Copolycarbonates and compositions thereof with high refractive index and low birefringence

Abstract

A copolycarbonate comprises at least 2 wt% soft repeating units and less than or equal to 98 wt% hard repeating units, based on the total weight of the copolycarbonate, wherein the hard repeating units comprise formula (A), wherein in Formula (A), a and b are each independently 0-4, c and d are each independently 0-5, and Ra, Rb, Rc, and Rd are each independently halogen, substituted or unsubstituted C1-36 hydrocarbyloxy, or substituted or unsubstituted C1-36 hydrocarbyl; and wherein the soft repeating units comprise: repeating units derived from C5-44 aliphatic dicarboxylic acids and its reactive derivatives or equivalents; repeating units derived from C5-44 aliphatic dicarboxylic acids and its reactive derivatives or equivalents and siloxane repeating units; or siloxane repeating units of formula (15) wherein in formula (15) each R is independently a hydrocarbyl or hydrocarbyloxy group; and E has an average value of 2 to 1,000.

Description

22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122 COPOLYCARBONATES AND COMPOSITIONS THEREOF WITH HIGH REFRACTIVE INDEX AND LOW BIREFRINGENCE CROSS REFERENCE TO RELATED APPLICATION This application claims priority to European Patent Application No.24153772, filed on January 24, 2024, the contents of which is hereby incorporated by reference in its entirety. BACKGROUND

[0001] This disclosure relates to copolycarbonate resins and compositions thereof, and in particular to copolycarbonate resins and compositions with optical properties (e.g., high refractive index and low birefringence), methods of manufacture, and uses thereof.

[0002] Polycarbonates are useful in the manufacture of articles and components for a wide range of applications, from automotive parts to electronic appliances. Because of their high refractive index, polycarbonates have been used in optical applications such as camera lenses, eyeglass and safety glass lenses, illumination lenses such as light fixtures, flashlight and lantern lenses, pickup lenses, Fresnel lenses, lenses for a laser printer, projection lenses, and motor vehicle headlight lenses and covers. However, some conventional polycarbonates do not have a sufficiently low birefringence for particular optical applications. In addition, some conventional monomers when incorporated into a polycarbonate can provide the desired combination of a high refractive index and low birefringence, however, the glass transition temperature of the polycarbonate is outside the range for what is suitable for ease of processing. Further, with miniaturization and thinning of electronics parts continue in the future, it is very desirable to have polycarbonates with sufficient fluidity to mold small, thin, and complex parts.

[0003] There accordingly remains a need in the art for copolycarbonates that have a combination of a high refractive index, low birefringence, improved fluidity, and a glass transition temperature suitable for processing. It would be a further advantage if the articles prepared from the copolycarbonates were scratch-resistant. SUMMARY

[0004] The above-described and other deficiencies of the art are met by a copolycarbonate comprising at least 2 wt% soft repeating units and less than or equal to 98 wt% hard repeating units, based on the total weight of the copolycarbonate, wherein the hard repeating units comprise formula (A) and optionally hard repeating units derived from formula (2)22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122wherein in Formula (A), a and b are each independently 0-4, c and d are each independently 0-5, and Ra, Rb, Rc, and Rd are each independently halogen, substituted or unsubstituted C1-36 hydrocarbyloxy, or substituted or unsubstituted C1-36 hydrocarbyl; and wherein in formula (2), each of A1and A2is a monocyclic divalent aromatic group and Y1is a single bond or a bridging group having one or more atoms that separate A1from A2; and wherein the soft repeating units comprise: repeating units derived from C5-44 aliphatic dicarboxylic acids and its reactive derivatives or equivalents; repeating units derived from C5-44 aliphatic dicarboxylic acids and its reactive derivatives or equivalents and siloxane repeating units; or siloxane repeating units of formula (15)wherein in formula (15) each R is independently a C1-13 alkyl, C1-13 alkoxy, C2-13 alkenyl, C2-13 alkenyloxy, C3-6 cycloalkyl, C3-6 cycloalkoxy, C6-14 aryl, C6-10 aryloxy, C7-13 arylalkylene, C7-13 arylalkylenoxy, C7-13 alkylarylene, or C7-13 alkylaryleneoxy; and E has an average value of 2 to 1,000.

[0005] In another aspect, a method of manufacture of the copolycarbonate comprises: polymerizing monomer precursors of the hard repeating units comprising formula (A) and optionally monomer precursors of the hard repeating units of formula (2) with the monomer precursors of the soft repeating units in the presence of a carbonyl source under conditions effective to provide the copolycarbonate.

[0006] In another aspect, a composition comprises the copolycarbonate and an additive composition.

[0007] In yet another aspect, an article comprises the above-described copolycarbonate or composition.

[0008] In still another aspect, a method of manufacture of an article comprises shaping, blow molding, injection molding, casting, thermoforming, laminating, or extruding the copolycarbonate or copolycarbonate composition to provide the article.22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122

[0009] The above described and other features are exemplified by the following drawing, detailed description, examples, and claims. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] The FIGURE shows rheology data (the effect of temperature on viscosity or the melt stability) for BCB homopolymer and conventional solutions EP4500 and OKP4, which shows that the conventional polymers can be processed (or stable) only at lower temperatures and starts to degrade at higher temperatures. DETAILED DESCRIPTION

[0011] Polycarbonates, relative to other thermoplastics, are noted for their optical properties, thermal resistance, and mechanical properties such as impact strength, for example, physical shock due to dropping the item, and extremes of temperature and humidity. However, many optical grade commercial polycarbonates have insufficiently low birefringence. It is desirable in optical applications such as lenses to provide a combination of a high refractive index and a low birefringence. Low birefringence in a molded plastic means that the molded plastic has low light distortion, optical aberrations and a better quality image, which is desired in lenses.

[0012] Birefringence (BR) is defined as the refractive index of a part having an x part thickness and expressed in units of thickness (e.g., nm). Birefringence is strongly dependent on molding conditions. Birefringence in a polymeric article is fundamentally related to orientation and deformation of its constituent polymer molecules. Residual birefringence of the molded or extruded thermoplastic polymeric article can be influenced by several factors including the chemical structure of the raw material from which the article is fabricated, the degree of molecular orientation therein, mechanical stresses applied during melt processing, cooling rate, and thermal relaxation or annealing of the polymeric article during the fabrication process.

[0013] Conventional approaches to minimizing birefringence include modifying the molding parameters by, for example, use of a higher molding temperature or by decreasing the holding time, thus promoting isotropy in the molded article. Birefringence may also occur due to the anisotropic effect of polymer shape on its flow properties, where the polymer chains in an injection molded plastic (as in a molded lens, for example) orient along the direction of flow. Desirably, a high flow results in more randomization and a lower degree of orientation, and hence lower birefringence is associated with higher flow materials.

[0014] Currently, exemplary commercially available materials for optical applications that have low birefringence and a high refractive index include materials such as OKP4,22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122 available from Osaka Gas Chemicals Co. OKP4 is a polycarbonate derived from ethoxylated bisphenol fluorene monomers. Polycarbonate copolymers from ethoxylated monomers are less thermally stable due to the beta elimination of the ethoxylated carbonate linkage. This limits processability to temperatures less than 270 °C, restricting the processing window. This means that a resin with a glass transition temperature (glass transition temperature) of 150 °C can only be processed at 120 °C greater than the glass transition temperature, which is 30 °C less than the typical target of 150 °C greater than the glass transition temperature. Generally, the target temperature for the processing of materials is the glass transition temperature plus 150 °C. However, at these temperatures, discoloration and decomposition of the OKP4 resin can occur due to the beta elimination of the ethoxylated carbonate linkage. Therefore, despite ethoxylated polycarbonates having a combination of a high refractive index and a low birefringence, the thermal stability and processing window for such materials is limited.

[0015] Not wishing to be bound by theory, the copolycarbonates and compositions of the present disclosure have an improved thermal stability due to the aromatic polycarbonate backbone. This improved stability translates into a broader processing window that can reduce cycle time and birefringence in the molded lens.

[0016] An additional disadvantage of polycarbonates derived from ethoxylated monomers is that they must be prepared by melt polymerization. In particular, the ethoxylated fluorene bisphenol monomer has insufficient acidity for interfacial polymerization. Furthermore, ethoxylated monomers can result in the release of formaldehyde and cause out-gassing issues. Polycarbonates derived from other commercially available high refractive index monomers that lack ethoxylated groups (and can be prepared using interfacial polymerization) have glass transition temperatures that are too high for ease of processing. For example, homopolymers of bisphenol fluorene (BPF) and biscresyl fluorene (BCF) have glass transition temperature values of 250 °C and 220 °C, respectively. These high glass transition temperature polycarbonates have limited use in optical applications which require much lower glass transition temperature values to allow for well-molded parts with low stress (i.e., stress optic coefficient).

[0017] The inventors have surprisingly discovered novel copolycarbonates that have a high refractive index and low birefringence suitable for optical applications, as well as a glass transition temperature of at least 130 °C for ease of processing, preferably a glass transition temperature ranging from 130-170 °C. The novel copolycarbonate includes at least 2 wt% soft repeating units and less than or equal to 98 wt% hard repeating units, based on the total weight of the copolycarbonate, wherein the hard repeating units include formula (A)22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122

[0018] It was surprising that such a high level of soft repeating units could be incorporated without adversely affecting the optical properties because typically, the achievement of a combination of high refractive index and low birefringence suitable for optical applications is a result of rigidity in the polymer backbone. Soft repeating units are typically amorphous in nature and provide the elastomeric properties of flexibility and reduce the glass transition temperature of the resin, potentially adversely affecting the optical properties. As used herein, “soft repeating units” refer to repeating units wherein the corresponding homopolymer has a glass transition temperature below room temperature. As used herein, “hard repeating units” refer to repeating units wherein the corresponding homopolymer has a glass transition temperature higher than the glass transition temperature of the copolycarbonate. Further, the presence of the crystalline hard repeating units results in a resin with a discrete melting point, higher heat and chemical resistance, and good mechanical strength.

[0019] Referring to Formula (A), a and b are each independently 0-4, c and d are each independently 0-5, and Ra, Rb, Rc, and Rdare each independently halogen, C1-36hydrocarbyloxy, or C1-36hydrocarbyl. In some aspects, a, b, c, and d are each independently 0-2, and Ra, Rb, Rc, and Rdare each independently halogen, C1-6hydrocarbyloxy, or C1-6hydrocarbyl. In some aspects, a, b, c, and d are each independently 0-2, and Ra, Rb, Rc, and Rdare each methyl or phenyl or combination thereof.

[0020] The copolycarbonate optionally comprises hard repeating units derived from formula (2) HO–A1–Y1–A2–OH (2) wherein in formula (2), each of A1and A2is a monocyclic divalent aromatic group and Y1is a single bond or a bridging group having one or more atoms that separate A1from A2.

[0021] The soft repeating units of the copolycarbonate comprise repeating units derived from C5-44 aliphatic dicarboxylic acids and its reactive derivatives or equivalents; repeating units derived from C5-44 aliphatic dicarboxylic acids and its reactive derivatives or equivalents and siloxane repeating units; or siloxane repeating units of formula (15)22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122wherein in formula (15) each R is independently a C1-13alkyl, C1-13alkoxy, C2-13alkenyl, C2-13alkenyloxy, C3-6cycloalkyl, C3-6cycloalkoxy, C6-14aryl, C6-10aryloxy, C7-13arylalkylene, C7-13arylalkylenoxy, C7-13alkylarylene, or C7-13alkylaryleneoxy.

[0022] In some aspects, formula (A) is of formula (A-1)

[0023] In formula (A-1), Ra1, Ra2, Rb1, and Rb2 are each independently hydrogen, halogen, C1-36 hydrocarbyloxy, or C1-36 hydrocarbyl, wherein at least two of Ra1, Ra2, Rb1, and Rb2 are not hydrogen. In some aspects, Ra1, Ra2, Rb1, and Rb2 are each independently hydrogen, halogen, C1-6 hydrocarbyloxy, or C1-6 hydrocarbyl, wherein at least two of Ra1, Ra2, Rb1, and Rb2 are not hydrogen. In some aspects, Ra1, Ra2, Rb1, and Rb2are each methyl or phenyl. In some aspects, at least two of Ra1,Ra2,Rb1,and Rb2are methyl or phenyl.

[0024] “Polycarbonate” as used herein means a polymer having repeating structural carbonate units of formula (1)in which at least 60 percent of the total number of R1groups contain aromatic moieties, such as, for example, R1groups of formula (A or A-1), and the balance thereof are aliphatic, alicyclic, or aromatic. In an aspect, each R1is a C6-30aromatic group, that is, contains at least one aromatic moiety. R1can be derived from an aromatic dihydroxy compound of the formula HO-R1-OH, in particular of formula (2) HO–A1–Y1–A2–OH (2) wherein each of A1and A2is a monocyclic divalent aromatic group and Y1is a single bond or a bridging group having one or more atoms that separate A1from A2. In an aspect, one atom separates A1from A2. Preferably, each R1can be derived from a bisphenol of formula (3)22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122wherein Raand Rbare each independently a halogen, C1-12 alkoxy, C1-12 alkenyl, C3-8 cycloalkyl, or C1-12 alkyl, and p and q are each independently integers of 0 to 4. It will be understood that when p or q is less than 4, the valence of each carbon of the ring is filled by hydrogen. Also in formula (3), Xais a bridging group connecting the two hydroxy-substituted aromatic groups, where the bridging group and the hydroxy substituent of each C6 arylene group are disposed ortho, meta, or para (preferably para) to each other on the C6 arylene group. In an aspect, the bridging group Xais single bond, -O-, -S-, -S(O)-, -S(O)2-, -C(O)-, -P(R)(=O)- (wherein R is a C1-8 alkyl or C6-12 aryl), or a C1-60 organic group. The organic bridging group can be cyclic or acyclic, aromatic or non-aromatic, and can further comprise heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorous. The C1-60 organic group can be disposed such that the C6arylene groups connected thereto are each connected to a common alkylidene carbon or to different carbons of the C1-60organic bridging group. In an aspect, p and q is each 1, and Raand Rbare each a C1-3alkyl group, preferably methyl or phenyl, disposed either ortho or meta to the hydroxy group on each arylene group.

[0025] Other useful dihydroxy compounds of the formula HO-R1-OH include aromatic dihydroxy compounds of formula (4)wherein each Rhis independently a halogen atom, C1-10 hydrocarbyl group such as a C1-10 alkyl, a halogen-substituted C1-10 alkyl, a C6-10 aryl, or a halogen-substituted C6-10 aryl, and n is 0 to 4. The halogen is usually bromine.

[0026] Some illustrative examples of specific dihydroxy compounds include the following: 4,4'-dihydroxybiphenyl, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)-1- naphthylmethane, 1,2-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2-(4-hydroxyphenyl)-2-(3-hydroxyphenyl)propane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 1,1-bis (hydroxyphenyl)cyclopentane, 1,1-bis(4- hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)isobutene, 1,1-bis(4- hydroxyphenyl)cyclododecane, trans-2,3-bis(4-hydroxyphenyl)-2-butene, 2,2-bis(4- hydroxyphenyl)adamantane, alpha, alpha'-bis(4-hydroxyphenyl)toluene,22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122 bis(4-hydroxyphenyl)acetonitrile, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3-ethyl-4- hydroxyphenyl)propane, 2,2-bis(3-n-propyl-4-hydroxyphenyl)propane, 2,2-bis(3-isopropyl-4- hydroxyphenyl)propane, 2,2-bis(3-sec-butyl-4-hydroxyphenyl)propane, 2,2-bis(3-t-butyl-4- hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2,2-bis(3-allyl-4- hydroxyphenyl)propane, 2,2-bis(3-methoxy-4-hydroxyphenyl)propane, 2,2-bis(4- hydroxyphenyl)hexafluoropropane, 1,1-dichloro-2,2-bis(4-hydroxyphenyl)ethylene, 1,1-dibromo-2,2-bis(4-hydroxyphenyl)ethylene, 1,1-dichloro-2,2-bis(5-phenoxy-4- hydroxyphenyl)ethylene, 4,4'-dihydroxybenzophenone, 3,3-bis(4-hydroxyphenyl)-2-butanone, 1,6-bis(4-hydroxyphenyl)-1,6-hexanedione, ethylene glycol bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfone, 9,9-bis(4-hydroxyphenyl)fluorine, 2,7-dihydroxypyrene, 6,6'-dihydroxy-3,3,3',3'- tetramethylspiro(bis)indane ("spirobisindane bisphenol"), 3,3-bis(4-hydroxyphenyl)phthalimide, 2,6-dihydroxydibenzo-p-dioxin, 2,6-dihydroxythianthrene, 2,7-dihydroxyphenoxathin, 2,7-dihydroxy-9,10-dimethylphenazine, 3,6-dihydroxydibenzofuran, 3,6-dihydroxydibenzothiophene, and 2,7-dihydroxycarbazole, resorcinol, substituted resorcinol compounds such as 5-methyl resorcinol, 5-ethyl resorcinol, 5-propyl resorcinol, 5-butyl resorcinol, 5-t-butyl resorcinol, 5-phenyl resorcinol, 5-cumyl, resorcinol, 2,4,5,6-tetrafluoro resorcinol, 2,4,5,6-tetrabromo resorcinol, or the like; catechol; hydroquinone; substituted hydroquinones such as 2-methyl hydroquinone, 2-ethyl hydroquinone, 2-propyl hydroquinone, 2-butyl hydroquinone, 2-t-butyl hydroquinone, 2-phenyl hydroquinone, 2-cumyl hydroquinone, 2,3,5,6-tetramethyl hydroquinone, 2,3,5,6-tetra-t-butyl hydroquinone, 2,3,5,6-tetrafluoro hydroquinone, 2,3,5,6-tetrabromo hydroquinone, or the like, or a combination thereof.

[0027] In addition to the hard repeating units of formula (A) and (A-1), the copolycarbonate may include other hard repeating units derived from high refractive index bisphenol monomers having at least 19 carbon atoms. As used herein, a “high refractive index bisphenol monomer” is a monomer of Formula (2) where the corresponding homopolycarbonate of the monomer has a glass transition temperature (Tg ) of 155°C or higher, as determined by differential scanning calorimetry (DSC) as per ASTM D3418 with a 20oC / min heating rate.

[0028] The high refractive index bisphenol monomer may be of Formula (3), wherein Xais a C1-18alkylene, a C3-18cycloalkylene, a fused C6-18cycloalkylene, or a group of the formula – J1–G–J2– wherein J1and J2are the same or different C1-6alkylene and G is a C3-12cycloalkylidene or a C6-16arylene. For example, Xacan be a substituted C3-18cycloalkylidene of formula (5)22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122wherein Rr, Rp, Rq, and Rtare each independently hydrogen, halogen, oxygen, or C1-12hydrocarbon groups; Q is a direct bond, a carbon, or a divalent oxygen, sulfur, or –N(Z)– where Z is hydrogen, halogen, hydroxy, C1-12alkyl, C1-12alkoxy, C6-12aryl, or C1-12acyl; r is 0 to 2, t is 1 or 2, q is 0 or 1, and k is 0 to 3, with the proviso that at least two of Rr, Rp, Rq, and Rttaken together are a fused cycloaliphatic, aromatic, or heteroaromatic ring. It will be understood that where the fused ring is aromatic, the ring as shown in formula (5) will have an unsaturated carbon-carbon linkage where the ring is fused. When k is 1 and q is 0, the ring as shown in formula (5) contains 4 carbon atoms, when k is 2, the ring as shown in formula (5) contains 5 carbon atoms, and when k is 3, the ring contains 6 carbon atoms. In an aspect, two adjacent groups (e.g., Rqand Rttaken together) form an aromatic group, and in another aspect, Rqand Rttaken together form one aromatic group and Rrand Rptaken together form a second aromatic group. When Rqand Rttaken together form an aromatic group, Rpcan be a double-bonded oxygen atom, i.e., a ketone, or Q can be –N(Z)– wherein Z is phenyl.

[0029] Examples of high refractive index bisphenol groups include groups of formulas (6) to (12)wherein Rcand Rdare each independently a C1-12 alkyl, C2-12 alkenyl, C3-8 cycloalkyl, or C1-12 alkoxy, each Rfis hydrogen or both Rftogether are a carbonyl group, each R3is independently C1-6 alkyl, R4is hydrogen, C1-6 alkyl, or phenyl optionally substituted with 1 to 5 C1-6 alkyl22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122 groups, R6is independently C1-3 alkyl, or phenyl, preferably methyl, Xais a C6-12 polycyclic aryl, C3-18 mono- or polycycloalkylene, C3-18 mono- or polycycloalkylidene, –C(Rf)(Rg)– wherein Rfis hydrogen, C1-12 alkyl, or C6-12 aryl and Rgis C6-10 alkyl, C6-8 cycloalkyl, or C6-12 aryl, or – (Qa)x-G-(Qb)y- group, wherein Qaand Qbare each independently a C1-3 alkylene, G is a C3-10 cycloalkylene, x is 0 or 1, and y is 0 or 1, and j, m, and n are each independently 0 to 4. A combination of high refractive index bisphenol groups can be used.

[0030] In an aspect, Rcand Rdare each independently a C1-3 alkyl, or C1-3 alkoxy, each R6is methyl, each R3is independently C1-3 alkyl, R4is methyl, or phenyl, each R6is independently C1-3alkyl, or phenyl, preferably methyl, Xais a C6-12polycyclic aryl, C3-18mono- or polycycloalkylene, C3-18mono- or polycycloalkylidene, –C(Rf)(Rg)– wherein Rfis hydrogen, C1-12alkyl, or C6-12aryl and Rgis C6-10alkyl, C6-8cycloalkyl, or C6-12aryl, or –(Q1)x-G-(Q2)y- group, wherein Q1and Q2are each independently a C1-3alkylene and G is a C3-10cycloalkylene, x is 0 or 1, and y is 0 or 1, and j, m, and n are each independently 0 or 1.

[0031] Exemplary high refractive index bisphenol groups include those of formulas (11a) and (12a) to (12i)22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122 wherein Rcand Rdare the same as defined for formulas (6) to (12), each R2is independently C1-4 alkyl, m and n are each independently 0 to 4, each R3is independently C1-4 alkyl or hydrogen, R4is C1-6 alkyl or phenyl optionally substituted with 1 to 5 C1-6 alkyl groups, and g is 0 to 10. In a specific aspect each bond of the bisphenol group is located para to the linking group that is Xa. In an aspect, Rcand Rdare each independently a C1-3 alkyl, or C1-3 alkoxy, each R2is methyl, x is 0 or 1, y is 1, and m and n are each independently 0 or 1.

[0032] The high refractive index bisphenol group is preferably of formula (11a-2) or (12a-2)wherein R4is methyl or phenyl, each R2is methyl, and g is 1 to 4. In certain aspects, the high refractive index bisphenol group is derived from 2-phenyl-3,3’-bis(4-hydroxyphenyl) phthalimidine (PPPBP) or from 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane (BP- TMC).

[0033] Specific examples of bisphenol compounds of formula (3) include 1,1-bis(4- hydroxyphenyl) methane, 1,1-bis(4-hydroxyphenyl) ethane, 2,2-bis(4-hydroxyphenyl) propane (hereinafter “bisphenol A” or “BPA”), 2,2-bis(4-hydroxyphenyl) butane, 2,2-bis(4- hydroxyphenyl) octane, 1,1-bis(4-hydroxyphenyl) propane, 1,1-bis(4-hydroxyphenyl) n-butane, 2,2-bis(4-hydroxy-2-methylphenyl) propane, 1,1-bis(4-hydroxy-t-butylphenyl) propane, 3,3- bis(4-hydroxyphenyl) phthalimidine, 2-phenyl-3,3-bis(4-hydroxyphenyl) phthalimidine (PPPBP), 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol TMC or BP-TMC), and 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane (DMBPC). A combination can also be used. In a specific aspect, the polycarbonate is a linear homopolymer derived from bisphenol A, in which each of A1and A2is p-phenylene and Y1is isopropylidene in formula (3).

[0034] Additional examples of high refractive index monomers other than Formula (A) are also described in JP62186201, JPH073481B2, WO2020196343A1, JP2015221850A, JP2005036200A, JP2000280414A, CN111187403A, WO2010150885A1, EP1489123A1, JP2006328106A, JP2002308978A, WO2009028699A1, and WO2020122122.22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122

[0035] The high refractive index monomer repeating units may be of formula HR:wherein j and k are each independently 0-4, l and m are each independently 0-4, and Rj, Rk, Rl, Rm are each independently halogen, substituted or unsubstituted C1-36 hydrocarbyloxy, or substituted or unsubstituted C1-36 hydrocarbyl, and X is (L)x-OH, wherein x is 0-3 and L is a divalent linking group. The divalent linking group may include a substituted or unsubstituted C1-6 hydrocarbyl group. In some aspects, j and k are each 0, l and m are each 1, Rl and Rm are each independently halogen, substituted or unsubstituted C1-6 hydrocarbyloxy, or substituted or unsubstituted C1-6hydrocarbyl and X is -(L)x-OH, wherein x is 0-1 and L is a divalent linking group. In some aspects, j and k are each 0, l and m are each 1, Rland Rmare each independently substituted or unsubstituted C1-6hydrocarbyl, and X is -(L)x-OH, wherein x is 0-1 and L is a divalent linking group. High refractive index monomers may include ethoxylated bisphenol fluorene (BPEF), bisphenol fluorene (BPF), biscresyl phenol fluorene (BCF), 9,9-bis [6-(2- hydroxyethoxy)naphthalen-2-yl]fluorene (BNEF), and the like, with the proviso that the repeating units derived from high refractive index monomers may be present only to the extent that the desired combination of properties is not adversely affected.

[0036] The soft repeating units of the copolycarbonate comprise repeating units derived from C5-44 aliphatic dicarboxylic acids and its reactive derivatives or equivalents; repeating units derived from C5-44 aliphatic dicarboxylic acids and its reactive derivatives or equivalents and siloxane repeating units; or siloxane repeating units of formula (15)wherein in formula (15) each R is independently a C1-13alkyl, C1-13alkoxy, C2-13alkenyl, C2-13alkenyloxy, C3-6cycloalkyl, C3-6cycloalkoxy, C6-14aryl, C6-10aryloxy, C7-13arylalkylene, C7-13arylalkylenoxy, C7-13alkylarylene, or C7-13alkylaryleneoxy.22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122

[0037] The copolycarbonates may include poly(ester-carbonate) repeating units. In some aspects, the copolycarbonate is a poly(ester-carbonate) copolymer. The poly(ester-carbonate) repeating units are of formula (13)wherein, J is a divalent group derived from a dihydroxy compound (which includes a reactive derivative thereof), and can be, for example, a C1-10 alkylene, a C6-20 cycloalkylene, a C5-20 arylene, or a polyoxyalkylene group in which the alkylene groups contain 2 to 6 carbon atoms, preferably, 2, 3, or 4 carbon atoms, a bisphenol derived from Formula (3), or a bisphenol derived from Formula (A); and T is a divalent group derived from a dicarboxylic acid (which includes a reactive derivative thereof), and can be, for example, a C1-20 alkylene, a C5-20 cycloalkylene, or a C6-20 arylene group. Different T or J groups can be used. The polyester units can be branched or linear.

[0038] Specific dihydroxy compounds include aromatic dihydroxy compounds of formula (2) (e.g., resorcinol), bisphenols of formula (3) (e.g., bisphenol A), a C1-8aliphatic diol such as ethane diol, n-propane diol, i-propane diol, 1,4-butane diol, 1,4-cyclohexane diol, 1,4-hydroxymethylcyclohexane, or a combination thereof dihydroxy compounds. Aliphatic dicarboxylic acids that can be used include C5-44aliphatic dicarboxylic acid,preferably from C5-20aliphatic dicarboxylic acids (which includes the terminal carboxyl groups), more preferably C8-12 aliphatic dicarboxylic acids. The aliphatic dicarboxylic acids may be straight chain (i.e. unbranched) or branched chain dicarboxylic acids, cycloalkyl or cycloalkylidene-containing dicarboxylic acids, or combination of these. Examples of the dicarboxylic acid include, but not limited to, adipic acid, 3,3^-dimethyl adipic acid, decanedioic acid (sebacic acid), 3,3,6-trimethyl sebacic acid, 3,3,5,5-tetramethyl sebacic acid, azelaic acid, alpha, omega-C12 dicarboxylic acids such as dodecanedioic acid (DDDA), alpha, omega-C16 dicarboxylic acid such as hexadecanedioic acid (HDDA), dimer acids, cyclohexane dicarboxylic acids, dimethyl cyclohexane dicarboxylic acid, norbornane dicarboxylic acids, adamantane dicarboxylic acids, cyclohexene dicarboxylic acids, C14, C18 and C20 diacids. Aromatic dicarboxylic acids that can be used include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, or a combination thereof acids. A combination of isophthalic acid and terephthalic acid wherein the weight ratio of isophthalic acid to terephthalic acid is 91:9 to 2:98 can be used. It should be noted that although referred to as diacids, any reactive derivatives or equivalents of diacids could be employed such as acid halides, specifically acid22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122 chlorides, and diaromatic esters of the diacid such as diphenyl, for example the diphenylester of sebacic acid.

[0039] Specific ester units other than those of Formula (A) include ethylene terephthalate units, n-propylene terephthalate units, n-butylene terephthalate units, ester units derived from isophthalic acid, terephthalic acid, and resorcinol (ITR ester units), and ester units derived from sebacic acid and bisphenol A. The molar ratio of ester units to carbonate units in the copolycarbonate can vary broadly, for example from 1:99 to 99:1, or from 10:90 to 90:10, or from 20:80 to 80:20, or from 1:99 to 50:50, or from 50:50 to 99:1.

[0040] A specific poly(aliphatic ester)-polycarbonate is of formula (14):wherein each R1comprises Formula (A or A-1) and optionally, Formula (2, 3, or 4), m is 4 to 18, preferably 4 to 10. In a specific aspect, the copolycarbonate comprises Formula (A)-sebacate ester units and Formula (A) carbonate units.

[0041] When the copolycarbonate is a poly(ester carbonate), then the ester units are present in an amount of at least 2 wt%. Within that range, the ester units may be present from 2 to 8 wt%, or 2 to 5 wt%, or 2 to 4.5 wt%, based on the total weight of the copolycarbonate. Referring to mole %, the ester units may be present in an amount ranging from 0.5 to 10 mol%, based on the total moles of the monomers of the copolycarbonate.

[0042] The soft repeating units of the copolycarbonates may include diorganosiloxane units as in formula (15)wherein each R is independently a C1-13monovalent organic group. For example, R can be a C1-13alkyl, C1-13alkoxy, C2-13alkenyl, C2-13alkenyloxy, C3-6cycloalkyl, C3-6cycloalkoxy, C6-14aryl, C6-10aryloxy, C7-13arylalkylene, C7-13arylalkylenoxy, C7-13alkylarylene, or C7-13alkylaryleneoxy. The foregoing groups can be fully or partially halogenated with fluorine, chlorine, bromine, or iodine, or a combination thereof. In an aspect, where a transparent poly(carbonate-siloxane) is desired, R is unsubstituted by halogen. Combinations of the foregoing R groups can be used in the same copolymer.

[0043] The value of E in formula (15) can vary widely depending on the type and relative amount of each component in the thermoplastic composition, the desired properties of22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122 the composition, and like considerations. Generally, E has an average value of 2 to 1,000, preferably 2 to 500, 2 to 200, or 2 to 125, 5 to 80, or 10 to 70. In an aspect, E has an average value of 10 to 80 or 10 to 40, and in still another aspect, E has an average value of 40 to 80, or 40 to 70. Where E is of a lower value, e.g., less than 40, it can be desirable to use a relatively larger amount of the poly(carbonate-siloxane) copolymer. Conversely, where E is of a higher value, e.g., greater than 40, a relatively lower amount of the poly(carbonate-siloxane) copolymer can be used. A combination of a first and a second (or more) poly(carbonate-siloxane) copolymers can be used, wherein the average value of E of the first copolymer is less than the average value of E of the second copolymer.

[0044] In an aspect, the polydiorganosiloxane blocks are of formula (16)wherein E and R are as defined in formula (15); each R can be the same or different, and is as defined above; and Ar can be the same or different, and is a substituted or unsubstituted C6-30 arylene, wherein the bonds are directly connected to an aromatic moiety. Useful Ar groups in formula (16) can be derived from a C6-30 dihydroxyarylene compound, for example a dihydroxyarylene compound of formula (2), (3) or (4) above. Combinations comprising at least one of the foregoing dihydroxyarylene compounds may also be used. Specific examples of dihydroxyarylene compounds are 1,1-bis(4-hydroxyphenyl) methane, 1,1-bis(4-hydroxyphenyl) ethane, 2,2-bis(4-hydroxyphenyl) propane, 2,2-bis(4-hydroxyphenyl) butane, 2,2-bis(4- hydroxyphenyl) octane, 1,1-bis(4-hydroxyphenyl) propane, 1,1-bis(4-hydroxyphenyl) n-butane, 2,2-bis(4-hydroxy-1-methylphenyl) propane, 1,1-bis(4-hydroxyphenyl) cyclohexane, bis(4- hydroxyphenyl sulfide), and 1,1-bis(4-hydroxy-t-butylphenyl) propane.

[0045] In another aspect, polydiorganosiloxane blocks are of formula (17)wherein R and E are as described above, and each R5is independently a divalent C1-30organic group, and wherein the polymerized polysiloxane unit is the reaction residue of its corresponding dihydroxy compound. In a specific aspect, the polydiorganosiloxane blocks are of formula (18):22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122wherein R and E are as defined above. R6in formula (18) is a divalent C2-8 aliphatic group. Each M in formula (18) can be the same or different, and can be a halogen, cyano, nitro, C1-8 alkylthio, C1-8 alkyl, C1-8 alkoxy, C2-8 alkenyl, C2-8 alkenyloxy, C3-8 cycloalkyl, C3-8 cycloalkoxy, C6-10 aryl, C6-10 aryloxy, C7-12 aralkyl, C7-12 aralkoxy, C7-12 alkylaryl, or C7-12 alkylaryloxy, wherein each n is independently 0, 1, 2, 3, or 4.

[0046] In an aspect, M is bromo or chloro, an alkyl such as methyl, ethyl, or propyl, an alkoxy such as methoxy, ethoxy, or propoxy, or an aryl such as phenyl, chlorophenyl, or tolyl; R6is a dimethylene, trimethylene or tetramethylene; and R is a C1-8 alkyl, haloalkyl such as trifluoropropyl, cyanoalkyl, or aryl such as phenyl, chlorophenyl or tolyl. In another aspect, R is methyl, or a combination of methyl and trifluoropropyl, or a combination of methyl and phenyl. In still another aspect, R is methyl, M is methoxy, n is one, and R6is a divalent C1-3aliphatic group. Specific polysiloxane blocks are one of the formulas 18(a) to 18(c), or a combination thereof, wherein E has an average value of 2 to 200, 2 to 125, 5 to 125, 5 to 100, 5 to 50, 20 to 80, or 5 to 20.

[0047] Blocks of formula (18) can be derived from the corresponding dihydroxy polysiloxane, which in turn can be prepared effecting a platinum-catalyzed addition between the siloxane hydride and an aliphatically unsaturated monohydric phenol such as eugenol, 2- alkylphenol, 4-allyl-2-methylphenol, 4-allyl-2-phenylphenol, 4-allyl-2-bromophenol, 4-allyl-2-t- butoxyphenol, 4-phenyl-2-phenylphenol, 2-methyl-4-propylphenol, 2-allyl-4,6-dimethylphenol, 2-allyl-4-bromo-6-methylphenol, 2-allyl-6-methoxy-4-methylphenol and 2-allyl-4,6- dimethylphenol. The poly(carbonate-siloxane) copolymers can then be manufactured, for example, by the synthetic procedure of European Patent Application Publication No.0524731 A1 of Hoover, page 5, Preparation 2.22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122

[0048] The copolycarbonate may include repeating siloxane units (18a), (18b), (18c), or a combination thereof (preferably of formula 18a), wherein E has an average value of 4 to 50, 4 to 15, preferably 5 to 15, more preferably 6 to 15, and still more preferably 7 to 10. The copolymers can be manufactured using one or both of the tube reactor processes described in U.S. Patent Application No.2004 / 0039145A1 or the process described in U.S. Patent No. 6,723,864 can be used to synthesize the poly(carbonate-siloxane) copolymers.

[0049] When the copolycarbonate includes siloxane repeating units, the siloxane repeating units may be present from 2-15 wt%. Within this range the siloxane repeating units may be present from 2-12 wt%, 2-10 wt%, or 2-8 wt%, based on the total weight of the copolycarbonate.

[0050] The copolycarbonates are prepared by a method including polymerizing monomer precursors of the hard repeating units comprising Formula (A) and optionally, monomer precursors of the hard repeating units of Formulas (2, 3, or 4) with the monomer precursors of the soft repeating units in the presence of a carbonyl source under conditions effective to provide the copolycarbonate.

[0051] In particular, the copolycarbonates can be manufactured by processes such as interfacial polymerization and melt polymerization, which are known, and are described, for example, in WO 2013 / 175448 A1 and WO 2014 / 072923 A1. An end-capping agent (also referred to as a chain stopper agent or chain terminating agent) can be included during polymerization to provide end groups, for example monocyclic phenols such as phenol, p- cyanophenol, and C1-22 alkyl-substituted phenols such as p-cumyl-phenol, resorcinol monobenzoate, and p-and tertiary-butyl phenol, monoethers of diphenols, such as p- methoxyphenol, monoesters of diphenols such as resorcinol monobenzoate, functionalized chlorides of aliphatic monocarboxylic acids such as acryloyl chloride and methacryoyl chloride, and mono-chloroformates such as phenyl chloroformate, alkyl-substituted phenyl chloroformates, p-cumyl phenyl chloroformate, and toluene chloroformate. Combinations of different end groups can be used. Branched polycarbonate blocks can be prepared by adding a branching agent during polymerization, for example trimellitic acid, trimellitic anhydride, trimellitic trichloride, tris-p-hydroxyphenylethane, isatin-bis-phenol, tris-phenol TC (1,3,5- tris((p-hydroxyphenyl)isopropyl)benzene), tris-phenol PA (4(4(1,1-bis(p-hydroxyphenyl)-ethyl) alpha, alpha-dimethyl benzyl)phenol), 4-chloroformyl phthalic anhydride, trimesic acid, and benzophenone tetracarboxylic acid. The branching agents can be added at a level of 0.05 to 2.0 wt. %. Combinations comprising linear polycarbonates and branched polycarbonates can be used.22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122

[0052] The copolycarbonates can have a glass transition temperature greater than 130oC to 250oC, preferably 145oC to 200oC, more preferably 150oC to 170oC, as determined by differential scanning calorimetry (DSC) as per ASTM D3418 with a 20oC / min heating rate.

[0053] Refractive index (RI) testing of the cast thin films (30-100 microns) and molded parts (2-3 mm thickness) may be performed in using a Metricon Model 2010 / M at a wavelength of 589 nm at room temperature (23 °C). The copolycarbonates can have a refractive index of greater than 1.59, preferably greater than 1.60 at 589 nm.

[0054] The copolycarbonates can have an Abbe number of less than 32 or less than 30 measured according to ISO 489 on a molded plaque with a thickness of 1 mm.

[0055] The copolycarbonates can have good scratch resistance according to the Erichson scratch test. The Erichson scratch test is performed using a needle held at an angle of 90 degrees relative to the surface being tested results in a scratch depth of less than 19 micrometers under a downward force of 6 Newtons.

[0056] The polycarbonate compositions have good thermal stability. “Thermal stability” as used herein refers to resistance of a polymer to molecular weight degradation under thermal conditions. Thus, a polymer with poor thermal stability can show significant molecular weight degradation under thermal conditions, such as during extrusion, molding, thermoforming, hot- pressing, and like conditions. Molecular weight degradation can also be manifest through color formation or in the degradation of other properties such as weatherability, gloss, mechanical properties, or thermal properties. Molecular weight degradation can also cause significant variation in processing conditions such as melt viscosity changes.

[0057] The polycarbonate compositions have good melt stability as well. Melt stability is defined as the change in melt volume rate (MVR). The term “Melt Volume Rate” (MVR) refers to the flow rate of a polymer in a melt phase as determined using the method of ASTM 1238-10. Melt volume flow rate (often abbreviated "MVR") measures the rate of extrusion of the copolycarbonate or compositions thereof through an orifice at a prescribed temperature and load. In particular, the MVR may be measured at 250ºC under a load of 10 kg and / or 260°C under a load of 2.16 kg and / or 300ºC under a load of 1.2 kg in accordance with ASTM D1238-04. MVR is expressed in cubic centimeter per 10 minutes. The higher the MVR value of a polymer at a specific temperature, the greater the flow of that polymer at that specific temperature. The copolycarbonate and the compositions thereof can have a change in MVR of less than or equal to 30%, specifically less than or equal to 10%. The MVR is determined at 6 minutes and again at 18 minutes, and the difference between these MVRs is less than or equal to 30% of the 6 minute value.22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122

[0058] Transparency is described by two parameters, percent transmission and percent haze. Percent transmission and percent haze for laboratory scale samples were determined using ASTM D1003. The term “percent transmission” or “% transmission” refers to the ratio of transmitted light to incident light, and may be measured according to ASTM D 1003-07. In an exemplary aspect, a molded sample having a thickness of 1 millimeter has a percent transmission of 85% or more according to ASTM D1003-00 and a percent haze of 10% or less according to ASTM D1003-00. In some aspects, a molded sample having a thickness of 1 millimeter has a percent haze of 2% or less according to ASTM D1003-00. In some aspects, a molded sample having a thickness of 1 millimeter has a yellowness index of 2 or less according to ASTM D1003-00.

[0059] The copolycarbonates can have low birefringence, as indicated by the stress optic coefficient (SOC) and expressed in units of Brewster (Br). When the SOC ranges from -120 to 44 Br, then the birefringence is minimized. SOC testing of the cast thin film (30-100 µm) may be measured using transmission ellipsometry (SENresearch 4.0 SER 850 DUV) equipped with custom setup for applying a load on the film. The load may be varied from 5 g to 1 kg and the phase angle and transmission measured. A plot of load vs. change in refractive index may provide the slope, which is the stress optic coefficient.

[0060] The copolycarbonate may have a water uptake of less than 0.2 wt% according to ASTM D570. The water uptake is determined by comparing the difference in the weight of a 1 mm molded sample that has been immersed in water for 24 hours with the dry weight of the same molded sample prior to immersion in water.

[0061] The copolycarbonate may be incorporated into a polycarbonate composition. The polycarbonate compositions can include various additives ordinarily incorporated into polymer compositions of this type, with the proviso that the additive(s) are selected so as to not significantly adversely affect the desired properties of the polycarbonate composition, in particular optical clarity and thermal properties. Such additives can be mixed at a suitable time during the mixing of the components for forming the composition. Additives include antioxidants, heat stabilizers, light stabilizers, ultraviolet (UV) light stabilizers, plasticizers, lubricants, mold release agents, antistatic agents, colorants such as organic dyes, surface effect additives, and radiation stabilizers. In an embodiment, the polycarbonate composition further comprises a processing aid, a heat stabilizer, an ultraviolet light absorber, and a colorant. A combination of additives can be used, for example a combination of a heat stabilizer, mold release agent, and ultraviolet light stabilizer. In general, the additives are used in the amounts generally known to be effective. For example, the total amount of the additives (other than any22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122 impact modifier, filler, or reinforcing agents) can be 0 to 5 wt% or 0.01 to 5 wt%, based on the total weight of the polycarbonate composition.

[0062] The polycarbonate compositions can be manufactured by various methods known in the art. For example, powdered polycarbonate, and other optional components are first blended, optionally with any fillers, in a high speed mixer or by hand mixing. The blend is then fed into the throat of a twin-screw extruder via a hopper. Alternatively, at least one of the components can be incorporated into the composition by feeding it directly into the extruder at the throat and / or downstream through a sidestuffer, or by being compounded into a masterbatch with a desired polymer and fed into the extruder. The extruder is generally operated at a temperature higher than that necessary to cause the composition to flow. The extrudate can be immediately quenched in a water bath and pelletized. The pellets so prepared can be one-fourth inch long or less as desired. Such pellets can be used for subsequent molding, shaping, or forming.

[0063] The copolycarbonates can be molded under standard molding conditions in range of 250 to 300ºC depending on the glass transition temperature of the composition. For example, the copolycarbonates can be molded at a temperature of 100 to 175oC above the glass transition temperature of the copolycarbonate for a residence time of 2 to 20 minutes.

[0064] The copolycarbonates can be provided as pellets, and are useful to form lenses via various methods. The methods to make the lenses are not particularly limited. Exemplary methods include part production via multi-cavity tools; molding such as injection molding, gas assist injection molding, vacuum molding, over-molding, compression molding, rotary molding, heat / cool molding, overmolding, transfer molding, or cavity molding; thermoforming; extruding; calendaring; casting; and the like.

[0065] Advantageously, the lenses have no significant part distortion or discoloration when the articles are subjected to a secondary operation such as over-molding, or coating with high temperature curing, or a combination thereof. High temperature cure of a coating can be, for example, 100°C or higher, for example 100 to 250°C. In some embodiments, “no significant part distortion” includes a volume distortion of less than 10 volume percent (vol%), or less than 5 vol%, or less than 1 vol%. Significant discoloration can be detected by the unaided eye at a distance of 18 inches. The polycarbonate compositions, which have good flow (MVR) for excellent mold filling properties while maintaining desirable mechanical properties can, in the manufacture of lenses, provide a high degree of reproducibility for successive lenses molded from the polycarbonate composition.22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122

[0066] The shape of the lenses is not particularly limited. The lens can be a planar (flat) lens, a curved lens, a cylindrical lens, a toric lens, a sphero-cylindrical lens, a Fresnel lens, a convex lens, a biconvex lens, a concave lens, a biconcave lens, a convex-concave lens, a plano- convex lens, a plano-concave lens, a lenticular lens, a gradient index lens, an axicon lens, a conical lens, an astigmatic lens, an aspheric lens, a corrective lens, a diverging lens, a converging lens, a compound lens, a photographic lens, a doublet lens, a triplet lens, an achromatic lens, or a multi-array lens. Thus, the lens can be a layer of a multi-layer lens.

[0067] The lenses can be defined by several dimensional features such as thickness, effective lens area, diameter of an effective lens area, and an overall diameter. Lens thickness, as defined herein, is measured at the center of the lens (i.e., along the z axis, orthogonal to the diameter of the lens which is measured in the x-y plane of the lens). Since lenses have curvature, the thickness of the lens may vary along the contour of the surface. Also, depending upon the type of the lens (convex, concave, etc.) the variation of the thickness can differ widely. In an embodiment, the lens has a thickness of 0.1 mm to 50 cm, or 0.1 mm to 10 cm, 0.1 mm to 1 cm, or 0.1 mm to 0.5 cm, or 0.1 mm to 50 mm, measured at the thickest part of the lens. In a specific embodiment, the lens has a thickness of 0.25 to 2.5 mm, or 0.5 to 2.4 mm, or 0.8 to 2.3 mm, measured at the center of the lens.

[0068] The size of the lens is characterized by the term "effective lens area,” which is defined as the area of the lens where the curvature is positive, and hence light which is refracted through this area is usable in actual imaging. "Curvature" as defined herein, is the reciprocal of the optical radius of the lens (as defined by the light path). For example, a flat surface has infinite radius and therefore zero curvature. For those lenses that include a flat portion around the periphery of the lens, which is used for mounting the lens into the optical assembly, this flat portion is not considered part of the effective lens area. A typical lens has at least two surfaces, a first and a second surface. On the first (incident) surface, light enters the lens and exits through the second (refractive) surface. One or both of these surfaces may have a curvature. The effective lens area as defined above may be the same for the first and second surfaces, or may be different for the first and second surfaces. Where different, the larger value of the effective surface area for the first and second surfaces is considered to be the effective lens area for the overall lens. The lens can have an effective lens area of 0.2 mm2to 10 m2, or 0.2 mm2to 1 m2, or 0.2 mm2to 10 cm2, or 0.2 mm2to 5 mm2, or 0.2 mm2to 100 mm2.

[0069] Effective lens area diameter as defined herein describes the diameter measured at the outermost periphery of the effective (optically useable) area of the lens; whereas overall diameter of the lens is the diameter which includes the non-optically relevant flat portion. The22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122 lenses disclosed herein can have a diameter of an effective lens area of 0.1 mm to 500 cm, or 0.25 mm to 50 cm, or 0.5 mm to 1 cm, or 0.5 mm to 10 mm, or an overall diameter of 0.1 mm to 2 m, or 0.25 mm to 100 cm, or 0.5 mm to 2 cm, or 0.5 mm to 20 mm.

[0070] The lens can have an overall diameter of 0.1 mm to 500 cm, or 0.25 mm to 100 cm, or 0.5 mm to 2 cm, or 0.5 mm to 20 mm.

[0071] The lenses can have surface textures such as a macrotexture, a microtexture, a nanotexture, or a combination thereof on a surface of the lenses. Textures can also be imparted to the lenses using methods known in the art including but not limited to calendaring or embossing techniques. In an embodiment, the lenses can pass through a gap between a pair of rolls with at least one roll having an embossed pattern thereon, to transfer the embossed pattern to a surface of the lenses. Textures can be applied to control gloss or reflection.

[0072] The lenses can further comprise an indicia or a coating disposed on at least a portion of one or both sides of the lens to impart additional properties such as scratch resistance, ultra violet light resistance, aesthetic appeal, hydrophilicity, hydrophobicity, and the like. In an embodiment, the coating is a hard coat, a UV protective coat, an anti-refractive coat, an anti- reflective coat, a scratch resistant coat, a hydrophobic coat, a hydrophilic coat, or a combination comprising at least one of the foregoing. Coatings can be applied through standard application techniques such as overmolding, rolling, spraying, dipping, brushing, flow coating, or combinations comprising at least one of the foregoing application techniques.

[0073] Depending on the applications, at least a portion of a surface of the lens is metallized in some embodiments. A metal layer can be disposed onto the surface of the lenses with the aid of electrocoating deposition, physical vapor deposition, or chemical vapor deposition or a suitable combination of these methods. Sputtering processes can also be used. The metal layer resulting from the metallizing process (e.g., by vapor deposition) can be 0.001 to 50 micrometers (µm) thick. Chrome, nickel, aluminum, and the like can be listed as examples of vaporizing metals. Aluminum vapor deposition is used in one embodiment as metal vapor deposition. The surface of the molded substrate can be treated with plasma, cleaned, or degreased before vapor deposition in order to increase adhesion.

[0074] The lenses can have low birefringence, which means that the lenses can have low light distortion and a better quality image.

[0075] Exemplary lenses include a camera lens, a sensor lens, an illumination lens, a safety glass lens, an ophthalmic corrective lens, or an imaging lens.

[0076] The foregoing types of lenses can be used in a wide variety of applications. For example, the camera lens can be a mobile phone camera lens, a table camera lens, a security22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122 camera lens, a mobile phone camera lens, a tablet camera lens, a laptop camera lens, a security camera lens, a camera sensor lens, a copier camera lens, or a vehicle camera lens (e.g., an automotive camera lens).

[0077] The sensor lens can be a motion detector lens, a proximity sensor lens, a gesture control lens, an infrared sensor lens, or a camera sensor lens.

[0078] The illumination lens can be an indoor lighting lens, an outdoor lighting lens, vehicle headlamp lens, a vehicle fog light lens, a vehicle rear light lens, a vehicle running light lens, a vehicle fog light lens, a vehicle interior lens, an a light emitting diode (LED) lens, or an organic light emitting diode (OLED) lens.

[0079] The safety glass lens is a glasses lens, a goggles lens, a visor, a helmet lens, or other protective gear.

[0080] The ophthalmic corrective lens can be incorporated into monocles, corrective glasses (including bifocals, trifocals, progressive lens, and the like), contact lenses, and the like.

[0081] The imaging lens can be a scanner lens, a projector lens, a magnifying glass lens, a microscope lens, a telescope lens, a security lens, reading glasses lens, and the like.

[0082] Accordingly, the lenses can be incorporated into a wide variety of devices, including a camera (including reflex cameras), an electronic device (such as mobile phones, tablets, laptop computers, and desk computers), a vehicle (which as used herein refers to any transportation devices, for example bicycles, scooters, motorcycles, automobiles, buses, trains, boats, ships, and aircraft) a flashlight, a business machine (such as a copier or a scanner), a lighting device (including indoor lighting such as table lamps and ceiling lights, outdoor lighting such as floodlights and streetlights, vehicle headlights, rear lights, side lights, running lights, fog lights, and interior lights), an imaging device (such as a microscope, a telescope, a projector, a security lens (e.g. in a door), or reading glasses), a safety article (such as goggles, glasses, and headgear such as helmets), a vision corrective article (glasses or contact lens), or a toy.

[0083] This disclosure is further illustrated by the following examples, which are non- limiting. EXAMPLES

[0084] The following components are used in the examples. Table 1. BPA 4,4'-Dihydroxy-2,2,-diphenylpropane SA Sebacic acid BCB 4,4'-(Diphenylmethylene)bis[2-methylphenol] D10 Eugenol capped polydimethyl siloxane (average Mw = 1,066 grams per mol (g / mol) as determined by gel permeation chromatography (GPC) PCP p-cumylphenol22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122 OKP4 Polyester resin having fluorene skeleton (average Mw = 7,500 g / mol) Osaka Gas Chemical EP4500 Polycarbonate resin Mitsubishi Gas Chemical

[0085] Synthesis of BCB homopolymer.35 g of 4,4'-(diphenylmethylene)bis[2- methylphenol] (BCB) and 0.73 g of p-cumylphenol (PCP) were charged into a 2 L reactor equipped with a mechanical stirrer, pH probe, gas inlet, caustic inlet, and a condenser vented to a scrubber.500 mL of methylene chloride, 300 mL of deionized water, and 0.38 mL of triethyl amine (TEA) were charged to the reactor and it was sealed and purged with nitrogen. After purging with nitrogen, phosgene was introduced to the reactor at a rate of 1g / min while aqueous sodium hydroxide was added to maintain a pH of 9.5. After 15 minutes, phosgene gas flow was stopped, and the reaction was purged with nitrogen. The organic layer was collected and washed with 500 mL of 1% HCl (aq.) followed by 500 mL of deionized water three times. Methylene chloride was removed, and the resulting polymer powder was analyzed by GPC and shown to have a molecular weight of 19,946 Da and a PDI of 2.35. Neat polymer powder was dissolved in methylene chloride and thin films were cast using standard procedure.

[0086] Synthesis of BCB homopolymer.30 g of 4,4'-(diphenylmethylene)bis[2- methylphenol] (BCB) and 1.325 of p-cumylphenol (PCP) were charged into a 2 L reactor equipped with a mechanical stirrer, pH probe, gas inlet, caustic inlet, and a condenser vented to a scrubber.500 mL of methylene chloride, 300 mL of deionized water, and 0.75 mL of triethyl amine (TEA) were charged to the reactor and it was sealed and purged with nitrogen. After purging with nitrogen, phosgene was introduced to the reactor at a rate of 1g / min while aqueous sodium hydroxide was added to maintain a pH of 10. After 21 minutes phosgene gas flow was stopped, and the reaction was purged with nitrogen for 5 min. The organic layer was collected and washed with 500 mL of 1% HCl (aq.) followed by 500 mL of deionized water three times. Methylene chloride was removed, and the resulting polymer powder was analyzed by GPC and shown to have a molecular weight of 19,469 Da and a PDI of 2.79.

[0087] Synthesis of BCB-Si copolycarbonate.33.61g of 4,4'-(diphenylmethylene)bis[2- methylphenol] (BCB), 1.40 g eugenol capped polydimethyl siloxane (average Mw = 1066 g / mol) and 0.713 of p-cumylphenol (PCP) were charged into a 2 L reactor equipped with a mechanical stirrer, pH probe, gas inlet, caustic inlet, and a condenser vented to a scrubber.500 mL of methylene chloride, 300 mL of deionized water, and 0.37 mL of triethyl amine (TEA) were charged to the reactor and it was sealed and purged with nitrogen. After purging with nitrogen, phosgene was introduced to the reactor at a rate of 1g / min while aqueous sodium hydroxide was added to maintain a pH of 9.5. After 15 minutes phosgene gas flow was stopped,22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122 and the reaction was purged with nitrogen for 5 mins. The organic layer was collected and washed with 500 mL of 1% HCl (aq.) followed by 500 mL of deionized water three times. Methylene chloride was removed, and the resulting polymer powder was analyzed by GPC and shown to have a molecular weight of 20,800 Da and a PDI of 2.59.

[0088] Synthesis of BCB-SA poly(ester-carbonate).33.45g of 4,4'-(diphenylmethylene)bis[2-methylphenol] (BCB), 1.55 g of sebacic acid, and 0.658 of p-cumylphenol (PCP) were charged into a 2 L reactor equipped with a mechanical stirrer, pH probe, gas inlet, caustic inlet, and a condenser vented to a scrubber.500 mL of methylene chloride, 300 mL of deionized water, and 0.60 mL of triethyl amine (TEA) were charged to the reactor and it was sealed and purged with nitrogen. After purging with nitrogen, phosgene was introduced to the reactor at a rate of 1g / min while aqueous sodium hydroxide was added to maintain a pH of 7.5. After 6.5 minutes, pH was increased to 10 and phosgene gas was allowed to flow for another 6.5 minutes at a rate of 1g / min. After phosgene gas flow was stopped, and the reaction was purged with nitrogen for 5 mins. The organic layer was collected and washed with 500 mL of 1% HCl (aq.) followed by 500 mL of deionized water three times. Methylene chloride was removed, and the resulting polymer powder was analyzed by GPC and shown to have a molecular weight of 20,982 Da and a PDI of 3.24.

[0089] The other copolymers of BCB + siloxane (D10) and BCB + sebacic acid were prepared similarly as the above procedures.

[0090] The testing samples were prepared as described below and the following test methods were used.

[0091] An Engel 45 molding machine was used to mold the test parts for standard physical property testing. The parameters are provided in Table 2.22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122 Table Parameters Unit Conditions Drying Temperature °F 250 Drying Time hour 4 Hopper temperature °F Nozzle Temperature °F 555 Rear - Zone 1 Temperature °F 555 Middle - Zone 2-3 Temperature °F 555 Front - Zone 4 Temperature °F 555

[0092] Sample preparation and testing methods are described in Table 3. Table 3. Property Standard Conditions Specimen Type glass transition measured by differential temperature ISO 11375-2:2020 scanning calorimetry at a pellet heating rate of 20 °C / min Stress-Optic Measured using ellipsometer Coefficient using various weights 10-1000g Film (100 microns) Refractive Index Measured at 589 nm 1-3 mm plaque Change in viscosity was Thermal stability measured at 260 and 300 °C pellet over a period of 30 min Viscosity Viscosity (Pa.s) measured at 280 °C pellet Table 4. Glass Water Transition Scratch depth Uptake Temperature (6N) Erichsen Eq. RI (°C) SOC Mw (g / mol) (µm) (wt%) BCB 1.624 166 17 19,948 5.2 0.12 homopolycarbonate* BCB-siloxane 1.624 164 17 19,343 5.5 0.12 copolycarbonate (BCB-Si), 0.5 wt% siloxane units BCB-Si, 1 wt% 1.624 164.3 17.5 19,453 5.5 0.1 siloxane units* BCB-Si 4 wt% 1.614 16,000 siloxane units BCB-Si 4 wt% 18,000 siloxane units BCB-Si 4 wt% 159 20,800 siloxane units BCB-Si 4 wt%, 24,000 siloxane units BCB-Si 8 wt% 149 18,975 siloxane units BCB-Si 10 wt% 1.621 162.1 21 19,891 8.4 0.09 siloxane units BCB-Si 12 wt% 143 19,891 siloxane units BPA-PC 1.585 145 80 21,023 23 0.25 homopolycarbonate*22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122 Glass Water Transition Scratch depth Uptake Temperature (6N) Erichsen Eq. RI (°C) SOC Mw (g / mol) (µm) (wt%) BPA-Si 1.585 144.7 80 22,434 22.5 0.25 copolycarbonate, 1% siloxane units* BPA-Si 1.584 143.3 82 21,543 24.3 0.22 copolycarbonate 10 wt% siloxane units* BPF 1.641 230 23 18,534 24 0.21 homopolycarbonate* BPF-Si 1.641 225 25 18,343 23.5 0.21 copolycarbonate, 1% sebacic acid units* BPF-Si 1.639 223 24 18,966 26.3 0.19 copolycarbonate, 10% siloxane units* BCB-SA poly(ester- 1.624 166 15 18,272 7 0.09 carbonate), 2.2% sebacic acid units BCB-SA poly(ester- 1.624 165 15 18,942 7 0.09 carbonate), 4.4% sebacic acid units BPA-SA poly(ester- 1.585 132 70 22,000 23.9 0.17 carbonate), 8% sebacic acid units OKP4* 1.607 121 30 25,000 23.1 0.21 EP4500* 1.614 147 45 20,938 21.9 0.17

[0093] Table 4 includes property data (refractive index, glass transition temperature, stress optic coefficient, scratch test results, and water uptake) for exemplary copolymers and comparative homopolymers and copolymers (indicated with a. It is desirable to have the desired glass transition temperature within the range of 130-250 °C and one or more of the following: an RI of greater than 1.59, an SOC of -120 to 44 Br, a scratch depth of less than 19 µm, and a water uptake of 0.20% or less at equilibrium. All of the samples shown in Table 4 except for OKP4 had a glass transition temperature within the range of 130-250 °C. The BPA homopolymer and copolymers failed to provide an RI greater than 1.59, an SOC of -120 to 44 Br, a scratch depth of less than 19 µm, or a water uptake of 0.20% or less at equilibrium. The BPF homopolymer and copolymers failed to provide a scratch depth of less than 19 µm. Copolymers derived from BCB and sebacic acid achieved an RI of greater than 1.59, an SOC of -120 to 44 Br, a scratch depth of less than 19 µm, and a water uptake of 0.20% or less at equilibrium.

[0094] This disclosure further encompasses the following aspects.

[0095] Aspect 1. A copolycarbonate comprising at least 2 wt% soft repeating units and less than or equal to 98 wt% hard repeating units, based on the total weight of the22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122 copolycarbonate, wherein the hard repeating units comprise formula (A) and optionally hard repeating units derived from formula (2)HO–A1–Y1–A2–OH (2) wherein in Formula (A), a and b are each independently 0-4, c and d are each independently 0-5, and Ra, Rb, Rc, and Rdare each independently halogen, substituted or unsubstituted C1-36hydrocarbyloxy, or substituted or unsubstituted C1-36hydrocarbyl; and wherein in formula (2), each of A1and A2is a monocyclic divalent aromatic group and Y1is a single bond or a bridging group having one or more atoms that separate A1from A2; and wherein the soft repeating units comprise: repeating units derived from C5-44 aliphatic dicarboxylic acids and its reactive derivatives or equivalents; repeating units derived from C5-44aliphatic dicarboxylic acids and its reactive derivatives or equivalents and siloxane repeating units; or siloxane repeating units of formula (15)wherein in formula (15) each R is independently a C1-13alkyl, C1-13alkoxy, C2-13alkenyl, C2-13alkenyloxy, C3-6cycloalkyl, C3-6cycloalkoxy, C6-14aryl, C6-10aryloxy, C7-13arylalkylene, C7-13arylalkylenoxy, C7-13 alkylarylene, or C7-13 alkylaryleneoxy; and E has an average value of 2 to 1,000.

[0096] Aspect 2. The copolycarbonate of Aspect 1 or Aspect 2, wherein the hard repeating units further comprise repeating units derived from high refractive index monomers having a refractive index of at least 1.60 as measured at 589 nm.

[0097] Aspect 3. The copolycarbonate of any of the preceding aspects, wherein the hard repeating units comprise repeating units derived from at least one high refractive index group of formulas (6) to (12)22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122wherein Rcand Rdare each independently a C1-12alkyl, C2-12alkenyl, C3-8cycloalkyl, or C1-12alkoxy, each Rfis hydrogen or both Rftogether are a carbonyl group, each R3is independently C1-6alkyl, R4is hydrogen, C1-6alkyl, or phenyl optionally substituted with 1 to 5 C1-6alkyl groups, R6is independently C1-3alkyl, or phenyl, Xais a C6-12polycyclic aryl, C3-18mono- or polycycloalkylene, C3-18mono- or polycycloalkylidene, –C(Rf)(Rg)– wherein Rfis hydrogen, C1-12alkyl, or C6-12aryl and Rgis C6-10alkyl, C6-8cycloalkyl, or C6-12aryl, or –(Qa)x-G-(Qb)y- group, wherein Qaand Qbare each independently a C1-3 alkylene, G is a C3-10 cycloalkylene, x is 0 or 1, and y is 0 or 1, and j, m, and n are each independently 0 to 4; preferably repeating units derived from at least one high refractive index group of formulas (11a), (12a) to (12i), and (HR)22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122in formulas (11a) and (12a) to (12i), Rcand Rdare the same as defined for formulas (6) to (12), each R2is independently C1-4alkyl, m and n are each independently 0 to 4, each R3is independently C1-4alkyl or hydrogen, R4is C1-6alkyl or phenyl optionally substituted with 1 to 5 C1-6alkyl groups, and g is 0 to 10,in formula (HR), j and k are each independently 0-4, l and m are each independently 0-4, and Rj, Rk, Rl, Rmare each independently halogen, substituted or unsubstituted C1-36hydrocarbyloxy, or substituted or unsubstituted C1-36hydrocarbyl, and X is (L)x-OH, wherein x is 0-3 and L is a divalent linking group.

[0098] Aspect 4. The copolycarbonate of any one of the preceding aspects, wherein a sample of the copolycarbonate has a glass transition temperature of 130 to 250 °C, according to ASTM D3418 with a 20oC / min heating rate, and one or more of the following: a hardness of greater than 300 N / mm2, preferably 350 N / mm2to 550 N / mm2, as measured in accordance with the Eriksen scratch hardness test at a force of 2 N; scratch depth of less than 19 µm according to the Eriksen scratch test using a needle under a downward force of 6 N held at an angle of 90 degrees relative to the surface being tested; an Abbe number of less than 32, preferably less than 30, as measured according to ISO 489 on a molded sample having a 1 mm thickness; a refractive index of greater than 1.59, preferably greater than 1.60, measured at a wavelength of 589 nm at room temperature (23 °C) on a cast thin film having a thickness of 30 to 100 µm; a refractive22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122 index of greater than 1.59, preferably greater than 1.60, as measured at a wavelength of 589 nm at room temperature (23 °C) on a molded sample having a thickness of 2 to 3 millimeters; a percent change in melt volume rate of 30% or less, wherein the change in melt volume rate is the difference between the melt volume rate at (6 min) and the melt volume rate at (what time 2) divided by the melt rate at (18 min) x 100%, wherein each melt volume rate is measured at 300 ºC under a load of 1.2 kg in accordance with ASTM D1238-04; a percent change in melt volume rate of 30% or less, wherein the change in melt volume rate is the difference between the melt volume rate at (6 min) and the melt volume rate at (what time 2) divided by the melt rate at (18 min) x 100%, wherein each melt volume rate is measured at 320 ºC under a load of 1.2 kg in accordance with ASTM D1238-04; a stress-optic coefficient ranging from -120 to 44 Brewster, wherein the stress-optic coefficient is the slope of a plot of load vs. change in refractive index as measured using transmission ellipsometry on a cast thin film having a thickness of 30 to 100 µm; a percent transmission of 85% or more according to ASTM D1003-00 on a molded sample having a thickness of 1 mm; a percent haze of 2% or less according to ASTM D1003-00 on a molded sample having a thickness of 1 mm; a yellowness index of 2 or less according to ASTM D1003-00 on a molded sample having a thickness of 1 mm, and a water uptake of 0.20% or less at equilibrium according to ASTM D570 on a molded sample having a thickness of 1 mm.

[0099] Aspect 5. The copolycarbonate of any one of the preceding aspects, wherein the repeating units of formula (A) comprise formula (A1)wherein Ra1, Ra2, Rb1, and Rb2 are each independently hydrogen, halogen, C1-36 hydrocarbyloxy, or C1-36hydrocarbyl, and at least two of Ra1, Ra2, Rb1, and Rb2are not hydrogen.

[0100] Aspect 6. The copolycarbonate of any one of the preceding aspects, wherein the repeating units of Formula (A) comprise formula (BCB)22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122Formula (BCB).

[0101] Aspect 7. The copolycarbonate of any one of the preceding aspects, wherein the copolycarbonate is a poly(ester carbonate) comprising repeating units of formula (7)wherein T comprises C1-20 alkylene or a C5-44 cycloalkylene, and J comprises formula (A).

[0102] Aspect 8. The copolycarbonate of Aspect 7 comprising repeating units of formula (8)wherein each R1comprises formula (A) and m is 4 to 18, preferably 4 to 10.

[0103] Aspect 9. The copolycarbonate of any one of the preceding aspects comprising repeating units of formula (A) and siloxane repeating units.

[0104] Aspect 10. A copolycarbonate composition comprising the copolycarbonate of any one of the preceding aspects and an additive composition.

[0105] Aspect 11. A method of making a copolycarbonate of any one of Aspects 1 to 10, the method comprising: polymerizing monomer precursors of the hard repeating units comprising Formula (A) and optionally, monomer precursors of the hard repeating units of Formula (2) with the monomer precursors of the soft repeating units in the presence of a carbonyl source under conditions effective to provide the copolycarbonate.

[0106] Aspect 12. The method of Aspect 11, wherein the polymerizing is under interfacial conditions.

[0107] Aspect 13. An article comprising the copolycarbonate of any of Aspects 1 to 9 or a copolycarbonate composition of Aspect 10.

[0108] Aspect 14. The article of aspect 13, wherein the article is an optical lens or an optical film, an optical media, an optical element, an optical laminate, or an optical sheet.

[0109] Aspect 15. A method of manufacturing the article of Aspect 13 or Aspect 14 comprising shaping, blow molding, injection molding, casting, thermoforming, laminating, or extruding the copolycarbonate to provide the article.22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122

[0110] The compositions, methods, and articles can alternatively comprise, consist of, or consist essentially of any appropriate materials, steps, or components herein disclosed. The compositions, methods, and articles can additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any materials (or species), steps, or components, that are otherwise not necessary to the achievement of the function or objectives of the compositions, methods, and articles.

[0111] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other (e.g., ranges of “up to 25 wt%, or, more specifically, 5 wt% to 20 wt%”, is inclusive of the endpoints and all intermediate values of the ranges of “5 wt% to 25 wt%,” etc.). “Combinations” is inclusive of blends, mixtures, alloys, reaction products, and the like. The terms “first,” “second,” and the like, do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The terms “a” and “an” and “the” do not denote a limitation of quantity and are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. “Or” means “and / or” unless clearly stated otherwise. Reference throughout the specification to “some embodiments”, “an embodiment”, and so forth, means that a particular element described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments. A “combination thereof” is open and includes any combination comprising at least one of the listed components or properties optionally together with a like or equivalent component or property not listed.

[0112] Unless specified to the contrary herein, all test standards are the most recent standard in effect as of the filing date of this application, or, if priority is claimed, the filing date of the earliest priority application in which the test standard appears.

[0113] Unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which this application belongs. All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in the present application contradicts or conflicts with a term in the incorporated reference, the term from the present application takes precedence over the conflicting term from the incorporated reference.

[0114] Compounds are described using standard nomenclature. For example, any position not substituted by any indicated group is understood to have its valency filled by a bond as indicated, or a hydrogen atom. A dash ("-") that is not between two letters or symbols is used22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122 to indicate a point of attachment for a substituent. For example, -CHO is attached through carbon of the carbonyl group.

[0115] As used herein, the term “hydrocarbyl”, whether used by itself, or as a prefix, suffix, or fragment of another term, refers to a residue that contains only carbon and hydrogen unless it is specifically identified as “substituted hydrocarbyl”. The hydrocarbyl residue can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It can also contain combinations of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties. When the hydrocarbyl residue is described as substituted, it can contain heteroatoms in addition to carbon and hydrogen.

[0116] The term "alkyl" means a branched or straight chain, unsaturated aliphatic hydrocarbon group, e.g., methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, s- pentyl, and n- and s-hexyl. “Alkenyl” means a straight or branched chain, monovalent hydrocarbon group having at least one carbon-carbon double bond (e.g., ethenyl (-HC=CH2)). “Alkoxy” means an alkyl group that is linked via an oxygen (i.e., alkyl-O-), for example methoxy, ethoxy, and sec-butyloxy groups. "Alkylene" means a straight or branched chain, saturated, divalent aliphatic hydrocarbon group (e.g., methylene (-CH2-) or, propylene (-(CH2)3- )). “Cycloalkylene” means a divalent cyclic alkylene group, -CnH2n-x, wherein x is the number of hydrogens replaced by cyclization(s). “Cycloalkenyl” means a monovalent group having one or more rings and one or more carbon-carbon double bonds in the ring, wherein all ring members are carbon (e.g., cyclopentyl and cyclohexyl). "Aryl" means an aromatic hydrocarbon group containing the specified number of carbon atoms, such as phenyl, tropone, indanyl, or naphthyl. “Arylene” means a divalent aryl group. “Alkylarylene” means an arylene group substituted with an alkyl group. “Arylalkylene” means an alkylene group substituted with an aryl group (e.g., benzyl). The prefix "halo" means a group or compound including one more of a fluoro, chloro, bromo, or iodo substituent. A combination of different halo groups (e.g., bromo and fluoro), or only chloro groups can be present. The prefix “hetero” means that the compound or group includes at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatom(s)), wherein the heteroatom(s) is each independently N, O, S, Si, or P. “Substituted” means that the compound or group is substituted with at least one (e.g., 1, 2, 3, or 4) substituents that can each independently be a C1-9alkoxy, a C1-9haloalkoxy, a nitro (-NO2), a cyano (-CN), a C1-6alkyl sulfonyl (-S(=O)2-alkyl), a C6-12aryl sulfonyl (-S(=O)2-aryl)a thiol (-SH), a thiocyano (-SCN), a tosyl (CH3C6H4SO2-), a C3-12cycloalkyl, a C2-12alkenyl, a C5-12cycloalkenyl, a C6-12aryl, a C7-13arylalkylene, a C4-12heterocycloalkyl, and a C3-12heteroaryl instead of hydrogen, provided that the substituted atom’s normal valence is not exceeded. The number of carbon atoms indicated in22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122 a group is exclusive of any substituents. For example -CH2CH2CN is a C2 alkyl group substituted with a nitrile.

[0117] While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are or may be presently unforeseen may arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they may be amended are intended to embrace all such alternatives, modifications variations, improvements, and substantial equivalents.

Claims

22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122 CLAIMS What is claimed is:

1. A copolycarbonate comprising at least 2 wt% soft repeating units and less than or equal to 98 wt% hard repeating units, based on the total weight of the copolycarbonate, wherein the hard repeating units comprise formula (A) and optionally hard repeating units derived from formula (2)HO–A1–Y1–A2–OH (2) wherein in Formula (A), a and b are each independently 0-4, c and d are each independently 0-5, and Ra, Rb, Rc, and Rd are each independently halogen, substituted or unsubstituted C1-36 hydrocarbyloxy, or substituted or unsubstituted C1-36 hydrocarbyl; and wherein in formula (2), each of A1and A2is a monocyclic divalent aromatic group and Y1is a single bond or a bridging group having one or more atoms that separate A1from A2; and wherein the soft repeating units comprise: repeating units derived from C5-44 aliphatic dicarboxylic acids and its reactive derivatives or equivalents; repeating units derived from C5-44 aliphatic dicarboxylic acids and its reactive derivatives or equivalents and siloxane repeating units; or siloxane repeating units of formula (15)wherein in formula (15) each R is independently a C1-13 alkyl, C1-13 alkoxy, C2-13 alkenyl, C2-13 alkenyloxy, C3-6 cycloalkyl, C3-6 cycloalkoxy, C6-14 aryl, C6-10 aryloxy, C7-13 arylalkylene, C7-13 arylalkylenoxy, C7-13 alkylarylene, or C7-13 alkylaryleneoxy; and E has an average value of 2 to 1,000.22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122 2. The copolycarbonate of Claim 1, wherein the hard repeating units further comprise repeating units derived from high refractive index monomers having a refractive index of at least 1.60 as measured at 589 nm.

3. The copolycarbonate of Claim 1 or Claim 2, wherein the hard repeating units further comprise repeating units derived from at least one high refractive index group of formulas (6) to (12)wherein Rcand Rdare each independently a C1-12 alkyl, C2-12 alkenyl, C3-8 cycloalkyl, or C1-12 alkoxy, each Rfis hydrogen or both Rftogether are a carbonyl group, each R3is independently C1-6 alkyl, R4is hydrogen, C1-6 alkyl, or phenyl optionally substituted with 1 to 5 C1-6 alkyl groups, R6is independently C1-3 alkyl, or phenyl, Xais a C6-12 polycyclic aryl, C3-18 mono- or polycycloalkylene, C3-18 mono- or polycycloalkylidene, – C(Rf)(Rg)– wherein Rfis hydrogen, C1-12 alkyl, or C6-12 aryl and Rgis C6-10 alkyl, C6-8 cycloalkyl, or C6-12 aryl, or –(Qa)x-G-(Qb)y- group, wherein Qaand Qbare each independently a C1-3 alkylene, G is a C3-10 cycloalkylene, x is 0 or 1, and y is 0 or 1, and j, m, and n are each independently 0 to 4; preferably repeating units derived from at least one high refractive index group of formulas (11a), (12a) to (12i), (HR)22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122in formulas (11a) and (12a) to (12i), Rcand Rdare the same as defined for formulas (6) to (12), each R2is independently C1-4alkyl, m and n are each independently 0 to 4, each R3is independently C1-4alkyl or hydrogen, R4is C1-6alkyl or phenyl optionally substituted with 1 to 5 C1-6 alkyl groups, and g is 0 to 10,in formula (HR), j and k are each independently 0-4, l and m are each independently 0-4, and Rj, Rk, Rl, Rmare each independently halogen, substituted or unsubstituted C1-36hydrocarbyloxy, or substituted or unsubstituted C1-36hydrocarbyl, and X is (L)x-OH, wherein x is 0-3 and L is a divalent linking group.

4. The copolycarbonate of Claim 1, wherein a sample of the copolycarbonate has:22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122 a glass transition temperature of 130 to 250 °C, according to ASTM D3418 with a 20 °C / min heating rate, and one or more of the following: a hardness of greater than 300 N / mm2, preferably 350 N / mm2to 550 N / mm2, as measured in accordance with the Eriksen scratch hardness test at a force of 2 N; scratch depth of less than 19 µm according to the Eriksen scratch test using a needle under a downward force of 6 N held at an angle of 90 degrees relative to the surface being tested; an Abbe number of less than 32, preferably less than 30, as measured according to ISO 489 on a molded sample having a 1 mm thickness; a refractive index of greater than 1.59, preferably greater than 1.60, measured at a wavelength of 589 nm at room temperature (23 °C) on a cast thin film having a thickness of 30 to 100 µm; a refractive index of greater than 1.59, preferably greater than 1.60, as measured at a wavelength of 589 nm at room temperature (23 °C) on a molded sample having a thickness of 2 to 3 millimeters; a percent change in melt volume rate of 30% or less, wherein the change in melt volume rate is the difference between the melt volume rate at 6 min and the melt volume rate at 18 min divided by the melt rate at 18 min x 100%, wherein each melt volume rate is measured at 300 ºC under a load of 1.2 kg in accordance with ASTM D1238-04; a percent change in melt volume rate of 30% or less, wherein the change in melt volume rate is the difference between the melt volume rate at 6 min and the melt volume rate at 18 min divided by the melt rate at 18 min x 100%, wherein each melt volume rate is measured at 320 ºC under a load of 1.2 kg in accordance with ASTM D1238-04; a stress-optic coefficient ranging from -120 to 44 Brewster, wherein the stress-optic coefficient is the slope of a plot of load vs. change in refractive index as measured using transmission ellipsometry on a cast thin film having a thickness of 30 to 100 µm; a percent transmission of 85% or more according to ASTM D1003-00 on a molded sample having a thickness of 1 mm; a percent haze of 2% or less according to ASTM D1003-00 on a molded sample having a thickness of 1 mm; a yellowness index of 2 or less according to ASTM D1003-00 on a molded sample having a thickness of 1 mm; and22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122 a water uptake of 0.20% or less at equilibrium according to ASTM D570 on a molded sample having a thickness of 1 mm.

5. The copolycarbonate of Claim 1, wherein the repeating units of formula (A) comprise formula (A1)wherein Ra1, Ra2, Rb1, and Rb2are each independently hydrogen, halogen, C1-36hydrocarbyloxy, or C1-36hydrocarbyl, and at least two of Ra1, Ra2, Rb1, and Rb2are not hydrogen.

6. The copolycarbonate of Claim 1, wherein the repeating units of formula (A) comprise formula (BCB)The copolycarbonate of Claim 1, wherein the copolycarbonate is a poly(ester carbonate) comprising repeating units of formula (7)wherein T comprises C1-20alkylene or a C5-44cycloalkylene, and J comprises formula (A).

8. The copolycarbonate of claim 6 comprising repeating units of formula (8)wherein each R1comprises Formula (A) and m is 4 to 18, preferably 4 to 10.

9. The copolycarbonate of Claim 1 comprising repeating units of formula (A) and siloxane repeating units.

10. A copolycarbonate composition comprising the copolycarbonate of any one of Claims 1 to 9 and an additive composition.

11. A method of making a copolycarbonate of any one of Claims 1 to 10, the method comprising:22SHPP0025-WO-PCT Confidential (SS290016PCT) 20250122 polymerizing monomer precursors of the hard repeating units comprising formula (A) and optionally, monomer precursors of the hard repeating units of formula (2) with the monomer precursors of the soft repeating units in the presence of a carbonyl source under conditions effective to provide the copolycarbonate.

12. The method of Claim 11, wherein the polymerizing is under interfacial conditions.

13. An article comprising the copolycarbonate of any of Claims 1 to 9 or a copolycarbonate composition of Claim 10.

14. The article of Claim 13, wherein the article is an optical lens or an optical film, an optical media, an optical element, an optical laminate, or an optical sheet.

15. A method of manufacturing the article of Claim 13 or Claim 14 comprising shaping, blow molding, injection molding, casting, thermoforming, laminating, or extruding the copolycarbonate to provide the article.

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