WO2025248024A1 - Composés de binaphtyle utilisés comme additifs dans des compositions de résine - Google Patents

Composés de binaphtyle utilisés comme additifs dans des compositions de résine

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Publication number
WO2025248024A1
WO2025248024A1 PCT/EP2025/064873 EP2025064873W WO2025248024A1 WO 2025248024 A1 WO2025248024 A1 WO 2025248024A1 EP 2025064873 W EP2025064873 W EP 2025064873W WO 2025248024 A1 WO2025248024 A1 WO 2025248024A1
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Prior art keywords
group
formula
phenyl
atoms
hetaryl
Prior art date
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Pending
Application number
PCT/EP2025/064873
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English (en)
Inventor
Karl Reuter
Vasyl Andrushko
Philipp KOSCHKER
Florian Stolz
Mark Kantor
Noriyuki Kato
Katsushi Nishimori
Atsushi MOTEGI
Kentaro Ishihara
Takafumi Watanabe
Kazutaka Takamatsu
Kaito YAMASHITA
Yutaro HARADA
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Reuter Chemische Apparatenbau eK
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Reuter Chemische Apparatenbau eK
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Publication of WO2025248024A1 publication Critical patent/WO2025248024A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/202—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring the aromatic ring being a naphthalene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/54—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and etherified hydroxy groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/257—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings
    • C07C43/275—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings having all ether-oxygen atoms bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/30—Hetero atoms other than halogen
    • C07D333/32—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/76—Dibenzothiophenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates
    • C08G64/307—General preparatory processes using carbonates and phenols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
    • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
    • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
    • C07C2603/18—Fluorenes; Hydrogenated fluorenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
    • C07C2603/26—Phenanthrenes; Hydrogenated phenanthrenes

Definitions

  • Binaphthyl Compounds as additives in resin compositions The present invention relates to binaphthyl compounds, which are suitable as additives in resin compositions, in particular in thermoplastic resin compositions for producing optical devices suchs as optical lenses.
  • the invention also relates to resin compositions containing such binaphthyl compounds and at least one resin, in particular at least one thermoplastic resin.
  • Optical devices, such as optical lenses made of optical resin instead of optical glass are advantageous in that they can be produced in large numbers by injection molding of resin materials, hereinafter referred to as optical resins and optical resin materials, re- spectively.
  • optical resins in particular, transparent polycarbonate resins, transparent polyester resins and transparent polyestercarbonate resins, are frequently used for producing camera lenses in optical systems of various cameras, such as cameras in smartphones, digital still cameras (DSC), cameras in automotive systems, video cam- eras and the like.
  • resins with a high refractive index are highly desira- ble, as they allow for reducing the size and weight of final products.
  • a lens element of the same re- fractive power can be achieved with a surface having less curvature, so that the amount of aberration generated on this surface can be reduced.
  • the resin material should have a low or moderate Abbe number to ensure low chromatic aberra- tion.
  • the resins should have excellent heat resistance and high transpar- ency.
  • the production of optical devices such as camera lenses typically requires the molding of the optical resin material used for the production of the optical device. Therefore, the optical resin material must also have a good moldibility.
  • a good moldability typi- cally requires a low melting or softening temperature and a low melt viscosity in order to reduce thermal stress and defects during the molding process.
  • Patent document 1 discloses resin compositions containing an optical bicycloolefine based resin and a monomeric binaphthyl compound having reactive hydroxyl or car- boxyl groups.
  • Patent document 2 discloses resin compositions containing an optical resin based on polycarbonates or polyesters of 9,9-bis (4-(2-hydroxyethoxy) phenyl) fluorene (BPEF) and/or 2,2 ′-bis (2-hydroxyethoxy) -1,1 ′-binaphthalene and an oligomer of 2,2 ′-bis (2-hydroxyethoxy) -1,1 ′-binaphthalene.
  • BPEF 9,9-bis (4-(2-hydroxyethoxy) phenyl) fluorene
  • 2,2 ′-bis (2-hydroxyethoxy) -1,1 ′-binaphthalene 2,2 ′-bis (2-hydroxyethoxy) -1,1 ′-binaphthalene
  • Patent document 1 EP 3904442
  • Patent document 2 WO 2021/014962 Therefore, there is an ongoing need for providing resin materials having both good op- tical properties, such as high refractive index and low Abbe number, and a good mold- ibiltiy.
  • Ar 1 is selected from the group consisting of a mono- or polycyclic aryl having from 6 to 50 carbon atoms as ring members and a mono- or polycyclic hetaryl having a total of 5 to 50 atoms, which are ring members, where 1, 2, 3
  • a second aspect of the present invention relates to compounds of the for- mula (I) that are novel.
  • a third aspect relates to resin compositions comprising at least one resin, such as in particular a thermoplastic resin, especially an optical thermoplastic resin, and at least one compound of the formula (I) as defined herein.
  • the invention further relates to an optical devices made of the resin compositions as defined herein.
  • the compounds of formula (I) may have axial chirality due to the limited rotation along the bond between the two naphthyl units of the central 1,1’-binaphthol moiety and therefore compounds of the formula (I) may exist in the form of one of the two enani- omers or in the form of a mixture of these enantiomers.
  • the present invention relates to the pure enatiomers of the compounds of formula (I) and any mixtures of the enan- tiomers, including racemic as well as non-racemic mixtures of these enantiomers.
  • C1-C6-alkylene may alternatively also be designated “alkandiyl having 1, 2, 3, 4, 5 or 6 carbon atoms” and refers to a bivalent, saturated, aliphatic hydrocarbon radical having 1, 2, 3, 4, 5 or 6 carbon atoms.
  • C1-C6-alkandiyl are in particular the methylene group (CH2), linear alkylene such as 1,2-ethylene (CH2CH2), 1,3-propylene (CH2CH2CH2), 1,4-butylene (CH2CH2CH2CH2), 1,6-hexylene (CH2CH2CH2CH2CH2CH2), but also branched alkandiyl such as 1-methyl- 1,2-ethylene, 1-methyl-1,2-propylene, 2-methyl-1,2-propylene, 2-methyl-1,3-propyl- ene, 1,3-butylene, 1,3-pentylene and 2-methyl-1,4-pentylene.
  • halogen refers to fluorine, chlorine, bro- mine or iodine radicals.
  • alkyl refers to an aliphatic saturated hy- drocarbon radical which may be linear or branched. Examples of C1-C2-alkyl are methyl and ethyl. Examples of C1-C3-alkyl are, in addition to those mentioned for C1-C2-alkyl, n-propyl and isopropyl.
  • C1-C4-alkyl examples are, in addition to those mentioned for C1-C3-alkyl, n-butyl, 2-butyl (sec-butyl), isobutyl and tert-butyl.
  • Examples for C1-C6-alkyl are, in addition to those mentioned for C1-C4-alkyl, n-pentyl, 1-methylbutyl, 2-methyl- butyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dime- thylbutyl, 3,3-dimethylbutyl, 1-
  • C1-C8- alkyl are, in addition to those mentioned for C1-C6-alkyl, n-heptyl, 1-methylhexyl, 2- methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylpentyl, 2-ethylpen- tyl, 3-ethylpentyl, n-octyl, 1-methyloctyl, 2-methylheptyl, 1-ethylhexyl, 2-ethylhexyl, 1,2-dimethylhexyl, 1-propylpentyl and 2-propylpentyl.
  • Examples for C1-C10-alkyl are, in addition to those mentioned for C1-C8-alkyl, nonyl, decyl, 2-propylheptyl and 3- propylheptyl.
  • Examples for C1-C18-alkyl are, in addition to those mentioned for C1-C10- alkyl, linear undecyl and its position isomers and branched isomers, lauryl and its posi- tion isomers and branched isomers, linear tridecyl and its position isomers and branched isomers, myristyl and its position isomers and branched isomers, palmityl and its position isomers and branched isomers, and stearyl and its position isomers and branched isomers.
  • C1-C20-alkyl examples are, in addition to those mentioned for C1- C18-alkyl, linear nonadecyl and its position isomers and branched isomers and eicosenyl and its position isomers and branched isomers.
  • cycloalkyl refers to a mono-, bi- or tricy-mann cycloaliphatic radical having from 5 to 20 carbon atoms (“C5-C20-cycloalkyl”), usu- ally from 5 to 10 carbon atoms (“C5-C10-cycloalkyl”), and preferably 5 to 10 carbon at- oms (“C5-C10 cycloalkyl").
  • Examples of monocyclic C5-C10 cycloalkyl are cyclopentyl, cy- clohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, bicyclo[2.1.1]hexyl, bicy- clo[2.2.1]heptyl, bicyclo[3.1.1]heptyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl, bicy- clo[3.2.1]octyl, bicyclo[3.1.0]hexyl, bicyclo[3.2.0]heptyl, bicyclo[3.3.0]octyl (1,2,3,3a,4,5,6,6a-octahydropentalenyl), bicyclo[4.2.0]octyl, bicyclo[4.3.0]nonyl (2,3,3a,4,5,6,7,7a-octahydro-1
  • alkoxy refers to a straight-chain or branched alkyl group having from 1 to 20 carbon atoms which is bound to the remain- der of the molecule via an oxygen atom.
  • Examples for C1-C20-alkoxy are methoxy, eth- oxy, n-propoxy, 1-methylethoxy (isopropoxy), butoxy, 1-methylpropoxy (sec-butoxy), 2-methylpropoxy (isobutoxy), 1,1-dimethylethoxy (tert-butoxy), pentoxy, 1-methylbut- oxy, 2-methylbutoxy, 3-methylbutoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, M/REUCTR-054-PC 7 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dime- th
  • the term “monocyclic aryl” refers to a monovalent aromatic monocyclic radical, such as in particular phenyl.
  • the term “monocyclic hetaryl” refers to a monovalent heteroaromatic monocyclic radical, i.e.
  • heteroaromatic monocycle linked by a single covalent bond to the remainder of the molecule, where the ring member atoms are part of a conjugate ⁇ -electron system, where the heteroaromatic monocycle has 5 or 6 ring atoms, which comprise as heterocyclic ring members 1, 2, 3 or 4 nitrogen atoms or 1 oxygen atom and 0, 1, 2 or 3 nitrogen atoms, or 1 sulphur atom and 0, 1, 2 or 3 nitrogen atoms, where the remaining ring atoms are carbon atoms.
  • the term “mono- or polycyclic aryl” refers to a mono- valent aromatic monocyclic radical as defined herein or to a monovalent aromatic poly- cyclic radical, i.e. a polycyclic arene linked by a single covalent bond to the remainder of the molecule, where the polycyclic arene is (i) an aromatic polycyclic hydrocarbon, i.e.
  • a completely unsaturated polycyclic hydro- carbon where each of the carbon atoms is part of a conjugate ⁇ -electron system
  • a polycyclic hydrocarbon which bears at least 1 phenyl ring which is fused to a sat- urated or unsaturated 4 to 10-membered mono- or bicyclic hydrocarbon ring
  • a polycyclic hydrocarbon which bears at least 2 phenyl rings which are linked to each other by a covalent bond or which are fused to each other directly and/or which are fused to a saturated or unsaturated 4 to 10-membered mono- or bicyclic hydrocar- bon ring
  • a polycyclic hydrocarbon which bears at least 2 phenyl rings which are linked to each other by a methylene bridge, where the methylene bridge may be unsubstituted or carry one or two substitutents selected from C1-C4-methyl, phenyl, naphthyl and phenant
  • Mono- or polycyclic aryl has from 6 to 50, often from 6 to 40 carbon atoms, e.g. 6, 9, 10, 12, 13, 14, 16, 17, 18, 19, 20, 22, 24, 26, 30, 33 or 40 carbon atoms as ring at- oms, in particular from 6 to 26 carbon atoms, especially 6, 10, 12, 13, 14, 16, 17, 18, 19, 20, 22, 24 or 26 carbon atoms.
  • Polycyclic aryl typically has 10 to 50 carbon atoms as ring atoms, in particular from 10 to 40 carbon atoms, especially 10, 12, 13, 14, 16, 17, 18, 19, 20, 22, 24, 26, 30, 33 or 40 carbon atoms.
  • polycyclic aryl bearing 2, 3 or 4 phenyl rings which are linked to each other via a single bond include e.g. biphenylyl and terphenylyl.
  • Polycyclic aryl bearing 2, 3 or 4 phenyl rings which are directly fused to each other include e.g. naphthyl, an- thracenyl, phenanthrenyl, pyrenyl, triphenylenyl, chrysenyl and benzo[c]phenanthrenyl.
  • Polycyclic aryl bearing 2, 3 or 4 phenyl rings which are fused to a saturated or unsatu- rated 4- to 10-membered mono- or bicyclic hydrocarbon ring include e.g.
  • Mono- or polycylic aryl includes, by way of example phenyl, naphthyl, 9H-fluorenyl, phenanthrenyl, anthracenyl, pyrenyl, chrysenyl, benzo[c]phenanthrenyl, acenaph- thenyl, acenaphthylenyl, 2,3-dihydro-1H-indenyl, 5,6,7,8-tetrahydro-naphthalenyl, cy- clopent[fg]acenaphthylenyl, 2,3-dihydrophenalenyl, 9,10-dihydroanthracen-1-yl, 1,2,3,4-tetrahydrophenanthrenyl, 5,6,7,8-tetrahydrophenanthrenyl, fluoranthenyl, benzo[k]fluoranthenyl, biphenylenyl, triphenylenyl,
  • the term “mono- or polycyclic hetaryl” refers to a monovalent heteroaromatic monocyclic radical as defined herein or to a monovalent heteroaromatic polycyclic radical, i.e. a polycyclic hetarene linked by a single covalent bond to the remainder of the molecule, where (i) the polycyclic hetarene bears a heteroaromatic monocycle as defined above and at least one, e.g.
  • aromatic rings selected from phenyl and het- eroaromatic monocycles as defined above, where the aromatic rings of the polycyclic M/REUCTR-054-PC 9 hetarene are linked to each other by a covalent bond and/or fused to each other di- rectly and/or fused to a saturated or unsaturated 4 to 10-membered mono- or bicyclic hydrocarbon ring, or (ii) the polycyclic hetarene bears at least one saturated or partially or fully unsaturated 5-, 6-, 7- or 8-membered heterocyclic ring bearing 1, 2 or 3 heteroatoms selected from oxygen, sulphur and nitrogen as ring atoms, such as 2H-pyran, 4H-pyran, thiopyran, 1,4-dihydropyridin, 4H-1,4-oxazin, 4H-1,4-thiazin, 1,4-dioxin, oxepin, thiepin, dioxin,
  • aromatic rings selected from phenyl and heteroaromatic monocycles as defined above where at least one of the aromatic rings is directly fused to the saturated or partially unsaturated 5- to 8-membered heterocyclic ring and where the aromatic rings of the polycyclic hetarene are linked to each other by a covalent bond or fused to each other directly and/or fused to a saturated or unsaturated 4 to 10-membered mono- or bicy-hack hydrocarbon ring, or (iii) the polycyclic hetarene bears at least two moncyclic aromatic rings selected from phenyl and heteroaromatic monocycles as defined above, where the two rings are linked to each other by a heteroatom selected from oxygen, sulphur and nitrogen, and are in particular linked by O, S, NRH, SO and SO2, where RH is hydrogen, C1-C4-alkyl, phenyl, naphthyl or phenanthrenyl.
  • Mono- or polycyclic hetaryl has from 5 to 50, often from 5 to 40 or 5 to 34 ring atoms, in particular 5 to 26 ring atoms, which comprise 1, 2, 3 or 4 atoms selected from nitro- gen atoms, sulphur atoms and oxygen atoms, where the remainder of the ring atoms are carbon atoms.
  • Polycyclic hetaryl generally has from 9 to 50, often from 9 to 34 ring atoms, in particular 9 to 26 ring atoms, which comprise 1, 2, 3 or 4 atoms selected from nitrogen atoms, sulphur atoms and oxygen atoms, where the remainder of the ring atoms are carbon atoms.
  • the term “monocyclic arylene” refers to a bivalent aromatic monocyclic radical, such as in particular phenylene.
  • the term “monocyclic hetarylene” refers to a bivalent heteroaromatic monocyclic radical, i.e.
  • heteroaromatic monocycle linked by two sin- gle covalent bonds to the two remaining parts of the molecule, where the ring member atoms are part of a conjugate ⁇ -electron system, where the heteroaromatic monocycle has 5 or 6 ring atoms, which comprise as heterocyclic ring members 1, 2, 3 or 4 nitro- gen atoms or 1 oxygen atom and 0, 1, 2 or 3 nitrogen atoms, or 1 sulphur atom and 0, 1, 2 or 3 nitrogen atoms, where the remaining ring atoms are carbon atoms.
  • the term “mono- or polycyclic arylene” refers to a bi- valent aromatic monocyclic radical as defined herein or to a bivalent aromatic polycy- stunt radical, i.e. a polycyclic arene linked by two single covalent bonds to the two re- maining parts of the molecule, where the polycyclic arene is M/REUCTR-054-PC 11 (i) an aromatic polycyclic hydrocarbon, i.e.
  • a completely unsaturated polycyclic hydro- carbon where each of the carbon atoms is part of a conjugate ⁇ -electron system
  • a polycyclic hydrocarbon which bears at least 1 phenyl ring which is fused to a sat- urated or unsaturated 4 to 10-membered mono- or bicyclic hydrocarbon ring
  • a polycyclic hydrocarbon which bears at least 2 phenyl rings which are linked to each other by a covalent bond or which are fused to each other directly and/or which are fused to a saturated or unsaturated 4 to 10-membered mono- or bicyclic hydrocar- bon ring
  • a polycyclic hydrocarbon which bears at least 2 phenyl rings which are linked to each other by a methylene bridge, where the methylene bridge may be unsubstituted or carry one or two substitutents selected from C1-C4-methyl, phenyl, naphthyl and phenant
  • Mono- or polycyclic arylene has from 6 to 26, often from 6 to 24 carbon atoms, e.g. 6, 9, 10, 12, 13, 14, 16, 17, 18, 19, 20, 22 or 24 carbon atoms as ring atoms, in particu- lar from 6 to 20 carbon atoms, especially 6, 10, 12, 13, 14, 16, 17 or 18 carbon atoms.
  • Polycyclic arylene typically has 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.
  • polycyclic arylene bearing 2, 3 or 4 phenyl rings which are linked to each other via a single bond include e.g. biphenylylene and terphenylylene.
  • Polycyclic arylene bearing 2, 3 or 4 phenyl rings which are directly fused to each other include e.g. naphthylene, anthracenylene, phenanthrenylene, pyrenylene, triphenylenylene, chrysenylene and benzo[c]phenanthrenylene.
  • Polycyclic arylene bearing 2, 3 or 4 phe- nyl rings which are fused to a saturated or unsaturated 4- to 10-membered mono- or bicyclic hydrocarbon ring include e.g.
  • the term “mono- or polycyclic hetarylene” refers to a bivalent heteroaromatic monocyclic radical as defined herein or to a bivalent heteroaro- matic polycyclic radical, i.e. a polycyclic hetarene linked by two single covalent bonds to the two remaining parts of the molecule, where (i) the polycyclic hetarene bears a heteroaromatic monocycle as defined above and at least one, e.g.
  • aromatic rings selected from phenyl and het- eroaromatic monocycles as defined above, where the aromatic rings of the polycyclic hetarene are linked to each other by a covalent bond and/or fused to each other di- rectly and/or fused to a saturated or unsaturated 4 to 10-membered mono- or bicyclic hydrocarbon ring, or (ii) the polycyclic hetarene bears at least one saturated or partially or fully unsaturated 5-, 6-, 7- or 8-membered heterocyclic ring bearing 1, 2 or 3 heteroatoms selected from oxygen, sulphur and nitrogen as ring atoms, such as 2H-pyran, 4H-pyran, thiopyran, 1,4-dihydropyridin, 4H-1,4-oxazin, 4H-1,4-thiazin, 1,4-dioxin, oxepin, thiepin, dioxin, dithiin, dioxepin, di
  • aromatic rings selected from phenyl and heteroaromatic monocycles as defined above where at least one of the aromatic rings is directly fused to the saturated or partially unsaturated 5- to 8-membered heterocyclic ring and where the aromatic rings of the polycyclic hetarene are linked to each other by a covalent bond or fused to each other directly and/or fused to a saturated or unsaturated 4 to 10-membered mono- or bicy-hack hydrocarbon ring, or (iii) the polycyclic hetarene bears at least two moncyclic aromatic rings selected from phenyl and heteroaromatic monocycles as defined above, where the two rings are linked to each other by a heteroatom selected from oxygen, sulphur and nitrogen, and are in particular linked by O, S, NR H , SO and SO2, where R H is hydrogen, C1-C4-alkyl, phenyl, naphthyl or phenanthrenyl.
  • Mono- or polycyclic hetarylene has from 5 to 26, often from 5 to 24 ring atoms, in par- ticular 5 to 20 ring atoms, which comprise 1, 2, 3 or 4 atoms selected from nitrogen at- oms, sulphur atoms and oxygen atoms, where the remainder of the ring atoms are carbon atoms.
  • Polycyclic hetaryl generally has from 9 to 26, often from 9 to 24 ring at- oms, in particular 9 to 20 ring atoms, which comprise 1, 2, 3 or 4 atoms selected from nitrogen atoms, sulphur atoms and oxygen atoms, where the remainder of the ring at- oms are carbon atoms.
  • the suffix “-ylene” means, as customary in the art, that the respective het(arene) moiety is in the form of its diradikal. Accordingly, the suffix “-ylene”, as e.g. in phenylene or 1,4-phenylene, is used here synonymously with the suffix “-diyl”, as e.g. in phendiyl or phen-1,4-diyl.
  • a “structural unit” is a structural element which is present repeatedly in the polymer backbone of the thermoplastic resin. Therefore, the terms “structural unit” and “repeating unit” are used synonymously.
  • optical device refers to a device that is transparent for visible light and manipulates light beams, in particular by refraction.
  • Optical devices include but are not limited to prisms, lenses, optical films and combina- tions thereof, especially lenses for cameras and lenses for glasses.
  • the remarks made below as to preferred embodiments of the variables (substituents) of the compounds of formulae (I), (Ia) and (Ib) are valid on their own as well as pref- erably in combination with each other.
  • variables A 1 , A 2 , X 1 , X 2 , Ar 1 , Ar 2 , L 1 , L 2 , R 1 , R 2 , k, l, p and q on their own or preferably in any combination preferably have the following meanings:
  • the variables A 1 and A 2 in formulae (I) and (Ia) are identical or different and independently selected from C1-C6-alkylene, preferably C1-C4-alkylene, which are unsubstituted or substituted by 1, 2, 3 or 4, preferably by 1 or 2, identical or different radicals R'", where R'" in each occurance has one of the meanings defined herein, in particular one of those mentioned herein as preferred.
  • the variables A 1 and A 2 in formulae (I) and (Ia) are independently selected from linear C2-C4-alkandiyl, such as 1,2-ethandiyl (CH2- CH2), 1,3-propandiyl or 1,4-butandiyl, and in particular 1,2-ethandiyl.
  • the variables A 1 and A 2 are identical to each other.
  • the variables A 1 and A 2 in formulae (I) and (Ia) are both -CH 2 -CH 2 -.
  • the moieties X 1 and X 2 in formulae (I) and (Ia) are both O.
  • variables Ar 1 and Ar 2 in formulae (I) and (Ia) that are inde- pendently is selected from mono- or polycyclic aryl having from 6 to 36, especially from 6 to 26, carbon atoms as ring members and mono- or polycyclic hetaryl having from 5 to 36, especially from 5 to 26, ring atoms, which comprise 1, 2, 3 or 4 atoms, in particular 1, 2 or 3 atoms, specifically 1 or 2 atoms, selected from nitrogen atoms, sul- fur atoms and oxygen atoms, where the remainder of the ring atoms are carbon at- M/REUCTR-054-PC 16 oms, where the mono- or polycyclic aryl and the mono- or polycyclic hetaryl are unsub- stituted or carry 1, 2 or 3 radicals R Ar ; wherein R Ar have the meanings defined herein, in particular those mentioned herein as preferred.
  • variables Ar 1 and Ar 2 are independently from each other selected from mono-or polycyclic aryl having from 6 to 36, preferably 6 to 26, in particular 6 to 20, carbon atoms as ring members, where Ar 1 and Ar 2 are in- dependently unsubstituted or carry 1, 2 or 3, preferably 1 or 2, in particular 1, substit- uents R Ar , wherein R Ar in each occurance has the meaning defined herein, in particular one mentioned herein as preferred.
  • the variable Ar 1 is phe- nyl, naphthyl or phenanthrenyl, where phenyl, naphthyl and phenanthrenyl are unsub- stituted or substituted by 1, 2, 3 or 4, preferably 1 or 2, in particular 1, identical or dif- ferent radicals R'"; or Ar 1 is a group represented by the following formula (Ar 1 -a): (Ar 1 -a), where # represents a connection point to L 1 , a and b are identical or different and independently 0 or 1, and R Ar1 and R Ar2 are identical or different and have the meanings defined herein for R Ar , in particular the preferred meanings.
  • the one or more radicals R' are preferably selected from phenyl, halogen, CN, CH3 and OCH3, especially from halogen and CN, while the variable b in formula (Ar 1 -a) is preferably 0.
  • the variable Ar 2 is phe- nyl, naphthyl or phenanthrenyl, where phenyl, naphthyl and phenanthrenyl are unsub- stituted or substituted by 1, 2, 3 or 4, preferably 1 or 2, in particular 1, identical or dif- ferent radicals R'"; or Ar 2 is a group represented by the following formula (Ar 2 -a): M/REUCTR-054-PC 17 (Ar 2 -a), where # represents a connection point to L 2 , a and b are identical or different and independently 0 or 1, and R Ar1 and R Ar2 are identical or different and have the meanings defined herein for R Ar , in particular the preferred meanings.
  • the one or more radicals R' are preferably selected from phenyl, halogen, CN, CH3 and OCH3, especially from halogen and CN, while the variable b in formula (Ar 1 -a) is preferably 0.
  • the variables Ar 1 and Ar 2 are identical, i.e.
  • radicals R 1 and Ar 2 are both either phenyl, naphthyl, phenan- threnyl or identical radicals (Ar 1 -a) and (Ar 2 -a), where phenyl, naphthyl and phenan- threnyl are optionally substituted and, if substituted, are preferably intendically substi- tuted, i.e. bearing one or two radicals R'" which between the groups Ar 1 and Ar 2 have the same meanings and are located in the same positions.
  • the radicals R' if present, have the meanings defined herein, in particular the preferred meanings.
  • variable Ar 1 is a radical of formula (Ar 1 -a) and the variable Ar 2 is an optionally sub- stituted phenyl, naphthyl or phenanthrenyl, where phenyl, naphthyl and phenan- threnyl, if substituted, preferably carry one or two radicals R'", which have the mean- ings defined herein, in particular the preferred meanings. If phenyl, naphthyl or phe- nanthrenyl are substituted with two radicals R'", they may be different or are prefera- bly identical.
  • the one or more radicals R Ar in formulae (I) and (Ia) are selected from the group consisting of R, OR and NR2, especially R and OR, where R Ar may be identical or different if more than one R Ar is present on the same (het)aryl group.
  • R has one of the meanings defined herein and is in par- ticular selected from the group consisting of methyl, ethyl, phenyl, benzyl, naphthyl, such as 1-naphthyl or 2-naphthyl, and phenanthrenyl, such as 9-phenanthrenyl, in par- M/REUCTR-054-PC 18 ticular from phenyl, benzyl and naphthyl, where R may be substituted with 1 or 2 radi- cals R'" and preferably is unsubstituted.
  • the one or more radicals R Ar are preferably selected from the group consisting of C 1 -C 4 - alkyl, phenyl, benzyl, naphthyl, phenanthrenyl, C1-C4-alkoxy, phenoxy, benzyloxy, naphthyloxy, phenanthrenyloxy, di(C 1 -C 4 -alkyl)amino, diphenylamino, dibenzylamino and dinaphthylamino, diphenanthrenylamino, and especially from the group consisting of phenyl, benzyl, naphthyl, phenoxy, benzyloxy and naphthyloxy.
  • the two moieties L 1 and L 2 are identical or different and are independently selected from the group consisting of a single bond and C 1 -C 4 -alkylene, such as in particular linear C 1 -C 4 -alkylene. More preference is given here to moieties L 1 and L 2 that are independently selected from a single bond, meth- ylene (CH2), 1,2-ethylene (CH2CH2), 1,3-propylene (CH2CH2CH2), in particular from a single bond and methylene.
  • the two moieties L 1 and L 2 are identical and preferably are both a single bond, methylene (CH 2 ), 1,2-ethylene (CH 2 CH 2 ) or 1,3-propylene, and more preferably are both a single bond or methylene.
  • the sum k+l of the varia- bles k and l in formulae (I) and (Ia) is 1 or 2 and both moieties L 1 and L 2 are single bonds, or the sum k+l is 0 and both moieties L 1 and L 2 are single bonds, methylene or mixtures thereof.
  • radicals R 1 and R 2 of formulae (I) and (Ia), if present, are independently selected from the group consisting of halogen, C2- C 3 -alkynyl, CN, R 11 and OR 11 , where R 11 is in particular selected from the group consist- ing of benzyl, mono- or polycyclic aryl having from 6 to 18 carbon atoms as ring atoms or are mono- or polycyclic hetaryl having a total of 5 to 18 atoms, which are ring mem- bers, where 1, 2, 3 or 4, in particular 1 or 2, of these ring member atoms of hetaryl are selected from nitrogen, sulfur and oxygen, while the remainder of these ring member atoms of hetaryl are carbon atoms, where aryl and hetaryl are unsubstituted or carry a substituent R'".
  • radicals R 1 and R 2 are independently selected from the group consisting of halogen, C2-C3-al- kynyl, CN, R 11 and OR 11 , where R 11 is selected from benzyl and mono- or polycyclic aryl having from 6 to 18 carbon atoms as ring atoms and mono- or polycyclic hetaryl hav- ing from 5 to 18 atoms as ring members, where 1, 2, 3 or 4, in particular 1 or 2, of these ring member atoms nitrogen, sulfur or oxygen, while the remainder of are car- bon atoms.
  • R 11 is preferably selected here from benzyl, phenyl, naphthyl, phenan- threnyl, triphenylenyl, dibenzo[b,d]thiophenyl and thianthrenyl, which radicals may be M/REUCTR-054-PC 19 unsubstituted or may carry a substituent R'" preferably selected from phenyl, halogen and CN.
  • R' preferably selected from phenyl, halogen and CN.
  • the var- iables p and q are independently 0 or 1.
  • the variables p and q are both 0, i.e. the central 1,1’-binaphthyl moiety of the com- pound of formulae (I) or (Ia) is devoid of substituents R 1 and R 2 .
  • the variables p and q are both 1, i.e.
  • the central 1,1’-binaphthyl moiety of the com- pound of formulae (I) or (Ia) carries one substituent R 1 and one substituent R 2 , where R 1 and R 2 preferably are independently selected from halogen, CN, phenyl, phenoxy, naphthyl, such as 1-naphthyl or 2-naphthyl, naphthyloxy, such as 1- or 2-naphthyloxy, phenanthrenyl, such as 9-phenanthrenyl, and thianthrenyl, such as 1-thianthrenyl or 2- thianthrenyl.
  • variables R 11 , Rh1, R, R', R", R'", s, p and q either alone or preferably in combination with each other and with the meanings and preferred meanings of the variables A 1 , A 2 , Ar 1 , Ar 2 , X 1 , X 2 , L 1 , L 2 , R 1 , R 2 , R Ar , k and l described above, have the following meanings.
  • R 11 is preferably selected from the group consisting of C1-C4-alkyl, benzyl, mono- or polycyclic aryl having from 6 to 18 carbon atoms as ring atoms and mono- or polycyclic hetaryl having a total of 5 to 18 atoms, which are ring members, where 1, 2, 3 or 4 of these ring member atoms of hetaryl are selected from nitrogen, sulfur and oxygen, while the remainder of these ring member atoms of hetaryl are carbon atoms, where benzyl, aryl and hetaryl are unsubstituted or substituted by 1, 2, 3 or 4 identical or dif- M/REUCTR-054-PC 20 ferent radicals R'", where R'", independently of each occurrence, has one of the mean- ings defined herein, in particular a preferred one.
  • R 11 is selected from methyl, ethyl, benzyl, phenyl, naphthyl, such as 1-naphthyl and 2-naphthyl, phenan- threnyl, such as 9-phenanthrenyl, triphenylenyl, such as 2-triphenylenyl, dibenzo[b,d]thiophenyl, such as 4-dibenzo[b,d]thiophenyl, and thianthrenyl, such as 1- thianthrenyl or 2-thianthrenyl, which are unsubstituted or substituted by 1, 2 or 3 iden- tical or different radicals R'", where R'", independently of each occurrence, has one of the meanings defined herein, in particular a preferred one.
  • R 11 is selected from the group consisting of benzyl, phenyl, naphthyl, phenanthrenyl, tri- phenylenyl, dibenzo[b,d]thiophenyl and thianthrenyl, which are unsubstituted.
  • R 11 is selected from the group consisting of phenyl, naphthyl, phenanthrenyl and thianthrenyl, which are unsubstituted.
  • R h1 is preferably selected from the group consisting of mono- or polycyclic aryl having from 6 to 18 carbon atoms as ring atoms and mono- or polycyclic hetaryl having a total of 5 to 18 atoms, which are ring members, where 1, 2, 3 or 4 of these ring member at- oms of hetaryl are selected from nitrogen, sulfur and oxygen, while the remainder of these ring member atoms of hetaryl are carbon atoms.
  • R h1 is selected from phenyl, naphthyl, such as 1-naphthyl and 2-naphthyl, phenanthrenyl, such as 9- phenanthrenyl, triphenylenyl, such as 2-triphenylenyl, dibenzo[b,d]thiophenyl, such as 4-dibenzo[b,d]thiophenyl, and thianthrenyl, such as 1-thianthrenyl or 2-thianthrenyl.
  • Rh1 is selected from the group consisting of benzyl, phenyl, naphthyl, phenanthrenyl, triphenylenyl, dibenzo[b,d]thiophenyl and thianthrenyl, which are unsubstituted.
  • R h1 is selected from the group consisting of phenyl, naphthyl, phenanthrenyl and thianthrenyl.
  • R is preferably selected from the group consisting of methyl, ethyl, phenyl, benzyl, naphthyl, such as 1-naphthyl or 2-naphthyl, and phenanthrenyl, such as 9-phenan- threnyl, which are unsubstituted or substituted by 1, 2 or 3, especially 1 or 2, identical or different radicals R'", where R'", independently of each occurrence, has one of the meanings defined herein, in particular a preferred one.
  • R is selected from the group consisting of phenyl, benzyl, naphthyl and phenanthrenyl, specifically phenyl, benzyl and naphthyl, which are all unsubstituted.
  • R' is preferably selected from the group consisting of phenyl, naphthyl, phenanthrenyl and triphenylenyl, which are unsubstituted or substituted by 1, 2 or 3, especially 1 or 2, identical or different radicals R'", where R'", independently of each occurrence, has one of the meanings defined herein, in particular a preferred one.
  • R' is selected from the group consisting of phenyl, naphthyl and phenanthrenyl, which are unsubstituted.
  • M/REUCTR-054-PC 21 R" is preferably selected from the group consisting of hydrogen, methyl, phenyl and naphthyl, where phenyl and naphthyl are unsubstituted or substituted by 1, 2 or 3, es- pecially 1 or 2, identical or different radicals R'", where R'", independently of each oc- currence, has one of the meanings defined herein, in particular a preferred one. More preferably, R" is unsubstituted phenyl or unsubstituted naphthyl.
  • R'" is preferably selected from the group consisting of phenyl, fluorine, chlorine, CN, OCH 3 and CH 3 , especially phenyl, fluorine and CN.
  • the variable s is preferably 1 or 2, and in particular is 2.
  • the variables p and q are preferably identical and are also preferably 0 or 1.
  • Examples of the particular subgroup (6a) are the compounds of the formula (Ib), in which the combination of the moieties Ar 1 , Ar 2 , L 1 , L 2 , R 1 , R 2 , and the variables p, q, k and l is as defined in any one of the lines 1 to 36 in table A below.
  • step b) of the process the two hydroxyl groups of the the compound (2) obtained in step a) are converted into leaving groups Z for example via reaction with mesyl chloride or tosyl chloride in the presence of a suitable base, such as triethylamine, to afford a compound (4).
  • a suitable base such as triethylamine
  • step c) the hydroxyl group of the the compound (8) is then converted into a leaving group Z for example via reaction with mesyl chloride or tosyl chloride in the presence of a suitable base, such as triethylamine, to afford a compound (9).
  • step d) the compound (9) is reacted with e.g.
  • the compounds of formula (Ib), where k is 0, l is 1, L 1 and L 2 are both CH2 moieties and Ar 1 and Ar 2 are independently seleced from (het)aryl groups as defined herein, can for example be prepared by analogy to the process shown in scheme 2, with the ex- ception that in step d) instead of a (het)aryl alcohol Ar 1 -OH for instance a (het)aryl methanol Ar 1 -CH 2 OH is used.
  • the compounds of formula (Ib), where k is 0, l is 1, L 1 and L 2 are both single bonds and Ar 1 and Ar 2 are independently seleced from (het)aryl groups as defined herein can for example be prepared by analogy to the process shown in scheme 2, with the exception that in step a) instead of a (het)aryl methylbromide Ar 2 -CH2Br for instance a (het)aryl alcohol Ar 2 -OH or (het)aryl fluoride Ar 2 -F is used.
  • these compounds of formula (Ib), where k and l are both 0, L 1 and L 2 are both single bonds and Ar 1 and Ar 2 are identical (het)aryl groups Ar as defined herein, can also be prepared by a copper- or copper/iron-catalyzed Ullmann coupling reaction, where 1,1’-bi-2-naphthol (1) is reacted with a (het)aryl halide, typically a (het)aryl bro- mide or iodide, in the presence of a base, such as K 2 CO 3 , and a suitable catalyst, such as especially a mixture of copper(I) iodide (CuI) and iron(III) acetylacetonate (Fe(acac)3) in a polar aprotic solvent, such as DMF or DMSO.
  • a base such as K 2 CO 3
  • a suitable catalyst such as especially a mixture of copper(I) iodide (CuI) and iron(III) ace
  • the intermediates in some cases result in the form of colorless or pale brownish, viscous oils, which are freed of volatiles or purified under reduced pressure and at moderately elevated temperature. If the intermediates are obtained as solids, the puri- fication can be achieved by recrystallization or washing procedures, such as slurry washing.
  • the starting compounds used in the syntheses shown in schemes 1, 2 and 3 above to prepare compounds of formula (I) are commercially available or can be prepared by methods known from the art. M/REUCTR-054-PC 29
  • the compounds of the present invention can be obtained in high purity, which means that a product is obtained, which does not contain significant amounts of organic impu- rities different from the compound of formula (I), except for volatiles.
  • the pu- rity of compounds of formula (I) is at least 95%, in particular at least 98% and espe- cially at least 99%, based on the non-volatile organic matter, i.e. the product contains at most 5%, in particular at most 2% and especially at most 1% of non-volatile impuri- ties different from the compound of formula (I).
  • volatiles refers to organic compounds, which have a boiling point of less than 200°C at standard pressure (10 5 Pa). Consequently, non-volatile organic matter is understood to mean compounds having a boiling point, which exceeds 200°C at stand- ard pressure.
  • the compounds of formula (I) and like- wise their solvates can often be obtained in crystalline form.
  • the compound of formula (I) may be present in pure form or in the form of a solvate with water or an organic solvent. Therefore, a particular aspect of the invention relates to the compounds of formula (I), which are essentially present in crystalline form.
  • the invention relates to crystalline forms, where the compound of formula (I) is present without solvent and to the crystalline solvates of the compounds of for- mula (I), where the crystals contain a solvent incorporated.
  • Suitable organic solvents for crystallizing the compounds of the formula (I) or their solvates in- clude but are not limited to aromatic hydrocarbons such as toluene or xylene, aliphatic ketones in particular ketones having from 3 to 6 carbon atoms, such as acetone, me- thyl ethyl ketone, methyl isopropyl ketone or diethyl ketone, aliphatic and alicyclic ethers, such as diethyl ether, dipropyl ether, methyl isobutyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, dioxane or tetrahydrofuran, 2-methyl-tetrahydrofur
  • a dissolved crude preparation of a compound of formula (I) may be subjected- tration, e.g. over cellite, prior to the crystallization step, in order to remove solid com- ponents that may be present in a crude preparation.
  • impurities, especially color forming impurities, that may be present in a crude preparation of a compound of formula (I) can be removed at any stage of the purification process, e.g. before a filtration step or a crystallization step, by standard procedures, such as treatment with an adsorbent, e.g. activated charcoal.
  • the compounds of the formula (I) and likewise their solvates can be ob- tained in purified form by employing other simple and efficient methods for purifying the raw products of these compounds, such as in particular slurry washing the raw sol- ids obtained directly after the conversion to prepare the compounds of formula (I).
  • Slurry washing is typically conducted at ambient temperature or elevated temperatures of usually about 30 to 90°C, in particular 40 to 80°C.
  • Suitable organic solvents here are in principle the same as those listed above as being suitable for crystallizing the com- pounds of formula (I), such as in particular the mentioned aromatic hydrocarbons, ali- phatic ketones and aliphatic ethers, e.g.
  • the compounds of formula (I) used as additives for thermoplastic resins, in particular polycarbonates, as defined herein, can be easily prepared and obtained in high yield and high purity.
  • compounds of formula (I) can be obtained in crystalline form, which allows for an efficient purification to the degree required in the preparation of optical resins.
  • these compounds can be obtained in a pu- rity which provides for high refractive indices and also low haze, which is particularly important for the use in the preparation of optical resin compositions of which the opti- cal devise is made of.
  • the compounds of formula (I) are particularly use- ful as additives in the preparation of the optical resin compositions.
  • the present invention further relates to resin composition comprising at least one resin and at least one additive selected from the compounds of formulae (I), (Ia) and (Ib) defined above.
  • the compounds (I), (Ia) and (Ib) are particularly useful as additives for thermoplastic resins, especially because they significantly reduce the glass-transistion temperature (Tg) of the resins and thus improve their fluidity and moldibility virtually without affecting their optical properties. Therefore, the compounds (I), (Ia) and (Ib) are specifically suited as additives in thermoplastic resins to be used for preparing lenses and other optical devices.
  • thermoplastic resins are typically selected from polycarbonates, polyestercarbonates,polyesters and mixtures thereof, especially se- lected from aromatic polycarbonates, aromatic polyestercarbonates, aromatic polyes- ters and mixtures thereof. Accordingly, a particular group of embodiment relates to a resin composition compris- ing at least one thermoplastic resin which is a polycarbonate, polyestercarbonate, poly- ester or a mixture thereof, and especially is an aromatic polycarbonate, an aromatic polyestercarbonate, an aromatic polyester or a mixture thereof.
  • Suitable thermoplastic resins which can be used in combination with the compounds of the formula (I) and which are particularly suitable for producing optical devices are well known in the art, e. g.
  • resin compositions comprising at least one ther- moplastic resin selected from polycarbonates, polyestercarbonates, polyesters or mix- tures thereof, and especially selected from aromatic polycarbonates, aromatic polyes- tercarbonates, aromatic polyesters and mixtures thereof.
  • R 11a has in particular one of the preferred meanings given for R 11 in the context of formulae (I) and (Ia).
  • the variables A 1a , A 2a , A 1b , A 2b , R 0 , R 1 , R 2 , Z 1 , Z 2 , a 1 , a 2 , b 1 , b 2 , n 1 , n 2 , m 1 and m 2 on their own or preferably in any combination preferably have the following meanings:
  • Both variables R 0 in formula (II-1) and (II-2), respecitvely, are identical or different and independently selected from C1-C6-alkylene, preferably C1-C4-alkylene, which are unsubstituted or substituted by 1, 2, 3 or 4, preferably by 1 or 2, identical or different radicals R'", where R'" in each occurance has one of the meanings defined herein, in particular one of those mentioned herein as preferred
  • both variables R 0 in formula (II-1) and (II- 2), respectively, are independently selected from unsubstituted C2-C6-alkandiyl which is preferably linear, such as 1,2-ethandiyl (CH2-CH2), 1,3-propandiyl or 1,4-butandiyl, and in particular 1,2-ethandiyl.
  • both variables R 0 in formula (II-1) or (II-2) are identical to each other.
  • M/REUCTR-054-PC 33 In a preferred subgroup (7.1) of group (7) of embodiments the both variables R 0 in formula (II-1) or (II-2) are both -CH2-CH2-.
  • both variables a 1 and b 1 of formula (II-1) or both variables a 2 and b 2 of formula (II-2) are idependently selected from 0 to 4 and in particular from 0 to 2.
  • both variables a 1 and b 1 of formula (II-1) or both variables a 2 and b 2 of formula (II-2) are 1.
  • the moieties A 1a and A 2a in formula (II-1) or the moieties A 1b and A 2b in formula (II-2) are both O.
  • the moiety Z 1 in formula (II-1) or the moi- ety Z 2 in formula (II-2) is selected from a single bond and a fluorene ring which is un- substituted or substituted by 1, 2 or 3, in particular 1 or 2, identical or different radi- cals R'"', where R'"' in each case is selected from the group consisting of chlorine, fluo- rine, methyl, methoxy, CN, phenyl and naphthyl, such as 1-naphthyl or 2-naphthyl.
  • the moiety Z 1 in formula (II-1) or the moiety Z 2 in formula (II-2) is selected from a single bond and a fluorene ring which is substituted by 2 identical radicals R'"', which are located in equivalent po- sitions of the fluorene ring, such as e.g. in positions 2 and 7 or in positions 3 and 8, where the radicals R'"' have the meaning defined above, in particular one of the pre- ferred meanings mentioned herein.
  • the moiety Z 1 in formula (II-1) or the moiety Z 2 in formula (II-2) is selected from a single bond and an fluorene ring which is unsubstituted.
  • both radicals R 1 and R 2 of formula (II-1) re- spectively (II-2), if present, are independently selected from the group consisting of halogen, C2-C3-alkynyl, CN, R 11a and OR 11a , where R 11a is in particular selected from the group consisting of benzyl, mono- or polycyclic aryl having from 6 to 18 carbon atoms as ring atoms or are mono- or polycyclic hetaryl having a total of 5 to 18 atoms, which are ring members, where 1, 2, 3 or 4, in particular 1 or 2, of these ring member atoms of hetaryl are selected from nitrogen, sulfur and oxygen, while the remainder of these M/REUCTR-054-PC 34 ring member atoms of hetaryl are carbon atoms, where aryl and hetaryl are unsubsti- tuted or carry a substituent R'".
  • both radicals R 1 and R 2 of formula (II-1) or (II-2), if present, are independently selected from the group con- sisting of halogen, C 2 -C 3 -alkynyl, CN, R 11a and OR 11a , where R 11a is selected from benzyl and mono- or polycyclic aryl having from 6 to 18 carbon atoms as ring atoms and mono- or polycyclic hetaryl having from 5 to 18 atoms as ring members, where 1, 2, 3 or 4, in particular 1 or 2, of these ring member atoms nitrogen, sulfur or oxygen, while the remainder of are carbon atoms.
  • R 11a is preferably selected here from benzyl, phe- nyl, naphthyl, phenanthrenyl, triphenylenyl, dibenzo[b,d]thiophenyl and thianthrenyl, more preferably from benzyl, phenyl, naphthyl, phenanthrenyl and thianthrenyl, which radicals may be unsubstituted or may carry a substituent R'" preferably selected from phenyl, halogen, especially fluorine or chlorine, and CN.
  • R' preferably selected from phenyl, halogen, especially fluorine or chlorine, and CN.
  • the variables m 1 and n 1 or m 2 and n 2 are independently 0 or 1.
  • both variables m 1 and n 1 of formula (II-1) or both variables m 2 and n 2 of for- mula (II-2) are 0, i.e. the aromatic core of the structural unit of formula (II-1) and (II- 2), respectively, is devoid of substituents R 1 and R 2 .
  • both variables m 1 and n 1 of formula (II-1) or both variables m 2 and n 2 of formula (II-2) are 1, i.e.
  • R 1 and R 2 pref- erably are independently selected from fluorine, chlorine, CN, phenyl, phenoxy, naph- thyl, such as 1-naphthyl or 2-naphthyl, naphthyloxy, such as 1- or 2-naphthyloxy, phe-
  • variables R 11a , R h1 , R, R', R", R'" and s either alone or preferably in combination with each other and with the meanings and preferred meanings of the variables A 1a , A 2a , A 1b , A 2b , R 0 , R 1 , R 2 , Z 1 , Z 2 , a 1 , a 2 , b 1 , b 2 , n 1 , n 2 , m 1 and m 2 described above, have the meanings de- fined above, and in particular the meanings mentioned herein as preferred.
  • thermoplastic resins such as especially those selected from polycarbonates, polyestercarbonates, polyesters or mixtures thereof, which com- prise at least one of the above structural units of formulae (II-1) and/or (II-2), can be prepared from corresponding monomers.
  • these monomers are of formulae (VI-1) and (VI-2), which are derived from formu- lae (II-1) or (II-2) by replacing the moieties #-A 1a and #-A 2a or #-A 1b and #-A 2b with groups capable of being converted in particular into ester or carbonate linkages, such as especially OH or C(O)OR x , where R x is in preferably selected from hydrogen, phenyl, benzyl and C1-C4-alkyl.
  • the monomers of formula (VI-1) or (VI-2) can be prepared in analogy to procedures well known in the art, as described e.g.
  • resin compositions comprising at least one aromatic polycarbonate, aromatic polyestercarbonate, aromatic polyester or mixture thereof, where the resins included in these compositions are made up of structural units which comprise at least one of a structural units represented by formula (II-3) below: where M/REUCTR-054-PC 36 # represents a connection point to a neighboring structural unit; C 1 and C 2 are independently selected from the group consisting of a mono- or polycy-mann arylene having from 6 to 26 carbon atoms as ring members and a mono- or polycyclic hetarylene having a total of 5 to 26 atoms, which are ring members, where 1, 2, 3 or 4 of these ring member atoms of hetarylene are selected from nitrogen, sulfur and oxygen, while the remainder of these ring member atoms of hetarylene are carbon atoms, where mono- or polycyclic arylene
  • R 11a has in particular one of the preferred meanings given for R 11 in the context of formulae (I) and (Ia).
  • the variables A 1c , A 2c , R 1 , R 2 , C 1 , C 2 , R Ar , p and q on their own or pref- erably in any combination preferably have the following meanings:
  • the moieties A 1c and A 2c in formula (II-3) are both -CH2O.
  • the variables C 1 and C 2 in formula (II-3) are independently selected from the group consisting of mono- or polycyclic arylene having from 6 to 22, in particular 6 to 18, carbon atoms as ring members and mono- or poly- cyclic hetarylene having from 9 to 24, in particular 9 to 20, atoms as ring members, where 1, 2, 3 or 4 of these atoms are nitrogen, oxygen or sulfur atoms, and in particu- lar 1, 2 or 3, such as 1 or 2, of these atoms are oxygen or sulfur atoms, while the re- mainder of these atoms are carbon atoms, where mono- or polycyclic arylene and mono- or polycyclic hetarylene are unsubstituted or carry 1, 2, 3 or 4, in particular 1 or 2, radicals R Ar , where R Ar has one of
  • C 1 and C 2 are inde- pendently selected from the group consisting of phenylene, naphthylene, bi- phenylylene, benzo[b]furanylene, dibenzo[b,d]furanylene, benzo[b]thienylene, dibenzo[b,d]thienylene, 9H-fluorenylene, oxanthrenylene, thianthrenylene, phenoxathi- inylene, 9H-xanthylene and 9H-thioxanthylene, preferably from the group consisting of phenylene, naphthylene, biphenylylene, dibenzo[b,d]thienylene, 9H-fluorenylene, oxanthrenylene, thianthrenylene, phenoxathiinylene, 9H-xanthylene and 9H-thioxanth- ylene, and in particular from the group consisting
  • C 1 and C 2 have the same meaning.
  • the one or more radicals RAr in formula (II-3) are selected from the group consisting of R, OR and NR 2 , especially R and OR, where R Ar may be identical or different if more than one R Ar is present on the same (het)aryl group.
  • R has one of the meanings defined herein and is in par- ticular selected from the group consisting of methyl, ethyl, phenyl, benzyl, naphthyl, such as 1-naphthyl or 2-naphthyl, and phenanthrenyl, such as 9-phenanthrenyl, in par- ticular from phenyl, benzyl and naphthyl, where R may be substituted with 1 or 2 radi- cals R'" and preferably is unsubstituted.
  • the one or more radicals R Ar are preferably selected from the group consisting of C1-C4-alkyl, phenyl, benzyl, naphthyl, phenanthrenyl, C1-C4-alkoxy, phenoxy, ben- zyloxy, naphthyloxy, phenanthrenyloxy, di(C 1 -C 4 -alkyl)amino, diphenylamino, dibenzyl- amino, dinaphthylamino, and diphenanthrenylamino, and especially from the group consisting of phenyl, benzyl, naphthyl, phenoxy, benzyloxy and naphthyloxy.
  • both radicals R 1 and R 2 of formula (II-3), if present, are independently selected from the group consisting of halogen, C2-C3-al- kynyl, CN, R 11a and OR 11a , where R 11a is in particular selected from the group consisting of benzyl, mono- or polycyclic aryl having from 6 to 18 carbon atoms as ring atoms or are mono- or polycyclic hetaryl having a total of 5 to 18 atoms, which are ring mem- bers, where 1, 2, 3 or 4, in particular 1 or 2, of these ring member atoms of hetaryl are selected from nitrogen, sulfur and oxygen, while the remainder of these ring member atoms of hetaryl are carbon atoms, where aryl and hetaryl are un
  • both radicals R 1 and R 2 of formula (II-3), if present, are independently selected from the group consisting of halogen, C 2 -C 3 -alkynyl, CN, R 11a and OR 11a , where R 11a is selected from benzyl and mono- or polycyclic aryl having from 6 to 18 carbon atoms as ring atoms and mono- or polycyclic hetaryl having from 5 to 18 atoms as ring members, where 1, 2, 3 or 4, in particular 1 or 2, of these ring member atoms nitrogen, sulfur or oxygen, while the re- mainder of are carbon atoms.
  • R 11a is preferably selected here from benzyl, phenyl, naphthyl, phenanthrenyl, triphenylenyl, dibenzo[b,d]thiophenyl and thianthrenyl, more preferably from benzyl, phenyl, naphthyl and thianthrenyl, which radicals may be un- substituted or may carry a substituent R'" preferably selected from phenyl, halogen, especially chlorine or fluorine, and CN.
  • the radicals R 1 and R 2 of formula (II-3), if present, are independently selected from fluorine, chlo- rine, CN, phenyl, phenoxy, naphthyl, such as 1-naphthyl or 2-naphthyl, naphthyloxy, M/REUCTR-054-PC 39 such as 1- or 2-naphthyloxy, phenanthrenyl, such as 9-phenanthrenyl, and thi- anthrenyl, such as 1-thianthrenyl or 2-thianthrenyl.
  • formula (II-3) Particular preference is given here to structural units of formula (II-3), where the radicals R 1 and R 2 have the same mean- ing.
  • the formula (II-3) is represented by the formula (II-3b), where each of the variables A 1c , A 2c , R 1 , R 2 , C 1 and C 2 has the meanings defined herein, in particular one of those mentioned herein as preferred.
  • thermoplastic resins such as especially those selected from polycarbonates, polyestercarbonates, polyesters or mixtures thereof, which com- prise at least one of the above structural units of formula (II-3), can be prepared from corresponding monomers.
  • thermoplastic resin may have structural units different therefrom.
  • these further structural units are derived from aromatic monomers of the formula (IV) resulting in structural units of the formula (V): HO-R z -A 3 -R z -OH (IV) #-O-R z -A 3 -R z -O-# (V) where # represents a connection point to a neighboring structural unit;
  • a 3 is a polycyclic radical bearing at least 2 benzene rings, wherein the benzene rings may be connected by W and/or directly fused to each other and/or fused by a non-benzene carbocycle and/or fused by two non-benzene carbocycles that are linked via a linker L, where A 3 is unsubstituted or substituted by 1, 2 or 3 radicals R aa , which are selected from the group consisting of halogen, C 1 -C 6 -alkyl, C 5 -C 6 - cycloalkyl, phenyl, naphthyl,
  • R z in formula (IV) is O-Alk 5 -C(O)
  • the esters, in particular the C1-C4-alkyl esters, of the monomers of formula (IV) may be used instead.
  • a 3 is in particular either a polycyclic radical bearing 2 benzene or naphthaline rings, wherein the benzene rings are connected by W or fused by two non-benzene carbocycles that are linked via a linker L, where W is in particular selected from the group consisting of a single bond, S, S(O), SO2, C(CH3)2, and a radical A' and where L is a single bond or C1-C4-alkylene.
  • R z is in particular O-Alk 4 -, where Alk 4 is in par- ticular linear alkandiyl having 2 to 4 carbon atoms and especially O-CH2CH2.
  • monomers of formula (IV) preference is given to monomers of the gen- eral formulae (IV-1) to (IV-8) M/REUCTR-054-PC 42 where a and b are 0, 1, 2 or 3, in particular 0 or 1; a’ and b’ are 0, 1, 2 or 3, in particular 0 or 1; c and d are 0, 1, 2, 3, 4 or 5, in particular 0 or 1; e and f are 0, 1, 2, 3, 4 or 5, in particular 0 or 1; W’ is S, S(O), SO 2 , O, single bond, CH 2 , CH(CH 3 ), C(CH 3 ) 2 , in particular S, S(O), SO 2 or C(CH 3 ) 2 ; and where R z , R
  • M/REUCTR-054-PC 46 where M/REUCTR-054-PC 47 a and b are 0, 1, 2 or 3, in particular 0 or 1; a’ and b’ are 0, 1, 2 or 3, in particular 0 or 1; c and d are 0, 1, 2, 3, 4 or 5, in particular 0 or 1; e and f are 0, 1, 2, 3, 4 or 5, in particular 0 or 1; W’ is S, S(O), SO 2 , O, single bond, CH 2 , CH(CH 3 ), C(CH 3 ) 2 , in particular S, S(O), SO 2 or C(CH 3 ) 2 ; and where R z , R aa , R ab , R 7a , R 7b and L are as defined for formula (V) and where R z is in particular selected from a single bond, CH 2 and
  • the thermoplastic resin of the present invention comprises at least one structural unit of the formulae (II-1), (II-2) and/or (II- 3) 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-12), structural units of the for- mula (V-13), structural units of the formula (V-14), structural units of the formula (V- 15), structural units of the formula (V-21) and structural units of the formula (V-22).
  • thermoplastic resins are preferred, where in the structural units of the formulae (V-11), (V-12), (V-13), (V-14), (V-15), (V-21) and (V-22) the radicals R z are O-CH2CH2.
  • the total molar ratio of the structural units of the formulae (II-1), (II-2) and/or (II-3), herein also called the structural units of formula (II), is in the range from 1 to 99 mol-%, preferably in the range from 5 to 98 mol-%, further preferably in the range from 10 to 97 mol-%, and even further preferably in the range from 20 to 95 mol-% of the total amount of structural units of the formula (II) and (V).
  • the compounds of the formulae (IV), (IV-1), (IV-2), (IV-3), (IV-4), (IV-5), (IV-6), (IV- 7), (IV-8), (IV-11), (IV-12), (IV-13), (IV-14), (IV-15), (IV-16), (IV-17), (IV-18), (IV- 19), (IV-20), (IV-21) and (IV-22) are known or can be prepared by analogy to known methods.
  • the compounds of the formula (IV-8) can be prepared by various synthe- sis methods, as disclosed e.g. in JP Publication No. 2014-227387, JP Publication No. 2014-227388, JP Publication No. 2015-168658, and JP Publication No. 2015-187098.
  • 1,1’-binaphthols may be reacted with ethylene glycol monotosylates; al- ternatively, 1,1’-binaphthols may be reacted with alkylene oxides, halogenoalkanols, or alkylene carbonates; and alternatively, 1,1’-binaphthols may be reacted with ethylene carbonates.
  • the compounds of the formula (IV-8) are obtained, where R z -OH is O-Alk 2 - or O-Alk 2 -[O-Alk 2 -]p-.
  • the compounds of the formula (IV-2) can be prepared by various synthe- sis methods, as disclosed e.g.
  • Examples include: (a) reacting fluorenes with hydroxy naphthalenes in the presence of hydrochloride gas and mercapto-carboxylic acid; (b) reacting 9-fluorene with hydroxy naphthalenes in the presence of acid catalyst (and alkyl mercaptan); M/REUCTR-054-PC 50 (c) reacting fluorenes with hydroxy naphthalenes in the presence of hydrochloride and thiols (such as, mercapto-carboxylic acid); (d) reacting fluorenes with hydroxy naphthalenes in the presence of sulfuric acid and thiols (such as, mercapto-carboxylic acid) and thereafter to crystallize the product from a crystallization solvent which consists of hydrocarbons and a polar solvent(s) to form bisnaphthol fluorenes with hydroxy naphthalenes in the presence of hydrochloride gas
  • compounds of the formula (IV-2) can be obtained, where R z is a single bond.
  • the compounds of formulae (IV), where R z is O-Alk 2 - or O-Alk 2 -[O-Alk 2 -] p - can be pre- pared from compounds of formulae (IV), where R z is a single bond, by reaction with al- kylene oxides or haloalkanols.
  • 9,9-bis(hydroxynaphthyl)-fluo- renes of the formula (IV-2) where R z is a single bond with alkylene oxides or haloalka- nols results in the compounds of the formula (IV-2) where R z is O-Alk 2 - or O-Alk 2 -[O- Alk 2 -] p -.
  • 9,9-bis[6-(2-hydroxyethoxy)naphthyl] fluorene can be prepared by reacting 9,9-bis[6-(2-hydroxynaphthyl] fluorene with 2-chloroethanol under alkaline conditions.
  • the monomers of formulae (VI-1), (VI-2) and or (VI-3), herein also called monomers of formula (VI), and likewise the co-monomers of formula (IV) used for producing the thermoplastic resin may contain impurities resulting from their preparation, e.g. hy- droxy compounds, which bear an OH group instead of e.g. a group O-CH 2 CH 2 -OH.
  • the total amount of such impurity compounds is preferably 5000 ppm or lower, more pref- erably 3000 ppm or lower, still more preferably 2000 ppm or lower, and especially preferably 1000 ppm or lower.
  • the total content of the impurities in the monomers used for preparing the thermoplastic resin is preferably 4000 ppm or lower in particular 1500 ppm or lower, and more preferably 1000 ppm or lower, and even more prefera- bly 500 ppm or lower.
  • the amount of impurities in the co-monomers of for- mula (IV) will be in the range given for the monomers of formula (VI).
  • Suitable resin compositions of the present invention for the preparation of optical de- vices, such as lenses comprise thermoplastic resins, that are in particular polycar- bonates, polyestercarbonates and polyesters.
  • Preferred resin compositions for the preparation of optical devices, such as lenses comprise thermoplastic resins that are in particular polycarbonates.
  • Said polycarbonates are structurally characterized by having structural units of at least one of the formulae (II-1), (II-2) and (II-3), respectively, optionally structural units de- rived from diol monomers, which are different from the monomer compound of the for- mula (VI), e.g. structural units of the formula (V), #-O-R z -A 3 -R z -O-# (V) M/REUCTR-054-PC 51 where #, R z and A 3 are as defined herein above; and a structural unit of formula (III-1) stemming from the carbonate forming compo- nent: (III-1) where each # represents a connection point to a neighboring structural unit, i.e.
  • polyesters are structurally characterized by having structural units of at least one of the formulae (II-1), (II-2) and (II-3), respectively, optionally structural units derived from diol monomers which are different from the monomer compound of the formula (VI), e.g. structural units of the formula V.
  • the polyesters may have structural units derived from one or more dicarboxylic acids, e.g.
  • each variable # represents a connection point to a neigh- boring structural unit, i.e. typically to O of the connection point of the structural unit of the formula (II) and, if present, to O of the connection point of the structural unit of the formula (V).
  • Said polyestercarbonates are structurally characterized by having structural units of at least one of the formulae (II-1), (II-2) and (II-3), respectively, optionally structural units derived from diol monomers which are different from the monomer compound of the formula (VI), e.g. structural units of the formula (V), a structural unit of formula (III-1) stemming from the carbonate forming component and structural units derived from dicarboxylic acid, e.g.
  • thermo- plastic copolymer resins such as in particular polycarbonates, polyestercarbonates and polyesters, which have both structural units of formula (II), i.e. structural units of for- mula (II-1), (II-2) or (II-3), and one or more structural units of formula (V), i.e.
  • resins in particular polycarbonates, polyestercarbonates and polyesters, which are obtainable by reacting at least one monomer of formula (VI) with one or more monomers of for- mula (IV).
  • the molar ratio of monomers of formula (VI) to monomers of formula (IV) and likewise the molar ratio of the structural units of formula (II) to struc- tural units of formula (V) are in the range from 1:99 to 99:1, in particular in the range from 10:90 to 99:1 and especially in the range from 15:85 to 97:3.
  • the molar ratio of the structural units of the formula (II) is usually from 1 to 99 mol-% in particular from 10 to 99 mol-%, and specifically in range from 15 to 97 mol-%, based on the total molar amount of structural units of the formulae (II) and (V). Accordingly, the molar ratio of the structural units of the formula (V) is usually from 1 to 99 mol-%, in particular from 1 to 90 mol-%, especially in the range from 3 to 85 mol-% based on the total molar amount of structural units of the formulae (II) and (V).
  • thermo- plastic copolymer resins such as in particular polycarbonates, polyestercarbonates and polyesters, which have both structural units of formula (II) and one or more structural units of formulae (V-11), (V-12), (V-13), (V-14), (V-15), (V-21) or (V-22), i.e.
  • resins in particular polycarbonates, polyestercarbonates and polyesters, which are obtainable by reacting at least one monomer of formula (VI) with one or more monomers of formu- lae (IV-11), (IV-12), (IV-13), (IV-14), (IV-15), (IV-21) or (IV-22).
  • the mo- lar ratio of monomers of formula (VI) to monomers of formulae (IV-11), (IV-12), (IV- 13), (IV-14), (IV-15), (IV-21) and (IV-22) and likewise the molar ratio of the structural units of formula (II) to structural units of formulae (V-11), (V-12), (V-13), (V-14), (V- 15), (V-21) and (V-22) are in the range from 1:99 to 99:1, in particular in the range from 10:90 to 99:1, and especially in the range from 15:85 to 97:3.
  • thermoplastic copolymer resins contained in the resin compostions of the present invention such as a polycarbonate resin, may include either one of a random copoly- mer structure, a block copolymer structure, and an alternating copolymer structure.
  • the thermoplastic resin contained in a resin composition according to the present in- vention does not need to include one or more of structural units (II) and one or more M/REUCTR-054-PC 53 different structural units (V) in one, same polymer molecule.
  • the thermoplastic copolymer resin according to the present invention may be a blend resin as long as the above-described structures are each included in any of a plurality of polymer mole- cules.
  • the thermoplastic resin including structural units (II) and structural units (V) described above may be a mixture of a homopolymer or a copolymer includ- ing at least one structural unit (II) and a homopolymer or a copolymer including at least one structural unit (V) or it may be a blend resin of a copolymer including at least one structural unit (II) and a first structural unit (V) and a copolymer including at least one structural unit (II) and at least one other structural unit (V) different from the first structural units (V); etc.
  • thermoplastic polycarbonates are obtainable by polycondensation of a diol component and a carbonate forming component.
  • thermoplastic polyesters and polyester- carbonates are obtainable by polycondensation of a diol component and a dicarboxylic acid, or an ester forming derivative thereof, and optionally a carbonate forming compo- nent.
  • thermoplastic resins polycarbonate resins
  • a method for preparing the thermoplastic resin preferably contained in the resin com- positions of the present invention, such as a polycarbonate resin includes a process of melt polycondensation of a dihydroxy component corresponding to the above-men- tioned structural units and a diester carbonate.
  • the dihydroxy compound preferably comprises at least one dihydroxy compound represented by the formula (VI), in partic- ular by at least one of formulae (VI-1), (VI-2) or (VI-3), as defined herein.
  • the dihydroxy compound may also comprise one or more dihydroxy compounds represented by the formula (IV), preferably by the formu- lae (IV-1) to (IV-8), in particular by the formulae (IV-11) to (IV-22), and especially by the formulae (IV-11), (IV-12), (IV-13), (IV-14), (IV-15), (IV-21) or (IV-22).
  • the polycarbonate resin can be formed by reacting a dihy- droxy component with a carbonate precursor, such as a diester carbonate, where the dihydroxy component preferably comprises at least one compound represented by the formulae (VI-1), (VI-2) and (VI-3), respectively, or a combination of at least one com- pound represented by the formulae ((VI-1), (VI-2) and (VI-3), respectively, and at least one compound represented by the formulae (IV), (IV-1), (IV-2), (IV-3), (IV-4), (IV-5), (IV-6), (IV-7), (IV-8), (IV-11), (IV-12), (IV-13), (IV-14), (IV-15), (IV-16), (IV- 17), (IV-18), (IV-19), (IV-20), (IV-21) or (IV-22).
  • a carbonate precursor such as a diester carbonate
  • the dihydroxy component preferably comprises at least one compound represented by the formulae (VI-1), (VI-2) and (VI-3), respectively, or a combination of at least
  • a polycarbonate resin can be formed by a melt polycondensation process in which the compound represented by the formulae (VI-1), (VI-2) and (VI-3), respectively, or a combination thereof with at least one compound of the formulae (IV), (IV-1), (IV-2), (IV-3), (IV-4), (IV-5), (IV- M/REUCTR-054-PC 54 6), (IV-7), (IV-8), (IV-11), (IV-12), (IV-13), (IV-14), (IV-15), (IV-16), (IV-17), (IV-18), (IV-19), (IV-20), (IV-21) or (IV-22) and a carbonate precursor, such as a diester car- bonate, are reacted in the presence of a basic compound catalyst, a transesterification catalyst, or a mixed catalyst thereof, or in the absence of a catalyst.
  • a carbonate precursor such as a diester car- bonate
  • thermoplastic resin (or a polymer) other than a polycarbonate resin, such as polyes- tercarbonates and polyesters is preferably obtained by using the dihydroxy compound represented by the formulae (VI-1), (VI-2) and (VI-3), respectively, or a combination thereof with at least one compound represented by the formulae (IV), (IV-1), (IV-2), (IV-3), (IV-4-), (IV-5), (IV-6), (IV-7), (IV-8), (IV-11), (IV-12), (IV-13), (IV-14), (IV-15), (IV-16), (IV-17), (IV-18), (IV-19), (IV-20), (IV-21) or (IV-22) as a material (or a mono- mer).
  • the monomers of formula (VI) and likewise the co-monomers of formula (IV) used for producing the thermoplastic resin may contain impurities result- ing from their preparation.
  • the monomers of the formulae (IV-1) and (IV-2), where R z is O-Alk 2 - or O-Alk 2 -[O-Alk 2 -]p- may include a dihydroxy compound in which both R z are a single bond, or a dihydroxy compound in which one of R z is a single bond, instead of O-Alk 2 - or O-Alk 2 -[O-Alk 2 -] p -.
  • the total amount of such dihydroxy compounds of the formulae (IV-1) or (IV-2) in which at least one of R z differs from O-Alk 4 - or O-Alk 4 -[O-Alk 4 -] w -, is preferably 3000 ppm or lower, more preferably 1500 ppm or lower, still more preferably 1000 ppm or lower, and especially preferably 500 ppm or lower; in the monomer(s) of which main component is the dihydroxy compound(s) represented by the formulae (IV- 1) or (IV-2).
  • the total content of the dihydroxy compounds in which at least one of the values of a and b or c and d differs from the formula (IV-1) or (IV-2) is still preferably 300 ppm or lower, and more preferably 200 ppm or lower.
  • the polycarbonate resins can be obtained by reacting the monomer compounds of the formula (VI) or by reacting combination of at least one monomer compound of the for- mula (VI), in particular at least one monomer (VI) mentioned herein as preferred, and one or more monomer compounds of the formula (IV), and in particular of the formu- lae (IV-11), (IV-12), (IV-13), (IV-14), (IV-15), IV-21) or (IV-22), and the like, as dihy- droxy components; with carbonate precursors, such as diester carbonates.
  • thermoplastic resin contained in the resin composition of the present invention may also contain minor amount of impurities, for example, as extra contents of ther- moplastic resin composition or a part of the polymer skeleton of the thermoplastic resin.
  • the examples of such impurities include phenols formed by a process for form- ing the thermoplastic resin, unreacted diester carbonates and monomers.
  • the total amount of impurities in the thermoplastic resin may be 5000 ppm or lower, or 2000 ppm or lower.
  • the total amount of impurities in the thermoplastic resin is prefer- ably 1000 ppm or lower, more preferably 500 ppm or lower, still more preferably 200 ppm or lower, and especially preferably 100 ppm or lower.
  • the total amount of phenols as impurities in the thermoplastic resin may be 3000 ppm or lower, or 2000 ppm or lower.
  • the total amount of phenols as impurities is prefera- bly 1000 ppm or lower, more preferably 800 ppm or lower, still more preferably 500 ppm or lower, and especially preferably 300 ppm or lower.
  • the total amount of diester carbonates as impurities in the thermoplastic resin is pref- erably 1000 ppm or lower, more preferably 500 ppm or lower, still more preferably 100 ppm or lower, and especially preferably 50 ppm or lower.
  • the total amount of unreacted monomers as impurities in the thermoplastic resin is preferably 3000 ppm or lower, more preferably 2000 ppm or lower, still more prefera- bly 1000 ppm or lower, and especially preferably 500 ppm or lower.
  • the lower limit of the total amount of these impurities is not important, but may be 0.1 ppm, or 1.0 ppm.
  • the total amount of residual heavy metals, e.g. palladium, as impurity in the thermo- plastic resin is preferably 50 ppm or lower, more preferably 10 ppm or lower.
  • the amount of residual palladium can be reduced by standard procedures like treatment with an adsorbent, e.g. active charcoal.
  • Thermoplastic resins having targeted characteristics can be formed by adjusting the amounts of phenols and diester carbonates.
  • the amounts of phenols, diester car- bonates, and monomers can be suitably adjusted by arranging the conditions for poly- condensation, the working conditions of devices used for polymerization, or the condi- tions for extrusion molding after the polycondensation process.
  • the weight-average molecular weight (Mw), as determined by GPC (gel permeation chromatography), of the resin, in particular the thermoplastic resin, contained in the resin composition according to the present invention is preferably in the range from 5000 to 100000 Dalton, more preferably 10000 to 80000 Dalton or 20000 to 65000 Dalton, especially in the range of 10000 to 50000 Dalton or 20000 to 40000 Dalton.
  • the GPC measurments may be calibrated by using polystyrene standards.
  • the Mw of a thermoplastic resin determined this way is also denoted herein as “polystyrene conver- sion weight-average molecular weight”.
  • the number-average molecular weight (Mn) of the thermoplastic resin contained in the resin according to the present invention is preferably in the range of 3000 to 30000, more preferably 5000 to 25000, and espe- cially in the range of 7000 to 20000.
  • the viscosity-average molecular weight (Mv) of the thermoplastic resin according to the present invention is preferably in the range from 8000 to 28000, more preferably 9000 to 22000, and still more preferably 10000 to 18000.
  • the value of the molecular weight distribution (Mw/Mn) of the thermoplastic resin con- tained in the resin compositon 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.
  • the resin composition according to the present invention can be prepared by mixing at least one compound of formulae (I), (Ia) or (Ib) with thermoplastic resin, such as in particular at least one of the thermoplastic resins described herein as preferred.
  • Mixing is preferably continued until a homogenous or almost homogenous compositon is ob- tained.
  • the mixing is accomplised by adding at least one compound of formulae (I), (Ia) or (Ib) and at least one thermoplastic resin into a suita- ble reactor and agitating this combination at an elevated temperature of from 100 to 350°C, preferably 200 to 300°C, in particular 240 to 290°C, and specifically 250 to 280°C over to a period of time to obtain at least almost homogeneous blend.
  • the pressure in the reactor may be kept close to the atmospheric pressure, i.e. in range of about 80 to 120 kPa.
  • the pressure within the re- actor may also me reduced to below 50 kPa, preferably to below 40 or 30 kPa, such as to pressure of 5 to 50 kPa, preferably 10 to 40 kPa and especially 15 to 30 kPa.
  • the resin composition according to the present invention preferably comprises 5 to 50 % by weight, in particular 10 to 40 % by weight and especially 15 to 30 % by weight, 18 to 27 % by weight, 20 to 25 % by weight or 22 to 27 % by weight of at least one compound of formulae (I), (Ia) or (Ib), and accordingly 50 to 95 % by weight, in particular 60 to 90 % by weight and especially 70 to 85 % by weight, 73 to 82 % by weight, 75 to 80 % by weight or 73 to 78 % by weight of thermoplastic resin, such as in particular one of the thermoplastic resin described herein as preferred.
  • thermoplastic resin contained in the resin compositon of the invention comprises 9% by weight or less, in particular 7% by weight or less and especially 5% by weight or less, e. g.
  • thermo- plastic resin 0.1 to 9% by weight, in particular 0.1 to 7% by weight and es- pecially 0.1 to 5% by weight, of low molecular weight compounds having molecular weight of less than 1000, based on the total weight of the thermoplastic resin, where the low molecular weight compounds are different from compounds of formulae (I), (Ia) and (Ib). If such low molecular weight compounds are present in the thermo- plastic resin in an amount within the above ranges, the mechanical strength of a molded body made from the resin composition containing the thermoplastic resin is commonly increased, especially compared to a molded body made from a resin compo- sition comprising thermoplastic resin with a higher amount of the low molecular weight compounds.
  • the resin compositions of the present invention such as especially those containing the above-mentioned polycarbonate resins, have a high refractive index (n D or n d ) and thus are suitable to an optical lens.
  • the values of the refractive index as referred herein are values of a film having a thickness of 0.1 mm may be measured by use of an Abbe refractive index meter by a method of JIS-K-7142.
  • the refractive index of the resin compositions of the present invention is, espe- cially in case the resin includes a structural unit (II), frequently 1.640 or higher, prefer- ably 1.650 or higher, more preferably 1.660 or higher, still more preferably 1.670 or higher, in particular 1.680 or higher, 1.685 or higher, or 1.690 or higher, and specifi- cally 1.695 or higher.
  • a structural unit (II) frequently 1.640 or higher, prefer- ably 1.650 or higher, more preferably 1.660 or higher, still more preferably 1.670 or higher, in particular 1.680 or higher, 1.685 or higher, or 1.690 or higher, and specifi- cally 1.695 or higher.
  • the refractive index of the resin composition com- prising a compound of formula (I) as additive and a copolycarbonate resin including at one or more of the the structural units (II) and optionally a structural unit (V) as de- scribed above is typically 1.640 to 1.730, preferably 1.650 to 1.730, preferably 1.660 to 1.730, still more preferably 1.670 to 1.730 or 1.680 to 1.730.
  • the refractive index of the resin composition according to the present invention is typi- cally 0.001 or more, preferably 0.01 or more, in particular 0.05 or more, and specifi- cally 0.1 or more higher than that of a reference resin composition having the same composition but without the compounds of formulae (I), (Ia) or (Ib), where the refer- ence resin usually corresponds to the thermoplastic resin contained in the resin compo- sition.
  • the Abbe number ( ⁇ or ⁇ d) of the resin composition of the present invention is typically 24 or lower, preferably 22 or lower, more preferably 20 or lower, even more preferably 19 or lower, and still more preferably 18 or lower, or 18.5 or lower, and specifically 17 or lower, or 17.5 or lower.
  • the Abbe number of the resin composition according to the present invention is typi- cally 0.05 or more, preferably 0.1 or more, more preferably 0.15 or more, in particular 0.2 or more, and specifically 0.25 ore more lower than that of a reference resin compo- sition having the same composition but without the compounds of formulae (I), (Ia) or (Ib), where the reference resin usually corresponds to the thermoplastic resin con- tained in the resin composition.
  • the glass transition temperature (Tg) of the resin composition of the present inven- tion is, in consideration of that the composition is usable for injection molding, frequently in the range of 90 to 185°C, preferably in the range of 90 to 150°C, more preferably in the range of 90 to 140°C, even more preferably in the range of 90 to 135°C or 95 to 135°C.
  • the lower limit of Tg is preferably 105°C and more preferably 110°C
  • the upper limit of Tg is preferably 160°C and more preferably 140°C.
  • a glass transition temperature (Tg) in the above given ranges provides a significant range of usable temperature and avoids the risk that the melting temperature of the resin composition may be too high, and thus the resin may be undesirably decomposed or colored. What is more, it allows for preparing molds having have a high surface accuracy.
  • the values given for the glass transition temperature refer to the values measured by differential scanning calorime- try (DSC) using a 10°C/minute heating program according to the protocol of JIS K7121-1987.
  • the glass transition temperature (Tg) of the resin composition according to the present invention is typically 5(°C) or more, preferably 10(°C) or more, more preferably 15(°C) or more, in particular 20(°C) or more, and specifically 25(°C) ore more lower than that of a reference resin composition having the same composition but without the com- pounds of formulae (I), (Ia) or (Ib), where the reference resin usually corresponds to the thermoplastic resin contained in the resin composition.
  • An optical molded body such as an optical element produced by using a resin composi- tion of the present invention has a total light transmittance of preferably 85% or M/REUCTR-054-PC 59 higher, more preferably 87% or higher, and especially preferably 88% or higher.
  • a to- tal light transmittance of preferably 85% or higher is as good as that provided by bi- sphenol A type polycarbonate resin or the like.
  • the resin composition according to the present invention has high moisture and heat resistance.
  • the moisture and heat resistance may be evaluated by performing a "PCT test" (pressure cooker test) on a molded body such as an optical element produced by use of the resin composition and then measuring the total light transmittance of the molded body after the PCT test.
  • PCT test pressure cooker test
  • an injection molded body having a diameter of 50 mm and a thickness of 3 mm is kept for 20 hours with PC305S III made by HIRAYAMA Corporation under the conditions of 120°C, 0.2 MPa, 100%RH for 20 hours.
  • the resin composition according to the present invention has a post-PCT test total light transmittance of 60% or higher, preferably 70% or higher, more preferably 75% or higher, still more preferably 80% or higher, and especially preferably 85% or higher. As long as the total light transmittance is 60% or higher, the resin composition is con- sidered to have a higher moisture and heat resistance than that of the conventional thermoplastic resin.
  • the resin composition according to the present invention has a b value, which repre- sents the hue, of preferably 5 or lower. As the b value is smaller, the color is less yel- lowish, which is good as a hue.
  • the diol component which is used in the preparation of the polycarbonates or polyesters contained in the resin composition, may additionally com- prise one or more diol monomers, which are different from the monomer compound of the formula (VI), such as one or more monomers of the formula (IV).
  • Suitable diol monomers, which are different from the monomer compound of the for- mula (VI) are those, which are conventionally used in the preparation of polycar- bonates, e.g.
  • - aliphatic diols such as ethylene glycol, propanediol, butanediol, pentanediol and hexanediol; - alicyclic diols such as tricyclo[5.2.1.02,6]decane dimethanol, cyclohexane-1,4-di- methanol, decalin-2,6-dimethanol, norbornane dimethanol, pentacyclopentadecane dimethanol, cyclopentane-1,3-dimethanol, spiroglycol, 1,4:3,6-dianhydro-D-sorbi- tol, 1,4:3,6-dianhydro-D-mannitol and 1,4:3,6-dianhydro-L-iditol are also included in examples of the diol; and M/REUCTR-054-PC 60 - aromatic diols, in particular aromatic diols of the formula (IV) such as bis(4-hydroxyphenyl)
  • the relative amount of monomer compound of formula (VI), based on the total weight of the diol component is at least 30 % by weight, preferably at least 50% or at least 70% by weight, in particular at least 85% by weight, especially at least 95% by weightor at leats 99 % by weight, typically in the range of 30 to 100% by weight, preferably in the range of 50 to 100% by weight, in particular in the range of 70 to 100% by weight, especially in the range of 85 to 100% by weight, specifically in the range of 90 to 100% by weight or even 95 to 100% by weight.
  • the relative molar amount of monomer compound of formula (IV), based on the total molar amount of the diol component, will not exceed 70 mol-% or 50 mol-% or 30 mol-%, in particular not exceed 15 mol-% and especially not exceed 5 mol-% or 1 mol-%, and is preferably in the range of 0 to 70 mol-% or in the range of 0 to 50 mol-% or in the range of 0 to 30 mol-% or in the range of 0 to 15 mol-%, in particular in the range of 0 to 5 mol-% or in the range of 0 to 1 mol-%.
  • the total molar amount of monomers of formula (VI) and monomers of for- mula (IV) is at least 80 mol-%, in particular at least 90 mol-%, especially at least 95 mol-% or up to 100 mol-%, based on the total molar amount of the diol monomers in the diol component.
  • Examples of further preferred aromatic dihydroxy compound, which can be used in ad- dition to the monomers of formula (I) and optionally monomers of formula (IV) in- M/REUCTR-054-PC 61 clude, but are not limited to bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bi- sphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, bisphenol Z and the like.
  • the monomers forming the thermoplastic polymer contained in the resin composition of the present invention may also include a monofunctional compound, in case of polycarbonates a monofunc- tional alcohol and in case of polyesters a monofunctional alcohol or a monofunctional carboxylic acid.
  • Suitable monoalcohols are butanol, hexanol and octanol.
  • Suitable mon- ocarboxylic acids include e.g. benzoic acid, propionic acid and butyric acid.
  • the monomers forming the ther- moplastic polymer may also include a polyfunctional compound, in case of polycar- bonates a polyfunctional alcohol having three or more hydroxyl groups and in case of polyesters a polyfunctional alcohol having three or more hydroxyl groups or a polyfunc- tional carboxylic acid having three or more carboxyl groups.
  • Suitable polyfunctional al- cohols are e.g. glycerine, trimethylol propane, pentaerythrit and 1,3,5-trihydroxy pen- tane.
  • Suitable polyfunctional carboxylic acids having three or more carboxyl groups are e.g. trimellitic acid and pyromellitic acid.
  • Suitable carbonate forming monomers are those, which are conventionally used as carbonate forming monomers in the preparation of polycarbonates, include, but are not limited to phosgene, diphosgene and diester carbonates such as diethyl carbonate, diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate and dinaphthyl carbonate. Out of these, diphenyl carbonate is particularly preferred.
  • the carbonate forming monomer is frequently used at a ratio of 0.97 to 1.20 mol, and more preferably 0.98 to 1.10 mol, with respect to 1 mol of the dihydroxy compound(s) in total.
  • 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]decane dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, decalin-2,6-dicarboxylic acid, and norbornandi- carboxylic acid; and - aromatic dicarboxylic acids, such as benzene dicarboxylic acids, specifically phthalic acid, isophthalic acid, 2-methylterephthalic acid or terephthalic acid
  • Suitable ester forming derivatives of dicarboxylic acids include, but are not limited to the dialkyl esters, the diphenyl esters and the ditolyl esters.
  • the ester forming monomer is frequently used at a ratio of 0.97 to 1.20 mol, and more preferably 0.98 to 1.10 mol, with respect to 1 mol of the dihy- droxy compound(s) in total.
  • the polycarbonates contained in resin composition of the present invention can be pre- pared by reacting a diol component comprising a monomer of formula (VI) and option- ally a further diol monomer such as a monomer of the formula (IV) and a carbonate forming monomer by analogy to the well known preparation of polycarbonates as de- scribed e.g. in US 9,360,593, US 2016/0319069 and US 2017/0276837, to which full reference is made.
  • polyesters contained in resin composition of the present invention can be prepared by reacting a diol component comprising a monomer of formula (VI) and optionally a further diol monomer such as a monomer of the formula (IV) and a dicarboxylic acid or its ester forming derivative by analogy to the well known preparation of polyesters as described e.g. in US 2017/044311 and the references cited therein, to which full refer- ence is made.
  • the polyestercarbonates contained in resin composition of the present invention can be prepared by reacting a diol component comprising a monomer of formula (VI) and optionally a further diol monomer such as a monomer of the formula (IV), a carbonate M/REUCTR-054-PC 63 forming monomer and a dicarboxylic acid or its ester forming derivative by analogy to the well known preparation of polyestercarbonates as described in the art.
  • the polycarbonates, polyesters and polyestercarbonates are usually prepared by react- ing the monomers of the diol component with the carbonate forming monomers and/or the ester forming monomers, i.e.
  • Suitable transesterification catalysts are basic compounds, which specifically include but are not limited to alkaline metal compounds, alkaline earth metal compound, nitro- gen-containing compounds, and the like.
  • suitable transesterification catalysts are acidic compounds, which specifically include but are not limited to Lewis acid com- pounds of polyvalent metals, including compounds such as zinc, tin, titanium, zirco- nium, lead, and the like.
  • alkaline metal compound examples include alkaline metal salts of an organic acid such as acetic acid, stearic acid, benzoic acid, or phenylphorsphoric acid, alkaline metal phenolates, alkaline metal oxides, alkaline metal carbonates, alkaline metal boro- hydrides, alkaline metal hydrogen carbonates, alkaline metal phosphate, alkaline metal hydrogenphosphate, alkaline metal hydroxides, alkaline metal hydrides, alkaline metal alkoxides, and the like.
  • organic acid such as acetic acid, stearic acid, benzoic acid, or phenylphorsphoric acid
  • alkaline metal phenolates alkaline metal oxides, alkaline metal carbonates, alkaline metal boro- hydrides, alkaline metal hydrogen carbonates, alkaline metal phosphate, alkaline metal hydrogenphosphate, alkaline metal hydroxides, alkaline metal hydrides, alkaline metal alkoxides, and the like.
  • Specific examples thereof include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stea- rate, cesium stearate, lithium stearate, sodium borohydride, sodium borophenoxide, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, and disodium phenylphosphate; and also include disodium salt, dipotassium salt, dice- sium salt, dilithium salt of bisphenol A, sodium salt, potassium salt, cesium salt and lithium salt of phenol; and the like.
  • alkaline earth metal compound examples include alkaline earth metal salts of an organic acid such as acetic acid, stearic acid, benzoic acid, or phenylphorsphoric acid, alkaline earth metal phenolates, alkaline earth metal earth oxides, alkaline earth metal carbonates, alkaline metal borohydrides, alkaline earth metal hydrogen carbonates, al- kaline earth metal hydroxides, alkaline earth metal hydrides, alkaline earth metal alkoxides, and the like.
  • organic acid such as acetic acid, stearic acid, benzoic acid, or phenylphorsphoric acid
  • alkaline earth metal phenolates alkaline earth metal earth oxides
  • alkaline earth metal carbonates alkaline metal borohydrides
  • alkaline earth metal hydrogen carbonates al- kaline earth metal hydroxides
  • alkaline earth metal hydrides alkaline earth metal alkoxides, and the like.
  • Specific examples thereof include magnesium hydroxide, cal- cium hydroxide, strontium hydroxide, barium hydroxide, magnesium hydrogen car- bonate, calcium hydrogen carbonate, strontium hydrogen carbonate, barium hydrogen M/REUCTR-054-PC 64 carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium car- bonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, mag- nesium stearate, calcium stearate, calcium benzoate, magnesium phenylphosphate, and the like.
  • the nitrogen-containing compound include quaternary ammoniumhydrox- ide, salt thereof, amines, and the like.
  • quaternary ammoniumhydroxides including an alkyl group, an aryl group or the like, such as tetra- methylammoniumhydroxide, tetraethylammoniumhydroxide, tetrapropylammoniumhy- droxide, tetrabutylammoniumhydroxide, trimethylbenzylammoniumhydroxide, 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-methylim- idazole, 2-phenylimidazole, benzoimidazole, and the like; bases or basic salts such as ammonia, tetramethylammoniumborohydride, tetrabutylammoniumboro
  • transesterification catalyst examples include salts of polyvalent metals such as zinc, tin, titanium, zirconium, lead, and the like, in particular the chlorides, alkoxyides, alkanoates, benzoates, acetylacetonates and the like. They may be used in- dependently or in a combination of two or more.
  • transesteri- fication catalyst examples include zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin chloride (II), tin chloride (IV), tin acetate (II), tin acetate (IV), dibutyltinlaurate, dibutyltinoxide, dibutyltinmethoxide, zirconiumacetylacetonate, zirconium oxyacetate, zirconiumtet- rabutoxide, lead acetate (II), lead acetate (IV), and the like.
  • the transesterification catalyst are frequently used at a ratio of 10 -9 to 10 -3 mol, prefer- ably 10 -7 to 10 -4 mol, with respect to 1 mol of the dihydroxy compound(s) in total.
  • the polycarbonates, polyesters and polyestercarbonates are prepared by a melt polycondensation method. In the melt polycondensation the monomers are re- acted in the absence of an additional inert solvent. While the reaction is performed any byproduct formed in the transesterification reaction is removed by heating the reaction mixture at ambient pressure or reduced pressure.
  • the melt polycondensation reaction preferably comprises charging the monomers and catalyst into a reactor and subjecting the reaction mixture to conditions, where the re- action between the monomers and the formation of the byproduct takes place.
  • the byproduct resides for at least a while in the polycon- densation reaction.
  • the pressure may be controlled by closing the reactor, or by increasing or decreasing the pressure.
  • the reaction time for this step is 20 minutes or longer and 240 minutes or shorter, preferably 40 minutes or longer and 180 minutes or shorter, and especially preferably 60 minutes or longer and 150 minutes or shorter.
  • the finally obtained thermoplastic resin has a low content of high molecular-weight resin molecules.
  • 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 in a batch system.
  • the reactor usable for the reaction may be of a vertical type including an anchor-type stirring blade, a Maxblend ® stirring blade, a helical ribbon-type stirring blade or the like; of a horizontal type including a paddle blade, a lattice blade, an eye glass-type blade or the like; or an extruder type including a screw.
  • a reactor including a combination of such reactors is preferably usable in consideration of the viscosity of the polymerization product.
  • the method for producing the thermoplastic resin, such as a polycar- bonate resin after the polymerization reaction is finished, the catalyst may be removed or deactivated in order to maintain the thermal stability and the hydrolysis stability.
  • a preferred method for deactivating the catalyst is the addition of an acidic substance.
  • the acidic substance include esters such as butyl benzoate and the like; aromatic sulfonates such as p-toluenesulfonic acid and the like; aromatic sul- fonic acid esters such as butyl p-toluenesulfonate, hexyl p-toluenesulfonate, and the like; phosphoric acids such as phosphorous acid, phosphoric acid, phosphonic acid, and the like; phosphorous acid esters such as triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, di-n-butyl phosphite, di-n- hexyl phosphite, dioctyl phosphite, monooctyl phosphite, and the like; phosphoric acids such
  • deactivators are frequently used at 0.01 to 50 mol, preferably 0.3 to 20 mol, with respect to the catalyst.
  • the distillation is preferably performed at reduced pressure, e.g. at a pressure of 0.1 to 1 mm Hg at a temperature of 200 to 350°C.
  • a horizontal device including a stirring blade having a high surface renewal capability such as a paddle blade, a lattice blade, an eye glass-type blade or the like, or a thin film evaporator is preferably used.
  • the thermoplastic resin such as a polycarbonate resin has a very small amount of foreign objects. Therefore, the molten product is preferably filtered to remove any solids from the melt.
  • the mesh of the filter is preferably 5 ⁇ m or less, and more preferably 1 ⁇ m or less. It is preferred that the generated polymer is filtrated by a polymer filter.
  • the mesh of the polymer filter is preferably 100 ⁇ m or less, and more preferably 30 ⁇ m or less.
  • a step of sampling a resin pellet needs to be performed in a low dust environment, needless to say.
  • the dust environment is preferably of class 6 or lower, and more preferably of class 5 or lower.
  • the resin composition may be molded by any conventional molding procedure for pro- ducing optical elements.
  • Suitable molding procedures include but are not limited to in- jection molding, compression molding, casting, roll processing, extrusion molding, ex- tension and the like. While it is possible to mold the resin composition of the invention as such, it is also possible to mold a resin composition, which contains at least one thermoplastic resin as described herein and which further contains at least one additive and/or further resin.
  • Suitable additives include antioxidants, processing stabilizers, photostabilizers, polymerization metal deactivators, flame retardants, lubricants, antistatic agents, sur- factants, antibacterial agents, releasing agents, ultraviolet absorbers, plasticizers, com- patibilizers, and the like.
  • Suitable further resins are e.g.
  • antioxidants include but are not limited to triethyleneglycol-bis[3-(3- tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-bu- tyl-4-hydroxyphenyl)propionate], pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydrox- yphenyl)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-
  • thermoplastic resin is preferably 0.001 to 0.3 parts by weight with respect to 100 parts by weight of the thermoplastic resin.
  • processing stabilizer examples include but are not limited to phosphorus-based processing stabilizers, sulfur-based processing stabilizers, and the like.
  • phosphorus-based processing stabilizer examples include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, esters thereof, and the like.
  • triphenylphosphite tris(nonylphenyl)phosphite, tris(2,4-di-tert-bu- tylphenyl)phosphite, tris(2,6-di-tert-butylphenyl)phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite, dioctylmonophe- nylphosphite, diisopropylmonophenylphosphite, monobutyldiphenylphosphite, monodecyldiphenylphosphite, monooctyldiphenylphosphite, bis(2,6-di-tert-butyl-4- methylphenyl)pentaerythritoldiphosphite,
  • the content of the phosphorus-based pro- cessing stabilizer in the thermoplastic resin composition is preferably 0.001 to 0.2 parts by weight with respect to 100 parts by weight of the thermoplastic resin.
  • the sulfur-based processing stabilizer include but are not limited to pen- taerythritol-tetrakis(3-laurylthiopropionate), pentaerythritol-tetrakis(3-myristylthiopropi- onate), pentaerythritol-tetrakis(3-stearylthiopropionate), dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, and the like.
  • the con- tent of the sulfur-based processing stabilizer in the thermoplastic resin compositon is preferably 0.001 to 0.2 parts by weight with respect to 100 parts by weight of the ther- moplastic resin.
  • Preferred releasing agents contain at least 90% by weight of an ester of an alcohol and a fatty acid.
  • Specific examples of the ester of an alcohol and a fatty acid include an ester of a monovalent alcohol and a fatty acid, and a partial ester or a total ester of a polyvalent alcohol and a fatty acid.
  • Preferred examples of the above-described ester M/REUCTR-054-PC 68 of an alcohol and a fatty acid include the esters of a monovalent alcohol having a car- bon number of 1 to 20 and a saturated fatty acid having a carbon number of 10 to 30.
  • Preferred examples of partial or total esters of a polyvalent alcohol and a fatty acid in- clude the partial or total ester of a polyvalent alcohol having a carbon number of 2 to 25 and a saturated fatty acid having a carbon number of 10 to 30.
  • ester of a monovalent alcohol and a fatty acid examples include stearyl stearate, palmityl pal- mitate, butyl stearate, methyl laurate, isopropyl palmitate, and the like.
  • Specific exam- ples of the partial or total ester of a polyvalent alcohol and a fatty acid include mono- glyceride stearate, monoglyceride stearate, diglyceride stearate, triglyceride stearate, monosorbitate stearate, monoglyceride behenate, monoglyceride caprylate, mono- glyceride laurate, pentaerythritol monostearate, pentaerythritol tetrastearate, pentae- rythritol tetrapelargonate, propyleneglycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexy
  • the content of the releasing agent in the resin composition is preferably 0.005 to 2.0 parts by weight, more preferably 0.01 to 0.6 parts by weight, and still more preferably 0.02 to 0.5 parts by weight, with re- spect to 100 parts by weight of the thermoplastic resin.
  • Preferred ultraviolet absorbers are selected from the group consisting of benzotriazole- based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, cyclic iminoester-based ultraviolet absorbers, and cyanoacrylate- based ultraviolet absorbers. Namely, the following ultraviolet absorbers may be used independently or in a combination of two or more.
  • benzotriazole-based ultraviolet absorbers examples include 2-(2-hydroxy-5- methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hy- droxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5- methylphenyl)-5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6- (2N-benzotriazole-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- amylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-o
  • benzophenone-based ultraviolet absorbers examples include 2,4-dihydroxybenzo- phenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid hydrate, 2,2'-dihydroxy-4-methoxy- benzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethox- ybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodiumsulfoxybenzophenone, bis(5- M/REUCTR-054-PC 69 benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophe- none, 2-hydroxy-4-methoxy-2
  • triazine-based ultraviolet absorbers examples include 2-(4,6-diphenyl-1,3,5-triazine- 2-yl)-5-([(hexyl)oxy]-phenol, 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5- ([(octyl)oxy]-phenol, and the like.
  • cyclic iminoester-based ultraviolet absorbers examples include 2,2'-bis(3,1-benzoxa- zine-4-one), 2,2'-p-phenylenebis(3,1-benzoxazine-4-one), 2,2'-m-phenylenebis(3,1- benzoxazine-4-one), 2,2'-(4,4'diphenylene)bis(3,1-benzoxazine-4-one), 2,2'-(2,6-naph- thalene)bis(3,1-benzoxazine-4-one), 2,2'-(1,5-naphthalene)bis(3,1-benzoxazine-4-one), 2,2'-(2-methyl-p-phenylene)bis(3,1-benzoxazine-4-one), 2,2'-(2-nitro-p-phe- nylene)bis(3,1-benzoxazine-4-one), 2,2'-(2-chloro-p-phenylene)bis(
  • cyanoacrylate-based ultraviolet absorbers examples include 1,3-bis-[(2'-cyano-3',3'- diphenylacryloyl)oxy]-2,2-bis(((2-cyano-3,3-diphenylacryloyl)oxy)methyl)propane, 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene, and the like.
  • the content of the ultraviolet absorber in the resin composition is preferably 0.01 to 3.0 parts by weight, more preferably 0.02 to 1.0 parts by weight, and still more prefer- ably 0.05 to 0.8 parts by weight, with respect to 100 parts by weight of the thermo- plastic resin.
  • thermoplastic polymer resins contained in the resin composi- tions of the present invention in particular the polycarbonate resins comprising repeat- ing units of formulae (II-1), (II-2) and (II-3), respectively, as described herein, provide high transparency and high refractive index to thermoplastic resins.
  • the resin composi- tions of the present invention containing these thermoplastic polymer resins are there- fore suitable for preparing optical devices, where high transparency and high refractive index is required.
  • the resin compositions of the present invention con- taining these thermoplastic polycarbonates having structural units of formulae (II-1), (II-2) and (II-3), respectively, are characterized by having 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 monomer of the formulae (VI-1), (VI-1 and (VI-3), respectively, to the refractive index of the thermoplastic resin, in particular a polycarbonate resin, contained in the resin composition of the invention will depend from the refractive in- dex of said monomer and the relative amount of said monomer in the thermoplastic M/REUCTR-054-PC 70 resin.
  • thermoplastic resin comprising structural units of the formula (II) can be calculated from the refractive indices of the monomers used for preparing the thermoplastic resin, either from the refractive index of the mon- omers or ab initio, e.g. by using the computer software ACD/ChemSketch 2012 (Ad- vanced Chemistry Development, Inc.).
  • the refractive index of the thermoplastic resin in particular a polycarbonate resin
  • n Dn are the refractive in- dices of the homopolymers synthesized from only one of the monomers 1, 2, .... n at a time.
  • x1, x2, .... xn are the mass fractions of the OH mono- mers 1, 2, .... n, based on the total amount of OH monomer. It is apparent that a higher refractive index of a homopolymer will result in a higher refractive index of the copolymer.
  • the refractive indices of the resin composition of the present invention and of thermo- plastic resins contained therein can be determined directly, whereas the refractive indi- ces of the thermoplastic resins can also be determinted indirectly.
  • the refractive indices n D of the resin compositions or the thermoplastic resins are measured at wavelength of 589 nm in accordance with the protocol JIS-K-7142 us- ing an Abbe refractometer and applying a 0.1 mm film of the composition or the resin.
  • the refractive indices of the homopolycarbonates of the compounds of for- mula (VI) can also be determined indirectly.
  • a co-poly- carbonate of the respective monomer of formula (VI) with 9,9-bis(4-(2-hydroxyeth- oxy)phenyl)fluorene and diphenyl carbonate is prepared according to the protocol of example 1 in column 48 of US 9,360,593 and the refractive indices nD of the co-poly- carbonate is measured at wavelength of 589 nm in accordance with the protocol JIS-K- 7142 using an Abbe refractometer and applying a 0.1 mm film of the co-polycarbonate.
  • M/REUCTR-054-PC 71 The compounds of formula (VI) can be obtained in a purity, which provides for a low yellowness index Y.I., as determined in accordance with ASTM E313, which may also be important for the use in the preparation of optical resins.
  • the yellowness index Y.I. as determined in accordance with ASTM E313, of the compounds of formula (VI) preferably does not exceed 100, more prefer- ably 50, even more preferably 20, in particular 10 or 5.
  • the resin composition according to the present invention has a high refractive index and a low Abbe number.
  • the resin composition of the present invention can be used for producing a transparent conductive substrate usable for a liquid crystal display, an organic EL display, a solar cell and the like.
  • the resin composition of the present invention can be used as a structural material for optical parts, such as, optical disks, liquid crystal panels, optical cards, optical sheets, optical fibers, connectors, evaporated plastic reflecting mirrors, displays, and the like; or used as optical devices suitable for functional material purpose.
  • optical devices can be formed using the resin compositions of the present invention.
  • the optical devices include optical lenses, and optical films.
  • the specific examples of the optical devices include lenses, films, mirrors, filters, prisms, and so on.
  • These optical devices can be formed by arbitrary production process, for example, by injection molding, compression molding, injection compres- sion molding, extrusion molding, or solution casting. Because of an excellent moldability and a high heat resistance, the resin compositions of the present invention are very suitable for production of optical lenses which re- quires injection molding.
  • the resin compositions of the present invention may further include other thermoplastic res- ins, for example, different polycarbonate resin, polyestercarbonate resin, polyester resin, and other resins, in mixed form.
  • the resin compositions of the present invention can be mixed with addi- tives for forming the optical devices, which are different from the compounds of for- mula (I), (Ia) or (Ib).
  • additives for forming the optical devices the above- mentioned ones can be used.
  • additives may include antioxidants, processing stabilizers, photostabilizers, polymerization metal deactivators, flame retardants, lubri- cants, antistatic agents, surfactants, antibacterial agents, releasing agents, ultraviolet absorbers, plasticizers, compatibilizers, and the like.
  • the resin composiiton M/REUCTR-054-PC 72 comprises a compound of formulae (I), (Ia) or (Ib) and a thermoplastic resin prefera- bly comprising a structural unit represented by the formula (II) and optionally of for- mula (V).
  • An optical device made of an optical resin composition as defined herein are usually optical molded articles such as optical lenses, for example car head lamp lenses, Fres- nel lenses, f ⁇ lenses for laser printers, camera lenses, lenses for glasses and projection lenses for rear projection TV's, CD-ROM pick-up lenses, but also optical disks, optical elements for image display media, optical films, film substrates, optical filters or prisms, liquid crystal panels, optical cards, optical sheets, optical fibers, optical con- nectors, eposition plastic reflective mirrors, and the like.
  • optical lenses and optical films are usually optical molded articles such as optical lenses, for example car head lamp lenses, Fres- nel lenses, f ⁇ lenses for laser printers, camera lenses, lenses for glasses and projection lenses for rear projection TV's, CD-ROM pick-up lenses, but also optical disks, optical elements for image display media, optical films, film substrates, optical filters or prisms, liquid crystal panels, optical cards, optical sheets, optical fibers, optical con- nectors, eposition plastic reflective mirrors,
  • Optical resin compositions comprising com- pounds of formulae (I), (Ia) or (Ib) and a thermoplastic resin preferably having a structural unit represented by the formula (II) and optionally of formula (V) are also useful for producing a transparent conductive substrate usable for an optical device suitable as a structural member or a functional member of a transparent conductive substrate for a liquid crystal display, an organic EL display, a solar cell and the like.
  • the optical lens produced from the resin composition according to the present inven- tion has a high refractive index, a low Abbe number and a low degree of birefringence, and is highly moisture and heat resistant.
  • the optical lens can be used in the field in which a costly glass lens having a high refractive index is conventionally used, such as for a telescope, binoculars, a TV projector and the like. It is preferred that the optical lens is used in the form of an aspherical lens. Merely one aspherical lens may make the spherical aberration substantially zero. Therefore, it is not neces- sary to use a plurality of spherical lenses to remove the spherical aberration. Thereby the weight and the production cost of a device including the spherical aberration is de- creased. An aspherical lens is useful especially as a camera lens among various types of optical lenses.
  • the present invention easily provides an aspherical lens having a high refractive index and a low level of birefringence, which is technologically difficult to produce by processing glass.
  • An optical lens of the present invention may be formed, for example, by injection molding, compression molding, injection compression molding or casting the resin composition comprising a compound of formula (I) and a thermoplasting resin prefera- bly having repeating units of the formula (II) and optionally repeating units of the for- mula (V) as defined herein.
  • the optical lens of the present invention is characterized by a small optical distortion.
  • An optical lens comprising a conventional optical resin has a large optical distortion.
  • the condition widths are very small, thereby making molding extremely dif- ficult. Since the resin composition including a compound (I) and a thermoplastic resin with repeating units of the formula (II) and optionally repeating units of the formula (V) as defined herein has an extremely small optical distortion caused by the orienta- tion of the resin and a small molding distortion, an excellent optical element can be ob- tained without setting molding conditions strictly.
  • the lens should be molded at a cylinder temperature of 260°C to 320°C and a mold temperature of 100°C to 140°C.
  • the optical lens of the present invention is advantageously used as an aspherical lens as required. Since spherical aberration can be substantially nullified with a single as- pherical lens, spherical aberration does not need to be removed with a combination of spherical lenses, thereby making it possible to reduce the weight and the production cost. Therefore, out of optical lenses, the aspherical lens is particularly useful as a camera lens.
  • resin compositions including a compound (I) and a thermoplastic resin preferably having repeating units of the formula (II) and optionally repeating units of the formula (V) as defined herein have a high moldability, they are particularly useful as the mate- rial of an optical lens, which is thin and small in size and has a complex shape.
  • the thickness of the center part of the lens is 0.05 to 3.0 mm, preferably 0.05 to 2.0 mm, more preferably 0.1 to 2.0 mm.
  • the diameter of the lens is 1.0 to 20.0 mm, preferably 1.0 to 10.0 mm, more preferably 3.0 to 10.0 mm. It is preferably a meniscus lens, which is convex on one side and concave on the other side.
  • the surface of the optical lens of the present invention may have a coating layer such as an antireflection layer or a hard coat layer as required.
  • the antireflection layer may be a single layer or a multi-layer and composed of an organic material or inorganic ma- terial but preferably an inorganic material.
  • the inorganic material include oxides and fluorides such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, magnesium oxide and magnesium fluoride.
  • the optical lens of the present invention may be formed by an arbitrary method such as metal molding, cutting, polishing, laser machining, discharge machining or edging. Metal molding is preferred.
  • An optical film produced by the use of the thermoplastic resin composition according to the present invention is high in transparency and heat resistance, and therefore is preferably usable for a liquid crystal substrate film, an optical memory card or the like.
  • M/REUCTR-054-PC 74 In order to avoid foreign objects from being incorporated into the optical film as much as possible, the molding needs to be performed in a low dust environment, needless to say.
  • the dust environment is preferably of class 6 or lower, and more preferably of class 5 or lower. The following examples serve as further illustration of the invention. 1.
  • DBNBNA 2,2'-bis(benzyloxy)-1,1’-binaphthalene
  • Example 2a Synthesis of 2'-(benzyloxy)-1,1'-binaphthalen-2-ol (building block 1; BnBNA) M/REUCTR-054-PC 76 To a mixture of racemic 1,1’-bi-2-naphthol (250 g, 873 mmol, 1.0 eq.) and K 2 CO 3 (350 g, 2.53 mol, 2.9 eq
  • Example 2b Synthesis of ethane-1,2-diyl bis(4-methylbenzene-1-sulfonate) (building block 2; EGDT)
  • a solution of ethylene glycol (50.0 g, 806 mmol, 1.0 eq.) in THF (450 g) was added a solution of NaOH (74.1 g, 1.85 mol, 2.3 eq.) in water (100 g) and stirred at r.t. for 2 h.
  • the mixture was then cooled to 0 °C and tosyl chloride (307 g, 1.61 mol, 2.0 eq.) was added portionwise over 2 h. Stirring was continued at 0 °C for 2 h.
  • BnBNA see Example 2a; 279
  • Example 3a Synthesis of [([1,1'-binaphthalene]-2,2'-diyl)bis(oxy)ethane-2,1-diyl] di- methanesulfonate (building block 3; BHBNADMs) 2,2'-Bis(2-hydroxyethoxy)-1,1'-binaphthyl (BHBNA; 300 g, 801 mmol, 1.0 eq.) and TEA (335
  • Methanesulfonyl chloride (186 mL, 2.40 mol, 3.0 eq.) was then added dropwise. Stirring was continued at 0°C for an additional 2 h and the reaction mixture was then allowed to warm to r.t.. The reaction mixture was stirred until TLC showed complete conversion. Water was added and the phases were separated. The organic phase was washed with a saturated aqueous solution of NaHCO3, dried over Na2SO4 and the solvent was removed in vacuo to give the crude product. The material M/REUCTR-054-PC 78 was stirred in acetone (500 g) at reflux for 1 h, followed by cooling to r.t.
  • BnBNA see Example 2a; 50.0 g, 133 mmol,
  • Refractive index (nD) The refractive index was measured using a disk shaped test piece with a thickness of 3 mm made by resin or resin composition as a test piece according to JIS B 7071- 2:2018. The measurement was conducted at 23 ⁇ C using the refractive index measure- ment device below.
  • Refractive index measurement device M/REUCTR-054-PC 81 KPR-3000 manufactured by Shimadzu Corporation Abbe number A disk shaped test piece with a thickness of 3 mm which is same as the test piece used in the refractive index measurement was used.
  • the refractive index values were meas- ured using the refractive index measurement device below at 23°C and at wavelengths of 486 nm, 589 nm and 656 nm. Then, the Abbe number was calculated using the be- low-described formula.
  • Differential scanning calorimetry device X-DSC7000 manufactured by Hitachi High-Tech Science Corporation Molecular weight
  • Mw weight average molecular weight
  • GPC device HLC-8420GPC (from Tosoh Corporation); Columns: three TSKgel SuperHM-M (from Tosoh Corporation), one guard column SuperHM-M (from Tosoh Corporation), one TSKgel SuperH-RC (from Tosoh Corporation); Detection Device: RI detection Standard polystyrene: PstQuick C as standard polystyrene kit (from Tosoh Corpora- tion); Eluent: tetrahydrofuran; Flow rate of eluent: 0.6 ml/min; M/REUCTR-054-PC 82 Column temperature: 40°C.
  • the number average molecular weight (Mn) values can be calculated using similar methods to those used for measuring the Mw values described above.
  • the polystyrene converted weight average molecular weights (Mw) and number average molecular weights (Mn) can be calculated using a previously prepared standard curve of polysty- rene.
  • the standard curve can be prepared using a standard polystyrene for which the molecular weight is known (“PStQuick C” from Tosoh Corporation).
  • a calibration curve can be obtained by plotting the elution time and molecular weight value of each of the peaks based on the measured data of the standard polystyrene, and conducting three-dimensional approximation.
  • the values for Mw and Mn can be calculated based on the following calculation formulae:
  • “i” represents the “i”th dividing point
  • “Wi” represents the molecular weight (g) of the polymer at the “i”th dividing point
  • “Ni” represents the number of the molecules of the polymer at the “i”th dividing point
  • “Mi” represents the molecular mass at the “i”th dividing point.
  • the molecular mass (M) represents the value of the molecular mass of polystyrene at the corresponding elution time in the calibration curve.
  • Contents of low molecular weight compounds (CLWC) The contents of low molecular weight compounds represent area ratios of compounds with the M W values lower than 1.000 on GPC analysis.
  • the GPC analysis of the low molecular weight compounds can be carried out as de- scribed above for measuring the molecular weight of the thermoplastic resins.
  • ⁇ n Birefringence
  • Re phase difference
  • d thickness
  • the criteria of birefringence ( ⁇ n) can be, for example, as shown in the table below.
  • thermoplastic polycarbonate Resin A As materials, 14.6245 g (0.0272 mol) of 2,2'-((9H-fluorene-9,9-diyl)bis(naphthalene- 6,2-diyl))bis(ethan-1-ol) (BNEF), 11.4371 g (0.0305 mol) of 2,2'-bis(2-hydroxyethoxy)- 1,1'-binaphthyl(BNE), 5.3555 g (0.0102 mol) of 2,2'-((6,6'-diphenyl-[1,1'-binaphtha- lene]-2,2'-diyl)bis(oxy))bis(ethan-1-ol) (DPBN), 14.9768 g (0.0699 mol) of diphenylcar- bonate (DPC) and 0.5628 ⁇ 10 -4 g (0.6700 ⁇ 10 -6 mol)
  • the reactor was flushed with nitrogen and the inside pressure was set to 101.3 kPa.
  • the reactor was immersed in an oil bath at 180 °C and then the ester exchange reac- tion started. Stirring of the mixture was started 5 minutes after the start of the reac- tion and 20 minutes later the pressure was reduced from 101.3 kPa to 93.33 kPa over 10 minutes. 10 Minutes later, the oil bath was heated to 190 °C over 10 minutes. Af- ter 10 minutes, the pressure of the reaction mixture was reduced from 93.33 kPa to 26.66 kPa over 10 minutes. Then, the oil bath was heated from 190 °C to 210 °C and the pressure was further reduced to 24.00 kPa over 10 minutes.
  • diol monomers BNEF, BNE and DPBN were used for preparing the ther- moplastic polycarbonate Resin A, see Polymerisation Example 1 above, and the diol monomers BNEF and BNE were used for preparing Resin B, see Polymerisation Exam- ple 2 below.
  • thermoplastic polycarbonate Resin B As materials, 26.2625 g (0.046 mol) of 2,2'-((9H-fluorene-9,9-diyl)bis(naphthalene-6,2- diyl))bis(ethan-1-ol) (BNEF), 7.5267 g (0.0203 mol) of 2,2'-bis(2-hydroxyethoxy)-1,1'- binaphthyl (BNE), 14.9768 g (0.0699 mol) of diphenylcarbonate (DPC) and 0.5628 ⁇ 10 -4 g (0.6700 ⁇ 10 -6 mol) of sodium hydrogen carbonate were put into a 300 milliliter reactor with a stirrer and a distillation device.
  • DPC diphenylcarbonate
  • DPC diphenylcarbonate
  • 0.5628 ⁇ 10 -4 g 0.5628 ⁇ 10 -4 g (0.6700 ⁇ 10 -6 mol) of sodium hydrogen carbonate
  • the reactor was flushed with ni- trogen and the inside pressure was set to 101.3 kPa.
  • the reactor was immersed in an oil bath at 180 °C and then the ester exchange reac- tion started. Stirring of the mixture was started 5 minutes after the start of the reac- tion and the oil bath was heated to 200 °C over 10 minutes. 20 minutes later, the pressure was reduced from 101.3 kPa to 93.33 kPa over 10 minutes. After 50 minutes, the pressure of the reaction mixture was reduced from 93.33 kPa to 26.66 kPa over 10 minutes. 10 Minutes later, the oil bath was heated from 200 °C to 220 °C over 10 minutes and it was further heated to 230 °C over 10 minutes.
  • the oil bath was heated to 250 °C and the pressure was reduced to 24.00 kPa over 10 minutes. After that, the pressure was reduced to 17.33 kPa over 10 minutes. Then, the oil bath was heated to 270 °C and the pressure was reduced to 17.33 kPa over 20 minutes. After 20 minutes the pressure was reduced to 0 kPa over 30 minutes. These conditions were afterwards maintained for 30 minutes. Finally, the pressure was increased back to M/REUCTR-054-PC 85 101.3 kPa by introducing nitrogen into the reactor to obtain the polycarbonate resin (Resin B). The characteristics of the obtained resin are summarized in Table 1 below.
  • the reactor was immersed in an oil bath at 260 °C. Stirring of the mixture at 200 rpm was started 10 minutes after the start of the heating, and 10 minutes later the pres- sure was reduced from 101.3 kPa to 26.7 kPa. These conditions were then maintained for 30 minutes. Finally the pressure was increased back to 101.3 kPa by introducing ni- trogen into the reactor to obtain the desired polycarbonate resin composition.
  • Table 2 The characteristics of the obtained resin composition are summarized in Table 2 below.
  • Example 6 Composition of Resin B and Compound DBBNABHBNA as additive As materials, 6.0348 g of the polycarbonate resin obtained by Polymerization Example 2 (Resin B) and 2.0238 g 2,2'-bis[2-(2-benzyloxy-1,1’-binaphthyl-2’-oxy)-1-ethyloxy]- 1,1'-binaphthalene (DBBNABHBNA, a compound of formula (Ia)) were put into a 10 milliliter reactor with a stirrer and a distillation device. The reactor was flushed with ni- trogen and the inside pressure was set to 101.3 kPa. The reactor was immersed in an oil bath at 260 °C.
  • Comparative Example 2 depicted in Tables 2 and 3 is the polycarbonate resin obtained in Polymerization Example 2 (Resin B). The characteristics of the resin are summarized in Tables 2 and 3.
  • Table 2 DBBNABHBNA Example 7 Composition of Resin A and Compound BNAD4PODCN as additive The composition resin was prepared in analogy to the procedure of Example 5 using Resin A and BNAD4PODCN as additive compound of the formula (Ia). M/REUCTR-054-PC 87 The characteristics of the obtained resin composition are summarized in Table 3 below.
  • Example 8 Composition of Resin B and Compound BNAD4PODCN as additive
  • the composition resin was prepared in analogy to the procedure of Example 6 using Resin B and BNAD4PODCN as additive compound of the formula (Ia).
  • the characteristics of the obtained resin composition are summarized in Table 3 below.
  • Table 3 Example 9: Composition of Resin A and Compound DBNBNA as additive
  • the composition resin was prepared in analogy to the procedure of Example 5 using Resin A and DBNBNA as additive compound of the formula (Ia).
  • the characteristics of the obtained resin composition are summarized in Table 4 below.

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Abstract

La présente invention concerne l'utilisation de composés de formule (I) ou d'un mélange de ceux-ci, qui sont appropriés en tant qu'additifs dans des compositions de résine. Les composés sont appropriés en tant qu'additifs, en particulier, pour des compositions de résine thermoplastique en vue de produire des dispositifs optiques tels que des lentilles optiques. La présente invention concerne également des compositions de résine contenant de tels composés de binaphtyle et une ou plusieurs résines. Dans la formule (I), A1 et A2 sont identiques ou différents et indépendamment choisis parmi des alkylènes en C1-C6 qui sont non substitués ou substitués par 1, 2, 3 ou 4 radicaux 0 identiques ou différents R'"; X1 et X2 sont identiques ou différents et indépendamment choisis dans le groupe constitué par O, C(=O), O-C(=O), S et SO2. Dans la formule (I), Ar1, Ar2, R1, R2, L1, L2, k, l, p et q sont tels que définis dans la description.
PCT/EP2025/064873 2024-05-29 2025-05-28 Composés de binaphtyle utilisés comme additifs dans des compositions de résine Pending WO2025248024A1 (fr)

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