POLYKETONE MOULDING COMPOUNDS WITH IMPROVED PROPERTIES, MOULDED ARTICLES PRODUCED THEREFROM AND ALSO METHOD FOR THE PRODUCTION THEREOF

Abstract

The present invention relates to polyketone moulding compounds based on partially crystalline, aliphatic polyketones. In particular, it relates to fibre-reinforced moulding compounds based on aliphatic polyketones which preferably comprise small quantities of phosphinic acid or the salts thereof. The moulding compounds are distinguished by improved mechanical properties and good processability in injection moulding. These moulding compounds are suitable for the production of in particular thin-walled moulded articles for the electrical and electronics industry, such as for example housings, housing components or connectors.

Claims

1-14. (canceled)

15. A polyketone moulding compound comprising or consisting of (A) 25-99.9% by weight of at least one aliphatic polyketone; (B) 0-70% by weight of filling- or reinforcing materials; (C) 0.1-6% by weight of at least one phosphorus-containing compound, selected from the group consisting of (C1) 0-6% by weight of at least one phosphinic acid or at least one diphosphinic acid, a metal salt and/or an organic derivative thereof; (C2) 0-2% by weight of at least one organic phosphite or phosphonite, wherein at least one of the phosphorus-containing compounds (C1) and (C2) is present in the polyketone moulding compound, so that the sum of the phosphorus-containing compounds (C1) and (C2) is at least 0.1% by weight, and (D) 0-20% by weight of at least one additive, the sum of (A) to (D) producing 100% by weight, the amounts for (A) to (D) including (C1) and (C2) respectively relating to the moulding compound or the sum of (A) to (D).

16. The polyketone moulding compound according to claim 15, wherein, respectively independently of each other or in combination with each other, the amount (A) of the at least one aliphatic polyketone is 32 to 89.7% by weight, (B) of the filling- or reinforcing materials is 10 to 60% by weight, (C) of the at least one phosphorus-containing compound is 0.2 to 4% by weight, and (D) of the at least one additive is 0.1 to 6% by weight.

17. The polyketone moulding compound according to claim 15, wherein the at least one polyketone (A) is a polymer of carbon monoxide and at least one olefinically unsaturated compound, and at least one further olefinically unsaturated compound with at least 3 carbon atoms, and mixtures thereof.

18. The polyketone moulding compound according to claim 15, wherein the at least one polyketone (A) is a terpolymer of the subsequent general formula
*CH.sub.2CH.sub.2CO.sub.x(Q-CO.sub.y* wherein Q is a divalent group derived from olefinically unsaturated compounds with at least 3 carbon atoms, and the molar ratio y:x is less than or equal to 0.5.

19. The polyketone moulding compound according to claim 15, wherein the at least one aliphatic polyketone a) is a partially crystalline polyketone, b) has a melt viscosity (MVR, melt volume-flow rate), determined according to ISO 1133 at 240 C. and with a load of 2.16 kg, in the range of 5-200 cm.sup.3/10 min, c) has a relative viscosity, measured on solutions of 0.5 g polyketone dissolved in 100 ml m-cresol at 20 C. with a capillary viscometer, of 1.5 to 2.5, and/or d) has a number-average molar mass, determined by means of GPC in hexafluoroisopropanol relative to PMMA standards, in the range of 20,000 to 100,000 g/mol.

20. The polyketone moulding compound according to claim 15, wherein the filling- or reinforcing materials are selected from the group consisting of fibrous or particulate filling materials or the mixtures thereof, which are optionally equipped with a size and/or an adhesive.

21. The polyketone moulding compound according to claim 20, wherein the fibrous filling materials a) are selected from the group consisting of glass fibres, carbon fibres, metal fibres, aramide fibres, basalt fibres and whiskers and mixtures or combinations thereof, b) are present in the form of endless strands and/or in cut form, and/or c) have a circular cross-section or a non-circular cross-section, mixtures thereof.

22. The polyketone moulding compound according to claim 20, wherein the particulate filling materials are selected from the group consisting of mineral particulate filling materials.

23. The polyketone moulding compound according to claim 15, wherein the at least one phosphorus-containing compound is selected from: 0.1-6% by weight of at least one phosphinic acid, of at least one diphosphinic acid and a metal salt of these phosphinic acids (component C1), or 0.1-2% by weight of an organic phosphite or phosphonite (component C2), or 0.1-6% by weight of a mixture of phosphinic acid or diphosphinic acid or a metal salt of these phosphinic acids (component C1) and of an organic phosphite or phosphonite (component C2), the mixture consisting up to 0.05-2% by weight of component C2 and up to 0.05-5.95% by weight of component C1.

24. The polyketone moulding compound according to claim 15, wherein the at least one phosphinic acid and the metal salts derived therefrom are of general formula (I) or the at least one diphosphinic acid and the metal salts derived therefrom of general formula (II) ##STR00002## wherein R1, R2 are the same or different and preferably are C1-C8 alkyl, linear or branched, saturated, unsaturated or partially unsaturated and/or aryl; R3 is C1-C10 alkylene, linear or branched, saturated, unsaturated or partially unsaturated, C6-C10 arylene, alkylarylene or arylalkylene; M is a hydrogen ion (proton) or a metal ion from the 2.sup.nd or 3.sup.rd main or subsidiary group of the periodic table; and m=2 or 3; n=1 or 3; x=1 or 2.

25. The polyketone moulding compound according to claim 15, wherein the at least one organic phosphite or phosphonite (component C2) is selected from the group consisting of triphenylphosphite, diphenylalkylphosphite, phenyldialkylphosphite, tris(nonylphenyl)phosphite, trilaurylphosphite, trioctadecylphosphite, di stearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diisodecylpentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tris-(tert-butylphenyl))pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphocine, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyldibenzo[d,g]-1,3,2-dioxaphosphocine, bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphite, and bis(2,4-di-tert-butyl-6-methylphenyl)ethylphosphite.

26. The polyketone moulding compound according to claim 15, wherein the at least one additive (component D) is selected from the group consisting of stabilisers, antioxidants, processing aids, polymers different from aliphatic polyketones, impact modifiers, adhesives, crystallisation accelerators or retarders, flow aids, lubricants, mould-release agents, plasticisers, radical collectors, antistatic agents, colouring- and marking substances, nanoparticles in lamellar form, layer silicates, conductivity additives, residues from polymerisation processes, oxygen-, nitrogen- or sulphur-containing metal compounds and regulators, and mixtures or combinations hereof.

27. A moulded article produced from a polyketone moulding compound according to claim 15.

28. A method for the production of a moulded article according to claim 27, comprising injection moulding, extrusion moulding, or blow-moulding.

Description

DESCRIPTION OF PREFERRED EMBODIMENTS

[0098] Preferred embodiments of the invention are described subsequently with reference to embodiments, given by way of example, which serve only for explanation and should not be interpreted as restrictive.

Production of the Polyketone Moulding Compounds:

[0099] The raw materials of components (A), (C) and (D) are mixed in advance and metered gravimetrically into the feed of a twin-screw extruder of the type ZSK25 (Werner and Pfleiderer). Component (B) is metered into the melt via a sidefeeder 4 housing units in front of the discharge. The process takes place at cylinder temperatures of 200-270 C. at a screw speed of rotation of 200 rpm and a throughput of 10 kg/h. The compound is discharged via a nozzle and granulated after cooling the strand. Subsequently drying takes place at 100 C. for 24 h in a vacuum.

Production of the Moulded Articles:

[0100] The production of the moulded articles is effected on an injection moulding machine, Arburg Allrounder 420C-1000-250, with a rising cylinder temperature profile in the range of 200-270 C. and injection pressures of 1,000-1,800 bar. The mould temperature is 80 C. The geometry of the moulded articles corresponds to the specifications of the corresponding testing standards.

[0101] The following materials were used: [0102] PK-EP (LV): Low-viscous aliphatic polyketone made of carbon monoxide, ethylene and propylene with a melting point of 220 C., MFR (240 C., 2.16 kg) of [0103] PK-EP (HV): Highly viscous aliphatic polyketone made of carbon monoxide, ethylene and propylene with a melting point of 220 C., MFR (240 C., 2.16 kg) of 6 g/10 min, Hyosung Co. Ltd. [0104] PA12: Polyamide PA12, solution viscosity of rel=1.95 (0.5 g polymer dissolved in 100 ml m-cresol, 20 C.), melting point of 178 C., EMS-CHEMIE AG. [0105] Polybond 3002: Maleic anhydride-modified polypropylene, BP Performance Polymers Inc [0106] Exolit OP1230: Aluminium-tris-diethylphosphinate, Clariant, CH [0107] Magnefin H10 IV: High-purity magnesium hydroxide, Albemarle [0108] Glass fibre: Glass fibre with a round cross-section for polyamides, fibre length 4.5 mm, diameter 10 m, Vetrotex [0109] Sandostab P-EPQ: Tetrakis(2,4-di-t-butylphenyl)-4,4-biphenylene diphosphonite (CAS: 38613-77-3), Clariant [0110] Stabiliser: Irganox 1010, sterically hindered phenolic antioxidant (BASF SE)

[0111] The compositions of the moulding compounds and the properties of the moulded articles according to the invention produced therefrom are compiled in Table 1, comparative examples are indicated in Table 2.

TABLE-US-00001 TABLE 1 Examples E1-E6 according to the invention: E1 E2 E3 E4 E5 E6 PK-EP (LV) % by weight 69.3 68.3 48.45 38.45 64.3 67.3 Glass fibres % by weight 30.0 30.0 50.0 60.0 30.0 30.0 Sandostab P-EPQ % by weight 0.2 0.2 0.15 0.15 0.2 0.2 Exolit OP1230 % by weight 1.0 1.0 1.0 5.0 2.0 Irganox 1010 % by weight 0.5 0.5 0.4 0.4 0.5 0.5 Properties Modulus of elasticity MPa 8,400 8,500 13,800 16,300 9,000 8,400 Breaking strength MPa 135 136 175 173 137 139 Breaking elongation % 3.5 5 3.2 3.1 5.2 5.3 Impact 23 C. kJ/m.sup.2 72 93 77 65 85 95 Impact 30 C. kJ/m.sup.2 66 87 64 64 84 85 Notch impact 23 C. kJ/m.sup.2 16 14 18 17 14 17 Notch impact 30 C. kJ/m.sup.2 11 11 14 12 10 12 HDT A (1.80 MPa) C. 207 204 212 212 205 208 HDT C (8.00 MPa) C. 158 143 185 183 155 164 MVR (250 C./21.6 kg) cm.sup.3/10 min 152 126 78 5 86 115 % by weight = percent by weight

TABLE-US-00002 TABLE 2 comparative examples CE1-CE7 CE1 CE2 CE3 CE4 CE5 CE6 CE7 PK-EP (LV) % by weight 69.5 49.5 68.5 64.5 34.7 64.6 64.0 PK-EP (HV) % by weight 34.8 Polybond 3002 % by weight 5.0 PA12 % by weight 5.0 Glass fibres % by weight 30.0 50.0 30.0 30.0 30.0 30.0 30.0 Exolit OP1230 % by weight Magnifin H10 IV % by weight 1 5 Stabiliser % by weight 0.5 0.5 0.5 0.5 0.5 0.4 0.5 Properties Modulus of elasticity MPa 8,500 13,700 8,500 8,600 8,200 8,300 6,700 Breaking strength MPa 112 105 110 105 99 96 103 Breaking elongation % 2.6 1.3 2.8 3.0 2.4 2.8 5.8 Impact 23 C. kJ/m.sup.2 52 34 50 55 40 32 84 Impact 30 C. kJ/m.sup.2 40 30 40 39 39 28 82 Notch impact 23 C. kJ/m.sup.2 12 11 11 11 13 11 17 Notch impact 30 C. kJ/m.sup.2 9 9 9 9 9 9 11 HDT A (1.80 MPa) C. 204 212 204 201 205 155 207 HDT C (8.00 MPa) C. 162 183 160 141 137 103 149 MVR (250 C./21.6 kg) cm.sup.3/10 min 326 98 253 235 97 590 65 % by weight = percent by weight

[0112] The measurements were implemented according to the following standards and on the following test pieces in the dry state. This means that the test pieces are stored after the injection moulding for at least 48 h at room temperature in a dry environment, over silica gel, before they are supplied for the tests.

[0113] The thermal behaviour (melting point (TM), melting enthalpy (Hm), glass transition-temperature (Tg)) was determined by means of the ISO standard 11357 (11357-2 for the glass transition temperature, 11357-3 for the melting temperature and the melting enthalpy) on the granulate. The differential scanning calorimetry (DSC) was implemented at a heating rate of 20 C./min.

[0114] The relative viscosity (rel) was determined according to DIN EN ISO 307 on solutions of 0.5 g polymer dissolved in 100 ml m-cresol at a temperature of 20 C. Granulate is used as sample.

[0115] Modulus of elasticity in tension, breaking strength and breaking elongation: modulus of elasticity in tension, breaking strength and breaking elongation were determined according to ISO 527 at a tensile speed of 1 mm/min (modulus of elasticity in tension) or at a tensile speed of 5 mm/min (breaking strength, breaking elongation) on the ISO test bar, standard ISO/CD 3167, type AI, 17020/104 mm at a temperature 23 C.

[0116] Impact strength and notch impact strength according to Charpy were measured according to ISO 179/keU or ISO 179/keA on the ISO test bar, standard ISO/CD 3167, type B1, 80104 mm at a temperature of 23 C.

[0117] The MVR (melt volume-flow rate) is determined according to ISO 1133 by means of a capillary rheometer, the material (granulate) being melted in a heatable cylinder at a temperature of 250 C. and being pressed through a defined nozzle (capillary) at a pressure produced by the overlay load of 21.6 kg. The emerging volume of the polymer melt is determined as a function of time.

[0118] The thermal dimensional stability in the form of HDT A (1.80 MPa) and HDT C (8.00 MPa) was determined according to ISO 75-1 and ISO 75-2 on ISO impact bars of the dimension 80104 mm (test pieces in flat-laid position).

[0119] By the use according to the invention of component (C), the mechanical properties, in particular the breaking strength, the breaking elongation and also the impact- and notch impact strength could be significantly improved.

[0120] Significantly higher property improvements are thereby achieved than when using normal adhesives, such as e.g. maleic anhydride-grafted polyolefins (CE6). By addition of aliphatic polyamide, such as e.g. PA12, the strength and the breaking elongation are in fact increased but, at the same time, rigidity and breaking strength are reduced (CE7). Only the use according to the invention of component C allows simultaneous improvement in strength, breaking elongation and breaking strength without the rigidity being reduced.