WO2017182986A1 - Methods of manufacture of 2-aryl-3,3-bis(hydroxyaryl)phthalimidines - Google Patents

Abstract

A method for the manufacture of a 2-aryl-3,3-bis(hydroxyaryl)phthalimidine via O- alkylation of a dihydroxy benzophenone, and formation of Schiff base, followed by cyclisation and de-O-alkylation to provide the product phthalimidine is provided. Polymers including structural units derived from the 2-aryl-3,3-bis(hydroxyaryl)phthalimidine are provided. Methods for the manufacture of a polycarbonate, including manufacturing the 2-aryl-3,3- bis(hydroxyaryl)phthalimidine, and polymerizing the 2-aryl-3,3-bis(hydroxyaryl)phthalimidine in the presence of a carbonate source are provided.

Description

METHODS OF MANUFACTURE OF 2-ARYL-3,3- B IS (HYDROXY ARYL)PHTHALIMIDINES

BACKGROUND

[0001] There is a need for methods for the production of 2-phenyl-3,3-bis(4- hydroxyphenyl)phthalimidine (also known as N-phenyl phenolphthalein bisphenol (PPPBP) or 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-l-one)) wherein the as- synthesized product contains reduced amounts of an aminophenol, or no aminophenol.

SUMMARY

[0002] A method for the manufacture of a 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I)

the method comprising: O-alkylating a benzophenone of formula (II)

to provide a dialkoxybenzophenone of formula (III)

(HI);

reacting the dialkoxybenzophenone of formula (III) with a primary aryl amine of formula

(IV)

in the presence of an acid catalyst, to provide an imine of formula (V)

cyclizing the imine of formula (V) in the presence of a cyclization catalyst and a benzoyl halide of formula (VI)

to provide a 2-aryl-3,3-bis(alkoxyaryl)phthalimidine of formula (VII)

dealkylating the 2-aryl-3,3-bis(alkoxyaryl)phthalimidine of formula (VII) in the presence of a dealkylating agent to provide the 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I); wherein in formulas (I), (II), (III), (IV), (V), (VI), and (VII) each occurrence of R¹ is the same or different, and is a phenyl or a Ci-25 hydrocarbyl, preferably a phenyl or a Ci-6 alkyl, more preferably a C1-3 alkyl, each occurrence of R² and R³ is independently a Ci-25 hydrocarbyl or halogen, preferably a Ci-6 alkyl, more preferably a C1-3 alkyl, each occurrence of R⁴ is independently a Ci-6 hydrocarbyl, preferably a Ci-6 alkyl, more preferably a C1-3 alkyl and r, p, and q are each independently an integer of 0 to 4, more preferably 0 or 1, preferably 0 is provided.

[0003] 2-Aryl-3,3-bis(4-hydroxyaryl)phthalimidines produced by the described method are also provided.

[0004] A 2-aryl-3,3-bis(4-hydroxyaryl) phthalimidine composition, comprising an as- synthesized phthalimidine of formula (I)

wherein each occurrence of R is the same or different, and is a phenyl or a Ci-25 hydrocarbyl, preferably a phenyl or a C_1-6 alkyl, more preferably a C1-3 alkyl, each occurrence of R² and R³ is independently a Ci-25 hydrocarbyl or halogen, preferably a C_1-6 alkyl, more preferably a C1-3 alkyl, and r, p, and q are each independently 0 to 4, more preferably 0 or 1, preferably 0; zero to 100 parts per million of an aminophenol, or zero to 50 parts per million of an aminophenol, or zero to 20 parts per million of an aminophenol, or zero to 5 parts per million of an aminophenol; or zero to 500 parts per million of a phenolphthalein, or zero to 50 parts per million of a phenolphthalein is also provided.

[0005] A method for the manufacture of a polycarbonate, comprising manufacturing the 2-aryl-3,3-bis(4-hydroxyaryl) phthalimidine of formula (I) in accordance with the methods provided; and polymerizing the 2-aryl-3,3-bis(4-hydroxyaryl) phthalimidine of formula (I) in the presence of a carbonate source to form a polycarbonate is also provided.

[0006] The above described and other features are exemplified by the following detailed description.

DETAILED DESCRIPTION

[0007] The present disclosure is generally directed to producing phenolphthalein derivatives, in particular 2-aryl-3,3-bis(4-hydroxyaryl)phthalimidines, which are suitable for use as monomers or comonomers for preparing polycarbonates and other polymers. Provided is a synthetic route for producing a 2-aryl-3,3-bis(4-hydroxyaryl)phthalimidine, preferably 2-phenyl- 3,3-bis(4-hydroxyphenyl)phthalimidine (PPPBP), using a dihydroxy benzophenone starting material. The synthesis proceeds via O-alkylation of the dihydroxy benzophenone, and formation of Schiff base, followed by cyclisation and de-O-alkylation to provide the product phthalimidine. In a highly advantageous feature, in an embodiment, the product can exhibit no detectable aminophenol, and less than 50 ppm of phenolphthalein can be formed. The method can thus advantageously reduce or eliminate the need for a separate purification step to remove the aminophenol. For example this method can avoid or minimize aminophenol impurity formation, thereby reducing or eliminating the existing downstream purification required using activated carbon/acidic ion exchange resin as an adsorbent for removing the aminophenol impurity. The method is further described in detail below.

[0008] The 2-aryl-3,3-bis(4-hydroxyaryl)phthalimidines produced in accordance with these methods can be used in the manufacture of polycarbonates and other polymers. The 2- aryl-3,3-bis(4-hydroxyaryl)phthalimidines produced are of formula (I):

wherein each occurrence of R is the same or different, and is a phenyl or a Ci-25 hydrocarbyl, preferably a phenyl or Ci-6 alkyl, more preferably a C1-3 alkyl, each occurrence of R² and R³ is independently a Ci-25 hydrocarbyl or halogen, preferably a Ci-6 alkyl, more preferably a C1-3 alkyl, and r, p, and q are each independently an integer of 0 to 4, more preferably 0 or 1, preferably 0. In some embodiments, R¹ is a C1-3 alkyl group, and R² is hydrogen, a C1-3 alkyl group, or a halogen, and q is 0.

[0009] The following reaction Scheme (I) shows generally a method for the manufacture of 2-aryl-3,3-bis(4-hydroxyphenyl)-2-phthalimidine (I).

Scheme I.

[0010] In Scheme I, each occurrence of R¹ is independently a phenyl or a Ci-25 hydrocarbyl, preferably a phenyl or a Ci-6 alkyl; each occurrence of R² and R³ is independently a Ci-25 hydrocarbyl or halogen, preferably a Ci-6 alkyl, more preferably a C1-3 alkyl; each occurrence of R⁴ is independently a Ci-6 hydrocarbyl, preferably a Ci-6 alkyl, more preferably a Ci-3 alkyl; and r, p, and q are each independently an integer of 0 to 4, more preferably 0 or 1, preferably 0.

[0011] Preferably in Scheme I, each occurrence of R¹ is the same or different, and is a phenyl or a Ci-6 alkyl; each occurrence of R² and R³ is independently a Ci-6 alkyl, more preferably a C1-3 alkyl; each occurrence of R⁴ is independently a Ci-6 alkyl, more preferably a Ci-3 alkyl; and r, p, and q are each independently 0 or 1, preferably 0.

[0012] The following reaction Scheme (II) shows generally a preferred method for the manufacture of preferred 2-aryl-3,3-bis(4-hydroxyphenyl)phthalimidine (la).

Scheme II

[0013] In Scheme II, each occurrence of R¹ is the same or different, and is a phenyl or a Ci-25 hydrocarbyl, preferably a phenyl or a Ci-6 alkyl; each occurrence of R³ is independently a Ci-25 hydrocarbyl or halogen, preferably a Ci-6 alkyl, more preferably a C1-3 alkyl; each occurrence of R⁴ is independently a Ci-6 hydrocarbyl, preferably a Ci-6 alkyl, more preferably a Ci-3 alkyl; and r, p, and q are each independently 0 to 4, more preferably 0 or 1, preferably 0. [0014] Preferably in Scheme II, each occurrence of R¹ is the same or different, and is a phenyl or a C_1-6 alkyl; each occurrence of R² and R³ is independently a C_1-6 alkyl, more preferably a C1-3 alkyl; each occurrence of R⁴ is independently a C1-3 alkyl; and r, p, and q are each independently and integer of 0 or 1, preferably 0.

[0015] As shown in Schemes I and II, the reaction of the benzophenone of formula (II) or (Ila) to form a dialkoxybenzophenone of formula (III) or (Ilia) can proceed by O-alkylating (or methylating) by reaction of a dihydroxy benzophenone is the presence of an alkylating agent with a base in a solvent. Exemplary alkylating agents include dimethyl sulfate, Ci-6 alkyl bromides or Ci -C₆ -alkyl iodides, such as methyl bromide, methyl iodide, ethyl bromide, ethyl iodide, benzyl chloride, benzoyl chloride, tetraalkylammonium salts, oxonium salts, dimethyl carbonate, diazomethanes, trialkyl silyl diazomethanes, dialkyl acetals of N,N-dimethyl formamide, O-methyl caprolactam, isourea ethers, tert-butyl ethers of derivatives of morphine, and thiazynes. In some embodiments, the alkylating agent is present at a concentration of 0.3 to 0.8 molar equivalents, preferably 0.35 to 0.75 molar equivalents of the benzophenone of formula (II).

[0016] The reaction of the dialkoxybenzophenone of formula (III) or (Ilia) to form an imine of formula (V) can proceed by reaction of the dialkoxybenzophenone of formula (III) with a hydrocarbyl amine, such as, for example, a primary aryl amine of formula (IV) in the presence of an acid catalyst in a solvent.

[0017] Exemplary primary aryl amines include aniline, alkyl, alkoxy, aryl, aryloxy, and aryl alkyl substituted aniline. In some embodiments, the primary aryl amine is present at a concentration of 0.05 to 0.2 molar equivalents of the dialkoxybenzophenone of formula (III).

[0018] Exemplary solvents include solvents include polar protic solvents such as methanol, ethanol, propanol, butanol and the like; polar aprotic solvents such as dimethyl formamide, dimethyl sulfoxide (DMSO), tetrahydrofuran, acetonitrile, and the like; chlorinated solvents such as methylene chloride, 1,2-dichloroethane, chlorobenzene, chloroform, tetrachloroethane, ortho dichloro benzene, trichloro benzene, and the like; other aromatic solvents such as benzene, toluene, xylenes, and the like.

[0019] Suitable acid catalysts include, but are not limited to, mineral acids such as hydrochloric acid (HC1), sulfuric acid, nitric acid, and phosphoric acid; weak inorganic acids such as boric acid, organic sulfonic acids such as methanesulfonic acid, triflic acid, Lewis acids such as stannic chloride, aluminium chloride, ferric chloride, indium chloride, and zinc chloride; sulfated zirconia; or combinations of two or more of the foregoing acid catalysts. Exemplary acid catalysts include mineral acids, including hydrochloric acid. Suitable acid catalysts also include amine salts of the above mineral acids. Amine salts of mineral acids can be formed from the reaction of mineral acids with amines. Examples of suitable amines for forming the acid catalysts include primary, secondary, and tertiary amines having any combination of aliphatic and aromatic groups bonded to the amine nitrogen. Exemplary amine salt catalysts include primary, secondary, and tertiary amine hydrochlorides. In some embodiments, the acid catalyst is introduced as a pre-formed salt of an amine and a mineral acid into the reactor. In another embodiment, the acid catalyst is generated in the reactor by first charging the amine into the reactor, and then adding about 1/3 to about 1 part by weight of an appropriate mineral acid to phenolphthalein compound. In another embodiment, the acid catalyst is generated in the reactor by first charging the amine and an appropriate mineral acid into the reactor, and then adding the phenolphthalein compound. In still another embodiment, about 0.1 parts to about 0.3 parts by weight of hydrogen chloride gas is introduced into a reactor charged with the amine to form an appropriate amount of the amine hydrochloride catalyst. More hydrochloric acid or more hydrogen chloride gas can also be used, but is generally not required. A solvent can optionally be used to initially form the amine hydrochloride from the primary hydrocarbyl amine. The solvent can then be removed (if desired), and the amine catalyst, e.g., an aryl amine salt, can be added to the reaction mixture. The mineral acids used for preparing the amine salts can be present in a fluid phase, for example, in a gaseous phase or in a liquid phase or in a combination of the gaseous and liquid phases. Non-limiting examples of mineral acids include hydrogen chloride liquid, hydrogen chloride gas, sulfuric acid, nitric acid, and the like. The acid catalyst can be present at a concentration of 0.5 to 1.5 molar equivalents, preferably 0.5 to 0.7 molar equivalents of the dialkoxybenzophenone of formula (III) or (Ilia).

[0020] The reaction of the imine of formula (V) or (Va) to provide a 2-aryl-3,3- bis(alkoxyaryl)phthalimidine of formula (VIII) or (Villa) can proceed by cyclizing the imine of formula (V) or (Va) in the presence of a cyclization catalyst and a benzoyl halide of formula (VI) or (Via) in a solvent. Exemplary cyclization catalysts include triflic acid,

trifluoromethanesulfonic acid, difluororaethane sulfonic acid, fiuoromethane sulfonic acid, trill Qoroacetic acid, difluoroacetic acid, fiuoroacetic acid, trifluoromethane sulfonic acid, difiuoroethane sulfonic acid, fluoroethane sulfonic acid, and the like. The cyclization catalyst can be a super acid. The benzoyl halide can be benzoyl chloride. In some embodiments, the cyclization catalyst is present at a concentration of 0.5 to 1.5 molar equivalents, preferably 0.62 molar equivalent of cyclization catalyst. The benzoyl halide concentration can be 0.015 molar equivalents to 0.052 molar equivalents, preferably 0.017 molar equivalents of the imine of formula (V). [0021] The reaction of a 2-aryl-3,3-bis(alkoxyaryl)phthalimidine of formula (VIII) or (Villa) to provide a 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I) or (la) can proceed by de-O-alkylating in the presence of a dealkylating agent in a solvent. Exemplary dealkylating agents include boron tribromide, boron trichloride, boron triiodide, aluminium chloride, indium chloride, pyridine hydrochloride, mineral acids such as 48% hydrobromic acid, hydroiodic acid, weak acids such as acetic acid and the like, iodoalkanes/dimethylformamide,

diorganophosphides, lithium chloride/dimethylformamide, lithium iodide, beryllium chloride, alkali metal cyanides/dimethylsulfoxide, alkaline fluorine containing catalysts such as aluminium borofluoride or zinc fluoride supported on alumina and the like, and carbon containing catalysts such as metal impregnated charcoals. In some embodiments, the dealkylating agent is present at a concentration of 0.005 to 0.020 molar equivalents, preferably 0.010 molar equivalents of the 2-aryl-3,3-bis(alkoxyaryl)phthalimidine of formula (VII). The reaction steps can proceed under atmospheric conditions or an inert atmosphere, for example at a temperature of 0°C to 60°C, preferably 25°C.

[0022] The as- synthesized 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I) comprises zero to 100 parts per million of an aminophenol, for example an aminophenol of the formula

or zero to 50 parts per million of an aminophenol, or zero to 20 parts per million of an aminophenol, or zero to 5 parts per million of an aminophenol before any additional

purification. The as-synthesized 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I) can comprise zero to 500 parts per million of a phenolphthalein, or zero to 50 parts per million of a phenolphthalein before any additional purification.

[0023] The product of each reaction step can be purified, including by filtration or extraction, before use in a subsequent step, or the product of each reaction step can be used as- synthesized.

[0024] In particular, the 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I) or (la) can be further purified, for example by trituration with a solvent such as methanol to provide a purified 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I) or (la). The purified 2-aryl-3,3- bis(hydroxyaryl)phthalimidine of formula (I) or (la) can comprise zero to 50 parts per million of an aminophenol, or zero to 20 parts per million of an aminophenol, or zero to 5 parts per million of an aminophenol; or zero to 100 parts per million of a phenolphthalein, or zero to 50 parts per million of a phenolphthalein.

[0025] In some embodiments the purified 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I) or (la) can comprise one or more, preferably all of less than 0.1% by weight of organic impurities other than an aminophenol or phenolphthalein; less than 3 ppm of iron; less than 50 ppm of methanol; or an APHA color of less than 40. The APHA color is determined by standard methods such as ASTM D1209 in effect as of the filing date of this application.

[0026] A polymer comprising structural units derived from the 2-aryl-3,3-bis(4- hydroxyaryl) phthalimidine manufactured by the methods described herein is also provided. The polymer can be a polycarbonate, preferably wherein the polymer is a copolycarbonate comprising units derived from the 2-aryl-3,3-bis(4-hydroxyaryl) phthalimidine of formula (I) and units derived from bisphenol A. A method for the manufacture of a polycarbonate, includes manufacturing the 2-aryl-3,3-bis(4-hydroxyaryl) phthalimidine of formula (I) in accordance with a method described herein; and polymerizing the 2-aryl-3,3-bis(4-hydroxyaryl) phthalimidine of formula (I) in the presence of a carbonate source.

[0027] The 2-aryl-3,3-bis(4-hydroxyaryl)phthalimidines, including the exemplary 2- phenyl-3,3-bis(4-hydroxyphenyl)phthalimidine (PPPBP), are commercially valuable monomers or comonomers for producing a variety of polymers formed by reactions of the phenolic OH groups of the 2-aryl-3,3-bis(4-hydroxyaryl)phthalimidines. Exemplary polymers that can be produced include homopolymers and copolymers of a polycarbonate, a polyestercarbonate, a polyester, a polyesteramide, a polyimide, a polyetherimide, a polyamideimide, a polyether, a polyethersulfone, a polycarbonate-polyorganosiloxane block copolymer, a copolymer comprising aromatic ester, ester carbonate, and carbonate repeat units, and a polyetherketone. An example of a copolymer comprising aromatic ester, estercarbonate, and carbonate repeat units is the copolymer produced by the reaction of a hydroxy-terminated polyester, such as the product of reaction of isophthaloyl chloride and terephthaloyl chloride with resorcinol, with phosgene and an aromatic dihydroxy compound, such as bisphenol A.

[0028] In some embodiments, polycarbonates having low color properties are synthesized, wherein the polycarbonates include structural units of formula (Va):

(Va)

which are derived from a 2-aryl-3,3-bis(4-hydroxyaryl)phthalimidine of formula (I), wherein R¹ and R² are as described previously; and the C=0 structural units are derived from a C=0 donor such as a carbonic acid diester in a melt transesterification process, or phosgene in an interfacial process.

[0029] Specific polycarbonates are copolycarbonates having structural units derived from a phthalimidine compound of formula (I) and a dihydroxy compound of the formula HO- R^OH, in particular of formula (Via)

HO-A^Y^-OH (Via)

wherein each of A¹ and A² is a monocyclic divalent aromatic group and Y¹ is a single bond or a bridging group having one or more atoms that separate A¹ from A². In an exemplary

embodiment, one atom separates A¹ from A². Specifically, each R¹ can be derived from a dihydroxy aromatic compound of formula VII):

wherein R^a and R^b each represent a halogen or Ci-12 alkyl group and can be the same or different; and p and q are each independently integers of 0 to 4. X^a represents a single bond or a bridging group connecting the two hydroxy-substituted aromatic groups, where the single bond or the bridging group and the hydroxy substituent of each C₆ arylene group are disposed ortho, meta, or para (specifically para) to each other on the C₆ arylene group. In an embodiment, the bridging group X^ais -0-, -S-, -S(O)-, -S(0)₂-, -C(O)-, or a CMS organic group. The CMS organic 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 CMS organic group can be disposed such that the C₆ arylene groups connected thereto are each connected to a common alkylidene carbon or to different carbons of the CMS organic group. In some embodiments, p and q is each 1, and R^a and R^b are each a C1-3 alkyl group, specifically methyl, disposed meta to the hydroxy group on each arylene group.

[0030] In an embodiment, X^a is a substituted or unsubstituted C3-18 cycloalkylidene, a Ci- 25 alkylidene of formula -C(R^c)(R^d) - wherein R^c and R^d are each independently hydrogen, Ci-12 alkyl, Ci-12 cycloalkyl, C7-12 arylalkyl, Ci-12 heteroalkyl, or cyclic C7-12 heteroarylalkyl, or a group of the formula -C(=R^e)- wherein R^e is a divalent Ci-12 hydrocarbon group. Exemplary groups of this type include methylene, cyclohexylmethylene, ethylidene, neopentylidene, and isopropylidene, as well as 2-[2.2.1]-bicycloheptylidene, cyclohexylidene, cyclopentylidene, cyclododecylidene, and adamantylidene. In another embodiment, X^A is a CMS alkylene group, a C3-18 cycloalkylene group, a fused C₆-i8 cycloalkylene group, or a group of the formula -E^-W- B²- wherein B¹ and B² are the same or different Ci-6 alkylene group and W is a C3-12

cycloalkylidene group or a C₆-i6 arylene group.

[0031] Other useful aromatic dihydroxy compounds of the formula HO-R^OH include compounds of formula (VIII):

wherein each R is independently a halogen atom, a Ci-10 hydrocarbyl such as a Ci-10 alkyl group, a halogen-substituted Ci-10 alkyl group, a C6-10 aryl group, or a halogen-substituted C6-10 aryl group, and n is 0 to 4. The halogen is usually bromine.

[0032] Some illustrative examples of specific aromatic 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, l,2-bis(4-hydroxyphenyl)ethane, l,l-bis(4-hydroxyphenyl)-l-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, l,l-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, 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, l,6-bis(4-hydroxyphenyl)-l,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 ("spirobiindane 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 combinations comprising at least one of the foregoing dihydroxy compounds.

[0033] Specific examples of bisphenol compounds of formula (VII) include l,l-bis(4- hydroxyphenyl) methane, l,l-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, l,l-bis(4-hydroxyphenyl) propane, l,l-bis(4-hydroxyphenyl) n-butane, 2,2-bis(4-hydroxy-2-methylphenyl) propane, l,l-bis(4-hydroxy-t-butylphenyl) propane, 3,3- bis(4-hydroxyphenyl) phthalimidine, and l,l-bis(4-hydroxy-3-methylphenyl)cyclohexane (DMBPC). Combinations comprising at least one of the foregoing dihydroxy compounds can also be used. In one specific embodiment, the polycarbonate is a linear homopolymer derived from bisphenol A, in which each of Al and A2 is p-phenylene and Yl is isopropylidene in formula (3).

[0034] Exemplary carbonic acid diesters useful in the formation of the polycarbonates in a melt transesterification process are of formula (IX):

(ZO)₂C=0 _(IX)

wherein each Z is independently an unsubstituted or substituted Ci-12 alkyl radical, or an unsubstituted or substituted C6-22 aryl radical. Examples of carbonic acid diesters include, but are not limited to, ditolyl carbonate, m-cresyl carbonate, dinaphthyl carbonate, diphenyl carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, and combinations thereof. Diphenyl carbonate is widely used as a carbonic acid diester due to its low cost and ready availability on a commercial scale. Use of activated aromatic carbonates that are more reactive than diphenyl carbonate is also contemplated. Specific non-limiting examples of activated aromatic carbonates include bis(o-methoxycarbonylphenyl)carbonate, bis(o- chlorophenyl)carbonate, bis(o-nitrophenyl)carbonate, bis(o-acetylphenyl)carbonate, bis(o- phenylketonephenyl)carbonate, bis(o-formylphenyl)carbonate. Unsymmetrical combinations of these structures are also contemplated. Exemplary ester-substituted diaryl carbonates include, but are not limited to, bis(methylsalicyl)carbonate (CAS Registry No. 82091-12-1) (also known as BMSC or bis(o-methoxycarbonylphenyl)carbonate), bis(ethyl salicyl)carbonate, bis(propyl salicyl) carbonate, bis(butylsalicyl) carbonate, bis(benzyl salicyl)carbonate, bis(methyl 4- chlorosalicyl)carbonate, and the like. In some embodiments, BMSC is used in the melt transesterification process.

[0035] The melt transesterification process is generally carried out by combining a catalyst, the carbonic acid diester of formula (IX), the phthalimidine compound of formula (I), and optionally a dihydroxy comonomer; and mixing the reaction mixture under reactive conditions for a time period effective to produce the polycarbonate product. Exemplary melt transesterification catalysts include alkali metal compounds, alkaline earth metal compounds, tetraorganoammonium compounds, tetraorganophosphonium compounds, and combinations comprising at least one of the foregoing catalysts. Specific examples of alkali metal compounds or alkaline earth metal compounds include, but are not limited to, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, sodium stearate, potassium stearate, sodium hydroxyborate, sodium phenoxyborate, sodium benzoate, potassium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium salts, dipotassium salts, and dilithium salts of bisphenol A, and sodium salts, potassium salts, lithium salts of phenol, and the like. Specific examples of tetraorganoammonium compounds and tetraorganophosphonium compounds include, but are not limited to tetramethylammonium hydroxide, tetrabutylammonium hydroxide, tetraethylphosphonium hydroxide,

tetrabutylphosphonium acetate, tetrabutylphosphonium hydroxide, and the like.

[0036] In some embodiments, the catalyst is tetrabutylphosphonium acetate. In an alternative embodiment, the catalyst comprises a mixture of an alkali metal salt or alkaline earth metal salt with at least one quaternary ammonium compound, at least one quaternary phosphonium compound, or a mixture thereof. For example, the catalyst can be a mixture of sodium hydroxide and tetrabutylphosphonium acetate. In another embodiment, the catalyst is a mixture of sodium hydroxide and tetramethylammonium hydroxide. In yet another

embodiment, the catalyst comprises the salt of a non- volatile inorganic acid, for example alkali metal salts of phosphites; alkaline earth metal salts of phosphites; alkali metal salts of phosphates; and alkaline earth metal salts of phosphates, including but not limited to NaH₂P03, NaH₂P0₄, Na₂H₂P0₃, KH₂P0₄, CsH₂P0₄, Cs₂H₂P0₄, or a mixture thereof. In some

embodiments, the transesterification catalyst comprises both the salt of a non-volatile acid and a basic co-catalyst such as an alkali metal hydroxide. This concept is exemplified by the use of a combination of NaH₂P0₄ and sodium hydroxide as the transesterification catalyst.

[0037] Any of the catalysts disclosed above can be used as combinations of two or more substances. Moreover, the catalyst can be added in a variety of forms. For example, the catalyst can be added as a solid as a powder, or it can be dissolved in a solvent, for example, in water or alcohol. The total catalyst composition can be about 1 X 10^"7 to about 2 X 10^"3 moles, and in other embodiments, about 1 X 10^"6 to about 4 X 10^"4 moles, for each mole of the combination of, for example, the purified PPPBP and the aromatic dihydroxy comonomer.

[0038] The progress of the polymerization reaction can be monitored by measuring the melt viscosity or the weight average molecular weight of the reaction mixture using techniques known in the art such as gel permeation chromatography. These properties can be measured by taking discreet samples or can be measured on-line. After the desired melt viscosity or molecular weight is reached, the final polycarbonate product can be isolated from the reactor in a solid or molten form. The method of making polycarbonates as described in the preceding sections can be made in a batch or a continuous process.

[0039] In some embodiments, the melt-polymerized polycarbonate is prepared in an extruder in the presence of one or more catalysts. The reactants for the polymerization reaction can be fed to the extruder in powder or molten form. In some embodiments, the reactants are dry blended prior to addition to the extruder. The extruder can be equipped with pressure reducing devices (e.g., vents) that serve to remove the activated phenol byproduct and thus drive the polymerization reaction toward completion. The molecular weight of the polycarbonate product can be manipulated by controlling, among other factors, the feed rate of the reactants, the type of extruder, the extruder screw design, and configuration, the residence time in the extruder, the reaction temperature, and the pressure reducing techniques present on the extruder. The molecular weight of the polycarbonate product can also depend upon the structures of the reactants and the catalyst employed. Many different screw designs and extruder configurations are commercially available that use single screws, double screws, vents, back flight and forward flight zones, seals, side-streams, and sizes.

[0040] Alternatively, the polycarbonates can be prepared by an interfacial

polymerization process. Although the reaction conditions for interfacial polymerization can vary, an exemplary process generally involves dissolving or dispersing a dihydric phenol reactant in aqueous caustic soda or potash, adding the resulting mixture to a water-immiscible solvent medium, and contacting the reactants with a carbonate precursor in the presence of a catalyst such as triethylamine or a phase transfer catalyst, under controlled pH conditions, e.g., about 8 to about 12. The most commonly used water immiscible solvents include methylene chloride, 1,2-dichloroethane, chlorobenzene, toluene, and the like.

[0041] Exemplary carbonate precursors for interfacial polymerization include a carbonyl halide such as carbonyl bromide or carbonyl chloride, or a haloformate such as a

bishaloformates of a dihydric phenol (e.g., the bischloroformates of bisphenol A, hydroquinone, or the like) or a glycol (e.g., the bishaloformate of ethylene glycol, neopentyl glycol,

polyethylene glycol, or the like). Combinations comprising at least one of the foregoing types of carbonate precursors can also be used. In an exemplary embodiment, an interfacial

polymerization reaction to form carbonate linkages uses phosgene as a carbonate precursor, and is referred to as a phosgenation reaction.

[0042] Among the phase transfer catalysts that can be used for interfacial polymerization are tetraorgano ammonium compounds and tetraorganophosphonium compounds of the formula (R3)4Q⁺X, wherein each R₃ is independently a Ci-io alkyl group; Q is a nitrogen or phosphorus atom; and X is a halogen atom or a C_1-8 alkoxy group or C₆-i8 aryloxy group. Exemplary phase transfer catalysts include, for example, [CH₃(CH₂)₃]₄NX, [CH₃(CH₂)₃]₄PX, [CH₃(CH₂)₅]₄NX, [CH₃(CH₂)₆]₄NX, [CH₃(CH₂)₄]₄NX, CH₃[CH₃(CH₂)₃]₃NX, and CH₃[CH₃(CH₂)₂]₃NX, wherein X is C1-, Br-, a C_1-8 alkoxy group or a C6-18 aryloxy group. An effective amount of a phase transfer catalyst can be about 0.1 to about 10 wt% based on the weight of bisphenol in the phosgenation mixture. In another embodiment an effective amount of phase transfer catalyst can be about 0.5 to about 2 wt% based on the weight of bisphenol in the phosgenation mixture.

[0043] All types of polycarbonate end groups are contemplated as being useful in the polycarbonate composition, provided that such end groups do not significantly adversely affect desired properties of the compositions. Branched polycarbonate blocks can be prepared by adding a branching agent during polymerization. A chain stopper (also referred to as a capping agent) can be included during polymerization. The chain stopper limits molecular weight growth rate, and so controls molecular weight in the polycarbonate. Exemplary chain stoppers include certain mono-phenolic compounds, mono-carboxylic acid chlorides, or mono- chloroformates.

[0044] The interfacial method described above can be suitably adapted to produce polycarbonates through the intermediate formation of 2-aryl-3,3-bis(4- hydroxyaryl)phthalimidine bischloroformate. This method is sometimes called the bischloroformate polymerization method. In some embodiments, the method comprises reacting a 2-aryl-3,3-bis(4-hydroxyaryl)phthalimidine with phosgene in an organic solvent, and then reacting the bischloroformate either with a 2-aryl-3,3-bis(4-hydroxyaryl)phthalimidine, or an aromatic dihydroxy compound in the presence of an acid acceptor and an aqueous base to form the polycarbonate. The interfacial polymerization method and the bischloroformate

polymerization method can be carried in a batch or a continuous mode using one or more reactor systems. To carry out the process in a continuous mode, one or more continuous reactors, such as for example, a tubular reactor can be used. In some embodiments, the continuous method comprises introducing into a tubular reactor system phosgene, at least one solvent (example, methylene chloride), at least one bisphenol, aqueous base, and optionally one or more catalysts (example, a trialkylamine) to form a flowing reaction mixture. The flowing mixture is then passed through the tubular reactor system until substantially all of the phosgene has been consumed. The resulting mixture is next treated with a mixture comprising an aqueous base, at least one endcapping agent, optionally one or more solvents, and at least one catalyst. The endcapped polycarbonate thus formed is continuously removed from the tubular reactor system.

[0045] The processes disclosed herein can advantageously be used to prepare, for example, PPPBP homopolycarbonate and copolycarbonates having a weight average molecular weight (Mw) of about 3,000 to about 150,000 Daltons and a glass transition temperature (Tg) of about 80°C to about 300°C. The number average molecular weights (Mn) of the

homopolycarbonate and copolycarbonates can be from about 1,500 to about 75,000 Daltons.

[0046] Polymers comprising structural units derived from the phthalimidines, in particular PPPBP can be used to manufacture polymer blends comprising the polymer and at least one other thermoplastic polymer. The at least one other thermoplastic polymer includes vinyl polymers, acrylic polymers, polyacrylonitrile, polystyrenes, polyolefins, polyesters, polyurethanes, polyamides, polysulfones, polyimides, polyetherimides, polyphenylene ethers, polyphenylene sulfides, polyether ketones, polyether ether ketones, ABS polymers,

polyethersulfones, poly(alkenylaromatic) polymers, polybutadiene, polyacetals, polycarbonates, polyphenylene ethers, ethylene-vinyl acetate copolymers, polyvinyl acetate, liquid crystal polymers, ethylene-tetrafluoroethylene copolymer, aromatic polyesters, polyvinyl fluoride, polyvinylidene fluoride, polyvinylidene chloride, tetrafluoroethylene, polycarbonate- polyorganosiloxane block copolymers, copolymers comprising aromatic ester, estercarbonate, and carbonate repeat units, and combinations comprising at least one of the foregoing polymers.

[0047] The polymers and polymer blends described hereinabove are valuable for producing articles. In some embodiments, an article comprises a polymer comprising structural units derived from a 2-aryl-3,3-bis(4-hydroxyaryl)phthalimidine of formula (I) prepared by following the process described above.

[0048] Polymers, particularly polycarbonate homopolymers and copolymers comprising structural units derived from the high purity 2-aryl-3,3-bis(4-hydroxyaryl)phthalimidine in general, and PPPBP in particular exhibit lower visual coloration. As such, these polycarbonate polymers are useful for producing articles having a number of useful properties, including lower visual color, among others. The polycarbonate homopolymers and copolymers have high glass transition temperatures of higher than or equal to about 180°C. One of the unique properties of these polycarbonates, especially those that have glass transition temperatures of greater than or equal to about 180°C is that during melt processing they exhibit a shear-thinning behavior. That is, the polymers have the ability to flow under an applied shear. Therefore, standard melt processing equipment used for BPA polycarbonates can advantageously be used for producing articles. The polycarbonates can also have high transparency, as measured by percent light transmission, of greater than or equal to about 85 percent.

[0049] In addition to the polymer, the thermoplastic compositions comprising the polymers 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 thermoplastic composition, in particular low color. Such additives can be mixed at a suitable time during the mixing of the components for forming the composition. The additive can be soluble or non-soluble in polycarbonate. The additive composition can include an impact modifier, flow modifier, filler (e.g., a particulate

polytetrafluoroethylene (PTFE), glass, carbon, mineral, or metal), reinforcing agent (e.g., glass fibers), antioxidant, heat stabilizer, light stabilizer, ultraviolet (UV) light stabilizer, UV absorbing additive, plasticizer, lubricant, release agent (such as a mold release agent), antistatic agent, anti-fog agent, antimicrobial agent, colorant (e.g., a dye or pigment), surface effect additive, radiation stabilizer, flame retardant, anti-drip agent (e.g., a PTFE-encapsulated styrene- acrylonitrile copolymer (TS AN)), or a combination comprising at least one or more of the foregoing. For example, a combination of a heat stabilizer, mold release agent, and ultraviolet light stabilizer can be used. In general, the additives are used in the amounts generally known to be effective. For example, the total amount of the additive composition (other than any impact modifier, filler, or reinforcing agent) can be 0.001 to 10.0 wt%, or 0.01 to 5 wt%, each based on the total weight of the polymer in the composition.

[0050] The disclosure is further illustrated by the following non-limiting examples. EXAMPLES

[0051] The following reaction Scheme III describes generally a method for the manufacture of 2-phenyl-3,3-bis(4-hydroxyphenyl)-2-phthalimidine (lb).

Scheme III.

Dihydroxy benzophenone Dimethoxy benzophenone 1 ,1 -bis(4-methoxyphenyl)-

(DHBP) (I) (DMBP) (lib) W-phenylmethanimine (IVb)

3,3-bis(4-methoxyphenyl)-2- 2-phenyl-3,3-bis(4-hydroxyphenyl) phenylisoindolin-1 -one (Vb) phthalimidine (PPPBP) (lb)

Preparation of dimethoxy benzophenone (lib) (DMBP):

[0052] Dihydroxy benzophenone (I) (20.0 grams (g), 0.0933 moles) and potassium carbonate (51.57 g, 0.3732 moles) were stirred with acetone (200 milliliters (ml)) at room temperature for 20 minutes. Dimethyl sulphate (DMS) (47.02 g, 0.3732 moles) was added to the reaction mixture over 30 minutes. Then the reaction mixture was heated to reflux temperature and maintained for 24 hours. Progress of the reaction was monitored by thin-layer

chromatography (TLC) (eluents: ethyl acetate (2 ml): hexane (8 ml)). Once dihydroxy benzophenone disappeared on the TLC plate, the resulting reaction mixture was filtered and the obtained filtrate was concentrated under vacuum. An off-white colored solid was obtained. The solid was purified with ethyl alcohol to provide 19.5 g of (lib) as a white crystalline solid was obtained. HPLC purity about 99.5%. Product confirmed by LC-MS, found M/Z: 242.0; M+2 peak: 244.2, molecular weight (Mol. wt): 242.27; ^lH NMR (400 MHz, CDC1₃): d = 3.84 (s, 6 H), 7.0 (d, 4 H), 7.71(d, 4 H)

Preparation of 1,1 -bis (4-methoxyphenyl)-N-phenylmethanimine (IVb): [0053] A flask was charged with the dimethoxy benzophenone (lib) (10 g, 0.0412 moles), AlCb, (14.66 g, 0.110 moles), and 100 ml chloroform. A solution of aniline (9.68 g, 0.104 moles) in Et₃N (33.51 g, 0.3312 moles) was then added dropwise with stirring. The resulting reaction mixture was stirred for 24 hours at 45 °C. After completion of the reaction (monitored by TLC), the mixture was treated with 4 molar (M) NaOH solution and then extracted three times with CH2CI2. The organic layer was washed with 3% aqueous

hydrochloric acid until no aniline was present in the reaction mixture, as monitored by thin layer chromatography. The combined organic extracts were dried over Na2S0₄ and concentrated under vacuum. The crude product (IVb) was analyzed by LC-MS (product about 82% and 15% starting material (lib)). This material was used for the next step without purification and the yield was calculated based on the weight of pure product percent. Product confirmed by LC- MS, found M/Z: 317; M+2 peak: 319.3, Mol. wt: 317.39.

Preparation of 3,3-bis(4-methoxyphenyl)-2-phenylisoindolin-l-one (Vb):

[0054] 1,1-Bis (4-methoxy phenyl)-N-phenyl methanimine (IVb) (5.0 g, 0.0157 moles) was dissolved in CH2CI2 (50 mL) and benzoyl chloride (2.42 g, 0.01727 moles) was added to the solution. After stirring for 2 hours, triflic acid (94.25 g, 0.628 moles) was added and stirred for 12 hours at room temperature. The product mixture was then poured over ice, and the aqueous solution was extracted with CHC1₃ (3 x 20 ml). The organic phase was washed with water and then with brine, after which it was dried with anhydrous Na2S0₄. The product was then purified by silica gel column chromatography (hexanes-chloroform). After removal of the

chromatography solvent, product (Vb) was isolated (2.5 g) as a white solid. Product confirmed by ^NMR and analyzed by LC-MS (about 99.37% purity) and HPLC purity was about 99.57%. Product confirmed by LC-MS, found M/Z: 421.0; M+2 peak: 423.5, Mol. wt.: 421.50 ^lH NMR (400 MHz, CDC1 ): d = 3.71 (s, 6 H), 6.72 (q, 4 H), 6.90 (d, 2 H), 7.12-7.28 (m, 8H), 7.48 (m, 2 H), 8.01 (s, 1 H).

Preparation of 2-phenyl-3,3-bis (4-hydroxyphenyl) phthalimidine (PPPBP) (lb):

[0055] 3,3-Bis (4-methoxy phenyl)-2-phenylisoindolin- 1 -one (Vb) (1.5 g, 0.0035 moles) was dissolved in CH2CI2 (25 mL) and BBr₃ (2.63 g, 0.0105 moles) was added to the solution at 0°C. The mixture was stirred for 10 hours at room temperature. After completion of the reaction (monitored by TLC), the product mixture was then poured over ice, and the product precipitated. The product was filtered and further purified by methanol trituration. The product (lb) was isolated (1.1 g) as a white solid. Product was confirmed by ^lH NMR and analyzed by LC-MS (about 99.62%) and HPLC. The weight percent of PPPBP purity was about 99.96%; phenolphthalein (PP) was 0.0044% (45 parts per million); the aminophenol impurity was not detectable (ND). There was also 0.0302% of an unknown impurity. Product confirmed by LC- MS, found M/Z: 393.0; M+2 peak: 395.4, Mol. wt: 393.44. ^lH NMR (400 MHz, DMSO): d = 6.67 (d, 4 H), 7.01 (t, 6H), 7.18-7.28 (m, 4 H), 7.49-7.68 (m, 2 H), 7.90 (d, 1 H), 9.54 (s, 2 H).

[0056] The methods and polymers are further illustrated by the following embodiments, which are non-limiting.

[0057] Embodiment 1: A method for the manufacture of a 2-aryl-3,3-

provide a dialkoxybenzophenone of formula (III) ^r4° ^0r4 (III); reacting the dialkoxybenzophenone of formula (III) with a primary aryl amine of formula (IV)

e presence of an acid catalyst, to provide an imine of formula (V)

(V); cyclizing the imine of formula (V) in the presence of a

cyclization catalyst and a benzoyl halide of formula (VI)

(VI), to provide a 2-aryl-3,3-bis(alkoxyaryl)phthalimidine of formula (VII)

(VII); and dealkylating the 2-aryl-3,3-bis(alkoxyaryl)phthalimidine of formula (VII) in the presence of a dealkylating agent to provide the 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I); wherein in formulas (I), (II), (III), (IV), (V), (VI), and (VII) each occurrence of R¹ is the same or different, and is a phenyl or a Ci-25 hydrocarbyl, preferably a phenyl or a C_1-6 alkyl, more preferably a C1-3 alkyl, each occurrence of R² and R³ is independently a Ci-25 hydrocarbyl or halogen, preferably a C_1-6 alkyl, more preferably a C1-3 alkyl, each occurrence of R⁴ is independently a C_1-6 hydrocarbyl, preferably a C_1-6 alkyl, more preferably a C1-3 alkyl and r, p, and q are each independently an integer of 0 to 4, more preferably 0 or 1, preferably 0.

[0058] Embodiment 2: The method of Embodiment 1, wherein the alkylating agent is dimethyl sulfate.

[0059] Embodiment 3: The method of any one or more of Embodiments 1 or 2, wherein the primary aryl amine of formula (IV) is aniline.

[0060] Embodiment 4: The method of any one or more of Embodiments 1 to 3, comprising cyclizing the imine of formula (V) without isolating the imine of formula (V).

[0061] Embodiment 5: The method of any one or more of Embodiments 1 to 4, wherein the cyclization catalyst is triflic acid.

[0062] Embodiment 6: The method of any one or more of Embodiments 1 to 5, wherein the dealkylating agent is boron tribromide.

[0063] Embodiment 7: The method of any one or more of Embodiments 1 to 6, further comprising at least one of isolating and purifying the dialkoxybenzophenone of formula (III); isolating and purifying the 2-aryl-3,3-bis(alkoxyaryl)phthalimidine of formula (VII).

[0064] Embodiment 8: The method of any one or more of Embodiments 1 to 7, further comprising precipitating the 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I) to provide an as- synthesized 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I), which comprises zero to 100 parts per million of an aminophenol, or zero to 50 parts per million of an

aminophenol, or zero to 20 parts per million of an aminophenol, or zero to 5 parts per million of an aminophenol; or zero to 500 parts per million of a phenolphthalein, or zero to 50 parts per million of a phenolphthalein. [0065] Embodiment 9: The method of any one or more of Embodiments 1 to 8, further comprising purifying the 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I).

[0066] Embodiment 10: The method of Embodiment 9, wherein the purifying comprises triturating the as- synthesized 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I) with methanol to provide a purified 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I).

[0067] Embodiment 11: The method of any one or more of Embodiments 9 or 10, wherein the purified 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I) comprises zero to 50 parts per million of an aminophenol, or zero to 20 parts per million of an aminophenol, or zero to 5 parts per million of an aminophenol; or zero to 500 parts per million of a

phenolphthalein, or zero to 50 parts per million of a phenolphthalein.

[0068] Embodiment 12: The method of any one or more of Embodiments 9 to 11, wherein the purified 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I) comprises less than 0.1% by weight of organic impurities other than an aminophenol or phenolphthalein; less than 3 ppm of iron; less than 50 ppm of methanol; and an APHA color of less than 40.

[0069] Embodiment 13: The method of any one or more of Embodiments 1 to 12, wherein the 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I) is of formula (la)

(la), wherein R¹ is a phenyl or a C1-3 alkyl, R³ is a C1-3 alkyl, q is 0 or 1, and r is 0 or 1; preferably wherein each of q and r is zero, and the 2-aryl-3,3- bis(hydroxyaryl)phthalimidine of formula (I) is 2-phenyl-3,3-bis(4-hydroxyphenyl)-2- phthalimidine.

[0070] Embodiment 14: The method of any one or more of Embodiments 1 to 13, wherein the benzophenone of formula (II) is dihydroxybenzophenone, the primary aryl amine is aniline, the alkylating agent is dimethyl sulfate, the cyclization catalyst is triflic acid, the dealkylating agent is boron Iribromide, the benzoyl halide is benzoyl chloride, and the acid catalyst is hydrochloric acid.

[0071] Embodiment 15: A 2-aryl-3,3-bis(4-hydroxyaryl) phthalimidine composition,

comprising an as- synthesized phthalimidine of formula (I)

wherein each occurrence of R¹ is the same or different, and is a phenyl or a Ci-25 hydrocarbyl, preferably a phenyl or a C_1-6 alkyl, more preferably a C1-3 alkyl, each occurrence of R² and R³ is independently a Ci-25 hydrocarbyl or halogen, preferably a C_1-6 alkyl, more preferably a C1-3 alkyl, and r, p, and q are each independently 0 to 4, more preferably 0 or 1, preferably 0; zero to 100 parts per million of an aminophenol, or zero to 50 parts per million of an aminophenol, or zero to 20 parts per million of an aminophenol, or zero to 5 parts per million of an aminophenol; or zero to 500 parts per million of a phenolphthalein, or zero to 50 parts per million of a phenolphthalein .

[0072] Embodiment 16: A method for the manufacture of a polycarbonate, comprising manufacturing the 2-aryl-3,3-bis(4-hydroxyaryl) phthalimidine of formula (I) in accordance with any one or more of Embodiments 1 to 14; and polymerizing the 2-aryl-3,3-bis(4-hydroxyaryl) phthalimidine of formula (I) in the presence of a carbonate source to form a polycarbonate.

[0073] The term "hydrocarbyl" is defined herein as a monovalent moiety formed by removing a hydrogen atom from a hydrocarbon. Representative hydrocarbyls are alkyl groups having 1 to 25 carbon atoms, such as, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, undecyl, decyl, dodecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, and the isomeric forms thereof; aryl groups having 6 to 25 carbon atoms, such as ring- substituted and ring-unsubstituted forms of phenyl, tolyl, xylyl, naphthyl, biphenyl, tetraphenyl, and the like; arylalkyl groups having 7 to 25 carbon atoms, such as ring-substituted and ring- unsubstituted forms of benzyl, phenethyl, phenpropyl, phenbutyl, naphthoctyl, and the like; and cycloalkyl groups, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like. The term "aryl" as used herein refers to various forms of aryl groups that have been described hereinabove for the "hydrocarbyl" group. "Alkyl" refers to a straight or branched chain, saturated monovalent hydrocarbon group. Unless otherwise indicated, each of the foregoing groups can be unsubstituted or substituted, provided that the substitution does not significantly adversely affect synthesis, stability, or use of the compound. The term

"substituted" as used herein means that at least one hydrogen on the designated atom or group is replaced with another group, provided that the designated atom's normal valence is not exceeded. When the substituent is oxo (i.e., =0), then two hydrogens on the atom are replaced. Combinations of substituents and/or variables are permissible provided that the substitutions do not significantly adversely affect synthesis or use of the compound. Exemplary groups that can be present on a "substituted" position include, but are not limited to, cyano; hydroxyl; nitro; azido; alkanoyl (such as a C2-6 alkanoyl group such as acyl); carboxamido; C_1-6 or C1-3 alkyl, cycloalkyl, alkenyl, and alkynyl (including groups having at least one unsaturated linkages and from 2 to 8, or 2 to 6 carbon atoms); C_1-6 or C1-3 alkoxys; C₆-io aryloxy such as phenoxy; C_1-6 alkylthio; C_1-6 or C1-3 alkylsulfinyl; C_1-6 or C1-3 alkylsulfonyl; aminodi(Ci-6 or Ci-₃)alkyl; C₆-i2 aryl having at least one aromatic rings (e.g., phenyl, biphenyl, naphthyl, or the like, each ring either substituted or unsubstituted aromatic); C7-19 arylalkyl having 1 to 3 separate or fused rings and from 6 to 18 ring carbon atoms; or arylalkoxy having 1 to 3 separate or fused rings and from 6 to 18 ring carbon atoms, with benzyloxy being an exemplary arylalkoxy.

[0074] The singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. "Or" means "and/or." The modifier "about" used in connection with a quantity is inclusive of the stated value and has the meaning dictated by the context (e.g., includes the degree of error associated with measurement of the particular quantity).

[0075] The endpoints of all ranges directed to the same component or property are inclusive and independently combinable (e.g., ranges of "less than or equal to 25 wt%, or 5 wt% to 20 wt%," is inclusive of the endpoints and all intermediate values of the ranges of "5 wt% to 25 wt%," etc.). Disclosure of a narrower range or more specific group in addition to a broader range is not a disclaimer of the broader range or larger group. "Optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event occurs and instances where it does not. 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 invention belongs. A

"combination" is inclusive of blends, mixtures, alloys, reaction products, and the like.

[0076] All publications, patents, and patent applications cited in this specification are herein incorporated by reference, and for any and all purposes, as if each individual publication, patent or patent application were specifically and individually indicated to be incorporated by reference. In the case of inconsistencies, the present disclosure will prevail.

[0077] While typical embodiments have been set forth for the purpose of illustration, the foregoing descriptions should not be deemed to be a limitation on the scope herein.

Accordingly, various modifications, adaptations, and alternatives can occur to one skilled in the art without departing from the spirit and scope herein.

Claims

CLAIMS What is claimed is:

1. A method for the manufacture of a 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I)

the method comprising:

O-alkylating a benzophenone of formula (II)

to provide a dialkoxybenzophenone of formula (III)

reacting the dialkoxybenzophenone of formula (III) with a primary aryl amine of formula

(IV)

in the presence of an acid catalyst, to provide an imine of formula (V)

;

cyclizing the imine of formula (V) in the presence of a cyclization catalyst and a benzoyl halide of formula (VI)

to provide a 2-aryl-3,3-bis(alkoxyaryl)phthalimidine of formula (VII)

(VII); and

dealkylating the 2-aryl-3,3-bis(alkoxyaryl)phthalimidine of formula (VII) in the presence of a dealkylating agent to provide the 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I); wherein in formulas (I), (II), (III), (IV), (V), (VI), and (VII)

each occurrence of R¹ is the same or different, and is a phenyl or a Ci-25 hydrocarbyl, preferably a phenyl or a C_1-6 alkyl, more preferably a C1-3 alkyl,

each occurrence of R² and R³ is independently a Ci-25 hydrocarbyl or halogen, preferably a C_1-6 alkyl, more preferably a C1-3 alkyl,

each occurrence of R⁴ is independently a C_1-6 hydrocarbyl, preferably a C_1-6 alkyl, more preferably a C1-3 alkyl and

r, p, and q are each independently an integer of 0 to 4, more preferably 0 or 1, preferably 0.

2. The method of claim 1, wherein the alkylating agent is dimethyl sulfate.

3. The method of any one or more of claims 1 or 2, wherein the primary aryl amine of formula (IV) is aniline.

4. The method of any one or more of the preceding claims, comprising cyclizing the imine of formula (V) without isolating the imine of formula (V).

5. The method of any one or more of the preceding claims, wherein the cyclization catalyst is triflic acid.

6. The method of any one or more of the preceding claims, wherein the dealkylating agent is boron tribromide.

7. The method of any one or more of the preceding claims, further comprising at least one of

isolating and purifying the dialkoxybenzophenone of formula (III);

isolating and purifying the 2-aryl-3,3-bis(alkoxyaryl)phthalimidine of formula (VII).

8. The method of any one or more of the preceding claims, further comprising precipitating the 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I) to provide an as- synthesized 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I), which comprises

zero to 100 parts per million of an aminophenol, or zero to 50 parts per million of an aminophenol, or zero to 20 parts per million of an aminophenol, or zero to 5 parts per million of an aminophenol; or

zero to 500 parts per million of a phenolphthalein, or zero to 50 parts per million of a phenolphthalein .

9. The method of any one or more of any one or more of the preceding claims, further comprising purifying the 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I).

10. The method of claim 9, wherein the purifying comprises triturating the as- synthesized 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I) with methanol to provide a purified 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I).

11. The method of claim 9 or 10, wherein the purified 2-aryl-3,3- bis(hydroxyaryl)phthalimidine of formula (I) comprises

zero to 50 parts per million of an aminophenol, or zero to 20 parts per million of an aminophenol, or zero to 5 parts per million of an aminophenol; or

zero to 500 parts per million of a phenolphthalein, or zero to 50 parts per million of a phenolphthalein .

12. The method of any one or more of claims 9 to 11, wherein the purified 2-aryl-3,3- bis(hydroxyaryl)phthalimidine of formula (I) has one or more, preferably all of less than 0.1% by weight of organic impurities other than an aminophenol or phenolphthalein ;

less than 3 ppm of iron;

less than 50 ppm of methanol; or

an APHA color of less than 40.

13. The method of any one or more of the preceding claims, wherein

the 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I) is of formula (la)

wherein R¹ is a phenyl or a C1-3 alkyl, R³ is a C1-3 alkyl, q is 0 or 1, and r is 0 or 1;

preferably wherein each of q and r is zero, and the 2-aryl-3,3- bis(hydroxyaryl)phthalimidine of formula (I) is 2-phenyl-3,3-bis(4-hydroxyphenyl)-2- phthalimidine.

14. The method of any one or more of the preceding claims, wherein the

benzophenone of formula (II) is dihydroxybenzophenone, the primary aryl amine is aniline, the alkylating agent is dimethyl sulfate, the cyclization catalyst is triflic acid, the dealkylating agent is boron tribromide, the benzoyl halide is benzoyl chloride, and the acid catalyst is hydrochloric acid.

A 2-aryl-3,3-bis(4-hydroxyaryl) phthalimidine composition, comprising synthesized phthalimidine of formula (I)

wherein each occurrence of R¹ is the same or different, and is a phenyl or a Ci-25 hydrocarbyl, preferably a phenyl or a C_1-6 alkyl, more preferably a C1-3 alkyl,

each occurrence of R² and R³ is independently a Ci-25 hydrocarbyl or halogen,

preferably a C_1-6 alkyl, more preferably a C1-3 alkyl, and

r, p, and q are each independently 0 to 4, more preferably 0 or 1, preferably 0;

zero to 100 parts per million of an aminophenol, or zero to 50 parts per million of an aminophenol, or zero to 20 parts per million of an aminophenol, or zero to 5 parts per million of an aminophenol; or

zero to 500 parts per million of a phenolphthalein, or zero to 50 parts per million of a phenolphthalein.

16. A method for the manufacture of a polycarbonate, comprising

manufacturing the 2-aryl-3,3-bis(4-hydroxyaryl) phthalimidine of formula (I) in accordance with any one or more of claims 1 to 14; and

polymerizing the 2-aryl-3,3-bis(4-hydroxyaryl) phthalimidine of formula (I) in the presence of a carbonate source to form a polycarbonate.