CN117940399A

CN117940399A - Heteroaryl or aryl substituted bisphenol compounds and thermoplastic resins

Info

Publication number: CN117940399A
Application number: CN202280060453.6A
Authority: CN
Inventors: 加藤宣之; 西森克吏; 茂木笃志; 石原健太朗; 池田慎也; 渡边贵文; 绪方龙展; 高松一贵; 原田祐太郎; V·安卓许科; K·鲁特; P·柯奇尔; F·史托兹; M·康图
Original assignee: Mitsubishi Gas Chemical Co Inc
Current assignee: Mitsubishi Gas Chemical Co Inc
Priority date: 2021-09-10
Filing date: 2022-09-08
Publication date: 2024-04-26

Abstract

The present invention relates to compounds of formula (I), X is selected from single bond, O, N- (C ₁-C₄) -alkyl, N-Ar ¹、CR⁵R⁶, S, S (O) and SO ₂;Z¹ and Z ² is independently selected from hydrogen 、-Alk-OH、-CH₂-Ar²-CH₂-OH、-Alk'-C(O)OR^x、-CH₂-Ar²-C(O)OR^x and-C (O) -Ar ²-C(O)OR^x,R^x is selected from hydrogen, phenyl, benzyl and C ₁-C₄ -alkyl; r ¹ and R ² are independently selected from optionally substituted mono-or polycyclic aryl groups having from 6 to 26 ring member carbon atoms and optionally substituted mono-or polycyclic heteroaryl groups having from 5 to 26 total ring member atoms, R ⁵ is selected from hydrogen, C ₁-C₄ -alkyl and Ar ¹ groups; r ⁶ is selected from hydrogen and C ₁-C₄ -alkyl; alk is C ₂-C₄ -alkanediyl; with the proviso that if R ³ and R ⁴ are hydrogen, R ¹ and R ² are not both phenyl. Also relates to the use of a compound of formula (I) as defined herein as a monomer for the manufacture of a thermoplastic resin comprising structural units of formula (II) below, # represents the point of attachment to an adjacent structural unit; x, Z ^1a、Z^2a、R¹、R²、R³ and R ⁴ are as defined herein, and to the thermoplastic resin. Also disclosed is an optical device comprising the thermoplastic resin comprising the structural unit represented by formula (II) as defined herein.

Description

Heteroaryl or aryl substituted bisphenol compounds and thermoplastic resins

Technical Field

The present invention relates to heteroaryl or aryl substituted bisphenol 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

An optical device, such as an optical lens made of an optical resin instead of an optical glass, is advantageous in the following aspects: 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 higher refractive indices are highly desirable because they allow for a reduction in size and weight of the final product. In general, when an optical material having a higher refractive index is used, a lens element having the same refractive power can be realized with a surface having a smaller curvature, so that the amount of aberration generated on the surface can be reduced. As a result, the number of lenses can be reduced to reduce decentration sensitivity of the lenses and/or to reduce the thickness of the lenses, thereby achieving weight saving.

EP2034337 describes copolycarbonate resins comprising 99 to 51mol% of recurring units derived from 9, 9-bis (4- (2-hydroxyethoxy) phenyl) fluorene and 1 to 49mol% of recurring units derived from bisphenol A. The resin is suitable for preparing optical lenses with low Abbe number (23 to 26) and refractive index of 1.62 to 1.64.

US9,360,593 describes polycarbonate resins having repeat units derived from 2,2' -bis (2-hydroxyethoxy) -1, 1-binaphthyl. Polycarbonate resins are said to have beneficial optical properties in terms of high refractive index, low abbe number, high transparency, low birefringence, and glass transition temperature suitable for injection molding. Copolycarbonates of bis (2-hydroxyethoxy) -1, 1-binaphthyl with 10, 10-bis (4-hydroxyphenyl) anthrone monomers and their use for the preparation of optical lenses are described in US 2016/0319069. The copolymer is reported to have good moisture resistance and a refractive index in the range of about 1.662 to 1.667.

WO 2019/043060 describes a thermoplastic resin for the manufacture of optical materials, wherein the thermoplastic resin comprises a polymeric compound of formula (2)

Wherein the method comprises the steps of

X is, for example, C ₂-C₄ -alkanediyl;

r and R' are identical or different and are selected from optionally substituted monocyclic or polycyclic aryl groups having 6 to 36 carbon atoms and optionally substituted monocyclic or polycyclic heteroaryl groups having a total of 5 to 36 atoms.

WO 2019/154727 describes a thermoplastic resin for manufacturing optical materials, wherein the thermoplastic resin comprises a polymeric compound of formula (3)

Wherein the method comprises the steps of

R ¹、R² is, for example, hydrogen;

Y is an alkylene group having 2, 3 or 4 carbon atoms,

Ar is selected from the group consisting of monocyclic or polycyclic aryl and monocyclic or polycyclic heteroaryl;

x ¹、X²、X³、X⁴ is CH, C-R ^x or N, provided that at most two of X ¹、X²、X³、X⁴ in each ring are N;

R ^x is, for example, halogen, CN, or ch=ch ₂.

WO 2020/079225 describes thermoplastic resins for the manufacture of optical materials, wherein the thermoplastic resins comprise a polymerized compound of formula (4)

Wherein the method comprises the steps of

A ¹、A² is selected from the group consisting of a monocyclic or bicyclic aromatic group and a monocyclic or bicyclic heteroaromatic group,

X represents, for example, a single bond, O, NH or an optionally substituted carbon atom

Y is, for example, absent or represents a single bond or has the same meaning as that of X;

R ¹、R² is hydrogen, an Ar' group, or an R ^a group;

r ³ is especially O-alkylene;

m, n are 0,1 or 2;

R ⁴、R⁵ is selected, for example, from CN and R ^a groups;

R ^a is selected from the group consisting of C.ident.C-R ¹¹ and Ar-C.ident.C-R ¹¹, wherein R ¹¹ and Ar are aromatic groups,

Wherein at least one of the groups attached to a ¹ or a ² is a group R ^a.

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

Monomers used to make thermoplastic resins with high refractive indices also typically result in positive birefringence values of the resin. For optics, birefringence is an undesirable property. To date, positive birefringence has been compensated for by using comonomers with negative birefringence, such as 9, 9-bis (4- (2-hydroxy-ethoxy) phenyl) fluorene. However, these comonomers reduce the refractive index of the resulting polymer. At present, few known monomers can provide high refractive index and low birefringence.

Despite advances in the field of optical resins, there is a continuing need for monomers for preparing optical resins, particularly polycarbonate resins and polyester resins, which result in high refractive indices and are therefore useful in the manufacture of optical devices, particularly lenses. In addition, the monomers should not impair other optical properties of the optical resin, such as low abbe number, high transparency, and low birefringence. In addition, the monomers should be easy to prepare. Furthermore, the resins obtained from these monomers, in particular polyesters and polycarbonates, should have good resistance to moisture and heat and they should have a sufficiently high glass transition temperature for injection molding.

CITATION LIST

Patent literature

Patent document 1: EP2034337

Patent document 2: US 9,360,593

Patent document 3: US2016/0319069

Patent document 4: WO 2019/043060

Patent document 5: WO 2019/154727

Patent document 6: WO 2020/079225

Non-patent literature

Non-patent document 1: S.R. Turner et al High Performance Polymers (2005) pp.361-376.

Disclosure of Invention

Technical problem

The above problems are recognized.

Solving the problems

The present invention solves these problems.

Advantageous effects of the invention

The present invention has the following advantageous effects.

Drawings

FIG. 1 shows the results of retardation or birefringence measurements of the resins prepared in examples 31, 33 and 34 and the polycarbonate resins prepared from bisphenol A.

Fig. 2 is a partially enlarged portion of fig. 1 showing retardation or birefringence of the polymers of examples 31, 33 and 34.

FIG. 3 shows a GPC chart of the resin of example 41.

Detailed Description

Surprisingly, it has been found that the compounds of formula (I) described herein are useful monomers for the preparation of thermoplastic resins, in particular polycarbonates and polyesters, which have high transparency and high refractive index and also impart suitable glass transition temperatures to the polycarbonates and polyesters. Therefore, such thermoplastic resins are suitable for use in the manufacture of optical resins requiring high transparency and high refractive index. Some of the monomers of formula (I) described herein provide high refractive index and low birefringence or even negative birefringence. Furthermore, the compounds of formula (I) can be readily incorporated into polyesters and polycarbonates and are thermally stable under the polymerization conditions. Thus, the resulting polyesters and polycarbonates have low yellowness (yellowness). Thus, thermoplastic resins containing polymerized form of monomers of formula (I) can be advantageously used to prepare optical devices made from the resins.

The present invention therefore relates to compounds of formula (I)

Wherein the method comprises the steps of

X is selected from single bond, O, N- (C ₁-C₄) -alkyl, N-Ar ¹、CR⁵R⁶, S, S (O) and SO ₂;

Z ¹ and Z ² are independently selected from hydrogen 、-Alk¹-OH、-CH₂-Ar²-CH₂-OH、-Alk²-C(O)OR^x、-CH₂-Ar²-C(O)OR^x and-C (O) -Ar ²-C(O)OR^x, wherein R ^x is selected from hydrogen, phenyl, benzyl and C ₁-C₄ -alkyl;

R ¹ and R ² are independently selected from the group consisting of monocyclic or polycyclic aryl groups having 6 to 26 carbon atoms as ring members and monocyclic or polycyclic heteroaryl groups having a total of 5 to 26 atoms as ring members, wherein 1,2, 3 or 4 of the ring member atoms of the heteroaryl groups are selected from nitrogen, sulfur and oxygen and the remaining atoms of the ring member atoms of the heteroaryl groups are carbon atoms, wherein the monocyclic or polycyclic aryl groups and the monocyclic or polycyclic heteroaryl groups are unsubstituted or carry 1,2, 3 or 4R ^Ar groups;

R ³ and R ⁴ are independently selected from hydrogen, a monocyclic or polycyclic aryl group having 6 to 26 carbon atoms as ring members, and a monocyclic or polycyclic heteroaryl group having a total of 5 to 26 atoms as ring members, wherein 1, 2, 3, or 4 of the ring member atoms of the heteroaryl group are selected from nitrogen, sulfur, and oxygen, and the remaining atoms of the ring member atoms of the heteroaryl group are carbon atoms, wherein the monocyclic or polycyclic aryl group and the monocyclic or polycyclic heteroaryl group are unsubstituted or carry 1, 2, 3, or 4R ^Ar groups;

r ⁵ is selected from hydrogen and C ₁-C₄ -alkyl;

r ⁶ is selected from hydrogen and C ₁-C₄ -alkyl;

Ar ¹ is selected from the group consisting of a monocyclic or polycyclic aryl group having from 6 to 26 carbon atoms as ring members and a monocyclic or polycyclic heteroaryl group having from 5 to 26 total atoms as ring members, wherein 1,2, 3 or 4 of the ring member atoms of the heteroaryl group are selected from nitrogen, sulfur and oxygen and the remaining atoms of the ring member atoms of the heteroaryl group are carbon atoms, wherein the monocyclic or polycyclic aryl group and the monocyclic or polycyclic heteroaryl group are unsubstituted or carry 1,2, 3 or 4R ^Ar groups;

Ar ² is selected from the group consisting of phenylene, naphthylene, and biphenylene (biphenylylene);

Alk is C ₂-C₄ -alkanediyl;

Alk' is C ₁-C₄ -alkanediyl;

R ^Ar is selected from R, OR, CH _nR_3-n、NR₂, and ch=chr', wherein R ^Ar may be the same OR different if more than one R ^Ar is present on the same heteroaryl OR aryl group;

r is selected from methyl, ethyl, phenyl, naphthyl, phenanthryl and Triphenylene (TRIPHENYLENYL), wherein phenyl, naphthyl, phenanthryl and triphenylene are unsubstituted or substituted with 1, 2,3 or 4R' groups which may be the same or different;

r 'is selected from hydrogen, methyl, phenyl and naphthyl, wherein phenyl and naphthyl are unsubstituted or substituted with 1,2, 3 or 4R' groups, which may be the same or different;

R' is selected from phenyl, OCH ₃、CH₃、N(CH₃)₂ and C (O) CH ₃; and

N is 0,1 or 2;

with the proviso that if R ³ and R ⁴ are both hydrogen, then R ¹ and R ² are not both phenyl.

The compounds described above are particularly useful for preparing thermoplastic resins, especially optical resins as defined herein, especially polycarbonate resins.

The compounds of formula (I) provide resins having a high refractive index when used as monomers for the preparation of optical resins, especially polycarbonate resins and polyester resins. Furthermore, the compounds of formula (I) provide high transparency of the resin and they do not significantly impair other optical and mechanical properties of the resin. In particular, these resins meet other requirements of optical resins, such as low abbe number, high transparency, and low birefringence. In addition, the monomers provide sufficiently high glass transition temperatures to the optical resins produced therefrom. In addition, the monomers of formula (I) can be prepared easily and obtained in high yields and purity. In particular, the compounds of formula (I) may be obtained in crystalline form, which allows for efficient purification to the extent required for the preparation of optical resins. In particular, the compounds of formula (I) can be obtained in a purity that provides low haze (haze), which is particularly important for use in the preparation of optical resins. Compounds of formula (I) without color imparting groups such as some of the R ¹、R²、R³、R⁴ and Ar ¹ groups can also be obtained in purities providing low yellowness index y.i. and low APHA color numbers as determined according to ASTM E313, which is also important for use in the preparation of optical resins.

The present invention also relates to a thermoplastic resin comprising polymerized units of a compound of formula (I), i.e. comprising structural units represented by the following formula (II);

Wherein the method comprises the steps of

# Represents the connection point with the adjacent structural unit;

And wherein Z ^1a and Z ^2a are derived from Z ¹ OR Z ², respectively, in formula (I), replacing hydrogen with a single bond if Z ¹ OR Z ² is hydrogen, OR replacing the-OH OR-OR ^x group of Z ¹ OR Z ² with an oxo (-O-) unit if Z ¹ OR Z ² is not hydrogen, and wherein Z ¹、Z²、X、R¹、R²、R³ and R ⁴ are as defined above.

The invention also relates to a thermoplastic resin selected from the group consisting of copolycarbonate resins, copolyestercarbonate (copolyestercarbonate) resins and copolyester resins, wherein the thermoplastic resin comprises structural units of formula (V) in addition to structural units of formula (II),

#-O-R^z-A¹-R^z-O-#- (V)

Wherein the method comprises the steps of

# Represents the connection point with the adjacent structural unit;

A ¹ is a polycyclic group with at least 2 benzene rings, wherein the benzene rings may be linked by A and/or fused directly to each other and/or fused through a non-benzene carbocyclic ring, wherein A ¹ is unsubstituted or substituted with 1, 2 or 3R ^aa groups selected from halogen, C ₁-C₆ -alkyl, C ₅-C₆ -cycloalkyl and phenyl;

a is selected from a single bond, O, C = O, S, SO ₂、CH₂、CH-Ar、CAr₂、CH(CH₃)、C(CH₃)₂ and a group of formula (a')

Wherein the method comprises the steps of

Q represents a single bond, O, NH, c= O, CH ₂ or ch=ch;

R ^7a、R^7b is independently selected from hydrogen, fluorine, CN, R, OR, CH _kR_3-k、NR₂, C (O) R, and C (O) NH ₂, wherein R is as defined herein, and k is 0,1,2, or 3; and

* Represents a point of attachment to a benzene ring;

Ar is selected from the group consisting of a monocyclic or polycyclic aryl group having from 6 to 26 carbon atoms as ring members and a monocyclic or polycyclic heteroaryl group having from 5 to 26 total atoms as ring members, wherein 1,2,3 or 4 of the ring member atoms of the heteroaryl group are selected from nitrogen, sulfur and oxygen and the remaining atoms of the ring member atoms of the heteroaryl group are carbon atoms, wherein Ar is unsubstituted or substituted with 1,2 or 3R ^ab groups selected from halogen, phenyl and C ₁-C₄ -alkyl;

R ^z is a single bond, alk ¹、O-Alk²-、O-Alk²-[O-Alk²-]_p -or O-Alk ³ -C (O) -, wherein O is bound to A ¹, and wherein

P is an integer of 1 to 10;

Alk ¹ is C ₁-C₄ -alkanediyl;

Alk ² is C ₂-C₄ -alkanediyl; and

Alk ³ is C ₁-C₄ -alkanediyl.

The invention also relates to an optical device made of a thermoplastic resin as defined above, in particular of a polyester and in particular of a polycarbonate.

Detailed description of the invention:

If X is a single bond, the compounds of formula (I) may have axial chirality, depending on the type and position of the substituents-O-Z ¹、-O-Z²、R¹、R²、R³ and R ⁴, since rotation along the bond between the two phenylene moieties may be limited. Thus, in this case, the compounds of formula (I) may exist in the form of their (S) -enantiomer and their (R) -enantiomer. Thus, the compounds of formula (I) may be present as racemic mixtures or as non-racemic mixtures or in the form of their pure (S) -and (R) -enantiomers, respectively. The present invention relates to racemic and non-racemic mixtures of enantiomers of compounds of formula (I) wherein X is a single bond, and also to their pure (S) -and (R) -enantiomers, provided that these enantiomers are present.

For the purposes of the present invention, the term "C ₁-C₄ -alkanediyl" is also referred to interchangeably as "alkylene having 1,2, 3 or 4 carbon atoms" and refers to divalent saturated aliphatic hydrocarbon radicals having 1,2, 3 or 4 carbon atoms. Examples of C ₂-C₄ -alkanediyl are in particular methylene (CH ₂), linear alkanediyl, such as 1, 2-ethanediyl (CH ₂CH₂), 1, 3-propanediyl (CH ₂CH₂CH₂) and 1, 4-butanediyl (CH ₂CH₂CH₂CH₂), but can also be branched alkanediyl, such as 1-methyl-1, 2-ethanediyl, 1-methyl-1, 2-propanediyl, 2-methyl-1, 3-propanediyl and 1, 3-butanediyl.

For the purposes of the present invention, the term "monocyclic aryl" refers to monovalent aromatic monocyclic groups, such as, in particular, phenyl.

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 remainder of the molecule by a single covalent bond, wherein the ring member atoms are part of a conjugated pi-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 heterocyclic members, wherein the remaining ring atoms are carbon atoms. Examples include furyl (furyl) (=furyl (furanyl)), pyrrolyl (=1H-pyrrolyl), thienyl (thienyl) (=phenylthio (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, pyridinyl (pyridyl) (=pyridinyl (pyridinyl)), pyrazinyl, pyridazinyl, pyrimidinyl, and triazinyl.

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

(I) Aromatic polycyclic hydrocarbons, i.e., fully unsaturated polycyclic hydrocarbon groups in which each carbon atom is part of a conjugated pi-electron system,

(Ii) Polycyclic hydrocarbons with at least 1 benzene ring fused to a saturated or unsaturated 4 to 10 membered monocyclic or bicyclic hydrocarbon ring,

(Iii) Polycyclic hydrocarbons with at least 2 benzene rings linked to each other by covalent bonds or fused directly to each other and/or fused to a saturated or unsaturated 4 to 10 membered monocyclic or bicyclic hydrocarbon ring.

A monocyclic or polycyclic aryl group has 6 to 26, typically 6 to 24, carbon atoms, for example 6, 9, 10, 12, 13, 14, 16, 17, 18, 19, 20, 22 or 24 carbon atoms as ring atoms, especially 6 to 20 carbon atoms, especially 6, 10, 12, 13, 14, 16, 17 or 18 carbon atoms. Polycyclic aryl groups generally have from 10 to 26 carbon atoms, in particular from 10 to 20 carbon atoms, in particular from 10, 12, 13, 14, 16, 17 or 18 carbon atoms, as ring atoms.

In this context, polycyclic aryl groups with 2,3 or 4 benzene rings linked to each other by a single bond include, for example, biphenyl and terphenyl (terphenylyl). Polycyclic aryl groups having 2,3 or 4 benzene rings directly fused to each other include, for example, naphthyl, anthryl, phenanthryl, pyrenyl, triphenylenyl (TRIPHENYLENYL),A group and a benzo [ c ] phenanthryl group. Polycyclic aryl groups with 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, biphenylene (biphenylenyl), tetraphenylene (TETRAPHENYLENYL), acenaphthylenyl (ACENAPHTHENYL) (1, 2-acenaphthylenyl), acenaphthylenyl (ACENAPHTHYLENYL), 9, 10-dihydro-anthracen-1-yl, 1,2,3, 4-tetrahydrophenanthryl, 5,6,7, 8-tetrahydrophenanthryl, cyclopenta [ fg ] acenaphthylenyl, phenalenyl (fluoranthenyl), benzo [ k ] fluoranthenyl, perylenyl, 9, 10-dihydro-9, 10[1',2' ] -benzoanthryl, dibenzo [ a, e ] [8] cycloalkenyl, 9 '-spirobi [ 9H-fluorenyl ] and spiro [ 1H-cyclobutene [ de ] naphthalene-1, 9' - [9H ] fluorenyl.

Monocyclic or polycyclic aryl groups include, by way of example, phenyl, naphthyl, 9H-fluorenyl, phenanthryl, anthracenyl, pyrenyl,Phenyl, benzo [ c ] phenanthryl, acenaphthylenyl, 2, 3-dihydro-1H-indenyl, 5,6,7, 8-tetrahydronaphthyl, cyclopent [ fg ] acenaphthylenyl, 2, 3-dihydrophenalenyl, 9, 10-dihydroanthracen-1-yl, 1,2,3, 4-tetrahydrophenanthrenyl, 5,6,7, 8-tetrahydrophenanthrenyl, fluoranthenyl, benzo [ k ] fluoranthenyl, biphenylene, triphenylene, tetraphenylene, 1, 2-dihydroacenaphthyl, dibenzo [ a, e ] [8] cycloalkenyl, perylene, biphenyl, terphenyl, naphthylphenyl (NAPHTHYLENPHENYL), phenanthrylphenyl, anthrylphenyl, pyrenylphenyl, 9H-fluorenylphenyl, di (naphthylene) phenyl, naphthylene biphenyl, tri (phenyl) phenyl, tetra (phenyl) phenyl, pentaphenyl (phenyl), phenyl naphthyl, binaphthyl, phenanthrenyl, anthracenyl, naphtalenaphthalenyl, biphenyl [ a, 9' -spirogyrene [9, 9' -biphenyl ] [9, 9' -4-spirogyrene, 9-1, 9' -spirogyrene [1, 9-4-spirogyrene, 9-4-d-4-biphenylenyl, 9' -biphenylenyl, 9-4-biphenylenyl.

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

(I) Polycyclic heteroaromatics carry a heteroaromatic monocyclic ring as defined above and at least one other aromatic ring, for example 1, 2, 3, 4 or 5, selected from phenyl and heteroaromatic monocyclic rings as defined above, wherein the aromatic rings of the polycyclic heteroaromatics 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

(Ii) Polycyclic heteroaromatics carry at least one saturated or partially or fully unsaturated 5-, 6-, 7-or 8-membered heterocyclic ring with 1,2 or 3 heteroatoms selected from oxygen, sulphur 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-dioxazine, oxaheptin, thietane, dioxin, dithiin, dioxaheptin, dioxacine (dioxocine), dithiocine (dithiocine), and at least one aromatic ring, for example 1,2, 3, 4 or 5, selected from phenyl and heteroaromatic monocyclic rings as defined above, wherein at least one aromatic ring is directly fused to a saturated or partially unsaturated 5-to 8-membered heterocyclic ring, and wherein the aromatic rings of the polycyclic heteroaromatics 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 bicyclic or monocyclic hydrocarbon.

Monocyclic or polycyclic heteroaryl groups have 5 to 26, typically 5 to 24, especially 5 to 20 ring atoms, which include 1,2,3 or4 atoms selected from nitrogen, sulfur and oxygen atoms, with the remaining atoms of the ring atoms being carbon atoms. Polycyclic heteroaryl groups typically have 9 to 26, typically 9 to 24, especially 9 to 20 ring atoms, which include 1,2,3 or4 atoms selected from nitrogen, sulfur and oxygen atoms, with the remaining atoms of the ring atoms being carbon atoms.

Examples of polycyclic heteroaryl groups include, but are not limited to, benzofuranyl, benzothienyl, dibenzofuranyl (=dibenzo [ b, d ] furanyl), dibenzothiophenyl (=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, oxaanthracenyl (oxanthrenyl), thianthrenyl (THIANTHRENYL), indolyl (=1H-indolyl), isoindolyl (=2H-isoindolyl), carbazolyl, indolizinyl (indolizinyl), 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, naphthyridinyl pyrrolyl, bipyridyl (dipyridyl), phenylpyridyl, naphthyridinyl, pyrido [4,3-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-chromene, 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 ' ] bisfuranyl, benzo [1,2-b ] bisfuranyl, naphthofuranyl, benzo [ b ] naphtho [1,2-d ] furanyl, benzo [ b ] naphtho [2,3-d ] furanyl, benzo [ b ] naphtho [2,1-d ] furanyl, tribenzo [ b, d, f ] oxaheptyl, dibenzo [ b, d ] thienyl, naphtho [1,2-b ] thienyl, naphtho [2,3-b ] thienyl, naphtho [2,1-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] benzothiophene [2, 3-c ] [ b, 4-thiobenzo [ b ] [2, 1-c ] [ 4-b ] thienyl, 4-b-thiobenzo [1,2, 3-c ] [2,3-d ] thienyl, benzo [ b ] [2, 3-c ] [2, 3-thienyl, 3-d ] thienyl, benzo [ b ] [2, 3-c ] thienyl, 5H- [1] benzothiophene, 5-b ] [2, 3-c ] thienyl, 4-b ] thia, 4-b-c, 4-c ] thienyl, 4-b-thiobenzo [2, 4-b ] thienyl, 4-b-c ] [2, 5H ] thia [2,3-d ] thienyl, 5H- [1, 3-d ] thienyl Dibenzo [ a, H ] thianthrenyl, dibenzo [ a, i ] thianthrenyl, dibenzo [ a, j ] thianthrenyl, dibenzo [ b, i ] thianthrenyl, 2H-naphtho [1,8-b, c ] thienyl, 5H-phenanthro [4,5-b, c, d ] thiopyranyl, 10, 11-dihydrodibenzo [ b, f ] thiazepinyl, 6, 7-dihydrodibenzo [ b, d ] thiazepinyl, dibenzo [ b, f ] thiazepinyl, dibenzo [ b, d ] thiazepinyl, 6H-dibenzo [ d, f ] [1,3] dithiepinyl, tribenzo [ b, d, f ] thiazepinyl, benzothieno [3,4-c, d ] thieno [2,3,4-j, k ] [2] benzothizepinyl, dinaphto [1, 8-bc; 1',8' -f, g ] [1,5] dithiooctyl (dithiocinyl), furo [3,2-g ] quinolinyl, furo [2,3-g ] quinoxalinyl, benzo [ g ] chromene, thieno [3,2-f ] [1] benzothienyl, thieno [2,3-f ] [1] benzothienyl, thieno [3,2-g ] quinolinyl, thieno [2,3-g ] quinoxalinyl, benzo [ g ] thiochromenyl, pyrrolo [3,2,1-H, i ] indolyl, benzo [ g ] quinoxalinyl, benzo [ f ] quinoxalinyl, and benzo [ H ] isoquinolinyl.

For the purposes of the present invention, the terms "phenylene", "naphthylene" and "biphenylene" as are conventional in the art refer to the diradicals of benzene, naphthalene and biphenyl, respectively. Thus, the terms "phenylene", "naphthylene" and "biphenylene" are used synonymously herein with the terms phenyldiyl, naphthyldiyl and biphenyldiyl, respectively.

In the present invention, "structural unit" means a structural element repeatedly existing in a polymer main chain of a thermoplastic resin. Thus, the terms "structural unit" and "repeat unit" are used synonymously.

For the purposes of the present invention, the term "optical device" refers to a device that is transparent to visible light and that manipulates a light beam, in particular by refraction. Optical devices include, but are not limited to, prisms, lenses, optical films, and combinations thereof, particularly lenses for cameras and lenses for spectacles.

The following description of the preferred embodiments of the variables (substituents) of the compounds of formula (I) and of the structural units of formula (II) is valid both individually and preferably in combination with one another.

The description below of the preferred embodiments of the variables, relating to the compounds of the formula (I) and the structural units of the formula (II) and, where applicable, to the use according to the invention, is valid both individually and preferably in combination with one another.

If R ³ and R ⁴ in formula (I) are both hydrogen, then the R ¹ and R ² groups are preferably selected from polycyclic aryl groups having from 10 to 26 carbon atoms as ring atoms and polycyclic heteroaryl groups having a total of from 9 to 26 atoms as ring member atoms, wherein 1, 2, 3 or 4 of the ring member atoms of the polycyclic heteroaryl groups are selected from nitrogen, sulfur and oxygen, and the remaining atoms of these ring member atoms of the heteroaryl groups are carbon atoms, wherein the polycyclic aryl groups and the polycyclic heteroaryl groups are unsubstituted or carry 1, 2, 3 or 4R ^Ar groups.

In formula (I) and also in formula (II), variables X, R ¹、R²、R³、R⁴、Z¹ and Z ², alone or preferably in any combination, preferably have the following meanings:

Preferably those variables Z ¹ and Z ² in formula (I) are independently selected from hydrogen, -Alk-OH, -CH ₂-Ar²-CH₂-OH、-Alk'-C(O)OR^x and-CH ₂-Ar²-C(O)OR^x, and correspondingly preferably those variables Z ^1a and Z ^2a in formula (II) are independently selected from-Alk-O-, -CH ₂-Ar²-CH₂ -O-, -Alk '-C (O) O-and-CH ₂-Ar² -C (O) O-, wherein Alk, -Alk', ar ² and R ^x have the meanings defined herein, especially preferred meanings.

In a preferred embodiment of group (1), the variables Z ¹ and Z ² in formula (I) are independently selected from the group consisting of-Alk-OH and-CH ₂-Ar²-CH₂ -OH and, correspondingly, the variables Z ^1a and Z ^2a in formula (II) are independently selected from the group consisting of-Alk-O-and-CH 38362-O-, wherein Alk is preferably a linear C ₂-C₄ -alkanediyl group, for example 1, 2-ethanediyl (CH ₂-CH₂), 1, 3-propanediyl or 1, 4-butanediyl, and in particular 1, 2-ethanediyl, and Ar ² is preferably selected from the group consisting of 1, 4-phenylene, 1, 3-phenylene, 2, 6-naphthylene, 1, 4-naphthylene, 1, 5-naphthylene and 4,4' -biphenylene. It is also preferred in this context that the variables Z ¹ and Z ² in formula (I) or the variables Z ^1a and Z ^2a in formula (II) are identical to one another.

Thus, in a particularly preferred embodiment of subgroup (1.1), the variables Z ¹ and Z ² in formula (I) are selected from 2-hydroxyethyl (i.e. 2- (HO) -ethyl), hydroxymethyl-phenyl-methyl (i.e. HO-methyl-phenyl-methyl), hydroxymethyl-naphthyl-methyl and hydroxymethyl-biphenyl-methyl, in particular from 2-hydroxyethyl, 4- (hydroxymethyl) phenyl-methyl, (3- (hydroxymethyl) phenyl) methyl, (4- (hydroxymethyl) -1-naphthyl) methyl, (5- (hydroxymethyl) -1-naphthyl) methyl, (6- (hydroxymethyl) -2-naphthyl) methyl and 4'- (hydroxymethyl) -1,1' -biphenyl-4-methyl, and in particular from 2-hydroxyethyl, 4- (hydroxymethyl) phenyl) methyl and (3- (hydroxymethyl) phenyl) methyl. Accordingly, in this particularly preferred embodiment of group (1.1), the variables Z ^1a and Z ^2a in formula (II) are selected from 2 (-O) -ethyl, -O-methyl-phenyl-methyl and-O-methyl-naphthyl-methyl, in particular from 2 (-O) -ethyl, (4 (-O-methyl) phenyl) methyl, (3 (-O-methyl) phenyl) methyl, (4 (-O-methyl) -1-naphthyl) methyl, (5 (-O-methyl) -1-naphthyl) methyl, (6 (-O-methyl) -2-naphthyl) methyl and 4 '(-O-methyl) -1,1' -biphenyl-4-methyl, and in particular from 2 (-O) -ethyl, (4 (-O-methyl) phenyl) methyl and (3 (-O-methyl) phenyl) methyl, (4 (-O-methyl) -1-naphthyl) methyl).

In a specific subgroup (1') of embodiments, the variables Z ¹ and Z ² in formula (I) have the same meaning, and likewise the variables Z ^1a and Z ^2a in formula (II) have the same meaning, selected from the meanings defined in the embodiments of groups (1) and (1.1).

In another set of embodiments of (2), variables Z ¹ and Z ² in formulas (I) and (II) are both hydrogen and, correspondingly, variables Z ^1a and Z ^2a in formula (II) are both single bonds.

In a preferred embodiment of group (3), the variables Z ¹ and Z ² in formula (I) are independently selected from the group consisting of-Alk ' -C (O) OR ^x and-CH ₂-Ar²-C(O)OR^x and, correspondingly, the variables Z ^1a and Z ^2a in formula (II) are independently selected from the group consisting of-Alk ' -C (O) O-and-CH ₂-Ar² -C (O) O-, wherein Alk ' is preferably a linear C ₁-C₄ -alkanediyl group, for example methylene OR 1, 2-ethanediyl (CH ₂-CH₂), and in particular methylene, ar ² is preferably selected from the group consisting of 1, 4-phenylene, 1, 3-phenylene, 2, 6-naphthylene, 1, 5-naphthylene and 1, 4-naphthylene, and R ^x is preferably hydrogen OR C ₁-C₄ -alkyl, and in particular methyl. It is also preferred in this context that the variables Z ¹ and Z ² or the variables Z ^1a and Z ^2a are identical to one another.

Thus, in a particularly preferred subgroup (3.1) of embodiments, the variables Z ¹ and Z ² in formula (I) are selected from methoxycarbonyl-methyl (i.e. CH ₃ O-C (O) -methyl), methoxycarbonyl-phenyl-methyl (i.e. CH ₃ O-C (O) -phenyl-methyl) and methoxycarbonyl-naphthyl-methyl, in particular from methoxycarbonyl-methyl, (4- (methoxycarbonyl) phenyl) methyl, (3- (methoxycarbonyl) phenyl) methyl, (4- (methoxycarbonyl) -1-naphthyl) methyl, (5- (methoxycarbonyl) -1-naphthyl) methyl and (6- (methoxycarbonyl) -2-naphthyl) methyl, and in particular from methoxycarbonyl-methyl, (4- (methoxycarbonyl) phenyl) methyl and (3- (methoxycarbonyl) phenyl) methyl. Accordingly, in this particularly preferred embodiment of group (3.1), the variables Z ^1a and Z ^2a in formula (II) are selected from the group consisting of-O-C (O) -methyl-O-C (O) -phenyl-methyl and-O-C (O) -naphthyl-methyl, in particular selected from the group consisting of-O-C (O) -methyl, (4 (-O-C (O) -phenyl) methyl, (3 (-O-C (O) -phenyl) methyl) (4- (-O-C (O) -) -1-naphthyl) methyl, (5- (-O-C (O) -) -1-naphthyl) methyl and (6- (-O-C (O) -) -2-naphthyl) methyl, (4- (-O-C (O) -) -1-naphthyl) methyl (5- (-O-C (O) -) -1-naphthyl) methyl and (6- (-O-C (O) -) -2-naphthyl) methyl.

In an embodiment of subgroup (3') of features, the variables Z ¹ and Z ² in formula (I) have the same meaning, and likewise the variables Z ^1a and Z ^2a in formula (II) have the same meaning, selected from the meanings defined in the embodiments of groups (3) and (3.1).

In a preferred embodiment of group (4), which is a combination of the embodiments of groups (1.1), (2) and (3.1), the variables Z ¹ and Z ² in formula (I) are selected from the group consisting of hydrogen, 2-hydroxyethyl, methoxycarbonyl-methyl, hydroxymethyl-phenyl-methyl, hydroxymethyl-naphthyl-methyl, hydroxymethyl-biphenyl-methyl, methoxycarbonyl-phenyl-methyl and methoxycarbonyl-naphthyl-methyl, in particular from the group consisting of hydrogen, 2-hydroxyethyl, methoxycarbonyl-methyl, (4- (hydroxymethyl) phenyl) methyl, (3- (hydroxymethyl) phenyl) methyl, (4- (hydroxymethyl) -1-naphthyl) methyl, (5- (hydroxymethyl) -1-naphthyl) methyl, (6- (hydroxymethyl) -2-naphthyl) methyl, 4'- (hydroxymethyl) -1,1' -biphenyl-4-methyl, (4- (methoxycarbonyl) phenyl) methyl, (3- (methoxycarbonyl) phenyl) methyl, (4- (methoxycarbonyl) -1-naphthyl) methyl, (5- (methoxycarbonyl) -1-naphthyl) methyl and (6- (methoxycarbonyl) -2-naphthyl) methyl, in particular from the group consisting of hydrogen 2-hydroxyethyl, methoxycarbonyl-methyl, (4- (hydroxymethyl) phenyl) methyl, (3- (hydroxymethyl) phenyl) methyl, (4- (methoxycarbonyl) phenyl) methyl and (3- (methoxycarbonyl) phenyl) methyl, and in particular are selected from hydrogen, 2-hydroxyethyl, (4- (hydroxymethyl) phenyl) methyl and (3- (hydroxymethyl) phenyl) methyl. Accordingly, in this preferred embodiment of group (4), the variables Z ^1a and Z ^2a in formula (II) are selected from the group consisting of single bond, 2 (-O) -ethyl, -O-C (O) -methyl, -O-methyl-phenyl-methyl, -O-methyl-naphthyl-methyl, -O-C (O) -phenyl-methyl and-O-C (O) -naphthyl-methyl, in particular from the group consisting of single bond, 2 (-O) -ethyl, -O-C (O) -methyl, (4 (-O-methyl) phenyl) methyl, (3 (-O-methyl) phenyl) methyl, (4 (-O-methyl) -1-naphthyl) methyl, (5 (-O-methyl) -1-naphthyl) methyl, (6 (-O-methyl) -2-naphthyl) methyl, (4 (-O-C (O) -phenyl) methyl, (3- (-O-C (O) -phenyl) methyl, (4- (-O-C (O) -) -1-naphthyl) methyl), (5- (-O-C (O) -) -1-naphthyl) methyl and (6- (methoxycarbonyl) -2-naphthyl) methyl, especially selected from single bond, 2 (-O) -ethyl, -O-C (O) -methyl, (4 (-O-methyl) phenyl) methyl, (3 (-O-methyl) phenyl) methyl, 4 (-O-C (O) -phenyl) methyl and (3- (-O-C (O) -phenyl) methyl, and especially selected from single bond, 2 (-O) -ethyl, (4 (-O-methyl) phenyl) methyl and (3 (-O-methyl) phenyl) methyl.

In a specific subgroup (4') of embodiments, the variables Z ¹ and Z ² in formula (I) have the same meaning, and likewise the variables Z ^1a and Z ^2a in formula (II) have the same meaning, selected from the meanings defined in the embodiments of group (4).

The variable X is preferably selected from the group consisting of single bond, O, N-methyl, N-ethyl, N-N-propyl, N-isopropyl, N-sec-butyl, N-isobutyl, N-tert-butyl 、N-Ar¹、CH₂、C(CH₃)₂、CH(CH₃)、C(CH₃)(CH₂CH₃)、S、SO and SO ₂, wherein Ar ¹ in N-Ar ¹ is as defined herein, and wherein Ar ¹ is selected from the group consisting of phenyl, naphthyl, phenanthryl, biphenyl, fluorenyl, pyrenyl,A group, benzo [ b ] furyl, dibenzo [ b, d ] furyl, naphtho [1,2-b ] furyl, naphtho [2,3-b ] furyl, naphtho [2,1-b ] furyl, oxaanthryl, benzo [ b ] thienyl, dibenzo [ b, d ] thienyl, naphtho [1,2-b ] thienyl, naphtho [2,3-b ] thienyl, naphtho [2,1-b ] thienyl and thianthrenyl, and is selected from the group consisting of phenyl, naphthyl, phenanthryl, biphenyl, fluorenyl, benzo [ b ] furyl, dibenzo [ b, d ] furyl, benzo [ b ] thienyl and dibenzo [ b, d ] thienyl, among others.

In particular, the variable X is selected from the group consisting of single bond, O, N-methyl, N-ethyl, N-N-propyl, N-isopropyl, N-tert-butyl 、N-Ar¹、CH₂、C(CH₃)₂、CH(CH₃)、C(CH₃)(CH₂CH₃)、S and SO ₂, wherein Ar ¹ is selected from the group consisting of phenyl, naphthyl, such as naphthalen-1-yl or naphthalen-2-yl, phenanthryl, such as phenanthren-1-yl, phenanthren-2-yl, phenanthren-3-yl, phenanthren-4-yl or phenanthren-9-yl, biphenyl, such as biphenyl-2-yl, biphenyl-3-yl or biphenyl-4-yl, fluorenyl, such as fluoren-1-yl, fluoren-2-yl, fluoren-3-yl or fluoren-4-yl, benzo [ b ] furanyl, such as benzo [ b ] furan-2-yl, benzo [ b ] furan-3-yl, benzo [ b ] furan-4-yl, benzo [ b ] furan-6-yl or benzo [ b ] furan-7-yl, dibenzo [ b, such as dibenzo [ b ] furan-2-yl, dibenzo [ b ] furan-3-yl or benzo [ b ] furan-4-yl, such as benzo [ b ] furan-2-yl, benzo [ b ] furan-3-yl, such as benzo [ b ] furan-3-yl, such as benzo [ b ] furan-2-yl Benzo [ b ] thiophen-6-yl or benzo [ b ] thiophen-7-yl, and dibenzo [ b, d ] thiophenyl, e.g., dibenzo [ b, d ] thiophen-1-yl, dibenzo [ b, d ] thiophen-2-yl, dibenzo [ b, d ] thiophen-3-yl or dibenzo [ b, d ] thiophen-4-yl.

In a preferred embodiment of group (5), the variable X is selected from the group consisting of single bond, O, N-phenyl, N-naphthyl, N-phenanthryl, CH ₂、C(CH₃)₂、CH(CH₃), S, S (O), and SO ₂, especially from the group consisting of single bond, O, N-phenyl, N-naphthalen-1-yl, N-naphthalen-2-yl, N-phenanthren-9-yl, CH ₂、C(CH₃)₂, S, S (O) and SO ₂, especially from the group consisting of single bond, O, CH ₂、C(CH₃)₂, S, S (O) and SO ₂, and especially from the group consisting of single bond, C (CH ₃)₂, S and SO ₂.

In an embodiment of a particular subgroup (5 '), the variable X is CH ₂、C(CH₃)₂ or CH (CH ₃), and in particular C (CH ₃)₂. In an embodiment of another particular subgroup (5 '), the variable X is S or SO ₂. In an embodiment of yet another particular subgroup (5 '), the variable X is a single bond.

Preferably, the variables R ¹ and R ² are independently selected from the group consisting of monocyclic or polycyclic aryl groups having 6 to 18 carbon atoms as ring atoms and polycyclic heteroaryl groups having a total of 9 to 26 atoms, especially 9 to 18 atoms, as ring members, wherein 1 or 2 of the ring member atoms of the heteroaryl groups are oxygen or sulfur atoms and the remaining atoms of the ring member atoms of the heteroaryl groups are carbon atoms, wherein the monocyclic or polycyclic aryl groups and the polycyclic heteroaryl groups are unsubstituted or carry 1 or 2R ^Ar groups, wherein R ^Ar has one of the meanings defined herein, especially as one of the meanings mentioned preferably (group 6 embodiment). More preferably, at least one of R ¹ and R ², in particular R ¹ and R ², is selected from the group consisting of polycyclic aryl groups having from 10 to 18 carbon atoms as ring member atoms and polycyclic heteroaryl groups having a total of from 9 to 18 ring member atoms.

According to a more preferred embodiment of group (6.1), R ¹ and R ² are independently selected from phenyl, naphthyl, e.g. naphthalen-1-yl or naphthalen-2-yl, 1, 2-dihydroacenaphthylyl, e.g. 1, 2-dihydroacenaphthylen-3-yl or 1, 2-dihydroacenaphthylen-5-yl, biphenyl, e.g. biphenyl-4-yl, biphenyl-3-yl or biphenyl-2-yl, fluorenyl, e.g. fluoren-1-yl, fluoren-2-yl, fluoren-3-yl or fluoren-4-yl, 11H-benzo [ a ] fluorenyl, e.g. 11H-benzo [ a ] fluoren-7-yl, 11H-benzo [ b ] fluoren-1-yl, 7H-benzo [ c ] fluoren-5-yl or 7H-benzo [ c ] fluoren-10-yl, e.g. 7H-benzo [ c ] fluoren-5-yl, phenanthren-3-yl, 11H-benzo [ c ] fluoren-7-yl, c-4-yl, e.g. benzo [ c-3-yl, c-4-benzopyrene.g. 4-yl, c-4-yl,Radicals, e.g./>-1-Yl,/>-2-Yl,/>-3-Yl/>-4-Yl/>-5-Yl or/>-6-Yl, picene-yl, e.g. picene-3-yl, triphenylene, e.g. triphenylene-1-yl or triphenylene-2-yl, benzo [ b ] furanyl, e.g. benzo [ b ] furan-2-yl, benzo [ b ] furan-3-yl, benzo [ b ] furan-4-yl, benzo [ b ] furan-5-yl, benzo [ b ] furan-6-yl or benzo [ b ] furan-7-yl, dibenzo [ b, d ] furanyl, e.g. dibenzo [ b, d ] furan-1-yl, dibenzo [ b, d ] furan-2-yl, dibenzo [ b, d ] furan-3-yl or dibenzo [ b, d ] furan-4-yl, naphtho [1,2-b ] furyl, for example naphtho [1,2-b ] furan-5-yl, naphtho [2,3-b ] furyl, for example naphtho [2,3-b ] furan-3-yl, naphtho [2,3-b ] furan-4-yl or naphtho [2,3-b ] furan-9-yl, naphtho [2,1-b ] furyl, for example naphtho [2,1-b ] furan-2-yl or naphtho [2,1-b ] furan-5-yl, benzo [ b ] naphtho [1,2-d ] furyl, for example benzo [ b ] naphtho [1,2-d ] furan-1-yl or benzo [ b ] naphtho [1,2-d ] furan-4-yl, benzo [ b ] naphtho [2,3-d ] furyl, such as benzo [ b ] naphtho [2,3-d ] furan-2-yl, benzo [ b ] naphtho [2,3-d ] furan-4-yl or benzo [ b ] naphtho [2,3-d ] furan-6-yl, benzo [ b ] naphtho [2,1-d ] furanyl, such as benzo [ b ] naphtho [2,1-d ] furan-6-yl or benzo [ b ] naphtho [2,1-d ] furan-7-yl, benzo [1,2-b:4,3-b ' ] bifuranyl, for example benzo [1,2-b:4,3-b ' ] bifuran-7-yl, benzo [1,2-b:6,5-b ' ] bifuranyl, for example benzo [1,2-b:6,5-b ' ] bifuran-4-yl, benzo [1,2-b:5,4-b ' ] bifuran-yl, for example benzo [1,2-b:5,4-b ' ] bifuran-4-yl or benzo [1,2-b:5,4-b ' ] bifuran-8-yl, benzo [1,2-b:4,5-b ' ] bifuran-yl, for example benzo [1,2-b:4,5-b ' ] bifuran-4-yl, tribenzo [ b, d, f ] oxaheptan-6-yl or tribenzo [ b, d, f ] oxaheptan-8-yl, 2H-naphtho [1,8-d, e ] [1,3] dioxanyl, for example 2H-naphtho [1,8, e ] [1,3] dioxa-2-e, 1-3 ] dioxa [1, 2-e ] [1, 3-e ],2-2-e ],3-naphthyridine-yl, dinaphtho [2,3-b:2',3' -d ] furyl, such as dinaphtho [2,3-b ] 2',3' -d ] furan-3-yl or dinaphtho [2,3-b ] furan-5-yl, xanthenyl, such as xanthen-1-yl or xanthen-2-yl, benzo [ a ] xanthenyl, such as benzo [ a ] xanthen-1-yl, benzo [ a ] xanthen-2-yl, benzo [ a ] xanthen-6-yl or benzo [ a ] xanthen-7-yl, benzo [ b ] xanthen-yl, such as benzo [ b ] xanthen-1-yl, benzo [ b ] xanthen-2-yl or benzo [ b ] xanthen-6-yl, benzo [ b ] thiophenyl, such as benzo [ b ] thiophen-2-yl, benzo [ b ] thiophen-3-yl, benzo [ b ] thiophen-4-yl, benzo [ b ] thiophen-5-yl, benzo [ b ] thiophen-2-yl, benzo [ b ] thiophen-6-yl, such as benzo [ b ] xanthen-2-yl, benzo [ b ] thiophen-6-yl, benzo [ b ] xanthen-6-yl, such as benzo [ b ] thiophen-2-yl, benzo [ b ] xanthen-6-yl, benzo [ b ] thiophen-6-yl, such as benzo [ b ] thiophen-2-yl, benzo [ b ] thiophen-2-yl, naphtho [2,3-b ] thiophen-4-yl or naphtho [2,3-b ] thiophen-9-yl, naphtho [2,1-b ] thiophenyl, for example naphtho [2,1-b ] thiophen-2-yl or naphtho [2,1-b ] thiophen-5-yl, benzo [ b ] naphtho [1,2-d ] thiophenyl, for example benzo [ b ] naphtho [1,2-d ] thiophen-1-yl or benzo [ b ] naphtho [1,2-d ] thiophen-4-yl, benzo [ b ] naphtho [2,3-d ] thiophenyl, for example benzo [ b ] naphtho [2,3-d ] thiophen-2-yl, benzo [ b ] thiophen [2,3-d ] thiophen-4-yl or benzo [ b ] naphtho [2,3-d ] thiophen-6-yl, benzo [ b ] naphtho [2,1-d ] thiophenyl, for example benzo [ b ] naphtho [1,2-d ] thiophen-yl, for example benzo [ b ] benzo [1,2-d ] thiophen-1-yl or benzo [ b ] benzo [2,3-d ] thiophen-6-yl, for example, benzo [ b ] benzo [2,3-d ] thiophen-4-yl, for example, 1, 3-b ] binapht-4-yl, such as benzo [1,2-b ] dithiophene-4-yl, 9H-thioxanthyl, such as 9H-thioxanth-4-yl, 6H-dibenzo [ b, d ] thiopyranyl, such as 6H-dibenzo [ b, d ] thiopyran-2-yl or 6H-dibenzo [ b, d ] thiopyran-4-yl, 1, 4-benzodithiino, such as 1, 4-benzodithiin-2-yl, 1, 4-benzodithiin-5-yl or 1, 4-benzodithiin-6-yl, naphtho [1,2-b ] [1,4] dithiin-2-yl or naphtho [1,2-b ] [1,4] dithiin-6-yl, naphtho [2,3-b ] [1,4] dithiin-2-yl, such as naphtho [2, 2-b ] [1,4] dithiin-6-yl, such as 1, 4-benzodithiin-5-yl or 1, 4-benzodithiin-6-yl, such as naphtho [1,2-b ] [1,4] dithiin-2-yl, such as naphthiin-6-yl, such as naphtho [1,2-b ] [1,4] dithiin-yl, such as naphthiin-6-yl, h ] thianthrenyl, for example dibenzo [ a, H ] thianthrene-6-yl, dibenzo [ a, i ] thianthrene-yl, for example dibenzo [ a, i ] thianthrene-6-yl, dibenzo [ a, j ] thianthrene-yl, for example dibenzo [ a, j ] thianthrene-6-yl, dibenzo [ b, i ] thianthrene-yl, for example dibenzo [ b, i ] thianthrene-5-yl, 2H-naphtho [1,8-b, c ] thienyl, for example 2H-naphtho [1,8-b, c ] thiophen-6-yl or 2H-naphtho [1,8-b, c ] thiophen-8-yl, dibenzo [ b, d ] thiaheptyl, for example dibenzo [ b, d ] thiazepin-2-yl, such as dibenzo [ b, f ] thiepin-2-yl or dibenzo [ b, f ] thiepin-4-yl, 5H-phenanthro [4,5-b, c, d ] thiopyranyl, such as 5H-phenanthro [4,5-b, c, d ] thiopyran-1-yl, 5H-phenanthro [4,5-b, c, d ] thiopyran-2-yl, 5H-phenanthro [4,5-b, c, d ] thiopyran-3-yl, 5H-phenanthro [4,5-b, c, d ] thiopyran-7-yl, 5H-phenanthro [4,5-b, c, d ] thiopyran-9-yl or 5H-phenanthro [4,5-b, c, d ] thiopyran-10-yl, tribenzo [ b, d, f ] thiaheptin-yl, such as tribenzo [ b, d, f ] thiopyran-6-yl or tribenzo [ b ], d, f ] thiepin-8-yl, 2, 5-dihydronaphtho [1,8-b, c:4,5-b ', c' ] bithiophene radicals, such as the 2, 5-dihydronaphtho [1,8-b, c:4,5-b ', c' ] bithiophene-3-yl or 2, 5-dihydronaphtho [1,8-b, c:4,5-b ', c' ] bithiophene-7-yl, 2, 6-dihydronaphtho [1,8-b, c:5,4-b ', c' ] bithiophene-yl, e.g. 2, 6-dihydronaphtho [1,8-b, c:5,4-b ', c' ] bithiophene-4-yl, tetrabenzo [ a, c, H, j ] thianthrenyl, e.g. tetrabenzo [ a, c, H, j ] thianthrene-3-yl, benzo [ b ] naphtho [1,8-e, f ] [1,4] dithienyl, e.g. benzo [ b ] naphtho [1,8-e, f ] [1,4] dithien-2-yl, dinaphto [2,3-b:2',3' -d ] thienyl, e.g. dinaphto [2, 3'-d ] thiophen-3-yl or dinaphtho [2, 3' -d ] thiophen-3-yl, e.g. 5-c [1,8-e, f ] [1,4] dithien-yl, 1, 7-b ] thiophenyl, e.g. 1, 7-c, 7-H, c ] thiophenyl, b ] thiophen-9-yl, dibenzo [ d, d '] benzo [1,2-b:4,5-b' ] bithiophene yl, for example dibenzo [ d, d '] benzo [1,2-b:4,5-b' ] bithiophene-4-yl or dibenzo [ d, d '] benzo [1,2-b:4,5-b' ] bithiophene-6-yl, and dibenzo [ d, d '] benzo [1,2-b:5,4-b' ] bithiophene yl, for example dibenzo [ d, d '] benzo [1,2-b:5,4-b' ] bithiophene-4-yl or dibenzo [ d, d '] benzo [1,2-b:5,4-b' ] bithiophene-6-yl, which is unsubstituted or may carry 1 or 2R ^Ar groups.

According to a particularly preferred embodiment of group (6.2), R ¹ and R ² are independently selected from phenyl, naphthyl, for example naphthalen-1-yl or naphthalen-2-yl, 1, 2-acenaphthylene, for example 1, 2-acenaphthylen-3-yl or 1, 2-acenaphthylen-5-yl, biphenyl, for example biphenyl-4-yl, biphenyl-3-yl or biphenyl-2-yl, fluorenyl, for example fluoren-1-yl, fluoren-2-yl, fluoren-3-yl or fluoren-4-yl, phenanthryl, for example phenanthren-1-yl, phenanthren-2-yl, phenanthren-3-yl, phenanthren-4-yl or phenanthren-9-yl, benzo [ c ] phenanthren-1-yl, benzo [ c ] phenanthren-2-yl, benzo [ c ] phenanthren-3-yl, benzo [ c ] phenanthren-4-yl, benzo [ c ] phenanthren-5-yl or benzo [ c ] 6-yl, for example pyrene-1-yl, pyrene-2-yl,Radicals, e.g./>-1-Yl,/>-2-Yl,/>-3-Yl/>-4-Yl/>-5-Yl or/>-6-Yl, triphenylene, e.g. triphenylen-1-yl or triphenylen-2-yl, benzo [ b ] furanyl, e.g. benzo [ b ] furan-2-yl, benzo [ b ] furan-3-yl, benzo [ b ] furan-4-yl, benzo [ b ] furan-5-yl, benzo [ b ] furan-6-yl or benzo [ b ] furan-7-yl, dibenzo [ b, d ] furanyl, e.g. dibenzo [ b, d ] furan-1-yl, dibenzo [ b, d ] furan-2-yl, dibenzo [ b, d ] furan-3-yl or dibenzo [ b, d ] furan-4-yl, naphtho [1,2-b ] furanyl, such as naphtho [1,2-b ] furan-5-yl, naphtho [2,3-b ] furan-yl, such as naphtho [2,3-b ] furan-3-yl, naphtho [2,3-b ] furan-4-yl or naphtho [2,3-b ] furan-9-yl, naphtho [2,1-b ] furan-yl, such as naphtho [2,1-b ] furan-2-yl or naphtho [2,1-b ] furan-5-yl, benzo [ b ] naphtho [1,2-d ] furan-yl, such as benzo [ b ] naphtho [1,2-d ] furan-1-yl or benzo [ b ] naphtho [1,2-d ] furan-4-yl, benzo [ b ] naphtho [2,3-d ] furan-yl, such as benzo [ b ] naphtho [2,3-d ] furan-2-yl, benzo [ b ] naphthalen [2,3-d ] furan-4-yl or benzo [ b ] naphthalen [2,3-d ] furan-6-yl, e.g. benzo [ b ] naphthalen [2,1-d ] furan-6-yl or benzo [ b ] naphthalen [2,1-d ] furan-7-yl, oxaanthracyl, e.g. oxazin-1-yl or oxazin-2-yl, benzo [ a ] oxaanthracyl, e.g. benzo [ a ] oxazin-1-yl, benzo [ a ] oxazin-2-yl, benzo [ a ] oxazin-6-yl or benzo [ a ] oxazin-7-yl, benzo [ b ] oxazinyl, e.g. benzo [ b ] oxazin-1-yl, benzo [ b ] oxazin-2-yl or benzo [ b ] oxazin-6-yl, e.g. benzo [ b ] oxazin-1-yl, benzo [ b ] thiophen-2-yl, benzo [ b ] oxazin-6-yl, benzo [ b ] thiophen-2-yl, benzo [ b ] oxazin-yl, benzo [ b ] oxazin-yl, naphtho [2,3-b ] thiophenyl, for example naphtho [2,3-b ] thiophen-3-yl, naphtho [2,3-b ] thiophen-4-yl or naphtho [2,3-b ] thiophen-9-yl, naphtho [2,1-b ] thiophenyl, for example naphtho [2,1-b ] thiophen-2-yl or naphtho [2,1-b ] thiophen-5-yl, benzo [ b ] naphthalen [1,2-d ] thiophenyl, for example benzo [ b ] naphtho [1,2-d ] thiophen-1-yl or benzo [ b ] naphtho [1,2-d ] thiophen-4-yl, benzo [ b ] naphtho [2,3-d ] thiophen-yl, for example benzo [ b ] naphtho [2,3-d ] thiophen-4-yl or benzo [ b ] naphtho [2,3-d ] thiophen-yl, for example benzo [2,3-d ] thiophen-4-yl, benzo [ b ] benzo [2,3-d ] thiophen-yl, for example, benzo [1,2-d ] thiophen-1-yl, for example, benzo [ b ] benzo [1, 7-d ] thiophen-yl, for example, benzo [1, 7-b ] benzothiaz-yl, for example, benzo [1, 7-b ] thiophen-yl, c ] thienyl, such as 2H-naphtho [1,8-b, c ] thiophen-6-yl or 2H-naphtho [1,8-b, c ] thiophen-8-yl, dibenzo [ b, d ] thiepinyl, such as dibenzo [ b, d ] thiepin-2-yl, dibenzo [ b, f ] thiepinyl, such as dibenzo [ b, f ] thiepin-2-yl or dibenzo [ b, f ] thiepin-4-yl, and tribenzo [ b, d, f ] thiepinyl, such as tribenzo [ b, d, f ] thiepin-6-yl or tribenzo [ b, d, f ] thiepin-8-yl, which is unsubstituted or can carry 1R ^Ar group.

In a particularly preferred embodiment of group (6.3), R ¹ and R ² are independently selected from the group consisting of phenyl, naphthyl, 1, 2-dihydroacenaphthyl, phenanthryl, pyrenyl, triphenylene, benzo [ b ] furanyl, dibenzo [ b, d ] furanyl, benzo [ b ] thiophenyl, dibenzo [ b, d ] thiophenyl and thianthrenyl, especially from the group consisting of phenyl, naphthalen-1-yl, naphthalen-2-yl, 1, 2-dihydroacenaphthyl-5-yl, phenanthren-9-yl, pyren-1-yl, pyren-2-yl, pyren-4-yl, triphenylen-1-yl, triphenylen-2-yl, dibenzo [ b, d ] furan-4-yl, benzo [ b ] thiophen-3-yl, benzo [ b ] thiophen-4-yl, benzo [ b ] thiophen-5-yl, benzo [ b ] thiophen-6-yl, benzo [ b ] thiophen-7-b-2-yl, dibenzo-2-d ] thiophen-yl, and dithienyl. In an embodiment of subgroup (6.3 a) of group (6.3), R ¹ and R ² are independently selected from phenyl, naphthyl, 1, 2-dihydroacenaphthenyl, phenanthryl, triphenylene, pyrenyl, dibenzo [ b, d ] furanyl, benzo [ b ] thienyl, dibenzo [ b, d ] thienyl and thianthrenyl, and in particular from phenyl, naphthyl, phenanthryl, dibenzo [ b, d ] thienyl and thianthrenyl.

In an embodiment of the specific subgroup (6'), the variables R ¹ and R ² have the same meaning, which is selected from the meanings defined herein for R ¹ and R ², especially those mentioned as preferred, and especially from the meanings defined in the embodiments of groups (6), (6.1), (6.2), (6.3) or (6.3 a).

In a preferred embodiment of group (7), the variables R ³ and R ⁴ are different from hydrogen. In other words, the variables R ³ and R ⁴ are selected from the group consisting of monocyclic or polycyclic aryl groups having 6 to 26 carbon atoms as ring member 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 the ring member atoms of the heteroaryl groups are selected from nitrogen, sulfur, and oxygen, and the remaining atoms of the ring member atoms of the heteroaryl groups are carbon atoms, wherein the monocyclic or polycyclic aryl groups and the monocyclic or polycyclic heteroaryl groups are unsubstituted or carry 1, 2, 3, or 4R ^Ar groups. More preferably, at least one of R ³ and R ⁴, in particular R ³ and R ⁴, is each selected from the group consisting of polycyclic aryl groups having from 10 to 18 carbon atoms and polycyclic heteroaryl groups having a total of from 9 to 26 atoms.

Preferably, in embodiments of this group (7), the variables R ³ and R ⁴ are independently selected from the group consisting of monocyclic or polycyclic aryl groups having 6 to 18 carbon atoms as ring members and polycyclic heteroaryl groups having a total of 9 to 26 carbon atoms as ring members, wherein 1 or 2 of these atoms are oxygen or sulfur atoms and the remaining atoms of these atoms are carbon atoms, wherein the monocyclic or polycyclic aryl groups and the polycyclic heteroaryl groups are unsubstituted or carry 1 or 2R ^Ar groups, wherein R ^Ar has one of the meanings defined herein, especially as one of the meanings mentioned preferably (hereinafter embodiment of group (7.1)).

More preferably, in an embodiment of group (7), R ³ and R ⁴ are independently selected from phenyl, naphthyl, e.g. naphthalen-1-yl or naphthalen-2-yl, 1, 2-dihydroacenaphthylyl, e.g. 1, 2-dihydroacenaphthylen-3-yl or 1, 2-dihydroacenaphthylen-5-yl, biphenyl, e.g. biphenyl-4-yl, biphenyl-3-yl or biphenyl-2-yl, fluorenyl, e.g. fluoren-1-yl, fluoren-2-yl, fluoren-3-yl or fluoren-4-yl, 11H-benzo [ a ] fluorenyl, e.g. 11H-benzo [ a ] fluoren-7-yl, 11H-benzo [ b ] fluoren-1-yl, 7H-benzo [ c ] fluorenyl, e.g. 7H-benzo [ c ] fluoren-5-yl or 7H-benzo [ c ] fluoren-10-yl, phenanthryl, e.g. 7H-benzo [ c ] fluoren-3-yl, benzo [ c ] fluoren-7-yl, e.g. 4-c-4-yl, c-benzo [ c ] fluoren-1-yl, c-4-yl,Radicals, e.g./>-1-Yl,/>-2-Yl,/>-3-Yl/>-4-Yl/>-5-Yl or/>-6-Yl, picene-yl, e.g. picene-3-yl, triphenylene, e.g. triphenylene-1-yl or triphenylene-2-yl, benzo [ b ] furanyl, e.g. benzo [ b ] furan-2-yl, benzo [ b ] furan-3-yl, benzo [ b ] furan-4-yl, benzo [ b ] furan-5-yl, benzo [ b ] furan-6-yl or benzo [ b ] furan-7-yl, dibenzo [ b, d ] furanyl, e.g. dibenzo [ b, d ] furan-1-yl, dibenzo [ b, d ] furan-2-yl, dibenzo [ b, d ] furan-3-yl or dibenzo [ b, d ] furan-4-yl, naphtho [1,2-b ] furyl, for example naphtho [1,2-b ] furan-5-yl, naphtho [2,3-b ] furyl, for example naphtho [2,3-b ] furan-3-yl, naphtho [2,3-b ] furan-4-yl or naphtho [2,3-b ] furan-9-yl, naphtho [2,1-b ] furyl, for example naphtho [2,1-b ] furan-2-yl or naphtho [2,1-b ] furan-5-yl, benzo [ b ] naphtho [1,2-d ] furyl, for example benzo [ b ] naphtho [1,2-d ] furan-1-yl or benzo [ b ] naphtho [1,2-d ] furan-4-yl, benzo [ b ] naphtho [2,3-d ] furyl, such as benzo [ b ] naphtho [2,3-d ] furan-2-yl, benzo [ b ] naphtho [2,3-d ] furan-4-yl or benzo [ b ] naphtho [2,3-d ] furan-6-yl, benzo [ b ] naphtho [2,1-d ] furanyl, such as benzo [ b ] naphtho [2,1-d ] furan-6-yl or benzo [ b ] naphtho [2,1-d ] furan-7-yl, benzo [1,2-b:4,3-b ' ] bifuranyl, for example benzo [1,2-b:4,3-b ' ] bifuran-7-yl, benzo [1,2-b:6,5-b ' ] bifuranyl, for example benzo [1,2-b:6,5-b ' ] bifuran-4-yl, benzo [1,2-b:5,4-b ' ] bifuran-yl, for example benzo [1,2-b:5,4-b ' ] bifuran-4-yl or benzo [1,2-b:5,4-b ' ] bifuran-8-yl, benzo [1,2-b:4,5-b ' ] bifuran-yl, for example benzo [1,2-b:4,5-b ' ] bifuran-4-yl, tribenzo [ b, d, f ] oxaheptan-6-yl or tribenzo [ b, d, f ] oxaheptan-8-yl, 2H-naphtho [1,8-d, e ] [1,3] dioxanyl, for example 2H-naphtho [1,8, e ] [1,3] dioxa-2-e, 1-3 ] dioxa [1, 2-e ] [1, 3-e ],2-2-e ],3-naphthyridine-yl, dinaphtho [2,3-b ] furan group, such as dinaphtho [2,3-b ] furan-3-yl or dinaphtho [2,3-b ] furan-5-yl, xanthen group, such as xanthen-1-yl or xanthen-2-yl, benzo [ a ] xanthen group, such as benzo [ a ] xanthen-1-yl, benzo [ a ] xanthen-2-yl, benzo [ a ] xanthen-6-yl or benzo [ a ] xanthen-7-yl, benzo [ b ] xanthen-yl, such as benzo [ b ] xanthen-1-yl, benzo [ b ] xanthen-2-yl or benzo [ b ] xanthen-6-yl, benzo [ b ] thiophenyl, such as benzo [ b ] thiophen-2-yl, benzo [ b ] thiophen-3-yl, benzo [ a ] xanthen-6-yl, benzo [ b ] thiophen-2-yl, benzo [ b ] thiophen-6-yl, benzo [ b ] thiophen-7-yl, such as benzo [ b ] thiophen-2-yl, benzo [ b ] thiophen-6-yl, benzo [ b ] thiophen-1-yl, benzo [ b ] thiophen-7-yl, such as naphtho [2,3-b ] thiophen-3-yl, naphtho [2,3-b ] thiophen-4-yl or naphtho [2,3-b ] thiophen-9-yl, naphtho [2,1-b ] thiophen-yl, such as naphtho [2,1-b ] thiophen-2-yl or naphtho [2,1-b ] thiophen-5-yl, benzo [ b ] naphtho [1,2-d ] thiophen-1-yl or benzo [ b ] naphtho [1,2-d ] thiophen-4-yl, benzo [ b ] naphtho [2,3-d ] thiophen-yl, such as benzo [ b ] naphtho [2,3-d ] thiophen-2-yl, benzo [ b ] naphtho [2,3-d ] thiophen-4-yl or benzo [ b ] naphtho [2,3-d ] thiophen-6-yl, benzo [ b ] naphtho [1,2-d ] thiophen-yl, such as benzo [1,2-d ] thiophen-1-yl or benzo [ b ] binapht-4-yl, such as benzo [2,3-d ] thiophen-2-yl, benzo [ b ] thien-6-yl, benzo [ b ] naphtho [1,2, 3-d ] thiophen-yl, such as benzo [2,3-d ] thiophen-yl, benzo [1,2-b ] dithiophene radicals, for example benzo [1,2-b:4,5-b' ] dithiophene-4-yl, 9H-thioxanthyl, for example 9H-thioxanth-4-yl, 6H-dibenzo [ b, d ] thiopyranyl, for example 6H-dibenzo [ b, d ] thiopyran-2-yl or 6H-dibenzo [ b, d ] thiopyran-4-yl, 1, 4-benzodithiino, for example 1, 4-benzodithiin-2-yl, 1, 4-benzodithiin-5-yl or 1, 4-benzodithiin-6-yl, naphtho [1,2-b ] [1,4] dithiin-yl, for example naphtho [1,2-b ] [1,4] dithiin-2-yl or naphtho [1,2-b ] [1,4] dithiin-2-yl, for example 1, 4-benzodithiin-5-yl, 1, 4-benzodithiin-6-yl, for example 1, 4-benzodithiin-a-6-yl, naphtho [1,2-b ] [1,4] dithiin-yl, for example 1, 4-diohiin-yl, c ] thianthrene-11-yl, dibenzo [ a, H ] thianthrene-yl, for example dibenzo [ a, H ] thianthrene-6-yl, dibenzo [ a, i ] thianthrene-yl, for example dibenzo [ a, i ] thianthrene-6-yl, dibenzo [ a, j ] thianthrene-yl, for example dibenzo [ a, j ] thianthrene-6-yl, dibenzo [ b, i ] thianthrene-yl, for example dibenzo [ b, i ] thianthrene-5-yl, 2H-naphtho [1,8-b, c ] thiophenyl, for example 2H-naphtho [1,8-b, c ] thiophen-6-yl or 2H-naphtho [1,8-b, c ] thiophen-8-yl, dibenzo [ b, d ] thiazepin-yl, for example dibenzo [ b, d ] thiazepin-2-yl, dibenzo [ b, f ] thiaheptin-yl, for example dibenzo [ b, f ] thiaheptin-2-yl or dibenzo [ b, f ] thiaheptin-4-yl, 5H-phenanthro [4,5-b, c, d ] thiopyranyl, for example 5H-phenanthro [4,5-b, c, d ] thiopyran-1-yl, 5H-phenanthro [4,5-b, c, d ] thiopyran-2-yl, 5H-phenanthro [4,5-b, c, d ] thiopyran-3-yl, 5H-phenanthro [4,5-b, c, d ] thiopyran-7-yl, 5H-phenanthro [4,5-b, c, d ] thiopyran-9-yl or 5H-phenanthro [4,5-b, c, d ] thiopyran-10-yl, trichromo [ b, d, f ] thiaheptin-yl, for example, a tribenzo [ b, d, f ] thiepinin-6-yl or a tribenzo [ b, d, f ] thiepinin-8-yl, 2, 5-dihydronaphtho [1,8-b, c:4,5-b ', c' ] bithiophene radicals, such as the 2, 5-dihydronaphtho [1,8-b, c:4,5-b ', c' ] dithiophene-3-yl or 2, 5-dihydronaphtho [1,8-b, c:4,5-b ', c' ] dithiophene-7-yl, 2, 6-dihydronaphtho [1,8-b, c:5,4-b ', c' ] dithiophene-yl, e.g. 2, 6-dihydronaphtho [1,8-b, c:5,4-b ', c' ] dithiophene-4-yl, tetrabenzo [ a, c, H, j ] thianthrenyl, e.g. tetrabenzo [ a, c, H, j ] thianthren-3-yl, benzo [ b ] naphtho [1,8-e, f ] [1,4] dithienyl, dinaphto [2,3-b:2',3' -d ] thienyl, e.g. dinaphtho [2, 3'-d ] thiophenyl, e.g. dinaphtho [2, 3' -d ] thiophen-3-yl, e, e.g. tetrabenzo [1,8-e, f ] [1,4] dithienyl, e.g. benzo [1,3, 4-dithienyl, b ] naphthyrido [1, 3-c, 5-c ] phenanthro [1,8-e ] [1,4] dithienyl, e ] naphthyrido [1, 5-b ] phenanthro [1, 7-b, 4-yl, b ] thiophen-1-yl or 7H-phenanthro [1,10-c, b ] thiophen-9-yl, dibenzo [ d, d '] benzo [1,2-b:4,5-b' ] bithiophene-yl, for example dibenzo [ d, d '] benzo [1,2-b:4,5-b' ] bithiophene-4-yl or dibenzo [ d, d '] benzo [1,2-b:4,5-b' ] bithiophene-6-yl, and dibenzo [ d, d '] benzo [1,2-b:5,4-b' ] bithiophene-yl, for example dibenzo [ d, d '] benzo [1,2-b:5,4-b' ] bithiophene-4-yl or dibenzo [ d, d '] benzo [1,2-b:5,4-b' ] bithiophene-6-yl, wherein the above mentioned monocyclic or polycyclic aryl and polycyclic heteroaryl groups are substituted or unsubstituted by one or more than two groups (R25) (the following group (R25. 7.2.7).

In particular, in an embodiment of group (7), R ³ and R ⁴ are independently selected from phenyl, naphthyl, e.g. naphthalen-1-yl or naphthalen-2-yl, 1, 2-dihydroacenaphthylene, e.g. 1, 2-dihydroacenaphthylen-3-yl or 1, 2-dihydroacenaphthylen-5-yl, biphenyl, e.g. biphenyl-4-yl, biphenyl-3-yl or biphenyl-2-yl, fluorenyl, e.g. fluoren-1-yl, fluoren-2-yl, fluoren-3-yl or fluoren-4-yl, phenanthryl, e.g. phenanthren-1-yl, phenanthren-2-yl, phenanthren-3-yl, phenanthren-4-yl or phenanthren-9-yl, benzo [ c ] phenanthren-1-yl, benzo [ c ] phenanthren-2-yl, benzo [ c ] phenanthren-3-yl, benzo [ c ] phenanthren-4-yl, benzo [ c ] phenanthren-5-yl or benzo [ c ] 6-yl, e.g. pyrene-1-yl, pyrene-4-yl,Radicals, e.g./>-1-Yl,/>-2-Yl,/>-3-Yl/>-4-Yl/>-5-Yl or/>-6-Yl, triphenylene, e.g. triphenylen-1-yl or triphenylen-2-yl, benzo [ b ] furanyl, e.g. benzo [ b ] furan-2-yl, benzo [ b ] furan-3-yl, benzo [ b ] furan-4-yl, benzo [ b ] furan-5-yl, benzo [ b ] furan-6-yl or benzo [ b ] furan-7-yl, dibenzo [ b, d ] furanyl, e.g. dibenzo [ b, d ] furan-1-yl, dibenzo [ b, d ] furan-2-yl, dibenzo [ b, d ] furan-3-yl or dibenzo [ b, d ] furan-4-yl, naphtho [1,2-b ] furanyl, such as naphtho [1,2-b ] furan-5-yl, naphtho [2,3-b ] furan-yl, such as naphtho [2,3-b ] furan-3-yl, naphtho [2,3-b ] furan-4-yl or naphtho [2,3-b ] furan-9-yl, naphtho [2,1-b ] furan-yl, such as naphtho [2,1-b ] furan-2-yl or naphtho [2,1-b ] furan-5-yl, benzo [ b ] naphtho [1,2-d ] furan-yl, such as benzo [ b ] naphtho [1,2-d ] furan-1-yl or benzo [ b ] naphtho [1,2-d ] furan-4-yl, benzo [ b ] naphtho [2,3-d ] furan-yl, such as benzo [ b ] naphtho [2,3-d ] furan-2-yl, benzo [ b ] naphthalen [2,3-d ] furan-4-yl or benzo [ b ] naphthalen [2,3-d ] furan-6-yl, e.g. benzo [ b ] naphthalen [2,1-d ] furan-6-yl or benzo [ b ] naphthalen [2,1-d ] furan-7-yl, oxaanthracyl, e.g. oxazin-1-yl or oxazin-2-yl, benzo [ a ] oxaanthracyl, e.g. benzo [ a ] oxazin-1-yl, benzo [ a ] oxazin-2-yl, benzo [ a ] oxazin-6-yl or benzo [ a ] oxazin-7-yl, benzo [ b ] oxazinyl, e.g. benzo [ b ] oxazin-1-yl, benzo [ b ] oxazin-2-yl or benzo [ b ] oxazin-6-yl, e.g. benzo [ b ] oxazin-1-yl, benzo [ b ] thiophen-2-yl, benzo [ b ] oxazin-6-yl, benzo [ b ] thiophen-2-yl, benzo [ b ] oxazin-yl, benzo [ b ] oxazin-yl, naphtho [2,3-b ] thiophenyl, for example naphtho [2,3-b ] thiophen-3-yl, naphtho [2,3-b ] thiophen-4-yl or naphtho [2,3-b ] thiophen-9-yl, naphtho [2,1-b ] thiophenyl, for example naphtho [2,1-b ] thiophen-2-yl or naphtho [2,1-b ] thiophen-5-yl, benzo [ b ] naphthalen [1,2-d ] thiophenyl, for example benzo [ b ] naphtho [1,2-d ] thiophen-1-yl or benzo [ b ] naphtho [1,2-d ] thiophen-4-yl, benzo [ b ] naphtho [2,3-d ] thiophen-yl, for example benzo [ b ] naphtho [2,3-d ] thiophen-4-yl or benzo [ b ] naphtho [2,3-d ] thiophen-yl, for example benzo [2,3-d ] thiophen-4-yl, or benzo [ b ] benzo [2,3-d ] thiophen-1, 2-d ] thiophen-yl, for example, benzo [ b ] benzo [1,2-d ] thiophen-4-yl, for example, benzo [ b ] benzo [1, 7-b ] thiophen-yl, for example, benzo [1, 7-b ] thiophen-yl, c ] thienyl, such as 2H-naphtho [1,8-b, c ] thiophen-6-yl or 2H-naphtho [1,8-b, c ] thiophen-8-yl, dibenzo [ b, d ] thiepinyl, such as dibenzo [ b, d ] thiepin-2-yl, dibenzo [ b, f ] thiepinyl, such as dibenzo [ b, f ] thiepin-2-yl or dibenzo [ b, f ] thiepin-4-yl, and tribenzo [ b, d, f ] thiepinyl, such as tribenzo [ b, d, f ] thiepin-6-yl or tribenzo [ b, d, f ] thiepin-8-yl, wherein the mono-or polycyclic aryl and polycyclic heteroaryl groups mentioned above are unsubstituted or carry 1R ^Ar group (embodiment of group (7.3) below).

In a particularly preferred embodiment of group (7.4), R ³ and R ⁴ are independently selected from the group consisting of phenyl, naphthyl, 1, 2-dihydroacenaphthyl, phenanthryl, pyrenyl, triphenylene, benzo [ b ] furanyl, dibenzo [ b, d ] furanyl, benzo [ b ] thiophenyl, dibenzo [ b, d ] thiophenyl and thianthrenyl, and are especially selected from the group consisting of phenyl, naphthalen-1-yl, naphthalen-2-yl, 1, 2-dihydroacenaphthyl-5-yl, phenanthren-9-yl, pyren-1-yl, pyren-2-yl, pyren-4-yl, triphenylen-1-yl, triphenylen-2-yl, dibenzo [ b, d ] furan-4-yl, benzo [ b ] thiophen-3-yl, benzo [ b ] thiophen-4-yl, benzo [ b ] thiophen-5-yl, benzo [ b ] thiophen-6-yl, benzo [ b ] thiophen-7-d-benzothiophen-2-yl, and dithienyl. In an embodiment of subgroup (7.4 a) of group (7.4), R ¹ and R ² are independently selected from naphthyl, 1, 2-dihydroacenaphthenyl, phenanthryl, benzo [ b ] furyl, dibenzo [ b, d ] furyl, benzo [ b ] thienyl and dibenzo [ b, d ] thienyl.

It has been found that the implementation of a specific subset (7.5) of the set (7) provides a high refractive index and negative birefringence. Embodiments of these subgroups (7.5) relate to compounds of formula (I), especially compounds of formula (Ia-1), wherein R ³ and R ⁴ are different from hydrogen and wherein at least two and preferably four of the substituents R ¹、R²、R³ and/or R ⁴ are bulky or sterically hindered substituents selected from the group consisting of polycyclic aryl and polycyclic heteroaryl groups as defined herein. In this context, bulky substituents R ¹、R²、R³ and/or R ⁴ are in particular substituents from the following groups:

Polycyclic aryl and polycyclic heteroaryl groups with at least one benzene ring bound to the benzene ring in formulae (I) and (Ia-1), wherein the benzene ring of R ¹、R²、R³ and/or R ⁴ is fused to at least one of an aromatic ring having 6 to 14 carbon atoms as ring member atoms and a saturated or partially or fully unsaturated heterocyclic ring having 5 to 13 ring member atoms, wherein at least one ring fused to the benzene ring is fused to a bond between ortho and meta to the benzene ring, and

Polycyclic aryl groups having from 14 to 26, in particular from 14 to 20, carbon atoms as ring member atoms and polycyclic heteroaryl groups having from 13 to 26, in particular from 13 to 20, atoms as ring members, wherein 1, 2, 3 or 4 of the ring member atoms are selected from nitrogen, sulfur and oxygen and the remaining atoms of the ring member atoms are carbon atoms.

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

While the reasons for this beneficial effect of bulky substituents R ¹、R²、R³ and/or R ⁴ are not completely understood, it is likely that due to their steric hindrance, these substituents are forced to orient within the resin in a direction perpendicular to the backbone, which reduces the birefringence of the resin.

Thus, by balancing the positive birefringence imparted to the resin by, for example, the comonomer of formula (IV) with the negative birefringence imparted by the monomer of formula (I), in particular the monomer of formula (Ia-1) according to embodiment (7.5), a thermoplastic resin with low birefringence can be obtained according to the present invention.

In a specific subgroup (7') of embodiments, the variables R ³ and R ⁴ have the same meaning, which is selected from the meanings defined herein for R ³ and R ⁴, especially those mentioned as preferred, and especially from the meanings defined in the embodiments of groups (7), (7.1), (7.2), (7.3), (7.4 a) or (7.5).

In particular group (8) embodiments, variables R ¹、R²、R³ and R ⁴ have the same meaning. In this embodiment of group (8), the same meanings of variables R ¹、R²、R³ and R ⁴ are preferably selected from the meanings defined herein, especially those mentioned as preferred, and are preferably selected from the meanings defined in group (6), especially as defined in the embodiment of group (6.1), more especially as defined in the embodiment of group (6.2), even more preferably as defined in the embodiment of group (6.3), and especially as defined in the embodiment of group (6.3 a). In this particular embodiment of group (8), the variables R ¹、R²、R³ and R ⁴ are more preferably as defined in the embodiments of groups (7.1), (7.2), (7.3), (7.4 a) or (7.5).

In another particular group (9) of embodiments, both variables R ³ and R ⁴ are hydrogen. In addition, in the embodiment of this group (9), the variables R ¹ and R ² preferably have the same meaning, selected from the meanings defined herein, in particular as preferably mentioned herein, and preferably from the meanings defined in group (6), in particular as defined in the embodiment of group (6.1), more in particular as defined in the embodiment of group (6.2), even more preferably as defined in the embodiment of group (6.3), and in particular as defined in the embodiment of group (6.3 a).

In a preferred group (10) of embodiments, the substituents R ¹、R²、R³ and R ⁴ of formula (I) are both located meta to the X moiety, i.e., according to this group of embodiments, the compound of formula (I) is a compound of formula (Ia),

Wherein variables X, Z ¹、Z²、R¹、R²、R³ and R ⁴ have the meanings defined herein, and in particular as preferably mentioned, and wherein R ³ and R ⁴ are preferably different from hydrogen, and in particular R ¹、R²、R³ and R ⁴ have the same meaning.

Likewise, according to this preferred embodiment of group (10), the structural unit of formula (II) is a structural unit of formula (IIa),

The skilled person will readily understand that in formulae (I), (Ia), (II) and (IIa), the meaning of Z ¹ and Z ² given in one or more of the embodiments of groups (1), (1.1) and (1 ') may be combined with the meaning of X according to one of the embodiments of groups (5) or (5 '), (5 ") and (5 '"), with the meaning of R ¹ and R ² according to one or more of the embodiments of groups (6), (6.1), (6.2), (6.3 a) and (6 '), and also with the meaning of R ³ and R ⁴ according to one or more of the embodiments of groups (7), (7.1), (7.2), (7.3), (7.4 a), (7.5) and (7 '), and also with the embodiment of group (8) or (9). The skilled person will also appreciate that in formulae (I), (Ia), (II) and (IIa), the meanings of Z ¹ and Z ² given in the embodiments of group (2) may be combined with the meaning of X according to the embodiments of one of groups (5) or (5 '), (5 ") and (5'"), with the meaning of R ¹ and R ² according to one or more of the embodiments of groups (6), (6.1), (6.2), (6.3 a) and (6 '), and also with the meaning of R ³ and R ⁴ according to one or more of the embodiments of groups (7), (7.1), (7.2), (7.3), (7.4 a), (7.5) and (7'), and also with the embodiments of groups (8) or (9). The skilled person will also appreciate that in formulae (I), (Ia), (II) and (IIa), the meaning of Z ¹ and Z ² given in one or more of the embodiments of groups (3), (3.1) and (3 ') may be combined with the meaning of X according to one of the embodiments of groups (5) or (5 '), (5 ") and (5 '"), with the meaning of R ¹ and R ² according to one or more of the embodiments of groups (6), (6.1), (6.2), (6.3 a) and (6 '), and also with the meaning of R ³ and R ⁴ according to one or more of the embodiments of groups (7), (7.1), (7.2), (7.3), (7.4 a), (7.5) and (7 '), and also with the embodiment of group (8) or (9). The skilled person will also appreciate that in formulae (I), (Ia), (II) and (IIa), the meaning of Z ¹ and Z ² given in one of the embodiments of groups (4) and (4.1) may be combined with the meaning of X according to one of the embodiments of groups (5) or (5 '), (5 ') or (5 ' "), with the meaning of R ¹ and R ² according to one or more of the embodiments of groups (6), (6.1), (6.2), (6.3 a) and (6 '), and also with the meaning of R ³ and R ⁴ according to one or more of the embodiments of groups (7), (7.1), (7.2), (7.3), (7.4 a), (7.5) and (7 '), and also with the embodiments of groups (8) or (9).

In addition, the variables Ar ¹、R⁵、R⁶、R^Ar, R, R', R "and n are, if not stated otherwise, combined individually or preferably with one another and with the meanings and preferred meanings of the variables X, R ¹、R²、R³、R⁴、Z¹ and Z ² described above.

Ar ¹ is preferably a monocyclic or polycyclic aryl group having 6 to 18 carbon atoms as ring member atoms and a polycyclic heteroaryl group having a total of 9 to 16 atoms as ring member atoms, wherein 1 or 2 of the ring member atoms of the heteroaryl group are sulfur atoms and the remaining atoms of the ring member atoms of the heteroaryl group are carbon atoms, wherein the monocyclic or polycyclic aryl and polycyclic heteroaryl groups are unsubstituted or carry 1 or 2R ^Ar groups, wherein R ^Ar has one of the meanings defined herein, especially as one of the meanings preferably mentioned. Preference is given here to the unsubstituted radical Ar ¹.

More preferably Ar ¹ is selected from phenyl, naphthyl, such as naphthalen-1-yl or naphthalen-2-yl, fluorenyl, such as fluoren-1-yl, fluoren-2-yl, fluoren-3-yl or fluoren-4-yl, 11H-benzo [ a ] fluorenyl, such as 11H-benzo [ a ] fluoren-7-yl, 11H-benzo [ b ] fluorenyl, such as 11H-benzo [ b ] fluoren-1-yl, 7H-benzo [ c ] fluorenyl, such as 7H-benzo [ c ] fluoren-5-yl or 7H-benzo [ c ] fluoren-10-yl, phenanthryl, such as phenanthren-1-yl, phenanthren-2-yl, phenanthren-4-yl or phenanthren-9-yl, benzo [ c ] phenanthren-1-yl, benzo [ c ] phenanthren-2-yl, benzo [ c ] phenanthren-3-yl, benzo [ c ] fluoren-5-yl, benzo [ c ] pyren-5-yl, or benzopyren-2-yl,Radicals, e.g./>-1-Yl,/>-2-Yl,/>-3-Yl,-4-Yl/>-5-Yl or/>-6-Yl, triphenylene, e.g. triphenylen-1-yl or triphenylen-2-yl, benzo [ b ] thiophenyl, e.g. benzo [ b ] thiophen-2-yl, benzo [ b ] thiophen-3-yl, benzo [ b ] thiophen-4-yl, benzo [ b ] thiophen-5-yl, benzo [ b ] thiophen-6-yl or benzo [ b ] thiophen-7-yl, dibenzo [ b, d ] thiophenyl, e.g. dibenzo [ b, d ] thiophen-1-yl, dibenzo [ b, d ] thiophen-3-yl or dibenzo [ b, d ] thiophen-4-yl, naphtho [1,2-b ] thiophenyl, e.g. naphtho [1,2-b ] thiophen-5-yl, naphtho [2,3-b ] thiophen-yl, e.g. naphtho [2,3-b ] thiophen-3-yl, naphtho [2,3-b ] thiophen-yl, naphtho-4-yl or naphtho [2,3-b ] thiophen-1-yl, e.g. dibenzo [ b, 3-b ] thiophen-3-yl, e.g. naphtho [2,3-b ] thiophen-3-yl, naphtho-1, d ] thiophen-yl, e.g. dibenzo [ b, 3-yl, 2,3-b ] thiophen-yl, e.g. 1,2-b ] thiophen-3-yl, e.g. dibenzo-2, 2-b-3-yl, such as benzo [1,2-b:5,4-b '] dithiophene-4-yl or benzo [1,2-b:5,4-b' ] dithiophene-8-yl, benzo [1,2-b:4,5-b '] dithiophene-yl, such as benzo [1,2-b:4,5-b' ] dithiophene-4-yl, and thianthrene-yl, such as thianthrene-1-yl or thianthrene-2-yl.

Even more preferably Ar ¹ is selected from phenyl, naphthyl, fluorenyl, phenanthryl, pyrenyl,Phenyl, triphenylene, benzo [ b ] furanyl, dibenzo [ b, d ] furanyl, benzo [ b ] thiophenyl, dibenzo [ b, d ] thiophenyl and thianthrenyl, in particular selected from phenyl, naphthyl, phenanthryl,/>Radicals and dibenzo [ b, d ] thiophenyl, in particular from the group consisting of phenyl, naphthyl and phenanthryl, in particular from the group consisting of phenyl, naphthalen-1-yl, naphthalen-2-yl and phenanthren-9-yl.

R ⁵ is preferably selected from the group consisting of hydrogen, methyl, ethyl and Ar ¹ groups, wherein Ar ¹ has one of the meanings defined herein, especially the preferred meaning. More preferably, R ⁵ is hydrogen, methyl or ethyl, especially hydrogen or methyl.

R ⁶ is preferably selected from hydrogen, methyl and ethyl, especially hydrogen or methyl.

R ^Ar is preferably selected from R, OR and CH _nR_3-n, more preferably from R and OR, where n is 0, 1 OR 2, in particular 1 OR 2, and the variable R has one of the meanings defined herein, in particular the preferred meaning. In particular, the R ^Ar group is selected from methyl, methoxy, phenyl, naphthyl, phenanthryl and triphenylene groups, and in particular phenyl, naphthyl or phenanthryl.

R is preferably selected from the group consisting of methyl, phenyl, naphthyl, phenanthryl and triphenylene, which is unsubstituted or substituted by 1,2 or 3 identical or different R 'groups, wherein R' independently for each occurrence has one of the meanings defined herein, in particular the preferred meaning. More preferably, R is selected from unsubstituted phenyl, naphthyl and phenanthryl.

R ' is preferably selected from the group consisting of hydrogen, methyl, phenyl and naphthyl, wherein phenyl and naphthyl are unsubstituted or substituted by 1,2 or 3 identical or different R ' groups, wherein R ' independently at each occurrence has one of the meanings defined herein, especially the preferred meaning. More preferably, R' is unsubstituted phenyl or unsubstituted naphthyl.

R' is preferably selected from phenyl, OCH ₃ and CH ₃.

The variable n is preferably 1 or 2.

In an embodiment of the specific subgroup (10.1) of group (10), wherein in formula (Ia) the radicals Z ¹ and Z ² are each Z, which has one of the meanings defined herein for Z ¹ and Z ², in particular one of the preferred meanings, and the radicals-O-Z are each located in para-position relative to the X moiety, the compound of formula (I) is a compound of formula (Ia-1),

Wherein X, R ¹、R²、R³ and R ⁴ have the meanings defined herein, in particular as mentioned as preferred, and wherein R ³ and R ⁴ are in particular different from hydrogen.

In an embodiment of this subgroup (10.1) of group (10), the structural unit of formula (II) or (IIa) is a structural unit of formula (IIa-1),

Wherein # denotes the point of attachment to the adjacent building block, and wherein Z ^a has one of the meanings defined herein for Z ^1a and Z ^2a, in particular one of the preferred meanings, the variables X, R ¹、R²、R³ and R ⁴ have the meanings defined herein, in particular as the preferred meanings mentioned, and wherein R ³ and R ⁴ in particular are different from hydrogen.

Preferably, the definition of the X moiety in formulae (Ia-1) and (IIa-1) is the same as in the embodiments of group (5), group (5') or group (5 "). Thus, the X moiety is here chosen in particular from single bond, O, N-phenyl, N-naphthyl, N-phenanthryl, CH ₂、C(CH₃)₂、CH(CH₃), S, S (O) and SO ₂, and more in particular from single bond, O, N-phenyl, N-naphthalen-1-yl, N-naphthalen-2-yl, N-phenanthren-9-yl, CH ₂、C(CH₃)₂、CH(CH₃), S and SO ₂, in particular from single bond, O, CH ₂、C(CH₃)₂, S and SO ₂, and in particular from single bond, C (CH ₃)₂, S and SO ₂. X is particularly preferably C (CH ₃)₂. X is also particularly preferably S or SO ₂ in this context).

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

Even more preferred are compounds of formula (Ia-1) and structural units of formula (IIa-1), wherein the substituents R ¹、R²、R³ and R ⁴ have the same meaning, especially as one of the meanings mentioned herein, and especially one of the meanings defined in the embodiments of groups (6), (6.1), (6.2), (6.3) and (6.3 a) and groups (7), (7.1), (7.2), (7.3), (7.4 a) and (7.5).

Particular preference is given to compounds of the formula (Ia-1) and structural units of the formula (IIa-1), in which the substituents R ¹、R²、R³ and R ⁴ have the same meaning, which are selected from phenyl, naphthalen-1-yl, naphthalen-2-yl, 1, 2-dihydroacenaphthylen-5-yl, phenanthren-9-yl, pyren-1-yl, pyren-2-yl, pyren-4-yl, triphenylen-1-yl, triphenylen-2-yl, dibenzo [ b, d ] furan-4-yl, benzo [ b ] thiophen-3-yl, benzo [ b ] thiophen-4-yl, benzo [ b ] thiophen-5-yl, benzo [ b ] thiophen-6-yl, benzo [ b, d ] thiophen-7-yl, dibenzo [ b, d ] thiophen-2-yl, thianthrene-1-yl and thianthrene-2-yl. Particular preference is given to compounds of the formula (Ia-1) and structural units of the formula (IIa-1), in which the substituents R ¹、R²、R³ and R ⁴ are independently selected from phenyl, naphthyl, 1, 2-dihydroacenaphthylyl, phenanthryl, benzo [ b ] thienyl, dibenzo [ b, d ] thienyl and thianthrenyl, and in particular from phenyl, naphthalen-1-yl, naphthalen-2-yl, phenanthren-9-yl, dibenzo [ b, d ] thiophen-2-yl, dibenzo [ b, d ] thiophen-4-yl, thianthrene-1-yl and thianthrene-2-yl.

Examples of specific subgroups (10.1) are compounds of formula (Ia-1) and structural units of formula (IIa-1) wherein the combination of moiety X, group Z and variable R ^y is as defined in any one of rows 1 to 442 in table a below, wherein variable R ^y represents the same meaning of substituents R ¹、R²、R³ and R ⁴.

Table A

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Of the compounds of formula (Ia-1) and structural units of formula (IIa-1) listed in Table A, particular preference is given to compounds of formula (Ia-1) and structural units of formula (IIa-1) in which the X moiety is C (CH ₃)₂、SO₂, S or a single bond, in other words, particular preference is given to compounds of formula (Ia-1) in which the combination of the X moiety, the group Z and the variable R ^y is as defined above in any of lines 1 to 95 and lines 243 to 442 of Table A, where the variable R ^y represents the same meaning of the substituents R ¹、R²、R³ and R ⁴.

In an embodiment of the specific subgroup (10.2) of group (10), wherein in formula (Ia) the radicals Z ¹ and Z ² are each Z, which has one of the meanings defined herein for Z ¹ and Z ², in particular one of the preferred meanings, and the radicals-O-Z are each located in ortho-position relative to the X moiety, the compound of formula (I) is a compound of formula (Ia-2),

In an embodiment of this subgroup (10.2) of group (10), the structural unit of formula (II) or (IIa) is a structural unit of formula (IIa-2),

Wherein # denotes the point of attachment to the adjacent building block, and wherein Z ^a has one of the meanings defined herein for Z ^1a and Z ^2a, in particular one of the preferred meanings, the variables X, R ¹、R²、R³ and R ⁴ have the meanings defined herein, in particular as the preferred reference, and wherein R ³ and R ⁴ are in particular different from hydrogen.

Preferably, the definition of the X moiety in formulae (Ia-2) and (IIa-2) is the same as in the embodiment of group (5) or group (5'). Thus, the X moiety is here chosen in particular from single bonds, O, N-phenyl, N-naphthyl, N-phenanthryl, CH ₂、C(CH₃)₂、CH(CH₃), S, S (O) and SO ₂, more in particular from single bonds, O, N-phenyl, N-naphthalen-1-yl, N-naphthalen-2-yl, N-phenanthren-9-yl, CH ₂、C(CH₃)₂、CH(CH₃), S and SO ₂, in particular from single bonds, O, CH ₂、C(CH₃)₂, S and SO ₂, and in particular from single bonds, C (CH ₃)₂, S and SO ₂. In this context it is particularly preferred that X is a single bond.

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

Even more preferred are compounds of formula (Ia-2) and structural units of formula (IIa-2), wherein the substituents R ¹、R²、R³ and R ⁴ have the same meaning, which is especially one of the meanings mentioned as preferred herein, and especially one of the meanings defined in the embodiments of groups (6), (6.1), (6.2), (6.3) and (6.3 a) and groups (7), (7.1), (7.2), (7.3), (7.4 a) and (7.5).

Particular preference is given to compounds of the formula (Ia-2) and structural units of the formula (IIa-2), in which the substituents R ¹、R²、R³ and R ⁴ have the same meaning, which are selected from the group consisting of phenyl, naphthalen-1-yl, naphthalen-2-yl, 1, 2-dihydroacenaphthylen-5-yl, phenanthren-9-yl, pyren-1-yl, pyren-2-yl, pyren-4-yl, triphenylen-1-yl, triphenylen-2-yl, dibenzo [ b, d ] furan-4-yl, benzo [ b ] thiophen-3-yl, benzo [ b ] thiophen-4-yl, benzo [ b ] thiophen-5-yl, benzo [ b ] thiophen-6-yl, benzo [ b ] thiophen-7-yl, dibenzo [ b, d ] thiophen-4-yl, thianthan-1-yl and thianthan-2-yl, and in particular from the group consisting of benzo [ b, benzo [ b ] thiophen-2-yl, benzo [ b ] thiophen-6-yl, benzo [ b, d ] thiophen-4-yl and thianthan-2-yl.

Examples of specific subgroups (10.2) are compounds of formula (Ia-2) and structural units of formula (IIa-2) wherein the combination of the X moiety and the variable R ^x is defined in any one of rows 1 to 64 of table B below, wherein the variable R ^y represents the same meaning of substituents R ¹、R²、R³ and R ⁴.

Table B

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Compounds of formula (I) in which X, Z ¹、Z²、R¹、R²、R³ and R ⁴ each have one of the meanings defined herein can be prepared, for example, by a process analogous to that shown in scheme 1 below, which is particularly suitable for compounds (I) in which R ¹、R²、R³ and R ⁴ have the same meaning and Z ¹ and Z ² are the same groups selected from-Alk-OH, -CH ₂-Ar²-CH₂-OH、Alk-C(O)OR^x and-CH ₂-Ar² -C (O) OR as defined herein. The corresponding compound (I) (wherein Z ¹ and Z ² are both hydrogen) can be obtained, for example, by modifying the process of scheme 1 such that step b) is omitted and compound (2) is directly subjected to reaction step c).

Route 1:

Each of the transformations of steps a), b) and c) in scheme 1 may be accomplished by employing one or more of the reaction steps in the methods described below in combination with schemes 2a, 2b, 2c, 3, 4a, 4b, 5, 6a, 6b, 6c, 7a and 7b, or by obvious variations of these reaction steps, or alternatively, by preparing a mature method in organic chemistry, or a combination thereof.

Compounds of formula (Ia '), which are compounds of formula (Ia) as defined herein, wherein R ¹、R²、R³ and R ⁴ have the same meaning, i.e. the same substituent Ar is selected from optionally substituted mono-or polycyclic heteroaryl or aryl groups as defined herein, and wherein Z ¹ and Z ² are the same group Z', which is selected from-Alk-OH, -CH ₂-Ar²-CH₂-OH、-Alk-C(O)OR^x and-CH ₂-Ar²-C(O)OR^x as defined herein, e.g. can be prepared by a reaction analogous to that described in scheme 2a below.

Route 2a:

in an initial step i), bisphenol (1') whose hydroxyl groups are each located in the ortho or para position relative to the X moiety is reacted with a suitable brominating agent to give the corresponding tetrabrominated derivative (4). Suitable brominating agents are in particular elemental bromine, which is generally used in an amount of from 3 to 15 times molar excess relative to bisphenol (1'). In step ii), tetrabromobisphenol (4) can be converted to compound (5) by reaction with reagent Y-Z 'in the presence of a base, such as an oxygen-containing base (oxo base), for example a basic carbonate such as potassium carbonate, wherein Y is a suitable leaving group, such as a chloro, bromo, iodo, tosylate or mesylate group and Z' is-Alk-OH, -CH ₂-Ar²-CH₂-OH、-Alk-C(O)OR^x or-CH ₂-Ar²-C(O)OR^x. The conversion in step iii) of scheme 2a can be accomplished by a Suzuki coupling reaction by treating tetrabromide (5) with boric acid of the formula Ar-B (OH) ₂, wherein Ar has one of the meanings defined herein for substituents R ¹ and R ², or with an ester or anhydride of said boric acid, in particular a C ₁-C₄ -alkyl ester thereof, in the presence of a transition metal catalyst, in particular a palladium catalyst. Suitable palladium catalysts are in particular those with at least one trisubstituted phosphine ligand, for example tetrakis (triphenylphosphine) palladium and tetrakis (triphenylphosphine) palladium. Typically, palladium catalysts are prepared in situ from a suitable palladium precursor such as palladium (II) acetate (Pd (OAc) ₂) and a suitable phosphine ligand such as, inter alia, triarylphosphines such as triphenylphosphine and triphenylphosphine. Typically, the reaction is carried out in the presence of a base, especially an oxygen-containing base such as an alkali metal carbonate or alkaline earth metal carbonate, e.g. potassium carbonate.

In the case where the group Z ' of compound (5) is hydroxyethyl, the conversion shown in reaction step ii) of scheme 2a can be carried out using 2-chloro-ethanol as reagent Y-Z ', or alternatively ethylene carbonate or ethylene oxide, in particular ethylene carbonate, can be used instead of reagent Y-Z '. This conversion with 2-chloro-ethanol, ethylene carbonate or ethylene oxide is carried out in the presence of a base, for example an oxygen-containing base, for example an alkaline carbonate such as potassium carbonate.

As a further example, if the group Z 'of compound (5) is-Alk-C (O) OR ^x, the transformations shown in reaction step ii) of scheme 2a can be carried out by analogy with the methods described, for example, in T.Ema, J.Org.Chem.,2010,75 (13), 4492-4500 OR T.Ema et al, org.Lett.,2006,8,17,3773-3775, using Hal-Alk-C (O) OR ^x as reagent Y-Z', wherein Hal is halogen, such as, inter alia, bromine OR chlorine. The ester groups O-Alk-C (O) R ^x thus introduced can, if desired, be subsequently converted into the corresponding acid groups O-Alk-C (O) OH using known ester hydrolysis methods.

Suitable reaction conditions and suitable reagents for step i) of scheme 2a may be employed from, for example, U.S. 3,363,007,US 5,208,389,JP H049346,CN 101100416,US 6,147,264,L.Kumar et al, organic Process Research & Development,2010,14 (1), 174-179, S. Dev et al, polymer,2017,133,20-29, R.—N.Wang et al, hebei Gongye Daxue Xuebao,2012,41 (3), 42-45, J.Lu et al, crystal Growth & Design,2011,11 (8), 3551-3557, K.—B.Oh et al, bioorganic & MEDICINAL CHEMISTRY LETTERS,2008,18 (1), 104-108, Y.Xin et al, huaxue Yanjiu Yu Yingyong,2006,18 (11), 1346-1348, Q.Yang et al, china CN 111072529,CN 103992209,CN102898337, and V.A. Orlova et al, trudy Vsesoyuznogo Instituta Gel' mintologiiimeni K.I.ryabina, 1971,18,201-205; for step ii) of route 2a, e.g. from JP S50105638 (a), JP S5846034 (a), JPs5251351 (a), imai, hirokazu; japanese patent application publication No. 2013249373,JP 2013249374,JP 2008143854, and JP H0338563 (A); and for step iii) of scheme 2 a), for example from 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, biorg. Med. Chem. Lett.,2001,9,3243-3253; zhang et al Tetrahedron Lett, 2011,52,311-313; S.Bourrain et al, synlett,2004,5,795-798; li et al, europ.J. org.chem.2011, 3932-3937.

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

Route 2b:

route 2c:

The reactions according to steps i), ii) and iii) of schemes 2b and 2c may be carried out using the same or very similar reaction conditions as those described for steps i), ii) and iii) of scheme 2 a. The compound of formula (Ia ") obtained in the second reaction step of scheme 2b is a compound of formula (Ia) as defined herein, wherein R ¹、R²、R³ and R ⁴ are both identical substituents Ar as defined in the context of scheme 2a, and wherein Z ¹ and Z ² are both hydrogen. The sequence of steps i) and iii) according to scheme 2 b) is therefore suitable for preparing such compounds (Ia) according to the invention.

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

Route 3:

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

As an alternative to the synthesis according to scheme 2a or 2c, the tetrabromides of formula (5), wherein X is S (O) and Z' is-Alk-OH, -CH ₂-Ar²-CH₂-OH、-Alk-C(O)OR^x or-CH ₂-Ar²-C(O)OR^x as defined herein, may also be prepared by reduction of the corresponding compound (5), wherein X is SO ₂. Conversely, the tetrabromide of formula (5), wherein X is S (O), can be reduced to the corresponding sulfide, thereby providing an alternative method of synthesizing compound (5) wherein X is S. Likewise, the compounds (Ia ') (where X is S (O) or S) can also be obtained by partial reduction of the corresponding compounds (Ia') with SO ₂ or S (O) at the X position. These transformations are summarized in schemes 4a and 4b below.

Route 4a:

route 4b:

The reductive transformations shown in schemes 4a and 4b may be performed using well established methods in the art for converting sulfones to sulfoxides and sulfoxides to sulfides, respectively. For example, the sulfoxide can be converted to the corresponding sulfoxide by initial reaction with 4-chlorodiazobenzene tetrafluoroborate, followed by reduction with sodium borohydride, and the sulfoxide can be converted to the corresponding sulfide by reduction with lithium aluminum hydride or elemental sulfur.

An alternative to the process according to schemes 2a to 2c for preparing compounds of formula (Ia-1) wherein X is N-Ar ¹ is the synthesis shown in scheme 5 below. The 2, 6-diaryl phenol or 2, 4-diaryl phenol (6) is first brominated and then its hydroxyl groups are converted to protective methoxymethyl (MOM) ether groups to give intermediate (7) which is subsequently reacted with aryl amine (8) in the presence of a palladium catalyst. The final deprotection gives compound (Ia ") where X is N-Ar ¹ (where Ar ¹ is as defined herein) which can be converted according to scheme 2b to the corresponding compound of formula (Ia'). A similar method is described in detail in Y.Matsuta et al Chemistry-An Asian Journal,2017,12 (15), 1889-1894.

Route 5:

Compounds of formula (Ia '), which are compounds of formula (Ia) of the present invention wherein X has one of the meanings defined herein, R ³ and R ⁴ are both hydrogen, R ¹ and R ² are the same substituents Ar selected from optionally substituted mono-or polycyclic heteroaryl or aryl groups as defined herein, and Z ¹ and Z ² are the same groups Z') selected from-Alk-OH, -CH ₂-Ar²-CH₂-OH、-Alk-C(O)OR^x and-CH ₂-Ar²-C(O)OR^x as defined herein can be prepared, for example, by analogy to the methods shown in scheme 6a below.

Route 6a:

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The reaction steps i), ii) and iii) of scheme 6a can in principle be carried out analogously to steps i) to iii) described above in connection with the preparation of the compounds of formula (Ia') shown in scheme 2 a. However, unlike the bromination in step i) of scheme 2a, the bromination in this step i) is typically performed using an excess of 1.5-to 5-fold relative to bisphenol (1'), as defined in the process context in scheme 2a above.

Suitable reaction conditions and suitable reagents for step i) of scheme 6a may be derived from the prior art literature listed above in connection with the process shown in scheme 2 a. In this regard, additional specific information regarding step ii) of route 6a, for example, may be obtained from CA 663542,US 4,093,555; GB,1 489 659a; and for step iii) of scheme 6a, can be obtained from JP H02111743 (A), JP H08208775 (A), and S.R. turner et al High Performance Polymers,2005,17 (3), 361-376.

Alternatively still, the compounds of formula (Ia' ") may be prepared by rearranging the order of steps i), ii) and iii) shown in scheme 6a according to schemes 6b and 6c below.

Route 6b:

route 6c:

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

As an alternative to the synthesis according to scheme 6a or 6c, the dibromides of formula (10), wherein X is S (O) and Z' is-Alk-OH, -CH ₂-Ar²-CH₂-OH、-Alk-C(O)OR^x or-CH ₂-Ar²-C(O)OR^x as defined herein, may also be prepared by reduction of the corresponding compound (10), wherein X is SO ₂. Conversely, bisphenol compounds of formula (10) wherein X is S (O) can be reduced to the corresponding sulfide, thereby providing an alternative method of synthesizing compound (10) wherein X is S. Likewise, the compounds (Ia '") (wherein X is S (O) or S) can also be obtained by partial reduction of the corresponding compounds (Ia'") with SO ₂ or S (O) at the X position. These transformations are summarized in schemes 7a and 7b below.

Route 7a:

route 7b:

The reductive transformations shown in schemes 7a and 7b may be performed using methods well established in the art for converting sulfones to sulfoxides and sulfoxides to sulfides, respectively, such as those described above in connection with the methods of schemes 4a and 4 b.

Alternative processes for preparing the bis-phenols dibromide of formula (9), wherein X is the CH ₂ moiety, and the compounds of formulae (Ia' ") and (Ia" "), wherein X is N-Ar ¹, can be readily derived from the processes described above in connection with schemes 3 and 5 by using 2-bromophenol or 4-bromophenol instead of 2, 6-dibromophenol and 2-arylphenol or 4-arylphenol instead of 2, 6-diarylphenol (6), respectively, as starting compounds.

Other compounds of formula (I) can be prepared by methods well established in the preparation of organic chemistry using obvious variations of the above reactions and combinations thereof.

The reaction mixtures obtained in the various steps for preparing the syntheses of the compounds described in schemes 1, 2a, 2b, 2c, 3, 4a, 4b, 5, 6a, 6b, 6c, 7a and 7b above are generally purified in a conventional manner, for example by mixing with water, separating the phases and, where appropriate, purifying the crude product by washing, chromatography or crystallization. In some cases, the intermediates are formed in the form of colorless or light brown viscous oils that are free of volatiles or purified at reduced pressure and moderately elevated temperatures. If a solid intermediate is obtained, purification can be achieved by recrystallization or washing methods such as slurry washing.

The starting compounds for preparing the compounds of formula (I) in the syntheses shown in schemes 1, 2a, 2b, 2c, 3, 4a, 4b, 5, 6a, 6b, 6c, 7a and 7b above are commercially available or can be prepared by methods known in the art.

As mentioned above, the compounds of the invention can be obtained in very high purity, which means that the obtained product contains no significant amounts of organic impurities other than the compounds of formula (I) other than volatiles. Typically, the purity of the compounds of formula (I) is at least 95%, in particular at least 98%, and in particular at least 99%, based on the nonvolatile organic matter, i.e. the product contains up to 5%, in particular up to 2% and in particular up to 1% of nonvolatile impurities other than the compounds of formula (I).

The term "volatiles" refers to organic compounds having a boiling point below 200 ℃ at standard pressure (10 ⁵ Pa). Thus, non-volatile organic material is understood to mean a compound having a boiling point exceeding 200 ℃ at standard pressure.

A particular benefit of the present invention is that the compounds of formula (I) and solvates thereof are generally available in crystalline form. In crystalline form, the compounds of formula (I) may be present in pure form or in the form of solvates with water or organic solvents. Accordingly, a particular aspect of the invention relates to compounds of formula (I) which are substantially present in crystalline form. In particular, the present invention relates to crystalline forms wherein the compound of formula (I) is present in the absence of a solvent, and to crystalline solvates of the compound of formula (I) wherein the crystals contain an incorporated solvent.

A particular benefit of the present invention is that the compounds of formula (I) and solvates thereof can generally be readily crystallized from conventional organic solvents. This allows for efficient purification of the compound of formula (I). Suitable organic solvents for crystallizing the compound of formula (I) or a solvate thereof include, but are not limited to, aromatic hydrocarbons such as toluene or xylene, aliphatic ketones, especially ketones having 3 to 6 carbon atoms such as acetone, methyl ethyl ketone, methyl isopropyl ketone or diethyl ketone, aliphatic and alicyclic ethers such as diethyl ether, dipropyl ether, methyl isobutyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, dioxane or tetrahydrofuran, aliphatic-aromatic ethers such as anisole, and aliphatic alcohols having 1 to 4 carbon atoms such as methanol, ethanol or isopropanol, and mixtures thereof.

Alternatively, the compounds of formula (I) and solvates thereof may be obtained in purified form by employing other simple and effective methods for purifying crude products of these compounds, such as, inter alia, crude solids obtained directly after slurry wash conversion, to prepare the compounds of formula (I). Slurry washing is typically carried out at ambient temperature or at elevated temperatures, typically about 30 to 90 ℃, especially 40 to 80 ℃. Suitable organic solvents are in principle the same as those listed above for the crystallization of the compounds of the 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.

Thus, the compounds of formula (I) for preparing the thermoplastic polymers defined herein, in particular polycarbonates, can be easily prepared and obtained in high yields and purity. In particular, the compounds of formula (I) can be obtained in crystalline form, which allows for efficient purification to the extent required in the preparation of optical resins. In particular, these compounds can be obtained in purities that provide high refractive indices and low haze, which is particularly important for the use of optical resins for the preparation of optical devices. In summary, the compounds of formula (I) are particularly useful as monomers in the preparation of optical resins.

The skilled person will readily understand that formula (I) of the monomers used corresponds to formula (II) of the structural units comprised in the thermoplastic resin. Likewise, the formulae (Ia), (Ia-1) and (Ia-2) of the monomers used correspond to the formulae (IIa), (IIa-1) and (IIa-2), respectively, of the structural units included in the thermoplastic resin.

The skilled person will also understand that the structural units of formulae (II), (IIa-1) and (IIa-2) are repeating units within the polymer chain of the thermoplastic resin.

In addition to the structural units of each of the formulae (II), (IIa-1) and (IIa-2), the thermoplastic resins may have structural units different therefrom. In a preferred embodiment, these other building blocks are derived from aromatic monomers of formula (IV), thereby producing building blocks of formula (V):

HO-R^z-A¹-R^z-OH (IV)

#-O-R^z-A¹-R^z-O-# (V)

Wherein the method comprises the steps of

# Represents the connection point with the adjacent structural unit;

Wherein the method comprises the steps of

Q represents a single bond, O, NH, c= O, CH ₂ or ch=ch;

* Represents a point of attachment to a benzene ring;

Ar is selected from the group consisting of a monocyclic or polycyclic aryl group having from 6 to 26 carbon atoms as ring member atoms and a monocyclic or polycyclic heteroaryl group having from 5 to 26 total atoms as ring members, wherein 1, 2,3 or 4 of the ring member atoms of the heteroaryl group are selected from nitrogen, sulfur and oxygen and the remaining atoms of the ring member atoms of the heteroaryl group are carbon atoms, wherein Ar is unsubstituted or substituted with 1, 2 or 3R ^ab groups selected from halogen, phenyl and C ₁-C₄ -alkyl;

P is an integer of 1 to 10;

Alk ¹ is C ₁-C₄ -alkanediyl;

Alk ² is C ₂-C₄ -alkanediyl; and

Alk ³ is C ₁-C₄ -alkanediyl.

If R ^z in formula (IV) is O-Alk ³ -C (O), esters of monomers of formula (IV), in particular C ₁-C₄ -alkyl esters, may alternatively be used.

In the context of the formulae (IV) and (V), A ¹ is in particular a polycyclic radical having 2 benzene or naphthalene rings, the benzene rings being linked via A. In this context, A is selected in particular from the group consisting of single bonds, CH-Ar, CAr ₂ and A'.

In the context of the formulae (IV) and (V), R ^z is in particular O-Alk ² -, where Alk ² is in particular a linear alkanediyl radical having from 2 to 4 carbon atoms, and in particular O-CH ₂CH₂.

Among the monomers of the formula (IV), preferred are monomers of the formulae (IV-1) to (IV-6)

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Wherein the method comprises the steps of

A and b are 0, 1, 2 or 3, in particular 0 or 1;

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

e and f are 0, 1,2, 3, 4 or 5, in particular 0 or 1;

and wherein R ^z、R^aa、R^ab、R^7a and R ^7b are as defined In (IV), and wherein R ^z is selected from among others a single bond, CH ₂ and OCH ₂CH₂.

Among the monomers of formula (IV), particular preference is given to monomers of the formulae (IV-11) to (IV-20), where R ^z and R ^aa are as defined herein, and R ^z is selected in particular from the group consisting of single bonds, CH ₂ and O-CH ₂CH₂, in particular O-CH ₂CH₂:

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Examples of compounds of the formulae (IV-11) to (IV-20) are 9, 9-bis (4-hydroxyphenyl) fluorene, 9-bis (4-hydroxy-3-methylphenyl) fluorene, 9-bis (4-hydroxy-3-isopropylphenyl) fluorene 9, 9-bis (4-hydroxy-3-tert-butylphenyl) fluorene, 9-bis (4-hydroxy-3-cyclohexylphenyl) fluorene, 9-bis (4-hydroxy-3-phenylphenyl) fluorene, 9-bis (4- (2-hydroxyethoxy) phenyl) fluorene 9, 9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene, 9-bis (4- (2-hydroxyethoxy) -3-isopropylphenyl) fluorene, 9-bis (4- (2-hydroxyethoxy) -3-tert-butylphenyl) fluorene, 9-bis (4- (2-hydroxyethoxy) -3-cyclohexylphenyl) fluorene, 9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene (also known as BPPEF), 9-bis (6-hydroxy-2-naphthyl) fluorene, 9, 9-bis (6- (2-hydroxyethoxy) -2-naphthyl) fluorene (also known as9, 9-bis (6- (2-hydroxyethoxy) naphthalen-2-yl) fluorene (BNEF)), 10-bis (4-hydroxyphenyl) anthracene-9-one, 10-bis (4- (2-hydroxyethoxy) phenyl) anthracene-9-one, 4 '-dihydroxytetraphenyl methane, 4' -bis- (2-hydroxyethoxy) -tetraphenyl methane, 3 '-diphenyl-4, 4' -dihydroxy-tetraphenyl methane, bis- (6-hydroxy-2-naphthyl) -diphenyl methane 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' -bis (1-hydroxyethoxy) -1,1 '-binaphthyl, 2' -bis (3-hydroxypropoxy) -1,1 '-binaphthyl, 2' -bis (4-hydroxybutoxy) -1,1 '-binaphthyl, 2' -bis (2-hydroxyethoxy) -6,6 '-diphenyl-1, 1' -binaphthyl, 2,2' -bis (2-hydroxyethoxy) -6,6' -bis (naphthalen-1-yl) -1,1' -binaphthyl, 2' -bis (2-hydroxyethoxy) -6,6' -diphenyl-1, 1' -binaphthyl, 2' -bis (2-hydroxyethoxy) -6,6' -bis (naphthalen-1-yl) -1,1' -binaphthyl, 2' -bis (2-hydroxypropoxy) -6,6' -diphenyl-1, 1' -binaphthyl 2,2' -bis (2-hydroxypropoxy) -6,6' -bis (naphthalen-1-yl) -1,1' -binaphthyl, 2' -bis (2-hydroxyethoxy) -6,6' -bis (naphthalen-2-yl) -1,1' -binaphthyl, 2' -bis (2-hydroxyethoxy) -6,6' -bis (9-phenanthryl) -1,1' -binaphthyl and the like. Among the monomers of the formulae (IV) or (IV-1) to (IV-6), particular preference is given to monomers of the formulae (IV-1), (IV-2), (IV-3) and (IV-6), more particular preference to monomers of the formulae (IV-2), (IV-3) and (IV-6), particularly preference being given to 2,2' -bis (2-hydroxyethoxy) -1,1' -binaphthyl (BNE or BHBNA), 2' -bis (2-hydroxyethoxy) -6,6' -diphenyl-1, 1' -binaphthyl (DPBHBNA), 9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (BPEF), 9-bis (6- (2-hydroxyethoxy) -2-naphthyl) fluorene (BNEF) and 9, 9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene (BPPEF).

Therefore, among the structural units of the formula (V) which can be included in the thermoplastic resin, structural units of the general formulae (V-1) to (V-6) are preferable,

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Wherein the method comprises the steps of

A and b are 0, 1, 2 or 3, in particular 0 or 1;

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

e and f are 0, 1,2, 3, 4 or 5, in particular 0 or 1;

And wherein R ^z、R^aa、R^ab、R^7a and R ^7b are as defined in formula (V), and wherein R ^z is selected from among others single bond, CH ₂ and OCH ₂CH₂.

Particularly preferred are structural units of the formulae (V-11) to (V-20), wherein R ^z and R ^aa are as defined herein, and wherein R ^z is selected in particular from the group consisting of single bonds, CH ₂ and O-CH ₂CH₂, in particular O-CH ₂CH₂:

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

In a particularly preferred group of embodiments, the thermoplastic resins of the present invention comprise at least one structural unit of formula (IIa-1) or (IIa-2) and at least one structural unit selected from the group consisting of structural units of formula (V-11), structural units of formula (V-19) and structural units of formula (V-20). In this particular group of embodiments, preference is given to those thermoplastic resins in which the substituents R ¹、R²、R³ and R ⁴ or R ¹ and R ² in the structural units of the formula (IIa-1) or (IIa-2) are identical and have one of the meanings defined herein, in particular as one of the meanings mentioned as preferred. In this particular group of embodiments, preference is given to those thermoplastic resins in which the radical R ^z in the structural units of the formulae (V-11), (V-19) and (V-20) is O-CH ₂CH₂.

In the thermoplastic resins of this group of particularly preferred embodiments, it is preferred that the total molar ratio of the structural units of the formula (IIa-1) or (IIa-2) to the total of the structural units of the formulae (II) and (V) is in the range of 1 to 70 mol%, preferably in the range of 5 to 60 mol%, more preferably in the range of 8 to 45 mol%, and even more preferably in the range of 10 to 30 mol%.

Another specific group (10) of embodiments of the present invention relates to thermoplastic resins having only low, little or no birefringence. The resins of this group (10) embodiment are characterized by having structural units of the formula (II), for example in particular of the formula (IIa-1), in which R ¹、R²、R³ and R ⁴ have the same definition as in the embodiment of group 5.5, and additionally having one or more structural units which are different from the structural units of the formula (II), preferably selected from structural units of the formula (V), in particular from structural units of the formulae (V-11), (V-12), (V-14), (V-19) and (V-20), and in particular from structural units of the formulae (V-11), (V-19) and (V-20). In the thermoplastic resin of this particularly preferred embodiment of group (10), it is preferred that the total molar ratio of the structural units of formula (IIa-1) or (IIa-2) to the total of the structural units of formulae (II) and (V) is in the range of 0.5 to 70 mol%, preferably in the range of 1 to 60 mol%, more preferably in the range of 2 to 45 mol%, and even more preferably in the range of 3 to 30 mol%.

The compounds of formulas (IV)、(IV-1)、(IV-2)、(IV-3)、(IV-4)、(IV-5)、(IV-6)、(IV-11)、(IV-12)、(IV-13)、(IV-14)、(IV-15)、(IV-16)、(IV-17)、(IV-18)、(IV-19) and (IV-20) are known or can be prepared by methods analogous to known methods.

For example, the compound of formula (IV-6) may be prepared by various synthetic methods, as disclosed, for example, in japanese laid-open publication No. 2014-227387, japanese laid-open publication No. 2014-227388, japanese laid-open publication No. 2015-168658, japanese laid-open publication No. 2015-187098. For example, 1' -binaphthol can be reacted with ethylene glycol monomethylenesulfonate; alternatively, the 1,1' -binaphthol may be reacted with an alkylene oxide, a haloalkol or an alkylene carbonate; alternatively, 1' -binaphthol may be reacted with ethylene carbonate. Thus, a compound of formula (IV-6) wherein R ^z -OH is O-Alk ² -or O-Alk ²-[O-Alk²-]_p -is obtained.

For example, the compound of formula (IV-2) may be prepared by various synthetic methods, as disclosed, for example, in Japanese patent laid-open No. 5442800 and Japanese laid-open No. 2014-028806. Examples include:

(a) Reacting fluorene with hydroxynaphthalene in the presence of hydrochloric acid gas and mercapto carboxylic acid;

(b) Reacting 9-fluorene with hydroxynaphthalene in the presence of an acid catalyst (and an alkyl mercaptan);

(c) Reacting fluorene with hydroxynaphthalene in the presence of hydrochloride and thiol (e.g., mercapto carboxylic acid);

(d) Reacting fluorene with hydroxynaphthalene in the presence of sulfuric acid and a thiol (e.g., mercapto carboxylic acid), and then crystallizing the product from a crystallization solvent consisting of a hydrocarbon and a polar solvent to form binaphthol fluorene; etc.

Thus, a compound of formula (IV-2) wherein R ^z is a single bond can be obtained.

Compounds of formula (IV) wherein R ^z is O-Alk ² -or O-Alk ²-[O-Alk²-]_p -may be prepared from compounds of formula (IV) wherein R ^z is a single bond by reaction with alkylene oxides or haloalkols. For example, reacting 9, 9-bis (hydroxynaphthyl) -fluorene of formula (IV-2) (wherein R ^z is a single bond) with an alkylene oxide or haloalkanol produces a compound of formula (IV-2) (wherein R ^z is O-Alk ² -or O-Alk ²-[O-Alk²-]_p -). For example, 9-bis [6- (2-hydroxyethoxy) naphthyl ] fluorene can be prepared by reacting 9, 9-bis [6- (2-hydroxynaphthyl ] fluorene with 2-chloroethanol under basic conditions.

The monomers of formula (I) and likewise the comonomers of formula (IV) used to produce the thermoplastic resins may contain certain impurities resulting from their preparation, for example hydroxy compounds which carry OH groups instead of the groups O-Z ¹ -OH or O-Z ² -OH, or which may contain the groups O-Alk ' - [ O-Alk ' ] _o instead of the groups O-Alk ' -, or which may contain halogen atoms instead of the groups R ¹、R²、R³ or R ⁴. The total amount of these impurity compounds is preferably 1000ppm or less, more preferably 500ppm or less, still more preferably 200ppm or less, and particularly preferably 100ppm or less. The total content of impurities in the monomer used for producing the thermoplastic resin is preferably 100ppm or less, particularly 50ppm or less, and more preferably 20ppm or less. In particular, in the monomer having the dihydroxy compound represented by formula (I) as a main component, the total amount of the dihydroxy compounds in which at least one of the groups Z ¹ or Z ² has a carbon number different from that of formula (I) is preferably 1000ppm or less, more preferably 500ppm or less, still more preferably 200ppm or less, and particularly preferably 100ppm or less. The total content of dihydroxy compounds in which at least one of the groups Z ¹ or Z ² has a carbon number different from that of formula (I) is further preferably 50ppm or less, and more preferably 20ppm or less. Also, the amount of impurities in the comonomer of formula (IV) will be within the ranges given for the monomer of formula (I).

Suitable thermoplastic resins for the production of optical devices such as lenses are in particular polycarbonates, polyester carbonates and polyesters. Preferred thermoplastic resins for the preparation of optical devices such as lenses are in particular polycarbonates.

The structure of the polycarbonates is characterized by structural units of at least one of the formulae (II), (IIa-1) and (IIa-2), respectively, optionally structural units derived from diol monomers other than the monomer compounds of the formula (I), for example structural units of the formula (V),

#-O-R^z-A¹-R^z-O-# (V)

Wherein the method comprises the steps of

#, R ^z, and a ¹ are as defined above;

and structural units of formula (III-1) derived from a carbonate forming component:

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 structure of the polyesters is characterized by having structural units of at least one of the formulae (II), (IIa-1) and (IIa-2), respectively, optionally structural units derived from diol monomers other than the monomer compounds of formula (I), for example structural units of formula V, and structural units derived from dicarboxylic acids, for example structures of formula (III-2) in the case of phthalic acid, of formula (III-3) in the case of naphthoic acid, of formula (III-4) in the case of oxalic acid and of formula (III-5) in the case of malonic acid:

in formulae (III-2) to (III-5), each variable # represents a point of attachment to an adjacent structural unit, i.e., O to a point of attachment to a structural unit of formula (II), and O to a point of attachment to a structural unit of formula (V), if present.

The structural features of the polyester carbonates are structural units of at least one of the formulae (II), (IIa-1) and (IIa-2), respectively, optionally structural units derived from diol monomers other than the monomer compounds of formula (I), for example structural units of formula (V), structural units of formula (III-1) derived from the carbonate forming component and structural units derived from dicarboxylic acids, for example in the case of phthalic acid, in the case of naphthoic acid, in the case of formula (III-3), in the case of oxalic acid, in the case of formula (III-4) and in the case of malonic acid, in the case of formula (III-5).

One 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 monomer of formula (I) to the monomer of formula (IV) and also of the structural unit of formula (II) to the structural unit of formula (V) is in the range from 5:95 to 80:20, in particular in the range from 10:90 to 70:30, and in particular in the range from 15:85 to 60:40, or in the range from 1:99 to 70:30, in particular in the range from 5:95 to 60:40, more preferably in the range from 8:92 to 45:55, or in the range from 10:90 to 40:60, and in particular in the range from 12:88 to 30:70, or in the range from 12:88 to 20:80. Thus, the molar ratio of the structural units of the formula (II) is generally in the range from 1 to 70 mol%, in particular from 5 to 60 mol%, more preferably from 8 to 45 mol%, or in the range from 10 to 40 mol%, in particular from 12 to 30 mol%, or in the range from 15 to 30 mol%, in particular from 12 to 20 mol%, or in the range from 15 to 20 mol%, based on the total molar amount of the structural units of the formulae (II) and (V). Thus, the molar ratio of the structural units of the formula (V) is generally in the range from 30 to 99 mol%, in particular from 40 to 95 mol%, more preferably from 55 to 92 mol%, or in the range from 60 to 90 mol%, in particular from 70 to 88 mol%, or in the range from 70 to 85 mol%, in particular from 80 to 88 mol%, or in the range from 80 to 85 mol%, based on the total molar amount of the structural units of the formulae (II) and (V).

The thermoplastic copolymer resin of the present invention, for example, a polycarbonate resin, may include any one of a random copolymer structure, a block copolymer structure and an alternating copolymer structure. The thermoplastic resins of the present invention need not include all structural units (II) and one or more different structural units (V) in one and the same polymer molecule. That is, the thermoplastic copolymer resin according to the present invention may be a blend resin as long as the above-described structures are each included in any one of a plurality of polymer molecules. For example, the thermoplastic resin comprising all the structural units (II) and the structural units (V) described above may be a copolymer comprising all the structural units (II) and the structural units (V), it may be a mixture of a homopolymer and a copolymer comprising at least one structural unit (II) and a homopolymer or a copolymer comprising at least one structural unit (V), or it may be a blend resin comprising a copolymer comprising at least one structural unit (II) and a first structural unit (V) and a copolymer comprising at least one structural unit (II) and at least one other structural unit (V) different from the first structural unit (V); etc.

Thermoplastic polycarbonates are obtainable by polycondensation of a diol component and a carbonate-forming component. Similarly, thermoplastic polyesters and polyester carbonates may be obtained by polycondensation of a diol component and a dicarboxylic acid or an ester-forming derivative thereof and optionally a carbonate-forming component.

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

The method for producing the thermoplastic resin of the present invention, for example, a polycarbonate resin, includes a process of melt-polycondensing 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), (Ia-1) or (Ia-2), respectively, as defined herein. In addition to the compounds of formula (I), the dihydroxy compounds may also include one or more dihydroxy compounds represented by formula (IV), preferably by formulas (IV-1) to (IV-6), especially by formulas (IV-11) to (IV-20), more especially by formulas (IV-11), (IV-12), (IV-14), (IV-19 or (IV-20), and especially by formulas (IV-11), (IV-19) or (IV-20).

As is apparent from the foregoing, the polycarbonate resin may be formed by reacting a dihydroxy component with a carbonate precursor such as a carbonic acid diester, wherein the dihydroxy component comprises at least one compound represented by formulas (I), (Ia-1), and (Ia-2), respectively, or a combination of at least one compound represented by formulas (I), (Ia-1), and (Ia-2), respectively, and at least one compound represented by formulas (IV)、(IV-1)、(IV-2)、(IV-3)、(IV-4)、(IV-5)、(IV-6)、(IV-11)、(IV-12)、(IV-13)、(IV-14)、(IV-15)、(IV-16)、(IV-17)、(IV-18)、(IV-19) or (IV-20). Specifically, the polycarbonate resin may be formed by a melt polycondensation method in which a compound represented by the formulas (I), (Ia-1) and (Ia-2), respectively, or a combination thereof with at least one compound represented by the formula (IV)、(IV-1)、(IV-2)、(IV-3)、(IV-4)、(IV-5)、(IV-6)、(IV-11)、(IV-12)、(IV-13)、(IV-14)、(IV-15)、(IV-16)、(IV-17)、(IV-18)、(IV-19) or (IV-20) is reacted with a carbonate precursor such as a carbonic acid diester in the presence of a basic compound catalyst, a transesterification catalyst or a mixed catalyst thereof, or in the absence of a catalyst.

Thermoplastic resins (or polymers) other than polycarbonate resins, such as polyester carbonates and polyesters, are obtained by using as a material (or monomer) a dihydroxy compound represented by formulas (I), (Ia-1) and (Ia-2), 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-11)、(IV-12)、(IV-13)、(IV-14)、(IV-15)、(IV-16)、(IV-17)、(IV-18)、(IV-19) or (IV-20).

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

For example, a compound of formula (Ia-2) wherein X is C (CH ₃)₂) and R ¹ and R ² are both naphthalen-2-yl, i.e., the compound 2,2' - (propane-2, 2-diylbis { [2- (naphthalen-2-yl) -4, 1-phenylene ] oxy }) di (ethan-1-ol) represented by formula (Ia-2.3)

As impurities, one or more of the following compounds may be included, for example, which are presented in the routes below:

In particular, the total amount of impurities in the compound of formula (Ia-2.3) is preferably 1000ppm or less, more preferably 500ppm or less, still more preferably 200ppm or less, and particularly preferably 100ppm or less. The total content of dihydroxy compounds in which at least one of the groups Z ¹ or Z ² has a carbon number different from that of formula (Ia-2.3) is further preferably 50ppm or less, and more preferably 20ppm or less.

For example, monomers of formulas (IV-2) and (IV-3) (wherein R ^z is O-Alk ² -or O-Alk ²-[O-Alk²-]_p -) may include dihydroxy compounds wherein both R ^z are single bonds, or dihydroxy compounds wherein one of R ^z is a single bond instead of O-Alk ² -or O-Alk ²-[O-Alk²-]_p -.

Among the monomers having the dihydroxy compound represented by formula (IV-2) or (IV-3) as a main component, the total amount of these dihydroxy compounds of formula (IV-2) or (IV-3) (wherein at least one R ^z is different from O-Alk ² -or O-Alk ²-[O-Alk²-]_p -) is preferably 1000ppm or less, more preferably 500ppm or less, still more preferably 200ppm or less, and particularly preferably 100ppm or less. The total content of the dihydroxy compounds in which at least one of the values of c and d is different from the formula (IV-2) or (IV-3) is also preferably 50ppm or less, and more preferably 20ppm or less.

The polycarbonate resin may be obtained by reacting a monomer compound of formula (I) with a carbonate precursor such as a carbonate diester, or may be obtained by reacting, as a dihydroxy component, a combination of at least one monomer compound of formula (I), particularly at least one monomer (I) as referred to herein as preferred, and one or more monomer compounds of formula (IV), particularly a monomer compound of formula (V-11), (V-12), (V-14), (V-19), or (V-20), and particularly a monomer compound of formula (IV-11), (IV-19), or (IV-20), and the like, with a carbonate precursor such as a carbonate diester.

However, during the polymerization process for making polycarbonate resins, some compounds of formulas (I) and (IV) may be converted to impurities in which one or both of the terminal-Z ¹OH、-Z² OH or-R ^z OH groups are replaced with a different group, such as a vinyl end group represented by-och=ch ₂. Since the amount of such impurities is generally small, the polymer product formed can be used as a polycarbonate resin without the need for a purification process.

The thermoplastic resins of the present invention may also contain minor amounts of impurities, for example, as an additional content of the thermoplastic resin composition or as part of the polymer backbone of the thermoplastic resin. Examples of such impurities include phenol, unreacted carbonic acid diester, and monomer formed by the process used to form the thermoplastic resin. The total amount of impurities in the thermoplastic resin may be 5000ppm or less, or 2000ppm or less. The total amount of impurities in the thermoplastic resin is preferably 1000ppm or less, more preferably 500ppm or less, still more preferably 200ppm or less, and particularly preferably 100ppm or less.

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

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

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

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

The total amount of palladium remaining as an impurity in the thermoplastic resin is preferably 50ppm or less, more preferably 10ppm or less. The amount of residual palladium can be reduced by standard methods, such as treatment with an adsorbent, e.g., activated carbon.

By adjusting the amounts of phenol and carbonic acid diester, a resin having the desired properties can be formed. The amounts of phenol, carbonic acid diester and monomer can be suitably adjusted by adjusting the polycondensation conditions, the working conditions of the apparatus used for polymerization, and the extrusion molding conditions after the polycondensation process.

The weight average molecular weight (Mw) of the thermoplastic resin according to the invention, as determined by GPC (gel permeation chromatography), is preferably in the range of 5000 to 100000 daltons, more preferably in the range of 10000 to 80000 daltons, still more preferably in the range of 10000 to 50000 daltons, especially in the range of 15000 to 50000 daltons. GPC measurements can be calibrated by using polystyrene as a standard. The Mw of the thermoplastic resin of the present invention measured in this way can also be expressed herein as "Mw in terms of polystyrene", or "Mw based on polystyrene measured by GPC". The number average molecular weight (Mn) of the thermoplastic resin of the present invention is preferably 3000 to 20000, more preferably 5000 to 15000, still more preferably 7000 to 14000.Mn can be determined similarly to Mw by GPC measurement calibrated against polystyrene as described below. The viscosity average molecular weight (Mv) of the thermoplastic resin according to the present invention is preferably in the range of 8000 to 20000, more preferably 9000 to 15000, still more preferably 10000 to 14000.

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

When the thermoplastic resin has a weight average molecular weight (Mw) value within the above-described suitable range, a molded article made of the thermoplastic resin has high strength. In addition, such a thermoplastic resin having an appropriate Mw value is advantageous for molding due to its excellent flowability.

In a specific set of embodiments, the thermoplastic resins of the present invention comprise 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.% of low molecular weight compounds having a molecular weight Mw of less than 1000, based on the total weight of the thermoplastic resin. The upper limit of the content of the low molecular weight compound having a Mw of less than 1000 is usually 7.0 wt%, preferably 5.0 wt%, more preferably 3.0 wt%, even more preferably 2.0 wt%, particularly 1.8 wt%, and particularly 1.7 wt%. Thus, in this particular set of embodiments, the content of low molecular weight compounds having a molecular weight Mw of less than 1000 in the thermoplastic resin is generally in the range from 0.3 to 7.0% by weight, preferably in the range from 0.5 to 5.0% by weight, more preferably in the range from 0.8 to 3.0% by weight, even more preferably in the range from 1.0 to 2.0% by weight, in particular in the range from 1.0 to 1.8% by weight, in particular in the range from 1.0 to 1.7% by weight, based in each case on the total weight of the thermoplastic resin. The low molecular weight compound may be present in an amount of less than 1.8 wt%, less than 1.7 wt%, or less than 1.7 wt% based on the total weight of the resin.

The thermoplastic resin of the present invention comprising a low molecular weight compound having a Mw value of less than 1000 and a content within the above-mentioned range forms a molded body having high mechanical strength. Such thermoplastic resins are particularly free or less prone to separation or precipitation of the low molecular weight compounds, also known as exudation, during molding processes such as injection molding processes. In addition, the thermoplastic resins of the present invention containing the low molecular weight compounds in the amounts defined above have the advantageous properties of high molding speed and reduced energy requirements of the molding process due to their high plasticity.

The content of the low molecular weight compound in the thermoplastic resin was determined based on the above-described chart of GPC analysis. Specifically, the content is calculated as a ratio of the total area of peaks of the low molecular weight compound to the total area of all peaks of the map obtained by GPC analysis of the thermoplastic resin. Accordingly, the content (CLWC) of the low molecular weight compound in the thermoplastic resin is represented by the following formula:

The polycarbonate resin has a high refractive index (n _D or n _d) and is therefore suitable for optical lenses. The refractive index value referred to herein is a value of a film having a thickness of 0.1mm, which can be measured by a method according to JIS-K-7142 using an Abbe refractometer. When the resin includes the structural unit (2), the refractive index of the polycarbonate resin according to the present invention at 23℃at a wavelength of 589nm is usually 1.640 or more, preferably 1.650 or more, more preferably 1.660 or more, still more preferably 1.670 or more, particularly 1.680 or more. For example, the refractive index of the copolycarbonate resin comprising the structural unit (2) and the structural unit (V) according to the present invention is preferably 1.660 to 1.720, more preferably 1.670 to 1.720, and particularly 1.680 to 1.720.

The Abbe number (. Nu.) of the polycarbonate resin is preferably 24 or less, more preferably 20 or less, still more preferably 18 or less. The Abbe number can be calculated by the following formula based on refractive indices at wavelengths of 487nm, 589nm and 656nm at 23 ℃.

ν＝(n_D-1)/(n_F-n_C)

N _D: refractive index at wavelength 589nm

N _C: refractive index at 656nm

N _F: refractive index at wavelength 486nm

In view of the fact that polycarbonates are useful for injection molding, the glass transition temperature (Tg) of the polycarbonate resin as an example of the thermoplastic resin according to the present invention is preferably 90 to 185 ℃, more preferably 125 to 175 ℃, and still more preferably 140 to 165 ℃. The lower limit of Tg is preferably 130 ℃, more preferably 135 ℃, and the upper limit of Tg is preferably 185 ℃, more preferably 175 ℃, in terms of molding flowability and molding heat resistance. Glass transition temperatures (Tg) within the above given ranges provide a significant range of useful temperatures and avoid the risk that the melting temperature of the resin may be too high and thus the resin may undesirably decompose or stain. In addition, it allows the preparation of molded articles (molds) having high surface accuracy.

In a preferred embodiment of group (10), the absolute value of the orientation birefringence of the thermoplastic resin is preferably in the range of 0 to 1x10 ^-2, more preferably in the range of 0 to 5x10 ^-3, even more preferably in the range of 0 to 2x10 ^-3, especially in the range of 0 to 1x10 ^-3, and especially in the range of 0 to 0.4x10 ^-3.

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

The thermoplastic resin of the present invention has high moisture and heat resistance. The moisture resistance and heat resistance can be evaluated by performing "PCT test" (autoclave test) on a molded body such as an optical element made of a thermoplastic resin, and then measuring the total light transmittance of the molded body after the PCT test. In the PCT test, first, an injection-molded article having a diameter of 50mm and a thickness of 3mm was held with PC305S III manufactured by HIRAYAMA Corporation for 20 hours, and the resultant was subjected to conditions of 120℃and 0.2MPa and 100% RH for 20 hours. Then, a sample of the injection molded body was taken out of the apparatus, and total light transmittance was measured according to the method of JIS-K-7361-1 using a model SE2000 spectroparallax instrument manufactured by Nippon Denshoku Industries Co., ltd.

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

The b value of the thermoplastic resin according to the present invention, which represents the hue (hue), is preferably 5 or less. The smaller the b value, the less yellow the color, which is good as a hue.

According to the invention, the diol component used for the preparation of the polycarbonate or polyester may additionally comprise one or more diol monomers which are different from the monomer compounds of formula (I), for example one or more monomers of formula (IV).

Suitable diol monomers other than the monomer compounds of formula (I) are those conventionally used in the preparation of polycarbonates, e.g.

Aliphatic diols, such as ethylene glycol, propylene glycol, butylene glycol, pentylene glycol and hexylene glycol;

Alicyclic diols such as tricyclo [5.2.1.02,6] decanedimethanol, cyclohexane-1, 4-dimethanol, decalin-2, 6-dimethanol, norbornanedimethanol, pentacyclopentadecane-dimethanol, cyclopentane-1, 3-dimethanol, spiroglycol, 1,4:3, 6-dianhydro-D-sorbitol, 1,4:3, 6-dianhydro-D-mannitol and 1,4:3, 6-dianhydro-L-iduronate are also included in the examples of diols; and

Aromatic diols, in particular of the formula (IV), such as bis (4-hydroxyphenyl) methane, 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-bis (4-hydroxyphenyl) propane, 2-bis (4-hydroxy-3-tert-butylphenyl) propane 2, 2-bis (4-hydroxy-3-methylphenyl) propane, 1-bis (4-hydroxyphenyl) cyclopentane, 1-bis (4-hydroxyphenyl) cyclohexane, 2-bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxyphenyl) diphenylmethane, 1-bis (4-hydroxyphenyl) -1-phenylethane, alpha, omega-bis [2- (p-hydroxyphenyl) ethyl ] polydimethylsiloxane, alpha, omega-bis [3- (o-hydroxyphenyl) propyl ] polydimethylsiloxane, 4' - [1, 3-phenylenebis (1-methylethylidene) hydroxyphenyl ] -1-phenylethane, 9-bis (4-hydroxyphenyl) fluorene, 9, 9-bis [4- (2-hydroxyethoxy) -3-methylphenyl ] fluorene, 9-bis [4- (2-hydroxyethoxy) -3-tert-butylphenyl ] fluorene, 9-bis [4- (2-hydroxyethoxy) -3-isopropylphenyl ] fluorene, 9-bis [4- (2-hydroxyethoxy) -3-cyclohexylphenyl ] fluorene, 9-bis (4-hydroxy-3-phenylphenyl) fluorene, 9-bis (4- (2-hydroxyethyl) phenyl) fluorene 9, 9-bis (4- (2-hydroxyethyl) -3-phenylphenyl) fluorene, 9-bis (6-hydroxy-2-naphthyl) fluorene, 9-bis (6- (2-hydroxyethyl) -2-naphthyl) fluorene, 10-bis (4-hydroxyphenyl) anthracene-9-one, 10-bis (4- (2-hydroxyethyl) phenyl) anthracene-9-one 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).

Preferably, the diol component comprises at least one monomer of formula (IV) in addition to the monomer of formula (I). In particular, the total amount of monomers of formulas (I) and (IV) contributes to the glycol component by at least 90% by weight based on the total weight of the glycol component, or the total molar amount of glycol monomers based on the glycol component is at least 90 mole%. In particular, the diol component comprises, in addition to the monomers of formula (I), at least one monomer selected from the group consisting of the monomers of formulae (IV-11) to (IV-20). More particularly, the diol component comprises, in addition to the monomers of formula (I), at least one monomer selected from the group consisting of the monomers of formulas (IV-11), (IV-12), (IV-14), (IV-19) and (IV-20). In particular, the diol component comprises, in addition to the monomers of formula (I), at least one monomer selected from the group consisting of 2,2' -bis (2-hydroxyethoxy) -1,1' -binaphthyl, 2' -bis (2-hydroxyethoxy) -6,6' -diphenyl-1, 1' -binaphthyl, 9-bis (6- (2-hydroxyethoxy) -2-naphthyl) fluorene, 9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, and 9, 9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene, and combinations thereof.

Generally, the relative amount of the monomer compounds of formula (I) is at least 1 wt.%, preferably at least 2 wt.%, or at least 5 wt.%, especially at least 8 wt.%, or at least 10 wt.%, especially at least 12 wt.%, or at least 15 wt.%, preferably in the range of 1-90 wt.%, or in the range of 5-90 wt.%, especially in the range of 2-80 wt.%, or in the range of 5-80 wt.%, or in the range of 8-80 wt.%, or in the range of 10-80 wt.%, especially in the range of 5-70 wt.%, or in the range of 8-70 wt.%, or in the range of 10-70 wt.%, or in the range of 15-70 wt.%, but may also be up to 100 wt.%, based on the total weight of the glycol component.

Generally, the relative molar amount of the monomer compounds of formula (I) is at least 1 mole%, preferably at least 2 mole%, or at least 5 mole%, especially at least 8 mole%, or at least 10 mole%, and especially at least 12 mole%, or at least 15 mole%, preferably in the range of 1 to 80 mole%, or in the range of 2 to 80 mole%, or in the range of 5 to 80 mole%, or in the range of 8 to 80 mole%, especially in the range of 2 to 70 mole%, or in the range of 5 to 70 mole%, or in the range of 8 to 70 mole%, or in the range of 10 to 70 mole%, especially in the range of 5 to 60 mole%, or in the range of 8 to 60 mole%, or in the range of 10 to 60 mole%, or in the range of 12 to 60 mole%, or in the range of 15 to 60 mole%, but may also be up to 100 mole%, based on the total moles of the diol component.

Thus, the relative molar amount of the monomer compounds of formula (IV) will not exceed 99 mole% or 98 mole% or 95 mole%, especially not exceed 92 mole% or 90 mole%, and especially not exceed 88 mole% or 85 mole%, and preferably be in the range of 20-99 mole%, or in the range of 20-98 mole%, or in the range of 20-95 mole%, or in the range of 20-92 mole%, especially in the range of 30-98 mole%, or in the range of 30-95 mole%, or in the range of 30-92 mole%, or in the range of 30-90 mole%, especially in the range of 40-95 mole%, or in the range of 40-92 mole%, or in the range of 40-90 mole%, or in the range of 40-88 mole%, or in the range of 40-85 mole%, but may also be up to 99.9 mole%, based on the total moles of the diol component.

Typically, the total molar amount of monomer of formula (I) and monomer of formula (IV) is at least 80 mole%, especially at least 90 mole%, especially at least 95 mole%, or at most 100 mole%, based on the total molar amount of diol monomers in the diol component.

Examples of further preferred aromatic dihydroxy compounds that may be used in addition to the monomers of formula (I) and optionally the monomers of formula (IV) include, but are not limited to, bisphenol a, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, bisphenol Z, and the like.

For the purpose of adjusting the molecular weight and melt viscosity, the monomers forming the thermoplastic polymer may also comprise monofunctional compounds, in the case of polycarbonates, monofunctional alcohols, in the case of polyesters, monofunctional alcohols or monofunctional carboxylic acids. Suitable monohydric alcohols are butanol, hexanol and octanol. Suitable monocarboxylic acids include, for example, benzoic acid, propionic acid, and butyric acid. In order to increase the molecular weight and melt viscosity, the thermoplastic polymer-forming monomers may also include a polyfunctional compound, in the case of polycarbonate, a polyfunctional alcohol having three or more hydroxyl groups, in the case of polyester, a polyfunctional alcohol having three or more hydroxyl groups, or a polyfunctional carboxylic acid having three or more carboxyl groups. Suitable polyfunctional alcohols are, for example: glycerol, trimethylolpropane, pentaerythritol and 1,3, 5-trihydroxypentane. Suitable polyfunctional carboxylic acids having three or more carboxyl groups are, for example: trimellitic acid and pyromellitic acid. The total amount of these compounds is generally not more than 10 mole% based on the molar amount of the diol component.

Suitable carbonate-forming monomers are those conventionally used as carbonate-forming monomers in the preparation of polycarbonates, which include, but are not limited to, phosgene, diphosgene, and diesters of carbonic acid 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 preferable. The proportion of the carbonate-forming monomer to be used is usually 0.97 to 1.20 mol, more preferably 0.98 to 1.10 mol, relative to 1mol of the total dihydroxy compound.

Suitable dicarboxylic acids include, but are not limited to

Aliphatic dicarboxylic acids, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid;

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

Aromatic dicarboxylic acids, such as phthalic acid, in particular phthalic acid, isophthalic acid, 2-methyl terephthalic 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 DC 1), 2- [9- (carboxymethyl) fluoren-9-yl ] propionic acid (formula DC 2), 2 '-bis (carboxymethoxy) -1,1' -binaphthyl (formula DC 3) and naphthalene-2, 7-dicarboxylic acid.

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

In the case of the 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.

The polycarbonates of the invention may be prepared by reacting a diol component comprising a monomer of formula (I) and optionally further diol monomers, e.g. monomers of formula (IV), with carbonate forming monomers in a similar preparation process to the preparation of known polycarbonates as described, for example, in US 9,360,593, US2016/0319069 and US2017/0276837, which are fully incorporated herein by reference.

The polyesters of the invention may be prepared by reacting a diol component comprising a monomer of formula (I) and optionally a further diol monomer, e.g. a monomer of formula (IV), with a dicarboxylic acid or an ester forming derivative thereof, in a similar preparation process to the preparation of known polyesters as described for example in US2017/044311 and the documents cited therein, which are fully incorporated herein by reference.

The polyester carbonates of the present invention may be prepared by reacting a diol component comprising the monomer of formula (I) and optionally further diol monomers such as the monomer of formula (IV), a carbonate forming monomer and a dicarboxylic acid or an ester forming derivative thereof by a process similar to the preparation of polyester carbonates known in the art.

In the case of using carbonate-forming monomers or ester-forming derivatives of polycarboxylic acids, polycarbonates, polyesters and polyester carbonates are generally prepared by the following methods: the monomers of the diol component are reacted 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, in particular a transesterification catalyst.

Suitable transesterification catalysts are basic compounds, which include, but are not limited to, inter alia, alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, and the like. Similarly, suitable transesterification catalysts are acidic compounds, which include, but are not limited to, lewis acid compounds of polyvalent metals, including compounds such as zinc, tin, titanium, zirconium, lead, and the like, among others.

Examples of suitable alkali metal compounds include alkali metal salts of organic acids such as acetic acid, stearic acid, benzoic acid or phenylphosphoric acid, alkali metal phenoxide salts, alkali metal oxides, alkali metal carbonates, alkali metal borohydrides, alkali metal hydrogencarbonates, alkali metal phosphates, alkali metal hydrogenphosphates, alkali metal hydroxides, alkali metal hydrides, alkali metal alkoxides, and the like. Specific examples thereof include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium borophenolate (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, dipotassium, cesium, dilithium, sodium, potassium, cesium and lithium salts of bisphenol A; etc.

Examples of the alkaline earth metal compound include alkaline earth metal salts of organic acids such as acetic acid, stearic acid, benzoic acid or phenylphosphoric acid, alkaline earth metal phenoxide, alkaline earth metal oxide (ALKALINE EARTH METAL EARTH oxide), alkaline earth metal carbonate, alkali metal borohydride, alkaline earth metal hydrogencarbonate, alkaline earth metal hydroxide, alkaline earth metal hydride, alkaline earth metal alkoxide, and the like. Specific examples thereof include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium bicarbonate, calcium bicarbonate, strontium bicarbonate, barium bicarbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium benzoate, magnesium phenylphosphate, and the like.

Examples of the nitrogen-containing compound include quaternary ammonium hydroxides, salts thereof, amines, and the like. Specific examples thereof include: quaternary ammonium hydroxides containing alkyl, aryl, etc., such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzyl ammonium hydroxide, etc.; tertiary amines such as triphenylamine, dimethylbenzylamine, triphenylamine, and the like; secondary amines such as diethylamine, dibutylamine, etc.; primary amines such as propylamine, butylamine, and the like; imidazoles such as 2-methylimidazole, 2-phenylimidazole, benzimidazole, and the like; a base or basic salt such as ammonia, tetramethylammonium borohydride, tetrabutylammonium tetraphenylborate, tetraphenylammonium tetraphenylborate, and the like.

Preferred examples of the transesterification catalyst include salts of polyvalent metals such as zinc, tin, titanium, zirconium, lead and the like, particularly chlorides, alkoxides, alkanoates, benzoates, acetylacetonates and the like. They may be used singly or in combination of two or more. Specific examples of such transesterification catalysts include zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin (II) chloride, tin (IV) chloride, tin (II) acetate, tin (IV) acetate, dibutyltin laurate, dibutyltin oxide, dibutyltin methoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead (II) acetate, lead (IV) acetate, and the like.

The transesterification catalyst is used in a proportion of usually 10 ^-9 to 10 ^-3 mol, preferably 10 ^-7 to 10 ^-4 mol, relative to 1 mol of the total dihydroxy compound.

In general, polycarbonates, polyesters and polyester carbonates are prepared by melt polycondensation processes. In melt polycondensation, monomers are reacted in the absence of additional inert solvents. Any by-products formed in the transesterification reaction are removed by heating the reaction mixture at ambient or reduced pressure while the reaction is being carried out.

The melt polycondensation reaction preferably comprises loading monomers and catalyst into a reactor and subjecting the reaction mixture to conditions wherein reaction between the monomers and formation of byproducts occurs. It has been found to be advantageous if the by-products remain in the polycondensation reaction for at least a period of time. However, in order to drive the polycondensation reaction to the product side, it is advantageous to remove at least a portion of the by-products formed during the polycondensation reaction or preferably at the end thereof. To allow byproducts to enter the reaction mixture, the pressure may be controlled by closing the reactor or by increasing or decreasing the pressure. The reaction time in this step is 20 minutes to 240 minutes, preferably 40 minutes to 180 minutes, and particularly preferably 60 minutes to 150 minutes. In this step, in the case where the by-product is removed by distillation soon after the production, the finally obtained thermoplastic resin has a low content of high molecular weight resin molecules. In contrast, in the case where the by-product is allowed to stay in the reactor for a certain time, the finally obtained thermoplastic resin has a high content of high molecular weight resin molecules.

The melt polycondensation reaction may be carried out in a continuous system or a batch system. The reactors which can be used for the reaction can be vertical and comprise anchor stirring blades,Stirring blades, helical ribbon stirring blades, etc.; horizontal, including paddle blades, grating blades, eyeglass type blades, etc.; or of the extruder type, including screws. In view of the viscosity of the polymerization product, a reactor comprising a combination of these reactors is preferably used.

According to the method for producing a thermoplastic resin such as a polycarbonate resin, after the polymerization reaction is completed, the catalyst may be removed or deactivated to maintain thermal stability and hydrolytic stability. The preferred method for deactivating the catalyst is to add an acidic substance. Specific examples of the acidic substance include esters such as butyl benzoate and the like; aromatic sulfonic acids (aromatic sulfonates), such as p-toluene sulfonic acid, and the like; aromatic sulfonates such as butyl p-toluenesulfonate, hexyl p-toluenesulfonate and the like; phosphoric acids, such as phosphorous acid, phosphoric acid, phosphonic acid, and the like; 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, and the like; phosphates such as triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, dibutyl phosphate, dioctyl phosphate, monooctyl phosphate and the like; phosphonic acids, such as diphenylphosphonic acid, dioctylphosphonic acid, dibutylphosphonic acid, and the like; phosphonates such as diethyl phenylphosphonate and the like; phosphines, such as triphenylphosphine, bis (diphenylphosphino) ethane, and the like; boric acids such as boric acid, phenylboric acid, and the like; aromatic sulfonates such as tetrabutylphosphonium dodecylbenzene sulfonate and the like; organic halides such as stearyl chloride (chloride stearate), benzoyl chloride, p-toluenesulfonic chloride (chloride p-toluenesulfonate), and the like; alkyl sulfonic acids such as dimethyl sulfonic acid and the like; organic halides such as benzyl chloride and the like. The amount of these deactivators used is generally from 0.01 to 50mol, preferably from 0.3 to 20mol, relative to the catalyst. After deactivation of the catalyst, there may be a step of removing low boilers from the polymer by distillation. The distillation is preferably carried out under reduced pressure, for example at a pressure of from 0.1 to 1mm Hg, at a temperature of from 200 to 350 ℃. For this step, a horizontal type apparatus including stirring blades having a high surface renewal capacity such as paddle blades, grating blades, spectacle blades, or the like, or a thin film evaporator is preferably used.

Desirably, thermoplastic resins such as polycarbonate resins have very small amounts of foreign matter. Thus, 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 6 or less, more preferably 5 or less.

The thermoplastic resin may 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 processing, extrusion molding, stretching, and the like.

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

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 (phospha-phospha), 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-hydroxyphenyl) benzene, N, 5-di-hydroxybenzyl) benzene, N-di-tert-butyl-2 (3H) -one, 5, 7-di-tert-butyl-3- (3, 4-dimethylphenyl) benzofuran-2 (3H) -one, 5-di-tert-butyl-hydroxy-4-hydroxybenzyl) amide, N, 5-di-hydroxybenzyl) amide Tris (3, 5-di-t-butyl-4-hydroxybenzyl) isocyanurate and 3, 9-bis {1, 1-dimethyl-2- [ β - (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] ethyl } -2,4,8, 10-tetraoxaspiro (5, 5) undecane, and the like. Of 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.

Examples of process stabilizers include, but are not limited to, phosphorus-based process stabilizers, sulfur-based process stabilizers, and the like. Examples of phosphorus-based processing stabilizers include phosphorous acid, phosphoric acid, phosphorous acid, phosphonic acid, esters thereof, and the like. Specific examples thereof include triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2, 4-di-t-butylphenyl) phosphite, tris (2, 6-di-t-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-t-butyl-4-methylphenyl) pentaerythritol diphosphite, 2-methylenebis (4, 6-di-t-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl mono-o-diphenyl 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-t-butylphenyl) -4-phenyl-phenylphosphinate, bis (2, 4-di-t-butylphenyl) -3-phenyl-phenylphosphinate, 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.

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, dimyristoyl-3, 3' -thiodipropionate, distearyl-3, 3' -thiodipropionate, and the like. 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.

Preferred release agents contain at least 90% by weight of esters of alcohols and fatty acids. Specific examples of esters of alcohols and fatty acids include esters of monohydric alcohols and fatty acids, and partial or complete esters of polyhydric alcohols and fatty acids. Preferred examples of the above esters of alcohols and fatty acids include esters of monohydric alcohols having 1 to 20 carbon atoms and saturated fatty acids having 10 to 30 carbon atoms. Preferred examples of the partial or complete esters of the polyhydric alcohol and the fatty acid include partial or complete esters of the polyhydric alcohol having 2 to 25 carbon atoms and the saturated fatty acid having 10 to 30 carbon atoms. Specific examples of esters of monohydric alcohols and fatty acids include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, and the like. Specific examples of partial or complete esters of polyols and fatty acids include glyceryl monostearate, glyceryl distearate, glyceryl stearate, glyceryl monostearate, glyceryl behenate, caprylate, lauric acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrasonanoate, propylene glycol monostearate, biphenyl diphenol ester (biphenyl biphenate), sorbitan monostearate, 2-ethylhexanol stearate, full or partial esters of dipentaerythritol, such as dipentaerythritol hexastearate, and the like. 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, still more preferably 0.02 to 0.5 parts by weight, relative to 100 parts by weight of the thermoplastic resin.

Preferred ultraviolet absorbers are selected from the group consisting of benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, cyclic imidoester-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers. That is, the following ultraviolet absorbers may be used singly or in combination of two or more.

Examples of benzotriazole-based ultraviolet absorbers include 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2' -methylenebis [4- (1, 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) -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' -methylenebis (4-cumyl-6-benzotriazolophenyl), 2' -p-phenylenebis (1, 3-benzoxazin-4-one), 2- [ 2-hydroxy-3- (3, 4,5, 6-tetrahydrophthalimidomethyl) -5-methylphenyl ] benzotriazole, and the like.

Examples of the benzophenone-type ultraviolet absorbers include 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxy-benzophenone, 2-hydroxy-4-methoxy-5-sulfinyloxy (sulfoxy) benzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid hydrate, 2 '-dihydroxy-4-methoxybenzophenone, 2',4 '-tetrahydroxybenzophenone, 2' -dihydroxy-4, 4 '-dimethoxybenzophenone, sodium 2,2' -dihydroxy-4, 4 '-dimethoxy-5-sulfoxylate (sodiumsulfoxy) benzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2' -carboxybenzophenone, and the like.

Examples of the triazine-based ultraviolet light 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.

Examples of the cyclic imidoester ultraviolet absorbers include 2,2 '-bis (3, 1-benzoxazin-4-one), 2' -p-phenylenebis (3, 1-benzoxazin-4-one), 2 '-m-phenylenebis (3, 1-benzoxazin-4-one), 2' - (4, 4 '-biphenylene) bis (3, 1-benzoxazin-4-one), 2' - (2, 6-naphtalene) bis (3, 1-benzoxazin-4-one), and 2,2'- (1, 5-naphthalene) bis (3, 1-benzoxazin-4-one), 2' - (2-methyl-p-phenylene) bis (3, 1-benzoxazin-4-one), 2'- (2-nitro-p-phenylene) bis (3, 1-benzoxazin-4-one), 2' - (2-chloro-p-phenylene) bis (3, 1-benzoxazin-4-one), and the like.

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.

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, still 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 such a content range can provide sufficient weatherability to the thermoplastic resin according to the use.

As described above, thermoplastic polymer resins, particularly polycarbonate resins, comprising repeating units of formulae (II), (IIa-1) and (IIa-2), 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 precisely, thermoplastic polycarbonates having structural units of the formulae (II), (IIa-1) and (IIa-2), respectively, are distinguished by a high refractive index, preferably at least 1.660, more preferably at least 1.680, in particular at least 1.690.

The contribution of the monomers of formulae (I), (Ia-1) and (Ia-2), respectively, to the refractive index of the thermoplastic resin, especially the polycarbonate resin, depends on the refractive index of the monomers and the relative amounts of the monomers in the thermoplastic resin. In general, the higher the refractive index of the monomer contained in the thermoplastic resin, the higher will be the refractive index of the resulting thermoplastic resin. In addition to this, the refractive index of the thermoplastic resin comprising the structural unit of formula (II) may be calculated from the refractive index of the monomer used to prepare the thermoplastic resin, from the refractive index of the monomer or from scratch, for example by using computer software ACD/ChemSketch 2012 (ADVANCED CHEMISTRY Development, inc.).

In the case of thermoplastic copolymer resins, the refractive index of the thermoplastic resin, particularly polycarbonate resin, can be calculated from the refractive index of the homopolymer of each monomer forming the copolymer resin by the following so-called "Fox equation":

1/n_D＝x₁/n_D1+x₂/n_D2+....x_n/n_Dn，

Where n _D is the refractive index of the copolymer, x ₁、x₂....x_n is the mass fraction of monomers 1, 2..n in the copolymer, and n _D1、n_D2....n_Dn is the refractive index of a homopolymer synthesized from only one of monomers 1, 2..n. In the case of polycarbonates, x ₁、x₂....x_n is the mass fraction of OH monomers 1, 2..n based on the total amount of OH monomers. Obviously, the higher the refractive index of the homopolymer will result in a higher refractive index of the copolymer.

The refractive index of the thermoplastic resin may be measured directly or indirectly. For direct measurement, the refractive index n _D of the thermoplastic resin was measured at a wavelength of 589nm using an Abbe refractometer and applying a thermoplastic resin film of 0.1mm according to JIS-K-7142 protocol. In the case of the refractive index of the homopolycarbonates of the compounds of the formula (I), the refractive index can also be determined indirectly. For this purpose, copolycarbonates of the respective 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 U.S. Pat. No. 3, 9,360,593, and refractive index n _D of the copolycarbonates was measured at a wavelength of 589nm according to the protocol of JIS-K-7142 using an Abbe refractometer and applying a 0.1mm copolycarbonate film. From the refractive index n _D thus measured, the refractive index of the homopolycarbonate of the corresponding monomer can be calculated by applying Fox equation and the known refractive index of 9, 9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (n _D (589 nm) = 1.639).

As previously mentioned, compounds of formula (I) without some of the color imparting groups, e.g., R ¹、R²、R³、R⁴ and Ar ¹ groups, may also be obtained in a purity that provides a low yellowness index y.i. as measured according to ASTM E313, which may also be important for the use in preparing optical resins.

More precisely, the compounds of formula (I) preferably have a yellowness index y.i. measured according to ASTM E313 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.

The thermoplastic resin according to the present invention has a high refractive index and a low abbe number. The thermoplastic resin of the present invention can be used for manufacturing a transparent conductive substrate useful for liquid crystal displays, organic EL displays, solar cells, and the like. In addition, the thermoplastic resin of the present invention can be used as a structural material for optical components such as optical discs, liquid crystal panels, optical cards, optical sheets, optical fibers, connectors, evaporating plastic mirrors, displays, and the like; or as an optical device suitable for functional material applications.

Accordingly, a molded article such as an optical device can be formed using the thermoplastic resin of the present invention. The optical device includes an optical lens and an optical film. Specific examples of the optical device include lenses, films, mirrors, filters, prisms, and the like. These optical devices may be formed by any manufacturing process, for example, by injection molding, compression molding, injection compression molding, extrusion molding, or solution casting.

The thermoplastic resin of the present invention is very suitable for manufacturing optical lenses requiring injection molding due to excellent moldability and high heat resistance. For molding, the thermoplastic resin of the present invention such as a polycarbonate resin may be used as a mixture with other thermoplastic resins such as a different polycarbonate resin, a polyester carbonate resin, a polyester resin and others.

In addition, the thermoplastic resin of the present invention may be mixed with additives for forming optical devices. As the additive for forming the optical device, the above-described additives can be used. Additives may include antioxidants, processing stabilizers, light stabilizers, polymeric metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, antimicrobial agents, mold release agents, ultraviolet light absorbers, plasticizers, compatibilizers, and the like.

As is apparent from the above, another aspect of the present invention relates to an optical device made of the thermoplastic resin as defined above, wherein the thermoplastic resin 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 the formulae (II) and (V), reference is made to the description given above.

The optical devices made from the optical resins comprising the repeating units of formula (II) and optionally (V) as defined herein are typically optical shaped articles such as optical lenses, e.g. automotive headlamp lenses, fresnel lenses, fθ lenses for laser printers, camera lenses, lenses for eyes and projection lenses for rear projection televisions, CD-ROM pick-up lenses, as well as 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, deposited (eposition) plastic mirrors, etc. Optical lenses and optical films are particularly preferred here. The optical resin comprising the repeating unit of formula (II) and optionally the repeating unit of formula (V) can also be used to manufacture transparent conductive substrates useful in optical devices suitable for use as structural or functional elements of transparent conductive substrates for liquid crystal displays, organic EL displays, solar cells, and the like.

The optical lens manufactured from 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 resistance and heat resistance. Therefore, the optical lens can be used in the field of conventionally using expensive glass lenses having a high refractive index, for example, in telescopes, binoculars, television projectors, and the like. Preferably, the optical lens is used in the form of an aspherical lens. Only one aspherical lens can make the spherical aberration substantially zero. Therefore, it is not necessary to use a plurality of spherical lenses to eliminate spherical aberration. Accordingly, the weight and manufacturing cost of the device including spherical aberration are reduced. Among various types of optical lenses, an aspherical lens is particularly useful as a camera lens. The present invention readily provides aspherical lenses with high refractive index and low level of birefringence that are technically difficult to manufacture by processing glass.

The optical lens of the present invention may be formed, for example, by 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.

The optical lens of the present invention is characterized by small optical distortion. Optical lenses including conventional optical resins have large optical distortions. Although it is not impossible to reduce the value of the optical distortion by molding conditions, the condition width is very small, making molding extremely difficult. Since the resin having the repeating unit of formula (II) and optionally the repeating unit of formula (V) as defined herein has extremely small optical distortion caused by resin orientation and small molding distortion, excellent optical elements can be obtained without strictly setting molding conditions.

In order to manufacture the optical lens of the present invention by injection molding, it is preferable that the lens is molded at a cylinder temperature of 260 to 320 ℃ and a mold temperature of 100 to 140 ℃.

The optical lens of the present invention is advantageously used as an aspherical lens as required. Since spherical aberration can be substantially eliminated with a single aspherical lens, there is no need to eliminate spherical aberration with a combination of spherical lenses, resulting in reduced weight and manufacturing costs. Therefore, among the optical lenses, an aspherical lens can be used particularly as a camera lens.

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

The surface of the optical lens of the present invention may have a coating layer, such as an antireflection layer or a hard coating layer, as required. The antireflection layer may be a single layer or a plurality of layers, and is composed of an organic material or an inorganic material, but is preferably composed of an inorganic material. Examples of the inorganic material include oxides and fluorides such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, magnesium oxide, and magnesium fluoride.

The optical lens of the present invention may be formed by any method such as metal molding, cutting, polishing, laser processing, electric discharge processing, or edging. Preferably metal forming.

The optical film manufactured using the thermoplastic resin according to the present invention has high transparency and heat resistance, and thus is preferably used for a liquid crystal substrate film, an optical memory card, and the like. Needless to say, in order to avoid incorporation of foreign matters into the optical film as much as possible, the molding needs to be performed in a low-dust environment. The dust environment is preferably 6 or less, more preferably 5 or less.

The following examples serve as further illustrations of the invention.

1. Abbreviations:

m.p.: melting point

RT: room temperature

THF: tetrahydrofuran (THF)

TLC: thin layer chromatography

2. Preparation of monomers of formula (I)

2.1 Analysis in relation to monomers of formula (I):

¹ H-NMR spectrum was measured at 23℃using an 80MHz NMR spectrometer (Magritek Spinsolve 80). Unless otherwise indicated, the solvent was CDCl ₃.

IR spectra were recorded by ATR FT-IR using a Shimadzu FTIR-8400S spectrometer (scan number: 45, resolution 4cm ^-1; apodization: happ-Genzel).

DSC (differential scanning calorimetry) measurements were performed using LINSEIS CHIP-DSC 10.

The melting Point of the compound is determined by Bu CHI MELTING Point B-545.

UPLC (ultra high performance liquid chromatography) analysis was performed using the following system and conditions:

Waters Acquity UPLC H-Class system; column: acquity UPLC BEH C18,1.7 μm,2.1x 100mm; column temperature: 25 ℃, gradient: acetonitrile/water: acetonitrile 80% at 0 min; 100% at 4.0 min; 100% at 6.0 min; 80% at 6.1 min; 80% at 8.0 min); sample injection amount: 2.0 μl; run time: 8min; detection was at 210 nm.

The yellowness index YI of a compound of formula (I) can be determined by a protocol similar to ASTM E313 using the following protocol: 1g of a compound of formula (I) is dissolved in 19g of a solvent, for example methanol or dichloromethane. The solution was transferred to a 50mm cuvette and the transmittance was determined by Shimadzu ultraviolet visible spectrophotometer UV-1900 in the range of 300 to 800 nm. The solvent itself (e.g., methanol) is used as a reference. From this spectrum, the yellowness index can be calculated using the software "RCA-software UV2DAT" according to ASTM E308 (standard practice of calculating object colors using the CIE system) and ASTM E313 (standard practice of calculating yellowness and whiteness index from instrumentally measured color coordinates).

2.2 Preparation examples:

example 1:2- [4- [1- [4- (2-hydroxyethoxy) -3, 5-diphenyl-phenyl ] -1-methyl-ethyl ] -2, 6-diphenyl-phenoxy ] ethanol (compound of formula (Ia-1) wherein x=c (CH ₃)₂,R¹＝R²＝R³＝R⁴ =phenyl, Z ¹＝Z² =2-hydroxyethyl; compound 33 of table a)

To 2- [2, 6-dibromo-4- [1- [3, 5-dibromo-4- (2-hydroxyethoxy) phenyl ] -1-methyl-ethyl ] phenoxy ] ethanol (135.91 g;200mmol; purity = 93%) was added phenylboronic acid (102.42 g; 84mmol; 4.2 equivalents), tris (o-tolyl) phosphine (243.5 mg;0.8 mmol) and anisole (800 mL). To this mixture was added K ₃PO₄ (178.3 g) dissolved in water (396 g). The mixture was stirred at 60-70 ℃ until two clear phases formed and purged with nitrogen. Pd (OCOCH ₃)₂ (45 mg;0.2 mmol) was added to the mixture under argon and the mixture was stirred under reflux until TLC showed complete conversion, then the reaction mixture was cooled to 70℃and the organic layer was separated at this temperature, then washed with aqueous NaOH (10 wt%), aqueous HCl (2M) and brine, the organic layer was taken up in activated charcoal @DX Ultra, cabot corp.) and the mixture was stirred for 2.5 hours. The mixture was then filtered through celite, and the solution was concentrated under reduced pressure. The resulting mixture was cooled to room temperature and stirred overnight. The crystals formed were collected by filtration to give the crude title compound as an off-white solid (97.8 g;79% yield). The crude material was recrystallized from acetone or ethanol mixtures to give the title compound as a white solid with a chemical purity >99% and a yellowness index of 1.3 (APHA 5).

m.p.(DSC):108.3℃；

¹H NMR(80MHz,CDCl₃):δ＝7.93-7.31(m,24H),3.44(m,8H),1.72(s,6H),1.2(s,2H,OH)ppm。

IR(ATR):725.3(84.84);746.5(60.86);842.9(88.30);883.4(72.19);1008.8(67.89);1022.3(74.21);1072.5(80.22);1182.4 88.48);1211.3(73.28);1361.8(85.89);1421.6(72.15);1467.9(75.76);1597.1(90.24);2357.1(92.49);2883.7(89.41);2935.8(89.02);2958.9(86.06);3030.3(90.52);3057.3(90.63);3184.6(91.52);3352.4(90.54)cm^-1.

Example 2:2- [4- [1- [4- (2-hydroxyethoxy) -3, 5-bis (naphthalen-1-yl) phenyl ] -1-methyl-ethyl ] -2, 6-bis (naphthalen-1-yl) phenoxy ] ethanol (a compound of formula (Ia-1) wherein x=c (CH ₃)₂,R¹＝R²＝R³＝R⁴ =naphthalen-1-yl, Z ¹＝Z² =2-hydroxyethyl; compound 34 of table a)

To 2- [2, 6-dibromo-4- [1- [3, 5-dibromo-4- (2-hydroxyethoxy) phenyl ] -1-methyl-ethyl ] phenoxy ] ethanol (90.4 g;133mmol; purity = 93%) was added naphthalene-1-ylboronic acid (114.4 g;665mmol;5 equiv.) and tris (o-tolyl) phosphine (1.62 g;5.32 mmol). To this mixture were added anisole (800 mL) and 148.2g K ₃PO₄ (148.2 g) dissolved in water (331 g). The mixture was stirred at 60-70 ℃ until two clear phases formed and purged with nitrogen. Pd (OCOCH ₃)₂ (299 mg;1.33 mmol) was added to the mixture under argon and the mixture was stirred under reflux until TLC showed complete conversion, then the reaction mixture was cooled to 70℃and the organic layer was separated at this temperature, then washed with aqueous NaOH (10 wt%), aqueous HCl (2M) and brine, the organic layer was treated with activated charcoal @DX Ultra, cabot corp.) and the mixture was stirred for 2.5 hours. The mixture was then filtered through celite, and the solution was concentrated under reduced pressure. The resulting mixture was cooled to room temperature and stirred overnight. The crystals formed were collected by filtration to give the crude title compound as an off-white (off-white) solid (86.3 g;83% yield) with a chemical purity of 96.7%. The crude material may be recrystallized from anisole or toluene/MeOH mixtures.

m.p.＝235.6-236.9℃；

m.p.(DSC):232.9℃；

¹H NMR(80MHz,CDCl₃):δ＝8.07-7.12(m,32H),3.24-2.76(m,4H),3.07-2.59(m,4H),1.81(s,6H),-0.72(s,2H,OH)ppm.

IR(ATR):731.1(78.73);777.3(46.43);798.6(65.68);889.2(80.73);1012.7(70.29);1068.6(73.00);1114.9(85.15);1221.0(74.61);1334.8(86.63);1386.9(76.67);1456.3(82.21);2870.2(90.63);2935.8(90.42);2964.7(90.34);3057.3(90.78);3556.9(88.32)cm^-1.

Example 3:2- [4- [1- [4- (2-hydroxyethoxy) -3, 5-bis (naphthalen-2-yl) phenyl ] -1-methyl-ethyl ] -2, 6-bis (naphthalen-2-yl) phenoxy ] ethanol (a compound of formula (Ia-1) wherein x=c (CH ₃)₂,R¹＝R²＝R³＝R⁴ =naphthalen-2-yl, Z ¹＝Z² =2-hydroxyethyl; compound 35 of table a)

To 2- [2, 6-dibromo-4- [1- [3, 5-dibromo-4- (2-hydroxyethoxy) phenyl ] -1-methyl-ethyl ] phenoxy ] ethanol (90.4 g;133mmol; purity = 93%) was added naphthalene-2-ylboronic acid (138 g;800mmol;6 eq.) and tris (o-tolyl) phosphine (1.62 g;5.32 mmol). Anisole (800 mL) and K ₃PO₄ (178 g) dissolved in water (396 g) were added to the mixture. The mixture was stirred at 60-70 ℃ until two clear phases formed and purged with nitrogen. Pd (OCOCH ₃)₂ (299 mg;1.33 mmol) was added to the mixture under argon and the mixture was stirred under reflux (about 5 to 6 hours) until TLC showed complete conversion the reaction mixture was then cooled to 70℃and the organic layer was separated at this temperature, followed by washing with aqueous NaOH (10 wt%), aqueous HCl (2M) and brine the organic layer was washed with activated charcoal @DX Ultra, cabot corp.) and the mixture was stirred for 2.5 hours. The mixture was then filtered through celite, and the solution was concentrated under reduced pressure. The resulting mixture was cooled to room temperature and stirred overnight. The crystals formed were collected by filtration to give the crude title compound as an off-white solid which was crystallized from a toluene/anisole mixture to give 92.3g of the title compound as an off-white solid with a chemical purity of 92%. After recrystallisation from methanol, the title compound was obtained as a white solid with a chemical purity of >95%.

m.p.＝210.1-211.7℃；

m.p.(DSC):207.1℃；

¹H NMR(80MHz,CDCl₃):δ＝8.19-7.75&7.74-7.35(m,32H),3.51-3.13(m,8H),1.82(s,6H),1.28(s,2H,OH)ppm.

IR(ATR):744.6(55.26);819.8(64.42);854.5(69.17);885.4(71.58);1003.0(78.82);1037.7(79.19);1072.5(81.63);1190.1(80.56);1207.5(73.83);1446.7(81.33);1462.1(81.60);1504.5(84.20);2870.2(90.17);2930.0(89.00);2964.7(86.99);3051.5(88.37);3281.0(90.10)cm^-1.

Example 4a:2, 6-bis (phenanthren-9-yl) -4- [1- (3, 5-bis (phenanthren-9-yl) -4-hydroxy-phenyl) -1-methyl-ethyl ] phenol (compound of formula (Ia-1) wherein x=c (CH ₃)₂,R¹＝R²＝R³ =r=phenanthren-9-yl, Z ¹＝Z² =hydrogen; compound 4 of table a)

To 2, 6-dibromo-4- [1- (3, 5-dibromo-4-hydroxy-phenyl) -1-methyl-ethyl ] phenol (=3, 3', 5' -tetrabromobisphenol a) (56.1 g;100mmol; purity=97%) was added phenanthrene-9-ylboronic acid (133.3 g;600mmol;6 eq.) and tris (o-tolyl) phosphine (1.22 g;4 mmol). Anisole (600 mL) and K ₃PO₄ (133 g) dissolved in water (198 g) were added to the mixture. The mixture was stirred at 60-70 ℃ until two clear phases formed and purged with nitrogen. Pd (OCOCH ₃)₂ (225 mg;1 mmol) was added to the mixture under argon and the mixture was stirred under reflux until TLC showed complete conversion, then the reaction mixture was cooled to 70℃and the organic layer was separated at this temperature, then washed with aqueous NaOH (10 wt%), aqueous HCl (2M) and brine, the organic layer was treated with activated charcoal @DX Ultra, cabot corp.) and the mixture was stirred for 2.5 hours. The mixture was then filtered through celite and the solvent was removed under reduced pressure. The crude title compound thus obtained as off-white solid was dissolved in a toluene/methanol mixture (400 g) at elevated temperature. The mixture was cooled to room temperature and stirred overnight. The crystals formed were collected by filtration to give the title compound as an off-white solid (90.9 g) which was 95% pure chemically and used in the next step without further purification.

Example 4b:2- [4- [1- [4- (2-hydroxyethoxy) -3, 5-bis (phenanthren-9-yl) -phenyl ] -1-methyl-ethyl ] -2, 6-bis (phenanthren-9-yl) -phenoxy ] ethanol (compound of formula (Ia-1) wherein x=c (CH ₃)₂,R¹＝R²＝R³＝R⁴ =phenanthren-9-yl, Z ¹＝Z² =2-hydroxyethyl; compound 36 of table a)

To 2, 6-bis (phenanthren-9-yl) -4- [1- (3, 5-bis (phenanthren-9-yl) -4-hydroxy-phenyl) -1-methyl-ethyl ] phenol (111.7 g;110mmol; purity = 95%) was added ethylene carbonate (77.5 g; 750 mmol;8 equivalents), anisole (315 g) and K ₂CO₃ (12.2 g) as a solid. The mixture was stirred at 135 ℃ until TLC showed complete conversion. The reaction mixture was then cooled to 70-75 ℃ and the organic layer was separated at that temperature, followed by washing with aqueous NaOH (10 wt%) and brine. Activated carbon used for organic layerDX Ultra, cabot corp.) and stirring the mixture for 2 to 3 hours. The mixture was then filtered through celite and the solvent was removed under reduced pressure. The crude title compound thus obtained was dissolved in methyl ethyl ketone (250 g) as an off-white solid under reflux. The mixture was then cooled to room temperature and stirred overnight. The crystals formed were collected by filtration to give the title compound as a white solid (90.5 g;79% yield), with a chemical purity >97% and a yellowness index of 2.9.

m.p.(DSC):299.7℃(302.5℃)；

¹H NMR(80MHz,CDCl₃):δ＝8.99-8.72(m,8H),8.13-7.69(m,32H),3.33-3.11(m,4H),3.10-2.87(m,4H),2.19(s,6H),1.16(s,2H,OH)ppm.

IR(ATR):725.3(71.39);750.3(69.02);763.8(83.89);792.8(90.23);856.4(92.27);891.1(85.61);1010.7(87.29);1066.7(89.17);1215.2(89.68);1278.9(93.54);1361.8(92.15);1448.6(89.01);1462.1(91.02);2283.8(95.22);2868.2(95.44);2918.4(95.24);3063.1(95.44);3551.1(93.88)cm^-1.

Example 5:2- [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 (compound of formula (Ia-1) wherein x=c (CH ₃)₂,R¹＝R²＝R³＝R⁴ =dibenzo [ b, d ] thiophen-4-yl, Z ¹＝Z² =2-hydroxyethyl; compound 51 of table a)

To 2- [2, 6-dibromo-4- [1- [3, 5-dibromo-4- (2-hydroxyethoxy) phenyl ] -1-methyl-ethyl ] phenoxy ] ethanol (74.75 g;110mmol; purity = 93%) was added (dibenzo [ b, d ] thiophen-4-yl) boronic acid (125.4 g;550mmol;5 eq.) and tris (o-tolyl) phosphine (4.02 g;13.2 mmol). Anisole (660 mL) and K ₃PO₄ (122.6 g) dissolved in water (285 g) were added to the mixture. The mixture was stirred at 60-70 ℃ until two clear phases formed and purged with nitrogen. Pd (OCOCH ₃)₂ (741 mg;3.3 mmol) was added to the mixture under argon and the mixture was stirred under reflux (about 5 to 6 hours) until TLC showed complete conversion, then the reaction mixture was cooled to room temperature and the grey solid product formed was collected by filtration, washed with water and methanol and dried, the crude product was dissolved in THF (790 mL) at 50℃and activated charcoal was added @DX Ultra, cabot corp.) and the mixture is stirred at 50 ℃ for 2 to 2.5 hours. The hot mixture was filtered through celite and the resulting solution was concentrated under reduced pressure. The resulting off-white solid was suspended in methanol (500 mL) and stirred at reflux for 2 to 3 hours. The product was filtered off, washed with methanol and dried in vacuo to give 87g of the title compound as a white powder. By repeated use of activated carbon again (/ >)DX Ultra, cabot corp.) and recrystallised from THF/toluene mixtures to give the title compound as a white crystalline powder, 87% yield and purity >98%.

m.p.(DSC):287.5℃；

¹H NMR(80MHz,CDCl₃):δ＝8.39-8.05(m,8H),7.89-7.13(m,24H),3.35-3.12(m,4H),3.12-2.89(m,4H),1.95(s,6H),1.2(s,2H,OH)ppm.

IR(ATR):727.2(64.11);752.3(28.21);804.3(76.60);866.1(80.90);893.1(71.52);1010.7(62.08);1045.5(65.61);1070.5(69.28);1107.2(77.73);1219.1(67.42);1248.0(78.54);1363.7(77.84);1379.2(66.51);1440.9(67.41);1466.0(76.10);2868.2(87.64);3061.1(88.60);3554.9(82.08)cm^-1.

Example 6:2- [4- [4- (2-hydroxyethoxy) -3, 5-bis (naphthalen-1-yl) phenyl ] sulfonyl-2, 6-bis (naphthalen-1-yl) phenoxy ] ethanol (a compound of formula (Ia-1) wherein x=so ₂,R¹＝R²＝R³＝R⁴ =naphthalen-1-yl, Z ¹＝Z² =2-hydroxyethyl; compound 55 of table a)

To 2- [4- [4- (2-hydroxyethoxy) -3, 5-dibromophenyl ] sulfonyl-2, 6-dibromophenoxy ] ethanol (170.3 g;250mmol; purity=96%) was added naphthalene-1-ylboronic acid (219.37 g;1.25mol;5 equivalents; purity=98%) and tris (o-tolyl) phosphine (1.52 g;5.0 mmol). Anisole (750 mL) and 276g K ₃PO₄ dissolved in 613g water were added to the mixture. The mixture was stirred at 60-70 ℃ until two clear phases formed and purged with nitrogen. Pd (OCOCH ₃)₂) (281mg; 1.25 mmol) was added to the mixture under argon and the mixture was stirred under reflux until TLC showed complete conversion the mixture was cooled to 70 ℃, the organic layer was separated at 70 ℃ and subsequently washed with aqueous NaOH (10 wt%), aqueous HCl (2M) and brine, activated carbon (Norit DX Ultra) was added to the organic layer and the mixture was stirred for 2.5 hours then the mixture was filtered through celite and the solution concentrated under reduced pressure the mixture was cooled to room temperature and stirred overnight.

m.p.(DSC):213.4℃；

¹H NMR(80MHz,CDCl₃):δ＝8.07(s,4H),7.83-7.12(m,28H),3.31-3.06(m,4H),3.04-2.72(m,4H),0.79(s,2H,OH)ppm.

IR(ATR):439.78(50.37);509.22(45.63);609.53(59.16);621.1(69.13);651.96(63.19);723.33(73.09);734.9(72.97);775.41(41.64);798.56(64.26);895.0(76.4);1018.45(71.93);1068.6(72.88);1091.75(66.93);1118.75(70.24);1147.68(56.44);1226.77(75.63);1323.21(70.4);1423.51(78.3);1506.46(86.42);1573.97(89.54);1593.25(91.18);2947.33(90.31);3057.27(90.11);3570.36(89.31)cm^-1.

Example 7:2- [4- [4- (2-hydroxyethoxy) -3, 5-bis (naphthalen-1-yl) phenyl ] sulfanyl-2, 6-bis (naphthalen-1-yl) phenoxy ] ethanol (a compound of formula (Ia-1) wherein x=s, R ¹＝R²＝R³＝R⁴ =naphthalen-1-yl, Z ¹＝Z² =2-hydroxyethyl; a compound 76 of table a)

To a cooled (-18 ℃) solution of lithium aluminum hydride (19 g;500 mmol) in THF (600 mL) was slowly added TiCl ₄ (47.5 g;250 mmol) in 2-methyl-THF (1L) and the mixture stirred under inert gas at 0deg.C for 30min. To this mixture was added slowly in portions 2- [4- [4- (2-hydroxyethoxy) -3, 5-bis (naphthalen-1-yl) phenyl ] sulfonyl-2, 6-bis (naphthalen-1-yl) phenoxy ] ethanol (43.9 g;50 mmol) obtained in example 6 at 0 ℃. After the addition was completed, the mixture was stirred at 0℃under an inert gas for another 30 minutes. The mixture was slowly warmed to room temperature and stirred at room temperature for 1 hour. TLC (eluent: cyclohexane: ethyl acetate 2:1) showed complete conversion. To this mixture was slowly added a mixture of water (19 g) and THF (30 mL) to break down the excess lithium aluminum hydride. The solvent was removed under reduced pressure, and the resulting residue was purified by column chromatography (silica gel; cyclohexane: ethyl acetate 5:1) to give 24.6g of the title compound as a white solid having a chemical purity of about 99.7%.

m.p.(DSC):97℃；

¹H NMR(80MHz,CDCl₃):δ＝8.1-7.2(m,32H),3.2-3.0(m,4H),2.8-2.5(m,4H),0.2-0.5(m,2H,OH)ppm.

Example 8:2- [4- [4- (2-hydroxyethoxy) -3, 5-bis (phenanthren-9-yl) phenyl ] sulfonyl-2, 6-bis (phenanthren-9-yl) phenoxy ] ethanol (a compound of formula (Ia-1) wherein x=so ₂,R¹＝R²＝R³＝R⁴ =phenanthren-9-yl, Z ¹＝Z² =2-hydroxyethyl; compound 57 of table a)

To 2- [4- [4- (2-hydroxyethoxy) -3, 5-dibromophenyl ] sulfonyl-2, 6-dibromophenoxy ] ethanol (148.0 g;217.26mmol; purity=96%) was added phenanthrene-9-ylboronic acid (246.13 g;1.0863mol;5 equivalents; purity=98%) and tris (o-tolyl) phosphine (1.33 g;4.35 mmol). Anisole (700 g) and 240g K ₃PO₄ dissolved in 532g of water were added to the mixture. The mixture was stirred at 60-70 ℃ until two clear phases formed and purged with nitrogen. Pd (OCOCH ₃)₂ (244 mg;1.086 mmol) was added to the mixture under argon and the mixture stirred at reflux for 9 hours because TLC (eluent: e.g. cyclohexane: ethyl acetate 1:2) then showed complete reaction, another portion of phenanthrene-9-yl boronic acid (24.313 g;108.63 mmol) and 24g K ₃PO₄ dissolved in 53.2g of water together with Pd-catalyst [ Pd (OCOCH ₃)₂ (24.4 mg;0.1086 mmol) and tris (o-tolyl) phosphine (133 mg;0.435 mmol) ] were added and the reaction mixture stirred at reflux for an additional 90 minutes until TLC (eluent: e.g. cyclohexane: ethyl acetate 1:2) showed almost complete conversion.

The crude product is filtered off, washed with anisole and 2-methyltetrahydrofuran and dried at 60 ℃. The crude product was dissolved in 3L THF and 10g of activated charcoal (Norit DX Ultra) were added. The mixture was stirred at 40 ℃ for 2 hours, and after filtration of the activated carbon over celite, the solvent was completely removed under reduced pressure. The product was crystallized from toluene to give 157.7g of the title compound as a white solid with a chemical purity >94%. The product was recrystallized from toluene to give the title compound with a chemical purity of >97%.

(DSC) 233.8 ℃ (toluene solvate); 242.2 DEG C

¹H NMR(80MHz,CDCl₃):δ＝8.43-9.03(m,8H),8.22(dd,J＝3.1,1.4Hz,4H),7.55-8.01(m,28H),7.20-7.27(m,4H),3.01-3.49(m,4H,-CH2-),2.50-2.92(m,4H,-CH2-),0.32-0.56(m,2H)ppm.

IR(ATR):405.06(29.54);561.3(78.99);615.31(63.9);632.67(63.18);723.33(48.06);744.55(52.77);763.84(75.45);887.28(76.3);964.44(83.77);1012.66(79.76);1066.67(82.66);1082.1(76.5);1091.75(75.17);1132.25(63.8);1145.75(76.3);1178.55(85.26);1230.63(81.87);1261.49(82.73);1319.35(80.0);1419.66(82.14);1450.52(81.1)cm^-1.

N _D calc:. 1.76 (calculated using software ACD/ChemSketch 2012 from ADVANCED CHEMISTRY Development, inc).

Example 9:2- [4- [4- (2-hydroxyethoxy) -3, 5-bis (dibenzo [ b, d ] thiophen-4-yl) phenyl ] sulfonyl-2, 6-dibenzo [ b, d ] thiophen-4-yl) phenoxy ] ethanol (a compound of formula (Ia-1) wherein x=so ₂,R¹＝R²＝R³＝R⁴ =dibenzo [ b, d ] thiophen-4-yl, Z ¹＝Z² =2-hydroxyethyl; compound 72 of table a

To 2- [4- [4- (2-hydroxyethoxy) -3, 5-dibromophenyl ] sulfonyl-2, 6-dibromophenoxy ] ethanol (143.05 g;210mmol; purity=96%) was added dibenzo [ b, d ] thiophen-4-ylboronic acid (244.37 g;1,05mol;5 eq; purity=98%) and tris (o-tolyl) phosphine (1.28 g;4.2 mmol). Anisole (700 g) and 232g K ₃PO₄ dissolved in 515g of water were added to the mixture. The mixture was stirred at 60-70 ℃ until two clear phases formed and purged with nitrogen. Pd (OCOCH ₃)₂ (236 mg;1.05 mmol) and stirring the mixture under reflux for 3 hours until TLC (eluent: e.g. cyclohexane: ethyl acetate 1:2) shows complete conversion (note: if according to TLC after 9 hours the reaction was incomplete, another portion of dibenzo [ b, d ] thiophen-4-ylboronic acid (24.44 g;105 mmol) and 23.2g K ₃PO₄ dissolved in 51.5g of water and Pd catalyst [ Pd (OCOCOCH ₃)₂ (23.6 mg;0.105 mmol) and tris (o-tolyl) phosphine (128 mg;0.42 mmol) ] should be added to the mixture under reflux, and the reaction mixture stirred under reflux until TLC shows at least almost complete conversion.) the mixture is cooled to 70 ℃, the organic layer is separated at 70 ℃, the aqueous phase is extracted with 250mL of 2-methyltetrahydrofuran. 10% aqueous NaOH solution (375 mL.) is added to the combined organic layer at 70 ℃ as the product crystallizes, the suspension is cooled to room temperature and cooled down to 60.5 g of THF and the crude product is then washed at 60.5 g.

The resulting solid was dissolved in 3L anisole under reflux and then cooled to 120 ℃. 10g of activated charcoal (Norit DX Ultra) were then added and the mixture was stirred at 120℃for 1 hour. The activated carbon was filtered off using celite at 120 ℃ and the solution was concentrated to about 1000g under reduced pressure. The clear solution was cooled to room temperature and THF (500 mL) was added. The crystals formed were collected by filtration and dried at 60℃to give the crude title compound as a white solid (174.4 g; 77.8%). The crude product may be recrystallized from anisole/THF (1/1 v/v) or anisole/2-propanol (1/1 v/v) mixtures to give the title compound with a chemical purity >95% (by NMR). (remark: if anisole/THF mixtures are used, THF solvates of the title compound are obtained).

(DSC) 204.1 ℃ (THF solvate); 294.1 DEG C

¹H NMR(80MHz,CDCl₃):δ＝8.52(s,4H),8.32-8.51(m,8H),7.09-7.88(m,20H),3.40-3.55(m,4H),3.13-3.29(m,4H),1.00(t,J＝6,5Hz,2H,OH)ppm.

IR(ATR):495.72(37.35);551.66(81.77);565.16(83.67);607.6(62.68);630.74(69.8);704.04(76.01);723.33(77.99);748.41(49.59);885.36(81.46);906.57(81.63);1003.02(77.16);1045.45(68.95);1068.6(80.44);1105.25(78.89);1120.68(80.61);1145.75(67.34);1234.48(80.97);1246.06(79.06);1303.92(81.87);1319.35(80.33);1375.29(80.49);1383.01(81.94);1429.3(77.66);1442.8(82.59)cm^-1.

N _D calc:. 1.79 (calculated using software ACD/ChemSketch 2012 from ADVANCED CHEMISTRY Development, inc).

Example 10:2- [4- [4- (2-hydroxyethoxy) -3, 5-bis (thianthrene-1-yl) phenyl ] sulfonyl-2, 6-bis (thianthrene-1-yl) phenoxy ] ethanol (a compound of formula (Ia-1) wherein x=so ₂,R¹＝R²＝R³＝R⁴ =thianthrene-1-yl, Z ¹＝Z² =2-hydroxyethyl; compound 73 of table a)

To 2- [4- [4- (2-hydroxyethoxy) -3, 5-dibromophenyl ] sulfonyl-2, 6-dibromophenoxy ] ethanol (143.05 g;210mmol; purity=96%) was added thianthrene-1-ylboronic acid (278.72 g;1.05mol;5 equivalents; purity=98%) and tris (o-tolyl) phosphine (1.28 g;4.2 mmol). Anisole (700 g) and 232g K ₃PO₄ dissolved in 515g of water were added to the mixture. The mixture was stirred at 60-70 ℃ until two clear phases formed, purged with nitrogen. Pd (OCOCH ₃)₂ (236 mg;1.05 mmol) was added to the mixture under argon and the mixture was stirred under reflux until TLC (eluent: e.g. cyclohexane: ethyl acetate 1:2) showed complete conversion (note: if according to TLC after 9 hours of reflux another part of thianthrene-1-yl boronic acid (27.87 g;105 mmol) and 23.2g K ₃PO₄ dissolved in 51.5g of water and Pd-catalyst [ Pd (OCOCH ₃)₂ (23.6 mg;0.105 mmol) and tris (o-tolyl) phosphine (128 mg;0.42 mmol) ] were added if the reaction was incomplete then the reaction mixture was stirred under reflux until TLC showed at least almost complete conversion.

The mixture was cooled to 70 ℃, the organic layer was separated at 70 ℃ and then washed with aqueous NaOH (10 wt%), aqueous HCl (2M) and brine. To the organic layer was added 100g Na ₂SO₄ and 10g activated carbon (Norit DX Ultra) and the mixture was stirred for 1 hour. The mixture was then filtered through celite and the solvent was completely removed under reduced pressure. The crude product was dissolved in 860-880mL of toluene/methanol (1/1 v/v) mixture at 55 ℃ and the clear solution was cooled to room temperature and stirred overnight. The crystals formed were collected by filtration and dried at 60℃to give the crude title compound as a white solid (210.6 g; 83.9%) with a chemical purity of 97.61%.

The product may be further purified by additional recrystallisation from a toluene/methanol mixture.

m.p.(DSC):224.0℃；

¹H NMR(80MHz,CDCl₃):δ＝8.25(s,4H),7.97-7.23(m,28H),3.55-3.35(m,4H),3.43-3.05(m,4H),1.41-1.30(m,2H,OH),ppm.

IR(ATR):572.88(85.64);615.31(56.0);663.53(83.11);700.18(68.44);721.4(79.65);746.48(51.87);783.13(72.49);794.7(79.81);904.64(81.82);1010.73(76.44);1057.03(84.15);1074.39(80.9);1099.46(73.27);1118.75(83.89);1145.75(63.26);1190.12(86.98);1226.77(80.11);1249.91(83.27);1319.35(71.87);1361.79(85.74);1394.58(74.99);1431.23(74.95);1448.59(80.7);1558.54(87.15)cm^-1.

N _D calc: 1.77 (calculated using software ACD/ChemSketch 2012 from ADVANCED CHEMISTRY Development, inc).

Example 11:2,2' - (sulfonylbis { [2, 6-bis (naphthalen-1-yl) -4, 1-phenylene ] oxy }) bis (ethan-1-ol) (compound of formula (Ia-1) wherein x=so ₂,R¹＝R²＝R³＝R⁴ =naphthalen-2-yl, Z ¹＝Z² =2-hydroxyethyl; compound 56 of table a)

To 2,2' - { sulfonylbis [ (2, 6-dibromo-4, 1-phenylene) oxy ] } di (ethan-1-ol) (170.3 g;250mmol; purity=96%) were added naphthalene-2-ylboronic acid (219.37 g;1.25mol;5 equivalents; purity=98%) and tris (o-tolyl) phosphine (1.52 g;5.0 mmol). Anisole (750 mL) and 276g K ₃PO₄ dissolved in 613g water were added to the mixture. The mixture was stirred at 60-70 ℃ until two clear phases formed and purged with argon. Pd (OCOCH ₃)₂ (281mg; 1.25 mmol) was added to the mixture under argon and the mixture was stirred under reflux until TLC showed complete conversion.

The mixture was cooled to 70 ℃, the organic layer was separated at 70 ℃ and then washed with aqueous NaOH (10 wt%), aqueous HCl (2M) and brine. Activated carbon (Norit DX Ultra) was added to the organic layer and the mixture was stirred at 70℃for 2.5 hours. The mixture was then filtered through celite, and the solution was concentrated under reduced pressure. The mixture was cooled to ambient temperature and stirred overnight. The crystals formed were collected by filtration to give the crude title compound as a white solid (149.33 g; 65%) having a chemical purity of 92.2%. The crude material was then recrystallized from toluene/MeOH (1/1 v/v) and then from methyl ethyl ketone to give 78.71g of the title compound as a white solid with a chemical purity of about 94%.

m.p.(DSC):252.2℃；

¹H NMR(80MHz,CDCl₃):δ＝8.21(s,4H,CAr-H),8.10–7.42(m,28H,CAr-H),3.44–3.34(m,4H,CH₂),3.22–3.11(m,4H,CH₂),1.11(bs,2H)ppm.

IR(ATR):740.69(60.15);812.06(67.64);866.07(73.57);895(74.44);949.01(80.71);1016.52(74.98);1101.39(65.76);1143.83(55.87);1219.05(75.88);1319.35(64.85);1421.58(79.99);1442.8(83.05)cm^-1.

Example 12:4,4' - (propane-2, 2-diyl) bis [2, 6-bis (thianthrene-1-yl) phenol ] (compound of formula (Ia-1) wherein x=c (CH ₃)₂,R¹＝R²＝R³＝R⁴ =thianthrene-1-yl, Z ¹＝Z² =hydrogen; compound 7 of table a)

To 4,4' - (propane-2, 2-diyl) bis (2, 6-dibromophenol) (70.1 g;125mmol; purity: 97%) was added thianthrene-1-ylboronic acid (166 g;625mmol;5 equivalents; purity: 98%) and tris (o-tolyl) phosphine (1.52 g;5.0 mmol). Anisole (500 g) and 11.4g K ₃PO₄ dissolved in 248g water were added to the mixture. The mixture was stirred at 60-70 ℃ until two clear phases formed and purged with argon. Pd (OCOCH ₃)₂ (281mg; 1.25 mmol) was added to the mixture under argon and the mixture was stirred under reflux until TLC (eluent: e.g. cyclohexane/ethyl acetate 3:1) showed complete conversion.

The mixture was cooled to 70 ℃, the organic layer was separated at 70 ℃ and then washed with aqueous NaHCO ₃ (10 wt%), aqueous HCl (2M) and brine. To the organic layer was added 6.75g of activated carbon (Norit DX Ultra) and 13.5g of Na ₂SO₄, and the mixture was stirred for 1 hour. The mixture was then filtered through celite and the solvent was completely removed under reduced pressure. The crude product was used in the next step without additional purification or recrystallisation from a toluene/MeOH (1/1 v/v) mixture.

Example 13:2,2' - (propane-2, 2-diylbis { [2, 6-bis (thianthrene-1-yl) -4, 1-phenylene ] oxy }) bis (ethan-1-ol) (compound of formula (Ia-1) wherein x=c (CH ₃)₂,R¹＝R²＝R³＝R⁴ =thianthrene-1-yl, Z ¹＝Z² =2-hydroxyethyl; compound 52 of table a)

To 4,4' - (propane-2, 2-diyl) bis [2, 6-bis (thianthin-1-yl) phenol ] (125 mmol) obtained in example 12 in anisole (360 g) were added 5.2g K ₂CO₃ and 33g ethylene carbonate. The reaction mixture was stirred under reflux until TLC (eluent: e.g. cyclohexane/ethyl acetate 3:1) showed complete conversion.

The mixture was cooled to 70-80 ℃, the organic layer was separated at 70 ℃ and then washed with brine, aqueous NaOH (10 wt%), aqueous HCl (2M) and brine. The organic layer was dried over Na ₂SO₄, filtered through celite and the solvent was completely removed under reduced pressure. The crude product was purified by column chromatography to give 70.8g of the title compound as a white solid with a chemical purity of about 97-98%.

m.p.(DSC):110.6℃；

¹H NMR(80MHz,CDCl₃):δ＝7.92–7.25(m,32H,C_Ar-H),3.5–3.0(m,8H,CH₂),2.1(bs,6H,CH₃),ppm.

IR(ATR):723.33(68.04);744.55(47.89);779.27(73.45);792.77(77.93);885.36(77.60);1026.16(74.34);1070.53(78.20);1111.03(80.06);1219.05(76.24);1247.99(79.74);1386.86(70.11);1448.59(64.40);1552.75(85.03);2848.96(83.56);2924.18(78.87);3053.42(87.35)cm^-1.

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

To a solution of 82.7mL (about 258 g) bromine in 750g methanol was slowly added a solution of 60g [1,1 '-biphenyl ] -4,4' -diol in 750g methanol at 0deg.C. The reaction mixture was stirred at 0 ℃ for an additional hour and then at ambient temperature overnight. The precipitated product was filtered off, then washed with cold methanol, then with aqueous ascorbic acid (20 wt%) and finally twice with water. The crude product (149 g) was crystallized from a THF/toluene mixture to give 130.3g of the title product as an off-white powder with a chemical purity of >97.5%.

¹H NMR(80MHz,DMSO-d₆):δ＝9.91(s,2H,OH),7.72(s,4H,C_Ar-H)ppm。

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

To a solution of 161.3g of 3,3', 5' -tetrabromo [1,1 '-biphenyl ] -4,4' -diol obtained in example 14a in 483g (ca. 512 mL) of DMF (homogenized at 60 ℃ C.) was added 172.4g K ₂CO₃. The mixture was stirred at 60℃for a further 10-20 minutes, then 201.24g of 2-chloroethan-1-ol were added. The reaction mixture was stirred at 120℃for 3 hours. After cooling to ambient temperature, the reaction mixture was poured into 1.5L of water, and a white precipitate formed. After slow neutralization with concentrated HCl, the crude product was filtered off and subsequently washed with water (3X 500 mL) and ethanol (500 mL). The crude product was dissolved in 1450g THF under reflux, 4.0g activated charcoal (Norit DX Ultra) was added and the mixture was stirred under reflux for 1 hour. The mixture was then filtered through celite at 60 ℃ and the solvent was removed under reduced pressure. After crystallization from a THF/toluene mixture, the resulting crystals were filtered off and washed with 500g toluene to give 157.3g (yield about 85.5%) of the title compound, which was > 97.7% pure chemically.

m.p.(DSC):232.1℃；

¹H NMR(80MHz,DMSO-d₆):δ＝7.8(s,4H,C_Ar-H),4.74(t,J＝5.4Hz,2H,OH),4.2–3.5(m,8H,CH₂)ppm.

Example 14c:2,2' - { [3,3', 5' -tetra (naphthalen-1-yl) [1,1' -biphenyl ] -4,4' -diyl ] bis (oxy) } di (ethan-1-ol) (compound of formula (Ia-1) wherein x=single bond, R ¹＝R²＝R³＝R⁴ =naphthalen-1-yl, Z ¹＝Z² =2-hydroxyethyl; compound 244 of table a

To 2,2' - [ (3, 3', 5' -tetrabromo [1,1' -biphenyl ] -4,4' -diyl) bis (oxy) ] di (ethan-1-ol) (74.5 g;123.77 mmol) obtained in example 14b were added naphthalene-1-ylboronic acid (110 g;626.8mmol;5.06 eq; purity=98%) and anisole (390 mL). 138g K ₃PO₄ dissolved in 306g of water was added to the mixture. The mixture was stirred at 60-70 ℃ until two clear phases formed, then purged with argon. To this mixture was added tris (o-tolyl) phosphine (1.5 g;4.95 mmol) and Pd (OCOCH ₃)₂ (281mg; 1.25 mmol) in 5mL anisole under argon, and the mixture was stirred under reflux until TLC showed complete conversion.

The mixture was cooled to 70 ℃, the organic layer was separated at 70 ℃ and then washed with aqueous NaOH (10 wt%), aqueous HCl (2M) and brine. To the organic layer 10g of activated charcoal (Norit DX Ultra) and 100g of Na ₂SO₄ were added and the mixture was stirred at 70℃for 1 hour. The mixture was then filtered through celite and the solvent was removed under reduced pressure. The crude product may be recrystallized from toluene/isopropanol or a mixture of toluene/MeOH (1/1 v/v) and/or purified by column chromatography (eluent: cyclohexane/ethyl acetate) to give the title compound as a white solid with a chemical purity of about 93%.

m.p.(DSC):249.6℃；

¹H NMR(80MHz,CDCl₃):δ＝8.20–7.73(m,16H,C_Ar-H),7.73–7.33(m,16H,C_Ar-H),3.3–2.96(m,4H,CH₂),3.0–2.53(m,4H,CH₂),0.45(bs,2H,OH)ppm.

IR(ATR):607.6(76.1);734.9(75.7);773.48(34.8);788.91(56.9);800.49(68.7);887.28(68.9);1018.45(66.0);1066.67(66.2);1087.89(74.9);1222.91(65.5);1361.79(78.5);1396.51(70.4);1427.37(72.5);1440.87(75.9);1506.46(75.0)cm^-1.

Example 15:2,2' - { [3,3', 5' -tetra (naphthalen-2-yl) [1,1' -biphenyl ] -4,4' -diyl ] bis (oxy) } di (ethan-1-ol) (compound of formula (Ia-1) wherein x=single bond, R ¹＝R²＝R³＝R⁴ =naphthalen-1-yl, Z ¹＝Z² =2-hydroxyethyl; compound 245 of table a

To 2,2' - [ (3, 3', 5' -tetrabromo [1,1' -biphenyl ] -4,4' -diyl) bis (oxy) ] bis (ethan-1-ol) (74.5 g;123.77 mmol) was added naphthalene-2-ylboronic acid (165 g;937.5mmol;7.5 eq; purity = 98%) and anisole (440 mL). 207g K ₃PO₄ dissolved in 460g of water was added to the mixture. The mixture was stirred at 60-70 ℃ until two clear phases formed and purged with argon. To this mixture was added tris (o-tolyl) phosphine (3.05 g;4.95 mmol) and Pd (OCOCH ₃)₂ (561 mg;2.5 mmol) in 10mL anisole under argon and the mixture was stirred under reflux until TLC showed complete conversion the mixture was cooled to 70 ℃, the organic layer was separated at 70 ℃ followed by washing with aqueous NaOH (10 wt%), aqueous HCl (2M) and brine 10g of activated carbon (Norit DX Ultra) and 100g of Na ₂SO₄ were added to the organic layer, the mixture was stirred at 70 ℃ for 1 hour, then the mixture was filtered through celite and the solvent was removed under reduced pressure the crude product was recrystallized from a toluene/MeOH (7/3 w/w) mixture and/or purified by column chromatography (eluent: cyclohexane/ethyl acetate) to give the title compound as a white solid with a chemical purity of about 94%.

m.p.(DSC):256.4℃；

¹H NMR(80MHz,CDCl₃):δ＝8.2(s,4H,C_Ar-H),8.12–7.77(m,20H,C_Ar-H),7.71–7.42(m,8H,C_Ar-H),3.57–3.38(m,4H,CH₂),3.37–3.13(m,4H,CH₂),1.13(m,2H,OH)ppm.

IR(ATR):515.01(67.1);651.96(78.1);744.55(37.5);775.41(77.9);800.49(77.7);823.63(53.4);860.28(51.3);893.07(71.0);906.57(74.4);995.3(77.1);1014.59(70.5);1045.45(74.2);1072.46(72.0);1080.17(68.6);1217.12(67,0);1236.41(76.2);1336.71(76.6);1419.66(67.7);1442.8(69.8);1504.53(76.0)cm^-1.

Example 16:2,2' - { [3,3', 5' -tetrakis (phenanthren-9-yl) [1,1' -biphenyl ] -4,4' -diyl ] bis (oxy) } di (ethan-1-ol) (compound of formula (Ia-1) wherein x=single bond, R ¹＝R²＝R³＝R⁴ =phenanthren-9-yl, Z ¹＝Z² =2-hydroxyethyl; compound 246 of table a)

To 2,2' - [ (3, 3', 5' -tetrabromo [1,1' -biphenyl ] -4,4' -diyl) bis (oxy) ] di (ethan-1-ol) (75.2 g;125 mmol) was added phenanthrene-9-ylboronic acid (141.61 g;625mmol;7.5 equivalents; purity: 98%) and anisole (390 mL). 138g K ₃PO₄ dissolved in 306g of water was added to the mixture. The mixture was stirred at 60-70 ℃ until two clear phases formed and purged with argon. To this mixture was added tris (o-tolyl) phosphine (1.52 g;5.0 mmol) and Pd (OCOCH ₃)₂ (281mg; 1.25 mmol) in 5mL anisole under argon, and the mixture was stirred under reflux until TLC showed complete conversion.

The mixture was cooled to 70 ℃, the organic layer was separated at 70 ℃ and then washed with aqueous NaOH (10 wt%), aqueous HCl (2M) and brine. To the organic layer 10g of activated charcoal (Norit DX Ultra) and 100g of Na ₂SO₄ were added and the mixture was stirred at 70℃for 1 hour. The mixture was then filtered through celite and the solvent was removed under reduced pressure. The crude product was recrystallized from a mixture of toluene/MeOH (7/3 w/w) and/or purified by column chromatography (eluent: cyclohexane/ethyl acetate) to give the title compound as a white solid with a chemical purity >98%.

M.p. (DSC) 347.2℃and 392.1 ℃;

¹H NMR(80MHz,CDCl₃):δ＝8.79–8.41(m,8H,C_Ar-H),8.09–7.32(m,32H,C_Ar-H),3.34–3.18(m,4H,CH₂),2.84–2.68(m,4H,CH₂),0.57–0.45(m,2H,OH)ppm.

IR(ATR):488.01(37.8);567.09(72.2);617.24(70.9);692.47(78.9);725.26(43.6);744.55(47.9);765.77(66.8);885.36(71.0);1014.59(74.9);1068.6(76.0);1220.98(71.6);1361.79(79.7);1429.3(67.4);1448.59(72.5)cm^-1.

example 17:2,2' - { [3,3', 5' -tetrakis (dibenzo [ b, d ] thiophen-4-yl) [1,1' -biphenyl ] -4,4' -diyl ] bis (oxy) } di (ethan-1-ol) (compound of formula (Ia-1) wherein X = single bond, R ¹＝R²＝R³＝R⁴ = dibenzo [ b, d ] thiophen-4-yl, Z ¹＝Z² = 2-hydroxyethyl; compound 248 of table a

To 2,2' - [ (3, 3', 5' -tetrabromo [1,1' -biphenyl ] -4,4' -diyl) bis (oxy) ] di (ethan-1-ol) (10 g;16.3 mmol) was added dibenzo [ b, d ] thiophen-4-ylboronic acid (19.1 g;81.37mmol;5 equivalents; purity = 98%) and anisole (51 mL). To this mixture was added 18g K ₃PO₄ dissolved in 40g of water. The mixture was stirred at 60-70 ℃ until two clear phases formed and purged with argon. To this mixture was added tris (o-tolyl) phosphine (198mg; 0.651 mmol) and Pd (OCOCH ₃)₂ (37 mg;0.163 mmol) in 5mL anisole under argon, the mixture was stirred under reflux until TLC showed complete conversion, the mixture was cooled to 70 ℃, the organic layer was separated at 70 ℃ and subsequently washed with aqueous NaOH (10 wt%), aqueous HCl (2M) and brine 1.0g activated carbon (Norit DX Ultra) and 10.0g Na ₂SO₄ were added to the organic layer, the mixture was stirred at 70 ℃ for 1 hour, then the mixture was filtered through celite and the solvent was removed under reduced pressure, the crude product was recrystallized from methyl ethyl ketone and/or purified by column chromatography (eluent: cyclohexane/ethyl acetate) to give the title compound as a white solid with a chemical purity >94%.

m.p.(DSC):390.9℃；

¹H NMR(80MHz,CDCl₃):δ＝8.21–6.98(m,32H,C_Ar-H),3.34–3.18(m,4H,CH₂),3.05–2.79(m,4H,CH₂),1.05–0.85(m,2H,OH)ppm.

IR(ATR):607.6(74.1);617.24(65.8);650.03(74.3);686.68(70.2);704.04(71.5);721.4(64.4);744.55(29.7);887.28(61.2);1031.95(63.0);1047.38(60.8);1078.24(64.8);1232.55(64.9);1249.91(74.9);1303.92(78.5);1357.93(75.7);1379.15(68.1);1442.8(65.3)cm^-1.

Example 18:2,2' - { [3,3', 5' -tetrakis (thianthrene-1-yl) [1,1' -biphenyl ] -4,4' -diyl ] bis (oxy) } di (ethan-1-ol) (compound of formula (Ia-1) wherein x=single bond, R ¹＝R²＝R³＝R⁴ =thianthrene-1-yl, Z ¹＝Z² =2-hydroxyethyl; compound 249 of table a

To 2,2' - [ (3, 3', 5' -tetrabromo [1,1' -biphenyl ] -4,4' -diyl) bis (oxy) ] di (ethan-1-ol) (12.04 g;20 mmol) was added thianthrene-1-ylboronic acid (26.5 g;100mmol;5 equivalents; purity: 98%) and anisole (62 mL). To this mixture was added 22.1g K ₃PO₄ dissolved in 49g of water. The mixture was stirred at 60-70 ℃ until two clear phases formed and purged with argon. To this mixture was added tris (o-tolyl) phosphine (244 mg;0.8 mmol) and Pd (OCOCH ₃)₂ (45 mg;0.2 mmol) in 5mL anisole under argon, and the mixture was stirred under reflux until TLC showed complete conversion.

The mixture was cooled to 70 ℃, the organic layer was separated at 70 ℃ and then washed with aqueous NaOH (10 wt%), aqueous HCl (2M) and brine. To the organic layer was added 1.0g of activated carbon (Norit DX Ultra) and 10.0g of Na ₂SO₄, and the mixture was stirred at 70℃for 1 hour. The mixture was then filtered through celite and the solvent was removed under reduced pressure. The crude product was purified by column chromatography (eluent: cyclohexane/ethyl acetate) to give the title compound as a white solid with a chemical purity >94%.

m.p.(DSC):276.5℃；

¹H NMR(80MHz,DMSO-d₆):δ＝7.85(s,4H,C_Ar-H),7.74–7.16(m,28H,C_Ar-H),4.15–4.00(m,2H,OH),3.27–3.05(m,4H,CH₂),2.90–2.70(m,4H,CH₂)ppm.

IR(ATR):410.85(5.61);432.07(43.16);461.00(48.69);476.43(49.07);663.53(75.92);725.26(68.4);746.48(45.2);790.84(73.4);875.71(75.99);1018.45(75.63);1070.53(77.53);1224.84(73.71);1390.72(71.63);1431.23(64.16);1446.66(65.87)cm^-1.

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

To a solution of 1,1 '-biphenyl-2, 2' -diol (25.0 g;134 mmol) in methanol (1000 mL) was added dropwise bromine (107 g,671mmol,5.0 eq.) at 0deg.C. The reaction was warmed to room temperature and stirred until TLC (heptane/ethyl acetate 2:1) showed complete conversion. The precipitate was filtered off and washed with cold methanol to give the crude product as a yellow solid (49.8 g,99.2mmol; yield: 74%). The crude product was recrystallized from acetone to yield 35.9g of the title compound as an off-white solid.

M.p. (DSC): decomposition at 300 ℃.

¹H NMR(80MHz,DMSO-d6):δ＝8.67(br s,2H),7.74(d,J＝2.4Hz,2H),7.29(d,J＝2.4Hz,2H)ppm。

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

To a suspension of 3,3', 5' -tetrabromo [1,1 '-biphenyl ] -2,2' -diol (29.0 g;57.8 mmol) obtained in example 19a in anisole (450 mL) was added K ₂CO₃ (31.9 g,231mmol,4.0 eq.) and the mixture was stirred at 50℃for 30 min. Ethylene carbonate (50.9 g,578mmol,10 eq.) was added in portions and the reaction heated to reflux until TLC (cyclohexane/ethyl acetate (2:1), containing about 1% acetic acid) showed complete conversion. The mixture was cooled to room temperature, ethyl acetate (200 mL) and water (100 mL) were added, and the phases were separated. The aqueous phase was extracted with ethyl acetate (100 mL). The combined organic phases were washed with water (2×100 ml), dried over Na ₂SO₄, and the solvent was removed under reduced pressure to give the crude product as an off-white solid (35.2 g,57.8mmol, 100%).

The crude product was recrystallized from toluene to yield 20g of the title compound as a pale off-white solid.

¹H NMR(80MHz,CDCl₃):δ＝7.76(d,J＝2.4Hz,2H),7.45(d,J＝2.4Hz,2H),3.85–3.49(m,8H),2.08(t,J＝5.6Hz,2H)ppm.

Example 19c:2,2' - { [3,3', 5' -tetrakis (phenanthren-9-yl) [1,1' -biphenyl ] -2,2' -diyl ] bis (oxy) } di (ethan-1-ol) (compound of formula (Ia-1) wherein x=single bond, R ¹＝R²＝R³＝R⁴ =thianthrene-1-yl, Z ¹＝Z² =2-hydroxyethyl; compound 12 of table B

To a mixture of 2,2' - [ (3, 3', 5' -tetrabromo [1,1' -biphenyl ] -2,2' -diyl) bis (oxy) ] di (ethan-1-ol) (17.0 g;28.8 mmol) and 9-phenanthrylboronic acid (32.0 g;144mmol;5.0 eq.) in anisole (100 g) obtained in example 19b was added a solution of K ₃PO₄ (31.8 g,150mmol,5.2 eq.) in water (70 g) and the mixture was heated to 70 ℃. Tris (o-tolyl) phosphine (0.175 g,0.576mmol,2.0 mol%) and Pd (OCOCH ₃)₂ (32.4 mg;0.144mmol,0.5 mol%) were added and the reaction mixture was heated to reflux until TLC (cyclohexane/ethyl acetate 3:1) showed no further progress.

The reaction mixture was cooled to room temperature, ethyl acetate (100 g) was added and the layers were separated. The aqueous phase was extracted with ethyl acetate (50 g). The combined organic phases were washed successively with water (100 g) and then brine (100 g), dried over Na ₂SO₄, and the solvent was removed under reduced pressure to give the crude product. Purification by column chromatography (cyclohexane/ethyl acetate 3:1) afforded 21.5g of the title compound as a white solid with a chemical purity of >95%.

m.p.＝196℃-205℃

¹H NMR(80MHz,CDCl₃):δ＝9.04-8.54(m,8H),8.43–7.42(m,32H),3.95–3.05(m,8H),1.71(t,J＝6.2Hz,2H)ppm.

2.3 Refractive index n _D of the monomer of formula (I):

Table C below lists the refractive indices of some monomers of formula (I) calculated using software ACD/ChemSketch 2012 (ADVANCED CHEMISTRY Development, inc.). Each monomer in table C is identified by its entry number in tables a and B, respectively. Furthermore, it was confirmed by quantum-chemical calculations of all monomers included in table C that they were not absorbed or only absorbed to a negligible extent in the visible range and thus were substantially colorless.

Table C

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3. Preparation of polycarbonate resins from monomers of formula (I)

3.1 Analysis related to resins prepared from monomers of formula (I):

refractive index (n _D):

the refractive index was measured according to JIS B7071-2:2018 using a disk-shaped test piece made of polycarbonate resin having a thickness of 3mm as a test piece. The measurements were made using the following refractive index measurement device at 23 ℃.

Refractive index measuring device:

KPR-3000 manufactured by Shimadzu Corporation

Abbe number (v):

A disc-shaped test piece having a thickness of 3mm, which is the same as that of the test piece used for refractive index measurement, was used. Refractive index values were measured at 23℃and at wavelengths of 486nm, 589nm and 656nm using the following refractive index measuring device. The abbe number is then calculated using the following formula.

Refractive index measuring device:

KPR-3000 manufactured by Shimadzu Corporation

ν＝(nD-1)/(nF-nC)

ND: refractive index at wavelength 589nm

NC: refractive index at 656nm

NF: refractive index at wavelength 486nm

Glass transition temperature (Tg):

The glass transition temperature was measured by Differential Scanning Calorimetry (DSC) according to JIS K7121-1987 using a heating program of 10℃per minute.

Differential scanning calorimeter:

X-DSC7000 manufactured by HITACHI HIGH-TECH SCIENCE Corporation

Molecular weight

The weight average molecular weight (Mw) value of the resin is measured according to Gel Permeation Chromatography (GPC) and calculated by standard polystyrene substitution algorithm. The following devices, columns and measurement conditions were used:

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

Column: three TSKgel SuperHM-M (from Tosoh Corporation),

One protective column SuperHM-M (from Tosoh Corporation),

One TSKgel SuperH-RC (from Tosoh Corporation);

the detection device comprises: RI detection

Standard polystyrene: pstQuick C as standard polystyrene kit (from Tosoh Corporation);

eluent: tetrahydrofuran;

eluent flow rate: 0.6ml/min;

Column temperature: 40 ℃.

The number average molecular weight (Mn) value may be calculated using a method similar to the method for measuring the Mw value described above. The weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of polystyrene were calculated using a polystyrene standard curve prepared in advance. Specifically, a standard curve was made using standard polystyrene (from Tosoh Corporation, "PStQuick C") of known molecular weight. In addition, based on measurement data of standard polystyrene, elution time and molecular weight values of each peak are plotted, and three-dimensional approximation is performed, thereby obtaining a calibration curve. The values of Mw and Mn are calculated based on the following calculation formula:

Mw＝Σ(Wi x Mi)÷Σ(Wi)

Mn＝Σ(Ni x Mi)÷Σ(Wi)

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

Content of Low molecular weight Compound (CLWC)

The content of low molecular weight compounds (CLWC) represents the ratio of the combined peak area to the total area of all peaks of compounds having a Mw value of less than 1000, wherein the peak area is determined according to the GPC analysis described above. Thus, CLWC values were determined using the following formula:

GPC analysis used in this context is performed similarly to the analysis described above for measuring the molecular weight of thermoplastic resins.

Birefringence (Δn):

Each resin example to be analyzed was dissolved in methylene chloride (solvent) to form a solution having a concentration of 10 wt%. The resulting solution was cast onto an SUS plate whose surface was subjected to plating treatment to prepare a casting film, and then the solvent was evaporated at 25 ℃. Square films of thickness 100 μm and 50mm per side were cut from the cast film. The film sheet is stretched to 1.5 times or less at a temperature 20 ℃ higher than the Tg of the resin. Stretching was performed using a stretcher SS-70 manufactured by Shibayama Scientific co. Retardation measurements were performed on the obtained stretched film using ellipsometer M-220 manufactured by JASCO Corporation.

From the retardation/phase difference Re, the birefringence value Δn is calculated by the following formula:

Δn＝|Re/d|

An: orientation birefringence

Re: phase difference [ nm ]

D: thickness [ nm ]

The algebraic sign of birefringence uses the refractive index in the stretching direction of the film (n _II) and the refractive index in the direction perpendicular to the stretching direction (n _⊥), expressed by the following formula:

Δn＝n_II-n_⊥

if Δn is positive, it is referred to as positive birefringence; and if deltan is negative, it is referred to as negative birefringence.

3.2 Preparation examples of homopolycarbonates:

Examples 20 to 30:

Table 1 below lists the physical properties of the homopolycarbonates of examples 20 to 30, namely refractive index (n _D), abbe number (. Nu.), glass transition temperature (Tg) and birefringence (. DELTA.n), which can be obtained by reacting one of the monomers of formula (Ia-1) prepared in examples 1,2, 3, 4, 5, 6, 7, 8, 9, 10 or 13 as diol component with a carbonate-forming monomer such as diphenyl carbonate by a similar method for preparing polyestercarbonates which is well known in the art. Table 1 also lists the n _D and Tg values of two comparative homopolycarbonates prepared from 9, 9-bis (4- (2-hydroxyethoxy) phenyl) fluorene and bisphenol A, respectively, as diol components. Thus, the homopolycarbonates of examples 20 to 30 each consisted of structural units of formula (IIa-1) and structural units of formula (III-1), whereas the comparative homopolycarbonates consisted of structural units derived from the monomers 9, 9-bis (4- (2-hydroxyethoxy) phenyl) fluorene and bisphenol A, respectively, and structural units of formula (III-1).

The n _D value, v value, tg value and Δn value of the homopolycarbonates of examples 20 to 30 given in table 1 are calculated from the corresponding values of the corresponding copolymers derived from the monomers of examples 1,2,3,4,5,6, 7, 8, 9, 10 or 13 by using the Fox equation described above. The preparation of these copolymers and their physical data are described in examples 31 to 40 below. The n _D and Tg values of the comparative homopolycarbonates were taken from US 9,360,593.

Table 1: properties of the homopolycarbonates of examples 20 to 30

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* Comparing the compounds; the n _D value and Tg value are as reported in US 9,360,593

3.3 Preparation of copolycarbonates examples:

example 31: copolymers prepared from the monomers of example 1 and BPEF

As starting materials, 3.00kg (4.83 mol) of 2- [4- [1- [4- (2-hydroxyethoxy) -3, 5-diphenyl-phenyl ] -1-methyl-ethyl ] -2, 6-diphenyl-phenoxy ] ethanol (see example 1, also referred to below as TPBHBPA), 12.01kg (27.39 mol) of 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene (BPEF), 7.11kg (33.19 mol) of diphenyl carbonate (DPC) and 15ml of 2.5X10: 10 ²mol/l(7.8×10^-4 mol) aqueous sodium bicarbonate were placed in a 50 liter reactor with stirrer and distillation apparatus.

After flushing the reactor with nitrogen, the reaction mixture was heated to 205℃for 1 hour and stirred at 760 Torr. After the reaction mixture was completely dissolved, the pressure was lowered to 150Torr in 15 minutes, and then the transesterification reaction was carried out at 205℃and 150Torr for 20 minutes. In addition, the reaction mixture was heated to 240℃at a heating rate of 37.5℃per hour, and the reaction conditions of 240℃and 150Torr were maintained for 10 minutes. Then, the pressure was reduced to 120Torr in 10 minutes, and the reaction conditions of 240℃and 120Torr were maintained for 70 minutes. Then, the pressure was reduced to 100Torr in 10 minutes, and the reaction conditions of 240℃and 100Torr were maintained for 10 minutes. Further, the pressure was reduced to 1Torr or less in 40 minutes, and the polymerization reaction was carried out by stirring at 240℃and 1Torr for 10 minutes. After the completion of the reaction, the pressure was increased by introducing nitrogen gas into the reactor, and the resultant polycarbonate resin was pelletized and taken out of the reactor. The properties of the resulting polycarbonate resin are summarized in table 2 below.

TABLE 2

* The values given for the homopolymer of example 20 correspond to the values already listed in table 1.

Example 32: copolymers prepared from the monomers of example 2 and BPEF

As starting materials, 4.70kg (5.72 mol) of 2- [4- [1- [4- (2-hydroxyethoxy) -3, 5-bis (naphthalen-1-yl) phenyl ] -1-methyl-ethyl ] -2, 6-bis (naphthalen-1-yl) phenoxy ] ethanol (see example 2, also referred to below as T1 NBHBPA), 10.04kg (22.90 mol) of 9, 9-bis [4- (2-hydroxyethoxy) phenyl) fluorene (BPEF), 6.41kg (29.90 mol) of diphenyl carbonate (DPC) and 11ml of an aqueous solution of 2.5X10 ^-2 mol/l (2.8X10-4 mol) of sodium hydrogencarbonate were placed in a 50 liter reactor with stirrer and distillation apparatus. After flushing the reactor with nitrogen, the reaction mixture was heated to 205℃for 1 hour and stirred at 760 Torr. After the reaction mixture was completely dissolved, the pressure was lowered to 150Torr in 15 minutes, and then the transesterification reaction was carried out at 205℃and 150Torr for 20 minutes. In addition, the reaction mixture was heated to 240℃at a heating rate of 37.5℃per hour, and the reaction conditions of 240℃and 150Torr were maintained for 10 minutes. Then, the pressure was reduced to 120Torr in 10 minutes, and the reaction conditions of 240℃and 120Torr were maintained for 70 minutes. Then, the pressure was reduced to 100Torr in 10 minutes, and the reaction conditions of 240℃and 100Torr were maintained for 10 minutes. Further, the pressure was reduced to 1Torr or less in 40 minutes, and the polymerization reaction was carried out by stirring at 240℃and 1Torr for 10 minutes. After the completion of the reaction, the pressure was increased by introducing nitrogen gas into the reactor, and the resultant polycarbonate resin was pelletized and taken out of the reactor. The properties of the resulting polycarbonate resin are summarized in table 3 below.

TABLE 3 Table 3

* The values given for the homopolymer of example 21 correspond to the values already listed in table 1.

Example 33: copolymers prepared from the monomers of example 3 and BPEF

As starting materials, 6.51kg (7.93 mol) of 2- [4- [1- [4- (2-hydroxyethoxy) -3, 5-bis (naphthalen-2-yl) phenyl ] -1-methyl-ethyl ] -2, 6-bis (naphthalen-2-yl) phenoxy ] ethanol (see example 3, also referred to below as T2 NBHBPA), 8.12kg (18.51 mol) of 9, 9-bis [4- (2-hydroxyethoxy) phenyl) fluorene (BPEF), 5.83kg (27.22 mol) of diphenyl carbonate (DPC) and 31ml of an aqueous solution of 2.5X10 ^-2 mol/l (7.8X10-4 mol) of sodium hydrogencarbonate were placed in a 50 liter reactor with stirrer and distillation apparatus. After flushing the reactor with nitrogen, the reaction mixture was heated to 205℃for 1 hour and stirred at 760 Torr. After the reaction mixture was completely dissolved, the pressure was reduced to 150Torr in 15 minutes, and then the transesterification reaction was carried out at 205℃and 150Torr for 20 minutes. In addition, the reaction mixture was heated to 240℃at a heating rate of 37.5℃per hour, and the reaction conditions of 240℃and 150Torr were maintained for 10 minutes. Then, the pressure was reduced to 120Torr in 10 minutes, and the reaction conditions of 240℃and 120Torr were maintained for 70 minutes. Then, the pressure was reduced to 100Torr in 10 minutes, and the reaction conditions of 240℃and 100Torr were maintained for 10 minutes. Further, the pressure was reduced to 1Torr or less in 40 minutes, and the polymerization reaction was carried out by stirring at 240℃and 1Torr for 10 minutes. After the completion of the reaction, the pressure was increased by introducing nitrogen gas into the reactor, and the resultant polycarbonate resin was pelletized and taken out of the reactor. The properties of the resulting polycarbonate resin are summarized in table 4 below.

TABLE 4 Table 4

* The values given for the homopolymer of example 22 correspond to the values already listed in table 1.

Example 34: copolymers prepared from the monomers of example 4b and BPEF

As starting materials, 8.32kg (8.16 mol) of 2- [4- [1- [4- (2-hydroxyethoxy) -3, 5-bis (phenanthr-9-yl) -phenyl ] -1-methyl-ethyl ] -2, 6-bis (phenanthr-9-yl) -phenoxy ] ethanol (see example 4b, also referred to below as T9 PNBHBPA), 8.35kg (19.04 mol) of 9, 9-bis [4- (2-hydroxyethoxy) phenyl) fluorene (BPEF), 6.00kg (28.01 mol) of diphenyl carbonate (DPC) and 32ml of an aqueous solution of 2.5X10-2 mol/l (7.8X10-4 mol) of sodium hydrogencarbonate were placed in a 50 liter reactor with stirrer and distillation apparatus. After flushing the reactor with nitrogen, the reaction mixture was heated to 205℃for 1 hour and stirred at 760 Torr. After the reaction mixture was completely dissolved, the pressure was reduced to 150Torr in 15 minutes, and then the transesterification reaction was carried out at 205℃and 150Torr for 20 minutes. In addition, the reaction mixture was heated to 240℃at a heating rate of 37.5℃per hour, and the reaction conditions of 240℃and 150Torr were maintained for 10 minutes. Then, the pressure was reduced to 120Torr in 10 minutes, and the reaction conditions of 240℃and 120Torr were maintained for 70 minutes. Then, the pressure was reduced to 100Torr in 10 minutes, and the reaction conditions of 240℃and 100Torr were maintained for 10 minutes. Further, the pressure was reduced to 1Torr or less in 40 minutes, and the polymerization reaction was carried out by stirring at 240℃and 1Torr for 10 minutes. After the completion of the reaction, the pressure was increased by introducing nitrogen gas into the reactor, and the resultant polycarbonate resin was pelletized and taken out of the reactor. The properties of the resulting polycarbonate resin are summarized in table 5 below.

TABLE 5

* The values given for the homopolymer of example 23 correspond to the values already listed in table 1.

Example 35: copolymers prepared from the monomers of example 5 and BPEF

As starting material 9.00kg (8.61 mol) of 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 (or 2,2' - ((propane-2, 2-diylbis (2, 6-bis (dibenzo [ b, d ] thiophen-4-yl) -4, 1-phenylene)) bis (oxy)) bis (ethan-1-ol), see example 5, also referred to hereinafter as T4 DBTBHBPA), 8.81kg (20.09 mol) of 9, 9-bis [4- (2-hydroxyethoxy) phenyl) fluorene (BPEF), 6.33kg (29.56 mol) of diphenyl carbonate (DPC) and 11ml of 2.5X 10 ^- ²mol/l(2.8×10^-4 mol) aqueous solution were placed in a reactor with stirrer and a distillation apparatus.

After flushing the reactor with nitrogen, the reaction mixture was heated to 205℃for 1 hour and stirred at 760 Torr. After the reaction mixture was completely dissolved, the pressure was reduced to 150Torr in 15 minutes, and then the transesterification reaction was carried out at 205℃and 150Torr for 20 minutes. In addition, the reaction mixture was heated to 240℃at a heating rate of 37.5℃per hour, and the reaction conditions of 240℃and 150Torr were maintained for 10 minutes. Then, the pressure was reduced to 120Torr in 10 minutes, and the reaction conditions of 240℃and 120Torr were maintained for 70 minutes. The pressure was then reduced to 100Torr in 10 minutes, and the reaction conditions of 240℃and 100Torr were maintained for 10 minutes. Further, the pressure was reduced to 1Torr or less in 40 minutes, and the polymerization reaction was carried out at 240℃and 1Torr for 10 minutes. After the reaction was completed, the pressure was increased by introducing nitrogen into the reactor, and the resultant polycarbonate resin was pelletized and taken out of the reactor. The properties of the resulting polycarbonate resin are summarized in table 6 below.

TABLE 6

* The values given for the homopolymer of example 24 correspond to the values already listed in table 1.

Example 36: copolymers prepared from the monomers of example 6 and BPEF

As starting materials, 7.00kg (8.30 mol) of 2- [4- [4- (2-hydroxyethoxy) -3, 5-bis (naphthalen-1-yl) phenyl ] sulfonyl-2, 6-bis (naphthalen-1-yl) phenoxy ] ethanol (see example 6, also referred to below as T1 NBHBPS), 8.50kg (19.38 mol) of 9, 9-bis [4- (2-hydroxyethoxy) phenyl) fluorene (BPEF), 6.11kg (28.51 mol) of diphenyl carbonate (DPC) and 11ml of 2.5X10: 10 ^-2mol/l(2.8×10^-4 mol) aqueous sodium bicarbonate were placed in a 50 liter reactor with stirrer and distillation apparatus. After flushing the reactor with nitrogen, the reaction mixture was heated to 205℃for 1 hour and stirred at 760 Torr. After the reaction mixture was completely dissolved, the pressure was reduced to 150Torr in 15 minutes, and then the transesterification reaction was carried out at 205℃and 150Torr for 20 minutes. In addition, the reaction mixture was heated to 240℃at a heating rate of 37.5℃per hour, and the reaction conditions of 240℃and 150Torr were maintained for 10 minutes. Then, the pressure was reduced to 120Torr in 10 minutes, and the reaction conditions of 240℃and 120Torr were maintained for 70 minutes. The pressure was then reduced to 100Torr in 10 minutes, and the reaction conditions of 240℃and 100Torr were maintained for 10 minutes. Further, the pressure was reduced to 1Torr or less in 40 minutes, and the polymerization reaction was carried out at 240℃and 1Torr for 10 minutes. After the reaction was completed, the pressure was increased by introducing nitrogen into the reactor, and the resultant polycarbonate resin was pelletized and taken out of the reactor. The properties of the resulting polycarbonate resin are summarized in table 7 below.

TABLE 7

* The values given for the homopolymer of example 25 correspond to the values already listed in table 1.

Example 37: copolymers prepared from the monomers of example 7 and BPEF

As starting materials, 4.50kg (5.55 mol) of 2- [4- [4- (2-hydroxyethoxy) -3, 5-bis (naphthalen-1-yl) phenyl ] sulfanyl-2, 6-bis (naphthalen-1-yl) phenoxy ] ethanol (or 2,2' - ((thiobis (2, 6-bis (naphthalen-1-yl) -4, 1-phenylene)) bis (oxy)) bis (ethan-1-ol), see example 7, also referred to as T1NBHTDP hereinafter), 9.73kg (22.19 mol) of 9, 9-bis [4- (2-hydroxyethoxy) phenyl) fluorene (BPEF), 6.64kg (28.58 mol) of diphenyl carbonate (DPC) and 11ml of 2.5X10: 10 ^-2mol/l(2.8×10^-4 mol) aqueous sodium bicarbonate were placed in a 50 liter reactor with stirrer and distillation apparatus.

After flushing the reactor with nitrogen, the reaction mixture was heated to 205℃for 1 hour and stirred at 760 Torr. After the reaction mixture was completely dissolved, the pressure was reduced to 150Torr in 15 minutes, and then the transesterification reaction was carried out at 205℃and 150Torr for 20 minutes. In addition, the reaction mixture was heated to 240℃at a heating rate of 37.5℃per hour, and the reaction conditions of 240℃and 150Torr were maintained for 10 minutes. Then, the pressure was reduced to 120Torr in 10 minutes, and the reaction conditions of 240℃and 120Torr were maintained for 70 minutes. Then, the pressure was reduced to 100Torr in 10 minutes, and the reaction conditions of 240℃and 100Torr were maintained for 10 minutes. Further, the pressure was reduced to 1Torr or less in 40 minutes, and the polymerization reaction was carried out at 240℃and 1Torr for 10 minutes. After the reaction was completed, the pressure was increased by introducing nitrogen into the reactor, and the resultant polycarbonate resin was pelletized and taken out of the reactor. The properties of the resulting polycarbonate resin are summarized in table 8 below.

TABLE 8

* The values given for the homopolymer of example 26 correspond to the values already listed in table 1.

Example 38: copolymers prepared from the monomers of example 8 and BPEF

As starting materials, a 50 liter reactor with stirrer and distillation apparatus was charged with 4.24kg (4.06 mol) of an aqueous solution of 2- [4- [4- (2-hydroxyethoxy) -3, 5-bis (phenanthr-9-yl) phenyl ] sulfonyl-2, 6-bis (phenanthr-9-yl) phenoxy ] ethanol (see example 8, also referred to below as T9 PNBHBPS), 10.09kg (23.02 mol) of 9, 9-bis [4- (2-hydroxyethoxy) phenyl) fluorene (also referred to as BPEF), 5.92kg (27.62 mol) of diphenyl carbonate (also referred to as DPC) and 11ml of a total amount of 2.5X10 ^-2mol/l(2.7×10^-4mol(10×10^-6 mol of dihydroxyl compounds).

After flushing the reactor with nitrogen, the reaction mixture was heated to 205℃for 1 hour and stirred at 760 Torr. After the reaction mixture was completely dissolved, the pressure was reduced to 150Torr in 15 minutes, and then the transesterification reaction was carried out at 205℃and 150Torr for 20 minutes. In addition, the reaction mixture was heated to 240℃at a heating rate of 37.5℃per hour, and the reaction conditions of 240℃and 150Torr were maintained for 10 minutes. Then, the pressure was reduced to 120Torr in 10 minutes, and the reaction conditions of 240℃and 120Torr were maintained for 70 minutes. Then, the pressure was reduced to 100Torr in 10 minutes, and the reaction conditions of 240℃and 100Torr were maintained for 10 minutes. Further, the pressure was reduced to 1Torr or less in 40 minutes, and the polymerization reaction was carried out by stirring at 240℃and 1Torr for 10 minutes. After the reaction was completed, the pressure was increased by introducing nitrogen into the reactor, and the resultant polycarbonate resin was pelletized and taken out of the reactor. The properties of the resulting polycarbonate resin are summarized in table 9 below.

TABLE 9

Example 39: copolymers prepared from the monomers of example 10 and BPEF

As starting materials, 5.06kg (4.23 mol) of 2- [4- [4- (2-hydroxyethoxy) -3, 5-bis (thianthin-1-yl) phenyl ] sulfonyl-2, 6-bis (thianthin-1-yl) phenoxy ] ethanol (or 2,2' - ((sulfonylbis (2, 6-bis (thianthin-1-yl) -4, 1-phenylene)) bis (oxy)) bis (ethan-1-ol), see example 10, also referred to as T1TNTBHBPS, 10.51kg (23.96 mol) of 9, 9-bis [4- (2-hydroxyethoxy) phenyl) fluorene (also referred to as BPEF), 6.19kg (28.89 mol) of diphenyl carbonate (also referred to as DPC) and 11ml of aqueous sodium bicarbonate solution (2.5X10 ^-2mol/l(2.8×10^-4mol(10×10^-6 mol relative to the total amount of 1mol of dihydroxy compound) were placed in a 50 liter reactor with stirrer and distillation apparatus.

After flushing the reactor with nitrogen, the reaction mixture was heated to 205℃for 1 hour and stirred at 760 Torr. After the reaction mixture was completely dissolved, the pressure was reduced to 150Torr in 15 minutes, and then the transesterification reaction was carried out at 205℃and 150Torr for 20 minutes. In addition, the reaction mixture was heated to 240℃at a heating rate of 37.5℃per hour, and the reaction conditions of 240℃and 150Torr were maintained for 10 minutes. Then, the pressure was reduced to 120Torr in 10 minutes, and the reaction conditions of 240℃and 120Torr were maintained for 70 minutes. Then, the pressure was reduced to 100Torr in 10 minutes, and the reaction conditions of 240℃and 100Torr were maintained for 10 minutes. Further, the pressure was reduced to 1Torr or less in 40 minutes, and the polymerization reaction was carried out by stirring at 240℃and 1Torr for 10 minutes. After the reaction was completed, the pressure was increased by introducing nitrogen into the reactor, and the resultant polycarbonate resin was pelletized and taken out of the reactor. The properties of the resulting polycarbonate resin are summarized in table 10 below.

Table 10

* The values given for the homopolymer of example 29 correspond to the values already listed in table 1.

Example 40: copolymers prepared from the monomers of example 13 and BPEF

As a starting material, 9.91kg (8.44 mol) of 2,2'- (propane-2, 2-diylbis { [2, 6-bis (thianthin-1-yl) -4, 1-phenylene ] oxy }) bis (ethan-1-ol) (or 2,2' - ((propane-2, 2-diylbis (2, 6-bis (thianthin-1-yl) -4, 1-phenylene)) bis (oxy)) bis (ethan-1-ol)) see example 13, also referred to hereinafter as T1 TNTBHBPA), 8.64kg (19.70 mol) of 9, 9-bis [4- (2-hydroxyethoxy) phenyl) fluorene (also referred to as BPEF), 6.21kg (28.99 mol) of diphenyl carbonate (also referred to as DPC) and 11ml of 2.5x10 ^-2mol/l(2.8×10^-4mol(10×10^-6 mol relative to the total amount of 1mol of dihydroxy compound) sodium bicarbonate were placed in a 50 liter reactor with stirrer and distillation apparatus.

After flushing the reactor with nitrogen, the reaction mixture was heated to 205℃for 1 hour and stirred at 760 Torr. After the reaction mixture was completely dissolved, the pressure was reduced to 150Torr in 15 minutes, and then the transesterification reaction was carried out at 205℃and 150Torr for 20 minutes. In addition, the reaction mixture was heated to 240℃at a heating rate of 37.5℃per hour, and the reaction conditions of 240℃and 150Torr were maintained for 10 minutes. Then, the pressure was reduced to 120Torr in 10 minutes, and the reaction conditions of 240℃and 120Torr were maintained for 70 minutes. Then, the pressure was reduced to 100Torr in 10 minutes, and the reaction conditions of 240℃and 100Torr were maintained for 10 minutes. Further, the pressure was reduced to 1Torr or less in 40 minutes, and the polymerization reaction was carried out by stirring at 240℃and 1Torr for 10 minutes. After the reaction was completed, the pressure was increased by introducing nitrogen into the reactor, and the resultant polycarbonate resin was pelletized and taken out of the reactor. The properties of the resulting polycarbonate resin are summarized in table 11 below.

TABLE 11

* The values given for the homopolymer of example 30 correspond to the values already listed in table 1.

Example 41: copolymers prepared from the monomers of example 15 and BPEF

As a starting material, 14.7047g (0.0335 mol) of 9, 9-bis [4- (2-hydroxyethoxy) phenyl) fluorene (BPEF), 11.1975g (0.0144 mol) of 2,2' - { [3,3', 5' -tetrakis (naphthalen-2-yl) [1,1' -biphenyl ] -4,4' -diyl ] bis (oxy) } bis (ethylene-1-ol) (T2 NBHB P), 10.5222g (0.0491 mol) of diphenyl carbonate (DPC) and 0.4025X 10 ^-4g(0.4771×10^-6 mol) of sodium hydrogencarbonate obtained in example 15 were placed in a 300 ml reactor with a stirrer and a distillation apparatus.

After flushing the reactor with nitrogen, the internal pressure was set at 101.3kPa. The reactor was immersed in an oil bath heated to 200 ℃ to initiate the transesterification reaction. The reaction mixture was stirred 5 minutes after the start of the reaction. After 20 minutes, the pressure was reduced from 101.3kPa to 26.66kPa during 10 minutes, during which the reaction mixture was heated to 210 ℃. The reaction mixture was further heated to 220 ° within 60 minutes after the start of the reaction. From the 80 minute point after the start of the reaction, the pressure was reduced to 20.00kPa within 10 minutes, and then the reaction mixture was heated to 240 ℃ while the pressure was reduced to below 0.1 kPa. Then, the temperature was 240℃and the pressure was kept below 0.1kPa for 30 minutes. The pressure was then restored to 101.3kPa by introducing nitrogen to obtain the desired polycarbonate resin. The properties of the resulting resin are summarized in table 12.

Example 42: copolymers prepared from the monomers of example 14c and BPEF

As a starting material, 16.0001g (0.0365 mol) of 9, 9-bis [4- (2-hydroxyethoxy) phenyl) fluorene (BPEF), 12.1815g (0.0156 mol) of 2,2' - { [3,3', 5' -tetrakis (naphthalen-1-yl) [1,1' -biphenyl ] -4,4' -diyl ] bis (oxy) } bis (ethan-1-ol) (T1 NBHB P), 11.4484g (0.0534 mol) of diphenyl carbonate (DPC) and 0.4379X 10 ^-4g(0.5213×10^-6 mol) of sodium hydrogencarbonate obtained in example 14c were placed in a 300 ml reactor with a stirrer and a distillation apparatus.

After flushing the reactor with nitrogen, the internal pressure was set at 101.3kPa. The reactor was immersed in an oil bath heated to 200 ℃ to initiate the transesterification reaction. The reaction mixture was stirred 5 minutes after the start of the reaction. After 20 minutes, the pressure was reduced from 101.3kPa to 26.66kPa during 10 minutes, during which the reaction mixture was heated to 210 ℃. The reaction mixture was further heated to 220 ℃ within 60 minutes after the start of the reaction. From the 80 minute point after the start of the reaction, the pressure was reduced to 20.00kPa within 10 minutes, and then the reaction mixture was heated to 240 ℃ while the pressure was reduced to below 0.1 kPa. Then, the temperature was 240℃and the pressure was kept below 0.1kPa for 30 minutes. The pressure was then restored to 101.3kPa by introducing nitrogen to obtain the desired polycarbonate resin. The properties of the resulting resin are summarized in table 12.

Comparative example: copolycarbonates prepared from BNE and BPEF

The copolycarbonate resin of this comparative example was prepared similarly to the method described in example 41 above, except that 2,2 '-bis (2-hydroxyethoxy) -1,1' -Binaphthyl (BNE) was used as a comonomer instead of T2NBHB P. The properties of the resulting resin are summarized in table 12.

Table 12

* The value CLWC (content of low molecular weight compound) was measured as follows.

The content (CLWC) of the low molecular weight compounds listed in table 12 was calculated using the method detailed above, which was based on GPC data calibrated against polystyrene standards. For example, CLWC values of the resin of example 41 reported in table 12 were calculated from the areas of the respective peaks obtained from the GPC diagram of the resin shown in fig. 3 using the above formula. The correlation peak data are summarized in tables 13 and 13-2 below. Specifically, the ratio of the sum of peak areas (66697+23135+12863= 102695) of the compounds having Mw values below 1000 to the total area (6318321) of all peaks was calculated. Thus, the content of the low molecular weight compound in the resin of example 41 was calculated to be 1.6% (102695/6318321×100).

Table 13: data of peaks of GPC chart of resin of example 41

Table 13-2: details of peaks of GPC chart of resin of example 41

Birefringence measurement:

Fig. 2 is a partially enlarged portion of the retardation or birefringence of the polymers of examples 31, 33 and 34 of fig. 1.

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

Fig. 1 demonstrates that TPBHBPA, T2NBHBPA, and T9PNBHBPA provide polycarbonates with very low absolute values of positive or negative birefringence. These properties have not been found in conventional materials, and TPBHBPA, T2NBHBPA, and T9PNBHBPA are particularly useful as optical materials.

Claims

1. A compound of formula (I),

Wherein the method comprises the steps of

Z ¹ and Z ² are independently selected from hydrogen 、-Alk-OH、-CH₂-Ar²-CH₂-OH、-Alk'-C(O)OR^x、-CH₂-Ar²-C(O)OR^x and-C (O) -Ar ²-C(O)OR^x, wherein R ^x is selected from hydrogen, phenyl, benzyl and C ₁-C₄ -alkyl;

r ⁵ is selected from hydrogen and C ₁-C₄ -alkyl;

r ⁶ is selected from hydrogen and C ₁-C₄ -alkyl;

Ar ¹ is selected from the group consisting of a monocyclic or polycyclic aryl group having from 6 to 26 carbon atoms as ring members and a monocyclic or polycyclic heteroaryl group having from 5 to 26 total atoms as ring members, wherein 1,2, 3 or 4 of the ring member atoms of the heteroaryl group are selected from nitrogen, sulfur and oxygen and the remaining atoms of the heteroaryl group are carbon atoms, wherein the monocyclic or polycyclic aryl group and the monocyclic or polycyclic heteroaryl group are unsubstituted or carry 1,2, 3 or 4R ^Ar groups;

Ar ² is selected from the group consisting of phenylene, naphthylene, and biphenylene;

Alk is C ₂-C₄ -alkanediyl;

Alk' is C ₁-C₄ -alkanediyl;

r is selected from methyl, ethyl, phenyl, naphthyl, phenanthryl and triphenylene wherein phenyl, naphthyl, phenanthryl and triphenylene are unsubstituted or substituted with 1, 2,3 or 4R' groups which may be the same or different;

R' is selected from phenyl, OCH ₃、CH₃、N(CH₃)₂ and C (O) CH ₃; and

N is 0,1 or 2;

2. The compound of claim 1, wherein formula (I) is represented by formula (Ia):

3. The compound according to claim 1 or claim 2, wherein X is selected from single bond, O, N-methyl, N-ethyl, N-isopropyl, N-phenyl, N-naphthyl, N-phenanthryl, CH ₂、C(CH₃)₂、CH(CH₃), S and SO ₂, and in particular from single bond, O, CH ₂、C(CH₃)₂、CH(CH₃), S and SO ₂.

4. The compound according to any one of the preceding claims, wherein Z ¹ and Z ² are selected from hydrogen, 2-hydroxyethyl, methoxycarbonyl-methyl, hydroxymethyl-phenyl-methyl, hydroxymethyl-naphthyl-methyl, hydroxymethyl-biphenyl-methyl, methoxycarbonyl-phenyl-methyl and methoxycarbonyl-naphthyl-methyl, in particular from hydrogen, 2-hydroxyethyl, methoxycarbonyl-methyl, (4- (hydroxymethyl) phenyl) methyl, (3- (hydroxymethyl) phenyl) methyl, (4- (hydroxymethyl) -1-naphthyl) methyl, (5- (hydroxymethyl) -1-naphthyl) methyl, (6- (hydroxymethyl) -2-naphthyl) methyl, 4'- (hydroxymethyl) -1,1' -biphenyl-4-methyl, (4- (methoxycarbonyl) phenyl) methyl, (3- (methoxycarbonyl) phenyl) methyl, (4- (methoxycarbonyl) -1-naphthyl) methyl and (6- (methoxycarbonyl) -2-naphthyl) methyl.

5. A compound according to any one of the preceding claims wherein R ¹ and R ² are independently selected from phenyl, naphthyl, 1, 2-dihydroacenaphthenyl, biphenyl, fluorenyl, 11H-benzo [ a ] fluorenyl, 11H-benzo [ b ] fluorenyl, 7H-benzo [ c ] fluorenyl, phenanthryl, benzo [ c ] phenanthryl, pyrenyl,A radical, picene radical, triphenylene radical, benzo [ b ] furyl radical, dibenzo [ b, d ] furyl radical, naphtho [1,2-b ] furyl radical, naphtho [2,3-b ] furyl radical, naphtho [2,1-b ] furyl radical, benzo [ b ] naphtho [1,2-d ] furyl radical, benzo [ b ] naphtho [2,3-d ] furyl radical, benzo [ b ] naphtho [2,1-d ] furyl radical, benzo [1,2-b:4,3-b ' ] bisfuranyl, benzo [1,2-b ] 6,5-b ' ] bisfuranyl, benzo [1,2-b ] 5,4-b ' ] bisfuranyl, benzo [1,2-b ] thienyl, naphtho [2,1-b ] thienyl, benzo [ b ] naphtho [1,8-d, e ] [1,3] dioxinyl, dinaphtho [2,3-b ] 2',3' -d ] furanyl, oxaanthracenyl, benzo [ a ] oxaanthracenyl, benzo [ b ] thienyl, benzo [ b, d ] thienyl, naphtho [1,2-b ] thienyl, naphtho [2,3-b ] thienyl, naphtho [2,1-b ] thienyl, benzo [ b ] naphtho [1,2-d ] thienyl, benzo [2,3-b ] thienyl, benzo [ a ] oxa [2,3-b ] thienyl, benzo [ b ] 2, 2-b ] thienyl, 5-b ] benzothienyl, benzo [1,2-b ] thienyl, 4-b ] thienyl, benzo [ b ] thienyl, 1, 3-b ] thienyl, benzo [ b ] thienyl, 4-b ] thienyl 1, 4-benzodithiinyl, naphtho [1,2-b ] [1,4] dithiinyl, naphtho [2,3-b ] [1,4] dithiinyl, thianthrenyl, benzo [ a ] thianthrenyl, benzo [ b ] thianthrenyl, dibenzo [ a, c ] thianthrenyl, dibenzo [ a, H ] thianthrenyl, dibenzo [ a, i ] thianthrenyl, dibenzo [ a, j ] thianthrenyl, dibenzo [ b, i ] thianthrenyl, 2H-naphtho [1,8-b, c ] thienyl, dibenzo [ b, d ] thianthrenyl, dibenzo [ b, f ] thianthrenyl, 5H-phenanthro [4,5-b, c, d ] thiapyranyl, tribenzo [ b, d, f ] thianthrenyl, 2, 5-dihydronaphtho [1,8-b, c); 4,5-b ', c' ] bithiophene radical, 2, 6-dihydronaphtho [1,8-b, c:5,4-b ', c' ] bithiophene radical, tribenzo [ a, c, i ] thianthrene radical, benzo [ b ] naphtho [1,8-e, f ] [1,4] dithienyl radical, dinaphtho [2,3-b:2',3' -d ] thiophene radical, 5H-phenanthro [1,10-b, c ] thiophene radical, 7H-phenanthro [1,10-c, b ] thiophene radical, dibenzo [ d, d '] benzo [1,2-b:4,5-b' ] bithiophene radical and dibenzo [ d, d '] benzo [1,2-b:5,4-b' ] bithiophene radical.

6. The compound of claim 5, wherein R ¹ and R ² are independently selected from phenyl, naphthyl, 1, 2-dihydroacenaphthylene, phenanthryl, pyrenyl, triphenylene, benzo [ b ] furanyl, dibenzo [ b, d ] furanyl, benzo [ b ] thiophenyl, dibenzo [ b, d ] thiophenyl, and thianthrenyl.

7. A compound according to any one of the preceding claims, wherein R ¹ and R ² have the same meaning.

8. The compound according to any one of the preceding claims, wherein R ³ and R ⁴ are 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 the ring member atoms of the heteroaryl groups are selected from nitrogen, sulfur and oxygen, while the remaining atoms of the ring member atoms of the heteroaryl groups are carbon atoms, wherein the monocyclic or polycyclic aryl groups and the monocyclic or polycyclic heteroaryl groups are unsubstituted or carry 1,2, 3 or 4R ^Ar groups.

9. The compound of claim 8, wherein R ³ and R ⁴ are independently selected from phenyl, naphthyl, 1, 2-dihydroacenaphthylenyl, biphenyl, fluorenyl, 11H-benzo [ a ] fluorenyl, 11H-benzo [ b ] fluorenyl, 7H-benzo [ c ] fluorenyl, phenanthryl, benzo [ c ] phenanthryl, pyrenyl,A radical, picene radical, triphenylene radical, benzo [ b ] furyl radical, dibenzo [ b, d ] furyl radical, naphtho [1,2-b ] furyl radical, naphtho [2,3-b ] furyl radical, naphtho [2,1-b ] furyl radical, benzo [ b ] naphtho [1,2-d ] furyl radical, benzo [ b ] naphtho [2,3-d ] furyl radical, benzo [ b ] naphtho [2,1-d ] furyl radical, benzo [1,2-b:4,3-b ' ] bisfuranyl, benzo [1,2-b ] 6,5-b ' ] bisfuranyl, benzo [1,2-b ] 5,4-b ' ] bisfuranyl, benzo [1,2-b ] thienyl, naphtho [2,1-b ] thienyl, benzo [ b ] naphtho [1,8-d, e ] [1,3] dioxinyl, dinaphtho [2,3-b ] 2',3' -d ] furanyl, oxaanthracenyl, benzo [ a ] oxaanthracenyl, benzo [ b ] thienyl, benzo [ b, d ] thienyl, naphtho [1,2-b ] thienyl, naphtho [2,3-b ] thienyl, naphtho [2,1-b ] thienyl, benzo [ b ] naphtho [1,2-d ] thienyl, benzo [2,3-b ] thienyl, benzo [ a ] oxa [2,3-b ] thienyl, benzo [ b ] 2, 2-b ] thienyl, 5-b ] benzothienyl, benzo [1,2-b ] thienyl, 4-b ] thienyl, benzo [ b ] thienyl, 1, 3-b ] thienyl, benzo [ b ] thienyl, 4-b ] thienyl 1, 4-benzodithiinyl, naphtho [1,2-b ] [1,4] dithiinyl, naphtho [2,3-b ] [1,4] dithiinyl, thianthrenyl, benzo [ a ] thianthrenyl, benzo [ b ] thianthrenyl, dibenzo [ a, c ] thianthrenyl, dibenzo [ a, H ] thianthrenyl, dibenzo [ a, i ] thianthrenyl, dibenzo [ a, j ] thianthrenyl, dibenzo [ b, i ] thianthrenyl, 2H-naphtho [1,8-b, c ] thienyl, dibenzo [ b, d ] thianthrenyl, dibenzo [ b, f ] thianthrenyl, 5H-phenanthro [4,5-b, c, d ] thiapyranyl, tribenzo [ b, d, f ] thianthrenyl, 2, 5-dihydronaphtho [1,8-b, c); 4,5-b ', c' ] bithiophene radical, 2, 6-dihydronaphtho [1,8-b, c:5,4-b ', c' ] bithiophene radical, tribenzo [ a, c, i ] thianthrene radical, benzo [ b ] naphtho [1,8-e, f ] [1,4] dithienyl radical, dinaphtho [2,3-b:2',3' -d ] thiophene radical, 5H-phenanthro [1,10-b, c ] thiophene radical, 7H-phenanthro [1,10-c, b ] thiophene radical, dibenzo [ d, d '] benzo [1,2-b:4,5-b' ] bithiophene radical and dibenzo [ d, d '] benzo [1,2-b:5,4-b' ] bithiophene radical.

10. The compound of claim 9, wherein R ³ and R ⁴ are independently selected from phenyl, naphthyl, 1, 2-dihydroacenaphthylene, phenanthryl, pyrenyl, triphenylene, benzo [ b ] furanyl, dibenzo [ b, d ] furanyl, benzo [ b ] thiophenyl, dibenzo [ b, d ] thiophenyl, and thianthrenyl.

11. A compound according to any one of the preceding claims, wherein R ¹、R²、R³ and R ⁴ have the same meaning.

12. A compound according to any one of the preceding claims, wherein formula (I) is represented by formula (Ia-1), wherein Z is as defined in claim 1 or claim 4 as Z ¹ and Z ²:

13. A compound according to claim 12, wherein R ^y, X and Z are as defined in one row of table a', wherein R ^y represents the same meaning of substituents R ¹、R²、R³ and R ⁴:

Table A'

14. A compound according to any one of the preceding claims, wherein formula (I) is represented by formula (Ia-2), wherein Z is as defined in claim 1 or claim 4 as Z ¹ and Z ²:

15. A compound according to claim 12, wherein R ^y, X and Z are as defined in one row of table B, wherein R ^y represents the same meaning of substituents R ¹、R²、R³ and R ⁴:

Table B

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16. A thermoplastic resin comprising a structural unit represented by the following formula (II)

Wherein the method comprises the steps of

# Represents the connection point with the adjacent structural unit;

And wherein Z ^1a and Z ^2a are derived from Z ¹ OR Z ², respectively, in formula (I), replacing hydrogen with a single bond if Z ¹ OR Z ² is hydrogen, OR replacing the-OH OR-OR ^x group of Z ¹ OR Z ² with an oxo (-O-) unit if Z ¹ OR Z ² is not hydrogen,

And wherein Z ¹、Z²、X、R¹、R²、R³ and R ⁴ are as defined in any one of claims 1 to 15.

17. The thermoplastic resin of claim 16, wherein formula (II) is represented by formula (IIa):

18. The thermoplastic resin according to claim 17, wherein the formula (IIa) is represented by formula (IIa-1), wherein the definition of Z ^a is the same as the definitions of Z ^1a and Z ^2a in claim 16:

19. The thermoplastic resin according to claim 17, wherein the formula (IIa) is represented by formula (IIa-2), wherein the definition of Z ^a is the same as the definitions of Z ^1a and Z ^2a in claim 16:

20. the thermoplastic resin according to any one of claims 16 to 19, wherein the structural unit of formula (II) in which Z ¹ and Z ² are selected from hydrogen, -Alk-OH and-CH ₂-Ar²-CH₂ -OH is linked to one of the structures represented by the following formulas (III-1) to (III-5),

Wherein the method comprises the steps of

# Denotes the connection point to the adjacent building block.

21. The thermoplastic resin according to any one of claims 16 to 20, which is selected from the group consisting of a copolycarbonate resin, a copolyestercarbonate resin and a copolyester resin, wherein the thermoplastic resin comprises structural units of formula (V) in addition to structural units of formula (II),

#-O-R^z-A¹-R^z-O-#- (V)

Wherein the method comprises the steps of

# Represents the connection point with the adjacent structural unit;

Wherein the method comprises the steps of

Q represents a single bond, O, NH, c= O, CH ₂ or ch=ch;

R ^7a、R^7b is independently selected from hydrogen, fluorine, CN, R, OR, CH _kR_3-k、NR₂, C (O) R and C (O) NH ₂, wherein R is as defined in claim 1 and k is 0, 1,2 or 3; and

* Represents a point of attachment to a benzene ring;

Ar is selected from the group consisting of a monocyclic or polycyclic aryl group having from 6 to 26 carbon atoms as ring atoms and a monocyclic or polycyclic heteroaryl group having from 5 to 26 total atoms as ring members, wherein 1, 2, 3 or 4 of the ring member atoms of the heteroaryl group are selected from nitrogen, sulfur and oxygen and the remaining atoms of the ring member atoms of the heteroaryl group are carbon atoms, wherein Ar is unsubstituted or substituted with 1, 2 or 3R ^ab groups selected from halogen, phenyl and C ₁-C₄ -alkyl;

P is an integer of 1 to 10;

Alk ¹ is C ₁-C₄ -alkanediyl;

Alk ² is C ₂-C₄ -alkanediyl; and

Alk ³ is C ₁-C₄ -alkanediyl.

22. The thermoplastic resin of claim 21, wherein the structural unit of formula V is represented by one of the following formulas V-1 to V-6:

Wherein the method comprises the steps of

A and b are 0, 1, 2 or 3, in particular 0 or 1;

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

e and f are 0, 1,2, 3, 4 or 5, in particular 0 or 1;

And wherein R ^z、R^aa、R^ab、R^7a and R ^7b are as defined in formula (V).

23. The thermoplastic resin of any one of claims 21 or 22, wherein the molar ratio of structural units of formula (II) is from 1 to 70 mole percent based on the total molar amount of structural units of formulae (II) and (V), and wherein the molar ratio of structural units of formula (V) is from 30 to 99 mole percent based on the total molar amount of structural units of formulae (II) and (V).

24. The thermoplastic resin according to any one of claims 16 to 23, having a refractive index of 1.640 or more.

25. The thermoplastic resin according to any one of claims 16 to 24, which has an abbe number of 24 or less.

26. The thermoplastic resin of any one of claims 16 to 25 having a glass transition temperature (Tg) of 90 to 185 ℃.

27. The thermoplastic resin of any one of claims 16 to 26 having a weight average molecular weight of 10000 to 50000 as measured by gel permeation chromatography, with polystyrene as a standard.

28. The thermoplastic resin of any one of claims 16-27, comprising a low molecular weight compound having a molecular weight (Mw) below 1000, wherein the content of the low molecular weight compound (CLWC) in the thermoplastic resin is in the range of 0.3 wt% to 7.0 wt%, based on the total weight of the thermoplastic resin, and wherein CLWC is represented by the formula:

29. An optical device made of the thermoplastic resin of any one of claims 16 to 28.

30. Use of a compound of formula (I) as defined in any one of claims 1 to 15 as a monomer of a thermoplastic resin as defined in any one of claims 16 to 29.