Title of Invention

"PHASE TRANSFER CATALYZED METHOD FOR PREPARATION OF POLYETEHRIMIDES."

Abstract Polyether polymers, such as polyetherimides, are prepared by the reaction of a dihydroxy-substituted aromatic hydrocarbon alkali metal salt, such as bisphenol A disodium salt, with a bis(N-(chlorophthalimido))aromatic compound, such as 1,3-and/or l,4-bis[N-(4-chlorophthalimido)]benzene, in a solvent such as o-dichlorobenzene and in the presence of a phase transfer catalyst such as a hexaalkylguanidinium chloride. Several embodiments may be employed to improve the method. They comprise employing substantially dry reagents, employing a high solids level in solvent, beginning with an excess of bis(N-(chlorophthalimido))-aromatic compound and incrementally adding alkali metal salt, employing alkali metal salt of small particle size, and using reagents of high purity.
Full Text PHASE TRANSFER CATALYZED METHOD FOR PREPARATION OF
POLYETHER1MIDES
BACKGROUND OF INVENTION
This invention relates to the preparation of polyether polymers and more particularly
to an improved method for such preparation in a phase transfer catalyzed reaction. In
a particular embodiment the invention relates to the preparation of polyetherimides in
a phase transfer catalyzed reaction.
Polyetherimides have become an important genus of engineering resins because of
their excellent properties. Conventionally, they have been prepared by the reaction of
an aromatic diamine with an aromatic dianhydride. This method, however, has a
disadvantage in that it requires many steps for preparation of the dianhydride,
including, for example, the conversion of phthalic anhydride to an N-alkylimide,
nitration of said N-alkylimide, displacement of the nitro group with an alkali metal
salt of a dihydroxy-substituted aromatic hydrocarbon and an exchange reaction with
phthalic anhydride to afford the dianhydride.
It has also long been known to prepare polyetherimides by a displacement reaction of
an alkali metal salt of a dihydroxy-substituted aromatic hydrocarbon with an aromatic
bis(substituted phthalimide). As originally developed, this reaction required the use of
expensive dipolar aprotic solvents and the product tended to develop color and be
contaminated with various by-products,
U.S. Patent 5,229.482 discloses a displacement method for the preparation of
polyetherimides from bis(chlorophthalimides) using a solvent of low polarity such as
o-dichlorobenzene, in the presence of a thermally stable phase transfer catalyst such
as a hexaalkylguanidinium halide. U.S. Patent 5,830,974 discloses a similar method
using a monoalkoxybenzene such as anisole as solvent. These methods made it
possible, for the first time, to envision the commercial production of polyetherimides
by the displacement method.
Nevenhekss, severai problems remain to be solved for the optimum development of
the displacement reaction for polyetherimide preparation. First, there has been no
method for control of molecular weight of the product, other than limiting reaction
time. Second, the amount of phase transfer catalyst required for polyetherimide
preparation in substantial yield is high, typically on the order of 5 mole percent based
on bis(chlorophtha)imide). Third, the product typically contains relatively large
proportions, typically 8-10% by weight, of cyclic oligomers. While the preparation
and ring-opening polymerization of cyclic poiyetherimide oligomers may be a useful
alternative to other polymerization methods, the presence of such oligomers as byproducts
in the linear polymer can adversely affect its properties and increase its
polydispersity (Mw/Mn). Fourth, endcapping methods that might minimize problems
resulting from the presence of reactive end groups have not been known. Fifth, the
effects of such variables as impurity level and stoichiometric imbalance of the
reagents have been unknown.
It is of interest, therefore, to continue development of the displacement method of
polyetherimide preparation and optimize the same.
SUMMARY OF INVENTION
The present invention is based on a series of studies that identified several variables in
the displacement process and led to the discovery of optimal conditions therefor.
In one embodiment the invention is a method for preparing an aromatic polyether
polymer which comprises contacting, in a solvent of low polarity, substantially
equimolar amounts of at least one alkali metal salt of a dihydroxy-substituted
aromatic hydrocarbon and at least one bis((N-(chlorophthalimido))-aromatic
compound, in the presence of a phase transfer catalyst which is substantially stable at
the temperatures employed; said method further comprising at least one of the
following embodiments:
(A) employing substantially dry solvent, alkali metal salt and bis(N-
(chlorophthalimido))aromatic compound such that the reaction mixture comprising
the same contains at most about 20 ppm by weight of water;
(B) starting the reaction by addition of phase transfei catalyst wherein the polymer
solids level in said solvent is at a value of at least about 15% and then concentratirm
the -2- mixture during reaction until the said value is in the range of between about 25%
polymer solids level and about 60% polymer solids level;
(C) maintaining the combined level of said alkali metal salt and bis(N-
(chlorophthalimido))aromatic compound in said solvent at a value in the range of
between aboul 25% polymer solids level and about 60% polymer solids level;
(D) beginning said contact using a molar excess of said bis(N-
(chlorophthalimido))aromatic compound up to about 5% and subsequently adding
alkali metal salt at least once to afford a polyether polymer of a desired molecular
weight;
(E) employing alkali metal salt having less than about 25% of particles with a
diameter of greater than about 200 nm, and
(F) employing at least one of
(1) an alkali metal salt which is stoichiometrically pure or contains at most about 0.3
mole % of free dihydroxy-substituted aromatic hydrocarbon or of free sodium
hydroxide, and
(2) a bis(N-(chlorophthalimido))aromatic compound which is stoichiometrically pure
or contains excess anhydride groups in a proportion up to 0.5 mole %, contains
phlhalides in a proportion no greater than about 1000 ppm, and contains
chlorobenzoic acids in a proportion no greater than about 0.15 mole %.
Various other features, aspects, and advantages of the present invention will become
more apparent with reference to the following description and appended claims.
BRIEF DESCRIPTION OF DRAWINGS
FIGURES 1-6 are graphical representations of the results of Examples 12-15 and 17-
.25. Molecular weights in FIGURES 1-6, read along the y-axes of the graphs, are in
kg/mole; that is, they are conventional molecular weights in g/mole divided by 1.000.
DETAILED DESCRIPTION
The alkali metal salts of dihydroxy-substituted aromatic hydrocarbons. which are
employed in the present invention are typically sodium or potassium salts. Sodium
sails are often used in particular embodiments by reason of their availability and
relatively low cost.
Suitable dihydroxy-substituted aromatic hydrocarbons include those represented by
the formula (I):
(Figure Removed)
wherein D is a divalent aromatic radical. In some embodiments, D has the structure
of formula (11):
(II)
(Figure Removed)
wherein A' represents an aromatic group including, but not limited to, phenylene,
biphenylene, naphthylene, etc. In some embodiments E may be an alkylene or
alkylidene group including, but not limited to, methylene, ethylene, ethylidene,
propylene, propylidene, isopropylidene, butylene, butylidene, isobutylidene, amylene,
amylidene, isoamylidene, etc. In other embodiments when E is an alkylene or
alkylidene group, it may also consist of two or more alkylene or alkylidene groups
connected by a moiety different from alkylene or alkylidene, including, but not
limited to, an aromatic linkage; 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, etc.; or a phosphoruscontaining
linkage including, but not limited to, phosphinyl, phosphonyl, etc. In other
embodiments E may be a cycloaliphatic group including, but not limited to.
cydopentylidene. cyclohexylidene, . 3,3,5-trimethylcyclohexylidene,
methylcyclohcxylidene, 2-[2.2.1]-bicycloheptylidene. neopentylidene,
cyclopentadecylidene, cyclododecylidene, adamantylidene, etc.; a sulfur-containing
linkage, including, but not limited to, sulfide. sulfoxide or sulfone; a phosphoruscontaining
linkage, including, but not limited to, phosphinyl or phosphonyl; an ether
linkage; a carbonyl group; a tertiary nitrogen group; or a silicon-containing linkage
including, but not limited to, silane or siloxy. R1 represents hydrogen or a
monovalent hydrocarbon group including, but not limited to, alkenyl, allyl, alkyl, aryl,
aralkyl, alkaryl, or cycloalkyl. In various embodiments a monovalent hydrocarbon
group of R may be halogen-substituted, particularly fluoro- or chloro-substituted, for
example as in dichloroalkylidene, particularly gem-dichloroalkylidene. Y1
independently at each occurrence may be an inorganic atom including, but not limited
to, halogen (fluorine, bromine, chlorine, iodine); an inorganic group containing more
than one inorganic atom including, but not limited to, nitro; an organic group
including, but not limited to, a monovalent hydrocarbon group including, but not
limited to, alkenyl, allyl, alkyl, aryl, aralkyl, alkaryl, or cycloalkyl, or an oxy group
including, but not limited to, OR wherein R is a monovalent hydrocarbon group
including, but not limited to, alkyl, aryl, aralkyl. alkaryl, or cycloalkyl; it being only
necessary that Y1 be inert to and unaffected by the reactants and reaction conditions
used to prepare the polymer. In some particular embodiments Y1 comprises a halo
group or C|-C6 alkyl group. The letter "m" represents any integer from and including
zero through the number of positions on A1 available for substitution; "p" represents
an integer from and including zero through the number of positions on E available for
substitution; "t" represents an integer equal to at least one; "s" represents an integer
equal to cither zero or one; and "u" represents any integer including zero.
In dihydroxy-substituted aromatic hydrocarbons in which D is represented by formula
(11) above, when more than one Y substituent is present, they may be the same or
different. The same holds true for the R1 substituent. Where "s" is zero in formula
(II) and "u" is not zero, the aromatic rings are directly joined by a covalent bond with
no intervening alkylidene or other bridge. The positions of the hydroxyl groups and
Y1 on the aromatic nuclear residues A1 can be varied in the orlho, meta, or para
positions and the groupings can be in vicinal, asymmetrical or symmetrical
relationship, where two or more ring carbon atoms of the hydrocarbon residue are
substituted with Y1 and hydroxyl groups. In some particular embodiments the
parameters "t", "s", and "u" each have the value of one; both A1 radicals are
unsubstituted phenylene radicals; and E is an alkylidene group such as isopropylidene.
In some particular embodiments both A1 radicals are p-phenylene, although both may
be o- or in-phenylene or one o- or m-phenylene and the other p-phenylene.
In some embodiments of dihydroxy-substituted aromatic hydrocarbons E may be an
unsaturated alkylidene group. Suitable dihydroxy-substituted aromatic hydrocarbons
of this type include those of the formula (III):
nowhere
independently each R is hydrogen, chlorine, bromine or a Cioo monovalent
hydrocarbon or hydrocarbonoxy group, each Z is hydrogen, chlorine or bromine,
subject to the provision that at least one Z is chlorine or bromine.
Suitable dihydroxy-substituted aromatic hydrocarbons also include those of the
formula (IV):
where independently each R4 is as defined hereinbefore, and independently Rg and Rh
are hydrogen or a CI.JQ hydrocarbon group.
In embodiments of the present invention dihydroxy-substituted aromatic
hydrocarbons that may be used include those disclosed by name or formula (generic
or specific) in U.S. Patents 2,991,273, 2,999,835, 3,028,365, 3,148,172, 3,271,367,
3,271,368, and 4,217,438. In some embodiments of the invention dihydroxysubstituted
aromatic hydrocarbons include 4,4'-(3,3,5-
trimethylcyclohexylidene)diphenol; 4,4'-bis(3,5-dimethyl)diphenol, 1,1 -bis(4-
hydroxy-3-methylpheny))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-rnelhoxyphenyl)methane; 1 ,l-bis(4-hydroxypheny])ethane; 1,2-bis(4-
hydroxyphenyl)ethane; 1,1 -bis(4-hydroxy-2-chlorophenyl)ethane; 2,2-bis(4-
hydroxyphenyl)propane (commonly known as bisphenol A); 2,2-bis(3-phenyl-4-
hydroxyphenyl)propane;2,2-bis(4-hydroxy-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)-i-phenylpropane; 2,4'-dihydroxyphenyI sulfone; dihydroxy
naphthalene; 2,6-dihydroxy naphthalene; hydroquinone; resorcinol; C|.3 alkylsubstituted
resorcinols; 2,2-bis-(4-hydroxyphenyl)butane; 2,2-bis-(4-hydroxyphenyl)-
2-methylbutane; l,l-bis-(4-hydroxyphenyl)cyclohexane; bis-(4-hydroxyphenyl); bis-
(4-hydroxyphenyl)sulphi,de;2-(3-methyl-4-hydroxyphenyl-2-(4-
hydroxyphenyl)propane;2-(3,5-dimethyl-4-hydroxyphenyl)-2-(4-
hydroxyphenyl)propane; 2-(3-rnethyl-4-hydroxyphenyl)-2-(3,5-dimethyl-4-
hydroxyphenyl)propane; bis-(3,5-dimelhylphenyl-4-hydroxyphenyl)methane; 1,1 -bis-
(3,5-dimethylphenyl-4-hydroxypheny])ethane; 2,2-bis-(3,5-dimethylphenyl-4-
hydroxyphenyl)propane; 2,4-bis-(3,5-dimethylphenyl-4-hydroxyphenyl)-2-
methylbutane; 3,3-bis-(3,5-dirnethylphenyl-4-hydroxyphenyl)pentane; ],1 -bis-(3;5-
dimethylphenyl-4-hydroxyphenyl)cyclopentane; l,l-bis-(3,5-dimethylphenyl-4-
hydroxyphenyl)cyclohexane; and bis-(3,5-dimethylphenyl-4-hydroxyphenyl)sulphide.
In a particular embodiment the dihydroxy-substituted aromatic hydrocarbon
comprises bisphenol A.
In some embodiments of dihydroxy-substituted aromatic hydrocarbons when E is an
alkylene or alkylidene group, said group may be pan of one or more fused rings
attached to one or more aromatic groups bearing one hydroxy substituent. Suitable
dihydroxy-substituted aromatic hydrocarbons of this type include those containing
indane structural units such as represented by the formula (V), which compound is 3-
(4-hydroxyphenyl)-),1,3-tiimethy]indan-5-ol, and by the formula (VI), which
compound is l-(4-hydroxyphenyl)-l,3,3-trirnethylindan-5-ol:
(Figure Removed)
Also included among suitable dihydroxy-substituted aromatic hydrocarbons of the
type comprising one or more alkylene or alkylidene groups as part of fused rings are
the 2,2,2'.2'-le(rahydro-lJ'-spirobi[lH-indene]diols having formula (VII):
(Figure Removed)
wherein each R6 is independently selected from monovalent hydrocarbon radicals and
halogen radicals; each R7. R8, R9, and R10 is independently C.6 alkyl; each R" and
R1 2 is independently H or C|.6 alkyl; and each n is independently selected from
positive integers having a value of from 0 to 3 inclusive. In a particular embodiment
ihe 2,2:2',2'--tctrahydro-1,1 '-spirobi[I H-indene]diol is 2,2,2',2'-tetrahydro-3,3,3',3'-
tetramethyl- I J ' - s p i r o b i f lH-indene]-6,6'-diol (sometimes known as "SB1"). Mixtures
of alkali metal salts derived from mixtures of any of the foregoing dihydroxysubstituted
aromatic hydrocarbons may also be employed.
The term "alkyl" as used in the various embodiments of the present invention is
intended to designate both linear alkyl, branched alkyl, aralkyl, cycloalkyl.
bicycloalkyl, tncycloalky! and polycycloalkyl radicals containing carbon and
hydrogen atoms, and optionally containing atoms in addition to carbon and hydrogen.
for example atoms selected from Groups 15, 16 and 17 of the Periodic Table. The
term "alkyl" also encompasses that alkyl portion of alkoxide groups. In various
embodiments normal and branched alkyl radicals are those containing from 1 to about
32 carbon atoms, and include as illustrative non-limiting examples C1-C32 alkyl
optionally substituted with one or more groups selected from C1-C32 alkyl, C3-C15
cycloalkyl or aryl; and C3-C15 cycloalkyl optionally substituted with one or more
groups selected from C1-C32 alkyl. Some particular illustrative examples comprise
methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tertiary-butyl, pentyl, neopentyl.
hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl. Some illustrative nonlimiting
examples of cycloalkyl and bicycloalkyl radicals include cyclobutyl,
cyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, bicycloheptyl and
adamantyl. In various embodiments aralkyl radicals are those containing from 7 to
about 14 carbon atoms; these include, but are not limited to, benzyl, phenylbutyl,
phenylpropyl, and phenylethy). In various embodiments aryl radicals used in the
various embodiments of the present invention are those substituted or unsubstituted
aryl radicals containing from 6 to 18 ring carbon atoms. Some illustrative nonl
i m i t i n g examples of these aryl radicals include C6-C15 aryl optionally substituted
with one or more groups selected from C1-C32 alkyl, C3-C15 cycloalkyl or aryl.
Some particular illustrative examples of aryl radicals comprise substituted or
unsubstituted phenyl, biphenyl, toluyl and naphthyl.
Typical bis(N-(chlorophthalimido))aromatic compounds (hereinafter sometimes
simply "hischlorophthalimides") employed according to the invention are prepared in
vaiious embodiments by reaction of a diamine with two equivalents of an anhydride
and include, but are not limited to, those having the formula (Vlll):
(Figure Removed)
In various embodiments of the invention R13 in formula (V11I) is derived from a
diamine selected from the group consisting of aliphatic, aromatic, and heterocyclic
diamines. Exemplary aliphatic moieties include, but are not limited to, straight-chain-,
branched-, and cycloalkyl radicals, and their substituted derivatives. Straight-chain
and branched alkyl radicals are typically those containing from 2 to 22 carbon atoms,
and include as illustrative non-limiting examples ethyl, propyl, butyl, neopentyl,
hexyl, dodecyl. Cycloalkyl radicals are typically those containing from 3 to 22 ring
carbon atoms. Some illustrative non-limiting examples of cycloalkyl radicals include
cyclobutyl, cycl6pentyl, cyclohexyl, methylcyclohexyl, and cycloheptyl. In various
embodiments the two amino groups in diamine-derived aliphatic moieties are
separated from each other by at least two and sometimes by at least three carbon
atoms. In particular embodiments for diamines, the two amino groups are in the alpha,
omega positions of a straight-chain or branched alkyl radical, or their substituted
derivatives; or in the ] ,4-positions of a cycloalkyl radical or its substituted derivatives.
In various embodiments substituents for said aliphatic moieties include one or more
halogen groups, such as fluoro, chloro, or bromo, or mixtures thereof; or one or more
aryl groups, such as phenyl groups, alkyl- or halogen-substituted phenyl groups, or
mixtures thereof. In some embodiments substituents for aliphatic moieties, when
present, are chloro or unsubstituted phenyl.
In other embodiments R13 in formulas (Vlll) comprises a divalent organic radical
selected from aromatic hydrocarbon radicals having 6 to about 22 carbon atoms and
substituted derivatives thereof. In various embodiments said aromatic hydrocarbon
radicals may be monocyclic, polycyclic or fused.
In still other embodiments R13 in formulas (Vlll) comprises divalent aromatic
hydrocarbon radicals of the general formula (IX)
(Figure Removed)
wherein the unassigned positional isomer about the aromatic ring is either meta or
para to Q, and Q is a covalent bond or a member selected from the group consisting of
formulas (X):
(Figure Removed)
and an alkylene or alkylidene group of the formula CyH2y, wherein y is an intecer
from 1 to 5 inclusive. ]n some particular embodiments y has the value of one or two.
Illustrative linking groups include, but are not limited to, methylene, ethylene.
ethylidene, vinylidene, halogen-substituted vinylidene, and isopropylidene. In other
particular embodiments the unassigned positional isomer about the aromatic ring in
formula (IX) is para to Q.
In various embodiments the two amino groups in diamine-derived aromatic
hydrocarbon radicals are separated by at least two and sometimes by at least three ring
carbon atoms. When the amino group or groups are located in different aromatic rings
of a polycyclic aromatic moiety, they are often separated from the direct linkage or
from the linking moiety between any two aromatic rings by at least two and
sometimes by at least three ring carbon atoms. Illustrative non-limiting examples of
aromatic hydrocarbon radicals include phenyl, biphenyl, naphthyl.
bis(phenyl)methane, bis(phenyl)-2,2-propane. and their substituted derivatives. In
particular embodiments substituents include one or more halogen groups, such as
fluoro, chloro, or bromo, or mixtures thereof; or one or more straight-chain-.
branched-, or cycloalkyl groups having from 1 to 22 carbon atoms, such as methyl,
ethyl, propyl, isopropyl, tert-butyl. or mixtures thereof. In particular embodiments;
substituents for aromatic hydrocarbon radicals, when present, are at least one of
chloro, methyl, ethyl or mixtures thereof. In other particular embodiments said
aromatic hydrocarbon radicals are unsubstituted. In some particular embodiments
diamines from which R1 may be derived include, but are not limited to, metaphenylenediamine;
para-phenylenediamine: mixtures of meta- and paraphenylenediamine;
isomeric 2-methyl- and 5-methyl-4,6-diethyl-l,3-phenylenediamines
or their mixtures; bis(4-aminophenyl)-2,2-propane:
bis(2-ch]oro-4-amino-3,5-diethylphenyl)methane, 4,4'-diaminodiphenyl, 3.4'-
diaminodiphenyl, 4,4'-ciiaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-
diaminodipheny] sulfone, 3,4'-diaminodiphenyl sulfone, 4.4'-diaminodiphenyl ketone,
3,4'-diaminodiphenyl ketone. and 2,4-toluenediamine. Mixtures of diamines may also
be employed.
In particular embodiments bischlorophthalimides of formula (VIII) comprise 1,3- and
l,4-bis[N-(4-chlorophthalimido)]benzene; 1,3- and l,4-bis[N-(3-
ch!orophthalimido)]benzene; 1,3- and l,4-[N-(3-chlorophthalimido)]-[ N-(4-
chlorophthalirnido)]benzene; 3,3'-, 3,4'- and 4,4'-bis[N-(3-chlorophthalimido)]phenyl
ether; 3,3'-, 3,4'- and 4,4'-bis[N-(4-chlorophthalimido)]phenyl ether; and 3,3'-, 3,4'-
and 4,4'-[N-(3-chlorophthalimido)]-[N-(4-chlorophthalimido)]phenyl ether. Mixtures
of compounds of the formula (VIII) may also be employed.
It is within the scope of the invention to employ the compound of formula (V1I1) in
admixture with other bis(halo) compounds including, but not limited to, bis(4-
fluorophenyl) sulfone, bis(4-fluorophenyl) ketone and the corresponding chloro
compounds. In that event, the polyetherimide obtained as a product will be a
copolymer also containing ether sulfone or ether ketone structural units, of the type
whose structure and preparation are disclosed in U.S. Patent 5,908,915.
There may also, optionally, be present at least one chain termination agent, hereinafter
sometimes "CTA". Suitable chain termination agents include, but are not limited to,
all those with an activated substituent suitable for displacement by a phenoxide group
during the polymerization process. In various embodiments suitable chain
termination agents include, but are not limited to. alkyl halides such as alkyl
chlorides, and aryl halides including, but not limited to, chlorides of formulas (XI)
and (XII):
(Figure Removed)
wherein the chlorine substituent is in the 3- or 4-position, and Z1 and Z comprise a
substituted or unsubstituted alkyl or aryl group. In some embodiments suitable chain
termination agents of formula (XI) comprise monochlorobenzophenone or
monochlorodiphenylsulfone. In some embodiments suitable chain termination agents
of formula (Xll) comprise at least one mono-substituted mono-phthalimide including,
but not limited to, a monochlorophthalimide such as 4-chIoro-N-methy]phthalimide.
4-chloro-N-butylphthalimide. 4-chloro-N-octadecylphthalimide, 3-chloro-Nmethylphthalimide,
3-chloro-N-butylphthalimide, 3-chloro-N-octadecylphthalimide,
4-chloro-N-phenylphthalimide or 3-chloro-N-phenylphthalimide. In other
embodiments suitable chain termination agents of formula (XII) comprise at least one
mono-substituted bis-phthalimide including, but not limited to, a
monochlorobisphthalimidobenzene including, but not limited to, l-[N-(4-
chloroph!halimido)]-3-(N-phthalimido)benzene (as in formula (Xlll)) or 1 -[N-(3-
chlorophthalimido)]-3-(N-phthalimido)benzene (as in fonnula (XIV)), the latter
CTA's often in admixture with the analogous bis(chloro-N-phthalimido)benzene
monomer.
(Figure Removed)
In still other embodiments suitable chain termination agents of formula (XII)
comprise other mono-substituted, bisphthalimido compounds including, but not
limited to, monochlorobisphthalimidodiphenyl sulfone,
monochlorobisphthalimidodiphenyl ketone, and monochlorobisphthalimidophenyl
ethers including, but not limited to, 4-[N-(4-chlorophthaIimido)]phenyl-4'-(Nphthalimido)
phenyl etlier (as in formula (XV)), or 4-[N-(3-
chlorophthalimido)phenyl]-4'-(N-phthalimido)phenyl ether (as in formula (XVI)), or
the corresponding isomers derived from 3,4'-diaminodiphenyl ether.
(Figure Removed)
Chain termination agents may optionally be in admixture with bis-substituted
bis(phthalimide) monomers. In one embodiment mono-substituted bis-phthalimide
chain termination agents may optionally be in admixture with bis-substituted bisphthalimide
monomers. In a particular embodiment
monochlorobisphthalimidophenyl ether chain termination agents may often be in
admixture w i t h at least one bis-substituted (N-phthalimido)phenyl ether including, but
not l i m i t e d to, at least one bis(chloro-N-phthalimido)phenyl ether.
Also present in embodiments of the invention is at least one solvent of low polarity,
usually substantially lower in polarity than that of the dipolar aprotic solvents
previously employed for the preparation of aromatic polyetherimides. In various
embodiments said solvent has a boiling point above about 150°C. in order to facilitate
the reaction which typically requires temperatures in the range of between about
125°C and about 250'C Suitable solvents of this type include, but are not limited to.
ortho-dichlorobenzene, para-dichlorobenzene, dichlorotoluene, 1,2.4-
trichloroben^cne, diphenyl sulfone, phenetole. anisole and veratrole, and mixtures
thereof.
Another feature of the invention is the presence of a phase transfer catalyst
(hereinafter sometimes "PTC"). In some embodiments the PTC is substantially stable
over the reaction temperature range, which range includes but is not limited to,
temperatures in the range of between about 125°C and about 250°C. Substantially
stable in the present context means that the PTC is sufficiently stable to effect the
desired reaction at a desired rate. Various types of PTC's may be employed for this
purpose. They include quaternary phosphonium salts of the type disclosed in U.S.
Patent -4,273, 712; N-alkyl-4-dialkylaminopyridinium salts of the type disclosed in
U.S. Patent Nos. 4,460,778 and 4,595,760; and guanidinium salts of the type
disclosed in U.S. Patent Nos. 5,132,423 and 5,116,975. In some particular
embodiments suitable phase transfer catalysts, by reason of their exceptional stability
at high temperatures and their effectiveness to produce high molecular weight
aromatic polyether polymers in high yield are alpha-omegabis(
pciaalkylguanidirnum)alkane salts and hexaalkylguanidimum salts including, but
not limited to, hexa.ilkylguanidinium halides and especially hexaalkylguanidinium
chlorides as disclosed, tor example, in U.S. Patent 5,229,482.
There arc various embodiments of the present invention that can be used individually
or in any combination. For each embodiment, the relevant parameters will be defined
immediately hereinafter. Then the broad parameters, applicable generically except as
dictated by one of the embodiments, will be delineated.
In embodiment A, the reagents (alkali metal salt, bischlorophthalimidc and solvent)
employed are substantially dry; i.e., the reaction mixture comprising the same
contains at most about 20 ppm by weight of water. In some particular embodiments
the amount of water in the reaction mixture is less than about 20 ppm, in other
embodiments less than about 15 ppm, and in still other embodiments less than about
10 ppm. The proportion of water may be determined by any convenient means and is
typically determined by Karl Fischer titration. In some embodiments the amount of
water in the reaction mixture is determined indirectly by measuring water content of
an over-head distillate or condensate.
In a particular subset of this embodiment, the alkali metal salt, in combination with a
portion of solvent, is dried, most often by distillation, in one embodiment to a water
content of at most about 20 ppm, and in another embodiment to a water content of at
most about ]0 ppm. Bischlorophthalimide, in combination with a portion of solvent
and optionally with chain termination agent, is similarly dried in one embodiment to a
water content of at most about 20 ppm, and in another embodiment to a water content
of at most about 10 ppm. This form of drying is generally and typically applicable to
embodiment A, although other effective forms may be employed. It is within the
scope of the invention to pre-dry the solvent, e.g., by contact with molecular sieves.
In another particular subset of this embodiment (embodiment Al), the two reagents,
alkali metal salt and bischlorophthalimide, may then be combined and, optionally,
further dried by distillation until the threshold value of about 20 ppm water or less is
attained. Dry PTC is then added, whereupon reaction immediately begins at a
temperature on the order of about 190°C. PTC may be added all at once or in portions
over time. In one particular embodiment PTC is added continuously over a period of
time to moderate the reaction exotherm. In the present context dry PTC means that in
one embodiment the catalyst contains less than about 50 ppm water, in another
embodiment the catalyst contains less than about 30 ppm water, and in still another
embodiment the catalyst contains less than about 20 ppm water. A substantially
greater reaction rate, as shown by the slope of the curve of molecular weight
attainment after a given time, is noted when embodiment A is employed than when
reagents containing a higher proportion of water are employed.
In another particular subset of embodiment A (embodiment A2),
bischlorophthalimide. ail or at least a portion of solvent and all or at least a portion of
PTC, optionally predried separately, may be combined and. if necessary, further dried
by distillation u n t i l the threshold value of about 20 ppm water or less is attained. Dry
alkali metal salt is then added, whereupon reaction immediately begins, typically at
solvent reflux temperature. Dry alkali metal salt may be added all at once or in
portions over time. In the present context dry alkali metal salt means that in various
embodiments the salt contains less than about 50 ppm water, or less than about 30
ppm water, or less than about 25 ppm water, or preferably less than about 20 ppm
water. In one particular embodiment dry alkali metal salt is added continuously over
a period of time to moderate the reaction exotherm. The reaction may be performed
at an i n i t i a l solids level of at least about 15%, or at a solids level in a range of between
about 15% and about 35%, or at a solids level in a range of between about 25% and
about 30%. In some embodiments the reaction is performed at an initial solids level
and then the mixture is concentrated to a higher solids level during reaction or after all
the salt has been added or both during reaction and after all the salt has been added.
The final solids level following complete addition of salt and any optional
concentration step may be at least about 15%, or in a range of between about 15% and
about 35%, or in a range of between about 25% and about 30%.
In another particular subset of embodiment A, a portion of solvent is removed from
the reaction vessel by distillation during the course of reaction, and, optionally, dry
solvent is added to make up for that solvent removed. In some embodiments the
solvent is ortho-dichlorobenzene dried to a level of at most 20 ppm water before
addition 10 the reaction mixture.
Embodiment B relates to starting the reaction by addition of phase transfer catalyst to
mixture comprising said alkali metal salt and bis(N-(chlorophthalimido))aromatic
compound in solvent wherein the solids level of polymer is at an initial value of at
least about 15%, and then concentrating the mixture during reaction. In another
embodiment the solids level of polymer is at an initial value of at least about 25%
before starting the reaction by addition of phase transfer catalyst. In various
embodiments following addition of phase transfer catalyst the mixture is concentrated
until the said value is in one embodiment in a range of between about 25% polymer
solids level and about 60% polymer solids level; in another embodiment in a range of
between about 25% polymer solids level and about 50% polymer solids level; in still
another embodiment in a range of between about 25% polymer solids level and about
40% polymer solids level; and in still another embodiment in a range of between
about 30% polymer solids level and about 40% polymer solids level. Solids level
(sometimes also referred to herein as "polymer solids level") is calculated as weight
polymer that would be formed divided by the sum of weight polymer than would be
formed and solvent. Concentration of the reaction mixture may be done by any
convenient method including, but not limited to, distillation of solvent. PTC may be
added all at once or in portions over time. In one particular embodiment PTC is
added continuously over a period of time to moderate the reaction exotherm.
Embodiment C relates to the combined level of alkali metal salt and
bischlorophthalimide reagents in solvent. Said combined level is maintained at a
value in one embodiment in a range of between about 25% polymer solids level and
about 60% polymer solids level; in another embodiment in a range of between about
25%) polymer solids level and about 50% polymer solids level; in another embodiment
in a range of between about 25% polymer solids level and about 40% polymer solids
level, and in still another embodiment in a range of between about 30% polymer
solids level and about 40% polymer solids level. Previously, values of 10-15% solids
level were most often employed.
At least two unexpected advantages of these relatively high solids levels have been
observed. In the first place, the proportion of cyclic oligomers relative to polymer is
substantially reduced, particularly in mixtures of 3- and 4-chlorophthalimide isomers.
Cyclic oligomer levels are in one embodiment less than about 5 wt. %, in another
embodiment less than about 4 wt. %, in another embodiment less than about 3 wt. %,
and in .still another embodiment less than about 2 wt. %, based on weight polymer.
Cyclics proportions may be determined by gel permeation chromatography using a
suitable column; for example, a Polymer Labs Mixed E column, which separates
materials of low molecular weight. In the second place, the reaction rate and
efficiency of the PTC is substantially improved.
Whereas total cyclic oliyomers, using o-dichlorobenzene as solvent, in
polyetherimides prepared from bisphenol A salts and mixtures of
1 ,3-bis[N-(4-chlorophthalirniclo)]benzcne and 1.3-bis["N-(3-chlorophthalimido)]-
benzene in proportions (weight and mole, interchangeably) from 3:1 to 0:1 reached
values on the order of 5% by weight at 15% of solids level in o-dichlorobenzene, the
values at solids levels of 25-30% ranged from about 1.1% to about 2.1% by weight
(calculated as weight cyclics divided by the sum of weight polymer and weight
cyclics). Likewise, product molecular weights attained at a PTC level in some
embodiments of 0.6-1.3 mole percent (based on alkali metal salt) and in other
embodiments of 1.0-1.3 mole percent (based on alkali metal salt) and a solids level of
22% were greater, particularly in reaction times of 60 minutes or greater, than those
attained at a PTC level of 1.8 mole percent and a solids level of 15%. In some
embodiments wherein lower catalyst levels are used at higher solids level, it is
believed that less catalyst degradation occurs which may also account at least in part
for attainment of higher product molecular weight.
Embodiment D is a refinement of a method for rough control of molecular weight of
the polyetherimide product. Previously, a slow approach to the desired molecular
weight was achieved by initially employing an excess of bischlorophthalimide, said
excess typically being provided by introducing only on the order of 70% of the
stoichiometric amount of alkali metal salt. After the reaction reached a plateau, the
molecular weight of the polyetherimide was determined and additional alkali metal
salt was introduced. After several repetitions of this procedure, the desired molecular
weight was reached and the reaction was stopped.
One effect of this gradual approach was the necessity to use a rather large amount of
PTC. It was discovered that this was, at least in part, a result of the instability of the
PTC in the presence of phenoxide-type anions at high temperatures. Another effect
was an undesirably long total reaction time, since many iterations of alkali metal salt
addition and molecular weight determination, sometimes requiring a total reaction
time of 8-10 hours, were required before the desired molecular weight was attained.
In embodiment D, therefore, the initial excess of bischlorophthalimide is only up to
about 5% on a molar basis. In one particular embodiment the initial excess of
bischlorophthalimide is in the range of between about 0.75% and about 3%, and in
another particular embodiment in the range of between about 0.75% and about 1.25%
on a molar basis. The weight average molecular weight of the initial polyetherimide
obtained is then generally in the range of between about 25,000 and about 37,000.
depending on the presence and amount, if any, of chain termination agent present. For
the most part, only one or two further additions of alkali metal salt are necessary to
reach the desired molecular weight. Moreover, the amount of PTC necessary to
conduct the reaction is substantially decreased, typically to a level as low as 0.6 mole
percent based on alkali metal salt. In some embodiments a first further addition of
alkali metal salt is done when the polymer solids level of the reaction mixture is in
one embodiment in a range of between about 25% polymer solids level and about
60% polymer solids level; in another embodiment in a range of between about 25%
polymer solids level and about 50% polymer solids level; in another embodiment in a
range of between about 25% polymer solids level and about 40% polymer solids
level, and in still another embodiment in a range of between about 30% polymer
solids level and about 40% polymer solids level.
Embodiment E is based on the discovery of unexpected advantages resulting from the
use of alkali metal salt of small particle size. Said salt exists in the reaction mixture in
the form of a slurry in solvent, and undergoes a pseudo-interfacial reaction, mediated
by the PTC, with the bischlorophthalimide which is in solution (being sparingly
soluble). Therefore, the surface area of the alkali metal salt is a factor in reaction rate.
In some preparative embodiments the alkali metal salt has an average particle size
below about 100 microns, as determined by laser diffraction using, for example, a
l.ascntec Size Analyzer. However, individual particles may be, without further
treatment, as large as 500-1,000 microns. It has been discovered that such particles of
lart.se size can persist for many hours during the polymerization reaction, resisting
dissolution and increasing the time necessary to reach a desired polymer molecular
weight, among other detrimental factors.
In embodiment E, the presence of particles of a diameter greater than about 200
microns is avoided, causing a substantial increase in molecular weight over time. The
percentage of particles with diameter greater than about 200 nm is in one embodiment
iess Ihan about 30%. in another embodiment less than about 25%, and in still another
embodiment less than about 20% of the total particles. In other embodiments the
percentage of particles with diameter greater than about 500 nm is in one embodiment
less than about 5%. in another embodiment less than about 2%, and in still another
embodiment less than about 1% of the total particles. In a particular embodiment the
percentage of particles with diameter greater than about 200 nm is less than about
25%, and the percentage of particles with diameter greater than about 500 nm is less
than about 1%, In one embodiment the desired particle size range may be achieved
by using commercially available grinders or their art-recognized equivalents, either
during or after preparation of the alkali metal salt, to reduce particle size in the salt as
required.
In another embodiment control of particle size may be achieved during preparation or
dehydration of the alkali metal salt. In a particular embodiment the alkali metal salt
of a dihydroxy-substiiuted aromatic hydrocarbon may be prepared by contacting in
water at leas! one dihydroxy-substituted aromatic hydrocarbon and at least one alkali
metal base, such as an alkali metal hydroxide. In one embodiment the alkali metal
hydroxide is sodium hydroxide. Contact is performed using amounts of dihydroxysubstituted
aromatic hydrocarbon and alkali metal base which are in one embodiment
stoichiometric, in another embodiment deviate from stoichiometry by no more than
plus/minus 0.1 mole c/b, in another embodiment deviate from stoichiometry by no
more than plus/minus 0.2 mole %, in another embodiment deviate from stoichiometry
by no more than plus minus 0.3 mole %, and in still another embodiment deviate from
stoichiometry by no more than plus/minus 0.4 mole %. Said contact may be
performed in water at a temperature in one embodiment above about 60°C, in another
embodiment above about 70°C, in another embodiment above about 80°C, and in still
another embodiment ;.bov« about 90°C. In a particular embodiment said contact is
performed at a temper,iiurt: in a range of between about 90°C and about 100°C. Said
contact may be performed under an inert atmosphere, such as under nitrogen. Said
contact may be performed at a solids level in one embodiment of greater than about
15%, in another embodiment of greater than about 20%, and in still another
embodiment of greater than about 25%, wherein solids level is weight reactants
divided by the sum of weight reactants and \veight solvent. In one particular
embodiment said con:act is performed at a solids level in a range of between about
26% and about 31%. and in another particular embodiment at a solids level in a ranee
of between about 27", and about 30%. The course of the reaction may be monitored
by known methods. The alkali metal salt reaction product may be isolated by known
methods. In a particular embodiment the salt reaction product may be isolated by
spraying of the aqueous solution containing the product into an organic solvent with
boiling point above that of water. In some embodiments said solution is sprayed at a
solids level similar to the solids level at which the salt was prepared. In other
embodiments said solution is diluted with additional solvent before spraying.
Spraying of the aqueous solution (sometimes referred to as atomization of the aqueous
solution) into an organic solvent prevents agglomeration of salt during removal of
water. In some embodiments the organic solvent is toluene, xylene, orthodichlorobenzene,
para-dichlorobenzene, dichlorotoluene, 1,2,4-trichlorobenzene,
diphenyl sulfone, phenetole, anisole or veratrole, or mixtures thereof. In some
embodiments said organic solvent forms an azeotrope with water. In one particular
embodiment the organic solvent is ortho-dichlorobenzene. In another particular
embodiment the organic solvent is toluene. In one embodiment the organic solvent is
contained in a vessel (sometimes referred to hereinafter as a dryer) which in various
embodiments comprises baffles beneath the surface of said solvent which are believed
to help prevent fouling of the vessel with salt cake. In various embodiments said
vessel contains means for agitation. In one particular embodiment said vessel
comprises a stirred tank with at least one stirring shaft agitator. The degree of
agitation is typically such as not to favor formation of salt cake which may be difficult
to remove from the dryer. Said vessel containing organic solvent may be fitted with
one or more spray nozzles for introduction of aqueous solution containing salt. Any
dead space cavities in the dryer may be heated externally or flushed with dry solvent
lo prevent any accumulation of water therein. In one embodiment the vessel sides and
top are traced with heating element. The rate of introduction of salt-containing
aqueous solution into the vessel containing organic solvent depends upon a number of
lactors including, but not limited to, vessel size, and may be determined without
undue experimentation by those skilled in the art. In some embodiments, if the rate of
introduction is too high, then the temperature of the organic solvent may fall and
alkali metal salt may tend to cake. On the other hand, if the rate of introduction is too
low, then process economics are less favorable. In particular embodiments saltcontaining
aqueous solution is introduced into the vessel in such a manner that said
solution does not impact the walls of the vessel or any stirrer shaft. The temperature
of the organic solvent into which the aqueous solution is sprayed is in one
embodiment in a ranee of between about 10G°C and about 220°C, in another
embodiment in a range of between about 110°C and about 200°C, in another
embodiment in a range of between about 130°C and about 180°C, and. in still another
embodiment in a range of between about 140°C and about 160°C. In some
embodiments heat is provided to the organic solvent by circulating said solvent
through a heat exchanger. In one particular embodiment the heat exchanger is a tubeshell
heat exchanger. In another particular embodiment the heat exchanger is a spiral
heat exchanger. When said solvent contains alkali metal salt, the rate of flow of the
solvent-salt mixture through the heat exchanger is such that turbulent flow is achieved
to prevent fouling of the exchanger by solid salt, and may be determined by those
skilled in the art without undue experimentation. In one embodiment the vessel
holding organic solvent into which the aqueous solution is introduced may be under
positive pressure so that the temperature of organic solvent may be above its normal
boiling point at atmospheric pressure. Said vessel may be at a pressure in one
particular embodiment in a range of between about and about 30 kilopascals (kPa)
and about 280 kPa, m another particular embodiment in a range of between about 65
kPa and about 240 kPa. and in another particular embodiment in a range of between
about 100 kPa and about 210 kPa. In another embodiment the vessel holding organic
solvent into which the aqueous solution is introduced may be under reduced pressure.
Any organic solvent exiting the vessel along with vaporized water may optionally be
replaced by adding additional organic solvent. In one embodiment additional organic
solvent is added simultaneously with water vaporization to keep the total volume of
solvent substantially the same. As water and organic solvent are removed from the
vessel some precipitated alkali metal salt may be entrained. In various embodiments
the entrained salt is recovered using any known means. In a particular embodiment
entrained salt may be knocked out of water-solvent mixture by a spray of organic
solvent introduced into a vent through which the water-solvent mixture with entrained
salt passes. Said salt in organic solvent may then be passed back to the dryer. The
salt reaction product may be isolated at a solids level in organic solvent of in one
embodiment between about 5% and about 30%, and in another embodiment between
about 10% and about 20%. Before or during transfer to a polymerization vessel the
salt reaction product in organic solvent may be subjected to at least one drying step
which may include, bu: is not limited to, combination with additional organic solvent
and distillation, optionally at reduced pressure, or distillation of organic solvent from
the mixture with addition of dry organic solvent at approximately the same rate as to
keep the solvent amount in the dryer roughly constant. Dry organic solvent in the
context of the present process means solvent with less than 100 ppm water. In other
embodiments the salt in organic solvent may be transferred from the dryer to at least
one other vessel for drying. The amount of water in the salt-containing organic
solvent may be determined using known methods. In some embodiments the amount
of water in the salt-containing organic solvent may be determined indirectly by
measuring water content of an over-head distillate. The amount of water in the saltcontaining
organic solvent before use in the polymerization reaction is in one
embodiment less than about 40 ppm, in another embodiment less than about 30 ppm.
and in still another embodiment less than about 20 ppm. Before or during transfer to
a polymerization vessel the salt reaction product in organic solvent may be subjected
to at least one particle size reduction step using equipment which may include, but is
not limited to, one or more centrifugal pumps, grinders, drop-down blenders, particle
size reduction homouenizer or delumpers. Embodiments of the process for making
alkali metal salt described herein may be performed in batch, continuous or semicontinuous
mode, and are capable of making alkali metal salts of not only dihydroxysubstituted
aromatic hydrocarbons but also monohydroxy-substitutcd aromatic
hydrocarbons, trihydroxy-substituted aromatic hydrocarbons and tetrahydroxysubstituted
aromatic hydrocarbons.
In embodiment F, careful control of the purity of one or both reagents is exercised,
thus maximizing reaction rate and improving efficiency in attaining the desired
molecular weight. Regarding the alkali metal salt (embodiment F-1), it has been found
that the presence of free dihydroxy-substituted aromatic hydrocarbon decreases the
molecular weight of the polyetherimide product. The amount of free dihydroxysubstituted
aromatic hydrocarbon is in one embodiment at most about 0.3 mole %. in
another embodiment at most about 0.2 mole %, and in yet another embodiment at
most about 0.15 mole % of the alkali metal salt. Also, the presence of free alkali metal
hydroxide may cause a substantial decrease in molecular weight over time. The
amount of free alkali metal hydroxide is in one embodiment at most about 0.3 mole
%, in another embodiment at most about 0.2 mole %, and in yet another embodiment
at most about 0.15 mole % of the alkali metal salt. Therefore, this embodiment
includes the employment of alkali metal salt in which said materials are present in
lesser proportions, and in a particular embodiment the employment of
stoichiornetrically pure salt; that is, salt that is typically prepared from a
sioichiometrically equivalent amount of dihydroxy-substituted aromatic hydrocarbon
and alkali metal hydroxide.
Regarding the bischlorophthalimide prepared by reaction of a diamine with two
equivalents of an anhydride (embodiment F-2), a reagent containing residual amine
often results in molecular weight below the desired value, as does the presence of
such common impurities as phthalide, chlorophthalides and chlorobenzoic acids.
Thus, bischlorophthalimide which is stoichiometrically pure (i.e., is within 0.02 mole
% of stoichiometric) or has up to 0.5 mole % of residual anhydride groups requires a
minimum of time to afford product of a specific desired molecular weight. The same
is true of bischlorophthalimide containing in one embodiment at most about 1000
ppm of phthalides and in another embodiment at most about 500 ppm phthalides,
including chlorophthalides, and at most about 0.15 mole % of chlorobenzoic acids.
Regulation of the amine to anhydride stoichiometry of the reactants producing the
bischlorophthalimide (e.g.. m-phenylenediamine and 4-chlorophthalic anhydride) may
be accomplished by known methods. Bischlorophthalimide purity will depend to
some extent on method of preparation. When necessary, phthalides may be removed
from the bischlorophthalimide by extraction of an aqueous solution of the
corresponding chlorophthalic acid with an organic solvent including, but not limited
to. toluene or xylene. while chlorobenzoic acids may be removed by extraction of an
organic solvent solution of the chlorophthalic anhydride with aqueous bicarbonate.
typically sodium bicarbonate.
Other than as prescribed hereinabove for specific embodiments, the alkali metal salt
and chlorophthalimide are typically employed over the cumulative course of the
reaction in substantially equimolar amounts. For maximum molecular weight, the
amounts should be as close as possible to exactly equimolar, but molecular weight
control may he achieved by employing one reagent or the other in slight excess. It is
also w i t h i n the scope of (he invention to employ chain termination agents, as noted
hereinabove.
.Reaction temperatures in embodiments of the invention are most often in the range of
between about 125°C and about 250°C in some embodiments, and in the range of
between about 180°C and about 225'C in other embodiments. The proportion of
phase transfer catalyst employed is generally about 0.5-10 mole percent based on
alkali metal salt, with lesser amounts within this range generally being necessary .
Following the desired level of completion of the reaction, the aromatic polyether
polymer may be isolated by conventional methods. This may include, but is not
limited to, steps of washing and precipitation by combination of the polymer solution
with a non-solvent for the polymer.
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
practicing the claimed invention. 'Hie examples provided are merely representative of
the work that contributes to the teaching of the present application. Accordingly,
these examples are not intended to limit the invention, as defined in the appended
claims, in any manner. Unless otherwise specified, all parts and percentages are by
weight. Reagent grade o-dichlorobenzene (ODCB, employed as solvent) was dried
over 4 angstrom molecular sieves; hexaethylguanidinium chloride (HEGC1) was used
as a 20% solution in ODCB; l,3-bis[N-(4-chlorophthalirnido)]benzene (Formula
XV11: sometimes referred to as "C1PAM1") (or the 3-chloro isomer when specified)
was ground in a Waring blender and dried in vacuum at 160°C for 24 hours:
bisphcnol A disodium salt (BPA-Na) was filtered from a toluene slurry, dried in
vacuum at 160L'C for 24 hours, ground in a Waring blender and dried for an additional
24 hours: and all leagents were stored and handled in a nitrogen-filled dry box.
Weight average molecular weights (Mw) and levels of cyclic oligomers were
determined by gel permeation chromatography relative to polystyrene standards. PTC
levels arc based on BPA-Na, and CTA (when employed) concentrations are based on
C1PAMI.
(Figure Removed)
EXAMPLE 1 (Embodiment A)
A slurry of C1PAM1 in ODCB was prepared by the reaction of m-phenylenediamine
with 4-chlorophthalic anhydride in a 250 ml three-necked flask and stored until use
under nitrogen, along with a measured amount of 1-[N-(4-chlorophtharirnido)]-3-(Nphthalimido)
benzene as CTA. The flask was fitted with a nitrogen sparge tube atop a
reflux condenser, a mechanical stirrer and a distillation apparatus. A further portion of
ODCB was added, and distillation was performed under nitrogen to dry the slurry to a
water content of at most about 10 ppm. BPA-Na slurry in ODCB was dried similarly
in a separate flask.
When both slurries were dry, the BPA-Na slurry was added to the C1PAMI slurry by
pouring quickly under nitrogen and rinsing with dry ODCB, in a molar ratio of aryl
chloride groups to ONa groups of 1.01:1 and a polymer solids level of 25%. A final
distillation was performed to reduce the water content to at most 10 ppm.
HEGC1, 0.8 mole % (based on BPA-Na), was added to the dried mixture at 190°C, a
timer was started and samples were removed periodically, quenched with acetic acid
and analyzed for molecular weight. The initial reaction rate was calculated as the
slope of the molecular weight-time curve from 0 to 30 minutes.
EXAMPLE 2 (Embodiment A)
Predried and isolated reagents C1PAMI, CTA, BPA-Na and dry ODCB (5 ppm water
content) were added together to a 250 ml three-necked flask and heated to reflux.
HEGC1, 0.8 mole % (based on BPA-Na), was added to the mixture at 190°C, a timer
was started and samples were removed periodically, quenched with acetic acid and
analyzed for molecular weight. The initial reaction rate (in units of kilograms/mole
minute) was calculated as the slope of the molecular weight-time curve from 0 to 30
minutes.
EXAMPLE 3 (Embodiment A)
The procedure of Example 1 was followed except that the reaction was spiked at
180°C with wet ODCB to a total water content of 45 ppm before catalyst addition.
The amount of additional ODCB added was such that the % solids level remained at
about 25%.
EXAMPLE 4 (Embodiment A)
The procedure of Example 1 was followed except that the reaction was cooled to
room temperature before spiking with wet ODCB to a total water content of 45 ppm
before catalyst addition. The amount of additional ODCB added was such that the %
solids level remained at about 25%.
EXAMPLE 5 (Embodiment A)
The procedure of Example 2 was followed except that the ODCB had an initial water
content of 57 ppm and was azeotropically dried'to a total water content of 5 ppm
before catalyst addition.
EXAMPLE 6 (Embodiment A)
The procedure of Example 2 was followed except that the ODCB had an initial water
content of 57 ppm and was azeotropically dried to a total water content of 5 ppm after
catalyst addition.
The results of Examples 1-6 are listed in Table 1, in comparison with a control
reaction which employed the procedure of Example 2, except that the ODCB had an
initial water content of 57 ppm and was not subsequently dried.
(Table Removed)
From a comparison of Example 1 with Example 2, the advantage of the particular
subset of embodiment A will be apparent. Example 1 when compared with
Comparison of Example 3 with Example 4 shows the unexpected advantage for
reaction rate and polymer molecular weight of having the reactants spend as little time
as possible in the presence of water. Examples 5 and 6, when compared with the
Control, show the advantage of drying, particularly before addition of the catalyst.
Comparison of Example 5 with Example 6 shows the unexpected advantage for
reaction rate and polymer molecular weight of having the reactants and catalyst spend
as little time as possible in the presence of water.
EXAMPLES 7-10 (Embodiment C)
The procedure of Example 1 was repeated at a total water content of less than 10 ppm.
using various proportions of PTC and 4-chloro-N-phenylphthalimide as CTA, varying
the solids level and employing, in certain examples, a mixture of 3- and 4-isomers of
C1PAMI. Proportions of cyclic oligomers having degrees of polymerization up to 4
were determined. Comparison was made with two controls:
Control A, at 15% polymer solids level;
Control B, a commercially available polyetherimide prepared by the reaction of mphenylenediamine
with 2,2-bis[4-(dicarboxyphenoxy)phenyl]propane dianhydride
(96:4 ratio of 3,4-dicarboxy to 2,3-dicarboxy isomer).
EXAMPLE 11 (Embodiment C)
The procedure of Example 1 was repeated, replacing the C1PAM1 with an analogous
compound prepared by the reaction of 4- and 3-chlorophthalic anhydrides (70:30
weight ratio) with 4,4'-diaminodiphenyl ether.
The results of Examples 7-11 are listed in Table U. Mole percentages of PTC are
based on BPA-Na; mole percentages of CTA on C1PAM1.
(Table Removed)
The results in Table 11 show the unexpected advantage at operating at a relatively high
solids level, which affords a product approaching, in low cyclics content, the
commercially available one prepared from a dianhydride and diamine. They further
show the particular advantage of a solids level of at least 30%. The relatively high
cyclics level in Example 5 is believed to be a steric effect of employing 100% 3-
isomer, which is more readily cyclized than the 4-isomer.
EXAMPLES 12-15 (Embodiment C)
The procedure of Example 1 was employed with the following solids and PTC levels:
Example 12: 15%, 1.8 mole percent;
Example 13: 22%, 1.8 mole percent;
Example 14: 22%, 1.3 mole percent;
Example 15: 22%, 1.0 mole percent.
The results are shown graphically in FIGURE 1. It is apparent that molecular weight
attained over time is substantially higher at 22% than at 15% solids level, at least after
reaction times of about 45 minutes, even with the use of lower PTC concentrations.
EXAMPLE 16 (Embodiment D)
The procedure of Example 1 was repeated at a solids level of 30%, a PTC proportion
of 0.8 mole percent PTC and 3.0-4.7 mole % (based on CIPAMI) of 4-chloro-Nphenylphthalimide
as CTA, except that in an initial stage of the reaction, a molar ratio
of CIPAMI to BPA-Na of 1.03:1 was employed. When aMw in the range of between
about 25,000 and about 37,000 (depending on CTA level) had been reached, further
BPA-Na was added in an amount determined from number average molecular weight
and the reaction was continued. As necessary, a further addition of BPA-Na was
made, to a total molar ratio of CIPAMI to BPA-Na of 1.01:1. It was found that said
constant molar ratio was possible, in contrast to previous experiments employing a
greater excess of CIPAMI in the initial stage when the molar ratio had to be varied
from 0.99:1 to 1.05:1. In addition, the level of unreactive N-phenylphthalimide end
groups was almost twice that determined in previous experiments, and total reaction
time was as low as 1.5 hours on a laboratory scale or 3 hours on a large scale, as
contrasted with 8-10 hours in previous work.
EXAMPLES 17-18 (Embodiment E)
The procedure of Example ] was repeated at a water content of less than 10 ppm, a
solids level of 25%, a CTA level of 3.6 mole percent and a PTC level of 0.7 mole
percent. The BPA-Na employed was ground by immersing a laboratory-scale tissue
homogcnizer in the slurry thereof for 5 minutes (Example 17) or 10 minutes (Example
18), reducing the maximum particle diameter in each example to about 200 microns.
The results are shown graphically in FIGURE 2, in comparison with Control H
employing unground BPA-Na. The unexpected advantage of using small particle size
BPA-Na is evident.
EXAMPLES 19-22 (Embodiment F-l)
The procedure of Example 1 was repeated with a PTC level of 0.8 mole percent, a
solids level of 25%, a CTA level of 3.6 mole percent and a water content of at most
10 ppm, using BPA-Na which had been prepared in toluene, filtered and dried in
vacuum. Four different grades of BPA-Na were employed: stoichiometrically pure to
within 0.05% (Example 19), varying from stoichiometric purity by at most 0.15%
(Example 20), BPA-nch by 0.3% (Example 21) and sodium hydroxide-rich by 0.3%
(Example 22).
The results are shown graphically in FIGURE 3, which shows a significant decrease
in molecular weight over time with the use of BPA-Na having any proportion of
impurities. The most significant decreases, at least over times up to about 75 minutes,
occur w i th the use of sal: containing greater than 0.15% impurities.
EXAMPLE 23 (Embodiment F-2)
The procedure of Example 1 was repeated with a PTC level of 0.8 mole percent, a
solids level of 25%, a CTA level of 3.7 mole percent and a water content of at most
10 ppm, using C1PAMI of various purities: within 0.02% of stoichiometric, 6.5% rich
in ainine, and 0.5% rich in anhydride. The results are shown graphically in FIGURE
4, and show the advantage of employing stoichiometrically pure or anhydride-rich
C1PAM1.
EXAMPLE 24 (Embodiment F-2)
The procedure of Example 1 was repeated with a PTC level of 0.8 mole percent, a
solids level of 25%. a CTA level of 3.7 mole percent and a water content of at most
10 ppm, using stoiehiometrically pure C1PAM1 and three samples which had been
spiked with 250, 500 and 3,700 ppm of phthalide. The results are shown graphically
in FIGURE 5. which shows that phthalide levels up to 500 ppm produce essentially
identical results but higher levels cause a substantial decrease in molecular weight
over time.
EXAMPLE 25 (Embodiment F-2)
The procedure of Example 1 was repeated with a PTC level of 0.8 mole percent, a
solids level of 25%, a CTA level of 3.5 mole percent and a water content of at most
10 ppm, using sloichiometrically pure C1PAMI and three samples which had been
spiked with 0.2 mole %, 0.5 mole % and 1.0 mole % of chlorobenzoic acids. The
results are shown graphically in FIGURE 6. which shows that chlorobenzoic acid
levels as low as 0.2 mole % cause a substantial decrease in molecular weight over
time.
While typical embodiments have been set forth for the purpose of illustration, the
foregoing descriptions and examples should not be deemed to be a limitation on the
scope of the invention. Accordingly, various modifications, adaptations, and
alternatives may occur to one skilled in the art without departing from the spirit arid
scope of the present invention. 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. All patents
cited herein are incorporated herein by reference.


We Claim:
1. A method for preparing an aromatic polyether polymer which comprises
contacting, in a solvent of low polarity, equimolar amounts of at least one alkali
metal salt of a dihydroxy-substituted aromatic hydrocarbon and at least one bis (
(N- (chlorophthalimido)) aromatic compound, in the presence of a phase transfer
catalyst which is substantially stable at the temperatures employed and a chain
termination agent;
wherein the at least one alkali metal salt of a dihydroxy-subsituted aromatic hydrocarbon has less than 25% of particles with a diameter of greater than 200 micrometers, said particle reduction of alkali metal salt preferably carried out in a manner as herein described.
2. The method as claimed in claim 1 wherein the solvent is at least one member selected from the group consisting of o-dichlorobenzene, dichlorotoluene, 1,2, 4-trichlorobenzene, diphenyl sulfone, phenetole, anisole and veratrole.
3. The method as claimed in claim 2 wherein the solvent is ortho- dichlorobenzene.
4. The method as claimed in claim 1, wherein the alkali metal salt is derived from at least one dihydroxy-substituted aromatic hydrocarbon of the formula
(Formula Removed)
wherein D has the structure of formula:
(Formula Removed)
wherein A1represents an aromatic group; E an alkylene or alkylidene group, which group may optionally be part of one or more fused rings attached to one or more aromatic groups bearing one hydroxy substituent; an unsaturated alkylidene group; or two or more alkylene or alkylidene groups connected by a moiety

different from alkylene or alkylidene and selected from the group consisting of an aromatic linkage, a tertiary nitrogen linkage; an ether linkage; a carbonyl linkage; a silicon- containing linkage; a sulfur-containing linkage; a phosphorus-containing linkage; R1 comprises hydrogen; a monovalent hydrocarbon group ; Y1 independently at each occurrence is selected from the group consisting of an inorganic atom; an inorganic group; an organic group; the letter "m" represents any integer from and including zero through the number of positions on Al available for substitution; the letter "p" represents an integer from and including zero through the number of positions on E available for substitution; the letter"t"represents an integer equal to at least one; the letter "s" represents an integer equal to either zero or one; and "u" represents any integer including zero.
5. The method as claimed in claim 1 wherein the alkali metal salt is derived from at least one dihydroxy-substituted aromatic hydrocarbon selected from the group consisting of; 4,4'-bis (3,5- dimethyl) diphenol,; 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; 1,2-bis (4-hydroxyphenyl) ethane; 1,1-bis (4-hydroxy-2- chlorophenyl) ethane; 2,2-bis (4-hydroxyphenyl) propane; 2,2-bis (3-phenyl-4- hydroxyphenyl) propane; 2,2-bis (4-hydroxy-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; 2,2-bis (4- hydroxyphenyl)-1-phenylpropane; 2, 4'-dihydroxyphenyl sulfone; 2, 2-bis- (4-hydroxyphenyl) butane; 2, 2-bis- (4-hydroxyphenyl)- 2-methylbutane; bis- (4-hydroxyphenyl); 2- (3-methyl-4-hydroxyphenyl-2- (4- hydroxyphenyl) propane; 2- (3, 5-dimethyl-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-dimethylphenyl-4- hydroxyphenyl) propane; 2,4-bis- (3, 5-dimethylphenyl-4-hydroxyphenyl) -2- methylbutane; 3,3-bis- (3, 5-

dimethylphenyl-4-hydroxyphenyl) pentane; 3- (4-hydroxyphenyl) -1, 1, 3-trimethylindan-5-ol, 1- (4-hydroxyphenyl)-1, 3,3- trimethylindan-5-ol, and mixtures thereof.
6. The method as claimed in claim 5 wherein the alkali metal salt is derived from bisphenol A.
7. The method as claimed in claim 6 wherein the bisphenol A salt is the disodium salt.
8. The method as claimed in claim 1 wherein the bis (N- (chlorophthalimido) ) aromatic compound has the formula
(Formula Removed)
wherein R13 comprises a C6-22 divalent aromatic hydrocarbon or halogenated hydrocarbon radical, a C2-22 alkylene or cycloalkylene radical or a divalent radical of the formula
in which Q is a covalent bond or a member selected from the group consisting of

(Formula Removed)
and an alkylene or alkylidene group of the formula CyH2y, wherein y is an integer from 1 to 5 inclusive.
9. The method as claimed in claim 8 wherein R is derived from at least one diamine selected from the group consisting of meta-phenylenediamine; para-phenylenediamine; 2-methyl-4,6-diethyl-l, 3-phenylenediamine; 5-methyl- 4,6-diethyl-1, 3-phenylenediamine; bis (4-aminophenyl) -2, 2-propane; bis (2-chloro-4-amino-3,5-diethylphenyl) methane, 4, 4'-diaminodiphenyl, 3,4'-diaminodiphenyl, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4, 4'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 2,4-toluenediamine ; and mixtures thereof.
10. The method as claimed in claim 1 wherein the phase transfer catalyst is a hexaalkylguanidinium salt.
11. The method as claimed in claim 10 wherein the hexaalkylguanidinium salt is a chloride.
12. The method as claimed in claim 4, wherein the inorganic atom is halogen and the inorganic group is nitro group.
13. The method as claimed in claim 4, wherein the organic group is selected from a monovalent hydrocarbon group, alkenyl, allyl, alkyl, aryl, aralkyi, alkaryl, cycloalkyl, and an alkoxy group.

14. The method as claimed in claim 1 wherein the chain termination agent is at least one member selected from the group consisting of alkyl halides, aryl halides, compounds of formula (XI) and compounds of formula(XII):
(Formula Removed)

wherein the chlorine substituent is in the 3-or 4-position, and Z1 and Z2 comprise a substituted or unsubstituted alkyl or aryl group.
15. The method as claimed in claim 14, wherein the alkyl halides is alkyl chlorides and the aryl halides is aryl chlorides.
16 The method as claimed in claim 14 wherein the chain termination agent comprises
at least one of 4-chloro-N-methylphthalimide, 4-chloro-N- butylphthalimide, 4-
chloro-N-octadecylphthalimide, 3-chloro-N-methylphthalimide, 3-chloro-N-
butylphthalimide, 3-chloro-N-octadecylphthalimide, 4-chloro-N-
phenylphthalimide,3-chloro-N-phenylphthalimide, 1 -N- (4-chlorophthalimido)-3-(N-phthalimido) benzene, 1-N- (3-chlorophthaiimido)-3- (N-phthalimido) benzene, 4-N- (3-chlorophthalimido) phenyl-4'- (N-phthalimido) phenyl ether, 4-N- (4-chlorophthalimido) phenyl-4'- (N-phthalimido) phenyl ether, or the corresponding isomers derived from 3,4'-diaminodiphenyl ether, wherein any mono- substituted bis-phthalimide chain termination agent is optionally in admixture with bis-substituted bis-phthalimide monomer.
17 The method as claimed in claim 1 wherein the alkali metal salt has less than 5% of particles with a diameter of greater than 500 micrometers.

18. The method as claimed in claim 1 wherein the alkali metal salt has less than 2% of particles with a diameter of greater than 500 micrometers.
19. The method as claimed in claim 1 wherein the alkali metal salt is subjected to at least one particle size reduction step using equipment which comprises one or more devices selected from the group consisting of a centrifugal pump, grinder, drop-down blender, particle size reduction homogenizer and delumper.
20 The method as claimed in claim 19 wherein the particle size reduction step is performed on a slurry of alkali metal salt in an organic solvent before or during transfer of alkali metal salt to a polymerization vessel.
21. A method for preparing an aromatic polyetherimide as claimed in claim 1 which
comprises contacting, in o-dichlorobenzene or anisole as solvent, equimolar
amounts of bisphenol A disodium salt and at least one bis (N-
(chlorophthalimido)) aromatic compound selected from the group consisting of
1,3- bis[N- (4-chlorophthalimido)]-benzene, 1, 4-bis[N- (4-chlorophthalimido)]
benzene, 4,4'-bis[N- (3-chlorophthalimido)] phenyl ether and 4,4'-bis [N- (4-
chlorophthalimido) ] phenyl ether, in the presence of a hexaalkylguanidinium
chloride as phase transfer catalyst and, optionally, at least one chain termination
agent selected from the group consisting of 4-chloro-N-methylphthalimide, 4-
chloro-N- butylphthalimide, 4-chloro-N-octadecylphthaIimide, 3-chloro-N-
methylphthalimide, 3-chloro-N-butylphthalimide, 3-chloro-N-
octadecylphthalimide, 4-chloro-N- phenylphthalimide, 3-chloro-N-phenylphthalimide, 1-N- (4-chlorophthalimido)-3- (N-phthalimido) benzene, 1-N-(3-chlorophthalimido)-3- (N-phthalimido) benzene, 4-N- (3-chlorophthalimido) phenyl-4'- (N-phthalimido) phenyl ether, 4-N- (4-chlorophthalimido) phenyl-4'-(N-phthalimido) phenyl ether, or the corresponding isomers derived from 3,4'-

diaminodiphenyl ether; wherein the bisphenol A disodium salt has less than 25% of particles with a diameter of greater than 200 micrometers.





Documents:

1000-DELNP-2006-Abstract-(17-03-2009).pdf

1000-delnp-2006-abstract.pdf

1000-DELNP-2006-Assignment-(04-08-2008).pdf

1000-DELNP-2006-Assignment-(17-03-2009).pdf

1000-delnp-2006-assignment.pdf

1000-DELNP-2006-Claims-(17-03-2009).pdf

1000-DELNP-2006-Claims-(30-03-2009).pdf

1000-DELNP-2006-Claims-(31-03-2009).pdf

1000-delnp-2006-claims.pdf

1000-delnp-2006-correspondence -others.pdf

1000-DELNP-2006-Correspondence-Others-(04-08-2008).pdf

1000-DELNP-2006-Correspondence-Others-(17-03-2009).pdf

1000-DELNP-2006-Correspondence-Others-(31-03-2009).pdf

1000-delnp-2006-description (complete).pdf

1000-DELNP-2006-Drawings-(17-03-2009).pdf

1000-DELNP-2006-Drawings-(31-03-2009).pdf

1000-delnp-2006-drawings.pdf

1000-DELNP-2006-Form-1-(04-08-2008).pdf

1000-DELNP-2006-Form-1-(17-03-2009).pdf

1000-delnp-2006-form-1.pdf

1000-DELNP-2006-Form-2-(04-08-2008).pdf

1000-DELNP-2006-Form-2-(17-03-2009).pdf

1000-delnp-2006-form-2.pdf

1000-DELNP-2006-Form-3-(17-03-2009).pdf

1000-delnp-2006-form-3.pdf

1000-delnp-2006-form-5.pdf

1000-delnp-2006-form-6-(04-08-2008).pdf

1000-DELNP-2006-GPA-(04-08-2008).pdf

1000-DELNP-2006-GPA-(17-03-2009).pdf

1000-delnp-2006-pct-101.pdf

1000-delnp-2006-pct-237.pdf

1000-delnp-2006-pct-304.pdf

1000-delnp-2006-pct-311.pdf


Patent Number 233952
Indian Patent Application Number 1000/DELNP/2006
PG Journal Number 21/2005
Publication Date 22-May-2009
Grant Date 22-Apr-2009
Date of Filing 24-Feb-2006
Name of Patentee SABIC INNOVATIVE PLASTICS IP B.V.
Applicant Address PLASTICSLAAN 1,4612 PX BERGEN OP ZOOM, NETHERLANDS
Inventors:
# Inventor's Name Inventor's Address
1 JOHNSON NORMAN ENOCH 1251 TANGLEWOOD DRIVE, MOUNT VERNON, IN 47620, U.S.A.
2 BRUNELLE DANIEL JOSEPH 4 WOODS EDGE,BRUNT HILLS,NY 12027, U.S.A.
3 ACAR HAVVA YAGCI 2009 LONDON SQUARE DRIVE,CLIFTON PARK,NY 1206. U.S.A.
4 KHOURI FARID FOUAD 6 TAMARACK LANE, CLIFTON PARK, NY 12065,U.S.A.
5 GUGGENHEIM THOMAS LINK 7160 UPTON ROAD, MOUNT VERNON, IN 47620, U.S.A.
6 WOODRUFF DAVID WINFIELD 20 VALENCIA LANE, CLIFTON PARK, NY 12065, U.S.A.
PCT International Classification Number C08G 73/12
PCT International Application Number PCT/US2004/025799
PCT International Filing date 2004-08-10
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 10/647,889 2003-08-25 U.S.A.