Voltage-resistant nylon composition as well as preparation method and application thereof

Abstract

The invention discloses a voltage-resistant nylon composition as well as a preparation method and application thereof. The nylon composition comprises the following components in parts by weight: 28-85 parts of nylon resin; 1.5 to 4.5 parts of a nucleating agent; 1.5 to 6.5 parts of a charge trapping agent; 4-12 parts of a flame retardant; 8 to 32 parts of reinforcing fiber; and 8-20 parts of a toughening agent. The nucleating agent and the charge trapping agent are added into the nylon resin, so that charges in a system are absorbed and charge accumulation is prevented while the condensation form of the nylon composition is improved, and the prepared nylon composition has relatively good voltage resistance and meets V-0 flame retardance at the same time.

Description

Technical Field

[0001] The present invention relates to the technical field of engineering plastics, and more specifically, to a voltage-resistant nylon composition, a preparation method thereof, and an application thereof. Background Art

[0002] Electric breakdown resistance is an inherent property of materials, that is, under high voltage, charges are injected into the insulating material or the accelerated carriers migrate in the insulating material, and the insulating matrix is quickly broken down. At this time, the maximum breakdown voltage that the material can withstand is measured.

[0003] Flame-retardant nylon composites have received extensive attention due to their excellent flame-retardant properties and mechanical properties. However, due to the ionization effect of nylon itself and a large number of ionic substances introduced to stabilize the precipitation of flame retardants during the preparation of flame-retardant nylon masterbatches, the voltage-resistant performance of flame-retardant nylon composites may be poor. In addition, there is a strong interaction between the amide bonds in nylon molecules and water molecules, resulting in the material being prone to water absorption. The water molecules form a conductive path in the composite material, reducing the resistivity of the material, increasing the leakage current, and restricting its application in connector fields such as photovoltaic connectors. Summary of the Invention

[0004] The purpose of the present invention is to overcome the defects or deficiencies of the poor voltage-resistant performance of the flame-retardant nylon composition in the above-mentioned prior art, and to provide a voltage-resistant nylon composition.

[0005] Another object of the present invention is to provide a preparation method of the voltage-resistant nylon composition.

[0006] Another object of the present invention is to provide an application of the voltage-resistant nylon composition.

[0007] To achieve the above object, the present invention is implemented by adopting the following technical solutions:

[0008] A voltage-resistant nylon composition, comprising the following components calculated by weight:

[0009]

[0010] The present invention provides a voltage-resistant nylon composition. By adding a nucleating agent and a charge-trapping agent to the nylon resin, the water absorption of the nylon composition can be reduced, and the voltage-resistant performance of the nylon composition can be improved. Specifically: adding a nucleating agent to the nylon composition can effectively adjust the aggregation morphology, and by adding a charge-trapping agent, the charge accumulation in the matrix material can be reduced, thereby improving the voltage-resistant performance of the polyamide composition.

[0011] In the present invention, the nucleating agent is 1.5 to 4.5 parts, such as but not limited to 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, 2.8 parts, 3 parts, 3.2 parts, 3.5 parts, 3.8 parts, 4 parts, 4.2 parts or 4.5 parts, etc., and the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the specific point values included in the scope of the present invention are not exhaustively listed herein.

[0012] In the present invention, the charge trapping agent is 1.5 to 6.5 parts, such as but not limited to 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, 2.8 parts, 3 parts, 3.2 parts, 3.5 parts, 3.8 parts, 4 parts, 4.2 parts, 4.5 parts, 4.8 parts, 5 parts, 5.2 parts, 5.5 parts, 5.8 parts, 6 parts, 6.2 parts or 6.5 parts, etc., and the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the specific point values included in the scope of the present invention are not exhaustively listed herein.

[0013] In the voltage-resistant nylon composition, the content of the nylon resin is preferably not less than 25 wt%.

[0014] Furthermore, the voltage-resistant nylon composition comprises the following components calculated by weight:

[0015]

[0016] Furthermore, the nylon resin includes one or more of aliphatic nylon resins and aromatic nylon resins.

[0017] Specifically, the aliphatic nylon resin is one or more of PA66, PA610, PA612, PA1010, PA1012, PA1212, PA6, PA7, PA11, PA12, PAPACM12.

[0018] The aromatic nylon resin is one or more of PA6T, PA9T, PA10T, PA11T, PA12T, PA13T, PA6T / 6I, PA6T / 6I / 66, PA6I, PA6I / 6T, PA10T / 66, PA10T / 1010, PA10T / 10I, PPTA.

[0019] Furthermore, the nylon resin is a mixture of aliphatic nylon resin and aromatic nylon resin.

[0020] In some preferred specific embodiments, the mass ratio of aliphatic nylon resin to aromatic nylon resin in the nylon resin is not higher than 10:1, such as but not limited to not higher than 10:1, 9.5:1, 9:1, 8.5:1, 8:1, 7.5:1, 7:1, 6.5:1, 6:1, 5.5:1, 5:1, 4.5:1, 4:1, 3.5:1, 3:1, 2.5:1, 2:1, 1.5:1, 1:1, 0.9:1, 0.8:1, 0.7:1, etc.

[0021] Furthermore, the mass ratio of aliphatic nylon resin to aromatic nylon resin in the nylon resin is 8:1 to 0.8:1.

[0022] Still further, the mass ratio of aliphatic nylon resin to aromatic nylon resin in the nylon resin is 6:1 to 1:1.

[0023] Still further, the mass ratio of aliphatic nylon resin to aromatic nylon resin in the nylon resin is 4:1 to 2:1.

[0024] Specifically, the relative viscosity of the aliphatic nylon resin is 2.0 to 2.8.

[0025] Specifically, the relative viscosity of the aromatic nylon resin is 1.8 to 2.5.

[0026] Specifically, the test standard for the relative viscosity is ASTM D789-19.

[0027] Furthermore, the nucleating agent includes one or more of inorganic nucleating agents, amide nucleating agents or phosphate nucleating agents.

[0028] Specifically, the inorganic nucleating agent includes one or more of graphene, carbon nanotubes, carbon black, montmorillonite, halloysite, nano calcium carbonate, boron nitride, molybdenum disulfide, tungsten disulfide, magnesium sulfate whiskers, nano silica and talcum powder.

[0029] The amide nucleating agent is one or more of polyethylenediamine oxalate, polydecamethylene terephthalate, polydecamethylene isophthalate, polynonamethylene terephthalate or polynonamethylene isophthalate.

[0030] The phosphate nucleating agent is one or more of sodium phenylphosphinate, sodium benzenephosphite, sodium 2,2-methylenebis(4,6-di-tert-butylphenyl) phosphate or aluminum bis[2,2'-methylenebis(4,6-di-tert-butylphenyl)] phosphate.

[0031] In some preferred specific embodiments, the average particle size of the magnesium sulfate whiskers is 0.1 to 2 μm.

[0032] Specifically, the average particle size is obtained by testing with a laser particle size analyzer.

[0033] In some preferred specific embodiments, the polyethylene glycol diacyl diamide is in powder form.

[0034] Specifically, the decomposition temperature of the polyethylene glycol diacyl diamide is 350 - 500 °C.

[0035] Further, the charge trapping agent includes aromatic polyimide and / or m-aminobenzoic acid.

[0036] Further, the monomers of the aromatic polyimide are aromatic dianhydride and aromatic diamine.

[0037] Even further, the monomers of the aromatic polyimide are biphenyltetracarboxylic dianhydride and p-phenylenediamine.

[0038] Further, the relative viscosity of the aromatic polyamideimide is 1.8 - 2.2.

[0039] Further, the test standard for the relative viscosity is ASTM D3835-16.

[0040] Further, the flame retardant includes one or more of brominated flame retardants, nitrogen-based flame retardants, or phosphorus-based flame retardants.

[0041] Specifically, the brominated flame retardants include one or more of decabromodiphenylethane, brominated polystyrene, brominated polycarbonate, brominated epoxy resin, pentabromobenzyl acrylate, or bromotriazine.

[0042] Specifically, the nitrogen-based flame retardants include one or more of tris(2-hydroxyethyl)isocyanurate, triglycidyl isocyanurate, melamine cyanurate, or melamine polyphosphate.

[0043] Specifically, the phosphorus-based flame retardants include one or more of trimethyl phosphate, red phosphorus, tricresyl phosphate, tetraphenyl resorcinol diphosphate, or ammonium polyphosphate.

[0044] Further, the reinforcing fiber includes glass fiber and / or carbon fiber.

[0045] Further, the average length of the reinforcing fiber is 3 - 6 mm.

[0046] Further, the toughening agent is a polyolefin containing polar groups.

[0047] Further, the polar groups in the toughening agent are one or more of maleic anhydride, epoxy group, or ester group.

[0048] Further, the polyolefin containing polar groups is one or more of MAH-g-SEBS, MAH-g-POE, ethylene-methyl acrylate copolymer, or GMA-g-POE.

[0049] Further, the voltage-resistant nylon composition further comprises 0.1 to 5 parts of an auxiliary agent.

[0050] Further, the auxiliary agent is an antioxidant and / or a lubricant.

[0051] In the present invention, common antioxidants can be selected according to the prior art, such as but not limited to one or more of hindered phenol antioxidants, phosphite antioxidants, diphenylamine antioxidants, or thioether antioxidants.

[0052] Specifically, the hindered phenol antioxidant is one or more of N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamide) (Irganox 1098), pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox1010), 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox 259), n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox 1076), or 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)acryloyl]-1,1-dimethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane (ADK AO-80).

[0053] The phosphite antioxidant is one or more of tris(2,4-di-tert-butylphenyl) phosphite (Irganox 168), bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite (PEP-36), or 627A.

[0054] The diphenylamine antioxidant is 4,4'-bis(α,α'-dimethylbenzyl) diphenylamine.

[0055] The thioether antioxidant is one or more of distearyl thiodipropionate, dilauryl thiodipropionate, or pentaerythritol tetrakis(3-laurylthiopropionate).

[0056] In the present invention, common lubricants can be selected according to the prior art. Such as but not limited to one or more of stearic acid lubricants, polyethylene lubricants, amide lubricants, paraffin lubricants, ester lubricants, or silicone lubricants.

[0057] Specifically, the stearic acid lubricant can be calcium stearate and / or zinc stearate.

[0058] The polyethylene-based lubricant may be polyethylene wax.

[0059] The amide-based lubricant may be one or more of oleic acid amide-based lubricants, EBS amide-based lubricants, or erucic acid amide-based lubricants.

[0060] The ester-based lubricant may be an aliphatic stearate, such as an oleic acid-based aliphatic polyester and / or an erucic acid-based aliphatic polyester.

[0061] The silicone-based lubricant may be polydimethylsiloxane.

[0062] The present invention also protects a method for preparing the above-mentioned voltage-resistant nylon composition, comprising the following steps:

[0063] Mix the components evenly to obtain a premix, and subject the premix to melt blending and extrusion granulation to obtain the voltage-resistant nylon composition.

[0064] Furthermore, the extrusion granulation is carried out in a twin-screw extruder.

[0065] Furthermore, the length-diameter ratio of the screw of the twin-screw extruder is 40-48:1.

[0066] Furthermore, the barrel temperature of the twin-screw extruder is 270-300 °C.

[0067] Furthermore, the screw rotation speed of the twin-screw extruder is 150-400 rpm.

[0068] The present invention also protects the use of the above-mentioned voltage-resistant nylon composition in the preparation of household items, electronic components, and household appliances. In particular, the above-mentioned voltage-resistant nylon composition is used in the preparation of articles with good voltage resistance performance 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, etc.

[0069] Compared with the prior art, the beneficial effects of the present invention are:

[0070] The present invention provides a voltage-resistant nylon composition. By adding a nucleating agent and a charge-trapping agent to the nylon resin, the nucleating agent can effectively adjust the aggregation morphology of the nylon composition, and the charge-trapping agent can reduce the charge accumulation in the system, improve the voltage resistance performance of the nylon composition, and at the same time have good flame retardant performance. Detailed Embodiments

[0071] The following further illustrates the present invention in conjunction with specific embodiments, but the embodiments do not impose any form of limitation on the present invention. Unless otherwise specified, the raw material reagents used in the embodiments of the present invention are conventional raw material reagents purchased.

[0072] 1. Raw materials used in each embodiment and comparative example of the present invention:

[0073] Nylon resin:

[0074] Nylon resin 1: PA66, PA66 U4800 NC01 SS, purchased from INVISTA;

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

[0076] Nylon resin 3: PA10T, Vicnyl 6100P NC013, purchased from Zhuhai Wantong Special Engineering Plastics Co., Ltd.;

[0077] Nylon resin 4: PA6I / 6T, TI1207, purchased from Shandong Guangyin New Materials Co., Ltd.;

[0078] Nucleating agent:

[0079] Nucleating agent 1: poly(ethylene glycol oxalamide), P22, purchased from Guangzhou Weiqi Trading Co., Ltd.;

[0080] Nucleating agent 2: magnesium sulfate whiskers, purchased from Shenyang Lyon New Materials Co., Ltd.;

[0081] Charge scavenger:

[0082] Charge capture agent 1: m-aminobenzoic acid, purchased from Aladdin;

[0083] Charge scavenger 2: aromatic polyimide, Visimiderm TM XL001, purchased from Zhuhai Wantong Special Engineering Plastics Co., Ltd.;

[0084] Flame retardant:

[0085] Flame retardant 1: red phosphorus masterbatch, FR9240KF, purchased from Tongcheng Xinde New Materials Co., Ltd.;

[0086] Flame retardant 2: decabromodiphenylethane, 8010, purchased from Albemarle Corporation;

[0087] Reinforcement fiber: glass fiber, S1HM435TM-10-3, average length 3 mm, purchased from Taishan Glass Fiber Co., Ltd.;

[0088] Toughening agent: MAH-g-SEBS, FG1901 G, purchased from Kraton;

[0089] Additives:

[0090] 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 comparative examples.

[0091] 2. The nylon compositions described in each of the examples and comparative examples were prepared according to the formulations in Tables 1 - 2 by the following preparation method:

[0092] Mix each component evenly to obtain a premix, and put the premix into a twin - screw extruder for melt blending and extrusion granulation to obtain the nylon composition; 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.

[0093] 3. Test methods:

[0094] (1) Flame - retardant performance test: The nylon compositions in each of the examples and comparative examples were injection - molded into specimens with dimensions of 125 mm×13 mm×1.0 mm, and the flame - retardant test was carried out with reference to the UL 94 - 2013 standard;

[0095] (2) Water absorption test: The nylon compositions in each of the examples and comparative examples were injection - molded into specimens with dimensions of 125 mm×13 mm×3.0 mm, and the water absorption was measured according to the ASTM D570 - 22 standard;

[0096] (3) Dielectric withstand voltage test: The nylon compositions in each of the examples and comparative examples were injection - molded into square plates with dimensions of 100 mm×100 mm×1.0 mm, and the dielectric withstand voltage performance was measured according to the IEC 61215 - 2005 standard; The industry requirement is that the insulation resistance ≥ 400 MΩ and the leakage current ≤ 50 μA.

[0097] Examples 1 - 13 and Comparative Examples 1 - 4

[0098] Table 1 Dosages of each component in the dielectric - withstand voltage nylon compositions in Examples 1 - 13 (unit: parts by weight)

[0099]

[0100]

[0101] Table 2 Dosages of each component in the dielectric - withstand voltage nylon compositions in Comparative Examples 1 - 4 (unit: parts by weight) and properties

[0102] Comparative Example 1 2 3 4 Nylon Resin 1 35.2 35.2 35.2 35.2 Nylon Resin 3 10 10 10 10 Nucleating Agent 1 2 6 / / Charge Trapping Agent 1 / / 4 6 Flame Retardant 1 8 8 8 8 Reinforcing Fiber 25 25 25 25 Strengthening Agent 15 15 15 15 Antioxidant 0.5 0.5 0.5 0.5 Lubricant 0.3 0.3 0.3 0.3 Flame Retardant Grade (1.0 mm) V-0 V-0 V-0 V-0 Water Absorption Rate (%) 2.67 2.64 2.53 2.47 Insulation Resistance (Ω) 891M 973M 1.26G 1.32G Leakage Current (μA) 78.9 75.4 56.8 52.8

[0103] As can be seen from Table 1, the nylon composition prepared by the present invention has good voltage resistance performance and low water absorption rate, and at the same time has good flame retardant performance; specifically: while the nylon composition meets the V-0 flame retardant requirement, its insulation resistance is not less than 400 MΩ, the leakage current is not higher than 50 μA, and the water absorption rate is not higher than 2.5%.

[0104] As can be seen from Examples 1, 5 and 8 to 11, by compounding aliphatic nylon resin and aromatic nylon resin, the performance of the prepared nylon composition is further improved.

[0105] As can be seen from Comparative Examples 1 to 4, if the nylon composition is prepared only by using a nucleating agent or a charge trapping agent, its voltage resistance performance cannot meet the requirements.

[0106] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, rather than limiting 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 voltage-resistant nylon composition, characterized in that: The composition comprises the following components calculated by weight:

2. The nylon composition according to claim 1, characterized in that: The nucleating agent includes one or more of an inorganic nucleating agent, an amide nucleating agent or a phosphate nucleating agent.

3. The nylon composition according to claim 1, characterized in that: The charge capture agent is aromatic polyimide and / or m-aminobenzoic acid.

4. The nylon composition according to claim 1, characterized in that: The nylon resin includes one or more of an aliphatic nylon resin and / or an aromatic nylon resin.

5. The nylon composition according to claim 1, characterized in that: The nylon resin is a mixture of aliphatic nylon resin and aromatic nylon resin; preferably, the mass ratio of aliphatic nylon resin to aromatic nylon resin in the nylon resin is not higher than 10:

1.

6. The nylon composition according to claim 1, characterized in that: The flame retardant includes one or more of a bromine-based flame retardant, a nitrogen-based flame retardant or a phosphorus-based flame retardant.

7. The nylon composition according to claim 1, characterized in that: The toughening agent is a polyolefin containing polar groups; preferably, the polar groups in the toughening agent are one or more of maleic anhydride, epoxy groups or ester groups.

8. The nylon composition according to claim 1, characterized in that: The nylon composition further comprises 0.1 to 5 parts of auxiliary agents.

9. A method for preparing the nylon composition according to any one of claims 1 to 8, characterized in that: The steps include: The components are mixed uniformly to obtain a premix, and the premix is ​​melt-blended and extruded to granulate to obtain a voltage-resistant nylon composition.

10. Use of the nylon composition according to any one of claims 1 to 8 in the preparation of household items, electronic components and household appliances.

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