Aryl(hetaryl)-substituted bisphenol compounds and thermoplastic resins

Abstract

The present invention relates to compounds of formula (I): [Formula 1] TIFF2024533305000113.tif2451 (wherein X is a single bond, O, N-(C1-C4)-alkyl, N-Ar 1 , C.R. 5 R 6 , S, S(O) and SO2; Z 1 and Z 2 is hydrogen, -Alk-OH, -CH2-Ar 2 -CH2-OH, -Alk'-C(O)OR x , -CH2-Ar 2 -C(O)OR x and -C(O)-Ar 2 -C(O)OR x (R x are independently selected from the group consisting of hydrogen, phenyl, benzyl and C1-C4-alkyl; R 1 and R 2 is independently selected from the group consisting of optionally substituted monocyclic or polycyclic aryl having 6 to 26 carbon atoms as ring members and optionally substituted monocyclic or polycyclic hetaryl having a total of 5 to 26 atoms as ring members; R 5 is hydrogen, C1-C4-alkyl and Ar 1 R 6 is selected from the group consisting of hydrogen and C1-C4-alkyl; Alk is C2-C4-alkanediyl, with the proviso that R 3 and R 4 If both are hydrogen, R 1 and R 2 and neither of them are phenyl. The present invention also relates to the use of compounds of formula (I) as defined herein as monomers for the preparation of thermoplastic resins comprising structural units of formula (II): [chemical 2] TIFF2024533305000114.tif2461 (wherein # represents a point of attachment to an adjacent structural unit; and X, Z 1a , Z 2a , R 1 , R 2 , R 3 and R4 The present invention also relates to an optical element made of a thermoplastic resin comprising a structural unit of formula (II) as defined herein.

Description

[Technical field]

[0001] The present invention relates to aryl(hetaryl)-substituted bisphenol compounds which have advantageous optical and mechanical properties and are suitable as monomers for the preparation of thermoplastic resins, such as polycarbonate resins, which can be used in the manufacture of optical elements. [Background technology]

[0002] Optical elements such as optical lenses made of optical resins instead of optical glass have the advantage that they can be mass-produced by injection molding. Recently, optical resins, especially transparent polycarbonate resins, are frequently used in the manufacture of camera lenses. In this regard, resins with a higher refractive index are highly desirable because they reduce the size and weight of the final product. Usually, when an optical material with a higher refractive index is used, a lens element with the same refractive power can be realized with a surface with a smaller curvature, and the amount of aberration generated by this surface can be reduced. As a result, weight reduction can be achieved by reducing the number of lenses, reducing the decentering sensitivity of the lens, and / or reducing the lens thickness.

[0003] European Patent No. 2,034,337 describes a copolycarbonate resin having 99-51 mol % of repeating units derived from 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene and 1-49 mol % of repeating units derived from bisphenol A. This resin is suitable for producing optical lenses having a low Abbe number of 23-26 and a refractive index of 1.62-1.64.

[0004] US Patent No. 9,360,593 describes polycarbonate resins having repeat units derived from 2,2'-bis(2-hydroxyethoxy)-1,1-binaphthyl. The polycarbonate resins are said to have advantageous optical properties in terms of high refractive index, low Abbe number, high transparency, low birefringence and glass transition temperature suitable for injection molding. Copolycarbonates of bis(2-hydroxyethoxy)-1,1-binaphthyl monomers and 10,10-bis(4-hydroxyphenyl)anthrone monomers and their use for producing optical lenses are described in US Patent Application Publication No. 2016 / 0319069. The copolycarbonates are reported to have excellent water resistance and a refractive index of about 1.662 to 1.667.

[0005] WO 2019 / 043060 describes a thermoplastic resin for producing an optical material, the thermoplastic resin comprising a polymerized compound of formula (2).

[0006] [ka]

[0007] During the ceremony, X is, for example, C2-C4-alkanediyl; R and R' are the same or different and are selected from optionally substituted monocyclic or polycyclic aryl having 6 to 36 carbon atoms and optionally substituted monocyclic or polycyclic hetaryl having a total of 5 to 36 atoms.

[0008] WO 2019 / 154727 describes a thermoplastic resin for producing an optical material, the thermoplastic resin comprising a polymerized compound of formula (3).

[0009] [ka]

[0010] During the ceremony, R 1 , R 2 is, for example, hydrogen; Y is an alkylene group having 2, 3 or 4 carbon atoms; Ar is selected from monocyclic or polycyclic aryl and monocyclic or polycyclic hetaryl; X 1 , X 2 , X 3 , X 4 , CH, CR x or N, provided that in each ring, X 1 , X 2 , X 3 , X 4 at most two of are N; R x is, for example, halogen, CN or CH=CH2.

[0011] WO 2020 / 079225 describes a thermoplastic resin for producing an optical material, the thermoplastic resin comprising a polymerized compound of formula (4).

[0012] [ka]

[0013] During the ceremony, A 1 , A 2 is selected from monocyclic or bicyclic aromatic groups and monocyclic or bicyclic heteroaromatic groups; X represents, for example, a single bond, O, NH, or an optionally substituted carbon atom; Y is, for example, absent or represents a single bond or has the meaning given for X; R 1 , R 2 is a hydrogen atom, an Ar′ group or R a It is a base; R 3 is in particular O-alkylene; m, n are 0, 1 or 2; R 4 , R 5For example, CN and R a selected from the group; R a is C≡CR 11 and Ar-C≡CR 11 (R 11 is selected from the group consisting of Ar and an aromatic group; A 1 Or A 2 At least one of the groups bonded to R a It is based on

[0014] SR Turner et al., High Performance Polymers 17 (2005) pp. 361-376, describes amorphous copolyesters derived from bisphenols such as bis(2-hydroxyethoxy)-2,2'-diphenyl]bisphenol S (=di-[4-(2-hydroxyethoxy)-2-phenyl]-phenylsulfone) and bis[(2-hydroxyethoxy)-2,2'phenyl]-4,4'-biphenol.

[0015] Also, monomers for producing thermoplastic resins with high refractive index generally result in positive birefringence values ​​for the resin. For optical elements, birefringence is an undesirable property. So far, positive birefringence has been compensated for by using comonomers with negative birefringence, such as 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene. However, these comonomers lower the refractive index of the resulting polymer. Currently, few monomers are known that provide high refractive index and low birefringence.

[0016] Despite the progress in the field of optical resins, there is still a continuing need for monomers that provide high refractive index for making optical resins, especially polycarbonate and polyester resins, and thus are useful for making optical elements, especially lenses.Apart from this, the monomers must not impair other optical properties of the optical resins, such as low Abbe number, high transparency and low birefringence.In addition, the monomers must be easy to prepare.In addition, the resins obtained from these monomers, especially polyesters and polycarbonates, are required to have good water resistance and heat resistance, and have a sufficiently high glass transition temperature suitable for injection molding. [Prior art documents] [Patent documents]

[0017] [Patent Document 1] EP2034337 [Patent Document 2] US9,360,593 [Patent Document 3] US2016 / 0319069 [Patent Document 4] International Publication No. 2019 / 043060 [Patent Document 5] International Publication No. 2019 / 154727 [Patent Document 6] International Publication No. 2020 / 079225 [Non-patent literature]

[0018] [Non-Patent Document 1] SR Turner et al., High Performance Polymers 17(2005) pp. 361-376 [Brief description of the drawings]

[0019] [Figure 1]1 shows the results of measuring the retardation or birefringence of the resins produced in Examples 31, 33 and 34 and a polycarbonate resin derived from bisphenol A. [Diagram 2] 2 is a partially enlarged portion of FIG. 1 for the retardation or birefringence of the polymers of Examples 31, 33 and 34. [Diagram 3] FIG. 2 shows a GPC diagram of the resin. Summary of the Invention

[0020] Surprisingly, it has been found that the compounds of formula (I) described herein are useful monomers for producing thermoplastic resins, particularly polycarbonates and polyesters, with high transparency and high refractive index, and also provide suitable glass transition temperatures to polycarbonates and polyesters. Thus, the thermoplastic resins are suitable for producing optical resins that require high transparency and high refractive index. Some of the monomers of formula (I) described herein provide both high refractive index and low or even negative birefringence. Furthermore, the compounds of formula (I) can be easily incorporated into polyesters and polycarbonates and are thermally stable under polymerization conditions. Thus, the resulting polyesters and polycarbonates have low yellowness. Thus, the thermoplastic resins containing the monomers of formula (I) in the polymerization formation can be advantageously used for producing optical elements made of the resin.

[0021] Thus, the present invention relates to compounds of formula (I):

[0022] [ka]

[0023] During the ceremony, X is a single bond, O, N-(C1-C4)-alkyl, N-Ar 1 , C.R. 5 R 6 , S, S(O) and SO2; Z 1 and Z 2is hydrogen, -Alk 1 -OH, -CH2-Ar 2 -CH2-OH, -Alk 2 -C(O)OR x , -CH2-Ar 2 -C(O)OR x and -C(O)-Ar 2 -C(O)OR x (R x are independently selected from the group consisting of hydrogen, phenyl, benzyl and C1-C4-alkyl; R 1 and R 2 are monocyclic or polycyclic aryls having 6 to 26 carbon atoms as ring members and monocyclic or polycyclic hetaryls having a total of 5 to 26 ring atoms, where 1, 2, 3 or 4 of these hetaryl ring atoms are selected from nitrogen, sulfur and oxygen, and the remaining hetaryl ring atoms are carbon atoms. The monocyclic or polycyclic aryls and monocyclic or polycyclic hetaryls are unsubstituted or substituted with 1, 2, 3 or 4 R Ar independently selected from the group consisting of: R 3 and R 4 are hydrogen, monocyclic or polycyclic aryl having 6 to 26 carbon atoms as ring members, and monocyclic or polycyclic hetaryl having a total of 5 to 26 ring atoms, where 1, 2, 3 or 4 of these ring atoms of the hetaryl are selected from nitrogen, sulfur and oxygen, and the remaining ring atoms of the hetaryl are carbon atoms. The monocyclic or polycyclic aryl and monocyclic or polycyclic hetaryl are unsubstituted or substituted with 1, 2, 3 or 4 R Ar independently selected from the group consisting of: R 5 is selected from the group consisting of hydrogen and C1-C4-alkyl; R 6 is selected from the group consisting of hydrogen and C1-C4-alkyl; Ar 1are monocyclic or polycyclic aryls having 6 to 26 carbon atoms as ring members and monocyclic or polycyclic hetaryls having a total of 5 to 26 ring atoms, where 1, 2, 3 or 4 of these hetaryl ring atoms are selected from nitrogen, sulfur and oxygen, and the remaining hetaryl ring atoms are carbon atoms. The monocyclic or polycyclic aryls and monocyclic or polycyclic hetaryls are unsubstituted or substituted with 1, 2, 3 or 4 R Ar a group having a aryl group; Ar 2 is selected from the group consisting of phenylene, naphthylene, and biphenylylene; Alk is C2-C4-alkanediyl; Alk' is C1-C4-alkanediyl; R Ar R, OR, CH n R 3-n , NR2 and CH=CHR', and R Ar When more than one is present, they may be the same or different; R is selected from the group consisting of methyl, ethyl, phenyl, naphthyl, phenanthrenyl and triphenylenyl, wherein phenyl, naphthyl, phenanthrenyl and triphenylenyl are unsubstituted or substituted with 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 with 1, 2, 3 or 4 identical or different R" groups; R″ is selected from the group consisting of phenyl, OCH3, CH3, N(CH3)2, and C(O)CH3; n is 0, 1 or 2. However, R 3 and R 4 If both are hydrogen, R 1 and R 2 Neither of them is phenyl.

[0024] The above compounds are particularly useful in the preparation of thermoplastic resins, especially optical resins as defined herein, especially polycarbonate resins.

[0025] When used as a monomer for the preparation of optical resins, particularly polycarbonate and polyester resins, the compounds of formula (I) provide the resins with a high refractive index. In addition, the compounds of formula (I) provide high transparency for the resins without significantly impairing other optical and mechanical properties of the resins. In particular, these resins meet other requirements for optical resins, such as low Abbe number, high transparency and low birefringence. Furthermore, the monomers provide the optical resins prepared therefrom with a sufficiently high glass transition temperature. Besides, the monomers of formula (I) can be easily prepared and obtained with high yield and high purity. In particular, the compounds of formula (I) can be obtained in a crystalline form that allows efficient purification to the extent required for the preparation of optical resins. In particular, the compounds of formula (I) can be obtained with a purity that results in low haze, which is particularly important for use in the preparation of optical resins. Some R 1 Group, R 2 Group, R 3 Group, R 4 Group and Ar 1 Compounds of formula (I) that do not have chromophoric groups such as the aryl group can also be obtained in high purity, with low yellowness index YI measured according to ASTM E313 and low APHA color numbers, which may be important for use in the manufacture of optical resins.

[0026] The present invention also relates to a thermoplastic resin containing a polymerized unit of the compound of formula (I), that is, a thermoplastic resin containing a structural unit represented by the following formula (II):

[0027] [ka]

[0028] During the ceremony, # represents the point of attachment to the adjacent structural unit; and Z 1a and Z 2a are Z, 1 Or Z 2 is hydrogen, by replacing the hydrogen with a single bond, or by Z 1 Or Z 2If is not hydrogen, Z 1 Or Z 2 -OH group or -OR x The Z group of formula (I) can be substituted with an oxo (-O-) unit. 1 or Z 2 Derived from, and Z 1 , Z 2 , X, R 1 , R 2 , R 3 and R 4 is as defined above.

[0029] The present invention further relates to a thermoplastic resin selected from copolycarbonate resins, copolyestercarbonate resins and copolyester resins, which in addition to the structural units of formula (II) also contain structural units of formula (V) #-OR z -A 1 -R z -O-#- (V)

[0030] During the ceremony, # represents the point of attachment to the adjacent structural unit; A 1 is a polycyclic group having at least two benzene rings, which may be linked by A and / or directly fused to each other and / or fused to a non-benzene carbocyclic ring, and A 1 is unsubstituted or 1, 2 or 3 R aa Group(R aa is substituted with selected from the group consisting of halogen, C1-C6-alkyl, C5-C6-cycloalkyl and phenyl; A is selected from the group consisting of a single bond, O, C=O, S, SO2, CH2, CH-Ar, CAr2, CH(CH3), C(CH3)2 and a group of formula (A');

[0031] [ka]

[0032] During the ceremony, Q represents a single bond, O, NH, C=O, CH2 or CH=CH; R 7a , R 7b are each independently hydrogen, fluorine, CN, R, OR, or CH k R 3-k , NR2, C(O)R and C(O)NH2, where R is as defined herein and k is 0, 1, 2 or 3; * represents the point of attachment to the benzene ring; Ar is selected from the group consisting of monocyclic or polycyclic aryl having 6 to 26 carbon atoms as ring members and monocyclic or polycyclic hetaryl having a total of 5 to 26 ring atoms, in which 1, 2, 3 or 4 of the hetaryl ring atoms are selected from nitrogen, sulfur and oxygen, and the remaining hetaryl ring atoms are carbon atoms, and Ar is unsubstituted or substituted with 1, 2 or 3 R ab Group(R ab is substituted with selected from the group consisting of halogen, phenyl and C1-C4-alkyl; R z is a single bond, Alk 1 , O-Alk 2 -, O-Alk 2 -[O-Alk 2 ] p - or O-Alk 3 -C(O)-(O is A 1 (bonded to); p is an integer from 1 to 10; Alk 1 is C1-C4-alkanediyl; Alk 2 is C2-C4-alkanediyl; and Alk 3 is C1-C4-alkanediyl.

[0033] The invention further relates to an optical element made of a thermoplastic resin as defined above, in particular a polyester, especially a polycarbonate.

[0034] When X is a single bond, the compound of formula (I) has the substituent -OZ 1 , -OZ 2 , R 1 , R 2 , R 3 and R 4 Depending on the type and position of the bond between the two phenylene moieties, the rotation of the bond between the two phenylene moieties is probably restricted, and therefore the compound of formula (I) may have axial asymmetry. In that case, the compound of formula (I) may exist in the form of the (S)-enantiomer and the (R)-enantiomer. As a result, the compound of formula (I) may exist as a racemic mixture or as a non-racemic mixture or in the form of the pure (S)- and (R)-enantiomers, respectively. The present invention relates to both the racemic and non-racemic mixtures of the enantiomers of the compound of formula (I) when X is a single bond, and also to the pure (S)- and (R)-enantiomers, insofar as these enantiomers exist.

[0035] In the present invention, the term "C1-C4-alkanediyl group", also indicated as "alkylene group having 1, 2, 3 or 4 carbon atoms", refers to a divalent saturated aliphatic hydrocarbon group having 1, 2, 3 or 4 carbon atoms. Examples of C2-C4-alkanediyl are in particular straight-chain alkanediyls such as methylene group (CH2), 1,2-ethanediyl (CH2CH2), 1,3-propanediyl (CH2CH2CH2) and 1,4-butanediyl (CH2CH2CH2CH2), but also branched-chain alkanediyls such as 1-methyl-1,2-ethanediyl, 1-methyl-1,2-propanediyl, 2-methyl-1,2-propanediyl, 2-methyl-1,3-propanediyl and 1,3-butanediyl.

[0036] In the present invention, the term "monocyclic aryl" refers in particular to a monovalent aromatic monocyclic group such as phenyl.

[0037] In the present invention, the term "monocyclic hetaryl" refers to a monovalent heteroaromatic monocyclic group, i.e., a heteroaromatic monocyclic ring attached to the remainder of the molecule by a single covalent bond. The ring atoms are part of a conjugated π-electron system, and the heteroaromatic monocyclic ring has 5 or 6 ring atoms (including 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, the remaining ring atoms being 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.

[0038] In the present invention, the term "monocyclic or polycyclic aryl" refers to a monovalent aromatic monocyclic group or a monovalent aromatic polycyclic group as defined herein, i.e., a polycyclic arene attached to the remainder of the molecule by a single covalent bond. Polycyclic arenes are: (i) aromatic polycyclic hydrocarbons (i.e., fully unsaturated polycyclic hydrocarbons in which each carbon atom is part of a conjugated pi-electron system); (ii) polycyclic hydrocarbons having at least one phenyl ring fused to a saturated or unsaturated 4- to 10-membered monocyclic or bicyclic hydrocarbon ring; (iii) Polycyclic hydrocarbons having at least two phenyl rings which are covalently bonded to each other or directly fused to each other and / or to a saturated or unsaturated 4-10 membered monocyclic or bicyclic hydrocarbon ring.

[0039] Monocyclic or polycyclic aryls have 6 to 26, often 6 to 24 carbon atoms as ring atoms, for example 6, 9, 10, 12, 13, 14, 16, 17, 18, 19, 20, 22 or 24 carbon atoms, in particular 6 to 20 carbon atoms, in particular 6, 10, 12, 13, 14, 16, 17 or 18 carbon atoms. Polycyclic aryls typically have 10 to 26, in particular 10 to 20 carbon atoms, in particular 10, 12, 13, 14, 16, 17 or 18 carbon atoms as ring atoms.

[0040] In the present specification, examples of polycyclic aryls having 2, 3 or 4 phenyl rings bonded to each other via single bonds include biphenylyl and terphenylyl. Examples of polycyclic aryls having 2, 3 or 4 phenyl rings directly fused to each other include naphthyl, anthracenyl, phenanthrenyl, pyrenyl, triphenylenyl, chrysenyl and benzo[c]phenanthrenyl. Examples of polycyclic aryls having 2, 3 or 4 phenyl rings fused to a saturated or unsaturated 4-10 membered monocyclic or bicyclic hydrocarbon ring include 9H-fluorenyl, biphenylenyl, tetraphenylenyl, acenaphthenyl (1,2-dihydroacenaphthylenyl), acenaphthylenyl, 9,10-dihydroanthracen-1-yl, 1,2,3,4-tetrahydrophenanthrenyl, 5,6,7,8 ... Examples of fluoranthrenyl include 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.

[0041] Examples of the monocyclic or polycyclic aryl include phenyl, naphthyl, 9H-fluorenyl, phenanthryl, anthracenyl, pyrenyl, chrysenyl, benzo[c]phenanthrenyl, acenaphthenyl, acenaphthylenyl, 2,3-dihydro-1H-indenyl, 5,6,7,8-tetrahydro-naphthalenyl, cyclopenta[fg]acenaphthylenyl, 2,3-dihydrophenalenyl, 9,10-dihydroanthracen-1-yl, 1,2,3,4-tetrahydrophenanthrenyl, 5,6,7,8-tetrahydrophenanthrenyl, fluoranthenyl, benzo[k]fluoranthenyl, biphenylenyl, triphenylenyl, tetraphenylenyl, 1,2-dihydroacenaphthylenyl, dibenzo[a,e][8]annulenyl, perylenyl, and biphenylyl. phenyl, terphenylyl, naphthylenephenyl, phenanthrylphenyl, anthracenylphenyl, pyrenylphenyl, 9H-fluorenylphenyl, di(naphthylene)phenyl, naphthylenebiphenyl, tri(phenyl)phenyl, tetra(phenyl)phenyl, pentaphenyl(phenyl), phenylnaphthyl, binaphthyl, phenanthrylnaphthyl, pyrenylnaphthyl, phenylanthracenyl, biphenylanthracenyl, naphthalenylanthracenyl, phenanthrylanthracenyl, dibenzo[a,e][8]annulenyl, 9,10-dihydro-9,10[1',2']benzoanthracenyl, 9,9'-spirobi-9H-fluorenyl, and spiro[1H-cyclobuta[de]naphthalene-1,9'-[9H]fluorenyl]yl.

[0042] In the present invention, the term "monocyclic or polycyclic hetaryl" denotes a monovalent heteroaromatic monocyclic group or a monovalent heteroaromatic polycyclic group as defined herein, i.e., a polycyclic hetaryl group attached to the remainder of the molecule by a single covalent bond. (i) the polycyclic hetarene has a heteroaromatic monocycle as defined above and at least one, e.g., 1, 2, 3, 4 or 5 further aromatic rings selected from phenyl and heteroaromatic monocycles as defined above, the aromatic rings of the polycyclic hetarene being covalently bonded to each other and / or directly fused to each other and / or fused to a saturated or unsaturated 4-10 membered monocyclic or bicyclic hydrocarbon ring; or (ii) the polycyclic hetaranes are at least one saturated or partially or completely unsaturated 5-, 6-, 7- or 8-membered heterocycle having one, two or three 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-dioxine, oxepin, thiepin, dioxine, dithiin, dioxepin, dithiepin, dioxo-xine ... Heterocyclic polyhetaranes have at least one aromatic ring, e.g., 1, 2, 3, 4 or 5 aromatic rings selected from heterocyclic, dithiocyanine, and phenyl and heteroaromatic monocycles as defined above, at least one of which is directly fused to a saturated or partially unsaturated 5-8 membered heterocycle, and the aromatic rings of polycyclic hetarenes are bonded to each other by covalent bonds or are directly fused to each other and / or to a saturated or unsaturated 4-10 membered monocyclic or bicyclic hydrocarbon ring.

[0043] Monocyclic or polycyclic hetaryls have 5 to 26, often 5 to 24, especially 5 to 20 ring atoms, including 1, 2, 3 or 4 atoms selected from nitrogen, sulfur and oxygen atoms, the remaining ring atoms being carbon atoms. Polycyclic hetaryls generally have 9 to 26, often 9 to 24, especially 9 to 20 ring atoms, including 1, 2, 3 or 4 atoms selected from nitrogen, sulfur and oxygen atoms, the remaining ring atoms being carbon atoms.

[0044] Examples of polycyclic hetaryl 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 aryl, pyrido[3,2-b]indolyl, pyrido[3,2-g]quinolinyl, pyrido[2,3-b][1,8]naphthyridinyl, pyrrolo[3,2-b]pyridinyl, pteridinyl, pryl, 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, ben zo[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]thio-pyranyl, 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']bisthienyl, 1,4-benzodithiynyl, naphtho[1,2-b][1,4]dithiynyl, 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, benzo[g]thiochromenyl, pyrrolo[3,2,1-hi]indolyl, benzo[g]quinoxalinyl, benzo[f]quinoxalinyl, and benzo[h]isoquinolinyl.

[0045] In the present invention, the terms "phenylene", "naphthylene" and "biphenylylene" refer to divalent substituents of benzene, naphthalene and biphenyl, respectively, as is conventional in the art. Thus, the terms "phenylene", "naphthylene" and "biphenylylene" are used herein synonymously with the terms phendiyl, naphthalenediyl and biphenyldiyl, respectively.

[0046] In the present invention, a "structural unit" is a structural element that occurs repeatedly in the polymer backbone of a thermoplastic resin. Thus, the terms "structural unit" and "repeating unit" are used interchangeably.

[0047] In the present invention, the term "optical element" refers to an element that is transparent to visible light and manipulates light rays, especially by refraction. Optical elements include, but are not limited to, prisms, lenses, optical films and combinations thereof, especially camera lenses and eyeglass lenses.

[0048] The following statements concerning preferred embodiments of the variables (substituents) of the compounds of formula (I) and of the structural units of formula (II) are valid on their own and, preferably, in combination with one another.

[0049] Furthermore, the following explanations regarding preferred embodiments of the variables are valid for compounds of formula (I) and structural units of formula (II) and, where applicable, for the uses according to the invention, on their own and preferably in combination with one another.

[0050] R in formula (I) 3 and R 4 If both are hydrogen, R 1 Groups and R 2 The group is preferably a polycyclic aryl having 10 to 26 carbon atoms as ring atoms and a polycyclic hetaryl having a total of 9 to 26 ring atoms, where 1, 2, 3 or 4 of the polycyclic hetaryl ring atoms are selected from the group consisting of nitrogen, sulfur and oxygen, and the remaining hetaryl ring atoms are carbon atoms. The polycyclic aryl and polycyclic hetaryl are unsubstituted or substituted with 1, 2, 3 or 4 RAr The aryl group is selected from the group consisting of aryl, aryl, and aryl groups.

[0051] In formula (I) and similarly in formula (II), the variables X, R 1 , R 2 , R 3 , R 4 , Z 1 and Z 2 alone or preferably in any combination, preferably has the following meanings:

[0052] Hydrogen, -Alk-OH, -CH2-Ar 2 -CH2-OH, -Alk'-C(O)OR x and -CH2-Ar 2 -C(O)OR x The variable Z of formula (I) is independently selected from 1 and Z 2 , thus -Alk-O-, -CH2-Ar 2 -CH2-O-, -Alk'-C(O)O- and -CH2-Ar 2 Variable Z of formula (II) is independently selected from -C(O)O- 1a and Z 2a (Alk, -Alk', Ar 2 and R x has the meanings defined herein, in particular the preferred meanings).

[0053] In a preferred group (1) of embodiments, the variable Z of formula (I) 1 and Z 2 -Alk-OH and -CH2-Ar 2 —CH—OH, and thus the variable Z of formula (II) 1a and Z 2a -Alk-O- and -CH2-Ar 2 -CH2-O- (Alk is preferably a linear C2-C4-alkanediyl such as 1,2-ethanediyl (CH2-CH2), 1,3-propanediyl or 1,4-butanediyl, in particular 1,2-ethanediyl; Ar 2is preferably selected from 1,4-phenylene, 1,3-phenylene, 2,6-naphthylene, 1,4-naphthylene, 1,5-naphthylene and 4,4'-biphenylylene. In this context, the variable Z 1 and Z 2 or the variable Z of formula (II) 1a and Z 2a are also preferably identical to each other.

[0054] Thus, in a particularly preferred subgroup (1.1) of embodiments, the variable Z 1 and Z 2 is selected from 2-hydroxyethyl (i.e. 2-(HO)-ethyl), hydroxymethyl-phenyl-methyl (i.e. HO-methyl-phenyl-methyl), hydroxymethyl-naphthyl-methyl and hydroxymethyl-biphenylyl-methyl, in particular from 2-hydroxyethyl, 4-(hydroxymethyl)phenyl)methyl, (3-(hydroxymethyl)phenyl)methyl, 4-(hydroxymethyl)-1-naphthyl)methyl, (5-(hydroxymethyl)-1-naphthyl)methyl, (6-(hydroxymethyl)-2-naphthyl)methyl and 4'-(hydroxymethyl)-1,1'-biphenylyl-4-methyl, in particular from 2-hydroxyethyl, 4-(hydroxymethyl)phenyl)methyl and (3-(hydroxymethyl)phenyl)methyl. Correspondingly, in a particularly preferred group (1.1) of this embodiment, the variable Z of formula (II) 1a and Z 2a is selected from 2(-O)-ethyl, -O-methyl-phenyl-methyl and -O-methyl-naphthyl-methyl, in particular from 2(-O)-ethyl, (4(-O-methyl)phenyl)methyl, (3(-O-methyl)phenyl)methyl, (4(-O-methyl)-1-naphthyl)methyl, (5(-O-methyl)-1-naphthyl)methyl, (6(-O-methyl)-2-naphthyl)methyl and 4'(-O-methyl)-1,1'-biphenylyl-4-methyl, in particular from 2(-O)-ethyl, (4(-O-methyl)phenyl)methyl and (3(-O-methyl)phenyl)methyl, (4(-O-methyl)-1-naphthyl)methyl.

[0055] In a particular subgroup (1′) of embodiments, the variable Z 1 and Z 2 have the same meaning, and similarly, the variable Z 1a and Z 2a have the same meaning and are selected from the meanings defined in groups (1) and (1.1) of the embodiments.

[0056] In another group (2) of embodiments, the variable Z of formulas (I) and (II) 1 and Z 2 are both hydrogen, and therefore the variable Z 1a and Z 2a Both are single bonds.

[0057] In a preferred group (3) of embodiments, the variable Z of formula (I) 1 and Z 2 is -Alk'-C(O)OR x and -CH2-Ar 2 -C(O)OR x and thus the variable Z of formula (II) is independently selected from 1a and Z 2a is -Alk'-C(O)O- and -CH2-Ar 2 -C(O)O- (Alk' is preferably methylene or a straight-chain C1-C4-alkanediyl such as 1,2-ethanediyl (CH2-CH2), in particular methylene, Ar 2 is preferably selected from 1,4-phenylene, 1,3-phenylene, 2,6-naphthylene, 1,5-naphthylene and 1,4-naphthylene, R x is preferably hydrogen or C1-C4-alkyl, in particular methyl). In this context, the variable Z 1 and Z 2 Or variable part Z 1a and Z 2a are also preferably identical to each other.

[0058] Thus, in a particularly preferred subgroup (3.1) of embodiments, the variable Z 1and Z 2 is selected from methoxycarbonyl-methyl (i.e. CHO-C(O)-methyl), methoxycarbonyl-phenyl-methyl (i.e. CHO-C(O)-phenyl-methyl) and methoxycarbonyl-naphthyl-methyl, in particular from methoxycarbonyl-methyl, (4-(methoxycarbonyl)phenyl)methyl, (3-(methoxycarbonyl)phenyl)methyl, (4-(methoxycarbonyl)-1-naphthyl)methyl, (5-(methoxycarbonyl)-1-naphthyl)methyl and (6-(methoxycarbonyl)-2-naphthyl)methyl, in particular from methoxycarbonyl-methyl, (4-(methoxycarbonyl)phenyl)methyl and (3-(methoxycarbonyl)phenyl)methyl. Correspondingly, in a particularly preferred group (3.1) of this embodiment, the variable Z of formula (II) is 1a and Z 2a is selected from -OC(O)-methyl, -OC(O)-phenyl-methyl and -OC(O)-naphthyl-methyl, in particular from -OC(O)-methyl, (4(-OC(O)-phenyl)methyl, (3(-OC(O)-phenyl)methyl, (4-(-OC(O)-)-1-naphthyl)methyl, (5-(-OC(O)-)-1-naphthyl)methyl and (6-(-OC(O)-)-2-naphthyl)methyl, in particular from -OC(O)-methyl, (4(-OC(O)-phenyl)methyl and (3(-OC(O)-phenyl)methyl.

[0059] In a particular subgroup (3') of embodiments, the variable Z of formula (I) 1 and Z 2 have the same meaning, and similarly, the variable Z 1a and Z 2a have the same meaning and are selected from the meanings defined in groups (3) and (3.1) of the embodiments.

[0060] In a preferred group of embodiments (4), which is a combination of groups (1.1), (2) and (3.1), the variable Z of formula (I) is 1 and Z 2from hydrogen, 2-hydroxyethyl, methoxycarbonyl-methyl, hydroxymethyl-phenyl-methyl, hydroxymethyl-naphthyl-methyl, hydroxymethyl-biphenylyl-methyl, methoxycarbonyl-phenyl-methyl and methoxycarbonyl-naphthyl-methyl, in particular hydrogen, 2-hydroxyethyl, methoxycarbonyl-methyl, (4-(hydroxymethyl)phenyl)methyl, (3-(hydroxymethyl)phenyl)methyl, (4-(hydroxymethyl)-1-naphthyl)methyl, (5-(hydroxymethyl)-1-naphthyl)methyl, (6-(hydroxymethyl)-2-naphthyl)methyl, 4'-(hydroxymethyl)-1,1'-biphenylyl-4-methyl, (4-(hydroxymethyl)-1,1'-biphenylyl-4-methyl, Correspondingly, in a preferred group (4) of this embodiment, the variable Z of formula (II) is selected from among hydrogen, 2-hydroxyethyl, methoxycarbonyl-methyl, (4-(hydroxymethyl)phenyl)methyl, (3-(hydroxymethyl)phenyl)methyl, (4-(methoxycarbonyl)-1-naphthyl)methyl, (5-(methoxycarbonyl)-1-naphthyl)methyl and (6-(methoxycarbonyl)-2-naphthyl)methyl, in particular from hydrogen, 2-hydroxyethyl, methoxycarbonyl-methyl, (4-(hydroxymethyl)phenyl)methyl, (3-(hydroxymethyl)phenyl)methyl, (4-(methoxycarbonyl)phenyl)methyl and (3-(methoxycarbonyl)phenyl)methyl. 1a and Z 2afrom the single bond, 2(-O)-ethyl, -OC(O)-methyl, -O-methyl-phenyl-methyl, -O-methyl-naphthyl-methyl, -OC(O)-phenyl-methyl and -OC(O)-naphthyl-methyl, in particular the single bond, 2(-O)-ethyl, -OC(O)-methyl, (4(-O-methyl)phenyl)methyl, (3(-O-methyl)phenyl)methyl, (4(-O-methyl)-1-naphthyl)methyl, (5(-O-methyl)-1-naphthyl)methyl, (6(-O-methyl)-2-naphthyl)methyl, (4(-OC(O)-phenyl)methyl, (3-(-OC(O) (-OC(O)-phenyl)methyl, (4-(-OC(O)-)-1-naphthyl)methyl, (5-(-OC(O)-)-1-naphthyl)methyl and (6-(methoxycarbonyl)-2-naphthyl)methyl, in particular from a single bond, 2(-O)-ethyl, -OC(O)-methyl, (4(-O-methyl)phenyl)methyl, (3(-O-methyl)phenyl)methyl, 4(-OC(O)-phenyl)methyl and (3-(-OC(O)-phenyl)methyl, in particular from a single bond, 2(-O)-ethyl, (4(-O-methyl)phenyl)methyl and (3(-O-methyl)phenyl)methyl.

[0061] In a particular subgroup (4') of embodiments, the variable Z 1 and Z 2 have the same meaning, and similarly, the variable Z 1a and Z 2a have the same meaning and are selected from the meanings defined in group (4) of embodiments.

[0062] The variable X is preferably a single bond, O, N-methyl, N-ethyl, Nn-propyl, N-isopropyl, N-sec-butyl, N-iso-butyl, N-tert-butyl, N-Ar 1 , CH2, C(CH3)2, CH(CH3), C(CH3)(CH2CH3), S, SO and SO2(N-Ar 1 Ar 1 is as defined herein, and Ar 1is in particular selected from the group consisting of phenyl, naphthyl, phenanthryl, biphenylyl, fluorenyl, pyrenyl, chrysenyl, benzo[b]furanyl, dibenzo[b,d]furanyl, naphtho[1,2-b]furanyl, naphtho[2,3-b]furanyl, naphtho[2,1-b]furanyl, oxanthreneyl, benzo[b]thienyl, dibenzo[b,d]thienyl, naphtho[1,2-b]thienyl, naphtho[2,3-b]thienyl, naphtho[2,1-b]thienyl and thianthrenyl, in particular selected from the group consisting of phenyl, naphthyl, phenanthryl, biphenylyl, fluorenyl, benzo[b]furanyl, dibenzo[b,d]furanyl, benzo[b]thienyl and dibenzo[b,d]thienyl.

[0063] In particular, the variable X can be a single bond, O, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-tert-butyl, N-Ar 1 , CH2, C(CH3)2, CH(CH3), C(CH3)(CH2CH3), S and SO2(Ar 1is naphthyl such as phenyl, naphth-1-yl or naphth-2-yl; phenanthryl such as phenanthren-1-yl, phenanthren-2-yl, phenanthren-3-yl, phenanthren-4-yl or phenanthren-9-yl; biphenylyl such as biphenyl-2-yl, biphenyl-3-yl or biphenyl-4-yl; fluorenyl such as fluoren-1-yl, fluoren-2-yl, fluoren-3-yl or fluoren-4-yl; benzo[b]furanyl such as benzo[b]furan-2-yl, benzo[b]furan-3-yl, benzo[b]furan-4-yl, benzo[b]furan-5-yl, benzo[b]furan-6-yl or benzo[b]furan-7-yl; dibenzo[b,d]furanyl such as dibenzo[b,d]furan-1-yl, dibenzo[b,d]furan-2-yl, dibenzo[b,d]furan-3-yl or dibenzo[b,d]furan-4-yl; benzo[b]thienyl such as benzo[b]thien-2-yl, benzo[b]thien-3-yl, benzo[b]thien-4-yl, benzo[b]thien-5-yl, benzo[b]thien-6-yl or benzo[b]thien-7-yl; and dibenzo[b,d]thienyl such as dibenzo[b,d]thien-1-yl, dibenzo[b,d]thien-2-yl, dibenzo[b,d]thien-3-yl or dibenzo[b,d]thien-4-yl).

[0064] In a preferred group (5) of embodiments, the variable X is selected from the group consisting of a single bond, O, N-phenyl, N-naphthyl, N-phenanthryl, CH2, C(CH3)2, CH(CH3), S, S(O) and SO2, in particular from the group consisting of a single bond, O, N-phenyl, N-naphth-1-yl, N-naphth-2-yl, N-phenanthren-9-yl, CH2, C(CH3)2, S, S(O) and SO2, in particular from the group consisting of a single bond, O, CH2, C(CH3)2, S, S(O) and SO2, in particular from the group consisting of a single bond, C(CH3)2, S and SO2.

[0065] In a particular subgroup (5') of embodiments, the variable X is CH2, C(CH3)2 or CH(CH3), in particular C(CH3)2. In another particular subgroup (5'') of embodiments, the variable X is S or SO2. In yet another particular subgroup (5''') of embodiments, the variable X is a single bond.

[0066] Preferably, the variable part R 1 and R 2 are monocyclic or polycyclic aryls having 6 to 18 carbon atoms as ring atoms and polycyclic hetaryls having a total of 9 to 26 ring atoms, in particular 9 to 18 ring atoms (one or two of these ring atoms of the hetaryl are oxygen or sulfur atoms, and the remaining hetaryls are carbon atoms). The monocyclic or polycyclic aryls and polycyclic hetaryls are unsubstituted or have one or two R Ar Group(R Ar is independently selected from the group consisting of one of the meanings defined herein, in particular one of the meanings described as preferred (group 6) of embodiments). More preferably, R 1 and R 2 At least one of the following, especially R 1 and R 2 are both selected from polycyclic aryl having 10 to 18 carbon atoms as ring atoms and polycyclic hetaryl having a total of 9 to 18 ring atoms.

[0067] According to a more preferred group of embodiments (6.1), R 1 and R 2is naphthyl such as phenyl, naphth-1-yl or naphth-2-yl; 1,2-dihydroacenaphthylenyl such as 1,2-dihydroacenaphthylen-3-yl or 1,2-dihydroacenaphthylen-5-yl; biphenylyl such as biphenyl-4-yl, biphenyl-3-yl or biphenyl-2-yl; fluorenyl such as fluoren-1-yl, fluoren-2-yl, fluoren-3-yl or fluoren-4-yl; 11H-benzo[a]fluorenyl such as 11H-benzo[a]fluoren-7-yl; 11H-benzo[b]fluoren-1-yl, etc. 11H-benzo[b]fluorenyl, 7H-benzo[c]fluoren-5-yl or 7H-benzo[c]fluoren-10-yl, phenanthrenyl, such as phenanthren-1-yl, phenanthren-2-yl, phenanthren-3-yl, phenanthren-4-yl or phenanthren-9-yl, benzo[c]phenanthren-1-yl, benzo[c]phenanthren-2-yl, benzo[c]phenanthren-3-yl, benzo[c]phenanthren-4-yl, benzo[c]phenanthren-5-yl or Examples of the aryl groups include benzo[c]phenanthrenyl such as benzo[c]phenanthren-6-yl, pyrenyl such as pyren-1-yl, pyren-2-yl, and pyren-4-yl, chrysenyl such as chrysen-1-yl, chrysen-2-yl, chrysen-3-yl, chrysen-4-yl, chrysen-5-yl, and chrysen-6-yl, picenyl such as picen-3-yl, triphenylenyl such as triphenylen-1-yl and triphenylen-2-yl, benzo[b]furan-2-yl, benzo[b]furan-3-yl, benzo[b]furan-4-yl, and benzo[b]furan-5-yl. benzo[b]furanyl such as benzo[b]furan-6-yl or benzo[b]furan-7-yl; dibenzo[b,d]furanyl such as dibenzo[b,d]furan-1-yl, dibenzo[b,d]furan-2-yl, dibenzo[b,d]furan-3-yl or dibenzo[b,d]furan-4-yl; naphtho[1,2-b]furanyl such as naphtho[1,2-b]furan-5-yl; naphtho[2,3-b]furan-3-yl, naphtho[2,3-b]furan-4-yl or naphtho[2,3-b]furan-9-yl; naphtho[2,naphtho[2,1-b]furanyl such as 1-b]furan-2-yl or naphtho[2,1-b]furan-5-yl, benzo[b]naphtho[1,2-d]furanyl such as benzo[b]naphtho[1,2-d]furan-1-yl or benzo[b]naphtho[1,2-d]furan-4-yl, benzo[b]naphtho[2,3-d]furan-2-yl, benzo[b]naphtho[2,3-d]furan-4-yl or benzo[b]naphtho[2,3-d benzo[b]naphtho[2,3-d]furanyl such as benzo[b]naphtho[2,1-d]furan-6-yl or benzo[b]naphtho[2,1-d]furan-7-yl; benzo[1,2-b:4,3-b']difuranyl such as benzo[1,2-b:4,3-b']difuran-7-yl; benzo[1,2-b:6,5-b']difuran-4-yl; ,2-b:6,5-b']difuranyl, benzo[1,2-b:5,4-b']difuran-4-yl or benzo[1,2-b:5,4-b']difuran-8-yl, benzo[1,2-b:4,5-b']difuranyl such as benzo[1,2-b:4,5-b']difuran-4-yl, tribenzo[b,d,f]oxepin-6-yl or tribenzo[b,d,f]oxepin tribenzo[b,d,f]oxepinyl such as 2H-naphtho[1,8-d,e][1,3]dioxin-2-yl or 2H-naphtho[1,8-d,e][1,3]dioxin-6-yl; dinaphtho[2,3-b:2',3'-d]furan-3-yl or dinaphtho[2,3-b:2',3'-d]furan-5-yl;3'-d]furanyl, oxanthrene such as oxanthrene-1-yl or oxanthrene-2-yl; benzo[a]oxanthrene such as benzo[a]oxanthrene-1-yl, benzo[a]oxanthrene-2-yl, benzo[a]oxanthrene-6-yl or benzo[a]oxanthrene-7-yl; benzo[b]oxanthrene such as benzo[b]oxanthrene-1-yl, benzo[b]oxanthrene-2-yl or benzo[b]oxanthrene-6-yl; benzo[b]thien-2-yl, benzo[b]thien-3-yl, benz[b]oxanthrene benzo[b]thienyl such as benzo[b]thien-4-yl, benzo[b]thien-5-yl, benzo[b]thien-6-yl or benzo[b]thien-7-yl; dibenzo[b,d]thienyl such as dibenzo[b,d]thien-1-yl, dibenzo[b,d]thien-2-yl, dibenzo[b,d]thien-3-yl or dibenzo[b,d]thien-4-yl; naphtho[1,2-b]thienyl such as naphtho[1,2-b]thien-5-yl; naphtho[2,3-b]thien-3-yl, naphtho[2,3-b]thien-4-yl or naphtho[2,3-b]thien naphtho[2,3-b]thienyl such as naphtho[2,1-b]thien-2-yl or naphtho[2,1-b]thien-5-yl; benzo[b]naphtho[1,2-d]thienyl such as benzo[b]naphtho[1,2-d]thien-1-yl or benzo[b]naphtho[1,2-d]thien-4-yl; benzo[b]naphtho[2,3-d]thien-2-yl, benzo[b]naphtho[2,3-d]thien-4-yl or benzo[b]naphtho[2,3-d]thien-6-yl; benzo[1,2-b:4,3-b']dithienyl such as benzo[1,2-b:4,3-b']dithienyl-7-yl; benzo[1,2-b:6,5-b']dithienyl such as benzo[1,2-b:6,5-b']dithien-4-yl; benzo[1,2-b:5,4-b']dithienyl such as benzo[1,2-b:5,4-b']dithien-8-yl; benzo[1,2-b:4,benzo[1,2-b:4,5-b']dithienyl such as benzo[1,2-b:5-b']dithien-4-yl, 9H-thioxanthenyl such as 9H-thioxanthen-4-yl, 6H-dibenzo[b,d]thiopyranyl such as 6H-dibenzo[b,d]thiopyran-2-yl or 6H-dibenzo[b,d]thiopyran-4-yl, 1,4-benzodithiinyl such as 1,4-benzodithiin-2-yl, 1,4-benzodithiin-5-yl or 1,4-benzodithiin-6-yl, naphtho[1,2-b][1,4]dithiin-2-yl or naphtho[1,2-b][1,4]dithiin-6-yl, naphtho[1,2-b][1,4]dithiynyl such as naphtho[2,3-b][1,4]dithiin-5-yl; thianthrenyl such as thianthren-1-yl or thianthren-2-yl; benzo[a]thianthrenyl such as benzo[a]thianthren-1-yl, benzo[a]thianthren-2-yl, benzo[a]thianthren-6-yl or benzo[a]thianthren-7-yl; benzo[b]thianthrenyl such as benzo[b]thianthren-1-yl, benzo[b]thianthren-2-yl or benzo[b]thianthren-6-yl. dibenzo[a,c]thianthrenyl such as dibenzo[a,c]thianthren-10-yl or dibenzo[a,c]thianthren-11-yl; dibenzo[a,h]thianthrenyl such as dibenzo[a,h]thianthren-6-yl; dibenzo[a,i]thianthrenyl such as dibenzo[a,j]thianthren-6-yl; dibenzo[a,j]thianthrenyl such as dibenzo[a,j]thianthren-6-yl; dibenzo[b,i]thianthrenyl such as dibenzo[b,i]thianthren-5-yl; 2H-naphtho[1,8-b,c]thienyl -6-yl or 2H-naphtho[1,8-b,c]thienyl such as 2H-naphtho[1,8-b,c]thien-8-yl, dibenzo[b,d]thiepinyl such as dibenzo[b,d]thiepin-2-yl, dibenzo[b,f]thiepinyl such as dibenzo[b,f]thiepin-2-yl or dibenzo[b,f]thiepin-4-yl, 5H-phenanthro[4,5-b,c,d]thiopyran-1-yl, 5H-phenanthro[4,5-b,c,d]thiopyran-2-yl, 5H-phenanthro[4,5-b,c,d]thiopyran-3-yl, 5H-phenanthro[4,5-b,5H-phenanthro[4,5-b,c,d]thiopyran-7-yl, 5H-phenanthro[4,5-b,c,d]thiopyran-9-yl or 5H-phenanthro[4,5-b,c,d]thiopyran-10-yl, tribenzo[b,d,f]thiepinyl such as tribenzo[b,d,f]thiepin-6-yl or tribenzo[b,d,f]thiepin-8-yl, 2,5-dihydronaphtho[1,8-b,c:4,5-b',c']dithien-3-yl or 2,5-dihydronaphtho[1,8-b,c:4,5-b',c']dithien-3-yl or 2,5-dihydronaphtho[1,8-b,c:4,5-b',c']dithien-4-yl, 2,5-dihydronaphtho[1,8-b,c:4,5-b',c']dithien-5-yl or 2,5-dihydronaphtho[1,8-b,c:4,5-b',c']dithien-6-yl or 2,5-dihydronaphtho[1,8-b,c:4,5-b',c']dithien-8-yl, 2,5-dihydronaphtho[1,8-b,c:4,5-b',c']dithien-9-yl or 2,5-dihydronaphtho[1,8-b,c:4,5-b',c']dithien-10-yl, ... 2,5-dihydronaphtho[1,8-b,c:4,5-b',c']dithienyl such as thien-7-yl, 2,6-dihydronaphtho[1,8-b,c:5,4-b',c']dithienyl such as 2,6-dihydronaphtho[1,8-b,c:5,4-b',c']dithien-4-yl, tetrabenzo[a,c,h,j]thianthrenyl such as tetrabenzo[a,c,h,j]thianthren-3-yl, benzo[b]naphtho[1,8-e,f][1,4]dithiepinyl such as benzo[b]naphtho[1,8-e,f][1,4]dithiepin-2-yl, dinaphtho[1,8-b,c:4,5-b',c']dithienyl, dinaphtho[2,3-b:2',3'-d]thienyl such as [2,3-b:2',3'-d]thien-3-yl or dinaphtho[2,3-b:2',3'-d]thien-5-yl; 5H-phenanthro[1,10-b,c]thien-1-yl or 5H-phenanthro[1,10-b,c]thien-3-yl; 7H-phenanthro[1,10-c,b]thienyl such as 7H-phenanthro[1,10-c,b]thien-1-yl or 7H-phenanthro[1,10-c,b]thien-9-yl; dibenzo[d,d']benzo[1,2-b:4,5-b']dithienyl, such as benzo[d,d']benzo[1,2-b:4,5-b']dithien-4-yl or dibenzo[d,d']benzo[1,2-b:4,5-b']dithien-6-yl, and dibenzo[d,d']benzo[1,2-b:5,4-b']dithienyl, such as dibenzo[d,d']benzo[1,2-b:5,4-b']dithien-4-yl or dibenzo[d,d']benzo[1,2-b:5,4-b']dithien-6-yl, which are unsubstituted or have one or two R, Ar It may have a group.

[0068] According to a particularly preferred group of embodiments (6.2), R 1 and R 2is phenyl, naphthyl such as naphth-1-yl or naphth-2-yl, 1,2-dihydroacenaphthylenyl such as 1,2-dihydroacenaphthylen-3-yl or 1,2-dihydroacenaphthylen-5-yl, biphenylyl such as biphenyl-4-yl, biphenyl-3-yl or biphenyl-2-yl, fluorenyl such as fluoren-1-yl, fluoren-2-yl, fluoren-3-yl or fluoren-4-yl, phenanthren-1-yl, phenanthren-2-yl, phenanthren-3-yl, phenanthren-4-yl or phenanthren- phenanthrenyl such as benzo[c]phenanthren-1-yl, benzo[c]phenanthren-2-yl, benzo[c]phenanthren-3-yl, benzo[c]phenanthren-4-yl, benzo[c]phenanthren-5-yl, or benzo[c]phenanthren-6-yl; pyrenyl such as pyren-1-yl, pyren-2-yl, or pyren-4-yl; chrysenyl such as chrysen-1-yl, chrysen-2-yl, chrysen-3-yl, chrysen-4-yl, chrysen-5-yl, or chrysen-6-yl; triphenyl ether such as chrysen-1-yl, chrysen-2-yl, chrysen-3-yl, chrysen-4-yl, chrysen-5-yl, or chrysen-6-yl; triphenylenyl such as phenylen-1-yl or triphenylen-2-yl; benzo[b]furanyl such as benzo[b]furan-2-yl, benzo[b]furan-3-yl, benzo[b]furan-4-yl, benzo[b]furan-5-yl, benzo[b]furan-6-yl or benzo[b]furan-7-yl; dibenzo[b,d]furanyl such as dibenzo[b,d]furan-1-yl, dibenzo[b,d]furan-2-yl, dibenzo[b,d]furan-3-yl or dibenzo[b,d]furan-4-yl; naphtho[1,2-b]furan-5-yl, etc. naphtho[2,3-b]furanyl such as naphtho[2,3-b]furan-3-yl, naphtho[2,3-b]furan-4-yl or naphtho[2,3-b]furan-9-yl; naphtho[2,1-b]furanyl such as naphtho[2,1-b]furan-2-yl or naphtho[2,1-b]furan-5-yl; benzo[b]naphtho[1,2-d]furanyl such as benzo[b]naphtho[1,2-d]furan-1-yl or benzo[b]naphtho[1,2-d]furan-4-yl; benzo[b]naphtho[2,3-d]furan-2-yl; benzo[b]naphtho[2,benzo[b]naphtho[2,3-d]furanyl such as benzo[b]naphtho[2,3-d]furan-4-yl or benzo[b]naphtho[2,3-d]furan-6-yl; benzo[b]naphtho[2,1-d]furanyl such as benzo[b]naphtho[2,1-d]furan-6-yl or benzo[b]naphtho[2,1-d]furan-7-yl; oxanthreneyl such as oxanthrene-1-yl or oxanthrene-2-yl; benzo[a]oxanthrene-1-yl, benzo[a]oxanthrene-2-yl, benzo[a]oxanthrene-6-yl; benzo[a]oxanthrene such as benzo[a]oxanthrene-7-yl or benzo[a]oxanthrene-1-yl, benzo[b]oxanthrene-2-yl or benzo[b]oxanthrene-6-yl; benzo[b]thienyl such as benzo[b]thien-2-yl, benzo[b]thien-3-yl, benzo[b]thien-4-yl, benzo[b]thien-5-yl, benzo[b]thien-6-yl or benzo[b]thien-7-yl; dibenzo[b,d]thienyl such as dibenzo[b,d]thienyl; dibenzo[b,d]thienyl such as dibenzo[b,d]thien-1-yl, dibenzo[b,d]thien-2-yl, dibenzo[b,d]thien-3-yl or dibenzo[b,d]thien-4-yl; naphtho[1,2-b]thienyl such as naphtho[1,2-b]thien-5-yl; naphtho[2,3-b]thienyl such as naphtho[2,3-b]thien-3-yl, naphtho[2,3-b]thien-4-yl or naphtho[2,3-b]thien-9-yl; naphtho[2,1-b]thien-2-yl or naphtho[2,1-b]thien-5-yl naphtho[2,1-b]thienyl such as benzo[b]naphtho[1,2-d]thienyl such as benzo[b]naphtho[1,2-d]thien-1-yl or benzo[b]naphtho[1,2-d]thien-4-yl; benzo[b]naphtho[2,3-d]thien-2-yl, benzo[b]naphtho[2,3-d]thien-4-yl or benzo[b]naphtho[2,3-d]thienyl such as benzo[b]naphtho[2,1-d]thien-7-yl;1-d]thienyl, thianthrenyl such as thianthren-1-yl or thianthren-2-yl, benzo[a]thianthrenyl such as benzo[a]thianthren-1-yl, benzo[a]thianthren-2-yl, benzo[a]thianthren-6-yl or benzo[a]thianthren-7-yl, benzo[b]thianthrenyl such as benzo[b]thianthren-1-yl, benzo[b]thianthren-2-yl or benzo[b]thianthren-6-yl, 2H-naphtho[1,8-b,c]thien-6-yl dibenzo[b,d]thiepinyl, such as dibenzo[b,d]thiepin-2-yl, dibenzo[b,f]thiepinyl, such as dibenzo[b,f]thiepin-2-yl or dibenzo[b,f]thiepin-4-yl, and tribenzo[b,d,f]thiepinyl, such as tribenzo[b,d,f]thiepin-6-yl or tribenzo[b,d,f]thiepin-8-yl, and are unsubstituted or contain one R, Ar It may have a group.

[0069] In a particularly preferred group (6.3) of embodiments, R 1 and R 2are independently selected from phenyl, naphthyl, 1,2-dihydroacenaphthylenyl, phenanthrenyl, pyrenyl, triphenylenyl, benzo[b]furanyl, dibenzo[b,d]furanyl, benzo[b]thienyl, dibenzo[b,d]thienyl and thianthrenyl, in particular phenyl, naphth-1-yl, naphth-2-yl, 1,2-dihydroacenaphthylen-5-yl, phenanthren-9-yl, pyren-1-yl, pyren-2-yl, pyren-4-yl In a subgroup (6.3a) of group (6.3) of embodiments, R is selected from the group consisting of benzo[b,d]furan-2-yl, dibenzo[b,d]furan-4-yl, benzo[b]thien-3-yl, benzo[b]thien-4-yl, benzo[b]thien-5-yl, benzo[b]thien-6-yl, benzo[b]thien-7-yl, dibenzo[b,d]thien-2-yl, dibenzo[b,d]thien-4-yl, thianthren-1-yl and thianthren-2-yl. 1 and R 2 are independently selected from phenyl, naphthyl, 1,2-dihydroacenaphthylenyl, phenanthrenyl, triphenylenyl, pyrenyl, dibenzo[b,d]furanyl, benzo[b]thienyl, dibenzo[b,d]thienyl and thianthrenyl, in particular selected from phenyl, naphthyl, phenanthrenyl, dibenzo[b,d]thienyl and thianthrenyl.

[0070] In a particular subgroup (6') of embodiments, the variable R 1 and R 2 is R 1 and R 2 has the same meaning as defined herein, in particular selected from the meanings mentioned as being preferred, in particular selected from the meanings defined in groups (6), (6.1), (6.2), (6.3) or (6.3a) of embodiments.

[0071] In a preferred group (7) of embodiments, the variable portion R 3 and R 4 is different from hydrogen. That is, the variable R 3 and R 4are monocyclic or polycyclic aryls having 6 to 26 carbon atoms as ring atoms and monocyclic or polycyclic hetaryls having a total of 5 to 26 ring atoms, where 1, 2, 3 or 4 of these ring atoms in the hetaryl are selected from nitrogen, sulfur and oxygen, and the remaining ring atoms in the hetaryl are carbon atoms. The monocyclic or polycyclic aryls and monocyclic or polycyclic hetaryls are unsubstituted or substituted with 1, 2, 3 or 4 R Ar More preferably, R 3 and R 4 At least one of the following, especially R 3 and R 4 are both selected from polycyclic aryl having 10 to 18 carbon atoms and polycyclic hetaryl having a total of 9 to 26 atoms.

[0072] Preferably, in this group (7) of embodiments, the variable portion R 3 and R 4 are monocyclic or polycyclic aryls having 6 to 18 carbon atoms as ring members and polycyclic hetaryls having a total of 9 to 26 ring atoms (one or two of these atoms are oxygen or sulfur atoms, the remaining atoms are carbon atoms. Monocyclic or polycyclic aryls and polycyclic hetaryls are unsubstituted or have one or two R Ar Group(R Ar has one of the meanings defined herein, in particular one of the meanings described as preferred) (hereinafter group (7.1) of embodiments).

[0073] More preferably, in this group (7) of embodiments, R 3 and R 4is naphthyl such as phenyl, naphth-1-yl or naphth-2-yl; 1,2-dihydroacenaphthylenyl such as 1,2-dihydroacenaphthylen-3-yl or 1,2-dihydroacenaphthylen-5-yl; biphenylyl such as biphenyl-4-yl, biphenyl-3-yl or biphenyl-2-yl; fluorenyl such as fluoren-1-yl, fluoren-2-yl, fluoren-3-yl or fluoren-4-yl; 11H-benzo[a]fluorenyl such as 11H-benzo[a]fluoren-7-yl; 11H-benzo[b]fluoren-1-yl, etc. 11H-benzo[b]fluorenyl, 7H-benzo[c]fluoren-5-yl or 7H-benzo[c]fluoren-10-yl, phenanthrenyl, such as phenanthren-1-yl, phenanthren-2-yl, phenanthren-3-yl, phenanthren-4-yl or phenanthren-9-yl, benzo[c]phenanthren-1-yl, benzo[c]phenanthren-2-yl, benzo[c]phenanthren-3-yl, benzo[c]phenanthren-4-yl, benzo[c]phenanthren-5-yl or Examples of the aryl groups include benzo[c]phenanthrenyl such as benzo[c]phenanthren-6-yl, pyrenyl such as pyren-1-yl, pyren-2-yl, and pyren-4-yl, chrysenyl such as chrysen-1-yl, chrysen-2-yl, chrysen-3-yl, chrysen-4-yl, chrysen-5-yl, and chrysen-6-yl, picenyl such as picen-3-yl, triphenylenyl such as triphenylen-1-yl and triphenylen-2-yl, benzo[b]furan-2-yl, benzo[b]furan-3-yl, benzo[b]furan-4-yl, and benzo[b]furan-5-yl. benzo[b]furanyl such as benzo[b]furan-6-yl or benzo[b]furan-7-yl; dibenzo[b,d]furanyl such as dibenzo[b,d]furan-1-yl, dibenzo[b,d]furan-2-yl, dibenzo[b,d]furan-3-yl or dibenzo[b,d]furan-4-yl; naphtho[1,2-b]furanyl such as naphtho[1,2-b]furan-5-yl; naphtho[2,3-b]furan-3-yl, naphtho[2,3-b]furan-4-yl or naphtho[2,3-b]furan-9-yl; naphtho[2,naphtho[2,1-b]furanyl such as 1-b]furan-2-yl or naphtho[2,1-b]furan-5-yl, benzo[b]naphtho[1,2-d]furanyl such as benzo[b]naphtho[1,2-d]furan-1-yl or benzo[b]naphtho[1,2-d]furan-4-yl, benzo[b]naphtho[2,3-d]furan-2-yl, benzo[b]naphtho[2,3-d]furan-4-yl or benzo[b]naphtho[2,3-d benzo[b]naphtho[2,3-d]furanyl such as benzo[b]naphtho[2,1-d]furan-6-yl or benzo[b]naphtho[2,1-d]furan-7-yl; benzo[1,2-b:4,3-b']difuranyl such as benzo[1,2-b:4,3-b']difuran-7-yl; benzo[1,2-b:6,5-b']difuran-4-yl; ,2-b:6,5-b']difuranyl, benzo[1,2-b:5,4-b']difuran-4-yl or benzo[1,2-b:5,4-b']difuran-8-yl, benzo[1,2-b:4,5-b']difuranyl such as benzo[1,2-b:4,5-b']difuran-4-yl, tribenzo[b,d,f]oxepin-6-yl or tribenzo[b,d,f]oxepin tribenzo[b,d,f]oxepinyl such as 2H-naphtho[1,8-d,e][1,3]dioxin-2-yl or 2H-naphtho[1,8-d,e][1,3]dioxin-6-yl; dinaphtho[2,3-b:2',3'-d]furan-3-yl or dinaphtho[2,3-b:2',3'-d]furan-5-yl;3'-d]furanyl, oxanthrene such as oxanthrene-1-yl or oxanthrene-2-yl; benzo[a]oxanthrene such as benzo[a]oxanthrene-1-yl, benzo[a]oxanthrene-2-yl, benzo[a]oxanthrene-6-yl or benzo[a]oxanthrene-7-yl; benzo[b]oxanthrene such as benzo[b]oxanthrene-1-yl, benzo[b]oxanthrene-2-yl or benzo[b]oxanthrene-6-yl; benzo[b]thien-2-yl, benzo[b]thien-3-yl, benz[b]oxanthrene benzo[b]thienyl such as benzo[b]thien-4-yl, benzo[b]thien-5-yl, benzo[b]thien-6-yl or benzo[b]thien-7-yl; dibenzo[b,d]thienyl such as dibenzo[b,d]thien-1-yl, dibenzo[b,d]thien-2-yl, dibenzo[b,d]thien-3-yl or dibenzo[b,d]thien-4-yl; naphtho[1,2-b]thienyl such as naphtho[1,2-b]thien-5-yl; naphtho[2,3-b]thien-3-yl, naphtho[2,3-b]thien-4-yl or naphtho[2,3-b]thien naphtho[2,3-b]thienyl such as naphtho[2,1-b]thien-2-yl or naphtho[2,1-b]thien-5-yl; benzo[b]naphtho[1,2-d]thienyl such as benzo[b]naphtho[1,2-d]thien-1-yl or benzo[b]naphtho[1,2-d]thien-4-yl; benzo[b]naphtho[2,3-d]thien-2-yl, benzo[b]naphtho[2,3-d]thien-4-yl or benzo[b]naphtho[2,3-d]thien-6-yl; benzo[1,2-b:4,3-b']dithienyl such as benzo[1,2-b:4,3-b']dithienyl-7-yl; benzo[1,2-b:6,5-b']dithienyl such as benzo[1,2-b:6,5-b']dithien-4-yl; benzo[1,2-b:5,4-b']dithienyl such as benzo[1,2-b:5,4-b']dithien-8-yl; benzo[1,2-b:4,benzo[1,2-b:4,5-b']dithienyl such as benzo[1,2-b:5-b']dithien-4-yl, 9H-thioxanthenyl such as 9H-thioxanthen-4-yl, 6H-dibenzo[b,d]thiopyranyl such as 6H-dibenzo[b,d]thiopyran-2-yl or 6H-dibenzo[b,d]thiopyran-4-yl, 1,4-benzodithiinyl such as 1,4-benzodithiin-2-yl, 1,4-benzodithiin-5-yl or 1,4-benzodithiin-6-yl, naphtho[1,2-b][1,4]dithiin-2-yl or naphtho[1,2-b][1,4]dithiin-6-yl, naphtho[1,2-b][1,4]dithiynyl such as naphtho[2,3-b][1,4]dithiin-5-yl; thianthrenyl such as thianthren-1-yl or thianthren-2-yl; benzo[a]thianthrenyl such as benzo[a]thianthren-1-yl, benzo[a]thianthren-2-yl, benzo[a]thianthren-6-yl or benzo[a]thianthren-7-yl; benzo[b]thianthrenyl such as benzo[b]thianthren-1-yl, benzo[b]thianthren-2-yl or benzo[b]thianthren-6-yl. dibenzo[a,c]thianthrenyl such as dibenzo[a,c]thianthren-10-yl or dibenzo[a,c]thianthren-11-yl; dibenzo[a,h]thianthrenyl such as dibenzo[a,h]thianthren-6-yl; dibenzo[a,i]thianthrenyl such as dibenzo[a,j]thianthren-6-yl; dibenzo[a,j]thianthrenyl such as dibenzo[a,j]thianthren-6-yl; dibenzo[b,i]thianthrenyl such as dibenzo[b,i]thianthren-5-yl; 2H-naphtho[1,8-b,c]thienyl -6-yl or 2H-naphtho[1,8-b,c]thienyl such as 2H-naphtho[1,8-b,c]thien-8-yl, dibenzo[b,d]thiepinyl such as dibenzo[b,d]thiepin-2-yl, dibenzo[b,f]thiepinyl such as dibenzo[b,f]thiepin-2-yl or dibenzo[b,f]thiepin-4-yl, 5H-phenanthro[4,5-b,c,d]thiopyran-1-yl, 5H-phenanthro[4,5-b,c,d]thiopyran-2-yl, 5H-phenanthro[4,5-b,c,d]thiopyran-3-yl, 5H-phenanthro[4,5-b,5H-phenanthro[4,5-b,c,d]thiopyran-7-yl, 5H-phenanthro[4,5-b,c,d]thiopyran-9-yl or 5H-phenanthro[4,5-b,c,d]thiopyran-10-yl, tribenzo[b,d,f]thiepinyl such as tribenzo[b,d,f]thiepin-6-yl or tribenzo[b,d,f]thiepin-8-yl, 2,5-dihydronaphtho[1,8-b,c:4,5-b',c']dithien-3-yl or 2,5-dihydronaphtho[1,8-b,c:4,5-b',c']dithien-7-yl, 5H-phenanthro[4,5-b,c,d]thiopyranyl such as 5H-phenanthro[4,5-b,c,d]thiopyran-9-yl or 5H-phenanthro[4,5-b,c,d]thiopyran-10-yl, 2,5-dihydronaphtho[1,8-b,c:4,5-b',c']dithienyl such as 2,6-dihydronaphtho[1,8-b,c:5,4-b',c']dithienyl such as 2,6-dihydronaphtho[1,8-b,c:5,4-b',c']dithien-4-yl; tetrabenzo[a,c,h,j]thianthrenyl such as tetrabenzo[a,c,h,j]thianthren-3-yl; benzo[b]naphtho[1,8-e,f][1,4]dithiepinyl such as benzo[b]naphtho[1,8-e,f][1,4]dithiepin-2-yl; dinaphtho[2,3-b:2',3'- dinaphtho[2,3-b:2',3'-d]thienyl such as 5H-phenanthro[1,10-b,c]thien-1-yl or 5H-phenanthro[1,10-b,c]thien-3-yl; 7H-phenanthro[1,10-c,b]thienyl such as 7H-phenanthro[1,10-c,b]thien-1-yl or 7H-phenanthro[1,10-c,b]thien-9-yl; dibenzo[d,d']benzo[1,2-b: dibenzo[d,d']benzo[1,2-b:4,5-b']dithienyl, such as dibenzo[d,d']benzo[1,2-b:4,5-b']dithien-4-yl or dibenzo[d,d']benzo[1,2-b:4,5-b']dithien-6-yl, and dibenzo[d,d']benzo[1,2-b:5,4-b']dithien-4-yl or dibenzo[d,d']benzo[1,2-b:5,4-b']dithien-6-yl, wherein the monocyclic or polycyclic aryl and polycyclic hetaryl are unsubstituted or have one or two R,Ar group (hereinafter, group (7.2) of the embodiment).

[0074] In particular, in this group (7) of embodiments, R 3 and R 4is phenyl, naphthyl such as naphth-1-yl or naphth-2-yl, 1,2-dihydroacenaphthylenyl such as 1,2-dihydroacenaphthylen-3-yl or 1,2-dihydroacenaphthylen-5-yl, biphenylyl such as biphenyl-4-yl, biphenyl-3-yl or biphenyl-2-yl, fluorenyl such as fluoren-1-yl, fluoren-2-yl, fluoren-3-yl or fluoren-4-yl, phenanthren-1-yl, phenanthren-2-yl, phenanthren-3-yl, phenanthren-4-yl or phenanthren- phenanthrenyl such as benzo[c]phenanthren-1-yl, benzo[c]phenanthren-2-yl, benzo[c]phenanthren-3-yl, benzo[c]phenanthren-4-yl, benzo[c]phenanthren-5-yl, or benzo[c]phenanthren-6-yl; pyrenyl such as pyren-1-yl, pyren-2-yl, or pyren-4-yl; chrysenyl such as chrysen-1-yl, chrysen-2-yl, chrysen-3-yl, chrysen-4-yl, chrysen-5-yl, or chrysen-6-yl; triphenyl ether such as chrysen-1-yl, chrysen-2-yl, chrysen-3-yl, chrysen-4-yl, chrysen-5-yl, or chrysen-6-yl; triphenylenyl such as phenylen-1-yl or triphenylen-2-yl; benzo[b]furanyl such as benzo[b]furan-2-yl, benzo[b]furan-3-yl, benzo[b]furan-4-yl, benzo[b]furan-5-yl, benzo[b]furan-6-yl or benzo[b]furan-7-yl; dibenzo[b,d]furanyl such as dibenzo[b,d]furan-1-yl, dibenzo[b,d]furan-2-yl, dibenzo[b,d]furan-3-yl or dibenzo[b,d]furan-4-yl; naphtho[1,2-b]furan-5-yl, etc. naphtho[2,3-b]furanyl such as naphtho[2,3-b]furan-3-yl, naphtho[2,3-b]furan-4-yl or naphtho[2,3-b]furan-9-yl; naphtho[2,1-b]furanyl such as naphtho[2,1-b]furan-2-yl or naphtho[2,1-b]furan-5-yl; benzo[b]naphtho[1,2-d]furanyl such as benzo[b]naphtho[1,2-d]furan-1-yl or benzo[b]naphtho[1,2-d]furan-4-yl; benzo[b]naphtho[2,3-d]furan-2-yl; benzo[b]naphtho[2,benzo[b]naphtho[2,3-d]furanyl such as benzo[b]naphtho[2,3-d]furan-4-yl or benzo[b]naphtho[2,3-d]furan-6-yl; benzo[b]naphtho[2,1-d]furanyl such as benzo[b]naphtho[2,1-d]furan-6-yl or benzo[b]naphtho[2,1-d]furan-7-yl; oxanthreneyl such as oxanthrene-1-yl or oxanthrene-2-yl; benzo[a]oxanthrene-1-yl, benzo[a]oxanthrene-2-yl, benzo[a]oxanthrene-6-yl; benzo[a]oxanthrene such as benzo[a]oxanthrene-7-yl or benzo[a]oxanthrene-1-yl, benzo[b]oxanthrene-2-yl or benzo[b]oxanthrene-6-yl; benzo[b]thienyl such as benzo[b]thien-2-yl, benzo[b]thien-3-yl, benzo[b]thien-4-yl, benzo[b]thien-5-yl, benzo[b]thien-6-yl or benzo[b]thien-7-yl; dibenzo[b,d]thienyl such as dibenzo[b,d]thienyl; dibenzo[b,d]thienyl such as dibenzo[b,d]thien-1-yl, dibenzo[b,d]thien-2-yl, dibenzo[b,d]thien-3-yl or dibenzo[b,d]thien-4-yl; naphtho[1,2-b]thienyl such as naphtho[1,2-b]thien-5-yl; naphtho[2,3-b]thienyl such as naphtho[2,3-b]thien-3-yl, naphtho[2,3-b]thien-4-yl or naphtho[2,3-b]thien-9-yl; naphtho[2,1-b]thien-2-yl or naphtho[2,1-b]thien-5-yl naphtho[2,1-b]thienyl such as benzo[b]naphtho[1,2-d]thienyl such as benzo[b]naphtho[1,2-d]thien-1-yl or benzo[b]naphtho[1,2-d]thien-4-yl; benzo[b]naphtho[2,3-d]thien-2-yl, benzo[b]naphtho[2,3-d]thien-4-yl or benzo[b]naphtho[2,3-d]thienyl such as benzo[b]naphtho[2,1-d]thien-7-yl;1-d]thienyl, thianthrenyl such as thianthren-1-yl or thianthren-2-yl; benzo[a]thianthrenyl such as benzo[a]thianthren-1-yl, benzo[a]thianthren-2-yl, benzo[a]thianthren-6-yl or benzo[a]thianthren-7-yl; benzo[b]thianthrenyl such as benzo[b]thianthren-1-yl, benzo[b]thianthren-2-yl or benzo[b]thianthren-6-yl; 2H-naphtho[1,8-b,c]thien-6-yl or 2H-naphtho[1,8 dibenzo[b,d]thiepinyl, such as dibenzo[b,f]thiepin-2-yl or dibenzo[b,f]thiepin-4-yl; and tribenzo[b,d,f]thiepinyl, such as tribenzo[b,d,f]thiepin-6-yl or tribenzo[b,d,f]thiepin-8-yl, wherein the monocyclic or polycyclic aryl and polycyclic hetaryl are unsubstituted or have one R, Ar group (hereinafter, group (7.3) of the embodiment).

[0075] In a particularly preferred group (7.4) of embodiments, R 3 and R 4are independently selected from phenyl, naphthyl, 1,2-dihydroacenaphthylenyl, phenanthrenyl, pyrenyl, triphenylenyl, benzo[b]furanyl, dibenzo[b,d]furanyl, benzo[b]thienyl, dibenzo[b,d]thienyl and thianthrenyl, in particular phenyl, naphth-1-yl, naphth-2-yl, 1,2-dihydroacenaphthylen-5-yl, phenanthren-9-yl, pyren-1-yl, pyren-2-yl, pyren-4-yl In a subgroup (7.4a) of group (7.4) of embodiments, R is selected from the group consisting of benzo[b,d]furan-2-yl, dibenzo[b,d]furan-4-yl, benzo[b]thien-3-yl, benzo[b]thien-4-yl, benzo[b]thien-5-yl, benzo[b]thien-6-yl, benzo[b]thien-7-yl, dibenzo[b,d]thien-2-yl, dibenzo[b,d]thien-4-yl, thianthren-1-yl and thianthren-2-yl. 1 and R 2 is independently selected from naphthyl, 1,2-dihydroacenaphthylenyl, phenanthrenyl, benzo[b]furanyl, dibenzo[b,d]furanyl, benzo[b]thienyl, and dibenzo[b,d]thienyl.

[0076] A particular subgroup (7.5) of the group (7) of embodiments has been found to provide high refractive index and negative birefringence. These subgroups (7.5) of embodiments are those in which R 3 and R 4 is different from hydrogen, and the substituent R 1 , R 2 , R 3 and / or R 4 In this context, the bulky substituent R 1 , R 2 , R 3 and / or R 4 is in particular a substituent of the following groups: - polycyclic aryl and polycyclic hetaryl (R 1 , R 2 , R 3 and / or R 4 wherein the phenyl ring is fused to at least one of an aromatic ring having 6 to 14 carbon atoms as ring member atoms and a partially or completely unsaturated heterocycle having 5 to 13 ring member atoms, and at least one of the rings fused to the phenyl ring is fused to a bond between the ortho and meta positions of the phenyl ring; and - polycyclic aryl having 14 to 26, in particular 14 to 20, carbon atoms as ring atoms and polycyclic hetaryl having 13 to 26, in particular 13 to 20, ring atoms, in which 1, 2, 3 or 4 of these ring atoms are selected from nitrogen, sulfur and oxygen, the remaining ring atoms being carbon atoms.

[0077] Examples of such bulky substituents include, but are not limited to, naphthyl, phenanthryl, pyrenyl, triphenylenyl, 1,2-dihydroacenaphthylenyl, dibenzo[b,d]thienyl, thianthrenyl, dibenzo[b,d]furanyl, and 9H-fluoren-3-yl, and in particular, but are not limited to, 1-naphthyl, 9-phenanthryl, pyren-1-yl, pyren-4-yl, 1-triphenylenyl, 1,2-dihydroacenaphthylenyl, dibenzo[b,d]thien-4-yl, dibenzo[b,d]furan-4-yl, and thianthren-1-yl.

[0078] Bulky mutual substituent R 1 , R 2 , R 3 and / or R 4 The reason for this beneficial effect of is not entirely clear, but it is likely that these substituents, due to their steric hindrance, are forced to orient within the resin perpendicular to the backbone, thereby lowering the birefringence of the resin.

[0079] Thus, by offsetting the positive birefringence imparted to the resin by a comonomer, such as a comonomer of formula (IV), with the negative birefringence imparted by a monomer of formula (I), particularly formula (Ia-1) according to embodiment (7.5), thermoplastic resins with low birefringence can be obtained in accordance with the present invention.

[0080] In a particular subgroup (7') of embodiments, the variable R 3 and R 4 is R 3 and R 4 has the same meaning as defined herein, in particular selected from the meanings mentioned as being preferred, in particular selected from the meanings defined in groups (7), (7.1), (7.2), (7.3), (7.4), (7.4a) or (7.5) of embodiments.

[0081] In a particular group (8) of embodiments, the variable portion R 1 , R 2 , R 3 and R 4 In this group (8) of embodiments, the variable part R 1 , R 2 , R 3 and R 4 The identical meanings of are preferably selected from the meanings defined herein, in particular the meanings mentioned as being preferred, preferably selected from the meanings defined in group (6), in particular the meanings defined in group (6.1), more particularly the meanings defined in group (6.2), even more preferably the meanings defined in group (6.3), in particular the meanings defined in group (6.3a). In this particular group (8) of embodiments, the variable R 1 , R 2 , R 3 and R 4 is more preferably as defined in group (7.1), (7.2), (7.3), (7.4), (7.4a) or (7.5) of embodiments.

[0082] In a further specific group (9) of embodiments, the variable portion R 3and R 4 and R are both hydrogen. Furthermore, in this group (9) of embodiments, the variable portion R 1 and R 2 has the same meaning, preferably selected from the meanings defined herein, particularly the meanings described herein as preferred, preferably selected from the meanings defined in group (6), in particular the meanings defined in group (6.1), more particularly the meanings defined in group (6.2), even more preferably the meanings defined in group (6.3), in particular the meanings defined in group (6.3a).

[0083] In a preferred group (10) of embodiments, the substituent R 1 , R 2 , R 3 and R 4 are all located in the meta position relative to the moiety X, i.e. according to this group of embodiments, the compound of formula (I) is a compound of formula (Ia):

[0084] [ka]

[0085] Wherein the variables X and Z 1 , Z 2 , R 1 , R 2 , R 3 and R 4 has the meanings defined herein, particularly the meanings described as being preferred, and R 3 and R 4 is preferably different from hydrogen, in particular R 1 , R 2 , R 3 and R 4 have the same meaning.

[0086] Likewise, according to this preferred group (10) of embodiments, the structural unit of formula (II) is a structural unit of formula (IIa):

[0087] [ka]

[0088] Wherein the variables X and Z 1 , Z 2 , R 1 , R 2 , R 3 and R 4 has the meanings defined herein and those described as being particularly preferred, R 3 and R 4 is preferably different from hydrogen, in particular R 1 , R 2 , R 3 and R 4 have the same meaning.

[0089] The skilled artisan will appreciate that in formulas (I), (Ia), (II) and (IIa), Z is given in one or more of groups (1), (1.1) and (1′) of embodiments. 1 and Z 2 The meaning of X according to one of the embodiments of group (5) or groups (5'), (5'') and (5''') and the meaning of R according to one or more of the embodiments of groups (6), (6.1), (6.2), (6.3), (6.3a) and (6') are combined. 1 and R 2 and also R according to one or more of groups (7), (7.1), (7.2), (7.3), (7.4), (7.4a), (7.5) and (7′) of embodiments. 3 and R 4 It will be readily understood that the Z group given in embodiment group (2) in formulas (I), (Ia), (II) and (IIa) can be combined with either of embodiment group (8) or group (9). 1 and Z 2 The meaning of X according to one of the embodiments (5) or (5'), (5'') or (5''') and the meaning of R according to one or more of the embodiments (6), (6.1), (6.2), (6.3), (6.3a) and (6') are combined. 1 and R 2and also R according to one or more of groups (7), (7.1), (7.2), (7.3), (7.4), (7.4a), (7.5) and (7′) of embodiments. 3 and R 4 and also may be combined with either group (8) or group (9) of the embodiments. A person skilled in the art will also understand that in formulas (I), (Ia), (II) and (IIa), Z as given in one or more of groups (3), (3.1) and (3′) of the embodiments may be combined with either group (8) or group (9). 1 and Z 2 The meaning of X according to one of the embodiments of group (5) or groups (5'), (5'') and (5''') and the meaning of R according to one or more of the embodiments of groups (6), (6.1), (6.2), (6.3), (6.3a) and (6') are combined. 1 and R 2 and also R according to one or more of groups (7), (7.1), (7.2), (7.3), (7.4), (7.4a), (7.5) and (7′) of embodiments. 3 and R 4 and also may be combined with either group (8) or group (9) of embodiments. A person skilled in the art will also understand that in formulas (I), (Ia), (II) and (IIa), Z as given in one of groups (4) and (4.1) of embodiments may be combined with either group (8) or group (9). 1 and Z 2 The meaning of X according to one of the embodiments (5) or (5'), (5'') or (5''') and the meaning of R according to one or more of the embodiments (6), (6.1), (6.2), (6.3), (6.3a) and (6') are combined. 1 and R 2 and also R according to one or more of groups (7), (7.1), (7.2), (7.3), (7.4), (7.4a), (7.5) and (7′) of embodiments. 3 and R 4 and also may be combined with either group (8) or group (9) of embodiments.

[0090] In addition, unless otherwise specified, the variable Ar 1 , R 5 , R 6 , R Ar , R, R', R'', and n are independently or preferably independently selected from each other and the variables X, R 1 , R 2 , R 3 , R 4 , Z 1 and Z 2 In combination with the meanings and preferred meanings of the formula (I) have the following meanings:

[0091] Ar 1 is preferably a monocyclic or polycyclic aryl having 6 to 18 carbon atoms as ring atoms and a polycyclic hetaryl having a total of 9 to 16 ring atoms (one or two of these ring atoms of the hetaryl are sulfur atoms, and the remaining ring atoms of the hetaryl are carbon atoms). The monocyclic or polycyclic aryl and polycyclic hetaryl are unsubstituted or substituted with one or two R Ar Group(R Ar The radical has one of the meanings defined herein, particularly one of the meanings mentioned as being preferred. Unsubstituted Ar1 radicals are preferred here.

[0092] More preferably, Ar 1is phenyl, naphthyl such as naphth-1-yl or naphth-2-yl, fluorenyl such as fluoren-1-yl, fluoren-2-yl, fluoren-3-yl or fluoren-4-yl, 11H-benzo[a]fluorenyl such as 11H-benzo[a]fluoren-7-yl, 11H-benzo[b]fluorenyl such as 11H-benzo[b]fluoren-1-yl, 7H-benzo[c]fluorenyl such as 7H-benzo[c]fluoren-5-yl or 7H-benzo[c]fluoren-10-yl, phenanthrene-1-yl, phenanthrene-2-yl, phenanthrenyl such as phenanthren-3-yl, phenanthren-4-yl, or phenanthren-9-yl; benzo[c]phenanthrenyl such as benzo[c]phenanthren-1-yl, benzo[c]phenanthren-2-yl, benzo[c]phenanthren-3-yl, benzo[c]phenanthren-4-yl, benzo[c]phenanthren-5-yl, or benzo[c]phenanthren-6-yl; pyrenyl such as pyren-1-yl, pyren-2-yl, or pyren-4-yl; chrysen-1-yl, chrysen-2-yl, chrysen-3-yl, Chrysenyl such as chrysen-4-yl, chrysen-5-yl, or chrysen-6-yl; triphenylenyl such as triphenylen-1-yl or triphenylen-2-yl; benzo[b]thienyl such as benzo[b]thien-2-yl, benzo[b]thien-3-yl, benzo[b]thien-4-yl, benzo[b]thien-5-yl, benzo[b]thien-6-yl, or benzo[b]thien-7-yl; dibenzo[b,d]thien-1-yl, dibenzo[b,d]thien-2-yl, dibenzo[b,d]thien-3-yl, or dibenzo[b,d]thien- naphtho[2,3-b]thienyl such as naphtho[2,3-b]thien-3-yl, naphtho[2,3-b]thien-4-yl or naphtho[2,3-b]thien-9-yl; naphtho[2,1-b]thienyl such as naphtho[2,1-b]thien-2-yl or naphtho[2,1-b]thien-5-yl; benzo[1,2-b:4,3-b']dithienyl such as benzo[1,2-b:4,3-b']dithien-7-yl; benzo[1,2-b:6,Benzo[1,2-b:6,5-b']dithienyl such as benzo[1,2-b:5,4-b']dithien-4-yl or benzo[1,2-b:5,4-b']dithien-8-yl, benzo[1,2-b:4,5-b']dithienyl such as benzo[1,2-b:4,5-b']dithien-4-yl, and thianthrenyl such as thianthren-1-yl or thianthren-2-yl.

[0093] Even more preferably, Ar 1 is selected from phenyl, naphthyl, fluorenyl, phenanthrenyl, pyrenyl, chrysenyl, triphenylenyl, benzo[b]furanyl, dibenzo[b,d]furanyl, benzo[b]thienyl, dibenzo[b,d]thienyl and thianthrenyl, in particular from phenyl, naphthyl, phenanthrenyl, chrysenyl and dibenzo[b,d]thienyl, in particular from phenyl, naphthyl and phenanthrenyl, in particular from phenyl, naphthyl and phenanthrenyl, in particular from phenyl, naphthyl, naphth-2-yl and phenanthren-9-yl.

[0094] R 5 is preferably hydrogen, methyl, ethyl and Ar 1 Group (Ar 1 has one of the meanings defined herein, particularly preferred meanings). More preferably, R 5 is hydrogen, methyl or ethyl, in particular hydrogen or methyl.

[0095] R 6 is preferably selected from the group consisting of hydrogen, methyl and ethyl, in particular hydrogen or methyl.

[0096] R Ar is preferably R, OR and CH n R 3-n and more preferably from the group consisting of R and OR, where n is 0, 1 or 2, in particular 1 or 2, and the variable R has one of the meanings defined herein, particularly preferred meanings. In particular, R ArThe radicals are selected from the group consisting of methyl, methoxy, phenyl, naphthyl, phenanthrenyl and triphenylenyl, in particular phenyl, naphthyl or phenanthrenyl.

[0097] R is preferably selected from the group consisting of methyl, phenyl, naphthyl, phenanthrenyl and triphenylenyl and is unsubstituted or substituted with one, two or three identical or different R" groups, where R" has, independently at each occurrence, one of the meanings defined herein, particularly the preferred meanings. More preferably, R is selected from the group consisting of phenyl, naphthyl and phenanthrenyl and is unsubstituted.

[0098] R' is preferably selected from the group consisting of hydrogen, methyl, phenyl and naphthyl, which are unsubstituted or substituted with one, two or three identical or different R" groups, where R" has, independently at each occurrence, one of the meanings defined herein, particularly the preferred meanings. More preferably, R' is unsubstituted phenyl or unsubstituted naphthyl.

[0099] R'' is preferably selected from the group consisting of phenyl, OCH3 and CH3.

[0100] The variable n is preferably 1 or 2.

[0101] In formula (Ia), Z 1 Group and Z 2 Both bases are Z 1 and Z 2 In a particular subgroup (10.1) of group (10) of embodiments, in which Z has one of the meanings defined herein, particularly one of the preferred meanings, and both -OZ groups are in the para position relative to the moiety X, the compounds of formula (I) are compounds of formula (Ia-1):

[0102] [ka]

[0103] In the formula, X, R 1 , R 2 , R 3 and R 4 has the meanings defined herein, particularly the meanings described as being preferred, and R 3 and R 4 is particularly different from hydrogen.

[0104] In a subgroup (10.1) of the group (10) of embodiments, the structural unit of formula (II) or (IIa) is a structural unit of formula (IIa-1):

[0105] [ka]

[0106] In the formula, # represents a point of attachment to an adjacent structural unit, and Z a is Z 1a and Z 2a and the variables X, R 1 , R 2 , R 3 and R 4 has the meanings defined herein, particularly the meanings described as being preferred, and R 3 and R 4 is particularly different from hydrogen.

[0107] Preferably, the moiety X of formulae (Ia-1) and (IIa-1) is as defined in group (5), group (5') or group (5'') of the embodiments. Thus, the moiety X here is in particular selected from the group consisting of a single bond, O, N-phenyl, N-naphthyl, N-phenanthryl, CH2, C(CH3)2, CH(CH3), S, S(O) and SO2, more in particular selected from the group consisting of a single bond, O, N-phenyl, N-naphth-1-yl, N-naphth-2-yl, N-phenanthren-9-yl, CH2, C(CH3)2, CH(CH3), S and SO2, in particular selected from the group consisting of a single bond, O, CH2, C(CH3)2, S and SO2, in particular selected from the group consisting of a single bond, C(CH3)2, S and SO2. Particularly preferably, in this context, X is C(CH3)2. Also particularly preferably, in this context, X is S or SO2.

[0108] Also preferred are compounds of formula (Ia-1) and structural units of formula (IIa-1) in which the substituent R 1 and R 2 are independently as defined in groups (6), (6.1), (6.2), (6.3) and (6.3a), respectively, of the embodiments, and the substituent R 3 and R 4 are, independently of one another, as defined in groups (7), (7.1), (7.2), (7.3), (7.4), (7.4a) and (7.5) of embodiments, respectively.

[0109] Even more preferred are compounds of formula (Ia-1) and structural units of formula (IIa-1) in which the substituent R 1 , R 2 , R 3 and R 4 has one of the meanings described herein as being particularly preferred, in particular one of the meanings defined in groups (6), (6.1), (6.2), (6.3) and (6.3a) of embodiments, and groups (7), (7.1), (7.2), (7.3), (7.4), (7.4a) and (7.5).

[0110] Particularly preferred are compounds of formula (Ia-1) and structural units of formula (IIa-1) in which the substituent R 1 , R 2 , R 3 and R 4 has the same meaning as selected from the group consisting of phenyl, naphth-1-yl, naphth-2-yl, 1,2-dihydroacenaphthylene-5-yl, phenanthren-9-yl, pyren-1-yl, pyren-2-yl, pyren-4-yl, triphenylen-1-yl, triphenylen-2-yl, dibenzo[b,d]furan-2-yl, dibenzo[b,d]furan-4-yl, benzo[b]thien-3-yl, benzo[b]thien-4-yl, benzo[b]thien-5-yl, benzo[b]thien-6-yl, benzo[b]thien-7-yl, dibenzo[b,d]thien-2-yl, dibenzo[b,d]thien-4-yl, thianthren-1-yl and thianthren-2-yl. Particularly preferred are compounds of formula (Ia-1) and structural units of formula (IIa-1) in which the substituent R 1 , R 2 , R 3 and R 4 are independently selected from phenyl, naphthyl, 1,2-dihydroacenaphthylenyl, phenanthrenyl, benzo[b]thienyl, dibenzo[b,d]thienyl and thianthrenyl, in particular selected from phenyl, naphth-1-yl, naphth-2-yl, phenanthren-9-yl, dibenzo[b,d]thien-2-yl, dibenzo[b,d]thien-4-yl, thianthren-1-yl and thianthren-2-yl.

[0111] Examples of a particular subgroup (10.1) are compounds of formula (Ia-1) and structural units of formula (IIa-1): y The combinations are defined in any one of rows 1 to 442 of Table A below. y is a substituent R 1 , R 2 , R 3 and R 4 represents the same meaning.

[0112]

Table 1-1

[0113]

Table 1-2

[0114]

Table 1-3

[0115]

Table 1-4

[0116]

Table 1-5

[0117]

Table 1-6

[0118]

Table 1-7

[0119]

Table 1-8

[0120]

Table 1-9

[0121]

Table 1-10

[0122]

Table 1-11

[0123] [Table 1-12]

[0124] [Table 1-13]

[0125] [Table 1-14]

[0126] Among the compounds of formula (Ia-1) and structural units of formula (IIa-1) shown in Table A, particularly preferred are those compounds and structural units of formula (Ia-1) and formula (IIa-1) in which the moiety X is C(CH3)2, SO2, S, or a single bond. That is, particularly preferred are compounds of formula (Ia-1) in which the moiety X, the group Z and the variable R y is as defined in any one of rows 1-95 and 243-442 of Table A above, and the variable R y is a substituent R 1 , R 2 , R 3 and R 4 These terms have the same meaning.

[0127] In formula (Ia), Z 1 Group and Z 2 Both groups are Z 1 and Z 2 In a particular subgroup (10.2) of group (10) of embodiments, in which Z has one of the meanings defined herein, particularly one of the preferred meanings, and both -OZ groups are in the ortho position relative to the moiety X, the compounds of formula (I) are compounds of formula (Ia-2):

[0128] [ka]

[0129] In the formula, X, R 1 , R 2 , R 3 and R 4 has the meanings defined herein, particularly the meanings described as being preferred, and R 3 and R 4 is particularly different from hydrogen.

[0130] In subgroup (10.2) of group (10) of embodiments, the structural unit of formula (II) or (IIa) is a structural unit of formula (IIa-2):

[0131] [ka]

[0132] In the formula, # represents a point of attachment to an adjacent structural unit, and Z a is Z 1a and Z 2a and the variables X, R 1 , R 2 , R 3 and R 4 has the meanings defined herein, particularly the meanings described as being preferred, and R 3 and R 4 is particularly different from hydrogen.

[0133] Preferably, the moiety X of formulae (Ia-2) and (IIa-2) is as defined in group (5) or group (5''') of the embodiments. Thus, the moiety X here is in particular selected from the group consisting of a single bond, O, N-phenyl, N-naphthyl, N-phenanthryl, CH2, C(CH3)2, CH(CH3), S, S(O) and SO2, more in particular selected from the group consisting of a single bond, O, N-phenyl, N-naphth-1-yl, N-naphth-2-yl, N-phenanthren-9-yl, CH2, C(CH3)2, CH(CH3), S and SO2, in particular selected from the group consisting of a single bond, O, CH2, C(CH3)2, S and SO2, in particular selected from the group consisting of a single bond, C(CH3)2, S and SO2. Particularly preferably, in this context, X is a single bond.

[0134] Also preferred are compounds of formula (Ia-2) and structural units of formula (IIa-2) in which the substituent R 1 and R 2 are independently as defined in groups (6), (6.1), (6.2), (6.3) and (6.3a), respectively, of the embodiments, and the substituent R 3 and R 4 are, independently of one another, as defined in groups (7), (7.1), (7.2), (7.3), (7.4), (7.4a) and (7.5) of embodiments, respectively.

[0135] Even more preferred are compounds of formula (Ia-2) and structural units of formula (IIa-2) in which the substituent R 1 , R 2 , R 3 and R 4 has one of the meanings described herein as being particularly preferred, in particular one of the meanings defined in groups (6), (6.1), (6.2), (6.3) and (6.3a) of embodiments, and groups (7), (7.1), (7.2), (7.3), (7.4), (7.4a) and (7.5).

[0136] Particularly preferred are compounds of formula (Ia-2) and structural units of formula (IIa-2) in which the substituent R 1 , R 2 , R 3 and R 4 Phenyl, naphth-1-yl, naphth-2-yl, 1,2-dihydroacenaphthylene-5-yl, phenanthren-9-yl, pyren-1-yl, pyren-2-yl, pyren-4-yl, triphenylen-1-yl, triphenylen-2-yl, dibenzo[b,d]furan-2-yl, dibenzo[b,d]furan-4-yl, benzo[b]thien-3-yl, benzo[b]thien-4-yl, benzo[b]thien-5-yl, benzo[b]thien-6-yl , benzo[b]thien-7-yl, dibenzo[b,d]thien-2-yl, dibenzo[b,d]thien-4-yl, thianthren-1-yl and thianthren-2-yl, in particular those having the same meaning selected from phenyl, naphth-1-yl, naphth-2-yl, phenanthren-9-yl, dibenzo[b,d]thien-2-yl, dibenzo[b,d]thien-4-yl, thianthren-1-yl and thianthren-2-yl.

[0137] Examples of a particular subgroup (10.2) are compounds of formula (Ia-2) and structural units of formula (IIa-2): y The combinations are defined in any one of rows 1 to 64 of Table B below. y is a substituent R 1 , R 2 , R 3 and R 4 represents the same meaning.

[0138] [Table 2-1]

[0139] [Table 2-2]

[0140] A compound of formula (I) (wherein X, Z1 , Z 2 , R 1 , R 2 , R 3 and R 4 Each of R has one of the meanings defined herein) can be prepared, for example, by the compound (I) 1 , R 2 , R 3 and R 4 have the same meaning, and Z 1 and Z 2 is -Alk-OH, -CH-Ar as defined herein 2 -CH2-OH, Alk-C(O)OR x and -CH2-Ar 2 -C(O)OR x The corresponding compounds (I) (wherein Z is the same group selected from the group consisting of 1 and Z 2 are both hydrogen) can be obtained, for example, by modifying the process of Scheme 1 to omit step b) and subject compound (2) directly to reaction step c).

[0141] [ka]

[0142] Each of the transformations of steps a), b) and c) of Scheme 1 can be achieved using one or more of the process steps described herein below in connection with Schemes 2a, 2b, 2c, 3, 4a, 4b, 5, 6a, 6b, 6c, 7a and 7b, or by obvious modifications of these reaction steps, or alternatively by procedures or combinations thereof that are well established in preparative organic chemistry.

[0143] A compound of formula (Ia') which is a compound of formula (Ia) as defined herein, 1 , R 2 , R 3 and R 4have the same meaning, i.e. are identical substituents Ar selected from optionally substituted monocyclic or polycyclic aryl(hetaryl) as defined herein, and Z 1 and Z 2 is -Alk-OH, -CH-Ar as defined herein 2 -CH2-OH, -Alk-C(O)OR x and -CH2-Ar 2 -C(O)OR x embedded image (Z′ groups selected from the same) can be prepared, for example, by a reaction similar to that depicted in Reaction Scheme 2a below.

[0144] [ka]

[0145] In a first step i), bisphenol (1') (whose hydroxyl group is either ortho or para to the moiety X, respectively) is reacted with a suitable brominating agent to give the corresponding tetrabrominated derivative (4). A suitable brominating agent is in particular elemental bromine, typically used in a 3-15 fold molar excess relative to bisphenol (1'). In step ii), tetrabromobisphenol (4) is reacted with the reagent Y-Z', where Y is a suitable leaving group such as a chloride, bromide, iodide, tosylate or mesitylate group and Z' is -Alk-OH, -CH2-Ar, in the presence of a base, for example an oxobase such as an alkali carbonate such as potassium carbonate, to give 2 -CH2-OH, -Alk-C(O)OR x or -CH2-Ar 2 -C(O)OR x The conversion in step iii) of scheme 2a can be carried out by reacting tetrabromide 5 with a boronic acid of formula Ar-B(OH)2, where Ar is a substituent R 1 and R 2The reaction can be achieved via Suzuki coupling reaction by treating with a boronic acid such as boronic acid ester or anhydride, in particular its C1-C4-alkyl ester, with a boronic acid ester or anhydride, in particular its C1-C4-alkyl ester. Suitable palladium catalysts are in particular those having at least one trisubstituted phosphine ligand, such as tetrakis(triphenylphosphine)palladium and tetrakis(tritolylphosphine)palladium. Often the palladium catalyst is prepared in situ from a suitable palladium precursor, such as palladium(II) acetate (Pd(OAc)2), and a suitable phosphine ligand, in particular a triarylphosphine, such as triphenylphosphine and tritolylphosphine. Usually the reaction is carried out in the presence of a base, in particular an oxobase, such as an alkali carbonate, for example potassium carbonate, or an alkaline earth carbonate.

[0146] When the Z' group of compound (5) is hydroxyethyl, the transformation shown in reaction step ii) of scheme 2a can be carried out using 2-chloro-ethanol as reagent Y-Z', or ethylene carbonate or ethylene oxide, in particular ethylene carbonate, in place of reagent Y-Z'. Such transformations using 2-chloro-ethanol, ethylene carbonate or ethylene oxide are carried out in the presence of a base, for example an oxobase such as an alkali carbonate, for example potassium carbonate.

[0147] As a further example, the Z′ group of compound (5) is -Alk-C(O)OR x In the latter case, the transformation shown in reaction step ii) of scheme 2a can be carried out by using Hal-Alk-C(O)OR as reagent Y-Z′ in a manner similar to that described, for example, in T. Ema, J. Org. Chem., 2010, 75(13), 4492-4500 or T. Ema et al., Org. Lett., 2006, 8, 17, 3773-3775. x (wherein Hal is in particular a halogen, such as bromine or chlorine). If necessary, the ester group O-Alk-C(O)R xcan then be converted to the corresponding acid group O-Alk-C(O)OH using well-known procedures for ester hydrolysis.

[0148] Suitable reaction conditions as well as suitable reagents for step i) of scheme 2a can be found, for example, in U.S. Pat. No. 3,363,007, U.S. Pat. No. 5,208,389, JP 04-009346, CN 101100416, U.S. Pat. No. 6,147,264, L. Kumar et al., Organic Process Research & Development, 2010, 14(1), 174-179, S. Dev et al., Polymer, 2017, 133, 20-29, R.-N. Wang et al., Hebei Gongye Daxue Xuebao, 2012, 41(3), 42-45, J. Lu et al., Crystal Growth & Design, 2011, 11(8), 3551-3557, K.-B. Oh et al., Bioorganic & Medicinal Chemistry Letters, 2008, 18(1), 104-108, Y. Xin et al., Huaxue Yanjiu Yu Yingyong, 2006, 18(11), 1346-1348, Q. Yang et al., China, Patent No. 111072529, China Patent No. 103992209, China Patent No. 102898337, and VA Orlova et al., Trudy Vsesoyuznogo Instituta Gel'mintologii imeni KI Skryabina, 1971, 18, 201-205; for step ii) of scheme 2a, for example, JP 50-105638, JP 58-046034, JP 52-051351, Imai, Hirokazu et al., Japan, JP 2013-249373, JP 2013-249374, JP 2008-143854, and JP 03-038563; for step iii) of scheme 2a, 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., 2011, 52, 311-313; S. Bourrain et al., Synlett, 2004, 5, 795-798; and B. Li et al., Europ. J. Org. Chem., 2011, 3932-3937.

[0149] Alternatively, the order of steps i), ii) and iii) shown in scheme 2a can be rearranged according to schemes 2b and 2c below to prepare compounds of formula (Ia').

[0150] [ka]

[0151] The reactions of steps i), ii) and iii) according to schemes 2b and 2c can be carried out using the same or very similar reaction conditions as described for steps i), ii) and iii) of scheme 2a. The compound of formula (Ia″) obtained in the second reaction step of scheme 2b can be converted to a compound of formula (Ia) as defined herein, where R 1 , R 2 , R 3 and R 4 are all identical substituents as defined in the context of Scheme 2a, and Z 1 and Z 2 are both hydrogen). Thus, the sequence of steps i) and iii) according to scheme 2b) is suitable for preparing such compounds (Ia) of the invention.

[0152] As an alternative to step i) of schemes 2a and 2b, the tetrabrominated bisphenols of formula (4), where X is the moiety CH, can also be prepared by condensation of 2,6-dibromophenol or 2,4-dibromophenol with formaldehyde, as depicted in scheme 3 below.

[0153] [ka]

[0154] This reaction is described by K.-W. Chi et al., Journal of the Korean Chemical Society, 2003, 47(4), 412-416.

[0155] As an alternative to the synthesis according to Scheme 2a or 2c, a tetrabromide of formula (5), where X is S(O) and Z′ is —Alk-OH, —CH—Ar as defined herein, may be prepared by the synthesis of 2 -CH2-OH, -Alk-C(O)OR x or -CH2-Ar 2 -C(O)OR x Compounds (Ia') (wherein X is S(O)) can also be prepared by reducing the corresponding compound (5) (wherein X is SO2). Similarly, the tetrabromide of formula (5) (wherein X is S(O)) can be reduced to the corresponding sulfide to provide an alternative approach to compound (5) (wherein X is S). Similarly, compound (Ia') (wherein X is S(O) or S) is also accessible via reduction of the corresponding compound (Ia') bearing a SO2 or S(O) moiety at the X position. These transformations are summarized in Schemes 4a and 4b below.

[0156] [ka]

[0157] The reductive transformations depicted in Schemes 4a and 4b can be carried out using procedures well established in the art for converting sulfones to sulfoxides and sulfoxides to sulfides, respectively. For example, sulfones can be converted to the respective sulfoxides by first reaction with 4-chlorobenzenediazonium tetrafluoroborate followed by reduction with sodium borohydride, and sulfoxides can be converted to the respective sulfides by reduction with lithium aluminum hydride or elemental sulfur.

[0158] Compounds of formula (Ia-1) 1 An alternative to the methods according to Schemes 2a-2c for the preparation of arylphenols (Ia″), where X is N-Ar, is the synthesis shown in Scheme 5 below. 2,6-diarylphenols or 2,4-diarylphenols (6) are first brominated and then their hydroxyl groups are converted to protected methoxymethyl (MOM) ether groups to generate intermediates (7), which are then reacted with arylamines (8) in the presence of a palladium catalyst. Final deprotection gives compounds (Ia″), where X is N-Ar. 1 and Ar 1 is as defined herein), which can be converted to the respective compound of formula (Ia') according to scheme 2b. A similar method is described in detail in Y. Matsuta et al., Chemistry - An Asian Journal, 2017, 12(15), 1889-1894.

[0159] [ka]

[0160] Compounds of formula (Ia) of the present invention include compounds of formula (Ia'"), in which X has one of the meanings defined herein and R 3 and R 4 are both hydrogen, and R 1 and R 2are identical substituents Ar selected from optionally substituted monocyclic or polycyclic aryl(hetaryl) as defined herein, Z 1 and Z 2 is -Alk-OH, -CH-Ar as defined herein 2 -CH2-OH, -Alk-C(O)OR x and -CH2-Ar 2 -C(O)OR x embedded image wherein Z′ is an identical Z′ group selected from

[0161] [ka]

[0162] Reaction steps i), ii) and iii) of Scheme 6a can in principle be carried out in a similar manner to steps i) to iii) described above in connection with the preparation of compounds of formula (Ia') according to Scheme 2a. However, the bromination of this step i) differs from the bromination of step i) of Scheme 2a and is typically carried out with a 1.5- to 5-fold excess of bromine relative to bisphenol (1'), as defined in the context of the process of Scheme 2a above.

[0163] Suitable reaction conditions and suitable reagents for step i) of scheme 6a can be derived from the prior art documents listed above in relation to the method represented by scheme 2a. In this regard, additional specific information for step ii) of scheme 6a can be cited, for example, from Canadian Patent No. 663542, U.S. Patent No. 4,093,555, and British Patent No. 1489659; additional specific information for step iii) of scheme 6a can be cited from JP-A-02-111743, JP-A-08-208775, and SR Turner et al., High Performance Polymers, 2005, 17(3), 361-376.

[0164] Alternatively, compounds of formula (Ia''') can be prepared by rearranging the order of steps i), ii) and iii) shown in Scheme 6a according to Schemes 6b and 6c below.

[0165] [ka]

[0166] The reactions of steps i), ii) and iii) according to schemes 6b and 6c can be carried out using the same or very similar reaction conditions as described for steps i), ii) and iii) of scheme 6a. The compounds of formula (Ia'''') obtained in the second reaction step of scheme 6b can be converted to compounds of formula (Ia) as defined herein, where R 3 and R 4 are both hydrogen, and R 1 and R 2 is the same substituent Ar as defined above, Z 1 and Z 2 are both hydrogen). Thus, the sequence of steps i) and iii) according to scheme 6b) is suitable for preparing such compounds (Ia) of the invention.

[0167] As an alternative to the synthesis according to Scheme 6a or 6c, a dibromide of formula (10), where X is S(O) and Z′ is —Alk-OH, —CH—Ar, as defined herein, may be prepared by the synthesis of 2 -CH2-OH, -Alk-C(O)OR x or -CH2-Ar 2 -C(O)OR xCompounds (Ia) (wherein X is S) can also be prepared by reducing the corresponding compounds (10) (wherein X is SO). Similarly, bisphenol compounds of formula (10) (wherein X is S(O)) can be reduced to the corresponding sulfides to provide an alternative approach to compound (10) (wherein X is S). Similarly, compounds (Ia''') (wherein X is S(O) or S) are also accessible via reduction of the corresponding compounds (Ia'') bearing a SO or S(O) moiety at the X position. These transformations are summarized in Schemes 7a and 7b below.

[0168] [ka]

[0169] The reductive transformations depicted in Schemes 7a and 7b can be carried out using procedures well established in the art for converting sulfones to sulfoxides and sulfoxides to sulfides, respectively, such as those described above in connection with the methods of Schemes 4a and 4b.

[0170] Dibrominated bisphenols of formula (9) where X is the moiety CH2 and compounds of formula (Ia''') and (Ia'''') where X is N-Ar 1 Alternative methods for the preparation of (which are) can be readily derived from the methods described above in connection with Schemes 3 and 5 by using 2- or 4-bromophenol instead of 2,6-dibromophenol and 2- or 4-aryl instead of 2,6-diarylphenol (6), respectively, as starting compounds.

[0171] Additional compounds of formula (I) may be prepared using obvious modifications of the above reactions and combinations thereof with procedures well established in preparative organic chemistry.

[0172] The reaction mixture obtained in each step of the synthesis for preparing the compounds of the above reaction schemes 1, 2a, 2b, 2c, 3, 4a, 4b, 5, 6a, 6b, 6c, 7a and 7b is usually treated by conventional methods, such as mixing with water, separating the phases, and purifying the crude product by washing, chromatography or crystallization, if necessary. In some cases, the intermediate is in the form of a colorless or light brown viscous oil, and the volatile components are removed or purified under reduced pressure at moderately elevated temperatures. If the intermediate is obtained as a solid, purification can be achieved by recrystallization or washing procedures such as slurry washing.

[0173] The starting compounds used in the syntheses shown in Schemes 1, 2a, 2b, 2c, 3, 4a, 4b, 5, 6a, 6b, 6c, 7a and 7b above to prepare compounds of formula (I) are either commercially available or can be prepared by methods known in the art.

[0174] As mentioned above, the compound of the present invention can be obtained with high purity.This means that the product obtained does not contain significant amounts of organic impurities other than volatile substances that are different from the compound of formula (I).Usually, the purity of the compound of formula (I) is at least 95%, particularly at least 98%, particularly at least 99% based on non-volatile organic matter.That is, the product contains at most 5%, particularly at most 2%, particularly at most 1% of non-volatile impurities other than the compound of formula (I).

[0175] The term "volatile substances" refers to substances at standard atmospheric pressure (10 5 Non-volatile organics are therefore understood to mean compounds having a boiling point above 200° C. at standard atmospheric pressure.

[0176] Particularly advantageously, the compounds of formula (I), as well as their solvates, can often 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 solvent. Thus, a particular aspect of the present invention relates to the compounds of formula (I) that exist essentially in crystalline form. In particular, the present invention relates to the crystalline forms in which the compounds of formula (I) exist without solvent and to the crystalline solvates (crystals containing incorporated solvent) of the compounds of formula (I).

[0177] Particularly advantageously, the compounds of formula (I), as well as their solvates, can often be easily crystallized by conventional organic solvents. This allows for efficient purification of the compounds of formula (I). Suitable organic solvents for crystallization of the compounds of formula (I) or their solvates include, but are not limited to, aromatic hydrocarbons such as toluene or xylene; aliphatic ketones, particularly ketones 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; and aliphatic alcohols having 1 to 4 carbon atoms, such as methanol, ethanol or isopropanol, and mixtures thereof.

[0178] Alternatively, the compounds of formula (I), as well as their solvates, can be obtained in purified form by using other simple and efficient methods for purifying the crude products of these compounds. For example, slurry washing, in particular of the crude solid obtained immediately after conversion to produce the compounds of formula (I). Slurry washing is generally carried out at room temperature or at elevated temperatures, usually about 30-90°C, in particular 40-80°C. Suitable organic solvents here are in principle the same as those listed above as suitable for the crystallization of the compounds of formula (I). For example, in particular the aromatic hydrocarbons, aliphatic ketones and aliphatic ethers mentioned above, such as toluene, methyl ethyl ketone and methyl tert-butyl ether.

[0179] Therefore, the compounds of formula (I) used for the manufacture of thermoplastic polymers, particularly polycarbonates, as defined herein, can be easily prepared and obtained with high yield and high purity, respectively. In particular, the compounds of formula (I) can be obtained in crystalline form, and therefore can be efficiently purified to the degree required for the manufacture of optical resins. In particular, these compounds can be obtained with a purity that provides high refractive index and low haze. This is particularly important for use in the manufacture of optical resins to manufacture optical elements. In conclusion, the compounds of formula (I) are particularly useful as monomers in the manufacture of optical resins.

[0180] Those skilled in the art will easily understand that the monomers of formula (I) used correspond to the structural units of formula (II) contained in the thermoplastic resin. Similarly, the monomers of formulas (Ia), (Ia-1) and (Ia-2) used correspond to the structural units of formulas (IIa), (IIa-1) and (IIa-2) contained in the thermoplastic resin, respectively.

[0181] Those skilled in the art will also understand that the structural units of formulae (II), (IIa), (IIa-1) and (IIa-2) are repeat units in the polymer chain of a thermoplastic resin.

[0182] In addition to the structural units of each of the formulae (II), (IIa), (IIa-1) and (IIa-2), the thermoplastic resin may have structural units different therefrom. In a preferred embodiment, these further structural units are derived from aromatic monomers of formula (IV) and result in structural units of formula (V): H.O.R. z -A 1 -R z -OH (IV) #-OR z -A 1 -R z -O-# (V)

[0183] During the ceremony, # represents the point of attachment to the adjacent structural unit; A 1 is a polycyclic group having at least two benzene rings, which may be linked by A and / or directly fused to each other and / or fused to a non-benzene carbocyclic ring, and A 1 is unsubstituted or 1, 2 or 3 R aa Group(R aa is substituted with selected from the group consisting of halogen, C1-C6-alkyl, C5-C6-cycloalkyl and phenyl; A is selected from the group consisting of a single bond, O, C=O, S, SO2, CH2, CH-Ar, CAr2, CH(CH3), C(CH3)2 and a group of formula (A');

[0184] [ka]

[0185] During the ceremony, Q represents a single bond, O, NH, C=O, CH2 or CH=CH; R 7a , R 7b are each independently hydrogen, fluorine, CN, R, OR, or CH k R 3-k, NR2, C(O)R and C(O)NH2, where R is as defined herein and k is 0, 1, 2 or 3; and * represents the point of attachment to the benzene ring; Ar is selected from the group consisting of monocyclic or polycyclic aryl having 6 to 26 carbon atoms as ring atoms and monocyclic or polycyclic hetaryl having a total of 5 to 26 ring atoms, in which 1, 2, 3 or 4 of the hetaryl ring atoms are selected from nitrogen, sulfur and oxygen, and the remaining hetaryl ring atoms are carbon atoms, and Ar is unsubstituted or substituted with 1, 2 or 3 R ab Group(R ab is substituted with selected from the group consisting of halogen, phenyl and C1-C4-alkyl; R z is a single bond, Alk 1 , O-Alk 2 -, O-Alk 2 -[O-Alk 2 -] p - or O-Alk 3 -C(O)-(O is A 1 (bonded to); p is an integer from 1 to 10; Alk 1 is C1-C4-alkanediyl; Alk 2 is C2-C4-alkanediyl; and Alk 3 is C1-C4-alkanediyl.

[0186] R in formula (IV) z O-Alk 3 When it is -C(O), an ester can be used instead, in particular a C1-C4-alkyl ester of a monomer of formula (IV).

[0187] In formulas (IV) and (V), A 1is in particular a polycyclic group having two benzene or naphthalene rings, the benzene ring being linked to A. In this respect, A is in particular selected from the group consisting of a single bond, a CH-Ar, CAr2, and a group A'.

[0188] In formulas (IV) and (V), R z In particular, O-Alk 2 -Alk 2 is in particular a straight-chain alkanediyl having 2 to 4 carbon atoms, in particular O-CH2CH2.

[0189] Among the monomers of formula (IV), those represented by the following general formulae (IV-1) to (IV-6) are preferred.

[0190] [ka]

[0191] During the ceremony, a and b are 0, 1, 2 or 3, in particular 0 or 1; c and d are 0, 1, 2, 3, 4 or 5, in particular 0 or 1; e and f are 0, 1, 2, 3, 4 or 5, in particular 0 or 1; R z , R aa , R ab , R 7a and R 7b is as defined in formula (IV), R z is in particular selected from a single bond, CH2 and OCH2CH2.

[0192] Among the monomers of formula (IV), particularly preferred are those represented by the general formulae (IV-11) to (IV-20) (wherein R z and R aa is as defined herein, and R z is in particular a monomer selected from a single bond, CH2 and O-CH2CH2, in particular O-CH2CH2:

[0193]

change

[0194] Examples of the compounds of formulae (IV-11) to (IV-20) include 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, Fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenylfluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-isopropylphenylfluorene, 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, also known as BPPEF, 9,9-bis(6-hydroxy-2-naphthyl)fluorene 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)fluorene, also known as 9,9-bis(6-(2-hydroxyethoxy)naphthalen-2-yl)fluorene (BNEF), 10,10-bis(4-hydroxyphenyl)anthracen-9-one, 10,10-bis(4-(2-hydroxyethoxy)phenyl)anthracen-9-one, 4,4'-dihydroxytetraphenylmethane, 4,4'-di-(2-hydroxyethoxy)-tetraphenylmethane, 3,3'-diphenyl-4,4'-dihydroxy-tetraphenylmethane , di-(6-hydroxy-2-naphthyl)-diphenylmethane, 2,2'-[1,1'-binaphthalene-2,2'-diylbis(oxy)]diethanol, also known as 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl or 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene (BNE), 2,2'-bis(1-hydroxymethoxy)-1,1'-binaphthyl, 2,2'-bis(3-hydroxypropyloxy)-1,1'-binaphthyl, 2,2'-bis(4-hydroxybutoxy)-1,1'-binaphthyl, 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-hydroxymethoxy)-6,6'-diphenyl-1,1'-binaphthalene, 2,2'-bis(2-hydroxymethoxy)-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'-di(naphthalen-1-yl)-1,1'-binaphthalene, 2,2'-bis(2-hydroxyethoxy)-6,6'-di(naphthalen-2-yl)-1,1'-binaphthalene, 2,2'-bis(2-hydroxyethoxy)-6,6'-di(9-phenanthryl)-1,1'-binaphthalene, etc. Among the monomers of general formula (IV) or formulae (IV-1) to (IV-6), more preferred are the monomers of formulae (IV-1), (IV-2), (IV-3) and (IV-6), particularly preferred are the monomers of formulae (IV-2), (IV-3) and (IV-6), and particularly preferred are 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl (BNE or BHBNA), 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl (DPBHBNA), 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (BPEF), 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)fluorene (BNEF) and 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene (BPPEF).

[0195] Therefore, the structural unit of formula (V) that can be contained in the thermoplastic resin is preferably the structural unit of general formulae (V-1) to (V-6).

[0196] [ka]

[0197] During the ceremony, a and b are 0, 1, 2 or 3, in particular 0 or 1; c and d are 0, 1, 2, 3, 4 or 5, in particular 0 or 1; e and f are 0, 1, 2, 3, 4 or 5, in particular 0 or 1; R z , R aa , R ab , R 7a and R 7b is as defined in formula (V), R z is preferably selected from a single bond, CH2 and OCH2CH2.

[0198] Particularly preferred structural units are those represented by the general formulae (V-11) to (V-20) (wherein R z and R aa is as defined herein, and R z is a structural unit selected in particular from a single bond, CH2 and O-CH2CH2, in particular O-CH2CH2.

[0199] [ka]

[0200] Among the structural units of the formulae (V-1) to (V-6), the structural units of the formulae (V-1), (V-2) and (V-6) are preferred. Among the structural units of the formulae (V-11) to (V-20), the structural units of the formulae (V-11), (V-12), (V-14), (V-19) and (V-20) are particularly preferred, and the structural units of the formulae (V-11), (V-19) and (V-20) are more preferred, and the structural units derived from 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl (BNE or BHBNA), 2,2-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl (DPBHBNA) and 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (BPEF) are particularly preferred.

[0201] In a particular preferred group of embodiments, the thermoplastic resin of the present invention has at least one structural unit of formula (IIa-1) or (IIa-2) and at least one structural unit selected from the group consisting of structural units of formula (V-11), structural units of formula (V-19) and structural units of formula (V-20). In this particular group of embodiments, the following thermoplastic resins are preferred: 1 , R 2 , R 3 and R 4 or R 1 and R 2 are preferred which are identical and have one of the meanings defined herein, particularly one of the meanings described as being preferred. In this particular group of embodiments, the following thermoplastic resins, namely the structural units of formulae (V-11), (V-19) and (V-20), have R z Preferred is where the group is O-CH2CH2.

[0202] In this particular preferred group of thermoplastic resins of the embodiment, the total molar ratio of structural units of formula (IIa-1) or (IIa-2) in the total molar amount of structural units of formula (II) and formula (V) is preferably in the range of 1 to 70 mol%, preferably in the range of 5 to 60 mol%, more preferably in the range of 8 to 45 mol%, and even more preferably in the range of 10 to 30 mol%.

[0203] A further particular group (10) of embodiments of the present invention relates to thermoplastic resins having very low, almost no or no birefringence. The resins of said group (10) of embodiments in particular comprise structural units of formula (II), such as formula (IIa-1), where R 1 , R 2 , R 3 and R 4is as defined for group 5.5 of embodiments), characterized in that it has one or more structural units different from the structural units of formula (II), preferably selected from the structural units of formula (V), in particular from the structural units of formulae (V-11), (V-12), (V-14), (V-19) and (V-20), in particular from the structural units of formulae (V-11), (V-19) and (V-20). In the thermoplastic resins of this particular embodiment group (10), the total molar ratio of the structural units of formula (IIa-1) or (IIa-2) in the amount of all the structural units of formulae (II) and (V) is in the range of 0.5 to 70 mol%, preferably in the range of 1 to 60 mol%, more preferably in the range of 2 to 45 mol%, even more preferably in the range of 3 to 30 mol%.

[0204] Compounds of formula (IV), (IV-1), (IV-2), (IV-3), (IV-4), (IV-5), (IV-6), (IV-11), (IV-12), (IV-13), (IV-14), (IV-15), (IV-16), (IV-17), (IV-18), (IV-19) and (IV-20) are known or can be prepared by methods analogous to known methods.

[0205] For example, the compound of formula (IV-6) can be produced by various synthesis methods, as described in, for example, JP 2014-227387 A, JP 2014-227388 A, JP 2015-168658 A, and JP 2015-187098 A. For example, the compound can be produced by a method of reacting 1,1'-binaphthol with ethylene glycol monotosylate, a method of reacting 1,1'-binaphthol with alkylene oxide, halogenoalkanol, or alkylene carbonate, a method of reacting 1,1'-binaphthol with ethylene carbonate, or the like. As a result, R z -OH is O-Alk 2 -Or O-Alk 2 -[Alk 2 -]p-, a compound of formula (IV-6) can be prepared.

[0206] For example, the compound of formula (IV-2) can be produced by various synthesis methods, as described in, for example, Japanese Patent Publication No. 5442800 and Japanese Patent Publication No. 2014-028806. Specific examples of the synthesis method include (a) a method of reacting fluorenes with hydroxynaphthalenes in the presence of hydrogen chloride gas and mercaptocarboxylic acid, (b) a method of reacting 9-fluorene with hydroxynaphthalenes in the presence of an acid catalyst (and alkyl mercaptan), (c) a method of reacting fluorenes with hydroxynaphthalenes in the presence of hydrochloric acid and thiols (mercaptocarboxylic acid, etc.), and (d) a method of reacting fluorenes with hydroxynaphthalenes in the presence of sulfuric acid and thiols (mercaptocarboxylic acid, etc.), and crystallizing the fluorenes with a crystallization solvent composed of a hydrocarbon and a polar solvent to produce bisnaphtholfluorene, to obtain 9,9-bis(hydroxynaphthyl)fluorenes, etc. As a result, R z Compounds of formula (IV-2) in which is a single bond can be prepared.

[0207] R z O-Alk 2 -Or O-Alk 2 -[O-Alk 2 -] p The compound of formula (IV) where R z It can be produced by reacting a compound of formula (IV) in which R is a single bond with an alkylene oxide or a haloalkanol. z By reacting alkylene oxides or haloalkanols with 9,9-bis(hydroxynaphthyl)fluorenes of formula (IV-2) in which R is a single bond, z O-Alk 2 -Or O-Alk 2 -[Alk 2 -] p For example, 9,9-bis[6-(2-hydroxyethoxy)naphthyl]fluorene may be obtained by reacting 9,9-bis[6-(2-hydroxynaphthyl]fluorene with 2-chloroethanol under alkaline conditions.

[0208] In addition, in the monomer of formula (I) and the comonomer of formula (IV) used to produce the thermoplastic resin, impurities that may arise from the production of the monomers, such as OZ 1 -OH or OZ 2 Hydroxy compounds that have an OH group instead of the -OH group, or O-Alk ’ -Alk instead of - group ’ -[O-Alk ’ -]o group or R 1 , R 2 , R 3 or R 4 The total amount of such impurities is preferably 1000 ppm or less, more preferably 500 ppm or less, even more preferably 200 ppm or less, and particularly preferably 100 ppm or less. The total amount of impurities contained in the monomers used to produce the thermoplastic resin is desirably 100 ppm or less, particularly desirably 50 ppm or less, and more desirably 20 ppm or less. In particular, the formula (I) refers to Z 1 or Z 2 The total amount of dihydroxy compounds having at least one carbon number different in the group is preferably 1000 ppm or less, more preferably 500 ppm or less, even more preferably 200 ppm or less, and particularly preferably 100 ppm or less, in the monomer mainly composed of the dihydroxy compound represented by formula (I). 1 or Z 2 The total content of dihydroxy compounds having at least one different carbon number value in at least one of the groups is preferably 50 ppm or less, more preferably 20 ppm or less.Similarly, the content of impurities in the comonomer of formula (IV) is within the ranges given above for the monomer of formula (I).

[0209] Suitable thermoplastic resins for the production of optical elements such as lenses are in particular polycarbonates, polyester carbonates and polyesters. Suitable thermoplastic resins for the production of optical elements such as lenses are in particular polycarbonates.

[0210] Said polycarbonates are structurally characterized by having at least one structural unit of formula (II), (IIa), (IIa-1) and (IIa-2), respectively, optionally derived from a diol monomer different from the monomer compound of formula (I), for example a structural unit of formula (V): #-OR z -A 1 -R z -O-# (V) (In the formula, #, R z and A 1 is as defined herein above);

[0211] and structural units of formula (III-1) derived from carbonate moieties.

[0212] [ka]

[0213] In the formula, each # represents a point of attachment to an adjacent structural unit, i.e., the point of attachment of the structural unit of formula (II) to O, and, if present, the point of attachment of the structural unit of formula (V) to O.

[0214] Said polyesters are structurally characterized by having at least one structural unit of formula (II), (IIa), (IIa-1) and (IIa-2), respectively, and optionally a structural unit derived from a diol monomer different from the monomer compound of formula (I). For example, a structural unit of formula V and a structural unit derived from a dicarboxylic acid. For example, a structural unit of formula (III-2) in the case of benzenedicarboxylic acid, a structural unit of formula (III-3) in the case of naphthalenecarboxylic acid, a structural unit of formula (III-4) in the case of oxalic acid and a structural unit of formula (III-5) in the case of malonic acid.

[0215] [ka]

[0216] In formulae (III-2) to (III-5), each variable # represents the point of attachment to the adjacent structural unit, i.e., the point of attachment of the structural unit of formula (II) to O, and, if present, the point of attachment of the structural unit of formula (V) to O.

[0217] Said polyester carbonates are structurally characterized by having at least one structural unit of formula (II), (IIa), (IIa-1) and (IIa-2), and optionally a structural unit derived from a diol monomer different from the monomer compound of formula (I). For example, the structural unit of formula (V), the structural unit of formula (III-1) derived from a carbonate-forming component and the structural unit derived from a dicarboxylic acid. For example, the structural unit of formula (III-2) in the case of benzenedicarboxylic acid, the structural unit of formula (III-3) in the case of naphthalenecarboxylic 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.

[0218] A particular group of embodiments relates to thermoplastic copolymer resins, in particular polycarbonates, polyestercarbonates and polyesters comprising both structural units of formula (II) and one or more structural units of formula (V), such as resins, in particular polycarbonate resins, polyestercarbonate resins and polyester resins obtained by reacting at least one monomer of formula (I) with one or more monomers of formula (IV). In this case, the molar ratio of the monomer of formula (I) to the monomer of formula (IV) and the molar ratio of the structural unit of formula (II) similar thereto to the structural unit of formula (V) are in the range of 5:95 to 80:20, in particular in the range of 10:90 to 70:30, in particular in the range of 15:85 to 60:40 or in the range of 1:99 to 70:30, in particular in the range of 5:95 to 60:40, more preferably in the range of 8:92 to 45:55 or in the range of 10:90 to 40:60, in particular in the range of 12:88 to 30:70 or in the range of 12:88 to 20:80. Therefore, the molar ratio of the structural unit of formula (II) is usually 1 to 70 mol%, particularly 5 to 60 mol%, based on the total molar amount of the structural units of formula (II) and formula (V), more preferably 8 to 45 mol% or 10 to 40 mol%, particularly 12 to 30 mol% or 15 to 30 mol%, particularly 12 to 20 mol% or 15 to 20 mol%. Therefore, the molar ratio of the structural unit of formula (V) is usually 30 to 99 mol%, particularly 40 to 95 mol%, more preferably 55 to 92 mol% or 60 to 90 mol%, particularly 70 to 88 mol% or 70 to 85 mol%, particularly 80 to 88 mol% or 80 to 85 mol%, based on the total molar amount of the structural units of formula (II) and formula (V).

[0219] The thermoplastic copolymer resin of the present invention, such as a polycarbonate resin, may have any of a random copolymer structure, a block copolymer structure, and an alternating copolymer structure. In the thermoplastic resin of the present invention, the above-mentioned structural unit (II) and one or more different structural units (V) may not all be contained in the same polymer molecule. That is, if the above-mentioned structure is contained in each of a plurality of polymer molecules, the thermoplastic copolymer resin of the present invention may be a blend resin. For example, the thermoplastic resin containing both the above-mentioned structural unit (II) and the structural unit (V) may be a copolymer containing both the structural unit (II) and the structural unit (V), or a mixture of a homopolymer or copolymer containing at least one structural unit (II) and a homopolymer or copolymer containing at least one structural unit (V), or a blend resin of a copolymer containing at least one structural unit (II) and a first structural unit (V) and a copolymer containing at least one structural unit (II) and at least one second structural unit (V) other than the first structural unit (V).

[0220] Thermoplastic polycarbonates can be obtained by polycondensation of a diol component with a carbonate-forming component.Similarly, thermoplastic polyesters and thermoplastic polyester carbonates can be obtained by polycondensation of a diol component with a dicarboxylic acid or an ester-forming derivative thereof, and an optional carbonate-forming component.

[0221] Specifically, the thermoplastic resin (polycarbonate resin) can be produced by the following method.

[0222] The method for producing a thermoplastic resin such as a polycarbonate resin of the present invention includes a step of melt polycondensing a dihydroxy component corresponding to the above-mentioned structural unit and a carbonate diester. The dihydroxy compound in the present invention includes at least one dihydroxy compound represented by formula (I), particularly a dihydroxy compound represented by formula (Ia), (Ia-1) or (Ia-2), each as defined herein. In addition to the compound of formula (I), the dihydroxy compound may include one or more dihydroxy compounds represented by formula (IV), preferably (IV-1) to (IV-6), particularly formula (IV-11) to (IV-20), particularly formula (IV-11), (IV-12), (IV-14), (IV-19 or (IV-20), particularly formula (IV-11), (IV-19) or (IV-20).

[0223] As is clear from the above, a dihydroxy component containing a combination of at least one compound represented by each of the above formulas (I), (Ia), (Ia-1) and (Ia-2) and at least one compound represented by formula (IV), (IV-1), (IV-2), (IV-3), (IV-4), (IV-5), (IV-6), (IV-11), (IV-12), (IV-13), (IV-14), (IV-15), (IV-16), (IV-17), (IV-18), (IV-19) or (IV-20) can be reacted with a carbonate precursor such as a carbonate diester to produce a polycarbonate resin. Specifically, a polycarbonate resin can be produced by reacting compounds represented by formulas (I), (Ia), (Ia-1) and (Ia-2), or a combination of these with at least one compound represented by formulas (IV), (IV-1), (IV-2), (IV-3), (IV-4), (IV-5), (IV-6), (IV-11), (IV-12), (IV-13), (IV-14), (IV-15), (IV-16), (IV-17), (IV-18), (IV-19) or (IV-20), and a carbonate precursor such as a carbonic acid diester, in the presence of a basic compound catalyst, an ester exchange catalyst or a mixed catalyst consisting of both, or in the absence of a catalyst, by a melt polycondensation method.

[0224] Thermoplastic resins (or polymers) other than polycarbonate resins, such as polyester carbonate resins and polyester resins, can be obtained by using, as raw materials (monomers), dihydroxy compounds represented by formulas (I), (Ia), (Ia-1) and (Ia-2), respectively, or combinations of these with at least one compound represented by formulas (IV), (IV-1), (IV-2), (IV-3), (IV-4), (IV-5), (IV-6), (IV-11), (IV-12), (IV-13), (IV-14), (IV-15), (IV-16), (IV-17), (IV-18), (IV-19) or (IV-20).

[0225] As mentioned above, the monomers of formula (I) and the comonomers of formula (IV) used to produce the thermoplastic resin may contain impurities that may arise from the production of those monomers.

[0226] For example, in a compound of formula (Ia-2) where X is C(CH) and R 1 and R 2 are both naphthalen-2-yl, i.e., the compound 2,2'-(propane-2,2-diylbis{[2-(naphthalen-2-yl)-4,1-phenylene]oxy})di(ethan-1-ol) represented by formula (Ia-2.3) may contain, as an impurity, one or more of the following compounds, which are represented by the following scheme:

[0227] [ka]

[0228] [ka]

[0229] In particular, in the compound of formula (Ia-2.3), the total amount of impurities is preferably 1000 ppm or less, more preferably 500 ppm or less, further preferably 200 ppm or less, and particularly preferably 100 ppm or less. Furthermore, the above formula (Ia-2.3) refers to Z 1 or Z 2 The total content of dihydroxy compounds having at least one carbon number different in the group is desirably 50 ppm or less, and more desirably 20 ppm or less.

[0230] For example, R z O-Alk 2 Or O-Alk 2 -[O-Alk 2 -] p The monomers of formulae (IV-2) and (IV-3) are O-Alk 2 -Or O-Alk 2 -[O-Alk2 -] p - Instead of R z are single bonds, or R z may include a dihydroxy compound in which one of the radicals is a single bond.

[0231] In formulas (IV-2) and (IV-3), R z At least one of them is O-Alk 2 -Or O-Alk 2 -[O-Alk 2 -] p The total amount of such dihydroxy compounds different from - in the monomer mainly composed of dihydroxy compounds represented by formulas (IV-2) and (IV-3) is preferably 1000 ppm or less, more preferably 500 ppm or less, further preferably 200 ppm or less, particularly preferably 100 ppm or less. The total content of dihydroxy compounds in which at least one of c and d is different from formulas (IV-2) and (IV-3) is desirably 50 ppm or less, more desirably 20 ppm or less.

[0232] The polycarbonate resin can be obtained by reacting a monomer compound of formula (I) as a dihydroxy component with a carbonate precursor such as a carbonic acid diester, or by reacting a combination of at least one monomer compound of formula (I) as a dihydroxy component, in particular at least one of the monomers (I) described herein as preferred, with one or more monomer compounds of formula (IV), in particular formula (V-11), (V-12), (V-14), (V-19) or (V-20), and in particular formula (IV-11), (IV-19) or (IV-20), with a carbonate precursor such as a carbonic acid diester.

[0233] However, in the polymerization process for producing polycarbonate resins, some compounds of formulas (I) and (IV) have a terminal -Z 1 OH, -Z 2 OH or -R zEither or both of the OH groups may be converted to impurities in which they are replaced with different groups, such as vinyl end groups represented as -OCH=CH2. The amount of such impurities is usually so small that the polymer produced can be used as a polycarbonate resin without purification.

[0234] The thermoplastic resin of the present invention may also contain some amount of impurities, such as excess amounts of the thermoplastic resin composition or part of the polymer backbone of the thermoplastic resin. Examples of such impurities include phenols, unreacted diester carbonates and monomers resulting from the manufacturing process of the thermoplastic resin. The total amount of impurities in the thermoplastic resin may be 5000 ppm or less, or 2000 ppm. The total amount of impurities in the thermoplastic resin is preferably 1000 ppm or less, more preferably 500 ppm or less, even more preferably 200 ppm or less, and particularly preferably 100 ppm or less.

[0235] The total amount of phenol as an impurity in the thermoplastic resin may be 3000 ppm or less, or 2000 ppm or less. The total amount of phenol as an impurity in the thermoplastic resin is preferably 1000 ppm or less, more preferably 800 ppm or less, even more preferably 500 ppm or less, and particularly preferably 300 ppm or less. The total amount of carbonate diesters as impurities in the thermoplastic resin is preferably 1000 ppm or less, more preferably 500 ppm or less, further preferably 100 ppm or less, and particularly preferably 50 ppm or less. The total amount of unreacted monomers as impurities in the thermoplastic resin is preferably 3000 ppm or less, more preferably 2000 ppm or less, even more preferably 1000 ppm or less, and particularly preferably 500 ppm or less. The lower limit for the total amount of these impurities is not critical but could be as low as 0.1 ppm or 1.0 ppm.

[0236] The total amount of residual palladium as an impurity 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 procedures such as treatment with adsorbents, e.g., activated carbon.

[0237] By adjusting the amounts of phenol and dicarbonate, a resin having properties according to the purpose can be obtained. The amounts of phenol, dicarbonate, and monomer can be appropriately adjusted by changing the polycondensation conditions and the operating conditions of the apparatus used in the polymerization. The amounts can also be adjusted by the conditions of extrusion molding after polycondensation.

[0238] The weight average molecular weight (Mw) of the thermoplastic resin of the present invention is preferably 5,000 to 100,000 daltons, more preferably 10,000 to 80,000 daltons, even more preferably 10,000 to 50,000 daltons, and particularly 15,000 to 50,000 daltons, as determined by GPC (gel permeation chromatography). GPC measurements can be calibrated using a polystyrene standard. The Mw of the thermoplastic resin of the present invention thus determined may also be referred to herein as "polystyrene converted Mw", "polystyrene converted Mw" or "Mw determined by GPC against a polystyrene standard". The number average molecular weight (Mn) of the thermoplastic resin of the present invention is preferably 3,000 to 20,000, more preferably 5,000 to 15,000, and even more preferably 7,000 to 14,000. Mn can be determined in the same manner as Mw by GPC measurements calibrated against a polystyrene standard, as described below. The viscosity average molecular weight (Mv) of the thermoplastic resin of the present invention is preferably in the range of 8,000 to 20,000, more preferably 9,000 to 15,000, and even more preferably 10,000 to 14,000.

[0239] The molecular weight distribution (Mw / Mn) of the thermoplastic resin of the present invention is preferably from 1.5 to 9.0, more preferably from 1.8 to 7.0, and further preferably from 2.0 to 4.0.

[0240] If the weight average molecular weight (Mw) of the thermoplastic resin is within the above-mentioned appropriate range, the molded article produced from the thermoplastic resin has sufficient strength. Furthermore, a thermoplastic resin having an appropriate weight average molecular weight (Mw) has an advantage in molding due to its high fluidity.

[0241] In a particular group of embodiments, the thermoplastic resin of the invention comprises at least 0.3% by weight, preferably at least 0.5% by weight, more preferably at least 0.8% by weight, in particular at least 1.0% by weight, of low molecular weight compounds with a molecular weight Mw of less than 1000, based on the total weight of the thermoplastic resin. The upper limit of said content of low molecular weight compounds with a molecular weight Mw of less than 1000 is typically 7.0% by weight, preferably 5.0% by weight, more preferably 3.0% by weight, even more preferably 2.0% by weight, in particular 1.8% by weight, in particular 1.7% by weight. Thus, in this particular group of embodiments, the content of low molecular weight compounds with a molecular weight Mw of less than 1000 in the thermoplastic resin is typically in the range of 0.3 to 7.0% by weight, preferably in the range of 0.5 to 5.0% by weight, more preferably in the range of 0.8 to 3.0% by weight, even more preferably in the range of 1.0 to 2.0% by weight, in particular in the range of 1.0 to 1.8% by weight, in particular in the range of 1.0 to 1.7% by weight, in each case based on the total weight of the thermoplastic resin.

[0242] The thermoplastic resin of the present invention containing the low molecular weight compound with Mw value less than 1000 in the above range forms a molded body with high mechanical strength. Such a thermoplastic resin is less susceptible or hardly susceptible to separation or precipitation of the low molecular weight compound, also known as bleed-out, especially during a molding process such as injection molding. Furthermore, the thermoplastic resin of the present invention containing the low molecular weight compound in the above-defined amount has the advantageous properties of high molding speed and reduced energy requirements for the molding process due to its high plasticity.

[0243] The content of low molecular weight compounds in thermoplastic resin is determined based on the diagram of the above GPC analysis.In particular, the content is calculated as the ratio of the total area of ​​the peaks of low molecular weight compounds obtained by GPC analysis of thermoplastic resin to the total area of ​​all peaks of the diagram.Therefore, the content of low molecular weight compounds in thermoplastic resin (CLWC) is expressed by the following formula:

[0244]

number

[0245] The polycarbonate resins described above have a high refractive index (nD or nd), and are therefore suitable for optical lenses. The refractive index values ​​described here can be measured for a 0.1 mm thick film using an Abbe refractometer according to the method of JIS-K-7142. The refractive index of the polycarbonate resin of the present invention at 23°C and a wavelength of 589 nm is usually 1.640 or more, preferably 1.650 or more, more preferably 1.660 or more, even more preferably 1.670 or more, and particularly 1.680 or more, when it contains the structural unit (2). For example, the refractive index of the copolycarbonate resin of the present invention having the structural unit (2) and the structural unit (V) is preferably 1.660 to 1.720, more preferably 1.670 to 1.720, and particularly 1.680 to 1.720.

[0246] The Abbe number (ν) of the polycarbonate resin is preferably not more than 24, more preferably not more than 20, and further preferably not more than 18. The Abbe number can be calculated from the refractive index at wavelengths of 487 nm, 589 nm, and 656 nm at 23° C. using the following formula. ν=(nD-1) / (nF-nC) nD: Refractive index at a wavelength of 589 nm nC: Refractive index at a wavelength of 656 nm nF: Refractive index at a wavelength of 486 nm

[0247] The preferred glass transition temperature (Tg) of the polycarbonate resin, which is an example of the thermoplastic resin of the present invention, is preferably 90 to 185°C, more preferably 125 to 175°C, and even more preferably 140 to 165°C, in consideration of use in injection molding. From the viewpoint of molding flowability 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 185°C, more preferably 175°C. According to the Tg in the above range, a sufficient use temperature range is given, and the possibility that the melting temperature of the resin becomes high and the resin is likely to decompose or become discolored can be prevented. Furthermore, it enables the production of molded products with strict surface accuracy.

[0248] In a preferred group (10) of embodiments, the absolute value of the orientation birefringence of the thermoplastic resin is preferably 0 to 1 × 10 -2 More preferably, it is in the range of 0 to 5×10 -3 More preferably, the range is 0 to 2×10 -3 In particular, the range is 0 to 1 × 10 -3 In particular, the range is 0 to 0.4 × 10 -3 The range is.

[0249] The optical molded article such as an optical member obtained by using the polycarbonate resin of the present invention preferably has a total light transmittance of 85% or more, more preferably 87% or more, and particularly preferably 88% or more. If the total light transmittance is 85% or more, it is comparable to that of bisphenol A type polycarbonate resin.

[0250] The thermoplastic resin of the present invention has high moisture resistance and heat resistance. The moisture and heat resistance can be evaluated by performing a "PCT test" (pressure cooker test) on a molded article such as an optical member obtained using the thermoplastic resin, and measuring the total light transmittance of the molded article after the PCT test. In the PCT test, first, an injection molded article having a diameter of 50 mm and a thickness of 3 mm is held for 20 hours under the conditions of 120°C, 0.2 MPa, 100% RH, and 20 hours by PC-305-S III manufactured by Hirayama Seisakusho. Then, the sample of the injection molded article is removed from the device, and the total light transmittance is measured by the method of JIS-K-7361-1 using a spectrophotometer SE2000 manufactured by Nippon Denshoku Kogyo Co., Ltd.

[0251] The thermoplastic resin of the present invention has a total light transmittance after PCT test of 60% or more, preferably 70% or more, more preferably 75% or more, even more preferably 80% or more, and particularly preferably 85% or more. If the total light transmittance is 60% or more, it can be said to have higher moist heat resistance than conventional thermoplastic resins.

[0252] The b value, which indicates the hue of the thermoplastic resin of the present invention, is preferably not more than 5. The smaller the b value, the weaker the yellowness, and the better the hue.

[0253] According to the present invention, the diol component used to prepare the polycarbonate or polyester may further comprise one or more diol monomers different from the monomeric compound of formula (I), such as one or more monomers of formula (IV).

[0254] Suitable diol monomers other than the monomeric compounds of formula (I) are customarily used in the preparation of polycarbonates, for example: aliphatic diols, such as ethylene glycol, propanediol, butanediol, pentanediol and hexanediol; alicyclic diols, such as tricyclo[5.2.1.02,6]decanedimethanol, cyclohexane-1,4-dimethanol, decalin-2,6-dimethanol, norbornane dimethanol, pentacyclopentadecanedimethanol, cyclopentane-1,3-dimethanol, spiroglycol, 1,4:3,6-dianhydro-D-sorbitol, 1,4:3,6-dianhydro-D-mannitol and 1,4:3,6-dianhydro-L-iditol, may also be mentioned as examples of diols; and aromatic diols, in particular aromatic diols of the formula (IV), such as, for example, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)ketone, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-t-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-methylethyl 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis[4-(2-hydroxyethoxy)-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-hydroxy-2-naphthyl)fluorene, 9,9-bis(6-(2-hydroxyethyl)-2-naphthyl)fluorene, 10,10-bis(4-hydroxyphenyl)anthracen-9-one, 10,10-bis(4-(2-hydroxyethyl)phenyl)anthracen-9-one and 2,2'-[1,1'-binaphthalene-2,2'-diylbis(oxy)]diethanol, also known as 2,2'-Bis(2-hydroxyethoxy)-1,1'-binaphthyl or 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene (BNE).

[0255] The diol component preferably contains at least one monomer of formula (IV) in addition to the monomer of formula (I). In particular, the total amount of the monomers of formula (I) and formula (IV) contributes to the diol component by being at least 90% by weight based on the total weight of the diol component, or at least 90 mol% based on the total molar amount of the diol monomers of the diol component. In particular, the diol component contains at least one monomer selected from the monomers of formulas (IV-11) to (IV-20) in addition to the monomer of formula (I). Furthermore, the diol component contains at least one monomer selected from the monomers of formulas (IV-11), (IV-12), (IV-14), (IV-19) and (IV-20) in addition to the monomer of formula (I). In particular, the diol component comprises, in addition to the monomer of formula (I), at least one monomer selected from 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene and 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene, and combinations thereof.

[0256] Often the relative amount of monomeric compounds of formula (I) will be at least 1% by weight, preferably at least 2% by weight or at least 5% by weight, in particular at least 8% by weight or at least 10% by weight, and in particular at least 12% by weight or at least 15% by weight, preferably in the range 1-90% by weight or 5-90% by weight, in particular in the range 2-80% by weight, 5-80% by weight, 8-80% by weight or 10-80% by weight, in particular in the range 5-70% by weight, 8-70% by weight, 10-70% by weight or 15-70% by weight, but may be as high as up to 100% by weight, based on the total weight of the diol component.

[0257] Often the relative molar amount of monomeric compounds of formula (I) will be at least 1 mol%, preferably at least 2 mol% or at least 5 mol%, in particular at least 8 mol% or at least 10 mol%, and in particular at least 12 mol% or at least 15 mol%, preferably in the range 1-80 mol% or 2-80 mol% or 5-80 mol% or 8-80 mol%, in particular in the range 2-70 mol% or 5-70 mol% or 8-70 mol% or 10-70 mol%, in particular in the range 5-60 mol% or 8-60 mol% or 10-60 mol% or 12-60 mol% or 15-60 mol%, but may be as high as up to 100 mol% based on the total molar amount of the diol components.

[0258] As a result, the relative molar amount of monomeric compounds of formula (IV), based on the total molar amount of diol components in the diol component, does not exceed 99 mol% or 98 mol% or 95 mol%, in particular does not exceed 92 mol% or 90 mol%, and in particular does not exceed 88 mol% or 85 mol%, preferably in the range of 20-99 mol% or 20-98 mol% or 20-95 mol% or 20-92 mol%, in particular in the range of 30-98 mol% or 30-95 mol% or 30-92 mol% or 30-90 mol%, in particular in the range of 40-95 mol% or 40-92 mol% or 40-90 mol% or 40-88 mol% or 40-85 mol%, but may be as high as up to 99.9 mol%.

[0259] Frequently, the total molar amount of monomers of formula (I) and monomers of formula (IV) is at least 80 mol %, in particular at least 90 mol %, and in particular at least 95 mol % or even up to 100 mol %, based on the total molar amount of diol monomers of the diol component.

[0260] Examples of further preferred aromatic dihydroxy compounds that may be used in addition to the monomer of formula (I) and, optionally, the monomer 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, and bisphenol Z.

[0261] To adjust the molecular weight and melt viscosity, the monomers forming the thermoplastic polymer may contain a monofunctional compound (monofunctional alcohol in the case of polycarbonate, monofunctional alcohol or monofunctional carboxylic acid in the case of polyester). Suitable monoalcohols 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 contain a polyfunctional compound (polyfunctional alcohol having three or more hydroxyl groups in the case of polycarbonate, polyfunctional alcohol having three or more hydroxyl groups or polyfunctional carboxylic acid having three or more carboxyl groups in the case of polyester). Suitable polyfunctional alcohols include, for example, glycerin, 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. The total amount of these compounds is often not more than 10 mol% based on the molar amount of the diol component.

[0262] Suitable carbonate-forming monomers are those conventionally used as carbonate-forming monomers in the production of polycarbonates, including, but not limited to, phosgene, diphosgene and diester carbonates, such as diethyl carbonate, diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate and dinaphthyl carbonate. Among these, diphenyl carbonate is particularly preferred. The carbonate-forming monomer is often used in a ratio of 0.97 to 1.20 mol, more preferably 0.98 to 1.10 mol, per mol of the total of dihydroxy compounds.

[0263] Suitable dicarboxylic acids include, but are not limited to, the following: - aliphatic dicarboxylic acids, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid; alicyclic dicarboxylic acids, such as tricyclo[5.2.1.02,6]decanedicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, decalin-2,6-dicarboxylic acid and norbornanedicarboxylic acid; and aromatic dicarboxylic acids, such as benzenedicarboxylic acids, in particular phthalic acid, isophthalic acid, 2-methylterephthalic acid or terephthalic acid, and naphthalene dicarboxylic acids, in particular naphthalene-1,3-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-1,6-dicarboxylic acid, naphthalene-1,7-dicarboxylic acid, naphthalene-2,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, 2-[9-(carboxymethyl)fluoren-9-yl]acetic acid (formula DC1), 2-[9-(carboxymethyl)fluoren-9-yl]propionic acid (formula DC2), 2,2'-bis(carboxymethyloxy)-1,1'-binaphthyl (formula DC3) and naphthalene-2,7-dicarboxylic acid.

[0264] [ka]

[0265] Suitable ester forming derivatives of dicarboxylic acids include, but are not limited to, dialkyl esters, diphenyl esters, and ditolyl esters.

[0266] In polyesters, the ester-forming monomers are often used in a ratio ranging from 0.97 to 1.20 mol, more preferably from 0.98 to 1.10 mol, per mol of the total of the dihydroxy compounds.

[0267] The polyestercarbonates of the present invention can be prepared by reacting a diol component comprising a monomer of formula (I) and, optionally, a diol monomer, such as a monomer of formula (IV), with carbonate-forming monomers, similar to the preparation of known polycarbonates, for example, as described in U.S. Pat. No. 9,360,593, U.S. Patent Application Publication No. 2016 / 0319069, and U.S. Patent Application Publication No. 2017 / 0276837, which are incorporated herein by reference in their entirety.

[0268] The polyesters of the present invention can be prepared by reacting a diol component comprising a monomer of formula (I) and, optionally, a diol monomer, such as a monomer of formula (IV), with a dicarboxylic acid or an ester-forming derivative thereof, similar to the preparation of known polyesters, for example, as described in U.S. Patent Application Publication No. 2017 / 044311, which is incorporated by reference in its entirety, and the references cited therein.

[0269] The polyestercarbonates of the present invention can be prepared by reacting a diol component comprising a monomer of formula (I) and, optionally, a diol monomer such as a monomer of formula (IV) with a carbonate-forming monomer and a dicarboxylic acid or an ester-forming derivative thereof in a manner similar to that used for preparing polyestercarbonates as known in the art.

[0270] Polycarbonates, polyesters and polyestercarbonates are usually produced by reacting a monomer of a diol component with a carbonate-forming monomer and / or an ester-forming monomer, such as a dicarboxylic acid or an ester-forming derivative thereof, in the presence of an esterification catalyst, and particularly, when a carbonate-forming monomer or an ester-forming derivative of a polycarboxylic acid is used, by reacting them in the presence of an ester exchange catalyst.

[0271] Suitable transesterification catalysts are specifically, but not limited to, basic compounds including alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, etc. Similarly, suitable transesterification catalysts are specifically, but not limited to, acidic compounds including Lewis acid compounds of polyvalent metals including compounds of zinc, tin, titanium, zirconium, lead, etc.

[0272] Suitable examples of the alkali metal compound include alkali metal salts of organic acids such as acetic acid, stearic acid, benzoic acid, and phenylphosphoric acid, alkali metal phenolates, alkali metal oxides, alkali metal carbonates, alkali metal borohydrides, alkali metal hydrogencarbonates, alkali metal phosphates, alkali metal hydrogenphosphates, alkali metal hydroxides, alkali metal hydrides, and alkali metal alkoxides. 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 phenylborohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenylphosphate, the disodium, dipotassium, or dicesium salt of bisphenol A, the sodium, potassium, cesium, or lithium salt of phenol, and the like.

[0273] Examples of the alkaline earth metal compound include alkaline earth metal salts of organic acids such as acetic acid, stearic acid, benzoic acid, and phenylphosphoric acid, alkaline earth metal phenolates, alkaline earth metal oxides, alkaline earth metal carbonates, alkaline earth metal borohydrides, alkaline earth metal hydrogen carbonates, alkaline earth metal hydroxides, alkaline earth metal hydrides, and alkaline earth metal alkoxides. Specific examples thereof include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium hydrogen carbonate, calcium hydrogen carbonate, strontium hydrogen carbonate, barium hydrogen carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, and magnesium phenylphosphate.

[0274] Examples of the nitrogen-containing compound include quaternary ammonium hydroxides and their salts, amines, etc. Specifically, quaternary ammonium hydroxides having an alkyl group, an aryl group, etc., such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide; tertiary amines such as triethylamine, dimethylbenzylamine, and triphenylamine; secondary amines such as diethylamine and dibutylamine; primary amines such as propylamine and butylamine; imidazoles such as 2-methylimidazole, 2-phenylimidazole, and benzimidazole; or bases or basic salts such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, and tetraphenylammonium tetraphenylborate, etc., are used.

[0275] Suitable examples of the transesterification catalyst include salts of polyvalent metals such as zinc, tin, titanium, zirconium, and lead, and in particular, chlorides, alkoxides, alkanoates, benzoates, acetylacetonates, and the like. They may be used independently 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 dimethoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead(II) acetate, lead(IV) acetate, and the like.

[0276] These transesterification catalysts are used in an amount of 10 -9 ~10 -3 In terms of mole ratio, preferably 10 -7 ~10 -4 It is often used as a molar ratio.

[0277] Polycarbonates, polyesters and polyestercarbonates are often produced by melt polycondensation processes, in which the monomers are reacted without the presence of additional inert solvents, during which the by-products resulting from the transesterification reaction are removed by heating the reaction mixture at atmospheric pressure or under reduced pressure.

[0278] The melt polycondensation reaction preferably involves charging the monomers and catalyst into a reaction vessel and subjecting the reaction mixture to conditions under which the monomers react to produce by-products. It has been found to be advantageous for the by-product residues to remain in the melt polycondensation reaction system for some time. However, in order to drive the melt polycondensation reaction towards the product, it is preferred to remove at least a portion of the by-products produced during the melt polycondensation reaction or, preferably, at the end of the melt polycondensation reaction. To allow the by-products in the reaction mixture, the pressure can be controlled by blocking, depressurizing or pressurizing the reactor. The reaction time for this step is from 20 to 240 minutes, preferably from 40 to 180 minutes, and particularly preferably from 60 to 150 minutes. In this case, if the by-products are distilled off immediately after production, the final thermoplastic resin will have a low content of high molecular weight resin molecules. However, if the by-products are allowed to remain in the reaction vessel for a certain period of time, the final thermoplastic resin will have a high content of high molecular weight resin molecules.

[0279] The melt polycondensation reaction may be carried out continuously or batchwise. The reaction apparatus used for the reaction may be a vertical type equipped with an anchor-type impeller, a Maxblend (registered trademark) impeller, a helical ribbon-type impeller, or the like, a horizontal type equipped with a paddle impeller, a lattice impeller, a spectacle impeller, or the like, or an extruder type equipped with a screw. In addition, it is preferable to use a reaction apparatus that is an appropriate combination of these reaction apparatuses, taking into consideration the viscosity of the polymer.

[0280] In the method for producing a thermoplastic resin used in the present invention, such as a polycarbonate resin, the catalyst may be removed or deactivated after the polymerization reaction is completed in order to maintain thermal stability and hydrolytic stability. A method of deactivating the catalyst by adding a known acidic substance can be preferably carried out. Specific examples of the acidic substance include esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid, aromatic sulfonic acid esters such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate, phosphoric acids such as phosphorous acid, phosphoric acid, and phosphonic acid, phosphoric acid esters such as triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, di-n-butyl phosphite, di-n-hexyl phosphite, dioctyl phosphite, and monooctyl phosphite, and esters such as triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, dibutyl phosphate, and dioctyl phosphate. Phosphates such as phosphate esters, monooctyl phosphate, etc.; phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid, dibutylphosphonic acid, etc.; phosphonic acid esters such as diethyl phenylphosphonate, etc.; phosphines such as triphenylphosphine, bis(diphenylphosphino)ethane, etc.; boric acid, phenylboric acid, etc.; aromatic sulfonates such as tetrabutylphosphonium dodecylbenzenesulfonate, etc.; organic halides such as stearic acid chloride, benzoyl chloride, p-toluenesulfonic acid chloride, etc.; alkyl sulfuric acid such as dimethyl sulfate, etc.; organic halides such as benzyl chloride, etc. are preferably used. These deactivators are often used in an amount of 0.01 to 50 times by mole, preferably 0.3 to 20 times by mole, based on the amount of the catalyst. After the catalyst deactivation, a step of volatilizing and removing low boiling point compounds in the polymer at a pressure of 0.1 to 1 mmHg and a temperature of 200 to 350°C may be provided. For this step, a horizontal apparatus equipped with stirring blades with excellent surface renewal capability, such as paddle blades, lattice blades, or spectacle blades, or a thin film evaporator is preferably used.

[0281] In thermoplastic resins such as polycarbonate resins, it is desirable to minimize the content of foreign matter, and therefore filtration of the melt and filtration of solid matter from the melt are preferably carried out. The mesh of the filter is preferably 5 μm or less, more preferably 1 μm or less. Furthermore, filtration of the produced polymer with a polymer filter is preferably carried out. The mesh of the polymer filter is preferably 100 μm or less, more preferably 30 μm or less. Furthermore, the process of collecting resin pellets must be carried out in a low-dust environment, preferably class 6 or less, more preferably class 5 or less.

[0282] The thermoplastic resins may be molded by any conventional molding procedure for producing optical components. Suitable molding procedures include, but are not limited to, injection molding, compression molding, casting, rolling, extrusion, stretching, and the like.

[0283] While the thermoplastic resin of the present invention can be molded as described above, it is also possible to mold a resin composition that further comprises at least one thermoplastic resin of the present invention and at least one additive and / or further thermoplastic resin. Suitable additives include antioxidants, processing stabilizers, light stabilizers, polymerized metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, antibacterial agents, mold release agents, UV absorbers, plasticizers, compatibilizers, etc. Suitable further resins, i.e., other polycarbonate resins, polyester carbonate resins, polyester resins, polyamides, polyacetals, etc., include those that do not contain the repeating unit of formula (I).

[0284] Examples of antioxidants include triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)benzofuran-2(3H)-one ... ,7-di-tert-butyl-3-(1,2-dimethylphenyl)benzofuran-2(3H)-one, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate and 3,9-bis{1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4,8,10-tetraoxaspiro(5,5)undecane. Among these, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)benzofuran-2(3H)-one, and 5,7-di-tert-butyl-3-(1,2-dimethylphenyl)benzofuran-2(3H)-one are more preferred. The content of the antioxidant in the thermoplastic resin is preferably 0.001 to 0.3 part by weight based on 100 parts by weight of the thermoplastic resin.

[0285] Examples of the processing stabilizer include, but are not limited to, phosphorus-based processing stabilizers, sulfur-based processing stabilizers, etc. Phosphorus-based processing stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specifically, triphenyl phosphite, tris(nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2,6-di-tert-butylphenyl)phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butyl phenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate, tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-t-butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,4-di-t-butylphenyl)-3,3'-biphenylene diphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, and bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite. The content of the phosphorus-based process stabilizer in the thermoplastic resin composition is preferably 0.001 to 0.2 parts by weight based on 100 parts by weight of the thermoplastic resin.

[0286] 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.

[0287] As an example of the release agent, it is preferable that 90% by weight or more of the release agent is composed of an ester of alcohol and a fatty acid. Specific examples of the ester of alcohol and a fatty acid include an ester of a monohydric alcohol and a fatty acid, and a partial ester or a full ester of a polyhydric alcohol and a fatty acid. As the ester of alcohol and a fatty acid, an ester of a monohydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms is preferable. In addition, as a partial ester or a full ester of a polyhydric alcohol and a fatty acid, a partial ester or a full ester of a polyhydric alcohol having 2 to 25 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms is preferable. 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. Examples of the partial or full ester of polyhydric alcohol and fatty acid include stearic acid monoglyceride, stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbitate, behenic acid monoglyceride, capric acid monoglyceride, lauric acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, and dipentaerythritol hexastearate. The content of the release agent in these resin compositions is preferably in the range of 0.005 to 2.0 parts by weight, more preferably in the range of 0.01 to 0.6 parts by weight, and even more preferably in the range of 0.02 to 0.5 parts by weight, relative to 100 parts by weight of the thermoplastic resin.

[0288] Examples of the ultraviolet absorbent include at least one ultraviolet absorbent selected from the group consisting of benzotriazole ultraviolet absorbents, benzophenone ultraviolet absorbents, triazine ultraviolet absorbents, cyclic iminoester ultraviolet absorbents, and cyanoacrylate ultraviolet absorbents. That is, the ultraviolet absorbents listed below may be used alone or in combination of two or more.

[0289] Examples of benzotriazole-based ultraviolet absorbers include 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2N-benzotriazol-2-yl)phenol], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 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-octoxyphenyl)benzotriazole, 2,2'-methylenebis(4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis(1,3-benzoxazin-4-one), 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole, and the like.

[0290] Examples of benzophenone-based ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 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-sodium sulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

[0291] Examples of triazine-based 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, and the like.

[0292] Examples of cyclic imino ester-based ultraviolet absorbers include 2,2'-bis(3,1-benzoxazine-4-one), 2,2'-p-phenylenebis(3,1-benzoxazine-4-one), 2,2'-m-phenylenebis(3,1-benzoxazine-4-one), 2,2'-(4,4'-diphenylene)bis(3,1-benzoxazine-4-one), 2,2'-(2,6-naphthalene)bis(3,1-benzoxazine-4-one), oxazin-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), and 2,2'-(2-chloro-p-phenylene)bis(3,1-benzoxazin-4-one).

[0293] Examples of cyanoacrylate ultraviolet absorbers include 1,3-bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis(((2-cyano-3,3-diphenylacryloyl)oxy)methyl)propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene.

[0294] The content of the ultraviolet absorber in the resin composition is preferably 0.01 to 3.0 parts by weight, more preferably 0.02 to 1.0 parts by weight, and further preferably 0.05 to 0.8 parts by weight, based on 100 parts by weight of the thermoplastic resin. If the content is within this range, it is possible to impart sufficient weather resistance to the thermoplastic resin depending on the application.

[0295] As mentioned above, the thermoplastic polymer resin, especially the polycarbonate resin comprising the repeating units of each of the formulae (II), (IIa), (IIa-1) and (IIa-2) described herein, provides the thermoplastic resin with high transparency and high refractive index. Therefore, it is suitable for manufacturing optical elements that require high transparency and high refractive index. More specifically, the thermoplastic polycarbonate having the structural units of each of the formulae (II), (IIa), (IIa-1) and (IIa-2) is characterized by having a high refractive index, preferably at least 1.660, more preferably at least 1.680, especially at least 1.690.

[0296] The contribution of each monomer of formula (I), (Ia), (Ia-1) and (Ia-2) to the refractive index of a thermoplastic resin, particularly a polycarbonate resin, depends on the refractive index of said monomer and the relative amount of said monomer in the thermoplastic resin. In general, the higher the refractive index of the monomer contained in the thermoplastic resin, the higher the refractive index of the resulting thermoplastic resin. Alternatively, the refractive index of a thermoplastic resin containing a structural unit of formula (II) can be calculated from the refractive index of the monomer used to prepare the thermoplastic resin (either from the refractive index of the monomer or from scratch, for example, using computer software ACD / ChemSketch 2012 (Advanced Chemistry Development, Inc.)).

[0297] In the case of a thermoplastic copolymer resin, the refractive index of the thermoplastic resin, particularly a polycarbonate resin, can be calculated from the refractive index of the homopolymer of each monomer forming the copolymer resin using the so-called "Fox formula" below. 1 / n D =x1 / n D1 +x2 / n D2 +....x n / n Dn , In the formula, n D are the refractive indices of the copolymer, and x1, x2,...x n are the mass fractions of monomers 1, 2, …, n in the copolymer, and n D1 , n D2 , n Dn is the refractive index of a homopolymer synthesized from only one type of monomer at a time, 1, 2, …, n. In the case of polycarbonate, x1, x2, …, x n is the mass fraction of OH monomers 1, 2, …n based on the total amount of OH monomers. It is clear that a higher refractive index of the homopolymer leads to a higher refractive index of the copolymer.

[0298] The refractive index of a thermoplastic resin can be measured directly or indirectly. In a direct measurement, the refractive index of the thermoplastic resin, n Dis measured at a wavelength of 589 nm, using an Abbe refractometer, applying a 0.1 mm film of the thermoplastic resin, according to the protocol of JIS-K-7142. In the case of the refractive index of the homopolycarbonate of the compound of formula (I), the refractive index can also be measured indirectly. For this, copolycarbonates of each monomer of formula (I) with 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene and diphenyl carbonate are prepared according to the protocol of Example 1 in column 48 of U.S. Pat. No. 9,360,593, and then the refractive index n of the copolycarbonate is measured. D is measured at a wavelength of 589 nm using an Abbe refractometer according to the protocol of JIS-K-7142, applying a 0.1 mm film of the copolycarbonate. The refractive index n D From the above, the refractive index of the homopolycarbonate of each monomer is calculated by the Fox formula and the refractive index of the known 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (n D (589 nm) = 1.639) can be applied to the calculation.

[0299] As mentioned above, some R 1 , R 2 , R 3 , R 4 and Ar 1 Compounds of formula (I) that do not have chromophoric groups such as groups can also be obtained in a purity that gives a low yellowness index YI (measured according to ASTM E313) which can be important for use in the manufacture of optical resins.

[0300] More particularly, the Yellowness Index YI of the compounds of formula (I), measured according to ASTM E313, preferably does not exceed 200, more preferably 100, even more preferably 50, in particular 20 or 10.

[0301] The thermoplastic resin of the present invention has a high refractive index and a low Abbe number. The thermoplastic resin of the present invention can be advantageously used to manufacture transparent conductive substrates and the like used in liquid crystal displays, organic EL displays, solar cells, and the like. Furthermore, the thermoplastic resin of the present invention can be advantageously used as an optical element suitable for structural or functional material applications of optical components such as optical disks, liquid crystal panels, optical cards, optical sheets, optical fibers, connectors, evaporated plastic reflectors, and displays.

[0302] Therefore, the thermoplastic resin of the present invention can be used to manufacture molded articles such as optical elements. Optical elements include optical lenses and optical films. Specific examples of optical elements include lenses, films, mirrors, filters, prisms, etc. These optical elements are molded by any manufacturing method such as injection molding, compression molding, injection compression molding, extrusion molding, solution casting, etc.

[0303] Due to its excellent moldability and heat resistance, the thermoplastic resin of the present invention is particularly suitable for the production of optical lenses that require injection molding. During molding, the thermoplastic resin such as the polycarbonate resin of the present invention can be mixed with other thermoplastic resins such as other polycarbonate resins, polyester carbonate resins, polyester resins, etc.

[0304] Furthermore, the thermoplastic resin of the present invention may be mixed with additives for forming optical elements. The additives for forming optical elements may be the above-mentioned ones. The additives may include antioxidants, processing stabilizers, light stabilizers, polymerized metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, antibacterial agents, release agents, ultraviolet absorbers, plasticizers, compatibilizers, etc.

[0305] As is clear from the above description, another aspect of the present invention relates to an optical element manufactured from the above thermoplastic resin comprising a structural unit of formula (II) and optionally a structural unit of formula (V). With regard to the preferred meanings and preferred embodiments of the structural units of formula (II) and formula (V), reference is made to the above description.

[0306] Optical elements produced from optical resins containing repeating units of formula (II) and optionally repeating units of formula (V) as defined herein are usually optical lenses, such as automobile headlamp lenses, Fresnel lenses, fθ lenses for laser printers, camera lenses, lenses for glasses and projection lenses for rear projection televisions, pickup lenses for CD-ROMs (optical disks), as well as optical disks; optical members for image display media; optical films; film substrates; optical filters; prisms, or optical molded products such as liquid crystal panels, optical cards, optical sheets, optical fibers, optical connectors, and evaporated plastic reflectors. Particularly preferred here are optical lenses and optical films. Optical resins containing repeating units of formula (II) and optionally repeating units of formula (V) are also useful for producing transparent conductive substrates usable in optical elements suitable as structural or functional members of transparent conductive substrates for liquid crystal displays, organic EL displays, solar cells, and the like.

[0307] The optical lens manufactured using the thermoplastic resin of the present invention has a high refractive index, a low Abbe number, low birefringence, and high resistance to moist heat. Therefore, the optical lens can be used in fields where expensive high refractive index glass lenses have been used in the past, such as telescopes, binoculars, and television projectors, and is extremely useful. The optical lens is preferably used in the form of an aspherical lens as necessary. Since an aspherical lens can substantially reduce spherical aberration to zero with a single lens, it is not necessary to remove spherical aberration by combining multiple spherical lenses, and it is possible to reduce weight and production costs. Therefore, the aspherical lens is particularly useful as a camera lens among optical lenses. According to the present invention, a high refractive index, low birefringence aspherical lens, which is technically difficult to process with a glass lens, can be obtained more easily.

[0308] The optical lenses of the present invention can be produced, for example, by injection molding, compression molding, injection compression molding, or co-molding of a resin of repeating units of formula (II) and, optionally, repeating units of formula (V) as defined herein.

[0309] The optical lens of the present invention is characterized by small optical distortion. Conventional optical lenses containing optical resins have large optical distortion. Although it is not impossible to reduce the value of optical distortion by changing molding conditions, the condition range is very narrow, and molding is very difficult. The resin having the repeating unit of formula (II) defined in this specification and the repeating unit of formula (V) optionally has very small optical distortion caused by the orientation of the resin, and small molding distortion, so that excellent optical members can be obtained without strictly setting molding conditions.

[0310] To produce the optical lens of the present invention by injection molding, it is preferable to carry out molding at a cylinder temperature of 260°C to 320°C and a mold temperature of 100°C to 140°C.

[0311] The optical lens of the present invention can be advantageously used as an aspherical lens as necessary. Since a single aspherical lens can substantially eliminate spherical aberration, it is not necessary to combine spherical lenses to eliminate spherical aberration, which can reduce weight and manufacturing costs. Therefore, among optical lenses, aspherical lenses are particularly useful as camera lenses.

[0312] Resins having the repeating unit of formula (II) and optionally the repeating unit of formula (V) as defined herein have good moldability and are particularly useful as materials for thin, small, and complex-shaped optical lenses. The lens size is 0.05-3.0 mm, preferably 0.05-2.0 mm, and more preferably 0.1-2.0 mm, in terms of thickness at the center of the lens. The lens diameter is 1.0-20.0 mm, preferably 1.0-10.0 mm, and more preferably 3.0-10.0 mm. Preferably, the lens is a meniscus lens with one surface convex and the other surface concave.

[0313] The surface of the optical lens of the present invention may have a coating layer such as an anti-reflection layer or a hard coat layer, if necessary. The anti-reflection layer may be a single layer or a multilayer, and may be composed of an organic material or an inorganic material, but is preferably composed of an inorganic material. Examples of inorganic materials include oxides and fluorides such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, magnesium oxide, and magnesium fluoride.

[0314] The optical lens of the present invention can be formed by any method such as metal forming, cutting, polishing, laser processing, electric discharge processing, deburring, etc. Metal forming is preferred.

[0315] The optical film produced using the thermoplastic resin of the present invention has excellent transparency and heat resistance, and is therefore suitable for use as a film for liquid crystal substrates, optical memory cards, etc. It goes without saying that the molding environment must be a low-dust environment in order to prevent foreign matter from being mixed into the optical film as much as possible. The dust environment is preferably class 6 or less, more preferably class 5 or less.

[0316] The following examples serve to further illustrate the invention. EXAMPLES

[0317] 1. Abbreviation: mp: melting point RT: room temperature THF: tetrahydrofuran TLC: Thin Layer Chromatography

[0318] 2. Preparation of Monomers of Formula (I) 2.1 Analysis for monomers of formula (I): 1 H-NMR spectra were recorded on an 80 MHz NMR spectrometer (Magritek Spinsolve 80) at 23 °C. The solvent was CDCl3 unless otherwise stated.

[0319] IR spectra were recorded by ATR FT-IR using a Shimadzu FTIR-8400S spectrometer (scan number: 45, resolution: 4 cm -1 ;Apodization:Happ-Genzel).

[0320] DSC (differential scanning calorimetry) measurements were performed using a Linseis Chip-DSC 10.

[0321] The melting points of the compounds were measured using a Büchi Melting Point B-545.

[0322] UPLC (ultra-performance liquid chromatography) analysis was performed using the following system and conditions: Waters Acquity UPLC H-Class system (column: Acquity UPLC BEH C18, 1.7 μm, 2.1 × 100 mm); column temperature: 25 °C; gradient: acetonitrile / water: acetonitrile 80% at 0 min, 100% at 4.0 min, 100% at 6.0 min, 80% at 6.1 min, 80% at 8.0 min; injection volume: 2.0 μl; runtime: 8 min; detection at 210 nm.

[0323] The yellowness index YI of the compound of formula (I) can be measured by a method similar to ASTM E313 using the following protocol: 1 g of the compound of formula (I) is dissolved in 19 g of a solvent, such as methanol or methylene chloride. The solution is transferred to a 50 mm cuvette and the transmittance is measured in the range of 300-800 nm using a Shimadzu UV-Visible Spectrophotometer UV-1900. The solvent itself, such as methanol, is used as a reference. The yellowness index can be calculated from the spectrum using the software "RCA-software UV2DAT" according to ASTM E308 (Standard Method for Calculating the Color of Objects Using the CIE System) and ASTM E313 (Standard Method for Calculating Yellowness and Whiteness from Instrumentally Measured Color Coordinates).

[0324] 2.2 Preparation example: Example 1: 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-diphenyl-phenyl]-1-methyl-ethyl]-2,6-diphenyl-phenoxy]ethanol (X=C(CH 3) 2 、R 1 =R 2 =R 3 =R 4 = Phenyl and Z 1 =Z 2 = 2-hydroxyethyl; compound 33 of Table A) of formula (Ia-1)

[0325] [ka] To 2-[2,6-dibromo-4-[1-[3,5-dibromo-4-(2-hydroxyethoxy)phenyl]-1-methylethyl]phenoxy]ethanol (135.91 g; 200 mmol; purity=93%) was added phenylboronic acid (102.42 g; 840 mmol; 4.2 equiv.), tris(o-tolyl)phosphane (243.5 mg; 0.8 mmol) and anisole (800 mL). To this mixture was added K3PO4 (178.3 g) dissolved in water (396 g). The mixture was stirred at 60-70 °C and purged with nitrogen until two clear phases formed. To this mixture was added Pd(OCOCH3)2 (45 mg; 0.2 mmol) under argon and the mixture was stirred under reflux until TLC showed complete conversion. The reaction mixture was then cooled to 70° C. and the organic layer was separated at this temperature and then washed with an aqueous solution of NaOH (10% by weight), an aqueous solution of HCl (2M) and brine. The organic layer was treated with activated carbon (Norit® DX Ultra, Cabot Corp.) and the mixture was stirred for 2.5 hours. The mixture was then filtered through Celite and the solution was concentrated under reduced pressure. The resulting mixture was cooled to room temperature and stirred overnight. The formed crystals were collected by filtration to give the crude title compound as an off-white solid (97.8 g; 79% yield). The crude material was recrystallized from an acetone or ethanol mixture to give the title compound as a white solid with a chemical purity of >99% and a yellowness index (APHA5) of 1.3. mp(DSC): 108.3℃; 1H NMR (80 MHz, CDCl3): δ = 7.93 - 7.31 (m, 24H), 3.44 (m, 8H), 1.72 (s, 6H), 1.2 (s, 2H, OH) ppm. IR (ATR): 725.3 (84.84); 746.5 (60.86); 842.9 (88.30); 883.4 (72.19); 1008.8 (67.89); 1022.3 (74.21); 1072.5 (80.22); 1182.4 1211.3 (73.28); 1361.8 (85.89); 1421.6 (72.15); 1467.9 (75.76); 1597.1 (90.24); 2357.1 (92.49); 2883.7 (89.41); 2935.8 (89.02); 2958.9 (86.06); 3030.3 (90.52); 3057.3 (90.63); 3184.6 (91.52); 3352.4 (90.54) cm -1 .

[0326] Example 2: 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-di(naphthalen-1-yl)phenyl]-1-methyl-ethyl]-2,6-di(naphthalen-1-yl)phenoxy]ethanol (X=C(CH 3 ) 2 、R 1 =R 2 =R 3 =R 4 = naphthalene-1-yl and Z 1 =Z 2 = 2-hydroxyethyl; compound 34 of Table A) of formula (Ia-1)

[0327] [ka] 2-[2,6-dibromo-4-[1-[3,5-dibromo-4-(2-hydroxyethoxy)phenyl]-1-methyl -To [ethyl]phenoxy]ethanol (90.4 g; 133 mmol; purity = 93%) was added naphthalen-1-ylboronic acid (114.4 g; 665 mmol; 5 equiv.) and tris(o-tolyl)phosphane (1.62 g; 5.32 mmol). To this mixture was added 148.2 g of K3PO4 (148.2 g) dissolved in anisole (800 mL) and water (331 g). The mixture was stirred at 60-70 °C until two clear phases were formed and purged with nitrogen. To this mixture was added Pd(OCOCH3)2 (299 mg; 1.33 mmol) under argon and the mixture was stirred under reflux until TLC showed complete conversion. The reaction mixture was then cooled to 70 °C and the organic layer was separated at this temperature and subsequently washed with an aqueous solution of NaOH (10 wt %), an aqueous solution of HCl (2 M) and brine. The organic layer was treated with activated charcoal (Norit® DX Ultra, Cabot Corp.) and the mixture was stirred for 2.5 h. The mixture was then filtered through Celite and the solution was concentrated under reduced pressure. The resulting mixture was cooled to room temperature and stirred overnight. The formed crystals were collected by filtration to give the crude title compound as an off-white solid with a chemical purity of 96.7% (86.3 g; 83% yield). The crude material can be recrystallized from anisole or toluene / MeOH mixture. mp=235.6~236.9℃; mp(DSC): 232.9℃; 1 H NMR (80 MHz, CDCl3): δ = 8.07 - 7.12 (m, 32H), 3.24 - 2.76 (m, 4H), 3.07 - 2.59 (m, 4H), 1.81 (s, 6H), -0.72 (s, 2H, OH) ppm. IR (ATR): 731.1 (78.73); 777.3 (46.43); 798.6 (65.68); 889.2 (80.73); 1012.7 (70.29); 1068.6 (73.00); 1114.9 (85.15); 1221.0 (74.61); 1334.8 (86.63); 1386.9 (76.67); 1456.3 (82.21); 2870.2 (90.63); 2935.8 (90.42); 2964.7 (90.34); 3057.3 (90.78); 3556.9 (88.32) cm -1 .

[0328] Example 3: 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-di(naphthalen-2-yl)phenyl]-1-methyl-ethyl]-2,6-di(naphthalen-2-yl)phenoxy]ethanol (X=C(CH 3 ) 2 、R 1 =R 2 =R 3 =R 4 = naphthalene-2-yl and Z 1 =Z 2 = 2-hydroxyethyl; compound 35 of Table A) of formula (Ia-1)

[0329] [ka] 2-[2,6-dibromo-4-[1-[3,5-dibromo-4-(2-hydroxyethoxy)phenyl]-1-methyl -To [ethyl]phenoxy]ethanol (90.4 g; 133 mmol; purity=93%) was added naphthalen-2-ylboronic acid (138 g; 800 mmol; 6 equiv.) and tris(o-tolyl)phosphane (1.62 g; 5.32 mmol). To this mixture was added K3PO4 (178 g) dissolved in anisole (800 mL) and water (396 g). The mixture was stirred at 60-70 °C until two clear phases were formed and purged with nitrogen. To this mixture was added Pd(OCOCH3)2 (299 mg; 1.33 mmol) under argon and the mixture was stirred under reflux until TLC showed complete conversion (about 5-6 h). The reaction mixture was then cooled to 70 °C and the organic layer was separated at this temperature and subsequently washed with an aqueous solution of NaOH (10 wt%), an aqueous solution of HCl (2 M) and brine. The organic layer was treated with activated carbon (Norit® DX Ultra, Cabot Corp.) and the mixture was stirred for 2.5 h. The mixture was then filtered through Celite and the solution was concentrated under reduced pressure. The resulting mixture was cooled to room temperature and stirred overnight. The formed crystals were collected by filtration to give the crude title compound as an off-white solid. This was crystallized from a toluene / anisole mixture to give 92.3 g of the title compound as an off-white solid with a chemical purity of 92%. After recrystallization from methanol, the title compound was obtained as a white solid with a chemical purity of >95%. mp=210.1~211.7℃; mp(DSC): 207.1℃; 1 H NMR (80 MHz, CDCl3): δ = 8.19 - 7.75 & 7.74 - 7.35 (m, 32H), 3.51 - 3.13 (m, 8H), 1.82 (s, 6H), 1.28 (s, 2H, OH) ppm. IR (ATR): 744.6 (55.26); 819.8 (64.42); 854.5 (69.17); 885.4 (71.58); 1003.0 (78.82); 1037.7 (79.19); 1072.5 (81.63); 1190.1 (80.56); 1207.5 (73.83); 1446.7 (81.33); 1462.1 (81.60); 1504.5 (84.20); 2870.2 (90.17); 2930.0 (89.00); 2964.7 (86.99); 3051.5 (88.37); 3281.0 (90.10) cm -1 .

[0330] Example 4a: 2,6-di(phenanthren-9-yl)-4-[1-(3,5-di(phenanthren-9-yl)-4-hydroxy-phenyl)-1-methyl-ethyl]phenol (X=C(CH 3 ) 2 、R 1 =R 2 =R 3 = R = phenanthren-9-yl and Z 1 =Z 2 = hydrogen; Compound 4 of Table A) To 2,6-dibromo-4-[1-(3,5-dibromo-4-hydroxy-phenyl)-1-methyl-ethyl]phenol (=3,3',5,5'-tetrabromobisphenol A) (56.1 g; 100 mmol; purity=97%) was added phenanthren-9-ylboronic acid (133.3 g; 600 mmol; 6 equiv.) and tris(o-tolyl)phosphane (1.22 g; 4 mmol). To this mixture was added K3PO4 (133 g) dissolved in anisole (600 mL) and water (198 g). The mixture was stirred at 60-70 °C and purged with nitrogen until two clear phases were formed. To this mixture was added Pd(OCOCH3)2 (225 mg; 1 mmol) under argon and the mixture was stirred under reflux until TLC showed complete conversion. The reaction mixture was then cooled to 70° C., and the organic layer was separated at this temperature, followed by washing with an aqueous solution of NaOH (10% by weight), an aqueous solution of HCl (2M), and brine. The organic layer was treated with activated carbon (Norit® DX Ultra, Cabot Corp.) and the mixture was stirred for 2.5 hours. The mixture was then filtered through Celite and the solvent was removed under reduced pressure. The crude title compound thus obtained as an off-white solid was dissolved in a toluene / methanol mixture (400 g) at high temperature. The mixture was cooled to room temperature and stirred overnight. The formed crystals were collected by filtration to give the crude title compound as an off-white solid with a chemical purity of 95% (90.9 g). This was used in the next step without further purification.

[0331] Example 4b: 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-di(phenanthren-9-yl)-phenyl]-1-methyl-ethyl]-2,6-di(phenanthren-9-yl)-phenoxy]ethanol (X=C(CH 3 ) 2 、R 1 =R 2 =R 3 =R 4 = phenanthren-9-yl and Z 1 =Z 2 = 2-hydroxyethyl; compound 36 of Table A) of formula (Ia-1)

[0332] [ka] To 2,6-di(phenanthren-9-yl)-4-[1-(3,5-di(phenanthren-9-yl)-4-hydroxy-phenyl)-1-methyl-ethyl]phenol (111.7 g; 110 mmol; purity=95%) was added ethylene carbonate (77.5 g; 880 mmol; 8 equiv.), anisole (315 g) and K2CO3 (12.2 g) as solids. The mixture was stirred at 135° C. until TLC showed complete conversion. The reaction mixture was then cooled to 70-75° C. and the organic layer was separated at this temperature and then washed with an aqueous solution of NaOH (10 wt.%) and brine. The organic layer was treated with activated charcoal (Norit® DX Ultra, Cabot Corp.) and the mixture was stirred for 2-3 h. The mixture was then filtered through Celite and the solvent was removed under reduced pressure. The crude title compound thus obtained as an off-white solid was dissolved in methyl ethyl ketone (250 g) at reflux. The mixture was then cooled to room temperature and stirred overnight. The formed crystals were collected by filtration to give the title compound as a white solid with a chemical purity of >97% and a yellowness index of 2.9 (90.5 g; 79% yield). mp(DSC):299.7℃(302.5℃); 1 H NMR (80 MHz, CDCl3): δ = 8.99 - 8.72 (m, 8H), 8.13 - 7.69 (m, 32H), 3.33 - 3.11 (m, 4H), 3.10 - 2.87 (m, 4H), 2.19 (s, 6H), 1.16 (s, 2H, OH) ppm. IR (ATR): 725.3 (71.39); 750.3 (69.02); 763.8 (83.89); 792.8 (90.23); 856.4 (92.27); 891.1 (85.61); 1010.7 (87.29); 1066.7 (89.17); 1215.2 (89.68); 1278.9 (93.54); 1361.8 (92.15); 1448.6 (89.01); 1462.1 (91.02); 2283.8 (95.22); 2868.2 (95.44); 2918.4 (95.24); 3063.1 (95.44); 3551.1 (93.88) cm -1 .

[0333] Example 5: 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-di(1,2-dibenzo[b,d]thien-4-yl)-phenyl]-1-methyl-ethyl]-2,6-di(1,2-dibenzo[b,d]thien-4-yl)-phenoxy]ethanol (X=C(CH 3 ) 2 、R 1 =R 2 =R 3 =R 4 = dibenzo[b,d]thiophen-4-yl and Z 1 =Z 2 = 2-hydroxyethyl; compound 51 of Table A) of formula (Ia-1)

[0334]

Chem.

[0335] Example 6: 2-[4-[4-(2-hydroxyethoxy)-3,5-di(naphthalen-1-yl)phenyl]sulfonyl-2,6-di(naphthalen-1-yl)phenoxy]ethanol (X=SO 2 、R 1 =R 2 =R 3 =R 4 = naphthalene-1-yl and Z 1 =Z 2 = 2-hydroxyethyl; compound 55 of Table A) of formula (Ia-1)

[0336]

Chem.

[0337] Example 7: 2-[4-[4-(2-hydroxyethoxy)-3,5-di(naphthalen-1-yl)phenyl]sulfanyl-2,6-di(naphthalen-1-yl)phenoxy]ethanol (X=S, R 1 =R 2 =R 3 =R 4 = naphthalene-1-yl and Z 1 =Z 2 = 2-hydroxyethyl; compound 76 of Table A) of formula (Ia-1)

[0338]

Chem.

[0339] Example 8: 2-[4-[4-(2-hydroxyethoxy)-3,5-di(phenanthren-9-yl)phenyl]sulfonyl-2,6-di(phenanthren-9-yl)phenoxy]ethanol (X=SO 2 、R 1 =R 2 =R 3 =R 4 = phenanthren-9-yl and Z 1 =Z 2 = 2-hydroxyethyl; compound 57 of Table A) of formula (Ia-1)

[0340] [ka] To 2-[4-[4-(2-hydroxyethoxy)-3,5-dibromophenyl]sulfonyl-2,6-dibromophenoxy]ethanol (148.0 g; 217.26 mmol; purity=96%) was added phenanthren-9-ylboronic acid (246.13 g; 1.0863 mol; 5 equiv; purity=98%) and tris(o-tolyl)phosphane (1.33 g; 4.35 mmol). To this mixture was added anisole (700 g) and 240 g of K3PO4 dissolved in 532 g of water. The mixture was stirred at 60-70 °C and purged with nitrogen until two clear phases were formed. To this mixture was added Pd(OCOCH3)2 (244 mg; 1.086 mmol) under argon and the mixture was stirred under reflux for 9 h. Then, TLC (eluent: e.g., cyclohexane:ethyl acetate 1:2) indicated the reaction was complete, so additional phenanthren-9-ylboronic acid (24.613 g; 108.63 mmol) and 24 g of K3PO4 dissolved in 53.2 g of water and Pd catalyst [Pd(OCOCH3)2 (24.4 mg; 0.1086 mmol) and tris(o-tolyl)phosphane (133 mg; 0.435 mmol)] were added. The reaction mixture was stirred under reflux for another 90 min until TLC (eluent: e.g., cyclohexane:ethyl acetate 1:2) indicated nearly complete conversion. The mixture was cooled to room temperature and stirred for 1 h.

[0341] The crude product was filtered off, washed with anisole and 2-methyltetrahydrofuran, and dried at 60° C. The crude product was dissolved in 3 L of THF and 10 g of activated carbon (Norit DX Ultra) was added. The mixture was stirred at 40° C. for 2 h, the activated carbon was filtered through Celite, and the solvent was then completely removed under reduced pressure. The product was crystallized from toluene to give 157.7 g of the title compound as a white solid with a chemical purity of >94%. The product was recrystallized from toluene to give the title compound with a chemical purity of >97%. mp(DSC): 233.8°C (toluene-solvate); 242.2°C 1H NMR (80 MHz, CDCl3): δ = 8.43 - 9.03 (m, 8H), 8.22 (dd, J = 3.1, 1.4 Hz, 4H), 7.55 - 8.01 (m, 28H), 7.20 - 7.27 (m, 4H), 3.01 - 3.49 (m, 4H, -CH2-), 2.50 - 2.92 (m, 4H, -CH2-), 0.32 - 0.56 (m, 2H) ppm. IR (ATR): 405.06 (29.54); 561.3 (78.99); 615.31 (63.9); 632.67 (63.18); 723.33 (48.06); 744.55 (52.77); 763.84 (75.45); 887.28 1012.66 (79.76); 1066.67 (82.66); 1082.1 (76.5); 1091.75 (75.17); 1132.25 (63.8); 1145.75 (76.3); 1178.55 (85.26); 1230.63 (81.87); 1261.49 (82.73); 1319.35 (80.0); 1419.66 (82.14); 1450.52 (81.1) cm -1 . n D Calculated value: 1.76 (calculated using software ACD / ChemSketch 2012 manufactured by Advanced Chemistry Development, Inc.)

[0342] Example 9: 2-[4-[4-(2-hydroxyethoxy)-3,5-di(dibenzo[b,d]thien-4-yl)phenyl]sulfonyl-2,6-dibenzo[b,d]thien-4-yl)phenoxy]ethanol (X=SO 2 、R 1 =R 2 =R 3 =R 4 = Dibenzo[b,d]thien-4-yl and Z 1 =Z 2 = 2-hydroxyethyl; compound 72 of Table A) of formula (Ia-1)

[0343] [ka] To 2-[4-[4-(2-hydroxyethoxy)-3,5-dibromophenyl]sulfonyl-2,6-dibromophenoxy]ethanol (143.05 g; 210 mmol; purity=96%) was added dibenzo[b,d]thiophen-4-ylboronic acid (244.37 g; 1.05 mol; 5 equiv; purity=98%) and tris(o-tolyl)phosphane (1.28 g; 4.2 mmol). To this mixture was added anisole (700 g) and 232 g of K3PO4 dissolved in 515 g of water. The mixture was stirred at 60-70 °C and purged with nitrogen until two clear phases were formed. To this mixture was added Pd(OCOCH3)2 (236 mg; 1.05 mmol) under argon and the mixture was stirred at reflux for 3 h until TLC (eluent: e.g., cyclohexane:ethyl acetate 1:2) showed complete conversion. (Note: if the reaction is not complete after 9 h at reflux by TLC, additional dibenzo[b,d]thiophen-4-ylboronic acid (24.44 g; 105 mmol) and 23.2 g K3PO4 dissolved in 51.5 g water and Pd catalyst [Pd(OCOCH3)2 (23.6 mg; 0.105 mmol) and tris(o-tolyl)phosphane (128 mg; 0.42 mmol)] should be added and the reaction mixture should be stirred at reflux until TLC shows at least near complete conversion.)

[0344] The mixture was cooled to 70° C., the organic layer was separated at 70° C., and the aqueous phase was extracted with 250 mL of 2-methyltetrahydrofuran. To the combined organic layers was added a 10% aqueous solution of NaOH (375 mL) at 70° C. The product crystallized, so the suspension was cooled to room temperature and the crude product was filtered off, then washed with water and THF and dried at 60° C. to give 207.5 g of crude product.

[0345] The resulting solid was dissolved in 3 L of anisole at reflux and then cooled to 120° C. Then 10 g of activated charcoal (Norit DX Ultra) was added and the mixture was stirred at 120° C. for 1 h. The activated charcoal was filtered off using Celite at 120° C. and the solution was concentrated under reduced pressure to about 1000 g. The clear solution was cooled to room temperature and THF (500 mL) was added. The formed crystals were collected by filtration and dried at 60° C. to give the crude title compound as a white solid (174.4 g; 77.8%). The crude product was recrystallized from anisole / THF (1 / 1 v / v) or anisole / 2-propanol (1 / 1 v / v) mixture to give the title compound with chemical purity >95% (by NMR) (Note: when anisole / THF mixture was used, the THF-solvate of the title compound was obtained). mp(DSC):204.1℃(THF-Solvate);294.1℃ 1 H NMR (80 MHz, CDCl3): δ = 8.52 (s, 4H), 8.32 - 8.51 (m, 8H), 7.09 - 7.88 (m, 20H), 3.40 - 3.55 (m, 4H), 3.13 - 3.29 (m, 4H), 1.00 (t, J = 6,5 Hz, 2H, OH) ppm. IR (ATR): 495.72 (37.35); 551.66 (81.77); 565.16 (83.67); 607.6 (62.68); 630.74 (69.8); 704.04 (76.01); 723.33 (77.99); 748.41 1003.02 (77.16); 1045.45 (68.95); 1068.6 (80.44); 1105.25 (78.89); 1120.68 (80.61); 1145.75 (67.34); 1234.48 (80.97); 1246.06 (79.06); 1303.92 (81.87); 1319.35 (80.33); 1375.29 (80.49); 1383.01 (81.94); 1429.3 (77.66); 1442.8 (82.59) cm-1 . n D Calculated value: 1.79 (calculated using software ACD / ChemSketch 2012 manufactured by Advanced Chemistry Development, Inc.)

[0346] Example 10: 2-[4-[4-(2-hydroxyethoxy)-3,5-di(thianthren-1-yl)phenyl]sulfonyl-2,6-di(thianthren-1-yl)phenoxy]ethanol (X=SO 2 、R 1 =R 2 =R 3 =R 4 = thianthren-1-yl and Z 1 =Z 2 = 2-hydroxyethyl; compound 73 of formula (Ia-1) in Table A)

[0347] [ka] To 2-[4-[4-(2-hydroxyethoxy)-3,5-dibromophenyl]sulfonyl-2,6-dibromophenoxy]ethanol (143.05 g; 210 mmol; purity=96%) was added thianthren-1-ylboronic acid (278.72 g; 1.05 mol; 5 equiv; purity=98%) and tris(o-tolyl)phosphane (1.28 g; 4.2 mmol). To this mixture was added anisole (700 g) and 232 g of K3PO4 dissolved in 515 g of water. The mixture was stirred at 60-70 °C and purged with nitrogen until two clear phases were formed. To this mixture was added Pd(OCOCH3)2 (236 mg; 1.05 mmol) under argon and the mixture was stirred at reflux until TLC (eluent: e.g., cyclohexane:ethyl acetate 1:2) showed complete conversion. (Note: if the reaction is not complete after 9 h at reflux by TLC, additional thianthren-1-ylboronic acid (27.87 g; 105 mmol) and 23.2 g of K3PO4 dissolved in 51.5 g of water and Pd catalyst [Pd(OCOCH3)2 (23.6 mg; 0.105 mmol) and tris(o-tolyl)phosphane (128 mg; 0.42 mmol)] should be added. The reaction mixture should then be stirred at reflux until TLC shows at least near complete conversion.)

[0348] The mixture was cooled to 70°C and the organic layer was separated at 70°C, then washed with an aqueous solution of NaOH (10 wt%), an aqueous solution of HCl (2M) and brine. To the organic layer, 100 g of Na2SO4 and 10 g of activated carbon (Norit DX Ultra) were added and the mixture was stirred for 1 h. The mixture was then filtered through Celite and the solvent was completely removed under reduced pressure. The crude product was dissolved in 860-880 mL of toluene / methanol (1 / 1 v / v) mixture at 55°C, then the clear solution was cooled to room temperature and stirred overnight. The formed crystals were collected by filtration and after drying at 60°C, the crude title compound was obtained as a white solid with a chemical purity of 97.61% (210.6 g; 83.9%). The product can be further purified by additional recrystallization from a toluene / methanol mixture. mp(DSC): 224.0℃; 1 H NMR (80 MHz, CDCl3): δ = 8.25 (s, 4H), 7.97 - 7.23 (m, 28H), 3.55 - 3.35 (m, 4H), 3.43 - 3.05 (m, 4H), 1.41 - 1.30 (m, 2H, OH), ppm. IR (ATR): 572.88 (85.64); 615.31 (56.0); 663.53 (83.11); 700.18 (68.44); 721.4 (79.65); 746.48 (51.87); 783.13 (72.49); 794.7 1010.73 (76.44); 1057.03 (84.15); 1074.39 (80.9); 1099.46 (73.27); 1118.75 (83.89); 1145.75 (63.26); 1190.12 (86.98); 1226.77 (80.11); 1249.91 (83.27); 1319.35 (71.87); 1361.79 (85.74); 1394.58 (74.99); 1431.23 (74.95); 1448.59 (80.7); 1558.54 (87.15) cm -1 . n D Calculated value: 1.77 (calculated using software ACD / ChemSketch 2012 manufactured by Advanced Chemistry Development, Inc.)

[0349] Example 11: 2,2'-(sulfonylbis{[2,6-di(naphthalen-1-yl)-4,1-phenylene]oxy})di(ethan-1-ol) (X=SO 2 、R 1 =R 2 =R 3 =R 4 = naphthalene-2-yl and Z 1 =Z 2 = 2-hydroxyethyl; compound 56 of Table A) of formula (Ia-1)

[0350] [ka] To 2,2'-{sulfonylbis[(2,6-dibromo-4,1-phenylene)oxy]}di(ethan-1-ol) (170.3 g; 250 mmol; purity=96%) was added naphthalen-2-ylboronic acid (219.37 g; 1.25 mol; 5 equiv; purity=98%) and tris(o-tolyl)phosphane (1.52 g; 5.0 mmol). To this mixture was added 276 g of K3PO4 dissolved in anisole (750 mL) and 613 g of water. The mixture was stirred at 60-70 °C and purged with argon until two clear phases were formed. To this mixture was added Pd(OCOCH3)2 (281 mg; 1.25 mmol) under argon and the mixture was stirred under reflux until TLC showed complete conversion.

[0351] The mixture was cooled to 70° C. and the organic layer was separated at 70° C. and then washed with an aqueous solution of NaOH (10% by weight), an aqueous solution of HCl (2M) and brine. To the organic layer, activated charcoal (Norit DX Ultra) was added and the mixture was stirred at 70° C. for 2.5 hours. The mixture was then filtered through Celite and the solution was concentrated under reduced pressure. The mixture was cooled to room temperature and stirred overnight. The crystals that formed were collected by filtration to give the crude title compound as a white solid with a chemical purity of 92.2% (149.33 g; 65%). The crude material was then recrystallized from toluene / MeOH (1 / 1 v / v) and then from methyl ethyl ketone to give 78.71 g of the title compound as a white solid with a chemical purity of about 94%. mp(DSC): 252.2℃; 1 H NMR (80 MHz, CDCl3): δ = 8.21 (s, 4H, CAr-H), 8.10 - 7.42 (m, 28H, CAr-H), 3.44 - 3.34 (m, 4H, CH2), 3.22 - 3.11 (m, 4H, CH2), 1.11 (bs, 2H) ppm. IR (ATR): 740.69 (60.15); 812.06 (67.64); 866.07 (73.57); 895 (74.44); 949.01 (80.71); 1016.52 (74.98); 1101.39 (65.76); 1143.83 (55.87); 1219.05 (75.88); 1319.35 (64.85); 1421.58 (79.99); 1442.8 (83.05) cm -1 .

[0352] Example 12: 4,4'-(propane-2,2-diyl)bis[2,6-di(thianthren-1-yl)phenol] (X = C(CH 3 ) 2 、R 1 =R 2 =R 3 =R 4 = thianthren-1-yl and Z 1 =Z 2 = hydrogen; Compound 7 of Table A)

[0353] [ka] To 4,4'-(propane-2,2-diyl)bis(2,6-dibromophenol) (70.1 g; 125 mmol; purity: 97%) was added thianthren-1-ylboronic acid (166 g; 625 mmol; 5 equiv; purity: 98%) and tris(o-tolyl)phosphane (1.52 g; 5.0 mmol). To this mixture was added anisole (500 g) and 11.4 g of K3PO4 dissolved in 248 g of water. The mixture was stirred at 60-70 °C and purged with argon until two clear phases were formed. To this mixture was added Pd(OCOCH3)2 (281 mg; 1.25 mmol) under argon and the mixture was stirred under reflux until TLC (eluent: e.g., cyclohexane / ethyl acetate 3:1) showed complete conversion.

[0354] The mixture was cooled to 70° C., and the organic layer was separated at 70° C., then washed with an aqueous solution of NaHCO3 (10 wt %), an aqueous solution of HCl (2M), and brine. To the organic layer, 6.75 g of activated carbon (Norit DX Ultra) and 13.5 g of Na2SO4 were added, and the mixture was stirred for 1 h. The mixture was then filtered through Celite, and the solvent was completely removed under reduced pressure. The crude product can be used in the next step without further purification or recrystallized from a toluene / MeOH (1 / 1 v / v) mixture.

[0355] Example 13: 2,2'-(propane-2,2-diylbis{[2,6-di(thianthren-1-yl)-4,1-phenylene]oxy})di(ethan-1-ol) (X=C(CH 3 ) 2 、R 1 =R 2 =R 3 =R 4 = thianthren-1-yl and Z 1 =Z 2 = 2-hydroxyethyl; compound 52 of Table A) of formula (Ia-1)

[0356] [ka] To 4,4'-(propane-2,2-diyl)bis[2,6-di(thianthren-1-yl)phenol] (125 mmol) obtained in Example 12 in anisole (360 g) was added 5.2 g of K2CO3 and 33 g of ethylene carbonate. The reaction mixture was stirred at reflux until TLC (eluent: e.g., cyclohexane / ethyl acetate 3:1) showed complete conversion.

[0357] The mixture was cooled to 70-80°C and the organic layer was separated at 70°C, then washed with brine, aqueous NaOH (10 wt%), aqueous HCl (2M) and brine. The organic layer was dried over Na2SO4 and filtered through Celite, after which the solvent was completely removed under reduced pressure. The crude product was purified by column chromatography to give 70.8 g of the title compound as a white solid with a chemical purity of about 97-98%. mp(DSC): 110.6℃; 1H NMR (80 MHz, CDCl3): δ = 7.92 - 7.25 (m, 32H, C Ar -H), 3.5 - 3.0 (m, 8H, CH2), 2.1 (bs, 6H, CH3), ppm. IR (ATR): 723.33 (68.04); 744.55 (47.89); 779.27 (73.45); 792.77 (77.93); 885.36 (77.60); 1026.16 (74.34); 1070.53 (78.20); 1111.03 (80.06); 1219.05 (76.24); 1247.99 (79.74); 1386.86 (70.11); 1448.59 (64.40); 1552.75 (85.03); 2848.96 (83.56); 2924.18 (78.87); 3053.42 (87.35) cm -1 .

[0358] Example 14a: 3,3',5,5'-Tetrabromo[1,1'-biphenyl]-4,4'-diol

[0359] [ka] To a solution of 82.7 mL (approximately 258 g) of bromine in 750 g of methanol was slowly added a solution of 60 g of [1,1'-biphenyl]-4,4'-diol in 750 g of methanol at 0° C. The reaction mixture was stirred for another hour at 0° C. and then overnight at room temperature. The precipitated product was filtered off and then washed twice with cold methanol, then with an aqueous solution of ascorbic acid (20 wt %) and finally with water. The crude product (149 g) was crystallized from a THF / toluene mixture to give 130.3 g of the title product as an off-white powder with a chemical purity of >97.5%. 1 H NMR (80 MHz, DMSO-d6): δ = 9.91 (s, 2H, OH), 7.72 (s, 4H, C Ar -H) ppm.

[0360] Example 14b: 2,2'-[(3,3',5,5'-tetrabromo[1,1'-biphenyl]-4,4'-diyl)bis(oxy)]di(ethan-1-ol)

[0361] [ka] To a solution of 161.3 g of 3,3',5,5'-tetrabromo[1,1'-biphenyl]-4,4'-diol obtained in Example 14a in 483 g (approximately 512 mL) of DMF (homogenized at 60° C.), 172.4 g of K2CO3 were added. The mixture was stirred at 60° C. for another 10-20 min, and then 201.24 g of 2-chloroethan-1-ol were added. The reaction mixture was stirred at 120° C. for 3 h. After cooling to room temperature, the reaction mixture was poured into 1.5 L of water, forming a white precipitate. After slow neutralization with concentrated HCl, the crude product was filtered off and then washed with water (3×500 mL) and ethanol (500 mL). The crude product was dissolved in 1450 g of THF at reflux, 4.0 g of activated carbon (Norit DX Ultra) was added, and the mixture was stirred at reflux for 1 h. The mixture was then filtered through Celite at 60° C. and the solvent was removed under reduced pressure. After crystallization from a THF / toluene mixture, the resulting crystals were filtered off and washed with 500 g of toluene to give 157.3 g (approximately 85.5% yield) of the title compound with a chemical purity of >97.7%. mp(DSC): 232.1℃; 1 H NMR (80 MHz, DMSO-d6): δ = 7.8 (s, 4H, C Ar -H), 4.74 (t, J = 5.4 Hz, 2H, OH), 4.2 - 3.5 (m, 8H, CH2) ppm.

[0362] Example 14c: 2,2'-{[3,3',5,5'-tetra(naphthalen-1-yl)[1,1'-biphenyl]-4,4'-diyl]bis(oxy)}di(ethan-1-ol) (X = single bond, R 1 =R 2 =R 3 =R 4 = naphthalene-1-yl and Z 1 =Z 2 = 2-hydroxyethyl; compound 244 of Table A) of formula (Ia-1)

[0363] [ka] To the 2,2'-[(3,3',5,5'-tetrabromo[1,1'-biphenyl]-4,4'-diyl)bis(oxy)]di(ethan-1-ol) (74.5 g; 123.77 mmol) obtained in Example 14b was added naphthalen-1-ylboronic acid (110 g; 626.8 mmol; 5.06 equiv; purity=98%) and anisole (390 mL). To this mixture was added 138 g of K3PO4 dissolved in 306 g of water. The mixture was stirred at 60-70 °C until two clear phases were formed and then purged with argon. To this mixture was added tris(o-tolyl)phosphane (1.5 g; 4.95 mmol) and Pd(OCOCH3)2 (281 mg; 1.25 mmol) in 5 mL of anisole under argon, and the mixture was stirred under reflux until TLC showed complete conversion.

[0364] The mixture was cooled to 70° C., and the organic layer was separated at 70° C., then washed with an aqueous solution of NaOH (10% by weight), an aqueous solution of HCl (2M), and brine. To the organic layer, 10 g of activated carbon (Norit DX Ultra) and 100 g of Na2SO4 were added, and the mixture was stirred at 70° C. for 1 h. The mixture was then filtered through Celite, and the solvent was removed under reduced pressure. The crude product can be recrystallized from a mixture of toluene / i-propanol or toluene / MeOH (1 / 1 v / v) and / or purified via column chromatography (eluent: cyclohexane / ethyl acetate) to give the title compound as a white solid with a chemical purity of about 93%. mp(DSC): 249.6℃; 1 H NMR (80 MHz, CDCl3): δ = 8.20 - 7.73 (m, 16H, C Ar -H), 7.73 - 7.33 (m, 16H, C Ar -H), 3.3 - 2.96 (m, 4H, CH2), 3.0 - 2.53 (m, 4H, CH2), 0.45 (bs, 2H, OH) ppm. IR (ATR): 607.6 (76.1); 734.9 (75.7); 773.48 (34.8); 788.91 (56.9); 800.49 (68.7); 887.28 (68.9); 1018.45 (66.0); 1066.67 (66.2); 1087.89 (74.9); 1222.91 (65.5); 1361.79 (78.5); 1396.51 (70.4); 1427.37 (72.5); 1440.87 (75.9); -1 .

[0365] Example 15: 2,2'-{[3,3',5,5'-tetra(naphthalen-2-yl)[1,1'-biphenyl]-4,4'-diyl]bis(oxy)}di(ethan-1-ol) (X = single bond, R 1 =R 2 =R 3 =R 4 = naphthalene-1-yl and Z 1 =Z 2 = 2-hydroxyethyl; compound 245 of Table A) of formula (Ia-1)

[0366] [ka] To 2,2'-[(3,3',5,5'-tetrabromo[1,1'-biphenyl]-4,4'-diyl)bis(oxy)]di(ethan-1-ol) (74.5 g; 123.77 mmol) was added naphthalen-2-ylboronic acid (165 g; 937.5 mmol; 7.5 equiv; purity = 98%) and anisole (440 mL). To this mixture was added 207 g of K3PO4 dissolved in 460 g of water. The mixture was stirred at 60-70 °C and purged with argon until two clear phases were formed. To this mixture was added tris(o-tolyl)phosphane (3.05 g; 4.95 mmol) and Pd(OCOCH3)2 (561 mg; 2.5 mmol) in 10 mL of anisole under argon and the mixture was stirred under reflux until TLC showed complete conversion.

[0367] The mixture was cooled to 70° C. and the organic layer was separated at 70° C. and then washed with an aqueous solution of NaOH (10 wt %), an aqueous solution of HCl (2M) and brine. To the organic layer, 10 g of activated carbon (Norit DX Ultra) and 100 g of Na2SO4 were added and the mixture was stirred at 70° C. for 1 h. The mixture was then filtered through Celite and the solvent was removed under reduced pressure. The crude product was recrystallized from a mixture of toluene / MeOH (7 / 3 w / w) and / or purified via column chromatography (eluent: cyclohexane / ethyl acetate) to give the title compound as a white solid with a chemical purity of about 94%. mp(DSC): 256.4℃; 1 H NMR (80 MHz, CDCl3): δ = 8.2 (s, 4H, C Ar -H), 8.12 - 7.77 (m, 20H, C Ar -H), 7.71 - 7.42 (m, 8H, C Ar -H), 3.57 - 3.38 (m, 4H, CH2), 3.37 - 3.13 (m, 4H, CH2), 1.13 (m, 2H, OH) ppm. IR (ATR): 515.01 (67.1); 651.96 (78.1); 744.55 (37.5); 775.41 (77.9); 800.49 (77.7); 823.63 (53.4); 860.28 (51.3); 893.07 1014.59 (70.5); 1045.45 (74.2); 1072.46 (72.0); 1080.17 (68.6); 1217.12 (67,0); 1236.41 (76.2); 1336.71 (76.6); 1419.66 (67.7); 1442.8 (69.8); 1504.53 (76.0) cm -1 .

[0368] Example 16: 2,2'-{[3,3',5,5'-tetra(phenanthren-9-yl)[1,1'-biphenyl]-4,4'-diyl]bis(oxy)}di(ethan-1-ol) (X = single bond, R 1 =R 2 =R 3=R 4 = phenanthren-9-yl and Z 1 =Z 2 = 2-hydroxyethyl; compound 246 of Table A) of formula (Ia-1)

[0369] [ka] To 2,2'-[(3,3',5,5'-tetrabromo[1,1'-biphenyl]-4,4'-diyl)bis(oxy)]di(ethan-1-ol) (75.2 g; 125 mmol) was added phenanthren-9-ylboronic acid (141.61 g; 625 mmol; 7.5 equiv; purity: 98%) and anisole (390 mL). To this mixture was added 138 g of K3PO4 dissolved in 306 g of water. The mixture was stirred at 60-70 °C and purged with argon until two clear phases were formed. To this mixture was added tris(o-tolyl)phosphane (1.52 g; 5.0 mmol) and Pd(OCOCH3)2 (281 mg; 1.25 mmol) in 5 mL of anisole under argon and the mixture was stirred under reflux until TLC showed complete conversion.

[0370] The mixture was cooled to 70° C. and the organic layer was separated at 70° C. and then washed with an aqueous solution of NaOH (10 wt %), an aqueous solution of HCl (2M) and brine. To the organic layer, 10 g of activated carbon (Norit DX Ultra) and 100 g of Na2SO4 were added and the mixture was stirred at 70° C. for 1 h. The mixture was then filtered through Celite and the solvent was removed under reduced pressure. The crude product was recrystallized from a mixture of toluene / MeOH (7 / 3 w / w) and / or purified via column chromatography (eluent: cyclohexane / ethyl acetate) to give the title compound as a white solid with a chemical purity of >98%. mp(DSC): 347.2℃ and 392.1℃; 1 H NMR (80 MHz, CDCl3): δ = 8.79 - 8.41 (m, 8H, C Ar -H), 8.09 - 7.32 (m, 32H, C Ar-H), 3.34 - 3.18 (m, 4H, CH2), 2.84 - 2.68 (m, 4H, CH2), 0.57 - 0.45 (m, 2H, OH) ppm. IR (ATR): 488.01 (37.8); 567.09 (72.2); 617.24 (70.9); 692.47 (78.9); 725.26 (43.6); 744.55 (47.9); 765.77 (66.8); 885.36 (71.0); 1014.59 (74.9); 1068.6 (76.0); 1220.98 (71.6); 1361.79 (79.7); 1429.3 (67.4); 1448.59 (72.5) cm -1 .

[0371] Example 17: 2,2'-{[3,3',5,5'-tetrakis(dibenzo[b,d]thiophen-4-yl)[1,1'-biphenyl]-4,4'-diyl]bis(oxy)}di(ethan-1-ol) (X = single bond, R 1 =R 2 =R 3 =R 4 = Dibenzo[b,d]thien-4-yl and Z 1 =Z 2 = 2-hydroxyethyl; compound 248 of Table A) of formula (Ia-1)

[0372] [ka] To 2,2'-[(3,3',5,5'-tetrabromo[1,1'-biphenyl]-4,4'-diyl)bis(oxy)]di(ethan-1-ol) (10 g; 16.3 mmol) was added dibenzo[b,d]thiophen-4-ylboronic acid (19.1 g; 81.37 mmol; 5 equiv; purity = 98%) and anisole (51 mL). To this mixture was added 18 g of K3PO4 dissolved in 40 g of water. The mixture was stirred at 60-70 °C and purged with argon until two clear phases were formed. To this mixture was added tris(o-tolyl)phosphane (198 mg; 0.651 mmol) and Pd(OCOCH3)2 (37 mg; 0.163 mmol) in 5 mL of anisole under argon and the mixture was stirred under reflux until TLC showed complete conversion.

[0373] The mixture was cooled to 70° C. and the organic layer was separated at 70° C. and then washed with an aqueous solution of NaOH (10 wt %), an aqueous solution of HCl (2M) and brine. To the organic layer, 1.0 g of activated carbon (Norit DX Ultra) and 10.0 g of Na2SO4 were added and the mixture was stirred at 70° C. for 1 h. The mixture was then filtered through Celite and the solvent was removed under reduced pressure. The crude product was recrystallized from methyl ethyl ketone and / or purified via column chromatography (eluent: cyclohexane / ethyl acetate) to give the title compound as a white solid with a chemical purity of >94%. mp(DSC): 390.9℃; 1 H NMR (80 MHz, CDCl3): δ = 8.21 - 6.98 (m, 32H, C Ar -H), 3.34 - 3.18 (m, 4H, CH2), 3.05 - 2.79 (m, 4H, CH2), 1.05 - 0.85 (m, 2H, OH) ppm. IR (ATR): 607.6 (74.1); 617.24 (65.8); 650.03 (74.3); 686.68 (70.2); 704.04 (71.5); 721.4 (64.4); 744.55 (29.7); 887.28 (61.2); 1031.95 (63.0); 1047.38 (60.8); 1078.24 (64.8); 1232.55 (64.9); 1249.91 (74.9); 1303.92 (78.5); 1357.93 (75.7); 1379.15 (68.1); 1442.8 (65.3) cm -1 .

[0374] Example 18: 2,2'-{[3,3',5,5'-tetra(thianthren-1-yl)[1,1'-biphenyl]-4,4'-diyl]bis(oxy)}di(ethan-1-ol) (X = single bond, R 1 =R 2 =R 3 =R 4 = thianthren-1-yl and Z 1 =Z 2 = 2-hydroxyethyl; compound 249 of Table A) of formula (Ia-1)

[0375] [ka] To 2,2'-[(3,3',5,5'-tetrabromo[1,1'-biphenyl]-4,4'-diyl)bis(oxy)]di(ethan-1-ol) (12.04 g; 20 mmol) was added thianthren-1-ylboronic acid (26.5 g; 100 mmol; 5 equiv; purity: 98%) and anisole (62 mL). To this mixture was added 22.1 g of K3PO4 dissolved in 49 g of water. The mixture was stirred at 60-70 °C and purged with argon until two clear phases were formed. To this mixture was added tris(o-tolyl)phosphane (244 mg; 0.8 mmol) and Pd(OCOCH3)2 (45 mg; 0.2 mmol) in 5 mL of anisole under argon and the mixture was stirred under reflux until TLC showed complete conversion.

[0376] The mixture was cooled to 70° C. and the organic layer was separated at 70° C. and then washed with an aqueous solution of NaOH (10 wt %), an aqueous solution of HCl (2M) and brine. To the organic layer, 1.0 g of activated carbon (Norit DX Ultra) and 10.0 g of Na2SO4 were added and the mixture was stirred at 70° C. for 1 h. The mixture was then filtered through Celite and the solvent was removed under reduced pressure. The crude product was purified via column chromatography (eluent: cyclohexane / ethyl acetate) to give the title compound as a white solid with chemical purity >94%. mp(DSC): 276.5℃; 1 H NMR (80 MHz, DMSO-d6): δ = 7.85 (s, 4H, C Ar -H), 7.74 - 7.16 (m, 28H, C Ar -H), 4.15 - 4.00 (m, 2H, OH), 3.27 - 3.05 (m, 4H, CH2), 2.90 - 2.70 (m, 4H, CH2) ppm. IR (ATR): 410.85 (5.61); 432.07 (43.16); 461.00 (48.69); 476.43 (49.07); 663.53 (75.92); 725.26 (68.4); 746.48 (45.2); 790.84 (73.4); 875.71 (75.99); 1018.45 (75.63); 1070.53 (77.53); 1224.84 (73.71); 1390.72 (71.63); -1 .

[0377] Example 19a: 3,3',5,5'-Tetrabromo[1,1'-biphenyl]-2,2'-diol

[0378] [ka] To a solution of 1,1'-biphenyl-2,2'-diol (25.0 g; 134 mmol) in methanol (1000 mL) was added bromine (107 g, 671 mmol, 5.0 equiv.) dropwise at 0° C. The reaction was warmed to room temperature and stirred until TLC (heptane / ethyl acetate 2:1) showed complete conversion. The precipitate was filtered off and washed with cold methanol to give the crude product as a yellow solid (49.8 g, 99.2 mmol; yield: 74%). The crude product was recrystallized from acetone to give 35.9 g of the title compound as an off-white solid. mp(DSC): Decomposed at 300℃. 1 H NMR (80 MHz, DMSO-d6): δ = 8.67 (br s, 2H), 7.74 (d, J = 2.4 Hz, 2H), 7.29 (d, J = 2.4 Hz, 2H) ppm.

[0379] Example 19b: 2,2'-[(3,3',5,5'-tetrabromo[1,1'-biphenyl]-2,2'-diyl)bis(oxy)]di(ethan-1-ol)

[0380] [ka] To a suspension of 3,3',5,5'-tetrabromo[1,1'-biphenyl]-2,2'-diol (29.0 g; 57.8 mmol) obtained in Example 19a in anisole (450 mL) was added K2CO3 (31.9 g, 231 mmol, 4.0 equiv.) and the mixture was stirred at 50°C for 30 min. Ethylene carbonate (50.9 g, 578 mmol, 10 equiv.) was added in portions and the reaction was heated to reflux until TLC (cyclohexane / ethyl acetate (2:1) with approximately 1% acetic acid) showed complete conversion. The mixture was cooled to room temperature, ethyl acetate (200 mL) and water (100 mL) were added and the phases were separated. The aqueous phase was extracted with ethyl acetate (100 mL). The combined organic phases were washed with water (2×100 mL), dried over Na2SO4, and the solvent was removed under reduced pressure to give the crude product as an off-white solid (35.2 g, 57.8 mmol, 100%). The crude product was recrystallized from toluene to give 20 g of the title compound as a slightly off-white solid. 1 H NMR (80 MHz, CDCl3): δ = 7.76 (d, J = 2.4 Hz, 2H), 7.45 (d, J = 2.4 Hz, 2H), 3.85 - 3.49 (m, 8H), 2.08 (t, J = 5.6 Hz, 2H) ppm.

[0381] Example 19c: 2,2'-{[3,3',5,5'-tetra(phenanthren-9-yl)[1,1'-biphenyl]-2,2'-diyl]bis(oxy)}di(ethan-1-ol) (X = single bond, R 1 =R 2 =R 3 =R 4 = thianthren-1-yl and Z 1 =Z 2 = 2-hydroxyethyl; compound 12 of Table B) of formula (Ia-1)

[0382] [ka] To a mixture of 2,2'-[(3,3',5,5'-tetrabromo[1,1'-biphenyl]-2,2'-diyl)bis(oxy)]di(ethan-1-ol) obtained in Example 19b (17.0 g; 28.8 mmol) and 9-phenanthrylboronic acid (32.0 g; 144 mmol; 5.0 equiv.) in anisole (100 g) was added a solution of KPO (31.8 g, 150 mmol, 5.2 equiv.) in water (70 g) and the mixture was heated to 70°C. Tris(o-tolyl)phosphane (0.175 g, 0.576 mmol, 2.0 mol%) and Pd(OCOCH3)2 (32.4 mg; 0.144 mmol, 0.5 mol%) were added and the reaction mixture was heated to reflux until TLC (cyclohexane / ethyl acetate 3:1) showed no further progress.

[0383] The reaction mixture was cooled to room temperature, ethyl acetate (100 g) was added and the layers were separated. The aqueous phase was extracted with ethyl acetate (50 g). The combined organic phases were washed successively with water (100 g) then brine (100 g), dried over Na2SO4 and the solvent was removed under reduced pressure to give the crude product. Purification via column chromatography (cyclohexane / ethyl acetate 3:1) afforded 21.5 g of the title compound as a white solid with chemical purity >95%. mp=196℃~205℃ 1 H NMR (80 MHz, CDCl3): δ = 9.04-8.54 (m, 8H), 8.43 - 7.42 (m, 32H), 3.95 - 3.05 (m, 8H), 1.71 (t, J = 6.2 Hz, 2H) ppm.

[0384] 2.3 Refractive index n of the monomer of formula (I) D : Table C below lists the refractive index of several monomers of formula (I) calculated using the software ACD / ChemSketch 2012 (Advanced Chemistry Development, Inc.). Individual monomers are identified in Table C by their entry numbers in Tables A and B, respectively. Furthermore, all monomers included in Table C have been confirmed by quantum chemical calculations to have no or only slight to negligible absorption in the visible light range and therefore are essentially colorless.

[0385] [Table 3-1]

[0386] [Table 3-2]

[0387] [Table 3-3]

[0388] [Table 3-4]

[0389] 3. Preparation of polycarbonate resin from monomer of formula (I) 3.1 Analysis of resins prepared from monomers of formula (I): Refractive index (n D ): The refractive index was measured using a 3 mm thick disk-shaped test piece made of polycarbonate resin according to JIS B 7071-2:2018. The measurement was performed at 23°C using the following refractive index measuring device. Refractometer: KPR-3000 manufactured by Shimadzu Corporation

[0390] Abbe number (ν): A disk-shaped test piece with a thickness of 3 mm was used, which was the same as the test piece used in the refractive index measurement. Using a refractive index measuring device, the refractive index values ​​were measured at wavelengths of 486 nm, 589 nm, and 656 nm at temperatures below 23° C. Then, the Abbe number was calculated using the following formula. Refractometer: KPR-3000 manufactured by Shimadzu Corporation ν=(nD-1) / (nF-nC) nD: Refractive index at a wavelength of 589 nm nC: Refractive index at a wavelength of 656 nm nF: Refractive index at a wavelength of 486 nm

[0391] Glass transition temperature (Tg): The glass transition temperature was measured by differential scanning calorimetry (DSC) using a heating program of 10° C. / min according to JIS K7121-1987. Differential scanning calorimetry: X-DSC7000 manufactured by Hitachi High-Tech Science Co., Ltd.

[0392] molecular weight The weight average molecular weight (Mw) values ​​of the resins were measured based on the gel permeation chromatography (GPC) method and calculated by the standard polystyrene conversion approach. The following equipment, columns and measurement conditions were used: GPC equipment: HLC-8420GPC (Tosoh Corporation); Columns: 3 TSKgel SuperHM-M (Tosoh Corporation), One guard column, SuperHM-M (Tosoh Corporation), One bottle of TSKgel SuperH-RC (manufactured by Tosoh Corporation); Detector: RI detector Standard polystyrene: PstQuick C (Tosoh Corporation) as a standard polystyrene kit; Eluent: tetrahydrofuran; Eluent flow rate: 0.6 ml / min; Column temperature: 40°C.

[0393] The number average molecular weight (Mn) value can be calculated using a method similar to that used to measure the Mw value described above. The polystyrene converted weight average molecular weight (Mw) and number average molecular weight (Mn) were calculated from a calibration curve of a standard polystyrene prepared in advance. Specifically, a calibration curve was prepared using a standard polystyrene (manufactured by Tosoh Corporation, "PStQuick C") with a known molecular weight. Furthermore, the elution time and molecular weight value of each peak were plotted from the measured data of the standard polystyrene, and a calibration curve was prepared by approximating the data using a cubic equation. The Mw and Mn values ​​were calculated using the following formula: Mw = Σ(Wi × Mi) ÷ Σ(Wi) Mn = Σ(Ni × Mi) ÷ Σ(Wi) Here, "i" is the "i"th division point, Wi is the molecular weight (g) of the "i"th polymer, "Ni" is the number of molecules of the "i"th polymer, and "Mi" is the mass of the "i"th molecule. The molecular weight (M) is the polystyrene molecular weight value at the same elution time on the calibration curve.

[0394] Low molecular weight compound content (CLWC) The content of low molecular weight compounds (CLWC) represents the ratio of the total peak area of ​​compounds with Mw values ​​less than 1000 to the total area of ​​all peaks (peak areas are determined based on the GPC analysis described above). Thus, the CLWC value was determined using the following formula:

[0395]

number

[0396] Birefringence(Δn): Each resin example to be analyzed was dissolved in methylene chloride (solvent) to form a solution with a concentration of 10% by weight. The resulting solution was cast onto a SUS plate whose surface had been treated with electroplating, and the solvent was evaporated at 25°C to produce a cast film. Square film pieces with a thickness of 100 μm and a length of 50 mm per side were cut from the cast film. The film pieces were stretched 1.5 times at a temperature 20°C higher than the Tg of the resin. Stretching was performed using a stretching machine SS-70 manufactured by Shibayama Scientific Instruments Manufacturing Co., Ltd. The resulting stretched film was subjected to phase difference measurement using an ellipsometer M-220 manufactured by JASCO Corporation.

[0397] From the retardation / phase difference Re, the birefringence value Δn is calculated by the following formula: Δn=|Re / d| Δn: Orientation birefringence Re: Phase difference [nm] d: thickness [nm] The mathematical symbol for birefringence is the refractive index in the stretch direction of the film (n II ) and the refractive index in the direction perpendicular to the stretching direction (n ⊥ ) is expressed by the following formula: Δn=n II -n ⊥ When Δn is positive, it is called positive birefringence, and when Δn is negative, it is called negative birefringence.

[0398] 3.2 Example for the production of homopolycarbonate: Examples 20 to 30: Table 1 below shows the physical properties, i.e. refractive index (n DTable 1 lists the n, Abbe number (ν), glass transition temperature (Tg) and birefringence (Δn) of two comparative homopolycarbonates made from 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene and bisphenol A as the diol component. D The Tg values ​​and Tb values ​​are listed below. Thus, the homopolycarbonates of Examples 20 to 30 are each composed of the structural units of formula (IIa-1) and the structural units of formula (III-1), and the comparative homopolycarbonates are each composed of structural units derived from the monomers 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene and bisphenol A, and the structural units of formula (III-1).

[0399] The n of homopolycarbonates of Examples 20 to 30 shown in Table 1 D The values ​​of n, v, Tg and Δn were calculated from the respective values ​​of the corresponding copolymers derived from the monomers of Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 13 using the Fox equation described above. The preparation of these copolymers and their physical data are described below in Examples 31-40. D Values ​​and Tg values ​​are taken from US Pat. No. 9,360,593.

[0400] [Table 4-1]

[0401] [Table 4-2]

[0402] 3.3 Example for the production of copolycarbonates: Example 31: Copolymers made from monomers of Example 1 and BPEF As raw materials, 3.00 kg (4.83 mol) of 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-diphenyl-phenyl]-1-methyl-ethyl]-2,6-diphenyl-phenoxy]ethanol (see Example 1, hereinafter also referred to as TPBHBPA), 12.01 kg (27.39 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl)fluorene (BPEF), 7.11 kg (33.19 mol) of diphenyl carbonate (DPC), and 15 ml of 2.5 × 10 2 mol / l(7.8×10 -4 An aqueous solution of sodium bicarbonate (1.0 mol) was placed in a 50 liter reactor equipped with a stirrer and a distillation apparatus.

[0403] After flushing the reactor with nitrogen, the reaction mixture was heated to 205°C for 1 hour and stirred at a pressure of 760 torr. After the reaction mixture was completely dissolved, the pressure was reduced to 150 torr in 15 minutes, and then the transesterification reaction was carried out at 205°C and 150 torr for 20 minutes. The reaction mixture was further heated to 240°C with a heating ratio of 37.5°C / hour, and the reaction conditions of 240°C and 150 torr were maintained for 10 minutes. The pressure was then reduced to 120 torr in 10 minutes, and the reaction conditions of 240°C and 120 torr were maintained for 70 minutes. The pressure was then reduced to 100 torr in 10 minutes, and the reaction conditions of 240°C and 100 torr were maintained for 10 minutes. The pressure was further reduced to 1 torr or less in 40 minutes, and the polymerization reaction was carried out at 240°C and 1 torr with stirring for 10 minutes. After the reaction was completed, nitrogen was introduced into the reactor to increase the pressure, and the produced polycarbonate resin was pelletized and removed from the reactor. The properties of the resulting polycarbonate resin are summarized in Table 2 below.

[0404] [Table 5]

[0405] Example 32: Copolymers made from monomers of Example 2 and BPEF As raw materials, 4.70 kg (5.72 mol) of 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-di(naphthalen-1-yl)phenyl]-1-methyl-ethyl]-2,6-di(naphthalen-1-yl)phenoxy]ethanol (see Example 2, hereinafter also referred to as T1NBHBPA), 10.04 kg (22.90 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl)fluorene (BPEF), 6.41 kg (29.90 mol) of diphenyl carbonate (DPC), and 11 ml of 2.5 × 10 -2 An aqueous solution of sodium bicarbonate (2.8×10−4 mol) was placed in a 50-liter reactor equipped with a stirrer and a distillation apparatus.

[0406] After flushing the reactor with nitrogen, the reaction mixture was heated to 205°C for 1 hour and stirred at a pressure of 760 torr. After the reaction mixture was completely dissolved, the pressure was reduced to 150 torr in 15 minutes, and then the transesterification reaction was carried out at 205°C and 150 torr for 20 minutes. The reaction mixture was further heated to 240°C with a heating ratio of 37.5°C / hour, and the reaction conditions of 240°C and 150 torr were maintained for 10 minutes. The pressure was then reduced to 120 torr in 10 minutes, and the reaction conditions of 240°C and 120 torr were maintained for 70 minutes. Thereafter, the pressure was reduced to 100 torr in 10 minutes, and the reaction conditions of 240°C and 100 torr were maintained for 10 minutes. The pressure was further reduced to 1 torr or less in 40 minutes, and the polymerization reaction was carried out at 240°C and 1 torr for 10 minutes with stirring. After the reaction was completed, nitrogen was introduced into the reactor to increase the pressure, and the produced polycarbonate resin was pelletized and removed from the reactor. The properties of the resulting polycarbonate resin are summarized in Table 3.

[0407] [Table 6]

[0408] Example 33: Copolymers made from monomers of Example 3 and BPEF As raw materials, 6.51 kg (7.93 mol) of 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-di(naphthalen-2-yl)phenyl]-1-methyl-ethyl]-2,6-di(naphthalen-2-yl)phenoxy]ethanol (see Example 3, hereinafter also referred to as T2NBHBPA), 8.12 kg (18.51 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl)fluorene (BPEF), 5.83 kg (27.22 mol) of diphenyl carbonate (DPC), and 31 ml of 2.5 × 10 -2 An aqueous solution of sodium bicarbonate (7.8×10−4 mol) was placed in a 50-liter reactor equipped with a stirrer and a distillation apparatus.

[0409] After flushing the reactor with nitrogen, the reaction mixture was heated to 205°C for 1 hour and stirred at a pressure of 760 torr. After the reaction mixture was completely dissolved, the pressure was reduced to 150 torr in 15 minutes, and then the transesterification reaction was carried out at 205°C and 150 torr for 20 minutes. The reaction mixture was further heated to 240°C with a heating ratio of 37.5°C / hour, and the reaction conditions of 240°C and 150 torr were maintained for 10 minutes. The pressure was then reduced to 120 torr in 10 minutes, and the reaction conditions of 240°C and 120 torr were maintained for 70 minutes. Thereafter, the pressure was reduced to 100 torr in 10 minutes, and the reaction conditions of 240°C and 100 torr were maintained for 10 minutes. The pressure was further reduced to 1 torr or less in 40 minutes, and the polymerization reaction was carried out at 240°C and 1 torr for 10 minutes with stirring. After the reaction was completed, nitrogen was introduced into the reactor to increase the pressure, and the produced polycarbonate resin was pelletized and removed from the reactor. The properties of the resulting polycarbonate resin are summarized in Table 4.

[0410] [Table 7]

[0411] Example 34: Copolymer made from monomers of Example 4b and BPEF As raw materials, 8.32 kg (8.16 mol) of 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-di(phenanthren-9-yl)-phenyl]-1-methyl-ethyl]-2,6-di(phenanthren-9-yl)-phenoxy]ethanol (see Example 4b, hereinafter also referred to as T9PNBHBPA), 8.35 kg (19.04 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl)fluorene (BPEF), 6.00 kg (28.01 mol) of diphenyl carbonate (DPC) and 32 ml of an aqueous solution of 2.5×10-2 mol / l (7.8×10-4 mol) of sodium bicarbonate were placed in a 50-liter reactor equipped with a stirrer and a distillation apparatus.

[0412] After flushing the reactor with nitrogen, the reaction mixture was heated to 205°C for 1 hour and stirred at a pressure of 760 torr. After the reaction mixture was completely dissolved, the pressure was reduced to 150 torr in 15 minutes, and then the transesterification reaction was carried out at 205°C and 150 torr for 20 minutes. The reaction mixture was further heated to 240°C with a heating ratio of 37.5°C / hour, and the reaction conditions of 240°C and 150 torr were maintained for 10 minutes. The pressure was then reduced to 120 torr in 10 minutes, and the reaction conditions of 240°C and 120 torr were maintained for 70 minutes. Thereafter, the pressure was reduced to 100 torr in 10 minutes, and the reaction conditions of 240°C and 100 torr were maintained for 10 minutes. The pressure was further reduced to 1 torr or less in 40 minutes, and the polymerization reaction was carried out at 240°C and 1 torr for 10 minutes with stirring. After the reaction was completed, nitrogen was introduced into the reactor to increase the pressure, and the produced polycarbonate resin was pelletized and removed from the reactor. The properties of the resulting polycarbonate resin are summarized in Table 5.

[0413] [Table 8]

[0414] Example 35: Copolymers made from monomers of Example 5 and BPEF As raw material, 9.00 kg (8.61 mol) of 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-di(1,2-dibenzo[b,d]thien-4-yl)-phenyl]-1-methyl-ethyl]-2,6-di(1,2-dibenzo[b,d]thien-4-yl)phenoxy]ethanol (or 2,2'-((propane-2,2-diylbis(2,6-bis(dibenzo[b,d] Thiophen-4-yl)-4,1-phenylene))bis(oxy))bis(ethan-1-ol, see Example 5, hereinafter also referred to as T4DBTBHBPA), 8.81 kg (20.09 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF), 6.33 kg (29.56 mol) of diphenyl carbonate (DPC), and 11 ml of 2.5 × 10 -2 mol / l(2.8×10 -4 An aqueous solution of sodium bicarbonate (1.0 mol) was placed in a 50 liter reactor equipped with a stirrer and a distillation apparatus.

[0415] After flushing the reactor with nitrogen, the reaction mixture was heated to 205°C for 1 hour and stirred at a pressure of 760 torr. After the reaction mixture was completely dissolved, the pressure was reduced to 150 torr in 15 minutes, and then the transesterification reaction was carried out at 205°C and 150 torr for 20 minutes. The reaction mixture was further heated to 240°C with a heating ratio of 37.5°C / hour, and the reaction conditions of 240°C and 150 torr were maintained for 10 minutes. Then, the pressure was reduced to 120 torr in 10 minutes, and the reaction conditions of 240°C and 120 torr were maintained for 70 minutes. Then, the pressure was reduced to 100 torr in 10 minutes, and the reaction conditions of 240°C and 100 torr were maintained for 10 minutes. Then, the pressure was reduced to 1 torr or less in 40 minutes, and the polymerization reaction was carried out at 240°C and 1 torr for 10 minutes. After the reaction was completed, nitrogen was introduced into the reactor to increase the pressure, and the produced polycarbonate resin was pelletized and removed from the reactor. The properties of the resulting polycarbonate resin are summarized in Table 6 below.

[0416] [Table 9]

[0417] Example 36: Copolymers made from monomers of Example 6 and BPEF As raw materials, 7.00 kg (8.30 mol) of 2-[4-[4-(2-hydroxyethoxy)-3,5-di(naphthalen-1-yl)phenyl]sulfonyl-2,6-di(naphthalen-1-yl)phenoxy]ethanol (see Example 6, hereinafter also referred to as T1NBHBPS), 8.50 kg (19.38 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl)fluorene (BPEF), 6.11 kg (28.51 mol) of diphenyl carbonate (DPC), and 11 ml of 2.5 × 10 -2 mol / l(2.8×10 -4 An aqueous solution of sodium bicarbonate (1.0 mol) was placed in a 50 liter reactor equipped with a stirrer and a distillation apparatus.

[0418] After flushing the reactor with nitrogen, the reaction mixture was heated to 205°C for 1 hour and stirred at a pressure of 760 torr. After the reaction mixture was completely dissolved, the pressure was reduced to 150 torr in 15 minutes, and then the transesterification reaction was carried out at 205°C and 150 torr for 20 minutes. The reaction mixture was further heated to 240°C with a heating ratio of 37.5°C / hour, and the reaction conditions of 240°C and 150 torr were maintained for 10 minutes. Then, the pressure was reduced to 120 torr in 10 minutes, and the reaction conditions of 240°C and 120 torr were maintained for 70 minutes. Then, the pressure was reduced to 100 torr in 10 minutes, and the reaction conditions of 240°C and 100 torr were maintained for 10 minutes. Then, the pressure was reduced to 1 torr or less in 40 minutes, and the polymerization reaction was carried out at 240°C and 1 torr for 10 minutes. After the reaction was completed, nitrogen was introduced into the reactor to increase the pressure, and the produced polycarbonate resin was pelletized and removed from the reactor. The properties of the resulting polycarbonate resin are summarized in Table 7 below.

[0419] [Table 10]

[0420] Example 37: Copolymer made from monomers of Example 7 and BPEF As raw materials, 4.50 kg (5.55 mol) of 2-[4-[4-(2-hydroxyethoxy)-3,5-di(naphthalen-1-yl)phenyl]sulfanyl-2,6-di(naphthalen-1-yl)phenoxy]ethanol (or 2,2'-((thiobis(2,6-di(naphthalen-1-yl)-4,1-phenylene))bis(oxy))bis(ethan-1-ol, see Example 7, hereinafter also referred to as T1NBHTDP), 9.73 kg (22.19 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl)fluorene (BPEF), 6.64 kg (28.58 mol) of diphenyl carbonate (DPC), and 11 ml of 2.5 x 10 -2 mol / l(2.8×10 -4 An aqueous solution of sodium bicarbonate (1.0 mol) was placed in a 50 liter reactor equipped with a stirrer and a distillation apparatus.

[0421] After flushing the reactor with nitrogen, the reaction mixture was heated to 205°C for 1 hour and stirred at a pressure of 760 torr. After the reaction mixture was completely dissolved, the pressure was reduced to 150 torr in 15 minutes, and then the transesterification reaction was carried out at 205°C and 150 torr for 20 minutes. The reaction mixture was further heated to 240°C with a heating ratio of 37.5°C / hour, and the reaction conditions of 240°C and 150 torr were maintained for 10 minutes. The pressure was then reduced to 120 torr in 10 minutes, and the reaction conditions of 240°C and 120 torr were maintained for 70 minutes. Thereafter, the pressure was reduced to 100 torr in 10 minutes, and the reaction conditions of 240°C and 100 torr were maintained for 10 minutes. The pressure was further reduced to 1 torr or less in 40 minutes, and the polymerization reaction was carried out at 240°C and 1 torr for 10 minutes. After the reaction was completed, nitrogen was introduced into the reactor to increase the pressure, and the produced polycarbonate resin was pelletized and removed from the reactor. The properties of the resulting polycarbonate resin are summarized in Table 8.

[0422] [Table 11]

[0423] Example 38: Copolymers made from monomers of Example 8 and BPEF As raw materials, 4.24 kg (4.06 mol) of 2-[4-[4-(2-hydroxyethoxy)-3,5-di(phenanthren-9-yl)phenyl]sulfonyl-2,6-di(phenanthren-9-yl)phenoxy]ethanol (see Example 8, hereinafter also referred to as T9PNBHBPS), 10.09 kg (23.02 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (also referred to as BPEF), 5.92 kg (27.62 mol) of diphenyl carbonate (also referred to as DPC), and 11 ml of 2.5 × 10 -2 mol / l(2.7×10 -4 mol(10×10 -6 An aqueous solution of sodium hydrogen carbonate containing 1.0 mol to 1 mol of dihydroxy compound) was placed in a 50-liter reactor equipped with a stirrer and a distillation apparatus.

[0424] After flushing the reactor with nitrogen, the reaction mixture was heated to 205°C for 1 hour and stirred at a pressure of 760 torr. After the reaction mixture was completely dissolved, the pressure was reduced to 150 torr within 15 minutes, and then the transesterification reaction was carried out at 205°C and 150 torr for 20 minutes. Furthermore, the reaction mixture was heated to 240°C with a heating ratio of 37.5°C / hour, and the reaction conditions of 240°C and 150 torr were maintained for 10 minutes. Then, the pressure was reduced to 120 torr in 10 minutes, and the reaction conditions of 240°C and 120 torr were maintained for 70 minutes. Thereafter, the pressure was reduced to 100 torr in 10 minutes, and the reaction conditions of 240°C and 100 torr were maintained for 10 minutes. Further, the pressure was reduced to 1 torr or less in 40 minutes, and the polymerization reaction was carried out at 240°C and 1 torr with stirring for 10 minutes. After the reaction was completed, nitrogen was introduced into the reactor to increase the pressure, and the produced polycarbonate resin was pelletized and removed from the reactor. The properties of the resulting polycarbonate resin are summarized in Table 9.

[0425] [Table 12]

[0426] Example 39: Copolymers made from monomers of Example 10 and BPEF As raw materials, 5.06 kg (4.23 mol) of 2-[4-[4-(2-hydroxyethoxy)-3,5-di(thianthren-1-yl)phenyl]sulfonyl-2,6-di(thianthren-1-yl)phenoxy]ethanol (or 2,2'-((sulfonylbis(2,6-di(thianthren-1-yl)-4,1-phenylene))bis(oxy))bis(ethan-1-ol), see Example 10, hereinafter also referred to as T1TNTBHBPS), 10.51 kg (23.96 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl)fluorene (also referred to as BPEF), 6.19 kg (28.89 mol) of diphenyl carbonate (also referred to as DPC), and 11 ml of 2.5 x 10 -2 mol / l(2.8×10 -4 mol(10×10 -6 An aqueous solution of sodium hydrogen carbonate containing 1.0 mol to 1 mol of dihydroxy compound) was placed in a 50-liter reactor equipped with a stirrer and a distillation apparatus.

[0427] After flushing the reactor with nitrogen, the reaction mixture was heated to 205°C for 1 hour and stirred at a pressure of 760 torr. After the reaction mixture was completely dissolved, the pressure was reduced to 150 torr within 15 minutes, and then the transesterification reaction was carried out at 205°C and 150 torr for 20 minutes. Furthermore, the reaction mixture was heated to 240°C with a heating ratio of 37.5°C / hour, and the reaction conditions of 240°C and 150 torr were maintained for 10 minutes. Then, the pressure was reduced to 120 torr in 10 minutes, and the reaction conditions of 240°C and 120 torr were maintained for 70 minutes. Thereafter, the pressure was reduced to 100 torr in 10 minutes, and the reaction conditions of 240°C and 100 torr were maintained for 10 minutes. Further, the pressure was reduced to 1 torr or less in 40 minutes, and the polymerization reaction was carried out at 240°C and 1 torr with stirring for 10 minutes. After the reaction was completed, nitrogen was introduced into the reactor to increase the pressure, and the produced polycarbonate resin was pelletized and removed from the reactor. The properties of the resulting polycarbonate resin are summarized in Table 10.

[0428] [Table 13]

[0429] Example 40: Copolymer made from monomers of Example 13 and BPEF As raw materials, 9.91 kg (8.44 mol) of 2,2'-(propane-2,2-diylbis{[2,6-di(thianthren-1-yl)-4,1-phenylene]oxy})di(ethan-1-ol) (or 2,2'-((propane-2,2-diylbis(2,6-di(thianthren-1-yl)-4,1-phenylene))bis(oxy))bis(ethan-1-ol)), see Example 13, hereinafter also referred to as T1TNTBHBPA), 8.64 kg (19.70 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (also referred to as BPEF), 6.21 kg (28.99 mol) of diphenyl carbonate (also referred to as DPC), and 11 ml of 2.5 x 10 -2 mol / l(2.8×10 -4 mol(10×10 -6 An aqueous solution of sodium hydrogen carbonate containing 1.0 mol to 1 mol of dihydroxy compound) was placed in a 50-liter reactor equipped with a stirrer and a distillation apparatus.

[0430] After flushing the reactor with nitrogen, the reaction mixture was heated to 205°C for 1 hour and stirred at a pressure of 760 torr. After the reaction mixture was completely dissolved, the pressure was reduced to 150 torr within 15 minutes, and then the transesterification reaction was carried out at 205°C and 150 torr for 20 minutes. Furthermore, the reaction mixture was heated to 240°C with a heating ratio of 37.5°C / hour, and the reaction conditions of 240°C and 150 torr were maintained for 10 minutes. Then, the pressure was reduced to 120 torr in 10 minutes, and the reaction conditions of 240°C and 120 torr were maintained for 70 minutes. Thereafter, the pressure was reduced to 100 torr in 10 minutes, and the reaction conditions of 240°C and 100 torr were maintained for 10 minutes. Further, the pressure was reduced to 1 torr or less in 40 minutes, and the polymerization reaction was carried out at 240°C and 1 torr with stirring for 10 minutes. After the reaction was completed, nitrogen was introduced into the reactor to increase the pressure, and the produced polycarbonate resin was pelletized and removed from the reactor. The properties of the resulting polycarbonate resin are summarized in Table 11.

[0431] [Table 14]

[0432] Example 41: Copolymer made from monomers of Example 15 and BPEF As raw materials, 14.7047 g (0.0335 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl)fluorene (BPEF), 11.1975 g (0.0144 mol) of 2,2'-{[3,3',5,5'-tetra(phenanthren-2-yl)[1,1'-biphenyl]-4,4'-diyl]bis(oxy)}di(ethan-1-ol) (T2NBHB4P) obtained in Example 15, 10.5222 g (0.0491 mol) of diphenyl carbonate (DPC), and 0.4025 × 10 -4 g(0.4771×10 -6 mol) of sodium bicarbonate was placed in a 300-mL reactor equipped with a stirrer and a distillation apparatus.

[0433] After flushing the reactor with nitrogen, the internal pressure was set to 101.3 kPa. The reactor was immersed in an oil bath heated to 200°C to initiate the transesterification reaction. Five minutes after the start of the reaction, stirring of the reaction mixture was started. After 20 minutes, the pressure was reduced from 101.3 kPa to 26.66 kPa over a period of 10 minutes while the reaction mixture was heated to 210°C. The reaction mixture was further heated to reach 220°C within 60 minutes after the start of the reaction. The pressure was reduced to 20.00 kPa over a period of 10 minutes from 80 minutes after the start of the reaction, and then reduced to 0.1 kPa or less while the reaction mixture was heated to 240°C. The conditions of 240°C and 0.1 kPa or less were then maintained for 30 minutes. Nitrogen gas was then introduced to return the pressure to 101.3 kPa, yielding the desired polycarbonate resin. The properties of the resulting resin are summarized in Table 12.

[0434] Example 42: Copolymer made from monomers of Example 14c and BPEF As raw materials, 16.0001 g (0.0365 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl)fluorene (BPEF), 12.1815 g (0.0156 mol) of 2,2'-{[3,3',5,5'-tetra(naphthalen-1-yl)[1,1'-biphenyl]-4,4'-diyl]bis(oxy)}di(ethan-1-ol) (T1NBHB4P) obtained in Example 14c, 11.4484 g (0.0534 mol) of diphenyl carbonate (DPC), and 0.4379 × 10 -4 g(0.5213×10 -6 mol) of sodium bicarbonate was placed in a 300-mL reactor equipped with a stirrer and a distillation apparatus.

[0435] After flushing the reactor with nitrogen, the internal pressure was set to 101.3 kPa. The reactor was immersed in an oil bath heated to 200°C to initiate the transesterification reaction. Five minutes after the start of the reaction, stirring of the reaction mixture was started. After 20 minutes, the pressure was reduced from 101.3 kPa to 26.66 kPa over a period of 10 minutes while the reaction mixture was heated to 210°C. The reaction mixture was further heated to reach 220°C within 60 minutes after the start of the reaction. The pressure was reduced to 20.00 kPa over a period of 10 minutes from 80 minutes after the start of the reaction, and then reduced to 0.1 kPa or less while the reaction mixture was heated to 240°C. The conditions of 240°C and 0.1 kPa or less were then maintained for 30 minutes. Nitrogen gas was then introduced to return the pressure to 101.3 kPa, yielding the desired polycarbonate resin. The properties of the resulting resin are summarized in Table 12.

[0436] Comparative Example: Copolycarbonate Made from BNE and BPEF This comparative copolycarbonate resin was prepared in a manner similar to that described for Example 41 above, except that 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl (BNE) was used as the comonomer instead of T2NBHB4P. The properties of the resulting resin are summarized in Table 12.

[0437] [Table 15]

[0438] The content of low molecular weight compounds (CLWC) listed in Table 12 was calculated using the procedure detailed above based on the GPC data calibrated with polystyrene standards. For example, the CLWC value reported in Table 12 for the resin of Example 14 was calculated from the area of ​​each peak obtained from the GPC diagram of the resin shown in Figure 3 using the above formula. The relevant peak data is summarized in Table 13 and Table 13-2 below. Specifically, the sum of the peak areas of compounds with Mw values ​​less than 1000 was calculated (66697+23135+12863=102695) and related to the total area of ​​all peaks (6318321). Therefore, the content of low molecular weight compounds in the resin of Example 41 was calculated to be 1.6% (102695 / 6318321×100).

[0439] [Table 16]

[0440] Birefringence measurement: FIG. 1 shows the results of measuring the retardation or birefringence of the resins produced in Examples 31, 33 and 34 and a polycarbonate resin derived from bisphenol A.

[0441] FIG. 2 is a partially enlarged portion of FIG. 1 for the retardation or birefringence of the polymers of Examples 31, 33 and 34.

[0442] In FIG. 1, "TPBHBPA / BPEF" represents the copolycarbonate of Example 31 (prepared from the monomers TPBHBPA and BPEF in a molar ratio of 15:85), "T2NBHBPA / BPEF" represents the copolycarbonate of Example 33 (prepared from the monomers T2NBHBPA and BPEF in a molar ratio of 30:70), "T9PNBHBPA / BPEF" represents the copolycarbonate of Example 34 (prepared from the monomers T9PNBHBPA and BPEF in a molar ratio of 30:70), and "BPA-PC" represents the homopolycarbonate prepared from bisphenol A (BPA) as the diol monomer (compare the last entry in Table 1).

[0443] Figure 1 confirms that TPBHBPA, T2NBHBPA and T9PNBHBPA provide polycarbonates with extremely low absolute values ​​of positive or negative birefringence. These properties have not been found in prior art materials, making TPBHBPA, T2NBHBPA and T9PNBHBPA particularly useful as optical materials.

Claims

1. Compounds of formula (I): 【Chemical 1】 (In the formula, X is a single bond, O, N—(C １ -C ４ )-alkyl, N-Ar １ , C.R. ５ R ６ , S, S(O) and SO ２ selected from the group consisting of: Z １ and Z ２ is hydrogen, -Alk-OH, -CH ２ -Ar ２ -CH ２ -OH, -Alk'-C(O)OR ｘ , -CH ２ -Ar ２ -C(O)OR ｘ and —C(O)—Ar ２ -C(O)OR ｘ (R ｘ is hydrogen, phenyl, benzyl and C １ -C ４ -alkyl); R １ and R ２ represents a monocyclic or polycyclic aryl having 6 to 26 carbon atoms as ring members and a monocyclic or polycyclic hetaryl having a total of 5 to 26 ring atoms, where one, two, three or four of the hetaryl ring atoms are selected from nitrogen, sulfur and oxygen, and the remaining hetaryl ring atoms are carbon atoms. The monocyclic or polycyclic aryl and monocyclic or polycyclic hetaryl may be unsubstituted or may have one, two, three or four R Ａｒ independently selected from the group consisting of: R ３ and R ４ represents hydrogen, monocyclic or polycyclic aryl having 6 to 26 carbon atoms as ring members, and monocyclic or polycyclic hetaryl having a total of 5 to 26 ring atoms, where one, two, three or four of the hetaryl ring atoms are selected from nitrogen, sulfur and oxygen, and the remaining hetaryl ring atoms are carbon atoms. The monocyclic or polycyclic aryl and monocyclic or polycyclic hetaryl may be unsubstituted or may have one, two, three or four R Ａｒ independently selected from the group consisting of: R ５ is hydrogen and C １ -C ４ - selected from the group consisting of alkyl; R ６ is hydrogen and C １ -C ４ - selected from the group consisting of alkyl; Ar １ represents a monocyclic or polycyclic aryl having 6 to 26 carbon atoms as ring members and a monocyclic or polycyclic hetaryl having a total of 5 to 26 ring atoms, where one, two, three or four of the hetaryl ring atoms are selected from nitrogen, sulfur and oxygen, and the remaining hetaryl ring atoms are carbon atoms. The monocyclic or polycyclic aryl and monocyclic or polycyclic hetaryl may be unsubstituted or may have one, two, three or four R Ａｒ a group; Ar ２ is selected from the group consisting of phenylene, naphthylene, and biphenylylene; Alk is C ２ -C ４ -alkanediyl; Alk' is C １ -C ４ -alkanediyl; R Ａｒ is R, OR, CH ｎ R ３－ｎ , N.R. ２ and CH=CHR′, and R Ａｒ When there are two or more, they may be the same or different; R is selected from the group consisting of methyl, ethyl, phenyl, naphthyl, phenanthrenyl, and triphenylenyl, wherein phenyl, naphthyl, phenanthrenyl, and triphenylenyl are unsubstituted or substituted with 1, 2, 3, or 4 identical or different R″ groups; R' is selected from hydrogen, methyl, phenyl and naphthyl, wherein phenyl and naphthyl are unsubstituted or substituted with 1, 2, 3 or 4 identical or different R" groups; R'' is phenyl, OCH ３ , C.H. ３ , N(CH ３ ) ２ and C(O)CH ３ selected from the group consisting of: n is 0, 1 or 2. However, R ３ and R ４ are both hydrogen, R １ and R ２ (Both are not phenyl).

2. The compound according to claim 1, wherein formula (I) is represented by formula (Ia): 【Chemistry 2】

3. X is a single bond, O, N-methyl, N-ethyl, N-isopropyl, N-phenyl, N-naphthyl, N-phenanthryl, CH ２ , C(CH ３ ) ２ , CH(CH ３ ), S and SO ２ In particular, a single bond, O, CH ２ , C(CH ３ ) ２ , CH(CH ３ ), S and SO ２ 3. The compound of claim 1 or claim 2, selected from the group consisting of:

4. Z １ and Z ２ is selected from hydrogen, 2-hydroxyethyl, methoxycarbonyl-methyl, hydroxymethyl-phenyl-methyl, hydroxymethyl-naphthyl-methyl, hydroxymethyl-biphenylyl-methyl, methoxycarbonyl-phenyl-methyl and methoxycarbonyl-naphthyl-methyl, in particular from hydrogen, 2-hydroxyethyl, methoxycarbonyl-methyl, (4-(hydroxymethyl)phenyl)methyl, (3-(hydroxymethyl)phenyl)methyl, (4-(hydroxymethyl)-1-naphthyl)methyl, (5-(hydroxymethyl)-1-naphthyl)methyl, (6-(hydroxymethyl)-2-naphthyl)methyl, 4'-(hydroxymethyl)-1,1'-biphenylyl-4-methyl, (4-(methoxycarbonyl)phenyl)methyl, (3-(methoxycarbonyl)phenyl)methyl, (4-(methoxycarbonyl)-1-naphthyl)methyl and (6-(methoxycarbonyl)-2-naphthyl)methyl.

5. R １ and R ２ phenyl, naphthyl, 1,2-dihydroacenaphthylenyl, biphenylyl, fluorenyl, 11H-benzo[a]fluorenyl, 11H-benzo[b]fluorenyl, 7H-benzo[c]fluorenyl, phenanthrenyl, benzo[c]phenanthrenyl, pyrenyl, chrysenyl, picenyl, triphenylenyl, benzo[b]furanyl, dibenzo[b,d]furanyl, naphtho[1,2-b]furanyl, naphtho[2,3-b]furanyl, naphtho[2,1-b]furanyl, benzo[b]naphtho[1,2-d]furanyl, benzo[b]naphtho[2,3-d] ]furanyl, benzo[b]naphtho[2,1-d]furanyl, 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, tribenzo[b,d,f]oxepinyl, 2H-naphtho[1,8-d,e][1,3]dioxinyl, dinaphtho[2,3-b:2',3'-d]furanyl, oxantrenyl, benzo[a]oxantrenyl, benzo[b]oxantrenyl, benzo[b]thienyl, dibenzo[b,d]thi enyl, 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, benzo[1,2-b:4,3-b']dithienyl, benzo[1,2-b:6,5-b']dithienyl, benzo[1,2-b:5,4-b']dithienyl, benzo[1,2-b:4,5-b']dithienyl, 9H-thioxanthenyl, 6H-dibenzo[b,d]thiopyranyl, 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, dibenzo[b,d]thiepinyl, dibenzo[b,f]thiepinyl, 5H-phenanthro[4,5-b,c,d]thiopyranyl, tribenzo[b,d,f]thiepinyl, 2,5-dihydronaphtho[1,8-b,c:4,5-b',c']dithienyl, 2,6-dihydronaphtho[1,8-b,c:5,4-b',c']dithienyl, tribenzo[a,c,i]thianthrenyl, benzo[b]naphtho[1,8-e,f][1,4]dithiepinyl, dinaphtho[2,3-b:2',3'-d]thiepinyl The compound according to claim 1 or claim 2, wherein the thienyl is independently selected from the group consisting of 5H-phenanthro[1,10-b,c]thienyl, 5H-phenanthro[1,10-c,b]thienyl, 7H-phenanthro[1,10-c,b]thienyl, dibenzo[d,d']benzo[1,2-b:4,5-b']dithienyl and dibenzo[d,d']benzo[1,2-b:5,4-b']dithienyl.

6. R １ and R ２ is independently selected from the group consisting of phenyl, naphthyl, 1,2-dihydroacenaphthylenyl, phenanthrenyl, pyrenyl, triphenylenyl, benzo[b]furanyl, dibenzo[b,d]furanyl, benzo[b]thienyl, dibenzo[b,d]thienyl, and thianthrenyl.

7. R １ and R ２ 3. A compound according to claim 1 or claim 2, wherein:

8. R ３ and R ４ monocyclic or polycyclic aryl having 6 to 26 carbon atoms as ring atoms and monocyclic or polycyclic hetaryl having a total of 5 to 26 ring atoms, where 1, 2, 3 or 4 of the hetaryl ring atoms are selected from nitrogen, sulfur and oxygen, and the remaining hetaryl ring atoms are carbon atoms. The monocyclic or polycyclic aryl and monocyclic or polycyclic hetaryl may be unsubstituted or may have 1, 2, 3 or 4 R Ａｒ 3. The compound of claim 1 or claim 2, wherein the compound is selected from the group consisting of:

9. R ３ and R ４ phenyl, naphthyl, 1,2-dihydroacenaphthylenyl, biphenylyl, fluorenyl, 11H-benzo[a]fluorenyl, 11H-benzo[b]fluorenyl, 7H-benzo[c]fluorenyl, phenanthrenyl, benzo[c]phenanthrenyl, pyrenyl, chrysenyl, picenyl, triphenylenyl, benzo[b]furanyl, dibenzo[b,d]furanyl, naphtho[1,2-b]furanyl, naphtho[2,3-b]furanyl, naphtho[2,1-b]furanyl, benzo[b]naphtho[1,2-d]furanyl, benzo[b]naphtho[2,3-d] ]furanyl, benzo[b]naphtho[2,1-d]furanyl, 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, tribenzo[b,d,f]oxepinyl, 2H-naphtho[1,8-d,e][1,3]dioxinyl, dinaphtho[2,3-b:2',3'-d]furanyl, oxantrenyl, benzo[a]oxantrenyl, benzo[b]oxantrenyl, benzo[b]thienyl, dibenzo[b,d]thi enyl, 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, benzo[1,2-b:4,3-b']dithienyl, benzo[1,2-b:6,5-b']dithienyl, benzo[1,2-b:5,4-b']dithienyl, benzo[1,2-b:4,5-b']dithienyl, 9H-thioxanthenyl, 6H-dibenzo[b,d]thiopyranyl, 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, dibenzo[b,d]thiepinyl, dibenzo[b,f]thiepinyl, 5H-phenanthro[4,5-b,c,d]thiopyranyl, tribenzo[b,d,10. The compound of claim 8, wherein the benzo[b]naphtho[1,8-e,f][1,4]dithiepinyl, dinaphtho[2,3-b:2',3'-d]thienyl, 5H-phenanthro[1,10-b,c]thienyl, 7H-phenanthro[1,10-c,b]thienyl, dibenzo[d,d']benzo[1,2-b:4,5-b']dithienyl, and dibenzo[d,d']benzo[1,2-b:5,4-b']dithienyl. ,

10. R ３ and R ４ is independently selected from the group consisting of phenyl, naphthyl, 1,2-dihydroacenaphthylenyl, phenanthrenyl, pyrenyl, triphenylenyl, benzo[b]furanyl, dibenzo[b,d]furanyl, benzo[b]thienyl, dibenzo[b,d]thienyl, and thianthrenyl.

11. R １ , R ２ , R ３ and R ４ 3. A compound according to claim 1 or claim 2, wherein:

12. Formula (I) is represented by formula (Ia-1), wherein Z is Z １ and Z ２ 3. The compound of claim 1 or claim 2, wherein: 【Chemistry 3】

13. R ｙ , X and Z are as defined in row 1 of Table A', and R ｙ is the substituent R １ , R ２ , R ３ and R ４ 13. The compound according to claim 12, wherein: 【Table 1-1】 【Table 1-2】 【Table 1-3】 【Table 1-4】 【Table 1-5】 【Table 1-6】 【Table 1-7】

14. Formula (I) is represented by formula (Ia-2), wherein Z is Z １ and Z ２ 3. The compound of claim 1 or claim 2, wherein: 【Chemistry 4】

15. R ｙ , X and Z are as defined in row 1 of Table B, and R ｙ is the substituent R １ , R ２ , R ３ and R ４ 13. The compound according to claim 12, wherein: 【Table 2-1】 【Table 2-2】

16. A thermoplastic resin containing a structural unit represented by the following formula (II): 【Chemistry 5】 (In the formula, # represents the point of attachment to the adjacent structural unit; and Z １ａ and Z ２ａ are respectively Z １ Or Z ２ is hydrogen, by replacing the hydrogen with a single bond, or by Z １ Or Z ２ If is not hydrogen, then Z １ Or Z ２ -OH group or -OR ｘ The Z group of formula (I) can be replaced with an oxo (—O—) unit. １ or Z ２ Derived from, and Z １ , Z ２ , X, R １ , R ２ , R ３ and R ４ is as defined in claim 1)

17. The thermoplastic resin according to claim 16, wherein formula (II) is represented by formula (IIa): 【Chemistry 6】

18. Formula (IIa) is represented by formula (IIa-1), wherein Z ａ is Z in claim 16 １ａ and Z ２ａ 18. The thermoplastic resin of claim 17, wherein: 【Chemistry 7】

19. Formula (IIa) is represented by formula (IIa-2), wherein Z ａ is Z in claim 16 １ａ and Z ２ａ 18. The thermoplastic resin of claim 17, wherein: 【Chemistry 8】

20. The structural unit of formula (II) is bonded to one of the structures represented by the following formulas (III-1) to (III-5), wherein Z １ and Z ２ is hydrogen, -Alk-OH and -CH ２ -Ar ２ -CH ２ The thermoplastic resin according to claim 16 or 17, wherein the group is selected from —OH. 【Chemistry 9】 (In the formula, # indicates the point of attachment to the adjacent structural unit)

21. 18. The thermoplastic resin according to claim 16 or 17, selected from copolycarbonate resins, copolyestercarbonate resins and copolyester resins, which contain structural units of formula (V) in addition to structural units of formula (II). #-O-R ｚ -A １ -R ｚ -O-# (V) (In the formula, # represents the point of attachment to the adjacent structural unit; A １ is a polycyclic group having at least two benzene rings, which may be linked by A and / or may be directly fused to each other and / or may be fused to a non-benzene carbocyclic ring; A １ is unsubstituted or 1, 2 or 3 R ａａ Group (R ａａ is halogen, C １ -C ６ -Alkyl, C ５ -C ６ -substituted with aryl, ... A is a single bond, O, C=O, S, SO ２ , C.H. ２ , CH-Ar, CAr ２ , CH(CH ３ ), C(CH ３ ) ２ and a group of formula (A'); 【Chemistry 10】 During the ceremony, Q is a single bond, O, NH, C=O, CH ２ or CH═CH; R ７ａ , R ７ｂ are each independently hydrogen, fluorine, CN, R, OR, CH ｋ R ３－ｋ , N.R. ２ , C(O)R and C(O)NH ２ wherein R is as defined in claim 1 and k is 0, 1, 2 or 3; ＊ represents the point of attachment to the benzene ring; Ar is selected from the group consisting of monocyclic or polycyclic aryl having 6 to 26 carbon atoms as ring atoms and monocyclic or polycyclic hetaryl having a total of 5 to 26 ring atoms, wherein 1, 2, 3, or 4 of the hetaryl ring atoms are selected from nitrogen, sulfur, and oxygen, and the remaining hetaryl ring atoms are carbon atoms, and Ar is unsubstituted or substituted with 1, 2, or 3 R ａｂ Group (R ａｂ is halogen, phenyl and C １ -C ４ -substituted with (selected from the group consisting of -alkyl); R ｚ is a single bond, Alk １ , O-Alk ２ -, O-Alk ２ -[O-Alk ２ -] ｐ - or O-Alk ３ -C(O)- (O is A １ ) and p is an integer from 1 to 10; Alk １ is C １ -C ４ -alkanediyl; Alk ２ is C ２ -C ４ -alkanediyl; and Alk ３ is C １ -C ４ -alkanediyl)

22. The thermoplastic resin according to claim 21, wherein the structural unit of formula V is represented by one of the following formulas V-1 to V-6: 【Chemistry 11】 (In the formula, a and b are 0, 1, 2 or 3, in particular 0 or 1; c and d are 0, 1, 2, 3, 4 or 5, in particular 0 or 1; e and f are 0, 1, 2, 3, 4 or 5, in particular 0 or 1; R ｚ , R ａａ , R ａｂ , R ７ａ and R ７ｂ is as defined in formula (IV)

23. The molar ratio of the structural unit of formula (II) is 1 to 70 mol% based on the total molar amount of the structural units of formulas (II) and (V), and the molar ratio of the structural unit of formula (V) is 30 to 99 mol% based on the total molar amount of the structural units of formulas (II) and (V). The thermoplastic resin according to claim 21.

24. 18. The thermoplastic resin according to claim 16 or 17, having a refractive index of 1.640 or greater.

25. 18. The thermoplastic resin according to claim 16 or 17, having an Abbe number of 24 or less.

26. The thermoplastic resin according to claim 16 or 17, having a glass transition temperature (Tg) of 90 to 185°C.

27. 18. Thermoplastic resin according to claim 16 or 17, having a weight average molecular weight of 10,000 to 50,000 as determined by gel permeation chromatography against polystyrene standards.

28. The thermoplastic resin according to claim 16 or 17, wherein the thermoplastic resin comprises a low molecular weight compound having a molecular weight (Mw) of less than 1000, and the content of the low molecular weight compound in the thermoplastic resin (CLWC) is in the range of 0.3 wt% to 7.0 wt% based on the total weight of the thermoplastic resin, and the CLWC is represented by the following formula: [Equation 1]

29. An optical element made of the thermoplastic resin according to claim 16 or 17.

30. 17. Use of a compound of formula (I) according to claim 1 as a monomer for a thermoplastic resin according to claim 16.

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