CN118043298A

CN118043298A - (Hetero) aryl-substituted bisphenol compound and thermoplastic resin

Info

Publication number: CN118043298A
Application number: CN202280066399.6A
Authority: CN
Inventors: 瓦西里·安德鲁什科; 卡尔·路特; 菲利普·科施克; 弗洛里安·斯托尔兹; 马克·坎托; 加藤宣之; 西森克吏; 茂木笃志; 石原健太朗; 池田慎也; 渡边贵史; 绪方龙展; 高松一贵; 原田祐太郎
Original assignee: Royt Chemical Instrument Manufacturing Co ltd
Current assignee: Royt Chemical Instrument Manufacturing Co ltd
Priority date: 2021-09-10
Filing date: 2022-09-08
Publication date: 2024-05-14

Abstract

The present invention relates to compounds of formula (I)Wherein 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 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 ¹ and R ² are independently selected from: optionally substituted mono-or polycyclic aryl groups having 6 to 26 carbon atoms as ring members and optionally substituted mono-or polycyclic heteroaryl groups having a total of 5 to 26 atoms as ring members, R ⁵ is selected from: hydrogen, C ₁-C₄ -alkyl and the radical Ar ¹;R⁶ are selected from: hydrogen and C ₁-C₄ -alkyl; alk is C ₂-C₄ -alkanediyl; provided that both R ³ and R ⁴ are hydrogen, then both R ¹ and R ² are not phenyl. The present invention 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 represented by the following formula (II)Wherein # denotes the point of attachment to the adjacent building block; and wherein X, Z ^1a、Z^2a、R¹、R²、R³ and R ⁴ are as defined herein, and also to such thermoplastic resins. The present invention also relates to an optical device made of a thermoplastic resin comprising a structural unit represented by formula (II) as defined herein.

Description

(Hetero) aryl-substituted bisphenol compound and thermoplastic resin

Technical Field

The present invention relates to (hetero) aryl substituted bisphenol compounds suitable as monomers for the preparation of thermoplastic resins, such as polycarbonate resins, which resins have advantageous optical and mechanical properties and are useful for the production of optical devices.

Background

Optical devices (such as optical lenses) made of optical resins instead of optical glasses have an advantage in that they can be mass-produced by injection molding. Optical resins, especially transparent polycarbonate resins, are often used today to manufacture camera lenses. In this regard, resins with higher refractive indices are highly desirable because they allow for a reduction in the size and weight of the final product. When an optical material having a higher refractive index is used, a lens element having generally the same refractive power can be realized with a surface having a smaller curvature, so that the amount of aberration generated on this surface can be reduced. Thus, it is possible to reduce the number of lenses, reduce the offset sensitivity of the lenses, and/or 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 producing an optical lens having a low Abbe number (Abbe number) of 23 to 26 and a refractive index of 1.62 to 1.64.

US 9,360,593 describes polycarbonate resins having repeat units derived from 2,2' -bis (2-hydroxyethoxy) -1, 1-binaphthyl. Polycarbonate resins are said to have favorable 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 and 10, 10-bis (4-hydroxyphenyl) -anthrone monomers and their use for the preparation of optical lenses are described in U.S. Pat. No. 5,2016,9069. The copolymers are reported to have good moisture resistance and have refractive indices in the range of about 1.662 to 1.667.

WO 2019/043060 describes thermoplastic resins for the manufacture of optical materials, wherein the thermoplastic resins comprise 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 mono-or polycyclic aryl groups having 6 to 36 carbon atoms and optionally substituted mono-or polycyclic heteroaryl groups having a total of 5 to 36 atoms.

WO 2019/154727 describes thermoplastic resins for the manufacture of optical materials, wherein the thermoplastic resins comprise 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 mono-or polycyclic aryl and mono-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 polymeric compound of formula (4)

Wherein the method comprises the steps of

A ¹、A² is selected from mono-or bicyclic aromatic radicals and mono-or bicyclic heteroaromatic radicals,

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 definition as X;

r ¹、R² is hydrogen, a free radical Ar' or a free radical R ^a;

R ³ is especially O-alkylene;

m, n are 0,1 or 2;

r ⁴、R⁵ is, for example, selected from CN and the radical R ^a;

R ^a is selected from: C.ident.C-R ¹¹ and Ar-C.ident.C-R ¹¹, where R ¹¹ and Ar are aromatic radicals,

Wherein at least one of the radicals attached to a ¹ or a ² is a radical 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 ] -benzenesulfone) and bis [ (2-hydroxyethoxy) -2,2' -phenyl ] -4,4' -bisphenol).

Monomers used to make thermoplastic resins having high refractive indices also typically result in positive birefringence values for the resin. Birefringence is an undesirable property of an optical device. Heretofore, positive birefringence has been compensated for by using comonomers having negative birefringence, such as 9, 9-bis (4- (2-hydroxy-ethoxy) phenyl) fluorene. However, such comonomers reduce the refractive index of the resulting polymer. There are few known monomers that 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 monomers 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. Furthermore, the monomers should be easy to prepare. In addition, resins obtained from such monomers (particularly polyesters and polycarbonates) should have good moisture and heat resistance, and such resins should have sufficiently high glass transition temperatures suitable for injection molding.

Reference list

Patent literature

Patent document 1: EP2034337

Patent document 2: US 9,360,593

Patent document 3: US 2016/0319069

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

Surprisingly, it was found that the compounds of formula (I) as described herein are useful monomers for the preparation of thermoplastic resins (in particular polycarbonates and polyesters) having high transparency and high refractive index, and also impart suitable glass transition temperatures to the polycarbonates and polyesters. Such thermoplastic resins are therefore suitable for the manufacture of optical resins where high transparency and high refractive index are required. Some of the monomers of formula (I) described herein provide both high refractive index and low or even negative birefringence. Moreover, 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. Thus, thermoplastic resins containing polymerized forms 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: mono-or polycyclic aryl groups having 6 to 26 carbon atoms as ring members and mono-or polycyclic heteroaryl groups having a total of 5 to 26 atoms as ring members, wherein 1,2, 3 or 4 of such ring member atoms of the heteroaryl group are selected from nitrogen, sulfur and oxygen, and the remaining atoms of such ring member atoms of the heteroaryl group are carbon atoms,

Wherein the mono-or polycyclic aryl and mono-or polycyclic heteroaryl are unsubstituted or contain 1, 2,3 or 4 radicals R ^Ar;

R ³ and R ⁴ are independently selected from: hydrogen, mono-or polycyclic aryl groups having from 6 to 26 carbon atoms as ring members, and mono-or polycyclic heteroaryl groups having a total of from 5 to 26 atoms as ring members, wherein 1, 2,3 or 4 of such ring member atoms of the heteroaryl group are selected from nitrogen, sulfur and oxygen, and the remaining atoms of such ring member atoms of the heteroaryl group are carbon atoms,

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: mono-or polycyclic aryl groups having 6 to 26 carbon atoms as ring members and mono-or polycyclic heteroaryl groups having a total of 5 to 26 atoms as ring members, wherein 1,2, 3 or 4 of such ring member atoms of the heteroaryl group are selected from nitrogen, sulfur and oxygen, and the remaining atoms of such ring member atoms of the heteroaryl group are carbon atoms,

Ar ² is selected from: phenylene, naphthylene, and biphenylene;

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', where R ^Ar may be the same OR different if more than one R ^Ar is present on the same (hetero) aryl group;

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 4 radicals R' which are identical or different;

R 'is selected from hydrogen, methyl, phenyl and naphthyl, wherein phenyl and naphthyl are unsubstituted or substituted with 1, 2, 3 or 4 radicals R' which are identical or different;

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

N is 0, 1 or 2;

Provided that both R ³ and R ⁴ are hydrogen, then both R ¹ and R ² are not phenyl.

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

When the compound of formula (I) is used as a monomer for preparing an optical resin (particularly a polycarbonate resin and a polyester resin), it provides a resin having a high refractive index. Moreover, the compounds of formula (I) provide resins of high transparency without significantly compromising other optical and mechanical properties of the resin. Such resins particularly meet other requirements of optical resins such as low abbe number, high transparency, and low birefringence. Moreover, the monomer provides a sufficiently high glass transition temperature to the optical resin thus produced. In addition, the monomers of formula (I) can be prepared easily and obtained in high yields and purity. The compounds of formula (I) are particularly obtainable in crystalline form, which can be purified effectively to the extent required for the preparation of optical resins. The compounds of formula (I) can be obtained particularly in purities which provide low haze, which is particularly important for the preparation of optical resins. Compounds of formula (I) that do not contain color-imparting free radicals, such as some of the free radicals R ¹、R²、R³、R⁴ and Ar ¹, can also provide purity gains of low yellow index y.i. and low APHA color number as determined according to ASTM E313, which is also important for use in preparing optical resins.

The present invention also relates to a thermoplastic resin comprising polymerized units of the compound of formula (I), i.e., a thermoplastic resin 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 ¹ a and Z ² a are each derived from Z ¹ or Z ² in formula (I), if Z ¹ or Z ² is hydrogen, the hydrogen is replaced by a single bond, or if Z ¹ or Z ² is not hydrogen, the-OH or-ORx group in Z ¹ or Z ² is replaced by an oxygen-containing (-O-) unit, and wherein Z ¹、Z²、X、R¹、R²、R³ and R ⁴ are as defined above.

The invention further relates to thermoplastic resins selected from the group consisting of copolycarbonate resins, 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 radical containing at least 2 benzene rings, wherein the benzene rings may be a linked and/or fused directly to each other and/or fused in a non-benzene carbocyclic ring, wherein a ¹ is unsubstituted or substituted with 1,2 or 3 radicals R ^aa selected from the group consisting of: halogen, C ₁-C₆ -alkyl, C ₅-C₆ -cycloalkyl and phenyl;

A is selected from: single bond, O, C = O, S, SO ₂、CH₂、CH-Ar、CAr₂、CH(CH₃)、C(CH₃)₂ and radical 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 are 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 is also provided with

* Represents a point of attachment to a benzene ring;

ar is selected from: mono-or polycyclic aryl groups having from 6 to 26 carbon atoms as ring members and mono-or polycyclic heteroaryl groups having a total of from 5 to 26 atoms as ring members, wherein 1, 2,3 or 4 of such ring member atoms of the heteroaryl group are selected from nitrogen, sulfur and oxygen and the remaining atoms of such ring member atoms of the heteroaryl group are carbon atoms, wherein Ar is unsubstituted or substituted with 1, 2 or 3 free radicals R ^ab 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 further relates to an optical device made of a thermoplastic resin as defined above, notably of a polyester, and in particular of a polycarbonate.

Drawings

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

FIG. 2 is a partial magnified view of the retardation or birefringence of the polymers of examples 31, 33, and 34 of FIG. 1.

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

Detailed Description

If X is a single bond, the compounds of formula (I) may have axial chirality depending on the type and position of substituents-O-Z ¹、-O-Z²、R¹、R²、R³ and R ⁴, which may be limited by rotation along the bond between the two phenylene moieties. In this case, the compounds of the formula (I) may thus be present 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 both racemic and non-racemic mixtures of enantiomers of compounds of formula (I) wherein X is a single bond, and in the case of enantiomers present in this class, the invention also relates to the pure (S) -and (R) -enantiomers thereof.

For the purposes of the present invention, the term "C ₁-C₄ -alkanediyl" is also denoted alternatively as "alkylene group having 1,2, 3 or 4 carbon atoms" and refers to a divalent, saturated, aliphatic hydrocarbon radical having 1,2, 3 or 4 carbon atoms. Examples of C ₂-C₄ -alkanediyl are in particular methylene (CH ₂) groups, straight-chain alkanediyl groups, such as 1, 2-ethanediyl (CH ₂CH₂), 1, 3-propanediyl (CH ₂CH₂CH₂) and 1, 4-butanediyl (CH ₂CH₂CH₂CH₂), but also branched alkanediyl groups, 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 radicals, 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 radical linked to the remainder of the molecule by a single covalent bond, in which the ring member atoms are part of a conjugated pi-electron system, in which the heteroaromatic monocyclic ring has 5 or 6 ring atoms which contain 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 ring members of a heterocycle, in which the remaining ring atoms are carbon atoms. Examples include furyl (furyl) (=furyl (furanyl)), pyrrolyl (=1H-pyrrolyl), thienyl (thienyl) (=thienyl (thiophenyl phenylthio)), imidazolyl (=1H-imidazolyl), pyrazolyl (=1H-pyrazolyl), 1,2, 3-triazolyl, 1,2, 4-triazolyl, tetrazolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, 1,3, 4-oxadiazolyl, 1,3, 4-thiadiazolyl, pyridyl (pyridyl) (=pyridyl (pyridinyl)), pyrazinyl, pyridazinyl, pyrimidinyl, and triazinyl.

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

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

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

(Iii) Polycyclic hydrocarbons containing at least 2 benzene rings covalently linked to each other or directly fused to each other and/or fused to a saturated or unsaturated 4-to 10-membered mono-or bicyclic hydrocarbon ring.

Mono-or polycyclic aryl groups have 6 to 26, frequently 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 as ring atoms, in particular from 10 to 20 carbon atoms, especially 10, 12, 13, 14, 16, 17 or 18 carbon atoms.

In this context, polycyclic aryl groups containing 2, 3 or 4 benzene rings linked to each other via single bonds include, for example, biphenyl and biphenyl groups. Polycyclic aryl groups containing 2, 3 or 4 benzene rings which are directly fused to each other include, for example, naphthyl, anthryl, phenanthryl, pyrenyl, triphenylenyl,A group (chrysenyl) and a benzo [ c ] phenanthryl group. Polycyclic aryl groups containing 2,3 or 4 benzene rings fused with saturated or unsaturated 4 to 10 membered mono-or bicyclic hydrocarbon rings include, for example, 9H-fluorenyl, biphenylenyl, tetraphenylenyl, acenaphthylenyl (ACENAPHTHENYL) (1, 2-acenaphthylenyl), acenaphthylenyl, 9, 10-dihydro-anthracene-1-yl, 1,2,3, 4-tetrahydrophenanthrenyl, 5,6,7, 8-tetrahydrophenanthrenyl, cyclopenta [ fg ] acenaphthylenyl, phenalenyl, allenecrenyl, benzo [ k ] allenecrenyl, perylenyl, 9, 10-dihydro-9, 10[1',2' ] -benzanthrenyl, dibenzo [ a, e ] [8] cycloalkenyl, 9 '-spirobis [ 9H-fluorenyl, and spiro [ 1H-cyclobutene ] naphthalene-1, 9' - [9H ] fluorenyl.

Mono-or polycyclic aryl groups include by way of example phenyl, naphthyl, 9H-fluorenyl, phenanthryl, anthracenyl, pyrenyl,A group, benzo [ c ] phenanthryl, acenaphthenyl, 2, 3-dihydro-1H-indenyl, 5,6,7, 8-tetrahydronaphthyl, cyclopenta [ fg ] acenaphthenyl, 2, 3-dihydrophenanyl, 9, 10-dihydroanthracen-1-yl, 1,2,3, 4-tetrahydrophenanthryl, 5,6,7, 8-tetrahydrophenanthryl, allene fluorenyl, benzo [ k ] allene fluorenyl, biphenylene, triphenylene, tetraphenylene, 1, 2-dihydroacenaphthylene, dibenzo [ a ], e ] [8] cycloalkenyl, perylene, biphenyl, naphthylene phenyl, phenanthrylphenyl, anthrylphenyl, pyrenylphenyl, 9H-fluorenylphenyl, di (naphthylene) phenyl, naphthylene biphenyl, tri (phenyl) phenyl, tetra (phenyl) phenyl, pentaphenyl (phenyl), phenylnaphthyl, binaphthyl, phenanthrylnaphthyl, pyrenylnaphthyl, phenylanthryl, biphenylanthryl, naphthylanthryl, phenanthrylanthrenyl, dibenzo [ a, e ] [8] cycloalkenyl, 9, 10-dihydro-9, 10[1',2' ] benzanthrenyl, 9 '-spirobis-9H-fluorenyl and spiro [ 1H-cyclobutene [ de ] naphthalene-1, 9' - [9H ] fluorenyl ].

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

(I) Polycyclic heteroaromatics contain a heteroaromatic monocyclic ring as defined above and at least one (e.g. 1, 2, 3, 4 or 5) further aromatic ring selected from phenyl and heteroaromatic monocyclic rings as defined above, wherein the aromatic rings of the polycyclic heteroaromatics are covalently linked to each other and/or directly fused to each other and/or fused to a saturated or unsaturated 4-to 10-membered mono-or bicyclic hydrocarbon ring, or

(Ii) Polycyclic heteroaromatics contain at least one saturated or partially or fully unsaturated 5, 6, 7 or 8 membered heterocyclic ring containing 1,2 or 3 heteroatoms selected from oxygen, sulfur and nitrogen as ring atoms, such as 2H-pyran, 4H-pyran, thiopyran, 1, 4-dihydropyridine, 4H-1, 4-oxazine, 4H-1, 4-thiazine, 1, 4-dioxazine (dioxain), oxazepine, thiazepine, dioxazine, dithiadienyl (dithiin), dioxazepine, dithiazepine, dioxaxin (dioxocine), dithiacine (dithiocine), and at least one (e.g. 1,2, 3, 4 or 5) aromatic ring selected from phenyl, and heteroaromatic monocyclic rings as defined above, wherein at least one of the aromatic rings is directly fused to the ring of the saturated or partially unsaturated 5 to 8 membered heterocyclic ring, and wherein the aromatic ring of the polycyclic aromatic ring is linked to each other by a covalent bond or is directly fused to each other and/or to the saturated or unsaturated or 4 to the 10 membered heterocyclic ring.

Mono-or polycyclic heteroaryl groups have 5 to 26, often 5 to 24, especially 5 to 20 ring atoms, which contain 1, 2, 3 or 4 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, often 9 to 24, especially 9 to 20 ring atoms, which contain 1, 2, 3 or 4 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 ] thiophenyl), naphthofuranyl, naphthothiophenyl, furo [3,2-b ] furanyl, furo [2,3-b ] furanyl, furo [3,4-b ] furanyl, thieno [3,2-b ] thiophenyl, thieno [2,3-b ] thiophenyl, thieno [3,4-b ] thiophenyl, oxaanthracenyl (oxanthrenyl), thianthrenyl, indolyl (=1h-indolyl), isoindolyl (=2h-isoindolyl), carbazolyl, indolylA group, a benzopyrazolyl group, a benzimidazolyl group, a benzoxazolyl group, a benzothiazolyl group, a benzo [ c, d ] indolyl group, a 1H-benzo [ g ] indolyl group, a quinolinyl group, an isoquinolinyl group, an acridinyl group, a phenazinyl group, a quinazolinyl group, a quinoxalinyl group, a kephaluzinyl group, a benzo [ b ] [1,5] naphthyridinyl group, a cinnolinyl group, a1, 5-naphthyridinyl group, a1, 8-naphthyridinyl group, a phenylpyrrolyl group, a naphthyridinyl group, a bipyridinyl group, a phenylpyridinyl group, a naphthyridinyl group, a pyrido [4,3-b ] indolyl group, a pyrido [3,2-b ] [1,8] naphthyridinyl group, a pyrrolo [3,2-b ] pyridinyl group, a pteridinyl group, a purinyl group, a 9H-oxaanthracenyl group, a 9H-thioxoanthracenyl group (thioxanthenyl), a 2H-alkenyl group, a benzo [4,3-b ] indolyl group, a pyrido [2, a 2-b ] naphthyridinyl group; 4,3-b '] difuranyl, benzo [1,2-b:6,5-b' ] difuranyl, benzo [1,2-b:5,4-b '] difuranyl, benzo [1,2-b:4,5-b' ] difuranyl, naphtho [1,2-d ] furanyl, benzo [ b ] naphtho [2,3-d ] furanyl, benzo [ b ] naphtho [2,1-d ] furanyl, tribenzo [ b, d, f ] oxazepine, dibenzo [ b, d ] thienyl, naphtho [1,2-b ] thienyl, naphtho [2,3-b ] thienyl, naphtho [2,1-b ] thienyl, benzo [ b ] naphtho [1,2-d ] thienyl, benzo [ b ] naphtho [2,3-d ] thienyl, benzo [ b ] naphtho [2,1-d ] thienyl, 6H-dibenzo [ b, d ] thiopyranyl, 5H,9H [1] benzothiopyranyl, 5,4,3-c, d, e ] [2] benzothiopyranyl, 5H,10H [1] benzothiopyrano [5,4,3-c, d, e ] [2] benzothiopyranyl, benzo [1,2-b:4,3-b '] dithiophene radical, benzo [1,2-b:6,5-b' ] dithiophene radical, benzo [1,2-b:5,4-b '] dithiophene, benzo [1,2-b ] [4, 5-b' ] dithiophene, 1, 4-benzodithiohexadienyl (benzodithiinyl), naphtho [1,2-b ] [1,4] dithiohexadienyl, thianthrenyl, benzo [ a ] thianthrenyl, benzo [ b ] thianthrenyl, dibenzo [ a, c ] thianthrenyl, dibenzo [ a, H ] thianthrenyl, dibenzo [ a, i ] thianthrenyl, dibenzo [ a, j ] thianthrenyl, dibenzo [ b, i ] thianthrenyl, 2H-naphtho [1,8-b, c ] thienyl, 5H-phenanthro [4,5-b, c, d ] thianthrenyl, 10, 11-dihydrodibenzo [ b, f ] thianthrenyl, 6, 7-dihydrobenzo [ b ] thianthrenyl, d [ c ] thianthrenyl, 2H-naphtho [ b, i ] thianthrenyl, 2H-naphtho [1,8-b, c ] thianthrenyl, 5H-phenanthro [4, c, d ] thianthrenyl, 10, 11-dihydrodibenzo [ b, f ] thianthrenyl, 6, 7-dihydrobenzo [ b, j ] thianthrenyl, d [ b, 3, i ] thianthrenyl, 3, c ] thianthrenyl, 2, 3H-thianthrenyl, 3, c [ b ] thianthrenyl, 3-thia [ b ] thia [ b, 3-thia [ b ] thia, 3-thia [ b ] thia [ b ] thia, 3-thia [ b ] thia [ b, thia [ b ] thia [ b, [ thia [ b ] -thia [ b, [ b- [ -b- -, 8' -f, g ] [1,5] dithia yl, 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 two groups of benzene, naphthalene and biphenyl, respectively, as are well known in the art. Accordingly, the terms "phenylene", "naphthylene" and "biphenylene" are used herein synonymously with the terms phenyldiyl, naphthyldiyl and biphenyldiyl, respectively.

For the purposes of the present invention, a "structural unit" is a structural element which is repeatedly present in the polymer main chain of the 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, particularly in refraction. Optical devices include, but are not limited to, prisms, lenses, optical films, and combinations thereof, particularly camera lenses and eyewear lenses.

The comments made below regarding the variables (substituents) of the compounds of formula (I) and the preferred embodiments of the structural units of formula (II) apply to themselves and preferably in combination with one another.

The comments made below regarding the preferred embodiments of the variables apply to the compounds of the formula (I) and to the structural units of the formula (II) themselves and preferably in combination with one another and, where applicable, to the use according to the invention.

If both R ³ and R ⁴ in formula (I) are hydrogen, the radicals R ¹ and R ² 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 the group consisting of: nitrogen, sulfur and oxygen, while the remaining atoms of such ring member atoms of heteroaryl groups are carbon atoms, wherein the polycyclic aryl groups and polycyclic heteroaryl groups are unsubstituted or contain 1,2, 3 or 4 free radicals R ^Ar.

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

Preferably those variables Z ¹ and Z ² of formula (I) which are independently selected from the group consisting of hydrogen, -Alk-OH, -CH ₂-Ar²-CH₂-OH、-Alk'-C(O)OR^x and-CH ₂-Ar²-C(O)OR^x, and accordingly preferably those variables Z ^1a and Z ^2a of formula (II), they are independently selected from the group consisting of-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, particularly preferred meanings.

In a preferred group (1) of embodiments, the variables Z ¹ and Z ² in formula (I) are independently selected from-Alk-OH and-CH ₂-Ar²-CH₂ -OH, and accordingly the variables Z ^1a and Z ^2a in formula (II) are independently selected from-Alk-O-and-CH ₂-Ar²-CH₂ -O-, wherein Alk is preferably a linear C ₂-C₄ -alkanediyl group, such as 1, 2-ethanediyl (CH ₂-CH₂), 1, 3-propanediyl or 1, 4-butanediyl, and especially 1, 2-ethanediyl, and Ar ² is preferably selected from 1, 4-phenylene, 1, 3-phenylene, 2, 6-naphthylene, 1, 4-naphthylene, 1, 5-naphthylene and 4,4' -biphenylene. In this context, it is likewise preferred that the variables Z ¹ and Z ² in the formula (I) or the variables Z ^1a and Z ^2a in the formula (II) are identical to one another.

Accordingly, in a particularly preferred subgroup (1.1) of embodiments, 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. Correspondingly, in this particularly preferred group (1.1) of embodiments, 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 particular subgroup (1') of embodiments, the variables 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 groups (1) and (1.1) of embodiments.

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

In a preferred group (3) of embodiments, 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 accordingly 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-, where Alk ' is preferably a linear C ₁-C₄ -alkanediyl group, such as methylene OR1, 2-ethanediyl (CH ₂-CH₂), and especially methylene, ar ² is preferably selected from 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 especially methyl. In this context, it is also preferred that the variables Z ¹ and Z ² or the variables Z ^1a and Z ^2a are identical to one another.

Accordingly, 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. Correspondingly, in this particularly preferred group (3.1) of embodiments, the variables Z ^1a and Z ^2a in formula (II) are selected from-O-C (O) -methyl, -O-C (O) -phenyl-methyl and-O-C (O) -naphthyl-methyl, in particular from-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, and in particular from-O-C (O) -methyl, (4 (-O-C (O) -phenyl) methyl and (3 (-O-C (O) -phenyl) methyl).

In a particular subgroup (3') 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 groups (3) and (3.1) of embodiments.

In a preferred group (4) of embodiments, which is a combination of groups (1.1), (2) and (3.1) of embodiments, 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, especially 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) -1-naphthyl) methyl, especially from the group is selected from the group consisting of hydrogen, methyl, 3- (methoxycarbonyl) -1-naphthyl-methyl, and (6-naphthyl) methyl 2-hydroxyethyl, methoxycarbonyl-methyl, (4- (hydroxymethyl) phenyl) methyl, (3- (hydroxymethyl) phenyl) methyl, (4- (methoxycarbonyl) phenyl) methyl and (3- (methoxycarbonyl) phenyl) methyl, and in particular selected from hydrogen, 2-hydroxyethyl, (4- (hydroxymethyl) phenyl) methyl and (3- (hydroxymethyl) phenyl) methyl. Correspondingly, in this preferred group (4) of embodiments, the variables Z ^1a and Z ^2a in formula (II) are selected from 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, especially from 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 group (4) of embodiments.

The variable X is preferably selected from: single bond, O, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-di-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 specifically selected from: phenyl, naphthyl, phenanthryl, biphenyl, fluorenyl, pyrenyl, and the like,A group, benzo [ b ] furyl, dibenzo [ b, d ] furyl, naphtho [1,2-b ] furyl, naphtho [2,3-b ] furyl, naphtho [2,1-b ] furyl, oxaanthracyl, 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 particularly selected from the group consisting of: phenyl, naphthyl, phenanthryl, biphenyl, fluorenyl, benzo [ b ] furanyl, dibenzo [ b, d ] furanyl, benzo [ b ] thiophenyl, and dibenzo [ b, d ] thiophenyl.

The variable X is chosen in particular from: single bond, O, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-t-butyl 、N-Ar¹、CH₂、C(CH₃)₂、CH(CH₃)、C(CH₃)(CH₂CH₃)、S and SO ₂, wherein Ar ¹ is selected from: 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-5-yl, benzo [ b ] furan-6-yl or benzo [ b ] furan-7-yl), dibenzo [ b, d ] furanyl (such as dibenzo [ b, d ] furan-1-yl, dibenzo [ b, d ] furan-3-yl or dibenzo [ b ] furan-4-yl, benzo [ b ] furan-7-yl, benzo [ b ] furan-5-yl, benzo [ b ] furan-6-yl, benzo [ b ] furan-7-yl, 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 group (5) of embodiments, the variable X is selected from: single bond, O, N-phenyl, N-naphthyl, N-phenanthryl, CH ₂、C(CH₃)₂、CH(CH₃), S, S (O) and SO ₂, particularly selected from: 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, in particular selected from: single bond, O, CH ₂、C(CH₃)₂, S, S (O) and SO ₂, and are selected in particular from: single bond, C (CH ₃)₂, S and SO ₂.

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

The variables R ¹ and R ² are preferably independently selected from: mono-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 such ring member atoms of the heteroaryl group are oxygen or sulfur atoms and the remaining atoms of such ring member atoms of the heteroaryl group are carbon atoms, wherein the mono-or polycyclic aryl and polycyclic heteroaryl groups are unsubstituted or contain 1 or 2 radicals R ^Ar, wherein R ^Ar has one of the meanings defined herein, especially one of the meanings mentioned as preferred (group 6 of embodiments). At least one of R ¹ and R ² (especially both R ¹ and R ²) is more preferably 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 group (6.1) of embodiments, R ¹ and R ² are independently selected from phenyl, naphthyl (such as naphthalen-1-yl or naphthalen-2-yl), 1, 2-dihydroacenaphthenyl (such as 1, 2-dihydroacenaphtho-3-yl or 1, 2-dihydroacenaphtho-5-yl), biphenyl (such as biphenyl-4-yl, biphenyl-3-yl or biphenyl-2-yl), fluorenyl (such as fluoren-1-yl, fluoren-2-yl, fluoren-3-yl or fluoren-4-yl), 11H-benzo [ a ] fluorenyl (such as 11H-benzo [ a ] fluoren-7-yl), 11H-benzo [ b ] 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, fluoren-3-yl or fluoren-4-yl), benzo [ c ] fluoren-1-yl, benzo [ c ] fluoren-6-c ] fluorenyl (such as 11H-benzo [ c ] fluoren-1-yl), benzo [ c ] fluoren-6-c ] fluoren-1-yl, benzo [ c ] fluoren-6-c ] fluorenyl Pyren-2-yl or pyren-4-yl),Radicals (such as/>-1-Yl,/>-2-Yl,/>-3-Yl/>-4-Yl/>-5-Yl or/>-6-Yl), picene (such as picene-3-yl), triphenylene (such as triphenylene-1-yl or triphenylene-2-yl), benzo [ b ] furanyl (such as benzo [ b ] furan-2-yl, benzo [ b ] furan-3-yl, benzo [ b ] furan-4-yl, benzo [ b ] furan-5-yl, benzo [ b ] furan-6-yl or benzo [ b ] furan-7-yl), dibenzo [ b, d ] furanyl (such as dibenzo [ b, d ] furan-1-yl, dibenzo [ b), d ] furan-2-yl, dibenzo [ b, d ] furan-3-yl or dibenzo [ b, d ] furan-4-yl), naphtho [1,2-b ] furanyl (such as naphtho [1,2-b ] furan-5-yl), naphtho [2,3-b ] furanyl (such as naphtho [2,3-b ] furan-3-yl, naphtho [2,3-b ] furan-4-yl or naphtho [2,3-b ] furan-9-yl), naphtho [2,1-b ] furanyl (such as naphtho [2,1-b ] furan-2-yl or naphtho [2,1-b ] furan-5-yl), benzo [ b ] naphthalen [1,2-d ] furanyl (such as benzo [ b ] naphthalen [1,2-d ] furan-1-yl or benzo [ b ] naphthalen [1,2-d ] furan-4-yl), benzo [ b ] naphthalen [2,3-d ] furanyl (such as benzo [ b ] naphthalen [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), benzo [ b ] naphthalen [2,1-d ] furanyl (such as benzo [ b ] naphthalen [2,1-d ] furan-6-yl or benzo [ b ] naphthalen [2,1-d ] furan-7-yl), benzo [1,2-b:4,3-b ' ] difuranyl (such as benzo [1,2-b:4,3-b ' ] difuran-7-yl), benzo [1,2-b:6,5-b ' ] difuranyl (such as benzo [1,2-b:6,5-b ' ] difuran-4-yl), benzo [1,2-b:5,4-b ' ] difuranyl (such as benzo [1,2-b:5,4-b ' ] difuran-4-yl or benzo [1,2-b:5,4-b ' ] difuran-8-yl), benzo [1,2-b:4,5-b ' ] difuranyl (such as benzo [1,2-b:4,5-b ' ] difuran-4-yl), tribenzo b, d, f ] oxa (such as tribenzo [ b, d, f ] oxazin-6-yl or tribenzo [ b, d, f ] oxazin-8-yl), 2H-naphtho [1,8-d, e ] [1,3] dioxanyl (such as 2H-naphtho [1,8-d, e ] [1,3] dioxan-2-yl or 2H-naphtho [1,8-d, e ] [1,3] dioxan-6-yl), dinapht [2,3-b:2',3' -d ] furanyl (such as dinapht [2,3-b:2',3' -d ] furan-3-yl or dinaphto [2,3-b:2',3' -d ] furan-5-yl), xanthenyl (such as xanthen-1-yl or xanthen-2-yl), benzo [ a ] xanthen-yl (such as benzo [ a ] xanthen-1-yl, benzo [ a ] oxa-2-yl, benzo [ a ] oxazin-6-yl), dinaphten-3-yl (such as benzo [2, 3' -d ] furan-3-yl) or dinaphten-2, 3-b ] furan-3-yl (such as benzo [2,3-b:2',3' -d ] furan-5-yl), xanthen-yl (such as benzo [ a ] oxa-1-yl), benzo [ a ] oxa-2-yl, benzo [ b ] oxa-6-yl, benzo [ b ] or benzo [ b ] thiophen-7-yl, dibenzo [ b, d ] thiophenyl (such as 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), naphtho [1,2-b ] thiophenyl (such as naphtho [1,2-b ] thiophen-5-yl), naphtho [2,3-b ] thiophenyl (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 ] thiophenyl (such as naphtho [2,1-b ] thiophen-2-yl or naphtho [2,1-b ] thiophen-5-yl) benzo [ b ] naphtalen [1,2-d ] thienyl (such as benzo [ b ] naphtalen [1,2-d ] thiophen-1-yl or benzo [ b ] naphtalen [1,2-d ] thiophen-4-yl), benzo [ b ] naphtalen [2,3-d ] thiophen-2-yl, benzo [ b ] naphtalen [2,3-d ] thiophen-4-yl or benzo [ b ] naphtalen [2,3-d ] thiophen-6-yl), benzo [ b ] naphtalen [2,1-d ] thienyl (such as benzo [ b ] naphtalen [2,1-d ] thiophen-7-yl), benzo [1,2-b:4,3-b '] dithiophene (such as benzo [1,2-b:4,3-b' ] dithiophene-7-yl), benzo [1,2-b:6,5-b '] dithiophene (such as benzo [1,2-b:6,5-b' ] dithiophene-4-yl), benzo [1,2-b:5,4-b '] dithiophene (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 (such as benzo [1,2-b:4,5-b '] dithiophene-4-yl), 9H-thioxoanthracenyl (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-benzodithio (such as benzo [1,2-b, 5-b' ] dithio-4-yl), benzo [1, 4-b ] [1,2-b ] [1,2-b ] [ thiofuran ] dithio-2-yl) or (such as) A naphtho [2,3-b ] [1,4] dithiocyclohexadienyl (such as naphtho [2,3-b ] [1,4] dithiocyclohexadien-5-yl), a thianthrenyl (such as thianthrene-1-yl or thianthrene-2-yl), a benzo [ a ] thianthrenyl (such as benzo [ a ] thianthrene-1-yl, benzo [ a ] thianthrene-2-yl, benzo [ a ] thianthrene-6-yl or benzo [ a ] thianthrene-7-yl), a benzo [ b ] thianthrene-yl (such as benzo [ b ] thianthrene-1-yl, benzo [ b ] thianthrene-2-yl or benzo [ b ] thianthrene-6-yl), a, c ] thianthrene (such as dibenzo [ a, c ] thianthrene-10-yl or dibenzo [ a, c ] thianthrene-11-yl), dibenzo [ a, H ] thianthrene-yl (such as dibenzo [ a, H ] thianthrene-6-yl), dibenzo [ a, i ] thianthrene-yl (such as dibenzo [ a, i ] thianthrene-6-yl), dibenzo [ a, j ] thianthrene-yl (such as dibenzo [ a, j ] thianthrene-6-yl), dibenzo [ b, i ] thianthrene-yl (such as dibenzo [ b, i ] thianthrene-5-yl), 2H-naphtho [1,8-b, c ] thiophene-6-yl or 2H-naphtho [1,8-b, c ] thiophene-8-yl), dibenzo [ b, d ] thiazepinyl (such as dibenzo [ b, d ] thiazepin-2-yl), dibenzo [ b, f ] thiazepinyl (such as dibenzo [ b, f ] thiazepin-2-yl or dibenzo [ b, f ] thiazepin-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-9-yl or 5H-phenanthro [4,5-b, c, d ] thiopyran-3-yl), 5H-benzo [4,5-b, c, d ] thiopyran-2-yl, 5H-benzopyran-7-yl, 5H-phenanthro [4,5-b, c, d ] thiopyran-3-yl, 5H-benzopyran-yl, 5-b, c, d ] thiopyran-8-yl, such as benzozepin-2-yl); 4,5-b ', c ' ] dithiophene radicals (such as 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 '] dithiophenethyl (such as 2, 6-dihydronaphtho [1,8-b, c:5,4-b', c '] dithiophene-4-yl), tetrabenzo [ a, c, H, j ] thianthrenyl (such as tetrabenzo [ a, c, H, j ] thianthrene-3-yl), benzo [ b ] naphtho [1,8-e, f ] [1,4] dithiorenyl (such as benzo [ b ] naphtho [1,8-e, f ] [1,4] dithiopin-2-yl), dinaphto [2,3-b:2',3'-d ] thiophenyl (such as dinaphtho [2,3-b:2',3'-d ] thiophen-3-yl or dinaphtho [2,3-b:2',3'-d ] thiophen-5-yl), 5H-phenanthro [1,10-b, c ] thiophenyl (such as 5H-phenanthro [1,10-b, c ] thiophenyl) or 5H-benzo [1,8-e, f ] [1,4] dithio [1,4] dithiopin-2-yl), dinaphtho [2,3-b:2',3'-d ] thiophen-yl (such as dinaphtho [2, 3' -b:2',3' -d ] thiophen-3-yl), 5H-phenanthro [1,10-b, c ] thiophenyl (such as 5H-H-b ] naphthas a, 5-b ] thiophenyl (such as 5H-benzo [1,10-b ] thiophenyl), 5-b ] dithio [1,10-b ] 2-yl (such as 1, 7-b ] 2, 7-b ] 2-yl, and dibenzo [ d, d '] benzo [1,2-b:5,4-b' ] dithiophene (such as dibenzo [ d, d '] benzo [1,2-b:5,4-b' ] dithiophene-4-yl or dibenzo [ d, d '] benzo [1,2-b:5,4-b' ] dithiophene-6-yl), which may be unsubstituted or may contain 1 or 2 free radicals R ^Ar.

Particularly preferred groups (6.2) according to embodiments, R ¹ and R ² are independently selected from phenyl, naphthyl (such as naphthalen-1-yl or naphthalen-2-yl), 1, 2-acenaphthylenyl (such as 1, 2-acenaphthylen-3-yl or 1, 2-acenaphthylen-5-yl), biphenyl (such as biphenyl-4-yl, biphenyl-3-yl or biphenyl-2-yl), fluorenyl (such as fluoren-1-yl, fluoren-2-yl, fluoren-3-yl or fluoren-4-yl), phenanthryl (such as phenanthren-1-yl, phenanthren-2-yl, phenanthren-3-yl, phenanthren-4-yl or phenanthren-9-yl), benzo [ c ] phenanthren-1-yl (such as benzo [ c ] phenanthren-2-yl, benzo [ c ] phenanthren-3-yl, benzo [ c ] phenanthren-4-yl, benzo [ c ] phenanthren-5-yl or benzo [ c ] phenanthren-6-yl), phenanthren-1-yl, pyrene-4-yl, pyrene-2-yl, and the like,Radicals (such as/>-1-Yl,/>-2-Yl,/>-3-Yl/>-4-Yl/>-5-Yl or/>-6-Yl), triphenylene (such as triphenylene-1-yl or triphenylene-2-yl), benzo [ b ] furanyl (such as benzo [ b ] furan-2-yl, benzo [ b ] furan-3-yl, benzo [ b ] furan-4-yl, benzo [ b ] furan-5-yl, benzo [ b ] furan-6-yl or benzo [ b ] furan-7-yl), dibenzo [ b, d ] furanyl (such as dibenzo [ b, d ] furan-1-yl, dibenzo [ b, d ] furan-2-yl, dibenzo [ b, d ] furan-3-yl or dibenzo [ b), d ] furan-4-yl), naphtho [1,2-b ] furan-yl (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 ] naphthalene [2,3-d ] furanyl (such as benzo [ b ] naphthalene [2,3-d ] furan-2-yl, benzo [ b ] naphthalene [2,3-d ] furan-4-yl or benzo [ b ] naphthalene [2,3-d ] furan-6-yl), benzo [ b ] naphthalene [2,1-d ] furan-6-yl or benzo [ b ] naphthalene [2,1-d ] furan-7-yl, oxaanthracenyl (such as oxa-1-yl or oxa-anthracene-2-yl), benzo [ a ] oxa-anthracen-1-yl, benzo [ a ] oxa-2-yl, benzo [ a ] oxa-6-yl or benzo [ a ] oxa-7-yl), benzo [ b ] oxa [ b ] naphthalene [2,1-d ] furan-6-yl or benzo [ b ] naphthalene [2, 1-yl, such as oxa-b-thiophen-1-yl, dibenzo [ b ] thiophen-2-yl, benzo [ b ] oxa-1-yl, such as oxa-1-yl, benzo [ a ] oxa-6-yl, benzo [ a ] oxa-yl, benzo [ b ] thiophen-2-yl, d ] thiophen-2-yl, dibenzo [ b, d ] thiophen-3-yl or dibenzo [ b, d ] thiophen-4-yl), naphtho [1,2-b ] thiophenyl (such as naphtho [1,2-b ] thiophen-5-yl), naphtho [2,3-b ] thiophen-3-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 ] thiophenyl (such as naphtho [2,1-b ] thiophen-2-yl or naphtho [2,1-b ] thiophen-5-yl), benzo [ b ] naphtho [1,2-d ] thiophenyl (such as 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 ] thienyl (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 [2,1-d ] thienyl (such as benzo [ b ] naphtho [2,1-d ] thiophen-7-yl), thianthrenyl (such as thianthrene-1-yl or thianthrene-2-yl), benzo [ a ] thianthrenyl (such as benzo [ a ] thianthrene-1-yl, benzo [ a ] thianthrene-2-yl, benzo [ a ] thianthrene-6-yl or benzo [ a ] thianthrene-7-yl), benzo [ b ] thianthrene-1-yl (such as benzo [ b ] thianthrene-2-yl or benzo [ b ] thianthrene-6-yl), 2H-naphtho [1,8-b, 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 ] thiazel (such as dibenzo [ b, d ] thiazel-2-yl), dibenzo [ b, f ] thiazel (such as dibenzo [ b, f ] thiazel-2-yl or dibenzo [ b, f ] thiazel-4-yl), tribenzo [ b, d, f ] thiazel (such as 2H-naphtho [1,8-b, c ] thiophen-6-yl or 2H-naphtho [1,8-b, c ] thiophen-6-yl), dibenzo [ b, f ] thiazel (such as benzob, f ] thiazel-2-yl) or benzol [ b, f ] thiazel-2-yl, or R-containing one or more may be unsubstituted.

In a particularly preferred group (6.3) of embodiments, 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, 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-thiophen-2-yl, dithienyl, benzo [ b-4-d ] thiophen-2-yl and dithienyl.

In a subgroup (6.3 a) of group (6.3) of embodiments, 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 are especially selected from phenyl, naphthyl, phenanthryl, dibenzo [ b, d ] thienyl and thianthrenyl.

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

In a preferred group (7) of embodiments, the variables R ³ and R ⁴ are not hydrogen. In other words, the variables R ³ and R ⁴ are selected from: mono-or polycyclic aryl groups having 6 to 26 carbon atoms as ring member atoms and mono-or polycyclic heteroaryl groups having a total of 5 to 26 atoms as ring members, wherein 1, 2, 3 or 4 of such ring member atoms of the heteroaryl groups are selected from nitrogen, sulfur and oxygen, while the remaining atoms of such ring member atoms of the heteroaryl groups are carbon atoms, wherein the mono-or polycyclic aryl groups and mono-or polycyclic heteroaryl groups are unsubstituted or contain at least one of the radicals R ^Ar.R³ and R ⁴ of 1, 2, 3 or 4, especially R ³ and R ⁴ are more preferably both selected from polycyclic aryl groups having 10 to 18 carbon atoms and polycyclic heteroaryl groups having a total of 9 to 26 atoms.

Preferably, in this group (7) of embodiments, the variables R ³ and R ⁴ are independently selected from: mono-or polycyclic aryl groups having 6 to 18 carbon atoms as ring members and polycyclic heteroaryl groups having a total of 9 to 26 atoms as ring members, wherein 1 or 2 of such atoms are oxygen or sulfur atoms and the remaining atoms of such atoms are carbon atoms, wherein the mono-or polycyclic aryl and polycyclic heteroaryl groups are unsubstituted or contain 1 or 2 free radicals R ^Ar, wherein R ^Ar has one of the meanings defined herein, in particular one of the meanings mentioned as preferred (group (7.1) of embodiments below).

More preferably, in this group (7) of embodiments, R ³ and R ⁴ are independently selected from phenyl, naphthyl (such as naphthalen-1-yl or naphthalen-2-yl), 1, 2-dihydroacenaphthyl (such as 1, 2-dihydroacenaphthylen-3-yl or 1, 2-dihydroacenaphthylen-5-yl), biphenyl (such as biphenyl-4-yl, biphenyl-3-yl or biphenyl-2-yl), fluorenyl (such as fluoren-1-yl, fluoren-2-yl, fluoren-3-yl or fluoren-4-yl), 11H-benzo [ a ] fluorenyl (such as 11H-benzo [ a ] fluoren-7-yl), 11H-benzo [ b ] 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 7H-benzo [ c ] fluoren-5-yl), fluoren-3-yl, fluoren-c [ c ] fluoren-3-yl, or fluoren-4-yl), 11H-benzo [ a ] fluorenyl (such as 11H-benzo [ a ] fluoren-3-yl), 11-benzo [ c ] fluorenyl, benzo [ c ] fluoren-3-yl, benzo [ c ] fluoren-4-yl, benzo [ c ] fluoren-2-yl, benzo [ c ] fluoren-3-yl, benzo [ c ] benzo ] fluoren-yl, benzo [ 3-yl, benzo [ c ] benzo ] 3-yl, or benzo [ c ] benzo [ 3-p-yl Pyren-2-yl or pyren-4-yl),Radicals (such as/>-1-Yl,/>-2-Yl,/>-3-Yl/>-4-Yl/>-5-Yl or/>-6-Yl), picene (such as picene-3-yl), triphenylene (such as triphenylene-1-yl or triphenylene-2-yl), benzo [ b ] furanyl (such as benzo [ b ] furan-2-yl, benzo [ b ] furan-3-yl, benzo [ b ] furan-4-yl, benzo [ b ] furan-5-yl, benzo [ b ] furan-6-yl or benzo [ b ] furan-7-yl), dibenzo [ b, d ] furanyl (such as dibenzo [ b, d ] furan-1-yl, dibenzo [ b), d ] furan-2-yl, dibenzo [ b, d ] furan-3-yl or dibenzo [ b, d ] furan-4-yl), naphtho [1,2-b ] furanyl (such as naphtho [1,2-b ] furan-5-yl), naphtho [2,3-b ] furanyl (such as naphtho [2,3-b ] furan-3-yl, naphtho [2,3-b ] furan-4-yl or naphtho [2,3-b ] furan-9-yl), naphtho [2,1-b ] furanyl (such as naphtho [2,1-b ] furan-2-yl or naphtho [2,1-b ] furan-5-yl), benzo [ b ] naphthalen [1,2-d ] furanyl (such as benzo [ b ] naphthalen [1,2-d ] furan-1-yl or benzo [ b ] naphthalen [1,2-d ] furan-4-yl), benzo [ b ] naphthalen [2,3-d ] furanyl (such as benzo [ b ] naphthalen [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), benzo [ b ] naphthalen [2,1-d ] furanyl (such as benzo [ b ] naphthalen [2,1-d ] furan-6-yl or benzo [ b ] naphthalen [2,1-d ] furan-7-yl), benzo [1,2-b:4,3-b ' ] difuranyl (such as benzo [1,2-b:4,3-b ' ] difuran-7-yl), benzo [1,2-b:6,5-b ' ] difuranyl (such as benzo [1,2-b:6,5-b ' ] difuran-4-yl), benzo [1,2-b:5,4-b ' ] difuranyl (such as benzo [1,2-b:5,4-b ' ] difuran-4-yl or benzo [1,2-b:5,4-b ' ] difuran-8-yl), benzo [1,2-b:4,5-b ' ] difuranyl (such as benzo [1,2-b:4,5-b ' ] difuran-4-yl), tribenzo b, d, f ] oxa (such as tribenzo [ b, d, f ] oxazin-6-yl or tribenzo [ b, d, f ] oxazin-8-yl), 2H-naphtho [1,8-d, e ] [1,3] dioxanyl (such as 2H-naphtho [1,8-d, e ] [1,3] dioxan-2-yl or 2H-naphtho [1,8-d, e ] [1,3] dioxan-6-yl), dinapht [2,3-b:2',3' -d ] furanyl (such as dinapht [2,3-b:2',3' -d ] furan-3-yl or dinaphto [2,3-b:2',3' -d ] furan-5-yl), xanthenyl (such as xanthen-1-yl or xanthen-2-yl), benzo [ a ] xanthen-yl (such as benzo [ a ] xanthen-1-yl, benzo [ a ] oxa-2-yl, benzo [ a ] oxazin-6-yl), dinaphten-3-yl (such as benzo [2, 3' -d ] furan-3-yl) or dinaphten-2, 3-b ] furan-3-yl (such as benzo [2,3-b:2',3' -d ] furan-5-yl), xanthen-yl (such as benzo [ a ] oxa-1-yl), benzo [ a ] oxa-2-yl, benzo [ b ] oxa-6-yl, benzo [ b ] or benzo [ b ] thiophen-7-yl, dibenzo [ b, d ] thiophenyl (such as 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), naphtho [1,2-b ] thiophenyl (such as naphtho [1,2-b ] thiophen-5-yl), naphtho [2,3-b ] thiophenyl (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 ] thiophenyl (such as naphtho [2,1-b ] thiophen-2-yl or naphtho [2,1-b ] thiophen-5-yl) benzo [ b ] naphtalen [1,2-d ] thienyl (such as benzo [ b ] naphtalen [1,2-d ] thiophen-1-yl or benzo [ b ] naphtalen [1,2-d ] thiophen-4-yl), benzo [ b ] naphtalen [2,3-d ] thiophen-2-yl, benzo [ b ] naphtalen [2,3-d ] thiophen-4-yl or benzo [ b ] naphtalen [2,3-d ] thiophen-6-yl), benzo [ b ] naphtalen [2,1-d ] thienyl (such as benzo [ b ] naphtalen [2,1-d ] thiophen-7-yl), benzo [1,2-b:4,3-b '] dithiophene (such as benzo [1,2-b:4,3-b' ] dithiophene-7-yl), benzo [1,2-b:6,5-b '] dithiophene (such as benzo [1,2-b:6,5-b' ] dithiophene-4-yl), benzo [1,2-b:5,4-b '] dithiophene (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 (such as benzo [1,2-b:4,5-b '] dithiophene-4-yl), 9H-thioxoanthracenyl (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-benzodithio (such as benzo [1,2-b, 5-b' ] dithio-4-yl), benzo [1, 4-b ] [1,2-b ] [1,2-b ] [ thiofuran ] dithio-2-yl) or (such as) A naphtho [2,3-b ] [1,4] dithiocyclohexadienyl (such as naphtho [2,3-b ] [1,4] dithiocyclohexadien-5-yl), a thianthrenyl (such as thianthrene-1-yl or thianthrene-2-yl), a benzo [ a ] thianthrenyl (such as benzo [ a ] thianthrene-1-yl, benzo [ a ] thianthrene-2-yl, benzo [ a ] thianthrene-6-yl or benzo [ a ] thianthrene-7-yl), a benzo [ b ] thianthrene-yl (such as benzo [ b ] thianthrene-1-yl, benzo [ b ] thianthrene-2-yl or benzo [ b ] thianthrene-6-yl), a, c ] thianthrene (such as dibenzo [ a, c ] thianthrene-10-yl or dibenzo [ a, c ] thianthrene-11-yl), dibenzo [ a, H ] thianthrene-yl (such as dibenzo [ a, H ] thianthrene-6-yl), dibenzo [ a, i ] thianthrene-yl (such as dibenzo [ a, i ] thianthrene-6-yl), dibenzo [ a, j ] thianthrene-yl (such as dibenzo [ a, j ] thianthrene-6-yl), dibenzo [ b, i ] thianthrene-yl (such as dibenzo [ b, i ] thianthrene-5-yl), 2H-naphtho [1,8-b, c ] thiophene-6-yl or 2H-naphtho [1,8-b, c ] thiophene-8-yl), dibenzo [ b, d ] thiazepinyl (such as dibenzo [ b, d ] thiazepin-2-yl), dibenzo [ b, f ] thiazepinyl (such as dibenzo [ b, f ] thiazepin-2-yl or dibenzo [ b, f ] thiazepin-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-9-yl or 5H-phenanthro [4,5-b, c, d ] thiopyran-3-yl), 5H-benzo [4,5-b, c, d ] thiopyran-2-yl, 5H-benzopyran-7-yl, 5H-phenanthro [4,5-b, c, d ] thiopyran-3-yl, 5H-benzopyran-yl, 5-b, c, d ] thiopyran-8-yl, such as benzozepin-2-yl); 4,5-b ', c ' ] dithiophene radicals (such as 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 '] dithiophenethyl (such as 2, 6-dihydronaphtho [1,8-b, c:5,4-b', c '] dithiophene-4-yl), tetrabenzo [ a, c, H, j ] thianthrenyl (such as tetrabenzo [ a, c, H, j ] thianthrene-3-yl), benzo [ b ] naphtho [1,8-e, f ] [1,4] dithiorenyl (such as benzo [ b ] naphtho [1,8-e, f ] [1,4] dithiopin-2-yl), dinaphto [2,3-b:2',3'-d ] thiophenyl (such as dinaphtho [2,3-b:2',3'-d ] thiophen-3-yl or dinaphtho [2,3-b:2',3'-d ] thiophen-5-yl), 5H-phenanthro [1,10-b, c ] thiophenyl (such as 5H-phenanthro [1,10-b, c ] thiophenyl) or 5H-benzo [1,8-e, f ] [1,4] dithio [1,4] dithiopin-2-yl), dinaphtho [2,3-b:2',3'-d ] thiophen-yl (such as dinaphtho [2, 3' -b:2',3' -d ] thiophen-3-yl), 5H-phenanthro [1,10-b, c ] thiophenyl (such as 5H-H-b ] naphthas a, 5-b ] thiophenyl (such as 5H-benzo [1,10-b ] thiophenyl), 5-b ] dithio [1,10-b ] 2-yl (such as 1, 7-b ] 2, 7-b ] 2-yl, and dibenzo [ d, d '] benzo [1,2-b:5,4-b' ] dithiophene groups (such as dibenzo [ d, d '] benzo [1,2-b:5,4-b' ] dithiophene-4-yl or dibenzo [ d, d '] benzo [1,2-b:5,4-b' ] dithiophene-6-yl), wherein the foregoing mono-or polycyclic aryl groups and polycyclic heteroaryl groups are unsubstituted or contain 1 or 2 free radicals R ^Ar (group (7.2) of embodiments below).

Particularly, in this group (7) of embodiments, R ³ and R ⁴ are independently selected from phenyl, naphthyl (such as naphthalen-1-yl or naphthalen-2-yl), 1, 2-acenaphthenyl (such as 1, 2-acenaphthylen-3-yl or 1, 2-acenaphthylen-5-yl), biphenyl (such as biphenyl-4-yl, biphenyl-3-yl or biphenyl-2-yl), fluorenyl (such as fluoren-1-yl, fluoren-2-yl, fluoren-3-yl or fluoren-4-yl), phenanthryl (such as phenanthren-1-yl, phenanthren-2-yl, phenanthren-3-yl, phenanthren-4-yl or phenanthren-9-yl), benzo [ c ] phenanthren-1-yl (such as benzo [ c ] phenanthren-2-yl, benzo [ c ] phenanthren-3-yl, benzo [ c ] phenanthren-4-yl, benzo [ c ] phenanthren-5-yl or benzo [ c ] pyrene-6-yl), pyrene-1-yl, pyrene-2-yl, and the like,Radicals (such as/>-1-Yl,/>-2-Yl,/>-3-Yl/>-4-Yl,-5-Yl or/>-6-Yl), triphenylene (such as triphenylene-1-yl or triphenylene-2-yl), benzo [ b ] furanyl (such as benzo [ b ] furan-2-yl, benzo [ b ] furan-3-yl, benzo [ b ] furan-4-yl, benzo [ b ] furan-5-yl, benzo [ b ] furan-6-yl or benzo [ b ] furan-7-yl), dibenzo [ b, d ] furanyl (such as dibenzo [ b, d ] furan-1-yl, dibenzo [ b, d ] furan-2-yl, dibenzo [ b, d ] furan-3-yl or dibenzo [ b), d ] furan-4-yl), naphtho [1,2-b ] furan-yl (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 ] naphthalene [2,3-d ] furanyl (such as benzo [ b ] naphthalene [2,3-d ] furan-2-yl, benzo [ b ] naphthalene [2,3-d ] furan-4-yl or benzo [ b ] naphthalene [2,3-d ] furan-6-yl), benzo [ b ] naphthalene [2,1-d ] furan-6-yl or benzo [ b ] naphthalene [2,1-d ] furan-7-yl, oxaanthracenyl (such as oxa-1-yl or oxa-anthracene-2-yl), benzo [ a ] oxa-anthracen-1-yl, benzo [ a ] oxa-2-yl, benzo [ a ] oxa-6-yl or benzo [ a ] oxa-7-yl), benzo [ b ] oxa [ b ] naphthalene [2,1-d ] furan-6-yl or benzo [ b ] naphthalene [2, 1-yl, such as oxa-b-thiophen-1-yl, dibenzo [ b ] thiophen-2-yl, benzo [ b ] oxa-1-yl, such as oxa-1-yl, benzo [ a ] oxa-6-yl, benzo [ a ] oxa-yl, benzo [ b ] thiophen-2-yl, d ] thiophen-2-yl, dibenzo [ b, d ] thiophen-3-yl or dibenzo [ b, d ] thiophen-4-yl), naphtho [1,2-b ] thiophenyl (such as naphtho [1,2-b ] thiophen-5-yl), naphtho [2,3-b ] thiophen-3-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 ] thiophenyl (such as naphtho [2,1-b ] thiophen-2-yl or naphtho [2,1-b ] thiophen-5-yl), benzo [ b ] naphtho [1,2-d ] thiophenyl (such as 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 ] thienyl (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 [2,1-d ] thienyl (such as benzo [ b ] naphtho [2,1-d ] thiophen-7-yl), thianthrenyl (such as thianthrene-1-yl or thianthrene-2-yl), benzo [ a ] thianthrenyl (such as benzo [ a ] thianthrene-1-yl, benzo [ a ] thianthrene-2-yl, benzo [ a ] thianthrene-6-yl or benzo [ a ] thianthrene-7-yl), benzo [ b ] thianthrene-yl (such as benzo [ b ] thianthrene-1-yl or benzo [ b ] thianthrene-6-yl), 2H-naphtho [1,8-b, 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 ] thiazepine (such as dibenzo [ b, d ] thiazepine-2-yl), dibenzo [ b, f ] thiazepine (such as dibenzo [ b, f ] thiazepine-2-yl or dibenzo [ b, f ] thiazepine-4-yl), tribenzo [ b, d, f ] thiazepine (such as 2H-naphtho [1,8-b, c ] thiophen-6-yl or 2H-naphtho [1,8-b, c ] thiophen-8-yl), dibenzo [ b, d ] thiazepine (such as dibenzo [ b, f ] thiazepine-2-yl or dibenzo [ b, f ] thiazepine-2-yl), or benzo [ b, f ] thiazepine (such as benzo [ b, f ] thiazepine-2-yl) or benzol (R-yl) (wherein R-7-yl) is a substituent).

In a particularly preferred group (7.4) of embodiments, 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-dihydroacenaphtho-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-benzothienyl and dithienyl. In a subgroup (7.4 a) of group (7.4) of embodiments, 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 a particular subset (7.5) of set (7) of embodiments provides a high refractive index and a negative birefringence. Such subgroup (7.5) of embodiments relates to compounds of formula (I), especially compounds of formula (Ia-1), wherein R ³ and R ⁴ are not hydrogen, and wherein at least two and preferably at least four of the substituents R ¹、R²、R³ and/or R ⁴ are bulky or sterically hindered substituents selected from polycyclic aryl and polycyclic heteroaryl groups as defined herein. In this context, the bulky substituents R ¹、R²、R³ and/or R ⁴ are in particular substituents selected from the group:

Polycyclic aryl and polycyclic heteroaryl groups containing 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 of the rings fused to the benzene ring is fused to the bond between the ortho and meta positions of the benzene ring, and

-Polycyclic aryl groups having from 14 to 26, especially from 14 to 20 carbon atoms as ring member atoms and polycyclic heteroaryl groups having from 13 to 26, especially from 13 to 20 atoms as ring members, wherein 1,2,3 or 4 of such ring member atoms are selected from nitrogen, sulfur and oxygen and the remaining atoms of such 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 the beneficial effects of the bulky substituents R ¹、R²、R³ and/or R ⁴ on this are not completely understood, it is likely that due to their steric hindrance, such substituents are forced to orient perpendicular to the backbone within the resin, which reduces the birefringence of the resin.

Accordingly, thermoplastic resins having low birefringence may be obtained according to the present invention by balancing the positive birefringence imparted to the resin by comonomers such as those of formula (IV) with the negative birefringence imparted by monomers of formula (I), in particular formula (Ia-1) according to embodiment (7.5).

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

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

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

In a preferred group (10) of embodiments, the substituents R ¹、R²、R³ and R ⁴ of formula (I) are all located in the meta-position relative to moiety X, 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 have the meanings mentioned as preferred, and wherein R ³ and R ⁴ are preferably not hydrogen, and wherein R ¹、R²、R³ and R ⁴ in particular have the same meaning.

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

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

Except and where not otherwise stated, the variables Ar ¹、R⁵、R⁶、R^Ar, R, R', R "and n, alone or preferably in combination with each other and with the meanings and preferred meanings of variables X, R ¹、R²、R³、R⁴、Z¹ and Z ² described above, have the following meanings.

Ar ¹ is preferably a mono-or polycyclic aryl group having from 6 to 18 carbon atoms as ring member atoms and a polycyclic heteroaryl group having a total of from 9 to 16 atoms as ring member atoms, wherein 1 or 2 of such ring member atoms of the heteroaryl group are sulfur atoms and the remaining atoms of such ring member atoms of the heteroaryl group are carbon atoms, wherein the mono-or polycyclic aryl and polycyclic heteroaryl groups are unsubstituted or contain 1 or 2 free radicals R ^Ar, wherein R ^Ar has one of the meanings defined herein, especially as mentioned as preferred. The unsubstituted radical Ar ¹ is preferred here.

Ar ¹ is more preferably 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 (such as benzo [ c ] phenanthren-2-yl), benzo [ c ] phenanthren-3-yl, benzo [ c ] fluoren-4-yl, benzo [ c ] fluoren-5-yl, benzo [ c ] pyrene-10-yl), benzopyrene-1-yl (such as pyrene-2-yl),Radicals (such as/>-1-Yl,/>-2-Yl,-3-Yl/>-4-Yl/>-5-Yl or/>-6-Yl), triphenylene (such as triphenylen-1-yl or triphenylen-2-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-6-yl or benzo [ b ] thiophen-7-yl), dibenzo [ b, d ] thiophenyl (such as 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), naphtho [1,2-b ] thiophenyl (such as naphtho [1,2-b ] thiophen-5-yl), naphtho [2,3-b ] thiophen-yl (such as naphtho [2,3-b ] thiophen-3-yl, naphtho [2, 3-b-thiophen-yl or naphtho [2,3-b ] thiophen-3-yl), benzo [2,3-b ] thiophen-yl (such as benzo [2,3-b ] thiophen-yl, or dibenzo [ 2-b-2-b ] thiophen-1-yl), benzo [2, 2-b ] thiophen-yl (such as benzo [1,2-b, 2-b ] thiophen-yl); 4,3-b '] dithiophene (such as benzo [1,2-b:4,3-b' ] dithiophene-7-yl), benzo [1,2-b:6,5-b ' ] dithiophene groups (such as benzo [1,2-b:6,5-b ' ] dithiophene-4-yl), benzo [1,2-b:5,4-b ' ] dithiophene groups (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 groups (such as benzo [1,2-b:4,5-b ' ] dithiophene-4-yl), and thianthrene groups (such as thianthrene-1-yl or thianthrene-2-yl).

Ar ¹ is even more preferably 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,/>The radicals and dibenzo [ b, d ] thienyl radicals are particularly selected from the group consisting of phenyl, naphthyl and phenanthryl radicals, and in particular from the group consisting of phenyl, naphthalen-1-yl, naphthalen-2-yl and phenanthren-9-yl.

R ⁵ is preferably selected from: hydrogen, methyl, ethyl and the radical Ar ¹, wherein Ar ¹ has one of the meanings defined herein, especially the preferred meaning. R ⁵ is more preferably hydrogen, methyl or ethyl, and especially hydrogen or methyl.

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

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

R is preferably selected from: methyl, phenyl, naphthyl, phenanthryl and triphenylene, which are unsubstituted or substituted by 1, 2 or 3 identical or different radicals R 'where R' independently at each occurrence has one of the meanings defined herein, particularly preferred. More preferably R is selected from: phenyl, naphthyl and phenanthryl, which are unsubstituted.

R' is preferably selected from: hydrogen, methyl, phenyl and naphthyl, wherein phenyl and naphthyl are unsubstituted or substituted by 1, 2 or 3 identical or different radicals R ", wherein R" independently at each occurrence has one of the meanings defined herein, particularly preferred. R' is more preferably 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 a particular subgroup (10.1) of group (10) of embodiments, wherein both groups Z ¹ and Z ² in formula (Ia) are Z, which has one of the meanings defined herein for Z ¹ and Z ², especially one of the preferred meanings, and the groups-O-Z are both in para-position relative to part X, 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, particularly have the meanings mentioned as preferred, and wherein R ³ and R ⁴ are particularly not hydrogen.

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

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, especially one of the preferred meanings, variables X, R ¹、R²、R³ and R ⁴ have the meanings defined herein, especially the meanings mentioned as preferred, and wherein R ³ and R ⁴ are especially not hydrogen.

The moiety X in formulae (Ia-1) and (IIa-1) is preferably as defined in group (5), group (5 ') or group (5') of the embodiments. Thus, moiety X is herein specifically selected 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 particularly selected 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 selected from: single bond, O, CH ₂、C(CH₃)₂, S and SO ₂, and are selected in particular from: single bond, C (CH ₃)₂, S and SO ₂. In this context, X is especially preferred to C (CH ₃)₂. In this context, X is also especially preferred to S or SO ₂).

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

Even more preferred are the compounds of formula (Ia-1) and the structural units of formula (IIa-1), wherein the substituents R ¹、R²、R³ and R ⁴ have the same meaning, which in particular have one of the meanings mentioned herein as preferred, and in particular one of the meanings defined in 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) of the embodiments.

Particular preference is given to compounds of the formula (Ia-1) and structural units of the formula (IIa-1), where the substituents R ¹、R²、R³ and R ⁴ have the same meaning and are selected from the group consisting of: phenyl, naphthalen-1-yl, naphthalen-2-yl, 1, 2-dihydroacenaphthene-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-2-yl, dibenzo [ b, d ] thiophen-4-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-dihydroacenaphthylenyl, 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 are as defined in any of rows 1 to 442 in table a below, wherein variable R ^y represents the same meaning as substituents R ¹、R²、R³ and R ⁴.

Table A

/>

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

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

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

The moiety X in formulae (Ia-2) and (IIa-2) is preferably as defined in group (5) or group (5' ") of the embodiments. Thus, moiety X is herein specifically selected from: single bond, O, N-phenyl, N-naphthyl, N-phenanthryl, CH ₂、C(CH₃)₂、CH(CH₃), S, S (O) and SO ₂, more particularly selected 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 selected from: single bond, O, CH ₂、C(CH₃)₂, S and SO ₂, and are selected in particular from: single bond, C (CH ₃)₂, S and SO ₂. In this context, X is particularly preferred as a single bond.

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

Even more preferred are the compounds of formula (Ia-2) and the structural units of formula (IIa-2), wherein the substituents R ¹、R²、R³ and R ⁴ have the same meaning, which in particular have one of the meanings mentioned herein as preferred, and in particular one of the meanings defined in 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) of the embodiments.

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

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

Table B

/>

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, in analogy to the procedure 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 radicals 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. The corresponding compounds (I) wherein both Z ¹ and Z ² are 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).

Scheme 1:

Each of the transformations in steps a), b) and c) of scheme 1 may be accomplished by using one or more of the reaction steps of the methods described below in connection with schemes 2a, 2b, 2c, 3, 4a, 4b, 5, 6a, 6b, 6c, 7a and 7b or by obvious variations of such reaction steps, or alternatively by preparing existing procedures in organic chemistry or combinations 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. are the same substituents Ar as defined herein selected from optionally substituted mono-or polycyclic (hetero) aryl groups, and wherein Z ¹ and Z ² are the same groups Z' as defined herein selected from-Alk-OH, -CH ₂-Ar²-CH₂-OH、-Alk-C(O)OR^x and-CH ₂-Ar²-C(O)OR^x, can be prepared, for example, in analogy to the reaction described in reaction scheme 2a below.

Scheme 2a:

in an initial step i), bisphenol (1') whose hydroxyl groups are respectively located in the ortho or para position with respect to moiety X 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 a 3 to 15-fold molar excess relative to bisphenol (1'). In step ii), tetrabromobisphenol (4) may be converted to compound (5) by reaction with a reagent Y-Z 'in the presence of a base (e.g., an oxygen-containing base, such as an alkali metal carbonate, e.g., 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 via 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 such 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 comprising at least one trisubstituted phosphine ligand, such as tetrakis (triphenylphosphine) palladium and tetrakis (trimethylphosphine) palladium. The palladium catalyst is often prepared in situ from a suitable palladium precursor, such as palladium (II) acetate (Pd (OAc) ₂) and a suitable phosphine ligand, such as especially triarylphosphines, such as triphenylphosphine and tricresylphosphine.

If the radical Z ' of the compound (5) is hydroxyethyl, the conversion shown in reaction step ii) of scheme 2a can be carried out using 2-chloroethanol as reagent Y-Z ', or alternatively using ethylene carbonate or ethylene oxide (in particular ethylene carbonate) instead of reagent Y-Z '. Such conversion with 2-chloroethanol, ethylene carbonate or ethylene oxide is carried out in the presence of a base, for example an oxygen-containing base such as an alkali metal carbonate, e.g. potassium carbonate.

As another example, if the group Z 'of compound (5) is-Alk-C (O) OR ^x, the conversion shown in reaction step ii) of scheme 2a can be carried out using Hal-Alk-C (O) OR ^x as reagent Y-Z', wherein Hal is halogen, such as in particular bromine OR chlorine, in a manner analogous to that described, for example, below: T.Ema, J.Org.Chem.,2010,75 (13), 4492-4500 or t.ema et al, org.lett.,2006,8,17,3773-3775. If necessary, the ester groups O-Alk-C (O) R ^x thus introduced can then be converted into the corresponding acid groups O-Alk-C (O) OH using well-known ester hydrolysis procedures.

Suitable reaction conditions for step i) of scheme 2a and suitable reagents may be taken from, for example, US 3,363,007, US 5,208,389, JP H049346, CN 101100416, US 6,147,264; kumar et al Organic Process Research & Development,2010,14 (1), 174-179; dev et al Polymer 2017,133,20-29; r. N.Wang et al Hebei Gongye Daxue Xuebao,2012,41 (3), 42-45; lu et al, crystal Growth & Design,2011,11 (8), 3551-3557; K. oh et al, bioorganic & MEDICINAL CHEMISTRY LETTERS,2008,18 (1), 104-108; xin et al, huaxue Yanjiu Yu Yingyong,2006,18 (11), 1346-1348; yang et al, china, CN 111072529, CN 103992209, CN102898337; and V.A. Orlova et al Trudy Vsesoyuznogo Instituta Gel' mintologiiimeni K.I. Skryabina,1971,18,201-205; suitable reaction conditions for step ii) of scheme 2a and suitable reagents may be taken from, for example, JP S50105638 (a), JP S5846034 (a), JPs5251351 (a); imai, hirokazu et al, japan, JP 2013249373, JP 2013249374, JP 2008143854 and JP H0338563 (a); and suitable reaction conditions and suitable reagents for step iii) of scheme 2a may be taken from, for example, a.suzuki et al chem.rev.,1995,95,2457-2483; 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; bourrain et al, synlett,2004,5,795-798; and B.Li et al, europ.J. org.chem.2011, 3932-3937.

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

Scheme 2b:

Scheme 2c:

The reactions according to steps i), ii) and iii) of schemes 2b and 2c can be carried out using the same or very similar reaction conditions as described for steps i), ii) and iii) of scheme 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 all the same substituents Ar as defined in the context of scheme 2a, and wherein both Z ¹ and Z ² are hydrogen. The sequence of steps i) and iii) according to scheme 2 b) is therefore suitable for preparing such compounds (Ia) of 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 condensation of 2, 6-dibromophenol or 2, 4-dibromophenol with formaldehyde, as described in scheme 3 below.

Scheme 3:

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

As an alternative step to the synthesis according to scheme 2a or 2c, the tetrabromide of formula (5) as defined herein, 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, can also be prepared by reduction of the corresponding compound (5) having X as SO ₂. The tetrabromide of formula (5) wherein X is S (O) may in turn be reduced to the corresponding sulfide, thus providing an alternative method for compound (5) having X as S. Similarly, a compound (Ia ') wherein X is S (O) or S is also obtained by reduction of the corresponding compound (Ia') having SO ₂ or S (O) moiety at position X. Such transformations are summarized in schemes 4a and 4b below.

Scheme 4a:

Scheme 4b:

The reductive transformations shown in schemes 4a and 4b can be performed using procedures well known in the art to convert sulfones to sulfoxides and sulfoxides to sulfides, respectively. For example, sulfoxides can be converted to the respective sulfoxides by an initial reaction with 4-chlorobenzenediazonium tetrafluoroborate followed by reduction with sodium borohydride, whereas sulfoxides can be converted to the respective sulfides by reduction with lithium aluminum hydride or elemental sulfur.

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

Scheme 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 (hetero) aryl 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, analogously to the process described in scheme 6a below.

Scheme 6a:

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

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

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

Scheme 6b:

Scheme 6c:

The reactions according to steps i), ii) and iii) of schemes 6b and 6c can 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) of the invention.

As an alternative to the synthesis according to schemes 6a or 6c, 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, the dibromides of formula (10) as defined herein can also be prepared by reduction of the corresponding compound (10) having X as SO ₂. Bisphenol compounds of formula (10) wherein X is S (O) may in turn be reduced to the corresponding sulfide, thus providing an alternative method for compounds (10) having X as S. Similarly, a compound (Ia '") wherein X is S (O) or S is also obtained via reduction of the corresponding compound (Ia'") having an SO ₂ or S (O) moiety at position X. Such transformations are summarized in schemes 7a and 7b below.

Scheme 7a:

Scheme 7b:

The reductive transformations shown in schemes 7a and 7b can be performed using procedures well known in the art to convert 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-brominated phenols of formula (9) wherein X is a CH ₂ moiety and 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 the starting compounds 2-or 4-bromophenol instead of 2, 6-dibromophenol and 2-or 4-arylphenol instead of 2, 6-diarylphenol (6), respectively.

Other compounds of formula (I) can be prepared by using obvious variations of the above reactions and combinations thereof with procedures already existing in the preparation of organic chemistry.

The reaction mixtures obtained in the various steps of the syntheses described in the above schemes 1, 2a, 2b, 2c, 3, 4a, 4b, 5, 6a, 6b, 6c, 7a and 7b for the preparation of the compounds are generally worked up in a conventional manner, for example by mixing with water, separating off the phase and purifying the crude product, where appropriate, by washing, chromatography or crystallization. The intermediates are in some cases obtained as viscous oils in colorless or pale brown form, which are free of volatiles or purified under reduced pressure and moderate elevated temperature. If the intermediate is obtained as a solid, purification can be achieved by recrystallization or a washing procedure (such as slurry washing).

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

As stated above, the compounds of the invention can be obtained in high purity, which means that products are obtained which, apart from volatiles, do not contain significant amounts of organic impurities other than the compounds of formula (I). The purity of the compounds of the formula (I) is generally at least 95%, in particular at least 98% and especially at least 99%, based on nonvolatile organic matter, i.e. the product contains up to 5%, in particular up to 2% and especially up to 1% of nonvolatile impurities other than the compounds of the 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 compounds are understood to mean compounds having a boiling point of more than 200 ℃ at standard pressure.

A particular benefit of the present invention is that the compounds of formula (I) and solvates thereof and the like are often available in crystalline form. The compounds of formula (I) in crystalline form may be present in pure form or in the form of solvates with water or organic solvents. Accordingly, a particular embodiment of the invention relates to compounds of formula (I) which are present substantially in crystalline form. The invention relates in particular to crystalline forms in which the compound of formula (I) is present without solvent and to crystalline solvates of the compound of formula (I) in which the crystals contain added solvent.

A particular benefit of the present invention is that the compounds of formula (I) and solvates thereof and the like are often readily crystallisable from existing organic solvents. This allows for efficient purification of the compound of formula (I). Organic solvents suitable for crystallization of the compound of formula (I) or a solvate thereof include, but are not limited to, aromatic hydrocarbons (such as toluene or xylene), aliphatic ketones, in particular 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 t-butyl ether, ethyl t-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 and the like may be obtained in purified form by purifying the crude product of such compounds using other simple and effective methods, such as in particular washing the crude solid obtained directly after conversion using a slurry to prepare the compounds of formula (I). Slurry cleaning is typically carried out at ambient temperature or at relatively high temperatures, typically about 30 to 90 ℃, especially 40 to 80 ℃. Suitable organic solvents herein are essentially the same as those listed above for the crystallization of the compounds of formula (I), such as the aromatic hydrocarbons, aliphatic ketones and aliphatic ethers mentioned in particular, for example toluene, methyl ethyl ketone and methyl tert-butyl ether.

Accordingly, the compounds of formula (I) for preparing thermoplastic polymers as defined herein, in particular polycarbonates, can be easily prepared and obtained in high yields and purity. The compounds of formula (I) may be obtained in particular in crystalline form, which allows efficient purification to the extent required for the preparation of optical resins. Such compounds are particularly obtainable in purities providing high refractive indices and low haze, which are particularly important for the preparation of optical resins from which optical devices are made. In summary, the compounds of formula (I) are particularly useful as monomers for preparing optical resins.

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

Those skilled in the art will also appreciate that the structural units of formulas (II), (IIa-1) and (IIa-2) are repeat units within the polymer chain of the thermoplastic resin.

In addition to the separate structural units of the formulae (II), (IIa-1) and (IIa-2), the thermoplastic resins may have structural units different from these. In a preferred embodiment, such other structural units are derived from aromatic monomers of formula (IV) which give structural units 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;

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

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 are 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 is also provided with

* Represents a point of attachment to a benzene ring;

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

Rz 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 is also provided with

Alk ³ is C ₁-C₄ -alkanediyl.

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

In the case of the formulae (IV) and (V), A ¹ is in particular a polycyclic radical containing 2 benzene or naphthalene rings, the benzene rings being linked by A. In this case, a is particularly selected from: single bond, CH-Ar, CAr ₂ and radical A'.

In the case 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), preference is given to the monomers of the formulae (IV-1) to (IV-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 (IV), and wherein R ^z is specifically selected from the group consisting of 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 particularly selected from the group consisting of single bonds, CH ₂ and O-CH ₂CH₂, and 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 as 9, 9-bis (6- (2-hydroxy-ethoxy) 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) -diphenylmethane 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-hydroxy-methoxy) -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 general 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), and particular preference 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-phenyl) fluorene (BPPEF).

Accordingly, among the structural units of the formula (V) which can be contained in the thermoplastic resin, structural units of the general formulae (V-1) to (V-6) are preferably selected,

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 for formula (V), and wherein R ^z is specifically selected from the group consisting of a single bond, CH ₂ and OCH ₂CH₂.

Particular preference is given to structural units of the formulae (V-11) to (V-20), where R ^z and R ^aa are as defined herein, and where R ^z is particularly selected from the group consisting of single bonds, CH ₂ and O-CH ₂CH₂, and 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 preferably selected. 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 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 the formula (V-11), structural units of the formula (V-19) and structural units of the formula (V-20). In this particular group of embodiments, thermoplastic resins are preferred 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 those thermoplastic resins having one of the meanings mentioned as preferred. Among this particular group of embodiments, preference is given to those thermoplastic resins in which the radicals R ^z in the structural units of the formulae (V-11), (V-19) and (V-20) are O-CH ₂CH₂.

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

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

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 may be prepared in analogy to known methods.

For example, the compound of formula (IV-6) may be prepared in various synthetic methods, as disclosed in, for example, JP publication No. 2014-227387, JP publication No. 2014-227388, JP publication No. 2015-168858 and JP publication No. 2015-187098. For example, 1' -binaphthol can be reacted with ethylene glycol monomethylenesulfonate; alternatively, 1' -binaphthol may be reacted with alkylene oxide, halohydrin, or alkylene carbonate; and alternatively, 1' -binaphthol may be reacted with ethylene carbonate. Whereby 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, compounds of formula (IV-2) may be prepared in various synthetic methods, as disclosed, for example, in JP publication 5442800 and JP publication 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 hydrochloric acid and a thiol (such as mercapto carboxylic acid);

(d) Reacting fluorene with hydroxynaphthalene in the presence of sulfuric acid and a thiol (such as mercaptocarboxylic acid), and thereafter crystallizing the product from a crystallization solvent comprised of hydrocarbon and polar solvent to form binaphthol fluorene; and the like.

Whereby a compound of formula (IV-2) wherein R ^z is a single bond is 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 oxide or a haloalkanol. For example, the reaction of 9, 9-bis (hydroxynaphthyl) -fluorene of formula (IV-2) wherein R ^z is a single bond with an alkylene oxide or a haloalkanol gives (IV-2) compounds 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 alkaline conditions.

The monomers of formula (I) and similar comonomers of formula (IV) used in the manufacture of the thermoplastic resins may contain specific impurities derived from their preparation, for example hydroxyl compounds containing OH groups in place of the groups O-Z ¹ -OH or O-Z ² -OH, or may contain the groups O-Alk ' - [ O-Alk ' ] _o in place of the groups O-Alk ' -or may contain halogen atoms in place of the groups R ¹、R²、R³ or R ⁴. The total amount of such 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, the total amount of the dihydroxy compounds in which the carbon number of at least one of the radicals Z ¹ or Z ² is different from that of the 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 main component in the monomer is a dihydroxy compound represented by formula (I). The total amount of the dihydroxy compounds in which the carbon number of at least one of the radicals Z ¹ or Z ² is different from formula (I) is more preferably 50ppm or less, and still more preferably 20ppm or less. Likewise, the amount of impurities in the comonomer of formula (IV) is within the range given for the monomer of formula (I).

Thermoplastic resins suitable for preparing optical devices such as lenses are especially polycarbonates, polyester carbonates and polyesters. Preferred thermoplastic resins for use in the preparation of optical devices such as lenses are especially polycarbonates.

The polycarbonates are structurally 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 which differ from 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 herein above;

and structural units of formula (III-1) originating from the carbonate-forming component:

Wherein each # represents a point of attachment to an adjacent structural unit, i.e., an O attached to a structural unit of formula (II), and (if present) an O attached to a structural unit of formula (V).

The polyesters are structurally characterized by structural units of at least one of the formulae (II), (IIa-1) and (IIa-2), optionally structural units derived from diol monomers other than the monomer compounds of the formula (I), such as structural units of the formula V, and structural units derived from dicarboxylic acids, such as structural units of the formula (III-2) derived in the case of benzenedicarboxylic acids, structural units of the formula (III-3) derived in the case of naphthalenecarboxylic acids, structural units of the formula (III-4) derived in the case of oxalic acids, and structural units of the formula (III-5) derived in the case of malonic acids, respectively.

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 (if present) O to a point of attachment to a structural unit of formula (V).

The polyester carbonates are structurally characterized by structural units having at least one of the formulae (II), (IIa-1) and (IIa-2), optionally structural units derived from diol monomers other than the monomer compounds of formula (I), such as structural units of formula (V), structural units of formula (III-1) originating from the carbonate forming component and structural units derived from dicarboxylic acids, such as structural units of formula (III-2) derived in the case of benzenedicarboxylic acids, structural units of formula (III-3) derived in the case of naphthalene carboxylic acids, structural units of formula (III-4) derived in the case of oxalic acid and structural units of formula (III-5) derived in the case of malonic acid, respectively.

A particular group of embodiments relates to thermoplastic copolymer resins, in particular polycarbonates, polyester carbonates and polyesters, having both structural units of formula (II) and one or more structural units of formula (V), i.e. resins, in particular polycarbonates, polyester carbonates and polyesters, which are obtained by reacting at least one monomer of formula (I) with one or more monomers of formula (IV). In this case, the molar ratio of the monomer of formula (I) to the monomer of formula (IV) and, similarly, of the structural unit of formula (II) to the structural unit of formula (V) is between 5:95 to 80:20, in particular in the range 10:90 to 70:30, and in particular at 15:85 to 60:40 or in the range of 1:99 to 70:30, in particular in the range 5:95 to 60:40, more preferably in the range of 8:92 to 45:55 or in the range of 10:90 to 40:60, and in particular at 12:88 to 30:70 or in the range of 12:88 to 20: 80. Accordingly, the molar ratio of the structural units of the formula (II) is generally in the range from 1 to 70mol-%, in particular from 5 to 60mol-%, more preferably in the range from 8 to 45mol-%, or in the range from 10 to 40mol-%, and in particular in the range from 12 to 30mol-%, or in the range from 15 to 30mol-%, and in particular in the range from 12 to 20mol-%, or in the range from 15 to 20mol-%, based on the total molar amount of the structural units of the formulae (II) and (V). Accordingly, the molar ratio of the structural units of the formula (V) is generally in the range from 30 to 99mol-%, in particular from 40 to 95mol-%, more preferably in the range from 55 to 92mol-%, or in the range from 60 to 90mol-%, in particular in the range from 70 to 88mol-%, or in the range from 70 to 85mol-%, and in particular in the range from 80 to 88mol-%, or in the range from 80 to 85mol-%, based on the total molar amount of the structural units of the formulae (II) and (V).

The thermoplastic copolymer resin of the present invention (such as a polycarbonate resin) may include any of a random copolymer structure, a block copolymer structure and an alternating copolymer structure. The thermoplastic resin according to the invention does not need to include all structural units (II) and one or more different structural units (V) in a single identical polymer molecule. That is, the thermoplastic copolymer resin according to the present invention may be a mixed resin as long as the above-described structures are respectively included in any 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 or copolymer comprising at least one structural unit (II) and a homopolymer or copolymer comprising at least one structural unit (V), or it may be a mixed resin of 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 obtained by polycondensation of a diol component with a carbonate-forming component. Likewise, thermoplastic polyesters and polyester carbonates are obtained by polycondensation of a diol component with a dicarboxylic acid or an ester-forming derivative thereof, and optionally a carbonate-forming component.

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

The method for producing the thermoplastic resin of the present invention, such as a polycarbonate resin, includes a melt polycondensation method of a dihydroxy component corresponding to the above-mentioned structural unit and a carbonic acid diester. According to the invention, the dihydroxy compound comprises at least one dihydroxy compound represented by formula (I), in particular formula (Ia), (Ia-1) or (Ia-2), respectively, as defined herein. In addition to the compounds of formula (I), the dihydroxy compounds may also comprise one or more dihydroxy compounds of formula (IV), preferably of formula (IV-1) to (IV-6), in particular of formula (IV-11) to (IV-20), more particularly of formula (IV-11), (IV-12), (IV-14), (IV-19 or (IV-20), and especially of formula (IV-11), (IV-19) or (IV-20).

As is clear 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). In particular, the polycarbonate resin may be formed in a melt polycondensation process in which a compound represented by the formulas (I), (Ia-1) and (Ia-2), respectively, or a combination thereof with at least one compound of the 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) 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 mentioned previously, the monomers of formula (I) and similarly the comonomers of formula (IV) used to make the thermoplastic resin may contain impurities derived 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., 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)

One or more of the following compounds, for example, represented by the following figures, may be included as impurities:

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 radicals Z ¹ or Z ² has a carbon number different from that of formula (Ia-2.3) is more preferably 50ppm or less, and still 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 two 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 -.

The total amount of such dihydroxy compounds of formula (IV-2) or (IV-3) in which at least one of 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 main component in the monomer is a dihydroxy compound represented by formula (IV-2) or (IV-3). Wherein the total amount of the dihydroxy compound in which at least one of the values of c and d is different from the formula (IV-2) or (IV-3) is again preferably 50ppm or less, and more preferably 20ppm or less.

The polycarbonate resin can be obtained by the following reaction: the monomer compound of formula (I), or at least one monomer compound of formula (I), especially at least one monomer compound mentioned herein as preferred, and one or more monomer compounds of formula (IV), especially formula (V-11), (V-12), (V-14), (V-19) or (V-20), and especially a combination of formula (IV-11), (IV-19) or (IV-20) and the like, is reacted as a dihydroxy component with a carbonate precursor, such as a carbonic acid diester.

However, in a 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 radicals are replaced with a different radical (such as a vinyl terminal radical represented by-och=ch ₂). Because such impurities are typically small, the polymer product formed can be used as a polycarbonate resin without the need for purification processes.

The thermoplastic resins of the present invention may also contain minor amounts of impurities, such as additional amounts of thermoplastic resin composition or a portion of the polymer backbone of the thermoplastic resin. Examples of such impurities include phenol, unreacted carbonic acid diester, and monomers formed in the process of forming 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 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 such impurities is not critical, but may be 0.1ppm or 1.0ppm.

The total amount of residual palladium 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 in standard procedures, such as treatment with an adsorbent (e.g., activated carbon).

Resins having the targeted characteristics can be formed by adjusting the amounts of phenol and carbonic acid diester. The amounts of phenol, carbonic acid diester and monomer can be appropriately adjusted by arranging conditions for polycondensation, operating conditions of a device for polymerization, or conditions for extrusion molding 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 10000 to 80000 daltons, still more preferably 10000 to 50000 daltons, and in particular in the range of 15000 to 50000 daltons. GPC measurements can be calibrated using polystyrene standards. The Mw of the thermoplastic resins of the present invention measured in this manner may also be expressed herein as "polystyrene conversion Mw", "Mw of polystyrene conversion" or "Mw measured in GPC relative to polystyrene standards". The number average molecular weight (Mn) of the thermoplastic resin according to the present invention is preferably 3000 to 20000, more preferably 5000 to 15000, and still more preferably 7000 to 14000.Mn can be measured similarly to Mw, measured by GPC calibrated against polystyrene standards 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, and still more preferably 10000 to 14000.

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

When the thermoplastic resin has a weight average molecular weight (Mw) value within the above-mentioned suitable range, the molded article made of the thermoplastic resin has high strength. In addition, such thermoplastic resins having suitable Mw values are advantageous for molding because of their excellent flowability.

In a particular group 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 this content of low molecular weight compounds having a Mw of less than 1000 is generally 7.0% by weight, preferably 5.0% by weight, more preferably 3.0% by weight, even more preferably 2.0% by weight, in particular 1.8% by weight, and especially 1.7% by weight. Accordingly, in this particular group 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, and especially in the range from 1.0 to 1.7% by weight, based on the total weight of the thermoplastic resin in each case.

The thermoplastic resin of the present invention containing the low molecular weight compound having a Mw value of less than 1000 in the amount within the above range forms a molded body having high mechanical strength. Such thermoplastic resins are particularly less or less prone to separating or precipitating the low molecular weight compound during molding processes such as injection molding, also known as bleed-out. 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 speeds and reduced energy requirements for 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 GPC analysis chart described above. The content is calculated in particular as the ratio of the total area of peaks of the low molecular weight compounds to the total area of all peaks of the graph obtained by GPC analysis of the thermoplastic resin. Accordingly, the low molecular weight compound content (CLWC) in the thermoplastic resin is represented by the following formula:

The polycarbonate resin mentioned above has a high refractive index (n _D or n _d) and is thus suitable for an optical lens. The refractive index value as referred to herein is a value of a film having a thickness of 0.1mm, which can be measured in the method of JIS-K-7142 using an Abbe refractometer. The refractive index of the polycarbonate resin according to the present invention at 23℃and 589nm wavelength is usually 1.640 or more, preferably 1.650 or more, more preferably 1.660 or more, still more preferably 1.670 or more, and particularly 1.680 or more in the case where the resin includes the structural unit (2). 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 (v) of the polycarbonate resin is preferably 24 or less, more preferably 20 or less, and still more preferably 18 or less. The Abbe number can be calculated using the following equation based on the 487nm, 589nm and 656nm wavelengths and the refractive index at 23 ℃.

v＝(n_D-1)/(n_F-n_C)

N _D: refractive index at 589nm wavelength

N _C: refractive index at 656nm wavelength

N _F: refractive index at 486nm wavelength

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 ℃, in view of the fact that the polycarbonate can be used for injection molding. Regarding the molding flowability and the heat resistance of the molded article, the lower limit of Tg is preferably 130℃and more preferably 135℃and the upper limit of Tg is preferably 185℃and more preferably 175 ℃. Glass transition temperatures (Tg) within the ranges provided above provide an effective usable temperature range and avoid the risk that the melting temperature of the resin may be too high and thus the resin may be subjected to unwanted decomposition or staining. Moreover, it allows the preparation of a mold with high surface accuracy.

In a preferred group (10) of embodiments, the absolute value of the oriented 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, in particular in the range of 0 to 1x10 ^-3, and in particular in the range of 0 to 0.4x10 ^-3.

An optical molded body (such as an optical element) manufactured using the polycarbonate resin of the present invention has a total light transmittance of 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 according to the present invention has high moisture resistance and heat resistance. Moisture resistance and heat resistance can be evaluated by performing a "PCT test" (autoclave test) on a molded body such as an optical element manufactured using a thermoplastic resin and then measuring the total light transmittance of the molded body after the PCT test. In the PCT test, first, PC305S III manufactured as HIRAYAMACorporation having an injection-molded body with a diameter of 50mm and a thickness of 3mm was held at 120℃under 0.2MPa at 100% RH for 20 hours. The injection-molded body sample was then removed from the apparatus, and the total light transmittance was measured in accordance with the method of JIS-K-7361-1 using a parallax measuring instrument of the SE2000 type, 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 resistance and heat resistance than conventional thermoplastic resins.

The thermoplastic resin according to the present invention has a b value, which represents chromaticity, of preferably 5 or less. When the value of b is smaller, the color is less yellowing, and the color is good.

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), such as one or more monomers of formula (IV).

Suitable diol monomers which differ from the monomer compounds of the formula (I) are those conventionally used for the preparation of polycarbonates, for example

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, norbornane dimethanol, pentacyclopentadecanedimethanol, cyclopentane-1, 3-dimethanol, spiroglycerol (spiroglycol), 1,4:3, 6-dianhydride-D-sorbitol, 1,4:3, 6-dianhydride-D-mannitol and 1,4:3, 6-dianhydride-L-iditol 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-t-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-bis [4- (2-hydroxyethoxy) -3-methylphenyl ] fluorene, 9, 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 (binaphthyl) or 2,2' -bis (2-hydroxyethoxy) -1,1' -binaphthyl (binaphthalene) (BNE).

In addition to the monomers of formula (I), the diol component preferably comprises at least one monomer of formula (IV). The total amount of monomers of formulae (I) and (IV) in particular contributes at least 90 wt.% of the diol component based on the total weight of the diol component, or at least 90mol-% of the diol component based on the total molar amount of diol monomers of the diol component. In addition to the monomers of formula (I), the diol component comprises in particular at least one monomer selected from the monomers of formulae (IV-11) to (IV-20). In addition to the monomers of formula (I), the diol component more particularly comprises at least one monomer selected from the group consisting of monomers of formulas (IV-11), (IV-12), (IV-14), (IV-19) and (IV-20). In addition to the monomers of formula (I), the glycol component comprises 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, among others.

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

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

Thus, the relative molar amount of the monomer compounds of formula (IV), based on the total mole of the diol component, is not more than 99mol-%, or 98mol-%, or 95mol-%, in particular not more than 92mol-%, or 90mol-%, and in particular not more than 88mol-%, or 85mol-%, and preferably in the range from 20 to 99mol-%, or 20 to 98mol-%, or 20 to 95mol-%, or 20 to 92mol-%, in particular in the range from 30 to 98mol-%, or 30 to 95mol-%, or 30 to 92mol-%, or in the range from 40 to 95mol-%, or 40 to 92mol-%, or 40 to 90mol-%, or 40 to 88mol-%, or 40 to 85mol-%, but also up to 99 mol-%.

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

Examples of other 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 include monofunctional compounds, in the case of polycarbonates monofunctional alcohols and in the case of polyesters monofunctional alcohols or monofunctional carboxylic acids. Suitable monoalcohols 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 polyfunctional compounds, in the case of polycarbonates polyfunctional alcohols having three or more hydroxyl groups and in the case of polyesters polyfunctional alcohols having three or more hydroxyl groups or polyfunctional carboxylic acids 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 such compounds is often not more than 10mol-%, based on the molar amount of the diol component.

Suitable carbonate-forming monomers are those conventionally used as carbonate-forming monomers for the preparation of polycarbonates, including, but not limited to, phosgene, diphosgene, and carbonic acid diesters, such as diethyl carbonate, diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, and dinaphthyl carbonate. Among these, diphenyl carbonate is particularly preferable. The carbonate-forming monomer is usually used in a ratio of 0.97 to 1.20 mol, and more preferably 0.98 to 1.10 mol, relative to 1 mol of the total amount of the dihydroxy compounds.

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 benzene dicarboxylic acids, 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 xylene esters.

In the case of polyesters, the ester-forming monomer is usually used in a ratio of 0.97 to 1.20 mol, and more preferably 0.98 to 1.10 mol, relative to 1mol of the total amount of the dihydroxy compounds.

The polycarbonates of the invention may be prepared by reacting a diol component comprising monomers of formula (I) and optionally other diol monomers such as monomers of formula (IV) with carbonate forming monomers in a manner similar to known polycarbonate preparation methods, as described, for example, in US 9,360,593, US2016/0319069 and US2017/0276837, which are incorporated herein by reference in their entirety.

The polyesters of the invention may be prepared by reacting a diol component comprising monomers of formula (I) and optionally other diol monomers such as monomers of formula (IV) with a dicarboxylic acid or ester-forming derivative thereof in a manner similar to known polyester preparation methods, as described for example in US2017/044311, which is incorporated herein in its entirety, and the references cited therein.

The polyester carbonates of the present invention may be prepared by reacting a diol component comprising monomers of formula (I) and optionally other diol monomers such as monomers of formula (IV), carbonate forming monomers, and dicarboxylic acids or ester forming derivatives thereof in a manner similar to known polyester carbonate preparation methods, as described in the art.

Polycarbonates, polyesters and polyester carbonates are generally prepared by reacting monomers of the diol component with carbonate-forming monomers and/or ester-forming monomers (i.e., dicarboxylic acids or ester-forming derivatives thereof), if carbonate-forming monomers or ester-forming derivatives of polycarboxylic acids are used, in the presence of an esterification catalyst, particularly a transesterification catalyst.

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

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, alkali metal oxide, alkali metal carbonate, alkali metal borohydride, alkali metal bicarbonate, alkali metal phosphate, alkali metal hydrogen phosphate, alkali metal hydroxide, alkali metal hydride, alkali metal alkoxide (alkoxide) 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 borophenol (sodium borophenoxide), sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, and disodium phenylphosphate; and also includes disodium, dipotassium, cesium and lithium salts of bisphenol a; sodium, potassium, cesium and lithium salts of phenols; and the like.

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 salts, alkaline earth metal oxides, alkaline earth metal carbonates, alkaline earth metal borohydrides, alkaline earth metal hydrogencarbonates, alkaline earth metal hydroxides, alkaline earth metal hydrides, alkaline earth metal alkoxides, 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 including alkyl groups, aryl groups, or the like, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, and the like; tertiary amines such as triphenylamine, dimethylbenzylamine, triphenylamine, and the like; secondary amines such as diethylamine, dibutylamine and the like; 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 and the like of polyvalent metals such as zinc, tin, titanium, zirconium, lead, particularly chlorides, alkoxides, alkanoates, benzoates, acetylacetonates and the like. These may be used independently or in a 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, dibutyl tin laurate, dibutyl tin oxide, dibutyl tin methoxide, zirconium acetylacetonate, zirconium (zirconium oxyacetate) oxide, zirconium tetrabutoxide, lead (II) acetate, lead (IV) acetate, and the like.

The transesterification catalyst is usually used in a ratio of 10 ^-9 to 10 ^-3 moles, preferably 10 ^-7 to 10 ^-4 moles, relative to 1 mole of the total amount of the dihydroxy compounds.

Polycarbonates, polyesters and polyester carbonates are often 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 charging monomers and catalyst into a reactor and subjecting the reaction mixture to conditions wherein reaction between the monomers occurs and byproducts are formed. It has been found to be advantageous if the by-products are at least temporarily retained in the polycondensation reaction. However, in order to drive the polycondensation reaction towards the product end, it is advantageous to remove at least a portion of the by-products formed during the polycondensation reaction or preferably at the end. To allow byproducts to be in 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 or more and 240 minutes or less, preferably 40 minutes or more and 180 minutes or less, and particularly preferably 60 minutes or more and 150 minutes or less. In this step, in the case where the by-product is removed by distillation soon after production, the finally obtained thermoplastic resin has a low content of high molecular weight resin molecules. In contrast, in the case where the byproducts are allowed to remain in the reactor for a certain period of time, the finally obtained thermoplastic resin has a high content of high molecular weight resin molecules.

The melt polycondensation reaction may be performed in a continuous system or a batch system. The reactors which can be used for the reaction can have vertical type, which include anchor stirring blades,Stirring blades, ribbon stirring blades or the like; horizontal, including paddle blades, grid blades (blade), eyeglass blades, or the like; or extrusion type including a screw. In view of the tackiness of the polymerization product, a reactor including a combination of such reactors may be preferably used.

According to the method for manufacturing a thermoplastic resin such as a polycarbonate resin, after completion of the polymerization reaction, the catalyst may be removed or deactivated to maintain thermal stability and hydrolytic stability. The preferred method for catalyst deactivation is the addition of an acidic substance. Specific examples of the acidic substance include esters such as butyl benzoate and the like; aromatic sulfonic acids such as p-toluene sulfonic acid and the like; aromatic sulfonates such as butyl p-toluenesulfonate, hexyl p-toluenesulfonate and the like; phosphoric acid, 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 acid such as boric acid, phenylboric acid, and the like; aromatic sulfonates such as tetrabutylphosphonium dodecylbenzenesulfonate and the like; organic halides such as chlorinated stearic acid, benzoyl chloride, chlorinated p-toluenesulfonic acid and the like; alkylsulfonic acids such as dimethyl sulfonic acid and the like; organic halides such as benzyl chloride and the like. Such deactivators are frequently used in amounts of from 0.01 to 50 mol, preferably from 0.3 to 20 mol, relative to the catalyst. After the catalyst has been deactivated, 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 0.1 to 1mm Hg) and at a temperature of 200 to 350 ℃. This step preferably uses a horizontal device including stirring blades (such as paddle blades, grid blades, spectacle blades or the like) having high surface renewal capacity, or a thin film evaporator.

It is desirable that the thermoplastic resin (such as polycarbonate resin) has a very small amount 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, and more preferably 1 μm or less. It is preferred that the resulting polymer is filtered through a polymer filter. The mesh size of the polymer filter is preferably 100 μm or less, and more preferably 30 μm or less. It goes without saying that the step of sampling the resin pellets must be performed in a low dust environment. The dust environment is preferably 6 grades or less, and more preferably 5 grades or less.

The thermoplastic resin may be molded by any conventional molding procedure used to manufacture optical elements. Suitable molding procedures include, but are not limited to, injection molding, compression molding, casting, roll processing, extrusion molding, extension, and the like.

Although it is possible to mold the thermoplastic resin of the present invention itself, it is also possible to mold a resin composition containing at least one thermoplastic resin of the present invention and further containing at least one additive and/or other resin. 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, further polycarbonate resins, polyester carbonate resins, polyester resins, polyamides, polyacetals and the like, which do not contain repeating units of the 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, 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-tert-butylbenzene, N-di-hydroxybenzenen-4-hydroxybenzeneamide, N, 5-di-butylidene-4-hydroxy-4-hydroxybenzenephosphonic acid, N, 5-di-tert-butylidene-4-hydroxybenzeneamide Tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate and 3, 9-bis {1, 1-dimethyl-2- [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] ethyl } -2,4,8, 10-tetraoxaspiro (5, 5) undecane and the like. Of such 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 antioxidant content 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 process 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, pentaerythritol-bis (2, 6-di-t-butyl-4-methylphenyl) phosphite, 2-methylenebis (4, 6-di-t-butylphenyl) octyl phosphite, pentaerythritol bis (nonylphenyl) 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-ortho-diphenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, dimethyl phenylphosphonate, diethyl phenylphosphonate, dipropyl phenylphosphonate, tetra (2, 4-di-tert-butylphenyl) diphosphinate, 4' -biphenylene, tetra (2, 4-di-tert-butylphenyl) 4,3' -biphenylene diphosphinate, tetra (2, 4-di-tert-butylphenyl) 3,3' -biphenylene diphosphonite, bis (2, 4-di-t-butylphenyl) -4-phenyl-phosphonite, bis (2, 4-di-t-butylphenyl) -3-phenyl phosphonite, 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 with fatty acids. Specific examples of esters of alcohols and fatty acids include esters of monovalent alcohols and fatty acids and partial or full esters of polyvalent alcohols and fatty acids. Preferred examples of the esters of the above alcohols and fatty acids include esters of monovalent alcohols having 1 to 20 carbon numbers and saturated fatty acids having 10 to 30 carbon numbers. Preferred examples of the partial or full esters of the polyvalent alcohols and fatty acids include partial or full esters of the polyvalent alcohols having a carbon number of 2 to 25 and saturated fatty acids having a carbon number of 10 to 30. Specific examples of esters of monovalent alcohols and fatty acids include stearyl stearate (STEARYL STEARATE), palmitoyl palmitate (PALMITYL PALMITATE), butyl stearate, methyl laurate, isopropyl palmitate, and the like. Specific examples of partial or full esters of polyvalent alcohols and fatty acids include glyceryl monostearate, diglyceryl stearate, glyceryl tristearate, glyceryl monostearate, glyceryl behenate, caprylic acid monoglyceride, lauric acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrasonanoate, propylene glycol monostearate, diphenol esters of diphenyl acid (biphenyl biphenate), sorbitan monostearate, 2-ethylhexyl stearate (2-ethylhexylstearate), full or partial esters of dipentaerythritol (such as dipentaerythritol hexastearate), and the like. The release agent content in the resin composition is preferably 0.005 to 2.0 parts by weight, more preferably 0.01 to 0.6 parts by weight, and still more preferably 0.02 to 0.5 parts by weight, relative to 100 parts by weight of the thermoplastic resin.

Preferred ultraviolet absorbers are selected from the group consisting of: benzotriazole is an ultraviolet absorber, benzophenone is an ultraviolet absorber, triazine is an ultraviolet absorber, cyclic imidoester is an ultraviolet absorber, and cyanoacrylate is an ultraviolet absorber. That is, the following ultraviolet absorbers may be used independently 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-diisopropylphenyl) 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-octylphenyl) benzotriazole, 2' -bis (2-hydroxy-3, 5-di-tert-butylphenyl) benzotriazole, 2' -bis (2-hydroxy-4-octylphenyl) benzotriazole, 2, 4-bis (2-p-phenylene) benzotriazole, 2, 4-bis (2-hydroxy-3, 5-di-tert-butylphenyl) benzotriazole, 2-p-butylphenyl) benzotriazole, 2- (2-hydroxy-3-hydroxy-5-tert-butylphenyl) benzotriazole, 2-bis (2-hydroxy-5-tert-butylphenyl) benzotriazole, 2-p-phenyl) benzotriazole, 2 2- [ 2-hydroxy-3- (3, 4,5, 6-tetrahydrophthalimidomethyl) -5-methylphenyl ] benzotriazole and the like.

Examples of the benzophenone-based ultraviolet light absorbers include 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-thioxy (sulfoxy) benzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid hydrate, 2 '-dihydroxy-4-methoxy-benzophenone, 2',4 '-tetrahydroxybenzophenone, 2' -dihydroxy-4, 4 '-dimethoxybenzophenone, 2' -dihydroxy-4, 4 '-dimethoxy-5-sodium thioxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2' -carboxybenzophenone, and the like.

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

Examples of the cyclic imidoester-based 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 '-diphenylenebis (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 cyanoacrylate-based ultraviolet absorbers include 1, 3-bis- [ (2 ' -cyano-3 ',3' -diphenylacryloyl) oxy ] -2, 2-bis (((2-cyano-3, 3-diphenylacryloyl) oxy) methyl) propane, 1, 3-bis- [ (2-cyano-3, 3-diphenylacryloyl) oxy ] benzene, and the like.

The ultraviolet absorber content in the resin composition is preferably 0.01 to 3.0 parts by weight, more preferably 0.02 to 1.0 parts by weight, and still more preferably 0.05 to 0.8 parts by weight, relative to 100 parts by weight of the thermoplastic resin. Depending on the application, inclusion of the ultraviolet absorber in this content range may provide sufficient weather resistance to the thermoplastic resin.

As mentioned above, thermoplastic polymer resins (particularly polycarbonate resins) comprising repeating units of formulae (II), (IIa-1) and (IIa-2), respectively, as described above, provide high transparency and high refractive index to the thermoplastic resin, which is thus suitable for the preparation of optical devices in which high transparency and high refractive index are required. More precisely, thermoplastic polycarbonates having structural units of the formulae (II), (IIa-1) and (IIa-2), respectively, are distinguished by a high refractive index, which is 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, in particular of the polycarbonate resin, depends on the refractive index of the monomer and on the relative amounts of the monomers in the thermoplastic resin. Generally, a higher refractive index of the monomer contained in the thermoplastic resin will result in a higher 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 a de novo algorithm (ab-initio), for example by using computer software ACD/chem skin 2012 (ADVANCED CHEMISTRY Development, inc.).

In the case of thermoplastic copolymer resins, the refractive index of the thermoplastic resin (specifically, 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. 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. It is clear that a higher 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 the direct measurement, the refractive index n _D of the thermoplastic resin was measured at a wavelength of 589nm according to the protocol JIS-K-7142 using an Abbe refractometer and applying a 0.1mm film of the thermoplastic resin. 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. In this regard, 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 of column 48 of U.S. Pat. No. 3, 9,360,593, and the refractive index n _D of the copolycarbonate was measured at a wavelength of 589nm using an Abbe refractometer at a film of 0.1mm using a thermoplastic resin according to the protocol JIS-K-7142. The refractive index of the homopolycarbonate of each monomer can be calculated from the thus measured refractive index n _D by applying the fox formula 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) that do not contain color-imparting free radicals, such as some of the free radicals R ¹、R²、R³、R⁴ and Ar ¹, may also provide purity gains of low yellow index y.i. (as determined according to ASTM E313), which may also be important for the preparation of optical resins.

More precisely, the yellow index y.i. (as determined according to ASTM E313) of the compound of formula (I) preferably does not exceed 200, more preferably does not exceed 100, even more preferably does not exceed 50, in particular does not exceed 20 or 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 producing transparent conductive substrates, which can be used for liquid crystal displays, organic EL displays, solar cells, and the like. Furthermore, the thermoplastic resin of the present invention can be used as a structural material for the following optical parts: such as optical discs, liquid crystal panels, optical cards (optical cards), optical sheets, optical fibers, connectors, vapor deposited plastic mirrors, displays, and the like; or as an optical device suitable for the purpose of the functional material.

Accordingly, molded articles (such as optical devices) can be formed using the thermoplastic resins of the present invention. The optical device includes an optical lens and an optical film. Specific examples of optical devices include lenses, films, mirrors, filters, prisms, and the like. Such optical devices may be formed by any manufacturing method, such as 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 because of excellent moldability and high heat resistance. The thermoplastic resin of the present invention, such as a polycarbonate resin, may be used as a mixture with other thermoplastic resins, such as different polycarbonate resins, polyester carbonate resins, polyester resins, and other resins, for molding.

In addition, the thermoplastic resins of the present invention may be mixed with additives to form optical devices. The above-mentioned additives may be used as additives for forming an optical device. 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.

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). For preferred meanings and preferred embodiments of the structural units of the formulae (II) and (V), reference is made to the description above.

The optical devices made of an optical resin comprising a repeating unit of formula (II) and optionally a repeating unit of formula (V) as defined herein are typically optical molded objects such as optical lenses, e.g. headlight lenses, fresnel lenses, fθ lenses of laser printers, camera lenses, spectacle lenses and projection lenses for rear projection of TV, CD-ROM admission lenses (pick-up lenses), but may also be optical discs, optical elements of image display media, optical films, film substrates, optical filters or prisms, liquid crystal panels, optical cards, optical sheets, optical fibers, optical connectors, deposited plastic mirrors and the like. Particularly preferred are optical lenses and optical films. The optical resin comprising the repeating unit of formula (II) and optionally the repeating unit of formula (V) is also useful for producing transparent conductive substrates, which can be used in optical devices suitable as structural elements 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 degree of birefringence, and has high moisture resistance and heat resistance. Accordingly, the optical lens can be used in the field where a high-cost glass lens having a high refractive index is conventionally used, such as in telescopes, binoculars, TV projectors, and the like. It is preferable that the optical lens is used in the form of an aspherical lens. Only one aspherical lens may make the spherical aberration substantially zero. Therefore, it is unnecessary to use a plurality of spherical lenses to eliminate spherical aberration. Thereby reducing the weight and manufacturing cost of the device including spherical aberration. Aspherical lenses are particularly used as camera lenses for various types of optical lenses. The present invention readily provides an aspherical lens having a high refractive index and a low level of birefringence, which is 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 of the repeating unit of formula (II) and optionally the repeating unit of formula (V) as defined herein.

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

In order to manufacture the optical lens of the present invention by injection molding, it is preferable that the lens should be 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 according to the requirements. Since the spherical aberration can be substantially canceled out by a single aspherical lens, the spherical aberration does not need to be canceled out by a combination of spherical lenses, thereby making it possible to reduce weight and manufacturing cost. Therefore, among the optical lenses, an aspherical lens is particularly used as a camera lens.

Since the resin having the repeating unit of formula (II) and optionally the repeating unit of formula (V) as defined herein has high moldability, it is particularly useful as a material for thin and small-sized and optical lenses having a complicated shape. As for the lens size, the thickness of the intermediate 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. It is preferably a meniscus lens with a convex mirror on one side and a concave mirror 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 coat layer, as required. The anti-reflection 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 in any method, such as metal molding, cutting, polishing, laser processing, electro-discharge machining, or edging. Preferably metal molding.

The optical film manufactured using the thermoplastic resin according to the present invention has high transparency and heat resistance, and thus is preferably useful for a liquid crystal substrate film, an optical memory card, or the like. In order to avoid incorporation of foreign substances into the optical film as much as possible, no further description is necessary, and molding must be performed in a low-dust environment. The dust environment is preferably 6 grades or less, and more preferably 5 grades or less.

The following examples are intended to be further illustrative of the present invention.

1. Abbreviations:

m.p.: melting point

RT: room temperature

THF: tetrahydrofuran (THF)

TLC: thin film chromatography

2. Preparation of monomers of formula (I)

2.1 Analysis of monomers of formula (I):

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

IR spectra were recorded as ATR FT-IR using a Shimadzu FTIR-8400S spectrometer (number of scans: 45, resolution: 4cm ^-1; diffraction-controlled imaging method: happ-Genzel).

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

The melting Point of the compounds was determined as Bu CHI MELTING Point B-545.

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

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

The yellowness index YI of a compound of formula (I) can be determined analogously 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 photopipe and the transmittance in the range 300 to 800nm was measured with a Shimadzu UV-visible spectroradiometer UV-1900. The solvent itself (e.g., methanol) is used as a reference. The yellowness index can be calculated from spectra using the software "RCA-software UV2DAT" in accordance with ASTM E308 (standard implementation of calculating object colors using the CIE system) and ASTM E313 (standard implementation 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), having x=c (CH ₃)₂,R¹＝R²＝R³＝R⁴ =phenyl, and Z ¹＝Z² =2-hydroxyethyl; compound 33 of table a)

Phenylboronic acid (102.42 g; 84mmol; 4.2 eq.) and tris (o-tolyl) phosphine (243.5 mg;0.8 mmol) and anisole (800 mL) were added 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%). K ₃PO₄ (178.3 g) dissolved in water (396 g) was added to this mixture. The mixture was stirred at 60 to 70 ℃ until two clear phases formed and purged with nitrogen. Pd (OCOCH ₃)₂ (45 mg;0.2 mmol) was added to this 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 and then washed with aqueous NaOH (10 wt%), aqueous HCl (2M) and brineDX 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 RT and stirred overnight. The crystals formed were collected by filtration to yield 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 provide the title compound as a white solid with a chemical purity of >99% and a yellowness index (APHA 5) of 1.3.

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 (compound of formula (Ia-1), having x=c (CH ₃)₂,R¹＝R²＝R³＝R⁴ =naphthalen-1-yl, and Z ¹＝Z² =2-hydroxyethyl; compound 34 of table a)

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Naphthalene-1-ylboronic acid (114.4 g;665mmol;5 eq.) and tris (o-tolyl) phosphane (1.62 g;5.32 mmol) were added 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%). Anisole (800 mL) and 148.2g K ₃PO₄ (148.2 g) dissolved in water (331 g) were added to this mixture. The mixture was stirred at 60 to 70 ℃ until two clear phases formed and purged with nitrogen. Pd (OCOCH ₃)₂ (299 mg;1.33 mmol) was added to this 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 and then washed with aqueous NaOH (10 wt%), aqueous HCl (2M) and brineDX 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 RT and stirred overnight. The crystals formed were collected by filtration to yield the crude title compound (86.3 g;83% yield) as an off-white solid 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 (compound of formula (Ia-1), having x=c (CH ₃)₂,R¹＝R²＝R³＝R⁴ =naphthalen-2-yl, and Z ¹＝Z² =2-hydroxyethyl; compound 35 of table a)

Naphthalene-2-ylboronic acid (138 g;800mmol;6 eq.) and tris (o-tolyl) phosphine (1.62 g;5.32 mmol) were added 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%). Anisole (800 mL) and K ₃PO₄ (178 g) dissolved in water (396 g) were added to this mixture. The mixture was stirred at 60 to 70 ℃ until two clear phases formed and purged with nitrogen. Pd (OCOCH ₃)₂ (299 mg;1.33 mmol) was added to this 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 and 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 RT and stirred overnight. The crystals formed were collected by filtration to yield the crude title compound as an off-white solid which was crystallized from a toluene/anisole mixture to provide 92.3g of the title compound as an off-white solid with 92% chemical purity. 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), having x=c (CH ₃)₂,R¹＝R²＝R³＝R⁴ =phenanthren-9-yl, and Z ¹＝Z² =hydrogen; compound 4 of table a)

Phenanthrene-9-ylboronic acid (133.3 g;600mmol;6 eq.) and tris (o-tolyl) phosphane (1.22 g;4 mmol) were added 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%). Anisole (600 mL) and K ₃PO₄ (133 g) dissolved in water (198 g) were added to this mixture. The mixture was stirred at 60 to 70 ℃ until two clear phases formed and purged with nitrogen. Pd (OCOCH ₃)₂ (225 mg;1 mmol) was added to this mixture under argon and the mixture was stirred under reflux until TLC showed complete conversion, then the reaction mixture was cooled to 70 ℃, the organic layer was separated at this temperature and 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 solvent was removed under reduced pressure. The crude title compound thus obtained as an off-white solid was dissolved in a toluene/methanol mixture (400 g) at elevated temperature. The mixture was cooled to RT and stirred overnight. The crystals formed were collected by filtration to yield the title compound (90.9 g) as an off-white solid with a chemical purity of 95% which was 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), having x=c (CH ₃)₂,R¹＝R²＝R³＝R⁴ =phenanthren-9-yl; and Z ¹＝Z² =2-hydroxyethyl; compound 36 of table a)

Ethylene carbonate (77.5 g; 660 mmol;8 eq), anisole (315 g) and K ₂CO₃ as a solid (12.2 g) were added 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%). The mixture was stirred at 135 ℃ until TLC showed complete conversion. The reaction mixture was then cooled to 70 to 75 ℃, the organic layer was separated at this temperature, and then washed with aqueous NaOH (10 wt%) and brine. The organic layer is treated with active carbonDX Ultra, cabot corp.) and the mixture is stirred 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 as an off-white solid was dissolved in methyl ethyl ketone (250 g) under reflux. The mixture was then cooled to RT and stirred overnight. The crystals formed were collected by filtration to yield the title compound as a white solid (90.5 g;79% yield) with a chemical purity of >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) having x=c (CH ₃)₂,R¹＝R²＝R³＝R⁴ =dibenzo [ b, d ] thiophen-4-yl, and Z ¹＝Z² =2-hydroxyethyl; compound 51 of table a)

(Dibenzo [ b, d ] thiophen-4-yl) boronic acid (125.4 g;550mmol;5 eq.) and tris (o-tolyl) phosphane (4.02 g;13.2 mmol) were added 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%). Anisole (660 mL) and K ₃PO₄ (122.6 g) dissolved in water (285 g) were added to this mixture. The mixture was stirred at 60 to 70 ℃ until two clear phases formed and purged with nitrogen. Pd (OCOCH ₃)₂ (741 mg;3.3 mmol) was added to this 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 RT 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℃followed by addition of activated charcoal @DX Ultra, cabot corp.) and the mixture was 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 afford 87g of the title compound as a white powder. Repeating the process again with activated carbon (/ >)DX Ultra, cabot corp.) and recrystallised from THF/toluene mixtures to provide the title compound as a white crystalline powder with 87% yield and >98% chemical purity.

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 (compound of formula (Ia-1), having x=so ₂,R¹＝R²＝R³＝R⁴ =naphthalen-1-yl, and Z ¹＝Z² =2-hydroxyethyl; compound 55 of table a)

Naphthalene-1-ylboronic acid (219.37 g;1,25mol;5eq.; purity=98%) and tris (o-tolyl) phosphane (1.52 g;5.0 mmol) were added to 2- [4- [4- (2-hydroxyethoxy) -3, 5-dibromophenyl ] sulfonyl-2, 6-dibromophenoxy ] ethanol (170.3 g;250mmol; purity=96%). Anisole (750 mL) and 276g K ₃PO₄ dissolved in 613g water were added to this mixture. The mixture was stirred at 60 to 70 ℃ until two clear phases formed and purged with nitrogen. Pd (OCOCH ₃)₂ (281mg; 1.25 mmol) was added to this 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 for 2.5 hours. The mixture was then filtered through celite and the solution was concentrated under reduced pressure. The mixture was cooled to RT and stirred overnight. The crystals formed were collected by filtration to yield the crude product (149.33 g; 65%) as a white solid with a chemical purity of 92.14%. The crude material can be recrystallized from a 1.6L toluene/MeOH (1:1 (v/v)) mixture to yield 79.6g of the title compound as a white solid with a chemical purity of about 97%.

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 ] thiol-2, 6-bis (naphthalen-1-yl) phenoxy ] ethanol (a compound of formula (Ia-1), having x=s, R ¹＝R²＝R³＝R⁴ =naphthalen-1-yl, and Z ¹＝Z² =2-hydroxyethyl; compound 76 of table a)

A solution of TiCl ₄ (47.5 g;250 mmol) in 2-methyl-THF (1L) was slowly added to a cooled (-18 ℃) solution of lithium aluminum hydride (19 g;500 mmol) in THF (600 mL) and the mixture stirred at 0deg.C under inert gas for 30min. 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 was slowly added in portions to this mixture at 0 ℃. After the addition was completed, the mixture was stirred at 0 ℃ under inert gas for another 30min. The mixture was slowly warmed to RT and stirred at RT for 1 hour. TLC (eluent: 2:1 cyclohexane: ethyl acetate) showed complete conversion. A mixture of water (19 g) and THF (30 mL) was slowly added to this mixture to eliminate excess lithium aluminum hydride. The solvent was removed under reduced pressure and the resulting residue was purified by column chromatography (silica gel; 5:1 cyclohexane: ethyl acetate) to yield 24.6g of the title compound as a white solid with 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 (compound of formula (Ia-1), having x=so ₂,R¹＝R²＝R³＝R⁴ =phenanthren-9-yl, and Z ¹＝Z² =2-hydroxyethyl; compound 57 of table a)

Phenanthrene-9-ylboronic acid (246.13 g;1,0863mol;5eq.; purity=98%) and tris (o-tolyl) phosphane (1.33 g;4.35 mmol) were added to 2- [4- [4- (2-hydroxyethoxy) -3, 5-dibromophenyl ] sulfonyl-2, 6-dibromophenoxy ] ethanol (148.0 g;217,26mmol; purity=96%). Anisole (700 g) and 240g of K ₃PO₄ dissolved in 532g of water were added to this mixture. The mixture was stirred at 60 to 70 ℃ until two clear phases formed and purged with nitrogen. Pd (OCOCH ₃)₂ (244 mg;1.086 mmol) was added to this mixture under argon and the mixture stirred under reflux for 9 hours because TLC (eluent: e.g. 1:2 cyclohexane: ethyl acetate) then showed complete reaction, another portion of phenanthrene-9-yl boronic acid (24.613 g;108.63 mmol) and 24g of K ₃PO₄ dissolved in 53.2g of water were added, along with Pd catalyst [ Pd (OCOCH 3) ₂ (24.4 mg;0.1086 mmol) and tris (o-tolyl) phosphane (133 mg;0.435 mmol) ] the reaction mixture was stirred under reflux for another 90 minutes until TLC (eluent: e.g. 1:2 cyclohexane: ethyl acetate) showed almost complete conversion.

The crude product is filtered off, washed with anisole and 2-methyl-tetrahydrofuran and dried at 60 ℃. The crude product was dissolved in 3L of THF and 10g of activated carbon (Norit DX Ultra) were added. The mixture was stirred at 40 ℃ for 2 hours, and after filtration of the activated carbon through 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 of > 94%. The product was recrystallized from toluene to provide the title compound with a chemical purity of > 97%.

M.p. (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.

Calculated n _D: 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) having x=so ₂,R¹＝R²＝R³＝R⁴ =dibenzo [ b, d ] thiophen-4-yl, and Z ¹＝Z² =2-hydroxyethyl; compound 72 of table a

Dibenzo [ b, d ] thiophen-4-ylboronic acid (244.37 g;1,05mol;5eq.; purity=98%) and tris (o-tolyl) phosphane (1.28 g;4.2 mmol) were added to 2- [4- [4- (2-hydroxyethoxy) -3, 5-dibromophenyl ] sulfonyl-2, 6-dibromophenoxy ] ethanol (143.05 g;210mmol; purity=96%). Anisole (700 g) and 232g of K ₃PO₄ dissolved in 515g of water were added to this mixture. The mixture was stirred at 60 to 70 ℃ until two clear phases formed and purged with nitrogen. Pd (OCOCH ₃)₂ (236 mg;1.05 mmol) was added to this mixture under argon and the mixture was stirred under reflux for 3 hours until TLC (eluent: e.g. 1:2 cyclohexane: ethyl acetate) showed complete conversion (note: if according to TLC the reaction was still incomplete after 9 hours under reflux, another portion of dibenzo [ b, d ] thiophen-4-ylboronic acid (24.44 g;105 mmol) and 23.2gK ₃PO₄ dissolved in 51.5g of water should be added, along with Pd catalyst [ Pd (OCOCOCH ₃)₂ (23.6 mg;0.105 mmol) and tris (o-tolyl) phosphane (128 mg;0.42 mmol) ] and the reaction mixture should be 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 the aqueous phase was extracted with 250mL of 2-methyltetrahydrofuran. 10% aqueous NaOH (375 mL) was added to the combined organic layers at 70 ℃. Because the product crystallized, the suspension was cooled to RT and the crude product was filtered off, then washed with water and THF and dried at 60 ℃ to afford 207.5g of crude product.

The solid obtained was dissolved in 3L of anisole under reflux and then cooled to 120 ℃. 10g of activated carbon (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 RT and THF (500 mL) was added. The crystals formed were collected by filtration and dried at 60 ℃ to give the crude title compound (174.4 g; 77.8%) as a white solid. 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 of >95% (by NMR). (remark: if anisole/THF mixtures are used, THF solvate of the title compound is obtained).

M.p. (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.

Calculated n _D: 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), having x=so ₂,R¹＝R²＝R³＝R⁴ =thianthrene-1-yl, and Z ¹＝Z² =2-hydroxyethyl; compound 73 of table a)

Thianthrene-1-yl boronic acid (278.72 g;1.05mol;5eq.; purity=98%) and tris (o-tolyl) phosphane (1.28 g;4.2 mmol) were added to 2- [4- [4- (2-hydroxyethoxy) -3, 5-dibromophenyl ] sulfonyl-2, 6-dibromophenoxy ] ethanol (143.05 g;210mmol; purity=96%). Anisole (700 g) and 232g of K ₃PO₄ dissolved in 515g of water were added to this mixture. The mixture was stirred at 60 to 70 ℃ until two clear phases formed and purged with nitrogen. Pd (OCOCH ₃)₂ (236 mg;1.05 mmol) was added to this mixture under argon and the mixture was stirred under reflux until TLC (eluent: e.g. 1:2 cyclohexane: ethyl acetate) showed complete conversion (note: if according to TLC the reaction was still incomplete after 9 hours at reflux, another part of thianthrene-1-yl boronic acid (27.87 g;105 mmol) and 23.2g of K ₃PO₄ dissolved in 51.5g of water should be added, as well as Pd catalyst [ Pd (OCOCH ₃)₂ (23.6 mg;0.105 mmol) and tris (o-tolyl) phosphane (128 mg;0.42 mmol) ] the reaction mixture should then be 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. 100g of Na ₂SO₄ and 10g of activated carbon (Norit DXUltra) were added to the organic layer, 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 to 880mL of toluene/methanol (1/1 v/v) mixture at 55 ℃ and then the clear solution was cooled to RT and stirred overnight. The crystals formed were collected by filtration and dried at 60℃to yield the crude title compound (210.6 g; 83.9%) as a white solid with a chemical purity of 97.61%.

The product may be further purified by further 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.

Calculated n _D: 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) having x=so ₂,R¹＝R²＝R³＝R⁴ =naphthalen-2-yl, and Z ¹＝Z² =2-hydroxyethyl; compound 56 of table a)

Naphthalene-2-ylboronic acid (219.37 g;1,25mol;5eq.; purity=98%) and tris (o-tolyl) phosphane (1.52 g;5.0 mmol) were added to 2,2' - { sulfonylbis [ (2, 6-dibromo-4, 1-phenylene) oxy ] } bis (ethan-1-ol) (170.3 g;250mmol; purity=96%). Anisole (750 mL) and 276g of K ₃PO₄ dissolved in 613g of water were added to this mixture. The mixture was stirred at 60 to 70 ℃ until two clear phases formed and purged with argon. Pd (OCOCH ₃)₂ (281mg; 1.25 mmol) was added to this 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 yield the crude title compound (149.33 g; 65%) as a white solid with 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,C_Ar-H),8.10-7.42(m,28H,C_Ar-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' - (propan-2, 2-diyl) bis [2, 6-bis (thianthrene-1-yl) phenol ] (compound of formula (Ia-1) having x=c (CH ₃)₂,R¹＝R²＝R³＝R⁴ =thianthrene-1-yl, and Z ¹＝Z² =hydrogen; compound 7 of table a)

Thianthrene-1-yl boronic acid (166 g;625mmol;5eq.; purity; 98%) and tris (o-tolyl) phosphane (1.52 g;5.0 mmol) were added to 4,4' - (propane-2, 2-diyl) bis (2, 6-dibromophenol) (70.1 g;125mmol; purity: 97%). Anisole (500 g) and 11.4g of K ₃PO₄ dissolved in 248g of water were added to this mixture. The mixture was stirred at 60 to 70 ℃ until two clear phases formed and purged with argon. Pd (OCOCH ₃)₂ (281mg; 1.25 mmol) was added to this mixture under argon and the mixture was stirred under reflux until TLC (eluent: e.g. 3:1 cyclohexane/ethyl acetate) 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. 6.75g of activated carbon (Norit DX Ultra) and 13.5g of Na ₂SO₄ were added to the organic layer 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) having x=c (CH ₃)₂,R¹＝R²＝R³＝R⁴ =thianthrene-1-yl, and Z ¹＝Z² =2-hydroxyethyl; compound 52 of table a)

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

The mixture was cooled to 70 to 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 and after filtration through celite the solvent was completely removed under reduced pressure. The crude product was purified by column chromatography to obtain 70.8g of the title compound as a white solid with a chemical purity of about 97 to 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

A solution of 60g of [1,1 '-biphenyl ] -4,4' -diol in 750g of methanol was slowly added to a solution of 82.7mL (about 258 g) of bromine in 750g of methanol at 0 ℃. The reaction mixture was stirred at 0 ℃ for an additional 1 hour and then at ambient temperature overnight. The precipitated product was filtered off, subsequently washed with cold methanol, then with ascorbic acid solution (20 wt%) and finally with water twice. 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) ] di (ethan-1-ol)

172.4G of K ₂CO₃ was added to a solution of 161.3g of 3,3', 5' -tetrabromo [1,1 '-biphenyl ] -4,4' -diol obtained in example 14a (homogenized at 60 ℃), in 483g (ca. 512 mL) of DMF. The mixture was stirred at 60 ℃ for an additional 10 to 20 minutes and 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 to form a white precipitate. After slow neutralization with concentrated HCl, the crude product was filtered off and then washed with water (3×500 mL) and ethanol (500 mL). The crude product was dissolved in 1450g of THF under reflux, 4.0g of activated carbon (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 THF/toluene mixtures, the crystals obtained were filtered off and washed with 500g of toluene to provide 157.3g (about 85.5% yield) of the title compound with >97.7% chemical purity.

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) having x=single bond, R ¹＝R²＝R³＝R⁴ =naphthalen-1-yl, and Z ¹＝Z² =2-hydroxyethyl; compound 244 of table a)

Naphthalene-1-ylboronic acid (110 g;626,8mmol;5.06eq.; purity=98%) and anisole (390 mL) were added 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) obtained in example 14 b. 138g of K ₃PO₄ dissolved in 306g of water are added to this mixture. The mixture was stirred at 60 to 70 ℃ until two clear phases were formed and then purged with argon. Tris (o-tolyl) phosphane (1.5 g;4.95 mmol) and Pd (OCOCH ₃)₂ (281mg; 1.25 mmol) in 5mL anisole were added to this mixture under argon and the mixture 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. 10g of activated carbon (Norit DX Ultra) and 100g of Na ₂SO₄ were added to the organic layer 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 via 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) having x=single bond, R ¹＝R²＝R³＝R⁴ =naphthalen-1-yl, and Z ¹＝Z² =2-hydroxyethyl; compound 245 of table a

Naphthalene-2-ylboronic acid (165 g;937.5mmol;7.5eq.; purity=98%) and anisole (440 mL) were added 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). 207g of K ₃PO₄ dissolved in 460g of water were added to this mixture. The mixture was stirred at 60 to 70 ℃ until two clear phases formed and purged with argon. Tris (o-tolyl) phosphane (3.05 g;4.95 mmol) and Pd (OCOCH ₃)₂ (560 mg;2.5 mmol) in 10mL anisole were added to this mixture under argon and the mixture 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. 10g of activated carbon (Norit DX Ultra) and 100g of Na ₂SO₄ were added to the organic layer 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 via 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) having x=single bond, R ¹＝R²＝R³＝R⁴ =phenanthren-9-yl, and Z ¹＝Z² =2-hydroxyethyl; compound 246 of table a)

Phenanthrene-9-ylboronic acid (141.61 g;625mmol;7.5eq.; purity: 98%) and anisole (390 mL) were added to 2,2' - [ (3, 3', 5' -tetrabromo [1,1' -biphenyl ] -4,4' -diyl) bis (oxy) ] bis (ethan-1-ol) (75.2 g;125 mmol). 138g of K ₃PO₄ dissolved in 306g of water are added to this mixture. The mixture was stirred at 60 to 70 ℃ until two clear phases formed and purged with argon. Tris (o-tolyl) phosphane (1.52 g;5.0 mmol) and Pd (OCOCH ₃)₂ (281mg; 1.25 mmol) in 5mL anisole were added to this mixture under argon and the mixture 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. 10g of activated carbon (Norit DX Ultra) and 100g of Na ₂SO₄ were added to the organic layer 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 via column chromatography (eluent: cyclohexane/ethyl acetate) to give the title compound as a white solid with a chemical purity of > 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) having x=single bond, R ¹＝R²＝R³＝R⁴ =dibenzo [ b, d ] thiophen-4-yl, and Z ¹＝Z² =2-hydroxyethyl; compound 248 of table a

Dibenzo [ b, d ] thiophen-4-ylboronic acid (19.1 g;81.37mmol;5eq.; purity = 98%) and anisole (51 mL) were added to 2,2' - [ (3, 3', 5' -tetrabromo [1,1' -biphenyl ] -4,4' -diyl) bis (oxy) ] bis (ethan-1-ol) (10 g;16.3 mmol). To this mixture 18g of K ₃PO₄ dissolved in 40g of water was added. The mixture was stirred at 60 to 70 ℃ until two clear phases formed and purged with argon. Tris (o-tolyl) phosphane (198mg; 0.651 mmol) and Pd (OCOCH ₃)₂ (37 mg;0.163 mmol) in 5mL anisole were added to this 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. 1.0g of activated carbon (Norit DX Ultra) and 10.0g of Na ₂SO₄ were added to the organic layer 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 methyl ethyl ketone and/or purified via column chromatography (eluent: cyclohexane/ethyl acetate) to give the title compound as a white solid with a chemical purity of > 94%.

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) having x=single bond, R ¹＝R²＝R³＝R⁴ =thianthrene-1-yl, and Z ¹＝Z² =2-hydroxyethyl; compound 249 of table a

Thianthrene-1-yl boronic acid (26.5 g;100mmol;5eq.; purity: 98%) and anisole (62 mL) are added to 2,2' - [ (3, 3', 5' -tetrabromo [1,1' -biphenyl ] -4,4' -diyl) bis (oxy) ] bis (ethan-1-ol) (12.04 g;20 mmol). 22.1g of K ₃PO₄ dissolved in 49g of water was added to this mixture. The mixture was stirred at 60 to 70 ℃ until two clear phases formed and purged with argon. Tris (o-tolyl) phosphane (244 mg;0.8 mmol) and Pd (OCOCH ₃)₂ (45 mg;0.2 mmol) in 5mL anisole were added to this mixture under argon and the mixture 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. 1.0g of activated carbon (Norit DX Ultra) and 10.0g of Na ₂SO₄ were added to the organic layer 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 >94% chemical purity.

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

Bromine (107 g,671mmol,5.0 eq.) was added dropwise to a solution of 1,1 '-biphenyl-2, 2' -diol (25.0 g;134 mmol) in methanol (1000 mL) at 0deg.C. The reaction was warmed to room temperature and stirred until TLC (2:1 heptane/ethyl acetate) 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): decomposing 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)

K ₂CO₃ (31.9 g,231mmol,4.0 eq) was added 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) and the mixture was stirred at 50℃for 30min. Ethylene carbonate (50.9 g,578mmol,10 eq.) was added in portions and the reaction was heated to reflux until TLC (cyclohexane/ethyl acetate with about 1% acetic acid (2:1)) 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 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) having x=single bond, R ¹＝R²＝R³＝R⁴ =thianthrene-1-yl, and Z ¹＝Z² =2-hydroxyethyl; compound 12 of table B

A solution of K ₃PO₄ (31.8 g,150mmol,5.2 eq.) in water (70 g) was added to a mixture of anisole (100 g) with 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.) obtained in example 19b and the mixture was heated to 70 ℃. Tris (o-tolyl) phosphane (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 (3:1 cyclohexane/ethyl acetate) 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), followed by brine (100 g), dried over Na ₂SO₄ and the solvent removed under reduced pressure to provide the crude product. Purification by column chromatography (3:1 cyclohexane/ethyl acetate) afforded 21.5g of the title compound as a white solid with >95% chemical purity.

M.p. =196 ℃ to 205 DEG C

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.). The individual monomers in Table C are identified by their accession codes in tables A and B, respectively. In addition, all monomers included in table C have been verified as quantum-stoichiometric, are not or only to a negligible extent absorbed in the visible range, and are therefore essentially colorless.

Table C

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

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

Refractive index (n _D):

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

Refractive index measuring device:

KPR-3000 manufactured by Shimadzu Corporation

Abbe number (v):

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

Refractive index measuring device:

KPR-3000 manufactured by Shimadzu Corporation

V three (nD-1)/(nF-nC)

ND: refractive index at 589nm wavelength

NC: refractive index at 656nm wavelength

NF: refractive index at 486nm wavelength

Glass transition temperature (Tg):

the glass transition temperature was measured in accordance with JIS K7121-1987 by Differential Scanning Calorimetry (DSC) using a heating program of 10℃per minute.

Differential scanning calorimetry apparatus:

X-DSC7000 manufactured by HITACHI HIGH-TECH SCIENCE Corporation

Molecular weight

The weight average molecular weight (Mw) value of the resin was measured according to the Gel Permeation Chromatography (GPC) method and calculated as a polystyrene standard conversion method. 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

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

Eluent: tetrahydrofuran;

Flow rate of eluent: 0.6ml/min;

column temperature: 40 ℃.

The number average molecular weight (Mn) value can be calculated using a method similar to that described above for measuring Mw values. The polystyrene-reduced weight average molecular weight (Mw) and the number average molecular weight (Mn) were calculated using a polystyrene standard curve prepared previously. Specifically, the standard curve was prepared using a polystyrene standard (from Tosoh Corporation, "PStQuick C") having a known molecular weight. Furthermore, a calibration curve was obtained by plotting the elution time and molecular weight value of each peak based on the measurement data of the polystyrene standard and performing a three-dimensional approximation method. The Mw and Mn values are calculated based on the following calculation formula:

Mw＝Σ(Wi_xMi)÷Σ(Wi)

Mn＝Σ(NixMi)÷Σ(Wi)

In the calculation formula, "i" represents the "i" th demarcation point, "Wi" represents the polymer molecular weight (g) at the "i" th demarcation point, "Ni" represents the polymer molecular number at the "i" th demarcation point, and "Mi" represents the molecular mass at the "i" th demarcation point. The molecular mass (M) represents the molecular mass value of polystyrene corresponding to the 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 of compounds having a Mw value of less than 1000 to the total area of all peaks, wherein the peak area is determined according to the GPC analysis described above. Thus, CLWC values were determined using the following formula:

GPC analysis as used in this context is performed in a manner similar to that 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 obtained solution was cast on SUS plate whose surface had been subjected to plating treatment, and then the solvent was evaporated at 25 ℃ to prepare a casting film. Square films 50mm per side with a thickness of 100 μm were cut from the cast film. The film is stretched no more than 1.5 times at a temperature 20 ℃ above the Tg of the resin. Stretching was performed using a stretcher SS-70 manufactured by Shibayama Scientific co. The resulting stretched film was subjected to retardation measurement using ellipsometer M-220 manufactured by JASCO Corporation.

The birefringence value Δn is calculated from the retardation phase difference Re by the following formula:

Δn＝|Re/d|

An: orientation double refractive index

Re: phase difference [ nm ]

D: thickness [ nm ]

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

Δn＝n_x|-n_⊥

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

3.2 Examples for the preparation 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), 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 a diol component with a carbonate-forming monomer such as diphenyl carbonate in a similar manner as is known in the art for preparing polyestercarbonates. Table 1 also lists the n _D values and Tg values of two comparative homopolycarbonates prepared from 9, 9-bis (4- (2-hydroxyethoxy) -phenyl) fluorene and bisphenol A, respectively, as diol components. Accordingly, the homopolycarbonates of examples 20 to 30 each consist of a structural unit of the formula (IIa-1) and a structural unit of the formula (III-1), respectively, whereas the comparative homopolycarbonates consist of structural units derived from the monomers 9, 9-bis (4- (2-hydroxyethoxy) phenyl) fluorene and bisphenol A, respectively, and structural units of the formula (III-1).

The n _D value, v value, tg value, and Δn value of the homopolycarbonates of examples 20 to 30 provided in table 1 were calculated from the respective values of the corresponding copolymers derived from the monomers of examples 1,2, 3, 4, 5, 6, 7, 8, 9, 10, or 13 using the above-mentioned fox equation. The preparation of such copolymers and their physical data are illustrated in examples 31 to 40 below. The n _D value and Tg value of the comparative homopolycarbonate 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; n _D value and Tg value reported in US 9,360,593

3.3 Examples of preparation of copolycarbonates:

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

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 indicated as TPBHBPA below), 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) of aqueous sodium bicarbonate as materials were placed in a 50 liter reactor with stirrer and distillation apparatus.

After the reactor had been flushed with nitrogen, the reaction mixture was heated to 205 ℃ over 1 hour and stirred at 760 torr. After complete dissolution of the reaction mixture, the pressure was reduced to 150 torr over 15 minutes, and then the transesterification reaction was carried out at 205 ℃ and 150 torr for 20 minutes. The reaction mixture was further heated to 240 ℃ at a heating rate of 37.5 ℃/h and maintained at 240 ℃ and 150 torr reaction conditions for 10 minutes. The pressure was then reduced to 120 torr over 10 minutes and maintained at 240 ℃ and 120 torr reaction conditions for 70 minutes. The pressure was then reduced to 100 torr over 10 minutes and maintained at 240 ℃ and 100 torr reaction conditions for 10 minutes. The pressure was further reduced to 1 torr or less in 40 minutes, and the polymerization was carried out at 240 ℃ and 1 torr with stirring for 10 minutes. After the reaction was completed, nitrogen was introduced into the reactor to increase the pressure, and the produced polycarbonate resin was pelletized and removed from the reactor. The characteristics of the obtained polycarbonate resin are summarized in table 2 below.

TABLE 2

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

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

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 indicated 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 2.5X10: 10 ^-2mol/l(2.8×10^-4 mol) of aqueous sodium hydrogen carbonate as material were placed in a 50 liter reactor with stirrer and distillation apparatus.

After the reactor had been flushed with nitrogen, the reaction mixture was heated to 205 ℃ over 1 hour and stirred at 760 torr. After complete dissolution of the reaction mixture, the pressure was reduced to 150 torr over 15 minutes, and then the transesterification reaction was carried out at 205 ℃ and 150 torr for 20 minutes. The reaction mixture was further heated to 240 ℃ at a heating rate of 37.5 ℃/h and maintained at 240 ℃ and 150 torr reaction conditions for 10 minutes. The pressure was then reduced to 120 torr over 10 minutes and maintained at 240 ℃ and 120 torr reaction conditions for 70 minutes. The pressure was then reduced to 100 torr over 10 minutes and maintained at 240 ℃ and 100 torr reaction conditions for 10 minutes. The pressure was further reduced to 1 torr or less in 40 minutes, and the polymerization was carried out at 240 ℃ and 1 torr with stirring for 10 minutes. After the reaction was completed, nitrogen was introduced into the reactor to increase the pressure, and the produced polycarbonate resin was pelletized and removed from the reactor. The characteristics of the obtained polycarbonate resin are summarized in the following table 3.

TABLE 3 Table 3

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

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

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 indicated 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 2.5X10. 10 ^-2mol/l(7.8×10^-4 mol) of aqueous sodium hydrogen carbonate as materials were placed in a 50 liter reactor with stirrer and distillation apparatus.

After the reactor had been flushed with nitrogen, the reaction mixture was heated to 205 ℃ over 1 hour and stirred at 760 torr. After complete dissolution of the reaction mixture, the pressure was reduced to 150 torr over 15 minutes, and then the transesterification reaction was carried out at 205 ℃ and 150 torr for 20 minutes. The reaction mixture was further heated to 240 ℃ at a heating rate of 37.5 ℃/h and maintained at 240 ℃ and 150 torr reaction conditions for 10 minutes. The pressure was then reduced to 120 torr over 10 minutes and maintained at 240 ℃ and 120 torr reaction conditions for 70 minutes. The pressure was then reduced to 100 torr over 10 minutes and maintained at 240 ℃ and 100 torr reaction conditions for 10 minutes. The pressure was further reduced to 1 torr or less in 40 minutes, and the polymerization was carried out at 240 ℃ and 1 torr with stirring for 10 minutes. After the reaction was completed, nitrogen was introduced into the reactor to increase the pressure, and the produced polycarbonate resin was pelletized and removed from the reactor. The characteristics of the obtained polycarbonate resin are summarized in table 4 below.

TABLE 4 Table 4

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

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

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 indicated 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 2.5X10. 10 ^-2mol/l(7.8×10^-4 mol) of aqueous sodium bicarbonate were placed as materials in a 50 liter reactor with stirrer and distillation apparatus.

After the reactor had been flushed with nitrogen, the reaction mixture was heated to 205 ℃ over 1 hour and stirred at 760 torr. After complete dissolution of the reaction mixture, the pressure was reduced to 150 torr over 15 minutes, and then the transesterification reaction was carried out at 205 ℃ and 150 torr for 20 minutes. The reaction mixture was further heated to 240 ℃ at a heating rate of 37.5 ℃/h and maintained at 240 ℃ and 150 torr reaction conditions for 10 minutes. The pressure was then reduced to 120 torr over 10 minutes and maintained at 240 ℃ and 120 torr reaction conditions for 70 minutes. The pressure was then reduced to 100 torr over 10 minutes and maintained at 240 ℃ and 100 torr reaction conditions for 10 minutes. The pressure was further reduced to 1 torr or less in 40 minutes, and the polymerization was carried out at 240 ℃ and 1 torr with stirring for 10 minutes. After the reaction was completed, nitrogen was introduced into the reactor to increase the pressure, and the produced polycarbonate resin was pelletized and removed from the reactor. The characteristics of the obtained polycarbonate resin are summarized in table 5 below.

TABLE 5

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

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

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 (ethyl-1-ol), also indicated below as T4DBTBHBPA, 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 2.5X10 ^-2mol/l(2.8×10^-4 mol) of aqueous solution were placed in a stirrer with a sodium hydrogencarbonate reactor 50.

After the reactor had been flushed with nitrogen, the reaction mixture was heated to 205 ℃ over 1 hour and stirred at 760 torr. After complete dissolution of the reaction mixture, the pressure was reduced to 150 torr over 15 minutes, and then the transesterification reaction was carried out at 205 ℃ and 150 torr for 20 minutes. The reaction mixture was further heated to 240 ℃ at a heating rate of 37.5 ℃/h and maintained at 240 ℃ and 150 torr reaction conditions for 10 minutes. The pressure was then reduced to 120 torr over 10 minutes and maintained at 240 ℃ and 120 torr reaction conditions for 70 minutes. The pressure was then reduced to 100 torr over 10 minutes and maintained at 240 ℃ and 100 torr reaction conditions for 10 minutes. The pressure was further reduced to 1 torr or less in 40 minutes and the polymerization was carried out at 240 ℃ and 1 torr for 10 minutes. After the reaction was completed, nitrogen was introduced into the reactor to increase the pressure, and the produced polycarbonate resin was pelletized and removed from the reactor. The characteristics of the polycarbonate resin obtained are summarized in table 6 below.

TABLE 6

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

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

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 designated hereinafter 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 aqueous sodium bicarbonate solution of 2.5X10: 10 ^-2mol/l(2.8×10^-4 mol) as materials were placed in a 50 liter reactor with a stirrer and a distillation apparatus.

After the reactor had been flushed with nitrogen, the reaction mixture was heated to 205 ℃ over 1 hour and stirred at 760 torr. After complete dissolution of the reaction mixture, the pressure was reduced to 150 torr over 15 minutes, and then the transesterification reaction was carried out at 205 ℃ and 150 torr for 20 minutes. The reaction mixture was further heated to 240 ℃ at a heating rate of 37.5 ℃/h and maintained at 240 ℃ and 150 torr reaction conditions for 10 minutes. The pressure was then reduced to 120 torr over 10 minutes and maintained at 240 ℃ and 120 torr reaction conditions for 70 minutes. The pressure was then reduced to 100 torr over 10 minutes and maintained at 240 ℃ and 100 torr reaction conditions for 10 minutes. The pressure was further reduced to 1 torr or less in 40 minutes and the polymerization was carried out at 240 ℃ and 1 torr for 10 minutes. After the reaction was completed, nitrogen was introduced into the reactor to increase the pressure, and the produced polycarbonate resin was pelletized and removed from the reactor. The characteristics of the obtained polycarbonate resin are summarized in the following table 7.

TABLE 7

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

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

4.50Kg (5.55 mol) of 2- [4- [4- (2-hydroxyethoxy) -3, 5-bis (naphthalen-1-yl) phenyl ] thiol-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 designated hereinafter as T1 NBHTDP), 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 aqueous sodium bicarbonate solution of 2.5X10: 10 ^-2mol/l(2.8×10^-4 mol) were placed in a 50 liter reactor with stirrer and distillation apparatus.

After the reactor had been flushed with nitrogen, the reaction mixture was heated to 205 ℃ over 1 hour and stirred at 760 torr. After complete dissolution of the reaction mixture, the pressure was reduced to 150 torr over 15 minutes, and then the transesterification reaction was carried out at 205 ℃ and 150 torr for 20 minutes. The reaction mixture was further heated to 240 ℃ at a heating rate of 37.5 ℃/h and maintained at 240 ℃ and 150 torr reaction conditions for 10 minutes. The pressure was then reduced to 120 torr over 10 minutes and maintained at 240 ℃ and 120 torr reaction conditions for 70 minutes. The pressure was then reduced to 100 torr over 10 minutes and maintained at 240 ℃ and 100 torr reaction conditions for 10 minutes. The pressure was further reduced to 1 torr or less in 40 minutes and the polymerization was carried out at 240 ℃ and 1 torr for 10 minutes. After the reaction was completed, nitrogen was introduced into the reactor to increase the pressure, and the produced polycarbonate resin was pelletized and removed from the reactor. The characteristics of the polycarbonate resin obtained are summarized in table 8 below.

TABLE 8

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

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

4.24Kg (4.06 mol) 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 denoted as T9PNBHBPS hereinafter), 10.09kg (23.02 mol) of 9, 9-bis [4- (2-hydroxyethoxy) phenyl) fluorene (also denoted as BPEF), 5.92kg (27.62 mol) of diphenyl carbonate (also denoted as DPC) and 11mL of a total amount of 2.5X10. 10 ^-2mol/l(2.7×10^-4mol(10×10^- ⁶ mol of dihydroxy compound (1 mol)) of aqueous sodium bicarbonate as material were placed in a 50 liter reactor with stirrer and distillation apparatus.

After the reactor had been flushed with nitrogen, the reaction mixture was heated to 205 ℃ over 1 hour and stirred at 760 torr. After complete dissolution of the reaction mixture, the pressure was reduced to 150 torr over 15 minutes, and then the transesterification reaction was carried out at 205 ℃ and 150 torr for 20 minutes. The reaction mixture was further heated to 240 ℃ at a heating rate of 37.5 ℃/h and maintained at 240 ℃ and 150 torr reaction conditions for 10 minutes. The pressure was then reduced to 120 torr over 10 minutes and maintained at 240 ℃ and 120 torr reaction conditions for 70 minutes. The pressure was then reduced to 100 torr over 10 minutes and maintained at 240 ℃ and 100 torr reaction conditions for 10 minutes. The pressure was further reduced to 1 torr or less in 40 minutes and the polymerization was carried out at 240 ℃ and 1 torr for 10 minutes. After the reaction was completed, nitrogen was introduced into the reactor to increase the pressure, and the produced polycarbonate resin was pelletized and removed from the reactor. The characteristics of the obtained polycarbonate resin are summarized in the following table 9.

TABLE 9

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

5.06Kg (4.23 mol) of 2- [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 indicated below as T1 TNTBHBPS), 10.51kg (23.96 mol) of 9, 9-bis [4- (2-hydroxyethoxy) phenyl) fluorene (also indicated as BPEF), 6.19kg (28.89 mol) of diphenyl carbonate (also indicated as DPC) and 11mL of 2.5X10 ^-2mol/l(2.8×10^-4mol(10×10^- ⁶ mol of total amount of dihydroxycompound to 1 mol) were placed in a 50 liter reactor with stirrer and distillation apparatus.

After the reactor had been flushed with nitrogen, the reaction mixture was heated to 205 ℃ over 1 hour and stirred at 760 torr. After complete dissolution of the reaction mixture, the pressure was reduced to 150 torr over 15 minutes, and then the transesterification reaction was carried out at 205 ℃ and 150 torr for 20 minutes. The reaction mixture was further heated to 240 ℃ at a heating rate of 37.5 ℃/h and maintained at 240 ℃ and 150 torr reaction conditions for 10 minutes. The pressure was then reduced to 120 torr over 10 minutes and maintained at 240 ℃ and 120 torr reaction conditions for 70 minutes. The pressure was then reduced to 100 torr over 10 minutes and maintained at 240 ℃ and 100 torr reaction conditions for 10 minutes. The pressure was further reduced to 1 torr or less in 40 minutes, and the polymerization was carried out at 240 ℃ and 1 torr with stirring for 10 minutes. After the reaction was completed, nitrogen was introduced into the reactor to increase the pressure, and the produced polycarbonate resin was pelletized and removed from the reactor. The characteristics of the polycarbonate resin obtained are summarized in table 10.

Table 10

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

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

9.91Kg (8.44 mol) of 2,2'- (propan-2, 2-diylbis { [2, 6-bis (thianthin-1-yl) -4, 1-phenylene ] oxy }) bis (ethan-1-ol) (or 2,2' - ((propan-2, 2-diylbis (2, 6-bis (thianthin-1-yl) -4, 1-phenylene)) bis (oxy)) bis (ethan-1-ol), see example 13, also indicated hereinafter as T1 TNTBHBPA), 8.64kg (19.70 mol) of 9, 9-bis [4- (2-hydroxyethoxy) phenyl) fluorene (also indicated as BPEF), 6.21kg (28.99 mol) of diphenyl carbonate (also indicated as DPC) and 11mL of 2.5X10. 10 ^-2mol/l(2.8×10^-4mol(10×10^-6 mol of total amount of dihydroxy compound) were placed in a 50 liter reactor with stirrer and distillation apparatus.

After the reactor had been flushed with nitrogen, the reaction mixture was heated to 205 ℃ over 1 hour and stirred at 760 torr. After complete dissolution of the reaction mixture, the pressure was reduced to 150 torr over 15 minutes, and then the transesterification reaction was carried out at 205 ℃ and 150 torr for 20 minutes. The reaction mixture was further heated to 240 ℃ at a heating rate of 37.5 ℃/h and maintained at 240 ℃ and 150 torr reaction conditions for 10 minutes. The pressure was then reduced to 120 torr over 10 minutes and maintained at 240 ℃ and 120 torr reaction conditions for 70 minutes. The pressure was then reduced to 100 torr over 10 minutes and maintained at 240 ℃ and 100 torr reaction conditions for 10 minutes. The pressure was further reduced to 1 torr or less in 40 minutes, and the polymerization was carried out at 240 ℃ and 1 torr with stirring for 10 minutes. After the reaction was completed, nitrogen was introduced into the reactor to increase the pressure, and the produced polycarbonate resin was pelletized and removed from the reactor. The characteristics of the obtained polycarbonate resin are summarized in table 11.

TABLE 11

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

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

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 the reactor had been flushed with nitrogen, the internal pressure was set to 101.3kPa. The reactor was immersed in an oil bath heated to 200 ℃ to initiate the transesterification reaction. Stirring of the reaction mixture was started 5 minutes after the start of the reaction. After 20 minutes, the pressure was reduced from 101.3kPa to 26.66kPa during 10 minutes, and the reaction mixture was heated to 210 ℃. The reaction mixture was further heated to 220 ℃ within 60 minutes after the start of the reaction. At 80 minutes from the start of the reaction, the pressure was reduced to 20.00kPa during 10 minutes, and then the reaction mixture was heated to 240 ℃ while the pressure was reduced to 0.1kPa or less. Then maintained at 240℃and 0.1kPa or less for 30 minutes. Nitrogen was then introduced to return the pressure to 101.3kPa to obtain the desired polycarbonate resin. The characteristics of the resins obtained are summarized in table 12.

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

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 the reactor had been flushed with nitrogen, the internal pressure was set to 101.3kPa. The reactor was immersed in an oil bath heated to 200 ℃ to initiate the transesterification reaction. Stirring of the reaction mixture was started 5 minutes after the start of the reaction. After 20 minutes, the pressure was reduced from 101.3kPa to 26.66kPa during 10 minutes, and the reaction mixture was heated to 210℃during this time. The reaction mixture was further heated to 220 ℃ within 60 minutes after the start of the reaction. At 80 minutes from the start of the reaction, the pressure was reduced to 20.00kPa during 10 minutes, and then the reaction mixture was heated to 240 ℃ while the pressure was reduced to 0.1kPa or less. Then maintained at 240℃and 0.1kPa or less for 30 minutes. The pressure was then returned to 101.3kPa by introducing nitrogen to obtain the desired polycarbonate resin. The characteristics of the resins obtained are summarized in table 12.

Comparative example: copolycarbonates prepared from BNE and BPEF

The copolycarbonate resin of this comparative example was prepared in a manner similar to that 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 characteristics of the resins obtained are summarized in table 12.

Table 12

* CLWC (low molecular weight compound content) values are specified below

The low molecular weight compound content (CLWC) listed in table 12 was calculated using the procedure detailed above, based on GPC data corrected with polystyrene standards. For example, the area of each peak obtained from the GPC diagram shown in fig. 3 was calculated using the above formula with CLWC values of the resin of example 41 reported in table 12. The relevant peak data are summarized in tables 13 and 13-2 below. In particular, the sum of peak areas for compounds with Mw values below 1000 was calculated (66697+23135+12863= 102695) and was related to the total area of all peaks (6318321). Accordingly, the content of the low molecular weight compound in the resin of example 41 was calculated to be 1.6% (102695/6318321X 100).

TABLE 13 peaks of GPC chart for resin of example 41

Birefringence measurement:

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

Fig. 2 is an enlarged view of a 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), and "BPA-PC" represents the homopolycarbonate prepared from bisphenol A (BPA) as the diol monomer (compare the last accession code of Table 1).

It was confirmed from fig. 1 that TPBHBPA, T2NBHBPA, and T9PNBHBPA provided polycarbonates with very low absolute values of positive or negative birefringence. Such features are not found in known 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, -CH ₂-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 ¹ and R ² are independently selected from: mono-or polycyclic aryl groups having from 6 to 26 carbon atoms as ring members and mono-or polycyclic heteroaryl groups having a total of from 5 to 26 atoms as ring members, wherein 1, 2, 3 or 4 of such ring member atoms of the heteroaryl group are selected from nitrogen, sulfur and oxygen and the remaining atoms of such ring member atoms of the heteroaryl group are carbon atoms, wherein the mono-or polycyclic aryl groups and the mono-or polycyclic heteroaryl groups are unsubstituted or contain 1, 2, 3 or 4 free radicals R ^Ar;

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: mono-or polycyclic aryl groups having 6 to 26 carbon atoms as ring members and mono-or polycyclic heteroaryl groups having a total of 5 to 26 atoms as ring members, wherein 1, 2, 3 or 4 of such ring member atoms of the heteroaryl group are selected from nitrogen, sulfur and oxygen, and the remaining atoms of such atoms of the heteroaryl group are carbon atoms,

Ar ² is selected from: phenylene, naphthylene, and biphenylene;

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', where if more than one R ^Ar are present on the same (hetero) aryl group, they may be the same OR different;

N is 0, 1 or 2;

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

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

3. The compound of 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 are specifically selected from: single bond, O, CH ₂、C(CH₃)₂、CH(CH₃), S, and SO ₂.

4. The compound of 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, particularly selected 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. The compound of 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 group (chrysenyl), a picene group, a triphenylene group, a benzo [ b ] furanyl group, a dibenzo [ b, d ] furanyl group, a naphtho [1,2-b ] furanyl group, a naphtho [2,3-b ] furanyl group, a naphtho [2,1-b ] furanyl group, a benzo [ b ] naphtho [1,2-d ] furanyl group, a benzo [ b ] naphtho [2,3-d ] furanyl group, a benzo [ b ] naphtho [2,1-d ] furanyl group, a benzo [1,2-b:4,3-b '] difuranyl, benzo [1,2-b:6,5-b' ] difuranyl, benzo [1,2-b:5,4-b '] difuranyl, benzo [1,2-b:4,5-b' ] difuranyl, tribenzo [ b, d, f ] oxazepine (oxepinyl), 2H-naphtho [1,8-d, e ] [1,3] dioxazinyl (dioxinyl), dinaphtho [2,3-b:2',3' -d ] furanyl, oxaanthracyl (oxanthrenyl), benzo [ a ] oxaanthracyl, benzo [ b ] oxaanthracenyl, benzo [ b ] thienyl, dibenzo [ b, d ] thienyl, naphtho [1,2-b ] thienyl, naphtho [2,3-b ] thienyl, naphtho [2,1-b ] thienyl, benzo [ b ] naphtho [2,3-d ] thienyl, benzo [2,3-b ] thienyl, benzo [2, 2-b ] benzothienyl, benzo [1,2-b ] dibenzo [2,3-b ] thienyl, benzo [2, 2-b ] thienyl, 5-b ] dibenzo [1, 4-b ] thienyl 9H-thioxoanthracenyl (thioxanthenyl), 6H-dibenzo [ b, d ] thiopyranyl, 1, 4-benzodithiocyclohexadienyl (benzodithiinyl), naphtho [1,2-b ] [1,4] dithiocyclohexadienyl, naphtho [2,3-b ] [1,4] dithiocyclohexadienyl, thiaanthracyl, benzo [ a ] thiaanthracyl, benzo [ b ] thiaanthracyl, dibenzo [ a, c ] thiaanthracyl, dibenzo [ a, H ] thiaanthracyl, dibenzo [ a, i ] thiaanthracyl, dibenzo [ a, j ] thiaanthracyl, dibenzo [ b, i ] thiaanthracyl, 2H-naphtho [1,8-b, c ] thienyl, dibenzo [ b, d ] thiazerenyl (thiepinyl), dibenzo [ b, f ] thiazeyl, 5H-phenanthro [4,5-b, c, d ] thianthrenyl, benzo [ a, i ] thianthrenyl, 2, c ] thianthrenyl; 4,5-b ', c' ] dithiophene, 2, 6-dihydronaphtho [1,8-b, c:5,4-b ', c' ] dithiophene, tribenzo [ a, c, i ] thianthrene, benzo [ b ] naphtho [1,8-e, f ] [1,4] dithio-zhuo, dinaphtho [2,3-b:2',3' -d ] thiophene, 5H-phenanthro [1,10-b, c ] thiophene, 7H-phenanthro [1,10-c, b ] thiophene, dibenzo [ d, d '] benzo [1,2-b:4,5-b' ] dithiophene and dibenzo [ d, d '] benzo [1,2-b:5,4-b' ] dithiophene.

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

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

8. The compound of any one of the preceding claims, wherein R ³ and R ⁴ are selected from: mono-or polycyclic aryl groups having 6 to 26 carbon atoms as ring atoms and mono-or polycyclic heteroaryl groups having a total of 5 to 26 atoms as ring members, wherein 1,2, 3 or 4 of such ring member atoms of the heteroaryl group are selected from nitrogen, sulfur and oxygen, and the remaining atoms of such ring member atoms of the heteroaryl group are carbon atoms,

Wherein the mono-or polycyclic aryl and the mono-or polycyclic heteroaryl are unsubstituted or contain 1, 2,3 or 4 radicals R ^Ar.

9. The compound of claim 8, wherein R ³ and R ⁴ 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 '] difuranyl, benzo [1,2-b:6,5-b' ] difuranyl, benzo [1,2-b ] difuranyl, tribenzo [ b, d, f ] oxazepine, 2H-naphtho [1,8-d, e ] [1,3] dioxazinyl, dinaphtho [2,3-b ] 2',3' -d ] furanyl, oxaanthracenyl, benzo [ a ] oxazinyl, benzo [ b ] oxaanthracyl, benzo [ b ] thienyl, dibenzo [ b, d ] thienyl, naphtho [1,2-b ] thienyl, naphtho [2,3-b ] thienyl, naphtho [2,1-b ] thienyl, benzo [ b ] naphtho [1,2-d ] thienyl, benzo [ b ] naphtho [2,3-b ] thienyl, benzo [2,3-d ] thienyl, benzo [1,2-b ] thienyl, benzo [1, 3-b ] thienyl, benzo [2,3-b ] thienyl, benzo [ b ] thienyl, 1, 3-b ] dibenzo [2,3-b ] thienyl, 5-b ] dibenzo [1,2-b ] thienyl, d ] thiopyranyl, 1, 4-benzodithiodienyl, naphtho [1,2-b ] [1,4] dithiohexenyl, naphtho [2,3-b ] [1,4] dithiohexenyl, 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 ] thiazenyl, dibenzo [ b, f ] thiazenyl, 5H-phenanthro [4,5-b, c, d ] thianthrenyl, tribenzo [ b, d, f ] thiazenyl, 2, 5-dihydronaphtho [1,8-b, c; 4,5-b ', c' ] dithiophene, 2, 6-dihydronaphtho [1,8-b, c:5,4-b ', c' ] dithiophene, tribenzo [ a, c, i ] thianthrene, benzo [ b ] naphtho [1,8-e, f ] [1,4] dithio-zhuo, dinaphtho [2,3-b:2',3' -d ] thiophene, 5H-phenanthro [1,10-b, c ] thiophene, 7H-phenanthro [1,10-c, b ] thiophene, dibenzo [ d, d '] benzo [1,2-b:4,5-b' ] dithiophene and dibenzo [ d, d '] benzo [1,2-b:5,4-b' ] dithiophene.

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

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

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

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

Table A'

/>

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

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

Table B

/>

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 each derived from Z ¹ OR Z ² in formula (I), if Z ¹ OR Z ² is hydrogen, the hydrogen is replaced by a single bond, OR if Z ¹ OR Z ² is not hydrogen, the-OH OR-OR ^x group in Z ¹ OR Z ² is replaced by an oxygen-containing (-O-) unit,

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 of claim 17, wherein formula (IIa) is represented by formula (IIa-1), wherein Z ^a is defined as Z ^1a and Z ^2a in claim 16:

19. The thermoplastic resin of claim 17, wherein formula (IIa) is represented by formula (IIa-2), wherein Za is as defined in Z ¹ a and Z ² a in claim 16:

20. The thermoplastic resin of any one of claims 16-19, wherein the structural unit of formula (II), wherein Z ¹ and Z ² are selected from hydrogen, -Alk-OH, and-CH ₂-Ar²-CH₂ -OH, is attached 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 claim 16 to 20, which is selected from the group consisting of copolycarbonate resins, copolyestercarbonate resins and copolyester resins, wherein the thermoplastic resin comprises structural units of the formula (V) in addition to structural units represented by the 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 radical containing at least 2 benzene rings, wherein the benzene rings may be a linked and/or directly fused to each other and/or fused in a non-benzene carbocyclic ring, wherein a ¹ is unsubstituted or substituted with 1, 2 or 3 radicals R ^aa selected from the group consisting of: halogen, C ₁-C₆ -alkyl, C ₅-C₆ -cycloalkyl and phenyl;

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 are 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 is also provided with

* Represents a point of attachment to a benzene ring;

Ar is selected from: mono-or polycyclic aryl groups having from 6 to 26 carbon atoms as ring atoms and mono-or polycyclic heteroaryl groups having a total of from 5 to 26 atoms as ring members, wherein 1, 2,3 or 4 of such ring member atoms of the heteroaryl group are selected from nitrogen, sulfur and oxygen and the remaining atoms of such ring member atoms of the heteroaryl group are carbon atoms, wherein Ar is unsubstituted or substituted with 1, 2 or 3 free radicals R ^ab 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 the structural units of formula (II) is 1 to 70mol-%, based on the total molar amount of the structural units of formula (II) and (V), and wherein the molar ratio of the structural units of formula (V) is 30 to 99mol-%, based on the total molar amount of the structural units of formula (II) and (V).

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

25. The thermoplastic resin of any one of claims 16 to 24, having an Abbe number (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 determined by gel permeation chromatography relative to polystyrene standards.

28. The thermoplastic resin of any one of claims 16-27, comprising a low molecular weight compound having a molecular weight (Mw) of less than 1000, wherein the low molecular weight compound content (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 the CLWC is represented by the following formula:

29. An optical device made of the thermoplastic resin as defined in 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.