Polymer blends containing recycled polymers with improved properties

Abstract

The present disclosure relates to a polymer blend comprising a composition having selected properties, the composition comprising one or more polypropylene-based polymers and one or more additives, and at least one recycled polymer. Further, the present disclosure relates to a method for preparing the polymer blend, the composition as defined above, the use of the composition in the polymer blend, and a molded article comprising the composition or the polymer blend.

Description

[Technical Field]

[0001] The present disclosure relates to compositions comprising one or more polypropylene-based polymers and one or more additives, and polymer blends comprising the compositions and at least one recycled polymer. The present disclosure also relates to methods for preparing the polymer blends and uses of the compositions. The present disclosure also provides molded articles comprising the compositions or polymer blends. [Background technology]

[0002] Virgin polypropylene polymer can be produced using petrochemical techniques such as slurry or gas-phase processes (see, for example, Pasquini, N., Polypropylene Handbook, 2nd Ed., 2005). The production of polypropylene homopolymer and random copolymers of propylene with other α-olefins requires a plant setup of at least one polymerization reactor. Polypropylene homopolymers can have high stiffness (e.g., high flexural modulus) but generally lack impact resistance at room temperature and low temperatures. Random copolymers, on the other hand, may exhibit higher impact resistance at room temperature but generally lack high stiffness. Impact copolymers, also known as heterophasic copolymers, combine high stiffness and high impact resistance because they contain fractions of polypropylene homopolymer and ethylene-propylene copolymer. However, the production of impact copolymers requires a minimum of two polymerization reactors in a cascade setup. Thus, the production of impact copolymers is inherently more demanding because it is more complex than the production of homopolymers or random copolymers.

[0003] A variety of catalysts, including Ziegler-Natta and metallocene catalysts, can be used to produce virgin polypropylene polymer. Over the past few decades, various internal donors have been developed for Ziegler-Natta catalysts, including phthalate, diether, succinate, or diester donors (e.g., Paulik et al. Macromol. Chem. Phys. 2021, 222, 2100302). The internal donor strongly influences the characteristics of the resulting polymer, determining the achievable degree of isotacticity, chemical composition distribution, molecular weight distribution, and comonomer incorporation.

[0004] All virgin polypropylene polymers use natural resources in the form of propylene gas and potentially other alpha-olefins. During the production of virgin polypropylene polymer, large amounts of energy are required to melt the polymer in the plant's extruders, heat it, compress the gas, stir it, and transport the final product from the petrochemical plant to distributors and converters. Therefore, the production of virgin polypropylene polymer requires a large use of natural resources and generates a certain carbon footprint (e.g., 1.72 kg-CO2eq / kg material; source: Table 4 average in Alsabri et al. Polymers 2021, 13, 3793).

[0005] Virgin polypropylene polymer compositions may be completely or partially replaced with recycled polymer compositions, for example, from post-consumer waste, depending on the application. However, in terms of physical properties, recycled polymer compositions exhibit inferior material properties compared to virgin polymer compositions because they contain a mixture of different polymers that results in an averaged property profile instead of differentiated properties for different applications, such as injection molding, film processing, or fiber and textile applications. As a result, recycled polymer compositions are used almost exclusively in less demanding injection molding applications, such as furniture, flower pots, or non-food contact packaging.

[0006] Several concepts for improving the properties of recycled polymer compositions are known in the art, such as the use of fillers (see WO 2022 / 084236 and WO 2014 / 167493), compatibilizers (see EP 3715410 and WO 2022 / 104275), and the addition of different types of virgin polymers (see WO 2022 / 084236, EP 3715410, and WO 2022 / 104275). (See, for example, WO 2021 / 032460, EP 3916047, WO 2021 / 032460, WO 2014 / 167493, WO 2021 / 165751, U.S. Patent Application Publication No. 2022 / 0145057, WO 2022 / 104275, WO 2022 / 123000, WO 2022 / 123002, and EP 3802689.) In the latter case, blending virgin and recycled polymer compositions has been shown to trade off advantageous physical properties and reduced carbon footprints (see, for example, WO 2022 / 084236 and WO 2021 / 165751). Prior art virgin polymer compositions frequently used to upgrade recycled polymer compositions are typically commercially available polymer products intended for use in compounding, injection molding, film, or fiber applications without the addition of the recycled polymer composition (see, for example, U.S. Patent Application Publication No. 2022 / 0145057, WO 2022 / 104275, WO 2022 / 123000, and WO 2022 / 123002). Therefore, the achievable physical properties of a blend of a recycled polymer composition with a prior art virgin polymer composition are a composite of the two and will not achieve the desired property profile of a fully virgin polymer composition. To address this issue, some applicants have disclosed compositions containing, for example, multiple olefin (co)polymers and / or polyethylenes. However, the polymers must be prepared using laborious polymerization techniques and complex plant setups, i.e., requiring high manufacturing complexity.

[0007] A different approach to solving the problem of improving the properties of blends of recycled and virgin polymer compositions has been found in the use of special internal donors for the polymerization of virgin polymers intended to be blended with recycled polymer compositions. Here, it has been found that non-phthalic esters, particularly those selected from optionally substituted malonates, maleates, succinates, glutarates, cyclohexene-1,2-dicarboxylates, benzoates, and derivatives and / or mixtures thereof, are particularly suitable (see EP 3916047 and WO 2021 / 032460). A preferred type of internal donor has been reported to be based on citraconates, such as bis(2-ethylhexyl)citraconate.

[0008] Overall, there is an unmet need for specialized polymer compositions that can improve the properties of recycled polymers or polymer compositions to virgin-like performance at low addition levels, which would be beneficial for reducing carbon footprints and more efficient use of natural resources. Furthermore, the polymers of these compositions should be obtainable through simple polymerization processes, i.e., have low manufacturing complexity. Summary of the Invention

[0009] One objective of the present disclosure is to provide a composition that, when blended with at least one recycled polymer, upgrades the at least one recycled polymer without the manufacturing complexity while maintaining a reduced carbon footprint. For example, the at least one recycled polymer can include one or more post-consumer waste polymers or post-consumer waste polymer compositions.

[0010] As used herein and in the claims that follow, upgrading is intended to include, for example, improving the mechanical, physical, and / or chemical properties of at least one recycled polymer.

[0011] It has now been found that the above objectives are achieved by a composition according to one aspect of the present disclosure.

[0012] In one aspect thereof, the present disclosure provides a composition comprising: one or more polypropylene-based polymers; one or more additives selected from the group including, for example, consisting of, antioxidants, acid scavengers, antistatic agents, nucleating agents, clarifiers, slip agents, and antiblocking agents; Including, The composition satisfies I>4.0, I is defined by the following formula (1):

number

number

[0013] Surprisingly, it has been found that compositions according to the present disclosure, when blended with at least one recycled polymer, exhibit material properties (e.g., stiffness) that are the same as or better than prior art polymer blends, even when the resulting polymer blend contains a large fraction of one or more recycled polymers, e.g., at least 40 wt.% or more, up to 85 wt.%, 90 wt.% or more, based on the total weight of the polymer blend, while using natural resources more efficiently, resulting in a polymer blend with a significantly lower carbon footprint. Furthermore, the compositions of the present disclosure are easy to manufacture.

[0014] Compositions according to the present disclosure may be used to replace virgin polymer compositions, such as, for example, heterophasic (impact) copolymer compositions, which combine high stiffness and high impact resistance at room temperature, but which have a higher carbon footprint, use natural resources less efficiently, and require complex manufacturing processes or plants.

[0015] As used herein and in the claims that follow, the terms "virgin polymer" or "virgin material" refer to a polymer or material, respectively, that is newly produced and has not yet been recycled prior to its first use. For example, one or more polypropylene-based polymers of compositions and polymer blends according to embodiments of the present disclosure comprise or are made from one or more virgin polymers.

[0016] In this specification and in the claims that follow, the term "polypropylene-based polymer" is used to designate any polymer or polymer composition or polymer blend that includes polypropylene. Polypropylene can include polypropylene homopolymer and / or polypropylene copolymer. According to one or more embodiments, the polypropylene-based polymer includes at least 50%, 60%, 70%, 80%, 90%, 95%, or 99% by weight of homopolymer. According to one or more embodiments, the polypropylene-based polymer is a homopolymer.

[0017] As used herein and in the claims that follow, the term "T3" refers to the peak maximum temperature (°C) determined by analytical temperature-rising elution fractionation (ATREF). ATREF is performed using an automated CRYSTAF-TREF instrument (PolymerChar SA, Spain) equipped with a heated infrared (IR) concentration detector with a composition sensor and a capillary viscometer detector. A polymer solution is prepared in 1,2-dichlorobenzene (stabilized with 500 ppm of 2,6-di-tert-butyl-4-methylphenol) at a concentration of 3 ± 0.25 mg / ml at 150°C for 90 min. After dissolution is complete, the sample is transferred to an ATREF column, and a stabilization, crystallization, and elution cycle is performed as follows: During stabilization, the column is cooled from 150°C to 95°C at -40°C / min, then held at 95°C for 45 min. Crystallization is performed by cooling from 95°C to 35°C at a cooling rate of -0.5°C / min. At the end of crystallization, the column is held at 35°C for 10 minutes. The contents of the column are then eluted for 10 minutes, and the soluble fraction is collected. Elution is performed by heating from 35°C to 140°C at a heating rate of +1°C / min while maintaining a constant solvent flow rate of 0.5 ml / min. The resulting ATREF curve is normalized to 100% integral, which includes the soluble fraction. The peak maximum temperature, T3, is assigned to the maximum observed in the temperature range from 100°C to 150°C.

[0018] As used herein and in the claims that follow, "T c The term "crystallization peak temperature" is the crystallization peak temperature (°C). M (T pm ) and the crystallization peak temperature T C (T pc The melting peak temperature T is determined according to ISO 11357-3. The heating and cooling protocol is as follows: [1] +10 K / min from 50 to 200 °C, [2] 200 °C for 5 min, [3] -10 K / min from 200 to 50 °C, [4] 50 °C for 5 min, [5] +10 K / min from 50 to 200 °C. M The second heating cycle (step [5]) is evaluated for the crystallization peak temperature T cFor this, evaluate the cooling cycle (step [3]).

[0019] As used herein and in the claims that follow, the term "XS" refers to the xylene cold soluble fraction (wt%). XS is determined according to ISO 16152 with a modified temperature profile as follows: For analysis, 5 grams of sample is added to a 1000 ml round-bottom flask and combined with 450 ml of ortho-xylene. The sample / xylene mixture is heated under reflux to 140 ± 2°C and held at this temperature for 60 minutes until a clear solution is obtained. The flask is cooled to 130°C until reflux ceases. The mixture is then stirred and cooled using an ice bath for a minimum of 20 minutes to reach 5°C, allowing a gel to precipitate. The ice bath is then removed and replaced with a water bath maintained at 23°C. The flask is left in the water bath with constant stirring for 30 minutes, then slowly reheated to room temperature. The mixture is then poured through a filter to recover the solvent. The precipitated gel is washed with an additional 50 ml of clean xylene. A 200 ml aliquot of the filtrate is taken and poured into a 250 ml round-bottom flask. The solvent is removed by evaporation until a constant weight is obtained. Calculation of xylene cold solubles (XS):

number

[0020] As used herein and in the claims that follow, the term "PI" refers to the rheological polydispersity index, determined as follows: Rheological oscillatory frequency sweep experiments are performed on compression-molded disks at 210°C, oscillatory strain amplitude γ = 10%, angular frequency ω = 389 - 0.1 rad / s, and using parallel plate geometry on a DHR-2 rheometer (TA Instruments, New Castle, CT, USA). The storage modulus G' and loss modulus G'' data are analyzed by performing a least-squares polynomial fit: ln(G') = a × [ln(G'')]. 2 + a1 × ln(G'') + a0. Crossover modulus G C is calculated from the fit parameters by:

number

[0021] The rheological polydispersity index (PI) is calculated based on the crossover modulus G C It is calculated from

number

[0022] In this specification and in the claims that follow, the term "MFR" refers to the melt mass flow rate determined in accordance with ISO 1133 at 230°C and a load of 2.16 kg.

[0023] Further embodiments of the composition are defined in the dependent claims.

[0024] In a further aspect thereof, the present disclosure relates to a composition comprising one or more polypropylene-based polymers and one or more additives, including, for example, selected from the group consisting of antioxidants, acid scavengers, antistatic agents, nucleating agents, clarifiers, slip agents, and antiblocking agents, wherein the one or more polypropylene-based polymers comprise homopolymers produced using a MgCl2-xROH-supported Ziegler-Natta catalyst having an internal donor to magnesium ratio (ID / Mg) of at least 0.14. For example, ID / Mg may be 0.14 to 0.40. According to one or more embodiments, the one or more polypropylene-based polymers are also produced using an external donor. The internal donor, external donor, and one or more additives may be according to any one of the embodiments disclosed herein. According to one or more embodiments, the internal donor, external donor, and one or more additives are selected such that the composition satisfies I>4.

[0025] Additionally, in a further aspect thereof, the present disclosure relates to a polymer blend comprising a composition according to any one of the embodiments disclosed herein and at least one recycled polymer. The at least one recycled polymer may comprise a recycled polymer composition.

[0026] In still a further aspect thereof, the present disclosure relates to a method of preparing a polymer blend according to any one of the embodiments disclosed herein, comprising mixing the composition with at least one recycled polymer or polymer composition.

[0027] Additionally, the present disclosure relates to the use of a composition according to any one of the embodiments disclosed herein in a polymer blend for upgrading one or more post-consumer or post-industrial polymers included in the polymer blend.

[0028] Additionally, the present disclosure relates to a molded article comprising a composition according to any one of the embodiments disclosed herein or a polymer blend according to any one of the embodiments disclosed herein. According to one or more embodiments, the molded article may be formed by injection molding or thermoforming.

[0029] The present disclosure is based on the discovery that selected compositions can be blended with high content recycled materials, for example from post-consumer waste, in polymer blends having properties (e.g., stiffness) that are at least comparable to those of fully virgin polymer compositions.

[0030] Compositions and polymer blends according to one or more embodiments of the present disclosure may have excellent mechanical properties, such as, for example, flexural modulus and / or Charpy (notched) impact strength, and therefore may have a reduced carbon footprint that contributes to more efficient use of natural resources and may be suitable for a wide range of applications, including injection molding, thermoforming, and fiber applications.

[0031] Embodiments of the compositions and polymer blends may have selected combinations of features such as molecular weight distribution, crystallinity, and stereoregularity, which can be used to prepare polymer blends with properties (e.g., stiffness) that are comparable to fully virgin polymer compositions, but with a high content of recycled materials and a low carbon footprint. [Brief explanation of the drawings]

[0032] [Figure 1] FIG. 1 shows the flexural modulus of example polymer blends according to one or more embodiments, comparative polymer blends, and comparative virgin polymer compositions. [Figure 2] FIG. 1 shows the carbon footprints of examples and comparative examples that exhibited comparable flexural modulus and Charpy (notched) impact resistance at 23° C. [Figure 3]FIG. 1 shows the stiffness improvement [%] versus the carbon footprint reduction [%] for the examples and comparative examples. [Figure 4] FIG. 1 shows the stiffness improvement [%] of the examples and comparative examples according to WO 2021 / 032460 relative to the carbon footprint reduction [%]. DETAILED DESCRIPTION OF THE INVENTION

[0033] The following are embodiments of polymer blends. Unless otherwise indicated, the composition embodiments may include the same features as the composition features included in any one of the polymer blend embodiments. In other words, all composition features described with reference to the composition of the polymer blend are also applicable to the composition used as such (and vice versa).

[0034] Polymer Blend Embodiments Embodiments of the present disclosure are directed to polymer blends, the polymer blends comprising: 1. A composition comprising: one or more polypropylene-based polymers; one or more additives selected from the group including, for example, consisting of, antioxidants, acid scavengers, antistatic agents, nucleating agents, clarifiers, slip agents, and antiblocking agents; a composition comprising: at least one recycled polymer; The composition satisfies I>4.0, I is defined by the following formula (1):

number

[0019] ; The PI ratio is defined by the following equation (2):

number

[0035] According to one or more embodiments, T3 in formula (1) may be 115.5°C to 140.0°C, preferably 116.0°C to 135.0°C, more preferably 116.5°C to 130.0°C, even more preferably 117.0°C to 125.0°C, even more preferably 117.2°C to 122.0°C, and most preferably 117.3°C to 120.0°C.

[0036] According to one or more embodiments, T in formula (1) c may be 115.0°C to 145.0°C, preferably 117.0°C to 140.0°C, more preferably 119.0°C to 139.0°C, even more preferably 120.0°C to 138.0°C, even more preferably 122.0°C to 137.0°C, even more preferably 125.0°C to 136.0°C, even more preferably 127.0°C to 135.0°C, and most preferably 129.0°C to 135.0°C.

[0037] According to one or more embodiments, XS in formula (1) may be ≦5.5 wt%, preferably ≦5.0 wt%, more preferably ≦4.5 wt%, even more preferably ≦4.0 wt%, even more preferably ≦3.5 wt%, even more preferably ≦3.0 wt%, even more preferably ≦2.5 wt%, and most preferably ≦2.4 wt%.

[0038] According to one or more embodiments, the PI ratio in formulas (1) and (2) is 0.91 to 1.20, preferably 0.92 to 1.18, more preferably 0.93 to 1.16, even more preferably 0.94 to 1.14, even most preferably 0.95 to 1.13, even more preferably 0.96 to 1.10, even more preferably 0.96 to 1.08, even more preferably 0.96 to 1.05, and most preferably 0.96 to 1.02.

[0039] According to one or more embodiments, the MFR (230°C, 2.16 kg, ISO1133) in formula (2) may be 0.1 to 200 g / 10 min, preferably 0.2 to 190 g / 10 min, even more preferably 0.3 to 180 g / 10 min, even more preferably 0.5 to 170 g / 10 min, even more preferably 0.6 to 160 g / 10 min, even more preferably 0.7 to 150 g / 10 min, and most preferably 0.8 to 140 g / 10 min.

[0040] Embodiments of the composition, whether used by itself or as a component of a polymer blend, exhibit a selected profile of properties (T3, T4, T5) that are useful for providing polymer blends with high content of one or more recycled polymers, properties at least equivalent to or better than fully virgin polymer compositions, with low manufacturing complexity, and resulting in a reduced carbon footprint. c , XS, PI ratio, MFR). The selected profile of properties of the composition is expressed according to equation (1) above, resulting in a predetermined I value that may be at least greater than 4.

[0041] According to one or more embodiments, I is >4.0, preferably ≧5.0, more preferably ≧6.0, even more preferably ≧7.0, even more preferably ≧8.0, even more preferably ≧9.0, even more preferably ≧9.5, and most preferably ≧9.6.

[0042] According to one or more embodiments, I is >4.0-30, preferably 5.0-25, more preferably 6.0-20, even more preferably 7.0-18, even more preferably 8.0-16, even more preferably 9.0-14, and most preferably 9.5-13.5.

[0043] According to one or more embodiments, in formula (1): T3 is 115.5℃ to 140.0℃, and T c is 115.0°C to 145.0°C, XS is ≦5.5 wt%, In equation (2), MFR is 0.1 to 200 g / 10 min. I is >4.0. According to one or more embodiments, in formula (1): T3 is 116.0℃ to 135.0℃, and T c is 117.0°C to 140.0°C, XS is ≦5.0 wt%, and the PI ratio is 0.91 to 1.20; In equation (2), MFR is 0.2 to 190 g / 10 min. I is >5.0.

[0044] According to one or more embodiments, in formula (1): T3 is 117.3°C to 120.0°C, Tc is 129.0°C to 135.0°C, XS is ≦2.4 wt%, and the PI ratio is 0.95 to 1.13 (for example, 0.96 to 1.02), In equation (2), MFR is 0.8 to 140 g / 10 min. I is ≥ 9.6.

[0045] one or more polypropylene-based polymers According to one or more embodiments, the one or more polypropylene-based polymers comprise homopolymers and / or copolymers. According to one or more embodiments, the one or more polypropylene-based polymers comprise homopolymers. According to one or more embodiments, the one or more polypropylene-based polymers comprise at least 50%, 60%, 70%, 80%, 90%, 95%, or 99% by weight of homopolymer. According to one or more embodiments, the one or more polypropylene-based polymers are homopolymers.

[0046] According to one or more embodiments, the combination of composition properties may be achieved by producing one or more polypropylene-based polymers using a non-phthalate catalyst.

[0047] According to one or more embodiments, the one or more polypropylene-based polymers are produced by using a Ziegler-Natta catalyst including an internal donor, optionally in combination with an external donor, and one or more optional proprietary additives.

[0048] According to one or more embodiments, the internal donor may be selected from the group of diethers, aliphatic diesters, aromatic diesters, succinates, citraconates, maleates, dibenzoates. According to one or more embodiments, the internal donor is selected from the group of 1,3-diethers.

[0049] According to one or more embodiments, the 1,3-diether internal donor comprises 2-isopropyl-2-isopentyl-1,3-dimethoxypropane (I3I5).

[0050] According to one or more embodiments, one or more polypropylene-based polymers are obtained by carrying out propylene polymerization in a vertically stirred gas-phase reactor, for example, of the Novolen type, at 30 bar and 75°C, using, for example, a stereospecific MgCl-xROH-supported Ziegler-Natta catalyst containing a 1,3-diether-based internal donor (ID), and by using an external donor, for example, isobutyl(isopropyl)dimethoxysilane (CAS 111439-76-0), to achieve a high isotacticity level. According to one or more embodiments, the 1,3-diether-based internal donor is preferably 2-isopropyl-2-isopentyl-1,3-dimethoxypropane (CAS 129228-11-1). According to one or more embodiments, the ID / Mg ratio is preferably 0.19.

[0051] According to one or more embodiments, the one or more polypropylene-based polymers are produced using a Ziegler-Natta catalyst having an internal donor to magnesium ratio (ID / Mg) of at least 0.14, preferably from 0.14 to 0.40, more preferably from 0.16 to 0.35, even more preferably from 0.18 to 0.30, even more preferably from 0.18 to 0.25, even more preferably from 0.18 to 0.20, and most preferably an internal donor to magnesium ratio (ID / Mg) of 0.19.

[0052] According to one or more embodiments, the one or more polypropylene-based polymers are produced using a Ziegler-Natta catalyst with an internal donor according to any one of the above embodiments in combination with an external donor selected from the group of alkoxysilanes, preferably from the group of dimethoxysilanes, most preferably wherein the external donor is isobutyl(isopropyl)dimethoxysilane (CAS111439-76-0).

[0053] According to one or more embodiments, the composition comprises one or more polypropylene-based polymers in an amount of 50% to 99.95% by weight, more preferably 55% to 99.92% by weight, even more preferably 60% to 99.90% by weight, even more preferably 65% ​​to 99.88% by weight, even more preferably 70% to 99.85% by weight, even more preferably 75% to 99.85% by weight, even more preferably 80% to 99.85% by weight, even more preferably 85% to 99.85% by weight, even more preferably 90% to 99.85% by weight, even more preferably 95% to 99.85% by weight, even more preferably 96% to 99.85% by weight, even more preferably 97% to 99.85% by weight, even more preferably 98% to 99.85% by weight, and most preferably 98.5% to 99.85% by weight, relative to the total weight of the composition.

[0054] one or more additives According to one or more embodiments, the composition further comprises one or more additives. According to one or more embodiments, the one or more additives may be used in the production of the one or more polypropylene-based polymers and / or added to the one or more polypropylene-based polymers after their production. In either case, the use of the one or more additives may provide increased process stability and improve the overall performance of the composition.

[0055] According to one or more embodiments, the one or more additives include or are selected from the group consisting of antioxidants, acid scavengers, antistatic agents, nucleating agents, clarifiers, slip agents, and antiblocking agents.

[0056] According to one or more embodiments, the antioxidant may comprise any suitable antioxidant known in the art. Preferably, the antioxidant is selected from the group consisting of phenolic antioxidants, amine antioxidants, hydroxylamine antioxidants, phosphite antioxidants, phosphonite antioxidants, benzofuranone antioxidants, thiodipropionate antioxidants, acryloyl antioxidants, and combinations thereof. For example, the phenolic antioxidant may comprise one or more sterically hindered phenolic compounds. Exemplary compounds of the sterically hindered phenolic compounds may include pentaerythritol tetrakis[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate (AO-1010), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (AO-1330), and 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (AO-3114). For example, the amine-based antioxidant may include a hindered amine compound. Exemplary compounds can be poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol-alt-1,4-butanedioic acid) (HAS622), bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate (HAS770), and poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino] (HAS944). For example, the hydroxylamine antioxidant can include bis(hydrogenated tallow alkyl)amine oxide. An exemplary compound can be bis(octadecyl)hydroxylamine (FS042). For example, the phosphite antioxidant can include a phosphite ester.Exemplary compounds can be tris(2,4-di-tert-butylphenyl)phosphite (AO-168), 3,9-bis(2,4-dicumylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol-diphosphite. For example, the phosphonite antioxidant can include a phosphonite ester. An exemplary compound can be tetrakis(2,4-di-tert-butylphenyl)[1,1'-biphenyl]-4,4'-diylbis(phosphonite) (PEPQ). For example, the benzofuranone antioxidant can include a 3-aryl-benzofuranone. An exemplary compound can be 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)3H-benzofuran-2-one. For example, a thiodipropionate-based antioxidant may include a thiodipropionic acid alkyl ester. An exemplary compound may be 3,3'-thiodipropionic acid dioctadecyl ester. For example, an acryloyl-based antioxidant may include an acryloyl-modified phenol. An exemplary compound may be 2-(1,1-dimethylethyl)-6-[[3-(1,1-dimethylethyl)-2-hydroxy-5-methylphenylmethyl-4-methylphenylacrylate.

[0057] According to one or more embodiments, the acid scavenger may include any suitable acid scavenger known in the art. According to one or more embodiments, the acid scavenger may be selected from the group including metal stearates, hydrotalcites, hydrocalumite, metal oxides, metal carbonates, and combinations thereof. For example, the metal stearates may include calcium stearate and zinc stearate. For example, the hydrotalcite may include Mg 4.3 Al2(OH) 12.6CO3·mH2O (DHT). For example, hydrocalumite can include [Ca2Al(OH)6]OH·mH2O, [Ca2Al(OH)6]CO3·mH2O, [Ca2Al(OH)6]HPO3·mH2O, [Ca2Al(OH)6]SO4·mH2O, [Ca2Al(OH)6]Cl·mH2O, and combinations thereof. For example, metal oxides can include zinc oxide, calcium oxide, magnesium oxide, and combinations thereof. For example, metal carbonates can include zinc carbonate, calcium carbonate, magnesium carbonate, and combinations thereof.

[0058] According to one or more embodiments, the nucleating or clarifying agent may include any suitable nucleating or clarifying agent known in the art. Furthermore, according to one or more embodiments, the nucleating or clarifying agent may be selected from the group including talc, metal benzoates, metal sulfates, carboxylates, phosphate ester salts, sorbitol-based clarifying agents, nonitol-based clarifying agents, and combinations thereof. For example, the metal benzoates may include sodium benzoate, lithium benzoate, and aluminum hydroxybis-(4-tert-butyl)benzoate. For example, the metal sulfates may include barium sulfate. For example, the carboxylates may include metal 1,2-cyclohexanedicarboxylic acid salts and metal bicyclo[2.2.1]heptane-2,3-dicarboxylic acid salts. For example, phosphate ester salts can include lithium 2,2'-methylene-bis-(4,6-di-tert-butylphenyl)phosphate, sodium 2,2'-methylene-bis-(4,6-di-tert-butylphenyl)phosphate, and aluminum hydroxy 2,2'-methylene-bis-(4,6-di-tert-butylphenyl)phosphate. For example, sorbitol-based fining agents can include 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol (DMDBS), 1,3:2,4-bis(p-methylbenzylidene)sorbitol (MDBS), and 1,3:2,4-dibenzylidenesorbitol (DBS). For example, nonitol-based fining agents can include 1,2,3-tridethoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene]nonitol. Commercially available examples of nucleating and fining agents include Milliken HPN-600ei, Milliken HPN-68L, Milliken HPN-20E, Milliken HPN-715, Milliken Millad 3988, Milliken Millad NX8000, Adeka MI.NA.08, Adeka NA-11, Adeka NA-21, Adeka NA-27, and Adeka NA-71.

[0059] According to one or more embodiments, the antistatic agent may include any suitable antistatic agent known in the art. According to one or more embodiments, the antistatic agent includes glycerol monostearate (GMS-55, GMS-90) or an ethoxylated alkylamine.

[0060] According to one or more embodiments, the slip agent may include any suitable slip agent known in the art. Slip agents include erucamide and oleamide.

[0061] According to one or more embodiments, the anti-blocking agent may include any suitable anti-blocking agent known in the art. According to one or more embodiments, the anti-blocking agent includes silica.

[0062] According to one or more embodiments, the one or more additives include an antioxidant, an acid scavenger, and a nucleating agent; preferably, the one or more additives include an antioxidant, an acid scavenger, an antistatic agent, and a nucleating agent; even more preferably, the one or more additives include an antioxidant, an acid scavenger, an antistatic agent, a nucleating agent, and a clarifier; even more preferably, the one or more additives include an antioxidant, an acid scavenger, an antistatic agent, a nucleating agent, a clarifier, and a slip agent; most preferably, the one or more additives include an antioxidant, an acid scavenger, an antistatic agent, a nucleating agent, a clarifier, a slip agent, and an antiblocking agent.

[0063] The polymer blends according to one or more embodiments provide superior material properties, reduced carbon footprints, and more efficient use of natural resources compared to prior art blends based on recycled polymers. Furthermore, the polymer blends according to one or more embodiments provide at least equivalent or superior material properties compared to fully virgin polymer compositions, but with a significantly lower carbon footprint and manufacturing complexity of the composition.

[0064] According to one or more embodiments, the composition comprises one or more additives in an amount of 0.05 to 5 wt. %, preferably 0.08 to 4 wt. %, more preferably 0.10 to 3 wt. %, even more preferably 0.12 to 2 wt. %, relative to the total weight of the composition, and most preferably the composition comprises one or more additives in an amount of 0.15 to 1.5 wt. %, relative to the total weight of the composition.

[0065] According to one or more embodiments, when the one or more additives are added to the one or more polypropylene-based polymers after the one or more polypropylene-based polymers have been produced, the one or more additives are selected from the group including, for example, consisting of, antioxidants and acid scavengers.

[0066] According to one or more embodiments, the composition is present in an amount of 1 wt% to 99 wt% of the total weight of the polymer blend, preferably 2 wt% to 90 wt%, more preferably 2 wt% to 80 wt%, even more preferably 2 wt% to 70 wt%, even more preferably 2 wt% to 60 wt%, even more preferably 3 wt% to 55 wt%, even more preferably 4 wt% to 50 wt%, even more preferably 5 wt% to 50 wt%, even more preferably 10 wt% to 50 wt%, even more preferably 15 wt% to 50 wt%, and most preferably the composition is present in an amount of 15 wt% to 45 wt% of the total weight of the polymer blend.

[0067] At least one recycled polymer In this specification and in the claims that follow, the term "recycled polymer" is used to indicate that the polymer is recovered from post-consumer or post-industrial waste. Post-consumer waste refers to waste that has completed at least its first use cycle (or life cycle), i.e., has already fulfilled its primary purpose, while post-industrial waste refers to manufacturing scrap that typically does not reach a customer.

[0068] According to one or more embodiments, the at least one recycled polymer may include up to 20 wt. %, preferably up to 17 wt. %, more preferably up to 3 wt. %, even more preferably up to 1 wt. %, and most preferably up to 0.1 wt. % of one or more polymers derived from a first use, in addition to one or more polymers recovered from post-consumer or industrial waste.

[0069] According to one or more embodiments, the at least one recycled polymer comprises one or more polypropylene-based polymers. The one or more recycled polypropylene-based polymers may include recycled polypropylene homopolymers, recycled polypropylene copolymers, and compositions or blends comprising recycled polypropylene homopolymers and / or recycled polypropylene copolymers.

[0070] According to one or more embodiments, the at least one recycled polymer comprises a recycled polymer composition obtained from recycled waste by a plastic recycling process known in the art. Recycled polymer compositions are commercially available, for example, from Systec Plastics GmbH (Germany), Interzero GmbH & Co. KG (Germany), Resource Plastics Corp. (Canada), Kruschitz GmbH, Plastics and Recycling (Austria), Vogt Plastik GmbH (Germany), mtm Plastics GmbH (Germany), CT Polymers (USA), and others. Non-exhaustive examples of recycled polymers include Systalen PP (Systec Plastics GmbH) and DIPOLEN PP (mtm Plastics GmbH). Embodiments of the present disclosure may use a wide range of recycled polymer compositions. The recycled polymer or polymer composition may be in the form of pellets.

[0071] According to one or more embodiments, the at least one recycled polymer may have a MFR value of 1 to 200 g / 10 min, preferably 2 to 150 g / 10 min, even more preferably 3 to 120 g / 10 min, even more preferably 4 to 100 g / 10 min, even more preferably 5 to 80 g / 10 min, even more preferably 6 to 60 g / 10 min, even more preferably 7 to 50 g / 10 min, even more preferably 8 to 40 g / 10 min, even more preferably 9 to 35 g / 10 min, even more preferably 10 to 30 g / 10 min, and most preferably 12 to 25 g / 10 min.

[0072] According to one or more embodiments, the at least one recycled polymer may comprise an ethylene content of ≦50 wt%, preferably ≦45 wt%, more preferably ≦40 wt%, even more preferably ≦35 wt%, even more preferably ≦30 wt%, even more preferably ≦25 wt%, even more preferably ≦20 wt%, even more preferably ≦18 wt%, even more preferably ≦17 wt%, even more preferably ≦16 wt%, and most preferably ≦15 wt%.

[0073] In this specification and in the claims that follow, the term "ethylene content" is used to indicate the fraction, in weight percent, of C2H4 units in a polymer derived from the polymerization of ethylene. The ethylene content is determined by Fourier transform infrared spectroscopy (FTIR) on 200±50 μm films using a Tensor 27 FTIR spectrometer (Bruker Corp., USA). Films are prepared in a hot press at 200 °C and 50 bar, and the spectral absorption is corrected for the actual film thickness. FTIR spectra are taken from 4000 to 400 cm. -1 The data was acquired in the mid-infrared region of 750-700 cm -1 The bands are evaluated using a partial least squares (PLS) algorithm by comparison with the spectrum of a reference sample calibrated by 13C NMR (Haaland et al. Anal. Chem. 1988, 60, 1193-1202).

[0074] According to one or more embodiments, the at least one recycled polymer may comprise a polypropylene homopolymer and / or copolymer content of ≥ 50 wt%, preferably ≥ 55 wt%, even more preferably ≥ 60 wt%, even more preferably ≥ 65 wt%, even more preferably ≥ 70 wt%, even more preferably ≥ 75 wt%, even more preferably ≥ 80 wt%, and most preferably 85-100 wt%.

[0075] In this specification and in the claims that follow, the term "polypropylene homopolymer and / or copolymer content" is used to indicate the fraction in weight percent of the polypropylene-based input material selected for the preparation of at least one recycled polymer.

[0076] According to one or more embodiments, at least the recycled polymer may comprise a post-consumer or post-industrial waste content of ≧5 wt%, preferably ≧10 wt%, even more preferably ≧30 wt%, even more preferably ≧50 wt%, even more preferably ≧60 wt%, even more preferably ≧70 wt%, even more preferably ≧80 wt%, even more preferably ≧90 wt%, even more preferably ≧92 wt%, even more preferably ≧95 wt%, even more preferably ≧97 wt%, even more preferably ≧98 wt%, and most preferably ≧99 wt%.

[0077] According to one or more embodiments, the at least one recycled polymer has a T of 90°C to 140°C, preferably 95°C to 135°C, more preferably 100°C to 130°C, even more preferably 105°C to 128°C, even more preferably 110°C to 127°C, even more preferably 112°C to 126°C, even more preferably 114°C to 126°C, even more preferably 116°C to 126°C, even more preferably 118°C to 126°C, even more preferably 120°C to 126°C, even more preferably 122°C to 126°C, and most preferably 123°C to 126°C. C (ISO11357-3).

[0078] According to one or more embodiments, the at least one recycled polymer may have a flexural modulus (ISO 178) of ≦2200 MPa, preferably ≦2000 MPa, more preferably ≦1800 MPa, even more preferably ≦1700 MPa, even more preferably ≦1600 MPa, even more preferably ≦1500 MPa, even more preferably ≦1400 MPa, even more preferably ≦1300 MPa, even more preferably ≦1250 MPa, and most preferably ≦1200 MPa.

[0079] According to one or more embodiments, at least one recycled polymer has a viscosity of 1.5 kJ / m 2 ~80kJ / m 2 , preferably 2.0 kJ / m 2 ~70kJ / m 2 , more preferably 2.5 kJ / m 2 ~60kJ / m 2 , and even more preferably 3.0 kJ / m 2 ~50kJ / m 2 , and even more preferably 3.5 kJ / m 2 ~40kJ / m 2 , and even more preferably 4.0 kJ / m 2 ~30kJ / m 2 , and even more preferably 4.5 kJ / m 2 ~20kJ / m 2 , and even more preferably 5.0 kJ / m 2 ~15kJ / m 2 , and even more preferably 5.0 kJ / m 2 ~10kJ / m 2 , and even more preferably 5.0 kJ / m 2 ~8kJ / m 2 , and even more preferably 5.0 kJ / m 2 ~7kJ / m 2 , and most preferably 5.0 kJ / m 2 ~6kJ / m 2 It may have a Charpy (notched) of 23°C (ISO 179-1).

[0080] According to one or more embodiments, the at least one recycled polymer may be present in the polymer blend in an amount of >0% to <100% by weight of the total weight of the polymer blend, preferably 10 to 99% by weight, more preferably 20 to 98% by weight, even more preferably 30 to 95% by weight, even more preferably 40 to 95% by weight, even more preferably 45 to 95% by weight, even more preferably 50 to 95% by weight, even more preferably 50 to 92% by weight, even more preferably 50 to 90% by weight, even more preferably 50 to 88% by weight, and most preferably 55 to 85% by weight of the total weight of the polymer blend.

[0081] Embodiments of the Method for Preparing the Polymer Blend According to one or more embodiments, a method of preparing a polymer blend includes mixing the composition with at least one recycled polymer.

[0082] The composition and the at least one recycled polymer may be mixed by any suitable method known in the art for mixing polymers. According to one or more embodiments, the composition and the at least one recycled polymer are mixed using an extruder or a tumble mixer.

[0083] According to one or more embodiments, the method of preparing the polymer blend further comprises preparing a composition. According to one or more embodiments, preparing the composition comprises synthesizing one or more polypropylene polymers.

[0084] According to one or more embodiments, synthesizing one or more polypropylene polymers includes carrying out propylene polymerization in a vertically stirred gas phase reactor, e.g., of the Novolen type, e.g., at 30 bar and 75°C, using, e.g., a stereospecific MgCl2-xROH-supported Ziegler-Natta catalyst containing a non-phthalate internal donor (ID), as well as by using an external donor.

[0085] According to one or more embodiments, the internal donor is selected from the group consisting of diethers, aliphatic diesters, aromatic diesters, succinates, citraconates, maleates, dibenzoates, preferably 1,3-diethers. More preferably, the internal donor is 2-isopropyl-2-isopentyl-1,3-dimethoxypropane (CAS 129228-11-1).

[0086] According to one or more embodiments, the one or more polypropylene polymers are synthesized as described above using a Ziegler-Natta catalyst having an internal donor to magnesium ratio (ID / Mg) of at least 0.14, preferably 0.14 to 0.40, more preferably 0.16 to 0.35, even more preferably 0.18 to 0.30, even more preferably 0.18 to 0.25, even more preferably 0.18 to 0.20, and most preferably an internal donor to magnesium ratio (ID / Mg) of 0.19.

[0087] According to one or more embodiments, the internal donor is 2-isopropyl-2-isopentyl-1,3 dimethoxypropane (CAS 129228-11-1) and has an ID / Mg ratio of at least 0.14, such as 0.19.

[0088] According to one or more embodiments, one or more polypropylene polymers are synthesized using a Ziegler-Natta catalyst with an internal donor as described above in combination with an external donor selected from the group of alkoxysilanes, preferably dimethoxysilanes. Preferably, the external donor is isobutyl(isopropyl)dimethoxysilane (CAS 111439-76-0).

[0089] According to one or more embodiments, a method of preparing a polymer blend includes mixing the composition, at least one recycled polymer, and optionally one or more additives as described above.

[0090] composition The present disclosure relates to the composition defined in any one of the polymer blend embodiments.

[0091] Embodiments of Use of the Composition and Molded Articles According to one or more embodiments of the present disclosure, the composition may be used in a polymer blend according to one or more embodiments of the present disclosure.

[0092] One or more embodiments are directed to the use of the composition in a polymer blend for upgrading one or more post-consumer or post-industrial polymers.

[0093] One or more embodiments are directed to a molded article comprising a composition according to any one of the embodiments described herein or a polymer blend according to any one of the embodiments described herein.

[0094] The shaped articles may be made by any suitable method known in the art for forming shaped articles from polymer compositions and / or polymer blends. [Example]

[0095] Compounding Test Examples IE-1 and IE-2 and Comparative Examples CE-7 to CE-10 according to embodiments of the present disclosure were prepared using a co-rotating twin-screw extruder (screw diameter D: 25.5 mm). The polymer compositions were extruded with an additive premix for process stabilization. The additive premix contained Irganox 1010 (BASF SE, Germany), Irganox 168 (BASF SE, Germany), calcium stearate (Baerlocher GmbH, Germany), and Systalen C45003 (Systec Plastics GmbH, Germany) in a ratio of 1:1:1.8:7.6. The additive premix was added so that the final composition further contained 450 ppm Irganox 1010, 450 ppm Irganox 168, and 800 ppm calcium stearate. All ingredients were added through the main feed port of the extruder using gravimetric feeders. The compositions were extruded using a standard screw configuration including conveying, kneading, transition, and backmixing elements. The extruder was operated at 350 rpm with a temperature profile ramping from 140°C to 210°C. The polymer strands produced were cooled in a cold water bath and pelletized using a granulator. Between preparations of different polymer blends, the extruder and feeder were cleaned to prevent cross-contamination.

[0096] Test specimens were prepared according to ISO 19069-2 and ISO 20753 from Examples IE-1 and IE-2 and Comparative Examples CE-7 to CE-10 prepared according to embodiments of the present disclosure. The specimens were conditioned at 23°C and 50% relative humidity for 7 days before testing. Flexural modulus values ​​were determined according to ISO 178. Charpy (notched) impact values ​​at 23°C were determined on notched specimens according to ISO 179-1 / 1eA.

number

[0097] The stiffness improvement calculation used the modulus of elasticity from either a bending test according to ISO 178 or a tensile test according to ISO 527-2.

[0098] Injection Molding Testing Examples IE-3 and IE-4 and Comparative Examples CE-11 and CE-12 according to embodiments of the present disclosure were prepared by blending pellets of PCR-1 and CP-1, CP-3, P-4, or P-5 using a tumble mixer. The blended pellet mixture was then fed directly into the hopper of an injection molding machine. The temperature profiles of the heating zones of the injection molding machine were as follows: for CE-11: 230°C / 225°C / 220°C / 215°C / 210°C; for CE-12: 200°C / 195°C / 190°C / 185°C / 180°C; for IE-3: 230°C / 225°C / 220°C / 215°C / 210°C; and for IE-4: 200°C / 195°C / 190°C / 185°C / 180°C. Test specimens for mechanical testing were prepared in accordance with ISO 19069-2 and ISO 20753. Specimens were conditioned at 23°C and 50% relative humidity for 7 days before testing. Flexural modulus values ​​were determined according to ISO 178. Charpy (notched) impact values ​​at 23°C were determined on notched specimens according to ISO 179-1 / 1eA.

[0099] Calculating natural resource usage and carbon footprint reductions The reduction in natural resource usage and carbon footprint was calculated based on the following formula and literature values. The calculation considered the weight fraction of the "virgin polymer composition," i.e., the final polymer material, including the polymer components and additives. The "virgin polymer composition" refers to a material that has not yet been converted into a molded article and is not yet in consumer or industrial use. Furthermore, the "virgin polymer composition" is characterized as not having been subjected to multiple high temperature treatments of ≥ 150°C.

number

[0100] Synthesis Example CP-1: Polypropylene polymer composition CP-1 was prepared by synthesizing polypropylene homopolymer in a vertically stirred gas-phase reactor (Novolen type) at 30 bar and 80 °C using a stereospecific MgCl2-supported granular Ziegler-Natta catalyst containing diisobutyl phthalate (DIBP) as the internal donor. An external donor (cyclohexylmethyl-dimethoxysilane) was fed to the reactor to enhance isotacticity. Hydrogen was supplied to the reactor to control the polymer molecular weight, and the feed rate was adjusted to achieve a MFR of approximately 1 g / 10 min (230 °C, 2.16 kg). The resulting powder was extruded in a twin-screw extruder with 160 ppm Cyanox 1790 (Solvay SA, Belgium), 600 ppm ADK STAB PEP-36 (ADEKA Corporation, Japan), and 600 ppm calcium stearate relative to the total composition.

[0101] Comparative Example CP-2: Polypropylene polymer composition CP-2 was prepared by synthesizing polypropylene homopolymer in a vertically stirred gas-phase reactor (Novolen type) at 30 bar and 80 °C using a stereospecific MgCl2-supported granular Ziegler-Natta catalyst containing diisobutyl phthalate (DIBP) as the internal donor. An external donor (cyclohexylmethyl-dimethoxysilane) was fed to the reactor to enhance isotacticity. Hydrogen was supplied to the reactor to control the polymer molecular weight, and the feed rate was adjusted to achieve an MFR of approximately 12 g / 10 min (230 °C, 2.16 kg). The resulting powder was extruded in a twin-screw extruder with 500 ppm Irganox 1010 (BASF SE, Germany), 500 ppm Irganox 168 (BASF SE, Germany), and 800 ppm calcium stearate relative to the total composition.

[0102] Comparative Example CP-3: Polypropylene polymer composition CP-3 was prepared by synthesizing polypropylene homopolymer in a vertically stirred gas-phase reactor (Novolen type) at 30 bar and 75 °C using a stereospecific MgCl2-xROH-supported Ziegler-Natta catalyst containing a diether-based internal donor. The catalyst was prepared according to U.S. Patent No. 10,066,034, using 2-isopropyl-2-isopentyl-1,3-dimethoxypropane (I3I5) as the internal donor (ID), with an ID / Mg ratio of 0.13, and a titanation step instead of Soxhlet extraction. An external donor (isobutyl(isopropyl)dimethoxysilane) was fed to the reactor to enhance isotacticity. Hydrogen was fed to the reactor to control the polymer molecular weight, and the feed rate was adjusted to achieve a MFR of approximately 145 g / 10 min (230 °C, 2.16 kg). The resulting powder was extruded in a twin-screw extruder together with 450 ppm Irganox 1010 (BASF SE, Germany), 450 ppm Irganox 168 (BASF SE, Germany), and 800 ppm calcium stearate relative to the total composition.

[0103] P-4: Polypropylene polymer composition P-4 according to an embodiment of the present disclosure was prepared by synthesizing polypropylene homopolymer in a vertically stirred gas-phase reactor (Novolen type) at 30 bar and 75°C using a stereospecific MgCl2-xROH-supported Ziegler-Natta catalyst containing a diether-based internal donor. The catalyst was prepared according to U.S. Patent No. 10,066,034, using 2-isopropyl-2-isopentyl-1,3-dimethoxypropane (I3I5) as the internal donor (ID), with an ID / Mg ratio of 0.19, and a titanation step instead of Soxhlet extraction. An external donor (isobutyl(isopropyl)dimethoxysilane) was fed to the reactor to enhance isotacticity. Hydrogen was fed to the reactor to control the polymer molecular weight, and the feed rate was adjusted to achieve a MFR of approximately 1 g / 10 min (230°C, 2.16 kg). The obtained powder was extruded in a twin-screw extruder with 450 ppm Irganox 1010 (BASF SE, Germany), 900 ppm Irganox 168 (BASF SE, Germany), 300 ppm DHT-4A (Kisuma Chemicals BV, The Netherlands), and 4500 ppm NA-27 (ADEKA Corporation, Japan) based on the total composition.

[0104] P-5: Polypropylene polymer composition P-5 according to an embodiment of the present disclosure was prepared by synthesizing polypropylene homopolymer in a vertically stirred gas-phase reactor (Novolen type) at 30 bar and 75°C using a stereospecific MgCl2-xROH-supported Ziegler-Natta catalyst containing a diether-based internal donor. The catalyst was prepared according to U.S. Patent No. 10,066,034, using 2-isopropyl-2-isopentyl-1,3-dimethoxypropane (I3I5) as the internal donor (ID), with an ID / Mg ratio of 0.19, and an immobilization step instead of Soxhlet extraction. An external donor (isobutyl(isopropyl)dimethoxysilane) was fed to the reactor to enhance isotacticity. Hydrogen was fed to the reactor to control the polymer molecular weight, and the feed rate was adjusted to achieve a MFR of approximately 135 g / 10 min (230°C, 2.16 kg). The obtained powder was extruded in a twin-screw extruder together with 450 ppm Irganox 1010 (BASF SE, Germany), 450 ppm Irganox 168 (BASF SE, Germany), 800 ppm calcium stearate, 600 ppm glycerol monostearate (GMS-55), and 500 ppm NA-27 (ADEKA Corporation, Japan) based on the total composition.

[0105] Comparative Examples of Virgin and Recycled Polypropylene Compositions: CE-1: Comparative Example CE-1 was a virgin polypropylene homopolymer composition prepared by synthesizing polypropylene homopolymer in a vertically stirred gas-phase reactor (Novolen type) using a stereospecific MgCl2-xROH-supported Ziegler-Natta catalyst containing a diether-based internal donor. The catalyst was prepared according to U.S. Patent No. 10,066,034, using 2-isopropyl-2-isopentyl-1,3-dimethoxypropane (I3I5) as the internal donor (ID), with an ID / Mg ratio of 0.13, and a fixed titanation step instead of Soxhlet extraction. An external donor was fed to the reactor to enhance isotacticity. Hydrogen was fed to the reactor to control the polymer molecular weight. The resulting powder was extruded in a twin-screw extruder with an additive package containing antioxidants, acid scavengers, and nucleating agents.

[0106] CE-2: Comparative Example CE-2 was a virgin polypropylene homopolymer composition prepared by synthesizing polypropylene homopolymer in a vertically stirred gas-phase reactor (Novolen type) using a stereospecific MgCl2-xROH-supported Ziegler-Natta catalyst containing a diether-based internal donor. The catalyst was prepared according to U.S. Patent No. 10,066,034, using 2-isopropyl-2-isopentyl-1,3-dimethoxypropane (I3I5) as the internal donor (ID), with an ID / Mg ratio of 0.13, and a fixed titanation step instead of Soxhlet extraction. An external donor was fed to the reactor to enhance isotacticity. Hydrogen was fed to the reactor to control the polymer molecular weight. The resulting powder was extruded in a twin-screw extruder with an additive package containing antioxidants, acid scavengers, but no nucleating agents.

[0107] CE-3: Comparative Example CE-3 was a virgin propylene-ethylene random copolymer composition prepared by synthesizing propylene-ethylene random copolymer in a vertically stirred gas-phase reactor (Novolen type) using a stereospecific MgCl2-xROH-supported Ziegler-Natta catalyst containing diisobutyl phthalate (DIBP) as the internal donor. An external donor was fed to the reactor to enhance isotacticity. Hydrogen was fed to the reactor to control the molecular weight of the polymer. The resulting powder was extruded in a twin-screw extruder with an additive package containing antioxidants, acid scavengers, and clarifiers.

[0108] CE-4: Comparative Example CE-4 was a virgin propylene-ethylene impact copolymer composition prepared by synthesizing propylene-ethylene impact copolymer in a vertically stirred, gas-phase, two-reactor cascade (Novolen type) using a stereospecific MgCl2-xROH-supported Ziegler-Natta catalyst containing diisobutyl phthalate (DIBP) as the internal donor. Propylene, hydrogen, and an external donor were fed to the first reactor to produce a low-molecular-weight homopolymer, which was then transferred to the second reactor. In the second reactor, propylene, ethylene, and isopropanol were fed to produce a propylene-ethylene impact copolymer with a heterophasic morphology. The resulting powder was extruded in a twin-screw extruder with an additive package containing antioxidants, acid scavengers, and nucleating agents.

[0109] CE-5: Comparative Example CE-5 was a recycled polymer composition PCR-1 from a polypropylene-based input stream, namely, the commercial product Systalen C45003 from Systec Plastics GmbH, Germany. This product was derived from >99% post-consumer waste.

[0110] CE-6: Comparative Example CE-6 was a recycled polymer composition PCR-2 from a polypropylene-based input stream, namely, the commercial product Systalen C14002 from Systec Plastics GmbH, Germany. This product was derived from >99% post-consumer waste.

[0111] Example of a blend test (for ingredients before adding additive premix for process stabilization): CE-7: 100% PCR-1 CE-8: Polymer blend: 60% PCR-1 + 40% CP-2 CE-9: Polymer blend: 80% PCR-1 + 20% CP-1 CE-10: Polymer blend: 60% PCR-1 + 40% CP-1 IE-1: Polymer blend: 80% PCR-1 + 20% P-4 IE-2: Polymer blend: 60% PCR-1 + 40% P-4

[0112] Injection molding test examples: CE-11: Polymer blend: 80% PCR-1 + 20% CP-1 CE-12: Polymer blend: 80% PCR-1 + 20% CP-3 IE-3: Polymer blend: 80% PCR-1 + 20% P-4 IE-4: Polymer blend: 80% PCR-1 + 20% P-5 result: Examples CP-1 to CP-3 and P-4 to P-5 were prepared as described above. Table 1 below shows the properties of the prepared polypropylene polymer compositions of Comparative Examples CP-1 to CP-3 and Examples P-4 and P-5 according to embodiments of the present disclosure. The properties MFR, XS, T3, PI, and T of Examples P-4 and P-5 according to embodiments of the present disclosure are shown. c It can be seen that the combinations above provide high I values ​​of 9.6 and 11.2, compared to the low I values ​​of 1.1 to 4.0 for Comparative Examples CP-1 to CP-3.

[0113] [Table 1]

[0114] Additionally, Comparative Examples CE-1 to CE-6 were either prepared as described above or commercially available. Table 2, Parts 1 and 2, show the properties of Comparative Examples CE-1 to CE-6. Additionally, values ​​for natural resource usage reduction, carbon footprint, and carbon footprint reduction are shown.

[0115] As can be seen, the fully virgin polymer compositions CE-1 through CE-4 had a high carbon footprint. The fully recycled polymer compositions of Comparative Examples CE-5 and CE-6 had a reduced carbon footprint and used reduced amounts of natural resources, but the flexural modulus values ​​(stiffness) of the fully recycled polymer compositions (1088-1164) were lower compared to the flexural modulus values ​​(1256-1500) of the fully virgin polymer compositions CE-1 through CE-4.

[0116] [Table 2-1]

[0117] [Table 2-2]

[0118] Additionally, Comparative Examples CE-7 to CE-10 and Examples IE-1 and IE-2 were prepared according to the "Compound Testing" method described above. The properties of CE-7 to CE-10, IE-1, and IE-2 are shown in Table 3, Parts 1 and 2, below. Additionally, the stiffness improvement, natural resource reduction, carbon footprint, and carbon footprint reduction values ​​are shown.

[0119] [Table 3-1]

[0120] [Table 3-2]

[0121] As can be seen from Table 3, Parts 1 and 2, the polymer blends of Examples IE-1 and IE-2 had carbon footprint reductions of 43% and 32% compared to the virgin polymer compositions of CE-1 to CE-4. Comparative Examples CE-7 to CE-10 had carbon footprint reductions of 32% to 53% compared to the virgin polymer compositions of CE-1 to CE-4. However, the flexural modulus value (stiffness) of Comparative Example CE-7, which contained 100% recycled polymer composition PCR-1, was lower than the flexural modulus values ​​of the completely virgin polymer compositions of Comparative Examples CE-1 to CE-4. In addition, the polymer blends of Comparative Examples CE-8 to CE-10, which contained virgin polymer compositions of Comparative Examples CP-1 and CP-2, only had modest improvements in stiffness of 7% to 15%.

[0122] The polymer blends of Examples IE-1 and IE-2, including the virgin polymer composition of Example P-4, which had a particular combination of properties resulting in an I value of >4.0, had high carbon footprint reductions and high reductions in natural resource usage, combined with high stiffness improvements of 21% to 36%. The stiffness improvements of IE-1 and IE-2 were higher than those of Comparative Examples CE-8 to CE-10.

[0123] Furthermore, as can be seen from Figure 1, the polymer blends of Examples IE-1 and IE-2 had higher flexural modulus values ​​compared to Comparative Examples CE-9 and CE-10, which contained the polymer composition of Comparative Example CP-1. Furthermore, the flexural modulus values ​​of the polymer blends of Examples IE-1 and IE-2 were comparable to or even higher than the flexural modulus values ​​of the fully virgin polymer compositions of CE-1 through CE-4. Thus, the polymer blends of Examples IE-1 and IE-2, which included a polypropylene polymer composition according to an embodiment of the present disclosure (according to Example P-4), had low carbon footprints and excellent stiffness values ​​that were comparable to or even improved compared to the fully virgin polymer compositions.

[0124] As shown in Figure 2, the polymer blend of Example IE-1, which had an excellent stiffness improvement of 21% (see Table 3, Part 2), had a 43% carbon footprint reduction. Meanwhile, the polymer blend of CE-10 had only a 32% carbon footprint reduction and a low stiffness improvement of 15% (see Table 3, Part 2). All of the Examples and Comparative Examples in Figure 2 had approximately the same flexural modulus (stiffness) of 1400 MPa (±5%). Thus, Example IE-1 provided the highest carbon footprint reduction while achieving identical material properties.

[0125] FIG. 3 illustrates carbon footprint reduction values ​​versus stiffness improvement values ​​for Comparative Examples CE-7 through CE-10 and Examples IE-1 and IE-2. From this figure, it can be determined that improved stiffness values ​​were achieved by using polypropylene polymer composition P-4 according to embodiments of the present disclosure in polymer blends according to embodiments of the present disclosure, compared to polymer blends containing the same amount of recycled polymer composition but including comparative polypropylene polymer compositions CP-1 or CP-2. Examples IE-1 and IE-2 according to embodiments of the present disclosure achieved improved stiffness values ​​with comparable carbon footprint reduction values. Thus, polymer blends according to embodiments of the present disclosure were highly sustainable and provided improved stiffness compared to other polymer blends containing recycled polymer compositions.

[0126] This can be additionally derived from the data in Figure 4, which is identical to Figure 3 but further shows comparative example values ​​according to the disclosure of WO 2021 / 032460 (stiffness improvement (tensile modulus) relative to CE2 in WO 2021 / 032460; carbon footprint reduction calculations as described herein). The WO 2021 / 032460 examples represent prior art polymer blends based on recycled polymer compositions. As can be seen from the plotted extrapolated lines in the diagram of Figure 4, examples according to embodiments of the present disclosure provided improved stiffness values ​​with comparable reductions in carbon footprint values. Thus, examples according to embodiments of the present disclosure were an improvement over the prior art WO 2021 / 032460.

[0127] Finally, Comparative Examples CE-11 and CE-12 and Examples IE-3 and IE-4 were prepared according to the above-mentioned method "Injection Molding Test." The properties of CE-5, CE-11, CE-12, IE-3, and IE-4 are shown in Table 4 below.

[0128] [Table 4]

[0129] As can be seen from Table 4, polymer blends according to embodiments of the present disclosure that included a polypropylene polymer composition according to embodiments of the present disclosure (P-4 or P-5) in addition to the recycled polymer composition (PCR-1) provided improved stiffness over Comparative Examples CE-5, CE-11, and CE-12. The results demonstrate that compositions according to embodiments of the present disclosure can be used to provide improved polymer blends according to embodiments of the present disclosure that have excellent material properties, low manufacturing complexity, and a reduced carbon footprint.

Claims

1. 1. A composition comprising: one or more polypropylene-based polymers; one or more additives selected from the group including antioxidants, acid scavengers, antistatic agents, nucleating agents, clarifiers, slip agents, and antiblocking agents; Including, The composition satisfies I>4.0, I is defined by the following formula (1): [Equation 1] During the ceremony, T ３ is the peak maximum temperature (°C) determined by analytical temperature rising elution fractionation, T ｃ is the crystallization peak temperature (°C) determined according to ISO 11357-3, XS is the xylene cold solubles (wt%) of the composition, determined in accordance with ISO 16152 using the temperature profile described in paragraph [0019]; The PI ratio is defined by the following equation (2): [Equation 2] During the ceremony, PI is the rheological polydispersity index determined by rheological oscillatory frequency sweep; the PI ratio is 0.90 to 1.23; MFR is the melt mass flow rate (g / 10 min) determined according to ISO 1133 at 230°C and a load of 2.16 kg, of the composition.

2. T ３ The composition of claim 1, wherein the temperature is 115.5°C to 140.0°C.

3. T ３ The composition according to claim 1 or claim 2, wherein the melting point is 115.5°C to 140.0°C.

4. T ｃ The composition according to claim 1 or claim 3, wherein the temperature is 115.0°C to 145.0°C.

5. 5. The composition of claim 1, wherein XS is ≦5.5 wt.%.

6. The composition according to any one of claims 1 to 5, wherein the MFR is 0.1 to 200 g / 10 min.

7. The composition of any one of claims 1 to 6, wherein I is > 9.

0.

8. T ３ is 117.3°C to 120.0°C, and T ｃ 8. The composition according to claim 1, wherein at least one of the following conditions is satisfied: XS is ≦2.4 wt.%, PI ratio is 0.95 to 1.13, MFR is 0.8 to 140 g / 10 min, and / or I is ≧9.

6.

9. A composition according to any one of claims 1 to 8; at least one recycled polymer; A polymer blend comprising:

10. 10. The polymer blend of claim 9, wherein the composition is present in an amount of 5% to 50% by weight based on the total weight of the polymer blend.

11. 11. The polymer blend of claim 9 or claim 10, wherein the at least one recycled polymer is present in an amount of 50% to 95% by weight, based on the total weight of the polymer blend.

12. 12. The polymer blend of any one of claims 9 to 11, wherein the at least one recycled polymer comprises >50 wt% polypropylene homopolymer and / or copolymer content.

13. A method for preparing the polymer blend of any one of claims 9 to 12, comprising mixing said composition with said at least one recycled polymer.

14. 9. Use of the composition of any one of claims 1 to 8 in a polymer blend for upgrading one or more post-consumer or post-industrial waste polymers.

15. The use according to claim 14, wherein the polymer blend is according to any one of claims 9 to 12.

16. 10. A method for upgrading one or more post-consumer or post-industrial waste polymers, comprising blending the one or more post-consumer or post-industrial waste polymers with the composition of any one of claims 1 to 8.

17. 17. The method of claim 16, wherein the one or more post-consumer or post-industrial polymers comprise one or more polypropylene-based polymers.

18. A molded article comprising the composition of any one of claims 1 to 8 or the polymer blend of any one of claims 9 to 12.

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