EP0579628A1

EP0579628A1 - Alloys of cycloolefin polymers and polyarylether ketones

Info

Publication number: EP0579628A1
Application number: EP92907067A
Authority: EP
Inventors: Ulrich Epple; Arnold Schneller; Harald Cherdron
Original assignee: Hoechst AG
Current assignee: Hoechst AG
Priority date: 1991-04-06
Filing date: 1992-03-21
Publication date: 1994-01-26
Also published as: DE4111197A1; JPH06506012A; WO1992017544A1; US5376725A

Abstract

Des alliages polymères contiennent (A) au moins un polymère de cyclooléfine et (B) au moins une cétone de polyaryléther, la quantité de (A) étant comprise entre 1 et 99 % en poids et la quantité de (B) étant comprise entre 99 et 1 % en poids, de sorte que les deux quantités ajoutées s'élèvent à 100 % en poids de l'alliage. Ces alliages polymères sont utiles comme matrices de matériaux composites ou pour produire des corps moulés.Polymer alloys contain (A) at least one cycloolefin polymer and (B) at least one polyarylether ketone, the amount of (A) being between 1 and 99% by weight and the amount of (B) being between 99 and 1% by weight, so that the two amounts added amount to 100% by weight of the alloy. These polymer alloys are useful as matrices for composite materials or for producing molded bodies.

Description

description

Alloys from cycloolefin polymers and polyaryl ether ketones

The synthesis and properties of cycloolefin polymers have been the subject of many publications in recent times. It is known that these olefins can be polymerized using various catalysts. Depending on the catalyst, the polymerization proceeds via ring opening (US-A-3557072, US-A-4178424) or with opening of the double bond (EP-A-156464, EP-A-283164, EP-A-291208, EP-A -291970, DE-A-3922546).

Cycloolefin homo- and copolymers are a class of polymers with an outstanding level of properties. Among other things, they excel from high heat resistance, hydrolytic stability, low water absorption, weather resistance and transparency. However, the processability at high temperatures and shear forces is limited by oxidative and thermal processes. Additives such as antioxidants and thermal stabilizers are used to increase the thermal processing range. High levels of additives can lead to a strong negative impact on mechanical properties such as the modulus of elasticity and the tensile strength. Additives can thus act as plasticizers, whereby the shear modulus is also reduced over a wide temperature range.

In order to ensure the processability of a polymer without the occurrence of high shear forces, the flowability of the polymer can be improved by flow improvers such as PE waxes. However, there is also a strong negative impairment of the mechanical properties mentioned above.

Polyaryl ether ketones are also well known, as evidenced by the large number of publications on synthesis and properties: US-A-3953400; US-A-3956240; US-A-4247682; US-A-4320224; US-A-4339568; Polymer 22: 1096-1103 (1981); Polymer 24 (1983), 953-958. Polyaryl ether ketones are also a valuable class of polymers, which are characterized, among other things, by good impact strength and high thermal resistance. Some polyaryl ether ketones are highly crystalline and show melting temperatures of well over 300 ° C, others are amorphous. Amorphous and partially crystalline polyaryl ether ketones with different molecular weights can be obtained by electrophilic aromatic substitution (US-A-3065205; US-A-3956240) or nucleophilic aromatic substitution (J. Polymer Sei., 1967, A-1, 5, 2415-2427; US -A-4107837; US-A-4175175, DE-B-1545106, CA-A-847963, DE-A-2803873).

Both polymer classes are processed thermoplastic. High and long-term thermal loads lead to decomposition and oxidation products in the cycloolefin polymers. Shorter thermal load intervals, i.e. higher output through improved flowability, when extruding or injection molding would therefore be an advantage. For some applications of the polyaryl ether ketones, for example as matrix materials for composites, their mechanical properties, for example the modulus of elasticity or the modulus of shear, are still in need of improvement. In this context, the high water absorption of amorphous polyaryl ether ketones is disruptive. It limits long-term use in high humidity as the dimensional stability is not guaranteed. A lower water absorption would therefore be an advantage. It is now known that important properties of polymers, such as those mentioned above, can be altered by alloying polymers with other polymers. To date, however, it is still a long way from being able to reliably predict the properties of an alloy from the properties of the individual components.

The object of the present invention is therefore to provide alloys made of cycloolefin polymers and polyaryl ether ketones with increased flowability with further improvement of the mechanical properties. The invention relates to polymer alloys containing at least two components (A) and (B), characterized in that

(A) at least one cycloolefin polymer and

(B) is at least one polyaryl ether ketone, (A) being present in amounts of 1 to 99% by weight and (B) being in amounts of 99 to 1% by weight and the amounts of (A) and (B) being relative add up to 100% by weight in relation to the total alloy.

Cycloolefin polymers (A) suitable for the alloys according to the invention contain structural units which are derived from at least one monomer of the formulas I to VI or VII

CH = CH

\ /

(CH ₂ ) _n (VII),

are derived, wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 are the} same or different and represent a hydrogen atom or a C ₁ -C ₈ alkyl radical, the same radicals in the different formulas can have different meanings and n is an integer from 2 to 10.

In addition to the structural units which are derived from at least one monomer of the formulas I to VII, the cycloolefin polymers (A) can contain further structural units which are derived from at least one acyclic 1-olefin of the formula VIII

are derived, wherein R ⁹ , R ¹⁰ , R ¹¹ and R ^{12 are} identical or different and denote a hydrogen atom or a C 1 -C ₈ -alkyl radical.

Preferred comonomers are ethylene or propylene. Copolymers of polycyclic olefins of the formulas I or III and the acyclic olefins of the formula VIII are used in particular. Particularly preferred cycloolefins are norbornene and tetracyclododecene, which are characterized by C -.- C. _j -Alkyl can be substituted, ethylene-norbornene copolymers being of particular importance. Of the monocyclic olefins of formula VII, cyclopentene, which may be substituted, is preferred. Mixtures of two or more olefins of the respective type are also to be understood as polycyclic olefins, monocyclic olefins and open-chain olefins. This means that cycloolefin homopolymers and copolymers such as bi-, ter- and multipolymers can be used.

The cycloolefin polymerizations which proceed with the opening of the double bond can either be homogeneous, which means that the catalyst system is soluble in the polymerization medium (DE-A-3 922 546, EP-A-0 203 799), or can be catalyzed using a conventional Ziegler catalyst system (DD -A-222 317, DD-A-239 409).

The cycloolefin homo- and copolymers which contain structural units derived from monomers of the formulas I to VI or VII are preferred with the aid of a homogeneous catalyst consisting of a metallocene, the central atom of which is a metal from the group consisting of titanium, zirconium, hafnium, vanadium, niobium and Tantalum, which forms a sandwich structure with two bridged mono- or polynuclear ligands, and an aluminoxane. The bridged metallocenes are prepared according to a known reaction scheme (cf. J. Organomet. Chem. 288 (1985) 63-67 and EP-A-320 762). The aluminoxane, which acts as a cocatalyst, can be obtained by various methods (cf. S. Pasynkiewicz, Polyhedron 9 (1990) 429). The structure as well as the synthesis of this catalyst and the suitable conditions for the polymerization of these cycloolefins are described in detail in DE-A-3 922 546 and in an earlier priority, not previously published patent application (DE-A-4 036 264). Cycloolefin polymers with a viscosity number greater than 20 cm ³ / g and a glass transition temperature between 100 and 200 ° C. are preferably used.

The alloys can also contain cycloolefin polymers which have been polymerized with ring opening in the presence of, for example, catalysts containing tungsten, molybdenum, rhodium or rhenium. The cycloolefin polymers obtained in this way have double bonds which can be removed by hydrogenation (US Pat. Nos. 3,557,072 and 4,178,424).

The cycloolefin polymers used for the alloys according to the invention can also be obtained by grafting with at least one monomer selected from the group consisting of (a) σ, β-unsaturated carboxylic acids and / or their derivatives, (b) styrenes, (c) organic silicone components contain an olefinic unsaturated bond and a hydrolyzable group and (d) unsaturated epoxy components, be modified. The modified cycloolefin polymers obtained have excellent properties similar to the unmodified cycloolefin polymers. In addition, they have a particularly good adhesion to metals and synthetic polymers. The good compatibility with other polymers should be emphasized.

Polyaryl ether ketones (B) suitable for the alloys according to the invention are composed of at least one structural unit of the formula IX

-f-O-Y-O-X-3- (IX)

built up, whereby -X- is selected from the bivalent residues

X ¹

the p-link for the middle one

and -Y- selected] is from the residues

wherein R ¹ and R ² are identical or different and are halogen, preferably bromine, C.-C alkyl or _β alkoxy, preferably C, -. C ₄ alkyl or alkoxy, aryl, preferably phenyl, or aryloxy groups, k and n are identical or different and are generally integers zero, 1, 2, 3 or 4, preferably zero, 1 or 2, in particular zero or 2 and D is a cycloalkylidene group or a group selected from the following bivalent groups: D ¹

D ⁴ D ⁵

-C (CH ₃ ) ₂ -C (CF ₃ ) ₂

D ⁶ D ⁷ D ⁸

D ⁹ (m or p)

D 10 (m or p)

The molar ratio of the monomers containing -X- or -Y- is generally 0.95 to 1.05 to 1.00, preferably 1: 1. In the case of polyaryl ether ketones which have been prepared using indane compounds with residues Y ⁶ and Y ⁷ , this molar ratio is generally 1 0001 to 1 0600 to 1, preferably 1 0020 to 1 0500 to 1 and in particular 1 0040 to 1 0500 to 1.

The polymers listed can be homopolycondensates, which therefore contain only one unit of the type -X- and one unit of the type -Y- per recurring unit, or copolycondensates which contain two or more different units of the type -X- and / or two or contain several different units of type -Y-.

-X- is preferably selected from X ¹ and X ² and X is particularly preferred. ² -Y- is preferably selected from Y \ Y ^2, Y ^3, Y is particularly preferable. ³ -b- is preferably D ² , D ³ , D ⁴ , D ⁵ , D ⁶ , D ⁷ , D ⁸ , D ⁹ , D ¹⁰ or a cycloalkylidene group. D ⁴ , D ⁵ , D ⁹ , D ¹⁰ or a cycloalkylidene group are particularly preferred.

If -X- has been selected from X ¹ and X ² , then -Y- does not represent Y ^4. If -Y- is Y ³ and n is zero, D ¹ and D ^{2 are} not selected in this case.

If in the structural unit of the formula (IX) -X- is X ³ , then -Y- is preferably Y ¹ or Y ² and n is zero, 1 or 2, in particular zero.

If it is in the polyaryletherketones not homopolymers but rather copolycondensates so -X- is also preferably selected from X ¹ and X ^2, X is particularly preferred. ² -Y- is preferably Y ¹ and / or a radical selected from Y ² to Y ⁸ . The combination Y ¹ and Y ³ is particularly preferred. The sum of the recurring structural units, defined in mol% as [a] dh - [- 0-Y ¹ -0-X ² -] - and [b] dh - [- 0-Y ³ -0-X ² -] - always 100 mol%. If [a] is 50 to 100 mol%, [b] 0 to 50 mol%, semi-crystalline polyaryl ether ketones result. If [a] is 0 to 49 mol% and [b] 51 to 100 mol%, amorphous polyaryl ether ketones result.

Amorphous polyaryl ether ketones differ from the partially crystalline polyaryl ether ketones, both in the alloys according to the invention can be used in that they have no melting point, but only a glass transition temperature of at least 140 ° C, preferably at least 155 ° C.

Homo- and copolycondensates which preferably contain X ² and / or X ³ can also be used for the alloys of the invention. Preferred copolycondensates are a combination of X ² and X ³ , where -Y- is Y ¹ and n is zero.

According to the invention, linear aromatic polyaryl ether ketones which are composed of at least one of the structural units (IX) and whose radical -Y- represents at least one radical Y ⁶ or Y ⁷ , which may also contain units of the radical Y ³ , in which -D- the group D ⁴ is used. Such polyaryl ether ketones have a glass transition temperature of at least 170 ° C, preferably at least 185 ° C.

The indane-containing polyaryl ether ketones preferably have the structure

or

^ω As mentioned, in addition to the indane grouping, a bivalent radical of the formula

- ^{c <PHJr} O ^" . The indices r and s generally have values above 10, the molecular weights resulting from the monomer ratios and expressed in the inherent viscosities of the polymers. Due to the small excess of the dihalo compounds used, the polyaryl ether ketones have Halogen atoms (shark), generally chlorine and preferably fluorine, on the chain ends.

In addition to the use of a homo- or a copolycondensate, polymer mixtures can also be used, consisting of two or more of the homopolycondensates mentioned above, one or more of the homopolycondensates mentioned and one or more of the copolycondensates mentioned or two or more of the copolycondensates mentioned.

The polyaryl ether ketones (B) are prepared under the usual conditions by the methods already mentioned, which are also described, for example, in High Performance Polymers, 1989, Vol. 1 (1), 41-59 and in Polymer, 29 (1988), 358-369 to be discribed.

The semi-crystalline polyaryl ether ketones have inherent viscosities, determined according to DIN 51562, as a measure of their molecular weight, measured in a solution of 0.1 g of the polymer in 100 ml of 96% sulfuric acid at 25 ° C., of generally 0.2 to 2 5 dl / g, preferably 0.4 to 2.5 dl / g and in particular 0.4 to 2.0 dl / g.

The inherent viscosity of the amorphous polyaryl ether ketones, measured in a solution of 0.1 g of the polymer in 100 ml of chloroform at 25 ° C., is in the generally at 0.2 to 2.5 dl / g, preferably at 0.4 to 1.5 dl / g. The indane-containing polyaryl ether ketones have a viscosity of at least 0.3 dl / g.

The alloys according to the invention preferably contain 3 to 97% by weight and particularly preferably 5 to 95% by weight of the cycloolefin polymers (A) and preferably 97 to 3% by weight and particularly preferably 95 to 5% by weight of the polyaryl ether ketones (B), where the proportions of components A and B, relative to the total alloy, add up to 100% by weight. The alloys according to the invention can contain one or more cycloolefin polymers and one or more polyaryl ether ketones as well as modified cycloolefin polymers, modified polyaryl ether ketones and graft copolymers.

The alloys according to the invention are manufactured and processed by standard methods known for thermoplastics, such as e.g. by kneading, extrusion or injection molding.

The alloys according to the invention can contain additives, for example thermal stabilizers, UV stabilizers, antistatic agents, flame retardants, plasticizers, dyes, pigments, inorganic and organic fillers, i.e. in particular also reinforcing additives such as glass, carbon or high-modulus fibers. The alloys can be used particularly advantageously as a matrix material for composite materials. They are also suitable for the production of moldings by the injection molding or extrusion process, for example in the form of plates, fibers, films and tubes.

The following polymers were produced using standard methods:

Cycloolefin copolymer A1 [COC A1]

A) Preparation of diphenylmethylene (9-fluorenyl) -cyclopentadienyl-zirconium dichloride - (metallocene L) All subsequent operations were carried out in an inert gas atmosphere using absolute solvents (Schlenk technology).

A solution of 5.10 g (30.7 mmol) of fluorene in 60 cm ^{3 of} THF was slowly mixed with 12.3 cm ³ (30.7 mmol) of a 2.5 molar hexane solution of n-butyllithium at room temperature. After 40 min, 7.07 g (30.7 mmol) of diphenylfulven was added to the orange solution and the mixture was stirred overnight. 60 cm ^{3 of} water were added to the dark red solution, the solution turning yellow and the solution etherifying. The ether phase dried over MgS0 ₄ was concentrated and left to crystallize at -35 ° C. 5.1 g (42%) of 1,1-cyclopentadienyl- (9-fluorenyl) -diphenylmethane were obtained as a beige powder.

2.0 g (5.0 mmol) of the compound were dissolved in 20 cm ^{3 of} THF and 6.4 cm ³ (10 mmol) of a 1.6 molar solution of butyllithium in hexane were added at 0 ° C. After stirring for 15 min at room temperature, the solvent was stripped off, the red residue was dried in an oil pump vacuum and washed several times with hexane. After drying in an oil pump vacuum, the red powder was added to a suspension of 1.16 g (5.00 mmol) of ZrCl ₄ at -78 ° C. After slowly warming up, the mixture was stirred for a further 2 h at room temperature. The pink suspension was filtered through a G3 frit. The pink residue was washed with 20 cm ³ CH ₂ CI ₂ , dried in an oil pump vacuum and extracted with 120 cm ³ toluene. After stripping off the solvent and drying in an oil pump vacuum, 0.55 g of the zircon complex was obtained in the form of a pink-red crystal powder.

The orange-red filtrate of the reaction mixture was concentrated and left to crystallize at -35 ° C. A further 0.45 g of the complex crystallize from CH ₂ CI ₂ .

Total yield 1.0 g (36%). Correct elementary analysis. The mass spectrum showed M ⁺ = 556. ¹ H-NMR spectrum (100 MHz, CDCI ₃ ): 6.90 - 8.25 (m, 16, Flu-H, Ph-H), 6.40 (m, 2 , Ph-H), 6.37 (t, 2, Cp-H), 5.80 (t, 2, Cp-H). B) Production of COC A1

A clean and dry 75 dm ³ polymerization reactor with stirrer was purged with nitrogen and then with ethylene and filled with 22,000 g of melted norbornene (Nb). The reactor was then brought to a temperature of 70 ° C. with stirring and 6 bar of ethylene were injected.

Thereafter, 580 cm ^{3 of} toluene solution of methylaluminoxane (10.1% by weight of methylaluminoxane with a molecular weight of 1,300 g / mol after cryoscopic determination) were metered into the reactor and the mixture was stirred at 70 ° C. for 15 minutes, the ethylene pressure being kept at 6 bar by further metering has been. In parallel, 500 mg of metallocene were dissolved in 500 cm ^{3 of} toluene methylaluminoxane solution (concentration and quality see above) and preactivated by standing for 15 minutes. The solution of the complex (cat. Solution) was then metered into the reactor (in order to reduce the molecular weight, hydrogen can be fed to the reaction vessel via a lock immediately after metering in the catalyst). The mixture was then polymerized with stirring (750 revolutions / minute) at 70 ° C. for 140 minutes, the ethylene pressure being kept at 6 bar by further metering. The contents of the reactor were then quickly discharged into a stirred vessel in which 200 cm ^{3 of} isopropanol (as a stopper) had been placed. The mixture was precipitated in acetone, stirred for 10 min and then the suspended polymeric solid was filtered off.

The filtered polymer was then mixed with a mixture of two parts of 3-normal hydrochloric acid and one part of ethanol and stirred for 2 hours. The polymer was then filtered off again, washed neutral with water and dried at 80 ° C. and 0.2 bar for 15 hours. A product amount of 4400 g was obtained.

Cycloolefin copolymer A2 [COC A2]

A) Preparation of rac-dimethylsilyl-bis- (1-indenyl) zirconium dichloride (metallocene A) All subsequent operations were carried out in an inert gas atmosphere using absolute solvents (Schlenk technology).

A solution of 30 g (0.23 mol) of indene (technical grade 91%) filtered through aluminum oxide in 200 cm ^{3 of} diethyl ether was cooled with ice with 80 cm ³ (0.20 mol) of a 2.5 molar solution of n-butyllithium in hexane. The mixture was stirred for a further 15 min at room temperature and the orange solution was added via a cannula to a solution of 13.0 g (0.10 mol) of dimethyldichlorosilane (99%) in 30 cm ^{3 of} diethyl ether within 2 hours. The orange suspension was stirred overnight and shaken three times with 100-150 cm ^{3 of} water. The yellow organic phase was dried twice over sodium sulfate and evaporated in a rotary evaporator. The remaining orange oil was kept in an oil pump vacuum at 40 ° C. for 4 to 5 hours and freed from excess indene, a white precipitate being formed. By adding 40 cm ^{3 of} methanol and crystallizing at -35 ° C., a total of 20.4 g (71%) of the compound (CH ₃ ) ₂ Si (Ind) _{2 could} be isolated as a white to beige powder. Mp 79-81 ° C (2 diastereomers).

A solution of 5.6 g (19.4 mmol) of (CH ₃ ) ₂ Si (Ind) ₂ in 40 cm ³ THF was slowly at room temperature with 15.5 cm ³ (38.7 mmol) of a 2.5 molar Hexane solution of butyllithium added. 1 hour after the end of the addition, the deep red solution was added dropwise to a suspension of 7.3 g (19.4 mmol) of ZrCl ₄ 2THF in 60 cm ³ THF within 4-6 hours. After stirring for 2 hours, the orange precipitate was filtered off with a glass frit and recrystallized from CH ₂ CI ₂ . 1.0 g (11%) of rac- (CH ₃ ) ₂ Si (Ind) ₂ ZrCl _{2 were obtained} in the form of orange crystals which gradually decompose from 200 ° C. Correct elementary analysis. The E1 mass spectrum showed M ⁺ = 448. ¹ H-NMR spectrum (CDCI ₃ ): 7.04 - 7.60 (m, 8, aromatic H), 6.90 (dd, 2, β-ind H) ), 6.08 (d, 2, σ-Ind H), 1.12 (s, 6, SiCH ₃ ). B) Production of COC A2

COC A2 was prepared analogously to that of COC A1, with some of the conditions summarized in Table 1 being changed.

Table 1

Cyclo-norbornene T pressure metallocene cat. Time amount olefin amount [° C] [bar] type amount solution [min] product copolymer [g] [mg] [ml] [g]

A2 25000 70 10 A 3000 1000 220 5100

Metallocene A: rac-dimethylsilyl-bis- (1-indenyl) zirconium dichloride

The physical characteristics of both cycloolefin copolymers are shown in Table 2.

* determined by C-nuclear magnetic resonance spectroscopy

VZ: Viscosity numbers determined according to DIN 53728 M _w , M _n : GPC 150-C ALC Millipore Waters Chromatograph

Column set: 4 Shodex columns AT-80 M / S solvent: o-dichlorobenzene at 135 ° C flow: 0.5 ml / min, concentration 0.1 g / dl Rl detector, calibration: polyethylene (901 PP)

Further characteristics of the cycloolefin copolymers can be found in the examples.

Semi-crystalline polyaryl ether ketone B1 and amorphous polyaryl ether ketone B3 with structural units a and b of the formulas

where B1 contains 70 mol% of structural units a and 30 mol% of structural units b and B3 40 mol% of structural units a and 60 mol% of structural units b. The inherent viscosity of B1, measured in 96% sulfuric acid at 25 ° C, is 0.45 dl / g. The inherent viscosity of B3, measured in chloroform at 25 ° C, is 0.50 dl / g.

Amorphous polyaryl ether ketones B2 and B4 with structural units of the formula

whose inherent viscosity, measured in chloroform at 25 ° C, is 0.65 dl / g (B2) and 0.50 dl / g (B4).

The polymers described above were first dried (130 ° C., 24 h, vacuum) and then in different weight ratios in a measuring kneader (from HAAKE (Karlsruhe), Rheocord System 40 / Rheomix 600) or measuring extruder (from HAAKE (Karlsruhe) , Rheocord System 90 / Rheomex TW 100) kneaded or extruded under protective gas (Ar). The ground or granulated alloys obtained were dried (130 ° C., 24 h, vacuum) and then pressed into sheets (120 × 1 mm) (vacuum press: Polystat 200 S, from Schwabenthan (Berlin)). The ground or granulated alloys were introduced into a suitable mold in the press preheated to 335 ° C., a vacuum was drawn and the mixture was melted for 10 minutes. At the above temperature, a pressure of 100 bar was reached, the mixture was left for 5 minutes and cooled to room temperature within 10 minutes. The melt press plates obtained were examined for their physical properties.

The following devices were used for this:

A differential scanning calorimeter (DSC-7) from Perkin-Elmer (Überlingen) for measuring, for example, glass levels, melting points and heat of fusion.

A torsion pendulum machine from Brabender (Duisburg) for measuring

Thrust module, damping and linear expansion.

A tensile strain testing machine (type: Instron 4302) from Instron

(Offenbach).

A MPS-D melt index tester from Goettfert (Buchen) for measuring

Fluidity. Melt index according to DIN 53735-MFI-B, stamp load / temperature variable; Cylinder: inner dimension 9.55 (+/- 0.01) mm, length at least 115 mm,

Outlet nozzle 2.095 (+/- 0.005) mm. 5 minutes was selected as the melting time.

The water content was determined in accordance with ASTM D 4019-81.

Example 1 :

Using the measuring kneader, the cycloolefin copolymer (A1) and the partially crystalline polyaryl ether ketone (B1) were kneaded together in various weight ratios after intensive drying under an argon atmosphere. The table below shows the thermal properties of the alloys.

2. Heating Tg Tm dHm Tg

(semi-crystall. (Cycloolefin-

Polyether ketone) copolymer)

[° C] [° C] [J / g] [° C]

183.0

162.2 322.1 11.0 182.7

162.4 323.0 19.0 182.8 162.5 320.7 26.0

Heating rate: 20 K / minute Example 2:

Using the measuring kneader, the cycloolefin copolymer (A1) and the partially crystalline polyaryl ether ketone (B1) were kneaded together in various weight ratios after intensive drying under an argon atmosphere and then ground. After intensive drying, the ground products were used to measure the flowability.

* Only to 200 cm ^3/10 min measured device-specific

Example 3:

Using the measuring kneader, the cycloolefin copolymer (A1) and the amorphous polyaryl ether ketone (B2) were kneaded together in various weight ratios after intensive drying under an argon atmosphere. The table below shows the thermal properties of the alloys.

Heating rate: 20 K / minute

Example 4:

Using the measuring kneader, the cycloolefin copolymer (A1) and the amorphous polyaryl ether ketone (B2) were kneaded together in various weight ratios after intensive drying under an argon atmosphere and then ground. The ground products were dried intensively and the water absorption was determined after storage, 564 h at 23 ° C. and 85% relative humidity.

Example 5:

Using the measuring kneader, the cycloolefin copolymer (A1) and the amorphous polyaryl ether ketone (B2) were kneaded together in various weight ratios after intensive drying under an argon atmosphere and then ground. After intensive drying, the ground products were used to measure the flowability.

Amorphous cycloolefin MFI (MVI) copolymer polyaryletherketone 3.8 kgf, 300 ° C (A1) (B2) [% by wt.] [% Wt.] [Cm ^3/10 minutes]

100 0 14.5

70 30 62.3

50 50 61.0

30 70 23.7

0 100 7.1

Example 6:

Using the measuring kneader, the cycloolefin copolymer (A1) and the amorphous polyaryl ether ketone (B3) were kneaded together in various weight ratios after intensive drying under an argon atmosphere. The table below shows the thermal properties of the alloys.

Heating rate: 20 K / minute

Example 7:

Using the measuring kneader, the cycloolefin copolymer (A1) and the amorphous polyaryl ether ketone (B3) were kneaded together in various weight ratios after intensive drying under an argon atmosphere and then ground. After intensive drying, the ground products were pressed into press plates. The table below shows the mechanical data of the alloys.

Cyclo-amorphous shear modulus G '(torsion pendulum) olefin-polyaryl ether- [N / mm * mm] copolymer ketone temperature [° C]

Example 8:

Using the measuring kneader, the cycloolefin copolymer (A1) and the amorphous polyaryl ether ketone (B3) were kneaded together in various weight ratios after intensive drying under an argon atmosphere and then ground. After intensive drying, the ground products were used to measure the flowability.

Amorphous cycloolefin MFI (MVI) copolymer polyaryletherketone 5 kgf, 310 ° C (A1) [wt.%] (B3) [wt.%] [Cm ^3/10 minutes]

100 0 37.9

70 30 108.3

50 50 131.7

30 70 149.0 0 100 3.2

Example 9:

Using the twin-screw extruder, the cycloolefin copolymer (A2) and the amorphous polyaryl ether ketone (B4) were mixed in different weight ratios intensive drying, extruded and granulated together under an argon atmosphere. The table below shows the thermal properties of the alloys.

Heating rate: 20 K / minute

Example 10:

Using the twin-screw extruder, the cycloolefin copolymer (A2) and the amorphous polyaryl ether ketone (B4) were extruded and granulated together in various weight ratios after intensive drying under an argon atmosphere. After intensive drying, the granules were then pressed into press plates. The table below shows the mechanical data of the alloys.

Claims

1. polymer alloys containing at least two components (A) and (B), characterized in that

(A) at least one cycloolefin polymer and

(B) is at least one polyaryl ether ketone, with (A) in amounts of 1 to 99% by weight and (B) in amounts of 99 to 1% by weight, based on the sum of (A) and (B) .

2. Polymer alloy according to claim 1, characterized in that the cycloolefin polymers (A) contain structural units which are derived from at least one monomer of the formulas I to VI or VII

are derived, wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 are} identical or different and denote a hydrogen atom or a C.-C _B alkyl radical, the same radicals in the different formulas can have different meanings and n is an integer from 2 to 10.

Alloy according to Claim 2, characterized in that the cycloolefin polymer (A) contains, in addition to the structural units which are derived from at least one monomer of the formulas I to VII, further structural units which are derived from at least one acylic 1-olefin of the formula VIII

are derived, wherein R ⁹ , R ¹⁰ , R ¹¹ and R ^{12 are the} same or different and represent a hydrogen atom or a ^ -C _a -alkyl radical.

4. Alloy according to claim 3, characterized in that the cycloolefin polymer (A) is a copolymer of polycyclic olefins of the formulas I or III and the acylic olefins of the formula VIII.

5. Alloy according to claim 4, characterized in that the cycloolefin polymer (A) is a copolymer of norbornene and ethylene.

6. Alloy according to claim 1, characterized in that the polyaryl ether ketone (B) from at least one structural unit of the formula IX

- O-Y-O-X -} - (IX)

built up, whereby -X- is selected from the bivalent residues

(meta- (m) or para- (p) substitution)

(m or p)

and -Y- is selected from the residues

wherein R ¹ and R ^{2 are} identical or different and represent halogen, CC ₈ alkyl or alkoxy, aryl or aryloxy groups, k and n are identical or different and generally mean integers zero, 1, 2, 3 or 4 and D is a cycloalkylidene group or a group selected from the following bivalent groups: D ¹ D ² D ³

-O-, ^ C = 0, -CH ₂ -, D ⁴ D ⁵

-C (CH ₃ ) ₂ -, -C (CF ₃ ) ₂ -,

D ⁷

CH ₃ H CH, II c- - c— C-

(m or p)

-, 10 (m or p)

Alloy according to claim 6, characterized in that -X- is selected from X ¹ , X ² , -Y- is at least one divalent radical selected from Y ¹ to Y ⁸ and -D- D ⁴ , D ⁵ , D ⁹ , D ¹⁰ or a cycloalkylidene group.

8. Alloy according to claim 7, characterized in that the polyaryl ether ketone (B) has structural units of the following formulas:

Alloy according to claim 1, characterized in that the cycloolefin polymer (A) is a copolymer of norbornene and ethylene and the polyaryl ether ketone (B) structural units of the formula

contains.

10. Alloy according to claim 1, characterized in that the

Cycloolefin polymer (A) a copolymer of norbornene and ethylene and the polyaryl ether ketone (B) structural units of the formula

- «o> - contains.

11. Use of an alloy according to claim 1 as a matrix material for composite materials or for the production of moldings.