MULTICOMPONENT ALLOY HAVING ONE GLASS TRANSITION TEMPERATURE

ALLIAGE MIXTE DONT TOUS LES COMPOSANTS ONT LA MEME TEMPERATURE DE TRANSITION VITREUSE

English Abstract

HOE 89/F 272
Abstract
Milticomponent alloy having one glass transition
temperature
Alloy of homogeneously mixed polymers, containing
(a) at least one polyaryl ether ketone,
(b) at least one polymide and
(c) at least one polyaryl ester.
The alloys have not only higher glass transition temper-
atures but also lower melt viscosities than the polyaryl
ether ketones alone.

Claims

_ 23 - HOE 89/F 272 CA
THE EMBODIMENT OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED IS DEFINED AS FOLLOWS:
1. An alloy of homogeneously mixed polymers, having one
glass transition temperature and containing
(a) at least one polyaryl ether ketone having an intrin-
sic viscosity of 0.2 to 5 dl/g,
(b) at least one polyimide having sn intrinsic viscosity
of 0.1 to 3 dl/g and
(c) at least one polyaryl ester having an intrinsic
viscosity of 0.1 to 2 dl/g.
2. The alloy as claimed in claim 1, wherein the com-
ponents are present in the following proportions:
a) polyaryl ether ketones: 98 to 45 % by weight,
b) polyimides: 1 to 50 % by weight and
c) polyaryl esters: 1 to 50 % by weight, relative in
each case to the total alloy.
3. The alloy as claimed in claim 1, wherein the polyaryl
ether ketone contains repeating units of one or more of
the following formulae:
<IMG>

- 24 -
<IMG>
in which Ar is a divalent aromatic radical selected from
phenylene, biphenylene or naphthylene, and X represents
O, CO or a direct bond, n is zero or is, as an integer,
1, 2 or 3; b, c, d and e are zero or 1, a is, as an
integer, 1, 2, 3 or 4.
4. The alloy as claimed in claim 1 or 2 or 3, wherein the
components have the following intrinsic viscosities:
a) polyaryl ether ketones from 0.5 to 2.5 dl/g,
b) polyimides from 0.3 to 1.5 dl/g and
c) polyaryl ester from 0.3 to 1.5 dl/g.
5. The alloy as claimed in claim 4, wherein the polyaryl
ether ketone has a structure containing the following
repeating units:

- 25 -
<IMG>
or
<IMG>
6. The alloy as claimed in one or more of claims 1 to 5,
wherein the polyimide has the following repeating units:
<IMG>
in which R1 is
(.alpha.) a substituted or unsubstituted aromatic radical of
the following formulae
<IMG> <IMG>
or
(.beta.) a divalent radical of the formula
<IMG>
in which R3 represents C1-C6-alkyl or halogen and R4
represents -O-, -S-, -CO-, -SO2-, -SO-, alkylene and

- 26 -
<IMG>
in which R3 represents C1-C6-alkyl or halogen and R4
represents -O-, -S-, -CO-, -SO2-, -SO-, alkylene and
alkylidene each having 1 to 6 carbon atoms or
cycloalkylene and cycloalkylidene each having 4 to
8 carbon atoms;
R2 is an aromatic hydrocarbon carbon radical having 6
to 20 carbon atoms or halogen or a halogen- or alkyl-
substituted derivative thereof, the alkyl group contain-
ing 1 to 6 carbon atoms, an alkylene or cycloalkylene
radical having 2 to 20 carbon atoms or a divalent radical
of the formula
<IMG>
in which R3 and R4 are as defined above and R4 may
also be a direct bond.
7. The alloy as claimed in claim 1 or 2 or 3, wherein the
polyimide contains repeating units of the following
formula:
<IMG>
in which R1 and R2 are as defined above,

- 27 -
<IMG> representing, <IMG>
in which R5, independently of one another, is hydrogen,
alkyl or alkoxy, each having 1 to 6 carbon atoms in the
alkyl radical, or is
<IMG> or <IMG>
in which the oxygen is linked to one of the rings and is
in an ortho- or para-position relative to one of the
bonds of the imide carbonyl group.
8. The alloy as claimed in claim 1 or 2 or 3, wherein the
polyimide has repeating units of the following formula:
<IMG>
9. The alloy as claimed in claim 1 or 2 or 3, wherein the
polyaryl ester c) is a polyester carbonate based on a
dihydroxyphenol, a carbonate precursor and an aromatic
dicarboxylic acid or a reactive derivative thereof, or is
derived from at least one dihydroxyphenol and at least
one aromatic dicarboxylic acid.
10. The alloy as claimed in claim 9, wherein the dihy-
droxyphenol has the following formula:

- 28 -
<IMG>
in which Y' is alkyl having 1 to 4 carbon atoms, cyclo-
alkyl having 6 to 12 carbon atoms or halogen, m',
independently of one another, is zero, 1, 2, 3 or 4 and
R' is alkylene or alkylidene each having 1 to 8 carbon
atoms or an arylene radical having 6 to 20 carbon atoms.
11. The alloy as claimed in claim 9, wherein the dihy-
droxyphenol is bisphenol A.
12. The alloy as claimed in claim 9, wherein the aromatic
dicarboxylic acid has the following formula:
HOOC - R" - COOH
in which R" is selected from the groups
<IMG> or <IMG>
or
<IMG>
in which f is zero or 1 and W represents O, S02, CO,
C(CH3)2, CHz, S or

- 29 -
<IMG>
in which W' has the meaning given above for W, T in the
formulae is alkyl having 1 to 6 carbon atoms or halogen.
13. The alloy as claimed in claim 9, wherein the aromatic
dicarboxylic acid is selected from isophthalic acid,
terephthalic acid and mixtures thereof; and in which the
reactive derivatives of the acids are selected from
terephthaloyl dichloride, isophthaloyl dichloride and
mixtures thereof.
14. The alloy as claimed in claim 9, wherein the carbon-
ate precursor is phosgene.
15. The alloy as claimed in claim 9, wherein the poly-
ester carbonate is a copolymer of bisphenol A, tere-
phthaloyl dichloride, isophthaloyl dichloride or mixtures
of these two, and phosgene.
16. The alloy as claimed in claim 9, wherein the dihy-
droxyphenol is bisphenol A, and the aromatic dicarboxylic
acids are terephthalic acid or isophthalic acid or
mixtures of these two.
17. The alloy as claimed in claim 1 or 2 or 3, wherein
the polyaryl ether ketone contains repeating unit of the
following formula
<IMG>
and the polyimide contains repeating units of the follow-
ing formula

- 30 -
<IMG>
and the polyaryl ester contains repeating units of the
following formula
<IMG>
18. The alloy as claimed in claim 1 or 2 or 3, wherein
the polyaryl ether ketone contains repeating units of the
following formula
<IMG>
and the polyimide contains repeating units of the follow-
ing formula
<IMG>
and the polyaryl ester contains repeating unit of the
following formula

- 31 -
<IMG>
19. The alloy as claimed in claim 1 or 2 or 3, wherein
the polyaryl ether ketone contains repeating units of the
following formula
<IMG>
and the polyaryl ester contains repeating units of the
following formula
<IMG>
and the polyaryl ester contains repeating units of the
following formula
<IMG>
20. A molded article prepared from an alloy as claimed in
claim 1.
21. A matrix material for composites, prepared from an
alloy as claimed in claim 1.
22. The matrix material as claimed in claim 21, combined
with carbon fibers or glass fibers.

- 32 -
23. The molded article as claimed in claim 20 in the form
of a fiber, a film, or a tube, prepared by injection
molding or extrusion.

- 33 -
24. The alloy as claimed in claim 1, and substantially
as described herein.

Description

2~23~
HOECHST AKTIENGESELLSCHAFT HOE 89/F 272 Dr. R/AP
Description
~ulticomponent alloy having one glass transition
temperature
During recent years, a large number of publications have
appeared which describe the synthesis and properties of
polyaryl ethers. One of the earliest works is concerned
with the electrophilic aromatic ~ubstitution of aromatic
dihalides using unsubstituted aromatic compounds such as
diphenyl ethers (US-A-3,06~,205). Johnson and co-workers
~Journal of Polymer Science, A-1, 5, 1967, 2,415 - 2,427;
US-A-4,107,837 and 4,175,175) describe nucleophilic
aromatic substitutions (condensations). This synthetic
pathway led to a new category of polyaryl ethers, the
polyaryl ether ketones.
In recent years interest in polyaryl ether ketones has
increased, as is shown by the appearance of a number of
publications: US-A-3,953,400; 3,956,240; 4,247,682;
4,320,224; 4,339,568; Polymer, 1981, 22, 1,096 - 1,103;
20- Polymer, 1983, 24, 9S3 - 958.
Several polyaryl ether ketones are already commercially
available, for example those having the following
structure:
(PEK)
~ o~
_~o~C~
(PEEK)
r O
~O~C~

2Q~J3~ ~
-- 2 --
Polyaryl ether ketones are also well known. These are a
valuable category of polym~rs having excellent proper
ties. In particular, they ha~e high heat resistance,
hydrolysis resistance and good solvent resistance. Some
polyaryl ether Xetones are highly crystalline and have
melting points far in excess of 300C. It is possible to
synthesize polyaryl ether ketones having different melt
temperatures and molecular weights.
For some applications, for example as matrix materials
for composites, higher glass transition temperatures and
lower melt viscosities are desirable. Consequently, it is
of great industrial interest to suitably modiy polyaryl
ether ketones to give, on ~he one hand, higher glass
transition temperatures and, on the other hand, improved
melt processibility. Furthermore, it is desirable that
the properties of the polyaryl ether ketones and of the
modified polyaryl ether ketones, for example water
absorption or impact strength, are at a comparable level.
It is known that technologically important properties of
polymers, for example of those mentioned above, can be
imparted by alloying polymers with other polymers. The
resulting alloys can be classified into two fundamentally
different categories. The non-homogeneously mixed cate-
gory of alloys are multiphase and usually have a plurality
of glass transition temperatures. The homogeneously mixed
category of alloys are single-phase and normally have a
single composition-dependent glass transition tempera-
ture. These alloys having a single compositiondependent
glass transition temperature are referred to in the
subsequent text by the term l'homogeneously mixedl~.
In this connection, there is particularly great indus-
trial interest in alloys of homogeneously mixed polymers,
since the technological properties of these alloys can be
selec-tively adapted to defined requirements by varying
the com-ponents and the mixing ratios (Olabisi, Robeson,
Shaw: Polymer-Polymer Miscibility, Academic Press, New

2~l3~
-- 3 --
York 1979).
However, it has not been remotely possible hitherto to
safely predict, from the properties of the individual
components, the homogeneous miscibility and the proper-
ties of an alloy. Consequently, the alloying of polymers
remains substantially empirical. In particular, the
homogeneous miscibility of the components in alloys
remains unpredictable despite a very large number of
experimental and theoretical studies in this field.
For instance, it is known that alloys of homogeneously
miscible polymers are rare (Journal of Polymer Science,
Polymer Physics Edition, Vol. 21, p. 11, 1983). In
Macromolecules, Vol. 16, p. 753, 1983, it is stated that
the number of blend systems which are known to be homo-
geneously miscible has increased in the last decade.
However, until now modern theories have had only limited
success in predicting miscibility. Consequently, there is
some doubt that it is possible to develop any practical
theory to take account of the actual complexities of
polymer-polymer interactions which result from natural
phenomena.
In contrast, the methods for the experimental determin-
ation of miscibility are known (Olabisi, Robeson, Shaw:
Polymer-Polymer Miscibility, Academic Press, New York,
p. 321-327, 1979): the most important criterion for
homogeneous miscibility is the existence of a single
glass transition temperature which is intermediate
between those of the components used to prepare the
mixture. The transparency of polymer alloys in the melt
and, insofar as these are not partly crystalline, in the
solid, is an indication that the components are homogen-
eously mixed.
Alloys of polyarylates with polyimides, which may addi-
tionally contain a thermoplastic polymer, have already
been described tUS-A-4,250,279). The amount of this third

2 0 ~ 3 ~ ~ Qe
-- 4
- component is only at most 40 percent by weight. The
advantage of these three-component mix~ures is supposed
to be that they have an acceptable balance of mechanical
properties Values for the combinati~n with polyaryl
ether ketones, which would provide a standardl are not to
be found in this publication. Neither does ~he publica-
tion mention that the alloys described in the present
invention are homogeneously miscible within a wide range
of concentration and have no~ only increased glass
transition temperatures but also lower melt viscositie5
than the polyaryl ether ketones alone.
Binary miscible alloys of a polyaryl ether ketone and
specific polyimides hav~ likewise been disclosed (EP-
A-0,257,150). This publicakion states that the addition
of a polyaryl ether ketone improves the melt process-
ibility of the polyimide. However, the applicant~s own
experiments have shown that the flowabilities of these
alloys (MFI) are either not significantly better, or even
worse, than those of the polyaryl ether ketones alone.
However, it is noteworthy that the melt viscosities during
processing, i.e. at 360C, are still inconveniently high.
In contrast, the multicomponent alloys according to the
invention have flowabilities which are significantly
better than those of polyaryl ether ketones and those of
the binary alloys of the above-cited EP patent
specification.
The object of the present invention is therefore to
provide alloys based on homogeneously mixed polyaryl
ether ketones and other polymers, having an increased
glass transition temperature and improved melt proces-
sibility, in particular for the preparation of compo-
sites.
Surprisingly, it has now been found that polyaryl ether
ketones are homogeneously miscible together with polyaryl
esters and polyimides within a wide concentration range
and give alloys which not only have higher glass trans-

2023~ Je
-- 5 --
ition temperatures but also lower melt viscosities than~he polyaryl ether ketones alone.
he present invention accordingly provides alloys of
homogeneously mixed polymers containing
(a) at least one polyaryl ether ketone,
(b) at least one polyimide and
(c) at least one polyaryl ester.
The individual components are used in the following
amounts: polyaryl ether ketones: 45 to 98, preferably 60
to 95 and in particular 75 to 95 percent by weight;
polyimides: 1 to 50, preferably 2 to 35 and in particular
2 to 20 percent by weight; polyaryl esters: 1 to 50,
preferably 2 to 35 and in particular 2 to 20 percent by
weight, relative in each case to the total alloy.
Polyaryl ether ketones a) which can be used in alloys
according to the present invention contain one or more
repeating units of the ~ollowing formulae:

2~23~
-- 6 --
{ ~a ~
~CO
~X~
~X~ X~
in which AX is a divalent aromatic radical ~elected from
phenylene, biphenylene or naphthylene, and X, independ-
ently of one another, represents 0~ CO or a direct bond,
n is zero or is, as an integer, 1, 2 or 3 b, c, d and e
are zero or 1, a is, as an integer, 1, 2, 3 or 4 and d is
preferably zero, if b i8 equal to 1. Preference i8 given
to polyaryl ether ketones ha~ing repeating units of the
following formulae:
.~W~
~o4~g~o_
--o~e~
o o
~ ~e-- J

2 ~ 2 ~
-- 7 --
~o~ o~ ~ e~ ~
~~
_
.
` ~
~o~ ~
__~~
. ~~
These polyaryl ether ketones can be synthesized by known
methods which have bePn described in CA-A-847,963;
US-A-4,176,222; US-A-3,953,400; US-A-3,441,538;
US-A-3,442,857; US-A-3,516,966; U5-A-4,396,755 and
US-A-4,398,020.

2~3~
The term polyaryl ether ke~ones in this context includes
homopolymers, copolymers, terpolymer~ and block copoly-
mers.
The polyaryl ether ketones have intrinsic viscosities of
0.2 to 5, preferably of 0.5 to 2.5 and particularly pre-
ferably of 0.7 to 2.0 dl/g, measured in 96 % strength
sulfuric acid at 25C.
~he alloy~ according to the invention contain poly-
imides b) having repeating unit-~ of the following
formula:
O O
-N~- R1 _o~-R2--
Il 11
O O
in which Rl is selected from
(~) a substituted or unsubstituted aromatic radical of
the following formulae
(R3)o-4 ~R3)o_4 (R3)o-4
or
(~) a divalent radical of the general formula
~ R3 ) o_43~ R3 ) o_~
in which R3 repre~ents Cl-C6-alkyl or halogen and R4
represents -O-, -S-, -CO-, -SOz-, -SO-, alkylene and
alkylidene each having 1 to 6 carbon atoms or
cycloalkylene and cycloalkylidene each having 4 to
8 carbon atoms. The indices "0-4" in the case of R3
denote the integers zero, one, two, three or four.

2 ~
- 9 -
R2 is an aromatic hydrocarbon radical having 6 to 20,
preferably 6 to 12 carbon a~oms, or a halogen- or alkyl-
substituted derivative thereof, the alkyl group contain-
ing 1 to 6 carbon atoms, or an alkylene or cycloalkylene
radical having 2 to 20, preferably 2 to 6 carbon atoms or
a divalent radical of the formula
~R3)o~4 (R3)o-4
~)- R4--~
in which R3 and R4 are as defined above and R4 may also be
a direct bond.
Other polyimides which are ~uitable for the purposes of
the invention include those having repeating unit~ of ~he
formula
O o
--O - Z N--R 2 - N Z--O--R 1--
Il ll
O O
in which R1 and R2 are as defined above,
~~Z~ representing ~
in which R5, independently of one another, i8 hydrogen,
alkyl or alkoxy, each having 1 to 6 carbon atoms in the
alkyl radical (here also, the index "0-3" represent~ the
integers zero, one, two or three), ox is

2~2~
_ 10 --
~ or
in which the ~xy~en i8 linked with one of the rings and
is in the or~ho- or para-posi~ion rela~ive to one of the
bonds of the imide carbonyl group.
S Pre~erred polyLmides according ~o the inv~ntion are those
having the following repeating unit~
N~ CH~ ~ ~
The te~m polyimides in ~his context includes homopoly-
mers, copolymers, terpolymers and block copolymers. The
polyimides used have intrinsic viscosities of Ool to 3,
preferably of 0.3 to 1.5 and in particular of 0.3 to
1 dl/g, measured at 25C, for example in N-methylpyr-
rolidone or methylene chloride.
The polyimides which are used according to the present
invention are known. Their synthesis has been de~cribed,
for example in US-A-3,847/867; 3l847,869; 3,850,885;
3,852,242; 3,85S,178; 3,887,558; 4,017,511; 4,024,110 and
4,250,279.
The polyaryl esters c) may be polyester carbonates, whose
syntheses have been descxibed for example in
US-A-3,030,331; 3,169,121; 4,194,038 and 4,156,069. ~hese
are copolyesters containing carbonate groups, carboxylate
groups and aromatic groups, at least some of the carboxyl
groups and at least some of the carbonate groups being

2~23~r
- 11 ~
bonded directly to the ring carbon atom6 o~ the aromatic
groups. These polymers are usually prepared by reacting
difunctional carboxylic acids with dihydroxyphenol~ and
carbonate precursors.
Dihydroxyphenols for the synthesi6 of polyester carbon-
ates which are ~uitable for ~he present invention have
the general formula
( Y )m ( R )p ( Y )
HO ~ ~ ~ E ~ ~ ~OH
in which A i6 an aromatic group such as phenylene,
biphenylene or naphthylene and ~ is selected from al~yl-
ene or alkylidene, ~uch as methylene, ethylene or iso-
propylidene. E may also be composed of two or more
alkylene or alkylidene groups linked by a non-alkylene or
non-alkylidene group such as, for example, an aromatic
group, a tertiary amino group, a carbonyl group, a
sulfide group, a sulfoxide group, a sulfone group or an
ether group. E may al~o be a cycloaliphati~ group, a
sulfide group, a ~ulfoxide group, a sulfone group, an
ether linkage or a carbonyl group.
R is selected from hydrogen, an alkyl group (Cl-C3), an
aryl group (C6-C~) or a cycloaliphatic group. Y may have
the meaning of R or be a halogen or a nitro group.
s, t and u, independently of one another, are zero or 1.
m and p, independently of one another, are zero or an
integer which is of the same magnitude as the maximum
number of substituents which A or E can carry.
If a plurality of the 8ub8tituent8 denoted by Y are pre-
sent, these may be identi~al or d.ifferent. The ame i
true for R. The hydroxyl group~ and Y can be linked para-,
meta- or ortho-po~itions on the aromatic radicals.

2 ~
- 12 -
Preferred dihydxoxyphenol~ for the preparation of the
polyaryl e~ters c) are ~hose of ~he fonmula
(Y )~T~' (Y )~
H O ~ ~ R ' ) 0~ oH
in which Y' is alkyl ~aving 1 to 4 carbon atoms,
cycloalkyl having 6 to 12 carbon atoms or halogen,
S preferably chlorine or fluorine. ~ach m~, independently
of one another, i~ ~ero, 1, 2, 3 or 4, preferably zero,
and R' i8 alkylene or alkylidene each having 1 to 8,
preferably 1 to 4 carbon atoms or an arylene radical
having ~ to 2~, preferably 6 to 12 carbon atom~, in
particular alkylidene having 3 carbon atoms. The index
"0-1" denotes zero or 1.
The dihy~roxyphenols can be used alone or as mixtures of
at least two dihydroxyphenols.
Aromatic dicarboxylic acids for the synthesi~ of polyaryl
esters c) which are cuitable for the pre~ent invention
ha~e the general formula:
HOOC - R" - COOH
in which R~ is selected from the groups
( T ) o_ 4~ ~ T ) o_~
or

2~2~
- 13 -
~ or
in which f is 2ero or 1 and M represent~ 0, SO2~ CO
C(CH~)2, CH2, S or
~T)o-4 (~0-4
-O~W'~O-
in which W~ has the meaning given ~bove for W.
In the formulae, T is selected from alkyl having ~ to
6 carbon atoms, preferably methyl, propyl or butyl, or
halogen, preferably F, Cl or Br. The indices "0-4" next
to T denotes the integers zero, one, two, three or four.
Preferred aromatic dicarboxylic acids are isophthalic
acid, terephthalic acid or mixture~ of these two. Prefer-
ence is also given to the use of reactive derivatives of
aromatic dicarboxylic acids uch as terephthaloyl di-
chloride, isophthaloyl dichloxide or mixtures of these
two.
Suitable carbonate precursors for the ~ynthesis of the
polyester carbonates are c~rbonyl halides, for exEmple
phosgene or carbonyl bromide, and carbonate esters, for
example diphenyl carbonate.
Moreover, the alloys according to the invention may
contain polyaryl esters which have been derived from at
least one of the abovementioned dihydroxyphenols and at
least one of the abovementioned aromatic dicaxboxylic
acids or reactive derivatives thereof.
These polyaryl esters can be prepared by one of the well-
known polyester~forming reactions, for example by react-
ing acid chlorides of aromatic dicarboxylic acids with
dihydroxyphenols or by reacting aromatic di-acids with

2~2~
- 14 -
di-ester deri~atives of dihydroxyphenols or by reacting
dihydroxyphenols with aromatic dicarboxylic acids and
diaryl carbonstes. Reactions of this type are described,
for example, in US-A-3,317,464; 3,395/119; 3,948,856;
3,780,148; 3,824,213 or 3,133,898.
As is well-known, these polyaryl esters are less heat
stable than the other components o~ the alloys according
to the invention. Consequently, the proportions by weight
of polyaryl esters of this type are preferably low in
those alloys which contain polyaryl ether ketones of
particularly high melting points, for example the one
having the repeating units given below.
~o-~c ~J
However, since the abovementioned polyester carbonates
are more heat stable than the other polyaryl esters which
have been described in the present text, preference is
given to the use of these polyester carbonate~ as poly-
aryl esters c) with the abovementioned polyaryl ether
ketones of particularly high melting points for the
preparation of an alloy according to the invention.
The polyaryl esters or polyester rarbonates u~ed have
intrinsic viscosities of 0~1 to 2, preferably 0.3 to 1~5
and in particular 0.3 to 1 dl/g, measured at 25C in p-
chlorophenol, methylene chloride or N-methylpyrrolidone.
The term polyaryl esters in this context includes homo~
polymers, copolymers, terpolymers and block copolymers.
The homogeneous miscibility of the components in the
alloys according to thc invenkion was proven u~ing a
plurality of the abovementioned methods.
For instance, the alloys according to the inventivn have

2 ~ 2 ~
_ 15 -
a single glass transition ~emperature which can be
identified by differential calorimetry, and moreover give
transparent melts.
The alloys according to the invention are prepared by
S known alloying me~hods. For instance, the alloying
components in powder or granule form are processed
together in an extruder to give strands and the strands
are cut to give granules and these are converted into the
desired shape, for example by pressing or injection
molding.
The alloys may contain additives, for example plastici-
zers, heat stabilizers, UV stabilizers, impact modifiers
or reinforcing additives such as glass fibers, carbon
fibers or high modulus fibers.
The alloys can be advantageously used, in particular as
matrix materials for composites since they have not only
a high qla;s transition temperature but also good flow-
ability. In particular, composites of the alloys
according to the invention with glass fibers or carbon
fibers are mechanically strong and can be prepared free
of gas bubbles. Furthermore, the alloys are suitable for
the production of molded articles by injection molding or
extrusion, for example in the form of fibers, films and
tubes.
~xamples
The following polymers were synthesized and used in the
examples:
Polyaryl ether ketone I having an intrinsic ViSCQSity of
1.2 dl/g, measured in 96 % strength sulfuric acid at
25C, and containing repeating units of the following
formula:

- 16 -
~O~C~
The polyaryl ether ketone II having an intrinsic vis-
cosity of 1.0 dl/g, measured in 96 ~ ~rength sulfuric
acid a~ 25C, and containing repeating unit~ of the
following formula:
~ ~
o~~c~
The polyaryl ether ketone III having an intrin~ic vis-
cosity of 1.0 dl/g, measured in 96 % strength 6ulfuric
acid at 25C, and containing repeating units of the
following formula:
r o~
~O~C~
Polyimide I having an intrinsic viscosity of 0.5 dl~g,
measured in chloroform at 25C, and containing repeating
units of the following formulas
~ 11 O~C~O o
Polyaryl ester I having an intrinsic vi8c05ity of
0.5 dl/g, measured in methylene chloride at 25C, and
containing repeating units of the following formula:

- - -
~ o ~ o-ol -~ ~
CH3
Polyaryl ester II having an intrinsic viscosity of
0.7 dl/g, measured in p-chlorophenol ~ 25C, and con-
taining repeating units of the following formula:
~ ~o-1-~3`~Y~ ~
CH3
The specified polymers were first dried (140C, 24 h,
reduced pressure~ and then in varying weight ratios either
kneaded in a laboratory compounder (Rheocord System 90/-
Rheomix 600, HAAKE, Karlsruhe, Federal Republic of
Germany) under an inert gas or extruded in a laborato~y
extruder under protective gas (Rheocord System 90/Rheomex
TW 100, HAAKE). Preference is given to the use of argon a.~
inert or protective gas. The resulting alloys were dried
(140C, 24 h, reduced pre~sure) and then either in~ection
molded to give moldings such as dumbbell test ~pecimens ox
impact test specimens (6 x 4 x 50 mm) (injection molding
machine: Stubbe S55d, DEMAG, ~alldorf, Federal Republic of
Germany) or tested for their physical propertie~. The
following instruments were u~ed for this purpo~e:
Melt index tes~ing apparatus ~PS-D, Goettfert, Buchen,
Federal Republic of Germany, and a capillary vi~cometer
for measuring the 10wabilities o the all~ys.
Automatic torsion apparatus, Brabender, O~fenbach, Federal
Republic of Germany and a differential calorimeter DSC 7,
Perkin Elmer, ~berlingen, Federal Republic of ~ermany, for
determining the glass transition temperatures of the
alloys.

2 Q ~
- 18 -
Pendulum Lmpact testing apparatus, Zwick, Nurember~,
Federal Republic of Germany, for determining Charpy
tnotched) impact strengths.
In the tables, "V" indicates a comparison.
Example 1:
The polyether ketone I, the polyLmide I and the polyaryl
ester I were kneaded together for 30 minutes at a temper-
ature of 360C and a rotor speed of 100 rpm in the
laboratory compounder, in various proportions by weight.
Table 1 shows that the great majority of the alloys are
composed of homogeneously miscible components since they
not only have a single composition-dependent ~lass
transition temperature but also give transparent melts.
Table 1: Miscibility
Polyaryl Poly- Poly- No. of glass Melt
ether imide I aryl transition trans-
ketone I (% by wt.) ester I temps. DC parency
V100 ~ 0 0 % one 142 yes
V0 % 100 0 % one 217 yes
V0 % 0 100 % one 190 yes
V80 % 20 0 % one 163 yes
V50 % 50 0 % one 180 yes
V20 % 80 0 % one 201 yes
80 % 10 10 % one 153 yes
60 % 20 20 % one 160 yes
50 % 25 25 % one 180 yes
V33.3 %33.3 33.3 % one 180 yes
V20 % 60 20 % one 185 yes
V20 % 20 60 % two no
V80 % 0 20 % one 145 yes
55 % 10 35 % one 165 yes
45 % 10 45 % one 170 yes
V40 % 20 40 % one 175 yes
V0 % 50 50 % one 195 yes
V0 % 75 25 % one 205 yes

3 ~
-- 19 --
This example shows that the components of the alloys
according to the invention are homogeneously miscible
within a wide concentration range and have higher glass
transition temperatures than the polyaryl ether ketone I
alone.
Example 2:
A twin-screw extruder (all four zones 360C) was used to
extrude together and granulate the polymers mentioned in
Example 1 in various ratios by weight, after these
polymers had been intensively dried (140C, 24 h, reduced
pressure). The granules were then dried under reduced
pressure at 140C for 24 hours and used for measurements
o~ the flowability of the alloys. Table 2 gives the
resulting MFI values (melt index in accordance with
DIN 53735-MFI-B, 360C) and the melt viscosities measured
using a capillary viscometer (2 shear rates).
Table 2: Flowability
Polyaryl Poly- Poly- MFI Viscosity at
ether imide I aryl (360C) 360C in Pas
20ketone I (% by wt.) ester I 300s-1I20s-
V100 % 0 0 % 5 9001,300
V0 % 100 0 % 30 260 270
V80 % 20 0 % 7 9001,300
V0 % 0 100 % 190 43 4g
V50 % 50 0 % 11 8301,300
V20 % 80 0 % 15 8301,280
80 % 10 10 % 20 500 ~00
60 % 20 20 % 29 300 360
V33.3 % 33.3 33.3 % 73
V20 % 60 % 20 % 60 230 270
This example shows that the melt viscosities of the
alloys according to the invention are significantly lower
than those of polyaryl ether ketone I alone, the ~is-
cosity reduction achievable by mixing polyimide I alonewith polyether ketone I being only slight.

2 ~
20 -
-
~ample 3:
The granules described in Example 2 were injection molded
at 360C to give impact test specimens and dumbbell test
specimens, and on these the impact strengths (Charpy,
S notched) and the water absorption (23C, 85 % rel.
humidity, 24 h) of the alloys were measured (Table 3).
Table 3: Impack strengths and water absorption
Polyaryl Poly- Poly- Water Impact
ether imide I aryl absorp- ~trength
ketone I (% by wt.) ester I tion in (mJ)
Y
V 100 % 0 0 % 0.2 110
V 0 % 100 0 % 0.51 80
V 80 ~ 20 0 % 0.24 120
V 50 % 50 0 % 0.38 115
V 20 % 80 0 % 0.43 80
80 % 10 10 ~ 0.23 105
60 ~ 20 20 % 0.27 100
V 33.3 % 33.3 33.3 % ~.39 g5
V 20 % 60 20 ~ 0.46 78
This example shows that a low water absorption and good
impact strengths are only obtained using the alloys
according to the invention which contain the individual
components in amounts within the claimed limits and that
these properties are comparable with those from alloys of
polyaryl ether ketones with polyimides alone.
Example 4:
The compounder was used at 100 xpm and 380C to knead
together for 30 minutes: polyaryl ether ketone II,
polyimide I and polyaryl ester II in various compo-
sitions. Table 4 shows that the majority of the com-
ponents of the alloys are homogeneously miscible since
these give transparent melts and a single composition-
dependent glass transition temperature.

Table 4: Miscibility
Polyaryl Poly- Poly- No. of Melt
ether imide I aryl glass trans-
Xetone I (% by wt.) ester II trans- parency
ition
temps, C
V lO0 ~ 0 0 ~ one 165 yes
V 75 % 25 0 % one 170 yes
V 50 ~ 50 0 ~ one 205 yes
V 20 % 75 0 % one 217 yes
80 % lO 10 % one 170 yes
60 % 20 20 % one 175 yes
V 33.3 % 33.3 33.3 ~ one 185 yes
V 0 % 50 50 % one 195 yes
~xample 5:
Films of thickness 0.3 mm were molded under reduced
pressure (100 bar) at 380C from the alloys (granules)
described in Example 2. Between each pair of these sheets
of film were laid commercially available webs of carbon
fibers and these sandwiches were molded under reduced
pressure at 380C to give composites. Gas bubble-free
composites resulted.
Example 6:
Polyaryl ether ketone I, polyaryl ether ketone II,
polyimide I and polyaryl ester II were kneaded together
in the ratios by weight given in Table 5 in the labora-
tory compounder at 380C and 100 rpm for 30 minutes. The
test alloys have a single composition-dependent glass
transition temperature and give transparent melts. They
were therefore considered to be homogeneously mixed.

~12~
- 22 -
Table 5: Miscibility
Polyaryl Polyaryl Poly- Poly- No. of Melt
ether ether Lmide I aryl glass tran~-
ketone II ke~one I ester trans- parency
(% by wt.) II ition
temp~-C
33.3 ~ 33.3 6.7 %16.7 ~ one 175 yes
V 33.3 % 33.3 33.3 %0 % one 180 yes
30 % 30 % 30 %10 ~ one 180 yes
~xample 7:
25 g of the polyaryl ether ketone III, 15 g of the
polyimide I and 5 g of the polyaryl ester II wexe kneaded
together in the compounder at 390C for 20 minutes at
100 rpm. This gave a transparent melt and the resulting
alloy had a single glass transition temperature at 165~C.