U.S. patent application number 12/061442 was filed with the patent office on 2008-12-18 for new polyarylene composition.
This patent application is currently assigned to SOLVAY ADVANCED POLYMERS, L.L.C.. Invention is credited to Romana B. Chavers, Mohammad Jamal El-Hibri, Nlkica Maljkovic, Henri Massillon.
Application Number | 20080312387 12/061442 |
Document ID | / |
Family ID | 40132945 |
Filed Date | 2008-12-18 |
United States Patent
Application |
20080312387 |
Kind Code |
A1 |
El-Hibri; Mohammad Jamal ;
et al. |
December 18, 2008 |
New Polyarylene Composition
Abstract
Blend (B) comprising at least one polyarylene in a form other
than fibers, and at least one poly(aryl ether ketone). Blend (T)
comprising at least one polyarylene, at least one poly(aryl ether
ketone) and at least one poly(aryl ether sulfone). Article or part
of an article comprising the blend (B) or the blend (T).
Inventors: |
El-Hibri; Mohammad Jamal;
(Atlanta, GA) ; Maljkovic; Nlkica; (New Orleans,
LA) ; Chavers; Romana B.; (Kiln, MS) ;
Massillon; Henri; (Waremme, BE) |
Correspondence
Address: |
Solvay Advanced Polymers, LLC;c/o Kim Manson, Esq.
4500 McGinnis Ferry Road
Alpharetta
GA
30005-3914
US
|
Assignee: |
SOLVAY ADVANCED POLYMERS,
L.L.C.
Alpharetta
GA
|
Family ID: |
40132945 |
Appl. No.: |
12/061442 |
Filed: |
April 2, 2008 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
PCT/EP2007/052102 |
Mar 6, 2007 |
|
|
|
12061442 |
|
|
|
|
11850739 |
Sep 6, 2007 |
|
|
|
PCT/EP2007/052102 |
|
|
|
|
60909514 |
Apr 2, 2007 |
|
|
|
60912989 |
Apr 20, 2007 |
|
|
|
60842365 |
Sep 6, 2006 |
|
|
|
60842366 |
Sep 6, 2006 |
|
|
|
60842369 |
Sep 6, 2006 |
|
|
|
60842368 |
Sep 6, 2006 |
|
|
|
60842367 |
Sep 6, 2006 |
|
|
|
60836946 |
Aug 11, 2006 |
|
|
|
Current U.S.
Class: |
525/471 |
Current CPC
Class: |
C08L 81/06 20130101;
C08G 75/23 20130101; C08L 81/06 20130101; C08G 2650/40 20130101;
C08L 71/00 20130101; C08L 2666/14 20130101; C08L 65/02 20130101;
C08L 65/02 20130101; C08L 2666/14 20130101; C08L 2666/14 20130101;
C08G 2261/312 20130101; C08L 71/08 20130101; C08L 71/00
20130101 |
Class at
Publication: |
525/471 |
International
Class: |
C08G 10/00 20060101
C08G010/00 |
Claims
1- A blend (B) comprising: at least one polyarylene (P1) in a form
other than fibers, and at least one poly(aryl ether ketone)
(P2).
2- The blend (B) according to claim 1, wherein more than 25 wt. %
of the recurring units of the polyarylene (P1) are recurring units
(R1) chosen from optionally substituted phenylene groups which are
linked by each of their two ends to two other optionally
substituted phenylene groups via a direct C--C linkage, said
recurring units (R1) being a mix of recurring units (R1-a) wherein
the optionally substituted phenylene groups are optionally
substituted p-phenylenes, with recurring units (R1-b) wherein the
optionally substituted phenylene groups are either optionally
substituted m-phenylenes or mixes of optionally substituted
m-phenylenes with optionally substituted o-phenylenes, wherein the
mole ratio of the recurring units (R1-b), based on the total number
of moles of the recurring units (R1-a) and (R1-b), ranges from 30%
to 95%.
3- The blend (B) according to claim 2, wherein the mole ratio of
the recurring units (R1-b), based on the total number of motes of
the recurring units (R1-a) and (R1-b), is of at least 40%.
4- The blend (B) according to claim 2, wherein the mole ratio of
the recurring units (R1-b), based on the total number of moles of
the recurring units (R1-a) and (R1-b), is of at most 80%.
5- The blend (B) according to claim 2, wherein more than 90 wt. %
of the recurring units of the polyarylene (P1) are recurring units
(R1), the recurring units (R1-a) are p-phenylene groups substituted
by at least one monovalent solubilizing group, and the recurring
units (R1-b) are m-phenylene groups optionally substituted by at
least one monovalent solubilizing group.
6- The blend (B) according to claim 2, wherein the polyarylene (P1)
is a polyphenylene copolymer, essentially all the recurring units
of which consist of a mix of phenylketone-substituted p-phenylene
groups with unsubstituted m-phenylene groups, in a mole ratio
p-phenylene:m-phenylene of from 30:70 to 70:30.
7- The blend (B) according to claim 2, wherein the poly(aryl ether
ketone) (P2) is a polyetheretherketone (PEEK) homopolymer,
essentially all the recurring units of which being of formula
##STR00031##
8- The blend (B) according to claim 2, wherein the weight of the
polyarylene (P1), based on the total weight of the polyarylene (P1)
and the poly(aryl ether ketone) (P2), ranges from 30% to 70%.
9- The blend (B) according to claim 2, wherein the total weight of
the polyarylene (P1) and the poly(aryl ether ketone) (P2), based on
the total weight of the blend (B), is above 80%.
10- A method for preparing the blend (B) according to claim 2,
which comprises mixing the polyarylene (P1) with the poly(aryl
ether ketone) (P2), at a temperature above the melt temperature of
the polyarylene (P1) and the melt temperature of the poly(aryl
ether ketone) (P2).
11- A shaped article or a part of a shaped article comprising the
blend (B) according to claim 2.
12- A blend (T) comprising: at least one polyarylene (P1.sup.+), at
least one poly(aryl ether ketone) (P2), and at least one poly(aryl
ether sulfone) (P3).
13- The blend (T) according to claim 12, wherein the weight of the
polyarylene (P1.sup.+), based on the total weight of the
polyarylene (P1.sup.+) and the poly(aryl ether ketone) (P2), ranges
from 15% to 90%.
14- The blend (T) according to claim 12, wherein the poly(aryl
ether sulfone) (P3) over polyarylene (P1.sup.+) weight ratio ranges
from 0.05 to 1, and the poly(aryl ether sulfone) (P3) over
poly(aryl ether ketone) (P2) weight ratio ranges also from 0.05 to
1.
15- The blend (T) according to claim 12, wherein the weight of the
polyarylene (P1.sup.+), based on the total weight of the
polyarylene (P1.sup.+) and the poly(aryl ether ketone) (P2), ranges
from 30% to 70%, the poly(aryl ether sulfone) (P3) over polyarylene
(P1.sup.+) weight ratio ranges from 0.15 to 0.50, and the poly(aryl
ether sulfone) (P3) over poly(aryl ether ketone) (P2) weight ratio
ranges from 0.15 to 0.50.
16- The blend (T) according to claim 12, wherein the total weight
of the polyarylene (P1.sup.+), the poly(aryl ether ketone) (P2) and
the poly(aryl ether sulfone) (P3), based on the total weight of the
blend (T), is above 95%.
17- The blend (T) according to claim 12, wherein the polyarylene
(P1.sup.+) is a polyarylene (P1) in a form other than fibers.
18- The blend (T) according to claim 12, wherein the polyarylene
(P1.sup.+) is a polyphenylene.
19- The blend (T) according to claim 12, wherein the polyarylene
(P1.sup.+) is a polyphenylene copolymer, essentially all the
recurring units of which consist of a mix of
phenylketone-substituted p-phenylene groups with unsubstituted
m-phenylene groups in a mole ratio p-phenylene:m-phenylene of from
5:95 to 95.5.
20. The blend (T) according to claim 12, wherein more than 50 wt. %
of the recurring units of the poly(aryl ether ketone) (P2) are
recurring units (R2) chosen from: ##STR00032## ##STR00033##
21- The blend (T) according to claim 12, wherein the poly(aryl
ether ketone) (P2) is a polyetheretherketone (PEEK) homopolymer,
essentially all the recurring units of which being of formula
##STR00034##
22- The blend (T) according to claim 12, wherein the poly(aryl
ether sulfone) (P3) is a poly(biphenyl ether sulfone).
23- The blend (T) according to claim 12, wherein the poly(aryl
ether sulfone) (P3) is a polyphenylsulfone homopolymer, essentially
all the recurring units of which being of formula ##STR00035##
24- A method for preparing the blend (T) according to claim 12,
which comprises mixing the polyarylene (P1.sup.+) with the
poly(aryl ether ketone) (P2) and the poly(aryl ether sulfone) (P3),
at a temperature above the melt temperature of the poly(aryl ether
ketone) (P2) and the melt temperature of the poly(aryl ether
sulfone) (P3).
25- A shaped article or a part of a shaped article comprising the
blend (T) according to claim 12.
26. A polymer blend (T') suitable for producing a layer of a
flexible pipe for transporting hydrocarbons, said polymer blend
(T') comprising at least one polyarylene (P1'), and a mix (M23')
selected from the group consisting of (i) mixes of at least one
poly(aryl ether ketone) (P2') and at least one poly(aryl ether
sulfone) (P3'), and (ii) mixes of at least one poly(aryl ether
ketone) (P2'), at least one poly(aryl ether sulfone) (P3') and at
least one fluoropolymer (P4'), wherein: more than 50 wt. % of the
recurring units of the polyarylene (P1') are recurring units (R1')
of one or more formulae consisting of an optionally substituted
arylene group, provided said optionally substituted arylene group
is linked by each of its two ends to two other optionally
substituted arylene groups via a direct C--C linkage, the poly(aryl
ether ketone) (P2') is a polycondensate, of which more than 50 wt.
% of the recurring units are recurring units (R2') of one or more
formulae containing at least one arylene group, at least one ether
group (--O--) and at least one ketone group [--C(.dbd.O)-], the
said one or more formulae being free of sulfone group
[--S(.dbd.O).sub.2-], and the poly(aryl ether sulfone) (P3') is a
polymer other than the polyarylene (P1'), of which more than 50 wt.
% of the recurring units are recurring units (R3') of one or more
formulae containing at least one arylene group, at least one and at
least one ether group (--O--) and at least one sulfone group
[--S(.dbd.O).sub.2-].
27- A polymer composition (T'') suitable for producing a layer of a
flexible pipe for transporting hydrocarbons, said polymer
composition (T'') comprising: at least one polyarylene (P1'')
selected from the group consisting of polyphenylenes, at least one
poly(aryl ether ketone) (P2''), said poly(aryl ether ketone) (P2'')
being a polymer of which more than 50 wt. % of the recurring units
are recurring units (R2'') of one or more formulae containing at
least one arylene group, at least one ether group (--O--) and at
least one ketone group [--C(.dbd.O)--], the said one or more
formulae being free of sulfone group [--S(.dbd.O).sub.2--], and at
least one poly(aryl ether sulfone) (P3''), said poly(aryl ether
sulfone) (P3'') being a polymer of which more than 50 wt. % of the
recurring units are recurring units (R3'') of one or more formulae
containing at least one arylene group, at least one ether group
(--O--) and at least one sulfone group [--S(.dbd.O).sub.2-],
wherein: the weight of the poly(aryl ether ketone) (P2''), based on
the total weight of the poly(aryl ether ketone) (P2'') and the
poly(aryl ether sulfone) (P3''), is from 35% to 95%, and the
polymer composition (T'') is free of epoxy resin modified by at
least one aromatic polyamine, or comprises the said epoxy resin
modified by at least one polyamine in a weight amount of at most
10%, based on the total weight of the polymer composition (T'').
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims the benefit under 35 USC
119(e) of (1) U.S. provisional application No. 60/909,514 filed
Apr. 20, 2007, (2) U.S. provisional application No. 60/912,989
filed Apr. 20, 2007; (3) is a continuation-in-part of PCT
application no. PCT/EP2007/052102 filed Mar. 6, 2007, which is a
continuation-in-part of PCT application no. PCT/EP2006/060535 filed
Mar. 7, 2006 (now U.S. application Ser. No. 11/850,739), PCT
application no. PCT/EP20071052102 claiming priority to U.S.
provisional application No. 60/836,946 filed Aug. 11, 2006, U.S.
provisional application No. 60/842,369 filed Sep. 6, 2006, U.S.
provisional application No. 60/842,367 filed Sep. 6, 2006, U.S.
provisional application No. 60/842,368 filed Sep. 6, 2006, U.S.
provisional application No. 60/842,366 filed Sep. 6, 2006, and U.S.
provisional application No. 60/842,365 filed Sep. 6, 2006, and (4)
is a continuation-in-part of U.S. application Ser. No. 11/850,739
filed Sep. 6, 2007, which is a continuation of PCT application no.
PCT/EP2006/060535 filed Mar. 7, 2006, the entirety of all
applications being herein incorporated by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to a new polyarylene
composition, and to articles and part of articles made thereof.
[0003] In particular, described herein are blends comprising a
polyarylene and a poly(aryl ether ketone).
BACKGROUND OF THE INVENTION
[0004] Polyarylenes, especially polyphenylenes, exhibit some
outstanding performance properties, including exceptionally high
strength, stiffness, hardness, scratch resistance and dimensional
stability. Unfortunately, polyarylenes have some limitations in
toughness-related properties, in particular in terms of impact
resistance and elongation properties. They have also limitations in
melt processability due to their high viscosities, and tend to be
anisotropic when melt fabricated under high shear such as during
injection molding. Also, they have some limitations in chemical
resistance. Also, they have some limitations in thermal resistance,
which may cause some undesirable outgassing (weight loss) when
submitted at very high temperature (380.degree. C. or so).
[0005] Poly(aryl ether ketone)s, especially polyetheretherketones,
exhibit also some outstanding properties, including exceptionally
high melting point, excellent chemical resistance (including
environmental stress cracking resistance) and excellent thermal
stability. They have also high strength, stiffness, although
somewhat lower than that of polyarylenes, and very good elongation
properties. On the other hand, like polyarylenes, they have some
limitations in terms of impact resistance.
[0006] Polymer blends have been widely taught and employed in the
art. As broad as this statement may be, the blending of polymers
remains an empirical art and the selection of polymers for a blend
giving special properties is, in the main, an Edisonian-like
choice. Certain attributes of polymer blends are more unique than
others. The more unique attributes when found in a blend tend to be
unanticipated properties. According to Zoller and Hoehn, Journal of
Polymer Science, Polymer Physics Edition, vol. 20, pp. 1385-1397
(1982): "Blending of polymers is a useful technique to obtain
properties in thermoplastic materials not readily achieved in a
single polymer. Virtually all technologically important properties
can be improved in this way, some of the more important ones being
flow properties, mechanical properties (especially impact
strength), thermal stability, and price ( . . . ). Ultimately, the
goal of such modeling and correlation studies should be the
prediction of blend properties from the properties of the pure
components alone. We are certainly very far from achieving this
goal."
[0007] In the field of miscibility or compatibility of polymer
blends, the art has found predictability to be unattainable, even
though considerable work on the matter has been done. According to
authorities, "It is well known that, regarding the mixing of
thermoplastic polymers, incompatibility is the rule and miscibility
and even partial miscibility is the exception. Since most
thermoplastic polymers are immiscible in other thermoplastic
polymers, the discovery of a homogeneous mixture or partially
miscible mixture of two or more thermoplastic polymers is, indeed,
inherently unpredictable with any degree of certainty, for example,
see P. J. Flory, Principles of Polymer Chemistry, Cornell
University Press, 1953, Chapter 13, page 555.
[0008] U.S. Pat. No. 5,654,392 describes a class of polyphenylene
polymers with phenylene units comprising a solubilizing side group
which, because of this side group, are taught to help somehow in
overcoming the problem of blending the rigid-rod and flexible
components into a stable homogeneous phase (see col. 2, 1. 60-63).
Per US'392, the rigid-rod polymers can be blended with
thermoplastics, thermosets, liquid crystalline polymers (LCP's),
rubbers, elastomers, or any natural or synthetic polymeric material
(col. 4, 1. 16-20); US'392 keeps silent about the miscibility and
compatibility of the polymers of such blends. It is of interest to
note that, per US'392, only polymer blends containing a low amount
of polyphenylene (at most 10 wt. %) with certain specific polymers
could be prepared by a melt process [with polybutylene (example
23), nylon-6 (example 24), polystyrene and PPO (examples 24 and
25), polyethylene and polypropylene (example 25)], while blends
comprising a higher amount of polyphenylene were prepared by
solution mixing [blends with polystyrene (example 26) and
polycarbonate (example 27)]; this suggests that the polymers
involved in such blends have a very poor reciprocal
miscibility/compatibility, or even are completely
immiscible/incompatible, as many other couple of polymers are.
[0009] Example 13 of the same patent is a prophetic description (as
evidenced by the use of the present tense and the absence of
detailed operating conditions) of a pultrusion process involving a
polyetheretherketone (PEEK) at molten state and fibers of a
rigid-rod polyparaphenylene with a solubilizing group of high
molecular weight, namely a poly 1,4-(4'-phenoxybenzoylphenylene).
Accordingly, a fiber tow composed of the polyparaphephenylene
fibers is continuously pulled through a PEEK melt and co-extruded
through a die to form ribbed panels, which can be viewed as a
composite material consisting of, as separate interconnected parts,
essentially parallel polyphenylene fibers interconnected by a PEEK
matrix so as to form a unified whole. In a pultrusion process, it
is mandatory to preserve the fibrous nature of the fibers, so as to
obtain a material with desirable properties, in particular a high
modulus and strength; that the fibrous nature of the fiber is
preserved in this prophetic example, is confirmed by the ribbed
attribute of the panels (the ribs are deemed to be polyphenylene
fibers), and also by the general teachings of US'392 about the
pultrusion of polyphenylene fibers with thermoplastics (of
undefined nature), from col. 21, 1. 54 to col. 22, 1. 3: "Related
to extrusion is pultrusion, wherein a fiber reinforcement is
continuously added to an extruded polymer. ( . . . ) the polymers
of the present invention may be used as the fiber for pultrusion of
a thermoplastic having a lower processing temperature. ( . . . )
lower cost thermoplastics having moderate moduli and strength can
be formed into composites with high moduli and strength by the
incorporation of rigid-rod or segmented rigid-rod polyphenylene
fibers. Such a composite is unique in that the reinforcing fibers
are themselves thermoplastic and further processing at temperatures
above the fiber Tg will result in novel structures as the fibers
physically and/or chemically mix with the matrix." Back to example
13 specifically, by giving credit to a pultrusion process
comprising which requires contacting, during a significant amount
of time, polyphenylene fibers (which have a Tg as low as about
160.degree. C.) with molten PEEK (PEEK at a temperature above about
340.degree. C.) without affecting the fibrous nature of the
polyphenylene fibers, US'392 gives thereby credit to the
incompatibility and the immiscibility of polyphenylene also with
PEEK, discarding thereby the skilled person from mixing a
polyphenylene in a form other than fibers with PEEK in a
significant amount so as to obtain a valuable blend, since, in such
a case, the expectation would be great to obtain an unstable
physical blend, highly subject to phase separation.
[0010] There remains a strong need for materials offering a
superior balance of properties, including part or all of the
following ones: [0011] very high strength; [0012] very high
stiffness [0013] good elongation properties [0014] good melt
processability (in particular, good injection moldability) [0015]
high chemical resistance; [0016] outstanding thermal resistance
[capable of inhibiting undesirable outgassing even when the
material is submitted at very high temperature (380.degree. C. or
so)], desirably as high as that neat poly(aryl ether ketone); and
[0017] outstanding impact resistance, as possibly characterized by
a standard no-notch IZOD test (ASTM D-4810), desirably higher than
that of neat polyarylene and neat poly(aryl ether ketone).
THE INVENTION
[0018] In its principal aspect, the present invention is directed
to a blend (B) comprising: [0019] at least one polyarylene (P1) in
a form other than fibers, and [0020] at least one poly(aryl ether
ketone) (P2).
[0021] Another aspect of the present invention is directed to a
method for preparing the blend (B) as above described which
comprises mixing at least one polyarylene (P1) in a form other than
fibers with at least one poly(aryl ether ketone) (P2), at a
temperature above the melt temperature of the polyarylene (P1) and
the melt temperature of the poly(aryl ether ketone) (P2).
[0022] Still another aspect of the present invention is directed to
a shaped article or a part of a shaped article comprising the blend
(B) as above described, or prepared by the method as above
described.
[0023] Still other aspects of the present invention are directed to
the use of at least one polyarylene (P1) as additive of a poly(aryl
ether ketone) composition (B2.degree.) comprising at least one
poly(aryl ether ketone) (P2), for increasing the level of the
impact resistance of the poly(aryl ether ketone) composition
(B2.degree.), as determined by a no-notch IZOD test (ASTM D-4810),
up to a level which is higher than both that of the impact
resistance of the poly(aryl ether ketone) composition (B2.degree.)
and that of the impact resistance of a polyarylene composition
(B1.degree.) obtained by replacing, weight for weight in the
poly(aryl ether ketone) composition (B2.degree.), all the poly(aryl
ether ketone) (P2) by the polyarylene (P1),
and, reciprocally, to the use of at least one poly(aryl ether
ketone) (P2) as additive of a polyarylene composition (B1.degree.)
comprising at least one polyarylene (P1), for increasing the level
of the impact resistance of the polyarylene composition
(B1.degree.), as determined by a no-notch IZOD test (ASTM D-4810),
up to a level which is higher than both that of the impact
resistance of the polyarylene composition (B1.degree.) and that of
the impact resistance of a poly(aryl ether ketone) composition
(B2.degree.) obtained by replacing, weight for weight in the
polyarylene composition (B1.degree.), all the polyarylene (P1) by
the poly(aryl ether ketone) (P2).
[0024] Still another aspect of the present invention is directed to
a blend (T) comprising: [0025] at least one polyarylene (P1.sup.+),
[0026] at least one poly(aryl ether ketone) (P2), and [0027] at
least one poly(aryl ether sulfone) (P3).
[0028] Still another aspect of the present invention is directed to
a method for preparing the blend (T) as above described which
comprises mixing the polyarylene (P1.sup.+) with the poly(aryl
ether ketone) (P2) and the poly(aryl ether sulfone) (P3), at a
temperature above the melt temperature of the poly(aryl ether
ketone) (P2) and the melt temperature of the poly(aryl ether
sulfone) (P3).
[0029] Still another aspect of the present invention is directed to
a shaped article or a part of a shaped article comprising the blend
(T) as above described, or prepared by the method as above
described. The polymer blend (T) is well suited notably for
producing a layer of a flexible pipe for transporting
hydrocarbons.
BRIEF DESCRIPTION OF THE DRAWINGS
[0030] For a detailed description of the invention, reference will
now be made to the accompanying drawings in which:
[0031] FIG. 1 represents a transmission electron microscope (TEM)
photomicrograph showing the morphology of a ternary blend (called
blend (T5)) with medium PEEK-polyphenylene content; and
[0032] FIG. 2 represents a transmission electron microscope (TEM)
photomicrograph of a binary blend (called blend B5) corresponding
to the ternary blend (T5).
DETAILED DESCRIPTION OF THE INVENTION
[0033] In the blend (B), the weight of the polyarylene (P1), based
on the total weight of the polyarylene (P1) and the poly(aryl ether
ketone) (P2), is advantageously of at least 15%, preferably at
least 30%, more preferably at least 40%, still more preferably at
least 50% and the most preferably at least 60%. On the other hand,
the weight of the polyarylene (P1), based on the total weight of
the polyarylene (P1) and the poly(aryl ether ketone) (P2), is
advantageously of at most 90%, preferably at most 80%, and more
preferably at most 70%.
[0034] In the blend (B), the total weight of the polyarylene (P1)
and of the poly(aryl ether ketone) (P2), based on the total weight
of the blend (B), is advantageously above 25%, preferably above
50%, more preferably above 80% and still more preferably above 95%.
Excellent results were obtained when the blend (B) consisted
essentially of, or even consisted of, the polyarylene (P1) and of
the poly(aryl ether ketone) (P2).
[0035] In the blend (B), the weight of the polyarylene (P1), based
on the total weight of the blend (B), is advantageously of at least
15%, preferably at least 30%, more preferably at least 40%, still
more preferably at least 50% and the most preferably at least 60%.
On the other hand, the weight of the polyarylene (P1), based on the
total weight of the blend (B), is advantageously of at most 90%,
preferably at most 80%, and still more preferably at most 70%.
[0036] In the blend (B), the weight of the poly(aryl ether ketone)
(P2), based on the total weight of the blend (B), is advantageously
of at least 10%, preferably at least 20% and more preferably at
least 30%. On the other hand, the weight of the poly(aryl ether
ketone) (P2), based on the total weight of the blend (B), is
advantageously of at most 85%, preferably at most 70%, more
preferably at most 60%, still more preferably at most 50% and the
most preferably at most 40%.
The Polyarylene (P1)
[0037] For the purpose of the present invention, an arylene group
is a hydrocarbon divalent group consisting of one core composed of
one benzenic ring or of a plurality of benzenic rings fused
together by sharing two or more neighboring ring carbon atoms, and
of two ends.
[0038] Non limitative examples or arylene groups are phenylenes,
naphthylenes, anthrylenes, phenanthrylenes, tetracenylenes,
triphenylylenes, pyrenylenes, and perylenylenes. The arylene groups
(especially the numbering of the ring carbon atoms) were named in
accordance with the recommendations of the CRC Handbook of
Chemistry and Physics, 64.sup.th edition, pages C1-C44, especially
p. C11-C12.
[0039] Arylene groups present usually a certain level of
aromaticity; for this reason, they are often reported as "aromatic"
groups. The level of aromaticity of the arylene groups depends on
the nature of the arylene group; as thoroughly explained in Chem.
Rev. 2003, 103, 3449-3605, "Aromaticity of Polycyclic Conjugated
Hydrocarbons", the level of aromaticity of a polycyclic aromatic
hydrocarbon can be notably quantified by the "index of benzene
character" B, as defined on p. 3531 of the same paper; values of B
for a large set of polycyclic aromatic hydrocarbon are reported on
table 40, same page.
[0040] An end of an arylene group is a free electron of a carbon
atom contained in a (or the) benzenic ring of the arylene group,
wherein an hydrogen atom linked to said carbon atom has been
removed. Each end of an arylene group is capable of forming a
linkage with another chemical group. An end of an arylene group, or
more precisely the linkage capable of being formed by said end, can
be characterized by a direction and by a sense; to the purpose of
the present invention, the sense of the end of an arylene group is
defined as going from the inside of the core of the arylene group
to the outside of said core. As concerns more precisely arylene
groups the ends of which have the same direction, such ends can be
either of the same or opposite sense; also, their ends can be in
the straight foregoing of each other, or not (otherwise said, they
can be disjoint).
[0041] A polyarylene is intended to denote a polymer, other than a
poly(aryl ether ketone) as defined below, of which more than 25 wt.
% of the recurring units are recurring units (R1) of one or more
formulae consisting of an optionally substituted arylene group,
provided said optionally substituted arylene group is linked by
each of its two ends to two other optionally substituted arylene
groups via a direct C--C linkage. That the optionally substituted
arylene group is linked by each of its two ends to two other
optionally substituted arylene groups via a direct C--C linkage, is
an essential feature of the recurring units (R1); thus, an arylene
recurring unit which is linked by at least one of its two ends to a
group other than an arylene group such as phenylene recurring units
.phi..sub.1, .phi..sub.2 and .phi..sub.2' below:
--O-.phi..sub.1-S(.dbd.O).sub.2--,
--O-.phi..sub.2-.phi..sub.2'-O--
are not recurring units (R1) in the sense of the present
invention.
[0042] The arylene groups of which the recurring units (R1) consist
can be unsubstituted. Alternatively, they can be substituted by at
least one monovalent substituting group.
[0043] The monovalent substituting group is usually not polymeric
in nature; its molecular weight is preferably below 500, more
preferably below 300, still more preferably below 200 and the most
preferably below 150.
[0044] The monovalent substituting group is advantageously a
solubilizing group. A solubilizing group is one increasing the
solubility of the polyarylene (P1) in at least one organic solvent,
in particular in at least one of dimethylformamide,
N-methylpyrrolidinone, hexamethylphosphoric triamide, benzene,
tetrahydrofuran and dimethoxyethane, which can be used as solvents
during the synthesis of the polyarylene (P1) by a solution
polymerization process.
[0045] The monovalent substituting group is also advantageously a
group which increases the fusibility of the polyarylene (P1), i.e.
it lowers its glass transition temperature and its melt viscosity,
so as to desirably make the polyarylene (P1) suitable for
thermoprocessing.
[0046] Preferably, the monovalent substituting group is chosen from
[0047] hydrocarbyls such as alkyls, aryls, alkylaryls and aralkyls;
[0048] halogenos such as --Cl, --Br, --F and --I; [0049]
hydrocarbyl groups partially or completely substituted by at least
one halogen atom such as halogenoalkyls, halogenoaryls,
halogenoalkylaryls and halogenoaralkyls; [0050] hydroxyl; [0051]
hydrocarbyl groups substituted by at least one hydroxyl group, such
as hydroxyalkyls, hydroxyaryls, hydroxyalkylaryls and
hydroxyaralkyls; [0052] hydrocarbyloxys [--O--R, where R is a
hydrocarbyl group], such as alkoxys, aryloxys, alkylaryloxys and
aralkyloxys; [0053] amino (--NH.sub.2); [0054] hydrocarbyl groups
substituted by at least one amino group, such as aminoalkyls and
aminoaryls; [0055] hydrocarbylamines [--NHR or --NR.sub.2, where R
is a hydrocarbyl group] such as alkylamines and arylamines; [0056]
carboxylic acids and their metal or ammonium salts, carboxylic acid
halides, carboxylic anhydrides; [0057] hydrocarbyl groups
substituted by at least one of carboxylic acids, metals or ammonium
salts thereof, carboxylic acid halides and carboxylic anhydrides,
such as --R--C(.dbd.O)OH where R is an alkyl or an aryl group;
[0058] hydrocarbylesters [--C(.dbd.O)OR or --O--C(.dbd.O)R, where R
is a hydrocarbyl group] such as alkylesters, arylesters,
alkylarylesters and aralkylesters [0059] amido
[--C(.dbd.O)NH.sub.2]; [0060] hydrocarbyl groups substituted by at
least one amido group; [0061] hydrocarbylamide monoesters
[--C(.dbd.O)NHR or --NH--C(.dbd.O)--R, where R is a hydrocarbyl
group], such as alkylamides, arylamides, alkylarylamides and
aralkylamides, and hydrocarbylamide diesters [--C(.dbd.O)NR.sub.2
or --N--C(.dbd.O)R.sub.2, where R are a hydrocarbyl groups], such
as dialkylamides and diarylamides; [0062] sulfinic acid
(--SO.sub.2H), sulfonic acid (--SO.sub.3H), their metal or ammonium
salts, [0063] hydrocarbylsulfones [--S(.dbd.O).sub.2--R, where R is
the hydrocarbyl group], such as alkylsulfones, arylsulfones,
alkylarylsulfones, aralkylsulfones; [0064] aldehyde [--C(.dbd.O)H]
and haloformyls [--C(.dbd.O)X, wherein X is a halogen atom]; [0065]
hydrocarbylketones [--C(.dbd.O)--R, where R is a hydrocarbyl
group], such as alkylketones, arylketones, alkylarylketones and
aralkylketones [0066] hydrocarbyloxyhydrocarbylketones
[--C(.dbd.O)--R.sup.1--O--R.sup.2, where R.sup.1 is a divalent
hydrocarbon group such as an alkylene, an arylene, an alkylarylene
or an aralkylene, preferably a C.sub.1-C.sub.18 alkylene, a
phenylene, a phenylene group substituted by at least one alkyl
group, or an alkylene group substituted by at least one phenyl
group; and R.sup.2 is a hydrocarbyl group, such as an alkyl, aryl,
alkylaryl or aralkyl group, such as alkyloxyalkylketones,
alkyloxyarylketones, alkyloxyalkylarylketones,
alkyloxyaralkylketones, aryloxyalkylketones, aryloxyarylketones,
aryloxyalkylarylketones and aryloxyaralkylketones; [0067] any of
the above groups comprising at least one hydrocarbyl group or a
divalent hydrocarbon group R.sup.1, wherein said hydrocarbyl group
or said R.sup.1 is itself substituted by at least one of the above
listed monovalent substituting groups, e.g. an arylketone
--C(.dbd.O)--R, where R is an aryl group substituted by one
hydroxyl group where: [0068] the hydrocarbyl groups contain
preferably from 1 and 30 carbon atoms, more preferably from 1 to 12
carbon atoms and still more preferably from 1 to 6 carbon atoms;
[0069] the alkyl groups contain preferably from 1 to 18 carbon
atoms, and more preferably from 1 to 6 carbon atoms; very
preferably, they are chosen from methyl, ethyl, n-propyl,
isopropyl, n-butyl, isobutyl and tert-butyl; [0070] the aryl groups
are defined as monovalent groups consisting of one end and one core
composed of one benzenic ring (such the phenyl group) or of a
plurality of benzenic rings directly linked to each other via a
carbon-carbon linkage (such as the biphenyl group) or fused
together by sharing two or more neighboring ring carbon atoms (such
as the naphthyl groups), and wherein the ring carbon atoms are
possibly substituted by at least one nitrogen, oxygen or sulfur
atom preferably, in the aryl groups, no ring carbon atom is
substituted; [0071] the aryl groups contain preferably from 6 to 30
carbon atoms; more preferably, they are phenyl groups; [0072] the
alkyl group which is contained in the alkylaryl groups meets the
preferences of the alkyl groups as above expressed; [0073] the aryl
group which is contained in the aralkyl groups meets the
preferences of the aryl groups as above expressed.
[0074] More preferably, the monovalent substituting group is chosen
from hydrocarbylketones [--C(--O)--R, where R is a hydrocarbyl
group] and hydrocarbyloxyhydrocarbylketones
[--C(.dbd.O)--R.sup.1--O--R.sup.2, where R.sup.1 is a divalent
hydrocarbon group and R.sup.2 is a hydrocarbyl group], said
hydrocarbylketones and hydrocarbyloxyhydrocarbylketones being
unsubstituted or substituted by at least one of the above listed
monovalent substituting groups.
[0075] Still more preferably, the monovalent substituting group is
chosen from arylketones and aryloxyarylketones, said arylketones
and aryloxyarylketones being unsubstituted or substituted by at
least one of the above listed monovalent substituting groups.
[0076] The most preferably, the monovalent substituting group is an
(unsubstituted) arylketone, in particular it is phenylketone
[--C(.dbd.O)-phenyl].
[0077] The core of the optionally substituted arylene group of the
recurring units (R1) is composed of preferably at most 3, more
preferably at most 2, and still more preferably at most one
benzenic ring. Then, when the core of the optionally substituted
arylene group of the recurring units (R1) is composed of one
benzenic ring, the recurring units (R1) are of one or more formulae
consisting of an optionally substituted phenylene group, provided
said optionally substituted phenylene group is linked by each of
its two ends to two other optionally substituted arylene groups via
a direct C--C linkage, and the polyarylene (P1) is called a
polyphenylene. Then, the polyarylene (P1) is preferably a
polyphenylene.
[0078] As above explained, the optionally substituted arylene group
of the recurring units (R1) is linked by each of its two ends to
two other optionally substituted arylene groups via a direct C--C
linkage. Preferably, it is linked by each of its two ends to two
other optionally substituted phenylene groups via a direct C--C
linkage.
[0079] As also above explained, both ends of the optionally
substituted arylene group of the recurring units (R1) can be
characterized notably by a direction and by a sense.
[0080] A first set of recurring units suitable as recurring units
(R1) is composed of optionally substituted arylene groups, the ends
of which [0081] have the same direction, [0082] are of opposite
sense, and [0083] are in the straight foregoing of each other
[hereafter, recurring units (R1-a)].
[0084] Non limitative examples of such optionally substituted
arylene groups include: 1,4-phenylylene (also named p-phenylene);
1,4-naphthylene; 1,4- and 2,7-phenanthrylenes; 1,4-, and
9,10-anthrylenes; 2,7-pyrenylene; 1,4- and 5,12-naphthacenylenes;
1,4-chrysenylene; 1,4- and 2,7-triphenylylenes; 1,4-, 5,14- and
6,13-pentacenylenes; 1,6-coronenylene; 1,4-, 2,9- and
5,18-trinaphtlylenylenes; and any of these groups substituted by at
least one monovalent substituting group, as above defined, in
particular by a phenylketone group.
[0085] Good results were obtained when recurring units (R1-a) are
optionally substituted p-phenylenes.
[0086] Recurring units (R1-a), when contained in the polyarylene
(P1), result in straight polymer chains exhibiting an outstanding
rigidity. For this reason, such polyarylenes (P1) are commonly
referred to as "rigid-rod polymers".
[0087] A second set of recurring units suitable as recurring (R1)
is composed of optionally substituted arylene groups, the ends of
which [0088] either have a different direction, forming thus
together an angle between 0 and 180.degree., said angle being
possibly acute or obtuse, [0089] or have the same direction and the
same sense, [0090] or have the same direction, are of opposite
sense and are disjoint (i.e. not in the straight foregoing of each
other) [globally hereafter referred to as recurring units
(R1-b)].
[0091] Then, a first subset of recurring units (R1-b) suitable as
recurring units (R1) is composed of optionally substituted arylene
groups, the ends of which have a different direction, forming
together an acute angle [recurring units (R1-b1)]. Non limitative
examples of optionally substituted arylene groups the ends of which
have a direction different from each other, include: 1,2-phenylene
(or o-phenylene); 1,2-, 2,3- and 1,7-naphthylenes; 1,2-, 1,8-,
1,9-, 2,3-, 2,5- and 2,10-phenanthrylenes; 1,2- and
1,7-anthrylenes; and any of these groups substituted by at least
one monovalent substituting group, as above defined, in particular
by a phenylketone group.
[0092] A second subset of recurring units (R1-b) suitable as
recurring units (R1) is composed of optionally substituted arylene
groups, the ends of which have a different direction, forming
together an obtuse angle [recurring units (R1-b2)]. Non limitative
examples of optionally substituted arylene groups the ends of which
have a direction different from each other, include: 1,3-phenylene
(or m-phenylene); 1,3- and 1,6-naphthylenes; 1,3-, 1,5-, 1,7-,
2,4-, 2,9- and 3,10-phenanthrylenes; 1,3- and 1,6-anthrylenes; and
any of these groups substituted by at least one monovalent
substituting group, as above defined, in particular by a
phenylketone group.
[0093] A third subset of recurring units (R1-b) is composed of
optionally substituted arylene groups, the ends of which have the
same direction and the same sense [recurring units (R1-b3)]. Non
limitative examples of optionally substituted arylene groups the
ends of which the same direction and the same sense include:
1,8-naphthylene; 1,10- and 3,5-phenanthrylenes; 1,8- and
1,9-anthrylenes; and any of these groups substituted by at least
one monovalent substituting group, as above defined, in particular
by a phenylketone group.
[0094] A fourth subset of recurring units (R1-b) is composed of
optionally substituted arylene groups, the ends of which have the
same direction, are of opposite sense and are disjoint [recurring
units (R1-b4)]. Non limitative examples of such optionally
substituted arylene groups include: 1,5- and 2,6-naphthylenes;
1,6-, 3,9- and 4,10-phenanthrylenes; and 1,5-, 1,10- and
2,6-anthrylenes; and any of these groups substituted by at least
one monovalent substituting group, as above defined, in particular
by a phenylketone group.
[0095] Preferably, recurring units (R1-b) are chosen from recurring
units (R1-b1), recurring units (R1-b2) and recurring units (R1-b4).
More preferably, recurring units (R1-b) are chosen from recurring
units (R1-b1) and recurring units (R1-b2). Still more preferably,
recurring units (R1-b) are chosen from recurring units (R1-b1).
Good results were obtained when recurring units (R1-b) are
optionally substituted m-phenylenes.
[0096] Recurring units (R1-b), when contained in the polyarylene
(P1), result in more or less kinked polymer chains, exhibiting a
higher solubility and fusibility than straight polymer chains. For
this reason, such polyarylenes (P1) are commonly referred to as
"kinked polymers".
[0097] Recurring units (R1) are preferably chosen from [0098]
recurring units (R1-a) which are substituted by at least one
monovalent substituting group [choice (A)]; and [0099] mixes of
recurring units (R1-a), which can be substituted or not by at least
one monovalent substituting group, with recurring units (R1-b),
which can be substituted or not by at least one monovalent
substituting group [choice (B)].
[0100] Choice (B) is generally more preferred than choice A.
Choice (A)
[0101] Recurring units of choice (A) are recurring units (R1-a)
which are substituted by at least one monovalent substituting
group.
[0102] Said recurring units are preferably p-phenylenes substituted
by at least one monovalent substituting group.
[0103] Very preferably, they are p-phenylenes substituted by at
least one monovalent substituting group chosen from
hydrocarbylketones [--C(.dbd.O)--R, where R is a hydrocarbyl group]
and hydrocarbyloxyhydrocarbylketones
[--C(--O)--R.sup.1--O--R.sup.2, where R.sup.1 is a divalent
hydrocarbon group and R.sup.2 is a hydrocarbyl group], said
hydrocarbylketones and hydrocarbyloxyhydrocarbylketones being
themselves unsubstituted or substituted by at least one monovalent
substituting group as those above listed.
[0104] Still more preferably, they are p-phenylenes substituted by
at least one monovalent substituting group chosen from arylketones
and aryloxyarylketones, said arylketones and aryloxyarylketones
being unsubstituted or substituted by at least one monovalent
substituting group as those above listed.
[0105] The most preferably, they are p-phenylenes substituted by an
arylketone group, in particular by the phenylketone group.
Choice (B)
[0106] Recurring units of choice (B) are a mix of recurring units
(R1-a), which can be substituted or not by at least one monovalent
substituting group, with recurring units (R1-b), which can be
substituted or not by at least one monovalent substituting group.
When such a mix of recurring units is contained in the polyarylene
(P1), said polyarylene (P1) is commonly referred to as "a kinked
rigid-rod polymer".
[0107] The recurring units of choice (B) are preferably a mix (M)
of recurring units (R1-a) chosen from optionally substituted
p-phenylenes, with recurring units (R1-b) chosen from (i)
optionally substituted m-phenylenes and (ii) mixes of optionally
substituted m-phenylenes with optionally substituted
o-phenylenes.
[0108] The recurring units (R1-a) of the mix (MB) are preferably
p-phenylene units substituted by at least one substituting group.
More preferably, the recurring units (R1-a) of the mix (MB) are
p-phenylenes substituted by at least one monovalent substituting
group chosen from hydrocarbylketones [--C(--O)--R, where R is a
hydrocarbyl group] and hydrocarbyloxyhydrocarbylketones
[--C(.dbd.O)--R'--O--R.sup.2, where R.sup.1 is a divalent
hydrocarbon group and R.sup.2 is a hydrocarbyl group], said
hydrocarbylketones and hydrocarbyloxyhydrocarbylketones being
themselves unsubstituted or substituted by at least one monovalent
substituting group as those above listed. Still more preferably,
the recurring units (R1-a) of the mix (MB) are p-phenylenes
substituted by at least one monovalent substituting group chosen
from arylketones and aryloxyarylketones, said arylketones and
aryloxyarylketones being unsubstituted or substituted by at least
one monovalent substituting group as those above listed. The most
preferably, they are p-phenylenes substituted by an arylketone
group, in particular by the phenylketone group.
[0109] Essentially all, if not all, the recurring units (R1-b) of
the mix (MB) are m-phenylene units optionally substituted by at
least one substituting group. More preferably, essentially all, if
not all, the recurring units (R1-b) of the mix (MB) are m-phenylene
units which are optionally substituted by at least one monovalent
substituting group chosen from hydrocarbylketones [--C(.dbd.O)--R,
where R is a hydrocarbyl group] and
hydrocarbyloxyhydrocarbylketones [--C(--O)--R.sup.1--O--R.sup.2,
where R.sup.1 is a divalent hydrocarbon group and R.sup.2 is a
hydrocarbyl group], said hydrocarbylketones and
hydrocarbyloxyhydrocarbylketones being themselves unsubstituted or
substituted by at least one monovalent substituting group as those
above listed. Still more preferably, essentially all, if not all,
the recurring units (R1-b) of the mix (MB) are unsubstituted
m-phenylene units. The most preferably, all the recurring units
(R1-b) are m-phenylene units.
[0110] In the mix (MB), the mole ratio of the recurring units
(R1-b), based on the total number of moles of the recurring units
(R1-a) and (R1-b), is usually of at least 1%, preferably at least
5%, more preferably at least 20%, still more preferably at least
30% and the most preferably at least 40%. On the other hand, in the
mix (MB), the mole ratio of the recurring units (R1-b), based on
the total number of moles of the recurring units (R1-a) and (R1-b),
is usually of at most 99%, preferably at most 95%, more preferably
at most 80%, still more preferably at most 70% and the most
preferably at most 60%.
[0111] Good results were obtained when the recurring units of
option (B) were a mix of p-phenylene substituted by a phenylketone
group with unsubstituted m-phenylene, in a mole ratio of about
50:50.
[0112] The polyarylene (P1) may be notably a homopolymer, a random,
alternating or block copolymer.
[0113] Optionally, the polyarylene (P1) may further comprise
recurring units (R1*), different from recurring units (R1).
[0114] Recurring units (R1*) may contain or not at least one strong
divalent electron withdrawing group linked on each of its ends to
an arylene group. Non limitative examples of recurring units (R1*)
free of such strong divalent electron withdrawing group are:
##STR00001##
[0115] Recurring units (R1*) contain preferably at least one strong
divalent electron withdrawing group linked on each of its ends to
an arylene group, in particular a p-phenylene group. The divalent
electron withdrawing group is preferably chosen from the sulfone
group [--S(.dbd.O).sub.2--], the carbonyl group [--C(.dbd.O)--],
the vinylene group [--CH.dbd.CH--], the sulfoxide group
[--S(.dbd.O)--] the azo group [--N.dbd.N--], saturated fluorocarbon
groups like --C(CF.sub.3).sub.2--, organic phosphine oxide groups
[--P(.dbd.O)(.dbd.R.sub.h)--, where R.sub.h is a hydrocarbyl group]
and the ethylidene group [--C(.dbd.CA.sub.2)-, where A can be
hydrogen or halogen]. More preferably, the divalent electron
withdrawing group is chosen from the sulfone group and the carbonyl
group. Still more preferably, recurring units (R1*) are chosen
from: [0116] (i) Recurring Units of Formula
[0116] ##STR00002## [0117] (ii) Recurring Units of Formula
##STR00003##
[0117] [hereinafter, formula (K)] wherein Q is a group chosen
from
##STR00004##
with R being:
##STR00005##
with n being an integer from 1 to 6 and n' being an integer from 2
to 6, Q being preferably chosen from
##STR00006## [0118] (iii) Recurring Units of Formula
[0118] ##STR00007## [0119] (iv) recurring units of formula (K'),
said recurring units being identical to the above recurring units
of formula (K), except that, in formula (K) itself, both sulfone
groups have been replaced by carbonyl groups.
[0120] Preferably more than 50 wt., and more preferably more than
90 wt. % of the recurring units of the polyarylene (P1) are
recurring units (R1). The most preferably, essentially all, if not
all, the recurring units of the polyarylene (P1) are recurring
units (R1).
[0121] Excellent results were obtained when the polyarylene (P1)
was a polyphenylene copolymer, essentially all, if not all, the
recurring units of which consisted of a mix of p-phenylene
substituted by a phenylketone group with unsubstituted m-phenylene
in a mole ratio p-phenylene:m-phenylene of from 5:95 to 95:5,
preferably of from 70:30 to 30:70, more preferably of from 60:40 to
40:60, and still more preferably of about 50:50. Such a
polyphenylene copolymer is commercially available from Solvay
Advanced Polymers, L.L.C. as PRIMOSPIRE.RTM. PR-250
polyphenylene.
[0122] The polyarylene (P1) has a number average molecular weight
of advantageously greater than 500 and, by increasing order of
preference, greater than 1000, 2000, 3000, 5000, 10000 and 15000.
On the other hand, the number average molecular weight of the
polyarylene (P1) is usually below 100000, and preferably below
70000. In a certain embodiment, the number average molecular weight
of the polyarylene (P1) is above 35000. In another embodiment, it
is of at most 35000; in this embodiment, it is often of at most
25000 and sometimes of at most 20000. The number average molecular
weight of a polyarylene, in particular that of the polyarylene
(P1), is advantageously determined by: (1) measuring a "relative"
number average molecular weight of the polyarylene by Gel
Permeation Chromatography (GPC) using polystyrene calibration
standards, then (2) dividing the so-measured "relative" number
average molecular weight by a factor 2. It is proceeded accordingly
because the skilled in the art, who is a specialist of
polyarylenes, knows that their "relative" number average molecular
weight, as measured by GPC, are generally off by a factor of about
2 times; it has already been accounted for this correction factor
in all the above cited lower and upper limits of molecular
weight.
[0123] The polyarylene (P1) can be amorphous (i.e. it has no
melting point) or semi-crystalline (i.e. it has a melting point).
It is preferably amorphous.
[0124] The polyarylene (P1) has a glass transition temperature of
advantageously above 50.degree. C., preferably above 120.degree. C.
and more preferably above 150.degree. C.
[0125] The polyarylene (P1) can be prepared by any method. Methods
well known in the art to prepare the polyarylene (P1) are described
notably in U.S. Pat. Nos. 5,227,457; 5,539,048; 5,565,543;
5,646,231; 5,654,392, 5,659,005, 5,668,245; 5,670,564; 5,721,335;
5,756,581; 5,760,131; 5,824,744; 5,827,927; 5,869,592; 5,886,130;
and 6,087,467, the whole content of which is incorporated herein by
reference. A suitable method for preparing the polyarylene (P1)
comprises polymerizing, preferably by reductive coupling, at least
one dihaloarylene molecular compound consisting of one optionally
substituted arylene group, which is linked on each of its two ends
to one halogen atom, such as chlorine, bromine, iodine. The
elimination of both halogen atoms from a dihaloarylene molecular
compound results in the formation of an optionally substituted
arylene group, suitable as a recurring unit (R1) of the polyarylene
(P1).
[0126] Thus, for example: [0127] the elimination of both chlorine
atoms from one molecule of p-dichlorobenzene, p-dichlorobiphenyl
and their homologous of general formula Cl-(.phi.).sub.N-Cl, N
being an integer from 3 to 10, results in the formation of
respectively 1, 2 or N adjacent p-phenylene units; thus,
p-dichlorobenzene, p-dichlorobiphenyl and their homologous of
general formula Cl-(.phi.).sub.N-Cl, N as above defined, can be
polymerized, so as to form p-phenylene units; [0128]
2,5-dichlorobenzophenone (p-dichlorobenzophenone) can be
polymerized, so as to form 1,4-(benzoylphenylene) units; [0129]
2,5-dichloro-4'-phenoxybenzophenone can be polymerized, so as to
form 1,4-(4'-phenoxybenzoylphenylene) units; [0130]
m-dichlorobenzene can be polymerized, so as to form m-phenylene
units.
[0131] The blend (B) can comprise one and only one polyarylene
(P1). Alternatively, it can comprise two, three, or even more than
three polyarylenes (P1).
[0132] In the blend (B), the polyarylene (P1) can be in any form,
except fibers. More generally, the blend (B) is usually free of any
polyarylene in the form of fibers.
[0133] Preferably, the polyarylene (P1) is in at least one out of
the two following forms: [0134] polyarylene (P1) solubilized in a
phase comprising poly(aryl ether ketone) (P2), possibly the matrix
phase of the blend (B); [0135] polyarylene (P1) forming a
dispersing phase, possibly the matrix phase of the blend (B), said
dispersing phase comprising, dispersed therein, poly(aryl ether
ketone) (P2) at solubilized state and, possibly in addition, in one
or more of the following forms: [0136] nodules of polyarylene (P1)
dispersed in a phase comprising poly(aryl ether ketone) (P2),
possibly the matrix phase of the blend (B); [0137] polyarylene (P1)
forming a dispersing phase, possibly the matrix phase of the blend
(B), said dispersing phase comprising, dispersed therein, nodules
of poly(aryl ether ketone) (P2).
[0138] Very preferably, the polyarylene (P1) is in the form of:
[0139] polyarylene (P1) solubilized in a phase comprising poly(aryl
ether ketone) (P2), possibly the matrix phase of the blend (B);
and, possibly in addition, in the form of: [0140] nodules of
polyarylene (P1) dispersed in a phase comprising poly(aryl ether
ketone) (P2), possibly the matrix phase of the blend (B) wherein:
[0141] certain nodules of polyarylene (P1) may be free of poly(aryl
ether ketone) (P2), and [0142] certain other nodules of polyarylene
(P1) may form themselves a dispersing phase, other than the matrix
phase, comprising, dispersed therein, poly(aryl ether ketone) (P2)
at solubilized state and/or in the form of sub-nodules. The
poly(aryl ether ketone) (P2)
[0143] As previously mentioned, the blend (B) comprises at least
one poly(aryl ether ketone) (P2).
[0144] For the purpose of the present invention, the term
"poly(aryl ether ketone)" is intended to denote any polymer of
which more than 50 wt. % of the recurring units are recurring units
(R2) comprising at least one carbonyl group in-between two arylene
groups, said recurring units (R2) being of one or more of the
following formulae
##STR00008##
wherein: [0145] Ar is independently a divalent aromatic radical
selected from phenylene, biphenylene or naphthylene, [0146] X is
independently O, C(.dbd.O) or a direct bond, [0147] n is an integer
of from 0 to 3, [0148] b, c, d and e are 0 or 1, [0149] a is an
integer of 1 to 4, and [0150] preferably, d is 0 when b is 1.
[0151] Recurring units (R2) may notably be chosen from:
##STR00009## ##STR00010##
[0152] Preferably, recurring (R2) are chosen from
##STR00011##
[0153] More preferably, recurring units (12) are
##STR00012##
[0154] For the purpose of the present invention, a
polyetheretherketone is intended to denote any polymer of which
more than 50 wt. % of the recurring units are recurring units (R2)
of formula (VII).
[0155] The poly(aryl ether ketone) (P2) may further comprise
recurring units (R2*) other than recurring units (R2). Non
limitative example of such recurring units include (i)
arylethersulfone units comprising containing at least one arylene
group, at least one ether group (--O--) and at least one sulfone
group [S(.dbd.O).sub.2], and arylcarbonate units containing at
least one arylene group and at least one carbonate group
(--O--C(.dbd.O)--O--).
[0156] Yet, preferably more than 70 wt. %, and more preferably more
than 85 wt. % of the recurring units of the poly(aryl ether ketone)
(P2) are recurring units (R2). Still more preferably, essentially
all the recurring units of the poly(aryl ether ketone) (P2) are
recurring units (R2). The most preferably, all the recurring units
of the poly(aryl ether ketone) (P2) are recurring units (R2).
[0157] Excellent results were obtained when the poly(aryl ether
ketone) (P2) is a polyetheretherketone homopolymer, i.e. a polymer
of which essentially all, if not all, the recurring units are of
formula (VII). VICTREX.RTM. 150 P and VICTREX.RTM. 450 P PEEKs from
Victrex Manufacturing Ltd., and KETASPIRE.RTM. and GATONE.RTM.
PEEKs from Solvay Advanced Polymers, L.L.C. are examples of
polyetheretherketone homopolymers.
[0158] The poly(aryl ether ketone) (P2) has advantageously a
reduced viscosity (RV) of at least 0.60 dl/g, as measured in 95-98%
sulfuric acid (d=1.84 g/ml) at a poly(aryl ether ketone)
concentration of 1 g/100 ml. The measurement is performed using a
No 50 Cannon-Fleske viscometer. RV is measured at 25.degree. C. in
a time less than 4 hours after dissolution, to limit sulfonation.
The RV of the poly(aryl ether ketone) (P2) is preferably of at
least 0.65 dl/g, more preferably of 0.70 dl/g. Besides, the RV of
the poly(aryl ether ketone) (P2) is advantageously of at most 1.20
dl/g, preferably at most 1.10 and still more preferably at most
1.00 dl/g.
[0159] The poly(aryl ether ketone) (P2) can be amorphous (i.e. it
has no melting point) or semi-crystalline (i.e. it has a melting
point). It is usually semi-crystalline; the case being, the melting
point of the poly(aryl ether ketone) (P2) is advantageously greater
than 150.degree. C., preferably greater than 250.degree. C., more
preferably greater than 300.degree. C. and still more preferably
greater than 325.degree. C.
[0160] The poly(aryl ketone) (P2) can be prepared by any
method.
[0161] One well known in the art method contains reacting a
substantially equimolar mixture of at least one bisphenol and at
least one dihalobenzoid compound or at least one halophenol
compound as described in Canadian Pat. No. 847,963. Non limitative
example of bisphenols useful in such a process are hydroquinone,
4,4'-dihydroxybiphenyl and 4,4'-dihydroxybenzophenone; non
limitative examples of dihalobenzoid compounds useful in such a
process are 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone
and 4-chloro-4'-fluorobenzophenone; non limitative examples of
halophenols compounds useful in such a process are
4-(4-chlorobenzoyl)phenol and (4-fluorobenzoyl)phenol. Accordingly,
PEEK homopolymers may notably be produced by the nucleophilic
process as described in, for example, U.S. Pat. No. 4,176,222, the
whole content of which is herein incorporated by reference.
[0162] Another well known in the art method to produce PEEK
homopolymers comprises electrophilically polymerizing
phenoxyphenoxybenzoic acid, using an alkane sulfonic acid as
solvent and in the presence of a condensing agent, as the process
described in U.S. Pat. No. 6,566,484, the whole content of which is
herein incorporated by reference. Other poly(aryl ether ketone)s
may be produced by the same method, starting from other monomers
than phenoxyphenoxybenzoic acid, such as those described in U.S.
Pat. Appl. 2003/0130476, the whole content of which is also herein
incorporated by reference.
[0163] The blend (B) can comprise one and only one poly(aryl ether
ketone) (P2). Alternatively, it can comprise two, three, or even
more than three poly(aryl ether ketone)s (P2). Certain preferred
mixes of poly(aryl ether ketone)s (P2) are: mixes consisting of (i)
at least one poly(aryl ether ketone) (P2a) of which more than 50
wt. % of the recurring units, preferably essentially all the
recurring units, and still more preferably all the recurring units
are of formula
##STR00013##
with (ii) at least one poly(aryl ether ketone) (P2b) of which more
than 50 wt. % of the recurring units, preferably essentially all
the recurring units, and still more preferably all the recurring
units are of formula
##STR00014##
and, optionally in addition, with (iii) at least one other
poly(aryl ether ketone) (P2c) different from poly(aryl ether
ketone)s (P2a) and (P2b); in particular, mixes consisting of (i) at
least one poly(aryl ether ketone) (P2a) of which essentially all,
if not all, the recurring units are of formula (VII) with (ii) at
least one poly(aryl ether ketone) (P2b) of which essentially all,
if not all, the recurring units are of formula (IX); still more
particularly, binary mixes consisting of (i) one poly(aryl ether
ketone) (P2a) of which all the recurring units are of formula (VII)
with (ii) one poly(aryl ether ketone) (P2b) of which all the
recurring units are of formula (IX).
EMBODIMENT (E*)
[0164] In a particular embodiment of the present invention (E*),
the poly(aryl ether ketone) (P2) is a poly(aryl ether sulfone),
namely a polymer of which at least 5 wt. % of the recurring units
are recurring units of one or more formulae comprising at least one
arylene group, at least one ether group (--O--) and at least one
sulfone group [--S(.dbd.O).sub.2--].
[0165] In embodiment (E*), the poly(aryl ether ketone) (P2) may
comprise: (i) repeating units (PhSO.sub.2Ph).sub.r linked through
ether and/or thioether, where n is 1 to 3 or can be fractional in
this range, and (ii) structural units (Ph).sub.k so linked, wherein
Ph is phenylene (especially para-phenylene), "k" is 1 to 3 or can
be fractional within this range, and at least part of such
phenylenes are linked linearly through a divalent --CO-- group, the
remaining part of such phenylenes, if any, being fused together or
are linked through a single chemical bond or a divalent group other
than SO.sub.2 and --CO--.
[0166] By "fractional" reference is made to the average value for a
given polymer chain containing units having various values of "n"
or "k".
[0167] In embodiment (E*), the polyarylene (P1) may meet all the
characteristics of the polyphenylenes described in
PCT/EP2006/060535, as long as they are compatible with those of the
polyarylene (P1) described in the present document.
[0168] The person skilled in the art will understand that the
invention is not intended to be limited to this particular
embodiment (E*), but encompasses also any embodiment other than
(E*) which is described in the present document. Besides, various
modifications to the embodiments described in the present document
will be readily apparent to those skilled in the art, and the
generic principles defined herein may be applied to other
embodiments without departing from the spirit and scope of the
invention; thus, this invention is also not intended to be limited
to all the embodiments shown, but is to be accorded the widest
scope consistent with the principles and features disclosed
herein.
Optional Ingredients of the Blend (B)
[0169] The blend (B) may further contain a variety of polymers
other than (P1) and (P2), additives, fillers, and the like,
collectively called ingredients. Conventional ingredients of
polyarylene and poly(aryl ether ketone) compositions, include
fibrous reinforcing agents, particulate fillers and nucleating
agents such as talc and silica, adhesion promoters,
compatibilizers, curing agents, lubricants, metal particles, mold
release agents, organic and/or inorganic pigments like TiO.sub.2
and carbon black, dyes, flame retardants, smoke-suppressing agents,
heat stabilizers, antioxidants, UV absorbers, tougheners such as
rubbers, plasticizers, anti-static agents, melt viscosity
depressants such as liquid crystalline polymers and the like.
[0170] The weight of said optional ingredients, based on the total
weight of the blend (B), is advantageously below 75%, preferably
below 50%, more preferably below 25% and still more preferably
below 10%. Good results were obtained when the blend (B) was
essentially free, or even was completely free, of said optional
ingredients.
[0171] In particular, the blend (B) may further contain a fibrous
reinforcing agent, in particular an inorganic fibrous reinforcing
agent such as glass fiber and carbon fiber. Thus, in a certain
particular non preferred embodiment, the blend (B) comprises from
10 to 50 wt. %, in particular from 20 to 30 wt. %, of a reinforcing
agent (all percentages based on the total weight of the blend); an
example of such a blend is one composed of 35 wt. % of a kinked
rigid-rod polyphenylene homopolymer, 35 wt. % of a
polyetheretherketone homopolymer and 30 wt. % of glass fiber. On
the other hand, preference is given to a blend (B) wherein the
weight of fibrous reinforcing agent, based on the total weight of
the blend (B), is below 10% and preferably below 5%, and excellent
results were obtained when the blend (B) was essentially free, or
even was completely free, of any fibrous reinforcing agent.
EMBODIMENT (E**)
Blend (T)
[0172] In an especially valuable embodiment of the present
invention, at least one polyarylene, at least one poly(aryl ether
ketone) and at least one poly(aryl ether sulfone) are contained in
a same blend. The Applicant has surprisingly found that the
additional presence of a poly(aryl ether sulfone) in a blend
comprising a polyarylene and a poly(aryl ether ketone), such as the
above described blend (B), resulted in a blend (T) having several
substantially improved properties when compared to the blend (B),
while maintaining all its beneficial properties at a high level.
Among the improved properties, the elongation at break and the
impact resistance are dramatically increased. Also, the poly(aryl
ether sulfone) act as a compatibilizer, by further increasing the
unexpectedly intrinsically good compatibility of the polyarylene
and the poly(aryl ether ketone), and providing blends of improved
morphology, wherein the polyarylene and the poly(aryl ether ketone)
domain sizes are substantially finer than absent the poly(aryl
ether sulfone).
[0173] The blend (B) as previously described and further containing
at least one poly(aryl ether sulfone) (P3) is a blend in accordance
with present embodiment (E**) of the present invention, said blend
(B) comprising then [0174] at least one polyarylene (P1) in a form
other than fibers, [0175] at least one poly(aryl ether ketone)
(P2), and [0176] at least one poly(aryl ether sulfone) (P3).
[0177] Another blend in accordance with embodiment (E**) comprises
[0178] polyarylene fibers, [0179] at least one poly(aryl ether
ketone) (P2), and [0180] at least one poly(aryl ether sulfone)
(P3).
[0181] Taken as a whole, the embodiment (E**) is thus directed to a
blend (T) comprising: [0182] at least one polyarylene (P1.sup.+),
[0183] at least one poly(aryl ether ketone) (P2), and [0184] at
least one poly(aryl ether sulfone) (P3).
[0185] The polyarylene (P1.sup.+) may be in any form. The
polyarylene (P1.sup.+) may consist of fibers, or it may be in a
form other than fibers. Preferably, the polyarylene (P1.sup.+) is
in a form other than fibers, like the polyarylene (P1).
[0186] Unless otherwise specified, the polyarylene (P1.sup.+)
complies preferably with all the preferred characteristics of the
polyarylene (P1), i.e., among other preferences, the polyarylene
(P1.sup.+) is preferably a polyphenylene, and excellent results
were obtained when the polyarylene (P1.sup.+) was a polyphenylene
copolymer, essentially all, if not all, the recurring units of
which consisted of a mix of p-phenylene substituted by a
phenylketone group with unsubstituted m-phenylene in a mole ratio
p-phenylene:m-phenylene of from 5:95 to 95:5, preferably of from
70:30 to 30:70, more preferably of from 60:40 to 40:60, and still
more preferably of about 50:50.
[0187] For the avoidance of doubt, the poly(aryl ether ketone) (P2)
of the blend (T) is the exactly the same poly(aryl ether ketone) as
the poly(aryl ether ketone) (P2) as above described, as an
ingredient of the blend (B).
[0188] In the blend (T), the weight of the polyarylene (P1.sup.+),
based on the total weight of the polyarylene (P1.sup.+) and the
poly(aryl ether ketone) (P2), is advantageously of at least 15%,
preferably at least 30% and more preferably at least 40%; it may be
of at least 45% or of at least 55%. On the other hand, the weight
of the polyarylene (P1.sup.+), based on the total weight of the
polyarylene (P1.sup.+) and the poly(aryl ether ketone) (P2), is
advantageously of at most 90%, preferably at most 80%, and more
preferably at most 70%.
[0189] In the blend (T), the poly(aryl ether sulfone) (P3) over
polyarylene (P1.sup.+) weight ratio may vary to a large extent,
depending on the encompassed end use. It may be notably of at least
0.01, 0.02, 0.05, 0.10, 0.20, 0.50, 1, 2 or 5 or 10. It may be
notably of at most 10, 5, 2, 1 or 0.50. Notably when the poly(aryl
ether sulfone) (P3) is used for the purpose of compatibilizing the
polyarylene (P1.sup.+) with the poly(aryl ether ketone) (P2), the
poly(aryl ether sulfone) (P3) over polyarylene (P1.sup.+) weight
ratio is advantageously of at least 0.05, preferably at least 0.10,
and more preferably at least 0.15; on the other hand, the poly(aryl
ether sulfone) (P3) over polyarylene (P1.sup.+) weight ratio is
advantageously of at most 1, preferably at most 0.50, and more
preferably at most 0.30.
[0190] Likewise, in the blend (T), the poly(aryl ether sulfone)
(P3) over poly(aryl ether ketone) (P2) weight ratio may vary to a
large extent, depending on the encompassed end use. It may be
notably of at least 0.01, 0.02, 0.05, 0.10, 0.20, 0.50, 1, 2 or 5
or 10. It may be notably of at most 10, 5, 2, 1 or 0.50. Notably
when the poly(aryl ether sulfone) (P3) is used for the purpose of
compatibilizing the polyarylene (P1) with the poly(aryl ether
ketone) (P2), the poly(aryl ether sulfone) (P3) over poly(aryl
ether ketone) (P2) weight ratio is advantageously of at least 0.05,
preferably at least 0.10, and more preferably at least 0.15; on the
other hand, it is advantageously of at most 1, preferably at most
0.50, and more preferably at most 0.30.
[0191] In the blend (T), the total weight of the polyarylene
(P1.sup.+), of the poly(aryl ether ketone) (P2) and of the
poly(aryl ether sulfone) (P3), based on the total weight of the
blend (T), is advantageously above 25%, preferably above 50%, more
preferably above 80% and still more preferably above 95%. Excellent
results were obtained when the blend (T) consisted essentially of,
or even consisted of, the polyarylene (P1.sup.+), the poly(aryl
ether ketone) (P2) and the poly(aryl ether sulfone) (P3).
[0192] In the blend (T), the weight of the polyarylene (P1.sup.+),
based on the total weight of the blend (T), is advantageously of at
least 15%, preferably at least 25%, more preferably at least 35%;
it may be of at least 40% or at least 50%. On the other hand, the
weight of the polyarylene (P1.sup.+), based on the total weight of
the blend (T), is advantageously of at most 85%, preferably at most
75%, more preferably at most 65%, and still more preferably at most
60%; it may be of at most 50% or at most 40%.
[0193] In the blend (T), the weight of the poly(aryl ether ketone)
(P2), based on the total weight of the blend (T), is advantageously
of at least 15%, preferably at least 25%, more preferably at least
35%; it may be of at least 40% or at least 50%. On the other hand,
the weight of the poly(aryl ether ketone) (P2), based on the total
weight of the blend (T), is advantageously of at most 85%,
preferably at most 75%, more preferably at most 65%, and still more
preferably at most 60%; it may be of at most 50% or at most
40%.
[0194] In the blend (T), the weight of the poly(aryl ether sulfone)
(P3), based on the total weight of the blend (T), may vary to a
large extent, for the same reasons as those above explained. It may
be of at least 1%, 2%, 5%, 10%, 20%, 40% or 60%; it may be of at
most 70%, 50%, 40%, 30%, 20%, 15% or 10%. Notably when the
poly(aryl ether sulfone) (P3) is used as compatibilizer, its
weight, based on the total weight of the blend (T), is
advantageously of at least 1%, preferably at least 2%, more
preferably at least 5%, and still more preferably at least 8%; on
the other hand, the weight of the poly(aryl ether sulfone) (P3),
based on the total weight of the blend (T), is advantageously of at
most 45%, preferably at most 35%, more preferably at most 18%, and
still more preferably at most 12%, based on the total weight of the
blend (T).
The poly(aryl ether sulfone) (P3)
[0195] For the purpose of the invention, a poly(aryl ether sulfone)
is intended to denote any polymer, generally a polycondensate, of
which more than 50 wt. % of the recurring units are recurring units
(R3) of one or more formulae containing at least one arylene group,
at least one ether group (--O--) and at least one sulfone group
[--S(.dbd.O).sub.2-]. The poly(aryl ether sulfone) (P3) differs
generally from the polyarylene (P1.sup.+) and the poly(aryl ether
ketone) (P2).
[0196] Non limitative examples of poly(aryl ether sulfone)s are
polymers of which more than 50 wt. %, up to 100 wt. %, of the
recurring units are recurring units (R3) of formula (1) and/or
(2):
##STR00015##
wherein: [0197] Q is a group chosen among the following
structures:
##STR00016##
[0197] with R being:
##STR00017##
with n=integer from 1 to 6, or an aliphatic divalent group, linear
or branched, of up to 6 carbon atoms; and mixtures thereof; [0198]
Ar is a group chosen among the following structures
##STR00018##
[0198] with R being:
##STR00019##
with n=integer from 1 to 6, or an aliphatic divalent group, linear
or branched, of up to 6 carbon atoms; and mixtures thereof; [0199]
Ar' is a group chosen among the following structures:
##STR00020##
[0199] with R being:
##STR00021##
with n=integer from 1 to 6, or an aliphatic divalent group, linear
or branched, of up to 6 carbon atoms; and mixtures thereof.
[0200] Among such polymers, it can be particularly cited the
polymers of which more than 50 wt. %, up to 100 wt. %, of the
recurring units are recurring units of one or more of formulae (3),
(4), (5) and (6):
##STR00022##
[0201] Polymers comprising more than 50 wt. % of recurring units of
formula (3) are commonly known as "polyphenylsulfones" (PPSU) and
are commercially available notably from SOLVAY ADVANCED POLYMERS,
L.L.C. as RADEL.RTM. R poly(aryl ether sulfone)s.
[0202] Polymers comprising more than 50 wt. % of recurring units of
formula (4) are commonly known as "polyetherethersulfones".
[0203] Polymers comprising more than 50 wt. % of recurring units of
formula (5) are commonly known as polyethersulfones and are
commercially available notably from SOLVAY ADVANCED POLYMERS,
L.L.C. as RADEL.RTM. A poly(aryl ether sulfone)s.
[0204] Polymers comprising more than 50 wt. % of recurring units of
formula (6) are commonly known as "bisphenol A polysulfones" (or
just "polysulfones") and are commercially available notably from
SOLVAY ADVANCED POLYMERS, L.L.C. as UDEL.RTM. poly(aryl ether
sulfone)s.
[0205] The blend (T) may contain one and only one poly(aryl ether
sulfone) (P3). Alternatively, the blend (T) may contain two or more
one poly(aryl ether sulfone)s (P3); for example, it may contain at
least one polyphenylsulfone and at least one polysulfone, or it may
contain at least one polyphenylsulfone and at least one
polyethersulfone.
[0206] Preferably, the recurring units (R3), as above defined,
contain at least one p-biphenylene group
##STR00023##
as the at least one arylene group. The case being, the poly(aryl
ether sulfone) is commonly known as a poly(biphenyl ether sulfone).
For the purpose of the present invention, a poly(biphenyl ether
sulfone) is intended to denote any polymer, generally a
polycondensate, of which more than 50 wt. % of the recurring units
are recurring units (R3) of one or more formulae containing at
least one p-biphenylene group:
##STR00024##
at least one ether group (--O--) and at least one sulfone group
[--S(.dbd.O).sub.2-]. A poly(biphenyl ether sulfone) may further
comprise one or more arylene groups other than the p-biphenylene
groups, such as phenylene and naphthylene groups.
Polyphenylsulfones are poly(biphenyl ether sulfone)s of a
particular type.
[0207] The blend (T) may contain one and only one poly(biphenyl
ether sulfone) (P3). Alternatively, the blend (T) may contain two
or more one poly(biphenyl ether sulfone)s (P3); for example, it may
contain at least one polyphenylsulfone and at least one
poly(biphenyl ether sulfone) of which the recurring units (R3)
containing at least 2 sulfone groups, such as the recurring units
of formulae (8) to (11) as defined afterwards.
[0208] More preferably, the recurring units (R3) are of one or more
formulae of the general type:
##STR00025##
wherein R.sub.1 through R.sub.4 are --O--, --SO.sub.2--, --S--,
--C(.dbd.O)--, with the proviso that at least one of R.sub.1
through R.sub.4 is --SO.sub.2-- and at least one of R.sub.1 through
R.sub.4 is --O--; Ar.sub.1, Ar.sub.2 and Ar.sub.3 are arylene
groups containing 6 to 24 carbon atoms, and are preferably
phenylene or p-biphenylene; and a and b are either 0 or 1.
[0209] Still more preferably, the recurring units (R3) are chosen
from
##STR00026##
and mixtures thereof.
[0210] The most preferably, the recurring units (R3) are
##STR00027##
[0211] Otherwise said, the most preferred poly(aryl ether sulfone)
is a polyphenylsulfone.
[0212] The poly(aryl ether sulfone) (P3) may be notably a
homopolymer, a random, alternating or block copolymer. When the
poly(aryl ether sulfone) (P3) is a copolymer, its recurring units
may notably be composed of: [0213] recurring units (R3) of at least
two different formulae chosen among formulae (3), (8), (9), (10)
and (11), or [0214] recurring units (R3) of one or more formulae
chosen among formulae (3), (8), (9), (10) and (11), and recurring
units (R3) of one or more formulae chosen among formulae (4), (5)
and (6).
[0215] Preferably more than 70 wt. %, more preferably more than 85
wt. % of the recurring units of the poly(aryl ether sulfone) (P3)
are recurring units (R3). Still more preferably, essentially all
the recurring units of the poly(aryl ether sulfone) (P3) are
recurring units (R3). The most preferably, all the recurring units
of the poly(aryl ether sulfone) (P3) are recurring units (R3).
[0216] Excellent results were obtained when the poly(aryl ether
sulfone) (P3) was a polyphenylsulfone homopolymer, i.e. a polymer
of which essentially all, if not all, the recurring units are of
formula (3).
[0217] The poly(aryl ether sulfone) (P3) can be prepared by any
method. Methods well known in the art are those described in U.S.
Pat. Nos. 3,634,355; 4,008,203; 4,108,837 and 4,175,175, the whole
content of which is herein incorporated by reference.
Optional Ingredients of the Blend (T)
[0218] The blend (T) may further contain a variety of polymers
other than (P1.sup.+), (P2) and (P3), and additives, fillers, and
the like, collectively called ingredients. Conventional ingredients
of polyarylene, poly(aryl ether ketone) and poly(aryl ether
sulfone) compositions, include fibrous reinforcing agents,
particulate fillers and nucleating agents such as talc and silica,
adhesion promoters, compatibilizers, curing agents, lubricants,
metal particles, mold release agents, organic and/or inorganic
pigments like TiO.sub.2 and carbon black, dyes, flame retardants,
smoke-suppressing agents, heat stabilizers, antioxidants, UV
absorbers, tougheners such as rubbers, plasticizers, anti-static
agents, melt viscosity depressants such as liquid crystalline
polymers and the like.
[0219] The weight of said optional ingredients, based on the total
weight of the blend (T), is advantageously below 75%, preferably
below 50%, more preferably below 25% and still more preferably
below 10%. Good results were obtained when the blend (T) was
essentially free, or even was completely free, of said optional
ingredients.
[0220] In particular, the blend (T) may further contain a fibrous
reinforcing agent, in particular an inorganic fibrous reinforcing
agent such as glass fiber and carbon fiber. Thus, in a certain
particular non preferred embodiment, the blend (T) comprises from
10 to 50 wt. %, in particular from 20 to 30 wt. %, of a reinforcing
agent (all percentages based on the total weight of the blend); an
example of such a blend is one composed of 35 wt. % of a kinked
rigid-rod polyphenylene homopolymer, 35 wt. % of a
polyetheretherketone homopolymer and 30 wt. % of glass fiber. On
the other hand, preference is given to a blend (T) wherein the
weight of fibrous reinforcing agent, based on the total weight of
the blend (T), is below 10% and preferably below 5%, and excellent
results were obtained when the blend (T) was essentially free, or
even was completely free, of any fibrous reinforcing agent.
The Polymer Blend (T) is Well Suited for Flexible Risers
Applications
[0221] The Applicant has surprisingly found that the polymer blend
(T) was well suited notably for producing certain layers of
flexible pipes for transporting hydrocarbons.
[0222] Then, a first particular aspect of the present invention, as
described in U.S. application No. 60/912,989, concerns a polymer
blend (T') suitable for producing a layer of a flexible pipe for
transporting hydrocarbons, said polymer blend (T') comprising:
[0223] at least one polyarylene (P1'), and [0224] a mix (M23')
selected from the group consisting of (i) mixes of at least one
poly(aryl ether ketone) (P2') and at least one poly(aryl ether
sulfone) (P3'), and (ii) mixes of at least one poly(aryl ether
ketone) (P2'), at least one poly(aryl ether sulfone) (P3') and at
least one fluoropolymer (P4').
[0225] Any polyarylene can be used as the polyarylene (P1'). The
polyarylene (P1') comprised in the polymer blend (T') is
advantageously a polymer of which more than 50 wt. % of the
recurring units are recurring units (R1') of one or more formulae
consisting of an optionally substituted arylene group, provided
said optionally substituted arylene group is linked by each of its
two ends to two other optionally substituted arylene groups via a
direct C--C linkage, as defined in U.S. application No. 60/912,989.
The polyarylene (P1') comprised in the polymer blend (T') is also
advantageously the polyarylene (P1) in a form other than fibers, as
above described. Good results are obtained when the polyarylene
(P1') is a polyphenylene.
[0226] Any poly(aryl ether ketone) can be used as the poly(aryl
ether ketone) (P2'). The poly(aryl ether ketone) (P2') is
advantageously a polycondensate, of which more than 50 wt. % of the
recurring units are recurring units (R2') of one or more formulae
containing at least one arylene group, at least one ether group
(--O--) and at least one ketone group [--C(.dbd.O)-], the said one
or more formulae being free of sulfone group [--S(.dbd.O).sub.2--],
as defined in U.S. application No. 60/912,989. The poly(aryl ether
ketone) (P2') comprised in the polymer blend (T') is also
advantageously the poly(aryl ether ketone) (P2) as above described.
Good results are obtained when the poly(aryl ether ketone) (P2') is
a polyetheretherketone.
[0227] Any poly(aryl ether sulfone) can be used as the poly(aryl
ether sulfone) (P3'). The poly(aryl ether sulfone) (P3') comprised
in the polymer blend (T') is advantageously a polymer other than
the polyarylene (P1'), generally a polycondensate, of which more
than 50 wt. % of the recurring units are recurring units (R3') of
one or more formulae containing at least one arylene group, at
least one and at least one ether group (--O--) and at least one
sulfone group [--S(.dbd.O).sub.2-]. The poly(aryl ether sulfone)
(P3') comprised in the polymer blend (T') is also advantageously
the poly(aryl ether sulfone) (P3) as above described. Good results
are obtained when the poly(aryl ether sulfone) (P3') is a
polyphenylsulfone.
[0228] Any fluoropolymer can be used as the fluoropolymer (P4').
The fluoropolymer (P4') may be a polytetrafluoroethylene, an ETFE,
a CTFE, an ECTFE, a polyvinylidene fluoride or a
perfluoroalkylvinylether [like perfluoromethylvinylether (MFA) and
perfluoropropylvinylether (PFA)]. Good results are obtained when
the fluoropolymer (P4') is a polytetrafluoroethylene.
[0229] The mix (M23') consists preferably of at least one poly(aryl
ether ketone) (P2') and at least one poly(aryl ether sulfone)
(P3').
[0230] In the polymer blend (T'), the weight of the polyarylene
(P1'), based on the weight of the polymer blend (T'), may be
notably of at least 1, 2, 5, 10, 20, 30, 40, 50, 60, 70, 80 or 90%.
On the other hand, the weight of the polyarylene (P1'), based on
the weight of the polymer blend (T'), may be notably of at most 90,
80, 70, 60, 50, 40, 30, 20 or 10%. The following amounts lower and
upper limits may be used as lower and upper limits for the weight
of the polyarylene (P1') notably for sub-embodiments (E'-1) and
(E'-2) as detailed below, insofar as these limits are compatible
with the requirements of these sub-embodiments.
[0231] In a first sub-embodiment (E'-1), the weight of the
polyarylene (P1'), based on the weight of the polymer blend (T'),
is preferably between 50% and 100%, more preferably between 55 and
85%, still more preferably between 60 and 70%. In sub-embodiment
(E'-1), the weight of the mix (M23'), based on the weight of the
polymer blend (T'), is preferably from 5 to 45%, more preferably
from 15 to 45%, still more preferably from 30 to 40%.
[0232] In a second sub-embodiment (E'-2), the weight of the
polyarylene (P1'), based on the weight of the polymer blend (T') is
of at most 50%; it is preferably of at most 40%. In sub-embodiment
(E'-2), the weight of the mix (M23'), based on the weight of the
polymer blend (T'), is preferably from 50 to 99%, more preferably
from 55 to 90%, and still more preferably from 60 to 70%. In
sub-embodiment (E'-2), the polymer blend (T') comprises preferably
from 0 to 40%, more preferably from 0 to 20%, still more preferably
from 0 to 5%, of at least one non polymeric ingredient; the most
preferably, the polymer blend (T') is essentially free, or even
free, of non polymeric ingredient.
[0233] Another particular aspect of the present invention, as
described in U.S. application No. 60/909,514, concerns a polymer
composition (T'') suitable for producing a layer of a flexible pipe
for transporting hydrocarbons, said polymer composition (T'')
comprising: [0234] at least one polyarylene (P1'') selected from
the group consisting of polyphenylenes, [0235] at least one
poly(aryl ether ketone) (P2''), and [0236] at least one poly(aryl
ether sulfone) (P3'') wherein: [0237] the weight of the poly(aryl
ether ketone) (P2''), based on the total weight of the poly(aryl
ether ketone) (P2'') and the poly(aryl ether sulfone) (P3''), is
from 35% to 95%, and [0238] the polymer composition (T'') is free
of epoxy resin modified by at least one aromatic polyamine, or
comprises the said epoxy resin modified by at least one polyamine
in a weight amount of at most 10%, based on the total weight of the
polymer composition (T'').
[0239] Any polyphenylene can be used as the polyarylene (P1''). The
polyarylene (P1'') comprised in the polymer composition (T'') is
advantageously the polyarylene (P1) in a form other than fibers as
above described, provided said polyarylene (P1) is selected from
the group consisting of polyphenylenes.
[0240] Any poly(aryl ether ketone) can be used as the poly(aryl
ether ketone) (P2''). The poly(aryl ether ketone) (P2'') comprised
in the polymer composition (T'') is advantageously a polymer,
generally a polycondensate, of which more than 50 wt. % of the
recurring units are recurring units (R2'') of one or more formulae
containing at least one arylene group, at least one ether group
(--O--) and at least one ketone group [--C(.dbd.O)--], the said one
or more formulae being free of sulfone group [--S(.dbd.O).sub.2--],
as defined in U.S. application No. 60/909,514. The poly(aryl ether
ketone) (P2'') comprised in the polymer composition (T'') is also
advantageously the poly(aryl ether ketone) (P2) as above described.
Good results are obtained when the poly(aryl ether ketone) (P2'')
is a polyetheretherketone.
[0241] Any poly(aryl ether sulfone) can be used as the poly(aryl
ether sulfone) (P3''). The poly(aryl ether sulfone) (P3'')
comprised in the polymer composition (T'') is advantageously a
polymer, generally a polycondensate, of which more than 50 wt. % of
the recurring units are recurring units (R3'') of one or more
formulae containing at least one arylene group, at least one and at
least one ether group (-O--) and at least one sulfone group
[--S(.dbd.O).sub.2-], as defined in U.S. application No.
60/909,514. The poly(aryl ether sulfone) (P3'') comprised in the
polymer composition (T'') is also advantageously the poly(aryl
ether sulfone) (P3) as above described. Good results are obtained
when the poly(aryl ether sulfone) (P3') is a polyphenylsulfone.
[0242] In the polymer composition (T''), the weight of the
poly(aryl ether ketone) (P2''), based on the total weight of the
poly(aryl ether ketone) (P2'') and the poly(aryl ether sulfone)
(P3''), may be of at least 40, 45 or 50%; it is preferably above
50%, more preferably above 55%, and still more preferably at most
60%. On the other hand, the weight of the poly(aryl ether ketone)
(P2''), based on the total weight of the poly(aryl ether ketone)
(P2'') and the poly(aryl ether sulfone) (P3''), may be of at most
90, 85 or 80%; it is preferably below 80%, more preferably below
75% and still more preferably below 70%.
[0243] In the polymer composition (T''), the total weight of the
poly(aryl ether ketone) (P2'') and the poly(aryl ether sulfone)
(P3''), based on the total weight of the polymer composition (T''),
is advantageously above 35%, preferably above 55%, more preferably
above 65%, and still more preferably above 75%. In certain
embodiments, the total weight of the poly(aryl ether ketone) (P2'')
and the poly(aryl ether sulfone) (P3''), based on the total weight
of the polymer composition (T''), may be above 80%, 90% or 95%.
[0244] In the polymer composition (T''), the weight amount of the
polyarylene (P1''), based on the total weight of the polymer
composition (T''), is generally below 30%; the weight amount of the
polymer (P1''), based on the total weight of the polymer
composition (T''), may be of at most 25%, 20%, 15% or 10%. Besides,
it may be of at least 1%, 2%, 3%, 5% or 10%, based on the total
weight of the polymer composition (T'').
[0245] The polymer blends (T') and (T'') may contain additional
ingredients. Unless incompatible with the nature of the polymer
blends (T') and (T''), all what was mentioned here above concerning
the optional ingredients of the polymer blend (T) can apply,
mutatis mutandis, to the polymer blends (T') and (T'').
[0246] As above said, the polymer blend (T) is well suited for
producing a polymer layer comprised in a flexible pipe for
transporting hydrocarbons, and still another particular aspect of
the present invention is directed to said flexible pipe itself; in
particular, the polymer blends (T') and (T'') are especially well
suited for this purpose. The polymer layer is advantageously an
antiwear polymer layer, which separates two metal armor plies, and
it may be produced by helically winding a tape composed of the
polymer blend (T), (T') or (T'').
The Preparation of the Invented Blends
[0247] The blends (B) and (T) can be prepared by any method.
[0248] An aspect of the present invention is directed to a method
for preparing the blend (B) as above described which comprises
mixing at least one polyarylene (P1) in a form other than fibers
with at least one poly(aryl ether ketone) (P2), at a temperature
above the melt temperature of the polyarylene (P1) and the melt
temperature of the poly(aryl ether ketone) (P2).
[0249] Another aspect of the present invention is directed to a
method for preparing the blend (T) as above described which
comprises mixing at least one polyarylene (P1) with at least one
poly(aryl ether ketone) (P2) and at least one poly(aryl ether
sulfone) (P3), at a temperature above the melt temperature of the
poly(aryl ether ketone) (P2) and the melt temperature of the
poly(aryl ether sulfone) (P3). The mixing takes preferably place at
a temperature which is also above the melt temperature of the
poly(arylene) (P1.sup.+).
[0250] For the purpose of the present invention, the melt
temperature of a polymer is its glass transition temperature, if
said polymer is amorphous, and its melting point, if said polymer
is semi-crystalline.
[0251] The melt temperature of the polyarylene (P1) [or
(P1.sup.+)], the melt temperature of the poly(aryl ether ketone)
(P2) and the melt temperature of the poly(aryl ether sulfone) (P3)
can be measured by any suitable technique known from the skilled in
the art. Very often, it is measured by Differential Scanning
Calorimetry, using for example a Universal V3.7A Instruments DSC
calorimeter. For this purpose, it is preliminarily checked that the
calorimeter is well-calibrated by means of a calibration sample.
Then, the polymer of which the melt temperature has to be measured
[polymer (P1) or (P2) or (P3) or the like] is submitted to the
following heating/cooling cycle: 1.sup.st heating from room
temperature (20.degree. C.) up to T.sub.max at a rate of 10.degree.
C./min, followed by cooling from T.sub.max down to room temperature
at a rate of 20.degree. C./min, followed by 2.sup.nd heating from
room temperature up to T.sub.max at a rate of 10.degree. C./min.
Here, T.sub.max denotes the maximum temperature of the cycle;
T.sub.max is chosen so as to be well above the melt temperature of
the polymer submitted to the determination, but well below the
temperature at which the polymer starts to degrade; values of
T.sub.max of from about 30.degree. C. to about 100.degree. C. above
the melt temperature are in general suitable; values of T.sub.max
of about 220.degree. C. may be appropriate to measure the melt
temperature, in particular the glass transition temperature, of the
polyarylene (P1), while values of T.sub.max of about 400.degree. C.
may be appropriate to measure the melt temperature, in particular
the melting point, of the poly(aryl ether ketone) (P2).
[0252] The melt temperature was measured during 2.sup.nd
heating.
[0253] When the melt temperature of the polymer (P1) or (P2) or
(P3) or the like is its melting point melting is an endothermic
first-order transition that appears as a negative peak on the DSC
scan. The melting point is advantageously determined by a certain
construction procedure on the heat flow curve the intersection of
the two lines that are tangent to the peak at the points of
inflection on either side of the peak define the peak temperature,
namely the melting point.
[0254] When the glass transition temperature of the polymer (P1) or
(P2) or (P3) or the like is its glass transition temperature, this
one is advantageously determined by a certain other construction
procedure on the heat flow curve: a first tangent line to the curve
above the transition region is constructed a second tangent line to
the curve below the transition region is also constructed; the
temperature on the curve halfway between the two tangent lines, or
1/2 delta Cp, is the glass transition temperature.
[0255] The mixing of the polyarylene (P1) [or (P1.sup.+)] with the
poly(aryl ether ketone) (P2) [and possibly in addition, with the
poly(aryl ether sulfone) (P3)] can be achieved by any appropriate
means. The mixing is advantageously made under a sufficiently high
shear, so as to achieve a high degree of mixing of all the polymers
in the blend (B) or (T) ("shear-mixing"). The mixing can notably be
achieved in a desirable manner by extruding the polyarylene (P1)
[or (P1.sup.+)] with the poly(aryl ether ketone) (P2) [and possibly
in addition, with the poly(aryl ether sulfone) (P3)], at a
temperature above the melt temperature of each of the extruded
polymers, so as to obtained strands of the blend (B) [or of the
blend (T)]. Very preferably, the so-obtained strands are then
chopped into pellets.
[0256] The invented method preferably further comprises the step of
dry mixing the polyarylene (P1) [or (P1.sup.+)] with the poly(aryl
ether ketone) (P2) [and possibly in addition, with the poly(aryl
ether sulfone) (P3)], preferably in powder or in granular form, at
a temperature below the melt temperature of each of the polymers,
prior to the mixing step itself.
End Uses of the Invented Blend
[0257] As previously mentioned, another aspect of the present
invention is directed to a shaped article or a part of a shaped
article comprising the blend (B) or the blend (T) as above
described.
Non limitative examples of shaped articles or part of shaped
articles in accordance with the present invention include
[0258] Films
[0259] Many different methods may be used to form films. Either
continuous or batch processes may be used.
[0260] Films may be formed from solution. The solution comprises
generally an organic liquid (solvent), which dissolves
advantageously the polyarylene (P1) [or (P1.sup.+)] and the
poly(aryl ether ketone) (P2) [and, if present, the poly(aryl ether
sulfone) (P3)].
[0261] Films may also be formed from the melt of the blend (B) or
the blend (T). Films may be extruded from the melt through a slit.
Films may be formed by blow extrusion. Films may also be further
processed by stretching and/or annealing. Special films such as
bilayers, laminates, porous films, textured films and the like may
be produced by techniques known in the art.
[0262] Films comprising the blend (B) or the blend (T) may be
oriented by stretching. Stretching along one dimension will result
in uniaxial orientation. Stretching in two dimensions will give
biaxial orientation. Stretching may be aided by heating near the
glass transition temperature. Stretching may also be aided by
plasticizers. More complex processes such as applying alternating
cycles of stretching and annealing may also be used with the blends
of the present invention.
[0263] Coatings
[0264] In contrast with films which are generally uncoated,
coatings are usually coated on a substrate. The expression "coated
on a substrate" should be understood in its common sense, i.e. that
the coating forms a cover over the surface of a substrate, thereby
without including any limitation as to the process used to achieve
the coating. The surface of the substrate may be partly or
completely covered by the coating.
[0265] The thickness of the coating is usually of at least 1 .mu.m,
preferably of at least 5 .mu.m, more preferably of at least 10
.mu.m, and still more preferably of at least 20 .mu.m. Besides, the
thickness of the coating is usually of at most 10000 .mu.m,
preferably of at most 1000 .mu.m, more preferably of at most 500
.mu.m. In certain embodiments, the thickness of the coating may be
of no more than 200 .mu.m, and even non more than 100 .mu.m.
[0266] Coatings may be formed by known techniques, including but
not limited to, powder coating, laminating preformed films, coating
from solution or from the melt, and like methods.
[0267] An aspect of the present invention is an article comprising
a substrate, onto which the coating as above described is
coated.
[0268] A particular aspect of the present invention of particularly
high technical interest is directed to the use of the coating as
above described, for ablative insulation. Accordingly, the coating
is coated on a substrate such as a metal, and the coating is
submitted to an aggressive agent which destroys partly or
completely the coating; the coating is then used as a "sacrificed"
layer, to protect the substrate against the aggressive agent. A
first type of aggressive agent is a body which is in relative
motion with regard to the coating and rubs against it; the body is
usually more abrasive than the coating itself. Another type of
aggressive agent lies in flames, which may originate from
uncontrolled or controlled fires, in particular from the deliberate
combustion of fuels. Still another type of aggressive agent is
chosen from chemicals. Combinations of these different types of
aggressive agents are also encompassed.
[0269] Membranes
[0270] The blend (B) and the blend (T) may be fabricated into
membranes useful for separations of mixed gases, liquids and
solids.
[0271] Other Shaped Articles or Parts of Shaped Articles
[0272] The blend (B) and the blend (T) may also be fabricated into
sheets, and various three-dimensional shaped articles and parts of
shaped articles. Various molding techniques may be used to form
shaped articles from the blends (B) and (T):
[0273] Molding Techniques
[0274] Powders, pellets, beads, flakes, reground material or other
forms of the blend (B) or of the blend (T) may be molded, with or
without liquid or other additives, premixed or fed separately. In
particular embodiments, the blend (B) and the blend (T) may be
compression molded. Exact conditions may be determined by trial and
error molding of small samples. Upper temperature limits may be
estimated from thermal analysis such as thermogravimetric analysis.
Lower temperature limits may be estimated from Tg as measured for
example by dynamic mechanical thermal analysis (DMTA), differential
scanning calorimetry (DSC), or like methods. The blend (B) and the
blend (T) can be injection molded. It is also desirable if the
blend (B) or (T) can be remelted several times without degradation,
so that regrind from molding processes can be used. One skilled in
the art will recognize that other factors also influence injection
moldability including the material's stress relaxation properties
and the temperature dependence of melt viscosity.
[0275] Extrusion Techniques
[0276] The blend (B) and the blend (T) can also be extruded.
Non-limiting examples include angle, channel, hexagonal bar, hollow
bar, I-beam, joining strip, tubes, rectangular tube, rod, sheet
plate, square bar, square tube, T-section, thin-walled tubes,
microtubes, strands, rectangular strands, or other shapes as is
required for a particular application. Related to extrusion is
pultrusion, wherein a fiber reinforcement, such as glass or carbon
fiber, is continuously added to a matrix of extruded blend (B) or
(T) at molten state; composites with exceptional moduli and
compressive strength will result.
[0277] Thermoforming
[0278] Sheet stock may be cut, stamped, welded, or thermally
formed. For example, printed wiring boards may be fabricated from
sheet or thick films by a process wherein copper is deposited on to
one or both sides, patterned by standard photolithographic methods,
etched, then holes are drilled, and several such sheets laminated
together to form a finished board. Sheet and film may also be
thermoformed into any variety of housings, cabinets, containers,
covers, chassis, plates, panels, fenders, hoods, and the like.
[0279] The present invention is described in greater detail below
by referring to the examples; however, the present invention is not
limited to these examples.
The Unexpected Merits of the Invention
[0280] It was surprisingly found that, in spite of substantial
discrepancies in their molecular structure, the polyarylene (P1)
and the poly(aryl ether ketone) (P2) contained in the blend (B)
were in general at least partially miscible with each other, the
miscible portion of both polymers forming then a single phase [(P1)
being solubilized in (P2) or the contrary, depending on the
relative amounts of both polymers].
[0281] Also surprisingly, the blend (B) exhibits an excellent
balance of properties, including: [0282] very high strength, [0283]
very high stiffness, [0284] good elongation properties, [0285] good
melt processability (in particular, they are well suited for
injection molding applications), and [0286] high chemical
resistance.
[0287] More surprisingly, the presently invented blend (B) exhibits
an outstanding thermal resistance, inhibiting thereby undesirable
outgassing even when submitted at very high temperature
(380.degree. C. or so); the thermal resistance of the invented
blend is generally as high as that of neat poly(aryl ether ketone),
even when a low amount of poly(aryl ether ketone) is contained in
the invented blend. Even more surprisingly, the presently invented
blend (B) exhibits an outstanding impact resistance, as
characterized by a standard no-notch IZOD test (ASTM D-4810); the
impact resistance of the invented blend is generally higher than
that of neat polyarylene and neat poly(aryl ether ketone) taken
individually; this synergistic behavior is so strong that optimized
blends have an impact resistance, as determined by no-notch IZOD
test defined in ASTM D-4810, which is as high as twice, or even
more, that of polyarylene and poly(aryl ether ketone) taken
individually.
[0288] On the other, the Applicant has surprisingly found that the
additional presence of a poly(aryl ether sulfone) (P3) in a blend
comprising a polyarylene and a poly(aryl ether ketone), such as the
above described blend (B), resulted in a blend (T) having several
substantially improved properties when compared to the blend (B),
while maintaining all its beneficial properties at a high level.
Among the improved properties, the elongation at break and the
impact resistance are dramatically increased. Also, the poly(aryl
ether sulfone) (P3) acts as a compatibilizer, and provides blends
of improved morphology, wherein the polyarylene and the poly(aryl
ether ketone) domain sizes are substantially finer than absent the
poly(aryl ether sulfone) (P3).
EXAMPLES
1.sup.st Set of Examples
[0289] The polymers that were used are: [0290] a polyphenylene
copolymer essentially all, if not alt, the recurring units of which
consisted of a mix of p-phenylene substituted by a phenylketone
group with unsubstituted m-phenylene in a mole ratio
p-phenylene:m-phenylene of about 50:50, commercially available from
Solvay Advanced Polymers, L.L.C. as PRIMOSPIRE.RTM. PR-250
polyphenylene, and [0291] a polyetheretherketone (PEEK)
homopolymer, essentially all, if not all, the recurring units are
of formula (VII)
##STR00028##
[0291] commercially available from Victrex Manufacturing Ltd. as
VICTREX.RTM. 150 P.
[0292] All the blends according to the present invention [(B1),
(B2) and (B3)], as well as the neat polyphenylene and PEEK controls
[(CE1) and (CE2)], were compounded on a Berstorff 25 mm twin-screw
co-rotating intermeshing extruder.
[0293] In the case of the two neat polymer controls (CE1) and
(CE2), the compounding step was to convert the resins from powder
to pellet form and to impart the same heat history seen by the
blends on the base polymers.
[0294] Mechanical property tests were conducted per the ASTM
methods indicated using 3.2 mm-thick ASTM specimens.
[0295] Isothermal thermogravimetric analysis (TGA) weight loss rate
was measured in nitrogen after rapid heat up to 380.degree. C.
(100.degree. C./min) followed by a hold duration of 40 minutes. The
rate of weight loss (ppm/min) was computed from the slope of the
TGA weight versus time plot over the time interval from 40 to 60
minutes.
[0296] The results are presented in table 1 below.
TABLE-US-00001 TABLE 1 ASTM Method (CE1) (B1) (B2) (B3) (CE2)
VICTREX .RTM. 150 P 100 70 50 30 -- PEEK (parts by weight)
PRIMOSPIRE .RTM. PR-250 -- 30 50 70 100 polyphenylene (parts by
weight) Tensile strength at yield D-638 14300 14900 17400 19600
23800 (psi) Tensile modulus (ksi) D-638 514 584 654 723 874 Tensile
elongation at D-638 5.5 4.4 4.6 4.8 No yield (%) Yield Flexural
strength (psi) D-790 21600 23400 26900 29900 36600 Flexural modulus
(ksi) D-790 538 594 677 757 921 Heat deflection D-648 147.0 147.8
149.0 149.7 152.1 temperature (.degree. C.) No-notch Izod
(ft-lb/in) D-4812 16 26 35 32 20 Weight loss rate by -- 10 10 10 10
30 isothermal TGA at 380.degree. C. (ppm/min)
[0297] Blends (B1) to (B3) (according to the invention), especially
blends (B2) and (B3), exhibited an excellent balance of properties,
including a very high strength, a very high stiffness.
[0298] They exhibited also good elongation properties, including
when an amount of polyphenylene as high as 70 parts by weight was
used, as it is the case for blend (B3).
[0299] Blends (B1) to (B3) exhibited also an outstanding thermal
resistance, inhibiting thereby undesirable outgassing even when
submitted at very high temperature (380.degree. C. or so); the
thermal resistance of the invented blend was indeed as high as that
of neat poly(aryl ether ketone), even when an amount of as low as
30 parts by weight of such poly(aryl ether ketone) was used, as it
was the case for blend (B3).
[0300] Finally, the presently invented blends (B1), (B2) and (B3)
exhibited an outstanding impact resistance, as characterized by a
standard no-notch IZOD test (ASTM D-4810); the impact resistance of
all the prepared blends was much higher than that of neat
polyarylene and neat poly(aryl ether ketone) taken individually
(strong synergistic behavior); in particular, the impact resistance
of blends (132) and (B3), as determined by no-notch IZOD test
defined in ASTM D-4810, is more than 1.5 times as high as that of
the impact resistance of the better polymer of the blend in terms
of impact resistance, here the polyphenylene.
2.sup.nd Set of Examples
[0301] The polymers that were used are [0302] polyphenylene
copolymer essentially all, if not all, the recurring units of which
consisted of a mix of p-phenylene substituted by a phenylketone
group with unsubstituted m-phenylene in a mole ratio
p-phenylene:m-phenylene of about 50:50, commercially available from
Solvay Advanced Polymers, L.L.C. as PRIMOSPIRE.RTM. PR-250P
polyphenylene, [0303] a polyetheretherketone (PEEK) homopolymer,
essentially all, if not all, the recurring units are of formula
(VII)
##STR00029##
[0303] commercially available from Victrex Manufacturing Ltd. as
VICTREX.RTM. 150 P, and [0304] a polyphenylsulfone (PPSU)
homopolymer, essentially all, if not all, the recurring units are
of formula (3)
##STR00030##
[0305] In the present set of examples, three binary blends
according to the present invention [(B4), (B5) and (B6)] composed
of the above mentioned polyphenylene copolymer and PEEK homopolymer
in various proportions, were compared with three ternary blends,
also in accordance with the present invention [named respectively
(T4), (T5) and (T6)], which were obtained by replacing, weight pro
weight, in the blends (B4), (B5) and (B6), 5 parts of the
polyphenylene copolymer and 5 parts of the PEEK homopolymer by 10
parts of the PPSU homopolymer.
[0306] The six polymer blends were prepared by first tumbling the
polymers to be compounded, in resinous form, for about 20 minutes,
followed by melt compounding using an 18 mm Leistritz corotating
intermeshing twin screw extruder having 6 barrel zones, with
barrels 2 to 6 being heated, as detailed below: [0307] barrel 2:
set point=305.degree. C., [0308] barrels 3, 4 and 5: set
point=355.degree. C., [0309] barrel 6: set point=360.degree. C.
[0310] The set point for the die temperature was fixed to
360.degree. C., and the set point for the screw speed was fixed to
250 rpm.
[0311] The feed rate was of about 10 lb/h, and the vacuum level was
of about 950 mbar.
[0312] The detailed formulations of the six blends are mentioned in
Table 2 below.
[0313] Mechanical property tests were conducted per the ASTM
methods indicated using 3.2 mm-thick (0.125 inch-thick) ASTM
specimens.
[0314] The results are also presented in table 2 below.
TABLE-US-00002 TABLE 2 ASTM Blend Blend Blend Blend Blend Blend
Method (B4) (T4) (B5) (T5) (B6) (T6) VICTREX .RTM. 150 60 55 50 45
40 35 P PEEK (parts by weight) PRIMOSPIRE .RTM. 40 35 50 45 60 55
PR-250P polyphenylene (parts by weight) RADEL .RTM. R-5000 -- 10 --
10 -- 10 NT PPSU (parts by weight) Tensile strength D-638 16500
15600 17500 16900 18900 18300 at yield (psi) Tensile strength D-638
15700 12800 14700 13700 15200 14700 at break (psi) Tensile modulus
D-638 603 574 627 607 674 624 (ksi) Tensile D-638 4.9 5.1 5.0 5.2
5.1 5.3 elongation at yield (%) Tensile D-638 6.8 11.6 11.3 21.1
11.5 14.1 elongation at break (%) Flexural strength D-790 23800
22200 25200 23900 26700 25800 (psi) Flexural modulus D-790 601 563
631 586 663 632 (ksi) No-notch Izod D-4812 37 No 37 No 33 50
(ft-lb/in) break break
[0315] Surprisingly, ternary blend (T5) exhibited a tensile
elongation at break about twice higher than that of the
corresponding binary blend (B5) free of poly(aryl ether
sulfone).
[0316] Further, the impact resistance of ternary blend (T5),
expressed in terms of no-notch Izod, was dramatically increased
when compared that of the corresponding binary blend (B5): the
improvement was such that no break at all was observed when ternary
blend (T5) passed the no-notch Izod test.
[0317] Similar observations were made for blends having a richer
poly(aryl ether ketone) content, e.g. for ternary blend (T4) and
the corresponding binary blend (B4) free of poly(aryl ether
sulfone).
[0318] Close observations were also made for blends having a richer
polyarylene content, e.g. for ternary blend (T6) and the
corresponding binary blend (B6) free of poly(aryl ether sulfone).
The ternary blend (T6) exhibited a substantially higher tensile
elongation at break than that of the corresponding binary blend
(B6) (+about 20%). Further, the additional presence of 10 parts of
polyphenylsulfone in the ternary blend (T6) resulted in a no-notch
Izod increase of about 50%, when compared to (B6).
[0319] More generally, blends (T4), (T5) and (T6) exhibited an
excellent balance of properties, a.o. a very high strength, a very
high stiffness, and good elongation properties at yield, similar or
close to that of the binary blends (B4), (B5) and (B6), and
exceeding by far the technical needs of most applications.
[0320] A transmission electron microscope (TEM) photomicrograph
showing the morphology of a ternary blend, namely the blend (T5)
with medium PEEK-polyphenylene content, is provided in FIG. 1. A
transmission electron microscope (TEM) photomicrograph of the
corresponding binary blend (B5) is provided for comparison in FIG.
2. Both photographs were taken using the same equipment, and in
identical conditions (e.g. same magnification). The bars shown on
micrographs corresponded to an effective length of 3 .mu.m; the
light phase was made of polyphenylene. As can be seen from the
photographs, the PEEK and polyphenylene domain sizes are much finer
in the case where PPSU was added relative to the case of the binary
blend. Since both the binary and the ternary blends were melt
processed under essentially identical conditions, the finer scale
dispersion of the phases in the ternary blend was taken as a clear
indication that the small amount of PPSU in the ternary blend (T5)
did act as a compatibilizer between the PEEK and the
polyphenylene.
3.sup.rd Set of Examples
Melt Viscosity Testing
[0321] Additional tests dealing with melt viscosity were made with
blends (B4) to (B6) and (T4) to (T6) as above detailed, as well as
with two neat PEEK and polyphenylene controls, namely the
VICTREX.RTM. 150 P PEEK and the PRIMOSPIRE.RTM. PR-250P
polyphenylene included in said blends (B4) to (B6) and (T4) to
(T6), hereinafter named respectively (CE3) and (CE4).
[0322] Melt thermal stability testing is a melt rheological test
performed to assess the ability of a polymer material to experience
exposure of the melt to excessive temperatures and/or for
significant times without adverse effects on the polymer material.
The melt thermal stability test was performed in a capillary
rheometer (Dynisco LCR 7001) using a capillary die 0.8 inch long by
0.040 inch in diameter and an entrance angle of 120 degrees. The
viscosity of the polymer material at 410.degree. C. and 50
sec.sup.-1 was measured initially after a 10 minute dwell time at
410.degree. C. in the barrel of the rheometer. The molten polymer
material was next allowed to sit in the barrel of the rheometer for
an additional 30 minutes (and a total dwell time of 40 minutes)
after which the viscosity was again measured and recorded. The
40-min/10-min viscosity ratio was referred to as VR.sub.40; it is a
measure of melt stability. Obviously, the closer the VR.sub.40
number to unity, the more stable the polymer material is. Typically
polymer materials with VR.sub.40 ratios of 1.0 to 2.0 are generally
considered melt stable, whereas VR.sub.40 numbers of 5 and above
are considered unacceptable. Values in between 2 and 5 are of
intermediate melt stability, with the lower numbers representing
better stability, naturally, consistent with a smaller change in
viscosity over time at a temperature of 410.degree. C.
[0323] Melt viscosity was measured as a function of shear rate at a
test temperature of 400.degree. C. also using the LCR 7001
capillary rheometer and die described above.
The results are reported in table 3 below.
TABLE-US-00003 TABLE 3 Blend Blend Blend Blend Blend Blend (CE3)
(B4) (T4) (B5) (T5) (B6) (T6) (CE4) VICTREX .RTM. 150 P PEEK 100 60
55 50 45 40 35 -- (parts by weight) PRIMOSPIRE .RTM. PR-250P -- 40
35 50 45 60 55 100 polyphenylene (parts by weight) RADEL .RTM.
R-5000 NT PPSU -- -- 10 -- 10 -- 10 -- (parts by weight) Melt
stability VR.sub.40 at 410.degree. C. 0.93 1.04 1.15 1.21 1.38 1.84
1.73 4.62 Melt viscosity .eta.(poise) at 400.degree. C. .eta. at
shear rate D = 25 s.sup.-1 4570 6610 6260 7300 7250 9050 8730 16250
.eta. at D = 100 s.sup.-1 3430 4910 4840 5290 5340 6170 6180 10420
.eta. at D = 500 s.sup.-1 2190 2900 2970 3050 3110 3330 3460 4910
.eta. at D = 1500 s.sup.-1 1500 1810 1880 1880 1920 1960 2090 2540
.eta. at D = 3500 s.sup.-1 1070 1180 1240 1210 1240 1230 1330
1410
The key observations were that: [0324] the melt stability of all
the binary and ternary blends was much improved when compared to
that of neat polyphenylene (CE4); the melt stability of the binary
blends (B4) to (B6) was better than would be expected based on the
weight average of stabilities of neat PEEK (CE3) and of neat
polyphenylene (CE4); the further addition of PPSU to the binary
blends did not substantially affect the melt stability of the
PEEK-polyphenylene two-component system; [0325] the viscosity of
all the binary and ternary blends at low shear rates (e.g. 25-100
s-1) was substantially lower than that for neat polyphenylene
(CE4); the viscosity of the binary blends was lower than expected
from additivity based on a weighted average of the neat polymers;
the viscosity of the blends at low shear rates (e.g. 25-100 s-1)
was essentially unchanged (very slightly decreased) after the
further addition of PPSU to the binary blends.
* * * * *