WO2025226647A1 - Toughened polyamides - Google Patents

Abstract

In some embodiments, a composition may comprise: a polyamide; an epoxy functional polyolefin comprising one or more epoxy ring functional groups; and a functionalized polyolefin comprising a polyolefin with ethylenically unsubstituted dicarboxylic acid or a derivative thereof, and wherein the mole ratio of the epoxy functional groups to the ethylenically unsubstituted dicarboxylic acid or a derivative thereof is from 20 to 235.

Description

TOUGHENED POLYAMIDES

CROSS-REFERENCE TO RELATED APPLICATIONS

[001] This application claims the benefit of U.S. Provisional Application Serial No. 63/639,263 filed April 26, 2024, the contents of which are incorporated in their entirety herein.

TECHNICAL FIELD

[002] The present disclosure relates to polymer compositions, and more specifically, to polymer compositions comprising polyamides.

TECHNICAL BACKGROUND

[003] Maleic anhydride grafted polyethylenes have long been used to toughen polyamides. However, these toughened polyamides have poor thermal aging properties, resulting in significant degradation of mechanical properties after sustained exposure to high temperatures (e.g., greater than 150 °C). Thus, these toughened polyamides are unsuitable for high temperature applications, such as combustion engine in-take manifolds.

BRIEF SUMMARY

[004] Accordingly, toughened polyamides, which retain their mechanical properties after thermal aging, are desired. Embodiments of the present disclosure meet this need by mixing the polyamide with an epoxy functional polyolefin and a functionalized polyolefin comprising a polyolefin with ethylenically unsubstituted dicarboxylic acid or a derivative thereof wherein the mole ratio of the epoxy functional groups to the ethylenically unsubstituted dicarboxylic acid or a derivative thereof is from 20 to 235. Generally, the poor thermal aging performance of toughened polyamides is believed to be caused by the presence of unreacted acid functionalities (e.g., anhydride) that catalyze the degradation of the polyamide backbone. The use of a specific molar ratio (e.g., from 20 to 235) of the epoxy functional groups to the ethylenically unsubstituted dicarboxylic acid or a derivative thereof is believed to prevent degradation of the polyamide backbone while still sufficiently toughening the composition. [005] Embodiments of the present disclosure are directed to a composition comprising: a polyamide; an epoxy functional polyolefin comprising one or more epoxy ring functional groups; and a functionalized polyolefin comprising a polyolefin with ethylenically unsubstituted dicarboxylic acid or a derivative thereof, and wherein the mole ratio of the epoxy functional groups to the ethylenically unsubstituted dicarboxylic acid or a derivative thereof is from 20 to 235.

[006] These and other embodiments are described in more detail in the Detailed Description. It is to be understood that both the foregoing general description and the following detailed description present embodiments of the presently disclosed technology, and are intended to provide an overview or framework for understanding the nature and character of the technology as it is claimed.

DETAILED DESCRIPTION

[007] The term “polymer” refers to a polymeric compound prepared by polymerizing monomers, whether of the same or a different type. The generic term polymer thus embraces the term “homopolymer,” usually employed to refer to polymers prepared from only one type of monomer as well as “copolymer” which refers to polymers prepared from two or more different monomer types.

[008] “Polyethylene” or “ethylene-based polymer” refers to polymers comprising greater than 50% by weight derived from ethylene monomer. This includes polyethylene homopolymers or copolymers (meaning units derived from two or more monomer types). Common forms of polyethylene known in the art include Low-density polyethylene (LDPE); Linear Low-density polyethylene (LLDPE); Ultra Low-density polyethylene (ULDPE); Very Low-density polyethylene (VLDPE); single-site catalyzed Linear Low-density polyethylene, including both linear and substantially linear low density resins (m-LLDPE); Medium Density Polyethylene (MDPE); and High Density Polyethylene (HDPE).

[009] The term “LDPE” may also be referred to as “high-pressure ethylene polymer” or “highly branched polyethylene” and is defined to mean that the polymer is partly or entirely homopolymerized or copolymerized in autoclave or tubular reactors at pressures above 14,500 psi (100 MPa) with the use of free-radical initiators, such as peroxides (see, for example, U.S. Patent No. 4,599,392, which is hereby incorporated by reference in its entirety). LDPE resins typically have a density in the range of 0.916 g/cm³ to 0.930 g/cm³.

[0010] The term “LLDPE,” includes resin made using Ziegler-Natta catalyst systems as well as resin made using single-site catalysts, including, but not limited to, bis-metallocene catalysts (sometimes referred to as “m-LLDPE”), phosphinimine, and constrained geometry catalysts, and resins made using post-metallocene, molecular catalysts, including, but not limited to, bis(biphenylphenoxy) catalysts (also referred to as polyvalent aryloxyether catalysts). LLDPE includes linear, substantially linear, or heterogeneous ethylene-based copolymers. LLDPEs contain less long chain branching than LDPEs and include the substantially linear ethylene polymers, which are further defined in U.S. Patent No. 5,272,236, U.S. Patent No. 5,278,272, U.S. Patent No. 5,582,923 and U.S. Patent No. 5,733,155 each of which are incorporated herein by reference in their entirety; the homogeneously branched linear ethylene polymer compositions such as those in U.S. Patent No. 3,645,992 which is incorporated herein by reference in its entirety; the heterogeneously branched ethylene polymers such as those prepared according to the process disclosed in U.S. Patent No. 4,076,698 which is incorporated herein by reference in its entirety; and blends thereof such as those disclosed in U.S. Patent No. 3,914,342 and U.S. Patent No. 5,854,045 which are incorporated herein by reference in their entirety. The LLDPE resins can be made via gas-phase, solution-phase, or slurry polymerization or any combination thereof, using any type of reactor or reactor configuration known in the art.

[0011] The term “HDPE” generally refers to polyethylenes having densities greater than about 0.930 g/cm³ and up to about 0.970 g/cm³, which are generally prepared with Ziegler- Natta catalysts, chrome catalysts or single-site catalysts including, but not limited to, substituted mono- or bis-cyclopentadienyl catalysts (typically referred to as metallocene), constrained geometry catalysts, phosphinimine catalysts & polyvalent aryloxyether catalysts (typically referred to as bisphenyl phenoxy).

[0012] As used herein, a “polyolefin” refers to an olefin-based polymer. As used herein, an “olefin,” which may also be referred to as an “alkene,” refers to a linear, branched, or cyclic compound including carbon and hydrogen and having at least one double bond. As used herein, when a polymer or copolymer, e.g., the polyolefin elastomer, is referred to as comprising an olefin, the olefin present in the polymer or copolymer is the polymerized form of the olefin.

[0013] A composition may comprise a polyamide; an epoxy functional polyolefin comprising one or more epoxy ring functional groups; and a functionalized polyolefin comprising a polyolefin with ethylenically unsubstituted dicarboxylic acid or a derivative thereof.

[0014] The polyamide may be polymers which comprise recurring amide (-CONH-) groups. The polyamide may comprise at least 20 wt. %, at least 30 wt. %, at least 40 wt. %, at least 50 wt. %, at least 51 wt. %, at least 60 wt. %, at least 70 wt. %, at least 80 wt. %, or even at least 90 wt. % of amide groups. The polyamide may have a melting point of from 160 to 320 °C, such as from 160 to 180 °C, from 180 to 200 °C, from 200 to 220 °C, from 220 to 240 °C, from 240 to 260 °C, from 260 to 280 °C, from 280 to 300 °C, from 300 to 320 °C, or any combination of two or more of these ranges. In embodiments, the polyamide may comprise one or more of polyamide 6, polyamide 11, polyamide 12, polyamide 66, polyamide 610, polyamide 612, polyamide 66/610, polyamide 666, polyamide 6/69, nylon 1010, nylon 1012, PA 6T, high temperature nylon, or blends thereof. Suitable polyamides may include Zytel® resin, available from DuPont.

[0015] In embodiment, the composition may comprise from 60 to 99 wt. %, such as from 60 to 65 wt. %, from 65 to 70 wt. %, from 70 to 75 wt. %, from 75 to 80 wt. %, from 80 to 85 wt. %, from 85 to 90 wt. %, from 90 to 95 wt. %, from 95 to 99 wt. %, or any combination of two or more of these ranges of the polyamide, on the basis of the total weight of the composition.

[0016] The epoxy functional polyolefin may be a polymer that comprises one or more epoxide rings. In embodiments, the epoxy functional polyolefin may be a copolymer, formed from two or more monomers (at least one or more of the monomers comprising at least one epoxide ring). The epoxy functional polyolefin may comprise an a-olefin, such a C2-C20 a- olefin. For example, the a-olefin may be C2, C3, C4, C5, Ce, C7, Cs, C9, C10, C11, C12, C13, C14, C15, Ci6, C17, Cis, C19, or C20 olefin. The epoxy functional polyolefin may comprise an alkyl acrylate, such as methyl acrylate, ethyl acrylate, or butyl acrylate. The epoxy functional polyolefin may comprise a monomer having an epoxy functionality, such as a glycidyl group, such as glycidyl acrylate, glycidyl alkyl acrylate, glycidyl methacrylate (GMA), or allyl glycidyl ether (AGE). Other suitable monomers having epoxy functionality include, without limitation, (3,4-epoxycyclohexyl) methyl acrylate, (3,4-epoxycyclohexyl) methyl acrylate, and l,2-epoxy-4-vinylcyclohexane. In embodiments, the epoxy functional polyolefin may be a terpolymers comprising the C2-C20 a-olefin, the alkyl acrylate, and the monomer having epoxy functionality. In embodiments, the epoxy functional polyolefin may be a terpolymer comprising ethylene, butyl acrylate, glycidyl methacrylate (E/nBA/GMA). In embodiments, the epoxy functional polyolefin (such as a terpolymer of ethylene, alkyl acrylate, and glycidyl alkyl acrylate) may comprise from 1 to 15 wt. %, such as from 1 to 3 wt. %, from 3 to 5 wt. %, from 5 to 8 wt. %, from 8 to 12 wt. %, from 12 to 15 wt. %, or any combination of two or more of these ranges of the glycidyl alkyl acrylate; and from 10 to 40 wt.%, such as from 10 to 15 wt. %, from 15 to 20 wt. %, from 20 to 25 wt. %, from 25 to 30 wt. %, from 30 to 35 wt. %, from 35 to 40 wt. %, or any combination of two or more of these ranges, of the alkyl acrylate. The epoxy functional polyolefin may have a melt index (I2) of 1.0 to 30 g/10 min, such as from 1.0 to 3.0 g/10 min, from 3.0 to 6.0 g/10 min, from 6.0 to 10 g/10 min, from 10 to 15 g/10 min, from 10 to 15 g/10 min, from 15 to 20 g/10 min, from 20 to 25 g/10 min, from 25 to 30 g/10 min, or any combination of two or more of these ranges. As those skilled in the art would understand, the concentration of the epoxy functional groups can be measured by Nuclear Magnetic Resonance (NMR).

[0017] In embodiments, the composition may comprise from 0.8 to 39 wt. %, such as from 0.8 to 2 wt. %, from 2 to 4 wt. %, from 4 to 8 wt. %, from 8 to 12 wt. %, from 12 to 15 wt. %, from 15 to 20 wt. %, from 20 to 25 wt. %, from 25 to 30 wt. %, from 30 to 35 wt. %, from 35 to 39 wt. %, or any combination of two or more of these ranges of the epoxy functional polyolefin, on the basis of the total weight of the composition.

[0018] As mentioned previously, the composition may comprise a functionalized polyolefin. The functionalized polyolefin may comprise at least one a-olefin, such as a C2- C14 a-olefin. Contemplated C2-C14 a-olefins include, by way of example and not limitation, C2, C3, C4, C5, Ce, C7, Cs, C9, C10, Cn, C12, C13, or C14 a-olefins. In embodiments, the a- olefin may be ethylene and the functionalized polyolefin may comprise functionalized polyethylene. In embodiments, the polyolefin may comprise EEDPE, HDPE, polyolefin elastomer (such as polyethylene elastomer), or polyolefin plastomer. In embodiments, the functionalized polyolefin may comprise at least two a-olefins. For example, the functionalized polyolefin may comprise ethylene and a C3-C14 a-olefin.

[0019] The functionalized polyolefin may be functionalized with an ethylenically unsubstituted dicarboxylic acid or derivative thereof. The functionalized polyolefin may be formed by co-polymerizing the ethylenically unsubstituted dicarboxylic acid or derivative with the one or more a-olefins or by grafting the ethylenically unsubstituted dicarboxylic acid or derivative onto the polyolefin. The ethylenically unsubstituted dicarboxylic acid or derivative thereof may be selected from maleic anhydride, itaconic anhydride, maleic acid diesters, fumaric diesters, maleic acid monoesters or fumaric acid monoesters, esters of Ci to C4 alcohols, maleic acid, itaconic acid, fumaric acid, or mixtures thereof. For example, the functionalized polyolefin, such as a functionalized polyethylene, may include an anhydride functionalized polyolefin, such as maleic anhydride functionalized polyolefin, such as maleic anhydride functionalized polyethylene, such as maleic anhydride grafted polyolefin. The functionalized polyolefin may have a functionalization level of from 0.1 to 3.0 wt. %, such as from 0.15 to 2.0 wt. %, from 0.1 to 0.5 wt. %, from 0.5 to 1.0 wt. %, from 1.0 to 1.5 wt. %, from 1.5 to 2.0 wt. %, from 2.0 to 2.5 wt. %, from 2.5 to 3.0 wt. %, or any combination of two or more of these ranges, of ethylenically unsubstituted dicarboxylic acid or derivative thereof. In embodiments, the functionalized polyolefin may have been grafted with from 0.1 to 3.0 wt. %, such as from 0.15 to 2.0 wt. %, from 0.1 to 0.5 wt. %, from 0.5 to 1.0 wt. %, from 1.0 to 1.5 wt. %, from 1.5 to 2.0 wt. %, from 2.0 to 2.5 wt. %, from 2.5 to 3.0 wt. %, or any combination of two or more of these ranges, of maleic anhydride. As those skilled in the art would understand, the concentration of the ethylenically unsubstituted dicarboxylic acid (or derivative thereof) can be measured by Fourier Transform Infrared (FTIR).

[0020] The polyolefin of the functionalized polyolefin (such as a polyethylene elastomer) may have a density of from 0.855 to 0.890 g/cc, such as from 0.855 to 0.860 g/cc, from 0.860 to 0.865 g/cc, from 0.865 to 0.875 g/cc, from 0.875 to 0.880 g/cc, from 0.880 to 0.885 g/cc, from 0.885 to 0.890 g/cc, or any combination of two or more of these ranges. The functionalized polyolefin may have a melt index (I2) of from 0.1 to 15 dg/min, such as from 0.1 to 0.5 dg/min, from 0.5 to 1.0 dg/min, from 1.0 to 3.0 dg/min, from 3.0 to 5 dg/min, from 5 to 10 dg/min, from 10 to 15 dg/min, or any combination of two or more of these ranges. [0021] In embodiments, the composition may comprise from 0.1 to 8 wt. %, such as from 0.1 to 0.5 wt. %, from 0.5 to 1 wt. %, from 1 to 2 wt. %, from 2 to 3 wt. %, from 3 to 4 wt. %, from 4 to 5 wt. %, from 5 to 6 wt. %, from 6 to 7 wt. %, from 7 to 8 wt. %, or any combination of two or more of these ranges of the functionalized polyolefin, on the basis of the total weight of the composition.

[0022] In embodiments, the composition may further comprise one or more epoxy oils or resins. The epoxy oils or resins may include, for example, epoxidized vegetable oils, such as epoxidized soybean oil. Such oils may comprise oxiranes and may have an oxirane oxygen level up to 8%. In embodiments, the composition may comprise up to 10 wt. %, such as from 0 to 10 wt. %, from 0.1 to 10 wt. %, from 0 to 0.1 wt. %, from 0.1 to 0.5 wt. %, from 0.5 to 1 wt. %, from 1 to 2 wt. %, from 2 to 4 wt. %, from 4 to 6 wt. %, from 6 to 8 wt. %, from 8 to 10 wt. %, or any combination of two or more of these ranges of the epoxy oils or resins. It should be understood that the ratio of epoxy functional groups includes both the epoxy functional groups in the epoxy functional polyolefin and the epoxy functional groups in the epoxy oils or resins.

[0023] The composition may comprise an inorganic filler, which can decrease cost or increase hardness. Suitable inorganic fillers may include CaCO3, clay, talc, coal ash, carbon black, silica, and glass fibers. Generally, inorganic fillers, such as CaCO3, may provide both volumetric filler and hardening properties at low cost. The inorganic filler may have a particle size or a fiber diameter of from 0.01 to 300 microns, such as from 0.01 to 30 microns, from 0.5 to 1 microns, from 1 to 5 microns, from 5 to 10 microns, from 10 to 15 microns, from 15 to 30 microns, from 30 to 50 microns, from 50 to 100 microns, from 100 to 200 microns, from 200 to 300 microns, or any combination of two or more of these ranges. Where fibers are used, the fibers may have a fiber length of less than 10 mm, such as less than 5 mm, less than 3 mm, less than 1 mm, at least 10 microns, at least 50 microns, at least 100 microns, at least 500 microns, at least 1000 microns, from 10 microns to 100 microns, from 100 microns to 250 microns, from 250 microns to 500 microns, from 500 microns to 1000 microns, from 1000 microns to 2000 microns, from 2000 microns to 3000 microns, or any combination of two or more of these ranges. In embodiments, the composition may comprise from 0 to 40 wt. %, such as from 0 to 30 wt. %, from 0 to 20 wt. %, from 0 to 10 wt. %, from 0 to 5 wt. %, from 0 to 1 wt. %, from 1 to 40 wt. %, from 1 to 30 wt. %, from 1 to 20 wt. %, or from 1 to 10 wt. % of the inorganic fillers.

[0024] It should be understood that the above-described compositions, may further include one or more stabilizers, including heat stabilizers, viscosity stabilizers, hydrolytic stabilizers, antioxidants, and ultraviolet light absorbers. In embodiments, the compositions produced therefrom, may comprise from 0 to 40 wt. %, such as from 0 to 30 wt. %, from 0 to 20 wt. %, from 0 to 10 wt. %, from 0 to 5 wt. %, from 0 to 1 wt. %, from 1 to 40 wt. %, from 1 to 30 wt. %, from 1 to 20 wt. %, or from 1 to 10 wt. % of the stabilizer.

[0025] It should be understood that the compositions, may further include one or more additives as known to those of skill in the art such as, for example, plasticizers, anti-static agents, dyes, pigments or other coloring agents, fire-retardants, lubricants, reinforcing agents such as glass fiber and flakes, synthetic (for example, aramid) fiber or pulp, foaming or blowing agents, processing aids, slip additives, anti-block agents such as silica or talc, release agents, tackifying resins, or combinations of two or more thereof. In embodiments, the compositions, may comprise from 0 to 40 wt. %, such as from 0 to 30 wt. %, from 0 to 20 wt. %, from 0 to 10 wt. %, from 0 to 5 wt. %, from 0 to 1 wt. %, from 0 to 0.1 wt. %, from 1 to 40 wt. %, from 1 to 30 wt. %, from 1 to 20 wt. %, or from 1 to 10 wt. % of additives.

[0026] In embodiments, the composition may further comprise an additional polymer. The additional polymer may include, without limitation, polyolefins, polyolefin elastomers, ethylene acid copolymers, and ionomers. The composition may comprise from 0 to 40 wt. %, such as from 0 to 30 wt. %, from 0 to 20 wt. %, from 0 to 10 wt. %, from 0 to 5 wt. %, from 0 to 1 wt. %, from 0 to 0.1 wt. %, from 1 to 40 wt. %, from 1 to 30 wt. %, from 1 to 20 wt. %, or from 1 to 10 wt. % of the additional polymer.

[0027] The mole ratio of the epoxy functional groups (generally provided by the epoxy functional polyolefin and, where present, by the epoxy oils or resins) to the ethylenically unsubstituted dicarboxylic acid or a derivative thereof (generally provided by the functionalized polyolefin) may be from 20 to 235, such as from 20 to 150, from 20 to 40, from 40 to 60, from 60 to 80, from 80 to 100, from 100 to 120, from 120 to 140, from 140 to 160, from 160 to 180, from 180 to 200, from 200 to 220, from 220 to 240, from 240 to 260, from 260 to 280, from 280 to 300, from 300 to 325, or any combination of two or more of these ranges. As described previously, without being limited by theory, it is believed that excess acid functionality in the composition may result in decreased thermal aging properties in the resultant composition by catalyzing the decomposition of the polyamide compound. Thus, it is believed that when the mole ratio of the epoxy functional groups to the ethylenically unsubstituted dicarboxylic acid or a derivative thereof is too low, such as less than 20, the composition will experience undue thermal aging. Additionally, it is believed that when the ratio of epoxy functional groups to the ethylenically unsubstituted dicarboxylic acid or a derivative thereof is too high, such as greater than 235, the composition will not be sufficiently toughened for use.

[0028] In some specific embodiments, the mole ratio of the glycidyl alkyl acrylate functional group to the ethylenically unsubstituted dicarboxylic acid or derivative thereof is from 16 to 150, such as from 25-135, from 16 to 20, from 20 to 30, from 30 to 50, from 50 to 75, from 75 to 100, from 100 to 125, from 125 to 150, or any combination of two or more of these ranges.

[0029] In some embodiments, the composition may comprise at least 50 wt. %, at least 60 wt. %, at least 70 wt. %, at least 80 wt. %, at least 90 wt. %, at least 95 wt. %, at least 99 wt.%, or even at least 99.9 wt. % of the combined weight of the polyamide; the epoxy functional polyolefin; the functionalized polyolefin; optionally, the inorganic filler; optionally, the stabilizers; optionally, the additives; and optionally, the additional polymers. In some embodiments, the composition comprises at least 50 wt. %, at least 60 wt. %, at least 70 wt. %, at least 80 wt. %, at least 90 wt. %, at least 95 wt. %, or even at least 99 wt.% of the combined weight of the polyamide, the epoxy functional polyolefin, and the functionalized polyolefin.

[0030] In some embodiments, an article may comprise the composition. The article may be a molded article, such as an injection molded article. The article (such as an injection molded article) may have a retention of impact strength equal or higher than 80%, such as equal to or higher than 85%, equal to or higher than 90 %, equal to or higher than 95%, equal to or higher than 98 %, or even equal to or higher than 99 % after 1000 hours thermal aging. The article (such as an injection molded article) may have a retention of impact strength equal or higher than 80%, such as equal to or higher than 85%, equal to or higher than 90 %, equal to or higher than 95%, equal to or higher than 98 %, or even equal to or higher than 99 % after 1500 hours thermal aging.

[0031] The article may have an initial (before thermal aging) impact strength equal or higher than 650 J/m, such as equal or higher than 650 J/m, equal or higher than 675 J/m, equal or higher than 700 J/m, equal or higher than 720 J/m, or equal or higher than 750 J/m.

[0032] The article may have an initial (before thermal aging) flexural modulus equal or higher than 1790 MPa, such as equal or higher than 1825 MPa, equal or higher than 1875 MPa, or equal or higher than 1900 MPa.

[0033] The article may have an initial (before thermal aging) stress at break equal or higher than 48 MPa, such as equal or higher than 49 MPa, equal or higher than 51 MPa, or equal or higher than 53 MPa .

TEST METHODS

[0034] Density

[0035] Samples for density measurement are prepared according to ASTM D 1928. Polymer samples are pressed at 190 °C and 30,000 psi for three minutes, and then at 21 °C and 207 MPa for one minute. Measurements are made within one hour of sample pressing using ASTM D792, Method B.

[0036] Melt Index (I2)

[0037] Melt index, or I2, (grams/10 minutes or dg/min) is measured in accordance with ASTM D 1238, Condition 190 °C/2.16 kg, Procedure B.

[0038] Izod Impact

[0039] Impact strength is determined according to ASTM D256.

[0040] Tensile Properties

[0041] Tensile properties (e.g., tensile elongation at break and tensile stress at break) are measured according to ASTM D-638. [0042] Flexural Properties

[0043] Flexural properties (e.g., flex modulus) are measured according to ASTM D-790.

[0044] GMA Level

[0045] The GMA level is quantified via the Nuclear Magnetic Resonance (*H NMR ) technique. NMR samples were prepared by adding ~0.1 g of sample to 3.25g of 50/50 by weight l,l,2,2-tetrachlorethane-d2/perchloroethylene (TCE/PCE) containing 0.001 M Cr(AcAc)3 and about 50 ppm butylated hydroxytoluene (BEIT), in a Norell 1001-7 10mm NMR tube. The tubes were capped and then heated and vortexed at 115 to 135°C to dissolve and ensure homogeneity. 1H NMR was performed on a Bruker AVANCE 400 MHz spectrometer equipped with a Bruker high-temperature CryoProbe at a sample temperature of 120oC. Spectra were acquired with ZG pulse, 1.6s AQ, 16 scans with a relaxation delay of 14s.

[0046] Glycidylmethacrylate (GMA) was quantitated using the integral areas of the three epoxide ring protons at about 3.2, 2.8, and 2.6 ppm. n-Butylacrylate (nBA) comonomer was quantitated using the integral area of the GMA plus nBA CH2 O" protons at about 3.7 to 4.6 ppm, minus 2X the moles of GMA. Ethylene was quantitated using the 0.5 to 2 ppm area, after subtracting the contribution from nBA and GMA to the region.

[0047] MAH Level

[0048] The MAH level is determined by the method described in WO2017116843A1. Where possible, it is preferred to measure the MAH level at the time of manufacture as it is known to those skilled in the art that MAH groups may hydrolyze during aging in ambient environment when exposed to moisture. The MAH may be regenerated by thermal conditioning in a controlled inert environment at temperature >150 °C)

EXAMPLES

[0049] The following examples illustrate features of the present disclosure but are not intended to limit the scope of the disclosure. The following experiments analyzed the performance of embodiments of the ethylene-based polymers described herein. [0050] Materials

[0051] MAH-Functionalized Polyolefin- 1 is a maleic anhydride modified polyethylene elastomer having a density of 0.870 g/cc and a melt index (12) of 1.6 g/10 min. The weight percentage of MAH in copolymer is 0.5%.

[0052] ZYTELTM 103 is a polyamide 66 (PA66) resin commercially available from Celanese.

[0053] Epoxy Terpolymer-1 is an E/nBA/GMA terpolymer having a density of 0.94 g/cm3 and a melt index (12) of 12 dg/min. The composition of Epoxy Terpolymer- 1 is described in more detail in Table 1.

Table 1 : EPOXY TERPOLYMER Composition

[0054] Sample Preparation

[0055] A series of samples were prepared by compounding the formulations described in Table 2 (below) in a ZSK 26 mm twin screw extruder (TSE) at 270-300 °C and a screw speed of 300 rpm. A Toyo Si-90 Injection Molder was used to prepare dumb-bell shaped bars for tensile, Izod impact and flexural modulus testing. The molding temperature was 275 °C - 290 °C, injection pressure was 2000 bar and cooling time was 20 s. As indicated in the tables below, aged samples were aged in an oven at 150 °C for 500 hr, 1000 hr, or 1500 hr. The GMA/MAH mole ratio described in Table 2 is calculated according to Equation (I).

Table 2: Sample Compositions

[0056] Sample Characterization

[0057] As described in the Test Methods section, each of the samples was then subjected to tensile, Izod impact, and flexural modulus testing. Results are given in Tables 3-5. The Retention of the performance is calculated according to Equation (II).

Eq (II) 100

Table 3: Impact Strength

[0058] As can be seen in Table 3, EX-A and EX-B showed far better retention of impact strength after 1000 and 1500 hours than the comparative examples. The exceptions being CE- 2 and CE-4, which showed very low initial impact strength. Thus, while they retained great amounts of strength, CE-2 and CE-4 did not have sufficient initial strength for relevant applications.

Table 4: Stress at Break

[0059] As can be seen in Table 4, EX-A, EX-B, and the comparative samples showed acceptable retention of stress at break after aging. However, comparative samples CE-1 and CE-4 showed insufficient initial (0 hrs) stress at break.

Table 5: Flexural Modulus

[0060] As can be seen in Table 5, EX-A and EX-B showed a superior flexural modulus of greater than 1790 Mpa, both before and after aging, relative to the comparative samples .

Claims

1. A composition comprising: a polyamide; an epoxy functional polyolefin comprising one or more epoxy ring functional groups; and a functionalized polyolefin comprising a polyolefin with ethylenically unsubstituted dicarboxylic acid or a derivative thereof, and wherein the mole ratio of the epoxy functional groups to the ethylenically unsubstituted dicarboxylic acid or a derivative thereof is from 20 to 235.

2. The composition of claim 1, wherein the composition further comprises one or more epoxy oils or resins.

3. The composition of either of claims 1 or 2, wherein the epoxy functional polyolefin is a terpolymer comprising alpha-olefin, alkyl acrylate, and glycidyl methacrylate.

4. The composition of any one of claims 1-3, wherein the functionalized polyolefin is grafted with ethylenically unsubstituted dicarboxylic acid or derivative thereof.

5. The composition of any one of claims 1-4, wherein the functionalized polyolefin comprises a polyethylene elastomer having a density of 0.855 to 0.890 g/cm³.

6. The composition of any one of claims 1-5, wherein the functionalized polyolefin is grafted with 0.1 to 3.0 wt.% maleic anhydride.

7. The composition of any one of claims 1-6, wherein the melt index (I2) of the functionalized polyolefin is from 0.1 to 15 g/10 min.

8. The composition of any one of claims 1-7, wherein the epoxy functional polyolefin comprises: 1 to 15 wt. % of glycidyl alkyl acrylate; and 10 to 40 wt. % of alkyl acrylate.

9. The composition of any one of claims 1-8, wherein the epoxy functional polyolefin has a melt index (I2) of 1.0 to 30 g/10 min as measured according to ASTM D1238 (190 C/2.16 kg).

10. The composition of any one of claims 1-9, wherein the mole ratio of the glycidyl alkyl acrylate functional group to the ethylenically unsubstituted dicarboxylic acid or derivative thereof is from 20 to 235.

11. The composition of any one of claims 1-10, wherein the composition comprises 60 to 99 wt. % of the polyamide; 0.8 to 39 wt. % of the epoxy functional polyolefin; and 0.1 to 8 wt. % of the functionalized polyolefin.

12. An article comprising the composition any one of claims 1 to 11.

13. The article of claim 12, wherein the article is an injection molded article.

14. The article of either of claims 12-13, wherein the injection molded article has a retention of impact strength equal or higher than 80% after 1000 hours thermal aging.

15. The article of any one of claims 12-14, wherein the injection molded article has an impact strength equal or higher than 650 J/m, an flexural modulus equal or higher than 1790 MPa, and a stress at break equal or higher than 48 MPa before thermal aging.