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 carrier of the red phosphorus master batch is syndiotactic polystyrene A, and the melt flow rate of the syndiotactic polystyrene A under the conditions of 300 DEG C and 1.2 kg is not less than 10 g / 10 min; the content of the coupling agent A in the red phosphorus master batch is not less than 0.5 wt%. The syndiotactic polystyrene with the specific melt flow rate is adopted as a red phosphorus master batch carrier, the content of the coupling agent in the red phosphorus master batch is adjusted, the prepared red phosphorus master batch is applied to the polyamide composite material, the voltage resistance of the polyamide composite material can be effectively improved, and the flame retardant property and the mechanical property are good.

Description

Technical Field

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

[0002] In recent years, the photovoltaic industry has developed rapidly. As an important component of the photovoltaic power generation system, photovoltaic connectors have a huge market space. Photovoltaic connectors are mainly composed of a body connector and a nut. Usually, PC and PPE are mainly selected for the body connector. However, due to the problem of oil cracking resistance of both PC and PPE, it brings great potential safety hazards to the photovoltaic power generation system. Gradually, high-toughness red phosphorus flame-retardant polyamide is used as the body connector in the photovoltaic industry. However, there are the following problems: the middle connector of the photovoltaic body connector is easy to break, and due to the high water absorption rate of polyamide, the withstand voltage performance is poor.

[0003] Syndiotactic polystyrene (sPS) is a new type of engineering plastic with high modulus, high melting point, and excellent electrical properties, heat resistance, solvent resistance, water resistance, chemical corrosion resistance, etc. Adding syndiotactic polystyrene and common red phosphorus masterbatch directly into the red phosphorus flame-retardant polyamide system has limited improvement in the withstand voltage performance of polyamide materials. Summary of the Invention

[0004] The purpose of the present invention is to overcome the defects or deficiencies of the poor withstand voltage performance of red phosphorus flame-retardant polyamide materials in the prior art, and to provide a red phosphorus masterbatch for a withstand voltage polyamide composite material.

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

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

[0007] Another purpose of the present invention is to provide an application of the withstand voltage polyamide 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 carrier of the red phosphorus masterbatch is syndiotactic polystyrene A, and the melt flow rate of the syndiotactic polystyrene A at 300 °C and 1.2 kg is not less than 10 g / 10 min; the content of coupling agent A in the red phosphorus masterbatch is not less than 0.5 wt%.

[0010] The present invention provides a red phosphorus masterbatch. By using syndiotactic polystyrene with a melt flow rate of not less than 10 g / 10 min as a carrier and adjusting the content of the coupling agent in the red phosphorus masterbatch to be not less than 0.5 wt%, a network structure can be formed. The benzene rings of syndiotactic polystyrene are alternately arranged on both sides of the molecular chain, reducing the disorder of some molecular chains in the system, reducing the generation of internal defects (such as voids and impurities) in the material, and the regular structure restricts the movement paths of free electrons or ions, thereby reducing the conductivity and improving the insulation performance of the material; moreover, the interfacial bonding performance of the red phosphorus masterbatch applied to the composite material enables the subsequent prepared composite material to have good withstand voltage performance and good mechanical properties.

[0011] In the present invention, the melt flow rate of the syndiotactic polystyrene A at 333 °C and 1.2 kg is not less than 13 g / 13 min. For example, but not limited to, not less than 13 g / 13 min, 12 g / 13 min, 15 g / 13 min, 18 g / 13 min, 23 g / 13 min, 22 g / 13 min, 25 g / 13 min, 28 g / 13 min, 33 g / 13 min, 32 g / 13 min, 35 g / 13 min, 38 g / 13 min or 43 g / 13 min, etc. can all achieve the present invention.

[0012] Further, the melt flow rate of the syndiotactic polystyrene A at 333 °C and 1.2 kg is 12 - 35 g / 13 min.

[0013] It should be noted that the test standard for the melt flow rate in the present invention is ISO 1133 - 1 - 2311.

[0014] In the present invention, the content of the coupling agent A in the red phosphorus masterbatch is not less than 3.5 wt%. For example, but not limited to, not less than 3.5 wt%, 3.8 wt%, 1 wt%, 1.2 wt%, 1.5 wt%, 1.8 wt%, 2 wt%, 2.5 wt%, 2.8 wt%, 3 wt%, 3.2 wt%, 3.5 wt%, 3.8 wt%, 4 wt%, 4.2 wt% or 4.5 wt%, etc. can all achieve the present invention.

[0015] Further, the red phosphorus masterbatch comprises the following components calculated by weight:

[0016]

[0017] Further, the average particle size of the red phosphorus powder is 153 - 333 μm.

[0018] Further, the toughening agent A is an olefin polymer containing polar groups.

[0019] Further, the olefin polymer of the polar group is one or more of MAH-g-SEBS, MAH-g-POE, ethylene-methyl acrylate copolymer, or GMA-g-POE.

[0020] Further, the coupling agent A is one or more of an amino group-containing silane coupling agent, an epoxy group-containing silane coupling agent, and a carboxyl group-containing olefin random copolymer.

[0021] Specifically, the amino group-containing silane coupling agent can be one or more of γ-aminopropylmethyldiethoxysilane, 3-aminopropyltriethoxysilane, N-aminoethyl-3-aminopropyltrimethoxysilane, etc.

[0022] The epoxy group-containing silane coupling agent can be one or more of 3-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethoxysilane, etc.

[0023] The carboxyl group-containing olefin random copolymer can be one or more of an ethylene-methyl acrylic acid-acrylate terpolymer resin, an ionic polymer of an ethylene-methyl acrylic acid-acrylate terpolymer resin, or ethylene-methyl acrylic acid.

[0024] Further, the red phosphorus masterbatch further includes 3.1 to 2 parts of an auxiliary agent.

[0025] Specifically, the auxiliary agent includes an antioxidant and / or a lubricant.

[0026] Further, the red phosphorus masterbatch is obtained by blending and kneading each component.

[0027] Specifically, the temperature of the kneading is 233 to 333 °C.

[0028] The present invention also provides a voltage-resistant polyamide composite material, comprising the following components calculated by weight:

[0029]

[0030] In the voltage-resistant polyamide composite material, the content of the polyamide resin is preferably not less than 28 wt%.

[0031] Further, the voltage-resistant polyamide composite material comprises the following components calculated by weight:

[0032]

[0033] Further, the polyamide resin is one or more of PA66, PA613, PA612, PA1313, PA1312, PA1212, PA6, PA7, PA11, PA12, PA6T, PA13T, PA6I / 6T, PA13T / 1312, PA MXD13, PA MXD6, etc.

[0034] Further, the relative viscosity of the polyamide resin is 2.3 to 2.8.

[0035] Further, the measuring method of the relative viscosity is ASTM D789-19.

[0036] It should be noted that syndiotactic polystyrene A and syndiotactic polystyrene B in the present invention can be the same or different.

[0037] In the present invention, toughening agent A and toughening agent B can be the same or different.

[0038] In the present invention, coupling agent A and coupling agent B can be the same or different.

[0039] Further, the melt flow rate of the syndiotactic polystyrene B under the conditions of 333 °C and 1.2 kg is 5 to 35 g / 13 min.

[0040] Further, the toughening agent B is an olefin polymer containing polar groups.

[0041] Furthermore, the olefin polymer containing polar groups is one or several of MAH-g-SEBS, MAH-g-POE, ethylene-methyl acrylate copolymer, or GMA-g-POE.

[0042] Further, the coupling agent B is one or several of a silane coupling agent containing an amino group, a silane coupling agent containing an epoxy group, and a random copolymer of olefins containing a carboxyl group.

[0043] Specifically, the silane coupling agent containing an amino group can be one or several of γ-aminopropylmethyldiethoxysilane, 3-aminopropyltriethoxysilane, N-aminoethyl-3-aminopropyltrimethoxysilane, etc.

[0044] The silane coupling agent containing an epoxy group can be one or several of 3-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethoxysilane, etc.

[0045] The random copolymer of olefins containing a carboxyl group can be one or several of an ethylene-methyl acrylic acid-acrylate terpolymer resin, an ionic polymer of an ethylene-methyl acrylic acid-acrylate terpolymer resin, or ethylene-methyl acrylic acid.

[0046] Specifically, the melt flow rate of the ethylene-methacrylic acid-acrylate terpolymer resin at 190 °C under a load of 2.16 kg is 6 to 15 g / 10 min.

[0047] Specifically, the content of methacrylic acid in the ethylene-methacrylic acid-acrylate terpolymer resin is 3.0 to 5.0 wt%.

[0048] Further, the reinforcing fiber includes glass fiber and / or carbon fiber.

[0049] Specifically, the average length of the reinforcing fiber is 3 to 6 mm.

[0050] Further, the voltage-resistant polyamide composite material further includes 0.1 to 5 parts of additives.

[0051] Specifically, the additives include antioxidant and / or lubricant.

[0052] In the present invention, common antioxidants can be selected, such as but not limited to one or several of hindered phenol antioxidants, phosphite antioxidants, diphenylamine antioxidants or thioether antioxidants.

[0053] Specifically, the hindered phenol antioxidant is one or several of N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamide) (Irganox 1098), pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox 1010), 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox 259), n-octadecyl β-(4-hydroxy-3,5-di-tert-butylphenyl)propionate (Irganox 1076) or 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)acrylic acid]-1,1-dimethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane (ADK AO-80).

[0054] The phosphite antioxidant is one or several of tris(2,4-di-tert-butylphenyl) phosphite (Irganox 168), bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite (PEP-36) or 627A.

[0055] The diphenylamine antioxidant is 4,4'-bis(α,α'-dimethylbenzyl) diphenylamine.

[0056] The thioether antioxidant is one or several of distearyl thiodipropionate, dilauryl thiodipropionate or pentaerythritol lauryl thiodipropionate.

[0057] 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, ester lubricants or silicone lubricants.

[0058] Specifically, the stearic acid lubricant can be calcium stearate and / or zinc stearate.

[0059] The polyethylene lubricant can be polyethylene wax.

[0060] The amide lubricant can be one or more of oleic acid amide lubricants, EBS amide lubricants or erucic acid amide lubricants.

[0061] The ester lubricant can be one or more of aliphatic stearic acid esters, oleic acid-based aliphatic polyesters or erucic acid-based aliphatic polyesters.

[0062] The silicone lubricant can be polydimethylsiloxane.

[0063] The present invention also protects a method for preparing the above-mentioned voltage-resistant polyamide composite material, comprising the following steps:

[0064] Mixing each component evenly to obtain a premix; subjecting the premix to melt blending and extrusion granulation to obtain a voltage-resistant polyamide composite material.

[0065] Further, the extrusion granulation is carried out in a twin-screw extruder.

[0066] Further, the length-diameter ratio of the screw of the twin-screw extruder is 40-48:1.

[0067] Further, the barrel temperature of the twin-screw extruder is 270-300 °C.

[0068] Further, the screw rotation speed of the twin-screw extruder is 150-400 rpm.

[0069] The present invention also protects the use of the above-mentioned voltage-resistant polyamide composite material in the preparation of electronic components and / or household appliances. In particular, the above polyamide composite material is used in the preparation of parts with good voltage resistance and mechanical properties. In particular, it is used in the preparation of connectors in the photovoltaic industry, such as materials for electrical switches, connectors and low-voltage circuit breakers.

[0070] Compared with the prior art, the beneficial effects of the present invention are:

[0071] The present invention provides a red phosphorus masterbatch for a voltage-resistant polyamide composite material. The red phosphorus masterbatch uses syndiotactic polystyrene with a specific melt flow rate as a carrier, and then a coupling agent is added, which can form a continuous network structure. When it is added to a polyamide resin, it can effectively improve the voltage-resistant performance of the obtained polyamide composite material, and at the same time has good flame retardant performance and mechanical properties. Detailed Embodiments

[0072] The present invention will be further described below in conjunction with the detailed embodiments, but the embodiments do not limit the present invention in any form. Unless otherwise specified, the raw material reagents used in the embodiments of the present invention are conventional raw material reagents purchased.

[0073] Raw materials used in the embodiments and comparative examples of the present invention:

[0074] Polyamide resin:

[0075] Polyamide resin 1: PA66, PA66 U4833 NC31 SS, purchased from Invista;

[0076] Polyamide resin 2: PA613, PA613 F153, Shandong Guangyin New Materials Co., Ltd.;

[0077] Red phosphorus powder:

[0078] Red phosphorus powder 1: Red phosphorus, average particle size 233μm, Chuan Phosphorus Chemical Co., Ltd.;

[0079] Red phosphorus powder 2: Red phosphorus, average particle size 253μm, Guangzhou Helong Trading Co., Ltd.;

[0080] Polyamide-coated red phosphorus masterbatch: FR9243KF, Tongcheng Xinde New Materials Co., Ltd.;

[0081] Syndiotactic polystyrene:

[0082] Syndiotactic polystyrene A1: XAREC TM 333ZC, melt flow rate at 333°C and 1.2 kg condition is 33 g / 13 min, purchased from Idemitsu;

[0083] Syndiotactic polystyrene A2: XAREC TM 143ZC, melt flow rate at 333°C and 1.2 kg condition is 14.2 g / 13 min, purchased from Idemitsu;

[0084] Syndiotactic polystyrene A3: XAREC TM 93ZC, melt flow rate at 333°C and 1.2 kg condition is 9 g / 13 min, purchased from Idemitsu;

[0085] Syndiotactic polystyrene B1: XAREC TM 333ZC, with a melt flow rate of 33 g / 13 min at 333 °C under a condition of 1.2 kg, purchased from Idemitsu;

[0086] Syndiotactic polystyrene B2: XAREC TM 143ZC, with a melt flow rate of 14.2 g / 13 min at 333 °C under a condition of 1.2 kg, purchased from Idemitsu;

[0087] Syndiotactic polystyrene B3: XAREC TM 93ZC, with a melt flow rate of 9 g / 13 min at 333 °C under a condition of 1.2 kg, purchased from Idemitsu;

[0088] Atactic polystyrene: PS 353K, with a melt flow rate of 14.7 g / 13 min at 333 °C under a condition of 1.2 kg, purchased from Guoxiong Chemical Co., Ltd.

[0089] Toughening agent A: MAH-g-SEBS, FG1931 G, purchased from Kraton;

[0090] Toughening agent B: MAH-g-SEBS, FG1931 G, purchased from Kraton;

[0091] Coupling agent A:

[0092] Coupling agent A1: Ethylene-methylacrylic acid-acrylate terpolymer resin, AN4228C, purchased from DuPont Chemical Co., USA;

[0093] Coupling agent A2: 3-Aminopropyltriethoxysilane, JH-A113, purchased from Hubei Jianghan New Materials Co., Ltd.;

[0094] Coupling agent A3: 3-Glycidoxypropyltrimethoxysilane, JH-O1871, purchased from Jingzhou Jianghan Fine Chemical Co., Ltd.;

[0095] Coupling agent B: 3-Glycidoxypropyltrimethoxysilane, JH-O1871, purchased from Jingzhou Jianghan Fine Chemical Co., Ltd.;

[0096] Reinforcing fiber: Glass fiber, S1HM435TM-13-3, with an average length of 3 mm, purchased from Taishan Fiberglass Inc.;

[0097] Auxiliary agent:

[0098] Antioxidant: hindered phenolic antioxidant, Inganox 1398; Lubricant: stearic acid lubricant, LOXIOL G32; Both the antioxidant and the lubricant are commercially available, and the same raw materials are used in the parallel experiments of the examples and comparative examples.

[0099] Examples 1-7 and Comparative Examples 1-3

[0100] According to the formula in Table 1, prepare the red phosphorus masterbatch according to the following preparation method:

[0101] Add the components in the red phosphorus masterbatch to a kneader in proportion, stir and mix evenly at high speed, and obtain it by kneading. The kneading temperature is 233-333 °C.

[0102] Dosage of each component in the red phosphorus masterbatch in each example and comparative example in Table 1 (unit: parts by weight)

[0103]

[0104] Examples 8-23 and Comparative Examples 4-7

[0105] For the polyamide composites in Examples 8-23 and Comparative Examples 4-7, prepare according to the formula in Tables 2-3 according to the following method:

[0106] Mix the components evenly to obtain a premix; put the premix into a twin-screw extruder and obtain the polyamide composite material through melt blending and extrusion granulation; the length-diameter ratio of the screw of the twin-screw extruder is 43-48:1; the barrel temperature of the twin-screw extruder is 273-333 °C, and the screw speed of the twin-screw extruder is 153-433 rpm.

[0107] Dosage of each component in the polyamide composite material in each example in Table 2 (unit: parts by weight)

[0108]

[0109]

[0110] Dosage of each component in the polyamide composite material in Comparative Examples 4-7 in Table 3 (unit: parts by weight)

[0111]

[0112] Performance test

[0113] 1. Test method

[0114] (1) Flame retardancy test: Inject the polyamide composite materials in each example and comparative example into test specimens with dimensions of 125 mm * 13 mm * 1 mm, and conduct a flame retardancy test with reference to the UL 94-2313 standard;

[0115] (2) Water absorption test: The polyamide composite materials in each example and comparative example were injection-molded into splines with dimensions of 125 mm * 13 mm * 3 mm, and the water absorption was measured according to the ASTM D573-22 standard;

[0116] (3) Dielectric withstand voltage test: The polyamide composite materials in each example and comparative example were injection-molded into splines with dimensions of 133 mm * 133 mm * 1.3 mm, and the dielectric withstand voltage performance was measured according to the IEC 61215-2335 standard; The industry requirement is that the insulation resistance ≥ 433 MΩ and the leakage current ≤ 53 μA;

[0117] (4) Izod notched impact strength test: The polyamide composite materials in each example and comparative example were injection-molded into splines with dimensions of 83 mm * 13 mm * 4 mm, and tested according to the ISO 178 2313 standard, and the notch type was Type A.

[0118] 2. Test results

[0119] The performance test results of the polyamide composite materials prepared in each example and comparative example are shown in Table 3.

[0120] Table 4 Performance test results of Examples 8 to 23 and Comparative Examples 4 to 7

[0121]

[0122]

[0123] As can be seen from Table 4, the polyamide composite materials prepared in each example of the present invention have good dielectric withstand voltage performance and good mechanical properties. Specifically: the prepared polyamide composite materials meet V-3 flame retardancy, the water absorption is not higher than 3.5%, the insulation resistance is ≥ 433 MΩ, the leakage current ≤ 53 μA, and the notched impact strength is not lower than 9.5 kJ / m 2 .

[0124] As can be seen from Comparative Example 4, when the melt flow rate of syndiotactic polystyrene in the red phosphorus masterbatch is too low, the leakage current of the prepared polyamide composite material increases significantly, fails to meet the requirements, and the notched impact strength decreases.

[0125] As can be seen from Comparative Example 5, if other resins are used to replace syndiotactic polystyrene as the carrier in the red phosphorus masterbatch, the comprehensive performance of the prepared polyamide composite material decreases significantly, the leakage current increases significantly, fails to meet the requirements, and the notched impact strength decreases.

[0126] As can be seen from Comparative Example 6, if the red phosphorus masterbatch does not contain a coupling agent, the subsequent application will lead to poor interfacial bonding, making the material more easily broken down, and its mechanical properties are also low.

[0127] It can be seen from Comparative Example 7 that if a conventional red phosphorus masterbatch is used instead of the red phosphorus masterbatch of the present invention, the water absorption rate of the obtained polyamide composite material is relatively high, and the withstand voltage performance is significantly poor.

[0128] Obviously, the above-mentioned 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 the implementation manners here. Any modifications, equivalent replacements, and improvements made within the spirit and principle of the present invention shall be included in the protection scope of the claims of the present invention.

Claims

1. A red phosphorus masterbatch, characterized in that: The carrier of the red phosphorus masterbatch is syndiotactic polystyrene A, and the melt flow rate of the syndiotactic polystyrene A under the conditions of 300° C. and 1.2 kg is not less than 10 g / 10 min; the content of the coupling agent A in the red phosphorus masterbatch is not less than 0.5 wt %.

2. The red phosphorus masterbatch according to claim 1, characterized in that: The red phosphorus masterbatch comprises the following components calculated in parts by weight:

3. The red phosphorus masterbatch according to claim 1, characterized in that: The melt flow rate of the syndiotactic polystyrene A at 300° C. and 1.2 kg is 12 to 35 g / 10 min.

4. The red phosphorus masterbatch according to claim 1, characterized in that: The average particle size of the red phosphorus powder is 150-300 μm.

5. The red phosphorus masterbatch according to claim 1, characterized in that: The toughening agent A is an olefin polymer containing a polar group; preferably, the olefin polymer containing a polar group is one or more of MAH-g-SEBS, MAH-g-POE, ethylene-methyl acrylate copolymer or GMA-g-POE; the coupling agent A is one or more of an amino-containing silane coupling agent, an epoxy-containing silane coupling agent, and a carboxyl-containing olefin random copolymer.

6. The red phosphorus masterbatch according to claim 2, characterized in that: The red phosphorus masterbatch is obtained by blending and kneading the components.

7. A voltage-resistant polyamide composite material, characterized in that: The composition comprises the following components calculated by weight:

8. The polyamide composite material according to claim 7, characterized in that: The melt flow rate of the syndiotactic polystyrene B at 300° C. and 1.2 kg is 5 to 35 g / 10 min.

9. A method for preparing the polyamide composite material according to claim 7 or 8, characterized in that: The steps include: The components are mixed uniformly to obtain a premix; the premix is ​​melt-blended and extruded to granulate to obtain a polyamide composite material.

10. Use of the polyamide composite material according to claim 7 or 8 in the preparation of electronic components and / or household appliances.

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