U.S. patent application number 16/255882 was filed with the patent office on 2019-05-23 for polyetherimide compositions and methods for the manufacture and use thereof.
The applicant listed for this patent is SABIC Global Technologies B.V.. Invention is credited to Stephen S. Dimond, Robert R. Gallucci, James A. Mahood, Roy R. Odle.
Application Number | 20190153160 16/255882 |
Document ID | / |
Family ID | 47744591 |
Filed Date | 2019-05-23 |
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United States Patent
Application |
20190153160 |
Kind Code |
A1 |
Gallucci; Robert R. ; et
al. |
May 23, 2019 |
POLYETHERIMIDE COMPOSITIONS AND METHODS FOR THE MANUFACTURE AND USE
THEREOF
Abstract
This disclosure relates to polyetherimide compositions whose
residual phenolic monomers exhibit little or no estradiol binding
activity. Also disclosed are methods for making the disclosed
polyetherimides and articles of manufacture comprising the
disclosed polyetherimides.
Inventors: |
Gallucci; Robert R.; (Mt.
Vernon, IN) ; Mahood; James A.; (Evansville, IN)
; Odle; Roy R.; (Mt. Vernon, IN) ; Dimond; Stephen
S.; (Bedford, NH) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SABIC Global Technologies B.V. |
Bergen op Zoom |
|
NL |
|
|
Family ID: |
47744591 |
Appl. No.: |
16/255882 |
Filed: |
January 24, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
15600992 |
May 22, 2017 |
10227452 |
|
|
16255882 |
|
|
|
|
14600797 |
Jan 20, 2015 |
9688816 |
|
|
15600992 |
|
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|
13564352 |
Aug 1, 2012 |
|
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14600797 |
|
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61526032 |
Aug 22, 2011 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G 73/1071 20130101;
C08G 73/1046 20130101; C08G 73/1053 20130101; C08K 5/13 20130101;
C08K 5/13 20130101; C08L 79/08 20130101 |
International
Class: |
C08G 73/10 20060101
C08G073/10; C08K 5/13 20060101 C08K005/13 |
Claims
1. A method of producing a polyetherimide having low estradiol
binding activity comprising, selecting both di-t-butyl hydroquinone
and bis-(hydroxy aryl)-N-aryl isoindolinone, or bis-(hydroxy
aryl)-N-aryl isoindolinone, or, selecting at least two phenolic
monomers from one of: (a) di-t-butyl hydroquinone, spiro biindane
bisphenols, resorcinol, hydroquinone, methyl hydroquinone, and
biphenols; (b) di-t-butyl hydroquinone, spiro biindane bisphenols,
hydroquinone, and biphenols; (c) di-t-butyl hydroquinone, spiro
biindane bisphenols, methyl hydroquinone, and biphenols; (d)
di-t-butyl hydroquinone, spiro biindane bisphenols, resorcinol,
hydroquinone, methyl hydroquinone, and tetramethyl bisphenol-A; (e)
di-t-butyl hydroquinone, spiro biindane bisphenols, hydroquinone,
and tetramethyl bisphenol-A; and, (f) di-t-butyl hydroquinone,
spiro biindane bisphenols, methyl hydroquinone, and tetramethyl
bisphenol-A; wherein each of said phenolic monomers do not exhibit
a half maximal inhibitory concentration (1050) less than 0.00025M
for alpha or beta in vitro estradiol receptors, and preparing a
polyetherimide from said phenolic monomers by (i) reacting a
diamine monomer with a halo or nitro anhydride to form a bis halo
or bis nitro phthalimide reaction product, followed by reacting the
bis halo or bis nitro phthalimide reaction product with said
phenolic monomers, or, (ii) reacting said phenolic monomers with a
mono halo or nitro N-alkyl phthalimide compound to form a bis alkyl
imide aromatic ether reaction product, converting the bis alkyl
imide aromatic ether reaction product to an aromatic ether
dianhydride reaction product, followed by reacting the aromatic
ether dianhydride reaction product with a diamine, the
polyetherimide comprising repeating units derived from the one or
more phenolic monomers, and wherein one or more residual phenolic
monomers are present at more than zero but less than or equal to
1,000 ppm and do not exhibit a half maximal inhibitory
concentration (IC50) less than 0.00025M for alpha or beta in vitro
estradiol receptors.
2. The method of claim 1 wherein the polyetherimide is end capped
with phenol.
3. The method of claim 1, wherein the polyetherimide is a
co-polyetherimide comprising repeating units derived from the
phenolic monomers.
4. The method of claim 1, further comprising combining the
polyetherimide with one or more additives in order to form a
polyetherimide composition, wherein each of the one or more
additives does not exhibit a half maximal inhibitory concentration
(IC50) less than 0.00025M for alpha or beta in vitro estradiol
receptors.
5. The method of claim 4, wherein the one or more additive
comprises a stabilizer, antioxidant, colorant, impact modifier,
flame retardant, anti-drip additive, mold release additive,
lubricant, plasticizer, mineral, reinforcement additive, or any
combination thereof.
6. The method of claim 4, wherein the one or more additive
comprises a phosphite and wherein when the phosphite, phosphonate
or mixture thereof is subjected to conditions effective to provide
one or more phosphite, or phosphonate hydrolysis product, each of
the one or more phosphite or phosphonate hydrolysis products does
not exhibit a half maximal inhibitory concentration (1050) less
than 0.00025M for alpha or beta in vitro estradiol receptors.
7. The method of claim 6, wherein the phosphite comprises a
diphenyl alkyl phosphite, phenyl dialkyl phosphite, trialkyl
phosphite, dialkyl phosphite, triphenyl phosphite, diphenyl
pentaerythritol diphosphite, or any combination thereof.
8. The method of claim 6, wherein the phosphite has a Mw greater
than 200 Daltons.
9. The method of claim 1, further comprising forming a
polyetherimide composition that includes the polyetherimide,
wherein the polyetherimide composition further comprises: a) a Mw
in the range of from 3,000 to 80,000 Daltons; b) a phenolic end
group content less than 20 meq/kg; c) a chloride content less than
1000 ppm; and d) a transition metal content less than 20 ppm; and
wherein the one or more residual phenolic monomers are present in
the polyetherimide composition at more than zero but less than 100
ppm.
10. The method of claim 1, wherein the polyetherimide has a Tg from
200 to 320.degree. C., a weight gain on immersion in water for 24
hours at 23.degree. C. of less than 3.5%, and a coefficient of
expansion from 30 to 50 ppm/.degree. C.
11. The method according to claim 1, wherein the phenolic monomers
in the polyetherimide consist of the selected phenolic
monomers.
12. A polyetherimide composition comprising the polyetherimide that
is produced according to the method of claim 1.
13. An article that is prepared from the polyetherimide composition
of claim 12.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. patent
application Ser. No. 15/600,992, filed on May 22, 2017, which is a
continuation of U.S. patent application Ser. No. 14/600,797, filed
on Jan. 20, 2015 (now U.S. Pat. No. 9,688,816), which is a
continuation of U.S. patent application Ser. No. 13/564,352, filed
Aug. 1, 2012 (abandoned), which claims the benefit of priority to
U.S. Provisional Application No. 61/526,032, filed Aug. 22, 2011,
the entire contents of each of which are hereby incorporated by
reference.
FIELD OF THE INVENTION
[0002] The present disclosure relates to polyetherimide
compositions having, among other characteristics, significantly
reduced or even no measurable level of estradiol like binding
activity. Also included herein are methods for preparing and/or
using the same, as well as articles formed from such compositions
and blends
BACKGROUND OF THE INVENTION
[0003] Polyimides (PI), and in particular polyetherimides (PEI),
are high performance polymers having a glass transition temperature
(Tg) of greater than 180.degree. C. These polymers further have
high strength, heat resistance, and modulus, and broad chemical
resistance. Polyetherimides are widely used in applications as
diverse as automotive, telecommunication, aerospace,
electrical/electronics, transportation, food service and
healthcare. Adding a reinforcing filler helps provide materials
that are particularly useful as molded parts for metal replacement,
for example in automotive and electrical/electronic applications
since these compositions offer good mechanical and thermal
properties.
[0004] However, when prepared under certain conditions,
polyetherimides can have small amounts of residual phenolic
monomers. In some instances these impurities may correspond to the
monomeric phenolic starting materials initially used to manufacture
the polyetherimide. Besides affecting polymer properties, residual
monomers can also be of concern in view of emerging regulatory
considerations. Therefore, complete conversion of monomers is
usually the desire of any polymer producer but is not always
attainable. To that end, there remains a need in the art for
thermoplastic polyetherimide compositions whose residual phenolic
monomers exhibit certain beneficial characteristics. Desirable
characteristics of such residual phenolic monomers include, among
others, relatively little or even no estradiol binding
activity.
SUMMARY OF THE INVENTION
[0005] This invention relates generally to polyetherimide
compositions whose residual phenolic monomers, if present, exhibit
relatively little or even no estradiol binding activity. The
polyetherimide compositions are manufactured from starting
materials that similarly exhibit relatively little or even no
estradiol binding activity.
[0006] In view of the foregoing, embodiments of the invention
generally provide a polyetherimide composition comprising repeating
units derived from one or more phenolic monomers, wherein each of
the one or more phenolic monomers does not exhibit a half maximal
inhibitory concentration (IC.sub.50) less than 0.00025M for alpha
or beta in vitro estradiol receptors. Additionally, when the
polyetherimide is prepared under conditions where small amounts of
residual phenolic monomer are present with the polymer, each of the
one or more residual phenolic monomers similarly does not exhibit a
half maximal inhibitory concentration (IC.sub.50) less than
0.00025M for alpha or beta in vitro estradiol receptors.
[0007] Further embodiments of the invention also provide polymer
blends comprising the polyetherimide compositions disclosed
herein.
[0008] In another embodiment, the present invention also provides
various articles of manufacture comprising the polyetherimide
compositions disclosed herein.
[0009] In still further embodiments, the invention provides methods
for the manufacture of the disclosed polyetherimide compositions.
According to some embodiments, a method is provided that generally
comprises reacting an aromatic dihydroxy monomer salt and a bis
halo or bis nitro phthalimide under conditions effective to provide
a polyetherimide reaction product. This type of polyetherimide
polymerization process is described, for example, in US patents;
U.S. Pat. Nos. 5,229,482; 4,554,357; 3,847,869 and 3,787,364. The
aromatic dihydroxy monomer is selected such that it does not
exhibit a half maximal inhibitory concentration (IC.sub.50) less
than 0.00025M for alpha or beta in vitro estradiol receptors. The
resulting polyetherimide is further characterized in that when the
polyetherimide is prepared under conditions where the aromatic
dihydroxy monomer is not completely incorporated into the polymer
or not subsequently removed from the polymer, each of the one or
more residual phenolic monomers does not exhibit a half maximal
inhibitory concentration (IC.sub.50) less than 0.00025M for alpha
or beta in vitro estradiol receptors. In some instances the
residual phenolic monomer content will be 100 ppm or less.
[0010] According to alternative embodiments, a method is provided
that generally comprises reacting an aromatic bis(ether anhydride)
with a diamine under conditions effective to provide a
polyetherimide reaction product (as described, for example, in US
patents; U.S. Pat. Nos. 4,585,852; 4,443,592 and 4,417,044). The
aromatic bis(ether anhydride) may be derived from an aromatic
dihydroxy monomer salt displacing a mono halo or nitro N-alkyl
phthalimide to make a bis alkyl imide aromatic ether (as described,
for example, in U.S. Pat. No. 4,257,953). The bis alkyl imide
aromatic ether can be subsequently converted to an aromatic ether
dianhydride, for example, as in US patents; U.S. Pat. Nos.
4,329,496; 4,329,292 and 4,318,857. The aromatic ether dianhydrides
can be reacted with aryl or alkyl diamines as described in the art
(for example US patents; U.S. Pat. Nos. 4,324,883; 4,324,883 and
4,293,683) to make polyetherimides. The aromatic bis(ether
anhydride) thereby derived is from an aromatic dihydroxy monomer
that does not exhibit a half maximal inhibitory concentration
(IC.sub.50) less than 0.00025M for alpha or beta in vitro estradiol
receptors. The resulting polyetherimide is further characterized in
that when the polyetherimide is prepared under conditions where the
aromatic dihydroxy monomer is not completely incorporated into the
bisimide monomer or polymer, or is not subsequently removed from
the polymer, each of the one or more residual monomers does not
exhibit a half maximal inhibitory concentration (IC.sub.50) less
than 0.00025M for alpha and/or beta in vitro estradiol
receptors.
[0011] Additional advantages will be set forth in part in the
description which follows. The advantages will be realized and
attained by means of the elements and combinations particularly
pointed out in the appended claims. It is to be understood that
both the foregoing general description and the following detailed
description are exemplary and explanatory only and are not
restrictive.
DETAILED DESCRIPTION OF THE INVENTION
[0012] The present invention can be understood more readily by
reference to the following detailed description, examples,
drawings, and claims, and their previous and following description.
However, before the present compositions, compounds, devices,
systems, and/or methods are disclosed and described, it is to be
understood that this invention is not limited to the specific
compositions, compounds, devices, systems, and/or methods disclosed
unless otherwise specified, as such can, of course, vary. It is
also to be understood that the terminology used herein is for the
purpose of describing particular aspects only and is not intended
to be limiting.
[0013] The following description of the invention is provided as an
enabling teaching of the invention in its best, currently known
embodiment. To this end, those of ordinary skill in the relevant
art will recognize and appreciate that many changes can be made to
the various aspects of the invention described herein, while still
obtaining the beneficial results of the present invention. It will
also be apparent that some of the desired benefits of the present
invention can be obtained by selecting some of the features of the
present invention without utilizing other features. Accordingly,
those of ordinary skill in the relevant art will recognize that
many modifications and adaptations to the present invention are
possible and can even be desirable in certain circumstances and are
a part of the present invention. Thus, the following description is
provided as illustrative of the principles of the present invention
and not in limitation thereof.
[0014] As used herein, the singular forms "a," "an" and "the"
include plural referents unless the context clearly dictates
otherwise. Thus, for example, reference to an "aromatic dihydroxy
monomer" can include two or more such monomers unless the context
indicates otherwise.
[0015] Ranges can be expressed herein as from "about" one
particular value, and/or to "about" another particular value. When
such a range is expressed, another aspect includes from the one
particular value and/or to the other particular value. Similarly,
when values are expressed as approximations, by use of the
antecedent "about," it will be understood that the particular
approximated value forms another aspect of the invention. It will
be further understood that the endpoints of each of the ranges are
significant both in relation to the other endpoint, and
independently of the other endpoint.
[0016] All ranges disclosed herein are inclusive of the endpoints
and are independently combinable. The endpoints of the ranges and
any values disclosed herein are not limited to the precise range or
value; they are sufficiently imprecise to include values
approximating these ranges and/or values. Ranges articulated within
this disclosure, e.g. numerics/values, shall include disclosure for
possession purposes and claim purposes of the individual points
within the range, sub-ranges, and combinations thereof. As an
example, for the recitation of numeric ranges herein, each
intervening number there between with the same degree of precision
is explicitly contemplated--for the range of 6-9, the numbers 7 and
8 are contemplated in addition to 6 and 9, and for the range
6.0-7.0, the number 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8,
6.9, and 7.0 are explicitly contemplated.
[0017] Various combinations of elements of this disclosure are
encompassed by this invention, e.g. combinations of elements from
dependent claims that depend upon the same independent claim.
[0018] As used herein, the terms "optional" or "optionally" mean
that the subsequently described event, condition, component, or
circumstance may or may not occur, and that the description
includes instances where said event or circumstance occurs and
instances where it does not.
[0019] A weight percent of a component, unless specifically stated
to the contrary, is based on the total weight of the formulation or
composition in which the component is included.
[0020] A residue of a chemical species, as used in the
specification and concluding claims, refers to the moiety that is
the resulting product of the chemical species in a particular
reaction scheme or subsequent formulation or chemical product,
regardless of whether the moiety is actually obtained from the
chemical species. Thus, an ethylene glycol residue in a polyester
refers to one or more --OCH.sub.2CH.sub.2O-- units in the
polyester, regardless of whether ethylene glycol was used to
prepare the polyester. Similarly, a sebacic acid residue in a
polyester refers to one or more --CO(CH.sub.2).sub.8CO-- moieties
in the polyester, regardless of whether the residue is obtained by
reacting sebacic acid or an ester thereof to obtain the
polyester.
[0021] Compounds are described using standard nomenclature. For
example, any position not substituted by any indicated group is
understood to have its valency filled by a bond as indicated, or a
hydrogen atom. A dash ("-") that is not between two letters or
symbols is used to indicate a point of attachment for a
substituent. For example, the aldehyde group --CHO is attached
through the carbon of the carbonyl group.
[0022] The term "aliphatic" refers to a linear or branched array of
atoms that is not cyclic and has a valence of at least one.
Aliphatic groups are defined to comprise at least one carbon atom.
The array of atoms may include heteroatoms such as nitrogen,
sulfur, silicon, selenium and oxygen or may be composed exclusively
of carbon and hydrogen ("Alkyl"). Aliphatic groups may be
substituted or unsubstituted. Exemplary aliphatic groups include,
but are not limited to, methyl, ethyl, isopropyl, isobutyl,
chloromethyl, hydroxymethyl (--CH.sub.2OH), mercaptomethyl
(--CH.sub.2SH), methoxy, methoxycarbonyl (CH.sub.3OCO--),
nitromethyl (--CH.sub.2NO.sub.2), and thiocarbonyl.
[0023] The term "alkyl group" as used herein is a branched or
unbranched saturated hydrocarbon group of 1 to 24 carbon atoms,
such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,
t-butyl, pentyl, hexyl, heptyl, octyl, decyl, tetradecyl,
hexadecyl, eicosyl, tetracosyl and the like. A "lower alkyl" group
is an alkyl group containing from one to six carbon atoms.
[0024] The term "alkoxy" as used herein is an alkyl group bound
through a single, terminal ether linkage; that is, an "alkoxy"
group can be defined as --OR where R is alkyl as defined above. A
"lower alkoxy" group is an alkoxy group containing from one to six
carbon atoms.
[0025] The term "alkenyl group" as used herein is a hydrocarbon
group of from 2 to 24 carbon atoms and structural formula
containing at least one carbon-carbon double bond. Asymmetric
structures such as (AB)C.dbd.C(CD) are intended to include both the
E and Z isomers. This can be presumed in structural formulae herein
wherein an asymmetric alkene is present, or it can be explicitly
indicated by the bond symbol C.
[0026] The term "alkynyl group" as used herein is a hydrocarbon
group of 2 to 24 carbon atoms and a structural formula containing
at least one carbon-carbon triple bond.
[0027] The term "aryl group" as used herein is any carbon-based
aromatic group including, but not limited to, benzene, naphthalene,
etc.
[0028] The term "aromatic" refers to an array of atoms having a
valence of at least one and comprising at least one aromatic group.
The array of atoms may include heteroatoms such as nitrogen,
sulfur, selenium, silicon and oxygen, or may be composed
exclusively of carbon and hydrogen. The aromatic group may also
include nonaromatic components. For example, a benzyl group is an
aromatic group that comprises a phenyl ring (the aromatic
component) and a methylene group (the nonaromatic component).
Exemplary aromatic groups include, but are not limited to, phenyl,
pyridyl, furanyl, thienyl, naphthyl, biphenyl,
4-trifluoromethylphenyl, 4-chloromethylphen-1-yl, and
3-trichloromethylphen-1-yl (3-CCl.sub.3Ph-).
[0029] The term "aromatic" also includes "heteroaryl group," which
is defined as an aromatic group that has at least one heteroatom
incorporated within the ring of the aromatic group. Examples of
heteroatoms include, but are not limited to, nitrogen, oxygen,
sulfur, and phosphorus. The aryl group can be substituted or
unsubstituted. The aryl group can be substituted with one or more
groups including, but not limited to, alkyl, alkynyl, alkenyl,
aryl, halide, nitro, amino, ester, ketone, aldehyde, hydroxy,
carboxylic acid, or alkoxy.
[0030] The term "cycloalkyl group" as used herein is a non-aromatic
carbon-based ring composed of at least three carbon atoms. Examples
of cycloalkyl groups include, but are not limited to, cyclopropyl,
cyclobutyl, cyclopentyl, cyclohexyl, etc. The term
"heterocycloalkyl group" is a cycloalkyl group as defined above
where at least one of the carbon atoms of the ring is substituted
with a heteroatom such as, but not limited to, nitrogen, oxygen,
sulfur, or phosphorus.
[0031] The term "aralkyl" as used herein is an aryl group having an
alkyl, alkynyl, or alkenyl group as defined above attached to the
aromatic group. An example of an aralkyl group is a benzyl
group.
[0032] The term "hydroxyalkyl group" as used herein is an alkyl,
alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or
heterocycloalkyl group described above that has at least one
hydrogen atom substituted with a hydroxyl group.
[0033] The term "alkoxyalkyl group" is defined as an alkyl,
alkenyl, alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or
heterocycloalkyl group described above that has at least one
hydrogen atom substituted with an alkoxy group described above.
[0034] The term "ester" as used herein is represented by the
formula --C(O)OA, where A can be an alkyl, halogenated alkyl,
alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl,
heterocycloalkyl, or heterocycloalkenyl group described above.
[0035] The term "carbonate group" as used herein is represented by
the formula --OC(O)OR, where R can be hydrogen, an alkyl, alkenyl,
alkynyl, aryl, aralkyl, cycloalkyl, halogenated alkyl, or
heterocycloalkyl group described above.
[0036] The term "carboxylic acid" as used herein is represented by
the formula --C(O)OH.
[0037] The term "aldehyde" as used herein is represented by the
formula --C(O)H.
[0038] The term "keto group" as used herein is represented by the
formula --C(O)R, where R is an alkyl, alkenyl, alkynyl, aryl,
aralkyl, cycloalkyl, halogenated alkyl, or heterocycloalkyl group
described above.
[0039] The term "carbonyl group" as used herein is represented by
the formula C.dbd.O.
[0040] The term "integer" means a whole number and includes zero.
For example, the expression "n is an integer from 0 to 4" means n
may be any whole number from 0 to 4, including 0.
[0041] As used herein, the term half maximal inhibitory
concentration (IC.sub.50) is a quantitative measure that indicates
how much of a particular substance, i.e., an inhibitor, is needed
to inhibit a given biological process or component of a process, by
one half. In other words, it is the half maximal (50%) inhibitory
concentration (IC) of a substance (50% IC, or IC.sub.50). It is
commonly known to one of ordinary skill in the art and used as a
measure of antagonist drug potency in pharmacological research. The
(IC.sub.50) of a particular substance can be determined using
conventional competition binding assays. In this type of assay, a
single concentration of radioligand (such as an agonist) is used in
every assay tube. The ligand is used at a low concentration,
usually at or below its K.sub.d value. The level of specific
binding of the radioligand is then determined in the presence of a
range of concentrations of other competing non-radioactive
compounds (usually antagonists), in order to measure the potency
with which they compete for the binding of the radioligand.
Competition curves may also be computer-fitted to a logistic
function as described under direct fit. The IC.sub.50 is the
concentration of competing ligand which displaces 50% of the
specific binding of the radioligand.
[0042] As summarized above, the present invention provides
polyetherimide compositions comprising repeating units derived in
part from one or more aromatic dihydroxy monomers. The aromatic
dihydroxy monomers used in the preparation of the polyetherimides
exhibit relatively little or even no measurable estradiol binding
activity as characterized by their half maximal inhibitory
concentration (IC.sub.50) for alpha or beta in vitro estradiol
receptors. Specifically, according to some embodiments, the
aromatic dihydroxy monomers of the invention do not exhibit a half
maximal inhibitory concentration (IC.sub.50) less than 0.00025M for
alpha or beta in vitro estradiol receptors. According to further
embodiments, each of the one or more aromatic dihydroxy monomers do
not exhibit a half maximal inhibitory concentration (IC.sub.50)
less than 0.0003M, 0.00035M, 0.0004M, 0.00045M, 0.0005M, 0.00075M,
or even 0.001M, for alpha or beta in vitro estradiol receptors. In
still other embodiments, aromatic dihydroxy monomers do not exhibit
any identifiable half maximal inhibitory concentration (IC.sub.50)
greater than or equal to about 0.00025M, 0.0003M, 0.00035M,
0.0004M, 0.00045M, 0.0005M, 0.00075M, or even 0.001M, for alpha
and/or beta in vitro estradiol receptors.
[0043] According to some embodiments, aromatic dihydroxy monomers
suitable for use in the polyetherimides of the invention include
phenolic monomers. These phenolic monomers can comprise dihydric
phenols (also known as bisphenols), mono phenols, or a combination
thereof. To that end, specific examples of suitable phenolic
monomers include, without limitation, resorcinol, hydroquinone,
methyl hydroquinone, t-butyl hydroquinone, di-t-butyl hydroquinones
(DTBHQ), biphenols, tetramethyl bisphenol-A, spiro biindane
bisphenols (SBIBP), bis-(hydroxy aryl)-N-aryl isoindolinones, or
any combination thereof. It should be understood that, in view of
this disclosure, any additional suitable aromatic dihydroxy
monomers exhibiting a lack of estradiol binding activity
characterized by the half maximal inhibitory concentration values
described above can be used.
[0044] As will be appreciated upon practice of the present
invention, when the disclosed polyetherimides are subjected to very
abusive conditions where the formation of one or more degradation
products might occur, the resulting degradants or other chemical
species if formed through an abusive degradation process will
similarly exhibit relatively little or even no measurable estradiol
binding activity as characterized by the half maximal inhibitory
concentration (IC.sub.50) for alpha or beta in vitro estradiol
receptors. For example, according to some embodiments, degradants
of the disclosed polyetherimides will not exhibit a half maximal
inhibitory concentration (IC.sub.50) less than 0.00025M for alpha
or beta in vitro estradiol receptors. According to further
embodiments, degradants of the disclosed polyetherimides do not
exhibit a half maximal inhibitory concentration (IC.sub.50) less
than 0.0003M, 0.00035M, 0.0004M, 0.00045M, 0.0005M, 0.00075M, or
even 0.001M, for alpha or beta in vitro estradiol receptors. In
still other embodiments, degradants of the disclosed
polyetherimides do not exhibit any identifiable half maximal
inhibitory concentration (IC.sub.50) greater than or equal to about
0.00025M, 0.0003M, 0.00035M, 0.0004M, 0.00045M, 0.0005M, 0.00075M,
or even 0.001M, for alpha and/or beta in vitro estradiol
receptors.
[0045] As will also be appreciated upon practice of the present
invention, any residual monomer content of the disclosed
polyetherimides will exhibit the half maximal inhibitory
concentration (IC.sub.50) values of the aromatic dihydroxy monomers
described above. For example, according to some embodiments, any
residual monomer content of the disclosed polyetherimides will not
exhibit a half maximal inhibitory concentration (IC.sub.50) less
than 0.00025M for alpha or beta in vitro estradiol receptors.
According to further embodiments, any residual monomer content of
the disclosed polyetherimides do not exhibit a half maximal
inhibitory concentration (IC.sub.50) less than 0.0003M, 0.00035M,
0.0004M, 0.00045M, 0.0005M, 0.00075M, or even 0.001M, for alpha or
beta in vitro estradiol receptors. In still other embodiments, any
residual monomer content of the disclosed polyetherimides do not
exhibit any identifiable half maximal inhibitory concentration
(IC.sub.50) greater than or equal to about 0.00025M, 0.0003M,
0.00035M, 0.0004M, 0.00045M, 0.0005M, 0.00075M, or even 0.001M, for
alpha and/or beta in vitro estradiol receptors. To that end,
according to embodiments of the invention, the disclosed
polyetherimides comprise a residual monomer content that is
preferably less than 100 ppm. According to still further
embodiments, the disclosed polyetherimide comprise a residual
monomer content less than 95 ppm, 90 ppm, 85, ppm, 80 ppm, 75 ppm,
70 ppm, 65 ppm, 60 ppm, 55 ppm, or event less than 50 ppm. Of
course, in still further embodiments, the disclosed polysulfones
contain essentially no residual monomer content. In some instances
the residual phenolic monomer will be present in the polyetherimide
polymer some number greater than zero and less than or equal to
1,000 ppm based on the polyetherimide polymer. In other instances
the residual phenolic monomer will be present in the polyetherimide
polymer at 0.1 to 1,000 ppm. In yet other instances the residual
phenolic monomer will be present in the polyetherimide polymer at 1
to 1,000 ppm.
[0046] The disclosed polyetherimides can be synthesized by any
conventionally known process for the manufacture of a
polyetherimide. For example, and without limitation, the disclosed
polyetherimides can be prepared by a conventional displacement
polymerization reaction whereby a halo or nitro substituted bis
phthalamide, such as a bis 4-chloro phthalimide, bis 4-fluoro
phthalimide or bis 4-nitro phthalimide is reacted with a dianion
salt of a disclosed aromatic dihydroxy compound under conditions
effective to result in the desired polymerization. These
displacement polymerizations are facilitated by the use of a phase
transfer catalyst such a tetra butyl ammonium chloride, tetra
phenyl phosphonium bromide, hexa ethyl guanidinium chloride or
other conventionally known phase transfer catalysts. In other
instances polyetherimde polymerization may be conducted in an
aprotic polar solvent. In these displacement polymerization
reactions the resulting resin can also be end capped to control
molecular weight. Exemplary and non-limiting endcapping agents that
can be used include mono chloro phthalimides or mono phenols. As
described in further detail below, according to some embodiments, a
preferred endcapping agent is phenol due to its lack of estradiol
binding activity. In particular, phenol does not exhibit a half
maximal inhibitory concentration (IC.sub.50) less than 0.00025M for
alpha or beta in vitro estradiol receptors
[0047] Substituted bis phthalamides suitable for reacting with the
dianion salt of a disclosed aromatic dihydroxy compound in a
displacement polymerization can themselves be synthesized by any
conventionally known process. According to some embodiments, such
bis phthalimides can be selected from those bis phthalimides
represented by the following structure:
##STR00001##
Linkage T in formula (I) includes substituted or unsubstituted
divalent organic radicals such as (a) aromatic hydrocarbon radicals
having about 6 to about 20 carbon atoms and halogenated derivatives
thereof; (b) straight or branched chain alkylene radicals having
about 2 to about 20 carbon atoms; (c) cycloalkylene radicals having
about 3 to about 20 carbon atoms, or (d) divalent radicals of the
general formula (II)
##STR00002##
wherein Q includes a divalent moiety selected from the group
consisting of --O--, --S--, --C(O)--, --SO2-, --SO--, --CyH2y- (y
being an integer from 1 to 5), and halogenated derivatives thereof,
including perfluoroalkylene groups. In a specific exemplary
embodiment, linkage T represents a phenylene moiety, such as
m-phenylene, which as one of ordinary skill in the art will
understand, can be derived from m-phenylene diamine (mPD).
Alternatively, in another specific and only exemplary embodiment,
linkage T represents a diphenyl sulfone, which as one of ordinary
skill in the art will again understand, can be derived from diamine
diphenyl sulfone (DDS). With further reference to formula (I), the
substituent R includes halogen or nitro. The substituents R are
beneficially located in the 3,3', 3,4', 4,3', or 4,4' positions,
and mixtures thereof.
[0048] In a second exemplary method, the disclosed polyetherimdes
can be prepared by the reaction of an aromatic bis(ether anhydride)
of the formula (III) with a stoichiometric amount of a diamine. The
aromatic bis(ether anhydride) can be selected from the group
represented by the following structure:
##STR00003##
[0049] wherein linkage Z represents an aryl diether linkage of the
general formula --O--Z'--O-- derived from the disclosed aromatic
dihydroxy compounds: including for example resorcinol,
hydroquinone, methyl hydroquinone, t-butyl hydroquinone, di-t-butyl
hydroquinones, biphenols, tetramethyl bisphenol-A, spiro biindane
bisphenols, bis-(hydroxy aryl)-N-aryl isoindolinones or any
combination thereof. Preferrably, the divalent bonds of the
--O--Z'--O-- group are located in the 3,3', 3,4', 4,3', or the 4,4'
positions. The bis(ether anhydride)s can, for example, be prepared
by the hydrolysis, followed by dehydration, of the reaction product
of a nitro substituted phenyl dinitrile with a metal salt of a
disclosed aromatic dihydroxy compound in the presence of a dipolar,
aprotic solvent. The ether dianhydrides can also be prepared by
exchange of a bis imide with an anhydride, for instance phthalic
anhydride. The polyetherimde may also be end capped with either
aniline or phthalic anhydride. Diamines that are well suited for
polymerization with the above-described aromatic bis(ether
anhydrides) include those represented by the formula:
H.sub.2N--Y--NH.sub.2 (IV),
wherein Y in formula (IV) represents substituted or unsubstituted
divalent organic radicals such as (a) aromatic hydrocarbon radicals
having about 6 to about 20 carbon atoms and halogenated derivatives
thereof; (b) straight or branched chain alkylene radicals having
about 2 to about 20 carbon atoms; (c) cycloalkylene radicals having
about 3 to about 20 carbon atoms, or (d) divalent radicals of the
general formula (II) as defined above. In a specific exemplary and
non-limiting embodiment, a preferred amines for reacting with the
disclosed aromatic bis(ether anhydrides) are aryl amines including
m-phenylene diamine (mPD) and p-phenylene diamine (pPD).
Alternatively, in another specific and only exemplary embodiment, a
preferred aryl amine for reacting with the disclosed aromatic
bis(ether anhydrides) includes diamino diphenyl sulfone (DDS). Such
a polymer is a polyetherimide sulfone. Mixtures of diamines may
also be employed. The substituents R are beneficially located in
the 3,3', 3,4', 4,3', or 4,4' positions, and mixtures thereof.
[0050] The polyetherimides of the present invention can be provided
as homopolymers comprising repeating units derived from a single
aromatic dihydroxy monomer. Alternatively, in other embodiments,
the polyetherimides of the invention can be provided as
co-polyetherimides, comprising repeating units derived from two or
more aromatic dihydroxy monomers or two or more diamines as
described herein. According to these embodiments, it should be
understood that the disclosed co-polyetherimides can be formulated
to provide any desired relative mole ratio of repeating units
within the chain of co-polyetherimides.
[0051] The relative mole ratio among the various monomeric
components present in a copolymer will depend, in part, upon the
total number of differing monomeric components present. The mole
ratios can be expressed as relative mole percentages whereby the
total mole percentage of monomeric components adds up to 100 mole
%. For example, a copolymer comprising a first aromatic dihydroxy
monomer and a second aromatic dihydroxy monomer can be provided
wherein the relative mole percentage ratio of the first monomer to
the second monomer is 90 mole % to 10 mole %, 80 mole % to 20 mole
%, 75 mole % to 25 mole %, 70 mole % to 30 mole %, 60 mole % to 40
mole %, or even 50 mole % to 50 mole %. Polyetherimide homopolymers
and copolymers may be blended separately or together in any
combination.
[0052] In addition to the structural units described above, it is
further contemplated that the polyetherimides of the present
invention can comprise one or more non-polyetherimide additives.
Preferably, the one or more non-polyetherimide additive also does
not exhibit a half maximal inhibitory concentration (IC.sub.50)
less than 0.00025M for alpha or beta in vitro estradiol receptors.
To that end, exemplary and non-limiting additives that can be
incorporated into the polyetherimides include stabilizers,
antioxidants, colorants, impact modifiers, flame retardants,
branching agents, anti drip additives, mold release additives,
lubricants, plasticizers, minerals (such as talc, clay, milled
glass or glass spheres), reinforcement additives such as carbon or
glass fibers, or any combination thereof. The amount of any such
additive that can be used is that amount sufficient to result in
the desired degree or effect for which the additive is intended.
For example, if the additive is an antioxidant, color stabilizer or
flame retardant the amount of additive will be that amount
sufficient to provide a desired level of intended performance e.g.
resistance to thermal aging, lower color or resistance to ignition.
Such amounts can be readily determined by one of ordinary skill in
the art without undue experimentation.
[0053] Any one or more of the above referenced non-polyetherimide
additives can be provided as a phosphorous containing compound.
Exemplary phosphorous containing compounds including phosphites and
phosphonates or mixtures thereof. Thus, according to embodiments of
the invention where phosphorous containing additives are present,
it is preferable that the particular phosphorous containing
additive similarly does not exhibit a half maximal inhibitory
concentration (IC.sub.50) less than 0.00025M for alpha or beta in
vitro estradiol receptors. To that end, when such phosphorous
containing additives are subjected to a hydrolysis reaction under
conditions effective to provide one or more hydrolysis products,
the hydrolysis product will similarly not exhibit a half maximal
inhibitory concentration (IC.sub.50) less than 0.00025M for alpha
or beta in vitro estradiol receptors.
[0054] According to embodiments of the invention, suitable
phosphite additives include diphenyl alkyl phosphites, phenyl
dialkyl phosphites, trialkyl phosphites, dialkyl phosphites,
triphenyl phosphites, diphenyl pentaerythritol diphosphite, or any
combination thereof. The phosphite additives can be present in any
desired or effective amount, when used the phosphite additives are
preferably present in an amount in the range of from 0.00001 to 0.3
wt % phosphite, 0.00001 to 0.2 wt % phosphite, or even in the range
of from 0.0001 to 0.01 wt % phosphite. Still further, it should be
understood that a phosphorous containing additive such as a
phosphite additive can have any desired molecular weight. However,
according to a preferred embodiment, the phosphite additive has a
molecular weight that is greater than 200 Daltons.
[0055] Conventional polymerization processes for manufacturing
polyetherimides also commonly employ the use of a chain stopper
(also referred to as an endcapping agent) during the polymerization
reaction. The chain stopper limits molecular weight growth rate,
and thus can be used to controls molecular weight in the
polyetherimide. To that end, many conventionally known end capping
agents exhibit undesirably high levels of estradiol binding
activity. In contrast, however, suitable end capping agents or
chain stoppers for use with the present invention exhibit estradiol
binding activity levels similar or even identical to that of the
selected aromatic dihydroxy monomers. More specifically, the end
capping agents suitable for use in the present invention also do
not exhibit a half maximal inhibitory concentration (IC.sub.50)
less than 0.00025M for alpha or beta in vitro estradiol receptors.
As such, any potential degradation product of the selected chain
stopper, if formed, will likewise not exhibit a half maximal
inhibitory concentration (IC.sub.50) less than 0.00025M for alpha
or beta in vitro estradiol receptors. Exemplary chain stoppers
include certain mono amines (for example aniline), mono anhydrides
(for example phthalic anhydride), mono-phenolic compounds and the
like. In one embodiment, a suitable chain stopper for use in the
present invention is phenol. Thus, when phenol is included as a
chain stopper, the resulting polyetherimide comprises phenol as an
end cap to the polymer chain. It should be understood however that
the polyetherimides disclosed herein can be produced having any
desired weight average molecular weight (Mw) with any end cap.
[0056] The disclosed polyetherimides can have any desired molecular
weight. For example, disclosed polyetherimides can have weight
average molecular weights in the range of from 3,000 to 80,000
Daltons, including exemplary molecular weights of 5,000, 7,000,
10,000, 15,000, 20,000, 25,000, 30,000, 35,000, 40,000 and 45,000,
50,000, 55,000, 60,000 and 65,000. 70,000 and 75,000. In still
further examples, the weight average molecular weight (Mw) of a
disclosed polyetherimides can be in a range of from any one of the
above mentioned values to any other of the above mentioned values.
For example, molecular weight of a disclosed polyetherimides can be
in the range of from 3,000 to 80,000 Daltons. In still a further
example, the molecular weight of a disclosed polyetherimides can be
expressed as a value less than any one of the above disclosed
values or, alternatively, can be expressed as a value greater than
any one of the above disclosed values. For example, the molecular
weight of a disclosed polyetherimides can be greater than 3,000
Daltons, or less than 80,000 Daltons. Molecular weight may be
determined by gel permeation chromatography (GPC) as described, for
example, in American Society for Testing Materials (ASTM) method
D5296.
[0057] As used in the specification and claims herein, the term
"compounding" refers to the intimate mixing of the polyetherimide
and non-polyetherimide additives such as the phosphorous containing
compound prior to preparation of a final product or article.
Compounding is commonly performed by combining as-synthesized
polyetherimide with the additive(s) and passing the mixture through
an extruder to produce compounded pellets that can be dried and
then further processed, for example into shaped articles. When
dried, the pellets preferably have a moisture content less than
about 100 ppm. Low moisture content is very important for formation
of molded articles (especially injection molded articles) free from
bubbles, voids or surface imperfections such as splay. Exemplary
further melt processing can include injection molding, blow
molding, extrusion, gas assist molding or compression molding
processes. The additive(s) can be combined with the as-synthesized
polyetherimide prior to any pelletizing, or after pelletization of
the as-synthesized polyetherimide.
[0058] Compounding can be performed either in a melt or in
solution. In the melt, the polyetherimide and additives can be melt
mixed or kneaded together in an extruder, melt kneader, reactor or
other system or device capable of melting and mixing the
polyetherimide and the additives, followed by extrusion or
pelletization, or by direct melt processing into shaped articles.
In solution processing, the polyetherimide and additive(s) are
combined in an inert solvent and maintained together for sufficient
reaction time and temperature to reduce the color of the
composition. The solvent is then removed, for example using vacuum.
In some instances residual solvent for example chlorobenzene,
o-dichlorobenzene, sulfolane, anisole or veratrole, should be less
than 100 ppm. In other instances residual solvent will be less than
50 ppm.
[0059] The temperature of the extruder in the foregoing methods
will generally be the conventional extruder temperature used for
forming pellets of a particular thermoplastic polyetherimide. The
appropriate extruder temperature will depend on the properties of
both the polyetherimide and the additives. Higher molecular weight
polyetherimides and/or high heat polyetherimides containing monomer
units that increase the glass transition temperature of the
polyetherimide will typically require higher extruder temperatures,
so that the melt viscosity is low enough for sufficient mixing with
the additives to occur. Suitable temperature ranges are 300 to
420.degree. C., specifically 330 to 370.degree. C. One skilled in
the art will understand that the temperature of the polymer melt
can vary somewhat from the extruder temperature depending on the
occurrence of exothermic and/or endothermic reactions and processes
and any heat generated by the mechanical mixing of the molten
polymer.
[0060] The polyetherimide compositions of the invention can further
be blended with additional thermoplastic resins or polymers. For
example, and without limitation, the polyetherimides of the
invention can be blended with polycarbonates, polyester carbonates,
polyarylates, polyamides, polyphenylene sulfides, polyphenylene
ethers, polyesters, polysulfones, polyethersulfones, polyphenylene
ether sulfones, polyolefins, or any combination thereof.
[0061] In some instance the disclosed polyetherimides may exhibit a
phenolic group content less than 20 meq/kg; a chloride content less
than 20 ppm; a transition metal content less than 20 ppm; and a
residual monomer content less than 100 ppm. Residual monomer
content can be measured using standard techniques, such as gas or
liquid chromatography, on an extract of the polymer. The extract
can also be titrated to determine phenolic content. Chloride
content can be determined for example by analysis of an aqueous
extract of the polymer using for example ion chromatography (IC).
Metals, including transition metals, and total chloride can be
determined by pyrolysis/ashing of the sample followed by ion plasma
chromatography (ICP) or other known techniques. Phenolic end groups
of the polymer may be measured by known techniques such as
titration, infrared spectroscopy (IR), and nuclear magnetic
resonance (NMR). In one instance .sup.31P NMR analysis using
phosphorous functionalization of end groups can be used to
characterize the resins. Wherein the polyetherimide (PEI) resin was
dissolved in CDCl.sub.3 with pyridine and chromium acetylacetonate
(CrAcAc) and the phenolic hydroxyl groups are phosphorylated with
o-phenylene phosphoro chloridite to enhance the NMR signal.
[0062] In other instances the polyetherimide will have a Tg from
200 to 320.degree. C., a weight gain on immersion in water for 24
hrs at 23.degree. C. of less than 3.5% and a coefficient of
expansion (CTE) from 30 to 50 ppm/.degree. C.
[0063] The polyetherimides of the present invention are well suited
for a variety of uses, including the manufacture of various
articles. For example, and without limitation, the polyetherimide
compositions of the invention can be used as either clear or opaque
resins for medical uses, food service uses, housewares,
electronics, packaging, computer enclosures, trays, drinking
glasses, pitchers, syringes, connectors, filter housings, pipes,
cell phone housings, keycaps, handles, bottles, films, coatings,
and the like. In some instances articles can be formed by melt
processing such as injection molding, extrusion or blow
molding.
[0064] Specific non-limiting examples of polyetherimide
compositions of the invention are illustrated below. In one
embodiment, a polyetherimide is disclosed wherein the repeating
units are derived from the reaction of the bis 4-chloro phthalimide
of m-phenylene with di-tert butyl hydroquinone. Phenol can also be
selected as the desired chain stopper. The resulting polyetherimide
structure is shown below, wherein "n" can be any desired integer
based upon the desired chain length for the co-polyetherimide.
##STR00004##
It is contemplated that this exemplified polyetherimide, and others
disclosed herein, can be obtained having a Mw in the range of from
3,000 to 80,000 Daltons; a phenolic group content less than 20
meq/kg; a chloride content less than 100 ppm; a transition metal
content less than 20 ppm; and a residual monomer content less than
100 ppm.
[0065] In another embodiment, a polyetherimide is disclosed wherein
the repeating units are derived from the reaction of the bis
4-chloro phthalimide of m-phenylene with spiro biindane bisphenol
(SBIBP). Phenol can again be selected as the desired chain stopper.
The resulting polyetherimide structure is shown below, wherein "n"
can be any desired integer based upon the desired chain length for
the polyetherimide.
##STR00005##
It is contemplated that this exemplified polyetherimide, and others
disclosed herein, can be obtained having a Mw in the range of from
3,000 to 80,000 Daltons; a phenolic group content less than 20
meq/kg; a chloride content less than 100 ppm; a transition metal
content less than 20 ppm; and a residual monomer content less than
100 ppm.
[0066] In another embodiment, a polyetherimide is disclosed wherein
the repeating units are derived from the reaction of the bis
4-chloro phthalimide of m-phenylene with resorcinol. Phenol can
again be selected as the desired chain stopper. The resulting
polyetherimide structure is shown below, wherein "n" can be any
desired integer based upon the desired chain length for the
polyetherimide.
##STR00006##
It is contemplated that this exemplified polyetherimide, and others
disclosed herein, can be obtained having a Mw in the range of from
3,000 to 80,000 Daltons; a phenolic group content less than 20
meq/kg; a chloride content less than 100 ppm; a transition metal
content less than 20 ppm; and a residual monomer content less than
100 ppm.
[0067] In still another embodiment, a polyetherimide is disclosed
wherein the repeating units are derived from the reaction of the
bis 4-chloro phthalimide of m-phenylene with N-phenyl
phenolphthalein bisphenol. Phenol can again be selected as the
desired chain stopper. The resulting polyetherimide structure is
shown below, wherein "n" can be any desired integer based upon the
desired chain length for the polyetherimide.
##STR00007##
It is contemplated that this exemplified polyetherimide, and others
disclosed herein, can be obtained having a Mw in the range of from
3,000 to 80,000 Daltons; a phenolic group content less than 20
meq/kg; a chloride content less than 100 ppm; a transition metal
content less than 20 ppm; and a residual monomer content less than
100 ppm.
[0068] In still further embodiments, a polyetherimide is disclosed
wherein the repeating units are derived from the reaction of the
bis 4-chloro phthalimide of diamino diphenyl sulfone with
resorcinol. Phenol can again be selected as the desired chain
stopper. The resulting polyetherimide structure is shown below,
wherein "n" can be any desired integer based upon the desired chain
length for the polyetherimide.
##STR00008##
It is contemplated that this exemplified polyetherimide, and others
disclosed herein, can be obtained having a Mw in the range of from
3,000 to 80,000 Daltons; a phenolic group content less than 20
meq/kg; a chloride content less than 100 ppm; a transition metal
content less than 20 ppm; and a residual monomer content less than
100 ppm.
[0069] In still another embodiment, a co-polyetherimide is
disclosed wherein the repeating units are derived from the reaction
of the bis 4-chloro phthalimide of diamino diphenyl sulfone with
spiro biindane bisphenol (SBIBP). Phenol can again be selected as
the desired chain stopper. The resulting polyetherimide structure
is shown below, wherein "n" can be any desired integer based upon
the desired chain length for the co-polyetherimide.
##STR00009##
It is contemplated that this exemplified co-polyetherimide, and
others disclosed herein, can be obtained having a Mw in the range
of from 3,000 to 80,000 Daltons; a phenolic group content less than
20 meq/kg; a chloride content less than 100 ppm; a transition metal
content less than 20 ppm; and a residual monomer content less than
100 ppm.
[0070] In yet another embodiment, a co-polyetherimide is disclosed
wherein the repeating units are derived from the reaction of the
bis 4-chloro phthalimide of m-phenylene diamine with resorcinol and
di t-butyl hydroquinone. Phenol can again be selected as the
desired chain stopper. The resulting polyetherimide structure is
shown below, wherein "n" can be any desired integer based upon the
desired chain length for the co-polyetherimide.
##STR00010##
It is contemplated that this exemplified co-polyetherimide, and
others disclosed herein, can be obtained having a Mw in the range
of from 3,000 to 80,000 Daltons; a phenolic group content less than
20 meq/kg; a chloride content less than 100 ppm; a transition metal
content less than 20 ppm; and a residual monomer content less than
100 ppm.
[0071] In a further embodiment, a co-polyetherimide is disclosed
wherein the repeating units are derived from the reaction of the
bis 4-chloro phthalimide of diamino diphenyl sulfone with spiro
biindane bisphenol and resorcinol. Phenol can again be selected as
the desired chain stopper. Other end groups are also contemplated.
The resulting polyetherimide structure is shown below, wherein "n"
can be any desired integer based upon the desired chain length for
the co-polyetherimide.
##STR00011##
[0072] It is contemplated that this exemplified co-polyetherimide,
and others disclosed herein, can be obtained having a Mw in the
range of from 3,000 to 80,000 Daltons; a phenolic group content
less than 20 meq/kg; a chloride content less than 100 ppm; a
transition metal content less than 20 ppm; and a residual monomer
content less than 100 ppm.
EXAMPLES
[0073] The following examples are put forth so as to provide those
of ordinary skill in the art with a complete disclosure and
description of how the methods, devices, and systems disclosed and
claimed herein are made and evaluated, and are intended to be
purely exemplary and are not intended to limit the disclosure.
Efforts have been made to ensure accuracy with respect to numbers
(e.g., amounts, temperature, etc.), but normal experimental
deviations should be accounted for. Unless indicated otherwise,
parts are parts by weight, temperature is in C or is at ambient
temperature, and pressure is at or near atmospheric. Examples of
the invention are designated by numbers, control experiments are
designated by letters.
[0074] Utilizing a conventional in vitro competitive binding assay
as described above, estradiol binding activity was quantified by
the half maximal inhibitory concentration (IC.sub.50) value, which
was evaluated for various phenolic compounds capable for use as
component starting materials in the manufacture of polyetherimide
compositions. These component starting materials might remain in
the polymer during polymerizations run under certain conditions as
resdival monomers. Specifically, (IC.sub.50) binding concentrations
for the alpha or beta in vitro estradiol receptors for various
compounds were tested. Three separate sets of tests were run using
a standard competitive binding assay. Samples were dissolved in
either ethanol or DMSO. The various phenolic compounds were then
tested at up to seven different concentrations for each test
phenolic compound. Each of those tests was run in triplicate. Tests
were conducted by displacement of a radio-ligand. For each set of
tests a 17b-estradiol control sample was run to ensure proper
binding of the natural hormone under the test conditions.
[0075] The polyetherimide hydrolysis product to be tested (Tables 1
to 3) was investigated as to its binding affinity for recombinant
human estradiol receptors (rhER) alpha (.alpha.) and beta 1
(.beta.1) in vitro. 17.beta.-Estradiol (E.sub.2) was used a
standard whose relative binding affinity was defined as 100%.
Competitive binding assays were performed by incubating rhER alpha
(.alpha.) and beta 1 (.beta.1) receptors with 10 nM
[.sup.3H]estradiol (the radio ligand) in the presence or absence of
increasing concentrations, 0.25 to 250,000 nM, of the phenolic test
compounds of Tables 1 to 3 (nM is nano molar). Each data point is
the average of at least two assays. Stock solutions of the
compounds of Tables 1 to 3 were prepared at 10.times.E-2 M in 100%
ethanol, water or DMSO (dimethyl sulfoxide). Compounds were diluted
10 fold in binding buffer and then 1:4 in the final assay mix. The
final concentration of ethanol or DMSO in the assay well was 5%.
The highest concentration of the hydrolysis test compound was
2.5.times. E-4 M (250,000 nM). The residual monomers of Tables 1 to
3 were tested at seven concentrations over log increments. The
lowest concentration was 2.5.times.E-10 M (0.25 nM). The IC50 Is
the concentration of test substance at which about 50% of the radio
labeled estradiol was displaced from the estradiol receptor.
[0076] In some very surprising instances (see Tables 1 to 3) the
disparate phenolic compounds: tetra methyl bisphenol-A (TMBPA),
phenol, N-phenyl phenolphthalein bisphenol (PPPBP), resorcinol,
biphenol (BP), spiro biindane bisphenol (SBIBP), di t-butyl
hydroquinone (DTBHQ) and methyl hydroquinone (MHQ) show no
estradiol binding, even at the highest concentration. In terms of
their ability to bind to alpha or beta estradiol hormone receptors
these phenolic compounds show a surprising reduction in activity.
In some instances no binding can be measured using standard
biochemical analysis techniques to test estradiol binding activity.
That is even at a concentration of 2.5.times.E-4 M there was no
displacement of estradiol. Note that 17b-estradiol binds at very
low concentrations of 1.0 to 14.7.times.E-9 M in our various
control experiments and is much more active than any of the
phenolic compounds tested.
[0077] The (IC.sub.50) values obtained from these experiments are
provided in the tables below. As shown, many mono and bisphenols
show an undesired high level of receptor binding. However very
surprisingly the preferred phenolic compounds utilized to prepare
the polyetherimide compositions of the invention (tetra methyl
bisphenol-A (TMBPA), phenol, N-phenyl phenolphthalein bisphenol
(PPPBP), resorcinol, biphenol (BP), spiro biindane bisphenol
(SBIBP), di t-butyl hydroquinone (DTBHQ) and methyl hydroquinone
(MHQ)) either did not show any detectable estradiol binding in
these tests or, at a minimum, did not exhibit an (IC.sub.50)
binding concentrations less than 2.5.times.E-4 M. An entry of
>2.5.times.E-4 for compounds in Tables 1 to 3 indicates that
those compounds did not compete to the extent of 50% with radio
labeled 17b-estradiol at the highest concentration (250,000 nM)
tested. There was no estradiol displacement and hence no 1050 could
be determined. The 1050, if identifiable at all, may be some value
greater than 2.5.times.E-4M.
[0078] The estradiol displacement experiments of set 1 (Table 1)
show that the phenolic compounds; p-cumyl phenol (control example
B), dihydroxy diphenyl ether (control example C), bisphenol
acetophenone (control example D), dimethyl acetophenone bisphenol
(control example E), diphenolic acid methyl ester (control example
F) and dimethyl cyclohexyl bisphenol (control example G) all
displace estradiol at low concentrations. Surprisingly, under the
same conditions, tetra methyl BPA (Example 1), phenol (Example 2),
N-phenyl phenolphthalein bisphenol (Example 3) and resorcinol
(Example 4) show no detectible estradiol displacement at either the
alpha or beta receptor at as high as 2.5.times.E-4 molar
concentration.
TABLE-US-00001 TABLE 1 Table 1: Experimental Set 1 Example
Compounds IC50 rhER alpha IC50 rhER beta A 17b-estradiol control
1.0 .times. E-9 8.2 .times. E-9 B p-Cumyl Phenol (CAS# 599-64-4)
1.4 .times. E-4 9.8 .times. E-6 C Dihydroxy Diphenyl Ether (CAS#
1965-09-9) 6.0 .times. E-5 1.4 .times. E-5 D Bisphenol Acetophenone
(CAS# 1571-75-1) 1.2 .times. E-5 1.4 .times. E-6 E Dimethyl
Acetophenone Bisphenol (CAS# 4754-63-6) 4.8 .times. E-6 3.5 .times.
E-6 F Diphenolic Acid Methyl Ester (CAS# 7297-85-0) 1.9 .times. E-5
1.1 .times. E-5 G Dimethyl Cyclohexyl Bisphenol (CAS# 2362-14-3)
1.3 .times. E-6 3.1 .times. E-6 1 Tetra Methyl BPA (CAS# 5613-46-7)
>2.5 .times. E-4 >2.5 .times. E-4 2 Phenol (CAS# 108-95-2)
>2.5 .times. E-4 >2.5 .times. E-4 3 N-Phenyl Phenolphthalein
Bisphenol (CAS# 6607-41-6) >2.5 .times. E-4 >2.5 .times. E-4
4 Resorcinol (CAS# 108-46-3) >2.5 .times. E-4 >2.5 .times.
E-4 IC50 is the conc. of the candidate that displaces 50% >2.5
.times. E4 compounds did not compete to the of the radioactive
ligand from the rhER cells extent of 50% with radiolabeled
17B-estradiol at the highest conc. (250,000 nM) tested, no IC50 can
be determined
[0079] In a second set of experiments (Table 2) phenolic compounds
structurally similar to, but not identical to those of set 1, were
tested as to their ability to displace estradiol. The surprising
and unpredictable trend of estradiol displacement is again
observed. The bis phenolic compounds: fluorenone bis o-cresol
(control example I), hydro isophorone bisphenol (control example
J), bisphenol M (control example K), and bis hydroxy phenyl
menthane (control example L) all displace estradiol at low
concentrations. On the other hand, spiro biindane bisphenol
(Example 5), biphenol (Example 6) and di t-butyl hydroquinone
(Example 7) all show no displacement of the estradiol at the alpha
receptor at 2.5.times.E-4 M concentration. Examples 5 and 7 also
show no displacement at the beta receptor. 17b-Estradiol (control
example H) binds at a very low concentration.
TABLE-US-00002 TABLE 2 Table 2: Experimental Set 2 Example
Compounds IC50 rhER alpha IC50 rhER beta H 17b-estradiol control
7.0 .times. E-9 6.6 .times. E-9 I Fluorenone Bis-o-Cresol (CAS#
88938-12-9) 9.7 .times. E-6 2.5 .times. E-5 J Hydro Isophorone
Bisphenol (CAS# 129188-99-4) 4.5 .times. E-7 1.1 .times. E-6 K
Bisphenol M (CAS# 13595-25-0) 2.1 .times. E-6 1.4 .times. E-6 L Bis
Hydroxy Phenyl Menthane (CAS# 58555-74-1) 4.9 .times. E-7 6.7
.times. E-7 5 Spiro Biindane Bisphenol (CAS# 1568-80-5) >2.5
.times. E-4 >2.5 .times. E-4 6 Biphenol (CAS# 92-88-6) >2.5
.times. E-4 1.7 .times. E-6 7 Di t-Butyl Hydroquinone (CAS#
88-58-4) >2.5 .times. E-4 >2.5 .times. E-4 IC50 is the conc.
of the candidate that displaces >2.5 .times. E4 compounds did
not compete to the 50% of the radioactive ligand from the rhER
cells extent of 50% with radiolabeled 17B-estradiol at the highest
conc. (250,000 nM) tested, no IC50 can be determined
[0080] In yet another set of experiments (Table 3) undesirable
estradiol displacement at low concentration is observed for the
bisphenols benzophenone bisphenol (control example N) and
phenolphthalein (control example 0) while methyl hydroquinone
(Example 8) surprisingly shows no alpha or beta estradiol
displacement at as high as 2.5.times.E-4 molar concentration. As in
the other sets of experiments (Tables 1 to 3) an estradiol control
(example M) was run as part of the set to establish a baseline of
estradiol displacement. Estradiol displaces at much lower
concentration than any of the phenolic compounds.
TABLE-US-00003 TABLE 3 Table 3: Experimental Set 3 IC50 rhER IC50
rhER Example Compounds alpha beta M 17b-estradiol control 10.0
.times. E-9 14.7 .times. E-9 N Benzophenone bisphenol 3.1 .times.
E-5 3.2 .times. E-6 (CAS# 611-99-4) O Phenolphthalein 3.7 .times.
E-6 1.4 .times. E-5 (CAS# 77-09-8) 8 Methyl Hydroquinone >2.5
.times. E-4 >2.5 .times. E-4 (CAS# 95-71-6) IC50 is the conc. of
the >2.5 .times. E4 compounds did not candidate that displaces
compete to the extent of 50% 50% of the radioactive with
radiolabeled 17B-estradiol ligand from the rhER at the highest
conc. cells (250,000 nM) tested, no IC50 can be determined
[0081] The estradiol binding of phenolic compounds seems to be very
unpredictable. It does not correlate with molecular weight,
phenolic group separation, molecular rigidity, solubility, steric
or electronic effects. Note that while the phenolic compounds of
our invention show no displacement at the alpha or beta estradiol
binding sites at concentration below the 2.5.times.E-4M limit of
detection, even the control examples, while showing some binding,
are not as reactive as estradiol (control examples A, H and M).
17b-Estradiol binds at a very low concentration.
Polyetherimide Preparation & Testing
[0082] Procedure for Dianhydride Preparation.
[0083] Under a nitrogen atmosphere, a mixture of (1 mol) of the
disodium salt of the bisphenols: bis-(4-hydroxyphenyl)-N-phenyl
phenolphthalein or 2,2'6'6'-tetramethyl bisphenol A and
4-fluorophthalic anhydride (2 mol) were dissolved in dried DMAC
(dimethyl acetamide) and heated at 180.degree. C. The solution
became homogeneous after 5 to 10 min. The solution was stirred for
a total of one hour and allowed to cool to room temperature. The
reaction mixture was then poured into a mixture of 200 ml of 1N
aqueous HCl and ice. The resulting yellow to white precipitate was
filtered and washed with 50 ml of water and then methanol to give
80 to 85% of the desired dianhydride shown in the FIGURES below.
The dianhydrides were recrystallized in acetic acid and acetic
anhydride respectively resulting in pure compounds (50 to 55%
yield).
[0084] Polymerization Procedure.
[0085] In a typical experiment a 25 ml test tube was charged with
(0.6870 mmol) of dianhydride and (0.6870 mmol) of
m-phenylenediamine (mPD). To the reaction mixture was added 3.6 g
of o-dichlorobenzene (ODCB) as a solvent. The reaction mixture was
refluxed at 180.degree. C. for 4 h. After 4 h, the reaction mixture
was poured into a Teflon coated aluminum foil made into a tube. The
tube was heated in a hot block up to 380.degree. C. for 20 min. to
remove the solvent yielding the N-phenyl phenolphthalein meta
phenylene diamine (mPD) polyetherimide (Example 9) and tetra methyl
BPA mPD polyetherimide (Example 10).
Example 9
##STR00012##
[0086] Example 10
##STR00013##
[0088] Molecular Weight Analysis by GPC.
[0089] Molecular weights were determined by gel permeation
chromatography (GPC) analysis with a Waters 2695 Separations Module
equipped with a Polymer Labs Plgel 5 .mu.m MIXED-C column and
Waters 2487 PDA detector at 254 nm. Elution was effected with
isocratic solvent system of dichloromethane at 1 mL/min and Mw is
reported relative to polystyrene standards obtained from Polymer
Labs. Each sample was run for 15 minutes with an injection volume
of 5 .mu.L.
[0090] TGA and DSC Measurements.
[0091] Thermal Gravimetric Analysis (TGA) measurements were
performed with a TA Q800 TGA. The samples were scanned from
40.degree. C. to 800.degree. C. under nitrogen with a heating rate
of 20.degree. C./min. Differential Scanning calorimetry (DSC)
measurements were performed with a TA Q1000 DSC. The samples were
scanned from 40.degree. C. to 350.degree. C. under nitrogen
atmosphere. The glass transition temperatures (T.sub.g), of the
polymers were determined from the second heating at the rate of
20.degree. C./min.
[0092] Characterization of the polymers of Examples 9 and 10 are
shown in Table 4. The N-phenyl phenolphthalein (PPPBP) mPD
polyetherimde (Example 9) had a Tg of 290.degree. C., the tetra
methyl BPA (TMeBPA) polyetherimide mPD (Example 10) had a Tg of
249.degree. C. both considerably above the 217.degree. C. Tg of the
bisphenol A (BPA) dianhydride based mPD polyetherimide (control
example P).
[0093] The polymers made from the indicated dianhydride and
m-phenylene diamine had weight average molecular weights (Mw) of
49,800 and 56,800 and number average (Mn) molecular weights of
24,300 and 26,800 which were above the BPA dianhydride derived
polyetherimide control (Table 4).
[0094] Thermal gravimetric analyses (TGA) were run in nitrogen to
determine the temperature of peak decomposition. Both the N-phenyl
phenolphthalein and tetra methyl BPA polyetherimides show very good
resistance to decomposition with a peak rate of decomposition above
500.degree. C. The total weight loss at 800.degree. C. was less
than 60% of the starting polymer weight.
TABLE-US-00004 TABLE 4 Polymer Properties peak % wt wt. loss
PEI-MPD GPC GPC Tg loss 800.degree. C. Example Polymer Mw Mn PDI
(.degree. C.) in N.sub.2 (N.sub.2) P BPA 38000 17700 2.15 217 554
49 9 PPPBP 49800 24300 2.05 290 581 45 10 TMeBPA 56800 26800 2.12
249 505 55
Examples 11 to 22
[0095] A further set of polyetherimides, examples 11 to 22 were
prepared from the phenolic monomers: di-tert butyl hydroquinone
(DTBHQ), methyl hydroquinone (MHQ), spiro biindane bisphenol
(SBIBP) and N-phenyl phenyl phenolphthalein (PPPBP) that show no
displacement at the alpha or beta estradiol binding sites at
concentration below the 2.5.times.E-4M. One equivalent of the
disodium salts of the aforementioned bisphenols were separately
reacted with two equivalents of 4-fluoro phthalic anhydride for 1
hr at 170.degree. C. in dimethyl acetamide (DMAC) as described in
the procedure for dianhydride preparation of examples 9 and 10. The
resultant dianhydrides were recovered from solution and purified by
methanol washing and/or recrystallization. The DTBHQ-dianhydride
and MHQ-dianhydride were recrystallized from methanol, the
SBIBP-dianhydride from acetic anhydride and the PPPBP dianhydride
from acetonitrile. The dianhydrides were then polymerized with one
equivalent of meta-phenylene diamine (mPD), para-phenylene diamine
(pPD) or diamino diphenyl sulfone (SDA) in a solution of DMAC at
room temperature for at least 1 hr. to make an amide acid imide
polymer. The 12.5% solids amide acid imide solutions were fully
imidized with removal of DMAC solvent under nitrogen to prepare
thin films by gradually heating from 25 to 375.degree. C. The
heating schedule to remove solvent and complete imidization is
shown in Table 5.
TABLE-US-00005 TABLE 5 Film Casting of Amide Acid DMAC Solution
Time (min.) 0 45 60 90 120 150 165 180 195 225 T .degree. C. 25 40
40 120 120 160 160 200 200 375
[0096] The polyimide films were characterized by: DSC to measure Tg
(20.degree. C./min heating rate), % wt. gain after 24 hr. immersion
in water at 23.degree. C. and the onset of weight loss under
nitrogen and air by thermo gravimetric analysis (TGA). Coefficient
of thermal expansion (CTE) was measured in ppm/.degree. C. by
thermo mechanical analyses during heating from -50 to 170.degree.
C. The data for the various polyetherimides is shown in Table 6.
The polyetherimides of examples 11 to 22 all show high heat
capability with a glass transition temperature (Tg) above
200.degree. C. Good thermal stability was shown by less than 1% TGA
weight loss below 400.degree. C. in either air or nitrogen. A CTE
of 36 to 47 ppm/.degree. C. showed good dimensional stability.
Moisture absorption is 3.15% or less for all the polyetherimides of
Table 6 with many polymers having 2.65% or less weight gain on
immersion in water at 23.degree. C. for 24 hrs. Note that example
20 is a replicate of example 9. In this instance the polymers with
pPD, examples 12 and 15, were too brittle to allow reliable
measurements to be made.
TABLE-US-00006 TABLE 6 Polyetherimide Properties Examples 11 to 22
TGA TGA decomp. decomp. Tg .degree. C. Temp. .degree. C. Temp.
.degree. C. CTE ppm Example Composition (DSC) (N2) (Air) % water
abs -50 to 170.degree. C. 11 DTBHQ-mPD 252 455 468 1.47 44.1 12
DTBHQ-pPD 272 490 490 1.25 film too brittle 13 DTBHQ-SDA 286 474
485 1.27 47.1 14 MHQ-mPD 253 458 450 2.01 41.3 15 MHQ-pPD not
detected 476 462 film too brittle film too brittle 16 MHQ-SDA 275
457 460 2.12 44.8 17 SBIBP-mPD 265 513 517 1.21 41.3 18 SBIBP-pPD
281 513 509 1.47 46.8 19 SBIBP-SDA 285 512 510 1.60 46.2 20
PPPBP-mPD 290 513 551 2.65 36.2 21 PPPBP-pPD 305 522 524 2.83 40.9
22 PPPBP-SDA 309 521 550 3.15 38.7
* * * * *