阅读说明：本技术 阻燃聚酰胺 (Flame-retardant polyamide ) 是由 O·S·赫兹 B·尼茨 T·朗格 于 2020-04-29 设计创作，主要内容包括：本发明涉及一种组合物,其包含至少一种由至少一种内酰胺和包含至少一种C-(32)-C-(40)二聚酸和至少一种C-(4)-C-(12)二胺的单体混合物(M)聚合制备的共聚酰胺(PA-1)作为组分(I),选自氰尿酸三聚氰胺、氢氧化镁和含磷阻燃剂的阻燃剂(F1)作为组分(II)。本发明还涉及制备这种组合物的方法,以及涉及所述组合物制备模制品部件的用途。(The invention relates to a composition comprising at least one lactam and at least one C 32 ‑C 40 Dimer acid and at least one C 4 ‑C 12 A copolyamide (PA-1) prepared by polymerization of a monomer mixture (M) of diamines as component (I) and a flame retardant (F1) selected from melamine cyanurate, magnesium hydroxide and phosphorus-containing flame retardants as component (II). The invention also relates to a method for producing said composition and to the use of said composition for producing moulded parts.)

1. A composition (Z-2) comprising at least

(I) Copolyamide (PA-1) prepared by polymerizing the following components:

(A) at least one lactam, and

(B) a monomer mixture (M) comprising:

(B1) at least one C₃₂-C₄₀Dimer acid and

(B2) at least one C₄-C₁₂A diamine;

and

(II) a flame retardant (F1) selected from the group consisting of melamine cyanurate, magnesium hydroxide and phosphorus containing flame retardants.

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

3. The composition according to any one of claims 1 and 2, wherein the composition comprises at least one first phosphorus-containing flame retardant (F1) selected from phosphoric acid derivatives and phosphonic acid derivatives and at least one other phosphorus-containing flame retardant (F2) selected from phosphinic acid derivatives.

4. The composition according to claim 3, wherein the phosphorus-containing flame retardant (F1) is a phosphonite.

5. The composition of claim 4, wherein the phosphinate is selected from aluminum phosphinates or zinc phosphinates.

6. The composition according to any one of claims 3 to 5, wherein the phosphorus containing flame retardant (F2) is a phosphate ester.

7. The composition according to any one of claims 3 to 6, wherein the flame retardant (F1) is selected from resorcinol bis (diphenyl phosphate) (RDP), bisphenol A bis (diphenyl phosphate) (BDP) and diphenyl cresyl phosphate (DPK).

8. A process for producing a composition (Z-2), in particular a composition (Z-2) according to any one of claims 1 to 7, comprising the following steps

(a) Provide for

(I) Copolyamide (PA-1) obtained by polymerization of at least one lactam and at least one C comprising component (B1)₃₂-C₄₀Dimer acid and (B2) at least one C₄-C₁₂Preparing a monomer mixture (M) of diamine; and

(II) a flame retardant selected from the group consisting of melamine cyanurate, magnesium hydroxide and phosphorus containing flame retardants,

(b) mixing the components (I) and (II).

9. Use of the composition (Z-2) according to any one of claims 1 to 7 for the production of shaped articles.

Examples

1. Using materials

Ultramid RX 2298: nylon-6 and Nylon-6, 36(PA 6/6.36) copolymers from BASF SE,67056Ludwigshafen, Germany, sold under the trade name Ultramid RX2298, the MVR (275 ℃/5kp) of which is 115cm³10' according to DIN 53727(0.005g/ml H)₂SO₄) Has a viscosity number of 28ml/g and a melting temperature (DSC, ISO 11)357) At 200 ℃ the density was 1.054 g/ml.

Exolit OP 1230: aluminum diethylphosphinate (CAS #: 225789-38-8, Clariant Produkte (Germany) GmbH, Chemiepark Knapack, 50351 Hurth), water content% (w/w) <0.2, and average particle size (D50) from 20 to 40 μm.

Ultrabatch 590A: a mixture of 63% aluminium hypophosphite (CAS 7784-22-7) and 37% melamine cyanurate (CAS 37640-57-6) (Italmatch Chemicals SpA, Via Pietro Chiesa 7/13 (pinano 8 ℃), Torri pinane-SanBenigno, 16149Genoa, Italy) with a phosphorus content (%) of 26-27, a nitrogen content (%) of 17.6-18.6, an average particle diameter (D50) of 3.4 μm and a water content% (w/w) < 0.2.

Fyrolflex RDP: resorcinol bis (diphenyl phosphate), CAS #: 125997-21-9, (Supresta netherlands b.v, Office Park De Hoef, Hoefseweg 1, 3821AE Amersfoort, netherlands), a viscosity at 25 ℃ of 700mPas, an acid value of <0.1mg KOH/g, a water content% (w/w) < 0.1.

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, (BASF SE,67056Ludwigshafen, germany), particle size D99% </50 μm, D50% </4.5 μm, water content% (w/w) < 0.2.

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

2. Production of materials

The following table lists compositions in which the individual ingredients are expressed in parts by weight (PW). The mixtures were each produced with a Berstorff ZE 40A twin-screw extruder with a screw length of 35D and divided into 10 barrel sections. Granulation was carried out using standard underwater granulation equipment from gala (uwg).

TABLE 1

Example numbering	1(CE)	2(IE)	3(IE)	4(IE)	5(IE)	6(CE)	7(IE)	8(IE)
									Ultramid RX2298	100	80	80	80	80	80	80	80
Exolit OP 1230	-	20	-	-	-	-	10	10
									Ultrabatch 590A	-	-	20	-	-	-	-	-
Melapur MC 15ED	-	-	-	20	-	-	10	-
									Melapur MPP 200/70	-	-	-	-	20	-	-	10
Fyrolflex RDP	-	-	-	-	-	20	-
										100	100	100	100	100	100	100	100

Pure Ultramid RX2298 was not extruded; films and injection-molded parts are produced from the starting granules. Composition 6 could not be produced. The crosslinking reaction occurred after addition of Fyrolflex RDP.

3. Determination of Properties

3.1 determination of MFR

TABLE 2

3.2 production of the film and mechanical Properties of the film

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

TABLE 3

The results of the film measurements are summarized in table 4.

TABLE 4

After production, the film was heat treated at 100 ℃ for 20 hours. Thereafter, the films were kept under standard climatic conditions for 3 days before determining the mechanical properties. All compositions according to the invention have very good mechanical properties.

3.3 production of injection moldings and mechanical Properties of the injection moldings

The specimens for taper measurement and for determining the mechanical properties with dimensions of 100X 5mm were injection molded on an Arburg 520S with a screw diameter of 30 mm. The material is injection molded at low temperature. For example, injection molding conditions are specified for producing specimens for taper measurement.

TABLE 5

The modulus of elasticity, impact resistance and notched impact resistance were determined on injection molded test specimens.

TABLE 6

The samples were heat treated at 100 ℃ for 20 hours. Thereafter, the test specimens were kept under standard climatic conditions for 3 days before the mechanical properties were determined. All compositions according to the invention have very good mechanical properties.

3.4 Cone test

To evaluate the flame retardancy, according to ISO 5660, part 1 and part 2 (2002-12), 35kW/m in a cone calorimeter²Test for radiation intensity level of 5mmAnd (5) sampling.

TABLE 7

The inventive examples all have a low Total Heat Release (THR) to some extent and the peak heat release rate (phr) is significantly reduced compared to the comparative examples. These advantageous flame retardant properties are particularly pronounced in inventive example 3.

4. Production example II

4.1 example 9

The mixture was prepared from Ultramid RX2298, Exolit OP1230 and melamine cyanurate 15 ED.

TABLE 8

4.2 example 10

Various exemplary mixtures were made from Ultramid RX2298, AC 85a12, 1160D10, Exolit OP1230, Fyrolflex RDP, melamine polyphosphate MC 200/70, and melamine cyanurate MC 15 ED.

TABLE 9

4.3 example 11

Various exemplary mixtures were made from Ultramid RX2298, AC 85a12, 1160D10, Exolit OP1230, Fyrolflex RDP, melamine polyphosphate MC 200/70, and melamine cyanurate MC 15 ED.

Watch 10

5. Measuring method

The density, Shore hardness, tensile strength, tear resistance, abrasion and elongation at break were determined on a film having a thickness of 1.6 mm. The films were extruded using an Arenz single screw extruder with a three zone screw (screw ratio 1:3) having a mixing section. The films were evaluated for their appearance.

UL 94V and HB flame tests were performed on 1.6mm films or 2mm injection molded plaques.

Modulus of elasticity, impact resistance and notched impact resistance were determined on injection molded test specimens. For this purpose, test specimens were produced on Arburg 520S with a screw diameter of 30 mm.

Burst pressure was measured on a hose having an outer diameter of 8.0mm and an inner diameter of 5.5 mm. The hose was extruded with a Kuhne single screw extruder with a three zone screw (screw ratio 1:3) of mixing sections.

Citations

EP 0 352 562 A1

DE 28 46 596 A1

WO 2018/050487 A1

EP 2878630 B1

WO 2017/063841 A1