Aliphatic and semiaromatic polyamides with dimer acids and dimeramines

Abstract

The present invention discloses a polyamide composition comprising 45 wt % to 95 wt % of a polyamide polymer and 5 wt % to 55 wt % of a modifier, wherein the modifier comprises C 18‑44 Dimer acid or C 18‑44 A diamine or a combination thereof. The number average molecular weight of the polyamide polymer is less than 30,000 g / mol. The polyamide composition exhibits chemical resistance as measured by exposure to HCl (10%) at 58° C. for 14 days resulting in a weight loss of less than 3.0 wt %; and a moisture absorption of less than about 2.0 wt % water at 95% RH. A method of preparing the polyamide composition is also disclosed.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Application No. 63 / 065,281, filed on August 13, 2020, which is incorporated herein by reference.

[0003] field

[0004] The present application generally relates to polyamide compositions having improved chemical resistance and reduced moisture absorption while maintaining mechanical properties and temperature resistance.

[0005] background

[0006] Many natural and artificial polyamides are used in various applications due to their high durability and strength. Some polyamide compositions can be formulated to have high melting points, high recrystallization temperatures, fast injection molding cycle times, high fluidity, toughness, elasticity, chemical resistance, inherent flame retardancy and / or abrasion resistance. These desired chemical and mechanical properties can make polyamide compositions suitable for the production of a variety of products, such as tubing, cable connectors, sports equipment and sportswear, gun stocks, window insulation bridges, aerosol valves, automotive / vehicle parts, textiles, industrial fibers, carpets, and electrical / electronic components.

[0007] As an example, in the automotive industry, the environmental requirements are to reduce emissions and improve the efficiency of fuel consumption. A way to achieve these goals is to reduce the weight of the entire vehicle by replacing metal components with thermoplastic components. Usually, polyamide compositions are used to provide this weight loss in the engine compartment. It is also found that some polyamide compositions are particularly suitable for automotive applications because they have the above-mentioned temperature resistance, mechanical strength and overall appearance. Exemplary applications can include pipes or jackets used in oil and gas or chemical applications, aerospace applications, wire and cable applications, back panels for the solar industry, various consumer product applications and automotive applications. These applications also include powder coatings for dishwasher racks and shopping carts, flexible pipes or hoses for oil and gas applications, electrical connectors, and solar back panel sheers, which require excellent hydrolysis resistance. Applications such as radiator sump or chassis components can also require chemical resistance, such as resistance to CaCl2.

[0008] U.S. Patent Application Publication No. US 2019 / 0194392 discloses a polymer film comprising at least one copolyamide. The copolyamide is obtained by polymerizing at least one C4-C 12 dicarboxylic acid and at least one C4-C 12 The first monomer mixture (M1) of diamine and at least one C 32 -C 40 dimer acid and at least one C4-C 12The invention relates to a method for preparing a polymer film and a copolyamide for polymer films for high temperature applications, such as packaging films, which exhibit high tear resistance and ductility. The copolyamide is prepared by polymerizing two separate monomer mixtures, wherein the resulting film has a melting temperature in the range of 220°C to 290°C.

[0009] Conventional polyamide compositions for films (see above) inherently lack properties for non-film applications, which typically require a high degree of chemical resistance and reduced moisture absorption, such as minimizing dimensional changes, and requiring mechanical strength. Therefore, even in view of the prior art, there is still a need for improved polyamide compositions that can effectively provide both mechanical strength and temperature resistance, as well as chemical resistance and reduced moisture absorption suitable for non-film applications.

[0010] Overview

[0011] In one embodiment, the present invention relates to a polyamide composition comprising 45% to 95% by weight of a polyamide polymer and 5% to 55% by weight of a modifier. The modifier includes dimer acid or dimeramine or a combination thereof. The polyamide composition may show a chemical resistance detected by exposure to HCl (10%) for 14 days at 58°C such that the weight loss is less than 3.0% by weight, and / or the moisture absorption rate at 95%RH is less than about 2.0% by weight of moisture. In certain embodiments, the polyamide composition has a methyl / amide ratio in the range of 6:1 to 15:1. In certain embodiments, the polyamide composition has a methyl / amide ratio in the range of 9:1 to 15:1. In certain embodiments, the polyamide composition includes 20% to 45% by weight of a modifier, the modifier including dimer acid or dimeramine or a combination thereof. In some cases, the polyamide composition may show a moisture absorption rate at 95%RH of less than about 1.6% by weight of moisture. In certain embodiments, the polyamide polymer includes PA10, PA11, PA12, PA6,6, PA6,9, PA6,10, PA6,11, PA6,12, PA6,13, PA6,14, PA6,15, PA6,16, PA6,17, PA6,18, PA10,10, PA10,12, PA12,12, PA9T, PA10T, PA11T, PA12T, PA6T / 66, PA6T / 6I, PA6T / 6I / 66, PA6T / DT, PA6,T / 6,10, PA6,T / 6,12, PA6,T / 6,13, PA6,T / 6,14, PA6,T / 6,15, PA6,T / 6,16, PA6,T / 6,17, PA6,T / 6,18, PA6,C / 6,10, PA6,C / 6,12, PA6,C / 6,13, PA6,C / 6,14, PA6,C / 6,15, PA6,C / 6,16, PA6,C / 6,17, PA6,C / 6,18, or a combination thereof. In certain embodiments, the polyamide polymer comprises PA6,6. In certain embodiments, the polyamide polymer comprises PA6,10. In certain embodiments, the polyamide polymer comprises PA6,12. In certain embodiments, the polyamide polymer comprises PA6T / 66, PA6T / 6I, PA6T / 6I / 66, PA6T / DT, PA6,T / 6,10, PA6,T / 6,12, PA6,T / 6,13, PA6,T / 6,14, PA6,T / 6,15, PA6,T / 6,16, PA6,T / 6,17, PA6,T / 6,18, or a combination thereof. In certain embodiments, the number average molecular weight of the polyamide polymer is in the range of 9,000 g / mol to 60,000 g / mol.In certain embodiments, the number average molecular weight of the polyamide polymer is in the range of 20,000g / mol to 45,000g / mol. In certain embodiments, the number average molecular weight of the polyamide polymer is in the range of 12,000g / mol to 20,000g / mol. In certain embodiments, the polyamide polymer has an amine end group content in the range of 10 micro equivalents / gram to 110 micro equivalents / gram. In certain embodiments, the polyamide polymer has an amine end group content in the range of 35 micro equivalents / gram to 80 micro equivalents / gram. In certain embodiments, the polyamide composition also includes up to 60% by weight of glass fiber. In certain embodiments, the polyamide composition also includes up to 2% by weight of lubricant. In certain embodiments, the polyamide composition also includes an additive selected from nigrosine dye, copper-containing compound, plasticizer or flame retardant or a combination thereof. In certain embodiments, the polyamide composition also includes up to 30% by weight of a mineral additive selected from calcium carbonate, talc, magnesium hydroxide, kaolin clay or a combination thereof. In certain embodiments, the polyamide composition further comprises an impact modifier selected from a modified olefin, an unmodified olefin, an olefin modified with maleic anhydride, an olefin not modified with maleic anhydride, an acrylate, or an acryl compound, or a combination thereof. In some embodiments, the polyamide polymer comprises PA6,12, the dimer modifier is a dimeramine present in an amount of 15 wt % to 50 wt %, and wherein the polyamide composition exhibits a tensile elongation of at least 50%. In some embodiments, the polyamide composition comprises a polyamide polymer PA6,12, the dimer modifier is a dimer acid present in an amount of 15 wt % to 50 wt %, and wherein the polyamide composition exhibits a tensile elongation of at least 20%. In some embodiments, the polyamide composition comprises a polyamide polymer PA6,12, the dimer modifier is a dimeramine present in an amount of 35 wt % to 55 wt %, and wherein the polyamide composition exhibits a notched Charpy impact energy consumption at 23°C of greater than 4.5 kJ / m. 2 In some embodiments, the polyamide composition comprises a polyamide polymer PA6,12, an amount of a dimer modifier of about 20 wt%, and wherein the polyamide composition exhibits a notched Charpy impact energy consumption at 23°C of greater than 3.5 kJ / m 2 , a tensile strength greater than 50 MPa, and a tensile modulus greater than 1950 MPa. In certain embodiments, the polyamide polymer includes a polyamide composition that exhibits a tensile elongation greater than 30%. In certain embodiments, the polyamide composition exhibits a notched Charpy impact energy consumption at 23°C of greater than 3 kJ / m 2In certain embodiments, the tensile modulus of the polyamide composition is greater than 650 MPa. In certain embodiments, the tensile elongation of the polyamide composition is greater than 13%. In certain embodiments, the wear resistance of the polyamide composition is greater than the wear resistance of the reference PA6,12 material or the reference PA12 material.

[0012] In another embodiment, the present invention relates to an injection molded article. The article comprises any one of the polyamide compositions described herein.

[0013] In yet another embodiment, the present invention relates to an article. The article comprises any one of the polyamide compositions described herein. The article can be an extruded article, a profile extruded article, a monofilament or a fiber. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 A graph showing the storage modulus as a function of temperature for polyamides according to some embodiments of the invention compared to homopolymers PA6,12 and PA12;

[0016] Figure 2 The glass transition temperature T shown by the Tan δ peak of the polyamide according to some embodiments of the present invention compared with the homopolymers PA6,12 and PA12 is shown. g Plots that vary with temperature;

[0017] Figure 3 A bar graph showing the moisture absorption of polyamides according to some embodiments of the present invention compared to homopolymers PA6,12 and PA12; and

[0018] Figure 4 Graph showing weight loss of polyamides according to some embodiments of the invention compared to homopolymers PA6,12 and PA12.

[0019] Details

[0020] This paper generally relates to polyamide compositions, which can provide favorable improved effects in chemical resistance and reduced moisture absorption when, for example, used in (non-film) extrusion and injection molding applications. For example, it is found that the extruded or molded thermoplastic parts produced by the polyamide compositions show high chemical resistance, which enables these parts to be used in various applications requiring the use of lightweight structural materials, and can replace metals. These molded plastic parts show reduced moisture absorption, so that the material is reduced as much as possible to reduce unwanted dimensional changes over time, and is independent of climate. As described herein, modulus is adjusted via dimer content to make the material have higher flexibility and high-level chemical resistance and low moisture absorption in a collaborative manner, and this ability is unique. These advantages are achieved by polyamide compositions as described herein, and production costs are reduced.

[0021] Conventional polyamide resins and compositions cannot meet these requirements simultaneously. One reason is that conventional modifications to polyamide compositions known in the art to improve chemical resistance or reduce moisture absorption can adversely affect the mechanical properties of materials. In some cases, conventional polyamide formulations intended for structural applications include fillers such as glass fibers, thereby providing additional reinforcement. However, the addition of glass fibers results in a reduction in mechanical properties such as elongation and impact strength required for automobiles and other applications.

[0022] As is well known in the art, polymer formulations developed for film applications are quite different from those developed for non-film applications. As some examples, film formulations ideally exhibit lower crystallinity, lower crystallization rates, and higher molecular weights; with respect to molecular weight, a number average molecular weight (M) greater than 25,000 g / mol or greater than 25,000 g / mol is typically employed in film applications. n ) values. In contrast, these properties are not required for non-film applications, such as the compositions described herein, because molded or extruded compounds typically have an M of 10,000 to 25,000 g / mol. n Values, especially for example for polyamides based on long chain polyamides (e.g. PA6,10, PA6,12, PA11, PA12, etc.). For molded articles, designing higher levels of crystallinity and fast crystallization rates is required for fast cycle times. In addition, film formulations do not consider the use of high levels of lubricants (e.g., greater than 1000 ppm), impact modifiers, plasticizers, colorants, glass as in some embodiments of the compositions described herein. Moreover, adding these components to film formulations will only add additional costs and lead to process complexity, with little or no benefit obtained thereby.

[0023] Additionally, film formulations are typically PA6-based formulations (or PA6,6), which inherently have high moisture absorption values. Therefore, conventional PA6-based formulations do not require modifiers to provide excellent moisture absorption performance. Advantageously, the formulations described herein and parts produced therefrom can achieve excellent chemical and hydrolysis resistance without PA-6.

[0024] As described herein, the use of dimer acids and / or dimeramines in polyamide compositions (e.g., long chain and / or high temperature polyamide compositions) can surprisingly provide materials with both improved chemical resistance and reduced moisture absorption, while still maintaining strength and high temperature performance, and in some aspects, can synergistically improve chemical resistance and / or moisture absorption performance with overall mechanical properties. In particular, the inventors have discovered that specific types, amounts, and ratios of polyamide polymers, dimer modifiers, glass fibers, impact modifiers, melt stabilizers (lubricants), and optional thermal stabilizers can be combined to prepare compositions with surprising chemical resistance and reduced moisture absorption, while maintaining mechanical and impact properties. Without being bound by any theory, it is believed that dimer modifiers, such as dimer acids and dimeramines, together with other components can synergistically meet requirements related to modulus, temperature resistance, impact strength, chemical resistance, and dimensional stability.

[0025] Generally speaking, dimer acids or dimeramines are known to have an adverse effect on tensile strength. However, when the modifiers described herein are used with the components of the polyamide composition described above, an unexpected balance is achieved and little or no loss in tensile properties is observed while surprisingly significantly improving chemical resistance and moisture absorption. In some cases, the formulations described herein may contain a single dimer modifier or a combination of multiple dimer modifiers to achieve the above performance benefits.

[0026] In contrast, conventional formulations, such as film formulations, such as US 2019 / 0194392, require the use of different diamines in each of at least two monomer mixtures and do not have chemical resistance and moisture absorption properties while maintaining strength properties. Again, these properties are not required for film applications, but rather for molded parts, such as automotive parts.

[0027] It should be noted that the importance of component ratios such as those described herein in achieving both favorable chemical resistance and moisture absorption properties has not been previously discovered. Additionally, an inverse linear relationship between moisture absorption and methyl / amide ratio has not been discovered. The methyl / amide ratio also increases proportionally with respect to tensile elongation, abrasion resistance, and Charpy impact properties. Another advantage, particularly for applications requiring light weight, is that density decreases as the methyl / amide ratio increases.

[0028] In one aspect, polyamide compositions are disclosed herein. The composition comprises a polyamide polymer and a modifier, which may comprise a dimer acid or a dimeramine or a combination thereof. As described in detail below, in some cases, the composition preferably comprises 45% to 95% by weight of a polyamide polymer and 5% to 55% by weight of a modifier. By using these components in a polymer composition (optionally in the concentrations and ratios described herein), a polyamide composition having improved chemical resistance and moisture absorption properties is obtained, for example, the polyamide composition shows improved chemical resistance to acids, bases, and various chemicals, and / or a moisture absorption rate of less than about 2.0% by weight of moisture at 95% relative humidity (RH). The polyamide compositions described herein also show favorable mechanical properties, including high tensile elongation, high impact strength as measured by notched Charpy impact energy consumption at 23°C, high tensile modulus, and high wear resistance.

[0029] The components of the polyamide composition are discussed below separately. It should be understood that these components can be used in combination with each other to form the above-mentioned polyamide composition.

[0030] Polyamide polymer

[0031] The polyamide in the composition described herein can vary widely and can include one polyamide polymer or two or more polyamide polymers. Exemplary polyamides and polyamide compositions can be found in Kirk-Othmer, Encyclopedia of Chemical Technology, Vol. 18, pp. 328-371 (Wiley 1982), the disclosure of which is incorporated herein by reference. In short, polyamides are products containing repeating amide groups as part of the entire polymer backbone. Linear polyamides are of particular interest and can be obtained by condensation reactions of difunctional monomers known in the art. Polyamides are commonly referred to as nylons. Specific polyamide polymers and copolymers and methods for preparing the same can be found, for example, in U.S. Patent Nos. 2,071,250; 2,071,251; 2,130,523; 2,130,948; 2,241,322; 2,312,966; 2,512,606; 3,236,914; 3,472,916; 3,373,223; 3,393,210; 3,984,497; 3,546,319; 4,031,1 64; 4,320,213; 4,346,200; 4,713,415; 4,760,129; 4,981,906; 5,504,185; 5,543,495; 5,698,658; 6,011,134; 6,136,947; 6,169,162; 6,197,855; 7,138,482; 7,381,788; and 8,759,475, the entire contents of each of which are incorporated herein by reference.

[0032] The polyamides described herein include aliphatic polyamides, semiaromatic polyamides, polyphthalamides, and combinations thereof. The polyamide composition may include one or more polyamides, such as PA10, PA11, PA12, PA6,6, PA6,9, PA6,10, PA6,11, PA6,12, PA6,13, PA6,14, PA6,15, PA6,16, PA6,17, PA6,18, PA10,10, PA10,12, PA12,12, PA9T, PA10T, PA11T, PA12T, PA6T / 66, PA6T / 6I, PA6T / 6I / 66, PA 6,17, or PA6,C / 6,18, or a combination thereof. In some embodiments, the polyamides described herein are free of or substantially free of PA6 and / or PA6,6, such as less than 5 wt% PA-6, such as less than 3 wt%, less than 1 wt%, less than 0.5 wt%, less than 0.1 wt%, or completely free of PA-6.

[0033] In some cases, the one or more polyamide polymers in the composition include aliphatic systems such as PA6,6, PA6,10 and PA6,12, which are known for their strength and temperature resistance. The one or more polyamide polymers in the composition may include aliphatic polyamides such as polyhexamethylene adipamide (PA6,6), polyhexamethylene sebacamide (PA6,10), polyhexamethylene dodecanamide (PA6,12), or other aliphatic nylons; polyamides with aromatic components such as p-phenylenediamine and terephthalic acid, and copolymers such as adipates with 2-methylpentamethylenediamine and 3,5-dicarboxybenzenesulfonic acid or sulfoisophthalic acid, which are in the form of sodium sulfonate salts. Polyamides may include polyaminoundecanoic acid, and polymers of di(p-aminocyclohexyl)methane and undecanoic acid. Other polyamides include poly(aminododecaneamide), polyhexamethylene sebacamide, poly(nonamethylene terephthalamide), poly(hexamethylene isophthalamide), and polyamides formed from di(p-aminocyclohexyl)methane and azelaic acid, sebacic acid and homologous aliphatic dicarboxylic acids. The terms "PA6,12 polymer" and "PA6,12 polyamide polymer" used herein also include copolymers in which PA6,12 is the main component. The terms "PA6,6 polymer" and "PA6,6 polyamide polymer" used herein also include copolymers in which PA6,6 is the main component. In some embodiments, copolymers such as PA-6,6 / 6I, PA-6I / 6T, or PA-6,6 / 6T or combinations thereof are contemplated as polyamide polymers. In some cases, physical blends of these polymers, such as melt blends, are contemplated. In one embodiment, the polyamide polymer comprises PA6,12, or PA12 or a combination thereof.

[0034] As mentioned above, long-chain polyamides are generally considered. In some cases, PA6,10, PA6,12, PA10 and / or PA12 show specific synergistic results with the above-mentioned dimer modifiers. Many literatures on film formulations often mention a wide range of polyamides, but these long-chain polyamides are not devoted to research. Conventional formulations also do not consider the synergistic benefits brought by long-chain polyamides as found and demonstrated herein.

[0035] In some embodiments, the polyamide composition comprises a polyamide prepared from ring-opening polymerization or polycondensation, including copolymerization and / or co-polycondensation of lactams. These polyamides can include, for example, those prepared from propiolactam, butyrolactam, valerolactam and caprolactam. For example, in some embodiments, the composition comprises a polyamide polymer derived from the polymerization reaction of caprolactam. In some embodiments, the polyamide composition can include laurolactam or PA12. In some cases, these lactam components can be optional.

[0036] In some cases, the compositions described herein may explicitly exclude one or more of the above-mentioned additives, such as by way of statement in the claims. For example, the statement in the claims may be modified to define the compositions, methods, etc. described as not using or not including one or more of the above-mentioned lactams. This applies to many of the additives and / or components described herein.

[0037] In some cases, the polyamide composition comprises a semi-aromatic polyamide, which is known for high strength, high temperature resistance, resistance to long-term thermal exposure and dielectric strength. The polyamide composition may comprise polyphthalamides, such as PA6T / 66, PA6T / 6I and PA6T / DT. Polyphthalamides are defined as semi-aromatic polyamides in which the residues of terephthalic acid and / or isophthalic acid constitute at least 55 mole % of the repeating units according to ASTM D5336 classification. For example, the polyamide may comprise a polyphthalamide selected from the group consisting of PA-4T / 4I; PA-4T / 6I; PA-5T / 5I; PA-6; PA-6,6; PA-6,6 / 6; PA-6,6 / 6T; PA-6T / 6I; PA-6T / 6I / 6; PA-6T / 6; PA-6T / 6I / 66; PA-6T / MPDMT (wherein MPDMT is a polyphthalamide based on a mixture of hexamethylenediamine and 2-methylpentamethylenediamine as diamine components and terephthalic acid as diacid component). Amide); PA-6T / 66; PA-6T / 610; PA-10T / 612; PA-10T / 106; PA-6T / 612; PA-6T / 10T; PA-6T / 10I; PA-9T; PA-10T; PA-12 T; PA-10T / 10I; PA-10T / 12; PA-10T / 11; PA-6T / 9T; PA-6T / 12T; PA-6T / 10T / 6I; PA-6T / 6I / 6; PA-6T / 61 / 12; and their combinations.

[0038] The concentration of one or more polyamide polymers in the whole polyamide composition can be, for example, in the range of 45 wt % to 95 wt %, for example, 45 wt % to 55 wt %, 50 wt % to 60 wt %, 55 wt % to 65 wt %, 60 wt % to 70 wt %, 65 wt % to 75 wt %, 70 wt % to 80 wt %, 75 wt % to 85 wt %, 80 wt % to 90 wt %, 85 wt % to 95 wt %, or any sub-range thereof. In some embodiments, the concentration of one or more polyamide polymers is in the range of 50 wt % to 85 wt %. In some aspects, the concentration of one or more polyamide polymers is in the range of 45 wt % to 65 wt %. With regard to the upper limit, the polyamide polymer concentration of the combination can be less than 95 wt %, for example, less than 90 wt %, less than 85 wt %, less than 80 wt %, less than 75 wt %, less than 70 wt %, less than 65 wt %, less than 60 wt %, less than 55 wt %, or less than 50 wt %. In terms of lower limits, the combined polyamide polymer concentration can be greater than 45 wt%, such as greater than 50 wt%, greater than 55 wt%, greater than 60 wt%, greater than 65 wt%, greater than 70 wt%, greater than 75 wt%, greater than 80 wt%, greater than 85 wt%, or greater than 90 wt%. Lower concentrations, such as less than 45 wt%, and higher concentrations, such as greater than 95 wt%, are also contemplated. These ranges and limits may also apply to individual polyamides.

[0039] As used herein, the expressions "greater than" and "greater than" limits may also include the numerical values ​​used therewith. In other words, "greater than" and "greater than" may be interpreted as "greater than or equal to" and "less than or equal to". It is contemplated that such expressions may be subsequently amended in a claim to include "or equal to". For example, "greater than 4.0" may be interpreted as "greater than or equal to 4.0" and subsequently amended in a claim to "greater than or equal to 4.0".

[0040] In some cases, the ranges and limits stated for one or more polyamide polymers apply to PA6,6. In some cases, the ranges and limits stated for one or more polyamide polymers apply to PA6,10. In some cases, the ranges and limits stated for one or more polyamide polymers apply to PA6,12. In some cases, the ranges and limits stated for one or more polyamide polymers apply to PA6T / 66, PA6T / 6I, PA6T / 6I / 66, PA6T / DT, PA6,T / 6,10, PA6,T / 6,12, PA6,T / 6,13, PA6,T / 6,14, PA6,T / 6,15, PA6,T / 6,16, PA6,T / 6,17, or PA6,T / 6,18, or a combination thereof.

[0041] In certain aspects, the one or more polyamide polymers include PA6,6 polymers. PA6,6 has high strength, as well as stiffness at high temperatures and excellent impact strength even at low temperatures, which makes it very advantageous for use in various applications seeking a balance of properties including strength, temperature resistance, toughness, and chemical resistance. In addition, PA6,6 polymers have both high crystallinity and a fast crystallization rate, so that polyamide polymers comprising PA6,6 can be suitably used in injection molding processes. The concentration of PA6,6 polymer in the one or more polyamide polymers can be, for example, in the range of 0 wt % to 100 wt %, such as 0 wt % to 60 wt %, 10 wt % to 70 wt %, 20 wt % to 80 wt %, 30 wt % to 90 wt %, 25 wt % to 100 wt %, or 40 wt % to 100 wt %. In terms of upper limits, the concentration of PA6,6 polymer in one or more polyamide polymers may be less than 100 wt%, such as less than 90 wt%, less than 80 wt%, less than 70 wt%, less than 60 wt%, less than 50 wt%, less than 40 wt%, less than 30 wt%, less than 20 wt%, or less than 10 wt%. In terms of lower limits, the concentration of PA6,6 polymer in one or more polyamide polymers may be greater than 0 wt%, such as greater than 10 wt%, greater than 20 wt%, greater than 30 wt%, greater than 40 wt%, greater than 50 wt%, greater than 60 wt%, greater than 70 wt%, greater than 80 wt%, or greater than 90 wt%. In some embodiments, the polyamides described herein are free of or substantially free of PA6,6, such as less than 5 wt% PA6,6, such as less than 3 wt%, less than 1 wt%, less than 0.5 wt%, less than 0.1 wt%, or completely free of PA6,6.

[0042] In certain aspects, the one or more polyamide polymers include PA6,10 polymers. PA6,10 has lower water absorption than PA6 or PA6,6, and has significantly higher strength than PA11, PA12 or PA6,12, which makes it very advantageous for use in applications seeking a balance of properties including strength, temperature resistance, reduced moisture absorption and chemical resistance. The concentration of PA6,10 polymer in the one or more polyamide polymers can be, for example, in the range of 0 wt % to 100 wt %, such as 0 wt % to 60 wt %, 10 wt % to 70 wt %, 20 wt % to 80 wt %, 30 wt % to 90 wt %, or 40 wt % to 100 wt %. In some embodiments, the one or more polyamide polymers contain 25 wt % to 100 wt % of PA6,10 polymers. In terms of upper limits, the concentration of the PA6,10 polymer in the one or more polyamide polymers may be less than 100 wt%, such as less than 90 wt%, less than 80 wt%, less than 70 wt%, less than 60 wt%, less than 50 wt%, less than 40 wt%, less than 30 wt%, less than 20 wt%, or less than 10 wt%. In terms of lower limits, the concentration of the PA6,10 polymer in the one or more polyamide polymers may be greater than 0 wt%, such as greater than 10 wt%, greater than 20 wt%, greater than 30 wt%, greater than 40 wt%, greater than 50 wt%, greater than 60 wt%, greater than 70 wt%, greater than 80 wt%, or greater than 90 wt%.

[0043] In certain aspects, the one or more polyamide polymers include PA6,12 polymers. The concentration of PA6,12 polymers in the one or more polyamide polymers can be, for example, in the range of 0 wt % to 100 wt %, such as 0 wt % to 60 wt %, 10 wt % to 70 wt %, 20 wt % to 80 wt %, 30 wt % to 90 wt %, or 40 wt % to 100 wt %. In some embodiments, the one or more polyamide polymers contain 0 wt % to 75 wt % of PA6,12 polymers. In terms of upper limits, the concentration of PA6,12 polymers in the one or more polyamide polymers can be less than 100 wt %, such as less than 90 wt %, less than 80 wt %, less than 70 wt %, less than 60 wt %, less than 50 wt %, less than 40 wt %, less than 30 wt %, less than 20 wt %, or less than 10 wt %. In terms of lower limits, the concentration of the PA 6,12 polymer in the one or more polyamide polymers can be greater than 0 wt%, for example greater than 10 wt%, greater than 20 wt%, greater than 30 wt%, greater than 40 wt%, greater than 50 wt%, greater than 60 wt%, greater than 70 wt%, greater than 80 wt%, or greater than 90 wt%.

[0044] In certain aspects, the one or more polyamide polymers include one of PA6T / 66, PA6T / 6I, PA6T / 6I / 66, PA6T / DT, PA6,T / 6,10, PA6,T / 6,12, PA6,T / 6,13, PA6,T / 6,14, PA6,T / 6,15, PA6,T / 6,16, PA6,T / 6,17, PA6,T / 6,18, or a combination thereof, and the content thereof may be, for example, in the range of 0 wt % to 100 wt %, for example, 0 wt % to 60 wt %, 10 wt % to 70 wt %, 20 wt % to 80 wt %, 30 wt % to 90 wt %, or 40 wt % to 100 wt %. In some embodiments, the one or more polyamide polymers include 0 wt % to 75 wt % of one of these polyamide polymers. In terms of upper limits, the concentration of these polyamide polymers can be less than 100 weight percent, for example, less than 90 weight percent, less than 80 weight percent, less than 70 weight percent, less than 60 weight percent, less than 50 weight percent, less than 40 weight percent, less than 30 weight percent, less than 20 weight percent, or less than 10 weight percent. In terms of lower limits, in one or more polyamide polymers, the polymer concentration of one or a combination of PA6T / 66, PA6T / 6I, PA6T / 6I / 66, PA6T / DT, PA6,T / 6,10, PA6,T / 6,12, PA6,T / 6,13, PA6,T / 6,14, PA6,T / 6,15, PA6,T / 6,16, PA6,T / 6,17, PA6,T / 6,18 can be greater than 0 weight percent, for example, greater than 10 weight percent, greater than 20 weight percent, greater than 30 weight percent, greater than 40 weight percent, greater than 50 weight percent, greater than 60 weight percent, greater than 70 weight percent, greater than 80 weight percent, or greater than 90 weight percent.

[0045] The polyamide composition can include a combination of multiple polyamides. By combining various polyamides, the final composition can introduce the desired properties of each polyamide component, such as mechanical properties. The combination of multiple polyamides can include any number of known polyamides. In some embodiments, the polyamide composition includes a combination of any of the above-mentioned polyamides, preferably used in the above-mentioned amount. For example, the polyamide composition 6T / 612 comprising dimer acid and / or dimeramine can have a 6T / 612 ratio of about 50 / 50. The polyamide composition can also include any polymer combination of 0 wt % to 100 wt %, such as 0 wt % to 60 wt %, 10 wt % to 70 wt %, 20 wt % to 80 wt %, 30 wt % to 90 wt %, or 40 wt % to 100 wt %, as described herein.

[0046] In some embodiments, one or more polyamides with a low melting temperature are used, for example, a polyamide having a melting temperature below 270° C., for example, below 265° C., below 250° C., below 240° C., below 230° C., below 220° C., below 215° C., below 210° C., below 200° C., below 190° C., below 180° C., or below 175° C. The melting temperature of the one or more polyamides may, for example, each independently be in the range of 165° C. to 270° C., for example, 165° C. to 220° C., 170° C. to 215° C., 175° C. to 215° C., 180° C. to 215° C., 185° C. to 225° C., 205° C. to 245° C., 225° C. to 265° C., or 240° C. to 270° C. In terms of lower limits, the melting temperature of each polyamide can be greater than 165° C., such as greater than 170° C., greater than 175° C., greater than 185° C., greater than 195° C., greater than 205° C., greater than 215° C., greater than 225° C., greater than 235° C., greater than 245° C., or greater than 255° C. Higher melting temperatures, such as greater than 265° C., and lower melting temperatures, such as less than 165° C., are also contemplated. In some embodiments, one or more amorphous polyamides are used, such as polyamides that do not have a defined melting point.

[0047] The melting temperature of the polyamide composition comprising dimer acid or dimer amine or a combination thereof as a modifier may be in the range of 165°C to 270°C. In some embodiments, the polyamide composition comprising PA6,12 and the modifier described herein has a melting temperature in the range of 165°C to 270°C. In other embodiments, for example, the polyamide composition comprising PA6,10 and the modifier has a melting temperature in the range of 165°C to 270°C. In another embodiment, for example, the polyamide composition comprising PA6,6 and the modifier has a melting temperature in the range of 240°C to 270°C.

[0048] In some embodiments, one or more polyamides having a low crystallization temperature are used, for example, a polyamide having a crystallization temperature of less than 250° C., less than 240° C., less than 230° C., less than 220° C., less than 210° C., less than 200° C., less than 190° C., less than 180° C., or less than 175° C. The crystallization temperature of the one or more polyamides may, for example, each independently be in the range of 100° C. to 240° C., for example, 110° C. to 230° C., 110° C. to 200° C., 110° C. to 190° C., 110° C. to 180° C., 150° C. to 230° C., 160° C. to 230° C., or 170° C. to 230° C. In terms of lower limits, the crystallization temperature of each polyamide may be greater than 100° C., for example, greater than 110° C., greater than 120° C., greater than 130° C., greater than 140° C., greater than 150° C., greater than 160° C., or greater than 170° C. Higher crystallization temperatures are also contemplated, for example greater than 250° C., as well as lower crystallization temperatures, for example less than 100° C. The one or more polyamides having a low crystallization temperature may have a crystallization temperature in the range of 110° C. to 180° C. for PA 6,10 and / or PA 6,12, or in the range of 170° C. to 230° C. for PA 6,6, for example.

[0049] In some embodiments, each of the one or more polyamide polymers is crystalline or semi-crystalline. In some embodiments, each of the one or more polyamide polymers is crystalline. In some embodiments, each of the one or more polyamide polymers is semi-crystalline.

[0050] In some embodiments, compared with a polyamide (terpolymer) with three components or a polyamide (tetrapolymer) with four components, a polyamide (copolymer) with two components is used to provide a higher level of crystallinity. The crystallinity level can be determined by the heat of fusion detected by differential scanning calorimetry (DSC), and / or by the above-mentioned crystallization temperature. In some embodiments, polyamide is a copolymer with two components (two repeating units). Copolymer is preferably used in applications requiring higher crystallinity and / or higher melting points. In other embodiments, polyamide is a terpolymer with three components (three repeating units). In some embodiments, polyamide is a tetrapolymer with four components (four repeating units). Tetrapolymer is preferably used in applications where lower modulus and lower crystallinity are desired, for example, for tubing.

[0051] In some embodiments, the polyamide compositions described herein include only a single modifier, such as a dimeramine or dimer acid described below. In some embodiments, the polyamide includes no more than one modifier, wherein the modifier is a dimer acid or a dimeramine. Compared to providing two modifiers in the polyamide composition, the crystallinity level can also be affected by only containing a single modifier. For example, using only one modifier can maintain a higher level of crystallinity, as well as other advantages suitable for tubing, such as beneficial chemical resistance, dimensional stability, and gas barrier properties.

[0052] In other embodiments, a combination of a single dimer acid and a single dimeramine is used in the polyamide composition.

[0053] The number average molecular weight (M) of the one or more polyamide polymers in the polyamide composition is n ) can, for example, each independently be in the range of 9,000 g / mol to 60,000 g / mol, for example 9,000 g / mol to 12,000 g / mol, 9,000 g / mol to 15,000 g / mol, 9,000 g / mol to 20,000 g / mol, 9,000 g / mol to 24,000 g / mol, 9,000 g / mol to 25,000 g / mol, 9,000 g / mol to 45,000 g / mol, 10,000 g / mol to 20,000 g / mol, 10,000 g / mol to 25,000 g / mol, 10,000 g / mol to 30,000 g / mol, 10,000 g / mol to 45,000 g / mol, 12,000 g / mol to 5 g / mol to 45,000 g / mol, 30,000 g / mol to 45,000 g / mol, 35,000 g / mol to 50,000 g / mol, 40,000 g / mol to 55,000 g / mol, or 45,000 g / mol to 60,000 g / mol. The use of materials with lower M is generally not considered in conventional film formulations. n Polyamide, such as M nTypically in the range of 25,000 g / mol to 50,000 g / mol (or greater). In some embodiments, an injection molded article comprising any polyamide composition described herein is provided, wherein the number average molecular weight can be 9,000 g / mol to 20,000 g / mol. In other embodiments, an extruded article comprising any polyamide composition described herein is provided, and can be a profile extruded article, a monofilament, a fiber, wherein the number average molecular weight can be 20,000 g / mol to 45,000 g / mol.

[0054] In terms of upper limits, the one or more polyamide polymers can have a number average molecular weight of less than 60,000 g / mol, for example, less than 55,000 g / mol, less than 50,000 g / mol, less than 45,000 g / mol, less than 40,000 g / mol, less than 35,000 g / mol, less than 30,000 g / mol, less than 25,000 g / mol, less than 24,000 g / mol, less than 20,000 g / mol, less than 18,000 g / mol, less than 15,000 g / mol, less than 12,000 g / mol, or less than 10,000 g / mol. In terms of lower limits, one or more polyamide polymers can have a number average molecular weight greater than 9,000 g / mol, such as greater than 10,000 g / mol, greater than 12,000 g / mol, greater than 13,000 g / mol, greater than 15,000 g / mol, greater than 20,000 g / mol, greater than 25,000 g / mol, greater than 30,000 g / mol, greater than 35,000 g / mol, greater than 40,000 g / mol, greater than 45,000 g / mol, greater than 50,000 g / mol, or greater than 55,000 g / mol. Also contemplated are larger molecular weights, such as greater than 60,000 g / mol, and smaller molecular weights, such as less than 9,000 g / mol.

[0055] One or more polyamides each independently have a specific end group structure, such as an amine end group, a carboxylic acid end group and a so-called inert end group, including monocarboxylic acids, monoamines, low-level dicarboxylic acids that can form inert imine end groups, phthalic acid and its derivatives. It is found that in some aspects, the polymer end groups can be selected to interact specifically with the modifier in the composition, thereby affecting the dispersion and the resulting mechanical properties. The polyamide polymer described herein can have, for example, an amine end group content in the range of 10 micro-equivalents / grams to 110 micro-equivalents / grams, such as 20 micro-equivalents / grams to 100 micro-equivalents / grams, 30 micro-equivalents / grams to 90 micro-equivalents / grams, or 35 micro-equivalents / grams to 80 micro-equivalents / grams. With regard to the upper limit, the polyamide polymer can have an amine end group content less than 110 micro-equivalents / grams, such as less than 100 micro-equivalents / grams, less than 90 micro-equivalents / grams, or less than 85 micro-equivalents / grams. In terms of lower limits, the polyamide polymer can have an amine end group content greater than 10 microequivalents / gram, such as greater than 20 microequivalents / gram, greater than 25 microequivalents / gram, or greater than 30 microequivalents / gram. In some embodiments, where one or more polyamides have a high number average molecular weight, i.e., greater than about 30,000 g / mol, a lower concentration of amine end groups may be present. In general, as the number average molecular weight increases, the content of amine end groups decreases.

[0056] In addition to the composition of the polyamide mixture, it is also found that the relative viscosity of one or more amide polymers can provide surprising benefits in both performance and processing. For example, if the relative viscosity of the amide polymer is within a specific range and / or limit, the production rate and tensile strength (and optionally impact resistance) can be improved. As described herein, "relative viscosity" or "RV" represents the comparison between the viscosity of a solution of a polymer in formic acid and the viscosity of formic acid itself, and is detected using 90% formic acid and a glass capillary Ubbelohde viscometer according to standard method ASTM D789-18 (2018). For samples containing glass fiber or other fillers, the weight of the sample to be dissolved is adjusted according to the amount of filler to provide the required 11.0 grams of neat resin / 100 ml of formic acid. The solution containing this filler is filtered before being loaded into the viscometer.

[0057] The relative viscosity of the one or more polyamides can each independently or in combination be, for example, in the range of 25 to 250, such as 25 to 160, 25 to 90, 35 to 80, 35 to 70, 47.5 to 182.5, 70 to 205, 92.5 to 227.5, or 115 to 250. In terms of upper limits, the polyamide relative viscosity can be less than 250, such as less than 227.5, less than 205, less than 182.5, less than 160, less than 137.5, less than 115, less than 92.5, less than 90, less than 80, less than 70, less than 65, less than 61, less than 57, less than 53, less than 49, less than 45, less than 41, less than 37, less than 33, or less than 29. In terms of lower limits, the relative viscosity of the polyamide can be greater than 25, such as greater than 29, greater than 33, greater than 35, greater than 37, greater than 41, greater than 45, greater than 49, greater than 53, greater than 57, greater than 61, greater than 65, greater than 70, greater than 92.5, greater than 115, greater than 137.5, greater than 160, greater than 182.5, greater than 205, greater than 227.5. Higher relative viscosities, such as greater than 250, and lower relative viscosities, such as less than 25, are also contemplated. Film formulations (and films) typically have higher RVs in the range of 80 to 280, depending on whether they are injection molded or blow molded. In contrast, formulations and articles, including molded and / or extruded articles described herein, have significantly lower relative viscosities, such as less than 80.

[0058] For example, for long-chain polyamide and high-temperature polyphthalamide, the viscosity number of one or more polyamides measured in sulfuric acid may be, for example, each independently or in combination, in the range of 65 to 350 cm 3 / g range, for example, 65 to 160 cm 3 / g, 85 to 200 cm 3 / g, 100 to 250 cm 3 / g, 150 to 300 cm 3 / g, or 200 to 350cm 3 / g. As for the upper limit, the viscosity of the polyamide can be less than 350cm 3 / g, for example, less than 325cm 3 / g, less than 300cm 3 / g, less than 275cm 3 / g, less than 250cm 3 / g, less than 225cm 3 / g, less than 220cm 3 / g, less than 215cm 3 / g, less than 210cm 3 / g, less than 205cm 3 / g, less than 200cm 3 / g, or less than 195cm 3 / g. As for the lower limit, the viscosity of the polyamide can be greater than 65cm 3 / g, for example, greater than 70cm 3 / g, greater than 75cm 3 / g, greater than 80cm 3 / g, greater than 85cm 3 / g, greater than 90cm 3 / g, greater than 95cm 3 / g, greater than 100cm 3 / g, greater than 105cm 3 / g, greater than 110cm 3 / g, greater than 115cm 3 / g, greater than 120cm 3 / g, greater than 125cm 3 / g, greater than 130cm 3 / g, greater than 135cm 3 / g, greater than 140cm 3 / g, greater than 145cm 3 / g, greater than 150cm 3 / g, greater than 155cm 3 / g. Higher viscosity numbers, such as greater than 350 cm 3 / g, and a lower viscosity, such as less than 65cm 3 / g.

[0059] Dimer Acid / Dimer Amine Modifier

[0060] The polyamide composition described herein includes a modifier. The modifier described herein may include dimer acid, or dimer amine, or a combination thereof. Dimer acid may be a dicarboxylic acid. In some cases, dimer acid or dimerized fatty acid is a dicarboxylic acid prepared by dimerization of unsaturated fatty acids obtained from tall oil, typically prepared in the presence of a clay catalyst. Dimer acid may include a chemical intermediate prepared by dimerization of unsaturated fatty acids (e.g., oleic acid, linolenic acid, linolenic acid, ricinoleic acid) in the presence of a catalyst, such as bentonite or montmorillonite clay. Commercially available dimer fatty acids are typically product mixtures in which dimer products dominate. Some commercially available dimer acids are prepared by dimerization of tall oil fatty acids. Dimer fatty acids may have 36 carbon atoms and two carboxylic acid groups. They may be saturated or unsaturated. In some cases, dimer acid or dimer amine are hydrogenated to remove unsaturation, thereby having better performance.

[0061] Examples of dimer fatty acids include dimerized oleic acid, trimerized oleic acid, dimerized linoleic acid, trimerized linoleic acid, dimerized linolenic acid, trimerized linolenic acid, or mixtures thereof. In some cases, the dimer acid may be primarily a dimer of stearic acid, also known as C 36 Dimer acid. The polyamide composition may include one or more dimer acids, such as adipic acid, or may be free of adipic acid or substantially free of adipic acid. The polyamide polymers described herein may include, for example, one or more dimer acids having at least 18 carbon atoms, preferably 18 to 44 carbon atoms, in the C 18 (including 18 carbon atoms) to C 44 (including 44 carbon atoms), for example, C 18 To C 40 , C 20 To C 38 , or C 22 To C 36 As regards the upper limit, the polyamide polymer may contain C 44 or less carbon atoms, such as C 44 Dimer acid, C 42 Dimer acid, C 40 Dimer acid, C 38 Dimer acid, or C 36 As a lower limit, the polyamide polymer may contain C 18 or more carbon atoms, such as C 18 Dimer acid, C 20 Dimer acid, C 22 Dimer acid, C 24 Dimer acid, C 26 Dimer acid, C 28 Dimer acid, C 30 Dimer acid, C 32 Dimer acid, or C 34 Dimer acids. Dimer acids with higher carbon numbers are also contemplated, for example, greater than C 44 , and dimer acids having lower carbon numbers, such as less than C 18 .

[0062] The dimer acid can be converted to a dimeramine by reaction with ammonia and subsequent reduction and can be an amine or amine derivative of a hydrocarbon-soluble polymerized fatty acid, in particular a dimeramine derived from a dicarboxylic acid containing at least 12, preferably 19 to 60 carbon atoms. The polyamide composition can contain one or more dimer acids and / or dimeramines, non-limiting examples of which are C 36 - unsaturated hydrogenated dimer acids, such as PRIPOL having a molecular weight of about 570 g / mol TM1009, and / or a diamine, such as C having a molecular weight of about 540 g / mol 36 PRIAMINE TM 1074 or PRIAMINE TM 1075 (each from Croda Inc., USA).

[0063] It has been found that the use of dimer acids and / or dimeramines can provide designable functionality to the entire polyamide composition while maintaining the above-mentioned initial desired polyamide functionality. In order to obtain the desired performance, a single dimer acid or a single dimeramine can be used in the polyamide composition. In some embodiments, the polyamide composition comprises a single dimer acid. In some embodiments, the polyamide composition comprises a single dimeramine. In other embodiments, the polyamide composition comprises at least one dimer acid or at least one dimeramine or a combination thereof.

[0064] The concentration of the modifier in the entire polyamide composition can be, for example, in the range of 5 wt % to 55 wt %, such as 5 wt % to 10 wt %, 15 wt % to 20 wt %, 20 wt % to 30 wt %, 25 wt % to 35 wt %, 30 wt % to 40 wt %, 15 wt % to 50 wt %, 20 wt % to 45 wt %, 35 wt % to 55 wt %, 35 wt % to 45 wt %, 40 wt % to 50 wt %, 45 wt % to 55 wt %, or any subranges thereof. In terms of upper limits, the concentration of the modifier can be less than 55 wt %, such as less than 50 wt %, less than 45 wt %, less than 40 wt %, less than 35 wt %, less than 30 wt %, less than 25 wt %, less than 20 wt %, less than 15 wt %, or less than 10 wt %. In terms of lower limits, the concentration of the combined polyamide polymers can be greater than 5 wt%, such as greater than 10 wt%, greater than 15 wt%, greater than 20 wt%, greater than 25 wt%, greater than 30 wt%, greater than 35 wt%, greater than 40 wt%, greater than 45 wt%, or greater than 50 wt%. Lower concentrations, such as less than 5 wt%, and higher concentrations, such as greater than 55 wt%, are also contemplated.

[0065] Structural formula

[0066] In certain embodiments, the polyamide composition comprises one or more polyamides represented by the following formulas (1)-(6):

[0067]

[0068]

[0069] In the above formulas (1) and (2), for copolymers, X+Y=100 wt%. In the above formulas (3)-(6), for terpolymers, X+Y+Z=100 wt%. In the above formulas (1)-(6), a=2-18, b=2-18, c=2-18, and d=2-18. In other embodiments, four different monomers (2 acids and 2 amines) are used to obtain a tetrapolymer. Alternatively, in other embodiments, the formulation may include dimeramine and dimer acid in the same polymer.

[0070] In some embodiments, the polyamide composition contains AA-BB type polyamide. In some embodiments, the polyamide composition contains 5 to 55 wt% of dimer acid and / or dimeramine repeating units and 45 to 95 wt% of AA-BB repeating units. The polyamide composition may, for example, contain 5 to 55 wt% of dimer acid and / or dimeramine repeating units, such as 5 to 15 wt%, 10 to 20 wt%, 15 to 25 wt%, 20 to 30 wt%, 25 to 35 wt%, 30 to 40 wt%, 35 to 45 wt%, 40 to 50 wt%, 45 to 55 wt%, or any sub-ranges thereof. In some embodiments, the polyamide composition may contain dimer acid and / or dimeramine repeating units in the range of 15 to 50 wt%, such as 20 to 45 wt%, 35 to 55 wt%, or any sub-ranges thereof. In terms of upper limits, the polyamide composition may, for example, contain less than 55% by weight of dimer acid and / or dimeramine repeating units, such as less than 50% by weight, less than 45% by weight, less than 40% by weight, less than 35% by weight, less than 30% by weight, less than 25% by weight, less than 20% by weight, less than 15% by weight, or less than 10% by weight. In terms of lower limits, the polyamide composition may, for example, contain more than 5% by weight of dimer acid and / or dimeramine repeating units, such as more than 10% by weight, more than 15% by weight, more than 20% by weight, more than 25% by weight, more than 30% by weight, more than 35% by weight, more than 40% by weight, more than 45% by weight, or more than 50% by weight. Lower amounts of dimer acid and / or dimeramine repeating units, such as less than 5% by weight, and higher amounts of dimer acid and / or dimeramine repeating units, such as more than 55% by weight, are also contemplated.

[0071] The polyamide composition may contain, for example, 45 to 95 wt% of AA-BB repeating units, such as 45 to 55 wt%, 50 to 60 wt%, 55 to 65 wt%, 60 to 70 wt%, 65 to 75 wt%, 70 to 80 wt%, 75 to 85 wt%, 80 to 90 wt%, 85 to 95 wt%, or any subranges thereof. In terms of upper limits, the polyamide composition may, for example, contain less than 95 wt% of AA-BB repeating units, such as less than 90 wt%, less than 85 wt%, less than 80 wt%, less than 75 wt%, less than 70 wt%, less than 65 wt%, less than 60 wt%, less than 55 wt%, or less than 50 wt%. In terms of lower limits, the polyamide composition may, for example, contain greater than 45 wt% AA-BB repeating units, such as greater than 50 wt%, greater than 55 wt%, greater than 60 wt%, greater than 65 wt%, greater than 70 wt%, greater than 75 wt%, greater than 80 wt%, greater than 85 wt%, or greater than 90 wt%. Lower amounts of AA-BB repeating units, such as less than 45 wt%, and higher amounts of AA-BB repeating units, such as greater than 95 wt%, are also contemplated.

[0072] The AA-BB repeating unit may be selected from products made from dicarboxylic acids and diamines, and includes but is not limited to: PA6,6; PA6,9; PA6,10; PA6,12; PA6,18; PA9,6; PA10,6; PA10,9: PA10,10; and PA10,12. In addition, the repeating unit may be selected from products made from polyphthalamide, and includes but is not limited to: PA6,T / 6,6; PA6,T / 6,I; and PA6,T / D,T.

[0073] The molecular structures of PA6,12-hydrogenated dimer acid and PA6,12-hydrogenated dimeramine are shown in the following formulas (A) and (B), respectively.

[0074]

[0075] Methyl / amide ratio

[0076] The polyamide composition comprising dimer acid or dimeramine or a combination thereof as a modifier can have a dimer concentration determined via a methyl / amide ratio. It is believed that the methyl / amide ratio is important because the main chain has a stronger aliphatic characteristic due to the presence of more CH2 (methylene) groups between the amides, and the resulting chain has significantly higher flexibility due to its free range of motion without being limited by the amide bond; in other words, the Brownian motion of the chain increases with the decrease of the amide functionality. In addition, the methyl group is hydrophobic and will not associate with water. Although the film has nothing to do with the moisture absorption rate, it is unexpected that the methyl / amide ratio possessed by the polyamide composition for non-membrane use described herein is beneficial and provides low moisture absorption rate and high chemical resistance. In addition, the methyl / amide ratio can be designed so that the polyamide composition can handle a strongly alkaline or strongly acidic environment, thereby providing the best chemical resistance in a specific environment. Therefore, the smaller the amide ratio, the lower the absorption potential for moisture. By combining a polyamide polymer with dimer acid and / or dimeramine, the methyl / amide ratio can be controlled. By increasing the methyl / amide ratio, it is believed that the resulting polyamide composition will have increased flexibility, increased chemical resistance, and reduced moisture absorption. The polyamide composition may, for example, have a methyl / amide ratio in the range of 6:1 to 15:1, such as 6:1 to 9:1, 6:1 to 12:1, 9:1 to 12:1, 9:1 to 15:1, or 12:1 to 15:1. A polyamide composition having a methyl / amide ratio in the range of 6:1 to 15:1 may, for example, be PA6,6 or PA6,12. This can be explained and calculated from the main chain structure. In the case of PA6,6, there are two amide bonds and 12 carbon atoms in each repeating unit, which provides a ratio of 12 / 2 or 6:1. In the case of PA6,12, there are two amide bonds and 18 carbon atoms in each repeating unit, which provides a ratio of 18 / 2 or 9:1. In embodiments with a PA6,12-s-PA6,36 system, the methyl / amide ratio can be calculated via the mole % of each component. For example, in the case of a 75 / 25 PA6,12 / PA6,36 composition, the methyl / amide ratio is 12:1.

[0077] The polyamide composition can be PA6,6 having a methyl / amide ratio of about 6:1 or greater. In other embodiments, the polyamide composition has a methyl / amide ratio in the range of 9:1 to 15:1. The polyamide composition can be PA6,12 having a methyl / amide ratio of about 9:1 or greater. The inventors surprisingly found that, for example, a polyamide composition comprising PA6,12 and up to about 45% by weight of a dimer modifier can increase the methyl / amide ratio from 9:1 (without modifier) ​​to 12:1. Any polyamide polymer described herein can be used and can have a methyl / amide ratio of 6:1 to 15:1. As the amount of dimer acid and / or dimeramine modifier increases, the methyl / amide ratio also increases. The increase in the methyl / amide ratio obtains advantages such as improved chemical resistance, reduced moisture absorption, improved mechanical properties (i.e., elongation, impact resistance, abrasion resistance), better transparency, UV resistance, etc.

[0078] Fiberglass

[0079] The polyamide composition optionally comprises reinforcing fillers, such as glass fibers. The glass fibers may include soda lime silicate, zirconium silicate, calcium borosilicate, calcium alumina-borosilicate, calcium aluminosilicate, magnesium aluminosilicate, or a combination thereof. The glass fibers may include long fibers, such as greater than 6 mm; short fibers, such as less than 6 mm, or a combination thereof. The glass fibers may be ground.

[0080] The glass fiber in the polyamide composition can be selected relative to the amount of other composition components, thereby advantageously providing additional strength, and can not adversely affect material ductility.The concentration of the glass fiber in the polyamide composition can be, for example, in the range of 0 wt % to 60 wt %, for example 0 wt % to 30 wt %, 5 wt % to 35 wt %, 10 wt % to 40 wt %, 15 wt % to 45 wt %, 20 wt % to 50 wt %, 25 wt % to 55 wt %, or 30 wt % to 60 wt %.In some embodiments, the concentration of glass fiber is in the range of 20 wt % to 40 wt %, for example 25 wt % to 35 wt %, 27 wt % to 33 wt %, 28 wt % to 32 wt %, or 29 wt % to 31 wt %.In some aspects, the concentration of glass fiber is in the range of 20 wt % to 40 wt %. In terms of upper limits, the concentration of glass fibers can be less than 60 wt %, such as less than 55 wt %, less than 50 wt %, less than 45 wt %, less than 40 wt %, less than 35 wt %, less than 33 wt %, less than 32 wt %, or less than 31 wt %, less than 30 wt %, less than 25 wt %, less than 20 wt %, less than 15 wt %, less than 10 wt %, or less than 5 wt %. In terms of lower limits, the concentration of glass fibers can be greater than 0 wt %, such as greater than 5 wt %, greater than 10 wt %, greater than 15 wt %, greater than 20 wt %, greater than 25 wt %, greater than 27 wt %, greater than 28 wt %, greater than 29 wt %, greater than 30 wt %, greater than 35 wt %, greater than 40 wt %, greater than 45 wt %, greater than 50 wt %, or greater than 55 wt %. Higher concentrations, such as greater than 60 wt %, are also contemplated. In some aspects, the concentration of glass fibers in the polyamide composition is greater than 5 wt %.

[0081] For the polyamide compositions described herein, the addition of reinforcing fillers is important because reinforcing fillers, such as glass fibers, contribute to the strength and performance of the resulting articles, such as extruded articles, profile extruded articles, monofilaments or fibers. In contrast, polyamides for film applications do not include glass and are free or substantially free of glass and / or glass fibers.

[0082] Melt Stabilizer / Lubricant

[0083] The polyamide composition can include one or more melt stabilizers (lubricants). The type and relative amount of the melt stabilizer can be selected to improve the processing of the composition, and simultaneously contribute to the high strength and ductility of the material. The concentration of the lubricant in the polyamide composition can be, for example, in the range of 0 wt % to 2 wt %, for example 0.1 wt % to 0.5 wt %, 0.1 wt % to 0.6 wt %, 0.1 wt % to 1.0 wt %, 0.1 wt % to 1.5 wt %, 0.1 wt % to 2.0 wt %, 0.5 wt % to 1.0 wt %, 0.5 wt % to 1.5 wt %, or 0.5 wt % to 2.0 wt %. In terms of upper limits, the concentration of the lubricant can be less than 2.0 wt%, such as less than 1.8 wt%, less than 1.6 wt%, less than 1.5 wt%, less than 1.4 wt%, less than 1.2 wt%, less than 1.0 wt%, less than 0.8 wt%, less than 0.6 wt%, less than 0.5 wt%, less than 0.4 wt%, less than 0.3 wt%, less than 0.2 wt%, or less than 0.1 wt%. In terms of lower limits, the concentration of the lubricant can be greater than 0 wt%, such as greater than 0.1 wt%, greater than 0.2 wt%, greater than 0.3 wt%, greater than 0.4 wt%, greater than 0.5 wt%, greater than 0.6 wt%, greater than 0.8 wt%, greater than 1.0 wt%, greater than 1.2 wt%, greater than 1.4 wt%, greater than 1.5 wt%, greater than 1.6 wt%, or greater than 1.8 wt%. Higher concentrations, such as greater than 2.0 wt%, are also contemplated.

[0084] In some embodiments, the melt stabilizer includes a saturated fatty acid. For example, the melt stabilizer may include stearic acid, behenic acid or a combination thereof or a salt thereof. In some cases, the melt stabilizer includes a stearate. In some cases, the melt stabilizer may include, for example, zinc stearate, calcium stearate, aluminum distearate, zinc stearate, calcium stearate, N, N'-ethylenebisstearamide, stearyl erucamide. In some cases, the melt stabilizer is a stearate combined with a wax, and the wax is, for example, a saponified ester wax. In some embodiments, the melt stabilizer does not include an ionic lubricant.

[0085] In some embodiments, the melt stabilizer can be a wax. In some embodiments, the melt stabilizer is composed of wax. In some embodiments, the wax includes fatty acids. In some embodiments, the melt stabilizer is composed of fatty acids. In some embodiments, the wax includes saturated fatty acids. In some embodiments, the melt stabilizer is composed of saturated fatty acids. In some embodiments, the wax includes stearic acid, behenic acid, or a salt thereof or a combination thereof. In some embodiments, the wax is composed of stearic acid, behenic acid or a salt thereof or a combination thereof. In some embodiments, the wax is a saponified ester wax. For example, a wax suitable for the polyamide composition described herein is montan wax, which is a saponified saponified ester wax including a dimerized alkyl chain, having a molecular weight of about 824 g / mol.

[0086] In some cases, the wax is a saponified ester wax combined with a stearate. In some embodiments, the wax is a montan wax and is further combined with a metal stearate, such as aluminum distearate or zinc stearate.

[0087] In some cases, the composition uses waxes having alkyl moieties or tails that are significantly longer than stearates, for example, 40% longer. 28 Some montan waxes are suitable in polyamide compositions because the higher chain length makes them more effective lubricants for longer chain polymers. In some embodiments, the lubricant includes more than C 18 , greater than C 20 , greater than C 22 , greater than C 24 , greater than C 26 or greater than C 28 In some embodiments, C is used in the polyamide compositions described herein. 28 Lubricants. Stearates such as aluminum distearate, zinc stearate, calcium stearate, or combinations thereof are not suitable for use alone, but may be suitably used in combination with other lubricants such as those described above.

[0088] Specifically, in some embodiments, the polyamide composition does not include stearate waxes such as ethylene bisstearamide (EBS), which is commonly used as Sold and has a molecular weight of about 593 g / mol and has C 18 In particular, in some embodiments, the polyamide composition does not include stearic acid. In some embodiments, the polyamide composition does not include stearyl erucamide. In some embodiments, the polyamide composition does not include C 18 This is because shorter chain C 18 Stearates have a stronger compatibility with PA6 or PA6,6 formulations for film applications. Importantly, C18 Stearate waxes / lubricants, such as EBS wax, are essential compatibilizers for membrane monomers. EBS wax is not suitable for use in the polyamide compositions described herein, which do not contain EBS wax. This is important because while EBS can be used in membrane formulations or in PA6 type polymers, EBS wax is not suitable for use in non-membrane formulations with more hydrophobic long chain polymers described herein. EBS wax simply cannot blend with the surface of the long chain polyamides described herein. The polyamide compositions described herein do not contain or are substantially free of EBS wax, stearyl erucamide and / or C 18 In some embodiments, the polyamide compositions described herein are free or substantially free of lubricants having shorter chain lengths, EBS wax, stearyl erucamide, C 18 Stearates and combinations thereof, e.g., containing less than 5 wt%, less than 3 wt%, less than 1 wt%, less than 0.5 wt%, less than 0.1 wt%, or no lubricants with shorter chain lengths, EBS waxes, stearyl erucamide, C 18 Stearates and combinations thereof. In some cases, the melt stabilizer does not include stearyl erucamide, aluminum distearate, zinc stearate, calcium stearate, or a combination thereof, e.g., less than 1.0 wt%, less than 0.5 wt%, less than 0.1 wt%, or completely. In some cases, stearyl erucamide, aluminum distearate, zinc stearate, calcium stearate, or a combination thereof, is present only in combination with other wax lubricants, such as montan wax.

[0089] In some embodiments, the polyamide composition comprises a lubricant or melt stabilizer having, for example, a molecular weight of 600 g / mol to 1200 g / mol, for example, 600 g / mol to 800 g / mol, 800 g / mol to 1000 g / mol, or 1000 g / mol to 1200 g / mol. In terms of upper limits, the molecular weight of the lubricant or melt stabilizer can be less than 1200 g / mol, for example, less than 1100 g / mol, less than 1000 g / mol, less than 900 g / mol, less than 800 g / mol, or less than 700 g / mol. In terms of lower limits, the molecular weight of the lubricant or melt stabilizer can be greater than 600 g / mol, for example, greater than 700 g / mol, greater than 800 g / mol, greater than 900 g / mol, greater than 1000 g / mol, or greater than 1100 g / mol. Lower molecular weights, for example, less than 600 g / mol, and higher molecular weights, for example, greater than 1200 g / mol are also contemplated. In some embodiments, the polyamide compositions described herein are free or substantially free of lubricants having a relatively low molecular weight, for example, having a molecular weight of less than 800 g / mol, or less than 700 g / mol, or less than 600 g / mol, for example, containing less than 5 wt%, for example, less than 3 wt%, less than 1 wt%, less than 0.5 wt%, less than 0.1 wt%, or no lubricants having a relatively low molecular weight.

[0090] In addition to other property-improving effects, the melt stabilizers also significantly improve the dispersion of the components in the polymer matrix, for example the dispersion of the impact modifier in the polyamide matrix, which advantageously improves the impact properties.

[0091] In the polyamide composition, the concentration of the melt stabilizer, such as stearic acid or a salt thereof, can be, for example, in the range of 0.01 wt % to 0.7 wt %, such as 0.01 wt % to 0.1 wt %, 0.05 wt % to 0.2 wt %, 0.1 wt % to 0.3 wt %, 0.1 wt % to 0.6 wt %, 0.2 wt % to 0.4 wt %, 0.3 wt % to 0.5 wt %, 0.4 wt % to 0.6 wt %, or 0.5 wt % to 0.7 wt %. In terms of upper limits, the concentration of the melt stabilizer can be less than 0.7 wt %, such as less than 0.6 wt %, less than 0.5 wt %, less than 0.4 wt %, less than 0.3 wt %, less than 0.2 wt %, less than 0.1 wt %, less than 0.05 wt %, less than 0.03 wt %, or less than 0.02 wt %. In terms of lower limit, the concentration of stearic acid or its salt can be greater than 0.01 weight %, for example, greater than 0.02 weight %, greater than 0.03 weight %, greater than 0.05 weight %, greater than 0.1 weight %, greater than 0.2 weight %, greater than 0.3 weight %, greater than 0.4 weight %, greater than 0.5 weight %, or greater than 0.6 weight %. Higher concentrations, for example, greater than 0.7 weight %, and lower concentrations, for example, less than 0.01 weight %. Suitable melt stabilizers or lubricants can be selected from N, N'-ethylene bis stearamide, stearyl erucic acid amide, distearate aluminum, zinc stearate, montan wax, or a combination thereof. In certain embodiments, a combination of multiple lubricants is used, for example, 0.3-0.4 weight % of stearyl erucic acid amide is mixed with 0.1-0.2 weight % of aluminum stearate or zinc stearate. Lubricants with lower or higher amounts can be designed according to the purpose.

[0092] In some preferred embodiments, stearates or metal stearates, such as aluminum distearate and / or zinc stearate, are used as lubricants in combination with saponified ester waxes, such as montan wax.

[0093] In these aspects, the polyamide compositions described herein include greater than 0.1 wt %, or greater than 0.2 wt %, or greater than 0.3 wt % lubricant. The compositions described herein may include at least about 0.3 wt % lubricant, which is atypical and absent in film compositions. In the case of injection molding, the lubricant content is preferably from about 0.3% to about 0.6%.

[0094] For the polyamide compositions described herein, the addition of lubricants or melt stabilizers is important because lubricants or melt stabilizers, such as glass fibers, contribute to the strength and performance of the resulting articles, such as extruded articles, profile extruded articles, monofilaments or fibers. In contrast, polyamides for film applications do not contain higher molecular weight lubricants and are free or substantially free of lubricants having higher molecular weights.

[0095] Color package (aniline black / carbon black)

[0096] The polyamide composition may include one or more colorants, such as soluble dyes, such as nigrosine (0.5%, 30% active ingredient) or solvent black 7. The concentration of nigrosine in the polyamide composition may be, for example, in the range of 0.1 to 5 wt%, such as 0.1 wt% to 1 wt%, 0.15 wt% to 1.5 wt%, 0.22 wt% to 2.3 wt%, 0.32 wt% to 3.4 wt%, or 0.48 wt% to 5.0 wt%. In some embodiments, the concentration of nigrosine is in the range of 1.0 wt% to 2.0 wt%, such as 1.0 wt% to 1.6 wt%, 1.1 wt% to 1.7 wt%, 1.2 wt% to 1.8 wt%, 1.3 wt% to 1.9 wt%, or 1.4 wt% to 2.0 wt%. In terms of upper limits, the concentration of nigrosine can be less than 5.0 wt%, for example, less than 3.4 wt%, less than 2.3 wt%, less than 2.0 wt%, less than 1.9 wt%, less than 1.8 wt%, less than 1.7 wt%, less than 1.6 wt%, less than 1.5 wt%, less than 1.4 wt%, less than 1.3 wt%, less than 1.2 wt%, less than 1.1 wt%, less than 1.0 wt%, less than 0.71 wt%, less than 0.48 wt%, less than 0.32 wt%, less than 0.22 wt%, or less than 0.15 wt%. In terms of lower limits, the concentration of nigrosine can be greater than 0.1 wt %, such as greater than 0.15 wt %, greater than 0.22 wt %, greater than 0.32 wt %, greater than 0.48 wt %, greater than 0.71 wt %, greater than 1.0 wt %, greater than 1.1 wt %, greater than 1.2 wt %, greater than 1.3 wt %, greater than 1.4 wt %, greater than 1.5 wt %, greater than 1.6 wt %, greater than 1.7 wt %, greater than 1.8 wt %, greater than 1.9 wt %, greater than 2.0 wt %, greater than 2.3 wt %, or greater than 3.4 wt %. Lower concentrations, such as less than 0.1 wt %, and higher concentrations, such as greater than 5.0 wt %, are also contemplated. In some cases, nigrosine is provided in a masterbatch, and the concentration of nigrosine or dye in the masterbatch and in the resulting composition can be easily calculated.

[0097] The polyamide composition may include one or more particles, such as carbon black (0.5%, 35% active ingredient). The concentration of the carbon black in the polyamide composition may be, for example, in the range of 0.1 to 5.0 wt %, such as 0.1 to 1.0 wt %, 0.15 to 1.5 wt %, 0.22 to 2.3 wt %, 0.32 to 3.4 wt %, or 0.48 to 5.0 wt %. In some embodiments, the concentration of the carbon black is in the range of 1.0 to 2.0 wt %, such as 1.0 to 1.6 wt %, 1.1 to 1.7 wt %, 1.2 to 1.8 wt %, 1.3 to 1.9 wt %, or 1.4 to 2.0 wt %. In terms of upper limits, the concentration of carbon black can be less than 5.0 wt%, for example, less than 3.4 wt%, less than 2.3 wt%, less than 2.0 wt%, less than 1.9 wt%, less than 1.8 wt%, less than 1.7 wt%, less than 1.6 wt%, less than 1.5 wt%, less than 1.4 wt%, less than 1.3 wt%, less than 1.2 wt%, less than 1.1 wt%, less than 1.0 wt%, less than 0.71 wt%, less than 0.48 wt%, less than 0.32 wt%, less than 0.22 wt%, or less than 0.15 wt%. In terms of lower limits, the concentration of carbon black can be greater than 0.1 wt %, such as greater than 0.15 wt %, greater than 0.22 wt %, greater than 0.32 wt %, greater than 0.48 wt %, greater than 0.71 wt %, greater than 1.0 wt %, greater than 1.1 wt %, greater than 1.2 wt %, greater than 1.3 wt %, greater than 1.4 wt %, greater than 1.5 wt %, greater than 1.6 wt %, greater than 1.7 wt %, greater than 1.8 wt %, greater than 1.9 wt %, greater than 2.0 wt %, greater than 2.3 wt %, or greater than 3.4 wt %. Lower concentrations, such as less than 0.1 wt %, and higher concentrations, such as greater than 5.0 wt %, are also contemplated. In some cases, carbon black is provided in a masterbatch, and the concentration of carbon black in the masterbatch and in the resulting composition can be easily calculated.

[0098] In the polyamide composition, the weight ratio between the one or more polyamide polymers and the aniline black and / or carbon black can be, for example, in the range of 1 to 85, such as 1 to 14, 1.6 to 22, 2.4 to 35, 3.8 to 55, or 5.9 to 85. In terms of upper limits, the ratio between the one or more polyamide polymers and the aniline black can be less than 85, such as less than 55, less than 35, less than 22, less than 14, less than 9.2, less than 5.9, less than 3.8, less than 2.4, or less than 1.6. In terms of lower limits, the ratio between the one or more polyamide polymers and the aniline black can be greater than 1, such as greater than 1.6, greater than 2.4, greater than 3.8, greater than 5.9, greater than 9.2, greater than 14, greater than 22, greater than 35, or greater than 55. Higher ratios, such as greater than 55, and lower ratios, such as less than 1, are also contemplated.

[0099] The polyamide composition can include one or more pigments, such as carbon black. The concentration of the carbon black in the polyamide composition can be, for example, in the range of 0.1 to 5.0 wt %, such as 0.1 wt % to 1.05 wt %, 0.15 wt % to 1.55 wt %, 0.22 wt % to 2.29 wt %, 0.32 wt % to 3.38 wt %, or 0.48 wt % to 5.0 wt %. In some embodiments, the concentration of carbon black is in the range of 0.2 wt % to 0.8 wt %. With regard to the upper limit, the concentration of carbon black can be less than 5.0 wt %, such as less than 3.4 wt %, less than 2.3 wt %, less than 1.5 wt %, less than 1.0 wt %, less than 0.71 wt %, less than 0.48 wt %, less than 0.32 wt %, less than 0.22 wt %, or less than 0.15 wt %. In some embodiments, the concentration of carbon black is less than 3.0 wt %. In terms of lower limits, the concentration of carbon black can be greater than 0.1 wt%, such as greater than 0.15 wt%, greater than 0.22 wt%, greater than 0.32 wt%, greater than 0.48 wt%, greater than 0.71 wt%, greater than 1.0 wt%, greater than 1.5 wt%, greater than 2.3 wt%, or greater than 3.4 wt%. Lower concentrations, such as less than 0.1 wt%, and higher concentrations, such as greater than 5.0 wt%, are also contemplated.

[0100] In these aspects, the concentration of the colorant in the polyamide composition is greater than 0.1 wt%.

[0101] For the polyamide compositions described herein, the addition of colorants is important because colorants, such as aniline black and / or carbon black, contribute to the properties of the resulting articles, such as extruded articles, profile extruded articles, monofilaments or fibers. In contrast, polyamides for film applications do not include one or more colorants because film applications are associated with transparency.

[0102] Mineral fillers

[0103] The polyamide composition optionally comprises a filler, such as an inorganic mineral filler. The inorganic mineral filler may include one or more of dolomite, silica, calcium carbonate, magnesium hydroxide, zinc borate, talc, vermiculite, diatomaceous earth, perlite, wollastonite, fly ash, kaolin clay, mica, or titanium dioxide, calcium carbonate, magnesium hydroxide, talc, wollastonite, fly ash, or a combination thereof.

[0104] The amount of the mineral filler in the polyamide composition relative to the other composition components can be selected to advantageously balance melt strength and formability. The concentration of the mineral filler in the polyamide composition can be, for example, in the range of 0 wt % to 30 wt %, for example, 0 wt % to 10 wt %, 5 wt % to 15 wt %, 10 wt % to 20 wt %, 15 wt % to 25 wt %, or 20 wt % to 30 wt %. With respect to the upper limit, the concentration of the mineral filler can be less than 30 wt %, for example, less than 25 wt %, less than 20 wt %, less than 15 wt %, less than 10 wt %, or less than 5 wt %. With respect to the lower limit, the concentration of the mineral filler can be greater than 0 wt %, for example, greater than 5 wt %, greater than 10 wt %, greater than 15 wt %, greater than 20 wt %, greater than 25 wt %, or greater than 30 wt %. Higher concentrations, for example, greater than 30 wt %, are also contemplated.

[0105] Impact modifier

[0106] The polyamide composition described herein comprises one or more impact modifiers. In some cases, the impact modifier comprises an olefin, an acrylate or an acryl compound, or a combination thereof, including polymers of these compounds, such as polyolefins or polyacrylates. These compounds can be unmodified or modified, such as (grafted) modified with maleic anhydride. In some embodiments, the impact modifier comprises an olefin modified with maleic anhydride, an olefin not modified with maleic anhydride, an acrylate, or an acryl compound, or a combination thereof. In some cases, the impact modifier comprises a modified olefin, such as an olefin modified with maleic anhydride. The impact modifier can include ethylene-octene and / or ethylene-acrylate copolymers modified with maleic anhydride.

[0107] In some embodiments, the impact modifier has a glass transition temperature in the range of 0°C to -100°C, such as -5°C to -80°C, -10°C to -70°C, -20°C to -60°C, or -25°C to -55°C. In terms of lower limits, the impact modifier may have a glass transition temperature greater than -100°C, such as greater than -80°C, greater than -70°C, greater than -60°C, or greater than -55°C. In terms of upper limits, the impact modifier may have a glass transition temperature less than 0°C, such as less than -5°C, less than -10°C, less than -15°C, or less than -25°C. Impact modifiers with such glass transition temperatures are believed to synergistically improve energy dissipation properties, such as impact performance. These particular impact modifiers have a glass transition temperature that is in a temperature range that can work with the polyamide and glass fiber to achieve improved impact performance, especially in the desired temperature range, such as -10°C to -70°C.

[0108] In some embodiments, the impact modifier may include a styrenic copolymer, such as acrylate-butadiene-styrene or methyl methacrylate-butadiene-styrene copolymer. The impact modifier may include an acryl polymer, or a polyethylene polymer such as chlorinated polyethylene. In some embodiments, the impact modifier includes an ethylene-octene copolymer. In some cases, the combination of an impact modifier and a melt stabilizer (optionally in the disclosed amounts and ratios) provides a surprising synergistic combination of performance characteristics, such as tensile / flexural properties and impact strength.

[0109] The concentration of the impact modifier in the polyamide composition can be, for example, in the range of 3 wt % to 30 wt %, such as 3 wt % to 19.2 wt %, 3 wt % to 25 wt %, 3 wt % to 20 wt %, 5.7 wt % to 21.9 wt %, 4.0 wt % to 15 wt %, 5.5 wt % to 14 wt %, 6.0 wt % to 11.5 wt %, 8.4 wt % to 24.6 wt %, 11.1 wt % to 27.3 wt %, or 13.8 wt % to 30 wt %. In some embodiments, the concentration of the impact modifier is in the range of 6 wt % to 20 wt %, such as 6 wt % to 14.4 wt %, 7.4 wt % to 15.8 wt %, 8.8 wt % to 17.2 wt %, 10.2 wt % to 18.6 wt %, or 11.6 wt % to 20 wt %. In terms of upper limits, the concentration of the impact modifier can be less than 30 weight percent, e.g., less than 27.3 weight percent, less than 25.0 weight percent, less than 24.6 weight percent, less than 21.9 weight percent, less than 20 weight percent, less than 18.6 weight percent, less than 17.2 weight percent, less than 15.8 weight percent, less than 15 weight percent, less than 14 weight percent, less than 14.4 weight percent, less than 13 weight percent, less than 11.6 weight percent, less than 11.5 weight percent, less than 10.2 weight percent, less than 8.8 weight percent, less than 7.4 weight percent, less than 6 weight percent, or less than 5.4 weight percent. In terms of lower limits, the concentration of the impact modifier can be greater than 3 wt%, greater than 4.0 wt%, greater than 5.5 wt%, greater than 5.4 wt%, greater than 6 wt%, greater than 7.4 wt%, greater than 8.8 wt%, greater than 10.2 wt%, greater than 11.6 wt%, greater than 13 wt%, greater than 14.4 wt%, greater than 15.8 wt%, greater than 17.2 wt%, greater than 18.6 wt%, greater than 20 wt%, greater than 21.9 wt%, greater than 24.6 wt%, greater than 25.0 wt%, or greater than 27.6 wt%. Lower concentrations, such as less than 3 wt%, and higher concentrations, such as greater than 30 wt%, are also contemplated.

[0110] In these aspects, the concentration of the impact modifier in the polyamide composition is greater than 3 wt%. In some cases, the combination of an impact modifier and a melt stabilizer (optionally in the disclosed amounts and ratios) provides a surprising synergistic combination of performance characteristics, such as tensile / flexural properties and impact strength.

[0111] For the polyamide compositions described herein, the addition of impact modifiers is important because impact modifiers, such as olefins, acrylates or acryl compounds, or combinations thereof, contribute to the mechanical properties of the resulting articles, including elongation, impact strength and reduced modulus, such as extruded articles, profile extrusions, monofilaments or fibers, as desired in automotive and other applications. In contrast, polyamides for film applications do not include impact modifiers and are free or substantially free of impact modifiers.

[0112] Other additives

[0113] The polyamide composition may also include one or more chain terminators, viscosity modifiers, plasticizers, UV stabilizers, catalysts, other polymers, flame retardants, delustering agents, microbicides, antistatic agents, fluorescent whitening agents, extenders, processing aids, copper-containing compounds, and other commonly used additives known to those skilled in the art. Other suitable additives can be found in Plastics Additives, AZ Index, edited by Geoffrey Pritchard (1998). In an exemplary embodiment, a stabilizer is optionally added to the additive dispersion. Stabilizers suitable for additive dispersions include, but are not limited to: polyethoxylates (e.g., polyethoxylated alkylphenol Triton X-100), polypropoxylates, block copolymerized polyethers, long chain alcohols, polyols, alkyl sulfates, alkyl sulfonates, alkylbenzene sulfonates, alkyl phosphates, alkyl phosphonates, alkyl naphthalene sulfonates, carboxylic acids, and perfluorinated compounds. In particular, the polyamide composition described herein for non-membrane applications will include an amount of additional additives that are atypical and absent in the film composition. For example, the polyamide composition may include a plasticizer.

[0114] The concentration of the plasticizer in the polyamide composition can be, for example, in the range of 0.01 wt % to 10 wt %, such as 0.01 wt % to 0.1 wt %, 0.05 wt % to 0.2 wt %, 0.1 wt % to 0.3 wt %, 0.2 wt % to 0.4 wt %, 0.3 wt % to 0.5 wt %, 0.4 wt % to 0.6 wt %, or 0.5 wt % to 0.7 wt %, 0.1 to 1.0 wt %, 0.2 to 2.0 wt %, 0.3 to 3.0 wt %, 0.4 to 4.0 wt %, 0.5 to 5.0 wt %, 0.6 to 6.0 wt %, 0.7 to 7.0 wt %, 0.8 to 8.0 wt %, 0.9 to 9.0 wt %, 1.0 to 10 wt %,. In terms of upper limits, the concentration of the plasticizer can be less than 10 weight percent, e.g., less than 9.0 weight percent, less than 8.0 weight percent, less than 7.0 weight percent, less than 6.0 weight percent, less than 5.0 weight percent, less than 4.0 weight percent, less than 3.0 weight percent, less than 2.0 weight percent, less than 1.0 weight percent, less than 0.7 weight percent, less than 0.6 weight percent, less than 0.5 weight percent, less than 0.4 weight percent, less than 0.3 weight percent, less than 0.2 weight percent, less than 0.1 weight percent, less than 0.05 weight percent, less than 0.03 weight percent, or less than 0.02 weight percent. In terms of lower limits, the plasticizer can be greater than 0.01 wt%, such as greater than 0.02 wt%, greater than 0.03 wt%, greater than 0.05 wt%, greater than 0.1 wt%, greater than 0.2 wt%, greater than 0.3 wt%, greater than 0.4 wt%, greater than 0.5 wt%, greater than 0.6 wt%, greater than 0.7 wt%, greater than 0.8 wt%, greater than 0.9 wt%, greater than 1.0 wt%, greater than 2.0 wt%, greater than 3.0 wt%, greater than 4.0 wt%, greater than 5.0 wt%, greater than 6.0 wt%, greater than 7.0 wt%, greater than 8.0 wt%, or greater than 9.0 wt%. Higher concentrations, such as greater than 10 wt%, and lower concentrations, such as less than 0.01 wt%, are also contemplated. In these aspects, the concentration of the plasticizer in the polyamide composition is greater than 0.1 wt%.

[0115] The addition of plasticizers is important for the polyamide compositions described herein because plasticizers contribute to flow and thermal properties, such as lowering the glass transition temperature (Tg) of the resulting article. g ) and the elastic modulus, the resulting article is, for example, an extruded article, a profile extruded article, a monofilament or a fiber. In contrast, the polyamide used for film applications does not contain a plasticizer, and contains no or substantially no plasticizer.

[0116] In some embodiments, polyamide compositions for non-film applications may include amounts of additives, such as flow and leveling agents, that are atypical and absent in film compositions. These additives may be used for non-film applications, such as powder coating and 3D printing applications.

[0117] In some glass-filled or impact-modified compositions described herein, additives such as primary antioxidants and / or secondary antioxidants may be considered. Primary antioxidants include hindered phenols, and secondary antioxidants include those based on phosphorus. In some embodiments, copper-based heat stabilizers are added, depending on the application requirements.

[0118] In some embodiments, the stain resistance of the polyamide composition can be improved by salt-blending the polyamide precursor with a cationic dye modifier, such as 5-sulfoisophthalic acid or a salt or other derivative thereof.

[0119] Chain extenders may also be included in the polyamide composition. Suitable chain extender compounds include bis-N-acyl bislactam compounds, isophthaloyl biscaprolactam (IBC), adipoyl biscaprolactam (ABC), terephthaloyl biscaprolactam (TBS), and mixtures thereof.

[0120] The polyamide composition may also include an anti-blocking agent. Inorganic solids, usually in the form of diatomaceous earth, represent a class of materials that can be added to the polyamide composition. Non-limiting examples include calcium carbonate, silicon dioxide, magnesium silicate, sodium silicate, aluminum silicate, potassium aluminum silicate, and silicon dioxide is an example of a suitable anti-blocking agent.

[0121] The polyamide composition may also include a nucleating agent to further improve transparency and oxygen barrier properties and improve oxygen barrier properties. Typically, these agents are insoluble, high melting point substances that provide a surface for forming crystallites. By introducing a nucleating agent, more crystals are formed, which are smaller in nature. More crystallites or a higher percentage of crystallinity are associated with more reinforcement / higher tensile strength, and more tortuous oxygen flow paths (increased barrier); smaller crystallites reduce light scattering, which is associated with improved transparency. Non-limiting examples include calcium fluoride, calcium carbonate, talc, and nylon 2,2.

[0122] The polyamide composition may also contain organic antioxidants in the form of hindered phenols, such as, but not limited to, Irganox 1010, Irganox 1076 and Irganox 1098; organic phosphites, such as, but not limited to, Irgafos 168 and Ultranox 626; aromatic amines, metal salts from Groups IB, IIB, III and IV of the Periodic Table, and metal halides of alkali metals and alkaline earth metals.

[0123] It is contemplated that some or all of these components may be used optionally. In some cases, the composition may explicitly exclude one or more of the above components, such as by excluding them through the language of the claims. For example, the language of the claims may be modified to state that the composition, method, etc. does not use or contain one or more of the above additives.

[0124] Mechanical properties

[0125] The polyamide composition can exhibit, for example, a tensile modulus in the range of 650 MPa to 2500 MPa, for example 650 MPa to 850 MPa, 650 MPa to 1050 MPa, 650 MPa to 1250 MPa, 650 MPa to 1500 MPa, 650 MPa to 1750 MPa, 650 MPa to 1950 MPa, 650 MPa to 2000 MPa, 650 MPa to 2250 MPa, 850 MPa to 1 050MPa, 850MPa to 1250MPa, 850MPa to 1500MPa, 850MPa to 1750MPa, 850MPa to 1950MPa, 850MPa to 2000MPa, 850MPa to 2250MPa, 850MPa to 2500MPa, 1050MPa to 1250MPa, 1050MPa to 1500MPa, 1050MPa to 1750MPa, 1050MPa a to 1950MPa, 1050MPa to 2000MPa, 1050MPa to 2250MPa, 1050MPa to 2500MPa, 1250MPa to 1500MPa, 1250MPa to 1750MPa, 1250MPa to 1950MPa, 1250MPa to 2000MPa, 1250MPa to 2250MPa, 1250 to 2500MPa, 1500MPa to 1750MPa In some embodiments, the tensile modulus may be less than 2500 MPa, such as less than 2250 MPa, less than 2000 MPa, less than 1950 MPa, less than 1750 MPa, less than 1500 MPa, less than 1250 MPa, less than 1050 MPa, or less than 850 MPa. In terms of lower limits, the tensile modulus can be greater than 650 MPa, such as greater than 850 MPa, greater than 1050 MPa, greater than 1250 MPa, greater than 1500 MPa, greater than 1750 MPa, greater than 1950 MPa, greater than 2000 MPa, or greater than 2250 MPa. Higher tensile moduli, such as greater than 2500 MPa, and lower tensile moduli, such as less than 650 MPa, are also contemplated. The tensile modulus of the polyamide composition can be measured using standard methods such as ISO 527-1 (2019).

[0126] The polyamide composition can exhibit, for example, a tensile strength at break in the range of 35 MPa to 75 MPa, for example, 35 MPa to 45 MPa, 40 MPa to 50 MPa, 45 MPa to 55 MPa, 50 MPa to 60 MPa, 55 MPa to 65 MPa, 60 MPa to 70 MPa, or 65 MPa to 75 MPa. In terms of upper limits, the tensile strength at break can be less than 75 MPa, for example, less than 70 MPa, less than 65 MPa, less than 60 MPa, less than 55 MPa, less than 50 MPa, less than 45 MPa, or less than 40 MPa. In terms of lower limits, the tensile strength at break can be greater than 35 MPa, for example, greater than 40 MPa, greater than 45 MPa, greater than 50 MPa, greater than 55 MPa, greater than 60 MPa, greater than 65 MPa, or greater than 70 MPa. Higher tensile strengths, for example, greater than 75 MPa, and lower tensile strengths, for example, less than 35 MPa are also contemplated. The tensile strength at break of the polyamide composition can be tested using standard methods such as ISO 527-1 (2019).

[0127] The polyamide composition can exhibit, for example, an elongation at break (stretch) in the range of 15 to 350%, for example 15 to 35%, 25 to 45%, 35 to 55%, 45 to 65%, 55 to 75%, 65 to 85%, 75 to 95%, 85 to 105%, 100 to 150%, 125 to 175%, 150 to 200%, 175 to 225%, 200 to 250%, 225 to 275%, 250 to 300%, 275 to 325%, or 300 to 350%. In terms of upper limits, the elongation at break may be less than 350%, such as less than 325%, less than 300%, less than 275%, less than 250%, less than 225%, less than 200%, less than 175%, less than 150%, less than 125%, less than 105%, less than 100%, less than 95%, less than 85%, less than 75%, less than 65%, less than 55%, less than 45%, less than 35%, or less than 25. In terms of lower limits, the elongation at break may be greater than 15%, such as greater than 25%, greater than 35%, greater than 45%, greater than 55%, greater than 65%, greater than 75%, greater than 85%, greater than 95%, greater than 100%, greater than 105%, greater than 125%, greater than 150%, greater than 175%, greater than 200%, greater than 225%, greater than 250%, greater than 275%, greater than 300%, or greater than 325. Greater elongations, such as greater than 350%, and lesser elongations, such as less than 15%, are also contemplated. The elongation at break of the polyamide composition can be measured using a standard method such as ISO 527-1 (2019).

[0128] The polyamide composition can show a Charpy notched impact energy consumption at 23°C, for example, at 3 kJ / m 2 Up to 17 kJ / m 2 In the range of, for example, 3kJ / m 2 Up to 5kJ / m 2 , 3.5kJ / m 2 Up to 5.5 kJ / m 2 , 4kJ / m 2 Up to 6kJ / m 2 , 4.5kJ / m 2 Up to 6.5 kJ / m 2 , 5kJ / m 2 Up to 7 kJ / m 2 , 6kJ / m 2 Up to 8kJ / m 2 , 7kJ / m 2 Up to 9kJ / m 2 , 8kJ / m 2 Up to 10kJ / m 2 , 9kJ / m 2 Up to 11kJ / m 2 , 10kJ / m 2 Up to 12kJ / m 2 , 11kJ / m 2 Up to 13kJ / m 2 , 12kJ / m 2 Up to 14kJ / m 2 , 13kJ / m 2 Up to 15kJ / m 2 , 14kJ / m 2 Up to 16kJ / m 2 , or 15 kJ / m 2 Up to 17 kJ / m 2 As for the upper limit, the Charpy notch impact energy consumption at 23°C can be less than 17 kJ / m 2 , for example, less than 16 kJ / m 2 , less than 15kJ / m 2 , less than 14kJ / m 2 , less than 13kJ / m 2 , less than 12kJ / m 2 , less than 11kJ / m 2 , less than 10kJ / m 2 , less than 9kJ / m 2 , less than 8kJ / m 2 , less than 7kJ / m 2 , less than 6kJ / m 2 , less than 5kJ / m 2 , less than 4.5kJ / m 2 , less than 4kJ / m2 , or less than 3.5 kJ / m 2 As for the lower limit, the Charpy notch impact energy consumption at 23°C can be greater than 3 kJ / m 2 , for example, greater than 4 kJ / m 2 , greater than 5kJ / m 2 , greater than 6kJ / m 2 , greater than 7kJ / m 2 , greater than 8kJ / m 2 , greater than 9kJ / m 2 , greater than 10kJ / m 2 , greater than 11kJ / m 2 , greater than 12kJ / m 2 , greater than 13kJ / m 2 , greater than 14kJ / m 2 , greater than 15kJ / m 2 , or greater than 16kJ / m 2 Higher Charpy impact energy consumption is also considered, for example, greater than 17 kJ / m 2 , and lower Charpy impact energy consumption, such as less than 3kJ / m 2 The Charpy notched impact energy of the polyamide composition can be measured using a standard method such as ISO 179-1 (2010).

[0129] The polyamide composition can exhibit, for example, a moisture absorption at 95% RH of 0 wt % to 2 wt % moisture, such as 0 wt % to 0.2 wt %, 0.1 wt % to 0.3 wt %, 0.2 wt % to 0.4 wt %, 0.3 wt % to 0.5 wt %, 0.4 wt % to 0.6 wt %, 0.5 wt % to 0.7 wt %, 0.6 wt % to 0.8 wt %, 0.9 wt % to 1.1 wt %, 1.0 wt % to 1.2 wt %, 1.1 wt % to 1.3 wt %, 1.2 wt % to 1.4 wt %, 1.3 wt % to 1.5 wt %, 1.4 wt % to 1.6 wt %, 1.5 wt % to 1.7 wt %, 1.6 wt % to 1.8 wt %, 1.7 wt % to 1.9 wt %, or 1.8 wt % to 2.0 wt %. In terms of an upper limit, the moisture absorption rate at 95% RH can be less than 2.0 wt % moisture, for example, less than 1.9 wt %, less than 1.8 wt %, less than 1.7 wt %, less than 1.6 wt %, less than 1.5 wt %, less than 1.4 wt %, less than 1.3 wt %, less than 1.2 wt %, less than 1.1 wt %, less than 1.0 wt %, less than 0.9 wt %, less than 0.8 wt %, less than 0.7 wt %, less than 0.6 wt %, less than 0.5 wt %, less than 0.4 wt %, less than 0.3 wt %, less than 0.2 wt %, or less than 0.1 wt %. In terms of lower limits, the moisture absorption at 95% RH can be greater than 0% water, such as greater than 0.1 wt%, greater than 0.2 wt%, greater than 0.3 wt%, greater than 0.4 wt%, greater than 0.5 wt%, greater than 0.6 wt%, greater than 0.7 wt%, greater than 0.8 wt%, greater than 0.9 wt%, greater than 1.0 wt%, greater than 1.1 wt%, greater than 1.2 wt%, greater than 1.3 wt%, greater than 1.4 wt%, greater than 1.5 wt%, greater than 1.6 wt%, greater than 1.7 wt%, greater than 1.8 wt%, or greater than 1.9 wt%. Larger moisture absorptions, such as greater than 2.0 wt% water at 95% RH, are also contemplated. The moisture absorption of the polyamide composition can be tested using standard methods such as ISO 62:2008, which is used to test the moisture absorption of pellets or parts in a controlled environment.

[0130] The polyamide composition can exhibit chemical resistance, resistance to various acids, bases, solvents, etc., as demonstrated by, for example, evaluating swelling, dissolution, weight loss, and other properties. The polyamide composition can exhibit wear resistance, for example, greater than or equal to the wear resistance of PA6,12 and / or PA12.

[0131] Preferred composition

[0132] In one embodiment, the polyamide composition comprises PA6,12, the dimer modifier is a dimeramine present in an amount of 15 wt% to 50 wt%, wherein the polyamide composition exhibits a tensile elongation of at least 50%, a chemical resistance such as measured by exposure to HCl (10%) at 58°C for 14 days resulting in a weight loss of less than 0.8 wt%, and a moisture absorption at 95% RH of less than about 2.0 wt% of moisture. The amount of PA6,12 present may range from 50 wt% to 85 wt%.

[0133] In one embodiment, the polyamide polymer composition comprises PA6,12, the dimer modifier is a dimer acid present in an amount of 15 wt% to 50 wt%, wherein the polyamide composition exhibits a tensile elongation of at least 20%, a chemical resistance such as measured by exposure to HCl (10%) at 58°C for 14 days resulting in a weight loss of less than 0.8 wt%, and a moisture absorption at 95% RH of less than about 2.0 wt% of moisture. The amount of PA6,12 present may range from 50 wt% to 85 wt%.

[0134] In one embodiment, the polyamide polymer composition comprises PA6,12, the dimer modifier is a dimeramine present in an amount of 35 wt % to 55 wt %, wherein the polyamide composition exhibits a notched Charpy impact energy consumption at 23° C. of greater than 4.5 kJ / m 2 , chemical resistance as measured by exposure to HCl (10%) at 58°C for 14 days results in a weight loss of less than 2.8 wt%, and a moisture absorption rate of less than about 2.0 wt% moisture at 95% RH. PA6,12 may be present in an amount ranging from 45 wt% to 65 wt%.

[0135] In one embodiment, the polyamide polymer composition comprises PA6,12, the dimer modifier is present in an amount of about 20 wt%, wherein the polyamide composition exhibits a notched Charpy impact energy consumption at 23°C of greater than 3.5 kJ / m 2 , a tensile strength of greater than 50 MPa, a tensile modulus of greater than 1950 MPa, a chemical resistance such as tested by exposure to HCl (10%) at 58°C for 14 days resulting in a weight loss of less than 2.8 wt%, and a moisture absorption rate of less than about 2.0 wt% of water at 95% RH. The PA6,12 may be present in an amount of about 80 wt%.

[0136] Preparation method

[0137] This article also relates to a method for preparing the polyamide composition. This method includes providing one or more polyamide polymers, a modifier comprising dimer acid or dimeramine or a combination thereof, and optionally glass fiber, mineral filler, impact modifier and one or more heat stabilizers or other additives. This method may further include selecting the type and relative amount of one or more polyamide polymers and the modifier comprising dimer acid or dimeramine or a combination thereof, thereby providing the required chemical resistance, reduced water absorption and mechanical properties to the resulting polyamide composition. This method also includes merging one or more polyamide polymers and the modifier comprising dimer acid or dimeramine or a combination thereof, thus preparing the polyamide composition. In some embodiments, this method also includes selecting, providing and / or combining one or more dyes such as aniline black, one or more pigments such as carbon black, one or more mineral fillers and / or one or more melt stabilizers / lubricants.

[0138] The components of the polyamide composition can be mixed and blended together to prepare the polyamide composition, or suitable reactants can be used to synthesize on site. Without further explanation, the term "addition" or "merging" includes adding the material itself to the composition, or the material formed in situ in the composition. In some embodiments, a high solid content method is used to prepare the polyamide composition from each component, rather than preparing from various aqueous salts. The solid content of the first solution containing the polymer component is greater than 80%. Then, this solution can be evaporated in an evaporator. The modifier can bypass the evaporator and then be added to form a single mixture. The modifier comprises dimer acid or dimer amine or a combination thereof, wherein the modifier comprises 18-44 carbon atoms. When using a hydrogenated dimer material with high hydrophobicity, such as hydrogenated dimer acid or hydrogenated dimer amine, the high solid content method is advantageous.

[0139] In other embodiments, suitable for pilot, scale production or industrial operation, the water-soluble nylon salt (e.g., PA6,6, PA6,10, PA6,12, etc.) is further processed by an evaporation step to increase the solid content from an initial range of 40% to 50% by weight to a range of 75% to 90% by weight. After evaporation, the salt is then pumped into a reactor and combined with a hydrogenation modifier, such as a hydrogenated dimer acid or a hydrogenated dimer amine. The temperature in this container is then raised to a temperature in the range of 220°C to 270°C at a pressure in the range of 185psia to 270psia. The pressure is then reduced to atmospheric pressure within 30 minutes to 90 minutes, while the temperature is maintained between 250°C and 270°C. After the pressure reaches atmospheric pressure, finishing is then carried out at atmospheric pressure or vacuum. When a vacuum is applied, the pressure is in the range of 2psia to 10psia. The finishing time can be in the range of 10 minutes to 60 minutes, depending on the desired viscosity / molecular weight. After conditioning, nitrogen head pressure was applied and the molten polymer was extruded through an annular die, immersed in water in a strand tray, and sent to a strand pelletizer. After pelletization, surface moisture was removed from the pellets in a rotary dryer, and residual heat and air were removed; these pellets were collected in a foil-lined container.

[0140] In another embodiment, two or more materials to be combined with the composition are added simultaneously via a masterbatch.

[0141] Molded products

[0142] The present invention also relates to articles comprising any of the polyamide compositions described herein. The articles can be produced, for example, by conventional injection molding, extrusion molding, blow molding, compression molding, compression molding, or gas-assisted molding techniques. Molding methods suitable for the compositions and articles described herein can be found in U.S. Patent Nos. 8,658,757; 4,707,513; 7,858,172; and 8,192,664, each of which is incorporated herein by reference in its entirety. Examples of articles that can be produced using the polyamide compositions described herein include those used in the following applications: electrical and electronic applications (e.g., but not limited to circuit breakers, terminal blocks, connectors, etc.), automotive applications (e.g., but not limited to air handling systems, radiator sump, fans, shrouds, etc.), furniture and appliance components, and wire positioning devices such as cable connectors.

[0143] In some embodiments, an injection molded article is provided comprising any of the polyamide compositions described herein. In other embodiments, an extruded article is provided comprising any of the polyamide compositions described herein, and may be a profile extrusion, a monofilament, or a fiber. Example

[0144] Examples 1-8 were prepared using the formulations shown in Table 2. Table 1 shows the dimer acid / amine content of Examples 1-8 and additional Examples 9-11, based on the total molecular weight of the repeating units of the dimer acid or dimeramine. For example, Example 1 has 20 wt% dimer acid repeating units, Example 5 has 10 wt% dimer acid repeating units and 10 wt% dimeramine repeating units. Examples 1-11 each have an M of less than 30,000 g / mol. n .

[0145]

[0146] Examples 1-8 were prepared by combining the components shown in Table 2 and mixing the mixture in an autoclave using a polymerization method, wherein the components were added to the reactor. The components were selected from the following molecular weights and available sources shown in parentheses: PA6,12 (100% solids, MW 346.5), hexamethylenediamine (50% aq, MW 116), dodecanedicarboxylic acid (MW 230, Acme Hardesty), dimer acid (MW 570, Pripol 1009, Croda), dimer diamine (MW 540, Priamine 1075, Croda), adipic acid (MW 146), phenolic antioxidant stabilizer (MW 531, 1098, Sigma Aldrich) and sodium hypophosphite (2 wt %) (MW 88). These additives were added to the melt. The target for each batch was 500 grams of solids. These example compositions were heated to 140°C to 160°C and then stirring was started at a pressure of 20psia to 45psia. The reactor vessel was then pressurized to 200-265psia while stirring and initial evaporation was observed. The pressure of 20-45psia was maintained until a temperature of 220°C to 250°C was reached, followed by a reduction in pressure over a period of 30 minutes ± 10%. As the pressure reached atmospheric conditions, the temperature was between 245°C and 265°C. After reaching atmospheric pressure, a vacuum was applied over a period of 30 minutes ± 10%, and the pressure was then maintained at 5psia ± 10%. The strands were then extruded over a period of 10 minutes to 30 minutes and granulated into a container under nitrogen (N2) protection.

[0147] All copolymer formulations were successfully prepared from the individual components (rather than from aqueous salts as in the pilot, scaled production or industrial process described above). This high solids process is important because the hydrogenated dimer material is highly hydrophobic. Therefore, in the initial batching as in the formulations that rely on aqueous salts, the presence of large amounts of water results in an inhomogeneous mixture, which results in impaired processing, particularly in the evaporation and pressure steps. In addition, stirring was avoided until the mixture temperature reached 140°C, which is above the melting point of dodecanedicarboxylic acid. Once this temperature is met, dodecanedicarboxylic acid dissolves the C36 monomer and a uniform reactive mixture of diamine, diacid and additives is obtained. The method used is highly reproducible, as shown in the data (e.g., melting points shown in Table 8). In addition, the high solids process was demonstrated to be a reliable method for various C36 modification levels within the dimer acid and / or dimeramine modification range as described herein.

[0148]

[0149] As described above, in Table 1, the percentages of dimer acid and / or dimeramine used for Examples 1-8 are expressed based on the total molecular weight of the repeating units of the dimer acid or dimeramine. The actual amount of pure dimer acid and / or dimeramine used in the preparation of the corresponding polyamide is lower. For example, 20% dimer acid repeating units are used in Example 1 and 45% dimer acid repeating units are used in Example 2, and the actual percentages of dimer acid used in the preparation are about 12.1% by weight and about 28.6% by weight of the polymer as shown in Table 2, respectively. Example 4A has the same dimer acid percentage as Example 4, except that adipic acid is not used in the formulation of Example 4A. Similarly, Example 8 has the same dimer acid and dimeramine percentages as Example 7, except that adipic acid is not used in the formulation of Example 7A. The properties of the polyamide can be designed by varying the amount of dimer acid and / or dimeramine introduced into the polyamide. For example, by introducing more dimer acid and / or dimer amine, a more flexible material with higher toughness (with lower modulus), a material with improved impact resistance and elongation at break can be obtained.

[0150] As shown in Tables 3 to 5, dimer acid and / or dimer diamine react into PA6,12 to provide properties such as tensile strength, modulus, elongation, impact strength, chemical resistance and moisture absorption, thereby obtaining a hybrid system with a balance of properties. Unmodified PA6,12 and unmodified PA12 are provided as comparative examples. It is believed that this approach produces a hybrid system with properties associated with a performance spectrum between the properties of PA6,12 and PA12.

[0151] Comparative Examples include Comparative Example A (PA6,12, but without dimer) and Comparative Example B (PA12, but without dimer).

[0152] Examples 9-11 were also prepared in a similar manner to the formulations of Examples 1-8 as shown in Table 2, wherein the dimer modifier was reacted into PA6,12 to provide the corresponding examples. Example 9 contained 15 wt% of dimer acid repeating units, Example 10 contained 35 wt% of dimer acid repeating units, and Example 11 contained 35 wt% of dimeramine repeating units.

[0153] Table 3 shows the comparison results between Example 2 containing 45 wt% dimer acid, Example 9 containing 15 wt% dimer acid and Comparative Example B. The equilibrium moisture absorption rate of Example 2 at 23°C and 50% RH is comparable to that of Comparative Example B (unmodified PA12), and Example 2 advantageously has a higher melting point than the unmodified PA12 polyamide. As also shown in Table 3, the tensile strength and tensile modulus of Example 9 containing 15 wt% dimer acid are greater than those of Comparative Example B (unmodified PA12), and Example 9 also advantageously has a higher melting temperature than the unmodified PA12 polyamide.

[0154]

[0155] Referring to Table 4, data on tensile strength, tensile modulus, elongation, impact strength, and melting point for Examples 1-4, 10, and 11 and Comparative Examples A and B are provided.

[0156]

[0157] As shown in Table 4, Example 1 exhibits similar tensile strength as Comparative Example A. Advantageously, improved chemical and moisture resistance was also observed during testing, see discussion below. Example 10 produced a material having similar tensile strength as Comparative Example B, but additionally having improved temperature resistance. Dimer acid modification has less effect on tensile strength than dimeramine modification. It is believed that dimeramine is more evenly distributed within the polymer chain, thereby affecting crystallinity and thus tensile strength.

[0158] As also shown in Table 4, the tensile modulus and elongation of Examples 1-4, 10 and 11, measured directly out of the reactor, can be designed to have a tensile modulus of about 650-2200 MPa and an elongation of about 15-100% (or up to 300% or more), respectively, by modifying the backbone. In other words, dimer content can be used as a compositional variable to adjust the desired properties. Advantageously, Example 4 was found to be quite flexible at a tensile modulus of about 650 MPa, which should also meet the modulus requirements for plasticized or reinforced PA6,12 applications. Example 4 also shows better impact resistance and elongation than PA12.

[0159] The tensile elongation requirement can also be designed by adjusting the type of comonomer and the amount of dimer modifier. In some cases, dimeramines affect tensile modulus and elongation more significantly than dimer acids. It is believed that dimeramines have a more pronounced effect on elongation due to the uniform distribution affecting crystallinity.

[0160] Referring again to Table 4, the polyamide composition samples containing dimer acid and / or dimeramine exhibit greater impact strength than Comparative Examples A and B. Example 4 is particularly good and exhibits even better impact strength than the other working examples, e.g., at least 3 times that of Examples 1, 2, 3, 10, and 11, and better than Comparative Examples A and B.

[0161] The chemical resistance data of Examples 1-4, which were introduced with dimer repeating units as described above, are summarized in Table 5. Chemical resistance can be tested by evaluating the weight gain / loss of various formulations after exposure to various acids, bases and solvents. Comparative Examples A and B are used for comparison; the unmodified PA12 reference material is Grilamid L 25A NZ (EMS-GRIVORY). Experiments with chemical agents include exposing Examples 1-4, Comparative Examples A and Comparative Examples B to each of the following chemical agents: exposure to HCl (10%) at 58°C for 14 days; exposure to H2SO4 (38%) at room temperature for 1 day; and exposure to methanol at room temperature for 7 days.

[0162] The data in Table 5 indicate the percentage of weight loss resulting from exposure over a defined period of time, wherein a smaller weight loss indicates a higher chemical resistance. The weight loss of each of Examples 1-4 was less than that of Comparative Example B in the case of exposure to HCl (10%) at 58°C for 14 days, indicating excellent chemical resistance. Even when compared to Examples 3 and 4, in which diamine was introduced, Examples 1 and 2 showed particularly improved resistance to HCl. The polyamides of Examples 1-4 were generally incompatible in the case of exposure to H2SO4 (38%) at room temperature for 1 day, indicating that this medium swelled, attacked or dissolved the polyamide samples. The data in Table 5 also indicate that Examples 1-4 have chemical resistance to methanol that is as good or better than Comparative Example B.

[0163]

[0164] Referring to Table 6, PA6,6 was reacted with a modifier comprising a dimer acid and / or a dimer amine to provide Example 12 comprising 10 wt% dimer acid repeating units, Example 13 comprising 20 wt% dimer acid repeating units, and Example 14 comprising 20 wt% dimer amine repeating units. It was observed that the introduction of the dimer into PA6,6 provided improved toughness and chemical resistance while maintaining thermal properties.

[0165]

[0166] The performance data of Example 1 and Example 4 are summarized in Table 7. Table 7 also shows the data of Comparative Example A and Comparative Example B. These results show that the polyamide compositions described herein can be modified to introduce different amounts of dimer acid or dimer amine and combinations thereof to tailor mechanical properties, improve chemical resistance and simultaneously reduce moisture absorption. Example 1 provides thermal and mechanical properties similar to unmodified PA6,12 and can be suitable for applications requiring high strength, stiffness and temperature resistance, and provides the additional benefits of reduced moisture absorption and improved chemical resistance. Modification of PA6,12 with, for example, dimer amine (Example 4) can provide improved softness / flexibility and can be suitable for a wide range of applications requiring high flexibility and toughness, such as for pipes, powder coatings, etc.

[0167]

[0168] Then, Examples 1-8 were subjected to thermal analysis, moisture absorption analysis, and Taber abrasion analysis.

[0169] The pellets prepared from the 2L container were thermally analyzed to determine T m (MTPT) and T c (REXC) Dynamic mechanical analysis (DMA) was performed using samples obtained by compression molding using a TA Q800 DMA in tensile mode with a temperature sweep from 50°C to 200°C at a frequency of 1 Hz and a heating rate of 3°C / min.

[0170] The bars obtained by compression molding were used to test the tensile properties according to ISO 527-2 and the notched Charpy impact properties according to ISO 179 / 1eA.

[0171] The samples were analyzed for moisture absorption. This analysis was performed using a Vapor Sorption analyzer from TA Instruments. The maximum moisture absorption was measured at 23°C, 50% RH and at 23°C, 95% RH.

[0172] Taber abrasion analysis was performed using sheets made by compression molding with a thickness of 3 mm. This test was performed using a 5130 Abraser and a CS-17 Calibrase grinding wheel, which was connected to a vacuum for vacuum sealing. The sample was prepared by wiping it clean with isopropyl alcohol and conditioning it at 50% + 10% humidity and 23°C + 2°C for 40 hours, and then weighed with a balance in this humidity and temperature controlled environment. The sample was stored in this environment before and after the test. The grinding wheel was conditioned with an abraser polishing disc (Abraser Refacing Discs) before the test and after each subsequent sample was tested. These discs were loaded and run for 50 cycles. Once completed, the polished turntable was discarded and the rest of the grinding wheel polishing was vacuumed before loading the sample. The sample was run for 1000 revolutions with a 1 kg weight. The sample was placed in a humidity and temperature controlled environment for a minimum of 40 hours and then weighed again to detect weight loss.

[0173]

[0174] The data of Examples 1-4 and 8 collected from multiple samples are shown in Table 8. As shown in Table 8, Examples 1-8 have melting points in the range of 172°C-213°C, which are close to the lower and upper limits of unmodified PA12 and PA6,12, respectively. It is observed that the melting point decreases as the amount of hydrogenated dimer acid or hydrogenated dimeramine added increases. In addition, the system containing hydrogenated dimeramine has a significantly greater degree of melting point depression than the case of dimer acid. The extrusion pressure is consistent with the standard viscosity of PA6,12 homopolymer (e.g., VNs ~ 110-130 mL / g), so the desired molecular weight is achieved.

[0175] From the results shown in Table 8, it is clear that C 36 Diacid and C 36 Effect of diamine on melting point. 36The diacids maintained a melting point equal to or greater than 200°C, even in the case of a dimer acid incorporation ratio of 45% as shown in Example 2. At this point, the ratio between methyl and amide groups essentially matches that of PA12, but the melting point of Example 2 is about 25°C higher than that of PA12. In addition, dimeramine modification was performed with and without a stoichiometric balance of adipic acid in Examples 4 and 4A, respectively. Compared to the case of simply using additional dodecanedicarboxylic acid to balance the C36 diamine in Example 4A, a significantly lower melting point of 174°C on average was detected in the case of adipic acid in excess of the C36 diamine functionality in Example 4. The reason for this difference is that the complexity of the backbone increases when adipic acid is added to the system; in this case, there are two diamines (HMD and C36 diamine) and two diacids (adipic acid and dodecanedicarboxylic acid). This is considered equivalent to the presence of four monomers, and results in four potential repeating units (6,12; 6,36; 36,6; and 36,12), thus forming a tetrapolymer. This backbone complexity prevents crystallization to a greater extent than a system with two possible repeating units (e.g., Example 4 could include 6,12 and 36,12 repeating units).

[0176]

[0177] As shown in Table 9, based on the dimer monomer type and dimer monomer concentration in the final polymer, these copolymers can be designed to have T values ​​in the range of 170-220°C and 25-60°C, respectively. m or T g (e.g. in the range between the melting points of PA12 and PA6,12). Moreover, the crystallization temperature can vary significantly depending on the type and concentration of the dimer monomer. High concentrations of dimer acid or dimer amine in the polymer show significantly lower T c This translates into a slower crystallization rate, which is an advantageous feature for applications such as powder coatings and 3D printing. It should be noted that the PA6,12+20% dimer acid formulation of Example 1 has a T value similar to that of PA6,12 (Comparative Example A). m and T c Therefore, the formulation of Example 1 will be processed in a very similar manner to PA6,12 by injection molding. For example, the formulation of Example 1 will have similar processing conditions and cycle times as PA6,12, while having performance advantages such as improved moisture and chemical resistance.

[0178] Figure 1The storage modulus obtained from DMA analysis is shown as a function of temperature. Curve 100 shows the copolymer compositions of Examples 1, 2, 3, 4 and 6 compared to Comparative Example A (PA6,12) and Comparative Example B (PA12). These data show that the storage modulus can be designed to match or exceed the storage modulus of monomeric PA6,12 or PA12. Higher amounts of dimer acid or dimeramine yield polymers with lower storage moduli in the temperature range of -50 to 150°C, represented by unit 110, as shown for Examples 2 and 4 and Comparative Example A (PA6,12) and Comparative Example B (PA12). At elevated temperatures (e.g., above 150°C as shown by unit 120), Examples 1, 2, 3 and 6 maintain a higher storage modulus than Comparative Example B (PA12), which is believed to allow these copolymers to have a higher service life or use temperature than PA12.

[0179] The glass transition T detected using DMA analysis is also depicted. g Temperature, shown as the peak value of Tanδ as it changes with temperature, such as Figure 2 As shown in the curve 200 in . Compared with comparative example A (PA6,12) and comparative example B (PA12), examples 1, 2, 3, 4 and 6 show a broader α transition (glass transition) and a higher peak intensity, thereby demonstrating that examples 1, 2, 3, 4 and 6 have improved damping properties and toughness.

[0180] The results of moisture absorption rate are as follows Figure 3 and Table 10. Graph 300 shows the moisture absorption of Examples 1 and 2 and Comparative Examples A (PA6,12) and Comparative Example B (PA12) at 23°C and 95% RH (shown by patterned bars) and at 23°C and 50% RH (shown by solid bars). Table 10 shows the values ​​set for the same data. Figure 3 Table 10 shows that Examples 1 and 2 have excellent moisture resistance. In the case of adding 20% ​​dimer acid to PA6,12 in Example 1, this result demonstrates that this copolymer has the same moisture resistance as PA12. It is believed that the dimer phase of these copolymers can reach the skin (or toward the surface) of the molded article, and the hydrophobicity of the dimer phase then provides the copolymer with an excellent moisture barrier effect. In addition, in the case of Comparative Example B (PA12) having an equal methyl / amide ratio to Example 2, Example 2 shows an even lower moisture absorption rate. This property is attractive for many applications requiring high dimensional stability and moisture inertness for mechanical properties, such as but not limited to flexible pipes, natural gas pipelines, and powder coatings.

[0181]

[0182] Figure 4The samples analyzed by Taber testing all showed excellent wear resistance, such as less than 0.1% weight loss. Wear resistance is related to the percentage crystallinity of the material, where the higher the crystallinity, the better the wear resistance. The comparative example (PA6,12) showed the best wear resistance (lowest % weight loss) because it had the highest percentage crystallinity. Moreover, Example 1, which introduced 20% dimer acid, showed slightly better wear resistance than comparative example B (PA12). Advantageously, the Taber test showed that all polyamides tested had high wear resistance, resulting in a weight loss of less than 1000 ppm. Please note that the Taber test described herein uses a Calibrase grinding wheel that has the highest wear resistance in the Taber abrasion test. Further optimization through additives is considered to reduce the friction coefficient and / or increase the molecular weight.

[0183] The chemical resistance tested for different agents is summarized in Table 11. These results show that higher levels of dimer acid or amine modification lead to excellent resistance to acids, bases, salts, and polar (methanol) and non-polar (hexane) solvents. Specifically, Example 2, which incorporates 45% dimer acid, performs significantly better than PA12 in acid resistance in HCl, NaOH, and ZnCl2, while Example 4, which incorporates 45% dimeramine, has excellent reagent resistance, but is best in NaOH. Both Examples 2 and 4 perform better than Comparative Example A (PA6,12) in NaOH and ZnCl2. In addition, the examples with higher dimer acid or dimeramine content show better resistance to hydrocarbon solvents (hexane) than Comparative Example A or Comparative Example B.

[0184]

[0185] As described herein, modifying properties with dimer acid and / or dimer amine provides advantageous properties designed for a wide range of applications. Referring to Tables 4 and 7, mechanical properties can also be fully designed by adding dimer acid and / or dimer amine. For example, the tensile modulus can be designed to be from 700 MPa to 2200 MPa (as shown in Table 4) without adding any impact modifier or plasticizer in the auxiliary mixing step.

[0186] Higher amounts of dimer acid or dimer amine (e.g. 45% comonomer content in Examples 2 and 4) resulted in materials with low modulus. Those copolymers with the same higher dimer content also showed very high notched Charpy impact strength values, see for example Example 4 in Table 4, where the average impact strength was 14.3 kJ / m 2. Embodiments with higher levels of dimer acid and / or dimer amine modifiers provide toughness and flexibility while also providing excellent chemical and moisture resistance, making them suitable for applications such as pipes and 3D printing. These compositions demonstrate that, for example, the addition of dimer modifiers to PA-6,12 can provide copolymers with moisture absorption rates that are advantageously even less than that of PA12. PA12 is known to be expensive and complex to prepare. This meets a long-standing industry need to provide an alternative to PA12 that provides a moisture inert material with stable mechanical properties and dimensional stability, even better than PA-12 compositions.

[0187] As good or even better performance than PA6,12 is obtained with lower amounts of dimer acid or dimeramine (e.g. 20% comonomer content in Examples 1 or 3) (and with lower production costs), and similar tensile properties as PA6,12 are advantageously maintained, but with higher toughness as shown in Table 4. The embodiments with lower levels of dimer acid and / or dimeramine modifiers are able to provide excellent moisture and chemical resistance comparable to PA12, and provide an overall balance of properties suitable for a wide range of applications.

[0188] Implementation

[0189] Consider the following embodiments. All combinations of these features and embodiments are contemplated.

[0190] Embodiment 1: A polyamide composition comprising: 45 wt% to 95 wt% of a polyamide polymer; 5 wt% to 55 wt% of a modifier comprising a dimer acid or a dimeramine or a combination thereof; wherein the polyamide composition exhibits: a chemical resistance as measured by exposure to HCl (10%) at 58°C for 14 days resulting in a weight loss of less than 3.0 wt%; and a moisture absorption at 95% RH of less than about 2.0 wt% moisture.

[0191] Embodiment 2: The embodiment according to embodiment 1, wherein the polyamide composition has a methyl / amide ratio in the range of 6:1 to 15:1.

[0192] Embodiment 3: The embodiment according to embodiment 1 or 2, wherein the polyamide composition has a methyl / amide ratio in the range of 9:1 to 15:1.

[0193] Embodiment 4: The embodiment according to any one of embodiments 1-3, wherein the polyamide composition comprises 20 wt% to 45 wt% of a modifier comprising a dimer acid or a dimeramine or a combination thereof.

[0194] Embodiment 5: The embodiment according to any one of embodiments 1-4, wherein the polyamide composition exhibits a moisture absorption at 95% RH of less than about 1.6 wt% water.

[0195] Embodiment 6: The embodiment according to any one of embodiments 1-5, wherein the polyamide polymer comprises PA6, PA10, PA11, PA12, PA6,6, PA6,9, PA6,10, PA6,11, PA6,12, PA6,13, PA6,14, PA6,15, PA6,16, PA6,17, PA6,18, PA10,10, PA10,12, PA12,12, PA9T, PA10T, PA11T, PA12T, PA6T / 66, PA6T / 6I, PA6 T / 6I / 66, PA6T / DT, PA6,T / 6,10, PA6,T / 6,12, PA6,T / 6,13, PA6,T / 6,14, PA6,T / 6,15, PA6,T / 6,16, PA6,T / 6,17, PA6,T / 6,18, PA6,C / 6,10, PA6,C / 6,12, PA6,C / 6,13, PA6,C / 6,14, PA6,C / 6,15, PA6,C / 6,16, PA6,C / 6,17, PA6,C / 6,18, or combinations thereof.

[0196] Embodiment 7: An embodiment according to any one of embodiments 1-6, wherein the polyamide polymer comprises PA6,6.

[0197] Embodiment 8: An embodiment according to any one of embodiments 1-7, wherein the polyamide polymer comprises PA 6,10.

[0198] Embodiment 9: An embodiment according to any one of embodiments 1-8, wherein the polyamide polymer comprises PA 6,12.

[0199] Embodiment 10: An embodiment according to any of embodiments 1-9, wherein the polyamide polymer comprises PA6T / 66, PA6T / 6I, PA6T / 6I / 66, PA6T / DT, PA6,T / 6,10, PA6,T / 6,12, PA6,T / 6,13, PA6,T / 6,14, PA6,T / 6,15, PA6,T / 6,16, PA6,T / 6,17, PA6,T / 6,18, or a combination thereof.

[0200] Embodiment 11: The embodiment according to any one of embodiments 1-10, wherein the number average molecular weight of the polyamide polymer is in the range of 9,000 g / mol to 60,000 g / mol.

[0201] Embodiment 12: An embodiment according to any one of embodiments 1-11, wherein the number average molecular weight of the polyamide polymer is in the range of 20,000 g / mol to 45,000 g / mol.

[0202] Embodiment 13: An embodiment according to any one of embodiments 1-11, wherein the number average molecular weight of the polyamide polymer is in the range of 12,000 g / mol to 20,000 g / mol.

[0203] Embodiment 14: An embodiment according to any of embodiments 1-13, wherein the polyamide polymer has an amine end group content of 10 microequivalents / gram to 110 microequivalents / gram.

[0204] Embodiment 15: An embodiment according to any of embodiments 1-14, wherein the polyamide polymer has an amine end group content of 35 microequivalents / gram to 80 microequivalents / gram.

[0205] Embodiment 16: The embodiment according to any one of embodiments 1-15, further comprising up to 60 wt% glass fibers.

[0206] Embodiment 17: The embodiment according to any one of embodiments 1-16, further comprising up to 2 wt % of a lubricant.

[0207] Embodiment 18: The embodiment according to any one of embodiments 1-17, further comprising an additive selected from nigrosine dye, a copper-containing compound, a plasticizer or a flame retardant or a combination thereof.

[0208] Embodiment 19: The embodiment according to any one of embodiments 1-18, further comprising up to 30% by weight of a mineral additive selected from calcium carbonate, talc, magnesium hydroxide, kaolin clay or a combination thereof.

[0209] Embodiment 20: According to any one of embodiments 1-19, it also contains an impact modifier selected from the following: modified olefins, unmodified olefins, maleic anhydride modified olefins, olefins not modified by maleic anhydride, acrylates, or acryl compounds, or combinations thereof.

[0210] Embodiment 21: The embodiment of any of embodiments 1-20, wherein the polyamide polymer comprises PA 6,12, the dimer modifier is a dimeramine present in an amount of 15 wt% to 50 wt%, and wherein the polyamide composition exhibits a tensile elongation of at least 50%.

[0211] Embodiment 22: The embodiment of any of embodiments 1-21, wherein the polyamide polymer comprises PA 6,12, the dimer modifier is a dimer acid present in an amount of 15 wt% to 50 wt%, and wherein the polyamide composition exhibits a tensile elongation of at least 20%.

[0212] Embodiment 23: An embodiment according to any one of embodiments 1-22, wherein the polyamide polymer comprises PA6,12, the dimer modifier is a dimeramine present in an amount of 35 wt% to 55 wt%, and wherein the polyamide composition exhibits a notched Charpy impact energy consumption at 23°C of greater than 4.5 kJ / m 2 .

[0213] Embodiment 24: An embodiment according to any one of embodiments 1-23, wherein the polyamide polymer comprises PA6,12, the amount of the dimer modifier is about 20 wt%, and wherein the polyamide composition exhibits a notched Charpy impact energy consumption at 23°C of greater than 3.5 kJ / m 2 , the tensile strength is greater than 50MPa, and the tensile modulus is greater than 1950MPa.

[0214] Embodiment 25: An embodiment according to any one of embodiments 1-24, wherein the polyamide composition exhibits a tensile elongation greater than 30%.

[0215] Embodiment 26: An embodiment according to any one of embodiments 1-25, wherein the polyamide composition exhibits a notched Charpy impact energy consumption at 23°C of greater than 3 kJ / m 2 .

[0216] Embodiment 27: An embodiment according to any one of embodiments 1-26, wherein the polyamide composition exhibits a tensile modulus greater than 650 MPa.

[0217] Embodiment 28: An embodiment according to any of embodiments 1-27, wherein the polyamide composition has any of the above-described or subsequently described features, wherein the polyamide composition exhibits a tensile elongation greater than 13%.

[0218] Embodiment 29: The embodiment according to any one of embodiments 1 to 28, wherein the polyamide composition exhibits a wear resistance greater than that of a reference PA6,12 material or a reference PA12 material.

[0219] Embodiment 30: An injection molded article comprising the polyamide composition according to any one of Embodiments 1-29.

[0220] Embodiment 31: An article comprising the polyamide composition according to any one of Embodiments 1-29, wherein the article is an extruded article, a profile extruded article, a monofilament or a fiber.

[0221] Embodiment 32: An embodiment according to any one of embodiments 1-31, wherein the polyamide composition comprises 45 wt% to 95 wt% of a polyamide polymer; 5 wt% to 55 wt% of a polyamide polymer comprising C 18-44 Dimer acid or C 18-44 A modifier of a diamine or a combination thereof; wherein the polyamide composition has: a number average molecular weight of the polyamide polymer of less than 30,000 g / mol; a chemical resistance as measured by exposure to HCl (10%) at 58° C. for 14 days resulting in a weight loss of less than 3.0 wt %; and a moisture absorption at 95% RH of less than about 2.0 wt % moisture.

[0222] Embodiment 33: An embodiment according to any one of embodiments 1-32, wherein the polyamide polymer comprises PA10, PA11, PA12, PA6,6, PA6,9, PA6,10, PA6,11, PA6,12, PA6,13, PA6,14, PA6,15, PA6,16, PA6,17, PA6,18, PA10,10, PA10,12, PA12,12, PA9T, PA10T, PA11T, PA12T, PA6T / 66, PA6T / 6I, PA6T / 6I / 66, PA6T / DT, PA6,T / 6,10, PA6,T / 6,12, PA6,T / 6,13, PA6,T / 6,14, PA6,T / 6,15, PA6,T / 6,16, PA6,T / 6,17, PA6,T / 6,18, PA6,C / 6,10, PA6,C / 6,12, PA6,C / 6,13, PA6,C / 6,14, PA6,C / 6,15, PA6,C / 6,16, PA6,C / 6,17, or PA6,C / 6,18, or combinations thereof.

[0223] Embodiment 34: An embodiment according to any of embodiments 1-33, wherein the polyamide polymer comprises PA 6,10, PA 6,12 or a combination thereof.

[0224] Embodiment 35: An embodiment according to any one of embodiments 1-34, wherein the modifying agent is a single modifying agent comprising a single dimer acid or a single dimer amine.

[0225] Embodiment 36: An embodiment according to any of embodiments 1-35, wherein the polyamide composition has a melting temperature of 165°C to 270°C.

[0226] Embodiment 37: An embodiment according to any of embodiments 1-36, wherein the polyamide composition has a melting temperature of 170°C to 215°C.

[0227] Embodiment 38: An embodiment according to any one of embodiments 1-37, wherein the polyamide composition comprises 20 wt% to 45 wt% of a modifier comprising a dimer acid or a dimeramine or a combination thereof.

[0228] Embodiment 39: An embodiment according to any one of embodiments 1-38, wherein the number average molecular weight of the polyamide polymer is in the range of 10,000 g / mol to 25,000 g / mol.

[0229] Embodiment 40: An embodiment according to any of embodiments 1-39, wherein the polyamide polymer has an amine end group content of 10 microequivalents / gram to 110 microequivalents / gram, or wherein the polyamide polymer has an amine end group content of 35 microequivalents / gram to 80 microequivalents / gram.

[0230] Embodiment 41: An embodiment according to any of embodiments 1-40, wherein the polyamide composition comprises greater than 5 weight percent glass fibers.

[0231] Embodiment 42: An embodiment according to any one of embodiments 1-41, wherein the polyamide composition comprises greater than 0.3 wt% of a lubricant.

[0232] Embodiment 43: An embodiment according to any one of embodiments 1-42, wherein the polyamide composition comprises greater than 3 weight percent of an impact modifier.

[0233] Embodiment 44: The embodiment according to any one of embodiments 1-43, wherein the polyamide polymer comprises PA6,12, and the dimer modifier is present in an amount of 15 wt.% to 50 wt.%, wherein one of the following conditions is met: the dimer modifier is a single dimer amine, and the polyamide composition exhibits a tensile elongation of at least 50%; and the dimer modifier is a single dimer acid, and the polyamide composition exhibits a tensile elongation of at least 20%.

[0234] Embodiment 45: An embodiment according to any one of embodiments 1-44, wherein the polyamide polymer comprises PA6,12, the dimer modifier is a single diamine present in an amount of 35 wt% to 55 wt%, and wherein the polyamide composition exhibits a notched Charpy impact energy consumption at 23°C of greater than 4.5 kJ / m 2 .

[0235] Embodiment 46: An embodiment according to any one of embodiments 1-45, wherein the polyamide polymer comprises PA6,12, the amount of the dimer modifier is about 20 wt%, and wherein the polyamide composition exhibits a notched Charpy impact energy consumption at 23°C of greater than 3.5 kJ / m 2 , the tensile strength is greater than 50MPa, and the tensile modulus is greater than 1950MPa.

[0236] Embodiment 47: The molded article of any one of Embodiments 1-46, wherein the article comprises a polyamide composition comprising 45% to 95% by weight of a polyamide polymer and 5% to 55% by weight of a polyamide comprising C 18-44 Dimer acid or C 18-44 Modifiers of diamines or combinations thereof, wherein the molded article composition has the following characteristics: the number average molecular weight of the polyamide polymer is less than 30,000 g / mol; the chemical resistance tested by exposure to HCl (10%) at 58°C for 14 days results in a weight loss of less than 3.0 wt%; and the moisture absorption at 95% RH is less than about 2.0 wt% moisture.

[0237] Embodiment 48: A method according to any one of embodiments 1-47, wherein the method comprises preparing a high solids monomer solution in an aqueous salt, wherein the solids content is greater than 80%; evaporating the high solids monomer solution in an evaporator, wherein the initial concentration is greater than 60 wt %; and adding a 18-44 Dimer acid or C 18-44 A modifier of a diamine or a combination thereof to form a single mixture, wherein the modifier bypasses the evaporator; wherein the polyamide composition exhibits: chemical resistance tested by exposure to HCl (10%) at 58°C for 14 days resulting in a weight loss of less than 3.0 wt%; and a moisture absorption at 95% RH of less than about 2.0 wt% water.

[0238] Embodiment 49: An embodiment according to any of embodiments 1-48, wherein the polyamide polymer comprises PA 6,10, PA 6,12 or a combination thereof.

[0239] Embodiment 50: An embodiment according to any one of embodiments 1 and 49, wherein the modifier is a single modifier comprising a single C 18-44 Dimer acid or single C 18-44 Diamine.

[0240] Although the present invention has been described in detail, it is easy for those skilled in the art to understand modifications within the spirit and scope of the present invention. Considering the above discussion, the relevant knowledge in the art and the references discussed in connection with "background" and "detailed description" above, the disclosures thereof are all introduced herein for reference. In addition, it should be understood that the various aspects of the present invention and the parts of the various embodiments and the various features listed below and / or in the appended claims can be combined or interchanged in whole or in part. In the previous description of the various embodiments, those embodiments with reference to another embodiment can be appropriately combined with other embodiments as recognized by those skilled in the art. In addition, it will be understood by those of ordinary skill in the art that the above description is only used as an example and does not limit the scope of the present invention.

Claims

1. A polyamide composition comprising: 45 wt% to 95 wt% of an aliphatic polyamide polymer having a melting temperature of 170°C to 215°C, wherein the aliphatic polyamide polymer comprises greater than 50 wt% PA6,10, PA6,12, or a combination thereof; and 5 to 55 wt % of a modifier comprising C 18-44 Dimer acid or C 18-44 Diamine or a combination thereof; wherein the number average molecular weight of the polyamide polymer is less than 30,000 g / mol; The polyamide composition has: Melting temperature of 165°C to 270°C; Chemical resistance tested by exposure to HCl (10%) at 58°C for 14 days resulted in a weight loss of less than 3.0 wt%; Moisture absorption at 95% RH is less than 2.0 wt% water; and Methyl / amide ratios in the range of 9:1 to 15:

1.

2. The polyamide composition of claim 1, wherein the polyamide composition comprises a single modifier comprising a single dimer acid or a single dimer amine.

3. The polyamide composition of claim 1, wherein the polyamide composition comprises 20 wt% to 45 wt% of the modifier.

4. The polyamide composition of claim 1, wherein the number average molecular weight of the polyamide polymer is in the range of 10,000 g / mol to 25,000 g / mol.

5. The polyamide composition of claim 1, wherein the polyamide polymer has an amine end group content in the range of 10 microequivalents / gram to 110 microequivalents / gram.

6. The polyamide composition of claim 1, wherein the polyamide polymer has an amine end group content in the range of 35 microequivalents / gram to 80 microequivalents / gram.

7. The polyamide composition of claim 1, further comprising at least one of the following components: Glass fibers present in an amount greater than 5% by weight; a lubricant present in an amount greater than 0.3 wt. %; and The impact modifier is present in an amount greater than 3 weight percent.

8. The polyamide composition of claim 1, wherein the polyamide polymer comprises PA6,12, and the dimer modifier is present in an amount ranging from 15 wt % to 50 wt %, wherein one of the following conditions is met: The dimer modifier is a single diamine and the polyamide composition exhibits a tensile elongation of at least 50%; and The dimer modifier is a single dimer acid and the polyamide composition exhibits a tensile elongation of at least 20%.

9. The polyamide composition of claim 1, wherein the polyamide polymer comprises PA 6,12, the dimer modifier is a single dimeramine present in an amount of 35 wt % to 55 wt %, and wherein the polyamide composition exhibits a notched Charpy impact energy at 23° C. of greater than 4.5 kJ / m 2 .

10. The polyamide composition of claim 1, wherein the polyamide polymer comprises PA 6,12, the amount of the dimer modifier is about 20 wt%, and wherein the polyamide composition exhibits a notched Charpy impact energy at 23°C of greater than 3.5 kJ / m 2 , the tensile strength is greater than 50 MPa, and the tensile modulus is greater than 1950 MPa.

11. A molded or extruded article comprising: The polyamide composition according to claim 1.

12. A method for preparing a polyamide composition, comprising: Evaporating a water-soluble salt of PA6,10, PA6,12 or a combination thereof having an initial solids content of 40 to 50 wt% in an evaporator, wherein the evaporation increases the solids content to 75 to 90 wt% to form a high solids salt solution; and Will contain C 18-44 Dimer acid or C 18-44 A hydrogenated modifier of the dimeramine or combination thereof is added to a high solids salt solution in a reaction vessel to form a single mixture wherein the modifier bypasses an evaporator; heating the single mixture to a temperature in the range of 220° C. to 270° C. at a pressure in the range of 185 psia to 270 psia; Wherein the polyamide composition is an aliphatic polyamide polymer comprising greater than 50 wt.% of PA6,10, PA6,12 or a combination thereof, and exhibits the following characteristics: The number average molecular weight of the polyamide polymer is less than 30,000 g / mol; Chemical resistance tested by exposure to HCl (10%) at 58°C for 14 days resulted in a weight loss of less than 3.0 wt%; Moisture absorption at 95% RH is less than 2.0 wt% water; and Methyl / amide ratios in the range of 9:1 to 15:

1.

13. An extruded article comprising the polyamide composition as claimed in any one of claims 1 to 10.

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