Flame retardant polyamide

Abstract

A composition contains at least a copolyamide (PA-1) as a component (I), produced by polymerization of at least one lactam and of a monomer mixture (M) which contains at least a C.sub.32-C.sub.40 dimer acid and at least a C.sub.4-C.sub.12 diamine; and a flame retardant (F1) as a component (II). The flame retardant (F1) is selected from melamine cyanurates, magnesium hydroxide, and phosphorus-containing flame retardants. A process can be used for preparing such compositions, and the composition can be used for producing shaped articles.

Claims

1-9. (canceled)

10. A composition, comprising at least: (I) a copolyamide (PA-1), prepared by polymerization of (A) at least one lactam, and (B) a monomer mixture (M) comprising the following components: (B1) at least one C.sub.32-C.sub.40 dimer acid, and (B2) at least one C.sub.4-C.sub.12 diamine; and (II) a flame retardant selected from the group consisting of a melamine cyanurate, magnesium hydroxide, and a phosphorus-containing flame retardant.

11. The composition according to claim 10, wherein a proportion of the copolyamide (PA-1) in the composition is in a range from 5% to 95% by weight, based on a sum total of components (I) and (II).

12. The composition according to claim 10, wherein the composition comprises at least one first phosphorus-containing flame retardant (F1) selected from the group consisting of a derivative of phosphoric acid and a derivative of phosphoric acid, and wherein the composition comprises at least one further phosphorus-containing flame retardant (F2) selected from the group consisting of a derivative of phosphinic acid.

13. The composition according to claim 12, wherein the at least one first phosphorus-containing flame retardant (F1) is selected from the group consisting of resorcinol bis(diphenyl phosphate) (RDP), bisphenol A bis(diphenyl phosphate) (BDP), and diphenyl cresyl phosphate (DPK).

14. A process for producing a composition (Z-2), comprising: (a) providing the following components (I) a copolyamide (PA-1), prepared by polymerizing at least one lactam and a monomer mixture (M) comprising (B1) at least one C.sub.32-C.sub.40 dimer acid, and (B2) at least one C.sub.4-C.sub.12 diamine; and (II) a flame retardant selected from the group consisting of a melamine cyanurate, magnesium hydroxide, and a phosphorus-containing flame retardant, and (b) mixing components (I) and (II).

15. A method, comprising: producing a shaped article with the composition according to claim 10.

16. A shaped article, comprising the composition according to claim 10.

Description

EXAMPLES

1. Materials Used

[0229] Ultramid RX2298: Copolymer of nylon-6 and nylon-6,36 (PA 6/6.36) from BASF SE, 67056 Ludwigshafen, Germany, sold under the Ultramid RX 2298 brand name, with an MVR (275° C./5 kp) 115 cm3/10′, a viscosity number to DIN 5372.7 (0.005 g/ml H2SO4) of 28 ml/g, a melting temperature (DSC, ISO 11357) of 200° C. and a density of 1.054 g/ml.

[0230] Exolit OP 1230: Aluminum diethylphosphinate, CAS#: 225789-38-8, Clariant Produkte (Germany) GmbH, Chemiepark Knapsack, 50351 Hürth, water content % (w/w)<0.2, average particle size (D50) 2.0-40 μm.

[0231] Ultrabatch 590A: Mixture of 63% by weight of aluminum hypophosphite, CAS 7784-22-7 and 37% by weight of melamine cyanurate, CAS 37640-57-6, Italmatch Chemicals S.p.A., Via Pietro Chiesa 7/13 (piano 8°), Torri Piane-SanBenigno, 16149 Genoa, Italy, phosphorus content (%) 26-27, nitrogen content (%) 17.6-18.6, average particle size (D50) 3.4 μm, water content % (w/w)<0.2.

[0232] Fyrolflex RDP: Resorcinol bis(diphenyl phosphate), CAS #: 125997-21-9, Supresta Netherlands B.V., Office Park De Hoef, Hoefseweg 1, 3821 AE Amersfoort, the Netherlands, viscosity at 25° C.=700 mPas, acid number<0.1 mg KOH/g, water content % (w/w)<0.1.

[0233] Melapur MC 15 ED: Melamine cyanurate (1,3,5-triazine-2,4,6(1H,3H,5H)-trione, compound with 1,3,5-triazine-2,4,6-triamine (1:1)), CAS #: 37640-57-6, BASE SE, 67056 Ludwigshafen, GERMANY, particle size D99%</=50 μm, D50%<=4.5 μm, water content % (w/w)<0.2.

[0234] Melapur MC 200/70: Melamine polyphosphate (nitrogen content 42-44wt %, phosphorus content 12-14wt %), CAS #: 218768-84-4, BASF SE, 67056 Ludwigshafen, GERMANY, particle size D99%</=70 μm, average particle diameter D50%<=10 μm, water content % (w/w)<0.3.

2. Production of the Materials

[0235] The tables that follow list compositions in which the individual constituents are stated in parts by weight (PW). The mixtures were each produced with a Berstorff ZE 40 A twin-screw extruder with screw length 35 D divided into 10 barrel sections. Pelletization was effected using standard underwater pelletization apparatus from Gala (UWG).

TABLE-US-00001 TABLE 1 Example No. 1 2 3 4 5 6 7 8 (CE) (IE) (IE) (IE) (IE) (CE) (IE) (IE) RX 2298 Polyamide 100 80 80 80 80 80 80 80 Exolit OP 1230 — 20 — — — 10 10 Ultrabatch 590A — — 20 — — — — — Melapur MC 15 ED — — — 20 — — 10 — Melapur MPP 200/70 — — — — 20 — — 10 Fyrolflex RDP — — — — — 20 — 100 100  100  100  100  100  100  100 

[0236] Pure Ultramid RX 2298 was not extruded; the films and injection moldings were produced with the original pellets. Composition 6 was not producible. There were crosslinking reactions on addition of the Fyrolflex RDP.

3. Determination of Properties

3.1 Determination of MFR

[0237]

TABLE-US-00002 TABLE 2 Example No. 1 2 3 4 5 7 8 (CE) (IE) (IE) (IE) (IE) (IE) (IE) [g/10 min] DIN EN ISO 1133 70 79 83 16 72 70

3.2 Production of Films and Mechanical Properties of the Films

[0238] Density, Shore hardness, tensile strength, the propagation resistance, abrasion and elongation at break were determined on films having a thickness of 1.6 mm. The films were extruded with an Arenz single-screw extruder having a three-zone screw with a mixing section (screw ratio 1:3). The films were produced at low processing temperatures.

TABLE-US-00003 TABLE 3 Melt Flow Draw Zone temperatures Intake temp. Speed rate rate Sample 1 2 3 4 5 6 7 ° C. ° C. Pressure 1/min % m/min 1 (CE) 185 195 200 215 225 225 225 24 210 6 33 20 0.4 2 (IE) 180 190 200 210 210 210 210 26 209 9 35 30 0.4 3 (IE) 185 195 205 215 215 215 215 26 215 9 33 20 0.4 4 (IE) 185 195 205 215 225 225 225 24 217 6 33 25 0.4 5 (IE) 185 195 205 215 225 225 225 24 224 39 33 35 0.4 7 (IE) 185 195 205 215 225 225 225 24 220 9 32 25 0.4 8 (IE) 185 195 205 215 225 225 225 24 220 11 32 35 0.4

[0239] The results of the measurements on the films are summarized in table 4.

TABLE-US-00004 TABLE 4 Example No. 1 2 3 4 5 7 8 (CE) (IE) (IE) (IE) (IE) (IE) (IE) Density [g/cm.sup.3] DIN EN ISO 1183-1, 1.06 1.14 1.16 1.14 1.15 1.13 1.13 A Shore [D] DIN ISO 7619-1 76 76 79 76 79 78 78 Tensile strength [MPa] DIN EN ISO 527 59 30 32 35 37 33 31 Elongation at break [%] DIN EN ISO 527 460 250 200 300 300 280 260 Tear propagation [kN/m] DIN ISO 34-1, 251 149 171 158 166 157 155 resistance B (b) Abrasion [mm.sup.3] DIN ISO 4649 38 72 60 82 41 62 68

[0240] After production, the films were subjected to heat treatment at 100° C., for 20 h. Thereafter, the films remained under standard climatic conditions for 3 days before the mechanical properties were determined. All compositions of the invention have very good mechanical properties.

3.3 Production of Injection Moldings and Mechanical Properties of the Injection-Molded Parts

[0241] The test specimens for the cone measurements with dimensions of 100×100×5 mm and the test specimens for the determination of the mechanical properties were injection-molded on an Arburg 520S with a screw diameter of 30 mm. The materials were injection-molded at low temperatures. By way of example, the injection molding conditions are specified for the production of the test specimens for the cone measurements.

TABLE-US-00005 TABLE 5 Injection Injection Cycle Zone Zone Zone Nozzle Mold Back- rate pressure time Zone 1 2 3 4 5 temperature Pro- Experiment pressure mm/s bar s ° C. ° C. ° C. ° C. ° C. ° C. Demolding cessing 1 (CE) 10 15 60 74 195 215 220 220 220 50 good good 2 (IE) 10 15 60 74 195 215 220 220 220 50 good good 3 (IE) 10 15 80 74 195 215 220 220 220 50 good good 4 (IE) 10 15 80 74 195 215 220 220 220 50 good good 5 (IE) 10 15 92 74 195 215 220 220 220 50 good good 7 (IE) 10 15 130 74 195 215 220 220 220 50 good good 8 (IE) 10 15 86 74 195 215 220 220 220 50 good good

[0242] Moduli of elasticity, impact resistances and notched impact resistances were determined on injection-molded test specimens.

TABLE-US-00006 TABLE 6 Example No. 1 2 3 4 5 7 8 (CE) (IE) (IE) (IE) (IE) (IE) (IE) Density [g/cm.sup.3] DIN EN ISO 1.06 1.14 1.17 1.14 1.15 1.13 1.13 1183-1, A Shore [D] DIN ISO 761.9-1 76 76 79 76 79 78 78 Tensile strength [MPa] DIN 53504 55 29 33 31 35 31 28 Elongation at break [%] DIN 53504 290 300 340 360 340 330 370 Modulus of elasticity [MPa] DIN EN ISO 527 1250 1342 1492 1430 1586 1549 1613 from tensile test

[0243] The test specimens were subjected to heat treatment at 100° C. for 20 h. Thereafter, the test specimens remained under standard climatic conditions for 3 days before the mechanical properties were determined. All compositions of the invention have very good mechanical properties.

3.4 Cone Test

[0244] In order to assess flame retardancy, a test specimen with thickness 5 mm was tested horizontally at a radiation intensity of 35 kW/m.sup.2 in a cone calorimeter in accordance with ISO 5660 Part 1 and Part 2 (2002-12).

TABLE-US-00007 TABLE 7 Example No. 1 2 3 4 5 7 8 (CE) (IE) (IE) (IE) (IE) (IE) (IE) Total heat [MJ/m.sup.2] ISO 5660 202 172 170 183 181 179 177 release (THR) part 1 Peak of heat [kW/m.sup.2] ISO 5660 1023 705 272 773 825 568 537 release rate part 1 (PHRR) Time to ignition [s] ISO 5660 188 143 84 138 93 134 110 part. 1 Initial mass ISO 5660 57 59 61 60 60 60 60 part 1 Total mass loss ISO 5660 53 53 51 56 52 55 54 part 1

[0245] The inventive examples, compared to the comparative example, all have a low total heat release (THR) to some degree, and a distinct reduction in peak heat release rate (PHRR). These advantageous flame-retardant properties are particularly marked in inventive example 3.

4. Production Examples II

4.1 Example 9

[0246] Mixtures were produced from Ultramid RX 2298, Exolit OP 1230 and melamine cyanurate 15ED.

TABLE-US-00008 TABLE 8 Example No. 9.1 9.2 Ultramid RX 80 70 2298 Melamine cyanurate 10 20 MC 15ED Exolit OP 1230 10 10 Density [g/cm.sup.3] DIN EN ISO 1.123 1.147 1183-1, A Shore A [A] DIN 53505 — — Shore D [D] DIN ISO 77 79 7619-1 Tensile strength [MPa] DIN EN ISO 41 36 527 Elongation at [%] DIN EN ISO 30 90 break 527 Tear propagation [kN/m] DIN ISO 34-1, 177 192 resistance B (b) Abrasion [mm.sup.3] DIN 53516 83 134 Modulus of [MPa] DIN EN ISO 1374 2032 elasticity 527 Charpy notched [kJ/m.sup.3] DIN EN ISO 4.03 not impact resis- 179-1/1eA determined tance 23° C. Charpy notched [kJ/m.sup.3] DIN EN ISO 3.29 not impact resis- 179-1/1eA determined tance −30° C. Visual assessment opaque opaque UL 94 V (1.6 mm) V2 V0

4.2 Example 10

[0247] Various illustrative mixtures were produced from Ultramid RX 2298, AC 85A12, 1160D10, Exolit OP 1230, Fyrolflex RDP, melamine polyphosphate MC 200/70 and melamine cyanurate MC 15ED.

TABLE-US-00009 TABLE 9 Example No. 10.1 10.2 10.3 10.4 Ultramid RX 2298 20 20 70 20 AC 85A12 50 10 60 1160D10 50 Melamine cyanurate MC 10 15ED Exolit OP 1230 20 20 10 10 Melamine polyphosphate 10 10 MC 200/70 Fyrolflex RDP 10 Density [g/cm.sup.3] DIN EN ISO 1.142 1.125 1.124 1.107 1183-1, A Shore A [A] DIN 53505 — 97 — 99 Shore D [D] DIN ISO 7619-1 69 62 75 62 Tensile strength [MPa] DIN EN ISO 527 26 7 35 25 Elongation at break [%] DIN EN ISO 527 300 70 50 330 Tear propagation [kN/m] DIN ISO 34-1, 143 90 152 133 resistance B (b) Abrasion [mm.sup.3] DIN 53516 129 125 109 110 Modulus of elasticity [MPa] DIN EN ISO 527 not not 1955 not determined determined determined Visual assessment opaque opaque opaque opaque UL 94 V (1.6 mm) V0 V2 V0 V2

4.3 Example 11

[0248] Various illustrative mixtures were produced from Ultramid RX 229, AC 85A12, 1160D10, Exolit OP 1230, Fyrolflex RDP, melamine polyphosphate MC 200/70 and melamine cyanurate MC 15ED.

TABLE-US-00010 TABLE 10 Example No. 11.1 11.2 11.3 11.4 11.5 11.6 Ultramid RX 2298 55 60 54 60 55 55 AC 85A12 5 5 5 5 5 5 Melamine cyanurate MC 10 10 10 20 15 ED Exolit OP 1230 10 20 20 20 20 10 Melaminepolyphosphate 10 10 MC 200/70 Fyrolflex RDP Chopvantage HP3550 20 5 10 5 10 10 EC10-3,8 Density [g/cm.sup.3] DIN EN ISO 1.282 1.174 1.197 1.186 1.236 1.197 1183-1, A Tensile strength [MPa] DIN EN ISO 527 57 37 56 41 57 62 Elongation at break [%] DIN EN ISO 527 5 12 8 12 8 8 Modulus of elasticity [MPa] DIN EN ISO 527 16726 2640 3695 2736 3818 4075 Visual assessment opaque opaque opaque opaque opaque opaque UL 94 V (2.0 mm) V0 V0 V0 V0 V0 V0

5. Methods of Measurement

[0249] Density, Shore hardness, tensile strength, tear propagation resistance, abrasion and elongation at break were determined on films having a thickness of 1.6 mm. The films were extruded with an Arenz single-screw extruder having a three-zone screw with a mixing section (screw ratio 1:3). The films were assessed in accordance with their appearance.

[0250] UL 94V and HB flame tests were conducted either on 1.6 mm films or on 2 mm injection-molded plaques.

[0251] Moduli of elasticity, impact resistances and notched impact resistances were determined on injection-molded test specimens. For this purpose, test specimens were produced on an Arburg 520S having a screw diameter of 30 mm.

[0252] Burst pressures were determined on hoses having an external diameter of 8.0 mm and an internal diameter of 5.5 mm. The hoses were extruded with a Kuhne single-screw extruder having a three-zone screw with a mixing section (screw ratio 1:3).

CITED LITERATURE

[0253] EP 0 352 562 A1

[0254] DE 28 46 596 A1

[0255] WO 2018/050487 A1

[0256] EP 2878630 B1

[0257] WO 2017/063841 A1