Red phosphorus master batch as well as preparation method and application thereof

Abstract

The invention discloses red phosphorus master batch as well as a preparation method and application thereof. The red phosphorus master batch comprises the following components in parts by weight: 50-70 parts of a red phosphorus flame retardant; 30 to 50 parts of a toughening agent; 1-4 parts of a stabilizing aid; wherein the stabilizing aid comprises one or more of zinc oxide, calcium oxide, chromic oxide, hydrotalcite, metazirconic acid or magnesium oxide. According to the invention, the toughening agent with a specific content is adopted to coat the red phosphorus flame retardant, and the stabilizing aid is added, so that the content of phosphine in the red phosphorus master batch in the use process can be effectively reduced, and when the red phosphorus master batch is added into the nylon resin, the prepared nylon composite material has relatively low phosphine content and relatively good flame retardant property.

Description

Technical Field

[0001] The present invention relates to the technical field of engineering plastics, and more specifically, to a red phosphorus masterbatch, a preparation method thereof, and an application thereof. Background Art

[0002] With the continuous growth of the demand for high-performance flame-retardant materials in industries such as electronics and electrical appliances, automobiles, construction, and aerospace, the market prospect of flame-retardant nylon materials is broad. Future flame-retardant nylon materials not only require excellent flame-retardant properties but also comprehensive properties such as mechanical strength and toughness. The development trend of multifunctional composite materials is to realize the synergistic optimization of material properties through reasonable design of the composite system.

[0003] The dispersibility and compatibility of flame retardants in nylon resins are poor, resulting in insufficient interfacial adhesion, which will have a significant impact on the overall performance of the materials. The flame retardant is unevenly dispersed in the nylon matrix, or has poor interfacial compatibility with the resin, or a non-flame-retardant toughening agent component is introduced, and the effective action of the flame retardant will be weakened. Red phosphorus has been used as a flame retardant for more than 20 years, and it is a new type of flame retardant that has received high attention. However, the disadvantage is that the presence of red phosphorus reduces the polymer molecular weight and the thermal decomposition temperature of nylon; usually, the red phosphorus flame retardant is added to the nylon resin in the form of a masterbatch during application, and the toughening agent-coated red phosphorus flame retardant will generate toxic PH3 gas during use, affecting its application in materials such as connectors and battery packs. Summary of the Invention

[0004] The purpose of the present invention is to overcome the above-mentioned defects or deficiencies in the prior art that the toughening agent-coated red phosphorus masterbatch will generate PH3 gas during use, and to provide a red phosphorus masterbatch.

[0005] Another purpose of the present invention is to provide a nylon composite material.

[0006] Another purpose of the present invention is to provide a preparation method of the nylon composite material.

[0007] Another purpose of the present invention is to provide an application of the nylon composite material.

[0008] To achieve the above purposes, the present invention is implemented by adopting the following technical solutions:

[0009] A red phosphorus masterbatch, the red phosphorus masterbatch comprising the following components calculated by weight:

[0010] Red phosphorus flame retardant 50 - 70 parts;

[0011] Toughening agent 30 - 50 parts;

[0012] Stabilizing assistant 1 - 4 parts;

[0013] Wherein the stabilizing agent includes one or more of zinc oxide, calcium oxide, chromium oxide, hydrotalcite, meta-zirconic acid or magnesium oxide.

[0014] The present invention provides a red phosphorus masterbatch, which coats a red phosphorus flame retardant with a toughening agent in a specific content and adds a stabilizing agent, and can effectively reduce the content of phosphine in the red phosphorus masterbatch during use.

[0015] Furthermore, the content of the toughening agent is not less than 25 wt% of the red phosphorus masterbatch.

[0016] Furthermore, the toughening agent includes one or more of maleic anhydride grafted olefin polymers, epoxy group grafted olefin polymers or ethylene-acrylate copolymers.

[0017] Even further, the toughening agent includes one or more of MAH-g-SEBS, MAH-g-POE, GMA-g-POE or EBA.

[0018] Furthermore, the content of maleic anhydride in the maleic anhydride grafted olefin polymer is 0.5 - 2.0 wt%.

[0019] Furthermore, the content of epoxy groups in the epoxy group grafted olefin polymer is 0.5 - 1.5 wt%.

[0020] Specifically, the EBA is an ethylene-methyl acrylate-acrylate terpolymer resin.

[0021] Specifically, the melt flow rate of the ethylene-methyl acrylate-acrylate terpolymer resin at 190 °C under a load of 2.16 kg is 6 - 15 g / 10 min.

[0022] Specifically, the content of methyl acrylate in the ethylene-methyl acrylate-acrylate terpolymer resin is 3.0 - 5.0 wt%.

[0023] Furthermore, the average particle size of the stabilizing agent is 1 - 200 μm.

[0024] Even further, the stabilizing agent is meta-zirconic acid and / or magnesium oxide.

[0025] Furthermore, the content of the red phosphorus flame retardant in the red phosphorus masterbatch is 30 - 70 wt%.

[0026] Furthermore, the average particle size of the red phosphorus flame retardant is 200 - 300 μm.

[0027] Furthermore, the red phosphorus masterbatch further includes 0.1 - 1 part of antioxidant.

[0028] The preparation method of the red phosphorus masterbatch can adopt the conventional masterbatch preparation methods in the prior art.

[0029] In some specific embodiments, the preparation method of the red phosphorus masterbatch includes the following steps:

[0030] Mix the components in the red phosphorus masterbatch evenly and obtain the red phosphorus masterbatch through internal mixing.

[0031] Specifically, the temperature of the internal mixing is 200 - 300 °C.

[0032] The present invention also provides a nylon composite material, which includes the following components calculated by weight:

[0033]

[0034] The nylon composite material provided by the present invention uses the above-mentioned red phosphorus masterbatch. The red phosphorus masterbatch is coated with a toughening agent and a stabilizing assistant. The stabilizing assistant can effectively prevent the red phosphorus flame retardant from reacting with moisture and oxygen in the air, and effectively reduce the phosphine content in the nylon composite material.

[0035] The addition of the polar assistant can further adjust the hydrogen bond network between nylon resin molecules, and cooperate with the red phosphorus masterbatch to further reduce the phosphine content in the nylon composite material. If the content of the polar assistant exceeds the above range, the rigidity of the composite material will decrease slightly.

[0036] It should be noted that in the nylon composite material of the present invention, the content of the nylon resin is preferably not less than 35 wt%.

[0037] Furthermore, the relative viscosity of the nylon resin is 2.0 - 2.8.

[0038] Furthermore, the test standard for the relative viscosity is ASTM D789 - 19.

[0039] Furthermore, the nylon resin is one or more of PA66, PA610, PA612, PA1010, PA1012, PA1212, PA6, PA7, PA11, PA12, PA6T, PA10T, PA6I / 6T, PA10T / 1012, PA MXD10, PA MXD6, etc.

[0040] The red phosphorus masterbatch in the nylon composite material of the present invention is 5 - 10 parts. For example, but not limited to, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts, 10 parts, etc. can all achieve the present invention.

[0041] The polar auxiliary agent is 1 to 3 parts. For example, but not limited to, 1 part, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, 2.8 parts or 3 parts, etc. can all achieve the present invention.

[0042] Further, the nylon composite material comprises the following components calculated by weight:

[0043]

[0044] Further, the polar auxiliary agent is a substance containing polar functional groups.

[0045] Still further, the polar functional groups include one or more of a keto group, an amide group, and a carboxyl group.

[0046] Still further, the polar auxiliary agent is one or more of polyvinylpyrrolidone, N-butylbenzenesulfonamide, or m-aminobenzoic acid.

[0047] Still further, the polar auxiliary agent is polyvinylpyrrolidone and / or N-butylbenzenesulfonamide.

[0048] Further, the number-average molecular weight of the polyvinylpyrrolidone is 10,000 to 50,000 g / mol.

[0049] Further, the reinforcing fiber includes glass fiber and / or carbon fiber.

[0050] Specifically, the average length of the reinforcing fiber is 3 to 6 mm.

[0051] Further, to improve the toughness of the nylon composite material, 10 to 15 parts of a toughening agent may also be included. The toughening agent may be the same as or different from the toughening agent of the red phosphorus masterbatch.

[0052] Further, the nylon composite material further includes 0.1 to 2 parts of an auxiliary agent.

[0053] Specifically, the auxiliary agent is an antioxidant and / or a lubricant.

[0054] In the present invention, common antioxidants can be selected according to the prior art, such as, for example, but not limited to, one or several of hindered phenol antioxidants, phosphite antioxidants, diphenylamine antioxidants, or thioether antioxidants.

[0055] Specifically, the hindered phenol antioxidant is one or more of N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamide) (Irganox 1098), pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox 1010), triethylene glycol bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] (Iragnox 259), n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Iragno 1076), or spiroglycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] (ADK AO-80).

[0056] The phosphite antioxidant is one or more of 2,4-di-tert-butylphenol (Irganox 168), bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite (PEP-36), or 627A.

[0057] The diphenylamine antioxidant is 4,4'-bis(α,α'-dimethylbenzyl)diphenylamine.

[0058] The thioether antioxidant is one or more of distearyl thiodipropionate, dilauryl thiodipropionate, or pentaerythritol tetrakis(3-laurylthiopropionate).

[0059] In the present invention, common lubricants can be selected according to the prior art. For example, but not limited to, one or more of stearic acid lubricants, polyethylene lubricants, amide lubricants, paraffin lubricants, or silicone lubricants.

[0060] Specifically, the stearic acid lubricant can be calcium stearate and / or zinc stearate.

[0061] The polyethylene lubricant can be polyethylene wax.

[0062] The amide lubricant can be one or more of oleic acid amide lubricants, EBS amide lubricants, or erucic acid amide lubricants.

[0063] The silicone lubricant can be polydimethylsiloxane.

[0064] The present invention also protects a method for preparing the above nylon composite material, comprising the following steps:

[0065] Mix the components evenly, and obtain the nylon composite material through melt blending and extrusion granulation.

[0066] In a specific embodiment, the extrusion granulation is carried out in a twin-screw extruder.

[0067] Specifically, the screw length-diameter ratio of the twin-screw extruder is 40-48:1, the barrel temperature of the twin-screw extruder is 270-300° C., and the screw speed of the twin-screw extruder is 150-400 rpm.

[0068] The present invention also protects the use of the above nylon composite material in the field of photovoltaics and new energy. In particular, the use of the above nylon composite material in the preparation of flame-retardant and odorless products. In particular, the use of the above nylon composite material in the preparation of connectors and battery packs.

[0069] Compared with the prior art, the present invention has the following beneficial effects:

[0070] The invention provides a red phosphorus masterbatch, wherein the red phosphorus masterbatch is coated with a toughening agent and a stabilizing agent is added, so that the generation of phosphine during use can be effectively reduced; and when the red phosphorus masterbatch is added into a nylon resin, the prepared nylon composite material has a lower phosphine content. DETAILED DESCRIPTION

[0071] The present invention is further described below in conjunction with specific embodiments, but the embodiments do not limit the present invention in any form. Unless otherwise specified, the raw materials and reagents used in the embodiments of the present invention are conventionally purchased raw materials and reagents.

[0072] 1. Raw materials used in various embodiments and comparative examples of the present invention:

[0073] Nylon resin:

[0074] Nylon resin 1: PA66 U4800 NC01 SS, INVISTA Nylon Chemical Co., Ltd.;

[0075] Nylon resin 2: PA56, 1273, purchased from Cathay Biomaterials Co., Ltd.;

[0076] Red phosphorus flame retardant: red phosphorus, average particle size 230 μm, purchased from Sichuan Phosphorus Chemical Co., Ltd.;

[0077] Reinforcement fiber: S1HM435TM-10-3, average length 3mm, Taishan Glass Fiber Co., Ltd.

[0078] Polar additives:

[0079] Polar additive 1: polyvinyl pyrrolidone, PVPK-90, Shanghai Kema New Materials Co., Ltd.;

[0080] Polar additive 2: m-aminobenzoic acid, m-ABA, Aladdin;

[0081] Polar additive 3: N-butylbenzenesulfonamide, N-BBSA, Aladdin;

[0082] Toughening agent:

[0083] Toughening agent 1: MAH-g-SEBS, FG1901 G, Kraton;

[0084] Toughening agent 2: ethylene-methyl acrylate-acrylate terpolymer resin, AN4228C, DuPont, USA;

[0085] Stabilizing agent:

[0086] Stabilizing agent 1: meta-zirconic acid, X-006, Gaoyang Chemical Industry;

[0087] Stabilizing agent 2: magnesium oxide, KYOWAMAG 150, Shanghai Huazhongrong Industry and Trade Co., Ltd.;

[0088] Stabilizing agent 3: hydrotalcite, DHT-4A, Kyowa Chemical Industry Co., Ltd.;

[0089] Antioxidant: Inganox@1098; Lubricant: LOXIOL G32; Both the antioxidant and the lubricant are commercially available, and the same antioxidant and lubricant are used in the parallel experiments of the examples and the comparative examples.

[0090] 2. Performance testing:

[0091] (1) Flame retardancy performance: The nylon composites prepared in each example and comparative example were injection molded into specimens with dimensions of 125 mm * 13 mm * 1.6 mm, and the flame retardancy test was carried out with reference to the UL 94-2013 standard;

[0092] (2) Determination of phosphine content: 100 g of the nylon composites described in each example and comparative example were placed in a sealed glass bottle and placed in an oven at 90 °C for 3 h, and then the phosphine content was measured using a phosphine test gun.

[0093] According to the formula in Table 1, the red phosphorus masterbatch was prepared according to the following preparation method:

[0094] The red phosphorus flame retardant, toughening agent, stabilizing agent and antioxidant were added to a mixer in proportion, stirred and mixed evenly at high speed, and kneaded at 200-300 °C to obtain the red phosphorus masterbatch.

[0095] Table 1 Dosages of each component in red phosphorus masterbatches 1-10 (unit: parts by weight)

[0096] Red phosphorus masterbatch 1 2 3 4 5 6 7 8 9 10 Red phosphorus flame retardant 60 60 60 60 60 60 50 70 60 60 Toughening agent 1 20 10 40 / 20 20 50 30 15 20 Toughening agent 2 20 30 / 40 20 20 / / / 20 Stabilizing aid 1 2 2 2 2 / / 4 1 2 / Stabilizing aid 2 / / / / 2 / / / / / Stabilizing aid 3 / / / / / 2 / / / / Antioxidant 0.5 0.5 0.5 0.5 0.5 0.5 / 1 0.5 0.5

[0097] Red phosphorus masterbatch 11: FR9240KF, nylon-coated red phosphorus masterbatch, Tongcheng Xinde New Materials Co., Ltd.;

[0098] Examples 1-12 and Comparative Examples 1-3

[0099] The nylon composites described in each of the examples and comparative examples were prepared according to the formulations in Tables 2 - 3 by the following preparation method:

[0100] Mix each component evenly, and obtain the nylon composite material through melt blending and extrusion granulation by a twin - screw extruder; the length - to - diameter ratio of the screw of the twin - screw extruder is 40 - 48:1; the barrel temperature of the twin - screw extruder is 270 - 300 °C, and the screw speed of the twin - screw extruder is 150 - 400 rpm;

[0101] Table 2 Dosages (unit: parts by weight) and properties of each component in the nylon composites in Examples 1 - 12

[0102]

[0103]

[0104] Table 3 Dosages (unit: parts by weight) and properties of each component in the nylon composites in Comparative Examples 1 - 3

[0105] Control ratio 1 2 3 Nylon resin 1 52.2 52.2 52.2 Red phosphorus flame retardant / / / Stabilizing aid 1 / / 0.16 Red phosphorus masterbatch 1 / / / Red phosphorus masterbatch 9 8 / / Red phosphorus masterbatch 10 / / 8 Red phosphorus masterbatch 11 / 8 / Reinforcing fiber 25 25 25 Polarity aid 1 2 2 2 Antioxidant 0.5 0.5 0.5 Lubricant 0.3 0.3 0.3 Flame retardancy (1.6 mm) V-0 V-0 V-0 Phosphine (ppm) 2.57 5.78 4.83

[0106] It can be seen from Tables 2 - 3 that the nylon composites prepared in each example of the present invention have a low phosphine content and good flame - retardant properties, and the phosphine content is not higher than 2.35 ppm.

[0107] It can be seen from Examples 1 - 5 that when the red phosphorus masterbatch is coated with a compound toughening agent, the comprehensive properties of the prepared nylon composite material are better.

[0108] It can be seen from Comparative Example 1 that if the content of the toughening agent in the red phosphorus masterbatch is too low, it cannot play a sufficient coating role, and the phosphine content is relatively high during use.

[0109] It can be seen from Comparative Example 2 that if a conventional red phosphorus masterbatch is used instead of the red phosphorus masterbatch in the present invention, the comprehensive properties of the prepared nylon composite material are poor.

[0110] It can be seen from Comparative Example 3 that if the stabilizing additive is not added to the red phosphorus masterbatch, even if the stabilizing additive is added to the nylon composite material, it cannot effectively reduce the reaction of the red phosphorus flame - retardant with moisture and oxygen in the air, resulting in a relatively high phosphine content.

[0111] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, rather than limitations on the implementation manners of the present invention. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to enumerate all implementation manners here. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the claims of the present invention.

Claims

1. A red phosphorus masterbatch, characterized in that: The red phosphorus masterbatch comprises the following components calculated in parts by weight: 50-70 parts of red phosphorus flame retardant; 30-50 parts of toughening agent; 1 to 4 parts of stabilizing agent; The stabilizing aid comprises one or more of zinc oxide, calcium oxide, chromium oxide, hydrotalcite, metazirconic acid or magnesium oxide.

2. The red phosphorus masterbatch according to claim 1, characterized in that: The content of the toughening agent is not less than 25wt% of the red phosphorus masterbatch.

3. The red phosphorus masterbatch according to claim 1 or 2, characterized in that: The toughening agent includes one or more of maleic anhydride grafted olefin polymers, epoxy group grafted olefin polymers or ethylene-acrylate copolymers; preferably, the toughening agent includes one or more of MAH-g-SEBS, MAH-g-POE, GMA-g-POE or EBA.

4. The red phosphorus masterbatch according to claim 1 or 2, characterized in that: The average particle size of the stabilizing agent is 1 to 200 μm.

5. The red phosphorus masterbatch according to claim 1 or 2, characterized in that: The content of the red phosphorus flame retardant in the red phosphorus masterbatch is 30-70wt%.

6. A nylon composite material, characterized in that: The composition comprises the following components calculated by weight:

7. The nylon composite material according to claim 6, characterized in that: The polar auxiliary agent is a substance containing a polar functional group, and the polar functional group includes one or more of a ketone group, an amide group, and a carboxyl group.

8. The nylon composite material according to claim 7, characterized in that: The polar auxiliary agent is one or more of polyvinyl pyrrolidone, N-butylbenzenesulfonamide or m-aminobenzoic acid.

9. A method for preparing the nylon composite material according to any one of claims 6 to 8, characterized in that: The steps include: The components are mixed evenly, melt blended and extruded into granules to obtain a nylon composite material.

10. Use of the nylon composite material according to any one of claims 6 to 8 in the fields of photovoltaics and new energy.

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