WO 2006/107940 PCT/US2006/012454
POLYARYLATE COMPOSITIONS AND ARTICLES THEREFROM
BACKGROUND OF THE INVENTION
This invention relates to thermoplastic resin compositions, more particularly to
polyarylate compositions, a method to synthesize the composition and articles made
from this and related compositions.
Optical films are well known in the art. Glass has been widely used for several optical
applications, due to its excellent characteristics, such as transparency, a high
transmittance in the visible light range and temperature resistance. Nevertheless, the
use of glass as a sub layer or support in optical applications has limitations in its
application, especially in the area of flexible optical devices, due to its high weight
and brittleness. In addition, the brittleness of glass, limits its use in continuous
processing leading to a very low final productivity.
It is desirable to replace glass in numerous applications with transparent polymeric
films, such as polyesters (e.g., polyethyleneterephthalate), polyacrylates (e.g.,
polymethylmethacrylate) or polycarbonate. Although these polymers have good
properties, they possess poor transmittance, limited heat resistance and a low glass
transition temperature (Tg), that would limit employment of these polymers in optical
applications.
U.S. Patents 3, 546,165; 4,387,209; 4,401,803 describe fluorene based polyesters with
isophthalic or terephthalic acids which are thermally stable but have unsatisfactory
mechanical properties and low inherent viscosity. While U.S. Patent 4,533,511
discloses a process for spinning fibers obtained from the polycondensation product of
9,9-bis-(4- hydroxyphenyl)- fluorene and a mixture of isophthalic acid chloride and
terephthalic acid chloride.
The U.S. Patent 4,967,306 discloses a fluorene diol with isophthalic and terephthalic
acid polyester containing a very low level of oligomeric material but having a tensile
strength, elongation, chemical resistance, temperature stability, ultraviolet resistance
and vacuum stability higher than the copolymers containing oligomeric species.
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However, the films containing small amounts of oligomer "yellow" or degrade upon
limited exposure to ultraviolet radiation.
Polyarylates composed of fluorene diol and isophthalic acid as reported in Journal of
Applied Polymer Science, Vol. 29, p. 35 to 43 (1984) was found to possess
insufficient abrasion resistance and film coating quality was poor. Polyarylates
derived from phenolphthalein and its derivatives exhibit combination of properties of
high softening temperature, good solubility, high thermal resistance and considerable
mechanical strength at higher temperatures. (B. D. Priddy, Jr.; J. E. McGrath, Polym
Preprints 33(2), 231 (1992); S. S. Vibhuthe et al J. Polym. Sci. Polym. Chem. 35,
3227 (1997). The various classes of polymers such as polyesters derived from
bis(hydroxyphenyl)fluorene, cyclic olefins and poly(aryl ether sulfone)s have been
considered for display applications under various trade names by Promerus, Ferrania,
and Sumitomo Bakelite Companies. These polymers show Tg from 223 to 330 °C.
The polymer film should show excellent optical properties in addition to good thermal
properties to allow high temperature processing, good mechanicals and also excellent
barrier properties in order to find its use in optical applications. There is a continuing
need for polymeric thermoplastic compositions to possess a good balance of
transparency and processability, in addition to good mechanical and thermal
properties.
BRIEF DESCRIPTION OF THE INVENTION
2
One embodiment of the present invention is a polyarylate composition comprising:
structural units derived from at least one substituted or unsubstituted diacid and at
least one aromatic dihydroxy compound of structure (I),


WO 2006/107940 PCT/US2006/012454
where Al is independently at each occurrence a C3-C20 aromatic radical; E is
independently at each occurrence a bond, a C1-C20 aliphatic radical, a C3-C20
cycloaliphatic radical, or a C5-C20 aromatic radical, a sulfur atom, a sulfinyl group, a
sulfonyl group, a selenium atom, or an oxygen atom; and t, s and u are independently
integers from 0-10 wherein at least one of t, s and u is not zero and an unsaturated
compound of structure (VIII)

wherein R5 and R6 are independently at any occurrence a carboxylate, oxygen,
carbonyl groups; R7 and R8 are independently at each occurrence hydrogen, aliphatic,
aromatic or cycloaliphatic groups. The composition disclosed possesses good optical
properties, coupled with enhanced thermal and mechanical properties. Also,
disclosed is a process to make the polyarylate compositions of the present invention
and articles derived from said composition.
Various other features, aspects, and advantages of the present invention will become
more apparent with reference to the following description, examples and appended
claims.
DETAILED DESCRIPTION OF THE INVENTION
The present invention may be understood more readily by reference to the following
detailed description of preferred embodiments of the invention and the examples
included herein. In this specification and in the claims, which follow, reference will
be made to a number of terms which shall be defined to have the following meanings.
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.
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As used herein the term "aliphatic radical" refers to a radical having a valence of at
least one comprising a linear or branched array of atoms which is not cyclic. The
array may include heteroatoms such as nitrogen, sulfur, silicon, selenium and oxygen
or may be composed exclusively of carbon and hydrogen. Aliphatic radicals may be
"substituted" or "unsubstituted". A substituted aliphatic radical is defined as an
aliphatic radical which comprises at least one substituent. A substituted aliphatic
radical may comprise as many substituents as there are positions available on the
aliphatic radical for substitution. Substituents which may be present on an aliphatic
radical include but are not limited to halogen atoms such as fluorine, chlorine,
bromine, and iodine. Substituted aliphatic radicals include trifluoromethyl,
hexafluoroisopropylidene, chloromethyl; difluorovinylidene; trichloromethyl,
bromoethyl, bromotrimethylene (e.g. -CH2CHBrCH2-), and the like. For convenience,
the term "unsubstituted aliphatic radical" is defined herein to encompass, as part of
the "linear or branched array of atoms which is not cyclic" comprising the
unsubstituted aliphatic radical, a wide range of functional groups. Examples of
unsubstituted aliphatic radicals include allyl, aminocarbonyl (i.e. -CONH2), carbonyl,
dicyanoisopropylidene (i.e. -CH2C(CN)2CH2-), methyl (i.e. -CH3), methylene (i.e. -
CH2-), ethyl, ethylene, formyl, hexyl, hexamethylene, hydroxymethyl (i.e.-CH2OH),
mercaptomethyl (i.e. -CH2SH), methylthio (i.e. -SCH3), methylthiomethyl (i.e. -
CH2SCH3), methoxy, methoxycarbonyl, nitromethyl (i.e. -CH2NO2), thiocarbonyl,
trimethylsilyl, t-butyldimethylsilyl, trimethyoxysilypropyl, vinyl, vinyledene and the
like. Aliphatic radicals are defined to comprise at least one carbon atom. A Q - C10
aliphatic radical includes substituted aliphatic radicals and unsubstituted aliphatic
radicals containing at least one but no more than 10 carbon atoms.
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
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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 (C6H3) fused to a nonaromatic
component -(CH2)4-. Aromatic radicals may be "substituted" or "unsubstituted". A
substituted aromatic radical is defined as an aromatic radical which comprises at least
one substituent. A substituted aromatic radical may comprise as many substituents as
there are positions available on the aromatic radical for substitution. Substituents
which may be present on an aromatic radical include, but are not limited to halogen
atoms such as fluorine, chlorine, bromine, and iodine. Substituted aromatic radicals
include trifluoromethylphenyl, hexafluoroisopropylidenebis(4-phenyloxy) (i.e. -
OPhC(CF3)2PhO-), chloromethylphenyl; 3-trifluorovinyl-2-thienyl; 3-
trichloromethylphenyl (i.e. 3-CCl3Ph-), bromopropylphenyl (i.e. BrCH2CH2CH2Ph-),
and the like. For convenience, the term "unsubstituted aromatic radical" is defined
herein to encompass, as part of the "array of atoms having a valence of at least one
comprising at least one aromatic group", a wide range of functional groups.
Examples of unsubstituted aromatic radicals include 4-allyloxyphenoxy, aminophenyl
(i.e. H2NPh-), aminocarbonylphenyl (i.e. NH2COPh-), 4-benzoylphenyl,
dicyanoisopropylidenebis(4-phenyloxy) (i.e. -OPhC(CN)2PhO-), 3-methylphenyl,
methylenebis(4-phenyloxy) (i.e. -OPhCH2PhO-), ethylphenyl, phenylethenyl, 3-
formyl-2-thienyl, 2-hexyl-5-furanyl; hexamethylene-l,6-bis(4-phenyloxy) (i.e. -
OPh(CH2)6PhO-); 4-hydroxymethylphenyl (i.e. 4-HOCH2Ph-), 4-
mercaptomethylphemyl (i.e. 4-HSCH2Ph-), 4-methylthiophenyl (i.e. 4-CH3SPh-),
methoxyphenyl, methoxycarbonylphenyloxy (e.g. methyl salicyl), nitromethylphenyl
(i.e. -PhCH2NO2), trimethylsilylphenyl, t-butyldimethylsilylphenyl, vinylphenyl,
vinylidenebis(phenyl), and the like. The term "a C3 - C10 aromatic radical" includes
substituted aromatic radicals and unsubstituted aromatic radicals containing at least
three but no more than 10 carbon atoms. The aromatic radical 1-imidazolyl (C3H2N2)
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represents a C3 aromatic radical. The benzyl radical (C7H8-) represents a C7 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 (C6H11CH12-) 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. Cycloaliphatic
radicals may be "substituted" or "unsubstituted". A substituted cycloaliphatic radical
is defined as a cycloaliphatic radical which comprises at least one substituent. A
substituted cycloaliphatic radical may comprise as many substituents as there are
positions available on the cycloaliphatic radical for substitution. Substituents which
may be present on a cycloaliphatic radical include but are not limited to halogen
atoms such as fluorine, chlorine, bromine, and iodine. Substituted cycloaliphatic
radicals include trifluoromethylcyclohexyl, hexafluoroisopropylidenebis(4-
cyclohexyloxy) (i.e. -OC6H11C(CF3)2C6H11O-), chloromethylcyclohexyl; 3-
trifluorovinyl-2-cyclopropyl; 3-trichloromethylcyclohexyl (i.e. 3-CCl3C6H11-),
bromopropylcyclohexyl (i.e. BrCHkCHbCHbCeHii-), and the like. For convenience,
the term "unsubstituted cycloaliphatic radical" is defined herein to encompass a wide
range of functional groups. Examples of unsubstituted cycloaliphatic radicals include
4-allyloxycyclohexyl, aminocyclohexyl (i.e. H2N C6H11-), aminocarbonylcyclopentyl
(i.e. NH2COC5H9-), 4-acetyloxycyclohexyl, dicyanoisopropylidenebis(4-
cyclohexyloxy) (i.e. -OC6H11C(CN)2C6H11O-), 3-methylcyclohexyl, mefhylenebis(4-
cyclohexyloxy) (i.e. -OC6H11CH2C6H11O-), ethylcyclobutyl, cyclopropylethenyl, 3-
formyl-2-terahydrofuranyl, 2-hexyl-5-tetrahydrofuranyl; hexamethylene-l,6-bis(4-
cyclohexyloxy) (i.e. -OC6H11(CH2)6 C6H11O-); 4-hydroxymethylcyclohexyl (i.e. 4-
HOCH2C6H11-), 4-mercaptomethylcyclohexyl (i.e. 4-HSCH2C6H11-), 4-
methylthiocyclohexyl (i.e. 4-CH3SC6H11-), 4-methoxycyclohexyl, 2-
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methoxycarbonylcyclohexyloxy (2-CH3OCO C6H11O-), nitromethylcyclohexyl (i.e.
NO2CH2C6H10-), trimethylsilylcyclohexyl, t-butyldimethylsilylcyclopentyl, 4-
trimethoxysilyethylcyclohexyl (e.g. (CH30)3SiCH2CH2C6H10-), vinylcyclohexenyl,
vinylidenebis(cyclohexyl), and the like. The term "a C3 - C10 cycloaliphatic radical"
includes substituted cycloaliphatic radicals and unsubstituted cycloaliphatic radicals
containing at least three but no more than 10 carbon atoms. The cycloaliphatic radical
2-tetrahydrofuranyl (C4H7O-) represents a C4 cycloaliphatic radical. The
cyclohexylmethyl radical (C6H11CH2-) represents a C7 cycloaliphatic radical.
The present inventors have unexpectedly discovered a polyarylate composition
comprising a substituted or unsubstituted diacid, an aromatic dihydroxy compound
and an unsaturated compound having good optical properties coupled with the
enhancement in the thermal properties.
A component of the composition of the invention is a substituted or unsubstituted
diacid. In one embodiment of the present invention the diacid is meant to include
carboxylic acids having two carboxyl groups each useful in the preparation of the
polyester resins of the present invention are preferably aliphatic, aromatic or
cycloaliphatic. Chemical equivalents of these diacids include esters, alkyl esters, e.g.,
dialkyl esters, diaryl esters, anhydrides, salts, acid chlorides, acid bromides, and the
like are also included. Examples of diacids are cyclo or bicyclo aliphatic acids, for
example, decahydro naphthalene dicarboxylic acids, norbornene dicarboxylic acids,
bicyclo octane dicarboxylic acids, 1,4-cyclohexanedicarboxylic acid or chemical
equivalents, and most preferred is trans-1,4-cyclohexanedicarboxylic acid or a
chemical equivalent. Linear dicarboxylic acids like adipic acid, azelaic acid,
dicarboxyl dodecanoic acid, and succinic acid may also be useful. Examples of
aromatic dicarboxylic acids are acids that contain a single aromatic ring per molecule
but are not limited to isophthalic or terephthalic acid, l,2-di(p-carboxyphenyl)ethane,
4,4'-dicarboxydiphenyl ether, 4,4'- bisbenzoic acid and mixtures thereof, as well as
acids containing fused rings such as, e.g., 1,4- or 1,5-naphthalene dicarboxylic acids.
In a preferred embodiment, the dicarboxylic acid precursor of residue is terephthalic
acid or alternatively a mixture of terephthalic and isophthalic acids. Non-limiting
examples of the polyvalent carboxylic acid include, an aromatic polyvalent carboxylic
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acid, an aromatic oxycarboxylic acid, an aliphatic dicarboxylic acid, and an alicyclic
dicarboxylic acid, including terephthalic acid, isophthalic acid, ortho- phthalic acid,
1,5- naphthalenedicarboxylic acid, 2,6- naphthalenedicarboxylic acid, diphenic acid,
sulfoterephthalic acid, 5- sulfoisophthalic acid, 4-sulfophthalic acid, 4-
sulfonaphthalene-2,7- dicarboxylic acid, 5-[4-sulfophenoxy] isophthalic acid,
sulfoterephthalic acid, diphenoxyethanedicarboxylic acid or 3-sulfoisophthalic acid,
p-oxybenzoic acid, p- (hydroxyethoxy)benzoic acid, succinic acid, oxalic acid, adipic
acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, fumaric acid, maleic acid,
itaconic acid, hexahydrophthalic acid, tetrahydrophthalic acid, trimethylphenyl
indanoic acid, trimellitic acid, trimesic acid, and pyrromellitic acid, dimeric acid, and
ester- forming derivatives thereof.
In one embodiment of the present invention the polyarylates comprise structural units
derived from aromatic polyols. In another embodiment the polyols are aromatic
dihydroxy compounds. In one embodiment at least one aromatic hydroxy compound
is a dihydroxy aromatic compound of the formula -I-

wherein A1 is independently at each occurrence a C3-C20 aromatic radical; E is
independently at each occurrence a bond, a C1-C20 aliphatic radical, a C3-C20
cycloaliphatic radical, or a C5-C20 aromatic radical, a sulfur atom, a sulfinyl group, a
sulfonyl group, a selenium atom, or an oxygen atom; and t, s and u are independently
integers from 0-10 wherein at least one of t, s and u is not zero.
Suitable aromatic radicals "A1" include, but are not limited to, phenylene,
biphenylene, naphthalene, and the like. Suitable groups "E" include but are not
limited to alkylene and alkylidene groups, for example methylene, ethylene,
ethylidene, propylene, propylidene, isopropylidene, butylene, butylidene,
isobutylidene, amylene, amylidene, isoamylidene, and the like. The group "E"
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includes C5-C20 aromatic radicals for example the C12 divalent aromatic radical
represented by structure -II-, the dashed lines (Structure -II-) indicating the points of
attachment of the radical to the A groups shown in structure -II-.

The group "E" may also be a tertiary nitrogen linkage; an ether linkage; a carbonyl
linkage; a silicon-containing linkage, silane, siloxy; or a sulfur-containing linkage
including, but not limited to sulfide, sulfoxide, sulfone, and the like; or a phosphorus-
containing linkage including but not limited to phosphinyl, phosphonyl and the like.
In other embodiments E may be a cycloaliphatic group including, but not limited to
1,1-cyclopentylidene; 1,1-cyclohexylidene; 3,3,5-trimethyl-l,l-cyclohexylidene; 3-
methyl-1,1-cyclohexylidene; 2-[2.2. l]-bicycloheptylidene, neopentylidene,
cyclopentadecylidene, cyclododecylidene, adamantylidene, and the like.
In one embodiment the dihydroxy aromatic compound represented by structure -I-, E
may be an unsaturated alkylidene group. Suitable dihydroxy-substituted aromatic
hydrocarbons of this type include those of the formula -III-:

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wherein independently each R2 is independently at each occurrence hydrogen,
chlorine, bromine, fluorine, or a C1-20 monovalent aliphatic radical (for example a
methyl group, a t-butyl group, or a methoxy group) and each Y is independently at
each occurrence hydrogen, chlorine, bromine or fluorine.
Suitable dihydroxy-substituted aromatic hydrocarbons also include those of the
formula -IV-:
wherein each R2 is independently hydrogen, chlorine, bromine, fluorine, or a C1-20
monovalent aliphatic radical (for example a methyl group, a t-butyl group, or a
methoxy group), and Rs and Rh are independently hydrogen, a C1-C20 aliphatic
radical, a C3-C20 cycloaliphatic radical or a C4-C20 aromatic radical. Further Rg and Rh
may together form a C4-C20 cycloaliphatic radical.
In some embodiments of the present invention, dihydroxy-substituted aromatic
hydrocarbons that may be used to comprise those disclosed by name or formula
(generic or specific) in U.S. Patent Nos. 2,991,273; 2,999,835; 3,028,365; 3,148,172;
3,153,008; 3,271,367; 3,271,368 and 4,217,438. In other embodiments of the
invention, dihydroxy-substituted aromatic hydrocarbons comprise bis(4-
hydroxyphenyl)sulfide; bis(4-hydroxyphenyl) ether; bis(4-hydroxyphenyl)sulfone;
bis(4-hydroxyphenyl)sulfoxide; 1,4-dihydroxybenzene; 4,4'-oxydiphenol; 2,2-bis(4-
hydroxyphenyl)hexafluoropropane; 4,4'-(3,3,5-trimethylcyclohexylidene)diphenol;
4,4'-bis(3,5-dimethyl)diphenol; l,l-bis(4-hydroxy-3-methylphenyl)cyclohexane; 4,4-
bis(4-hydroxyphenyl)heptane; 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; l,2-bis(4-hydroxyphenyl)ethane; l,l-bis(4-hydroxy-2-
chlorophenyl)ethane; 2,2-bis(3-phenyl-4-hydroxyphenyl)propane; 2,2-bis(4-hydroxy-
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3-methylphenyl)propane; 2,2-bis(4-hydroxy-3-ethylphenyl)propane; 2,2-bis(4-
hydroxy-3-isopropylphenyl)propane; 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane;
3,5,3',5'-tetrachloro-4,4'-dihydroxyphenyl)propane; bis(4-
hydroxyphenyl)cyclohexylmethane; 2,2-bis(4-hydroxyphenyl)-1 -phenylpropane; 2,4'-
dihydroxyphenyl sulfone; 2, 5-dihydroxy naphthalene; 2,6-dihydroxy naphthalene;
hydroquinone; resorcinol; C1-3 alkyl-substituted resorcinols; 4-methyl resorcinol;
catechol; l,4-dihydroxy-3-methylbenzene; 2,2-bis(4-hydroxyphenyl)butane; 2,2-
bis(4-hydroxyphenyl)-2-methylbutane; l,l-bis(4-hydroxyphenyl)cyclohexane; 4,4'-
dihydroxydiphenyl; 2-(3 -methyl-4-hydroxyphenyl)-2-(4-hydroxyphenyl)propane; 2-
(3,5-diraethyl-4-hydroxyphenyl)-2-(4-hydroxyphenyl)propane; 2-(3 -methyl-4-
hydroxyphenyl)-2-(3,5-dimethyl-4-hydroxyphenyl)propane; bis(3,5-dimethylphenyl-
4-hydroxyphenyl)methane; 1,1 -bis(3,5-dimethylphenyl-4-hydroxyphenyl)ethane; 2,2-
bis(3,5-dimetliylphenyl-4-hydroxyphenyl)propane; 2,4-bis(3,5-dimethylphenyl-4-
hydroxyphenyl)-2-methylbutane; 3,3 -bis(3,5-dimethylphenyl-4-
hydroxyphenyl)pentane; 1,1 -bis(3,5-dimethylphenyl-4-hydroxyphenyl)cyclopentane;
l,l-bis(3,5-dimethylphenyl-4-hydroxyphenyl)cyclohexane; bis(3,5-dimethyl-4-
hydroxyphenyl) sulfoxide; bis(3,5-dimethyl-4-hydroxyphenyl) sulfone; bis(3,5-
dimethylphenyI-4-hydroxyphenyl)sulfide; and like bisphenols. In a particular
embodiment the dihydroxy-substituted aromatic hydrocarbon is bisphenol A.
In some embodiments the dihydroxy-substituted aromatic compounds represented by
structure -I- includes compounds comprising one or more fused rings represented by
component "E", attached to one or more aromatic groups A1. Suitable dihydroxy-
substituted aromatic hydrocarbons of this type include those containing indane
structural units such as represented by the formula (-V-), 3-(4-hydroxyphenyl)-l,l,3-
trimethylindan-5-ol; and by the formula (-VI-), l-(4-hydroxyphenyl)-l,3,3-
trimediylindan-5-ol.
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Also included with the class of dihydroxy aromatic compounds represented by
formula -I- are bisphenols comprising spirocyclic structures as component "E", for
example as in 2,2,2',21-tetrahydro-l,l'-spirobi[lH-indene]diol. The term "alkyl" as
used in the various embodiments of the present invention falls within the definition of
an "aliphatic radical" as defined herein.
In one embodiment of the present invention the aromatic diols include its chemical
equivalents. Chemical equivalents to the diols include esters, such as dialkylesters,
diaryl esters, and the like.
In one embodiment of the present invention the aromatic dihydroxy compound is of
structure -VII-

wherein R3 is a substituted or unsubstituted aryl group and R4 is selected from the
group consisting of substituted or unsubstituted (secondary) alkyl, substituted or
unsubstituted cycloaliphatic, substituted or unsubstituted heterocyclic group, or R
and R4 can be linked together to form at least five member substituted or
unsubstituted ring. In another embodiment of the present invention the five member
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ring may also comprise of a heteroatom, examples of heteroatom include but are not
limited to oxygen, nitrogen, sulfur and the like.
In one embodiment of the present invention the polyarylate composition comprises
structural units derived from an unsaturated compound of structure (VIII).

wherein R5and R6 are independently at any occurrence a carboxylate, oxygen or
carbonyl groups; R7 and R8 are independently at each occurrence hydrogen, aliphatic,
aromatic or cycloaliphatic groups. In one embodiment of the present invention the
unsaturated compound could be an unsaturated dicarboxylic acid, unsaturated esters,
unsaturated modified esters or unsaturated ethers. The unsaturated compound can be
aliphatic, cycloaliphatic or aromatic, such as fumaric, maleic, itaconic, citraconic,
mesaconiCj_aconitic, traconic, hexenedioic, octenedioic or 5-norbornene-2,3-
dicarboxylic, or 4,4'-stilbenedicarboxylic acid . The unsaturated compound may also
be an unsaturated diol such as 2-butene-l,4-diol. In one embodiment the unsaturated
compound is fumaryl chloride. In one embodiment the unsaturated compound may be
present in the polymer backbone or as a pendant group thereby enabling cross-linking
and grafting and enhancing the properties.
The ratio of reactants in the composition of the present invention is important. In one
embodiment the diacid is present in a range from about 1 to about 99 mole percent. In
one embodiment, the composition comprises the dihydroxy aromatic compound in the
range of between about 99 mole percent and about 1 mole percent. Typically, the
unsaturated compound is present in a range of between about 0 weight percent and
about 30 weight percent based on the total weight of the polyarylate composition. In
another embodiment the unsaturated compound is present in a range of between about
1 weight percent and about 30 weight percent based on the total weight of the
polyarylate composition. In yet another embodiment the unsaturated compound is
preferably present in a range corresponding to between about 5 to about 10 weight
percent based on the amount of polyarylate composition. In another embodiment the
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dihydroxy compound and the diacid are present in stiochiometric ratio. In one
embodiment the polyarylate composition may be random or block structures.
The composition of the present invention may include additional components which
do not interfere with the previously mentioned desirable properties but enhance other
favorable properties such as anti-oxidants, flame retardants, reinforcing materials,
colorants, mold release agents, fillers, nucleating agents, UV light and heat stabilizers,
lubricants and the like. Additionally, additives such as antioxidants, minerals such as
talc, clay, mica, barite, wollastonite and other stabilizers including but not limited to
UV stabilizers, such as benzotriazole, supplemental reinforcing fillers such as flaked
or milled glass and the like, flame retardants, pigments or combinations thereof may
be added to the compositions of the present invention.
Flame-retardant additives are desirably present in an amount at least sufficient to
reduce the flammability of the polyester resin, preferably to a UL94 V-0 rating. The
amount will vary with the nature of the resin and with the efficiency of the additive.
In general, however, the amount of additive will be from 1 to 30 percent by weight
based on the weight of resin. A preferred range will be from about 5 to 20 percent.
Typically halogenated aromatic flame-retardants include tetrabromobisphenol A
polycarbonate oligomer, polybromophenyl ether, brominated polystyrene, brominated
BPA polyepoxide, brominated imides, brominated polycarbonate, poly (haloaryl
acrylate), poly (haloaryl methacrylate) or mixtures thereof. Examples of other
suitable flame retardants are brominated polystyrenes such as polydibromostyrene and
polytribromostyrene, decabromobiphenyl ethane, tetrabromobiphenyl, brominated
alpha, omega -alkylene-bis-phthalimides, e.g. N,N'-ethylene-bis-
tetrabromophthalimide, oligomeric brominated carbonates, especially carbonates
derived from tetrabromobisphenol A, which, if desired, are end-capped with phenoxy
radicals or with brominated phenoxy radicals or brominated epoxy resins.
The flame retardants are typically used with a synergist, particularly inorganic
artimony compounds. Such compounds are widely available or can be made in
known ways. Typical, inorganic synergist compounds include Sb2O5, SbS3, sodium
14

WO 2006/107940 PCT/US2006/012454
antimonate and the like. Especially preferred is antimony trioxide (Sb2Ch3).
Synergists such as antimony oxides, are typically used at about 0.1 to 10 by weight
based on the weight percent of resin in the final composition. Also, the final
composition may contain polytetrafluoroethylene (PTFE) type resins or copolymers
used to reduce dripping in flame retardant thermoplastics.
Also halogen-free flame retardants can be used. Typical flame-retardants are P-based
flame retardants as organic phosphates (e.g. P(=O)(OR1)(OR2)(OR3) etc),
phosphonates (e.g. R-P(=O)(OR1)(OR2) etc), phosphinates (e.g. R1,R2-P(=O)(OR3)
etc, phosphine oxides (e.g. R1,R2,R3-P(=O) etc) as well as the corresponding
phosphate, phosphonate and/or phosphinate salts of these P-compounds. Besides P-
based flame retardants also N-containing compounds can be used like triazine
derivatives as melamine cyanurate, melamine (pyro or poly)phosphates, etc. Also
other compounds as Zn-borates, hydroxides or carbonates as Mg- and/or Al-
hydroxides or carbonates, Si-based compounds like silanes or siloxanes, Sulfur based
compounds as aryl sulphonates (including salts) or sulphoxides, Sn-compounds as
stannates can be used as well often in combination with one or more of the other
possible flame retardants.
Other additional ingredients may include antioxidants and UV absorbers and other
stabilizers. Antioxidants include i) alkylated monophenols, for example: 2,6-di-tert-
butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-
ethylphenol, 2,6-di-tert-butyl~4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-
dicyclopentyl-4-methylphenol, 2-(alpha-methylcyclohexyl)-4,6 dimethylphenol, 2,6-
di-octadecyl-4-methylphenol, 2,4,6-tricyclohexyphenol, 2,6~di-tert-butyl-4-
methoxymethylphenol; ii) alkylated hydroquinones, for example, 2,6-di-tert-butyl-4-
methoxyphenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone, 2,6-
diphenyl-4-octadecyloxyphenol; iii) hydroxylated thiodiphenyl ethers; iv) alkylidene-
bisphenols; v) benzyl compounds, for example, l,3,5-tris-(3,5-di-tert-butyl-4-
hydroxybenzyl)-2,4,6-trimethylbenzene; vi) acylaminophenols, for example, 4-
hydroxy-lauric acid anilide; vii) esters of beta-(3,5-di-tert-butyl-4-hydroxyphenol)~
propionic acid with monohydric or polyhydric alcohols; viii) esters of beta-(5-tert-
butyl-4-hydroxy-3-methylphenyl)-propionic acid with monohydric or polyhydric
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WO 2006/107940 PCT/US2006/012454
alcohols; vii) esters of beta-(5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid
with mono-or polyhydric alcohols, e.g., with methanol, diethylene glycol,
octadecanol, triethylene glycol, 1,6-hexanediol, pentaerythritol, neopentyl glycol,
tris(hydroxyethyl) isocyanurate, thiodiethylene glycol, N,N-bis(hydroxyethyl) oxalic
acid diamide. Typical, UV absorbers and light stabilizers include i) 2-(2'-
hydroxyphenyl)-benzotriazoles, for example, the 5'-methyl-,3'5'-di-tert-butyl-,5'-tert-
butyl-,5'(l,l,3,3-tetramethylbutyl)-,5-chloro-3',5'-di-tert-butyl-,5-chloro-3'tert-butyl-
S'methyl-3'sec-butyl-S'tert-butyl-4'-octoxy.3'5''-ditert-amyl-3'.5'-bis-Calpha, alpha-
dimethylbenzyl)-derivatives; ii) 2.2 2-Hydroxy-benzophenones, for example, the 4-
hydroxy-4-methoxy-,4-octoxy,4-decloxy-,4-dodecyloxy-,4-benzyloxy,4,2',4'-
trihydroxy-and 2'hydroxy-4,4'-dimethoxy derivative, and iii) esters of substituted and
unsubstituted benzoic acids for example, phenyl salicylate, 4-tert-butylphenyl-
salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis-(4-tert-butylbenzoyl)-
resorcinol, benzoylresorcinol, 2,4-di-tert-butyl-phenyl-3,5-di~tert-butyl-4-
hydroxybenzoate and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate. Phosphites and
phosphonites stabilizers, for example, include triphenyl phosphite, diphenylalkyl
phosphites, phenyldialkyl phosphites, tris(nonyl-phenyl)phosphite, trilauryl phosphite,
trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert~
butylphenyl)phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-
butylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, and
tetrakis(2,4-di-tert-butylphenyl)4,4'-biphenylenediphosphonite.
Dyes or pigments may be used to give a background coloration. Dyes are typically
organic materials that are soluble in the resin matrix while pigments may be organic
complexes or even inorganic compounds or complexes, which are typically insoluble
in the resin matrix. These organic dyes and pigments include the following classes
and examples: furnace carbon black, titanium oxide, phthalocyanine blues or greens,
anthraquinone dyes, scarlet 3b Lake, azo compounds and acid azo pigments,
quinacridones, chromophfhalocyanine pyrroles, halogenated phthalocyanines,
quinolines, heterocyclic dyes, perinone dyes, anthracenedione dyes, thioxanthene
dyes, parazolone dyes, polymethine pigments and others.
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WO 2006/107940 PCT/US2006/012454
Typically, in the hydrogenation, two isomers are obtained in which the carboxylic
acid groups are in cis- or trans- positions. The cis- and trans- isomers can be separated
by crystallization with or without a solvent, for example, n-heptane, or by distillation.
The cis-isomer tends to blend better; however, the trans- isomer has higher melting
and crystallization temperatures and may be preferred. Mixtures of the cis- and trans-
isomers are useful herein as well. When the mixture of isomers or more than one
diacid or diol is used, a copolyester or a mixture of two polyesters may be used as the
present cycloaliphatic polyester resin.
Optionally a catalyst may be present for the synthesis of the polyarylates of the
present invention. In one embodiment the catalysts include, but are not limited to
metal salts and chelates of Ti, Zn, Ge, Ga, Sn, Ca, Li and Sb. Other known catalysts
may also be used for this step-growth polymerization. The choice of catalyst being
determined by the nature of reactants. The various catalysts for use herein are very
well known in the art and are too numerous to mention individually herein. A few
examples of the catalysts which may be employed in the above process include but
are not limited to titanium alkoxides. such as tetramethyl, tetraethyl, tetra(n-propyl),
tetraisopropyl and tetrabutyl titanates; dialkyl tin compounds, such as di-(n-butyl) tin
dilaurate. di-(n-butyl) tin oxide and di-(n-butyl) tin diacetate; and oxides, acetate salts
and sulfate salts of metals, such as magnesium, calcium, germanium, zinc, antimony,
etc. Conveniently titanium alkoxides are employed. The catalyst level is employed in
an effective amount to enable the copolymer formation and is not critical and is
dependent on the catalyst that is used. Generally, the catalyst is used in concentration
ranges of about 10 to about 500 ppm, preferably about less than about 200 ppm and
most preferably about 20 to about 300 ppm.
In one embodiment of the present invention the polyarylates are prepared by melt
processes that are well known to those skilled in the art and consist of several steps.
The first reaction step is generally done under a nitrogen sweep with efficient stirring
and the reactants may be heated slowly or quickly. Appropriate reaction conditions
for a variety of acid-alcohol polymerizations are known in the art. Any
polymerization temperature which gives a clear melt under the addition conditions
and affords a reasonable rate of polymerization without unwanted amount of side
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WO 2006/107940 PCT/US2006/012454
reaction and degradation may be used. In one embodiment the temperature of the
reaction is between about 175 °C and about 350 °C. In another embodiment the
temperature is between about 200 °C and about 3OO.°C. The reaction is maintained in
this stage for 0.5 to 3 hours with the condensation reaction of esterification taking
place. In one embodiment the reaction is then carried out under vacuum of about 0.1
Torr while the reaction occurs and polyarylate of desired molecular weight is built. In
one embodiment the polyarylate is recovered in the last step by either cooling and
isolating the polymer and grinding or by extruding the hot polymer melt, cooling and
pelletizing.
The reaction may be conducted optionally in presence of a solvent or in neat
conditions without the solvent. The organic solvent used in the above process
according to the invention should be capable of dissolving the polyarylate to an extent
of at least 0.01 g/per ml at 25°C and should have a boiling point in the range of 140 -
290 °C at atmospheric pressure. Preferred examples of the solvent include but are not
limited to amide solvents, in particular, N-methyl-2-pyrrolidone, N- acetyl-2-
pyrrolidone, N,N'-dimethyl formamide, N,N'-dimethyl acetamide, N, N'-diethyl
acetamide, N,N'-dimethyl propionic acid amide, N,N'-diethyl propionic acid amide,
tetramethyl urea, tetraethyl urea, hexamethylphosphor triamide, N-methyl
caprolactam and the like. Other solvents may also be employed, for example,
methylene chloride, chloroform, 1,2-dichloroethane, tetrahydrofuran, diethyl ether,
dioxane, benzene, toluene, chlorobenzene, o-dichlorobenzene and the like.
In one embodiment the polyarylate composition may be made by conventional
blending techniques. The production of the compositions may utilize any of the
blending operations known for the blending of thermoplastics, for example blending
in a kneading machine such as a B anbury mixer or an extruder. To prepare the
composition, the components may be mixed by any known methods. Typically, there
are two distinct mixing steps: a premixing step and a melt mixing step. In the
premixing step, the dry ingredients are mixed together. The premixing step is
typically performed using a tumbler mixer or ribbon blender. However, if desired, the
premix may be manufactured using a high shear mixer such as a Henschel mixer or
similar high intensity device. The premixing step is typically followed by a melt
18

WO 2006/107940 PCT/US2006/012454
mixing step in which the premix is melted and mixed again as a melt. Alternatively,
the premixing step may be omitted and raw materials may be added directly into the
feed section of a melt mixing device, preferably via multiple feeding systems, hi the
melt mixing step, the ingredients are typically melt kneaded in a single screw or twin
screw extruder, a Banbury mixer, a two roll mill, or similar device. In one
embodiment the polyarylate synthesized by melt mixing process the pre mixing is
carried out at a temperature range of between about 200 °C to about 375 °C. The
heating or melt mixing is typically carried out at a temperature range of about 250 °C
to about 300 °C.
In one embodiment of the present invention the composition could be prepared by
solution method. The solution method involves dissolving all the ingredients in a
common solvent (or) a mixture of solvents and either precipitation in a non-solvent or
evaporating the solvent either at room temperature or a higher temperature of at least
about 50 °C to about 80 °C. In one embodiment, the reactants can be mixed with a
relatively volatile solvent, preferably an organic solvent, which is substantially inert
towards the polymer, and will not attack and adversely affect the polymer. Some
suitable organic solvents include ethylene glycol diacetate, butoxyethanol,
methoxypropanol, the lower alkanols, chloroform, acetone, methylene chloride,
carbon tetrachloride, tetrahydrofuran and the like. In one embodiment of the present
invention the non solvent is at least one selected from the group consisting of mono
alcohols such as ethanol, methanol, isopropanol, butanols and lower alcohols with Cl
to about C12 carbon atoms, hi one embodiment the solvent is chloroform.
The preferred polyarylates are preferably high molecular weight polymers have an
intrinsic viscosity (as measured in 60: 40 solvent mixture of phenol/tetrachloroethane
at 25°C) ranging from about 0.30 deciliters per gram to about 1.8 deciliters per gram.
In another embodiment the intrinsic viscosity is in the range between about 0.30
deciliters per gram to about 1.2 deciliters per gram. In one embodiment of the present
invention the polyarylates may be branched or unbranched and having a weight
average molecular weight of at least greater than 15,000, preferably from about
20,000 to about 2,00,000 as measured by viscosity measurements in Phenol /
19

WO 2006/107940 PCT/US2006/01245^
tetrachloroethane (60:40, volume / volume ratio) solvent mixture. It is contemplated
that the polyarylates may have various known end groups.
In one embodiment the glass transition temperatures (Tg) of the polyarylates are
substiatially high. The polyarylates of the present invention have a glass transition
temperature in the range of between about 150 °C and about 450 °C and preferably
between about 200 °C to about 350 °C.
The polyarylate of the present invention are soluble in low boiling chlorinated
solvents like methylene chloride, ethylene chloride, chloroform, carbontetrachloride,
tetrachloroethane and the like. In one embodiment the polyarylate of the present
invention are chemical resistant to lower alcohols and ketones with Cl to about C12
carbon atoms like acetone. In yet another embodiment the polyarylate compositions
are colourless.
The compositions can be molded into useful articles by a variety of means, for
example injection molding, extrusion molding, rotation molding, foam molding,
calendar molding, blow molding, thermoforming, compaction, melt spinning and the
like, to form articles. Suitable articles are exemplified but are not limited to aircraft,
automotive, truck, military vehicle (including automotive, aircraft, and water-borne
vehicles), scooter, and motorcycle exterior and interior components, including panels,
quarter panels, rocker panels, trim, fenders, doors, decklids, trunk lids, 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, aircraft components; 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; wall panels, and doors; counter tops;
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WO 2006/107940 PCT/US2006/012454
protected graphics; outdoor and indoor signs; enclosures, housings, panels, and parts
for automatic teller machines (ATM); computer; desk-top computer; portable
computer; lap-top computer; palm- held computer housings; monitor; printer;
keyboards; FAX machine; copier; telephone; phone bezels; mobile phone; radio
sender; radio receiver; 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;
shoe laces; articles made from plastic-wood combinations; golf course markers; utility
pit covers; 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 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.
In one embodiment of the present invention the polyarylate composition of the present
invention, because of their advantageous thermal, mechanical and optical
characteristics, especially preferred are articles for optical applications. The
compositions in one embodiment can be employed as substrate for optical articles like
the organic light emitting diode (OLED). The article of the present invention would
include various electronic applications like for example flexible circuits, liquid crystal
displays, organic light emitting diode (OLED) displays, and the like. The
compositions also find application for headlight covers, markers for anti piracy, etc.
EXAMPLES
Without further elaboration, it is believed that one skilled in the art can, using the
description herein, utilize the present invention to its fullest extent. The following
examples are included to provide additional guidance to those skilled in the art in
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WO 2006/107940 PCT/US2006/012454
practicing the claimed invention. The examples provided are merely representative of
the work that contributes to the teaching of the present application. While only
certain features of the invention have been illustrated and described herein, many
modifications and changes will occur to those skilled in the art. Accordingly, these
examples are not intended to limit the invention, as defined in the appended claims, in
any manner.
In the following examples values for glass transition temperatures (Tg) were
determined by differential scanning calorimetry (DSC) at a heating rate of 20°C per
minute. The intrinsic viscosity (IV) was measured in Ubbelhode suspended
viscometer in phenol / tetrachloroethane 60 / 40 volume by volume ratio of the
solvent mixture at 25 °C in thermostated viscosity bath and viscosity average
molecular weight was determined. Also the Yellow index or YI was measured on a
Gardner Colorimeter model XL-835. The percentage transmission was determined in
accordance with test method ASTM D-1003. The various abbreviations used herein
are tabulated in Table 1.
Table 1

1,3-BHPM 1,3- Bishydroxyphenyl menthane
TCDBP 4,4'-(Octahydro-4,7-methane-5H-inden-5-yliden)bisphenol
PPPBP N-Phenyl-(3,3 '-bis-(4-hydroxyphenyl)phthalimide
BPA 4,4' Isopropylidene bisphenol
TPC 1,4- benzenedicarbonyl chloride
EPC 1,3-benzenedicarbonyl chloride
DMBPC 1,1' Bis(4-hydroxy-3-methylphenyl) cyclohexane
TMBPC 1,1'Bis (4-hydroxy-3,5-dimethyl phenyl) cyclohexane
TMBPTBC 1,1 Bis (4-hydroxy-3,5- dimethyl phenyl) -4-tertiary bytyl cyclohexane
DCBP 3,8-Dihydroxy-5a, lOb-diphenyl coumarono[2,3-b]coumarane
BPAP 4,4'-(l -phenylethylidene) bisphenol
TMBPF 4,4'-Methylene bisphenol
BPF 4,4'-(9-Flouorenylidene) diphenol
SBI 3,3,3 '3 '-Tetramethy 1-1,1 '-Spirobiindane-6,6 '-diol
BDO 1,4-Butanediol
FC Fumaryl Chloride
EG 1,2-Ethanediol
TMBPA 4,4' -Isopropyl idenebis(2,6-dimethylphenol)
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PREPARATION OF POLYARLATES
A 4- neck 1000 mL round bottom flask was fitted with cooling condenser, stirrer
blade, 50 ml addition funnel and a 250 ml addition funnel. Anhydrous potassium
carbonate (1.275 grams; 9.24 mmol) and 75 ml dichloromethane were added into the
flask. 1,4-Butane Diol (0.5543grams; 6.2 mmol) was weighed in a vial and fed into
the reactor with 75 mL dichloromethane. Fumaryl chloride (0.4704 grams; 3.1mmol)
was weighed in a vial and added in 25mL of dichloromethane through the addition
funnel. The solution was added dropwise over a period of 15-20 minutes. The
addition funnel was washed with 15 mL dichloromethane couple of times and reaction
mixture was stirred for an additional 30 minutes. Benzyl triethyl ammonium
chloride(0.1822 gram) and 4,4'-(Octahydro-4,7-methane-5H-inden-5-yliden)
bisphenol (18.719 grams; 58.5mmol) were added to the solution, followed by addition
of a solution of sodium hydroxide (NaOH; 9.348grams; 233.7mmol) in 150mL DM
water under stirring conditions. The stirring was allowed to proceed for 15 minutes,
after which freshly crystallized (in hexane) isophthaloyl chloride (12.490 grams; 62
mmol) of was weighed and transferred into 250 mL addition funnel in 60mL
dichloromethane. The addition was carried out dropwise over a period of 30-40
minutes. After completion of addition, stirring was continued for about 60 minutes at
room temperature. A solution 0.0264gram benzoyl chloride in dichloro methane (10
mL) was added and stirred for 45 minutes. Stirring was stopped and the reaction
mixture was transferred to a separator funnel, the organic layer was allowed to settle
to bottom while the aqueous layer was drained off. Organic layer was repeatedly
washed with 250mL 1.0M hydrochloric acid solution. The organic layer was washed
with water (250 mL), and slowly added into cold solution of 1000 mL methanol with
stirring. The polymer thus formed was filtered under suction and washed with
methanol and dried overnight in an oven at 80 °C. The procedure was repeated for
preparation of polyarylates using the various monomer and the data is reported in
Table 2.
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-24-

WO 2006/107940 PCT/US2006/012454
In a 100 mL round bottomed two neck flask equipped with a magnetic stirrer,
nitrogen gas inlet, CaCl2 guard tube was charged with 4,4'-(Octahydro-4,7-methane-
5H-inden-5-yliden) bisphenol (1 gm; 3.12 mmol), (15 mL) methylene dichloride, and
0.78 gm ( 7.8 mmol) triethyl amine. The resulting reaction mixture was stirred at
room temperature. The bisphenol dissolved in methylene chloride and a clear solution
was obtained. The reaction flask placed in an ice salt mixture and cooled to about 0
°C. To this solution, 0.633 gm (3.12 mmol) terephthaloyl dichloride dissolved in
methylene chloride was added dropwise over a period of 10 minutes. An additional
amount of (5 mL) methylene chloride was added to wash the terephthaloyl chloride
in to the reaction mixture. The reaction mixture was stirred at O °C for 30 minutes.
The reaction mixture was brought to room temperature and stirred for about another
2.5 hours. The reaction mixture was diluted with methylene chloride and washed
repeatedly with distilled water. The solution was poured slowly into methanol with
stirring to precipitate the white fibrous polymer. It was filtered under suction, washed
with water and dried in oven at 80 °C for 12 h. The viscosity of the polymer is 0.38
dL/g. and the Tg of the polymer is 288 °C. The polyarylates given in Table 3 were
synthesized using this method and are reported in Table 3.
Table 3

Polymer Monomers rv MW(IV) Tg(°C)
Bisphenol AcidChloride (dL/g)
10. UBHPM-PA 1.3BHPM TPC 0.82 54,300 285
11. 1,3BHPM-PA 1.3BHPM IPC 0.69 73,600 251
12. 1,3BHPM-PA 1.3BHPM TPC/IPC(50/50) 0.65 61,200 273
13. TCDBP-PA TCDBP TPC 0.38 41,400 288
14. TCDBP-PA TCDBP IPC 0.32 30,100 267
15. PPPBP-PA PPPBP TPC 0.33 20,100 289
16. PPPBP-PA PPPBP IPC 0.24 22,200 267
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PREPARATION OF POLYARYLATE BY INTERFACIAL METHOD:
In a two neck round bottom flask, 200 milligram of NaOH (5 mmol) was dissolved in
12 ml of deionised water at room temperature. To this 1 gm (2.5 mmol) of 3,8-
dihydroxy-5a,10-diphenyl coumarono[2,3-b]coumarane (DCBP) was added and with
gradual stirring till it dissolved completely in NaOH. The clear solution was obtained
and 5 mg of benzyltriethylammonium chloride was added and reaction flask was
placed in an ice salt mixture and stirred. The 0.513 gin (2.5 mmol) of terephthaloyl
chloride dissolved in 10 ml of dry chloroform was added dropwise through addition
funnel in 10 min. After the addition was complete the reaction mixture was rapidly
stirred (1500 rpm) for 45 min followed by dilution with chloroform. The reaction
mixture was then washed with dilute HC1 solution repeatedly with distilled water in
a separatory funnel till the pH of the solution turned neutral. The organic layer was
poured slowly into methanol, and the white fibrous polymer was separated. It was
filtered under suction, washed with water and dried in oven at 80 °C for 12 h. The
viscosity of the polymer in PhOH/TCE solvent mixture is 0.54 dL/g. and the Tg of the
polymer is 343 °C. Polyarylates compositions in Table 4 have been synthesized using
this procedure.
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Table 4

Polyarylate Composition FilmThickness(micron)a Tg(°C)b MW(byIV) rvc YI
17. DMBPC/TPC 100/100 125-140 233 165000 1.61 1.7
18. TMBPC/TPC 100/100 125-140 279 108000 1.12 0.9
19. TMBPTBC/TPC 100/100 130-140 277 60000 1.09 1.1
20. TMBPA/TPC 100/100 85-110 212 32700 0.41 0.6
21. DCBP/TPC 100/100 20-35 343 45300 0.54 1
22. BPAP/TPC 100/100 120-150 282 147000 1.45 2
23. PPPBP/TPC 100/100 120-150 325 143000 1.42 1.6
24. PPPBP/IPC 100/100 120-150 300 112000 1.16 1.2
25. TCDBP/TPC 100/100 120-150 285 68510 0.76 1.1
26. TCDBP/IPC 100/100 130-140 265 23900 0.32 1.5
27. BPAP/TPC 100/100 125-150 223 93700 1 0.9
28. BPAP/TMBPF/TPC 30/70/100 120-130 255 104400 1.09 1.1
29. BPF/TMBPF/TPC 30/70/100 125-140 280 151900 1.5 2
30. BPF/BPA/TPC 70/30/100 125-145 310 89500 0.96 1.2
31. BPAP/BPF/TPC 30/70/100 130-140 300 32000 0.41 1.8
32. SBI/TMBPF/TPC 70/30/100 85-110 286 46500 0.56 1
33. BPAP/TMBPF/BPC 30/70/100 20-35 217 142000 1.42 1.8
a: casted film in dichloromethane & solvent evaporated at room temp.b: frommin. .c: In phenol/TCE at 3:2 V/V at 25 °C. DSC at 10 UC
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WO 2006/107940 PCT/US2006/012454
CLAIMS:
1. A polyarylate composition, wherein said polyarylate comprises structural units
derived from
(a) a substituted or unsubstituted diacid;
(b) an aromatic dihydroxy compound of the structure (I):

wherein A1 is independently at each occurrence a C3-C20 aromatic radical; E is
independently at each occurrence a bond, a C1-C20 aliphatic radical, a C3-C20
cycloaliphatic radical, or a C5-C20 aromatic radical, a sulfur atom, a sulfinyl group, a
sulfonyl group, a selenium atom, or an oxygen atom; and t, s and u are independently
integers from 0-10 wherein at least one of t, s and u is not zero and;
(c) an unsaturated compound of structure (VIII)
R5 CR7=CR8-R6 (VIII)
wherein R ,and R6 are independently at any occurrence an carboxylate, oxygen,
carbonyl groups; R7 and R8 are independently at each occurrence hydrogen, aliphatic,
aromatic or cycloaliphatic groups.
2. The composition according to claim 1, wherein said dihydroxy compound is of
the structure (VII)

28

O 2006/107940 PCT/US2006/012454
wherein R3 is a substituted or unsubstituted aryl group and R4 is selected from the
group consisting of substituted or unsubstituted alkyl, substituted or unsubstituted
cycloaliphatic, substituted or unsubstituted heterocyclic group, or R3 and R4 can be
linked together to form at least five member substituted or unsubstituted ring.
3. The composition according to claim 2, wherein said at least five member ring
may optionally comprise at least one heteroatom.
4. The article of claim 1, wherein said diacid is at least one selected from the
group consisting of linear acids, cycloaliphatic acids, terephthalic acids, isophthalic
acids, bicyclo aliphatic acids, decahydro naphthalene dicarboxylic acids, norbornene
dicarboxylic acids, bicyclo octane dicarboxylic acids, 1,4-cyclohexanedicarboxylic
acid, adipic acid, azelaic acid, dicarboxyl dodecanoic acid, and succinic acid, dialkyl
esters, diaryl esters, anhydrides, salts, acid chlorides and acid bromides.
5. The composition of claim 1, wherein said unsaturated compound is at least
one selected from the group consisting of fumaric acid, maleic acid, itaconic acid,
citraconic acid, mesaconic acid^aconitic acid, traconic acid, hexenedioic acid,
octenedioic acid, 5-norbornene-2,3-dicarboxylic, 4,4'-stilbenedicarboxylic acid
fumaryl chloride, 2-butene-l,4-diol, hexenediol, pentenediol, long chain unsaturated
aliphatic diols and aromatic diols like stilbene-diol, and derivatives thereof.
6. The composition of claim 1, wherein said unsaturated compound is present in
a range of between about 0 to about 30 percent by weight based on the total weight of
said composition.
7. The composition of claim 1, wherein said unsaturated compound is present in
a range of between about 5 to about 10 percent by weight based on the total weight of
said composition.
8. The composition of claim 1, wherein said polyarylate may optionally comprise
a stabilizing additive.
9. The composition of claim 8, wherein said stabilizing additive is selected from
the group consisting of anti-oxidants, flame retardants, reinforcing materials,
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colorants, mold release agents, fillers, nucleating agents, UV light stabilizers, heat
stabilizers, lubricants, antioxidants flame retardants, pigments or combinations thereof
10. The composition of claim 8, wherein said stabilizing additive is present at a
level from about 0 to about 10 percent by weight based on the total weight of said
composition.
11. The composition of claim 1, wherein said diacid is present in a range of
between about 1 mole percent and about 99 mole percent.
12. The composition of claim 1, wherein said diol is present in a range of between
about 99 mole percent and about 1 mole percent.
13. The composition of claim 1, wherein said polyarylate has an intrinsic viscosity
of at least greater than about 0.25 dL/g.
14. The composition of claim 1, wherein said polyarylate has a glass transition
temperature of between about 150 °C and about 450 °C.
15. The composition of claim 1, wherein said polyarylate has a yellowness index
of less than about 2.
16. The composition of claim 1, wherein said polyarylate composition transmits
about greater than 90 percent light in the region of about 400 nm to about 800 nm.
17. An article comprising a polyarylate composition, wherein said polyarylate
comprises structural units derived from

(a) a substituted or unsubstituted diacid and;
(b) an aromatic dihydroxy compound of the structure (I):
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wherein A1 is independently at each occurrence a C3-C20 aromatic radical; E is
independently at each occurrence a bond, a C1-C20 aliphatic radical, a C3-C20
cycloaliphatic radical, or a C5-C20 aromatic radical, a sulfur atom, a sulfinyl group, a
sulfonyl group, a selenium atom or an oxygen atom; and t, s and u are independently
integers from 0-10 wherein at least one of t, s and u is not zero.
18. The article according to claim 17, wherein said dihydroxy compound is of the
structure (VII)
wherein R3 is a substituted or unsubstituted aryl group and R4 is selected from the
group consisting of substituted or unsubstituted (secondary) alkyl, substituted or
unsubstituted cycloaliphatic, substituted or unsubstituted heterocyclic group, or R3
and R4 can be linked together to form at least five member substituted or
unsubstituted ring.
19. The article according to claim 18, wherein said at least five member ring may
optionally comprise at least one heteroatom.
20. The article of claim 17, wherein said polyarylate may further comprise an
unsaturated compound of structure (VIII)
R5 CR7=CR8-R6 (VIII)
wherein R5 and R6 are independently at any occurrence a carboxylate, oxygen,
carbonyl groups; R7 and R8 are independently at each occurrence hydrogen, aliphatic,
aromatic or cycloaliphatic groups.
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21. The article of claim 20, wherein said unsaturated compound is at least one
selected from the group consisting of fumaric acid, maleic acid, itaconic acid,
citraconic acid, mesaconic acid aconitic acid, traconic acid, hexenedioic acid,
octenedioic acid, 5-norbornene-2,3-dicarboxylic, 4,4'-stilbenedicarboxylic acid
fumaryl chloride, 2-butene-l,4-diol, hexenediol, pentenediol, long chain unsaturated
aliphatic diols and aromatic diols like stilbene-diol, and derivatives thereof.
22. The article of claim 20, wherein said unsaturated compound is present in a
range of between about 0 to about 30 percent by weight based on the total weight of
said composition.
23. The article of claim 20, wherein said unsaturated compound is present in a
range of between about 0 to about 10 percent by weight based on the total weight of
said composition.
24. The article of claim 17, wherein said polyarylate may optionally comprise a
stabilizing additive, wherein said stabilizing additive is selected from the group
consisting of anti-oxidants, flame retardants, reinforcing materials, colorants, mold
release agents, fillers, nucleating agents, UV light stabilizers, heat stabilizers,
lubricants, antioxidants, flame retardants, pigments or combinations thereof.
25. The article of claim 17, wherein said polyarylate has an intrinsic viscosity of at
least greater than about 0.25 dL/g.
26. The article of claim 17, wherein said polyarylate has a glass transition
temperature of between about 150 °C and about 450 °C.
27. The article of claim 17, wherein said polyarylate has a yellowness index of
less than about 2.
28. The article of claim 17, wherein said polyarylate composition transmits about
greater than 90 percent light in the region of about 400 nm to about 800 nm.
29. The article of claim 17, wherein said article is used as a substrate for optical
applications.
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30. A method to make an article according to claim 17, wherein said article
comprises comprising a polyarylate composition, wherein said polyarylate comprises
structural units derived from
(a) a substituted or unsubstituted diacid or a derivative and;
(b) an aromatic dihydroxy compound of the structure (I):
wherein A1 is independently at each occurrence a C3-C20 aromatic radical; E is
independently at each occurrence a bond, a C1-C20 aliphatic radical, a C3-C20
cycloaliphatic radical, or a C5-C20 aromatic radical, a sulfur atom, a sulfinyl group, a
sulfonyl group, a selenium atom, or an oxygen atom; and t, s and u are independently
integers from 0-10 wherein at least one of t, s and u is not zero.
33
31. The method of claim 30, wherein said method may optionally be carried out in
presence of a solvent.

A polyarylate composition comprising ; structural units derives at least one substituted
or unsubstituted diacid, at least one aromatic dihydroxy compound, and an unsaturated
compound. The composition possesses good optical properties, flow, stability and
mechanical property.