A voltage-resistant nylon composition and a method for preparing and using the same

Abstract

The application discloses a voltage-resistant nylon composition and a preparation method and application thereof. The nylon composition comprises the following components in parts by weight: 28-85 parts of nylon resin, 1.5-4.5 parts of a nucleating agent, 1.5-6.5 parts of a charge capturing agent, 4-12 parts of a flame retardant, 8-32 parts of reinforcing fibers and 8-20 parts of a toughening agent. In the application, the nucleating agent and the charge capturing agent are added into the nylon resin, so that the condensed state of the nylon composition is improved, the charges in the system are absorbed, the charge accumulation is prevented, the prepared nylon composition has good voltage-resistant performance, and the V-0 flame retardation is met.

Description

Technical Field

[0001] This invention relates to the field of engineering plastics technology, and more specifically, to a voltage-resistant nylon composition, its preparation method, and its application. Background Technology

[0002] Electrical breakdown resistance is an inherent property of materials. Under high voltage, charge is injected into the insulating material or the migration of charge carriers in the insulating material is accelerated, 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 widespread attention due to their excellent flame-retardant and mechanical properties. However, the ionization effect of nylon itself and the large amount of ionic substances introduced during the preparation of flame retardant masterbatches to stabilize the precipitation of flame retardants may lead to poor voltage resistance. Furthermore, the strong interaction between the amide bonds in nylon molecules and water molecules makes the material prone to water absorption. Water molecules form conductive pathways in the composite material, reducing the resistivity of the material and increasing leakage current, thus limiting its application in connector fields such as photovoltaic connectors. Summary of the Invention

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

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

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

[0007] To achieve the above objectives, the present invention employs the following technical solution:

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

[0009]

[0010] This 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 resistance of the nylon composition can be improved. Specifically, adding a nucleating agent to the nylon composition can effectively adjust the aggregation morphology, and adding a charge trapping agent can reduce the charge accumulation in the matrix material, thereby improving the voltage resistance of the polyamide composition.

[0011] The nucleating agent described in this invention is 1.5 to 4.5 parts, for example, 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 ​​are not exhaustively listed in this invention due to space limitations and for the sake of brevity.

[0012] The charge-capturing agent described in this invention is 1.5 to 6.5 parts, for example, 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, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the specific values ​​included in the range are not exhaustively listed in this invention.

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

[0014] Further, the voltage-resistant nylon composition comprises the following components in parts by weight:

[0015]

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

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

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

[0020] In some preferred embodiments, the mass ratio of aliphatic nylon resin to aromatic nylon resin in the nylon resin is not higher than 10:1, for example, 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] Furthermore, the mass ratio of aliphatic nylon resin to aromatic nylon resin in the nylon resin is 6:1 to 1:1.

[0023] Furthermore, 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 talc.

[0029] The amide nucleating agent is one or more of polyethylene glycol, polydecylamine terephthalic acid, polydecylamine isophthalic acid, polynonadiamine terephthalic acid, or polynonadiamine isophthalic acid.

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

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

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

[0033] In some preferred embodiments, the polyethylene glycol is in the form of a powder.

[0034] Specifically, the decomposition temperature of the poly(ethylene glycol) is 350–500°C.

[0035] Furthermore, the charge-scavenging agent comprises aromatic polyimide and / or m-aminobenzoic acid.

[0036] Furthermore, the monomers of the aromatic polyimide are aromatic dianhydrides and aromatic diamines.

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

[0038] Furthermore, the relative viscosity of the aromatic polyamide imide is 1.8 to 2.2.

[0039] Furthermore, the relative viscosity is tested according to the standard ASTM D3835-16.

[0040] Furthermore, 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 retardant includes one or more of decabromodiphenyl ethane, brominated polystyrene, brominated polycarbonate, brominated epoxy resin, pentabromobenzyl polyacrylate, or bromotriazine.

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

[0043] Specifically, the phosphorus-based flame retardant includes one or more of trimethyl phosphate, red phosphorus, tricresyl phosphate, tetraphenylresorcinol diphosphate, or ammonium polyphosphate.

[0044] Furthermore, the reinforcing fibers include glass fibers and / or carbon fibers.

[0045] Furthermore, the average length of the reinforcing fiber is 3 to 6 mm.

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

[0047] Furthermore, the polar group in the toughening agent is one or more of maleic anhydride, epoxy group or ester group.

[0048] Furthermore, 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] Furthermore, the voltage-resistant nylon composition also includes 0.1 to 5 parts of additives.

[0050] Furthermore, the additive is an antioxidant and / or a lubricant.

[0051] In this invention, commonly used antioxidants can be selected according to existing technology, such as, but not limited to, one or more of hindered phenolic antioxidants, phosphite antioxidants, diphenylamine antioxidants, or thioether antioxidants.

[0052] Specifically, the hindered phenolic antioxidant is one or more of N,N'-hexamethylene bis(3,5-di-tert-butyl-4-hydroxyphenylpropionamide) (Irganox 1098), pentaerythritol tetrakis[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), 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-tetraoxaspirocycloundecane (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-tolyl) pentaerythritol phosphite (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 distearate thiodipropionate, dilaurate thiodipropionate, or pentaerythritol-based dodecathiopropyl ester.

[0056] In this invention, commonly used lubricants can be selected based on existing technology. For example, 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 may be calcium stearate and / or zinc stearate.

[0058] The polyethylene lubricant may be polyethylene wax.

[0059] The amide lubricant may be one or more of oleamide lubricants, EBS amide lubricants, or erucamide lubricants.

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

[0061] The silicone lubricant may be polydimethylsiloxane.

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

[0063] The components are mixed evenly to obtain a premix, and the premix is ​​melt-blended and extruded to obtain a voltage-resistant nylon composition.

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

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

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

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

[0068] This invention also protects the use of the above-described voltage-resistant nylon composition in the manufacture of household goods, electronic components, and household appliances. In particular, it protects the use of the above-described voltage-resistant nylon composition in the manufacture of parts with good voltage resistance and mechanical properties. Specifically, it protects its use in the manufacture of connectors in the photovoltaic industry, such as materials for electrical switches, connectors, and low-voltage circuit breakers.

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

[0070] This invention provides a voltage-resistant nylon composition. By adding a nucleating agent and a charge-scavenging agent to the nylon resin, the nucleating agent can effectively adjust the aggregation morphology of the nylon composition, and the charge-scavenging agent can reduce the charge accumulation in the system, thereby improving the voltage resistance of the nylon composition, while also exhibiting good flame retardant properties. Detailed Implementation

[0071] The present invention will be further described below with reference to specific embodiments, but the embodiments do not limit the present invention in any way. Unless otherwise stated, 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 the various embodiments and comparative examples 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 Kaisai 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 Material Co., Ltd.;

[0078] Nucleating agent:

[0079] Nucleating agent 1: Polyethylene glycol diamine, 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 trapping agent:

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

[0083] Charge scavenger 2: Aromatic polyimide, Visimiderm TM XL001 was 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: decabromodiphenyl ethane, 8010, purchased from Albemarle;

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

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

[0089] Additives:

[0090] Antioxidant: Inganox@1098; Lubricant: LOXIOL G32; Both antioxidants and lubricants are commercially available, and the same antioxidants and lubricants were used in parallel experiments of the examples and comparative examples.

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

[0092] The components are mixed evenly to obtain a premix, which is then fed into a twin-screw extruder for melt blending, extrusion granulation to obtain a nylon composition. The twin-screw extruder has a screw length-to-diameter ratio of 40 to 48:1, a barrel temperature of 270 to 300°C, and a screw speed of 150 to 400 rpm.

[0093] 3. Testing Method:

[0094] (1) Flame retardant performance test: The nylon compositions in each example and comparative example were injection molded into strips with dimensions of 125mm×13mm×1.0mm, and flame retardant tests were conducted in accordance with UL 94-2013 standard;

[0095] (2) Water absorption test: The water absorption of the nylon compositions in each example and comparative example was measured according to ASTM D570-22 standard by injection molding 125mm×13mm×3.0mm specimens.

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

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

[0098] Table 1. Amounts of each component in the voltage-resistant nylon compositions of Examples 1-13 (unit: parts by weight)

[0099]

[0100]

[0101] Table 2. Amounts (parts by weight) and properties of each component in the voltage-resistant nylon compositions of Comparative Examples 1–4

[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 trap 1 / / 4 6 Flame retardant 1 8 8 8 8 Reinforcing fibers 25 25 25 25 enhancer 15 15 15 15 antioxidants 0.5 0.5 0.5 0.5 lubricant 0.3 0.3 0.3 0.3 Flame retardant rating (1.0mm) 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 and low water absorption, while also having good flame retardant properties. Specifically, the nylon composition meets the V-0 flame retardant requirement, while having an insulation resistance of not less than 400 MΩ, a leakage current of not more than 50 μA, and a water absorption rate of not more than 2.5%.

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

[0105] As can be seen from Comparative Examples 1 to 4, the voltage resistance of nylon compositions prepared by using only nucleating agents or charge trapping agents cannot meet the requirements.

[0106] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. Those skilled in the art can make other variations or modifications based on the above description. It is neither necessary nor possible to exhaustively describe all embodiments here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A voltage-resistant nylon composition, characterized in that, Includes the following components, calculated in parts by weight: 28-85 parts of nylon resin; Nucleating agent: 1.5-4.5 parts; 1.5 to 6.5 parts of charge-trapping agent; 4-12 parts flame retardant; 8-32 parts of reinforcing fiber; The toughening agent is 8-20 parts; the charge-scavenging agent is m-aminobenzoic acid; the nylon resin is a mixture of aliphatic nylon resin and aromatic nylon resin, wherein the mass ratio of aliphatic nylon resin to aromatic nylon resin in the nylon resin is not higher than 10:1; the nucleating agent includes amide nucleating agents and / or magnesium sulfate whiskers.

2. The nylon composition according to claim 1, characterized in that, The flame retardant includes one or more of the following: brominated flame retardants, nitrogen-based flame retardants, or phosphorus-based flame retardants.

3. The nylon composition according to claim 1, characterized in that, The toughening agent is a polyolefin containing polar groups.

4. The nylon composition according to claim 3, characterized in that, The polar groups in the toughening agent are one or more of maleic anhydride, epoxy groups, or ester groups.

5. The nylon composition according to claim 1, characterized in that, The nylon composition further includes 0.1 to 5 parts of additives; the additives are antioxidants and / or lubricants.

6. A method for preparing the nylon composition according to any one of claims 1 to 5, characterized in that, Includes the following steps: The components are mixed evenly to obtain a premix, and the premix is ​​melt-blended and extruded to obtain a voltage-resistant nylon composition.

7. The use of the nylon composition according to any one of claims 1 to 5 in the preparation of household goods, electronic components and household appliances.

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