Thermoplastic polymer composition with enhanced sag resistance

Abstract

The present disclosure relates generally to a thermoplastic polymer composition. The thermoplastic polymer composition may be particularly suited for blow molding applications. The thermoplastic polymer composition may include a first polyamide, a second polyamide, and a third polyamide.

Description

Related applications

[0001] This application is based on and claims priority to U.S. Provisional Patent Application Serial No. 63 / 590,010, filed October 13, 2023, which is incorporated herein by reference in its entirety. Background Technology

[0002] In recent years, corporate sustainability initiatives and national environmental initiatives have become increasingly prominent and influential. For example, electric vehicles have gained increasing prominence as consumers and various industries strive to reduce carbon emissions. Notably, fuel cell vehicles (a type of electric vehicle) involve fuel cells that generate electricity by reacting hydrogen with oxygen. Typically, hydrogen-containing tanks are used to store hydrogen in fuel cell vehicles. An important consideration in manufacturing tanks suitable for containing hydrogen is the tank's gas permeability. In fact, the small molecular size of hydrogen makes it particularly difficult to retain in containers such as tanks. Therefore, hydrogen tanks often include polymer linings to prevent or reduce hydrogen permeation to the outside of the tank. Furthermore, hydrogen internal combustion engines may use polymer linings in one or more of their components.

[0003] Typically, polymer liners used in gas tanks can be formed by injection molding, extrusion molding, or blow molding. Both injection molding and extrusion molding processes may require manufacturing the polymer liner in two or more parts, which are typically welded together in a second step. Notably, blow molding can form a complete polymer liner as a single integral part, and therefore does not require subsequent welding steps. Therefore, blow molding can be a generally preferred method for large-size liners. It is noteworthy that blow molding is a demanding process, preferably using polymer materials with good melt sag resistance and melt solidification characteristics suitable for forming reliable clamp welds during molding cycles. Furthermore, conventional polymer liners formed by blow molding may have limited sag resistance, may have sharp solidification points, and may have limited cold shock resistance or toughness.

[0004] Therefore, there is a need for a thermoplastic polymer composition suitable as a polymer liner for tanks, particularly hydrogen tanks used in fuel cell vehicles. Summary of the Invention

[0005] In general, this disclosure relates to a thermoplastic polymer composition. This thermoplastic polymer composition may be particularly suitable for blow molding applications.

[0006] In one aspect, the thermoplastic polymer composition may include a first polyamide comprising a first aliphatic homopolyamide; a second polyamide comprising a semi-aromatic copolyamide; a third polyamide comprising a second aliphatic homopolyamide, wherein the first aliphatic homopolyamide and the second aliphatic homopolyamide may be present in the thermoplastic polymer composition in a weight ratio of about 5:4 or greater; and an impact modifier present in the thermoplastic polymer composition in an amount greater than about 5 wt.%.

[0007] In one aspect, the first aliphatic homopolymer may comprise repeating units derived from lactams having 6 to 20 carbon atoms. In another aspect, the second aliphatic homopolymer may comprise repeating units derived from aliphatic dicarboxylic acids having 6 to 20 carbon atoms and aliphatic diamines having 4 to 20 carbon atoms.

[0008] In one aspect, the semi-aromatic copolyamide may comprise repeating units derived from an aromatic dicarboxylic acid having 8 to 20 carbon atoms and an aliphatic diamine having 4 to 20 carbon atoms. The semi-aromatic copolyamide may further comprise repeating units derived from an aliphatic dicarboxylic acid having 6 to 20 carbon atoms and an aliphatic diamine having 4 to 20 carbon atoms. Notably, the semi-aromatic copolyamide may comprise a first repeating unit present in an amount from about 50 mol percent to about 90 mol percent of the semi-aromatic copolyamide and a second repeating unit present in an amount from about 10 mol percent to about 50 mol percent. On one hand, the first repeating unit can be an aliphatic repeating unit, and the second repeating unit can be an aromatic repeating unit. In one aspect, the semi-aromatic copolyamide may comprise a first repeating unit present in an amount from about 60 mole percent to about 80 mole percent of the semi-aromatic copolyamide and a second repeating unit present in an amount from about 20 mole percent to about 40 mole percent. In another aspect, the first repeating unit may be an aliphatic repeating unit, and the second repeating unit may be an aromatic repeating unit.

[0009] On the one hand, the aliphatic repeating unit of semi-aromatic copolyamides is essentially the same as the repeating unit of one type of aliphatic homopolyamide.

[0010] Typically, the first aliphatic homopolymer and the second aliphatic homopolymer can be present in the thermoplastic polymer composition in a weight ratio of about 3:2 or greater.

[0011] On one hand, the impact modifier can be functionalized. On the other hand, the impact modifier can contain anhydride groups. The impact modifier can be present in the thermoplastic polymer composition in an amount of less than about 50 wt.%.

[0012] Typically, a first aliphatic homopolyamide may be present in the thermoplastic polymer composition in an amount from about 20 wt.% to about 70 wt.%. Furthermore, a second aliphatic homopolyamide may be present in the thermoplastic polymer composition in an amount from about 2 wt.% to about 20 wt.%. Additionally, a semi-aromatic copolyamide may be present in the thermoplastic polymer composition in an amount from about 2 wt.% to about 30 wt.%.

[0013] On the other hand, the thermoplastic polymer composition may include a first polyamide comprising an aliphatic copolyamide; a second polyamide comprising a semi-aromatic copolyamide; a third polyamide comprising an aliphatic homopolymer, wherein the aliphatic copolyamide and the semi-aromatic copolyamide may be present in the thermoplastic polymer composition in a weight ratio of about 6:5 or greater; and an impact modifier present in the thermoplastic polymer composition in an amount greater than about 5 wt.%.

[0014] Notably, aliphatic copolyamides may comprise repeating units derived from aliphatic dicarboxylic acids having 6 to 20 carbon atoms and aliphatic diamines having 4 to 20 carbon atoms. Aliphatic copolyamides may further comprise repeating units derived from lactams having 6 to 20 carbon atoms.

[0015] On one hand, the semi-aromatic copolyamide may comprise repeating units derived from an aromatic dicarboxylic acid having 8 to 20 carbon atoms and an aliphatic diamine having 4 to 20 carbon atoms. Furthermore, the semi-aromatic copolyamide may further comprise repeating units derived from an aliphatic dicarboxylic acid having 6 to 20 carbon atoms and an aliphatic diamine having 4 to 20 carbon atoms.

[0016] Typically, aliphatic homopolymers may contain repeating units derived from aliphatic dicarboxylic acids having 6 to 20 carbon atoms and aliphatic diamines having 4 to 20 carbon atoms. In one respect, the aliphatic repeating units of semi-aromatic copolyamides are substantially the same as those of aliphatic homopolymers. Attached Figure Description

[0017] The full and achievable disclosures of this specification are set forth in more detail in the remainder of the specification (including reference to the accompanying drawings), in which:

[0018] Figure 1 A cross-sectional view showing an embodiment of a can lined with a thermoplastic polymer composition according to this disclosure;

[0019] Figure 2 A perspective view of one embodiment of the anti-sagging testing system according to this disclosure is shown; and

[0020] Figure 3 A graphical representation of the anti-sagging properties of an embodiment of the thermoplastic polymer composition and the comparative composition according to this disclosure is shown.

[0021] Reference numerals used repeatedly in this specification and drawings are intended to denote the same or similar features or elements of the invention. Detailed Implementation

[0022] Reference will now be made in detail to various embodiments of the disclosed subject matter, one or more of which are set forth below. Each embodiment is provided by way of explanation and not limitation of the subject matter. In fact, it will be apparent to those skilled in the art that various modifications and variations may be made in this disclosure without departing from the scope or spirit of the subject matter. For example, a feature shown or described as part of one embodiment may be used in another embodiment to produce yet another embodiment.

[0023] In general, this disclosure relates to a thermoplastic polymer composition and related methods. The thermoplastic polymer composition may contain one or more polyamides, such as three polyamides. For example, the thermoplastic polymer composition may contain one or more semi-aromatic copolyamides, one or more aliphatic copolyamides, and / or one or more aliphatic homopolymers. Additionally, the one or more polyamides may be crystalline or semi-crystalline. Notably, the use of three polyamides in a thermoplastic polymer composition can be particularly advantageous, as opposed to using two polyamides. The thermoplastic polymer composition may be particularly suitable for blow molding applications. Notably, the thermoplastic polymer composition may have enhanced anti-sagging properties, reduced gas permeability, enhanced cold shock resistance or toughness, enhanced high-temperature rigidity, and / or may allow for increased molding time and clamping weld formation time during the blow molding production steps.

[0024] It should be understood that throughout this specification, every numerical value disclosed (e.g., weight percentage) should be interpreted as modified by the term "about" (unless explicitly stated otherwise) and again as not modified otherwise. For example, the value "100" should be understood to disclose both "100" and "about 100". Furthermore, it should be understood that throughout this specification, when describing ranges of numerical values ​​(e.g., weight percentage), any and every quantity within that range is disclosed, including the endpoints and all quantities in between. For example, the range "1 to 100" should be understood to disclose both the range "1 to 100 (inclusive)" and the range "about 1 to about 100 (inclusive)". Quantities in between may be separated by any incremental values. It should be understood that, unless otherwise stated, any standards listed herein (e.g., ASTM) are the latest versions available up to the year of the most recent revision. It is noteworthy that some aspects of this disclosure may omit one or more of the features disclosed herein.

[0025] Notably, the thermoplastic polymer compositions manufactured according to this disclosure can be formed into tubular components, such as can linings. For example, Figure 1 An embodiment of the tank liner 12 of the gas tank 10 is shown. Figure 1 In the gas tank 10, there is a housing 14, which may be formed of fiber-reinforced plastic or metal. Furthermore, Figure 1 The gas canister 10 includes a canister valve 16. One method of forming a thermoplastic polymer composition into a tubular member is by blow molding, which is particularly useful for manufacturing large hollow articles such as bottles, barrels, and cans from thermoplastic materials. During blow molding, the thermoplastic polymer composition can first be heated and extruded using a mold attached to an extrusion device. The extruded molten tubular member is suspended on the mold and is referred to as a "preform". The preform can then be received into a molding apparatus, which can be formed by one or more parts forming a three-dimensional mold cavity. In some aspects, a robotic arm can be used to manipulate the preform in the molding apparatus. The molding apparatus can be closed and the preform can be sealed. The preform can then be sealed at its open end by bringing together the opposing inner molten surfaces of the preform and forming a clamp through the mold wall. The clamp formed in this way can form a weld, thereby creating a leak-proof seal during subsequent forming and curing steps. This weld can be referred to as a "clamp weld".

[0026] Once the molding apparatus is closed, gas (e.g., air, nitrogen, inert gas) is fed from a gas supply source into the preform. The gas supplies sufficient pressure to the inner surface of the preform, causing it to conform to the shape of the mold cavity. After the blow-molded article (e.g., a blow-molded thermoplastic polymer composition) has cured, the various parts of the molding apparatus can be opened or removed, and the final molded article (e.g., a can liner) can then be removed. Alternatively, cold air can be injected into the molded part (e.g., a can liner) to cure the thermoplastic polymer composition before it is removed from the molding apparatus.

[0027] It is noteworthy that during and after parison formation, the parison is typically suspended for a period of time after leaving the extrusion unit. In this respect, from parison formation, the movement of the parison to engagement with the molding apparatus, the closing of the mold and clamping of the parison ends, the blowing of the parison to conform to the mold cavity, and its solidification, a certain period of time elapses. During these stages of the method, the melt strength of the thermoplastic polymer composition is preferably high enough that the parison generally maintains its tubular shape without collapsing or excessively thinning along its length. Indeed, when the parison is formed, the thermoplastic polymer composition must have sufficient melt strength to prevent gravity from undesirably elongating (i.e., sagging) multiple sections of the parison and thereby creating uneven wall thickness and other defects. In this respect, it is preferable that the parison does not flow or deform significantly before the molding step. Another consideration is that the thermoplastic polymer composition is preferably able to remain in a semi-fluid state and not solidify too quickly before the blow molding step begins, so that the parison can conform to the details of the molding apparatus. To facilitate the formation of strong clamping welds, it is also desirable that the thermoplastic polymer composition does not have a sharp solidification point, but rather cures over a wider temperature range.

[0028] Typically, thermoplastic polymer compositions may contain one or more polyamides. For example, a thermoplastic polymer composition may contain a first polyamide, a second polyamide, and a third polyamide. Typically, the first polyamide, the second polyamide, and / or the third polyamide may contain one or more homopolymers and / or one or more copolymers, including any homopolymers and / or copolymers disclosed herein. For example, in one aspect, a thermoplastic polymer composition may contain a first polyamide comprising a first aliphatic homopolymer; a second polyamide comprising a semi-aromatic copolyamide; and a third polyamide comprising a second aliphatic homopolymer. In another aspect, a thermoplastic polymer composition may contain a first polyamide comprising an aliphatic copolyamide; a second polyamide comprising a semi-aromatic copolyamide; and a third polyamide comprising an aliphatic homopolymer.

[0029] Notably, in contrast to two or more polyamides having different repeating units, the use of two or more polyamides having at least some of the same repeating units (i.e., derived from the same diacid (e.g., aliphatic dicarboxylic acid) and the same diamine (e.g., aliphatic diamine)) in a thermoplastic polymer composition formed according to this disclosure can have enhanced compatibility. For example, in one aspect, a thermoplastic polymer composition formed according to this disclosure may contain a semi-aromatic copolyamide and an aliphatic homopolymer having the same aliphatic repeating units.

[0030] In some aspects, the thermoplastic polymer composition may contain a first polyamide in amounts from about 20 wt.% to about 70 wt.% (including all increments of 1 wt.% therebetween), such as about 20 wt.% or more, such as about 30 wt.% or more, such as about 35 wt.% or more, such as about 40 wt.% or more, such as about 45 wt.% or more, such as about 50 wt.% or more, such as about 55 wt.% or more, such as about 60 wt.% or more, such as about 70 wt.% or less, such as about 60 wt.% or less, such as about 55 wt.% or less, such as about 45 wt.% or less, such as about 40 wt.% or less, such as about 35 wt.% or less, such as about 30 wt.% or less.

[0031] In some aspects, the thermoplastic polymer composition may contain a second polyamide in amounts from about 2 wt.% to about 30 wt.% (including all increments of 1 wt.% therebetween), such as about 2 wt.% or more, such as about 5 wt.% or more, such as about 10 wt.% or more, such as about 15 wt.% or more, such as about 20 wt.% or more, such as about 25 wt.% or more, such as about 30 wt.% or less, such as about 25 wt.% or less, such as about 20 wt.% or less, such as about 15 wt.% or less, such as about 10 wt.% or less, such as about 5 wt.% or less.

[0032] In some aspects, the thermoplastic polymer composition may contain a third polyamide in amounts from about 2 wt.% to about 20 wt.% (including all increments of 1 wt.% therebetween), such as about 2 wt.% or more, such as about 5 wt.% or more, such as about 10 wt.% or more, such as about 15 wt.% or more, such as about 20 wt.% or less, such as about 15 wt.% or less, such as about 10 wt.% or less, such as about 5 wt.% or less.

[0033] Typically, thermoplastic polymer compositions and / or their polyamides (e.g., first polyamide, second polyamide, third polyamide) may contain one or more aliphatic homopolymers, such as first aliphatic homopolymer and second aliphatic homopolymer. It is noteworthy that the first aliphatic homopolyamide and the second aliphatic homopolyamide may be present in the thermoplastic polymer composition in a weight ratio of about 5:4 or greater, such as about 3:2 or greater, such as about 2:1 or greater, such as about 3:1 or greater, such as about 4:1 or greater, such as about 5:1 or greater, such as about 6:1 or greater, such as about 8:1 or greater, such as about 10:1 or greater, such as about 12:1 or less, such as about 10:1 or less, such as about 8:1 or less, such as about 6:1 or less, such as about 5:1 or less, such as about 4:1 or less, such as about 3:1 or less, such as about 2:1 or less, such as about 3:2 or less.

[0034] Typically, thermoplastic polymer compositions and / or their polyamides (e.g., first polyamide, second polyamide, third polyamide) may contain one or more aliphatic copolyamides and / or one or more semi-aromatic copolyamides. It is noteworthy that aliphatic copolyamides and semi-aromatic copolyamides may be present in the thermoplastic polymer composition in weight ratios of about 6:5 or greater, such as about 5:4 or greater, such as about 3:2 or greater, such as about 2:1 or greater, such as about 3:1 or greater, such as about 4:1 or greater, such as about 5:1 or greater, such as about 6:1 or greater, such as about 8:1 or greater, such as about 10:1 or greater, such as about 12:1 or less, such as about 10:1 or less, such as about 8:1 or less, such as about 6:1 or less, such as about 5:1 or less, such as about 4:1 or less, such as about 3:1 or less, such as about 2:1 or less, such as about 3:2 or less, such as about 5:4 or less.

[0035] It is worth noting that the polyamides disclosed herein can be homopolymers and / or copolymers. Homopolymers and copolymers are identified by their respective repeating units. The following list exemplifies the abbreviations used to identify monomers and repeating units in homopolymer polyamides and copolymer polyamides: Table 1

[0036] It is noteworthy that, as previously disclosed herein, the above list (i.e., Table 1) illustrates abbreviations for monomers and repeating units used to identify homopolymers and copolymers. In this regard, one or more homopolymers and / or one or more copolymers of a thermoplastic polymer composition, such as one or more homopolymers and / or one or more copolymers of a first polyamide, a second polyamide, and / or a third polyamide, may comprise or be formed from the following: HMD, T, AA, DMD, 6, DDA, DDDA, I, MXD, 2-MPMD, TMD, 4T, 6T, DT, MXD6, 66, 10T, 410, 510, 610, 612, 6, 11, 12, or combinations thereof.

[0037] With respect to Table 1, and more generally to the entirety of this disclosure, it should be understood that the term "6," when used alone, indicates that it is derived from... - A repeating unit in a polymer formed from caprolactam. Alternatively, when "6" is used in combination with a diacid such as T, for example 6T, "6" refers to HMD. In repeating units containing both a diamine and a diacid, the diamine is specified first. Furthermore, when "6" is used in combination with a diamine, for example 66, the first "6" refers to the diamine HMD, and the second "6" refers to adipic acid. Similarly, repeating units derived from other amino acids or lactams are specified as a single number indicating the number of carbon atoms.

[0038] Typically, repeating units in copolyamides are separated by one or more forward slashes (i.e., / ). For example, poly(decamethylene sebacam / decamethylene terephthalamide) is abbreviated as PA1010 / 10T (75 / 25), where the value in parentheses is the molar percentage of each repeating unit in the copolyamide. Generally, the repeating unit present in a higher proportion is indicated first, followed by the repeating unit present in a lower proportion. It is noteworthy that if a range of repeating units relative to the molar percentage of repeating units in the copolyamide is disclosed, it should be understood that the range covers all numbers between two corresponding values ​​occupying their respective positions in the description of the copolyamide or ternary polyamide. For example, PA 612 / 6T (85 / 15) to (55 / 45) would include all numbers between 85 and 55 (inclusive) before the forward slash and all numbers between 15 and 45 (inclusive) after the forward slash. In this regard, PA 612 / 6T (85 / 15) to (55 / 45) can include, for example, PA 612 / 6T (75 / 25), PA 612 / 6T (70 / 30), or PA 612 / 6T (60 / 40). Furthermore, if the copolyamide has three repeating units (e.g., a ternary polyamide), the range will include all numbers between the two digits before the first slash (inclusive), all numbers between the two digits after the first slash (inclusive), and all numbers between the two digits after the second slash (inclusive). As used herein, the value before the slash can be referred to as the first repeating unit, and the value after the slash can be referred to as the second repeating unit. When using a ternary polyamide, the value after the second slash can be referred to as the third repeating unit. Notably, the first repeating unit, the second repeating unit, and / or the third repeating unit can refer to an aliphatic repeating unit or an aromatic repeating unit.

[0039] Typically, one or more copolyamides (e.g., semi-aromatic copolyamides, aliphatic copolyamides) may have a first repeating unit in mole% repeating units ranging from about 50 to about 90 (inclusive of all increments of 1 mol%). For example, one or more copolyamides may have a first repeating unit in mole% repeating units ranging from about 50% or more, such as about 55% or more, such as about 60% or more, such as about 65% or more, such as about 70% or more, such as about 75% or more, such as about 80% or more, such as about 85% or more, such as about 90% or less, such as about 85% or less, such as about 80% or less, such as about 75% or less, such as about 70% or less, such as about 65% or less, such as about 60% or less, such as about 55% or less. Notably, for semi-aromatic copolyamides, the first repeating unit may refer to an aliphatic repeating unit of the polymer chain.

[0040] Typically, one or more copolyamides (e.g., semi-aromatic copolyamides, aliphatic copolyamides) may have a second repeating unit in mole% repeating units ranging from about 10 to about 50 (including all increments of 1 mol%). For example, one or more copolyamides may have a second repeating unit in mole% repeating units ranging from about 10% or more, such as about 15% or more, such as about 20% or more, such as about 25% or more, such as about 30% or more, such as about 35% or more, such as about 40% or more, such as about 45% or more, such as about 50% or less, such as about 45% or less, such as about 40% or less, such as about 35% or less, such as about 30% or less, such as about 25% or less, such as about 20% or less, such as about 15% or less. Notably, for semi-aromatic copolyamides, the second repeating unit may refer to an aromatic repeating unit of the polymer chain.

[0041] Typically, one or more polyamides (e.g., one or more homopolymers and / or one or more copolymers) in a thermoplastic polymer composition can be aliphatic (i.e., containing only aliphatic monomer units) and / or semi-aromatic (i.e., containing both aliphatic and aromatic monomer units). In this regard, combinations of one or more aliphatic polyamides and / or one or more semi-aromatic polyamides can be included in thermoplastic polymer compositions formed according to this disclosure. Typically, one or more aliphatic polyamides and / or one or more semi-aromatic polyamides can be included in a first polyamide, a second polyamide, and / or a third polyamide.

[0042] Notably, aliphatic polyamides (e.g., aliphatic homopolymers, aliphatic copolymers) can be derived from one or more carboxylic acid components (e.g., one or more dicarboxylic acid components) and one or more diamine components. In this regard, for example, aliphatic polyamides can have aliphatic repeating units derived from one or more aliphatic carboxylic acid components (e.g., one or more aliphatic dicarboxylic acid components) and one or more aliphatic diamine components. On another aspect, aliphatic polyamides can have aliphatic repeating units derived from one or more aliphatic amino acids or lactams.

[0043] Notably, in one aspect, the thermoplastic polymer composition may contain one or more aliphatic homopolyamides, such as PA 6, PA 66, PA 610, PA 612, or combinations thereof. In another aspect, the thermoplastic polymer composition may contain one or more aliphatic copolyamides, such as PA 66 / 6 (85 / 15) to PA 6 / 66 (85 / 15) (e.g., PA 66 / 6 (75 / 25)).

[0044] Notably, semi-aromatic polyamides (e.g., semi-aromatic copolyamides) can be derived from one or more carboxylic acid components (e.g., one or more dicarboxylic acid components) and one or more diamine components. In this regard, for example, semi-aromatic polyamides can have aromatic repeating units derived from one or more aromatic carboxylic acid components (e.g., one or more aromatic dicarboxylic acid components) and one or more aliphatic diamine components. Additionally, for example, semi-aromatic polyamides can have aromatic repeating units derived from one or more aliphatic carboxylic acid components (e.g., one or more aliphatic dicarboxylic acid components) and one or more aromatic diamine components. Furthermore, for example, semi-aromatic polyamides can have aliphatic repeating units derived from one or more aliphatic carboxylic acid components (e.g., one or more aliphatic dicarboxylic acid components) and one or more aliphatic diamine components. In one aspect, semi-aromatic polyamides (e.g., semi-aromatic copolyamides) can have aliphatic repeating units derived from one or more aliphatic amino acids or lactams. Notably, in one aspect, the semi-aromatic copolyamides according to this disclosure can have at least 50 molar percentages of aliphatic repeating units.

[0045] It is noteworthy that, on one hand, the thermoplastic polymer composition may contain one or more semi-aromatic copolyamides, such as PA 612 / 6T (85 / 15) to (55 / 45) (e.g., PA 612 / 6T (75 / 25), PA 612 / 6T (70 / 30) and PA 612 / 6T (60 / 40)) and such as PA 610 / 6T (85 / 15) to (55 / 45) (e.g., PA 610 / 6T (80 / 20), PA 610 / 6T (75 / 25) and PA 610 / 6T (60 / 40)).

[0046] Typically, aromatic dicarboxylic acids can be terephthalic acid, isophthalic acid, or 2,6-naphthalic acid. In one aspect, aromatic dicarboxylic acids can have from 8 to 20 carbon atoms, including all increments of one carbon atom in between. For example, aromatic dicarboxylic acids can have 8 or more carbon atoms, such as 10 or more carbon atoms, such as 12 or more carbon atoms, such as 14 or more carbon atoms, such as 16 or more carbon atoms, such as 18 or more carbon atoms, such as 20 or fewer carbon atoms, such as 18 or fewer carbon atoms, such as 16 or fewer carbon atoms, such as 14 or fewer carbon atoms, such as 12 or fewer carbon atoms, such as 10 or fewer carbon atoms.

[0047] Typically, aliphatic dicarboxylic acids can be adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, decanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, hexadecanoic acid, or octadecanoic acid. In one aspect, aliphatic dicarboxylic acids can have from 6 to 20 carbon atoms, including all increments of one carbon atom in between. For example, aliphatic dicarboxylic acids can have 6 or more carbon atoms, such as 8 or more carbon atoms, such as 10 or more carbon atoms, such as 12 or more carbon atoms, such as 14 or more carbon atoms, such as 16 or more carbon atoms, such as 18 or more carbon atoms, such as 20 or fewer carbon atoms, such as 18 or fewer carbon atoms, such as 16 or fewer carbon atoms, such as 14 or fewer carbon atoms, such as 12 or fewer carbon atoms, such as 10 or fewer carbon atoms, such as 8 or fewer carbon atoms.

[0048] Typically, aliphatic diamines can be hexamethylenediamine (HMD), 1,10-decanediamine, 1,12-dodecanediamine, or 2-methyl-1,5-pentamethylenediamine. In one aspect, aliphatic diamines can have from 4 to 20 carbon atoms, including all increments of one carbon atom in between. For example, aliphatic diamines can have 4 or more carbon atoms, such as 6 or more carbon atoms, such as 8 or more carbon atoms, such as 10 or more carbon atoms, such as 12 or more carbon atoms, such as 14 or more carbon atoms, such as 16 or more carbon atoms, such as 18 or more carbon atoms, such as 20 or fewer carbon atoms, such as 18 or fewer carbon atoms, such as 16 or fewer carbon atoms, such as 14 or fewer carbon atoms, such as 12 or fewer carbon atoms, such as 10 or fewer carbon atoms, such as 8 or fewer carbon atoms, such as 6 or fewer carbon atoms.

[0049] Typically, aliphatic amino acids (e.g., aliphatic aminocarboxylic acids) or lactams can be 11-aminoundecanoic acid, 12-aminododecanoic acid, or their respective lactams. In one aspect, aliphatic amino acids or lactams can have from 6 to 20 carbon atoms, including all increments of one carbon atom in between. For example, aliphatic amino acids or lactams can have 6 or more carbon atoms, such as 8 or more carbon atoms, such as 10 or more carbon atoms, such as 12 or more carbon atoms, such as 14 or more carbon atoms, such as 16 or more carbon atoms, such as 18 or more carbon atoms, such as 20 or fewer carbon atoms, such as 18 or fewer carbon atoms, such as 16 or fewer carbon atoms, such as 14 or fewer carbon atoms, such as 12 or fewer carbon atoms, such as 10 or fewer carbon atoms, such as 8 or fewer carbon atoms.

[0050] As previously disclosed herein, the thermoplastic polymer composition may contain one or more polyamides. For example, the thermoplastic polymer composition may contain a first polyamide, a second polyamide, and a third polyamide. Typically, the thermoplastic polymer composition may contain from about 20 wt.% to about 70 wt.% of PA 6 homopolymer, such as about 20 wt.% or more, about 30 wt.% or more, about 35 wt.% or more, about 40 wt.% or more, about 45 wt.% or more, about 50 wt.% or more, about 55 wt.% or more, about 60 wt.% or more, about 70 wt.% or less, about 60 wt.% or less, about 55 wt.% or less, about 45 wt.% or less, about 40 wt.% or less, about 35 wt.% or less, or about 30 wt.% or less.

[0051] Typically, the thermoplastic polymer composition may contain from about 20 wt.% to about 70 wt.% of PA 66 / 6 copolymer, such as about 20 wt.% or more, such as about 30 wt.% or more, such as about 35 wt.% or more, such as about 40 wt.% or more, such as about 45 wt.% or more, such as about 50 wt.% or more, such as about 55 wt.% or more, such as about 60 wt.% or more, such as about 70 wt.% or less, such as about 60 wt.% or less, such as about 55 wt.% or less, such as about 45 wt.% or less, such as about 40 wt.% or less, such as about 35 wt.% or less, such as about 30 wt.% or less.

[0052] Typically, the thermoplastic polymer composition may contain from about 2 wt.% to about 30 wt.% of PA 610 / 6T copolymer, such as about 2 wt.% or more, such as about 5 wt.% or more, such as about 10 wt.% or more, such as about 15 wt.% or more, such as about 20 wt.% or more, such as about 25 wt.% or more, such as about 30 wt.% or less, such as about 25 wt.% or less, such as about 20 wt.% or less, such as about 15 wt.% or less, such as about 10 wt.% or less, such as about 5 wt.% or less.

[0053] Typically, the thermoplastic polymer composition may contain from about 2 wt.% to about 30 wt.% of PA 612 / 6T copolymer, such as about 2 wt.% or more, such as about 5 wt.% or more, such as about 10 wt.% or more, such as about 15 wt.% or more, such as about 20 wt.% or more, such as about 25 wt.% or more, such as about 30 wt.% or less, such as about 25 wt.% or less, such as about 20 wt.% or less, such as about 15 wt.% or less, such as about 10 wt.% or less, such as about 5 wt.% or less.

[0054] Typically, the thermoplastic polymer composition may contain from about 2 wt.% to about 20 wt.% of PA 610 homopolymer, such as about 2 wt.% or more, such as about 5 wt.% or more, such as about 10 wt.% or more, such as about 15 wt.% or more, such as about 20 wt.% or less, such as about 15 wt.% or less, such as about 10 wt.% or less, such as about 5 wt.% or less.

[0055] Typically, the thermoplastic polymer composition may contain from about 2 wt.% to about 20 wt.% of PA 612 homopolymer, such as about 2 wt.% or more, about 5 wt.% or more, about 10 wt.% or more, about 15 wt.% or more, about 20 wt.% or less, about 15 wt.% or less, about 10 wt.% or less, or about 5 wt.% or less. The PA 612 homopolymer may be a component of a first polyamide, a second polyamide, and / or a third polyamide. Impact modifier

[0056] Typically, the thermoplastic polymer compositions formed according to this disclosure may contain one or more impact modifiers. In some aspects, the impact modifiers may be unfunctionalized or functionalized. When present, the one or more impact modifiers may include, but are not limited to, one or more polymeric impact modifiers, wherein the impact modifiers contain acid, epoxy, or anhydride functional groups. Such functional groups are typically incorporated into the impact modifier by grafting small molecules onto an existing polymer backbone or by directly copolymerizing a monomer containing the desired functional group into the polymer backbone of the impact modifier. For example, as an example of a suitable type of grafted impact modifier, maleic anhydride can be grafted onto hydrocarbon rubbers (e.g., EPDM) and / or olefinic thermoplastics (e.g., ethylene / α-olefin copolymers, where α-olefins are straight-chain olefins with terminal double bonds, such as propylene or 1-octene) using free radical grafting techniques. The resulting grafted polymer may have carboxylic anhydride and / or carboxyl groups attached thereto. In one specific aspect, the impact modifier can be a maleic anhydride-grafted ethylene copolymer.

[0057] Functionalized ethylene copolymers are examples of polymer impact modifiers in which functional groups are directly copolymerized into the polymer backbone, such as direct copolymers of ethylene and (meth)acrylic acid monomers. In addition to (meth)acrylic acid monomers, ethylene copolymers may also contain acrylate monomers, methacrylate monomers, or mixtures of both. Examples of acrylate and methacrylate monomers include ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, and cyclohexyl (meth)acrylate. Useful compounds containing functional groups include (meth)acrylic acid, 2-hydroxyethyl (meth)acrylic acid, glycidyl (meth)acrylate, and 2-isocyanoethyl (meth)acrylic acid. As used herein, the prefix "(meth)" refers to an optional methyl group. For example, "(meth)acrylic acid" refers to acrylic acid, methacrylic acid, or both acrylic acid and methacrylic acid. Suitable functionalized ethylene copolymers for use as impact modifiers include, but are not limited to, those described in U.S. Patent No. 4,174,358.

[0058] Another suitable type of impact modifier is a polymer containing a carboxylic acid metal salt. Such polymers can be prepared by grafting a compound containing a carboxylic acid or carboxylic anhydride onto the polymer or by directly copolymerizing a comonomer containing an acid or anhydride. Subsequently, some or all of the acid or anhydride groups are neutralized. Useful materials of this type include Surlyn™ ionomers available from Dow Chemical Company, Midland, 48674, USA, and neutralized maleic anhydride-grafted ethylene / α-olefin polymers with a metal cation as a counterion. Preferred metal cations for these carboxylic acids include Na, Zn, Li, Mg, and Mn cations.

[0059] In this document, the term "ethylene copolymer" includes ethylene binary copolymers, i.e., copolymers of ethylene with one comonomer; ethylene terpolymers, i.e., copolymers of ethylene with two comonomers; and ethylene multipolymers, i.e., copolymers having more than three different repeating units. Ethylene copolymers that can be used as impact modifiers include those selected from the group consisting of ethylene copolymers having the formula E / X / Y, wherein:

[0060] E represents a repeating unit derived from ethylene;

[0061] X represents a repeating unit derived from one or more comonomers having the following formula. CH2=CH(R 1 )—C(O)—OR 2 Where R 1 It is H, CH3 or C2H5, and R 2X is an alkyl group having 1 to 8 carbon atoms; or X represents a repeating unit derived from vinyl acetate alone or in combination with one or more other comonomers X; wherein the amount of X is from 0 to 50% by weight of the E / X / Y copolymer; Y represents a repeating unit derived from one or more monomers selected from the group consisting of: carbon monoxide, sulfur dioxide, acrylonitrile, maleic anhydride, maleic acid diester, (meth)acrylic acid, maleic acid, maleic acid monoester, itaconic acid, fumaric acid, fumaric acid monoester and potassium, sodium and zinc salts of the aforementioned acids, glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-isocyanate ethyl (meth)acrylate and glycidyl vinyl ether; wherein the amount of Y is from 0.5 to 35% by weight of the E / X / Y copolymer, and preferably from 0.5 to 20% by weight of the E / X / Y copolymer, and E is the remaining weight percentage and preferably includes 40-90% by weight of the E / X / Y copolymer.

[0062] In some respects, functionalized impact modifiers may contain repeating units from about 0.1 wt.% to about 15 wt.% (including all increments of about 0.01 wt.% therebetween) and / or grafted molecules containing functional groups or carboxylates (including metals). For example, by weight of the impact modifier, the functionalized impact modifier may contain about 0.1 wt.% of repeating units and / or grafted molecules containing functional groups or carboxylates (including metals) or more, such as about 0.2 wt.% or more, about 0.3 wt.% or more, about 0.4 wt.% or more, about 0.5 wt.% or more, about 1 wt.% or more, about 2 wt.% or more, about 4 wt.% or more, about 6 wt.% or more, about 8 wt.% or more, about 10 wt.% or more, about 12 wt.% or more, about 14 wt.% or more, about 15 wt.% or less, about 14 wt.% or less, about 12 wt.% or less, about 10 wt.% or less, about 8 wt.% or less, about 6 wt.% or less, etc. wt.% or less, such as about 4 wt.% or less, such as about 2 wt.% or less, such as about 1 wt.% or less, such as about 0.5 wt.% or less, such as about 0.4 wt.% or less, such as about 0.3 wt.% or less, such as about 0.2 wt.% or less. In general, more than one type of functional monomer and / or more than one polymer impact modifier may be present in the polymer impact modifier.

[0063] In addition to functionalized impact modifiers, non-functionalized impact modifiers may also be present. Non-functionalized impact modifiers include polymers such as ethylene / α-olefin / diene (EPDM) rubber, polyolefins (including polyethylene (PE) and polypropylene), and ethylene / α-olefin (EP) elastomers such as ethylene / 1-octene copolymers, and similar products such as those commercially available copolymers under the trademark ENGAGE® from Dow Chemical Company, Midland, Michigan. Other non-functionalized impact modifiers include styrene-containing polymers, including acrylonitrile-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, styrene-isoprene-styrene copolymers, styrene-hydrogenated isoprene-styrene copolymers, styrene-butadiene-styrene copolymers, styrene-hydrogenated butadiene-styrene copolymers, styrene block copolymers, and polystyrene. For example, acrylonitrile-butadiene-styrene or ABS is a terpolymer prepared by polymerizing styrene and acrylonitrile in the presence of polybutadiene. The proportions can vary from 15% to 35% acrylonitrile, 5% to 30% butadiene, and 40% to 60% styrene. The result is a cross between the long chains of polybutadiene and the shorter chains of polystyrene and acrylonitrile.

[0064] Typically, thermoplastic polymer compositions may contain an amount of impact modifier (e.g., maleic anhydride-grafted ethylene copolymer) ranging from about 5 wt.% to about 50 wt.% (including all increments of about 0.01 wt.% therebetween). For example, the thermoplastic polymer composition may contain, by weight, an amount of impact modifier (e.g., maleic anhydride-grafted ethylene copolymer) of about 5 wt.% or more, such as about 10 wt.% or more, such as about 15 wt.% or more, such as about 20 wt.% or more, such as about 25 wt.% or more, such as about 30 wt.% or more, such as about 35 wt.% or more, such as about 40 wt.% or more, such as about 45 wt.% or more, such as about 50 wt.% or less, such as about 45 wt.% or less, such as about 40 wt.% or less, such as about 35 wt.% or less, such as about 30 wt.% or less, such as about 25 wt.% or less, such as about 20 wt.% or less, such as about 15 wt.% or less, such as about 10 wt.% or less. stabilizer

[0065] Typically, thermoplastic polymer compositions may contain one or more stabilizers. Notably, one or more stabilizers may include one or more antioxidants.

[0066] On the one hand, stabilizers that can be incorporated into thermoplastic polymer compositions are heat stabilizers containing hindered phenolic antioxidants. Examples of such phenolic antioxidants include, for example, calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate) (Irganox® 1425); terephthalic acid, 1,4-dithio-, S,S-bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) ester (Cyanox® 1729); triethylene glycol bis(3-tert-butyl-4-hydroxy-5-methylhydrocinnamate); hexamethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate) ester (Irganox® 259); 1,2-bis(3,5,di-tert-butyl-4-hydroxyhydrocinnamoyl) hydrazide (Irganox® 1024); 4,4′-di-tert-octyl diphenylamine (Naugalube® 438R); phosphonic acid, (3,5-di-tert-butyl-4-hydroxybenzyl)-, Dioctadecyl ester (Irganox® 1093); 1,3,5-trimethyl-2,4,6-tris(3′,5′-di-tert-butyl-4′-hydroxybenzyl)benzene (Irganox® 1330); 2,4-bis(octylthio)-6-(4-hydroxy-3,5-di-tert-butylaniline)-1,3,5-triazine (Irganox® 565); isooctyl ester of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox® 1135); octadecyl ester of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox® 1076); 3,7-bis(1,1,3,3-tetramethylbutyl)-10H-phenthiazine (Irganox® LO) 3); 2,2′-methylenebis(4-methyl-6-tert-butylphenol) monoacrylate (Irganox® 3052); 2-tert-butyl-6-[1-(3-tert-butyl-2-hydroxy-5-methylphenyl)ethyl]-4-methylphenyl acrylate (Sumilizer® TM 4039); 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate (Sumilizer® GS); 1,3-dihydro-2H-benzimidazole (Sumilizer® MB); 2-methyl-4,6-bis[(octylthio)methyl]phenol (Irganox® 1520); N,N′-trimethylenebis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide (Irganox® 1019); 4-n-octadecyloxy-2,6-diphenylphenol (Irganox® 1063); 2,2′-Ethylenebis[4,6-di-tert-butylphenol] (Irganox® 129); NN′-Hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoamide) (Irganox® 1098);(3,5-Di-tert-butyl-4-hydroxybenzyl)phosphonate diethyl ester (Irganox® 1222); 4,4′-Di-tert-octyldiphenylamine (Irganox® 5057); N-phenyl-1-naphthylamine (Irganox® L 05); Tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-6-methylphenylthio)-5-methylphenyl]phosphite (Hostanox® OSP 1); Zinc dinonanodithiocarbamate (Hostanox® VP-ZNCS 1); 3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]-2,4,8,10-tetraoxazolo[5,5]undecane (Sumilizer®) AG80); pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox® 1010); ethylene-bis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate (Irganox® 245); 3,5-di-tert-butyl-4-hydroxytoluene (Lowinox BHT, Chemitura), etc.

[0067] Some examples of suitable sterically hindered phenolic antioxidants for use in the compositions of the present invention are triazine antioxidants having the following general formula: Each R is independently a phenolic group, which may be attached to the triazine ring via a C1 to C5 alkyl or ester substituent. Preferably, each R is one of the following formulas (I)-(III):

[0068] Commercially available examples of such triazine-based antioxidants can be obtained from American Cyanamid under the name Cyanox® 1790 (where each R group is represented by Formula III) and from Ciba Specialty Chemicals under the names Irganox® 3114 (where each R group is represented by Formula I) and Irganox® 3125 (where each R group is represented by Formula II).

[0069] In one embodiment, the heat stabilizer may comprise copper iodobis(triphenylphosphine)iodide. Alternatively, the heat stabilizer may be a metal halide, such as a metal iodide. The metal iodide may be potassium iodide, copper iodide, or a mixture thereof (e.g., CuI / KI).

[0070] On one hand, the heat stabilizer may include a copper compound, which may include copper(I) salts, copper(II) salts, copper complexes, or combinations thereof. For example, copper(I) salts may be CuI, CuBr, CuCl, CuCN, Cu2O, or combinations thereof, and / or copper(II) salts may be copper acetate, copper stearate, copper sulfate, copper propionate, copper butyrate, copper lactate, copper benzoate, copper nitrate, CuO, CuCl2, or combinations thereof. In some embodiments, the copper compound may be a copper complex containing an organic ligand, such as alkylphosphine, such as trialkylphosphine (e.g., tri-(n-butyl)phosphine) and / or dialkylphosphine (e.g., 2-bis-(dimethylphosphinyl)-ethane); aromatic phosphine, such as triarylphosphine (e.g., triphenylphosphine or substituted triphenylphosphine) and / or diarylphosphine (e.g., 1,6-(bis-(diphenylphosphinyl))-hexane, 1,5-bis-(diphenylphosphinyl)-pentane, bis-(diphenylphosphinyl)methane, 1,2-bis-(diphenylphosphinyl)ethane, 1,3-bis-(diphenylphosphinyl)propane, 1,4-bis-(diphenylphosphinyl)butane, etc.); mercaptobenzimidazole; glycine; oxalate; pyridine (e.g., bipyridine); amine (e.g., ethylenediaminetetraacetate, diethylenetriamine, triethylenetetraamine, etc.); acetylacetone compounds; etc., and combinations thereof. Particularly suitable copper complexes for use in heat stabilizers may include, for example, copper acetylacetonate, copper oxalate, copper EDTA, [Cu(PPh3)3X], [Cu2X(PPH3)3], [Cu(PPh3)X], [Cu(PPh3)2X], [CuX(PPh3)-2,2'-bipyridine], [CuX(PPh3)-2,2'-biquinoline], or combinations thereof, wherein PPh3 is triphenylphosphine and X is CI, Br, I, CN, SCN, or 2-mercaptobenzimidazole. Other suitable complexes may also include 1,10-phenanthroline, o-phenylenebis(dimethylarsene), 1,2-bis(diphenylphosphino)-ethane, terpyridine, etc.

[0071] When used, copper complexes can be formed by reacting copper ions (e.g., copper(I) ions) with organic ligand compounds (e.g., triphenylphosphine or mercaptobenzimidazole compounds). For example, these complexes can be obtained by reacting triphenylphosphine with copper(I) halides suspended in chloroform (G. Kosta, E. Reisenhofer and L. Stafani, J.lnorg. Nukl. Chem. [Journal of Inorganic and Nuclear Chemistry] 27 (1965) 2581). However, copper(II) compounds can also be reduced with triphenylphosphine to obtain copper(I) addition compounds (FU Jardine, L. Rule, AGVohrei, J. Chem. Soc. [Journal of Chemistry] (A) 238-241 (1970)). However, the complexes used according to the invention can also be produced by any other suitable method. Suitable copper compounds for preparing these complexes are copper(I) or copper(II) salts of hydrohalic acids, hydrocyanic acids, or copper salts of aliphatic carboxylic acids. Examples of suitable copper salts include copper chloride (I), copper bromide (I), copper iodide (I), copper cyanide (I), copper chloride (II), copper acetate (II), copper stearate (II), and combinations thereof. Copper iodide (I) and copper cyanide (I) are particularly suitable.

[0072] In addition to copper compounds, heat stabilizers may also contain halogen-containing synergists. When used, the copper compound and the halogen-containing synergist are typically used in amounts providing a copper:halogen molar ratio from about 1:1 to about 1:50, in some embodiments from about 1:4 to about 1:20, and in some embodiments from about 1:6 to about 1:15. For example, the halogen content of the thermoplastic polymer composition may be from about 1 ppm to about 10,000 ppm, in some embodiments from about 50 ppm to about 5,000 ppm, in some embodiments from about 100 ppm to about 2,000 ppm, and in some embodiments from about 300 ppm to about 1,500 ppm. On the other hand, the halogen content of the thermoplastic polymer composition is less than about 1000 ppm, such as less than about 600 ppm, such as less than about 500 ppm, such as less than about 400 ppm.

[0073] Halogenation synergists typically include organic halogenated compounds such as aromatic and / or aliphatic halogenated phosphates, aromatic and / or aliphatic halogenated hydrocarbons, and combinations thereof. For example, suitable halogenated aliphatic phosphates may include tris(haloalkyl)-phosphates and / or phosphonates. Tris(bromoalkyl)phosphates (brominated aliphatic phosphates) are particularly suitable. In particular, in these compounds, no hydrogen atom is attached to the alkyl C atom at the α-position of the C atom attached to the halogen. This minimizes the extent to which dehydrohalogenation reactions can occur, which further enhances the stability of the thermoplastic polymer composition. Specific exemplary compounds are tris(3-bromo-2,2-bis(bromomethyl)propyl)phosphate, tris(dibromoneopentyl)phosphate, tris(trichloroneopentyl)phosphate, tris(bromodichloroneopentyl)phosphate, tris(chlorodibromoneopentyl)phosphate, tris(tribromoneopentyl)phosphate, or combinations thereof. Suitable halogenated aromatic hydrocarbons may include halogenated aromatic polymers (including oligomers), such as brominated styrene polymers (e.g., polydibromostyrene, polytribromostyrene, etc.); halogenated aromatic monomers, such as brominated phenols (e.g., tetrabromobisphenol-A); and combinations thereof.

[0074] Thermoplastic polymer compositions may optionally include a light stabilizer, which may comprise a hindered amine light stabilizer. Regardless of the compound from which it is derived, the hindered amine may be an oligomer or polymeric compound with a number average molecular weight of about 1,000 or greater, from about 1,000 to about 20,000 in some embodiments, from about 1,500 to about 15,000 in some embodiments, and from about 2,000 to about 5,000 in some embodiments. Such compounds typically contain at least one 2,2,6,6-tetraalkylpiperidinyl group (e.g., 1 to 4) per polymer repeating unit. Furthermore, low molecular weight hindered amines may also be used in thermoplastic polymer compositions. Such hindered amines are typically monomeric in nature and have a molecular weight of about 1,000 or less, from about 155 to about 800 in some embodiments, and from about 300 to about 800 in some embodiments.

[0075] Examples of light stabilizers that can be incorporated into this disclosure include phthalamides. Light stabilizers may also comprise any compound derived from an alkyl-substituted piperidinyl, piperidinyl, or piperazine compound, or a substituted alkoxypiperidinyl compound. Other suitable HALS are those derived from 2,2,6,6-tetramethylpiperidine. Preferred specific examples of HALS include: ~2,2,6,6-tetramethyl-4-piperidinone, ~2,2,6,6-tetramethyl-4-piperidinol, ~bis-(2,2,6,6-tetramethyl-4-piperidinyl)-sebate, ~mixtures of 2,2,6,6-tetramethyl-4-piperidinol and fatty acid esters, ~bis-(2,2,6,6-tetramethyl-4-piperidinyl)-succinate, ~bis-(1-octoxy-2,2,6,6-tetramethyl-4-piperidinyl)-sebate, ~bis-(1,2,2,6,6-pentamethyl-4-piperidinyl)-sebate, ~tetra-(2,2,6,6-tetramethyl-4-piperidinyl)-1,2,3, 4-Butane-tetracarboxylic acid ester, ~N-Butyl-2,2,6,6-Tetramethyl-4-piperidinamine, ~N,N'-Bis-(2,2,6,6-Tetramethyl-4-piperidinyl)-hexane-1,6-diamine, ~2,2'-[(2,2,6,6-Tetramethyl-4-piperidinyl)-imino]-bis-[ethanol], ~5-(2,2,6,6-Tetramethyl-4-piperidinyl)-2-cyclo-undecyl-oxazole), ~mixtures of the following: 2,2,4,4-Tetramethyl-21-oxo-7-oxa-3,20-diazabispiro[5.1.11.2]eicosane-20-propionate dodecyl ester and 2,2,4,4-Tetramethyl-21-oxo-7; Oxa-3,20-diazabispiro[5,1,11,2]-eicosano-20-propionic acid; tetradecyl ester, ~diacetam 5 (CAS Registry No.: 76505-58-3), ~malonic acid, [(4-methoxyphenyl)methylene]-, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester, ~1,3-phenylenediamide, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl), ~3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidinyl)-pyrrolidine-2,5-dione, ~formamide, N,N'-1,6-hexanediylbis[N-(2,2,6,6-tetramethyl-4-piperidinyl, ~3-dodecyl-1- (1,2,2,6,6-pentamethyl-4-piperidinyl)-pyrrolidine-2,5-dione, ~1,5-dioxaspiro(5,5)undecane-3,3-dicarboxylic acid, bis(2,2,6,6-tetramethyl-4-piperidinyl) ester, ~1,5-dioxaspiro(5,5)undecane-3,3-dicarboxylic acid, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester, ~bis(1,2,2,6,6-pentamethyl-4-piperidinyl)(3,5-Di-tert-butyl-4-hydroxybenzyl)-butylmalonate, ~tetra-(1,2,2,6,6-pentamethyl-4-piperidinyl)-1,2,3,4-butane-tetra-carboxylic acid ester, ~1,2,3,4-butanetetracarboxylic acid, tetra(2,2,6,6-tetramethyl-4-piperidinyl) ester, ~1,2,3,4-butane-tetracarboxylic acid-1,2,3-tris(1,2,2,6,6-pentamethyl-4-piperidinyl)-4-tetrazyl ester, ~8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro(4,5)decane-2,4-dione, ~N-2,2,6,6-tetramethyl-4-piperidinyl-N-amino 4-Acryloyloxy-1,2,2,6,6-pentamethyl-4-piperidine, 1,5,8,12-tetra[2',4'-bis(1'',2'',2'',6'',6''-pentamethyl-4''-piperidinyl(butyl)amino)-1',3',5'-triazin-6'-yl]-1,5,8,12-tetraazadodecane, 1,1'-(1,2-ethane-di-yl)-bis-(3,3',5,5'-tetramethyl-piperazinone) (Goodrite) 3034), ~propaneamide, 2-methyl-N-(2,2,6,6-tetramethyl-4-piperidinyl)-2-[(2,2,6,6-tetramethyl-4-piperidinyl)amino], ~N-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol and succinic acid oligomer, ~poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl][2, 2,6,6-Tetramethyl-4-piperidinyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidinyl)imino]], ~poly[(6-morpholino-S-triazine-2,4-diyl)[(2,2,6,6-tetramethyl-4-piperidinyl)imino]hexamethylene-[(2,2,6,6-tetramethyl-4-piperidinyl)imino]], ~poly[(6-morpholino-S-triazine] Azine-2,4-diyl)[1,2,2,6,6-pentamethyl-4-piperidinyl)imino]-hexamethylene[(2,2,6,6-tetramethyl-4-piperidinyl)imino], ~α-methylstyrene with n-(2,2,6,6-tetramethyl-piperidinyl)-4-maleimide and N-stearoyl-maleimide polymethylpropyl-3-oxy-[4(2,2,6,6-tetramethyl)-piperidinyl] [Piridine]-siloxane copolymer, ~1,2,3,4-butanetetracarboxylic acid, and 8,8,8',8'-tetramethyl-2,4,8,10-tetraoxazolo[5,5]undecane-3,9-diethanol, a polymer of 1,2,2,6,6-pentamethyl-4-piperidine ester, ~1,2,3,4-butanetetracarboxylic acid, and 8,8,8',8'-tetramethyl-2,4,8,10-tetraoxazolo[5,5] Polymer of undecane-3,9-diethanol, 2,2,6,6-tetramethyl-4-piperidinyl ester, ~7-oxa-3,20-diazabispiro[5,1,11,2]cosicosando-21-one, 2,2,4,4-tetramethyl-20-(epoxyethylenemethyl) oligomer, ~1,3,5-triazine-2,4,6-triamine, N,N''-[1,2-ethanediylbis[[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine- -2-yl]imino]-3,1-propanediyl]]-bis[N.N''-dibutyl-N.N''-bis(1,2,2,6,6-pentamethyl-4-piperidinyl), ~1,3-propanediamine, N,N-1,2-ethanediylbis-, polymers with 2,4,6-trichloro-1,3,5-triazine, reaction products with N-butyl-2,2,6,6-tetramethyl-4-piperidinylamine, ~1,6-hexanediamine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)- polymers with 2,4,6-trichloro-1,3,5-triazine, with N-butyl-1-butylamine and N-butyl-2,2,6,6-tetramethyl The reaction product of -4-piperidinamine, ~2,9,11,13,15,22,24,26,27,28-decaazatricyclo[21,3,1,110,14]octadec-1(27), 10,12,14(28), 23,25-hexane-12,25-diamine, N,N'-bis(1,1,3,3-tetramethylbutyl)-2,9,15,22-tetra(2,2,6,6-tetramethyl-4-piperidinyl)-, ~1,1,1''-(1,3,5-triazine-2,4,6-triyltri((cyclohexylimino)-2,1-ethanediyl)tri(3,3,5,5-tetramethylpiperazinone), ~ 1,1,1''-(1,3,5-triazine-2,4,6-triyltris((cyclohexylimino)-2,1-ethylenediyl)tris(3,3,4,5,5-tetramethylpiperazinone), ~1,6-hexanediamine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-, polymers with 2,4,6-trichloro-1,3,5-triazine, with 3-bromo-1-propene, n-butyl-1-butylamine and N The reaction product of butyl-2,2,6,6-tetramethyl-4-piperidinamine, oxidized, hydrogenated, ~olefin, (C20-24)-4α-, polymer with maleic anhydride, reaction product with 2,2,6,6-tetramethyl-4-piperidinamine, ~N-2,2,6,6-tetramethyl-4-piperidinyl-N-amino-oxalamide; 4-acryloyloxy-1,2,2,6,6-pentamethyl-4-piperidin; HALS PB-41 or mixtures thereof.

[0076] In some respects, one or more stabilizers containing secondary amines can also be used in thermoplastic polymer compositions. Secondary amines can be aromatic in nature, such as N-phenylnaphthylamine (e.g., Naugard® PAN from Uniroyal Chemical); diphenylamines, such as 4,4′-bis(dimethylbenzyl)-diphenylamine (e.g., Naugard® 445 from Uniroyal Chemical); p-phenylenediamine (e.g., Wingstay® 300 from Goodyear); quinolones, etc. Particularly suitable secondary amines are oligomeric or polymeric amines, such as homopolymers or copolymers of polyamides. Examples of such polyamides can include nylon 3 (poly-β-alanine), nylon 6, nylon 10, nylon 11, nylon 12, nylon 6 / 6, nylon 6 / 9, nylon 6 / 10, nylon 6 / 11, nylon 6 / 12, polyesteramides, polyamide-imides, polyacrylamides, etc. In one specific embodiment, the amine is a polyamide terpolymer with a melting point in the range of 120°C to 220°C. Suitable terpolymers may be based on nylons selected from the group consisting of nylon 6, nylon 6 / 6, nylon 6 / 9, nylon 6 / 10, and nylon 6 / 12, and may include nylon 6-66-69; nylon 6-66-610, and nylon 6-66-612. An example of such nylon terpolymer is a terpolymer of nylon 6-66-610, and it is commercially available from Celanese under the name Elvamide® 8063R. The secondary amine may comprise from about 0.01 wt.% to about 2 wt.% of the total polymer composition.

[0077] On one hand, the thermoplastic polymer composition may contain a phosphorus-containing antioxidant. Phosphorus-containing antioxidants may include, for example, phosphonites having the following structure: [RP(OR1)2] m (1) in, R is a monovalent or polyvalent aliphatic, aromatic, or heteroaromatic organic group, such as cyclohexyl, phenyl, phenylene, and / or biphenyl; and R1 is independently a compound having structure (II). Alternatively, the two groups R1 can form a bridging group with structure (III). in A represents a direct bond, O, S, and C. 1-18 Alkylene (straight-chain or branched), or C 1-18 Mesenchymalyl groups (straight-chain or branched); R2 is independently C 1-12Alkyl (straight-chain or branched), C 1-12 alkoxy, or C 5-12 cycloalkyl; n ranges from 0 to 5, in some embodiments from 1 to 4, and in some embodiments from 2 to 3. m ranges from 1 to 4, from 1 to 3 in some embodiments, and from 1 to 2 (e.g., 2) in some embodiments.

[0078] The preferred formulation is based on the foregoing requirements, comprising compounds prepared by reacting an aromatic or heteroaromatic system (such as benzene, biphenyl, or diphenyl ether) with a phosphorus trihalide (preferably phosphorus trichloride) in the presence of a Fried-Krawst catalyst (such as aluminum chloride, zinc chloride, ferric chloride, etc.) via a Fried-Krawst reaction, followed by a reaction with a phenol in structures (II) and (III). The invention also explicitly encompasses mixtures of phosphites produced from excess phosphorus trihalide and the aforementioned phenols in a specified reaction sequence.

[0079] In one specific embodiment, R1 is a group having structure (II). Among this group of compounds, antioxidants having a general structure (V) are particularly suitable: Where n is as defined above.

[0080] In one specific embodiment, for example, n in formula (V) is 1, such that the antioxidant is tetrakis(2,4-di-tert-butylphenyl)4,4'-biphenyl-diphosphonite.

[0081] In one embodiment, the antioxidant may be the reaction product of 2,4-di-tert-butylphenol, phosphorus trichloride, and 1,1'-biphenyl.

[0082] In one embodiment, the antioxidant may be a mixture of hindered phenolic antioxidants and phosphites. For example, the antioxidant may be a mixture of NN′-hexamethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoamide) and tris(2,4-di-tert-butylphenyl) phosphite.

[0083] Typically, the thermoplastic polymer composition formed according to this disclosure may contain one or more stabilizers (e.g., one or more heat stabilizers, one or more light stabilizers, etc.) in amounts from about 0 wt.% to about 5 wt.% (including all increments of 0.01 wt.%). For example, the thermoplastic polymer composition formed according to this disclosure may contain one or more stabilizers in an amount of about 0 wt.% or more, such as about 0.01 wt.% or more, such as about 0.05 wt.% or more, such as about 0.1 wt.% or more, such as about 0.2 wt.% or more, such as about 0.25 wt.% or more, such as about 0.5 wt.% or more, such as about 0.75 wt.% or more, such as about 1 wt.% or more, such as about 1.25 wt.% or more, such as about 1.5 wt.% or more, such as about 2 wt.% or more, such as about 3 wt.% or more, such as about 4 wt.% or more, such as about 5 wt.% or less, such as about 4 wt.% or less, such as about 3 wt.% or less, such as about 2 wt.% or less, such as about 1.5 wt.% or less, such as about 1.25 wt.% or less, such as about 1 wt.% or less, such as about 0.75 wt.% or less, such as about 0.5 wt.% or less, such as about 0.25 wt.% or less, such as about 0.2 wt.% or less, such as about 0.1 wt.% or less, such as about 0.05 wt.% or less.

[0084] In addition to the components mentioned above, the thermoplastic polymer composition may contain a variety of other components. Examples of such optional components may include, for example, reinforcing and / or EMI fillers, compatibilizers, particulate fillers, lubricants, colorants, flow modifiers, pigments, and other materials added to enhance performance and processability. For example, EMI fillers may be used when EMI shielding performance is desired. EMI fillers are typically formed of conductive materials that can provide the desired level of electromagnetic interference shielding. In some embodiments, for example, the material contains metals such as stainless steel, aluminum, zinc, iron, copper, silver, nickel, gold, chromium, etc., and alloys or mixtures thereof. EMI fillers may also be in a variety of different forms, such as granules (e.g., iron powder), flakes (e.g., aluminum flakes, stainless steel flakes, etc.), or fibers. Particularly suitable EMI fillers are metal-containing fibers. In such embodiments, the fibers may be formed primarily of metal (e.g., stainless steel fibers), or the fibers may be formed of a core material coated with metal. When a metal coating is used, the core material may be formed of a material that is inherently conductive or insulating. For example, the core material may be formed of carbon, glass, or a polymer. An example of such fibers is nickel-coated carbon fiber. lubricant

[0085] On one hand, the lubricant can be present in the thermoplastic polymer composition. Any suitable lubricant can be incorporated into the thermoplastic polymer composition. On the other hand, the lubricant can contain partially saponified ester waxes. For example, the lubricant can contain C... 22 To C 36 Partially saponified ester waxes of fatty acids. For example, fatty acids can include lignite wax. On one hand, lubricants can contain 1-methyl-1,3-propanediyl ester. On the other hand, lubricants can be fatty acid amides, including primary fatty acid amides, secondary fatty acid amides, and so on. Other suitable lubricants include metal salts of fatty acids, such as calcium stearate, aluminum distearate, zinc stearate, magnesium stearate, and mixtures thereof.

[0086] Typically, the lubricant may be present in the thermoplastic polymer composition in an amount greater than about 0.01% by weight, such as greater than about 0.05% by weight, such as greater than about 0.08% by weight, such as greater than about 0.1% by weight, such as greater than about 0.2% by weight, such as greater than about 0.3% by weight, such as greater than about 0.4% by weight, and generally in an amount less than about 3% by weight, such as less than about 2.5% by weight, such as less than about 2% by weight, such as less than about 1.5% by weight, such as less than about 1% by weight, such as less than about 0.8% by weight, such as less than about 0.5% by weight.

[0087] Other disclosures

[0088] Differential scanning calorimetry can typically be used to determine various properties of thermoplastic polymer compositions formed according to this disclosure.

[0089] The freezing point, which may be referred to as the crystallization peak temperature of a thermoplastic polymer composition, can be determined by differential scanning calorimetry (“DSC”), a method known in the art. The crystallization peak temperature is measured during the cooling phase of the differential scanning calorimetry process and represents the maximum value of the exothermic peak obtained during the cooling process.

[0090] The thermoplastic polymer compositions disclosed herein can exhibit a freezing point from about 120°C to about 200°C (inclusive of all 1°C increments therein), as determined by differential scanning calorimetry, such as about 120°C or higher, about 125°C or higher, about 130°C or higher, about 135°C or higher, about 140°C or higher, about 145°C or higher, about 150°C or higher, about 155°C or higher, about 160°C or higher, about 165°C or higher, about 170°C or higher, about 175°C or higher, about 180°C or higher. The freezing point can be determined according to ASTM D3418:2015. (The remaining text appears to be a list of temperature ranges and values, which are not translated as they are not part of the main text.)

[0091] The melting point, which may be referred to as the melting peak temperature, can be determined using differential scanning calorimetry (“DSC”), a method known in the art. The melting peak temperature is measured during the second heating stage of the differential scanning calorimetry process and represents the maximum value of the endothermic peak during the second heating stage of the DSC process.

[0092] The thermoplastic polymer compositions disclosed herein may exhibit at least one melting point from about 175°C to about 250°C (inclusive of all 1°C increments therein), as determined by differential scanning calorimetry, such as about 175°C or higher, about 180°C or higher, about 190°C or higher, about 200°C or higher, about 210°C or higher, about 215°C or higher, or about 220°C or higher. The melting point can be determined according to ASTM D3418:2015. (The remaining text appears to be a list of temperature ranges and values, which are not translated as they are not part of the main text.)

[0093] The heat of fusion of the thermoplastic polymer composition can be further determined by differential scanning calorimetry (DSC). As used herein, heat of fusion refers to the heat of fusion during the second heating stage of the DSC process. The thermoplastic polymer compositions disclosed herein can exhibit heats of fusion from about 10 J / g to about 60 J / g (inclusive of all increments of 1 J / g). For example, thermoplastic polymer compositions may exhibit heats of melting of about 10 J / g or greater, such as about 15 J / g or greater, such as about 20 J / g or greater, such as about 25 J / g or greater, such as about 30 J / g or greater, such as about 35 J / g or greater, such as about 40 J / g or greater, such as about 45 J / g or greater, such as about 50 J / g or greater, such as about 55 J / g or greater, such as about 60 J / g or less, such as about 55 J / g or less, such as about 50 J / g or less, such as about 45 J / g or less, such as about 40 J / g or less, such as about 35 J / g or less, such as about 30 J / g or less, such as about 25 J / g or less, such as about 20 J / g or less, such as about 15 J / g or less. Heats of melting can be determined according to ASTM D3418:2015.

[0094] In some respects, the thermoplastic polyamide compositions formed according to this disclosure can have melt viscosities from about 500 Pa·s to about 15,000 Pa·s (inclusive of all increments of 1 Pa·s therein). Typically, the melt viscosity can be determined according to ASTM D3835 at 250°C or 260°C and within 10 s. -1 30 s -1 100 s -1 300 s -1 500 s -1 1000 s -1 2000 s -1 Or 3000 s -1 The shear rate was determined using a capillary rheometer (Kayeness). For example, the thermoplastic polyamide composition formed according to this disclosure can have the shear rate as specified in ASTM D3835 at 250°C and 1000 s. -1 Melt viscosities ranging from about 500 Pa·s to about 1500 Pa·s were measured at shear rates. Furthermore, for example, the thermoplastic polyamide compositions formed according to this disclosure can have melt viscosities as specified in ASTM D3835 at a temperature of 250°C and a melting point of 30 s. -1 Melt viscosity, measured at shear rates from approximately 5000 Pa·s to approximately 10000 Pa·s.

[0095] In some respects, the thermoplastic polyamide compositions formed according to this disclosure can have a strength from about 5 kJ / m 2 Approximately 30 kJ / m2 (including 1 kJ / m) 2 Charpy impact strength (e.g., notched Charpy impact strength) is measured according to ISO 179-1:2023 at temperatures of -30°C, -40°C, -50°C, or -60°C. For example, the thermoplastic polyamide composition formed according to this disclosure can have a Charpy impact strength from about 5 kJ / m² as measured according to ISO 179-1:2023 at a temperature of -50°C. 2 Approximately 25 kJ / m 2 Charpy impact strength. Example Test methods

[0096] Sagging Resistance Test: Sagging resistance tests are performed according to the following description to determine the sag stress experienced by various thermoplastic polymer compositions. The thermoplastic polymer composition formulations listed below (i.e., samples 1-5 and control samples C1-C7) are compounded in a 25 mm twin-screw extruder or obtained as commercial products. The thermoplastic polymer compositions are molded into ASTM D638 Type IV tensile bars. Figure 2 As shown, the tensile bar 20 of the anti-sagging test system 18 is vertically suspended at the upper end of a narrow gauge section by two suspension bars 22 in an oven preheated to three different blow molding process temperatures. A 10-gram weight 24 is suspended from the lower end of the narrow gauge section of the tensile bar by ropes 26. This places the gauge section of the tensile bar under tensile load while it is heated above its melting point to the expected processing temperature. This setup is used to simulate a blow molding scenario where a preform of a molten thermoplastic polymer composition is formed and suspended on the die head under its own weight. By attaching thermocouples to the surface of the tensile bar and measuring its temperature rise over time after being positioned inside the preheated oven, it was determined that it took 6 minutes for the tensile bar to heat to the oven temperature. Starting with an initial suspension weight of 10 grams, an additional 3 minutes are allowed after the 6-minute heating time. In this respect, the weight is suspended on each tensile bar for a total of 9 minutes. Once the tensile bar is able to support the suspended weight without collapsing due to melt sagging and stretching over the total duration, the next test is conducted with a new bar of the same composition, increasing the suspended weight to 30 grams in 5-gram increments. This test is performed at three oven temperatures of 235°C, 240°C, and 250°C to determine the maximum weight that the bar of each composition can support at each temperature. The total weight is divided by the cross-sectional area of ​​the gauge length to determine the tensile strength (in gm / cm²) that the bar can withstand. 2 The design of the flow stress.

[0097] Heat of fusion test: Heat of fusion can be determined by differential scanning calorimetry (“DSC”) as known in the art. Heat of fusion is differential scanning calorimetry (DSC) heat of fusion with a second heating stage as determined by ASTM D3418:2015. Under the DSC procedure, the sample is heated and cooled at 10°C per minute using a DSC measurement performed on a TA Q2000 instrument as described in ASTM D3418:2015.

[0098] Melting point test: The melting point was determined by differential scanning calorimetry (“DSC”) as known in the art. The melting point is the melting peak temperature of the differential scanning calorimetry (DSC) as determined by ASTM D3418:2015. Under the DSC procedure, the sample was heated and cooled at 10°C per minute using a DSC measurement performed on a TA Q2000 instrument as described in ASTM D3418:2015.

[0099] Freezing Point Test: The freezing point was determined by differential scanning calorimetry (“DSC”) as known in the art. The freezing point is the crystallization peak temperature as determined by differential scanning calorimetry (DSC) according to ASTM D3418:2015. Under the DSC procedure, using DSC measurements performed on a TAQ2000 instrument, the sample was heated and cooled at 10°C per minute as described in ASTM D3418:2015.

[0100] Parison drop test: using an extruder screw with a diameter of 65 mm and an 890 cm diameter. 3A Mono-ST brand blow molding machine with a feeder head performs a preform drop test to measure the melt sag resistance of a thermoplastic polymer composition under conditions similar to preform suspension during actual blow molding operations. The machine has an extruder for melting and forming a pool of thermoplastic material, which is transferred to a feeder via a delivery line. A die with an outer diameter set to 16 mm is attached to the bottom of the feeder. The melt is ejected vertically downwards as a cylindrical preform at a controlled, fixed speed by the action of a piston acting on the melt pool in the feeder, and is suspended on the die. A series of 10 infrared light sources and receivers are positioned below the die along the preform's stroke. The first pair is located 2.5 cm from the die exit (“Sensor 1”). Subsequent pairs are located at distances of 3 cm (“Sensor 2”), 7 cm (“Sensor 3”), 12 cm (“Sensor 4”), 22 cm (“Sensor 5”), 32 cm (“Sensor 6”), 42 cm (“Sensor 7”), 57 cm (“Sensor 8”), 82 cm (“Sensor 9”), and 110 cm (“Sensor 10”) from the first pair. The sensors are connected to a data acquisition system. When the extrudate passes the light source, it blocks the beam path. The corresponding receiver detects this beam obstruction and records the cut-off time. In this way, a curve of the time versus the distance traveled at the front end of the parison is recorded. The actual parison travel is affected by the extrusion rate, die swell, and melt sag. Die swell refers to the increase in the parison diameter due to the release of stress applied to the melt, relative to the diameter of the die geometry. A measure of the degree of sag exhibited by the melt can be obtained by comparing the measured curves with theoretical curves based solely on the extrusion rate (without sag and swelling). Curves for various materials can also be compared to rank their respective anti-sag properties. The test was conducted under the following process conditions: the extruder barrel has seven heating zones, with the temperature distribution ranging from 54°C in the feed zone to 245°C in zone 2, and then decreasing to 235°C towards the end of the extruder. The feed line and reservoir were set to 235°C. The extruder screw RPM was 50. The actual melt temperature was 247°C. The piston speed during the discharge process was set to 2 mm / s, resulting in a nominal parison discharge speed of 2 cm / s at the die exit. Example 1

[0101] Thermoplastic polymer compositions comprising three polyamides (i.e., Samples 1-5) were formed and their respective anti-sagging properties were tested. Table 2 shows the weight percentages of the corresponding polyamide and impact modifier in each corresponding sample. Each sample in Table 2 contains an impact modifier. The impact modifier is a maleic anhydride-grafted ethylene copolymer. Each sample in Table 2 contains 0.5 wt.% of a hindered phenolic antioxidant, 0.5 wt.% of a secondary amine, 2 wt.% of a black masterbatch, and 0.1 wt.% of aluminum distearate. As used herein, “black masterbatch” refers to 45 wt.% carbon black in an ethylene / methacrylate copolymer carrier. Table 3 shows the sagging stresses borne by the corresponding samples at 235°C, 240°C, and 250°C. The sagging stresses borne were determined according to previously disclosed anti-sagging tests. Notably, for Samples 2 and 3, no anti-sagging test was performed at 240°C. Freezing point, melting point, and heat of fusion were determined according to previously disclosed freezing point, melting point, and heat of fusion tests. Table 4 shows the freezing point, melting point, and heat of fusion. Table 2 Table 3 Table 4

[0102] Comparative compositions were formed, one composition containing three polyamides (i.e., C1) and the remaining compositions containing two or one polyamide, and their respective anti-sagging properties were tested. Table 5 shows the weight percentages of the corresponding polyamides and impact modifiers in each corresponding sample. The impact modifier for samples C1-C4 was a maleic anhydride-grafted ethylene copolymer. The impact modifier for sample C5 was 15 wt.% maleic anhydride-grafted ethylene copolymer and 7 wt.% maleic anhydride-modified EPDM. The impact modifier for samples C6-C7 was maleic anhydride-modified EPDM. Sample C1 further contained 0.5 wt.% hindered phenolic antioxidant, 0.5 wt.% secondary amine, 2 wt.% black masterbatch, and 0.1 wt.% aluminum distearate. Samples C2-C6 further comprise 0.5 wt.% of hindered phenolic antioxidant, 0.5 wt.% of secondary amine, 2 wt.% of black masterbatch, and 0.1 wt.% of aluminum distearate. Sample C7 further comprises 0.75 wt.% of a first hindered phenolic antioxidant, 0.3 wt.% of copper iodide / aluminum iodide stabilizer, 0.25 wt.% of a second hindered phenolic antioxidant, and 1.2 wt.% of black masterbatch. Table 6 shows the sag stresses experienced by the corresponding comparative samples at 235°C, 240°C, and 250°C. The sag stresses were determined according to previously disclosed anti-sag tests. Freezing point, melting point, and heat of fusion were determined according to previously disclosed freezing point, melting point, and heat of fusion tests. Table 7 shows the freezing point, melting point, and heat of fusion. It is noteworthy that the freezing point, melting point, and heat of fusion of C7 were not determined. Table 5 Table 6 Table 7 Example 2

[0103] Thermoplastic polymer compositions and two comparative compositions were formed and their H2 permeability was tested. Table 8 shows the weight percentages of the corresponding polyamide and impact modifier in each respective sample, and further shows the H2 permeability of each sample. Permeability values ​​were measured according to ISO 15105-1:2007. Sample size was 100 mm × 100 mm × 1 mm. Conditions were 25°C and 42% RH. The impact modifier of sample 6 was a maleic anhydride-grafted ethylene copolymer. Sample 6 further contained 0.7 wt.% of hindered phenolic antioxidant, 0.5 wt.% of secondary amine, 2 wt.% of black masterbatch, and 0.1 wt.% of aluminum distearate. Sample C7 was the same as sample C7 previously disclosed herein. The impact modifier of comparative composition C8 was maleic anhydride-modified EPDM. Comparative composition C8 further comprises 0.6 wt.% of a mixture of hindered phenolic antioxidants and organic phosphites, and 1 wt.% of diol stearate. Table 8 Example 3

[0104] Melt viscosity characteristics were tested for the thermoplastic polymer composition (i.e., sample 6) and two comparative compositions (i.e., samples C1 and C7) as previously disclosed herein. Melt viscosity (Pa·s) was measured according to ASTM D3835 at 250°C or 260°C and within 10 s. -1 30 s -1 100 s -1 300 s -1 500 s -1 1000 s -1 2000 s -1 Or 3000 s -1 The shear rate was measured using a capillary rheometer (Kayeness). Table 9 Example 4

[0105] The thermoplastic polymer composition (i.e., Sample 6) and the comparative composition (i.e., Sample C7) as previously disclosed herein were subjected to a preform drop test as previously disclosed herein. The preform end distance travel versus time curves for both compositions, as well as the theoretical curves without sagging, are numerically presented in Table 10 and... Figure 3 It is illustrated in the text. Table 10

[0106] As observed in Table 10 and as... Figure 3 As shown, sample 6 has significantly better anti-sagging properties than sample C7. Example 5

[0107] The thermoplastic polymer composition (i.e., Sample 6) and the comparative composition (i.e., Sample C7) as previously disclosed herein were injection molded to form test bars for Charpy impact testing according to test method ISO 179-1:2023. These test bars were notched and tested in their molded-as-is condition or conditioned to constant weight at 63% RH and 70°C, and then tested at different temperatures from 23°C to -60°C. The results are shown in Table 11. “-” in Table 11 indicates that the corresponding sample was not tested at the corresponding temperature. Table 11

[0108] As observed in Table 11, Sample 6 exhibits better impact toughness than Sample C7 at lower temperatures. It is noteworthy that the hydrogen tank lining may be exposed to low temperatures during rapid fill-out cycles. In this respect, high impact toughness at low temperatures is generally advantageous.

[0109] While specific embodiments of this disclosure have been shown and described, it will be apparent to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of this disclosure. Therefore, all such changes and modifications are intended to be covered within the scope of this disclosure in the appended claims.

Claims

1. A thermoplastic polymer composition comprising: A first polyamide, the first polyamide comprising a first aliphatic homopolymer; A second polyamide, wherein the second polyamide comprises a semi-aromatic copolyamide; A third polyamide, comprising a second aliphatic homopolymer, wherein the first aliphatic homopolymer and the second aliphatic homopolymer are present in the thermoplastic polymer composition in a weight ratio of about 5:4 or greater; and An impact modifier is present in the thermoplastic polymer composition in an amount greater than about 5 wt.%.

2. The thermoplastic polymer composition of claim 1, wherein, The first aliphatic homopolymer contains repeating units derived from lactams having 6 to 20 carbon atoms.

3. The thermoplastic polymer composition of claim 1, wherein, The second aliphatic homopolymer comprises repeating units derived from aliphatic dicarboxylic acids having 6 to 20 carbon atoms and aliphatic diamines having 4 to 20 carbon atoms.

4. The thermoplastic polymer composition of claim 1, wherein, The semi-aromatic copolyamide comprises repeating units derived from aromatic dicarboxylic acids having 8 to 20 carbon atoms and aliphatic diamines having 4 to 20 carbon atoms.

5. The thermoplastic polymer composition of claim 4, wherein, The semi-aromatic copolyamide further comprises repeating units derived from aliphatic dicarboxylic acids having 6 to 20 carbon atoms and aliphatic diamines having 4 to 20 carbon atoms.

6. The thermoplastic polymer composition of claim 1, wherein, The semi-aromatic copolyamide comprises a first repeating unit present in an amount from about 50 mole percent to about 90 mole percent of the semi-aromatic copolyamide and a second repeating unit present in an amount from about 10 mole percent to about 50 mole percent.

7. The thermoplastic polymer composition of claim 6, wherein, The first repeating unit is an aliphatic repeating unit, and the second repeating unit is an aromatic repeating unit.

8. The thermoplastic polymer composition of claim 1, wherein, The semi-aromatic copolyamide comprises a first repeating unit present in an amount from about 60 mol percent to about 80 mol percent of the semi-aromatic copolyamide and a second repeating unit present in an amount from about 20 mol percent to about 40 mol percent of the semi-aromatic copolyamide.

9. The thermoplastic polymer composition of claim 8, wherein, The first repeating unit is an aliphatic repeating unit, and the second repeating unit is an aromatic repeating unit.

10. The thermoplastic polymer composition of claim 1, wherein, The first aliphatic homopolymer and the second aliphatic homopolymer exist in the thermoplastic polymer composition in a weight ratio of about 3:2 or greater.

11. The thermoplastic polymer composition of claim 1, wherein, The impact modifier was functionalized.

12. The thermoplastic polymer composition of claim 1, wherein, This impact modifier contains anhydride groups.

13. The thermoplastic polymer composition of claim 1, wherein, The first aliphatic homopolymer amide is present in the thermoplastic polymer composition in an amount from about 20 wt.% to about 70 wt.%.

14. The thermoplastic polymer composition of claim 1, wherein, The second aliphatic homopolymer amide is present in the thermoplastic polymer composition in an amount from about 2 wt.% to about 20 wt.%.

15. The thermoplastic polymer composition of claim 1, wherein, The semi-aromatic copolyamide is present in the thermoplastic polymer composition in an amount from about 2 wt.% to about 30 wt.%.

16. The thermoplastic polymer composition of claim 1, wherein, The impact modifier is present in the thermoplastic polymer composition in an amount of less than about 50 wt.%.

17. The thermoplastic polymer composition of claim 1, wherein, The semi-aromatic copolyamide and the second aliphatic homopolyamide contain repeating units derived from the same diacid and the same diamine.

18. The thermoplastic polymer composition of claim 1, wherein, The semi-aromatic copolyamide comprises aliphatic repeating units, wherein the second aliphatic homopolyamide comprises aliphatic repeating units, wherein the aliphatic repeating units of the semi-aromatic copolyamide and the aliphatic repeating units of the second aliphatic homopolyamide are derived from the same diacid and the same diamine.

19. The thermoplastic polymer composition of claim 1, wherein, The first aliphatic homopolymer is PA 6, wherein the semi-aromatic copolymer is PA 610 / 6T, and wherein the second aliphatic homopolymer is PA 610.

20. The thermoplastic polymer composition of claim 19, wherein, The first aliphatic homopolymer is present in the thermoplastic polymer composition in an amount from about 30 wt.% to about 60 wt.%, wherein the semi-aromatic copolyamide is present in the thermoplastic polymer composition in an amount from about 5 wt.% to about 25 wt.%, the semi-aromatic copolyamide comprising an aliphatic repeating unit present in an amount from about 60 mol percent to about 90 mol percent of the semi-aromatic copolyamide and an aromatic repeating unit present in an amount from about 10 mol percent to about 40 mol percent, wherein the second aliphatic homopolymer is present in the thermoplastic polymer composition in an amount from about 5 wt.% to about 15 wt.%, and wherein the impact modifier is present in the thermoplastic polymer composition in an amount from about 15 wt.% to about 40 wt.%.

21. A thermoplastic polymer composition comprising: A first polyamide, the first polyamide comprising an aliphatic copolyamide; A second polyamide, wherein the second polyamide comprises a semi-aromatic copolyamide; A third polyamide comprising an aliphatic homopolymer, wherein the aliphatic copolymer and the semi-aromatic copolymer are present in the thermoplastic polymer composition in a weight ratio of about 6:5 or greater; and An impact modifier is present in the thermoplastic polymer composition in an amount greater than about 5 wt.%.

22. The thermoplastic polymer composition of claim 21, wherein, The aliphatic copolyamide comprises repeating units derived from aliphatic dicarboxylic acids having 6 to 20 carbon atoms and aliphatic diamines having 4 to 20 carbon atoms.

23. The thermoplastic polymer composition of claim 21, wherein, The aliphatic copolyamide further comprises repeating units derived from lactams having 6 to 20 carbon atoms.

24. The thermoplastic polymer composition of claim 21, wherein, The semi-aromatic copolyamide comprises repeating units derived from aromatic dicarboxylic acids having 8 to 20 carbon atoms and aliphatic diamines having 4 to 20 carbon atoms.

25. The thermoplastic polymer composition of claim 24, wherein, The semi-aromatic copolyamide further comprises repeating units derived from aliphatic dicarboxylic acids having 6 to 20 carbon atoms and aliphatic diamines having 4 to 20 carbon atoms.

26. The thermoplastic polymer composition of claim 21, wherein, The aliphatic homopolyamide comprises repeating units derived from aliphatic dicarboxylic acids having 6 to 20 carbon atoms and aliphatic diamines having 4 to 20 carbon atoms.

27. The thermoplastic polymer composition of claim 21, wherein, The semi-aromatic copolyamide and the aliphatic homopolyamide contain repeating units derived from the same diacid and the same diamine.

28. The thermoplastic polymer composition of claim 21, wherein, The semi-aromatic copolyamide comprises aliphatic repeating units, wherein the aliphatic homopolyamide comprises aliphatic repeating units, wherein the aliphatic repeating units of the semi-aromatic copolyamide and the aliphatic repeating units of the aliphatic homopolyamide are derived from the same diacid and the same diamine.

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