Halogen-free flame-retardant polyamide compositions and process for their preparation

Abstract

The application discloses a kind of halogen-free flame-retardant polyamide compositions and preparation method thereof, by the following components are prepared by weight parts: long carbon chain polyamide resin 35-70 parts, polyamide elastomer 5-32 parts, flame retardant A 5-15 parts, flame retardant B 5-20 parts, plasticizer 2-20 parts, chain extender 0.1-3 parts, antioxidant 0.1-3 parts, color mother 0-3 parts;Wherein, the flame retardant A is melamine urea salt, the flame retardant B is melamine polyphosphate salt.The application uses long-chain nylon elastomer as toughening agent, uses good flame retardant amino silicon oil as plasticizer, provides high flexibility while synergistic effect with flame retardant, compared with commonly used polyamide plasticizer N-butyl benzene sulfonamide BBSA, can provide better flame retardant performance;Flame retardant uses melamine cyanurate MCA and melamine polyphosphate salt, reaches good halogen-free flame retardant performance.

Description

Technical Field

[0001] This invention relates to the field of polymer composite materials technology, specifically a halogen-free flame-retardant polyamide composition and its preparation method. Background Technology

[0002] With the rapid development of new energy vehicles, increasingly higher requirements are being placed on the cooling pipes of these vehicles. The original non-flame-retardant pipes have been replaced by high-flexibility polyamide cooling pipe materials with flame retardant V0 rating and resistance to hydrolysis. Currently, after flame retardant modification, polyamide pipe materials can usually only achieve a V2 level of flame retardancy, which greatly limits the application of the materials. Summary of the Invention

[0003] In view of this, the present invention provides a halogen-free flame-retardant polyamide composition and its preparation method to solve the problems mentioned in the background art. Through the formulation and process innovation of raw materials such as long carbon chain polyamide, flame retardant, chain extender, and plasticizer, the problem of V0 flame retardancy of the pipe is solved while ensuring the pipe's resistance to low temperature and hydrolysis.

[0004] To achieve the above objectives, the present invention provides the following technical solution:

[0005] On one hand, the present invention discloses a halogen-free flame-retardant polyamide composition, which is prepared from the following components in parts by weight:

[0006]

[0007] Wherein, flame retardant A is melamine urea salt, and flame retardant B is melamine polyphosphate.

[0008] As a further aspect of the present invention: the long-chain polyamide resin is at least one of polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide 613, polyamide 614, polyamide 615, polyamide 616, polyamide 1010, polyamide 1012, polyamide 1013, polyamide 1014, polyamide 1015, polyamide 1016, polyamide 1210, polyamide 1212, polyamide 1213, polyamide 1214, polyamide 1215, and polyamide 1216.

[0009] As a further embodiment of the present invention: the polyamide elastomer is a polyetheramide with one of the following as the hard segment: polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide 613, polyamide 614, polyamide 615, polyamide 616, polyamide 1010, polyamide 1012, polyamide 1013, polyamide 1014, polyamide 1015, polyamide 1016, polyamide 1210, polyamide 1212, polyamide 1213, polyamide 1214, polyamide 1215, and polyamide 1216, and polyether as the soft segment.

[0010] As a further aspect of the present invention: the plasticizer is amino silicone oil.

[0011] As a further aspect of the present invention: the chain extender is an SMA resin copolymerized with styrene and maleic anhydride.

[0012] As a further aspect of the present invention: the antioxidant is at least one of antioxidant 1098, antioxidant 245, and antioxidant 168.

[0013] As a further aspect of the present invention, the mass ratio of flame retardant A to flame retardant B is (1:3)-(3:1).

[0014] On the other hand, the present invention discloses a method for preparing the halogen-free flame-retardant polyamide composition as described above, comprising the following steps:

[0015] Mixing: Long-chain polyamide resin, polyamide elastomer, flame retardant, chain extender, antioxidant, and color masterbatch are mixed evenly to obtain material A;

[0016] Extrusion: Material A is added to the main hopper of a twin-screw extruder, and the plasticizer is injected into the side hopper of the twin-screw extruder. After stretching, pelletizing, and drying, a halogen-free flame-retardant polyamide composition is obtained.

[0017] As a further aspect of the present invention: the temperature of the first zone of the twin-screw extruder is 170-240℃, and the temperatures of the other zones and the die head are 225-280℃; the speed of the extruder is 50-1000 r / min.

[0018] Compared with the prior art, the beneficial effects of the present invention are:

[0019] (1) This invention has developed a new energy cooling pipe material with good low-temperature toughness, good hydrolysis resistance, and flame retardancy of V0; using long-chain nylon elastomer as a toughening agent provides good low-temperature toughness;

[0020] (2) The present invention uses amino silicone oil with good flame retardancy as plasticizer. While providing high flexibility, it has a synergistic effect with flame retardant. Compared with the commonly used polyamide plasticizer N-butylbenzene sulfonamide BBSA, it can provide better flame retardant performance. The flame retardant is a compound of melamine cyanurate salt MCA and melamine polyphosphate, which can achieve good halogen-free flame retardant performance.

[0021] (3) The combined use of melamine ureate and melamine polyphosphate greatly improves the flame retardant performance. When melamine ureate is heated, it generates non-combustible gases such as ammonia. These gases dilute the combustibles and oxygen produced by the polymer, reducing the concentration of combustible gases. The phosphoric acid substances produced by the decomposition of melamine polyphosphate at high temperature form a large amount of char residue on the surface of the material, effectively isolating oxygen and heat from entering the interior of the material and hindering the continuous spread of the flame. The combined use of the two can slow down the spread of fire in both the gas phase and the solid phase, and has a good synergistic effect.

[0022] (4) The present invention uses SMA resin copolymerized with styrene and maleic anhydride as a chain extender to increase the molecular weight of polyamide during modification, thereby increasing the viscosity of the composition and improving the hydrolysis resistance of the composition, making the composition particularly suitable for the application of cooling water pipes in new energy vehicles. Detailed Implementation

[0023] To facilitate understanding of the present invention, a more comprehensive description will be given below with reference to specific embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure of the present invention.

[0024] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0025] The specific information of the raw materials used in the following examples and comparative examples is as follows:

[0026] Polyamide 612, tested at 235℃ and 2.16 kg, melt index 0.3 g / 10 min, produced by Huitong New Materials Co., Ltd.

[0027] Polyamide 1012, tested at 235℃ and 2.16 kg, melt index 3.2 g / 10 min, produced by Huitong New Materials Co., Ltd.

[0028] Polyamide 1010, tested at 235℃ and 2.16 kg, melt index 9.5 g / 10 min, produced by Huitong New Materials Co., Ltd.

[0029] Polyamide 614, tested at 235℃ and 2.16 kg, melt index 5.7 g / 10 min, produced by Huitong New Materials Co., Ltd.

[0030] Polyamide elastomers: PA12, PPBAPP 3533; PA12, PPBAPP 2533; PA12, PPBAPP 6333, all produced by Arkema;

[0031] Flame retardant A: MCA, BASF Melapur P MC 25; or, MCA, BASF Melapur P MC 50;

[0032] Flame retardant B: Melamine polyphosphate JLS-PNA350 or melamine polyphosphate JLS-PNA, Hangzhou Jiersi;

[0033] Chain extenders: SMA PIRANP 9000, SMA PIRANP 3500, SMA PIRANP 1000, and SMA PIRANP 2000, all produced by POLYSCOPP in the Netherlands;

[0034] Antioxidant 1098, Antioxidant 168, Antioxidant 245, and Antioxidant 1098 are all produced by BASF.

[0035] Toughening agents: ShinPtsu KF-868 monoamine amino silicone oil, ShinPtsu KF-393 monoamine amino silicone oil, and ShinPtsu KF-860 monoamine amino silicone oil produced by Shin-Etsu Chemical Co., Ltd. of Japan, and DY-N322 diamine amino silicone oil produced by Shandong Dayi Chemical Co., Ltd.

[0036] All materials are commercially available, commonly used products.

[0037] It is understood that the above-mentioned raw materials and reagents are merely examples of some specific embodiments of the present invention, making the technical solution of the present invention clearer, and do not mean that the present invention can only use the above-mentioned reagents. The specific scope shall be determined by the claims. In addition, unless otherwise specified, "parts" in the examples and comparative examples refer to parts by weight.

[0038] Any range described in this invention includes the endpoint, any value between the endpoints, and any subrange consisting of the endpoint or any value between the endpoints.

[0039] Example 1

[0040] Weigh out 46.5 kg of polyamide 612, 20 kg of PA12 polyamide elastomer PPBAPP 3533, 6 kg of flame retardant MCAMMelapurP MC 25M, 13 kg of melamine polyphosphate JLS-PNA350, 2 kg of SMA resin (PIRANP9000), 0.5 kg of antioxidant 1098, 0.5 kg of antioxidant 168, and 1.5 kg of PA6 black masterbatch. Mix the above materials evenly using a high-speed mixer and add them to the main weighing scale. Add 10 kg of ShinPtsu KF-868 monoamine amino silicone oil to the liquid weighing scale. Granulate using a twin-screw extruder, dry the injection-molded samples, and test their mechanical and flame-retardant properties.

[0041] Twin-screw extruder parameters:

[0042] The temperature in zone 1 is 180℃, zone 2 is 220℃, zone 3 is 220℃, zone 4 is 220℃, zone 5 is 220℃, zone 6 is 220℃, zone 7 is 220℃, zone 8 is 220℃, zone 9 is 220℃, and zone 10 is 230℃; the die head temperature is 230℃; the extruder speed is 200 r / min.

[0043] Injection molding parameters: Zone 1 temperature 180℃, Zone 2 temperature 230℃, Zone 3 temperature 230℃, Die head temperature 230℃, Nozzle temperature 230℃; Mold temperature 50℃; Plasticizing pressure 70MPa; Back pressure 10MPa; Injection pressure 60MPa; Injection speed 50mm / s.

[0044] Example 2

[0045] Weigh out 70 kg of polyamide 1012, 9 kg of PA12 polyamide elastomer PPBAPP 2533, 5 kg of flame retardant MCAMMelapurP MC 50M, 8.5 kg of melamine polyphosphate JLS-PNA, 0.5 kg of SMA resin (PIRANP3500), 3 kg of antioxidant 245, and 2 kg of antioxidant 168. Mix the above materials thoroughly using a high-speed mixer and add them to the main weighing scale. Add 2 kg of ShinPtsu KF-393 monoamine amino silicone oil to the liquid weighing scale. Granulate using a twin-screw extruder, dry the injection-molded samples, and test their mechanical and flame-retardant properties.

[0046] The parameters for the twin-screw extruder and the injection molding parameters are the same as in Example 1.

[0047] Example 3

[0048] Weigh out 36.8 kg of polyamide 1010, 5 kg of PA12 polyamide elastomer PPBAPP 2533, 15 kg of flame retardant MCAMMelapurP MC 25M, 20 kg of melamine polyphosphate JLS-PNA370, 0.1 kg of SMA resin (PIRANP1000), 0.1 kg of antioxidant 1098, and 3 kg of PA6 black masterbatch. Mix the above materials thoroughly using a high-speed mixer and add them to the main weighing scale. Add 20 kg of diamine amino silicone oil DY-N322 to the liquid weighing scale. Granulate using a twin-screw extruder, dry the injection-molded samples, and test their mechanical and flame-retardant properties.

[0049] The parameters for the twin-screw extruder and the injection molding parameters are the same as in Example 1.

[0050] Example 4

[0051] Weigh out 35 kg of polyamide 614, 32 kg of PA12 polyamide elastomer PPBAPP 6333, 14 kg of flame retardant MCAMMelapurP MC 50M, 5 kg of melamine polyphosphate JLS-PNA370, 3 kg of SMA resin (PIRANP2000), 1 kg of antioxidant 245, and 1 kg of antioxidant 168. Mix the above materials thoroughly using a high-speed mixer and add them to the main weighing scale. Add 9 kg of ShinPtsu KF-860 monoamine amino silicone oil to the liquid weighing scale. Granulate using a twin-screw extruder, dry the injection-molded samples, and test their mechanical and flame-retardant properties.

[0052] The parameters for the twin-screw extruder and the injection molding parameters are the same as in Example 1.

[0053] Comparative Example 1

[0054] Weigh out 46.5 kg of polyamide 612, 20 kg of PA12 polyamide elastomer PPBAPP 3533, 6 kg of flame retardant MCAMMelapurP MC 25M, 13 kg of melamine polyphosphate JLS-PNA350, 2 kg of SMA resin (PIRANP9000), 0.5 kg of antioxidant 1098, 0.5 kg of antioxidant 168, and 1.5 kg of PA6 black masterbatch. Mix the above materials evenly using a high-speed mixer, then add them to the main weighing scale. Granulate using a twin-screw extruder, dry the injection-molded samples, and test their mechanical and flame-retardant properties.

[0055] The parameters for the twin-screw extruder and the injection molding parameters are the same as in Example 1.

[0056] Comparative Example 2

[0057] Weigh out 46.5 kg of polyamide 612, 20 kg of PA12 polyamide elastomer PPBAPP 3533, 6 kg of flame retardant MCAMMelapurP MC 25M, 13 kg of melamine polyphosphate JLS-PNA350, 2 kg of SMA resin (PIRANP9000), 0.5 kg of antioxidant 1098, 0.5 kg of antioxidant 168, and 1.5 kg of PA6 black masterbatch. Mix the above materials thoroughly using a high-speed mixer and add them to the main weighing scale. Add 10 kg of Provita BBSA PROVIPLASPP 024 to the liquid weighing scale. Granulate using a twin-screw extruder, dry the injection-molded samples, and test their mechanical and flame-retardant properties.

[0058] The parameters for the twin-screw extruder and the injection molding parameters are the same as in Example 1.

[0059] Comparative Example 3

[0060] Weigh out 46.5 kg of polyamide 612, 20 kg of PA12 polyamide elastomer PPBAPP 3533, 6 kg of flame retardant MCAMMelapurP MC 25M, 13 kg of melamine polyphosphate JLS-PNA350, 0.5 kg of antioxidant 1098, 0.5 kg of antioxidant 168, and 1.5 kg of PA6 black masterbatch. Mix the above materials evenly using a high-speed mixer and add them to the main weighing scale. Add 10 kg of monoamine amino silicone oil KF-868 to the liquid weighing scale. Granulate using a twin-screw extruder, dry the injection-molded samples, and test their mechanical and flame-retardant properties.

[0061] The parameters for the twin-screw extruder and the injection molding parameters are the same as in Example 1.

[0062] Comparative Example 4

[0063] Weigh out 46.5 kg of polyamide 612, 6 kg of flame retardant MCAMMelapur P MC 25M, 13 kg of melamine polyphosphate JLS-PNA350, 2 kg of SMA resin (PIRANP 9000), 0.5 kg of antioxidant 1098, 0.5 kg of antioxidant 168, and 1.5 kg of PA6 black masterbatch. Mix the above materials evenly using a high-speed mixer and add them to the main weighing scale. Add 10 kg of monoamine amino silicone oil KF-868 to the liquid weighing scale. Granulate using a twin-screw extruder, dry the injection-molded samples, and test their mechanical and flame-retardant properties.

[0064] The parameters for the twin-screw extruder and the injection molding parameters are the same as in Example 1.

[0065] The mechanical properties and flame retardant properties of the materials prepared in Examples 1-4 and Comparative Examples 1-4 were tested. Tensile testing was performed using ISO 527 1A type specimens, simply supported beam impact testing used ISO 179 1eA specimens, and flame retardant testing used UL94 1.6mm specimens. The test results are shown in Table 1.

[0066] Table 1

[0067]

[0068] Conclusion Analysis:

[0069] 1. Compared with Example 1, Comparative Example 1, which did not add amino silicone oil plasticizer, had a notched impact strength of 14.5 kJ / m at 23°C. 2 It dropped to 7.7 kJ / m 2 The flexibility decreased; the flame retardancy dropped from V0 to V1, indicating that amino silicone oil has a synergistic effect on flame retardancy.

[0070] 2. In Comparative Example 2, the use of BBSA plasticizer reduced the flame retardant performance of the material from UL94 1.6mm V0 to V2.

[0071] 3. In Comparative Example 3, the SMA resin without chain extender showed a significant decrease in hydrolysis resistance. After hydrolysis at 130°C and 50% ethylene glycol aqueous solution for 1000 hours, the tensile strength decreased from 20.2 MPa to 12.1 MPa.

[0072] 4. In Comparative Example 4, without the addition of polyamide elastomer, the notched impact strength at -30℃ was 5.6 kJ / m. 2 It dropped to 1.8 kJ / m 2 It has poor low-temperature impact resistance.

[0073] Although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

[0074] Therefore, the above description is only a preferred embodiment of this application and is not intended to limit the scope of this application; that is, all equivalent modifications made in accordance with the scope of the claims of this application shall be within the protection scope of the claims of this application.

Claims

1. A halogen-free flame-retardant polyamide composition, characterized in that, It is prepared from the following components in parts by weight: 35-70 parts of long-chain polyamide resin, 5-32 parts of polyamide elastomer Flame retardant A5-15 parts, Flame retardant B5-20 parts, Plasticizer 2-20 parts, Chain extender 0.1-3 parts, Antioxidant 0.1-3 parts, 0-3 parts of color masterbatch; Wherein, flame retardant A is melamine urea salt, and flame retardant B is melamine polyphosphate; The plasticizer is amino silicone oil; The chain extender is SMA resin copolymerized with styrene and maleic anhydride.

2. The halogen-free flame-retardant polyamide composition according to claim 1, characterized in that, The long-chain polyamide resin is at least one of polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide 613, polyamide 614, polyamide 615, polyamide 616, polyamide 1010, polyamide 1012, polyamide 1013, polyamide 1014, polyamide 1015, polyamide 1016, polyamide 1210, polyamide 1212, polyamide 1213, polyamide 1214, polyamide 1215, and polyamide 1216.

3. The halogen-free flame-retardant polyamide composition according to claim 1, characterized in that, The polyamide elastomer is a polyetheramide with one of the following as the hard segment: polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide 613, polyamide 614, polyamide 615, polyamide 616, polyamide 1010, polyamide 1012, polyamide 1013, polyamide 1014, polyamide 1015, polyamide 1016, polyamide 1210, polyamide 1212, polyamide 1213, polyamide 1214, polyamide 1215, and polyamide 1216, and polyetheramide as the soft segment.

4. The halogen-free flame-retardant polyamide composition according to claim 1, characterized in that, The antioxidant is at least one of antioxidant 1098, antioxidant 245, and antioxidant 168.

5. The halogen-free flame-retardant polyamide composition according to claim 1, characterized in that, The mass ratio of flame retardant A to flame retardant B is (1:3) - (3:1).

6. The method for preparing the halogen-free flame-retardant polyamide composition according to any one of claims 1-5, characterized in that: Includes the following steps: Mixing: Long-chain polyamide resin, polyamide elastomer, flame retardant, chain extender, antioxidant, and color masterbatch are mixed evenly to obtain material A; Extrusion: Material A is added to the main hopper of a twin-screw extruder, and the plasticizer is injected into the side hopper of the twin-screw extruder. After stretching, pelletizing, and drying, a halogen-free flame-retardant polyamide composition is obtained.

7. The preparation method according to claim 6, characterized in that, The temperature of the first zone of the twin-screw extruder is 170-240℃, and the temperatures of the other zones and the die head are 225-280℃; the speed of the extruder is 50-1000 r / min.

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