Polyamide composition, method of making, method of producing article, and article made from composition

Abstract

The present invention relates to an impact modified polyamide composition comprising up to 77.5 parts by weight (pbw) of an aliphatic polyamide (APA) having a relative viscosity (RV) of up to 2.40, measured by the method according to ISO 307: 2019, at 0.01 g / ml, in 96% sulfuric acid and at 25 DEG C; and at least 22.5 pbw of a modified polyolefin impact modifier (MIM) having a melt flow rate (MFR) of at most 15 g / 10 minutes measured by the method according to ISO 1133: 2011 at 230 DEG C and a test load of 2.16 kg wherein the sum of the two amounts is 100 pbw. The invention also relates to a method for preparing the impact-modified polyamide composition, to a method for producing molded articles from the impact-modified polyamide composition, and to molded articles made from the impact-modified polyamide composition.

Description

Technical Field

[0001] The present invention relates to polyamide compositions, and more particularly to impact-modified polyamide compositions comprising an aliphatic polyamide (APA) and a modified polyolefin impact modifier (MIM). The present invention also relates to a method for preparing the impact-modified polyamide composition, a method for producing molded articles from the impact-modified polyamide composition, and molded articles made from the impact-modified polyamide composition. Background Art

[0002] The present invention relates particularly to impact-modified polyamide compositions that can be used in rotational molding applications, such as gas containers and fuel tanks; the technology used for their production is also known as roto-molding or rotational molding. For rotational molding, good flow properties are required to produce high-quality products with low porosity, uniform wall thickness and smooth surfaces, while for applications in pressurized gas containers and fuel tanks, good mechanical properties and high impact resistance at low temperatures are also required.

[0003] Impact-modified polyamide compositions are known in the art. Impact-modified polyamide compositions and rotational molded articles prepared therefrom are described, for example, in US2021 / 0139699A1. In US2021 / 0139699A1, two other patent documents are referenced: WO2017 / 094720 (=US2021 / 0301131A1) and JP2013-532748 (=US9309406B2). Both documents describe impact-modified polyamide compositions, wherein US2021 / 0301131A1 primarily relates to injection molded parts, while US9309406B2 relates to fuel components that can be made by injection molding, blow molding, or roto-molding.

[0004] According to US2021 / 0301131A1, a polyamide resin composition having excellent moldability (measured by spiral fluidity during injection molding) or appearance (surface gloss) as a molded product is required, which does not damage the inherent mechanical strength (impact resistance) exhibited by the polyamide resin as much as possible and has flexibility. US2021 / 0301131A1 mentions that there may be problems with the fluidity of the polyamide composition; and although the fluidity can be improved by using a polyamide resin with a low molecular weight or using a flow modifier (plasticizer or wax), these methods in turn have different problems, such as reduced impact strength, and are therefore limited in their application. US2021 / 0301131A1 claims that these problems have been solved by using a specific acid-modified modified polyolefin (Q) in an amount of 1 to 50 wt.% in combination with 50 to 99 wt.% of polyamide, the acid-modified modified polyolefin (Q) having a melt flow rate (MFR) of 50 to 200 g / 10 minutes at 230°C and under a load of 2.16 kg. According to US2021 / 0301131A1, by controlling the MFR of the acid-modified polyolefin (Q) to be within this range, a polyamide resin molded product having an excellent balance between impact resistance and specular gloss or an excellent balance between impact resistance and fluidity during molding of the molded product is obtained. In the example of US20210301131A1, the viscosity value is set to 145-150 cm 3 / g of polyamide 66 was used for polyamide (P), and two grades (grades) of modified polyolefin Q were tested separately and used in an amount of 10wt.% or 20wt.%. However, in the case of 10wt.%, the value of the elongation at break (23°C) was very low, and in the case of 20wt.%, the melt viscosity was very high even at a temperature of up to 290°C, making these materials unsuitable for rotational molding. In addition, US2021 / 0139699 also discloses that although in US20210301131A1, the fluidity was improved by using a polyolefin with a relatively low viscosity as the acid-modified polyolefin, the impact resistance (especially at low temperatures) was reduced.

[0005] US9309406B2 (corresponding to JP2013-532748) relates to a fuel component comprising a polymer composition comprising: a polyamide having a terminal carboxyl group concentration relative to a terminal amino group concentration of 1 or greater; microtalc (talc) in an amount of 0.001 to 1 wt.% based on the total polymer composition; and an impact modifier in an amount of at least 1.0 wt.% based on the total polymer composition. Examples include polyamide PA6; microtalc (median diameter of 0.50 μm, 99% less than 5 μm, 92% less than 2 μm, and 75% less than 1 μm); and a maleic anhydride (MAH)-grafted ethylene copolymer as an impact modifier. Examples are reported with 9.75 wt.% and 20 wt.% of the impact modifier. Patent document JP2013-532748 is reviewed in US2021 / 0139699A1, which discloses that a blend of an impact modifier and a polyamide resin causes a significant increase in the viscosity of the polyamide resin composition obtained by a chemical reaction therebetween; and that the rotational molded article obtained by rotational molding of such a polyamide resin composition has poor surface properties, so that particles tend to remain on the surface, which is not suitable for rotational molding applications.

[0006] US2021 / 0139699A1 describes an impact-modified polyamide resin composition for rotational molding and a rotational molded article using the composition. The polyamide resin composition of US2021 / 0139699A1 comprises:

[0007] - Component (A): an aliphatic polyamide having a relative viscosity (ηr) of less than 2.6 (measured under the conditions of 96 wt.% sulfuric acid, 1 wt.% polymer concentration and 25°C according to JIS K6920) in an amount of: "a" parts by weight (pbw);

[0008] - component (B): a modified polyolefin having a density of 0.895 g / cm2 or less as measured according to ASTM D1505 in an amount of "b" pbw; and

[0009] - Component (C): "c" unmodified polyolefin in an amount pbw having an MFR value of 3.0 to 30 g / 10 min, the MFR value being measured at 190° C. under a load of 2.16 kg;

[0010] Wherein, the polyamide resin composition satisfies the following equation:

[0011] 50≤c / (b+c)x100=70, and 10≤(b+c) / (a+b+c)x100≤40.

[0012] In other words, the amount of modified polyolefin (B) is at most half the combined amount of modified polyolefin (B) and unmodified polyolefin (C), and (B) is also at most 20 pbw relative to the total amount of polyamide (A), components (B) and (C).

[0013] In the examples of US2021 / 0139699A1, polyamide 6 having a relative viscosity (ηr) of 2.20 or a relative viscosity (ηr) of 2.45 is used as component (A), a maleic anhydride-modified ethylene-α-olefin copolymer (TAFMER MH5020, density = 0.866) is used as component (B) (amount of 6.8 to 13.0 pbw), and an unmodified polyolefin (EVOLUE SP0540, MFR value at 190°C, 2.16 kg = 3.8 g / 10 min; ISO 1133) is used as component (C) (amount of 13.2-17.2 pbw). In most compositions, a semi-aromatic polyamide (8.0 pbw or 15 pbw) is present. The amount of polyamide 6 (component A) is supplemented to a total amount of 100 pbw. Among the properties reported are surface quality, Charpy impact strength values ​​at -60°C, and tensile elongation at 23°C, indicating that the presence of unmodified polyolefin is essential for the results. However, while the surface quality of the composition with polyamide 6 having a relative viscosity (ηr) of 2.20 is better, the mechanical properties of impact strength and tensile elongation are better for the composition of polyamide 6 having a relative viscosity (ηr) of 2.45 combined with 15 pbw of semi-aromatic polyamide. Furthermore, comparative experiments show that while mechanical properties are improved with a higher content of unmodified polyolefin, surface properties are unsatisfactory, while mechanical properties are reduced with lower contents of unmodified polyolefin or the absence of semi-aromatic polyamide.

[0014] US2021261773A1 relates to a composition comprising: a) 30-90 wt% of a polyamide and b) 10-40 wt% of a polyethylene elastomer (POE) composition, wherein the amounts of a) and b) are relative to the total composition, wherein the total amount of a) and b) is at least 60 wt% relative to the total composition, wherein the POE composition is composed of: b1) 20-95 wt% of a non-functionalized polyethylene elastomer and b2) 5-80 wt% of a functionalized polyethylene elastomer, wherein the amounts of b1) and b2) are relative to the POE composition. US2021261773A1 mentions that the composition can be used for rotational molding.

[0015] JP 2004 346240A relates to a polyamide resin composition that can provide molded articles with excellent rigidity, heat-resistant rigidity, dimensional stability, impact resistance, toughness, flowability, and appearance. The composition is described as being suitable as a structural member or exterior member for electrical / electronic and automotive parts. The thermoplastic polyamide resin composition contains (A) a thermoplastic polyamide resin component, (B) an olefin-based polymer component grafted / modified with an unsaturated dicarboxylic acid, (C) a talc component, and (D) a pentaerythritol-type phosphite component in specific proportions. Summary of the Invention

[0016] Despite the importance of material flowability for obtaining products with low porosity, uniform wall thickness, and a smooth surface, as well as good mechanical properties in tensile tests and high impact resistance in Charpy impact tests at room and low temperatures, the inventors have observed that impact-modified polyamide compositions often exhibit poor or even bad results in drop-dart impact tests. Drop-dart impact test results are an indicator of the mechanical properties of the produced cans. Poor drop-dart impact results indicate that the cans fail the mechanical requirements, typically performed at -40°C and from a specific height. This property can be relevant during transportation of the rotomoulded product or in actual use.

[0017] It is therefore an object of the present invention to provide a polyamide composition which is preferably suitable for rotational molding and which has a good balance of flowability, mechanical properties and impact resistance at room temperature and low temperatures and which shows good results in the drop weight impact test. Another object is to provide rotational molded articles which have a good balance of surface quality, mechanical properties and impact resistance at room temperature and low temperatures and which show satisfactory results in the drop weight impact test.

[0018] These objects have been achieved by the polyamide composition according to the invention and rotationally molded articles using the same polyamide composition.

[0019] The polyamide composition according to the present invention is an impact-modified polyamide composition consisting of:

[0020] - X parts by weight (pbw) of aliphatic polyamide (APA), and

[0021] - Y parts by weight (pbw) of a modified polyolefin impact modifier (MIM), and

[0022] - one or more other polymer components and / or one or more additives (referred to herein together as other components Z), which are different from X and different from Y and which, in combination, amount to 0 to 30 pbw, as defined relative to 100 pbw of the sum of X and Y);

[0023] in

[0024] aliphatic polyamide (APA) having a relative viscosity (RV) of at most 2.40, measured at 0.01 g / ml in 96% sulfuric acid at 25° C. according to ISO 307:2019;

[0025] - the modified polyolefin impact modifier (MIM) has a melt flow rate (MFR) of at most 15 g / 10 min as measured according to ISO 1133:2011 at 230°C and using a test load of 2.16 kg; and

[0026] - the sum of X and Y is 100 pbw, and wherein X is at most 77.5 pbw and Y is at least 22.5 pbw, wherein

[0027] - for a relative viscosity (RV) of the aliphatic polyamide (APA) up to and including 2.20, X is at least 60 pbw and Y is at most 40 pbw;

[0028] - for a relative viscosity (RV) of the aliphatic polyamide (APA) in the range of greater than 2.20 up to and including 2.33, X is at least 65 pbw and Y is at most 35 pbw; and

[0029] - for a relative viscosity (RV) of the aliphatic polyamide (APA) in the range of greater than 2.33 up to and including 2.40, X is at least 70 pbw and Y is at most 30 pbw; and,

[0030] wherein the further component Z comprises not more than 10 pbw of unmodified polyolefin and not more than 2 pbw of micro talc relative to 100 pbw of the combined amount of X and Y, provided that the one or more further polymer components and the one or more additives (together referred to as further component Z) are different from X and also different from Y, and the combined total amounts to an amount in the range of 0-30 pbw relative to 100 pbw of the sum of X and Y.

[0031] The impact-modified polyamide composition according to the present invention, comprising a polyamide and a modified polyolefin impact modifier having the aforementioned parameters in the aforementioned amount, has the following effects: not only does the polyamide composition have a good balance of fluidity, mechanical properties, and impact resistance at room temperature and low temperatures, but also exhibits positive drop weight impact test results at low temperatures. Another effect is that the polyamide composition is suitable for rotational molding, and rotational molded articles prepared therefrom not only have a good balance of surface quality, mechanical properties, and impact resistance at room temperature and low temperatures, but also exhibit toughness properties in a drop weight impact test at low temperatures.

[0032] With respect to the limitation of the polyamide composition comprising a limited amount of the other component Z, it is noted that the present inventors have discovered that the presence of excessive amounts of the other component can adversely affect one or more of the flowability, mechanical properties, impact resistance at room and low temperatures, drop weight impact properties at low temperatures, and / or gas barrier properties of the polyamide composition. In particular, the present inventors have discovered that one or more of the flowability and barrier properties can be gradually adversely affected by the addition of excessive amounts of unmodified polyolefin (including unmodified impact modifier), and correspondingly, by the addition of excessive amounts of inorganic filler particles (particularly micro talc).

[0033] These results are very surprising in several respects, namely, not only the good flow properties obtained with modified polyolefin impact modifiers having a low melt flow rate even when said modified polyolefin impact modifiers are used in relatively large amounts, but also the good mechanical properties and impact resistance obtained with polyamides having in particular a low relative viscosity (RV) even in the absence or presence of low amounts of unmodified polyolefin or semi-aromatic polyamide, while also showing positive results in the drop weight impact test.

[0034] The aliphatic polyamide in the composition according to the present invention is a polyamide obtainable by polymerizing lactam, aminocarboxylic acid, or aliphatic diamine and aliphatic dicarboxylic acid as raw materials, or copolymerizing any combination thereof, by known methods such as melt polymerization, solution polymerization, or solid phase polymerization. The aliphatic polyamide may be any of the following:

[0035] - AB polyamides obtained by polymerizing lactams and / or aminocarboxylic acids; or

[0036] - polyamides of the AABB type obtained by copolymerization of aliphatic diamines and aliphatic dicarboxylic acids; or

[0037] AB / AABB type polyamides, which are polyamide copolymers obtainable by copolymerization of lactams and / or aminocarboxylic acids in combination with aliphatic diamines and aliphatic dicarboxylic acids.

[0038] The example of lactam comprises caprolactam, enantolactam (enantolactam), undecanoic acid, laurolactam, α-pyrrolidone and α-piperidone.The example of aminocarboxylic acid comprises 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid.In AB type polyamide or AB / AABB copolymer, can use one lactam or two or more lactams.

[0039] In the AA / BB type polyamide or AB / AABB copolymer, one aliphatic diamine or two or more thereof can be used. The aliphatic diamine is suitably a C2-C20 diamine, i.e., a diamine containing 2 to 20 carbon atoms, preferably a C4-C12 diamine. The aliphatic diamine can be a linear aliphatic diamine, a branched aliphatic diamine, or a cyclic diamine, or any combination thereof. Examples of linear aliphatic diamines having 2 to 20 carbon atoms are 1,2-ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,15-pentadecanediamine, 1,16-hexadecanediamine, 1,17-heptadecanediamine, 1,18-octadecanediamine, 1,19-nonadecanediamine, 1,20-eicosanediamine. Branched aliphatic diamines are suitably diamines having a methyl-substituted aliphatic chain. Examples of the branched aliphatic diamine having 4 to 12 carbon atoms are 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, 2-methyl-1,8-octanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, and 5-methyl-1,9-nonanediamine.

[0040] Examples of aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, and eicosanedioic acid. In the AA / BB type polyamide or the AB / AABB copolymer, one aliphatic dicarboxylic acid or two or more thereof may be used.

[0041] Examples of AB type polyamides are homopolymers polycaprolactam (polyamide 6), polyundecanamide (polyamide 11), polydodecaneamide (polyamide 12); and any copolymers thereof. Examples of AA / BB type polyamides are polytetramethylene sebacamide (polyamide 410), polyhexamethylene adipamide (polyhexamethylene adipamide) (polyamide 66), polyhexamethylene suberamide (polyamide 68), polyhexamethylene azelaic acid (polyamide 69), polyhexamethylene sebacamide (polyamide 610), polyhexamethylene dodecaneamide (polyamide 612). Examples of copolymers of AB / AABB type polyamides are polyamide 6 / 66, polyamide 6 / 410, polyamide 6 / 68, polyamide 6 / 610, and polyamide 6 / 6 / 12.

[0042] Aliphatic polyamides (APAs) may include monomer components other than those based on lactams, aminocarboxylic acids, aliphatic diamines, and aliphatic dicarboxylic acids; and are referred to herein as other or additional monomer components. Examples of other monomer components include monoamines, triamines and polyamines, monocarboxylic acids, dicarboxylic acids, and tricarboxylic acids. These other monomer components may be aliphatic monomer components or aromatic monomer components. The other monomer components may also include other aromatic monomer components, such as aromatic diamines and aromatic dicarboxylic acids. The aliphatic polyamide in the composition according to the present invention suitably includes other monomer components in an amount of up to 10 mol %. In this article, the aliphatic polyamide may include up to 5 mol % and including 5 mol % of an aromatic monomer component while still being considered an aliphatic polyamide. For example, the aliphatic polyamide may include 3 mol % of an aromatic monomer component in combination with up to 7 mol % of other aliphatic monomer components, or 5 mol % of an aromatic monomer component in combination with up to 5 mol % of other aliphatic monomer components. Preferably, the aliphatic polyamide includes 0-5 mol %, more preferably 0-2 mol % of another monomer component. In this article, the other monomer components can be one other monomer component, or two or more other monomer components. In this article, the mole percentage (mol %) is relative to the total molar amount of the lactam or carboxylic acid, aliphatic diamine, aliphatic dicarboxylic acid and other monomer components copolymerized in the aliphatic polymer. Examples of other monomer components that can be copolymerized into aliphatic polyamides are known in the art.

[0043] Among the aliphatic polyamides that can be used in the composition according to the invention, the following are preferred: polyamide 6, polyamide 11 and polyamide 12; and polyamide-6 copolymers obtained by copolymerization of caprolactam or 6-aminocaproic acid or a combination thereof with an aliphatic comonomer chosen from:

[0044] - another lactam and / or aminocarboxylic acid, or

[0045] - an aliphatic diamine and an aliphatic dicarboxylic acid, or

[0046] - another lactam and / or an aminocarboxylic acid, as well as an aliphatic diamine and an aliphatic dicarboxylic acid.

[0047] These polyamides are preferred for their thermal stability and molding processability during molding. More preferably, the polyamide is a polyamide 6 polymer, a polyamide 6 homopolymer, or a polyamide 6 copolymer comprising up to 25 mol % of an aliphatic comonomer. Even more preferably, the polyamide-6 polymer comprises 0-10 mol %, even more preferably 0-5 mol %, and most preferably 0-2 mol % of an aliphatic comonomer. As used herein, mole percentages (mol %) are relative to the total amount of caprolactam or 6-aminocaproic acid and aliphatic comonomer copolymerized in the aliphatic polymer.

[0048] The aliphatic polyamide in the composition according to the invention is suitably a semi-crystalline polyamide. The semi-crystalline polyamide may have a melting temperature (T m ). Suitably, the melting temperature T m As high as 280°C or higher, or as low as 160°C or lower. Herein, T is measured by the method according to ISO 11357-3:2018 m , wherein the heating rate is 10°C / min. Preferably, T m In the range of 180-260° C., more preferably in the range of 190-240° C. The advantage is that the composition has a more balanced combination of properties in terms of molding processability, thermal stability during molding and mechanical properties of molded parts.

[0049] In this document, ranges are understood to also include lower and upper limits. Thus, for example, in the expression "in the range of 180-260°C", the range includes a lower limit of 180°C and an upper limit of 260°C.

[0050] The aliphatic polyamide may be a mixture of two or more polyamides. In this context, the polyamides may have different relative viscosities (RV). In this case, the relative viscosity (RV) of the aliphatic polyamide in the composition according to the present invention is the relative viscosity measured for a mixture of two or more polyamides, the relative viscosity being measured at 25° C. using a method according to ISO 307:2019 at a concentration of 0.01 g of a mixture of two or more polyamides in 1 ml of 96% sulfuric acid.

[0051] For the composition of the present invention, it is important that the relative viscosity (RV) of the aliphatic polyamide is at most 2.40, not only to achieve good fluidity, but also to make it possible to use a modified polyolefin impact modifier (MIM) in a sufficiently high amount to obtain the effects of the present invention. For RVs exceeding 2.40, the inventors have found that the ability of the composition to achieve the appropriate quality of rotomolding (rotamoulding, rotational molding) is gradually reduced when combined with an appropriate amount of MIM. Below 2.40, the relative viscosity (RV) can vary over a wide range. Suitably, the relative viscosity (RV) is as low as 1.90, or even lower, such as 1.80. Preferably, the relative viscosity (RV) is at least 1.90, more preferably at least 2.00. For example, the RV can be in the range of 1.80-2.40, preferably 1.90-2.40, more preferably 2.00-2.40. This has the advantage that mechanical properties are better maintained at a high level, including good Charpy impact resistance and acceptable drop impact resistance. Also preferably, the viscosity is at most 2.35, more preferably at most 2.30, even more preferably at most 2.25. This has the advantage that flowability is improved while mechanical properties are maintained at a significant level, including good Charpy impact resistance and acceptable drop weight impact resistance.

[0052] In the composition according to the invention, the modified polyolefin impact modifier (MIM) has a melt flow rate (MFR) of at most 15 g / 10 min, measured at 230° C. and a test load of 2.16 kg, according to the method of ISO 1133:2011. The MFR can vary over a wide range and can be as low as, for example, 0.25 g / 10 min. At too low MFR values, the flowability of the composition is too greatly hampered for its practical use, for example in rotational molding. When the MFR value of the modified polyolefin impact modifier (MIM) is too high, the mechanical properties are poor, in particular for polyamides having the relative viscosity (RV) according to the invention.

[0053] Preferably, the MFR of the modified polyolefin impact modifier (MIM) is at least 0.5 g / 10 min, more preferably at least 0.6 g / 10 min, even more preferably at least 0.8 g / 10 min. Also preferably, the MFR of the modified polyolefin impact modifier (MIM) is at most 10.0 g / 10 min, more preferably at most 7.0 g / 10 min, even more preferably at most 5.0 g / 10 min. Most preferably, the MFR of the modified polyolefin impact modifier (MIM) is in the range of 0.5-10 g / 10 min, or in the range of 0.8-5 g / 10 min, or in the range of 1.0-3 g / 10 min.

[0054] Modified polyolefin impact modifiers are understood herein to be polymers comprising a polyolefin backbone modified with functional groups. The polyolefin backbone is suitably a copolymer of different olefin monomers, specifically a copolymer of α-olefin monomers having 2 to 20 carbon atoms. Examples of such α-olefin monomers include ethylene, propylene, 1-butene (butylene), isobutylene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene, and 4-methyl-1-pentene. The polyolefin backbone is preferably a copolymer of two olefins selected from ethylene, propylene, and butene; or a copolymer of at least one olefin selected from ethylene, propylene, and butene and at least one other α-olefin monomer having 4 to 20 carbon atoms. In this article, ethylene-α-olefin copolymers and propylene-α-olefin copolymers are preferred. Herein, the ethylene in the ethylene-α-olefin copolymer and the propylene in the propylene-α-olefin copolymer are suitably present in an amount of at least 20 mol %, more preferably at least 40 mol %. Among these copolymers, the ethylene-α-olefin copolymer is more preferred, and the ethylene-butene copolymer and the ethylene-1-octene copolymer are even more preferred.

[0055] The polyolefin backbone may further include monomer units derived from unsaturated monomers other than olefin monomers. These other unsaturated monomers or other unsaturated monomers may be, for example, diene monomers or aromatic monomers or combinations thereof. Examples of diene monomers (for example, included in ethylene-α-olefin copolymers or propylene-α-olefin copolymers) include non-conjugated diene components, such as 1,4-hexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene and 2,5-norbornadiene; and conjugated diene components, such as butadiene, isoprene and piperylene. Examples of aromatic monomers (for example, aromatic monomers that may be included in ethylene-α-olefin copolymers or propylene-α-olefin copolymers) include styrene. If present, other unsaturated monomers may be present in an amount of up to 20 mol %, preferably up to 10 mol %, and more preferably 0-5 mol %. In this article, mol % is the total molar amount relative to the olefin monomers and other unsaturated monomers in the polyolefin backbone. Polyolefins comprising other unsaturated monomers copolymerized with olefin monomer combinations, and modified polyolefin impact modifiers comprising a polyolefin backbone having other copolymerized unsaturated monomers are known in the art.

[0056] The modified polyolefin impact modifier comprises a polyolefin backbone modified with a functional group. Examples of suitable functional groups include acid groups, epoxy groups and glycidyl groups. The modified polyolefin impact modifier used in the present invention is preferably an acid-modified polyolefin, an epoxy-modified polyolefin or a glycidyl-modified polyolefin or any combination thereof. Among these, acid-modified polyolefins are particularly preferred. Acid-modified polyolefins can be obtained by modifying a polyolefin with an unsaturated carboxylic acid or its anhydride. Examples of unsaturated carboxylic acids or their anhydrides include maleic acid, fumaric acid (fumaric acid), itaconic acid, acrylic acid, methacrylic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, maleic anhydride, itaconic anhydride and cis-4-cyclohexene-1,2-dicarboxylic anhydride. Among these, maleic anhydride or itaconic anhydride are preferred, and maleic anhydride is more preferred. As an alternative to unsaturated carboxylic acids or their anhydrides, derivatives such as amides and acid esters can be used.

[0057] The amount of modifying functional groups in the modified polyolefin impact modifier can vary. The amount of functional groups can be expressed as the amount of functional modification expressed as weight percent (wt. %) relative to the weight of the modified polyolefin impact modifier (MIM).

[0058] Suitably, the modified polyolefin impact modifier (MIM) has a functionally modified amount of at least 0.25 wt.%. Also suitably, the functionally modified amount of the modified polyolefin impact modifier (MIM) is at most 2.5 wt.%, preferably at most 2.0 wt.%. More preferably, the functionally modified amount is in the range of 0.3-1.5 wt.%; even more preferably in the range of 0.4-1.0 wt.%. In this article, weight percent (wt%) is relative to the total weight of the modified polyolefin impact modifier. Where an acid-modified polyolefin is particularly preferred, the acid-modified amount of the modified polyolefin impact modifier (MIM) is preferably at least 0.25 wt.% and at most 2.0 wt.%, more preferably in the range of 0.3-1.5 wt.%, and most preferably in the range of 0.4-1.0 wt.%. A particularly preferred acid-modified polyolefin is a polyolefin modified with maleic anhydride. The corresponding maleic anhydride modified polyolefin suitably comprises at least 0.25 wt.%, or at most 2.5 wt.%, preferably 0.3-1.5 wt.%, more preferably 0.4-1.0 wt.% maleic anhydride relative to the weight of the modified polyolefin impact modifier.

[0059] Suitably, the glass transition temperature (T g ) is below 0°C and can be as low as -70°C, and even lower. Preferably, the T gis at most -40°C, more particularly in the range of -40°C to -70°C, more preferably at most -50°C, more preferably at most -55°C, and most preferably at most -60°C. In this context, T is measured by the method according to ISO 11357-2:2020 at a heating rate of 10°C / min. g .

[0060] The modified polyolefin impact modifier (MIM) preferably has a glass transition temperature (T g ), and can be as low as -70°C, and even lower. More preferably, the T g is at most -55°C, even more preferably at most -60°C. In this context, T is measured by the method according to ISO 11357-2:2020 at a heating rate of 10°C / min. g From the perspective of mechanical properties at low temperatures, low T g .

[0061] Preferably, the modified polyolefin impact modifier (MIM) has a density of less than 1 g / cm 3 The density can be as low as 0.80g / cm 3 , or even lower, but suitably 0.80 g / cm 3 or higher, such as at least 0.84 g / cm 3 More preferably, the density of the modified polyolefin impact modifier (MIM) is at most 0.95 g / cm 3 , even more preferably at most 0.90 g / cm 3 , more specifically 0.80-0.90 g / cm 3 and most preferably up to 0.88 g / cm 3 More specifically, the density is between 0.84-0.88 g / cm 3 In this article, the density is measured by the method according to ASTM D1505-03. From the perspective of mechanical properties at low temperatures, low density is preferred.

[0062] Preferably, the Shore A hardness of the modified polyolefin impact modifier (MIM) is less than 100. The Shore A hardness may be as low as 40, or even lower, but suitably higher than 45 or higher, for example at least 50. More preferably, the Shore A hardness of the modified polyolefin impact modifier (MIM) is at most 90, even more preferably at most 80, more particularly in the range of 45-80, and most preferably at most 75. More particularly, the Shore A hardness is in the range of 50-75. Herein, the Shore A hardness is measured by the method according to ASTM D2240-15. From the perspective of mechanical properties at low temperatures, a low Shore A hardness is preferred.

[0063] The modified polyolefin impact modifier (MIM) may be present in the composition according to the present invention in an amount of at least 22.5 pbw, and in an amount within a range depending on the relative viscosity of the aliphatic polyamide.

[0064] For relative viscosities (RV) of the aliphatic polyamide (APA) up to and including 2.20, X is at least 60 pbw and Y is at most 40 pbw. For relative viscosities (RV) of the aliphatic polyamide (APA) within the stated ranges, preferably X is in the range of 62.5-75 pbw and Y is in the range of 25-37.5 pbw.

[0065] For a relative viscosity (RV) of the aliphatic polyamide (APA) in the range of greater than 2.20 and up to 2.33, X is at least 65 pbw and Y is at most 35 pbw. Preferably, for a relative viscosity (RV) of the aliphatic polyamide (APA) in the range of greater than 2.20 and up to 2.27, X is in the range of 65-75 pbw and Y is in the range of 25-35 pbw; however, for a relative viscosity (RV) of the aliphatic polyamide (APA) in the range of greater than 2.27 and up to 2.33, preferably X is at least 69 and Y is at most 31 pbw.

[0066] For a relative viscosity (RV) of the aliphatic polyamide (APA) in the range of greater than 2.33 and up to 2.40, X is at least 70 pbw and Y is at most 30 pbw. Preferably, for a relative viscosity (RV) of the aliphatic polyamide (APA) in the range, X is at least 72.5 pbw and Y is at most 27.5 pbw.

[0067] An advantage of the amount of modified polyolefin impact modifier (MIM) in the above preferred range in combination with the said range of relative viscosity (RV) of aliphatic polyamide (APA) is that the composition has an improved balance of properties, particularly in terms of flow and mechanical properties.

[0068] Preferably, the impact-modified polyamide composition has a combination of properties that meets all of the following parameters:

[0069] - a complex viscosity (η*) of at most 700 Pa·s at 250° C.;

[0070] - at -40°C, an elongation at break of at least 17.5%;

[0071] - At 23°C, the notched impact strength is at least 70KJ / m 2 ;as well as

[0072] - At -40°C, the drop weight impact resistance pass rate is at least 60%.

[0073] In this paper, various properties were measured by the following methods:

[0074] - The complex viscosity (η*) was measured by dynamic mechanical spectroscopy (DMS) according to ISO 6721-10, with a loading time of 5 minutes and an angular frequency of 0.1 rad / s.

[0075] - elongation at break measured by the method according to ISO 527-2:2012 Type 1A at a tensile rate of 50 mm / min;

[0076] - notched impact strength measured by the method according to ISO 179-2:2020; and

[0077] - Drop weight impact resistance was measured on five 80*80*2 mm injection-molded panels according to the method of ISO 6603-2-2000-10, and the pass rate was determined as the percentage of panels that passed the test.

[0078] The complex viscosity (η*) value of the composition may be, for example, about 550 Pa·s, about 425 Pa·s, about 300 Pa·s, or about 250 Pa·s. Suitably, the complex viscosity (η*) is at least 200 Pa·s.

[0079] More preferably, the complex viscosity (η*) of the impact-modified polyamide composition is at most 600 Pa·s, more preferably at most 500 Pa·s at 250° C. The advantage of a lower complex viscosity is that the composition is processed more smoothly and, during processing, a lower molding temperature is required to obtain a high-quality product.

[0080] Still more preferably, the impact-modified polyamide composition has a combination of properties that complies with one or more of the following parameters:

[0081] - an elongation at break of at least 20% at -40°C; and / or

[0082] - At 23°C, the notched impact strength is at least 75 kJ / m 2 , most preferably at least 80KJ / m 2 .

[0083] The composite elongation at break value of the composition at -40°C may be, for example, about 20%, about 25%, about 36%, about 43% or about 48%. Suitably, the elongation at break at -40°C is at most 60%, or even at most 50%, while still achieving good to very good results.

[0084] The notched impact strength at 23°C may be, for example, about 83 kJ / m 2 , or about 88KJ / m 2 , or about 97KJ / m 2 , and the notched impact strength can be higher than (for example) 110KJ / m 2 , which is suitably at most 110 KJ / m 2 , more specifically up to 105KJ / m 2 .

[0085] More preferably, the impact-modified polyamide composition has a drop weight impact resistance pass rate of at least 80% at -40° C. The pass rate can be as high as 100%, wherein all test panels successfully pass the test.

[0086] In addition to aliphatic polyamide and MIM, the impact-modified polyamide composition according to the present invention can also include one or more other polymer components and / or one or more additives, which constitute a part for other components. As required, these other components can exist with the amount in the scope that does not damage the purpose of the present invention. Additive and / or other polymer components can suitably exist with the amount in the scope of 0.001-30pbw, preferably in the scope of 0.01-20pbw and more preferably in the scope of 0.1-10pbw. In this article, parts by weight (pbw) are the amount of the merging of X and Y relative to 100pbw, wherein X represents the amount of the aliphatic polyamide in pbw, and wherein, Y represents the amount of the modified polyolefin impact modifier (MIM) in pbw. The inventors have found that adding other components (other Z) with an amount exceeding 30pbw (relative to the summation of X and Y) can adversely affect one or more properties of said composition.

[0087] The other polymer component may be any polymer component or mixture of polymer components commonly used in non-reinforced impact-modified polyamide compositions, as long as it does not impair the objects of the present invention. Suitable examples of the other polymer component are semi-aromatic polyamides, other thermoplastic polymers, unmodified polyolefins and rubbers.

[0088] The unmodified polyolefin in other polymer components can be (for example) polyolefin homopolymer or polyolefin copolymer.The example of polyolefin homopolymer is polyethylene and polypropylene.The example of polyolefin copolymer is the unmodified polyolefin copolymer for main chain in MIM.Preferably, unmodified polyolefin is selected from polyethylene, polypropylene, ethylene-alpha-olefin copolymer and propylene-alpha-olefin copolymer.Unmodified polyolefin can exist with the amount of 10pbw at the most, more preferably 7.5pbw at the most and at least 1pbw.Even more preferably, with respect to the amount of merging of X and Y of 100pbw, the amount of unmodified polyolefin is in the scope of 0-5pbw.

[0089] The semi-aromatic polyamide in the other polymer components may be a copolymer of an aromatic dicarboxylic acid and an aliphatic diamine; or a copolymer of an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid and an aliphatic diamine; or a copolymer of an aliphatic dicarboxylic acid, an aromatic diamine and an aliphatic diamine; or a copolymer of an aliphatic dicarboxylic acid and an aromatic diamine; or a copolymer of an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, an aromatic diamine and an aliphatic diamine. The semi-aromatic polyamide may be a semi-crystalline semi-aromatic polyamide or an amorphous semi-aromatic polyamide. Preferably, the melting temperature (T m ) is at most 260° C., more preferably at most 240° C., and suitably is at least 190° C. Even more preferably, the semi-aromatic polyamide is an amorphous semi-aromatic polyamide.

[0090] The semi-aromatic polyamide in the other polymer components may contain aliphatic diamine units having 6 to 12 carbon atoms, which are derived from a diamine or a combination of diamines selected from the group consisting of 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, and 1,12-dodecanediamine. In addition to the aliphatic diamine, the semi-aromatic polyamide may contain aromatic dicarboxylic acid units derived from a dicarboxylic acid selected from terephthalic acid, isophthalic acid, and naphthalene dicarboxylic acid.

[0091] In particular, the semi-aromatic polyamide may be a 6T copolymer, ie the copolymer comprises 6T units in addition to units from other monomers. Specific examples of semi-aromatic polyamides suitable for use in the composition according to the present invention include poly(hexamethylene terephthalamide / hexamethylene isophthalamide) copolymer (polyamide 6T / 61), poly(hexamethylene terephthalamide / hexamethylene adipamide) copolymer (polyamide 6T / 66), poly(hexamethylene terephthalamide / hexamethylene sebacamide) copolymer (polyamide 6T / 610), poly(hexamethylene terephthalamide / hexamethylene dodecane diamide) copolymer (polyamide 6T / 612), poly(hexamethylene terephthalamide / hexamethylene isophthalamide / hexamethylene adipamide) copolymer (polyamide 6T / 61 / 66), poly(hexamethylene terephthalamide / 2-methylpentamethylene terephthalamide) copolymer (polyamide 6T / M5T), and poly(hexamethylene terephthalamide / caproamide) copolymer (polyamide 6T / 6). More preferred examples include poly(hexamethylene isophthalamide / hexamethylene terephthalamide) copolymer (polyamide 6I / 6T), poly(hexamethylene isophthalamide / hexamethylene terephthalamide / hexamethylene adipamide) copolymer (polyamide 6I / 6T / 66), and mixtures thereof.

[0092] Preferably, the semi-aromatic polyamide in the other polymer components is present in an amount of at most 10 pbw, more preferably at most 7.5 pbw, even more preferably at most 5.0 pbw. Most preferably, the amount of semi-aromatic polyamide is in the range of 0-2.5 pbw relative to 100 pbw of the combined amount of X and Y.

[0093] The additives that may be further present in the impact-modified polyamide composition according to the present invention may be any additive or mixture of additives selected from the group consisting of auxiliary additives commonly used in non-reinforced impact-modified polyamide compositions. Without being limited to the following, the additives may be selected from the group consisting of stabilizers (including heat stabilizers, UV absorbers, light stabilizers, and antioxidants), antistatic agents, lubricants, antiblocking agents, fillers, crystal nucleating agents, release agents, plasticizers, crosslinking agents, foaming agents, and colorants (pigments, dyes).

[0094] Preferably, the amount of additive is at most 10 pbw, more preferably at most 7.5 pbw. Although the amount may be 0 pbw, even more preferably the amount of additive is in the range of 0.1-5 pbw relative to 100 pbw of the combined amount of X and Y.

[0095] The inventors have found that higher relative contents of further components (Z) may adversely affect one or more flow behaviour and mechanical properties of the rotomoulded part, such as impact resistance, in particular at low temperatures.

[0096] Preferably, the impact-modified polyamide composition comprises at least one stabilizer. This has the advantage of better maintaining the quality of the molded product in the presence of oxygen during processing. The stabilizer can be an organic stabilizer, an inorganic stabilizer, or a combination thereof.

[0097] Examples of organic stabilizers include antioxidants such as phenolic antioxidants, thioether antioxidants, and / or phosphorus antioxidants. The organic stabilizer is preferably at least one selected from the group consisting of phenolic antioxidants and phosphorus antioxidants, and more preferably at least one selected from the group consisting of hindered phenolic antioxidants having a tert-butyl group at the ortho position and phosphite antioxidants of phenol having a tert-butyl group at the ortho position. Suitably, the organic stabilizer is present in an amount within the range of 0.1-2 pbw, more specifically 0.3-1.5 pbw, and preferably 0.5-1.2 pbw, relative to 100 pbw of the combined amount of X and Y.

[0098] Examples of inorganic stabilizers include metal halides such as copper halide. A specific example of such an inorganic stabilizer is a mixture of cuprous iodide and potassium bromide (CuI / KBr).

[0099] Preferably, the impact-modified polyamide composition comprises at least an inorganic stabilizer, more preferably a copper halide. Even more preferably, the composition comprises a copper halide stabilizer in an amount of at least 50 ppm, preferably at least 100 ppm, of Cu relative to the total weight of the impact-modified polyamide composition.

[0100] More preferably, the impact-modified polyamide composition comprises an organic stabilizer in an amount of at least 0.5 pbw and a copper-based inorganic stabilizer in an amount of at least 50 ppm, preferably at least 100 ppm, of Cu. Herein, parts by weight (pbw) are relative to 100 pbw of the combined amount of the aliphatic polyamide (X) and the modified polyolefin impact modifier MIM (Y). Herein, parts per million (ppm) are relative to the total weight of the impact-modified polyamide composition.

[0101] Most preferably, a combination of a hindered phenolic antioxidant having a tert-butyl group at the ortho position and a copper-based inorganic stabilizer is used, more particularly, a combination of a hindered phenolic antioxidant having a tert-butyl group at the ortho position and CuI / KBr is used.

[0102] The additive in the impact-modified polyamide composition can include fillers. An example is talc, which is hydrated magnesium silicate or micro-talc. Preferably, the composition includes micro-talc. Micro-talc can be any known micro-talc suitable for polyamide compositions. Micro-talc preferably has a median diameter (d50) of less than 1 micron, more preferably less than 70 microns, even more preferably less than 50 microns. The particle size distribution of micro-talc is determined using a high-speed image analyzer. The analyzer projects all particles in a limited sample into a two-dimensional image and measures the actual surface area of ​​all captured individual particles. These surface areas are then recalculated as circles with the same surface area, and their diameters are calculated. The median (d50) of the particle size distribution is then determined by a known method.

[0103] Micro-talcum powder can be present in the polymer composition with an amount up to 10pbw, for example, with an amount of 0.001pbw to 10pbw. Preferably, micro-talcum powder can be present in the impact-modified polyamide composition with an amount in the range of 0.01-5.0pbw, more preferably in the range of 0.01-3.0pbw, even more preferably in the range of 0.01-2.0pbw, most preferably in the range of 0.01 to 0.5pbw. For example, in one embodiment, relative to the gross mass of the composition, the amount of micro-talcum powder can be preferably 0.05wt%. The inventors have found that at least 0.01 to as much as about 3pbw, preferably to as much as about 2pbw, most preferably to as much as about 1pbw amount gradually helps to provide good impact resistance at low temperatures. Excessive talcum powder, for example, when used as bulk filler, can cause high brittleness at low temperatures. Herein, the amount of micro talc expressed in parts by weight (pbw) is the amount relative to 100 pbw of X and Y combined.

[0104] The present invention also relates to a method for preparing an impact-modified polyamide composition according to the present invention. The impact-modified polyamide composition is obtainable by melt mixing an aliphatic polyamide (APA) and a modified polyolefin impact modifier (MIM) having the parameters mentioned above in the amounts mentioned above. The impact-modified polyamide composition can be prepared by various methods known in the related art, for example, by melt mixing an aliphatic polyamide, a MIM and optional other components added as needed. In particular, the impact-modified polyamide composition can be obtained by simultaneously or sequentially adding each component to a mixing device, such as a Henschel mixer, a V-blender, a tumble mixer and a ribbon mixer (bibbon mixer, ribbon mixer), heating and mixing them, and melt-kneading the mixture using, for example, a single screw extruder, a multi-screw extruder, a kneader or a Banbury mixer (Banbury mixer). In particular, if an apparatus having excellent kneading performance, such as a multi-screw extruder, a kneader, and a Banbury mixer, is used, a high-quality impact-modified polyamide composition in which the components are more uniformly dispersed can be obtained.

[0105] The present invention also relates to a process for producing molded articles from the impact-modified polyamide composition and to molded articles made from the impact-modified polyamide composition.

[0106] Method according to the present invention is to use the rotational molding method of the impact-modified polyamide composition according to the present invention, and any specific or preferred embodiment thereof, as described above. Any rotational molding method known in the art can be used. The molding of the impact-modified polyamide composition according to the present invention by the rotational molding method can, for example, be carried out by the following method. For example, first, a metal mold can be attached to a known rotational molding device, which can be rotated, inverted or moved with a swing on a single shaft or multiple shafts, and the impact-modified polyamide composition in the form of, for example, powder or pellets can be loaded into the metal mold. Then, the metal mold interior can be heated to a temperature of 100°C. m +5℃ and b)T m +80℃. In this article, T m is the melting temperature of the aliphatic polyamide. In other words, the metal mold can be heated to a temperature in the range of 5-80°C higher than the melting temperature of the aliphatic polyamide. At this temperature, the impact-modified polyamide composition is molded while the aliphatic polyamide is melted. Thereafter, the metal mold is cooled to c) the glass transition temperature (T g ) and d) temperature T m -10 ℃ to cool and solidify the rotational molded article. Thereafter, the rotational molded article is removed from the metal mold. The cooling time varies depending on the thickness of the rotational molded article, but the cooling time is generally in the range of a few minutes to a few hours. During rotational molding, in order to prevent coloring and deterioration (deterioration, aging) of the rotational molded article, an inert atmosphere such as nitrogen is preferred because it contains no or substantially no oxygen inside the metal mold. Alternatively, the impact-modified polyamide composition can be added to the metal mold in a molten form; for example, the impact-modified polyamide composition is first added to an extruder, heated and melted in the extruder, and then the molten impact-modified polyamide composition is directly extruded into a preheated metal mold.

[0107] In this article, the T of the above-mentioned aliphatic polyamide g The T of the aliphatic polyamide mentioned above is measured by the method according to ISO 11357-2:2020 at a heating rate of 10°C / min. m It is measured by the method according to ISO 11357-3:2018 at a heating rate of 10°C / min.

[0108] The molded article according to the present invention is a rotationally molded article made from the impact modified polyamide composition according to the present invention and / or any of its preferred embodiments as described above.

[0109] The rotationally molded article according to the invention and obtained by the rotational molding process according to the invention may be, for example, a container or a tank and may be used for different purposes, for example, for pressurized gas containers, fuel tanks, and the like.

[0110] Due to its advantageous properties, the impact-modified polyamide composition according to the invention can also be advantageously used in other molding processes, such as injection molding or blow molding.

[0111] Therefore, the present invention also comprises a process comprising injection molding or blow molding the impact modified polyamide composition according to the present invention and any preferred embodiment thereof as described herein.

[0112] The present invention also includes a molded article, which is an injection-molded article or a blow-molded article made from the impact-modified polyamide composition according to the present invention and any preferred embodiment thereof as described above.

[0113] Additionally or alternatively, the present invention relates to the following variations.

[0114] In variant 1), an impact-modified polyamide composition is provided, comprising

[0115] - X parts by weight (pbw) of aliphatic polyamide (APA), and

[0116] - Y parts by weight (pbw) of a modified polyolefin impact modifier (MIM),

[0117] in

[0118] aliphatic polyamide (APA) having a relative viscosity (RV) at 0.01 g / ml in 96% sulfuric acid at 25° C., measured by the method according to ISO 307:2019, of at most 2.40;

[0119] - the modified polyolefin impact modifier (MIM) has a melt flow rate (MFR) of at most 15 g / 10 min at 230° C. and a test load of 2.16 kg, measured by the method according to ISO 1133:2011; and

[0120] -The sum of X and Y is 100 pbw, and where

[0121] o X is at most 77.5 pbw and Y is at least 22.5 pbw, and

[0122] o For aliphatic polyamide (APA) relative viscosities (RV) up to and including 2.20, X is at least 60 pbw and Y is at most 40 pbw;

[0123] o For relative viscosities (RV) of aliphatic polyamides (APAs) ranging from greater than 2.20 and up to and including 2.33, X is at least 65 pbw and Y is at most 35 pbw; and

[0124] o For relative viscosities (RV) of the aliphatic polyamide (APA) ranging from greater than 2.33 and up to and including 2.40, X is at least 70 pbw and Y is at most 30 pbw.

[0125] In a second variant, the impact-modified polyamide composition is according to variant 1, wherein the aliphatic polyamide (APA) is an AB polymer or an AB / AABB polymer, preferably an AB polymer, more preferably a polyamide 6 / 66 copolymer or an AB polymer selected from polyamide 6 (PA-6), polyamide 11 (PA-11) and polyamide 12 (PA-12), and copolymers or mixtures thereof.

[0126] In a third variant, the impact-modified polyamide composition is according to variant one or variant two, wherein the aliphatic polyamide (APA) has a melting temperature (T m ) is at most 260°C.

[0127] In a fourth embodiment, the impact modified polyamide composition is according to any one of embodiments 1-3, wherein the relative viscosity (RV) of the aliphatic polyamide (APA) is in the range of 1.86-2.37, preferably in the range of 1.98-2.31.

[0128] In a fifth variant, the impact-modified polyamide composition is according to any one of variants 1 to 4, wherein the melt flow rate (MFR) of the modified polyolefin impact modifier (MIM) is in the range of 0.5-10 g / 10 min, preferably in the range of 0.8-5 g / 10 min, more preferably in the range of 1.0-3 g / 10 min.

[0129] In a sixth variation, the impact-modified polyamide composition is according to any one of variations 1 to 5, wherein the modified polyolefin impact modifier (MIM) comprises a polyolefin copolymer backbone modified with acid functional groups.

[0130] In a seventh variation, the impact-modified polyamide composition is according to any one of variations 1 to 6, wherein the modified polyolefin impact modifier (MIM) has

[0131] - a glass transition temperature (T ) of at most -50°C, preferably at most -55°C, measured by the method according to ISO 11357-2:2020 g ); and / or

[0132] - Up to 0.95 g / cm3 as measured by the method according to ASTM D1505-03 3 ; preferably up to 0.90g / cm 3 , and more preferably at most 0.85 g / cm 3 density; and / or

[0133] - a Shore A hardness of at most 90, preferably at most 80, more preferably at most 75, measured by the method according to ASTM D2240-15.

[0134] In an eighth variation, the impact-modified polyamide composition is according to any one of variations 1 to 7, wherein

[0135] o For aliphatic polyamide (APA) relative viscosity (RV) up to and including 2.20, X is in the range of 62.5-75 pbw and Y is in the range of 25-37.5 pbw;

[0136] o For relative viscosities (RV) of aliphatic polyamides (APAs) greater than 2.20 up to and including 2.27, X is in the range of 65-75 pbw, and Y is in the range of 25-35 pbw;

[0137] o For relative viscosities (RV) of aliphatic polyamides (APAs) ranging from greater than 2.27 and up to and including 2.33, X is at least 69 and Y is at most 31 pbw;

[0138] o For relative viscosities (RV) of the aliphatic polyamide (APA) ranging above 2.33 and up to and including 2.40, X is at least 72.5 pbw and Y is at most 27.5 pbw.

[0139] In a ninth variation, the impact-modified polyamide composition is according to any one of variations 1 to 8, having

[0140] - a complex viscosity (η*) of at most 700 Pa·s at 250°C;

[0141] - an elongation at break of at least 17.5% at -40°C;

[0142] -At least 70KJ / m at 23℃ 2 Notched impact strength; and

[0143] - At least 60% of the drop weight impact resistance pass rate at -40°C;

[0144] in

[0145] o Complex viscosity (η*) was measured using dynamic mechanical spectroscopy (DMS) by the method according to ISO 6721-10 with a loading time of t = 5 min and an angular frequency of 0.1 rad / s;

[0146] o Elongation at break is measured according to ISO 527-2:2012 Type 1A method at a tensile rate of 50 mm / min;

[0147] o Notched impact strength is measured according to ISO 179-2:2020; and

[0148] o Drop impact resistance was measured on an injection molded plaque of 80*80*2 mm by the method according to ISO 6603-2-2000-10.

[0149] In a tenth variation, the impact-modified polyamide composition is according to any one of variations 1 to 9, wherein the composition comprises a total amount of one or more other polymer components and / or one or more additives in the range of 0.001-30 pbw relative to 100 pbw of the combined amount of X of the aliphatic polyamide (APA) and Y of the modified polyolefin impact modifier (MIM).

[0150] In an eleventh variant, the impact-modified polyamide composition is according to any one of variants 1 to 10, comprising

[0151] a. an organic stabilizer in an amount of at least 0.5 pbw relative to 100 pbw of aliphatic polyamide (APA) X and modified polyolefin impact modifier (MIM) Y combined amount; and

[0152] b. A copper-based inorganic stabilizer in an amount of at least 50 parts per million (ppm) of Cu relative to the total weight of the composition.

[0153] In a twelfth variation, there is provided a method for preparing an impact-modified polyamide composition, the method comprising melt mixing:

[0154] - X parts by weight of aliphatic polyamide (APA), and

[0155] -Y parts by weight of a modified polyolefin impact modifier (MIM),

[0156] wherein APA and MIM, and X and Y are according to any one of variations 1-11.

[0157] In a thirteenth variation, there is provided a method for preparing an impact modified article, the method comprising melt processing a polyamide composition comprising:

[0158] - X parts by weight of aliphatic polyamide (APA), and

[0159] -Y parts by weight of a modified polyolefin impact modifier (MIM),

[0160] wherein the impact-modified polyamide composition, the APA, and the MIM, and X and Y are according to any one of variations 1-11.

[0161] In a fourteenth embodiment, the method is according to variant 13, wherein the melt processing is performed by rotational molding.

[0162] In a variant embodiment, there is provided a rotationally molded article made from an impact-modified polyamide composition comprising

[0163] - X parts by weight of aliphatic polyamide (APA), and

[0164] -Y parts by weight of a modified polyolefin impact modifier (IM),

[0165] wherein the polyamide composition and the APA and the MIM, and X and Y are according to any one of variants 1-11.

[0166] The present invention is further illustrated by the following examples and comparative experiments. DETAILED DESCRIPTION

[0167] Examples and comparative experiments and test results

[0168] Material

[0169] Polyamide-1 Polyamide 6 (PA6), T m = 220° C., relative viscosity (RV) at 0.01 g / ml in 96% sulfuric acid at 25° C. is 2.51 (from DSM).

[0170] Polyamide-2 Polyamide 6 (PA6), T m = 220° C., relative viscosity (RV) at 0.01 g / ml in 96% sulfuric acid at 25° C. is 2.09 (from DSM).

[0171] Impact modifier-1 Acid-modified ethylene-butene polyolefin: 0.5wt.% maleic anhydride; at 190℃, 2.16kg, MFR is 0.9g / 10min; at 230℃, 2.16kg, MFR is 1.8g / 10min; T g -65℃; density is 870kg / m 3 ; Shore A hardness of 70 (from Mitsui).

[0172] Impact modifier-2 Acid-modified ethylene-butene polyolefin: 1 wt.% maleic anhydride; at 190°C, 2.16 kg, MFR is 0.6 g / 10 min; at 230°C, 2.16 kg, MFR is 1.2 g / 10 min; T g -65℃; density is 866kg / m 3 ; Shore A hardness of 55 (from Mitsui).

[0173] Impact modifier-3 Acid-modified ethylene-butene polyolefin: 1.0 wt.% maleic anhydride; at 190°C, 2.16 kg, MFR is 3.6 g / 10 minutes; at 230°C, 2.16 kg, MFR is 7.4 g / 10 minutes; T g -48℃; density 882kg / m 3 (From DOW).

[0174] Impact modifier-4 Ethylene-1-octene polyolefin; at 190℃, 2.16kg, MFR is 1.1g / 10min; T g -50℃; density is 885kg / m 3 (From Borealis).

[0175] Impact modifier-5 Acid-modified ethylene-butene polyolefin: 0.5 wt.% maleic anhydride; MFR 40 g / 10 min at 190°C, 2.16 kg; MFR 70 g / 10 min at 230°C, 2.16 kg; density 872 kg / m 3 ; Shore A hardness of 72 (from Mitsui).

[0176] Impact modifier-6 Acid-modified ethylene-butene polyolefin: 0.75wt.% maleic anhydride; at 190℃, 2.16kg, MFR is 11g / 10min; at 230℃, 2.16kg, MFR is 23g / 10min; T g -65℃; density is 896kg / m 3 ; Shore A hardness is 89; (from Mitsui).

[0177] Lubricant Calcium salt of a long-chain, saturated, linear carboxylic acid (montanic acid, nonacosanoic acid) (from Clariant).

[0178] Talc Microtalc (from Mineral Group).

[0179] Stabilizer-1 Irganox 1098 (N,N'-(hexane-1,6-diyl)bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], primary antioxidant) (from BASF).

[0180] Stabilizer-2 Chimassorb 944 (poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino]]): oligomeric hindered amine light stabilizer (HALS) and heat stabilizer) (from BASF).

[0181] Stabilizer - 3 CuI / KBr (3 wt.% copper) (from PolyAdd Services).

[0182] Aromatic PA Zytel HTN301, T m =230-280℃, density is 1190kg / m 3 (From DuPont).

[0183] Glass fiber E6CR10-4,5-568H, filament diameter (single filament diameter) of 9-11 μm, chop length (chop length) of 3.50-5.50 μm (from Jushi).

[0184] Black colorant N54-1033, PA6 containing 40% solvent black 7 (aniline black), density 1.19g / cm 3 (From Colloids).

[0185] Processing

[0186] Cooperate

[0187] The molding compositions were produced in a ZSK25 twin-screw extruder with a flat temperature profile of 250 to 260° C. and pelletizing. The components (see Table 1) were premixed and added at the throat. Unless otherwise specified, all compositions were prepared using an additive package consisting of 8.5 wt.% lubricant, 1.5 wt.% talc, 20 wt.% Irganox 1098, 10 wt.% Chimassorb 944, and 10 wt.% CuI / KBr, the weight percentages (wt.%) being based on the total weight of the additive package, all premixed in a masterbatch with 50 wt.% polyamide-1.

[0188] As indicated above, the comparative examples and compositions according to the invention listed in Tables 5-6 were prepared by adding micro talc and IM-4 to the amounts indicated in Tables 5-6.

[0189] Molding

[0190] Before molding, all materials were dried in a vacuum oven at 120°C with N2 purge for 16 h. For the preparation of test specimens, injection molding was performed on a Fanuc-2 injection molding machine model α-S50iA equipped with an appropriate mold cavity and using a barrel temperature of 260°C and a cavity temperature of 90°C.

[0191] Test Method

[0192] Relative viscosity

[0193] The relative viscosity of the individual polyamide polymers of their mixtures was measured in sulfuric acid at a concentration of 1 g / 100 g of m-cresol at a temperature of 25° C. by the method according to ISO 307.

[0194] Flow resistance

[0195] The resistance to flow was measured as dynamic viscosity using dynamic mechanical spectroscopy (DMS) by a method according to ISO 6721-10 with a loading time of t = 5 minutes, an angular frequency of 100-0.1 rad / s and 3 measurement points per decade. From these measurements, the complex viscosity (η*) at 0.1 rad / s was reported.

[0196] Tensile properties DAM

[0197] In the tensile test, the elongation at break was measured by the method according to ISO 527-2:2012 at -40°C at a tensile rate of 50 mm / min on a Type 1A test specimen.

[0198] Notch impact resistance

[0199] The notched impact strength was measured at 23°C by the method according to ISO 179-2:2020.

[0200] Drop hammer impact resistance

[0201] The drop weight impact resistance was measured by the method according to ISO 6603-2-2000-10 on injection-molded plaques measuring 80*80*2 mm at −40° C. The number of brittle fractures in 5 tests was reported.

[0202] Composition and test results

[0203] Compositions according to the invention (Examples, EX) and comparative experiments (CE), as well as the test results obtained by these examples and comparative experiments, are reported in Tables 1, 2, 3, 4, 5 and 6. The wt% is based on the total weight of the impact-modified polyamide composition.

[0204] Table 1. Compositions and test results of comparative experiments 1-9

[0205]

[0206]

[0207] a) greater than 700 Pa·s: x = poor; 500-700 Pa·s: o = acceptable; less than 500 Pa·s: oo = good;

[0208] b) less than 17.5%: x = poor; 17.5-20%: o = acceptable; greater than 20%: oo = good;

[0209] c) Less than 60KJ / m 3 :x = difference; 60-80KJ / m 3 :o=Acceptable; greater than 80KJ / m 3 :oo=good;

[0210] d) 3-5 breaks out of 5: x = poor; 2 breaks out of 5: o = acceptable; 0-1 breaks out of 5: oo = good.

[0211] The results in Table 1 show that the mechanical properties of a polyamide without an impact modifier (CE-1) can be improved by adding an impact modifier, however, at the expense of increased flow resistance (see CE-2; containing an acid-modified polyolefin impact modifier; CE-4 containing a combination of an acid-modified polyolefin impact modifier and an unmodified polyolefin). Flow properties can be improved by using polyamides with lower viscosities; however, mechanical properties are barely improved, or even decrease, and in particular, impact resistance decreases sharply when the relative viscosity of the polyamide is further reduced (see CE-3; containing an acid-modified polyolefin impact modifier; CE-4 and CE-5 containing the same combination of an acid-modified polyolefin impact modifier and an unmodified polyolefin). Furthermore, the differences between compositions CE-2 and CE-3 (containing a single acid-modified polyolefin impact modifier) ​​on the one hand, and compositions CE-4 and CE-6 (containing the same combination of an acid-modified polyolefin impact modifier and an unmodified polyolefin) on the other hand, are limited, with one composition performing slightly better in one property and worse in another. In addition, all of these comparative experiments failed in the drop weight impact test.

[0212] By further increasing the amount of acid-modified polyolefin impact modifier in combination with the unmodified polyolefin, impact resistance improved, but still to an insufficient degree and at the expense of a sharp decrease in flowability. CE-8 illustrates this point compared to CE-7 and CE-5. When the polyamide of CE-8 is replaced by a polyamide with a lower viscosity, not only does flowability improve, but impact resistance also improves, which is quite unexpected and contrary to common observations and contrary to the results observed above for CE-3 relative to CE-2, while the elongation at break value is also at an acceptable level. However, this composition also failed the drop weight impact test.

[0213] Table 2 shows the compositions and results of Comparative Experiments 10-12 and Examples AD with modified polyolefin impact modifiers according to the present invention. The compositions of Comparative Experiments CE-10-12 contain a modified polyolefin impact modifier in an amount of 20 wt.%, based on the total weight of the composition. Although the impact resistance of CE-10 is at an acceptable level, the flow resistance is too high. The flow resistance can be reduced by using polyamides with lower relative viscosities (RV), such as shown in CE-11 and CE-12; however, the impact resistance drops sharply, especially when the relative viscosity (RV) is further reduced from 2.31 in CE-11 to 2.09 in CE-12. At the same time, as shown in CE-11, these compositions also fail the drop weight impact test.

[0214] Table 2. Compositions and test results of Comparative Experiments 10-12 and Examples AD.

[0215]

[0216] The ratings for a), b), c), and d) are the same as in Table 1 above.

[0217] In contrast to the above results for CE-10-12, the compositions of Examples AD according to the present invention showed good or improved results for all properties, including good drop weight resistance values. More particularly, Example A contained a higher amount of modified polyolefin impact modifier compared to CE-11, which not only resulted in improved impact resistance and good elongation at break values, but also in maintained flowability and, surprisingly, acceptable drop weight impact test results.

[0218] The difference in the effect of the impact modifier combinations used in the comparative experiments is clearly demonstrated by a comparison between CE-7 and CE-8 on the one hand and CE-11, EX-A and EX-B on the other hand (all based on the same polyamide blend). CE-7 contains 20 wt.% of the impact modifier combination and has an impact modifier strength of 48.0 kJ / m 2In CE-8, the amount of the impact modifier combination was increased to 30 wt.%, which resulted in a moderate increase in the Charpy impact resistance to 55.4 KJ / m 2 CE-11 contains 20 wt.% of the modified polyolefin impact modifier according to the present invention, which shows 56.15 kJ / m 2 In Example A (EX-A), the amount of modified polyolefin impact modifier was increased to 25 wt.%, which resulted in a significant increase in Charpy impact resistance to 86.7 kJ / m2. In Example B (EX-B), the amount of modified polyolefin impact modifier was further increased to 30 wt.%, which resulted in a further increase in Charpy impact resistance to 96.0 kJ / m2. Further increases in the amount of modified polyolefin impact modifier, such as in Example B, resulted in further improvements in impact resistance and elongation at break, while flowability remained at an acceptable level and good results were obtained in the drop weight impact test. Compared to Example B, as performed in Example C (EX-C), reducing the relative viscosity (RV) of the composition with 30 wt.% modified polyolefin impact modifier not only improves the flow resistance, but also further improves the elongation at break, while maintaining the impact resistance at a high level, which is in contrast to the opposite results of CE-11 and CE12, and the drop weight impact test results are good, which is in sharp contrast to the results of CE-9 mentioned above. As shown in Example D (EX-D), the amount of impact modifier can be increased even further, which maintains very good mechanical properties while the flowability is still at an acceptable level.

[0219] Table 3 shows the compositions and test results for Examples EF and Comparative Experiments 13-14, where the only difference is the modified impact modifier. Examples EF contain a modified impact modifier according to the present invention, which is different from the impact modifier used in Examples AD, but both have a melt flow rate (MFR) of at most 15 g / 10 min, as measured according to ISO 1133:2011 at 230°C and a test load of 2.16 kg. As shown in the results, both Example E (EX-E) and Example F (EX-F) exhibit good mechanical properties, including good drop resistance at low temperatures, as well as good flowability.

[0220] Table 3. Compositions and test results of Examples EF and Comparative Experiments 13-14

[0221]

[0222]

[0223] The ratings for a), b), c), and d) are the same as in Table 1 above.

[0224] Comparative Experiments 13-14 (CE-13 and CE-14) contain different modified impact modifiers, neither of which is according to the present invention, while having a melt flow rate (MFR) of at most 15 g / 10 min as measured at 230° C. and a test load of 2.16 kg according to ISO 1133:2011. As shown in the results, both comparative experiments exhibit good flow properties, but poor mechanical properties, particularly in terms of drop weight resistance at low temperatures.

[0225] Table 4 shows various embodiments (Examples GM) using different compositions according to the present invention. Example GK shows that the additive package can be widely varied without affecting mechanical properties while maintaining good flowability. Example LN shows that a polymer other than a modified polyolefin impact modifier can be added while maintaining good mechanical properties and acceptable flowability, as long as the amount (Y) of the combined modified polyolefin impact modifier (MIM) and the amount (X) of the aliphatic polyamide (APA) relative to 100 pbw is at least 22.5 pbw in the composition. This is in contrast to compositions in which the amount of the modified impact modifier is less than the minimum amount according to the present invention, even when the total amount of the impact modifier remains constant. In this regard, a comparison of Example M (EX-M) with Comparative Experiments 8 and 9 (CE-8 and CE-9) shows relevant results. All three compositions had the same total amount of impact modifier (30 wt.%), however, CE-8 and CE-9 (compositions and results shown in Table 1) contained less modified polyolefin impact modifier (MIM) and more unmodified polyolefin impact modifier than EX-M. Composition EX-M according to the invention exhibited acceptable flow and good mechanical properties, while comparative experiments CE-8 and CE-9 failed at least in terms of flow or drop resistance at low temperatures.

[0226] Table 4. Composition and test results of Example GN

[0227]

[0228] The ratings for a), b), c), and d) are the same as in Table 1 above.

[0229] Table 5 shows examples using different compositions according to the present invention (Example OP). Example OP shows that compositions with micro-talc contents of 0.5 and 1.85 wt% (relative to the total mass of the composition) achieve beneficial properties. As can be seen from Comparative Examples 15-19, the addition of excess amounts of other components Z, specifically exemplified by compositions with greater than 30 pbw of glass fiber (CE-15), greater than 30 pbw of aromatic polyamide (CE-16), greater than 30 pbw of aromatic PA + GF (CE-17), and greater than 2 pbw of micro-talc (CE-18 and CE-19), adversely affects one or more of the following: flow properties, tensile properties, notched impact resistance, and drop resistance.

[0230] Note that for samples according to the present invention, i.e., having their individual components within the claimed ranges and without excess amounts of other components (component Z), no such adverse effects were observed. In terms of impact resistance, the results confirm that samples with up to 1 pbw of micro talc have good performance, samples with up to 2 pbw of micro talc have acceptable impact ratings, while samples with higher micro talc contents have relatively degraded performance.

[0231] Table 5. Compositions and test results of Examples 0-5 and Comparative Experiments 15-19

[0232] <![CDATA[ Experimental / Component (wt.%) ]]> EX-O EX-P CE-15 CE-16 CE-17 CE-18 CE-19 Polyamide-2 66.45 67.8 33.25 33.25 28.25 55.80 65.80 Impact modifier 1 30 30 30 30 30 30 30 Amorphous PPA 35 20 fiberglass 35 20 Micro talc 1.85 0.5 0.05 0.05 0.05 12.5 2.5 lubricant 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Stabilizer package 1.4 1.4 1.4 1.4 1.4 1.4 1.4 <![CDATA[ parameter ]]> RV-PA 2.09 2.09 2.09 2.09 2.09 2.09 2.09 X (pbw, relative to X+Y) 67.9 69.9 52.6 52.6 48.5 65.7 69.3 Y (pbw, relative to X+Y) 32.1 30.1 47.4 47.4 51.5 34.3 30.7 <![CDATA[ Test results ]]> η*[Pa·s] 259 248 35507 5567 92347 655 291 <![CDATA[Rating a) > oo oo x x x o oo Elongation at break -40℃[%] 48.7 56.7 6.6 93.1 6.6 58.2 43.5 Rating b) oo oo x oo x oo oo <![CDATA[Impact [KJ / m 2 > 75.2 85.7 54.1 121.7 39.7 21.9 70.6 <![CDATA[Rating c) > o oo x oo x x o Hammer Drop (#) 0 <![CDATA[0 e) ]]> 5 1 5 5 5 <![CDATA[Rating d) > oo oo x oo x x x

[0233] The ratings for a), b), c), and d) are the same as in Table 1 above. e) 0 failures out of 4 tests.

[0234] Table 6 shows the results of the examples (EX-Q, EX-R) and comparative examples CE-20 and CE-21 using different compositions according to the present invention. It can be seen that the addition of more than 10 pbw of unmodified IM (IM-4) has a negative impact on roto-molding properties, particularly in terms of showing relatively poor flowability, which is believed to be due to phase inversion (phase inversion, opposite conversion) causing a system with discontinuous polyamide phases in an olefin matrix. In contrast, examples L, M, Q and R, which do not contain an excess of unmodified impact modifier, exhibit good performance in terms of flowability, tensile properties and drop resistance, while showing at least acceptable performance in terms of impact resistance. The performance differences in flow properties and impact ratings between EX-R and EX-Q are believed to be related to the differences in maleic anhydride content.

[0235] Table 6. Compositions and test results of Example QR and Comparative Experiments 20-21

[0236]

[0237]

[0238] The ratings for a), b), c), and d) are the same as in Table 1 above.

Claims

1. An impact-modified polyamide composition, comprising: - X parts by weight (pbw) of aliphatic polyamide (APA), and - Y parts by weight (pbw) of a modified polyolefin impact modifier (MIM), and - 0-30 parts by weight (pbw) of one or more other polymer components and / or one or more additives, collectively referred to as other components Z, relative to 100 pbw of X and Y combined; in the aliphatic polyamide (APA) has a relative viscosity (RV) at 0.01 g / ml in 96% sulfuric acid at 25° C., measured by the method according to ISO 307:2019, of at most 2.40; - the modified polyolefin impact modifier (MIM) has a melt flow rate (MFR) of at most 15 g / 10 min at 230° C. and a test load of 2.16 kg, as measured by the method according to ISO 1133:2011; and -The sum of X and Y is 100 pbw, and where - X is at most 77.5 pbw and Y is at least 22.5 pbw, and - for a relative viscosity (RV) of the aliphatic polyamide (APA) up to and including 2.20, X is at least 60 pbw and Y is at most 40 pbw; - for a relative viscosity (RV) of the aliphatic polyamide (APA) in the range of greater than 2.20 and up to and including 2.33, X is at least 65 pbw and Y is at most 35 pbw; and - for a relative viscosity (RV) of the aliphatic polyamide (APA) in the range of greater than 2.33 and up to and including 2.40, X is at least 70 pbw and Y is at most 30 pbw; And among them, The other component Z comprises, relative to 100 pbw of the combined amount of X and Y, 0-10 pbw of unmodified polyolefin, and 0-2 pbw of micro talc.

2. The impact-modified polyamide composition according to claim 1, wherein The aliphatic polyamide (APA) is an AB polymer or an AB / AABB polymer; preferably an AB polymer; more preferably a polyamide 6 / 66 copolymer; or an AB polymer selected from polyamide 6 (PA-6), polyamide 11 (PA-11) and polyamide 12 (PA-12); and copolymers or mixtures thereof.

3. The impact-modified polyamide composition according to claim 1 or 2, wherein The melting temperature (T) of the aliphatic polyamide (APA) is measured according to ISO 11357-3:2018 at a heating rate of 10°C / min. m ) is up to 260°C.

4. The impact-modified polyamide composition according to any one of claims 1 to 3, wherein The relative viscosity (RV) of the aliphatic polyamide (APA) is in the range of 1.86-2.37, preferably in the range of 1.98-2.

31.

5. The impact-modified polyamide composition according to any one of claims 1 to 4, wherein The melt flow rate (MFR) of the modified polyolefin impact modifier (MIM) is in the range of 0.5-10 g / 10 min, preferably in the range of 0.8-5 g / 10 min, more preferably in the range of 1.0-3 g / 10 min.

6. The impact-modified polyamide composition according to any one of claims 1 to 5, wherein The modified polyolefin impact modifier (MIM) comprises a polyolefin copolymer backbone modified with acid functional groups.

7. The impact-modified polyamide composition according to any one of claims 1 to 6, wherein The modified polyolefin impact modifier (MIM) has - a glass transition temperature (T ) of at most -50°C, preferably at most -55°C, measured by the method according to ISO 11357-2:2020 g ); and / or - Up to 0.95 g / cm3 as measured by the method according to ASTM D1505-03 3 , preferably at most 0.90 g / cm 3 , and more preferably at most 0.85 g / cm 3 density; and / or - a Shore A hardness of at most 90, preferably at most 80, more preferably at most 75, measured by the method according to ASTM D2240-15.

8. The impact-modified polyamide composition according to any one of claims 1 to 7, wherein - for a relative viscosity (RV) of the aliphatic polyamide (APA) up to and including 2.20, X is in the range of 62.5-75 pbw and Y is in the range of 25-37.5 pbw; - for a relative viscosity (RV) of the aliphatic polyamide (APA) greater than 2.20 up to and including 2.27, X is in the range of 65-75 pbw and Y is in the range of 25-35 pbw; - for a relative viscosity (RV) of the aliphatic polyamide (APA) in the range of greater than 2.27 and up to and including 2.33, X is at least 69 and Y is at most 31 pbw; - For a relative viscosity (RV) of the aliphatic polyamide (APA) in the range of greater than 2.33 and up to and including 2.40, X is at least 72.5 pbw and Y is at most 27.5 pbw.

9. The impact-modified polyamide composition according to any one of claims 1 to 8, having - a complex viscosity (η*) of at most 700 Pa·s at 250°C; - an elongation at break of at least 17.5% at -40°C; -At least 70KJ / m at 23℃ 2 Notched impact strength; and - At least 60% of the drop weight impact resistance pass rate at -40°C; in - the complex viscosity (η*) is measured using dynamic mechanical spectroscopy (DMS) by a method according to ISO 6721-10 with a loading time of t=5 minutes and an angular frequency of 0.1 rad / s; - the elongation at break is measured by the method according to ISO 527-2:2012 Type 1A at a tensile rate of 50 mm / min; - the notched impact strength is measured by a method according to ISO 179-2:2020; and - Drop impact resistance is measured by the method according to ISO 6603-2-2000-10 on an injection molded plaque of 80*80*2 mm.

10. The impact-modified polyamide composition according to any one of claims 1 to 9, wherein The composition comprises 0.001-1 pbw of micro talc relative to 100 pbw of the combined amount of X and Y.

11. The impact-modified polyamide composition according to any one of claims 1 to 10, comprising: a. an organic stabilizer in an amount of at least 0.5 pbw relative to 100 pbw of the aliphatic polyamide (APA) X and the modified polyolefin impact modifier (MIM) Y combined amount; and b. a copper-based inorganic stabilizer in an amount of at least 50 parts per million (ppm) of Cu relative to the total weight of the composition.

12. A method for preparing an impact-modified polyamide composition, the method comprising melt mixing the following components: - X parts by weight of aliphatic polyamide (APA), - Y parts by weight of a modified polyolefin impact modifier (MIM), and - 0-30 parts by weight (pbw) of one or more other polymer components and / or one or more additives, collectively referred to as other components Z, relative to 100 pbw of X and Y combined; in, The APA and the MIM, and X, Y and Z are according to any one of claims 1-11.

13. A method for preparing an impact-modified article, the method comprising melt processing a polyamide composition consisting of: - X parts by weight of aliphatic polyamide (APA), - Y parts by weight of a modified polyolefin impact modifier (MIM), and - 0-30 parts by weight (pbw) of one or more other polymer components and / or one or more additives, collectively referred to as other components Z, relative to 100 pbw of X and Y combined; in, The impact-modified polyamide composition, the APA and the MIM, and X, Y and Z are according to any one of claims 1-11.

14. The method according to claim 13, wherein The melt processing is performed by rotational molding.

15. A rotationally molded article made from an impact-modified polyamide composition comprising: - X parts by weight of aliphatic polyamide (APA), - Y parts by weight of a modified polyolefin impact modifier (IM), and - 0-30 parts by weight (pbw) of one or more other polymer components and / or one or more additives, collectively referred to as other components Z, relative to 100 pbw of X and Y combined; in, The polyamide composition, the APA and the MIM, and X, Y and Z are according to any one of claims 1-11.

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