Flame-retardant polyamide composition

Abstract

The present invention relates to a random copolymer comprising a) i) a first linear aliphatic condensation polyamide; and ii) a second condensation polyamide comprising a branched diamine and an aromatic diacid, wherein the mass ratio of the first linear aliphatic condensation polyamide to the second condensation polyamide is 85:15 or more to 99:1 or less; and b) a composition of a material comprising 5% by weight to 25% by weight of a non-halogenated flame retardant additive, wherein the flame retardant (FR) performance, as measured by a flammability measurement according to the Underwriters Laboratories standard (UL 94) for a vertical combustion test of the composition, exceeds the FR performance of a control essentially composed of nylon-6,6 characterized by a formic acid relative viscosity (RV) within ±3 of the random copolymer (a) and amine end groups (AEG) within ±5, wherein the composition of the material contains 50% to 80% of a non-halogenated flame retardant (FR) additive compared to the control.

Description

Technology Field

[0001] In this specification, the invention relates to a modified nylon polymer resin for use in articles and molded parts. Background Technology

[0002] The homopolymer polyhexamethylene adipamide (commonly known in the art as PA66 or N66) can crystallize very rapidly when cooled from a molten state. The crystallization rate of N66 is known to be strongly temperature-dependent, reaching a maximum rate at approximately 220°C. At this temperature, the kinetic half-time (t) of crystallization 1 / 2 The time is about 1 minute. For some polymer applications, this can be disadvantageous, for example, in terms of surface appearance and dimensional stability of parts molded from glass fiber (i.e., GF) reinforced resins. N66-based copolymers can provide better results if the crystallization rate is sufficiently slowed down.

[0003] An aliphatic nylon copolyamide comprising 60 to 99.5 mol% of hexamethylene adipamide units and 0.5 to 40 mol% of 2-methyl-pentamethylene adipamide units is described in U.S. Patent No. 5,194,578. The present disclosure relates to fiber and fabric applications of copolyamides.

[0004] U.S. Patent No. 10,711,104 B2 relates to a composition comprising about 65 to about 95 weight percent of an aliphatic polyamide and about 40 to about 60 mol percent of 2-methyl-1,5-pentamethyleneterephthalamide ("MPMD-T") units and about 40 to about 60 mol percent of 2-methyl-1,5-pentamethyleneisophthalamide ("MPMD-I") units.

[0005] A composition is disclosed that exhibits improved sensitivity to a halogen-free phosphorus-containing flame retardant (FR) additive. As understood by those skilled in the art, improved sensitivity to a halogen-free phosphorus-containing FR additive means that less halogen-free phosphorus-containing FR additive is required in the composition to achieve the same flame retardant performance. Consequently, the resulting composition has improved persistence as less material is used. Furthermore, considering the high cost of halogen-free phosphorus-containing FR additives typically used in the art, the resulting composition containing less halogen-free phosphorus-containing additive is more economical.

[0006] The present invention

[0007] a)

[0008] i) a first linear aliphatic condensation polyamide; and

[0009] ii) a random copolymer of a second condensation polyamide comprising a branched diamine and an aromatic diacid,

[0010] A random copolymer in which the mass ratio of the first linear aliphatic condensation polyamide to the second condensation polyamide is 85:15 or more to 99:1 or less; and

[0011] b) The invention relates to a composition of a material comprising 5 weight% or more to 25 weight% or less of a non-halogenated flame-retardant additive;

[0012] Herein, the flame retardant (FR) performance, as measured by the flammability measurement according to the Underwriters Laboratories standard (UL 94) for vertical combustion testing of the composition, exceeds the FR performance of a control essentially made of nylon-6,6 characterized by a formic acid relative viscosity (RV) within ±3 of the random copolymer (a) and amine end groups (AEG) within ±5, wherein the composition of the material contains 50% or more to 80% or less of a non-halogenated flame retardant (FR) additive compared to the control.

[0013] As used herein, "essentially composed of" or "essentially composed of" means that certain additional components may be present, provided that they do not substantially affect the essential characteristics of the composition. Thus, if the control is essentially composed of nylon-6,6, this means that the control does not contain any other components that substantially affect the essential characteristics of the control. In particular, if the control is essentially composed of nylon-6,6, it does not contain any other polyamide or any other diamine or discrete monomer.

[0014] As is understood, the control group described in this specification is identical to the composition of the material except for the amount of FR additive present and the polyamide identity.

[0015] The present invention also relates to the use of said random copolymer to provide a composition of a material comprising said random copolymer having similar or improved flame retardant (FR) performance compared with a control group, said flame retardant (FR) performance being measured by flammability measurements according to the Underwriters Laboratories standard (UL 94) for vertical combustion testing; said composition of said material

[0016] a)

[0017] i) a first linear aliphatic condensation polyamide; and

[0018] ii) as the random copolymer of the second condensation polyamide comprising a branched diamine and an aromatic diacid,

[0019] A random copolymer in which the mass ratio of the first linear aliphatic condensation polyamide to the second condensation polyamide is 85:15 or more to 99:1 or less; and

[0020] b) comprising 5 weight% or more to 25 weight% or less of a non-halogenated flame-retardant additive;

[0021] Herein, the control group is essentially composed of nylon-6,6 characterized by a formic acid relative viscosity (RV) within ±3 of the random copolymer (a) and amine terminal groups (AEG) within ±5;

[0022] Here, the composition of the above material contains 50% or more to 80% or less of a non-halogenated flame retardant (FR) additive compared to the control group.

[0023] As used herein, the terms “non-halogenated” and “halogen-free” are used interchangeably to refer to flame-retardant additives that do not contain any carbon-halogen bonds.

[0024] Preferably, the halogen-free flame retardant (FR) additive is a halogen-free phosphorus-containing FR additive. Accordingly, the composition according to the present invention may contain 50% by weight or more to 80% by weight or less of a halogen-free phosphorus-containing FR additive compared to a control group.

[0025] Advantageously, the composition according to the present invention may contain 50% by weight and up to 80% by weight of FR additives compared to a control group without impairing any FR performance (as measured by flammability measurements according to Underwriters Laboratories Standard (UL 94) for vertical combustion tests).

[0026] Furthermore, the composition according to the present invention may advantageously contain 50% by weight and 80% by weight of FR additives compared to a control group without impairing any mechanical strength (e.g., yield stress, tensile strength, elongation at break, cord modulus, notched Charpie and / or non-notched Charpie). In fact, the composition according to the present invention provides a flame-retardant specimen having improved mechanical strength compared to a control flame-retardant specimen essentially made of nylon-6,6, wherein the composition contains 50% to 80% of non-halogenated flame-retardant (FR) additives compared to the control group composition.

[0027] Preferably, the mass ratio of the first linear aliphatic condensed polyamide to the second condensed polyamide is 90:10 or more to 97:3 or less.

[0028] Suitable first straight-chain aliphatic condensed polyamide comprises at least one of PA 46, PA 66; PA 69; PA 610, PA 612, PA 1012, PA 1212, PA 66 / 6T, PA 6I / 6T, PA 66 / 6I / 6T or blends, e.g., PA6 / PA66, polyhexamethylene decanamide (N610), polyhexamethylene dodecanamide (N612), polyhexamethylene succinamide (N46), polyhexamethylene azelamide (N69), polydecamethylene sebacaramide (N1010), polydodecamethylene dodecanamide (N1212), nylon 6 (N6), nylon 11 (N11), and polylaurolactam (N12). Preferably, in the composition according to the present invention, the first straight-chain condensed polyamide is PA 66.

[0029] Branched diamines are C4 to C 12 It could be diamine.

[0030] For example, the branched diamine may be at least one of 1,3-pentanediamine, 2-ethyl-butanediamine, 2-methylpentamethylene diamine, 3-methylpentamethylene diamine, 2-methylhexamethylene diamine, 3-methylhexamethylene diamine, 2,5-dimethylhexamethylene diamine, 2,2,4-trimethylhexamethylene diamine, 2,4,4-trimethylhexamethylene diamine, 2,7-dimethyloctamethylene diamine, and 2,2,7,7-tetramethyloctamethylene diamine. Preferably, in the composition according to the present invention, the branched diamine is 2-methylpentamethylene diamine, which is also referred to as MPMD.

[0031] Suitable aromatic diacids are C5 to C5 containing one or more to three or fewer aromatic rings per monomer unit. 12 Includes this mountain.

[0032] Suitable aromatic diacids have the chemical formula HO-C(O)-R 1 At least one discrete of -C(O)-OH, and in the above equation, variable R 1 It is substituted or unsubstituted furan, benzofuranyl, phenyl, naphthyl, or anthracenyl.

[0033] Preferably, the aromatic diacid may include one or more of terephthalic acid and isophthalic acid. More preferably, the aromatic diacid includes isophthalic acid.

[0034] Preferably, the composition according to the present invention comprises a random copolymer composed of or essentially composed of n-6,6 / DI having a weight ratio of n-6,6 to (D + I) of 85:15 to 99:1. Preferably, the composition according to the present invention comprises a random copolymer composed of or essentially composed of n-6,6 / DI having a weight ratio of n-6,6 to (D + I) of 90:10 to 97:3.

[0035] The disclosed composition comprises a non-halogenated flame retardant additive that does not contain, for example, carbon-iodine, carbon-bromine, or carbon-chlorine bonds. The disclosed composition may comprise the non-halogenated flame retardant additive alone or in combination with a phosphorus-based FR additive, for example, an organophosphorus acid, e.g., diarylphosphinic acid, diarylphosphonic acid, diarylphosphinic acid or dialkylphosphinic acid or dialkylphosphonic acid and salts thereof (including metal salts or organic salts), dihydrooxaphosphaphenanthrene (DOPO) and derivatives thereof, polyphosphazene; an organic-nitrogen-based FR additive comprising melamine and salts thereof; a boron-based FR additive comprising a metal borate; and a silicon-based FR additive, e.g., silicon. Preferably, the non-halogenated flame retardant additive is a non-halogenated phosphorus-containing (i.e., phosphorus-based) flame retardant additive.

[0036] Non-halogenated flame retardant additives may be selected from melamine cyanurate, aluminum diethylphosphinate, melamine polyphosphate, antimony trioxide, dehydrated zinc borate, and combinations thereof.

[0037] Non-limiting examples of various commercially available flame retardant additives include BASF Melapur™ MC25 halogen-free flame retardant or BASF Irganox ® B1171 Polymer Additive Products; Mastertek from Campine, NY ® Antimony trioxide concentrate masterbatch; Clariant Exolit ® OP1314 or OP1400 non-halogenated organic phosphinate flame retardant; Presafer (Quingyuan) Phosphor Chemical Co. Ltd. Preniphor™ EPFR-MPP300 halogen-free melamine polyphosphate flame retardant; Albemarle SAYTEX ®HP 7010 Brominated flame retardant; Campine PA 261717, a 50% masterbatch of Antimony Trioxide in Nylon 6 [CAS No. 1309-64-4]; Borax Europe Ltd Firebrake ® It may include 500 dehydrated zinc borate-based flame retardants, or a combination thereof.

[0038] also,

[0039] a)

[0040] (1) A first aliphatic condensed polyamide containing less than 0.1 weight% of a monomer selected from branched diamines and aromatic diacids;

[0041] (2) Random copolymer of a second condensation polyamide comprising a branched diamine and an aromatic diacid; and

[0042] b) A composition of a material comprising a halogen-free phosphorus-containing flame-retardant additive is disclosed, wherein

[0043] i) The weight ratio of the first aliphatic condensed polyamide (1) to the second condensed polyamide (2) is 90:10 or more to 94:6 or less;

[0044] ii) The flame retardant (FR) performance of the random copolymer, as measured by the UL 94 vertical combustion test, is,

[0045] (1) First aliphatic condensation polyamide;

[0046] (2) a second condensed polyamide of 0 to 0.1 weight% or less; and

[0047] (3) Exceeds the performance of a control group containing an equal amount (i.e., ± 0.5% based on the weight of the additive) of a halogen-free phosphorus-containing flame retardant additive (as measured by the same UL 94 vertical combustion test), wherein the first aliphatic condensed polyamide of (ii)(1) and the random copolymer of (a) both have the same formic acid relative viscosity (RV; i.e. within ±3 of each other) and the same amine terminal group (AEG; i.e. within ±5 of each other), wherein the composition of the material contains 50% or more to 80% or less of a halogen-free phosphorus-containing FR additive compared to the control group.

[0048] In the case of the composition described immediately above, both the composition according to the present invention and the control group may additionally include 5% by weight or more to 25% by weight or less of a halogen-free phosphorus-containing flame retardant additive.

[0049] Advantageously, the composition of the present invention has improved FR additive sensitivity while containing 50% by weight to 80% by weight of a halogen-free phosphorus-containing FR additive as a control.

[0050] Preferably, the first linear aliphatic condensed polyamide comprises an aliphatic diamine.

[0051] Branched diamines

[0052] a) 0 or more to 1 or less;

[0053] b) 0.2 or more to 0.8 or less; and

[0054] c) It may be a C4 to C20 diamine characterized by a carbon branching rate selected from the group consisting of 0.25 or more to 0.75 or less (as defined in this specification).

[0055] In the case of an embodiment in which specific FR sensitivity can be observed, the branched diamine may be at least one of ESN (i.e., 2-ethylsuccinonitrile) and MPMD (i.e., 2-methylpentamethylene diamine).

[0056] The disclosed composition is an aromatic diacid, for example, a C4 to C4 containing one or more to three or fewer aromatic rings per monomer unit. 12 It may include diacids, for example, aromatic diacids have the chemical formula HO-C(O)-R 1 Includes at least one discrete of -C(O)-OH, and the variable R in the above formula 1 is substituted or unsubstituted furan, benzofuranyl, phenyl, naphthyl, or anthracenyl. Aromatic diacid may include at least one selected from terephthalic acid and isophthalic acid.

[0057] also,

[0058] a) a random copolymer of n-6,6 / DI having a weight ratio of n-6,6 to DI of 85:15 or more to 99:1 or less; and

[0059] b) A composition of a material comprising 5 weight% or more to 25 weight% or less of a halogen-free phosphorus-containing flame-retardant additive is disclosed;

[0060] i) Here, the FR performance of the composition comprising (a) and (b) as measured by the UL 94 vertical combustion test is

[0061] (i) Nylon-6,6 containing 0.1 wt% or less of DI, wherein the Nylon-6,6 is characterized by a formic acid RV within ±3 of the random copolymer (a) and an AEG within ±5 of the random copolymer (a); and

[0062] (ii) exceeding the performance of a control group containing 5 weight% or more to 25 weight% or less of a halogen-free phosphorus-containing flame retardant additive (as measured by the same UL 94 vertical combustion test), and

[0063] Here, the composition of the material including (a) and (b) contains 50% or more to 80% or less of a halogen-free phosphorus-containing flame retardant additive compared to the control group. Specific details for implementing the invention

[0064] The terms "Nylon-6", "Polyamide 6", "PA6", and "N6" are used interchangeably and refer to polycaproamide, which is a homo-polyamide formed from caprolactam.

[0065] The terms "Nylon-6,6", "Polyamide 66", "PA66", "N66", "Nylon 6-6", "n-6,6", or "Nylon 6 / 6" are used interchangeably and refer to polyhexamethylene adipamide, which is a polyamide formed by a polycondensation reaction between hexamethylene diamine (HMD) and adipic acid (AA).

[0066] As used herein, “PA66 (20 to 36 RV)” refers to a polyhexamethylene adipamide having a relative viscosity (RV) of 20 to 36. Such a polyamide is described in International Patent Application Publication WO2019 / 125379A1 and is commercially available under the trademark HYPERFLOW™ polyamide from INVISTA Intermediates.

[0067] As used herein, "PA66 / DI" refers to a type of co-polyamide formed by combining an N66 salt solution with a DI salt solution, where "D" is an abbreviation for 2-methyl-1,5-pentamethylenediamine (also known as MPMD) and "I" is an abbreviation for commercially available isophthalic acid. MPMD is a trademark registered in INVISTA S. a r. 1. DYTEK ®It is commercially available under A Amine (CAS registration number 15520-10-2). PA66 / DI may contain about 80 to 99% PA66 and about 1 to 20% DI by mass, for example, about 99:1 or 97:3 or 95:5 or 92:8 or 90:10 or 85:15 or 80:20 (on a wt:wt basis) for the PA66:DI ratio achieved for the salt on a dry matter basis. The “DI” portion in PA66 / DI is about 50:50 (mol) or about 40:60 D:I (mass ratio). PA66 / DI is known as a copolymer of hexamethylene adipamide and 2-methyl-1,5-pentamethylene-isophthalamide. The PA66 / DI used in the examples has a relative viscosity (RV) of 45. However, the RV range for PA66 / DI may be 35 to 60 and may contain 40 to 80 meg / kg, e.g. 60 to 80 meg / kg, or 65 meg / kg, or 70 meg / kg of amine terminal groups (AEG). Standard batch evaporation and batch autoclave polymerization processes are used to produce the copolymer. These methods are polymerization processes generally known to those skilled in the art.

[0068] As used herein, "PA66 / D6" refers to a type of copolyamide formed by combining a PA66 salt solution with a D6 salt solution (wherein "D" is an abbreviation for 2-methyl-1,5-pentamethylene diamine (MPMD) and "6" refers to adipic acid, a C6 dicarboxylic acid), having a ratio of approximately 90 / 10, 87 / 13, 85 / 15, 82 / 18, 80 / 20, 75 / 25, or 70 / 30 (based on wt:wt mass) for the PA66 / D6 achieved for the salt on a dry matter basis. Standard batch evaporation and batch autoclave polymerization processes are used to produce said copolymer. The diacid equivalent is adipic acid (abbreviated as "6"), which is used with the same diamine "D" as described above. These copolyamide resins have a calculated formic acid solution RV of 45, a moisture content of 0.144 wt%, and a maximum crystallization rate at about 150°C. A copolyamide N66 / D6 (70 / 30) prepared by combining a PA66 salt solution with a D6 salt solution and using a 70 / 30 mass ratio of salt on a dry matter basis is disclosed. Standard batch evaporation and batch autoclave polymerization processes are used to produce the copolymer. The diacid equivalent may be adipic acid, which is a 6-carbon dicarboxylic acid.

[0069] The present invention provides a modified nylon comprising, or composed of, or essentially composed of, a random copolymer of N66 / DI in which 5 to 15 mol% of HMD is substituted with D and 5 mol% to 15 mol% of adipic acid is substituted with isophthalic acid (I), having a slower crystallization rate than that of an N66 homopolymer, which can additionally provide improved surface appearance and gloss in extruded and molded parts.

[0070] The term “carbon branching ratio” used in the present invention describes the degree to which aliphatic carbons are present in the branch relative to the skeletal chain of the molecule. For example, at a carbon branching ratio of 1:3 (i.e., 0.33), isobutane has one carbon in the branch and three carbons in the skeletal chain. At a carbon branching ratio of 1:5 (i.e., 0.2), MPMD contains six (6) carbon atoms, one of which is present in the branch. At a carbon branching ratio of 2:4 (i.e., 0.5), 2-ethyl-butanediamine contains six (6) carbon atoms, two of which are present in the branch. At a carbon branching ratio of 0:6 (i.e., 0), 1,6-hexamethylenediamine (HMD) contains six (6) carbon atoms, none of which are present in the branch. As is understood by those skilled in the art, the branching of linear aliphatic chains is always 0.

[0071] Polyamides can be prepared by the polymerization of diamines with dicarboxylic acids and diacid derivatives. In some cases, polyamides can be prepared through the polymerization of aminocarboxylic acids, aminonitriles, or lactams. The dicarboxylic acid component is suitably of the molecular formula HO2C-R 1 -CO2H is at least one dicarboxylic acid; where, R 1 represents a divalent aliphatic, alicyclic, or aromatic radical or covalent bond. R 1 It suitably comprises 2 to 20 carbon atoms, for example, 2 to 12 carbon atoms, for example, 2 to 10 carbon atoms. For example, R 1 is an alkylene radical comprising 2 to 12 carbon atoms, or 2 to 10 carbon atoms, for example, 2, 4, 6, or 8 carbon atoms, e.g., an alkylene radical. R 1may be a linear or branched (e.g., linear) alkylene radical, an unsubstituted phenylene radical, or an unsubstituted cyclohexylene radical comprising 2 to 12 carbon atoms, or 2 to 10 carbon atoms, e.g., 2, 4, 6, or 8 carbon atoms. Optionally, R 1 It may contain one or more ether groups.

[0072] Specific examples of suitable dicarboxylic acids include hexane-1,6-dicarboxylic acid (adipic acid), octane-1,8-dicarboxylic acid (suberic acid), decane-1,10-dicarboxylic acid (sebacic acid), dodecane-1,12-dicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanediacetic acid, 1,3-cyclohexanediacetic acid, benzene-1,2-dicarboxylic acid (phthalic acid), benzene-1,3-dicarboxylic acid (isophthalic acid), benzene-1,4-dicarboxylic acid (terephthalic acid), 4,4'-oxybis(benzoic acid), and 2,6-naphthalene dicarboxylic acid. A suitable dicarboxylic acid is hexane-1,6-dioic acid (adipic acid).

[0073] The diamine component is suitably the chemical formula H2N-R 2 -At least one diamine of -NH2; where, R 2 represents a divalent aliphatic, alicyclic, or aromatic radical. R 2 It suitably comprises 2 to 20 carbon atoms, for example, 4 to 12 carbon atoms, for example, 4 to 10 carbon atoms. For example, R 2 is an alkylene radical comprising 4 to 12 carbon atoms, or 4 to 10 carbon atoms, for example, 2, 4, 6, or 8 carbon atoms, for example, a linear alkylene radical. 2may be a linear or branched (e.g., linear) alkylene radical comprising 4 to 12 carbon atoms, for example, 4 to 10 carbon atoms, for example, 4, 6, or 8 carbon atoms, an unsubstituted phenylene radical, or an unsubstituted cyclohexylene radical. Optionally, R 2 It may contain one or more ether groups.

[0074] Specific examples of suitable diamines include tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, octamethylene diamine, decamethylene diamine, dodecamethylene diamine, 1,3-pentanediamine, 2-ethyl-butanediamine, 2-methylpentamethylene diamine, 3-methylpentamethylene diamine, 2-methylhexamethylene diamine, 3-methylhexamethylene diamine, 2,5-dimethylhexamethylene diamine, 2,2,4-trimethylhexamethylene diamine, 2,4,4-trimethylhexamethylene diamine, 2,7-dimethyloctamethylene diamine, 2,2,7,7-tetramethyloctamethylene diamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine. 4,4'-Diaminodicyclohexylmethane, benzene-1,2-diamine, benzene-1,3-diamine, and benzene-1,4-diamine are included. A suitable diamine is hexamethylene diamine.

[0075] Aromatic diacids are suitably chemical formula HO-C(O)-R 3 At least one discrete of -C(O)-OH, and in the above equation, variable R 3 is a substituted or unsubstituted aryl, e.g., phenyl. In one embodiment, the aromatic diacid is terephthalic acid. In another embodiment, the aromatic diacid is isophthalic acid.

[0076] The branched diamine is suitably selected from 1,3-pentanediamine, 2-ethyl-butanediamine, 2-methylpentamethylene diamine, 3-methylpentamethylene diamine, 2-methylhexamethylene diamine, 3-methylhexamethylene diamine, 2,5-dimethylhexamethylene diamine, 2,2,4-trimethylhexamethylene diamine, 2,4,4-trimethylhexamethylene diamine, 2,7-dimethyloctamethylene diamine, and 2,2,7,7-tetramethyloctamethylene diamine. Preferably, the branched diamine is 2-methylpentamethylene diamine.

[0077] The polyamide resin may further comprise a catalyst. In one embodiment, the catalyst may be present in the polyamide resin in an amount ranging from 10 ppm to 1,000 ppm (by weight). In another embodiment, the catalyst may be present in an amount ranging from 10 ppm to 300 ppm (by weight).

[0078] The catalyst may, without limitation, comprise phosphorus and oxyphosphorus compounds, such as phosphoric acid, phosphorous acid, hypophosphorous acid, hypophosphorous acid, arylphosphonic acid, arylphosphinic acid, salts thereof, and mixtures thereof. In one embodiment, the catalyst may be sodium hypophosphite (SHP), manganese hypophosphite, sodium phenylphosphinate, sodium phenylphosphonate, potassium phenylphosphinate, potassium phenylphosphonate, hexamethylenediammonium bis-phenylphosphinate, potassium tolylphosphinate, or a mixture thereof. In one embodiment, the catalyst may be sodium hypophosphite (SHP).

[0079] The polyamides described herein may be terminated in any suitable manner. In some embodiments, the polyamide may be terminald with a suitable polymerization initiator, -H, -OH, -CO2H, -NH2, CO2 - , -NH3 + , substituted or unsubstituted (C1-C 20 ) Hydrocarbil (e.g., (C1-C 10 ) alkyl or (C6-C 20) aryl) - which interposes 0, 1, 2, or 3 groups independently selected from -O-, substituted or unsubstituted -NH-, and -S- -, poly(substituted or unsubstituted (C1-C 20 ) hydrocarbyloxy), and poly(substituted or unsubstituted (C1-C 20 It can be terminated with a terminal group independently selected from ) hydrocarbilamino). In a preferred embodiment, the polyamide is a carboxylic acid (-CO2H, -CO2 - ), amine (-NH2, -NH3 + It is terminated by a combination consisting of ) and acetyl (-CO2Me) terminal groups.

[0080] Preferably, the composition of the present invention comprises a random copolymer as defined herein having a relative viscosity (RV) as measured in an 8.4 weight percent solution of 90% formic acid, which is 20 to 60 RV, preferably 22 to 45 or 35 to 50 RV.

[0081] Preferably, the composition of the present invention comprises a random copolymer as defined herein having 40 to 90 meg / kg, preferably 60 to 80 meg / kg, amine terminal groups (AEG).

[0082] Preferably, the composition according to the present invention may optionally contain acetic acid. Preferably, the random copolymer according to the present invention may optionally contain acetic acid. More preferably, the random copolymer according to the present invention (which may be suitably considered as a modified nylon polymer) may contain an amount of acetic acid of 1 to about 10,000 ppmw (parts per million) by weight.

[0083] Preferably, the composition of the present invention comprises one or more fibers. Non-limiting examples of fibers may include carbon fibers, carbon nanofibers, glass fibers, basalt fibers, natural fibers, mineral fibers, nanocellulose fibers, wood fibers, non-wood plant fibers, or combinations thereof. Non-limiting examples of fillers may include talc, mica, clay, silica, alumina, carbon black, wood flour, sawdust, wood shavings, newspaper paper, paper, flax, hemp, straw, rice bran, hemp, jute, sisal, peanut shells, soybean hulls, or combinations thereof. Preferably, the composition of the present invention comprises one or more glass fibers.

[0084] In various preferred embodiments, the present invention provides a glass fiber-filled polyamide composition. The glass fiber-filled polyamide composition comprises glass fibers blended with the polyamide, preferably in an amount of 10 to 60 weight percent or less based on the weight of the polyamide containing the glass fibers. The disclosed composition may contain, preferably in an amount of 10 to 60 weight percent or less of glass fibers, for example, 15 to 55 weight percent or less of glass fibers, 20 to 40 weight percent or less of glass fibers, for example, 25 weight percent or 30 weight percent or 35 weight percent or 40 weight percent or 45 weight percent or 50 weight percent of glass fibers, based on the weight of the final polyamide composition containing all additives and fillers (including glass fibers).

[0085] In the present invention, the term "glass fiber" is abbreviated as "GF," which is understood to be the standard nomenclature in the polymer and compounding industry. Unless otherwise noted, the amount of GF in a polymer sample is expressed as a weight percent of the total.

[0086] The disclosed composition comprises monomers comprising hexamethylenediamine and adipic acid. For example, the disclosed polyamide may include polyamide PA 46, PA 66; PA 69; PA 610, PA 612, PA 1012, PA 1212, PA 6, PA 11, PA 12, PA 66 / 6T, PA 6I / 6T, PA 66 / 6I / 6T or a blend, e.g., PA6 / PA66. The naming convention is well known in the art and is, for example, polycaproamide (N6), polyhexamethylene decanamide (N610), polyhexamethylene dodecanamide (N612), polyhexamethylene succinamide (N46), polyhexamethylene azelamide (N69), polydecamethylene sebamide (N1010), polydodecamethylene dodecanamide (N1212), nylon 11 (N11), polylaurolactam (N12), nylon 6T / DT.

[0087] The aliphatic condensed polyamide suitable for inclusion in the disclosed composition comprises having a carbon branching rate of 0 to 1, for example, 0.2 to 0.8, for example, 0.25 to 0.75.

[0088] The composition of the present invention may include conventional plastic additives in an amount sufficient to obtain desired processing or performance characteristics for the compound. This amount should not waste the additives nor be detrimental to the processing or performance of the composition. Those skilled in the art of thermoplastic formulation technology may select from many different types of additives to include in the composition of the present invention without excessive experimentation, but by referring to publications such as the Plastics Additives Database from the Plastics Design Library (2004) (see website elsevier.com).

[0089] Non-limiting examples of optional additives include adhesion promoters, biocides, anti-fogging agents, antistatic agents, antioxidants, binders, foaming agents and foaming agents, catalysts, dispersants, extenders, smoke suppressants, shock modifiers, initiators, lubricants, nucleants, pigments, colorants and dyes, optical brighteners, plasticizers, processing aids, release agents, silanes, titanates and zirconates, slip agents, anti-blocking agents, stabilizers, stearates, ultraviolet light absorbers, waxes, catalyst deactivators, and combinations thereof.

[0090] PA66 / DI and PA66 / D6 manufacturing .

[0091] According to the conventional batch autoclave method used herein, a 40 to 60% polyamide salt solution formed from equimolar amounts of diamine and diamine in water is introduced into a pre-evaporator vessel operated at a temperature of about 130 to 160°C and a pressure of about 180 to about 690 kPa (absolute pressure), where the polyamide salt solution is concentrated to about 70 to 80%. This concentrated solution is transferred to an autoclave, where it is continuously heated as the pressure inside the vessel rises from about 1100 kPa (absolute pressure) to about 4000 kPa (absolute pressure). Steam is discharged until the batch temperature reaches about 220 to 260°C. Subsequently, the pressure is gradually reduced to about 100 kPa (absolute pressure) or less (over about 30 to 90 minutes). The polymer molecular weight is controlled by the holding time and pressure at this stage. Salt concentration, pressure, and temperature may vary depending on the specific polyamide being processed. After the desired holding time, the polyamide is then extruded into strands, cooled, and cut into pellets (also known as granules).

[0092] In this batch process, a phosphorus compound or other additive may be introduced before polymerization (i.e., into a solution of at least one polyamide-forming reactant), or at any point during polymerization, or even after polymerization (i.e., by introducing the phosphorus compound and base into the polyamide melt using conventional mixing equipment, such as an extruder). The phosphorus compound and additive may be introduced individually or all at once. As a means of protection against oxidation and thermal decomposition, the phosphorus compound and additive are provided early in the polymerization process, for example, at the start of the polymerization process. The additive, which may be in a solid form, may be provided as a solid or as an aqueous solution.

[0093] INVISTA S. r. 1. It may also be possible to use a pre-prepared amine mixture of DYTEK® A Amine (CAS registration number 15520-10-2) and HMD. In such a mixture, the individual component strength may depend on the n-66 / DI wt / wt composition of the final interest. Non-limiting examples of such amine mixtures may include INVISTA DYTEK® A Amine:HMD blends (wt:wt) such as 10:90, 20:80, 25:75, 30:70, 35:65, 40:60, 45:55, 50:50, 55:45, 60:40, 65:35, 70:30, 75:25, 80:20, 90:10.

[0094] INVISTA Dytek® A amine is commercially produced by hydrogenating 2-methylglutaronitrile (or "MGN"). MGN is a branched C6 dinitrile obtained as a byproduct from the butadiene dihydrocyanide process of adiponitrile (or "ADN") production. The MGN byproduct, which would otherwise be discarded, can be recycled and reused in the production of INVISTA Dytek® A amine or the "D" portion; thus, PA66 / DI produced by this process is considered to have a recycled amine content derived from the "D" portion.

[0095] In one embodiment of the present invention, the composition comprises one or more C4-C 12 It may include branched diamines, which are recovered from the manufacturing process and corresponding C4-C 12 It is converted into a branched diamine and incorporated into a polymer as an alternative to burning branched dinitrile as fuel. In non-limiting examples, C4-C 12 Branched dinitrile includes 2-ethylsuccinonitrile and 2-methylglutaronitrile.

[0096] There are various tests and standards that can be used to evaluate the flame retardant properties of polymer resin systems. Underwriters' Laboratories test number UL-94 serves as one industry standard test for flame-retardant thermoplastic compounds. The standard ["UL-94 Standard for Tests for Flammability of Plastic Materials for Parts in Devices and Appliances"] provides details of the criteria for test methods and grades. Test method ASTM D635 is a standard [Standard Test Method for Rate of Burning and / or Extent and Time of Burning of Plastics in a Horizontal Position]. Test method ASTM D3801 is a standard [Standard Test Method for Measuring the Comparative Burning Characteristics of Solid Plastics in a Vertical Position]. Unless otherwise noted, flame retardant (FR) performance is measured herein according to the UL-94 vertical flame test.

[0097] There exist other tests and instruments for evaluating flammability, such as but not limited to the following: the Limiting Oxygen Index (LOI) test (ASTM 2863); the cone calorimeter (which measures the amount and rate of heat release during combustion, and both ASTM E 1354 and ISO 5660-1 standards are based on this instrument); the glow wire flammability test (IEC 60695-2-12); and the glow wire ignition test (IEC 60695-2-13).

[0098] Other tests existing to evaluate flame retardancy include, but are not limited to, tests determining smoke generation rate, smoke obscuration, and the toxicity of smoke and combustion gases. Other tests exist to evaluate application-specific flame retardancy, including, but not limited to, applications such as clothing fabrics, upholstery fabrics, airbag fabrics, carpets, or rugs.

[0099] Test method

[0100] As used herein, the following terms and test procedures are defined as follows:

[0101] ASTM D789-19 - Relative viscosity of formic acid solution.

[0102] ISO 1183-1:2019 - Density of a sample.

[0103] ISO 527-1:2019 - Tensile properties of molded and extruded plastics, including tensile modulus (MPa), % elongation at break of test material, tensile strength, and cord modulus. ISO 179-2:2020 - Charpy impact strength (unless otherwise noted, 23°C, kJ / m² 2 ).

[0104] ISO 11357-1:2016 - Differential Scanning Calorimetry (DSC) for Melting Temperature and Crystallization Temperature of Plastics.

[0105] Melting point (MP) - Endothermic peak occurring during heating of a small sample in differential scanning calorimetry (DSC) (measured according to ISO 11357-1:2016).

[0106] Melt viscosity (MV) - An indicator of the melt flow characteristics of a resin, measured in Pascal-seconds (Pa·sec) using a Kayness capillary rheometer at 280°C under constant force conditions.

[0107] The molecular weight of polyamide resins is typically inferred by measuring solution viscosity. The two most common methods are: (i) ASTM D789-19 for the measurement of relative viscosity (RV), and (ii) ISO 307:2019 for obtaining viscosity number (VN) values ​​using sulfuric acid. The viscosity values ​​and trends to be considered are determined by the same method, regardless of which method is selected.

[0108] Relative viscosity (RV) of the resin

[0109] The polyamide may have any suitable RV (e.g., as measured in an 8.4 wt% solution in 90% formic acid), e.g., 20 to 50 RV. The RV may be determined without glass fibers mixed with the polyamide, wherein the polyamide is optionally devoid of any other material present in the glass fiber-filled polyamide composition (e.g., substantially pure polyamide is measured for RV), or such material is optionally included in the polyamide during the RV determination, as if these materials affect the RV. Other methods for determining the RV, such as a 1 wt% solution in concentrated sulfuric acid, may be used, and, as used herein, a suitable correlation of RV between the method used and the 8.4 wt% solution in 90% formic acid may be determined. RV measurements are typically performed at room temperature and atmospheric pressure.

[0110] Unless otherwise noted, the term "RV" used in the Examples refers to the relative viscosity of a polymer sample as measured in an 8.4 wt% solution in 90% formic acid at room temperature and atmospheric pressure according to ASTM D789-19. RV is the ratio of the viscosity of the solution to the viscosity of the solvent used. The solution is an 8.4 wt% polyamide solution in 90% formic acid. Formic acid is the solvent used.

[0111] Amine terminal group (AEG)

[0112] Unless otherwise noted, AEG is determined by the potentiometric titration of a polymer dissolved in a 68% phenol / methanol mixture with 0.05 M perchloric acid in propan-1-ol.

[0113] Unless otherwise noted, as used in this specification, room temperature is 25°C.

[0114] Unless otherwise noted, as used in this specification, atmospheric pressure is 1 bar.

[0115] Examples

[0116] Various aspects of the present invention may be better understood by referring to the following examples provided as examples. The present invention is not limited to the examples provided herein.

[0117] Unless otherwise noted, in the following examples, all are mass ratios or weight ratios and weight percentages (weight%).

[0118] Example 1:

[0119] 7392 g of deionized water, 6800 g (25.92 mol) of nylon 66 salt, 243.5 g (2.095 mol) of 2-methylpentamethylenediamine, 348.0 g (2.95 mol) of isophthalic acid, 7.4 g (0.12 mol) of acetic acid, and 47.0 g (0.24 mol) of a 60 wt% aqueous solution of hexamethylenediamine (1330 g, 11.44 mol) were added to a 20 L temperature-controlled jacketed glass vessel equipped with an overhead stirrer and condenser and maintained under a nitrogen atmosphere. This produced a solution of about 50 wt% strength with an N66 / DI molar ratio of about 92.5 / 7.5, containing 0.44 mol% added acetic acid (equivalent to about 19.3 mol / million gram [mpmg] for the final polymer) based on the combined molar of adipic acid and isophthalic acid, and 0.86 mol% excess amine groups from hexamethylenediamine (HMD) based on the combined molar of carboxylic acids from adipic acid, terephthalic acid, and acetic acid. Excess hexamethylenediamine (HMD) was added to achieve the desired AEG target (65 mpmg in this example) and also to compensate for evaporation losses during the polymerization process.

[0120] This solution was added to a clean 24 L oil-heated autoclave with a stirrer along with 0.51 g of a 50 wt% aqueous solution of Silwet L7605 antifoaming agent (40 ppm active ingredient based on the final polymer).

[0121] In the first cycle of the polymerization process, when the pressure reached 170 psia, the solution was heated and evacuated, and the process continued until the temperature reached 198°C. In the second cycle, evacuation was stopped, and the pressure was increased to 265 psia over 13 minutes until the temperature of the contents increased to approximately 216°C. In the third cycle, evacuation was continued for 42 minutes while maintaining the system at 265 psia until the temperature of the contents reached 245°C. In the fourth cycle, the pressure was lowered to atmospheric pressure over 33 minutes, and the temperature of the contents increased to 271°C. In the fifth cycle, a vacuum was applied, the pressure was lowered to 483 mbar over 6 minutes and maintained for 7 minutes, the vacuum was released with nitrogen over 1 minute, and the temperature reached 275°C. In the 6th cycle, the polymer is extruded over a metal casting chute through which cold water flows from an autoclave by a bottom extrusion valve using a maximum nitrogen pressure of 25 psia, and then the solidified polymer race is placed into a second chute using a countercurrent of cold water and sent to a pelletizing device.

[0122] The polymer had an RV of 33.8 and an AEG of 67.4. The RV was determined at 8.4 w / w% in 90% formic acid according to ASTM D789-19, and the AEG was determined by potentiometric titration of the polymer dissolved in a 68% phenol / methanol mixture with 0.05 M perchloric acid in propan-1-ol.

[0123] Examples 2 to 13

[0124] The polymers of Examples 2 to 13 were prepared in a manner similar to Example 1, and the measurement data for RV and AEG for Examples 1 to 13 are summarized in Table 1 below. In Table 1, the term "m% DI" indicates the mole% of DI in the formulation. The term "AcOH m%" indicates the mole% of acetic acid present in the final polymer. The term "AcOH mpmg" indicates the mole per million gram (mpmg) of acetic acid present in the final polymer. The term "excess HMD (60%) (g)" indicates 60 wt% aqueous HMD in grams. The terms "excess HMD (m%)" and "excess HMD mpmg" indicate excess HMD in mole% and mole per million gram (mpmg), respectively.

[0125] [Table 1]

[0126]

[0127] In the examples of Table 1, the nylon-6,6 portion can be determined as m% nylon 66 = 100% - m% DI. Accordingly, in Examples 1 to 3, Examples 7 to 9 and Example 11, the nylon-6,6 portion is 92.5 m%; in Examples 4 and 12, it is 94.4 m%; in Examples 5 to 6 and Example 10, it is 96.3 m%; and in the case of Example 13, it is 90.6 m%. Thus, Table 1 presents nylon 66:DI final product formulations having a range of 90:10 to 97:3 (mol:mol), an RV range of 22 to 45, and an AEG range of 40 to 90 milliequivalents / kg (meq / kg).

[0128] Examples 14 to 20

[0129] According to the present invention, Table 2 describes several variations of nylon-6,6 copolymers that can be prepared in combination with DI and D6 components. In Table 2, Examples 14 to 20 were prepared in a manner similar to Example 1. In these formulations, the term "DI salt" refers to an amide salt obtained from 2-methylpentamethylene diamine (MPMD, sold under the trade name Dytek® A Amine at INVISTA), known as 2-methylpentamethylene isophthalamide, and isophthalic acid. The term "D6 salt" refers to an amide salt obtained from 2-methylpentamethylene diamine and adipic acid, also known as 2-methylpentamethylene adipamide.

[0130] [Table 2]

[0131]

[0132] Several nylon-6,6 formulations from Table 2 were compounded with glass fiber (GF), and mechanical properties were measured for these GF-reinforced specimens. The results are shown in Table 3. The GF reinforcement ranged from 30 to 50 wt% based on the mass of the final polymer as presented in Table 3. For comparison, high-AEG (60-90) nylon 66 specimens reinforced with 30 wt% GF and standard 48 RV and 50 AEG nylon 66 specimens reinforced with 50 wt% GF were also tested.

[0133] [Table 3]

[0134]

[0135] Examples 21 to 26

[0136] Examples 21 to 26 were prepared according to the formulations provided in Table 4, and their refractory properties were measured. Reference Examples 21 and 23 contain INYISTA HyperFlow™ U2501 PA66 Resin (which contains 0 wt% DI), whereas Examples 25 and 26 contain the copolymer of Example 14 (which contains 92 / 8 n-66 / DI (wt / wt)), and Examples 22 and 23 contain a combination of INYISTA HyperFlow™ U2501 PA66 Resin and the copolymer of Example 14.

[0137] [Table 4]

[0138]

[0139] Examples 27A to Examples 27L

[0140] [Table 5]

[0141]

[0142] The twin-screw compounder used was a 26-mm diameter idle screw with a 48 L / D ratio (i.e., an L / D ratio of 48). In the compounding of Table 5, the moisture level in the feedstock resin was less than 0.5 wt%. The polymer feedstock and the heat stabilizer [e.g., a commercially available Cu-based additive from Americhem] were pre-mixed at a ratio of 98.5% to 1.5% (wt / wt). The glass fibers used were commercially obtained from Nippon Electric Glass [NEG]. All feedstocks were loaded into the main hopper of the twin-screw compounder, and the conditions were carried out as detailed in Table 5.

[0143] Next, the mechanical properties of Examples 27A to 27L are measured, and the results are provided in Table 6.

[0144] [Table 6]

[0145]

[0146] Examples 28A to 28H

[0147] In Table 7, Examples 28A to 28D were prepared without a DI component in the total polyamide portion (i.e., 0 wt% DI). On the other hand, Examples 28E to 28H were prepared as a 50:50 (wt:wt) blend of INVISTA HyperFlow™ U2501 PA66 Resin and the copolymer of Example 14 [which is 92 / 8 n-66 / DI (wt / wt)]. The effective n-66 / DI present in the total polyamide portion of Examples 28E to 28H was 96:4 (wt:wt). In both cases, the flame retardant [FR] additive varied from 0 wt% to 14 wt% in the total composition.

[0148] In particular, for the test specimens of Examples 28E to 28EH with 10 wt% and 14 wt% FR additive levels and a thickness of 3.0 mm, an improved UL-94 vertical combustion test performance rating was observed compared to the specimens of Examples 28A to 28D.

[0149] [Table 7]

[0150]

[0151]

[0152] As can be seen from the data in Table 7, Examples 28E and 28F showed improved mechanical strength compared to Examples 28A through 28D. In fact, Examples 28E and 28F exhibited improved tensile properties despite having less flame retardant additive than Examples 28C and 28D, thereby demonstrating one of the advantages of the present invention, particularly that the presence of 96 / 4 (wt / wt) n-66 / DI material can reduce the use of FR additive.

[0153] Compared to the control n-66 with 0 wt% DI, an excellent FR rating [UL-94 V-0 rating] was observed for 3 mm thick specimens of 96 / 4 (wt / wt) n-66 / DI material under both RT and thermal aging conditions and for FR levels of 10 wt% or higher. The FR performance was similar for 0.4 mm, 0.75 mm, and 1.5 mm thick specimens.

[0154] Aspects of the present invention

[0155] An aspect of the present invention includes the following:

[0156] 1) As a composition of a substance,

[0157] a)

[0158] i) a first linear aliphatic condensation polyamide; and

[0159] ii) a random copolymer of a second condensation polyamide comprising a branched diamine and an aromatic diacid,

[0160] A random copolymer in which the mass ratio of the first linear aliphatic condensation polyamide to the second condensation polyamide is 85:15 or more to 99:1 or less; and

[0161] b) a composition of a material comprising 5% by weight to 25% by weight of a non-halogenated flame retardant additive; wherein the flame retardant (FR) performance, as measured by flammability measurement according to Underwriters Laboratories Standard (UL 94) for vertical combustion testing of the composition, exceeds the FR performance of a control essentially composed of nylon-6,6, characterized by a formic acid RV within ±3 and an AEG within ±5 compared to a random copolymer (a).

[0162] 2) In embodiment 1, the composition comprises 50% or more to 80% or less of a halogen-free phosphorus-containing FR additive as a control.

[0163] 3) A composition according to embodiment 1, wherein the first linear aliphatic condensed polyamide comprises at least one of PA 46, PA 66; PA 69; PA 610, PA 612, PA 1012, PA 1212, PA 66 / 6T, PA 6I / 6T, PA 66 / 6I / 6T or a blend, e.g., PA6 / PA66, polyhexamethylene decanamide (N610), polyhexamethylene dodecanamide (N612), polyhexamethylene succinamide (N46), polyhexamethylene azelamide (N69), polydecamethylene sebacaramide (N1010), polydodecamethylene dodecanamide (N1212), nylon 6 (N6), nylon 11 (N11), and polylaurolactam (N12).

[0164] 4) A composition according to embodiment 1, wherein the branched diamine is a C4 to C12 diamine.

[0165] 5) A composition according to embodiment 1, wherein the branched diamine is at least one of 1,3-pentanediamine, 2-ethyl-butanediamine, 2-methylpentamethylene diamine, 3-methylpentamethylene diamine, 2-methylhexamethylene diamine, 3-methylhexamethylene diamine, 2,5-dimethylhexamethylene diamine, 2,2,4-trimethylhexamethylene diamine, 2,4,4-trimethylhexamethylene diamine, 2,7-dimethyloctamethylene diamine and 2,2,2,7-tetramethyloctamethylene diamine.

[0166] 6) A composition according to embodiment 1, wherein the aromatic diacid is a C5 to C12 diacid containing one or more to three or fewer aromatic rings per monomer unit.

[0167] 7) A composition according to embodiment 6, wherein the aromatic diacid comprises at least one diacid of the chemical formula HO-C(O)-R1-C(O)-OH, and variable R1 is a substituted or unsubstituted furan, benzofuranyl, phenyl, naphthyl, or anthracenyl.

[0168] 8) A composition according to embodiment 7, wherein the aromatic acid comprises terephthalic acid and isophthalic acid.

[0169] 9) In any one of the above embodiments, the non-halogenated flame retardant additive is,

[0170] a) organophosphorus acids, e.g., diarylphosphinic acid or diarylphosphonic acid or dialkylphosphinic acid or dialkylphosphonic acid and their salts (including metal salts and organic salts);

[0171] b) Dihydrooxaphosphaphenanthrene (DOPO) and derivatives thereof;

[0172] c) Polyphosphazene;

[0173] d) an organic-nitrogen-based FR additive comprising melamine and its salts;

[0174] e) a boron-based FR additive containing a metal borate; and

[0175] f) A composition comprising at least one selected from the group consisting of silicon-based FR additives, e.g., phosphorus-based FR additives made of silicon.

[0176] 10) A composition in embodiment 9, wherein the non-halogenated flame retardant additive is selected from melamine cyanurate, aluminum diethylphosphinate, melamine polyphosphate, antimony trioxide, dehydrated zinc borate, and combinations thereof.

[0177] 11) A composition of a material comprising the following is disclosed:

[0178] a)

[0179] (1) A first aliphatic condensed polyamide containing less than 0.1 weight% of a monomer selected from branched diamines and aromatic diacids;

[0180] (2) Random copolymer of a second condensation polyamide comprising a branched diamine and an aromatic diacid; and

[0181] b) Halogen-free phosphorus-containing flame retardant additive.

[0182] 12) In mode 11,

[0183] a) The weight ratio of the first aliphatic condensation polyamide a)(1) to the second condensation polyamide a)(2) is 90:10 or more to 94:6 or less;

[0184] b) The flame retardant performance of the random copolymer, as measured by the Underwriters Laboratories standard [UL 94] vertical combustion test, is,

[0185] (1) a)(1) first aliphatic condensation polyamide;

[0186] (2) a)(2) second condensation polyamide of 0 to 0.1 weight% or less; and

[0187] (3) A composition that exceeds the performance of a control group containing an equal amount (i.e., ± 0.5% based on the weight of the additive) of a halogen-free phosphorus-containing flame retardant additive (as measured by the same UL 94 vertical combustion test), wherein the first aliphatic condensed polyamide of a)(2) and the random copolymer of a) both have the same formic acid RV within ±3 and the same AEG within ±5,

[0188] 13) A composition according to embodiment 12, wherein both the composition and the control group further comprise 5% by weight or more to 25% by weight or less of a halogen-free phosphorus-containing flame-retardant additive.

[0189] 14) In any embodiment 12 or 13, the composition comprises 50% or more to 80% or less of a halogen-free phosphorus-containing FR additive compared to the control group.

[0190] 15) A composition in any one of embodiments 12 to 14, wherein the first linear aliphatic condensed polyamide comprises an aliphatic diamine.

[0191] 16) In embodiment 15, the branched diamine is

[0192] a) 0 or more to 1 or less;

[0193] b) 0.2 or more to 0.8 or less; and

[0194] c) a C4 to C12 diamine characterized by a carbon branching rate selected from the group consisting of 0.25 or more to 0.75 or less;

[0195] A composition in which the carbon branching rate is defined as the degree to which aliphatic carbons exist in the branch relative to the skeletal chain of the molecule.

[0196] 17) A composition according to embodiment 16, wherein the branched diamine is at least one of 1,3-pentanediamine, 2-ethyl-butanediamine and 2-methylpentamethylenediamine.

[0197] 18) A composition according to embodiment 16, wherein the aromatic diacid is a C5 to C12 diacid containing one or more to three or fewer aromatic rings per monomer unit.

[0198] 19) A composition according to embodiment 18, wherein the aromatic diacid comprises at least one of the compositions of claim 6, wherein the aromatic diacid comprises at least one diacid of the formula HO-C(O)-R1-C(O)-OH, and variable R1 is a substituted or unsubstituted furan, benzofuranyl, phenyl, naphthyl, or anthracenyl.

[0199] 20) A composition according to embodiment 19, wherein the aromatic acid comprises terephthalic acid and isophthalic acid.

[0200] 21) In any one of embodiments 11 to 20, the non-halogenated flame retardant additive is,

[0201] a) organophosphorus acids, e.g., diarylphosphinic acid or diarylphosphonic acid or dialkylphosphinic acid or dialkylphosphonic acid and their salts (including metal salts and organic salts);

[0202] b) Dihydrooxaphosphaphenanthrene (DOPO) and derivatives thereof;

[0203] c) Polyphosphazene;

[0204] d) an organic-nitrogen-based FR additive comprising melamine and its salts;

[0205] e) a boron-based FR additive containing a metal borate; and

[0206] f) A composition comprising at least one selected from the group consisting of silicon-based FR additives, e.g., phosphorus-based FR additives made of silicon.

[0207] 22) A composition in embodiment 21, wherein the halogen-free phosphorus-containing flame retardant additive is selected from melamine cyanurate, aluminum diethylphosphinate, melamine polyphosphate, antimony trioxide, dehydrated zinc borate, and combinations thereof.

[0208] 23) As a composition of a substance,

[0209] a) a random copolymer of n-6,6 / DI having a weight ratio of n-6,6 to (D + I) of 85:15 to 99:1; and

[0210] b) comprising 5% by weight or more to 25% by weight or less of a halogen-free phosphorus-containing flame-retardant additive;

[0211] i) Here, the performance of the composition comprising (a) and (b) as measured by the UL 94 vertical combustion test is

[0212] 1. Nylon-6,6 containing 0.1 weight% or less of (D + I), wherein the nylon-6,6 is characterized by a formic acid RV within ±3 and an AEG within ±5 compared to a random copolymer (a); and

[0213] 2. A composition of a material that exceeds the performance of a control group (as measured by the same UL 94 vertical combustion test) containing 5 weight% or more to 25 weight% or less of a halogen-free phosphorus-containing flame retardant additive.

[0214] 24) In embodiment 23, the composition comprising (a) and (b) contains 50% or more to 80% or less of a halogen-free phosphorus-containing flame retardant additive as a control.

[0215] 25) A composition according to embodiment 23 or embodiment 24, wherein the flame retardant additive is at least one selected from the group consisting of melamine cyanurate, aluminum diethylphosphinate, melamine polyphosphate, antimony trioxide, dehydrated zinc borate, and combinations thereof.

Claims

Claim 1 A random copolymer comprising a) i) a first linear aliphatic condensation polyamide; and ii) a second condensation polyamide comprising a branched diamine and an aromatic diacid, wherein the mass ratio of the first linear aliphatic condensation polyamide to the second condensation polyamide is 85:15 or more and 99:1 or less; and b) comprising 5% by weight or more to 25% by weight or less of a non-halogenated flame retardant additive; wherein the flame retardant (FR) performance measured by flammability measurement according to Underwriters Laboratories Standard (UL 94) for vertical combustion test of the composition exceeds the FR performance of a control essentially composed of nylon-6,6 characterized by a formic acid relative viscosity (RV) within ±3 of the random copolymer (a) and amine end groups (AEG) within ±5, and wherein the composition of the material contains 50% or more to 80% or less of a non-halogenated flame retardant (FR) additive compared to the control. Claim 2 A composition of a material according to claim 1, wherein the first straight-chain aliphatic condensed polyamide contains less than 0.1 weight% of a monomer selected from branched diamines and aromatic diacids. Claim 3 A composition of a material according to claim 1, wherein the first linear aliphatic condensed polyamide is a linear aliphatic condensed polyamide comprising an aliphatic diamine. Claim 4 A composition of a material according to claim 1, wherein both the composition and the control group comprise a non-halogenated phosphorus-containing flame retardant additive in an amount of 5% by weight or more to 25% by weight or less. Claim 5 A composition of a material, wherein the non-halogenated flame retardant additive is a non-halogenated phosphorus-containing flame retardant additive. Claim 6 A composition of a material according to claim 1, wherein the non-halogenated flame retardant (FR) additive is a non-halogenated phosphorus-containing flame retardant (FR) additive, and the composition contains 50% or more to 80% or less of the non-halogenated phosphorus-containing flame retardant (FR) additive compared to a control group. Claim 7 A composition of a material according to claim 1, wherein the first linear aliphatic condensed polyamide comprises PA 46, PA 66, PA 69, PA 610, PA 612, PA 1012, PA 1212, PA 66 / 6T, PA 6I / 6T, PA 66 / 6I / 6T, PA6 / PA66, polyhexamethylene decanamide (N610), polyhexamethylene dodecanamide (N612), polyhexamethylene succinamide (N46), polyhexamethylene azelamide (N69), polydecamethylene sebacaramide (N1010), polydodecamethylene dodecanamide (N1212), nylon 6 (N6), nylon 11 (N11), polylaurolactam (N12), or a combination thereof. Claim 8 In paragraph 1, the branched diamine is C4 to C 12 Composition of a substance that is a diamine. Claim 9 A composition of a material according to claim 1, wherein the branched diamine is at least one of 1,3-pentanediamine, 2-ethyl-butanediamine, 2-methylpentamethylene diamine, 3-methylpentamethylene diamine, 2-methylhexamethylene diamine, 3-methylhexamethylene diamine, 2,5-dimethylhexamethylene diamine, 2,2,4-trimethylhexamethylene diamine, 2,4,4-trimethylhexamethylene diamine, 2,7-dimethyloctamethylene diamine, and 2,2,7,7-tetramethyloctamethylene diamine. Claim 10 In claim 1, the aromatic diacid is a C5 to C5 containing one or more to three or fewer aromatic rings per monomer unit. 12 A composition of a substance. Claim 11 In claim 1, the aromatic diacid is the chemical formula HO-C(O)-R 1 It includes at least one discrete of -C(O)-OH, where variable R 1 A composition of a substance which is substituted or unsubstituted furan, benzofuranyl, phenyl, naphthyl, or anthracenyl. Claim 12 In claim 1, the aromatic diacid is a composition of a substance comprising terephthalic acid and / or isophthalic acid. Claim 13 A composition of a material according to claim 1, wherein the random copolymer is n-6,6 / DI having a weight ratio of n-6,6 to (D + I) of 85:15 or more to 99:1 or less. Claim 14 A composition of a material according to claim 1, wherein the non-halogenated flame retardant additive is at least one selected from the group consisting of a) organophosphorus acid; b) dihydrooxaphosphaphenanthrene (DOPO) or a derivative thereof; c) polyphosphazene; d) organic-nitrogen-based FR additive; e) boron-based FR additive; and f) silicon-based FR additive. Claim 15 A composition of a material, wherein the non-halogenated flame retardant additive is selected from melamine cyanurate, aluminum diethylphosphinate, melamine polyphosphate, antimony trioxide, dehydrated zinc borate, and combinations thereof. Claim 16 In paragraph 4, the composition of the material is a non-halogenated phosphorus-containing flame retardant additive selected from aluminum diethylphosphinate, melamine polyphosphate, and combinations thereof. Claim 17 As a composition of the material, a) a first aliphatic condensed polyamide containing less than 0.1 weight% of a monomer selected from branched diamines and aromatic diacids; (2) a random copolymer of a second condensed polyamide containing branched diamines and aromatic diacids; and b) a non-halogenated phosphorus-containing flame retardant (FR) additive in an amount of 5 weight% or more to 25 weight% or less, wherein i) the weight ratio of the first aliphatic condensed polyamide a)(1) to the second condensed polyamide a)(2) is 90:10 or more to 94:6 or less; and ii) the flame retardant performance of the random copolymer measured by the Underwriters Laboratories Standard (UL 94) vertical combustion test is (1) the first aliphatic condensed polyamide of a)(1); and (2) 0 to 0.1 weight% or less of the second condensed polyamide of a)(2); and (3) exceeding the performance of a control group (measured by the same UL 94 vertical combustion test) containing the same amount (i.e., ± 0.5% based on the weight of the additive) of a non-halogenated phosphorus-containing flame retardant additive, wherein ii) the first aliphatic condensed polyamide of (1) and the random copolymer of a) both have the same formic acid relative viscosity (RV) (i.e., within ±3 of each other) and the same amine terminal group AEG (i.e., within ±5 of each other); wherein the composition of the material contains at least 50% and no more than 80% of a non-halogenated phosphorus-containing FR additive compared to the control group. Claim 18 As a composition of the material, a) a random copolymer of n-6,6 / DI having a weight ratio of n-6,6 to (D + I) of 85:15 to 99:1; and b) a non-halogenated phosphorus-containing flame retardant additive comprising 5 weight% to 25 weight%; i) wherein the performance of the composition comprising (a) and (b) as measured by the UL 94 vertical combustion test is 1. nylon-6,6 containing 0.1 weight% or less of (D + I), wherein the nylon-6,6 is characterized by a formic acid RV within ±3 of the random copolymer (a) and an AEG within ±5; and 2. A composition of a material comprising a non-halogenated phosphorus-containing flame retardant additive in an amount of 5% to 25% by weight or less, which exceeds the performance of a control group (measured by the same UL 94 vertical combustion test), wherein the composition of the material comprising (a) and (b) contains 50% to 80% of a non-halogenated phosphorus-containing flame retardant additive compared to the control group. Claim 19 A method for forming a composition of the material of claim 1, comprising combining a random copolymer and a non-halogenated flame retardant additive to form a composition of the material; wherein the flame retardant (FR) performance measured by a flammability measurement according to the Underwriters Laboratories standard (UL 94) for a vertical combustion test of the composition exceeds the FR performance of a control essentially composed of nylon-6,6 characterized by a formic acid relative viscosity (RV) within ±3 of the random copolymer (a) and amine end groups (AEG) within ±5, and wherein the composition of the material contains 50% or more to 80% or less of a non-halogenated flame retardant (FR) additive compared to the control. Claim 20 In paragraph 19, the branched diamine comprises one or more C4-C 12 It is obtained from branched dinitrile(s), which are recovered from the manufacturing process, and the corresponding C4-C 12 A method in which a branched diamine is converted and incorporated into a random copolymer as an alternative to burning a branched dinitrile as fuel. Claim 21 delete Claim 22 delete Claim 23 delete Claim 24 delete Claim 25 delete Claim 26 delete Claim 27 delete Claim 28 delete Claim 29 delete Claim 30 delete Claim 31 delete

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