Patent Publication Number: US-2013245223-A1

Title: High heat polyethersulfone compositions

Description:
BACKGROUND 
     This invention relates to high heat polyethersulfone compositions, methods for their preparation, and articles made therefrom. 
     Polyethersulfones are a commercially important family of high performance, high temperature thermoplastics. These polymers are of interest to many industries because of their combination of high ductility, high heat resistance, hydrolysis resistance in steam and hot water environments and good overall chemical resistance. In addition, polyethersulfones are frequently transparent, unlike many non-transparent, semi-crystalline materials which are also used in high temperature applications. 
     Polyethersulfones can be produced by a variety of methods. For example, U.S. Pat. Nos. 4,108,837 and 4,175,175 describe the preparation of polyarylethers and in particular polyarylethersulfones. U.S. Pat. No. 6,228,970 describes the preparation polyarylethersulfones with improved polydispersity and reduced oligomer content. British patent GB 1,264,900 teaches a process for production of a polyethersulfone comprising structural units derived from 4,4′-biphenol, bisphenol-A, and bis(4-chlorophenyl)sulfone. 
     Currently available polyethersulfones typically possess an intermediate level of heat resistance. Commercially important polyarylethersulfones include polysulfone (PSU), polyphenylsulfone (PPSU) and polyethersulfone (PES). PSU is a well-known high temperature amorphous engineering thermoplastic resin exhibiting a glass transition temperature (Tg) of about 185° C., high strength, stiffness and toughness over a temperature range of from about −100° to 150° C. PSU has an Izod impact strength value (Notched Izod value) of about 69 Jm −1  (1.3 ft-lb/in). PSU was commercially introduced in 1965 by the Union Carbide Corporation and is commercially available as UDEL® polysulfone from Solvay Advanced Polymers LLC. Another versatile polyarylethersulfone polymer is polyphenylsulfone (PPSU). PPSU is commercially available from Solvay Advanced Polymers LLC under the trademark of RADEL®. It has a Tg of 220° C. and an hod impact strength value of about 700 Jm −1  (13 ft-lb/in). 
     In various applications it would be highly desirable to produce polyethersulfones with increased heat resistance (higher glass transition temperatures) relative to known polyethersulfones, while maintaining a useful level of impact strength. 
     BRIEF DESCRIPTION 
     In one embodiment, the present invention provides a polyethersulfone composition comprising structural units I 
     
       
         
         
             
             
         
       
     
     wherein R 1 , R 2 , R 3 , and R 4  are independently at each occurrence halogen, nitro, a C 1 -C 20  aliphatic radical, a C 3 -C 20  cycloaliphatic radical, or a C 2 -C 20  aromatic radical; and “a”, “b”, “c”, “d”, “e”, “f”, “g” and “h” are independently integers from 0 to 4. 
     In another embodiment, the present invention provides a polyethersulfone composition comprising structural units derived from at least one fluorenone bisphenol VI 
     
       
         
         
             
             
         
       
     
     wherein R 1  and R 2  are independently at each occurrence halogen, nitro, a C 1 -C 20  aliphatic radical, a C 3 -C 20  cycloaliphatic radical, or a C 2 -C 20  aromatic radical; and “a”, “b”, “c”, and “d” are independently integers from 0 to 4;
 
at least one biphenyl-bissulfone VII
 
     
       
         
         
             
             
         
       
     
     wherein X 1  and X 2  are independently halogen or nitro; R 3  and R 4  are independently at each occurrence halogen, nitro, a C 1 -C 20  aliphatic radical, a C 3 -C 20  cycloaliphatic radical, or a C 2 -C 20  aromatic radical; and “e”, “f”, “g”, and “h” are independently integers from 0 to 4; and
 
optionally structural units derived from at least one biphenol VIII
 
     
       
         
         
             
             
         
       
     
     wherein R 5  is independently at each occurrence halogen, nitro, a C 1 -C 20  aliphatic radical, a C 3 -C 20  cycloaliphatic radical, or a C 2 -C 20  aromatic radical; and “i” and “j” are independently integers from 0 to 4. 
     In various aspects and embodiments, the invention may provide one or more molded articles comprising at least one polyethersulfone composition of the present invention. In various other embodiments, there is provided a method for making the polyethersulfone compositions of the present invention. 
    
    
     DETAILED DESCRIPTION 
     Approximating language, as used herein throughout the specification and claims, may be applied to modify any quantitative representation that could permissibly vary without resulting in a change in the basic function to which it is related. Accordingly, a value modified by a term or terms, such as “about” and “substantially”, are not to be limited to the precise value specified. In at least some instances, the approximating language may correspond to the precision of an instrument for measuring the value. Here and throughout the specification and claims, range limitations may be combined and/or interchanged, such ranges are identified and include all the sub-ranges contained therein unless context or language indicates otherwise. 
     The singular forms “a”, “an” and “the” include plural referents unless the context clearly dictates otherwise. 
     “Optional” or “optionally” means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event occurs and instances where it does not. 
     As used herein the term “FBPA” is an acronym representing the fluorenone bisphenol 9,9-bis(4-hydroxyphenyl)fluorene. 
     As used herein, the term “aromatic radical” refers to an array of atoms having a valence of at least one comprising at least one aromatic group. The array of atoms having a valence of at least one comprising at least one aromatic group may include heteroatoms such as nitrogen, sulfur, selenium, silicon and oxygen, or may be composed exclusively of carbon and hydrogen. As used herein, the term “aromatic radical” includes but is not limited to phenyl, pyridyl, furanyl, thienyl, naphthyl, phenylene, and biphenyl radicals. As noted, the aromatic radical contains at least one aromatic group. The aromatic group is invariably a cyclic structure having 4n+2 “delocalized” electrons where “n” is an integer equal to 1 or greater, as illustrated by phenyl groups (n=1), thienyl groups (n=1), furanyl groups (n=1), naphthyl groups (n=2), azulenyl groups (n=2), anthraceneyl groups (n=3) and the like. The aromatic radical may also include nonaromatic components. For example, a benzyl group is an aromatic radical which comprises a phenyl ring (the aromatic group) and a methylene group (the nonaromatic component). Similarly a tetrahydronaphthyl radical is an aromatic radical comprising an aromatic group (C 6 H 3 ) fused to a nonaromatic component —(CH 2 ) 4 —. For convenience, the term “aromatic radical” is defined herein to encompass a wide range of functional groups such as alkyl groups, alkenyl groups, alkynyl groups, haloalkyl groups, haloaromatic groups, conjugated dienyl groups, alcohol groups, ether groups, aldehydes groups, ketone groups, carboxylic acid groups, acyl groups (for example carboxylic acid derivatives such as esters and amides), amine groups, nitro groups, and the like. For example, the 4-methylphenyl radical is a C 7  aromatic radical comprising a methyl group, the methyl group being a functional group which is an alkyl group. Similarly, the 2-nitrophenyl group is a C 6  aromatic radical comprising a nitro group, the nitro group being a functional group. Aromatic radicals include halogenated aromatic radicals such as 4-trifluoromethylphenyl, hexafluoroisopropylidenebis(4-phen-1-yloxy) (i.e., OPhC(CF 3 ) 2 PhO—), 4-chloromethylphen-1-yl, 3-trifluorovinyl-2-thienyl, 3-trichloromethylphen-1-yl (i.e., 3-CCl 3 Ph-), 4-(3-bromoprop-1-yl)phen-1-yl (i.e., 4-BrCH 2 CH 2 CH 2 Ph-), and the like. Further examples of aromatic radicals include 4-allyloxyphen-1-oxy, 4-aminophen-1-yl (i.e., 4-H 2 NPh-), 3-aminocarbonylphen-1-yl (i.e., NH 2 COPh-), 4-benzoylphen-1-yl, dicyanomethylidenebis(4-phen-1-yloxy) (i.e., —OPhC(CN) 2 PhO—), 3-methylphen-1-yl, methylenebis(4-phen-1-yloxy) (i.e., —OPhCH 2 PhO—), 2-ethylphen-1-yl, phenylethenyl, 3-formyl-2-thienyl, 2-hexyl-5-furanyl, hexamethylene-1,6-bis(4-phen-1-yloxy) (i.e., —OPh(CH 2 ) 6 PhO—), 4-hydroxymethylphen-1-yl (i.e., 4-HOCH 2 Ph-), 4-mercaptomethylphen-1-yl (i.e., 4-HSCH 2 Ph-), 4-methylthiophen-1-yl (i.e., 4-CH 3 SPh-), 3-methoxyphen-1-yl, 2-methoxycarbonylphen-1-yloxy (e.g., methyl salicyl), 2-nitromethylphen-1-yl (i.e., 2-NO 2 CH 2 Ph), 3-trimethylsilylphen-1-yl, 4-t-butyldimethylsilylphenl-1-yl, 4-vinylphen-1-yl, vinylidenebis(phenyl), and the like. The term “a C 3 -C 10  aromatic radical” includes aromatic radicals containing at least three but no more than 10 carbon atoms. The aromatic radical 1-imidazolyl (C 3 H 2 N 2 —) represents a C 3  aromatic radical. The benzyl radical (C 7 H 7 —) represents a C 7  aromatic radical. 
     As used herein the term “cycloaliphatic radical” refers to a radical having a valence of at least one, and comprising an array of atoms which is cyclic but which is not aromatic. As defined herein a “cycloaliphatic radical” does not contain an aromatic group. A “cycloaliphatic radical” may comprise one or more noncyclic components. For example, a cyclohexylmethyl group (C 6 H 11 CH 2 —) is an cycloaliphatic radical which comprises a cyclohexyl ring (the array of atoms which is cyclic but which is not aromatic) and a methylene group (the noncyclic component). The cycloaliphatic radical may include heteroatoms such as nitrogen, sulfur, selenium, silicon and oxygen, or may be composed exclusively of carbon and hydrogen. For convenience, the term “cycloaliphatic radical” is defined herein to encompass a wide range of functional groups such as alkyl groups, alkenyl groups, alkynyl groups, haloalkyl groups, conjugated dienyl groups, alcohol groups, ether groups, aldehyde groups, ketone groups, carboxylic acid groups, acyl groups (for example carboxylic acid derivatives such as esters and amides), amine groups, nitro groups, and the like. For example, the 4-methylcyclopent-1-yl radical is a C 6  cycloaliphatic radical comprising a methyl group, the methyl group being a functional group which is an alkyl group. Similarly, the 2-nitrocyclobut-1-yl radical is a C 4  cycloaliphatic radical comprising a nitro group, the nitro group being a functional group. A cycloaliphatic radical may comprise one or more halogen atoms which may be the same or different. Halogen atoms include, for example; fluorine, chlorine, bromine, and iodine. Cycloaliphatic radicals comprising one or more halogen atoms include 2-trifluoromethylcyclohex-1-yl, 4-bromodifluoromethylcyclooct-1-yl, 2-chlorodifluoromethylcyclohex-1-yl, hexafluoroisopropylidene-2,2-bis(cyclohex-4-yl) (i.e., —C 6 H 10 C(CF 3 ) 2 C 6 H 10 —), 2-chloromethylcyclohex-1-yl, 3-difluoromethylenecyclohex-1-yl, 4-trichloromethylcyclohex-1-yloxy, 4-bromodichloromethylcyclohex-1-ylthio, 2-bromoethylcyclopent-1-yl, 2-bromopropylcyclohex-1-yloxy (e.g., CH 3 CHBrCH 2 C 6 H 10 O—), and the like. Further examples of cycloaliphatic radicals include 4-allyloxycyclohex-1-yl, 4-aminocyclohex-1-yl (i.e., H 2 NC 6 H 10 —), 4-aminocarbonylcyclopent-1-yl (i.e., NH 2 COC 5 H 8 —), 4-acetyloxycyclohex-1-yl, 2,2-dicyanoisopropylidenebis(cyclohex-4-yloxy) (i.e., —OC 6 H 10 C(CN) 2 C 6 H 10 O—), 3-methylcyclohex-1-yl, methylenebis(cyclohex-4-yloxy) (i.e., —OC 6 H 10 CH 2 C 6 H 10 O—), 1-ethylcyclobut-1-yl, cyclopropylethenyl, 3-formyl-2-terahydrofuranyl, 2-hexyl-5-tetrahydrofuranyl, hexamethylene-1,6-bis(cyclohex-4-yloxy) (i.e., —OC 6 H 10 (CH 2 ) 6 C 6 H 10 O—), 4-hydroxymethylcyclohex-1-yl (i.e., 4-HOCH 2 C 6 H 10 —), 4-mercaptomethylcyclohex-1-yl (i.e., 4-HSCH 2 C 6 H 10 —), 4-methylthiocyclohex-1-yl (i.e., 4-CH 3 SC 6 H 10 —), 4-methoxycyclohex-1-yl, 2-methoxycarbonylcyclohex-1-yloxy(2-CH 3 OCOC 6 H 10 O—), 4-nitromethylcyclohex-1-yl (i.e., NO 2 CH 2 C 6 H 10 —), 3-trimethylsilylcyclohex-1-yl, 2-t-butyldimethylsilylcyclopent-1-yl, 4-trimethoxysilylethylcyclohex-1-yl (e.g., (CH 3 O) 3 SiCH 2 CH 2 C 6 H 10 —), 4-vinylcyclohexen-1-yl, vinylidenebis(cyclohexyl), and the like. The term “a C 3 -C 10  cycloaliphatic radical” includes cycloaliphatic radicals containing at least three but no more than 10 carbon atoms. The cycloaliphatic radical 2-tetrahydrofuranyl (C 4 H 7 O—) represents a C 4  cycloaliphatic radical. The cyclohexylmethyl radical (C 6 H 11 CH 2 —) represents a C 7  cycloaliphatic radical. 
     As used herein the term “aliphatic radical” refers to an organic radical having a valence of at least one consisting of a linear or branched array of atoms which is not cyclic. Aliphatic radicals are defined to comprise at least one carbon atom. The array of atoms comprising the aliphatic radical may include heteroatoms such as nitrogen, sulfur, silicon, selenium and oxygen or may be composed exclusively of carbon and hydrogen. For convenience, the term “aliphatic radical” is defined herein to encompass, as part of the “linear or branched array of atoms which is not cyclic” a wide range of functional groups such as alkyl groups, alkenyl groups, alkynyl groups, haloalkyl groups, conjugated dienyl groups, alcohol groups, ether groups, aldehyde groups, ketone groups, carboxylic acid groups, acyl groups (for example carboxylic acid derivatives such as esters and amides), amine groups, nitro groups, and the like. For example, the 4-methylpent-1-yl radical is a C 6  aliphatic radical comprising a methyl group, the methyl group being a functional group which is an alkyl group. Similarly, the 4-nitrobut-1-yl group is a C 4  aliphatic radical comprising a nitro group, the nitro group being a functional group. An aliphatic radical may be a haloalkyl group which comprises one or more halogen atoms which may be the same or different. Halogen atoms include, for example; fluorine, chlorine, bromine, and iodine. Aliphatic radicals comprising one or more halogen atoms include the alkyl halides trifluoromethyl, bromodifluoromethyl, chlorodifluoromethyl, hexafluoroisopropylidene, chloromethyl, difluorovinylidene, trichloromethyl, bromodichloromethyl, bromoethyl, 2-bromotrimethylene (e.g., —CH 2 CHBrCH 2 —), and the like. Further examples of aliphatic radicals include allyl, aminocarbonyl (i.e., —CONH 2 ), carbonyl, 2,2-dicyanoisopropylidene (i.e., —CH 2 C(CN) 2 CH 2 —), methyl (i.e., —CH 3 ), methylene (i.e., —CH 2 —), ethyl, ethylene, formyl (i.e., —CHO), hexyl, hexamethylene, hydroxymethyl (i.e., —CH 2 OH), mercaptomethyl (i.e., —CH 2 SH), methylthio (i.e., —SCH 3 ), methylthiomethyl (i.e., —CH 2 SCH 3 ), methoxy, methoxycarbonyl (i.e., CH 3 OCO—), nitromethyl (i.e., —CH 2 NO 2 ), thiocarbonyl, trimethylsilyl (i.e., (CH 3 ) 3 Si—), t-butyldimethylsilyl, 3-trimethyoxysilypropyl (i.e., (CH 3 O) 3 SiCH 2 CH 2 CH 2 —), vinyl, vinylidene, and the like. By way of further example, a C 1 -C 10  aliphatic radical contains at least one but no more than 10 carbon atoms. A methyl group (i.e., CH 3 —) is an example of a C 1  aliphatic radical. A decyl group (i.e., CH 3 (CH 2 ) 9 —) is an example of a C 10  aliphatic radical. 
     As noted, the present invention provides a polyethersulfone composition comprising structural units I 
     
       
         
         
             
             
         
       
     
     wherein R 1 , R 2 , R 3 , and R 4  are independently at each occurrence halogen, nitro, a C 1 -C 20  aliphatic radical, a C 3 -C 20  cycloaliphatic radical, or a C 2 -C 20  aromatic radical; and “a”, “b”, “c”, “d”, “e”, “f”, “g” and “h” are independently integers from 0 to 4. 
     Structural units I present in the polyethersulfone compositions of the present invention are illustrated in Table 1 below wherein illustrative substitution patterns and definitions for R 1 , R 2 , R 3 , and R 4 ; and integers “a”, “b”, “c”, “d”, “e”, “f”, “g” and “h” are given. 
     
       
         
           
               
             
               
                 TABLE 1 
               
             
            
               
                   
               
               
                 Examples of Structural Units I 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                 Entry 
                 R 1   
                 R 2   
                 R 3   
                 R 4   
                 “a” 
                 “b” 
                 “c” 
                 “d” 
                 “e” 
                 “f” 
                 “g” 
                 “h” 
               
               
                   
               
               
                 I-1 
                 — 
                 — 
                 — 
                 — 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
               
               
                 I-2 
                 3-Me 
                 — 
                 — 
                 — 
                 1 
                 1 
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
               
               
                 I-3 
                 — 
                 — 
                 3-Cl 
                 — 
                 0 
                 0 
                 0 
                 0 
                 1 
                 1 
                 0 
                 0 
               
               
                 I-4 
                 — 
                 3-Me 
                 — 
                 3-Cl 
                 0 
                 0 
                 1 
                 0 
                 0 
                 0 
                 1 
                 1 
               
               
                   
               
               
                 With respect to groups R 1 -R 4 , “—” indicates default substitution by hydrogen. 
               
            
           
         
       
     
     Polymer compositions comprising structural units I are referred to herein polyethersulfones, owing to the presence of both ether linkages (—O—), and sulfone (—SO 2 —) linkages as features of the polymer structure. Structure I need not be regarded as the “repeat unit” of the polymer, but rather structure I may be regarded as a structural feature occurring at least once in the polymer. For example, a polymer composition might comprise a plurality of structural units I as part of the polymer chain and yet no two structural units I are adjacent to one another in the polymer chain (i.e. repeat). Alternatively, structure I may constitute essentially all of the internal structural units (all structural units apart from the end groups of the polymer chain) of the composition and as such represent the “repeat unit” of the polymer chain. In structure I, and throughout this disclosure, the dashed line ( - - - - - - ) signals the point of attachment of one structural unit to an adjacent structural unit. 
     Polyethersulfone compositions comprising structural units I have been found to possess exceptionally high glass transition temperatures (Tg) making them suitable for use in high heat applications. In one embodiment, the present invention provides a polyethersulfone composition having a glass transition temperature of at least 300° C. In an alternate embodiment, the present invention provides a polyethersulfone composition having a glass transition temperature of at least 270° C. In yet another embodiment, the present invention provides a polyethersulfone composition having a glass transition temperature of at least 250° C. 
     In one embodiment, the polyethersulfone composition further comprises structural units II 
     
       
         
         
             
             
         
       
     
     wherein R 5  and R 6  are independently at each occurrence halogen, nitro, a C 1 -C 20  aliphatic radical, a C 3 -C 20  cycloaliphatic radical, or a C 2 -C 20  aromatic radical; and “i”, “j”, “k”, and “l” are independently integers from 0 to 4. As in the case of structural unit I, structural unit II need not be a “repeat” unit but may simply be a structural feature of the polyethersulfone composition. Alternatively, structural unit II may represent a repeat unit of the composition. 
     In yet another embodiment, the polyethersulfone composition of the present invention further comprises structural units III 
     
       
         
         
             
             
         
       
     
     wherein R 3 , R 4 , and R 5  are independently at each occurrence halogen, nitro, a C 1 -C 20  aliphatic radical, a C 3 -C 20  cycloaliphatic radical, or a C 2 -C 20  aromatic radical; and “e”, “f”, “g”, “h”, “i”, and “j” are independently integers from 0 to 4. As in the cases of structural groups I and II, structural group III may or may not represent a “repeat unit” of the composition. 
     In yet still another embodiment, the present invention provides a composition further comprising structural units IV 
     
       
         
         
             
             
         
       
     
     wherein R 1 , R 2 , and R 6  are independently at each occurrence halogen, nitro, a C 1 -C 20  aliphatic radical, a C 3 -C 20  cycloaliphatic radical, or a C 2 -C 20  aromatic radical; and “a”, “b”, “c”, “d”, “k”, and “l” are independently integers from 0 to 4. As in the cases of structural groups I, II, and III, structural group VI may or may not represent a “repeat unit” of the composition. It should be stressed that notwithstanding the presence of additional structural units (for example one or more of structural groups II, III and IV), each of the compositions of the present invention comprises at least one structural unit I. 
     In one embodiment, the present invention provides a polyethersulfone composition comprising structural units I which are “unsubstituted”. This is the case when each of the variables “a”, “b”, “c”, “d”, “e”, “f”, “g” and “h” is zero. This condition is illustrated in Table 1 by Entry I-1. As will be appreciated by those skilled in the art, all positions within a structural group capable of accommodating a substituent group, default to substitution by hydrogen when a variable, for example the variable “e”, is defined to be zero. In one embodiment, the present invention provides a polyethersulfone composition comprising structural units I and II wherein the variables “i”, “j”, “k”, and “l” of structure II are each zero. In another embodiment, the present invention provides a polyethersulfone composition comprising structural units I and III wherein the variables “e”, “f”, “g”, “h”, “i”, and “j” of structures I and III are each zero. In yet another embodiment, the present invention provides a polyethersulfone composition comprising structural units I and IV wherein the variables “a”, “b”, “c”, “d”, “k”, and “l” of structures I and IV are each zero. 
     In one embodiment, the polyethersulfone composition provided by the present invention further comprises structural units derived from at least one bisphenol having structure V 
     
       
         
         
             
             
         
       
     
     wherein R 7  is independently at each occurrence halogen, nitro, a C 1 -C 20  aliphatic radical, a C 3 -C 20  cycloaliphatic radical, or a C 2 -C 20  aromatic radical; W an oxygen atom, a sulfur atom, a selenium atom, a divalent C 1 -C 20  aliphatic radical, a divalent C 3 -C 20  cycloaliphatic radical, or a divalent C 2 -C 20  aromatic radical; and “m”, and “n” are independently integers from 0 to 4. 
     Bisphenols having structure V are illustrated by 1,1-bis(4-hydroxyphenyl)cyclopentane; 2,2-bis(3-allyl-4-hydroxyphenyl)propane; 2,2-bis(2-t-butyl-4-hydroxy-5-methylphenyl)propane; 2,2-bis(3-t-butyl-4-hydroxy-6-methylphenyl)propane; 2,2-bis(3-t-butyl-4-hydroxy-6-methylphenyl)butane; 2,2-bis(3-methyl-4-hydroxyphenyl)propane; 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane; 1,1-bis(4-hydroxyphenyl-2,2,2-trichloroethane; 1,1-bis(4-hydroxyphenyl)norbornane; 1,2-bis(4-hydroxyphenyl)ethane; 1,3-bis(4-hydroxyphenyl)propenone; bis(4-hydroxyphenyl)sulfide; 4,4-bis(4-hydroxyphenyl)pentanoic acid; 4,4-bis(3,5-dimethyl-4-hydroxyphenyl)pentanoic acid; 2,2-bis(4-hydroxyphenyl)acetic acid; 2,4′-dihydroxydiphenylmethane; bis(2-hydroxyphenyl)methane; bis(4-hydroxyphenyl)methane; bis(4-hydroxy-5-nitrophenyl)methane; bis(4-hydroxy-2,6-dimethyl-3-methoxyphenyl)methane; 1,1-bis(4-hydroxyphenyl)ethane; 1,1-bis(4-hydroxy-2-chlorophenyl)ethane; 2,2-bis(4-hydroxyphenyl)propane (bisphenol-A); 1,1-bis(4-hydroxyphenyl)propane; 2,2-bis(3-chloro-4-hydroxyphenyl)propane; 2,2-bis(3-bromo-4-hydroxyphenyl)propane; 2,2-bis(4-hydroxy-3-methylphenyl)propane; 2,2-bis(4-hydroxy-3-isopropylphenyl)propane; 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane; 2,2-bis(3-phenyl-4-hydroxyphenyl)propane; 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane; 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane; 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane; 2,2-bis(3-chloro-4-hydroxy-5-methylphenyl)propane; 2,2-bis(3-bromo-4-hydroxy-5-methylphenyl)propane; 2,2-bis(3-chloro-4-hydroxy-5-isopropylphenyl)propane; 2,2-bis(3-bromo-4-hydroxy-5-isopropylphenyl)propane; 2,2-bis(3-t-butyl-5-chloro-4-hydroxyphenyl)propane; 2,2-bis(3-bromo-5-t-butyl-4-hydroxyphenyl)propane; 2,2-bis(3-chloro-5-phenyl-4-hydroxyphenyl)propane; 2,2-bis(3-bromo-5-phenyl-4-hydroxyphenyl)propane; 2,2-bis(3,5-disopropyl-4-hydroxyphenyl)propane; 2,2-bis(3,5-di-t-butyl-4-hydroxyphenyl)propane; 2,2-bis(3,5-diphenyl-4-hydroxyphenyl)propane; 2,2-bis(4-hydroxy-2,3,5,6-tetrachlorophenyl)propane; 2,2-bis(4-hydroxy-2,3,5,6-tetrabromophenyl)propane; 2,2-bis(4-hydroxy-2,3,5,6-tetramethylphenyl)propane; 2,2-bis(2,6-dichloro-3,5-dimethyl-4-hydroxyphenyl)propane; 2,2-bis(2,6-dibromo-3,5-dimethyl-4-hydroxyphenyl)propane; 2,2-bis(4-hydroxy-3-ethylphenyl)propane; 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane; 2,2-bis(3,5,3′,5′-tetrachloro-4,4′-dihydroxyphenyl)propane; 1,1-bis(4-hydroxyphenyl)cyclohexylmethane; 2,2-bis(4-hydroxyphenyl)-1-phenylpropane; 1,1-bis(4-hydroxyphenyl)cyclohexane; 1,1-bis(3-chloro-4-hydroxyphenyl)cyclohexane; 1,1-bis(3-bromo-4-hydroxyphenyl)cyclohexane; 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane; 1,1-bis(4-hydroxy-3-isopropylphenyl)cyclohexane; 1,1-bis(3-t-butyl-4-hydroxyphenyl)cyclohexane; 1,1-bis(3-phenyl-4-hydroxyphenyl)cyclohexane; 1,1-bis(3,5-dichloro-4-hydroxyphenyl)cyclohexane; 1,1-bis(3,5-dibromo-4-hydroxyphenyl)cyclohexane; 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane; 1,1-bis(3-chloro-4-hydroxy-5-methylphenyl)cyclohexane; 1,1-bis(3-bromo-4-hydroxy-5-methylphenyl)cyclohexane; 1,1-bis(3-chloro-4-hydroxy-5-isopropylphenyl)cyclohexane; 1,1-bis(3-bromo-4-hydroxy-5-isopropylphenyl)cyclohexane; 1,1-bis(3-t-butyl-5-chloro-4-hydroxyphenyl)cyclohexane; 1,1-bis(3-bromo-5-t-butyl-4-hydroxyphenyl)cyclohexane; 1,1-bis(3-chloro-5-phenyl-4-hydroxyphenyl)cyclohexane; 1,1-bis(3-bromo-5-phenyl-4-hydroxyphenyl)cyclohexane; 1,1-bis(3,5-disopropyl-4-hydroxyphenyl)cyclohexane; 1,1-bis(3,5-di-t-butyl-4-hydroxyphenyl)cyclohexane; 1,1-bis(3,5-diphenyl-4-hydroxyphenyl)cyclohexane; 1,1-bis(4-hydroxy-2,3,5,6-tetrachlorophenyl)cyclohexane; 1,1-bis(4-hydroxy-2,3,5,6-tetrabromophenyl)cyclohexane; 1,1-bis(4-hydroxy-2,3,5,6-tetramethylphenyl)cyclohexane; 1,1-bis(2,6-dichloro-3,5-dimethyl-4-hydroxyphenyl)cyclohexane; 1,1-bis(2,6-dibromo-3,5-dimethyl-4-hydroxyphenyl)cyclohexane; 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(3-chloro-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(3-bromo-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(4-hydroxy-3-isopropylphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(3-t-butyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(3-phenyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(3,5-dichloro-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(3,5-dibromo-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(3-chloro-4-hydroxy-5-methylphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(3-bromo-4-hydroxy-5-methylphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(3-chloro-4-hydroxy-5-isopropylphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(3-bromo-4-hydroxy-5-isopropylphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(3-t-butyl-5-chloro-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(3-bromo-5-t-butyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane; bis(3-chloro-5-phenyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(3-bromo-5-phenyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(3,5-disopropyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(3,5-di-t-butyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(3,5-diphenyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(4-hydroxy-2,3,5,6-tetrachlorophenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(4-hydroxy-2,3,5,6-tetrabromophenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(4-hydroxy-2,3,5,6-tetramethylphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(2,6-dichloro-3,5-dimethyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane; 1,1-bis(2,6-dibromo-3,5-dimethyl-4-hydroxyphenyl)-3,3,5-trimethylcyclohexane; 4,4-bis(4-hydroxyphenyl)heptane; 1,1-bis(4-hydroxyphenyl)decane; 1,1-bis(4-hydroxyphenyl)cyclododecane; and 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclododecane. 
     In one embodiment, the present invention provides a polyethersulfone composition comprising structural units I, said polyethersulfone composition further comprising structural units derived from bisphenol A. In an alternate embodiment, the present invention provides a polyethersulfone composition comprising structural units I, II, and structural units derived from bisphenol A. In yet another embodiment, the present invention provides a polyethersulfone composition comprising structural units I, II, III, and structural units derived from bisphenol A. In yet still another embodiment, the present invention provides a polyethersulfone composition comprising structural units I, II, III, IV and structural units derived from bisphenol A. 
     Polyethersulfone compositions comprising structural units I may be prepared by reacting a fluorenone bisphenol such as 9,9-bis(4-hydroxyphenyl)fluorene (“FBPA”) with a biphenyl-bissulfone such as 4,4′-bis((4-chlorophenyl)sulfonyl)-1,1′-biphenyl (“DCBPS”) in a solvent at elevated temperature in the presence of a base and optionally a phase transfer catalyst. The product polyethersulfone compositions so prepared comprise structural units derived from the bisphenol and the biphenyl-bissulfone. 
     In one embodiment, a preformed salt of a fluorenone bisphenol (for example the sodium salt of FBPA (FBPANa 2 ) is reacted with 4,4′-bis((4-chlorophenyl)sulfonyl)-1,1′-biphenyl (“DCBPS”) in orthodichlorobenzene (“oDCB”) in the presence of a phase transfer catalyst which helps solubilize the preformed salt of the fluorenone bisphenol. The reaction temperature is such that the polymerization proceeds at a synthetically useful rate, typically at one or more temperatures in a range between about 100° C. and about 250° C. In one embodiment, the reaction temperature is in a range between about 145° C. and about 220° C. In another embodiment, the reaction temperature is in a range between about 165° C. and about 200° C. The solvent employed is typically a solvent which is relatively inert under the reaction conditions. Suitable solvents include chlorobenzene, diphenyl sulfone, diphenyl ether, oDCB, dichlorotoluenes, trichlorobenzene, xylenes, chloronaphthalene, sulfolane, N-methyl-2-pyrrolidone (NMP), dimethyl formamide (DMF), dimethylacetamide (DMAc), mixtures of two or more of the foregoing solvents, and the like. 
     Suitable phase transfer catalysts include hexaalkylguanidinium salts, and bis-guanidinium salts. Typically, the phase transfer catalyst comprises an anionic species such as chloride, bromide, fluoride, mesylate, tosylate, tetrafluoroborate, acetate, and the like, as the charge-balancing counterion(s). Suitable guanidinium salts include those disclosed in U.S. Pat. Nos. 5,132,423; 5,116,975; and 5,081,298. Other suitable phase transfer catalysts include p-dialkylaminopyridinium salts, bis-dialkylaminopyridinium salts, bis-quaternary ammonium salts, bis-quaternary phosphonium salts, and phosphazenium salts. Suitable bis-quaternary ammonium and phosphonium salts are disclosed in U.S. Pat. No. 4,554,357. Suitable aminopyridinium salts are disclosed in U.S. Pat. Nos. 4,460,778; 4,513,141 and 4,681,949. Suitable phosphazenium salts include those disclosed in U.S. patent application Ser. No. 10/950,874 paragraphs 25, 26, 27, 28, 29, and 30 of which are incorporated herein by reference. Additionally, in certain embodiments, quaternary ammonium and phosphonium salts as disclosed in U.S. Pat. No. 4,273,712 are suitable for use in the preparation of the polyethersulfone compositions of the present invention. 
     When a polar aprotic solvent such as sulfolane is employed the use of the phase transfer catalyst may be optional. In one embodiment, the preformed salt of a fluorenone bisphenol and the preformed salt of at least one other bisphenol is employed. 
     An alternate method for preparing the polyethersulfone compositions of the present invention involves the in situ formation of the salt of the fluorenone bisphenol in the presence of a base. In some embodiments, the use of a polar solvent such as sulfolane, solubilizes the salt of the fluorenone bisphenol sufficiently for polymerization to be carried out in the absence of a phase transfer catalyst. In one embodiment, a fluorenone bisphenol and at least one additional bisphenol (for example 4,4′-biphenol) is employed. 
     In one embodiment, the polyethersulfone composition of the present invention comprises structural units derived from at least one fluorenone bisphenol VI 
     
       
         
         
             
             
         
       
     
     wherein R 1  and R 2  are independently at each occurrence halogen, nitro, a C 1 -C 20  aliphatic radical, a C 3 -C 20  cycloaliphatic radical, or a C 2 -C 20  aromatic radical; and “a”, “b”, “c”, and “d” are independently integers from 0 to 4;
 
at least one biphenyl-bissulfone VII
 
     
       
         
         
             
             
         
       
     
     wherein X 1  and X 2  are independently halogen, or nitro; R 3  and R 4  are independently at each occurrence halogen, nitro, a C 1 -C 20  aliphatic radical, a C 3 -C 20  cycloaliphatic radical, or a C 2 -C 20  aromatic radical; and “e”, “f”, “g”, and “h” are independently integers from 0 to 4; and
 
optionally structural units derived from at least one biphenol VIII
 
     
       
         
         
             
             
         
       
     
     wherein R 5  is independently at each occurrence halogen, nitro, a C 1 -C 20  aliphatic radical, a C 3 -C 20  cycloaliphatic radical, or a C 2 -C 20  aromatic radical; and “i” and “j” are independently integers from 0 to 4. 
     Suitable fluorenone bisphenols VI are illustrated by the bisphenols listed in Table 2, and the like. 
     
       
         
           
               
             
               
                 TABLE 2 
               
             
            
               
                   
               
               
                 Illustrative Fluorenone Bisphenols VI 
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                 Entry 
                 R 1   
                 R 2   
                 “a” 
                 “b” 
                 “c” 
                 “d” 
                 Chemical name 
               
               
                   
               
               
                 VI-1 
                 — 
                 — 
                 0 
                 0 
                 0 
                 0 
                 9,9-bis(4-hydroxy- 
               
               
                   
                   
                   
                   
                   
                   
                   
                 phenyl)fluorene (FBPA) 
               
               
                 VI-2 
                 3-Me 
                 — 
                 1 
                 1 
                 0 
                 0 
                 9,9-bis(4-hydroxy-3- 
               
               
                   
                   
                   
                   
                   
                   
                   
                 methylphenyl)fluorene 
               
               
                 VI-3 
                 3-Pr 
                 — 
                 1 
                 1 
                 0 
                 0 
                 9,9-bis(4-hydroxy-3- 
               
               
                   
                   
                   
                   
                   
                   
                   
                 propylphenyl)fluorene 
               
               
                 VI-4 
                 — 
                 3-Me, 
                 0 
                 0 
                 1 
                 1 
                 9,9-bis(4-hydroxyphenyl)-3,6- 
               
               
                   
                   
                 6-Me 
                   
                   
                   
                   
                 dimethylfluorene 
               
               
                 IV-5 
                 — 
                 3-Cl, 
                 0 
                 0 
                 1 
                 1 
                 9,9-bis(4-hydroxyphenyl)-3,6- 
               
               
                   
                   
                 6-Cl 
                   
                   
                   
                   
                 dichlorofluorene 
               
               
                   
               
            
           
         
       
     
     Suitable biphenyl-bissulfones VII are illustrated by the biphenyl-bissulfones listed in Table 3 and the like. 
     
       
         
           
               
             
               
                 TABLE 3 
               
             
            
               
                   
               
               
                 Illustrative Biphenyl-Bissulfones VII 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                 Entry 
                 R 3   
                 R 4   
                 “e” 
                 “f” 
                 “g” 
                 “h” 
                 X 1   
                 X 2   
                 Chemical name 
               
               
                   
               
               
                 VII-1 
                 — 
                 — 
                 0 
                 0 
                 0 
                 0 
                 Cl 
                 Cl 
                 4,4′-bis((4-chloro- 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 phenyl)sulfonyl)- 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 1,1′-biphenyl 
               
               
                 VII-2 
                 — 
                 — 
                 0 
                 0 
                 0 
                 0 
                 F 
                 F 
                 4,4′-bis((4-fluoro- 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 phenyl)sulfonyl)- 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 1,1′-biphenyl 
               
               
                 VII-3 
                 3-Cl 
                 — 
                 1 
                 1 
                 0 
                 0 
                 Cl 
                 Cl 
                 4,4′-bis((3,4- 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 dichlorophenyl)sulfo- 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 nyl)-1,1′-biphenyl 
               
               
                 VII-4 
                 — 
                 3-Cl, 
                 0 
                 0 
                 1 
                 1 
                 F 
                 F 
                 4,4′-bis((4-fluoro- 
               
               
                   
                   
                 3′-Cl 
                   
                   
                   
                   
                   
                   
                 phenyl)sulfonyl)- 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 3,3′-dichloro- 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 1,1′-bipheny 1 
               
               
                   
               
            
           
         
       
     
     Suitable biphenols VIII are illustrated by the biphenols listed in Table 4, and the like. 
     
       
         
           
               
             
               
                 TABLE 4 
               
             
            
               
                   
               
               
                 Illustrative Biphenols VIII 
               
            
           
           
               
               
               
               
               
               
            
               
                 Entry 
                 R 5   
                 “i” 
                 “j” 
                 Chemical name 
                 Structure 
               
               
                   
               
               
                 VIII-1 
                 — 
                 0 
                 0 
                 4,4′-biphenol (also called 4,4′-dihydroxy- 1,1′biphenyl) 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 VIII-2 
                 3-Me, 3′-Me 
                 1 
                 1 
                 3,-3′-dimethyl-4,4′- biphenol 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 VIII-3 
                 3-Me 
                 1 
                 0 
                 3-methyl-4,4′-biphenol 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 VIII-4 
                 2-Ph 
                 1 
                 0 
                 2-phenyl-4,4′-biphenol 
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 *When a variable is defined as zero, default substitution by “H” (hydrogen″ is intended 
               
            
           
         
       
     
     In one embodiment, the present invention provides a polyethersulfone composition wherein the structural units derived from fluorenone bisphenol VI represent from about 10 mole percent to about 100 mole percent of all structural groups derived from a dihydroxy aromatic compound present in the composition. In another embodiment, the present invention provides a polyethersulfone composition wherein the structural units derived from fluorenone bisphenol VI represent from about 10 mole percent to about 50 mole percent of all structural groups derived from a dihydroxy aromatic compound present in the composition. In yet another embodiment, the present invention provides a polyethersulfone composition wherein the structural units derived from fluorenone bisphenol VI represent from about 10 mole percent to about 25 mole percent of all structural groups derived from a dihydroxy aromatic compound present in the composition. 
     In one embodiment, the polyethersulfone compositions of the present invention, structural units derived from biphenyl-bissulfone VII represent from about 10 to about 100 mole percent of all structural groups derived from an electrophilic sulfone monomer. In another embodiment, the polyethersulfone compositions of the present invention, structural units derived from biphenyl-bissulfone VII represent from about 10 to about 70 mole percent of all structural groups derived from an electrophilic sulfone monomer. In yet another embodiment, the polyethersulfone compositions of the present invention, structural units derived from biphenyl-bissulfone VII represent from about 10 to about 50 mole percent of all structural groups derived from an electrophilic sulfone monomer. Those skilled in the art will appreciate that electrophilic sulfone monomers are sulfone monomers capable of undergoing a nucleophilic displacement reaction with the salt of an aromatic hydroxy compound. Electrophilic sulfone monomers are illustrated by 4,4′-bis((4-chlorophenyl)sulfonyl)-1,1′-biphenyl (See Entry VII-1 Table 3) and bis(4-chlorophenyl)sulfone. Those skilled in the art will appreciate that 4,4′-bis((4-chlorophenyl)sulfonyl)-1,1′-biphenyl and bis(4-chlorophenyl)sulfone are capable of undergoing a nucleophilic displacement reaction with the salt of an aromatic hydroxy compound, for example the disodium salt of bisphenol A. It is stressed that all of the biphenyl-bissulfones listed in Table 3 represent electrophilic sulfone monomers 
     As noted, the presence of structural units derived from biphenol VIII is optional and thus, in one embodiment, the structural units derived from biphenol VIII represent from about 0 mole percent to about 90 mole percent of all structural groups derived from a dihydroxy aromatic compound present in the composition. In another embodiment, the structural units derived from biphenol VIII represent from about 5 mole percent to about 70 mole percent of all structural groups derived from a dihydroxy aromatic compound present in the composition. In yet another embodiment, the structural units derived from biphenol VIII represent from about 5 mole percent to about 50 mole percent of all structural groups derived from a dihydroxy aromatic compound present in the composition. 
     In one embodiment, the polyethersulfone compositions of the present invention further comprise structural units derived from at least one sulfone IX 
     
       
         
         
             
             
         
       
     
     wherein X 3  and X 4  are independently halogen, or nitro; R 6  is independently at each occurrence halogen, nitro, a C 1 -C 20  aliphatic radical, a C 3 -C 20  cycloaliphatic radical, or a C 2 -C 20  aromatic radical; and “k” and “l” are independently integers from 0 to 4. 
     Suitable sulfones IX are illustrated by bis(4-chlorophenyl)sulfone (DCDPS), bis(3,4-dichlorophenyl)sulfone, bis(3,4,5-trichlorophenyl)sulfone, bis(4-fluorophenyl)sulfone, bis(3,4-difluorophenyl)sulfone, bis(4-nitrophenyl)sulfone, bis(4-chloro-3-nitrophenyl)sulfone, and the like. 
     In one embodiment, the present invention provides a polyethersulfone composition in which structural units derived from sulfone IX represent from about 5 to about 90 mole percent of all structural groups derived from an electrophilic sulfone monomer. In another embodiment, the present invention provides a polyethersulfone composition in which structural units derived from sulfone IX represent from about 5 to about 50 mole percent of all structural groups derived from an electrophilic sulfone monomer. In yet another embodiment, the present invention provides a polyethersulfone composition in which structural units derived from sulfone IX represent from about 5 to about 25 mole percent of all structural groups derived from an electrophilic sulfone monomer. In one embodiment, the present invention provides a polyethersulfone composition comprising structural units derived from biphenyl-bissulfone VII and sulfone IX, wherein the structural units derived from biphenyl-bissulfone VII represent from about 20 mole percent to about 95 mole percent of all structural groups derived from an electrophilic sulfone monomer. In another embodiment, the present invention provides a polyethersulfone composition comprising structural units derived from biphenyl-bissulfone VII and sulfone IX, wherein the structural units derived from sulfone IX represent from about 5 mole percent to about 70 mole percent of all structural groups derived from an electrophilic sulfone monomer. 
     In one embodiment, the present invention provides a polyethersulfone composition comprising structural groups derived from 9,9-bis(4-hydroxyphenyl)fluorene and 4,4′-bis((4-chloropheyl)sulfonyl)-1,1′-biphenyl. In another embodiment, the present invention provides a polyethersulfone composition comprising structural groups derived from 9,9-bis(4-hydroxyphenyl)fluorene; 4,4′-bis((4-chloropheyl)sulfonyl)-1,1′-biphenyl; and bis(4-chlorophenyl)sulfone. In yet another embodiment the present invention provides a polyethersulfone composition comprising structural groups derived from 9,9-bis(4-hydroxyphenyl)fluorene; 4,4′-bis((4-chloropheyl)sulfonyl)-1,1′-biphenyl; bis(4-chlorophenyl)sulfone and 4,4′-biphenol. 
     Standard additives may be added to the polyethersulfone compositions of the present invention to the invention, preferably in quantities of from about 0.00001 to about 80% by weight and more preferably in quantities of from about 0 to about 60% by weight, based on the weight of the composition. These additives include such materials as thermal stabilizers, antioxidants, UV stabilizers, plasticizers, visual effect enhancers, extenders, antistatic agents, catalyst quenchers, mold releasing agents, fire retardants, blowing agents, impact modifiers and processing aids. The different additives that can be incorporated into the polyethersulfone compositions of the present invention are typically commonly used in resin compounding and are known to those skilled in the art. 
     Visual effect enhancers which may be included in the polyethersulfone composition, sometimes known as visual effects additives or pigments may be present in an encapsulated form, a non-encapsulated form, or laminated to a particle comprising polymeric resin. Some non-limiting examples of visual effects additives are aluminum, gold, silver, copper, nickel, titanium, stainless steel, nickel sulfide, cobalt sulfide, manganese sulfide, metal oxides, white mica, black mica, pearl mica, synthetic mica, mica coated with titanium dioxide, metal-coated glass flakes, and colorants, including but not limited, to Perylene Red. The visual effect additive may have a high or low aspect ratio and may comprise greater than 1 facet. Dyes may be employed such as Solvent Blue 35, Solvent Blue 36, Disperse Violet 26, Solvent Green 3, Anaplast Orange LFP, Perylene Red, and Morplas Red 36. Fluorescent dyes may also be employed including, but not limited to, Permanent Pink R (Color Index Pigment Red 181, from Clariant Corporation), Hostasol Red 5B (Color Index #73300, CAS #522-75-8, from Clariant Corporation) and Macrolex Fluorescent Yellow 10GN (Color Index Solvent Yellow 160:1, from Bayer Corporation). Pigments such as titanium dioxide, zinc sulfide, carbon black, cobalt chromate, cobalt titanate, cadmium sulfides, iron oxide, sodium aluminum sulfosilicate, sodium sulfosilicate, chrome antimony titanium rutile, nickel antimony titanium rutile, and zinc oxide may be employed. Visual effect additives in encapsulated form usually comprise a visual effect material such as a high aspect ratio material like aluminum flakes encapsulated by a polymer. The encapsulated visual effect additive has the shape of a bead. 
     Non-limiting examples of antioxidants which may be included in the polyethersulfone composition include tris(2,4-di-tert-butylphenyl)phosphite; 3,9-di(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro(5.5)undecane; 3,9-di(2,4-dicumylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro(5.5)undecane; tris(p-nonylphenyl)phosphite; 2,2′,2″-nitrilo(triethyl-tris(3,3′,5,5′-tetra-tertbutyl-1,1′-biphenyl-2′-diyl)phosphite); 3,9-distearyloxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro(5.5)undecane; dilauryl phosphite; 3,9-di(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro(5.5)undecane; tetrakis(2,4-di-tert-butylphenyl)-4,4′-bis(diphenylene)phosphonite; distearyl pentaerythritol diphosphite; diisodecyl pentaerythritol diphosphite; 2,4,6-tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite; tristearyl sorbitol triphosphite; tetrakis(2,4-di-tert-butylphenyl)-4,4′-biphenylene diphosphonite; (2,4,6-tri-tert-butylphenyl)-2-butyl-2-ethyl-1,3-propanediolphosphite; triisodecylphosphite; and mixtures of phosphites containing at least one of the foregoing. Tris(2,4-di-tert-butylphenyl)phosphite; 2,4,6-tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite; bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite are especially preferred, as well as mixtures of phosphites containing at least one of the foregoing phosphites, and the like. 
     The polyethersulfone compositions of the present invention may optionally comprise an impact modifier. The impact modifier resin may be added to the polyethersulfone in an amount corresponding to about 1% to about 30% by weight, based on the total weight of the composition. Suitable impact modifiers include those comprising one of several different rubbery modifiers such as graft or core shell rubbers or combinations of two or more of these modifiers. Impact modifiers are illustrated by acrylic rubber, ASA rubber, diene rubber, organosiloxane rubber, ethylene propylene diene monomer (EPDM) rubber, styrene-butadiene-styrene (SBS) rubber, styrene-ethylene-butadiene-styrene (SEBS) rubber, acrylonitrile-butadiene-styrene (ABS) rubber, methacrylate-butadiene-styrene (MBS) rubber, styrene acrylonitrile copolymer and glycidyl ester impact modifier. 
     Non-limiting examples of processing aids which may be included in the polyethersulfone composition include, Doverlube® FL-599 (available from Dover Chemical Corporation), Polyoxyter® (available from Polychem Alloy Inc.), Glycolube P (available from Lonza Chemical Company), pentaerythritol tetrastearate, Metablen A-3000 (available from Mitsubishi Rayon), neopentyl glycol dibenzoate, and the like. 
     Non-limiting examples of UV stabilizers which may be included in the polyethersulfone composition include 2-(2′-Hydroxyphenyl)-benzotriazoles, e.g., the 5′-methyl-; 3′,5′-di-tert.-butyl-; 5′-tert.-butyl-; 5′-(1,1,3,3-tetramethylbutyl)-; 5-chloro-3′,5′-di-tert.-butyl-; 5-chloro-3′-tert.-butyl-5′-methyl-; 3′-sec.-butyl-5′-tert.-butyl-; 3′-alpha-methylbenzyl-5′-methyl; 3′-alpha-methylbenzyl-5′-methyl-5-chloro-; 4′-hydroxy-; 4′-methoxy-; 4′-octoxy-; 3′,5′-di-tert.-amyl-; 3′-methyl-5′-carbomethoxyethyl-; 5-chloro-3′,5′-di-tert.-amyl-derivatives; and Tinuvin® 234 (available from Ciba Specialty Chemicals). Also suitable are the 2,4-bis-(2′-hydroxyphenyl)-6-alkyl-s-triazines, e.g., the 6-ethyl-; 6-heptadecyl- or 6-undecyl-derivatives. 2-Hydroxybenzophenones e.g., the 4-hydroxy-; 4-methoxy-; 4-octoxy-; 4-decyloxy-; 4-dodecyloxy-; 4-benzyloxy-; 4,2′,4′-trihydroxy-; 2,2′,4,4′-tetrahydroxy- or 2′-hydroxy-4,4′-dimethoxy-derivative. 1,3-bis-(2′-Hydroxybenzoyl)-benzenes, e.g., 1,3-bis-(2′-hydroxy-4′-hexyloxy-benzoyl)-benzene; 1,3-bis-(2′-hydroxy-4′-octyloxy-benzoyl)-benzene or 1,3-bis-(2′-hydroxy-4′-dodecyloxybenzoyl)-benzene may also be employed. Esters of optionally substituted benzoic acids, e.g., phenylsalicylate; octylphenylsalicylate; dibenzoylresorcin; bis-(4-tert.-butylbenzoyl)-resorcin; benzoylresorcin; 3,5-di-tert.-butyl-4-hydroxybenzoic acid-2,4-di-tert.-butylphenyl ester or -octadecyl ester or -2-methyl-4,6-di-tert.-butyl ester may likewise be employed. Acrylates, e.g., alpha-cyano-beta, beta-diphenylacrylic acid-ethyl ester or isooctyl ester, alpha-carbomethoxy-cinnamic acid methyl ester, alpha-cyano-beta-methyl-p-methoxy-cinnamic acid methyl ester or -butyl ester or N-(beta-carbomethoxyvinyl)-2-methyl-indoline may likewise be employed. Oxalic acid diamides, e.g., 4,4′-di-octyloxy-oxanilide; 2,2′-di-octyloxy-5,5′-di-tert.-butyl-oxanilide; 2,2′-di-dodecyloxy-5,5-di-tert.-butyl-oxanilide; 2-ethoxy-2′-ethyl-oxanilide; N,N′-bis-(3-dimethyl-aminopropyl)-oxalamide; 2-ethoxy-5-tert.-butyl-2′-ethyloxanilide and the mixture thereof with 2-ethoxy-2′-ethyl-5,4′-di-tert.-butyl-oxanilide; or mixtures of ortho- and para-methoxy- as well as of o- and p-ethoxy-disubstituted oxanilides are also suitable as UV stabilizers. Preferably the ultraviolet light absorber used in the instant compositions is 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole; 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole; 2-(2-hydroxy-3,5-di-(alpha,alpha-dimethylbenzyl)phenyl)-2H-benzotriazole; 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole; 2-hydroxy-4-octyloxybenzophenone; nickel bis(O-ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate); 2,4-dihydroxybenzophenone; 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole; nickel butylamine complex with 2,2′-thiobis(4-tert-butylphenol); 2-ethoxy-2′-ethyloxanilide; 2-ethoxy-2′-ethyl-5,5′-ditert-butyloxanilide or a mixture thereof. 
     Non-limiting examples of fire retardants which may be included in the polyethersulfone composition include potassium nonafluorobutylsulfonate, potassium diphenylsulfone sulfonate, and phosphite esters of polyhydric phenols, such as resorcinol and bisphenol A. 
     Non-limiting examples of mold release compositions which may be included in the polyethersulfone composition include esters of long-chain aliphatic acids and alcohols such as pentaerythritol, guerbet alcohols, long-chain ketones, siloxanes, alpha.-olefin polymers, long-chain alkanes and hydrocarbons having 15 to 600 carbon atoms. 
     The polyethersulfone compositions according to the invention may also be mixed in known manner with other known polymers to form for example, polymer blends, polymer mixtures, and polymer alloys. 
     Articles comprising a polyethersulfone composition of the present invention are another embodiment of the present invention. In one embodiment, the article is a molded article. In another embodiment, the article is an extruded film. In another embodiment, the article comprises a polyethersulfone composition of the present invention as a solvent cast film. In yet another embodiment, the article comprises a polyethersulfone composition of the present invention as a spin coated film. In various embodiments articles may comprise the polyethersulfone composition, for example in admixture with additives known in the art, such as conventional UV screeners, for use for example in applications such as injection molding, thermoforming, in-mold decoration, and like applications. 
     In other embodiments articles of the present invention are multilayer articles comprising two or more layers, typically in contiguous superposed contact with one another. In various embodiments multilayer articles comprise a substrate layer comprising the polyethersulfone composition of the present invention. In alternative embodiments the article comprises a substrate comprising at least one thermoplastic polymer, thermoset polymer, cellulosic material, glass, ceramic, or metal, and at least one coating layer thereon, said coating layer comprising a polyethersulfone composition provided by the present invention. Optionally, the multilayer articles may further comprise an interlayer, for example an adhesive interlayer (or tie layer), between any substrate layer and any coating layer. Multilayer articles of the invention include, but are not limited to, those which comprise a substrate layer and a coating layer comprising a polyethersulfone composition provided by present invention; those which comprise a substrate layer comprising said polyethersulfone composition and a coating layer comprising a resorcinol polyarylate material. In another embodiment, the article comprises at least two layers comprising the polyethersulfone composition of the present invention. Any interlayer may be transparent and/or may contain an additive, for example a colorant or decorative material such as metal flake. 
     Representative articles which can be made comprising the polyethersulfone compositions of the invention include aircraft, automotive, truck, military vehicle (including automotive, aircraft, and water-borne vehicles), and motorcycle exterior and interior components, including panels, quarter panels, rocker panels, trim, fenders, doors, decklids, trunklids, hoods, bonnets, roofs, bumpers, fascia, grilles, mirror housings, pillar appliques, cladding, body side moldings, wheel covers, hubcaps, door handles, spoilers, window frames, headlamp bezels, headlamps, tail lamps, tail lamp housings, tail lamp bezels, license plate enclosures, roof racks, and running boards; enclosures, housings, panels, and parts for outdoor vehicles and devices; enclosures for electrical and telecommunication devices; outdoor furniture; boats and marine equipment, including trim, enclosures, and housings; outboard motor housings; depth finder housings, personal water-craft; jet-skis; pools; spas; hot-tubs; steps; step coverings; building and construction applications such as glazing, roofs, windows, floors, decorative window furnishings or treatments; treated glass covers for pictures, paintings, posters, and like display items; optical lenses; ophthalmic lenses; corrective ophthalmic lenses; implantable ophthalmic lenses; wall panels, and doors; protected graphics; outdoor and indoor signs; enclosures, housings, panels, and parts for automatic teller machines (ATM); enclosures, housings, panels, and parts for lawn and garden tractors, lawn mowers, and tools, including lawn and garden tools; window and door trim; sports equipment and toys; enclosures, housings, panels, and parts for snowmobiles; recreational vehicle panels and components; playground equipment; articles made from plastic-wood combinations; golf course markers; utility pit covers; computer housings; desk-top computer housings; portable computer housings; lap-top computer housings; palm-held computer housings; monitor housings; printer housings; keyboards; FAX machine housings; copier housings; telephone housings; mobile phone housings; radio sender housings; radio receiver housings; light fixtures; lighting appliances; network interface device housings; transformer housings; air conditioner housings; cladding or seating for public transportation; cladding or seating for trains, subways, or buses; meter housings; antenna housings; cladding for satellite dishes; coated helmets and personal protective equipment; coated synthetic or natural textiles; coated photographic film and photographic prints; coated painted articles; coated dyed articles; coated fluorescent articles; coated foam articles; and like applications. The invention further contemplates additional fabrication operations on said articles, such as, but not limited to, molding, in-mold decoration, baking in a paint oven, lamination, and/or thermoforming. 
     EXAMPLES 
     The following examples are intended only to illustrate methods and embodiments in accordance with the invention, and as such should not be construed as imposing limitations upon the claims. Unless specified otherwise, all ingredients are commercially available. The acronym, “FBPA”, stands for 9,9-bis(4-hydroxyphenyl)fluorene. The acronym, “DCBPS”, stands for 4,4′-bis((4-chlorophenyl)sulfonyl)-1,1′-biphenyl. The acronym, “DCDPS”, stands for bis(4-chlorophenyl)sulfone (DCDPS). The acronym, “FBPANa 2 ”, stands for the disodium salt of FBPA. The acronym, “BPNa 2 ” stands for the disodium salt of 4,4′-biphenol. The disodium salt of 4,4′-biphenol was prepared and isolated by known methods. Polymerizations were typically carried out at concentration in a range corresponding to between about 25 and about 30 percent solids. 
     Example 1 
     Synthesis of FBPA/DCBPS Copolymer 
     To a nitrogen purged 250 mL 3-neck flask equipped with a nitrogen inlet, mechanical stirrer and short path distillation apparatus, was charged FBPA (10.00 g, 0.02854 moles), DCBPS (14.37 g, 0.02854 moles), potassium carbonate (4.50 g, 0.03256 moles) and 50 mL of sulfolane. Toluene was added and distilled, and the distillate was sampled an analyzed until the concentration of water in the distillate was less than 80 ppm by Karl-Fisher titration. Following water removal, the temperature was raised to 200° C. After stirring for 9.25 hours at 200° C., the reaction was allowed to cool to room temperature, and 150 mL of orthodichlorobenzene (oDCB) was added. The mixture was then heated to 120° C. to dissolve the polymer, and filtered to remove undissolved potassium chloride. The filtrate (100 mL) was added to about 500 mL of vigorously stirred methanol in a blender to yield a fluffy white solid that was filtered and then subsequently dissolved in 250 mL hot chloroform. The chloroform solution was added in 100 mL portions to about 500 mL of vigorously stirred methanol in a blender to yield upon filtration, the product polyethersulfone copolymer which was shown by gel permeation chromatography (gpc) to have a weight average molecular weight (Mw) of 54,000 grams per mole with a polydispersity index (PDI) of 2.9. The solid was dried in a vacuum oven at 90° C. and 26 in-29 in of pressure. The glass transition temperature (T g ) of the resulting white powder was determined by differential scanning calorimetry (DSC) to be 301° C. 
     Example 2 
     Synthesis of 50/50 FBPA/BP DCBPS Copolymer 
     To a nitrogen purged 250 mL 3-neck flask equipped with a nitrogen inlet, mechanical stirrer and short path distillation apparatus was charged FBPANa 2  (3.425 g, 0.008685 moles), BPNa 2  (2.152 g 0.009348 moles), 75 mL oDCB and 100 mL chlorobenzene. To assure a high level of dryness, chlorobenzene was distilled from the mixture until the concentration of water in the distillate was less than 20 ppm by Karl-Fisher titration. At this point, DCBPS (8.63 g, 0.01714 moles) and 100 mL additional chlorobenzene were added under positive nitrogen pressure. The mixture was further dried by distillation of chlorobenzene until less than 20 ppm of water remained in the distillate as determined by Karl-Fischer analysis. The temperature was raised to 180° C. and hexaethylguanidinium chloride (HEGC1, 0.9 mL of a 0.96 M solution in oDCB) was added via syringe. Within one half hour, the light brown suspension became a dark brown solution. Within 120 minutes, the weight average molecular weight (Mw) of the product copolymer was about 56,000 grams per mole with a PDI of about 2.5. It was noted that the product copolymer began to fall out of solution as it approached the target molecular weight. The target molecular weight was the approximate molecular weight anticipated based upon the relative amounts of the reactants employed. The solution was then cooled to room temperature and the oDCB decanted away from the product copolymer. The copolymer was dissolved in 200 mL sulfolane at 100° C. and filtered to remove the sodium chloride by-product, and the filtrate was added to vigorously stirred methanol in a blender, the ratio of sulfolane to methanol being about 75 mL sulfolane/500 mL methanol. The resultant white solid product copolymer was filtered, and then dissolved in 250 mL hot chloroform. A portion of the chloroform solution was used to form a colorless film. The remaining chloroform solution was added to vigorously stirred methanol in a blender (80 mL chloroform/500 mL methanol), and the resultant precipitate was filtered to provide the product copolymer as a white solid which was rinsed with methanol three times. The product copolymer was dried in a vacuum oven and had a Mw 55,000 grams per mole and a single observable glass transition temperature (T g ) of 292° C. No melting point was observed at temperatures up to 450° C. 
     Examples 3-8 
     Synthesis of 25/75 FBPA/BP, 50/50 DCBPS/DCDPS 
     Examples 3 and 4 were carried out as described in Example 1. Examples 5-8 followed the procedure of Example 2. Results for Examples 1-9 are gathered in Table 5. 
     
       
         
           
               
             
               
                 TABLE 5 
               
             
            
               
                   
               
               
                 Polyethersulfone Copolymer Compositions 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                   
                 4,4′- 
                 Molar Ratio 
                   
                   
                 Rxn 
                   
                   
                 NI 
               
               
                   
                 biphenol/ 
                 of DCDPS/ 
                   
                 Catalyst/ 
                 Temp. 
                   
                 T g   
                 (ft- 
               
               
                 Example 
                 FBPA 
                 DCBPS 
                 Solvent 
                 base 
                 (° C.) 
                 Mw 
                 (° C.) 
                 lb/in) 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 1 
                  0/100 
                  0/100 
                 sulfolane 
                 K 2 CO 3   
                 200 
                 58k 
                 301 
                 — 
               
               
                 2 
                 50/50 
                  0/100 
                 oDCB 
                 HEGCl 
                 180 
                 56k 
                 292 
                 — 
               
               
                 3 
                 75/25 
                  0/100 
                 sulfolane 
                 Na 2 CO 3   
                 250 
                 52k 
                 289 
                 — 
               
               
                 4 
                 100/0  
                  0/100 
                 sulfolane 
                 Na 2 CO 3   
                 250 
                 55k 
                 271 
                 — 
               
               
                 5 
                 75/25 
                 50/50 
                 oDCB 
                 HEGCl 
                 180 
                 50k 
                 264 
                 — 
               
               
                 6 
                 75/25 
                 50/50 
                 oDCB 
                 HEGCl 
                 180 
                 43k 
                 266 
                 1.8 
               
               
                 7 
                 75/25 
                 50/50 
                 oDCB 
                 HEGCl 
                 180 
                 44k 
                 265 
                 2.6 
               
               
                 8 
                 85/15 
                 70/30 
                 oDCB 
                 HEGCl 
                 180 
                 44k 
                 247 
                 — 
               
               
                 9 
                 85/15 
                 70/30 
                 oDCB 
                 HEGCl 
                 180 
                 57k 
                 248 
                 7.0 
               
               
                   
               
            
           
         
       
     
     Example 9 
     FBPA (55.08 g, 0.1572 mol) and 4,4′-biphenol (165.88 g, 0.8908 mol) were charged into a 2000 mL argon purged, round-bottom flask and slurried in degassed methanol (923 mL). Sodium hydroxide solution (NaOH 50.7% w/w) was added at room temperature (165.35 g solution, 2.0960 mole NaOH). The resulting orange solution was then slowly (8 mL/min) added to a second reactor equipped for stirring and distillation, the second reactor containing hot (165° C.), vigorously stirred oDCB (1000 mL). When approximately 1000 mL of distillate had been collected, additional oDCB was added in portions to dry the bisphenol salts by azeotropic distillation. When the water content of the distillate was found to be about 18 ppm (as determined by Karl Fischer titration) the aryl halide monomers (DCBPS: 210.68 g, 0.73365 mol; DCBPS: 158.29 g, 0.31443 mol) were added. Additional oDCB was added and distillation continued. When the water content of the distillate was found to be about 12 ppm hexaethylguanidinium chloride phase transfer catalyst (hexaethylguanidinium chloride, 0.042 mol) was added to initiate the polymerization reaction. After 7 hours at 180° C., the molecular weight of the product copolymer had leveled off at about 37,000 grams per mole (PDI=2.2) as determined by GPC. An aliquot of BPNa 2  (2.10 g) was then added and the reaction was continued for an additional 3 hours at 180° C. At this stage the molecular weight of the product copolymer was about 47,000 gram per mole (PDI=2.4). Another aliquot of BPNa 2  (1.126 g) was then added and after additional 10 hours at 180° C. the molecular weight of the product copolymer was about 57,000 grams per mole (PDI=2.6). The polymerization mixture was then quenched by cautious addition of 85% H 3 PO 4  (9.4 g) and diluted with oDCB (1700 g) and veratrole (1700 g). The solution comprising the product copolymer was brought to 90° C., water (21 mL) was then added while stirring at 350 rpm. After stirring at 350 rpm for 2 minutes the speed of the stirrer was decreased to 150 rpm and the temperature was raised to 130° C. under a sweep of nitrogen. Subsequently, the polymer solution was filtered at 120° C. in an ERTEL ALSOP pressure vessel through a NOMEX filter pad. The resulting clear solution was precipitated into methanol. The fluffy polymer powder was collected, dried and redissolved in chloroform (3100 mL). After precipitation into methanol, vacuum drying at 130° C. for several days afforded the product copolymer (465 g, 91%) as an off-white powder: T g  248° C.; Mw 58,000 grams per mole as determined by gel permeation chromatography; Notched izod impact: 7 ft-lb/in. 
     The product copolymers listed in Table 5 each displayed only one T g , indicating random character. The data show also that there is not a linear relationship between glass transition temperature and mole % FBPA for polymers comprising FBPA, BP and DCBPS. The data indicate that unexpected enhancement and control of T g  are observed in certain compositions. Additionally, the data show that compositions comprising lower levels of FBPA-derived structural units, exhibit greater notched izod impact resistance. Example 9 illustrates a composition comprising about 15 mol % FBPA-derived structural units having good ductility (7 ft-lb/in). Additionally, increased solubility in oDCB was observed for copolymers comprising structural units derived FBPA, a feature which enhances the utility of oDCB as a solvent in reactions mediated by a phase transfer catalyst. 
     The foregoing examples are merely illustrative, serving to illustrate various aspects of the invention. The appended claims are intended to claim the invention as broadly as it has been conceived and the examples herein presented are illustrative of selected embodiments from a manifold of all possible embodiments. Accordingly, it is Applicants&#39; intention that the appended claims are not to be limited by the choice of examples utilized to illustrate features of the present invention. As used in the claims, the word “comprises” and its grammatical variants logically also subtend and include phrases of varying and differing extent such as for example, but not limited thereto, “consisting essentially of” and “consisting of.” Where necessary, ranges have been supplied, those ranges are inclusive of all sub-ranges there between. It is to be expected that variations in these ranges will suggest themselves to a practitioner having ordinary skill in the art and where not already dedicated to the public, those variations should where possible be construed to be covered by the appended claims. It is also anticipated that advances in science and technology will make equivalents and substitutions possible that are not now contemplated by reason of the imprecision of language and these variations should also be construed where possible to be covered by the appended claims.