KR20140043362A - High purity bisphenol-a and polycarbonate materials prepared thereform - Google Patents

Abstract

A method of conducting a condensation reaction is disclosed. Specifically, various methods for preparing high purity bisphenol-A are disclosed, wherein the attached promoter ion exchange resin catalyst system is combined with a solvent crystallization step.

Description

HIGH PURITY BISPHENOL-A AND POLYCARBONATE MATERIALS PREPARED THEREFORM

The present application relates to catalyst systems, specifically accelerator ion exchange resin catalyst systems.

Many common condensation reactions utilize inorganic acid catalysts such as sulfuric acid or hydrochloric acid. With the use of such inorganic acid catalysts, unwanted by-products which have to be separated in the reaction system can be formed. Ion exchange resin catalyst systems may also be used, but inherent low acid concentrations may require the use of accelerators or rate accelerators.

When used as part of a catalyst system, reaction promoters can improve the reaction rate and selectivity. In the case of the condensation reaction of phenol and ketone to form bisphenol-A (BPA), it is possible to improve the selectivity to the desired para-para BPA isomer as a reaction promoter.

A reaction promoter can be used as the bulk promoter, which is present as an unattached molecule in the reaction medium, or as an attached promoter, which is attached to the acidic portion of the sulfonic acid of the catalyst system.

In the synthesis of BPA, the use of 3-mercaptopropionic acid (3-MPA) can produce significant amounts of the less preferred o, p-BPA isomers, unlike the preferred p, p-BPA isomers.

Although much effort has been made in the development and use of bulk and attached promoter systems, there remains a need for production methods and accelerator catalyst systems that can provide high purity reaction products. Thus, there is a need to address these and other shortcomings associated with existing accelerator catalyst systems. These and other needs are met by the compositions and methods of the present disclosure.

In accordance with the object (s) of the present invention, as embodied and broadly described herein, the present disclosure relates, in one aspect, to a catalyst system, and specifically to an promoter ion exchange resin catalyst system.

In one aspect, the present disclosure provides a method for a chemical condensation reaction, wherein the method comprises contacting two or more chemical reagents with an attached promoter ion exchange resin catalyst system to obtain an eluate, and then performing a solvent crystallization step with the eluate. Performing the steps.

In a second aspect, the present disclosure provides a method comprising contacting two or more chemical reagents with an attached promoter ion exchange resin catalyst system in contact with an eluent and then performing a solvent crystallization step with the eluent, wherein The attached promoter ion exchange resin catalyst system comprises a crosslinked, sulfonated ion exchange resin with sulfone groups, with a degree of cross-linking of 1% to 4%.

In a third aspect, the present disclosure provides a method comprising contacting two or more 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. Include.

In a fourth aspect, the present disclosure provides a method comprising contacting two or more chemical reagents with an attached promoter ion exchange resin catalyst system, wherein the attached promoter ion exchange resin catalyst system is present in the ion exchange resin. Promoters that ionically bind from about 18% to about 25% of sulfonic acid groups.

In a fifth aspect, the present disclosure provides a method of treating the reactor eluate with one or more of individual ion exchange resin beds, water removal steps, phenol recovery steps, or combinations thereof, prior to the solvent crystallization step.

In a sixth aspect, the present disclosure provides bisphenol A reaction products that contain no or substantially no inorganic and / or sulfur impurities.

In another aspect, the present disclosure provides an organic purity of at least about 99.5% by weight and a sulfur concentration of less than about 5 ppm and a yellowness (YI) of about 1.5 when formed of polycarbonate resin and molded into 2.5 mm plaques. It provides less than bisphenol-A monomer.

In another aspect, the present disclosure provides bisphenol-A monomers having a sulfur concentration of less than about 2 ppm.

In another aspect, the present disclosure provides bisphenol-A monomers having a yellowness (YI) of less than about 1.3 when formed from polycarbonate resin and molded into 2.5 mm plaques.

In another aspect, the present disclosure discloses a bisphenol having a yellowness (YI) of less than about 10 after heat aging at about 130 ° C. for 2,000 hours when formed from polycarbonate resin and molded into 2.5 mm plaques. -A monomer is provided.

In another aspect, the present disclosure relates to bisphenol-A monomers having a yellowness (YI) of less than about 7 after heat aging at about 130 ° C. for 2,000 hours when formed from polycarbonate resin and molded into 2.5 mm plaques. to provide.

In another aspect, the present disclosure requires high transmittance and low chromaticity, prepared by contacting two or more chemical reagents with an attached promoter ion exchange resin catalyst system to obtain an eluate, and then performing a solvent crystallization step with the eluent. And bisphenol-A having a purity level suitable for preparing polycarbonates for optical use.

In another aspect, the present disclosure provides polycarbonates prepared from bisphenol-A described herein.

The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate various aspects in conjunction with the detailed description that serves to explain the principles of the invention.
1 shows the yellowness in a plastic 2.5mm color chip immediately after molding as a function of monomer synthesis catalyst & promoter system.
FIG. 2 shows the yellowness in plastic 2.5 mm color chips as a function of monomer synthesis catalyst & promoter system after 2,000 hours of heat aging at 130 ° C. FIG.
3 shows the yellowness in a plastic 2.5 mm color chip immediately after molding as a function of monomer organic purity and monomer synthesis catalyst & promoter system.
4 shows the yellowness in a plastic 2.5 mm color chip after 2,000 hours of heat aging at 130 ° C. as a function of monomer organic purity and monomer synthesis catalyst & promoter system.

The invention may be more readily understood by reference to the following detailed description of the application and the examples included therein.

Before disclosing and describing the compounds, compositions, articles, systems, devices, and / or methods of the present invention, unless otherwise specified, they are not limited to specific synthetic methods, or unless otherwise specified, and therefore are not limited to specific reagents. It should be understood as possible. Also, the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, examples of the methods and materials are now described.

All publications mentioned herein are incorporated herein by reference in their entirety and describe the methods and / or materials in connection with those in which the publications are mentioned.

Justice

Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, examples of the methods and materials are now described.

As used in the appended claims, the singular forms “a,” “an,” and “the” include plural unless the context clearly dictates otherwise. That is, for example, "ketone" includes a mixture of two or more ketones.

A range can be expressed herein from "about" one particular value and / or "about" another particular value. In expressing such a range, another aspect includes from one particular value and / or up to another particular value. Similarly, when a value is expressed as an approximation, it will be understood that a particular value forms another aspect using the preceding expression “about”. It is also to be understood that each endpoint of the range is noted independently of the other endpoints as well as with respect to the other endpoints, and may be combined independently of the endpoints of the range expressed differently for the same property. In addition, there are many values disclosed herein, and it is understood that each value is also disclosed herein as "about" for that particular value in addition to that value itself. In addition, it is understood that each unit between two specific units is also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.

As used herein, the term “selective” or “optionally” means that a phenomenon or environment described continuously may or may not occur, and this description may include examples in which such phenomenon or environment occurs, and It includes examples that do not. For example, "optionally substituted alkyl" means that the alkyl group may be substituted or unsubstituted, and this description includes both substituted and unsubstituted alkyl groups.

Disclosed are the components used to prepare the compositions of the present invention as well as the compositions used in the methods disclosed herein. These and other materials are disclosed herein and, when incorporating combinations, subsets, interactions, and groups of these materials, are directed to the various individual and collective combinations and permutations of each of these compounds. While references may not be explicitly disclosed, each is understood to be specifically considered and described herein. For example, if a particular compound is disclosed and described and a number of modifications can be made to a number of molecules, including the compound, specific and possible combinations and permutations of each and all possible combinations for the compound and modification are specifically indicated, unless specifically indicated otherwise. Consider. That is, when an example of molecules A, B, and C class as well as molecules D, E, and F class, and combination molecules are disclosed, AD is disclosed, and even if each is not mentioned individually, each is individually and Combining the contemplated considerations globally, AE, AF, BD, BE, BF, CD, CE, and CF are considered to be disclosed. Likewise, subsets or combinations thereof are also disclosed. That is, for example, a subset of A-E, B-F, and C-E will be considered to be disclosed. This concept applies to all aspects of this application, including but not limited to steps in the methods of making and using the compositions of the present invention. Thus, where there are a variety of additional steps that can be performed, it is understood that each of these additional steps can be performed in any particular embodiment or combination of embodiments of the method of the present invention.

Reference in the detailed description and conclusive claims to parts by weight of a particular element or component in the composition or article refers to the weight relationship between the element or component and other elements or components in the composition or article, expressed in parts by weight. That is, in a compound comprising 2 parts by weight of X component and 5 parts by weight of Y component, X and Y are present in a weight ratio of 2: 5, regardless of whether additional components are included in the compound.

Weight percentages of the components are based on the total weight of the formulation or composition in which the components are included, unless specifically stated otherwise.

As used in the description and the conclusive claims, a residue of a species refers to a moiety that is the resulting product of the species in a particular reaction scheme or subsequent formulation or chemical product, wherein the moiety is actually the species. It does not matter whether it is obtained from. Thus, ethylene glycol residues in polyester refer to one or more —OCH ₂ CH ₂ O— units in the polyester, whether or not ethylene glycol is used in the preparation of the polyester. Similarly, a sebacic acid residue in a polyester, the residue is sebacic acid, or in one or more of the esters thereof and the reaction was independent of the support is obtained by creating a polyester, the polyester -CO (CH _{2) 8} CO -Refers to a moiety.

As used herein, the term "alkyl group" refers to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl, tetra Such as kosyl and the like, branched or unbranched saturated hydrocarbon groups having 1 to 24 carbon atoms. A "lower alkyl" group is an alkyl group containing from 1 to 6 carbon atoms.

As used herein, the term "alkoxy" refers to an alkyl group bonded through a single, terminal ether linking group; That is, an "alkoxy" group can be defined as -OR, wherein R is alkyl as defined above. A "lower alkoxy" group is an alkoxy group containing 1 to 6 carbon atoms.

As used herein, the term “alkenyl group” is a hydrocarbon group having 2 to 24 carbon atoms and having a structural formula comprising at least one carbon-carbon double bond. Asymmetric structures such as (AB) C═C (CD) are intended to include both E and Z isomers. This may be inferred from the structural formulas herein where asymmetric alkenes are present, or may be explicitly indicated by the binding code C.

As used herein, the term “alkynyl group” is a hydrocarbon group having 2 to 24 carbon atoms and having a structural formula that includes one or more carbon-carbon triple bonds.

As used herein, the term "aryl group" is a carbon-based aromatic group, including but not limited to benzene, naphthalene, and the like. The term "aromatic" also includes "heteroaryl groups", which are defined as aromatic groups in which one or more heteroatoms are incorporated in a ring of aromatic groups. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Aryl groups can be substituted or unsubstituted. Aryl groups may be substituted with one or more groups, including, but not limited to, alkyl, alkynyl, alkenyl, aryl, halides, nitro, amino, esters, ketones, aldehydes, hydroxy, carboxylic acids, or alkoxy.

As used herein, the term "cycloalkyl group" is a non-aromatic carbon-based ring of three or more carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. The term “heterocycloalkyl group” is a cycloalkyl group as defined above wherein at least one of the carbon atoms of the ring is substituted with a heteroatom such as but not limited to nitrogen, oxygen, sulfur, or phosphorus.

As used herein, the term “aralkyl” is an aryl group wherein an alkyl, alkynyl, or alkenyl group, as defined above, is attached to an aromatic group. One example of an aralkyl group is a benzyl group.

As used herein, the term “hydroxyalkyl group” refers to an alkyl, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or heterocycloalkyl group, wherein one or more hydrogen atoms are substituted with hydroxyl groups.

As used herein, the term "alkoxyalkyl group" is defined as the aforementioned alkyl, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or heterocycloalkyl group, wherein at least one hydrogen atom is substituted with the alkoxy group described above. .

As used herein, the term “ester” is represented by the formula —C (O) OA, wherein A is alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclo Alkyl, or heterocycloalkenyl groups.

As used herein, the term “carbonate group” is represented by the formula —OC (O) OR, wherein R is hydrogen, alkyl, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or It may be a heterocycloalkyl group.

As used herein, the term "carboxylic acid" is represented by the formula -C (O) OH.

As used herein, the term "aldehyde" is represented by the formula -C (O) H.

As used herein, the term "keto group" is represented by the formula -C (O) R, wherein R is an alkyl, alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or heterocycloalkyl group described above. .

As used herein, the term “carbonyl group” is represented by the formula C═O.

As used herein, the term “ether” is represented by the formula AOA ¹ , wherein A and A ¹ are independently the aforementioned alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl , Heterocycloalkyl, or heterocycloalkenyl group.

As used herein, the term “sulfo-oxo group” is represented by the formula —S (O) ₂ R, —OS (O) ₂ R, or —OS (O) ₂ OR—, wherein R is hydrogen, alkyl, Alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or heterocycloalkyl groups.

As used herein, the term “promoter catalyst system” is intended to refer to a catalyst system that includes an accelerator, unless specifically stated otherwise. Accelerator catalyst systems may also be referred to as accelerated catalyst systems, which means that accelerators are present in the catalyst system.

Herein, unless specifically stated otherwise, the term "polycarbonate" is intended to refer to a composition comprising repeating structural carbonate units of formula (1):

Wherein at least 60% of the total number of R ¹ groups comprise an aromatic moiety, the balance of which is aliphatic, cycloaliphatic, or aromatic. In one aspect, each R ¹ is a C _{6 -30} aromatic group, i.e., contains at least one aromatic moiety. R ¹ may be derived from the formula HO-R ¹ -OH, in particular the dihydroxy compounds of formula (2):

Wherein A ¹ and A ² are each monocyclic divalent aromatic groups and Y ¹ is a crosslinking group or single bond having one or more atoms separating A ¹ from A ² . In one aspect, one atom separates A ¹ from A ² . Specifically, each R ¹ may be derived from a dihydroxy aromatic compound of formula (3):

(Wherein R, R ^a and R ^b are each independently halogen, C _{1 -12} alkyl, or C _{1 -12} alkyl; p and q are each independently an integer 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. In addition, in the formula (3), X ^a is ^a bridging group connecting two hydroxy-substituted aromatic groups, wherein the hydroxy substituent of the crosslinking group and each C ₆ arylene group is a C ₆ arylene group In ortho, meta, or para (specifically para). In one aspect, the bridging group X ^a is -S single bond, -O-, -S-, (O) -, -S (O) 2 -, -C (O) -, or C _{1 -18} organic group to be. The C _{1 -18} organic bridging group is cyclic or acyclic, aromatic or non-may further comprise a heteroatom such may be aromatic, halogen, oxygen, nitrogen, sulfur, silicon, or phosphorus. C _{1 -18} organic group, is connected to C ₆ arylene groups connected to a respective common alkylidene carbon or to different carbons of the C _{1 -18} organic bridging group which, may be placed. In one aspect, p and q are each 1, R ^a and R ^b are, respectively, disposed in a meta-hydroxy groups of the respective arylene groups, C _{1 -3} alkyl, in particular methyl.

In another aspect, X is ^a formula ^{-C (R c) (R d} ) - [ wherein R, R ^c and R ^d are each independently hydrogen, C _{1 -12} alkyl, C _{1 -12-cycloalkyl,} C _{7 - 12} arylalkyl, C _{1 -12} alkyl, heterocyclic, or a cyclic C _{7 -12} heteroarylalkyl, or the formula -C (= R ^e) - giim (wherein, R ^e is a divalent C _1-12 hydrocarbon giim) of; of a substituted or unsubstituted C _{3 -18} cycloalkyl alkylidene, C _{1 -25} alkylidene. Groups of this type include methylene, cyclohexylmethylene, ethylidene, neopentylidene, and isopropylidene, as well as 2- [2.2.1] -bicycloheptylidene, cyclohexylidene, cyclopentylidene , Cyclododecylidene, and adamantylidene.

In another aspect, X is ^a C _{1 -18} alkylene group, a C _{3 -18} cycloalkylene group, a fused C _{6 -18} cycloalkylene group, or the formula -B ¹ -GB ² - group (wherein R B ¹ and B ² are identical or different C _{1 -6} alkylene group, G is a C _{3 -12} cyclo alkylidene group or a C _{6 -16} arylene group). For example, X may be ^a substituted indenyl C _{3 -18} cycloalkyl Li of formula 4:

(Wherein, R ^r, R ^p, R ^q, and R ^t are each independently hydrogen, halogen, oxygen, or C _{1 -12} hydrocarbon group; Q is a bond (direct bond), carbon, or a divalent oxygen , sulfur, or -N (Z) - (wherein, Z is hydrogen, halogen, hydroxy, C _{1 -12} alkyl, C _{1 -12} alkyl, or C _{1 -12} acyl) a; r is from 0 to 2 , t is 1 or 2, q is 0 or 1, k is 0 to 3, and two or more of R ^r , R ^p , R ^q , and R ^t together are fused alicyclic, aromatic, or hetero Aromatic rings). When the fused ring is aromatic, it will be understood that the ring represented by formula (4) has an unsaturated carbon-carbon linking group to which the ring is fused. when k is 1 and i is 0, the ring represented by formula (4) comprises four carbon atoms, and when k is 2, the ring represented by formula (4) comprises five carbon atoms, When k is 3, the ring contains 6 carbon atoms. In one aspect, two adjacent groups (eg, R ^q and R ^t together) form an aromatic group, and in another aspect, R ^q and R ^t together form one aromatic group, R ^r and R ^p Together form a second aromatic group. When R ^q and R ^t together form an aromatic group, R ^p is a double-bonded oxygen atom, ie a ketone.

In one aspect, bisphenol (4) can be used to prepare polycarbonates comprising phthalimine carbonate units of formula (4a):

^{(Wherein, R a, R b, p} , and q are as defined in the formula bar (4), R ³ is an alkyl group each independently a C _{1 -6,} j = 0 to _4, R 4 is a C _1-6 a phenyl substituted with alkyl, phenyl, or C _1-6 alkyl groups of 5 or less). In particular, the phthalimidine carbonate units are of formula (4b):

(Wherein, R ⁵ is hydrogen or C _{1 -6} alkyl). In one aspect, R ⁵ is hydrogen. The carbonate unit (4a), wherein R ⁵ is hydrogen, is 2-phenyl-3,3'-bis (4-hydroxy phenyl) phthalimidine (also known as N-phenyl phenolphthalein bisphenol, or "PPPBP") (3 , 3-bis (4-hydroxyphenyl) -2-phenylisoindolin-1-one).

Other bisphenol carbonate repeat units of this type are the isatin carbonate units of formulas (4c) and (4d):

(Wherein R, R ^a and R ^b are each independently a C _{1 -12} alkyl, p and q are each independently 0 to 4, R ⁱ is a C _{1 -12} alkyl, 1 to 5 C _{1 -10} alkyl phenyl, or with 1 to 5 C _{1 -10} being benzyl, which is optionally substituted by alkyl), which is optionally substituted by. In one aspect, R ^a and R ^b are each methyl, p and q are each independently 0 or 1, R ⁱ is C _{1 -4} alkyl or phenyl.

Examples of the bisphenol-carbonate units of X ^b is derived from a bisphenol (4) substituted or unsubstituted C _{3 -18} cycloalkyl alkylidene is, cyclohexylidene of formula (4e) - substituted bisphenol-cross-linked, alkyl Contains:

(And wherein R, R ^a and R ^b are each independently a C _{1 -12} alkyl, R ^g is a C _{1 -12} alkyl, p and q are each independently 0 to 4, t is 0-10). In certain aspects, at least one of each R ^a and R ^b is disposed meta to the cyclohexylidene bridging group. In another aspect, R ^a and R ^b are each independently a C _{1 -4} alkyl, R ^g is a C _{1 -4} alkyl, p and q is 0 or 1, t is 0 to 5. In another aspect, R ^a , R ^b , and R ^g are each methyl, r and s are each 0 or 1 and t is 0 or 3, specifically 0. E.g,

Examples of other bisphenol carbonate units are derived from bisphenol X ^b (4) substituted or unsubstituted C _{3 -18} cycloalkyl alkylidene, ah and adamantyl units include (4f) and the unit (4g):

(Wherein R, R ^a and R ^b are each independently a C _{1 -12} alkyl, p and q each being independently from 1 to 4). In certain aspects, at least one of each R ^a and R ^b is disposed meta to the cyclohexylidene bridging group. In one aspect, R ^a and R ^b are each independently a C _{1 -3} alkyl, p and q are each 0 or 1. In another particular aspect, R ^a , R ^b are each methyl and p and q are each 0 or 1. Carbonates comprising units (4a) to (4g) are useful for producing polycarbonates having a high glass transition temperature (Tg) and a high heat distortion temperature.

Other useful aromatic dihydroxy compounds of the formula HO-R ¹ -OH include compounds of formula (5):

(Wherein each R ^h is independently a halogen atom, C _{1 -10} hydrocarbyl, for example C _{1 -10} alkyl, halogen-substituted C _{1 -10} alkyl, C _{6 -10} aryl group, or a halogen-substituted C _{6 -10} aryl groups, n is 0-4. Halogen is usually bromine.

Some illustrative examples of certain aromatic dihydroxy compounds include 4,4'-dihydroxybiphenyl, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, bis (4-hydroxyphenyl) Methane, bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) -1-naphthylmethane, 1,2-bis (4-hydroxyphenyl) ethane, 1,1-bis (4 -Hydroxyphenyl) -1-phenylethane, 2- (4-hydroxyphenyl) -2- (3-hydroxyphenyl) propane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4 -Hydroxy-3-bromophenyl) propane, 1,1-bis (hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy Phenyl) isobutene, 1,1-bis (4-hydroxyphenyl) cyclododecane, trans-2,3-bis (4-hydroxyphenyl) -2-butene, 2,2-bis (4-hydroxy Hydroxyphenyl) adamantane, alpha, alpha'-bis (4-hydroxyphenyl) toluene, bis (4-high Hydroxyphenyl) acetonitrile, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-ethyl-4-hydroxyphenyl) propane, 2,2-bis (3- n-propyl-4-hydroxyphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis (3-sec-butyl-4-hydroxyphenyl) propane , 2,2-bis (3-t-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 2,2-bis (3-allyl- 4-hydroxyphenyl) propane, 2,2-bis (3-methoxy-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 1,1-dichloro -2,2-bis (4-hydroxyphenyl) ethylene, 1,1-dibromo-2,2-bis (4-hydroxyphenyl) ethylene, 1,1-dichloro-2,2-bis (5 -Phenoxy-4-hydroxyphenyl) ethylene, 4,4'-dihydroxybenzophenone, 3,3-bis (4-hydroxyphenyl) -2-butanone, 1,6-bis (4-hydroxy Roxyphenyl) -1,6-hexanedione, ethylene writing Recall bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) Sulfone, 9,9-bis (4-hydroxyphenyl) fluorine, 2,7-dihydroxypyrene, 6,6'-dihydroxy-3,3,3 ', 3'-tetramethylspiro (bis) Indane (“spirobyin dan bisphenol”), 3,3-bis (4-hydroxyphenyl) phthalimide, 2,6-dihydroxydibenzo-p-dioxin, 2,6-dihydroxythianthrene, 2,7-dihydroxyphenoxatin, 2,7-dihydroxy-9,10-dimethylphenazine, 3,6-dihydroxydibenzofuran, 3,6-dihydroxydibenzothiophene, And 2,7-dihydroxycarbazole, resorcinol, substituted resorcinol compounds such as 5-methyl resorcinol, 5-ethyl resorcinol, 5-propyl resorcinol, 5-butyl Resorcinol, 5-t-butyl resorcinol, 5-phenyl reso Sinol, 5-cumyl resorcinol, a 2,4,5,6- tetrafluoro resorcinol, such as 2,4,5,6- tetrabromo resorcinol; Catechol; Hydroquinone; Substituted hydroquinones such as 2-methyl hydroquinone, 2-ethyl hydroquinone, 2-propyl hydroquinone, 2-butyl hydroquinone, 2-t-butyl hydroquinone, 2-phenyl hydroquinone, 2-cumyl hydroquinone, 2 , 3,5,6-tetramethyl hydroquinone, 2,3,5,6-tetra-t-butyl hydroquinone, 2,3,5,6-tetrafluoro hydroquinone, 2,3,5,6- Tetrabromo hydroquinone and the like, or combinations comprising at least one of the foregoing dihydroxy compounds.

Specific examples of the bisphenol compound of the general formula (3) include 1,1-bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxy Phenyl) propane (hereinafter “bisphenol A” or “BPA”, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 1,1-bis (4 -Hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) n-butane, 2,2-bis (4-hydroxy-2-methylphenyl) propane, 1,1-bis (4-hydroxy -t-butylphenyl) propane, 3,3-bis (4-hydroxyphenyl) phthalimidine, 2-phenyl-3,3-bis (4-hydroxyphenyl) phthalimidine (PPPBP), and 1, 1-bis (4-hydroxy-3-methylphenyl) cyclohexane (DMBPC) Combinations comprising at least one of the foregoing dihydroxy compounds can also be used. Nate is A ¹ and A ² are each p-phenylene, Y ¹ is isopro of formula (3) It is a linear homopolymer derived from bisphenol A, which is filidene.

In addition to the foregoing description, the term "polycarbonate" refers to homopolycarbonates, wherein each R ¹ in the polymer is the same, a copolymer comprising different R ¹ moieties in the carbonate ( "Copolycarbonate"), copolymers comprising other types of polymer units such as carbonate units and ester units, and combinations comprising one or more of homopolycarbonates and / or copolycarbonates It is intended to refer to.

Particular types of copolymers are polyester carbonates, also known as polyester-polycarbonates. Such copolymers further comprise repeating units of formula (6), in addition to repeating carbonate chain units of formula (1):

(Wherein, J is a group of 2 is derived from a dihydroxy compound, e.g., C _{2 -10} alkylene, C _{6 -20} cycloalkylene, C _{6 -20} aryl alkylene, or polyoxyalkylene date Wherein said alkylene group contains 2 to 6 carbon atoms, specifically 2, 3, or 4 carbon atoms; T is a divalent group derived from a dicarboxylic acid, for example C _2-10 alkylene, C _{6 -20} cycloalkyl that alkylene, or C _{6 -20} aryl can renil). Copolyesters comprising a combination of different T and / or J groups can be used. The polyester can be branched or linear.

In one aspect, J is a C _{2 -30} alkylene group having a straight, branched, or cyclic (including poly-cyclic) structure. In another aspect, J is derived from an aromatic dihydroxy compound of formula (3) above. In another aspect, J is derived from an aromatic dihydroxy compound of formula (4) above. In another aspect, 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 acid or terephthalic acid, 1,2-di (p-carboxyphenyl) ethane, 4,4'-dicarboxydiphenyl ether, 4,4 '-Bisbenzoic acid, or combinations comprising at least one of the foregoing acids. Acids containing fused rings may also be present, such as 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, or 2,6-naphthalenedicarboxylic acid. Specific dicarboxylic acids include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, cyclohexane dicarboxylic acid, or combinations comprising one or more of the foregoing acids. Particular dicarboxylic acids include a combination of isophthalic acid and terephthalic acid, with the weight ratio of isophthalic acid to terephthalic acid being 91: 9 to 2:98. In another particular aspect, J is C _{2 -6} alkylene group, T is p- phenylene, m- phenylene, naphthalene, a divalent cycloaliphatic group, or combinations thereof. Polyesters of this class include poly (alkylene terephthalates).

The weight ratio of ester units to carbonate units in the copolymer can vary widely, depending on the desired properties of the final composition, for example 1:99 to 99: 1, specifically 10:90 to 90:10, More specifically, it is 25: 75-75: 25.

In certain aspects, the polyester units of the polyester-polycarbonate are derived from the reaction of resorcinol with a combination of isophthalic acid and terephthalic acid (or derivatives thereof). In another particular aspect, the polyester units of the polyester-polycarbonate are derived from the reaction of bisphenol A with a combination of isophthalic acid and terephthalic acid. In certain aspects, the polycarbonate units are derived from bisphenol A. In another particular aspect, the polycarbonate units are derived from the reaction of resorcinol and bisphenol A, wherein the molar ratio of resorcinol carbonate units: bisphenol A carbonate units is from 1:99 to 99: 1. do.

Polycarbonates can be prepared by processes such as interfacial polymerization and melt polymerization. Branched polycarbonate blocks can be prepared by adding a branching agent during polymerization. These branching agents include polyfunctional organic compounds comprising at least three functional groups selected from hydroxyl, carboxyl, carboxylic anhydride, haloformyl, and mixtures of the foregoing functional groups. Specific examples include trimellitic acid, trimellitic anhydride, trimellitic trichloride, tris-p-hydroxy phenyl ethane, isatin-bis-phenol, tris-phenol TC (1,3,5-tris ((p -Hydroxyphenyl) isopropyl) benzene), tris-phenol PA (4 (4 (1,1-bis (p-hydroxyphenyl) -ethyl) alpha, alpha-dimethyl benzyl) phenol), 4-chloroform Mill phthalic anhydride, trimesic acid, and benzophenone tetracarboxylic acid. The branching agent may be added at a concentration of 0.05% to 2.0% by weight. Mixtures comprising linear polycarbonates and branched polycarbonates can be used.

Chain stoppers (also referred to as capping agents) may be included during the polymerization. The chain stopper limits the molecular weight growth rate, thereby controlling the molecular weight in the polycarbonate. Chain stoppers include certain mono-phenol compounds, mono-carboxylic acid chlorides, and / or mono-chloroformates. Mono-phenol chain stoppers include monocyclic phenols such as phenol and C ₁ -C ₂₂ alkyl-substituted phenols such as p-cumyl-phenol, resorcinol monobenzoate, and p- and tert-butyl phenol; Take the monoether of diphenols, such as p-methoxyphenol, for example. Alkyl-substituted phenols having branched alkyl substituents having 8 to 9 carbon atoms may be specifically mentioned. Certain mono-phenol UV absorbers such as 4-substituted-2-hydroxybenzophenone and derivatives thereof, aryl salicylates, monoesters of diphenols such as resorcinol monobenzoate, 2- (2- Hydroxyaryl) -benzotriazole and derivatives thereof, 2- (2-hydroxyaryl) -1,3,5-triazine and derivatives thereof and the like can be used as the capping agent.

Mono-carboxylic acid chlorides can also be used as chain stoppers. These include monocyclic, mono-carboxylic acid chlorides such as benzoyl chloride, C ₁ -C ₂₂ alkyl-substituted benzoyl chlorides, toluyl chlorides, halogen-substituted benzoyl chlorides, bromobenzoyl chlorides, cinnamoyl chlorides, 4-nada Imidobenzoyl chloride, and combinations thereof; Polycyclic, mono-carboxylic acid chlorides such as trimellitic anhydride chloride, and naphthoyl chloride; Combinations of monocyclic and polycyclic mono-carboxylic acid chlorides. Chlorides of aliphatic monocarboxylic acids having up to 22 carbon atoms are useful. Aliphatic monocarboxylic acid functionalized chlorides such as acryloyl chloride and methacryloyl chloride are also useful. In addition, mono-chloroformates, including monocyclic, mono-chloroformates such as phenyl chloroformate, alkyl-substituted phenyl chloroformates, p-cumyl phenyl chloroformates, toluene chloroformates, and combinations thereof, useful.

In another example, a polycarbonate can be prepared using a melting method. Polyester-polycarbonates can also be produced by interfacial polymerization. Rather than using dicarboxylic acids or diols themselves, reactive derivatives of these acids or diols can be used, such as the corresponding acid halides, in particular acid dichlorides and acid dibromide. That is, for example, instead of using isophthalic acid, terephthalic acid, or a combination comprising one or more of the foregoing acids, such as isophthaloyl dichloride, terephthaloyl dichloride, or one or more of the foregoing dichlorides. Can be used in combination.

In addition to the polycarbonates described above, combinations of polycarbonates with other thermoplastic polymers can be used, for example homopolycarbonates and / or combinations of polycarbonate copolymers and polyesters. Useful polyesters may include, for example, polyesters having repeat units of formula (6), which include poly (alkylene dicarboxylates), liquid crystalline polyesters, and polyester copolymers. Include. The polyesters described herein are generally completely miscible with the polycarbonate when blended.

The polyester may be obtained by the above-mentioned interfacial polymerization or melt-process condensation, solution phase condensation, or transesterification polymerization, for example, dialkyl esters such as dimethyl terephthalate may be converted into ethylene glycol using an acid catalyst. Can be transesterified to produce poly (ethylene terephthalate). Branching agents, for example branched polyesters incorporating glycols with three or more hydroxyl groups or trifunctional or polyfunctional carboxylic acids can be used. In addition, depending on the ultimate end use of the composition, it may be desirable to have acid and hydroxyl end groups in various concentrations in the polyester.

Useful polyesters may include aromatic polyesters, poly (alkylene esters) including poly (alkylene arylate) s, and poly (cycloalkylene diesters). The aromatic polyester may have a polyester structure according to formula (6), wherein J and T are each the aforementioned aromatic groups. In one aspect, useful aromatic polyesters include, for example, poly (isophthalate-terephthalate-resorcinol) esters, poly (isophthalate-terephthalate-bisphenol A) esters, poly [(isophthalate-tere) Phthalate-resorcinol) ester- co- (isophthalate-terephthalate-bisphenol A)] ester, or a combination comprising one or more thereof. In addition, to prepare copolyesters, consider aromatic polyesters having a small amount of units derived from aliphatic diacids and / or aliphatic polyols, such as from 0.5% to 10% by weight based on the total weight of the polyester. The poly (alkylene arylate) may have a polyester structure according to formula (6), wherein T comprises groups derived from aromatic dicarboxylates, cycloaliphatic dicarboxylic acids, or derivatives thereof. Specific examples of useful T groups include 1,2-phenylene, 1,3-phenylene, and 1,4-phenylene; 1,4-naphthylene and 1,5-naphthylene; cis-1,4-cyclohexylene or trans-1,4-cyclohexylene and the like. Specifically, when T is 1,4-phenylene, poly (alkylene arylate) is poly (alkylene terephthalate). In addition, for poly (alkylene arylate), particularly useful alkylene groups J include, for example, ethylene, 1,4-butylene, and cis-1,4- (cyclohexylene) dimethylene and / Or bis- (alkylene-2 substituted cyclohexane), including trans-1,4- (cyclohexylene) dimethylene. Examples of poly (alkylene terephthalates) include poly (ethylene terephthalate) (PET), poly (1,4-butylene terephthalate) (PBT), and poly (propylene terephthalate) (PPT). Also useful are poly (alkylene naphthoates) such as poly (ethylene naphthoate) (PEN), and poly (butylene naphthoate) (PBN). Particularly useful poly (cycloalkylene diesters) are poly (cyclohexanedimethylene terephthalates) (PCT). Combinations comprising at least one of the foregoing polyesters can also be used.

Copolymers comprising alkylene terephthalate repeating ester units and other ester groups may also be useful. Specifically useful ester units may comprise different alkylene terephthalate units, which may be present in the polymer chain as individual units or as blocks of poly (alkylene terephthalates). Copolymers of this type include poly (cyclohexanedimethylene terephthalate) -co-poly (ethylene terephthalate), which is shortened to PETG when the polymer contains at least 50 mol% poly (ethylene terephthalate). When the polymer contains 50 mol% or more of poly (1,4-cyclohexanedimethylene terephthalate), it is referred to as PCTG for short.

The poly (cycloalkylene diester) may also include poly (alkylene cyclohexanedicarboxylate). Among these, specific examples are poly (1,4-cyclohexane-dimethanol-1,4-cyclohexanedicarboxylate) (PCCD) having repeat units of formula (7):

(Wherein, using the formula (6), J is a 1,4-cyclohexanedimethylene group derived from 1,4-cyclohexanedimethanol, and T is a cyclohexane derived from cyclohexanedicarboxylate.) Rings or their chemical equivalents, and may include cis-isomers, trans-isomers, or combinations comprising at least one of the foregoing isomers).

Polycarbonates and polyesters may be used in a weight ratio of 1:99 to 99: 1, specifically 10:90 to 90:10, more specifically 30:70 to 70:30, depending on the desired function and properties. have.

These polyester and polycarbonate blends have an MVR of 5 to 150 cc / 10 min., Specifically 7 to 125 cc / 10 when measured at a load of 1.2 kg at 300 ° C. according to ASTM D1238-04. min, more specifically 9 to 110 cc / 10 min, even more preferably 10 to 100 cc / 10 min.

In another aspect, the polycarbonate may comprise a polysiloxane-polycarbonate copolymer, also referred to as polysiloxane-polycarbonate. The polydiorganosiloxane (also referred to as "polysiloxane") block of the copolymer comprises repeating diorganosiloxane units in formula (8):

Wherein each R is independently a C _{1 -13} monovalent organic group. For example, R is C ₁ -C ₁₃ alkyl, C ₁ -C ₁₃ alkoxy, C ₂ -C ₁₃ alkenyl group, C ₂ -C ₁₃ alkenyloxy, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkoxy, C ₆ -C ₁₄ aryl, C ₆ -C ₁₀ aryloxy, C ₇ -C ₁₃ arylalkyl, C ₇ -C ₁₃ aralkoxy, C ₇ -C ₁₃ alkylaryl, or C ₇ -C ₁₃ alkyl Aryloxy. The aforementioned groups may be completely or partially halogenated with fluorine, chlorine, bromine, or iodine, or a combination thereof. In one aspect, where transparent polysiloxane-polycarbonates are desired, R is unsubstituted by halogen. Combinations of the foregoing R groups can be used in the same copolymer.

The value of E in formula (8) may vary considerably depending on considerations such as the type and relative amount of each component in the thermoplastic composition, the desired properties of the composition, and the like. In general, E has an average value of 2 to 1,000, specifically 2 to 500, or 2 to 200, more specifically 5 to 100. In one aspect, E has an average value of 10 to 75, and in another aspect, E has an average value of 40 to 60. If the value of E is as low as less than 40, it may be desirable to use a relatively large amount of polycarbonate-polysiloxane copolymer. In contrast, when the value of E is as high as more than 40, relatively small amounts of polycarbonate-polysiloxane copolymers can be used.

Combinations of first and second (or higher) polycarbonate-polysiloxane copolymers can be used, with an average value of E of the first copolymer being lower than an average value of E of the second copolymer.

In one aspect, the polydiorganosiloxane block is of formula (9):

Wherein E is as defined above; each R may be the same or different and as defined above; Ar is the same or different and is a substituted or unsubstituted C ₆ -C ₃₀ arylene group, wherein The bond is directly connected to the aromatic moiety). The Ar group in formula (9) may be derived from a C ₆ -C ₃₀ dihydroxyarylene compound, for example the dihydroxyarylene compound of formula (3) or (5) above. The dihydroxyarylene compound is 1,1-bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2 , 2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 1,1-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxy Hydroxyphenyl) n-butane, 2,2-bis (4-hydroxy-1-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl sulfide), and 1,1-bis (4-hydroxy-t-butylphenyl) propane. Combinations comprising at least one of the foregoing dihydroxy compounds can also be used.

In another aspect, the polydiorganosiloxane block is of formula (10):

Wherein R and E are as described above and each R ⁵ is independently a divalent C ₁ -C ₃₀ organic group, wherein the polymerized polysiloxane units are the reaction moieties of their corresponding dihydroxy compounds) . In certain aspects, the polydiorganosiloxane block is of formula (11):

Wherein R and E are as defined above. R ⁶ in formula (11) is a divalent C ₂ -C ₈ aliphatic group. Each M in formula (11) may be the same or different and is halogen, cyano, nitro, C ₁ -C ₈ alkylthio, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, C ₂ -C ₈ Alkenyl, C ₂ -C ₈ alkenyloxy groups, C ₃ -C ₈ cycloalkyl, C ₃ -C ₈ cycloalkoxy, C ₆ -C ₁₀ aryl, C ₆ -C ₁₀ aryloxy, C ₇ -C ₁₂ are Alkyl, C ₇ -C ₁₂ aralkoxy, C ₇ -C ₁₂ alkylaryl, or C ₇ -C ₁₂ alkylaryloxy, wherein each n is independently 0, 1, 2, 3, or 4 Can be.

In one aspect, M is bromo or an alkyl group such as chloro, 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; R is aryl, such as haloalkyl, cyanoalkyl, or phenyl, chlorophenyl or tolyl, such as a profile with a C _{1 -8} alkyl, trifluoromethyl. In another aspect, R is methyl, or a combination of methyl and trifluoropropyl, or a combination of methyl and phenyl. In another aspect, M is methoxy, n is 1, R ² is a divalent C ₁ -C ₃ aliphatic group and R is methyl.

The block of formula (11) may be derived from the corresponding dihydroxy polydiorganosiloxane (12):

Wherein R, E, M, R ⁶ , and n are as described above. Such dihydroxy polysiloxanes can be prepared by influencing the platinum-catalyzed addition between siloxane anhydrides of formula (13):

Wherein R and E are as defined above and are aliphatic unsaturated monohydric phenols. Aliphatic unsaturated monohydric phenols include eugenol, 2-alkylphenol, 4-allyl-2-methylphenol, 4-allyl-2-phenylphenol, 4-allyl-2-bromophenol, and 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 may also be used.

The polyorganosiloxane-polycarbonate may comprise from 50% to 99% by weight of carbonate units and from 1% to 50% by weight of siloxane units. Within this range, the polyorganosiloxane-polycarbonate copolymer has 70 to 98 weight percent of carbonate units, more specifically 75 to 97 weight percent and 2 weight percent of siloxane units. To 30% by weight, more specifically 3% to 25% by weight.

The polyorganosiloxane-polycarbonate is measured by gel permeation chromatography using a styrene-divinyl benzene column crosslinked at a sample concentration of 1 mg / ml, and weight average molecular weight when calibrated with polycarbonate standards. It can have to 2,000 to 100,000 Daltons, specifically 5,000 to 50,000 Daltons.

The polyorganosiloxane-polycarbonate has a melt volume flow rate of 1 cm 3 to 50 cm 3 (cc / 10 min) per 10 minutes, specifically 2 cc / 10 min to 30 cc /, as measured at 300 ° C./1.2 kg. 10 min. Mixtures of polyorganosiloxane-polycarbonates with different flow characteristics can be used to achieve the overall desired flow characteristics.

In another aspect, the polycarbonate material may comprise a flame retardant. In another aspect, the BPA polycarbonate material may comprise a second polycarbonate derived from bisphenol-A, wherein the second polycarbonate is different from the BPA polycarbonate. In another aspect, the BPA polycarbonate material may comprise a second polycarbonate derived from bisphenol-A, wherein the second polycarbonate comprises homopolycarbonates derived from bisphenols; Copolycarbonates derived from more than on bisphenols; And copolymers derived from the at least one bisphenol and comprising at least one aliphatic ester unit or aromatic ester unit or siloxane unit. In yet another aspect, the BPA polycarbonate may comprise one or more additives selected from one or more of UV stabilizing additives, thermal stabilizing additives, mold release agents, colorants, organic fillers, inorganic fillers, and gamma-stabilizing agents.

Each of the materials disclosed herein are commercially available and / or methods for their preparation are known to those skilled in the art.

It is understood that the present compositions have certain functions. The present disclosure discloses 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 with respect to the disclosed structure, which structures will typically achieve the same results.

As briefly mentioned above, the present disclosure provides methods of preparation and accelerator catalyst systems that may be useful for condensation reactions, such as synthesis, of bisphenol-A. Conventional ion exchange resin based BPA production methods utilize sulfur-containing bulk promoters such as 3-mercaptopropionic acid (3-MPA) which can degrade and produce undesirable sulfur compounds in the final product. These compounds may limit or hinder the use of BPA in demanding applications, such as polycarbonates of food contact grade.

In one aspect, the present disclosure provides a process for producing high purity BPA that is free of or substantially free of inorganic, sulfur, or thermally degraded components. In one aspect, the present disclosure provides a process for producing high purity BPA with little or no sulfur present. In another aspect, the present disclosure provides a manufacturing method that does not use a bulk promoter, such as 3-MPA. In still another aspect, the present disclosure provides a manufacturing method capable of producing high purity BPA suitable for use in food contact polycarbonate application, healthcare application optical application, or a combination thereof. In still another aspect, the present disclosure provides a method of preparation comprising an accelerator catalyst attached with solvent crystallization.

An accelerator system may also be attached, wherein the accelerator is attached to a catalyst system such as an ion exchange resin. Exemplary attached promoter systems utilize pyridyl ethylmercaptone (PEM) promoters.

In one aspect, the methods disclosed herein may be useful for the preparation of BPA. It should also be noted that the reactants for the bisphenol condensation reaction may include phenols, ketones and / or aldehydes, or mixtures thereof. In one aspect, specifically referring to a ketone or aldehyde, such as acetone, refers to aspects using only the species mentioned, aspects using other species (eg aldehydes for ketones), and combinations of species. It is intended to encompass the aspects of use. In other aspects, the methods described herein may be useful for the preparation of other species, such as condensation reactions.

In one aspect, the phenol reactant may comprise an aromatic hydroxy compound having one or more unsubstituted positions, and optionally one or more inert substituents such as hydrocarbyl or halogen at one or more ring positions. In one aspect, the inert substituents are substituents that do not unnecessarily interfere with the condensation of phenols with ketones or aldehydes and are not catalytic in themselves. In another aspect, the phenol reactant is unsubstituted in the para position relative to the hydroxyl group. As mentioned herein, hydrocarbyl functional groups include carbon and hydrogen atoms, for example, alkylene, alkyl, cycloaliphatic, aryl, arylene, alkylarylene, arylalkylene, alkylcycloaliphatic and alkyl Ranges are cyclic hydrocarbyl groups, ie functional groups containing carbon and hydrogen atoms.

In one aspect, an alkyl group, when present in a phenolic species, comprises from 1 to about 20 carbon atoms, or from 1 to 5 carbon atoms, or from 1 to 3 carbon atoms, for example, Eggplant methyl, ethyl, propyl, butyl and pentyl isomers. In one aspect, the alkyl, aryl, alkaryl and aralkyl substituents are suitable hydrocarbyl substituents on the phenol reactant.

In one aspect, other inert phenolic substituents include, but may not be limited to, alkoxy, aryloxy or alkaryloxy, wherein alkoxy is methoxy, ethoxy, propyloxy, butoxy, pentoxy, hexoxy, hep Oxy, octyloxy, nonyloxy, decyloxy and polyoxyethylene, as well as higher homologs; Aryloxy, phenoxy, biphenoxy, naphthyloxy and the like, and alkaryloxy includes alkyl, alkenyl and alkylyl-substituted phenols. Additional inert phenolic substituents may include halo such as bromo, chloro or iodine.

Without intending to be limiting, exemplary phenols include 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. In another aspect, the phenol reactant may include phenol, 2-cresol or 3-cresol, 2,6-dimethylphenol, resorcinol, naphthol, and / or combinations or mixtures thereof. In one aspect, the phenol is unsubstituted.

In one aspect, the phenol starting material may be a commercial grade or better. As one of ordinary skill in the art will readily understand, commercial grade reagents include, in particular, acetone, alpha-methylstyrene, acetophenone, alkyl benzene, cumene, cresol, water, hydroxyacetone, methyl benzofuran, methyl cyclopentenone, And typical impurities such as mesityl oxide at measurable levels.

In one aspect, where a ketone is used, it may comprise a ketone having a single carbonyl (C═O) group or several carbonyl groups and is reactive under the conditions used. In another aspect, the ketone may be substituted with a substituent which is inert under the conditions used, for example, the aforementioned inert substituent in the case of phenol.

In one aspect, the ketone may comprise aliphatic, aromatic, cycloaliphatic or mixed aromatic-aliphatic ketones, diketones or polyketones, among which acetone, methyl ethyl ketone, diethyl ketone, benzyl, acetyl acetone, methyl iso Propyl ketone, methyl isobutyl ketone, acetophenone, ethyl phenyl ketone, cyclohexanone, cyclopentanone, benzophenone, fluorenone, indanone, 3,3,5-trimethylcyclohexanone, anthraquinone, 4-hydroxy Acetophenone, acenaphthequinone, quinone, benzoylacetone and diacetyl are representative examples. In another aspect, ketones with halo, nitrile or nitro substituents can also be used, such as 1,3-dichloroacetone or hexafluoroacetone.

Exemplary aliphatic ketones may include acetone, ethyl methyl ketone, isobutyl methyl ketone, 1,3-dichloroacetone, hexafluoroacetone, or combinations thereof. In one aspect, the ketone is acetone, which can be condensed with phenol to produce 2,2-bis- (4-hydroxyphenyl) -propane, commonly known as bisphenol A. In another aspect, the ketone comprises hexafluoroacetone which can react with 2 moles of phenol to produce 2,2-bis- (4-hydroxyphenyl) -hexafluoropropane (bisphenol AF). In another aspect, the ketone may comprise a ketone having one or more hydrocarbyl groups including aryl groups such as phenyl, tolyl, naphthyl, xylyl or 4-hydroxyphenyl groups.

Other exemplary ketones may include 9-fluorenone, cyclohexanone, 3,3,5-trimethylcyclohexanone, indanone, indenone, anthraquinone, or combinations thereof. Still other exemplary ketones may include benzophenone, acetophenone, 4-hydroxyacetophenone, 4,4'-dihydroxybenzophenone, or a combination thereof.

In one aspect, the ketone reactant may be a commercial grade or better. As one of ordinary skill in the art will readily appreciate, commercial grade reagents will include, in measurable levels, typical impurities such as aldehydes, acetophenones, benzene, cumene, diacetone alcohol, water, mesityl oxide, and methanol, in particular. Can be. In one aspect, a ketone such as acetone has less than about 250 ppm of methanol. In another aspect, the catalyst system of the present invention may be tolerant to higher concentrations of impurities such that the ketone may comprise greater than about 250 ppm methanol.

In another aspect, the various methods and catalyst systems described herein can be used to form phenol into formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, or higher homologs of the formula RCHO, wherein R is alkyl, for example, And alkyl having 1 to 20 carbon atoms. In one aspect, condensation of 2 moles of phenol and 1 mole of formaldehyde yields bis- (4-hydroxyphenyl) methane, also known as bisphenol F. It should also be understood that dialdehydes and ketoaldehydes such as glyoxal, phenylglyoxal or pyruvic acid aldehydes may optionally be used.

Accelerator Catalyst System-Ion Exchange Resin

Accelerator catalyst systems of the present disclosure include ion exchange resin catalysts and accelerators. In one aspect, the ion exchange resin comprises an ion exchange resin suitable for use in the catalyst system of the present invention. In another aspect, the ion exchange resin comprises a crosslinked cationic exchange resin. In another aspect, the ion exchange resin comprises a crosslinked sulfonated ion exchange resin having a plurality of sulfonic acid moieties. In another aspect, the ion exchange resin is acidic or strongly acidic. In one aspect, at least some of the ion exchange resins include sodium polystyrene sulfonate. In still other aspects, the ion exchange resin may comprise a monodisperse resin, a polydisperse resin, or a combination thereof.

The specific chemistry for the ion exchange resin, or one or more polymeric materials that form part of the ion exchange resin, may vary, and in the context of the present disclosure, one of ordinary skill in the art can readily select an appropriate ion exchange resin. In one aspect, the ion exchange resin comprises polystyrene or derivatized polystyrene. In another aspect, the ion exchange resin includes polysiloxanes or derivatized polysiloxanes. In addition, it should be understood that the catalyst system may, in one aspect, comprise multiple ion exchange resins having the same composition, acidity, and / or degree of cross-linking.

In one aspect, the ion exchange resins can be crosslinked with the same or different polymeric materials. In various aspects, the degree of crosslinking may be from about 1% to about 8%, for example about 1, 2, 3, 4, 5, 6, 7, 8%; About 1% to about 4%, 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 4%; Or about 1.5% to about 2.5%, 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%. In other aspects, the degree of crosslinking may be less than 1% or greater than 8%, and the invention is not intended to be limited to the degree of crosslinking of the specific values referred to herein. In certain aspects, the degree of crosslinking is about 2%. In another aspect, the ion exchange resin is not crosslinked. While not wishing to be bound by theory, crosslinking of the ion exchange resin is not necessary, but may provide additional stability to the resin and the resulting catalyst system.

In one aspect, the ion exchange resin can be crosslinked using conventional crosslinking agents such as polycyclic aromatic divinyl monomers, divinyl benzene, divinyl toluene, divinyl biphenyl monomers, or combinations thereof.

In another aspect, the ion exchange resin comprises a plurality of acid sites and when dried prior to modification, the acid is at least about 3 milliequivalents / g (meq / g), at least about 3.5 meq / g, at least about 4 meq / g or more, about 5 meq / g or more. In certain aspects, the ion exchange resin has at least about 3.5 milliequivalents / g of acid upon drying prior to modification. In various aspects, the plurality of acid moieties in the ion exchange resin may be sulfonic acid functional groups that generate sulfonate anion functional groups upon deprotonation, phosphonic acid functional groups that generate phosphonate anion functional groups upon deprotonation, or deprotonation. Carboxylic acid functional groups that produce a carboxylate anionic functional group.

Exemplary ion exchange resins include 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 resin (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).

Accelerator Catalyst System-Accelerator

Accelerators of the attached promoter catalyst systems of the present invention may include any promoter suitable for use in the various methods described herein and may provide a desired high purity product.

In one aspect, the promoter of the present invention may comprise pyridyl ethylmercaptone (PEM). In another aspect, the promoter of the invention may comprise dimethyl thiazolidine (DMT). In another aspect, the promoter of the invention may include derivatives and / or analogs of pyridyl ethylmercaptone, dimethyl thiazolidine, or combinations thereof. In other aspects the promoters of the invention may include other promoter species not specifically mentioned herein. In another aspect, the promoter of the present invention may be represented by the formula:

Wherein dimethyl thiazolidine is combined with an ion exchange resin to provide a cysteamine attached ion exchange resin.

In one aspect, the promoter can be contacted with the ion exchange resin to neutralize and bind to at least some of the acid sites available on the ion exchange resin. In various aspects, the ion exchange resin can comprise from about 10% to about 40% of the acid sites available with the promoter; Or by neutralizing from about 18% to about 25% of the available acid sites with a promoter. In another aspect, the promoter is bound to 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. In another aspect, the promoter is bound to about 20% to about 24% of the acid sites on the ion exchange resin. In another aspect, the promoter is bound to about 22% of the acid sites on the ion exchange resin.

In an exemplary method, the promoter is contacted with a solvent to form a mixture. The mixture may further comprise an acid to improve the solubility of the promoter. In one aspect, the amount of acid may be sufficient to dissolve the promoter but not enough to prevent modification of the ion exchange resin. In one aspect, the amount of acid is typically 1 equivalent or less, based on the moles of promoter; Or about 0.25 equivalent or less. Exemplary acids include, but are not limited to hydrochloric acid (HCl), p-toluenesulfonic acid, trifluoroacetic acid, and acetic acid. In this aspect, the mixture may be contacted with an ion exchange resin to create an ionic linker between the promoter cation and the anion (deprotonated acid moiety) of the ion exchange resin. The formation of ionic linkages neutralizes the acid sites.

The degree of neutralization can be measured in many ways. In one aspect, the modified ion exchange resin catalyst may be titrated to determine the amount of residual acid sites.

After reforming (neutralization), the modified ion exchange resin catalyst may optionally be washed with a continuous flow of phenol to remove residual amounts of solvent after reforming. In another example, when an acid is used to improve the solubility of the promoter, the modified ion exchange resin may optionally be washed with deionized water prior to washing with phenol. In one aspect, herein, substantially removing all water is defined as removing at least about 75%, at least about 80%, or at least about 85%, based on the total amount of water initially applied.

In one aspect, at least some of the accelerators ionically bind to available acid sites of the ion exchange resin. In another aspect, all or substantially all of the promoter is ionically bonded to the acid sites of the ion exchange resin. In another aspect, at least some of the promoter is covalently bound to at least some of the ion exchange resins. In still other aspects, all or substantially all of the promoter is at least covalently bonded to the ion exchange resin. In another aspect, the degree of adhesion or bond between the promoter and the ion exchange resin may vary, for example, covalent bonds, ionic bonds, and / or other interactions or adhesion and the invention is limited to specific degrees of adhesion. It is not intended.

It should be noted that the methods described herein include multiple selection steps, and that no specific or required order of steps is intended except where this order is not functional. One skilled in the art can readily determine the order of the optional steps to be used and the reaction steps that must be performed to obtain the desired result.

Condensation reaction

In one aspect, one or more of the reactants, phenol or optionally purified phenol, and ketones or aldehydes may be fed and contacted to the reactor vessel. In another aspect, the reactants may be mixed in the reactor vessel at one time, for example using a static mixer. After contacting and / or mixing, the reactor feed comprising the reactants can be cooled to a predetermined temperature using, for example, a plate heat exchanger. In one aspect, using an attached promoter catalyst system can reduce the amount of acetone in the reactor feed stream, for example, from about 9.5 weight percent to about 5 weight percent. In this aspect, the reactor eluate may have a low solids content and a large amount of phenol.

A bed of attached promoter ion exchange resin catalyst system, such as a crosslinked ion exchange resin catalyst with dimethyl thiazolidine promoter, may be placed in the reaction vessel such that the reactants flow through the bed. In one aspect, the reaction vessel and the phase can be oriented such that the reactants flow downwardly (eg, in the direction of gravity) through the catalyst phase.

In various aspects, the reaction can be controlled to a predetermined temperature, such as about 55 ° C or 65 ° C. The change in temperature can affect the reaction rate and the rate of isomerization of the resulting BPA. Other temperatures not mentioned herein can be used, and one of ordinary skill in the art can readily determine the appropriate temperature at which to perform a particular condensation reaction.

In one aspect, the reactor can convert at least about 90% of this acetone if acetone is present in the reactor feed. In another aspect, the reactor may convert at least about 92%, 94%, 96%, 98%, or more of acetone if acetone is present in the reactor feed. In another aspect, the reactor and attached promoter catalyst system produce the p, p-BPA isomer with at least about 90%, at least about 92%, at least about 93%, at least about 95%, at least about 97%, or more selectivity. can do.

Once passed through the catalyst bed, the reactor eluate can optionally be treated with an individual ion exchange resin bed to remove unwanted materials such as oligomers from the process stream. In one aspect, the reactor eluate is treated with a separate ion exchange resin to remove unwanted material. In another aspect, the reactor eluate is not treated with individual ion exchange resins.

Water removal

After the reaction, the eluent stream may optionally be subjected to a water removal step to remove residual water. In various aspects, when performing the water removal step, this may include placing one or multiple columns in succession.

In one aspect, the reactor eluate stream may comprise water, acetone, phenol, toluene and / or other aromatic solvents such as benzene and xylene. In one aspect, the eluate (ie, steam) can be treated with a water cooled process condenser. In another aspect, vent gas from this process condenser may be transported to a brine vent condenser and cooled, for example, with chilled brine at a temperature of about 8 ° C. Certain parameters (eg, temperature) described herein are intended to be illustrative and non-limiting, and one of ordinary skill in the art can readily determine appropriate experimental conditions for a given process setup in the context of the present disclosure. It is intended to be.

In another aspect, an inert gas, such as nitrogen, may be introduced into the condenser unit to at least partially prevent condensation of aromatic solvents, such as toluene, that may be present in the eluent stream.

After passing the water removal step, the reactor eluate (ie, the dehydrated reactor eluate) has a water content of less than about 0.5 weight percent, less than about 0.4 weight percent, less than about 0.3 weight percent, less than about 0.2 weight percent, or about 0.1 weight. It may have less than%. In one aspect, the dehydrated reactor eluate has a water content of less than about 0.2 weight percent. In another aspect, the dehydrated reactor eluate has a water content of less than about 0.1 weight percent.

Phenol recovery

In order to change the reactor eluate from the use of an attached promoter ion exchange resin catalyst system, optionally after passing through separate ion exchange resin beds and / or water removal steps, the reactor eluate stream is, in one aspect, phenol flash (ie, phenol Recovery) unit.

In various aspects, the phenol flash unit may comprise a single column or a plurality of individual columns. In various aspects, any combination of columns or order of columns may be used. In one aspect, the phenol flash unit comprises three separate columns, a phenol flash column, a top phenol column, and a bottom phenol column. In another aspect, a single column or multiple columns can be removed from the process. It is to be noted that the terms "top" and "bottom" are not intended to require a particular orientation, and that each column may be placed in a geometric arrangement appropriate for a particular process.

In one aspect, the phenol flash column removes all or part of the phenol reactant from the eluent stream. In certain aspects, reactor eluate, such as dehydrated reactor eluate, may be heated before entering the phenol flash column. In another aspect, the phenol flash column can be operated at elevated temperature and / or under vacuum such as about 750 mbar.

In one aspect, the flashed phenol can be removed from the eluent stream and then condensed. In another aspect, the flashed phenol can be at least partially condensed into a flash column as a cooling medium using a feed stream. In this regard, some or more of the energy extended with flash phenol can be recovered. If residual phenol vapor is present, it can be recovered, for example, in a vacuum system.

In one aspect, first, the eluate stream can be treated with a phenol flash column. The eluate from the phenol flash column can then be treated with an upper phenol column and then, if present, with a lower phenol column.

In one aspect, for example, after passing through a phenol flash column, an upper phenol column, and a lower phenol column, the free phenol content of the eluate from the phenol flash unit is less than about 1.0 weight percent, less than about 0.75 weight percent, or about May be less than 0.5% by weight. In certain aspects, the free phenol content of the eluate from the phenol flash unit is less than about 0.5 weight percent.

It should be noted that at any point in the process, the eluate stream may optionally be returned back through one or more units and / or columns of the reaction process to further react and / or purify the eluate. One skilled in the art can readily determine, in the context of the present disclosure, the point of application of this recycle loop to apply to produce the desired product.

Solvent crystallization

In one aspect, the reactor eluate can be treated with a phenol flash unit and then fed to a solvent crystallization unit. In one aspect, using a solvent crystallization unit, o, p-BPA, Chroman, BPX 1 and / or 2, cyclic dimers (CD1 and / or 2), linear dimers (LD2 and / or 2), or these By-products such as BPA can be removed. The structures of these BPA impurities are described, for example, in Nowakowska et al., Polish J. Appl. Chem., XI (3), 247-254, 1996. In one aspect, the solvent crystallization unit may remove at least some of the BPA byproducts from the eluate stream. In one aspect, solubility in the eluate stream of one or more individual components can be known or measured. In other aspects, such solubility data can be used by those skilled in the art to optimize crystallization parameters to provide improved products.

Properties of the resulting bisphenol-A and BPA polycarbonates

The reaction products of the various methods of the present invention may, in various aspects, exhibit higher levels of purity than those obtainable using conventional manufacturing methods. In one aspect, the use of an attached promoter ion exchange resin catalyst system, such as a dimethyl thiazolidine catalyst system, can provide the resulting BPA product free or substantially free of inorganic or sulfur impurities. Moreover, the combination of the attached accelerator catalyst system and the solvent crystallization step can yield a high purity product suitable for use in the manufacture of materials and food contact grade materials that require optimal application. For example, BPA produced by the process of the present invention can be used to prepare food-grade polycarbonate products.

In one aspect, BPA synthesized using the method of the present invention may be useful for preparing polycarbonates having enhanced optical properties as compared to conventional polycarbonates made from conventional BPA materials. In one aspect, BPA prepared by the process of the present invention can produce polycarbonates with good impact strength (durability). Conventional polycarbonates may age with exposure to heat, light, and / or over time, resulting in a decrease in light transmittance and color change of the material.

Conventional bulk promoter catalyst systems utilizing resin catalyst systems with sulfonic acid groups and 3MPA promoters may leave up to about 20 ppm or less of sulfur in the resulting BPA, even after purification. In one aspect, the methods described herein include less than about 10 ppm, less than about 5 ppm, less than about 4 ppm, less than about 3 ppm, about 2 ppm, or, for example, as measured by combustion and / or colorimeter methods, or A BPA of about 1 ppm can be provided. In certain aspects, the methods described herein can provide BPA having about 2 ppm sulfur. In another aspect, the methods described herein can provide BPA free or substantially free of sulfur.

In another aspect, improved purity of the BPA produced by the methods described herein, such as reduction of sulfur and organic contaminants, can improve the color properties of the polycarbonate material. In one aspect, polycarbonates prepared from the BPA produced by the methods of the present disclosure, even after aging at elevated temperatures, appear to have a lower chromaticity, such as yellowness, compared to conventional polycarbonate materials. In one aspect, polycarbonates prepared from BPA produced by the methods of the present disclosure can exhibit surprisingly low chromaticity after aging at about 130 ° C. for 2,000 hours.

In another aspect, BPA produced by the methods described herein, or polycarbonates prepared therefrom, such as BPA polycarbonate, have less than about 150 ppm free hydroxyl groups, such as about 150 , 125, 100, 75, 50 ppm or less.

In one aspect, when measuring 2.5 mm thick polycarbonate plaques formed from bisphenol-A monomers according to ASTM D1925 using the methods of the present disclosure, their yellowness (YI) is less than about 1.6, for example about Less than 1.6, less than about 1.5, less than about 1.4, or less than about 1.3. In certain aspects, the yellowness of the 2.5 mm thick polycarbonate plaque may be less than about 1.5. In another aspect, the yellowness of the 2.5 mm thick polycarbonate plaque may be less than about 1.3. In another aspect, after heat aging at about 130 ° C. for 2,000 hours, the yellowness of the 2.5 mm thick polycarbonate plaque formed from bisphenol-A monomer using the method of the present disclosure as measured according to ASTM D1925 (YI) may have a yellowness (YI) of 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. In certain aspects, the yellowness of the 2.5 mm thick polycarbonate plaques after heat aging may be less than about 10. In another aspect, the yellowness of the 2.5 mm thick polycarbonate plaques after heat aging may be less than about 7. In another aspect, the yellowness of the 2.5 mm thick polycarbonate plaques after heat aging may be less than about 5. In another aspect, the yellowness of the 2.5 mm thick polycarbonate plaques after heat aging may be less than about 2.

In another aspect, the BPA polycarbonates produced by the methods described herein may have a purity level suitable for use in optical applications where high transmittance and low chromaticity are required, wherein the BPA polycarbonates are The above chemical reagent is contacted with the attached promoter ion exchange resin catalyst system to generate an eluate, and then prepared from bisphenol-A produced by performing a solvent crystallization step with the eluate.

In one aspect, the BPA polycarbonates prepared from bisphenol-A produced by the methods described herein have at least about 90%, for example about 90%, at a thickness of 2.5 mm, measured according to ASTM D1003-00. , 92%, 94%, 96%, 98%, or more. In another aspect, as described herein, the BPA polycarbonate may be free or substantially free of sulfur impurities. In another aspect, as described herein, the organic purity of the BPA polycarbonate may be at least about 99.5%. In another aspect, as described herein, BPA polycarbonate may have up to about 150 ppm of free hydroxyl groups. In another aspect, as described herein, BPA polycarbonate may have a sulfur concentration of less than about 5 ppm, or less than about 2 ppm.

In another aspect, the invention may include articles comprising BPA polycarbonates, such as polycarbonates made from BPA produced by the methods described herein. In another aspect, such an article may be selected from one or more of a light guide, light guide panel, lens, cover, sheet, light bulb, and film. In certain aspects, the article may comprise an LED lens. In another aspect, the article may include one or more of a portion of a roof, a portion of a greenhouse, and a portion of a veranda.

In another aspect, the BPA produced by the methods described herein may be a polycarbonate resin and / or a polycarbonate copolymer material, such as a polyester-polycarbonate copolymer, a polysiloxane-polycarbonate copolymer It can be used to prepare copolymers, alkylene terephthalate-polycarbonate copolymers, or combinations thereof. In another aspect, the BPA produced by the methods described herein can be used to prepare other polycarbonate copolymers not specifically mentioned herein, and the present invention is directed to any particular polycarbonate and / or poly It is not intended to be limited to carbonate copolymer materials.

In one aspect, bisphenol-A, polycarbonate, and articles of the present disclosure may include any combination of components, purity, and properties described herein, including various aspects, including individual components, purity, And / or properties such as sulfur concentration, yellowness, organic purity, and / or transmittance can be included in or excluded from the composition. Accordingly, combinations are contemplated that include one or more components, purity, and / or properties, but exclude other components, purity, and / or properties mentioned herein.

Examples of Embodiments

In one embodiment, the organic purity of the bisphenol-A monomer is at least about 99.5% by weight and the sulfur concentration is less than about 5 ppm, and the yellowness (YI) is about when formed from polycarbonate resin and molded into 2.5 mm plaques. Less than 1.5.

In another embodiment, the BPA polycarbonate has a purity level suitable for use in optical applications where high transmittance and low chromaticity are required, wherein the BPA polycarbonate has an accelerator ion exchanger attached to two or more chemical reagents. It is prepared from bisphenol-A produced by contact with a resin catalyst system to produce an eluate and then performing a solvent crystallization step with the eluate.

In various embodiments, (i) the sulfur concentration of the bisphenol-A monomer is less than about 2 ppm; And / or (ii) when formed from polycarbonate resins and molded into 2.5 mm plaques, the yellowness (YI) of the bisphenol-A monomer is less than about 1.3 as measured according to ASTM D1925; And / or (iii) when formed from polycarbonate resin and molded into 2.5 mm plaques, the bisphenol-A monomer has a yellowness (YI) as measured according to ASTM D1925 after heat aging at about 130 ° C. for 2,000 hours. Less than about 10; And / or (iv) when formed from polycarbonate resin and molded into 2.5 mm plaques, the bisphenol-A monomer has a yellowness (YI) as measured according to ASTM D1925 after heat aging at about 130 ° C. for 2,000 hours. Less than about 7; And / or (v) when formed from polycarbonate resin, the transfer rate of bisphenol-A monomer at 2.5 mm thickness as measured according to ASTM D1003-00 is at least about 90%; And / or (vi) the bisphenol-A monomer when formed from a polycarbonate resin has up to about 150 ppm of free hydroxyl groups; And / or (vii) the polycarbonate or copolymer comprises a polycarbonate prepared from any of the foregoing bisphenol-A embodiments; And / or (viii) the polycarbonate or copolymer is selected from the group consisting of polyester-polycarbonate copolymers, polysiloxane-polycarbonate copolymers, alkylene terephthalate-polycarbonate copolymers, or combinations thereof. One or more; And / or (ix) the yellowness (YI) of the polycarbonate or copolymer when molded into a 2.5 mm thick plaque is less than about 1.3 as measured according to ASTM D1925; And / or (x) after heat aging at about 130 ° C. for 2,000 hours when molded into a 2.5 mm thick plaque, the yellowness (YI) of the polycarbonate or copolymer is less than about 10 as measured according to ASTM D1925. Is; And / or (xi) the polycarbonate is free or substantially free of sulfur impurities; And / or (xii) the organic purity of the polycarbonate is at least about 99.5%; And / or (xiii) the polycarbonate has up to about 150 ppm of free hydroxyl groups; And / or (xiv) the transmittance of the polycarbonate is at least about 90% at 2.5 mm thickness as measured according to ASTM D1003-00; And / or (xv) the sulfur concentration of the polycarbonate is less than about 5 ppm; And / or (xvi) the sulfur concentration of the polycarbonate is less than about 2 ppm; And / or (xvii) the yellowness (YI) of the polycarbonate is less than about 1.5 when measured according to ASTM D1925 at 2.5 mm thickness; And / or (xviii) after heat aging at about 130 ° C. for 2,000 hours, the yellowness (YI) of the polycarbonate is less than about 10 as measured according to ASTM D1925 at 2.5 mm thickness; And / or (xix) after heat aging at about 130 ° C. for 2,000 hours, the yellowness (YI) of the polycarbonate is less than about 7, measured according to ASTM D1925 at 2.5 mm thickness; And / or (xx) after heat aging at about 130 ° C. for 2,000 hours, the yellowness (YI) of the polycarbonate is less than about 2 as measured according to ASTM D1925 at 2.5 mm thickness; And / or (xxi) BPA polycarbonate is an interpolymerized polycarbonate; And / or (xxii) the polycarbonate comprises a flame retardant; And / or (xxiii) the polycarbonate further comprises a second polycarbonate derived from bisphenol-A, wherein the second polycarbonate is different from the BPA polycarbonate; And / or (xxiv) the second polycarbonate comprises a homopolycarbonate wherein the second polycarbonate is derived from bisphenol; Copolycarbonates derived from more than bisphenols; And at least one copolymer derived from at least one bisphenol and comprising at least one aliphatic ester unit or aromatic ester unit or siloxane unit; And / or (xxv) the polycarbonate further comprises one or more additives selected from one or more of UV stabilizing additives, thermal stabilizing additives, mold release agents, colorants, organic fillers, inorganic fillers, and gamma-stabilizing agents; And / or (xxvi) the article comprises bisphenol-A and / or polycarbonate of one or a combination of the foregoing embodiments; And / or (xxvii) the article comprises one or more of a light guide, light guide panel, lens, cover, sheet, light bulb, and film; And / or (xxviii) the article is an LED lens; And / or (xxix) the article comprises at least one of a portion of a roof, a portion of a greenhouse, and a portion of a veranda.

Example

The following examples are presented to provide one of ordinary skill in the art with complete disclosure and description of methods of making and evaluating the compounds, compositions, articles, devices, and / or methods claimed herein, and the present invention. It is intended to be purely illustrative, and is not intended to limit the scope that the inventors regard as their invention. Efforts have been made to ensure accuracy with respect to numbers (eg amounts, temperature, etc.) but some errors and deviations should be accounted for. Unless indicated otherwise, par is parts by weight, temperature is in degrees Centigrade or ambient temperature, and pressure is at or near atmospheric.

1. General method

In the first embodiment, phenol and acetone are respectively fed to the reactor, which are mixed continuously using a fixed mixer. Before feeding the reactor feed to the reactor vessel, it is cooled using a plate heat exchanger. The phase of the ion exchange resin with attached promoter (2% crosslinked ion exchange resin catalyst + DMT attached promoter) is placed in the reactor such that the reactor feed flows downward through the reactor. The conversion of acetone in the reactor is planned to be at least about 90%, while the p, p-BPA selectivity is at least about 93%.

After the reaction, the eluent stream is transferred to a separate vessel, where the stream passes through an anion exchange resin to remove free oligomers. The eluate is then subjected to a water removal step. After the water removal step, the dewatered eluate stream is subjected to a phenol recovery step, using a phenol flash column to remove phenol remaining in the eluate stream. The solvent crystallization unit can remove all or substantially all of the BPA byproducts. The remaining eluate stream is then treated in a solvent recovery system to remove aromatic solvent (s) such as toluene. Thus, toluene or other aromatic solvent is removed from the BPA isomer stream.

2. Preparation of BPA

In a second example, polycarbonate resins were prepared using BPA samples from different sources (eg, BPA process catalysts and promoters). Polycarbonate resin was manufactured in a single manufacturing facility using an interfacial polymerization process. Then, the molded plaque was prepared from a polycarbonate resin stabilized with 0.05 wt.% IRGAFOS ^® 168 tris-aryl phosphite processing stabilizer.

The sulfur content and organic purity of each BPA sample was measured. Sulfur measurement was carried out by the combustion and colorimeter method for total sulfur measurement. Organic purity was measured using ultraviolet detection after high performance chromatography separation (see HPLC Method in Nowakowska et al., Polish J. Appl. Chem., XI (3), 247-254, 1996). Organic purity defines 100% by weight of the total of unknown and known impurities detected at 280 nm through ultraviolet light.

The chromaticity of each 2.5 mm plaque was measured according to ASTM D1925 after molding (YI0) as well as after heat aging at 130 ° C. for 2,000 hours (YI, 2000hrs 130C). Table 1 below shows the chromaticity, purity, and sulfur concentration of each sample. Samples prepared using BPA from a conventional bulk accelerator system using ion exchange resins with sulfonic acid groups with 3MPA promoters were defined as "BP" in the BPA process column. Samples prepared using BPA from a process using hydrochloric acid as catalyst are defined as "HCl" in the BPA process column. Samples prepared using BPA from the attached promoter methods of the present invention described herein are defined as "AP" in a BPA process column.

Color and Purity Analysis of BPA Substances Example YI
(-) YI (2000hrs 130C) BPA Purity
(% w) sulfur
(ppm) BPA process
Catalyst / Accelerator Comparative Example 1 1.88 13.40 99.44 25 BP Comparative Example 2 1.85 13.07 99.52 23 BP Comparative Example 3 1.96 13.37 99.45 25 BP Comparative Example 4 1.78 13.20 99.52 23 BP Comparative Example 5 2.01 13.61 99.44 25 BP Comparative Example 6 1.59 10.29 99.54 19 BP Comparative Example 7 1.65 11.74 99.47 17 BP Comparative Example 8 1.47 10.92 99.45 21 BP Comparative Example 9 1.80 10.61 99.39 23 BP Comparative Example 10 1.57 14.33 99.50 18 BP Comparative Example 11 1.49 12.40 99.51 16 BP Comparative Example 12 1.39 10.01 99.57 18 BP Comparative Example 13 1.65 11.72 99.47 21 BP Comparative Example 14 1.69 10.76 99.61 <2 HCl Comparative Example 15 1.66 10.45 99.62 <2 HCl Example 16 1.20 6.79 99.53 <2 AP Example 17 1.35 6.24 99.54 <2 AP Example 18 1.26 6.72 99.54 <2 AP Example 19 1.29 7.63 99.57 <2 AP Example 20 1.27 8.66 99.50 <2 AP Example 21 1.31 8.71 99.56 <2 AP Example 22 1.25 4.93 99.78 <2 AP Example 23 1.39 8.92 99.55 <2 AP Example 24 1.42 8.04 99.57 <2 AP Example 25 1.33 5.38 99.75 <2 AP Example 26 1.36 4.57 99.78 <2 AP

BPA prepared using conventional bulk accelerator systems had about 20 ppm sulfur even after purification of the monomers. BPA prepared using HCl showed a sulfur concentration of less than about 2 ppm. Similarly, BPA produced from the attached promoter system described herein exhibited a sulfur concentration of less than about 2 ppm, ie, below the detection limit of the measurement equipment.

As shown in Table 1, the color (ie, yellowing) of the polycarbonate plaques prepared from each of the BPA samples was measured. Polycarbonate resins prepared from conventional bulk accelerators (BP) and HCl derived BPA are significantly more than resins prepared from BPA derived from attached promoters (AP), both for molded plaques and heat-aged plaques. Higher yellowing. Graphical summaries for color measurements (yellowness) after molding and after heat aging at 130 ° C. for 2,000 hours are shown in FIGS. 1 and 2, respectively. For both shaping and heat-aging plaques, polycarbonate resins prepared from BPA produced by the attached promoter methods of the present disclosure are polycarbonate resins prepared from HCl and conventional bulk promoter (BP) BPA. The yellowness was significantly lower than that of.

Although BPA prepared from HCl may exhibit good purity and low sulfur concentrations, the polycarbonates produced therefrom are to the extent that polycarbonates produced from BPA produced from the attached promoter methods of the present disclosure have. It does not have a yellowing reduction advantage. BPAs produced from conventional bulk accelerator (BP) systems exhibit both higher sulfur content and yellowness (in derivatized polycarbonates) as compared to BPAs produced by the attached promoter methods of the present disclosure.

For both forming and heat-aging plaques, plots of BPA purity versus color (ie yellowness) are shown in FIGS. 3 and 4.

Statistical analysis (ANOVA) indicates that there is a significant difference (95% confidence) between the AP derived sample and other materials, both for the starting color as well as the color after heat aging. Comparing Examples 16 to 26 of the present invention with Comparative Examples 14 and 15, this improved color is not simply related to the sulfur content in the resin, which is one of the differences in comparison of AP and BP derived materials. , Total organic concentration itself is a factor in determining color and color stability as shown in the more detailed graphs (FIGS. 3 and 4). While higher organic monomer purity appears to result in lower yellowness for BP derived samples, AP derived samples are clearly superior to BP materials, for example 99.55% in terms of given purity.

Those skilled in the art will appreciate that various modifications and changes can be made to the present invention without departing from the spirit or scope of the invention. Other embodiments of the present invention will be apparent to those skilled in the art in view of the detailed description and practice of the invention disclosed herein. It is intended that the description and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.

Claims (31)

Bisphenol-A monomer having an organic purity of at least about 99.5% by weight and a sulfur concentration of less than about 5 ppm,
Bisphenol-A monomer, characterized in that the yellowness (YI) is less than about 1.5 when formed from polycarbonate resin and molded into 2.5 mm plaques. The method according to claim 1,
Bisphenol-A monomer, characterized in that the sulfur concentration is less than about 2 ppm. 3. The method according to claim 1 or 2,
Bisphenol-A monomer, when formed of polycarbonate resin and molded into 2.5 mm plaque, characterized by a yellowness (YI) of less than about 1.3 as measured according to ASTM D1925. 4. The method according to any one of claims 1 to 3,
When formed of polycarbonate resin and molded into 2.5 mm plaques, after heat aging at about 130 ° C. for 2,000 hours, the yellowness (YI) as measured according to ASTM D1925 is characterized by less than about 10 , Bisphenol-A monomer. 5. The method of claim 4,
Bisphenol-A, which is formed of polycarbonate resin and molded into 2.5 mm plaque, after heat aging at about 130 ° C. for 2,000 hours, has a yellowness (YI) of less than about 7 as measured according to ASTM D1925. Monomers. 6. The method according to any one of claims 1 to 5,
Bisphenol-A monomer, when formed of polycarbonate resin, characterized in that it has a transmission level of at least about 90% at a thickness of 2.5 mm as measured according to ASTM D1003-00. 7. The method according to any one of claims 1 to 6,
Bisphenol-A monomer, when formed from polycarbonate resin, has free hydroxyl groups of about 150 ppm or less. Polycarbonate prepared from bisphenol-A according to any one of claims 1 to 7, or a copolymer comprising polycarbonate. 9. The method of claim 8,
Polycarbonate, characterized in that it comprises at least one of a polyester-polycarbonate copolymer, a polysiloxane-polycarbonate copolymer, an alkylene terephthalate-polycarbonate copolymer, or a combination thereof Or copolymers. 10. The method according to claim 8 or 9,
Polycarbonate or copolymer, when shaped into a 2.5 mm thick plaque, characterized by a yellowness (YI) of less than about 1.3 as measured according to ASTM D1925. 11. The method according to any one of claims 8 to 10,
Polycarbonate or copolymer, characterized by a yellowness (YI) of less than about 10 when measured according to ASTM D1925 when molded into a 2.5 mm thick plaque and heat aged at about 130 ° C. for 2,000 hours. BPA polycarbonate having a purity level suitable for use in optical applications where high transmittance and lower color are required,
The BPA polycarbonate is prepared from bisphenol-A produced by contacting two or more chemical reagents with an attached promoter ion exchange resin catalyst system to obtain an eluate and then performing a solvent crystallization step with the eluate. , BPA polycarbonate. 13. The method of claim 12,
BPA polycarbonate, characterized in that it contains no or substantially no sulfur impurities. The method according to claim 12 or 13,
BPA polycarbonate, characterized in that the organic purity is at least about 99.5%. 15. The method according to any one of claims 12 to 14,
BPA polycarbonate, characterized by having less than about 150 ppm free hydroxyl groups. 16. The method according to any one of claims 12 to 15,
BPA polycarbonate, characterized in that the transmittance is at least about 90% at 2.5 mm thickness, measured according to ASTM D1003-00. 17. The method according to any one of claims 12 to 16,
BPA polycarbonate, characterized in that the sulfur concentration is less than about 5 ppm. 18. The method of claim 17,
BPA polycarbonate, characterized in that the sulfur concentration is less than about 2 ppm. The method according to any one of claims 12 to 18,
BPA polycarbonate, characterized by a yellowness (YI) of less than about 1.5 at 2.5 mm thickness, measured according to ASTM D1925. The method according to any one of claims 12 to 19,
BPA polycarbonate, characterized by a yellowness (YI) of less than about 10 at 2.5 mm thickness, after heat aging at about 130 ° C. for 2,000 hours, measured according to ASTM D1925. 21. The method of claim 20,
BPA polycarbonate, characterized by a yellowness (YI) of less than about 7, at 2.5 mm thickness, after heat aging at about 130 ° C. for 2,000 hours, measured according to ASTM D1925. 22. The method of claim 21,
BPA polycarbonate, characterized by a yellowness (YI) of less than about 2 at 2.5 mm thickness after heat aging at about 130 ° C. for 2,000 hours, measured according to ASTM D1925. The method according to any one of claims 12 to 22,
BPA polycarbonate, characterized in that the BPA polycarbonate is an interpolymerized polycarbonate. The method according to any one of claims 12 to 23, wherein
BPA polycarbonate, characterized in that it comprises a flame retardant. The method according to any one of claims 12 to 24,
Further comprising a second polycarbonate from bisphenol-A,
BPA polycarbonate, characterized in that the second polycarbonate is different from the BPA polycarbonate. 26. The method of claim 25,
The second polycarbonate is a homopolycarbonate derived from bisphenol; Copolycarbonates derived from more than on bisphenols; And at least one of a copolymer derived from one or more bisphenols and comprising one or more aliphatic ester units or aromatic ester units or siloxane units. The method according to any one of claims 1 to 26,
BPA polycarbonate, characterized in that it further comprises one or more additives selected from one or more of UV stabilizing additives, thermal stabilizing additives, mold release agents, colorants, organic fillers, inorganic fillers, and gamma-stabilizers. An article comprising bisphenol A according to any one of claims 1 to 7 or polycarbonate according to any one of claims 8 to 27. 29. The method of claim 28,
And the article is selected from one or more of a light guide, a light guide panel, a lens, a cover, a sheet, a light bulb, and a film. 29. The method of claim 28,
The article of claim 1, wherein the article is an LED lens. 29. The method of claim 28,
Wherein the article comprises at least one of a portion of a roof, a portion of a greenhouse, and a portion of a veranda.

Images