Dibenzothiophene-substituted aromatic compounds and thermoplastic resins prepared from them.

Abstract

The present invention relates to compounds of formula (I), wherein X 1 and X 2 are, independently of each other, a bond or a C1-C5-alkanediyl; Z 1 and Z 2 are, independently of each other, OH or C(O)OR x and R x is selected from the group consisting of hydrogen, C1-C4-alkyl, phenyl and benzyl; R a , R b , R c and R d The present invention also relates to the use of structural units represented by formula (III) (wherein # represents the point of attachment to the adjacent structural unit; Z 11 is a bridging group -O- or -C(O)-O-, and the carbon atom of the -C(O)-O- group is X 1 Z 12 is a bridging group -O- or -C(O)-O-, and the carbon atom of the -C(O)-O- group is X 2 It is bonded to X 1 , X 2 , R a , R b , R c and R d is as defined above). [Formula 1] TIFF2026508450000056.tif12799

Description

[Technical Field]

[0001] The present invention relates to the use of aromatic compounds of formula (I) as defined below, which have one or two dibenzothiophene groups and two further directly or indirectly attached hydroxyl or carboxyl (carboxylate) groups, as monomers for preparing polymers, especially thermoplastics, in particular polycarbonates, polyesters or polyestercarbonates, to polymers containing such monomers in polymerized (polycondensed) form, especially thermoplastics, in particular polycarbonates, polyesters or polyestercarbonates, and to certain aromatic compounds of formula (I) themselves. [Background technology]

[0002] Optical devices, such as optical lenses, made from optical resins instead of optical glass have the advantage of being mass-produced by injection molding. Recently, optical resins, particularly transparent polycarbonate resins, have been frequently used in the manufacture of camera lenses. In this regard, resins with higher refractive indices are highly desirable because they allow for the reduction of the size and weight of the final product. In general, using optical materials with higher refractive indices allows for the same optical power to be achieved with a lens element having a smaller surface curvature, thereby reducing the amount of aberrations that occur at this surface. As a result, it is possible to reduce the number of lenses, decrease the lens's decentering sensitivity, and / or reduce the lens thickness, thereby achieving weight reduction.

[0003] WO 2010 / 004877 discloses a polymerizable composition containing a plurality of organic layers, wherein at least one of the organic layers independently contains a compound of formula (1).

[0004] [ka] and a compound of formula (2)

[0005] [ka] The reference relates to an organic electroluminescent device containing the compound. X in formula (1) may be, in particular, a phenylene or naphthylene group, which is unsubstituted. Furthermore, the reference does not disclose polymers containing such compounds.

[0006] JP 2019-016809 A relates to a method for sublimating and purifying a host material for an organic electroluminescent device, and a host material purified by the sublimation and purification method. In particular, a compound of formula (4-2)

[0007] [ka] are listed as suitable host materials. f is 1 to 4, and R8 can be various substituents, but at least one of R8 is a carbazolyl group or a dibenzothiophenyl group of formula (5):

[0008] [ka] (wherein X is N or S) Other possible meanings of R8 are halogen, alkoxy, cyano, nitro, alkyl, aryl, heterocyclic groups, and the substituent of general formula (5). There is no mention of hydroxyl- or carboxyl (carboxylate)-containing substituents R8, nor of such compounds being suitable as monomers for preparing polycarbonates or polyesters.

[0009] JP 1997-071642 (JP 09-071642 A) discloses a compound useful as an electrophotographic photoreceptor, which comprises a structural unit of formula (I):

[0010] [ka] (In the formula, Ar 1 , Ar 3 , Ar 4 , Ar 5 and Ar6 are independently a substituted or unsubstituted arylene group, and Ar 2 and Ar 7 are independently a substituted or unsubstituted aryl group. The polycarbonate resin further comprises a structural unit represented by general formula (II):

[0011] [ka] wherein X may in particular be a divalent aromatic group. When X has this meaning, suitable diols include, among many others, 3,6-dihydroxydibenzothiophene.

[0012] WO 2022 / 245079 discloses a repeating unit of the formula:

[0013] [ka] (wherein Ar1 and Ar2 may particularly be heteroaryl groups, X1 to X4 are O or S, Z1 and Z2 are particularly alkylene groups, and a and b are integers of 1 to 10). The present invention relates to a polymer resin, particularly a polyester or polycarbonate, comprising 2,5-di-(dibenzothiophen-2-yl)-benzene-1,4-diol, which is used as an intermediate in the synthesis of a specific monomer (monomer 5) used to prepare the polymer resin. However, 2,5-di-(dibenzothiophen-2-yl)-benzene-1,4-diol itself is not used as a monomer.

[0014] Chinese Patent No. 110790771 relates to compounds based on dithioindolefluorene units and their use in organic light-emitting diodes. In the multi-step synthesis of such dithioindolefluorenes, dimethyl 2,5-di(dibenzothiophen-2-yl)benzene-1,4-dicarboxylate is listed as an intermediate.

[0015] Despite advances in the field of optical resins, there remains a need for monomers for preparing optical resins, particularly polycarbonate and polyester resins, that provide a high refractive index and are therefore useful in the manufacture of optical devices, particularly lenses. Apart from that, the monomers should not impair other optical properties of the optical resins, such as low Abbe number, high transparency, and low birefringence. Furthermore, the monomers should be easy to prepare. Furthermore, the resins obtained from these monomers, particularly polyesters and polycarbonates, should have good moisture and heat resistance and glass transition temperatures suitable for injection molding. Summary of the Invention

[0016] These objects are achieved by the monomeric compounds of formula (I), which are suitable for preparing polymers, more precisely thermoplastics, in particular polycarbonates, polyesters and their mixed forms (i.e. polyestercarbonates), which are useful for preparing optical devices.

[0017] The present invention therefore relates to the use of compounds of formula (I) as monomers, in particular for preparing polymers, in particular thermoplastics, more particularly thermoplastics selected from the group consisting of polycarbonates, polyesters and polyestercarbonates, in particular polycarbonates and polyesters:

[0018] [ka] (In the formula, X 1 and X 2 are, independently of each other, a bond or C1-C5-alkanediyl; Z 1 and Z 2 are, independently of each other, OH or C(O)OR x and R xis selected from the group consisting of hydrogen, C1-C4-alkyl, phenyl and benzyl; R a , R b , R c and R d one or two of which are dibenzothiophene groups of formula (II):

[0019] [ka] where # indicates the point of attachment to the rest of the molecule. and; R a , R b , R c and R d The other two or three are hydrogen, halogen, C2-C3-alkynyl, CN, R, S(O) k each independently selected from the group consisting of R, NHR, NR2, OR, and C(O)R; each R is independently selected from the group consisting of C1-C4-alkyl, phenyl, benzyl, and naphthyl; k is 0, 1, or 2; or R c and R d may be joined together with the carbon atoms to which they are attached to form a fused benzene ring (in which case, of course, R a and R b is a dibenzothiophene group of formula (II), and R a and R b When only one of the groups is a dibenzothiophene group of formula (II), the other group is hydrogen, halogen, C2-C3-alkynyl, CN, R, S(O) k R, NHR, NR2, OR and C(O)R]).

[0020] The present invention further relates to compounds (I) as defined above per se, with the exception of the following compounds: dimethyl 2,5-di(dibenzothiophen-2-yl)benzene-1,4-dicarboxylate, i.e. the compound of the following formula:

[0021] [ka] ; and 2,5-di(dibenzothiophen-2-yl)benzene-1,4-diol, i.e. the compound of the following formula:

[0022] [ka]

[0023] Compound (I) (including the two previously disclaimed in the context of compound (I) according to the present invention) is a suitable monomer for preparing polymers such as polyesters, polycarbonates and their mixed forms.

[0024] The present invention therefore also relates to polymers, in particular thermoplastics, derived from compound (I) and comprising structural units of formula (III):

[0025] [ka] (In the formula, # represents the point of attachment to the adjacent structural unit; Z 11 is a bridging group -O- or -C(O)-O-, and the carbon atom of the -C(O)-O- group is X 1 is bound to; Z 12 is a bridging group -O- or -C(O)-O-, and the carbon atom of the -C(O)-O- group is X 2 is bound to; X 1 , X 2 , R a , R b , R c and R d is as defined above in the context of the use according to the invention of compound (I).

[0026] The present invention also relates to optical devices made from said thermoplastic resins. DETAILED DESCRIPTION OF THE INVENTION

[0027] definition The central phenyl ring (i.e., R a , R b , R c and R d Depending on the substitution on the central phenyl ring (the phenyl ring bearing the R group), compound (I) may have a carbon ring atom of the central phenyl ring and a R a , R b , R c and R d Axial chirality may be present due to the possibility that rotation along the bond between one or more of the groups may be restricted. a and R b Both or R c and R d are sterically demanding radicals of formula (II), or more generally, when a substituent ortho to the (II) group is sterically demanding to the extent that it prevents rotation about the bond between the central phenyl ring and the (II) group (e.g., as in the case of a tert-butyl group). a , R b , R c and R d One or more of R, S(O) k R, NHR, NR2, OR or C(O)R, where R is sec-butyl (stereocenter is the 2-carbon atom of sec-butyl), or Z 1 and Z 2 One or both of the following are C(O)OR x and R x is sec-butyl, or the linking group X 1 and X 2is a non-linear C3-C5-alkanediyl having a stereocenter (for example, the 2-carbon atom of propane-2,3-diyl), compound (I) may contain one or more stereocenters. In these cases, the compounds of formula (I) can exist in the form of pure stereoisomers (pure enantiomers or pure diastereomers) or in the form of mixtures of stereoisomers, including racemic mixtures. The present invention relates to both pure stereoisomers of the compounds of formula (I), e.g., pure enantiomers or pure diastereomers, and mixtures of stereoisomers, including racemic and non-racemic mixtures of enantiomers, as well as mixtures of diastereomers (if stereoisomers exist, of course).

[0028] In the present context, the term compound (I) refers to the form of the compound obtained using a non-stereoselective method for its production, when it is not defined as a specific stereoisomer or a mixture of specific stereoisomers, despite the presence of axial asymmetry and / or one or more stereocenters. However, the term is also used when it is not necessary or feasible to specify the stereochemistry of compound (I) in more detail.

[0029] In the context of the present invention, halogen denotes fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine or bromine.

[0030] C1-C4-Alkyl is a linear or branched saturated aliphatic hydrocarbon radical containing 1, 2, 3 or 4 carbon atoms. Examples are methyl, ethyl, n-propyl, 2-propyl (isopropyl), n-butyl, 2-butyl (1-methylpropyl; sec-butyl), (sec-butyl), 2-methylpropyl (isobutyl) or 1,1-dimethylethyl (tert-butyl). C1-C6-Alkyl is a linear or branched saturated aliphatic hydrocarbon radical containing 1 to 6 carbon atoms. Examples, in addition to those listed for C1-C4-alkyl, are n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl or 1-ethyl-2-methylpropyl.

[0031] C2-C3-Alkynyl is ethynyl, propyn-1-yl or propyn-3-yl (propargyl).

[0032] C1-C5-alkanediyl, also called "C1-C5-alkylene", is a divalent saturated aliphatic hydrocarbon group having 1, 2, 3, 4 or 5 carbon atoms. Examples are the methylene group (CH), straight-chain C1-C5-alkanediyls such as 1,2-ethanediyl (ethylene; CH2CH2), 1,3-propanediyl (n-propylene; CH2CH2CH2), 1,4-butanediyl (n-butylene; CH2CH2CH2CH2) and 1,5-pentanediyl (n-pentylene; CH2CH2CH2CH2), but also 1,1-ethanediyl (-CH(CH3)-, 1-methyl-1,2-ethanediyl (propane-2,3-diyl), 1-methyl-1,2-propanediyl, 2-methyl-1,2-propanediyl, 2-methyl-1,3-propanediyl, 1, Also branched C2-C5-alkanediyl / alkylene such as 3-butanediyl. C1-C4-alkanediyl, also called "C1-C4-alkylene", is a divalent saturated aliphatic hydrocarbon radical having 1, 2, 3 or 4 carbon atoms. Examples are those listed above for C1-C5-alkanediyl, excluding 1,5-pentanediyl. C2-C4-alkanediyl, also called "C2-C4-alkylene", is a divalent saturated aliphatic hydrocarbon radical having 2, 3 or 4 carbon atoms. Examples are those listed above for C1-C4-alkanediyl, excluding methylene.

[0033] C5-C6-cycloalkyl is cyclopentyl or cyclohexyl.

[0034] In the context of this invention, the term "monocyclic aryl" refers in particular to a monovalent aromatic monocyclic group such as phenyl.

[0035] In the context of this invention, the term "monocyclic hetaryl" refers to a monovalent heteroaromatic monocyclic group, i.e., a heteroaromatic monocyclic ring attached to the rest of the molecule by a single covalent bond, the ring atoms being part of a conjugated π-electron system, and the heteroaromatic monocyclic ring having 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 heterocyclic 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, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, pyridyl (= pyridinyl), pyrazinyl, pyridazinyl, pyrimidinyl and triazinyl.

[0036] In the context of this 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 rest of the molecule by a single covalent bond, wherein the polycyclic arene is: (i) aromatic polycyclic hydrocarbons, i.e., fully unsaturated polycyclic hydrocarbons in which each carbon atom is part of a conjugated π-electron system; (ii) a polycyclic hydrocarbon 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 covalently bonded to each other or directly fused to each other and / or fused to a saturated or unsaturated 4- to 10-membered monocyclic or bicyclic hydrocarbon ring.

[0037] Monocyclic or polycyclic aryls have 6 to 26, usually 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, particularly 6 to 20 carbon atoms, especially 6, 10, 12, 13, 14, 16, 17 or 18 carbon atoms. Polycyclic aryls typically have 10 to 26, especially 10 to 20 carbon atoms, especially 10, 12, 13, 14, 16, 17 or 18 carbon atoms as ring atoms.

[0038] In this context, examples of polycyclic aryls having two, three, or four phenyl rings bonded to one another via single bonds include biphenylyl and terphenylyl. Examples of polycyclic aryls having two, three, or four phenyl rings directly fused to one another include naphthyl, anthracenyl, phenanthrenyl, pyrenyl, triphenylenyl, chrysenyl, and benzo[c]phenanthrenyl. Examples of polycyclic aryls having two, three, or four phenyl rings fused to a saturated or unsaturated 4- to 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-tetrahydrophenanthrenyl, and benzo[c]phenanthrenyl. These include 9,10-dihydro-9,10[1',2']-benzenoanthracenyl, dibenzo[a,e][8]annulenyl, 9,9'-spirobi[9H-fluoren]yl, and spiro[1H-cyclobut[de]naphthalene-1,9'-[9H]fluoren]yl.

[0039] Examples of 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, biphenylenyl, 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']benzanthracenyl, 9,9'-spirobi-9H-fluorenyl, and spiro[1H-cyclobuta[de]naphthalene-1,9'-[9H]fluorenyl]yl.

[0040] In the context of the present invention, the term "monocyclic or polycyclic hetaryl" refers to a monovalent heteroaromatic monocyclic group or a monovalent heteroaromatic polycyclic group as defined herein, i.e., a polycyclic hetaryl attached to the rest 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 the heteroaromatic monocycles as defined above, wherein the aromatic rings of the polycyclic hetarene are covalently bonded to each other and / or directly fused to each other and / or fused to a saturated or unsaturated 4- to 10-membered monocyclic or bicyclic hydrocarbon ring; or (ii) Polycyclic hetaranes are 5, 6, 7 or 8 saturated or partially or fully unsaturated ring-type hetaranes having 1, 2 or 3 heteroatoms selected from oxygen, sulfur and nitrogen as ring atoms, such as 2H-pyran, 4H-pyran, thiopyran, 1,4-dihydropyridine, 4H-1,4-oxazine, 4H-1,4-thiazine, 1,4-dioxine, oxepin, thiepin, dioxin, dithiin, dioxepin, dithiepin, dioxocine, dithiocine, etc. and at least one, e.g., 1, 2, 3, 4, or 5, aromatic rings selected from phenyl and heteroaromatic monocycles as defined above, wherein at least one aromatic ring is directly fused to a saturated or partially unsaturated 5- to 8-membered heterocyclic ring, and the aromatic rings of the polycyclic hetarene are covalently bonded to each other or are directly fused to each other and / or are fused to a saturated or unsaturated 4- to 10-membered monocyclic or bicyclic hydrocarbon ring.

[0041] Monocyclic or polycyclic hetaryls have 5 to 26, usually 5 to 24, especially 5 to 20 ring atoms, including 1, 2, 3, or 4 atoms selected from nitrogen, sulfur, and oxygen, with the remaining ring atoms being carbon atoms. Polycyclic hetaryls generally have 9 to 26, usually 9 to 24, especially 9 to 20 ring atoms, including 1, 2, 3, or 4 atoms selected from nitrogen, sulfur, and oxygen, with the remaining ring atoms being carbon atoms.

[0042] Examples of polycyclic hetaryls include 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, fentiazinyl, benzo[b][1,5]naphthyridinyl, cinnolinyl, 1,5-naphthyridinyl, 1,8-naphthyridinyl, phenylpyrrolyl, naphthylpyrrolyl, dipyridyl, phenylpyridyl, naphthylpyridyl, pyrido[4,3-b]indolyl, pyrido[3,2-b]indolyl Doryl, 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, benzo[b]naphtho[1,2-d]furanyl nyl, benzo[b]naphtho[2,3-d]furanyl, benzo[b]naphtho[2,1-d]furanyl, tribenzo[b,d,f]oxepinyl, dibenzo[b,d]thienyl, naphtho[1,2-b]thienyl, naphtho[2,3-b]thienyl, naphtho[2,1-b]thienyl, benzo[b]naphtho[1,2-d]thienyl, benzo[b]naphtho[2,3-d]thienyl, benzo[b]naphtho[2,1-d]thienyl, 6H-dibenzo[b,d]thiopyranyl, 5H,9H-[1]benzothiopyrano[5,4,3-c,d,e][2]benzothiopyranyl, 5H,10H-[1]benzothiopyrano[5,4,3-c,d,e][2]benzothiopyranyl, benzo[1,2-b:4,3-b']bisthienyl, benzo[1,2-b:6,5-b']bisthienyl, benzo[1,2-b:5,4-b']bisthienyl, benzo[1,2-b:4,5-b']bisthienyl, 1,4-benzodithiinyl, naphtho[1,2-b][1,4]dithiinyl, naphtho[2,3-b][1,4]dithiinyl, thianthrenyl, Benzo[a]thianthrenyl, benzo[b]thianthrenyl, dibenzo[a,c]thianthrenyl, dibenzo[a,h]thianthrenyl, dibenzo[a,i]thianthrenyl, dibenzo[a,j]thianthrenyl, dibenzo[b,i]thianthrenyl, 2H-naphtho[1,8-b,c]thienyl, 5H-phenanthro[4,5-b,c,d]thiopyranyl, 10,11-dihydrodibenzo[b,f]thiepinyl, 6,7-dihydrodibenzo[b,d ]thiepinyl, dibenzo[b,f]thiepinyl, dibenzo[b,d]thiepinyl, 6H-dibenzo[d,f][1,3]dithiepinyl, tribenzo[b,d,f]thiepinyl, benzothieno[3,4-c,d]thieno[2,3,4-j,k][2]benzothiepinyl, dinaphtho[1,8-bc:1',8'-f,g][1,5]dithiocinyl, furo[3,2-g]quinolinyl, furo[2,3-g]quinolinyl, furo[2,3-g]quinoxalinyl, Examples include, but are not limited to, 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-h,i]indolyl, benzo[g]quinoxalinyl, benzo[f]quinoxalinyl, and benzo[h]isoquinolinyl.

[0043] For purposes of this invention, the terms "phenylene," "naphthylene," and "biphenylylene" are used conventionally in the art to refer to divalent radicals of benzene, naphthalene, and biphenyl, respectively. Thus, the terms "phenylene," "naphthylene," and "biphenylylene" are used herein synonymously with the terms phendiyl, naphthalenediyl, and biphenyldiyl, respectively.

[0044] For purposes of 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.

[0045] In the context of the present invention, the term "optical device" refers to a device that is transparent to visible light and manipulates light rays, particularly by refraction. Optical devices include, but are not limited to, prisms, lenses, optical films, and combinations thereof, particularly camera lenses and eyeglass lenses.

[0046] The remarks made below on preferred embodiments of the variables (substituents) of the compounds of formula (I) and of the structural units of formula (III) are valid both alone and preferably in combination with one another.

[0047] The remarks made below regarding preferred embodiments of the variables are furthermore valid, alone and preferably in combination with one another, for the compounds of formula (I) and the structural units of formula (III) and, where applicable, for the uses according to the invention. However, while the above disclaimers apply in the case of compounds (I) according to the invention, they do not apply in the case of the uses according to the invention or the resins according to the invention.

[0048] In formula (I), and, where applicable or interchangeable, in formula (III), the variable X 1 , X 2 , Z 1 , Z 2 , R a , R b , Rc and R d has, alone or preferably in any combination, preferably the following meanings:

[0049] In a preferred embodiment, in particular Z 1 and Z 2 If both are OH, X 1 and X 2 are each independently a C1-C5-alkanediyl, more preferably methylene or 1,2-ethylene.

[0050] In another preferred embodiment, X 1 and X 2 have the same meaning.

[0051] In a more preferred embodiment, X 1 and X 2 have the same meaning and are both C1-C5-alkanediyl. Even more preferably, X 1 and X 2 has the same meaning and is methylene or 1,2-ethylene. In particular, X 1 and X 2 are both methylene.

[0052] In a preferred embodiment, Z 1 and Z 2 have the same meaning.

[0053] In another preferred embodiment, Z 1 and Z 2 are both OH.

[0054] In a more preferred embodiment, X 1 and X 2 have the same meaning and are both methylene or 1,2-ethylene, and Z 1 and Z 2 and are both OH. Even more preferably, X 1 and X 2 are both methylene, and Z 1 and Z 2 are both OH.

[0055] In an alternative preferred embodiment, X 1 and X 2 are both bonds.

[0056] In an alternative preferred embodiment, Z 1 and Z 2 is C(O)OR x R x is preferably selected from the group consisting of hydrogen and C1-C4-alkyl, more preferably hydrogen.

[0057] In an alternative more preferred embodiment, X 1 and X 2 are both bonds, and Z 1 and Z 2 is C(O)OR x and R x is preferably selected from the group consisting of hydrogen and C1-C4-alkyl.

[0058] However, X 1 and X 2 have the same meaning and are both C1-C5-alkanediyl, even more preferably methylene or 1,2-ethylene, especially methylene; Z 1 and Z 2 Compound (I), in which both are OH, is more preferred.

[0059] In a preferred embodiment, R a , R b , R c and R d Two of the groups are dibenzothiophene groups of formula (II). Preferably, the two dibenzothiophene groups (II) are not closely bonded (i.e., they are not ortho to each other), which means that, for example, R a is a dibenzothiophene group (II), the second dibenzothiophene group (II) is preferably R c or R d and R bMore preferably, the two dibenzothiophene groups (II) are in the para position relative to each other, which means that, for example, R a and R d is a dibenzothiophene group of formula (II).

[0060] In a preferred embodiment, R is not a dibenzothiophene group of formula (II). a , R b , R c and R d The groups are preferably, independently of one another, hydrogen or C1-C4-alkyl, more preferably hydrogen. Even more preferably, R a , R b , R c and R d Two of the groups are dibenzothiophene groups of formula (II) and the other two R a , R b , R c and R d The group is hydrogen. Particularly preferred is R a is a dibenzothiophene group (II), and R c or R d is the second dibenzothiophene group (II), and the other two R b and R c or R d The group is hydrogen. In particular, R a and R d is a dibenzothiophene group of formula (II), and R b and R c is hydrogen.

[0061] The dibenzothiophene group (II) can be attached primarily through any of the four carbon atoms of one of the two phenyl rings, i.e., at the 1, 2, 3 or 4 position, the numbering of the positions being as follows:

[0062] [ka]

[0063] However, the dibenzothiophene group (II) is preferably attached via its 4-position and is therefore preferably a group of formula (II.1):

[0064] [ka] where # indicates the point of attachment to the rest of the molecule.

[0065] Thus, in a more preferred embodiment, R a , R b , R c and R d Two of the groups are dibenzothiophene groups of formula (II.1) and the other two R a , R b , R c and R d The group is hydrogen. Even more preferably, R a is a dibenzothiophene group of formula (II.1), and R c or R d is the second dibenzothiophene group (II.1), and the other two R b and R c or R d The group is hydrogen. In particular, R a and R d is a dibenzothiophene group of formula (II.1), and R b and R c is hydrogen.

[0066] In certain embodiments, X 1 and X 2 have the same meaning and are both methylene or 1,2-ethylene, preferably methylene; Z 1 and Z 2 are both OH; R a , R b , R c and R d two of the groups are dibenzothiophene groups of formula (II), and the two groups that are dibenzothiophene groups of formula (II) are not adjacently bonded; R of formula (II) which is not a dibenzothiophene group a , R b , R c and R d The group is hydrogen.

[0067] In more detail, X 1 and X 2 have the same meaning and are both methylene or 1,2-ethylene, preferably methylene; Z 1 and Z 2 are both OH; R a , R b , R c and R d two of the groups are dibenzothiophene groups of formula (II.1), and the two groups that are dibenzothiophene groups of formula (II.1) are not adjacently bonded; R of formula (II.1) which is not a dibenzothiophene group a , R b , R c and R d The group is hydrogen.

[0068] In an alternative specific embodiment, X 1 and X 2 are both bonds; Z 1 and Z 2 Both are C(O)OR x and R x is selected from the group consisting of hydrogen and C1-C4-alkyl; R a , R b , R c and R d two of the groups are dibenzothiophene groups of formula (II), preferably (II.1), and the two groups that are dibenzothiophene groups of formula (II) are not closely linked; R of formula (II) which is not a dibenzothiophene group a , R b , R c and R d The group is hydrogen.

[0069] Specifically, compound (I) is a compound of formula (I.1):

[0070] [ka]

[0071] Compound (I) can be prepared by standard reactions in organic chemistry, such as the Suzuki reaction (also known as Suzuki coupling, Suzuki-Miyaura reaction, or Suzuki-Miyaura coupling) of a central phenyl moiety and an appropriate precursor of the dibenzothiophene moiety (II), as shown in Scheme 1.

[0072] [ka]

[0073] A of compounds 1 and I' 1 -X 1 -Z 1 group or its precursor, and similarly, A of compounds 1 and I' 2 -X 2 -Z 2 LG is a leaving group such as a halogen atom, particularly Br or I, or a sulfonate, where the sulfonate is particularly a fluorinated alkyl sulfonate or tosylate, specifically a triflate (trifluoromethyl sulfonate) or a nonaflate (nonafluorobutyl sulfonate). Each R' is independently an R other than group (II). a , R b , R c and R d and G is also a leaving group LG or (R a , R b , R c and R d (When preparing compound (I) in which two of the groups are groups (II)), or independently, R excluding the group (II) a , R b , R c and R d has one of the meanings of (Ra , R b , R c and R d In compound I', G' is either a (II) group (when G in compound 1 is LG) or a R group other than a (II) group. a , R b , R c and R d(when G in compound 1 is not LG). Instead of boronic acid 2, a suitable derivative thereof, such as its ester, particularly its C1-C4-alkyl ester, can be used (thus, this group is -B(O-C1-C4-alkyl)2 instead of -B(OH)2). Suzuki couplings are generally carried out in the presence of a transition metal catalyst, primarily a Pd or Ni catalyst, more frequently a Pd catalyst, and also generally in the presence of a base. Pd or Ni catalysts are usually used with phosphorus ligands, such as trisubstituted phosphine ligands, for example, 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, particularly a triarylphosphine, for example, triphenylphosphine and tritolylphosphine. The suitable base can be inorganic or organic. Examples of suitable inorganic bases are alkali metal carbonates, such as Li2CO3, Na2CO3, K2CO3 or Cs2CO3, alkali metal bicarbonates, such as LiHCO3, NaHCO3, KHCO3 or CsHCO3, alkali metal hydroxides, such as LiOH, NaOH or KOH, or phosphates, such as Li3PO4, Na3PO4, K3PO4 or Cs3PO4. Examples of suitable organic bases are open-chain amines, such as trimethylamine, triethylamine, tripropylamine, ethyldiisopropylamine, morpholine, pyridine, lutidine, basic N-heterocycles, such as DABCO, DBU or DBN, or alkoxylates, such as sodium or potassium methanolate, ethanolate, propanolate, isopropanolate, butanolate or tert-butanolate. Often, inorganic oxobases, such as the alkali metal carbonates listed above, are used.

[0074] For better illustration, Scheme 2 shows the R a and R d is a dibenzothiophene group (II.1), and R b and R cThe synthesis of compound I″ where is hydrogen is shown as a representative example.

[0075] [ka]

[0076] As in Scheme 1, A of compounds 1′ and I″ 1 -X 1 -Z 1 group or its precursor, and similarly, A in compounds 1′ and I″ 2 -X 2 -Z 2 LG is a group or a precursor thereof. LG is a halogen atom, especially Br or I, or a leaving group such as a sulfonate, especially a fluorinated alkylsulfonate or a tosylate, specifically a triflate or nonaflate.

[0077] Conversely, the use of Suzuki reactive groups in starting compounds, i.e., boronic acid (derivatives) of the central phenyl moiety (i.e., A 1 and A 2 Although it is primarily possible to start from a dibenzothiophene having a -substituted phenyl ring (wherein the -substituted phenyl ring carries one or two -B(OH) groups or derivatives thereof) and a leaving group LG, it has proven more convenient to use the starting compounds 1, 2, 1' and 2' shown in Schemes 1 and 2, especially when preparing compounds (II) having two (II) groups.

[0078] A of compound I' or I" 1 and A 2 One or both of the desired -X 1 -Z 1 or -X 2 -Z 2 If the group is a precursor of the formula (I), then it is converted into the desired group.

[0079] -X 1 -Z 1 or -X 2 -Z 2Suitable precursors of the -CH2-OH group as a group are, for example, carboxylic acid or carboxylate groups -C(O)OR x1 (R x1 is hydrogen or C1-C4 alkyl). 1 and A 2 or both of the compounds I' or I" are -C(O)OR x1 group, this is 1 and A 2 Both are -C(O)OR x1 This can be converted to the desired -CH-OH group by a reduction reaction, as representatively shown in Scheme 3 for compound I' (in this case referred to as I'"), which is: Useful reducing agents are, for example, hydride complexes such as lithium aluminum hydride or sodium borohydride, with lithium aluminum hydride being preferred.

[0080] [ka]

[0081] -X 1 -Z 1 or -X 2 -Z 2 Another suitable precursor of the -CH2-OH group is the formyl group (-CHO). Thus, in Schemes 1 and 2, in compounds 1 and 1', A 1 and A 2 One or both of the groups may be a formyl group. 1 and A 2 Compound I' (in this case, I v As shown in Scheme 4, each of -X 1 -Z 1 and / or -X 2 -Z 2This can be converted to compound (I) in which the group is -CH-OH. Useful reducing agents are again, for example, hydride complexes such as lithium aluminum hydride or sodium borohydride, with sodium borohydride being preferred.

[0082] [ka]

[0083] -X 1 -Z 1 or -X 2 -Z 2 A suitable precursor of the -CHCH-OH group as a group is, for example, the vinyl group -CH=CH. Thus, in Schemes 1 and 2, in compounds 1 and 1', A 1 and A 2 One or both of the compounds I' and I" may be a vinyl group -CH=CH2. 1 and A 2 Compound I' (in this case, I vi As shown representatively in Scheme 5 for (referred to as "(N- ... vii By changing each -X 1 -Z 1 and / or -X 2 -Z 2 The compound (I) can be converted to the compound (I) in which the group is CH2CH2-OH. This reaction is generally carried out in the presence of a base, suitable bases being those listed above. Here, an alkali metal hydroxide is preferably used.

[0084] [ka]

[0085] Compound I viFor example, the Wittig reaction using the Wittig reagent (Ph)3P=CH2 (Ph=phenyl) yields the respective formyl compounds I v can be obtained from

[0086] The formyl group -CHO can also be -X 1 -Z 1 or -X 2 -Z 2 -CH2CH2CH2-OH group or -CH2CH2-C(O)OR as a group x Thus, in Schemes 1 and 2, in compounds 1 and 1′, A 1 and A 2 One or both of the compounds I' and I" may be a formyl group -CHO. 1 and A 2 Compound I' (in this case, I v For example, as shown in Scheme 6 for the Wittig reagent (Ph)P=CH-C(O)OR x Wittig reaction using formyl compound I v By reacting each of the -X 1 -Z 1 and / or -X 2 -Z 2 The group is -CH2CH2CH2-OH or -CH2CH2-C(O)OR x The resulting unsaturated ester 3 can be converted to compound (I), which is a group. viii This can be hydrogenated to give diol I, if desired. ix or the unsaturated ester 3 can be reduced to the unsaturated diol 4, which can then be converted to the diol I ix Ester 3 can be hydrogenated to ester I. viii Hydrogenation of diol 4 to diol I ix The hydrogenation to ester I is typically carried out in the presence of a hydrogenation catalyst, generally a transition metal catalyst such as Pd. viii Diol I ixor reduction of ester 3 to diol 4 can be carried out, for example, using a hydride complex such as lithium aluminum hydride or sodium borohydride under the conditions described above in the context of Scheme 3, with lithium aluminum hydride being preferred.

[0087] [ka]

[0088] Alternatively, the precursor group A shown in Schemes 3-6 1 and A 2 -X 1 -Z 1 and -X 2 -Z 2 The conversion reactions to groups can of course be applied to the respective substituted starting compounds 1 as well. 1 and A 2 -C(O)OR x1 Compound 1, 1 and A 2 can be reduced to compound 1, where A is —CH—OH; or A 1 and A 2 is formyl, to afford compound 1, under reaction conditions similar to those described above in the context of Scheme 4, 1 and A 2 can be reduced to compound 1, where A is —CH—OH; or A 1 and A 2 Compound 1, in which is formyl, can be subjected to a Wittig reaction using, for example, the Wittig reagent (Ph)P=CH (Ph=phenyl) under reaction conditions similar to those described above in the context of Scheme 5 to give A 1 and A 2 Compound 1, in which A is both vinyl, can be obtained, which can be subjected to hydroboration / oxidation to give A 1 and A 2 Compound 1 can be obtained in which A is -CH2CH2-OH; or 1 and A 2is formyl, can be reacted with, for example, the Wittig reagent (Ph)P=CH—C(O)OR under reaction conditions similar to those described above in the context of Scheme 6. x A was subjected to a Wittig reaction using 1 and A 2 -CH=CH-C(O)OR x Compound 1 can be obtained, which is subjected to hydrogenation to give compound A 1 and A 2 -CH2CH2-C(O)OR x Compound 1 can be obtained, which, if desired, can be reduced to give compound A 1 and A 2 Compound 1 can be obtained in which A is -CH2CH2CH2-OH, or 1 and A 2 -CH=CH-C(O)OR x Compound 1 is subjected to a reduction reaction to obtain A 1 and A 2 Compound 1, in which is -CH=CH-CH2-OH, can be obtained by reacting A 1 and A 2 Compound 1 can then be reacted with compound 2 in the Suzuki reaction described above to give the desired -X 1 -Z 1 and -X 2 -Z 2 The compound (I) having the group can be obtained directly.

[0089] The above scheme is -X 1 -Z 1 and -X 2 -Z 2 The preparation of compound (I) is shown below, where the groups -X have the same meaning. 1 -Z 1 and -X 2 -Z 2 Compounds (I) in which the radicals have different meanings can be prepared by the desired different -X 1 -Z 1 and -X 2 -Z 2 -X groups already present or different -X groups as desired. 1 -Z1 and -X 2 -Z 2 Alternatively, the same precursor group A can be prepared by using starting compound 1 having the appropriate precursor group A to obtain the group. 1 and A 2 These can be selectively subjected to different transformation reactions. 1 and A 2 In compound 1, where both are formyl, only one formyl group can be converted using the Wittig reagent (Ph)P=CH-C(O)OR. x to give -CH=CH-C(O)OR x group, which can then be subjected to the hydrogenation and reduction reactions described in the context of Scheme 6, and the remaining formyl group can then be reduced to a —CHOH group. 1 -Z 1 and -X 2 -Z 2 One of the groups is -CH2OH and the other is -CH2CH2CH2-OH or -CH2CH2-C(O)OR x Compound (I) is obtained.

[0090] The starting compounds 1 and 2 are either commercially available or can be synthesized by various A 1 and A 2 They can be obtained by standard reactions of organic chemistry, such as those shown above for the transformation of groups.

[0091] The reaction products are usually worked up in customary manner, for example by mixing with water, separating the phases and, if necessary, purifying the crude product by washing, chromatography or crystallization.

[0092] As described above, the compound (I) of the present invention can be obtained with high purity (meaning that the product does not contain a significant amount of organic impurities other than the compound of formula (I) except for volatile substances).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, i.e., 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).

[0093] The term "volatiles" refers to the amount of 5 Non-volatile organic compounds refer to organic compounds having a boiling point of less than 200°C at standard pressure. Consequently, non-volatile organic compounds are understood to mean compounds having a boiling point of more than 200°C at standard pressure.

[0094] A particular advantage of the present invention is that the compounds of formula (I) and 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 a solvate with water or an organic solvent.Therefore, 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 form in which the compounds of formula (I) exist without solvent, and to the crystalline solvates of the compounds of formula (I) that incorporate solvent.

[0095] A particular advantage of the present invention is that compounds of formula (I) and their solvates can often be easily crystallized from conventional organic solvents. This allows for efficient purification of the compounds of formula (I). Suitable organic solvents for crystallizing 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 alicyclic ethers such as diethyl ether, dipropyl ether, methyl isobutyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, dioxane, or tetrahydrofuran, aliphatic-aromatic ethers such as anisole, and aliphatic alcohols having 1 to 4 carbon atoms such as methanol, ethanol, or isopropanol, and mixtures thereof.

[0096] Furthermore, impurities that may be present in crude preparations of compounds of formula (I), in particular colour-forming impurities and heavy metals (the latter generally resulting from the Suzuki reaction), can be removed at any stage of the purification process, for example before the filtration or crystallisation step, by standard procedures such as treatment with adsorbents, e.g. activated carbon.

[0097] Alternatively, the compounds of formula (I) and their solvates can be obtained in purified form by using other simple and efficient methods for purifying the raw products of these compounds, such as slurry washing the raw solids obtained immediately after the conversion to prepare the compounds of formula (I). Slurry washing is typically carried out at ambient temperature or at elevated temperatures, usually about 30-90°C, especially 40-80°C. Suitable organic solvents here are in principle the same as those listed above as being suitable for crystallizing the compounds of formula (I), including, in particular, aromatic hydrocarbons, aliphatic ketones, and aliphatic ethers, such as toluene, methyl ethyl ketone, and methyl tert-butyl ether, or aliphatic alcohols such as methanol, and alkanes such as pentane or hexane.

[0098] Therefore, the compounds of formula (I) used in the preparation of thermoplastic polymers, particularly polycarbonates, as defined herein can be easily prepared and obtained in high yield and high purity. In particular, the compounds of formula (I) can be obtained in a crystalline form that allows for efficient purification to the extent required in the preparation of optical resins. In particular, these compounds can be obtained with a purity that provides a high refractive index and also low haze, which are particularly important for use in the preparation of optical resins for making optical devices. In conclusion, the compounds of formula (I) are particularly useful as monomers in the preparation of optical resins.

[0099] In a further aspect, the present invention relates to a thermoplastic resin comprising structural units of formula (III):

[0100] [ka] (In the formula, # represents the point of attachment to the adjacent structural unit; Z 11 is a bridging group -O- or -C(O)-O-, and the carbon atom of the -C(O)-O- group is X 1 is bound to; Z 12 is a bridging group -O- or -C(O)-O-, and the carbon atom of the -C(O)-O- group is X 2 is bound to; X 1 , X 2 , R a , R b , R c and R d is as defined above in the context of compound (I).

[0101] Those skilled in the art will readily understand that the structural unit (III) contained in the thermoplastic resin is derived from the corresponding compound (I). Similarly, the structural unit (III.1.1) shown below is derived from compound (I.1).

[0102] Those skilled in the art will also understand that the structural unit of formula (III) is a repeating unit within the polymer chain of a thermoplastic resin.

[0103] X 1 , X 2 , R a , R b , R c and R d Preferred meanings of are those described in the context of compound (I), and preferred bridging groups Z 11 and Z 12 is Z as described in the context of compound (I). 1 and Z 2 This is derived from the preferred meaning of

[0104] Therefore, in a preferred embodiment, in the structural unit (III), X 1 and X 2 are each independently a C1-C5-alkanediyl, more preferably methylene or 1,2-ethylene.

[0105] In another preferred embodiment, X 1 and X 2 have the same meaning.

[0106] In a more preferred embodiment, X 1 and X 2 have the same meaning and are both C1-C5-alkanediyl. Even more preferably, X 1 and X 2 has the same meaning and is methylene or 1,2-ethylene. In particular, X 1 and X 2 are both methylene.

[0107] In a preferred embodiment, Z 11 and Z 12 have the same meaning.

[0108] In another preferred embodiment, Z 11 and Z 12are both bridging groups -O- and the structural unit is in this case a structural unit of formula (III.1):

[0109] [ka]

[0110] In a more preferred embodiment, X 1 and X 2 have the same meaning and are both methylene or 1,2-ethylene, and Z 11 and Z 12 and X are both bridging groups -O-. Even more preferably, X 1 and X 2 are both methylene, and Z 11 and Z 12 are both bridging groups -O-.

[0111] In an alternative preferred embodiment, X 1 and X 2 are both bonds.

[0112] In an alternative preferred embodiment, Z 11 and Z 12 are both bridging groups -C(O)O-, the carbon atoms of which are 1 and X 2 is bonded to.

[0113] In an alternative more preferred embodiment, X 1 and X 2 are both bonds, and Z 11 and Z 12 are both bridging groups -C(O)O-, the carbon atoms of which are 1 and X 2 is bonded to.

[0114] However, X 1 and X 2 have the same meaning, both are C1-C5-alkanediyl, even more preferably methylene or 1,2-ethylene, in particular methylene, and Z 11 and Z12 and (III) are both bridging groups -O-.

[0115] In a preferred embodiment, R a , R b , R c and R d Two of the groups are dibenzothiophene groups of formula (II). Preferably, the two dibenzothiophene groups (II) are not adjacently bonded; i.e., R a is a dibenzothiophene group (II), the second dibenzothiophene group (II) is R c or R d More preferably, R a and R d is a dibenzothiophene group of formula (II).

[0116] In another preferred embodiment, R is a group of formula (II) that is not a dibenzothiophene group. a , R b , R c and R d The groups are preferably, independently of one another, hydrogen or C1-C4-alkyl, more preferably hydrogen. Even more preferably, R a , R b , R c and R d Two of the groups are dibenzothiophene groups of formula (II) and the other two R a , R b , R c and R d The group is hydrogen. Particularly preferred is R a is a dibenzothiophene group (II), and R c or R d is the second dibenzothiophene group (II), and the other two R b and R c or R d The group is hydrogen. In particular, R a and R d is a dibenzothiophene group of formula (II), and R b and R c is hydrogen.

[0117] The dibenzothiophene group (II) can be attached primarily through any of the four carbon atoms of one of the two phenyl rings, i.e., at the 1, 2, 3 or 4 position, the numbering of the positions being as follows:

[0118] [ka]

[0119] However, the dibenzothiophene group (II) is preferably attached via its 4-position and is therefore preferably a group of formula (II.1):

[0120] [ka] where # indicates the point of attachment to the rest of the molecule.

[0121] Thus, in a more preferred embodiment, R a , R b , R c and R d Two of the groups are dibenzothiophene groups of formula (II.1) and the other two R a , R b , R c and R d The group is hydrogen. Even more preferably, R a is a dibenzothiophene group (II.1), and R c or R d is the second dibenzothiophene group (II.1), and the other two R b and R c or R d The group is hydrogen. In particular, R a and R d is a dibenzothiophene group of formula (II.1), and R b and R c is hydrogen.

[0122] In particular embodiments of structural unit (III), X 1 and X 2have the same meaning and are both methylene or 1,2-ethylene; Z 11 and Z 12 are both bridging groups -O-; R a , R b , R c and R d two of the groups are dibenzothiophene groups of formula (II), and the two groups that are dibenzothiophene groups of formula (II) are not adjacently bonded; R of formula (II) which is not a dibenzothiophene group a , R b , R c and R d The group is hydrogen.

[0123] In more detail, X 1 and X 2 have the same meaning and are both methylene or 1,2-ethylene, preferably methylene; Z 11 and Z 12 are both bridging groups -O-; R a , R b , R c and R d two of the groups are dibenzothiophene groups of formula (II.1), and the two groups that are dibenzothiophene groups of formula (II.1) are not adjacently bonded; R of formula (II.1) which is not a dibenzothiophene group a , R b , R c and R d The group is hydrogen.

[0124] In an alternative specific embodiment, X 1 and X 2 are both bonds; Z 11 and Z 12 are both bridging groups -C(O)O-, the carbon atoms of which are 1 and X 2 is bound to; Ra , R b , R c and R d two of the groups are dibenzothiophene groups of formula (II), preferably (II.1), and the two groups that are dibenzothiophene groups of formula (II) are not closely linked; R of formula (II) which is not a dibenzothiophene group a , R b , R c and R d The group is hydrogen.

[0125] However, in particular, the structural unit (III) is a unit of formula (III.1.1):

[0126] [ka] (where # represents the point of attachment to the adjacent structural unit).

[0127] In addition to the structural units of formula (III), the thermoplastic resin may have structural units different therefrom. In a preferred embodiment, these further structural units are derived from aromatic monomers of formula (VI) to give structural units of formula (V): HO-R z -A 1 -R z -OH (VI) #-OR 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 directly fused to each other and / or fused to a non-benzene carbocyclic ring), and A 1 is unsubstituted or contains 1, 2 or 3 R aa Group(R aais substituted with a substituted aryl group 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'):

[0128] [ka] (In the formula, Q' represents a single bond, O, NH, C=O, CH2 or CH=CH; R 7a , R 7b are independently hydrogen, fluorine, CN, R, OR, CH k R 3-k , NR2, C(O)R and C(O)NH2 (wherein R is as defined herein and k is 0, 1, 2 or 3); * denotes 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 ring atoms of the hetaryl are selected from nitrogen, sulfur, and oxygen, and the remainder of the ring atoms of the hetaryl are carbon atoms, and Ar is unsubstituted or has 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 ) and p is an integer from 1 to 10; Alk 1is C1-C4-alkanediyl; Alk 2 is C2-C4-alkanediyl; Alk 3 is C1-C4-alkanediyl).

[0129] R in formula (VI) z O-Alk 3 When it is -C(O), an ester of the monomer of formula (VI) can be used instead, in particular a C1-C4-alkyl ester.

[0130] In the context of formulas (VI) and (V), A 1 is in particular a polycyclic group having two benzene or naphthalene rings, the benzene rings being linked by A. In this context, A is in particular selected from the group consisting of a single bond, a CH—Ar, a CAr2, and an A′ group.

[0131] In the context of formulas (VI) and (V), R z is especially O-Alk 2 -(Alk 2 is especially a straight-chain alkanediyl having 2 to 4 carbon atoms), especially O—CH2CH2.

[0132] Among the monomers of formula (VI), the monomers of general formulae (VI-1) to (VI-6) are preferred:

[0133] [ka] (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 for formula (VI), and Rz is in particular selected from a single bond, CH2 and OCH2CH2).

[0134] Among the monomers of formula (VI), R z and R aa is as defined herein, and R z Particularly preferred are monomers of the general formulae (VI-11) to (VI-20), in which is in particular selected from a single bond, CH and O—CHCH, in particular O—CHCH:

[0135] [ka]

[0136] [ka]

[0137] [ka]

[0138] Examples of compounds of formulae (VI-11) to (VI-20) are 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-isopropylphenyl)fluorene, 9,9-bis(4-hydroxy-3-tert.-butylphenyl)fluorene, 9,9-bis(4-hydroxy-3-cyclohexylphenyl)fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxyphenyl)fluorene), also known as BPEF. )phenyl)fluorene (), 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-isopropylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-tert.-butylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-cyclohexylphenyl)fluorene, also known as BPPEF, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene (), 9,9-bis(6-hydroxyethoxy)- 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'-dihydro 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, Examples include 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, and 2,2'-bis(2-hydroxyethoxy)-6,6'-di(9-phenanthryl)-1,1'-binaphthalene. Among the monomers of general formula (VI) or formulas (VI-1) to (VI-6), monomers of formulas (VI-1), (VI-2), (VI-3), and (VI-6) are particularly preferred, and monomers of formulas (VI-1) and (VI-2), especially (VI-1), are more preferred. Among the monomers of formulae (VI-11) to (VI-20), the monomers of formulae (VI-11), (VI-12), (VI-14), (VI-19) and (VI-20) are particularly preferred, and the monomer of formulae (VI-11), (VI-19) and (VI-20), especially (VI-11), is more preferred. 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) are particularly preferred. 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) is more particularly preferred, and 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene is very particularly preferred.

[0139] Therefore, among the structural units of formula (V) that can be contained in the thermoplastic resin, structural units of general formulae (V-1) to (V-6) are preferred:

[0140] [ka] (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 for formula (V), and R z is in particular selected from a single bond, CH2 and OCH2CH2).

[0141] R z and R aa is as defined herein, and R z Particularly preferred are structural units of the general formulae (V-11) to (V-20), in which is in particular selected from a single bond, CH and O—CHCH, in particular O—CHCH:

[0142] [ka]

[0143] [ka]

[0144] Among the structural units of formulae (V-1) to (V-6), structural units of formulae (V-1), (V-2), and (V-6) are particularly preferred. Among the structural units of formulae (V-11) to (V-20), structural units of formulae (V-11), (V-12), (V-14), (V-19), and (V-20) are particularly preferred, with structural units of formulae (V-11), (V-19), and (V-20), especially (V-11), being more preferred. 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 especially 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (BPEF) are particularly preferred.

[0145] In a particularly preferred group of embodiments, the thermoplastic resin of the present invention comprises at least one structural unit of formula (III.1) or (III.1.1) 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, in the structural units of formula (V-11), (V-19) and (V-20), R z Preferred are thermoplastic resins in which the group is O-CH2CH2. More particularly, the thermoplastic resins of the present invention comprise at least one structural unit of formula (III.1.1) and at least one structural unit of formula (V-11). In this particular embodiment, in the structural unit of formula (V-11), R z Thermoplastic resins in which the group is O-CH2CH2 are preferred.

[0146] In the thermoplastic resin, the total molar ratio of the structural units of formula (III) is preferably in the range of 1 to 70 mol%, preferably 5 to 60 mol%, more preferably 8 to 45 mol%, and even more preferably 10 to 30 mol%, of the total amount of the structural units of formula (III) and formula (V).The molar ratio of the structural units of formula (V) is also preferably in the range of 30 to 99 mol%, preferably 40 to 95 mol%, more preferably 55 to 92 mol%, and even more preferably 70 to 90 mol%, based on the total amount of the structural units of formula (III) and formula (V).

[0147] A further embodiment of the present invention relates to thermoplastic resins having only low, almost no or no birefringence, characterized in that they have structural units of formula (III), such as in particular formula (III.1) or (III.1.1), in which the variables have one of the above-mentioned preferred meanings, and also one or more structural units different from those of formula (III), preferably selected from structural units of formula (V), in particular structural units of formulae (V-11), (V-12), (V-14), (V-19) and (V-20), in particular structural units of formulae (V-11), (V-19) and (V-20). In the thermoplastic resin of this particular preferred embodiment, it is preferred that the total molar ratio of structural units of formula (III), (III.1) or (III.1.1) is 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 % of the total amount of structural units of formula (III) and formula (V).

[0148] Compounds of formula (VI), (VI-1), (VI-2), (VI-3), (VI-4), (VI-5), (VI-6), (VI-11), (VI-12), (VI-13), (VI-14), (VI-15), (VI-16), (VI-17), (VI-18), (VI-19) and (VI-20) are known or can be prepared analogously to known methods.

[0149] For example, the compound of formula (VI-6) can be prepared by various synthesis methods disclosed in, for example, JP 2014-227387 A, JP 2014-227388 A, JP 2015-168658 A, and JP 2015-187098 A. For example, 1,1'-binaphthol may be reacted with ethylene glycol monotosylate; alternatively, 1,1'-binaphthol may be reacted with alkylene oxide, halogenoalkanol, or alkylene carbonate; alternatively, 1,1'-binaphthol may be reacted with ethylene carbonate. Thereby, R z -OH is O-Alk 2 or O-Alk 2 -[O-Alk 2 -] p The compound of formula (IV-6) is obtained.

[0150] For example, the compound of formula (VI-2) can be prepared by various synthetic methods disclosed in, for example, Japanese Patent No. 5442800 and Japanese Patent Application Laid-Open No. 2014-028806. Examples include the following: (a) reacting fluorene with hydroxynaphthalene in the presence of hydrochloride gas and mercapto-carboxylic acid; (b) 9-fluorene is reacted with hydroxynaphthalene in the presence of an acid catalyst (and an alkyl mercaptan); (c) reacting fluorene with hydroxynaphthalene in the presence of hydrochloride and thiols (such as mercapto-carboxylic acids); (d) Reacting fluorene with hydroxynaphthalene in the presence of sulfuric acid and thiols (such as mercapto-carboxylic acids), followed by crystallization of the product from a crystallization solvent consisting of a hydrocarbon and a polar solvent, to form bisnaphtholfluorene; etc. Thereby, R z A compound of formula (VI-2) in which is a single bond can be obtained.

[0151] R z O-Alk 2 - or O-Alk 2-[O-Alk 2 -] p - can be obtained by reaction with an alkylene oxide or a haloalkanol to give R z can be prepared from a compound of formula (VI) where R z When 9,9-bis(hydroxynaphthyl)fluorene of formula (VI-2), in which R is a single bond, is reacted with an alkylene oxide or a haloalkanol, R z O-Alk 2 - or O-Alk 2 -[O-Alk 2 -] p For example, 9,9-bis[6-(2-hydroxyethoxy)naphthyl]fluorene can be prepared by reacting 9,9-bis[6-(2-hydroxynaphthyl]fluorene with 2-chloroethanol under alkaline conditions.

[0152] The monomer of formula (I) and likewise the comonomer of formula (VI) used to prepare thermoplastic resins may contain certain impurities resulting from their preparation. For example, compound (I) may contain a halogen atom or a sulfonate group instead of the (II) group (the halogen atom or sulfonate group corresponds to LG in Scheme 1 above and results from incomplete conversion in the Suzuki reaction); for example, comonomer (VI) may contain, for example, O-Alk 2 It may contain hydroxy compounds with OH groups instead of -OH groups, or O-Alk 2 - group instead of O-Alk 2 -[O-Alk 2 ] p - group. The total amount of such impurity compounds is preferably 5000 ppm or less, more preferably 3000 ppm or less, even more preferably 2000 ppm or less, and particularly preferably 1000 ppm or less. The total content of impurities in the monomers used to prepare the thermoplastic resin is preferably 4000 ppm or less, particularly 1500 ppm or less, and more preferably 1000 ppm or less. In particular, at least one R zThe total amount of dihydroxy compounds having a carbon number of the -OH group different from that of formula (VI) is preferably 3000 ppm or less, more preferably 1500 ppm or less, even more preferably 1000 ppm or less, and particularly preferably 500 ppm or less; the main component of the monomer is the dihydroxy compound represented by formula (VI). z The total content of dihydroxy compounds having a carbon number in the -OH group different from that of formula (VI) is more preferably 1000 ppm or less, more preferably 500 ppm or less.Similarly, the amount of impurities in the monomer of formula (I) is in the range given for the monomer of formula (VI).

[0153] Suitable thermoplastic resins for preparing optical devices such as lenses are in particular polycarbonates, polyester carbonates and polyesters. Preferred thermoplastic resins for preparing optical devices such as lenses are in particular polycarbonates.

[0154] Structurally, the polycarbonates contain structural units of formula (III.1) and optionally structural units (Z) derived from diol monomers different from the monomer compounds of formula (I). 1 and Z 2 is OH), in particular structural units of formula (V): #-OR z -A 1 -R z -O-# (V) (In the formula, #, R z and A 1 is as defined hereinabove), and Structural units of formula (IV-1) resulting from carbonate-forming components:

[0155] [ka] (wherein each # represents the point of attachment to the adjacent structural unit, i.e., O at the point of attachment of the structural unit of formula (III.1) and, if present, O at the point of attachment of the structural unit of formula (V)). The thermoplastic resin can be a polyester carbonate and / or a polyester, and therefore the structural units represented by formulas (V) and (IV-1) or the following formulas (IV-2) to (IV-5) can be changed so that the thermoplastic resin contains polyester carbonate units and / or polyester units.

[0156] The polyester structurally comprises at least a structural unit of formula (III) and a crosslinking group Z 11 and Z 12 Depending on the nature of the dicarboxylic acid, structural units (Z 11 and Z 12 is -O-; some examples of suitable units derived from dicarboxylic acids are shown in the following formulae (IV-2) to (IV-5)) or structural units derived from diols (Z 11 and Z 12 is -C(O)O-; examples of suitable units derived from diols are characterized by having units of formula (V) above and any of the units derived from other diols, such as 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, norbornanedimethanol, 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-ididol, or aromatic diols different from diol (VI). 11 or Z 12is —O— and the other is —C(O)O—, further structural units need not be present, but preferably at least one unit derived from at least one diol, in particular at least one of the diols mentioned above, and / or at least one unit derived from at least one dicarboxylic acid, in particular at least one unit derived from at least one of the dicarboxylic acids mentioned above.

[0157] Preferably, however, the polyesters structurally comprise at least structural units of formula (III.1) and optionally structural units (Z) derived from diol monomers different from the monomer compounds of formula (I). 1 and Z 2 is OH), in particular of formula (V), and structural units derived from dicarboxylic acids, for example of formula (IV-2) for benzenedicarboxylic acid, of formula (IV-3) for naphthalenecarboxylic acid, of formula (IV-4) for oxalic acid and of formula (IV-5) for malonic acid:

[0158] [ka]

[0159] In formulae (IV-2) to (IV-5), each variable # represents the point of attachment to the adjacent structural unit, i.e., the O of the point of attachment of the structural unit of formula (III.1) and, if present, the O of the point of attachment of the structural unit of formula (V).

[0160] The polyester carbonate structurally comprises a structural unit of formula (III), a structural unit of formula (IV-1) derived from a carbonate-forming component, and a crosslinking group Z 11 and Z 12 Depending on the nature of the dicarboxylic acid, structural units (Z 11 and Z 12 is —O—; examples of suitable units derived from dicarboxylic acids are shown in the above formulae (IV-2) to (IV-5)) or structural units derived from diols (Z 11 and Z 12is —C(O)O—; examples of suitable units derived from diols are either units of formula (V) above or from the above-mentioned diols different from diol (VI).

[0161] Preferably, however, the polyester carbonates structurally comprise structural units of formula (III.1) and optionally structural units (Z) derived from diol monomers different from the monomer compounds of formula (I). 1 and Z 2 is OH), in particular structural units of formula (V), structural units of formula (IV-1) resulting from carbonate-forming components, and structural units derived from dicarboxylic acids, for example of formula (IV-2) in the case of benzenedicarboxylic acid, of formula (IV-3) in the case of naphthalenecarboxylic acid, of formula (IV-4) in the case of oxalic acid, and of formula (IV-5) in the case of malonic acid.

[0162] A particular group of embodiments are thermoplastic copolymer resins, especially polycarbonates, polyester carbonates and polyesters, having both structural units of formula (III), especially (III.1), and one or more structural units of formula (V), i.e., at least one monomer of formula (I), especially Z 1 and Z 2is OH with one or more monomers of formula (VI), in particular polycarbonates, polyestercarbonates and polyesters, in which the molar ratio of monomers of formula (I) to monomers of formula (VI) and likewise the molar ratio of structural units of formula (III), in particular (III.1), to structural units of formula (V) is 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 10:90 to 30:70 or in the range of 15:85 to 25:75. Therefore, the molar ratio of structural units of formula (III), particularly (III.1), based on the total molar amount of structural units of formula (III.1) and formula (V), is usually 1 to 70 mol%, particularly 5 to 60 mol%, more preferably 8 to 45 mol% or 10 to 40 mol%, particularly 10 to 30 mol% or 15 to 30 mol%, specifically 12 to 25 mol% or 15 to 25 mol%. Therefore, the molar ratio of structural units of formula (V), based on the total molar amount of structural units of formula (III.1) and 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 90 mol% or 70 to 85 mol%, specifically 75 to 88 mol% or 75 to 85 mol%.

[0163] The thermoplastic copolymer resin of the present invention, such as a polycarbonate resin, can have any one of a random copolymer structure, a block copolymer structure, and an alternating copolymer structure. The thermoplastic resin of the present invention does not necessarily contain all of the structural unit (III) and one or more different structural units (V) in the same polymer molecule. That is, the thermoplastic copolymer resin of the present invention may be a blend resin, as long as each of the above structures is contained in one of multiple polymer molecules. For example, a thermoplastic resin containing all of the structural units (III) and (V) may be a copolymer containing all of the structural units (III) and (V), a mixture of a homopolymer or copolymer containing at least one structural unit (III) and a homopolymer or copolymer containing at least one structural unit (V), a blend resin of a copolymer containing at least one structural unit (III) and a first structural unit (V) and a copolymer containing at least one structural unit (III) and at least one other structural unit (V) different from the first structural unit (V), etc.

[0164] Thermoplastic polycarbonates can be obtained by polycondensation of a diol component with a carbonate-forming component. Similarly, thermoplastic polyesters can be obtained by polycondensation of a diol component with a dicarboxylic acid or its ester-forming derivative, or by polycondensation of a Z-type diol component with a dicarboxylic acid or its ester-forming derivative. 1 and Z 2 One of them is -OH and the other is -C(O)OR x The polyester carbonate can be obtained by polycondensation of a compound (I) which is: The polyester carbonate can be obtained by polycondensation of a diol component, a dicarboxylic acid or an ester-forming derivative thereof, and a carbonate-forming component.

[0165] The present invention also relates to a method for preparing the resins according to the invention by subjecting the monomeric compound (I) to a polycondensation reaction with a suitable counterpart monomer to obtain a polycarbonate, polyester or polyester carbonate. The suitable counterpart is selected from the group consisting of the resin to be prepared and the Z of the monomer (I). 1 Groups and Z 2Depends on the nature of the group.

[0166] For example, when preparing polycarbonate, Z 1 and Z 2 is OH, the monomer compound (I) is 1 -C(=O)-LG 1 (Each LG 1 are independently a halogen atom, OCCl or an OR group (R is C alkyl, phenyl, chlorophenyl, tolyl, naphthyl, etc.), and are subjected to a polycondensation reaction with a carbonate-forming compound (also called a carbonate precursor), such as phosgene, diphosgene, and diester carbonates, e.g., diethyl carbonate, diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, and dinaphthyl carbonate.

[0167] For example, when preparing polyester, Z 1 and Z 2 The monomer compound (I), in which X is OH, is subjected to a polycondensation reaction with a dicarboxylic acid or a suitable derivative thereof, such as a dicarboxylic acid halide or diester. Suitable dicarboxylic acid (derivatives) are, for example, compounds (VII-2) to (VII-5), in which X is -OH, a halogen atom, in particular Cl or Br, or an -OR group (R is C1-C4-alkyl, phenyl, etc.):

[0168] [ka]

[0169] Further examples of suitable dicarboxylic acids (derivatives) are mentioned below.

[0170] Alternatively, when preparing polyesters, Z 1 and Z 2 -C(O)OR xThe monomer compound (I), which is: is subjected to a polycondensation reaction with a diol. Suitable diols are compound (VI) and diols different from compound (VI) mentioned above or below.

[0171] For example, when preparing polyester carbonate, Z 1 and Z 2 is OH, the monomer compound (I) is 1 -C(=O)-LG 1 and a dicarboxylic acid such as the dicarboxylic acid (derivatives) mentioned above or a suitable derivative thereof, or 1 and Z 2 -C(O)OR x The monomer compound (I) is reacted with the compound LG 1 -C(=O)-LG 1 and a diol such as those mentioned above in the context of polyesters.

[0172] Preferably, the method for preparing the polycarbonate comprises the steps of: 1 and Z 2 is OH, the monomer compound (I) is 1 -C(=O)-LG 1 and optionally a diol different from said compound (I), preferably diol (VI), more preferably one of the preferred diols (VI) such as (VI-11). In particular, the method for preparing polycarbonates comprises subjecting the monomer compound (I.1) to a polycondensation reaction with a carbonate-forming compound such as compound LG 1 -C(=O)-LG 1 and optionally a diol different from compound (I), preferably diol (VI), more preferably one of the preferred diols (VI) such as (VI-11). Further details about the method are provided below.

[0173] Specifically, the thermoplastic resin (polycarbonate resin) can be prepared by the following method.

[0174] The method for preparing the thermoplastic resins of the present invention, such as polycarbonate resins, comprises a process of melt polycondensation of a dihydroxy component corresponding to the structural unit described above with a carbonic acid diester. According to the present invention, the dihydroxy compound is Z 1 and Z 2 is OH. In addition to the compounds of formula (I), the dihydroxy compounds may also include one or more dihydroxy compounds of formula (VI), preferably of formulae (VI-1) to (VI-6), in particular of formulae (VI-11) to (VI-20), more in particular of formulae (VI-11), (VI-12), (VI-14), (VI-19) or (VI-20), in particular of formulae (VI-11), (VI-19) or (VI-20), very in particular of formula (VI-11).

[0175] As is clear from the above, polycarbonate resins contain dihydroxy components in LG 1 -C(=O)-LG 1 , with a carbonate precursor, such as a carbonic acid diester (the dihydroxy component comprising at least one compound of formula (I), particularly (I.1), and at least one compound of formula (VI), (VI-1), (VI-2), (VI-3), (VI-4), (VI-5), (VI-6), (VI-11), (VI-12), (VI-13), (VI-14), (VI-15), (VI-16), (VI-17), (VI-18), (VI-19) or (VI-20)). Specifically, the polycarbonate resin is a compound represented by formula (I), in particular (I.1), or a combination thereof with at least one compound of formula (VI), (VI-1), (VI-2), (VI-3), (VI-4), (VI-5), (VI-6), (VI-11), (VI-12), (VI-13), (VI-14), (VI-15), (VI-16), (VI-17), (VI-18), (VI-19) or (VI-20), and LG 1-C(=O)-LG 1 The copolymer can be formed by a melt polycondensation process in which a carbonate precursor, such as a carbonic acid diester, is reacted in the presence of a basic compound catalyst, a transesterification catalyst, or a mixture thereof, or in the absence of a catalyst.

[0176] Similarly, thermoplastic resins (or polymers) other than polycarbonate resins, such as polyesters and polyester carbonates, may be used, for example, Z 1 and Z 2 a dihydroxy compound of formula (I), in particular of formula (I.1), wherein R is OH, or a combination thereof with at least one compound of formula (VI), (VI-1), (VI-2), (VI-3), (VI-4), (VI-5), (VI-6), (VI-11), (VI-12), (VI-13), (VI-14), (VI-15), (VI-16), (VI-17), (VI-18), (VI-19) or (VI-20) as starting material (or monomer), and a dicarboxylic acid (derivative), in particular one of the compounds (VII-2) to (VII-5), or 1 and Z 2 -C(O)OR x The polyester carbonates can be obtained by melt polycondensation using the dicarboxylic acid compound (I) and one of the diols mentioned above, in particular the diol (VI). 1 -C(=O)-LG 1 Carbonate-forming compounds such as

[0177] As previously mentioned, the monomers of formula (I) and likewise the comonomers of formula (VI) used to prepare the thermoplastic resin may contain impurities resulting from their preparation.

[0178] In particular, the total amount of impurities in the compound of formula (I) 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.

[0179] The polycarbonate resin is preferably Z 1 and Z 2 is OH, or Z 1 and Z 2 at least one monomeric compound of formula (I) in which is OH, Z 1 and Z 2 and one or more monomeric compounds of formula (VI), in particular of formula (VI-11), (VI-12), (VI-14), (VI-19) or (VI-20), in particular of formula (VI-11), (VI-19) or (VI-20), very particularly of (VI-11), as dihydroxy component, to form compound LG 1 -C(=O)-LG 1 , for example, by reacting with a carbonate precursor such as a carbonic acid diester.

[0180] However, in the polymerization process for producing polycarbonate resins, some compounds of formula (I) and (VI) may be converted into impurities. For example, in compound (VI), one or both of the terminal OH groups may be replaced with a different group, such as a vinyl end group represented by -OCH=CH2, and X 1 -Z 1 and / or X 2 -Z 2 In compounds (I) where is C2-C5-alkylene-OH, this group can be replaced with an olefin moiety (e.g., -CHCH-OH with -CH=CH2) via water elimination. The amount of such impurities is generally small, so the formed polymer product can be used as a polycarbonate resin without a purification process.

[0181] The thermoplastic resin of the present invention may also contain trace amounts of impurities, for example, as an excess content of the thermoplastic resin composition or as part of the polymer backbone of the thermoplastic resin. Examples of such impurities include phenols (e.g., when diphenyl carbonate is used as a carbonate-forming component), unreacted carbonate diesters, and monomers formed during the process for forming the thermoplastic resin. The total amount of impurities in the thermoplastic resin may be 5,000 ppm or less, or 2,000 ppm or less. The total amount of impurities in the thermoplastic resin is preferably 1,000 ppm or less, more preferably 500 ppm or less, even more preferably 200 ppm or less, and particularly preferably 100 ppm or less.

[0182] The total amount of phenols as impurities in the thermoplastic resin may be 3000 ppm or less, or 2000 ppm or less, 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.

[0183] The total amount of carbonate diesters as impurities in the thermoplastic resin is preferably 1000 ppm or less, more preferably 500 ppm or less, even more preferably 100 ppm or less, and particularly preferably 50 ppm or less.

[0184] 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.

[0185] The lower limit of the total amount of these impurities is not critical, but may be 0.1 ppm or 1.0 ppm.

[0186] The total amount of residual transition metals, such as palladium, as impurities in the thermoplastic resin (which typically result from the esterification catalyst (if any transition metal-containing catalyst is used) and / or the Suzuki reaction used to prepare monomer (I)) 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 an adsorbent, e.g., activated carbon.

[0187] Resins with targeted characteristics can be formed by adjusting the amounts of phenol and diester carbonate. The amounts of phenol, diester carbonate, and monomer can be suitably adjusted by adjusting the polycondensation conditions, the operating conditions of the device used for polymerization, or the conditions for extrusion molding after the polycondensation process.

[0188] The weight average molecular weight (Mw) of the thermoplastic resin of the present invention, as determined by GPC (gel permeation chromatography), is preferably in the range of 5,000 to 100,000 daltons, more preferably 10,000 to 80,000 daltons, even more preferably 10,000 to 50,000 daltons, 15,000 to 55,000 daltons, or 20,000 to 60,000 daltons, particularly 15,000 to 50,000 daltons, 15,000 to 55,000 daltons, 20,000 to 50,000 daltons, 20,000 to 55,000 daltons, 25,000 to 50,000 daltons, or 30,000 to 50,000 daltons. GPC measurements can be calibrated using polystyrene standards. The Mw of the thermoplastic resin of the present invention thus determined is w Also, in this specification, "polystyrene equivalent M w (polystyrene conversion M w ) and "Polystyrene equivalent M w (polystyrene converted M w ) or "M determined by GPC against polystyrene standards" w The number average molecular weight (M n) is preferably 3,000 to 20,000, more preferably 5,000 to 15,000, and even more preferably 7,000 to 14,000. n is determined by GPC measurements calibrated against polystyrene standards as described herein below. w The viscosity average molecular weight (Mv) of the thermoplastic resin according to 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.

[0189] The molecular weight distribution (Mw / Mn) of the thermoplastic resin according to the present invention is preferably 1.5 to 9.0, more preferably 1.8 to 7.0, and even more preferably 2.0 to 4.0.

[0190] When a thermoplastic resin has a weight average molecular weight (Mw) value within the above-mentioned appropriate range, molded articles made from the thermoplastic resin have high strength. Furthermore, such a thermoplastic resin having an appropriate Mw value is advantageous for molding due to its excellent fluidity.

[0191] In a particular group of embodiments, the thermoplastic resin of the present invention comprises at least 0.3 wt. %, preferably at least 0.5 wt. %, more preferably at least 0.8 wt. %, and especially at least 1.0 wt. %, based on the total weight of the thermoplastic resin, of a molecular weight M of less than 1000. w It includes low molecular weight compounds having an M of less than 1000. w The upper limit of said content of low molecular weight compounds having a molecular weight M of less than 1000 in the thermoplastic resin is typically 7.0 wt%, preferably 5.0 wt%, more preferably 3.0 wt%, even more preferably 2.0 wt%, in particular 1.8 wt%, and in particular 1.7 wt%. Thus, in this particular group of embodiments, wis typically in the range of 0.3 to 7.0 wt. %, preferably in the range of 0.5 to 5.0 wt. %, more preferably in the range of 0.8 to 3.0 wt. %, even more preferably in the range of 1.0 to 2.0 wt. %, in particular in the range of 1.0 to 1.8 wt. %, and specifically in the range of 1.0 to 1.7 wt. %, in each case based on the total weight of the thermoplastic resin.

[0192] M less than 1000 in the amount within the above range w The thermoplastic resin of the present invention containing the low molecular weight compound having the above-defined amount forms a molded article having high mechanical strength. Such a thermoplastic resin does not or only tends to undergo little separation or precipitation of the low molecular weight compound, also known as bleed-out, particularly during a molding process such as injection molding. Furthermore, the thermoplastic resin of the present invention containing the above-defined amount of the low molecular weight compound has the advantageous properties of high molding speed and reduced energy requirement for the molding process due to its high plasticity.

[0193] The content of low molecular weight compounds in a 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 to the total area of ​​all peaks in the diagram obtained by GPC analysis of the thermoplastic resin. Therefore, the content of low molecular weight compounds (CLWC) in a thermoplastic resin is expressed by the following formula:

[0194]

number

[0195] The polycarbonate resin mentioned above has a high refractive index (n D or n d) and is therefore suitable for optical lenses. The refractive index values ​​referred to herein are those of a 0.1 mm thick film, which can be measured using an Abbe refractometer according to the method of JIS-K-7142. The refractive index of the polycarbonate resin according to the present invention at 23°C and a wavelength of 589 nm, when the resin contains structural unit (III), is usually 1.640 or more, preferably 1.645 or more, and more preferably 1.650 or more. The thermoplastic resin of the present invention may have a refractive index of 1.660 or more, or 1.670 or more; preferably 1.680 or more or 1.690 or more; and more preferably 1.6950 or more or 1.700 or more.

[0196] For example, the refractive index of the copolycarbonate resin according to the present invention containing the structural unit (III.1) and the structural unit (V) is preferably 1.650 to 1.670 or 1.650 to 1.660. The thermoplastic resin according to the present invention may have a refractive index of 1.650 to 1.705, 1.655 to 1.700, or 1.660 to 1.690.

[0197] The Abbe number (ν) of the polycarbonate resin is preferably 24 or less, more preferably 23 or less, and even more preferably 22 or less, 20 or less, or 18 or less. The Abbe number can be calculated by using the following formula based on the refractive index at wavelengths of 487 nm, 589 nm, and 656 nm at 23° C.: ν=(n D -1) / (n F -n C ) n D : Refractive index at wavelength 589 nm n C : Refractive index at wavelength 656 nm n F : Refractive index at wavelength 486 nm

[0198] The glass transition temperature (T gThe glass transition temperature (T ) of a polycarbonate resin, which is an example of a thermoplastic resin according to the present invention, can be 80 to 290°C or 90 to 290°C, preferably 95 to 280°C or 100 to 285°C, and more preferably 110 to 275°C or 120 to 280°C. g Considering that the polycarbonate can be used for injection molding, the Tg is preferably 90 to 185°C, more preferably 125 to 175°C, and even more preferably 140 to 165°C. Regarding 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. A glass transition temperature (Tg) in the range given above provides a significant usable temperature range and avoids the risk of the resin's melting temperature being too high, which could result in unnecessary decomposition or discoloration. Furthermore, it enables the preparation of molds with high surface accuracy. The value given for the glass transition temperature refers to the value measured by differential scanning calorimetry (DSC) using a 10°C / min heating program according to the JIS K7121-1987 protocol.

[0199] In a preferred embodiment, the absolute value of the orientation birefringence of the thermoplastic resin is preferably 0 to 1×10 -1 or 0 to 1 x 10 -2 range, more preferably 0 to 5 × 10 -3 and more preferably in the range of 0 to 2 × 10 -3 In particular, the range of 0 to 1 × 10 -3 The range is 0 to 0.4 × 10 -3 is in the range.

[0200] The optical molded article, for example, an optical element, produced 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. The total light transmittance of preferably 85% or more is as good as that provided by bisphenol A polycarbonate resin, etc.

[0201] The thermoplastic resin of the present invention has high moist heat resistance. Moist heat resistance can be evaluated by performing a "PCT test" (pressure cooker test) on a molded article, such as an optical element, manufactured using the thermoplastic resin and then measuring the total luminous transmittance of the molded article after the PCT test. In the PCT test, an injection-molded article with a diameter of 50 mm and a thickness of 3 mm is first held for 20 hours under conditions of 120°C, 0.2 MPa, 100% RH, and 20 hours using a PC305S III tester manufactured by Hirayama Seisakusho. The injection-molded article sample is then removed from the device, and the total luminous transmittance is measured using a Nippon Denshoku Industries SE2000 spectroscopic parallax analyzer according to the method of JIS-K-7361-1.

[0202] The thermoplastic resin according to the present invention has a total light transmittance after a 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. As long as the total light transmittance is 60% or more, the thermoplastic resin is considered to have higher moist heat resistance than conventional thermoplastic resins.

[0203] The thermoplastic resin according to the present invention preferably has a b value, which indicates hue, of not more than 5. The smaller the b value, the weaker the yellowness and the better the hue.

[0204] According to the present invention, the diol component used in the preparation of the polycarbonate or polyester is a monomer compound of formula (I) 1 and Z 2 is OH), for example, one or more monomers of formula (VI).

[0205] Monomer compounds of formula (I) 1 and Z 2 Suitable diol monomers other than (wherein is OH) are those conventionally used in the preparation of polycarbonates, such as: aliphatic diols, such as ethylene glycol, propanediol, butanediol, pentanediol and hexanediol; Examples of diols include 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; and aromatic diols, in particular aromatic diols of formula (VI), such as bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)ketone, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-tert-butylphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)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-(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 , also known as 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 and 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl or 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene (BNE)2'-[1,1'-binaphthalene-2,2'-diylbis(oxy)]diethanol.

[0206] Preferably, the diol component comprises, in addition to the monomer of formula (I), at least one monomer of formula (VI). In particular, the combined amount of the monomers of formulas (I) and (VI) contributes to the diol component by at least 90 wt % 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 comprises, in addition to the monomer of formula (I), at least one monomer selected from the monomers of formulas (VI-11) to (VI-20). More particularly, the diol component comprises, in addition to the monomer of formula (I), at least one monomer selected from the monomers of formulas (VI-11), (VI-12), (VI-14), (VI-19), and (VI-20). 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; more particularly 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene.

[0207] Often the relative amount of monomeric compounds of formula (I), based on the total weight of the diol components, is 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, in particular at least 12% by weight or at least 15% by weight, preferably in the range of 1 to 90% by weight or in the range of 5 to 90% by weight, in particular in the range of 2 to 80% by weight or in the range of 5 to 80% by weight or in the range of 8 to 80% by weight or in the range of 10 to 80% by weight, in particular in the range of 5 to 70% by weight or in the range of 8 to 70% by weight or in the range of 10 to 70% by weight or in the range of 15 to 70% by weight, more in particular in the range of 5 to 30% by weight or in the range of 8 to 30% by weight or in the range of 10 to 30% by weight or in the range of 15 to 30% by weight, but may be as high as 100% by weight.

[0208] Often the relative molar amount of the monomeric compounds of formula (I), based on the total moles of diol components, is 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%, in particular at least 12 mol% or at least 15 mol%, preferably in the range of 1 to 80 mol% or in the range of 2 to 80 mol% or in the range of 5 to 80 mol% or in the range of 8 to 80 mol%, in particular in the range of 2 to 70 mol% or in the range of 5 to 70 mol% or in the range of 8 to 70 mol% or in the range of 10 to 70 mol%, in particular in the range of 5 to 60 mol% or in the range of 8 to 60 mol% or in the range of 10 to 60 mol% or in the range of 12 to 60 mol% or in the range of 15 to 60 mol%, more in particular in the range of 5 to 30 mol% or in the range of 8 to 30 mol% or in the range of 10 to 30 mol% or in the range of 12 to 30 mol% or in the range of 15 to 30 mol% or in the range of 15 to 25 mol%, but may be as high as 100 mol%.

[0209] As a result, the relative molar amount of the monomeric compounds of formula (VI), based on the total molar amount of the diol components, does not exceed 99 mol% or 98 mol% or 95 mol%, in particular does not exceed 92 mol% or 90 mol%, in particular does not exceed 88 mol% or 85 mol%, preferably in the range of 20-99 mol% or in the range of 20-98 mol% or in the range of 20-95 mol% or in the range of 20-92 mol%, in particular in the range of 30-98 mol% or in the range of 30-95 mol% or in the range of 30-92 mol%. in the range of 1 to 92 mol% or 30 to 90 mol%, particularly 40 to 95 mol% or 40 to 92 mol% or 40 to 90 mol% or 40 to 88 mol% or 40 to 85 mol%, more particularly 70 to 95 mol% or 70 to 92 mol% or 70 to 90 mol% or 70 to 88 mol% or 70 to 85 mol% or 75 to 85 mol%, but may be as high as 99.9 mol%.

[0210] Often, the total molar amount of the monomers of formula (I) and formula (VI) is at least 80 mol %, particularly at least 90 mol %, and especially at least 95 mol % or up to 100 mol %, based on the total molar amount of the diol monomers in the diol component.

[0211] Further preferred examples of aromatic dihydroxy compounds that may be used in addition to the monomers of formula (I) and optionally the monomers of formula (VI) include, but are not limited to, bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, bisphenol Z, and the like.

[0212] To adjust molecular weight and melt viscosity, the monomers forming the thermoplastic polymer may also contain monofunctional compounds, such as monofunctional alcohols in the case of polycarbonates, and monofunctional alcohols or monofunctional carboxylic acids in the case of polyesters. Suitable monoalcohols include butanol, hexanol, and octanol. Suitable monocarboxylic acids include, for example, benzoic acid, propionic acid, and butyric acid. To increase molecular weight and melt viscosity, the monomers forming the thermoplastic polymer may also contain polyfunctional compounds, such as polyfunctional alcohols with three or more hydroxyl groups in the case of polycarbonates, or polyfunctional alcohols with three or more hydroxyl groups or polyfunctional carboxylic acids with three or more carboxyl groups in the case of polyesters. Suitable polyfunctional alcohols include, for example, glycerin, trimethylolpropane, pentaerythritol, and 1,3,5-trihydroxypentane. Suitable polyfunctional carboxylic acids with three or more carboxyl groups include trimellitic acid and pyromellitic acid. The total amount of these compounds often does not exceed 10 mol% based on the molar amount of the diol component.

[0213] Suitable carbonate-forming monomers are those commonly used as carbonate-forming monomers in the preparation of polycarbonates, including, but not limited to, phosgene, diphosgene, and carbonic acid diesters such as diethyl carbonate, diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, and dinaphthyl carbonate. Among 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 dihydroxy compounds.

[0214] Suitable dicarboxylic acids include, but are not limited to: aliphatic dicarboxylic acids, such as 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.

[0215] [ka]

[0216] Suitable ester-forming derivatives of dicarboxylic acids include, but are not limited to, dialkyl esters, diphenyl esters, and ditolyl esters.

[0217] In the case of polyesters, the ester-forming monomers are often used in a ratio of 0.97 to 1.20 mol, more preferably 0.98 to 1.10 mol, per 1 mol of the total dihydroxy compounds.

[0218] The polycarbonates of the present invention can be prepared by the polymerization of monomers of formula (I), wherein Z 1 and Z 2 is OH) and optionally a further diol monomer such as a monomer of formula (VI) with a carbonate-forming monomer.

[0219] The polyesters of the present invention can be prepared by reacting monomers of formula (I) (wherein Z 1 and Z 2 is OH) and optionally a further diol monomer such as a monomer of formula (VI) with a dicarboxylic acid or an ester-forming derivative thereof.

[0220] The polyestercarbonates of the present invention can be prepared by reacting monomers of formula (I) (wherein Z 1 and Z 2 is OH) and optionally a further diol monomer such as a monomer of formula (VI), a carbonate-forming monomer and a dicarboxylic acid or an ester-forming derivative thereof.

[0221] Polycarbonates, polyesters and polyestercarbonates are usually prepared by reacting the monomers of the diol component with carbonate-forming monomers and / or ester-forming monomers, i.e., dicarboxylic acids or their ester-forming derivatives, in the presence of an esterification catalyst, particularly in the presence of a transesterification catalyst when carbonate-forming monomers or ester-forming derivatives of polycarboxylic acids are used.

[0222] Suitable transesterification catalysts are basic compounds, including, but not limited to, alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, etc. Similarly, suitable transesterification catalysts are acidic compounds, including, but not limited to, Lewis acid compounds of polyvalent metals, including, but not limited to, compounds of zinc, tin, titanium, zirconium, lead, etc.

[0223] Examples of suitable alkali metal compounds include alkali metal salts of organic acids such as acetic acid, stearic acid, benzoic acid, or phenylphosphoric acid, alkali metal phenolates, alkali metal oxides, alkali metal carbonates, alkali metal borohydrides, alkali metal hydrogencarbonates, alkali metal phosphates, alkali metal hydrogenphosphates, alkali metal hydroxides, alkali metal hydrides, alkali metal alkoxides, and the like. Specific examples thereof include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cerium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium borophenoxide, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, and disodium phenylphosphate; disodium, dipotassium, dicesium, and dilithium salts of bisphenol A; and sodium, potassium, cesium, and lithium salts of phenol.

[0224] Examples of alkaline earth metal compounds include alkaline earth metal salts of organic acids such as acetic acid, stearic acid, benzoic acid, or phenylphosphoric acid, alkaline earth metal phenolates, alkaline earth metal oxides, alkaline earth metal carbonates, alkali metal borohydrides, alkaline earth metal bicarbonates, alkaline earth metal hydroxides, alkaline earth metal hydrides, alkaline earth metal alkoxides, etc. Specific examples thereof include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium bicarbonate, calcium bicarbonate, strontium bicarbonate, barium bicarbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, magnesium phenylphosphate, etc.

[0225] Examples of nitrogen-containing compounds include quaternary ammonium hydroxides, their salts, and amines. Specific examples include quaternary ammonium hydroxides containing alkyl or aryl groups, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide; tertiary amines, such as triphenylamine, 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; and bases or basic salts, such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, and tetraphenylammonium tetraphenylborate.

[0226] Preferred examples of transesterification catalysts include salts of polyvalent metals such as zinc, tin, titanium, zirconium, and lead, particularly chlorides, alkoxides, alkanoates, benzoates, and acetylacetonates. These 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 laurate, dibutyltin oxide, dibutyltin methoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead(II) acetate, and lead(IV) acetate.

[0227] It is also preferred to use a base as the transesterification catalyst, more preferably an inorganic basic salt, in particular an alkali metal-containing base such as an alkali metal oxide, alkali metal carbonate, alkali metal borohydride, alkali metal bicarbonate, alkali metal phosphate, alkali metal hydrogen phosphate, alkali metal hydroxide, or alkali metal hydride. In a specific embodiment, an alkali metal carbonate or bicarbonate is used.

[0228] The transesterification catalyst is often used in an amount of 10 moles per mole of the total dihydroxy compounds. -9 ~10 -3 mol, preferably 10 -7 ~10 -4 Used in molar ratios.

[0229] Polycarbonates, polyesters, and polyestercarbonates are often prepared by melt polycondensation, in which the monomers are reacted in the absence of an additional inert solvent. During the reaction, the reaction mixture is heated at ambient or reduced pressure to remove by-products formed in the transesterification reaction.

[0230] The melt polycondensation reaction preferably involves charging monomers and a catalyst into a reactor and subjecting the reaction mixture to conditions that allow reaction between the monomers and the formation of by-products. It has been found to be advantageous for the by-products to be present in the polycondensation reaction for at least some time. However, to drive the polycondensation reaction toward the product side, it is beneficial to remove at least a portion of the formed by-products during the polycondensation reaction or, preferably, at the end of the polycondensation reaction. To allow the by-products to remain in the reaction mixture, the pressure may be controlled by closing the reactor or increasing or decreasing the pressure. The reaction time for this step is 20 to 240 minutes, preferably 40 to 180 minutes, and particularly preferably 60 to 150 minutes. In this step, if the by-products are removed by distillation immediately after their formation, the final thermoplastic resin will have a low content of high-molecular-weight resin molecules. In contrast, if the by-products are allowed to remain in the reactor for a certain period of time, the final thermoplastic resin will have a high content of high-molecular-weight resin molecules.

[0231] The melt polycondensation reaction may be carried out continuously or batchwise. The reactor that can be used for the reaction may be a vertical type including an anchor-type impeller, Maxblend (registered trademark) impeller, helical ribbon impeller, etc., a horizontal type including a paddle impeller, lattice impeller, spectacle impeller, etc., or an extruder type including a screw. In consideration of the viscosity of the polymerization product, a reactor including a combination of such reactors can be preferably used.

[0232] In some methods for producing thermoplastic resins such as polycarbonate resins, catalysts may be removed or deactivated after the polymerization reaction to maintain thermal and hydrolytic stability. A preferred method for deactivating a catalyst is the addition of an acidic substance. Specific examples of acidic substances 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; phosphite 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; triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, dibutyl phosphate, dioctyl phosphate, and phosphate. Examples of suitable deactivators include phosphate esters such as monooctyl phosphate; phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid, and dibutylphosphonic acid; phosphonic acid esters such as diethyl phenylphosphonate; phosphines such as triphenylphosphine and bis(diphenylphosphino)ethane; boric acids such as boric acid and phenylboric acid; aromatic sulfonates such as tetrabutylphosphonium dodecylbenzenesulfonate; organic halides such as stearic acid chloride, benzoyl chloride, and p-toluenesulfonic acid chloride; alkylsulfonic acids such as dimethylsulfonic acid; and organic halides such as benzyl chloride. These deactivators are often used in an amount of 0.01 to 50 mol, preferably 0.3 to 20 mol, relative to the catalyst.

[0233] After deactivating the catalyst, a step of removing low-boiling compounds from the polymer by distillation may be performed. The distillation is preferably carried out at reduced pressure, for example, 0.1 to 1 mmHg, and at a temperature of 200 to 350°C. For this step, a horizontal device containing stirring blades with high surface renewal capacity, such as paddle blades, lattice blades, or spectacle blades, or a thin-film evaporator is preferably used.

[0234] It is desirable for thermoplastic resins such as polycarbonate resins to have an extremely low amount of foreign matter. Therefore, the molten product is preferably filtered to remove solids from the melt. The mesh of the filter is preferably 5 μm or less, more preferably 1 μm or less. The produced polymer is preferably filtered through a polymer filter. The mesh of the polymer filter is preferably 100 μm or less, more preferably 30 μm or less. Needless to say, the step of sampling the resin pellets must be carried out in a low-dust environment. The dust environment is preferably class 6 or less, more preferably class 5 or less.

[0235] Thermoplastic resins can be molded by any conventional molding procedure for producing optical elements. Suitable molding procedures include, but are not limited to, injection molding, compression molding, casting, rolling, extrusion, drawing, etc.

[0236] While the thermoplastic resin of the present invention can be molded in this manner, it is also possible to mold a resin composition containing at least one thermoplastic resin of the present invention and further containing at least one additive and / or additional 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 additional resins include, for example, other polycarbonate resins, polyestercarbonate resins, polyester resins, polyamides, polyacetals, etc. that do not contain the repeating unit of formula (III).

[0237] 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, 5,7-di-tert-butyl-3-(1,2dimethylphenyl)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) Examples include, but are not limited to, t-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. , 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)benzofuran-2(3H)-one, and 5,7-di-tert-butyl-3-(1,2 dimethylphenyl)benzofuran-2(3H)-one are more preferred. The content of the antioxidant in the thermoplastic resin is preferably 0.001 to 0.3 parts by weight based on 100 parts by weight of the thermoplastic resin.

[0238] Examples of processing stabilizers include, but are not limited to, phosphorus-based processing stabilizers, sulfur-based processing stabilizers, etc. Examples of phosphorus-based processing stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, esters thereof, etc. Specific examples of these include triphenyl phosphite, tris(nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2,6-di-tert-butylphenyl)phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, diphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, dimethyl benzene phosphonate, diethyl benzene phosphonate, dipropyl benzene phosphonate, 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, bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, and the like. The content of the phosphorus-based processing stabilizer in the thermoplastic resin composition is preferably 0.001 to 0.2 parts by weight based on 100 parts by weight of the thermoplastic resin.

[0239] 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 per 100 parts by weight of the thermoplastic resin.

[0240] A preferred release agent contains at least 90% by weight of an ester of alcohol and fatty acid. Specific examples of the ester of alcohol and fatty acid include an ester of monohydric alcohol and fatty acid, and a partial or full ester of polyhydric alcohol and fatty acid. A preferred example of the ester of alcohol and fatty acid is an ester of a monohydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. A preferred example of a partial or full ester of a polyhydric alcohol and fatty acid is a partial or full ester of a polyhydric alcohol having 2 to 25 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. Specific examples of the ester of monohydric alcohol and fatty acid include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, etc. Specific examples of partial or full esters of polyhydric alcohols and fatty acids 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 full or partial esters such as dipentaerythritol hexastearate. The content of the release agent in the resin composition is preferably 0.005 to 2.0 parts by weight, more preferably 0.01 to 0.6 parts by weight, and even more preferably 0.02 to 0.5 parts by weight, per 100 parts by weight of the thermoplastic resin.

[0241] Preferred UV absorbers are selected from the group consisting of benzotriazole-based UV absorbers, benzophenone-based UV absorbers, triazine-based UV absorbers, cyclic iminoester-based UV absorbers, and cyanoacrylate-based UV absorbers. That is, the following UV absorbers may be used independently or in combination of two or more.

[0242] Examples of the benzotriazole-based ultraviolet absorber 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.

[0243] 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-sodiumsulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

[0244] 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.

[0245] Examples of cyclic iminoester-based ultraviolet absorbers include 2,2'-bis(3,1-benzoxazin-4-one), 2,2'-p-phenylenebis(3,1-benzoxazin-4-one), 2,2'-m-phenylenebis(3,1-benzoxazin-4-one), 2,2'-(4,4'diphenylene)bis(3,1-benzoxazin-4-one), 2,2'-(2,6-naphthalene)bis(3,1-benzoxazin-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), 2,2'-(2-chloro-p-phenylene)bis(3,1-benzoxazin-4-one), and the like.

[0246] 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.

[0247] 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 part by weight, and even more preferably 0.05 to 0.8 parts by weight, relative to 100 parts by weight of the thermoplastic resin. If the ultraviolet absorber is contained within such a content range, it can provide the thermoplastic resin with sufficient weather resistance depending on the application.

[0248] As mentioned above, the thermoplastic polymer resins, particularly polycarbonate resins, comprising the repeating units of formula (III) described herein provide the thermoplastic resins with high transparency and high refractive index, and are therefore suitable for preparing optical devices requiring high transparency and high refractive index. More precisely, the thermoplastic polycarbonates having structural units of formula (III) are characterized by a high refractive index, preferably at least 1.640, more preferably at least 1.645, and even more preferably at least 1.650.

[0249] The contribution of the monomer of formula (I) to the refractive index of thermoplastic resin, especially polycarbonate resin, depends on the refractive index of said monomer and the relative amount of said monomer in thermoplastic resin.Generally, the higher the refractive index of the monomer contained in thermoplastic resin, the higher the refractive index of the resulting thermoplastic resin.In addition, the refractive index of the thermoplastic resin that comprises the structural unit of formula (III) can be calculated from the refractive index of the monomer used to prepare thermoplastic resin, or from the beginning, for example, by using computer software ACD / ChemSketch 2012 (Advanced Chemistry Development, Inc.).

[0250] In the case of thermoplastic copolymer resins, the refractive index of a thermoplastic resin, in particular a polycarbonate resin, can be calculated from the refractive index of the homopolymers of the respective monomers forming the copolymer resin by the so-called "Fox equation" as follows: 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 is the mass fraction 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 monomer at a time (x1, x2, ....n). For 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 the higher the refractive index of the homopolymer, the higher the refractive index of the copolymer.

[0251] The refractive index of the thermoplastic resin can be determined directly or indirectly. In the case of direct determination, the refractive index of the thermoplastic resin, n D is measured at a wavelength of 589 nm using an Abbe refractometer according to protocol JIS-K-7142, applying a 0.1 mm film of the thermoplastic resin. In the case of the refractive index of the homopolycarbonate of the compound of formula (I), the refractive index can also be determined indirectly. For this purpose, 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 the refractive index of the copolycarbonate, n D is measured at a wavelength of 589 nm using an Abbe refractometer, applying a 0.1 mm film of the copolycarbonate, according to protocol JIS-K-7142. The refractive index n DFrom the above, the refractive index of the homopolycarbonate of each monomer was calculated using the Fox formula and the known refractive index of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (n D (589 nm) = 1.639).

[0252] As mentioned above, R a , R b , R c , R d Compounds of formula (I) that do not have coloring groups, such as part of the group, can also be obtained in a purity that provides a low Yellowness Index YI, determined according to ASTM E313, which can be equally important for use in the preparation of optical resins.

[0253] More precisely, the Yellowness Index YI of the compounds of formula (I), determined according to ASTM E313, preferably does not exceed 200, more preferably 100, even more preferably 50, in particular 20, more particularly 10, even more particularly 5.

[0254] The thermoplastic resin according to the present invention has a high refractive index and a low Abbe number. The thermoplastic resin according to the present invention can be used to produce transparent conductive substrates that can be used in liquid crystal displays, organic electroluminescence displays, solar cells, and the like. Similarly, the thermoplastic resin according to the present invention can be used as a structural material for optical components such as optical disks, liquid crystal panels, optical cards, optical sheets, optical fibers, connectors, vapor-deposited plastic reflectors, and displays; or as an optical device suitable for functional material applications.

[0255] Thus, the thermoplastic resins of the present invention can be used to form molded articles such as optical devices. Optical devices include optical lenses and optical films. Specific examples of optical devices include lenses, films, mirrors, filters, prisms, etc. These optical devices can be formed by any manufacturing process, such as injection molding, compression molding, injection-compression molding, extrusion, or solution casting.

[0256] Due to their excellent moldability and high heat resistance, the thermoplastic resins of the present invention are highly suitable for the production of optical lenses requiring injection molding. For molding, the thermoplastic resins of the present invention, such as polycarbonate resins, can be used as mixtures with other thermoplastic resins, such as different polycarbonate resins, polyestercarbonate resins, polyester resins, and other resins.

[0257] Furthermore, the thermoplastic resin of the present invention can be mixed with additives for forming optical devices. The additives for forming optical devices can include those described above. Examples of additives include antioxidants, processing stabilizers, light stabilizers, polymerized metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, antibacterial agents, mold release agents, UV absorbers, plasticizers, and compatibilizers.

[0258] As is clear from the above, another aspect of the present invention relates to an optical device made from a thermoplastic resin as defined above, which comprises structural units of formula (III) and optionally formula (V). With regard to the preferred meanings and preferred embodiments of the structural units of formula (III) and formula (V), reference is made to the above statements.

[0259] Optical devices made from optical resins containing repeating units of formula (III) and optionally repeating units of formula (V) as defined herein are typically optical lenses, such as automobile headlamp lenses, Fresnel lenses, fθ lenses for laser printers, camera lenses, eyeglass lenses, and rear-projection TV projection lenses, CD-ROM pickup lenses, as well as optical molded articles such as optical disks, optical elements for image display media, optical films, film substrates, optical filters or prisms, liquid crystal panels, optical cards, optical sheets, optical fibers, optical connectors, and vapor-deposited plastic reflectors. Optical lenses and optical films are particularly preferred. Optical resins containing repeating units of formula (III) and optionally repeating units of formula (V) are also useful for producing transparent conductive substrates suitable for use in optical devices as structural or functional components of transparent conductive substrates for liquid crystal displays, organic electroluminescent displays, solar cells, and the like.

[0260] Optical lenses made from the thermoplastic resins of the present invention have a high refractive index, a low Abbe number, and low birefringence, and are highly resistant to humidity and heat. Therefore, the optical lenses can be used in fields where expensive glass lenses with high refractive indices are commonly used, such as telescopes, binoculars, and TV projectors. It is preferable that the optical lenses be used in the form of aspherical lenses. Spherical aberration can be substantially eliminated with a single aspherical lens. Therefore, it is not necessary to use multiple spherical lenses to eliminate spherical aberration. This reduces the weight and manufacturing costs of devices containing spherical aberration. Among various types of optical lenses, aspherical lenses are particularly useful as camera lenses. The present invention easily provides aspherical lenses with a high refractive index and low birefringence, which are technically difficult to manufacture by processing glass.

[0261] The optical lenses of the present invention can be formed, for example, by injection molding, compression molding, injection-compression molding, or casting a resin containing repeating units of formula (III) and optionally repeating units of formula (V), as defined herein.

[0262] The optical lens of the present invention is characterized by small optical distortion. Optical lenses containing conventional optical resins have large optical distortion. Although it is not impossible to reduce the value of optical distortion by adjusting molding conditions, the range of conditions is very narrow, making molding extremely difficult. The resin having the repeating unit of formula (III) and optionally the repeating unit of formula (V) defined in this specification has extremely small optical distortion caused by the orientation of the resin and small molding distortion, so that excellent optical elements can be obtained without strictly setting molding conditions.

[0263] To produce the optical lens of the present invention by injection molding, it is preferable to mold the lens at a cylinder temperature of 260°C to 320°C and a mold temperature of 100°C to 140°C.

[0264] The optical lens of the present invention can be advantageously used as an aspherical lens if necessary. Because a single aspherical lens can substantially eliminate spherical aberration, it is not necessary to eliminate spherical aberration by combining spherical lenses, thereby reducing weight and manufacturing costs. Therefore, among optical lenses, aspherical lenses are particularly useful as camera lenses.

[0265] Resins having repeating units of formula (III) and optionally repeating units of formula (V) as defined herein have high moldability and are therefore particularly useful as materials for thin, small, and complex-shaped optical lenses. The lens size is such that the thickness at the center is 0.05 to 3.0 mm, preferably 0.05 to 2.0 mm, and more preferably 0.1 to 2.0 mm. The lens diameter is 1.0 to 20.0 mm, preferably 1.0 to 10.0 mm, and more preferably 3.0 to 10.0 mm. The lens is preferably a meniscus lens with one convex surface and the other concave surface.

[0266] 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 multiple layers, 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.

[0267] The optical lenses of the present invention can be formed by any method such as metal forming, cutting, polishing, laser machining, electrical discharge machining or deburring, with metal forming being preferred.

[0268] Optical films produced using the thermoplastic resin of the present invention have high transparency and heat resistance, and are therefore suitable for use as liquid crystal substrate films, optical memory cards, etc. To prevent foreign matter from being incorporated into the optical film as much as possible, molding must be carried out in a low-dust environment. The dust environment is preferably class 6 or less, more preferably class 5 or less.

[0269] The following examples serve as further illustration of the present invention.

[0270] 1. Abbreviation: mp: melting point rt: room temperature THF: tetrahydrofuran TLC: Thin Layer Chromatography DSC: Differential scanning calorimetry

[0271] 2. Preparation of Monomers of Formula (I) 2.1 Analysis of the monomer of formula (I): 1 H-NMR spectra were determined using an 80 MHz NMR spectrometer (Magritek Spinsolve 80) at 23° C. The solvent was DMSO-d6 unless otherwise stated.

[0272] IR spectra were obtained using a Shimadzu FTIR-8400S spectrometer (scan number: 45, resolution: 4 cm). -1 ATR FT-IR was recorded using apodization (Happ-Genzel).

[0273] DSC (differential scanning calorimetry) measurements were carried out using a Linseis Chip-DSC 10.

[0274] Unless otherwise stated, the melting points of compounds were determined by Buchi Melting Point B-545.

[0275] UPLC (ultra-performance liquid chromatography) analysis was performed using the following system and conditions: Waters Acquity UPLC H-Class Systems; Column: Acquity UPLC BEH C18, 1.7 μm, 2.1 × 100 mm; Column temperature: 40 °C; Gradient: acetonitrile / 0.1% HClO4 in water: acetonitrile 60% at 0 min, 100% at 3.5 min; 60% at 3.6 min; 60% at 5 min; Injection volume: 2.0 μl; Run time: 6 min; Detection at 210 nm.

[0276] The yellowness index YI of a compound of formula (I) can be determined similarly to ASTM E313 using the following protocol: 1 g of a 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 to 800 nm using a Shimadzu UV-Visible Spectrophotometer UV-1900. The solvent itself, such as methanol, is used as the reference. From the spectrum, the yellowness index can be calculated using the software "RCA-Software UV2DAT" according to ASTM E308 (Standard Practice for Calculating the Color of Objects Using the CIE System) and ASTM E313 (Standard Practice for Calculating the Yellowness Index and Whiteness Index from Instrumentally Measured Color Coordinates).

[0277] 2.2 Preparation example: 2.2.1 Preparation of Monomer (I.1) a) Synthesis of diethyl 2,5-bis(dibenzo[b,d]thiophen-4-yl)benzene-1,4-dicarboxylate [B4DBTPDAEt]:

[0278] [ka] Diethyl 2,5-dibromoterephthalate (78.46 g; 206.46 mmol) was added to dibenzo[b,d]thiophen-4-ylboronic acid (98.88 g; 433.56 mmol; 2.1 equiv.). To this mixture was added 62.77 g of K2CO3 dissolved in 600 mL of anisole and 214 g of water. The mixture was stirred at 60-70 °C and purged with argon until two distinct phases formed. To this mixture, tris(o-tolyl)phosphane (2.513 g; 8.26 mmol) and Pd(OCOCH3)2 (464 mg; 2.065 mmol) were added under an argon atmosphere, and the mixture was stirred at reflux until TLC showed complete conversion. The mixture was cooled to rt and the precipitated solid was filtered off, then washed with water (50 mL), methanol (3×200 mL), and pentane (400 mL), and finally dried overnight at 60° C. The resulting grey solid was used in the next step without further purification. 1 H NMR (80 MHz, DMSO-d6): δ = 8.58 - 8.25 (m, 4H), 8.21 - 7.92 (m, 4H), 7.82 - 7.35 (m, 8H), 3.89 (q, J = 7.1 Hz, 4H), 0.68 (t, J = 7.1 Hz, 6H).

[0279] b) Synthesis of [2,5-bis(dibenzo[b,d]thiophen-4-yl)-1,4-phenylene]dimethanol [B4DBTPDMO; compound (I.1)]:

[0280] [ka] Lithium aluminum hydride [LiAlH4] (2.57 g; 67.70 mmol; 3 equiv.) was dissolved in tetrahydrofuran (800 g; ca. 900 mL) at rt, and the solution was cooled to 0 °C. Then, 13.24 g (22.57 mmol) of 2,5-bis(dibenzo[b,d]thiophen-4-yl)benzene-1,4-dicarboxylate [B4DBTPDAEt] was added portionwise as a solid. The reaction mixture was stirred at 0 °C for 1 h, then warmed to rt, and stirred at rt for an additional 1–2 h until TLC indicated complete conversion. The mixture was carefully quenched at rt with 4.85 g of water in 25 mL of THF. Then, 4.85 mL of 15% NaOH solution was added, followed by water (9.7 g) under vigorous stirring. The reaction mixture was stirred at rt for an additional 30 min. The resulting aluminum salts were filtered off, and the filter cake was washed with THF (3 × 100 mL) [warmed to 50–60 °C]. The organic extracts were combined, and the THF was evaporated to give 9.64 g (83.6% yield; 98.37% purity) of the crude title product, which was dried in vacuo (20–50 mbar, 60 °C). The crude product was recrystallized from THF to give the desired product in 99.23% purity. 1 H NMR (80 MHz, DMSO-d6): δ =8.62 - 8.28 (m, 4H), 8.21 - 7.86 (m, 2H), 7.86 - 7.39 (m, 10H), 5.22 (t, J= 4.7, 2H), 4.46 (d, J= 4.7, Hz, 4H).mp (DSC): 295.5℃

[0281] 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 ): Refractive index measurements were performed using specimens obtained by the general procedure for preparing homopolycarbonates described in Section 3.2 below, using a Rudolph Instruments J257 autorefractometer at 23°C and 589 nm.

[0282] Abbe number (ν): The Abbe number was determined using the same approximately 3 mm thick sample used in the refractive index measurement method described above. Refractive index values ​​were measured using a Metricon 2010M Prism Coupler at a temperature of 23°C and wavelengths of 486 nm, 589 nm, and 656 nm. The Abbe number was then calculated using the following formula: ν=(n D -1) / (n F -n C ) n D : Refractive index at wavelength 589 nm n C : Refractive index at wavelength 656 nm n F : Refractive index at wavelength 486 nm

[0283] Glass transition temperature (Tg): The glass transition temperature was measured by differential scanning calorimetry (DSC) using a 10°C / min heating program according to JIS K7121-1987.

[0284] Differential scanning calorimetry device: X-DSC7000 manufactured by Hitachi High-Tech Science Corporation

[0285] molecular weight Resin weight average molecular weight (M w The values ​​of (a) and (b) are measured by gel permeation chromatography (GPC) and calculated using standard polystyrene standards. The following device, column, and measurement conditions were used: GPC device: HLC-8420GPC (Tosoh Corporation); Columns: three TSKgel SuperHM-M (Tosoh Corporation); One guard column, SuperHM-M (Tosoh Corporation), one TSKgel SuperH-RC (manufactured by Tosoh Corporation); Detection device: RI detection Standard polystyrene: PstQuick C (Tosoh Corporation) as a standard polystyrene kit; Eluent: tetrahydrofuran; Eluent flow rate: 0.6 ml / min; Column temperature: 40°C.

[0286] 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 weight average molecular weight (Mw) and number average molecular weight (Mn) converted to polystyrene were calculated using a previously prepared polystyrene standard curve. Specifically, a standard curve was prepared using a standard polystyrene ("PStQuick C" manufactured by Tosoh Corporation) with a known molecular weight. Furthermore, a calibration curve was obtained by plotting the elution time and molecular weight value of each peak based on the measured data of the standard polystyrene and performing a three-dimensional fit. The values ​​for Mw and Mn were calculated based on the following formula: Mw = Σ(Wi × Mi) ÷ Σ(Wi) Mn = Σ(Ni × Mi) ÷ Σ(Wi) In the formula, "i" represents the "i"th division point, "Wi" represents the molecular weight (g) of the polymer at the "i"th division point, "Ni" represents the number of polymer molecules at the "i"th division point, and "Mi" represents the molecular mass at the "i"th division point. The molecular mass (M) represents the value of the molecular mass of polystyrene at the corresponding elution time of the calibration curve.

[0287] Low molecular weight compound (CLWC) content 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, where the peak area is determined according to the GPC analysis described above. Therefore, the CLWC value can be determined using the following formula:

[0288]

number

[0289] Low molecular weight compounds M w The value of can be determined using the methods described in the "Molecular Weight" section above.

[0290] Birefringence (Δn): The birefringence (Δn) value of a resin can be measured, for example, according to the following method: Each resin example to be analyzed is dissolved in methylene chloride (solvent) to form a solution with a concentration of 10% by weight. The resulting solution is cast onto a SUS plate whose surface has been treated with electroplating to produce a cast film, after which the solvent is evaporated at 25°C. A square film piece with a thickness of 100 μm and a side length of 50 mm is cut from the cast film. The film piece is then cut into a square piece with a thickness of 100 μm and a side length of 50 mm ... g The film is stretched 1.5 times at a temperature 20°C higher than the initial temperature. The stretching can be performed using a stretching machine SS-70 manufactured by Shibayama Scientific Instruments Manufacturing Co., Ltd. The resulting stretched film is subjected to retardation measurement using an ellipsometer M-220 manufactured by JASCO Corporation.

[0291] From the retardation / phase difference Re, the birefringence value Δn can be calculated by the following formula: Δn=|Re / d| Δn: Orientation birefringence Re: Phase difference [nm] d: thickness [nm]

[0292] The arithmetic sign of birefringence is the refractive index in the stretching 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=nII -n ⊥

[0293] When Δn is positive, it is called positive birefringence, and when Δn is negative, it is called negative birefringence.

[0294] 3.2 Example of preparation of homopolycarbonate: [Example 2] Homopolycarbonate prepared from B4DBTPDMO and diphenyl carbonate The homopolycarbonate of Example 2 was prepared by reacting B4DBTPDMO, the monomer compound of formula (I.1) prepared in Example 1, with diphenyl carbonate as the diol component in a manner similar to that used to prepare the copolycarbonate of Example 3 below (the difference being that BPEF was omitted). Table 1 below lists the physical properties of the resulting B4DBTPDMO homopolycarbonate, namely, the refractive index (n D ), Abbe number (ν) and glass transition temperature (T g For comparison, the table lists the n of a comparative homopolycarbonate similarly prepared from 9,9-bis(4-(2-hydroxyethoxy)-phenyl)fluorine (BPEF) and diphenyl carbonate as the diol component. D -, ν and T g The B4DBTPDMO homopolycarbonate of Example 2 consists of structural units of formula (III.1.1) and structural units of formula (IV-1), and the comparative BPEF homopolycarbonate consists of structural units derived from the monomer 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene and structural units of formula (IV-1).

[0295] The n of B4DBTPDMO homopolycarbonate of Example 2 shown in Table 1 D -, ν and T g The values ​​were calculated from the respective values ​​of the corresponding copolymer derived from the monomers of Example 1 by using the Fox equation described above. The preparation of this copolymer and its physical data are described in Example 3 below.

[0296] [Table 1] [ka]

[0297] 3.3 Example of preparation of copolycarbonate: [Example 3] Copolymer prepared from B4DBTPDMO, BPEF and diphenyl carbonate The materials used were 3.00 kg (5.97 mol) of (2,5-bis(dibenzo[b,d]thiophen-4-yl)-1,4-phenylene)dimethanol (B4DBTPDMO; compound (I.1) prepared in Example 1), 10.47 kg (23.87 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF), 6.58 kg (30.74 mol) of diphenyl carbonate (DPC), and 2.5 × 10 -2 mol / l (3.0 × 10 -4 mol (10 × 10 for 1 mol of total dihydroxy compounds) -6A 50-liter reactor equipped with a stirrer and distillation device was charged with 12 ml of an aqueous solution of sodium bicarbonate (12 mol). The reactor was flushed with nitrogen, and the reaction mixture was heated to 205°C for 1 hour and stirred at 760 Torr. After complete dissolution, the pressure was reduced to 150 Torr over 15 minutes, and the transesterification reaction was carried out at 205°C and 150 Torr for 20 minutes. The reaction mixture was then heated to 240°C at a heating rate of 37.5°C / h, and the reaction conditions of 240°C and 150 Torr were maintained for 10 minutes. The pressure was then reduced to 120 Torr over 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 over 10 minutes, and the reaction conditions of 240°C and 100 Torr were maintained for 10 minutes. The pressure was further reduced to below 1 Torr over 40 minutes, and the polymerization reaction was carried out at 240°C and 1 Torr for 10 minutes. After the reaction was completed, the pressure was increased by introducing nitrogen into the reactor, and the resulting polycarbonate resin was pelletized and removed from the reactor. The characteristics of the resulting copolycarbonate resin are summarized in Table 2. For easy comparison, the values ​​for the homopolymer of Example 2 are also listed. The weight average molecular weight (M) of the copolycarbonate resin of Example 3 was w ) was 52,000.

[0298] [Table 2]

Claims

1. Use of compounds of formula (I) as monomers for the preparation of thermoplastic resins selected from the group consisting of polycarbonates, polyesters and polyestercarbonates, in particular polycarbonates and polyesters: 【Chemistry 1】 (In the formula, X １ and X ２ are each independently a bond or C １ ~C ５ -alkanediyl; Z １ and Z ２ are, independently of one another, OH or C(O)OR ｘ and R ｘ is hydrogen, C １ ~C ４ - selected from the group consisting of alkyl, phenyl and benzyl; R ａ , R ｂ , R ｃ and R ｄ one or two of which are dibenzothiophene groups of formula (II): 【Chemistry 2】 where # indicates the point of attachment to the rest of the molecule. and R ａ , R ｂ , R ｃ and R ｄ The other two or three are hydrogen, halogen, C ２ ~C ３ -Alkynyl, CN, R, S(O) ｋ R, NHR, NR ２ , OR and C(O)R; or R ｃ and R ｄ may be taken together with the carbon atoms to which they are attached to form a fused benzene ring; Each R is C １ ~C ４ - independently selected from the group consisting of alkyl, phenyl, benzyl and naphthyl; and k is 0, 1 or 2.

2. X １ and X ２ However, independently of each other, C １ ~C ５ 2. The use according to claim 1, wherein the alkanediyl is -alkanediyl.

3. X １ and X ２ The use according to claim 2, wherein both are methylene.

4. Z １ and Z ２ The use according to any one of claims 1 to 3, wherein both are OH.

5. X １ and X ２ are both bonds, and Z １ and Z ２ is C(O)OR ｘ and R ｘ but preferably hydrogen and C １ ~C ４ 2. The method according to claim 1, wherein the aryl group is selected from the group consisting of - alkyl, more preferably hydrogen.

6. R ａ , R ｂ , R ｃ and R ｄ 6. The use according to any one of claims 1 to 5, wherein two of are dibenzothiophene groups of formula (II).

7. R which is not a dibenzothiophene group of formula (II) ａ , R ｂ , R ｃ and R ｄ 7. The use according to any one of claims 1 to 6, wherein the group is hydrogen.

8. R ａ and R ｄ is a dibenzothiophene group of formula (II), and R ｂ and R ｃ The use according to any one of claims 1 to 7, wherein is hydrogen.

9. 9. Use according to any one of claims 1 to 8, wherein the dibenzothiophene group of formula (II) is a group of formula (II.1): 【Transformation 3】 (where # indicates the point of attachment to the rest of the molecule).

10. Use according to any one of claims 1 to 9, wherein the compound of formula (I) is a compound of formula (I.1): 【Chemistry 4】

11. 22. Use according to any one of claims 1 to 10 as a monomer for producing a thermoplastic resin as defined in any one of claims 13 to 21.

12. A compound of formula (I) as defined in any one of claims 1 to 10, excluding the following compounds: dimethyl 2,5-di(dibenzothiophen-2-yl)benzene-1,4-dicarboxylate; and 2,5-di(dibenzothiophen-2-yl)benzene-1,4-diol.

13. A thermoplastic resin comprising a structural unit represented by formula (III): 【Transformation 5】 (In the formula, # represents the point of attachment to the adjacent structural unit; Z １１ is a bridging group -O- or -C(O)-O-, and the carbon atom of the -C(O)-O- group is X １ is bound to; Z １２ is a bridging group -O- or -C(O)-O-, and the carbon atom of the -C(O)-O- group is X ２ is bound to; X １ , X ２ , R ａ , R ｂ , R ｃ and R ｄ is as defined in any one of claims 1 to 10).

14. 14. Thermoplastic resin according to claim 13, selected from the group consisting of polycarbonates, polyesters and polyestercarbonates, in particular polycarbonates and polyesters.

15. A structural unit represented by formula (III) (wherein Z １１ and Z １２ and (III.1) are both bridging groups -O-, and the structural unit is in this case a structural unit of formula (III.1): 【Transformation 6】

16. The structural unit of formula (III) １１ and Z １２ and (IV-1) are both bridging groups -O-) are bonded to one of the structures represented by formulas (IV-1) to (IV-5): 【Transformation 7】 (In the formula, # represents the point of attachment to the adjacent structural unit).

17. 17. The thermoplastic resin according to any one of claims 13 to 16, wherein the thermoplastic resin is selected from copolycarbonate resins, copolyestercarbonate resins and copolyester resins, which, in addition to structural units represented by formula (III), also contain structural units of formula (V): #-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 directly fused to each other and / or fused to a non-benzene carbocyclic ring; １ is unsubstituted or contains 1, 2 or 3 R ａａ Group (R ａａ is a 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'): 【Transformation 8】 (In the formula, 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 ring atoms of the hetaryl are selected from nitrogen, sulfur, and oxygen, and the remainder of the ring atoms of the hetaryl are carbon atoms; Ar is unsubstituted or contains 1, 2, or 3 R ａｂ Group (R ａｂ is halogen, phenyl and C １ ~C ４ -alkyl); and 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; Alk ３ is C １ ~C ４ -alkanediyl).

18. The thermoplastic resin according to claim 17, wherein the structural unit of formula V is represented by one of the following formulas V-1 to V-6: 【Chemistry 9】 (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 for formula (V).

19. 19. Thermoplastic resin according to claim 17 or 18, wherein the molar ratio of the structural units of formula (III) is 1 to 70 mol %, in particular 5 to 60 mol % or 10 to 40 mol %, based on the total molar amount of the structural units of formulae (III) and (V), and the molar ratio of the structural units of formula (V) is 30 to 99 mol %, in particular 40 to 95 mol % or 60 to 90 mol %, based on the total molar amount of the structural units of formulae (III) and (V).

20. 20. The thermoplastic resin according to any one of claims 13 to 19, having a refractive index of 1.640 or greater.

21. 21. The thermoplastic resin of any one of claims 13 to 20, having an Abbe number of 24 or less.

22. Glass transition temperature (T ｇ 22. The thermoplastic resin according to any one of claims 13 to 21, wherein

23. The thermoplastic resin according to any one of claims 13 to 22, having a glass transition temperature (Tg) of 90 to 185°C.

24. 24. An optical device made from a thermoplastic resin as defined in any one of claims 13 to 23.

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