CA2023514A1 - Multicomponent alloy having one glass transition temperature - Google Patents

Abstract

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.

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~ ~

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~

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 - 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 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~

{ ~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 ~

~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 ~

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 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 ~

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~

~ 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~

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:

~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 -~ ~

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~ ~

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 ~

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 ~

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 ~

-~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~

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.

Claims (24)

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:

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:

or

6. The alloy as claimed in one or more of claims 1 to 5, wherein the polyimide has the following repeating units:

in which R1 is (.alpha.) a substituted or unsubstituted aromatic radical of the following formulae or (.beta.) a divalent radical of the formula in which R3 represents C1-C6-alkyl or halogen and R4 represents -O-, -S-, -CO-, -SO2-, -SO-, alkylene and 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 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:

in which R1 and R2 are as defined above, representing, 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 or 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:

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:

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 or or in which f is zero or 1 and W represents O, S02, CO, C(CH3)2, CHz, S or 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 and the polyimide contains repeating units of the follow-ing formula and the polyaryl ester contains repeating units of the following formula

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

19. The alloy as claimed in claim 1 or 2 or 3, wherein the polyaryl ether ketone contains repeating units of the following formula and the polyaryl ester contains repeating units of the following formula and the polyaryl ester contains repeating units of the following formula

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.

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.

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