WO2017182983A1 - Procédés de production de 2-aryl-3,3-bis(hydroxyaryl)phtalimidines - Google Patents

Procédés de production de 2-aryl-3,3-bis(hydroxyaryl)phtalimidines Download PDF

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WO2017182983A1
WO2017182983A1 PCT/IB2017/052287 IB2017052287W WO2017182983A1 WO 2017182983 A1 WO2017182983 A1 WO 2017182983A1 IB 2017052287 W IB2017052287 W IB 2017052287W WO 2017182983 A1 WO2017182983 A1 WO 2017182983A1
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formula
bis
phthalimidine
aryl
alkyl
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Shivakumar KONDA
Shubashree Swaminathan
Gaurav Mediratta
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SABIC Global Technologies BV
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C07D209/46—Iso-indoles; Hydrogenated iso-indoles with an oxygen atom in position 1

Definitions

  • each occurrence of R 1 is independently 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 R 2 and R 3 is independently a Ci-25 hydrocarbyl or halogen, preferably a C 1-6 alkyl, more preferably a Ci-3 alkyl
  • r, p, and q are each independently an integer of 0 to 4, more preferably 0 or 1, preferably 0 is provided.
  • a 2-aryl-3,3-bis(4-hydroxyaryl) phthalimidine composition comprising an as- synthesized phthalimidine of formula (I)
  • each occurrence of R is independently a phenyl or a Ci-25 hydrocarbyl, preferably a phenyl or C 1-6 alkyl, more preferably a C1-3 alkyl
  • each occurrence of R 2 and R 3 is independently a Ci-25 hydrocarbyl or halogen, preferably a C 1-6 alkyl, more preferably a C1-3 alkyl
  • 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, or zero to 50 parts per million of the precursor phenolphthalein of formula (II) is provided.
  • a method for the manufacture of a polycarbonate comprising manufacturing the 2- aryl-3,3-bis(4-hydroxyaryl) phthalimidine of formula (I) by the described method;
  • the dihydrophenolphthalein is conveniently obtained by reduction of a precursor phenolphthalein that is commonly used in the manufacture of phthalimidines. Formation of the dihydrophenolphthalein is followed by activation, amide formation, and oxidation to provide the product phthalimidine.
  • no detectable aminophenol is present in the product, and 50 ppm or less of the starting phenolphthalein is formed.
  • the method can thus advantageously reduce or eliminate the need for a separate purification step to remove the aminophenol.
  • 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.
  • 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.
  • each occurrence of R is independently a phenyl or a Ci-25 hydrocarbyl, preferably a phenyl or C 1-6 alkyl, more preferably a C1-3 alkyl
  • each occurrence of R 2 and R 3 is independently a Ci-25 hydrocarbyl or halogen, preferably a C 1-6 alkyl, more preferably a C1-3 alkyl
  • r, p, and q are each independently an integer of 0 to 4, more preferably 0 or 1, preferably 0.
  • R 1 is a C1-3 alkyl group
  • R 2 is hydrogen, a C1-3 alkyl group, or a halogen
  • q is 0.
  • a preferred 2-aryl-3,3-bis(4-hydroxyaryl)phthalimidine is of formula (la)
  • R 1 is a C1-3 alkyl
  • R 3 is a C1-3 alkyl
  • q is 0 or 1
  • r is 0 or 1; preferably wherein each of p and r is zero.
  • a preferred 2-aryl-3,3-bis(4-hydroxyaryl)phthalimidine is 2-phenyl- 3,3-bis(4- hydroxyphenyl)phthalimidine .
  • reaction Scheme (I) shows generally a method for the manufacture of 2-aryl-3,3-bis(4-hydroxaryl)phthalimidine (I).
  • each occurrence of R is independently a phenyl or a Ci-25 hydrocarbyl, preferably a phenyl or a Ci-6 alkyl; each occurrence of R 2 and R 3 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.
  • each occurrence of R 1 is independently a Ci-6 alkyl; each occurrence of R 2 and R 3 is independently a phenyl or Ci-6 alkyl, more preferably a C1-3 alkyl, and r, p, and q are each independently 0 or 1, preferably 0.
  • the activated compound phenolphthalein precursor (IV) can be isolated, or can be used in the method as prepared without separate isolation.
  • the following reaction Scheme (II) shows generally a method for the manufacture a preferred 2-aryl-3,3-bis(4-hydroxyphenyl)phthalimidine (la). cheme II
  • each occurrence of R 1 is independently a phenyl or a Ci-25 hydrocarbyl, preferably a phenyl or Ci-6 alkyl; each occurrence of R 3 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 0 to 4, more preferably 0 or 1, preferably 0.
  • each occurrence of R 1 is independently a C 1-6 alkyl; each occurrence of R 2 and R 3 is independently a phenyl or C 1-6 alkyl, more preferably a C1-3 alkyl, and r, p, and q are each independently and integer of 0 or 1, preferably 0.
  • the reaction proceeds by hydrolysis of a phenolphthalein precursor, followed by amide formation and cyclization.
  • the reaction of the dihydrophenolphthalein of formula (III) to form an activated phenolphthalein precursor of formula (IV) can proceed by an esterification reaction in the presence of an activating agent.
  • activating agents include N-hydroxysuccinimide, N- hydroxybenzotriazole (HOBt), N-hydroxy-5-norbornene-endo-2,3-dicarboximide (HONB), 4- dimethylaminopyridine (DMAP), and the sulfo-derivative of N-hydroxysuccinimide.
  • Exemplary coupling agents include water soluble carbodiimides, including l-ethyl-2-(3- dimethylaminopropyl)carbodiimide, or carbodiimides soluble in an organic solvent, such as dicyclohexylcarbodiimide, diisopropylcarbodiimide, or carbonyldiimidazole.
  • carbodiimides e.g., diethylcarbodiimides, N,N'-carbonyl-di(2-methylimidazole), benzotriazole, 1- hydroxybenzotriazole (HOBt)-6-sulfonamidomethyl resin ⁇ HC1, hydroxy-3,4-dihydro-4-oxo- l,2,3- benzotriazine (HOOBt), l-hydroxy-7-aza- lH-benzotriazole (HO At), ethyl 2-cyano-2- (hydroximino)acetate (Oxyma Pure Novabiochem®), benzotriazol- l-yloxy-tris(dimethylamino)- phosphonium hexafluorophosphate (BOP), benzotriazol-l-yloxy-tripyrrolidino- phosphoniumhexafluorophosphate (PyBOP), bromo-tripyrrolidino-phosphonium hex
  • Tetramethylfluoroformamidinium hexafluorophosphate THFH
  • pentamethyleneketene-N-cyclohexylimine diphenylketene-N-cyclohexylimine
  • alkoxyacetylenes 1-alkoxy- l-chloroethylenes
  • tetraalkyl phosphites isopropyl polyphosphate, phosphorus oxychloride, phosphorus trichloride, thionyl chloride, oxalyl chloride, and triphenyl phosphines can also be used as coupling agents.
  • the reducing agent can be zinc, or other reducing agents such as alkali or alkaline earth and transition metals (Li, K, Ca, Na, Mg, Mn, Fe, Ni etc.).
  • the base can be sodium hydroxide, alkali metal and alkaline earth hydroxides, an amine, or other base.
  • the reaction can proceed under atmospheric conditions or an inert atmosphere.
  • the reaction can proceed at any useful temperature, for example at a temperature of 25 to 90°C, preferably 25 to 45°C, more preferably 25 to 30°C.
  • the activating agent can be present in a concentration from 0.02 moles to 0.08 moles, preferably 0.04 moles to 0.06 moles.
  • the coupling agent can be present in a concentration of 0.02 moles to 0.1 moles, preferably 0.04 moles to 0.07 moles, more preferably 0.034 moles to 0.036 moles.
  • the reaction of the activated phenolphthalein of formula (IV) to form a benzamide phenolphthalein of formula (VI) can proceed by an amide formation reaction in the presence of the primary aryl amine (VI).
  • exemplary primary aryl amines include aniline.
  • the primary aryl amine is present at a concentration of 3.0-5.0 molar equivalents of the precursor phenolphthalein of formula (II).
  • the benzamide phenolphthalein of formula (VI) can be oxidized, to form the 2-aryl- 3,3-bis(hydroxyaryl)phthalimidine of formula (I).
  • exemplary oxidizing agents include 2,3- dichloro-5,6-dicyanobenzoquinone (DDQ), p-chloranil, other dehydrogenating agents known in literature such as the transition metal oxides/chlorides, e.g., ferric chloride, silver oxide, vanadium oxide, and others known in the art.
  • the oxidizing agent can be present at a concentration of 0.5 moles to 1 moles, preferably 0.5 to 0.75 moles.
  • the as- synthesized 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I) comprises zero to 100 parts per million of an aminophenol.
  • 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
  • the as- synthesized 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I) can comprise zero to 500 parts per million, or zero to 50 parts per million of the precursor
  • the as- synthesized 2-aryl-3,3- bis(hydroxyaryl)phthalimidine of formula (I) can comprise less than 500 parts per million, or less than 50 parts per million of the precursor phenolphthalein of formula (II).
  • the purified 2-hydrocarbyl-3,3-bis(hydroxyaryl)phthalimidine of formula (I) can comprise zero to 50 parts per million of an aminophenol, preferably zero to 5 parts per million of an aminophenol; or zero to 500 parts per million, preferably from zero to 50 parts per million of the precursor phenolphthalein of formula (II).
  • the purified 2-hydrocarbyl-3,3-bis(hydroxyaryl)phthalimidine of formula (I) can comprise less than 50 parts per million of an aminophenol, preferably less than 5 parts per million of an aminophenol; or less than 500 parts per million, preferably less than 50 parts per million of the precursor
  • 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
  • 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.
  • PPPBP 2-phenyl- 3,3-bis(4-hydroxyphenyl)phthalimidine
  • 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.
  • 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.
  • 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.
  • polycarbonates having low color properties are synthesized, wherein the polycarbonates include structural units of formula (Va):
  • 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)
  • each of A 1 and A 2 is a monocyclic divalent aromatic group and Y 1 is a single bond or a bridging group having one or more atoms that separate A 1 from A 2 .
  • one atom separates A 1 from A 2 .
  • each R 1 can be derived from a dihydroxy aromatic compound of formula (VII):
  • 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 C 6 arylene group are disposed ortho, meta, or para (specifically para) to each other on the C 6 arylene group.
  • the bridging group X a is -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 C 6 arylene groups connected thereto are each connected to a common alkylidene carbon or to different carbons of the CMS organic group.
  • p and q is each 1
  • R a and R b are each a C1-3 alkyl group, specifically methyl, disposed meta to the hydroxy group on each arylene 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.
  • X A is a CMS alkylene group, a C3-18 cycloalkylene group, a fused C 6 -i8 cycloalkylene group, or a group of the formula -E ⁇ -W-B 2 - wherein B 1 and B 2 are the same or different Ci-6 alkylene group and W is a C3-12 cycloalkylidene group or a C 6 -i6 arylene group.
  • each R h is independently a halogen atom, a Ci-10 hydrocarbyl such as a Ci-10 alkyl group, a halogen-substituted Ci-10 alkyl group, a C 6 -io aryl group, or a halogen-substituted C6-10 aryl group, and n is 0 to 4.
  • the halogen is usually bromine.
  • 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)-l- 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
  • 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
  • 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).
  • BPA 2,2-bisphenol A
  • BPA 2,2-bis(4-hydroxyphenyl) but
  • 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).
  • Exemplary carbonic acid diesters useful in the formation of the polycarbonates in a melt transesterification process are of formula (IX):
  • each Z is independently an unsubstituted or substituted Ci-12 alkyl radical, or an
  • 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.
  • 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,
  • BMSC 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.
  • BMSC is used in the melt transesterification process.
  • 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.
  • 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,
  • the catalyst is tetrabutylphosphonium acetate.
  • 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.
  • the catalyst can be a mixture of sodium hydroxide and tetrabutylphosphonium acetate.
  • the catalyst is a mixture of sodium hydroxide and tetramethylammonium hydroxide.
  • 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 NaH 2 P03, NaH 2 P0 4 , Na 2 H 2 P0 3 , KH 2 P0 4 , CsH 2 P0 4 , Cs 2 H 2 P0 4 , or a mixture thereof.
  • 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 NaH 2 P0 4 and sodium hydroxide as the transesterification catalyst.
  • any of the catalysts disclosed above can be used as combinations of two or more substances.
  • the catalyst can be added in a variety of forms.
  • 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.
  • 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.
  • 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.
  • the polycarbonates can be prepared by an interfacial polymerization process.
  • 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.
  • a catalyst such as triethylamine or a phase transfer catalyst
  • 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.
  • an interfacial polymerization reaction to form carbonate linkages uses phosgene as a carbonate precursor, and is referred to as a phosgenation reaction.
  • Exemplary phase transfer catalysts include, for example, [CH 3 (CH 2 ) 3 ] 4 NX, [CH 3 (CH 2 ) 3 ] 4 PX, [CH 3 (CH 2 ) 5 ] 4 NX, [CH 3 (CH 2 ) 6 ] 4 NX, [CH 3 (CH 2 ) 4 ] 4 NX, CH 3 [CH 3 (CH 2 ) 3 ] 3 NX, and CH 3 [CH 3 (CH 2 ) 2 ] 3 NX, wherein X is C1-, Br-, a C 1-8 alkoxy group or a C 6 -is 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.
  • Branched polycarbonate blocks can be prepared by adding a branching agent during polymerization.
  • a chain stopper also referred to as a capping agent
  • 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.
  • 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.
  • 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.
  • one or more continuous reactors such as for example, a tubular reactor can be used.
  • 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.
  • phosgene at least one solvent
  • aqueous base at least one bisphenol
  • aqueous base at least one bisphenol
  • aqueous base e.g., aqueous base
  • catalysts example, a trialkylamine
  • 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
  • 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.
  • Mw weight average molecular weight
  • Tg glass transition temperature
  • Mn number average molecular weights of the homopolycarbonate and copolycarbonates can be from about 1,500 to about 75,000 Daltons.
  • 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
  • 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.
  • 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.
  • 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.
  • 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 (TSAN)), or a combination comprising at least one or more of the foregoing.
  • filler e.g., a particulate polytetrafluoroethylene (PTFE), glass, carbon, mineral, or metal
  • reinforcing agent e.g., glass fibers
  • the additives are used in the amounts generally known to be effective.
  • 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.
  • reaction Scheme (III) shows generally a method for the manufacture of 2-phenyl-3,3-bis(4-hydroxyphenyl)-2-phthalimidine (lb).
  • Embodiment 1 A method for the manufacture of a 2-aryl-3,3- bis(hydroxyaryl)phthalimidine of formula (I)
  • each occurrence of R 1 is independently a phenyl or a Ci-25 hydrocarbyl, preferably a phenyl or a Ci- 6 alkyl, more preferably a C1-3 alkyl, each occurrence of R 2 and R 3 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.
  • Embodiment 2 The method of Embodiment 1, wherein the reducing agent is zinc.
  • Embodiment 3 The method of any one of more of Embodiments 1 or 2, further comprising isolating, washing, and then acidifying the product of the reducing to provide the dihydrophenolphthalein of formula (III).
  • Embodiment 4 The method of any one of more of Embodiments 1 to 3, wherein the activating agent is N-hydroxysuccinimide.
  • Embodiment 5 The method of any one of more of Embodiments 1 to 4, wherein the coupling agent is dicyclohexylcarbodiimide.
  • Embodiment 6 The method of any one of more of Embodiments 1 to 5, wherein the primary aryl amine is aniline.
  • Embodiment 7 The method of any one of more of Embodiments 1 to 6, further comprising isolating and washing the activated phenolphthalein precursor of formula (IV) before the reacting with the primary aryl amine of formula (V).
  • Embodiment 8 The method of any one of more of Embodiments 1 to 7, wherein the reacting with the primary aryl amine of formula (V) is at 25 to 50°C, preferably 30 to 40°C.
  • Embodiment 9 The method of any one of more of Embodiments 1 to 8, wherein the oxidizing agent is dichlorodicyanoquinone.
  • Embodiment 10 The method of any one of more of Embodiments 1 to 9, further comprising isolating and washing the product of the oxidizing to obtain 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, or zero to 50 parts per million of the precursor phenolphthalein of formula (II).
  • 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, or zero to 50 parts per million of the precursor phenolphthalein of formula (II).
  • Embodiment 11 The method of any one of more of Embodiments 1 to 10, further comprising purifying the 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I).
  • Embodiment 12 The method of any one of more of Embodiments 1 to 11, wherein the purifying comprises dissolving the 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I) in an aqueous base to form a solution, and extracting the solution with an organic solvent; contacting the extracted aqueous solution with charcoal, and removing the charcoal to provide a decolorized solution; and neutralizing the decolorized aqueous solution to provide a precipitate comprising the 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I); and optionally, triturating the precipitate to provide the purified the 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I).
  • Embodiment 13 The method of any one of more of Embodiments 1 to 12, wherein the purified 2-hydrocarbyl-3,3-bis(hydroxyaryl)phthalimidine of formula (I) comprises zero to 50 parts per million of an aminophenol, preferably zero to 5 parts per million of an aminophenol; or zero to 500 parts per million, preferably from zero to 50 parts per million of the precursor phenolphthalein of formula (II).
  • Embodiment 14 The method of Embodiments 11 to 13, wherein the purified 2- hydrocarbyl-3,3-bis(hydroxyaryl)phthalimidine of formula (I) comprises less than 0.1% by weight of impurities other than an aminophenol or precursor phenolphthalein of formula (II); less than 3 ppm of iron; less than 50 ppm of methanol; and an APHA color of less than 40.
  • Embodiment 15 The method of any one of more of Embodiments 1 to 14, wherein the 2-aryl-3,3-bis(hydroxyaryl)phthalimidine of formula (I) is of formula (la)
  • Embodiment 16 The method of any one or more of Embodiments 1 to 15, wherein
  • the precursor phenolphthalein is , wherein p is 0, each occurrence is a Ci-3 alkyl, and q is 1, the reducing agent is zinc, the activating agent is N-hydroxysuccinimide, the coupling agent is dicyclohexylcarbodiimide, the primary aryl amine is aniline, the oxidizing agent is dichlorodicyanoquinone.
  • Embodiment 17 A 2-aryl-3,3-bis(4-hydroxyaryl) phthalimidine composition, comprising an as- synthesized phthalimidine of formula (I) (I), wherein each occurrence of R 1 is independently 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 R 2 and R 3 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, or zero to 50 parts per million of the precursor
  • each occurrence of R 1 is independently a phenyl or a Ci-25 hydrocarbyl, preferably a phenyl or a C 1-6 alkyl, more preferably a Ci-3 alkyl
  • each occurrence of R 2 and R 3 is independently a Ci-25 hydrocarbyl or halogen, preferably a C 1-6 alkyl, more preferably a C1-3 alkyl
  • r, p, and q are each independently 0 to 4, more preferably 0 or 1, preferably 0.
  • Embodiment 18 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 16; 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.
  • 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
  • aryl 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.
  • substituents and/or variables are permissible provided that the substitutions do not significantly adversely affect synthesis or use of the compound.
  • substituents and/or variables 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; C 6 -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; Ce-n aryl having at least one aromatic rings (e.g., phenyl, biphenyl, naphthyl, or the like, each ring either substituted or unsubstituted aromatic); C-7-19 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.

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Abstract

L'invention concerne une voie de synthèse de production d'une 2-phényl-3,3-bis(4-hydroxyphényl)phtalimidine, en utilisant un intermédiaire de dihydrophénolphtaléine. La dihydrophénolphtaléine peut être obtenue par réduction d'un précurseur de phénolphtaléine qui est couramment utilisé dans la fabrication des phtalimidines. La formation de la dihydrophénolphtaléine est suivie d'une activation, de la formation d'un amide et d'une oxydation pour obtenir le produit phtalimidine.
PCT/IB2017/052287 2016-04-22 2017-04-20 Procédés de production de 2-aryl-3,3-bis(hydroxyaryl)phtalimidines Ceased WO2017182983A1 (fr)

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US12291529B2 (en) 2023-02-16 2025-05-06 Gasherbrum Bio, Inc. Heterocyclic GLP-1 agonists
US12595264B2 (en) 2020-09-10 2026-04-07 Gasherbrum Bio, Inc. Heterocyclic GLP-1 agonists

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US11492365B2 (en) 2020-02-07 2022-11-08 Gasherbrum Bio, Inc. Heterocyclic GLP-1 agonists
US11926643B2 (en) 2020-02-07 2024-03-12 Gasherbrum Bio, Inc. Heterocyclic GLP-1 agonists
US12595264B2 (en) 2020-09-10 2026-04-07 Gasherbrum Bio, Inc. Heterocyclic GLP-1 agonists
US12291529B2 (en) 2023-02-16 2025-05-06 Gasherbrum Bio, Inc. Heterocyclic GLP-1 agonists

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