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WO2025088066A1 - Composés binaphtyles oligomères et résines thermoplastiques - Google Patents

Composés binaphtyles oligomères et résines thermoplastiques Download PDF

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Publication number
WO2025088066A1
WO2025088066A1 PCT/EP2024/080131 EP2024080131W WO2025088066A1 WO 2025088066 A1 WO2025088066 A1 WO 2025088066A1 EP 2024080131 W EP2024080131 W EP 2024080131W WO 2025088066 A1 WO2025088066 A1 WO 2025088066A1
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formula
reuctr
rca
trimer
phenyl
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Inventor
Karl Reuter
Philipp KOSCHKER
Vasyl Andrushko
Florian Stolz
Mark Kantor
Björn Schmalzbauer
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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    • 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
    • C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/54—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings
    • C07C13/547—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings at least one ring not being six-membered, the other rings being at the most six-membered
    • C07C13/567—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings at least one ring not being six-membered, the other rings being at the most six-membered with a fluorene or hydrogenated fluorene ring system
    • 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
    • C08G64/16—Aliphatic-aromatic or araliphatic polycarbonates
    • C08G64/1608—Aliphatic-aromatic or araliphatic polycarbonates saturated
    • 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
    • C08G64/305—General preparatory processes using carbonates and alcohols
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • 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
    • C07C2603/24—Anthracenes; Hydrogenated anthracenes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/96—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings spiro-condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
    • C07D339/08—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/10—Spiro-condensed systems
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group

Definitions

  • RCA-EO_Trimer 1 Oligomeric binaphthyl compounds and thermoplastic resins
  • the present invention relates to oligomeric binaphthyl compounds that are suitable as monomers for preparing thermoplastic resins, such as polycarbonate resins, which have beneficial optical and mechanical properties and can be used for pro- ducing optical devices.
  • thermoplastic resins such as polycarbonate resins
  • 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 mold- ing.
  • optical resins in particular, transparent polycarbonate resins, are frequently used for producing camera lenses.
  • resins with a higher refractive index are highly desirable, as they allow for reducing the size and weight of final products.
  • the polycar- bonate resins have beneficial optical properties in terms of a high refractive index, a low Abbe's number, a high degree of transparency, low birefringence, and a glass transition temperature suitable for injection molding.
  • Co-Polycarbonates of monomers of the formula (A) with 10,10-bis(4- hydroxyphenyl)anthrone monomers and their use for preparing optical lenses are described in US 2016/0319069.
  • M/REUCTR-037-PC RCA-EO_Trimer 2 WO 2019/043060 describes thermoplastic resins for producing optical materials, where the thermoplastic resins comprise a polymerized compound of formula (B) where X is e.g.
  • R and R' are identical or different and selected from optionally substituted mono or polycyclic aryl having from 6 to 36 carbon atoms and optionally substituted mono- or polycyclic hetaryl having a total of 5 to 36 atoms.
  • binaphthyl de- rived monomers such as those of formulae A and B above, despite their multiple advantages, suffer from the disadvantage that they form a significant proportion of undesirable cyclic oligomers when used as monomers in the production of thermo- plastic resins such as in the production of polyesters and polycarbonates.
  • cyclic oligomes may aggravate the molecular weight build-up and/or worsen the product properties of the resin, such as reduced mechanical strength, lower glass transition temperature and/or optical properties.
  • those cyclic compo- nents can hardly be removed from the resin in an efficient way.
  • a first aspect of the present invention relates to the use of the com- pound of the formula (I) or a mixture thereof
  • Ar is selected from the group consisting of mono- and polycyclic arylene having from 6 to 40 carbon atoms as ring members and mono- and polycyclic he- tarylene having
  • the compounds of the formula (I) are novel, except for the compound of formula (I), where X 1 and X 2 are both H, Y 1 and Y 2 are both CH 2 CH 2 , E 1 and E 2 are both O and Ar is 1,1’-binaphtalene-2,2’-yl.
  • This compound is known from H. C. Aspinall et al., Tetrahedron 2003, 59(52), 10453-10463.
  • M/REUCTR-037-PC RCA-EO_Trimer 5 Therefore, a second aspect relates to compounds of the formula (I) that are novel.
  • the second aspect relates to compounds of the formula (I) except for the compound of formula (I), where the combination of X 1 , X 2 , Y 1 , Y 2 , E 1 , E 2 and Ar is as follows: X 1 and X 2 are both H, Y 1 and Y 2 are both CH 2 CH 2 , E 1 and E 2 are both O and Ar is 1,1’-binaphtalene-2,2’-yl.
  • a third aspect relates to a thermoplastic resin comprising a polymerized unit of the compound of formula (I), i.e.
  • thermoplastic resin comprising a structural unit rep- resented by formula (II) below; where # represents a connection point to a neighboring structural unit; and where X 1a and X 2a , respectively, is derived from X 1 or X 2 in formula (I) such that, if X 1 or X 2 is hydrogen, hydrogen is replaced by a single bond, or, if X 1 or X 2 is not hydrogen, the -OH or -OR x group of X 1 or X 2 is replaced by an oxo (-O-) unit, and where X 1 , X 2 , Y 1 , Y 2 , E 1 , E 2 , Ar, R 1 , R 2 , R 3 , R 4 , n, m, p, q and s are as defined herein above.
  • the invention further relates to an optical device made of a thermoplastic resin as defined above, in particular from a polyester and especially from a polycarbonate.
  • the present invention relates to the pure stere- oisomers of the compounds of formula (I) and the mixtures of any of the stereoiso- mers, including racemic as well as non-racemic mixtures of the respective two ste- reoisomerswhich together constitute an enantiomeric pair.
  • the term "C 1 -C 4 -alkandiyl group” may alternatively also be designated "alkylene group having 1, 2, 3 or 4 carbon atoms" and refers to a bivalent, saturated, aliphatic hydrocarbon radical having 1, 2, 3 or 4 carbon atoms.
  • C 1 -C 4 -alkandiyl are in particular the methylene group (CH 2 ), linear al- kandiyl such as 1,2-ethandiyl (CH 2 CH 2 ), 1,3-propandiyl (CH 2 CH 2 CH 2 ) and 1,4- butdandiyl (CH 2 CH 2 CH 2 CH 2 ), but also branched alkandiyl such as 1-methyl-1,2- ethandiyl, 1-methyl-1,2-propandiyl, 2-methyl-1,2-propandiyl, 2-methyl-1,3- propandiyl and 1,3-butandiyl.
  • the term “monocyclic aryl” refers to a monovalent aromatic monocyclic radical, such as in particular phenyl.
  • the term “monocyclic hetaryl” refers to a monova- lent heteroaromatic monocyclic radical, i.e.
  • heteroaromatic monocycle linked by a single covalent bond to the remainder of the molecule, where the ring member at- oms are part of a conjugate ⁇ -electron system, where the heteroaromatic monocy- cle 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 monovalent aromatic monocyclic radical as defined herein or to a monovalent aro- matic polycyclic 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 hy- drocarbon where each of the carbon atoms is part of a conjugate ⁇ -electron sys- tem
  • a polycyclic hydrocarbon which bears at least 1 phenyl ring which is fused to a saturated 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 M/REUCTR-037-PC RCA-EO_Trimer 7 which are fused to a saturated or unsaturated 4 to 10-membered mono- or bicyclic hydrocarbon ring.
  • Mono- or polycyclic aryl 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 particular from 6 to 20 carbon atoms, especially 6, 10, 12, 13, 14, 16, 17 or 18 carbon atoms.
  • Polycyclic aryl 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 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 bear- ing 2, 3 or 4 phenyl rings which are directly fused to each other include e.g. naph- thyl, anthracenyl, phenanthrenyl, pyrenyl, triphenylenyl, chrysenyl and ben- zo[c]phenanthrenyl.
  • Polycyclic aryl bearing 2, 3 or 4 phenyl rings which are fused to a saturated or unsaturated 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, phenanthryl, anthracenyl, pyrenyl, chrysenyl, benzo[c]phenanthrenyl, acenaph- thenyl, acenaphthylenyl, 2,3-dihydro-1H-indenyl, 5,6,7,8-tetrahydro-naphthalenyl, cyclopent[fg]acenaphthylenyl, 2,3-dihydrophenalenyl, 9,10-dihydroanthracen-1-yl, 1,2,3,4-tetrahydrophenanthrenyl, 5,6,7,8-tetrahydrophenanthrenyl, fluoranthenyl, benzo[k]fluoranthenyl, biphenylenyl, triphenylenyl, tetraphen
  • the term “mono- or polycyclic hetaryl” refers to a monovalent heteroaromatic monocyclic radical as defined herein or to a monovalent M/REUCTR-037-PC RCA-EO_Trimer 8 heteroaromatic polycyclic radical, i.e. a polycyclic hetarene linked by a single cova- lent 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 polycy-root hetarene are linked to each other by a covalent bond and/or fused to each oth- er directly 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 unsatu- rated 5-, 6-, 7- or 8-membered heterocyclic ring bearing 1, 2 or 3 heteroatoms se- lected 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, ox- epin, thiepin, dioxi
  • 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 un- saturated 4 to 10-membered mono- or bicyclic hydrocarbon ring.
  • Mono- or polycyclic hetaryl 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 atoms, 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 atoms, 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 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 biva- lent heteroaromatic monocyclic radical, i.e.
  • a heteroaromatic monocycle linked by two single covalent bonds to the two remaining parts of the molecule where the ring member atoms are part of a conjugate ⁇ -electron system, where the het- eroaromatic 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 at- oms, 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 bivalent aromatic monocyclic radical as defined herein or to a bivalent aromatic polycyclic radical, i.e. a polycyclic arene linked by two single covalent bonds to the two remaining parts of the molecule, where the polycyclic arene is (i) an aromatic polycyclic hydrocarbon, i.e.
  • a completely unsaturated polycyclic hy- drocarbon where each of the carbon atoms is part of a conjugate ⁇ -electron sys- tem
  • a polycyclic hydrocarbon which bears at least 1 phenyl ring which is fused to a saturated 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 hydrocarbon 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 unsubstitut- ed or carry one or two substitutents selected from C 1 -C 4 -methyl, phenyl
  • Mono- or polycyclic arylene has from 6 to 40, often from 6 to 33 carbon atoms, e.g. 6, 9, 10, 12, 13, 14, 16, 17, 18, 19, 20, 22, 24, 26, 30 or 33 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 arylene typically has 10 to 40 carbon atoms as ring atoms, in particular from 10 to 33 carbon atoms, especially 10, 12, 13, 14, 16, 17, 18, 19, 20, 22, 24, 26, 30 or 33 carbon atoms.
  • polycyclic arylene bearing 2, 3 or 4 phenyl rings which are linked to each other via a single bond include e.g.
  • Polycy-grass arylene bearing 2, 3 or 4 phenyl rings which are directly fused to each other include e.g. naphthylene, anthracenylene, phenanthrenylene, pyrenylene, tri- phenylenylene, chrysenylene and benzo[c]phenanthrenylene.
  • Polycyclic arylene bearing 2, 3 or 4 phenyl 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 heteroaromatic polycyclic radical, i.e. a polycyclic hetarene linked by two single co- valent 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 polycy-root hetarene are linked to each other by a covalent bond and/or fused to each oth- er directly 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 unsatu- rated 5-, 6-, 7- or 8-membered heterocyclic ring bearing 1, 2 or 3 heteroatoms se- lected 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, ox- epin, thiepin, dioxi
  • 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 M/REUCTR-037-PC RCA-EO_Trimer 12 a covalent bond or fused to each other directly and/or fused to a saturated or un- saturated 4 to 10-membered mono- or bicyclic 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 nitro- gen, and are in particular linked by O, S, NR H , SO and SO 2 , where R H is hydrogen, C 1 -C 4 -alkyl, phenyl,
  • Mono- or polycyclic hetarylene has from 5 to 40, often from 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 at- oms are carbon atoms.
  • Polycyclic hetarylene generally has from 9 to 40, often from 9 to 34 ring atoms, in particular 9 to 26 ring atoms, which comprise 1, 2, 3 or 4 at- oms selected from nitrogen atoms, sulphur atoms and oxygen atoms, where the remainder of the ring atoms 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 synony- mously with the 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 com- binations thereof, especially lenses for cameras and lenses for glasses.
  • the remarks made below as to preferred embodiments of the variables (substitu- ents) of the compounds of formula (I) and of the structural units of formula (II) are valid on their own as well as preferably in combination with each other.
  • variables X 1 , X 2 , Y 1 , Y 2 , E 1 , E 2 , R 1 , R 2 , R 3 , R 4 , Ar, n, m, p, q and s on their own or preferably in any combination preferably have the following meanings:
  • the variables X 1 and X 2 in formula (I) are independently selected from hydrogen, -Alk 1 -OH, -CH 2 -A-CH 2 -OH, -Alk 2 -C(O)OR x and -CH 2 -A-C(O)OR x , and accordingly to those variables X 1a and X 2a in formula (II) that are independently selected from -Alk 1 -O-, -CH 2 -A-CH 2 -O-, -Alk 2 -C(O)O- and -CH 2 -A-C(O)O-, where Alk 1
  • the variables X 1 and X 2 in formula (I) are independently selected from -Alk 1 -OH and -CH 2 -A-CH 2 -OH and accordingly the variables X 1a and X 2a in formula (II) are independently selected from -Alk 1 -O- and -CH 2 -A-CH 2 -O-, wherein Alk 1 is preferably a linear C 2 -C 4 -alkandiyl, such as 1,2- ethandiyl (CH 2 -CH 2 ), 1,3-propandiyl or 1,4-butandiyl, and in particular is 1,2- ethandiyl, and A is preferably selected from 1,4-phenylene, 1,3-phenylene, 2,6- naphthylene, 1,4-naphthylene and 1,5-naphthylene.
  • variables X 1 and X 2 in formula (I) or the variables X 1a and X 2a in formula (II) are identical to each other. Accordingly, in a particularly preferred subgroup (1.1) of embodiments the variables X 1 and X 2 in formula (I) are selected from 2-hydroxyethyl (i.e. 2-(HO)-ethyl), hy- droxymethyl-phenyl-methyl (i.e.
  • HO-methyl-phenyl-methyl) and hydroxymethyl- naphthyl-methyl especially from 2-hydroxyethyl, 4-(hydroxymethyl)phenyl)methyl, (3-(hydroxymethyl)phenyl)methyl, (4-(hydroxymethyl)-1-naphthyl)methyl, (5- (hydroxymethyl)-1-naphthyl)methyl and (6-(hydroxymethyl)-2-naphthyl)methyl, and specifically from 2-hydroxyethyl, 4-(hydroxymethyl)phenyl)methyl and (3- (hydroxymethyl)phenyl)methyl.
  • variables X 1a and X 2a in formula (II) are selected from 2(- O)-ethyl, -O-methyl-phenyl-methyl and -O-methyl-naphthyl-methyl, especially from 2(-O)-ethyl, (4(-O- methyl)phenyl)methyl, (3(-O-methyl)phenyl)methyl, (4(-O-methyl)-1- naphthyl)methyl, (5(-O-methyl)-1-naphthyl)methyl and (6(-O-methyl)-2- naphthyl)methyl, and specifically from 2(-O)-ethyl, (4(-O-methyl)phenyl)methyl and (3(-O-methyl)phenyl)methyl.
  • variables X 1 and X 2 in formula (I) have identical meanings and, likewise, the variables X 1a and X 2a in formula (II) have M/REUCTR-037-PC RCA-EO_Trimer 15 identical meanings, which are selected from the meanings defined in groups (1) and (1.1), of embodiments.
  • variables X 1 and X 2 in formulae (I) and (II) are both hydrogen and accordingly the variables X 1a and X 2a in formula (II) are both a single bond.
  • the variables X 1 and X 2 in formula (I) are independently selected from -Alk 2 -C(O)OR x and -CH 2 -A-C(O)OR x and accordingly the variables X 1a and X 2a in formula (II) are independently selected from –Alk 2 - C(O)O- and -CH 2 -A-C(O)O-, wherein Alk 2 is preferably a linear C 1 -C 4 -alkandiyl, such as meth- ylene or 1,2-ethandiyl (CH 2 -CH 2 ), and in particular is methylene, A is preferably se- lected from 1,4-phenylene, 1,3-phenylene, 2,6-naphthylene, 1,5-naphthylene and 1,4-naphthylene, and R x is preferably hydrogen or C 1 -C 4 -alkyl, and in particular is methyl
  • variables X 1 and X 2 or the varia- bles X 1a and X 2a are identical to each other. Accordingly, in a particularly preferred subgroup (3.1) of embodiments the variables X 1 and X 2 in formula (I) are selected from methoxycarbonyl-C 1 -C 4 -alkyl methyl, such as methoxycarbonyl-methyl (i.e. CH 3 O-C(O)-methyl), methoxycarbonyl-phenyl- methyl (i.e.
  • variables X 1a and X 2a in formula (II) are selected from -O-C(O)-methyl, -O-C(O)-phenyl-methyl and -O-C(O)-naphthyl-methyl, especially from -O-C(O)-methyl, (4(-O-C(O)-phenyl)methyl, (3(-O-C(O)-phenyl)methyl, (4-(- O-C(O)-)-1-naphthyl)methyl, (5-(-O-C(O)-)-1-naphthyl)methyl and (6-(-O-C(O)-)- 2-naphthyl)methyl, and specifically from -O-C(O)-methyl, (4(-O-C(O)- phenyl)methyl and (3(-O-C(O)-phenyl)methyl.
  • variables X 1 and X 2 in formula (I) have identical meanings and, likewise, the variables X 1a and X 2a in formula (II) have identical meanings, which are selected from the meanings defined in groups (3) and (3.1), of embodiments.
  • the variables X 1 and X 2 in formula (I) are selected from hydrogen, 2-hydroxyethyl, methoxycarbonyl-C 1 -C 4 -alkyl, hydroxymethyl-phenyl- methyl, hydroxymethyl-naphthyl-methyl, methoxycarbonyl-phenyl-methyl and methoxycarbonyl-naphthyl-methyl, in particular selected from hydrogen, 2- hydroxyethyl, methoxycarbonyl-methyl, (4-(hydroxymethyl)phenyl)methyl, (3- (hydroxymethyl)phenyl)methyl, (4-(hydroxymethyl)-1-naphthyl)methyl, (6- (hydroxymethyl)-2-naphthyl)methyl, (4-(methoxycarbonyl)phenyl)methyl, (3- (methoxycarbonyl)
  • variables X 1a and X 2a in formula (II) are selected from a single bond, 2(-O)-ethyl, -O-C(O)-C 1 -C 4 -alkyl, -O- methyl-phenyl-methyl, -O-methyl-naphthyl-methyl, -O-C(O)-phenyl-methyl and -O- C(O)-naphthyl-methyl, in particular selected from a single bond, 2(-O)-ethyl, -O- C(O)-methyl, (4(-O-methyl)phenyl)methyl, (3(-O-methyl)phenyl)methyl, (4(-O- methyl)-1-naphthyl)methyl, (6(-O-methyl)-2-naphthyl)methyl, (4(-O-C(O)- phenyl)methyl, (3-(-O-C(O)- phenyl)methyl, (3-(-
  • variables X 1 and X 2 in formula (I) have identical meanings and, likewise, the variables X 1a and X 2a in formula (II) have identical meanings, which are selected from the meanings defined in group (4) of embodiments.
  • variable Ar in formulae (I) and (II) that is selected from a mono- or polycyclic arylene having from 6 to 33 carbon atoms as ring members and mono- or polycyclic hetarylene having from 5 to 34 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, sulphur atoms and oxygen atoms, where the remainder of the ring atoms are carbon atoms, where the mono- or polycyclic arylene and the mono- or polycyclic hetarylene are unsubstituted or carry 1, 2, 3 or 4 radicals R Ar ; wherein R Ar have the meanings defined herein, in particular those mentioned herein as pre- ferred.
  • variable Ar in formulae (I) and (II) is selected from the group consisting of: phenylene, naphthylene, phenanthrendiyl, triphenylene, where phenylene, naph- thylene and phenanthrendiyl are unsubstituted or carry 1, 2 or 3 radicals R Ar , the moiety of the formula Ar-1, the moiety of the formula Ar-2, the moiety of the formula Ar-3, the moiety of the formula Ar-4, the moiety of the formula Ar-5 and the moiety of the formula Ar-6: where # indicates the bond to E 1 and E 2 , respectively, where in the formulae Ar-1 and Ar-2 Z is O, S, CH 2 , CH-Ar’, with Ar’ being phenyl or naphthyl; Z’ is a single bond, O, S or a group of the formula (A), M/REUCTR-0
  • the variables Z and Z’ in the moieties of formulae Ar-1 and Ar-2 are defined as follows: Z is a CH 2 , O, S, CH-phenyl or CH-naphthyl; Z’ is a single bond, O, S or a group of the formula (A), wherein the moiety Q is a single bond, O or S; More preferably, the variables Z and Z’ in formulae Ar-1 and Ar-2 have the following meanings: if Z’ is a single bond, Z is CH 2 , O or S, in particular CH 2 or S; if Z’ is O, Z is CH-phenyl or CH-naphthyl; if Z’ is S, Z is S; and if Z’ is a group of the formula (A), Z is O.
  • variable Ar in formulae (I) and (II) is selected from the group consisting of phenylene, naphthylene, phenanthrendiyl, M/REUCTR-037-PC RCA-EO_Trimer 19 dibenzo[b,d]thiophendiyl, biphenyldiyl, triphenylenediyl, 9H-fluorendiyl, thi- anthrendiyl, di(thiantren-1-yl)phenylene, di(thianthren-2-yl)phenylene, tri(thianthren-1-yl)phenylene, tri(thianthren-2-yl)phenylene, di(naphthalene-1- yl)phenylene, di(naphthalene-2-yl)phenylene, tri(naphthalene-1-yl)phenylene, tri(naphthalene-2-yl)phenylene, 3,3',5,5'-te
  • Ar is selected from • 1,3-phenylene; • 1,4-phenylene; • 1,2-phenylene; • 2,4,6-tri(naphthalen-2-yl)-1,3-phenylene; • 2,4,6-tri(thianthren-2-yl)-1,3-phenylene; • 2,5-di(naphthalen-2-yl)-1,4-phenylene; • 2,5-di(thianthren-1-yl)-1,4-phenylene; • 4,5-di(naphthalen-2-yl)-1,2-phenylene; • 2,5-di(thianthren-2-yl)-1,4-phenylene; • 4,5-di(thianthren-2-yl)-1,2-phenylene; • 2,3-naphthylene; • 2,7-naphthylene; • 2,6-naphthylene; • 1,4-naphthylene; • 1,5-na
  • variables Y 1 and Y 2 in formulae (I) and (II) that are se- lected from linear C 2 -C 4 -alkandiyl, such as 1,2-ethandiyl (CH 2 -CH 2 ), 1,3-propandiyl or 1,4-butandiyl, and in particular 1,2-ethandiyl.
  • the variables Y 1 and Y 2 are identical to each other.
  • the variables Y 1 and Y 2 in formulae (I) and (II) are both -CH 2 -CH 2 -.
  • the moieties E 1 and E 2 in formulae (I) and (II) are both O.
  • the substituents R 1 , R 2 , R 3 and R 4 in formulae (I) and (II) have one of the meanings defined herein, especially those mentioned herein as preferred. In this context, it is preferred that R 1 , R 2 , R 3 and R 4 , if present, all have the same meaning.
  • R 1 , R 2 , R 3 and R 4 are attached to the corre- sponding positions of their respective naphthyl units.
  • the variables m, n, p and q in formulae (I) and (II) are 0, 1 or 2, and preferably all have the same meaning. If present, the variable s in formulae (I) and (II) is preferably 0, 1 or 2, and in partic- ular is 1 or 2. In a particularly preferred group (9) of embodiments the variables m, n, p and q in formulae (I) and (II) all have the same meaning and are 0 or 1.
  • variables R 1 , R 2 , R 3 , R 4 , R Ar , R, R’, R’’ and R’’’ either alone or preferably in combination with each other and with the meanings and preferred meanings of the variables X 1 , X 2 , Ar, Y 1 , Y 2 , E 1 , E 2 , n, m, p, q, R x , Alk 1 and Alk 2 described above, have the following meanings.
  • R 1 , R 2 , R 3 and R 4 are preferably, independently of one another, selected from the group consisting of halogen, CN, R, OR and CH s R' 3-s , and more preferably from the group of fluorine, bromine, CN, R and OR, where s is 1 or 2, especially 2, and the variable R and R’ each have one of the meanings defined herein, especially a preferred one.
  • the radicals R 1 , R 2 , R 3 and R 4 are idependently selected from 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.
  • the radicals R 1 , R 2 , R 3 and R 4 are idependently selected from the group consisting of phenyl, naphthyl, such as 1- naphthyl and 2-naphthyl, phenanthrenyl, such as 9-phenanthrenyl, and thianthrenyl, such as 1-thianthrenyl and 2-thianthrenyl.
  • the radicals R 1 , R 2 , R 3 and R 4 have identical meanings and are selected from the group consisting of naphthyl, such as in particular 2-naphthyl, and thianthrenyl, such as in particular 2- thianthrenyl.
  • R Ar is preferably selected from the group consisting of halogen, CN, R, OR and CH t R’ 3-t , and more preferably from the group of halogen, CN and R, where t is 1 or 2, especially 2, and the variables R and R’ each have one of the meanings defined herein, especially a preferred one.
  • R Ar is selected from fluorine, bro- mine, cyano, phenyl, naphthyl, such as 1-naphthyl and 2-naphthyl, phenanthrenyl, such as 9-phenanthrenyl, dibenzo[b,d]thiophenyl, such as 4- dibenzo[b,d]thiophenyl, and thianthrenyl, such as 1-thianthrenyl or 2-thianthrenyl, and specifically is selected from bromine, CN, phenyl, 1-naphthyl, 2-naphthyl, 9- phenanthrenyl, 4-dibenzo[b,d]thiophenyl 1-thianthrenyl and 2-thianthrenyl.
  • M/REUCTR-037-PC RCA-EO_Trimer 26 R is preferably selected from the group consisting of methyl, ethyl, mono- or poly- cyclic 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 oxy- gen, while the remainder of these ring member atoms of hetaryl are carbon atoms, where aryl and hetaryl are unsubstituted or substituted by 1, 2, 3 or 4 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 select- ed from methyl, ethyl, phenyl, naphthyl, such as 1-naphthyl and 2-naphthyl, phe- nanthrenyl, such as 9-phenanthrenyl, 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 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, phenanthrenyl, dibenzo[b,d]thiophenyl and thi- anthrenyl, which are unsubstituted.
  • R’ is preferably selected from the group consisting of phenyl, naphthyl, phenan- threnyl and triphenylenyl, which are unsubstituted or substituted by 1, 2 or 3 identi- cal 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.
  • 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, 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. More preferably, R’’ is unsubstituted phenyl or unsubstituted naphthyl.
  • R'" is preferably selected from the group consisting of phenyl, OCH 3 and CH 3 .
  • the compound of formula (I) is a compound of the formula (Ia), M/REUCTR-037-PC RCA-EO_Trimer 27 where the variable a is either 0 or 1, where the groups R a are identical and have one of the meanings given herein for R 1 , R 2 , R 3 and R 4 , respectively, in particular one of the meanings mentioned as preferred, and where X 1 , X 2 and Ar have the meanings defined herein, in particular the meanings mentioned as preferred.
  • the structural unit of the formula (II) is a structural unit of the formula (IIa), where # represents a connection point to a neighboring structural unit, where the variable a is either 0 or 1, where the groups R a are identical and have one of the meanings given for R 1 , R 2 , R 3 and R 4 , respectively, in particular one of the meanings mentioned as preferred, and where X 1a , X 2a and Ar have the meanings defined here- in, in particular the meanings mentioned as preferred.
  • the moieties X 1 and X 2 in formula (Ia) as well as the moieties X 1a and X 2a in formula (IIa) are defined either as in one of groups (1), (1.1) and (1’) of the M/REUCTR-037-PC RCA-EO_Trimer 28 embodiments, in group (2) of the embodiments, in one of groups (3), (3.1) and (3') of the embodiments, or in one of groups (4) and (4') of the embodiments. More preferably, the moieties X in formula (Ia) as well as the moieties X a in formula (IIa) are defined as in one of groups (4) and (4') of the embodiments.
  • the moieties X 1 and X 2 in formula (Ia) are here in particular selected from the group consisting of hydrogen, 2-hydroxyethyl, methoxycarbonyl-methyl, hydroxymethyl-phenyl-methyl, hydroxymethyl-naphthyl-methyl, methoxycarbonyl-phenyl-methyl and methoxycarbonyl-naphthyl-methyl, in particular selected from hydrogen, 2- hydroxyethyl, methoxycarbonyl-methyl, (4-(hydroxymethyl)phenyl)methyl, (3- (hydroxymethyl)phenyl)methyl, (4-(hydroxymethyl)-1-naphthyl)methyl, (6- (hydroxymethyl)-2-naphthyl)methyl, (4-(methoxycarbonyl)phenyl)methyl, (3- (methoxycarbonyl)phenyl)methyl, (4-(methoxycarbonyl)-1-naphthyl)methyl and (6- (methoxycarbonyl)-2-naph
  • variables X 1a and X 2a in formula (II) are selected from a single bond, 2(-O)-ethyl, -O-C(O)-methyl, -O- methyl-phenyl-methyl, -O-methyl-naphthyl-methyl, -O-C(O)-phenyl-methyl and -O- C(O)-naphthyl-methyl, in particular selected from a single bond, 2(-O)-ethyl, -O- C(O)-methyl, (4(-O-methyl)phenyl)methyl, (3(-O-methyl)phenyl)methyl, (4(-O- methyl)-1-naphthyl)methyl, (6(-O-methyl)-2-naphthyl)methyl, (4(-O-C(O)- phenyl)methyl, (3-(-O-C(O)-phenyl)methyl, (4(-O-C(O)-phenyl)methyl
  • the moiety Ar in formulae (Ia) and (IIa) is here in particular selected from the group consisting of 1,3-phenylene, 1,4-phenylene, 1,2- phenylene, 2,4,6-tri(naphthalen-2-yl)-1,3-phenylene, 2,4,6-tri(thianthren-2-yl)-1,3- phenylene, 2,5-di(naphthalen-2-yl)-1,4-phenylene, 2,5-di(thianthren-1-yl)-1,4- phenylene, 4,5-di(naphthalen-2-yl)-1,2-phenylene, 2,5-di(thianthren-2-yl)-1,4- phenylene, 4,5-di(thianthren-2-yl)-1,2-phenylene, 2,3-naphthylene, 2,7- naphthylene, 2,6-naphthylene, 1,4-naphthylene, 1,5-na
  • Examples of the particular subgroup (7a) are the compounds of the formula (Ia) and the structural units of formula (IIa), in which the combination of the moieties X 1 and X 2 or moieties X 1a and X 2a , respectively, the variable Ar and the substituents (R a ) a is as defined in any one of the lines 1 to 222 in table A below, where X 1a or X 2a is derived in each case from X 1 or X 2 in formula (Ia) such that, if X 1 or X 2 is hydro- gen, hydrogen is replaced by a single bond, or, if X 1 or X 2 is not hydrogen, the -OH or -OR x group of X 1 or X 2 is replaced by an oxo (-O-) unit, and where X 1 and X 2 , re- spectively, has one of the meanings defined herein, especially one of those men- tioned herein as preferred.
  • M/REUCTR-037-PC RCA-EO_Trimer 30 M/REUCTR-037-PC RCA-EO_Trimer 31 M/REUCTR-037-PC RCA-EO_Trimer 32 M/REUCTR-037-PC RCA-EO_Trimer 33 M/REUCTR-037-PC RCA-EO_Trimer 34 M/REUCTR-037-PC RCA-EO_Trimer 35 M/REUCTR-037-PC RCA-EO_Trimer 36 M/REUCTR-037-PC RCA-EO_Trimer 37 M/REUCTR-037-PC RCA-EO_Trimer 38 M/REUCTR-037-PC RCA-EO_Trimer 39 M/REUCTR-037-PC RCA-EO_Trimer 40 M/REUCTR-037-PC RCA-EO_Trimer 41 M/REUCTR-037-PC RCA-EO_Trimer 42 M/REUCTR-037-PC RCA-EO_Trimer 43
  • the obtained compound (3) is a compound of the formula (Ia), where the variable a is 0 and X is hydrogen.
  • Suitable solvents for this reaction are polar aprotic organic solvents, such as for example dimethylformamide or acetone.
  • the compounds of formula (Ia), where X 1 and X 2 are identical -Alk 1 -OH, -CH 2 -A- CH 2 -OH, -Alk 2 -C(O)OR x or -CH 2 -A-C(O)OR x and the variable a is 0, can, for exam- ple, be prepared from the compounds of formula (3) described above by analogy to the process shown in the following reaction scheme 2.
  • a compound of formula (3) is reacted with a compound of formula (4), where Z is a suitable leaving group, such as a chloride, bromide, iodide, tosylate or mesitylate group and L is -Alk 1 -OH, -CH 2 -A-CH 2 -OH, -Alk 2 -C(O)OR x or -CH 2 -A-C(O)OR x , in the presence of a base, e.g.
  • oxo base such as an alkaline carbonate
  • X 1 and X 2 are iden- tical having one of the meanings listed above for the group L and the variable a is 0.
  • Suitable solvents for this reaction of scheme 2 are polar aprotic organic solvents, such as for example dimethylformamide.
  • the compounds of the formula (Ia), where X 1 and X 2 are identical and selected from hydrogen, especial- ly hydrogen, -Alk 1 -OH and -Alk 2 -C(O)OR x , and the variable a is 0, can for example also be prepared by analogy to the 3- to 4-step process shown in the following re- action scheme 3.
  • step a) of the process only one of the two hydroxyl groups of 1,1’-bi-2-naphthol of formula (1) is protected by introducing a protecting group, which is preferably an arylmethyl group, such as in particular a benzyl group.
  • a protecting group which is preferably an arylmethyl group, such as in particular a benzyl group.
  • Arylmethyl groups, particu- larly a benzyl group can be introduced by procedures well established in the art, e.g.
  • step b) about 2 molar equivalents of the monoprotected 1,1’-bi-2- naphthol derivative (6) are reacted with a compound of formula (2), where Ar is mono- or polycyclic (het)arylene as defined herein and Z is a suitable leaving group, such as a bromide, iodide, tosylate or mesitylate group, in the presence of a base, for instance an oxo base, such as an alkaline metal carbonate, e.g. potassium car- bonate, or an alkaline metal hydride, e.g. sodium hydride, to yield the compound of formula (7).
  • a base for instance an oxo base, such as an alkaline metal carbonate, e.g. potassium car- bonate, or an alkaline metal hydride, e.g. sodium hydride, to yield the compound of formula (7).
  • deprotection of the compound (7) to the corresponding diol of formula (3) can be carried out using well-established measures, such as e.g. catalytic hydrogenation if the protecting group to be re- moved is benzyl.
  • the obtained diol (3) is a compound of the formula (Ia), where X 1 and X 2 are hydrogen and the variable a is 0.
  • step d) the diol (3) is con- verted to a corresponding compound of formula (5), which is also a compound of formula (Ia), where, however, X 1 and X 2 are identical groups Alk 1 -OH, -CH 2 -A-CH 2 - OH, -Alk 2 -C(O)OR x or -CH 2 -A-C(O)OR x .
  • X 1 and X 2 are identical groups Alk 1 -OH, -CH 2 -A-CH 2 - OH, -Alk 2 -C(O)OR x or -CH 2 -A-C(O)OR x .
  • the compounds of the formula (Ia), wherein X 1 and X 2 are identical groups - Alk 1 -OH, -CH 2 -A-CH 2 -OH, -Alk 2 -C(O)OR x or -CH 2 -A-C(O)OR x , especially -Alk 1 -OH or -Alk 2 - C(O)OR x , and the variable a is 0, can for example also be prepared by analogy to the 2-step process shown in the following reaction scheme 4.
  • step a) of the process 1,1’-bi-2-naphthol of formula (1) is reacted with usually 0.5 to 1.5 molar equivalents of a compound of the formula (4), where Z is a suitable leaving group, such as a chloride, bromide, iodide, tosylate or mesitylate group and the presence of a base, e.g. an oxo base, such as an alkaline metal carbonate, e.g. potassium car- bonate, to yield the compound (8).
  • Z is a suitable leaving group, such as a chloride, bromide, iodide, tosylate or mesitylate group and the presence of a base, e.g. an oxo base, such as an alkaline metal carbonate, e.g. potassium car- bonate, to yield the compound (8).
  • a base e.g. an oxo base, such as an alkaline metal carbonate, e.g. potassium car- bon
  • a suitable solvent for this reaction step is pref- erably selected from polar aprotic organic solvents, such as for example meth- ylethylketone.
  • step b) about 2 molar equivalents of the compound (8) are reacted with a compound of formula (2), where Ar is mono- or polycyclic (het)arylene as defined herein and Z is a suitable leaving group, such as a chloride, bromide, io- dide, tosylate or mesitylate group, in the presence of a base, e.g. an oxo base, such as an alkaline carbonate like potassium carbonate.
  • a base e.g. an oxo base, such as an alkaline carbonate like potassium carbonate.
  • Suitable solvents for this reac- tion step are polar aprotic organic solvents, such as for example dimethylformamide or acetone.
  • the compound of formula (5) obtained by this reaction is the desired compound of formula (Ia) where X 1 and X 2 are identical moieties different from hy- drogen.
  • compounds of the formula (Ia), where X 1 and X 2 are identical groups that are different from hydro- gen and the variable a is 0, can for example also be prepared by analogy to the 4- step process shown in the following reaction scheme 5.
  • step a) of the process 1,1’-bi-2-naphthol of formula (3) is mono-protected by introducing a suitable protecting group PG’, which is selected from hydroxyl pro- tecting groups established in the art, such as for example 2-tetrahydropyranyl, ben- zyl, diphenylmethyl, trityl, allyl, propargyl or tert-butyloxycarbonyl (Boc), yielding a compound of formula (9).
  • PG’ group should be chosen such that the conditions for its introduction, as well as for its removal, are compatible with other functional groups of the compound to be protected.
  • step a) The in- troduction of the protecting group PG’ in step a) and also its removal in step c), which affords an alcohol of the formula (8), can be conducted in analogy to respec- tive procedures established in the art (see e.g. EP 0915073 B1; T. Song et al., Ad- vanced Synthesis & Catalysis 2014, 356(8), 1708-1718; C. Dong et al., Catalysis Science & Technology 2015, 5(10), 4755-4759; L. Jin et al., Tetrahedron: Asymmetry 2008, 19(16), 1947-1953; A. R. Abreu et al., Tetrahedron 2010, 66(3), 743-749; Y.
  • the final step d) yielding the desired product of formula (5) can for example be carried out in analogy to any one of the reactions of the steps b) in schemes 3 and 4.
  • the conversions shown in these schemes is preferably con- ducted using 2-chloro-ethanol as compound of formula (4) or, alternatively, using ethylene carbonate or ethylene oxide, in particular ethylene carbonate, instead of a M/REUCTR-037-PC RCA-EO_Trimer 52 compound (4).
  • Such conversions with ethylene carbonate or ethylene oxide are also carried out in the presence of a base, e.g.
  • compounds (Ia), where the vari- able a is 1 and R a is bromine can be obtained by using in the reactions of schemes 1, 3, 4 or 5, instead of 1,1'-bi-2-naphthol, 6,6'-dibromo-1,1'-bi-2-naphthol, which can be prepared by selective bromation of 1,1’-bi-2-naphthol in the positions 6 and 6’ using as brominating reagent bromine or N-bromosuccinimide, as described e.g. in WO 2019/043060 and the documents cited therein.
  • 1,1’-bi-2-naphthol that are substituted with (het)aryl groups in position 6 and 6’ can readily be ob- tained e.g. from the aforementioned 6,6’-dibromo-1,1’-bi-2-naphthol via a Suzuki coupling reaction, as also described in WO 2019/043060 and the documents cited therein.
  • the thus obtained 6,6’-di((het)aryl)-1,1’-bi-2-naphthol allows access to the corresponding compounds (Ia), where the variable a is 1 and the four substituents R a are mono- or polycyclic (het)aryl.
  • the intermediates in some cases result in the form of colourless 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 purification can be achieved by recrystallization or washing proce- dures, such as slurry washing.
  • M/REUCTR-037-PC RCA-EO_Trimer 53 The starting compounds used in the syntheses shown in schemes 1, 2, 3, 4 and 5 above to prepare compounds of formula (I) are commercially available or can be prepared by methods known from the art. 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 impurities different from the compound of formula (I), except for volatiles.
  • the purity of compounds of formula (I) is at least 95%, in particular at least 98% and especially 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 impurities 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 mat- ter is understood to mean compounds having a boiling point, which exceeds 200°C at standard pressure. It is a particular benefit of the invention that the compounds of formula (I) and likewise 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 in- vention 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 formula (I), where the crystals contain a solvent incorporated. It is a particular benefit of the invention that the compounds of the formula (I) and likewise their solvates, can often be easily crystallized from conventional organic solvents. This allows for an efficient purification of the compounds of formula (I).
  • Suitable organic solvents for crystallizing the compounds of the formula (I) or their solvates include 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, methyl ethyl ketone, methyl isopropyl ketone or diethyl ketone, aliphatic and alicyclic ethers, such as diethyl ether, dipropyl ether, methyl isobutyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, dioxane or tetrahydrofuran, aliphatic-aromatic ethers, such as anisole, and aliphatic alcohols having 1 to 4 car- bon atoms, such as methanol, ethanol or isopropanol, as well as mixtures thereof.
  • aromatic hydrocarbons such as toluene or
  • 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 obtained in purified form by employing other simple and efficient methods for puri- fying the raw products of these compounds, such as in particular slurry washing the raw solids obtained directly after the conversion to prepare the compounds of for- mula (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 or- ganic solvents here are in principle the same as those listed above as being suita- ble for crystallizing the compounds of formula (I), such as in particular the men- tioned aromatic hydrocarbons, aliphatic ketones and aliphatic ethers, e.g.
  • the compounds of formula (I) used for the preparation of the thermo- plastic polymers, in particular the 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 purifi- cation to the degree required in the preparation of optical resins.
  • these compounds can be obtained in a purity which provides for high refractive in- dices and also low haze, which is particularly important for the use in the prepara- tion of optical resins of which the optical devise is made of.
  • the com- pounds of formula (I) are particularly useful as monomers in the preparation of the optical resins.
  • the formula (I) of the monomer used corresponds to the formula (II) of the structural unit comprised in the thermoplastic resin.
  • the formula (Ia) of the monomer used corresponds to the formula (IIa) of the structural unit comprised in the thermoplastic resin.
  • the structural units of the formulae (II) and (IIa) are repeating units within the polymer chains of the thermoplastic resin.
  • the 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) M/REUCTR-037-PC RCA-EO_Trimer 55 #-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 carbo- cycles 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 halo- gen, C 1 -C 6 -alkyl, C 5 -C
  • R z in formula (IV) is O-Alk 5 -C(O)
  • the esters, in particular the C 1 -C 4 -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), SO 2 , C(CH 3 ) 2 , and a radical A' and where L is a single bond or C 1 -C 4 -alkylene.
  • R z is in particular O-Alk 4 -, where Alk 4 is in particular linear alkandiyl having 2 to 4 carbon atoms and especially O-CH 2 CH 2 .
  • monomers of formula (IV) preference is given to monomers of the general formulae (IV-1) to (IV-8) M/REUCTR-037-PC RCA-EO_Trimer 57 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
  • the thermoplastic resin of the pre- sent invention comprises at least one structural unit of the formula (IIa) 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 formula (V-13), structural units of the formula (V-14), structural units of the formu- la (V-15), structural units of the formula (V-21) and structural units of the formula (V-22).
  • those thermoplastic resins are pre- ferred, 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-CH 2 CH 2 .
  • the total molar ratio of the structural units of the formula (II) or (IIa) is in the range from 1 to 99 mol-%, preferably in the range from 5 to 98 mol-%, fur- ther preferably in the range from 10 to 97 mol-%, 10 to 90 mol-%, 10 to 70 mol-%, 10 to 50 mol-%, 10 to 30 mol-%, 15 to 95 mol-%, 15 to 70 mol-%, 15 to 50 mol-% or 15 to 30 mol-% and even further preferably in the range from 15 to 55 mol-%, 15 to 35 mol-%, 15 to 30 mol-%, 20 to 50 mol-%, 20 to 70 mol-%, 20 to 95 mol-% or 30 to 98 mol-% of the total amount of structural units of the formulae (II) and (V).
  • the total molar ratio of the structural units of the formula (II) or (IIa) is in the range from 1 to 99 mol-%, preferably in the range from 5 to 98 mol-%, fur- ther preferably in the range from 10 to 97 mol-%, 10 to 90 mol-%, 10 to 70 mol-%, 10 to 50 mol-%, 10 to 30 mol-%, 15 to 95 mol-%, 15 to 70 mol-%, 15 to 50 mol-% or 15 to 30 mol-%, and even further preferably in the range from 15 to 55 mol-%, 15 to 35 mol-%, 15 to 30 mol-%, 20 to 50 mol-%, 20 to 70 mol-%, 20 to 95 mol-% or 30 to 98 mol-% of the total amount of structural units of the In the thermoplastic resins M/REUCTR-037-PC RCA-EO_Trimer 65 of this particular preferred
  • 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 syn- thesis 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 monoto- sylates; alternatively, 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 syn- thesis 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); (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 fluorene; and the like.
  • 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 prepared from compounds of formulae (IV), where R z is a single bond, by reaction M/REUCTR-037-PC RCA-EO_Trimer 66 with alkylene oxides or haloalkanols.
  • 9,9- bis(hydroxynaphthyl)-fluorenes of the formula (IV-2) where R z is a single bond with alkylene oxides or haloalkanols 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 total amount of such impurity compounds is preferably 5000 ppm or lower, more preferably 3000 ppm or lower, still more prefer- ably 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.
  • the total amount of dihydroxy com- pounds in which a carbon number of at least one of the radicals X 1 or X 2 differs from the formula (I) 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 the main component is the dihydroxy com- pound(s) represented by the formula (I).
  • the total content of the dihydroxy com- pounds in which a carbon number of at least one of the radicals X 1 or X 2 differs from the formula (I) is further preferably 1000 ppm or lower, and more preferably 500 ppm or lower.
  • thermoplastic resins for the preparation of optical devices are in particular polycarbonates, polyestercarbonates and polyesters.
  • Preferred thermoplastic resins for the preparation of optical devices, such as lenses are in particular polycarbonates.
  • Said polycarbonates are structurally characterized by having structural units of at least one of the formulae (II) and (IIa), respectively, optionally structural units de- rived from diol monomers, which are different from the monomer compound of the formula (I), e.g.
  • each # represents a connection point to a neighboring structural unit, i.e. to O at the connection point of the structural unit of the formula (II) and, if present, to O at the connection point of the structural unit of the formula (V).
  • Said polyesters are structurally characterized by having structural units of at least one of the formulae (II) and (IIa), respectively, optionally structural units derived from diol monomers which are different from the monomer compound of the formu- la (I), e.g. structural units of the formula V. If X 1a and X 2a in formulae (II) and (IIa) are selected from a single bond, -Alk 1 -O-- and -CH 2 -A-CH 2 -O-, 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. 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) and (IIa), respectively, optionally structural units derived from diol monomers which are different from the monomer compound of M/REUCTR-037-PC RCA-EO_Trimer 68 the formula (I), e.g. structural units of the formula (V), a structural unit of formula (III-1) stemming from the carbonate forming component and structural units de- rived from dicarboxylic acid, e.g.
  • thermoplastic copolymer resins in particular polycarbonates, polyestercarbonates and polyesters, which have both structural units of formula (II) 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 (I) with one or more mon- omers of formula (IV).
  • the molar ratio of monomers of formula (I) to monomers of formula (IV) and likewise the molar ratio of the structural units of formula (II) to structural units of formula (V) are in the range from 1:99 to 99:1, in particular in the range from 5:95 to 80:20 or 20:80 to 98:2 and especially in the range from 30:70 to 97:3 or in the range from 10:90 to 99:1 or 10:90 to 60:40, in par- ticular in the range from 15:85 to 98:2, 15:85 to 90:10, 15:85 to 80:20 or 15:85 to 70:30, more preferably in the range from 20:80 to 97:3 or 20:80 to 85:15, or in the range from 25:75 to 97:3, 25:75 to 85:15 or 25:75 to 80:20, especially in the range from 27:73 to 75:25, 27:73 to 80:20, 27:73 to 97:3 or in the range from 27:73 to 99:1,
  • the molar ratio of the structural units of the formula (II) is usual- ly from 1 to 99 mol-% in particular from 5 to 80 mol-% or 20 to 98 mol-%, more preferably in the range from 30 to 97 mol-% or in the range from 10 to 99 mol-% or 10 to 60 mol-%, especially in the range from 20 to 97 mol-% or in the range from 27 to 97 mol-%, even more preferably in the range from 27 to 90 mol-% and specifically in range from 30 to 80 mol-% or in the range from 35 to 70 mol-%, based on the total molar amount of structural units of the formulae (II) and (V).
  • the molar ratio of the structural units of the formula (V) is usually from 1 to 99 mol-%, in particular from 2 to 80 mol-%, more preferably in the range from 3 to 70 mol-% or in the range from 1 to 90 mol-%, especially in the range from 2 to 85 mol-% or in the range from 3 to 80 mol-%, even more preferably in the range of 10 to 73 mol-% and specifically in range from 20 to 70 mol-% or in the range from 15 to 40 mol-%, 20 to 45 mol-% or 30 to 65 mol-%, based on the total molar amount of structural units of the formulae (II) and (V).
  • thermoplastic copolymer resins in par- ticular polycarbonates, polyestercarbonates and polyesters, which have both struc- M/REUCTR-037-PC RCA-EO_Trimer 69 tural units of formula (II) and one or more structural units of formulae (V-14) or (V- 15), i.e.
  • resins in particular polycarbonates, polyestercarbonates and polyesters, which are obtainable by reacting at least one monomer of formula (I) with one or more monomers of formulae (IV-14) or (IV-15).
  • the molar ratio of mon- omers of formula (I) to monomers of formulae (IV-14) and (IV-15) and likewise the molar ratio of the structural units of formula (II) to structural units of formulae (V- 14) and (V-15) are in the range from 50:50 to 99:1, in particular in the range from 70:30 to 98:2 and especially in the range from 80:20 to 97:3.
  • thermoplastic copolymer resins 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-21) or (V-22), i.e. resins, in particular polycarbonates, polyester- carbonates and polyesters, which are obtainable by reacting at least one monomer of formula (I) with one or more monomers of formulae (IV-11), (IV-12), (IV-13), (IV- 21) or (IV-22).
  • the molar ratio of monomers of formula (I) to monomers of formulae (IV-11), (IV-12), (IV-13), (IV-21) and (I-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-21) and (V-22) are in the range from 10:90 to 90:10, 15:85 to 80:20, 20:80 to 70:30, 25:75 to 80:20, 30:70 to 90:10 or 30:70 to 80:20, in particular in the range from 35:65 to 75:25, 35:65 to 70:30, 40:60 to 85:15 or 40:60 to 80:20, and especially in the range from 50:50 to 80:20.
  • thermoplastic copolymer resins of the present invention such as a polycar- bonate resin may include either one of a random copolymer structure, a block co- polymer structure, and an alternating copolymer structure.
  • the thermoplastic resin according to the present invention does not need to include all of structural units (II) and one or more 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 molecules.
  • thermoplastic resin including all of structural units (II) and structural units (V) described above may be a copoly- mer including all of structural units (II) and structural units (V), it may be a mixture of a homopolymer or a copolymer including 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 M/REUCTR-037-PC RCA-EO_Trimer 70 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 compo- nent and a carbonate forming component.
  • thermoplastic polyesters and polyestercarbonates are obtainable by polycondensation of a diol component and a dicarboxylic acid, or an ester forming derivative thereof, and optionally a carbonate forming component.
  • thermoplastic resins can be prepared by the following methods.
  • a method for preparing the thermoplastic resin of the present invention, such as a polycarbonate resin includes a process of melt polycondensation of a dihydroxy component corresponding to the above-mentioned structural units and a diester carbonate.
  • the dihydroxy compound comprises at least one dihydroxy compound represented by the formula (I), in particular by the formula (Ia), as defined herein.
  • the di- hydroxy compound may also comprise one or more dihydroxy compounds repre- sented by the formula (IV), preferably by the formulae (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 dihydroxy component with a carbonate precursor, such as a diester carbonate, where the dihydroxy component comprises at least one compound represented by the formulae (I) and (Ia), respectively, or a combination of at least one compound represented by the formulae (I) and (Ia), 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
  • a polycarbonate resin can be formed by a melt polycondensation process in which the compound represented by the formulae (I) and (Ia), 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-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 carbonate, 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 carbonate
  • thermoplastic resin (or a polymer) other than a polycarbonate resin, such as pol- yestercarbonates and polyesters is obtained by using the dihydroxy compound rep- M/REUCTR-037-PC RCA-EO_Trimer 71 resented by the formulae (I) and (Ia), 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 monomer).
  • the monomers of formula (I) and likewise the co-monomers of formula (IV) used for producing the thermoplastic resin may contain impurities resulting 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 formu- lae (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 (I) or by reacting combination of at least one monomer compound of the formula (I), in particular at least one monomer (I) mentioned herein as pre- ferred, and one or more monomer compounds of the formula (IV), and in particular of the formulae (IV-11), (IV-12), (IV-13), (IV-14), (IV-15), IV-21) or (IV-22), and the like, as dihydroxy components; with carbonate precursors, such as diester car- bonates.
  • the thermoplastic resin of the present invention may also contain minor amount of impurities, for example, as extra contents of thermoplastic resin composition or a M/REUCTR-037-PC RCA-EO_Trimer 72 part of the polymer skeleton of the thermoplastic resin.
  • im- purities include phenols formed by a process for forming 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 preferably 1000 ppm or lower, more preferably 500 ppm or lower, still more preferably 200 ppm or lower, and es- pecially 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 impuri- ties is preferably 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 preferably 1000 ppm or lower, more preferably 500 ppm or lower, still more prefera- bly 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 prefer- ably 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 ther- moplastic 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 treat- ment with an adsorbent, e.g. active charcoal.
  • Resins having targeted characteristics can be formed by adjusting the amounts of phenols and diester carbonates.
  • the amounts of phenols, diester carbonates, and monomers can be suitably adjusted by arranging the conditions for polycondensa- tion, the working conditions of devices used for polymerization, or the conditions for extrusion molding after the polycondensation process.
  • the weight-average molecular weight (Mw), as determined by GPC (gel permeation chromatography), of the thermoplastic resin 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 20000 to 70000 Dalton, 30000 to 60000 Dalton 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 of the present invention determined this way is also denot- ed herein as “polystyrene conversion weight-average molecular weight”.
  • the num- ber-average molecular weight (Mn) of the thermoplastic resin according to the pre- M/REUCTR-037-PC RCA-EO_Trimer 73 sent invention is preferably in the range of 3000 to 30000, more preferably 5000 to 25000, and especially in the range of 7000 to 20000.
  • the viscosity-average molecu- lar 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 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.
  • a thermoplastic resin has the value of the weight-average molecular weight (Mw) within the above-mentioned suitable range, a molded article made from the thermoplastic resin has high strength.
  • such a thermoplastic resin with the suitable Mw value is advantageous for molding because of its excellent fluidity.
  • the thermoplastic resin comprises 9% by weight or less, in particular 7% by weight or less and especially 5% by weight or less, e. g.
  • a ther- moplastic resin according to this embodiment comprising 9% by weight or less, in particular 7% by weight or less and especially 5% by weight of low molecular weight compounds with molecular weights of less than 1000, is not or only slightly prone to precipitation of the low molecular weight compounds, which is also known as bleed-out during a molding process, such as an injection molding process.
  • a molding process such as an injection molding process.
  • molding of a thermoplastic resin with a higher amount of the low molecular weight compounds may be accompanied by bleed-out to a greater extent.
  • the thermoplastic resin comprises 0.1% by weight or more, in par- ticular 0.3% by weight or more or 0.5% by weight or more, and especially 1.0% by weight or more, e. g.
  • thermoplastic resin of the present invention such as especially the above- mentioned polycarbonate resin, has a high refractive index (n D or n d ) and thus is suitable to an optical lens.
  • the values of the refractive index as referred herein are M/REUCTR-037-PC RCA-EO_Trimer 74 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 ther- moplastic resin of the present invention, in particular the polycarbonate resin of the present invention, at 23°C and at a wavelength of 589 nm is, in case the resin in- cludes the structural unit (II), frequently 1.630 or higher, preferably 1.635 or higher, or 1.640 or higher, more preferably 1.645 or higher, or 1.650 or higher, still more preferably 1.655 or higher, or 1.660 or higher, in particular 1.665 or higher, 1.670 or higher, 1.675 or higher, or 1.680 or higher, and specifically 1.685 or higher.
  • the structural unit (II) frequently 1.630 or higher, preferably 1.635 or higher, or 1.640 or higher, more preferably 1.645 or higher, or 1.650 or higher, still more preferably 1.655 or higher, or 1.660 or higher, in particular 1.665 or higher, 1.670 or higher, 1.675 or higher, or 1.680 or higher, and specifically 1.685 or higher.
  • the refractive index of the copolycarbonate resin including the structural unit (II) and a structural unit (V) according to the present invention is preferably 1.640 to 1.730, preferably 1.650 to 1.730, still more preferably 1.660 to 1.730.
  • the Abbe number ( ⁇ or ⁇ d) of the thermoplastic resin of the present invention, in particular the polycarbonate resin of the present invention is preferably 26 or lower, 25 or lower, 24 or lower, or 23 or lower, more preferably 22 or lower, or 21 or lower, and still more preferably 20 or lower, or 19 or lower.
  • Tg glass transition temperature of the thermoplastic resin of the present in- vention, in particular the polycarbonate resin of the present invention, is, in consid- eration of that the polycarbonate is usable for injection molding, frequently in the range of 90 to 185°C, preferably in the range of 90 to 180°C, more preferably in the range of 100 to 170°C or 110 to 170°C, and especially in the range of 110 to 160°C, 120 to 165°C or 130 to 160°
  • the lower limit of Tg is preferably 130°C and more pref- erably 135°C, and the upper limit of Tg is preferably 180°C and more preferably 170°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 tem- perature of the resin may be too high, and thus the resin may be undesirably de- composed 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 calorimetry (DSC) using a 10° C/minute heating program according to the protocol of JIS K7121-1987.
  • the absolute value of the orientation birefringence of the thermoplastic resin is preferably in the range of 0 to 1x10 -2 , more preferable in the range of 0 to 5x10 -3 , even more preferable . in the range of 0 to 2x10 -3 , in particular in the range of 0 to 1x10 -3 , and specifically in the range of 0 to 0.4x10 -3 .
  • An optical molded body such as an optical element produced by using a polycar- bonate resin of the present invention has a total light transmittance of preferably 85% or higher, more preferably 87% or higher, and especially preferably 88% or higher.
  • a total light transmittance of preferably 85% or higher is as good as that provided by bisphenol A type polycarbonate resin or the like.
  • the thermoplastic resin according to the present invention has high moisture 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 thermoplastic resin and then measuring the total light transmittance of the molded body after the PCT test.
  • PCT test pressure cooker test
  • an injec- tion 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.
  • thermoplastic resin 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 thermoplastic resin is considered to have a higher moisture and heat resistance than that of the conventional thermoplastic resin.
  • the thermoplastic resin according to the present invention has a b value, which represents the hue, of preferably 5 or lower. As the b value is smaller, the color is less yellowish, which is good as a hue.
  • the diol component which is used in the preparation of the polycarbonates or polyesters, may additionally comprise one or more diol mon- omers, which are different from the monomer compound of the formula (I), such as one or more monomers of the formula (IV).
  • M/REUCTR-037-PC RCA-EO_Trimer 76 Suitable diol monomers, which are different from the monomer compound of the formula (I), 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- dimethanol, decalin-2,6-dimethanol, norbornane dimethanol, pentacyclopenta- decane dimethanol, cyclopentane-1,3-dimethanol, spiroglycol, 1,4:3,6- dianhydro-D-sorbitol, 1,4:3,6-dianhydro-D-mannitol and 1,4:3,6-dianhydro-L- iditol are also included in examples of the diol; and - aromatic diols, in particular aromatic diols of the formula (IV) such as bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxy
  • the diol component comprises at least one monomer of the formula (IV) in addition to the monomer of formula (I).
  • the total amount of mono- mers of formulae (I) and (IV) contribute to the diol component by at least 90% by weight, based on the total weight of the diol component or by at least 90 mol-%, M/REUCTR-037-PC RCA-EO_Trimer 77 based on the total molar amount of the diol monomers of the diol component.
  • the diol component comprises at least one monomer selected from the monomers of formulae (IV-11) to (IV-22) in addition to the monomer of formula (I).
  • the diol component comprises at least one monomer selected from the monomers of formulae (IV-11), (IV-12), (IV-13), (IV-14), (IV-15), (IV-21) and (IV-22) in addition to the monomer of formula (I).
  • the diol compo- nent comprises at least one monomer selected from 2,2'-bis(2-hydroxyethoxy)-1,1'- binaphthyl, 2,2'-bis(2-hydroxyethoxy)-6,6’-diphenyl-1,1'-binaphthyl, 9,9-bis(6-(2- hydroxyethoxy)-2-naphthyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 2-[4-[4-(2-hydroxyethoxy)-3,5-di(thianthrene-1-yl)phenyl]sulfonyl-2,6- di(thianthrene-1-yl)phenoxy]ethanol,
  • the relative amount of monomer compound of formula (I), based on the total weight of the diol component is at least 1% by weight, preferably at least 10% or at least 30% by weight, in particular at least 15% by weight or at least 20% by weight and especially at least 25% by weight or at least 30% by weight, preferably in the range of 1 to 99% by weight or in the range of 10 to 98% by weight, in par- ticular in the range of 20 to 98% by weight or in the range of 25 to 98% by weight or in the range of 30 to 98% by weight or in the range 30 to 97% by weight, especially in the range of of 15 to 96% by weight or in the range of 20 to 95% by weight or in the range 30 to 95% by weight or in the range of 30 to 93% by weight, but may also be as high as 100% by weight.
  • the relative molar amount of monomer compound of formula (I), based on the total molar amount of the diol component is at least 1 mol-%, preferably at least 10 mol-% or at least 30 mol-%, in particular at least 15 mol-% or at least 20 mol-% and especially at least 25 mol-% or at least 30 mol-%, preferably in the range of 1 to 99 mol-% or in the range of 10 to 98 mol-% or in the range of 20 to 98 mol-% or in the range of 25 to 98 mol-%, in particular in the range of 15 to 96 mol-% or in the range of 20 to 95 mol-% or in the range of 30 to 95 mol-% or in the range of 30 to 93 mol-%, especially in the range of 20 to 90 mol-% or in the range of 25 to 90 mol-% or in the range of 30 to 90 mol-% or in the range of 32 to 90 mol-% or in the range of 35
  • the relative molar amount of monomer compound of formula (IV), based on the total molar amount of the diol component, will not exceed 99 mol-% or M/REUCTR-037-PC RCA-EO_Trimer 78 90 mol-% or 70 mol-%, in particular not exceed 85 mol-% or 80 mol-% and especial- ly not exceed 75 mol-% or 70 mol-%, and is preferably in the range of 1 to 99 mol-% or in the range of 2 to 90 mol-% or in the range of 2 to 80 mol-% or in the range of 2 to 75 mol-%, in particular in the range of 4 to 85 mol-% or in the range of 5 to 80 mol-% or in the range of 5 to 70 mol-% or in the range of 7 to 70 mol-% , especially in the range of 10 to 80 mol-% or in the range of 10 to 75 mol-% or in the range of 10 to 70 mol-% or in the range of 10
  • the total molar amount of monomers of formula (I) and monomers of formula (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 mono- mers in the diol component.
  • Examples of further preferred aromatic dihydroxy compound which can be used in addition to the monomers of formula (I) and optionally monomers of formula (IV) include, but are not limited to bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bi- sphenol S, bisphenol P, bisphenol PH, bisphenol TMC, bisphenol Z and the like.
  • the monomers form- ing the thermoplastic polymer may also include a monofunctional compound, in case of polycarbonates a monofunctional alcohol and in case of polyesters a mono- functional alcohol or a monofunctional carboxylic acid.
  • Suitable monoalcohols are butanol, hexanol and octanol.
  • Suitable monocarboxylic acids include e.g. benzoic acid, propionic acid and butyric acid.
  • the monomers forming the thermoplastic polymer may also in- clude a polyfunctional compound, in case of polycarbonates a polyfunctional alco- hol having three or more hydroxyl groups and in case of polyesters a polyfunctional alcohol having three or more hydroxyl groups or a polyfunctional carboxylic acid having three or more carboxyl groups.
  • Suitable polyfunctional alcohols are e.g.
  • glyc- erine trimethylol propane, pentaerythrit and 1,3,5-trihydroxy pentane.
  • Suitable polyfunctional carboxylic acids having three or more carboxyl groups are e.g. trimellitic acid and pyromellitic acid. The total amount of these compounds, will frequently not exceed 10 mol-%, based on the molar amount of the diol component.
  • 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 car- bonate, diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p- chlorophenyl carbonate and dinaphthyl carbonate. Out of these, diphenyl carbonate M/REUCTR-037-PC RCA-EO_Trimer 79 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, glu- taric 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 nor- bornandicarboxylic acid; and - aromatic dicarboxylic acids, such as benzene dicarboxylic acids, specifically phthalic acid, isophthalic acid, 2-methylterephthalic acid or ter
  • 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 dihydroxy compound(s) in total.
  • the polycarbonates of the present invention can be prepared by reacting a diol component comprising a monomer of formula (I) and optionally a further diol mon- omer such as a monomer of the formula (IV) and a carbonate forming monomer by analogy to the well known preparation of polycarbonates as described e.g. in US 9,360,593, US 2016/0319069 and US 2017/0276837, to which full reference is made.
  • the polyesters of the present invention can be prepared by reacting a diol compo- nent comprising a monomer of formula (I) 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 reference is made.
  • the polyestercarbonates of the present invention can be prepared by reacting a diol component comprising a monomer of formula (I) and optionally a further diol mon- omer such as a monomer of the formula (IV), a carbonate forming monomer and a dicarboxylic acid or its ester forming derivative by analogy to the well known prepa- ration of polyestercarbonates as described in the art.
  • the polycarbonates, polyesters and polyestercarbonates are usually prepared by reacting the monomers of the diol component with the carbonate forming mono- mers and/or the ester forming monomers, i.e.
  • transesterification catalysts are basic compounds, which specifically in- clude but are not limited to alkaline metal compounds, alkaline earth metal com- pound, nitrogen-containing compounds, and the like.
  • suitable transesteri- fication catalysts are acidic compounds, which specifically include but are not lim- ited to Lewis acid compounds of polyvalent metals, including compounds such as zinc, tin, titanium, zirconium, 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 borohydrides, 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 borohydrides, alkaline metal hydrogen carbonates, alkaline metal phosphate, alkaline metal hydrogenphosphate, alkaline metal hydroxides, alkaline metal hydrides, alkaline metal alkoxides, and the like.
  • M/REUCTR-037-PC RCA-EO_Trimer 81 include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydrox- ide, sodium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stea- rate, 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, dicesium 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 phe- nylphorsphoric acid, alkaline earth metal phenolates, alkaline earth metal earth oxides, alkaline earth metal carbonates, alkaline metal borohydrides, alkaline earth metal hydrogen carbonates, alkaline 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 phe- nylphorsphoric acid
  • alkaline earth metal phenolates alkaline earth metal earth oxides
  • alkaline earth metal carbonates alkaline metal borohydrides
  • alkaline earth metal hydrogen carbonates alkaline earth metal hydroxides
  • alkaline earth metal hydrides alkaline earth metal alkoxides, and the like.
  • the nitrogen-containing compound include quaternary ammoniumhy- droxide, salt thereof, amines, and the like.
  • qua- ternary ammoniumhydroxides including an alkyl group, an aryl group or the like, such as tetramethylammoniumhydroxide, tetraethylammoniumhydroxide, tetraprop- ylammoniumhydroxide, tetrabutylammoniumhydroxide, trimethylbenzylammoni- umhydroxide, and the like; tertiary amines such as triphenylamine, dimethylbenzyl- amine, triphenylamine, and the like; secondary amines such as diethylamine, dibu- tylamine, and the like; primary amines such as propylamine, butylamine, and the like; imidazoles such as 2-methylimidazole, 2-phenylimidazole, benzoimidazole, and the like; bases or basic salts such as ammonia, tetramethylammoniumborohydride, tetrabutylammonium
  • 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.
  • M/REUCTR-037-PC RCA-EO_Trimer 82 may be used independently or in a combination of two or more.
  • transesterification 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, zirconiumtetrabutoxide, 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, preferably 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 reacted in the absence of an additional inert solvent. While the reaction is per- formed 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 reaction between the monomers and the formation of the byproduct takes place.
  • the byproduct resides for at least a while in the polycondensation 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.
  • thermo- plastic resin in the case where the byproduct is removed by distillation soon after being generated, the finally obtained thermo- plastic resin has a low content of high molecular-weight resin molecules.
  • thermo- trast in the case where the byproduct is allowed to reside in the reactor for a cer- tain time, the finally obtained thermoplastic resin has a high content of high molec- ular-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 includ- ing 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 M/REUCTR-037-PC RCA-EO_Trimer 83 reactor including a combination of such reactors is preferably usable in considera- tion of the viscosity of the polymerization product.
  • the catalyst may be re- moved 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 acid- ic substance.
  • deactiva- tors 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.
  • 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 fil- trated 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 M/REUCTR-037-PC RCA-EO_Trimer 84 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 thermoplastic resin may be molded by any conventional molding procedure for producing optical elements.
  • Suitable molding procedures include but are not limited to injection molding, compression molding, casting, roll processing, extrusion mold- ing, extension and the like. While it is possible to mold the thermoplastic resin of the invention as such, it is also possible to mold a resin composition, which contains at least one thermo- plastic resin of the invention 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, surfactants, antibacterial agents, releasing agents, ultraviolet ab- sorbers, plasticizers, compatibilizers, 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-butyl-4-hydroxyphenyl)propionate], pentaerythritol-tetrakis[3-(3,5-di-tert- butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10- tetraoxa-3,9-diphosphaspiro[5.5]undecane, 5,7-
  • 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, M/REUCTR-037-PC RCA-EO_Trimer 85 phosphoric acid, phosphonous acid, phosphonic acid, esters thereof, and the like.
  • triphenylphosphite tris(nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2,6-di-tert-butylphenyl)phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophe- nylphosphite, dioctylmonophenylphosphite, diisopropylmonophenylphosphite, monobutyldiphenylphosphite, monodecyldiphenylphosphite, monooctyldiphenyl- phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritoldiphosphite, 2,2-
  • the content of the phosphorus-based processing stabilizer in the thermo- plastic 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 pentaerythritol-tetrakis(3-laurylthiopropionate), pentaerythritol-tetrakis(3- myristylthiopropionate), pentaerythritol-tetrakis(3-stearylthiopropionate), dilauryl- 3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'- thiodipropionate, and the like.
  • the content 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 thermoplastic 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 in- clude 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 of an alcohol and a fatty acid include the esters of a monovalent alcohol having a carbon number of 1 to 20 and a saturated fatty acid having a car- bon number of 10 to 30.
  • Preferred examples of partial or total esters of a polyvalent alcohol and a fatty acid include the partial or total ester of a polyvalent alcohol hav- ing a carbon number of 2 to 25 and a saturated fatty acid having a carbon number of 10 to 30.
  • Specific examples of the ester of a monovalent alcohol and a fatty acid M/REUCTR-037-PC RCA-EO_Trimer 86 include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, and the like.
  • partial or total ester of a polyvalent alcohol and a fatty acid include monoglyceride stearate, monoglyceride stearate, diglyceride stearate, triglyceride stearate, monosorbitate stearate, monoglyceride behenate, monoglyceride caprylate, monoglyceride laurate, pentaerythritol monos- tearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propyl- eneglycol monostearate, biphenyl biphenate, sorbitan monostearate, 2- ethylhexylstearate, total or partial esters of dipentaerythritol such as dipentaeryth- ritol hexastearate and the like, etc.
  • 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 respect to 100 parts by weight of the thermoplastic resin.
  • Preferred ultraviolet absorbers are selected from the group consisting of benzotria- zole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, tria- zine-based ultraviolet absorbers, cyclic iminoester-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers. Namely, the following ultraviolet ab- sorbers 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- hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5- methylphenyl)-5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3- tetramethylbutyl)-6-(2N-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-octy
  • benzophenone-based ultraviolet absorbers examples include 2,4- dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4- octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy- 5-sulfoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid hy- drate, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5- sodiumsulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2'- carboxybenzophenone, and the like.
  • 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- benzoxazine-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-naphthalene)bis(3,1-benzoxazine-4-one), 2,2'-(1,5- naphthalene)bis(3,1-benzoxazine-4-one), 2,2'-(2-methyl-p-phenylene)bis(3,1- benzoxazine-4-one), 2,2'-(2-nitro-p-phenylene)bis(3,1-benzoxazine-4-one), 2,2'-(2- chloro-p-phenylene)bis(3,1-benzoxazine
  • 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 pref- erably 0.05 to 0.8 parts by weight, with respect to 100 parts by weight of the ther- moplastic resin.
  • thermo- plastic resins in particular the polycar- bonate resins, comprising repeating units of formulae (II) and (IIa), respectively, as described herein, provide high transparency and high refractive index to thermo- plastic resins, which therefore are suitable for preparing optical devices, where high transparency and high refractive index is required.
  • thermo- plastic polycarbonates having structural units of formulae (II) and (IIa), respective- ly are characterized by having a high refractive index, which is preferably at least 1.640, more preferably at least 1.660, in particular at least 1.670.
  • thermoplastic resin in particular a polycarbonate resin
  • the contribution of the monomer of the formulae (I) and (Ia), respectively, to the refractive index of the thermoplastic resin, in particular a polycarbonate resin, will depend from the refractive index of said monomer and the relative amount of said monomer in the thermoplastic resin. In general, a higher refractive index of the monomer contained in the thermoplastic resin will result in a higher refractive index of the resulting thermoplastic resin.
  • the refractive index of a ther- moplastic resin comprising structural units of the formula (II) can be calculated M/REUCTR-037-PC RCA-EO_Trimer 88 from the refractive indices of the monomers used for preparing the thermoplastic resin, either from the refractive index of the monomers or ab initio, e.g. by using the computer software ACD/ChemSketch 2012 (Advanced Chemistry Development, Inc.).
  • the refractive index of the thermoplastic resin in particular a polycarbonate resin
  • n Dn are the refractive indices of the homopolymers synthesized from only one of the monomers 1, 2, .... n at a time.
  • x 1 , x 2 , .... x n are the mass fractions of the OH monomers 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 thermoplastic resins can be determined directly or in- directly.
  • the refractive indices n D of the thermoplastic res- ins are 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 thermoplastic resin.
  • the refractive indices of the homopolycarbonates of the com- pounds of formula (I) can also be determined indirectly.
  • a co-polycarbonate of the respective monomer of formula (I) with 9,9-bis(4-(2- hydroxyethoxy)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 n D of the co-polycarbonate 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.
  • the compounds of formula (I) 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 (I) preferably does not exceed 100, more pref- erably 50, even more preferably 20, in particular 10 or 5.
  • the thermoplastic resin according to the present invention has a high refractive index and a low Abbe number.
  • the thermoplastic resin of the present invention can be used for producing a transparent conductive substrate usable for a liquid crystal display, an organic EL display, a solar cell and the like.
  • thermoplastic resin 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. Accordingly, molded articles, such as optical devices can be formed using the ther- moplastic resins 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, com- pression molding, injection compression molding, extrusion molding, or solution casting.
  • thermoplastic resins of the present invention are very suitable for production of optical lenses which requires injection molding.
  • the thermoplastic resins of the pre- sent invention such as the polycarbonate resin
  • the thermoplastic resins of the pre- sent invention can be used with other thermo- plastic resins, for example, different polycarbonate resin, polyestercarbonate resin, polyester resin, and other resins, as a mixture.
  • the thermoplastic resins of the present invention can be mixed with additives for forming the optical devices.
  • additives for forming the optical devices above-mentioned ones can be used.
  • the additives may include antioxi- dants, processing stabilizers, photostabilizers, polymerization metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, antibacterial agents, releasing agents, ultraviolet absorbers, plasticizers, compatibilizers, and the like.
  • another aspect of the present invention relates to an optical device made of a thermoplastic resin as defined above, where the thermo- plastic resin comprising a structural unit represented by the formula (II) and op- tionally of formula (V).
  • the thermo- plastic resin comprising a structural unit represented by the formula (II) and op- tionally of formula (V).
  • An optical device made of an optical resin comprising the repeating units of the formula (II) and optionally repeating units of the formula (V) as defined herein are usually optical molded articles such as optical lenses, for example car head lamp lenses, Fresnel 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 sub- strates, optical filters or prisms, liquid crystal panels, optical cards, optical sheets, optical fibers, optical connectors, 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, Fresnel 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 sub- strates, optical filters or prisms, liquid crystal panels,
  • Optical resins comprising repeating units of the formula (II) and optionally repeating units of the 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 thermoplastic resin according to the present invention has a high refractive index, a low Abbe number and a low degree of bire- fringence, and is highly moisture and heat resistant. Therefore, 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.
  • the optical lens is used in the form of an aspherical lens.
  • an aspherical lens may make the spherical aberration substantially zero. Therefore, it is not necessary to use a plurality of spherical lenses to remove the spherical ab- erration. Thereby the weight and the production cost of a device including the spherical aberration is decreased.
  • An aspherical lens is useful especially as a cam- era lens among various types of optical lenses.
  • the present invention easily pro- vides an aspherical lens having a high refractive index and a low level of birefrin- gence, 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 the repeating units of the formula (II) and optionally repeating units of the formula (V) as defined herein.
  • the optical lens of the present invention is characterized by a small optical distor- tion.
  • An optical lens comprising a conventional optical resin has a large optical dis- tortion. Although it is not impossible to reduce the value of an optical distortion by molding conditions, the condition widths are very small, thereby making molding extremely difficult.
  • the resin having repeating units of the formula (II) and optionally repeating units of the formula (V) as defined herein has an extremely M/REUCTR-037-PC RCA-EO_Trimer 91 small optical distortion caused by the orientation of the resin and a small molding distortion, an excellent optical element can be obtained 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.
  • the aspherical lens is par- ticularly useful as a camera lens. Since resins 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 material 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 material but preferably an inorganic material.
  • the inorganic material examples include oxides and fluorides such as silicon oxide, aluminum oxide, zirco- nium oxide, titanium oxide, cerium oxide, magnesium oxide and magnesium fluo- ride.
  • 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 according to the pre- sent invention is high in transparency and heat resistance, and therefore is prefer- ably usable for a liquid crystal substrate film, an optical memory card or the like.
  • the dust environment is preferably of class 6 or lower, and more pref- erably of class 5 or lower.
  • the following examples serve as further illustration of the invention. 1.
  • the solid was collected by centrifugation and the filter cake was washed twice with acetone to yield the crude MHBNA (321 kg). This material was stirred in 1280 kg of water for 2 h at room temperature. The solid was collected by filtration, the filter cake was washed twice with water and twice with acetone to yield 222 kg of the crude product. This crude product was further puri- fied by repeated crystallization from acetone to yield the title compound with a chemical purity of >99%.
  • Methanesulfonyl chloride (130.3 g, 1.138 mol, 3 eq.) was then added dropwise. The stirring was continued at 0°C for additional 2 h and the reaction mixture was then allowed to warm to room temperature. The reaction mixture was stirred until complete conversion is achieved according to TLC. Water was added and the phases were separated. The organic phase was washed with a saturated sodium bicarbonate solution, dried over sodium sulfate and the solvent was removed in vacuo to gain the dimesylated product as a white solid.
  • Methanesulfonyl chlo- ride (21.1 g, 208 mol, 3 eq.) was then added dropwise. The stirring was continued at 0°C for additional 2 h and the reaction mixture was then allowed to warm to room temperature. The reaction mixture was stirred until complete conversion was achieved according to TLC (heptane/EtOAc 1:5). Water was then added and the phases were separated. The organic phase was washed with a saturated aqueous sodium bicarbonate solution, dried over sodium sulfate and the solvent was re- moved in vacuo to gain the desired dimesylated product as a white solid. The crude material was purified be stirring in pentane at room temperature. Yield 46.7 g (97%) of the title compound.
  • thermoplastic resins from monomers of formula (I) 3.1 Analytics relating to resins prepared from monomers of formula (I):
  • Refractive index (n D ) The refractive index was measured using a disk shaped test piece with a thickness of 3 mm made by polycarbonate resin as a test piece according to JIS B 7071- 2:2018. The measurement was conducted at 23 ⁇ C using the refractive index measurement device KPR-3000 manufactured by Shimadzu Corporation.
  • Abbe number ( ⁇ ) A disk shaped test piece with a thickness of 3 mm which is the same as the test piece used in the refractive index measurement.
  • the refractive index values were measured 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 calculat- ed using the below-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; Column temperature: 40°C.
  • the number average molecular weight (Mn) values were calculated using similar methods to those used for measuring the Mw values described above.
  • the polysty- rene converted weight average molecular weights (Mw) and number average mo- lecular weights (Mn) were calculated using a previously prepared standard curve of polystyrene. Specifically, the standard curve was prepared using a standard poly- styrene for which the molecular weight was known (“PStQuick C” from Tosoh Cor- poration). Further, a calibration curve was 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.
  • Mw and Mn were calculated based on the following calculation formulae: M/REUCTR-037-PC RCA-EO_Trimer 104
  • “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.
  • the GPC analysis of the low molecular weight compounds is 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 resins 3.2.1 Polycarbonate resins
  • Example 2 As materials, 16.0004 g (0.0365 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF) having the molecular structure represented by the formula below, 9.1079g (0.0091 mol) of 2,2'-[[1,1'-binaphthalene]-2,2'-diylbis(oxyethane-2,1-diyloxy[1,1'- binaphthalene]-2',2-diyloxy)]di(ethan-1-ol) (compound of formula (Ia)) that was obtained in the above-mentioned Preparation Example 1c, 10.0155g (0.0468 mol) of diphenylcarbonate (DPC) and 0.3832 ⁇ 10 -4 g (0.4561 ⁇ 10 -6 mol) of sodium hydrogen carbonate were put
  • the reactor was flushed with nitrogen and the inside pressure was set to 101.3 kPa.
  • the reactor was immersed in an oil bath that had been heated to 180 ⁇ C and then the ester exchange reaction started. Stirring of the reaction mixture started 5 minutes after the start time of the reaction. 20 minutes later, the pressure of the reaction mixture was reduced from 101.3 kPa to 93.33 kPa over 10 minutes. 10 minutes later, heating of the reaction mixture was started and then the reaction mixture was heated to 190 ⁇ C over 10 minutes.10 minutes later, the pressure of the reaction mixture was reduced from 93.33 kPa to 26.66 kPa over 10 minutes.
  • reaction mixture was heated from 190 ⁇ C to 210 ⁇ C and the pressure of the reaction mixture was further reduced to 24.00 kPa over 20 minutes.
  • the reac- tion mixture was heated to 220 ⁇ C and the pressure of the reaction mixture was further reduced to 20.00 kPa over 10 minutes.
  • the reaction mixture was heated to 240 ⁇ C and the pressure of the reaction mixture was reduced to 17.33 kPa over 10 minutes and maintained at this level for 30 minutes.
  • the pressure of the reaction mixture was then reduced to 0 kPa and maintained at this level for 30 minutes. Nitrogen gas was introduced into the reactor and, the pressure of the reaction mix- ture was recovered to 101.3 kPa to finally obtain the polycarbonate resin.
  • Comparative example 1 As materials, 20.9700g (0.0478 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF) having the molecular structure represented by the formula below, 4.4765g M/REUCTR-037-PC RCA-EO_Trimer 106 (0.0120mol) of 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl(BNE), 13.1254g(0.0613 mol) of diphenylcarbonate (DPC) and 0.5022 ⁇ 10 -4 g (0.5978 ⁇ 10 -6 mol) of sodium hydrogen carbonate were put into a 300 milliliter reactor with a stirrer and a distil- lation device.
  • BPEF 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene
  • the reactor was flushed with nitrogen and the inside pressure was set to 101.3 kPa.
  • the reactor was immersed in an oil bath that had been heated to 180 ⁇ C and then the ester exchange reaction started. Stirring of the reaction mixture started 5 minutes after the start time of the reaction. 20 minutes later, the pressure of the reaction mixture was reduced from 101.3 kPa to 93.33 kPa over 10 minutes. 10 minutes later, heating of the reaction mixture was started and then the reaction mixture was heated to 190 ⁇ C over 10 minutes.10 minutes later, the pressure of the reaction mixture was reduced from 93.33 kPa to 26.66 kPa over 10 minutes.
  • reaction mixture was heated from 190 ⁇ C to 210 ⁇ C and the pressure of the reaction mixture was further reduced to 24.00 kPa over 20 minutes.
  • the reac- tion mixture was heated to 220 ⁇ C and the pressure of the reaction mixture was further reduced to 20.00 kPa over 10 minutes.
  • the reaction mixture was heated to 240 ⁇ C and the pressure of the reaction mixture was reduced to 17.33 kPa over 10 minutes and maintained at this level for 30 minutes.
  • the pressure of the reaction mixture was then reduced to 0 kPa and maintained at this level for 30 minutes. Nitrogen gas was introduced into the reactor and, the pressure of the reaction mix- ture was recovered to 101.3 kPa to finally obtain the polycarbonate resin.

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Abstract

La présente invention concerne des composés binaphtyles oligomères de formule (I) qui sont appropriés en tant que monomères pour préparer des résines thermoplastiques, telles que des résines polycarbonate, qui ont des propriétés optiques et mécaniques bénéfiques et peuvent être utilisées pour produire des dispositifs optiques. Dans la formule (I), X1, X2, Y1, Y2, E1, E2, Ar, R1, R2, R3, R4, m, n, p et q sont tels que définis dans la présente description.
PCT/EP2024/080131 2023-10-25 2024-10-24 Composés binaphtyles oligomères et résines thermoplastiques Pending WO2025088066A1 (fr)

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