Polymer blends comprising recycled polymers with enhanced properties

Abstract

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

Description

Technical Field

[0001] The present disclosure relates to a composition comprising one or more polypropylene-based polymers and one or more additives, and a polymer blend comprising the composition and at least one recycled polymer. Furthermore, the present disclosure relates to a method for preparing the polymer blend and uses of the composition. The present disclosure also provides an article comprising the composition or the polymer blend. Background Art

[0002] Virgin polypropylene polymers can be produced using petrochemical technology, such as slurry or gas phase processes (see, for example, Pasquini, N., Polypropylene Handbook, 2nd edition, 2005). For the production of polypropylene homopolymers and random copolymers of propylene and other α-olefins, a factory setup with at least one polymerization reactor is required. Polypropylene homopolymers can have high stiffness (e.g., high flexural modulus), but generally lack impact resistance at room temperature and lower temperatures. On the other hand, random copolymers can have higher impact resistance at room temperature, but generally lack high stiffness. Impact copolymers, also known as heterophasic copolymers, provide a combination of high stiffness and high impact resistance because they contain portions of polypropylene homopolymer and ethylene-propylene copolymer. However, for the production of impact copolymers, at least two polymerization reactors are required in a cascade setup. Therefore, the production of impact copolymers is inherently more demanding because it is more complicated than the production of homopolymers or random copolymers.

[0003] For the production of virgin polypropylene polymers, different catalysts can be used, including Ziegler-Natta or metallocene type catalysts. For Ziegler-Natta catalysts, different internal donors have been developed over the past few decades, such as phthalate-, diether-, succinate-, or diester-based donors (see, for example, Paulik et al., Macromol. Chem. Phys. 2021, 222, 2100302). Internal donors have a significant impact on the properties of the produced polymers because they determine the achievable isotacticity, chemical composition distribution, molecular weight distribution, and comonomer insertion rate.

[0004] For all virgin polypropylene polymers, natural resources are used in the form of propylene gas and potentially other α-olefins. In the production process of virgin polypropylene polymers, a large amount of energy is required to melt the polymer in the factory extruder, heat, compress the gas, stir, and transport the final product from the petrochemical plant to distributors and processors. Therefore, the production of virgin polypropylene polymers requires a large amount of natural resources and produces a certain carbon footprint (e.g., 1.72 kg CO2-equivalent / kg material. Source: Alsabri et al., Polymers 2021, 13, 3793, average value of Table 4).

[0005] In some applications, compositions of virgin polypropylene polymers can be replaced in whole or in part by polymer compositions derived from, for example, post-consumer waste. However, in terms of physical properties, recycled polymer compositions exhibit poorer material properties than virgin polymer compositions because they contain a mixture of different polymers, which results in an average performance profile rather than significant performance for different applications, such as injection molding, film processing, or fiber and textile applications. Therefore, recycled polymer compositions are almost exclusively used in low-demand 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, for example, the use of fillers (see WO 2022 / 084236 A1 and WO 2014 / 167493 A1), compatibilizers (see EP 3715410 A1 and WO 2022 / 104275 A1), and the addition of different types of virgin polymers (see WO 2022 / 084236 A1, EP 3715410 A1, EP3916047 A1, WO 2021 / 032460 A1, WO 2014 / 167493 A1, WO 2021 / 165751 A1, US 2022 / 0145057 A1, WO 2022 / 104275 A1, WO 2022 / 123000 A1, WO 2022 / 123002 A1 and EP 3916047 A1). 3802689B1). With regard to the latter, the blend of virgin polymer composition and the polymer composition recovered has been shown to be a trade-off between good physical properties and reducing carbon footprint (see WO 2022 / 084236 A1 and WO 2021 / 165751A1). The prior art virgin polymer composition often used for the polymer composition of upgraded recycling is generally a commercial polymer product, which is intended to be used for compounding, injection molding, film or fiber applications without adding the polymer composition recovered (see, for example, US2022 / 0145057 A1, WO 2022 / 104275 A1, WO 2022 / 123000A1 and WO 2022 / 123002 A1). Therefore, the physical properties that can be achieved by the blend between the polymer composition recovered and the prior art virgin polymer composition are the superposition between the two, and a kind of performance profile required for the pure virgin polymer composition cannot be achieved. To address this problem, some applicants have disclosed compositions comprising, for example, multiolefin (co)polymers and / or polyethylene, wherein the polymers need to be prepared using laborious polymerization techniques and complex plant setups, ie requiring high manufacturing complexity.

[0007] A different approach to the problem of improving the blend properties between recycled and virgin polymer compositions has been found when using special internal donors for the polymerization of virgin polymers intended for blending with recycled polymer compositions. Non-phthalic acid esters, in particular, selected from optionally substituted malonates, maleates, succinates, glutarates, cyclohexene-1,2-dicarboxylates, benzoates, derivatives thereof, and / or mixtures thereof, have been found to be particularly suitable (see EP 3916047 A1 and WO 2021 / 032460 A1). Preferred types of internal donors are reportedly based on citraconates, for example, bis(2-ethylhexyl)citraconate.

[0008] In general, there is an unmet need for specialized polymer compositions that can enhance the properties of recycled polymers or recycled polymer compositions to virgin-like properties at low addition levels, which would contribute to a reduced carbon footprint and more efficient use of natural resources. In addition, the polymers used in these compositions should be obtainable via simple polymerization processes, i.e., have low manufacturing complexity. Summary of the Invention

[0009] One of the objects of the present disclosure is to provide a composition that, once blended with at least one recycled polymer, can upgrade at least one recycled polymer without the need for manufacturing complexity while maintaining a low carbon footprint. For example, the at least one recycled polymer can comprise one or more post-consumer waste polymers or post-consumer waste polymer compositions.

[0010] In this specification and the claims that follow, upgrading is intended to include, for example, the improvement of the mechanical, physical and / or chemical properties of at least one recycled polymer.

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

[0012] In another aspect, the present disclosure relates to a composition comprising:

[0013] one or more polypropylene-based polymers; and

[0014] One or more additives selected from the group consisting of, for example, antioxidants, acid scavengers, antistatic agents, nucleating agents, clarifying agents, slip agents, and antiblocking agents,

[0015] wherein the composition satisfies I>4.0,

[0016] where I is defined by the following equation (1):

[0017]

[0018] in

[0019] T3 is the highest peak temperature determined by analytical temperature-elution fractionation method, in °C;

[0020] T c is the peak crystallization temperature determined according to ISO 11357-3, in °C;

[0021] XS is the xylene cold soluble content of the composition, expressed in weight percent; and

[0022] The PI ratio is defined by the following equation (2):

[0023]

[0024] in

[0025] PI is the rheological polydispersity index determined by rheological oscillation frequency sweep;

[0026] The PI ratio is from 0.90 to 1.23; and

[0027] MFR is the melt mass flow rate determined according to ISO 1133 at 230° C. and a load of 2.16 kg, and is expressed in g / 10 minutes.

[0028] Surprisingly, it was found that when the composition according to the present disclosure is blended with at least one recycled polymer, even if the resulting polymer blend contains a large portion of the one or more recycled polymers (such as, for example, at least 40% by weight or more, up to 85% by weight, 90% by weight or more of the total weight of the polymer blend), the polymer blend can still exhibit the same or better material properties (e.g., stiffness) than the prior art polymer blends, while having a significantly reduced carbon footprint and more efficient use of natural resources. In addition, the composition of the present disclosure is easy to manufacture.

[0029] The compositions according to the present disclosure can be used to replace virgin polymer compositions, such as, for example, heterophasic (impact) copolymer compositions, which have both high stiffness and high impact resistance at room temperature, but have a higher carbon footprint, are less efficient in the use of natural resources, and require complex manufacturing methods or equipment.

[0030] In this specification and the claims that follow, the terms "virgin polymer" or "virgin material" refer to a polymer or material, respectively, that has been newly produced prior to first use and has not been recycled. For example, one or more polypropylene-based polymers in the compositions and polymer blends according to embodiments of the present disclosure comprise or are made from one or more virgin polymers.

[0031] In this specification and the claims that follow, the term "polypropylene-based polymer" is used to refer to any polymer, polymer composition, or polymer blend comprising polypropylene. Polypropylene may comprise a polypropylene homopolymer and / or a polypropylene copolymer. According to one or more embodiments, the polypropylene-based polymer comprises at least 50 wt%, 60 wt%, 70 wt%, 80 wt%, 90 wt%, 95 wt%, or 99 wt% homopolymer. According to one or more embodiments, the polypropylene-based polymer is a homopolymer.

[0032] Throughout this specification and the claims below, the term "T3" refers to the peak maximum temperature, expressed in °C, as determined by analytical temperature-rising elution fractionation (ATREF). ATREF was performed using an automated CRYSTAF-TREF instrument (PolymerChar SA, Spain) equipped with a heated infrared (IR) concentration detector and a capillary viscometer detector with a composition sensor. A polymer solution at a concentration of 3 ± 0.25 mg / ml was prepared in 1,2-dichlorobenzene (stabilized with 500 ppm of 2,6-di-tert-butyl-4-methylphenol) at 150°C for 90 minutes. After dissolution was complete, the sample was transferred to an ATREF column, where stabilization, crystallization, and elution cycles were performed as follows. During stabilization, the column was cooled from 150°C to 95°C at a rate of -40°C / min and then held at 95°C for 45 minutes. Crystallization was performed by cooling from 95°C to 35°C at a cooling rate of -0.5°C / min. After crystallization was complete, the column was held at 35°C for 10 minutes. Subsequently, the column contents were eluted over 10 minutes to collect the soluble fraction. Elution was 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 was normalized to 100% integration of the soluble fraction. The peak maximum temperature, T3, was designated as the maximum value observed within the temperature range from 100°C to 150°C.

[0033] In this specification and the following claims, the term " c " is the peak crystallization temperature in °C. The peak melting temperature T is determined according to ISO 11357-3 M (equivalent to T pm ) and peak crystallization temperature T C (equivalent to T pc ). The heating and cooling schedule is as follows: [1] 50 to 200°C at +10K / min; [2] 200°C for 5 minutes; [3] 200 to 50°C at -10K / min; [4] 50°C for 5 minutes; [5] 50 to 200°C at +10K / min. For the peak melting temperature T M , evaluate the second heating cycle (step [5]). For the peak crystallization temperature T c , evaluate the cooling cycle (step [3]).

[0034] In this specification and the claims below, the term "XS" is the xylene cold soluble content, expressed in weight percent. XS is determined according to ISO 16152 using the following modified temperature profile. For analysis, 5 grams of sample are added to a 1000 ml round-bottom flask and combined with 450 ml of o-xylene. The sample / xylene mixture is heated to 140 ± 2°C under reflux and maintained at this temperature for 60 minutes until a clear solution is obtained. The flask is cooled to 130°C until the reflux stops. Subsequently, the mixture is stirred and cooled in an ice bath for at least 20 minutes until the temperature reaches 5°C and a gel precipitates. The ice bath is then removed and replaced with a water bath maintained at 23°C. The flask is stirred continuously in the water bath for 30 minutes and slowly reheated to room temperature. The mixture is then poured into a filter and the solvent is collected. The precipitated gel is washed with another 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 was removed by evaporation until constant weight was reached.

[0035] Calculation method of xylene cold soluble content (XS):

[0036]

[0037] where m p : mass of the sample (g); m XYL : the mass of total xylene used (g); ρ XYL : Density of xylene used (g / ml); m RBF : Mass of 250ml empty round-bottom flask (g); m XS : Mass of the 250 ml round-bottom flask containing the residue (g); V XYL : the total volume of xylene used (ml); V 样品 : Volume of aliquot in 250 ml round bottom flask (ml).

[0038] In this specification and in the claims that follow, the term "PI" refers to the rheological polydispersity index determined as follows. Rheological oscillation frequency sweep experiments were performed on compression molded discs using a parallel plate geometry at 210°C with an oscillation strain amplitude γ0 = 10%, an angular frequency ω = 389 to 0.1 rad / s, and a DHR-2 rheometer (TA Instruments, Newcastle, USA). The storage modulus G' and loss modulus G" data were analyzed by performing a least squares polynomial fit: ln(G') = a2 × [ln(G")] 2 +a1×ln(G”)+a0. Cross modulus G C is calculated from the fitting parameters:

[0039]

[0040] The rheological polydispersity index (PI) is calculated from the cross modulus G C Calculated:

[0041]

[0042] In this specification and the claims that follow, "MFR" is the melt mass flow rate determined according to ISO 1133 at 230°C and a load of 2.16 kg.

[0043] Further embodiments of the composition are defined in the dependent claims.

[0044] In another aspect thereof, the present disclosure relates to a composition comprising one or more polypropylene-based polymers and one or more additives selected from, for example, antioxidants, acid scavengers, antistatic agents, nucleating agents, clarifying agents, slip agents, and antiblocking agents, wherein the one or more polypropylene-based polymers include a homopolymer prepared using a Ziegler-Natta catalyst supported by MgCl2-xROH, and the ratio of its internal donor to magnesium (ID / Mg) is at least 0.14. For example, ID / Mg can be from 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, the external donor, and the one or more additives can be according to any embodiment disclosed herein. According to one or more embodiments, the internal donor, the external donor, and the one or more additives are selected so that the composition satisfies I>4.

[0045] Furthermore, in another aspect thereof, the present disclosure relates to a polymer blend comprising a composition according to any embodiment disclosed herein and at least one recycled polymer. The at least one recycled polymer may include a recycled polymer composition.

[0046] In yet another of its aspects, the present disclosure relates to a method of preparing a polymer blend according to any of the embodiments disclosed herein, comprising mixing the composition with the at least one recycled polymer or polymer composition.

[0047] Furthermore, the present disclosure also relates to the use of the composition according to any embodiment disclosed herein in a polymer blend for upgrading one or more post-consumer waste polymers or industrial waste polymers comprised in the polymer blend.

[0048] In addition, the present disclosure also relates to an article comprising a composition according to any embodiment disclosed herein or a polymer blend according to any embodiment disclosed herein. According to one or more embodiments, the article can be formed by injection molding or thermoforming.

[0049] The present disclosure is based on the discovery that selected compositions can be blended with high levels of recycled materials (e.g., post-consumer waste) in polymer blends that have properties (e.g., stiffness) at least comparable to those of pure virgin polymer compositions.

[0050] The compositions and polymer blends according to one or more embodiments of the present disclosure can have excellent mechanical properties, such as, for example, flexural modulus and / or Charpy (notched) impact strength. Therefore, these compositions and polymer blends can contribute to a more efficient use of natural resources and can have a reduced carbon footprint, suitable for a wide range of applications including injection molding, thermoforming, and fiber applications.

[0051] Embodiments of the compositions and polymer blends can have a selected combination of characteristics (such as molecular weight distribution, crystallinity, and stereoregularity) that can be used to prepare polymer blends with a high content of recycled materials and a low carbon footprint, while having properties (e.g., stiffness) comparable to fully virgin polymer compositions. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] Figure 1 The flexural modulus of examples of polymer blends according to one or more embodiments, comparative examples of polymer blends, and comparative virgin polymer compositions are shown.

[0053] Figure 2 The carbon footprints of Examples and Comparative Examples showing comparable flexural modulus and Charpy (notched) impact resistance at 23°C are shown.

[0054] Figure 3 The relationship between the stiffness improvement [%] and the carbon footprint reduction [%] for the examples and comparative examples is shown.

[0055] Figure 4 The stiffness improvement [%] versus the carbon footprint reduction [%] for examples and comparative examples according to WO 2021 / 032460 A1 is shown. DETAILED DESCRIPTION

[0056] Embodiments of polymer blends are provided below. Unless otherwise indicated, embodiments of the compositions may include the same features as the composition features in any embodiment of the polymer blend. In other words, all features of the composition referenced for the polymer blend also apply to the composition used therein (and vice versa).

[0057] Polymer Blend Embodiments

[0058] Embodiments of the present disclosure are directed to a polymer blend comprising:

[0059] A composition comprising:

[0060] one or more polypropylene-based polymers; and

[0061] One or more additives selected from the group consisting of, for example, antioxidants, acid scavengers, antistatic agents, nucleating agents, clarifying agents, slip agents, and antiblocking agents; and

[0062] at least one recycled polymer,

[0063] wherein the composition satisfies I>4.0,

[0064] where I is defined by the following equation (1):

[0065]

[0066] in

[0067] T3 is the highest peak temperature determined by analytical temperature-elution fractionation method, in °C;

[0068] T c is the peak crystallization temperature determined according to ISO 11357-3, in °C;

[0069] XS is the xylene cold soluble content of the composition, in % by weight, determined according to ISO 16152 using the temperature profile described in paragraph

[0019] ; and

[0070] The PI ratio is defined by the following equation (2):

[0071]

[0072] in

[0073] PI is the rheological polydispersity index determined by rheological oscillation frequency sweep;

[0074] The PI ratio is from 0.90 to 1.23; and

[0075] MFR is the melt mass flow rate determined according to ISO 1133 at 230° C. and a load of 2.16 kg, and is expressed in g / 10 minutes.

[0076] According to one or more embodiments, T3 in equation (1) may be from 115.5°C to 140.0°C, preferably from 116.0°C to 135.0°C, more preferably from 116.5°C to 130.0°C, still more preferably from 117.0°C to 125.0°C, still more preferably from 117.2°C to 122.0°C, and most preferably from 117.3°C to 120.0°C.

[0077] According to one or more embodiments, T in equation (1) c It can be from 115.0℃ to 145.0℃, preferably from 117.0℃ to 140.0℃, more preferably from 119.0℃ to 139.0℃, still more preferably from 120.0℃ to 138.0℃, still more preferably from 122.0℃ to 137.0℃, still more preferably from 125.0℃ to 136.0℃, still more preferably from 127.0℃ to 135.0℃, and most preferably from 129.0℃ to 135.0℃.

[0078] According to one or more embodiments, XS in equation (1) may be ≤5.5 wt%, preferably ≤5.0 wt%, more preferably ≤4.5 wt%, still more preferably ≤4.0 wt%, still more preferably ≤3.5 wt%, still more preferably ≤3.0 wt%, still more preferably ≤2.5 wt%, and most preferably ≤2.4 wt%.

[0079] According to one or more embodiments, the PI ratio in equations (1) and (2) is from 0.91 to 1.20, preferably from 0.92 to 1.18, more preferably from 0.93 to 1.16, even more preferably from 0.94 to 1.14, even more preferably from 0.95 to 1.13, even more preferably from 0.96 to 1.10, even more preferably from 0.96 to 1.08, even more preferably from 0.96 to 1.05, and most preferably from 0.96 to 1.02.

[0080] According to one or more embodiments, the MFR (230°C, 2.16 kg, ISO 1133) in equation (2) may be from 0.1 to 200 g / 10 min, preferably from 0.2 to 190 g / 10 min, still more preferably from 0.3 to 180 g / 10 min, still more preferably from 0.5 to 170 g / 10 min, still more preferably from 0.6 to 160 g / 10 min, still more preferably from 0.7 to 150 g / 10 min, and most preferably from 0.8 to 140 g / 10 min.

[0081] Embodiments of the composition, whether used as a composition itself or as a component of a polymer blend, can have a selected property profile (including T3, T c , XS, PI ratio, MFR), which can be used to provide polymer blends with high levels of one or more recycled polymers, whose properties are at least comparable to or better than those of fully virgin polymer compositions, involve low manufacturing complexity, and result in a reduced carbon footprint. The profile of selected properties of the composition is expressed according to equation (1) above, and results in a predetermined value of I, which can be at least greater than 4.

[0082] According to one or more embodiments, I is >4.0, preferably ≥5.0, more preferably ≥6.0, still more preferably ≥7.0, still more preferably ≥8.0, still more preferably ≥9.0, still more preferably ≥9.5, and most preferably ≥9.6.

[0083] According to one or more embodiments, I is from >4.0 to 30, preferably from 5.0 to 25, more preferably from 6.0 to 20, more preferably from 7.0 to 18, more preferably from 8.0 to 16, more preferably from 9.0 to 14, and most preferably from 9.5 to 13.5.

[0084] According to one or more embodiments, in equation (1):

[0085] T3 is from 115.5℃ to 140.0℃, T c From 115.0℃ to 145.0℃, XS is ≤5.5wt%, t

[0086] In equation (2):

[0087] MFR is from 0.1 to 200 g / 10 minutes, and

[0088] I is >4.0.

[0089] According to one or more embodiments, in equation (1):

[0090] T3 is from 116.0℃ to 135.0℃, T c from 117.0°C to 140.0°C, XS is ≤5.0 wt%, PI ratio is from 0.91 to 1.20,

[0091] In equation (2):

[0092] MFR is from 0.2 to 190 g / 10 min, and

[0093] I is >5.0.

[0094] According to one or more embodiments, in equation (1):

[0095] T3 is from 117.3°C to 120.0°C, Tc is from 129.0°C to 135.0°C, XS is ≤ 2.4 wt%, and PI ratio is from 0.95 to 1.13 (e.g., from 0.96 to 1.02),

[0096] In equation (2):

[0097] MFR is from 0.8 to 140 g / 10 min, and

[0098] I is ≥9.6.

[0099] One or more polypropylene-based polymers

[0100] 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 wt%, 60 wt%, 70 wt%, 80 wt%, 90 wt%, 95 wt%, or 99 wt% homopolymers. According to one or more embodiments, the one or more polypropylene-based polymers are homopolymers.

[0101] According to one or more embodiments, the combination of properties of the composition can be achieved by producing one or more polypropylene-based polymers using a non-phthalate catalyst.

[0102] According to one or more embodiments, the one or more polypropylene-based polymers are prepared by using a Ziegler-Natta catalyst comprising an internal donor, optionally in combination with an external donor, and one or more optional specialized additives.

[0103] According to one or more embodiments, the internal donor may be selected from diethers, aliphatic diesters, aromatic diesters, succinates, citraconates, maleates, dibenzoates. According to one or more embodiments, the internal donor is selected from 1,3-diethers.

[0104] According to one or more embodiments, the 1,3-diether internal donor comprises 2-isopropyl-2-isopentyl-1,3-dimethoxypropane (I3I5).

[0105] According to one or more embodiments, the one or more polypropylene-based polymers are obtained by polymerization of propylene in a vertically stirred gas phase reactor (e.g., a Novolen-type reactor), for example, using a stereospecific MgCl2-xROH-supported Ziegler-Natta catalyst containing an internal donor (ID) based on a 1,3-diether, for example, at 30 bar and 75° C., and using an external donor such as, for example, isobutyl(isopropyl)dimethoxysilane (CAS 111439-76-0) to achieve a high level of isotacticity. According to one or more embodiments, the internal donor based on a 1,3-diether 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.

[0106] 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, still more preferably from 0.18 to 0.30, still more preferably from 0.18 to 0.25, still more preferably from 0.18 to 0.20, and an optimal internal donor to magnesium ratio (ID / Mg) of 0.19.

[0107] 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 of the above embodiments in combination with an external donor selected from alkoxysilanes, preferably from dimethoxysilanes, most preferably the external donor is isobutyl(isopropyl)dimethoxysilane (CAS 111439-76-0).

[0108] According to one or more embodiments, the composition comprises one or more polypropylene-based polymers in an amount of from 50% to 99.95% by weight relative to the total weight of the composition according to a), more preferably from 55% to 99.92% by weight, still more preferably from 60% to 99.90% by weight, still more preferably from 65% to 99.88% by weight, still more preferably from 70% to 99.85% by weight, still more preferably from 75% to 99.85% by weight, still more preferably from 99.85% to 99.85% by weight, still more preferably from 99.92% to 99.92% by weight, still more preferably from 99.92% to 99.92% by weight, still more preferably from 99.90% to 99.88% by weight, still more preferably from 99.85% to 99.85 ... From 80 wt.-% to 99.85 wt.-%, still more preferably from 85 wt.-% to 99.85 wt.-%, still more preferably from 90 wt.-% to 99.85 wt.-%, still more preferably from 95 wt.-% to 99.85 wt.-%, still more preferably from 96 wt.-% to 99.85 wt.-%, still more preferably from 97 wt.-% to 99.85 wt.-%, still more preferably from 98 wt.-% to 99.85 wt.-%, and most preferably from 98.5 wt.-% to 99.85 wt.-%, relative to the total weight of the composition.

[0109] One or more additives

[0110] 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 can be used to produce the one or more polypropylene-based polymers and / or can be added to the one or more polypropylene-based polymers after production. In either case, the use of one or more additives can result in high process stability and enhance the performance of the overall composition.

[0111] According to one or more embodiments, the one or more additives are selected from the group consisting of antioxidants, acid scavengers, antistatic agents, nucleating agents, clarifying agents, slip agents, and antiblocking agents.

[0112] 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 phenol compound 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 antioxidant may include a hindered amine compound. Exemplary compounds may be poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidinethanol-alt-1,4-butanedioic acid) (HAS 622), bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (HAS 770), and poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidinyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidinyl)imino] (HAS 944). For example, the hydroxylamine antioxidant may comprise oxidized bis(hydrogenated tallow alkyl)amine. An exemplary compound may be bis(octadecyl)hydroxylamine (FS 042). For example, the phosphite antioxidant may comprise a phosphite. Exemplary compounds may be tris(2,4-di-tert-butylphenyl)phosphite (AO-168), 3,9-bis(2,4-diisopropylphenylphenoxy)-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 phosphinate antioxidant may comprise a phosphinate. An exemplary compound may be tetrakis(2,4-di-tert-butylphenyl)[1,1'-biphenyl]-4,4'-diylbis(phosphinate) (PEPQ). For example, the benzofuranone antioxidant may comprise a 3-arylbenzofuranone. An exemplary compound may be 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one. For example, the thiodipropionate antioxidant may comprise an alkylthiodipropionate. An exemplary compound may be dioctadecyl 3,3'-thiodipropionate.For example, the acryl antioxidant may include acryl-modified phenols.An exemplary compound may be 2-(1,1-dimethylethyl)-6-[[3-(1,1-dimethylethyl)-2-hydroxy-5-methylphenylmethyl-4-methylphenylacrylate.

[0113] According to one or more embodiments, the acid scavenger may comprise any suitable acid scavenger known in the art. According to one or more embodiments, the acid scavenger is selected from metal stearates, hydrotalcites, hydrocalumites, metal oxides, metal carbonates, and combinations thereof. For example, the metal stearates may comprise calcium stearate and zinc stearate. For example, the hydrotalcites may comprise Mg 4.3 Al2(OH) 12.6 CO3·mH2O(DHT). For example, hydrocalumite may 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, the metal oxide may include zinc oxide, calcium oxide, magnesium oxide, and combinations thereof. For example, the metal carbonate may include zinc carbonate, calcium carbonate, magnesium carbonate, and combinations thereof.

[0114] According to one or more embodiments, the nucleating agent or clarifier may include any suitable nucleating agent or clarifier known in the art. In addition, according to one or more embodiments, the nucleating agent or clarifier may be selected from talc, metal benzoates, metal sulfates, carboxylates, phosphates, sorbitol-based clarifiers, nonanol-based clarifiers, and combinations thereof. For example, metal benzoates may include sodium benzoate, lithium benzoate, and hydroxybis(4-tert-butyl)aluminum benzoate. For example, metal sulfates may include barium sulfate. For example, carboxylates may include 1,2-cyclohexanedicarboxylic acid metal salts and bicyclo[2.2.1]heptane-2,3-dicarboxylic acid metal salts. For example, phosphates may include 2,2'-methylene-bis-(4,6-di-tert-butylphenyl) lithium phosphate, 2,2'-methylene-bis-(4,6-di-tert-butylphenyl) sodium phosphate, 2,2'-methylene-bis-(4,6-di-tert-butylphenyl) hydroxyaluminum phosphate. For example, sorbitol-based clarifying agents may include 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol (DMDBS), 1,3:2,4-bis(p-methylbenzylidene)sorbitol (MDBS), 1,3:2,4-dibenzylidenesorbitol (DBS). For example, nonanol-based clarifying agents may include 1,2,3-trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene]nonanol. Commercial examples of nucleating and clarifying 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.

[0115] According to one or more embodiments, the antistatic agent may comprise any suitable antistatic agent known in the art. According to one or more embodiments, the antistatic agent comprises glyceryl monostearate (GMS-55, GMS-90) or ethoxylated alkylamine.

[0116] According to one or more embodiments, the slip agent may comprise any suitable slip agent known in the art. Slip agents include erucamide and oleamide.

[0117] According to one or more embodiments, the anti-blocking agent may comprise any suitable anti-blocking agent known in the art. According to one or more embodiments, the anti-blocking agent comprises silica.

[0118] According to one or more embodiments, the one or more additives include antioxidants, acid scavengers and nucleating agents, preferably, the one or more additives include antioxidants, acid scavengers, antistatic agents and nucleating agents, even more preferably, the one or more additives include antioxidants, acid scavengers, antistatic agents, nucleating agents and clarifiers, even more preferably, the one or more additives include antioxidants, acid scavengers, antistatic agents, nucleating agents, clarifiers and slip agents, and most preferably, the one or more additives include antioxidants, acid scavengers, antistatic agents, nucleating agents, clarifiers, slip agents and antiblocking agents.

[0119] Compared to prior art blends based on recycled polymers, polymer blends according to one or more embodiments provide better material properties, a smaller carbon footprint, and more efficient use of natural resources. In addition, polymer blends according to one or more embodiments provide material properties that are at least comparable to or better than fully virgin polymer compositions, while having a significantly lower carbon footprint and manufacturing complexity.

[0120] According to one or more embodiments, the composition comprises from 0.05 to 5 wt% of one or more additives, preferably from 0.08 to 4 wt%, more preferably from 0.10 to 3 wt%, still more preferably from 0.12 to 2 wt%, most preferably the composition comprises from 0.15 to 1.5 wt% of one or more additives, based on the total weight of the composition.

[0121] According to one or more embodiments, when one or more additives are added to one or more polypropylene-based polymers after the one or more polypropylene-based polymers are produced, the one or more additives are selected from, for example, antioxidants and acid scavengers.

[0122] According to one or more embodiments, the composition is present in an amount of from 1 wt % to 99 wt %, preferably from 2 wt % to 90 wt %, more preferably from 2 wt % to 80 wt %, more preferably from 2 wt % to 70 wt %, more preferably from 2 wt % to 60 wt %, more preferably from 3 wt % to 55 wt %, more preferably from 4 wt % to 50 wt %, more preferably from 5 wt % to 50 wt %, more preferably from 10 wt % to 50 wt %, more preferably from 15 wt % to 50 wt %, most preferably from 15 wt % to 45 wt % of the total weight of the polymer blend.

[0123] At least one recycled polymer

[0124] In this specification and in the claims that follow, the term "recycled polymer" is used to denote polymers that have been recovered from post-consumer waste or industrial waste. Post-consumer waste refers to items that have completed at least their first use cycle (or life cycle), i.e., have reached their first end use, while industrial waste refers to manufacturing waste that does not normally reach the consumer.

[0125] According to one or more embodiments, in addition to one or more polymers recycled from post-consumer waste or industrial waste, the at least one recycled polymer may also comprise up to 20 wt%, preferably up to 17 wt%, more preferably up to 3 wt%, still more preferably up to 1 wt%, and most preferably up to 0.1 wt% of one or more polymers originating from virgin use.

[0126] 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 comprise recycled polypropylene homopolymers, recycled polypropylene copolymers, and compositions or blends comprising recycled polypropylene homopolymers and / or recycled polypropylene copolymers.

[0127] 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. The recycled polymer composition can be, for example, commercially available 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), etc. Non-exhaustive examples of recycled polymers are Systalen PP (Systec Plastics GmbH) and DIPOLEN PP (mtm Plastics GmbH). Embodiments of the present disclosure can use a variety of recycled polymer compositions. The recycled polymer or polymer composition can be in the form of pellets.

[0128] According to one or more embodiments, the at least one recycled polymer may have an MFR value of from 1 to 200 g / 10 min, preferably from 2 to 150 g / 10 min, still more preferably from 3 to 120 g / 10 min, still more preferably from 4 to 100 g / 10 min, still more preferably from 5 to 80 g / 10 min, still more preferably from 6 to 60 g / 10 min, still more preferably from 7 to 50 g / 10 min, still more preferably from 8 to 40 g / 10 min, still more preferably from 9 to 35 g / 10 min, still more preferably from 10 to 30 g / 10 min, and most preferably from 12 to 25 g / 10 min.

[0129] According to one or more embodiments, the at least one recycled polymer may have an ethylene content of ≤50 wt%, preferably ≤45 wt%, more preferably ≤40 wt%, still more preferably ≤35 wt%, still more preferably ≤30 wt%, still more preferably ≤25 wt%, still more preferably ≤20 wt%, still more preferably ≤18 wt%, still more preferably ≤17 wt%, still more preferably ≤16 wt%, and most preferably ≤15 wt%.

[0130] In this specification and the claims below, the term "ethylene content" is used to indicate the fraction of C2H4 units in a polymer derived from ethylene polymerization in units of % by weight. The ethylene content was determined by Fourier transform infrared (FTIR) spectroscopy using a Tensor 27 FTIR spectrometer (Bruker, USA) on a 200 ± 50 μm film. The film was prepared using a hot press at 200 ° C and 50 bar, and the spectral absorption was corrected for the actual film thickness. The FTIR spectra were collected at 4000–400 cm -1 The mid-infrared region was selected and the 750–700 cm -1 The spectral bands between the two groups were evaluated by comparison with the spectrum of reference samples calibrated by 13C NMR (Haaland et al., Anal. Chem. 1988, 60, 1193-1202).

[0131] 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.-%, still more preferably ≥ 60 wt.-%, still more preferably ≥ 65 wt.-%, still more preferably ≥ 70 wt.-%, still more preferably ≥ 75 wt.-%, still more preferably ≥ 80 wt.-%, and most preferably from 85 to 100 wt.-%.

[0132] In the present description and in the following claims, the term "polypropylene homopolymer and / or copolymer content" is used to indicate the fraction of polypropylene-based input material in wt.-% selected for the preparation of at least one recycled polymer.

[0133] According to one or more embodiments, the at least one recycled polymer may comprise ≥5 wt% post-consumer waste or industrial waste content, preferably ≥10 wt%, still more preferably ≥30 wt%, still more preferably ≥50 wt%, still more preferably ≥60 wt%, still more preferably ≥70 wt%, still more preferably ≥80 wt%, still more preferably ≥90 wt%, still more preferably ≥92 wt%, still more preferably ≥95 wt%, still more preferably ≥97 wt%, still more preferably ≥98 wt%, and most preferably ≥99 wt%.

[0134] According to one or more embodiments, the at least one recycled polymer may have a T from 90°C to 140°C. C (ISO 11357-3), preferably from 95°C to 135°C, more preferably from 100°C to 130°C, still more preferably from 105°C to 128°C, still more preferably from 110°C to 127°C, still more preferably from 112°C to 126°C, still more preferably from 114°C to 126°C, still more preferably from 116°C to 126°C, still more preferably from 118°C to 126°C, still more preferably from 120°C to 126°C, still more preferably from 122°C to 126°C, and most preferably from 123°C to 126°C.

[0135] 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, still more preferably ≤1700 MPa, still more preferably ≤1600 MPa, still more preferably ≤1500 MPa, still more preferably ≤1400 MPa, still more preferably ≤1300 MPa, still more preferably ≤1250 MPa, and most preferably ≤1200 MPa.

[0136] According to one or more embodiments, the at least one recycled polymer may have a 2 Up to 80kJ / m 2 Charpy (notched) 23 ° C (ISO 179-1), preferably from 2.0 kJ / m 2 Up to 70kJ / m 2 , more preferably from 2.5 kJ / m 2 Up to 60kJ / m 2, and more preferably from 3.0 kJ / m 2 Up to 50kJ / m 2 , still more preferably from 3.5 kJ / m 2 Up to 40kJ / m 2 , and more preferably from 4.0 kJ / m 2 Up to 30kJ / m 2 , and more preferably from 4.5 kJ / m 2 Up to 20kJ / m 2 , and more preferably from 5.0 kJ / m 2 Up to 15kJ / m 2 , and more preferably from 5.0 kJ / m 2 Up to 10kJ / m 2 , and more preferably from 5.0 kJ / m 2 Up to 8kJ / m 2 , and more preferably from 5.0 kJ / m 2 Up to 7kJ / m 2 , and most preferably from 5.0 kJ / m 2 Up to 6kJ / m 2 .

[0137] According to one or more embodiments, the at least one recycled polymer may be present in the polymer blend in an amount of from >0 wt % to <100 wt %, preferably from 10 to 99 wt %, more preferably from 20 to 98 wt %, still more preferably from 30 to 95 wt %, still more preferably from 40 to 95 wt %, still more preferably from 45 to 95 wt %, still more preferably from 50 to 95 wt %, still more preferably from 50 to 92 wt %, still more preferably from 50 to 90 wt %, still more preferably from 50 to 88 wt %, and most preferably from 55 to 85 wt % of the total weight of the polymer blend.

[0138] Embodiments of a method for preparing a polymer blend

[0139] According to one or more embodiments, the method of preparing a polymer blend includes mixing the composition with the at least one recycled polymer.

[0140] The composition and the at least one recycled polymer can be mixed by any suitable polymer mixing method known in the art.According to one or more embodiments, the composition and the at least one recycled polymer are mixed using an extruder or a drum mixer.

[0141] According to one or more embodiments, the method of preparing the polymer blend further comprises preparing the composition. According to one or more embodiments, preparing the composition comprises synthesizing one or more polypropylene polymers.

[0142] According to one or more embodiments, the synthesis of the one or more polypropylene polymers comprises polymerizing propylene in a vertically stirred gas phase reactor (e.g., a Novolen type reactor), for example, using a MgCl2-xROH supported Ziegler-Natta catalyst containing a non-phthalate internal donor (ID), for example, at 30 bar and 75°C, and using an external donor.

[0143] According to one or more embodiments, the internal donor is selected from 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).

[0144] 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 from 0.14 to 0.40, more preferably from 0.16 to 0.35, still more preferably from 0.18 to 0.30, still more preferably from 0.18 to 0.25, still more preferably from 0.18 to 0.20, and most preferably the ratio between internal donor and magnesium (ID / Mg) is 0.19.

[0145] According to one or more embodiments, the internal donor is 2-isopropyl-2-isopentyl-1,3 dimethoxypropane (CAS 129228-11-1) and the ID / Mg ratio is at least 0.14, and for example 0.19.

[0146] According to one or more embodiments, the one or more polypropylene polymers are synthesized using a Ziegler-Natta catalyst having an internal donor as described above in combination with an external donor selected from alkoxysilanes, preferably dimethoxysilanes. Preferably, the external donor is isobutyl(isopropyl)dimethoxysilane (CAS 111439-76-0).

[0147] According to one or more embodiments, a method of preparing a polymer blend includes combining a composition, at least one recycled polymer, and optionally one or more additives as described above.

[0148] Composition

[0149] The present disclosure relates to a composition as defined in any one of the embodiments of a polymer blend.

[0150] Composition and product use embodiments

[0151] 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.

[0152] One or more embodiments relate to the use of the composition in a polymer blend for upgrading one or more post-consumer waste polymers or industrial waste polymers.

[0153] One or more embodiments are directed to an article comprising a composition according to any embodiment described herein or a polymer blend according to any embodiment described herein.

[0154] The article may be formed from the polymer composition and / or polymer blend by any suitable method known in the art.

[0155] Examples

[0156] Compounding test

[0157] Examples IE-1 and IE-2 according to embodiments of the present disclosure, as well as comparative examples CE-7 to CE-10, were prepared using a co-rotating twin-screw extruder (screw diameter D: 25.5 mm). The polymer compositions were extruded together with an additive premix for process stabilization. The additive premix comprised Irganox 1010 (BASF, Germany), Irganox 168 (BASF, Germany), calcium stearate (Berloch, Germany), and Systalen C45003 (Systec Plastics, Germany) in a ratio of 1:1:1.8:7.6. The additive premix was dosed in such a manner that the final composition contained an additional 450 ppm of Irganox 1010, 450 ppm of Irganox 168, and 800 ppm of calcium stearate. All ingredients were fed through the main feed port of the extruder using a gravimetric feeder. The compositions were extruded using a standard screw configuration comprising conveying, kneading, transition, and backmixing elements. The extruder was operated at 350 rpm with a temperature profile of 140 to 210°C. The produced polymer strands were cooled in a cold water bath and pelletized using a pelletizer. The extruder and feeder were cleaned between the preparation of different polymer blends to prevent cross contamination.

[0158] For IE-1 and IE-2 prepared according to the examples of the present disclosure, as well as comparative examples CE-7 to CE-10, test specimens were prepared according to ISO 19069-2 and ISO 20753. Prior to testing, the specimens were conditioned at 23°C and 50% relative humidity for 7 days. 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.

[0159]

[0160] To calculate the stiffness improvement, the elastic modulus is used, whether in a bending test according to ISO 178 or in a tensile test according to ISO 527-2.

[0161] Injection molding test

[0162] Examples IE-3 and IE-4 according to embodiments of the present disclosure and comparative examples CE-11 and CE-12 were prepared by blending pellets of PCR-1 and CP-1, CP-3, P-4, or P-5 using a drum mixer. The blended pellet mixture was then fed directly into the hopper of an injection molding machine. The temperature profile of the injection molding machine's heating zones was 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; for IE-4: 200°C / 195°C / 190°C / 185°C / 180°C. Test specimens for mechanical testing were prepared according to ISO 19069-2 and ISO 20753. Before testing, the specimens were conditioned for 7 days at 23° C. and 50% relative humidity. The flexural modulus values ​​were determined in accordance with ISO 178. The Charpy (notched) impact values ​​at 23° C. were determined on notched specimens in accordance with ISO 179-1 / 1eA.

[0163] Reduction of natural resource use and calculation of carbon footprint

[0164] The reduction in natural resource use and carbon footprint were calculated based on the equation below and literature values. The calculations took into account the weight fraction of the "virgin polymer composition," including the polymer components and additives, i.e., the final polymer material. "Virgin polymer composition" refers to material that has not yet been converted into an article and used by consumers or industry. Furthermore, "virgin polymer composition" is characterized by not having been processed more than once at elevated temperatures of 150°C or higher.

[0165]

[0166] Carbon footprint [kg CO2-equivalent / kg material]

[0167] =f 原生 ×(Carbon Footprint) 原生 +f 回收的 ×(Carbon Footprint) 回收的

[0168] Where f: weight fraction [wt%] / 100 wt%

[0169]

[0170] Values ​​considered in carbon footprint calculation:

[0171] Virgin polymer composition: 1.72 kg CO2-equivalent / kg material. Source: Average value from Table 4 of Alsabri et al., Polymers 2021, 13, 3793.

[0172] Recycled polymer composition: 0.8 kg CO2 equivalent / kg material. Source: Systec Plastics GmbH, Germany (supplier of PCR-1 (CE-5) and PCR-2 (CE-6)).

[0173] Synthetic Example

[0174] CP-1: Polypropylene polymer composition CP-1 was prepared by synthesizing a polypropylene homopolymer in a vertically stirred gas phase reactor (Novolen type) at 30 bar pressure and 80° C. using a stereospecific MgCl2-supported granular Ziegler-Natta catalyst containing diisobutyl phthalate (DIBP) as an internal donor. An external donor (cyclohexylmethyldimethoxysilane) was fed to the reactor to increase isotacticity. Hydrogen was fed to the reactor to control the polymer molecular weight, and the feed rate was adjusted to achieve an MFR of approximately 1 g / 10 min (230° C., 2.16 kg). The resulting powder was extruded on a twin-screw extruder along with 160 ppm of Cyanox 1790 (Solvay SA, Belgium), 600 ppm of ADK STAB PEP-36 (Adeka Corp., Japan), and 600 ppm of calcium stearate, relative to the total composition.

[0175] Comparative Example CP-2: Polypropylene polymer composition CP-2 was prepared by synthesizing a polypropylene homopolymer in a vertically stirred gas phase reactor (Novolen type) at 30 bar pressure and 80° C. using a stereospecific MgCl2-supported granular Ziegler-Natta catalyst containing diisobutyl phthalate (DIBP) as an internal donor. An external donor (cyclohexylmethyldimethoxysilane) was fed to the reactor to increase isotacticity. Hydrogen was fed 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 on a twin-screw extruder along with 500 ppm of Irganox 1010 (BASF, Germany), 500 ppm of Irganox 168 (BASF, Germany), and 800 ppm of calcium stearate, relative to the total composition.

[0176] Comparative Example CP-3: Polypropylene polymer composition CP-3 was prepared in a vertically stirred gas-phase reactor (Novolen type) at 30 bar pressure and 75°C using a stereospecific MgCl2-xROH-supported Ziegler-Natta catalyst containing a diether-based internal donor. The catalyst was prepared according to US Pat. No. 10,066,034 B2, using 2-isopropyl-2-isopentyl-1,3-dimethoxypropane (I3I5) as the internal donor (ID) with an ID / Mg ratio of 0.13, except that a fixed titanation step was used instead of Soxhlet extraction. An external donor (isobutyl(isopropyl)dimethoxysilane) was fed to the reactor to increase isotacticity. Hydrogen was fed to the reactor to control polymer molecular weight, and the feed rate was adjusted to achieve an MFR of approximately 145 g / 10 min (230°C, 2.16 kg). The resulting powder was extruded on a twin-screw extruder together with 450 ppm of Irganox 1010 (BASF, Germany), 450 ppm of Irganox 168 (BASF, Germany) and 800 ppm of calcium stearate, relative to the total composition.

[0177] P-4: Polypropylene polymer composition P-4 according to an embodiment of the present disclosure was prepared by synthesizing a 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 internal donor. The catalyst was prepared according to US 10,066,034 B2 with 2-isopropyl-2-isopentyl-1,3-dimethoxypropane (I3I5) as the internal donor (ID) with an ID / Mg ratio of 0.19, except that a fixed titanation step was used instead of Soxhlet extraction. An external donor (isobutyl(isopropyl)dimethoxysilane) was fed to the reactor to increase the isotacticity. Hydrogen was fed to the reactor to control the polymer molecular weight, and the feed rate was adjusted to achieve an MFR of about 1 g / 10 min (230° C., 2.16 kg). The obtained powder was extruded on a twin-screw extruder together with 450 ppm of Irganox 1010 (BASF, Germany), 900 ppm of Irganox 168 (BASF, Germany), 300 ppm of DHT-4A (Kisuma Chemicals BV, The Netherlands), and 4500 ppm of NA-27 (Adeka, Japan), relative to the total composition.

[0178] P-5: The polypropylene polymer composition P-5 according to an embodiment of the present disclosure was prepared by synthesizing a 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 internal donor. The catalyst was prepared according to US 10,066,034 B2 with 2-isopropyl-2-isopentyl-1,3-dimethoxypropane (I3I5) as the internal donor (ID) with an ID / Mg ratio of 0.19, except that a fixed titanation step was used instead of Soxhlet extraction. An external donor (isobutyl(isopropyl)dimethoxysilane) was fed to the reactor to increase the isotacticity. Hydrogen was fed to the reactor to control the polymer molecular weight, and the feed rate was adjusted to achieve an MFR of about 135 g / 10 min (230° C., 2.16 kg). The obtained powder was extruded on a twin-screw extruder together with 450 ppm of Irganox 1010 (BASF, Germany), 450 ppm of Irganox 168 (BASF, Germany), 800 ppm of calcium stearate, 600 ppm of glycerol monostearate (GMS-55), and 500 ppm of NA-27 (Adeka, Japan), relative to the total composition.

[0179] Comparative Example of Virgin and Recycled Polypropylene Compositions:

[0180] CE-1: Comparative Example CE-1 is a virgin polypropylene homopolymer composition prepared by synthesizing a 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 US Pat. No. 10,066,034 B2, using 2-isopropyl-2-isopentyl-1,3-dimethoxypropane (I3I5) as the internal donor (ID) with an ID / Mg ratio of 0.13, except that a fixed titanation step was used instead of Soxhlet extraction. An external donor was fed to the reactor to increase isotacticity. Hydrogen was fed to the reactor to control polymer molecular weight. The resulting powder was extruded on a twin-screw extruder along with an additive package containing an antioxidant, an acid scavenger, and a nucleating agent.

[0181] CE-2: Comparative Example CE-2 is a virgin polypropylene homopolymer composition prepared by synthesizing a 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 US Pat. No. 10,066,034 B2, using 2-isopropyl-2-isopentyl-1,3-dimethoxypropane (I3I5) as the internal donor (ID) with an ID / Mg ratio of 0.13, except that a fixed titanation step was used instead of Soxhlet extraction. An external donor was fed to the reactor to increase isotacticity. Hydrogen was fed to the reactor to control polymer molecular weight. The resulting powder was extruded on a twin-screw extruder along with an additive package containing an antioxidant, an acid scavenger, but no nucleating agent.

[0182] CE-3: Comparative Example CE-3 is a virgin propylene-ethylene random copolymer composition prepared by synthesizing a 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 increase isotacticity. Hydrogen was fed to the reactor to control polymer molecular weight. The resulting powder was extruded on a twin-screw extruder along with an additive package containing an antioxidant, an acid scavenger, and a clarifier.

[0183] CE-4: Comparative Example CE-4 is a virgin propylene ethylene impact copolymer composition prepared by synthesizing a propylene ethylene impact copolymer in a vertically stirred gas-phase dual 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 are fed to the first reactor to produce a low molecular weight homopolymer, which is then transferred to the second reactor. In the second reactor, propylene, ethylene, and isopropanol are fed to obtain a propylene ethylene impact copolymer with a heterogeneous morphology. The resulting powder is extruded on a twin-screw extruder along with an additive package containing an antioxidant, an acid scavenger, and a nucleating agent.

[0184] CE-5: Comparative Example CE-5 is a polymer composition PCR-1 recycled from a polypropylene-based input stream, ie, the commercial product Systalen C45003 from Systec Plastics GmbH, Germany. This product is derived from >99% post-consumer waste.

[0185] CE-6: Comparative Example CE-6 is a polymer composition PCR-2 recycled from a polypropylene-based input stream, ie, the commercial product Systalen C14002 from Systec Plastics GmbH, Germany. This product is derived from >99% post-consumer waste.

[0186] Examples from compounding trials (regarding the components before addition of the additive premix for process stabilization):

[0187] CE-7: 100% PCR-1

[0188] CE-8: Polymer blend: 60% PCR-1 + 40% CP-2

[0189] CE-9: Polymer blend: 80% PCR-1 + 20% CP-1

[0190] CE-10: Polymer blend: 60% PCR-1 + 40% CP-1

[0191] IE-1: Polymer blend: 80% PCR-1 + 20% P-4

[0192] IE-2: Polymer blend: 60% PCR-1 + 40% P-4

[0193] Examples from injection molding trials:

[0194] CE-11: Polymer blend: 80% PCR-1 + 20% CP-1

[0195] CE-12: Polymer blend: 80% PCR-1 + 20% CP-3

[0196] IE-3: Polymer blend: 80% PCR-1 + 20% P-4

[0197] IE-4: Polymer blend: 80% PCR-1 + 20% P-5

[0198] result:

[0199] Examples CP-1 to CP-3 and P-4 to P-5 were prepared as described above. The properties of the polypropylene polymer compositions prepared from Comparative Examples CP-1 to CP-3 and Examples P-4 and P-5 according to embodiments of the present disclosure are shown in Table 1 below. It can be seen that compared to the lower I values ​​of 1.1 to 4.0 for Comparative Examples CP-1 to CP-3, the properties MFR, XS, T3, PI, and T c The combination of α and β resulted in higher I values ​​of 9.6 and 11.2.

[0200] Table 1: Properties of polymer compositions used to prepare inventive and comparative examples.

[0201]

[0202] Comparative Examples CE-1 to CE-6 were prepared as described above or are commercially available. The properties of Comparative Examples CE-1 to CE-6 are shown in Part 1 and Part 2 of Table 2. Furthermore, the reduction in natural resource use, carbon footprint, and the value of the reduction in carbon footprint are also shown.

[0203] As can be seen, the fully virgin polymer compositions of CE-1 to CE-4 have a high carbon footprint. The fully recycled polymer compositions of Comparative Examples CE-5 and CE-6 have a reduced carbon footprint and use reduced amounts of natural resources, but the flexural modulus (stiffness) of the fully recycled polymer compositions (1088 to 1164) is lower than the flexural modulus (1256 to 1500) of the fully virgin polymer compositions of CE-1 to CE-4.

[0204] Table 2 Part 1: Properties of comparative examples of virgin and recycled polypropylene compositions.

[0205]

[0206]

[0207] Table 2 Part 2: Properties of comparative examples of virgin and recycled polypropylene compositions.

[0208]

[0209] Comparative Examples CE-7 to CE-10 and Examples IE-1 and IE-2 were prepared according to the "Mix Test" 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. The values ​​for stiffness improvement, reduction in natural resource use, carbon footprint, and the amount of carbon footprint reduction are also shown.

[0210] Table 3 Part 1: Properties of comparative examples CE-7 to CE-10 and examples IE-1 and IE-2 of the mixing tests.

[0211]

[0212]

[0213] (*): relative to the composition before addition of the additive premix for process stabilization.

[0214] Table 3 Part 2: Properties of comparative examples CE-7 to CE-10 and examples IE-1 and IE-2 of the mixing tests. (*): relative to the composition before addition of the additive premix for process stabilization.

[0215] As can be seen from Table 3, Part 1 and Part 2, the polymer blends of Examples IE-1 and IE-2 have a carbon footprint reduction of 43% and 32% compared to the virgin polymer compositions of CE-1 to CE-4. Comparative Examples CE-7 to CE-10 have a carbon footprint reduction 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 contains 100% recycled polymer composition PCR-1, is low compared to the flexural modulus values ​​of the fully virgin polymer compositions of Comparative Examples CE-1 to CE-4. In addition, it can be seen that the polymer blends of Comparative Examples CE-8 to CE-10, which contain virgin polymer compositions according to Comparative Examples CP-1 and CP-2, have only a low stiffness improvement of 7% to 15%.

[0216] The polymer blends of Examples IE-1 and IE-2, which contain the virgin polymer composition of Example P-4 having a specific combination of properties resulting in an I value > 4.0, have a high carbon footprint reduction, a high reduction in natural resource use, and a high stiffness improvement of 21% to 36%. The stiffness improvements of IE-1 and IE-2 are higher than the stiffness improvements of Comparative Examples CE-8 to CE-10.

[0217] In addition, from Figure 1As can be seen, the polymer blends of Examples IE-1 and IE-2 have higher flexural modulus values ​​than Comparative Examples CE-9 and CE-10, which contain the polymer composition of Comparative Example CP-1. Furthermore, the flexural modulus values ​​of the polymer blends of Examples IE-1 and IE-2 are comparable to or even higher than the flexural modulus values ​​of the fully virgin polymer compositions of CE-1 to CE-4. Thus, the polymer blends of Examples IE-1 and IE-2, which contain the polypropylene polymer composition according to the examples of the present disclosure (according to Example P-4), have a low carbon footprint and excellent stiffness values ​​that are comparable to or even improved compared to the fully virgin polymer compositions.

[0218] like Figure 2 As shown, the polymer blend of Example IE-1 has an excellent 21% stiffness improvement (see Table 3, Part 2) with a 43% reduction in carbon footprint, while the polymer blend of CE-10 has only a 32% reduction in carbon footprint and a low stiffness improvement of 15% (see Table 3, Part 2). Figure 2 All examples and comparative examples in have approximately the same flexural modulus (stiffness) of 1400 MPa (±5%). Thus, Example IE-1 provides the highest carbon footprint reduction while achieving the same material properties.

[0219] Figure 3 is a graph showing the reduction in carbon footprint relative to the improvement in stiffness for Comparative Examples CE-7 to CE-10 and Examples IE-1 and IE-2. From this graph, it can be determined that improved stiffness values ​​are achieved by using the polypropylene polymer composition P-4 according to an embodiment of the present disclosure in a polymer blend according to an embodiment of the present disclosure, compared to polymer blends containing the same amount of recycled polymer composition, but the recycled polymer composition contains the comparative polypropylene polymer composition CP-1 or CP-2. Examples IE-1 and IE-2 according to embodiments of the present disclosure achieve improved stiffness values ​​at comparable values ​​of carbon footprint reduction. Thus, polymer blends according to embodiments of the present disclosure are highly sustainable and provide improved stiffness compared to other polymer blends containing recycled polymer compositions.

[0220] This can also be obtained from Figure 4 It is found from the data that Figure 4 and Figure 3 Same as, but further showing the values ​​according to the comparative example disclosed in WO 2021 / 032460A1 (stiffness improvement (tensile modulus) relative to CE2 in WO 2021 / 032460 A1; calculation of the reduction in carbon footprint as described herein). The examples of WO 2021 / 032460 A1 represent prior art polymer blends based on recycled polymer compositions. Figure 4As can be seen from the extrapolated line drawn in the graph of , the examples according to the embodiments of the present disclosure provide improved stiffness values ​​with a comparable reduction in carbon footprint values. Therefore, the examples according to the embodiments of the present disclosure are an improvement over the prior art WO 2021 / 032460 A1.

[0221] Finally, comparative examples CE-11 and CE-12 and examples IE-3 and IE-4 were prepared according to the "Injection Molding Test" method described above. The properties of CE-5, CE-11, CE-12, IE-3 and IE-4 are shown in Table 4 below.

[0222] Table 4. Comparative and Examples from injection molding trials.

[0223]

[0224] As can be seen from Table 4, the polymer blends according to embodiments of the present disclosure, in addition to the recycled polymer composition (PCR-1), further comprised a polypropylene polymer composition according to embodiments of the present disclosure (P-4 or P-5), and had improved stiffness compared to comparative examples CE-5, CE-11, and CE-12. Thus, it has been demonstrated that the compositions according to embodiments of the present disclosure can be used to provide improved polymer blends according to embodiments of the present disclosure having excellent material properties, low manufacturing complexity, and a reduced carbon footprint.

Claims

1. A composition comprising: one or more polypropylene-based polymers; and One or more additives selected from the group consisting of antioxidants, acid scavengers, antistatic agents, nucleating agents, clarifying agents, slip agents, and antiblocking agents, wherein the composition satisfies I>4.0, where I is defined by the following equation (1): in T3 is the highest peak temperature determined by analytical temperature-elution fractionation method, in °C; T c is the peak crystallization temperature determined according to ISO 11357-3, in °C; XS is the xylene cold soluble content of the composition, in wt. %, determined according to ISO 16152 using the temperature profile described in paragraph [0019]; and The PI ratio is defined by the following equation (2): in PI is the rheological polydispersity index determined by rheological oscillation frequency sweep; The PI ratio is from 0.90 to 1.23; and MFR is the melt mass flow rate determined according to ISO 1133 at 230° C. and a load of 2.16 kg and is expressed in g / 10 minutes.

2. The composition of claim 1, wherein T3 is from 115.5°C to 140.0°C.

3. The composition of claim 1 or claim 2, wherein T3 is from 115.5°C to 140.0°C.

4. The composition according to claim 1 or claim 3, wherein T c From 115.0℃ to 145.0℃.

5. The composition according to any one of claims 1 to 4, wherein XS is ≤ 5.5 wt%.

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

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

0.

8. The composition according to any one of claims 1 to 7, wherein at least one of the following conditions is met: T3 is from 117.3°C to 120.0°C, T c is from 129.0°C to 135.0°C, XS is ≤2.4 wt%, PI ratio is from 0.95 to 1.13, MFR is from 0.8 to 140 g / 10 min, and / or I ≥9.

6.

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

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

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

12. The polymer blend according to 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 of preparing a polymer blend according to any one of claims 9 to 12, said method comprising mixing said composition with said at least one recycled polymer.

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

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

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

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

18. An 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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