U.S. patent application number 16/472131 was filed with the patent office on 2020-04-16 for branched polyimide compositions, method of manufacture, and uses thereof.
The applicant listed for this patent is SABIC GLOBAL TECHNOLOGIES B.V.. Invention is credited to Joseph Michael DENNIS, Thomas Link GUGGENHEIM, Lioba Maria KLOPPENBURG, Timothy Edward LONG, Roy Ray ODLE.
Application Number | 20200115501 16/472131 |
Document ID | / |
Family ID | 61054500 |
Filed Date | 2020-04-16 |
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United States Patent
Application |
20200115501 |
Kind Code |
A1 |
ODLE; Roy Ray ; et
al. |
April 16, 2020 |
BRANCHED POLYIMIDE COMPOSITIONS, METHOD OF MANUFACTURE, AND USES
THEREOF
Abstract
A branched polyimide of the formula (I) wherein G is a group
having a valence of t present in an amount 0.01 to 20 mol %, each Q
is independently the same or different, and is a divalent
C.sub.1-60 hydrocarbon group, each M is independently the same or
different, and is --O--, --C(O)--, --OC(O)--, --OC(O)O--, --NHC(O),
--(O)CNH--, --S--, --S(O)--, or --S(O).sub.2--, D is a phenylene,
each V is independently the same or different, and is a tetravalent
C.sub.4-40 hydrocarbon group, each R is independently the same or
different, and is a C.sub.1-20 divalent hydrocarbon group, q is 0
or 1, m is 0 or 1, d is 0 or 1, p is 1 or 2, t is 2 to 6, and each
n is independently the same or different, and is 1 to 1,000,
provided that the total of all values of n is greater than 4.
##STR00001##
Inventors: |
ODLE; Roy Ray; (Mt. Vernon,
IN) ; GUGGENHEIM; Thomas Link; (Mt. Vernon, IN)
; KLOPPENBURG; Lioba Maria; (Mt. Vernon, IN) ;
LONG; Timothy Edward; (Blacksburg, VA) ; DENNIS;
Joseph Michael; (San Jose, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SABIC GLOBAL TECHNOLOGIES B.V. |
Bergen Op Zoom |
|
NL |
|
|
Family ID: |
61054500 |
Appl. No.: |
16/472131 |
Filed: |
December 29, 2017 |
PCT Filed: |
December 29, 2017 |
PCT NO: |
PCT/US2017/068966 |
371 Date: |
June 20, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62441226 |
Dec 31, 2016 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08L 2203/12 20130101;
C08G 73/1071 20130101; C08G 73/1007 20130101; C08L 79/08 20130101;
C08G 73/101 20130101; C08L 2205/03 20130101; C08L 2205/025
20130101; C08G 73/122 20130101; C08L 2203/14 20130101; C08G 73/1046
20130101; C08L 79/08 20130101; C08L 79/08 20130101 |
International
Class: |
C08G 73/10 20060101
C08G073/10 |
Claims
1. A branched polyimide of the formula ##STR00036## wherein G is a
group having a valence of t, present in an amount of 0.01 to 20
mole percent; each Q is independently the same or different, and is
a divalent C.sub.1-60 hydrocarbon group, each M is independently
the same or different, and is --O--, --C(O)--, --OC(O)--,
--OC(O)O--, --NHC(O), --(O)CNH--, --S--, --S(O)--, or
--S(O).sub.2--, D is a phenylene, each V is independently the same
or different, and is a tetravalent C.sub.4-40 hydrocarbon group,
each R is independently the same or different, and is a C.sub.1-20
divalent hydrocarbon group, q is 0 or 1, m is 0 or 1, d is 0 or 1,
p is 1 or 2, t is 2 to 6, when t is 2, G is --O--, --C(O)--,
--OC(O)--, --(O)CO--, --NHC(O), --(O)CNH--, --S--, --S(O)--,
--S(O).sub.2--, or --P(R.sup.a)(O)-- wherein R.sup.a is a C.sub.1-8
alkyl or C.sub.6-12 aryl, and each n is independently the same or
different, and is 1 to 1,000, to 500, r provided that the total of
all values of n is greater than 4.
2. The branched polyimide of claim 1, wherein when t is 3, G is a
nitrogen, phosphorus, or pentavalent P(O); or G is a C.sub.1-60
hydrocarbon group having a valence oft.
3. The branched polyimide of claim 1, wherein G is --O-- when m is
0, or G is pentavalent P(O), a C.sub.6-50 hydrocarbon having at
least one aromatic group, a C.sub.2-20 aliphatic group, a C.sub.4-8
cycloaliphatic group, a C.sub.3-12 heteroarylene, or a polymer
moiety.
4. The branched polyimide of claim 1, wherein q is 1, Q is a
C.sub.6-20 arylene, m is 1, and M is --O--.
5. The branched polyimide of claim 1, wherein V is a group of the
formula ##STR00037## wherein W is --O--, --S--, --C(O)--,
--SO.sub.2--, --SO--, --P(R.sup.a)(.dbd.O)-- wherein R.sup.a is a
C.sub.1-8 alkyl or C.sub.6-12 aryl, --C.sub.yH.sub.2y-- wherein y
is an integer from 1 to 5 or a halogenated derivative thereof, or a
group of the formula --O--Z--O-- wherein Z is an aromatic
C.sub.6-24 monocyclic or polycyclic moiety optionally substituted
with 1 to 6 C.sub.1-8 alkyl groups, 1 to 8 halogen atoms, or a
combination thereof, provided that the valence of Z is not
exceeded.
6. The branched polyimide of claim 1, wherein the branched
polyimide is a branched polyetherimide of the formula ##STR00038##
wherein each Z is independently an aromatic C.sub.6-24 monocyclic
or polycyclic moiety optionally substituted with 1 to 6 C.sub.1-8
alkyl groups, 1 to 8 halogen atoms, or a combination thereof,
provided that the valence of Z is not exceeded.
7. The branched polyimide of claim 6, wherein Z is a divalent group
of the formula ##STR00039## wherein J is --O--, --S--, --C(O)--,
--SO.sub.2--, --SO--, or --C.sub.yH.sub.2y-- wherein y is an
integer from 1 to 5 or a halogenated derivative thereof, and R is
m-phenylene, p-phenylene, bis(4,4'-phenylene)sulfone,
bis(3,4'-phenylene)sulfone, or bis(3,3'-phenylene)sulfone.
8. A method for the manufacture of the branched polyimide of claim
1, the method comprising reacting a polyamine of the formula
##STR00040## and a diamine of the formula H.sub.2N--R--NH.sub.2
with either a dianhydride of the formula ##STR00041## or an
anhydride of the formula ##STR00042## in a solvent and under
conditions effective to provide the branched polyimide, wherein G,
Q, M, D, R, V, q, m, d, p, and t are as defined in claim 1, and
wherein X is a nitro group or halogen.
9. The method of claim 8, further comprising pre-dissolving the
polyamine and the diamine in the solvent before adding the
dianhydride.
10. The method of claim 8, wherein the branched polyimide is a
branched polyetherimide, the method comprising: reacting the
polyamine of the formula ##STR00043## and the diamine of the
formula H.sub.2N--R--NH.sub.2 with the anhydride of the formula
##STR00044## wherein X is defined in claim 8, to provide
intermediate bis(phthalimide)s of the formulas ##STR00045## and
reacting the bis(phthalimide)s with an alkali metal salt of a
dihydroxy aromatic compound having the formula AMO--Z-OAM wherein
AM is an alkali metal, to provide the branched polyetherimide,
wherein G, Q, M, D, R, V, Z, q, m, d, p, and t are as defined in
claim 1.
11. The method of claim 8, wherein the polyamine is of the formulas
##STR00046##
12. The method of claim 8, wherein the dianhydride is
2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, and the
diamine is bis-(4-aminophenyl) sulfone or m-phenylenediamine.
13. The branched polyimide of claim 1, having one or more of the
following properties: a T.sub.g greater than 100.degree. C.; or an
average branch molecular weight of 12,000 to 50,000 grams per mole;
or less than 5 weight percent of a gel, based on the total weight
of the branched polyimide; a polydispersity of 1.5 to 3.0, as
determined by size exclusion chromatography multi-angle light
scattering; or a UL94 rating that is the better than or equal to a
UL94 rating of the same polyimide manufactured without the
polyamine.
14. (canceled)
15. A polymer composition, comprising: 1 to 99 weight percent of
the branched polyimide of claim 1.
16. (canceled)
17. The polymer composition of claim 15, further comprising: a
polymer different from the branched polyimide.
18. The polymer composition of claim 17, wherein the polymer is a
polyacetal, poly(C.sub.1-6 alkyl)acrylate, polyacrylamide,
polyacrylonitrile, polyamide, polyamideimide, polyanhydride,
polyarylene ether, polyarylene ether ketone, polyarylene ketone,
polyarylene sulfide, polyarylene sulfone, polybenzothiazole,
polybenzoxazole, polybenzimidazole, polycarbonate, polyester,
polyetherimide, polyimide, poly(C.sub.1-6 alkyl)methacrylate,
polymethacrylamide, cyclic olefin polymer, polyolefin,
polyoxadiazole, polyoxymethylene, polyphthalide, polysilazane,
polysiloxane, polystyrene, polysulfide, polysulfonamide,
polysulfonate, polythioester, polytriazine, polyurea, polyurethane,
vinyl polymer, or a combination thereof.
19. (canceled)
20. (canceled)
21. The polymer composition of claim 15, further comprising 99 to 1
weight percent of a second polyimide that is not the same as the
branched polyimide, wherein each amount is based on a total weight
of the branched polyimide and the second polyimide.
22. The branched polyimide of claim 1, wherein group G is derived
from a polyamine of the formula ##STR00047## wherein the amount of
the polyamine present during the preparation of the branched
polyimide is substantially the same as the amount of group G
present in the branched polyimide.
23. The method of claim 8, wherein the polyamine is at least one
compound of the formulas (8a) to (8t) ##STR00048## ##STR00049##
##STR00050## ##STR00051## ##STR00052## wherein, in formula (8f), Z
is a divalent C.sub.1-60 hydrocarbon group.
24. The method of claim 8, wherein the polyamine is present in the
reacting step in an amount of 0.01 to 20 mole percent, based on the
total number of moles of amine functionality of the polyamine and
the diamine.
Description
BACKGROUND
[0001] Polyimides (PIs), and in particular polyetherimides (PEIs),
are amorphous, transparent, high performance polymers having a high
glass transition temperature. Polyetherimides further have high
strength, heat resistance, and modulus, and broad chemical
resistance, and thus are widely used in applications as diverse as
automotive, telecommunication, aerospace, electrical/electronics,
transportation, and healthcare. Moreover, PEIs can be recycled,
whereas some PIs are thermosets that cannot be recycled.
[0002] An ongoing challenge associated with polyimides and
polyetherimides is synthesizing desirable polyimides and
polyetherimides having long-chain branches (LCBs). The inclusion of
long-chain branches can influence the melt strength of the
polymers, and can reduce the melt viscosity of higher molecular
weight polymers for a given processing temperature. Furthermore,
long-chain branches can improve shear-thinning and extensional flow
processing over linear analogues. For instance, the introduction of
long-chain branches into polyesters (e.g., poly(ethylene
terephthalate)) can improve melt strength and reduce the rate of
crystallinity.
[0003] Accordingly, there remains a continuing need in the art for
polyimides and polyetherimides that have long-chain branches.
SUMMARY
[0004] A branched polyimide has the formula
##STR00002##
wherein G is a group having a valence of t, present in an amount of
0.01 to 20 mol %, or 0.1 to 20 mol %, or 0.5 to 10 mol %, or 1.0 to
5 mol %, or 1.5 to 4 mol %, or 0.01 to 2 mol %, each Q is
independently the same or different, and is a divalent C.sub.1-60
hydrocarbon group, each M is independently the same or different,
and is --O--, --C(O)--, --OC(O)--, --OC(O)O--, --NHC(O),
--(O)CNH--, --S--, --S(O)--, or --S(O).sub.2--, D is a phenylene,
each V is independently the same or different, and is a tetravalent
C.sub.4-40 hydrocarbon group, each R is independently the same or
different, and is a C.sub.1-20 divalent hydrocarbon group, q is 0
or 1, m is 0 or 1, d is 0 or 1, p is 1 or 2, t is 2 to 6,
preferably 2 to 4, and each n is independently the same or
different, and is 1 to 1,000, preferably 2 to 500, or 3 to 100, the
total of all values of n is greater than 4, preferably greater than
10, or greater than 20, or greater than 50, or greater than 100, or
greater than 250.
[0005] A method for the manufacture of the branched polyimide
includes reacting a polyamine of the formula
##STR00003##
and a diamine of the formula
H.sub.2N--R--NH.sub.2
with a dianhydride of the formula
##STR00004##
in a solvent and under conditions effective to provide the branched
polyimide, wherein G, Q, M, D, R, V, q, m, d, p, and t are as
defined above.
[0006] Another method for the manufacture of a branched
polyetherimide includes reacting a polyamine of the formula
##STR00005##
and a diamine of the formula
H.sub.2N--R--NH.sub.2
with an anhydride of the formula
##STR00006##
wherein X is a nitro group or halogen, to provide intermediate
bis(phthalimide)s of the formulas
##STR00007##
and reacting the bis(phthalimide)s with an alkali metal salt of a
dihydroxy aromatic compound having the formula
AMO--Z--OAM
wherein AM is an alkali metal, to provide the branched
polyetherimide, wherein G, Q, M, D, R, V, Z, q, m, d, p, and t are
as defined above.
[0007] A polyimide composition includes 1 to 99 wt %, or 10 to 90
wt %, or 0.1 to 20 wt %, or 0.5 to 10 wt %, or 1 to 5 wt % of a
branched polyimide; and 91 to 1 wt %, or 90 to 10 wt %, or 99.9 to
80 wt %, or 99.5 to 90 wt %, or 99 to 95 wt % of the above branched
polyimide and a second polyimide that is not the same as the
branched polyimide, wherein each amount is based on the total
weight of the branched polyimide and the polyimide.
[0008] A polymer composition includes the polyimide composition;
and a second polymer that is not the same as the branched polyimide
or the second polyimide.
[0009] An article includes the branched polyimide, the polyimide
composition, or the polymer composition.
[0010] The above described and other features are exemplified by
the following figures and detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] The following figures are exemplary embodiments wherein the
like elements are numbered alike.
[0012] FIG. 1 is a chart showing dianhydrides according to an
embodiment.
[0013] FIG. 2 is a chart showing diamines according to an
embodiment.
[0014] FIG. 3 is a graph of average branch molecular weight (grams
per mole (g/mol), Mb) versus mole percent (mol %) of
tris((p-aminophenoxy)phenyl) ethane (TAPE) as measured by size
exclusion chromatography-multiple angle light scattering (SEC-MALS)
and .sup.1H NMR spectroscopy.
[0015] FIG. 4 is a graph of viscosity (pascal seconds (Pa s),
.eta.) versus shear rate (radians per second (rad/s), .omega.) and
shows a correlation between viscosity and shear rate.
[0016] FIG. 5 is a graph of molecular weight (g/mol) versus mole
percent (% BA, TAPE) versus torque (Newtonmeters, Nm).
[0017] FIG. 6 is a graph of molecular weight (g/mol) versus mole
percent (% BA, TAPE) versus torque (Nm).
[0018] FIG. 7 shows photographs of a homogeneous polyetherimide
with 1 wt % TAPE via a pre-dissolved amines method (left) and a
homogenous polyetherimide with dark gel spots at 1.5 wt % TAPE
prepared by without pre-dissolving in amines (right).
DETAILED DESCRIPTION
[0019] The inventors hereof have discovered that the synthesis of
poly-functional aryl amines (polyamines), and subsequent
polymerization with a dianhydride and a diamine, provides long
chain branched poly(imides) (LCB-PIs) and polyetherimides
(LCB-PEIs). Careful consideration of the reaction conditions and
molar ratios permits the use of higher molar ratios of the
polyamines without forming an insoluble network during the
synthetic steps. In contrast to LCB polyesters, LCB-PEIs prepared
with 0.5 mole percent (mol %) of polyamine had comparable melt
viscosities and processibility as compared to PEIs without the
long-chain branching. Higher incorporation (2 mol %) of the
polyamines into PEI resulted in LCB-PEIs having a reduced melt
viscosity. Furthermore, the chain dispersity increased at the
higher incorporation of the polyamines in the LCB-PEI. The
increased chain distribution includes concentrations of both higher
and lower molecular weight species.
[0020] Such properties are especially useful in the manufacture of
thin-wall parts, where high-flow properties, especially low melt
viscosity under the high shear conditions are important in
injection molding. The LCB-PI and LCB-PEI can satisfy this
criterion and fare better than the linear chained counterpart of
the same molecular weight. Without being bound by theory, under
melt conditions, polymers display shear-thinning property being a
non-Newtonian fluid. An LCB-PI and LCB-PEI can shear thin faster
(akin to any branched polymer over its linear counterpart), giving
lower viscosity and subsequently higher flow rates with less
processing demands. While the viscosity under shear can be lowered
for linear PI or PEI by either increasing the temperature or using
lower molecular weight polymers, such solutions can lead to
degradation at high heat or lower impact properties of the molded
materials, respectively.
[0021] The LCB-PI is a branched polyimide of formula (1) or
(1').
##STR00008##
[0022] In formula (1) and (1'), G is a group having a valence of t,
present in an amount of 0.01 to 20 mol %, or 0.1 to 20 mol %, or
0.5 to 10 mol %, or 1.0 to 5 mol %, or 1.5 to 4 mol %, or 0.01 to 2
mol %, and q is 0 or 1, m is 0 or 1, d is 0 or 1, p is 1 or 2, t is
2 to 6, preferably 2 to 4. In an embodiment, t is 2, and G is
--O--, --C(O)--, --OC(O)--, --(O)CO--, --NHC(O), --(O)CNH--, --S--,
--S(O)--, --S(O).sub.2--, or --P(R.sup.a)(O)-- (wherein R.sup.a is
a C.sub.1-8 alkyl or C.sub.6-12 aryl). In another embodiment, t is
3, and G is nitrogen, phosphorus, or P(O). In still another
embodiment, G is a C.sub.1-60 hydrocarbon group having a valence of
t. In a preferred embodiment, G is --O-- when m is 0, pentavalent
P(O), a C.sub.6-60 hydrocarbon having at least one aromatic group,
for example a C.sub.6-40 aromatic hydrocarbon group, a C.sub.2-20
aliphatic group, a C.sub.4-8 cycloaliphatic group, a C.sub.3-12
heteroarylene, or a polymer moiety; or G is --O--, --S(O).sub.2--,
pentavalent P(O), a C.sub.6-20 aromatic hydrocarbon group, a
C.sub.2-20 aliphatic group, or a C.sub.4-8 cycloaliphatic group. In
a specific embodiment, G is --O--, pentavalent P(O), or a
C.sub.6-50 hydrocarbon having at least one aromatic group. When q,
m, and d are 0, G can be a saturated C.sub.2-20 aliphatic group,
C.sub.3-12 heteroarylene or a polymeric moiety, for example an
amino resin such as a urea-formaldehyde, a melamine-formaldehyde,
or other resin having active amine groups.
[0023] In formula (1) and (1'), each Q is independently the same or
different, and is a divalent C.sub.1-60 hydrocarbon group. In a
preferred embodiment, Q is a C.sub.6-20 arylene, a C.sub.1-20
alkylene, or a C.sub.3-8 cycloalkylene. In a more preferred
embodiment, Q is a C.sub.6-20 arylene.
[0024] In formula (1) and (1'), each M is independently the same or
different, and is --O--, --C(O)--, --OC(O)--, --OC(O)O--, --NHC(O),
--(O)CNH--, --S--, --S(O)--, --S(O).sub.2--. In another embodiment,
M is --O--, --C(O)--, --OC(O)--, --P(R.sup.a)--, or
--P(O)R.sup.a--. In an embodiment, M is --O--, --C(O)--, --OC(O)--,
--P(R.sup.a)--, or --P(O)R.sup.a-- wherein R.sup.a is a C.sub.1-8
alkyl or C.sub.6-12 aryl.
[0025] In formula (1) and (1'), each D is phenylene. In an
embodiment, each D is the same or different, and is m-phenylene or
p-phenylene.
[0026] Further in formula (1) and (1'), each V is independently the
same or different, and is a tetravalent C.sub.4-40 hydrocarbon
group. In an embodiment, V is a C.sub.6-20 aromatic hydrocarbon
group. Exemplary aromatic hydrocarbon groups include any of those
of the formulas (2)
##STR00009##
wherein W is --O--, --S--, --C(O)--, --SO.sub.2--, --SO--,
--P(R.sup.a)(.dbd.O)-- wherein R.sup.a is a C.sub.1-8 alkyl or
C.sub.6-12 aryl, --C.sub.yH.sub.2y-- wherein y is an integer from 1
to 5 or a halogenated derivative thereof (which includes
perfluoroalkylene groups), or a group of the formula --O--Z--O-- as
described in formula (1a) and (1a') below.
[0027] Also in formula (1) and (1'), each R is independently the
same or different, and is a C.sub.1-20 divalent hydrocarbon group.
Specifically, each R can be the same or different, and is a
divalent organic group, such as a C.sub.6-20 aromatic hydrocarbon
group or a halogenated derivative thereof, a straight or branched
chain C.sub.2-20 alkylene group or a halogenated derivative
thereof, a C.sub.3-8 cycloalkylene group or halogenated derivative
thereof, in particular a divalent group of any of formulas (3)
##STR00010##
wherein Q.sup.1 is --O--, --S--, --C(O)--, --SO.sub.2--, --SO--,
--P(R.sup.a)(.dbd.O)-- wherein R.sup.a is a C.sub.1-8 alkyl or
C.sub.6-12 aryl, --C.sub.yH.sub.2y-- wherein y is an integer from 1
to 5 or a halogenated derivative thereof (which includes
perfluoroalkylene groups), or --(C.sub.6H.sub.10).sub.z-- wherein z
is an integer from 1 to 4. In an embodiment R is m-phenylene,
p-phenylene, or a diarylene sulfone.
[0028] Still further in formula (1) and (1'), each n is
independently the same or different, and is 1 to 1,000, preferably
2 to 500, or 3 to 100, provided that the total of all values of n
is greater than 4, preferably greater than 10, more preferably
greater than 20, or greater than 50, or greater than 100, or
greater than 250, or 4 to 50, or 10 to 50, or 20 to 50, or 4 to
100, or 10 to 100, or 20 to 100.
[0029] In another specific embodiment, the branched polyimide of
formula (1) or (1') can be a branched polyetherimide of formula
(1a), preferably (1a')
##STR00011##
wherein G, Q, M, D, R, q, m, d, n, p, and t are as defined in
formula (1) and (1'), and wherein the divalent bonds of the
--O--Z--O-- group are in the 3,3', 3,4', 4,3', or the 4,4'
positions. The group Z in --O--Z--O-- of formula (1a) and (1a') is
a divalent organic group, and can be an aromatic C.sub.6-24
monocyclic or polycyclic moiety optionally substituted with 1 to 6
C.sub.1-8 alkyl groups, 1 to 8 halogen atoms, or a combination
thereof, provided that the valence of Z is not exceeded. Exemplary
groups Z include groups derived from a dihydroxy compound of
formula (4)
##STR00012##
wherein R.sup.a and R.sup.b can be the same or different and are a
halogen atom or a monovalent C.sub.1-6 alkyl group, for example; p'
and q' are each independently integers of 0 to 4; c is 0 to 4; and
X.sup.a is a bridging group connecting the hydroxy-substituted
aromatic groups, where the bridging group and the hydroxy
substituent of each C.sub.6 arylene group are disposed ortho, meta,
or para (preferably para) to each other on the C.sub.6 arylene
group. The bridging group X.sup.a can be a single bond, --O--,
--S--, --S(O)--, --S(O).sub.2--, --C(O)--, or a C.sub.1-18 organic
bridging group. The C.sub.1-18 organic bridging group can be cyclic
or acyclic, aromatic or non-aromatic, and can further comprise
heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or
phosphorous. The C.sub.1-18 organic group can be disposed such that
the C.sub.6 arylene groups connected thereto are each connected to
a common alkylidene carbon or to different carbons of the
C.sub.1-18 organic bridging group. A specific example of a group Z
is a divalent group of formula (4a)
##STR00013##
wherein J is --O--, --S--, --C(O)--, --SO.sub.2--, --SO--, or
--C.sub.yH.sub.2y-- wherein y is an integer from 1 to 5 or a
halogenated derivative thereof (including a perfluoroalkylene
group). In a specific embodiment Z is a derived from bisphenol A,
such that J in formula (4a) is 2,2-isopropylidene.
[0030] In an embodiment in formulas (1), (1'), (1a), and (1a')
(hereinafter collectively "branched polyimide" for convenience) R
is m-phenylene or p-phenylene, bis(4,4'-phenylene)sulfone,
bis(3,4'-phenylene)sulfone, or bis(3,3'-phenylene)sulfone. In this
embodiment, Z can be a divalent group of formula (4a). In an
alternative embodiment, R is m-phenylene or p-phenylene and Z is a
divalent group of formula (4a) and J is 2,2-isopropylidene.
[0031] In some embodiments, the branched polyimide can be a
copolymer, for example a polyetherimide sulfone copolymer
comprising structural units of formulas (1), (1'), (1a), or (1a')
wherein at least 50 mol % of the R groups are of formula (3)
wherein Q.sup.1 is --SO.sub.2-- and the remaining R groups are
independently p-phenylene or m-phenylene or a combination thereof;
and Z is 2,2'-(4-phenylene)isopropylidene. Alternatively, the
branched polyetherimide copolymer optionally comprises additional
structural imide units, for example imide units wherein V is of
formula (2a) wherein R and V are as described in formula (2a), for
example V is
##STR00014##
wherein W is a single bond, --O--, --S--, --C(O)--, --SO.sub.2--,
--SO--, --P(R.sup.a)(.dbd.O)-- wherein R.sup.a is a C.sub.1-8 alkyl
or C.sub.6-12 aryl, or --C.sub.yH.sub.2y-- wherein y is an integer
from 1 to 5 or a halogenated derivative thereof (which includes
perfluoroalkylene groups). These additional structural imide units
can comprise less than 20 mol % of the total number of units, or 0
to 10 mol % of the total number of units, or 0 to 5 mol % of the
total number of units, or 0 to 2 mol % of the total number of
units. In some embodiments, no additional imide units are present
in the branched polyimides other than polyetherimide units.
[0032] The branched polyimides (which as indicated above include
polyimides (1) and (1') and the branched polyetherimides (1a) and
(1a')), can be prepared by methods known in the art, including a
polycondensation or ether-forming polymerization. In any process,
the appropriate amount of a polyamine of formula (8), preferably of
formula (8')
##STR00015##
is introduced during manufacture of the branched polyimides as
described in further detail below. In formula (8) and (8'), G, Q,
M, D, q, m, d, p, and t are defined as described in formulas (1)
(1'), (1a), and (1a').
[0033] Exemplary polyamines (8) and (8') can include any of
formulas (8a)-(8t).
##STR00016## ##STR00017## ##STR00018## ##STR00019##
wherein, in formula (8f), Z is a divalent C.sub.1-600 hydrocarbon
group, or a C.sub.6-40 aromatic hydrocarbon group, a C.sub.2-20
aliphatic group, or a C.sub.4-8 cycloaliphatic group.
[0034] Methods for the synthesis of the polyamines are known in the
art. An exemplary method for the synthesis of the polyamine of
formulas (8) and (8') uses a two-step sequence as exemplified in
Examples 1 and 2. The first step, is a nucleophilic aromatic
substitution of a halogenated aromatic nitro compound (e.g.,
1-chloro-4-nitrobenzene) with a polyphenol (e.g.,
1,1,1-tris(4-hydroxyphenyl) ethane) that is converted to a
polyphenoxide in-situ, providing a sufficiently nucleophilic oxygen
to displace the activated halide. A polar aprotic solvent (e.g.,
dimethylacetamide) can promote the substitution reaction to afford
a poly(nitrophenyl) compound (e.g.,
1,1,1-tris((p-nitrophenoxy)phenyl) ethane). The second step is a
reduction of the poly(nitrophenyl) compound to the polyamine of
formula (10) using, for example, a palladium catalyst with a
reducing agent, an iron-based catalyst, vasicine, zinc, samarium,
and hydrazine.
[0035] The branched polyimide can be prepared by polycondensation,
which includes an imidization of a dianhydride of formula (9) or
formula (9a)
##STR00020##
or a chemical equivalent thereof, with a combination of an organic
diamine of formula (10)
H.sub.2N--R--NH.sub.2 (10)
and a polyamine of formula (8), preferably of formula (8')
##STR00021##
wherein V, Z, R, G, Q, M, D, q, m, d, p, and t are defined as
described in formulas (1), (1'), (1a), and (1a'). The polyamine
(8), preferably (8') can be present in the reaction in an amount of
0.01 to 20 mol %, or 0.1 to 20 mol %, or 0.5 to 10 mol %, or 1.0 to
5 mol %, or 1.5 to 4 mol %, or 0.01 to 2 mol % to achieve increased
branching and increased PDI.
[0036] Exemplary dianhydrides include
3,3-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride;
4,4'-bis(3,4-dicarboxyphenoxy)diphenyl ether dianhydride;
4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride;
4,4'-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride;
4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride;
2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride;
4,4'-bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride;
4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfide dianhydride;
4,4'-bis(2,3-dicarboxyphenoxy)benzophenone dianhydride;
4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfone dianhydride;
4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl-2,2-propane
dianhydride;
4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl ether
dianhydride;
4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl sulfide
dianhydride;
4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)benzophenone
dianhydride; and,
4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl sulfone
dianhydride, as well as various combinations thereof.
[0037] Still other specific dianhydrides include any of those as
shown in FIG. 1, wherein Y' is --C(O)--, --C(CF.sub.3).sub.2--,
--C(CH.sub.3).sub.2--, --SO.sub.2--, or --C.ident.C--.
[0038] Specific examples of organic diamines include
hexamethylenediamine, polymethylated 1,6-n-hexanediamine,
heptamethylenediamine, octamethylenediamine, nonamethylenediamine,
decamethylenediamine, 1,12-dodecanediamine, 1,18-octadecanediamine,
3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine,
4-methylnonamethylenediamine, 5-methylnonamethylenediamine,
2,5-dimethylhexamethylenediamine,
2,5-dimethylheptamethylenediamine, 2, 2-dimethylpropylenediamine,
N-methyl-bis (3-aminopropyl) amine, 3-methoxyhexamethylenediamine,
1,2-bis(3-aminopropoxy) ethane, bis(3-aminopropyl) sulfide,
1,4-cyclohexanediamine, bis-(4-aminocyclohexyl) methane,
m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene,
2,6-diaminotoluene, m-xylylenediamine, p-xylylenediamine,
2-methyl-4,6-diethyl-1,3-phenylene-diamine,
5-methyl-4,6-diethyl-1,3-phenylene-diamine, benzidine,
3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine,
1,5-diaminonaphthalene, bis(4-aminophenyl) methane,
bis(2-chloro-4-amino-3,5-diethylphenyl) methane, bis(4-aminophenyl)
propane, 2,4-bis(p-amino-t-butyl) toluene,
bis(p-amino-t-butylphenyl) ether, bis(p-methyl-o-aminophenyl)
benzene, bis(p-methyl-o-aminopentyl) benzene, 1,
3-diamino-4-isopropylbenzene, bis(4-aminophenyl) sulfide,
bis-(4-aminophenyl) sulfone (also known as 4,4'-diaminodiphenyl
sulfone (DDS)), and bis(4-aminophenyl) ether. Any regioisomer of
the foregoing compounds can be used. Combinations of these
compounds can also be used. In some embodiments the organic diamine
is m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenyl
sulfone, or a combination thereof.
[0039] Still other organic diamines can include any of those as
shown in FIG. 2, wherein A is --O--, --CH.sub.2--,
--CH.sub.2CH.sub.2--, --SO.sub.2, --C(CF.sub.3).sub.2--, --S--,
--S--S--, --CH.dbd.CH--, --C(O)--, --NH--, or
--C(CH.sub.3).sub.2--; A.sub.1 is --Cl, --OH, --OCH.sub.3,
--CH.sub.3, or --CH.sub.2CH.sub.3; A.sub.2 is --CH.sub.3,
--CF.sub.3, or --SO.sub.3H; A.sub.3 is --CH.sub.3 or --OH; and n'
is 1, 2, or 3.
[0040] An endcapping agent can be present during imidization, in
particular a monofunctional compound that can react with an amine
or anhydride. Exemplary compounds include monofunctional aromatic
anhydrides such as phthalic anhydride, an aliphatic monoanhydride
such as maleic anhydride, or monofunctional aldehydes, ketones,
esters isocyanates, aromatic monoamines such as aniline, or
C.sub.1-C.sub.18 linear or cyclic aliphatic monoamines. A
monofunctional bisphthalimide can also be added before or during
imidization. The amount of endcapping agent that can be added
depends on the desired amount of chain terminating agent, and can
be, for example, more than 0 to 10 mole percent (mol %), or 0.1 to
10 mol %, or 0.1 to 6 mol %, based on the moles of endcapping agent
and amine or anhydride reactant.
[0041] A catalyst can be present during imidization. Exemplary
catalysts include sodium aryl phosphinates, guanidinium salts,
pyridinium salts, imidazolium salts, tetra(C.sub.7-24 arylalkylene)
ammonium salts, dialkyl heterocycloaliphatic ammonium salts,
bis-alkyl quaternary ammonium salts, (C.sub.7-24
arylalkylene)(C.sub.1-16 alkyl) phosphonium salts, (C.sub.6-24
aryl)(C.sub.1-16 alkyl) phosphonium salts, phosphazenium salts, and
combinations thereof. The anionic component of the salt is not
particularly limited, and can be, for example, chloride, bromide,
iodide, sulfate, phosphate, acetate, maculate, tosylate, and the
like. A combination of different anions can be used. A
catalytically active amount of the catalyst can be determined by
one of skill in the art without undue experimentation, and can be,
for example, more than 0 to 5 mol % percent, or 0.01 to 2 mol %, or
0.1 to 1.5 mol %, or 0.2 to 1.0 mol % based on the moles of
polyamine (8) or (8') and organic diamine (10).
[0042] A general synthesis of the branched polyetherimides via this
embodiment is shown in Scheme 1.
##STR00022##
In Scheme 1, T can be a group of the formula O--Z--O as described
in formula (1a) and (1a'), and G is a C.sub.1-60 hydrocarbon group
having a valence of 2, or a C.sub.6-40 aromatic hydrocarbon group,
a C.sub.2-20 aliphatic group, or a C.sub.4-8 cycloaliphatic group,
and x'', y'', z'', and p'' each have a value of n as described in
formulas (1), (1'), (1a), and (1a').
[0043] Conditions effective to provide the polyimides are generally
known. Polymerization is generally carried out in a solvent, for
example relatively non-polar solvents with a boiling point above
100.degree. C., or above 150.degree. C., for example
o-dichlorobenzene, dichlorotoluene, 1,2,4-trichlorobenzene,
diphenyl sulfone, or a monoalkoxybenzene such as anisole,
veratrole, diphenylether, or phenetole. Ortho-dichlorobenzene and
anisole can be particularly mentioned. The polymerization is
generally at least 110.degree. C., or 150 to 275.degree. C., or 175
to 225.degree. C. for solution polymerization. At temperatures
below 110.degree. C., reaction rates may be too slow for economical
operation. Atmospheric or super-atmospheric pressures can be used,
for example up to 5 atmospheres, to facilitate the use of high
temperatures without causing solvent to be lost by evaporation.
Effective times depend on the particular reactants and reaction
conditions, and can be 0.5 hours to 3 days, for example, generally
for 0.5 to 72 hours, preferably 1 to 30 or 1 to 20 hours.
Advantageously, the reaction is complete 20 hours or less,
preferably 10 hours or less, more preferably 3 hours or less.
[0044] It has been found that improved compositions can be obtained
by pre-dissolving the polyamine (8), preferably (8'), and the
diamine (10) before adding the dianhydride (9) or (9a), or before
adding the diamine/polyamine to the dianhydride. The catalyst can
be added any time during the reaction between the polyamine (8),
preferably (8'), and organic diamine (10), and the dianhydride (9)
or (9a) continuously or in portions during the course of the
reaction. In some embodiments, the catalyst is added after
pre-dissolution the polyamine (8), preferably (8'), and organic
diamine (10), with the dianhydride (9) or (9a).
[0045] The solvent, polyamine (8), preferably (8'), diamine (10),
dianhydride (9) or (9a), and optional components (e.g., catalyst
and endcapping agent) (i.e., the reaction mixture) can be combined
in amounts such that the total solids content the during the
reaction to form the branched polyimide are 5 to 70 weight percent
(wt %), preferably 10 to 70 wt %, more preferably 20 to 70 wt %.
"Total solids content" expresses the proportion of the reactants as
a percentage of the total weight including liquids present in the
reaction at any given time. It can be desirable to have low water
content in the reaction mixture, for example the reaction mixture
can comprise 200 parts per million by weight (ppm) or less of
water, 100 ppm or less of water, or 50 ppm or less of water, or to
25 ppm or less of water, based on parts by weight of the reaction
mixture.
[0046] A molar ratio of dianhydride (9) or (9a) to a combination of
polyamine (8), preferably (8'), and diamine (10) of 0.9:1 to 1.1:1,
or 1:1 can be used. While other ratios can be used, a slight excess
of dianhydride or diamine may be desirable. A proper stoichiometric
balance between the dianhydride and combination of polyamine (8),
preferably (8'), and diamine (10) is maintained to allow for the
production of the desired molecular weight of the polymer, or
prevent the formation of polymer with significant amounts of amine
end groups. Accordingly, in an embodiment, imidization proceeds via
forming an initial reaction mixture having a targeted initial molar
ratio of dianhydride (9) or (9a) to a combination of polyamine (8),
preferably (8'), and diamine (10); heating the reaction mixture to
a temperature of at least 100.degree. C. to initiate
polymerization; analyzing the molar ratio of the heated reaction
mixture to determine the actual initial molar ratio of dianhydride
(9) or (9a) to polyamine (8), preferably (8'), and diamine (10),
using, e.g., an infrared spectroscopy technique, a titration
technique, or a NMR technique; and, if necessary, adding
dianhydride (9) or (9a), or polyamine (8), preferably (8'), or
diamine (10) to the analyzed reaction mixture to adjust the molar
ratio of dianhydride (9) or (9a) to polyamine (8), preferably (8'),
and diamine (10) to 0.9:1 to 1.1:1.
[0047] If an amine-containing endcapping agent is used, the amount
can be more than 0 to 10 mol % based on the total amount of
dianhydride (9) or (9a). If an anhydride-containing endcapping
agent is used, the amount can be in the range of more than 0 to 20
mol %, or 1 to 10 mol % based on the amount of the polyamine (8),
preferably (8'), and diamine (10) combined. In general, due to the
presence of the polyamines, an anhydride-containing endcapping
agent is used to decrease the number of amine end groups in the
branched polyimides and polyetherimides. The endcapping agent can
be added at any time. In some embodiments, the endcapping agents
are mixed with or dissolved into reactants having the similar
functionality. For example, anhydride-containing endcapping agent
can be combined with dianhydride (9) or (9a). Where an
anhydride-containing endcapping agent is used, in order to achieve
maximum molecular weight, the quantity of amine functionality
([2.times.diamine moles]+[t.times.polyamine, moles wherein t is the
number of reactive amino groups])=moles of anhydride functionality
([2.times.dianhydride moles+moles of anhydride in the endcapping
agent]). As described above, the stoichiometry condition of the
polymerization reaction mixture can be analyzed, and the
stoichiometry corrected if needed to provide a stoichiometry within
+0.2 mol % of a stoichiometry of 1:1.
[0048] In other embodiments, the branched polyimides can be
synthesized by an ether-forming polymerization, which proceeds via
an imidization, i.e., reaction of the polyamine of formula (8),
preferably (8'), and the diamine of formula (10) with an anhydride
of formula (11)
##STR00023##
wherein X is a nitro group or halogen, to provide intermediate
bis(phthalimide)s of the formulas (12a) and (12b)
##STR00024##
wherein G, Q, M, q, m, p, and t are as described in formula (1) and
(1a) and X is as described in formula (11). The polyamine (8),
preferably (8'), can be present in the reaction in an amount of
0.01 to 20 mol %, or 0.1 to 20 mol %, or 0.5 to 10 mol %, or 1.0 to
5 mol %, or 1.5 to 4 mol %, or 0.01 to 2 mol % to achieve increased
branching. An optional catalyst or optional monofunctional chain
terminating agent as described above can be present during
imidization.
[0049] The bis(phthalimide)s (12a) and (12b) are reacted with an
alkali metal salt of a dihydroxy aromatic compound of formula
(13)
AMO--Z--OAM (13)
wherein AM is an alkali metal and Z is as defined above, to provide
the branched polyetherimide. Polymerization conditions effective to
provide the branched polyimides are generally known, and can be
conducted in a solvent as described above. This polymerization can
also be conducted in the melt, for example at 250 to 350.degree.
C., where a solvent is generally not present.
[0050] In another embodiment, an anhydride of formula (11), for
example 4-chlorophthalic anhydride (Cl-PA), is reacted with
meta-phenylenediamine (mPD) to produce the intermediate
bis(phthalimide) (Cl-PAMI). Alternatively, a polyamine of formula
(8'), for example a triamine such as 2,4,4'-triaminodiphenyl ether
(TADE), can be reacted with 4Cl-PA to produce a reactive tris-imide
branching agent. These reactions are illustrated in Scheme 2a.
##STR00025##
The reactive tris-imide branching agent can then be reacted with
the alkali metal salt of a dihydroxy aromatic compound (13) to
provide the branched polyimide. In an exemplary embodiment, the
intermediate bis(phthalimide) of formula (12a) is prepared by
reacting Cl-PAMI with BPA, which can then be reacted with the
alkali metal salt of a dihydroxy aromatic compound of formula (13)
to provide the branched polyimide. This embodiment is shown in
Scheme 2b.
##STR00026##
In other embodiments, other branching phenols such as THPE can be
reacted with Cl-PAMI to provide a tris(phthalimide) intermediate a
shown in Scheme 2c. The tris(phthalimide) intermediate can then be
reacted with the alkali metal salt of a dihydroxy aromatic compound
of formula (13) to provide the branched polyimide.
##STR00027##
[0051] The branched polyimide can have one or more of the following
properties. The branched polyimide can have a T.sub.g greater than
100.degree. C., preferably 100 to 395.degree. C., more preferably
180 to 280.degree. C., even more preferably 200 to 250.degree. C.
The branched polyimide can have an average branch molecular weight
(M.sub.b) of 12,000 to 50,000 grams per mole (g/mol), preferably
15,000 to 40,000 g/mol, more preferably 23,000 to 38,000 g/mol, as
determined by size exclusion chromatography or proton nuclear
magnetic resonance. In some embodiments, the branched polyimide can
have a viscosity of greater than 25,000 pascal-seconds at a
frequency of 0.1 radians per second. The branched polyimide can
have a polydispersity (PDI) of 1.5 to 3.0, as determined by size
exclusion chromatography multi-angle light scattering (SEC-MALS).
The branched polyimide can have a melt index of 0.1 to 10 grams per
minute (g/min), as measured by American Society for Testing
Materials (ASTM) D1238 at 340 to 370.degree. C., using a 6.7
kilogram (kg) weight. The branched polyimide can have a weight
average molecular weight (M.sub.w) of 1,000 to 150,000 g/mol, or
10,000 to 80,000 g/mol, or 20,000 to 60,000 g/mol, as measured by
gel permeation chromatography (GPC), using polystyrene standards,
light scattering, and/or triple point detector. In some
embodiments, the branched polyimide can have an intrinsic viscosity
greater than 0.2 deciliters per gram (dL/g), or, more preferably,
0.35 to 0.7 dL/g, as measured in m-cresol at 25.degree. C.
[0052] In a specific embodiment, the branched polyimide can have
less than 5 wt %, or less than 3 wt %, or less than 1 wt %, or less
than 0.5 wt % of a gel. The gel can be observed visually. In an
embodiment, no gel is observable.
[0053] The branched polyimide can have a UL94 rating of V-1 or
better, as measured following the procedure of Underwriter's
Laboratory Bulletin 94 entitled "Tests for Flammability of Plastic
Materials for Parts in Devices and Appliances" (ISBN
0-7629-0082-2), Fifth Edition, Dated Oct. 29, 1996, incorporating
revisions through and including Dec. 12, 2003. In an embodiment,
the branched polyimide has a UL94 rating of V-0 or V-1 at a
thickness of 0.2, 0.3, 0.5, 0.6, 0.75, 0.9, 1, 1.2, 1.5, 2, 2.5, or
3 mm. In some embodiments, the branched polyimide has a UL94 rating
of V-0 at a thickness of 0.3, 0.5, 0.75, 0.9, 1, 1.5, 2, or 3 mm.
In a preferred embodiment, the branched polyimide has a UL94 rating
of V-0 at a thickness of 0.5 mm or of 1.5 mm. In another preferred
embodiment, the branched polyimide can have a flame retardance that
is greater than or equal to the same polyimide manufactured without
the polyamine (8) or (8').
[0054] As described above, the polyamines (8), preferably (8'), and
diamines (10) are reacted in combination, wherein the polyamine is
present in an amount of 0.01 to 20 mol %, or 0.1 to 20 mol %, or
0.5 to 10 mol %, or 1.0 to 5 mol %, or 1.5 to 4 mol %, or 0.01 to 2
mol % to achieve increased branching and increased PDI. Under these
conditions, it is possible that both branched and unbranched
poly(imides) are formed, to provide a polyimide composition
comprising the branched polyimides and a second polyimide that is
not the same as the branched polyimide. This second polyimide is
generally an unbranched polyimide that comprises more than 1, for
example 5 to 1000, or 5 to 500, or 10 to 100, structural units of
formula (15)
##STR00028##
wherein V and R are as described in formula (1) and (1'). It is
also possible to combine the branched polyimide or polyimide
composition with a second polyimide that is separately
manufactured, and contains a different degree of branching or no
branching, to obtain the polyimide composition. In an embodiment,
the polyimide composition includes 1 to 99 wt %, or 10 to 90 wt %,
or 0.1 to 20 wt %, or 0.5 to 10 wt %, or 1 to 5 wt % of a branched
polyimide and 99 to 1 wt %, or 90 to 10 wt %, or 99.9 to 80 wt %,
or 99.5 to 90 wt %, or 99 to 95 wt % of a second polyimide.
[0055] Similarly, both branched and unbranched poly(etherimides)
can be formed, to provide a polyetherimide composition comprising
the branched polyetherimides (1a) or (1a') and a second
polyetherimide that is not the same as the branched
polyetherimides. This second polyetherimide is generally an
unbranched polyetherimide that comprises more than 1, for example 5
to 1000, or 5 to 500, or 10 to 100, structural units of formula
(16)
##STR00029##
wherein Z and R are as described in formula (1a) and (1a'). In an
embodiment, the polyetherimide composition includes 1 to 99 wt %,
or 10 to 90 wt %, or 0.1 to 20 wt %, or 0.5 to 10 wt %, or 1 to 5
wt % of a branched polyetherimide (1a) or (1a') and 99 to 1 wt %,
or 90 to 10 wt %, 99.9 to 80 wt %, or 99.5 to 90 wt %, or 99 to 95
wt % of a second polyetherimide.
[0056] It is also possible to combine the polyimide composition or
the polyetherimide compositions with a third polymer that is not
the same as the branched polyimide and second polyimide (or the
branched polyetherimide and second polyetherimide). Such polymer
compositions can include 1 to 99 wt % of the polyimide or
polyetherimide composition and 1 to 99 wt % of the third polymer,
or 10 to 90% of the polyimide or polyetherimide composition and 10
to 90 wt % of the third polymer.
[0057] Illustrative examples of third polymers include a
polyacetal, poly(C.sub.1-6 alkyl)acrylate, polyacrylamide,
polyacrylonitrile, polyamide, polyamideimide, polyanhydride,
polyarylene ether, polyarylene ether ketone, polyarylene ketone,
polyarylene sulfide, polyarylene sulfone, polybenzothiazole,
polybenzoxazole, polybenzimidazole, polycarbonate, polyester,
poly(C.sub.1-6 alkyl)methacrylate, polymethacrylamide, cyclic
olefin polymer, polyolefin, polyoxadiazole, polyoxymethylene,
polyphthalide, polysilazane, polysiloxane, polystyrene,
polysulfide, polysulfonamide, polysulfonate, polythioester,
polytriazine, polyurea, polyurethane, vinyl polymer, or a
combination comprising at least one of the foregoing.
[0058] The branched polyimide, the polyimide composition, the
polyetherimide composition, and the polymer composition can include
various additives ordinarily incorporated into compositions of this
type, with the proviso that any additive is selected so as to not
significantly adversely affect the desired properties of the
composition. Exemplary additives include antioxidants, thermal
stabilizers, light stabilizers, ultraviolet light (UV) absorbing
additives, quenchers, plasticizers, lubricants, mold release
agents, antistatic agents, visual effect additives such as dyes,
pigments, and light effect additives, flame resistances, anti-drip
agents, and radiation stabilizers. Other useful additives include
carbon nanotubes, exfoliated nanoclays, carbon nanowires, carbon
nanospheres, carbon-metal nanospheres, carbon nanorods,
carbon-metal nanorods, nanoparticles, or insoluble polymers.
Combinations of additives can be used. The foregoing additives can
be present individually in an amount from 0.005 to 10 wt %, or
combined in an amount from 0.005 to 20 wt %, preferably 0.01 to 10
wt %, based on the total weight of the composition. Particulate
fillers and reinforcing fillers can also be present.
[0059] A wide variety of articles can be manufactured using the
branched polyimide, the polyimide compositions, the polyetherimide
compositions, and the polymer compositions, for example articles of
utility in automotive, telecommunication, aerospace,
electrical/electronics, battery manufacturing, wire coatings,
transportation, food industry, and healthcare applications. Such
articles can include films, fibers, foams (both open- and
closed-cell foams), thin sheets, small parts, coatings, fibers,
preforms, matrices for polymer composites, or the like. In a
particular embodiment, the article is an open- or closed-cell foam,
preferably a closed-cell foam. The articles can be extruded or
molded, for example injection molded. In some embodiments, the
articles can be made by an additive manufacturing method, for
example three dimensional printing. Components for electronic
devices and components for sterilizable medical articles are
preferably mentioned. Thin-wall components manufactured by
injection molding are also preferred, such as a wall having a
thickness from 0.1 to 10 millimeters (mm), or 0.2 to 5 mm, or 0.5
to 2 mm. In some embodiments, a film can be manufactured by
solution-casting or melt processing the branched polyimide, the
polyimide compositions, the polyetherimide compositions, and the
polymer compositions described herein.
[0060] The polyimides and polyetherimides are further illustrated
by the following non-limiting examples.
EXAMPLES
[0061] Table 1 list components that are used in the examples.
Unless specifically indicated otherwise, the amount of each
component is in weight percent in the following examples, based on
the total weight of the composition.
TABLE-US-00001 TABLE 1 Component Description THPE
1,1,1-tris(4-hydroxyphenyl) ethane (Sigma-Aldrich) TADE
2,4,4'-triaminodiphenyl ether (TCI America) 4ClPA 4-chlorophthalic
anhydride (Sigma-Aldrich) Pd/C 10 wt % palladium over carbon
(Sigma-Aldrich) mPD m-phenylene diamine (Sigma-Aldrich) pPD
p-phenylene diamine (Sigma-Aldrich) PA phthalic anhydride (SABIC)
BPA bisphenol A (Sigma-Aldrich) CaO calcium oxide (Sigma-Aldrich)
4-AA 4-amino acetophenone (Sigma-Aldrich) TsOH p-toluenesulfonic
acid (Sigma-Aldrich) oDCB o-dicholorobenzene (Sigma-Aldrich) BPA-DA
2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride
(4,4'-Bisphenol A dianhydride) (SABIC)
[0062] Physical testing of the compositions was conducted according
to the following test methods and procedures. Unless indicated
otherwise, all test standards set forth herein are the test
standards in effect as of 2016.
[0063] Proton nuclear magnetic resonance (.sup.1H NMR) spectroscopy
characterization was performed on a Varian Unity 400 at 399.98 MHz
in deuterated chloroform.
[0064] Carbon nuclear magnetic resonance (.sup.13C NMR)
spectroscopy characterization was performed on a Varian Unity 400
at 100 MHz in deuterated chloroform.
[0065] Glass transition temperature (T.sub.g) and melting
temperature (T.sub.m) were determined using Differential Scanning
Calorimetry (DSC) according to ASTM D3418. The test was performed
using a TA Q1000 DSC instrument. In a typical procedure, a polymer
sample (10-20 milligrams) was heated from 40 to 400.degree. C. at a
rate of 20.degree. C./min, held at 400.degree. C. for 1 minute,
cooled to 40.degree. C. at a rate of 20.degree. C./min, then held
at 40.degree. C. for 1 minute, and the above heating/cooling cycle
was repeated. The second heating cycle is usually used to obtain
the T.sub.g and T.sub.m.
[0066] Average branch molecular weight was determined by size
exclusion chromatography (SEC) and .sup.1H NMR spectroscopy.
Chloroform size exclusion chromatography (SEC) provided absolute
molecular weights using a Waters 1515 Isocratic HPLC Pump and
Waters 717 plus Autosampler with Waters 2414 refractive index and
Wyatt MiniDAWN MALS detectors (flow rate 1.0 mL min.sup.-1).
[0067] Polydispersity was determined by size exclusion
chromatography-multiple angle light scattering SEC-MALS in
chloroform using dn/dc=0.271 or determined by GPC using polystyrene
standards (or a light scattering detector in combination with a
refractive index detector, or a triple detector).
[0068] Weight average molecular weight (M.sub.w) was determined by
SEC or determined by GPC using polystyrene standards (or a light
scattering detector in combination with a refractive index
detector, or a triple detector).
[0069] Torque was determined using a Haake.TM. torque rheometer
from Thermo Scientific.
Example 1: Synthesis of tris((p-nitrophenoxy)phenyl) ethane
(TNPE)
[0070] A general synthesis of (TNPE) is shown in Scheme 3, where R
is 1,1,1-ethane.
##STR00030##
[0071] Specifically, 1,1,1-tris(4-hydroxyphenyl) ethane (20 g, 65.3
millimoles (mmol)), potassium carbonate (45.1 g), dimethylacetamide
(115 milliliter (mL)), and toluene (58 mL) were charged to a
three-necked, 500-mL, round-bottomed flask. A Dean-Stark trap with
condenser, glass stir rod with Teflon blade and glass bearing, and
rubber septa were attached to each of the three necks,
respectively. Purging the whole setup with nitrogen for 20 minutes
(min) provided an inert atmosphere. Next, the round-bottomed flask
was lowered into a 180.degree. C. preheated oil bath resulting in a
reflux of toluene to the Dean-Stark trap. Deprotonation of the
phenol proceeded at 180.degree. C., and was monitored through
collection of water in the Dean-Stark trap. Once water removal
ceased, toluene removal proceeded by distillation through the
Dean-Stark trap. A solution of 1-chloro-4-nitrobenzene (33.9 g,
215.5 mmol) in dimethylacetamide (115 mL) was charged drop-wise to
the reaction. After addition of the 1-chloro-4-nitrobenzene, the
resulting solution color changed from pale pink to dark brown. The
reaction proceeded at 180.degree. C. overnight to afford a
heterogeneous dark brown solution.
[0072] Filtration of the heterogeneous solution through a fritted
funnel equipped with a Celite cake (2.5 cm.times.15 cm) resulted in
a brown, transparent solution. Precipitation into 1.0 molar (M)
NH.sub.4OH aqueous solution afforded a fine, yellow precipitate.
The yellow precipitate was filtered and washed until a filtrate pH
of 7 was obtained, and then the precipitate was dried in-vacuo at
120.degree. C. overnight. Recrystallization from ethyl acetate
isolated the target compound in >90% overall yield. NMR
spectroscopy and mass spectrometry confirmed the structure and
purity.
Example 2: Synthesis of tris((p-aminophenoxy)phenyl) ethane (TAPE)
via Pd--C Reduction
[0073] A general synthesis of
tris((p-aminophenoxy)phenyl)-1,1,1-ethane (TAPE) is shown in Scheme
4 wherein R is 1,1,1-ethane.
##STR00031##
[0074] In particular, tris((p-nitrophenoxy)phenyl) ethane (60 g,
89.6 mmol) and tetrahydrofuran (270 mL) were charged to the Parr
reactor, and subsequently purged with nitrogen for 20 minutes.
Next, 10 wt % palladium over carbon (10 g) was added, and the
reactor sealed and purged with nitrogen for 20 minutes. Three
successive cycles of pressurizing the reactor to 100 psi with
hydrogen ensured saturation of the solution with hydrogen, and the
reaction proceeded under 100 psi of hydrogen pressure. After 24
hours, the pressure was released and the black, heterogeneous
solution was recovered. Filtration of the heterogeneous solution
through a fritted funnel equipped with a Celite cake (2.5
cm.times.15 cm) resulted in a brown, transparent solution.
Evaporation of the solvent afforded the target compound as a light
brown powder in a 98% yield.
[0075] The complete synthesis of tris((p-aminophenoxy)phenyl) 1,1,1
ethane (TAPE) is shown in Scheme 5.
##STR00032##
[0076] Further purification of TAPE was afforded by flash column
chromatography on silica gel using ethyl acetate and hexanes, and
further including tetrahydrofuran and triethylamine as
co-eluents.
Example 3: Synthesis of tris((p-aminophenoxy)phenyl) ethane (TAPE)
via Hydrazine Reduction
[0077] Tris((p-nitrophenoxy)phenyl) ethane (60 g, 89.6 mmol), 10 wt
% palladium over carbon (10 g), and tetrahydrofuran (200 mL) were
charged to a two-necked, round-bottomed, 500 mL flask. The flask
was equipped with a condenser and addition funnel and subsequently
purged with nitrogen for 20 minutes. A solution of hydrazine (537.6
mmol) in tetrahydrofuran (70 mL) was added to the addition funnel.
Under a constant nitrogen purge, the round-bottomed flask was
heated to 80.degree. C. Over the course of 1 h, the hydrazine
solution was added dropwise to the round-bottomed flask. After
addition, the reaction was maintained at 80.degree. C. and reflux
for several hours until the reaction was completed (98% yield).
Example 4: Synthesis of tris(p-aminophenyl)benzene (TAPB)
[0078] The synthesis of tris(p-aminophenyl)benzene (TAPB) is shown
in Scheme 6.
##STR00033##
[0079] The synthesis of 1,3,5-triphenylbenzene, and related
derivatives, is by an acid catalyzed cyclotrimerization of
acetophenone or a derivative thereof, which provides a one-step
method for making a triamine without hydrogenation of a nitro
derivative. The trimerization of 4-amino acetophenone to give
1,3,5-tris(4-aminophenyl)benzene in a one-pot reaction is low
yielding (.about.5%) due to the unfavorable side reaction which
yields a polyamine. This can be overcome by protecting the amine
group during the reaction. Protecting the amine by preparing an
ammonium salt results in an increase in product yield.
Example 5. Synthesis of tris(p-aminophenyl)benzene (TAPB)
[0080] Tris(p-aminophenyl)benzene (TAPB) is synthesized from an
ammonium salt of 4-amino acetophenone (4-AA), as shown in Scheme
7.
##STR00034##
[0081] An acetone solution of 4-AA is added to an acetone solution
of p-toluenesulfonic acid (TsOH), where the TsOH is provided in a
20% molar excess of the 4-AA. Immediate precipitation of the
ammonium tosylate salt is observed. This is filtered, dried (1.4
g), and placed in a round bottom flask with TsOH (20%, as a
catalyst) and heated at 160.degree. C. overnight. The resulting
dark red material is washed with a saturated aqueous NaHCO.sub.3
solution, extracted into methylene chloride, and dried with
MgSO.sub.4. The solvent was removed by rotary evaporation under
vacuum to give a crude red product. A purified yellow product is
obtained after flash column chromatography on silica gel with ethyl
acetate and hexanes as eluents (elution gradient of 0-40% ethyl
acetate over 25 minutes), to obtain the TAPB (.about.20%
yield).
Example 6: Synthesis of Long-Chain Branched Polyetherimides
(LCB-PEIs)
[0082] A synthesis of a 45 kg/mol polyetherimide branched with 1
mol % of TAPE follows as an example. TAPE (0.12 g, 0.34 mmol),
m-phenylene diamine (5.52 g, 51.0 mmol), and o-dichlorobenzene (75
mL) were charged to a three-necked, 500-mL, round-bottomed flask.
The flask was then equipped with a rubber septum, glass stir rod
with Teflon blade, and Dean-Stark trap. A condenser completed the
set up on the Dean-Stark trap, and the contents purged with
nitrogen for 20 minutes. The round-bottomed flask was then heated
to 100.degree. C. to generate a homogeneous solution. Next, BPA-DA
(26.3 g, 50.6 mmol), phthalic anhydride (PA) (0.691 g, 4.6 mmol),
and oDCB (25 mL) were added. The flask was then heated to
180.degree. C., where the reaction proceeded for 18 hours.
Devolatilization of the solvent and thermal imidization was
completed utilizing a melt kneader operating at 380.degree. C.,
resulting in an orange, transparent product.
Example 7: Synthesis of Long-Chain Branched Polyetherimides
(LCB-PEIs)
[0083] The synthetic procedure of Example 6 was followed to prepare
larger batches of long-chain branched polyetherimides.
Specifically, a 500 mL, 3-neck round, bottom-flask connected to a
stirrer and a Dean-Stark trap was charged with mPD (16.8 g, 155
mmol) and TAPE via an addition funnel. Degassed oDCB (120 mL) was
then added and residual solids from the sides of the flask were
rinsed into the solution. While stirring, the flask was lowered
into an oil bath pre-heated to 80.degree. C. The mixture of amines
was stirred for 30 minutes under N.sub.2, and the temperature was
slowly increased to 100.degree. C. over the course of 15 minutes. A
flashlight was used to ensure the complete solvation of the amines.
BPA-DA (80 g, 154 mmol) and PA (2.1 g, 14 mmol) were then slowly
added to the amine solution using additional oDCB (120 mL). The
temperature of the oil-bath was then raised to 160.degree. C.
Stirring was gradually slowed to a halt as the heterogeneous
mixture began to react and clump, and water vapor begins to release
at a temperature of around 140.degree. C. Once the clumped material
begins to dissolve, stirring is resumed and a homogeneous
amber-yellow solution is obtained after 20-30 hours. The
temperature is then increased to 190.degree. C. and a
stoichiometric analysis is performed after 1.5-3 hours. For
example, if the polymer media is found to be rich in mPD by 0.5-1
mol %, then an appropriate additional amount of BPA-DA can be
added. The temperature is then lowered to 170.degree. C. and after
24 hours of heating, a second stoichiometric analysis is performed
to evaluate if stoichiometric conditions are met. The polymer is
then let to heat for an additional 24 h if desired. The reaction
product is subsequently isolated by precipitation with hexanes (2-3
L) in an industrial blender or in the vessel of a Haake
rheometer.
Example 8: Synthesis of bis(2,4-dinitrophenoxy)bisphenol A
[0084] Synthesis of bis(2,4-dinitrophenoxy)bisphenol A follows
similar procedures as Example 1. Bisphenol A (24.4 g, 107 mmol),
potassium carbonate (24 g), dimethylacetamide (150 mL), and toluene
(75 mL) were charged to a three-necked, 500-mL, round-bottomed
flask. A dean-stark trap with condenser, glass stir rod with Teflon
blade and glass bearing, and rubber septa was attached to the three
necks, respectively. Purging the whole setup with nitrogen for 20
min provided an inert atmosphere. Next, the round-bottomed flask
was lowered into a 180.degree. C. preheated oil bath resulting in a
reflux of toluene to the Dean-Stark trap. Deprotonation of the
phenol proceeded at 180.degree. C., and was monitored through
collection of water in the Dean-Stark trap. Once water removal
ceased, toluene removal proceeded by distillation through the
Dean-Stark trap. A solution of 1-chloro-2,4-dinitrobenzene (45.5 g,
225 mmol) in dimethylacetamide (150 mL) was charged drop-wise to
the reaction. After addition of the 1-chloro-2,4-dinitrobenzene,
the resulting solution color changed from pale pink to dark brown.
The reaction proceeded at 180.degree. C. overnight to afford a
heterogeneous dark brown solution.
[0085] Filtration of the heterogeneous solution through a fritted
funnel equipped with a Celite cake (2.5 cm.times.15 cm) resulted in
a brown, transparent solution. Precipitation into 1.0 M NH.sub.4OH
aqueous solution afforded a fine, yellow precipitate. The yellow
precipitate was filtered and washed until a filtrate pH of 7 was
obtained, and then the precipitate was dried in-vacuo at
120.degree. C. overnight. (92% yield).
Example 9: Synthesis of bis(2,4-diaminophenoxy)bisphenol A
[0086] Reduction of bis(2,4-dinitrophenoxy)bisphenol A to
bis(2,4-diaminophenoxy)bisphenol A follows similar procedures as
Example 2. Bis(2,4-dinitrophenoxy)bisphenol A (55 g, 98.1 mmol) and
tetrahydrofuran (250 mL) were charged to a Parr reactor, and
subsequently purged with nitrogen for 20 minutes. Next, 10 wt %
palladium over carbon (10 g) was added, and the reactor sealed and
purged with nitrogen for 20 minutes. Three successive cycles of
pressurizing the reactor to 100 psi with hydrogen ensured
saturation of the solution with hydrogen, and the reaction
proceeded under 100 psi of hydrogen pressure. After 24 hours, the
pressure was released and the black, heterogeneous solution was
recovered. Filtration of the heterogeneous solution through a
fritted funnel equipped with a Celite cake (2.5 cm.times.15 cm)
resulted in a brown, transparent solution. Evaporation of the
solvent afforded the target compound as a light brown powder.
Example 10: Synthesis of
bis(3,5-diaminobenzylcarboxy)hydroquinone
[0087] Synthesis of multi-functional aryl-amines based on aromatic
esters is illustrated by the synthesis of
bis(3,5-diaminobenzylcarboxy)hydroquinone and is shown in Scheme
10.
##STR00035##
[0088] 3,5-Dinitrobenzoic acid (4.0000 g, 18.856 mmol) and
hydroquinone diacetate (1.8307 g, 9.428 mmol) were charged to a
one-neck, 100-mL, round-bottomed flask. The flask was then equipped
with a metal stir rod with metal blade, a t-neck glass adapter with
a gas inlet, stir rod adapter, and outlet, and condensing tube
connected to a collection flask. The contents were purged with
nitrogen for 20 minutes. Under constant nitrogen flow, the
round-bottomed flask was then heated to 160.degree. C. to generate
a melt. The reaction proceeded for 8 h and the removal of acetic
acid helped monitor the reaction progress. The resulting materials
were collected, washed, and purified. Reduction of the nitro group
followed the same procedure as discussed in Example 3.
Example 11: Synthesis of Long-Chain Branched Polyetherimides
[0089] Synthesis of long-chain branched follows similar procedures
as Example 6. The synthesis of a 36 kg/mol polyetherimide branched
with 1 mol % of bis(2,4-diaminophenoxy)bisphenol A follows.
[0090] Bis(2,4-diaminophenoxy)bisphenol A (0.267 g, 0.26 mmol),
m-phenylene diamine (5.57 g, 51.4 mmol), and o-dichlorobenzene (75
mL) were charged to a three-necked, 500-mL, round-bottomed flask.
The flask was then equipped with a rubber septum, glass stir rod
with Teflon blade, and Dean-Stark trap. A condenser completed the
set up on the Dean-Stark trap, and the contents were purged with
nitrogen for 20 minutes. The round-bottomed flask was then heated
to 100.degree. C. to generate a homogeneous solution. Next, BPA-DA
(26.3 g, 50.6 mmol), phthalic anhydride (0.494 g, 3.3 mmol), and
o-dichlorobenzene (25 mL) were added. The flask was then heated to
180.degree. C., where the reaction proceeded for 18 hours.
Devolatilization of the solvent and thermal imidization was
completed utilizing a melt kneader operating at 380.degree. C.,
resulting in an orange, transparent product.
Example 12: Long-Chain Branched Polyetherimides
[0091] Table 2a shows the M.sub.w for a series of long-chain
branched polyetherimides synthesized in the presence of different
amounts of TAPE, as determined by SEC-MALS in chloroform with
dn/dc=0.271. Table 2b shows the absolute M.sub.w for the same PEIs,
as determined by a triple point detector in chloroform.
TABLE-US-00002 TABLE 2a TAPE (mol %) Targeted M.sub.w 0 0.11 0.26
0.56 0.92 1.1 1.3 1.5 2 2.5 3 (kg/mol) Measured M.sub.w
(kg/mol).sup.a 45 40.2 42.4 39.9 39.7 33.5 40.7 40.7 44.2 36.4 35.7
39.1 40 30.3 36.8 29.8 36.1 56.2 36.2 38.6 35.4 31.2 40.0 41.3 35
31.6 36.0 39.0 33.6 34.4 37.6 28.7 32.7 N/A N/A N/A 30 37.2 N/A N/A
30.0 28.4 27.7 29.1 26.8 N/A N/A N/A .sup.aStd. dev. = 5%
TABLE-US-00003 TABLE 2b TAPE (mol %) Targeted M.sub.w 0 0.11 0.26
0.56 0.92 1.1 1.3 1.5 2 2.5 3 (kg/mol) Measured Absolute M.sub.w
(kg/mol).sup.a 45 47.8 53.8 48.0 43.1 38.2 49.5 50.0 50.3 48.3 45.7
47.2 40 33.1 44.1 42.1 43.8 62.2 47.6 43.1 45.0 42.5 44.5 42.8 35
36.2 41.3 49.4 39.9 36.2 39.4 31.3 36.9 N/A N/A N/A 30 32.4 N/A N/A
33.0 34.2 32.6 32.6 33.4 N/A N/A N/A .sup.aStd. dev. = 5%
[0092] Minimal changes in polydispersity are observed at
incorporations below 1.0 mol % TAPE, but at relatively higher
incorporations of the triamine, the polydispersity dramatically
increases. With targeted M.sub.w closely matching measured values,
a direct correlation between branching and dispersity is
achieved.
[0093] Coupling the SEC molecular weight information with .sup.1H
NMR spectroscopy enabled determination of the average molecular
weight of the branches (M.sub.b) as shown in FIG. 3, where the top
solid line corresponds to predicted values for M.sub.b of 30 kg/mol
and the bottom solid line corresponds to predicted values for
M.sub.b of 15 kg/mol. Without being bound by theory, at higher
incorporations of polyamine, greater deviations between the
experimental data and the theoretical predictions are observed,
which can be as a result of increased cyclization. Furthermore, the
M.sub.b remains greater than the molecular weight of the
entanglements (M.sub.e), which may indicate that these long-chain
branches are of significant length to entangle. Overall, these
results are consistent with long chain branching in the branched
PEIs.
[0094] DSC was used to identify the thermal transitions of the
LCB-PEIs, and the results are shown in Table 3.
TABLE-US-00004 TABLE 3 TAPE (mol %) M.sub.w 0 0.11 0.26 0.56 0.92
1.1 1.3 1.5 2 2.5 3 (kg/mol) Measured T.sub.g (.degree. C.) 45 214
215 213 214 214 213 210 216 209 209 207 40 212 214 212 220 214 210
212 210 212 207 213 35 212 212 211 214 212 210 210 210 N/A N/A N/A
30 212 N/A N/A 212 212 210 208 N/A N/A N/A N/A
[0095] The observation of a glass transition temperature (T.sub.g)
near 215.degree. C. correlated well to linear PEI controls. Without
being bound by theory, increasing the amount of the branching agent
may not significantly affect the onset of segmental motion. The
relatively low concentration of long-chain branches
(M.sub.b>>M.sub.e) may not significantly promote or retard
the onset of segmental motion, and may allow for the use of these
branched materials in typical PEI applications. However,
introduction of the long-chain branches affects the rheological
properties.
Example 13: Long-Chain Branched Polyetherimides
[0096] In an exemplary procedure, TADE, m-phenylene diamine, and
BPA-DA were reacted in the presence of either phthalic anhydride or
aniline as an endcapping agent. The LCB-PEI was obtained following
imidization according to the procedure of Example 11.
[0097] DSC was used to identify the thermal transitions of the
LCB-PEIs prepared using TADE and different endcapping agents, and
the results are shown in Table 4.
TABLE-US-00005 TABLE 4 Target M.sub.w TADE Tg Endcapping (kg/mol)
(mol %) (.degree. C.) Agent 38 0.1 216 PA 38 0.5 211 Aniline 38 1
214 PA 38 1.5 211 PA 40 3 215 Aniline 38 3 213 PA 38 4.4 212
Aniline
[0098] As shown in Table 4, the use of triamine branching agents
such as TADE provides LCB-PEIs having glass transition temperatures
from 210 to 215.degree. C. These results are similar to those
observed with TAPE as branching agent and also correlated well to
linear PEI controls.
Example 14: Properties of Long-Chain Branched Polyetherimides
[0099] Measurement of viscosity as a function of angular frequency
provided insight into the processibility of the LCB-PEIs as
compared to the linear analogues. Comparing samples with molecular
weights within the SEC-instrumental margin of error helped to
isolate the long-chain branching effects from the molecular weight
effects. FIG. 4 shows the viscosity profiles of the LCB-PEIs having
various branching densities.
[0100] Across the relevant processing window of 0.1 to 100 rad/s,
the PEIs with a greater incorporation of branching agent (>2.0
mol %) demonstrated significant reductions in the observed melt
viscosity. Without being held to theory, it is believed that the
length and the dispersity of polymer chains and branches play an
instrumental role in this observation. As noted above, the
dispersity of the polymer increased with greater incorporations of
TAPE. As a result, the lower molecular weight chains and branches
may help to plasticize the melt and reduce the overall viscosity.
In contrast, the lower incorporations of TAPE had an increased melt
viscosity as compared to the linear analogue. The M.sub.b at these
incorporations were relatively long and their distribution does not
involve the molecular weights that plasticize the melt.
Example 15: Long-Chain Branched Polyetherimides
[0101] A second series of LCB-PEIs with varying amounts of TAPE
were prepared on a small scale (ca. 4 g). Samples were prepared
with 0, 0.3, 0.6, 1.0 and 3.0 mol % of TAPE, and each sample
included 3.07 mol % of an endcapping agent. The solutions obtained
were homogeneous, with the exception of the LCB-PEI prepared using
3.0 mol % TAPE, which was a dark brown gel-like material a few
millimeters wide.
[0102] Table 5 shows the apparent weight average molecular weight
(Apparent M.sub.w), absolute weight average molecular weight
(Absolute M.sub.w), polydispersity (PDI), and PDI*, respectively,
obtained for the second series of LCB-PEIs prepared with different
amounts of TAPE.
TABLE-US-00006 TABLE 5 .sup..dagger-dbl.Apparent M.sub.w/ TAPE (mol
%) .sup..dagger.Absolute M.sub.w (g/mol) PDI* (M.sub.z/M.sub.w) PDI
(M.sub.w/M.sub.n) 0 53,552.sup..dagger-dbl./38,094.sup..dagger.
1.62.sup..dagger-dbl./1.61.sup..dagger.
2.68.sup..dagger-dbl./1.54.sup..dagger. 0.3
57,860.sup..dagger-dbl./42,305.sup..dagger.
1.72.sup..dagger-dbl./1.78.sup..dagger.
2.79.sup..dagger-dbl./1.62.sup..dagger. 0.6
56,731.sup..dagger-dbl./43,125.sup..dagger.
2.05.sup..dagger-dbl./2.07.sup..dagger.
2.91.sup..dagger-dbl./1.75.sup..dagger. 1.0
74,295.sup..dagger-dbl./58,400.sup..dagger.
2.46.sup..dagger-dbl./2.33.sup..dagger.
3.77.sup..dagger-dbl./1.98.sup..dagger. 3.0
163,529.sup..dagger-dbl./280,607.sup..dagger.
3.85.sup..dagger-dbl./6.55.sup..dagger.
7.60.sup..dagger-dbl./5.57.sup..dagger. .sup..dagger-dbl.GPC data
based on polystyrene standard; .sup..dagger.Data from GPC coupled
with triple-detector Note: GPC integrations for apparent M.sub.w
include the small overlapping lower M.sub.w peaks. Hence, higher
than theoretical PDI is observed but the trends are consistent.
[0103] The data in Table 5 shows an exponential increase in the
M.sub.w correlated to an increase in the amount of branching agent.
This increase is also reflected in the polydispersity index (PDI)
and PDI* values, which indicated a broader M.sub.w distribution and
more branching, respectively, as the amount of TAPE is increased in
the samples.
Example 16: Long-Chain Branched Polyetherimides
[0104] A third series of LCB-PEIs with varying amounts of TAPE were
prepared on a larger scale (ca. 80 g). LCB-PEIs were prepared with
0, 0.5, and 1.5 mol % TAPE, and each sample included 3.07 mol % of
an endcapping agent. After 21 hours of reaction time, the control
sample (0 mol % TAPE) was a clear amber solution, while the samples
prepared with 0.5 and 1.5 mol % TAPE were dark gels interspersed
throughout the solution media. These gels were found to be
insoluble even in a 30% hexafluoroisopropanol in methylene chloride
solution. While GPC data on the soluble mixture does show an
increase in M.sub.w and PDI* with higher amounts of TAPE, it is to
be noted that a homogeneous branched polymer mixture is not
obtained when the reagents are first combined in oDCB and then
heated with stirring. This method, at least at the larger scale,
appears to cause higher molecular weight PEIs to rapidly form in
isolated regions and results in gel spots.
[0105] The torque was measured after 15 minutes for each of the
LCB-PEIs of the third series of samples. The torque increased based
on the increase in M.sub.w, which in turn was as a result of higher
incorporation of TAPE loading (FIG. 5).
Example 17: Long-Chain Branched Polyetherimides
[0106] To achieve branching homogeneity in the polymer mixtures, an
alternate method of preparation was explored. A fourth series of
LCB-PEIs were prepared on a smaller scale (ca. 4 g). The LCB-PEIs
each included 1 wt % of TAPE, with variations between the M.sub.w
for each of the PEIs. Three of the samples were prepared from
amines that were pre-dissolved in a heated oDCB solution, whereas
the other three samples were prepared by way of a "regular
addition"-all reagents were combine in oDCB and then heated with
stirring. The appearance of the resulting polymer mixtures after
reaching stoichiometric conditions were evaluated and physical
properties were identified by GPC. These results are shown in Table
6.
TABLE-US-00007 TABLE 6 Entry Method Gel spots M.sub.w (g/mol) PDI*
PDI 1 Regular yes 49,071 2.046 3.12 2 Pre-dissolved no 58,397 2.295
3.69 3 Pre-dissolved no 56,311 2.052 3.42 4 Regular yes 64,054
2.008 3.36 5 Pre-dissolved no 68,346 2.222 3.92 6 Pre-dissolved no
66,393 2.282 3.81 Note: GPC data collected at 32.degree. C. Values
are underestimated by ~5 to 9 kg/mol, but trends are consistent.
The PDI values are larger as the smaller traces of low M.sub.w
peaks were integrated as well.
[0107] The polymer mixtures prepared via the pre-dissolved amines
method appeared homogeneous and lighter in color, and gels did not
form. The samples prepared by the regular addition method--where
the reagents were combined and heated together with oDCB, had a
darker color and gel spotting was observed. In addition, the
M.sub.w of the PEIs prepared by the pre-dissolved amines method
were heavier than the PEIs prepared by the regular addition method
by 4 to 9 kg/mol.
[0108] An additional large scale preparation (ca. 80 g) of LCB-PEIs
was used to determine the efficacy of the pre-dissolved amines
method on the synthesis of LCB-PEIs with 1 mol % of TAPE. After 21
hours of reaction time and reaching stoichiometric conditions, no
gels were observed. In contrast, a larger scale preparation of
LCB-PEIs that were prepared by the regular addition method, wherein
all reagents are added cool and heated together with oDCB, formed
gels with as little as 0.5 mol % TAPE. Upon closer inspection,
smaller dark specks can be observed in the polymer media, but this
could very well be the charred unreacted 5% impurity present in the
triamine. The GPC and torque data are displayed in FIG. 6. The
M.sub.w of the LCB-PEIs obtained with 1 mol % TAPE using the
pre-dissolved amines method is similar to the data obtained for the
LCB-PEIs prepared with 1.5 mol % TAPE using the regular addition
method. This further validates that the pre-dissolved amines method
provides more efficient branching, which also translated into a
decreased amount of gel formation. Pictures of the polymer media at
the end of these reactions are shown in FIG. 7.
Example 18. Endcapping Agent
[0109] With the method of preparation for LCB-PEIs shown to be
important in preventing the formation of gel spots, LCP-PEIs with
varying degrees of branching were synthesized at a targeted M.sub.w
by the incorporation of additional amounts of endcapping agent
(phthalic anhydride) to cap the additional endgroups introduced by
the TAPE branching agent. A series of LCB-PEIs were prepared with
0.3, 0.5, 1.0, and 1.5 mol % TAPE on an 80 g scale by
pre-dissolving the amines in hot oDCB followed by the addition of
anhydrides. The polymers were heated for 2 days under
stoichiometric conditions and then precipitated as white flakes in
hexanes in a large industrial blender. GPC measurements on the
stoichiometric films after 1 day of heating shows that the M.sub.w
was centered around 51 kg/mol.+-.3 kg/mol (Table 7). The formation
of gels was not observed in any of the samples. Tiny black specks
were observed for 1.0 and 1.5 mol % TAPE samples, but are
attributed to charred triamine impurities (presumably more visible
in these two batches due to higher loadings), as described
herein.
TABLE-US-00008 TABLE 7 TAPE (mol %) M.sub.w (g/mol) PDI* PDI 0
54,437 1.597 2.08 0.3 52,087 1.654 2.10 0.5 48,203 1.674 2.11 1.0
55,434 1.857 2.31 1.5 48,770 1.916 2.35 M.sub.w is from integration
of the major GPC trace, and excluding the smaller low M.sub.w
peaks. GPC data is from stoichiometric films after 1 day of
heating.
[0110] The experiments revealed that LCB-PEIs with varying degrees
of branching at a targeted M.sub.w can be prepared without the
formation of gels in the polymer media. This can be successfully
done using the pre-dissolved amines method.
[0111] In a separate set of experiments, no differences were
observed in the M.sub.w for LCB-PEIs prepared using different
endcapping agents (PA versus aniline).
[0112] This disclosure is further illustrated by the following
aspects.
[0113] Aspect 1. A branched polyimide of formula (1), preferably
formula (1'), wherein G is a group having a valence of t, present
in an amount of 0.01 to 20 mol %, or 0.1 to 20 mol %, or 0.5 to 10
mol %, or 1.0 to 5 mol %, or 1.5 to 4 mol %, or 0.01 to 2 mol %,
each Q is independently the same or different, and is a divalent
C.sub.1-60 hydrocarbon group, each M is independently the same or
different, and is --O--, --C(O)--, --OC(O)--, --OC(O)O--, --NHC(O),
--(O)CNH--, --S--, --S(O)--, or --S(O).sub.2--, D is a phenylene,
each V is independently the same or different, and is a tetravalent
C.sub.4-40 hydrocarbon group, each R is independently the same or
different, and is a C.sub.1-20 divalent hydrocarbon group, q is 0
or 1, m is 0 or 1, d is 0 or 1, p is 1 or 2, t is 2 to 6,
preferably 2 to 4, and each n is independently the same or
different, and is 1 to 1,000, preferably 1 to 500, or 1 to 100, the
total of all values of n is greater than 4, or greater than 10, or
greater than 20, or greater than 50, or greater than 100, or
greater than 250.
[0114] Aspect 2. The branched polyimide of aspect 1, wherein when t
is 2, G is --O--, --C(O)--, --OC(O)--, --(O)CO--, --NHC(O),
--(O)CNH--, --S--, --S(O)--, --S(O).sub.2--, or --P(R.sup.a)(O)--
wherein R.sup.a is a C.sub.1-8 alkyl or C.sub.6-12 aryl; or when t
is 3, G is a nitrogen, phosphorus, or pentavalent P(O); or G is a
C.sub.1-60 hydrocarbon group having a valence of t.
[0115] Aspect 3. The branched polyimide of aspect 1 or 2, wherein G
is --O-- when m is 0, pentavalent P(O), a C.sub.6-50 hydrocarbon
having at least one aromatic group, a C.sub.2-20 aliphatic group, a
C.sub.4-8 cycloaliphatic group, or a C.sub.3-12 heteroarylene, or a
polymer moiety.
[0116] Aspect 4. The branched polyimide of any one or more of
aspects 1 to 3, wherein q is 1, Q is a C.sub.6-20 arylene, m is 1,
and M is --O--.
[0117] Aspect 5. The branched polyimide of any one or more of
aspects 1 to 4, wherein V is of the formula (2), wherein W is
--O--, --S--, --C(O)--, --SO.sub.2--, --SO--,
--P(R.sup.a)(.dbd.O)-- wherein R.sup.a is a C.sub.1-8 alkyl or
C.sub.6-12 aryl, --C.sub.yH.sub.2y-- wherein y is an integer from 1
to 5 or a halogenated derivative thereof, or a group of the formula
--O--Z--O-- wherein Z is an aromatic C.sub.6-24 monocyclic or
polycyclic moiety optionally substituted with 1 to 6 C.sub.1-8
alkyl groups, 1 to 8 halogen atoms, or a combination comprising at
least one of the foregoing, provided that the valence of Z is not
exceeded.
[0118] Aspect 6. The branched polyimide of any one or more of
aspects 1 to 5, wherein the branched polyimide is a branched
polyetherimide of formula (1a), preferably (1a'), wherein each Z is
independently an aromatic C.sub.6-24 monocyclic or polycyclic
moiety optionally substituted with 1 to 6 C.sub.1-8 alkyl groups, 1
to 8 halogen atoms, or a combination comprising at least one of the
foregoing, provided that the valence of Z is not exceeded.
[0119] Aspect 7. The branched polyimide of aspect 6, wherein Z is a
divalent group of formula (7a) wherein J is --O--, --S--, --C(O)--,
--SO.sub.2--, --SO--, or --C.sub.yH.sub.2y-- wherein y is an
integer from 1 to 5 or a halogenated derivative thereof and R is
m-phenylene, p-phenylene, bis(4,4'-phenylene)sulfone,
bis(3,4'-phenylene)sulfone, or bis(3,3'-phenylene)sulfone.
[0120] Aspect 8. A method for the manufacture of the branched
polyimide of any one or more of aspects 1 to 7, the method
comprising: reacting a polyamine of formula (8) and a diamine of
formula (10) with a dianhydride of formula (9) or (9a) in a solvent
and under conditions effective to provide the branched polyimide,
wherein G, Q, M, D, R, V, q, m, d, p and t are as defined in any
one or more of aspects 1 to 7.
[0121] Aspect 9. The aspect of aspect 8, further comprising
pre-dissolving the polyamine and the diamine in the solvent before
adding the dianhydride.
[0122] Aspect 10. A method for the manufacture of the branched
polyimide of any one or more of aspects 1 to 7, wherein the
branched polyimide is a branched polyetherimide, the method
comprising: reacting a polyamine of formula (8) and a diamine of
formula (10) with an anhydride of the formula (11) wherein X is a
nitro group or halogen, to provide intermediate bis(phthalimide)s
of the formulas (12) and (12a); and reacting the bis(phthalimide)s
with an alkali metal salt of a dihydroxy aromatic compound of
formula (13) wherein AM is an alkali metal, to provide the branched
polyetherimide, wherein G, Q, M, D, R, V, q, m, d, p, and t are as
defined in any one or more of aspects 1 to 7.
[0123] Aspect 11. The method of any one or more of aspects 8 to 10,
wherein the polyamine is of the formulas (8b), (8k), (8r), (8s), or
(8t).
[0124] Aspect 12. The method of any one or more of aspects 8, 9, or
11, wherein the dianhydride is
2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, and the
diamine is bis-(4-aminophenyl) sulfone or m-phenylenediamine.
[0125] Aspect 13. The branched polyimide of any one or more of
claims 1 to 7, or made by the method of any one or more of claims 8
to 12, having one or more of the following properties: a T.sub.g
greater than 100.degree. C., preferably 100 to 395.degree. C., more
preferably 180 to 280.degree. C., even more preferably 200 to
250.degree. C.; or an average branch molecular weight of 12,000 to
50,000 g/mol, preferably 15,000 to 40,000 g/mol, more preferably
23,000 to 38,000 g/mol; or a viscosity of greater than 25,000
pascal seconds at a frequency of 0.1 radians per second; or less
than 5 wt %, or less than 3 wt %, or less than 1 wt %, or less than
0.5 wt % of a gel, based on the total weight of the branched
polyimide; or a polydispersity of 1.5 to 3.0, as determined by size
exclusion chromatography multi-angle light scattering; a UL94
rating that is the better than or equal to a UL94 rating of the
same polyimide manufactured without the polyamine.
[0126] Aspect 14. An article comprising the branched polyimide of
any one or more of aspects 1 to 7 or 13, or made by any one or more
of the methods of aspects 8 to 12.
[0127] Aspect 15. A polyimide composition, comprising 1 to 99 wt %,
or 10 to 90 wt %, 0.1 to 20 wt %, or 0.5 to 10 wt %, or 1 to 5 wt %
of the branched polyimide of any one or more of aspects 1 to 7 or
13, or made by the method of aspects 8 to 12; and 1 to 99 wt %, or
10 to 90 wt %, or 0.9 to 80 wt %, or 99.5 to 90 wt %, or 99 to 95
wt % of a polyimide a second polyimide that is not the same as the
branched polyimide; and wherein each amount is based on the total
weight of the branched polyimide and the polyimide.
[0128] Aspect 16. An article comprising the polyimide composition
of aspect 15.
[0129] Aspect 17. A polymer composition comprising the polyimide
composition of aspect 14; and a third polymer different from the
branched polyimide and the second polyimide.
[0130] Aspect 18. The polymer composition of aspect 17, wherein the
second polymer is a polyacetal, poly(C.sub.1-6 alkyl)acrylate,
polyacrylamide, polyacrylonitrile, polyamide, polyamideimide,
polyanhydride, polyarylene ether, polyarylene ether ketone,
polyarylene ketone, polyarylene sulfide, polyarylene sulfone,
polybenzothiazole, polybenzoxazole, polybenzimidazole,
polycarbonate, polyester, polyetherimide, polyimide, poly(C.sub.1-6
alkyl)methacrylate, polymethacrylamide, cyclic olefin polymer,
polyolefin, polyoxadiazole, polyoxymethylene, polyphthalide,
polysilazane, polysiloxane, polystyrene, polysulfide,
polysulfonamide, polysulfonate, polythioester, polytriazine,
polyurea, polyurethane, vinyl polymer, or combination thereof.
[0131] Aspect 19: An article comprising the polymer composition of
aspect 17 or 18.
[0132] The article of aspects 16 or 19, wherein the article is a
foam, preferably a closed cell foam.
[0133] The compositions, methods, and articles can alternatively
comprise, consist of, or consist essentially of, any appropriate
components or steps herein disclosed. The compositions, methods,
and articles can additionally, or alternatively, be formulated so
as to be devoid, or substantially free, of any steps, components,
materials, ingredients, adjuvants, or species that are otherwise
not necessary to the achievement of the function or objectives of
the compositions, methods, and articles.
[0134] The singular forms "a," "an," and "the" include plural
referents unless the context clearly dictates otherwise. "Or" means
"and/or" unless clearly indicated otherwise by context. The
endpoints of all ranges directed to the same component or property
are inclusive and independently combinable. Disclosure of a
narrower range or more specific group in addition to a broader
range is not a disclaimer of the broader range or larger group.
"Combination thereof" as used herein means that a combination
comprising one or more of the listed items, optionally with one or
more like items not listed. A "combination" is inclusive of blends,
mixtures, alloys, reaction products, and the like.
[0135] Unless defined otherwise, technical and scientific terms
used herein have the same meaning as is commonly understood by one
of skill in the art to which this disclosure belongs. As used
herein, an unattached line, e.g., "O--" indicates a bond, not a
methyl group, which is indicated by "--CH.sub.3". The terms
"hydrocarbyl" and "hydrocarbon" refer broadly to a group comprising
carbon and hydrogen, optionally with 1 to 3 heteroatoms, for
example, oxygen, nitrogen, halogen, silicon, sulfur, or a
combination thereof; the term "aliphatic" means a branched or
unbranched, saturated or unsaturated group containing carbon and
hydrogen, optionally with 1 to 3 heteroatoms, for example, oxygen,
nitrogen, halogen, silicon, sulfur, or a combination thereof; the
term "cycloaliphatic" means a saturated or unsaturated group
comprising carbon and hydrogen optionally with 1 to 3 heteroatoms,
for example, oxygen, nitrogen, halogen, silicon, sulfur, or a
combination thereof; "alkyl" means a straight or branched chain,
saturated monovalent hydrocarbon group; "alkylene" means a straight
or branched chain, saturated, divalent hydrocarbon group;
"alkylidene" means a straight or branched chain, saturated divalent
hydrocarbon group, with both valences on a single common carbon
atom; "alkenyl" means a straight or branched chain monovalent
hydrocarbon group having at least two carbons joined by a
carbon-carbon double bond; "cycloalkyl" means a non-aromatic
monovalent monocyclic or multicyclic hydrocarbon group having at
least three carbon atoms, "cycloalkenyl" means a non-aromatic
cyclic divalent hydrocarbon group having at least three carbon
atoms, with at least one degree of unsaturation; "aryl" and
"arylene" means a monovalent group and divalent group respectively
containing at least one aromatic ring and optionally a nonaromatic
ring, and having only carbon in the ring or rings; "alkylarylene"
means an aryl group that has been substituted with an alkyl group
as defined above, with 4-methylphenyl being an exemplary
alkylarylene group; "arylalkylene" means an alkyl group that has
been substituted with an aryl group as defined above, with benzyl
being an exemplary arylalkylene group; "heteroaryl" and
"heteroarylene" means a monovalent group and divalent group
respectively wherein at least one carbon in a ring is replaced by a
heteroatom (S, O, P, or N); "acyl" means an alkyl group as defined
above with the indicated number of carbon atoms attached through a
carbonyl carbon bridge (--C(.dbd.O)--); "alkoxy" means an alkyl
group as defined above with the indicated number of carbon atoms
attached through an oxygen bridge (--O--); and "aryloxy" means an
aryl group as defined above with the indicated number of carbon
atoms attached through an oxygen bridge (--O--).
[0136] Unless otherwise indicated, each of the foregoing groups can
be unsubstituted or substituted, provided that the substitution
does not significantly adversely affect synthesis, stability, or
use of the compound. The term "substituted" as used herein means
that at least one hydrogen on the designated atom or group is
replaced with another group, provided that the designated atom's
normal valence is not exceeded. When the substituent is oxo (i.e.,
.dbd.O), then two hydrogens on the atom are replaced. Combinations
of substituents or variables are permissible provided that the
substitutions do not significantly adversely affect synthesis or
use of the compound. Exemplary groups that can be present on a
"substituted" position include, but are not limited to, cyano;
hydroxyl; nitro; alkanoyl (such as a C.sub.2-6 alkanoyl group such
as acyl); carboxamido; C.sub.1-6 or C.sub.1-3 alkyl, cycloalkyl,
alkenyl, and alkynyl (including groups having at least one
unsaturated linkages and from 2 to 8, or 2 to 6 carbon atoms);
C.sub.1-6 or C.sub.1-3 alkoxys; C.sub.6-10 aryloxy such as phenoxy;
C.sub.1-6 alkylthio; C.sub.1-6 or C.sub.1-3 alkylsulfinyl;
C.sub.1-6 or C.sub.1-3 alkylsulfonyl; amino di(C.sub.1-6 or
C.sub.1-3)alkyl; C.sub.6-12 aryl having at least one aromatic rings
(e.g., phenyl, biphenyl, naphthyl, or the like); C.sub.7-19
arylalkylene having 1 to 3 separate or fused rings and from 6 to 18
ring carbon atoms; or C.sub.7-19 arylalkyleneoxy having 1 to 3
separate or fused rings and from 6 to 18 ring carbon atoms, with
benzyloxy being an exemplary arylalkyleneoxy. When a group is
substituted, the indicated number of carbon atoms includes the
substituent.
[0137] All cited patents, patent applications, and other references
are incorporated herein by reference in their entirety. However, if
a term in the present application contradicts or conflicts with a
term in the incorporated reference, the term from the present
application takes precedence over the conflicting term from the
incorporated reference.
[0138] While particular embodiments have been described,
alternatives, modifications, variations, improvements, and
substantial equivalents that are or may be presently unforeseen may
arise to applicants or others skilled in the art. Accordingly, the
appended claims as filed and as they may be amended are intended to
embrace all such alternatives, modifications variations,
improvements, and substantial equivalents.
* * * * *