Polyamide composition with resistance to tracking and erosion in the bevel

Abstract

This invention relates to a method for improving inclined plane tracking (IPT) performance at voltages above 1 kV using a polyamide composition. The polyamide composition comprises a) 10-50 wt% of at least one semi-crystalline aliphatic polyamide, each amide group having an average of 3-5 carbon atoms, excluding carbon atoms in the carbonyl group; b) 1-40 wt% of at least one long-chain aliphatic polyamide, each amide group having an average of equal to or more than 6 carbon atoms, excluding carbon atoms in the carbonyl group; c) 0-35 wt% of a flame retardant; d) 0-50 wt% of fiber and / or particulate filler; e) 1-25 wt% of an impact modifier; and f) 0-20 wt% of other additives.

Description

Technical Field

[0001] This invention relates to a method for improving inclined plane tracking (IPT) performance at voltages above 1 kV using a polyamide composition. The polyamide composition comprises a) 10-50 wt% of at least one semi-crystalline aliphatic polyamide, each amide group having an average of 3-5 carbon atoms, excluding carbon atoms in the carbonyl group; b) 1-40 wt% of at least one long-chain aliphatic polyamide, each amide group having an average of equal to or more than 6 carbon atoms, excluding carbon atoms in the carbonyl group; c) 0-35 wt% of a flame retardant; d) 0-50 wt% of fiber and / or particulate filler; e) 1-25 wt% of an impact modifier; and f) 0-20 wt% of other additives. The invention also relates to the polyamide composition and articles thereof. Background Technology

[0002] Since the introduction of epoxy resin in the 1950s, polymer materials have been widely used as high-voltage insulation materials. Initially, polymers were used in indoor environments. Rosenthal introduced composite insulators made of silicone in 1976. Polymer insulators can have complex shapes, and their components can be thinner than ceramic insulators. Unfortunately, polymers are much less resistant to surface discharge than ceramic materials. Therefore, several methods have been proposed to improve the high-voltage degradation resistance of polymers.

[0003] Polyamide 66 (PA 66) is a very important engineering thermoplastic polymer because it combines several desirable properties, such as high strength and rigidity, high toughness, high heat resistance, excellent abrasion resistance, good electrical properties and chemical resistance, high flowability, and excellent processability. PA 66 is widely used as an insulating material in the automotive, electrical, and electronics industries.

[0004] According to IEC 60112, the relative tracking index (CTI) is the most common test for evaluating the susceptibility of plastics to surface tracking, providing an indicator of the performance of insulating materials. CTI is an accelerated testing method under wet and contaminated conditions, which involves applying a voltage between two electrodes placed on the surface of the material.

[0005] Surface tracking (IPT) is an effective method for evaluating the corrosion resistance and tracking resistance of insulating materials under high-voltage (>1kV) discharge effects in humid conditions. Polymers are organic materials composed of molecules that are not as tightly bonded as molecules in inorganic materials such as ceramics and glass. They can degrade at temperatures much lower than ceramics. The carbon formed during degradation makes the surface conductive and leads to electrical faults, making it unable to withstand applied voltage. The formation of carbon conductive pathways on the surface is called tracking. The most common polymer materials used for high-voltage applications are silicone rubber, EPR rubber, alicyclic epoxy resins, and polycarbonate because of their excellent performance in terms of tracking resistance, corrosion resistance, hydrophobicity, and UV stability. Factors such as the type of organic filler, filler size, filler conductivity, and carbon content of the base polymer all affect the IPT value. Under normal circumstances, the voltage test range for IPT is no higher than 1kV.

[0006] CN 102732002A discloses a glass fiber reinforced PA66 / PA11 alloy with a high CTI value. The CTI value is improved through a combination of iron oxide red phosphorus removal, an anti-migration agent, and a high CTI value reagent. However, this patent application does not disclose the definition of a high CTI value reagent.

[0007] CN 102105119A discloses the application of PA 1010 and polypropylene resin in improving the toughness and flexibility of PA 66. CN 103224703A discloses that styrene-acrylonitrile can improve the toughness of polyamide composites containing PA 66 and PA 1212. This combination of polyamides primarily improves toughness, and is unrelated to the tracking resistance of the polyamide resin.

[0008] The photovoltaic (“PV”) market is shifting from 1kVA grids to 1.5kVA grids, a shift that has led to new regulations for PV connectors and junction boxes. In the field of engineering plastics, many products are used in PV applications; however, applications at high voltages, particularly 1.2kV, 1.5kV, or 2kV, have previously received little attention. Polyamides with low carbon atom numbers, such as dicarboxylic acids or lactams, like PA 6 and PA 66, are widely used in the PV market due to their good mechanical and processing properties. However, these polyamides do not meet the requirements for PV applications with voltages higher than 1.5kV. Summary of the Invention

[0009] One object of the present invention is to provide a method for improving the tracking performance of inclined surfaces at voltages above 1 kV by using long-chain aliphatic polyamides having an average of 6 carbon atoms (excluding carbon atoms in the amide groups) per amide group.

[0010] Another object of the present invention is to provide a method for improving the tracking performance of a sloped surface at voltages above 1 kV by using a polyamide composition, said composition comprising:

[0011] a) 10-50% by weight of at least one semi-crystalline aliphatic polyamide, each amide group having an average of 3-5 carbon atoms, excluding carbon atoms in the carbonyl group;

[0012] b) 1-40% by weight of at least one long-chain aliphatic polyamide, each amide group having an average of 6 or more carbon atoms, excluding carbon atoms in the carbonyl group;

[0013] c) 0-35% by weight flame retardant;

[0014] d) 0-50% by weight of fiber and / or particulate fillers;

[0015] e) 1-25% by weight of impact modifier, and

[0016] f) 0-20% by weight of other additives.

[0017] In a preferred embodiment, the long-chain aliphatic polyamide is selected from polyamide 1212, polyamide 610, polyamide 612, polyamide 1010, and polyamide 6 / 6.36.

[0018] In a preferred embodiment, based on the total weight of the polyamide composition, the flame retardant comprises (c1) 3-15% by weight of red phosphorus and (c2) 1-10% by weight of a triazine flame retardant. The triazine flame retardant is preferably melamine phosphate, bismelamine phosphate, melamine pyrophosphate, melamine polyphosphate, bismelamine pyrophosphate, dimethylpyrazine phosphate, or melamine polyphosphate.

[0019] In a preferred embodiment, the filler is glass fiber, preferably alkali-free E-glass fiber. Other additives f) may include antioxidants and lubricating dispersants.

[0020] In a preferred embodiment, the weight ratio of polyamide components a) and b) in the polyamide composition is 5:1 to 1:1, preferably 4:1 to 1:1, more preferably 3.5:1 to 2.5:1, and especially 3:1.

[0021] Compared with the prior art, the polyamide composition provided by the present invention has a high Charpy notched impact strength (≥16kJ / m at 23°C). 2 ≥8kJ / m at -40℃ 2 ) and unnotched impact strength (≥75kJ / m at 23℃) 2 ≥65kJ / m at -40℃ 2With advantages such as high CTI value (>600V), UL 94V0 thickness in 1.6mm and 0.8mm, and high IPT value (≥60 minutes at 1.5kV), it can be widely used in electrical applications such as photovoltaic connector nuts and bodies, and outdoor electrical insulation plastic parts.

[0022] Another object of the present invention is to provide an article produced from a polyamide composition that exhibits excellent resistance to tracking at voltages above 1 kV, such as 1.2 kV or higher, 1.5 kV or higher, or up to 2 kV. The article is preferably a nut or body of a photovoltaic connector or an electrically insulating plastic component.

[0023] Another object of the present invention is to provide a polyamide composition comprising...

[0024] a) 10-50% by weight of at least one semi-crystalline aliphatic polyamide, each amide group having an average of 3-5 carbon atoms, excluding carbon atoms in the carbonyl group;

[0025] b) 1-40% by weight of at least one long-chain aliphatic polyamide, each amide group having an average of 6 or more carbon atoms, excluding carbon atoms in the carbonyl group;

[0026] c) 4-25% by weight of flame retardant, comprising component c1) red phosphorus and component c2) triazine flame retardant, wherein the triazine flame retardant is preferably melamine phosphate, bismelamine phosphate, melamine pyrophosphate, melamine polyphosphate, bismelamine pyrophosphate, dimethylpyrazine phosphate or melamine polyphosphate;

[0027] d) 0-50% by weight of fiber and / or particulate fillers;

[0028] e) 1-25% by weight of impact modifier, and

[0029] f) 0-20% by weight of other additives. Detailed Implementation

[0030] Unless otherwise defined, all technical and scientific terms used herein have the meanings commonly understood by one of ordinary skill in the art to which this invention pertains. Unless otherwise stated, the following terms have the meanings assigned to them as follows.

[0031] As used in this article, the articles “a” and “an” refer to one or more (i.e., at least one) grammatical objects of the article. For example, “an element” means one or more elements.

[0032] As used herein, the term “approximately” is understood to refer to a range of numbers that a person skilled in the art would consider equivalent to the value in a context that achieves the same function or result.

[0033] As used herein, the term "additive" refers to an additive included in a formulation system to enhance its physical or chemical properties and provide desired results. Such additives include, but are not limited to, dyes, pigments, toughening agents, impact modifiers, rheology modifiers, plasticizers, thixotropic agents, natural or synthetic rubber, fillers, reinforcing agents, thickeners, opacifiers, inhibitors, fluorescent or other labeling agents, thermally degradable reducing agents, thermally resistive agents, surfactants, wetting agents, defoamers, dispersants, flow or slip agents, biocides, and stabilizers.

[0034] Unless otherwise stated, all percentages (%) are "weight percentages".

[0035] The basic definitions or descriptions given above in the general terminology or preferred areas apply to the final product and, correspondingly, to the starting materials and intermediates. These basic definitions may be combined with each other as needed, i.e., combinations between general definitions and / or their respective preferred scopes and / or embodiments.

[0036] All embodiments and preferred embodiments disclosed herein may be combined as needed, and they are also considered to be included within the scope of the invention.

[0037] The "AB" in AB-polyamide indicates that the repeating unit of AB-polyamide contains one nitrogen atom and one carbonyl group;

[0038] The “AABB” in AABB-polyamide indicates that there are two nitrogen atoms and two carbonyl groups in the repeating unit of AABB-polyamide.

[0039] Unless otherwise stated, temperature refers to room temperature and pressure refers to ambient pressure.

[0040] Unless otherwise stated, solvents refer to all organic and inorganic solvents known to those skilled in the art, excluding any type of monomer molecules.

[0041] The inventors of this invention have surprisingly discovered that polyamide compositions can improve slope tracking performance at voltages above 1 kV by using long-chain aliphatic polyamides in which each amide group has an average of 6 carbon atoms (excluding carbon atoms in the carbonyl group).

[0042] This invention provides a method for improving the tracking performance of inclined surfaces at voltages above 1 kV by using a polyamide composition, the composition comprising:

[0043] a) 10-50% by weight of at least one semi-crystalline aliphatic polyamide, each amide group having an average of 3-5 carbon atoms, excluding carbon atoms in the carbonyl group;

[0044] b) 1-40% by weight of at least one long-chain aliphatic polyamide, each amide group having an average of 6 or more carbon atoms, excluding carbon atoms in the carbonyl group;

[0045] c) 0-35% by weight of flame retardant;

[0046] d) 0-50% by weight of fiber and / or particulate fillers;

[0047] e) 1-25% by weight of impact modifier, and

[0048] f) 0-20% by weight of other additives.

[0049] The high voltage is higher than 1kV, preferably 1.2kV or higher, more preferably 1.5kV or higher, or even up to 2kV.

[0050] Number of carbon atoms per amide group

[0051] In the case of AB-polyamides, the number of carbon atoms in each amide group is defined as the number of carbon atoms between the nitrogen atom and the carbonyl group in each amide group. An example of AB-polyamide is polyamide 6, derived from its own lactam, where the number of carbon atoms between the nitrogen atom and the carbonyl group is 5; therefore, each amide group in polyamide 6 has 5 carbon atoms. Another example of AB-polyamide is polyamide 11, derived from dodecalactam, where each amide group in polyamide 11 has 10 carbon atoms.

[0052] In the case of AABB-polyamides derived from diamines and dicarboxylic acids, the number of carbon atoms in each amide group is equal to the number of carbon atoms between the two nitrogen atoms of the diamine (C2). DA The number of carbon atoms between the two carbonyl groups of dicarboxylic acids (C) DS The average value of ). In this case, the number of carbon atoms per amide group is determined by C. DA and C DS The sum divided by 2 is obtained, i.e. (C DA +C DS Dividing by 2 is necessary because two nitrogen atoms and two carboxyl groups can form two amide groups. The carbon atom between the two nitrogen atoms (C) DA This includes the carbon atoms in the diamine branch chain. The carbon atom between the two carbonyl groups (C...) DS This includes carbon atoms in the dicarboxylic acid branch. An example of AABB-polyamide is polyamide 610, produced from hexamethylenediamine and sebacic acid. Since polyamide 610 has 6 carbon atoms between two nitrogen atoms and 8 carbon atoms between two carbonyl groups, each amide group in polyamide 610 has (6+8) / 2 = 7 carbon atoms.

[0053] The number of carbon atoms per amide group in a mixture of polyamides (a) or (b) is the average number of carbon atoms in all polyamides (a) or (b), taking into account the weight ratio of polyamides (a) or (b) in the mixture.

[0054] a) Semi-crystalline aliphatic polyamides with an average of 3-5 carbon atoms per amide group

[0055] Component a) in this invention may be derived from aliphatic dicarboxylic acids and aliphatic diamines, lactams and / or amino acids, wherein the aliphatic dicarboxylic acid preferably has 4-6 carbon atoms, the aliphatic diamine preferably has 4-6 carbon atoms, and the lactam preferably has 4-6 carbon atoms, wherein the carbon atoms include all the carbon atoms constituting the dicarboxylic acid, diamine or lactam.

[0056] Component a) in this invention includes a copolyamide or blend of at least one semi-crystalline aliphatic polyamide (a) in this invention.

[0057] Examples of component a) in this invention include PA 4, PA 6, PA 56, PA 46, PA 66 and / or PA 6 / 66, preferably PA 66. PA 66 has excellent flame retardancy, and conventional PA 66 products commonly used in the polyamide industry can be appropriately selected in this invention. Preferably, PA 66 suitable for use as component a) can have a viscosity value of 90-300 ml / g, preferably 110-200 ml / g, more preferably 110-170 ml / g, measured in 96% sulfuric acid at a concentration of 0.005 g / ml according to ISO 307-2007. Suitable PA 66 can be commercially available from DuPont. 101NC 010, from AKRO-PLASTIC A. From LANXESS A30S, from BASF A.

[0058] PA6 exhibits excellent flame retardancy, and in this invention, conventional PA6 products commonly used in the polyamide industry can be appropriately selected. Preferably, the PA6 suitable for use as component a) has a viscosity value of 90-260 ml / g, preferably 110-200 ml / g, measured in 96% sulfuric acid at a concentration of 0.005 g / ml according to ISO 307-2007. Suitable PA6 can be commercially available from DuPont. 7301NC 010, from AKRO-PLASTIC B. From LANXESS B30SFN30, from BASF B.

[0059] Based on the total weight of the polyamide composition, the amount of polyamide component a) is 10-50% by weight, preferably 15-45% by weight, and particularly 20-40% by weight.

[0060] b) Long-chain aliphatic polyamides with an average of 6 or more carbon atoms per amide group

[0061] Component b) in this invention may be derived from aliphatic dicarboxylic acids and aliphatic diamines, lactams and / or amino acids, wherein the aliphatic dicarboxylic acid preferably has 6 or more carbon atoms, the aliphatic diamine preferably has 6 or more carbon atoms, and the lactam preferably has 6 or more carbon atoms, wherein the carbon atoms include all the carbon atoms constituting the dicarboxylic acid, diamine or lactam.

[0062] Based on the total weight of the polyamide composition, the amount of polyamide component b) is 1-40% by weight, preferably 5-30% by weight, more preferably 8-25% by weight, and particularly 10-25% by weight.

[0063] The aliphatic dicarboxylic acid forming the long-chain aliphatic polyamide of this invention is a conventional diacid used in the production of polyamides, preferably an aliphatic dicarboxylic acid with 6-40 carbon atoms, more preferably an aliphatic dicarboxylic acid with 6-36 carbon atoms, even more preferably an aliphatic dicarboxylic acid with 6-20 or 36 carbon atoms, and most preferably an aliphatic dicarboxylic acid with 6, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 and / or 36 carbon atoms. The aliphatic diamine forming the long-chain aliphatic polyamide of this invention is a conventional diamine used in the production of polyamides, preferably an aliphatic diamine with 6-24 carbon atoms, more preferably an aliphatic diamine with 6-18 carbon atoms, and most preferably an aliphatic diamine with 6, 8, 9, 10, 11, 12, 13 and / or 14 carbon atoms. Here, carbon atoms include all carbon atoms constituting the dicarboxylic acid or diamine.

[0064] The lactam that forms the long-chain aliphatic polyamide in this invention can be decanolamine, octylolamine, and / or dodecylolamine.

[0065] The long-chain aliphatic polyamide is preferably at least one selected from PA 7, PA 8, PA 9, PA 11, PA 12, PA 68, PA 610, PA 612, PA 614, PA 618, PA 88, PA 810, PA 812, PA 1010, PA 1012, PA 1014, PA 1018, PA 1210, PA 1212, PA 1214, PA 1218, PA 1313, PA 1410, PA 1412, PA 1414, PA 1418, and PA 6.36, more preferably PA 610, PA 1010, PA 1012, PA 1210, and / or PA 1212. In a preferred embodiment, component b) is PA 1212.

[0066] Component b) in this invention may include a blend of at least two long-chain aliphatic polyamides and / or copolyamides copolymerized from long-chain aliphatic polyamides.

[0067] The copolyamide of the long-chain aliphatic polyamide copolymer is a polyamide copolymer, wherein the building blocks of the polyamide copolymer include at least one long-chain aliphatic polyamide segment (segment A), and the remaining segments of the polyamide copolymer may be non-long-chain aliphatic polyamide segments or other long-chain segments other than segment A. Examples of the remaining segments may be PA6 or PA 66. A notable example is PA 6 / 6.36, which is a copolymer of PA 6 and PA 6.36, the latter being formed from hexamethylenediamine and C36 dicarboxylic acid. Other examples include PA 66 / 610, PA 6 / 610, and PA66 / 6 / 610.

[0068] There are no restrictions on the type of copolymer; for example, block copolymers, random copolymers, graft copolymers, or alternating copolymers are applicable to this invention.

[0069] The long-chain aliphatic polyamide in this invention can have the conventional molecular weight of a polyamide composition, and the intrinsic viscosity of the long-chain polyamide is preferably 90 to 200 ml / g, as determined by ISO 307 in a polyamide solution with a concentration of 0.005 g / ml in 96% sulfuric acid at 25°C.

[0070] In a preferred embodiment, the weight ratio of polyamide components a) and b) in the polyamide composition is 5:1 to 1:1, preferably 4:1 to 1:1, more preferably 3.5:1 to 2.5:1, and especially 3:1.

[0071] c) Flame retardants

[0072] Flame retardant c) is preferably a phosphorus-based flame retardant, a halogenated flame retardant, a nitrogen-based flame retardant, and / or a mineral-based flame retardant. It can be used in its untreated form.

[0073] Examples of mineral-based flame retardants include antimony trioxide, alkaline earth metal oxides such as zinc oxide or magnesium oxide, metal hydroxides such as magnesium hydroxide or aluminum hydroxide, and metal borates such as zinc borate.

[0074] Phosphorus-based flame retardants include inorganic and organic phosphorus-containing flame retardants.

[0075] Examples of inorganic phosphorus-containing flame retardants include red phosphorus, zinc phosphate, ammonium phosphate, ammonium pyrophosphate, and ammonium polyphosphate, with red phosphorus being the preferred choice.

[0076] Examples of organophosphorus flame retardants are ethylenediamine phosphate, piperazine phosphate, piperazine pyrophosphate, dialkyl phosphate, or combinations of dialkyl phosphate and metal phosphate salts.

[0077] The dialkyl phosphate ester can be aluminum dimethyl phosphinate, aluminum ethyl methyl phosphinate, aluminum diethyl phosphinate, aluminum methyl n-propyl phosphinate, calcium dimethyl phosphinate, magnesium dimethyl phosphinate, zinc dimethyl phosphinate, calcium ethyl methyl phosphinate, magnesium ethyl phosphinate, zinc ethyl methyl phosphinate, calcium diethyl phosphinate, magnesium diethyl phosphinate, zinc diethyl phosphinate, calcium methyl n-propyl phosphinate, magnesium methyl n-propyl phosphinate, and / or zinc methyl n-propyl phosphinate. Among these, aluminum diethyl phosphinate, zinc diethyl phosphinate, aluminum dimethyl phosphinate, and zinc dimethyl phosphinate are more preferred.

[0078] Phosphorus-containing metal salts can be Al(H2PO3)3, Al2(HPO3)3, Zn(HPO3), Al2(HPO3)3·4H2O and / or Al(OH)(H2PO3)2·2H2O. Suitable organophosphorus flame retardants are commercially available from Clariant under the names OP 1230 and OP 1400.

[0079] Nitrogen-based flame retardants are preferably triazine-based flame retardants. Examples of triazine-based flame retardants are melamine or its derivatives, such as melam, meleme, melamine cyanurate, melamine sulfate, melamine borate, melamine oxalate, melamine silicate, melamine phosphate, bismelamine phosphate, melamine pyrophosphate, melamine polyphosphate, bismelamine pyrophosphate, dimethazine phosphate or melamine polyphosphate, melam pyrophosphate, melam polyphosphate, meleme phosphate, meleme pyrophosphate, meleme polyphosphate, and phosphate esters, pyrophosphate esters, meleme neopentyl glycol borate and polyphosphate esters of higher condensation products of melamine and / or meleme. Preferred are melamine polyphosphates derived from 1,3,5-triazine compounds, wherein the average degree of condensation (n) is 20-200, and the content of the 1,3,5-triazine compound per mole of phosphorus is 1.1-2.0 mol, wherein the 1,3,5-triazine compound is selected from melamine, meliamine, melamine, cyanuramide, ammeline, cyanuramide, 2-ureidomelamine, methylguanidine, phenylmelamine, and diaminophenyltriazine. Preferably, the n value of this type of salt is typically 40 to 150, and the molar ratio of 1,3,5-triazine compound to phosphorus is 1.2 to 1.8.

[0080] An example of a halogenated flame retardant is brominated polystyrene.

[0081] Based on the total weight of the polyamide composition, the amount of flame retardant as component c) is 0-35% by weight, preferably 4-25% by weight, and particularly 8-18% by weight.

[0082] In a preferred embodiment, the flame retardant of the present invention may be selected from red phosphorus, antimony trioxide, dialkyl phosphate, a combination of dialkyl phosphate and metal phosphite salts, and triazine flame retardants.

[0083] In a preferred embodiment, the flame retardant in this invention may be red phosphorus.

[0084] Red phosphorus can be used in the form of red phosphorus masterbatch. The red phosphorus content in the masterbatch can be 30%-60% by weight. The base resin in the masterbatch can be the impact modifier e of this invention.

[0085] In a preferred embodiment, the flame retardant of the present invention comprises component c1) red phosphorus and component c2) a triazine flame retardant, wherein the triazine flame retardant is preferably melamine phosphate, bismelamine phosphate, melamine pyrophosphate, melamine polyphosphate, bismelamine pyrophosphate, dimethylpyrazine phosphate, or melamine polyphosphate. Component c1) is preferably 3-20% by weight of the polyamide composition, more preferably 10-15% by weight. Component c2) is preferably 1-10% by weight of the polyamide composition, more preferably 3-8% by weight.

[0086] In a preferred embodiment, based on the total weight of the polyamide composition, the flame retardant of the present invention comprises 3-20% by weight, preferably 10-15% by weight, of red phosphorus as component c1, and 1-10% by weight, preferably 3-8% by weight, of melamine phosphate and / or bismelamine phosphate as component c2.

[0087] In a preferred embodiment, the flame retardant of the present invention comprises 15-35% by weight of an organic phosphorus-containing flame retardant based on the total weight of the polyamide composition.

[0088] In a preferred embodiment, the flame retardant of the present invention comprises 15-35% by weight of a dialkyl phosphate or a combination of a dialkyl phosphate and a metal salt of phosphorus, based on the total weight of the polyamide composition.

[0089] In a preferred embodiment, the flame retardant of the present invention comprises 20-25% by weight of a dialkyl phosphate or a combination of a dialkyl phosphate and a metal salt of phosphorus, based on the total weight of the polyamide composition.

[0090] In a preferred embodiment, the flame retardant of the present invention comprises 15-35% by weight of a dialkyl phosphate based on the total weight of the polyamide composition, said dialkyl phosphate being selected from aluminum dimethyl phosphonate, aluminum ethyl methyl phosphonate, aluminum diethyl phosphonate, aluminum methyl n-propyl phosphonate, zinc diethyl phosphonate, and zinc dimethyl phosphonate.

[0091] In a preferred embodiment, based on the total weight of the polyamide composition, the flame retardant of the present invention comprises 15-35% by weight of a combination of a dialkyl phosphate ester and a metal salt of phosphorus. The dialkyl phosphate ester is selected from aluminum dimethyl phosphinate, aluminum ethyl methyl phosphinate, aluminum diethyl phosphinate, aluminum methyl n-propyl phosphinate, zinc diethyl phosphinate, and zinc dimethyl phosphinate, and the metal salt of phosphorus is selected from Al(H₂PO₃)₃, Al₂(HPO₃)₃, Zn(HPO₃), Al₂(HPO₃)₃·4H₂O, and / or Al(OH)(H₂PO₃)₂·2H₂O.

[0092] The average particle size (d) of organophosphorus flame retardant particles dispersed in the polyamide composition50 The preferred range is 0.0001-0.5 mm, especially 0.001-0.2 mm.

[0093] In a preferred embodiment, based on the total weight of the polyamide composition, the flame retardant of the present invention comprises 5-15 wt%, preferably 5-10 wt%, of a mineral flame retardant and 10-30 wt%, preferably 15-25 wt%, of a halogenated flame retardant. The mineral flame retardant is preferably antimony trioxide. The halogenated flame retardant is preferably brominated polystyrene.

[0094] Those skilled in the art are aware of other suitable nitrogen-containing flame retardants.

[0095] d) Fiber and / or particulate fillers

[0096] The fiber and / or particulate filler in this invention can be a conventional filler in a polyamide composition. The filler may include fibers selected, for example, from glass fibers, carbon fibers, and mineral fibers. Preferably, the composition comprises at least glass fibers, carbon fibers, or combinations thereof. The glass fibers may be selected, for example, from A-glass, C-glass, D-glass, E-glass, H-glass, M-glass, R-glass, and S-glass fibers, or any mixture thereof. Alkali-free E-glass fibers are preferred, or mixtures of glass fibers comprising E-glass fibers and one or more other glass fibers. These may be used in the form of untwisted rovings or in the form of commercially available cullet. The glass fibers may have an average length of 2 to 7 mm, more preferably 3 to 6 mm. The diameter of the glass fibers is preferably 3 to 20 μm, more preferably 7 to 13 μm. Examples of the cross-sectional shape of the fiber reinforcement include circular, rectangular, elliptical, and other non-circular cross-sections, preferably circular.

[0097] All fillers that can be used are particulate fillers known to those skilled in the art. These include, in particular, particulate fillers selected from minerals, talc, mica, dolomite, silicates, quartz, wollastonite, kaolin, silica, magnesium carbonate, magnesium hydroxide, chalk, frosted glass, glass flakes, glass beads, hollow glass beads, and mixtures thereof.

[0098] In a preferred embodiment, the fiber and / or particulate filler in this invention is chopped glass fiber and / or carbon glass fiber.

[0099] Based on the total weight of the polyamide composition, the polyamide composition of the present invention comprises 0-50% by weight, preferably 10-40% by weight, more preferably 15-30% by weight of component d).

[0100] e) Impact modifier

[0101] Based on the total weight of the polyamide composition, the polyamide composition contains 1-25% by weight, preferably 5-20% by weight, and particularly 8-15% by weight of an impact modifier (also commonly referred to as an elastomeric polymer, elastomer, or rubber) as component e).

[0102] The impact modifier is preferably derived from at least two monomers selected from α-olefins, dienes, olefinically unsaturated nitrile and olefinically unsaturated carboxylic acids and their epoxides, esters and anhydrides, more preferably derived from at least one of α-olefins, dienes, olefinically unsaturated carboxylic acids, unsaturated carboxylic acid esters and olefinically unsaturated nitrile, and at least one of epoxides or unsaturated carboxylic acid anhydrides.

[0103] α-olefins preferably have 2-20 carbon atoms, more preferably 4-10 carbon atoms. Examples of α-olefins are ethylene, propylene, 1-butene, isobutene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-pentene, 3,5,5-trimethyl-1-hexene, 1-decene, and mixtures thereof, more preferably ethylene, propylene, 1-butene, 1-hexene, isobutene, mixtures of ethylene and propylene, mixtures of ethylene and 1-octene, mixtures of ethylene and 1-butene, mixtures of propylene and 4-methyl-1-pentene, mixtures of propylene and 1-butene, mixtures of ethylene, propylene, and 1-butene, and mixtures of 1-decene and 1-methyl-1-pentene, most preferably ethylene, 1-butene, 1-propylene, 1-pentene, and mixtures of ethylene and 1-octene.

[0104] Preferred dienes include conjugated dienes such as 1,3-butadiene, 1,3-pentadiene, isoprene, 1,3-hexadiene, and mixtures thereof; non-conjugated dienes having 5-25 carbon atoms such as 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene, 1,4-octadiene, and mixtures thereof; cyclic dienes such as cyclopentadiene, cyclohexadiene, cyclooctadiene, and dicyclopentadiene; alkenyl norbornene such as 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methylallyl-5-norbornene, and 2-isopropenyl-5-norbornene; and tricyclic dienes such as 3-methyltricyclic...

[0105] [5.2.1.0.2.6]-3,8-decadiene and mixtures thereof. Preferably 1,3-butadiene, 1,3-pentadiene and / or isoprene, more preferably 1,3-butadiene.

[0106] The olefinically bonded unsaturated nitrile monomer is preferably selected from acrylonitrile, methacrylonitrile, fumaric acid and α-cyanoethyl acrylonitrile, more preferably acrylonitrile and / or methacrylonitrile, and most preferably acrylonitrile.

[0107] The olefinically unsaturated carboxylic acid has at least one carbon-carbon double bond and at least one carboxyl group. Examples of olefinically unsaturated carboxylic acids are acrylic acid, methacrylic acid, maleic acid, fumaric acid, pentenoic acid, itaconic acid, citraconic acid, 2-ethylacrylic acid, 2-chloroacrylic acid, crotonic acid, isocrotonic acid, succinic acid, sorbic acid, succinic acid, cinnamic acid, and more preferably acrylic acid, methacrylic acid, maleic acid, fumaric acid, and / or citraconic acid.

[0108] The epoxy compounds of olefinically unsaturated carboxylic acids can be glycidyl esters, glycidyl ethers, and / or similar compounds. Examples of epoxy compounds of olefinically unsaturated acids are glycidyl acrylate, glycidyl methacrylate, 1-glycidyl maleate, diglycidyl maleate, itaconic acid monoglycidyl ester, itaconic acid diglycidyl ester, citraconic acid monoglycidyl ester, citraconic acid diglycidyl ester, and butene tricarboxylic acid monoglycidyl ester, preferably glycidyl acrylate and / or glycidyl methacrylate.

[0109] Alkenyl-bonded unsaturated carboxylic acid esters are preferably esters of acrylic acid and / or acetic acid, more preferably alkyl esters and / or hydroxyalkyl esters of acrylic acid and / or acetic acid, such as C1-C esters of acrylic acid and / or acetic acid. 18 More preferably C1-C 12 The most preferred C1-C4 alkyl esters and / or C1-C 18 More preferably C1-C 12 The preferred option is C1-C4 hydroxyalkyl esters. Examples of olefinically unsaturated carboxylic acid esters include methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, octyl acrylate, octyl methacrylate, decyl acrylate, decyl methacrylate, isodecyl acrylate, isodecyl methacrylate, isodecyl methacrylate, lauryl acrylate, lauryl methacrylate, dimethyl maleate, monomethyl maleate, hydroxyethyl methacrylate (HEMA), stearyl methacrylate, stearyl acrylate, isobornyl acrylate, isobornyl methacrylate, hydroxypropyl methacrylate, and vinyl acetate; more preferably, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, and / or isobutyl methacrylate; most preferably, methyl methacrylate, methyl acrylate, butyl acrylate, and / or butyl methacrylate.

[0110] The anhydride of the olefinically unsaturated carboxylic acid is preferably selected from maleic anhydride (MAH), acrylic anhydride, methacrylic anhydride, itaconic anhydride, citraconic anhydride, fumaric anhydride, nadic anhydride, methyl nadic anhydride, nadic anhydride, and methyl nadic anhydride, and more preferably maleic anhydride, (meth)acrylic anhydride, and / or fumaric anhydride.

[0111] The monomers of the impact modifier are preferably selected from ethylene, 1-butene, 1-propylene, 1-pentene, 1-octene, 1,3-butadiene, acrylonitrile, methacrylonitrile, glycidyl acrylate, glycidyl methacrylate, methyl methacrylate, methyl acrylate, butyl acrylate, butyl methacrylate, maleic anhydride, acrylic anhydride, glycidyl acrylate and glycidyl methacrylate.

[0112] Impact modifiers are described by example in Houben-Weyl, Method of Organischen Chemie, Vol. 4 / 1 (Georg-Thieme-Verlag, Stuttgart, 1961), pp. 392–406, and in CBBucknal’s monograph “Toughened Plastics” (Applied Science Publishers, London, 1977).

[0113] Some preferred types of these impact modifiers are described below.

[0114] In one embodiment of the invention, the impact modifier is derived from at least two α-olefin monomers, or a combination of α-olefin and conjugated diene.

[0115] In one embodiment of the invention, the impact modifier is derived from two monomers: ethylene, propylene, and / or octene. The impact modifier is preferably ethylene-propylene (EPM) rubber or an ethylene-octene copolymer.

[0116] In one embodiment of the invention, the impact modifier is derived from α-olefins and dienes. The impact modifier is preferably ethylene-propylene-diene (EPDM) rubber.

[0117] EPM rubber typically has almost no residual double bonds, while EPDM rubber may have 1 to 20 double bonds per 100 carbon atoms.

[0118] Examples of diene monomers for EPDM rubber that may be mentioned are conjugated dienes, such as isoprene and butadiene; non-conjugated dienes having 5-25 carbon atoms, such as 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene, and 1,4-octadiene; cyclic dienes such as cyclopentadiene, cyclooctadiene, and dicyclopentadiene; alkenyl norbornene such as 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methylallyl-5-norbornene, and 2-isopropenyl-5-norbornene; and tricyclic dienes such as 3-methyltricyclo[5.2.1.0.2.6]-3,8-decadiene, and mixtures thereof. 1,5-hexadiene, 5-ethylidene norbornene, and dicyclopentadiene are preferred. Based on the total weight of the rubber, the diene content of the EPDM rubber is preferably 0.5 to 50% by weight, particularly 1 to 8% by weight.

[0119] EPM and EPDM rubbers can also preferably be grafted with olefinically unsaturated carboxylic acids and / or their epoxides, esters, and anhydrides. Examples of grafted monomers are acrylic acid, methacrylic acid, glycidyl (meth)acrylate, and maleic anhydride.

[0120] In one embodiment of the invention, the impact modifier is derived from α-olefins, epoxy compounds of olefinically unsaturated carboxylic acids, and styrene. Preferably, the α-olefin is ethylene, butene, and / or propylene, more preferably ethylene and butene. Examples of epoxy compounds of olefinically unsaturated carboxylic acids are preferably glycidyl acrylate and / or glycidyl methacrylate (GMA). Preferably, the epoxy compounds of olefinically unsaturated carboxylic acids are grafted onto or copolymerized into polyolefin / polystyrene coblocks.

[0121] In a preferred embodiment of the invention, the impact modifier is GMA-grafted polypropylene or GMA-grafted styrene-ethylene-butene (SEBS) copolymer.

[0122] In one embodiment of the invention, the impact modifier is derived from an epoxy compound of at least one α-olefin, at least one olefinically unsaturated carboxylic acid, and at least one olefinically unsaturated carboxylic acid. Examples of α-olefins herein are ethylene, butene, and propylene. Examples of olefinically unsaturated carboxylic acids are acrylic acid, methacrylic acid, maleic acid, and fumaric acid, preferably acrylic acid and methacrylic acid. Examples of epoxy compounds of olefinically unsaturated carboxylic acids herein are preferably glycidyl acrylate and / or glycidyl methacrylate (GMA). The impact modifier is preferably an ethylene / acrylic acid / GMA terpolymer.

[0123] In one embodiment of the invention, the impact modifier is derived from at least one α-olefin, at least one olefinically unsaturated carboxylic acid ester, and at least one polyester ether elastomer. Examples of α-olefins herein are ethylene and / or butene. Examples of olefinically unsaturated carboxylic acid esters herein are methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, and / or butyl methacrylate.

[0124] Copolymers of (e-1) α-olefins with (e-2) olefinically unsaturated carboxylic acids, epoxides, esters and / or anhydrides of olefinically unsaturated carboxylic acids are another group of preferred rubbers. The copolymer can be a block copolymer, alternating copolymer, random copolymer or graft copolymer, preferably a block copolymer and / or graft copolymer. The (e-1) α-olefin is preferably ethylene, butene, propylene and / or octene. Component (e-2) is preferably one or more of acrylic acid, methacrylic acid, maleic acid, fumaric acid, methyl methacrylate, methyl acrylate, butyl acrylate, butyl methacrylate, maleic anhydride, (meth)acrylic anhydride, fumaric anhydride, glycidyl acrylate and glycidyl methacrylate.

[0125] In one embodiment of the invention, the impact modifier is derived from at least one monomer of an α-olefin (e-1), and an epoxy compound of an olefinically unsaturated carboxylic acid and / or at least one monomer of an anhydride of an olefinically unsaturated carboxylic acid (e-2). The α-olefin herein is preferably ethylene, butene, propylene, and / or octene. Examples of the epoxy compounds of the olefinically unsaturated carboxylic acid herein are preferably glycidyl acrylate and / or glycidyl methacrylate (GMA). The anhydride of the olefinically unsaturated carboxylic acid is preferably maleic anhydride. The monomer (e-2) herein is preferably grafted onto or copolymerized onto a polyolefin block. The impact modifier is preferably GMA-grafted ethylene, GMA-grafted polypropylene, GMA-grafted ethylene-butene copolymer, or GMA-grafted ethylene-octene.

[0126] In a preferred embodiment, the impact modifier in this invention may be derived from ethylene and octene.

[0127] The copolymer is advantageously composed of 50-98 wt% (e-1)α-olefin and 0.1-20 wt% (e-2) component.

[0128] Copolymers composed of the following components are particularly preferred:

[0129] 50 to 98% by weight, particularly 55 to 95% by weight, of ethylene and / or octene.

[0130] 0.1 to 20% by weight, particularly 0.3 to 20% by weight, of glycidyl acrylate and / or glycidyl methacrylate, (meth)acrylic anhydride and / or maleic anhydride, and

[0131] 1-45% by weight, particularly 5-40% by weight (meth)acrylic acid, n-butyl acrylate and / or 2-ethylhexyl acrylate.

[0132] The aforementioned ethylene copolymers can be produced by methods known per se, preferably by random copolymerization under high pressure and high temperature. Suitable processes are well known.

[0133] The preferred impact modifiers are selected from maleic anhydride-functionalized polyolefins, maleic anhydride-functionalized polyethylene copolymers, glycidyl methacrylate-functionalized ethylene and methyl acrylate terpolymers, or combinations thereof.

[0134] The molar mass of the impact modifier is preferably from 10,000 to 500,000 g / mol, more preferably from 15,000 to 400,000 g / mol (Mn, determined by GPC calibrated with PS in 1,2,4-trichlorobenzene).

[0135] Of course, a mixture of the various impact modifiers listed above can also be used.

[0136] f) Additives

[0137] The polyamide composition contains 0-20% by weight of other additives, including antioxidants, lubricating dispersants, UV stabilizers, pigments, colorants, antistatic agents, thickeners, thixotropic agents, surfactants, viscosity modifiers, plasticizers, or nucleating agents.

[0138] Suitable antioxidants that can be mentioned are hindered phenolic antioxidants that form the phosphate ester antioxidant lipid compound system. Suitable hindered phenols are, in principle, all compounds with a phenolic structure and at least one large group on the phenolic ring.

[0139] Examples of compounds that may be preferred are compounds of formula I.

[0140]

[0141] in:

[0142] R 1 and R 2 It is an alkyl, a substituted alkyl, or a substituted triazole, wherein R 1 and R 2 They can be the same or different, R 3 It is an alkyl, substituted alkyl, alkoxy, or substituted amino group.

[0143] Another preferred group of hindered phenols is provided by hindered phenols derived from substituted phenylcarboxylic acids, particularly those derived from substituted phenylpropionic acids.

[0144] The most preferred compounds in this class are those of formula II.

[0145]

[0146] Where R 4 R 5 R 7 and R 8 Each of these groups can independently possess substituted C1-C8-alkyl groups (at least one of which is a large group), R 6 It is a divalent aliphatic group with 1-10 carbon atoms and its main chain may also have CO bonds.

[0147] The compounds that have proven particularly effective and are therefore preferred are 2,2'-methylenebis(4-methyl-6-tert-butylphenol) and 1,6-hexanediol bis(3,5-di-tert-butyl-4-hydroxyphenyl) propionate. 259), pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and N,N'-hexamethylene-bis-3,5-di-tert-butyl-4-hydroxyhydrocinnamate ( 1098), and the aforementioned products from BASF SE. 245, which has particularly good applicability.

[0148] Suitable flame retardant accelerators include zinc oxide, modified zinc oxide, zinc borate, zinc stannate, MgO, Mg(OH)2, ZnCO3, MgCO3, CaCO3, and AlOOH, with zinc oxide and modified zinc oxide being particularly preferred.

[0149] Suitable lubricating dispersants include zinc stearate, calcium stearate, ethylene distearate amine, oleamide, erucamide, polyethylene wax, or combinations thereof.

[0150] Suitable colorants include inorganic pigments such as titanium dioxide, iron oxide, and carbon black.

[0151] In a preferred embodiment, a method for improving the tracking performance of a slope at voltages above 1 kV is described by using a polyamide composition comprising:

[0152] a) 20-40% by weight of at least one semi-crystalline aliphatic polyamide selected from PA 6, PA 66 and PA 6 / 66;

[0153] b) 8-25% by weight of at least one long-chain aliphatic polyamide selected from PA 1212, 610, 612, 1010 and PA 6 / 6.36;

[0154] c) 3-20% by weight of red phosphorus and 1-10% by weight of triazine flame retardants;

[0155] d) 10-40% by weight of fiber and / or particulate fillers;

[0156] e) 0-15% by weight of impact modifier, and

[0157] f) 0-20% by weight of other additives; based on the total weight of the polyamide composition.

[0158] In a preferred embodiment, a method for improving the tracking performance of a slope at voltages above 1 kV is described by using a polyamide composition comprising:

[0159] a) 20-40% by weight of at least one semi-crystalline aliphatic polyamide selected from PA 6, PA 66 and PA 6 / 66;

[0160] b) 8-25% by weight of at least one long-chain aliphatic polyamide selected from PA 1212, 610, 612, 1010 and PA 6 / 6.36;

[0161] c) 3-20% by weight of red phosphorus and 1-10% by weight of triazine flame retardants;

[0162] d) 10-40% by weight of fiber and / or particulate fillers;

[0163] e) 5-15% by weight of impact modifier, and

[0164] f) 0-20% by weight of other additives; based on the total weight of the polyamide composition.

[0165] In a preferred embodiment, a method for improving the tracking performance of a slope at voltages above 1 kV is described by using a polyamide composition comprising:

[0166] a) 20-40% by weight of at least one semi-crystalline aliphatic polyamide selected from PA 6, PA 66 and PA 6 / 66;

[0167] b) 8-15% by weight of at least one long-chain aliphatic polyamide selected from PA 1212, 610, 612, 1010 and PA 6 / 6.36; wherein the weight ratio of component a) to b) is 3.5:1 to 2.5:1;

[0168] c) 4-25% by weight of flame retardant;

[0169] d) 20-40% by weight of fiber and / or particulate fillers;

[0170] e) 5-15% by weight of impact modifier, and

[0171] f) 0-20% by weight of other additives; based on the total weight of the polyamide composition.

[0172] In a preferred embodiment, a method for improving the tracking performance of a slope at voltages above 1 kV is described by using a polyamide composition comprising:

[0173] a) 20-40% by weight of at least one semi-crystalline aliphatic polyamide selected from PA 6, PA 66 and PA 6 / 66;

[0174] b) 8-15% by weight of at least one long-chain aliphatic polyamide selected from PA 1212, 610, 612, 1010 and PA 6 / 6.36; wherein the weight ratio of component a) to b) is 3.5:1 to 2.5:1;

[0175] c) 3-20% by weight of red phosphorus, or a combination of 3-20% by weight of red phosphorus and 1-10% by weight of triazine flame retardant;

[0176] d) 20-40% by weight of fiber and / or particulate fillers;

[0177] e) 5-15% by weight of impact modifier, and

[0178] f) 0-20% by weight of other additives; based on the total weight of the polyamide composition.

[0179] In a preferred embodiment, a method for improving the tracking performance of a slope at voltages above 1 kV is described by using a polyamide composition comprising:

[0180] a) 20-40% by weight of at least one semi-crystalline aliphatic polyamide selected from PA 6, PA 66 and PA 6 / 66;

[0181] b) 8-15% by weight of at least one long-chain aliphatic polyamide selected from PA 1212, 610, 612, 1010 and PA 6 / 6.36; wherein the weight ratio of component a) to b) is 3.5:1 to 2.5:1;

[0182] c) 15-35% by weight of dialkyl phosphate, or a combination of dialkyl phosphate and a metal salt of phosphorus; wherein the dialkyl phosphate is selected from aluminum dimethyl phosphonate, aluminum ethyl methyl phosphonate, aluminum diethyl phosphonate, aluminum methyl n-propyl phosphonate, zinc diethyl phosphonate, and zinc dimethyl phosphonate, and the metal salt of phosphorus is selected from Al(H2PO3)3, Al2(HPO3)3, Zn(HPO3), Al2(HPO3)3·4H2O, and / or Al(OH)(H2PO3)2·2H2O;

[0183] d) 20-40% by weight of fiber and / or particulate fillers;

[0184] e) 0-15% by weight of impact modifier, and

[0185] f) 0-20% by weight of other additives; based on the total weight of the polyamide composition.

[0186] In a preferred embodiment, a method for improving the tracking performance of a slope at voltages above 1 kV is described by using a polyamide composition comprising:

[0187] a) 20-40% by weight of at least one semi-crystalline aliphatic polyamide selected from PA 6, PA 66 and PA 6 / 66;

[0188] b) 8-15% by weight of at least one long-chain aliphatic polyamide selected from PA 1212, 610, 612, 1010 and PA 6 / 6.36; wherein the weight ratio of component a) to b) is 3.5:1 to 2.5:1;

[0189] c) 5-15% by weight of a mineral flame retardant and 10-30% by weight of a halogenated flame retardant, based on the total weight of the polyamide composition; the mineral flame retardant is preferably antimony trioxide; the halogenated flame retardant is preferably brominated polystyrene;

[0190] d) 20-40% by weight of fiber and / or particulate fillers;

[0191] e) 0-15% by weight of impact modifier, and

[0192] f) 0-20% by weight of other additives; based on the total weight of the polyamide composition.

[0193] Preparation of polyamide compositions

[0194] The polyamide compositions of the present invention can be produced by methods known per se, by mixing the components in conventional mixing equipment, such as a screw extruder, Brabender mixer, or Banbury mixer, and then extruding them. The extrudate can be cooled and granulated. Alternatively, individual components can be premixed, and then the remaining components added individually and / or in the same manner as a mixture. Generally, the screw diameter is 20-40 mm, the screw speed is 300-500 rpm, the output is 25-35 kg / h, and the melt temperature is 230-320 °C.

[0195] In a preferred embodiment, the polyamide composition is produced by (1) introducing a semi-crystalline aliphatic polyamide (a), a long-chain aliphatic polyamide (b), an impact modifier (e), and an additive (f) into an extruder, and (2) introducing fiber and / or particulate filler (d) and a flame retardant (c) into the extruder through a downstream feed zone, followed by kneading and extrusion.

[0196] The polyamide compositions of the present invention have good mechanical properties and a highly reproducible flame retardant rating according to UL 94, and also have very good electrical properties at high voltages, such as high IPT and CTI values ​​at voltages above 1 kV, up to 1.2 kV, 1.5 kV or even 2 kV.

[0197] Polyamide compositions are suitable for producing any type of fiber, film, and molding. Some examples include plug connectors, plugs, plug components, cable harness components, circuit mounts, circuit mount components, three-dimensional injection molded circuit mounts, electrical connection elements, and electromechanical components. Due to their excellent electrical properties under high voltage, these materials are particularly suitable for producing photovoltaic connector nuts and bodies, and outdoor electrical insulating plastic parts.

[0198] Another object of the present invention is to provide an article produced from a polyamide composition that exhibits excellent anti-tracking properties at voltages above 1 kV, for example 1.2 kV or above, 1.5 kV or above, or up to 2 kV. This article is preferably a nut or body of a photovoltaic connector or an electrically insulating plastic component.

[0199] Another object of the present invention is to provide a polyamide composition comprising...

[0200] a) 10-50% by weight of at least one semi-crystalline aliphatic polyamide, wherein each amide group has an average of 3-5 carbon atoms, excluding the carbon atoms in the amide group;

[0201] b) 1-40% by weight of at least one long-chain aliphatic polyamide, each amide group having an average of 6 or more carbon atoms, excluding carbon atoms in the amide group; the weight ratio of components a) and b) in the polyamide composition is 3.5:1 to 2.5:1;

[0202] c) 4-25% by weight of flame retardant, comprising component c1) red phosphorus and component c2) triazine flame retardant, wherein the triazine flame retardant is preferably melamine phosphate, bismelamine phosphate, melamine pyrophosphate, melamine polyphosphate, bismelamine pyrophosphate, dimethylpyrazine phosphate or melamine polyphosphate;

[0203] d) 0-50% by weight of fiber and / or particulate fillers;

[0204] e) 1-25% by weight of impact modifier, and

[0205] f) 0-20% by weight of other additives.

[0206] Component a) is preferably 15-45% by weight, particularly 20-40% by weight, based on the total weight of the polyamide composition. Component b) is preferably 5-30% by weight, more preferably 8-25% by weight, particularly 10-20% by weight, based on the total weight of the polyamide composition. In component c), component c1) is preferably 3-15% by weight of the polyamide composition, more preferably 5-10% by weight, and component c2) is preferably 1-10% by weight of the polyamide composition, more preferably 3-8% by weight.

[0207] Example

[0208] The invention will now be described with reference to embodiments and comparative examples, which are not intended to limit the invention.

[0209] Use the following starting materials:

[0210] Polyamide 66, BASF, Ultramid A27, viscosity value 150 cm⁻¹ according to ISO 307,1157 3 / g.

[0211] Polyamide 66, BASF, Ultramid A24, viscosity value 125 cm⁻¹ according to ISO 307,1157 3 / g.

[0212] Polyamide 1212, polydodecylmethylene dodecylamide, Shandong Dongchen New Technology Co., Ltd., PA 1212 type II.

[0213] Polyamide 610, poly[imino-1,6-hexamethylenediimino(1,10-dioxo-1,10-decanoyl)], Shandong Dongchen New Technology Co., Ltd., PA 610 type II.

[0214] Polyamide 6 / 6.36, BASF, Ultramid Flex F 29.

[0215] Polyamide 6I / 6T, DuPont, Selar 3426.

[0216] Glass fiber, NEC Glass Co., Ltd., NEG-T 251H, length = 4.5mm, diameter = 10μm.

[0217] Red phosphorus masterbatch, comprising 50% by weight red phosphorus with an average particle size (d50) of 20-25 μm and 50% by weight olefin polymer, Italmatch Chemicals, Masterbatch 11452-1270, olefin polymer: 59.8% by weight ethylene, 35% by weight n-butyl acrylate, 4.5% by weight acrylic acid and 0.7% by weight maleic anhydride.

[0218] Melamine phosphate, BASF, Melapur 200-70.

[0219] A mixture of OP 1400, 80 wt% OP 1230 (aluminum diethylphosphinate) and 20 wt% PHOPHAL (aluminum phosphate), Clariant.

[0220] Brominated polystyrene, Shandong Brothers Technology, XZ-6700H.

[0221] Antimony trioxide masterbatch, 90% by weight Sb2O3 in low-density polyethylene (LDPE), Dongguan Jeff Flame Retardant Materials Co., Ltd., LDPE90B.

[0222] Ethylene octene copolymer grafted with MAH, DuPont, Fusabond N493.

[0223] Lotader AX 8900 is a random terpolymer of ethylene, acrylate and glycidyl methacrylate, comprising 8% by weight glycidyl methacrylate and 24% by weight acrylate, Arkema.

[0224] Wax esters, lubricants, Emery Oleochemicals Co., Loxiol G 32.

[0225] Irganox 1098, an antioxidant, BASF.

[0226] Zinc oxide, Shenlong, 99.8% zinc oxide.

[0227] UB 434, Colloids Ltd., Black Colorant Masterbatch (MB).

[0228] Measurement methods

[0229] The interphase tracking (IPT) value on the bevel is measured according to ASTM D 2303;

[0230] The flame retardancy rating was measured according to UL 94, and the sample size was 127mm*12.7mm*1.6mm (length*width*thickness).

[0231] The Comparative Test Index (CTI) value is measured according to IEC 60112;

[0232] Tensile strength, fracture strain and E-modulus were measured on a Z050 (Zwick Roell, Germany) using type 1A specimens according to ISO 527-2.

[0233] The notch Charpy was completed by HIT25P (Zwick Roell, Germany) according to ISO 179 / 1eA;

[0234] Unnotched Charpy was measured by HIT25P (Zwick Roell, Germany) according to ISO 179 / 1eU.

[0235] Example 1:

[0236] Processing steps:

[0237] (1) The components, including 31.9 wt% polyamide 66 (Ultramid A27), 10.5 wt% polyamide 1212, 8.7 wt% impact modifier (Fusabond N493), 2 wt% AX 8900, 0.35 wt% lubricant (Loxiol G32), 0.35 wt% antioxidant (Irganox 1098), 0.7 wt% flame retardant accelerator (ZnO) and 2.5 wt% black colorant MB (UB 434), are mixed in a high-speed mixer.

[0238] (2) Feed the mixture into the throat region of a twin-screw extruder;

[0239] (3) 25% by weight of glass fiber (NEG-T251H) is fed into the extruder through the side fiber feeder;

[0240] (4) 15% by weight of red phosphorus masterbatch and 3% by weight of Melapur 200-70 are fed into the extruder through the side powder feeder;

[0241] (5) Add to a twin-screw extruder for granulation, and cut the extrudate into granules;

[0242] (6) The screw diameter is 26mm, the screw speed is 300rpm~500rpm, the output is 25~35kg / h, and the melt temperature is 280℃.

[0243] Example 2:

[0244] Processing steps:

[0245] (1) The components, including 31.9 wt% polyamide 66 (Ultramid A27), 10.5 wt% polyamide 610, 8.7 wt% impact modifier (Fusabond N493), 2 wt% AX 8900, 0.35 wt% lubricant (Loxiol G32), 0.35 wt% antioxidant (Irganox 1098), 0.7 wt% flame retardant accelerator (ZnO) and 2.5 wt% black colorant MB (UB 434), are mixed in a high-speed mixer.

[0246] (2) Feed the mixture into the throat region of a twin-screw extruder;

[0247] (3) 25% by weight of glass fiber (NEG-T251H) is fed into the extruder through the side fiber feeder;

[0248] (4) 15% by weight of red phosphorus masterbatch and 3% by weight of Melapur 200-70 are fed into the extruder through the side powder feeder;

[0249] (5) Add to a twin-screw extruder for granulation, and cut the extrudate into granules;

[0250] (6) The screw diameter is 26mm, the screw speed is 300rpm~500rpm, the output is 25~35kg / h, and the melt temperature is 280℃.

[0251] Example 3:

[0252] Processing steps:

[0253] (1) The components, including 31.9 wt% polyamide 66 (Ultramid A27), 10.5 wt% polyamide 6 / 636, 8.7 wt% impact modifier (Fusabond N493), 2 wt% AX 8900, 0.35 wt% lubricant (Loxiol G32), 0.35 wt% antioxidant (Irganox 1098), 0.7 wt% flame retardant accelerator (ZnO) and 2.5 wt% black colorant MB (UB 434), are mixed in a high-speed mixer.

[0254] (2) Feed the mixture into the throat region of a twin-screw extruder;

[0255] (3) 25% by weight of glass fiber (NEG-T251H) is fed into the extruder through the side fiber feeder;

[0256] (4) 15% by weight of flame retardant red phosphorus masterbatch and 3% by weight of Melapur 200-70 are fed into the extruder through a side powder feeder;

[0257] (5) Add to a twin-screw extruder for granulation, and cut the extrudate into granules;

[0258] (6) The screw diameter is 26mm, the screw speed is 300rpm~500rpm, the output is 25~35kg / h, and the melt temperature is 280℃.

[0259] Comparative Example 1:

[0260] Processing steps:

[0261] (1) The components, including 46.9 wt% polyamide 66 (Ultramid A27), 12.2 wt% impact modifier (Fusabond N493), 0.35 wt% lubricant (Loxiol G32), 0.35 wt% antioxidant (Irganox1098), 0.7 wt% flame retardant accelerator (ZnO) and 2.5 wt% black colorant MB (UB 434), are mixed in a high-speed mixer.

[0262] (2) Feed the mixture into the throat region of a twin-screw extruder;

[0263] (3) 25% by weight of glass fiber (NEG-T251H) is fed into the extruder through the side fiber feeder;

[0264] (4) 12% by weight of red phosphorus masterbatch is fed into the extruder through a side powder feeder;

[0265] (5) Add to a twin-screw extruder for granulation, and cut the extrudate into granules;

[0266] (6) The screw diameter is 26mm, the screw speed is 300rpm~500rpm, the output is 25~35kg / h, and the melt temperature is 280℃.

[0267] Comparative Example 2:

[0268] Processing steps:

[0269] (1) The components including 31.9 wt% polyamide 66 (Ultramid A27), 10.5 wt% Selar 3426, 8.7 wt% impact modifier (Fusabond N493), 2 wt% AX 8900, 0.35 wt% lubricant (Loxiol G32), 0.35 wt% antioxidant (Irganox 1098), 0.7 wt% flame retardant accelerator (ZnO) and 2.5 wt% black colorant MB (UB 434) were mixed in a high-speed mixer.

[0270] (2) Feed the mixture into the throat region of a twin-screw extruder;

[0271] (3) 25% by weight of glass fiber (NEG-T251H) is fed into the extruder through the side fiber feeder;

[0272] (4) 15% by weight of flame retardant red phosphorus masterbatch and 3% by weight of Melapur 200-70 are fed into the extruder through a side powder feeder;

[0273] (5) Add to a twin-screw extruder for granulation, and cut the extrudate into granules;

[0274] (6) The screw diameter is 26mm, the screw speed is 300rpm~500rpm, the output is 25~35kg / h, and the melt temperature is 280℃.

[0275] The flame retardant, electrical, and mechanical properties of the products manufactured using the above embodiments were tested, and the results are summarized in Table 1 below:

[0276] Table 1: Properties of the polyamide compositions of Examples 1-3 and Comparative Examples 1-2

[0277]

[0278] * "EX" refers to an embodiment, and "CE" refers to a comparative example.

[0279] As can be seen from the table above, PA 66 alone, as a polyamide component, results in poor performance of the composition at high voltages above 1 kV, i.e., a very low IPT value, making it unsuitable for applications in the electrical technology field. Conversely, the polyamide compositions according to the present invention simultaneously possess excellent electrical properties at high voltages, high levels of flame retardancy, and good mechanical properties, making these compositions ideal materials for applications such as photovoltaic connector nuts and bodies, and outdoor electrical insulation plastic components. Among these aliphatic long-chain polyamides, PA 1212 exhibits better overall performance, achieving high IPT values ​​at both 1.5 and 2.0 kV.

[0280] In particular, as shown in Comparative Example 2, when aromatic polyamide is used instead of long-chain aliphatic polyamide, the IPT value at 1.5kV is significantly lower than that obtained by long-chain aliphatic polyamide, which cannot meet the requirements of photovoltaic applications at higher voltages.

[0281] Example 4:

[0282] Processing steps:

[0283] (1) The components, including 23.45 wt% polyamide 66 (Ultramid A27), 23.45 wt% polyamide 1212, 12.2 wt% impact modifier (Fusabond N493), 0.35 wt% lubricant (Loxiol G32), 0.35 wt% antioxidant (Irganox 1098), 0.7 wt% flame retardant accelerator (ZnO) and 2.5 wt% black colorant masterbatch (UB434), are mixed in a high-speed mixer.

[0284] (2) Feed the mixture into the throat region of a twin-screw extruder;

[0285] (3) 25% by weight of glass fiber (NEG-T251H) is fed into the extruder through the side fiber feeder;

[0286] (4) 12% by weight of flame retardant (red phosphorus masterbatch) is fed into the extruder through the side powder feeder;

[0287] (5) Add to a twin-screw extruder for granulation, and cut the extrudate into granules;

[0288] (6) The screw diameter is 26mm, the screw speed is 300rpm~500rpm, the output is 25~35kg / h, and the melt temperature is 280℃.

[0289] Example 5:

[0290] Processing steps:

[0291] (1) The components, including 31.4 wt% polyamide 66 (Ultramid A27), 15.5 wt% polyamide 1212, 12.2 wt% impact modifier (Fusabond N493), 0.35 wt% lubricant (Loxiol G32), 0.35 wt% antioxidant (Irganox 1098), 0.7 wt% flame retardant accelerator (ZnO) and 2.5 wt% black colorant masterbatch (UB434), are mixed in a high-speed mixer.

[0292] (2) Feed the mixture into the throat region of a twin-screw extruder;

[0293] (3) 25% by weight of glass fiber (NEG-T251H) is fed into the extruder through a side fiber feeder;

[0294] (4) 12% by weight of flame retardant (red phosphorus masterbatch) is fed into the extruder through a side powder feeder;

[0295] (5) Add to a twin-screw extruder for granulation, and cut the extrudate into granules;

[0296] (6) The screw diameter is 26mm, the screw speed is 300rpm~500rpm, the output is 25~35kg / h, and the melt temperature is 280℃.

[0297] Example 6:

[0298] Processing steps:

[0299] (1) The components, including 35.1 wt% polyamide 66 (Ultramid A27), 11.8 wt% polyamide 1212, 12.2 wt% impact modifier (Fusabond N493), 0.35 wt% lubricant (Loxiol G32), 0.35 wt% antioxidant (Irganox 1098), 0.7 wt% flame retardant accelerator (ZnO) and 2.5 wt% black colorant masterbatch, are mixed in a high-speed mixer.

[0300] (2) Feed the mixture into the throat region of a twin-screw extruder;

[0301] (3) 25% by weight of glass fiber (NEG-T251H) is fed into the extruder through the side fiber feeder;

[0302] (4) 12% by weight of flame retardant (red phosphorus masterbatch) is fed into the extruder through the side powder feeder;

[0303] (5) Add to a twin-screw extruder for granulation, and cut the extrudate into granules;

[0304] (6) The screw diameter is 26mm, the screw speed is 300rpm~500rpm, the output is 25~35kg / h, and the melt temperature is 280℃.

[0305] The flame retardant and electrical properties of the products prepared in Examples 4-6 above were tested, and the results are summarized in Table 2 below:

[0306] Table 2: Properties of the polyamide compositions in Examples 4-6

[0307]

[0308] Examples 7-12 and Comparative Examples 3-4

[0309] Except for the amounts of components listed in Tables 3-4 below, Examples 7-12 were carried out following the processing steps of Examples 1-6, and Comparative Examples 3-4 were carried out following the processing steps of Comparative Examples 1-2. The flame retardant and electrical properties of the products manufactured from the above examples were tested, and the results are summarized in Tables 3-4 below:

[0310] Table 3: Performance of the polyamide compositions of Comparative Example 3 and Examples 7-9

[0311]

[0312] Table 4: Performance of the polyamide compositions of Comparative Example 4 and Examples 10-12

[0313]

[0314] At a high voltage of 1.5 kV, the polyamide composition of the present invention achieves a significantly improved IPT value, while PA 66 alone, even in the same amount, results in a much lower IPT value at such a high voltage.

[0315] The structures, materials, compositions, and methods described herein are intended as representative embodiments of the invention, and it should be understood that the scope of the invention is not limited to the scope of these embodiments. Those skilled in the art will recognize that the invention can be practiced by variations of the disclosed structures, materials, compositions, and methods, and such variations are considered to be within the scope of the invention. Therefore, the invention is intended to cover such modifications and variations that fall within the scope of the appended claims and their equivalents.

Claims

1. A method for improving tracking performance on a sloped surface using a polyamide composition at voltages above 1 kV, said composition comprising: a) 10-50% by weight of at least one semi-crystalline aliphatic polyamide, each amide group having an average of 3-5 carbon atoms, excluding carbon atoms in the carbonyl group; b) 1-40% by weight of at least one long-chain aliphatic polyamide, wherein each amide group has an average of 6 or more carbon atoms, excluding carbon atoms in the carbonyl group; c) 0-35% by weight of flame retardant; d) 0-50% by weight of fiber and / or particulate fillers; e) 1-25% by weight of impact modifier, and f) 0-20% by weight of other additives.

2. The method according to claim 1, wherein the semi-crystalline aliphatic polyamide is selected from polyamide 4, polyamide 6, polyamide 56, polyamide 46, polyamide 66 and / or polyamide 6 / 66.

3. The method according to claim 2, wherein the semi-crystalline aliphatic polyamide is polyamide 66.

4. The method according to claim 1 or 2, wherein the amount of component a) is 15-45% by weight, based on the total weight of the polyamide composition.

5. The method according to claim 1 or 2, wherein the amount of component a) is 20-40% by weight, based on the total weight of the polyamide composition.

6. The method according to claim 1 or 2, wherein the at least one long-chain aliphatic polyamide is selected from polyamide 1212, polyamide 610, polyamide 612, polyamide 1010 and polyamide 6 / 6.

36.

7. The method according to claim 1 or 2, wherein the amount of component b) is 5-30% by weight, based on the total weight of the polyamide composition.

8. The method according to claim 1 or 2, wherein the amount of component b) is 8-25% by weight, based on the total weight of the polyamide composition.

9. The method according to claim 1 or 2, wherein the amount of component b) is 10-25% by weight, based on the total weight of the polyamide composition.

10. The method according to claim 1 or 2, wherein the flame retardant comprises (c1) 3-15% by weight of red phosphorus and (c2) 1-10% by weight of triazine flame retardant, based on the total weight of the polyamide composition.

11. The method according to claim 10, wherein the triazine flame retardant is selected from melamine phosphate, bismelamine phosphate, melamine pyrophosphate, bismelamine pyrophosphate, dimethylpyrazine phosphate, or melamine polyphosphate.

12. The method according to claim 1 or 2, wherein the amount of said flame retardant c) is 4-25% by weight, based on the total weight of the polyamide composition.

13. The method according to claim 1 or 2, wherein the amount of the flame retardant c) is 8-18% by weight, based on the total weight of the polyamide composition.

14. The method according to claim 1 or 2, wherein the fiber is glass fiber.

15. The method according to claim 1 or 2, wherein the fiber is alkali-free E-glass fiber.

16. The method according to claim 1 or 2, wherein the impact modifier is selected from maleic anhydride-functionalized polyolefins, glycidyl methacrylate-functionalized ethylene terpolymers, or combinations thereof.

17. The method of claim 16, wherein the maleic anhydride-functionalized polyolefin is selected from maleic anhydride-functionalized polyethylene copolymers.

18. The method according to claim 1 or 2, wherein the weight ratio of components a) and b) in the polyamide composition is from 5:1 to 1:

1.

19. The method according to claim 1 or 2, wherein the weight ratio of polyamide components a) and b) in the polyamide composition is from 4:1 to 1:

1.

20. The method according to claim 1 or 2, wherein the weight ratio of polyamide components a) and b) in the polyamide composition is from 3.5:1 to 2.5:

1.

21. The method according to claim 1 or 2, wherein the weight ratio of polyamide components a) and b) in the polyamide composition is 3:

1.

22. The method according to claim 1 or 2, wherein the voltage is 1.2 kV or higher and up to 2 kV.

23. The method of claim 22, wherein the voltage is 1.5 kV or higher and up to 2 kV.

24. The method according to claim 1 or 2, wherein the polyamide composition comprises a) 10-50% by weight of at least one semi-crystalline aliphatic polyamide, each amide group having an average of 3-5 carbon atoms, excluding carbon atoms in the carbonyl group; b) 1-40% by weight of at least one long-chain aliphatic polyamide, wherein each amide group has an average of 6 or more carbon atoms, excluding carbon atoms in the carbonyl group; c) 4-25% by weight of flame retardant, including component c1) red phosphorus and component c2) triazine flame retardant; d) 0-50% by weight of fiber and / or particulate fillers; e) 1-25% by weight of impact modifier, and f) 0-20% by weight of other additives.

25. The method according to claim 24, wherein the triazine flame retardant is melamine phosphate, bismelamine phosphate, melamine pyrophosphate, bismelamine pyrophosphate, dimethylpyrazine phosphate, or melamine polyphosphate.

26. The method according to claim 1 or 2, wherein the polyamide composition is used to produce a nut or body or an electrically insulating plastic component for a photovoltaic connector.

27. A polyamide composition comprising a) 10-50% by weight of at least one semi-crystalline aliphatic polyamide, wherein the semi-crystalline aliphatic polyamide is PA66; b) 8-25% by weight of at least one long-chain aliphatic polyamide, wherein the long-chain aliphatic polyamide is PA 610, PA1010, PA 1012, PA 1210, PA 1212 and / or PA6 / 6.36; c) 4-25% by weight of flame retardant, including component c1) red phosphorus and component c2) triazine flame retardant; d) 0-50% by weight of fiber and / or particulate fillers; e) 1-25% by weight of impact modifier, and f) 0-20% by weight of other additives.

28. The polyamide composition according to claim 27, wherein the triazine flame retardant is melamine phosphate, bismelamine phosphate, melamine pyrophosphate, bismelamine pyrophosphate, dimethylpyrazine phosphate, or melamine polyphosphate.

29. The polyamide composition according to claim 27 or 28, wherein the weight ratio of components a) and b) in the polyamide composition is from 5:1 to 1:

1.

30. The polyamide composition according to claim 27 or 28, wherein the weight ratio of components a) and b) in the polyamide composition is from 4:1 to 1:

1.

31. The polyamide composition according to claim 27 or 28, wherein component c1) is in the polyamide composition in a weight ratio of 3-15% and component c2) is in the polyamide composition in a weight ratio of 1-10%.

32. The polyamide composition according to claim 31, wherein component c1) is in the polyamide composition at a weight ratio of 5-10%.

33. The polyamide composition according to claim 31, wherein component c2) is in the polyamide composition at a weight ratio of 3-8%.

34. Articles made from the polyamide composition as defined in any one of claims 1-33.

35. The article of claim 34, wherein it is a nut or body or an electrically insulating plastic component of a photovoltaic connector.

36. Use of the polyamide composition as defined in any one of claims 1-33 for improving tracking properties on inclined surfaces at voltages above 1 kV and up to 2 kV.

37. The use according to claim 36, wherein the voltage is 1.2 kV or higher and up to 2 kV.

38. The use according to claim 36, wherein the voltage is 1.5 kV or higher and up to 2 kV.

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