EP2705016A1 - Bisphénol a de grande pureté et matériaux de type polycarbonate préparés à partir de celui-ci - Google Patents

Bisphénol a de grande pureté et matériaux de type polycarbonate préparés à partir de celui-ci

Info

Publication number
EP2705016A1
EP2705016A1 EP12722886.4A EP12722886A EP2705016A1 EP 2705016 A1 EP2705016 A1 EP 2705016A1 EP 12722886 A EP12722886 A EP 12722886A EP 2705016 A1 EP2705016 A1 EP 2705016A1
Authority
EP
European Patent Office
Prior art keywords
polycarbonate
less
bpa
bisphenol
astm
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP12722886.4A
Other languages
German (de)
English (en)
Inventor
Johannes DE BROUWER
Paulus Johannes Maria EIJSBOUTS
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SABIC Global Technologies BV
Original Assignee
SABIC Innovative Plastics IP BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US13/099,032 external-priority patent/US20120283485A1/en
Priority claimed from US13/099,026 external-priority patent/US8735634B2/en
Application filed by SABIC Innovative Plastics IP BV filed Critical SABIC Innovative Plastics IP BV
Publication of EP2705016A1 publication Critical patent/EP2705016A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
    • C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol
    • C07C39/16—Bis-(hydroxyphenyl) alkanes; Tris-(hydroxyphenyl)alkanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/18—Block or graft polymers
    • C08G64/186—Block or graft polymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
    • C08G77/448—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences containing polycarbonate sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

  • the present disclosure relates to catalyst systems, and specifically to promoter ion exchange resin catalyst systems.
  • reaction promoters When used as part of the catalyst system, reaction promoters can improve reaction rate and selectivity. In the case of the condensation of phenol and ketone to form bisphenol-A (BPA), reaction promoters can improve selectivity for the desired para-para BPA isomer.
  • BPA bisphenol-A
  • Reaction promoters can be used as bulk promoters, where the promoter is present as an unattached molecule in the reaction medium, or as an attached promoter, where the promoter is attached to a sulphonic acidic portion of the catalyst system.
  • this disclosure in one aspect, relates to catalyst systems, and specifically to promoter ion exchange resin catalyst systems.
  • the present disclosure provides a process for a chemical condensation reaction, the process comprising contacting at least two chemical reagents with an attached promoter ion exchange resin catalyst system to produce an effluent, and then subjecting the effluent to a solvent crystallization step.
  • the present disclosure provides a process comprising contacting at least two chemical reagents with an attached promoter ion exchange resin catalyst system to produce an effluent, and then subjecting the effluent to a solvent crystallization step, wherein the attached promoter ion exchange resin catalyst system comprises cross-linked, sulfonated ion exchange resin having sulfonic groups and a degree of cross-linking of from 1 % to 4 %.
  • the present disclosure provides a process comprising contacting at least two chemical reagents with an attached promoter ion exchange resin catalyst system, wherein the attached promoter ion exchange resin catalyst system comprises a dimethyl thiazolidine promoter.
  • the present disclosure provides a process comprising contacting at least two chemical reagents with an attached promoter ion exchange resin catalyst system, wherein the attached promoter ion exchange resin catalyst system comprises a promoter that is ionically bound to from about 18 % to about 25 % of sulfonic acid groups present on the ion exchange resin.
  • the present disclosure provides a process wherein prior to a solvent crystallization step, a reactor effluent is subjected to at least one of a separate ion exchange resin bed, a water removal step, a phenol recovery step, or a combination thereof.
  • the present disclosure provides a bisphenol A reaction product having no or substantially no inorganic and/or sulfur impurities.
  • the present disclosure provides a bisphenol- A monomer having an organic purity of at least about 99.5 wt.% and a sulfur concentration of less than about 5 ppm, wherein when formed into a polycarbonate resin and molded into a 2.5 mm plaque, exhibits a color (YI) of less than about 1.5.
  • the present disclosure provides a bisphenol-A monomer, having a sulfur concentration of less than about 2 ppm.
  • the present disclosure provides a bisphenol-A monomer, wherein when formed into a polycarbonate resin and molded into a 2.5 mm plaque, exhibits a color (YI) of less than about 1.3.
  • the present disclosure provides a bisphenol-A monomer, wherein when formed into a polycarbonate resin and molded into a 2.5 mm plaque, exhibits a color (YI) of less than about 10 after heat aging for 2,000 hours at about 130 °C.
  • the present disclosure provides a bisphenol-A monomer, wherein when formed into a polycarbonate resin and molded into a 2.5 mm plaque, exhibits a color (YI) of less than about 7 after heat aging for 2,000 hours at about 130 °C.
  • the present disclosure provides a bisphenol-A prepared by contacting at least two chemical reagents with an attached promoter ion exchange resin catalyst system to produce an effluent, and then subjecting the effluent to a solvent crystallization step, having a purity level suitable for use in the manufacture of polycarbonate for optical applications and requiring high transmission and low color.
  • the present disclosure provides a polycarbonate prepared from the bisphenol-A described herein.
  • FIG. 1 illustrates the yellowness index in a plastic 2.5mm color chip directly after molding as a function of monomer synthesis catalyst & promoter system.
  • FIG. 2 illustrates the yellowness index in a plastic 2.5mm color chip after 2,000 hrs of heat aging at 130 °C as a function of monomer synthesis catalyst & promoter system.
  • FIG. 3 illustrates the yellowness index in a plastic 2.5mm color chip directly after molding as a function of monomer organic purity and monomer synthesis catalyst & promoter system.
  • FIG. 4 illustrates the yellowness index in a plastic 2.5mm color chip after 2,000 hrs of heat aging at 130 °C as a function of monomer organic purity and monomer synthesis catalyst & promoter system.
  • Ranges can be expressed herein as from “about” one particular value, and/or to "about” another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about,” it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint, and are independently combinable with endpoints of other expressed ranges for the same property. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as “about” that particular value in addition to the value itself.
  • the terms “optional” or “optionally” means that the subsequently described event or circumstance can or can not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.
  • the phrase “optionally substituted alkyl” means that the alkyl group can or can not be substituted and that the description includes both substituted and unsubstituted alkyl groups.
  • compositions of the invention Disclosed are the components to be used to prepare the compositions of the invention as well as the compositions themselves to be used within the methods disclosed herein. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each various individual and collective combinations and permutation of these compounds can not be explicitly disclosed, each is specifically contemplated and described herein. For example, if a particular compound is disclosed and discussed and a number of modifications that can be made to a number of molecules including the compounds are discussed, specifically contemplated is each and every combination and permutation of the compound and the modifications that are possible unless specifically indicated to the contrary.
  • references in the specification and concluding claims to parts by weight of a particular element or component in a composition or article denote the weight relationship between the element or component and any other elements or components in the composition or article for which a part by weight is expressed.
  • X and Y are present at a weight ratio of 2:5, and are present in such ratio regardless of whether additional components are contained in the compound.
  • a weight percent of a component is based on the total weight of the formulation or composition in which the component is included.
  • a residue of a chemical species refers to the moiety that is the resulting product of the chemical species in a particular reaction scheme or subsequent formulation or chemical product, regardless of whether the moiety is actually obtained from the chemical species.
  • an ethylene glycol residue in a polyester refers to one or more -OCH 2 CH 2 0- units in the polyester, regardless of whether ethylene glycol was used to prepare the polyester.
  • a sebacic acid residue in a polyester refers to one or more -CO(CH 2 ) 8 CO- moieties in the polyester, regardless of whether the residue is obtained by reacting sebacic acid or an ester thereof to obtain the polyester.
  • alkyl group as used herein is a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl, tetracosyl and the like.
  • a "lower alkyl” group is an alkyl group containing from one to six carbon atoms.
  • alkoxy as used herein is an alkyl group bound through a single, terminal ether linkage; that is, an "alkoxy” group may be defined as -OR where R is alkyl as defined above.
  • a "lower alkoxy” group is an alkoxy group containing from one to six carbon atoms.
  • alkenyl group as used herein is a hydrocarbon group of from 2 to 24 carbon atoms and structural formula containing at least one carbon-carbon double bond.
  • alkynyl group as used herein is a hydrocarbon group of 2 to 24 carbon atoms and a structural formula containing at least one carbon-carbon triple bond.
  • aryl group as used herein is any carbon-based aromatic group including, but not limited to, benzene, naphthalene, etc.
  • aromatic also includes “heteroaryl group,” which is defined as an aromatic group that has at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus.
  • the aryl group can be substituted or unsubstituted.
  • the aryl group can be substituted with one or more groups including, but not limited to, alkyl, alkynyl, alkenyl, aryl, halide, nitro, amino, ester, ketone, aldehyde, hydroxy, carboxylic acid, or alkoxy.
  • cycloalkyl group is a non-aromatic carbon-based ring composed of at least three carbon atoms.
  • examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.
  • heterocycloalkyl group is a cycloalkyl group as defined above where at least one of the carbon atoms of the ring is substituted with a heteroatom such as, but not limited to, nitrogen, oxygen, sulphur, or phosphorus.
  • aralkyl as used herein is an aryl group having an alkyl, alkynyl, or alkenyl group as defined above attached to the aromatic group.
  • An example of an aralkyl group is a benzyl group.
  • hydroxyalkyl group as used herein is an alkyl, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or heterocycloalkyl group described above that has at least one hydrogen atom substituted with a hydroxyl group.
  • alkoxyalkyl group is defined as an alkyl, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or heterocycloalkyl group described above that has at least one hydrogen atom substituted with an alkoxy group described above.
  • esters as used herein is represented by the formula— C(0)OA, where A can be an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above.
  • carbonate group as used herein is represented by the formula -OC(0)OR, where R can be hydrogen, an alkyl, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or heterocycloalkyl group described above.
  • aldehyde as used herein is represented by the formula -C(0)H.
  • keto group as used herein is represented by the formula - C(0)R, where R is an alkyl, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or heterocycloalkyl group described above.
  • ether as used herein is represented by the formula AOA 1 , where A and A 1 can be, independently, an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above.
  • sulfo-oxo group as used herein is represented by the formulas -S(0) 2 , -OS(0) 2 , or , -OS(0) 2 0R, where R can be hydrogen, an alkyl, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or heterocycloalkyl group described above.
  • promoter catalyst system is intended to refer to a catalyst system comprising a promoter, unless specifically stated to the contrary.
  • a promoter catalyst system can also be referred to as a promoted catalyst system, indicating the presence of a promoter in the catalyst system.
  • polycarbonate is intended to refer to compositions having repeating structural carbonate units of formula (1)
  • each R 1 is a C6-30 aromatic group, that is, contains at least one aromatic moiety.
  • R 1 can be derived from a dihydroxy compound of the formula HO-R ⁇ OH, in particular of formula (2)
  • each of A and A is a monocyclic divalent aromatic group and Y is a single bond or a bridging group having one or more atoms that separate A 1 from A 2 .
  • each R can be derived from a dihydroxy aromatic com ound of formula (3)
  • R a and R b are each independently a halogen, Ci_i 2 alkoxy, or Ci_i 2 alkyl; and p and q are each independently integers of 0 to 4. It will be understood that R a is hydrogen when p is 0, and likewise R b is hydrogen when q is 0. Also in formula (3), X a is a bridging group connecting the two hydroxy-substituted aromatic groups, where the bridging group and the hydroxy substituent of each e arylene group are disposed ortho, meta, or para (specifically para) to each other on the e arylene group.
  • the bridging group X a is single bond, -0-, -S-, -S(O)-, -S(0) 2 -, -C(O)-, or a Ci-is organic group.
  • the Ci-is organic bridging group can be cyclic or acyclic, aromatic or non-aromatic, and can further comprise heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorous.
  • the CMS organic group can be disposed such that the Ce arylene groups connected thereto are each connected to a common alkylidene carbon or to different carbons of the CMS organic bridging 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.
  • X a is a Ci_is alkylene group, a C3_is cycloalkylene group,
  • X a can be a substituted C3 8 cycloalkylidene of formula (4)
  • R r , R p , R q , and R l are each independently hydrogen, halogen, oxygen, or Ci_i2 hydrocarbon groups;
  • Q is a direct bond, a carbon, or a divalent oxygen, sulfur, or -N(Z)- where Z is hydrogen, halogen, hydroxy, Ci_i2 alkyl, Ci_i2 alkoxy, or Ci_i2 acyl;
  • r is 0 to 2
  • t is 1 or 2
  • q is 0 or 1
  • k is 0 to 3, with the proviso that at least two of R r , R p , R q , and R l taken together are a fused cycloaliphatic, aromatic, or heteroaromatic ring.
  • the ring as shown in formula (4) will have an unsaturated carbon-carbon linkage where the ring is fused.
  • the ring as shown in formula (4) contains 4 carbon atoms
  • the ring as shown in formula (4) contains 5 carbon atoms
  • the ring contains 6 carbon atoms.
  • two adjacent groups e.g., R q and R l taken together
  • R q and R l taken together form one aromatic group
  • R r and R p taken together form a second aromatic group.
  • R p can be a double-bonded oxygen atom, i.e., a ketone.
  • bisphenols (4) can be used in the manufacture of polycarbonates containing phthalimidine carbonate units of formula (4a)
  • R a , R b , p, and q are as in formula (4), R 3 is each independently a Ci_6 alkyl group, j is 0 to 4, and R4 is a Ci_6 alkyl, phenyl, or phenyl substituted with up to five Ci_6 alkyl g nate units are of formula (4b)
  • R 5 is hydrogen or a Ci_6 alkyl.
  • R 5 is hydrogen.
  • Carbonate units (4a) wherein R 5 is hydrogen can be derived from 2-phenyl-3,3'-bis(4-hydroxy
  • phenyl)phthalimidine also known as N-phenyl phenolphthalein bisphenol, or "PPPBP”
  • PPPBP N-phenyl phenolphthalein bisphenol
  • R a and R b are each independently Ci_i2 alkyl, p and q are each independently 0 to 4, and R 1 is Ci_i2 alkyl, phenyl, optionally substituted with 1 5 to Ci_io alkyl, or benzyl optionally substituted with 1 to 5 Ci_io alkyl.
  • R a and R b are each methyl, p and q are each independently 0 or 1, and R 1 is C alkyl or phenyl.
  • Examples of bisphenol carbonate units derived from bisphenols (4) wherein X b is a substituted or unsubstituted C3_i8 cycloalkylidene include the cyclohexylidene- bridged, alkyl-substituted bisphenol of formula (4e) wherein R a and R b are each independently C1-12 alkyl, R s is C1-12 alkyl, p and q are each independently 0 to 4, and t is 0 to 10.
  • at least one of each of R a and R b are disposed meta to the cyclohexylidene bridging group.
  • R a and R b are each independently Ci_ 4 alkyl, R s is Ci_ 4 alkyl, p and q are each 0 or 1 , and t is 0 to 5.
  • R a , R b , and R s are each methyl, r and s are each 0 or 1, and t is 0 or 3, specifically 0.
  • R a , R b , and R s are each methyl, r and s are each 0 or 1, and t is 0 or 3, specifically 0.
  • Examples of other bisphenol carbonate units derived from bisphenol (4) wherein X b is a substituted or unsubstituted C3 8 cycloalkylidene include adamantyl units (4f) and units (4g)
  • R a and R b are each independently C1-12 alkyl, and p and q are each independently 1 to 4.
  • at least one of each of R a and R b are disposed meta to the cycloalkylidene bridging group.
  • R a and R b are each independently C1-3 alkyl, and p and q are each 0 or 1.
  • R a , R b are each methyl, p and q are each 0 or 1.
  • Carbonates containing units (4a) to (4g) are useful for making
  • polycarbonates with high glass transition temperatures (Tg) and high heat distortion temperatures.
  • each R h is independently a halogen atom, a Ci_i 0 hydrocarbyl such as a Ci_i 0 alkyl group, a halogen-substituted Ci_io 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.
  • 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 -naphthylme thane, 1 ,2-bis(4- hydroxyphenyl)ethane, 1 , 1 -bis(4-hydroxyphenyl)- 1 -phenylethane, 2-(4-hydroxyphenyl)-2-(3- hydroxyphenyl)propane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-3- bromophenyl)propane, 1,1 -bis (hydroxyphenyl)cyclopentane, l,l-bis(4- hydroxyphenyl)cyclohexane, 1
  • bisphenol compounds of formula (3) include 1,1- 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, 2-phenyl-3,3-bis(4-hydroxyphenyl) phthalimidine (PPPBP), and
  • the polycarbonate is a linear homopolymer derived from bisphenol A, in which each of A 1 and A2 is p-phenylene and Y 1 is isopropylidene in formula (3).
  • polycarbonates is intended to refer to homopolycarbonates (wherein each R 1 in the polymer is the same), copolymers comprising different R 1 moieties in the carbonate (“copolycarbonates”), copolymers comprising carbonate units and other types of polymer units, such as ester units, and combinations comprising at least one of homopolycarbonates and/or copolycarbonates.
  • a specific type of copolymer is a polyester carbonate, also known as a polyester-polycarbonate. Such copolymers further contain, in addition to recurring carbonate chain units of formula (1), repeating units of formula (6)
  • J is a divalent group derived from a dihydroxy compound, and can be, for example, a C2-10 alkylene, a C -20 cycloalkylene a C -20 arylene, or a polyoxyalkylene group in which the alkylene groups contain 2 to 6 carbon atoms, specifically 2, 3, or 4 carbon atoms; and T is a divalent group derived from a dicarboxylic acid, and can be, for example, a C2-10 alkylene, a Ce-20 cycloalkylene, or a Ce-20 arylene.
  • Copolyesters containing a combination of different T and/or J groups can be used.
  • the polyesters can be branched or linear.
  • J is a C2-30 alkylene group having a straight chain, branched chain, or cyclic (including polycyclic) structure.
  • J is derived from an aromatic dihydroxy compound of formula (3) above.
  • J is derived from an aromatic dihydroxy compound of formula (4) above.
  • J is derived from an aromatic dihydroxy compound of formula (5) above.
  • Aromatic dicarboxylic acids that can be used to prepare the polyester units include isophthalic or terephthalic acid, 1 ,2-di(p-carboxyphenyl)ethane, 4,4'- dicarboxydiphenyl ether, 4,4'-bisbenzoic acid, or a combination comprising at least one of the foregoing acids. Acids containing fused rings can also be present, such as in 1,4-, 1 ,5-, or 2,6-naphthalenedicarboxylic acids.
  • Specific dicarboxylic acids include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, cyclohexane dicarboxylic acid, or a combination comprising at least one of the foregoing acids.
  • a specific dicarboxylic acid comprises a combination of isophthalic acid and terephthalic acid wherein the weight ratio of isophthalic acid to terephthalic acid is 91 :9 to 2:98.
  • J is a C2-6 alkylene group and T is p-phenylene, m-phenylene, naphthalene, a divalent cycloaliphatic group, or a combination thereof.
  • This class of polyester includes the poly(alkylene terephthalates).
  • the molar ratio of ester units to carbonate units in the copolymers can vary broadly, for example 1 :99 to 99: 1, specifically 10:90 to 90:10, more specifically 25:75 to 75:25, depending on the desired properties of the final composition.
  • the polyester unit of a polyester-polycarbonate is derived from the reaction of a combination of isophthalic and terephthalic diacids (or derivatives thereof) with resorcinol.
  • the polyester unit of a polyester-polycarbonate is derived from the reaction of a combination of isophthalic acid and terephthalic acid with bisphenol A.
  • the polycarbonate units are derived from bisphenol A.
  • the polycarbonate units are derived from resorcinol and bisphenol A in a molar ratio of resorcinol carbonate units to bisphenol A carbonate units of 1 :99 to 99: 1.
  • Polycarbonates can be manufactured by processes such as interfacial polymerization and melt polymerization.
  • Branched polycarbonate blocks can be prepared by adding a branching agent during polymerization.
  • branching agents include polyfunctional organic compounds containing at least three functional groups selected from hydroxyl, carboxyl, carboxylic anhydride, haloformyl, and mixtures of the foregoing functional groups.
  • trimellitic acid trimellitic anhydride
  • trimellitic trichloride tris-p-hydroxy phenyl ethane
  • isatin-bis-phenol tris-phenol TC (l,3,5-tris((p- hydroxyphenyl)isopropyl)benzene)
  • tris-phenol PA (4(4(1, l-bis(p-hydroxyphenyl)-ethyl) alpha, alpha-dimethyl benzyl)phenol), 4-chloroformyl phthalic anhydride, trimesic acid, and benzophenone tetracarboxylic acid.
  • the branching agents can be added at a level of 0.05 to 2.0 wt%. Mixtures comprising linear polycarbonates and branched polycarbonates can be used.
  • 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
  • chain stoppers include certain mono-phenolic compounds, mono-carboxylic acid chlorides, and/or mono-chloroformates.
  • Mono-phenolic chain stoppers are exemplified by monocyclic phenols such as phenol and C1-C 22 alkyl- substituted phenols such as p-cumyl-phenol, resorcinol monobenzoate, and p-and tertiary- butyl phenol; and monoethers of diphenols, such as p-methoxyphenol.
  • Alkyl-substituted phenols with branched chain alkyl substituents having 8 to 9 carbon atom can be specifically mentioned.
  • Certain mono-phenolic UV absorbers can also be used as a capping agent, for example 4-substituted-2-hydroxybenzophenones and their derivatives, aryl salicylates, monoesters of diphenols such as resorcinol monobenzoate, 2-(2-hydroxyaryl)-benzotriazoles and their derivatives, 2-(2-hydroxyaryl)-l,3,5-triazines and their derivatives, and the like.
  • Mono-carboxylic acid chlorides can also be used as chain stoppers. These include monocyclic, mono-carboxylic acid chlorides such as benzoyl chloride, C1-C 22 alkyl- substituted benzoyl chloride, toluoyl chloride, halogen-substituted benzoyl chloride, bromobenzoyl chloride, cinnamoyl chloride, 4-nadimidobenzoyl chloride, and combinations thereof; polycyclic, mono-carboxylic acid chlorides such as trimellitic anhydride chloride, and naphthoyl chloride; and combinations of monocyclic and polycyclic mono-carboxylic acid chlorides.
  • monocyclic, mono-carboxylic acid chlorides such as benzoyl chloride, C1-C 22 alkyl- substituted benzoyl chloride, toluoyl chloride, halogen-substituted benzoyl chloride, bromobenzoyl chloride,
  • Chlorides of aliphatic monocarboxylic acids with less than or equal to 22 carbon atoms are useful.
  • Functionalized chlorides of aliphatic monocarboxylic acids such as acryloyl chloride and methacryoyl chloride, are also useful.
  • mono- chloroformates including monocyclic, mono-chloroformates, such as phenyl chloroformate, alkyl-substituted phenyl chloroformate, p-cumyl phenyl chloroformate, toluene
  • melt processes can be used to make the polycarbonates.
  • the polyester-polycarbonates can also be prepared by interfacial polymerization.
  • the reactive derivatives of the acid or diol such as the corresponding acid halides, in particular the acid dichlorides and the acid dibromides can be used.
  • isophthalic acid, terephthalic acid, or a combination comprising at least one of the foregoing acids isophthaloyl dichloride, terephthaloyl dichloride, or a combination comprising at least one of the foregoing dichlorides can be used.
  • combinations of the polycarbonate with other thermoplastic polymers for example combinations of
  • polyesters can include, for example, polyesters having repeating units of formula (6), which include poly(alkylene dicarboxylates), liquid crystalline polyesters, and polyester copolymers.
  • the polyesters described herein are generally completely miscible with the polycarbonates when blended.
  • polyesters can be obtained by interfacial polymerization or melt- process condensation as described above, by solution phase condensation, or by
  • transesterification polymerization wherein, for example, a dialkyl ester such as dimethyl terephthalate can be transesterified with ethylene glycol using acid catalysis, to generate poly(ethylene terephthalate).
  • a branched polyester in which a branching agent, for example, a glycol having three or more hydroxyl groups or a trifunctional or multifunctional carboxylic acid has been incorporated, can be used.
  • a branching agent for example, a glycol having three or more hydroxyl groups or a trifunctional or multifunctional carboxylic acid has been incorporated, can be used.
  • Useful polyesters can include aromatic polyesters, poly(alkylene esters) including poly(alkylene arylates), and poly(cycloalkylene diesters).
  • Aromatic polyesters can have a polyester structure according to formula (6), wherein J and T are each aromatic groups as described hereinabove.
  • useful aromatic polyesters can include, for example, poly(isophthalate-terephthalate-resorcinol) esters, poly(isophthalate-terephthalate-bisphenol A) esters, poly[(isophthalate-terephthalate-resorcinol) ester-co-(isophthalate-terephthalate- bisphenol A)] ester, or a combination comprising at least one of these.
  • aromatic polyesters with a minor amount, e.g., 0.5 to 10 weight percent, based on the total weight of the polyester, of units derived from an aliphatic diacid and/or an aliphatic polyol to make copolyesters.
  • Poly(alkylene arylates) can have a polyester structure according to formula (6), wherein T comprises groups derived from aromatic dicarboxylates,
  • T groups include 1,2-, 1,3-, and 1,4-phenylene; 1,4- and 1,5- naphthylenes; cis- or trans-1,4- cyclohexylene; and the like.
  • T is 1,4-phenylene
  • the poly(alkylene arylate) is a poly(alkylene terephthalate).
  • alkylene groups J include, for example, ethylene, 1 ,4-butylene, and bis-(alkylene- disubstituted cyclohexane) including cis- and/or trans- 1 ,4-(cyclohexylene)dimethylene.
  • poly(alkylene terephthalates) include poly(ethylene terephthalate) (PET), poly(l,4-butylene terephthalate) (PBT), and poly(propylene terephthalate) (PPT).
  • poly(alkylene naphthoates) such as poly(ethylene naphthanoate) (PEN), and poly(butylene naphthanoate) (PBN).
  • a specifically useful poly(cycloalkylene diester) is poly(cyclohexanedimethylene terephthalate) (PCT). Combinations comprising at least one of the foregoing polyesters can also be used.
  • Copolymers comprising alkylene terephthalate repeating ester units with other ester groups can also be useful.
  • Specifically useful ester units can include different alkylene terephthalate units, which can be present in the polymer chain as individual units, or as blocks of poly (alkylene terephthalates). copolymers of this type include
  • PETG poly(cyclohexanedimethylene terephthalate)-co-poly(ethylene terephthalate)
  • PCTG poly(l,4-cyclohexanedimethylene terephthalate)
  • Poly(cycloalkylene diester)s can also include poly(alkylene
  • cyclohexanedicarboxylate s.
  • PCCD poly(l,4-cyclohexane- dimethanol-l,4-cyclohexanedicarboxylate)
  • J is a 1 ,4-cyclohexanedimethylene group derived from 1,4-cyclohexanedimethanol
  • T is a cyclohexane ring derived from cyclohexanedicarboxylate or a chemical equivalent thereof, and can comprise the cis-isomer, the trans-isomer, or a combination comprising at least one of the foregoing isomers.
  • the polycarbonate and polyester can be used in a weight ratio of 1 :99 to 99: 1, specifically 10:90 to 90: 10, and more specifically 30:70 to 70:30, depending on the function and properties desired.
  • polyester and polycarbonate blend it is desirable for such a polyester and polycarbonate blend to have an MVR of 5 to 150 cc/10 min., specifically 7 to 125 cc/10 min, more specifically 9 to 110 cc/10 min, and still more specifically 10 to 100 cc/10 min., measured at 300°C and a load of 1.2 kilograms according to ASTM D1238-04.
  • a polycarbonate can comprise a polysiloxane - polycarbonate copolymer, also referred to as a polysiloxane -polycarbonate.
  • polysiloxane blocks of the copolymer comprise repeating diorganosiloxane units as in formula (8)
  • each R is independently a C1 3 monovalent organic group.
  • R can be a C1-C1 3 alkyl, C1-C1 3 alkoxy, C2-C1 3 alkenyl group, C2-C1 3 alkenyloxy, C3-C6 cycloalkyl, C3-C6 cycloalkoxy, C6-C14 aryl, C6-C10 aryloxy, C7-C13 arylalkyl, C7-C13 aralkoxy, C7-C1 3 alkylaryl, or C7-C1 3 alkylaryloxy.
  • the foregoing groups can be fully or partially halogenated with fluorine, chlorine, bromine, or iodine, or a combination thereof.
  • R is unsubstituted by halogen. Combinations of the foregoing R groups can be used in the same copolymer.
  • E in formula (8) can vary widely depending on the type and relative amount of each component in the thermoplastic composition, the desired properties of the composition, and like considerations. Generally, E has an average value of 2 to 1,000, specifically 2 to 500, or 2 to 200, more specifically 5 to 100. In an aspect, E has an average value of 10 to 75, and in still another aspect, E has an average value of 40 to 60. Where E is of a lower value, e.g., less than 40, it can be desirable to use a relatively larger amount of the polycarbonate -polysiloxane copolymer. Conversely, where E is of a higher value, e.g., greater than 40, a relatively lower amount of the polycarbonate -polysiloxane copolymer can be used.
  • a combination of a first and a second (or more) polycarbonate- polysiloxane copolymers can be used, wherein the average value of E of the first copolymer is less than the average value of E of the second copolymer.
  • polydiorganosiloxane blocks are of formula (9)
  • each R can be the same or different, and is as defined above; and Ar can be the same or different, and is a substituted or unsubstituted C6-C 30 arylene group, wherein the bonds are directly connected to an aromatic moiety.
  • Ar groups in formula (9) can be derived from a C6-C 30 dihydroxyarylene compound, for example a dihydroxyarylene compound of formula (3) or (5) above, dihydroxyarylene compounds are l,l-bis(4-hydroxyphenyl) methane, l,l-bis(4-hydroxyphenyl) ethane, 2,2-bis(4- hydroxyphenyl) propane, 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-l- methylphenyl) propane, l,l-bis(4-hydroxyphenyl) cyclohexane, bis(4-hydroxyphenyl sulfide), and l,l-bis(4-hydroxy-t-butylphenyl) propane.
  • Combinations comprising at least one
  • polydiorganosiloxane blocks are of formula (10)
  • R and E are as described above, and each R is independently a divalent C1-C30 organic group, and wherein the polymerized polysiloxane unit is the reaction residue of its corresponding dihydroxy compound.
  • the polymerized polysiloxane unit is the reaction residue of its corresponding dihydroxy compound.
  • polydiorganosiloxane blocks are of formula (11):
  • R in formula (11) is a divalent C2- Cs aliphatic group.
  • Each M in formula (11) can be the same or different, and can be a halogen, cyano, nitro, Ci-Cs alkylthio, Ci-Cs alkyl, Ci-Cs alkoxy, C2-C8 alkenyl, C2-C8 alkenyloxy group, C3-C8 cycloalkyl, C Cs cycloalkoxy, C6-C10 aryl, C6-C10 aryloxy, C7-C12 aralkyl, C7-C12 aralkoxy, C7-C12 alkylaryl, or C7-C12 alkylaryloxy, wherein each n is independently 0, 1, 2, 3, or 4.
  • M is bromo or chloro, an alkyl group such as methyl, ethyl, or propyl, an alkoxy group such as methoxy, ethoxy, or propoxy, or an aryl group such as phenyl, chlorophenyl, or tolyl;
  • R 2 is a dimethylene, trimethylene or tetramethylene group; and
  • R is a Ci_s alkyl, haloalkyl such as trifluoropropyl, cyanoalkyl, or aryl such as phenyl, chlorophenyl or tolyl.
  • R is methyl, or a combination of methyl and trifluoropropyl, or a combination of methyl and phenyl.
  • M is methoxy
  • n is one
  • R 2 is a divalent C1-C3 aliphatic group
  • R is methyl.
  • Blocks of formula (11) can be derived from the corresponding dihydroxy polydiorganosiloxane (12)
  • dihydroxy polysiloxanes can be made by effecting a platinum-catalyzed addition between a siloxane hydride of formula (13)
  • R and E are as previously defined, and an aliphatically unsaturated monohydric phenol, aliphatically unsaturated monohydric phenols include eugenol, 2- alkylphenol, 4-allyl-2-methylphenol, 4-allyl-2-phenylphenol, 4-allyl-2-bromophenol, 4-allyl- 2-t-butoxyphenol, 4-phenyl-2-phenylphenol, 2-methyl-4-propylphenol, 2-allyl-4,6- dimethylphenol, 2-allyl-4-bromo-6-methylphenol, 2-allyl-6-methoxy-4-methylphenol and 2- allyl-4,6-dimethylphenol. Combinations comprising at least one of the foregoing can also be used.
  • the polyorganosiloxane -polycarbonate can comprise 50 to 99 weight percent of carbonate units and 1 to 50 weight percent siloxane units. Within this range, the polyorganosiloxane -polycarbonate copolymer can comprise 70 to 98 weight percent, more specifically 75 to 97 weight percent of carbonate units and 2 to 30 weight percent, more specifically 3 to 25 weight percent siloxane units.
  • Polyorganosiloxane -polycarbonates can have a weight average molecular weight of 2,000 to 100,000 Daltons, specifically 5,000 to 50,000 Daltons as measured by gel permeation chromatography using a crosslinked styrene-divinyl benzene column, at a sample concentration of 1 milligram per milliliter, and as calibrated with polycarbonate standards.
  • the polyorganosiloxane -polycarbonate can have a melt volume flow rate, measured at 300°C/1.2 kg, of 1 to 50 cubic centimeters per 10 minutes (cc/10 min), specifically 2 to 30 cc/10 min. Mixtures of polyorganosiloxane -polycarbonates of different flow properties can be used to achieve the overall desired flow property.
  • a polycarbonate material can comprise a flame retardant.
  • a BPA polycarbonate material can comprise a second polycarbonate derived from bisphenol-A, wherein the second polycarbonate is different than the BPA polycarbonate.
  • a BPA polycarbonate material can comprise a second polycarbonate derived from bisphenol-A, wherein the second polycarbonate is selected from at least one of the following: a homopolycarbonate derived from a bisphenol; a
  • a BPA polycarbonate can comprise one or more additives selected from at least one of the following: UV stabilizing additives, thermal stabilizing additives, mold release agents, colorants, organic fillers, inorganic fillers, and gamma-stabilizing agents.
  • compositions disclosed herein have certain functions. Disclosed herein are certain structural requirements for performing the disclosed functions, and it is understood that there are a variety of structures that can perform the same function that are related to the disclosed structures, and that these structures will typically achieve the same result.
  • the present disclosure provides a manufacturing process and a promoter catalyst system that can be useful in condensation reactions, such as, for example, the synthesis of bisphenol-A.
  • Conventional ion exchange resin based BPA manufacturing processes utilize sulfur containing bulk promoters, such as
  • 3-mercaptopropionic acid (3-MPA), that can degrade and generate undesirable sulfur compounds in the final product.
  • These compounds can limit or prevent the use of BPA in demanding applications, such as food contact grade polycarbonate.
  • the present disclosure provides a manufacturing process that can produce high purity BPA, with no or substantially no inorganic, sulfur, or thermally degraded components.
  • the present disclosure provides a manufacturing process that can produce high purity BPA having low or no sulfur present.
  • the present disclosure provides a manufacturing process that does not utilize a bulk promoter, such as, for example, 3-MPA.
  • the present disclosure provides a manufacturing process and catalyst system that can provide high purity BPA, suitable for use in food contact polycarbonate applications, healthcare applications, optical applications, or a combination thereof.
  • the present disclosure provides a manufacturing process that comprises an attached promoter catalyst in combination with solvent crystallization.
  • Promoter systems can also be attached, wherein the promoter is attached to the catalyst system, such as the ion exchange resin.
  • An exemplary attached promoter system utilizes a pyridyl ethylmercapton (PEM) promoter.
  • the methods described here can be useful for the preparation of BPA.
  • reactants for bisphenol condensation reactions can comprise phenols, ketones and/or aldehydes, or mixtures thereof.
  • any specific recitation of a ketone, such as acetone, or an aldehyde is intended to include aspects where only the recited species is used, aspects wherein the other species (e.g., aldehyde for ketone) is used, and aspects wherein a combination of species is used.
  • the methods described herein can be useful for the preparation of other chemical species from, for example, condensation reactions.
  • phenol reactants can comprise an aromatic hydroxy compound having at least one unsubstituted position, and optionally one or more inert substituents such as hydrocarbyl or halogen at one or more ring positions.
  • an inert substituent is a substituent which does not interfere undesirably with the condensation of the phenol and ketone or aldehyde and which is not, itself, catalytic.
  • phenol reactants are unsubstituted in the position para to the hydroxyl group.
  • hydrocarbyl functionalities comprise carbon and hydrogen atoms, such as, for example, alkylene, alkyl, cycloaliphatic, aryl, arylene, alkylarylene, arylalkylene, alkylcycloaliphatic and alkylenecycloaliphatic are hydrocarbyl functions, that is, functions containing carbon and hydrogen atoms.
  • an alkyl group if present in a phenol species, comprises from 1 to about 20 carbon atoms, or from 1 to about 5 carbon atoms, or from 1 to about 3 carbon atoms, such as, for example, various methyl, ethyl, propyl, butyl and pentyl isomers.
  • alkyl, aryl, alkaryl and aralkyl substituents are suitable hydrocarbyl substituents on the phenol reactant.
  • other inert phenol substituents can include, but are not limited to alkoxy, aryloxy or alkaryloxy, wherein alkoxy includes methoxy, ethoxy, propyloxy, butoxy, pentoxy, hexoxy, heptoxy, octyloxy, nonyloxy, decyloxy and
  • polyoxyethylene as well as higher homologues; aryloxy, phenoxy, biphenoxy, naphthyloxy, etc. and alkaryloxy includes alkyl, alkenyl and alkylnyl-substituted phenolics. Additional inert phenol substituents can include halo, such as bromo, chloro or iodo.
  • exemplary phenols can comprise, phenol, 2-cresol, 3-cresol, 4-cresol, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 2-tert- butylphenol, 2,4-dimethylphenol, 2-ethyl-6-methylphenol, 2-bromophenol, 2-fluorophenol, 2-phenoxyphenol, 3-methoxyphenol, 2,3,6-trimethylphenol, 2,3,5,6-tetramethylphenol, 2,6- xylenol, 2,6-dichlorophenol, 3,5-diethylphenol, 2-benzylphenol, 2,6-di-tertbutylphenol, 2- phenylphenol, 1-naphthol, 2-naphthol, and/or combinations thereof.
  • phenol reactants can comprise phenol, 2- or 3-cresol, 2,6-dimethylphenol, resorcinol, naphthols, and/or combinations or mixtures thereof.
  • a phenol is unsubstituted.
  • the phenol starting materials can be commercial grade or better.
  • commercial grade reagents may contain measurable levels of typical impurities such as acetone, alpha-methylstyrene, acetophenone, alkyl benzenes, cumene, cresols, water, hydroxyacetone, methyl benzofuran, methyl cyclopentenone, and mesityl oxide, among others.
  • ketones can be substituted with substituents that are inert under the conditions used, such as, for example those inert substituents recited above with respect to phenols.
  • a ketone can comprise aliphatic, aromatic, alicyclic or mixed aromatic-aliphatic ketones, diketones or polyketones, of which acetone, methyl ethyl ketone, diethyl ketone, benzyl, acetyl acetone, methyl isopropyl ketone, methyl isobutyl ketone, acetophenone, ethyl phenyl ketone, cyclohexanone, cyclopentanone, benzophenone, fluorenone, indanone, 3,3,5-trimethylcyclohexanone, anthraquinone,
  • acetophenone 4-hydroxy acetophenone, acenaphthenequinone, quinone, benzoylacetone and diacetyl are representative examples.
  • a ketone having halo, nitrile or nitro substituents can also be used, for example, 1,3-dichloroacetone or hexafluoroacetone.
  • Exemplary aliphatic ketones can comprise acetone, ethyl methyl ketone, isobutyl methyl ketone, 1,3-dichloroacetone, hexafluoroacetone, or combinations thereof.
  • the ketone is acetone, which can condense with phenol to produce 2,2-bis-(4- hydroxyphenyl)-propane, commonly known as bisphenol A.
  • a ketone comprises hexafluoroacetone, which can react with two moles of phenol to produce 2,2-bis- (4-hydroxyphenyl)-hexafluoropropane (bisphenol AF).
  • a ketone can comprise a ketone having at least one hydrocarbyl group containing an aryl group, for example, a phenyl, tolyl, naphthyl, xylyl or 4-hydroxyphenyl group.
  • ketones can include 9-fluorenone, cyclohexanone, 3,3,5- trimethylcyclohexanone, indanone, indenone, anthraquinone, or combinations thereof. Still other exemplary ketones can include benzophenone, acetophenone, 4-hydroxyacetophenone, 4,4'-dihydroxybenzophenone, or combinations thereof.
  • a ketone reactant can be commercial grade or better.
  • commercial grade reagents may contain measurable levels of typical impurities such as aldehydes, acetophenone, benzene, cumene, diacetone alcohol, water, mesityl oxide, and methanol, among others.
  • a ketone, such as, for example, acetone has less than about 250 ppm of methanol.
  • the inventive catalyst systems of the present invention can tolerate higher
  • a ketone can comprise more than 250 ppm of methanol.
  • the various methods and catalyst systems described herein can be used for the condensation of phenols with aldehydes, for example, with formaldehyde, acetaldehyde, propionaidehyde, butyraldehyde or higher homologues of the formula RCHO, wherein R is alkyl of, for example, 1 to 20 carbon atoms.
  • R is alkyl of, for example, 1 to 20 carbon atoms.
  • the condensation of two moles of phenol with one mole of formaldehyde produces bis-(4- hydroxyphenyl)methane, also known as Bisphenol F.
  • dialdehydes and ketoaldehdyes for example, glyoxal, phenylglyoxal or pyruvic aldehyde, can optionally be used.
  • the promoter catalyst system of the present disclosure comprises an ion exchange resin catalyst and a promoter.
  • the ion exchange resin can comprise any ion exchange resin suitable for use in the catalyst system of the present invention.
  • the ion exchange resin comprises a cross-linked cationic exchange resin.
  • the ion exchange resin comprises a cross-linked sulfonated ion exchange resin having a plurality of sulfonic acid sites.
  • the ion exchange resin is acidic or strongly acidic.
  • at least a portion of the ion exchange resin comprises sodium polystyrene sulfonate.
  • the ion exchange resin can comprise a monodispersed resin, a polydispersed resin, or a combination thereof.
  • the specific chemistry of an ion exchange resin or any one or more polymer materials that form a part of an ion exchange resin can vary, and one of skill in the art, in possession of this disclosure, could readily select an appropriate ion exchange resin.
  • the ion exchange resin comprises polystyrene or a derivatized polystyrene.
  • the ion exchange resin comprises a polysiloxane or derivatized polysiloxane.
  • the catalyst system can, in one aspect, comprise multiple ion exchange resins of the same or varying composition, acidity, and/or degree of cross-linking.
  • the ion exchange resin can be cross-linked with the same or a different polymer material.
  • the degree of cross-linking is from about 1 percent to about 8 percent, for example, about 1, 2, 3, 4, 5, 6, 7, 8, percent; from about 1 percent to about 4 percent, for example, about 1, 1.2, 1.4, 1.6, 1.8, 2, 2.2, 2.4, 2.6, 2.8, 3, 3.2, 3.4, 3.6, 3.8, or or 4 percent; or from about 1.5 percent to about 2.5 percent, for example, about 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, or 2.5 percent.
  • the degree of cross-linking can be less than 1 percent or greater than 8 percent, and the present invention is not intended to be limited to any particular degree of cross-linking recited here. In a specific aspect, the degree of cross-linking is about 2 percent.
  • the ion exchange resin is not cross-linked. While not wishing to be bound by theory, cross-linking of an ion exchange resin is not necessary, but can provide additional stability to the resin and the resulting catalyst system.
  • the ion exchange resin can be cross-linked using any conventional cross-linking agents, such as, for example, polycyclic aromatic divinyl monomers, divinyl benzene, divinyl toluene, divinyl biphenyl monomers, or combinations thereof.
  • any conventional cross-linking agents such as, for example, polycyclic aromatic divinyl monomers, divinyl benzene, divinyl toluene, divinyl biphenyl monomers, or combinations thereof.
  • the ion exchange resin comprises a plurality of acid sites, and has, before modification, at least about 3, at least about 3.5, at least about 4, at least about 5, or more acid milliequivalents per gram (meq/g) when dry.
  • the ion exchange resin, before modification has at least about 3.5 acid milliequivalents per gram when dry.
  • any of the plurality of acid sites on an ion exchange resin can comprise a sulfonic acid functionality, which upon deprotonation produces a sulfonate anion functionality, a phosphonic acid functionality, which upon deprotonation produces a phosphonate anion functionality, or a carboxylic acid functionality, which upon
  • Exemplary ion exchange resins can include, but are not limited to, DIAION® SK104, DIAION® SK1B, DIAION® PK208, DIAION® PK212 and DIAION® PK216 (manufactured by Mitsubishi Chemical Industries, Limited), A-121, A-232, and A- 131, (manufactured by Rohm & Haas), T-38, T-66 and T-3825 (manufactured by Thermax), LEWATIT® K1131, LEWATIT® K1221 (manufactured by Lanxess), DOWEX® 50W2X, DOWEX® 50W4X, DOWEX® 50W8X resins (manufactured by Dow Chemical), Indion 180, Indion 225 (manufactured by Ion Exchange India Limited), and PUROLITE® CT-222 and PUROLITE® CT-122 (manufactured by Purolite).
  • the promoter of the attached promoter catalyst system of the present invention can comprise any promoter species suitable for use in the various methods described herein, and that can provide a desired high-purity product.
  • the promoter of the present invention can comprise pyridyl ethylmercapton (PEM). In another aspect, the promoter of the present invention can comprise dimethyl thiazolidine (DMT). In other aspects, the promoter of the present invention can comprise derivatives and/or analogues of pyridyl ethylmercapton, dimethyl thiazolidine, or a combination thereof. In another aspect the promoter of the present invention can comprise other promoter species not specifically recited herein. In another aspect, the promoter of the present invention can be represented by the formula below:
  • dimethyl thiazolidine is combined with an ion exchange resin so as to provide a cysteamine attached ion exchange resin.
  • the promoter can be contacted with the ion exchange resin so as to neutralize at least a portion of the available acid sites on the ion exchange resin, and attach thereto.
  • the ion exchange resin is modified by neutralizing from about 10 % to about 40 % of the available acid sites with the promoter; or from about 18 % to about 25 % of the available acid sites with the promoter.
  • the promoter is bound to from about 18 % to about 25 %, for example, about 18, 19, 20, 21, 22, 23, 24, or 25 % of the acid sites on the ion exchange resin.
  • the promoter is bound to from about 20 % to about 24 % of the acid sites on the ion exchange resin.
  • the promoter is bound to about 22 % of the acid sites of the ion exchange resin.
  • the promoter is combined with a solvent to form a mixture.
  • the mixture may further comprise an acid to improve solubility of the promoter.
  • the amount of acid can be sufficient to solubilize the promoter but not enough to impede modification of the ion exchange resin.
  • the amount of acid is typically less than or equal to about 1 equivalent; or less than or equal to about 0.25 equivalents, based on the number of moles of the promoter.
  • Exemplary acids include, but are not limited to, hydrochloric acid (HC1), p-toluenesulfonic acid, trifluorocacetic acid, and acetic acid.
  • the mixture can be contacted with the ion exchange resin resulting in an ionic linkage between the promoter cation and anion (deprotonated acid site) of the ion exchange resin. Formation of the ionic linkage neutralizes the acid site.
  • the degree of neutralization may be determined in a number of ways.
  • the modified ion exchange resin catalyst can be titrated to determine the amount of remaining acid sites.
  • the modified ion exchange resin catalyst can optionally be rinsed with a continuous flow of phenol to remove any remaining amounts of solvent from the modification.
  • the modified ion exchange resin can optionally be rinsed with deionized water prior to rinsing with phenol.
  • removing substantially all of the water is herein defined as removing greater than or equal to about 75%, greater than or equal to about 80%, or greater than or equal to about 85%, based on the total amount of water initially employed.
  • the promoter is ionically bound to the available acid sites of the ion exchange resin. In another aspect, all or substantially all of the promoter is ionically bound to acid sites of the ion exchange resin. In another aspect, at least a portion of the promoter is covalently bound to at least a portion of the ion exchange resin. In still another aspect, all or substantially all of the promoter is at least covalently bound to the ion exchange resin. In yet another aspect, the degree of attachment or binding between a promoter and an ion exchange resin can vary, such as, for example, covalent binding, ionic binding, and/or other interactions or attraction forces, and the present invention is not intended to be limited to any particular degree of attachment.
  • the reactants, phenol or optionally purified phenol, and at least one of a ketone or aldehyde can be fed into a reactor vessel and contacted.
  • the reactants, once in a reactor vessel can be mixed using, for example, a static mixer.
  • the reactor feed comprising the reactants can be cooled to a predetermined temperature using, for example, a plate heat exchanger.
  • use of the attached promoter catalyst system can allow for a reduction in the amount of acetone in the reactor feed stream, for example, from about 9.5 wt.% to about 5 wt.%.
  • the reactor effluent can have a lower solids content and a higher quantity of phenol.
  • a bed of the attached promoter ion exchange resin catalyst system such as, for example, a cross-linked ion exchange resin catalyst with attached dimethyl thiazolidine promoter
  • the reaction vessel and bed can be oriented such that the reactants flow downward (e.g., gravity- fed) through the catalyst bed.
  • the reaction can be controlled to a predetermined temperature, for example, about 55 ° C or 65 ° C. Variations in temperature can affect the rate of reaction and rate of isomerization of any produced BPA. Other temperatures not recited herein can be utilized, and one of skill in the art could readily determine an appropriate temperature at which to conduct a particular condensation reaction.
  • the reactor can be capable of converting at least about 90 % of the acetone, if present, in the reactor feed. In other aspects, the reactor can be capable of converting at least about 92 %, 94 %, 96 %, 98 %, or more of the acetone, if present, in the reactor feed. In another aspect, the reactor and attached promoter catalyst system can be capable of producing the ⁇ , ⁇ -BPA isomer with a selectivity of at least about 90 %.
  • the reactor and attached promoter catalyst system can be capable of producing the ⁇ , ⁇ -BPA isomer with a selectivity of at least about 90 %, at least about 92 %, at least about 93 %, at least about 95 %, at least about 97 %, or more.
  • the reactor effluent can optionally be subjected to a separate ion exchange resin bed to remove any undesired materials, such as, for example, oligomers, from the process stream.
  • the reactor effluent is subjected to a separate ion exchange resin bed to remove any undesired materials.
  • the reactor effluent is not subjected to a separate ion exchange resin bed.
  • the effluent stream can optionally be subjected to a water removal step to remove residual water.
  • a water removal step if performed, can comprise one or multiple columns positioned in sequence.
  • the reactor effluent stream can comprise water, acetone, phenol, toluene and/or other aromatic solvents, such as, for example benzene and xylene.
  • the effluent i.e., vapor
  • the vent gas from such process condenser can be conveyed to a brine vent condenser, cooled by, for example, chilled brine at a temperature of about 8 ° C.
  • an inert gas such as, for example, nitrogen
  • an aromatic solvent such as, for example, toluene
  • the reactor effluent (i.e., dehydrated reactor effluent) can have water content of less than about 0.5 wt.%, less than about 0.4 wt.%, less than about 0.3 wt.%, less than about 0.2 wt.%, or less than about 0.1 wt.%.
  • the dehydrated reactor effluent has a water content of less than about 0.2 wt.%. In another aspect, the dehydrated reactor effluent has a water content of about 0.1 wt.%.
  • the reactor effluent stream after optionally passing through a separate ion exchange resin bed and/or water removal step, can, in one aspect, comprise a phenol flash (i.e., phenol recovery) unit.
  • a phenol flash i.e., phenol recovery
  • a phenol flash unit can comprise a single column or a plurality of individual columns. In various aspects, any combination of columns or order of columns can be utilized. In one aspect, a phenol flash unit comprises three individual columns: a phenol flash column, an upper phenol column, and a lower phenol column. In another aspect, any one or multiple columns can be removed from a process. It should be noted that the terms “upper” and “lower” are not intended to require a particular orientation, and the respective columns can be positioned in any geometric arrangement appropriate for a particular process.
  • the phenol flash column removes all or a portion of phenol reactants from the effluent stream.
  • the reactor effluent such as, for example, the dehydrated reactor effluent
  • the phenol flash column can be operated at an elevated temperature and/or under vacuum, such as for example, about 750 mbar.
  • flashed phenol can be condensed after removal from the effluent stream.
  • flashed phenol can be at least partially condensed using the feed stream to the flash column as a cooling medium.
  • at least a portion of the energy expended to flash the phenol can be recovered. Any remaining phenol vapors, if present, can be recovered by, for example, a vacuum system.
  • the effluent stream can be first subjected to a phenol flash column.
  • the effluent from the phenol flash column can then be subjected to an upper phenol column, if present, and then to a lower phenol column.
  • the effluent from the phenol flash unit for example, after passing through a phenol flash column, an upper phenol column, and a lower phenol column, can have a free phenol content of less than about 1.0 wt.%, less than about 0.75 wt.%, or less than about 0.5 wt.%. In a specific aspect, the effluent from the phenol flash unit has a free phenol content of less than about 0.5 wt.%.
  • an effluent stream can optionally be redirected back through one or more units and/or columns of the reaction process so as to further react and/or purify the effluent.
  • the reactor effluent after being subjected to the phenol flash unit, can be fed to a solvent crystallization unit.
  • a solvent crystallization unit can be used to remove BPA byproducts, such as, for example, o,p-BPA, chromans, BPX 1 and/or 2, cyclic dimers (CD1 and/or 2), linear dimers (LD2 and/or 2), or a combination thereof. Structures of these BPA impurities are shown in e.g. Nowakowska et al., Polish J. Appl. Chem., XI(3), 247-254, 1996.
  • the solvent crystallization unit can remove at least a portion of the BPA byproducts from the effluent stream.
  • the solubility of one or more individual components in an effluent stream can be known or determined.
  • such solubility data can be used by one of skill in the art to optimize the crystallization parameters so as to provide an improved product.
  • Reaction products of the various methods of the present invention can, in various aspects, exhibit higher purity levels than are attainable using conventional manufacturing processes.
  • an attached promoter ion exchange resin catalyst system such as, for example, a dimethyl thiazolidine catalyst system, can provide a resulting BPA product that has no or substantially no inorganic or sulfur impurities.
  • the combination of an attached promoter catalyst system and a solvent crystallization step can provide products having high purity levels and that are suitable for use in the manufacture of food contact grade materials and materials for demanding optical applications.
  • BPA produced using the methods of the present invention can be utilized in the manufacture of food-grade polycarbonate products.
  • BPA synthesized using the methods of the present invention can be useful in producing polycarbonate having enhanced optical properties as compared to a conventional polycarbonate produced from a conventional BPA material.
  • BPA prepared from the methods of the present invention can produce a polycarbonate having good impact strength (ductility).
  • Conventional polycarbonates can age upon exposure to heat, light, and/or over time, resulting in reduced light transmission and color changes within the material
  • the methods described herein can provide a BPA having less than about 10 ppm, less than about 5 ppm, less than about 4 ppm, less than about 3 ppm, less than about 2 ppm, or less than about 1 ppm sulfur, for example, as measured by combustion and/or coulometric methods.
  • the methods described herein can provide a BPA having less than about 2 ppm sulfur.
  • the methods described herein can provide a BPA that is free of or substantially free of sulfur.
  • the improved purity, for example, reduced sulfur and organic contaminants, of BPA produced using the methods described herein can result in polycarbonate materials having improved color properties.
  • polycarbonate produced from BPA prepared by the methods of the present disclosure can exhibit reduced color, for example, yellowness, as compared to conventional polycarbonate materials, even after aging at elevated temperatures.
  • a polycarbonate produced from BPA prepared by the methods of the present disclosure can exhibit surprisingly low color after aging for 2,000 hours at about 130 °C.
  • the BPA produced by the methods described herein, or a polycarbonate, for example, a BPA polycarbonate, prepared therefrom can comprise less than or equal to about 150 ppm of free hydroxyl groups, for example, about 150, 125, 100, 75, 50 ppm, or less free hydroxyl groups.
  • the yellowness index (YI), as measured by ASTM D1925, of a 2.5 mm thick polycarbonate plaque formed from a bisphenol-A monomer using the methods of the present disclosure can be less than about 1.6, for example, less than about 1.6, less than about 1.5, less than about 1.4, or less than about 1.3.
  • a 2.5 mm thick polycarbonate plaque can have a yellowness index of less than about 1.5.
  • a 2.5 mm thick polycarbonate plaque can have a yellowness index of less than about 1.3.
  • the yellowness index (YI), as measured by ASTM D1925, of a 2.5 mm thick polycarbonate plaque formed from a bisphenol-A monomer using the methods of the present disclosure, , after heat aging for 2,000 hours at about 130 °C, can be less than about 10, for example, less than about 10, less than about 9, less than about 8, less than about 7, less than about 6, or less than about 5.
  • the yellowness index of a 2.5 mm thick polycarbonate plaque, after heat-aging can be less than about 10.
  • the yellowness index of a 2.5 mm thick polycarbonate plaque, after heat-aging can be less than about 7.
  • the yellowness index of a 2.5 mm thick polycarbonate plaque, after heat-aging can be less than about 5.
  • the yellowness index of a 2.5 mm thick polycarbonate plaque, after heat-aging can be less than about 2.
  • BPA polycarbonate produced from the methods described herein can have a purity level suitable for use in optical applications requiring high transmission and low color, wherein the BPA polycarbonate is manufactured from bisphenol- A prepared by contacting at least two chemical reagents with an attached promoter ion exchange resin catalyst system to produce an effluent, and then subjecting the effluent to a solvent crystallization step.
  • BPA polycarbonate manufactured from bisphenol-A prepared by the methods described herein can have a transmission of at least about 90 %, for example, about 90 %, 92 %, 94 %, 96 %, 98 %, or more, at a thickness of 2.5 mm, as measured by ASTM D1003-00.
  • a BPA polycarbonate, as described herein can have no or substantially no sulfur impurities.
  • a BPA polycarbonate, as described herein can have an organic purity of at least about 99.5 %.
  • a BPA polycarbonate, as described herein can have less than or equal to about 150 ppm free hydroxyl groups.
  • a BPA polycarbonate, as described herein can have a sulfur concentration of less than about 5 ppm or less than about 2 ppm.
  • the invention can comprise an article comprising a BPA polycarbonate, for example, a polycarbonate manufactured from BPA produced by the methods described herein.
  • a BPA polycarbonate for example, a polycarbonate manufactured from BPA produced by the methods described herein.
  • such an article can be selected from at least one of the following: a light guide, a light guide panel, a lens, a cover, a sheet, a bulb, and a film.
  • the article can comprise a LED lens.
  • the article can comprise at least one of the following: a portion of a roof, a portion of a greenhouse, and a portion of a veranda.
  • BPA prepared by the methods described herein can be used to produce polycarbonate resins and/or polycarbonate copolymer materials, for example a polyester-polycarbonate copolymer, a polysiloxane-polycarbonate copolymer, an alkylene terephthalate -polycarbonate copolymer, or a combination thereof.
  • BPA prepared by the methods described herein can be used to produce other polycarbonate copolymers not specifically recited herein, and the present invention is not intended to be limited to any particular polycarbonate and/or polycarbonate copolymer material.
  • the bisphenol-A, polycarbonate, and article of the present disclosure can comprise any combination of components, purities, and properties described herein, including various aspects wherein any individual component, purity, and/or property, such as, for example, sulfur level, yellowness index, organic purity, and/or transmission can be either included or excluded from the composition.
  • any individual component, purity, and/or property such as, for example, sulfur level, yellowness index, organic purity, and/or transmission can be either included or excluded from the composition.
  • combinations wherein comprising any one or more components, purities, and/or properties, but excluding other components, purities, and/or properties recited herein are contemplated.
  • a bisphenol-A monomer has an organic purity of at least about 99.5 wt.% and a sulfur concentration of less than about 5 ppm, wherein when formed into a polycarbonate resin and molded into a 2.5 mm plaque, exhibits a color (YI) of less than about 1.5.
  • a BPA polycarbonate has a purity level suitable for use in optical applications requiring high transmission and low color, wherein the BPA polycarbonate is manufactured from bisphenol-A prepared by contacting at least two chemical reagents with an attached promoter ion exchange resin catalyst system to produce an effluent, and then subjecting the effluent to a solvent crystallization step
  • the bisphenol-A monomer has a sulfur concentration of less than about 2 ppm; and/or (ii) the bisphenol-A monomer, when formed into a polycarbonate resin and molded into a 2.5 mm plaque, exhibits a yellowness index (YI) of less than about 1.3, as measured by ASTM D1925; and/or (iii) the bisphenol-A monomer, when formed into a polycarbonate resin and molded into a 2.5 mm plaque, exhibits a yellowness index (YI), as measured by ASTM D1925, of less than about 10 after heat aging for 2,000 hours at about 130 °C; and/or (iv) the bisphenol-A monomer, when formed into a polycarbonate resin and molded into a 2.5 mm plaque, exhibits a yellowness index, as measured by ASTM D1925, (YI) of less than about 7 after heat aging for 2,000 hours at about 130 °C; and/or (v) the
  • polycarbonate or copolymer has a yellowness index (YI) of less than about 1.3, as measured by ASTM D1925, when formed into a 2.5 mm thick plaque; and/or (x) the polycarbonate or copolymer has a yellowness index (YI) of less than about 10, as measured by ASTM Dl 925, when formed into a 2.5 mm thick plaque and heat aged for 2,000 hours at about 130 °C; and/or (xi) the polycarbonate has no or substantially no sulfur impurities; and/or (xii) the polycarbonate has an organic purity of at least about 99.5 %; and/or (xiii) the polycarbonate has less than or equal to about 150 ppm free hydroxyl groups; and/or (xiv) the polycarbonate has a transmission of at least about 90 % at 2.5 mm thickness, as measured by ASTM D1003-00; and/or (xv) the polycarbonate has a sulfur level of less than about 5 ppm; and/or (x
  • the article is selected from at least one of the following: a light guide, a light guide panel, a lens, a cover, a sheet, a bulb, and a film; and/or (xxviii) the article is a LED lens; and/or (xxix) the article comprises at least one of the following: a portion of a roof, a portion of a greenhouse, and a portion of a veranda.
  • phenol and acetone are each fed to a reactor, where they are subsequently mixed using a static mixer.
  • the reactor feeds are cooled using a plate heat exchanger before reaching the reactor vessel.
  • a bed of ion exchange resin having an attached promoter (2 % cross-linked ion exchange resin catalyst with DMT attached promoter) is disposed in the reactor such that the reactor feeds flow through the reactor in a downward fashion. Conversion of acetone in the reactor is designed to be at least about 90 %, with a ⁇ , ⁇ -BPA selective of at least about 93 %.
  • the effluent stream is transferred to a separate vessel, where it passes through a bed of anion exchange resin to remove any free oligomer.
  • the effluent is then subjected to a water removal step.
  • the dehydrated effluent stream is subjected to a phenol recovery step where a phenol flash column is used to remove phenol remaining in the effluent stream.
  • the solvent crystallization unit can remove all or substantially all of the BPA byproducts.
  • the remaining effluent stream can then be treated in a solvent recovery system to remove the aromatic solvent(s), such as toluene.
  • the toluene or other aromatic solvent is thus separated from the BPA isomer stream.
  • BPA samples from different sources were used to produce polycarbonate resins.
  • the polycarbonate resins were produced in a single production facility using an interfacial polymerization process. Molded plaques were then prepared from polycarbonate resin stabilized with 0.05 wt.% IRGAFOS® 168 trisarylphosphite processing stabilizer.
  • each 2.5 mm plaque was determined, according to ASTM D1925, after molding (YI0), as well as after heat aging for 2,000 hours at 130 °C (YI,2000hrs 130C). Table 1, below illustrates the color, purity, and sulfur concentration for each sample.
  • Samples prepared prepared using BPA from a production process using hydrochloric acid as a catalyst are identified as "HCl” in the BPA process column.
  • Samples prepared using BPA from the inventive attached promoter methods described herein are identified as "AP" in the BPA process column.
  • the BPA prepared using conventional bulk promoter systems has about 20 ppm sulfur, even after purification of the monomer.
  • the BPA prepared using HCl exhibited a sulfur level of less than about 2 ppm.
  • the BPA prepared from the attached prompter systems described herein exhibited less than about 2 ppm sulfur (i.e., a level below the detection limit of the measurement equipment).
  • polycarbonate resins produced from BPA prepared by the attached promoter methods of the present disclosure exhibited significantly less yellowing, as compared to polycarbonate resins produced from HC1 and conventional bulk promoter (BP) BPA.
  • BPA prepared from HC1 can exhibit good purity and low sulfur levels, the polycarbonate that is made from it does not have the reduced yellowing benefit as the polycarbonate that is obtained from BPA prepared with the attached promoter methods described in the present disclosure.
  • BPA prepared from conventional bulk promoter (BP) systems exhibits both higher sulfur content and yellowing (in the derived polycarbonate), as compared to BPA prepared with the attached promoter methods of the present disclosure.
  • FIGS. 3 and 4 Plots of BPA purity versus color (i.e., yellowing) for as-molded plaques and for heat-aged plaques, are illustrated in FIGS. 3 and 4.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

Cette invention concerne des procédés de mise en œuvre d'une réaction de condensation. Plus spécifiquement, divers procédés de production de bisphénol A très pur sont décrits, lesdits procédés consistant à combiner un système de catalyseur de type résine échangeuse d'ions lié à un promoteur avec une étape de cristallisation par solvant.
EP12722886.4A 2011-05-02 2012-05-02 Bisphénol a de grande pureté et matériaux de type polycarbonate préparés à partir de celui-ci Withdrawn EP2705016A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US13/099,032 US20120283485A1 (en) 2011-05-02 2011-05-02 Robust promoter catalyst system
US13/099,026 US8735634B2 (en) 2011-05-02 2011-05-02 Promoter catalyst system with solvent purification
US201261618351P 2012-03-30 2012-03-30
PCT/IB2012/052198 WO2012150559A1 (fr) 2011-05-02 2012-05-02 Bisphénol a de grande pureté et matériaux de type polycarbonate préparés à partir de celui-ci

Publications (1)

Publication Number Publication Date
EP2705016A1 true EP2705016A1 (fr) 2014-03-12

Family

ID=46147546

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12722886.4A Withdrawn EP2705016A1 (fr) 2011-05-02 2012-05-02 Bisphénol a de grande pureté et matériaux de type polycarbonate préparés à partir de celui-ci

Country Status (4)

Country Link
EP (1) EP2705016A1 (fr)
KR (1) KR20140043362A (fr)
CN (1) CN103502192A (fr)
WO (1) WO2012150559A1 (fr)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8735634B2 (en) * 2011-05-02 2014-05-27 Sabic Innovative Plastics Ip B.V. Promoter catalyst system with solvent purification
US9290618B2 (en) 2011-08-05 2016-03-22 Sabic Global Technologies B.V. Polycarbonate compositions having enhanced optical properties, methods of making and articles comprising the polycarbonate compositions
US8962117B2 (en) 2011-10-27 2015-02-24 Sabic Global Technologies B.V. Process for producing bisphenol A with reduced sulfur content, polycarbonate made from the bisphenol A, and containers formed from the polycarbonate
CN104205376B (zh) 2012-02-03 2018-04-27 沙特基础全球技术有限公司 发光二极管器件及用于生产其的包括转换材料化学的方法
CN104144902A (zh) 2012-02-29 2014-11-12 沙特基础创新塑料Ip私人有限责任公司 用于生产低硫双酚a的方法、用于生产聚碳酸酯的方法以及由聚碳酸酯制作的制品
EP2820106B1 (fr) * 2012-02-29 2017-11-22 SABIC Global Technologies B.V. Compositions de polycarbonate contenant la chimie des conversions de matériau et possédant des propriétés optiques améliorées, procédés de fabrication et articles les comprenant
US9346949B2 (en) 2013-02-12 2016-05-24 Sabic Global Technologies B.V. High reflectance polycarbonate
US9821523B2 (en) 2012-10-25 2017-11-21 Sabic Global Technologies B.V. Light emitting diode devices, method of manufacture, uses thereof
WO2014186548A1 (fr) 2013-05-16 2014-11-20 Sabic Innovative Plastics Ip B.V. Compositions de polycarbonate ramifié présentant des propriétés chimiques d'un matériau de conversion, et articles associés
US9006378B2 (en) 2013-05-29 2015-04-14 Sabic Global Technologies B.V. Color stable thermoplastic composition
EP3004234B1 (fr) 2013-05-29 2021-08-18 SABIC Global Technologies B.V. Dispositifs d'éclairage ayant des articles thermoplastiques, transmettant de la lumière, de couleur stable
US10005709B2 (en) 2016-05-10 2018-06-26 Sabic Global Technologies B.V. Method for producing a Bisphenol
US20190203043A1 (en) * 2016-05-27 2019-07-04 Sabic Global Technologies B.V. Copolycarbonate lenses, methods of manufacture, and applications thereof
US10723877B2 (en) 2016-05-27 2020-07-28 Sabic Global Technologies B.V. Copolycarbonate lenses, methods of manufacture, and applications thereof
CN109415534B (zh) 2016-07-25 2020-11-10 沙特基础工业全球技术有限公司 具有增强的光学性质的聚碳酸酯组合物、由其形成的制品和制造方法
CN111848956B (zh) * 2019-04-30 2022-03-11 万华化学集团股份有限公司 一种端基为酚基的聚硅氧烷及其制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08319248A (ja) * 1995-05-23 1996-12-03 Mitsubishi Chem Corp ビスフェノールａの製造方法
DE102004005723A1 (de) * 2004-02-05 2005-08-25 Bayer Materialscience Ag Herstellung von Bisphenol A mit verringertem Schwefelgehalt
PL210812B1 (pl) * 2007-02-14 2012-03-30 Inst Ciężkiej Syntezy Organicznej Blachownia Sposób otrzymywania bisfenolu A

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2012150559A1 *

Also Published As

Publication number Publication date
WO2012150559A1 (fr) 2012-11-08
CN103502192A (zh) 2014-01-08
KR20140043362A (ko) 2014-04-09

Similar Documents

Publication Publication Date Title
EP2705016A1 (fr) Bisphénol a de grande pureté et matériaux de type polycarbonate préparés à partir de celui-ci
US20140051802A1 (en) High purity bisphenol-a and polycarbonate materials prepared therefrom
EP2705017A1 (fr) Bisphénol a de grande pureté et matériaux de type polycarbonate préparés à partir de celui-ci
US20140051803A1 (en) High purity bisphenol-a and polycarbonate materials prepared therefrom
EP2707418B1 (fr) Copolymères élastomères de polycarbonate de silicone
ES2751459T3 (es) Preparación de copolicarbonatos de bloques que contienen siloxano por medio de extrusión reactiva
CN105612196A (zh) 使用弱酸的盐制备聚硅氧烷-聚碳酸酯嵌段共缩合物的方法
KR101289201B1 (ko) 에스테르 결합을 갖는 히드록시 말단 실록산, 폴리실록산-폴리카보네이트 공중합체 및 그 제조 방법
KR102270558B1 (ko) 개선된 레올로지 특성을 갖는 폴리실록산-폴리카르보네이트 블록 공축합물
EP2970653B1 (fr) Mélange de poly(téréphtalate de butylène), polycarbonate-polydiorganosiloxane et polyestercarbonate renforcé et article le comprenant
EP3099743B1 (fr) Compositions de moulage en polycarbonate/polyester thermoplastique ignifuges sans halogène à base d'un agent ignifuge phosphoré polymère
TWI649354B (zh) 聚矽氧烷-聚碳酸酯嵌段共縮合物
KR102257686B1 (ko) 폴리실록산-폴리카보네이트 블록 공축합물의 제조 방법
EP2342281A1 (fr) Composition polymère thermoplastique retardatrice de flamme, procédé de fabrication et article formé à partir de celle-ci
KR20170045092A (ko) 투명성 및 난연성이 향상된 폴리실록산-폴리카보네이트 공중합체 및 그 제조방법
CN110072918B (zh) 借助相容剂制造含硅氧烷的嵌段共聚碳酸酯
AU2016213893A1 (en) Microfluidic Device and Microwell Made From a Polyester-Polycarbonate
KR20110021630A (ko) 우레탄 결합을 갖는 히드록시 말단 실록산, 폴리실록산-폴리카보네이트 공중합체 및 그 제조 방법
CN113614176A (zh) 具有小的畴尺寸的含硅氧烷的嵌段共聚碳酸酯
KR102115799B1 (ko) 투명성 및 저온 내충격성이 향상된 폴리실록산-폴리카보네이트 공중합체 및 그 제조방법
WO2013120275A1 (fr) Article transparent à parois minces résistant à la rayure
WO2023166427A1 (fr) Compositions transparentes de polycarbonates

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20131129

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: SABIC GLOBAL TECHNOLOGIES B.V.

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20161201