High voltage resistant polyamide composition

Abstract

The present invention relates to a polyamide composition comprising, based on the total weight of the polyamide composition, (A) 40% to 80% by weight of a polyamide containing at least one monomer unit having at least eight carbon atoms, and (B) 20% to 60% by weight of a lamellar-shaped filler having a diameter / thickness ratio of at least 70, and also to its use as an insulating material that can withstand high electrical stress.

Description

[Technical Field]

[0001] The present invention relates to high-voltage resistant polyamide compositions and their use as insulating materials that can withstand high electrical stress, particularly as insulating plastic materials in high-voltage power transmission and distribution systems.

[0002] Background of the Invention High-voltage power transmission and distribution require insulating materials in almost all applications, including circuit breakers, reclosers, and transformers. Insulating materials in such applications must be able to withstand the high electrical stress resulting from the applied high voltage, and therefore require excellent dielectric properties. Ceramics, as well as thermosetting materials such as epoxy resins and silicone rubber, are commonly used as insulating materials in many applications. However, because thermoplastic materials generally do not have sufficient high-voltage resistance, they have rarely been developed as insulating materials for high-voltage power transmission and distribution applications.

[0003] U.S. Patent No. 6,653,571 (B1) describes a high-voltage electrical insulating material comprising a polymer material and an ester compound having a fluorinated alkyl-terminated group as a water-repellent additive. The polymer materials of the insulating material described in this patent include polyolefins, olefin copolymers, substituted polyolefins, substituted olefin copolymers, particularly ethylene-vinyl acetate copolymers (EVA); linear low-density polyethylene (LLDPE); acrylic rubber, silicone polymers, epoxy resins, polyurethanes, and polyethers. The patent states that the electrical insulating material can be used in a wide variety of applications where electrical components are exposed to voltages exceeding approximately 1 kV.

[0004] The application of some thermoplastics as insulating materials is hindered by other properties in addition to insufficient high-voltage tolerance. For example, polyamides, a general-purpose engineering thermoplastic, have not been well developed for high-voltage insulation applications due to their inherent hygroscopic properties.

[0005] U.S. Patent Application Publication No. 20180033519(A1) describes thermoplastic composites for insulating and / or sealing electrical components, comprising a polymer matrix and micro-sized and / or nano-sized fillers. The polymer matrix may be polyamide, polyimide, fluoropolymer, polyester, polyolefin, polystyrene, cyclic olefin copolymer, or blends thereof. The fillers may be in the form of microparticles, microtubes, microplatelets, microfibers, nanoparticles, nanotubes, nanoplatelets, nanofibers, or blends thereof. This patent application does not mention high voltage resistance of any thermoplastic composite. In particular, polyamide is mentioned as an option for the polymer matrix in this patent application, but no applications or performance tests of this material are described.

[0006] Developing thermoplastic polyamide materials with desirable high-voltage insulation performance is extremely difficult.

[0007] Summary of the Invention The object of the present invention is to provide a polyamide composition useful as an insulating material for high-voltage applications, which has high voltage resistance and preferably exhibits excellent toughness, color stability, and / or low hygroscopicity.

[0008] Surprisingly, the inventors have found that this objective can be achieved by a polyamide composition comprising a long-chain polyamide and a lamellar filler having a high diameter-to-thickness ratio (D / T ratio).

[0009] Therefore, in the first aspect, the present invention is Based on the total weight of the polyamide composition, (A) A polyamide containing 40% to 80% by weight of at least one monomer unit having at least 8 carbon atoms, (B) A lamellar-shaped filler having a diameter / thickness ratio of at least 70, in an amount of 20% to 60% by weight. Provided is a polyamide composition comprising

[0010] In a second aspect, the present invention relates to the use of the polyamide composition described herein as an insulating material in high-voltage power transmission and distribution systems, particularly in circuit breakers, reclosing switches, and transformers.

[0011] In a third aspect, the present invention relates to an article manufactured using the polyamide composition described herein, particularly an article in a high-voltage power transmission and distribution system such as a circuit breaker, a reclosing switch, and a transformer.

[0012] Detailed Description of the Invention The present invention will be described in detail below. It should be understood that the present invention can be embodied in many different ways and should not be construed as limited to the embodiments described herein.

[0013] The singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise. The terms "comprise", "comprising", etc. are used interchangeably with "contain", "containing", etc. and should be construed in an open, non-limiting sense. That is, for example, additional components or elements may be present. The expression "consists of" or a cognate expression can be subsumed within "comprises" or a cognate expression.

[0014] Various aspects of the present invention are defined in more detail. Each such defined aspect can be combined with any other aspect(s), unless clearly indicated otherwise. In particular, any property indicated as preferred can be combined with any other property or properties generally described or indicated as preferred.

[0015] In this specification, any reference to “some embodiments” means that certain components, quantities, compositions, or properties described in relation to the embodiments are included in some exemplary embodiments of the present invention. Therefore, occurrences of the phrase “in some embodiments” or similar phrases in various places throughout this description do not necessarily all refer to the same embodiment, although they may. Furthermore, components, quantities, compositions, or properties can be combined in any suitable manner that will become apparent to those skilled in the art from the disclosures in more embodiments.

[0016] In this specification, the terms “high-voltage” and “high voltage” refer to alternating (AC) voltages of 1 kV or greater, particularly 1.5 kV or greater, and more specifically 2.0 kV or greater.

[0017] In this specification, the term "diameter / thickness ratio" refers to the value given by the following formula: D / T = 3π × (D a / D s ) 2 / 2 During the ceremony, D a This is based on static laser diffraction in accordance with GB / T 19077-2016, determining the particle size (D 50 ) and D s This is based on the particle size (D) determined by gravity liquid sedimentation method in accordance with ISO 13317-3:2001. 50 )

[0018] The method for determining the "diameter / thickness ratio" is publicly known, for example, described by Daniel Gantenbein et al., "Determining the size distribution-defined aspect ratio of platy particles," Applied Clay Science 53 (2011), pp. 544-552. In this specification, the term "D / T ratio" is also used as an abbreviation for diameter / thickness ratio.

[0019] As used herein, the term “structural unit,” also called “monomer unit,” is intended to refer to the smallest molecular residue produced after polymerization from each monomer molecule. For example, PA6 has a structural unit of the type -NH(CH2)5CO-, PA66 has two structural units, namely -NH(CH2)6NH- and -CO(CH2)4CO-, and so on.

[0020] As used herein, the term “repeating unit” is intended to refer to the smallest unit in a polymer having the same chemical composition. A repeating unit may consist of one or more structural units. For example, PA6 has the same repeating unit as its structural unit, namely -NH(CH2)5CO-, and PA66 has the repeating unit -NH(CH2)6NHCO(CH2)4CO-, which consists of two structural units, namely -NH(CH2)6NH- derived from a diamine monomer and -CO(CH2)4CO- derived from a dicarboxylic acid monomer.

[0021] Polyamide composition In the first aspect, the present invention is Based on the total weight of the polyamide composition, (A) A polyamide containing 40% to 80% by weight of at least one monomer unit having at least 8 carbon atoms, (B) A lamellar-shaped filler having a diameter / thickness ratio of at least 70, in an amount of 20% to 60% by weight. The present invention provides a polyamide composition containing [a specific compound / component].

[0022] (A) Polyamide Polyamides, as is well known in the art, refer to polymers that contain a repeating amide moiety (-CONH-) in the main chain of the polymer. Generally, polyamides are composed of many identical repeating units linked by covalent bonds. It is well known that the repeating units of polyamides are typically derived from one or more monomers selected from lactams, amino acids, combinations of dicarboxylic acids and diamines, and combinations of dicarboxylic acid chlorides and diamines.

[0023] Suitable polyamides as component (A) in the polyamide composition according to the invention are of the formula (I):

Chemical formula

[0024] The linear C 1 -alkylene, C 7-24 -alkylene, or C 8-20 -alkylene given to R in formula (I) may be unsubstituted or substituted with C 9-16 -alkyl, especially C 1-8 -alkyl. 1-6

[0025] Polyamides having repeating units of formula (I) are typically derived from at least one aliphatic monomer selected from lactams, amino acids, or any combination thereof. Suitable lactams preferably have 8 to 25 carbon atoms, more preferably 9 to 21 carbon atoms, particularly 10 to 17 carbon atoms. Examples of lactams include, but are not limited to, caprylolactam (2-azacyclononanone), caprinolactam (azacycloundecan-2-one), laurolactam (2-azacyclotridecanone), or any combination thereof. Suitable amino acids preferably have 8 to 25 carbon atoms, more preferably 9 to 21 carbon atoms, particularly 10 to 17 carbon atoms. Examples of amino acids include, but are not limited to, 8-aminocaprylic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, or any combination thereof.

[0026] ​Alternatively, a suitable polyamide as component (A) in the polyamide composition according to the present invention is a polyamide of formula (II): [ka] (In the formula, R 2 This refers to unsubstituted or substituted linear C chains. 4-24 -Alkylene, preferably C 4-20 -Alkylene, more comfortably 4-16 -It is an alkylene, R 3 C is aliphatic or aromatic. 4-30 -Hydrocarboxylen, preferably C 6-20 -Hydrocarbylene, farC 6-16 -It is hydrochlorbilene, However, -NH-R 2 -NH- part and [ka] (At least one of the parts has at least 8 carbon atoms.) It may have repeating units.

[0027] R in equation (II) 2 A linear chain C is given to 4-24 -Alkylene, C 4-20 -Alkylene, or C 4-16 -Alkylene may be unsubstituted, C 1-8 -Alkyl, especially C 1-6 - May be substituted with alkyl.

[0028] R in equation (II) 3 The C given to 4-30 - Hydrocarbylene, C 6-20 - Hydrocarbylene, or C 6-16 -Hydrocarbylene may be unsubstituted or substituted alkylene, cycloalkylene or arylene. Preferably, R 3 C 6-20 -Alkylene group, C 6-20 -Cycloalkylene group, or C 6-20-Arylene group, more preferably C 6-16 -Alkylene group, C 6-16 -Cycloalkylene group, or C 6-16 - This is an arylene group.

[0029] Polyamides having the repeating unit of formula (II) are typically derived from aliphatic or aromatic dicarboxylic acids or dicarboxylic acid chlorides having 6 to 32 carbon atoms, and aliphatic diamines having 4 to 24 carbon atoms, wherein at least one of the diamine and the dicarboxylic acid or dicarboxylic acid chloride has at least 8 carbon atoms.

[0030] Aliphatic diamines may be linear or branched. Examples of aliphatic diamines include 1,5-hexanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine, 1,18-octadecanediamine, 1,20-eicosanediamine, 1,22-docosanediamine, 2,3-dimethylheptane-1,7-diamine, 2,4-dimethylheptane-1,7-diamine, and 2,5-dimethylheptane-1,7-diamine. Examples include, but are not limited to, amines, 2,2-dimethylheptane-1,7-diamine, 2-methyloctane-1,8-diamine, 1,3-dimethyloctane-1,8-diamine, 1,4-dimethyloctane-1,8-diamine, 2,4-dimethyloctane-1,8-diamine, 3,4-dimethyloctane-1,8-diamine, 4,5-dimethyloctane-1,8-diamine, 2,2-dimethyloctane-1,8-diamine, 3,3-dimethyloctane-1,8-diamine, 4,4-dimethyloctane-1,8-diamine, 5-methylnonane-1,9-diamine, and any combination thereof.

[0031] Examples of dicarboxylic acids include, but are not limited to, adipic acid, pimelic acid, suberic acid, nonanoic acid, sebacic acid, undecanediic acid, dodecanediic acid, tridecanediic acid, tetradecanediic acid, pentadecanediic acid, hexadecanedioic acid, octadecanediic acid, terephthalic acid, isophthalic acid, and any combination thereof.

[0032] Examples of dicarboxylic acid chlorides include, but are not limited to, adipoyl dichloride, heptanedioyl dichloride, octanoyl chloride, azerayl dichloride, sebacoyl dichloride, undecanedioyl dichloride, lauroyl dichloride, tridecanedioyl dichloride, tetradecanedioyl dichloride, pentadecanedioyl dichloride, hexadecanedioyl dichloride, octadecanedioyl dichloride, terephthaloyl chloride, isophthaloyl acid, and any combination thereof.

[0033] For example, the polyamide used as component (A) can be selected from the group consisting of PA11, PA12, PA510, PA610, PA612, PA1010, PA1012, PA1212, PA9T, PA10T, PA11T, PA12T, or any combination thereof.

[0034] Useful polyamides may also be blends or copolymers of polyamides as described above (copolyamides). There are no limitations on the type of copolyamide, and they may be block copolymers, random copolymers, graft copolymers, or alternating copolymers, such as PA10T / 610, PA5T / 510, PA10T / 1010, PA9T / 612, PA9T / 1010, or any combination thereof.

[0035] In some embodiments of the present invention, polyamides having repeating units of formula (II) are particularly useful as component (A) in the polyamide composition, with PA1212, PA610, and PA9T being more preferred.

[0036] The polyamide as component (A) in the polyamide composition according to the present invention may have any suitable molecular weight, without limitation. The relative viscosity of the polyamide is in the range of 1.8 to 4.0, measured in 96% by weight sulfuric acid at 25°C.

[0037] The polyamide as component (A) in the polyamide composition according to the present invention may have any suitable melting temperature, without limitation. For example, the melting temperature is in the range of 150 to 350°C, as measured by differential scanning calorimetry (DSC).

[0038] Component (A) may be present in the polyamide composition according to the present invention in an amount of 40% to 80% by weight, for example, 45% to 70% by weight, or 50% to 65% by weight, based on the total weight of the polyamide composition.

[0039] The polyamides disclosed herein should not be limited to those prepared from unused crude oil monomers, and may be entirely or at least partially bio-based, or derived from waste flows or recycling activities. In other words, the polyamides used in the present invention may be based on renewable materials, secondary raw materials, or recycled raw materials. For example, PA610, PA1212, PA9T, PA10T, and PA11T, which are useful as component (A) in the present invention, can be prepared, obtained, or derived from monomers obtained in a remonomerization process.

[0040] (B) Lamellar-shaped filler The polyamide composition according to the present invention comprises, as component (B), a lamellar-shaped filler having a diameter / thickness ratio of at least 70, preferably at least 100 (also referred to herein as a "lamellar filler").

[0041] There is no particular upper limit on the diameter / thickness ratio. Lamellar fillers may have a diameter / thickness ratio of 250 or less, for example, 200 or less, or 150 or less. Lamellar fillers may have a diameter / thickness ratio within the range of 70 to 250, or 70 to 200, or 70 to 150, preferably within the range of 100 to 250, or 100 to 200, or 100 to 150.

[0042] The lamellar filler was measured using a laser diffraction particle size distribution analyzer and had a particle size D in the range of 1 to 30 microns (μm), more preferably in the range of 3 to 20 μm. 50 It may have.

[0043] The lamellar filler may be a microplatelet or nanoplatelet, preferably a microplatelet. Materials useful as lamellar fillers may be organic materials such as polymer materials that do not melt during processing (such as blending and molding) of the polyamide composition, or inorganic materials such as refractory synthetic compounds or natural minerals. Preferably, the lamellar filler is an inorganic material. Examples of materials useful as inorganic lamellar fillers include, but are not limited to, boron nitride, kaolin, chalk, talc, calcium carbonate, silicate, graphite, mica, vermiculite, montmorillonite, and glass.

[0044] The lamellar filler may be present in the polyamide composition according to the present invention in an amount of 20% to 60% by weight, preferably 25% to 55% by weight, and more preferably 25% to 50% by weight, based on the total weight of the polyamide composition.

[0045] In particular, if the polyamide composition contains at least one additional filler in an amount of 5% by weight or less, the lamellar filler may be present in the polyamide composition according to the present invention in an amount of 20% to 60% by weight, preferably 30% to 55% by weight, and more preferably 35% to 50% by weight, based on the total weight of the polyamide composition.

[0046] (C) Additional filler In some cases, the polyamide composition according to the present invention may also contain additional fillers, i.e., fillers other than component (B) (i.e., lamellar fillers having a diameter / thickness ratio of at least 70).

[0047] The additional fillers may be of various types, not particularly limited, such as fibers, whiskers, platelets, and particles. The additional filters can be selected from fibrous fillers and particulate fillers in particular.

[0048] Examples of fibrous fillers include, but are not limited to, metal fibers such as brass fibers, stainless steel fibers, steel fibers, metallized inorganic fibers, metallized synthetic fibers, glass fibers, carbon fibers, boron fibers, asbestos fibers, ceramic fibers, mineral fibers, basalt fibers, kenaf fibers, jute fibers, bamboo fibers, flax fibers, hemp fibers, bagasse fibers, cellulosic fibers, sisal fibers, and coir fibers. Preferably, the fibrous filler can be selected from metallized synthetic fibers, glass fibers, carbon fibers, ceramic fibers, mineral fibers, basalt fibers, kenaf fibers, and jute fibers, with glass fibers and carbon fibers being more preferred among these.

[0049] There are no particular restrictions on the fiber length and fiber diameter of the fibrous filler. For example, chopped fibers or continuous fibers having a length in the range of 1 to 10 mm, preferably 2 to 6 mm, may be used as the starting material for the reinforcing agent. During processing of the polyamide composition, for example during kneading, the fibers will be broken down to lengths of several hundred microns present in the resulting molded product. The fiber diameter is generally in the range of 3 to 20 μm, preferably 7 to 13 μm. The fibrous filler may have a cross-section with an aspect ratio in the range of 1:1 to 5:1.

[0050] Glass fibers are particularly useful as additional fillers in the polyamide composition according to the present invention. The glass fibers may be surface-treated with a silane coupling agent, such as a vinylsilane coupling agent, an acrylicsilane coupling agent, an epoxysilane coupling agent, and an aminosilane coupling agent, preferably an aminosilane coupling agent. The silane coupling agent may be dispersed in a sizing agent. Examples of sizing agents include acrylic compounds, acrylic / maleic acid derivative modified compounds, epoxy compounds, urethane compounds, urethane / maleic acid derivative modified compounds, and urethane / amine modified compounds.

[0051] The particulate filler may be organic or inorganic, and may have a variety of particle sizes, from fine dust particles to coarse particles. Examples of materials that can be used as inorganic particulate fillers include, but are not limited to, kaolin, chalk, wollastonite, talc, calcium carbonate, silicate, titanium dioxide, zinc oxide, graphite, mica, vermiculite, montmorillonite, and glass particles (e.g., glass beads).

[0052] In some embodiments, the additional filler as component (C) is selected from glass fibers. The glass fibers may be any other high modulus or high strength glass fibers, such as E glass fibers, A glass fibers, D glass fibers, AR glass fibers, C glass fibers and S glass fibers, or M glass fibers and HMG glass fibers.

[0053] If included, additional fillers may be present in the polyamide composition according to the present invention in an amount of 20% by weight or less, 15% by weight or less, 10% by weight or less, or 5% by weight or less.

[0054] In some embodiments, the additional filler may be present in an amount of, for example, 5% to 20% by weight, more preferably 5% to 15% by weight, based on the total weight of the polyamide composition.

[0055] Therefore, in some embodiments, the present invention is Based on the total weight of the polyamide composition, (A) A polyamide containing 40% to 80% by weight of at least one monomer unit having at least 8 carbon atoms, (B) A lamellar-shaped filler having a diameter / thickness ratio of at least 70, in an amount of 20% to 60% by weight, (C) Fillers other than lamellar-shaped fillers having a diameter / thickness ratio of at least 70, in an amount of 0% to 20% by weight. The present invention provides a polyamide composition containing [a specific compound / component].

[0056] It will be understood that the sum of the lamellar filler as component (B) and the additional filler as component (C) does not exceed 60% by weight based on the total weight of the polyamide composition. Preferably, the sum of the lamellar filler as component (B) and the additional filler as component (C) does not exceed 55% by weight, particularly 50% by weight, based on the total weight of the polyamide composition.

[0057] D) Additives Depending on the circumstances, the polyamide composition according to the present invention may also contain at least one additive, such as a UV absorber, a hindered amine light stabilizer, an antioxidant, a lubricant, a nucleating agent, a colorant, a release agent, a drip inhibitor, an impact modifier, a compatibilizer, a plasticizer, a surfactant, a flame retardant, a flame retardant coordinator, a coupling agent, an antimicrobial agent, an antistatic agent, and any combination thereof.

[0058] At least one additive, if present, may be present in conventional amounts. For example, the polyamide composition may contain at least one additional additive in a total amount of 25% by weight or less, or 15% by weight or less, or 10% by weight or less, based on the total weight of the polyamide composition.

[0059] In some embodiments, the polyamide composition according to the present invention includes a UV absorber. There are no particular limitations on the UV absorber useful in the polyamide composition according to the present invention, and any known UV absorber can be selected from, for example, hydroxyphenylbenzotriazole, hydroxyphenyltriazine, benzophenone, cyanoacrylate, benzooxazinon, benzylidene malonate, and salicylic acid esters, as well as any combination thereof. Examples of useful commercially available UV absorbers include Tinuvin Registered Trademark 328 (2-(2'-hydroxy-3',5'-di-tert-amylphenyl)benzotriazole), Tinuvin Registered Trademark 360 (2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-1,1,3,3-tetramethylbutyl)phenol]), Tinuvin Registered Trademark 900 (2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole), and Tinuvin Registered Trademark 1577ED (2-(4,6-diphenyl-1,3,5- Examples include, but are not limited to, triazine-2-yl)-5-hexyloxyphenol, Tinuvin registered trademark 1600 (2,4-bis-biphenyl-6-[2-hydroxy-4-(2-ethylhexyloxy)phenyl]-1,3,5-triazine), Cyasorb registered trademark UV-531 (2-hydroxy-4-octyloxy(cctyloxy)benzophenone), and Cyasorb registered trademark UV-1164 (2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5-(octyloxy)phenol).

[0060] If included, UV absorbers may be present in an amount of 0.05% to 5% by weight, preferably 0.1% to 2% by weight, based on the total weight of the polyamide composition.

[0061] In some embodiments, the polyamide composition according to the present invention comprises a hindered amine light stabilizer (HALS). There are no particular limitations on the hindered amine light stabilizer useful in the polyamide composition according to the present invention, and any known hindered amine light stabilizer can be selected, for example, monomer compounds, oligomer compounds, and polymer compounds based on 2,2,6,6-tetramethylpiperidine. Examples of useful commercially available UV absorbers include Chimassorb Registered Trademark 944 (poly-{6-[(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidyl)imino)}) and Chimassorb Registered Trademark 2020 (a polymer using 1,6-hexanediamine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl), and 2,4,6-trichloro-1,3,5-triazine, containing N-butyl-1-butanamine and N-butyl-2,2,6,6-tetramethyl-4-piperidine) Examples include, but are not limited to, those of the reaction product with lysineamine, Tinuvin Registered Trademark 123 (bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate), Tinuvin Registered Trademark 770 (bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate), Tinuvin Registered Trademark 292 (bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate), and Cyasorb Registered Trademark UV-3529 (a polymer using morpholine-2,4,6-trichloro-1,3,5-triazine with 1,6-hexanediamine and N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)).

[0062] If present, the hindered amine light stabilizer may be present in an amount of 0.05% to 3% by weight, preferably 0.1% to 1% by weight, based on the total weight of the polyamide composition.

[0063] In some embodiments, the polyamide composition according to the present invention includes an antioxidant. There are no particular limitations on the antioxidant useful in the polyamide composition according to the present invention, and any known antioxidant can be selected, such as hindered phenol antioxidants, phosphite antioxidants, phosphonite antioxidants, aromatic amine antioxidants, and any combination thereof. Examples of useful commercially available UV absorbers include Irganox Registered Trademark 1098 (N,N'-(hexane-1,6-diyl)bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanamide]), Irganox Registered Trademark 1010 (pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)), Irganox Registered Trademark 1726 (2,4-bis[(dodecylthio)methyl]-o-cresol), Irganox Registered Trademark 1035 (2,2-thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]), and Irgafos Registered Trademark 168 (tris(2,4-di-tert-butyl Examples include, but are not limited to, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, Doverphos registered trademark S-9228 (bis(2,4-dicumylphenyl)pentaerythritol diphosphite), Doverphos registered trademark TNPP (trisnonylphenol phosphite), ULTRANOX registered trademark 627 (bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphonite), Doverphos registered trademark S-9228PC (bis(2,4-dicumylphenyl)pentaerythritol diphosphite), and Hostanox registered trademark P-EPQ (tetrakis(2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4'-diylbisphosphonite).

[0064] If present, antioxidants may be present in an amount of 0.01% to 5% by weight, for example, 0.1% to 2% by weight, based on the total weight of the polyamide composition.

[0065] In some embodiments, the polyamide composition according to the present invention includes a lubricant. The lubricant useful for the polyamide composition according to the present invention is not particularly limited and can be selected from any known lubricant, such as long-chain fatty acids and their salts, such as stearic acid or behenic acid and their salts; esters or amides of saturated or unsaturated aliphatic carboxylic acids, such as N,N'-ethylenedi(stearamide), glycerol distearate, glycerol tristearate, glycerol monopalmitate, glycerol trilaurate, glycerol monobehenate, and pentaerythritol tetrastearate; and waxes, such as natural waxes, montan wax, paraffin wax, polyethylene wax, and polypropylene wax.

[0066] If included, the lubricant may be present in an amount of 0.1% to 5% by weight, for example, 0.3% to 3% by weight, based on the total weight of the polyamide composition.

[0067] In some embodiments, the polyamide composition according to the present invention includes a nucleating agent. There are no particular limitations on the nucleating agent useful for the polyamide composition according to the present invention, and any known nucleating agent can be selected from, for example, talc, boron nitride, mica, kaolin, alkali metal or alkaline earth metal carbonates, bicarbonates or sulfates, alkali metal titanates, silicon nitride, and molybdenum disulfide.

[0068] If present, the nucleating agent may be present in an amount of 0.01% to 5% by weight, preferably 0.01% to 2% by weight, based on the total weight of the polyamide composition.

[0069] combination With respect to components A), B), C), and D), it will be understood that any of the choices for molecular species and / or amounts described herein, either generally or as preferred examples, can be combined in any way without any limitation. For example, the present invention includes combinations of a component in a general range of amounts with other components in any preferred range of amounts, or combinations of a component in a preferred range of amounts with other components in a general range of amounts.

[0070] The following embodiments illustrate examples of the formulation of the polyamide composition according to the present invention.

[0071] In some embodiments, the polyamide according to the present invention is Based on the total weight of the polyamide composition, (A) A polyamide containing 40% to 80% by weight of at least one monomer unit having at least 8 carbon atoms, (B) A lamellar-shaped filler having a diameter / thickness ratio of at least 70, in an amount of 20% to 60% by weight, (C) Fillers other than lamellar-shaped fillers having a diameter / thickness ratio of at least 70, in an amount of 0% to 20% by weight, (D) Additives in an amount of 0% to 25% by weight and Includes.

[0072] In some further embodiments, the polyamide according to the present invention is Based on the total weight of the polyamide composition, (A) A polyamide containing 45% to 70% by weight of at least one monomer unit having at least 8 carbon atoms, (B) A lamellar-shaped filler having a diameter / thickness ratio of at least 70, in an amount of 25% to 55% by weight, (C) Fillers other than lamellar-shaped fillers having a diameter / thickness ratio of at least 70, in an amount of 0% to 20% by weight, (D) Additives in an amount of 0% to 25% by weight and Includes.

[0073] In further embodiments, the polyamide according to the present invention is Based on the total weight of the polyamide composition, (A) A polyamide containing 50% to 65% by weight of at least one monomer unit having at least 8 carbon atoms, (B) A lamellar-shaped filler having a diameter / thickness ratio of at least 70, in an amount of 25% to 50% by weight, (C) Fillers other than lamellar-shaped fillers having a diameter / thickness ratio in the range of 0% to 20% by weight, (D) Additives in an amount of 0% to 25% by weight and Includes.

[0074] In some specific embodiments, the polyamide according to the present invention is Based on the total weight of the polyamide composition, (A) A polyamide containing 45% to 70% by weight of at least one monomer unit having at least 8 carbon atoms, (B) A lamellar-shaped filler having a diameter / thickness ratio of at least 70, in an amount of 25% to 50% by weight, (C) Fillers other than lamellar-shaped fillers having a diameter / thickness ratio of at least 70, in an amount of 5% to 20% by weight, (D) Additives in an amount of 0% to 25% by weight and Includes.

[0075] Preferably, the polyamide according to the present invention is Based on the total weight of the polyamide composition, (A) A polyamide containing 50% to 65% by weight of at least one monomer unit having at least 8 carbon atoms, (B) A lamellar-shaped filler having a diameter / thickness ratio of at least 70, in an amount of 25% to 45% by weight, (C) Fillers other than lamellar-shaped fillers having a diameter / thickness ratio of at least 70, in an amount of 5% to 15% by weight, (D) Additives in an amount of 0% to 15% by weight and Includes.

[0076] In some other specific embodiments, the polyamide according to the present invention is Based on the total weight of the polyamide composition, (A) A polyamide containing 45% to 70% by weight of at least one monomer unit having at least 8 carbon atoms, (B) A lamellar-shaped filler having a diameter / thickness ratio of at least 70, in an amount of 30% to 55% by weight, (C) Fillers other than lamellar-shaped fillers having a diameter / thickness ratio of at least 70, in an amount of 0% to 5% by weight, (D) Additives in an amount of 0% to 25% by weight and Includes.

[0077] Preferably, the polyamide according to the present invention is Based on the total weight of the polyamide composition, (A) A polyamide containing 50% to 65% by weight of at least one monomer unit having at least 8 carbon atoms, (B) A lamellar-shaped filler having a diameter / thickness ratio of at least 70, in an amount of 35% to 50% by weight, (C) Fillers other than lamellar-shaped fillers having a diameter / thickness ratio of at least 70, in an amount of 0% to 5% by weight, (D) Additives in an amount of 0% to 15% by weight and Includes.

[0078] The polyamide compositions according to the present invention can be processed by any conventional method without particular limitation. This method typically includes at least a step of compounding the components described herein. Compounding itself is a well-known technique to those skilled in the art of polymer processing and manufacturing and involves preparing a plastic formulation by mixing and / or blending the components in a molten state. Mixing can be carried out at a rotational speed in the range of 200 rpm to 320 rpm. It is understood in the art that compounding is different from blending or mixing processes carried out at a temperature lower than the melting point of the components. Compounding can be used, for example, to form a masterbatch composition. Compounding can include, for example, adding a masterbatch composition to a polymer to form a further polymer composition. Compounding can be carried out at a temperature of 220°C to 350°C.

[0079] Polyamide compositions can be processed and molded into articles of a desired form by molding methods such as compression molding, injection molding, stretch blow molding, injection blow molding, hollow molding, extrusion, casting, or thermoforming.

[0080] Use of polyamide compositions Surprisingly, as the inventors have found, the polyamide composition as an insulating material according to the present invention can exhibit excellent high-voltage resistance, while also showing good dielectric strength and electrical resistivity.

[0081] Accordingly, in a second aspect, the present invention provides the use of the polyamide compositions described herein as insulating materials in high-voltage power transmission and distribution systems.

[0082] In particular, the present invention provides the use of the polyamide compositions described herein as insulating materials in circuit breakers, reclosers, and transformers.

[0083] Goods In a third aspect, the present invention relates to articles manufactured using the polyamide compositions described herein. Articles manufactured using the polyamide compositions are useful in a variety of applications, particularly in high-voltage power transmission and distribution systems.

[0084] For example, articles manufactured using polyamide compositions may be circuit breakers, reclosers, and transformers in high-voltage power transmission and distribution systems.

[0085] Embodiment Various embodiments are listed below. It will be understood that the embodiments listed below can be combined with all aspects and other embodiments that are within the scope of the present invention.

[0086] 1. Based on the total weight of the polyamide composition, (A) A polyamide containing 40% to 80% by weight of at least one monomer unit having at least 8 carbon atoms, (B) A lamellar-shaped filler having a diameter / thickness ratio of at least 70, in an amount of 20% to 60% by weight. A polyamide composition containing the following:

[0087] 2. The polyamide composition according to Embodiment 1, wherein the polyamide is selected from PA11, PA12, PA510, PA610, PA612, PA1010, PA1012, PA1212, PA9T, PA10T, PA11T, PA12T, or any combination thereof, with PA610, PA1212, and PA9T being preferred.

[0088] 3. The polyamide composition according to Embodiment 1 or 2, wherein the polyamide is present in an amount of 45% to 70% by weight based on the total weight of the polyamide composition.

[0089] 4. The polyamide composition according to Embodiment 3, wherein the polyamide is present in an amount of 50% to 65% by weight based on the total weight of the polyamide composition.

[0090] 5. A polyamide composition according to any of the prior embodiments, wherein the diameter / thickness ratio of the lamellar-shaped filler is at least 100.

[0091] 6. A polyamide composition according to any of the preceding embodiments, wherein the diameter / thickness ratio of the lamellar-shaped filler is 250 or less.

[0092] 7. The polyamide composition according to Embodiment 6, wherein the diameter / thickness ratio of the lamellar-shaped filler is 200 or less.

[0093] 8. The polyamide composition according to Embodiment 7, wherein the diameter / thickness ratio of the lamellar-shaped filler is 150 or less.

[0094] 9. A polyamide composition according to any of the preceding embodiments, wherein the lamellar-shaped filler is selected from microplatelets or nanoplatelets of boron nitride, kaolin, chalk, talc, calcium carbonate, silicate, graphite, mica, vermiculite, montmorillonite, glass, or any combination thereof.

[0095] 10. A polyamide composition according to any of the preceding embodiments, wherein a lamellar-shaped filler is present in an amount of 25% to 55% by weight, based on the total weight of the polyamide composition.

[0096] 11. The polyamide composition according to Embodiment 10, wherein a lamellar-shaped filler is present in an amount of 25% to 50% by weight based on the total weight of the polyamide composition.

[0097] 12.C) A polyamide composition according to any of the prior embodiments, comprising an additional filler other than a lamellar-shaped filler in an amount of 20% by weight or less based on the total weight of the polyamide composition.

[0098] 13. The polyamide composition according to Embodiment 12, comprising 30% to 55% by weight of lamellar filler and 5% by weight or less of additional filler, based on the total weight of the polyamide composition.

[0099] 14. The polyamide composition according to Embodiment 13, comprising 35% to 50% by weight of a lamellar-shaped filler and 5% or less by weight of an additional filler, based on the total weight of the polyamide composition.

[0100] 15. A polyamide composition according to any of the preceding embodiments 12 to 14, wherein an additional filler is selected from glass fibers.

[0101] 16. A polyamide composition according to any of the preceding embodiments, comprising at least one additive selected from UV absorbers, hindered amine light stabilizers, antioxidants, lubricants, nucleating agents, colorants, release agents, drip inhibitors, impact modifiers, compatibilizers, plasticizers, surfactants, flame retardants, flame retardant coordinators, coupling agents, antimicrobial agents, and antistatic agents.

[0102] 17. The polyamide composition according to Embodiment 16, comprising a UV absorber in an amount of 0.05% to 5% by weight, preferably 0.1% to 2% by weight, based on the total weight of the polyamide composition.

[0103] 18. The polyamide composition according to Embodiment 16 or 17, comprising a hindered amine light stabilizer in an amount of 0.05% to 3% by weight, preferably 0.1% to 1% by weight, based on the total weight of the polyamide composition.

[0104] 19. Use of a polyamide composition according to any of the preceding embodiments as an insulating material in high-voltage power transmission and distribution systems.

[0105] 20. Use of the polyamide composition described in Embodiment 19 in circuit breakers, reclosers, and transformers.

[0106] 21. An article manufactured using a polyamide composition described in any of the preceding embodiments 1 to 18.

[0107] 22. The article according to Embodiment 21, which is an article in a high-voltage power transmission and distribution system, such as a circuit breaker, reclosing device, and transformer. [Examples]

[0108] The embodiments of the present invention will be described in more detail below with reference to examples, but these examples are provided to illustrate certain aspects of the present invention and should not be construed as limiting them.

[0109] [Table 1]

[0110] Preparation of test specimens Test specimens were prepared according to the formulations shown in Table 1 below.

[0111] All raw materials except the filler were mixed together in a Turbula T50A high-speed agitator and fed into a ZE25Ax (Berstorff) twin-screw extruder via the throat, with the filler then supplied downstream using a side feeder. The mixed materials were melt-extruded and pelletized at temperatures of 320°C for PA9T, 285°C for PA66, 275°C for PA6, 275°C for PA610, and 220°C for PA1212 to obtain polyamide compositions in pellet form. The screw diameter was 26 mm, the screw speed was 300 rpm, and the throughput was 15-30 kg / h.

[0112] The dried pellets were processed using a Krauss Maffei KM130CX injection molding machine with a clamping force of 130T and a melting temperature of 240°C to 320°C depending on the specific polyamide to obtain test specimens.

[0113] Measurement and test methods (1) Diameter / thickness ratio (D / T ratio) The D / T ratio was calculated according to the following formula. D / T = 3π × (D a / D s ) 2 / 2 During the ceremony, D a The particle size (D) is measured according to static laser diffraction, in accordance with GB / T 19077-2016 and using a Malvern Mastersizer 2000. 50 ) and D s The particle size (D) is measured according to the gravity liquid sedimentation method, in accordance with ISO 13317-3:2001, using a Micromeritics Sedigraph 5100. 50 )

[0114] (2) Mechanical properties Tensile strength, tensile modulus, tensile elongation, flexural modulus, and flexural strength were measured on 4 mm thick specimens using a Z050 testing machine (Zwick Roell, Germany) in accordance with ISO 527-1-2012. Type 1 test specimens as described in ISO 527-1-2012 were used.

[0115] The impact strength with and without a Charpy notch was measured by edgewise impact using a HIT25P testing machine (Zwick Roell, Germany) in accordance with ISO 179-1-2010. The test specimen for the test without a Charpy notch was a Type 1 specimen with dimensions of 80 mm × 10 mm × 4 mm (length × width × thickness). The test specimen for the test with a Charpy notch was a Type 1 specimen of Type A with a notch.

[0116] All test specimens were conditioned at 23°C and 50% relative humidity for 16 hours. The tests were conducted under the same conditions as the conditioning.

[0117] (3) Insulation characteristics Tracking resistance and erosion resistance under high voltage were evaluated by inclined plate testing (IPT) in accordance with GB / T 6553-2014, corresponding to IEC 60587:2007. Specimens (130 mm × 50 mm × 4 mm) were tested at voltages of 2.0 and 3.5 kV using the time to tracking method.

[0118] Dielectric strength was measured using the short-time (rapid voltage boost) method in accordance with IEC 60243-1:2013. A 2mm thick specimen was pre-conditioned at 23°C and 50% relative humidity for 24 hours and tested under a voltage application frequency of 50Hz. The voltage boost rate was 2000V / s.

[0119] Dielectric loss was measured in accordance with IEC 62631-2-1:2018. A 2 mm thick specimen was pre-conditioned at 23°C and 50% relative humidity for 96 hours and then tested at a frequency of 1 MHz.

[0120] Volume resistivity and surface resistivity were tested at 500V with a sample thickness of 3 mm in accordance with IEC 62631-3-1:2016.

[0121] The formulations and results of the tested polyamide compositions are summarized in Table 1.

[0122] [Table 2-1] [Table 2-2]

[0123] As can be seen from the results shown in Table 1, the Ex.2, Ex.3, and Ex.7 specimens according to the present invention, prepared from a polyamide composition containing PA9T and a lamellar talc filler with a high D / T ratio, showed excellent resistance to tracking and erosion under a high voltage of 2.0 kV, and no failure conditions (currents exceeding 60 mA or dielectric breakdown, ignition during testing) were observed for 213 minutes, and even for 360 minutes (i.e., 6 hours). Such excellent performance reliably meets the actual operating conditions in high-voltage power transmission and distribution applications. In contrast, specimens prepared from comparative polyamide compositions containing PA9T and a non-lamellar filler (Comp.2-Comp.5), comparative polyamide composition containing PA9T and a lamellar talc filler with a low D / T ratio (Comp.1), and comparative polyamide compositions containing PA6 or PA66 and a lamellar talc filler (Comp.6 and Comp.7) showed very poor resistance to high voltage at 2.0kV, with failure observed after less than an hour, and even after just a few minutes. Specimens of Ex.8 prepared from the polyamide composition according to the present invention, containing PA9T and a lamellar talc filler with a high D / T ratio, also showed significantly improved resistance to tracking and erosion compared to specimens prepared from comparative polyamide compositions, even with a much lower amount of lamellar talc filler.

[0124] Similarly, specimens prepared from polyamide compositions (Ex.1, Ex.4~Ex.6) containing PA9T, PA610, or PA1212 and lamellar boron nitride packing also exhibit excellent high-voltage tolerance at 2.0kV.

[0125] It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the scope or spirit of the invention. Embodiments and examples are intended to be considered merely illustrative. Accordingly, the present invention is intended to encompass modifications and variations that fall within the scope of the appended claims and their equivalents.

Claims

1. Based on the total weight of the polyamide composition, (A) A polyamide containing 40% to 80% by weight of at least one monomer unit having at least eight carbon atoms, (B) 20% to 60% by weight of a lamellar-shaped filler having a diameter / thickness ratio of at least 70 A polyamide composition containing the following:

2. The polyamide composition according to claim 1, wherein the polyamide is selected from PA11, PA12, PA510, PA610, PA612, PA1010, PA1012, PA1212, PA9T, PA10T, PA11T, PA12T, or any combination thereof, with PA610, PA1212, and PA9T being preferred.

3. The polyamide composition according to claim 1 or 2, wherein the polyamide is present in an amount of 45% to 70% by weight, or 50% to 65% by weight, based on the total weight of the polyamide composition.

4. The polyamide composition according to any one of claims 1 to 3, wherein the diameter / thickness ratio of the lamellar-shaped filler is at least 100.

5. The polyamide composition according to any one of claims 1 to 4, wherein the diameter / thickness ratio of the lamellar-shaped filler is 250 or less, or 200 or less, or 150 or less.

6. The polyamide composition according to any one of claims 1 to 5, wherein the lamellar-shaped filler is selected from microplatelets or nanoplatelets of boron nitride, kaolin, chalk, talc, calcium carbonate, silicate, graphite, mica, vermiculite, montmorillonite, glass, or any combination thereof.

7. The polyamide composition according to any one of claims 1 to 6, wherein the lamellar-shaped filler is present in an amount of 25% to 55% by weight, more preferably 25% to 50% by weight, based on the total weight of the polyamide composition.

8. C) The polyamide composition according to any one of claims 1 to 7, comprising an additional filler other than the lamellar-shaped filler in an amount of 20% by weight or less based on the total weight of the polyamide composition.

9. The polyamide composition according to claim 8, comprising 30% to 55% by weight, preferably 35% to 50% by weight, of the lamellar-shaped filler, and an amount of 5% by weight or less of the additional filler, based on the total weight of the polyamide composition.

10. The polyamide composition according to claim 8 or 9, wherein the additional filler is selected from glass fibers.

11. A polyamide composition according to any one of claims 1 to 10, comprising at least one additive selected from UV absorbers, hindered amine light stabilizers, antioxidants, lubricants, nucleating agents, colorants, release agents, drip inhibitors, impact modifiers, compatibilizers, plasticizers, surfactants, flame retardants, flame retardant coordinators, coupling agents, antimicrobial agents, and antistatic agents.

12. The polyamide composition according to claim 11, comprising a UV absorber in an amount of 0.05% to 5% by weight, preferably 0.1% to 2% by weight, based on the total weight of the polyamide composition.

13. The polyamide composition according to claim 11 or 12, comprising 0.05% to 3% by weight, preferably 0.1% to 1% by weight, of a hindered amine light stabilizer based on the total weight of the polyamide composition.

14. Use of the polyamide composition according to any one of claims 1 to 13 as an insulating material in high-voltage power transmission and distribution systems.

15. Use of the polyamide composition according to claim 14 in circuit breakers, reclosers and transformers.

16. An article manufactured using the polyamide composition described in any one of claims 1 to 13.

17. The article according to claim 16, which is an article in a high-voltage power transmission and distribution system, such as a circuit breaker, recloser, and transformer.

Images