Sulfur-containing heterocyclic compound and thermoplastic resin

Abstract

The present invention relates to compounds of formula (I): wherein X1 and X2 are independently selected from the group consisting of-(C1-C5-alkanediyl)-OH and-C (O) ORx, wherein Rx is selected from the group consisting of hydrogen and C1-C4-alkyl; a1 and A2 are independently selected from a single bond and a monocyclic or polycyclic arylene group having 6 to 26 carbon atoms as ring members, wherein the monocyclic or polycyclic arylene group is unsubstituted or carries 1, 2, 3 or 4 RAr groups; z1 and Z2 are selected from phenylene and naphthylene; and the other groups are as defined in the specification, their use as monomers for the manufacture of thermoplastic resins selected from the group consisting of polycarbonates, polyesters and polyestercarbonates. The present invention also relates to a thermoplastic resin selected from the group consisting of polycarbonates, polyesters, and polyestercarbonates, comprising a structural unit represented by the following formula (II): wherein # represents a connection point to an adjacent structural unit; x1a and X2a are respectively derived from X1 and X2, and the-OH or-ORx group of X1 or X2 is replaced by an oxo (-O-) moiety; and X1, X2, A1, A2, R1, R2, n, p and q are as defined above.

Description

Technical Field

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

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

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

[0004]

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

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

[0007] WO 2007 / 064608 describes, inter alia, dihydroxyheterocyclic compounds and their use for preparing polymers.

[0008] DE 197 33 882 describes thianthrene polymers as hole-transport layers in optical devices such as light-emitting diodes.

[0009] Despite the progress made in the field of optical resins, there is still a continuing need for optical resins, particularly polycarbonate resins, which have a high refractive index and can therefore be used to manufacture optical devices, particularly lenses. In addition, the resin should meet the requirements of optical resins, such as low Abbe number, high transparency and a suitable glass transition temperature (T g ). In addition, the resin should be easy to prepare and have good mechanical properties. SUMMARY OF THE INVENTION

[0010] Thus, a first aspect of the present invention relates to the use of a compound of formula (I) or a mixture of different compounds of formula (I) as a monomer for the production of a thermoplastic resin selected from polycarbonates, polyesters and polyester carbonates, in particular for the production of polycarbonates,

[0011]

[0012] wherein

[0013] X 1 and X 2 are independently selected from -(C1-C5-alkanediyl)-OH and -C(O)OR x ,

[0014] where R x is selected from hydrogen and C1-C4-alkyl;

[0015] A 1 and A 2 are independently selected from a single bond and a monocyclic or polycyclic arylene having 6 to 26 carbon atoms as ring members, wherein the monocyclic or polycyclic arylene is unsubstituted or bears 1, 2, 3 or 4 R Ar groups;

[0016] Z 1 and Z 2 are selected from phenylene and naphthylene;

[0017] Y is selected from a single bond, O, S, S(O) and S(O)2;

[0018] R 1 and R 2 are independently selected from halogen, C2-C3-alkynyl, CN, R, OR, CH s R' 3-s , NR2, C(O)R and CH=CHR", and if p+q>1, then R 1 and R 2 can be the same or different, where s is 0, 1 or 2 each time it appears;

[0019] n is 0, 1 or 2;

[0020] p and q are independently 0, 1 or 2;

[0021] R is selected from C1-C4-alkyl, phenyl, naphthyl, phenanthryl and triphenylenyl, wherein phenyl, naphthyl, phenanthryl and triphenylenyl are unsubstituted or substituted by 1, 2, 3 or 4 identical or different R'" groups;

[0022] R' is selected from phenyl, naphthyl, phenanthrenyl and triphenylene, wherein phenyl, naphthyl, phenanthrenyl and triphenylene are unsubstituted or substituted with 1, 2, 3 or 4 identical or different R'" groups;

[0023] R" is selected from hydrogen, methyl, phenyl and naphthyl, wherein phenyl and naphthyl are unsubstituted or substituted with 1, 2, 3 or 4 identical or different R'" groups;

[0024] R'" is selected from phenyl, halogen, OCH3, CH3, N(CH3)2 and C(O)CH3;

[0025] R Ar Selected from fluorine, bromine, chlorine, CN, R 3 , OR 3 , benzyl, NR 3 2. C(O)R 3 and C(O)NH2, if more than one R Ar , then R Ar may be the same or different; and

[0026] R 3 is selected from C1-C4-alkyl, phenyl and naphthyl.

[0027] The second aspect relates to a thermoplastic resin comprising polymerized units of a compound of formula (I), namely a thermoplastic resin selected from polycarbonates, polyesters and polyester carbonates, in particular polycarbonates and polyesters comprising structural units represented by the following formula (II);

[0028]

[0029] in

[0030] # indicates the connection point with the adjacent structural unit;

[0031] X 1a and X 2a Derived from X 1 and X 2 , replacing X with an oxo (-O-) moiety 1 or X 2 -OH or -OR x group; and

[0032] X 1 、X 2 、A 1 、A 2 、R 1 、R 2 , n, p and q are as defined above.

[0033] A third aspect of the invention relates to an optical device made from a thermoplastic resin as defined above, in particular a polyester, especially a polycarbonate.

[0034] Another aspect of the present invention relates to compounds of formula (I), which are to some extent novel. DETAILED DESCRIPTION

[0035] For the purposes of the present invention, the term "C1-C5-alkanediyl", which may also be referred to alternatively as "C1-C5-alkylene", refers to a divalent saturated aliphatic hydrocarbon radical having 1, 2, 3, 4 or 5 carbon atoms. Examples of C1-C5-alkanediyl are in particular methylene (CH2), straight-chain alkanediyl groups such as 1,2-ethanediyl (CH2CH2), 1,3-propanediyl (CH2CH2CH2), 1,4-butanediyl (CH2CH2CH2CH2) and 1,5-pentanediyl (CH2CH2CH2CH2CH2), but also branched alkanediyl groups such as 1-methyl-1,2-ethanediyl, 1-methyl-1,2-propanediyl, 2-methyl-1,2-propanediyl, 2-methyl-1,3-propanediyl and 1,3-butanediyl.

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

[0037] For the purposes of the present invention, the term "monocyclic heteroaryl" refers to a monovalent heteroaromatic monocyclic radical, i.e. a heteroaromatic monocyclic ring which is linked to the rest of the molecule by a single covalent bond, wherein the ring member atoms are part of a conjugated π-electron system, wherein the heteroaromatic monocyclic ring has 5 or 6 ring atoms which include 1, 2, 3 or 4 nitrogen atoms or 1 oxygen atom and 0, 1, 2 or 3 nitrogen atoms or 1 sulfur atom and 0, 1, 2 or 3 nitrogen atoms as heteroring members, wherein the remaining ring atoms are carbon atoms. Examples include furyl (=furanyl), pyrrolyl (=1H-pyrrolyl), thienyl (=thiophenyl), imidazolyl (=1H-imidazolyl), pyrazolyl (=1H-pyrazolyl), 1,2,3-triazolyl, 1,2,4-triazolyl, tetrazolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, 1,3,4-oxadiazolyl, 1,3,4-thiadiazolyl, pyridyl (=pyridinyl), pyrazinyl, pyridazinyl, pyrimidinyl and triazinyl.

[0038] For the purposes of the present invention, the term "monocyclic or polycyclic aromatic group" refers to a monovalent aromatic monocyclic radical as defined herein, or to a monovalent aromatic polycyclic radical, i.e. a polycyclic aromatic hydrocarbon linked to the rest of the molecule by a single covalent bond, wherein the polycyclic aromatic hydrocarbon is

[0039] (i) aromatic polycyclic hydrocarbons, i.e. fully unsaturated polycyclic hydrocarbon radicals in which each carbon atom is part of a conjugated π-electron system,

[0040] (ii) a polycyclic hydrocarbon having at least one benzene ring fused to a saturated or unsaturated 4- to 10-membered monocyclic or bicyclic hydrocarbon ring,

[0041] (iii) Polycyclic hydrocarbons having at least two benzene rings which are linked to each other by covalent bonds or directly fused to each other and / or to a saturated or unsaturated 4- to 10-membered monocyclic or bicyclic hydrocarbon ring.

[0042] Monocyclic or polycyclic aryl groups have 6 to 26, typically 6 to 24, for example 6, 9, 10, 12, 13, 14, 16, 17, 18, 19, 20, 22 or 24 carbon atoms as ring atoms, in particular 6 to 20, especially 6, 10, 12, 13, 14, 16, 17 or 18 carbon atoms. Polycyclic aryl groups usually have 10 to 26, especially 10 to 20, in particular 10, 12, 13, 14, 16, 17 or 18 carbon atoms as ring atoms.

[0043] In this context, polycyclic aromatic radicals having 2, 3 or 4 benzene rings linked to one another by single bonds include, for example, biphenyl and terphenyl. Polycyclic aromatic radicals having 2, 3 or 4 benzene rings directly fused to one another include, for example, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, triphenylenyl, Polycyclic aromatic groups having 2, 3 or 4 benzene rings fused to a saturated or unsaturated 4- to 10-membered monocyclic or bicyclic hydrocarbon ring include, for example, 9H-fluorenyl, biphenylenyl, tetraphenylenyl, acenaphthenyl (1,2-dihydroacenaphthenyl), acenaphthylenyl, 9,10-dihydroanthracene-1 -yl, 1,2,3,4-tetrahydrophenanthrenyl, 5,6,7,8-tetrahydrophenanthrenyl, cyclopenta[fg]acenaphthenyl, phenalenyl, fluoranthenyl, benzo[k]fluoranthenyl, perylenyl, 9,10-dihydro-9,10[1',2']-benzanthryl, dibenzo[a,e][8]annulenyl, 9,9'-spiro[9H-fluorenyl]yl and spiro[1H-cyclobut[de]naphthalene-1,9'-[9H]fluorenyl]yl.

[0044] Monocyclic or polycyclic aromatic groups include, by way of example, phenyl, naphthyl, 9H-fluorenyl, phenanthrenyl, anthracenyl, pyrenyl, phenyl, benzo[c]phenanthrenyl, acenaphthenyl, acenaphthenyl, 2,3-dihydro-1H-indenyl, 5,6,7,8-tetrahydronaphthyl, cyclopenta[fg]acenaphthenyl, 2,3-dihydrophenanthrenyl, 9,10-dihydroanthracen-1-yl, 1,2,3,4-tetrahydrophenanthrenyl, 5,6,7,8-tetrahydrophenanthrenyl, fluoranthenyl, benzo[k]fluoranthenyl, biphenylene, triphenylene, tetraphenylene, 1,2-dihydroacenaphthenyl, dibenzo[a,e][8]annulyl, perylenyl, biphenyl, terphenylene, naphthylphenyl (naphthylenpheny l), phenanthrenylphenyl, anthracenylphenyl, pyrenylphenyl, 9H-fluorenylphenyl, di(naphthylene)phenyl, naphthylenebiphenyl, tri(phenyl)phenyl, tetra(phenyl)phenyl, pentaphenyl(phenyl), phenylnaphthyl, binaphthyl, phenanthrennaphthyl, pyrenylnaphthyl, phenylanthracenyl, biphenylanthracenyl, naphthylanthracenyl, phenanthrenanthracenyl, dibenzo[a,e][8]annulenyl, 9,10-dihydro-9,10[1',2']benzanthryl, 9,9'-spirobi-9H-fluorenyl and spiro[1H-cyclobut[de]naphthyl-1,9'-[9H]fluorenyl]yl.

[0045] For the purposes of the present invention, the term "monocyclic or polycyclic heteroaryl" refers to a monovalent heteroaromatic monocyclic radical as defined herein, or to a monovalent heteroaromatic polycyclic radical, i.e. a polycyclic heteroarene linked to the rest of the molecule by a single covalent bond, wherein

[0046] (i) a polycyclic heteroarene carrying a heteroaromatic monocyclic ring as defined above and at least one, for example 1, 2, 3, 4 or 5, further aromatic rings selected from phenyl and heteroaromatic monocyclic rings as defined above, wherein the aromatic rings of the polycyclic heteroarene are linked to one another by covalent bonds and / or are directly fused to one another and / or to a saturated or unsaturated 4- to 10-membered monocyclic or bicyclic hydrocarbon ring, or

[0047] (ii) polycyclic heteroaromatic hydrocarbons carrying at least one saturated or partially or completely unsaturated 5-, 6-, 7- or 8-membered heterocyclic ring carrying 1, 2 or 3 heteroatoms selected from oxygen, sulfur and nitrogen as ring atoms, for example 2H-pyran, 4H-pyran, thiopyran, 1,4-dihydropyridine, 4H-1,4-oxazine, 4H-1,4-thiazine, 1,4-dioxin, oxepin, thiophenin, dioxin, dithiophenin, dithiophenin, dioxoc ... dioxocine), dithiocine, and at least one, for example 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 heterocycle, and wherein the aromatic rings of the polycyclic heteroarenes are linked to each other by covalent bonds or are directly fused to each other and / or to a saturated or unsaturated 4- to 10-membered monocyclic or bicyclic hydrocarbon ring.

[0048] Monocyclic or polycyclic heteroaryl groups have 5 to 26, typically 5 to 24, in particular 5 to 20 ring atoms, including 1, 2, 3 or 4 atoms selected from nitrogen atoms, sulfur atoms and oxygen atoms, wherein the remaining atoms in the ring atoms are carbon atoms. Polycyclic heteroaryl groups usually have 9 to 26, typically 9 to 24, in particular 9 to 20 ring atoms, including 1, 2, 3 or 4 atoms selected from nitrogen atoms, sulfur atoms and oxygen atoms, wherein the remaining atoms in the ring atoms are carbon atoms.

[0049] Examples of polycyclic heteroaryl groups include, but are not limited to, benzofuranyl, benzothienyl, dibenzofuranyl (=dibenzo[b,d]furanyl), dibenzothienyl (=dibenzo[b,d]thienyl), naphthofuranyl, naphthothienyl, 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, yl), benzopyrazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, benzo[c,d]indolyl, 1H-benzo[g]indolyl, quinolinyl, isoquinolinyl, acridinyl, phenazinyl, quinazolinyl, quinoxalinyl, phenoxazinyl, phenothiazinyl, benzo[b][1,5]naphthyridinyl, cinnolinyl, 1,5-naphthyridinyl, 1,8-naphthyridinyl, phenylpyrrolyl, naphthylpyrrolyl, dipyridyl, phenylpyridinyl, naphthylpyridinyl, pyrido[4,3-b]indolyl, pyrido[3,2-b]indolyl, pyrido[3,2-g]quinolinyl, pyrido[2,3-b][1,8]naphthyridinyl, pyrrolo[3,2-b]pyridinyl, pteridinyl, purinyl, 9H- Xanthenyl, 9H-thioxanthenyl, 2H-chromenyl, 2H-thiochromenyl, phenanthridinyl, phenanthrolinyl, benzo[1,2-b:4,3-b']bifuranyl, benzo[1,2-b:6,5-b']bifuranyl, benzo[1,2-b:5,4-b']bifuranyl, benzo[1,2-b:4,5-b']bifuranyl, naphthofuranofuranyl, pyranyl, benzo[b]naphtho[1,2-d]furyl, benzo[b]naphtho[2,3-d]furyl, benzo[b]naphtho[2,1-d]furyl, 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,d]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']bithienyl, benzo[1,2-b:6,5-b']bithienyl, benzo[1,2-b:5,4-b']bithienyl, benzo[1,2-b:4,5-b']bithienyl, 1,4-benzodithiinyl, naphtho[1,2-b][1,4]dithianyl, naphtho[2,3-b][1,4]dithianyl, thianthrenyl, benzo[a]thianthrenyl, benzo[b]thianthrenyl, dibenzo[a,c]thianthrenyl, dibenzo[a,h]thianthrenyl, dibenzo[a,i]thianthrenyl, dibenzo[a,j]thianthrenyl, dibenzo[b,i]thianthrenyl, 2H-naphtho[1,8-b,c]thienyl, 5H-phenanthrene benzo[4,5-b,c,d]thiopyranyl, 10,11-dihydrodibenzo[b,f]thiophene-inyl, 6,7-dihydrodibenzo[b,d]thiophene-inyl, dibenzo[b,f]thiophene-inyl, dibenzo[b,d]thiophene-inyl, 6H-dibenzo[d,f][1,3]dithiophene-inyl, tribenzo[b,d,f]thiophene-inyl, 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]quinolyl, furo[2,3-g]quinolyl, furo[2,3-g]quinoxalinyl, benzo[g]chromenyl, thieno[3,2-f [1]benzothiophenyl, thieno[2,3-f][1]benzothiophenyl, thieno[3,2-g]quinolyl, thieno[2,3-g]quinolyl, thieno[2,3-g]quinoxalinyl, benzo[g]thiochromenyl, pyrrolo[3,2,1-h,i]indolyl, benzo[g]quinoxalinyl, benzo[f]quinoxalinyl and benzo[h]isoquinolyl.

[0050] For the purposes of the present invention, the term "monocyclic arylene" refers to a divalent aromatic monocyclic radical, such as, in particular, phenylene.

[0051] For the purposes of the present invention, the term "monocyclic or polycyclic arylene" refers to a divalent aromatic monocyclic radical or a divalent aromatic polycyclic radical as defined herein, i.e. a polycyclic aromatic hydrocarbon linked to two other parts of the molecule by two single covalent bonds, wherein the polycyclic aromatic hydrocarbon is

[0052] (i) aromatic polycyclic hydrocarbons, i.e. fully unsaturated polycyclic hydrocarbon radicals in which each carbon atom is part of a conjugated π-electron system,

[0053] (ii) a polycyclic hydrocarbon having at least one benzene ring fused to a saturated or unsaturated 4- to 10-membered monocyclic or bicyclic hydrocarbon ring,

[0054] (iii) Polycyclic hydrocarbons having at least two benzene rings linked to each other by covalent bonds, via oxygen atoms or sulfur atoms, or directly fused to each other and / or to a saturated or unsaturated 4- to 10-membered monocyclic or bicyclic hydrocarbon ring.

[0055] Monocyclic or polycyclic arylene groups have 6 to 26, typically 6 to 24, for example 6, 9, 10, 12, 13, 14, 16, 17, 18, 19, 20, 22 or 24 carbon atoms as ring atoms, in particular 6 to 20, especially 6, 10, 12, 13, 14, 16, 17 or 18 carbon atoms. Polycyclic arylene groups usually have 10 to 26, especially 10 to 20, in particular 10, 12, 13, 14, 16, 17 or 18 carbon atoms as ring atoms.

[0056] In this context, polycyclic arylene groups having 2, 3 or 4 benzene rings linked to one another by single bonds or by oxygen or sulfur atoms include, for example, biphenylene and terphenylene, 1,1'-oxydiphenylene and 1,1'-thiodiphenylene. Polycyclic arylene groups having 2, 3 or 4 benzene rings directly fused to one another include, for example, naphthylene, anthracenylene, phenanthrenylene, pyrenylene, triphenylenylene, terphenylene, 1,1'-oxydiphenylene and 1,1'-thiodiphenylene. Chrysenylene and benzo[c]phenanthrenylene. Polycyclic arylene groups having 2, 3 or 4 benzene rings fused to a saturated or unsaturated 4- to 10-membered monocyclic or bicyclic hydrocarbon ring include, for example, 9H-fluorenylene, biphenylenylene, tetraphenylenylene, acenaphthenylene (1,2-dihydroacenaphthenylene), acenaphthylenylene, 9,10-dihydroanthracen-1-ylene, 1,2,3,4-tetrahydrophenanthrenylene, 5,6,7,8-tetrahydrophenanthrenylene, cyclopent[fg]acenaphthylenylene, phenal enylene), fluoranthenylene, benzo[k]fluoranthenylene, perylenylene, 9,10-dihydro-9,10[1',2']-benzenoanthracenylene, dibenzo[a,e][8]annulenylene, 9,9'-spiro[9H-fluoren]ylene, and spiro[1H-cyclobuta[de]naphthalene-1,9'-[9H]fluoren]ylene.

[0057] Monocyclic or polycyclic arylene groups include, by way of example, phenylene, naphthylene, 9H-fluorenylene, phenanthrenylene, anthrylene, pyrenylene, pyrenylene, phenylene, benzo[c]phenanthrenyl, acenaphthylene, acenaphthylene, 2,3-dihydro-1H-indenylene, 5,6,7,8-tetrahydro-naphthalenylene, cyclopenta[fg]acenaphthylene, 2,3-dihydrophenalenylene, 9,10-dihydroanthracen-1-yl, 1,2,3,4-tetrahydrophenanthrenyl, 5,6,7,8-tetrahydrophenanthrenyl, fluoranthenylene, benzo[k]fluoranthenylene, biphenylene, triphenylene, tetraphenylene Phenylene, 1,2-dihydroacenaphthenylene, dibenzo[a,e][8]annulenylene, perylene, biphenylene, terphenylene, naphthylphenylene, phenanthrylphenylene, anthracenylphenylene, pyrenylphenylene, 9H-fluorenylphenylene, di(naphthyl)phenylene, naphthylbiphenyl ...1,2-dihydroacenaphthenylene, dibenzo[a,e][8]annulenylene, dibenzo[a,e][8]annulenylene, dibenzo[a,e]phenylene, terphenylene, naphthylphenylene, 1,2-dihydroacenaphthenylene, dibenzo[a,e]phenylene, dibenzo[a,e]phenylene, terphenylene, terphenylene, terphenylene, terphenylene, terphenylene, terphenylene, terphenylene, terphenylene, terphenylene, terphenylene, terphenylene, terphenylene, terphenylene, terphenylene, terphenylene, terphenylene, terphenylene, terphenylene, terphenylene, terphenylene, terphenylene, terphenylene, terphenylene, terphenylene, terphenylene, terphenylene, terphenylene, terphenylene, terphenylene, terphenylene, ter aphthylenbiphenylene), tri(phenyl)phenylene, tetra(phenyl)phenylene, pentaphenyl(phenylene), phenylnaphthylene, binaphthylene, phenanthrylnaphthylene, pyrenylnaphthylene, phenylanthrylene 1H-cyclobutane-1,9'-[9H]fluorenyl]ylidene.

[0058] For the purposes of the present invention, the suffix "-ylene" indicates that, according to the convention in the art, the corresponding heteroarene or arene moiety is in its diradical form. Thus, the suffix "-ylene" (e.g., in phenylene or 1,4-phenylene) is used herein synonymously with the suffix "-diyl" (e.g., in benzenediyl or benzene-1,4-diyl).

[0059] In the context of the present invention, a "structural unit" refers to a structural element that is repeated in the polymer backbone of a thermoplastic resin. Therefore, the terms "structural unit" and "repeating unit" are used synonymously.

[0060] For the purposes of the present invention, an "optical device" is a device that is transparent to visible light and manipulates light beams, especially by refraction. Optical devices include, but are not limited to, prisms, lenses, optical films, and combinations thereof, especially lenses for cameras and lenses for glasses.

[0061] The statements made below regarding preferred embodiments of the variables (substituents) of the compounds of the formula (I) and the structural elements of the formula (II) are valid both individually and preferably in combination with one another.

[0062] The following statements regarding preferred embodiments of the variables with respect to the compounds of the formula (I) and the structural elements of the formula (II) and, where applicable, with respect to the use according to the invention, are valid both individually and preferably in combination with one another.

[0063] In formula (I) and also in formula (II), the variable X 1 、X 2 、A 1 、A 2 、R 1 、R 2 , n, p and q have the following meanings alone or preferably in any combination:

[0064] Preferred variables X in formula (I) are those 1 and X 2 Independently selected from -CH2OH and -C(O)OR x , where R x are selected from hydrogen and C1-C4-alkyl, and correspondingly preferred are those variables X in formula (II) which are independently selected from -CH2O- and -C(O)O- 1a and X 2a .

[0065] In a preferred embodiment of group (1), the variable X in formula (I) 1 and X 2 have the same meanings, which are selected from -CH2OH and -C(O)OR x , where R xis hydrogen or C1-C4-alkyl, in particular selected from -CH2OH, -C(O)OH, -C(O)OCH3 and -C(O)OCH2CH3, in particular selected from -CH2OH, -C(O)OH and -C(O)OCH3, in particular selected from -CH2OH and -C(O)OCH3. Accordingly, in this preferred embodiment of group (3), the variable X in formula (II) 1a and X 2a All are -CH2O- or -C(O)O-.

[0066] In a preferred embodiment of group (2), the variable X in formula (I) 1 and X 2 are -CH2OH, and correspondingly the variable X in formula (II) 1a and X 2a All are -CH2O-.

[0067] In a preferred embodiment of group (3), the variable X in formula (I) 1 and X 2 are -C(O)OH or -C(O)OCH3. Accordingly, in the preferred embodiment of group (1.2), the variable X in formula (II) 1a and X 2a All are -C(O)O-.

[0068] In a preferred embodiment of group (4), the variable A in formulas (I) and (II) is 1 and A 2 independently selected from single bonds and monocyclic or polycyclic arylene groups having 6 to 22, in particular 6 to 18, carbon atoms as ring members, wherein the monocyclic or polycyclic arylene group is unsubstituted or carries 1, 2, 3 or 4, in particular 1 or 2 R Ar Group, where R Ar has one of the meanings defined herein, in particular one of the preferred meanings mentioned herein.

[0069] In a more preferred embodiment of subgroup (4.1), A 1 and A 2 independently selected from single bonds, phenylene, naphthylene, 1,2-dihydroacenaphthene, biphenylene, 9H-fluorenylene, 11H-benzo[a]fluorenylene, 11H-benzo[b]fluorenylene, 7H-benzo[c]fluorenylene, anthracenylene, phenanthrenylene, benzo[c]phenanthrenylene, py ... phenylene, picenylene, trimethylene, wherein the above monocyclic or polycyclic arylene group is unsubstituted or carries 1 or 2 R Ar group.

[0070] In a particularly preferred subgroup (4.2) of embodiments, A 1 and A 2 are independently selected from a single bond, phenylene and naphthylene, wherein phenylene and naphthylene are unsubstituted or carry 1 or 2 R Ar The groups are, in particular, unsubstituted.

[0071] In a particularly preferred subgroup (4.3) of embodiments, A 1 and A 2 independently selected from a single bond, 1,4-phenylene, 1,2-phenylene, 1,3-phenylene, 1,4-naphthylene, 1,5-naphthylene, 2,7-naphthylene, 2,6-naphthylene, 2,3-naphthylene, 1,8-naphthylene, 1,7-naphthylene, 2,8-naphthylene, 1,6-naphthylene, 2,5-naphthylene, 2,4-naphthylene, 1,3-naphthylene, 2,1-naphthylene and 1,2-naphthylene, wherein the aforementioned monocyclic or polycyclic arylene groups are unsubstituted or carry 1 or 2 R Ar The groups are, in particular, unsubstituted.

[0072] In a particularly preferred subgroup (4.4) of embodiments, A 1 and A 2 Independently selected from a single bond, 1,4-phenylene, 1,3-phenylene and 1,4-naphthylene.

[0073] In a particular subgroup (4') of embodiments, the variable A in formulas (I) and (II) is 1 and A 2 have the same meaning as that of A 1 and A 2 The defined meanings, in particular those mentioned as preferred meanings, and in particular the meanings defined in the embodiments selected from groups (4), (4.1), (4.2), (4.3) and (4.4).

[0074] In a preferred embodiment of group (5), the variable R in formulas (I) and (II) is 1 and R 2 (if present) are independently selected from halogen, C2-C3-alkynyl, CN, R, OR and CH s R' 3-s , more preferably selected from fluorine, CN, R and OR, wherein s is 1 or 2, especially 2, and the variables R and R' each have one of the meanings defined herein, especially the preferred meanings.

[0075] In a particularly preferred subgroup (5.1) of embodiments, R 1 and R 2(if present) are independently selected from fluorine, CN, methyl, methoxy, benzyl, phenyl, naphthyl (e.g. 1-naphthyl or 2-naphthyl) and phenanthrenyl (e.g. 1-phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl or 9-phenanthrenyl), and in particular selected from fluorine, phenyl and naphthyl (e.g. 1-naphthyl or 2-naphthyl).

[0076] In a specific subgroup (5') of embodiments, the variable R in formulas (I) and (II) is 1 and R 2 have the same meaning as that of R 1 and R 2 The defined meanings, in particular those mentioned as preferred meanings, and in particular the meanings defined in the embodiments selected from groups (5) and (5.1).

[0077] Preferably, the variables p and q in formulae (I) and (II) have the same meaning, which is selected from 0, 1 and 2.

[0078] In a preferred embodiment of group (6), the variables p and q in formulae (I) and (II) have the same meaning and are both 1 or 0, and in particular are both 0. The latter refers to Z in formulae (I) and (II) 1 and Z 2 Part does not carry a substituent R 1 Nor does it carry a substituent R 2 .

[0079] In a preferred embodiment of group (7), the variable Y is a single bond.

[0080] In a preferred embodiment of group (8), the variable Y is S, O, S(O) or S(O)2, in particular S or O.

[0081] In a preferred embodiment of group (9), the variable Z in formulas (I) and (II) is 1 and Z 2 All of them are phenylene.

[0082] In a preferred embodiment of group (10), the variable Z in formulas (I) and (II) is 1 and Z 2 All are naphthylene.

[0083] In a preferred embodiment of group (11), the variable n in formulae (I) and (II) is 0.

[0084] Those skilled in the art will readily appreciate that in formulas (I) and (II), the X given in the embodiments of group (1) 1 and X 2The meaning of may be the same as that of A according to one or more of the embodiments of groups (4), (4.1), (4.2), (4.3), (4.4) and (4'). 1 and A 2 The meanings of the combination, with R in the embodiments according to one or more groups (5), (5.1) and (5') 1 and R 2 , optionally in combination with the meanings of p and q according to the embodiment of group (6), in combination with the meaning of Y according to the embodiment of group (7) or the embodiment of group (8), in combination with the meaning of Z according to the embodiment of group (9) or the embodiment of group (10) 1 and Z 2 The meanings of and are optionally combined with the meanings of n in the embodiments according to group (11). A person skilled in the art will also understand that in formula (I) and (II), X given in the embodiments of group (2) 1 and X 2 The meaning of may be the same as that of A according to one or more of the embodiments of groups (4), (4.1), (4.2), (4.3), (4.4) and (4'). 1 and A 2 The meanings of the combination, with R in the embodiments according to one or more groups (5), (5.1) and (5') 1 and R 2 , optionally in combination with the meanings of p and q according to the embodiment of group (6), in combination with the meaning of Y according to the embodiment of group (7) or the embodiment of group (8), in combination with the meaning of Z according to the embodiment of group (9) or the embodiment of group (10) 1 and Z 2 The meanings of and are optionally combined with the meanings of n in the embodiments according to group (11). A person skilled in the art will also understand that in formula (I) and (II), X given in the embodiments of group (3) 1 and X 2 The meaning of may be the same as that of A according to one or more of the embodiments of groups (4), (4.1), (4.2), (4.3), (4.4) and (4'). 1 and A 2 The meanings of the combination, with R in the embodiments according to one or more groups (5), (5.1) and (5') 1 and R 2 , optionally in combination with the meanings of p and q according to the embodiment of group (6), in combination with the meaning of Y according to the embodiment of group (7) or the embodiment of group (8), in combination with the meaning of Z according to the embodiment of group (9) or the embodiment of group (10) 1 and Z 2and optionally in combination with the meanings of n in the embodiments according to group (11).

[0085] In addition and if not otherwise stated, the variable R Ar , R, R', R" and R'" alone or in combination with each other, and with the above variables X 1 、X 1 、A 1 、A 2 、R 1 、R 2 The meanings and preferred combinations of the meanings of , p and q have the following meanings.

[0086] R Ar Preferably selected from fluorine, CN, R 3 , OR 3 and benzyl, and more preferably selected from R 3 OR 3 In particular, R Ar The radical is selected from methyl, methoxy, phenyl, naphthyl, in particular from phenyl, naphthyl (eg 1-naphthyl or 2-naphthyl).

[0087] R is preferably selected from methyl, ethyl, phenyl, naphthyl, phenanthrenyl and triphenylene, which are unsubstituted or substituted by 1, 2 or 3 identical or different R' groups, wherein R'' independently has one of the meanings defined herein for each occurrence, particularly one of the preferred meanings. More preferably, R is selected from phenyl, naphthyl (e.g. 1-naphthyl or 2-naphthyl) and phenanthrenyl (e.g. 1-phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl or 9-phenanthrenyl), which are unsubstituted.

[0088] R' is preferably selected from phenyl, naphthyl, phenanthrenyl and triphenylene, which are unsubstituted or substituted by 1, 2 or 3 identical or different R' groups, wherein R'' independently has one of the meanings defined herein for each occurrence, particularly one of the preferred meanings. More preferably, R' is selected from phenyl, naphthyl (e.g. 1-naphthyl or 2-naphthyl) and phenanthrenyl (e.g. 1-phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl or 9-phenanthrenyl), which are unsubstituted.

[0089] R" is preferably selected from hydrogen, methyl, phenyl and naphthyl, wherein phenyl and naphthyl are unsubstituted or substituted by 1, 2 or 3, in particular 1 or 2, identical or different R"' groups, wherein R"' independently at each occurrence has one of the meanings defined herein, in particular one of the preferred meanings. More preferably, R" is unsubstituted phenyl or unsubstituted naphthyl, for example 1-naphthyl or 2-naphthyl.

[0090] R''' is preferably selected from phenyl, OCH3 and CH3.

[0091] In the embodiments of specific subgroups (7a), (1), (4'), (5') and (9) of group (7), wherein Z in formula (I) 1 and Z 2 The groups are all phenylene, the Y part is a single bond, and the X 1 and X 2 The groups have the same meaning, A 1 and A 2 The groups have the same meanings, and the substituent R 1 and R 2 (if present) have the same meaning, compounds of formula (I) are compounds of formula (Ia),

[0092]

[0093] where X 0 Indicates the same X 1 and X 2 Group, where A 0 Indicates the same A 1 and A 2 Group, where R 0 Indicates the same R 1 and R 2 group, and wherein X 1 、X 2 、A 1 、A 2 、R 1 、R 2 , n, p and q have the meanings defined herein, especially the meanings mentioned herein as being preferred.

[0094] In the embodiments of this subgroup (7a), (1), (4'), (5') and (9) of group (7), the structural unit of formula (II) is a structural unit of formula (IIa),

[0095]

[0096] Where # represents the connection point with the adjacent structural unit, and X 0a Indicates the same X 1a and X 2a Group, where A 0 Indicates the same A 1 and A 2 Group, where R 0 Indicates the same R 1 and R 2 group, and where the variable X 1a 、X 2a 、A 1 、A 2 、R 1 、R 2, n, p and q have the meanings defined herein, especially the meanings mentioned as being preferred.

[0097] Preferably, X in formula (Ia) 0 Part and X in formula (IIa) 0a The moiety is as defined in the embodiment of group (1). Therefore, X in formula (Ia) is 0 The moiety is particularly selected from -CH2OH (ie hydroxymethyl) and -C(O)OR x , where R x is hydrogen or C1-C4-alkyl, in particular selected from -CH2OH, -C(O)OH and -C(O)OCH3. Thus, X in formula (IIa) is 0a The moiety is selected from -CH2O- and -C(O)O-.

[0098] Preference is also given to compounds of the formula (Ia) and structural units of the formula (IIa) in which A 0 The moiety is defined as one of the embodiments of groups (4), (4.1), (4.2), (4.3) and (4.4). More preferably, A in formula (Ia) and formula (IIa) 0 The moiety is as defined in the embodiment of group (4.4). Thus, A in formula (Ia) and (IIa) 0 The moiety is especially selected from a single bond, 1,4-phenylene, 1,3-phenylene and 1,4-naphthylene.

[0099] Preferably, the substituent R in formula (Ia) and (IIa) is 0 (if present) as defined in one of the embodiments of groups (5) and (5.1), in particular as defined in one of the embodiments of group (5.1). 0 If present, it is especially selected from fluorine, phenyl and naphthyl, such as 1-naphthyl or 2-naphthyl.

[0100] Preferably, the variables p and q in formula (Ia) and (IIa) are as defined in the embodiment of group (6). Thus, p and q are both 0 or 1, in particular both 0.

[0101] If p and q are both 1, then the two substituents R 0 (if present) are preferably each located in the group S(O) n counterpoint.

[0102] Preferably, the variable n in formula (Ia) and (IIa) is as defined in the embodiment of group (11). Therefore, n is particularly 0, i.e. S(O) in formula (Ia) and (IIa) n The portion is in particular the S portion.

[0103] Examples of a specific subgroup (7a) are compounds of formula (Ia) and structural units of formula (IIa) wherein X 0 Partial or X 0a Part A 0 The combination of the part and the variables n, p and q are defined in any of the rows 1 to 12 of Table A below, where X 0a In each case, by adding X 0 -OH or -OR x The group is derived from X in formula (Ia) by replacing it with an oxo (-O-) unit 0 .

[0104] Table A:

[0105] # <![CDATA[X 0 ]]> <![CDATA[A 0 *)]]> n=p=q 1 <![CDATA[-CH2OH]]> single bond 0 2 <![CDATA[-CH2OH]]> 1,4-phenylene 0 3 <![CDATA[-CH2OH]]> 1,3-phenylene 0 4 <![CDATA[-CH2OH]]> 1,4-naphthylene 0 5 -C(O)OH single bond 0 6 -C(O)OH 1,4-phenylene 0 7 -C(O)OH 1,3-phenylene 0 8 -C(O)OH 1,4-naphthylene 0 9 <![CDATA[-C(O)OCH3]]> single bond 0 10 <![CDATA[-C(O)OCH3]]> 1,4-phenylene 0 11 <![CDATA[-C(O)OCH3]]> 1,3-phenylene 0 12 <![CDATA[-C(O)OCH3]]> 1,4-naphthylene 0

[0106] *)A 0 The names of the parts containing the connecting bond position "n,m-" should be understood as the first one, that is, n, representing the connection with X 0 The position of the carbon atom of attachment, the second one, ie, m, represents the position of the carbon atom to which one of the phenylene groups in formula (Ia) or (IIa) is attached.

[0107] Among the compounds of formula (Ia) listed in Table A, the following compounds are particularly preferred:

[0108] -(dibenzo[b,d]thiophene-4,6-diyl)dimethanol, also known as 4,6-bis(hydroxymethyl)-dibenzo[b,d]thiophene;

[0109] -dibenzo[b,d]thiophene-4,6-dicarboxylic acid; and

[0110] -dimethyl dibenzo[b,d]thiophene-4,6-dicarboxylate.

[0111] Among the compounds of formula (Ia), more preferred are:

[0112] -(dibenzo[b,d]thiophene-4,6-diyl)dimethanol.

[0113] In certain subgroups (7b), (1), (4'), (5') and (9) of group (7), wherein Z in formula (I) 1 and Z 2 Parts are all phenylene, Y group is a single bond, X 1 and X 2 The groups have the same meaning, A 1 and A 2 The groups have the same meaning, and R 1 and R 2The groups (if present) have the same meanings, the compounds of formula (I) are the compounds of formula (Ib),

[0114]

[0115] where X 0 Indicates the same X 1 and X 2 Group, where A 0 Indicates the same A 1 and A 2 Group, where R 0 Indicates the same R 1 and R 2 group, and wherein X 1 、X 2 、A 1 、A 2 、R 1 、R 2 , n, p and q have the meanings defined herein, in particular the meanings mentioned herein as being preferred.

[0116] In the embodiments of this subgroup (7a), (1), (4'), (5') and (9) of group (7), the structural unit of formula (II) is a structural unit of formula (IIb),

[0117]

[0118] Where # represents the connection point with the adjacent structural unit, and X 0a Indicates the same X 1a and X 2a Group, where A 0 Indicates the same A 1 and A 2 Group, where R 0 Indicates the same R 1 and R 2 group, and where the variable X 1a 、X 2a 、A 1 、A 2 、R 1 、R 2 , n, p and q have the meanings defined herein, in particular the meanings mentioned as being preferred.

[0119] Preferably, X in formula (Ib) 0 Part and X in formula (IIb) 0a The moiety is as defined in the embodiment of group (1). Therefore, X in formula (Ib) is 0 The moiety is particularly selected from -CH2OH (ie hydroxymethyl) and -C(O)OR x , where Rx is hydrogen or C1-C4-alkyl and is particularly selected from -CH2OH, -C(O)OH and -C(O)OCH3. Thus, X in formula (IIb) is 0a The moiety is selected from -CH2O- and -C(O)O-.

[0120] Also preferred are the following compounds (Ib) and structural units of formula (IIb): wherein A 0 The moiety is as defined in one of the embodiments of groups (4), (4.1), (4.2), (4.3) and (4.4). More preferably, A in formula (Ib) and formula (IIb) 0 The moiety is as defined in the embodiment of group (4.3) or (4.4). Thus, A in formula (Ib) and (IIb) 0 The moiety is especially selected from a single bond, 1,4-phenylene, 1,2-phenylene, 1,3-phenylene, 1,4-naphthylene, 1,5-naphthylene, 2,7-naphthylene, 2,6-naphthylene, 2,3-naphthylene, 1,8-naphthylene, 1,7-naphthylene, 2,8-naphthylene, 1,6-naphthylene, 2,5-naphthylene, 2,4-naphthylene, 1,3-naphthylene, 2,1-naphthylene and 1,2-naphthylene.

[0121] Preferably, the substituent R in formula (Ib) and (IIb) is 0 (if present) as defined in one of the embodiments of groups (5) and (5.1), and in particular as defined in the embodiments of group (5.1). 0 If present, it is especially selected from fluorine, phenyl and naphthyl, such as 1-naphthyl or 2-naphthyl.

[0122] Preferably, the variables p and q in formula (Ib) and (IIb) are as defined in the embodiment of group (6). Thus, p and q are both 0 or 1, in particular both 0.

[0123] If p and q are both 1, then the two substituents R 0 (if present) are preferably each located at S(O) n ortho position of the group.

[0124] Preferably, the variable n in formula (Ib) and (IIb) is as defined in the embodiment of group (11). Therefore, n is particularly 0, i.e. S(O) in formula (Ib) and (IIb) n The portion is in particular the S portion.

[0125] Examples of a specific subgroup (7b) are compounds of formula (Ib) and structural units of formula (IIb) wherein X 0 Partial or X 0a Part A 0The combination of the part and the variables n, p, and q are defined in any of the rows 1 to 54 of Table B below, where X 0a In each case, by adding X 0 -OH or -OR x The group is derived from X in formula (Ib) by replacing it with an oxo (-O-) unit 0 .

[0126] Table B:

[0127]

[0128]

[0129]

[0130] *)A 0 The names of the parts containing the connection position "n,m-" should be understood as the first one, namely n, representing the connection with X 0 The position of the carbon atom of attachment, the second one, ie, m, represents the position of the carbon atom to which one of the phenylene groups in formula (Ib) or (IIb) is attached.

[0131] Among the compounds of formula (Ib) listed in Table B, the following compounds are particularly preferred:

[0132] -(Dibenzo[b,d]thiophene-2,8-diyl)dimethanol, also known as 2,8-bis(hydroxymethyl)-dibenzo[b,d]thiophene;

[0133] -Dibenzo[b,d]thiophene-2,8-dicarboxylic acid

[0134] -Dimethyl dibenzo[b,d]thiophene-2,8-dicarboxylate

[0135] -[Dibenzo[b,d]thiophene-2,8-diylbis(3,1-phenylene)]dimethanol

[0136] -[Dibenzo[b,d]thiophene-2,8-diylbis(4,1-phenylene)]dimethanol

[0137] -[Dibenzo[b,d]thiophene-2,8-diylbis(4,1-naphthylene)]dimethanol

[0138] -3,3'-(dibenzo[b,d]thiophene-2,8-diyl)dibenzoic acid

[0139] -4,4'-(dibenzo[b,d]thiophene-2,8-diyl)dibenzoic acid

[0140] -4,4'-(dibenzo[b,d]thiophene-2,8-diyl)di(naphthalene-1-carboxylic acid)

[0141] -Dimethyl 3,3'-(dibenzo[b,d]thiophene-2,8-diyl)dibenzoate

[0142] -Dimethyl 4,4'-(dibenzo[b,d]thiophene-2,8-diyl)dibenzoate

[0143] -4,4'-(dibenzo[b,d]thiophene-2,8-diyl)di(naphthalene-1-carboxylic acid)dimethyl ester.

[0144] Among the compounds of formula (Ib), more preferred are:

[0145] -(dibenzo[b,d]thiophene-2,8-diyl)dimethanol.

[0146] In certain subgroups (8a), (1), (4'), (5') and (9) of group (8), wherein Z in formula (I) 1 and Z 2 Parts are all phenylene, X 1 and X 2 The groups have the same meaning, A 1 and A 2 The groups have the same meaning, and R 1 and R 2 The substituents, if present, have the same meanings, the compound of formula (I) is the compound of formula (Ic),

[0147]

[0148] where X 0 Indicates the same X 1 and X 2 Group, where A 0 Indicates the same A 1 and A 2 Group, where R 0 Indicates the same R 1 and R 2 group, and wherein X 1 、X 2 、A 1 、A 2 、R 1 、R 2 , n, p and q have the meanings defined herein, especially the meanings mentioned herein as being preferred.

[0149] In the embodiments of this subgroup (8a), (1), (4'), (5') and (9) of group (8), the structural unit of formula (II) is a structural unit of formula (IIc),

[0150]

[0151] Where # represents the connection point with the adjacent structural unit, and X 0a Indicates the same X 1a and X 2a Group, where A 0 Indicates the same A 1 and A 2 Group, where R 0 Indicates the same R 1 and R 2 group, and where the variable X 1a 、X 2a 、A 1 、A 2 、R 1 、R 2 , Y, n, p and q have the meanings defined herein, especially the meanings mentioned as being preferred.

[0152] Preferably, X in formula (Ic) 0 Part and X in formula (IIc) 0a The moiety is as defined in the embodiment of group (1). Therefore, X in formula (Ic) 0 The moiety is particularly selected from -CH2OH (ie hydroxymethyl) and -C(O)OR x , where R x is hydrogen or C1-C4-alkyl, in particular selected from -CH2OH, -C(O)OH and -C(O)OCH3. Thus, X in formula (IIc) is 0a The moiety is selected from -CH2O- and -C(O)O-.

[0153] Preference is also given to compounds of the formula (Ic) and structural units of the formula (IIc) in which A 0 The moiety is as defined in one of the embodiments of groups (4), (4.1), (4.2), (4.3) and (4.4). More preferably, A in formula (Ic) and formula (IIc) 0 The moiety is as defined in the embodiment of group (4.3) or (4.4). Thus, A in formula (Ic) and (IIc) 0 The moiety is especially selected from a single bond, 1,4-phenylene, 1,2-phenylene, 1,3-phenylene, 1,4-naphthylene, 1,5-naphthylene, 2,7-naphthylene, 2,6-naphthylene, 2,3-naphthylene, 1,8-naphthylene, 1,7-naphthylene, 2,8-naphthylene, 1,6-naphthylene, 2,5-naphthylene, 2,4-naphthylene, 1,3-naphthylene, 2,1-naphthylene and 1,2-naphthylene.

[0154] Preferably, the two -A in formula (Ic) 0 -X 0The group and the two -A in formula (IIc) 0 -X 0a The groups are located in the meta or para position, respectively, relative to the point of attachment of Y.

[0155] Preferably, R in formula (Ic) and (IIc) 0 The substituents, if present, are as defined in one of the embodiments of groups (5) and (5.1), and in particular as defined in the embodiments of group (5.1). 0 The substituents, if present, are especially selected from fluorine, phenyl and naphthyl, such as 1-naphthyl or 2-naphthyl.

[0156] Preferably, the variables p and q in formulae (Ic) and (IIc) are as defined in the embodiments of group (6). Thus, p and q are particularly both 0.

[0157] Preferably, the variable n in formulae (Ic) and (IIc) is as defined in the embodiments of group (11). Thus, n is especially 0.

[0158] Preferably, the Y group in formula (Ic) and (IIc) is S or O, especially S.

[0159] In a specific embodiment of subgroup (8a-1) of subgroup (8a), the variables n, p and q are all 0, and the Y group is S, i.e., the compound of formula (Ic) and the structural unit of formula (IIc) represent two -A 0 -X 0 Group or two -A 0 -X 0a Group-substituted thianthrene.

[0160] In the embodiment of this subgroup (8a-1), preferably the two -A in formula (Ic) and (IIc) 0 -X 0 or -A 0 -X 0a The groups are both located in the meta position relative to the Y group, or one group is located in the meta position relative to Y and the other is located in the para position relative to Y. Therefore, the compound of formula (Ic) and the structural unit of formula (IIc) here represent two -A groups at positions 2 and 7 or positions 2 and 8, respectively. 0 -X 0 Group or two -A 0 -X 0a Group-substituted thianthrene.

[0161] Examples of a specific subgroup (8a-1) are compounds of formula (Ic) and structural units of formula (IIc), wherein X 0 Partial or X 0a Part A 0part, variable Y, variables n, p and q, and A 0 The combinations of positions of the parts relative to Y are defined in any of rows 1 to 108 of Table C below, where X 0a In each case, by adding X 0 -OH or -OR x The group is derived from X in formula (Ic) by replacing it with an oxo (-O-) unit 0 .

[0162] Table C:

[0163]

[0164]

[0165]

[0166]

[0167] *)A 0 The names of the parts containing the connection position "n,m-" should be understood as the first one, namely n, representing the connection with X 0 The position of the carbon atom of attachment, the second one, ie, m, represents the position of the carbon atom to which one of the phenylene groups in formula (Ic) or (IIc) is attached.

[0168] Among the compounds of formula (Ic) listed in Table C, the following compounds are particularly preferred: -(thianthrene-2,8-diyl)dimethanol

[0169] -Thianthrene-2,8-dicarboxylic acid

[0170] -Thianthrene-2,8-dicarboxylic acid dimethyl ester

[0171] -(thianthrene-2,7-diyl)dimethanol

[0172] -Thianthrene-2,7-dicarboxylic acid

[0173] -Thianthrene-2,7-dicarboxylic acid dimethyl ester

[0174] -[Thianthrene-2,8-diylbis(3,1-phenylene)]dimethanol

[0175] -[Thianthrene-2,8-diylbis(4,1-phenylene)]dimethanol

[0176] -[Thianthrene-2,8-diylbis(4,1-naphthylene)]dimethanol

[0177] -[Thianthrene-2,7-diylbis(3,1-phenylene)]dimethanol

[0178] -[Thianthrene-2,7-diylbis(4,1-phenylene)]dimethanol

[0179] -[Thianthrene-2,7-diyldi(4,1-naphthylene)]dimethanol

[0180] -3,3'-(thianthrene-2,8-diyl)dibenzoic acid

[0181] -4,4'-(thianthrene-2,8-diyl)dibenzoic acid

[0182] -4,4'-(thianthrene-2,8-diyl)di(naphthalene-1-carboxylic acid)

[0183] -3,3'-(thianthrene-2,7-diyl)dibenzoic acid

[0184] -4,4'-(thianthrene-2,7-diyl)dibenzoic acid

[0185] -4,4'-(thianthrene-2,7-diyl)di(naphthalene-1-carboxylic acid)

[0186] -Dimethyl 3,3'-(thianthrene-2,8-diyl)dibenzoate

[0187] -Dimethyl 4,4'-(thianthrene-2,8-diyl)dibenzoate

[0188] -4,4'-(thianthrene-2,8-diyl)di(naphthalene-1-carboxylic acid) dimethyl ester

[0189] -3,3'-(thianthrene-2,7-diyl)dibenzoic acid dimethyl ester

[0190] -Dimethyl 4,4'-(thianthrene-2,7-diyl)dibenzoate

[0191] -4,4'-(thianthrene-2,7-diyl)di(naphthalene-1-carboxylic acid) dimethyl ester

[0192] Among the compounds of formula (Ic), more preferred are:

[0193] -(thianthrene-2,8-diyl)dimethanol

[0194] -(thianthrene-2,7-diyl)dimethanol.

[0195] In the embodiments of specific subgroups (8b), (1), (4'), (5') and (10) of group (8), wherein Z in formula (I) 1 and Z 2 Part of them are naphthylene, X 1 and X 2 The groups have the same meaning, A 1 and A 2 The groups have the same meaning, and R1 and R 2 The substituents, if present, have the same meanings, the compound of formula (I) is the compound of formula (Id),

[0196]

[0197] where X 0 Indicates the same X 1 and X 2 Group, where A 0 Indicates the same A 1 and A 2 Group, where R 0 Indicates the same R 1 and R 2 group, and wherein X 1 、X 2 、A 1 、A 2 、R 1 、R 2 , Y, n, p and q have the meanings defined herein, especially the meanings mentioned herein as being preferred.

[0198] In the embodiments of this subgroup (8b), (1), (4'), (5') and (10) of group (8), the structural unit of formula (II) is a structural unit of formula (IId),

[0199]

[0200] Where # represents the connection point with the adjacent structural unit, and X 0a Indicates the same X 1a and X 2a Group, where A 0 Indicates the same A 1 and A 2 Group, where R 0 Indicates the same R 1 and R 2 group, and where the variable X 1a 、X 2a 、A 1 、A 2 、R 1 、R 2 , Y, n, p and q have the meanings defined herein, especially the meanings mentioned as being preferred.

[0201] Preferably, X in formula (Id) 0 Part and X in formula (IId) 0a The moiety is as defined in the embodiment of group (1). Therefore, X in formula (Id) 0The moiety is particularly selected from -CH2OH (ie hydroxymethyl) and -C(O)OR x , where R x is hydrogen or C1-C4-alkyl, in particular selected from -CH2OH, -C(O)OH and -C(O)OCH3. Thus, X in formula (IId) is 0a The moiety is selected from -CH2O- and -C(O)O-.

[0202] Preference is also given to compounds of the formula (Id) and structural units of the formula (IIc) in which A 0 The moiety is as defined in one of the embodiments of groups (4), (4.1), (4.2), (4.3) and (4.4). More preferably, A in formula (Id) and formula (IId) 0 The moiety is as defined in the embodiments of group (4.3) or (4.4). Thus, A in formula (Id) and (IId) 0 The moiety is especially selected from a single bond, 1,4-phenylene, 1,2-phenylene, 1,3-phenylene, 1,4-naphthylene, 1,5-naphthylene, 2,7-naphthylene, 2,6-naphthylene, 2,3-naphthylene, 1,8-naphthylene, 1,7-naphthylene, 2,8-naphthylene, 1,6-naphthylene, 2,5-naphthylene, 2,4-naphthylene, 1,3-naphthylene, 2,1-naphthylene and 1,2-naphthylene.

[0203] Preferably, R in formula (Id) and (IId) 0 The substituents, if present, are as defined in one of the embodiments of groups (5) and (5.1), and in particular as defined in the embodiments of group (5.1). 0 The substituents, if present, are especially selected from fluorine, phenyl and naphthyl, such as 1-naphthyl or 2-naphthyl.

[0204] Preferably, the variables p and q in formulae (Id) and (IId) are as defined in the embodiments of group (6). Thus, p and q are particularly both 0.

[0205] Preferably, the Y group in formula (Id) and (IId) is S or O, especially O.

[0206] Examples of a specific subgroup (8b) are compounds of formula (Id) and structural units of formula (IId), wherein X 0 Partial or X 0a Part A 0 The combination of moiety, group Y and variables n, p and q are as defined in any of rows 1 to 162 of Table D below, wherein X 0a In each case, by adding X 0 -OH or -OR xThe group is derived from X in formula (Id) by replacing it with an oxo (-O-) unit 0 .

[0207] Table D:

[0208]

[0209]

[0210]

[0211]

[0212]

[0213] *)A 0 The names of the parts containing the connection position "n,m-" should be understood as the first one, namely n, representing the connection with X 0 The position of the carbon atom of attachment, the second one, ie, m, represents the position of the carbon atom to which one of the naphthylene groups in formula (Id) or (IId) is attached.

[0214] Among the compounds of formula (Id) listed in Table D, the following compounds are particularly preferred:

[0215] -(Dibenzo[a,j]thiophene-3,11-diyl)dimethanol

[0216] -Dibenzo[a,j]phenoxathiol-3,11-dicarboxylic acid

[0217] -Dimethyl dibenzo[a,j]phenthiothioate-3,11-dicarboxylate

[0218] -3,11-bis(hydroxymethyl)-14H-14λ 4 -Dibenzo[a,j]phenoxathian-14-one

[0219] -14-oxo-14H-14λ 4 -Dibenzo[a,j]phenoxathiol-3,11-dicarboxylic acid

[0220] -14-oxo-14H-14λ 4 -Dimethyl dibenzo[a,j]phenthiothioate-3,11-dicarboxylate

[0221] -3,11-bis(hydroxymethyl)-14H-14λ 6 -Dibenzo[a,j]phenoxathiol-14,14-dione

[0222] -14,14-dioxo-14H-14λ 6 -Dibenzo[a,j]phenoxathiol-3,11-dicarboxylic acid

[0223] -14,14-dioxo-14H-14λ 6 -Dimethyl dibenzo[a,j]phenthiothioate-3,11-dicarboxylate

[0224] -[Dibenzo[a,j]phenoxathiol-3,11-diylbis(3,1-phenylene)]dimethanol

[0225] -[Dibenzo[a,j]phenoxathiol-3,11-diylbis(4,1-phenylene)]dimethanol

[0226] -[Dibenzo[a,j]phenoxathiol-3,11-diylbis(4,1-naphthylene)]dimethanol

[0227] -3,3'-(dibenzo[a,j]thiophene-3,11-diyl)dibenzoic acid

[0228] -4,4'-(dibenzo[a,j]thiophene-3,11-diyl)dibenzoic acid

[0229] -4,4'-(dibenzo[a,j]phenoxathiol-3,11-diyl)di(naphthalene-1-carboxylic acid)

[0230] -3,3'-(dibenzo[a,j]phenthiothiol-3,11-diyl)dibenzoic acid dimethyl ester

[0231] -4,4'-(dibenzo[a,j]phenthiothiol-3,11-diyl)dibenzoate dimethyl ester

[0232] -4,4'-(dibenzo[a,j]phenoxathiol-3,11-diyl)di(naphthalene-1-carboxylic acid) dimethyl ester

[0233] -3,11-bis[3-(hydroxymethyl)phenyl]-14H-14λ 4 -Dibenzo[a,j]phenoxathian-14-one

[0234] -3,11-bis[4-(hydroxymethyl)phenyl]-14H-14λ 4 -Dibenzo[a,j]phenoxathian-14-one

[0235] -3,11-bis[4-(hydroxymethyl)naphthalen-1-yl]-14H-14λ 4 -Dibenzo[a,j]phenoxathian-14-one

[0236] -3,3'-(14-oxo-14H-14λ 4 -Dibenzo[a,j]phenoxathiol-3,11-diyl)dibenzoic acid

[0237] -4,4'-(14-oxo-14H-14λ4 -Dibenzo[a,j]phenoxathiol-3,11-diyl)dibenzoic acid

[0238] -4,4'-(14-oxo-14H-14λ 4 -Dibenzo[a,j]phenoxathiol-3,11-diyl)di(naphthalene-1-carboxylic acid)

[0239] -3,3'-(14-oxo-14H-14λ 4 -Dibenzo[a,j]phenoxathiol-3,11-diyl)dibenzoic acid dimethyl ester

[0240] -4,4'-(14-oxo-14H-14λ 4 -Dibenzo[a,j]phenoxathiol-3,11-diyl)dibenzoic acid dimethyl ester

[0241] -4,4'-(14-oxo-14H-14λ 4 -Dibenzo[a,j]phenoxathiol-3,11-diyl)di(naphthalene-1-carboxylic acid) dimethyl ester

[0242] -3,11-bis[3-(hydroxymethyl)phenyl]-14H-14λ 6 -Dibenzo[a,j]phenoxathiol-14,14-dione

[0243] -3,11-bis[4-(hydroxymethyl)phenyl]-14H-14λ 6 -Dibenzo[a,j]phenoxathiol-14,14-dione

[0244] -3,11-bis[4-(hydroxymethyl)naphthalen-1-yl]-14H-14λ 6 -Dibenzo[a,j]phenoxathiol-14,14-dione

[0245] -3,3'-(14,14-dioxo-14H-14λ 6 -Dibenzo[a,j]phenoxathiol-3,11-diyl)dibenzoic acid

[0246] -4,4'-(14,14-dioxo-14H-14λ 6 -Dibenzo[a,j]phenoxathiol-3,11-diyl)dibenzoic acid

[0247] -4,4'-(14,14-dioxo-14H-14λ 6 -Dibenzo[a,j]phenoxathiol-3,11-diyl)di(naphthalene-1-carboxylic acid)

[0248] -3,3'-(14,14-dioxo-14H-14λ 6-Dibenzo[a,j]phenoxathiol-3,11-diyl)dibenzoic acid dimethyl ester

[0249] -4,4'-(14,14-dioxo-14H-14λ 6 -Dibenzo[a,j]phenoxathiol-3,11-diyl)dibenzoic acid dimethyl ester

[0250] -4,4'-(14,14-dioxo-14H-14λ 6 -Dibenzo[a,j]phenoxathiol-3,11-diyl)di(naphthalene-1-carboxylic acid) dimethyl ester

[0251] Among the compounds of formula (Id), more preferred are:

[0252] -(Dibenzo[a,j]thiophene-3,11-diyl)dimethanol

[0253] -3,11-bis(hydroxymethyl)-14H-14λ 4 -Dibenzo[a,j]phenoxathian-14-one

[0254] -3,11-bis(hydroxymethyl)-14H-14λ 6 -Dibenzo[a,j]phenoxathiol-14,14-dione

[0255] A compound of formula (Ia) wherein A 0 Part is a single bond, X 0 The group is -CH2OH or -C(O)OR x , variables p, q and n are all 0, can be prepared, for example, by the method shown in the following reaction scheme 1, wherein R x’ is C1-C4-alkyl, especially methyl.

[0256] Option 1:

[0257]

[0258] In step i) of the process according to Scheme 1, the dibenzo[b,d]thiophene of formula (1) is first treated with a strong base, such as in particular n-butyllithium, and then reacted with N,N-dimethylformamide (DMF) to give, after acidic workup, a diformyl derivative of formula (2), which can be oxidized in step ii) with a suitable oxidizing agent to give a dicarboxylic acid of formula (3). Another alternative route to the preparation of the dicarboxylic acid is to treat the dibenzo[b,d]thiophene (1) with n-butyllithium and then react it with carbon dioxide and workup under acidic conditions. As further shown in steps iii) and iv) of Scheme 1, the diformyl derivative (2) can also be converted into 4,6-bis(hydroxymethyl)-dibenzo[b,d]thiophene of formula (4) by reducing it with a suitable reducing agent, such as sodium borohydride, while reacting it with an alcohol R x’ Alternatively, the dimethylolated derivative (4) can be obtained by first reacting dibenzo[b,d]thiophene (1) with n-butyllithium and then treating with paraformaldehyde.

[0259] The compounds of formula (3), (4) and (5) shown in Scheme 1 are compounds of formula (Ia) of the present invention, wherein, respectively, A 0 The part is a single bond, the variables p, q, and n are all 0, and X 0 The groups are -CH2OH or -C(O)OR x .

[0260] Detailed information on the reactions listed in Scheme 1 and other related reactions can be found in D. Rosario-Amorin et al., Inorg. Chem. 2014, 53(11), 5698-5711; J. Korang et al., J. Am. Chem. Soc. 2010, 132(12), 4466-4476; C. Kuehm-Caubere et al., Tetrahedron 1996, 52(27), 9087-9092; A. Voituriez et al., Tetrahedron Letters 2002, 43(28), 4907-4909; and JP 2001-139573.

[0261] A compound of formula (Ib) wherein A 0 Part is a single bond, X 0 The groups are all -CH2OH, and the variables p, q and n are all 0, and can be prepared, for example, by the method shown in the following reaction scheme 2,

[0262] Option 2:

[0263]

[0264] In step i) of the method according to Scheme 2, dibenzo[b,d]thiophene (1) is first reacted with bromine or N-bromosuccinimide to obtain 2,8-dibromodibenzo[b,d]thiophene of formula (6); 2,8-dibromodibenzo[b,d]thiophene is converted into the corresponding diformyl derivative by reacting with magnesium in step ii) to obtain the corresponding Grignard reagent, which is then reacted with DMF and treated under acidic conditions to obtain 2,8-diformyldibenzo[b,d]thiophene of formula (7). In the subsequent step iii), the diformyl derivative (7) is reduced to 2,8-bis(hydroxymethyl)-dibenzo[b,d]thiophene of formula (8) using a suitable reducing agent (e.g., sodium borohydride).

[0265] The compound of formula (8) shown in Scheme 2 is a compound of formula (Ib) of the present invention, wherein A 0 The part is a single bond, the variables p, q, and n are all 0, and X 0 The groups are all -CH2OH.

[0266] Detailed information on the reactions listed in Scheme 2 and other related reactions can be found in J. Korang et al., J. Am. Chem. Soc. 2010, 132(12), 4466-4476; RB DuVernet et al., J. Am. Chem. Soc. 1978, 100(8), 2457-2464; and LV Dunkerton et al., J. Hetero-cyc. Chem. 1987, 24(3), 749-755.

[0267] A compound of formula (Ib) wherein A 0 Part is a single bond, the same X 0 The group is -C(O)OH or -C(O)OR x , and the variables p, q and n are all 0, can be prepared, for example, by the method shown in the following reaction scheme 3, wherein R x’ is C1-C4-alkyl, especially methyl.

[0268] Option 3:

[0269]

[0270] In step i) of the process according to Scheme 3, 2,8-dibromodibenzo[b,d]thiophene of formula (6) obtained by the process described in Scheme 2 above can be converted into the corresponding dicarboxylic acid (9) by treatment with n-butyllithium followed by reaction with carbon dioxide and acidic treatment. In the subsequent reaction step ii), the dicarboxylic acid can be reacted with an alcohol R x’-OH (e.g. methanol) to give the corresponding diester of formula (10).

[0271] The compounds of formula (9) and formula (10) shown in Scheme 3 are compounds of formula (Ib) of the present invention, wherein A 0 The part is a single bond, the variables p, q, and n are all 0, and X 0 The groups are all -C(O)OR x .

[0272] Detailed information on the reactions listed in Scheme 3 and other related reactions can be found in WO 2022 / 255235 A1; S. Ma et al., Inorg. Chem. Commun. 2016, 70, 10-13; and US 3,952,014.

[0273] Compounds of formula (Ib) wherein variables p, q and n are all 0, the same A 0 The moiety is a monocyclic or polycyclic arylene group (such as phenylene or naphthylene), and the same X 0 The group is -CH2OH or -C(O)OR x , where R x is a C1-C4-alkyl group, which can be prepared, for example, by the method shown in the following reaction scheme 4, wherein A 0’ is a monocyclic or polycyclic arylene group, in particular a phenylene group or a naphthylene group, and X 0’ -CH2OH or -C(O)OR x’ , where R x’ is C1-C4-alkyl, especially methyl.

[0274] Option 4:

[0275]

[0276] In step i) of Scheme 4, 2,8-dibromodibenzo[b,d]thiophene of formula (6) obtained by the method described in Scheme 2 above is reacted with an arylboron compound of formula (12)

[0277] X 0’ -A 0’ -B(OH)2(12)

[0278] where X 0’ and A 0’ As defined above, or with an ester or anhydride of (12), especially a C1-C 4-alkyl ester reaction, the reaction is carried out in the presence of a transition metal catalyst (especially a palladium catalyst) to produce a compound of formula (11). Typically, step i) is carried out under so-called "Suzuki coupling" conditions in the presence of a catalyst (for example, especially a palladium catalyst) and a base. Suitable reaction conditions as well as suitable catalysts and bases can be found in, for example, A. Suzuki et al., Chem. Rev. 1995, 95, 2457-2483; N. Zhe et al., J. Med. Chem. 2005, 48(5), 1569-1609; Young et al., J. Med. Chem. 2004, 47(6), 1547-1552; C. Slee et al., Bioorg. Med. Chem. Lett. 2001, 9, 3243-3253; T. Zhang et al., Tetrahedron Lett. 2011, 52, 311-313; S. Bourrain et al., Synlett 2004, 5, 795-798; and B. Li et al., Europ. J. Org. Chem. 2011 3932-3937.

[0279] The compound of formula (11) obtained by the coupling reaction of Scheme 4 is the compound of formula (Ib) of the present invention, wherein A 0 The moieties are identical monocyclic or polycyclic arylene moieties, such as, in particular, phenylene or naphthylene, the variables p, q and n are all 0, and X 0 The groups are the same -CH2OH or -C(O)OR x’ Group, where R x’ is C1-C4-alkyl, especially methyl.

[0280] Compounds of formula (Ib) wherein variables p, q and n are all 0, the same A 0 The moiety is a monocyclic or polycyclic arylene group, such as a phenylene group or a naphthylene group, and X 0 The group is -C(O)OH, which can be prepared from the aforementioned diester according to formula (11), wherein X 0 Same as -C(O)OR x’ , R x’ It is a C1-C4-alkyl group, and the preparation method is an ester cleavage method known in the art.

[0281] Compounds 2,7-dibromo-thianthrene of formula (14) and 2,8-dibromo-thianthrene of formula (15) can be used as precursors for preparing compounds of formula (Ic) of the present invention according to the method of Scheme 6 described below, for example, by following the conversion shown in Reaction Scheme 5 below.

[0282] Option 5:

[0283]

[0284] In step i) of Scheme 5, thianthrene is reacted with, for example, bromine or N-bromosuccinimide according to suitable bromination methods established in the prior art to obtain a mixture of dibrominated compounds of formula (14) and (15), i.e., a mixture of dibrominated 2,7-dibromo-thianthrene and 2,8-dibromo-thianthrene. In the subsequent steps of Scheme 5, the mixture of compounds of formula (14) and (15) is subjected to a suitable separation procedure, such as column chromatography, to obtain compounds (14) and (15) in separated form. The individual compounds, i.e., 2,7-dibromo-thianthrene or 2,8-dibromo-thianthrene, can then be used in the following process of Scheme 6.

[0285] Compounds of formula (Ic) wherein variables p, q and n are all 0, Y is S, and the same -A 0 -X 0 Part is -CH2OH or -C(O)OR x’ , where R x’ is C1-C4-alkyl, such as especially methyl, and wherein -A 0 -X 0 The moieties are both located in the meta position relative to the Y group, or one group is located in the meta position relative to Y and the other is located in the para position relative to Y, and can be prepared according to the method shown in the following reaction scheme 6.

[0286] Option 6:

[0287]

[0288] In step (i) of Scheme 6, compounds of formula (14) and formula (15), i.e., 2,7- or 2,8-dibromo-thianthrene obtained by the process described in Scheme 5 above, are converted to the corresponding 2,7- or 2,8-diformyl derivatives by reacting with magnesium to obtain the corresponding Grignard reagent, which is then reacted with DMF and treated under acidic conditions to obtain the corresponding 2,7-diformylthianthrene of formula (16) or 2,8-diformylthianthrene of formula (17). In the following step ii), the diformyl derivatives (16) or (17) are reduced to 2,7-di(hydroxymethyl)-thianthrene of formula (18) or 2,8-di(hydroxymethyl)-thianthrene of formula (19), respectively, using a suitable reducing agent, such as sodium borohydride. Alternatively, according to step iii), the 2,7-diformylthianthrene of formula (16) or the 2,8-diformylthianthrene of formula (17) can be reacted in the presence of an alcohol R x’ -OH in the presence of oxidation, where R x’is C1-C4-alkyl, in particular methyl, to obtain the corresponding dicarboxylic acid diester of formula (20) or (21), i.e. di(C1-C4-alkyl)thianthrene-2,7-dicarboxylate or di(C1-C4-alkyl)thianthrene-2,8-dicarboxylate. Suitable oxidizing agents for this reaction are in principle known in the prior art.

[0289] Each of the compounds of formula (18), (19), (20) or (21) shown in Scheme 6, i.e., 2,7-bis(hydroxymethyl)-thianthrene, 2,8-bis(hydroxymethyl)-thianthrene, di(C1-C4-alkyl)thianthrene-2,7-dicarboxylate or di(C1-C4-alkyl)thianthrene-2,8-dicarboxylate, is a compound of formula (Ic) of the present invention, wherein each A 0 is a single bond, the variables p, q, and n are all 0, Y is S, and each X 0 is -CH2-OH or -C(O)O-(C1-C4-alkyl), and -A 0 -X 0 The moieties are both located in the meta position relative to the Y group, or one group is located in the meta position relative to Y and the other is located in the para position relative to Y.

[0290] Compounds of formula (Ic) wherein variables p, q and n are all 0, Y is S, and -A 0 -X 0 The parts are all -C(O)OH, and -A 0 -X 0 The compounds thianthrene-2,7-dicarboxylic acid and thianthrene-2,8-dicarboxylic acid are both located in the meta position relative to the Y group, or one group is located in the meta position relative to Y and the other is located in the para position relative to Y, i.e., the compounds thianthrene-2,7-dicarboxylic acid and thianthrene-2,8-dicarboxylic acid can be prepared, for example, from the above-mentioned diesters of the corresponding formula (20) or (21) by ester cleavage methods known in the art.

[0291] Compounds of formula (Ic) wherein variables p, q and n are all 0, Y is S, and the same A 0 Part is a monocyclic or polycyclic arylene group, such as phenylene or naphthylene, and the same X 0 The group is -CH2OH or -C(O)OR x , where R x is C1-C4-alkyl, and wherein -A 0 -X 0 The moieties are both located at the meta position relative to the Y group, or one group is located at the meta position relative to Y and the other is located at the para position relative to Y, and can be prepared, for example, according to the method shown in the following reaction scheme 7, wherein A 0’ is a monocyclic or polycyclic arylene group, especially a phenylene group or a naphthylene group, X 0’ -CH2OH or -C(O)OR x’, where R x’ is C1-C4-alkyl, especially methyl.

[0292] Option 7:

[0293]

[0294] In step i) of Scheme 7, a 2,7- or 2,8-dibromothianthrene of formula (14) or (15) obtained by the method described in Scheme 5 above is reacted with an arylboron compound of formula (12) (i.e., X as described above) in a Suzuki coupling reaction similar to that outlined in Scheme 4. 0’ -A 0’ -B(OH)2 compound) to obtain a compound of formula (22) or (23).

[0295] The compounds of formula (22) and formula (23) are compounds of formula (Ic) of the present invention, wherein A 0 The moieties are identical monocyclic or polycyclic arylene moieties, the variables p, q, and n are all 0, Y is S, and X 0 The groups are the same -CH2OH or -C(O)OR x’ Group, where R x’ is C1-C4-alkyl, and two -A 0 -X 0 The moieties are located at positions 2 and 7 or positions 2 and 8 of the thianthrene skeleton.

[0296] The compound of formula (Ic) of the present invention, wherein A 0 The moieties are identical monocyclic or polycyclic arylene moieties, the variables p, q and n are all 0, Y is S, X 0 The groups are all -C(O)OH, and two of them are -A 0 -X 0 The moiety is located at positions 2 and 7 or positions 2 and 8 of the thianthrene skeleton and can be prepared from the diester according to formula (22) or (23) by ester cleavage methods known in the art, wherein the two X 0 All are -C(O)OR x’ , R x’ It is C1-C4-alkyl.

[0297] The compound 3,11-dibromo-dibenzo[a,j]phenoxathiol of formula (26) and its sulfinyl and sulfonyl derivatives of formulas (27) and (28), namely the compound 3,11-dibromo-14H-14λ 4 -dibenzo[a,j]phenoxathian-14-one and 3,11-dibromo-14H-14λ 6-dibenzo[a,j]phenoxathiol-14,14-dione, which can serve as a precursor for the preparation of the compound of formula (Id) of the present invention according to the method described in Scheme 9 below, which can be prepared, for example, by the transformations shown in the following reaction schemes 8a and 8b.

[0298] Option 8a:

[0299]

[0300] In step i) of Scheme 8a, 6-bromonaphthalene-2-ol of formula (24) is reacted with thionyl chloride to obtain 1,1′-sulfonyldiyl-bis(6-bromonaphthalene-2-ol) of formula (25), which is then condensed by heating to obtain the desired dibrominated thiophene derivative of formula (26).

[0301] The compound of formula (26) is then oxidized to the corresponding dibrominated sulfinyl and sulfonyl derivatives of formula (27) and (28) by employing oxidation methods known in the art, as shown in Scheme 8b below.

[0302] Option 8b:

[0303]

[0304] Alternatively, the sulfanyl group of formula (25) is oxidized to the corresponding sulfinyl or sulfonyl derivative in a manner analogous to methods known in the art, which is then condensed with heat to afford the cyclized sulfinyl and sulfonyl derivatives of formula (27) and (28), respectively.

[0305] For detailed information on reactions similar to Schemes 8a and 8b and other related reactions, see W. Wang et al., Tianjin Huagong 2013, 27(4), 32-34; M. Kamali et al., ARKIVOC (Gainesville, FL, US), 2014, (4), 242-251; A. Shockravi et al., Phosph., Sulfur & Silicon & Rel. Elem. 2007, 182(9), 2115-2123; O. Hinsberg, J. Prakt. Chem. (Leipzig) 1914, 90, 345-353; WO 2021 / 114313A1.

[0306] Compounds of formula (Id) wherein variables p and q are both 0, n is 0, 1 or 2, Y is O, and the same -A 0 -X 0 Part is -CH2OH or -C(O)OR x’ , where R x’is C1-C4-alkyl, such as in particular methyl, and can be prepared, for example, by the method shown in the following reaction scheme 9.

[0307] Option 9:

[0308]

[0309] In step (i) of Scheme 9, the compound of formula (26), (27) or (28), i.e., 3,11-dibromo-dibenzo[a,j]phenoxathiol or its sulfinyl or sulfonyl derivative obtained by the methods described in Schemes 8a and 8b above, is converted to the corresponding 3,11-diformyl derivative by reacting with magnesium to obtain the corresponding Grignard reagent, which is then reacted with DMF and treated under acidic conditions to obtain the corresponding 3,11-diformyl compound of formula (29), (30) or (31). In the following step ii), the diformyl derivative (29), (30) or (31) is reduced to the corresponding 3,11-bis(hydroxymethyl) derivative of formula (32), (33) or (34) using a suitable reducing agent (e.g., sodium borohydride). Alternatively, according to step iii), the 3,11-diformyl compound of formula (29), (30) or (31) can be reacted with an alcohol R x’ -OH in the presence of oxidation, where R x’ is C1-C4-alkyl, in particular methyl, to give the corresponding dicarboxylic acid diesters of the formula (35), (36) or (37). Oxidants suitable for this reaction are in principle known from the prior art.

[0310] Each of the compounds of formula (32), (33), (34), (35), (36) or (37) shown in Scheme 9 is a compound of formula (Id) of the present invention, wherein each A 0 is a single bond, variables p and q are both 0, Y is O, and each X 0 is -CH2-OH or -C(O)O-(C1-C4-alkyl), and the variable n is 0, 1 or 2.

[0311] Compounds of formula (Id) wherein variables p and q are both 0, Y is O, and -A 0 -X 0 Part of them are -C(O)OH, namely the compounds dibenzo[a,j]phenoxathiol-3,11-dicarboxylic acid, 14-oxo-14H-14λ 4 -dibenzo[a,j]phenoxathiol-3,11-dicarboxylic acid and 14,14-dioxo-14H-14λ 6 -Dibenzo[a,j]phenoxathiol-3,11-dicarboxylic acid can be prepared, for example, from the corresponding diester of formula (35), (36) or (37) above by ester cleavage methods known in the art.

[0312] Compounds of formula (Id) wherein variables p and q are both 0, Y is O, and the same A 0 Part is a monocyclic or polycyclic arylene group, such as phenylene or naphthylene, and the same X 0 The group is -CH2OH or -C(O)OR x , where R x is a C1-C4-alkyl group, which can be prepared, for example, by the method shown in the following reaction scheme 10, wherein A 0’ is a monocyclic or polycyclic arylene group, especially a phenylene group or a naphthylene group, X 0’ -CH2OH or -C(O)OR x’ , where R x’ is C1-C4-alkyl, especially methyl.

[0313] Option 10:

[0314]

[0315] In step i) of Scheme 10, a compound of formula (26), (27) or (28), i.e., 3,11-dibromo-dibenzo[a,j]phenoxathiol or a sulfinyl or sulfonyl derivative thereof, obtained by the methods described in Schemes 8a and 8b above, is reacted with an arylboronic acid compound of formula (12), i.e., compound X above, in a Suzuki coupling reaction similar to that outlined in Scheme 4. 0’ -A 0’ -B(OH)2 is reacted to obtain a compound of formula (38), (39) or (40).

[0316] The compound of formula (38), (39) or (40) is a compound of formula (Id) of the present invention, wherein A 0 The moieties are identical monocyclic or polycyclic arylene moieties, the variables p, q and n are all 0, Y is O, X 0 The groups are the same -CH2OH or -C(O)OR x’ Group, where R x’ is C1-C4-alkyl, and the variable n is 0, 1 or 2.

[0317] The compound of formula (Id) of the present invention, wherein A 0 The moieties are identical monocyclic or polycyclic arylene moieties, the variables p and q are both 0, Y is O, X 0 The groups are all -C(O)OH, which can be prepared from the diesters according to formula (38), (39) or (40) by ester cleavage methods known in the art, wherein the two X 0 All are -C(O)OR x’ , R x’It is C1-C4-alkyl.

[0318] As is apparent from the above, the compounds of formula (Ia), (Ib), (Ic) and (Id), which are 0 Substituents, i.e., at least one of the variables p and q is different from 0, can be prepared, for example, by syntheses analogous to the above-described schemes 1 to 10, by using the corresponding substituted dibromides instead of the unsubstituted dibromides of formula (6), (14), (15), (26), (27) or (28). These substituted dibromides can in principle be obtained in a manner analogous to the unsubstituted dibromides from the corresponding substituted precursors.

[0319] The transformations of Schemes 1 to 10 and related Schemes above can be accomplished by the reactions in the above Schemes or by obvious variations thereof, or alternatively, by well-established methods in preparative organic chemistry or a combination thereof.

[0320] Other compounds of formula (I) can be prepared by employing obvious variations of the above reactions and their combination with well-established methods in preparative organic chemistry.

[0321] The reaction mixture obtained in each step of the synthesis of the compound described in the above-mentioned reaction schemes 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10 is usually refined in a conventional manner, for example, by mixing with water, separating each phase and, where appropriate, by washing, treating with an adsorbent (e.g., activated carbon) or chromatography or crystallization to purify the crude product. In some cases, the intermediate forms a colorless or light brown viscous oil that does not contain volatiles or is purified at a reduced pressure and appropriately elevated temperature. If a solid intermediate is obtained, purification can be achieved by recrystallization or washing methods such as slurry washing.

[0322] The starting compounds for preparing compounds of formula (I) used in the syntheses shown in Schemes 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10 above are commercially available or can be prepared by methods known in the art.

[0323] As mentioned above, the compounds of the invention can be obtained in very high purity, which means that the product obtained does not contain, apart from volatiles, a significant amount of organic impurities other than the compound of formula (I). Typically, the purity of the compound of formula (I) based on non-volatile organic matter is at least 95%, in particular at least 98%, and in particular at least 99%, i.e. the product contains at most 5%, in particular at most 2% and in particular at most 1% of non-volatile impurities other than the compound of formula (I).

[0324] In this context, it should be mentioned that mixtures of different compounds of formula (I) are also useful, since they can be used as monomer compositions for preparing useful thermoplastic resins (e.g., polycarbonate resins) comprising different structural units of formula (II) derived from different monomers of formula (I). Therefore, mixtures of different compounds of formula (I) and corresponding thermoplastic resins comprising different structural units of formula (II) are also part of the present invention.

[0325] The term "volatiles" refers to the 5 Non-volatile organic substances are therefore understood to mean compounds with a boiling point of more than 200° C. at standard pressure.

[0326] A special benefit of the present invention is that compounds of formula (I) and solvates thereof are generally available in crystalline form. In crystalline form, compounds of formula (I) may exist in pure form or in the form of solvates with water or organic solvents. Therefore, a specific aspect of the present invention relates to compounds of formula (I) that exist essentially in crystalline form. Specifically, the present invention relates to crystalline forms in which compounds of formula (I) exist in the absence of solvents, and to crystalline solvates of compounds of formula (I) in which the crystals contain incorporated solvents.

[0327] A special benefit of the present invention is that the compound of formula (I) and its solvate can be easily crystallized from conventional organic solvents usually.This allows the compound of formula (I) to be effectively purified.For making the compound of formula (I) or its solvate crystallization suitable organic solvent include, but not limited to, aromatic hydrocarbons (such as toluene or xylene), aliphatic ketones especially ketones (such as acetone, methyl ethyl ketone, methyl isopropyl ketone or diethyl ketone) with 3 to 6 carbon atoms, aliphatic and alicyclic ethers (such as diethyl ether, dipropyl ether, methyl isobutyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, dioxane or tetrahydrofuran), aliphatic-aromatic ethers (such as anisole), aliphatic alcohols (such as methanol, ethanol or isopropanol) and aliphatic esters (such as ethyl acetate) with 1 to 4 carbon atoms and mixtures thereof.Before the crystallization step, it may be beneficial to filter (such as by diatomaceous earth) the dissolved compound of formula (I) crude preparation to remove the solid components that may exist in the crude preparation.

[0328] Furthermore, impurities that may be present in the crude preparation of the compound of formula (I), in particular color-forming impurities and heavy metals, can be removed at any stage of the purification process, for example before the filtration step or the crystallization step, by standard procedures, such as treatment with an adsorbent (e.g. activated carbon).

[0329] Alternatively, compounds of formula (I) and solvates thereof can be obtained in purified form by adopting other simple and effective methods for purifying the crude products of these compounds, such as, in particular, slurry washing of the crude solid obtained directly after conversion, to prepare compounds of formula (I). Slurry washing is typically carried out at ambient temperature or generally at an elevated temperature of about 30 to 90° C., in particular 40 to 80° C. Suitable organic solvents are, in principle, the same as those listed above for being suitable for crystallizing compounds of formula (I), such as, in particular, the aromatic hydrocarbons, aliphatic ketones and aliphatic ethers mentioned, such as toluene, methyl ethyl ketone and methyl tert-butyl ether.

[0330] Therefore, the compound of formula (I) for the preparation of thermoplastic polymers, especially polycarbonates defined herein can be easily prepared and obtained in high yield and high purity. In particular, the compound of formula (I) can be obtained in crystalline form, which allows effective purification to the degree required in the preparation of optical resins. In particular, these compounds can be obtained with a purity that provides high refractive index and low haze, which is particularly important for the purposes of preparing the optical resin used for optical devices. In a word, the compound of formula (I) is particularly useful as a monomer in the preparation of optical resins.

[0331] A skilled person will readily understand that the formula (I) of the monomer used corresponds to the formula (II) of the structural unit included in the thermoplastic resin. Similarly, the formulas (Ia), (Ib), (Ic) and (Id) of the monomer used correspond to the formulas (IIa), (IIb), (IIc) and (IId) of the structural unit included in the thermoplastic resin, respectively.

[0332] It will also be understood by those skilled in the art that the structural units of formula (II), (IIa), (IIb), (IIc) and (IId) are repeating units within the polymer chain of the thermoplastic resin. In addition to the structural units of each of formula (II), (IIa), (IIb), (IIc) and (IId), the thermoplastic resin may also have structural units different therefrom. In a preferred embodiment, these other structural units are derived from aromatic monomers of formula (IV), thereby producing structural units of formula (V):

[0333] HO-R z -A 3 -R z -OH (IV)

[0334] #-OR z -A 3 -R z -O-#(V)

[0335] in

[0336] # indicates the connection point with the adjacent structural unit;

[0337] A 3 is a polycyclic group with at least two benzene rings, wherein the benzene rings may be connected via W and / or directly fused to each other and / or fused via a non-benzene carbocyclic ring and / or fused via two non-benzene carbocyclic rings connected via a linker L, wherein A 3 R is unsubstituted or substituted by 1, 2 or 3 groups selected from halogen, C1-C6-alkyl, C5-C6-cycloalkyl, phenyl, naphthyl, 1,2-dihydroacenaphthenyl, phenanthrenyl, pyrenyl, triphenylene, benzo[b]furanyl, dibenzo[b,d]furanyl, benzo[b]thienyl, dibenzo[b,d]thienyl and thianthrenyl. aa group substitution;

[0338] W is selected from a single bond, O, C=O, S, S(O), SO2, CH2, CH-Ar, CAr2, CH(CH3), C(CH3)2 and a group of formula (A')

[0339]

[0340] in

[0341] Q' represents a single bond, O, NH, C=O, CH2 or CH=CH, especially a single bond, O, C=O or CH2;

[0342] R 7a 、R 7b independently selected from hydrogen, fluorine, CN, R, OR, CH v R' 3-v , NR2, C(O)R and C(O)NH2, wherein R and R' are as defined above, and v is 0, 1 or 2; and

[0343] * indicates the point of attachment to the benzene ring;

[0344] L is selected from a single bond, C1-C4-alkylene, C4-C7-cycloalkylene, C4-C7-cycloalkylene dimethylene, phenylene dimethylene, wherein L is unsubstituted or replaced by 1 or 2 R selected from C1-C4-alkyl, halogen, C1-C4-haloalkyl, C4-C7-cycloalkyl and phenyl L Group substitution,

[0345] Ar is selected from monocyclic or polycyclic aromatic radicals having 6 to 26 carbon atoms as ring atoms and monocyclic or polycyclic heteroaromatic radicals having a total of 5 to 26 atoms as ring members, wherein 1, 2, 3 or 4 of these ring member atoms of the heteroaromatic radical are selected from nitrogen, sulfur and oxygen, and the remaining atoms of these ring member atoms of the heteroaromatic radical are carbon atoms, wherein Ar is unsubstituted or replaced by 1, 2 or 3 R selected from halogen, phenyl and C1-C4-alkyl ab group substitution;

[0346] R z For single bond, Alk 1 、O-Alk 2 -、O-Alk 2 -[O-Alk 2 -] w - or O-Alk 3 -C(O)-, where O is bound to A 3 , and among them

[0347] w is an integer from 1 to 10;

[0348] Alk 1 is C1-C4-alkanediyl;

[0349] Alk 2 is C2-C4-alkanediyl; and

[0350] Alk 3 It is C1-C4-alkanediyl.

[0351] If R in formula (IV) z It's O-Alk 3 -C(O), esters of the monomers of formula (IV), in particular C1-C4-alkyl esters, can be used instead.

[0352] In the context of formulae (IV) and (V), A 3 In particular, polycyclic groups with at least two benzene or naphthalene rings, wherein the benzene rings are linked via W or fused via two non-benzene carbon rings linked via a linker L, wherein W is in particular selected from a single bond, S, S(O), SO2, C(CH3)2 and an A' group, and wherein L is a single bond or a C1-C4-alkylene group.

[0353] In the context of formulae (IV) and (V), R z Especially O-Alk 2 -, where Alk 2 Especially linear alkanediyl having 2 to 4 carbon atoms and in particular O-CH2CH2.

[0354] Among the monomers of formula (IV), monomers of general formulae (IV-1) to (IV-8) are preferred.

[0355]

[0356]

[0357] in

[0358] a and b are 0, 1, 2 or 3, especially 0 or 1;

[0359] a' and b' are 0, 1, 2 or 3, especially 0 or 1;

[0360] c and d are 0, 1, 2, 3, 4 or 5, especially 0 or 1;

[0361] e and f are 0, 1, 2, 3, 4 or 5, especially 0 or 1;

[0362] W' is S, S(O), SO2, O, a single bond, CH2, CH(CH3), C(CH3)2, in particular S, S(O), SO2 or C(CH3)2;

[0363] And where R z 、R aa 、R ab 、R 7a 、R 7b and L are as defined for formula (IV), and wherein R z In particular it is selected from a single bond, CH2 and OCH2CH2.

[0364] Among the monomers of formula (IV), monomers of general formulae (IV-11) to (IV-22) are particularly preferred, wherein R z and R aa As defined herein, and R z In particular selected from single bonds, CH2 and O-CH2CH2, in particular O-CH2CH2:

[0365]

[0366]

[0367] Examples of compounds of formulae (IV-11) to (IV-22) are 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-isopropylphenyl)fluorene, 9,9-bis(4-hydroxy-3-tert-butylphenyl)fluorene, 9,9-bis(4-hydroxy-3-cyclohexylphenyl)fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (BPEF), 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-isopropylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butylphenyl)fluorene. 9,9-bis(6-hydroxy-2-naphthyl)fluorene, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)fluorene (also known as 9,9-bis(6-(2-hydroxyethoxy)naphth-2-yl)fluorene (BNEF) or 6,6'-(9-fluorenylene)bis(2-naphthyloxyethanol) (NOLE)), 10,10-bis(4-hydroxyphenyl)anthracen-9-one, 10,10-bis(4-(2-hydroxyethoxy)phenyl)anthracen-9-one, 4,4'-dihydroxytetraphenylmethane, 4,4'-di- (2-Hydroxyethoxy)-tetraphenylmethane, 3,3'-diphenyl-4,4'-dihydroxy-tetraphenylmethane, di-(6-hydroxy-2-naphthyl)-diphenylmethane, 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-diphenyl-phenyl]-1-methyl-ethyl]-2,6-diphenyl-phenoxy]ethanol, 2-[4-[1-[4-(2-hydroxyethoxy)-3-phenyl-phenyl]-1-methyl-ethyl]-2,6-diphenyl-phenoxy]ethanol, 9,9'-dihydroxymethyl-9,9'-difluorene, 2,2'-[1,1'-binaphthyl-2,2'-diylbis(oxy)]diethanol (also known as 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl) or 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl (BNE)), 2,2'-bis(1-hydroxymethoxy)-1,1'-binaphthyl, 2,2'-bis(3-hydroxypropoxy)-1,1'-binaphthyl, 2,2'-bis(4-hydroxybutoxy)-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-6,6'-di(naphth-1-yl)-1,1'-binaphthyl, 2,2'-bis(2-hydroxymethoxy)-6,6'-diphenyl-1,1'-binaphthyl, 2,2'-bis(2-hydroxymethoxy)-6,6'-di(naphth-1-yl)-1,1'-binaphthyl, 2,2'-bis(2-hydroxymethoxy)-6,6'-diphenyl-1,1'-binaphthyl, 2,2'-bis(2-hydroxymethoxy)-6,6'-di(naphth-1-yl)-1,1'-binaphthyl,2'-bis(2-hydroxypropoxy)-6,6'-diphenyl-1,1'-binaphthyl, 2,2'-bis(2-hydroxypropoxy)-6,6'-di(naphth-1-yl)-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-6,6'-di(naphth-2-yl)-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-6,6'-di(9-phenanthrenyl)-1,1'-binaphthyl, 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-di(naphth-1-yl)-phenyl]-1-methyl-ethyl]-2,6-di(naphth-1-yl) )-phenoxy]ethanol, 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-di(naphthalen-2-yl)-phenyl]-1-methyl-ethyl]-2,6-di(naphthalen-2-yl)-phenoxy]ethanol, 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-di(phenanthren-9-yl)-phenyl]-1-methylethyl]-2,6-di(phenanthren-9-yl)-phenoxy]ethanol, 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-di(1,2-dibenzo[b,d]thiophen-4-yl)-phenyl]-1-methyl-ethyl]- 2,6-bis(1,2-dibenzo[b,d]thiophen-4-yl)-phenoxy]ethanol, 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-di(thianthren-1-yl)-phenyl]-1-methyl-ethyl]-2,6-di(thianthren-1-yl)-phenoxy]ethanol, 2-[4-[4-(2-hydroxyethoxy)-3,5-di(naphthalen-1-yl)phenyl]sulfonyl-2,6-di(naphthalen-1-yl)-phenoxy]ethanol, 2-[4-[4-(2-hydroxyethoxy)-3,5-di(naphthalen-2-yl)phenyl]sulfonyl-2,6-di( phenoxy]ethanol, 2-[4-[4-(2-hydroxyethoxy)-3,5-di(phenanthren-9-yl)phenyl]sulfonyl-2,6-di(phenanthren-9-yl)-phenoxy]ethanol, 2-[4-[4-(2-hydroxyethoxy)-3,5-di(thianthren-1-yl)phenyl]sulfonyl-2,6-di(thianthren-1-yl)phenoxy]ethanol and 2-[4-[4-(2-hydroxyethoxy)-3,5-di(dibenzo[b,d]thiophen-4-yl)phenyl]sulfonyl-2,6-dibenzo[b,d]thiophen-4-yl)phenoxy]ethanol, etc.

[0368] Among the monomers of the general formula (IV) or formulae (IV-1) to (IV-8), monomers of formulae (IV-1), (IV-2), (IV-3) and (IV-8) are particularly preferred, and monomers of formulae (IV-11), (IV-12), (IV-13), (IV-14), (IV-15), (IV-21) and (IV-22) are even more preferred, and 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl (BNE or BHBNA), 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl (BNE or BHBNA), 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)fluorene (BNEF), 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene (BPPEF), 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-di(phenanthren-9-yl)-phenyl]-1-methylethyl]-2,6-di( phenoxy]ethanol, 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-bis(1,2-dibenzo[b,d]thiophen-4-yl)-phenyl]-1-methyl-ethyl]-2,6-bis(1,2-dibenzo[b,d]thiophen-4-yl)-phenoxy]ethanol, 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-bis(thianthren-1-yl)-phenyl]-1-methyl-ethyl]-2,6-bis(thianthren-1-yl)-phenoxy]ethanol, 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-bis(thianthren-1-yl)-phenyl]-1-methyl-ethyl]-2,6-bis(thianthren-1-yl)-phenoxy]ethanol, [4-(2-Hydroxyethoxy)-3,5-di(phenanthrene-9-yl)phenyl]sulfonyl-2,6-di(phenanthrene-9-yl)-phenoxy]ethanol, 2-[4-[4-(2-hydroxyethoxy)-3,5-di(thianthren-1-yl)phenyl]sulfonyl-2,6-di(thianthren-1-yl)phenoxy]ethanol and 2-[4-[4-(2-hydroxyethoxy)-3,5-di(dibenzo[b,d]thien-4-yl)phenyl]sulfonyl-2,6-dibenzo[b,d]thien-4-yl)phenoxy]ethanol.

[0369] Therefore, among the structural units of formula (V) that can be included in the thermoplastic resin, structural units of general formulae (V-1) to (V-8) are preferred.

[0370]

[0371] in

[0372] a and b are 0, 1, 2 or 3, especially 0 or 1;

[0373] a' and b' are 0, 1, 2 or 3, especially 0 or 1;

[0374] c and d are 0, 1, 2, 3, 4 or 5, especially 0 or 1;

[0375] e and f are 0, 1, 2, 3, 4 or 5, especially 0 or 1;

[0376] W' is S, S(O), SO2, O, a single bond, CH2, CH(CH3), C(CH3)2, in particular S, S(O), SO2 or C(CH3)2;

[0377] And where R z 、R aa 、R ab 、R 7a 、R 7b and L are as defined for formula (V), and wherein R z In particular it is selected from a single bond, CH2 and OCH2CH2.

[0378] Particular preference is given to structural units of the general formulae (V-11) to (V-22) in which R z and R aa As defined herein, and wherein R z In particular, it is selected from a single bond, CH2 and O-CH2CH2, and in particular O-CH2CH2:

[0379]

[0380]

[0381] Among the structural units of formulae (V-1) to (V-8), structural units of formulae (V-1), (V-2), (V-3) and (V-8) are particularly preferred. Among the structural units of formulae (V-11) to (V-22), structural units of formulae (V-11), (V-12), (V-13), (V-14), (V-15), (V-21) and (V-22) are particularly preferred, and structural units derived from 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl (BNE or BHBNA), 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl (DPBN or DPBHBNA), 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (BPEF), 9,9-bis(6-(2-hydroxyethoxy)naphthalen-2-yl)fluorene (BNEF), 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene (BPPEF), 2-[4-[4-(2-hydroxyethoxy)-3,5-di(thianthren-1-yl)phenyl]sulfonyl-2,6-di(thianthren-1-yl)phenoxy]ethanol, 2-[4-[4-(2-hydroxyethoxy)-3,5-di(thianthren-1-yl)phenyl]sulfonyl-2,6-di(thianthren-1-yl)phenoxy]ethanol 2-[4-[4-(2-hydroxyethoxy)-3,5-di(phenanthren-9-yl)phenyl]sulfonyl-2,6-di(phenanthren-9-yl)-phenoxy]ethanol, 2-[4-[4-(2-hydroxyethoxy)-3,5-di(dibenzo[b,d]thiophen-4-yl)phenyl]sulfonyl-2,6-dibenzo[b,d]thiophen-4-yl)phenoxy]ethanol, 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-di(phenanthren-9-yl)phenyl]sulfonyl-2,6-dibenzo[b,d]thiophen-4-yl)phenoxy]ethanol -yl)-phenoxy]ethanol, 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-bis(1,2-dibenzo[b,d]thiophen-4-yl)-phenyl]-1-methyl-ethyl]-2,6-bis(1,2-dibenzo[b,d]thiophen-4-yl)-phenoxy]ethanol and 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-bis(thianthren-1-yl)-phenyl]-1-methyl-ethyl]-2,6-bis(thianthren-1-yl)-phenoxy]ethanol.

[0382] In a particularly preferred embodiment, the thermoplastic resin of the present invention comprises at least one structural unit of formula (IIa), (IIb), (IIc) or (IId) and at least one structural unit selected from the group consisting of a structural unit of formula (V-11), a structural unit of formula (V-12), a structural unit of formula (V-13), a structural unit of formula (V-14), a structural unit of formula (V-15), a structural unit of formula (V-21) and a structural unit of formula (V-22). In this specific embodiment, it is preferred that the group R z Those thermoplastic resins which are O-CH2CH2.

[0383] In the thermoplastic resin of this group of particularly preferred embodiments, preferably, the total molar ratio of the structural units of formula (IIa), (IIb), (IIc) or (IId) is in the range of 1 to 99 mol%, preferably in the range of 10 to 99 mol%, further preferably in the range of 15 to 97 mol%, and even further preferably in the range of 25 to 95 mol%, based on the total amount of the structural units of formula (II) and (V).

[0384] Compounds of formula (IV), (IV-1), (IV-2), (IV-3), (IV-4), (IV-5), (IV-6), (IV-7), (IV-8), (IV-11), (IV-12), (IV-13), (IV-14), (IV-15), (IV-16), (IV-17), (IV-18), (IV-19), (IV-20), (IV-21) and (IV-22) are known or can be prepared by methods analogous to known methods.

[0385] For example, the compound of formula (IV-8) can be prepared by various synthesis methods, for example, as disclosed in Japanese Patent Application No. 2014-227387, Japanese Patent Application No. 2014-227388, Japanese Patent Application No. 2015-168658, and Japanese Patent Application No. 2015-187098. For example, 1,1'-binaphthol can be reacted with ethylene glycol monotoluenesulfonate (monotosylates); alternatively, 1,1'-binaphthol can be reacted with alkylene oxides, halogenated alkanols, or alkylene carbonates; alternatively, 1,1'-binaphthol can be reacted with ethylene carbonate (ethylene carbonates). Thus, a compound of formula (IV-8) is obtained, wherein R z -OH is O-Alk 2 -OH or O-Alk 2-[O-Alk 2 -] w -OH.

[0386] For example, the compound of formula (IV-2) can be prepared by various synthetic methods, for example, as disclosed in Japanese Patent Publication No. 5442800 and Japanese Publication No. 2014-028806. Examples include:

[0387] (a) reacting fluorene with hydroxynaphthalene in the presence of hydrochloric acid gas and mercaptocarboxylic acid;

[0388] (b) reacting 9-fluorene with hydroxynaphthalene in the presence of an acid catalyst (and an alkyl mercaptan);

[0389] (c) reacting fluorene with hydroxynaphthalene in the presence of hydrochloric acid and a thiol (e.g., mercaptocarboxylic acid);

[0390] (d) reacting fluorene with hydroxynaphthalene in the presence of sulfuric acid and a mercaptan (e.g., mercaptocarboxylic acid), and then crystallizing the product from a crystallization solvent consisting of a hydrocarbon and a polar solvent to form bis-naphthol fluorene; etc.

[0391] Thus, compounds of formula (IV-2) can be obtained, wherein R z It is a single bond.

[0392] The compound of formula (IV) (wherein R z O-Alk 2 - or O-Alk 2 -[O-Alk 2 -] w -) can be made from a compound of formula (IV) (wherein R z is a single bond) is prepared by reacting with an alkylene oxide or a halogenated alkanol. For example, z is a single bond) is reacted with an alkylene oxide or a haloalkanol to produce a compound of formula (IV-2) (wherein R z It's O-Alk 2 - or O-Alk 2 -[O-Alk 2 -] w For example, 9,9-bis[6-(2-hydroxyethoxy)naphthyl]fluorene can be prepared by reacting 9,9-bis[6-(2-hydroxynaphthyl]fluorene with 2-chloroethanol under alkaline conditions.

[0393] The monomers of formula (I) and (IV) used to make the thermoplastic resin may contain certain impurities resulting from their preparation, for example, the comonomer (IV) may contain hydroxyl compounds carrying OH groups instead of, for example, O-Alk 2 -OH group, or may contain O-Alk2 -[O-Alk 2 ] w - group instead of O-Alk 2 -group. The total amount of these impurity compounds is preferably 5000 ppm or less, more preferably 3000 ppm or less, still more preferably 2000 ppm or less, and particularly preferably 1000 ppm or less. The total content of impurities in the monomers used to prepare the thermoplastic resin is preferably 4000 ppm or less, especially 1500 ppm or less, and more preferably 1000 ppm or less. In particular, in the monomers having the dihydroxy compound represented by formula (IV) as the main component, wherein R Z The total amount of dihydroxy compounds in which at least one of the -OH groups has a carbon number different from that of formula (IV) is preferably 3000 ppm or less, more preferably 1500 ppm or less, still more preferably 1000 ppm or less, and particularly preferably 500 ppm or less. Z The total content of dihydroxy compounds in which at least one of the -OH groups has a carbon number different from that of formula (IV) is further preferably 1000 ppm or less, and more preferably 500 ppm or less. Similarly, the amount of impurities in the monomers of formula (I) will be within the ranges given for the monomers of formula (IV).

[0394] Suitable thermoplastic resins for producing optical devices such as lenses are in particular polycarbonates, polyester carbonates and polyesters. Preferred thermoplastic resins for producing optical devices such as lenses are in particular polycarbonates.

[0395] The polycarbonate is characterized in that it has structural units of at least one of formula (II), (IIa), (IIb), (IIc) and (IId), respectively, optionally structural units derived from diol monomers other than monomer compounds of formula (I), such as structural units of formula (V),

[0396] #-OR z -A 3 -R z -O-#(V)

[0397] in

[0398] #、R z and A 3 As defined above;

[0399] and structural units of formula (III-1) derived from carbonate-forming components:

[0400]

[0401] wherein each # represents a point of attachment to an adjacent structural unit, i.e., O at the point of attachment to the structural unit of formula (II), and O at the point of attachment to the structural unit of formula (V) (if present). The thermoplastic resin may be a polyester carbonate and / or a polyester, and thus, the structural units represented by the following formulas (V) and (III-1) or formulas (III-2) to (III-5) may be varied so that the thermoplastic resin includes polyester carbonate units and / or polyester units.

[0402] The polyester structure is characterized by having structural units of at least one of formula (II), (IIa), (IIb), (IIc) and (IId), respectively, optionally derived from structural units of diol monomers other than the monomer compound of formula (I), such as structural units of formula V. If X in formula (II) 1a and X 2a or X in formula (IIa), (IIb), (IIc) and (IId) 0a is selected from -CH2O-, the polyester may have structural units derived from one or more dicarboxylic acids, for example structural units of formula (III-2) in the case of phthalic acid, structural units of formula (III-3) in the case of naphthoic acid, structural units of formula (III-4) in the case of oxalic acid and structural units of formula (III-5) in the case of malonic acid:

[0403]

[0404] In formulae (III-2) to (III-5), each variable # represents the point of attachment to the adjacent structural unit, i.e., O to the point of attachment to the structural unit of formula (II) and O to the point of attachment to the structural unit of formula (V), if present.

[0405] The polyester carbonate structure is characterized by having structural units of at least one of the formulae (II), (IIa), (IIb), (IIc) and (IId), respectively, optionally structural units derived from diol monomers other than monomer compounds of the formula (I), such as structural units of the formula (V), structural units of the formula (III-1) derived from carbonate-forming components and structural units derived from dicarboxylic acids, such as structural units of the formula (III-2) in the case of phthalic acid, structural units of the formula (III-3) in the case of naphthoic acid, structural units of the formula (III-4) in the case of oxalic acid and structural units of the formula (III-5) in the case of malonic acid.

[0406] A particular group of embodiments relates to thermoplastic copolymer resins, in particular polycarbonates, polyester carbonates and polyesters, having structural units of formula (II) and one or more structural units of formula (V), i.e. resins, in particular polycarbonates, polyester carbonates and polyesters, obtainable by reacting at least one monomer of formula (I) with one or more monomers of formula (IV). In this case, the molar ratio of the monomers of formula (I) to the monomers of formula (IV) and similarly the molar ratio of the structural units of formula (II) to the structural units of formula (V) is in the range of 1:99 to 99:1, in particular in the range of 10:90 to 99:1, in particular in the range of 30:70 to 97:3, or in the range of 10:90 to 99:1, in particular in the range of 15:85 to 97:3, more preferably in the range of 20:80 to 96:4, or in the range of 25:75 to 96:4, in particular in the range of 27:73 to 96:4 or in the range of 27:73 to 99:1, even more preferably in the range of 27:73 to 90:10, and in particular in the range of 30:70 to 80:20 or in the range of 35:65 to 70:30. Therefore, the molar ratio of the structural units of the formula (II), based on the total molar amount of the structural units of the formulae (II) and (V), is generally 1 to 99 mol%, in particular 10 to 99 mol%, more preferably in the range of 15 to 97 mol% or in the range of 5 to 99 mol%, in particular in the range of 10 to 97 mol% or 15 to 95 mol% or in the range of 17 to 97 mol% or 20 to 97 mol%, even more preferably in the range of 17 to 90 mol%, and in particular in the range of 20 to 80 mol% or in the range of 25 to 70 mol%. Therefore, the molar ratio of the structural units of the formula (V), based on the total molar amount of the structural units of the formulae (II) and (V), is generally 1 to 99 mol%, in particular 1 to 90 mol%, more preferably in the range of 3 to 85 mol% or 5 to 85 mol% or in the range of 1 to 95 mol%, in particular in the range of 3 to 90 mol% or 3 to 80 mol% or in the range of 3 to 83 mol%, even more preferably in the range of 10 to 83 mol%, and in particular in the range of 20 to 80 mol% or in the range of 30 to 75 mol%.

[0407] A particular group of embodiments relates to thermoplastic copolymer resins, in particular polycarbonates, polyester carbonates and polyesters, having structural units of formula (II) and one or more structural units of formula (V-14) or (V-15), i.e. resins, in particular polycarbonates, polyester carbonates and polyesters, obtainable by reacting at least one monomer of formula (I) with one or more monomers of formula (IV-14) or (IV-15). In this case, the molar ratio of the monomer of formula (I) to the monomers of formula (IV-14) and (IV-15), and similarly the molar ratio of the structural units of formula (II) to the structural units of formula (V-14) and (V-15), is in the range of 50:50 to 99:1, in particular in the range of 70:30 to 98:2, and in particular in the range of 80:20 to 97:3.

[0408] Another specific group of embodiments relates to thermoplastic copolymer resins, in particular polycarbonates, polyester carbonates and polyesters, which have structural units of formula (II) and one or more structural units of formula (V-11), (V-12), (V-13), (V-21) or (V-22), i.e. resins, in particular polycarbonates, polyester carbonates and polyesters, which are obtainable by reacting at least one monomer of formula (I) with one or more monomers of formula (IV-11), (IV-12), (IV-13), (IV-21) or (IV-22). In this case, the molar ratio of the monomers of formula (I) to the monomers of formulae (IV-11), (IV-12), (IV-13), (IV-21) and (IV-22) and similarly the molar ratio of the structural units of formula (II) to the structural units of formulae (V-11), (V-12), (V-13), (V-21) and (V-22) is in the range of 30:70 to 90:10, in particular in the range of 40:60 to 85:15, in particular in the range of 50:50 to 80:20.

[0409] Thermoplastic copolymer resin of the present invention, such as polycarbonate resin, can include any one of random copolymer structure, block copolymer structure and alternating copolymer structure. Thermoplastic resin according to the present invention does not need to include all structural units (II) and one or more different structural units (V) in the same polymer molecule. That is, the thermoplastic copolymer resin according to the present invention can be a blended resin, as long as the above-mentioned structure is included in any one of multiple polymer molecules. For example, the thermoplastic resin including all of the above-mentioned structural units (II) and structural unit (V) can be a copolymer including all of the structural units (II) and structural unit (V), it can be a homopolymer and copolymer including at least one structural unit (II) and a mixture of a homopolymer or copolymer including at least one structural unit (V), or it can be a copolymer including at least one structural unit (II) and the first structural unit (V) and a blended resin including at least one structural unit (II) and the copolymer including at least one other structural unit (V) different from the first structural unit (V); etc.

[0410] Thermoplastic polycarbonates can be obtained by polycondensation of a diol component and a carbonate-forming component. Similarly, thermoplastic polyesters can be obtained by polycondensation of a diol component and a dicarboxylic acid or an ester-forming derivative thereof, or by polycondensation of a diol component and a carbonate-forming component. 1 and X 2 One of them is -(C1-C5-alkanediyl)-OH and the other is -C(O)OR x Polyester carbonates can be obtained by polycondensation of a diol component, a dicarboxylic acid or an ester-forming derivative thereof, and a carbonate-forming component.

[0411] The present invention also relates to a process for preparing a resin according to the invention by polycondensing a monomeric compound (I) with a suitable counterpart thereof to obtain a polycarbonate, polyester or polyester carbonate. The suitable counterpart depends on the resin to be prepared and on the X in the monomer (I). 1 and X 2 For example, to prepare polycarbonate, monomer compound (I) (wherein X 1 and X 2 The carbonate-forming compound is subjected to a polycondensation reaction, wherein the carbonate-forming compound can be, for example, a compound LG-C(=O)-LG, wherein each LG is independently a suitable leaving group, such as a halogen atom, OCCl3 or an OR group, wherein R is a C1-C4-alkyl, a phenyl, a chlorophenyl, a tolyl, a naphthyl, etc.; such as phosgene, diphosgene and a carbonic acid diester, such as diethyl carbonate, diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate and dinaphthyl carbonate. For example, in order to prepare a polyester, the monomer compound (I) (wherein X1 and X 2 -(C1-C5-alkanediyl)-OH) with a dicarboxylic acid or a suitable derivative thereof (e.g. a dicarboxylic acid halide or diester) to undergo a polycondensation reaction. Suitable dicarboxylic acids (derivatives) are, for example, compounds (VI-2) to (VI-5), wherein X is -OH, a halogen atom (especially Cl or Br) or an -OR group, wherein R is C1-C4-alkyl, phenyl, etc.:

[0412]

[0413] Further examples of suitable dicarboxylic acids (derivatives) are mentioned below.

[0414] Alternatively, to prepare polyesters, monomeric compound (I) (wherein X 1 and X 2 -C(O)OR x ) and diols for polycondensation. Suitable diols are compound (IV) and diols different from compound (IV) mentioned below. For example, to prepare polyester carbonate, monomer compound (I) (wherein X 1 and X 2 -(C1-C5-alkanediyl)-OH) with a carbonate-forming compound (e.g., the above-mentioned compound LG-C(=O)-LG) and a dicarboxylic acid or a suitable derivative thereof (e.g., the above-mentioned dicarboxylic acid (derivative)); or a monomer compound (I) (wherein X 1 and X 2 -C(O)OR x ) is subjected to a polycondensation reaction with a carbonate-forming compound (eg the compound LG-C(=O)-LG mentioned above) and a diol (eg the diols mentioned above in the context of the polyester).

[0415] Preferably, the method for preparing polycarbonate comprises making monomer compound (I) (wherein X 1 and X 2-(C1-C5-alkanediyl)-OH) with a carbonate-forming compound (e.g. the above-mentioned compound LG-C(=O)-LG), and optionally with a diol different from the compound (I), preferably with diol (IV) and more preferably with one of the preferred diols (IV) (e.g. (IV-11), (IV-12), (IV-13), (IV-14), (IV-15), (IV-21) or (IV-22)). Specifically, the method for preparing polycarbonates comprises polycondensing a monomeric compound of formula (Ia), (Ib), (Ic) or (Id) with a carbonate-forming compound (e.g., compound LG-C(=O)-LG), and optionally with a diol different from compound (I), preferably with diol (IV) and more preferably with one of the preferred diols (IV) (e.g., (IV-11), (IV-12), (IV-13), (IV-14), (IV-15), (IV-21) or (IV-22). Further details of the method are as follows.

[0416] Specifically, the thermoplastic resin (polycarbonate resin) can be prepared by the following method.

[0417] The method for preparing a thermoplastic resin such as a polycarbonate resin of the present invention comprises a process for melt polycondensation of a dihydroxy component corresponding to the above-mentioned structural unit with a carbonic acid diester. According to the present invention, the dihydroxy compound comprises at least one dihydroxy compound represented by formula (I), in particular a dihydroxy compound represented by formula (Ia), (Ib), (Ic) and (Id) as defined herein. In addition to the compound of formula (I), the dihydroxy compound may also comprise one or more dihydroxy compounds represented by formula (IV), preferably formulas (IV-1) to (IV-8), in particular formulas (IV-11) to (IV-22), in particular dihydroxy compounds represented by formulas (IV-11), (IV-12), (IV-13), (IV-14), (IV-15), (IV-21) or (IV-22).

[0418] As is clear from the above, a polycarbonate resin can be formed by reacting a dihydroxy component with a carbonate precursor, such as a carbonic acid diester, wherein the dihydroxy component includes at least one compound represented by Formula (I), (Ia), (Ib), (Ic) and (Id), respectively, or a combination of at least one compound represented by Formula (I), (Ia), (Ib), (Ic) and (Id), respectively, and at least one compound represented by Formula (IV), (IV-1), (IV-2), (IV-3), (IV-4), (IV-5), (IV-6), (IV-7), (IV-8), (IV-11), (IV-12), (IV-13), (IV-14), (IV-15), (IV-16), (IV-17), (IV-18), (IV-19), (IV-20), (IV-21) or (IV-22). Specifically, the polycarbonate resin can be formed by a melt polycondensation process, wherein compounds represented by formula (I), (Ia), (Ib), (Ic) and (Id), respectively, or a combination thereof with at least one compound represented by formula (IV), (IV-1), (IV-2), (IV-3), (IV-4), (IV-5), (IV-6), (IV-7), (IV-8), (IV-11), (IV-12), (IV-13), (IV-14), (IV-15), (IV-16), (IV-17), (IV-18), (IV-19), (IV-20), (IV-21) or (IV-22), are reacted with a carbonate precursor such as a carbonic acid diester in the presence of a basic compound catalyst, an ester exchange catalyst or a mixed catalyst thereof, or in the absence of a catalyst.

[0419] Thermoplastic resins (or polymers) other than polycarbonate resins, such as polyester carbonates and polyesters, are obtained by using dihydroxy compounds represented by formula (I), (Ia), (Ib), (Ic) and (Id), respectively, or a combination thereof with at least one compound represented by formula (IV), (IV-1), (IV-2), (IV-3), (IV-4), (IV-5), (IV-6), (IV-7), (IV-8), (IV-11), (IV-12), (IV-13), (IV-14), (IV-15), (IV-16), (IV-17), (IV-18), (IV-19), (IV-20) (IV-21) or (IV-22) as a material (or monomer).

[0420] As previously mentioned, the monomers of formula (I), and similarly the comonomers of formula (IV), used to make the thermoplastic resins may contain impurities resulting from their preparation.

[0421] For example, monomers of formula (IV-1) and (IV-2) (wherein R z It's O-Alk 2 - or O-Alk 2 -[O-Alk 2 -] w -) can include two of the R z are all dihydroxy compounds with single bonds, or R z One of the bonds is a single bond instead of O-Alk 2 - or O-Alk 2 -[O-Alk 2 -] w -dihydroxy compounds.

[0422] In the monomers having a dihydroxy compound represented by formula (IV-1) or (IV-2) as the main component, such dihydroxy compound represented by formula (IV-1) or (IV-2) (wherein at least one R z Different from O-Alk 2 - or O-Alk 2 -[O-Alk 2 -] w The total amount of dihydroxy compounds in which at least one of the values ​​of a and b or c and d is different from that of formula (IV-1) or (IV-2) is preferably 3000 ppm or less, more preferably 1500 ppm or less, still more preferably 1000 ppm or less, and particularly preferably 500 ppm or less. The total content of dihydroxy compounds in which at least one of the values ​​of a and b or c and d is different from that of formula (IV-1) or (IV-2) is also preferably 300 ppm or less, and more preferably 200 ppm or less.

[0423] The polycarbonate resin can be obtained by reacting a monomer compound of formula (I) with a carbonate precursor such as a carbonic acid diester, or can be obtained by reacting a combination of at least one monomer compound of formula (I), especially at least one monomer (I) mentioned herein as preferred, and one or more monomer compounds of formula (IV), especially monomer compounds of formula (IV-11), (IV-12), (IV-13), (IV-14), (IV-15), (IV-21), or (IV-22), etc. as a dihydroxy component with a carbonate precursor such as a carbonic acid diester.

[0424] However, during the polymerization process for making polycarbonate resins, some of the compound of formula (IV) may be converted into impurities, wherein the terminal R z One or both of the OH groups are replaced with a different group, such as a vinyl end group represented by -OCH=CH2.Since the amount of such impurities is usually small, the resulting polymer product can be used as a polycarbonate resin without purification.

[0425] The thermoplastic resin of the present invention may also contain a small amount of impurities, for example, as additional content of the thermoplastic resin composition or as part of the polymer backbone of the thermoplastic resin. Examples of such impurities include phenols, unreacted carbonic acid diesters, and monomers formed during the process of forming the thermoplastic resin. The total amount of impurities in the thermoplastic resin may be 5000 ppm or less, or 2000 ppm or less. The total amount of impurities in the thermoplastic resin is preferably 1000 ppm or less, more preferably 500 ppm or less, even more preferably 200 ppm or less, and particularly preferably 100 ppm or less.

[0426] The total amount of phenol as an impurity in the thermoplastic resin may be 3000 ppm or less, or 2000 ppm or less. The total amount of phenol as an impurity is preferably 1000 ppm or less, more preferably 800 ppm or less, still more preferably 500 ppm or less, particularly preferably 300 ppm or less.

[0427] The total amount of carbonic acid diester as an impurity in the thermoplastic resin is preferably 1000 ppm or less, more preferably 500 ppm or less, still more preferably 100 ppm or less, particularly preferably 50 ppm or less.

[0428] The total amount of unreacted monomers as impurities in the thermoplastic resin is preferably 3000 ppm or less, more preferably 2000 ppm or less, still more preferably 1000 ppm or less, particularly preferably 500 ppm or less.

[0429] The lower limit of the total amount of these impurities is not critical, but may be 0.1 ppm or 1.0 ppm.

[0430] The total amount of residual heavy metals such as palladium as impurities in the thermoplastic resin is preferably 50 ppm or less, more preferably 10 ppm or less. The amount of residual palladium can be reduced by standard methods, such as treatment with an adsorbent such as activated carbon.

[0431] By adjusting the amounts of phenol and carbonic acid diester, a resin with desired properties can be formed. The amounts of phenol, carbonic acid diester, and monomer can be appropriately adjusted by adjusting the polycondensation conditions, the operating conditions of the polymerization apparatus, and the extrusion molding conditions after the polycondensation process.

[0432] As measured by GPC (gel permeation chromatography), the weight average molecular weight (Mw) of the thermoplastic resin according to the present invention is preferably in the range of 5,000 to 100,000 Daltons, more preferably in the range of 10,000 to 80,000 Daltons, in particular in the range of 10,000 to 50,000 Daltons, 15,000 to 55,000 Daltons or 20,000 to 60,000 Daltons, and in particular in the range of 15,000 to 50,000 Daltons, 20,000 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 according to the present invention measured in this way is also expressed herein as "weight average molecular weight based on polystyrene". The number average molecular weight (Mn) of the thermoplastic resin according to the present invention is generally in the range of 3,000 to 30,000, preferably in the range of 3,000 to 20,000, more preferably in the range of 5,000 to 15,000, and particularly in the range of 7,000 to 14,000. The viscosity average molecular weight (Mv) of the thermoplastic resin according to the present invention is generally in the range of 8,000 to 28,000, preferably in the range of 8,000 to 20,000, more preferably in the range of 9,000 to 15,000, and even more preferably in the range of 10,000 to 14,000.

[0433] The value of the molecular weight distribution (Mw / Mn) of the thermoplastic resin according to the present invention is preferably from 1.5 to 9.0, more preferably from 1.8 to 7.0, still more preferably from 2.0 to 4.0.

[0434] When the thermoplastic resin has a weight average molecular weight (Mw) value within the above-mentioned suitable range, the molded article made of the thermoplastic resin has high strength. In addition, the thermoplastic resin with a suitable Mw value is advantageous for molding due to its excellent fluidity.

[0435] 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. w Low molecular weight compounds less than 1000. w The upper limit of the content of low molecular weight compounds of less than 1000 is generally 7.0% by weight, preferably 5.0% by weight, more preferably 3.0% by weight, even more preferably 2.0% by weight, particularly 1.8% by weight, and especially 1.7% by weight. Thus, in this particular group of embodiments, the molecular weight M in the thermoplastic resin is 1.5%, based on the total weight of the thermoplastic resin in each case. wThe content of low molecular weight compounds of less than 1000 is generally 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. %, especially in the range of 1.0 to 1.8 wt. %, particularly in the range of 1.0 to 1.7 wt. %.

[0436] The thermoplastic resin of the present invention includes M in the above content range. w Low molecular weight compounds with a value of less than 1000 can form molded articles with high mechanical strength. During molding processes (e.g., injection molding), such thermoplastic resins are particularly susceptible to or almost to separation or precipitation (also known as bleed-out) of the low molecular weight compounds. Furthermore, due to the high plasticity of the thermoplastic resins of the present invention, the thermoplastic resins containing the low molecular weight compounds in the above-defined amounts have advantageous properties such as fast molding speed and reduced energy requirements during the molding process.

[0437] The content of low molecular weight compounds in the thermoplastic resin is determined based on the above-mentioned GPC analysis spectrum. Specifically, 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 spectrum obtained by GPC analysis of the thermoplastic resin. Therefore, the content of low molecular weight compounds in the thermoplastic resin (CLWC) can be expressed by the following formula:

[0438]

[0439] The thermoplastic resin of the present invention, such as the polycarbonate resin mentioned above, has a high refractive index (n D or n d ), and is therefore suitable for producing optical lenses. The refractive index value referred to herein is a value for a film having a thickness of 0.1 mm, and can be measured using an Abbe refractometer according to the method of JIS-K-7142. The refractive index of the thermoplastic resin of the present invention, especially the polycarbonate resin of the present invention, at 23°C and a wavelength of 589 nm, is generally 1.640 or higher, preferably 1.650 or higher, more preferably 1.660 or higher, even more preferably 1.670 or higher, still more preferably 1.680 or higher, especially 1.690 or higher, for example 1.700 or higher, when the resin includes structural unit (II). For example, the refractive index of the copolycarbonate resin including the structural unit (II) and the structural unit (V) according to the present invention is preferably 1.640 to 1.690, 1.645 to 1.695, 1.640 to 1.700, 1.650 to 1.720, or 1.660 to 1.730, more preferably 1.670 to 1.740, and still more preferably 1.680 to 1.750.

[0440] The thermoplastic resin of the present invention, especially the polycarbonate resin of the present invention, preferably has an Abbe number (ν) of 26 or less, more preferably 24 or less, 23 or less, still more preferably 22 or less, or 21 or less, and particularly 20 or less, or 19 or less. The Abbe number can be calculated by the following formula based on the refractive index at wavelengths of 487 nm, 589 nm, and 656 nm at 23° C.

[0441] v=(n D -1) / (n F -n C )

[0442] n D : Refractive index at a wavelength of 589nm

[0443] n C : Refractive index at a wavelength of 656nm

[0444] n F : Refractive index at a wavelength of 486nm

[0445] The glass transition temperature (Tg) of the thermoplastic resin of the present invention, particularly the polycarbonate resin of the present invention, is generally in the range of 90 to 185°C, preferably 90 to 180°C, more preferably 100 to 170°C, and particularly 110 to 160°C, considering that polycarbonate can be used for injection molding. In terms of molding fluidity and molding heat resistance, the lower limit of Tg is preferably 120°C or 130°C, more preferably 135°C, and even more preferably 140°C; and the upper limit of Tg is preferably 180°C, more preferably 170°C, and even more preferably 160°C. A glass transition temperature (Tg) within the above-given range provides a significant range of usable temperatures and avoids the risk that the resin's melting temperature might be too high, causing the resin to decompose or discolor undesirably. Furthermore, it allows the production of molded articles with high surface finish. The values ​​given for the glass transition temperatures refer to values ​​measured by differential scanning calorimetry (DSC) using a 10° C. / min heating program in accordance with the protocol of JIS K7121-1987.

[0446] The absolute value of the orientation birefringence of the thermoplastic resin of the present invention, especially the polycarbonate resin of the present invention, is preferably from 0 to 1×10 -1 or 0 to 1x10 -2 in the range of 0 to 5x10 -3 in the range of 0 to 2x10 -3 In the range of 0 to 1x10 -3 In the range of 0 to 0.4x10 -3 within the range.

[0447] The total light transmittance of an optical molded article, such as an optical element, produced using the polycarbonate resin of the present invention is preferably 85% or higher, more preferably 87% or higher, and particularly preferably 88% or higher. A total light transmittance of preferably 85% or higher is comparable to that achieved by, for example, bisphenol A polycarbonate resins.

[0448] The thermoplastic resin according to the present invention has high moisture and heat resistance. Moisture and heat resistance can be evaluated by the following method: a molded body made using a thermoplastic resin, such as an optical element, is subjected to a "PCT test" (pressure cooker test), and then the total light transmittance of the molded body after the PCT test is measured. In the PCT test, first, an injection molded body having a diameter of 50 mm and a thickness of 3 mm is kept for 20 hours using PC305S III manufactured by HIRAYAMA Corporation, at 120°C, 0.2 MPa, and 100% RH for 20 hours. Then, the injection molded body sample is taken out of the device and the total light transmittance is measured using a SE2000 spectrophotometer manufactured by Nippon Denshoku Industries Co., Ltd. according to the method of JIS-K-7361-1.

[0449] The total light transmittance of the thermoplastic resin according to the present invention after the PCT test is 60% or higher, preferably 70% or higher, more preferably 75% or higher, even more preferably 80% or higher, and particularly preferably 85% or higher. As long as the total light transmittance is 60% or higher, the thermoplastic resin is considered to have higher moisture and heat resistance than conventional thermoplastic resins.

[0450] The thermoplastic resin according to the present invention preferably has a b value (indicating hue) of 5 or less. The smaller the b value, the less yellowish the color, and the better the hue.

[0451] According to the present invention, the diol component used to prepare the polycarbonate or polyester may additionally include one or more diol monomers other than the monomer compound of formula (I), for example one or more monomers of formula (IV).

[0452] Suitable diol monomers other than the monomer compounds of formula (I) are those conventionally used for the preparation of polycarbonates, for example

[0453] - aliphatic diols, such as ethylene glycol, propylene glycol, butanediol, pentanediol and hexanediol;

[0454] - 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, spiroglycerol, 1,4:3,6-dianhydro-D-sorbitol, 1,4:3,6-dianhydro-D-mannitol and 1,4:3,6-dianhydro-L-idiol are also included in examples of diols; and

[0455] Aromatic diols, especially aromatic diols of the formula (IV), for example bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)ketone, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-tert-butylphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, bis(4-hydroxyphenyl)propane )diphenylmethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, α,ω-bis[2-(p-hydroxyphenyl)ethyl]polydimethylsiloxane, α,ω-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane, 4,4'-[1,3-phenylenebis(1-methylethylidene)hydroxyphenyl]-1-phenylethane, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-tert-butylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-isopropylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-isopropylphenyl]fluorene, 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethyl)phenyl)fluorene, 9,9-bis(4-(2-hydroxyethyl)-3-phenylphenyl)fluorene, 9,9-bis(6-hydroxy-2-naphthyl)fluorene, 9,9-bis(6-(2-hydroxyethyl)-2-naphthyl)fluorene, 10,10-bis(4-hydroxyphenyl)anthracen-9-one, 10,10-bis(4-(2-hydroxyethyl)phenyl)anthracen-9-one, 2-[4-[4-(2-hydroxyethoxy)-3,5-di(thianthren-1-yl)phenyl]sulfonyl-2,6-di(thianthren-1-yl)phenoxy]ethanol , 2-[4-[4-(2-hydroxyethoxy)-3,5-di(dibenzo[b,d]thiophen-4-yl)phenyl]sulfonyl-2,6-dibenzo[b,d]thiophen-4-yl)phenoxy]ethanol, 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-di(phenanthren-9-yl)-phenyl]-1-methylethyl]-2,6-di(phenanthren-9-yl)-phenoxy]ethanol, and 2,2'-[1,1'-binaphthyl-2,2'-diylbis(oxy)]diethanol (also known as 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl or 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl (BNE)).

[0456] Preferably, in addition to the monomer of formula (I), the diol component also includes a monomer of at least one formula (IV). Especially, the total amount of the monomers of formula (I) and (IV) accounts for at least 90 weight % of the diol component based on the total weight of the diol component, or accounts for at least 90 mol % of the diol component based on the total molar amount of the diol monomers of the diol component. Especially, in addition to the monomer of formula (I), the diol component also includes at least one monomer selected from the monomers of formulas (IV-11) to (IV-22). More particularly, in addition to the monomer of formula (I), the diol component also includes at least one monomer selected from the monomers of formulas (IV-11), (IV-12), (IV-13), (IV-14), (IV-15), (IV-21) and (IV-22). In particular, in addition to the monomer of formula (I), the diol component further comprises at least one monomer selected from the group consisting of 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl, 9,9-bis(6-(2-hydroxyethoxy)-2-naphthyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 2-[4-[4-(2-hydroxyethoxy)-3,5-di(thianthren-1-yl)phenyl]sulfonyl-2,6-di( thien-1-yl)phenoxy]ethanol, 2-[4-[4-(2-hydroxyethoxy)-3,5-di(dibenzo[b,d]thien-4-yl)phenyl]sulfonyl-2,6-dibenzo[b,d]thien-4-yl)phenoxy]ethanol, 2-[4-[1-[4-(2-hydroxyethoxy)-3,5-di(phenanthren-9-yl)-phenyl]-1-methylethyl]-2,6-di(phenanthren-9-yl)-phenoxy]ethanol and 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene and combinations thereof.

[0457] Typically, the relative amount of monomeric compounds of formula (I), based on the total weight of the diol component, is at least 1% by weight, preferably at least 10% by weight, or at least 25% by weight, especially at least 15% by weight, or at least 20% by weight, in particular at least 15% by weight, or at least 25% by weight, preferably in the range of 1 to 99% by weight, or in the range of 10 to 98% by weight, in particular in the range of 15 to 98% by weight, or in the range of 20 to 98% by weight, or in the range of 25 to 98% by weight, or in the range of 25 to 97% by weight, in particular in the range of 10 to 96% by weight, or in the range of 15 to 95% by weight, or in the range of 25 to 95% by weight, or in the range of 25 to 93% by weight, but can also be up to 100% by weight.

[0458] Typically, the relative molar amount of the monomeric compounds of formula (I), based on the total molar amount of the diol component, is at least 1 mol%, preferably at least 10 mol%, or at least 25 mol%, especially at least 15 mol%, or at least 20 mol%, in particular at least 15 mol%, or at least 25 mol%, preferably in the range of 1 to 99 mol%, or in the range of 10 to 98 mol%, or in the range of 15 to 98 mol%, or in the range of 20 to 98 mol%, in particular in the range of 10 to 96 mol%, or in the range of 15 to 95 mol%, or in the range of 25 to 95 mol%, or in the range of 25 to 93 mol%, in particular in the range of 15 to 90 mol%, or in the range of 20 to 90 mol%, or in the range of 25 to 90 mol%, or in the range of 30 to 90 mol%, but can also be up to 100 mol%.

[0459] Thus, the relative molar amount of the monomeric compound of formula (IV), based on the total molar amount of the diol component, will not exceed 99 mol % or 90 mol % or 75 mol %, in particular not exceed 85 mol % or 80 mol %, in particular not exceed 85 mol % or 75 mol %, and is preferably in the range of 1 to 99 mol %, or in the range of 2 to 90 mol %, or in the range of 2 to 85 mol %, or in the range of 3 to 75 mol %, in particular in the range of 4 to 90 mol %, or in the range of 5 to 85 mol %, or in the range of 5 to 75 mol %, or in particular in the range of 10 to 85 mol %, or in the range of 10 to 80 mol %, or in the range of 10 to 75 mol %, or in the range of 10 to 70 mol %, but may also be up to 99.9 mol %.

[0460] Typically, the total molar amount of monomers of formula (I) and monomers of formula (IV) is at least 80 mol%, particularly at least 90 mol%, especially at least 95 mol%, or up to 100 mol%, based on the total molar amount of diol monomers in the diol component.

[0461] In addition to the monomer of formula (I) and the optional monomer of formula (IV), examples of further preferred aromatic dihydroxy compounds that can be used include, but are not limited to, bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, bisphenol Z, and the like.

[0462] To adjust the molecular weight and melt viscosity, the monomers forming the thermoplastic polymer may also include monofunctional compounds, such as monofunctional alcohols in the case of polycarbonates and monofunctional alcohols or monofunctional carboxylic acids in the case of polyesters. Suitable monohydric alcohols include butanol, hexanol, and octanol. Suitable monocarboxylic acids include, for example, benzoic acid, propionic acid, and butyric acid. To increase the molecular weight and melt viscosity, the monomers forming the thermoplastic polymer may also include polyfunctional compounds, such as polyfunctional alcohols having three or more hydroxyl groups in the case of polycarbonates and polyfunctional alcohols having three or more hydroxyl groups or polyfunctional carboxylic acids having three or more carboxyl groups in the case of polyesters. Suitable polyfunctional alcohols include, for example, glycerol, trimethylolpropane, pentaerythritol, and 1,3,5-trihydroxypentane. Suitable polyfunctional carboxylic acids having three or more carboxyl groups include, for example, trimellitic acid and pyromellitic acid. The total amount of these compounds, based on the molar amount of the diol component, generally does not exceed 10 mol%.

[0463] Suitable carbonate forming monomers are those conventionally 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 them, diphenyl carbonate is particularly preferred. Relative to a total of 1 mole of dihydroxy compounds, the usage ratio of carbonate forming monomers is generally 0.97 to 1.20 moles, more preferably 0.98 to 1.10 moles.

[0464] Suitable dicarboxylic acids include, but are not limited to

[0465] - aliphatic dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid;

[0466] - cycloaliphatic dicarboxylic acids, for example tricyclo[5.2.1.02,6]decanedicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, decalin-2,6-dicarboxylic acid and norbornanedicarboxylic acid; and

[0467] Aromatic dicarboxylic acids, for example phthalic acid, in particular phthalic acid, isophthalic acid, 2-methylterephthalic acid or terephthalic acid, and naphthalene dicarboxylic acids, in particular naphthalene-1,3-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-1,6-dicarboxylic acid, naphthalene-1,7-dicarboxylic acid, naphthalene-2,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, 2-[9-(carboxymethyl)fluoren-9-yl]acetic acid (Formula DC1), 2-[9-(carboxymethyl)fluoren-9-yl]propionic acid (Formula DC2), 2,2′-bis(carboxymethoxy)-1,1′-binaphthyl (Formula DC3) and naphthalene-2,7-dicarboxylic acid.

[0468]

[0469] Suitable ester-forming derivatives of dicarboxylic acids include, but are not limited to, dialkyl esters, diphenyl esters, and ditolyl esters.

[0470] In the case of polyester, the ester-forming monomer is used in a proportion of usually 0.97 to 1.20 mol, more preferably 0.98 to 1.10 mol, relative to 1 mol of the total dihydroxy compound.

[0471] The polycarbonates of the present invention can be prepared by reacting a diol component comprising a monomer of formula (I) and optionally an additional diol monomer, such as a monomer of formula (IV), with a carbonate-forming monomer by a preparation method similar to the known polycarbonate preparation described in, for example, US 9,360,593, US 2016 / 0319069 and US 2017 / 0276837 (all incorporated by reference).

[0472] The polyesters of the present invention can be prepared by reacting a diol component comprising a monomer of formula (I) and optionally an additional diol monomer, such as a monomer of formula (IV), with a dicarboxylic acid or an ester-forming derivative thereof by a preparation method similar to the known polyester preparation described, for example, in US 2017 / 044311 and the documents cited therein (which are fully incorporated herein by reference).

[0473] The polyester carbonates of the present invention can be prepared by reacting a diol component comprising a monomer of formula (I) and optionally an additional diol monomer, such as a monomer of formula (IV), a carbonate-forming monomer and a dicarboxylic acid or an ester-forming derivative thereof, by a preparation method similar to that of polyester carbonates known in the art.

[0474] In the case of using carbonate-forming monomers or ester-forming derivatives of polycarboxylic acids, polycarbonates, polyesters and polyester carbonates are generally prepared by reacting monomers of the diol component with carbonate-forming monomers and / or ester-forming monomers, i.e., dicarboxylic acids or ester-forming derivatives thereof, in the presence of an esterification catalyst, especially an ester exchange catalyst.

[0475] Suitable transesterification catalysts include basic compounds, which specifically include but are not limited to alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, etc. Similarly, suitable transesterification catalysts include acidic compounds, which specifically include but are not limited to Lewis acid compounds of polyvalent metals, including compounds of zinc, tin, titanium, zirconium, lead, etc.

[0476] Examples of suitable alkali metal compounds include alkali metal salts of organic acids such as acetic acid, stearic acid, benzoic acid or phenylphosphonic acid, alkali metal phenates, alkali metal oxides, alkali metal carbonates, alkali metal borohydrides, alkali metal bicarbonates, alkali metal phosphates, alkali metal hydrogenphosphates, alkali metal hydroxides, alkali metal hydrides, alkali metal alkoxides and the like. Specific examples thereof include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium borophenoxide, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, and disodium phenylphosphate; also included are disodium salt, dipotassium salt, dicesium salt, dilithium salt of bisphenol A; sodium salt, potassium salt, cesium salt, and lithium salt of phenol; and the like.

[0477] Examples of the alkaline earth metal compound include alkaline earth metal salts of organic acids such as acetic acid, stearic acid, benzoic acid or phenylphosphonic acid, alkaline earth metal phenoxides, alkaline earth metal oxides, alkaline earth metal carbonates, alkali metal borohydrides, alkaline earth metal hydrogen carbonates, alkaline earth metal hydroxides, alkaline earth metal hydrides, alkaline earth metal alkoxides, etc. Specific examples thereof include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium hydrogen carbonate, calcium hydrogen carbonate, strontium hydrogen carbonate, barium hydrogen carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, magnesium phenylphosphate, etc.

[0478] Examples of nitrogen-containing compounds include quaternary ammonium hydroxides, salts thereof, amines, etc. Specific examples thereof include quaternary ammonium hydroxides containing an alkyl group, an aryl group, etc., such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, etc.; tertiary amines such as triphenylamine, dimethylbenzylamine, triphenylamine, etc.; secondary amines such as diethylamine, dibutylamine, etc.; primary amines such as propylamine, butylamine, etc.; imidazoles such as 2-methylimidazole, 2-phenylimidazole, benzimidazole, etc.; bases or basic salts such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, tetraphenylammonium tetraphenylborate, etc.

[0479] The example of preferred transesterification catalyst comprises the salt of polyvalent metal such as zinc, tin, titanium, zirconium, lead etc., especially chloride, alkoxide, alkanoate, benzoate, acetylacetonate etc. They can be used alone or in combination of two or more. The specific example of this type of transesterification catalyst comprises zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin chloride (II), tin chloride (IV), tin acetate (II), tin acetate (IV), dibutyltin laurate, dibutyltin oxide, dibutyltin methoxide, zirconium acetylacetonate, zirconium oxyacetate, tetrabutoxy zirconium, lead acetate (II), lead acetate (IV) etc.

[0480] The ratio of the transesterification catalyst used is usually 10 to 1 mol of the total dihydroxy compound. -9 to 10 -3 mole, preferably 10 -7 to 10 -4 Moore.

[0481] Typically, polycarbonates, polyesters, and polyester carbonates are produced by melt polycondensation. In melt polycondensation, monomers are reacted in the absence of an additional inert solvent. While the reaction is proceeding, any byproducts formed during the transesterification reaction are removed by heating the reaction mixture under ambient pressure or reduced pressure.

[0482] Melt polycondensation reaction preferably comprises monomer and catalyst loading into reactor, and makes reaction mixture stand the condition that reaction between monomer and by-product are formed wherein.It has been found that if by-product stops at least for a period of time in polycondensation reaction, it is advantageous.But, in order to drive polycondensation reaction to product side, it is beneficial to remove at least a portion of by-product formed during polycondensation reaction or preferably at the end thereof.In order to allow by-product to enter reaction mixture, pressure can be controlled by closing reactor or by increasing or reducing pressure.The reaction time of this step is 20 minutes or longer and 240 minutes or shorter, preferably 40 minutes or longer and 180 minutes or shorter, particularly preferably 60 minutes or longer and 150 minutes or shorter.In this step, when by-product is removed very quickly by distillation after generation, the thermoplastic resin finally obtained has the high molecular weight resin molecule of low content.On the contrary, when by-product is allowed to stop certain time in reactor, the thermoplastic resin finally obtained has the high molecular weight resin molecule of high content.

[0483] The melt polycondensation reaction can be carried out in a continuous system or a batch system. The reactor that can be used for the reaction can be a vertical reactor, including an anchor stirring blade, Agitator blades, spiral ribbon agitator blades, etc.; horizontal reactors including paddle blades, cascade blades, spectacle blades, etc.; or extruder reactors including screws. Considering the viscosity of the polymer product, a reactor including a combination of these reactors is preferably used.

[0484] According to the method for manufacturing thermoplastic resins such as polycarbonate resins, after the polymerization reaction is completed, the catalyst can be removed or deactivated to maintain thermal stability and hydrolytic stability. A preferred method for deactivating the catalyst is to add an acidic substance. Specific examples of acidic substances include esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid, aromatic sulfonates such as butyl p-toluenesulfonate, hexyl p-toluenesulfonate, phosphoric acids such as phosphorous acid, phosphoric acid, phosphonic acid, etc. Phosphites such as triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, di-n-butyl phosphite, di-n-hexyl phosphite, dioctyl phosphite, monooctyl phosphite, etc. Phosphates such as triphenyl phosphate, monophenyl phosphite, diethyl phosphite, di-n-propyl phosphite, di-n-butyl phosphite, di-n-hexyl phosphite, dioctyl phosphite, monooctyl phosphite, etc. 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 stearyl chloride, benzoyl chloride, and p-toluenesulfonate; alkylsulfonic acids such as dimethylsulfonic acid; and organic halides such as benzyl chloride. The amount of these deactivators used is generally 0.01 to 50 mol, preferably 0.3 to 20 mol, relative to the catalyst. After the catalyst is deactivated, a step of removing low-boiling point compounds from the polymer by distillation may be performed. The distillation is preferably carried out under reduced pressure, for example, at a pressure of 0.1 to 1 mm Hg at a temperature of 200 to 350° C. For this step, a horizontal apparatus including a stirring blade having a high surface renewal ability, for example, a paddle blade, a cascade blade, a glasses blade, etc., or a thin film evaporator is preferably used.

[0485] Desirably, thermoplastic resins such as polycarbonate resins have very small amounts of foreign matter. Therefore, the molten product is preferably filtered to remove any solids from the melt. The mesh size of the filter is preferably 5 μm or less, more preferably 1 μm or less. Preferably, the produced polymer is filtered through a polymer filter. The mesh size of the polymer filter is preferably 100 μm or less, more preferably 30 μm or less. Needless to say, the step of sampling the resin pellets needs to be performed in a low dust environment. The dust environment is preferably Class 6 or lower, more preferably Class 5 or lower.

[0486] The thermoplastic resin can be molded by any molding method conventionally used for manufacturing optical elements. Suitable molding methods include, but are not limited to, injection molding, compression molding, casting, roll forming, extrusion molding, stretching, and the like.

[0487] Although the thermoplastic resin of the present invention can be molded as such, a resin composition can also be molded, which contains at least one thermoplastic resin of the present invention and also contains at least one additive and / or other resin. Suitable additives include antioxidants, processing stabilizers, light stabilizers, polymer metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, antibacterial agents, mold release agents, ultraviolet absorbers, plasticizers, compatibilizers, etc. Suitable other resins are, for example, other polycarbonate resins, polyester carbonate resins, polyester resins, polyamides, polyacetals, etc. that do not contain repeating units of formula (I).

[0488] Examples of antioxidants include, but are not limited to, triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane phaspiro[5.5]undecane), 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)benzofuran-2(3H)-one, 5,7-di-tert-butyl-3-(1,2-dimethylphenyl)benzofuran-2(3H)-one, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate and 3,9-bis{1,1-dimethyl Examples include 2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4,8,10-tetraoxaspiro(5,5)undecane. Among these examples, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane, 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)benzofuran-2(3H)-one, and 5,7-di-tert-butyl-3-(1,2-dimethylphenyl)benzofuran-2(3H)-one are more preferred. The content of the antioxidant in the thermoplastic resin is preferably 0.001 to 0.3 parts by weight relative to 100 parts by weight of the thermoplastic resin.

[0489] Examples of the processing stabilizer include, but are not limited to, phosphorus-based processing stabilizers, sulfur-based processing stabilizers, etc. Examples of the phosphorus-based processing stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, esters thereof, and the like. Specific examples thereof include triphenyl phosphite, tris(nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2,6-di-tert-butylphenyl)phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphites, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenylmonoorthoxenylphosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, dimethyl phenylphosphonate, diethyl phenylphosphonate, dipropyl phenylphosphonate, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, and the like. The content of the phosphorus-based processing stabilizer in the thermoplastic resin composition is preferably 0.001 to 0.2 parts by weight relative to 100 parts by weight of the thermoplastic resin.

[0490] 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, and distearyl-3,3'-thiodipropionate. The content of the sulfur-based processing stabilizer in the thermoplastic resin composition is preferably 0.001 to 0.2 parts by weight relative to 100 parts by weight of the thermoplastic resin.

[0491] The preferred release agent contains at least 90% by weight of an ester of an alcohol and a fatty acid. Specific examples of the ester of an alcohol and a fatty acid include esters of a monohydric alcohol and a fatty acid, and partial or complete esters of a polyhydric alcohol and a fatty acid. Preferred examples of the ester of the above-mentioned alcohol and a fatty acid include esters of a monohydric alcohol with a carbon number of 1 to 20 and esters of saturated fatty acids with a carbon number of 10 to 30. Preferred examples of the partial or complete ester of a polyhydric alcohol and a fatty acid include polyhydric alcohol with a carbon number of 2 to 25 and partial or complete esters of saturated fatty acids with a carbon number of 10 to 30. Specific examples of the ester of a monohydric alcohol and a fatty acid include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, etc. Specific examples of the partial or complete esters of polyols and fatty acids include glyceryl monostearate, glyceryl monostearate, glyceryl distearate, glyceryl tristearate, sorbitan monostearate, glyceryl behenate, glyceryl caprylate, glyceryl laurate, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, complete or partial esters of dipentaerythritol such as dipentaerythritol hexastearate, etc. The content of the release agent in the resin composition is preferably 0.005 to 2.0 parts by weight, more preferably 0.01 to 0.6 parts by weight, and even more preferably 0.02 to 0.5 parts by weight relative to 100 parts by weight of the thermoplastic resin.

[0492] Preferred UV absorbers are selected from benzotriazole UV absorbers, benzophenone UV absorbers, triazine UV absorbers, cyclic imine UV absorbers, and cyanoacrylate UV absorbers. Specifically, the following UV absorbers can be used alone or in combination of two or more.

[0493] Examples of the benzotriazole-based ultraviolet absorbers include 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2N-benzotriazol-2-yl)phenol)], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-pentylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-octyloxyphenyl)benzotriazole, 2,2'-methylenebis(4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis(1,3-benzoxazin-4-one), 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidemethyl)-5-methylphenyl]benzotriazole, etc.

[0494] Examples of the benzophenone-based ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfinyloxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid hydrate, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 ',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodiumsulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, etc.

[0495] Examples of the triazine-based ultraviolet absorber include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-([(hexyl)oxy]-phenol, 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-([(octyl)oxy]-phenol, and the like.

[0496] Examples of the cyclic imidoester-based ultraviolet absorbers include 2,2'-bis(3,1-benzoxazin-4-one), 2,2'-p-phenylenebis(3,1-benzoxazin-4-one), 2,2'-m-phenylenebis(3,1-benzoxazin-4-one), 2,2'-(4,4'-biphenylene)bis(3,1-benzoxazin-4-one), 2,2'-(2,6-naphthylene)bis(3, 1-benzoxazine-4-one), 2,2'-(1,5-naphthalene)bis(3,1-benzoxazine-4-one), 2,2'-(2-methyl-p-phenylene)bis(3,1-benzoxazine-4-one), 2,2'-(2-nitro-p-phenylene)bis(3,1-benzoxazine-4-one), 2,2'-(2-chloro-p-phenylene)bis(3,1-benzoxazine-4-one), etc.

[0497] Examples of the cyanoacrylate-based ultraviolet absorber include 1,3-bis-[(2′-cyano-3′,3′-diphenylacryloyl)oxy]-2,2-bis(((2-cyano-3,3-diphenylacryloyl)oxy)methyl)propane, 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene, and the like.

[0498] The content of the ultraviolet absorber in the resin composition is preferably 0.01 to 3.0 parts by weight, more preferably 0.02 to 1.0 parts by weight, and even more preferably 0.05 to 0.8 parts by weight, relative to 100 parts by weight of the thermoplastic resin. The ultraviolet absorber contained in this content range can provide sufficient weather resistance to the thermoplastic resin depending on the intended use.

[0499] As described above, thermoplastic polymer resins, particularly polycarbonate resins, comprising repeating units of formula (II), (IIa), (IIb), (IIc), and (IId), respectively, as described herein, provide thermoplastic resins with high transparency and high refractive index, and are therefore suitable for use in the preparation of optical devices requiring high transparency and high refractive index. More specifically, thermoplastic polycarbonates comprising structural units of formula (II), (IIa), (IIb), (IIc), and (IId), respectively, are characterized by having a high refractive index, preferably at least 1.640, more preferably at least 1.660, and especially at least 1.670.

[0500] The contribution of the monomers of formula (I), (Ia), (Ib), (Ic) and (Id), respectively, to the refractive index of a thermoplastic resin, particularly a polycarbonate resin, will depend on the refractive index of the monomer and the relative amount of the monomer in the thermoplastic resin. Generally, a higher refractive index of the monomers contained in the thermoplastic resin will result in a higher refractive index of the resulting thermoplastic resin. In addition, the refractive index of a thermoplastic resin comprising a structural unit of formula (II) can be calculated from the refractive index of the monomers used to prepare the thermoplastic resin, which in turn can be determined by refractometer measurement or by ab initio calculation, for example using the computer software ACD / ChemSketch 2012 (Advanced Chemistry Development, Inc.).

[0501] In the case of a thermoplastic copolymer resin, particularly a polycarbonate resin, the refractive index of the thermoplastic resin can be calculated from the refractive indices of the homopolymers of the respective monomers forming the copolymer resin by the following so-called "Fox equation":

[0502] 1 / n D =x1 / n D1 +x2 / n D2 +....x n / x Dn ,

[0503] where n D is the refractive index of the copolymer, x1, x2....x n is the mass fraction of monomers 1, 2, ..., n in the copolymer, D1 、n D2 ....n Dn is the refractive index of a homopolymer synthesized from only one of the monomers 1, 2, ... n. In the case of polycarbonate, x1, x2, ... x n is the mass fraction of OH monomers 1, 2, ....n based on the total amount of OH monomers. Obviously, a higher refractive index of the homopolymer will result in a higher refractive index of the copolymer.

[0504] The refractive index of a thermoplastic resin can be measured directly or indirectly. For direct measurement, the refractive index n of the thermoplastic resin is measured at a wavelength of 589 nm using an Abbe refractometer and applying a 0.1 mm thermoplastic resin film according to the protocol of JIS-K-7142. DIn the case of the refractive index of homopolycarbonates of compounds of formula (I), the refractive index can also be determined indirectly. For this purpose, copolycarbonates of the individual monomers of formula (I) with 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene and diphenyl carbonate were prepared according to the protocol of Example 1 in column 48 of US Pat. No. 9,360,593, and the refractive index n of the copolycarbonate was measured at a wavelength of 589 nm using an Abbe refractometer and a 0.1 mm film of the copolycarbonate according to the protocol of JIS-K-7142. D According to the refractive index n measured D The refractive index of the homopolycarbonate of the corresponding monomer can be determined by applying the Fox equation and the known refractive index of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (n D (589nm)=1.639).

[0505] The compounds of formula (I) can be obtained in a purity that provides a low yellowness index YI as measured according to ASTM E313, which can also be very important for use in the preparation of optical resins.

[0506] More precisely, the compounds of formula (I) preferably have a yellowness index YI of not more than 200, more preferably not more than 100, even more preferably not more than 50, in particular not more than 20 or not more than 10, determined according to ASTM E313.

[0507] The thermoplastic resin according to the present invention has a high refractive index and a low Abbe number. It can be used to manufacture transparent conductive substrates for liquid crystal displays, organic EL displays, solar cells, and the like. Furthermore, the thermoplastic resin can be used as a structural material for optical components such as optical discs, liquid crystal panels, optical cards, optical sheets, optical fibers, connectors, evaporated plastic mirrors, and displays; or as an optical device suitable for functional material applications.

[0508] Therefore, the thermoplastic resin of the present invention can be used to form molded articles such as optical devices. Optical devices include optical lenses and optical films. Specific examples of optical devices include lenses, films, mirrors, filters, prisms, and the like. These optical devices can be formed by any manufacturing process, for example, by injection molding, compression molding, injection-compression molding, extrusion molding, or solution casting.

[0509] Due to excellent moldability and high heat resistance, the thermoplastic resin of the present invention is very suitable for use in the manufacture of optical lenses that require injection molding. For molding, the thermoplastic resin of the present invention, such as polycarbonate resin, can be used as a mixture with other thermoplastic resins, such as different polycarbonate resins, polyester carbonate resins, polyester resins, and other resins.

[0510] In addition, the thermoplastic resin of the present invention may be mixed with additives for forming optical devices. The additives described above may be used as additives for forming optical devices. The additives may include antioxidants, processing stabilizers, light stabilizers, polymer metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, antimicrobial agents, mold release agents, ultraviolet absorbers, plasticizers, and compatibilizers.

[0511] As is apparent from the above, another aspect of the present invention relates to an optical device made of a thermoplastic resin as defined above, wherein the thermoplastic resin comprises structural units represented by formula (II) and optionally formula (V). With regard to the preferred meanings and preferred embodiments of the structural units of formulae (II) and (V), reference is made to the explanations given above.

[0512] Optical devices made from optical resins comprising repeating units of formula (II) and optionally repeating units of formula (V) as defined herein are typically optical molded articles, such as optical lenses, such as automotive headlight lenses, Fresnel lenses, fθ lenses for laser printers, camera lenses, lenses for glasses, and projection lenses for rear-projection televisions, CD-ROM pickup lenses, and optical discs, optical elements for image display media, optical films, film substrates, filters or prisms, liquid crystal panels, optical cards, optical sheets, optical fibers, optical connectors, deposition (eposition) plastic reflectors, and the like. Optical lenses and optical films are particularly preferred. Optical resins comprising repeating units of formula (II) and optionally repeating units of formula (V) can also be used to manufacture transparent conductive substrates that can be used for optical devices, which are suitable as structural elements or functional elements of transparent conductive substrates for liquid crystal displays, organic EL displays, solar cells, and the like.

[0513] The optical lens manufactured by the thermoplastic resin according to the present invention has a high refractive index, a low Abbe number and a low birefringence, and has high moisture and heat resistance. Therefore, the optical lens can be used in fields where expensive glass lenses with high refractive index are conventionally used, such as for telescopes, binoculars, television projectors, etc. Preferably, the optical lens is used in the form of an aspheric lens. Only one aspheric lens can substantially reduce spherical aberration to zero. Therefore, there is no need to use multiple spherical lenses to eliminate spherical aberration. Therefore, the weight and manufacturing cost of the device including spherical aberration are reduced. Among various types of optical lenses, aspheric lenses are particularly useful as camera lenses. The present invention easily provides an aspheric lens with a high refractive index and a low birefringence level that is technically difficult to manufacture by processing glass.

[0514] The optical lens of the present invention can be formed by, for example, injection molding, compression molding, injection compression molding, or casting a resin comprising a repeating unit of formula (II) and optionally a repeating unit of formula (V) as defined herein.

[0515] The optical lens of the present invention is characterized by minimal optical distortion. Optical lenses comprising conventional optical resins have significant optical distortion. While it is possible to reduce the optical distortion value by adjusting the molding conditions, the range of conditions is very narrow, making molding extremely difficult. Because the resin comprising the repeating units of formula (II) and the optional repeating units of formula (V) as defined herein has minimal optical distortion caused by resin orientation and minimal molding distortion, excellent optical elements can be obtained without requiring strict molding conditions.

[0516] In order to manufacture the optical lens of the present invention by injection molding, preferably, the lens is molded at a cylinder temperature of 260°C to 320°C and a mold temperature of 100°C to 140°C.

[0517] The optical lens of the present invention can be advantageously used as an aspheric lens, as needed. Since a single aspheric lens can substantially eliminate spherical aberration, there is no need to use a combination of spherical lenses to eliminate spherical aberration, thereby reducing weight and manufacturing costs. Therefore, among optical lenses, aspheric lenses are particularly useful as camera lenses.

[0518] Since the resins having the repeating units of formula (II) and optionally the repeating units of formula (V) as defined herein have high moldability, they are particularly useful as materials for thin optical lenses that are small in size and complex in shape. As for the lens size, the thickness of the central portion of the lens is 0.05 to 3.0 mm, preferably 0.05 to 2.0 mm, and more preferably 0.1 to 2.0 mm. The diameter of the lens is 1.0 to 20.0 mm, preferably 1.0 to 10.0 mm, and more preferably 3.0 to 10.0 mm. Meniscus lenses are preferred, which are convex on one side and concave on the other side.

[0519] The surface of the optical lens of the present invention may be coated, as desired, with a coating such as an antireflection layer or a hard coat. The antireflection layer may be a single layer or multiple layers and may be composed of an organic or 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.

[0520] The optical lens of the present invention can be formed by any method such as metal forming, cutting, polishing, laser processing, electrical discharge machining or edge grinding, preferably metal forming.

[0521] Optical films produced using the thermoplastic resin according to the present invention have high transparency and heat resistance, making them suitable for use in liquid crystal substrate films, optical memory cards, and the like. Needless to say, molding the optical film requires a low-dust environment to minimize the incorporation of foreign matter. The dust level is preferably 6 or lower, more preferably 5 or lower.

[0522] The following examples serve to further illustrate the present invention.

[0523] 1. Preparation of diol monomer of formula (I)

[0524] 1.1 Analysis related to the monomer of formula (I):

[0525] The results were measured at 23 °C using an 80 MHz NMR spectrometer (Magritek Spinsolve 80). 1 H-NMR spectrum.

[0526] DSC (Differential Scanning Calorimetry) measurements were performed using a Linseis Chip-DSC 10.

[0527] 1.2 Preparation Example of Monomer of Formula (I):

[0528] Example 1: Preparation of (dibenzo[b,d]thiophene-4,6-diyl)dimethanol (Also referred to herein as 4,6-bis(hydroxymethyl)-dibenzo[b,d]thiophene or DMO46DBT; prepared similarly to the method disclosed in C. Kuehm-Caubere et al., Tetrahedron 1996, 52(27), 9087-9092):

[0529]

[0530] At room temperature, dibenzothiophene (55.3 g; 300 mmol) was dissolved in 810 mL of tetrahydrofuran, and tetramethylethylenediamine (TMEDA, 104.6 g; 900 mmol) was added. The mixture was cooled to -78°C and stirred at this temperature for 30 minutes. 450 mL of a 2M solution of n-butyllithium in tetrahydrofuran was then added dropwise over 90 minutes. The reaction mixture was stirred at -78°C for 60 minutes, then finally warmed to room temperature and stirred at this temperature for 60 minutes. The reaction mixture was then cooled to -70°C again. After adding solid paraformaldehyde (31.5 g), the mixture was slowly warmed to 0°C, stirred at this temperature for 2 hours, then warmed to room temperature and stirred overnight. Finally, the mixture was quenched with saturated ammonium chloride solution (250 mL) and subsequently washed with 20% aqueous sodium hydroxide solution (250 mL), water (250 mL), and brine (250 mL). In the presence of 1% activated carbon, use Na2SO4 after drying, filter out inorganic matter, and evaporate the solvent completely. The crude product is recrystallized with methyl tert-butyl ether (MTBE). In the case of incomplete hydroxymethylation (that is, if a mixture of the desired product and the monomethylolated intermediate is obtained), the mixture is again hydroxymethylated according to the above steps. The productive rate of the obtained target product is 31 to 45%. After recrystallization from MTBE, the purity reaches 99.47%.

[0531] 1 H NMR (80MHz, DMSO-d6): δ = 8.21 (t, J = 4.6Hz, 2H), 7.59-7.21 (m, 4H), 5.50 (t, J = 5.6Hz, 2H), 4.74 (d, J = 5.3Hz, 4H) ppm.

[0532] mp (DSC): 216.4°C (melting point reported in literature: 216-218°C (see D. Rosario-Amorin; Inorganic Chemistry 2014, 53(11), 5698-5711)).

[0533] 2. Preparation of polycarbonate resin from monomers of formula (I)

[0534] 2.1 Analysis related to the resin prepared from the monomer of formula (I):

[0535] Refractive index (n D ):

[0536] The refractive index was measured using a test piece obtained by the general method for preparing homopolycarbonate described in Section 3.2 below. The measurement was performed at a temperature of 23° C. and a wavelength of 589 nm using a Rudolph Instruments J257 automatic refractometer.

[0537] Abbe number (ν):

[0538] The Abbe number was determined using the same approximately 3 mm thick sample as the test piece used in the refractive index measurement method above. Refractive index values ​​were measured at 23°C and wavelengths of 486 nm, 589 nm, and 656 nm using a Metricon 2010M prism coupler. The Abbe number was then calculated using the following formula:

[0539] v=(n D -1) / (n F -n C )

[0540] n D : Refractive index at a wavelength of 589nm

[0541] n C : Refractive index at a wavelength of 656nm

[0542] n F : Refractive index at a wavelength of 486nm

[0543] Glass transition temperature (Tg):

[0544] The glass transition temperature is measured by differential scanning calorimetry (DSC) using a heating program of 10° C. / min in accordance with JIS K7121-1987.

[0545] Differential Scanning Calorimetry Apparatus:

[0546] X-DSC7000, manufactured by Hitachi High-Tech Science Corporation.

[0547] Molecular weight

[0548] The weight average molecular weight of the resin (M w ) values ​​were measured according to gel permeation chromatography (GPC) and calculated by standard polystyrene conversion method. The apparatus, column and measurement conditions used were as follows:

[0549] GPC device: HLC-8420GPC (from Tosoh Corporation);

[0550] Columns: three TSKgel SuperHM-M (from Tosoh Corporation),

[0551] a guard column SuperHM-M (from Tosoh Corporation),

[0552] a TSKgel SuperH-RC (from Tosoh Corporation);

[0553] Detection device: RI detection

[0554] Standard polystyrene: PstQuick C as a standard polystyrene kit (from Tosoh Corporation);

[0555] Eluent: tetrahydrofuran;

[0556] Eluent flow rate: 0.6 ml / min;

[0557] Column temperature: 40℃.

[0558] Number average molecular weight (M n ) value can be used to measure the above M w The weight average molecular weight (M) in terms of polystyrene was calculated using a pre-made polystyrene standard curve. w ) and number average molecular weight (M n Specifically, a standard polystyrene with a known molecular weight ("PStQuick C" from Tosoh Corporation) can be used to prepare a calibration curve. In addition, based on the measurement data of the standard polystyrene, the elution time and molecular weight value of each peak are plotted and three-dimensionally approximated to obtain a calibration curve. w and M n The value of is calculated based on the following formula:

[0559] M w =Σ(Wi x Mi)÷Σ(Wi)

[0560] M n =∑(Ni x Mi)÷∑(Wi)

[0561] In the calculation formula, "i" represents the i-th cutoff point, "Wi" represents the molecular weight (g) of the polymer at the i-th cutoff point, "Ni" represents the number of polymer molecules at the i-th cutoff point, and "Mi" represents the molecular mass at the i-th cutoff point. Molecular mass (M) represents the molecular mass of polystyrene at the corresponding elution time in the calibration curve.

[0562] Low molecular weight compound content (CLWC)

[0563] The low molecular weight compound content (CLWC) represents the ratio of the total peak area of ​​compounds with Mw values ​​below 1000 to the total area of ​​all peaks, where the peak areas are determined according to the GPC analysis described above. Therefore, the CLWC value can be determined using the following formula:

[0564]

[0565] M of low molecular weight compounds w The values ​​can be determined using the method described above in the section "Molecular Weight".

[0566] Birefringence (Δn):

[0567] The birefringence (Δn) value of a resin can be measured, for example, by the following method: Each resin example to be analyzed is dissolved in dichloromethane (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 electroplated, and a cast film is prepared by evaporating the solvent at 25°C. A square film piece with a side of 50 mm and a thickness of 100 μm is cut from the cast film. At a temperature lower than the T of the resin, the birefringence (Δn) value is measured. g The film was stretched to 1.5 times or less at a temperature 20° C. higher. The stretching was performed using a stretcher SS-70 manufactured by Shibayama Scientific Co., Ltd. The retardation of the obtained stretched film was measured using an ellipsometer M-220 manufactured by JASCO Corporation.

[0568] Based on the retardation / phase difference Re, the birefringence value Δn can be calculated by the following formula:

[0569] Δn=|Re / d|

[0570] Δn: Orientation birefringence

[0571] Re: Phase difference [nm]

[0572] d: thickness [nm]

[0573] The algebraic symbol for birefringence uses the refractive index in the stretched direction of the film (n II ) and the refractive index in the direction perpendicular to the stretching direction (n ⊥ ), expressed as follows:

[0574] Δn=n II -n ⊥

[0575] If Δn is positive, it is called positive birefringence, and if Δn is negative, it is called negative birefringence.

[0576] 2.2 Preparation Examples of Homopolycarbonate and Copolycarbonate Resins

[0577] Example 2: Copolymer prepared from monomers DMO46DBT and BPEF

[0578] As raw materials, 2.50 kg (10.23 mol) of (dibenzo[b,d]thiophene-4,6-diyl) dimethanol (hereinafter also referred to as DMO46DBT), 13.46 kg (30.70 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (also referred to as BPEF), 9.03 kg (42.16 mol) of diphenyl carbonate (also referred to as DPC) and 16 ml of 2.5×10 -2 mol / l(4.1×10 -4 mol, that is, every 1 mol of the total amount of dihydroxy compound contains 10×10 -6 A 50-liter reactor equipped with a stirrer and a distillation apparatus was charged with a 100-mol sodium bicarbonate aqueous solution. After flushing the reactor with nitrogen, the reaction mixture was heated to 205°C for 1 hour and stirred at a pressure of 760 Torr. After the reaction mixture was completely dissolved, the pressure was reduced to 150 Torr over 15 minutes, and then a transesterification reaction was carried out at 205°C and 150 Torr for 20 minutes. Furthermore, the reaction mixture was heated to 240°C at a heating rate of 37.5°C / h, and the reaction conditions were maintained at 240°C and 150 Torr for 10 minutes. Then, the pressure was reduced to 120 Torr over 10 minutes, and the reaction conditions at 240°C and 120 Torr were maintained for 70 minutes. Subsequently, the pressure was reduced to 100 Torr over 10 minutes, and the reaction conditions at 240°C and 100 Torr were maintained for 10 minutes. Furthermore, the pressure was reduced to 1 Torr or less over 40 minutes, and a polymerization reaction was carried out at 240°C and 1 Torr for 10 minutes. After the reaction was completed, nitrogen was introduced into the reactor to increase the pressure, and the resulting polycarbonate resin was pelletized and taken out of the reactor. The properties of the resulting polycarbonate resin are summarized in Table 1.

[0579] Examples 3 to 5 and Comparative Examples

[0580] The polycarbonate resins of Examples 3 to 5 and Comparative Examples were prepared in a manner similar to that described in Example 2 above, except that the monomers specified in Table 1 below were used instead of DMO46DBT and BPEF, and the relative molar amounts of the monomers are also given in Table 1. The properties of the resulting resins are also summarized in Table 1.

[0581] Table 1:

[0582]

[0583] *) The full name and structure of the monomer are as follows:

[0584] DMO46DBT:(dibenzo[b,d]thiophene-4,6-diyl)dimethanol

[0585]

[0586] BPEF: 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene

[0587]

[0588] BNEF: 9,9-bis(6-(2-hydroxyethoxy)naphthalen-2-yl)fluorene

[0589]

[0590] DPBN: 2,2'-bis(2-hydroxyethoxy)-6,6'-diphenyl-1,1'-binaphthyl

[0591]

Claims

1. Use of a compound of formula (I) as a monomer for the preparation of a thermoplastic resin selected from polycarbonates, polyesters and polyester carbonates, in particular polycarbonates and polyesters, in X 1 and X 2 independently selected from -(C1-C5-alkanediyl)-OH and -C(O)OR x , where R x is selected from hydrogen and C1-C4-alkyl; A 1 and A 2 independently selected from a single bond and a monocyclic or polycyclic arylene group having 6 to 26 carbon atoms as ring members, wherein the monocyclic or polycyclic arylene group is unsubstituted or carries 1, 2, 3 or 4 R Ar group; Z 1 and Z 2 selected from phenylene and naphthylene; Y is selected from a single bond, O, S, S(O) and S(O)2; R 1 and R 2 are independently selected from halogen, C2-C3-alkynyl, CN, R, OR, CH s R' 3-s , NR2, C(O)R and CH=CHR", where if p + q>1, then R 1 and R 2 may be the same or different, where s is 0, 1 or 2 each time it appears; n is 0, 1, or 2; p and q are independently 0, 1 or 2; R is selected from C1-C4-alkyl, phenyl, naphthyl, phenanthrenyl and triphenylene, wherein phenyl, naphthyl, phenanthrenyl and triphenylene are unsubstituted or substituted by 1, 2, 3 or 4 identical or different R'" groups; R' is selected from phenyl, naphthyl, phenanthrenyl and triphenylene, wherein phenyl, naphthyl, phenanthrenyl and triphenylene are unsubstituted or substituted with 1, 2, 3 or 4 identical or different R'" groups; R" is selected from hydrogen, methyl, phenyl and naphthyl, wherein phenyl and naphthyl are unsubstituted or substituted with 1, 2, 3 or 4 identical or different R'" groups; R'" is selected from phenyl, halogen, OCH3, CH3, N(CH3)2 and C(O)CH3; R Ar Selected from fluorine, bromine, chlorine, CN, R 3 , OR 3 , benzyl, NR 3 2. C(O)R 3 and C(O)NH2, if more than one R Ar , then R Ar Can be the same or different; R 3 is selected from C1-C4-alkyl, phenyl and naphthyl.

2. The use of the compound according to claim 1, wherein X 1 and X 2 has the same meaning and is -CH2-OH or -C(O)OR x , where R x is hydrogen or methyl, especially methyl.

3. The use of a compound according to claim 1 or claim 2, wherein A 1 and A 2 have the same meanings and are selected from a single bond, a phenylene group and a naphthylene group.

4. The use of a compound according to any one of the preceding claims, wherein R 1 and R 2 If present, it has the same meaning and is independently selected from fluorine, CN, methyl, methoxy, benzyl, phenyl, naphthyl and phenanthrenyl, in particular from fluorine, phenyl and naphthyl.

5. Use of a compound according to any one of the preceding claims, wherein p and q have the same meaning and are 0 or 1, in particular 0.

6. The use of a compound according to any one of the preceding claims, wherein formula (I) is represented by formula (Ia):

7. The use according to claim 6 or the compound of formula (Ia), wherein R 0 Substituents, if present, are each located on the S(O) n The para position of the group.

8. The use of a compound according to any one of claims 1 to 5, wherein formula (I) is represented by formula (Ib):

9. The use according to claim 8 or the compound of formula (Ib), wherein R 0 Substituents, if present, are each located on the S(O) n ortho position of the group.

10. The use or compound according to any one of claims 6 to 9, wherein the variable n is 0.

11. The use of a compound according to any one of claims 1 to 5, wherein formula (I) is represented by formula (Ic):

12. The use of a compound of formula (Ic) according to claim 11, wherein -A 0 -X 0 The group is located in the meta or para position relative to the point of attachment of Y.

13. Use of a compound of formula (Ic) according to claim 11 or claim 12, wherein Y is S or O, especially S.

14. The use of a compound according to any one of claims 1 to 5, wherein formula (I) is represented by formula (Id):

15. Use of the compound according to claim 14, wherein Y is O.

16. Use of a compound of formula (Ia) according to claim 6, wherein the compound is 4,6-bis(hydroxymethyl)-dibenzo[b,d]thiophene.

17. Use of a compound of formula (Ib) according to claim 8, wherein the compound is 2,8-bis(hydroxymethyl)-dibenzo[b,d]thiophene.

18. A thermoplastic resin selected from polycarbonate, polyester and polyester carbonate, comprising a structural unit represented by the following formula (II) in # indicates the connection point with the adjacent structural unit; X 1a and X 2a Derived from X 1 and X 2 , replacing X with an oxo-, i.e. -O-, moiety 1 or X 2 -OH or -OR x group; and X 1 、X 2 、A 1 、A 2 、R 1 、R 2 , n, p and q are as defined in any one of claims 1 to 5.

19. The thermoplastic resin according to claim 18, wherein X in the structural unit of formula (II) 1a and X 2a All are -CH2O-, and are connected to one of the structures represented by the following formulae (III-1) to (III-5): in # indicates the connection point with the adjacent structural unit.

20. The thermoplastic resin according to any one of claims 18 or 19, which is selected from copolycarbonate resins, copolyestercarbonate resins and copolyester resins, wherein the thermoplastic resin further comprises a structural unit of formula (V) in addition to the structural unit represented by formula (II), #-O-R z -A 3 -R z -O-#-(V) in # indicates the connection point with the adjacent structural unit; A 3 is a polycyclic group with at least two benzene rings, wherein the benzene rings may be connected via W and / or directly fused to each other and / or fused via a non-benzene carbocyclic ring and / or fused via two non-benzene carbocyclic rings connected via a linker L, wherein A 3 Unsubstituted or replaced by 1, 2 or 3 R aa Group substituted, the R aa the radical is selected from halogen, C1-C6-alkyl, C5-C6-cycloalkyl, phenyl, naphthyl, 1,2-dihydroacenaphthenyl, phenanthrenyl, pyrenyl, triphenylene, benzo[b]furanyl, dibenzo[b,d]furanyl, benzo[b]thienyl, dibenzo[b,d]thienyl and thianthrenyl; W is selected from a single bond, O, C=O, S, S(O), SO2, CH2, CH-Ar, CAr2, CH(CH3), C(CH3)2 and a group of formula (A') in Q' represents a single bond, O, NH, C=O, CH2 or CH=CH; R 7a 、R 7b independently selected from hydrogen, fluorine, CN, R, OR, CH v R' 3-v , NR2, C(O)R and C(O)NH2, wherein R and R' are as defined in claim 1, and v is 0, 1 or 2; and * indicates the point of attachment to the benzene ring; L is selected from a single bond, C1-C4-alkylene, C4-C7-cycloalkylene, C4-C7-cycloalkylene dimethylene, phenylenedimethylene, wherein L is unsubstituted or replaced by 1 or 2 R L Group substituted, the R L a radical selected from the group consisting of C1-C4-alkyl, halogen, C1-C4-haloalkyl, C4-C7-cycloalkyl and phenyl, Ar is selected from monocyclic or polycyclic aryl groups having 6 to 26 carbon atoms as ring atoms and monocyclic or polycyclic heteroaryl groups having a total of 5 to 26 atoms as ring members, wherein 1, 2, 3 or 4 of these ring member atoms of the heteroaryl group are selected from nitrogen, sulfur and oxygen, and the remaining atoms of these ring member atoms of the heteroaryl group are carbon atoms, wherein Ar is unsubstituted or replaced by 1, 2 or 3 R ab Group substituted, the R ab A group is selected from halogen, phenyl and C1-C4-alkyl; and R z For single bond, Alk 1 、O-Alk 2 -、O-Alk 2 -[O-Alk 2 -] w - or O-Alk 3 -C(O)-, where O is bound to A 3 ,in w is an integer from 1 to 10; Alk 1 is C1-C4-alkanediyl; Alk 2 is C2-C4-alkanediyl; and Alk 3 It is C1-C4-alkanediyl.

21. The thermoplastic resin according to claim 20, wherein the structural unit of formula V is represented by one of the following formulas V-1 to V-8: in a and b are 0, 1, 2 or 3, in particular 0 or 1; a' and b' are 0, 1, 2 or 3, in particular 0 or 1; c and d are 0, 1, 2, 3, 4 or 5, especially 0 or 1; e and f are 0, 1, 2, 3, 4 or 5, especially 0 or 1; W' is S, S(O), SO2, O, a single bond, CH2, CH(CH3) or C(CH3)2, in particular S, S(O), SO2 or C(CH3)2; And where R z 、R aa 、R ab 、R 7a 、R 7b and L are as defined for formula (V).

22. The thermoplastic resin according to any one of claims 20 or 21, wherein The molar ratio of the structural units of formula (II), based on the total molar amount of the structural units of formula (II) and the structural units of formula (V), is 1 to 99 mol %, preferably 10 to 99 mol %, in particular 15 to 97 mol %, 15 to 95 mol % or 20 to 97 mol %, and the molar ratio of the structural units of formula (V), based on the total molar amount of the structural units of formula (II) and the structural units of formula (V), is 1 to 99 mol %, preferably 1 to 90 mol %, in particular 3 to 85 mol %, 3 to 80 mol % or 5 to 85 mol %.

23. The thermoplastic resin according to any one of claims 18 to 22, which has a refractive index of 1.640 or higher.

24. The thermoplastic resin according to any one of claims 18 to 23, which has an Abbe number of 26 or less.

25. The thermoplastic resin according to any one of claims 18 to 24, having a glass transition temperature T g 90 to 185°C.

26. An optical device made of the thermoplastic resin as defined in any one of claims 18 to 25.

Images