Polyamide composition for materials

Abstract

The invention relates to a magnetic composite material, characterized in that it comprises: - from 4 to 30% by weight of a copolymer, - from 70 to 96% by weight of a magnetic powder, - from 0 to 5% by weight of at least one coupling agent, - from 0 to 5% by weight of at least one additive, the total of the copolymer, the magnetic powder, the coupling agent and the additive being 100% by weight, the copolymer consisting of: - at least one unit (A) chosen from polyamide units, - at least one monocarboxylic acid unit (B), - at least one diamine unit (C), - at least one triamine unit (D), - optionally at least one polyetheramide unit (E), the total of the constituents A, B, C, D and E being 100% by weight relative to the total weight of the copolymer.

Description

Technical Field

[0001] This invention relates to compositions for use in magnetic composite materials and such composite materials. Existing technology

[0002] Magnetic composite materials are increasingly used, especially in motor vehicles as sensors, automotive alternators, generators or magneto motors, in electrical and electronic systems as speakers or microphones, and in telephones as telephone chargers.

[0003] Compositions for use in magnetic materials are known, and involve mixtures of polyamides with magnetic fillers in powder form, wherein the magnetic fillers constitute the majority.

[0004] Therefore, producing a composition containing polyamide resin and a large amount of magnetic powder requires mixing a large amount of magnetic powder with a composition containing molten polyamide resin. However, a very sharp increase in viscosity has been observed, which makes processing impossible. Furthermore, the mixture of polyamide and magnetic powder is unstable.

[0005] This variability is related to the acid and / or amine chain ends of the polyamide, so the strategy is to reduce this content by using monofunctional chain transfer agents (such as stearic acid).

[0006] This strategy has two drawbacks: the polyamide must have a limited molecular weight to retain the fluid, and the material with magnetic filler is brittle.

[0007] International patent application WO2014050631 attempts to address this problem by using two types of chain transfer agents to make the mixture more stable, so as to provide a composition containing a polyamide resin, wherein the concentration of terminal amino groups and terminal carboxyl groups in the polyamide resin is from 10 μeq / g to 40 μeq / g.

[0008] This second strategy allows for a slight increase in molecular weight, but the final mixture's ductility must be improved.

[0009] Therefore, there is a need to discover new compositions for magnetic materials that allow for overcoming these various problems, and this is the object of the present invention. The present invention relates to magnetic composite materials, characterized in that the magnetic composite material comprises:

[0010] 4% to 30% by weight of copolymers,

[0011] 70% to 96% by weight of magnetic powder,

[0012] At least one coupling agent, ranging from 0% to 5% by weight.

[0013] At least one additive, ranging from 0% to 5% by weight.

[0014] The total amount of copolymers, magnetic powders, coupling agents, and additives is 100% by weight.

[0015] The copolymer has the following composition:

[0016] - At least one unit (A), selected from polyamide units,

[0017] - At least one monocarboxylic acid unit (B),

[0018] - At least one (at least one) diamine unit (C),

[0019] - At least one triamine unit (D),

[0020] -Optionally at least one (at least one) polyetheramide unit (E),

[0021] The sum of components A, B, C, D and E is 100% by weight, relative to the total weight of the copolymer.

[0022] Therefore, the inventors have surprisingly discovered that a mixture of a specific copolymer comprising at least one monocarboxylic acid unit (B), at least one diamine unit (C), and at least one triamine unit (D) with a magnetic powder provides a magnetic material that benefits not only from its stability during mixing but also from its lack of a sharp increase in viscosity during mixing, thereby enabling efficient processing.

[0023] Furthermore, the molecular weight of polyamide is not limited, and the resulting material with magnetic filler is ductile.

[0024] Regarding copolymers

[0025] The copolymer comprises at least one unit (A), at least one monocarboxylic acid unit (B), at least one diamine unit (C), at least one triamine unit (D), and optionally at least one polyetheramide unit (E).

[0026] The copolymer advantageously has an acid end content of less than 10 μeq / g.

[0027] The copolymer advantageously has an amine end content of less than 80 μeq / g.

[0028] The copolymer is more advantageously characterized by an acid end content of less than 10 μeq / g and an amine end content of less than 80 μeq / g.

[0029] The acid and amine chain ends can be determined by potentiometry or by NMR.

[0030] Determination of acid chain ends by total acidity measurement:

[0031] Acidity was measured as follows: 1 g of polyamide was dissolved in 80 ml of benzyl alcohol at high temperature. The sample was then cooled. Subsequently, the sample was determined by potentiometry using a Metrohm titrator (888 or 716) with a composite pH electrode and a 0.02 N tetrabutylammonium hydroxide solution. The potential diagram as a function of volume showed the jump at the equivalent volume, from which the acid chain end was calculated using the following formula:

[0032] [Mathematical Expression 1]

[0033]

[0034] in

[0035] Veq represents the equivalent volume obtained by potentiometric measurement.

[0036] [TBAOH] indicates the concentration of the tetrabutylammonium hydroxide solution, i.e., 0.02N.

[0037] m represents the mass of the sample, i.e., 1g.

[0038] This method determines the acid chain termini and the H3PO4 introduced into the composition. By understanding the amount of H3PO4 introduced into the composition, the proportion of acid chain termini can be deduced.

[0039] Determination of the amine chain ends:

[0040] The amine chain terminus was determined by potentiometry.

[0041] Unit A

[0042] Unit A is a semi-crystalline or amorphous polyamide.

[0043] For the purposes of this invention, semi-crystalline polyamide refers to a polyamide having a glass transition temperature in DSC according to standard ISO 11357-2:2013 and a melting point (Tm) in DSC according to standard ISO 11357-3:2013.

[0044] For the purposes of this invention, amorphous polyamide refers to a transparent amorphous polyamide having only a glass transition temperature (no melting point (Tm)), or a polyamide with extremely low crystallinity, having a glass transition temperature and melting point such that the enthalpy of crystallization during the cooling step at a rate of 20 K / min, as measured by differential scanning calorimetry (DSC) according to standard ISO 11357-3:2013, is less than 30 J / g, particularly less than 20 J / g, and preferably less than 15 J / g. For these polyamides, the glass transition temperature (Tg) measured by DSC at a heating rate of 20 K / min according to standards ISO 11357-1:2009 and ISO 11357-2:2013 is advantageously greater than 75°C.

[0045] The nomenclature used to define polyamides is described in standard ISO 1874-1:2011 "Plastics - Polyamide (PA) molding and extrusion materials - Part 1: Designation", particularly page 3 (Tables 1 and 2), and is well known to those skilled in the art.

[0046] The term "polyamide" refers to homopolymer or copolymer. It can be clearly understood that it can be a mixture of aliphatic polyamides.

[0047] The average number of carbon atoms relative to a nitrogen atom is greater than or equal to 6.

[0048] Advantageously, it is greater than or equal to 8.

[0049] In the case of PAXY type homopolymer, the number of carbon atoms per nitrogen atom is the average of the X and Y units.

[0050] In the case of copolyamides, the number of carbon atoms per nitrogen atom is calculated using the same principle. This calculation is based on the molar ratio of each amide unit.

[0051] The polyamide unit is derived from the following polycondensation: at least one lactam, or at least one aminocarboxylic acid, or at least one diamine and at least one dicarboxylic acid.

[0052] In the first embodiment:

[0053] In a first variant of this first embodiment, the semi-crystalline polyamide is obtained by polycondensation of at least one aminocarboxylic acid containing 6 to 18 carbon atoms, preferably 8 to 12 carbon atoms, and more preferably 10 to 12 carbon atoms. Therefore, it may be selected from 6-aminohexanoic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid, 13-aminotridecanoic acid, 14-aminotetradecanoic acid, 15-aminopentadecanoic acid, 16-aminohexadecanoic acid, 17-aminoheptadecanoic acid, and 18-aminooctadecanoic acid.

[0054] Preferably, the semi-crystalline polyamide is obtained by polycondensation of a single aminocarboxylic acid.

[0055] In a second variant of the first embodiment, the semi-crystalline polyamide is obtained by polycondensation of at least one lactam containing 6 to 18 carbon atoms, preferably 8 to 12 carbon atoms, and more preferably 10 to 12 carbon atoms.

[0056] Preferably, the semi-crystalline polyamide is obtained by polycondensation of a single lactam.

[0057] In a third variant of the first embodiment, the semi-crystalline polyamide is obtained by polycondensation of at least one diamine comprising 4 to 36 carbon atoms, advantageously 6 to 18 carbon atoms, advantageously 6 to 12 carbon atoms, or advantageously 10 to 12 carbon atoms, with at least one dicarboxylic acid comprising 4 to 36 carbon atoms, advantageously 6 to 18 carbon atoms, advantageously 6 to 12 carbon atoms, or advantageously 8 to 12 carbon atoms.

[0058] The diamine used to obtain the repeating unit XY can be an aliphatic or alkyl aromatic diamine.

[0059] Aliphatic diamines have a linear backbone containing at least 4 carbon atoms.

[0060] Where appropriate, the linear backbone may contain one or more methyl and / or ethyl substituents; in this configuration, the term "branched aliphatic diamine" is used. When the backbone does not contain substituents, the aliphatic diamine is called a "linear aliphatic diamine".

[0061] Regardless of whether its main chain contains methyl and / or ethyl substituents, the aliphatic diamine used to obtain the repeating unit XY contains 4 to 36 carbon atoms, advantageously 4 to 18 carbon atoms, advantageously 6 to 18 carbon atoms, and advantageously 6 to 14 carbon atoms.

[0062] When the diamine is a linear aliphatic diamine, then the diamine corresponds to the formula H2N-(CH2). x-NH2, and can be selected from, for example, butanediamine, pentanedanediamine, hexanediamine, heptanedanediamine, octanediamine, nonanediamine, decanedanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, hexadecanediamine, octadecanediamine, and octadecenediamine. The linear aliphatic diamines just mentioned can all be bio-based as defined in standard ASTM D6866.

[0063] When the diamine is a branched aliphatic diamine, it may be particularly 2-methylpentanediamine, 2-methyl-1,8-octanediamine or (2,2,4- or 2,4,4-)trimethylenehexanediamine.

[0064] The alkyl aromatic diamine can be selected from 1,3-phenylenediamine and 1,4-phenylenediamine.

[0065] Dicarboxylic acids can be selected from linear or branched aliphatic dicarboxylic acids.

[0066] Dicarboxylic acids can be aliphatic, alicyclic, or aromatic.

[0067] When the dicarboxylic acid is aliphatic or linear, it can be selected from succinic acid (4), glutaric acid (5), adipic acid (6), pimelic acid (7), octanoic acid (8), azelaic acid (9), sebacic acid (10), undecanoic acid (11), dodecanoic acid (12), brassic acid (13), tetradecanoic acid (14), hexadecanoic acid (16), octadecanoic acid (18), octadecenoic acid (18), eicosanoic acid (20) and docosanoic acid (22).

[0068] When the dicarboxylic acid is alicyclic, it may contain the following carbon backbones: norbornelmethane, cyclohexane, cyclohexylmethane, dicyclohexylmethane, dicyclohexylpropane, di(methylcyclohexyl) or di(methylcyclohexyl)propane.

[0069] When the dicarboxylic acid is aromatic, it can be selected from terephthalic acid (denoted as T), isophthalic acid (denoted as I), and naphthic acid (denoted as N).

[0070] In a fourth variant of this first embodiment, the semi-crystalline aliphatic polyamide is obtained by mixing these three variants.

[0071] The polyamide unit is advantageously derived from the condensation polymerization of at least one lactam, or at least one aminocarboxylic acid, or at least one aliphatic diamine with at least one aliphatic dicarboxylic acid.

[0072] The polyamide is advantageously a semi-crystalline aliphatic polyamide.

[0073] The semi-crystalline aliphatic polyamide is advantageously selected from PA410, PA510, PA512, PA514, PA610, PA612, PA1010, PA1012, PA1212, PA1014, PA11 and PA12, and more particularly PA1010, PA1012, PA1212, PA11 and PA12.

[0074] Semi-crystalline aliphatic polyamides are advantageously selected from PA6, PA66, PA11 and PA12, or mixtures thereof, or copolyamides thereof.

[0075] Advantageously, the semi-crystalline aliphatic polyamide is selected from PA11 and PA12, more particularly PA11.

[0076] Advantageously, a single semi-crystalline polyamide is present in the composition.

[0077] amorphous polyamide

[0078] Amorphous polyamides are polyamides of the formula X1Y1 or W / XY, wherein:

[0079] -W represents an aliphatic repeating unit, selected from units obtained by the condensation polymerization of at least one amino acid, units obtained by the condensation polymerization of at least one lactam, and units obtained by the condensation polymerization of at least one aliphatic diamine and at least one aliphatic diacid.

[0080] -X1 is at least one alicyclic diamine, and

[0081] -Y1 is at least one dicarboxylic acid, wherein the dicarboxylic acid is selected from aliphatic diacids, linear or branched alicyclic diacids, and aromatic diacids.

[0082] The diamine X1 and the diacid Y1 contain 4 to 36 carbon atoms, advantageously 4 to 18 carbon atoms, advantageously 6 to 18 carbon atoms, and advantageously 6 to 14 carbon atoms.

[0083] Amorphous polyamides are advantageously polyamides of the formula W / XY. The constituent amino acids, lactams, diamines, and dicarboxylic acids of unit W are as defined above for semi-crystalline aliphatic polyamides.

[0084] Amorphous polyamides can be homopolymers or copolymers.

[0085] The molar ratio of diamine X1 and dicarboxylic acid Y1 is preferably stoichiometric.

[0086] The alicyclic diamine X1 may be selected from, for example, bis(3,5-dialkyl-4-aminocyclohexyl)methane, bis(3,5-dialkyl-4-aminocyclohexyl)ethane, bis(3,5-dialkyl-4-aminocyclohexyl)propane, bis(3,5-dialkyl-4-aminocyclohexyl)butane, bis(3-methyl-4-aminocyclohexyl)methane or 3'-dimethyl-4,4'-diaminodicyclohexylmethane (commonly referred to as "BMACM" or "MACM", and hereinafter referred to as B), p-bis(aminocyclohexyl)methane (commonly referred to as "PACM", and hereinafter referred to as P), isopropylidene di(cyclohexylamine) (commonly referred to as "PACP"), isophorone diamine (hereinafter referred to as IPD), and 2,6-bis(aminomethyl)norbornene (commonly referred to as "BAMN").

[0087] A non-exhaustive list of these alicyclic diamines is given in the publication "Cycloaliphatic Amines" (Encyclopedia of Chemical Technology, Kirk-Othmer, 4th edition (1992), pp. 386-405).

[0088] Dicarboxylic acid Y1 can be selected from linear or branched aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and aromatic dicarboxylic acids.

[0089] When the dicarboxylic acid Y1 is aliphatic and linear, it is as defined above for dicarboxylic acid Y.

[0090] When dicarboxylic acid Y1 is alicyclic, it may contain the following carbon backbones: norbornelmethane, cyclohexane, cyclohexylmethane, dicyclohexylmethane, dicyclohexylpropane, di(methylcyclohexyl) or di(methylcyclohexyl)propane.

[0091] When the dicarboxylic acid Y1 is aromatic, it can be selected from terephthalic acid (denoted as T), isophthalic acid (denoted as I), and naphthic acid.

[0092] Advantageously, the dicarboxylic acid Y1 is aromatic and can be selected from terephthalic acid (denoted as T) and isophthalic acid (denoted as I).

[0093] Advantageously, amorphous polyamides are partially or entirely bio-based.

[0094] Advantageously, the amorphous polyamide is selected from 11 / B10, 12 / B10, 11 / P10, 12 / P10, 11 / BI / BT, 12 / BI / BT, 11 / PI / BT, 12 / PI / BT, 11 / PI / PT, 12 / PI / PT, 11 / BI, 12 / BI, 11 / PI and 12 / PI, especially 11 / B10.

[0095] Monocarboxylic acid unit B

[0096] Monocarboxylic acids can be aliphatic monocarboxylic acids, alicyclic acids, monounsaturated fatty acids, or aromatic monocarboxylic acids.

[0097] Aliphatic monocarboxylic acids are acids containing 2 to 18 carbon atoms.

[0098] Examples of aliphatic monocarboxylic acids are acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, hexanoic acid, decanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, and neopentanoic acid.

[0099] Alicyclic monocarboxylic acids are, for example, cyclohexane carboxylic acids;

[0100] Aromatic monocarboxylic acids include, for example, benzoic acid, benzoic acid, α- / β-naphthoic acid, methylnaphthoic acid, and phenylacetic acid, as well as their derivatives.

[0101] Monounsaturated fatty acids include, for example, palmitoleic acid, oleic acid, and undecenoic acid.

[0102] In one embodiment, the monocarboxylic acid is an aliphatic monocarboxylic acid, more particularly selected from isobutyric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, and neopentanoic acid.

[0103] In another embodiment, the monocarboxylic acid is a monounsaturated fatty acid, more specifically undecenoic acid.

[0104] diamine unit C

[0105] Diamine C can be an aliphatic diamine as defined above for X, and more particularly nonamethylenediamine, decamethylenediamine, and dodecamethylenediamine. Alicyclic diamines can be cyclohexanediamine, methylcyclohexanediamine, or an alicyclic diamine as defined above for X1, or an aromatic diamine as defined above for X.

[0106] In one embodiment, the diamine is an aliphatic diamine, more particularly hexamethylenediamine.

[0107] Triamine unit D

[0108] Triamine D can be an aliphatic triamine, such as diethylenetriamine (DETA), bis(hexamethylene)triamine, or polyether triamine.

[0109] Polyether triamines are, for example, of the following formula (I):

[0110]

[0111] Where R = H or C2H5,

[0112] x+y+z is between 4 and 100 and n = 0 or 1.

[0113] These products are especially characterized by their names. sell.

[0114] The triamine is advantageously selected from diethylenetriamine (DETA), bis(hexamethylene)triamine or polyethertriamine.

[0115] Advantageously, the aliphatic triamine is diethylenetriamine (DETA).

[0116] Optional polyetheramide unit E

[0117] The polyether amide unit is derived from the condensation polymerization of at least one polyether diamine with at least one aliphatic dicarboxylic acid.

[0118] In the first embodiment, the copolymer comprises the following:

[0119] - At least one unit (A), selected from semi-crystalline polyamide units,

[0120] - At least one monocarboxylic acid unit (B),

[0121] -At least one diamine unit (C),

[0122] -At least one triamine unit (D),

[0123] The sum of components A, B, C and D is 100% by weight, relative to the total weight of the copolymer.

[0124] In this first embodiment:

[0125] In the first variant, the copolymer consists of the following:

[0126] - At least one unit (A), selected from semi-crystalline aliphatic polyamide units,

[0127] - At least one monocarboxylic acid unit (B),

[0128] -At least one diamine unit (C),

[0129] -At least one triamine unit (D),

[0130] The sum of components A, B, C, D and E is 100% by weight, relative to the total weight of the copolymer.

[0131] In the second variant, the copolymer consists of the following:

[0132] - At least one unit (A), selected from semi-crystalline polyamide units,

[0133] - At least one monocarboxylic acid unit (B), which is undecenoic acid,

[0134] -At least one diamine unit (C),

[0135] -At least one triamine unit (D),

[0136] The sum of components A, B, C and D is 100% by weight, relative to the total weight of the copolymer.

[0137] In the third variant, the copolymer consists of the following:

[0138] - At least one unit (A), selected from semi-crystalline polyamide units,

[0139] - At least one monocarboxylic acid unit (B),

[0140] - At least one diamine unit (C), which is hexamethylenediamine,

[0141] -At least one triamine unit (D),

[0142] The sum of components A, B, C and D is 100% by weight, relative to the total weight of the copolymer.

[0143] In the fourth variant, the copolymer consists of the following:

[0144] - At least one unit (A), selected from semi-crystalline polyamide units,

[0145] - At least one monocarboxylic acid unit (B),

[0146] -At least one diamine unit (C),

[0147] - At least one triamine unit (D), which is diethylenetriamine,

[0148] The sum of components A, B, C and D is 100% by weight, relative to the total weight of the copolymer.

[0149] In the fifth variant, the copolymer consists of the following:

[0150] - At least one unit (A), selected from semi-crystalline aliphatic polyamide units,

[0151] - At least one monocarboxylic acid unit (B), which is undecenoic acid,

[0152] -At least one diamine unit (C),

[0153] -At least one triamine unit (D),

[0154] The sum of components A, B, C and D is 100% by weight, relative to the total weight of the copolymer.

[0155] In the sixth variant, the copolymer consists of the following:

[0156] - At least one unit (A), selected from semi-crystalline aliphatic polyamide units,

[0157] - At least one monocarboxylic acid unit (B),

[0158] - At least one diamine unit (C), which is hexamethylenediamine,

[0159] -At least one triamine unit (D),

[0160] The sum of components A, B, C and D is 100% by weight, relative to the total weight of the copolymer.

[0161] In the seventh variant, the copolymer consists of the following:

[0162] - At least one unit (A), selected from semi-crystalline aliphatic polyamide units,

[0163] - At least one monocarboxylic acid unit (B),

[0164] -At least one diamine unit (C),

[0165] - At least one triamine unit (D), which is diethylenetriamine,

[0166] The sum of components A, B, C and D is 100% by weight, relative to the total weight of the copolymer.

[0167] In the eighth variant, the copolymer consists of the following:

[0168] - At least one unit (A), selected from semi-crystalline aliphatic polyamide units,

[0169] - At least one monocarboxylic acid unit (B), which is undecenoic acid,

[0170] - At least one diamine unit (C), which is hexamethylenediamine,

[0171] -At least one triamine unit (D),

[0172] The sum of components A, B, C and D is 100% by weight, relative to the total weight of the copolymer.

[0173] In the ninth variant, the copolymer consists of the following:

[0174] - At least one unit (A), selected from semi-crystalline aliphatic polyamide units,

[0175] - At least one monocarboxylic acid unit (B), which is undecenoic acid,

[0176] -At least one diamine unit (C),

[0177] - At least one triamine unit (D), which is diethylenetriamine,

[0178] The sum of components A, B, C and D is 100% by weight, relative to the total weight of the copolymer.

[0179] In the tenth variant, the copolymer consists of the following:

[0180] - At least one unit (A), selected from semi-crystalline aliphatic polyamide units,

[0181] - At least one monocarboxylic acid unit (B), which is undecenoic acid,

[0182] - At least one diamine unit (C), which is hexamethylenediamine,

[0183] - At least one triamine unit (D), which is diethylenetriamine,

[0184] The sum of components A, B, C and D is 100% by weight, relative to the total weight of the copolymer.

[0185] Advantageously, in these ten variants, the molar proportion of unit A is twice the molar proportion of the sum of units B and C.

[0186] Advantageously, among these ten variants, the semi-crystalline polyamide is PA11.

[0187] Advantageously, in these ten variants, the molar ratio of unit A is twice the molar ratio of the sum of units B and C, and the semi-crystalline polyamide is PA11.

[0188] In the second embodiment, the copolymer comprises the following:

[0189] - At least one unit (A), selected from semi-crystalline polyamide units,

[0190] - At least one monocarboxylic acid unit (B),

[0191] -At least one diamine unit (C),

[0192] -At least one triamine unit (D),

[0193] - At least one polyetheramide unit (E),

[0194] The sum of components A, B, C, D and E is 100% by weight, relative to the total weight of the copolymer.

[0195] In this second embodiment, the ten variations defined above are also possible.

[0196] In these first and second embodiments, the same ten variations exist for each embodiment, except that the polyamide is a semi-crystalline, semi-aromatic polyamide.

[0197] Advantageously, in these later variants, the molar proportion of unit A is twice the molar proportion of the sum of units B and C.

[0198] Advantageously, the semi-crystalline semi-aromatic polyamide is selected from PA6I / 6T, PA11 / 10T, PABACT / 6T, PA11 / BACT / 6T, PABACT / 10T, PA11 / BACT / 10T, and PAMXD10.

[0199] In the third embodiment, the copolymer comprises the following:

[0200] - At least one unit (A), selected from amorphous polyamide units,

[0201] - At least one monocarboxylic acid unit (B),

[0202] -At least one diamine unit (C),

[0203] -At least one triamine unit (D),

[0204] The sum of components A, B, C and D is 100% by weight, relative to the total weight of the copolymer.

[0205] In the fourth embodiment, the copolymer comprises the following:

[0206] - At least one unit (A), selected from amorphous polyamide units,

[0207] - At least one monocarboxylic acid unit (B),

[0208] -At least one diamine unit (C),

[0209] -At least one triamine unit (D),

[0210] - At least one polyetheramide unit (E),

[0211] The sum of components A, B, C, D and E is 100% by weight, relative to the total weight of the copolymer.

[0212] In these third and fourth embodiments, in addition to the polyamide being amorphous polyamide, there are ten variations defined for the first and second embodiments.

[0213] Advantageously, in these variations of the third and fourth embodiments, the molar ratio of unit A is twice the molar ratio of the sum of unit B and unit C.

[0214] Advantageously, the amorphous polyamide is selected from B10, P10, B12, P12, B14, P14, 11 / B10 and copolyamides such as 6 / 66 / 12.

[0215] Advantageously, the amorphous polyamide is selected from B10, P10, B12, P12, B14, P14 and 11 / B10.

[0216] P represents bis(4-aminocyclohexyl)methane, also referred to as PACM or P in the specification.

[0217] B represents bis(4-amino-3-methylcyclohexyl)methane, also referred to as MACM or BMACM or B in the specification.

[0218] 10 represents sebacic acid, 12 represents dodecanedioic acid, and 14 represents tetradecanedioic acid.

[0219] 11 represents aminoundecanedioic acid.

[0220] Advantageously,

[0221] About magnetic composite materials

[0222] Magnetic composite materials include:

[0223] 4% to 30% by weight of copolymers as defined above,

[0224] 70% to 96% by weight of magnetic powder,

[0225] At least one coupling agent, ranging from 0% to 5% by weight.

[0226] At least one additive, ranging from 0% to 5% by weight.

[0227] The total amount of copolymers, magnetic powders, coupling agents, and additives is 100% by weight.

[0228] In one embodiment, the magnetic composite material comprises the following:

[0229] 4% to 30% by weight of copolymers as defined above,

[0230] 70% to 96% by weight of magnetic powder,

[0231] At least one coupling agent, ranging from 0% to 5% by weight.

[0232] At least one additive, ranging from 0% to 5% by weight.

[0233] The total amount of copolymers, magnetic powders, coupling agents, and additives is 100% by weight.

[0234] Magnetic powder

[0235] The magnetic powders used in the magnetic composite materials defined above are selected from iron-nickel-aluminum alloys, ferrites, samarium-cobalt alloys, neodymium-iron-boron alloys, manganese-aluminum-carbon alloys, and samarium-iron-nitrogen alloys.

[0236] The magnetic powders for the magnetic composite materials defined above are advantageously selected from iron-nickel-aluminum alloys, ferrites, samarium-cobalt alloys, neodymium-iron-boron alloys, and manganese-aluminum-carbon alloys.

[0237] Coupling agent

[0238] Magnetic metal powders can be pretreated with a coupling agent to improve the adhesion between the powder and the polyamide resin.

[0239] Examples of coupling agents include silane compounds, titanate compounds, aluminum compounds, chromium compounds, methacrylate compounds, and organophosphorus compounds such as phosphites.

[0240] In one embodiment, the coupling agent is present in the form of 0.1% to 5% by weight.

[0241] additive

[0242] The additives may be any additives known to those skilled in the art, especially catalysts, particularly H3PO4 and H3PO2, antioxidants, especially phenolic or phosphoric acid antioxidants or hindered amine light stabilizers (HALS), UV stabilizers, and defoamers.

[0243] In one embodiment, talc, graphite, and magnesium oxide are excluded from the magnetic composite material.

[0244] In another embodiment, Sm-Fe-N is excluded from magnetic powders, and therefore from magnetic composite materials.

[0245] In yet another embodiment, the dendritic silane-polyamide-amine polymer is excluded from the magnetic composite material.

[0246] In the last and other embodiments, lubricants are excluded from additives, and therefore from magnetic composite materials.

[0247] The four implementation methods defined above can also be combined in pairs, or three of the four implementation methods can be combined, or all four of the four implementation methods defined above can be combined.

[0248] In one embodiment, the coupling agent is present in the form of 0.1% to 5% by weight.

[0249] In another aspect, the present invention relates to a method for producing a magnetic composite material as defined above, characterized in that the method comprises the steps of mixing a copolymer as defined above in pellet form with a magnetic powder, and optionally at least one coupling agent and at least one additive, said magnetic powder being more particularly as defined above.

[0250] In one embodiment, the method for producing the magnetic composite material includes the steps of extruding and granulating a mixture of magnetic powder with the copolymer in particulate form and optionally a coupling agent and / or additives. Example

[0251] Example 1: Preparation of the copolymer of the present invention and the comparative copolymer

[0252] Embodiment I1 of the present invention

[0253] Add 5000g of 11-aminoundecanoic acid, 11.5g of diethylenetriamine (DETA), 66g of hexamethylenediamine (HMDA), 209g of undecenoic acid, and 5g of [other substances] to a high-pressure reactor equipped with a stirrer. 1098 g of 85% phosphoric acid, 0.2 g of siliconol 1000, and 150 g of water were used. The reactor was heated to 250°C (material temperature) under autogenous pressure and stirring. This condition was maintained for 1 hour, then the reactor was depressurized to atmospheric pressure and the temperature was lowered to 240°C. A nitrogen purging phase was run for 30 minutes, followed by establishing a 50 mbar depressurization for 90 minutes, after which the reactor was vented.

[0254] Embodiment I2 of the present invention

[0255] 2000g of caprolactam, 11.5g of diethylenetriamine (DETA), 508.96g of hexamethylenediamine (HMDA), 557.04g of adipic acid, 2000g of laurylactam, 209g of undecenoic acid, and 5g of [unclear - possibly a specific ingredient or substance] were added to a high-pressure reactor equipped with a stirrer. 1098 g of 85% phosphoric acid, 0.2 g of siliconol 1000, and 200 g of water were used. The reactor was heated to 260°C (material temperature) under autogenous pressure and stirring. This condition was maintained for 4 hours, then the reactor was allowed to depressurize to atmospheric pressure and the temperature was lowered to 240°C. A nitrogen purging phase was run for 30 minutes, followed by establishing a 50 mbar depressurization for 90 minutes, after which the reactor was vented.

[0256] Counterexample C1

[0257] 5000g of 11-aminoundecanoic acid, 70g of lauric acid, 0.2g of siliconol 1000, and 150g of water were added to a high-pressure reactor equipped with a stirrer. The reactor was heated to 250°C (material temperature) under autogenous pressure and stirring. This condition was maintained for 1 hour, then the reactor was allowed to decrease to atmospheric pressure and the temperature to 240°C. A nitrogen purging phase was run for 30 minutes, followed by establishing a 50 mbar depressurization for 90 minutes, after which the reactor was emptied.

[0258] Counterexample C2

[0259] 1000g of 11-aminoundecanoic acid, 1894g of decamethyldiamine, 2160g of sebacic acid, 90g of stearic acid, 0.2g of siliconol 1000, and 150g of water were charged into a high-pressure reactor equipped with a stirrer. The reactor was heated to 250°C (material temperature) under autogenous pressure and stirring. This condition was maintained for 1 hour, then the reactor was allowed to decrease to atmospheric pressure and the temperature to 240°C. A nitrogen purging phase was run for 30 minutes, followed by establishing a 50 mbar depressurization for 90 minutes, after which the reactor was emptied.

[0260] Counterexample C3

[0261] 1100g of caprolactam, 398.7g of hexamethylenediamine (HMDA), 581.3g of adipic acid, 3000g of dodecyl lactam, and 5g of [unspecified ingredient] were added to an autoclave equipped with a stirrer. 1098, 0.2 g of siliconol 1000, and 200 g of water. The reactor was heated to 260°C (material temperature) under autogenous pressure and stirring. This condition was maintained for 4 hours, then the reactor was allowed to decrease to atmospheric pressure and the temperature to 240°C. A nitrogen purging phase was run for 30 minutes, followed by establishing a 50 mbar depressurization for 90 minutes, after which the reactor was emptied.

[0262] Counterexample C4

[0263] 1100g of caprolactam, 710.1g of hexamethylenediamine (HMDA), 779.9g of adipic acid, 2500g of dodecyl lactam, and 5g of [unspecified ingredient] were added to an autoclave equipped with a stirrer. 1098, 0.2 g of siliconol 1000, and 200 g of water. The reactor was heated to 260°C (material temperature) under autogenous pressure and stirring. This condition was maintained for 4 hours, then the reactor was allowed to decrease to atmospheric pressure and the temperature to 240°C. A nitrogen purging phase was run for 30 minutes, followed by establishing a 50 mbar depressurization for 90 minutes, after which the reactor was emptied.

[0264] Example 2: Acidity and basicity analysis of the copolymer from Example 1

[0265] Alkalinity and acidity were measured as described in the text and are shown in Table 1.

[0266] [Table 1]

[0267]

[0268]

[0269] Example 3: Rheological analysis of magnetic composite materials obtained by mixing comparative and the copolymers of the present invention with NdFeB (5 / 95 wt / wt) ferrite powder.

[0270] The polymers of Examples I1, I2 and C1 to C4 were ground in liquid nitrogen and mixed with magnetic fillers.

[0271] After drying under reduced pressure at 90°C for 12 hours, the sample was placed in a rheometer (MCR301) to measure the melt viscosity. A 30-minute time sweep was performed between two parallel plates with a diameter of 25 mm under nitrogen atmosphere at 1 Hz and 210°C.

[0272] The initial viscosity corresponds to the measurement value after the rheometer is started: t0+10 seconds is used to record the measurement value.

[0273] The viscosity after 30 minutes corresponds to the measurement value after scanning in the rheometer for 30 minutes.

[0274] Table 2 shows that, compared with the comparative examples, the copolymers of the present invention exhibit viscosity stability.

[0275] [Table 2]

[0276] copolymer I1 / NdFeB 1300 3850 copolymer I2 / NdFeB 1370 3920 copolymer C1 / NdFeB 6398 13 390 copolymer C2 / NdFeB 5620 12 350 copolymer C3 / NdFeB 3970 21 800 copolymer C4 / NdFeB 2710 10 000

Claims

1. A magnetic composite material, characterized in that... It includes: 4% to 30% by weight of copolymers, 70% to 96% by weight of magnetic powder, At least one coupling agent, ranging from 0% to 5% by weight. At least one additive, ranging from 0% to 5% by weight. The total amount of the copolymer, the magnetic powder, the coupling agent, and the additive is 100% by weight. The copolymer has the following composition: - At least one unit (A), said unit (A) being selected from polyamide units with an average carbon number relative to a nitrogen atom greater than or equal to 6. - At least one monocarboxylic acid unit (B), -At least one diamine unit (C), -At least one triamine unit (D), -Optionally at least one polyetheramide unit (E), The sum of components A, B, C, D, and E is 100% by weight relative to the total weight of the copolymer.

2. The magnetic composite material according to claim 1, characterized in that... The copolyamide has an acid chain end content of less than 10 μeq / g.

3. The magnetic composite material according to claim 1 or 2, characterized in that... The copolyamide has an amine end content of less than 80 μeq / g.

4. The magnetic composite material according to claim 1 or 2, characterized in that... The polyamide unit is derived from the following polycondensation: at least one lactam, or at least one aminocarboxylic acid, or at least one diamine and at least one dicarboxylic acid.

5. The magnetic composite material according to claim 4, characterized in that... The polyamide unit is derived from the following polycondensation: at least one lactam, or at least one aminocarboxylic acid, or at least one aliphatic diamine and at least one aliphatic dicarboxylic acid.

6. The magnetic composite material according to claim 1 or 2, characterized in that... The polyamide is a semi-crystalline aliphatic polyamide.

7. The magnetic composite material according to claim 6, characterized in that... The polyamide is selected from PA410, PA510, PA512, PA514, PA610, PA612, PA1010, PA1012, PA1212, PA1014, PA6, PA66, PA11 and PA12.

8. The magnetic composite material according to claim 7, characterized in that... The polyamide is selected from PA1010, PA1012, PA1212, PA11, and PA12.

9. The magnetic composite material according to claim 6, characterized in that... The semi-crystalline aliphatic polyamide is selected from PA6, PA66, PA11 and PA12, or mixtures thereof, or copolyamides thereof.

10. The magnetic composite material according to claim 6, characterized in that... The polyamide is selected from PA11 and PA12.

11. The magnetic composite material according to claim 10, characterized in that... The polyamide is PA11.

12. The magnetic composite material according to claim 1 or 2, characterized in that... The polyamide is an amorphous polyamide.

13. The magnetic composite material according to claim 12, characterized in that... The polyamide is selected from 11 / B10, 12 / B10, 11 / P10, 12 / P10, 11 / BI / BT, 12 / BI / BT, 11 / PI / BT, 12 / PI / BT, 11 / PI / PT, 12 / PI / PT, 11 / BI, 12 / BI, 11 / PI and 12 / PI.

14. The magnetic composite material according to claim 13, characterized in that... The polyamide is 11 / B10.

15. The magnetic composite material according to claim 1 or 2, characterized in that... The polyetheramide unit is derived from the polycondensation of at least one polyether diamine and at least one aliphatic dicarboxylic acid.

16. The magnetic composite material according to claim 1 or 2, characterized in that... The monocarboxylic acid is selected from aliphatic monocarboxylic acids.

17. The magnetic composite material according to claim 16, characterized in that... The monocarboxylic acid is selected from tridecanoic acid, myristic acid, palmitic acid, stearic acid, neopentanoic acid, and isobutyric acid.

18. The magnetic composite material according to claim 1 or 2, characterized in that... The monocarboxylic acid is selected from monounsaturated fatty acids.

19. The magnetic composite material according to claim 18, characterized in that... The monounsaturated fatty acid is undecenoic acid.

20. The magnetic composite material according to claim 1 or 2, characterized in that... The diamine is an aliphatic diamine.

21. The magnetic composite material according to claim 20, characterized in that... The diamine is hexamethylenediamine.

22. The magnetic composite material according to claim 1 or 2, characterized in that... The triamine is selected from diethylenetriamine (DETA), bis(hexamethylene)triamine, or polyethertriamine.

23. The magnetic composite material according to claim 1 or 2, characterized in that... The magnetic powder is selected from iron-nickel-aluminum alloys, ferrites, samarium-cobalt alloys, neodymium-iron-boron alloys, manganese-aluminum-carbon alloys, and samarium-iron-nitrogen alloys.

24. A method for producing a magnetic composite material as defined in any one of claims 1 to 23, characterized in that... It includes the following steps: mixing the copolymer in particulate form as defined in any one of claims 1 to 23 with magnetic powder, and optionally at least one coupling agent and at least one additive.

25. The method for producing magnetic composite materials according to claim 24, characterized in that... The magnetic powder is as defined in claim 23.

26. The method for producing magnetic composite materials according to claim 24 or 25, characterized in that... The method includes the following steps: extruding and granulating a mixture of magnetic powder with the copolymer in particulate form and optionally the coupling agent and / or the additive.

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