diylbis(methyleneoxy)]dibenzoate

[0169] -Dimethyl 3,3'-[[1,1'-binaphthalene]-2,2'-diylbis(methyleneoxy)]dibenzoate

[0170] -Dimethyl 2,2'-[[1,1'-binaphthalene]-2,2'-diylbis(methyleneoxy)]dibenzoate

[0171] -Dimethyl 4,4'-[[1,1'-binaphthalene]-2,2'-diylbis(methyleneoxy)]bis(naphthalene-1-carboxylate)

[0172] -Dimethyl 5,5'-[[1,1'-binaphthalene]-2,2'-diylbis(methyleneoxy)]bis(naphthalene-1-carboxylate)

[0173] -Dimethyl 7,7'-[[1,1'-binaphthalene]-2,2'-diylbis(methyleneoxy)]bis(naphthalene-2-carboxylate)

[0174] -Dimethyl 6,6'-[[1,1'-binaphthalene]-2,2'-diylbis(methyleneoxy)]bis(naphthalene-2-carboxylate)

[0175] -Dimethyl 3,3'-[[1,1'-binaphthalene]-2,2'-diylbis(methyleneoxy)]bis(naphthalene-2-carboxylate)

[0176] -Dimethyl 2,2'-[[1,1'-binaphthalene]-2,2'-diylbis(methyleneoxy)]bis(naphthalene-1-carboxylate)

[0177] -Dimethyl 1,1'-[[1,1'-binaphthalene]-2,2'-diylbis(methyleneoxy)]bis(naphthalene-2-carboxylate)

[0178] -Dimethyl 4,4'-[[1,1'-binaphthalene]-2,2'-diylbis(methyleneoxy)]bis(naphthalene-2-carboxylate)

[0179] -Dimethyl 3,3'-[[1,1'-binaphthalene]-2,2'-diylbis(methyleneoxy)]bis(naphthalene-1-carboxylate)

[0180] -Dimethyl 4',4”-[[1,1'-binaphthalene]-2,2'-diylbis(methyleneoxy)]bis([1,1'-biphenyl]-4-carboxylate)

[0181] -Dimethyl 4',4”-[[1,1'-binaphthalene]-2,2'-diylbis(methyleneoxy)]bis([1,1'-biphenyl]-3-carboxylate)

[0182] -Dimethyl 3',3”-[[1,1'-binaphthalene]-2,2'-diylbis(methyleneoxy)]bis([1,1'-biphenyl]-3-carboxylate)

[0183] -Dimethyl 3',3”-[[1,1'-binaphthalene]-2,2'-diylbis(methyleneoxy)]bis([1,1'-biphenyl]-4-carboxylate)

[0184] -Dimethyl 8,8'-[[1,1'-binaphthalene]-2,2'-diylbis(methyleneoxy)]bis(dibenzo[b,d]thiophene-2-carboxylate)

[0185] -Dimethyl 6,6'-[[1,1'-binaphthalene]-2,2'-diylbis(methyleneoxy)]bis(dibenzo[b,d]thiophene-4-carboxylate)

[0186] -Dimethyl 8,8'-[[1,1'-binaphthalene]-2,2'-diylbis(methyleneoxy)]bis(thianthrene-2-carboxylate)

[0187] -Dimethyl 9,9'-[[1,1'-binaphthalene]-2,2'-diylbis(methyleneoxy)]bis(thianthrene-1-carboxylate)

[0188] In embodiments of specific subgroups (7a) of groups (7), (7.2), (3') and (4'), where both variables p and q in formula (I) are 1, X 1 and X 2 groups have the same meaning, A 1 and A 2 groups have the same meaning, and R 1 and R 2 groups have the same meaning, the compound of formula (I) is a compound of formula (Ib),

[0189]

[0190] wherein X represents the same X 1 and X 2 group, wherein A represents the same A 1 and A 2 group, wherein R 0 represents the same R 1 and R 2 group, and wherein X 1 、X 2 、A 1 、A 2 、R 1 and R 2 have the meanings defined herein, in particular the meanings mentioned as preferred herein.

[0191] In an embodiment of this subgroup (7a) of groups (7), (7.2), (3') and (4'), the structural unit of formula (II) is the structural unit of formula (IIb),

[0192]

[0193] where # represents the point of attachment to the adjacent structural unit, wherein X a represents the same X 1a and X 2a group, wherein A a represents the same A 1 and A 2 group, wherein R 0 represents the same R 1 and R 2 group, and wherein the variable X 1a 、X 2a 、A 1 、A 2 、R 1 and R 2 have the meanings defined herein, in particular the meanings mentioned as preferred.

[0194] Preferably, the X moiety in formula (Ib) and the X a moiety in formula (IIb) 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 , wherein R x is hydrogen or C1-C4-alkyl, particularly 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. Thus, the X in formula (IIa) hereina Partially selected from -CH2O- and -C(O)O-.

[0195] Also preferred are compounds of the following formula (Ib) and structural units of formula (IIb): wherein the A moiety is as defined in one of the embodiments of groups (4), (4.1), (4.2), (4.3) and (4.4). More preferably, the X moiety in formula (Ib) and formula (IIb) is as defined in the embodiment of group (4.4). Accordingly, the A moiety in formula (Ib) and (IIb) herein is particularly selected from 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 1,4-naphthylene, 1,5-naphthylene, 2,7-naphthylene, 2,6-naphthylene, 2,3-naphthylene, 1,8-naphthylene, 1,7-naphthylene, 2,8-naphthylene, 1,6-naphthylene, 2,5-naphthylene, 2,4-naphthylene, 1,3-naphthylene, 2,1-naphthylene, 1,2-naphthylene, 4,4'-biphenylene, 3,4'-biphenylene, 3,3'-biphenylene, 4,3'-biphenylene, 2,2'-biphenylene, 4,2'-biphenylene, 3,2'-biphenylene, 2,4'-biphenylene, 2,3'-biphenylene, 3,6-9H-fluorene-1,6-diyl, 1,6-9H-fluorene-1,6-diyl, 2,6-9H-fluorene-1,6-diyl, 4,6-9H-fluorene-1,6-diyl, 1,3-9H-fluorene-1,6-diyl, 4,3-9H-fluorene-1,6-diyl, 2,3-9H-fluorene-1,6-diyl, 3,8-9H-fluorene-1,6-diyl, 1,8-9H-fluorene-1,6-diyl, 2,8-9H-fluorene-1,6-diyl, 4,8-9H-fluorene-1,6-diyl, 3,1-9H-fluorene-1,6-diyl, 4,1-9H-fluorene-1,6-diyl, 2,1-9H-fluorene-1,6-diyl, 3,2-9H-fluorene-1,6-diyl, 1,2-9H-fluorene-1,6-diyl, 2,4-9H-fluorene-1,6-diyl, 4,7-9H-fluorene-1,6-diyl, 1,7-9H-fluorene-1,6-diyl, 2,7-9H-fluorene-1,6-diyl, 3,7-9H-fluorene-1,6-diyl, 3,5-9H-fluorene-1,6-diyl, 4,5-9H-fluorene-1,6-diyl, 2,5-9H-fluorene-1,6-diyl, 1,5-9H-fluorene-1,6-diyl, 1,4-9H-fluorene-1,6-diyl, 2,4-9H-fluorene-1,6-diyl, 3,4-9H-fluorene-1,6-diyl, 2,8-dibenzo[b,d]thiophene-2,8-diyl, 4,6-dibenzo[b,d]thiophene-2,8-diyl, 2,9-dibenzo[b,d]thiophene-2,8-diyl, 1,2-dibenzo[b,d]thiophene-2,8-diyl, 2,4-dibenzo[b,d]thiophene-2,8-diyl, 3,6-dibenzo[b,d]furanyl, 4,8-dibenzo[b,d]furanyl, 2,6-dibenzo[b,d]furanyl, 3,2-dibenzo[b,d]furanyl, 3,8-dibenzo[b,d]furanyl, 1,6-dibenzo[b,d]furanyl, 1,4-dibenzo[b,d]furanyl, 3,4-dibenzo[b,d]furanyl, 4,2-dibenzo[b,d]furanyl, 2,7-thianthrenyl, 2,8-thianthrenyl, 1,8-thianthrenyl, 1,7-thianthrenyl, 1,3-thianthrenyl, 2,3-thianthrenyl, 1,2-thianthrenyl, 2,1-thianthrenyl, 2,4-thianthrenyl, 1,4-thianthrenyl, 2,9-thianthrenyl, 1,9-thianthrenyl, 2,6-thianthrenyl, 1,6-thianthrenyl, wherein the aforementioned monocyclic or polycyclic aryl and polycyclic heteroaryl are unsubstituted or carry 1 or 2 R, Ar groups.

[0196] Compounds of formula (Ib) and structural units of formula (IIb) are also preferred, wherein R 0 groups are defined as one or more of the embodiments in groups (5), (5.1), and (5'). More preferably, R 0 groups in formula (Ib) and formula (IIb) are defined as in the embodiment of group (5.1). Therefore, R 0 groups in formula (Ib) and (IIb) herein are particularly selected from fluorine, CN, methyl, methoxy, phenyl, naphthyl (e.g., 1-naphthyl or 2-naphthyl) and phenanthryl (e.g., 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl or 9-phenanthryl), and are especially selected from fluorine, phenyl or naphthyl (e.g., 1-naphthyl or 2-naphthyl).

[0197] Examples of specific subgroup (7a) are compounds of formula (Ib) and structural units of formula (IIb), wherein the X moiety or the X a moiety, the A moiety and the combination of R 0 groups are defined respectively as any one of rows 1 to 42 in Table B below, wherein X a in each case is derived from X in formula (Ib) by replacing the -OH or -OR x group of X with an oxo (-O-) unit.

[0198] Table B:

[0199]

[0200]

[0201] *) The linking position "n,m-" contained in the name of part A should be understood as follows: the first one, i.e., n, represents the position of the carbon atom connected to X, and the second one, i.e., m, represents the position of the carbon atom connected to the group -CH2-.

[0202] Among the compounds of formula (Ib) listed in Table B, the following compounds of formula (Ib) are particularly preferred:

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

[0204] -[(6,6'-Diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis(methylenedioxy-3,1-phenylene)]dimethanol

[0205] -[(6,6'-Diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis(methylenedioxynaphthalene-4,1-diyl)]dimethanol

[0206] -[(6,6'-Diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis(methylenedioxynaphthalene-5,1-diyl)]dimethanol

[0207] -[(6,6'-Diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis(methylenedioxynaphthalene-6,2-diyl)]dimethanol

[0208] -[(6,6'-Bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(methylenedioxy-4,1-phenylene)]dimethanol

[0209] -[(6,6'-Bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(methylenedioxy-3,1-phenylene)]dimethanol

[0210] -[(6,6'-Bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(methylenedioxynaphthalene-4,1-diyl)]dimethanol

[0211] -[(6,6'-Bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(methylenedioxynaphthalene-5,1-diyl)]dimethanol

[0212] -[(6,6'-Bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(methylenedioxynaphthalene-6,2-diyl)]dimethanol

[0213] -Dimethyl 4,4'-[(6,6'-Diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis(methylenedioxy)]dibenzoate

[0214] -Dimethyl 3,3'-[(6,6'-diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis(methylenoxy)]dibenzoate

[0215] -Dimethyl 4,4'-[(6,6'-diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis(methylenoxy)]bis(naphthalene-1-carboxylate)

[0216] -Dimethyl 5,5'-[(6,6'-diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis(methylenoxy)]bis(naphthalene-1-carboxylate)

[0217] -Dimethyl 6,6'-[(6,6'-diphenyl[1,1'-binaphthalene]-2,2'-diyl)bis(methylenoxy)]bis(naphthalene-2-carboxylate)

[0218] -Dimethyl 4,4'-[(6,6'-bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(methylenoxy)]dibenzoate

[0219] -Dimethyl 3,3'-[(6,6'-bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(methylenoxy)]dibenzoate

[0220] -Dimethyl 4,4'-[(6,6'-bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(methylenoxy)]bis(naphthalene-1-carboxylate)

[0221] -Dimethyl 5,5'-[(6,6'-bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(methylenoxy)]bis(naphthalene-1-carboxylate)

[0222] -Dimethyl 6,6'-[(6,6'-bis(naphthalen-2-yl)[1,1'-binaphthalene]-2,2'-diyl)bis(methylenoxy)]bis(naphthalene-2-carboxylate)

[0223] The compound of formula (Ia) can be prepared by the method shown in the following reaction route 1, wherein 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.

[0224] Route 1:

[0225]

[0226] In the presence of a base (such as an oxo base, such as an alkaline carbonate or an alkaline hydride, especially an alkaline carbonate, such as potassium carbonate), 1,1'-bi-2-naphthol of formula (1) is reacted with about 2 to 2.5 molar equivalents of a compound of formula (2), where Z is a suitable leaving group, such as a chlorine, bromine, iodine, tosylate or mesitylate group, especially chlorine or bromine, to form a compound of formula (Ia). A suitable solvent for this reaction is a polar aprotic organic solvent, such as acetone.

[0227] The compound of formula (Ib) can be prepared by a method similar to that for preparing the compound of formula (Ia) shown in Reaction Route 1 above, i.e., using the correspondingly substituted 1,1'-bi-2-naphthol of formula (3) instead of the unsubstituted 1,1'-bi-2-naphthol (1) as the starting compound, where R 0 has one of the meanings defined above in this text, especially one of the preferred meanings. This compound of formula (3) can in turn be prepared by the method shown in Reaction Route 2 below, especially when R 0 is an optionally substituted phenyl, naphthyl, phenanthryl or triphenylenyl group.

[0228] Route 2:

[0229]

[0230] In step i) of the process according to Route 2, 1,1'-bi-2-naphthol of formula (1) is brominated to selectively produce 6,6'-dibromo-1,1'-bi-2-naphthol of formula (4). The 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, which is 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 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. More 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 the bromination reaction with elemental bromine, such as 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.

[0231] As another alternative, 6,6'-dibromo-1,1'-binaphthol of formula (4) 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.

[0232] In step ii) of Route 2, in the presence of a transition metal catalyst, especially in the presence of a palladium catalyst, the compound of formula (4) is reacted with an arylboron compound of formula (5),

[0233] R 0 -B(OH)2(5)

[0234] wherein R 0React with those defined above, or with an ester or acid anhydride of (5), in particular a C1-C4-alkyl ester of (5). Generally, step ii) is carried out under so-called "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. 2011 3932-3937). Suitable transition metal catalysts are in particular palladium compounds which carry 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)). Generally, 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 in particular tris(substituted)phosphines, such as triarylphosphines, such as triphenylphosphine, tritolyphosphine or 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP), tricycloalkylphosphines, such as tri-n-butylphosphine, tris(tert-butyl)phosphine or tricyclohexylphosphine, or dicyclohexyl-(2',4',6'-triisopropyl-1,1'-biphenyl-2-yl)-phosphine (X-Phos). Generally, the reaction is carried out in the presence of a base, in particular an oxygen-containing base such as an alkaline alcoholate, an alkaline hydroxide, an alkaline carbonate or an alkaline earth carbonate, such as sodium ethoxide, sodium tert-butoxide, lithium hydroxide, sodium carbonate or potassium carbonate. Generally, 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 (such as toluene, anisole or xylene), acyclic and cyclic ethers (such as methyl tert-butyl ether, diisopropyl ether, dioxane or tetrahydrofuran), and aliphatic alcohols having 1 to 4 carbon atoms (such as methanol, ethanol or isopropanol) and mixtures thereof. The reaction according to step ii) of route 2 is generally carried out at a temperature in the range from 50 to 150 °C.

[0235] Then, as described above, by a method similar to that shown in Route 1, the compound of formula (Ib) can be prepared by the method of the following Reaction Route 3 using the compound of formula (3) as the starting compound, wherein R 0 、X and A each have one of the meanings defined hereinabove for R 1 and R 2 、X 1 and X 2 or A 1 and A 2 Specifically, R 0 is phenyl, naphthyl, phenanthryl or triphenylenyl, these groups being unsubstituted or usually substituted by 1 or 2 groups selected from phenyl, OCH3 and CH3, X is -CH2OH or -C(O)OR x , wherein R x is usually C1-C4 alkyl, and A is a monocyclic or polycyclic heteroarylene or arylene as defined for A 1 and A 2 .

[0236] Route 3:

[0237]

[0238] As shown in Route 3, the 6,6'-substituted 1,1'-bi-2-naphthol of formula (3) is converted with about 2 to 2.5 molar equivalents of the compound of formula (2) to obtain the compound of formula (Ib), and this conversion can be carried out under reaction conditions substantially the same as those described for Route 1 above.

[0239] The compounds of formula (I), especially those having different A 1 and A 2 moieties and / or even different X 1 and X 2 groups, can be prepared in two steps, for example, by the method shown in the following Reaction Route 4, wherein p, q, R 1 、R 2 、X 1 、X 2 、A 1 and A 2 are as defined above. However, the method according to Route 4 is particularly suitable for preparing the following compounds of formula (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.

[0240] Route 4:

[0241]

[0242] In reaction step i) of the process according to Route 4, an optionally substituted 1,1'-bi-2-naphthol of formula (6) (such as a compound of formula (1) or (3)) is reacted with about 0.7 to 1.1 molar equivalents of a compound of formula (2a), where Z is a suitable leaving group such as a chlorine, bromine, iodine, tosylate or mesylate group, especially chlorine or bromine. Then, in step ii), the mono-etherified product of formula (7) obtained in step i) is further etherified with about 1.0 to 1.5 molar equivalents of a compound of formula (2b), where Z is as defined above, to obtain the target product of formula (I). In addition, both reaction steps i) and ii) can be carried out under reaction conditions substantially similar to those in Route 1 above.

[0243] The compound of formula (I), wherein A 1 and A 2 are the same or different biphenylene moieties and can be prepared, for example, in two, three or four steps by a method similar to that shown in the following Reaction Route 5. The method according to Route 5 and similar methods are particularly suitable for preparing 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 Route 5 illustrates the preparation of the following compounds (I): wherein p = q = 0, X 1 and X 2 are both -CH2OH, A 1 is 3,4'-biphenylene, and A 2 is 3,3'-biphenylene.

[0244] Route 5:

[0245]

[0246]

[0247] In reaction step i) of the process according to Route 5, 1,1'-bi-2-naphthol (1) is reacted with about 0.7 to 1.1 molar equivalents of the bromide of formula (8a), where Z is a suitable leaving group such as a chlorine, bromine, iodine, tosylate or mesylate group, especially chlorine or bromine. Then, in step ii), the mono-etherified product of formula (9) obtained in step i) is further etherified with about 1.0 to 1.5 molar equivalents of the compound of formula (8b), where Z is as defined above, to obtain the dibromide of formula (10). The above reaction steps i) and ii) can be carried out under reaction conditions substantially similar to those in Route 1 above. Then, the dibromide (10) can be reacted with about two molar equivalents of the phenylboron compound of formula (11), similar to the coupling step ii) in Route 2 above, to obtain compound (12), which is a compound of formula (I), where both p and q are 0, X 1 and X 2 are both -CH2OH, A 1 is 3,4'-biphenylene, and A 2 is 3,3'-biphenylene.

[0248] The compound of formula (12'), which differs from compound (12) prepared in Route 5 above only in that A 1 and A 2 have the same meaning, for example 3,4'-biphenylene, and thus it is a compound of the following formula (I): where p = q = 0, X 1 = X 2 = -CH2OH, and A 1 = A 2 = 3,4'-biphenylene, can be prepared by an improved step i) of Route 5, where 1,1'-bi-2-naphthol (1) is reacted with about 2 molar equivalents of the bromide of formula (8a), and then reaction step iii) of Route 5 is carried out.

[0249] The compound of formula (12''), which differs from compound (12) prepared in Route 5 above only in that X 1 and X 2 have different meanings, and thus it is a compound of the following formula (I): where p = q = 0, X 1 is for example -C(O)OCH3, X 2 is for example -C(O)OH, A 1 is 4,3'-biphenylene, A 2is 3,3'-biphenylylene and can also be prepared by a variant of the method according to Route 5. Specifically, the compound (9) obtained in step i) of the method of Route 5 is reacted with approximately one molar equivalent of the compound (11'), which is the compound (11) in which the -CH2OH group has been replaced by a -C(O)OCH3 group, by a method similar to step iii). Then, the intermediate product thus obtained is reacted with the compound (8b) according to step ii) of Route 5. Finally, the obtained bromide is reacted with approximately one molar equivalent of the compound (11''), which is the compound (11) in which the -CH2OH group has been replaced by a -C(O)OCH3 group, by a method similar to step iii).

[0250] The compounds of formula (I) include, as A 1 and A 2 the same or different bi(het)arylene groups which are not biphenylylene, and in which the variables p, q, R 1 、R 2 、X 1 and X 2 have the meanings defined herein, and can also be prepared in generally two, three or four reaction 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.

[0251] The transformations shown in Routes 1 to 5 can be carried out by the reactions in the above routes or by obvious variants of these reactions, or alternatively, by methods well established in organic chemistry or combinations thereof.

[0252] Other compounds of formula (I) can be prepared by using obvious variants of the above reactions and combinations thereof with methods well established in organic chemistry.

[0253] The reaction mixtures obtained in the individual steps for the synthesis of the compounds described in Reaction Routes 1, 2, 3, 4 and 5 above are generally refined 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 as a colorless or light brown viscous oil which contains no volatiles or is purified under reduced pressure and at a moderately elevated temperature. If a solid intermediate is obtained, purification can be achieved by recrystallization or washing methods such as slurry washing.

[0254] The starting compounds for preparing the compounds of formula (I) used in the syntheses shown in Routes 1, 2, 3, 4 and 5 above are commercially available or can be prepared by methods known in the art.

[0255] As described above, the compounds of the present invention can be obtained in very high purity, which means that the obtained product contains no significant amount of organic impurities different from the compounds of formula (I) other than volatiles. Generally, based on non-volatile organic substances, 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).

[0256] 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 preparing useful thermoplastic resins (such as polycarbonate resins), and the above thermoplastic resins include different structural units of formula (II) derived from different monomers of formula (I). Therefore, 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.

[0257] The term "volatile" refers to organic compounds having a boiling point below 200 °C at standard pressure (10 5 Pa). Therefore, non-volatile organic substances should be understood to mean compounds having a boiling point above 200 °C at standard pressure.

[0258] 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 crystalline form, the compounds of formula (I) can exist in pure form or in the form of 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. Specifically, 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), in which the crystals contain incorporated solvent.

[0259] 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. Prior to the crystallization step, it may be beneficial to filter the crude preparation of the dissolved compound of formula (I) (such as through diatomaceous earth) in order to remove solid components that may be present in the crude preparation.

[0260] Furthermore, impurities that may be present in the crude preparation of the compounds 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).

[0261] Alternatively, the compounds of formula (I) and their solvates can be obtained in purified form by employing other simple and effective methods for purifying the crude products of these compounds, such as in particular 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 suitable for crystallizing the compounds of formula (I), such as in particular the aromatic hydrocarbons, aliphatic ketones and aliphatic ethers mentioned, such as toluene, methyl ethyl ketone and methyl tert-butyl ether.

[0262] Thus, the compounds of formula (I) for preparing the thermoplastic polymers defined herein, especially polycarbonates, can be readily prepared and obtained in high yield and high purity. In particular, the compounds of formula (I) can be obtained in crystalline form, which allows for 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 for the preparation of optical devices. In summary, the compounds of formula (I) can be used in particular as monomers in the preparation of optical resins.

[0263] 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 formulas (Ia) and (Ib) of the monomers used respectively correspond to the formulas (IIa) and (IIb) of the structural units included in the thermoplastic resin.

[0264] Those skilled in the art should also understand that the structural units of formulas (II), (IIa), and (IIb) are repeating units within the polymer chains of the thermoplastic resin. In addition to the structural units of formulas (II), (IIa), and (IIb) respectively, 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 generating structural units of formula (V):

[0265] HO-R z -A 3 -R z -OH (IV)

[0266] #-O-R z -A 3 -R z -O-# (V)

[0267] wherein

[0268] # represents the connection point to the adjacent structural unit;

[0269] A 3 is a polycyclic group with at least 2 benzene rings, wherein the benzene rings can be connected by W and / or directly fused to each other and / or fused through non-benzene carbocyclic rings and / or fused through two non-benzene carbocyclic rings connected by a linking group L, where A 3 is unsubstituted or substituted by 1, 2, or 3 R aa groups 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;

[0270] 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’)

[0271]

[0272] wherein

[0273] Q’ represents a single bond, O, C=O, or CH2;

[0274] R 7a 、R7b Each independently 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

[0275] * represents the point of attachment to the benzene ring;

[0276] 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 R L groups selected from C1-C4-alkyl, halogen, C1-C4-haloalkyl, C4-C7-cycloalkyl and phenyl;

[0277] Ar is selected from monocyclic or polycyclic aryl having 6 to 26 carbon atoms as ring atoms and monocyclic or polycyclic heteroaryl 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 are selected from nitrogen, sulfur and oxygen, and the remaining atoms of these ring member atoms of the heteroaryl are carbon atoms, where Ar is unsubstituted or substituted by 1, 2 or 3 R ab groups selected from halogen, phenyl and C1-C4-alkyl;

[0278] R z is a single bond, Alk 3 , O-Alk 4 -, O-Alk 4 -[O-Alk 4 -] w - or O-Alk 5 -C(O)-, where O is bonded to A 3 , and where

[0279] w is an integer from 1 to 10;

[0280] Alk 3 is C1-C4-alkanediyl;

[0281] Alk 4 is C2-C4-alkanediyl; and

[0282] Alk 5 is C1-C4-alkanediyl.

[0283] 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.

[0284] In the context of formulas (IV) and (V), A 3 especially a polycyclic group having at least 2 benzene rings or naphthalene rings, wherein the benzene rings are connected by W or fused via two non-benzene carbocyclic rings connected by a linking group L, wherein W is especially selected from a single bond, S, S(O), SO2, C(CH3)2 and group A', and wherein L is a single bond or a C1-C4-alkylene group.

[0285] In the context of formulas (IV) and (V), R z especially O-Alk 4 -, wherein Alk 4 especially a straight-chain alkanediyl having 2 to 4 carbon atoms, and especially O-CH2CH2.

[0286] Among the monomers of formula (IV), monomers of general formulas (IV-1) to (IV-8) are preferred

[0287]

[0288]

[0289] wherein

[0290] a and b are 0, 1, 2 or 3, especially 0 or 1;

[0291] a' and b' are 0, 1, 2 or 3, especially 0 or 1;

[0292] c and d are 0, 1, 2, 3, 4 or 5, especially 0 or 1;

[0293] e and f are 0, 1, 2, 3, 4 or 5, especially 0 or 1;

[0294] 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;

[0295] 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.

[0296] 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 zEspecially selected from single bonds, CH2 and O-CH2CH2, in particular O-CH2CH2:

[0297]

[0298]

[0299] Examples of the compounds of formulae (IV-11) to (IV-22) are 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-isopropylphenyl)fluorene, 9,9-bis(4-hydroxy-3-tert-butylphenyl)fluorene, 9,9-bis(4-hydroxy-3-cyclohexylphenyl)fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (BPEF), 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-isopropylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butylphenyl)fluorene, 9,9-bis(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'-di(naphthalen-1-yl)-1,1'-binaphthalene, 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthalene, 2,2'-bis(2-hydroxyethoxy)-6,6'-di(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-dibenzothiophen-4-yl)phenyl]-1-methylethyl]-2,6-bis(1,2-dibenzothiophen-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(dibenzothiophen-4-yl)phenyl]sulfonyl-2,6-dibenzothiophen-4-yl)phenoxy]ethanol, etc.,

[0300] 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, 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.

[0301] 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,

[0302]

[0303]

[0304] wherein

[0305] a and b are 0, 1, 2 or 3, especially 0 or 1;

[0306] a' and b' are 0, 1, 2 or 3, especially 0 or 1;

[0307] c and d are 0, 1, 2, 3, 4 or 5, especially 0 or 1;

[0308] e and f are 0, 1, 2, 3, 4 or 5, especially 0 or 1;

[0309] 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;

[0310] 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.

[0311] Structural units of the 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:

[0312]

[0313]

[0314] 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-bis(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-methylethyl]-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-methylethyl]-2,6-bis(thianthren-1-yl)phenoxy]ethanol.

[0315] In a particularly preferred group 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 group 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 in which it is O-CH2CH2.

[0316] Among the thermoplastic resins of this group of particularly preferred embodiments, preferably, based on the total amount of the structural units of formulas (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%.

[0317] The compounds of formulas (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 to known methods.

[0318] 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. Thereby, the compound of formula (IV-8) is obtained, wherein R z -OH is O-Alk 4 -OH or O-Alk 4 -[O-Alk 4 -] w -OH.

[0319] 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:

[0320] (a) React fluorene with hydroxy naphthalene in the presence of hydrogen chloride gas and mercapto carboxylic acid; (b) React 9-fluorene with hydroxy naphthalene in the presence of an acid catalyst (and alkyl mercaptan); (c) React fluorene with hydroxy naphthalene in the presence of hydrochloric acid and a mercaptan (e.g., mercapto carboxylic acid); (d) React fluorene with hydroxy naphthalene 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 bis(naphthol)fluorene; etc. Thus, a compound of formula (IV-2) can be obtained, wherein R z is a single bond.

[0321] 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 haloalkyl alcohol. For example, react 9,9-bis(hydroxy naphthyl)fluorene of formula (IV-2) (wherein R z is a single bond) with an epoxide or a haloalkyl alcohol 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)naphthyl]fluorene can be prepared by reacting 9,9-bis[6-(2-hydroxynaphthyl]fluorene with 2-chloroethanol under basic conditions.

[0322] The monomers of formula (I) and (IV) for manufacturing thermoplastic resins 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 thermoplastic resins 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 dihydroxy compounds in which at least one of the -OH has a carbon number different from that of the dihydroxy compound of 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 dihydroxy compounds in which at least one of the -OH has a carbon number different from that of the dihydroxy compound of 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 formula (I) will be within the range given for the monomer of formula (IV).

[0323] 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.

[0324] The polycarbonate is characterized by having structural units of at least one of formula (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),

[0325] #-O-R z -A 3 -R z -O-#(V)

[0326] wherein

[0327] #, R z and A 3 are as defined above;

[0328] and a structural unit of formula (III-1) derived from a carbonate-forming component:[[]]

[0329]

[0330] where each # represents a connection point to an adjacent structural unit, i.e., the O at the connection point to the structural unit of formula (II), and the O at the connection point to the structural unit of formula (V) (if present).

[0331] The polyester is characterized by having structural units of at least one of formula (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. If X in formula (II) 1a and X 2a or X in formula (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:

[0332]

[0333] In formulas (III-2) to (III-5), each variable # represents a connection point to an adjacent structural unit, i.e., 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).

[0334] 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.

[0335] Embodiments of a particular group relate to thermoplastic copolymer resins, especially polycarbonates, polyester carbonates, and polyesters, having structural units of formula (II) and one or more structural units of formula (V), i.e., resins, especially 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, especially in the range of 10:90 to 99:1, particularly in the range of 30:70 to 97:3, or in the range of 10:90 to 99:1, especially 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, particularly in the range of 25:75 to 90:10 or 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 25:75 to 85:15 or in the range of 27:73 to 90:10, and particularly in the range of 25:75 to 70:30 or 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%, especially 10 to 99 mol%, more preferably in the range of 15 to 97 mol% or in the range of 5 to 99 mol%, particularly 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 particularly 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%, especially 1 to 90 mol%, more preferably in the range of 3 to 85 mol% or in the range of 1 to 95 mol%, particularly 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 particularly in the range of 20 to 80 mol% or in the range of 30 to 75 mol%.

[0336] 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), is in the range of 50:50 to 99:1, in particular in the range of 70:30 to 98:2, especially in the range of 80:20 to 97:3.

[0337] 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 (I-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), is in the range of 30:70 to 90:10, in particular in the range of 40:60 to 85:15, especially in the range of 50:50 to 80:20.

[0338] 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 blend resin as long as the above structures are included in any of a plurality of polymer molecules. For example, a thermoplastic resin including all of the above structural units (II) and the structural unit (V) may be a copolymer including all of the structural units (II) and the structural unit (V), it may be a mixture of a homopolymer and a copolymer including at least one of the structural units (II) and a homopolymer or a copolymer including at least one of the structural units (V), or it may be a blend resin of a copolymer including at least one of the structural units (II) and a first structural unit (V) and a copolymer including at least one of the structural units (II) and at least one other structural unit (V) different from the first structural unit (V); etc.

[0339] 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.

[0340] Specifically, the thermoplastic resin (polycarbonate resin) can be prepared by the following method.

[0341] 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 carbonate diester. According to the present invention, the dihydroxy compound includes at least one dihydroxy compound represented by the formula (I), especially the dihydroxy compounds represented by the formula (Ia) or (Ib) as defined herein respectively. In addition to the compound of the formula (I), the dihydroxy compound may further include one or more dihydroxy compounds represented by the formula (IV), preferably the formula (IV-1) to (IV-8), especially the dihydroxy compounds represented by the formula (IV-11) to (IV-22), particularly the dihydroxy compounds represented by the formula (IV-11), (IV-12), (IV-13), (IV-14), (IV-15), (IV-21) or (IV-22).

[0342] As is clear from the above, the polycarbonate resin can be formed by reacting a dihydroxy component with a carbonate precursor such as a dicarbonate, 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 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), or (IV-22). Specifically, the polycarbonate resin 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 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), or (IV-22) react with a carbonate precursor such as a dicarbonate in the presence of a basic compound catalyst, a transesterification catalyst, or a mixed catalyst thereof, or under catalyst-free conditions.

[0343] Thermoplastic resins (or polymers) other than the polycarbonate resin, such as polyester carbonate and polyester, are obtained by using the dihydroxy compounds represented by formula (I), (Ia), and (Ib), respectively, or a combination thereof with at least one 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), or (IV-22) as materials (or monomers).

[0344] As mentioned above, the monomers of formula (I) for manufacturing thermoplastic resins and similarly the comonomers of formula (IV) can contain impurities generated from their preparation.

[0345] 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 in which one of the Rs z is a single bond instead of O - Alk 4 - or O - Alk 4 -[O - Alk 4 -] w -.

[0346] 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.

[0347] The polycarbonate resin can be obtained by reacting a monomer compound of formula (I) with a carbonate precursor such as a carbonate diester, or can be obtained by reacting at least one monomer compound of formula (I), especially at least one monomer (I) preferably mentioned herein, with a combination of one or more monomer compounds of formula (IV), especially 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 carbonate diester.

[0348] However, during the polymerization process for manufacturing the polycarbonate resin, some compounds of formula (I) and (IV) may be converted into impurities, where one or both of the terminal R z OH groups are replaced by 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.

[0349] 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.

[0350] 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.

[0351] 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.

[0352] 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.

[0353] The lower limit of the total amount of these impurities is not important, but may be 0.1 ppm or 1.0 ppm.

[0354] 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.

[0355] 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.

[0356] 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, particularly in the range of 10,000 to 50,000 daltons, especially in the range of 15,000 to 50,000 daltons. The 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 referred to 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, 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, still more preferably 10,000 to 18,000.

[0357] 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, still more preferably 2.0 to 4.0.

[0358] 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.

[0359] The thermoplastic resin may include low molecular weight compounds. Preferably, based on the total weight of the thermoplastic resin, the thermoplastic resin includes 9 wt% or less, especially 7 wt% or less, and particularly 5 wt% or less, or 0.01 wt% or more, especially 0.1 wt% or more, and particularly 1 wt% or more; for example, 0.1 to 9 wt%, especially 0.1 to 7 wt%, particularly 0.1 to 5 wt%, especially 0.5 to 5 wt%, 1 to 5 wt%, 1 to 4 wt% or 1 to 3 wt% 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 an amount within the above range, the mechanical strength of the molded body made of such a thermoplastic resin generally increases, especially compared to the 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 includes 9 wt% or less, especially 7 wt% or less, particularly 5 wt% 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 likely to precipitate or only slightly precipitate (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.

[0360] The thermoplastic resin of the present invention, for example, particularly the above-mentioned polycarbonate resin, has a high refractive index (n D or n d ), and thus is suitable for preparing optical lenses. The value of the refractive index referred to herein is the value of a film with a thickness of 0.1 mm, and 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, particularly 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 1.640 or more, preferably 1.650 or more, more preferably 1.660 or more, still more preferably 1.670 or more, still more preferably 1.680 or more, particularly 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 1.640 to 1.700, 1.650 to 1.750 or 1.660 to 1.800, more preferably 1.670 to 1.800, still more preferably 1.680 to 1.800.

[0361] The Abbe number (ν) of the thermoplastic resin of the present invention, particularly 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.

[0362] ν = (n D -1) / (n F -n C )

[0363] n D : Refractive index at a wavelength of 589 nm

[0364] n C : Refractive index at a wavelength of 656 nm

[0365] n F : Refractive index at a wavelength of 486 nm

[0366] The glass transition temperature (Tg) of the thermoplastic resin of the present invention, particularly 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, and particularly 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 available temperatures and avoids the risk that the resin melting temperature may be too high, and thus the resin will decompose or color undesirably. In addition, it allows the preparation of molded articles (molds) 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.

[0367] 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 1x10 -2 , more preferably in the range of 0 to 5x10 -3 , even more preferably in the range of 0 to 2x10 -3 , particularly in the range of 0 to 1x10 -3 , especially in the range of 0 to 0.4x10 -3 .

[0368] The total light transmittance of an optical molded article such as an optical element made of 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 bisphenol A type polycarbonate resin and the like.

[0369] 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 from the device, and the total light transmittance is measured according to the method of JIS-K-7361-1 using a SE2000 type spectro-parallax measuring instrument manufactured by Nippon Denshoku Industries Co., Ltd.

[0370] The total light transmittance of the thermoplastic resin according to the present invention after PCT testing 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.

[0371] The b value (indicating hue) of the thermoplastic resin according to the present invention is preferably 5 or less. The smaller the b value, the less yellowish the color is, and the better the hue is.

[0372] According to the present invention, the diol component for preparing polycarbonate or polyester may additionally include one or more diol monomers different from the monomer compound of formula (I), for example, one or more monomers of formula (IV).

[0373] Suitable diol monomers different from the monomer compound of formula (I) are those conventionally used for preparing polycarbonate, such as

[0374] - aliphatic diols, such as ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, and hexylene glycol;

[0375] - alicyclic 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

[0376] - 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)).

[0377] 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). Specifically, 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.

[0378] 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, especially at least 15% by weight, or at least 20% by weight, particularly 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, especially 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, particularly 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 may also be up to 100% by weight.

[0379] 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%.

[0380] Accordingly, 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%.

[0381] 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%.

[0382] 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.

[0383] To adjust the molecular weight and melt viscosity, the monomers forming the thermoplastic polymer may also include monofunctional compounds, which are monofunctional alcohols in the case of polycarbonates and monofunctional alcohols or monofunctional carboxylic acids in the case of polyesters. Suitable monohydric alcohols are butanol, hexanol, and octanol. Suitable monocarboxylic acids include, for example, benzoic acid, propionic acid, and butyric acid. To increase the molecular weight and melt viscosity, the monomers forming the thermoplastic polymer may also 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%.

[0384] 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, ditolyl carbonate, phenyltolyl carbonate, dichlorophenyl 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 moles, more preferably 0.98 to 1.10 moles, relative to a total of 1 mole of the dihydroxy compound.

[0385] Suitable dicarboxylic acids include, but are not limited to

[0386] -aliphatic dicarboxylic acids, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid;

[0387] -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

[0388] -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.

[0389]

[0390]

[0391] Suitable ester-forming derivatives of the dicarboxylic acid include, but are not limited to, dialkyl esters, diphenyl esters, and xylenyl esters.

[0392] In the case of the polyester, the usage ratio of the ester-forming monomer 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.

[0393] The polycarbonate of the present invention can be prepared by reacting a glycol component including the monomer of formula (I) and optionally an additional glycol monomer such as the monomer of formula (IV) with a carbonate-forming monomer by a preparation method similar to the known polycarbonate preparation described in, for example, US 9,360,593, US2016 / 0319069, and US2017 / 0276837 (which are incorporated herein by reference in their entirety).

[0394] The polyester of the present invention can be prepared by reacting a glycol component including the monomer of formula (I) and optionally an additional glycol monomer such as the monomer of formula (IV) with a dicarboxylic acid or its ester-forming derivative by a preparation method similar to the known polyester preparation described in, for example, US2017 / 044311 and the documents cited therein (which are incorporated herein by reference in their entirety).

[0395] The poly(ester carbonate) of the present invention can be prepared by reacting a glycol component including the monomer of formula (I) and optionally an additional glycol monomer such as the monomer 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 poly(ester carbonate) known in the art.

[0396] In the case of using a carbonate-forming monomer or an ester-forming derivative of a polycarboxylic acid, the polycarbonate, polyester, and poly(ester carbonate) are generally prepared by reacting the monomers of the glycol component with the carbonate-forming monomer and / or the ester-forming monomer, i.e., the dicarboxylic acid or its ester-forming derivative, in the presence of an esterification catalyst, especially a transesterification catalyst.

[0397] Suitable transesterification catalysts are basic compounds, which specifically include but are not limited to alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, etc. Similarly, suitable transesterification catalysts are acidic compounds, which specifically include but are not limited to Lewis acid compounds of polyvalent metals, including compounds of, for example, zinc, tin, titanium, zirconium, lead, etc.

[0398] 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 salt, dipotassium salt, dicesium salt, dilithium salt of bisphenol A, sodium salt, potassium salt, cesium salt and lithium salt of phenol; and so on.

[0399] 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.

[0400] 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.

[0401] 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.

[0402] The usage ratio of the transesterification catalyst is usually 10 -9 to 10 -3 moles, preferably 10 -7 to 10 -4 moles, relative to a total of 1 mole of the dihydroxy compound.

[0403] Generally, polycarbonates, polyesters and polyester carbonates are prepared by melt polycondensation. In melt polycondensation, the monomers react in the absence of additional inert solvents. 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.

[0404] 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 advantageous 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.

[0405] 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 stirring blades, stirring blades, helical ribbon stirring blades, etc.; horizontal reactors, including paddle blades, grid blades, spectacle blades, etc.; or extruder reactors, including screws. Considering the viscosity of the polymerization product, it is preferred to use a reactor including a combination of these reactors.

[0406] According to a method for manufacturing a thermoplastic resin such as polycarbonate resin, after the completion of the polymerization reaction, 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, etc.; aromatic sulfonates such as p-toluenesulfonic acid, etc.; aromatic sulfonic esters such as butyl p-toluenesulfonate, hexyl p-toluenesulfonate, etc.; phosphoric acids such as phosphorous acid, phosphoric acid, phosphonic acid, etc.; phosphites such as triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, di-n-butyl phosphite, di-n-hexyl phosphite, dioctyl phosphite, monooctyl phosphite, etc.; phosphates such as triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, dibutyl phosphate, dioctyl phosphate, monooctyl phosphate, etc.; phosphonic acids such as diphenyl phosphonic acid, dioctyl phosphonic acid, dibutyl phosphonic acid, etc.; phosphonic esters such as diethyl phenylphosphonate, etc.; phosphines such as triphenylphosphine, bis(diphenylphosphino)ethane, etc.; boric acids such as boric acid, phenylboric acid, etc.; aromatic sulfonates such as tetrabutylphosphonium dodecylbenzenesulfonate, etc.; organic halides such as stearoyl chloride, benzoyl chloride, p-toluenesulfonyl chloride, etc.; alkyl sulfonic acids such as dimethylsulfonic acid, etc.; organic halides such as benzyl chloride, etc. The amount of these deactivators is usually 0.01 to 50 mol, preferably 0.3 to 20 mol, relative to the catalyst. After the catalyst is deactivated, there may be a step of removing low-boiling compounds from the polymer by distillation. The distillation is preferably carried out under reduced pressure, for example, at a pressure of 0.1 to 1 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.

[0407] 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.

[0408] 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 forming, extrusion molding, stretching, and the like.

[0409] Although the thermoplastic resin of the present invention can be molded as such, the 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).

[0410] 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.

[0411] 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, trioctadecyl phosphite, diphenylmonodecyl phosphite, diphenyloctyl phosphite, diphenylmonoisopropyl phosphite, monophenyldibutyl phosphite, monophenyldidecyl phosphite, monophenyldioctyl phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl) octyl phosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenylmonoorthoxenylphosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, dimethyl phenylphosphonate, diethyl phenylphosphonate, dipropyl phenylphosphonate, tetra(2,4-di-tert-butylphenyl)-4,4'-biphenyldiphosphonite, tetra(2,4-di-tert-butylphenyl)-4,3'-biphenyldiphosphonite, tetra(2,4-di-tert-butylphenyl)-3,3'-biphenyldiphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl-benzenephosphonite, bis(2,4-di-tert-butylphenyl)-3-phenyl-benzenephosphonite, etc. The content of the phosphorus-based processing stabilizer in the thermoplastic resin composition is preferably 0.001 to 0.2 parts by weight relative to 100 parts by weight of the thermoplastic resin.

[0412] 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. The content of the sulfur-based processing stabilizer in the thermoplastic resin composition is preferably 0.001 to 0.2 parts by weight relative to 100 parts by weight of the thermoplastic resin.

[0413] The preferred 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, palmityl 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 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.

[0414] 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.

[0415] Examples of benzotriazole ultraviolet absorbers include 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(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.

[0416] Examples of benzophenone ultraviolet 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-dodecyloxylbenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, etc.

[0417] Examples of triazine ultraviolet 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.

[0418] Examples of the cyclic iminoester-based ultraviolet 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'-biphenylene) 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), and the like.

[0419] Examples of the cyanoacrylate-based ultraviolet 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, and the like.

[0420] With respect to 100 parts by weight of the thermoplastic resin, the content of the ultraviolet 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 ultraviolet absorber contained in such a content range according to the use can provide sufficient weather resistance to the thermoplastic resin.

[0421] As described above, the thermoplastic polymer resins respectively including the repeating units of formulas (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 formulas (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, and particularly at least 1.670.

[0422] 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 including a structural unit of formula (II) can be calculated from the refractive index of the monomers for preparing the thermoplastic resin, and the refractive index of the monomers for preparing the thermoplastic resin can be measured by a refractometer or determined ab initio, for example, using computer software ACD / ChemSketch 2012 (Advanced Chemistry Development, Inc.).

[0423] In the case of a thermoplastic copolymer resin, the refractive index of a thermoplastic resin, especially a polycarbonate resin, can be calculated from the refractive indices of the homopolymers of the respective monomers forming the copolymer resin by the following so-called "Fox equation":

[0424] 1 / n D = x1 / n D1 + x2 / n D2 +....x n / n Dn ,

[0425] 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 synthesized solely from each of monomers 1, 2...n. 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.

[0426] The refractive index of a thermoplastic resin can be measured directly or indirectly. For direct measurement, according to the protocol of JIS-K-7142, using an Abbe refractometer and applying a 0.1 mm film of the thermoplastic resin, the refractive index n of the thermoplastic resin is measured at a wavelength of 589 nm 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).

[0427] 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.

[0428] 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.

[0429] 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.

[0430] 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.

[0431] 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.

[0432] In addition, the thermoplastic resin of the present invention can be mixed with additives for forming optical devices. As 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.

[0433] 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.

[0434] Optical devices made of an optical resin including repeating units of formula (II) defined herein and optionally repeating units of formula (V) are generally optical molded articles, such as optical lenses, such as automotive headlamp lenses, Fresnel lenses, fθ lenses for laser printers, camera lenses, lenses for glasses, and projection lenses for rear projection televisions, 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, and the like. 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, and the like.

[0435] 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 that is technically difficult to manufacture by processing glass.

[0436] 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).

[0437] 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 width of the conditions 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.

[0438] 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.

[0439] 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.

[0440] 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.

[0441] 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.

[0442] 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.

[0443] 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 incorporation of foreign substances into the optical film as much as possible, molding needs to be carried out in a low-dust environment. The dust environment is preferably level 6 or lower, more preferably level 5 or lower.

[0444] The following examples are used for further illustration of the present invention.

[0445] 1. Abbreviation:

[0446] m.p.: melting point

[0447] eq.: molar equivalent

[0448] THF: tetrahydrofuran

[0449] TBME: tert-butyl methyl ether

[0450] MeOH: methanol

[0451] THF: tetrahydrofuran

[0452] K2CO3: potassium carbonate

[0453] KI: potassium iodide

[0454] NaHCO3: sodium bicarbonate

[0455] NaOH: sodium hydroxide

[0456] NH4Cl: ammonium chloride

[0457] Na2SO4: sodium sulfate

[0458] HCl: hydrochloric acid

[0459] TLC: thin layer chromatography

[0460] n D : refractive index

[0461] 2. Preparation of the monomer of formula (I)

[0462] 2.1 Analysis related to the monomer of formula (I):

[0463] Measured using an 80 MHz NMR spectrometer (Magritek Spinsolve 80) at 23 °C 1 1H-NMR spectrum.

[0464] The melting point of the compound was determined by Büchi Melting Point B-545.

[0465] 2.2 Preparation examples:

[0466] Example 1: [[1,1'-Binaphthalene]-2,2'-diylbis(methylenoxy-4,1-phenylene)]dimethanol (compound of formula (Ia) where X = -CH2OH and A = 1,4-phenylene; compound 1 in Table A)

[0467]

[0468] Racemic 1,1'-bi-2-naphthol (40 g, 140 mmol, 1.00 eq.), 4-(chloromethyl)benzyl alcohol (50.32 g, 321 mmol, 2.3 eq.) and K2CO3 (57.92 g, 419 mmol, 3 eq.) were mixed with acetone (500 mL). KI (2.3 g, 13.9 mmol, 0.1 eq.) was added to the mixture, and then the mixture was stirred at 60 °C until TLC control (cyclohexane / ethyl acetate 1:1) showed complete conversion. The reaction mixture was filtered hot through celite to remove inorganic salts, and then the solvent was removed completely under reduced pressure. The crude product thus obtained was recrystallized from toluene / ethyl acetate (100 mL / 7.5 mL). The crystals obtained were recrystallized again from toluene / ethyl acetate (100 mL / 7.5 mL), where the solution was treated with activated carbon (5 g, Norit DX Ultra) before the start of crystallization, to give the title compound as a white solid (52.7 g, 100 mmol, 71% yield) with a chemical purity of 98.3%.

[0469] Melting point = 138 - 140 °C.

[0470] 1 1H-NMR (80 MHz, CDCl3, ppm): δ = 8.03 - 7.74 (m, 4H), 7.50 - 7.11 (m, 8H), 7.09 - 6.78 (s, 8H), 5.04 (s, 4H), 4.51 (d, J = 4.5 Hz, 4H), 1.95 (t, J = 4.5 Hz, 2H).

[0471] Example 2: Dimethyl 4,4'-[[1,1'-binaphthalene]-2,2'-diylbis(methylenoxy)]dibenzoate (formula (Ia) compound, where X = -C(O)OCH3 and A = 1,4-phenylene; 193 of the compounds in Table A)

[0472]

[0473] Racemic 1,1'-bi-2-naphthol (11 g, 38.4 mmol, 1.00 eq.), methyl (4-chloromethyl)benzoate (16.2 g, 87.7 mmol, 2.3 eq.) and K2CO3 (15.93 g, 115 mmol, 3 eq.) were mixed with acetone (300 mL). The mixture was stirred at 60 °C until TLC control (cyclohexane / ethyl acetate 2:1) showed complete conversion. The reaction mixture was filtered through Celite while hot to remove inorganic salts, and then the solvent was removed completely under reduced pressure. The crude product was recrystallized from ethyl acetate to give the title compound as a white solid (8.9 g, 15.3 mmol, yield 39.8%), with a chemical purity of 96.2%.

[0474] m.p. = 164 - 166 °C.

[0475] 1 1H-NMR (80 MHz, CDCl3, ppm): δ = 8.05 - 7.62 (m, 8H), 7.51 - 7.12 (m, 8H), 6.94 (d, J = 8.2 Hz, 4H), 5.07 (s, 4H), 3.86 (s, 6H).

[0476] Example 3a: 2,2'-Bis[(4-bromophenyl)methoxy]-1,1'-binaphthalene

[0477]

[0478] To a mixture of racemic 1,1'-bi-2-naphthol (100 g, 349 mmol, 1.00 eq.) and K2CO3 (120.7 g, 873 mmol, 2.5 eq.) in acetone (900 mL) was added 4-bromobenzyl bromide (187.7 g, 751 mmol, 2.15 eq.). The reaction mixture was stirred at 60 °C until TLC control (cyclohexane / ethyl acetate 2:1) showed complete conversion. The reaction mixture was filtered through Celite to remove inorganic salts, and then acetone was removed under reduced pressure. The crude product was recrystallized from ethyl acetate to give the title compound as a white solid (181 g, 289.9 mmol, yield 83%), with a chemical purity of 99.9%.

[0479] m.p. = 122 - 124 °C.

[0480] 1 1H-NMR (80 MHz, CDCl3, ppm): δ = 8.05 - 7.78 (m, 4H), 7.49 - 7.06 (m, 12H), 6.74 (d, J = 8.4 Hz, 4H), 4.96 (s, 4H).

[0481] Example 3b: [[1,1'-Binaphthalene]-2,2'-diylbis(methylenoxy[1,1'-biphenyl]-4',4-diyl)]di methanol (compound of formula (Ia), where X = -CH2OH and A = 4,4'-biphenylylene; compound 18 in Table A)

[0482]

[0483] To a mixture of racemic 2,2'-bis[(4-bromophenyl)methoxy]-1,1'-binaphthalene (25 g, 40 mmol, 1.00 eq.) and [4-(hydroxymethyl)phenyl]boronic acid (18 g, 118.46 mmol, 2.96 eq.) in THF (500 mL) was added an aqueous solution of K2CO3 (2 M, 350 mL). Subsequently, a mixture of palladium(II) acetate (90 mg, 0.4 mmol) and tris(o-tolyl)phosphine (488 mg, 1.6 mmol) was added to the reaction mixture, and then the mixture was stirred under reflux until TLC control (cyclohexane / ethyl acetate 1:1) showed complete conversion. After cooling to ambient temperature, the phases were separated, the aqueous phase was extracted with THF (100 mL), and the combined organic phases were washed with an aqueous solution of NaOH (10 wt%, 100 mL), washed twice each with a mixture of saturated aqueous NH4Cl (20 mL) and aqueous HCl (3 M, 50 mL), and finally washed with saturated aqueous NH4Cl (50 mL). The THF solution was treated with activated carbon (5 g, Norit DX Ultra) and Na2SO4 (50 g) at 55 °C for 1 hour, and then filtered through diatomaceous earth and cellulose after cooling to ambient temperature. The solvent was removed in vacuo, and the crude product was dissolved in 8-fold weight of THF. Then it was precipitated by adding twice the volume of cyclohexane. The resulting solid was filtered off by suction and washed twice with a 1:1 mixture of 50 mL THF and cyclohexane. The product was dried in vacuo to give the title compound as a white solid (21.8 g, 32.1 mmol, yield 80.3%), with a chemical purity of 95.8%.

[0484] m.p. = 235 - 240 °C (decomp.).

[0485] 1 H NMR (80 MHz, DMSO-d6, ppm): δ = 8.18 - 7.84 (m, 4H), 7.74 - 6.92 (m, 24H), 5.22 (s, 4H), 5.18 (t, J = 5.6 Hz, 2H), 4.50 (d, J = 5.6 Hz, 4H).

[0486] Example 4a: [(6,6'-Dibromo[1,1'-binaphthalene]-2,2'-diyl)bis(methylenoxy-4,1-phenylene)] dimethanol

[0487]

[0488] Racemic 6,6'-dibromo[1,1'-binaphthalene]-2,2'-diol (100 g, 0.225 mol, 1.0 eq.), 4-chloromethylbenzyl alcohol (81.1 g, 0.518 mol, 2.3 eq.) and K2CO3 (93.36 g, 3.0 eq.) were mixed with acetone (1000 mL). KI (0.5 g, 3 mmol, 0.013 eq.) was added to the mixture, and the mixture was stirred at 60 °C until TLC control (cyclohexane / ethyl acetate 1:1) showed complete conversion. The reaction mixture was filtered through celite while hot to remove inorganic salts, and then the solvent was removed completely under reduced pressure. The resulting crude product was washed twice with 500 mL of TBME, and then recrystallized twice from toluene / ethyl acetate (500 mL / 50 mL) to give the title compound as a white solid, which was obtained as a toluene solvate containing one equivalent of toluene (137.1 g, 0.177 mol, yield 78.7%), with a chemical purity of 97.6%.

[0489] 1 H NMR (80 MHz, DMSO-d6, ppm): δ = 8.31 - 6.75 (m, 23H), 5.13 (s, 4H), 5.07 (t, J = 5.6 Hz, 2H), 4.39 (d, J = 5.6 Hz, 4H), 2.30 (s, 3H).

[0490] Example 4b: [(6,6'-Di-2-naphthyl-[1,1'-binaphthalene]-2,2'-diyl)bis(methylenoxy-4,1-ya phenyl)]dimethanol, a compound of formula (Ia) wherein X = -CH2OH; A = 1,4-phenylene and R 0 = 2-naphthyl; the compound of Table B compound 8)

[0491]

[0492] [(6,6'-Dibromo[1,1'-binaphthalene]-2,2'-diyl)bis(methyleneoxy-4,1-phenylene)]dimethanol (56.69 g, 0.073 mol, 1.0 eq.) containing one equivalent of toluene and 2-naphthylboronic acid (30.16 g, 0.175 mol, 2.4 eq.) were mixed with THF (500 mL) and 250 mL of 2 molar aqueous K2CO3 solution. Palladium(II) acetate (0.2 g, 0.89 mmol, 0.012 eq.) and tris(o-tolyl)phosphine (0.68 g, 2.23 mmol, 0.03 eq.) were added to the mixture. The reaction mixture was heated to reflux until TLC control (MeOH / water 3:1) showed complete conversion. The reaction mixture was filtered hot through diatomaceous earth to remove impurities. Then, the organic phase was separated and washed with 20% (w / w) aqueous NaOH solution (2 x 100 mL), saturated aqueous NH4Cl solution (100 mL), 4 molar aqueous HCl solution (100 mL), and again with saturated aqueous NH4Cl solution (100 mL). The resulting solution was dried over Na2SO4, filtered through diatomaceous earth and cellulose in sequence, and then treated with activated carbon (5 g, Norit DX Ultra) at a temperature of 55 °C for 1 hour. The solution was cooled to ambient temperature, filtered through diatomaceous earth and cellulose in sequence, and then the solvent was removed under reduced pressure. The crude product thus obtained was recrystallized from toluene / ethyl acetate (600 mL, 10:1), where the solution was treated with activated carbon (5 g, Norit DX Ultra) before the start of crystallization, and then recrystallized twice from toluene / methanol (91 g and 35 g). After drying at 60 °C, the title compound as a white solid (20.7 g, 0.027 mol, yield 36.4%) with a chemical purity of 97.6% was obtained.

[0493] m.p. 188 - 191 °C.

[0494] 1 1H NMR (80 MHz, DMSO-d6, ppm): δ = 8.53 - 7.12 (m, 24H), 7.07 (s, 8H), 5.19 (s, 4H), 5.07 (t, J = 5.6 Hz, 2H), 4.38 (d, J = 5.6 Hz, 4H).

[0495] Example 5: [(6,6'-Diphenyl-[1,1'-binaphthalene]-2,2'-diyl)bis(methylenoxy-4,1-phenylene 2-(4-phenylphenyl)-1,3-propanediol (compound of formula (Ia) where X = -CH2OH; A = 1,4-phenylene and R 0 = phenyl; compound of Table B 1)

[0496]

[0497] 6,6'-Diphenyl[1,1'-binaphthalene]-2,2'-diol (50 g, 0.114 mol, 1.0 eq.), 4-chloromethylbenzyl alcohol (39.28 g, 0.251 mol, 2.2 eq.) and K2CO3 (47.28 g, 3.0 eq.) were mixed with acetone (500 mL). KI (1 g, 6 mmol, 0.05 eq.) was added to the mixture and the mixture was stirred at 60 °C until TLC control (cyclohexane / ethyl acetate 1:1) showed complete conversion. The reaction mixture was filtered hot through diatomaceous earth to remove inorganic salts and then the solvent was removed completely under reduced pressure. The crude product thus obtained was recrystallized from toluene / ethyl acetate (232 mL / 19 mL), where the solution was treated with activated carbon (4 g Norit DX Ultra) before the start of crystallization and then recrystallized again from toluene / ethyl acetate (174 mL / 14 mL) to give the title compound as a white solid (19.8 g, 0.029 mmol, yield 25.6%), with a chemical purity of 95.4%.

[0498] m.p. = 170 - 171 °C.

[0499] 1 1H NMR (80 MHz, CDCl3, ppm): δ = 8.17 - 7.30 (m, 20H), 6.98 (s, 8H) 5.09 (s, 4H), 4.51 (d, J = 2.8 Hz, 2H), 2.03 (t, J = 2.8 Hz, 2H).

[0500] 2.3 Refractive index n of the monomer of formula (I) D :[[-END]]

[0501] Table C below lists the refractive indices of some monomers of formula (I) calculated using the software ACD / ChemSketch 2012 (Advanced Chemistry Development, Inc.). Each monomer in Table C is identified by its number in Tables A and B. In addition, it was confirmed by quantum chemical calculations of all monomers included in Table C that they do not absorb or absorb only to a negligible extent in the visible light range and are thus essentially colorless.

[0502] Table C

[0503]

[0504]

[0505]

[0506] 3. Preparation of polycarbonate resin from the monomer of formula (I)

[0507] 3.1 Analysis related to the resin prepared from the monomer of formula (I):

[0508] Refractive index (n D ):

[0509] The refractive index was measured using test pieces 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.

[0510] Abbe number (ν):

[0511] Samples having the same thickness of about 3 mm as the test pieces used in the above refractive index measurement method were 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:

[0512] ν = (n D - 1) / (n F - n C )

[0513] n D : Refractive index at a wavelength of 589 nm

[0514] n C : Refractive index at a wavelength of 656 nm

[0515] n F : Refractive index at a wavelength of 486 nm

[0516] Glass transition temperature (Tg):

[0517] The glass transition temperature was measured by differential scanning calorimetry (DSC) according to JIS K7121-1987 using a heating program of 10 °C / min.

[0518] Differential scanning calorimeter:

[0519] X-DSC7000, manufactured by Hitachi High-Tech Science Corporation

[0520] Molecular weight

[0521] The molecular weight distribution of the resin molecules, particularly the value of the weight-average molecular weight (Mw) of the resin, was measured by gel permeation chromatography (GPC) and calculated by standard polystyrene conversion. The following apparatus, columns, and measurement conditions were used:

[0522] GPC apparatus: HLC-8420GPC (from Tosoh Corporation);

[0523] Columns: Three TSKgel SuperHM-M (from Tosoh Corporation),

[0524] One guard column SuperHM-M (from Tosoh Corporation),

[0525] One TSKgel SuperH-RC (from Tosoh Corporation);

[0526] Detection device: RI detection

[0527] Standard polystyrene: PstQuick C as a standard polystyrene kit (from Tosoh Corporation);

[0528] Eluent: Tetrahydrofuran;

[0529] Eluent flow rate: 0.6 ml / min;

[0530] Column temperature: 40 °C.

[0531] The number-average molecular weight (Mn) value can be calculated using a method similar to the method used for measuring the above Mw value. The weight-average molecular weight (Mw) and number-average molecular weight (Mn) converted to polystyrene are calculated using a pre-made polystyrene standard curve. Specifically, a standard curve is made using standard polystyrene with a known molecular weight ("PStQuick C" from Tosoh Corporation). Additionally, based on the measurement data of the standard polystyrene, the elution time and molecular weight values of each peak are plotted and three-dimensionally approximated to obtain a calibration curve. The Mw and Mn values are calculated based on the following calculation formulas:

[0532] Mw = Σ(Wi × Mi) ÷ Σ(Wi)

[0533] Mn = Σ(Ni × Mi) ÷ Σ(Wi)

[0534] In the calculation formulas, "i" represents the "i"-th breakpoint, "Wi" represents the molecular weight (g) of the polymer at the "i"-th breakpoint, "Ni" represents the number of polymer molecules at the "i"-th breakpoint, and "Mi" represents the molecular mass at the "i"-th breakpoint. The molecular mass (M) represents the molecular mass value of polystyrene at the corresponding elution time in the calibration curve.

[0535] Content of low molecular weight compounds (CLWC)

[0536] The content of the low-molecular-weight compound represents the area ratio of compounds with an Mw value of less than 1,000 in GPC analysis. Therefore, the content of the low-molecular-weight compound is determined according to the following formula:

[0537]

[0538] The GPC analysis of the low-molecular-weight compound was carried out as described above for measuring the molecular weight of the thermoplastic resin.

[0539] 3.2 Preparation examples of homopolycarbonate:

[0540] General method:

[0541] 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 remove the obtained test piece lens. The homopolycarbonate prepared by this method, the refractive index measured thereon, and the Abbe number are listed in Table D below.

[0542] Table D

[0543]

[0544] 3.3 Preparation examples of copolycarbonate resin:

[0545] Example 6 (E6)

[0546] 19.8339 g (0.0452 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF), 10.2092 g (0.0194 mol) of [[1,1'-binaphthalene]-2,2'-diylbis(methyleneoxy-4,1-phenylene)]dimethanol (i.e., the compound of formula (Ia) where X = -CH2OH and A = 1,4-phenylene) obtained in Example 1, 14.2581 g (0.0666 mol) of diphenyl carbonate (DPC), and 0.5428×10 -4 g (0.6462×10 -6 mol) of sodium bicarbonate were used as raw materials and placed in a 300-ml reactor equipped with a stirrer and a distillation device. The reactor was filled with nitrogen, and the internal pressure was set to 101.3 kPa.

[0547] The reactor was immersed in an oil bath at 200 °C, and then the transesterification reaction was started. Stirring of the reaction mixture was started 5 minutes after the start of the reaction. After 20 minutes, the pressure was reduced from 101.3 kPa to 26.66 kPa within 10 minutes. During this pressure reduction process, the mixture was heated to 210 °C. Then it was further heated to 220 °C 60 minutes after the start of the reaction. From 80 minutes after the start of the reaction, the pressure was reduced to 20.00 kPa within 10 min. Then the reaction mixture was heated to 240 °C and the pressure was reduced to 0 kPa, and these conditions were maintained for 30 minutes. Finally, the pressure was raised back to 101.3 kPa by introducing nitrogen gas into the reactor to obtain the desired polycarbonate resin.

[0548] The refractive index of the obtained polycarbonate resin was 1.6487, the Abbe number was 22.09, the Tg was 138 °C, and the polystyrene-reduced weight-average molecular weight (Mw) was 35,067. The ratio of the diol compound and the properties of the obtained resin are summarized in Table E below.

[0549]

[0550] Comparative Example 1 (CE1):

[0551] The method in Example 6 above was repeated to prepare a polycarbonate resin, except that the same molar amount of 2,2-bis(2-hydroxyethoxy)-1,1'-binaphthalene (BNE) was used instead of the monomer of Example 1 as the diol component. The properties of the obtained resin are also summarized in Table E below.

[0552] Comparative Example 2 (CE2):

[0553] The method in Example 6 above was repeated to prepare a polycarbonate resin, except that only 0.0646 mol of BPEF was used as the diol component instead of the mixture of the monomer of Example 1 and BPEF. The properties of the obtained resin are also summarized in Table E below.

[0554]

[0555] Table E: Properties of the polycarbonate resins of E6, CE1, and CE2

[0556]

Claims

1. Use of a compound of formula (I) as a monomer for the production of a thermoplastic resin 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 each independently selected from monocyclic or polycyclic arylene having 6 to 26 carbon atoms as ring members and monocyclic or polycyclic heteroarylene having a total of 5 to 26 atoms as ring members, wherein 1, 2, 3 or 4 of these ring member atoms of the heteroarylene 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 Ar groups; R 1 and R 2 are independently selected from halogen, C2-C3-alkynyl, CN, R, OR, CH s R' 3-s , NR2, C(O)R and CH=CHR”, provided that if p + q > 1, R 1 and R 2 may be the same or different, where s is 0, 1 or 2 each time it appears; p and q are independently 0, 1 or 2; R Ar Selected from R, OR, CH t R' 3-t , NR2 and CH=CHR”, where if there are more than one R on the same heteroarylene or arylene Ar , then the R Ar can be the same or different, where t is 0, 1 or 2 each time it appears; R is selected from C1-C4-alkyl, phenyl, naphthyl, phenanthryl and triphenylenyl, where phenyl, naphthyl, phenanthryl and triphenylenyl are unsubstituted or substituted by 1, 2, 3 or 4 identical or different R'" groups; R' is selected from phenyl, naphthyl, phenanthryl and triphenylenyl, where phenyl, naphthyl, phenanthryl and triphenylenyl are unsubstituted or substituted by 1, 2, 3 or 4 identical or different R'" groups; R” is selected from hydrogen, methyl, phenyl and naphthyl, where 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 26 carbon atoms as ring members and monocyclic or polycyclic heteroarylenes having a total of 5 to 26 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 Ar groups; R 1 and R 2 are each independently selected from halogen, C2-C3-alkynyl, CN, R, OR, CH s R' 3-s , NR2, C(O)R and CH=CHR”, provided that if p + q > 1, R 1 and R 2 may be the same or different, where s is 0, 1 or 2 each time it appears; p and q are independently 0, 1 or 2; R Ar selected from R, OR, CH t R' 3-t , NR2 and CH═CHR”, where if there are more than one R on the same heteroaryl or aryl or heteroarylene or arylene Ar , then the R Ar may be the same or different, where t is 0, 1 or 2 each time it appears; R is selected from C1-C4 alkyl, phenyl, naphthyl, phenanthryl and triphenylenyl, where phenyl, naphthyl, phenanthryl and triphenylenyl are unsubstituted or substituted by 1, 2, 3 or 4 identical or different R'" groups; R' is selected from phenyl, naphthyl, phenanthryl and triphenylenyl, where phenyl, naphthyl, phenanthryl and triphenylenyl are unsubstituted or substituted by 1, 2, 3 or 4 identical or different R'" groups; R” is selected from hydrogen, methyl, phenyl and naphthyl, where 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) below: wherein A 1 and A 2 are both unsubstituted phenylene groups, p and q are both 0, and X 1 and X 2 are both -CH2OH or -C(O)OR x wherein R x is hydrogen, methyl or ethyl.

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, particularly from hydrogen, methyl and ethyl, and especially from hydrogen and methyl.

5. The use or compound according to any one of the preceding claims, wherein A 1 and A 2 at least one of which comprises a first benzene ring and at least one additional ring selected from benzene rings, 5-membered heterocycles and 6-membered heterocycles, wherein the additional ring is fused to the first benzene ring or linked to the first benzene ring by a single bond.

6. 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'-sulfonyldiphenylene, 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-11,12-diyl, pyrene-1,6-diyl, Group, methylene, triphenylenylene, furyl, benzofuran-2-yl, dibenzofuran-4-yl, naphtho[1,2-b]furan-3-yl, naphtho[2,3-b]furan-4-yl, naphtho[2,1-b]furan-3-yl, benzonaphtho[1,2-d]furan-5-yl, benzonaphtho[2,3-d]furan-6-yl, benzonaphtho[2,1-d]furan-5-yl, benzofuro[1,2-b:4,3-b']bifuran-6-yl, benzofuro[1,2-b:6,5-b']bifuran-7-yl, benzofuro[1,2-b:5,4-b']bifuran-6-yl, benzofuro[1,2-b:4,5-b']bifuran-7-yl, 9H-xanthenyl, tribenzo[b,d,f]oxepin-5-yl, xanthenyl, 2H-naphtho[1,8-d,e][1,3]dioxin-6-yl, phenoxathiin-3-yl, dinaphtho[2,3-b:2',3'-d]furan-6-yl, xanthenyl, benzo[a]xanthenyl, benzo[b]xanthenyl, thienyl, benzothiophen-2-yl, dibenzothiophen-4-yl, naphtho[1,2-b]thiophen-3-yl, naphtho[2,3-b]thiophen-4-yl, naphtho[2,1-b]thiophen-3-yl, benzonaphtho[1,2-d]thiophen-5-yl, benzonaphtho[2,3-d]thiophen-6-yl, benzonaphtho[2,1-d]thiophen-5-yl, benzothieno[1,2-b:4,3-b']bithiophen-6-yl, benzothieno[1,2-b:6,5-b']bithiophen-7-yl, benzothieno[1,2-b:5,4-b']bithiophen-6-yl, benzothieno[1,2-b:4,5-b']bithiophen-7-yl, 9H-thioxanthenyl, 6H-dibenz[b,d]thiopyran-5-yl, 1,4-benzodithiin-3-yl, naphtho[1,2-b][1,4]dithiin-4-yl, naphtho[2,3-b][1,4]dithiin-5-yl, 9H-10-thiaxanthenyl, thianthren-3-yl, benzo[a]thianthren-4-yl, benzo[b]thianthren-3-yl, dibenzo[a,c]thianthren-5-yl, dibenzo[a,h]thianthren-6-yl, dibenzo[a,i]thianthren-6-yl, dibenzo[a,j]thianthren-6-yl, dibenzo[b,i]thianthren-5-yl, 2H-naphtho[1,8-b,c]thiophen-4-yl, dibenz[b,d]thiepin-5-yl, dibenz[b,f]thiepin-5-yl, 5H-phenanthro[4,5-b,c,d]thiopyran-6-yl, tribenzo[b,d,f]thiepin-5-yl, 2,5-dihydronaphtho[1,8-b,c:4,5-b',c']bithiophen-6-yl, 2,6-dihydronaphtho[1,8-b,c:5,4-b',c']bithiophen-7-yl, tribenzo[a,c,i]thianthren-6-yl, benzonaphtho[1,8-e,f][1,4]dithiepin-7-yl, dinaphtho[2,3-b:2',3'-d]thiophen-6-yl, 5H-phenanthro[1,10-b,c]thiophen-6-yl, 7H-phenanthro[1,10-c,b]Thienyl, dibenzo[d,d']benzo[1,2-b:4,5-b']bithiophenyl and dibenzo[d,d']benzo[1,2-b:5,4-b']bithiophenyl., 7. The use or compound according to claim 6, wherein A 1 and A 2 are each independently selected from phenylene, naphthylene, biphenylene, benz[b]furylene, dibenz[b,d]furylene, benz[b]thiophenylene, dibenz[b,d]thiophenylene, 9H-fluorene-9,9-diyl, xanthene-9,9-diyl, thianthren-2,2-diyl, phenoxathiin-10,10-diyl, 9H-xanthen-9,9-diyl and 9H-thioxanthene-9,9-diyl, preferably selected from phenylene, naphthylene, biphenylene, dibenz[b,d]thiophenylene, 9H-fluorene-9,9-diyl, xanthene-9,9-diyl, thianthren-2,2-diyl, phenoxathiin-10,10-diyl, 9H-xanthen-9,9-diyl and 9H-thioxanthene-9,9-diyl, and particularly preferably selected from phenylene, naphthylene, biphenylene, dibenz[b,d]thiophenylene and thianthren-2,2-diyl.

8. The use or compound according to claim 7, wherein A 1 and A 2 are independently selected from 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 1,4-naphthylene, 1,5-naphthylene, 2,7-naphthylene, 2,6-naphthylene, 1,3-naphthylene, 3,1-naphthylene, 2,3-naphthylene, 1,2-naphthylene, 2,1-naphthylene, 4,4'-biphenylene, 3,4'-biphenylene, 3,3'-biphenylene, 4,3'-biphenylene, 2,2'-biphenylene, 4,2'-biphenylene, 3,2'-biphenylene, 2,4'-biphenylene, 2,3'-biphenylene, 2,8-dibenzo[b,d]thiophene-2,8-diyl, 4,6-dibenzo[b,d]thiophene-4,6-diyl, 2,8-thianthren-2,8-diyl and 1,9-thianthren-1,9-diyl.

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

10. 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, phenyl, naphthyl and phenanthryl, particularly preferably from phenyl and naphthyl.

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

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

13. The use or compound according to any one of the preceding claims, wherein formula (I) is represented by formula (Ia), where the definition of X is the same as that of X in any one of claims 1 to 4 1 and X 2 has the same definition, and where the definition of A is the same as that of A in any one of claims 1, 2 and 5 to 9 1 and A 2 has the same definition:

14. Use or compound according to claim 13, wherein X and A are defined as in a row of Table A: Table A: *) The connection positions "n,m-" contained 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 group -CH2-.

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

16. The use or compound according to any one of the preceding claims, wherein formula (I) is represented by formula (Ib), where the definition of X is the same as X in any one of claims 1 to 4 1 and X 2 has the same definition, where the definition of A is the same as A in any one of claims 1, 2 and 5 to 9 1 and A 2 has the same definition, and where R 0 has the same definition as R in any one of claims 1, 2, 10 and 11 1 and R 2 has the same definition:

17. The use or compound according to claim 16, wherein X, A and R 0 are defined as a row in Table B: Table B: *) The connection positions "n,m-" contained 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 group -CH2-.

18. Use according to claim 1 and any one of claims 3 to 17, wherein the thermoplastic resin is selected from polycarbonates, polyesters and polyester carbonates.

19. A thermoplastic resin comprising a structural unit represented by the following formula (II) wherein # represents the connection point to an adjacent structural unit; and wherein X 1a and X 2a are respectively derived from X 1 and X 2 , replacing X 1 or X 2 with an oxo (-O-) moiety for the -OH or -OR x group, and wherein X 1 、X 2 、A 1 、A 2 、R 1 、R 2 、p and q are as defined in any one of claims 1 to 12 and 15.

20. The thermoplastic resin according to claim 19 has the formula (IIa), wherein X a is defined as X in claim 19 1a and X 2a are defined identically, and wherein A is defined as A in any one of claims 1, 2, and 5 to 9 1 and A 2 are defined identically:

21. The thermoplastic resin according to claim 19, which has formula (IIb), wherein the definition of X a is the same as that of X in claim 19 1a and the definition of X 2a is the same, wherein the definition of A is the same as that of A in any one of claims 1, 2, and 5 to 9 1 and the definition of A 2 is the same, and wherein the definition of R 0 is the same as that of R in any one of claims 1, 2, 10, and 11 1 and the definition of R 2 is the same:

22. The thermoplastic resin according to any one of claims 19 to 21, wherein the structural unit of formula (II) is connected to one of the structures represented by formulae (III-1) to (III-5), and in the structural unit of formula (II), X 1a and X 2a are both -CH2O-, wherein # represents the connection point to an adjacent structural unit.

23. The thermoplastic resin according to any one of claims 19 to 22, which is selected from copolycarbonate resins, copolyester carbonate resins and copolyester resins, wherein in addition to the structural unit represented by formula (II), the thermoplastic resin further comprises a structural unit of formula (V), #-O-R z -A 3 -R z -O-#-(V) wherein # represents the connection point to an adjacent structural unit; A 3 is a polycyclic group with at least 2 benzene rings, where the benzene rings can be fused to each other through W-linkages and / or directly and / or through non-benzene carbocyclic rings and / or through two non-benzene carbocyclic rings fused via a linking group L, where A 3 is unsubstituted or substituted by 1, 2 or 3 R aa groups, and the R aa groups are selected from halogen, C1-C6-alkyl, C5-C6-cycloalkyl, phenyl, naphthyl, 1,2-dihydroacenaphthylenyl, phenanthrenyl, pyrenyl, triphenylenyl, benz[b]furanyl, dibenz[b,d]furanyl, benz[b]thiophenyl, dibenz[b,d]thiophenyl and thianthrenyl; 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') wherein Q' represents a single bond, O, C═O, CH2, S or SO2; and R 7a 、R 7b are each independently 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 in claim 1, and v is 0, 1 or 2; and * represents the point of attachment to the benzene ring; 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 R L groups, and the R L groups are selected from C1-C4-alkyl, halogen, C1-C4-haloalkyl, C4-C7-cycloalkyl and phenyl, 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 R ab groups, said R ab groups are selected from halogen, phenyl and C1-C4-alkyl; R z is a single bond, Alk 3 , O-Alk 4 -, O-Alk 4 -[O-Alk 4 -] w - or O-Alk 5 -C(O)-, where O is bonded to A 3 and where w is an integer from 1 to 10; Alk 3 is a C1-C4-alkanediyl; Alk 4 is a C2-C4-alkanediyl; and Alk 5 is a C1-C4-alkanediyl group.

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

25. The thermoplastic resin according to any one of claims 23 or 24, wherein based on the total molar amount of the structural unit of formula (II) and the structural unit of formula (V), the molar ratio of the structural unit of formula (II) is 1 to 99 mol%, preferably 10 to 99 mol%, especially 15 to 97 mol%, and based on the total molar amount of the structural unit of formula (II) and the structural unit of formula (V), the molar ratio of the structural unit of formula (V) is 1 to 99 mol%, preferably 1 to 90 mol%, especially 3 to 85 mol%.

26. The thermoplastic resin according to any one of claims 23 to 25, having a refractive index of 1.640 or more.

27. The thermoplastic resin according to any one of claims 23 to 26, having an Abbe number of 24 or less.

28. The thermoplastic resin according to any one of claims 23 to 27, having a glass transition temperature (Tg) of 90 to 185 °C.

29. The thermoplastic resin according to any one of claims 23 to 28, having a weight-average molecular weight measured by gel permeation chromatography using polystyrene as a standard of 10,000 to 50,000.

30. The thermoplastic resin according to any one of claims 23 to 29, based on the total weight of the thermoplastic resin, comprising 9 wt% or less of low molecular weight compounds having a molecular weight of less than 1000.

31. The thermoplastic resin according to any one of claims 23 to 30, wherein the thermoplastic resin is selected from polycarbonate, polyester and polyester carbonate.

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

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