Method for improving the viscosity of recycled polyethylene

Abstract

A method of making a polyolefin composition is provided, the method comprising: 1) extruding at least one recycled polyolefin in the presence of at least one free radical initiator (E) to make an extruded vis-broken recycled polyolefin; and 2) melt blending (A) from about 60 wt% to about 96 wt% of the extruded recycled polyolefin; (B) from about 2 wt% to about 20 wt% of at least one random alpha-olefin copolymer; and (C) optionally from about 2 wt% to about 20 wt% of at least one tackifier; (D) optionally at least one additional polymer; wherein the polyolefin composition has a weight ratio of random alpha-olefin copolymer to tackifier of between about 0.2 to about 5.0; and wherein the extruded vis-broken polyolefin composition has an increase in melt flow rate of from about 5% to about 1500% compared to the recycled polyolefin.

Description

TECHNICAL FIELD

[0001] The present invention relates to a polyolefin composition comprising: A) from about 60 wt% to about 96 wt% of at least one recycled polyolefin; B) from about 2 wt% to about 20 wt% of at least one random alpha-olefin copolymer; and C) from about 2 wt% to about 20 wt% of at least one tackifier; wherein the polyolefin composition has a weight ratio of random alpha-olefin copolymer to tackifier of between about 0.2 to about 5.0; and wherein the polyolefin composition has an increase in melt flow rate of from about 5% to about 400% compared to the same polyolefin composition without the random alpha-olefin copolymer and the tackifier. The present invention also relates to a method of making the polyolefin composition and to an article comprising the polyolefin composition. BACKGROUND

[0002] Polyolefins, particularly polyethylene and polypropylene, are increasingly consumed in large quantities in a wide range of applications, including packaging of food and other goods, fibers, automotive parts, containers, and a wide variety of articles.

[0003] In the past decade, concerns have arisen about the environmental sustainability of plastics and their use in current quantities. This has led to new legislation for the disposal, collection, and recycling of polyolefin materials. Additionally, some countries are also working to increase the percentage of recycled plastic materials, rather than sending them to landfills.

[0004] Accordingly, the use of recycled materials derived from a variety of post-consumer and post-industrial sources is an increasing demand in the polyolefin field. However, commonly available recycled streams have limited rheological and mechanical properties, reducing commercially attractive end-uses. Commercial flow and impact modifiers currently available for upgrading recycled streams are either too expensive, thereby making recycling so uneconomical, or tend to result in an imbalance of rheological and mechanical properties, for example, sacrificing impact strength for yield strength, or sacrificing Young’s modulus or viscosity for impact strength.

[0005] In particular, mechanically recycled polymers typically show defects in flow characteristics (low MFI, high viscosity) and impact properties (reduced Izod or Charpy impact strength, notched and unnotched) resulting from the recycling process (extrusion) and the use of the article before recycling (e.g. exposure to UV, heat, etc.). Currently available commercial solutions typically focus on the improvement of a single property (e.g. only flow or only impact strength), which makes an integrated, easy-to-use solution that simultaneously optimizes and balances multiple properties to produce a good combination of processability and preferred end-use characteristics desirable.

[0006] Simultaneous optimization of flowability and impact strength can also be beneficial for certain virgin polyolefins such as polypropylene homopolymers. If customers can adjust lower-impact polypropylene homopolymers to higher-impact grades, it will create more purchasing power for them. Similarly, virgin polypropylene and polyethylene copolymers can also benefit from simultaneous optimization and balance of properties.

[0007] In blends primarily composed of polyethylene and polypropylene, higher impact strength can be achieved by adding an elastomer (such as conventional ethylene-propylene rubber or EPDM) as a compatibilizer. However, this addition limits the stiffness of the resulting composition.

[0008] Recently developed highly crystalline metallocene-based polypropylene-ethylene elastomers (e.g., Vistamaxx) TM 6102 (from ExxonMobil Chemical Company, Houston, TX, USA) increases impact strength by acting as a compatibilizer between the polyethylene and polypropylene portions in recycled compounds. However, these solutions still show a reduction in stiffness and yield strength, with only a modest improvement in rheology.

[0009] Literature suggests incorporating heterogeneous ethylene-propylene copolymers (HECO) containing ethylene-octene copolymers. HECO can be marketed under various trade names. Purchased from Borealis Plastomers (NL), under the brand name Engage TM Purchased from Dow Chemical Company (Midland, MI, USA) or ENI SpA (IT). However, the use of arbitrary heterogeneous ethylene-propylene copolymer (HECO) yielded poor results, particularly in terms of stiffness.

[0010] It is generally believed that limited stiffness can only be achieved by using plastics with block copolymer structures (such as those made from Dow Chemical INFUSE). TM Olefin block copolymer (OBC) or Intune TM OBC plastic bodies provide solutions to overcome this. For example, the introduction of INTUNE TM Polypropylene-based OBCs (PP-OBCs) are used as compatibilizers rather than elastomers. They contain propylene-rich blocks compatible with polypropylene and ethylene-rich blocks compatible with polyethylene. It is easy to understand that block copolymers introduce the option of certain highly crystalline regions with higher stiffness, thus increasing overall stiffness. However, plastics with block copolymer properties have the disadvantage of being relatively expensive.

[0011] As suggested in the literature, polyethylene elastomers (e.g., Vistamaxx) TMElastomers and acrylic plastics (e.g., Engage) TM The combination of ethylene-octene copolymers is limited by the economic feasibility of the proposed solution and focuses on enhanced impact strength while sacrificing modulus and significant viscosity optimization.

[0012] The literature also suggests that adding a C2C8 plasmid with a melt flow rate (MFR) of 1.5 g / 10 min (ISO 1133, 190 °C, 2.16 kg) is a more economical solution compared to using a combination of elastomers and plasmids. This solution can improve impact strength with a moderate reduction in Young's modulus, but still sacrifices rheological properties.

[0013] Therefore, there remains an urgent need for a good balance of viscosity, stiffness and impact strength in polyolefin compositions containing recycled polyolefins.

[0014] In particular, there is an urgent need for upgraded polyolefin compositions containing recycled polyolefins, wherein the composition has an increased MFR compared to recycled polyolefins alone, while maintaining the desired mechanical properties.

[0015] This invention is based on the surprising discovery that combining random α-olefin copolymers with hydrocarbon tackifier resins (“tackifiers”) results in a significant increase in MFR (ISO 1133) while balancing mechanical properties such as yield strength (ISO 527-2) and impact strength (ISO 179-1). This invention also achieves this using relatively inexpensive modifiers, providing a sustainable and economical solution for the recycled polyolefin market.

[0016] In one embodiment, the invention is based on the surprising discovery that combining random α-olefin copolymers with hydrocarbon tackifier resins (“tackifiers”) in polyethylene-rich recycled polyolefin compositions results in a significant increase in MFR (ISO 1133) and elongation at break or elongation at yield, while balancing other mechanical properties.

[0017] In another embodiment, the invention is based on the surprising discovery that non-rubber polymers such as linear low-density polyethylene (LLDPE), ethylene-acrylate copolymers, and medium-density polyethylene (MDPE) can be combined with at least one random α-olefin copolymer and at least one hydrocarbon tackifier resin to improve the impact strength of polyolefin compositions containing recycled polyolefins.

[0018] The present invention is also based on the surprising discovery that a novel method involving the de-tack cracking of recycled polyolefins followed by melt blending with at least one random α-olefin copolymer also results in a significant increase in MFR while balancing mechanical properties such as yield strength and impact strength. More specifically, a method has been discovered comprising: 1) extruding at least one recycled polyolefin in the presence of at least one free radical initiator to prepare a viscous cracked recycled polyolefin; and 2) contacting (A) about 60 wt% to about 96 wt% of the viscous cracked recycled polyolefin; (B) about 2 wt% to about 20 wt% of at least one random α-olefin copolymer; and (C) optionally about 2 wt% to about 20 wt% of at least one tackifier; wherein the polyolefin composition has a weight ratio of random α-olefin copolymer to the tackifier between about 0.2 and about 5.0; and wherein the extruded viscous cracked polyolefin composition has a melt flow rate increase of about 5% to about 400% compared to the same polyolefin composition without melt blending with random α-olefin copolymer and optional tackifier; and wherein the polyolefin composition has a melt flow rate increase of about 5% to about 1500% compared to the same polyolefin composition without the viscous cracking extrusion and melt blending with random α-olefin copolymer and optional tackifier. Summary of the Invention

[0019] In one embodiment of the invention, a polyolefin composition is provided comprising: (A) about 60% to about 96% by weight of at least one recycled polyolefin; (B) about 2% to about 20% by weight of at least one random α-olefin copolymer; and (C) about 2% to about 20% by weight of at least one tackifier; wherein the polyolefin composition has a weight ratio of random α-olefin copolymer to tackifier between about 0.2 and about 5.0; and wherein the polyolefin composition has an increase in melt flow rate of about 5% to about 400% compared to the same polyolefin composition without random α-olefin copolymer and tackifier.

[0020] In another embodiment, a method for preparing a polyolefin composition is provided, the method comprising: 1) extruding at least one recycled polyolefin in the presence of at least one free radical initiator (E) to prepare an extruded, tack-reduced, cracked recycled polyolefin; and 2) melt blending (A) about 60 wt% to about 96 wt% of the extruded recycled polyolefin; (B) about 2 wt% to about 20 wt% of at least one random α-olefin copolymer; and (C) optionally about 2 wt% to about 20 wt% of at least one tackifier; and (D) optionally at least one additional polymer; wherein the polyolefin composition has a weight ratio of random α-olefin copolymer to tackifier between about 0.2 and about 5.0; and wherein the extruded, tack-reduced, cracked polyolefin composition has an increase in melt flow rate of about 5% to about 1500% compared to the recycled polyolefin.

[0021] In another embodiment, a method for preparing a polyolefin composition is provided, the method comprising melt blending: (A) about 60 wt% to about 96 wt% of at least one recycled polyolefin; (B) about 2 wt% to about 20 wt% of at least one random α-olefin copolymer; and (C) about 2 wt% to about 20 wt% of at least one tackifier; and (D) optionally at least one additional polymer; wherein the polyolefin composition has a weight ratio of random α-olefin copolymer to tackifier between about 0.2 and about 5.0; and wherein the polyolefin composition has an increase in melt flow rate of about 5% to about 400% compared to the same polyolefin composition without random α-olefin copolymer, tackifier and optionally additional polymer.

[0022] In another embodiment, a polyolefin composition is provided comprising: (A) at least one recycled polyolefin of about 60% to about 96% by weight; (B) at least one random α-olefin copolymer of about 2% to about 20% by weight; (C) at least one tackifier; (D) at least one additional polymer of about 1% to about 60% by weight; and wherein the polyolefin composition has a weight ratio of random α-olefin copolymer to tackifier between about 0.2 and about 5.0; and wherein the polyolefin composition has an increase in melt flow rate of about 5% to about 400% compared to the same polyolefin composition without random α-olefin copolymer, tackifier and additional polymer. Attached Figure Description

[0023] The invention will now be described with reference to the accompanying drawings. The drawings, which are incorporated in and constitute a part of this specification, illustrate certain embodiments and, together with the written description, serve to explain certain principles of the constructs and methods disclosed herein.

[0024] Figure 1It describes the linear variable as a function of the percentage of amorphous poly-(α)olefins.

[0025] Figure 2 The linear variable depicted as a function of the percentage of hydrogenated amorphous poly-(α)olefins Detailed Implementation

[0026] It should be understood that the following detailed description is provided to give the reader a more complete understanding of certain embodiments, features and details of various aspects of the invention, and should not be construed as limiting the scope of the invention.

[0027] Certain terms used throughout this disclosure are defined below to facilitate a better understanding of the invention. Additional definitions are set forth throughout the disclosure.

[0028] Every term not explicitly defined in this application shall be understood to have a meaning commonly accepted by those skilled in the art. If the construction of a term would render it meaningless or substantially meaningless in its context, the definition of that term shall be derived from a standard dictionary.

[0029] Unless otherwise explicitly indicated, the use of numerical values ​​within the various ranges specified herein is considered an approximation, as both the minimum and maximum values ​​within the range are preceded by the word "approximately". In this context, the term "approximately" means covering a deviation of ±1%, 2%, 3%, 4%, or no more than 5% of the value. In this way, slightly higher and lower than the ranges can achieve substantially the same results as values ​​within the ranges. Furthermore, these ranges are intended to be presented as continuous ranges encompassing each value between the minimum and maximum values.

[0030] Unless otherwise stated, % solids or weight % (wt%) are given with reference to the total weight of a particular formulation, composition, blend or masterbatch.

[0031] As used herein, “polymer” can refer to homopolymers, copolymers, interpolymers, terpolymers, etc. A “polymer” has two or more identical or different monomer-derived units. A “homogeneous polymer” is a polymer having identical derived monomer units. A “copolymer” is a polymer having two or more different derived monomer units. A “terpolymer” is a polymer having three different monomer-derived units. The term “different” used to refer to monomer-derived units means that the monomer-derived units differ from each other by at least one atom or are isomerically different. Therefore, as used herein, the definition of a copolymer includes terpolymers, etc. Similarly, as used herein, the definition of a polymer includes copolymers, etc.

[0032] In this invention, a polyolefin composition is provided comprising: (A) about 60% to about 96% by weight of at least one recycled polyolefin; (B) about 2% to about 20% by weight of at least one random α-olefin copolymer; and (C) about 2% to about 20% by weight of at least one tackifier; wherein the polyolefin composition has a weight ratio of random α-olefin copolymer to tackifier between about 0.2 and about 5.0; and wherein the polyolefin composition has an increase in melt flow rate of about 5% to about 400% compared to the same polyolefin composition without random α-olefin copolymer and tackifier.

[0033] For the purposes of this specification and the following claims, the term "recycled polyolefin" is used to refer to materials recycled from post-consumer waste (PCR), industrial waste, and / or post-industrial waste (PIR), as opposed to virgin polymers.

[0034] "Post-consumer waste" refers to items that have completed at least their first use cycle (or life cycle), meaning they have fulfilled their primary purpose; while "post-industrial waste" and "industrial waste" refer to manufacturing waste that typically does not reach consumers. The term "virgin" indicates newly prepared materials and / or objects that have not yet been recycled before their first use.

[0035] Regenerated polyolefins comprise at least one polymer selected from ethylene polymers and propylene polymers. Any type of ethylene polymer or propylene polymer known in the art can be used as a known recycled polyolefin.

[0036] Ethylene polymers, also known as "polyethylene," include polyethylene homopolymers and ethylene-α-olefin copolymers containing at least 50 mol% ethylene-derived units. Based on the total weight of polymerizable monomers, ethylene-α-olefin copolymers may have an α-olefin comonomer content of greater than 5 wt%, greater than 7 wt%, or greater than 10 wt%.

[0037] Ethylene-α-olefin copolymers include those containing one or more C3 to C4 groups. 40 Comonomers of olefin-derived units. In another embodiment, the ethylene-α-olefin copolymer comprises C3 to C4. 40 Olefin-derived units. C3 to C4 40 Olefin monomers can be linear, branched, or cyclic. (C3 to C4) 40 Cyclic olefins can be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and / or one or more functional groups.

[0038] Examples C3 to C 40Olefin comonomers include, but are not limited to, propylene, butene, pentene, hexene, hepten, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbomene, 7-oxanorbornadiene, and their substituted derivatives and isomers. Examples of substituted derivatives and isomers are, but are not limited to, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, and norbornadiene.

[0039] Exemplary comonomers include, but are not limited to, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, and 1-octene, non-conjugated dienes, polyenes, butadiene, isoprene, pentene, hexadiene (e.g., 1,4-hexadiene), octadiene, styrene, halogenated styrene, alkylated styrene, tetrafluoroethylene, vinylbenzocyclobutene, cycloalkanes, cycloolefins (e.g., cyclopentene, cyclohexene, cyclooctene), and mixtures thereof. Typically, ethylene is comonomerized with a C3-C... 20 α-olefin copolymerization.

[0040] Exemplary diene or triene comonomers include, but are not limited to, 7-methyl-1,6-octadiene; 3,7-dimethyl-1,6-octadiene; 5,7-dimethyl-1,6-octadiene; 3,7,11-trimethyl-1,6,10-octtriene; 6-methyl-1,5-heptadiene; 1,3-butadiene; 1,3-pentadiene, norbornadiene, 1,6-heptadiene; 1,7-octadiene; 1,8-nonadiene; 1,9-decadiene; 1,10-undecadiene; norbornene; tetracyclododecene; or mixtures thereof. In another embodiment, the diene or triene comonomer is selected from at least one of butadiene, hexadiene, and octadiene. In yet another embodiment, the diene or triene comonomer is selected from 1,4-hexadiene; 1,9-decadiene; 4-methyl-1,4-hexadiene; 5-methyl-1,4-hexadiene; dicyclopentadiene; and 5-ethylidene-2-norbornene (ENB), 1,3-butadiene, 1,3-pentadiene, norbornene, and dicyclopentadiene; C8-C 40 Vinyl aromatic compounds, including styrene, o-, m- and p-methylstyrene, divinylbenzene, vinylbiphenyl, vinylnaphthalene; and halogen-substituted C8-C... 40 Vinyl aromatic compounds such as at least one of chlorostyrene and fluorostyrene.

[0041] Polyethylene polymers include, but are not limited to, low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, ultra-low-density polyethylene, and ultra-high molecular weight polyethylene.

[0042] Low-density polyethylene (LDPE) is typically prepared under high pressure using free radical initiators or in a gas-phase process using Ziegler-Natta or vanadium catalysts. LDL typically has a density of approximately 0.916 g / cm³. 3 To approximately 0.950 g / cm 3 The density ranges from [specific value range]. Low-density polyethylene, typically prepared using free radical initiators, is known in industry as "LDPE". LDPE is also called "branched" or "heterogeneously branched" polyethylene because of the relatively large number of long branches extending from the main polymer backbone.

[0043] At 0.916 g / cm 3 Up to 0.950 g / cm 3 Polyethylene in the same density range (that is linear and does not contain long branching) is called linear low-density polyethylene (LLDPE) and is typically prepared using conventional Ziegler-Natta catalysts or metallocene catalysts. “Linear” means that polyethylene has few (if any) long branches.

[0044] Medium-density polyethylene (MDPE) typically has a density between 0.926 g / cm³. 3 and 0.940 g / cm 3 The density between these parameters is typically achieved through low-pressure polymerization using transition metal catalysts such as Ziegler-Natta or metallocene catalysts.

[0045] High-density polyethylene (HDPE) typically has a density greater than approximately 0.950 g / cm³. 3 The density is such that it is usually prepared using Ziegler-Natta catalysts or chromium catalysts.

[0046] Ultra-high molecular weight polyethylene (UHMWPE) refers to HDPE with a much higher molecular weight (typically 10 times higher). UHMWPE is usually prepared using metallocene catalysts.

[0047] Ultra-low density polyethylene (ULDPE) can be prepared by many different methods, resulting in a density of less than approximately 0.916 g / cm³. 3 The polyethylene. In other embodiments, ULDPE has a content of approximately 0.890 g / cm³. 3 Approximately 0.915 g / cm³ 3 or approximately 0.900 g / cm 3 Approximately 0.915 g / cm³ 3 The density within the range.

[0048] Propylene polymers also referred to as "polypropylene" include propylene homopolymers and propylene copolymers containing at least 50 mol% propylene-derived units. The term "polypropylene" includes, but is not limited to, atactic polypropylene (aPP), isotactic polypropylene (iPP) (defined as having at least 10% or more isotactic pentamelic units), highly isotactic polypropylene (defined as having 50% or more isotactic pentamelic units), syndiotactic polypropylene (sPP) (defined as having 10% or more syndiotactic pentamelic units), polypropylene homopolymers (hPP) (also known as propylene homopolymers or homopolymers), and so-called random copolymer polypropylene (RCP) (also known as propylene random copolymers). In this document, RCP may comprise copolymers of propylene and 1% to 10% by weight of olefin-derived units selected from ethylene and C4 to C8 α-olefins. If the polyolefin has less than 10% isotactic or syndiotactic pentamelic units, it is "atactic" and also referred to as "amorphous".

[0049] Propylene copolymers, also known as "propylene-α-olefin copolymers," comprise propylene and ethylene or a C4-C... 20 Polymers copolymerized with α-olefins.

[0050] Suitable comonomers for copolymerization with propylene include, but are not limited to, ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 4-methyl-1-pentene, 4-methyl-1-hexene, 5-methyl-1-hexene, vinylcyclohexene, and styrene.

[0051] Exemplary propylene copolymers include propylene / ethylene, propylene / 1-butene, propylene / 1-hexene, propylene / 4-methyl-1-pentene, propylene / 1-octene, propylene / ethylene / 1-butene, propylene / ethylene / ethylene-norbornene (ENB), propylene / ethylene / 1-hexene, propylene / ethylene / 1-octene, propylene / styrene, and propylene / ethylene / styrene derivative units.

[0052] Propylene copolymers contain ethylene-derived units or C4-C 20The α-olefin-derived units (or "comonomer-derived units") range from 5% to 50% by weight, 6% to 40% by weight, 7% to 35% by weight, 8% to 20% by weight, and 10% to 15% by weight of the copolymer. Propylene-α-olefin copolymers may also contain derivative units of two different comonomer-derived units. Furthermore, these copolymers and terpolymers may contain diene-derived units. Based on the total weight of the terpolymer, the amount of diene-derived units may range from 10% by weight or less, 8% by weight or less, 5% by weight or less, and 3% by weight or less. In another embodiment, the amount of diene-derived units may range from 0.1% by weight to 10% by weight, 0.5% by weight to 8% by weight, and 1% by weight to 5% by weight.

[0053] Suitable dienes include, but are not limited to, 1,4-hexadiene, 1,6-octadiene, 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, dicyclopentadiene (DCPD), ethylidene norbornene (ENB), norbornadiene, 5-vinyl-2-norbornene (VNB), or combinations thereof.

[0054] Propylene copolymers can be random or block copolymers, propylene-based terpolymers, or branched polypropylene, or any variant thereof (each with its own properties). Random propylene copolymers have comonomer-derived units randomly distributed along the polymer backbone. Block copolymers have comonomer-derived units appearing in long sequences.

[0055] The propylene homopolymers and copolymers described herein can be prepared using any suitable catalysts and / or methods known for the preparation of polypropylene homopolymers and copolymers. The polypropylene homopolymers and copolymers can be conventional in composition and prepared by gas-phase, slurry, or solution-type methods.

[0056] The definition of waste implies, and is known to those skilled in the art, that impurities can be present in recycled polyolefins. Impurities include materials that are intentionally or unintentionally added to the waste stream. These impurities include, but are not limited to, other polymers, additives, and fillers.

[0057] Polymers that may exist as impurities in recycled polyolefins include, but are not limited to, ethylene vinyl acetate, ethylene methyl acrylate, copolymers of acrylic acid, polymethyl methacrylate or any other polymer that can be polymerized by a high-pressure free radical method, polyvinyl chloride, polybutene-1, isotactic polybutene, acrylonitrile butadiene styrene (ABS) resin, ethylene propylene rubber (EPR), vulcanized EPR, ethylene propylene diene monomer rubber (EPDM), block copolymers, styrene block copolymers, polyamides, polycarbonates, polyethylene terephthalate (PET) resin, cross-linked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymers containing aromatic monomers, polyesters, polyacetals, polyvinylidene fluoride, polyethylene glycol, polyisobutylene and / or combinations thereof. An example of a polymer containing aromatic monomers is polystyrene.

[0058] Such additives that may exist as impurities in recycled polyolefins include, but are not limited to, antioxidants (AO), anti-acid agents, anti-adhesion additives, plasticizers, tackifiers, UV stabilizers, anti-blocking agents, crosslinking agents, mold release agents, antistatic agents, antimicrobial agents, biocides, foaming agents, bleaching agents, clarifying agents, flame retardants, catalysts, pigments, colorants, dyes, waxes, or combinations thereof. Examples of antioxidants include, but are not limited to, hindered phenolic plastics, such as BASF's IRGANOX. TM 1010 or IRGANOX TM 1076; Phosphorus-based AO, such as BASF's IRGAFOS TM 168; thiolated AO, such as BASF's Irganox PS-802FL TM Nitrogen-based AOs, such as 4,4'-bis(1,1'-dimethylbenzyl)diphenylamine; and AO blends. Examples of antacids include, but are not limited to, calcium stearate, sodium stearate, zinc stearate, magnesium oxide and zinc oxide, synthetic hydrotalcite, lactates and alkenyl lactates, and combinations thereof. Examples of tackifiers include, but are not limited to, polybutene, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal and glyceryl stearates, and hydrogenated rosin. Examples of UV stabilizers include, but are not limited to, bis-(2'2'6'6-tetramethyl-4-piperidinyl)-sebate. Examples of nucleating agents include, but are not limited to, sodium benzoate and 1,3:2,4-bis(3,4-dimethylbenzyl)sorbitol. Examples of antiblocking agents include, but are not limited to, diatomaceous earth, synthetic silica, silicates, and synthetic zeolites. Silicates include, but are not limited to, kaolin, sodium aluminum silicate, calcined kaolin, aluminum silicate, or calcium silicate. Examples of antistatic agents include, but are not limited to, glycerides, ethoxylated amines, and ethoxylated amides. Typically, these additives may be present in amounts from about 100 ppm to about 2000 ppm for each individual additive.

[0059] Such fillers, which may exist as impurities in recycled polyolefins, include, but are not limited to, coal, fly ash, calcium carbonate, barium sulfate, carbon black, metal oxides, inorganic materials, natural materials, alumina trihydrate, magnesium hydroxide, bauxite, talc, mica, barite, kaolinite, silica, post-consumer or post-industrial glass, synthetic fibers and natural fibers, or any combination thereof. The fillers may be organic, inorganic, or a combination of both, and may have different forms.

[0060] In one embodiment, based on the weight of the recycled polyolefin, the percentage of impurities in the recycled polyolefin is at least 0.1 wt%, 0.5 wt%, 1 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, or 35 wt% and / or not exceeding 90 wt%, 85 wt%, 80 wt%, 75 wt%, 70 wt%, 65 wt%, or 60 wt%. In other embodiments, based on the weight of the recycled polyolefin in the polyolefin composition, the percentage of impurities can range from about 0.1 wt% to about 86 wt%, about 0.5 wt% to about 85 wt%, about 1 wt% to about 80 wt%, about 5 wt% to about 75 wt%, about 10 wt% to about 70 wt%, about 15 wt% to about 65 wt%, and about 20 wt% to about 60 wt%. Other amounts below and above these ranges may be present.

[0061] In another embodiment of some types of recycled polyolefins, the percentage of impurities in the recycled polyolefin is from about 0.1 wt% to about 10 wt%, from about 0.1 wt% to about 5 wt%, from about 0.5 wt% to about 5 wt%, and from about 0.5 wt% to about 3 wt%, based on the weight of the recycled polyolefin in the polyolefin composition. Other amounts below and above these ranges may be present.

[0062] In at least one other embodiment, the percentage of filler in the recycled polyolefin is about 5% to about 85% by weight, about 10% to about 85% by weight, about 20% to about 85% by weight, about 30% to about 85% by weight, about 40% to about 85% by weight, and 50% to about 85% by weight, based on the weight of the recycled polyolefin in the polyolefin composition. Other amounts below and above these ranges may be present.

[0063] For the purposes of this invention, the weight percentage of recycled polyolefins should be considered as the weight percentage of recycled polyethylene-rich polyolefins and / or polypropylene-rich recycled polyolefins (including impurities).

[0064] In other embodiments of the invention, the amount of recycled polyolefin in the polyolefin composition may be at least 60 wt%, 61 wt%, 62 wt%, 63 wt%, 64 wt%, 65 wt%, 66 wt%, 67 wt%, 68 wt%, 69 wt%, 70 wt%, 71 wt%, 72 wt%, 73 wt%, 74 wt%, 75 wt%, 76 wt%, 77 wt%, 78 wt%, 79 wt%, 80 wt%, 81 wt%, 82 wt%, 83 wt%, 84 wt%, 85 wt%, 86 wt%, 87 wt%, 88 wt%, or 89 wt% and / or not greater than 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt%, 95 wt%, or 96 wt%, based on the weight of the polyolefin composition. Other ranges may be about 60% to about 96% by weight, about 65% to about 90% by weight, about 70% to about 85% by weight, and about 75% to about 85% by weight, depending on the weight of the polyolefin composition.

[0065] A recycled polyolefin is considered to be a polyethylene-rich recycled polyolefin when it contains at least 50 wt%, at least 55 wt%, at least 60 wt%, at least 65 wt%, at least 70 wt%, at least 80 wt%, at least 85 wt%, at least 90 wt%, at least 95 wt%, at least 97 wt%, or at least 98 wt% ethylene polymer. In such a polyethylene-rich recycled polyolefin, polyethylene is also referred to as the major component.

[0066] Recycled polyolefins are considered polypropylene-rich recycled polyolefins when they contain at least 50 wt%, at least 55 wt%, at least 60 wt%, at least 65 wt%, at least 70 wt%, at least 75 wt%, at least 80 wt%, at least 85 wt%, at least 90 wt%, at least 95 wt%, at least 97 wt%, or at least 98% of propylene polymer. In such polypropylene-rich recycled polyolefins, polypropylene is also referred to as the major component.

[0067] Random α-olefin polymers can be any polymer known in the art, including but not limited to homopolymers and copolymers. Random α-olefin copolymers can be any random α-olefin copolymer known in the art. In one embodiment of the invention, random α-olefin copolymers are also referred to as amorphous polyolefins (APO) or amorphous poly-α-olefins (APAO), and include, but are not limited to, amorphous propylene-ethylene copolymers, which may contain varying amounts of ethylene or propylene. For example, propylene-ethylene copolymers may contain at least 1 wt%, 3 wt%, 5 wt%, 7 wt%, 10 wt%, 12 wt%, 14 wt%, 15 wt%, 17 wt%, 18 wt%, or 20 wt% and / or no more than 70 wt%, 65 wt%, 60 wt%, 55 wt%, 50 wt%, 45 wt%, 40 wt%, 35 wt%, 30 wt%, 27 wt%, or 25 wt% of ethylene. Furthermore, the propylene-ethylene copolymer may contain ethylene in the range of about 1 wt% to about 70 wt%, about 3 wt% to about 65 wt%, about 5 wt% to about 60 wt%, about 7 wt% to about 55 wt%, about 10 wt% to about 50 wt%, about 12 wt% to about 45 wt%, about 14 wt% to about 40 wt%, about 15 wt% to about 35 wt%, about 17 wt% to about 30 wt%, about 18 wt% to about 27 wt%, or about 20 wt% to about 25 wt%. For example, the propylene-ethylene copolymer may contain at least 40 wt%, 50 wt%, 60 wt%, 65 wt%, or 70 wt% and / or no more than 99 wt%, 95 wt%, 90 wt%, 85 wt%, or 80 wt% of propylene. In addition, the propylene-ethylene copolymer may contain propylene in the range of about 40% to about 99% by weight, about 50% to about 95% by weight, about 60% to about 90% by weight, about 65% to about 85% by weight, or about 70% to about 80% by weight.

[0068] In addition, APO may include propylene-ethylene copolymers, which may contain one or more C4-C4 copolymers. 10 Derivative units of α-olefins. These C4-C 10 α-olefins may include, for example, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and combinations thereof. According to one or more embodiments, the copolymer may contain at least 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, or 5 wt% and / or no more than 40 wt%, 30 wt%, 25 wt%, 20 wt%, 15 wt%, or 10 wt% of at least one C4-C olefin. 10α-olefin. Furthermore, the copolymer may contain at least one C4-C olefin in the range of about 0.5 wt% to about 40 wt%, about 1 wt% to about 30 wt%, about 2 wt% to about 25 wt%, about 3 wt% to about 20 wt%, about 4 wt% to about 15 wt%, or about 5 wt% to about 10 wt%. 10 α-olefins. Exemplary commercially available random α-olefin copolymers include Aerafin from Eastman Chemical Company. TM 17 and Eastoflex TM E1200.

[0069] In addition, APO may include polypropylene homopolymers. Exemplary commercially available random α-olefin homopolymers include Eastoflex from Eastman Chemical Company. TM P1010 and Eastoflex TM P1023

[0070] In one embodiment of the invention, the random α-olefin copolymer may have a number-average molecular weight of 25,000 mol / g or 10,000 mol / g or less. In other embodiments, the number-average molecular weight may be from 2,500 g / mol to 25,000 g / mol and / or from 4,500 g / mol to 10,000 g / mol. The polydispersity index of the random α-olefin copolymer may be from about 4.0 to about 10.0 or from about 5.0 to about 7.5.

[0071] Number-average molecular weight was measured using a Malvern Viscotek HT-350A high-temperature gel permeation chromatography (HTGPC) system equipped with two Viscotek VE1122 pumps, a Viscotek 430 vortex heater with stirring autosampler, a VE7510GPC degassing unit, an HTGPC Module 350A oven, a Microlab 500 series autoinjector for sample preparation, and a triple detection system consisting of a laser scattering, refractometer, and differential viscosity detector. The GPC consisted of a 1×PLGel 5 μm Guard 50×7.5 mm column and two×PLGel 5 μm Mix-C 300×7.5 mm columns, running at 135 °C and a flow rate of 0.7 mL / min using 1,2,4-trichlorobenzene as solvent. Weigh 50 mg to 70 mg of each sample into a sample vial and mix with 10 mL of 1,2,4-trichlorobenzene to prepare blends of 5.0 mg / mL to 7.0 mg / mL. Place the vials in a Viscotek 430 vortex heated autosampler to equilibrate at room temperature for approximately 1 hour, then heat the samples at 135°C for no more than 4 hours with magnetic stirring. For each sample, perform two injections and collect chromatograms from each injection. Analyze the samples using routine GPC calibration with a single narrow polystyrene standard, light scattering, triple detection, and universal calibration. Analyze the light scattering data, routine GPC analysis, triple detection analysis, and universal calibration analysis using the same Malvern OmniSEC software.

[0072] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of each sample were determined using Malvern OmniSEC software. The polydispersity index (PDI) was calculated by dividing the weight-average molecular weight by the number-average molecular weight (PDI = Mw / Mn).

[0073] Random α-olefin copolymers may have a glass transition temperature (Tg) equal to or below -10°C, equal to or below -25°C, or equal to or below -35°C (differential scanning calorimetry according to ASTM D3418-15; 20°C / min).

[0074] Tackifiers (also known as “tackifier resins”) include, but are not limited to, alicyclic hydrocarbon resins, C5 hydrocarbon resins, C5 / C9 hydrocarbon resins, aromatically modified C5 resins, C9 hydrocarbon resins, pure monomer resins, C5 and C9 resins, terpene resins, terpene phenolic resins, terpene styrene resins, rosin esters, modified rosin esters, liquid resins of fully or partially hydrogenated rosin, fully or partially hydrogenated rosin esters, fully or partially hydrogenated modified rosin resins, fully or partially hydrogenated rosin alcohols, fully or partially hydrogenated C5 resins, fully or partially hydrogenated C5 / C9 resins, fully or partially hydrogenated aromatically modified C5 resins, fully or partially hydrogenated C9 resins, fully or partially hydrogenated pure monomer resins, fully or partially hydrogenated C5 / alicyclic resins, fully or partially hydrogenated C5 / alicyclic / styrene / C9 resins, fully or partially hydrogenated cycloalicyclic resins; and combinations thereof. Exemplary commercial tackifiers include Regalite from Eastman Chemical Company. TM and Eastotac TM Hydrocarbon resins. Furthermore, tackifiers may contain functionalized groups.

[0075] As used herein, the term "PMR" refers to a pure monomer resin. Pure monomer resins are prepared by the polymerization of styrene-based monomers such as styrene, α-methylstyrene, vinyltoluene, and other alkyl-substituted styrene. Pure monomer resins are prepared by any method known in the art. The pure monomer feedstock used to prepare pure monomer resins is, in some cases, a synthetically produced or highly purified monomeric substance. For example, styrene can be produced from ethylbenzene, or α-methylstyrene can be produced from cumene. In one embodiment, a pure monomer hydrocarbon resin is prepared by cationic polymerization of styrene-based monomers such as styrene, α-methylstyrene, vinyltoluene, and other alkyl-substituted styrene using a Friedel-Crafts polymerization catalyst such as a Lewis acid (e.g., boron trifluoride (BF3), boron trifluoride complexes, aluminum trichloride (AlCl3), and alkylaluminum chloride). Solid acid catalysts can also be used to prepare pure monomer resins. The pure monomer resins disclosed herein are unhydrogenated, partially hydrogenated, or fully hydrogenated resins. As used herein, the term "hydrogenated" is also alternatively abbreviated as "H2," and when H2 is used before or after the resin type, it is intended to indicate that the resin type is hydrogenated or partially hydrogenated, such as, for example, "PMR H2" and "C5 H2." When "H2" is used herein, "H2" is intended to encompass both fully hydrogenated and partially hydrogenated resin samples. Thus, "H2" refers to a state in which the resin is fully hydrogenated or at least partially hydrogenated. In some cases, pure monomer resins are... Styrene hydrocarbon resin, Styrene / alkylstyrene hydrocarbon resin, Alkyl styrene hydrocarbon resins and The hydrogenated or partially hydrogenated pure monomer resins were obtained from Eastman Chemical Company (Kingsport, TN, US).

[0076] As used herein, the term "C5 resin" refers to an aliphatic C5 hydrocarbon resin, which is produced by the polymerization of monomers comprising C5 and / or C6 olefinic substances boiling at atmospheric pressure in the range of about 20°C to about 200°C. These monomers are typically produced from petroleum processing, such as cracking. The aliphatic C5 hydrocarbon resin of the present invention can be prepared by any method known in the art. In one embodiment, the aliphatic C5 hydrocarbon thermoplastic resin is prepared by cationic polymerization of a cracked petroleum feedstock containing C5 and C6 paraffins, olefins, and dienes, also referred to as "C5 monomers". These monomer streams consist of cationically polymerizable monomers, such as 1,3-pentadiene, which is the main reactive component along with cyclopentene, pentene, 2-methyl-2-butene, 2-methyl-2-pentene, cyclopentadiene, and dicyclopentadiene. Polymerization is catalyzed using Friedel-Crafts polymerization catalysts such as Lewis acids (e.g., boron trifluoride (BF3), boron trifluoride complexes, aluminum trichloride (AlCl3), and alkyl aluminum chloride). Besides the reactive components, the non-polymerizable components in the feed include saturated hydrocarbons, which in some cases are co-distilled with unsaturated components such as pentane, cyclopentane, or 2-methylpentane. Solid acid catalysts can also be used to prepare aliphatic C5 hydrocarbon resins. Aliphatic C5 hydrocarbon resins include non-hydrogenated, partially hydrogenated, or fully hydrogenated resins. Aliphatic C5 resins can be used as... C5 and C5H2 resin was obtained from Eastman Chemical Company (Kingsport, TN, US).

[0077] As used herein, the term "C5 / C9 resin" refers to an aliphatic / aromatic C5 / C9 resin produced by the polymerization of a monomer comprising at least one unsaturated aromatic C8, C9, and / or C10 substance boiling at atmospheric pressure in the range of about 100°C to about 300°C, and a monomer comprising at least one C5 and / or C6 olefin substance boiling at atmospheric pressure in the range of about 20°C to about 200°C. In one embodiment, the C5 and / or C6 substance comprises paraffin, olefins, and dienes, also referred to as "C5 monomers". These monomer streams consist of cationicly polymerizable monomers, such as 1,3-pentadiene, which is the main reactive component along with cyclopentene, pentene, 2-methyl-2-butene, 2-methyl-2-pentene, cyclopentadiene, and dicyclopentadiene. In one embodiment, the unsaturated aromatic C8, C9, and / or C10 monomers are derived from petroleum distillates from naphtha cracking and are referred to as "C9 monomers". These monomer streams consist of cationically polymerizable monomers such as styrene, α-methylstyrene, β-methylstyrene, vinyltoluene, indene, dicyclopentadiene, divinylbenzene, and other alkyl-substituted derivatives of these components. In some cases, cationic polymerization is catalyzed using Friedel-Crafts polymerization catalysts such as Lewis acids (e.g., boron trifluoride (BF3), boron trifluoride complexes, aluminum trichloride (AlCl3), and alkylaluminum chloride). Solid acid catalysts are also used to prepare aliphatic / aromatic C5 / C9 hydrocarbon thermoplastic resins. In addition to the reactive components, non-polymerizable components include aromatic hydrocarbons such as xylene, ethylbenzene, cumene, ethyltoluene, dihydroindene, methyldihydroindene, naphthalene, and other similar substances. In some embodiments, the non-polymerizable components of the feed stream are incorporated into the resin via an alkylation reaction. Aliphatic / aromatic C5 / C9 hydrocarbon resins include non-hydrogenated resins, partially hydrogenated resins, and hydrogenated resins. Aliphatic / aromatic C5 / C9 thermoplastic resins can... The resin is sourced from Eastman Chemical Company. The C5 to C9 ratio is unrestricted. In other words, the amount of C5 monomer in a C5 / C9 resin can be from 0.1% to 100%, and vice versa.

[0078] As used herein, the term "C9 resin" refers to an aromatic C9 hydrocarbon resin, which is a resin produced by the polymerization of monomers comprising unsaturated aromatic C8, C9, and / or C10 substances boiling at atmospheric pressure in the range of about 100°C to about 300°C. These monomers are typically produced from petroleum processing, such as cracking. The aromatic C9 hydrocarbon thermoplastic resin of the present invention can be prepared by any method known in the art. In one embodiment, the aromatic C9 hydrocarbon resin is prepared by cationic polymerization of aromatic C8, C9, and / or C10 unsaturated monomers derived from petroleum distillates from naphtha cracking, and is referred to as "C9 monomers". These monomer streams consist of cationically polymerizable monomers such as styrene, α-methylstyrene (AMS), β-methylstyrene, vinyltoluene, indene, dicyclopentadiene, divinylbenzene, and other alkyl-substituted derivatives of these components. In some embodiments of the C9 resin, aliphatic olefin monomers having four to six carbon atoms are also present during polymerization. In some cases, polymerization is catalyzed using Friedel-Crafts polymerization catalysts such as Lewis acids (e.g., boron trifluoride (BF3), boron trifluoride complexes, aluminum trichloride (AlCl3), and alkylaluminum chloride). In addition to the reactive components, non-polymerizing components include, but are not limited to, aromatic hydrocarbons such as xylene, ethylbenzene, cumene, ethyltoluene, dihydroindene, methyldihydroindene, naphthalene, and other similar chemicals. In some embodiments, the non-polymerizing components of the feed stream are incorporated into the thermoplastic resin via an alkylation reaction. C9 hydrocarbon resins include non-hydrogenated, partially hydrogenated, or fully hydrogenated resins. Aromatic C9 hydrocarbon resins can... C9 resins can be obtained, and aliphatic hydrogenated and aliphatic / aromatic partially hydrogenated C9 H2 hydrocarbon resins can be produced. The resin was obtained from Eastman Chemical Company.

[0079] As used herein, the term "DCPD resin" refers to dicyclopentadiene (DCPD), most commonly formed by ring-opening metathesis polymerization (ROMP) or thermal polymerization of dicyclopentadiene in the presence of a strong acid catalyst such as maleic acid or aqueous sulfuric acid. In some embodiments, dicyclopentadiene is also formed from two cyclopentadiene molecules via the Diels-Alder reaction and exists as two stereoisomers: internal-DCPD and external-DCPD. Typically, over 90% of the DCPD molecules present in commercially available DCPD are internal-type. DCPD thermoplastic resins include aromatic-modified DCPD resins as well as hydrogenated, partially hydrogenated, and non-hydrogenated resins, although only H2 DCPD is described in most cases herein, as it is the most readily available commercial form of DCPD. Aromatic-modified DCPD is also considered as a DCPD resin. Aromatic modification is carried out, for example, by C9 resin oil, styrene, or α-methylstyrene (AMS). Hydrogenated and partially hydrogenated DCPD, as well as aromatic-modified DCPD resins, can be... 5000 series resin (ExxonMobil Chemical Company, TX, US) was commercially available.

[0080] As used herein, the term "terpene resin" or "polyterpene resin" means a resin prepared from at least one terpene monomer. For example, α-pinene, β-pinene, d-limonene, and dipentene can be polymerized in the presence of aluminum chloride to provide polyterpene thermoplastic resins. Other examples of polyterpene thermoplastic resins include... TR 1100 and 4125 terpene thermoplastic resin (AZ Chem Holdings, LP, Jacksonville, FL, US) and A125 is a terpene thermoplastic resin (Pinova, Inc., Brunswick, GA, US). Terpene resins can also be modified with aromatic compounds. ZT105LT and ZT 115LT terpene resin is an aromatic modified resin (Az Chem Holdings, LP, Jacksonville, FL, US).

[0081] It should be understood that, in the above definition of certain types of thermoplastic resins (such as DCPD, PMR, C5, C9, C5 / C9, terpenes, etc., including hydrogenated, partially hydrogenated and non-hydrogenated forms of these resins), these resins include similar types of resins produced by mixing or blending different raw materials to prepare heterogeneous mixtures of raw materials for the production of thermoplastic resins. Furthermore, it should be understood that, at least for the PMR and terpene resins discussed herein, these resins include various known derivatives of such resins, such as phenol-modified and rosin-modified forms of the resins.

[0082] The tackifier has a glass transition temperature (Tg) of 25°C or greater, 30°C or greater, 35°C or greater, 40°C or greater, 45°C or greater, 50°C or greater, 55°C or greater, 60°C or greater, 65°C or greater, 70°C or greater, 75°C or greater, 80°C or greater, or 85°C (differential scanning calorimetry according to ASTM D3418-15; 20°C / min). In other embodiments, the tackifier has a glass transition temperature ranging from about 30°C to about 90°C, about 35°C to about 90°C, about 40°C to about 90°C, about 45°C to about 90°C, about 50°C to about 90°C, about 55°C to about 90°C, about 60°C to about 90°C, about 65°C to about 90°C, about 70°C to about 90°C, about 75°C to about 90°C, and about 80°C to about 90°C (differential scanning calorimetry according to ASTM D3418-15; 20°C / min).

[0083] This invention relates to polyolefin compositions having improved flow properties while maintaining acceptable mechanical properties. Recycled polyolefin compositions rich in polyethylene can in particular have improved flowability and improved elongation at break, while maintaining acceptable mechanical properties and / or providing a favorable balance of properties for specific applications. This invention provides compositions comprising at least one recycled polyolefin (A), at least one random α-olefin copolymer (B), and at least one tackifier (C). In some embodiments, the compositions and methods described herein relate to recycled polyolefins selected from ethylene-rich or propylene-rich recycled polyolefins, wherein the random α-olefin copolymer is at least one amorphous propylene-ethylene random copolymer, such as Aerafin. TM and Eastoflex TM (from Eastman Chemical), and at least one hydrogenated C9-based tackifier, such as Regalite TM R1125 and Plastolyn TM R1140 (obtained from Eastman Chemical), and a method for preparing such polyolefin compositions. In at least one embodiment, by using low levels of propylene-ethylene random copolymers such as Aerafin TM and hydrogenated C9-based tackifiers such as Regalite TM Adding to recycled polyolefins can improve flow properties such as melt flow rate (MFR) while maintaining acceptable mechanical properties of the resulting polyolefin composition containing recycled polyolefins. Low molecular weight Aerafin TM and Regalite TM It can reduce MFR and has an unexpected synergistic effect on mechanical properties. Acceptable mechanical properties are then defined in this disclosure.

[0084] The surprisingly improved elongation at break results in polyethylene-rich polyolefin compositions that are less brittle, easier to demold without cracking, and more resistant to high filler content in recycled polyolefin feed streams and the final composition. High filler content is typically used to increase the modulus of recycled polyolefin materials, where the corresponding drawback is that the final composition is too brittle. This invention, with its surprisingly increased elongation at break, enables these highly filled recycled feed streams to be used in applications where these streams were previously too brittle. Possible applications that can benefit from the increased elongation at break and the resulting flexibility include, but are not limited to, stretch films, packaging films, agricultural films, flooring materials, latches and spring locks, storage containers, and garden furniture.

[0085] In at least one embodiment, the recycled polyolefin may have a melt flow rate (MFR) of about 0.1 g / 10 min to about 10 g / 10 min, about 0.1 g / 10 min to about 5 g / 10 min, and about 0.1 g / 10 min to about 2 g / 10 min, as measured according to ISO 1133 at 2.16 kg and 190 °C. For polyethylene-rich recycled polyolefins, it has an MFR of about 10 g / 10 min or less, about 5 g / 10 min or less, or about 0.5 g / 10 min or less, as measured according to ISO 1133 at 2.16 kg and 190 °C.

[0086] In at least one embodiment, the recycled polyolefin may have a melt flow rate (MFR) of about 0.1 g / 10 min to about 10 g / 10 min, about 0.1 g / 10 min to about 5 g / 10 min, and about 0.1 g / 10 min to about 2 g / 10 min, as measured according to ISO 1133 at 2.16 kg and 230 °C. For polypropylene-rich recycled polyolefins, it has an MFR of about 10 g / 10 min or less, about 5 g / 10 min or less, or about 0.5 g / 10 min or less, as measured according to ISO 1133 at 2.16 kg and 230 °C.

[0087] In at least one embodiment, the percentages of the random α-olefin copolymer (B) and the tackifier (C) in the polyolefin composition are about 4% to about 40% by weight, about 4% to about 20% by weight, about 4% to about 14% by weight, or about 7% to about 10% by weight, based on the weight of the polyolefin composition. In another embodiment, based on the weight of the polyolefin composition, the amount of random α-olefin copolymer (B) and tackifier (C) in the polyolefin composition is at least 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, or 15 wt%, and not more than 40 wt%, 39 wt%, 38 wt%, 37 wt%, 36 wt%, 35 wt%, 34 wt%, 33 wt%, 32 wt%, 31 wt%, 30 wt%, 29 wt%, 28 wt%, 27 wt%, 26 wt%, 25 wt%, 24 wt%, 23 wt%, 22 wt%, 21 wt%, or 20 wt%.

[0088] Based on the weight of the polyolefin composition, the percentage of the random α-olefin polymer may be at least 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, or 10 wt% and / or not more than 20 wt%, 19 wt%, 18 wt%, 17 wt%, 16 wt%, or 15 wt%. Based on the weight of the polyolefin composition, the percentage of the random α-olefin copolymer (B) may range from about 2 wt% to about 20 wt%, from about 2 wt% to about 10 wt%, or from about 5 wt% to about 10 wt%. Based on the weight of the polyolefin composition, the percentage of the tackifier (C) may be at least 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, or 10 wt% and / or not more than 20 wt%, 19 wt%, 18 wt%, 17 wt%, 16 wt%, 15 wt%, 14 wt%, 13 wt%, 12 wt%, or 11 wt%. The percentage of tackifier (C) is from about 2 wt% to about 20 wt%, from about 2 wt% to about 10 wt%, from about 2 wt% to about 7 wt%, and from about 2 wt% to about 5 wt%. The weight ratio of random α-olefin copolymer (B) to tackifier (C) is between 0.2 and 5.0, 0.3 and 5.0, 0.4 and 5.0, 0.5 and 5.0, 0.6 and 5.0, 0.7 and 5.0, 0.8 and 5.0, 0.9 and 5.0, 1.0 and 5.0, 1.1 and 5.0, 1.2 and 5.0, 1.3 and 5.0, 1.4 and 5.0, 1.5 and 5.0, 1.6 and 5.0, 1.7 and 5.0, 1.8 and 5.0, and 1.9 and 5.0, respectively. Between 2.0 and 5.0, 2.1 and 5.0, 2.2 and 5.0, 2.3 and 5.0, 2.4 and 5.0, 2.5 and 5.0, 2.6 and 5.0, 2.7 and 5.0, 2.8 and 5.0, 2.9 and 5.0, 3.0 and 5.0, 3.1 and 5.0, 3.2 and 5.0, 3.3 and 5.0, 3.4 and 5.0, 3.5 and 5.0, 3.6 and 5.0, 3.7 and 5.0, 3.8 and 5.0, 3.9 and 5.0, or between 4.0 and 5.0.

[0089] In one embodiment of the invention, a polyolefin composition is provided comprising (A) about 60 wt% to about 96 wt% of at least one recycled polyolefin with an MFR < 10 g / 10 min (ISO 1133); (B) about 2 wt% to about 20 wt% of at least one random α-olefin copolymer with a Brinell viscosity equal to or less than 25,000 mPa·s (ASTM D 3236, 190°C); and (C) about 2 wt% to about 20 wt% of at least one tackifier with a ring and ball softening point equal to or greater than 70°C (ASTM E 28 or ASTM D6090 or ASTM D6166); wherein the weight ratio of B / C is between 0.2 and 5.0; and wherein the composition has an MFR increase of about 5% to about 400% compared to the same polyolefin composition without the random α-olefin copolymer and tackifier. In this embodiment, the polyolefin composition retains acceptable mechanical properties. Acceptable mechanical properties are defined subsequently in this disclosure.

[0090] In another embodiment of the invention, the polyolefin composition comprises (A) about 60 wt% to about 96 wt% of at least one recycled polyolefin with an MFR < 10 g / 10 min (ISO 1133); (B) about 2 wt% to about 20 wt% of at least one random α-olefin copolymer with a glass transition temperature equal to or below -10 °C (ASTM D 3418-15); and (C) about 2 wt% to about 20 wt% of at least one tackifier with a glass transition temperature equal to or above 25 °C (ASTM D 3418-15); wherein the weight ratio of B / C is between 0.2 and 5.0; and wherein the polyolefin composition has an MFR increase of about 5% to about 400% compared to the same polyolefin composition without the random α-olefin copolymer and tackifier. In this embodiment, the polyolefin composition retains acceptable mechanical properties. Acceptable mechanical properties are defined herein.

[0091] In another embodiment of the invention, a polyolefin composition is provided comprising (A) about 60 wt% to about 96 wt% of at least one recycled polyolefin with an MFR < 10 g / 10 min (ISO 1133); (B) about 2 wt% to about 20 wt% of at least one random α-olefin copolymer with a glass transition temperature equal to or below -10 °C (ASTM D 3418-15) and a nominal molecular weight equal to or below 25,000 g / mol (ISO 16014); and (C) about 2 wt% to about 20 wt% of at least one tackifier with a glass transition temperature equal to or above 25 °C (ASTM D 3418-15); wherein the weight ratio of B to C is between 0.2 and 5.0; and wherein the polyolefin composition has an MFR increase of about 5% to about 400% compared to the same polyolefin composition without the random α-olefin copolymer and the tackifier. In at least one aspect of this embodiment, the polyolefin composition retains acceptable mechanical properties. Acceptable mechanical properties are defined subsequently in this disclosure.

[0092] In another embodiment of the invention, a polyolefin composition is provided comprising (A) about 60 wt% to about 96 wt% of at least one recycled polyolefin with an MFR < 10 g / 10 min (ISO 1133); (B) about 2 wt% to about 20 wt% of at least one random α-olefin copolymer with a glass transition temperature equal to or below -10 °C (ASTM D 3418-15) and a nominal molecular weight equal to or below 25,000 g / mol (ISO 16014); and (C) about 2 wt% to about 20 wt% of at least one tackifier with a glass transition temperature equal to or above 45 °C (ASTM D 3418-15); wherein the weight ratio of B to C is between 0.2 and 5.0; and wherein, compared to the same polyolefin composition without the random α-olefin copolymer and the tackifier, the polyolefin composition has an MFR increase of about 5% to about 400%, and the polyolefin composition maintains acceptable mechanical properties. Acceptable mechanical properties are defined herein.

[0093] In another embodiment of the invention, a polyolefin composition is provided comprising (A) about 60 wt% to about 96 wt% of at least one recycled polyolefin with an MFR < 10 g / 10 min (ISO 1133); (B) about 2 wt% to about 20 wt% of at least one random α-olefin copolymer with a glass transition temperature equal to or below -10 °C (ASTM D 3418-15) and a nominal molecular weight equal to or below 10,000 g / mol (ISO 16014); and (C) about 2 wt% to about 20 wt% of at least one tackifier with a glass transition temperature equal to or above 45 °C (ASTM D 3418-15); wherein the weight ratio of B to C is between 0.2 and 5.0; and wherein the polyolefin composition has an MFR increase of about 5% to about 400% compared to the same polyolefin composition without the random α-olefin copolymer and the tackifier. In at least one aspect of this embodiment, the polyolefin composition retains acceptable mechanical properties. Acceptable mechanical properties are defined subsequently in this disclosure.

[0094] In at least one embodiment, the random-α-olefin is a propylene homopolymer. In at least one embodiment, the at least one random-α-olefin copolymer comprises a propylene homopolymer and an ethylene-propylene copolymer.

[0095] In embodiments of the invention, compared to the same polyolefin composition without random α-olefin copolymers and tackifiers, the polyolefin composition, measured according to ISO 1133 at 2.16 kg at 190°C, may have at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, ... MFR increases of 100%, 105%, 110%, 115%, 120%, 125%, 130%, 135%, 140%, 145%, 150%, 155%, 160%, 165%, 170%, 175%, 180%, 185%, 190%, 200%, 225%, 250%, 275%, 300%, 325%, 350%, 375%, or 400%. In other embodiments, the polyolefin composition may have an MFR increase ranging from about 5% to about 400%, about 20% to about 400%, about 50% to about 400%, about 5% to about 200%, about 15% to about 200%, about 20% to about 200%, about 5% to about 150%, about 10% to about 150%, about 15% to about 150%, or about 30% to about 300% compared to the same polyolefin composition without random α-olefin copolymer and tackifier.

[0096] Besides MFR, other rheological parameters, such as helical flow and melt viscosity, can also be positively affected. Polyolefin compositions may have helical flows that are about 5% to about 200%, about 10% to about 175%, about 25% to about 150%, about 50% to about 125%, or about 50% to about 100% higher than those of the same polyolefin composition without random α-olefin copolymers and tackifiers. Helical flow is measured using a die with a helix having a width of 10 mm and a depth of 2 mm. The length of the helix can reach 800 mm. Polyolefin compositions may have melt viscosities that are about 5% to about 200%, about 10% to about 175%, about 25% to 150%, about 50% to about 125%, or about 50% to about 100% higher than those of the same polyolefin composition without random α-olefin copolymers and tackifiers. Melt viscosity is measured using a rheometer.

[0097] In addition, the polyolefin composition may have at least one acceptable mechanical property selected from tensile yield strength (yield strength ISO 527-2 or ASTM D882), elongation at break, elongation at yield (yield tensile strain), Young's modulus (elastic modulus or E-modulus), maximum load tensile strength, maximum load tensile strain, tensile strength at break, tensile strain at break, flexural strength, toughness, film toughness, flexural modulus (flexural modulus or G-modulus ISO 178), 1% secant modulus, 2% secant modulus, unnotched simply supported beam impact strength, notched simply supported beam impact strength (notched impact strength ISO 179-1), unnotched cantilever beam impact strength, notched cantilever beam impact strength (ISO 180), dart impact strength (ASTM D1709A), Elmendorf tear strength (ASTM D1922), and puncture resistance.

[0098] As used herein, “acceptable mechanical property” means at least one mechanical property associated with a polyolefin composition or any article comprising a polyolefin composition, wherein the mechanical property is at least 80%, 85%, 90%, 100%, 105%, 110%, 115%, 120%, 125%, 130%, 135%, 140%, 150%, 155%, 160%, 165%, 170%, 175%, 180%, 185%, 190%, 200%, 225%, 250%, 275%, 300%, 325%, 350%, 375%, 400%, 425%, 450%, 475%, 500%, 525%, 550%, or 575% or about 600% compared to the mechanical properties of the same polyolefin composition without the random α-olefin copolymer and the tackifier.

[0099] In other embodiments of the invention, if at least one mechanical property of the polyolefin composition or any article comprising the polyolefin composition is about 80% to 600%, about 80% to 550%, about 80% to 500%, about 80% to 450%, about 80% to 400%, about 80% to 350%, about 80% to 300%, about 80% to 250%, about 80% to 200%, about 80% to 150%, about 80% to 120%, 90% to 600%, about 90% to 550%, about 90% to 500%, about The mechanical properties are “acceptable” if they are 90% to about 450%, about 90% to about 400%, about 90% to about 350%, about 90% to about 300%, about 90% to about 250%, about 90% to about 200%, about 90% to about 150%, about 90% to about 120%, 100% to about 600%, about 100% to about 550%, about 100% to about 500%, about 100% to about 450%, about 100% to about 400%, about 100% to about 350%, about 100% to about 300%, about 100% to about 250%, about 100% to about 200%, about 100% to about 150%, or about 100% to about 120%.

[0100] Various end-use applications of polyolefin compositions may require different balances of mechanical properties, some of which may be outside the “acceptable” range, and the composition may be suitable for that application.

[0101] In another embodiment, a polyolefin composition is provided comprising about 85% to about 96% by weight of at least one recycled polyolefin, about 2% to about 10% by weight of at least one random α-olefin copolymer, and about 2% to about 5% by weight of at least one tackifier; wherein the MFR of the polyolefin composition, measured according to ISO 1133 (for polyethylene-rich recycled polyolefins at 2.16 kg at 230°C, for polypropylene-rich recycled polyolefins at 190°C), is about 25% to about 80% higher than the MFR of the same polyolefin composition without the random α-olefin copolymer and tackifier; wherein the polyolefin composition has a yield strength (ISO 527-2) that is about 5% to about 15% lower than the yield strength of the same polyolefin composition without the random α-olefin copolymer and tackifier, and a flexural modulus (ISO 178 or ASTM) that is about 10% to about 20% lower than the yield strength of the same polyolefin composition without the random α-olefin copolymer and tackifier. D882), and notched impact strength that is about 5% to about 15% lower than that of the same polyolefin composition without random α-olefin copolymer and tackifier (ISO178 or ASTM D256).

[0102] In another embodiment of the invention, the polyolefin composition or any article containing a polyolefin composition may exhibit a change in at least one property that is directly or indirectly related to a change in mechanical properties. Such properties include, but are not limited to, thermal properties (Vicat softening point, thermal flexural temperature, sealing temperature, seal strength (ASTM F2029, hot tack ASTM F1921), optical properties (haze such as ASTM D1003, gloss such as ASTM D2457, light transmittance, transparency), dimensional stability, heat resistance, barrier properties (MVTR such as ASTM F1249, OTR such as ASTM D3985), cold flexibility, melt temperature, density, longitudinal (MD) and transverse (TD) tensile ratio, reinforced uniaxial or biaxial orientation, shrinkage, or melt strength.

[0103] A method for preparing a polyolefin composition is provided, the method comprising melt blending: A) about 60 wt% to about 96 wt% of at least one recycled polyolefin; B) about 2 wt% to about 20 wt% of at least one random α-olefin copolymer; C) about 2 wt% to about 20 wt% of at least one tackifier; and D) optionally at least one additional polymer; wherein the polyolefin composition has a weight ratio of random α-olefin copolymer to tackifier between about 0.2 and about 5.0; and wherein the polyolefin composition has an increase in melt flow rate of about 5% to about 400% compared to the same polyolefin composition without random α-olefin copolymer and tackifier.

[0104] In another embodiment, a method for preparing a polyolefin composition is provided, the method comprising: 1) dry blending A) about 60 wt% to about 96 wt% of at least one recycled polyolefin, B) about 2 wt% to about 20 wt% of at least one random α-olefin copolymer, C) about 2 wt% to about 20 wt% of at least one tackifier, and D) optionally at least one additional polymer; wherein the polyolefin composition has a weight ratio of random α-olefin copolymer to tackifier between about 0.2 and about 5.0; and 2) melt blending these components; wherein the polyolefin composition has an increase in melt flow rate of about 5% to about 400% compared to the same polyolefin composition without random α-olefin copolymer and tackifier.

[0105] Polyolefin compositions can be formed by melt blending recycled polyolefin (A), random α-olefin copolymer (B), tackifier (C), and optionally additional polymer (D) by any means known in the art. In one embodiment, a dry blending powder, flakes, granules, or combination is used prior to the melt blending step. Examples of equipment used in dry blending include, but are not limited to, drum mixers, screw mixers, Henschel mixers, double cone mixers, or other suitable mixers, in which the recycled polyolefin (A), random α-olefin copolymer (B), tackifier (C), optionally at least one additive and optionally at least one filler, and optionally at least one additional polymer (D) are first contacted without close mixing; and these components are then melt blended in a mixer or extruder or any other type of mixing equipment known to those skilled in the art.

[0106] In another embodiment, the polyolefin composition can be formed by directly melt-blending recycled polyolefin (A), random α-olefin copolymer (B), and tackifier (C), optionally at least one additive, optionally at least one filler, and optionally at least one additional polymer (D) as powder, flakes, granules, or combinations thereof in a mixer, a single-screw extruder, a twin-screw extruder, or other equipment known to those skilled in the art; or alternatively, these compositions can be formed by (drying) blending recycled polyolefin (A), random α-olefin copolymer (B), and tackifier (C), optionally at least one additive, optionally at least one filler, and optionally at least one additional polymer (D) as powder, flakes, granules, or combinations thereof in the main hopper or side feeder of a profile or film extruder, or an injection molding machine, or any other type of polymer processing equipment known to those skilled in the art, and then melt-blending in the aforementioned processing equipment. The processing equipment can be the final stage of blending as part of the article manufacturing step, such as in an extruder for melting and conveying the composition, and then forming sheets or granules.

[0107] As used herein, the term "melt blending" refers to the use of shear force, tensile force, compressive force, ultrasonic energy, electromagnetic energy, thermal energy, or a combination thereof, in a processing apparatus, wherein such force is applied by a single screw, multi-screw, intermeshing screws rotating in the same or opposite directions, non-intermeshing screws rotating in the same or opposite directions, reciprocating screw, screw with pin, barrel with pin, roller, plunger, helical rotor, or a combination thereof. Melt blending can be performed in machines such as single-screw or multi-screw extruders, Buss kneaders, Eirich mixers, Farrel continuous mixers, Haake mixers, Brabender internal mixers, helicones, Ross mixers, Banbury mixers, roller mills, molding machines such as injection molding machines, vacuum forming machines, blow molding machines, etc., or a combination thereof. Typically, it is desirable to impart a specific energy of about 0.01 kW h / kg to about 10 kW h / kg during the melting of the composition. In another embodiment, melt blending is carried out in a twin-screw extruder such as a Brabender co-rotating twin-screw extruder, wherein for polyethylene-rich recycled polyethylene, the screw temperature zone is set to about 110°C to about 200°C, and for polypropylene-rich recycled polyolefins, the screw temperature zone is set to about 140°C to about 220°C.

[0108] In at least one embodiment, the addition of a random α-olefin copolymer (B), a tackifier (C), or a combination of both involves a “masterbatch” method, wherein the final concentration of the random α-olefin copolymer and / or tackifier is achieved by combining the recycled polyolefin with an appropriate amount of the random α-olefin copolymer and / or tackifier that has been previously prepared in a “carrier polymer” (masterbatch) at a higher additive concentration.

[0109] Such "carrier polymers" used for masterbatches can be ethylene polymers and / or propylene polymers, including but not limited to LDPE, LLDPE, HDPE, aPP, iPP, sPP, hPP, RCP, and / or combinations thereof. The carrier polymer can be virgin or recycled polyolefin. The carrier polymer may be the same as or different from the major component in the recycled polyolefin (A).

[0110] As used herein, the term "identical" means at least identical in terms of source (such as consumer waste), chemical backbone (such as polyethylene), morphology (such as LLDPE), physical properties (such as density), and rheological properties (such as MFR). For example, both are derived from post-consumer waste, both are recycled polyolefins rich in polypropylene, both primarily contain HDPE, and both have a density of 0.950 g / cm³. 2Two polymers with densities above 3 g / 10 min and an MFR of 3 g / 10 min are considered to be the same.

[0111] As used herein, the term “different” may include, but is not limited to, differences in origin (such as consumer waste), chemical backbone (such as polyethylene), morphology (such as LLDPE), physical properties (such as density), and rheological properties (such as MFR). For example, using polypropylene as a carrier polymer in a composition containing recycled polyolefins rich in polyethylene as recycled polyolefin (A), or using polyethylene with an MFR of 7.5 g / 10 min (ISO 1133, 190 °C, 2,16 kg) as a carrier polymer in a composition containing recycled polyolefins rich in polyethylene with an MFR of 2.0 g / 10 min (ISO 1133, 190 °C, 2,16 kg) as recycled polyolefin (A), is considered different from recycled polyolefin (A).

[0112] In at least one embodiment, the percentage of the random α-olefin copolymer (B), tackifier (C), or a combination of both (B+C) is from about 5% by weight to about 70% by weight, based on the weight of the masterbatch composition. In other embodiments, the percentage of the random α-olefin copolymer (B), tackifier (C), or a combination of both (B+C) ranges from about 20% by weight to about 60% by weight or from about 40% by weight to about 50% by weight. The masterbatch composition may include additional additives, fillers, or polymers.

[0113] The masterbatch composition can be formed by any method known in the art. In one embodiment, the masterbatch composition is formed by first drying the blended powder, flakes, granules, or combinations thereof using, for example, a drum mixer, wherein the carrier polymer and at least one random α-olefin copolymer and / or tackifier (and optional additives, fillers, or other polymers) are first contacted without thoroughly mixing the carrier polymer and the random α-olefin copolymer and / or tackifier, and then melt-blended in a mixer or any other type of mixing equipment known to those skilled in the art.

[0114] In another embodiment, the masterbatch composition is formed by directly melt-blending a carrier polymer and at least one random α-olefin copolymer and / or tackifier (and optional additives, fillers, or other polymers) as powder, flakes, granules, or combinations thereof in a mixer, single-screw extruder, twin-screw extruder, or other equipment known to those skilled in the art; or by (drying) blending a carrier polymer and at least one random α-olefin copolymer and / or tackifier (and optional additives, fillers, or other polymers) as powder, flakes, granules, or combinations thereof in the main hopper or side feeder of a profile or film extruder or any other type of polymer processing equipment known to those skilled in the art in powder, flakes, granules, or combinations thereof in the aforementioned processing equipment.

[0115] The carrier polymer used in the masterbatch may have an MFR (ISO 1133, 190°C, 2.16 kg) ranging from about 0.5 g / 10 min to about 25 g / 10 min, about 4 g / 10 min to about 25 g / 10 min, about 5 g / 10 min to about 25 g / 10 min, about 6 g / 10 min to about 25 g / 10 min, about 7 g / 10 min to about 25 g / 10 min, about 8 g / 10 min to about 25 g / 10 min, about 9 g / 10 min to about 25 g / 10 min, about 10 g / 10 min to about 25 g / 10 min, about 11 g / 10 min to about 25 g / 10 min, about 12 g / 10 min to about 25 g / 10 min, about 13 g / 10 min to about 25 g / 10 min, about 14 g / 10 min to about 25 g / 10 min, and about 15 g / 10 min to about 25 g / 10 min.

[0116] The carrier polymer used in the masterbatch may have an MFR (ISO 1133, 230°C, 2.16 kg) in the range of about 0.5 g / 10 min to about 25 g / 10 min, about 4 g / 10 min to about 25 g / 10 min, about 5 g / 10 min to about 25 g / 10 min, about 6 g / 10 min to about 25 g / 10 min, about 7 g / 10 min to about 25 g / 10 min, about 8 g / 10 min to about 25 g / 10 min, about 9 g / 10 min to about 25 g / 10 min, about 10 g / 10 min to about 25 g / 10 min, about 11 g / 10 min to about 25 g / 10 min, about 12 g / 10 min to about 25 g / 10 min, about 13 g / 10 min to about 25 g / 10 min, about 14 g / 10 min to about 25 g / 10 min, and about 15 g / 10 min to about 25 g / 10 min.

[0117] In another embodiment, a masterbatch composition is formed by melt blending a carrier polymer and a random α-olefin copolymer (B) and / or a tackifier (C) in a twin-screw extruder such as a Brabender co-rotating twin-screw extruder, wherein for a masterbatch composition using virgin LDPE with an MFR of about 2 g / 10 min to about 7.5 g / 10 min (ISO 1133, 190°C, 2.16 kg), the screw temperature zone is set to about 85°C to about 160°C, and for a masterbatch composition using virgin iPP with an MFR of about 2 g / 10 min to about 25 g / 10 min (ISO 1133, 230°C, 2.16 kg), the screw temperature zone is set to about 120°C to about 185°C.

[0118] The masterbatch composition may be in the form of granules, pellets, powders, or flakes, and may also be additionally coated or powdered to improve processing. Such coatings or release agents include, but are not limited to, polyethylene wax, polypropylene wax, talc, or silica.

[0119] In at least one embodiment, the prepared polyolefin composition is in the form of granules, pellets, powder, or flakes, suitable for further processing into articles containing such compositions.

[0120] Additionally, as needed, the polyolefin composition, one or more components of the composition, and / or the product formed from the composition (such as a film) may contain other polymers, additives, or fillers.

[0121] Other polymers that may be included in the composition may include, but are not limited to, ethylene vinyl acetate, ethylene methyl acrylate, ethylene ethyl acrylate, ethylene n-butyl acrylate, terpolymers of ethylene, ethyl acrylate and maleic anhydride, copolymers of acrylic acid, polymethyl methacrylate or any other polymer that can be polymerized by a high-pressure free radical method, LLDPE, LDPE, MDPE, HDPE, ethylene-1-hexene copolymers, copolymers and terpolymers of ethylene and α-olefins, copolymers and terpolymers of propylene and α-olefins, plasmons, metallocene-catalyzed polyolefins, maleic acid-modified polyolefins, and maleic acid-modified polypropylene. Polyethylene and polyethylene-based polymers, polyvinyl chloride, polybutene-1, isotactic polybutene, acrylonitrile butadiene styrene (ABS) resin, MBS (methacrylate butadiene styrene) resin, ethylene propylene rubber (EPR), vulcanized EPR, EPDM (ethylene propylene diene monomer rubber), block copolymers, styrene block copolymers, maleic acid modified styrene block copolymers, polyamides, polycarbonates, PET resins, cross-linked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymers of aromatic monomers such as polystyrene, polyesters, polyacetals, polyvinylidene fluoride, polyethylene glycol, polyisobutylene, and / or combinations thereof.

[0122] In at least one embodiment, at least one of the “other polymers” may be used as a carrier polymer.

[0123] In at least one embodiment of the invention, a polyolefin composition is provided comprising at least one “other polymer” as an “additional polymer”. The terms “other polymer” and “additional polymer” are used interchangeably.

[0124] Surprisingly, some of these "other" or "additional" polymers have been found to improve the impact resistance of the polyolefin compositions of the present invention. At least one rheological, physical, and mechanical property, such as MFR, elongation, tensile strength, flexural strength, flexural modulus, and Young's modulus (E-modulus), has been unexpectedly improved and / or provides a favorable balance of physical and rheological properties by the addition of other polymers. These "other" or "additional" polymers may be used as carriers in masterbatch processes, additives in masterbatches, dry-blended into compositions, or incorporated into polyolefin compositions by any method known to those skilled in the art. The at least one "other" or "additional" polymer included in the polyolefin composition may be from about 1% to about 60% of the polyolefin composition, from about 2% to about 60% of the polyolefin composition, from about 3% to about 60% of the polyolefin composition, from about 4% to about 60% of the polyolefin composition, from about 5% to about 60% of the polyolefin composition, from about 6% to about 60% of the polyolefin composition, from about 7% to about 60% of the polyolefin composition, from about 8% to about 60% of the polyolefin composition, from about 9% to about 60% of the polyolefin composition, from about 10% to about 60% of the polyolefin composition, from about 11% to about 60% of the polyolefin composition, from about 12% to about 60% of the polyolefin composition, from about 13% to about 60% of the polyolefin composition, from about 14% to about 60% of the polyolefin composition, from about 15% to about 60% of the polyolefin composition, from about 16% to about 60% of the polyolefin composition, from about 17% to about 60% of the polyolefin composition, from about 18% to about 60% of the polyolefin composition, from about 19% to about 60% of the polyolefin composition, from about 20% to about 60% of the polyolefin composition, from about 25% to about 60% of the polyolefin composition, from about 30% to about 60% of the polyolefin composition, from about 35% to about 60% of the polyolefin composition, from about 40% to about 60% of the polyolefin composition, and from about 45% to about 60% of the polyolefin composition.

[0125] In at least one embodiment of the invention, the at least one "other" or "additional" polymer included in the polyolefin composition may be from about 1% to about 45% by weight of the polyolefin composition, from about 2% to about 45% by weight, from about 3% to about 45% by weight, from about 4% to about 45% by weight, from about 5% to about 45% by weight, from about 6% to about 45% by weight, from about 7% to about 45% by weight, from about 8% to about 45% by weight, from about 9% to about 45% by weight, from about 10% to about 45% by weight, from about 1% by weight, or from about 1% by weight. 1 wt% to about 45 wt%, about 12 wt% to about 45 wt%, about 13 wt% to about 45 wt%, about 14 wt% to about 45 wt%, about 15 wt% to about 45 wt%, about 16 wt% to about 45 wt%, about 17 wt% to about 45 wt%, about 18 wt% to about 45 wt%, about 19 wt% to about 45 wt%, about 20 wt% to about 45 wt%, about 25 wt% to about 45 wt%, about 30 wt% to about 45 wt%, about 35 wt% to about 45 wt%, about 40 wt% to about 45 wt%. In at least one embodiment of the invention, the at least one "other" or "additional" polymer included in the polyolefin composition may be from about 1% to about 25% by weight of the polyolefin composition, from about 2% to about 25% by weight, from about 3% to about 25% by weight, from about 4% to about 25% by weight, from about 5% to about 25% by weight, from about 6% to about 25% by weight, from about 7% to about 25% by weight, from about 8% to about 25% by weight, from about 9% to about 25% by weight, from about 10% to about 25% by weight, from about 11% to about 25% by weight, from about 12% to about 25% by weight, from about 13% to about 25% by weight, from about 14% to about 25% by weight, from about 15% to about 25% by weight, from about 16% to about 25% by weight, from about 17% to about 25% by weight, from about 18% to about 25% by weight, from about 19% to about 25% by weight, or from about 20% to about 25% by weight.

[0126] In one embodiment, at least one “other” or “additional” polymer that modifies the impact resistance and / or other physical and / or rheological properties of the polyolefin composition can be prepared as a masterbatch comprising: (A) about 40% to about 60% by weight of at least one random α-olefin copolymer; and (B) about 40% to about 60% by weight of at least one “other” or “additional” polymer. Suitable “other” or “additional” polymers include, but are not limited to, for example: ethylene-acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-methyl acrylate copolymers, ethylene-butyl acrylate copolymers, and terpolymers of ethylene, ethyl acrylate, and maleic anhydride (which can be used as a loter). TM4700 (obtained from SK Functional Polymers, Paris, France), MDPE, HDPE, LLDPE, LDPE, virgin PP homopolymer, PP copolymer, ethylene-hexene, ethylene-octene copolymer, ethylene-butene copolymer (can be used as an engine). TM AFFINITY TM and AFFINITY TM (GA sourced from Dow Chemical, USA). Depending on the application and desired final properties, the amount of masterbatch can vary from about 5% by weight to about 50% by weight of the polyolefin composition. In at least one aspect of this embodiment, the amount of masterbatch can range from about 2% by weight to about 50% by weight, about 3% by weight to about 50% by weight, about 4% by weight to about 50% by weight, about 5% by weight to about 50% by weight, about 6% by weight to about 50% by weight, about 7% by weight to about 50% by weight, about 8% by weight to about 50% by weight, about 9% by weight to about 50% by weight, about 10% by weight to about 50% by weight, about 11% by weight to about 50% by weight, about 12% by weight to about 50% by weight, and so on. 50 wt%, about 13 wt% to about 50 wt%, about 14 wt% to about 50 wt%, about 15 wt% to about 50 wt%, about 16 wt% to about 50 wt%, about 17 wt% to about 50 wt%, about 18 wt% to about 50 wt%, about 19 wt% to about 50 wt%, about 20 wt% to about 50 wt%, about 25 wt% to about 50 wt%, about 30 wt% to about 50 wt%, about 35 wt% to about 50 wt%, and about 40 wt% to about 50 wt%.

[0127] In at least one embodiment, a polyolefin composition is provided comprising: (A) about 60% to about 96% by weight of at least one recycled polyolefin; (B) about 2% to about 20% by weight of at least one random α-olefin copolymer; (C) at least one tackifier; and (D) about 2% to about 20% by weight of at least one additional polymer selected from ethylene vinyl acetate, ethylene methyl acrylate, ethylene ethyl acrylate, ethylene n-butyl acrylate, and terpolymers of ethylene, ethyl acrylate, and maleic anhydride; wherein the polyolefin composition has a weight ratio of random α-olefin copolymer to tackifier between about 0.2 and about 5.0; and wherein the polyolefin composition has an increase in melt flow rate of about 5% to about 400% compared to the same polyolefin composition without random α-olefin copolymer and tackifier; and wherein the polyolefin composition maintains acceptable mechanical properties. In at least one embodiment, a polyolefin composition is provided comprising: (A) about 60% to about 96% by weight of at least one recycled polyolefin; (B) about 2% to about 20% by weight of at least one random α-olefin copolymer; (C) at least one tackifier; and (D) about 2% to about 20% by weight of at least one additional polymer; wherein the polyolefin composition has a weight ratio of random α-olefin copolymer to tackifier between about 0.2 and about 5.0; and wherein the polyolefin composition has an increase in melt flow rate of about 5% to about 600% compared to the same polyolefin composition without the random α-olefin copolymer, the additional polymer, and the tackifier; and wherein the polyolefin composition maintains acceptable mechanical properties.

[0128] In at least one embodiment, the polyolefin composition comprises a recycled polyolefin (A), at least one random α-olefin copolymer (B), at least one tackifier resin (C), and at least one additional polymer (D), wherein the at least one additional polymer is selected from linear low-density polyethylene, low-density polyethylene, medium-density polyethylene, ethylene-hexene copolymer, ethylene-butene copolymer, and ethylene-octene copolymer; wherein the percentage of B+C+D is from about 10% by weight to about 60% by weight based on the weight of the total polyolefin composition. In other embodiments, the percentage of B+C+D ranges from about 20% by weight to 45% by weight and from about 10% to 20% by weight. In other embodiments of the invention, the weight ratio of B+C to D is between about 0.2 and about 20, between about 0.2 and about 5.0, and between about 0.5 and about 2.0. In other embodiments, the weight ratio of B to C is between 0.2 and 5.0. Compared to the same polyolefin composition without at least one random α-olefin copolymer, tackifier resin, and other polymers, the polyolefin composition may have an MFR increase of about 5% to 400%. In at least one aspect of the above embodiments, compared to the same polyolefin composition without said at least one random α-olefin copolymer, tackifier resin, and other polymers, the polyolefin composition has an MFR increase of about 3% to about 400% and an elongation at break increase of about 30% to about 150%; and said polyolefin composition maintains acceptable mechanical properties.

[0129] In at least one embodiment, the polyolefin composition comprises a recycled polyolefin (A), at least one random α-olefin copolymer (B), at least one tackifier resin (C), and at least one additional polymer (D), wherein the at least one additional polymer is selected from linear low-density polyethylene, low-density polyethylene, medium-density polyethylene, ethylene-hexene copolymer, ethylene-butene copolymer, and ethylene-octene copolymer; wherein, based on the weight of the total polyolefin composition, the percentage of B+C+D ranges from about 10 wt% to about 60 wt%, from about 20 wt% to about 45 wt%, or from about 10 wt% to about 20 wt%; wherein the weight ratio of B+C to D is between about 0. The weight ratio of B to C is between 0.2 and about 20, between about 0.2 and about 5.0, or between about 0.5 and about 2.0; wherein the weight ratio of B to C is between 0.2 and 5.0; wherein the polyolefin composition has an increase in MFR of about 5% to 400% compared to the same polyolefin composition without at least one random α-olefin copolymer, tackifier resin, and other polymers; and wherein the polyolefin composition has an increase in elongation at break of about 30% to about 150% compared to the same polyolefin composition without said at least one random α-olefin copolymer, tackifier resin, and other polymers; and wherein the polyolefin composition maintains acceptable mechanical properties. Acceptable mechanical properties are defined in this specification.

[0130] In at least one embodiment, the polyolefin composition comprises a polyethylene-rich recycled polyolefin (A), at least one random α-olefin copolymer (B), at least one tackifier resin (C), and at least one additional polymer (D). The additional polymer may be, but is not limited to, linear low-density polyethylene, low-density polyethylene, medium-density polyethylene, ethylene-hexene copolymer, ethylene-butene copolymer, or ethylene-octene copolymer. The polyolefin composition can be prepared in which the percentage of B+C+D is from about 10% to about 60% by weight or from about 20% to about 45% by weight, based on the weight of the total polyolefin composition. The weight ratio of B to C in the polyolefin composition may be between 0.2 and 5.0. Furthermore, in some embodiments, compared to the same polyolefin composition without at least one random α-olefin copolymer, tackifier resin, and the additional polymer, the polyolefin composition has an increase in MFR of about 100% to 250% and an increase in elongation at break of about 100% to about 600%; and the polyolefin maintains acceptable mechanical properties.

[0131] In at least one embodiment, the polyolefin composition comprises a polyethylene-rich recycled polyolefin (A), at least one random α-olefin copolymer (B), at least one tackifier resin (C), and at least one additional polymer (D); wherein the additional polymer is selected from linear low-density polyethylene, low-density polyethylene, medium-density polyethylene, ethylene-hexene copolymer, ethylene-butene copolymer, or ethylene-octene copolymer; wherein the percentage of B+C+D is from about 10% to about 60% by weight or from about 20% to about 45% by weight, based on the weight of the total polyolefin composition; wherein the weight ratio of B to C in the polyolefin composition is from about 0.2 to 5.0; wherein the polyolefin composition has an increase of about 100% to 250% in MFR and an increase of about 100% to about 600% in elongation at break compared to the same polyolefin composition without at least one random α-olefin copolymer, tackifier resin, and the additional polymer; and wherein the polyolefin maintains acceptable mechanical properties.

[0132] In at least one embodiment of the invention, a polyolefin composition is provided comprising a polypropylene-rich recycled polyolefin (A), at least one random α-olefin copolymer (B), at least one tackifier resin (C), and at least one additional polymer (D); wherein, based on the weight of the total polyolefin composition, the percentage of B+C+D can range from about 10 wt% to about 60 wt% or from about 20 wt% to about 45 wt%. The weight ratio of B to C can be between 0.2 and 5.0. Compared to the same polyolefin composition without at least one random α-olefin copolymer, tackifier resin, and additional polymer, this polyolefin composition can have an increase in MFR of about 3% to about 60% while maintaining acceptable mechanical properties. In some aspects of this embodiment, the polyolefin composition also has an increase in elongation at break of about 30% to about 150%. In other aspects of this embodiment, the polyolefin composition also has an increase in flexural strength of about 40% while maintaining acceptable mechanical properties.

[0133] In at least one embodiment of the invention, a polyolefin composition is provided comprising a polypropylene-rich recycled polyolefin (A), at least one random α-olefin copolymer (B), at least one tackifier resin (C), and at least one additional polymer (D); wherein the percentage of B+C+D, based on the weight of the total polyolefin composition, is from about 10% to about 60% by weight or from about 20% to about 45% by weight; wherein the weight ratio of B to C is between 0.2 and 5.0; wherein, compared to the same polyolefin composition without at least one random α-olefin copolymer, tackifier resin, and additional polymer, the polyolefin composition has an increase in MFR of about 3% to about 60%, and the polyolefin composition also has an increase in flexural strength of about 40% while maintaining acceptable mechanical properties. In some aspects of this embodiment, the polyolefin composition also has an increase in elongation at break of about 30% to about 150%.

[0134] In at least one embodiment of the present invention, a polyolefin composition is provided comprising a recycled polyolefin (A), a random α-olefin copolymer (B) with a glass transition temperature equal to or below -10°C (ASTM D 3418-15) and a nominal molecular weight equal to or below 25,000 g / mol (ISO 16014), and a glass transition temperature equal to or above 45°C (ASTM D 3418-15). The tackifier (C), (C) and additional polymer (D) of D3418-15, wherein the additional polymer may be, but is not limited to, linear low-density polyethylene, medium-density polyethylene, ethylene methyl acrylate copolymer, ethylene-hexene copolymer, ethylene-butene copolymer or ethylene-octene copolymer, wherein the percentage of B+C+D is from about 5% to about 30% by weight or from about 10% to about 20% by weight based on the weight of the total polyolefin composition; wherein the weight ratio of B+C to D is from about 0.2 to 20.0, from about 0.2 to about 5.0 or from about 0.5 to 2.0; wherein the weight ratio of B to C is between about 0.2 and 5.0; wherein the polyolefin composition has an increase of about 5% to 400% in MFR compared to the same polyolefin composition without random α-olefin copolymer, tackifier and additional polymer; and wherein the polyolefin composition maintains acceptable mechanical properties.

[0135] In at least one embodiment of the present invention, a polyolefin composition is provided comprising a recycled polyolefin (A), a random α-olefin copolymer (B) with a glass transition temperature equal to or below -10°C (ASTM D 3418-15) and a nominal molecular weight equal to or below 10,000 g / mol (ISO 16014), and a glass transition temperature equal to or above 45°C (ASTM D 3418-15). The tackifier (C), (C) and additional polymer (D) of D3418-15, wherein the additional polymer may be, but is not limited to, linear low-density polyethylene, medium-density polyethylene, ethylene methyl acrylate copolymer, ethylene-hexene copolymer, ethylene-butene copolymer or ethylene-octene copolymer, wherein the percentage of B+C+D is from about 5% to about 30% by weight or from about 10% to about 20% by weight based on the weight of the total polyolefin composition; wherein the weight ratio of B+C to D is from about 0.2 to 20.0, from about 0.2 to about 5.0 or from about 0.5 to 2.0; wherein the weight ratio of B to C is between about 0.2 and 5.0; wherein the polyolefin composition has an increase of about 5% to 400% in MFR compared to the same polyolefin composition without random α-olefin copolymer, tackifier and additional polymer; and wherein the polyolefin composition maintains acceptable mechanical properties.

[0136] In at least one embodiment of the invention, a polyolefin composition is provided comprising a recycled polyolefin (A), a random α-olefin copolymer (B), a tackifier (C), and an additional polymer (D), wherein the additional polymer may be, but is not limited to, linear low-density polyethylene, medium-density polyethylene, ethylene methyl acrylate copolymer, ethylene-hexene copolymer, ethylene-butene copolymer, or ethylene-octene copolymer, wherein the percentage of B+C+D is from about 5% to about 30% by weight or from about 10% to about 20% by weight based on the weight of the total polyolefin composition; wherein the weight ratio of B+C to D is from about 0.2 to 20.0, from about 0.2 to about 5.0, or from about 0.5 to 2.0; wherein the weight ratio of B to C is between about 0.2 and 5.0; wherein the polyolefin composition has an MFR increase of about 5% to 400% compared to the same polyolefin composition without the random α-olefin copolymer, tackifier, and additional polymer; and wherein the polyolefin composition maintains acceptable mechanical properties.

[0137] In a specific aspect of this embodiment, the additional polymer (D) is maleic acid-modified polyethylene or polypropylene, wherein the percentage of D is between about 1% and 5% by weight or about 1% and 3% by weight; wherein the weight ratio of B+C to D is between about 2 to 20 or about 5 to 10; wherein the polyolefin composition has an increase of about 5% to 100% in MFR and exhibits improved compatibility with impurities present in the recycled polyolefin (A); and wherein the polyolefin composition maintains acceptable mechanical properties.

[0138] In another specific aspect of this embodiment, the additional polymer (D) is linear low-density polyethylene (LLDPE) and the recycled polyolefin is a polypropylene-rich recycled polyolefin, wherein the percentage of D is between about 5% by weight and about 30% by weight, about 10% by weight and about 20% by weight; wherein the weight ratio of B+C to D is between about 0.2 and about 2 or about 0.3 and about 1; wherein, compared with the same polyolefin composition without random α-olefin copolymers, tackifiers and additional polymers, the polyolefin composition has an increase of about 5% to 100% in MFR and an increase of about 5% to 200% in notched impact strength, and wherein the polyolefin composition maintains acceptable mechanical properties.

[0139] In another specific aspect of this embodiment, a polyolefin composition is prepared, wherein a further polymer is used as a carrier polymer of the masterbatch, wherein the percentage of B+C is between about 5% by weight and about 70% by weight, or about 40% by weight and about 60% by weight, based on the weight of the masterbatch. The percentage of the masterbatch may range from about 5% by weight to about 40% by weight, or from about 10% by weight to about 20% by weight of the total polyolefin composition; wherein the polyolefin composition has an increase of about 5% to 100% in MFR compared to the same polyolefin composition without the masterbatch, and wherein the polyolefin composition maintains acceptable mechanical properties.

[0140] In at least one embodiment, a polyolefin composition is provided comprising a recycled polyolefin (A), a random α-olefin copolymer (B), a tackifier (C), and an additional polymer (D), wherein the α-olefin copolymer (B) and the tackifier (C) are first prepared as a masterbatch using a carrier polymer. The carrier polymer may be a virgin or recycled polyolefin and may be the same as or different from the recycled polyolefin (A) or the major component in the recycled polyolefin (A) or the additional polymer (D). Based on the weight of the masterbatch, the percentage of B+C is between about 5% by weight and about 70% by weight or about 40% by weight and about 60% by weight, and the weight ratio of B to C is between 0.2 and 5.0. The percentage of the masterbatch may range from about 5% to about 40% or 10% to 20% of the total polyolefin composition. The ratio of the masterbatch to the additional polymer (D) can range from about 0.2 to about 20, or about 0.2 to about 5.0, or about 0.5 to about 2.0, and wherein the polyolefin composition has an increase of about 5% to 400% in MFR compared to the same polyolefin composition without random α-olefin copolymers, tackifiers and additional polymers, and wherein the polyolefin composition maintains acceptable mechanical properties.

[0141] In at least one embodiment, a polyolefin composition is provided comprising a recycled polyolefin (A), a random α-olefin copolymer (B) with a glass transition temperature equal to or below -10°C (ASTM D 3418-15) and a nominal molecular weight equal to or below 25,000 g / mol (ISO 16014), a tackifier (C) with a glass transition temperature equal to or above 45°C (ASTM D 3418-15), and an additional polymer (D), wherein the α-olefin copolymer (B) and the tackifier (C) are first prepared as a masterbatch using a carrier polymer. The carrier polymer may be a virgin or recycled polyolefin and may be the same as or different from the recycled polyolefin (A) or the major component in the recycled polyolefin (A) or the additional polymer (D). Based on the weight of the masterbatch, the percentage of B+C is between about 5% by weight and about 70% by weight or about 40% by weight and about 60% by weight, and the weight ratio of B to C is between 0.2 and 5.0. The percentage of masterbatch can range from about 5% to about 40% or from 10% to 20% of the total polyolefin composition. The ratio of masterbatch to additional polymer (D) can range from about 0.2 to about 20, or about 0.2 to about 5.0, or about 0.5 to about 2.0, and wherein the polyolefin composition has an increase of about 5% to about 400% in MFR compared to the same polyolefin composition without random α-olefin copolymers, tackifiers and additional polymers, and wherein the polyolefin composition maintains acceptable mechanical properties.

[0142] In another aspect of this embodiment, the additional polymer may be, but is not limited to, linear low-density polyethylene, medium-density polyethylene, ethylene methyl acrylate copolymer, ethylene-hexene copolymer, ethylene-butene copolymer, or ethylene-octene copolymer.

[0143] Surprisingly, the standard deviation of the polyolefin composition was significantly lower than that of the unmodified recycled polyolefin sample. This significant reduction in test variation indicates that the polyolefin composition has a more consistent composition and quality than the unmodified recycled polyolefin. This is industrially advantageous for producing consistent products from recycled polyolefins.

[0144] Such additives that may be included in polyolefin compositions may include, but are not limited to, antioxidants (AOs) (e.g., sterically hindered phenols such as BASF's IRGANOX). TM 1010 or IRGANOX TM 1076, phosphorus-based AO such as BASF's IRGAFOS TM 168, sulfur-based AO such as BASF's Irganox PS-802FL TMNitrogen-based AOs such as 4,4'-bis(1,1'-dimethylbenzyl)diphenylamine or AO blends), acid stabilizers (e.g., calcium stearate, sodium stearate, zinc stearate, magnesium oxide and zinc oxide, synthetic hydrotalcite, lactates and alkenyl lactates), anti-adhesion additives, plasticizers, tackifiers (e.g., polybutene, terpene resins, aliphatic and aromatic hydrocarbon resins, alkali metal and glyceryl stearates and hydrogenated rosin), UV stabilizers (e.g., bis-(2'2'6'6-tetramethyl-4-piperidinyl)-sebate), heat stabilizers Agents, nucleating agents (e.g., sodium benzoate, 1,3:2,4-bis(3,4-dimethylbenzyl)sorbitol), anti-blocking agents (e.g., diatomaceous earth; synthetic silica; silicates such as kaolin, sodium aluminum silicate, calcined kaolin, aluminum silicate, or calcium silicate; synthetic zeolite), crosslinking agents, release agents, antistatic agents (e.g., glycerides, ethoxylated amines, ethoxylated amides), antimicrobial agents, biocides, foaming agents, bubbling agents, clarifying agents, flame retardants, catalysts, pigments, colorants, dyes, waxes, or combinations thereof. Typically, for each individual additive, the amount of these additives can range from about 100 ppm to about 2000 ppm.

[0145] Such fillers that may be included in the composition may include, but are not limited to, coal, fly ash, calcium carbonate, barium sulfate, carbon black, metal oxides, inorganic materials, natural materials, alumina trihydrate, magnesium hydroxide, bauxite, talc, mica, barite, kaolinite, silica, post-consumer or post-industrial glass, sawdust, synthetic fibers and natural fibers, or any combination thereof. The fillers may be organic, inorganic, or a combination of both, and may have different forms.

[0146] Other polymers, additives, and fillers may be added in amounts known to those skilled in the art. For example, the amount of additives in the polyolefin composition may be less than 10% by weight, less than 5% by weight, less than 1% by weight, and less than 0.3% by weight, based on the weight of the polyolefin composition. In other embodiments of the invention, the amount of filler in the polyolefin composition may be from about 5% by weight to about 85% by weight, from about 5% by weight to about 75% by weight, from about 5% by weight to about 65% by weight, from about 5% by weight to about 55% by weight, from about 5% by weight to about 45% by weight, from about 5% by weight to about 35% by weight, from about 5% by weight to about 25% by weight, and from about 5% by weight to about 20% by weight, based on the weight of the polyolefin composition.

[0147] Visbreaking process for preparing a polyolefin composition

[0148] In another embodiment of the invention, a method for preparing a polyolefin composition is provided, the method comprising: 1) extruding at least one recycled polyethylene-rich polyolefin in the presence of at least one free radical initiator to prepare an extruded, viscous-reduced, cracked recycled polyethylene-rich polyolefin; and 2) melt blending (A) about 60 wt% to about 96 wt% of the viscous-reduced, cracked recycled polyethylene-rich polyolefin; B) about 2 wt% to about 20 wt% of at least one random α-olefin copolymer; C) optionally about 2 wt% to about 20 wt% of at least one tackifier; and D) optionally at least one additional polymer; wherein the extruded, viscous-reduced, cracked polyolefin composition has a weight ratio of random α-olefin copolymer to tackifier between about 0.2 and about 5.0; and wherein the extruded, viscous-reduced, cracked polyolefin composition has an increase in melt flow rate of about 5% to about 1500% compared to the recycled polyolefin.

[0149] Regenerated polyethylene-rich polyolefins, random α-olefin copolymers, tackifiers, and other polymers have previously been described in this specification.

[0150] This invention relates to a novel method for de-thickening and cracking recycled polyolefins and blending them to form polyolefin compositions. De-thickening is defined as subjecting the polyolefin to chain scission, which reduces the molecular weight and increases the melt flow rate. In one embodiment, the method employs a single extrusion step, resulting in a significant increase in the MFR of the initial recycled polyolefin without any crosslinking.

[0151] Starting materials for the visbreaking process for preparing a polyolefin composition

[0152] In one embodiment of the invention, the method uses starting polyethylene from a post-consumer or post-industrial polyethylene-rich polyolefin stream with a density of about 910 kg / m³ to about 1050 kg / m³, or an ethylene plasmid or elastomer with a density of about 855 kg / m³ to about 960 kg / m³. The ethylene elastomer may have a density of about 855 kg / m³ to about 950 kg / m³, and the ethylene plasmid may have a density of about 880 kg / m³ to about 950 kg / m³.

[0153] Extrusion conditions for the visbreaking process

[0154] To improve the melt flow rate of initially regenerated polyethylene-rich polyolefins (MFRs) in a viscous cracking process, the regenerated MFRs are extruded under specific conditions using a specific free radical initiator. In one embodiment of the invention, the extrusion process is performed using at least one of high temperature, high shear, and / or high speed. Furthermore, the desired increase in MFR can be achieved using a single extrusion step. Many prior art methods require complex multiple extrusions. In this invention, a significant increase in MFR can be achieved using a single extrusion step.

[0155] Therefore, the extruder can be a single-screw extruder, a twin-screw extruder, such as a co-rotating twin-screw extruder or a counter-rotating twin-screw extruder; or a multi-screw extruder, such as a ring extruder. Suitable extruders include single-screw extruders or twin-screw extruders. In one embodiment of the invention, the extruder is a co-rotating twin-screw extruder.

[0156] Suitable extruder lengths are typically 125cm to 2540cm, 510cm to 1270cm, or 635cm to 1020cm. The residence time of the polymer feedstock in the extruder is typically from about 30 seconds to about 5 minutes or from about 30 seconds to about 3 minutes.

[0157] Extruders typically have multiple heating zones. It is important to note that a significant amount of heat is usually generated by shear heating during the extrusion process. Therefore, the temperature of the polymer melt in the extruder can be significantly higher than the temperature set in the heating zone at the screw and barrel, and can also be significantly higher than the actual zone temperature readings in the extruder. Furthermore, the actual zone temperature readings in different stages of the extruder can also be higher than the temperatures set in the heating zones. The temperatures referred to in this article are those set in the heating zones.

[0158] Such extruders are well known in the art and are supplied by companies such as Coperion, Japan Steel Works, Krauss Maffei Berstorff, or Leisteritz.

[0159] In one embodiment of the invention, the extrusion is high-temperature extrusion. High temperature means that the highest barrel temperature is set to a minimum of 250°C or a minimum of 300°C. In other embodiments, the highest barrel temperature is at least 310°C, at least 325°C, at least 340°C, or at least 350°C. The upper limit for the highest barrel temperature zone of the extruder can be 400°C.

[0160] This can be translated into a melt temperature of the polymer melt leaving the die head of at least 240°C, at least 290°C, at least 310°C, at least 320°C, at least 330°C, or at least 340°C. The upper limit of the melt temperature leaving the die head can be 390°C.

[0161] In another embodiment of the invention, the extruder has 10 to 14 zones, such as 12 zones. In yet another embodiment, a high extrusion temperature is applied through zone 3. The maximum extrusion temperature can be applied by zone 3 and maintained across the remaining zones in the extruder.

[0162] The temperature of the template can be from about 120°C to about 180°C. In another embodiment, the temperature distribution can be set as follows: zone 1 is below 80°C, zone 2 is between 80°C and 120°C, and zones 3 to 12 are at 250°C or higher. In another embodiment, the temperature distribution can be set as follows: zone 1 is at 20°C, zone 2 is at 100°C, zones 3 to 12 are at 350°C, and the template is at 150°C.

[0163] Not wanting to be limited by theory, we recognize that higher temperatures lead to an increase in MFR, and thus a decrease in molecular weight.

[0164] In another embodiment of the invention, the extruder can operate at a high screw speed. High screw speed means that the extruder screw rotates at a speed of at least 300 rpm, at least 350 rpm, or at least 400 rpm. Much higher screw speeds can also be used, such as 600 rpm or higher, 800 rpm or higher, or 1000 rpm or higher. The upper limit of the screw speed is determined by the extruder used, but can be 1300 rpm. The screw speed range can be from 450 rpm to 1200 rpm. Preferably, the screw speed remains constant throughout the method. Not wishing to be limited by theory, we recognize that higher screw speeds lead to an increase in MFR and thus a decrease in molecular weight.

[0165] The yield rate is also related to the increase in MFR. The higher the yield rate, the lower the increase in MFR, because the polymer has less opportunity to undergo viscous cracking conditions in the extruder. Therefore, although high screw speeds are generally required, it is preferable to keep the yield rate low. Suitable yield rates on industrial extruders can be 5 kg / h to 40 kg / h or 10 kg / h to 20 kg / h. Lower yield rates result in higher MFR.

[0166] Screw speed is also related to residence time in the extruder. Faster screw speed means shorter residence time. The residence time in the extruder in the method of this invention can range from 30 seconds to 1.5 minutes or from 35 seconds to 70 seconds.

[0167] In this respect, the specific energy input (SEI) is also a factor to consider in this method. Specific energy input (SEI) is the amount of power supplied to the extruder motor per kilogram of polymer material. Higher screw speeds mean more power to the motor. Higher output requires more power to the motor. High SEI leads to a high final MFR. The correlation between SEI and MFR is essentially linear.

[0168] The energy input to the extruder motor can be measured from the extruder itself. It is the available output from the extruder. It should be understood that the SEI value depends on the size and nature of the extruder used. Therefore, the SEI measured using a Coperion ZSK32 can be at least 0.2 kWh / kg or at least 0.4 kWh / kg.

[0169] The method of the present invention can also utilize high shear. The high shear effect can originate from one or more kneader 90° screw elements, which can be positioned within the mixing zone of the extruder. The extruder screw elements and screw configuration can be designed to promote a strong shear effect with optimized melt mixing.

[0170] Extruded, viscous, cracked, polyethylene-rich recycled polyolefins exiting the extruder die can be collected in a sealed container and kept liquid for transport to the next step or extruder for modification with additives and / or fillers at a lower temperature prior to granulation. In one embodiment of the invention, conventional granulation techniques can be used to granulate the extruded, viscous, cracked, polyethylene-rich recycled polyolefins exiting the extruder die. Therefore, another aspect of the invention is the granulation of extruded, viscous, cracked, recycled polyethylene-rich polyolefins exiting the extruder.

[0171] Extruders for the visbreaking process

[0172] More specifically, an extruder typically includes a feed zone, a melting zone, a mixing zone, and a die zone. Furthermore, the melt extruded through the die is typically solidified and cut into pellets in a pelletizer. Extruders typically have an length-to-diameter ratio (L / D) of about 6:1 to about 65:1 or about 8:1 to 60:1. As is well known in the art, co-rotating twin-screw extruders typically have a larger L / D than counter-rotating twin-screw extruders. An extruder may have one or more discharge or vent ports for removing gaseous components from the extruder.

[0173] This discharge port should be placed sufficiently downstream to allow adequate reaction time between the initiator and the recycled polyolefin. Suitablely, the discharge port may be located within the downstream end of the melt zone or within the mixing zone.

[0174] A stripping agent, such as water, steam, or nitrogen, is appropriately added to the extruder to help remove volatile components from the polymer melt. When using such a stripping agent, it is added upstream of the discharge port or upstream of the most downstream discharge port (if multiple discharge ports exist).

[0175] The extruder may also have one or more feed ports for feeding other components such as polymers, additives, etc. into the extruder. The location of such additional feed ports depends on the type of material added through the port.

[0176] Feed zone for the visbreaking process

[0177] Recycled polyethylene-rich polyolefins are introduced into the extruder through a feed zone. The feed zone introduces the recycled polyethylene-rich polyolefins into the melt zone. Typically, the feed zone consists of a feed hopper and a connecting pipe that connects the feed hopper to the melt zone. The polymer typically flows through the feed zone under gravity, i.e., it usually flows downwards.

[0178] The residence time of recycled polyethylene-rich polyolefins (and other components) in the feed zone is typically short, usually not exceeding 30 seconds, more often not exceeding 20 seconds, such as not exceeding 10 seconds. Typically, the residence time is at least 0.1 seconds or at least 1 second.

[0179] Melt zone for the visbreaking process

[0180] Recycled polyethylene-rich polyolefin enters the melting zone from the feed zone. In the melting zone, the recycled polyethylene-rich polyolefin melts. The recycled polyethylene-rich polyolefin is conveyed by the resistance caused by the rotating screw. The temperature then rises along the length of the screw through the dissipation of frictional heat, reaching a level above the polymer's melting temperature. As a result, the solid particles begin to melt.

[0181] Preferably, the screw in the molten zone is designed such that the molten zone is completely filled. This results in a dense bed of solid particles within the molten zone. This occurs when sufficient pressure is generated in the screw channel and the screw channel is completely filled. Typically, the screw in the molten zone includes conveying elements with virtually no backflow. However, to achieve a dense bed, it may be necessary to install some barriers or backmixing elements in suitable locations, such as near the downstream end of the molten zone. Screw designs for achieving a dense particle bed are well-known in the extruder industry. Due to frictional heat, the temperature increases along the length of the screw, and the recycled polyolefin begins to melt.

[0182] Mixing zone for the visbreaking process

[0183] Following the melting zone, the regenerated polyethylene-rich polyolefin passes through a mixing zone. The screw in the mixing zone typically includes one or more mixing sections, which incorporate screw elements that provide a degree of recirculation. In the mixing zone, the polymer melt is mixed to obtain a homogeneous mixture. The mixing zone may also contain additional elements such as throttle valves or gear pumps.

[0184] The temperature in the mixing zone is higher than the melt temperature of the recycled polyolefin. Furthermore, this temperature needs to be higher than the decomposition temperature of the initiator. This temperature also needs to be lower than the decomposition temperature of the recycled polyolefin.

[0185] The total average residence time in the combined melting and mixing zones of the extruder can be at least about 25 seconds and / or at least about 30 seconds. Typically, the average residence time does not exceed 60 seconds or 55 seconds. Good results have been obtained when the average residence time is in the range of 30 to 45 seconds.

[0186] As discussed above, ideally, gaseous material is removed from the extruder via one or more discharge ports, sometimes referred to as exhaust ports. More than one discharge port may be used. For example, two ports may exist: an upstream port for coarse degassing and a downstream port for removing residual volatile material. This arrangement is advantageous if a large amount of gaseous material is present in the extruder.

[0187] The vents are suitably located in the mixing zone. However, they can also be located at the downstream end of the melting zone. In particular, if multiple vents are present, it is sometimes advantageous to have the upstream vent in the melting zone and the subsequent vents in the mixing zone. Stripping agents, such as water, steam, CO2, or N2, can also be added to the extruder.

[0188] When using this stripping agent, it is introduced upstream of the vent, or, when multiple vents exist, upstream of the most downstream vent and downstream of the upstream vent. Typically, the stripping agent is introduced into the mixing zone or at the downstream end of the melting zone.

[0189] The die area typically includes a template, sometimes called a perforated plate, which is a thick metal disc with multiple holes. These holes are parallel to the screw axis. Molten recycled polyolefin is extruded through the template. The molten recycled polyolefin thus forms many strands. These strands are then fed into a granulator. The function of the template is to prevent the helical movement of the recycled polyolefin melt and force it to flow in one direction. The die area may also include one or more screens, typically supported by the template. The screens are used to remove foreign material from the recycled polyolefin melt and to remove gel from the polymer. Gel is typically an undispersed high molecular weight polymer, such as a crosslinked polymer.

[0190] Radical initiator for the visbreaking process for preparing a polyolefin composition

[0191] The free radical initiator used in the method of the present invention is any free radical initiator known in the art. In one embodiment, the free radical initiator is a free radical initiator that decomposes at a high temperature (i.e., at least 200°C). This means that the self-accelerating decomposition temperature (SADT) of the initiator of the present invention is preferably at least 200°C. Therefore, the initiator is stable up to this temperature. Thus, the initiator typically does not begin to degrade until the polymer melt passes through the extruder, possibly reaching zone 3.

[0192] If an initiator that decomposes at low temperatures is used, the initiator will decompose too early or too quickly in this method, and the desired increase in MFR cannot be achieved. For example, peroxides quickly lose their activity, making them unsuitable for use in the method of this invention. Alternatively, it can be considered that the initiator is not a peroxide. Peroxide initiators typically decompose at temperatures too low for use in this invention.

[0193] Based on the amount of recycled polyolefin present, the free radical initiator may be present in the method of the present invention in amounts of at least 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt%, 1.1 wt%, 1.2 wt%, or 1.3 wt% and / or not exceeding 2.0 wt%, 1.9 wt%, 1.8 wt%, 1.7 wt%, 1.6 wt%, 1.5 wt%, or 1.4 wt%. In another embodiment of the invention, based on the amount of recycled polyolefin present, the free radical initiator may be from about 0.01 wt% to about 2.0 wt%, from about 0.02 wt% to about 2.0 wt%, from about 0.03 wt% to about 2.0 wt%, from about 0.04 wt% to about 2.0 wt%, from about 0.04 wt% to about 2.0 wt%, from about 0.05 wt% to about 2.0 wt%, from about 0.06 wt% to about 2.0 wt%, from about 0.07 wt% to about 2.0 wt%, from about 0.08 wt% to about 2.0 wt%, from about 0.09 wt% to about 2.0 wt%, from about 0.1 wt% to about 2.0 wt%, or from about 0.2 wt%. The amounts present in the method of the present invention are about 2.0 wt%, about 0.3 wt% to about 2.0 wt%, about 0.4 wt% to about 2.0 wt%, about 0.5 wt% to about 2.0 wt%, about 0.6 wt% to about 2.0 wt%, about 0.7 wt% to about 2.0 wt%, about 0.8 wt% to about 2.0 wt%, about 0.9 wt% to about 2.0 wt%, about 1.0 wt% to about 2.0 wt%, about 1.1 wt% to about 2.0 wt%, about 1.2 wt% to about 2.0 wt%, about 1.3 wt% to about 2.0 wt%, about 1.4 wt% to about 2.0 wt%, or about 1.5 wt% to about 2.0 wt%. In other embodiments, the amount of free radical initiator ranges from about 0.1 wt% to about 1 wt%, about 0.2 wt% to about 1.0 wt%, about 0.3 wt% to about 1.0 wt%, about 0.4 wt% to about 1.0 wt%, about 0.5 wt% to about 1.0 wt%, or about 0.6 wt% to about 1.0 wt%, depending on the amount of recycled polyolefin present. Therefore, if 100 g of recycled polyolefin is used, 0.1 g to 2.0 g of free radical initiator may be present. The above-mentioned amounts of free radical initiator are the total amount added. It should be understood that the free radical initiator may be added in batches or in separate batches in different parts of the extruder.

[0194] However, in one embodiment, all initiators are added at the beginning of the method. "Beginning of the method" means adding the free radical initiator along with the recycled polyolefin to the first zone of the extruder.

[0195] In one embodiment of the invention, a portion of the free radical initiator is added at the beginning of the extrusion method, and another portion is added later during the method. In this embodiment, the amount added at the beginning of the method is 30% to 70% by weight, 40% to 60% by weight, or about 50% by weight of the total amount of free radical initiator added. The amount added after the beginning of the method may be 30% to 70% by weight, 40% to 60% by weight, or 50% by weight of the total amount of free radical initiator added.

[0196] The free radical initiator added later in this method can be added to any later zone of the extrusion process, such as zone 4, zone 5, zone 6, or zone 7, particularly zone 6. In one embodiment of the invention, the extruder has 12 zones.

[0197] In another embodiment of the invention, the initial recycled polyolefin is metered into the main hopper of the extruder. The free radical initiator may be metered immediately into the first zone of the extruder, or metered simultaneously into the first and sixth zones based on half of its amount.

[0198] The amount of initiator added can be used to control the MFR of the viscous cracked recycled polyethylene-rich polyolefin in the final extrusion. Higher amounts of initiator tend to result in higher MFR values.

[0199] The radical initiator used in this invention is preferably not a peroxide. The initiator is at least one compound (E) capable of thermally decomposing into a carbobased radical by breaking at least one single bond (such as a carbon-carbon single bond or a carbon-hydrogen bond). The carbobased radical may have formula (I) or (II).

[0200]

[0201] In formula (I), each of R1, R2 and R3 may be independently selected from hydrogen, a straight-chain, branched or cyclic saturated or monounsaturated hydrocarbon having 1 to 12 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon having 6 to 12 carbon atoms, or a carboxylic acid ester group COOX, wherein X is a C1-C6-alkyl group, and thus at least one of R1, R2 and R3 is a substituted or unsubstituted aromatic hydrocarbon having 6 to 12 carbon atoms.

[0202] In formula (II), R4 and R6 are independently selected from hydrogen, substituted and unsubstituted straight-chain, branched and cyclic hydrocarbons having 1 to 12 carbon atoms, and substituted and unsubstituted aromatic hydrocarbons having 6 to 12 carbon atoms, and R5 is selected from substituted and unsubstituted straight-chain, branched and cyclic hydrocarbons having 1 to 12 carbon atoms, and substituted and unsubstituted aromatic hydrocarbons having 6 to 12 carbon atoms, wherein at least one of R4, R5 and R6 is a substituted or unsubstituted aromatic hydrocarbon having 6 to 12 carbon atoms.

[0203] Suitable carbon-based radicals of formula (I) or (II) are known, for example, from Chemicals Reviews, 2014, Vol. 114, p. 5013. Figure 1 Groups R1 to R61 are incorporated herein by reference to the extent that they do not contradict the statements herein. Each of R1 and R3 may be independently selected from hydrogen, substituted and unsubstituted straight-chain, branched and cyclic hydrocarbons having 1 to 12 carbon atoms, and substituted and unsubstituted aromatic hydrocarbons having 6 to 12 carbon atoms, and R2 may be selected from substituted and unsubstituted straight-chain, branched and cyclic hydrocarbons having 1 to 12 carbon atoms, and substituted and unsubstituted aromatic hydrocarbons having 6 to 12 carbon atoms.

[0204] As described above, at least one of groups R1, R2, and R3 or R4, R5, and R6 is a substituted or unsubstituted aromatic hydrocarbon having 6 to 12 carbon atoms. The carbohydrate radicals of formula (I) or (II) applicable to the present invention are therefore preferably generated from one or more compounds (E) of formula (III), wherein each of R1, R3, R4, and R6 is independently selected from hydrogen, substituted and unsubstituted straight-chain, branched, and cyclic hydrocarbons having 1 to 12 carbon atoms, and substituted and unsubstituted aromatic hydrocarbons having 6 to 12 carbon atoms, and each of R2 and R5 is independently selected from substituted and unsubstituted straight-chain, branched, and cyclic hydrocarbons having 1 to 12 carbon atoms, and substituted and unsubstituted aromatic hydrocarbons having 6 to 12 carbon atoms, and wherein at least one of R1, R2, R3, R4, R5, and R6 is a substituted or unsubstituted aromatic hydrocarbon having 6 to 12 carbon atoms.

[0205]

[0206] Compound (E) of formula (III) may have symmetrical and asymmetrical structures. Each of R2 and R5 is independently selected from substituted or unsubstituted aromatic hydrocarbons having 6 to 12 carbon atoms, or from substituted or unsubstituted aryl groups having 6 to 10 carbon atoms, and each of R1, R3, R4 and R6 is independently selected from hydrogen and C1-C6 alkyl groups.

[0207] In another embodiment, the initiator (E) has formula (IV).

[0208]

[0209] Each of R7, R8, R9 and R10 is independently selected from hydrogen atoms, C1-6 alkyl groups, C1-2 alkoxy groups, nitrile groups and halogen atoms, and each of R1, R3, R4 and R6 is independently selected from hydrogen and C1-6 alkyl groups.

[0210] In yet another embodiment, the initiator (E) is selected from 2,3-dimethyl-2,3-diphenylbutane, 2,3-dipropyl-2,3-diphenylbutane, 2,3-dibutyl-2,3-diphenylbutane, 2,3-dihexyl-2,3-diphenylbutane, 2-methyl-3-ethyl-2,3-diphenylbutane, 2-methyl-2,3-diphenylbutane, 2,3-diphenylbutane, 2,3-dimethyl-2,3-di-(p-methoxyphenyl)-butane, 2,3-dimethyl-2,3-di-(p-methylphenyl)-butane, 2,3-dimethyl-2-methylphenyl-3-(p-2'3'-dimethyl-3'-methylphenyl-butyl)-phenyl-butane, 3,4-dimethyl-3,4-diphenylhexane, 3,4-diethyl -3,4-diphenylhexane, 3,4-dipropyl-3,4-diphenylhexane, 4,5-dipropyl-4,5-diphenyloctane, 2,3-diisobutyl-2,3-diphenylbutane, 3,4-diisobutyl-3,4-5-diphenylhexane, 2,3-dimethyl-2,3-di(tert-butyl)-phenyl-butane, 5,6-dimethyl-5,6-diphenyldecane, 6,7-dimethyl-6,7-diphenyldodecane, 7,8-dimethyl-7,8-di(methoxyphenyl)-tetradecane, 2,3-diethyl-2,3-diphenylbutane, 2,3-dimethyl-2,3-di(p-chlorophenyl)butane, 2,3-dimethyl-2,3-di(p-iodophenyl)butane, and 2,3-dimethyl-2,3-di(p-nitrophenyl)butane.

[0211] In another embodiment, the initiator (E) is selected from 2,3-dimethyl-2,3-diphenylbutane and 3,4-dimethyl-3,4-diphenylhexane.

[0212] Final extruded polyolefin composition by the visbreaking process

[0213] Extruded, viscous-reduced, cracked, recycled polyethylene-rich polyolefins exiting the extruder have a higher molecular weight flow rate (MFR) and a lower molecular weight than recycled polyolefins. Extruded, viscous-reduced, cracked, recycled polyethylene-rich polyolefins can have an MFR of at least 4 g / 10 min. The increase in MFR of extruded, viscous-reduced, cracked, recycled polyethylene-rich polyolefins can be at least 3 times (i.e., 3 × or 200%) higher than that of recycled polyolefins. In other embodiments, extruded, viscous-reduced, cracked, recycled polyethylene-rich polyolefins can have an MFR at least 4 times (300%) higher, at least 4.5 times (350%) higher, or at least 5 times (400%) higher than that of the initial recycled polyolefin.

[0214] When the initial MFR of the recycled polyethylene-rich polyolefin is low (e.g., less than 10 g / 10 min), the increase in the MFR of the extruded, viscous-reduced, cracked recycled polyethylene-rich polyolefin may be even more significant. Therefore, in embodiments of the invention, the increase in the MFR of the extruded, viscous-reduced, cracked recycled polyethylene-rich polyolefin can be 10 times (900%) or more, 12 times (1100%) or more, 13 times (1200%) or more, 14 times (1300%) or more, 15 times (1400%) or more, or 20 times (1900%) or more. The MFR value of the extruded, viscous-reduced, cracked recycled polyethylene-rich polyolefin, regardless of the initial recycled polyolefin, can be at least 8 g / 10 min, at least 10 g / 10 min, at least 20 g / 10 min, at least 25 g / 10 min, or at least 50 g / 10 min. The MFR value of extruded, viscous cracked, recycled polyethylene-rich polyolefins can be 100 g / 10 min or greater.

[0215] The extruded, viscous-reduced, cracked, recycled polyethylene-rich polyolefin material did not exhibit a significant amount of crosslinking. The degree of crosslinking of the extruded, viscous-reduced, cracked, recycled polyethylene-rich polyolefin may be less than 0.5% by weight (as explained in the examples, determined by XHU), less than 0.4% by weight, or less than 0.3% by weight. In some embodiments, the crosslinking may be 0.1% by weight or less, or 0.05% by weight or less.

[0216] The density of extruded, viscous cracked, recycled polyethylene-rich polyolefins (also known as viscous cracked polymers) remains essentially unchanged. Extruded, viscous cracked, recycled polyethylene-rich polyolefins can be LDPE with a density of 910 kg / m³ to 1000 kg / m³ or 915 kg / m³ to 985 kg / m³, MDPE with a density of 926 kg / m³ to 940 kg / m³, or HDPE with a density of 855 kg / m³ to 980 kg / m³.

[0217] It is also worth noting that the Mw / Mn values ​​of the extruded, viscous cracked, recycled polyethylene-rich polyolefins appear to remain unchanged. Therefore, the post-extrusion Mw / Mn range can be from 1.5 to 4.0. The pre-extrusion values ​​listed above also apply to the post-extrusion recycled polyolefins.

[0218] The melting point of the viscous cracked recycled polyolefin (measured by DSC according to ISO 11357-1) may be below 100°C, below 90°C, or below 85°C. In one embodiment of the invention, the melting point of the ethylene copolymer, such as LLDPE, is 120°C or lower.

[0219] Because the extruded, viscous-reduced, cracked, recycled polyethylene-rich polyolefins of this invention originate from a viscous cracking method rather than directly from a polymerization method, the extruded, viscous-reduced, cracked, recycled polyethylene-rich polyolefins may contain residues derived from the initiator. For example, when the initiator is one of the above formulas (III), free radicals are generated via the splitting of C-C bonds, leaving free radical groups R1R2R3C and R4R5R6C. When these free radicals acquire protons, the resulting compounds can be detected as impurities in the final polymer. Detection methods include NMR. The detection of these compounds confirms that, unlike direct synthesis, the extruded, viscous-reduced, cracked recycled polymer originates from viscous cracking.

[0220] Groups R1R2R3C or R4R5R6C can also be attached to the polymer chain.

[0221] If desired, the extruded, viscous, cracked, recycled polyethylene-rich polymer may have additional additives added to it; however, this is usually not necessary. Various amounts of additives, such as pigments, nucleating agents, antistatic agents, fillers, antioxidants, etc., may be present.

[0222] The tack-reduced cracked recycled polyethylene-rich polyolefin is then melt-blended to form an extruded tack-reduced cracked polyolefin composition comprising (A) about 60% to about 96% by weight of the extruded tack-reduced cracked recycled polyethylene-rich polyolefin; (B) about 2% to about 20% by weight of at least one random α-olefin copolymer; (C) optionally about 2% to about 20% by weight of at least one tackifier; and (D) optionally at least one additional polymer; wherein the polyolefin composition has a weight ratio of random α-olefin copolymer to tackifier between about 0.2 and about 5.0; and wherein the polyolefin composition has a melt flow rate increase of about 5% to about 1500% compared to an unextruded, non-tack-reduced cracked recycled polyolefin, and wherein the extruded tack-reduced cracked polyolefin composition has a melt flow rate increase of about 5% to about 400% compared to an identical extruded tack-reduced cracked polyolefin composition without melt blending of random α-olefin copolymer, optional tackifier resin, and additional polymer. The melt blending step, as well as the random α-olefin copolymer and the tackifier, have been previously discussed in this disclosure. In at least one embodiment of the invention, the polyolefin composition comprises a recycled polyethylene-rich polyolefin (A) subjected to a tack-reducing cracking process that results in reduced notched impact strength, at least one random α-olefin copolymer (B), optionally at least one tackifier (C), and optionally at least one additional polymer (D), wherein the percentage of B+D is about 10% to about 30% by weight or about 10% to about 20% by weight based on the weight of the total polyolefin composition; wherein the weight ratio of B to D is between about 0.3 to about 3.0 or about 0.2 to about 2.0; and wherein the extruded tack-reducing cracked polyolefin composition has an MFR increase of about 5% to about 100% and a notched impact strength increase of about 5% to about 200% compared to the same extruded tack-reducing cracked polyolefin composition without melt blending of random α-olefin copolymer, optional tackifier resin, and additional polymer; and wherein the extruded tack-reducing cracked polyolefin composition maintains acceptable mechanical properties.

[0223] In at least one embodiment of the invention, the polyolefin composition comprises a recycled polyethylene-rich polyolefin (A) subjected to a viscous cracking process that results in reduced notched impact strength, at least one random α-olefin copolymer (B) having a glass transition temperature equal to or below -10°C (ASTM D 3418-15) and a nominal molecular weight equal to or below 25,000 g / mol (ISO 16014), and optionally a glass transition temperature equal to or above 45°C (ASTM D 3418-15). The composition comprises at least one tackifier (C) of 3418-15, and optionally at least one additional polymer (D), wherein the percentage of B+D is from about 10% to about 30% by weight or from about 10% to about 20% by weight based on the weight of the total polyolefin composition; wherein the weight ratio of B to D is between about 0.3 to about 3.0 or from about 0.2 to about 2.0; and wherein, compared with the same extruded, tack-reduced, cracked polyolefin composition without melt blending of random α-olefin copolymer, optionally tackifier resin and additional polymer, the extruded, tack-reduced, cracked polyolefin composition has an increase of about 5% to about 100% in MFR and an increase of about 5% to about 200% in notched impact strength; and wherein the extruded, tack-reduced, cracked polyolefin composition maintains acceptable mechanical properties.

[0224] In at least one embodiment of the invention, a polyolefin composition is provided comprising a polyethylene-rich recycled polyolefin (A) extruded by a tack-reducing cracking method that results in reduced notched impact strength, at least one random α-olefin copolymer (B), optionally at least one tackifier (C), and optionally at least one additional polymer (D), wherein the additional polymer may be, but is not limited to, linear low-density polyethylene, medium-density polyethylene, ethylene-methyl acrylate copolymer, ethylene-hexene copolymer, ethylene-butene copolymer, or ethylene-octene copolymer, wherein the extruded tack-reducing cracked polyolefin composition is prepared by... Based on the weight of the total polyolefin composition, the percentage of B+D is from about 10% to about 30% by weight, more preferably from about 10% to 20% by weight, and wherein the weight ratio of B to D is between 0.3 and 3.0, more preferably between 0.2 and 2.0; and wherein, compared with the same extruded tack-reducing cracked polyolefin composition without random α-olefin copolymers, optional tackifying resins and other polymers, the extruded tack-reducing cracked polyolefin composition has an increase of about 5% to about 100% in MFR and an increase of about 5% to about 200% in notched impact strength, and wherein the polyolefin composition maintains acceptable mechanical properties.

[0225] In at least one embodiment of the invention, a polyolefin composition is provided comprising a polyethylene-rich recycled polyolefin (A) subjected to a viscous cracking process that results in reduced notched impact strength, at least one random α-olefin copolymer (B) having a glass transition temperature equal to or below -10°C (ASTM D 3418-15) and a nominal molecular weight equal to or below 25,000 g / mol (ISO 16014), and optionally a glass transition temperature equal to or above 45°C (ASTM D 3418-15). The extruded, tack-reducing, cracked polyolefin composition comprises at least one tackifier (C), (C), and optionally at least one additional polymer (D), wherein the additional polymer may be, but is not limited to, linear low-density polyethylene, medium-density polyethylene, ethylene methyl acrylate copolymer, ethylene-hexene copolymer, ethylene-butene copolymer, or ethylene-octene copolymer, wherein the extruded, tack-reducing, cracked polyolefin composition is prepared in a manner that, based on the weight of the total polyolefin composition, has a percentage of B+D of about 10% to about 30% by weight, more preferably about 10% to 20% by weight, and wherein the weight ratio of B to D is between 0.3 and 3.0, more preferably between 0.2 and 2.0; and wherein, compared with the same extruded, tack-reducing, cracked polyolefin composition without random α-olefin copolymer, optional tackifier resin, and additional polymer, the extruded, tack-reducing, cracked polyolefin composition has an increase of about 5% to 100% in MFR and an increase of about 5% to about 200% in notched impact strength, and wherein the extruded, tack-reducing, cracked polyolefin composition maintains acceptable mechanical properties.

[0226] In at least one aspect of this embodiment, the extruded tack-reducing cracked polyolefin composition exhibits an increase of about 5% to 100% in MFR and an increase of about 5% to 100% in yield elongation, while maintaining acceptable mechanical properties, compared to the same extruded tack-reducing cracked polyolefin composition without random α-olefin copolymers, optional tackifier resins and other polymers.

[0227] In another aspect of this embodiment, the additional polymer (D) is a virgin polymer with graded melt flow rate (MFR < 1, measured at 190°C in 2.16 kg according to ISO 1133), and in yet another aspect of this embodiment, the additional polymer is a recycled polyolefin having a notched impact strength that is 100% to 1000% higher than that of the recycled polyethylene-rich polyolefin (A) after de-tack cracking.

[0228] In at least one embodiment, the polyolefin composition is prepared in a second process step following viscous cracking according to melt blending as previously discussed in this disclosure. After the viscous cracking step and before the melt blending step, the viscous cracked polyethylene-rich recycled polyolefin can be stored in the form of, but not limited to, granules, flakes, or powder, according to conditions known to those skilled in the art. In at least one embodiment, the viscous cracked polyethylene-rich polyolefin can be stabilized with additives known to those skilled in the art and stored in melt form.

[0229] In at least one other embodiment, the viscous-reduced, polyethylene-rich recycled polyolefin is fed directly into the melt blending process without intermediate storage. The melt blending process for achieving the extruded viscous-reduced, cracked polyolefin composition (which is carried out concurrently with the viscous-reducing process) can only be carried out when the viscous-reduced, polyethylene-rich recycled polyolefin has been sufficiently cooled (preferably below 250°C, more preferably below 220°C) to allow for proper feeding and melt blending. This melt blending method has been previously discussed in this disclosure.

[0230] In another specific aspect of this embodiment, the metering level of the random α-olefin copolymer and / or tackifier and / or other polymers in the extruded, viscous, cracked polyolefin composition can be metered by measuring the melt viscosity of the viscous, cracked polyethylene-rich recycled polyolefin using an online rheometer and adjusting the metering level based on the measured melt viscosity to achieve a target melt viscosity. Such online rheometers are available from companies such as Haake, Leistritz, and Brabender.

[0231] Applications

[0232] In another embodiment of the invention, an article comprising the polyolefin composition is provided. Articles include, but are not limited to, films (such as single-layer or multi-layer films for packaging, uniaxially oriented or biaxially oriented films, cast films, shrink films, outer packaging films, laminated films, extruded films for plastic bags, agricultural films, protective films for coating components or cell phone screens, protective packaging films, films for vertically formed filled sealable packaging, films for horizontally formed filled sealable packaging, building films for basement moisture barriers, sheets, extruded parts (such as mono-extruded profiles, co-extruded profiles and multi-extruded profiles, tubes, fibers and pipes, sheathed wires), injection-molded parts (such as battery boxes), blow-molded parts (such as rigid packaging, bottles and containers for passenger cars, food or personal care), thermoformed articles (such as deep-drawn containers or cups for home care, food or personal care), rotationally molded articles (such as sinks), woven and non-woven textiles, and foamed articles (such as gaskets). Other articles include carpets, flooring materials, roofing materials, composite materials (such as exterior covers), synthetic paper, and human... This disclosure pertains to turf, fibers, thermoplastic elastomers (such as TPO sheets or (external) molded articles), automotive parts (such as dashboards and window seals), computer parts, healthcare parts, building materials, home appliances, electronic parts, electrical parts, toys, and footwear parts. The membranes disclosed herein encompass any suitable membrane structure and membrane application. Specific end-use membranes include, for example, blown films, cast films, stretch films, stretch / cast films, stretch cling films, stretch tear-off films, machine-stretched packaging, shrink films, shrink wrap films, greenhouse films, laminates, and laminated films. Exemplary films are prepared using any suitable technique, such as those used for preparing blown, extruded, and / or cast stretch and / or shrink films. Multilayer films (or multiple layers of film) can be formed by any suitable method. The total thickness of the multilayer film can vary depending on the desired application. Sheets made from the compositions of this disclosure can be used to form containers. Such containers can be formed by thermoforming, solid-state pressure forming, stamping, and other forming techniques. Sheets can also be fanned to cover a base plate, wall, or other surface.

[0233] The compositions of the present invention can be formed into articles by one of several conventional methods and equipment known to those skilled in the art. Exemplary methods include, but are not limited to, casting, extrusion, extrusion coating, co-extrusion, extrusion foaming, compression molding, calendering, injection molding, thin-wall injection molding, low-pressure molding, direct injection expanded foam molding, compression molding, transfer molding, blow molding, rotational molding, or combinations thereof, such as post-extrusion thermoforming or biaxial orientation. Combinations of methods can be carried out online or as a method consisting of separate preparation steps that allow intermediate storage of semi-finished products (e.g., secondary orientation of extruded films). Articles can also be prepared by in-situ melting methods (such as heat-setting) or cold forming methods (also known as solid-state forming). Additionally, articles can be prepared by additive manufacturing methods, including but not limited to stereolithography (SLA), fusion deposition melting (FDM), selective laser sintering (SLS), multi-jet melting (MJF), vacuum casting, or combinations thereof.

[0234] The embodiments of the invention imply that the compositions described herein may also comprise virgin polyolefin polymers, and those skilled in the art can modify compositions comprising up to 96% by weight of a virgin polyolefin polymer based on the weight of the composition using this specification and the appended claims. The virgin polymer may be the same as (except for the source) as the primary polymer of a recycled polyolefin or a recycled polyolefin.

[0235] Examples

[0236] These and other aspects of the invention will be more fully understood by referring to the following embodiments, which are merely illustrative of preferred embodiments of the invention and should not be construed as limiting the invention.

[0237] The materials used in Examples 1 to 19 are shown in Table 1.

[0238] Table 1

[0239]

[0240] *PCR PE contains small percentages of polypropylene (<0.5%) and carbon black (<1.3%), as well as trace amounts of other polymers (<0.03% of polyvinyl chloride, polyethylene terephthalate, polycarbonate, polystyrene, acrylonitrile-butadiene-styrene, polyamide, and polyurethane).

[0241] The following explains the meaning of the symbols used in these embodiments, the units representing the variables mentioned, and the methods for measuring these variables.

[0242] Table 2 below provides the testing methods used for the data in these Examples 1 to 23.

[0243] Table 2

[0244]

[0245] *General test specimens were prepared by injection molding using an Engel Victory VC 300 / 80Tech pro injection molding machine (800kN clamping force and 35mm screw diameter) at a screw temperature distribution of 200°C to 230°C and a set mold cavity temperature of 25°C.

[0246] Examples 1 to 8 MB modified polyethylene rich PCR with tackifier or random alpha-olefin copolymer

[0247] The polyolefin composition comprises 89.9% to 99.9% by weight (MFR 0.8 (190°C, 2.16 kg)) of post-consumer polyethylene (PCR PE) and 0% to 2% by weight of fully hydrogenated hydrocarbon tackifier resin (Plastolyn). TM R1140), 0% to 5% by weight of amorphous poly-α-olefins (Aerafin) TM 17) and 0.1% by weight of antioxidant / stabilizer (Irganox) TM 1010 and Irgafos TM The polyolefin composition of 168) was prepared by mixing PCR PE with 50% virgin low-density polyethylene (MFR 22 (190°C, 2.16 kg)) in Plastolyn. TM Aerafin with R1140 masterbatch and 50% virgin low-density polyethylene (LDPE) masterbatch (MFR 22 (190°C, 2.16 kg)). TM 17 Amorphous polyalphaolefins and Irganox in powder form TM 1010 and Irgafos TM Following manual drying and blending, the masterbatch was compounded on a Leistritz twin-screw extruder at a screw temperature distribution of 145°C to 160°C and a screw speed of 170 rpm. The composition and properties of these examples are given in Tables 3 and 4. Following manual drying and blending, the masterbatch was compounded on a Leistritz twin-screw extruder at a screw temperature distribution of 85°C to 135°C and a screw speed of 170 rpm.

[0248]

[0249] The results in Table 3 demonstrate that the properties of the present invention are improved compared to those of PCR PE modified with only hydrogenated hydrocarbon resins or only amorphous poly-(α-)olefins in Comparative Examples 3 to 6. A single-dosage addition of the amorphous poly-(α-)olefin at the level required for a significant increase in MFR resulted in a decrease in yield tensile strength (Comparative Example 4), while a lower dosage addition did not show the desired increase in MFR (Comparative Example 3). A single-dosage addition of the hydrogenated hydrocarbon resin at the level required for a significant increase in MFR resulted in a decrease in simply supported beam impact strength (Comparative Example 6), while a lower dosage addition did not show the desired increase in MFR (Comparative Example 5). Compared to the comparative examples, the MFR, yield tensile strength, and simply supported beam impact strength results in Example 2 of the present invention show surprising and unexpected improvements when both hydrogenated hydrocarbon tackifier resin and amorphous poly-(α-)olefin are dosage-added.

[0250]

[0251] The results in Table 4 demonstrate that the properties of the present invention (Example 7) are improved compared to the calculated properties of PCR PE modified with hydrogenated hydrocarbon resin and amorphous poly-(α-)olefin (Calculated Example 8). The increase in MFR is higher than the calculated MFR based on the weight-average increase in MFR based solely on the addition of hydrogenated hydrocarbon resin or amorphous poly-(α-)olefin (Calculated Example 8). Unexpectedly, the yield strength is also higher than the expected yield strength in Calculated Example 8.

[0252] Examples 9 to 11 MB modified polypropylene rich PCR with tackifier resin or random alpha-olefin copolymer

[0253] The total weight of the polyolefin composition contains 80% to 100% post-consumer polypropylene (PCRPP) and 0% to 10% amorphous poly-α-olefin (Aerafin). TM 17) and 0% to 2% by weight of fully hydrogenated hydrocarbon tackifier resin (Plastolyn) TM The polyolefin composition (R1140) was prepared by mixing PCR PP with 50% by weight of virgin polypropylene in Aerafin. TM Plastolyn contains 17 masterbatch (MFR of 25 (230°C, 2.16 kg)) and 50% by weight of virgin polypropylene. TMR1140 masterbatch (MFR of 25 g / 10 min (230°C, 2.16 kg)) was manually dried and blended, then compounded on a Collin ZK25P twin-screw extruder at a screw temperature distribution of 150°C to 210°C and a screw speed of 250 rpm. The composition and properties of these examples are given in Table 5. After manual drying and blending, the masterbatch was compounded on a Leistritz twin-screw extruder at a screw temperature distribution of 120°C to 180°C and a screw speed of 130 rpm.

[0254] Table 5

[0255]

[0256] The results in Table 5 demonstrate that the properties of the present invention are improved compared to the modification of PCR PP with only amorphous poly-(α-)olefin in Example 11. The MFR is increased significantly compared to the MFR when only a metric amount of amorphous poly-(α-)olefin is added (Example 10).

[0257] Comparative examples 12 to 16 Random alpha-olefin copolymer in PCR PE

[0258] The total weight of the polyolefin composition comprises 80% to 95% post-consumer polyethylene (PCR PE) and 2.5% to 10% amorphous poly-α-olefin (Aerafin). TM 17) The comparative polyolefin composition was prepared by compounding on a Collin ZK25P twin-screw extruder at a screw temperature distribution of 150°C to 210°C and a screw speed of 200 rpm. The composition was prepared by manually drying and blending PCR PE with 50% by weight of virgin low-density polyethylene in Aerafin. TM After 17 masterbatch (MFR of 7.5 g / 10 min (190 °C, 2.16 kg) was manually dried and blended, it was then compounded with post-consumer polyethylene on a Leistritz twin-screw extruder at a screw temperature distribution of 85 °C to 135 °C and a screw speed of 170 rpm. This was done without the addition of Aerafin. TM In the case of 17 masterbatches, the preparation method is similar to that in Reference Example 12.

[0259]

[0260] The results in Table 6a support the linear hypothesis that the percentage of total stoichiometric addition relative to amorphous poly-(α-)olefins affects the variable (in Example 8).

[0261] Comparative examples 17 to 20 Tackifier resin in PCR PP

[0262] The total weight of the polyolefin composition comprises 80% to 95% by weight of polypropylene homopolymer (MoplenHP400H) and 5% to 20% by weight of fully hydrogenated hydrocarbon tackifier resin (Plastolyn). TM R1140) Comparative polyolefin compositions using 20% ​​Moplen HP400H Plastolyn TM R1140 masterbatch was dry-blended and prepared by compounding on a Coperion ZSK 18 co-rotating 18mm twin-screw extruder at a screw temperature distribution of 80°C to 190°C and a screw speed of 300 rpm. General test specimens were prepared by dry blending via injection molding using an Engel Victory VC 300 / 80Tech pro injection molding machine (800kN clamping force and 35mm screw diameter) at a screw temperature distribution of 200°C to 220°C and a set cavity temperature of 15°C. Plastronyn was not added. TM In the case of R1140 masterbatch, it was prepared similarly to Reference Example 17.

[0263]

[0264] The results in Table 6b support the linear hypothesis that the effect of the variable is relative to the total percentage of hydrogenated hydrocarbon resin added (in Example 8).

[0265] The materials used in Examples 21 to 23 are shown in Table 7.

[0266] Table 7

[0267]

[0268] *PCR PE contains small percentages of polypropylene (<0.5%) and carbon black (<1.3%), as well as trace amounts of other polymers (<0.03% of polyvinyl chloride, polyethylene terephthalate, polycarbonate, polystyrene, acrylonitrile-butadiene-styrene, polyamide, and polyurethane).

[0269] Comparative example 21 Extrusion of PCR PE

[0270] The compound containing 100% post-consumer polyethylene (PCR PE, 0.8 MFR) was prepared by compounding on a Collin ZK 25ELD 42 twin-screw extruder at a screw temperature distribution of 250°C to 350°C and a screw speed of 150 rpm.

[0271] Comparative example 22 Visbreaking of PCR PE

[0272] The compound containing 99.9% post-consumer polyethylene (PCR PE, 0.8 MFR) and 0.1% 2,3-dimethyl-2,3-diphenylbutane (free radical initiator) was prepared by manually drying the PCR PE and free radical initiator, followed by compounding on a Collin ZK 25E LD 42 twin-screw extruder at a screw temperature distribution of 250°C to 350°C and a screw speed of 150 rpm.

[0273] Example 23 Visbroken rPE modified with random alpha-olefin copolymer

[0274] Contains 79.7% of Comparative Example 22 and 10% of amorphous poly-α-olefin (Aerafin). TM 17) and 0.3% antioxidant / stabilizer (Irganox) TM 1010 and Irgafos TM The compound of 168) was prepared by mixing Comparative Example 22 with 50% virgin low-density polyethylene in Aerafin. TM Irganox 17 masterbatch (MFR 7.5 (190°C, 2.16 kg)) and 75% calcium stearate. TM 1010 and Irgafos TM 168 masterbatch (1:2 ratio of Irganox) TM 1010 and Irgafos TM 168) After manual drying and blending, Aerafin was compounded on a Collin ZK 25E LD 42 twin-screw extruder at a screw temperature distribution of 145°C to 170°C and a screw speed of 20 rpm. After manual drying and blending, Aerafin was compounded on a Leistritz twin-screw extruder at a screw temperature distribution of 120°C to 180°C and a screw speed of 130 rpm. TM 17. Masterbatch.

[0275] Table 8

[0276]

[0277] The results in Table 8 demonstrate that the properties of the present invention (Example 23) are improved compared to PCR PE modified by high-temperature extrusion (Comparative Example 21) or by high-temperature extrusion (thickness reduction cracking) in the presence of a free radical initiator (Comparative Example 22). Modification with amorphous poly-α-olefin (thickness reduction cracking) after high-temperature extrusion in the presence of a free radical initiator resulted in an MFR that was 62.9% higher than that of high-temperature extrusion in the presence of a free radical initiator alone, and an MFR that was 430% higher than that of high-temperature extrusion without a free radical initiator. Compared to the original unmodified PCR PE, Example 23 of the present invention exhibited an MFR that was 1160% higher.

[0278] The materials used in Examples 24 to 51 are shown in Table 9.

[0279] Table 9

[0280]

[0281] *PCR PE2 contains small percentages of polypropylene (<0.5%), CaCO3 (<1.5%), and inorganic pigments (<0.5%), as well as trace amounts of other polymers (<0.03% of polyvinyl chloride, polyethylene terephthalate, polycarbonate, polystyrene, acrylonitrile-butadiene-styrene, polyamide, and polyurethane).

[0282] Table 10 below provides the testing methods for the data used in Examples 24 to 51.

[0283] Table 10

[0284]

[0285]

[0286] *The general test specimens are prepared by injection molding using a Toyo injection molding machine (90 tons clamping force and 32 mm screw diameter) at a screw temperature distribution of 170°C to 195°C and a set mold cavity temperature of 20°C.

[0287] Example 24 PCR PE composition prepared using masterbatch

[0288] Three masterbatches (MBs) were compounded on a 40 mm diameter, 40 / 1 L / D Werner Pfleiderer twin-screw extruder at the compositions, screw temperature distributions, and screw speeds listed in Table 11. During the masterbatch process, two feeders for the random α-olefin copolymer or tackifier resin and the carrier polymer were used in the main hopper.

[0289] Table 11. Composition and processing conditions of the PE masterbatch (MB) used in examples 24 to 34 .

[0290]

[0291]

[0292] The polyolefin composition contains 90% by weight of post-consumer polyethylene (PCR PE2) and 5% by weight of fully hydrogenated hydrocarbon tackifier resin (Eastotac). TM H-142W) and 5% Dowlex TM The 2045G LLDPE carrier polyolefin composition is obtained by combining it with 50% of the previously described virgin Dowlex. TM Eastotac with 2045G linear low-density polyethylene carrier TM H-142W tackifier resin masterbatch (MFR 1.0, 190°C, 2.16 kg) was obtained by manual drying and blending. The blend was injection molded using a 90-ton Toyo injection molding machine at a barrel temperature distribution of 170°C to 195°C and a mold cavity temperature of 20°C.

[0293] Examples 25 to 34 PCR PE composition prepared using masterbatch

[0294] The polyolefin compositions of Examples 25 to 34 were prepared as in Example 24, and their composition and properties are shown in Tables 12 and 13. Reference Example 30 was also prepared as in Example 24, but without the addition of random α-olefin copolymers or tackifying resins.

[0295] All examples demonstrate an increase in MFR measured at 190°C and 2.16 kg. Analysis of the data and composition shows that the LLDPE carrier, random α-olefin copolymer, and tackifier resin all contribute to improving the MFR. However, surprisingly, the increase in the weight percentage of each component is not linear.

[0296] Compared to the original PCR in Reference Example 30, Example 31 of the present invention, containing 5% by weight of each of Aerafin 17 and Eastotac H-142W, showed a surprising 289% increase in elongation, while Comparative Example 28, with 5% Aerafin 17, achieved a 104% increase in elongation, and Comparative Example 24, with 5% Eastotac H-142W resin, achieved only a 49% increase in elongation.

[0297] Compared to the original unmodified PCR in Reference Example 30, Example 34 of the present invention, which added 5% Plastolyn R1140 to the composition of Comparative Example 29, showed a surprising 526% increase in elongation, while Example 29 obtained an elongation increase of 299% with 10% Aerafin 17, and Comparative Example 27 obtained an elongation increase of only 93% with 10% resin Plastolyn R1140.

[0298] Compared to the original PCR in Reference Example 30, Example 33 of the present invention, with the addition of 10% Eastotac H-142W to the composition of Example 28, showed a surprising 589% increase in elongation, while Example 28 achieved a 104% increase in elongation with 5% Aerafin 17, and Example 25 achieved only a 130% increase in elongation with 10% resin Eastotac H-142W. This increase in MFR and elongation resulted in a more favorable balance of MFR and physical properties than using the tackifier resin alone or the random α-olefin copolymer alone.

[0299] Comparative Examples 24 through 27 illustrate that adding only hydrogenated hydrocarbon resin to the LLDPE carrier resin results in a reduction of up to 84% in the impact strength of notched cantilever beams. These compositions contain up to 20% LLDPE.

[0300] Although the notched cantilever beam impact value at room temperature could not be measured on dog bones due to the very high flexibility of the LLDPE carrier, it was surprisingly found that Examples 28-29 and Examples 31-34 of the present invention, containing up to 45% polyolefin composition of LLDPE, exhibited improved notched cantilever beams compared to the original PCR PE in Reference Example 30. The notched cantilever beams of the examples containing only random α-olefin polymers (Comparative Examples 28 and 29) were 45% and 142% higher than the original PCR (Reference Example 30), respectively, while the notched cantilever beam values ​​of Examples 31-34 of the present invention were 38% to 159% higher than the original PCR.

[0301] Other polymers can be similarly incorporated into the masterbatch composition to improve the impact resistance or other physical properties of the final composition.

[0302]

[0303]

[0304] Example 35 Post-consumer polyolefin rich in polypropylene modified via masterbatch

[0305] Preparation of the PP masterbatch used in examples 35 to 44

[0306] Masterbatch (MB) was formulated on a 40 mm diameter, 40 / 1 L / D Werner & Pfleiderer twin-screw extruder at the screw temperature distribution and screw speed listed in Table 14. During the masterbatch process, two feeders for random α-olefin copolymers or tackifier resins and carrier polymers were used in the main hopper.

[0307] Table 14. Composition and processing conditions of the PP masterbatch (MB) used in examples 35 to 44 .

[0308]

[0309] The polyolefin composition contains 80% by weight of a polypropylene-rich post-consumer polyolefin (PCR PP) and 10% by weight of a fully hydrogenated hydrocarbon resin (Eastotac). TM H-142W) and 10% by weight of Pinnacle TM The polyolefin composition of 1112 carrier (MFR 12g / 10min, 230°C, 2.16kg) was synthesized by combining with 50% of the previously described native Pinnacle. TM Eastotac 1112 polypropylene carrier TM H-142W fully hydrogenated hydrocarbon resin masterbatch (MFR 12.0 (230°C, 2.16 kg)) was obtained by manual drying and blending. The blend was injection molded on a 90-ton Toyo injection molding machine at a barrel temperature distribution of 170°C to 195°C and a mold cavity temperature of 20°C.

[0310] Examples 36 to 44 Post-consumer polyolefin rich in polypropylene modified via masterbatch

[0311] The polypropylene-rich polyolefin compositions of Examples 36 to 44 were prepared as in Example 35, and their compositions and properties are shown in Tables 15 and 16. Reference Example 39 PCR PP was prepared without the addition of random α-olefin copolymers or tackifying resins.

[0312]

[0313]

[0314] Example 43 of the present invention demonstrates that adding 5% Plastolyn R1140 resin to the composition of Comparative Example 38 resulted in a 31% higher MFR than the unmodified PP PCR (Reference Example 39), which is twice the percentage improvement obtained from adding only 5% Plastolyn R1140 in Comparative Example 36. The present invention also exhibits unexpectedly higher flexural strength (39%) and flexural modulus (84%) than the values ​​of the unmodified PP PCR; these values ​​are also greater than those of Comparative Example 38 containing only 5% Aerafin 17APO.

[0315] Example 44 of this invention combines 10% Plastolyn R1140 resin with 5% Aerafin 17APO, resulting in even greater increases in MFR (58%), flexural strength (45%), and flexural modulus (104%) compared to the unmodified PP PCR. Surprisingly, Young's modulus also increases (15%) higher than that of the unmodified PP PCR (refer to Example 39) and Comparative Example 38. The surprisingly improved properties of Examples 43 and 44 of this invention result in a more favorable balance of MFR and physical properties than using the tackifier resin alone or the random α-olefin copolymer alone.

[0316] Example 42 of the present invention, containing 5% Eastotac H-142W resin and 10% Aerafin 17APO, exhibited a higher MFR than Comparative Example 41, which contained only 10% Aerafin 17APO. Furthermore, the present invention surprisingly showed an elongation at break 152% greater than unmodified PCR PP, while maintaining other physical properties. The elongation at break of the present invention was also greater than that of Comparative Examples 41 and 35, which contained only equal amounts of random α-olefin copolymer or only equal amounts of tackifier resin.

[0317] Examples 45 to 51 PCR PE composition prepared by direct addition

[0318] Dry blends without masterbatch were fully compounded on an 18 mm diameter, 40 / 1 L / D Leistritz twin-screw extruder at the screw temperature profiles and screw speeds listed in Table 17. During the full compounding process, a dry blend mixture for atactic α-olefin copolymers and / or tackifier resins, along with a raw material feeder for PCR PE2, was used in the main hopper.

[0319] Test samples were prepared by injection molding on a 90-ton Toyo injection molding machine at a barrel temperature distribution of 170°C to 195°C, a screw diameter of 32 mm, and a mold cavity temperature of 20°C.

[0320]

[0321] Examples 45 through 51 increased the MFR of the blend by 49% to 114% compared to Example 45, and increased the elongation at break of the blend by 4% to 70% compared to the elongation of the unmodified reference Example 45. Surprisingly, Examples 47, 49, and 51 of the present invention, comprising both the tackifier resin and the amorphous poly-α-olefin, significantly increased the elongation at break, exceeding the elongation obtained when only the amorphous poly-α-olefin was added to the unmodified PCR PE2. For example, Example 47 exhibited 70% higher elongation than the unmodified PCR PE compared to the 19% increase in elongation obtained in Comparative Example 46, and Example 49 of the present invention had 41% higher elongation than the unmodified PCR PE compared to the 4% increase in elongation in Comparative Example 48. The unexpected interaction between the tackifier resin, the random α-olefin copolymer, and the PCR all improved the rheological properties (flowability) of the PCR and provided the ability to balance the physical properties of the polyolefin composition according to the needs of the target application.

[0322] Surprisingly, the standard deviation of the modified PCR samples was significantly lower than that of the unmodified PCR samples. This significant reduction in test variation indicates that the modified PCR polyolefin compositions have a more consistent composition and quality than the unmodified PCR.

[0323] Table 18

[0324]

[0325] Other materials used in the following examples are listed in Table 19 below. The test methods used are listed in Table 2.

[0326] Table 19

[0327]

[0328] Examples 52 to 56 Visbroken rHDPE modified with MB containing random alpha-olefin and ethylene-1-octene or ethylene-1-hexene MDPE polyolefin polymer Table 20. MB composition used in examples 53 to 56

[0329] After manually drying the blending components, two masterbatches were prepared on a Leistritz twin-screw extruder at a screw temperature distribution of 135°C to 165°C and a screw speed of 150 rpm.

[0330] Masterbatch MB1 uses 50% by weight of Elite from DOW TM 5940ST, medium-density graded melt C8 reinforced polyethylene resin (MDPE) and 50% by weight Aerafin TM 180. Preparation of propylene-ethylene amorphous random copolymer.

[0331] Masterbatch MB2 uses 50% by weight of Enable from Exxon Mobile TM 4009MC Blown, medium-density graded melt ethylene-1-hexene copolymer and 50% by weight Aerafin TM 180. Preparation of propylene-ethylene amorphous random copolymer.

[0332] Table 21: Composition examples 52 to 56 in wt%

[0333]

[0334] Both MB1 and MB2 are used to modify recycled polyethylene-rich HDPE streams (PCR PE) that exhibit reduced impact strength due to exposure to viscosity degradation (thickness reduction cracking) methods (induced chain scission in the presence of free radical initiators) and elevated temperatures (e.g., above 320°C). This method reduces the notched impact strength of simply supported beams in thickened, viscosity-reduced recycled HDPE (refer to Example 52) from 35.8 kJ / m. 2 Reduced to 4.1 kJ / m 2 (ISO 179-1).

[0335] Using a Collin ZK25P twin-screw extruder, 10 wt% or 20 wt% of MB1 or MB2 were compounded into the reduced-thickness cracked recycled HDPE at a screw temperature distribution of 145°C to 170°C and a screw speed of 200 rpm. The resulting polyolefin composition was used to prepare injection-molded test bars to evaluate MFR, tensile properties, and notched impact strength. Tables 21 and 22 below list the composition and measured properties.

[0336] Table 22: Measured properties of composition examples 52 to 56

[0337]

[0338] Examples 57 to 63 Visbroken r-HDPE modified with random alpha-olefin and MDPE via direct metering addition

[0339]

[0340]

[0341] Compared to the unmodified reference, Examples 53 to 56 of the present invention show an increase of 30% to 90% in impact strength of notched simply supported beams, and at the same time, Examples 53 to 56 of the present invention show an increase of 25% to 50% in MFR, both of which are caused by the combination of graded melt MDPE and low viscosity amorphous polyolefin.

[0342] Examples 64 to 67 Visbroken PCR PE modified with random alpha-olefin and ethylene- acrylic ester copolymer via masterbatch

[0343] Eltex, a linear medium-density polyethylene grade obtained from Ineos Olefins & Polymers (Rolle, Switzerland). TM HD3930UA and Aerafin, an amorphous random copolymer of propylene and ethylene obtained from Eastman Chemical (Kingsport, TN, USA). TM Combination 180 was used to modify recycled HDPE streams, which exhibited reduced impact strength due to exposure to viscosity-degrading (thickening cracking) methods (in the presence of free radical initiators) and elevated temperatures (e.g., above 320°C). This method reduced the notched impact strength of simply supported beams of thickened recycled HDPE from 35.8 kJ / m². 2 Reduced to 4.1 kJ / m 2 (ISO 179-1).

[0344] Using a Collin ZK25P twin-screw extruder, 20 wt%, 40 wt%, or 60 wt% of Eltex HD3930UA was blended alone or in combination with 5 wt% Aerafin 180 into the reduced-thickness cracked recycled HDPE at a screw temperature distribution of 145°C to 170°C and a screw speed of 200 rpm. Aerafin 180 was dried and blended with the reduced-thickness cracked recycled HDPE and added to the main hopper, while Eltex HD3930UA was added using the second feed hopper. Both were metered at the inlet of the mixer. The resulting polyolefin compositions were used to prepare injection-molded test bars to evaluate MFR, tensile properties, and notched impact strength. Tables 23 and 24 below list the blend compositions and measured properties.

[0345]

[0346] Table 24 shows that Comparative Examples 57 to 59, which contain additional polymers, reduced the MFR of the recycled polyolefin compositions by 12% to 24%, while improving notched impact strength and maintaining elongation. Examples 61 to 63 of the present invention show an unexpectedly greater improvement in impact performance based on the properties of additional MDPE polymers and random α-olefin copolymers, as well as a reduction in MFR due to the addition of lower MFR MDPE (e.g., Example 61 of the present invention compared to Comparative Example 57). The notched simply supported beam impact strength of Example 62 of the present invention is 15% higher than that of Comparative Example 58. In particular, the inventors were surprised to note that Example 61 of the present invention, which contains both additional polymers and random α-olefin copolymers, has an MFR equal to that of the unmodified, viscous cracked r-HDPE PCR PE of Reference Example 52 (14% higher than Comparative Example 57 which only contains additional polymers), a yield elongation 17% higher than that of Comparative Example 57, and a notched simply supported beam impact strength 28% higher than that of Comparative Example 57.

[0347] Table 25. Masterbatch 3 and masterbatch 4 compositions MB3

[0348] The first masterbatch (MB3) uses 50% by weight of medium viscosity ethylene acrylate copolymer (EMAC) from Westlake Chemicals (Houston, Texas, USA). TM SP2202 and 50% by weight of propylene-ethylene amorphous random copolymer (Eastman) Aerafin TM Preparation at 180°C. This MB was prepared on a 26mm twin-screw extruder manufactured by Coperion at 80°C to 190°C. ℃ The material is prepared at a processing temperature of 150 screw rpm. EMAC is precisely controlled using two separate feeders. TM SP2202 and Aerafin TM The feed rate is 180°, and the materials are fed through the main hopper. The total output obtained is 9 kg / hr.

[0349] The second masterbatch (MB4) is made from 50% by weight of medium-viscosity ethylene acrylate copolymer (EMAC) obtained from Westlake Chemicals. TM SP2205 and 50% by weight of Aerafin TM 180 was prepared using the same method.

[0350] MB4

[0351] EMAC SP2202 50 wt% EMAC SP2205 50 wt% Aerafin 180 50 wt% 50 wt% Table 26: Blend composition of examples 64 to 67 Table 27: Measured properties composition examples 64 to 67

[0352] MB3 and MB4 are used alone to modify recycled post-consumer HDPE streams (PCR PE) that exhibit reduced impact strength due to exposure to viscosity-breaking (thickness reduction cracking) methods (induced chain scission in the presence of free radical initiators) and exposure to elevated temperatures (e.g., above 320°C). This method reduces notched impact strength from 35.8 kJ / m. 2 Reduced to 4.1 kJ / m 2 (ISO179-1).

[0353] Using a Collin ZK25P twin-screw extruder, 10 wt% or 20 wt% of MB3 or MB4 were blended into reduced-thickness cracked recycled HDPE at a screw temperature distribution of 145°C to 170°C and a screw speed of 200 rpm. This blend was used to prepare injection-molded test bars to evaluate MFR, tensile properties, and notched impact strength. Table 26 lists the blend composition. Table 27 lists the measured properties of the prepared polyolefin compositions.

[0354] ​

[0355]

[0356] ​

[0357]

[0358] As can be seen in Table 27, the compositions of the present invention containing both ethylene-acrylate copolymers and random α-olefin copolymers (Examples 64 to 67 of the present invention) surprisingly all showed simultaneous increases in MFR and notched impact strength. Compared to the unmodified viscous cracked r-HDPE (PCR PE) of Reference Example 52, Example 56 of the present invention showed an increase in MFR of 51%, with a surprising increase in notched impact strength of 216%. In addition, the examples of the present invention also showed an unexpected increase in yield elongation of 20% to 34% compared to Reference Example 52.

Claims

1. A method for preparing a polyolefin composition, the method comprising: 1) Extruding at least one recycled polyolefin in the presence of at least one free radical initiator (E) to prepare extruded, viscous, cracked recycled polyolefin; And 2) melt blending (A) 60% to 96% by weight of the extruded recycled polyolefin; (B) 2% to 20% by weight of at least one random α-olefin copolymer; and (C) optionally 2% to 20% by weight of at least one tackifier; (D) optionally at least one other polymer; wherein the polyolefin composition has a weight ratio of random α-olefin copolymer to tackifier between 0.2 and 5.0; and wherein the extruded tack-reducing cracked polyolefin composition has a melt flow rate increase of 5% to 1500% compared to the recycled polyolefin; wherein the free radical initiator (E) has an auto-accelerated decomposition temperature (SADT) of at least 200°C and is selected from compounds capable of decomposing into carbon-based free radicals by breaking at least one single bond; wherein the tackifier includes polybutene, terpene resin, aliphatic hydrocarbon resin, or aromatic hydrocarbon resin.

2. The method according to claim 1, wherein the recycled polyolefin is at least one recycled polyolefin selected from post-consumer polyethylene-rich polyolefins, post-industrial polyethylene-rich polyolefins, ethylene plastomers, and ethylene elastomers; wherein the post-consumer polyethylene-rich polyolefin and the post-industrial polyethylene-rich polyolefin have a content of 910 kg / m³. 3 Up to 1050kg / m 3 The density of the ethylene plastic and the ethylene elastomer is 855 kg / m³. 3 Up to 960kg / m 3 The density.

3. The method according to claim 1, wherein the free radical initiator (E) is selected from 2,3-dimethyl-2,3-diphenylbutane, 2,3-dipropyl-2,3-diphenylbutane, 2,3-dibutyl-2,3-diphenylbutane, 2,3-dihexyl-2,3-diphenylbutane, 2-methyl-3-ethyl-2,3-diphenylbutane, 2-methyl-2,3-diphenylbutane, 2,3-diphenylbutane, 2,3-dimethyl-2,3-di-(p-methoxyphenyl)-butane, 2,3-dimethyl-2,3-di-(p-methylphenyl)-butane, 2,3-dimethyl-2-methylphenyl-3-(p-2'3'-dimethyl-3'-methylphenyl-butyl)-phenyl-butane, 3,4-dimethyl-3,4-diphenylhexane, 3,4-di-di-di-phenyl-butane, 2,3-dimethyl-2,3-diphenylbutane, 2,3-dimethyl-2,3-diphenylbutane, 2,3-dimethyl-2,3-diphenylbutane, 2,3-dimethyl-3'-diphenyl-butane, 2,3-dimethyl-2,3-diphenylbutane, 2,3-dimethyl-3'-diphenyl-butane, 2,3-diphenyl-2' ... The first one of ethyl-3,4-diphenylhexane, 3,4-dipropyl-3,4-diphenylhexane, 4,5-dipropyl-4,5-diphenyloctane, 2,3-diisobutyl-2,3-diphenylbutane, 3,4-diisobutyl-3,4-5-diphenylhexane, 2,3-dimethyl-2,3-di-p-(tert-butyl)-phenyl-butane, 5,6-dimethyl-5,6-diphenyldecane, 6,7-dimethyl-6,7-diphenyldodecane, 7,8-dimethyl-7,8-di(methoxyphenyl)-tetradecane, 2,3-diethyl-2,3-diphenylbutane, 2,3-dimethyl-2,3-di(p-chlorophenyl)butane, 2,3-dimethyl-2,3-di(p-iodophenyl)butane, and 2,3-dimethyl-2,3-di(p-nitrophenyl)butane.

4. The method of claim 1, wherein the metered addition level of the free radical initiator (E) is 0.1% to 2%.

5. The method according to claim 1, wherein the free radical initiator (E) is in the form of granules, particles, powders, flakes or combinations thereof, or wherein the free radical initiator is in the form of a masterbatch.

6. The method of claim 1, wherein the free radical initiator (E) is added at the start of the extrusion process, or wherein the free radical initiator (E) is partially added at the start of the extrusion process at 30% to 70% of the total metering level, and partially added after the extrusion process at 30% to 70% of the total metering level.

7. The method of claim 1, wherein the temperature in the combined melting and mixing zone of the extrusion method is greater than the SADT of the free radical initiator (E) and less than the decomposition temperature of the recycled polyolefin (A), and wherein the residence time in the combined melting and mixing zone is 25 to 60 seconds.

8. The method of claim 1, wherein the extrusion in the presence of a free radical initiator (E) is performed using an extruder having 10 to 14 zones, wherein the temperature of the highest zone is set to 250°C to 300°C.

9. The method of claim 8, wherein the highest zone temperature is applied by zone 3.

10. The method of claim 1, wherein the extruded, tack-reduced, cracked, recycled polyolefin is stored in the form of granules, pellets, flakes, or powders or combinations thereof prior to melt blending with the random α-olefin copolymer (B) and / or tackifier (C) to prepare the polyolefin composition.

11. The method of claim 1, wherein the extruded, viscous-reduced, cracked recycled polyolefin is fed directly into the melt blending process without intermediate storage.

12. The method according to claim 1, wherein the random α-olefin copolymer (B) and / or tackifier (C) are added simultaneously in a melt blending process after the extrusion of the recycled polyolefin (A) in the presence of a free radical initiator (E), wherein the extruded, tack-reduced, cracked recycled polyolefin has a melt temperature below 250°C when the random α-olefin copolymer (B) and / or tackifier (C) are metered in.

13. The method of claim 10, wherein the metered addition level of the random α-olefin copolymer (B) and / or tackifier (C) is metered by measuring the melt viscosity of the extruded, tack-reduced, cracked recycled polyolefin using an online rheometer.

14. The method of claim 1, wherein the recycled polyolefin (A), the random α-olefin copolymer (B), and the tackifier (C) are in the form of granules, particles, powders, flakes, or combinations thereof, wherein the granules, particles, powders, or flakes of the random α-olefin copolymer may be additionally coated or powdered with polyethylene wax, polypropylene wax, talc, or silica to improve processing.

15. The method of claim 1, wherein the extruded, viscous-reduced, cracked recycled polyolefin has an MFR at least 4 times higher than that of the starting recycled polyolefin.

16. The method of claim 1, wherein the additional polymer (D) is a virgin polymer having a graded melt, wherein the MFR is <1 as measured at 190°C in 2.16 kg according to ISO 1133, or the additional polymer is a recycled polyolefin having a notched impact strength 100% to 1000% higher than that of a recycled polyethylene-rich polyolefin (A) after de-tack cracking.

17. The method of claim 1, wherein the polyolefin composition comprises a recycled polyethylene-rich polyolefin (A) subjected to a tack-reducing cracking process that results in reduced notched impact strength, at least one random α-olefin copolymer (B), optionally at least one tackifier (C), and optionally at least one additional polymer (D), wherein the percentage of B+D is 10% to 30% by weight or 10% to 20% by weight based on the total weight of the polyolefin composition; wherein the weight ratio of B to D is between 0.3 and 3.0; and wherein the extruded tack-reducing cracked polyolefin composition has a 5% to 100% increase in MFR and a 5% to 200% increase in notched impact strength compared to the same extruded tack-reducing cracked polyolefin composition without the random α-olefin copolymer, optionally the tackifier resin, and the additional polymer; and wherein the extruded tack-reducing cracked polyolefin composition maintains acceptable mechanical properties.

18. The method of claim 1, wherein the polyolefin composition comprises a polyethylene-rich recycled polyolefin (A) extruded by a tackifying cracking process that results in reduced notched impact strength, at least one random α-olefin copolymer (B), optionally at least one tackifier (C), and optionally at least one additional polymer (D), wherein the additional polymer is selected from ethylene-hexene copolymers, ethylene-octene copolymers, ethylene-butene copolymers, ethylene-acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-methyl acrylate copolymers, ethylene-butyl acrylate copolymers, terpolymers of ethylene, ethyl acrylate, and maleic anhydride, MDPE, and HDP. E, LLDPE, LDPE, virgin PP homopolymer and PP copolymer, wherein the percentage of B+D is 10% to 30% by weight based on the total weight of the polyolefin composition, wherein the weight ratio of B to D is between 0.3 and 3.0; wherein the polyolefin composition has a 5% to 100% increase in MFR and a 5% to 200% increase in notched impact strength compared to the same polyolefin composition without the random α-olefin copolymer, optional tackifier resin and other polymers; wherein the extruded, tack-reduced, cracked polyolefin composition retains acceptable mechanical properties; and wherein the polyolefin composition further comprises one or more additives and / or fillers.

19. The method of claim 1, wherein the polyolefin composition has a 5% to 100% increase in MFR and a 5% to 100% increase in yield elongation compared to the same extruded, tackifying polyolefin composition without the random α-olefin copolymer, optional tackifying resin and additional polymer, while maintaining acceptable mechanical properties.

Images