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EP2705017A1 - 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
EP2705017A1
EP2705017A1 EP12722887.2A EP12722887A EP2705017A1 EP 2705017 A1 EP2705017 A1 EP 2705017A1 EP 12722887 A EP12722887 A EP 12722887A EP 2705017 A1 EP2705017 A1 EP 2705017A1
Authority
EP
European Patent Office
Prior art keywords
polycarbonate
copolymer
bisphenol
less
bpa
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Withdrawn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
EP12722887.2A
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 US13/099,026 external-priority patent/US8735634B2/en
Priority claimed from US13/099,032 external-priority patent/US20120283485A1/en
Application filed by SABIC Innovative Plastics IP BV filed Critical SABIC Innovative Plastics IP BV
Publication of EP2705017A1 publication Critical patent/EP2705017A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • 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
    • C08G64/18—Block or graft polymers
    • C08G64/186—Block or graft polymers containing polysiloxane sequences
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the present disclosure relates to catalyst systems, and specifically to promoter ion exchange resin catalyst systems and the products derived from them.
  • 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 portion of the catalyst system.
  • Existing attached promoter systems can be susceptible to reactant impurities.
  • hydroxyacetone (HA) and methanol can be present in phenol and acetone reactants, respectively.
  • impurities such as HA and methanol
  • Such attached promoter systems can also be susceptible to impurities in recycle feeds of reaction processes, reducing the lifetime and performance 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 catalyst system comprising a cross-linked, sulfonated ion exchange resin catalyst and a dimethyl thiazolidine promoter.
  • the present disclosure provides a catalyst system comprising a cross-linked, sulfonated ion exchange resin catalyst and a dimethyl thiazolidine promoter, wherein the cross-linked,sulfonated ion exchange resin comprises a plurality of sulfonic acid groups and has a degree of cross-linking of from about 1 % to about 4 %.
  • the present disclosure provides a catalyst system comprising a cross-linked, sulfonated ion exchange resin catalyst and a dimethyl thiazolidine promoter, wherein the dimethyl thiazolidine promoter is at least partially bound to the cross- linked, sulfonated ion exchange resin.
  • the present disclosure provides a catalyst system comprising a cross-linked, sulfonated ion exchange resin catalyst and a dimethyl thiazolidine promoter, wherein the dimethyl thiazolidine promoter is bound to from about 18 % to about 25 % of the sulfonic acid groups of the cross-linked, sulfonated ion exchange resin.
  • the present disclosure provides an attached promoter catalyst system comprising an ion exchange resin and a dimethyl thiazolidine promoter, wherein the catalyst system is more resistant to hydroxyacetone than a conventional bulk promoter system.
  • the present disclosure provides a method for catalyzing a condensation reaction, the method comprising contacting two or more reactants with a modified ion exchange resin catalyst in the absence of a bulk promoter.
  • the present disclosure provides a method for catalyzing a condensation reaction, the method comprising contacting two or more reactants with a modified ion exchange resin catalyst in the absence of a bulk promoter, wherein the modified ion exchange resin catalyst comprises a cross-linked, sulfonated ion exchange resin.
  • the present disclosure provides a method for catalyzing a condensation reaction, the method comprising contacting two or more reactants with a modified ion exchange resin catalyst in the absence of a bulk promoter, wherein the modified ion exchange resin catalyst comprises an attached dimethyl thiazolidine promoter.
  • the present disclosure provides a method for the production of bisphenol-A, the method comprising contact a phenol and at least one of a ketone, an aldehyde, or a combination thereof in the presence of an attached ion exchange resin catalyst comprising a dimethyl thiazolidine promoter, wherein the method does not comprise a pretreatment and/or purification step for the phenol, ketone, and/or aldehyde.
  • FIG. 1 illustrates a comparison of ⁇ , ⁇ -BPA formation using an inventive catalyst, both with and without hydroxyacetone present.
  • FIG. 2 represents data from a methanol spiking experiment with the inventive catalyst system, illustrating the formation of ⁇ , ⁇ -BPA over time in the presence of methanol.
  • FIG. 3 represents data from a methanol spiking experiment with the inventive catalyst system, illustrating catalyst selectivity over time in the presence of methanol.
  • FIG. 4 represents data from a methanol spiking experiment with the inventive catalyst system, illustrating catalyst selectivity vs. methanol concentration.
  • FIG. 5 represents data from a methanol spiking experiment with the inventive catalyst system, illustrating ⁇ , ⁇ -BPA formation in the presence of varying methanol concentration.
  • FIG. 6 illustrates the yellowness index in a plastic 2.5mm color chip directly after molding as a function of monomer synthesis catalyst & promotor system.
  • FIG. 7 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 & promotor system.
  • FIG. 8 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 & promotor system.
  • FIG. 9 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 & promotor 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. For example, if the value "10” is disclosed, then “about 10" is also disclosed. It is also understood that each unit between two particular units are also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.
  • 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.
  • 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.
  • R can be hydrogen, an alkyl, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or heterocycloalkyl group described above.
  • 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)
  • a bridging group having one or more atoms that separate A from A .
  • one atom is
  • each R can be derived from a dihydroxy aromatic compound of formula 3)
  • R a and R b are each independently a halogen, Ci_i2 alkoxy, or Ci_i2 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 C S 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 Ci_is organic group can be disposed such that the e arylene groups connected thereto are each connected to a common alkylidene carbon or to different carbons of the Ci_is 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_i 8 alkylene group, a C 3 _i 8 cycloalkylene group, a
  • 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, Cy.u alkyl, C1 2 alkoxy, or C1 2 acyl;
  • r is 0 to 2, t is 1 or 2, q is 0 or 1, and k is 0 to 3, with the proviso that at least two of 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 , 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 groups.
  • R a , R , 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 groups.
  • 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”) (also known as 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-l-one).
  • 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 Cuo alkyl, or benzyl optionally substituted with 1 to 5 Cno 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_is cycloalkylidene include the cyclohexylidene- bridged, alkyl-substituted bisphenol of formula (4e)
  • R a and R b are each independently Ci_i2 alkyl, R s is Ci_i2 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.
  • 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. In a specific aspect, at least one of each of R a and R b are disposed meta to the
  • R a and R b are each independently C1-3 alkyl, and p and q are each 0 or 1. In another specific aspect, 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.
  • R h is independently a halogen atom, a Ci_io hydrocarbyl such as a Ci_io alkyl group, a halogen-substituted Ci_io alkyl group, a C6-10 aryl group, or a halogen-substituted e- 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)cyclohe
  • hydroquinone or the like, or combinations comprising at least one of the foregoing dihydroxy compounds.
  • bisphenol compounds of formula (3) 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, 2-phenyl-3,3-bis(4-hydroxyphenyl) phthalimidine (PPPBP), and l,l-bis(4-hydroxy-3-methylphenyl)cyclohexane
  • BPA 2,2-
  • 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 C 2 -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 C 2 -10 alkylene, a C -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 C 2 -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 C 2 -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.
  • 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.
  • the 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- l,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 a specific example is poly(l,4-cyclohexane- dimethanol-l,4-cyclohexanedicarboxylate) (PCCD), having recurring units of formula (7) wherein, as described using formula (6), J is a 1 ,4-cyclohexanedimethylene group derived from 1 ,4-cyclohexanedimethanol, and 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.
  • the polydiorganosiloxane (also referred to herein as "polysiloxane") blocks of the copolymer comprise repeating
  • each R is independently a C1 3 monovalent organic group.
  • R can be a C1-C13 alkyl, C1-C13 alkoxy, C2-C13 alkenyl group, C2-C13 alkenyloxy, C3-C6 cycloalkyl, C3- (, cycloalkoxy, C6-C14 aryl, C6-C10 aryloxy, C7-C13 arylalkyl, C7-C13 aralkoxy, C7-C13 alkylaryl, or C7-C13 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.
  • 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-C30 arylene group, wherein the bonds are directly connected to an aromatic moiety.
  • Ar groups in formula (9) can be derived from a C6-C30 dihydroxyarylene compound, for example a
  • 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 of the foregoing dihydroxy compounds can also be used.
  • polydiorganosiloxane blocks are of formula (10)
  • the polydiorganosiloxane blocks are of formula (11): (11) wherein R and E are as defined above.
  • R in formula (11) is a divalent C 2 -C 8 aliphatic group.
  • Each M in formula (11) can be the same or different, and can be a halogen, cyano, nitro, Ci- C8 alkylthio, d-Cs alkyl, Ci-Cs alkoxy, C 2 -C8 alkenyl, C 2 -C8 alkenyloxy group, C3-C8 cycloalkyl, C 3 -C 8 cycloalkoxy, C6-C1 0 aryl, C6-C1 0 aryloxy, C 7 -C1 2 aralkyl, C 7 -C1 2 aralkoxy, C7-C1 2 alkylaryl, or C7-C1 2 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-C 3 aliphatic group
  • R is methyl.
  • Blocks of formula (11) can be derived from the corresponding dihydroxy polydiorganosiloxane (12)
  • I ddiihh)y ⁇ droxy polysiloxanes can be made by effecting a platinum-catalyzed addition between a siloxane hydride of formula (13) wherein 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 poly organosiloxane -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
  • 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 (BPA).
  • BPA can be synthesized by the acid catalyzed condensation of phenol and acetone using either an HC1 catalyst or a sulphonated ion exchange resin (IER) catalyst. Due to the inherent low number of acid sites on conventional ion exchange resins, IER processes typically incorporate a promoter system to improve reaction rates.
  • Promoter systems can be bulk, wherein the promoter species is disposed in the reaction medium, or attached, wherein the promoter species is attached to another portion of the catalyst system.
  • a conventional IER based process utilizes 3-mercaptopropionic acid (3-MPA) as a bulk promoter. While bulk promoters can improve the reaction rate, they require recovery of the promoter species and typically do not provide a high degree of selectivity.
  • 3-MPA promoter can provide a wide range of BPA isomers. Specifically, 3-MPA based systems can result in the production of a significant quantity of o,p-BPA, as opposed to more desirable ⁇ , ⁇ -BPA. As such, separate isomerization reactions can be necessary to convert ⁇ , ⁇ -BPA to the more desirable p,p-BPA.
  • promoter systems can be attached, wherein the promoter is attached to portion of the catalyst system, such as the ion exchange resin.
  • An exemplary attached promoter system utilizes a pyridyl ethylmercapton (PEM) promoter.
  • PEM pyridyl ethylmercapton
  • Conventional attached promoter catalyst systems such as a PEM based system, can be sensitive to impurities in reactant and recycle streams. For example, in the production of BPA, phenol and acetone reactants can contain impurities such as hydroxyacetone (HA) and methanol, respectively. These impurities can deactivate the catalyst system, resulting in slower reaction rates and shorter catalyst lifetimes.
  • 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.
  • BPA produced by the methods described herein can can exhibit low levels of organic impurities.
  • 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 promoter catalyst system that is more selective than conventional promoter catalyst systems.
  • the present disclosure provides a manufacturing process and catalyst system for the production of BPA that can selectively produce ⁇ , ⁇ -BPA without necessitating additional isomerizations reactions.
  • the present disclosure provides a promoter catalyst system that can tolerate impurities, such as hydroxyacetone and methanol, in reactant and/or recycle streams.
  • 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, 4- hydroxyacetophenone, acenaphthenequinone, quinone, benzoylacetone and diacetyl are representative examples.
  • a ketone having halo, nitrile or nitro substituents can also be used, for example, 1,3-dichlor
  • 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 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,
  • the degree of cross-linking can be less than 1 percent or greater than 4 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 present invention comprises dimethyl thiazolidine (DMT).
  • DMT dimethyl thiazolidine
  • the promoter of the present invention can comprise derivatives and/or analogues of dimethyl thiazolidine.
  • the promoter of the present invention can be represented by the formula:
  • 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 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 can thus neutralize 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.
  • both phenol and acetone reactants can contain impurities, such as hydroxyacetone (HA) and methanol, respectively. These reactants can interfere with and/or deactivate catalyst systems, resulting in shortened catalyst lifetimes and/or decreased reaction rates.
  • a conventional approach to prevent such deactivation is to subject the reactants to a pretreatment step, such as an adsorption bed, to remove the impurities.
  • the DMT attached promoter catalyst system of the present invention can tolerate phenol and alcohol impurities without reducing the lifetime of the catalyst system.
  • the DMT attached promoter catalyst system can tolerate other impurities detrimental to conventional catalyst systems.
  • the DMT attached promoter catalyst system can provide performance equivalent to or greater than that of conventional bulk promoter systems.
  • the DMT catalyst system can exhibit no significant change in catalyst activity level after exposure to HA.
  • the DMT catalyst system can eliminate the need for separate purification and/or pretreatment steps.
  • a manufacturing process using the DMT catalyst system can require a reduced level of pretreatment and/or purification of reactants.
  • a bisphenol manufacturing process can utilize phenol and acetone reactants as received, without the need for a pretreatment step.
  • the lifetime of a DMT promoter catalyst system, after exposed to HA and/or methanol, can be longer than that for conventional bulk or attached promoter catalyst systems.
  • the DMT catalyst system can tolerate a greater amount of hydroxyacetone than a comparative PEM catalyst system.
  • the DMT catalyst system upon exposure to about 10 ppm hydroxyacetone, can maintain at least about 60, at least about 65, at least about 70, at least about 75, or at least about 80 % of its initial performance after 200 hours of operation, in terms of the amount of ⁇ , ⁇ -BPA produced.
  • the DMT catalyst system upon exposure to about 10 ppm hydroxyacetone, can maintain at least about 10, at least about 15, at least about 20, or at least about 25 % of its initial performance after 500 hours of operation, in terms of the amount of p,p-BPA produced.
  • the DMT catalyst system can be more resistant to deactivation than other catalyst systems.
  • the DMT catalyst system can substantially maintain its acid strength after 100 hours of operation under 20 ppm of hydroxyacetone.
  • the acid strength (meq/g) of the DMT catalyst system, after 100 hours of exposure to 20 ppm hydroxyacetone is within 10 %, within 8 %, within 6 %, within 4 %, or within 2 % of the acid strength for a DMT catalyst system not exposed to hydroxyacetone.
  • the acid strength of the DMT catalyst system, after 100 hours of exposure to 20 ppm hydroxyacetone is within 5 % of the acid strength for a DMT catalyst system not exposed to hydroxyacetone.
  • the DMT catalyst system can tolerate exposure to alcohols, such as methanol, with substantially no change in performance.
  • the DMT catalyst system can tolerate up to about 100 ppm, up to about 250 ppm, up to about 500 ppm, up to about 1,000 ppm, up to about 1,500 ppm, up to about 2,000 ppm, up to about 2,500 ppm, up to about 3,000 ppm, up to about 4,000 ppm, up to about 5,000 ppm, up to about 6,000, or more of methanol with no or substantially no detectable decrease in performance.
  • the DMT catalyst system can maintain a production rate of ⁇ , ⁇ -BPA upon exposure to up to about 3,000 ppm methanol. In other aspects, exposure to methanol at each of the concentrations recited above, does not result in any significant change in the selectivity of the DMT catalyst system.
  • the DMT attached promoter catalyst system of the present invention can tolerate recycle stream containinglO to 14 wt % of p,p-BPA, 2 to 4 wt % of o,p-BPA, and 4 to 8 wt % of other BPA impurities, without reducing the lifetime of the catalyst system.
  • the DMT attached promoter catalyst system can tolerate other impurities detrimental to conventional catalyst systems.
  • the DMT attached promoter catalyst system can provide performance equivalent to or greater than that of conventional bulk promoter systems.
  • the DMT promoter catalyst system can prevent the need for a separate purification step for process recycle streams.
  • the DMT catalyst system when using a recycled phenol stream, can provide levels of ⁇ , ⁇ -BPA that are within about 10 %, within about 8 %, within about 6 %, within about 4 %, or within about 2 % of values obtained using a fresh phenol stream. In a specific aspect, when using a recycled phenol stream, the DMT catalyst system can provide levels of ⁇ , ⁇ -BPA that are within about 5 % of values obtained using a fresh phenol stream. [0135] Thus, in various aspects, the DMT catalyst system can tolerate recycle stream impurities with no significant degradation in catalyst performance.
  • Bulk promoter systems typically provide a ⁇ , ⁇ / ⁇ , ⁇ -BPA ratio of 10 to 15.
  • the DMT catalyst system can exhibit a higher ⁇ , ⁇ -BPA to ⁇ , ⁇ -BPA ratio than a conventional bulk promoter system.
  • the p,p/o,p ratio for the DMT catalyst system can be at least about twice that for conventional bulk promoter systems.
  • a DMT catalyst system can exhibit a p,p/o,p BPA ratio of at least about 20, at least about 30, at least about 40, at least about 50, at least about 60, or more.
  • a DMT catalyst system can exhibit a ⁇ , ⁇ / ⁇ , ⁇ -BPA ratio of at least about 25, for example, about 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 40, or more.
  • a DMT catalyst system (22 % attachment) can exhibit a ⁇ , ⁇ / ⁇ , ⁇ -BPA ratio of from about 25 to about 35.
  • the improved selectivity of the DMT catalyst system can eliminate the need for a separate isomerization process.
  • the inventive DMT catalyst system can provide simplified methods for catalyzing condensation reactions.
  • the present invention provides a process for catalyzing a condensation reaction that utilizes a modified ion exchange resin catalyst having an attached dimethyl thiazolidine promoter.
  • the present invention provides a process for catalyzing a condensation reaction that does not utilize a bulk promoter system.
  • the inventive DMT catalyst system can allow a simplified BPA manufacturing process, wherein one or more of the following are not needed: phenol pretreatment/purification step, acetone pretreatment/purification step, BPA recycle stream purification step, separate isomerization reaction, or a combination thereof.
  • a manufacturing process comprising the inventive DMT catalyst can provide an efficient, selective, longer lifetime catalyst system than conventional attached promoter catalyst systems.
  • 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.
  • BPA prepared from the methods described herein can exhibit lower levels of inorganic contaminants as compared to conventional BPA materials.
  • BPA prepared from the methods described herein can exhibit lower levels of organic contaminants as compared to conventional BPA materials.
  • BPA prepared from the methods described herein can exhibit lower levels of sulfur as compared to conventional BPA materials.
  • BPA prepared from the methods described herein can have a level of organic impurities of less than about 0.5 wt.%, for example, 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.%.
  • Conventional bulk promoter catalyst systems that utilize resin catalyst systems with sulfonic acid groups and 3MPA promotors can leave up to about 20 ppm sulfur or more in the resulting BPA, even after purification.
  • 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, inorganic contaminants, and/or 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 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 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. In another aspect, 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 is prepared by contacting a phenol and at least one of a ketone, an aldehyde, or a combination thereof in the presence of an attached ion exchange resin catalyst comprising a dimethyl thiazolidine promoter, wherein the method does not comprise a pretreatment and/or purification step for the phenol, ketone, and/or aldehydebisphenol.
  • the bisphenol-A has no or substantially no inorganic impurities; and/or (ii) the bisphenol-A has no or substantially no sulfur impurities; and/or (iii) the bisphenol-A has a sulfur concentration of less than about 2 ppm; and/or (iv) the bisphenol A, 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 1.3; and/or (v) the bisphenol-A, 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 (vi) the bisphenol-A, when formed into a polycarbonate resin and molded into a 2.5 mm plaque, exhibits a yellowness index (YI),
  • a single column reactor was utilized to determine the inventive catalyst system's tolerance for hydroxyacetone (HA) impurities.
  • Parallel reactions were performed: one with 20 ppm HA present in the phenol reactant, the other without HA in the phenol reactant. Reactions were carried out at 75 ° C, for 100 hours, using 7.5 wt.% acetone, and at WHSV of 20.
  • the ion exchange resin utilized was Lanxess K1221 SH, modified to a level of 20 % with the inventive DMT promoter.
  • FIG. 2 illustrates the amount of ⁇ , ⁇ -BPA produced as the column was spiked with methanol (550 ppm, 3157 ppm, and 110 ppm).
  • methanol 550 ppm, 3157 ppm, and 110 ppm.
  • the observed deactivation profile was identical to that expected when no methanol is present.
  • the presence of methanol has no detectable effect on the performance of the catalyst system and the formation of p,p-BPA.
  • FIG. 3 illustrates the selectivity of the inventive catalyst system in the same methanol spiking experiment illustrated in FIG. 2.
  • the presence of methanol in the reaction did not have an effect on the high selectivity of the DMT catalyst towards p,p-BPA.
  • the amount of methanol present in the system was varied between 0 and 5,000 ppm.
  • the selectivity was then monitored as the concentration of methanol in the system varied.
  • the inventive DMT catalyst system exhibited virtually no change in selectivity over the varying concentration range of methanol.
  • a single column reactor was operated (WHSV 1 and 2) at 65 ° C and 75 ° C with a reactant feed of 4.5 wt.% acetone and phenol with 2% ⁇ , ⁇ -BPA.
  • the catalyst system comprised a 2% cross-linked A121 ion exchange resin with 22 % attached dimethyl thiazolidine (DMT).
  • DMT dimethyl thiazolidine
  • the DMT catalyst provides effective isomerization and selectivity for the production of ⁇ , ⁇ -BPA.
  • the DMT catalyst provided a high ratio of ⁇ , ⁇ - ⁇ / ⁇ , ⁇ -BPA and a high degree of selectivity.
  • 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 polycarbonate plaque was determined after molding (YD, as well as after heat aging for 2,000 hours at 130 °C (YI,2000hrs 130C), according to ASTM DI925. Table 3, 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 HC1 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, it does not provide the reduced yellowing benefit obtained for 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, as compared to BPA prepared with the attached promoter methods of the present disclosure.
  • FIGS. 8 and 9 Plots of BPA purity versus color (i.e., yellowing) for as-molded plaques and for heat-aged plaques, are illustrated in FIGS. 8 and 9.

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Abstract

Cette invention concerne un catalyseur de type résine échangeuse d'ions modifié lié à un promoteur diméthylthiazolidine. Un procédé de catalyse de réactions de condensation entre des phénols et des cétones comprenant la mise en contact des réactifs avec un catalyseur de type résine échangeuse d'ions modifié lié à un promoteur diméthylthiazolidine est également décrit, ainsi qu'un procédé de catalyse de réactions de condensation entre des phénols et des cétones qui n'utilise pas de promoteur en vrac.
EP12722887.2A 2011-05-02 2012-05-02 Bisphénol a de grande pureté et matériaux de type polycarbonate préparés à partir de celui-ci Withdrawn EP2705017A1 (fr)

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US13/099,026 US8735634B2 (en) 2011-05-02 2011-05-02 Promoter catalyst system with solvent purification
US13/099,032 US20120283485A1 (en) 2011-05-02 2011-05-02 Robust promoter catalyst system
US201261618360P 2012-03-30 2012-03-30
PCT/IB2012/052199 WO2012150560A1 (fr) 2011-05-02 2012-05-02 Bisphénol a de grande pureté et matériaux de type polycarbonate préparés à partir de celui-ci

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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
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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
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