Flameproof, aliphatic polyketone materials, moulded articles produced therefrom and also method for the production thereof

Abstract

The present invention relates to polyketone molding compounds based on partially crystalline, aliphatic polyketones. In particular, it relates to halogen-free, flameproof molding compounds based on aliphatic polyketones which preferably comprise salts of phosphinic acids as flame retardant. The molding compounds fulfill the fire protection classification V0 according to UL94 and display good mechanical properties. These molding compounds are suitable for the production of in particular thin-walled molded articles for the electrical and electronics industry, such as for example housings, housing components or connectors.

Claims

1. A flameproof polyketone moulding compound consisting of: (A) 30-94% by weight of at least one partially crystalline, aliphatic polyketone with a melting temperature (T.sub.m) in the range of 180 C.-280 C., measured by means of DSC according to ISO 11357-3 and at a heating rate of 20 K/min; (B) greater than zero to 50% by weight of at least one filling- or reinforcing material; (C) 6-15% by weight of at least one halogen-free flame retardant; (D) 0-2.0% by weight of at least one organic phosphite and/or phosphonite; and (E) greater than zero to 10% by weight of at least one additive; the percentages by weight of components (A) to (E) together producing 100%; and wherein the polyketone moulding compound is free of magnesium hydroxide; wherein the at least one halogen-free flame retardant (C) is selected from the group consisting of at least one phosphinic acid, at least one diphosphinic acid, a metal salt or an organic derivative thereof, and mixtures or combinations thereof, optionally in combination with a synergist; and wherein the at least one additive (E) is selected from the group consisting of stabilisers, antioxidants, processing aids, polymers different from aliphatic polyketones, acid- or anhydride-modified polyolefins, polyesters, polyamides, impact modifiers, adhesives, crystallisation accelerators or retarders, flow aids, lubricants, mould-release agents, plasticisers, radical interceptors, antistatic agents, pigments, colouring- and marking substances, nanoparticles in laminar form, layer silicates, conductivity additives, residues from polymerisation processes, oxygen-, nitrogen- or sulphur-containing metal compounds, regulators, and mixtures or combinations thereof.

2. The polyketone moulding compound according to claim 1, wherein, independently of each other or in combination with each other, the content (A) of the at least one aliphatic polyketone is 35-83.85% by weight, (B) of the at least one filling- or reinforcing material is 10-50% by weight, (C) of the at least one halogen-free flame retardant is 7-12% by weight, (D) of the at least one organic phosphite and/or phosphonite is 0.05 to 1.5% by weight, and/or (E) of the at least one additive is 0.1-5% by weight.

3. The polyketone moulding compound according to claim 1, wherein the at least one polyketone (A) is a polymer of carbon monoxide and at least one olefinically unsaturated compound.

4. The polyketone moulding compound according to claim 1, wherein the at least one polyketone (A) is a terpolymer of the general formula ##STR00003## 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.

5. The polyketone moulding compound according to claim 1, 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. with an overlayer 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 a temperature of 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.

6. The polyketone moulding compound according to claim 1, wherein the at least one filling- or reinforcing material is selected from the group consisting of fibrous filling materials, particulate filling materials and mixtures thereof, which are optionally equipped with a size and/or an adhesive.

7. The polyketone moulding compound according to claim 6, wherein the fibrous filling materials a) are selected from the group consisting of glass fibres, carbon fibres, metal fibres, aramide fibres, basalt fibres, 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, a non-circular cross-section, or both.

8. The polyketone moulding compound according to claim 6, wherein the particulate filling materials are mineral particulate filling materials.

9. The polyketone moulding compound according to claim 1, wherein the at least one halogen-free flame retardant consists of (C1) 60-100% by weight of at least one phosphinic acid, at least one diphosphinic acid, a metal salt and/or an organic derivative thereof and (C2) 0-40% by weight of at least one synergist.

10. The polyketone moulding compound according to claim 9, wherein (C1) the at least one phosphinic acid and the metal salts derived therefrom are of formula I or the at least one diphosphinic acid and the metal salts derived therefrom are of formula II ##STR00004## wherein R1, R2 are the same or different and 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 group IIA, IIB, IIIA, or IIIB of the periodic table; m=2 or 3; n=1 or 3; and x=1 or 2; and/or (C2) the at least one synergist is selected from the group consisting of nitrogen and/or phosphorus-containing synergists, and oxygen-, nitrogen- or sulphur-containing metal compounds.

11. The polyketone moulding compound according to claim 2, wherein the at least one organic phosphite and/or phosphonite is selected from the group consisting of triphenylphosphite, diphenylalkylphosphite, phenyldialkylphosphite, tris(nonylphenyl)phosphite, trilaurylphosphite, trioctadecylphosphite, di stearylpentaerythritoldiphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diisodecylpentaerythritoldiphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritoldiphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritoldiphosphite, diisodecyloxypentaerythritoldiphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritoldiphosphite, bis(2,4,6-tris-(tert-butylphenyl))pentaerythritoldiphosphite, tristearylsorbitoltriphosphite, 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.

12. The polyketone moulding compound according to claim 1, which is of a classification V0 with 0.35 to 3.0 mm thick test pieces according to UL94.

13. A moulded article produced from a polyketone moulding compound according to claim 1.

14. The moulded article according to claim 13, which is selected from the group consisting of housings, functional parts for pumps, transmissions, valves, water meters, throttle valves, cylinders, pistons, headlight housings, reflectors, bend-light adjustment, toothed wheels, engine and transmission bearings, plug-in connections, connectors, profiles, foils or layers of multilayer foils, fibres, electronic components, tools, composite materials, fluid-conducting pipes and containers, fittings for connecting hoses, corrugated pipes and media-conducting pipes, components of multilayer pipes, individual layers in multilayer containers, hydraulic pipes, brake pipes, clutch pipes, coolant pipes and brake fluid containers.

15. A method for the production of a moulded article according to claim 14, which comprises injection moulding, extrusion or blow-moulding.

16. The polyketone moulding compound according to claim 3, wherein the at least one olefinically unsaturated compound is selected from the group consisting of ethene and at least one further olefinically unsaturated compound with at least 3 carbon atoms, and mixtures or combinations thereof.

Description

DESCRIPTION OF PREFERRED EMBODIMENTS

(1) 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.

(2) Production of the Polyketone Moulding Compounds:

(3) The raw materials of components (A), (C) and (D) are mixed in advance and metered gravimetrically into the feed of a twin-shaft 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.

(4) Production of the Moulded Articles:

(5) 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.

(6) The compositions of the moulding compounds and the properties of the moulded articles produced therefrom are compiled in table 1.

(7) The Following Materials were Used:

(8) PK-EP: average-viscous aliphatic polyketone made of carbon monoxide, ethylene and propylene with a melting point of 220 C., MFR (240 C., 2.16 kg) of 60 g/10 min, Hyosung Co. Ltd. Exolit OP1230: aluminium-tris-diethylphosphinate, Clariant, CH Magnifin H10 IV: high-purity magnesium hydroxide, Albemarle Glass fibre: glass fibre with a round cross-section for polyamides, fibre length 4.5 mm, diameter 10 m, Vetrotex Sandostab P-EPQ: tetrakis(2,4-di-t-butylphenyl)-4,4-biphenylene diphosphonite (CAS: 38613-77-3), Clariant Stabiliser: Irganox 1010, sterically hindered phenolic antioxidant (BASF SE)

(9) TABLE-US-00001 TABLE 1 Examples E1-E3 according to the invention and comparative examples CE1-CE4 E1 E2 E3 CE1 CE2 CE3 CE4 PK-EP % by weight 59.3 59.7 62.3 39.7 49.7 54.7 69.5 Glass fibres % by weight 30.0 30.0 30.0 30.0 20.0 15.0 30.0 Sandostab P-EPQ % by weight 0.2 0.2 Exolit OP1230 % by weight 10.0 10.0 7.0 Magnifin H10 IV % by weight 30.0 30.0 30.0 Stabiliser % by weight 0.5 0.3 0.5 0.3 0.3 0.3 0.5 Properties Modulus of elasticity MPa 9,300 9,300 9,100 11,700 9,100 7,500 8,500 Breaking strength MPa 126 123 132 130 114 107 112 Breaking elongation % 5.0 5.1 5.2 2.6 2.8 3.4 2.6 Impact 23 C. kJ/m.sup.2 85 78 86 54 52 56 52 Impact 30 C. kJ/m.sup.2 76 70 75 30 32 33 40 Notch impact 23 C. kJ/m.sup.2 13 13 14 9 8 8 12 Notch impact 30 C. kJ/m.sup.2 10 10 11 6 6 5 9 Fire test t Thickness 0.75 mm V0 V0 V0 V0 V0 V0 HB Thickness 1.5 mm V0 V0 V0 V0 V0 V0 HB HDT A (1.80 MPa) C. 205 208 205 174 170 168 204 HDT C (8.00 MPa) C. 145 148 143 122 115 108 162 MVR (250 C./21.6 kg) cm.sup.3/10 min 51 60 68 32 36 20 326 % by weight = percent by weight

(10) 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.

(11) 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. 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.

(12) 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 temperature 23 C.

(13) 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.

(14) 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.

(15) 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).

(16) The fire test was effected according to UL-94 (Tests for Flammability of Plastic Materials for Parts in Devices and Applications of the Underwriters Laboratories) on test pieces of the dimension 12712.70.35, 12712.70.75, 12513.01.5 and 12513.03.0 mm with normal conditioning (7 days, 70 C.).

(17) Results:

(18) Moulded articles according to the state of the art, equipped with magnesium hydroxide, have, with the same glass fibre content (CE1), significantly higher moduli of elasticity than the moulding compounds according to the invention since a higher concentration of this inorganic flame retardant is required in order reliably to reach the fire protection classification V0.

(19) The breaking strength of the moulding compounds according to the invention is at least at the level of the moulding compounds of the state of the art, however outmatch these when compared with moulding compounds with similar rigidity.

(20) Breaking elongation and also impact and notch impact, both at room temperature and at low temperatures, are significantly above the comparative examples. Furthermore, the flame retardant according to the invention prevents an all too steep increase in melting viscosity (MVR) so that the moulding compounds according to the invention are still sufficiently flowable in order to be able to produce even thin-walled moulded parts without difficulty.

(21) If necessary, it can also be possible that the polyketone moulding compounds are free of magnesium hydroxide.