Polyamide compositions, methods for preparation, articles and methods for producing articles made with the compositions

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 in 96% sulfuric acid at 0.01 g / ml and 25°C according to ISO 307:2019, and at least 22.5 pbw of a modified polyolefin impact modifier (MIM) having a melt flow rate (MFR) of up to 15 g / 10 min, measured at 230°C and a 2.16 kg test load according to ISO 1133:2011, the total amount of both being 100 pbw. The present invention also relates to a process for preparing the impact-modified polyamide composition, a process for producing a molded article from the impact-modified polyamide composition, and a molded article made from the impact-modified polyamide composition.

Description

[Technical Field]

[0001] The present invention relates to a polyamide composition, more specifically to an impact-modified polyamide composition comprising an aliphatic polyamide (APA) and a modified polyolefin impact modifier (MIM). The present invention also relates to a process for preparing the impact-modified polyamide composition, a process for producing a molded article from the impact-modified polyamide composition, and a molded article made with the impact-modified polyamide composition. [Background technology]

[0002] The present invention is particularly directed to impact-modified polyamide compositions that can be used in rotational molding applications, such as gas containers and fuel tanks. The technique used for their production is also called rotomolding 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 pressurized gas container and fuel tank applications, good mechanical properties and high impact resistance at low temperatures are additionally required.

[0003] Impact-modified polyamide compositions are known in the art. Impact-modified polyamide compositions and rotationally molded articles made therefrom are described, for example, in US 2021 / 0139699 A1. US 2021 / 0139699 A1 references two other patent documents: WO 2017 / 094720 (=US 2021 / 0301131 A1) and JP 2013-532748 (=US 9309406 B2). Both documents describe impact-modified polyamide compositions, with US 2021 / 0301131 A1 primarily directed to injection-molded parts, while US 9309406 B2 is directed to fuel parts that can be made by injection molding, blow molding, or rotomolding.

[0004] According to US 2021 / 0301131A1, there has been a demand for a polyamide resin composition that has excellent moldability (measured by spiral flowability during injection molding) or appearance (surface gloss) as a molded product, and that has flexibility without impairing the mechanical strength (impact resistance) that polyamide resins should inherently exhibit. US 2021 / 0301131A1 describes the possibility of problems with the flowability of polyamide compositions, and suggests that flowability can be improved by using a polyamide resin with a low molecular weight or by using a flow modifier (plasticizer or wax), but these methods instead pose other problems, such as a decrease in impact strength, and therefore limit their applications. US 2021 / 0301131A1 claims that these problems are solved by using a specific acid-modified polyolefin (Q) having a melt flow rate (MFR) of 50 to 200 g / 10 min at 230°C under a load of 2.16 kg in an amount of 1 to 50 mass % in combination with 50 to 99 mass % of a polyamide. According to US 2021 / 0301131A1, by controlling the MFR of the acid-modified polyolefin (Q) within this range, a polyamide resin molded product can be obtained that has an excellent balance between impact resistance and specular gloss, or an excellent balance between impact resistance and flowability during molding. In the examples of US 20210301131A1, a viscosity number of 145 to 150 cm is obtained. 3 Polyamide 66 having a viscosity of 1 / g was used for the polyamide (P), and two grades of modified polyolefin Q were individually tested, used in amounts of 10% or 20% by weight. However, at 10% by weight, the values ​​for elongation at break (23°C) were very low, while at 20% by weight, the melt viscosity was very high even at a high temperature of 290°C, making these materials unsuitable for use in rotational molding. Furthermore, US2021 / 0139699 also discloses that, although the flow state was improved by using a relatively low-viscosity polyolefin as the acid-modified polyolefin in US20210301131A1, impact resistance, especially at low temperatures, was reduced.

[0005] US9309406B2 (corresponding to JP2013-532748) relates to a fuel portion containing a polymer composition comprising: a polyamide having a ratio of terminal carboxyl group concentration to terminal amino group concentration of 1 or more; fine talcum in an amount of 0.001 to 1% by mass relative to the total amount of the polymer composition; and an impact modifier in an amount of at least 1.0% by mass relative to the total amount of the polymer composition. In the examples, the following components were used: polyamide PA6; fine talcum (median diameter 0.50 micrometers, 99% less than 5 micrometers, 92% less than 2 micrometers, and 75% less than 1 micrometer); and maleic anhydride (MAH)-grafted ethene copolymer as an impact modifier. Examples with 9.75% and 20% by mass of impact modifier were reported. Patent document JP2013-532748 commented on US2021 / 0139699A1 by disclosing that: blending an impact modifier with a polyamide resin results in a significant increase in the viscosity of the polyamide resin composition caused by a chemical reaction between them, and rotationally molded articles obtained by rotationally molding such polyamide resin compositions have poor surface properties, as fine particles tend to remain on the surface and are 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 same. The polyamide resin composition of US2021 / 0139699A1 is - Component (A): aliphatic polyamide, relative viscosity (ηr): less than 2.6 (measured according to JIS K6920 under conditions of 96% by mass of sulfuric acid, 1% by mass of polymer concentration and 25°C), amount: "a" parts by mass (pbw); - Component (B): Modified polyolefin, density: 0.895 g / cm 2 The following (measured in accordance with ASTM D1505): "b" pbw; and - Component (C): Unmodified polyolefin, MFR value: 3.0-30g / 10min (measured at 190°C under a load of 2.16kg), amount: "c" pbw; wherein the polyamide resin composition satisfies the following equation: 50≦c / (b+c)×100=70, and 10≦(b+c) / (a+b+c)×100≦40.

[0007] In other words, the amount of modified polyolefin (B) is at most half of the total 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) and components (B) and (C).

[0008] In the examples of US2021 / 0139699A1, polyamide 6 with a relative viscosity (ηr) of 2.20 or 2.45 was used for component (A), maleic anhydride-modified ethylene-α-olefin copolymer (TAFMER MH5020, density = 0.866) was used for component (B) (amounts: 6.8 to 13.0 pbw), and unmodified polyolefin (EVOLU SP0540, MFR value = 3.8 g / 10 min, 190 °C, 2.16 kg; ISO 1133) was used for component (C) (amounts: 13.2 to 17.2 pbw). In most compositions, semi-aromatic polyamide (8.0 pbw or 15 pbw) was present. The amount of polyamide 6 (component A) was configured to a total of 100 pbw. Among the reported properties were surface quality, Charpy impact strength values ​​at -60°C, and tensile elongation at 23°C, indicating that the presence of unmodified polyolefin was essential for these results. However, while surface quality was better for compositions using polyamide 6 with a relative viscosity (ηr) of 2.20, mechanical properties such as impact strength and tensile elongation were better for compositions using polyamide 6 with a relative viscosity (ηr) of 2.45 in combination with 15 pbw of semi-aromatic polyamide. Furthermore, comparative experiments showed that while a higher content of unmodified polyolefin improved mechanical properties, surface properties were unsatisfactory, while a lower content of unmodified polyolefin or the absence of semi-aromatic polyamide reduced mechanical properties.

[0009] US2021261773A1 relates to a composition comprising a) 30 to 90% by mass of a polyamide and b) 10 to 40% by mass of a polyethylene elastomer (POE) composition, wherein the amounts of a) and b) are based on the total composition, and the sum of a) and b) is at least 60% by mass of the total composition, and the POE composition consists of b1) 20 to 95% by mass of a non-functionalized polyethylene elastomer and b2) 5 to 80% by mass of a functionalized polyethylene elastomer, and the amounts of b1) and b2) are based on the POE composition. US2021261773A1 describes that this composition can be used for rotational molding.

[0010] JP 2004 346240 A relates to a polyamide resin composition that can provide molded articles with excellent rigidity, heat resistance, dimensional stability, impact resistance, toughness, flow properties, and appearance. The composition is described as being suitable for structural or exterior components of electrical / electronic components 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 ratios.

[0011] Apart from the importance of material flowability in obtaining a product with low porosity, uniform wall thickness, and smooth surface, good mechanical properties in tensile tests, and high impact resistance in Charpy impact tests at both room and low temperatures, the inventors have observed that impact-modified polyamide compositions generally show poor or even worse results in impact tests using a drop weight. The drop weight impact test results are indicative of the mechanical performance of the resulting tank. A poor drop weight impact result indicates that the tank will not pass the mechanical requirements, typically a drop test from a certain height at -40°C. This property may be relevant during transportation or in the practical use of the roto-molded product. [Prior art documents] [Patent documents]

[0012] [Patent Document 1] US2021 / 0139699A1 [Patent Document 2] WO2017 / 094720(=US2021 / 0301131A1) [Patent Document 3] JP2013-532748(=US9309406B2) [Patent Document 4] US2021 / 0301131A1 [Patent Document 5] US9309406B2 [Patent Document 6] JP2013-532748 [Patent Document 7] US2021261773A1 [Patent Document 8] JP 2004 346240 A Summary of the Invention [Problem to be solved by the invention]

[0013] It is therefore an object of the present invention to provide a polyamide composition which is preferably suitable for rotomoulding, has a good balance of flowability, mechanical properties and impact resistance at room and low temperatures, and shows good results in the drop weight impact test.A further object is to provide a rotomoulded article which has a good balance of surface quality, mechanical properties and impact resistance at room and low temperatures, and shows satisfactory results in the drop weight impact test. [Means for solving the problem]

[0014] These objects are achieved with the polyamide composition according to the invention and with rotomoulded articles made using said polyamide composition.

[0015] The polyamide composition according to the present invention comprises - X parts by weight (pbw) of an aliphatic polyamide (APA), - Y parts by weight (pbw) of a modified polyolefin impact modifier (MIM); one or more other polymeric components and / or one or more additives different from X and different from Y (together referred to herein as other component Z) in an amount of from 0 to 30 pbw in total, as defined relative to 100 pbw of the sum of X and Y; An impact modified polyamide composition comprising: - the aliphatic polyamide (APA) has a maximum relative viscosity (RV) of 2.40, measured in 96% sulfuric acid at 0.01 g / ml and 25°C according to ISO 307:2019; - The modified polyolefin impact modifier (MIM) has a melt flow rate (MFR) of up to 15 g / 10 min, measured at 230 °C and a test load of 2.16 kg according to a method in accordance with ISO 1133:2011; - the sum of X and Y is 100 pbw, X is at most 77.5 pbw, and Y is at least 22.5 pbw; - the relative viscosity (RV) of the aliphatic polyamide (APA) is 2.20 or less, X is at least 60 pbw and Y is at most 40 pbw; - the relative viscosity (RV) of the aliphatic polyamide (APA): in the range of more than 2.20 to 2.33 or less, X is at least 65 pbw and Y is at most 35 pbw; - the relative viscosity (RV) of the aliphatic polyamide (APA): in the range of more than 2.33 to 2.40 or less, X is at least 70 pbw and Y is at most 30 pbw; Other component Z comprises not more than 10 pbw of unmodified polyolefin and not more than 2 pbw of fine talcum per 100 pbw of the total of X and Y, provided that one or more other polymeric components and one or more additives (together referred to herein as other component Z) are different from X and different from Y and are present in a total amount ranging from 0 to 30 pbw per 100 pbw of the total of X and Y; It is a polyamide composition.

[0016] The advantage of the impact-modified polyamide composition according to the invention, comprising a polyamide having the above parameters in the above amounts and a modified polyolefin impact modifier, is that the polyamide composition not only has a good balance of flowability, mechanical properties, and impact resistance at room and low temperatures, but also has positive results in drop weight impact tests at low temperatures.A further advantage is that the polyamide composition is suitable for rotomoulding, and rotomoulded articles made therefrom not only have a good balance of surface quality, mechanical properties, and impact resistance at room and low temperatures, but also show robust performance in drop weight impact tests at low temperatures.

[0017] With regard to the limitations of the polyamide composition containing limited amounts of other Z, it is noted that the inventors have found that the presence of excessive other constituents can adversely affect one or more of the flowability, mechanical properties, room temperature and low temperature impact resistance, low temperature drop weight impact properties, and / or gas barrier properties of the polyamide composition. The inventors have particularly found that the addition of excessive amounts of unmodified polyolefin (including unmodified impact modifiers), and excessive amounts of inorganic filler particles, specifically fine talcum, can have an increasingly adverse effect on one or more of the flowability and barrier properties.

[0018] These results are quite surprising in several respects, namely that good flow properties are obtained with modified polyolefin impact modifiers having low melt flow rates, even when used in relatively high amounts, but also that good mechanical properties and impact resistance are obtained even in the absence or presence of only small amounts of unmodified polyolefin or semi-aromatic polyamide, especially when using polyamides with low relative viscosities (RV), while also showing positive results in drop weight impact tests.

[0019] The aliphatic polyamide in the composition according to the present invention is a polyamide that can be obtained by polymerizing a lactam, an aminocarboxylic acid, an aliphatic diamine and an aliphatic dicarboxylic acid as raw materials, or by copolymerizing any combination thereof, via a known method, for example, melt polymerization, solution polymerization, or solid-state polymerization. AB polyamides obtainable by polymerizing lactams and / or aminocarboxylic acids; or AABB type polyamides, obtainable by copolymerizing aliphatic diamines and aliphatic dicarboxylic acids; or - AB / AABB type polyamide, which is a polyamide copolymer obtainable by copolymerizing aliphatic diamines and aliphatic dicarboxylic acids in combination. It can be either of the following.

[0020] Examples of lactams include caprolactam, enantholactam, undecane lactam, dodecane lactam, α-pyrrolidone, and α-piperidone. Examples of aminocarboxylic acids include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. In the AB polyamide or AB / AABB copolymer, one type of lactam or two or more types of lactams can be used.

[0021] In the AA / BB polyamide or AB / AABB copolymer, one aliphatic diamine or two or more aliphatic diamines 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-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 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, and 1,20-eicosanediamine. Branched aliphatic diamines are suitably diamines with methyl-substituted aliphatic chains. Examples of branched aliphatic diamines 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.

[0022] 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 AB / AABB copolymer, one aliphatic dicarboxylic acid or two or more aliphatic dicarboxylic acids can be used.

[0023] Examples of AB polyamides include homopolymers such as polycaprolactam (polyamide 6), polyundecaneamide (polyamide 11), and polydodecanamide (polyamide 12), as well as any copolymers thereof. Examples of AA / BB polyamides include polytetramethylene sebacamide (polyamide 410), polyhexamethylene adipamide (polyamide 66), polyhexamethylene suberamide (polyamide 68), polyhexamethylene azelamide (polyamide 69), polyhexamethylene sebacamide (polyamide 610), and polyhexamethylene dodecamide (polyamide 612). Examples of AB / AABB polyamide copolymers include polyamide 6 / 66, polyamide 6 / 410, polyamide 6 / 68, polyamide 6 / 610, and polyamide 6 / 6 / 12.

[0024] Aliphatic polyamides (APAs) may contain monomer components other than those based on lactams, aminocarboxylic acids, aliphatic diamines, and aliphatic dicarboxylic acids; and monomer components 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 either aliphatic 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 polyamides in the compositions according to the present invention suitably contain up to 10 mol% of other monomer components. As used herein, an aliphatic polyamide may contain up to 5 mol% of an aromatic monomer component, yet still be considered an aliphatic polyamide. For example, an aliphatic polyamide may contain 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 contains 0-5 mol%, more preferably 0-2 mol%, of other monomer components. As used herein, the other monomer component can be one other monomer component, or two or more other monomer components. As used herein, the molar percentage (mol%) is based on 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 in aliphatic polyamides are known in the art.

[0025] 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 caprolactam or 6-aminocaproic acid or combinations thereof, another lactam and / or aminocarboxylic acid, or aliphatic diamines and aliphatic dicarboxylic acids, or - other lactams and / or aminocarboxylic acids, as well as aliphatic diamines and aliphatic dicarboxylic acids Polyamide 6 copolymer obtainable by copolymerization with an aliphatic comonomer selected from:

[0026] These polyamides are preferred for their thermal stability during molding and for their moldability. More preferably, the polyamide is a polyamide 6 polymer, which is a polyamide 6 homopolymer or a polyamide 6 copolymer containing up to 25 mol % of an aliphatic comonomer. Even more preferably, the polyamide 6 polymer contains 0 to 10 mol %, even more preferably 0 to 5 mol %, and most preferably 0 to 2 mol % of an aliphatic comonomer. As used herein, the mole percentage (mol %) is relative to the total amount of caprolactam or 6-aminocaproic acid and aliphatic comonomer copolymerized in the aliphatic polymer.

[0027] The aliphatic polyamide of the composition according to the invention is suitably a semi-crystalline polyamide. Semi-crystalline polyamides have melting temperatures (T m ) Suitably, the melting temperature T m can be as high as 280°C or higher or as low as 160°C or lower. m is measured at a heating rate of 10°C / min according to a method in accordance with ISO 11357-3:2018. m is in the range of 180 to 260° C., more preferably in the range of 190 to 240° C. The advantage is that the composition has a more balanced combination of properties in terms of moldability, thermal stability during molding, and mechanical properties for molded parts.

[0028] As used herein, ranges are also considered to be inclusive of lower and upper limits. Thus, for example, in the phrase "in the range of 180 to 260°C," the range includes the lower limit of 180°C and the upper limit of 260°C.

[0029] The aliphatic polyamide may be a mixture of two or more polyamides. In this specification, the polyamides may have different relative viscosities (RV). In this case, the relative viscosity (RV) of the aliphatic polyamide of the composition according to the present invention is the relative viscosity measured at 25°C in 96% sulfuric acid at a concentration of 0.01 g of the mixture of two or more polyamides per ml according to a method in accordance with ISO 307:2019.

[0030] For the compositions of the present invention, it is essential that the aliphatic polyamide have a relative viscosity (RV) of up to 2.40, not only to achieve good flowability but also to enable the use of a modified polyolefin impact modifier (MIM) in a sufficiently high amount to achieve the benefits of the present invention. The inventors have found that when the RV exceeds 2.40, the ability of the composition to simultaneously achieve suitable qualities for roto-molding, when combined with an appropriate amount of MIM, becomes increasingly impaired. 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, for example, to 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 to 2.40, preferably 1.90 to 2.40, and more preferably 2.00 to 2.40. This has the advantage of better retention of high levels of mechanical properties, including good Charpy impact resistance and acceptable drop weight impact resistance. Also preferably, the viscosity is at most 2.35, more preferably at most 2.30 and even more preferably at most 2.25, which has the advantage that flowability is improved while mechanical properties, including good Charpy impact resistance and acceptable drop weight impact resistance, are maintained at outstanding levels.

[0031] The modified polyolefin impact modifier (MIM) in the composition according to the present invention has a melt flow rate (MFR) of up to 15 g / 10 min, measured at 230 ° C and a test load of 2.16 kg according to a method in accordance with ISO 1133:2011. The MFR may vary over a wider range, for example, as low as 0.25 g / 10 min. At too low an MFR value, the flowability of the composition is too hindered in its practical use, for example, in rotational molding. If the MFR value for the modified polyolefin impact modifier (MIM) is too high, the mechanical properties are not good, especially for polyamides with the relative viscosity (RV) according to the present invention.

[0032] 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, and 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, and 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 to 10 g / 10 min, or in the range of 0.8 to 5 g / 10 min, or in the range of 1.0 to 3 g / 10 min.

[0033] By polymer-modified polyolefin impact modifiers, we mean polymers containing a polyolefin backbone modified with functional groups. The polyolefin backbone is suitably a copolymer of different olefin monomers, in particular 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 butylene; or a copolymer of ethylene, propylene, and butylene; or a copolymer of at least one olefin selected from ethylene, propylene, and butylene with at least one other α-olefin monomer having 4 to 20 carbon atoms. Herein, 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%, respectively. Among these, ethylene-α-olefin copolymers are more preferred, and ethylene-butylene copolymers and ethylene-1-octene copolymers are even more preferred.

[0034] The polyolefin backbone may further contain monomer units derived from unsaturated monomers other than olefin monomers. These other unsaturated monomers may be, for example, diene monomers or aromatic monomers, or a combination thereof. Examples of diene monomers (e.g., those contained 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 (e.g., those contained in ethylene-α-olefin copolymers or propylene-α-olefin copolymers) include styrene. Other unsaturated monomers, if any, may be present in an amount of up to 20 mol %, preferably up to 10 mol %, and more preferably 0 to 5 mol %. As used herein, mole percent refers to the total molar amount of olefin monomers and other unsaturated monomers in the polyolefin backbone. Modified polyolefin impact modifiers comprising polyolefins having other unsaturated monomers copolymerized in combination with olefin monomers, and polyolefin backbones having other copolymerized unsaturated monomers, are known in the art.

[0035] The modified polyolefin impact modifier comprises a polyolefin backbone modified with a functional group. Examples of suitable functional groups include acidic, epoxy, and glycidyl groups. The modified polyolefin impact modifier used in the present invention is preferably an acid-modified polyolefin, an epoxy-modified polyolefin, a glycidyl-modified polyolefin, or any combination thereof. Among these, acid-modified polyolefins are particularly preferred. Acid-modified polyolefins can be obtained by modifying polyolefins with unsaturated carboxylic acids or their acid anhydrides. Examples of unsaturated carboxylic acids or their acid anhydrides include maleic 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 is preferred, with maleic anhydride being more preferred. As a substitute for the unsaturated carboxylic acid or its anhydride, derivatives such as acid amides and acid esters can be used.

[0036] The amount of modifying functional group in the modified polyolefin impact modifier can vary and can be expressed as the amount of functional group modification expressed as a weight percentage (wt%) relative to the weight of the modified polyolefin impact modifier (MIM).

[0037] Suitably, the modified polyolefin impact modifier (MIM) has a functional group modification level of at least 0.25 wt. Also suitably, the modified polyolefin impact modifier (MIM) has a functional group modification level of up to 2.5 wt. %, preferably up to 2.0 wt. More preferably, the functional group modification level is in the range of 0.3 to 1.5 wt. %, even more preferably in the range of 0.4 to 1.0 wt. As used herein, mass percentages (mass %) are based on the total mass of the modified polyolefin impact modifier. Acid-modified polyolefins are particularly preferred, and the modified polyolefin impact modifier (MIM) preferably has an acid modification level of at least 0.25 wt. % and up to 2.0 wt. %, more preferably in the range of 0.3 to 1.5 wt. %, most preferably in the range of 0.4 to 1.0 wt. A particularly preferred acid-modified polyolefin is a polyolefin modified with maleic anhydride. The corresponding maleic anhydride modified polyolefin suitably contains at least 0.25% or at most 2.5%, preferably 0.3 to 1.5%, more preferably 0.4 to 1.0% by weight of maleic anhydride based on the weight of the modified polyolefin impact modifier.

[0038] Suitably, the modified polyolefin impact modifier (MIM) has a glass transition temperature (T g ) and the glass transition temperature may be as low as -70°C or even lower. Preferably, the modified polyolefin impact modifier (MIM) has a T of up to -40°C. g , more specifically 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. g In this specification, T g is measured at a heating rate of 10°C / min according to a method in accordance with ISO 11357-2:2020.

[0039] The modified polyolefin impact modifier (MIM) preferably has a glass transition temperature (T g ) and the glass transition temperature is as low as -70°C, and may be even lower. More preferably, the modified polyolefin impact modifier (MIM) has a T of at most -55°C, and even more preferably at most -60°C.g In this specification, T g is measured at a heating rate of 10°C / min according to the method of ISO 11357-2:2020. g is preferred.

[0040] Preferably, the modified polyolefin impact modifier (MIM) is 1 g / cm 3 It has a density of less than 0.80 g / cm 3 It may be as low as 0.80 g / cm or even lower, but is suitably 0.80 g / cm 3 or more, e.g., at least 0.84 g / cm 3 More preferably, the modified polyolefin impact modifier (MIM) is at most 0.95 g / cm 3 , and even more preferably up to 0.90 g / cm 3 , more specifically 0.80 to 0.90 g / cm 3 in the range of 0.88 g / cm 3 More specifically, the density is 0.84 to 0.88 g / cm 3 In this specification, the density is measured by a method in accordance with ASTM D1505-03. From the viewpoint of mechanical properties at low temperatures, a low density is preferred.

[0041] Preferably, the modified polyolefin impact modifier (MIM) has a Shore A hardness of less than 100. The Shore A hardness may be as low as 40 or even lower, but is suitably 45 or higher, for example at least 50. More preferably, the modified polyolefin impact modifier (MIM) has a Shore A hardness of at most 90, even more preferably at most 80, more specifically in the range of 45 to 80, and most preferably at most 75. More specifically, the Shore A hardness is in the range of 50 to 75. In this specification, the Shore A hardness is measured by a method in accordance with ASTM D2240-15. A low Shore A hardness is preferred from the viewpoint of mechanical properties at low temperatures.

[0042] The modified polyolefin impact modifier (MIM) may be present in compositions according to the invention in an amount of at least 22.5 pbw, and in a range depending on the relative viscosity of the aliphatic polyamide.

[0043] When the relative viscosity (RV) of the aliphatic polyamide (APA) is 2.20 or less, X is at least 60 pbw and Y is at most 40 pbw. When the relative viscosity (RV) of the aliphatic polyamide (APA) is within the above range, X is preferably in the range of 62.5 to 75 pbw and Y is in the range of 25 to 37.5 pbw.

[0044] When the relative viscosity (RV) of the aliphatic polyamide (APA) is in the range of more than 2.20 and up to 2.33, X is at least 65 pbw and Y is at most 35 pbw. Preferably, when the relative viscosity (RV) of the aliphatic polyamide (APA) is in the range of more 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, whereas when the relative viscosity (RV) of the aliphatic polyamide (APA) is in the range of more than 2.27 and up to 2.33, X is preferably at least 69 and Y is at most 31 pbw.

[0045] When the relative viscosity (RV) of the aliphatic polyamide (APA) is in the range of more than 2.33 and up to 2.40, X is at least 70 pbw and Y is at most 30 pbw. Preferably, when the relative viscosity (RV) of the aliphatic polyamide (APA) is in the above range, X is at least 72.5 pbw and Y is at most 27.5 pbw.

[0046] The advantage of the amount of modified polyolefin impact modifier (MIM) within the above preferred ranges in combination with the above ranges for the relative viscosity (RV) of the aliphatic polyamide (APA) is that the composition has an improved balance of properties, particularly in terms of flow and mechanical properties.

[0047] Preferably, the impact modified polyamide composition has a combination of properties that meet all of the following parameters: - Complex viscosity at 250°C (Eta* ): Max. 700Pa·s; - Elongation at break at -40°C: at least 17.5%; - Notched impact strength at 23°C: at least 70KJ / m 2 and - Drop weight impact resistance at -40°C: at least 60% success rate.

[0048] In this specification, various properties are measured by the following methods: - Complex viscosity (Eta * ) is 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. - The elongation at break is measured according to ISO 527-2:2012 Type 1A at a pulling speed of 50 mm / min; - Notched impact strength is determined according to ISO 179-2:2020; and - Drop weight impact resistance is measured on five 80 x 80 x 2 mm injection-molded plaques using a method in accordance with ISO 6603-2-2000-10, and the success rate is determined as the percentage of plaques that pass the test.

[0049] The complex viscosity (Eta * ) can be, for example, about 550 Pa·s, about 425 Pa·s, about 300 Pa·s, or about 250 Pa·s. Suitably, the complex viscosity (Eta * ) is at least 200 Pa·s.

[0050] More preferably, the impact modified polyamide composition has a complex viscosity (Eta) of up to 600 Pa·s at 250°C. * ), more preferably a complex viscosity (Eta) of up to 500 Pa·s * The advantage of a lower complex viscosity is that the processing of the composition runs more smoothly and in processing, the molding temperatures required to obtain a high quality product are not as high.

[0051] Even more preferably, the impact modified polyamide composition has the following parameters: - elongation at break at -40°C: at least 20%; and / or - Notched impact strength at 23°C: at least 75KJ / m 2 , most preferably at least 80 KJ / m 2 It has a combination of properties that meet one or more of the following criteria:

[0052] The value for the composite elongation at break of the composition at -40°C can be, for example, about 20%, about 25%, about 36%, about 43% or about 48%. Suitably, the elongation at break at -40°C is up to 60%, or even up to 50%, and still provide good to very good results.

[0053] The notched impact strength at 23°C is, for example, about 83KJ / m 2 , or about 88 KJ / m 2 , or about 97 KJ / m 2 while the notched impact strength may be higher, for example, 110 KJ / m 2 may be up to 110KJ / m 2 , more specifically up to 105KJ / m 2 is.

[0054] More preferably, the impact modified polyamide composition has a drop weight impact resistance of at least 80% success rate at −40° C. The success rate can be as high as 100%, where all tested plaques successfully pass the test.

[0055] The impact-modified polyamide composition of the present invention may also contain, in addition to the aliphatic polyamide and MIM, one or more other polymeric components and / or one or more additives, which constitute part of the other components. These other components may be present, if desired, in amounts that do not impair the objectives of the present invention. The additives and / or other polymeric components may suitably be present in an amount ranging from 0.001 to 30 pbw, preferably from 0.01 to 20 pbw, and more preferably from 0.1 to 10 pbw. As used herein, parts by mass (pbw) are based on the total weight of X and Y (100 pbw), where X represents the amount of aliphatic polyamide (in pbw) and Y represents the amount of modified polyolefin impact modifier (MIM) (in pbw). The inventors have found that adding the other component (other component Z) in an amount greater than 30 pbw (relative to the sum of X and Y) may adversely affect one or more of the properties of the composition.

[0056] The other polymer component can 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 objectives of the present invention. Suitable examples of the other polymer component include semi-aromatic polyamides, other thermoplastic polymers, unmodified polyolefins, and rubbers.

[0057] The unmodified polyolefin among the other polymer components can be, for example, a polyolefin homopolymer or a polyolefin copolymer. Examples of polyolefin homopolymers include polyethylene and polypropylene. An example of a polyolefin copolymer is the unmodified polyolefin copolymer used in the backbone of the MIM. Preferably, the unmodified polyolefin is selected from polyethylene, polypropylene, ethylene-α-olefin copolymer, and propylene-α-olefin copolymer. The unmodified polyolefin can be present in an amount of up to 10 pbw, more preferably up to 7.5 pbw, and at least 1 pbw. Even more preferably, the amount of unmodified polyolefin is in the range of 0 to 5 pbw, based on 100 pbw of the total amount of X and Y.

[0058] The semi-aromatic polyamide in the other polymer component can 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 can be a semi-crystalline semi-aromatic polyamide or an amorphous semi-aromatic polyamide. Preferably, the semi-crystalline semi-aromatic polyamide has a melting temperature (T m ) at most 260° C., more preferably at most 240° C., and suitably at least 190° C. Even more preferably, the semi-aromatic polyamide is an amorphous semi-aromatic polyamide.

[0059] The semi-aromatic polyamide of the other polymer component can include aliphatic diamine units having 6 to 12 carbon atoms derived from a diamine or 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 can include aromatic dicarboxylic acid units derived from a dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid.

[0060] The semi-aromatic polyamide may in particular be a 6T copolymer, i.e. a copolymer comprising 6T units in addition to units derived from other monomers. Specific examples of semi-aromatic polyamides suitable for use in the compositions according to the 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 sebacamide) copolymer (polyamide 6T / 611), poly(hexamethylene terephthalamide / hexamethylene sebacamide) copolymer (polyamide 6T / 612), poly(hexamethylene terephthalamide / hexamethylene sebacamide) copolymer (polyamide 6T / 613), poly(hexamethylene terephthalamide / hexamethylene sebacamide) copolymer (polyamide 6T / 614), poly(hexamethylene terephthalamide / hexamethylene sebacamide) copolymer (polyamide 6T / 615), poly(hexamethylene terephthalamide / hexamethylene sebacamide) copolymer (polyamide 6T / 616), poly(hexamethylene terephthalamide / hexamethylene sebacamide) copolymer (polyamide 6T / 617), poly(hexamethylene terephthalamide / hexamethylene sebacamide) copolymer (polyamide 6T / 618), poly(hexamethylene terephthalamide / hexamethylene sebacamide) copolymer (polyamide 6T / 619), poly(hexamethylene terephthalamide / hexamethylene sebacamide) copolymer (polyamide 6T / 620), poly(hexamethylene terephthalamide / hexamethylene sebacamide) copolymer (polyamide 6T / 621). Poly(hexamethylene dodecamide) 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), 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.

[0061] Preferably, the semi-aromatic polyamide in the other polymeric components is present in an amount of at most 10 pbw, more preferably at most 7.5 pbw, and even more preferably at most 5.0 pbw. Most preferably, the amount of semi-aromatic polyamide is in the range of 0 to 2.5 pbw, per 100 pbw of the combined amount of X and Y.

[0062] The additives that may be further present in the impact-modified polyamide composition according to the present invention can be any additive or mixture of additives selected from the auxiliary additives commonly used in non-reinforced impact-modified polyamide compositions, including, but not limited to, stabilizers (including heat stabilizers, UV absorbers, light stabilizers, and antioxidants), antistatic agents, lubricants, antiblocking agents, fillers, nucleating agents, mold release agents, plasticizers, crosslinking agents, foaming agents, colorants (pigments, dyes).

[0063] Preferably, the additive is present in an amount of up to 10 pbw, more preferably up to 7.5 pbw, and although the amount may be 0 pbw, even more preferably the amount of additive is in the range of 0.1 to 5 pbw, relative to a total amount of X and Y of 100 pbw.

[0064] The inventors have found that higher relative contents of the other constituents (Z) can adversely affect the flow behavior and one or more of the mechanical properties of the roto-molded part, such as impact resistance, especially at low temperatures.

[0065] Preferably, the impact-modified polyamide composition includes at least one stabilizer, the advantage of which is that molding quality is better preserved in the presence of oxygen during processing. The stabilizer can be an organic stabilizer, an inorganic stabilizer, or a combination thereof.

[0066] Examples of organic stabilizers include antioxidants, such as phenol-based antioxidants, thioether-based antioxidants, and / or phosphorus-based antioxidants. The organic stabilizer is preferably at least one selected from the group consisting of phenol-based antioxidants and phosphorus-based antioxidants, more preferably at least one selected from the group consisting of hindered phenol-based antioxidants having a t-butyl group in the ortho position and phosphite ester-based antioxidants of phenols having a t-butyl group in the ortho position. Suitably, the organic stabilizer is present in an amount ranging from 0.1 to 2 pbw, more specifically 0.3 to 1.5 pbw, preferably 0.5 to 1.2 pbw, based on 100 pbw of the total amount of X and Y.

[0067] Examples of inorganic stabilizers include metal halides, such as copper halides. A specific example of such an inorganic stabilizer is cuprous iodide mixed with potassium bromide (CuI / KBr).

[0068] Preferably, the impact modified polyamide composition comprises at least an inorganic stabilizer, which is 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 Cu, based on the total weight of the impact modified polyamide composition.

[0069] 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 Cu. As used herein, parts by weight (pbw) are based on a total weight of 100 pbw of aliphatic polyamide (X) and modified polyolefin impact modifier MIM (Y). As used herein, parts by million (ppm) are based on the total weight of the impact-modified polyamide composition.

[0070] Most preferably, a combination of a hindered phenol-based antioxidant having a t-butyl group at the ortho position and a copper-based inorganic stabilizer is used, more specifically, a combination of a hindered phenol-based antioxidant having a t-butyl group at the ortho position and CuI / KBr is used.

[0071] The additives for the impact-modified polyamide composition may include a filler. An example is talcum, which may be hydrated magnesium silicate or fine talcum. Preferably, the composition includes fine talcum. The fine talcum may be any known fine talcum suitable for use in polyamide compositions. The fine talcum preferably has a median diameter (d50) of less than 1 micrometer, more preferably less than 70 micrometers, and even more preferably less than 50 micrometers. The particle size distribution of the fine talcum is determined using a high-speed image analyzer. This analyzer projects all particles in a limited sample as a two-dimensional image and measures the actual surface area of ​​all recorded individual particles. These surface areas are then recalculated to a circle having the same surface area as the calculated diameter. The mean value (d50) of the particle size distribution is then determined by known means.

[0072] Fine talcum can be present in the polymer composition in an amount up to 10 pbw, e.g., 0.001 pbw to 10 pbw. Preferably, fine talcum can be present in the impact-modified polyamide composition in an amount ranging from 0.01 to 5.0 pbw, more preferably from 0.01 to 3.0 pbw, even more preferably from 0.01 to 2.0 pbw, and most preferably from 0.01 to 0.5 pbw. For example, in one embodiment, the amount of fine talcum can preferably be 0.05 wt.%, based on the total weight of the composition. The inventors have found that amounts ranging from at least 0.01 to about 3 pbw, preferably up to about 2 pbw, and most preferably up to 1 pbw, are increasingly beneficial in providing good impact resistance at low temperatures. Excessive amounts of talcum can result in increased brittleness at low temperatures, for example, when using a bulking agent. As used herein, the amount of fine talcum is in parts by weight (pbw) relative to the total weight of X and Y, 100 pbw.

[0073] The present invention also relates to a method for preparing the impact-modified polyamide composition of the present invention. The impact-modified polyamide composition can be obtained by melt-mixing an aliphatic polyamide (APA) and a modified polyolefin impact modifier (MIM) according to the amount parameters described hereinabove. The impact-modified polyamide composition can be prepared, for example, by melt-mixing the aliphatic polyamide, the MIM, and optionally additional components, if desired, using various methods known in the relevant art. Specifically, 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 tumbler mixer, or a ribbon blender, heating and mixing the components, and melt-kneading the mixture using, for example, a single-screw extruder, a multi-screw extruder, a kneader, or a Banbury mixer. In particular, when a device with excellent kneading performance, such as a multi-screw extruder, a kneader, or a Banbury mixer, is used, a high-quality impact-modified polyamide composition in which each component is more uniformly dispersed can be obtained.

[0074] The present invention also relates to a method for producing molded articles from the impact modified polyamide composition, and to molded articles made with the impact modified polyamide composition.

[0075] The method according to the present invention is a rotational molding method using the impact-modified polyamide composition according to the present invention and any special or preferred embodiment thereof as described hereinabove. Any rotational molding method known in the art can be used. Molding of the impact-modified polyamide composition according to the present invention by the rotational molding method can be carried out, for example, in the following manner. For example, first, a mold can be attached to a known rotational molding device, which can move in a single or multiple axes, rotating, counter-rotating, or pendulum motion, and the impact-modified polyamide composition, for example in the form of powder or pellets, is introduced into the mold. Then, the interior of the mold is heated by: a) T m+5℃~b)T m The temperature can be between +80°C and 100°C. m is the melting temperature of the aliphatic polyamide. In other words, the mold can be heated to a temperature range of 5 to 80°C higher than the melting temperature of the aliphatic polyamide. The impact-modified polyamide composition is molded while the aliphatic polyamide is melted at this temperature. Thereafter, the mold is heated to a temperature higher than the glass transition temperature (T g )~d)Temperature T m The rotomolded article is cooled to a temperature between -10°C to allow it to cool and solidify. The rotomolded article is then removed from the mold. The cooling time varies depending on the thickness of the rotomolded article, but is generally within the range of several minutes to several hours. During rotomolding, an inert gas atmosphere, such as nitrogen gas, is preferred inside the mold, since it is oxygen-free or substantially oxygen-free, to prevent discoloration and deterioration of the rotomolded article. The impact-modified polyamide composition can alternatively be introduced into the mold in molten form; for example, the impact-modified polyamide composition can be first introduced into an extruder, where it is heated and melted, and then the molten impact-modified polyamide composition can be directly extruded into a preheated mold.

[0076] In this specification, the T of the aliphatic polyamide described above g is measured at a heating rate of 10°C / min by a method according to ISO 11357-2:2020. m is measured at a heating rate of 10°C / min according to a method in accordance with ISO 11357-3:2018.

[0077] The molded article according to the present invention is a rotomolded article made from the impact modified polyamide composition according to the present invention and / or any preferred embodiment thereof, as described herein above.

[0078] The rotomoulded articles according to the invention and obtainable by the rotomoulding process according to the invention can be, for example, containers or tanks and can be used for various purposes, for example pressurised gas containers, fuel tanks etc.

[0079] Due to their favourable properties, the impact modified polyamide compositions according to the invention can also be advantageously used in other moulding processes, for example injection moulding processes or blow moulding processes.

[0080] Thus, the present invention also includes a process comprising injection molding or blow molding an impact modified polyamide composition according to the present invention, or any preferred embodiment thereof described herein.

[0081] The present invention also includes a molded article that is an injection molded or blow molded article made from the impact modified polyamide composition according to the present invention, and any preferred embodiment thereof described herein above. DETAILED DESCRIPTION OF THE INVENTION

[0082] Additionally or alternatively, the present invention relates to the following variations:

[0083] In variant 1), - X parts by weight (pbw) of an aliphatic polyamide (APA), - Y parts by weight (pbw) of modified polyolefin impact modifier (MIM); 1. An impact modified polyamide composition comprising: - the aliphatic polyamide (APA) has a maximum relative viscosity (RV) of 2.40, measured at 25°C in 96% sulfuric acid at 0.01 g / ml according to ISO 307:2019; - the modified polyolefin impact modifier (MIM) has a melt flow rate (MFR) of up to 15 g / 10 min, measured at 230 °C and a test load of 2.16 kg according to a method in accordance with ISO 1133:2011; and - The sum of X and Y is 100pbw, and X is at most 77.5 pbw and Y is at least 22.5 pbw; X is at least 60 pbw and Y is at most 40 pbw when the relative viscosity (RV) of the aliphatic polyamide (APA) is 2.20 or less; When the relative viscosity (RV) of the aliphatic polyamide (APA) is in the range of more than 2.20 but not more than 2.33, X is at least 65 pbw and Y is at most 35 pbw; When the relative viscosity (RV) of the aliphatic polyamide (APA) is in the range of more than 2.33 but not more than 2.40, X is at least 70 pbw and Y is at most 30 pbw; An impact modified polyamide composition is provided.

[0084] In a second variant, the impact-modified polyamide composition is according to variant 1, in which 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 chosen from polyamide 6 (PA-6), polyamide 11 (PA-11) and polyamide 12 (PA-12), and copolymers or mixtures thereof.

[0085] In a third variant, the impact-modified polyamide composition is according to variant 1 or 2, wherein the aliphatic polyamide (APA) has a melting temperature (Tm) of up to 260°C, measured by a method according to ISO 11357-3:2018 at a heating rate of 10°C / min.

[0086] In a fourth embodiment, the impact modified polyamide composition is according to any one of the first to third embodiments, wherein the aliphatic polyamide (APA) has a relative viscosity (RV) in the range of 1.86 to 2.37, preferably in the range of 1.98 to 2.31.

[0087] In a fifth variant, the impact-modified polyamide composition is according to any one of variants 1 to 4, wherein the modified polyolefin impact modifier (MIM) has a melt flow rate (MFR) in the range of 0.5 to 10 g / 10 min, preferably in the range of 0.8 to 5 g / 10 min, more preferably in the range of 1.0 to 3 g / 10 min.

[0088] In a sixth variant, the impact-modified polyamide composition is according to any one of variants 1 to 5 above, wherein the modified polyolefin impact modifier (MIM) comprises a polyolefin copolymer backbone modified with acid functional groups.

[0089] In a seventh variant, the impact-modified polyamide composition is according to any one of variants 1 to 6, wherein the modified polyolefin impact modifier (MIM) is a glass transition temperature (Tg) measured according to ISO 11357-2:2020: maximum of −50° C., preferably maximum of −55° C., and / or - Density measured according to ASTM D1505-03: up to 0.95 g / cm 3 , preferably up to 0.90 g / cm 3 , more preferably up to 0.85 g / cm 3 and / or Shore A hardness measured according to the method in accordance with ASTM D2240-15: maximum 90, preferably maximum 80, more preferably maximum 75 It has.

[0090] In an eighth variant, the impact-modified polyamide composition is according to any one of variants 1 to 7, When the relative viscosity (RV) of the aliphatic polyamide (APA) is 2.20 or less, X is in the range of 62.5 to 75 pbw, and Y is in the range of 25 to 37.5 pbw; When the relative viscosity (RV) of the aliphatic polyamide (APA) is more than 2.20 but not more than 2.27, X is in the range of 65 to 75 pbw and Y is in the range of 25 to 35 pbw; When the relative viscosity (RV) of the aliphatic polyamide (APA) is in the range of more than 2.27 but not more than 2.33, X is at least 69 and Y is at most 31 pbw; If the relative viscosity (RV) of the aliphatic polyamide (APA) is greater than 2.33 but less than or equal to 2.40, X is at least 72.5 pbw and Y is at most 27.5 pbw.

[0091] In a ninth variant, the impact-modified polyamide composition is according to any one of variants 1 to 8, - Complex viscosity at 250°C (Eta * ): Max. 700Pa·s, - elongation at break at -40°C: at least 17.5%, - Notched impact strength at 23°C: at least 70KJ / m 2 , and - Drop weight resistance at -40℃: At least 60% success rate and Complex viscosity (Eta * ) is measured by dynamic mechanical spectroscopy (DMS) according to ISO 6721-10 at a loading time of t = 5 min and an angular frequency of 0.1 rad / s. Elongation at break is measured according to ISO 527-2:2012 Type 1A at a pulling rate of 50 mm / min. Notched impact strength is measured according to ISO 179-2:2020. Drop weight impact resistance is measured on injection-molded plaques of 80 x 80 x 2 mm according to a method in accordance with ISO 6603-2-2000-10.

[0092] In a tenth variant, the impact-modified polyamide composition is according to any of variants 1 to 9, wherein the composition comprises one or more other polymeric components and / or one or more additives in a total amount ranging from 0.001 to 30 pbw, per 100 pbw of the total amount of the aliphatic polyamide (APA), X, and the modified polyolefin impact modifier (MIM), Y.

[0093] In an eleventh variant, the impact-modified polyamide composition is according to any one of variants 1 to 10, a. an organic stabilizer in an amount of at least 0.5 pbw per 100 pbw of the total weight of X of the aliphatic polyamide (APA) and Y of the modified polyolefin impact modifier (MIM); and b. a copper-based inorganic stabilizer in an amount of at least 50 parts per million (ppm) of Cu, based on the total weight of the composition; Includes:

[0094] In a twelfth variant, there is provided a method for making an impact modified polyamide composition, comprising: - X parts by weight of an aliphatic polyamide (APA), - Y parts by weight of a modified polyolefin impact modifier (MIM); melt-mixing the APA and MIM, and X and Y are according to any one of variants 1 to 11; A method is provided.

[0095] In a thirteenth variation, there is provided a method for making an impact modified article, comprising the steps of: - X parts by weight of an aliphatic polyamide (APA), - Y parts by weight of a modified polyolefin impact modifier (MIM); melt processing the polyamide composition, impact-modified polyamide composition and APA and MIM, and X and Y according to any one of variants 1 to 11; A method is provided.

[0096] In a fourteenth variant, the method is according to variant 13, wherein melt processing is carried out by rotational molding.

[0097] In an alternative embodiment, - X parts by weight of an aliphatic polyamide (APA), - Y parts by weight of a modified polyolefin impact modifier (IM); 1. A rotomolded article made of an impact modified polyamide composition comprising: The polyamide composition and the APA and the MIM, and X and Y are according to any of the variants 1 to 11, A rotationally molded article is provided.

[0098] The present invention is further illustrated by the following examples and comparative experiments.

[0099] Examples and comparative experiments and test results material Polyamide-1 Polyamide 6 (PA6), T m Relative viscosity (RV) at 220°C, 0.01 g / ml in 96% sulfuric acid and 25°C: 2.51 (manufactured by DSM). Polyamide-2 Polyamide 6 (PA6), T m Relative viscosity (RV) at 220°C, 0.01 g / ml in 96% sulfuric acid and 25°C: 2.09 (manufactured by DSM). Impact Modifier-1 Acid-modified ethylene-butylene polyolefin: 0.5 wt% maleic anhydride; MFR at 190°C, 2.16 kg: 0.9 g / 10 min; MFR at 230°C, 2.16 kg: 1.8 g / 10 min; T g -65℃; density 870kg / m 3 ;Shore A hardness 70 (manufactured by Mitsui). Impact Modifier-2 Acid-modified ethylene-butylene polyolefin: 1 wt.% maleic anhydride; MFR at 190°C, 2.16 kg: 0.6 g / 10 min; MFR at 230°C, 2.16 kg: 1.2 g / 10 min; T g -65℃; density 866kg / m 3 ; Shore A hardness 55 (Mitsui). Impact Modifier-3 Acid-modified ethylene-butylene polyolefin, 1.0 wt.% maleic anhydride; MFR at 190°C, 2.16 kg: 3.6 g / 10 min; MFR at 230°C, 2.16 kg: 7.4 g / 10 min; T g -48℃; density 882kg / m 3 (Manufactured by DOW). Impact modifier-4 Ethylene 1-octylene olefin; MFR at 190°C, 2.16 kg: 1.1 g / 10 min; T g -50℃; density 885kg / m 3 (Manufactured by Borealis). Impact Modifier-5 Acid-modified ethylene-butylene polyolefin: 0.5 wt.% maleic anhydride; MFR at 190°C, 2.16 kg: 40 g / 10 min; MFR at 230°C, 2.16 kg: 70 g / 10 min; density 872 kg / m 3 ;Shore A hardness 72 (manufactured by Mitsui). Impact Modifier-6 Acid-modified ethylene-butylene polyolefin: 0.75 wt.% maleic anhydride; MFR at 190°C, 2.16 kg: 11 g / 10 min; MFR at 230°C, 2.16 kg: 23 g / 10 min; T g -65℃; density 896kg / m 3 ; Shore A hardness 89 (Mitsui). Lubricant: Calcium salt of a long-chain, saturated, straight-chain carboxylic acid (montanic acid) (Clariant). Talcum Fine talcum (Mineral Group). Stabilizer-1: Irganox 1098 (N,N'-(hexane-1,6-diyl)bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanamide], primary antioxidant) (BASF) 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 (manufactured by BASF). Stabilizer-3 CuI / KBr (3% copper by weight) (PolyAdd Services). Aromatic PA Zytel HTN301, Tm=230~280℃, density 1190kg / m 3 (Manufactured by DuPont). Glass fiber E6CR10-4,5-568H, filament diameter 9-11 micrometers, cut length 3.50-5.50 micrometers (manufactured by Jushi). Black colorant N54-1033, 40% Solvent Black 7 (Nigrosine) in PA6, density 1.19 g / cm 3 (Manufactured by Colloids).

[0100] Processing combination Molding compositions were produced in a ZSK25 twin-screw extruder with a flat temperature profile of 250-260°C and pelletized. The ingredients (see Table 1) were premixed and fed through the feed throat. Unless otherwise specified, all compositions were prepared with an additive package consisting of 8.5 wt.% lubricant, 1.5 wt.% talcum, 20 wt.% Irganox 1098, 10 wt.% Chimassorb 944, and 10 wt.% CuI / KBr, where the weight percentages (wt.%) are based on the total weight of the additive package, all premixed in a masterbatch with 50 wt.% polyamide-1.

[0101] The comparative examples and compositions according to the present invention listed in Tables 5-6 were prepared as specified above, with the addition of fine talcum and IM-4 to the amounts specified in Tables 5-6.

[0102] molding Prior to molding, all materials were dried in a vacuum oven purged with N2 at 120°C for 16 hours. For the preparation of test samples, injection molding was carried out on a Fanuc-2 injection molding machine, model α-S50iA, equipped with an appropriate mold cavity, applying a barrel temperature of 260°C and a mold cavity temperature of 90°C.

[0103] Test Method Relative Viscosity The relative viscosity of the polyamide polymer and the mixture thereof was measured in sulfuric acid at a concentration of 1 g in 100 g of m-cresol at 25°C according to a method in accordance with ISO 307.

[0104] Flow Resistance Flow resistance was measured as kinematic viscosity using dynamic mechanical spectroscopy (DMS) according to ISO 6721-10, with a loading time of t = 5 min, angular frequencies of 100 to 0.1 rad / s, and three measurement points per logarithmic scale. From these measurements, the complex viscosity (Eta) at 0.1 rad / s was calculated. * ) is reported.

[0105] Tensile Properties DAM The elongation at break was measured in a tensile test on type 1A test specimens at -40°C and a pulling rate of 50 mm / min according to a method according to ISO 527-2:2012.

[0106] Notched impact resistant Notched impact strength was measured at 23°C according to ISO 179-2:2020.

[0107] Drop weight impact resistance Drop weight impact resistance was measured on 80 x 80 x 2 mm injection molded plaques at -40°C according to a method in accordance with ISO 6603-2-2000-10. The number of brittle fractures out of five tests is reported.

[0108] Composition and Test Results Compositions according to the invention (Examples, EX) and Comparative Experiments (CE) and the test results obtained using these Examples and Comparative Experiments are reported in Tables 1, 2, 3, 4, 5, and 6. The weight percentages are based on the total weight of the impact-modified polyamide composition.

[0109] [Table 1]

[0110] The results in Table 1 show that the mechanical properties of polyamides without impact modifier (CE-1) can be improved by adding impact modifier, but at the expense of increased flow resistance (see CE-2, which contains an acid-modified polyolefin impact modifier; and CE-4, which contains a combination of acid-modified polyolefin impact modifier and unmodified polyolefin). Flow can be improved by using polyamides with lower viscosities; however, mechanical properties are barely increased or even decreased. Impact resistance, in particular, decreases significantly with further reductions in the relative viscosity of the polyamide (see CE-3, which contains an acid-modified polyolefin impact modifier; and CE-4 and CE-5, which contain the same combination of acid-modified polyolefin impact modifier and 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 CE-4 and CE-6 (containing the same combination of acid-modified polyolefin impact modifier and unmodified polyolefin) on the other hand are limited, with one being slightly better in some properties and worse in others. Furthermore, all of these comparative experiments failed the drop weight impact test.

[0111] By further increasing the amount of acid-modified polyolefin impact modifier in combination with unmodified polyolefin, impact resistance becomes better, but not to a sufficient extent, at the expense of a significant decrease in flowability. This is exemplified by CE-8 compared to CE-7 and CE-5. When the polyamide of CE-8 is replaced with a polyamide having a lower viscosity, not only is flowability improved, but impact resistance also improves, which is quite surprising and contrary to common knowledge and the results observed above for CE-3 compared to CE-2, while the values ​​for elongation at break are also acceptable to good. However, this composition also fails the impact test using a drop weight.

[0112] Table 2 shows the compositions and results of Comparative Experiments 10-12 and Examples A-D containing a modified polyolefin impact modifier according to the present invention. The compositions of Comparative Experiments CE-10-12 contain a modified polyolefin impact modifier in an amount of 20% by weight, based on the total weight of the composition. While the impact resistance is acceptable for CE-10, the flow resistance is too high. The flow resistance can be reduced by using a polyamide with a lower relative viscosity (RV), as exemplified by CE-11 and CE-12. However, further reductions in the relative viscosity (RV), particularly from 2.31 for CE-11 to 2.09 for CE-12, significantly reduce the impact resistance. However, these compositions also fail the drop weight impact test, as shown for CE-11.

[0113] [Table 2]

[0114] Contrary to the above results for CE-10-12, the compositions of Examples A-D according to the present invention show good or improved results for all properties, including good values ​​for falling weight resistance. More specifically, Example A contains a higher amount of modified polyolefin impact modifier compared to CE-11, which results in not only improved impact resistance and good values ​​for elongation at break, but also retention of flowability and, more surprisingly, acceptable results for the falling weight impact test.

[0115] The difference in effectiveness due to 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 blend of polyamides. CE-7 contained 20% by weight of the impact modifier combination and had an impact strength of 48.0 kJ / m 2 In CE-8, the amount of impact modifier combination was increased by 30% by mass, which resulted in a Charpy impact resistance of 55.4 kJ / m 2CE-11 contains 20 wt. % modified polyolefin impact modifier consistent with the present invention, resulting in a moderate increase to 56.15 kJ / m 2 In Example A (EX-A), the amount of modified polyolefin impact modifier was increased to 25% by mass, which resulted in a Charpy impact resistance of 86.7 kJ / m 2 In Example B (EX-B), the amount of modified polyolefin impact modifier was further increased to 30 wt %, which resulted in a significant increase in Charpy impact resistance to 96.0 kJ / m 2 Further increases in the amount of modified polyolefin impact modifier, as in Example B, result in further improvements in the resulting impact resistance and elongation at break, as well as maintaining acceptable levels of flowability and good results in the drop weight impact test. Lowering the relative viscosity (RV) for compositions with 30 wt.% modified polyolefin impact modifier, as done in Example C (EX-C), not only improves flow resistance compared to Example B, but even further improves elongation at break while maintaining high levels of impact resistance, contrary to the opposite results for CE-11 and CE-12, and also results in good results in the drop weight impact test, in stark contrast to the results for CE-9 discussed above. As shown in Example D (EX-D), the amount of impact modifier can be further increased while still maintaining acceptable levels of flowability and maintaining very good mechanical properties.

[0116] Table 3 shows the compositions and test results for Examples E-F and Comparative Experiments 13-14, with the only difference being the modified impact modifier. Although Examples E-F contain a modified impact modifier according to the present invention, different from that used in Examples A-D, both have a melt flow rate (MFR) of up to 15 g / 10 min, measured at 230°C and a test load of 2.16 kg according to a method in accordance with ISO 1133:2011. As the results show, both Example E (EX-E) and Example F (EX-F) exhibit good mechanical properties, including good drop weight resistance at low temperatures combined with good flowability.

[0117] [Table 3]

[0118] Comparative Experiments 13-14 (CE-13 and CE14) contain different modified impact modifiers, neither of which is in accordance with the present invention, and have a melt flow rate (MFR) of up to 15 g / 10 min measured at 230°C and a test load of 2.16 kg according to a method in accordance with ISO 1133:2011. As the results show, both comparative experiments exhibit good flow properties but fail in mechanical properties, especially in drop weight resistance at low temperatures.

[0119] Table 4 shows various examples (Examples G-M) using different compositions according to the invention. Examples G-K demonstrate that the additive package can be varied widely with little effect on mechanical properties while maintaining good flow. Examples L-N demonstrate that polymers other than modified polyolefin impact modifiers can be added while maintaining acceptable flow and good mechanical properties, provided that the amount of modified polyolefin impact modifier (Y) in the composition is at least 22.5 pbw per 100 pbw of the total amount of modified polyolefin impact modifier (MIM) (Y) and aliphatic polyamide (APA) (X). This contrasts with compositions in which the amount of modified impact modifier is less than the minimum amount according to the invention, even if the total amount of impact modifier is held constant. In this regard, a comparison of Example M (EX-M) with Comparative Experiments 8 and 9 (CE-8 and CE-9) demonstrates relevant results. All three compositions have the same total amount of impact modifier (30 wt%), but CE-8 and CE-9 (compositions and results shown in Table 1) contain less modified polyolefin impact modifier (MIM) and more unmodified polyolefin impact modifier compared to EX-M. While composition EX-M according to the invention exhibits acceptable flowability and good mechanical properties, comparative experiments CE-8 and CE-9 fail in flowability or drop weight resistance at low temperature.

[0120] [Table 4]

[0121] Table 5 shows examples (Examples O-P) using different compositions according to the present invention. Examples O-P show that compositions with fine talcum contents of 0.5 and 1.85 wt. % (relative to the total weight of the composition) achieve beneficial properties. Comparative Examples 15-19 show that the incorporation of excessive other component Z adversely affects one or more of flow properties, tensile properties, notched impact resistance, and drop weight resistance, as specifically exemplified for compositions with more than 30 pbw glass fiber (CE-15), more than 30 pbw aromatic polyamide (CE-16), more than 30 pbw aromatic PA+GF (CE-17), and more than 2 pbw fine talcum (CE-18 and CE-19), respectively.

[0122] It should be noted that no such adverse effects were observed for samples according to the invention, i.e., samples having each of these constituents within the claimed ranges, but without an excess of the other (component Z). In terms of impact resistance, the results confirm good performance for samples having up to 1 pbw fine talcum, acceptable impact ratings for samples having up to 2 pbw fine talcum, and relatively poor performance for samples having higher fine talcum contents.

[0123] [Table 5]

[0124] Table 6 shows the results for Examples (EX-Q, EX-R) using different compositions according to the present invention, as well as Comparative Examples CE-20 and CE-21. The addition of more than 10 pbw of unmodified IM (IM-4) adversely affected roto-moldability, particularly in terms of relatively poor flow, which is believed to be caused by phase inversion to a system with a discontinuous polyamide phase within an olefin matrix. In contrast, Examples L, M, Q, and R, which do not contain excessive amounts of unmodified impact modifier, exhibit good performance in flow, tensile properties, and drop weight resistance, along with at least acceptable performance in terms of impact resistance. The difference in flow and impact performance ratings between EX-R and EX-Q is believed to be related to the difference in maleic anhydride content.

[0125] [Table 6]

Claims

1. - X parts by weight (pbw) of an aliphatic polyamide (APA), - Y parts by weight (pbw) of a modified polyolefin impact modifier (MIM); - 0 to 30 parts by mass (pbw) of one or more other polymeric components and / or one or more additives (together referred to as other component Z), per 100 pbw of the sum of X and Y; An impact modified polyamide composition comprising: - the aliphatic polyamide (APA) has a relative viscosity (RV) of up to 2.40, measured in 96% sulfuric acid at 0.01 g / ml and 25°C according to a method in accordance with ISO 307:2019; - the modified polyolefin impact modifier (MIM) has a melt flow rate (MFR) of up to 15 g / 10 min, measured at 230 °C and a test load of 2.16 kg according to a method in accordance with ISO 1133:2011; - the sum of X and Y is 100pbw, - X is at most 77.5 pbw and Y is at least 22.5 pbw; - X is at least 60 pbw and Y is at most 40 pbw when the aliphatic polyamide (APA) has a relative viscosity (RV) of 2.20 or less; - X is at least 65 pbw and Y is at most 35 pbw when the relative viscosity (RV) of the aliphatic polyamide (APA) is in the range of more than 2.20 to 2.33 or less; - X is at least 70 pbw and Y is at most 30 pbw when the relative viscosity (RV) of the aliphatic polyamide (APA) is in the range of more than 2.33 and less than or equal to 2.40; Other component Z comprises 0-10 pbw of unmodified polyolefin and 0-2 pbw of fine talcum per 100 pbw of the total weight of X and Y; Impact modified polyamide compositions.

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

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

31.

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

6. 6. The impact modified polyamide composition of 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. Modified polyolefin impact modifier (MIM) a glass transition temperature (Tg) of at most -50°C, preferably at most -55°C, measured according to a method in accordance with ISO 11357-2:2020, and / or - Density up to 0.95 g / cm, measured according to ASTM D1505-03 3 , preferably up to 0.90 g / cm 3 , more preferably up to 0.85 g / cm 3 and / or Shore A hardness of up to 90, preferably up to 80, more preferably up to 75, measured according to the method in accordance with ASTM D2240-15 7. The impact modified polyamide composition of claim 1, wherein

8. - When the relative viscosity (RV) of the aliphatic polyamide (APA) is 2.20 or less, X is in the range of 62.5 to 75 pbw and Y is in the range of 25 to 37.5 pbw; - When the relative viscosity (RV) of the aliphatic polyamide (APA) is greater than 2.20 but less than or equal to 2.27, X is in the range of 65 to 75 pbw and Y is in the range of 25 to 35 pbw; - X is at least 69 and Y is at most 31 pbw when the relative viscosity (RV) of the aliphatic polyamide (APA) is in the range of more than 2.27 but not more than 2.33; - X is at least 72.5 pbw and Y is at most 27.5 pbw when the relative viscosity (RV) of the aliphatic polyamide (APA) is in the range of more than 2.33 but not more than 2.40; 8. An impact-modified polyamide composition according to any one of claims 1 to 7.

9. - Complex viscosity at 250°C (Eta * ):Maximum 700Pa・s; - Elongation at break at -40°C: at least 17.5%; - Notched impact strength at 23°C: at least 70KJ / m 2 and - Drop weight impact resistance at -40℃: at least 60% success rate; and - Complex viscosity (Eta * ) was measured by dynamic mechanical spectroscopy (DMS) according to ISO 6721-10 at a loading time of t = 5 min and an angular frequency of 0.1 rad / s. - the elongation at break is measured according to ISO 527-2:2012 Type 1A at a pulling rate of 50 mm / min; - Notched impact strength measured according to ISO 179-2:2020 - Drop weight impact resistance measured on injection-molded plaques of 80 x 80 x 2 mm according to the method in accordance with ISO 6603-2-2000-10, 9. An impact-modified polyamide composition according to any one of claims 1 to 8.

10. 10. The impact-modified polyamide composition of claim 1, comprising 0.001 to 1 pbw of fine talcum per 100 pbw of the total amount of X and Y.

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

12. 1. A method for making an impact modified polyamide composition, comprising: - X parts by weight of an aliphatic polyamide (APA), - Y parts by weight of a modified polyolefin impact modifier (MIM); - 0 to 30 parts by mass (pbw) of one or more other polymeric components and / or one or more additives (together referred to as other component Z), per 100 pbw of the sum of X and Y; melt-mixing the 12. The method of claim 1, wherein APA and MIM, and X, Y and Z are as defined in any one of claims 1 to 11.

13. 1. A method for making an impact modified article, comprising: - X parts by weight of an aliphatic polyamide (APA), - Y parts by weight of a modified polyolefin impact modifier (MIM); - 0 to 30 parts by mass (pbw) of one or more other polymeric components and / or one or more additives (together referred to as other component Z), per 100 pbw of the sum of X and Y; melt processing a polyamide composition comprising 12. An impact-modified polyamide composition and an APA and an MIM, and X, Y and Z are as defined in any one of claims 1 to 11. method.

14. 14. The method of claim 13, wherein the melt processing is performed by rotational molding.

15. 1. A rotomolded article made from an impact modified polyamide composition, comprising: - X parts by weight of an aliphatic polyamide (APA), - Y parts by weight of a modified polyolefin impact modifier (IM); - 0 to 30 parts by mass (pbw) of one or more other polymeric components and / or one or more additives (together referred to as other component Z), per 100 pbw of the sum of X and Y; Including, The polyamide composition and the APA and the MIM, and X, Y and Z are as defined in any one of claims 1 to 11, Rotational molding.

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