An organic phosphine flame-retardant nylon composition with excellent wet-state electrical properties, and a preparation method and application thereof

Abstract

The application discloses an organic phosphine flame-retardant nylon composition with excellent wet-state electric performance and a preparation method and application thereof. The organic phosphine flame-retardant nylon composition comprises the following components in parts by weight: short carbon chain aliphatic nylon resin 23-53 parts, long carbon chain aliphatic nylon resin 10-15 parts, semi-aromatic nylon resin 5-10 parts, glass fiber 20-30 parts, hypophosphite 10-16 parts, inorganic synergist 2-6 parts, and the glass transition temperature of the semi-aromatic nylon resin is greater than or equal to 88 DEG C. The glass fiber is hydrolysis-resistant glass fiber. The organic phosphine flame-retardant nylon composition can realize the unification of high flame-retardant performance and high wet-state electric performance, and has high mechanical performance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high molecular materials, in particular to an organic phosphorus flame-retardant nylon composition with excellent wet-state electrical performance and a preparation method and application thereof. BACKGROUND

[0002] The organic phosphorus flame-retardant nylon has excellent flame-retardant performance, mechanical performance, low smoke, halogen-free and environmental protection and the like, and is widely used in electronic appliances, new energy and rail transit and the like. The nylon has excellent electrical performance in a dry state, but the nylon is easily water-absorbed in a wet-state environment, and the electrical performance of the nylon is greatly reduced after water absorption, and the introduction of the organic phosphorus flame retardant further deteriorates the wet-state electrical performance of the nylon.

[0003] In the new energy industry, it is often required that the material still has excellent electrical performance after high-temperature and high-humidity treatment (treated at 85 DEG C and 85% RH for 1008 h). However, the organic phosphorus flame-retardant nylon has low wet-state electrical performance, which seriously limits its application in the new energy industry. Therefore, it is urgent to develop an organic phosphorus flame-retardant nylon composition which can balance high flame-retardant performance and wet-state electrical performance, and also can maintain excellent mechanical performance, so as to meet the application requirements of the material in the new energy industry. SUMMARY

[0004] In view of the defects in the prior art, the present application provides an organic phosphorus flame-retardant nylon composition with excellent wet-state electrical performance and a preparation method and application thereof.

[0005] The present application provides an organic phosphorus flame-retardant nylon composition, which comprises the following components in parts by weight: short carbon chain aliphatic nylon resin 23-53 parts, such as 23, 25, 30, 35, 40, 45, 50, 53 parts; long carbon chain aliphatic nylon resin 10-15 parts, such as 10, 11, 12, 13, 14, 15 parts; semi-aromatic nylon resin 5-10 parts, such as 5, 6, 7, 8, 9, 10 parts; glass fiber 20-30 parts, such as 20, 22, 24, 26, 28, 30 parts; hypophosphite 10-16 parts, such as 10, 11, 12, 13, 14, 15, 16 parts; inorganic synergist 2-6 parts, such as 2, 3, 4, 5, 6 parts; wherein the mass percentage content of the nylon resin in the composition is not less than 48%.

[0006] The glass transition temperature of the semi-aromatic nylon resin is ≥ 88 DEG C, preferably 90-130 DEG C, and the glass transition temperature is tested by a differential scanning calorimeter according to ISO 11357-3:2013, and the inventors find that the glass transition temperature of the semi-aromatic nylon resin ≥ 88 DEG C can promote the barrier effect of the nylon composition under high-temperature and high-humidity conditions, and promote carbonization to further improve the flame-retardant performance;

[0007] The glass fiber is a hydrolysis-resistant glass fiber, which can inhibit the hydrolysis of the nylon molecular chain under high temperature and high humidity, thereby improving the wet-state electrical property of the composition.

[0008] The inorganic synergist is used as a flame-retardant synergist in the system, which has the advantages of good stability and inhibition of the decomposition of the nylon molecular chain.

[0009] The low moisture absorption property of the long-carbon-chain aliphatic nylon resin and the barrier property of the semi-aromatic nylon resin are synergized to reduce the water absorption rate and water absorption of the nylon molecular chain, thereby improving the wet-state electrical property of the organic phosphorus flame-retardant nylon; by limiting the content of the semi-aromatic nylon resin and the long-carbon-chain aliphatic nylon resin, the wet-state electrical property of the organic phosphorus flame-retardant nylon composition is significantly improved, while the flame-retardant property and mechanical property are still good; by specially selecting the glass transition temperature of the semi-aromatic nylon resin, the flame-retardant property and mechanical property are further improved, and the comprehensive performance is unified; by optimizing the hydrolysis-resistant glass fiber and the flame-retardant synergist, the hydrolysis of the nylon molecular chain under high temperature and high humidity is reduced, thereby improving the wet-state electrical property of the organic phosphorus flame-retardant nylon.

[0010] Further, the short-carbon-chain aliphatic nylon resin is one or more of PA66, PA6, PA56, and PA66 / 6.

[0011] Further, the long-carbon-chain aliphatic nylon resin is one or more of PA610, PA612, or PA1010; the melting point of the long-carbon-chain aliphatic nylon resin is ≥200℃, preferably 200-230℃, and the melting point is tested by a differential scanning calorimeter according to the ISO 11357-3:2011 standard.

[0012] Further, the semi-aromatic nylon resin is one or more of PA6T / 66, PA6I / 6T, or PA6T / M-5T, and the PA6T / 66 has a 6T content of 54-65%.

[0013] Further, the hydrolysis-resistant glass fiber is an E glass fiber, preferably an E glass fiber surface-modified by a silane coupling agent.

[0014] Further, the inorganic synergist is any one or more of boehmite or polyaluminum phosphate.

[0015] Further, the nylon composition further includes 0.1-1 parts by weight of an antioxidant and / or 0.1-1 parts by weight of a lubricant, and can further include other auxiliaries.

[0016] Further, the hypophosphite salt is one or more of aluminum hypophosphite, diethyl aluminum hypophosphite, diisopropyl aluminum hypophosphite, and preferably diethyl aluminum hypophosphite.

[0017] The application also provides a preparation method of the nylon composition, comprising the following steps:

[0018] The components are weighed by parts by weight, and the components are put into a mixer for mixing until uniform to obtain a premix, and then the obtained premix is put into a twin-screw extruder for melt mixing and extrusion granulation to obtain the nylon composition.

[0019] The screw rotation speed of the twin-screw extruder is 250-350 rpm, the length-diameter ratio is (40-48):1, and the barrel temperature is 200-290 DEG C.

[0020] The application also provides application of the nylon composition in high-voltage connectors and new energy batteries.

[0021] Compared with the prior art, the application achieves the following technical effects:

[0022] (1) The nylon composition provided by the application has excellent mechanical properties;

[0023] (2) The nylon composition provided by the application can maintain excellent wet-state electrical properties while taking into account high flame retardant properties. DETAILED DESCRIPTION

[0024] In order to enable personnel in the art to better understand the application scheme, the technical solutions in the embodiments of the application will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor should belong to the scope of protection of the application.

[0025] EMBODIMENTS

[0026] The application will be further described below in combination with specific embodiments and comparative examples. The following specific embodiments are preferred embodiments of the application, but the embodiments of the application are not limited by the following examples, and in particular, are not limited to the types of raw materials used in the following specific examples.

[0027] I. Sources of raw materials for the examples and comparative examples are as follows:

[0028] Short carbon chain aliphatic nylon resin #1: PA66, brand PA66 EP-158, Huafeng Group;

[0029] Short carbon chain aliphatic nylon resin #2: PA6, brand PA6 HY-2800A, Haiyang Chemical Fiber Co., Ltd.;

[0030] Long carbon chain aliphatic nylon resin #1 : PA612, brand PA612 A120, melting point 215℃, Shandong Guangyin New Material Co., Ltd.;

[0031] Long carbon chain aliphatic nylon resin #2: PA610, brand PA610 F120, melting point 222℃, Shandong Guangyin New Material Co., Ltd.;

[0032] Long carbon chain aliphatic nylon resin #3: PA1212, brand PA1212, melting point 184℃, Shandong Dongchen Ruisen New Material Technology Co., Ltd.;

[0033] Semi-aromatic nylon resin #1 : PA6I / 6T, brand TI1207, glass transition temperature 130℃, Shandong Guangyin New Material Co., Ltd.;

[0034] Semi-aromatic nylon resin #2: PA6T / 66, 6T content 55%, brand VicnyI 400PNC003, glass transition temperature 95℃, Zhuhai Wantong Special Engineering Plastics Co., Ltd.;

[0035] Semi-aromatic nylon resin #3: PA6T / M-5T, brand PA6T / M-5T, glass transition temperature 135℃, DuPont Company, USA;

[0036] Semi-aromatic nylon resin #4: PA66 / 6T, 6T content 25%, brand NPD-652, glass transition temperature 70℃, Ineos Ltd.;

[0037] Hypophosphite: diethyl aluminum hypophosphite, brand OP1230, Clariant Co., Ltd.;

[0038] Inorganic synergist #1 : boehmite, brand BG-613SO, Anhui Yishitong Material Science and Technology Co., Ltd.;

[0039] Inorganic synergist #2: polyaluminum phosphate, brand PA2103, Shenzhen Ruishixing Technology Co., Ltd.;

[0040] Flame-retardant synergist #3: melamine polyphosphate, brand BUDIT 3141, purchased from Budenheim Iberica Co., Ltd., Germany;

[0041] Glass fiber #1 : E glass fiber, brand ECS10-3.0-568H, surface modifier is silane coupling agent, China Jushi Co., Ltd.;

[0042] Glass fiber 2: TLD glass fiber, model TLD-CS10-3.0-T436S, surface modifier is silane coupling agent, Taishan Glass Fiber Co., Ltd.

[0043] Antioxidant: model RIANOX 1098, the same substance is used in parallel test;

[0044] Lubricant: model A-C540A, the same substance is used in parallel test.

[0045] The preparation method of the polyamide / polyolefin composite material of the embodiment and the comparative example comprises the following steps:

[0046] The components are weighed by weight parts, and the components are put into a mixer for mixing until uniform to obtain a premix, and then the obtained premix is put into a twin-screw extruder for melt mixing and extrusion granulation to obtain the nylon composition;

[0047] The screw rotation speed of the twin-screw extruder is 250-350 rpm, the length-diameter ratio is (40-48):1, and the barrel temperature is 200-290 DEG C.

[0048] II. Performance test method

[0049] (1) Flame retardant performance: according to the relevant standards of UL 94-2015, the sample is tested for flame retardant performance, the sample thickness is 0.8 mm, the flame retardant grade is divided into V-0, V-1, V-2 and no grade (NR), the flame retardant performance is of great significance to electrical safety, and the UL94 flame retardant grade needs to reach V-0 to meet the application requirements;

[0050] (2) Tensile strength: tested according to ISO 527-2012;

[0051] (3) Wet-state electrical performance test: test the insulation resistance, first treat the square plate (sample size 100*100*1mm) under double 85 conditions (85 DEG C / 85 RH) for 1008h, place for 4h, wipe off the surface moisture, test according to IEC 62631-3-3-2015, test voltage 1000V DC, pressure time 1min.

[0052] Table 1 technical scheme and effect of the embodiment (unit: weight parts)

[0053]

[0054] Table 2 technical scheme and effect of the comparative example (unit: weight parts) Comparative example 4

[0055]

[0056] The short carbon chain aliphatic nylon resin, the long carbon chain aliphatic nylon resin, the semi-aromatic nylon resin with a specific glass transition temperature, and the specific flame retardant synergist and glass fiber are simultaneously introduced in examples 1-9, and the organic phosphorus flame-retardant nylon composition is achieved by the formula combination to have high wet-state electrical performance while obtaining high flame retardant performance, and has high mechanical performance. Among them, the vertical burning performance of the nylon composition reaches V-2 level or above, basically reaches V-0 level, the tensile strength reaches 108 MPa or above, basically reaches 120 MPa or above. At the same time, the insulation resistance of the composition after treatment under high temperature and high humidity conditions is maintained at 23 GΩ or above, has excellent wet-state electrical performance, and realizes the unification of high flame retardant performance and wet-state electrical performance of the organic phosphorus nylon composition.

[0057] Comparative examples 1-7 are compared with example 3, and comparative example 1 only adds a conventional short carbon chain aliphatic nylon resin, without compounding with a long carbon chain aliphatic nylon resin and a semi-aromatic nylon resin. From the test data, it can be known that the conventional organic phosphorus flame-retardant nylon resin has poor wet-state electrical performance; the long carbon chain aliphatic nylon resin in comparative example 3 is added in too small an amount, and cannot play a good role in reducing the water absorption rate in the system, so that the wet-state electrical performance of the nylon composition is significantly reduced; the semi-aromatic nylon resin in comparative example 3 is added in too small an amount, and cannot play a good role in reducing the water absorption rate and limiting the ion migration in the system, so that the organic phosphorus flame-retardant nylon composition has poor flame retardant performance and wet-state electrical performance; too much semi-aromatic nylon resin is added in comparative example 4, so that the organic phosphorus flame-retardant nylon composition has poor compatibility, resulting in a decline in mechanical performance and wet-state electrical performance; the semi-aromatic nylon resin used in comparative example 5 has a glass transition temperature lower than 90℃, so that the semi-aromatic nylon resin cannot play a good barrier role under high heat and high humidity conditions, and the carbonization property is also poor, so that the flame retardant performance and wet-state electrical performance of the nylon composition are reduced; the glass fiber used in comparative example 6 is non-hydrolysis-resistant glass fiber, so that under high temperature and high humidity conditions, the glass fiber cannot well inhibit the hydrolysis of the nylon molecular chain, thereby reducing the wet-state electrical performance of the organic phosphorus flame-retardant nylon composition; melamine phosphate is used as a flame retardant synergist in comparative example 7, although it can give the organic phosphorus flame-retardant nylon composition good flame retardant performance and mechanical performance, but will seriously deteriorate its wet-state electrical performance, because melamine polyphosphate has poor thermal stability, is easy to degrade to produce phosphoric acid, and further promotes the degradation of the nylon molecular chain under high temperature and high humidity conditions, thereby resulting in poor wet-state electrical performance of the organic phosphorus flame-retardant nylon composition. The above comparative examples cannot achieve high flame retardant performance while considering wet-state electrical performance, and have good mechanical performance.

[0058] Based on the test data of vertical burning performance, tensile strength, and insulation resistance in tables 1 and 2, the organic phosphorus flame-retardant nylon composition prepared by examples 1-9 has obvious advantages compared with comparative examples, and can effectively meet the high standard needs of customers and the market.

[0059] The above description is only the preferred embodiment of the present application, and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. An organophosphorus flame-retardant nylon composition, comprising, by weight, the following components: 23-53 parts of short-chain aliphatic nylon resin 10-15 parts of long-chain aliphatic nylon resin 5-10 parts of semi-aromatic nylon resin 20-30 parts glass fiber 10-16 parts hypophosphite Inorganic synergist 2-6 parts; The glass transition temperature of the semi-aromatic nylon resin is ≥88℃; The glass fiber is a hydrolysis-resistant glass fiber; The inorganic synergist is any one or more of boehmite or aluminum polyphosphite; The hypophosphite is one or more of aluminum hypophosphite, diethylaluminum hypophosphite, and diisopropylaluminum hypophosphite.

2. The nylon composition according to claim 1, characterized in that, The short-chain aliphatic nylon resin is one or more of PA66, PA6, PA56, and PA66 / 6.

3. The nylon composition according to claim 1, characterized in that, The long-chain aliphatic nylon resin is one or more of PA610, PA612, or PA1010.

4. The nylon composition according to claim 3, characterized in that, The melting point of the long-chain aliphatic nylon resin is ≥200℃.

5. The nylon composition according to claim 1, characterized in that, The semi-aromatic nylon resin is one or more of PA6T / 66, PA6I / 6T, or PA6T / M-5T.

6. The nylon composition according to claim 1, characterized in that, The hydrolysis-resistant glass fiber is E-glass fiber.

7. The nylon composition according to claim 6, characterized in that, The hydrolysis-resistant glass fiber is E-glass fiber that has been surface modified with a silane coupling agent.

8. The nylon composition according to claim 1, characterized in that, The glass transition temperature of the semi-aromatic nylon resin is 90-130℃.

9. A method for preparing the nylon composition according to any one of claims 1-8, characterized in that, Includes the following steps: Weigh each component according to the weight parts, put each component into a mixer and mix until uniform to obtain a premix. Then, put the obtained premix into a twin-screw extruder for melt mixing and extrusion granulation to obtain the nylon composition.

10. The use of the nylon composition according to any one of claims 1-8 in high-voltage connectors and new energy batteries.

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