Copolymers, Methods of Making Same, and Uses Thereof

Abstract

Copolymers and compositions thereof and polymer blends and methods of making and uses thereof. A copolymer comprises first group(s) comprising a plurality of groups independently formed from ethylenically unsaturated monomer(s) (such as, for example, olefin monomer(s) or the like) and second group(s) independently comprising a plurality of groups independently formed from ethylenically unsaturated monomer(s), where each second group is different from a first group and at least one of the second group(s) is covalently bonded to one or a plurality of first group(s). In various examples, a copolymer or copolymers is / are made by contacting two or more different polymers with one or more radical(s). In various examples, a method is an in situ polymer compatibilization method. A copolymer may be (or be suitable for use as) a thermoplastic material, a compatibilizer, or a thermoplastic elastomer.

Description

Attorney Docket No.: CRNL-118-B-WO COPOLYMERS, METHODS OF MAKING SAME, AND USES THEREOF CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 764,675, filed February 28, 2025, and entitled “Copolymers, Methods of Making Same, and Uses Thereof.” The entire contents of the above-identified priority application are hereby fully incorporated herein by reference in their entirety.STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH

[0002] This invention was made with government support under DE-AC02-07CH11358 awarded by the U.S. Department of Energy. The government has certain rights in the invention.BACKGROUND

[0003] Increasing plastic production and the associated waste generation necessitate improved recycling methods that are inexpensive, effective, and accessible. Low-density polyethylene (LDPE), high-density polyethylene (HDPE), and isotactic polypropylene (iPP) comprise about 57% of the total polymer waste produced annually. While innovative solutions for chemical recycling of these polyolefins are being developed, they mostly undergo mechanical recycling. Unfortunately, mechanical recycling leads to loss of material properties by chain degradation or crosslinking. Furthermore, HDPE and iPP are inherently difficult to separate by current sorting methods, resulting in immiscible HDPE / iPP blends. The immiscibility of HDPE and iPP stems from the high interfacial tension between the two homopolymers, leading to phase separation and poor mechanical properties. Lowering the interfacial tension between HDPE / iPP phases using a compatibilizer has emerged as a solution, improving miscibility and ultimately enhancing mechanical properties.

[0004] Compatibilization of immiscible polymers can be subdivided into two different categories: (1) addition of non-reactive copolymers or (2) reactive compatibilization of immiscible phases in situ. Commonly used copolymeric compatibilizers include ethylenepropylene random copolymers, ethyl ene / propylene diene monomer copolymers, and olefin block copolymers. Usually, 10 wt % of these copolymers relative to the polyolefin blend are required to achieve effective compatibilization. Recently, more effective compatibilization was achieved using well-defined copolymer architectures like linear multiblock copolymers, graft copolymers, or polyesters. These approaches enabled effective compatibilization at loadings as low as 1 wt % but required synthesis of new polymer architectures utilizingexpensive reagents and catalysts. Reactive compatibilization is an alternative approach in which chemical bonds are formed in situ between two immiscible polymer phases. The undefined copolymers generated at the interface serve as compatibilizers. These processes typically require highly reactive molecules like diaziridines, azides, ozone, anhydrides, or radicals with alkenes. Drawbacks of in situ compatibilization include the use of expensive chemicals with multi-step syntheses and high reagent loadings, limiting broad applicability.

[0005] Braun and coworkers previously investigated grafting reactions in melt and demonstrated some preliminary reactions in solution, but did not explore compatibilization. (“Peroxy-initiated chain degradation, crosslinking, and grafting in PP-PE blends,” J. Appl. Polym. Sci. 1998, 68, 2019-2028). Gloger and coworkers recently reported the synthesis of graft copolymers under melt extrusion conditions by reacting low-viscosity HDPE and iPP in the presence of a peroxide. (“Combining the Incompatible Melt State Grafting between High Density Polyethylene and Isotactic Polypropylene without a Coupling Agent,” ACS Appl. Polym. Mater. 2025, 6, 10824-10841). However, low yields of graft copolymer rendered this synthetic route unfeasible for large-scale synthesis of effective compatibilizers.SUMMARY OF THE DISCLOSURE

[0006] In various aspects and examples, the present disclosure describes copolymers and compositions thereof and polymer blends and uses thereof. Also described are methods of making copolymers and methods of making copolymer blends.

[0007] In an aspect, the present disclosure provides copolymers. In various examples, a copolymer is a compatibilizer or the like. In various examples, a copolymer, which may be a graft copolymer or the like, comprises one or more first group(s) (e.g., a segment or segments, which may be a first segment or first segments, or a backbone group or groups, or the like) comprising a plurality of groups (e.g., repeat units) independently formed from one or more ethylenically unsaturated monomer(s); and one or more second group(s) (e.g., a segment or segments, which may be a second segment or segments, or the like) independently comprising a plurality of groups (e.g., repeat units) independently formed from one or more ethylenically unsaturated monomer(s), where each second group is different from one or more first group(s), and where at least one or a plurality of second group(s) is covalently bonded to one or a plurality of first group(s). In various examples, the first group(s) is / are (or independently comprise) a polyolefin group or groups, a polyester group or groups, a polystyrene group or groups, or a structural analog or analogs thereof, or the like, or any combination thereof and / or the second group(s) is / are (or independently comprise) apolyolefin group or groups, a polystyrene group or groups, or a structural analog or structural analogs thereof, or the like, or any combination thereof. In various examples, the copolymer is suitable for use as a thermoplastic material, a compatibilizer, a thermoplastic elastomer, or the like, or any combination thereof.

[0008] In an aspect, the present disclosure provides polymer blends. In various examples, a polymer blend is a compatibilized blend. In various examples, a polymer blend comprises one or more copolymer(s) of the present disclosure and one or more polymer(s) (e.g., two or more polymers, such as, for example, a first polymer, a second polymer, etc.). In various examples, the polymers are independently chosen from polyolefins, polyesters, polybutadienes, polystyrenes, and structural analogs thereof, and the like, and copolymers comprising one or more thereof.

[0009] In an aspect, the present disclosure provides compositions. In various examples, a composition comprises one or more copolymer(s) of the present disclosure. In various examples, the composition further comprises one or more additive(s) (e.g., as described herein).

[0010] In an aspect, the present disclosure provides methods of making copolymers. In various examples, a method comprises contacting one or more (e.g., two or more) polymers, which may be referred to as precursor polymer(s), with one or more radical(s), and optionally, one or more additives and / or solvent(s); and optionally, heating the polymers, radical(s), and, if present, additive(s) and / or solvent(s). In various examples, a method is an in situ method (such as, for example, an in situ compatibilization method or the like). In various examples, a method comprises (or consists essentially of or consists of) a single step (such as, for example, a single copolymer production step or the like). In various examples, a method produces one or more copolymer(s) of the present disclosure. In various examples, the polymers are chosen from polyolefins (such as, for example, polyethylenes (e.g., high-density polyethylenes, low-density polyethylenes, medium-density polyethylenes, linear low-density polyethylenes, and structural analogs thereof, and the like), polypropylenes (such as, for example, isotactic polypropylenes, atactic polypropylenes, syndiotactic polypropylenes, and structural analogs thereof, and the like), polymethylpentenes, and structural analogs thereof, and the like), polybutadienes, polyesters (such as, for example, aliphatic polyesters (e.g., polycaprolactones, poly(3-hydroxybutyrate)s, long-chain aliphatic polyesters (such as, for example, PE- 18, 18, and structural analogs thereof, and the like), polystyrenes, copolymers of ethylene and propylene (such as, for example, ethylene-propylene rubbers, ethylene propylene diene monomer copolymers, and structural analogs thereof, and the like),polyolefin copolymers (such as, for example, styrene-butadiene-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, and structural analogs thereof, and the like), and structural analogs thereof, and the like, and combinations thereof. In various examples, the two or more polymers comprise (or are) an HDPE and an iPP. In various examples, the contacting one or more polymer(s) results in formation of a polymer or polymers comprising radical(s) (which can react with radical(s) of another polymer or polymers). In various examples, the method comprises macroradical recombination or the like.

[0011] In an aspect, the present disclosure provides compositions. In various examples, a composition is used (or is suitable for use in) a method of the present disclosure (such as, for example, a method of making a copolymer of the present disclosure or a method of making a polymer blend of the present disclosure). In various examples, a composition (which, in various examples, may be referred to as a polymer blend composition) comprises: two or more polymers; one or more radical source(s); and optionally, one or more quencher(s) and / or one or more solvent(s).

[0012] In an aspect, the present disclosure provides methods of making polymer blends. In various examples, a method of making a polymer blend comprises blending (such as, for example, solvent blending, melt blending, ball-milling, or the like, or any combination thereof) one or more copolymer(s) of the present disclosure, and two or more polymers. In various examples, a polymer blend (which may be a compatibilized polymer blend, such as, for example, a compatibilized polymer blend as described herein) is formed.

[0013] In an aspect, the present disclosure provides articles of manufacture. In various examples, an article of manufacture comprises one or more copolymer(s) of the present disclosure, one or more or all of which may be made by a method of the present disclosure, one or more polymer blend(s) of the present disclosure, one or more or all of which may be made by a method of the present disclosure, one or more composition(s) of the present disclosure, or any combination thereof. In various examples, an article of manufacture is chosen from containers (such as, for example, food storage containers, consumer product containers, water bottles (e.g., reusable water bottles and the like), and the like), plastic grocery bags, packaging, pipes, insulating panels, bathtubs, window panel doors, floors, tiles, syringes, petri dishes, specimen bottles, safety helmets, tendon prostheses, tracheal tubes, automobile components, electronic components, clothing (such as, for example, waterproof clothing, fiber form for clothing, and the like), carpets, non-stick pots and pans, eye-wear, CDs and DVDs, furniture, outdoor play equipment, toys, and the like.

[0014] In various examples, a method directly accesses copolymers, which may be graft copolymers or the like, formed from one or more ethylenically unsaturated monomer(s) (e.g., polyolefin copolymers, such as, for example, HDPE-g-iPP copolymers or the like), in a one-step radical recombination reaction from pre-existing polymers, such as, for example, polymers formed from one or more ethylenically unsaturated monomer(s) (e.g., polyolefins, such as, for example, HDPE, iPP, and the like) without any monomers and / or polymerization (e.g., catalysis or the like). In various examples, a copolymer or copolymers act(s) as compatibilizers for various ranges of polymer blends comprising polymers formed from one or more ethylenically unsaturated monomer(s) (e.g., polyolefins, such as, for example, HDPE, iPP, and the like) (e.g., HDPE / iPP blends) on loadings of about 2.5 to about 10 wt % relative to the polymer blend. Accordingly, a method can provide a simple, fast, scalable, economically viable, etc. new synthesis route to mixed polyolefin compatibilization additives.BRIEF DESCRIPTION OF THE FIGURES

[0015] For a fuller understanding of the nature and objects of the disclosure, reference should be made to the following detailed description taken in conjunction with the accompanying figures.

[0016] FIG.l shows radical-induced grafting of pre-existing homopolymers.

[0017] FIG. 2 shows radical reactivity of HDPE with polyethylene crosslinking.

[0018] FIG. 3 shows radical reactivity of iPP with polypropylene degradation by β-chain scission.

[0019] FIG. 4 shows radical reactivity of HDPE combined with iPP with synthesis of polyethylene-graft-polypropylene (HDPE-g-iPP) copolymers via macroradical recombination induced by a commonly used alkyl peroxide.

[0020] FIG. 5 shows average elongation at break of 70 / 30 HDPE / iPP blends with 10 wt % loading of HDPE-g-iPP copolymers after reaction times of 0 to 15 min (min = minute(s)) (0 - 12.8 t1 / 2, t1 / 2,180°C= 1.17 min).

[0021] FIG. 6 shows effects of reaction time on DSC (2nd heating cycle) of HDPE-g-iPP copolymers.

[0022] FIG. 7 shows effects of reaction time on SEC measurements of HDPE-g-iPP copolymers.

[0023] FIG. 8 shows effects of reaction time on oscillatory melt rheology frequency sweeps of HDPE-g-iPP copolymers.

[0024] FIG. 9 shows the effect of varying HDPE backbone chain length on DSC measurements (2nd heating) of HDPE-g-iPP prepared in a standard grafting reaction with different Mn,rel HDPEs.

[0025] FIG. 10 shows the effect of varying HDPE backbone chain length on tensile curves of 70 / 30 HDPE / iPP blends compatibilized with different loadings of the 44 kg / mol HDPE-based graft copolymer.

[0026] FIG. 11 shows the synthesis of a waste-based compatibilizer from post-consumer plastic waste (water jug HDPE, yogurt container iPP) and compatibilization of HDPE / iPP 70 / 30 blends with 10 wt % and 5.0 wt % waste HDPE-g-iPP loading.

[0027] FIG. 12 shows reaction conditions, DSC, SEC, rheology, and tensile testing results for the reaction kinetics of the radical recombination reaction of HDPE and iPP to form HDPE-g-iPP at different temperatures and reaction times.

[0028] FIG. 13 shows reaction conditions, DSC, SEC, rheology, and tensile testing results for the reaction kinetics of the radical recombination reaction of HDPE and iPP to form HDPE-g-iPP at different temperatures and reaction times.

[0029] FIG. 14 shows DSC, SEC, rheology and tensile testing results for the HDPE-g-iPP copolymers obtained with narrow-dispersity HDPEs or iPPs as starting materials under standard reaction conditions (HDPE:iPP = 30:70, 180 °C, 7.0 min, 5 wt % peroxide, 0.15 g / mL concentration).DETAILED DESCRIPTION OF THE DISCLOSURE

[0030] Although subject matter of the present disclosure is described, inter alia, in terms of certain examples, other examples, including examples that do not provide all of the benefits and features set forth herein, are also within the scope of this disclosure. For example, various structural, logical, and process step changes may be made without departing from the scope of the disclosure.

[0031] As used herein, unless otherwise indicated, “about”, “substantially”, or “the like”, when used in connection with a measurable variable (such as, for example, a parameter, an amount, a temporal duration, or the like) or a list of alternatives, is meant to encompass variations of and from the specified value including, but not limited to, those within experimental error (which can be determined by, e.g., a given data set, an art-accepted standard, etc. and / or with, e.g., a given confidence interval (e.g., 90%, 95%, or more confidence interval from the mean), such as, for example, variations of + / - 10% or less, + / -5% or less, + / -!% or less, and + / -0.1% or less of and from the specified value), insofar as suchvariations in a variable and / or variations in the alternatives are appropriate to perform in the instant disclosure. As used herein, the term “about” may mean that the amount or value in question is the exact value or a value that provides equivalent results or effects as recited in the claims or taught herein. That is, it is understood that amounts, sizes, compositions, parameters, and other quantities and characteristics are not and need not be exact, but may be approximate and / or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error, or the like, or other factors known to those of skill in the art such that equivalent results or effects are obtained. In general, an amount, size, composition, parameter, or other quantity or characteristic, or alternative is “about” or “the like,” whether or not expressly stated to be such. It is understood that where “about” is used before a quantitative value, the parameter also includes the specific quantitative value itself, unless specifically stated otherwise.

[0032] Ranges of values are disclosed herein. The ranges set out a lower limit value and an upper limit value. Unless otherwise stated, the ranges include the lower limit value, the upper limit value, and all values between the lower limit value and the upper limit value, including, but not limited to, all values to the magnitude of the smallest value (either the lower limit value or the upper limit value) of a range. It is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. To illustrate, a numerical range of “0.1% to 5%” should be interpreted to include not only the explicitly recited values of 0.1% to 5%, but also, unless otherwise stated, include individual values (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.5% to 1.1%; 0.5% to 2.4%; 0.5% to 3.2%, and 0.5% to 4.4%, and other possible sub-ranges) within the indicated range. It is also understood (as presented above) that there are a number of values disclosed herein, and that each value is also herein disclosed as “about” that particular value in addition to the value itself. For example, if the value “10” is disclosed, then “about 10” is also disclosed. Ranges can be expressed herein as from “about” one particular value, and / or to “about” another particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms a further disclosure. For example, if the value “about 10” is disclosed, then “10” is also disclosed.

[0033] As used herein, unless otherwise stated, the term “group” refers to a chemical entity that is monovalent (i.e., has one terminus that can be covalently bonded to otherchemical species), divalent, or polyvalent (i.e., has two or more termini that can be covalently bonded to other chemical species). The term “group” also includes radicals (e.g., monovalent and multivalent, such as, for example, divalent radicals, trivalent radicals, and the like).Illustrative examples of groups include:

[0034] As used herein, unless otherwise indicated, the term “aliphatic groups” refers to branched or unbranched hydrocarbon groups that, optionally, contain one or more degrees of unsaturation. Degrees of unsaturation include, but are not limited to, alkenyl groups, alkynyl groups, and aliphatic cyclic groups. Aliphatic groups may be a Ci to C20 aliphatic group, including all integer numbers of carbons and ranges of numbers of carbons therebetween (e.g., Ci, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, and C20). Aliphatic groups may be unsubstituted or substituted with one or more substituents.Examples of substituents include, but are not limited to, halogens (-F, -Cl, -Br, and -I), aliphatic groups (e.g., alkyl groups, alkenyl groups, alkynyl groups, and the like), halogenated aliphatic groups (e.g., trifluorom ethyl group and the like), aryl groups, halogenated aryl groups, alkoxide groups, amine groups, nitro groups, carboxylate groups, carboxylic acids, ether groups, alcohol groups, alkyne groups (e.g., acetylenyl groups and the like), and the like, and combinations thereof. Aliphatic groups may be alkyl groups, alkenyl groups, alkynyl groups, or carbocyclic groups, and the like.

[0035] As used herein, unless otherwise indicated, the term “alkyl group” refers to branched or unbranched saturated hydrocarbon groups. Examples of alkyl groups include, but are not limited to, methyl groups, ethyl groups, propyl groups, butyl groups, isopropyl groups, tert-butyl groups, and the like. For example, the alkyl group is Ci to C20, including all integer numbers of carbons and ranges of numbers of carbons therebetween (e.g., Ci, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, and C20). The alkyl group may be unsubstituted or substituted with one or more substituents. Examples of substituents include, but are not limited to, various substituents such as, for example, halogens (-F, -Cl, -Br, and -I), aliphatic groups (e.g., alkyl groups, alkenyl groups, alkynyl groups, and the like), aryl groups, alkoxide groups, carboxylate groups, carboxylic acids, ether groups, amine groups, and the like, and combinations thereof.

[0036] As used herein, unless otherwise stated, the term “structural analog” refers to any copolymer, reactant (e.g., polymer, radical source, or the like), reaction component (e.g.,solvent, quencher, or the like), additive, or the like, or any portion thereof (such as, for example, one or more group(s) thereof or the like) or group if one atom or group of atoms, functional group or functional groups, or substructure or substructures is / are replaced with another atom or group of atoms, functional group or functional groups, substructure or substructures, or the like. In various examples, the term “structural analog” refers to any group that is derived from an original copolymer, reactant (e.g., polymer, radical source, or the like), reaction component (e.g., solvent, quencher, or the like), additive, or the like, or any portion thereof (such as, for example, one or more group(s) thereof or the like) or group by a chemical reaction, where the copolymer, reactant (e.g., polymer, radical source, or the like), reaction component (e.g., solvent, quencher, or the like), additive, or the like, or any portion thereof (such as, for example, one or more group(s) thereof or the like) or the group is modified or partially substituted such that at least one structural feature of the copolymer, reactant (e.g., polymer, radical source, or the like), reaction component (e.g., solvent, quencher, or the like), additive, or the like, or any portion thereof (such as, for example, one or more group(s) thereof or the like) or the group is retained.

[0037] The following abbreviations, inter alia, are used herein. Atactic polypropylene, aPP; 2,5-dimethyl-2,5-(di- / c / 7-butylperoxy)hexane, DHBP; differential scanning calorimetry, DSC; high-density polyethylene, HDPE; high-density polyethylene isotactic polypropylene graft copolymers, HDPE-g-iPP; isotactic polypropylene, iPP; low-density polyethylene, LDPE; size-exclusion chromatography, SEC; 1, 2, 4-tri chlorobenzene, TCB.

[0038] The present disclosure provides, inter alia, copolymers and compositions thereof and polymer blends and uses thereof. Also provided are methods of making copolymers and methods of making copolymer blends.

[0039] In an aspect, the present disclosure provides copolymers. In various examples, a copolymer is a compatibilizer or the like. In various examples, a copolymer is produced by a method of the present disclosure. Non-limiting examples of copolymers are disclosed herein.

[0040] In various examples, a copolymer comprises (or consists essentially of or consists of) one or more (e.g., a plurality of) first group(s) (e.g., a segment or segments, which may be a first segment or first segments, or a backbone group or groups, or the like) comprising a plurality of groups (e.g., repeat units) independently formed from one or more ethylenically unsaturated monomer(s); and one or more (e.g., a plurality of) second group(s) (e.g., a segment or segments, which may be a second segment or segments, or the like) independently comprising a plurality of groups (e.g., repeat units) independently formed from one or more ethylenically unsaturated monomer(s), where each second group (e.g., segment,which may be a second segment, or the like) is different (e.g., compositionally different and / or constitutionally different and / or configurationally different) from one or more first group(s) (e.g., segment(s), which may be a first segment, or the like), and where at least one or a plurality of second group(s) (e.g., segment(s), which may be a second segment, or the like) is covalently bonded to one or a plurality of first group(s) (e.g., segment(s), which may be a first segment, or backbone group, or the like).

[0041] A copolymer comprises one or more (e.g., a plurality of) first group(s) (e.g., a segment or segments, which may be a first segment or first segments, or a backbone group or groups, or the like). In various examples, a first group comprises a plurality of groups (e.g., repeat units) and each group is formed from one or more ethylenically unsaturated monomer(s) (such as for example, olefin monomer(s) or the like, one or more or all of which are terminal olefin(s)). In various examples, a first group is formed from olefin monomer(s), one or more or all of which are terminal olefin(s). In various examples, an ethylenically unsaturated monomer is a C2 to C12 ethylenically unsaturated monomer, including all integer number of carbons and ranges therebetween (e.g., C2, C3, C4, C5, Ce, C7, Cs, C9, C10, C11, or C12). Non-limiting examples of ethylenically unsaturated monomers include styrene monomers, diacid monomer(s) (e.g., C4 to C40 diacid monomer(s), including all integer number of carbons and ranges therebetween), diol monomer(s) (e.g., C2 to C40 diol monomer(s), including all integer number of carbons and ranges therebetween), or a structural analog thereof, or the like, or any combination thereof. In various examples, a first group is a polyolefin group, a polyester group, a polystyrene group, or a structural analog thereof, or the like, or any combination thereof.

[0042] A copolymer comprises one or more (e.g., a plurality of) second group(s) (e.g., a segment or segments, which may be a second segment or segments, or the like). In various examples, a second group comprises a plurality of groups (e.g., repeat units). In various examples, each group is formed from one or more ethylenically unsaturated monomer(s) (such as, for example, olefin monomer(s) or the like, one or more or all of which are terminal olefin(s)). In various examples, an ethylenically unsaturated monomer is a C2 to C12 ethylenically unsaturated monomer, including all integer number of carbons and ranges therebetween (e.g., C2, C3, C4, C5, Ce, C7, Cs, C9, C10, C11, or C12). Non-limiting examples of ethylenically unsaturated monomers include styrene monomers, or a structural analog thereof, or the like, or any combination thereof. In various examples, a second group comprises or is a polyolefin group, a polystyrene group, or a structural analog thereof, or the like, or any combination thereof.

[0043] In various examples, each second group (e.g., segment, which may be a second segment, or the like) is different (e.g., compositionally different and / or constitutionally different and / or configurationally different) from the first group (e.g., segment, which may be a first segment, or the like). By “compositionally distinct” it is meant that a first group and a second group or a first polymer and a second polymer comprise different nominal molecular structure (e.g., different constituent atomic components or the like). In an illustrative example, a linear polyethylene group or polymer and a polystyrene group or polymer are compositionally distinct. By “constitutionally distinct” it is meant that a first group and a second group or a first polymer and a second polymer comprise different connectivity, other than nominal molecular structure. Non-limiting examples of different connectivity include different linkage group structures, different branching, or the like, or any combination thereof. In an illustrative example, a high-density polyethylene (HDPE) group or polymer and a low-density polyethylene (LDPE) group or polymer (which have the same or substantially the same molecular formula or repeat group structure) are constitutionally distinct (e.g., comprise different linkage group structure and / or different branching). By “configurationally distinct” it is meant that a first group and a second group or a first polymer and a second polymer comprise different spatial orientations, other than nominal molecular structure or different connectivity. In an illustrative example, a syndiotactic polypropylene group or polymer and an isotactic polypropylene group or polymer are configurationally distinct (e.g., comprise different spatial orientations (stereochemistry or the like)).

[0044] In various examples, a first group or groups and / or a second group or groups independently comprise(s) (or is / are) a homopolymer group or groups or a copolymer group or groups. In various examples, a first group or groups and / or a second group or groups is / are independently formed from a polymer (e.g., a homopolymer or copolymer) disclosed herein (such as, for example, a polymer that undergoes H-abstraction or the like). Non-limiting examples of polymers include HDPE, LDPE, LLDPE, PMP, zPP, sPP, aPP, PS, PBD, long-chain aliphatic polyesters, SBS, EPR, EPDM, ABS, and structural analogs thereof, and the like.

[0045] In various examples, a first group or groups and / or second group or groups independently comprise (or is / are) a polyolefin group. Non-limiting examples of polyolefin groups include high-density polyethylene (HDPE) groups, low-density polyethylene (LDPE) groups, linear low-density polyethylene (LLDPE) groups, polymethylpentene (PMP) groups, isotactic polypropylene (iPP) groups, syndiotactic (sPP) groups, atactic polypropylene (aPP) groups, polybutadiene (PBD) groups, polyester groups, polystyrene (PS) groups, long-chainaliphatic polyester groups (e.g., about C8to C20aliphatic polyester groups or the like), styrene-butadiene-styrene (SBS) rubbers, ethylene propylene rubbers (EPRs), ethylene propylene diene monomer copolymers (EPDMs), acrylonitrile-butadiene-styrene (ABS) copolymers, structural analogs thereof, and the like.

[0046] In various examples, substantially all, or all of one or more or all of the first groups and / or second groups are independently derived from (or formed from) a virgin resin (such as, for example, a polymer or polymers directly after polymerization without any additional treatment / compounding steps or the like), a specifically synthesized polymer or polymers, a post-production waste polymer or polymers (such as, for example, a polymer resin or resins left as waste from industrial processes, e.g., punching machine leftovers or the like, or the like), a post-consumer waste polymer (such as, for example, polymer or polymers recovered from any type of consumer application, e.g., food containers, water bottles, or the like, or the like, which may be purified), a recycled material or materials (such as, for example, a recovered polymer waste or wastes (e.g., from industrial recycling facilities or the like), which may be comingled or the like), a reclaimed material or materials (e.g., waste polymer or polymers recovered from the environment or the like), or the like, or any combination thereof.

[0047] A copolymer can have various molecular weights (e.g., number-averaged molecular weight (Mn), Mp(most abundant molecular weight), or the like, or both). In various examples, a copolymer comprises a number-averaged molecular weight (Mn) of about 1 kDa (kDa = kilodalton(s)) to about 1,000 kDa (which may be determined as described herein) and / or the copolymer comprises a Mp(molecular weight peak maximum determined by GPC as described herein) of about 500 kDa or less, about 450 kDa or less, about 400 kDa or less, about 250 kDa or less, about 150 kDa or less, about 100 kDa or less, about 75 kDa or less, or about 50 kDa or less, or about 10 kDa to about 500 kDa. In various examples, a copolymer comprises a lower Mn(or relative to) and / or a lower Mvthan (or relative to) a polymer or polymers used to make the copolymer and / or a physical blend of a polymer or polymers used to make the copolymer.

[0048] In various examples, a gel permeation chromatogram of a copolymer is unimodal. In various examples, a gel permeation chromatogram of a copolymer is not multimodal.

[0049] In various examples, a copolymer comprises one or more (or a plurality of) linking group(s). In various examples, each linking group is covalently bonded to a first polymer group and a second polymer group. In various examples, linking groups are chosen from:HDPE- HDPE HDPE-HDPEY-branch H-branch H-branchHDPE-HY-branch(where the dotted lines represent a bond to a polymer group (e.g., a first polymer group, a second polymer group, or the like) and structural analogs thereof, and the like. In various examples, a copolymer does not comprise a linking group having the following structure:HDPE- Y-branch, or a structural analog thereof, or the like. In various examples, a first methyl group (relative to, proximate to the first group, or attached to a first group) of a linking group or a second group (such as, for example, a polypropylene group or the like) bears no stereoinformation relative to the other repeat units of the linking group or second group (such as, for example, propylene repeat units of the linking group or second group). In various examples, at least a portion, substantially all, or all of the methyl groups (such as, for example, first methyl groups or the like) (relative to, proximate to the first group, or attached to a first group) of the linking groups or second groups (such as, for example, polypropylene groups or the like) of a copolymer comprise (or are) a racemic mixture of R and S stereocenters. Without intending to be bound by any particular theory, in certain examples, it is considered that the stereochemistry of at least a portion, substantially all, or all the groups (such as, for example, first methyl groups or the like) (relative to, proximate to the first group, or attached to a first group) of the linking groups or second groups (such as, for example, polypropylene groups or the like) of a copolymer from the starting polymer(s) usedto form the groups is lost during formation of the copolymer (e.g., the radical attachment reaction during formation of the copolymer).

[0050] A copolymer can comprise various end groups. In various examples, a copolymer comprises end groups independently chosen from alkyl groups, alkenyl groups (which may be terminal alkenyl groups), and the like, and any combination thereof. Non-limiting examples of end groups include:polyethylene end groups:polypropylene end groups:’ (where the dotted lines represent a bond to a polymer group (e.g., a first polymer group, a second polymer group, or the like) and structural analogs thereof, and the like.

[0051] In various examples, a copolymer has desirable solubility in a solvent or combination of solvents, such as, for example, chlorobenzene, dichlorobenzene (such as, for example, 1,2-di chlorobenzene or a structural analog thereof, or the like), tri chlorobenzene (such as, for example, 1, 2, 4-tri chlorobenzene or a structural analog thereof, or the like), an alkyl aromatic compound (e.g., toluene, xylenes (such as, for example, o-xylene, / ?-xylene, m-xylene), or the like), 1,1,2,2-tetrachloroethane, 1,2-di chloroethane, diphenyl ether, benzene, biphenyl, hydrocarbon solvents (such as, for example, dodecane or a structural analog thereof, or the like), tetrahydrofuran, or a structural analog thereof, or the like, or a combination thereof. In various examples, a copolymer (e.g., at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95%, at least about 99%, at least about 100% by weight (wt %) (such as, for example, at least about 50 wt % to at least about 100 wt %) of the copolymer (based on the total weight of the copolymer)) is soluble in one or more solvent(s) (e.g., as described herein) and / or a copolymer comprises about 50 wt % or less, about 40 wt % or less, about 30 wt % or less, about 20 wt % or less, about 10 wt % or less, about 5 wt % or less, about 1 wt % or less, or does not comprise an observable (e.g., by gravimetric analysis or the like) insoluble fraction in one or more solvent(s) (e.g., as described herein).

[0052] In various examples, a copolymer comprises or exhibits one or both of: a melting point or melting points independently ranging from the melting point of a highest melting point of a polymer from which a first group or a second group is formed or derived to about 100 °C lower than a lowest melting point of a polymer from which a first group or a second group is formed or derived. In various illustrative examples, for HDPE / zPP copolymers the melting point(s) independently range from about 160 °C to about 100 °C (e.g., a HDPE fraction range of about 111 °C to about 105 °C and an zPP fraction range of about 152 °C to about 142 °C); or a copolymer exhibits shear-thinning behavior (e.g., where the polymers from which the copolymer was (e.g., first group(s) and / or second group(s) were) formed are Newtonian behaving polymer melts), as defined by a ratio of a melt viscosity at 0.1 Hz divided by a melt viscosity at 250 Hz (= R*), where the ratio (R*) is about 20 to about 300, including all 0.1 ratio values and ranges therebetween.

[0053] A copolymer can be suitable for various uses (e.g., as described herein). In various examples, a copolymer is suitable for use as a thermoplastic material, a compatibilizer, a thermoplastic elastomer, or the like, or any combination thereof.

[0054] In various examples, a copolymer is a thermoplastic material with improved properties compared to a physical blend of the polymers from which the copolymer was (e.g., the first group and second group(s) were) formed. As an illustrative example, for a HDPE / zPP copolymer and a HDPE / zPP physical blend (of the same polymers as those used to form the copolymer (e.g., first group and second group(s)), the copolymer has a uniaxial elongation at break of at least about 2 times or greater, at least about 3 times or greater, at least about 50 times or greater, or at least about 70 times or greater compared to the physical blend.

[0055] In various examples, a copolymer of the present disclosure is a means for improving (e.g., increasing, which may be substantially increasing, or the like) (e.g., increasing by 10% or more, 20% or more, about 50% or more, about 100% or more, about 150% or more, 200% or more, 500% or more, or 1000% or more) the uniaxial elongation at break, yield stress, impact resistance, shear or compressive strength, or the like, or any combination thereof of a composition comprising two or more polymers (e.g., polymers independently derived from ethylenically unsaturated monomers (which independently may be a homopolymer or copolymer), such as, for example, polyolefin blends (such as, for example, HDPE / zPP blends and the like) or the like) and the copolymer(s) compared to a same composition that does not comprise the copolymer(s). In various examples, a composition has at least about 2 times or greater, at least about 3 times or greater, at least about 50 times or greater, at least about 70 times or greater uniaxial elongation at break or thelike (which may be for an HDPE / zPP blend or the like), compared to the composition without the copolymer(s).

[0056] In various examples, a copolymer is a means of compatibilizing two or more polymers. In various examples, addition of about 0.05 weight % (wt %) to about 20 wt % (individually or in the aggregate) of one or more copolymer(s) (based on the total weight of the polymer blend) results in compatibilization of two or more polymers. By “compatibilization” it is meant one or more propert(ies) (such as, for example, uniaxial elongation at break, yield stress, impact resistance, shear or compressive strength, or the like, or any combination thereof) of a blend of two or more polymers comprising one or more copolymer(s) of the present disclosure is improved relative to a blend of the same two or more polymers which does not comprise those same one or more copolymer(s) of the present disclosure.

[0057] In an aspect, the present disclosure provides polymer blends. In various examples, a polymer blend comprises one or more copolymer(s) of the present disclosure. In various examples, a polymer blend is a compatibilized blend. In various examples, a polymer blend is made by a method of the present disclosure. Non-limiting examples of polymer blends are disclosed herein.

[0058] In various examples, a polymer blend comprises (or consists essentially of or consists of) one or more copolymer(s) of the present disclosure and one or more polymer(s) (e.g., two or more polymers, such as, for example, a first polymer, a second polymer, etc.). In various examples, the polymers are independently homopolymers or copolymers.

[0059] A polymer blend can have various amounts of copolymer(s). In various examples, the one or more copolymer(s) is / are present at a concentration of about 0.05 wt % to about 20 wt % (based on the total weight of the polymer blend), including all 0.01 wt % values and ranges therebetween (e.g., about 1 wt % or about 5 wt %).

[0060] A polymer blend can have various polymers. Combinations of specific polymers are disclosed herein. In various examples, a polymer blend comprises one polymer or two or more different (structurally and / or compositionally different) polymers. Non-limiting examples of polymers include polyolefins, polyesters, polybutadienes, polystyrenes, and structural analogs thereof, and the like, and copolymers comprising one or more thereof. In various examples, a polymer comprises one or more group(s) formed from these exemplary polymers.

[0061] A polymer blend can have various polymer ratios. In various examples, a first polymer / second polymer ratio (e.g., the first polymer / second polymer ratio) (e.g., HDPE / z'PPor the like) is about 95 / 5 to about 5 / 95 (w / w), including all 0.1 ratio values and ranges therebetween.

[0062] Polymers from various sources can be used herein (e.g., as described herein). Non-limiting sources of polymers include virgin resins, specifically synthesized polymer(s), post-production waste polymer(s), post-consumer waste polymer(s), reclaimed materials, and the like, and any combination thereof.

[0063] A polymer blend can have various forms (e.g., as described herein). Non-limiting examples of polymer blends include monoliths, fibers, sheets, films (such as, for example, thin films), pellets, powders, foams, and the like.

[0064] A polymer can have various molecular weights. In various examples, the polymer(s) independently comprise a number-averaged molecular weight (n) of about 1 to about 5,000 kDa (which may be determined as described herein), including all integer kDa values and ranges therebetween (e.g., about 10 kDa to about 500 kDa, which may be for a HDPE / zPP copolymer or the like).

[0065] A polymer blend can have desirable properties. In various examples, a polymer blend has (or exhibits) increased uniaxial elongation or the like, compared to the polymer blend without the copolymer(s) (e.g., at least 2 times or greater, at least 3 times or greater, at least 50 times or greater, at least 70 times or greater, uniaxial elongation or the like, compared to the polymer blend without the copolymer(s)). For HDPE / zPP blends, a polymer blend has (or exhibits) at least 2 times or greater, at least 3 times or greater, at least 50 times or greater, at least 70 times or greater, uniaxial elongation or the like, compared to the polymer blend without the copolymer. Without any compatibilizer(s) added to the polymer blend, most physical properties of polymer blends typically exhibit worse behavior than expected according to the parallel model (the polymer blend without any compatibilizer(s)). In various examples, properties (P) like elasticity, yield strength, strain at yield, strain at break, impact resistance, shear or compressive strength, or the like, of polymer blends are predicted by superposition of the properties of the pure polymers pi and their weight fraction in the blend %i as P = pi • xi. In various examples, addition of compatibilizer(s) (e.g., copolymer(s) of the present disclosure) to a polymer blend results in restoration of one or more or all of the physical properties of the polymer blends (e.g., uniaxial elongation, yield stress, impact resistance, shear or compressive strength, or the like, or any combination thereof) to about (e.g., substantially or within 10% or less, within 5% or less, or within 1% or less) the expected values of those physical propert(ies) (e.g., the expected values from aparallel model (the polymer blend without any compatibilizer(s) (e.g., copolymer(s) of the present disclosure))).

[0066] In an aspect, the present disclosure provides compositions. In various examples, a composition comprises one or more copolymer(s) of the present disclosure. Non-limiting examples of compositions are disclosed herein.

[0067] In various examples, a composition comprises (or consists essentially of or consists of) one or more copolymer(s) of the present disclosure. In various examples, the composition further comprises one or more additive(s) (e.g., as described herein).

[0068] A composition can have various forms (e.g., as described herein). Non-limiting examples of polymer blends include monoliths, fibers, sheets, films (such as, for example, thin films), pellets, powders, foams, and the like.

[0069] In an aspect, the present disclosure provides methods of making copolymers. In various examples, a method comprises contacting one or more (e.g., two or more) polymers, which may be referred to as precursor polymer(s), with one or more radical(s), and optionally, one or more additives and / or solvent(s); and optionally, heating the polymers, radical(s), and, if present, additive(s) and / or solvent(s). In various examples, a method is an in situ method (such as, for example, an in situ compatibilization method or the like). In various examples, a method comprises (or consists essentially of or consists of) a single step (such as, for example, a single copolymer production step or the like). In various examples, a method produces one or more copolymer(s) of the present disclosure. Non-limiting examples of methods of making copolymers are disclosed herein.

[0070] In various examples, a method of making one or more copolymer(s) comprises (or consists essentially of or consists of) contacting (e.g., in a reaction mixture, which may be a homogeneous mixture, a solution or the like) two or more polymers (e.g., a first polymer, a second polymer, etc.) (e.g., where the polymers are independently homopolymers or copolymers) with one or more radical(s), and optionally, one or more solvent(s) (e.g., solvent(s) that at least partially solubilize, substantially solubilize, or completely solubilize the polymer); and optionally, heating the polymers, radical source(s), and solvent(s) (e.g., where the copolymer(s) is / are produced). In various examples, at least two or more of the polymers are different (e.g., compositionally different and / or constitutionally different and / or configurationally different) In various examples, the two or more polymers (e.g., first polymer and second polymer or the like) comprise (or are) HDPE / zPP or the like.

[0071] Various polymers can be used. In various examples, a polymer (a homopolymer or a copolymer) is a linear or branched polymer. Combinations of specific polymers aredisclosed herein. In various examples, a polymer comprises one or more hydrogen group(s) (e.g., a backbone hydrogen group or groups, a side-chain hydrogen group or groups, or any combination thereof) that can react with a radical (e.g., via H-atom extraction or the like) to form a radical. In various examples, the two or more polymers are independently chosen from polyolefins, polyesters, polystyrenes, and structural analogs thereof, and the like, and copolymers thereof. Non-limiting examples of polymers include polyolefins (such as, for example, polyethylenes (e.g., high-density polyethylenes, low-density polyethylenes, medium-density polyethylenes, linear low-density polyethylenes, and structural analogs thereof, and the like), polypropylenes (such as, for example, isotactic polypropylenes, atactic polypropylenes, syndiotactic polypropylenes, and structural analogs thereof, and the like), polymethylpentenes, and structural analogs thereof, and the like), polybutadienes, polyesters (such as, for example, aliphatic polyesters (e.g., polycaprolactones, poly(3-hydroxybutyrate)s, long-chain aliphatic polyesters (such as, for example, PE-18,18, and structural analogs thereof, and the like), polystyrenes, copolymers of ethylene and propylene (such as, for example, ethylene-propylene rubbers, ethylene propylene diene monomer copolymers, and structural analogs thereof, and the like), polyolefin copolymers (such as, for example, styrene-butadiene-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, and structural analogs thereof, and the like), and structural analogs thereof, and the like, and combinations thereof. In various examples, the two or more polymers comprise (or are) an HDPE and an zPP.

[0072] Various amounts and ratios of two or more polymers can be used. In various examples, two or more polymers (e.g., the first polymer, the second polymer, etc.) are present at (e.g., a reaction mixture comprises) about 0.1 wt % to about 70 wt %, including all 0.1 wt % values and ranges therebetween (e.g., about 5 wt % to about 25 wt %, or about 50 wt %), based on the total weight of polymer(s), radical(s) (e.g., radical precursor(s) or the like), and solvent(s), if present. In various examples, the polymers are present at (e.g., a reaction mixture comprises) at about 5 wt % to about 25 wt % (e.g., based on the total weight of the reaction mixture), including all 0.1 wt % values and ranges therebetween (e.g., about 10 wt % to about 25 wt %), which may be for HDPE and zPP. In various examples, a ratio of two or more of the two or more polymers (such as, for example, first polymer(s) / second polymer(s) (e.g., zPP / HDPE or the like)) is about 95 / 5 to about 5 / 95 (w / w), including all 0.1 ratio values and ranges therebetween (e.g., about 10 / 90, about 50 / 50, about 70 / 30 (w / w), which may be an zPP / HDPE ratio).

[0073] Polymers from various sources can be used herein (e.g., as described herein). Non-limiting sources of polymers include virgin resins, specifically synthesized polymer(s), post-production waste polymer(s), post-consumer waste polymer(s), reclaimed materials, and the like, and any combination thereof.

[0074] Various radicals can be used. A single radical source or a combination of radical sources may be used. A radical precursor forms one or more radical(s) on homolytic cleavage of one or more bond(s) of the radical precursor. In various examples, one or more or all of the radical(s) is / are independently formed from one or more radical source(s). Non-limiting examples of radical precursors include organic radical precursors, inorganic radical precursors, and the like. In various examples, one or more, or all radical source(s) is / are a radical precursor or precursors (such as, for example, a small molecule that forms one or more radical(s) as a result of homolytic bond cleavage or the like). In various examples, a radical source is used. In various examples, one or more or all of the radical(s) is / are independently formed from one or more radical source(s). Non-limiting examples of radical sources and radical precursors are described herein.

[0075] Various amounts of radicals can be used. In various examples, a radical precursor or precursors is / are present at about 0.01 weight percent (wt %) to about 10 wt % (based on the total weight of the polymers), including all 0.1 wt % values and ranges therebetween (e.g., about 3 wt % to about 5 wt %, which may be for HDPE and zPP or the like).

[0076] Various solvents can be used. A single solvent or a combination of solvents may be used. In various examples, the solvent(s) are the remainder of a reaction mixture. Nonlimiting examples of solvents include chlorobenzene, dichlorobenzenes, (such as, for example, 1,2-di chlorobenzene or a structural analog thereof, or the like), tri chlorobenzenes (such as, for example, 1, 2, 4-tri chlorobenzene or a structural analog thereof, or the like), diphenyl ether, benzene, biphenyl, and structural analogs thereof, and the like.

[0077] Additives may be used. A single additive or a combination of additives may be used. In various examples, a method includes use of (e.g., a reaction mixture also comprises) one or more additive(s) (e.g., as described herein). In various examples, an additive is used (e.g., added to the reaction mixture) before, after, or during the contacting, or any combination thereof, or before or after the heating, or both.

[0078] Various amounts of additives may be used. In various examples, additive(s) is / are present (individually or in the aggregate) at about 0.1 weight percent (wt %) to about 10 wt % (based on the total weight of the polymers), including all 0.1 wt % values and ranges therebetween.

[0079] In various examples, a contacting is carried out by mixing, stirring (such as, for example, magnetic stirring, mechanical stirring, ball-milling, sonication, or the like), or the like, or any combination thereof. In various examples, a contacting is carried out in a melt extruder or the like. In various examples, the contacting is not carried out in a melt extruder or the like.

[0080] In various examples, contacting one or more polymer(s) results in formation of a polymer or polymers comprising radical(s) (which can react with radical(s) of another polymer or polymers). In various examples, a method comprises macroradical recombination or the like.

[0081] In various examples, a method further comprises forming a reaction mixture (such as, for example, a solution, a melt, a suspension, an emulsion, or the like) comprising two or more polymers and optionally, one or more solvent(s) prior to contacting the reaction mixture (e.g., adding) with the radical(s). In various examples, a method further comprises carrying out the contacting in a melt extruder (e.g., melt extruding a reaction mixture (such as, for example, a solution, a melt, a gel, or the like)) comprising two or more polymers, the radical(s), and optionally, one or more solvent(s).

[0082] A method or a portion / portions thereof (e.g., contacting, forming a reaction mixture, holding the reaction mixture, mixing the reaction mixture, or the like, or any combination thereof) can be performed under various reaction conditions. A method or a portion / portions thereof (e.g., contacting, forming a reaction mixture, holding the reaction mixture, mixing the reaction mixture, or the like, or any combination thereof) can comprise one or more step(s) and each step can be performed under the same or different reaction conditions as other steps.

[0083] A method or a portion thereof (e.g., contacting, forming a reaction mixture, holding the reaction mixture, mixing the reaction mixture, or the like, or any combination thereof) can be carried out at various temperatures. In various examples, a method or a portion / portions thereof (e.g., contacting, forming a reaction mixture, holding the reaction mixture, mixing the reaction mixture, or the like, or any combination thereof) is / are carried out at a selected temperature or individual selected temperatures (e.g., as described herein) (e.g., where each portion / step of a method (e.g., contacting, forming a reaction mixture, holding the reaction mixture, mixing the reaction mixture, or the like, or any combination thereof) is performed at the same or a different temperature as one or more of the other portions / steps). A method or a portion / portions thereof (e.g., contacting, forming a reaction mixture, holding the reaction mixture, mixing the reaction mixture, or the like, or anycombination thereof) can be carried out at various pressures. In various examples, a method or a portion / portions thereof (e.g., contacting, forming a reaction mixture, holding the reaction mixture, mixing the reaction mixture, or the like, or any combination thereof) is carried out at atmospheric pressure (e.g., 1 standard atmosphere (atm) at sea level), which may be ambient pressure, at greater than atmospheric pressure (e.g., heating in a sealed pressurized reaction vessel and the like), or any combination thereof (e.g., where each portion / step of a method (e.g., contacting, forming a reaction mixture, holding the reaction mixture, mixing the reaction mixture, or the like, or any combination thereof) is performed at the same or a different pressure as one or more of the other portions / steps).

[0084] A method or a portion / portions thereof (e.g., contacting, forming a reaction mixture, holding the reaction mixture, mixing the reaction mixture, or the like, or any combination thereof) can be carried out for various selected times (e.g., as described herein). The reaction time may depend on factors such as, for example, temperature, pressure, mixing (e.g., stirring or the like), reaction kinetics, or the like, or any combination thereof. In various examples, reaction times range from about seconds (e.g., about 10 seconds) to greater than about 48 hours, including all integer second values and ranges therebetween, or any combination thereof (e.g., where each portion / step of a method (e.g., forming a reaction mixture, holding the reaction mixture, mixing the reaction mixture, or the like, or any combination thereof) is performed at the same or a different temperature as one or more of the other portions / steps). In various examples, a contacting is carried out for about 1 minute to about 48 hours, including all 0.1 minute values and ranges therebetween, and / or for a time equivalent to a radical half-life time (t1 / 2) of about 0.1 t1 / 2to about 20 t1 / 2, including all 0.1 t1 / 2values and ranges therebetween.

[0085] A method may comprise quenching (e.g., quenching the reaction mixture). A single quencher or a combination of quenchers may be used. In various examples, a method further comprises quenching (e.g., after a desired reaction time or the like) the contacted polymers and radical(s) (e.g., the reaction mixture or the like) (or addition of one or more quencher(s) (which may be referred to as quenching agent(s)) or the like). In illustrative examples, a reaction is quenched by addition of one or more radical scavenging agent(s) that terminates any macroradical reactivity (such as, for example, 2,6-di-tert-butyl-4-methylphenol, 2,2,6,6-tetramethylpiperidinyloxyl, hydroquinone, or the like, structural analogs thereof, or any combination thereof).

[0086] A method may comprise isolation of the copolymer(s) (e.g., as described herein). One of ordinary skill in the art will envision suitable isolation methods, processes, etc.

[0087] In various examples, a method does not result in an undesirable fraction of copolymer(s) (such as, for example, insoluble in a solvent as described herein). In various examples, a method does not result in more than about 50 wt % or greater, about 40 wt % or greater, about 30 wt % or greater, about 20 wt % or greater, about 10 wt % or greater, about 5 wt % or greater, about 1 wt % or greater, or an observable (e.g., by gravimetric analysis or the like) insoluble fraction (such as, for example, insoluble in a solvent as described herein) of the copolymer(s).

[0088] A method can result in a change in one or more properties of one or more polymer(s). In various examples, a method changes the polymer(s) melt flow behavior and introduces a degree of shear-thinning to otherwise Newtonian behaving polymer melts, as defined by the ratio of a melt viscosity at 0.1 Hz divided by a melt viscosity at 250 Hz (= R*) (e.g., ratios from 20 to 300, including all 0.1 values and ranges therebetween).

[0089] In an aspect, the present disclosure provides compositions. In various examples, a composition is used (or is suitable for use in) a method of the present disclosure (such as, for example, a method of making a copolymer of the present disclosure or a method of making a polymer blend of the present disclosure). In various examples, a composition is suitable for melt processing or is a melt-processable composition. Non-limiting examples of compositions are disclosed herein.

[0090] In various examples, a composition (which, in various examples, may be referred to as a polymer blend composition) comprises: two or more polymers (e.g., a first polymer, a second polymer, etc.) (e.g., where the polymers are independently homopolymers or copolymers); one or more radical source(s); and optionally, one or more quencher(s) and / or one or more solvent(s) (e.g., solvent(s) that at least partially solubilize, substantially solubilize, or completely solubilize the polymers). In various examples, a composition is suitable to produce a copolymer or copolymers of the present disclosure, copolymer(s) made by a method of the present disclosure and / or one or more polymer blend(s) of the present disclosure, polymer blend(s) made by a method of the present disclosure and / or one or more composition(s) of the present disclosure. In various examples, a composition may be suitable for use in a method of the present disclosure (such as, for example, a method of making a copolymer of the present disclosure or a method of making a polymer blend of the present disclosure). In various examples, a composition is suitable for melt processing or is a melt-processable composition.

[0091] In various examples, a composition comprises two or more polymers (e.g., a first polymer, a second polymer, etc.); one or more radical source(s); optionally, one or morequencher(s); and optionally, one or more additive(s) and / or one or more solvent(s) (e.g., solvent(s) that at least partially solubilize, substantially solubilize, or completely solubilize the polymer(s)). Non-limiting examples of polymers, radical sources, quencher, additives, and solvents and amounts of each are described herein. In various examples, the two or more polymers comprise (or are) an HDPE and an zPP. In various examples, a composition is suitable for use in a method of the present disclosure (such as, for example, a method of making a copolymer or copolymers of the present disclosure or a method of making a polymer blend of the present disclosure). In various examples, a composition is suitable for melt processing or is a melt-processable composition. In various examples, the composition components (such as, for example, the two or more polymers (e.g., a first polymer, a second polymer, etc.) and / or the one or more radical source(s) and / or the one or more quencher(s), if present, and / or one or more solvent(s), if present, can be combined in any order (e.g., relative to one or more or all of the other component(s)) and / or at any time (e.g., relative to one or more or all of the other component(s)).

[0092] In an aspect, the present disclosure provides a method of making a polymer blend. In various examples, a copolymer blend is made by blending one or more copolymer(s) of the present disclosure and two or more polymers (which are not copolymers of the present disclosure). Non-limiting examples of methods of making polymer blends are disclosed herein.

[0093] In various examples, a method of making a polymer blend comprises (or consists essentially of or consists of) blending (such as, for example, solvent blending, melt blending, ball-milling, or the like, or any combination thereof) one or more copolymer(s) of the present disclosure, and two or more polymers. In various examples, a polymer blend (which may be a compatibilized polymer blend, such as, for example, a compatibilized polymer blend as described herein) is formed.

[0094] In an aspect, the present disclosure provides articles of manufacture. In various examples, an article of manufacture comprises one or more copolymer(s) of the present disclosure, one or more or all of which may be made by a method of the present disclosure, one or more polymer blend(s) of the present disclosure, one or more or all of which may be made by a method of the present disclosure, one or more composition(s) of the present disclosure, or any combination thereof. Non-limiting examples of articles of manufacture are disclosed herein.

[0095] In various examples, an article of manufacture is an article of manufacture that can be or is typically made from a polymer or polymers (such as, for example, precursorpolymer or polymers of a polymer blend) disclosed herein. Non-limiting examples of articles of manufacture include containers (such as, for example, food storage containers, consumer product containers, water bottles (e.g., reusable water bottles and the like), and the like), plastic grocery bags, packaging, pipes, insulating panels, bathtubs, window panel doors, floors, tiles, syringes, petri dishes, specimen bottles, safety helmets, tendon prostheses, tracheal tubes, automobile components, electronic components, clothing (such as, for example, waterproof clothing, fiber form for clothing, and the like), carpets, non-stick pots and pans, eye-wear, CDs and DVDs, furniture, outdoor play equipment, toys, and the like.

[0096] Methods of making articles of manufacture using copolymers and / or polymer blends and / or compositions of the present disclosure are known in the art. In various examples, an article of manufacture is made by injection molding, extrusion, blow molding, or thermoforming, rotation molding, electrospinning, 3D printing, compression molding, CNC machining, or the like, or any combination thereof.

[0097] The following Statements describe various examples of copolymers, polymer blends, copolymer compositions, methods of making copolymers, polymer blend precursor compositions, methods of making polymer blends, and articles of manufacture of the present disclosure and are not intended to be limiting in any manner.Statement 1. A copolymer comprising: one or more (e.g., a plurality of) first group(s) (e.g., a segment or segments, which may be a first segment or first segments, or a backbone group or groups, or the like) comprising a plurality of groups (e.g., repeat units) independently formed from one or more ethylenically unsaturated monomer(s) (such as, for example, olefin monomer(s) or the like) (e.g., independently C2 to C12 ethylenically unsaturated monomer(s), such as, for example, olefin monomer(s), which may be terminal olefin monomer(s), or the like), one or more styrene monomers, one or more diacid monomer(s) (e.g., C4 to C40 diacid monomer(s)) and one or more diol monomer(s) (e.g., C2 to C40 diol monomer(s)), or a structural analog thereof, or the like, or any combination thereof (or a polyolefin group, a polyester group, a polystyrene group, or a structural analog thereof, or the like, or any combination thereof); and one or more (e.g., a plurality of) second group(s) (e.g., a segment or segments, which may be a second segment or segments, or the like) independently comprising a plurality of groups (e.g., repeat units) independently formed from one or more ethylenically unsaturated monomer(s) (such as, for example, olefin monomer(s) or the like) (e.g., independently C2 to C12 ethylenically unsaturated monomer(s), such as, for example, olefin monomer(s), which may be terminal olefin monomer(s), or the like), one or more styrene monomers, or a structural analog thereof, or the like, or any combination thereof (or apolyolefin group, a polystyrene group, or a structural analog thereof, or the like, or any combination thereof), with the proviso that each second group (e.g., segment, which may be a second segment, or the like) is different (e.g., compositionally different and / or constitutionally different and / or configurationally different) from the one or more first group(s) (e.g., segment or segments, which may be a first segment or first segments, or the like), where one or more or all or a plurality of second group(s) (e.g., segment or segments, which may be a second segment or second segments, or the like) is covalently bonded to one or a plurality of first segment(s) (e.g., segment(s), which may be a first segment or first segments, or a backbone group or groups, or the like).Statement 2. A copolymer according to Statement 1, where the copolymer (e.g., at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95%, at least about 99%, at least about 100% by weight (wt %) (such as, for example, at least about 50 wt % to at least about 100 wt %) of the copolymer (based on the total weight of the copolymer)) is soluble in chlorobenzene, di chlorobenzene (such as, for example, 1,2-di chlorobenzene or a structural analog thereof, or the like), trichlorobenzene (such as, for example, 1, 2, 4-tri chlorobenzene or a structural analog thereof, or the like), an alkyl aromatic compound (e.g., toluene, xylenes (such as, for example, o-xylene, / ?-xylene, m-xylene), or the like), 1,1,2,2-tetrachloroethane, 1,2-di chloroethane, diphenyl ether, benzene, biphenyl, hydrocarbon solvent (such as, for example, dodecane or a structural analog thereof, or the like), tetrahydrofuran, or a structural analog thereof, or the like, or a combination thereof at a temperature of about ambient temperature (about 25 °C) to about 250 °C, including all 0.1 °C values and ranges therebetween; and / or the copolymer comprises about 50 wt % or less, about 40 wt % or less, about 30 wt % or less, about 20 wt % or less, about 10 wt % or less, about 5 wt % or less, about 1 wt % or less, or does not comprise an observable (e.g., by gravimetric analysis or the like) insoluble fraction (such as, for example, insoluble in chlorobenzene, di chlorobenzene (such as, for example, 1,2-di chlorobenzene or a structural analog thereof, or the like), tri chlorobenzene (such as, for example, 1,2, 4-tri chlorobenzene or a structural analog thereof, or the like), an alkyl aromatic compound (e.g., toluene, xylenes (such as, for example, o-xylene, / ?-xylene, m-xylene), or the like), 1,1,2,2-tetrachloroethane, 1,2-di chloroethane, diphenyl ether, benzene, biphenyl, hydrocarbon solvents (such as, for example, dodecane or a structural analog thereof, or the like), tetrahydrofuran, or a structural analog thereof, or the like, or a combination thereof at a temperature of about ambient temperature (about 25 °C) to about 250 °C, including all 0.1 °C values and ranges therebetween.Statement 3. A copolymer according to Statement 1 or 2, where the copolymer comprises or exhibits a melting point or melting points independently from the melting point of the highest melting of a polymer from which a first group or a second group is formed or derived to about 100 °C lower than the lowest melting point of a polymer from which a first group or a second group is formed or derived.Statement 4. A copolymer according to any one of the preceding Statements, where the copolymer exhibits shear-thinning behavior (e.g., where the polymers from which the copolymer was (e.g., first group(s) and / or second group(s) were) formed are Newtonian behaving polymer melts), as defined by the ratio of the melt viscosity at 0.1 Hz divided by the melt viscosity at 250 Hz (= R*), with ratios from 20 to 300, including all 0.1 ratio values and ranges therebetween.Statement 5. A copolymer according to any one of the preceding Statements, where the number-averaged molecular weight (n) of the copolymer is about 1 kDa (kDa = kilodalton(s)) to about 1,000 kDa (which may be determined by gel permeation chromatography (GPC) (e.g., calibrated relative to polyethylene standards, which may be linear and / or narrowly dispersed polyethylene standards, or the like), multi -detector size exclusion chromatography (e.g., with light scattering detectors, which may be multi -angle light scattering detectors or the like, viscometer detectors, or the like, or any combination thereof), size exclusion chromatography (SEC), or the like), including all integer kDa values and ranges therebetween (e.g., about 10 kDa to about 35 kDa, which may be for a HDPE / zPP copolymer or the like), and / or the Mp(most abundant molecular weight) (molecular weight peak maximum determined by GPC as described herein) of the copolymer is about 500 kDa or less, about 450 kDa or less, about 400 kDa or less, about 250 kDa or less, about 150 kDa or less, about 100 kDa or less, about 75 kDa or less, or about 50 kDa or less, or about 10 kDa to about 500 kDa, including all 0.1 kDa values and ranges therebetween (e.g., about 20 kDa to about 500 kDa, about 20 to about 50 kDa, about 20 kDa to about 60 kDa (e.g., for an HDPE / iPP copolymer or the like), about 25 kDa to about 80 kDa, about 30 kDa to about 50 kDa, or about 40 kDa to about 60 kDa), and / or the copolymer comprises a lower (e.g., about 10% to 50% lower, including all 0.1% values and ranges therebetween, or 10% or more lower, 15% or more lower, 20% or more lower, or 25% or more lower) number average molecular weight Mnand / or a lower (e.g., about 10% to 50% lower, including all 0.1% values and ranges therebetween, or 10% or more lower, 15% or more lower, 20% or more lower, or 25% or more lower) Mp(most abundant molecular weight) (molecular weight peak maximumdetermined by GPC as described herein) than (or relative to) the polymers used to make the copolymer and / or a physical blend of the polymers used to make the copolymer.Statement 6. A copolymer according to any one of the preceding Statements, where the copolymer comprises one or more (or a plurality of) linking group(s) (non-limiting examples of which are provided herein), where each linking group is covalently bonded to a first polymer group and a second polymer group.Statement 7. A copolymer according to any one of the preceding Statements, where the copolymer end groups are independently chosen from alkyl groups (non-limiting examples of which are provided herein), alkenyl groups (which may be terminal alkenyl groups) (nonlimiting examples of which are provided herein), and the like.Statement 8. A copolymer according to any one of the preceding Statements, where the first group or groups and / or second group or groups independently comprise(s) (or is / are) a polyolefin group (such as, for example, a high-density polyethylene (HDPE) group, a low-density polyethylene (LDPE) group, a linear low-density polyethylene (LLDPE) group, a polymethylpentene (PMP) group, an isotactic polypropylene (zPP) group, a syndiotactic (sPP) group, an atactic polypropylene (aPP) group, or a structural analog thereof, or the like), a polybutadiene (PBD) group, a polyester group, a polystyrene (PS) group, a long-chain aliphatic polyester group, a styrene-butadiene-styrene (SBS) rubber, an ethylene propylene rubber (EPR), an ethylene propylene diene monomer copolymer (EPDM), an acrylonitrilebutadiene- styrene (ABS) copolymer, or a structural analog thereof, or the like.Statement 9. A copolymer according to any one of the preceding Statements, where the copolymer is (or is suitable for use as) a thermoplastic material, a compatibilizer, a thermoplastic elastomer or the like, or any combination thereof.Statement 10. A copolymer according to any one of the preceding Statements, where the copolymer is made by a method of the present disclosure (e.g., a method according to any of Statements 25 to 42).Statement 11. A copolymer, where the copolymer is made by a method of the present disclosure (e.g., a method according to any one of Statements 25 to 42).12. A polymer blend comprising one or more copolymer(s) of the present disclosure (e.g., copolymer(s) according to any one of the preceding Statements) and one or more polymer(s) (e.g., two or more polymers, such as, for example, a first polymer, a second polymer, etc.) (e.g., where the polymers are independently homopolymers or copolymers).Statement 13. A polymer blend according to Statement 12, where the total concentration of the one or more copolymer(s) is about 0.05 to about 20 wt % (based on the total weight of thepolymer blend), including all 0.01 wt % values and ranges therebetween (e.g., about 1 wt % or about 5 wt %).Statement 14. A polymer blend according to any one of Statements 12 or 13, where the polymer(s) is / are independently chosen from polyolefins, polyesters, polybutadienes, polystyrenes, and structural analogs thereof, and the like, and copolymers comprising one or more thereof (e.g., group(s) formed therefrom).Statement 15. A polymer blend according to any one of Statements 12-14, where a first polymer or polymers and / or a second polymer or polymers is / are independently a polyolefin (such as, for example, a polyethylene (e.g., a high-density polyethylene, a low-density polyethylene, a medium-density polyethylene, a linear low-density polyethylene, or a structural analog thereof, or the like), a polypropylene (such as, for example, an isotactic polypropylene, an atactic polypropylene, a syndiotactic polypropylene, or a structural analog thereof, or the like), a polymethylpentene, or a structural analog thereof, or the like), a polybutadiene, a polyester (such as, for example, an aliphatic polyester (e.g., polycaprolactone, poly (3 -hydroxybutyrate), long-chain (e.g., C12 to C200, including all integer number of carbons and ranges therebetween) aliphatic polyester (such as, for example, PE-18, 18, or a structural analog thereof, or the like), or a structural analog thereof, or the like), a polystyrene, a copolymer of ethylene and propylene (such as, for example, an ethylenepropylene rubber, an ethylene-propylene diene monomer copolymer, or a structural analog thereof, or the like), a polyolefin copolymer (such as, for example, a styrene-butadiene-styrene copolymer, an acrylonitrile-butadiene-styrene copolymer), or a structural analog thereof, or the like.Statement 16. A polymer blend according to any one of Statements 12-15, where a first polymer / second polymer ratio (e.g., the first polymer / second polymer ratio) (e.g., HDPE / zPP or the like) is about 95 / 5 to about 5 / 95 (w / w), including all 0.1 ratio values and ranges therebetween.Statement 17. A polymer blend according to any one of Statements 12-16, where at least a portion, substantially all, or all of one or more or all of the polymer(s) is / are independently chosen from virgin resins (such as, for example, polymer(s) directly after polymerization without any additional treatment / compounding steps or the like), specifically synthesized polymer(s), post-production waste polymer(s) (such as, for example, polymer resin(s) left as waste from industrial processes, e.g., punching machine leftovers or the like, or the like), post-consumer waste polymer(s) (such as, for example, polymer(s) recovered from any type of consumer application, e.g., food containers, water bottles, or the like, or the like), whichmay be purified, recycled material(s) (such as, for example, a recovered polymer waste or wastes (e.g., from industrial recycling facilities or the like), which may be comingled or the like), a reclaimed material or materials (e.g., waste polymer or polymers recovered from the environment or the like), or the like, or any combination thereof.Statement 18. A polymer blend according to any one of Statements 12-17, where the polymer blend is a monolith, a fiber, a sheet, a film (such as, for example, a thin film), a pellet, a powder, a foam, or the like.Statement 19. A polymer blend according to any one of Statements 12-18, where the number-averaged molecular weight (n) of the polymer(s) is / are independently about 1 to about 5,000 kDa (which may be determined by gel permeation chromatography (GPC) (e.g., calibrated relative to linear, narrowly-dispersed polyethylene standards or the like), size exclusion chromatography (SEC), or the like), including all integer kDa values and ranges therebetween (e.g., about 10 kDa to about 500 kDa, which may be for a HDPE / zPP copolymer or the like).Statement 20. A polymer blend according to any one of Statements 12-19, where the polymer blend has (or exhibits) increased uniaxial elongation or the like, compared to the polymer blend without the copolymer(s) (e.g., at least 2 times or greater, at least 3 times or greater, at least 50 times or greater, at least 70 times or greater, uniaxial elongation or the like, compared to the polymer blend without the copolymer(s)).Statement 21. A composition comprising one or more copolymer(s) of the present disclosure (e.g., copolymer(s) of any one of Statements 1-11).Statement 22. A composition according to Statement 21, further comprising one or more additive(s) or the like, or any combination thereof.Statement 23. A composition according to Statement 22, where the additive(s) is / are present (individually or in the aggregate) at about 0.1 weight percent (wt %) to about 10 wt % (based on the total weight of the polymer(s)), including all 0.1 wt % values and ranges therebetween. Statement 24. A composition according to any one of Statements 21-23, where the composition is a monolith, a fiber, a sheet, a film (such as, for example, a thin film), a pellet, a powder, a foam, or the like.Statement 25. A method of making one or more copolymer(s) (such as, for example, a copolymer of the present disclosure (e.g., a copolymer according to any one of Statements 1-11), a polymer blend of the present disclosure (e.g., a polymer blend of any of Statements 12-20)) comprising: contacting (e.g., in a reaction mixture, which may be a homogeneous mixture, a solution, or the like) two or more polymers (e.g., a first polymer, a secondpolymer, etc.) (e.g., where the polymers are independently homopolymers or copolymers) (e.g., HDPE / zPP or the like) (non-limiting examples of which are provided herein) with one or more radical(s) (non-limiting examples of which are provided herein), and optionally, one or more solvent(s) (e.g., solvent(s) that at least partially solubilize, substantially solubilize, or completely solubilize the polymer(s) (non-limiting examples of which are provided herein)); and optionally, heating the polymers, radical(s), and, if present, solvent(s), where the copolymer(s) is / are produced.Statement 26. A method according to Statement 25, where the method changes the polymer(s) melt flow behavior and introduces a degree of shear-thinning to otherwise Newtonian behaving polymer melts, as defined by the ratio of the melt viscosity at 0.1 Hz divided by the melt viscosity at 250 Hz (= R*) (e.g., ratios from 20 to 300, including all 0.1 ratio values and ranges therebetween).Statement 27. A method according to Statement 25 or 26, further comprising (i) forming a reaction mixture (which may be a solution, a melt, a suspension, an emulsion, or the like) comprising the two or more polymers and optionally, one or more solvent(s) prior to contacting the reaction mixture (e.g., adding) with the radical(s); or (ii) carrying out the contacting in a melt extruder (e.g., melt extruding a reaction mixture (which may be a solution, a melt, a gel, or the like)) comprising the two or more polymers, the radical(s), and optionally, one or more solvent(s).Statement 28. A method according to any one of Statements 25-27, where the two or more polymers are independently chosen from polyolefins (non-limiting examples of which are provided herein), polyesters (non-limiting examples of which are provided herein), polystyrenes (non-limiting examples of which are provided herein), and structural analogs thereof, and the like, and copolymers thereof.Statement 29. A method according to any one of Statements 25-28, where at least a portion, substantially all, or all of the polymers are virgin resins (such as, for example, polymers directly after polymerization without any additional treatment / compounding steps or the like), specifically synthesized polymers (for this application), post-production waste polymers (such as, for example, polymer resins left as waste from industrial processes, e.g., punching machine leftovers or the like, or the like), post-consumer waste polymers (such as, for example, polymers, which may be pure polymers, recovered from a consumer application, e.g., any type of consumer application, such as, for example, food containers, water bottles, or the like), recycled materials (such as, for example, recovered and potentially commingled polymer wastes from industrial recycling facilities or the like), reclaimed materials (such as,for example, waste polymers recovered from the environment or the like)), or the like, or any combination thereof.Statement 30. A method according to any one of Statements 25-29, where the ratio of two or more of the two or more polymers (such as, for example, first polymer(s) / second polymer(s) (e.g., zPP / HDPE or the like)) is about 95 / 5 to about 5 / 95 (w / w), including all 0.1 ratio values and ranges therebetween (e.g., about 10 / 90, about 50 / 50, about 70 / 30 (w / w), which may be an zPP / HDPE ratio)).Statement 31. A method according to any one of Statements 25-30, where the polymers (e.g., the first polymer, the second polymer, etc.) are present at (e.g., a reaction mixture comprises) about 0.1 wt % to about 70 wt %, including all 0.1 wt % values and ranges therebetween (e.g., about 5 wt % to about 25 wt %, or about 50 wt %), based on the total weight of polymer(s), the radical source(s) (e.g., radical precursor(s) or the like), and the solvent(s), if present. In various examples, the polymers are present at (e.g., a reaction mixture comprises) at about 5 wt % to about 25 wt % (e.g., based on the total weight of the reaction mixture), including all 0.1 wt % values and ranges therebetween (e.g., about 10 wt % to about 25 wt %), which may be for HDPE and zPP.Statement 32. A method according to any one of Statements 25-31, where one or more or all of the radical(s) is / are independently formed from a radical source.Statement 33. A method according to Statement 32, where the radical source is a radical precursor (such as, for example, a small molecule that forms one or more radical(s) as a result of homolytic bond cleavage or the like).Statement 34. A method according to Statement 33, where the radical precursor comprises or the radical precursors independently comprise one or more peroxide group(s), one or more azide group(s), one or more diazo group(s), one or more halogen group(s), one or more N-halo or N-xanthylamide group(s) or O-alkenylhydroxamate group(s), one or more aminoxyl radical group(s), or one or more structural analog(s) thereof, or the like.Statement 35. A method according to Statement 33 or 34, where the radical precursor or precursors is / are chosen from organic radical precursors (e.g., peroxides (such as, for example, peracids (e.g., peroxyacetic acid, performic acid, and structural analogs thereof, and the like), peroxy esters (such as, for example, tert-butylperoxybenzoate, tez7-amylperoxy-2-ethylhexanoate, tert-butyl peroxy acetate, and the like, and structural analogs thereof), diacyl peroxides (such as, for example, dibenzoylperoxide, dilauroyl peroxide, and structural analogs thereof, and the like), alkyl peroxides (such as, for example, 2,5-dimethyl-di-(2,5-tert-butylperoxy)hexane (DHBP), 1,1 -di (tert-amyl peroxy) cyclohexane, di-tert-butylperoxide, dicumyl peroxide, and structural analogs thereof, and the like), peroxy carbonates (such as, for example, diacetylperoxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, / c / 7-butylperoxy-2-ethyl hexyl carbonate, and structural analogs thereof, and the like), hydroperoxides (such as, for example, hydrogen peroxide, Zc / 7-butyl-hydroperoxide, methyl ethyl ketone peroxide, acetylacetone peroxide, and structural analogs thereof, and the like), azide compounds (such as, for example, benzenesulfonyl azide, 4-acetamidobenzenesulfonyl azide, and structural analogs thereof, and the like), diazo compounds (such as, for example, azobisisobutyronitrile, l,l’-azobis (cyclohexanecarbonitrile), 4,4’ -azobis(4-cyanoval eric acid), and structural analogs thereof, and the like), alkenylhydroxamates, and structural analogs thereof, and the like); inorganic peroxide precursors (such as, for example, ammonium persulfate, potassium peroxymonosulfate, potassium persulfate, and structural analogs thereof, and the like), halogens (such as, for example, chlorine, bromine, iodine, and the like), and structural analogs thereof, and the like), and structural analogs thereof, and the like, and any combination thereof.Statement 36. A method according to any one of Statements 33-35, where the radical precursor(s) is / are present at about 0.01 weight percent (wt %) to about 10 wt % (based on the total weight of the polymers), including all 0.1 wt % values and ranges therebetween (e.g., about 3 wt % to about 5 wt %, which may be for HDPE and zPP or the like).Statement 37. A method according to any one of Statements 25-36, where the method includes use of (e.g., a reaction mixture also comprises) one or more additive(s) (non-limiting examples of which are provided herein).Statement 38. A method according to Statement 37, where the additive(s) is / are present (individually or in the aggregate) at about 0.1 weight percent (wt %) to about 10 wt % (based on the total weight of the polymers), including all 0.1 wt % values and ranges therebetween. Statement 39. A method according to any one of Statements 25-38, where the contacting is carried out at a temperature of about ambient temperature (about 25 °C) to about 250 °C, including all 0.1 °C values and ranges therebetween (e.g., about 160 °C to about 180 °C, which may be for HDPE and zPP or the like), or at a temperature sufficient to form the radical(s).Statement 40. A method according to any one of Statements 25-39, where the contacting is carried out for about 1 minute to about 48 hours, including all 0.1 minute values and ranges therebetween, and / or for a time equivalent to a radical half-life time (ti / 2) of about 0.1 ti / 2 to about 20 ti / 2, including all 0.1 t₁₂ values and ranges therebetween.Statement 41. A method according to any one of Statements 25-40, the method further comprising quenching the contacted polymers and radical(s) (e.g., the reaction mixture or the like) (or addition of one or more quencher(s) or the like (non-limiting examples of which are provided herein)).Statement 42. A method according to any one of Statements 25-41, where the copolymer(s) is / are isolated (e.g., isolated by precipitation into non-solvents like alcohols (e.g., alcohols, such as, for example, methanol, ethanol, structural analogs thereof, and the like, and any combination thereof), selective precipitation out of a solvent by heating and controlled cooling), filtration, or the like).Statement 43. A composition comprising two or more polymers (e.g., a first polymer, a second polymer, etc.) (e.g., where the polymers are independently homopolymers or copolymers); one or more radical source(s); optionally, one or more quencher(s); and optionally, one or more solvent(s) (e.g., solvent(s) that at least partially solubilize, substantially solubilize, or completely solubilize the polymer(s)), where the composition may be suitable to produce a copolymer or copolymers of the present disclosure (such as, for example, copolymer(s) of any of Statements 1-11, copolymer(s) made by a method of the present disclosure (such as, for example, copolymer(s) made by a method of any of Statements 25-42), or any combination thereof) and / or one or more polymer blend(s) of the present disclosure (e.g., a polymer blend of any of Statements 12-20, polymer blend(s) made by a method of the present disclosure (such as, for example, polymer blend(s) made by a method of any of Statement 56)) and / or one or more composition(s) of the present disclosure (e.g., composition(s) according to any of Statements 21-24).Statement 44. A composition according to Statement 43, where the two or more polymers are independently chosen from polyolefins (non-limiting examples of which are provided herein), polyesters (non-limiting examples of which are provided herein), polystyrenes (nonlimiting examples of which are provided herein), and structural analogs thereof, and the like, and copolymers thereof.Statement 45. A composition according to Statement 43 or 44, where at least a portion, substantially all, or all of the polymer(s) is / are virgin resins (such as, for example, polymers directly after polymerization without any additional treatment / compounding steps or the like), specifically synthesized polymers (for this application), post-production waste polymers (such as, for example, polymer resins left as waste from industrial processes, e.g., punching machine leftovers or the like, or the like), post-consumer waste polymers (such as, for example, polymers, which may be pure polymers, recovered from a consumer application,e.g., any type of consumer application, such as, for example, food containers, water bottles, or the like), recycled materials (such as, for example, recovered and potentially comingled polymer wastes from industrial recycling facilities or the like), reclaimed materials (such as, for example, waste polymers recovered from the environment or the like), or the like, or any combination thereof.Statement 46. A composition according to Statement 43-45, where the ratio of two or more of the two or more polymers (such as, for example, first polymer(s) / second polymer(s) (e.g., iPP / HDPE or the like)) is about 95 / 5 to about 5 / 95 (w / w), including all 0.1 ratio values and ranges therebetween (e.g., about 10 / 90, about 50 / 50, about 70 / 30 (w / w), which may be an zPP / HDPE ratio).Statement 47. A composition according to Statement 43-46, where the composition comprises the two or more polymers (e.g., the first polymer, the second polymer, etc.) (e.g., HDPE / iPP or the like) (individually or in the aggregate) at about 0.1 wt % to about 70 wt %, including all 0.1 wt % values and ranges therebetween (e.g., about 5 wt % to about 25 wt %, or about 50 wt %), based on the total weight of the polymers, radical source(s) (e.g., radical precursor(s) or the like), and the quencher(s) and / or the solvent(s), if present. In various examples, the polymer(s) are present at (e.g., a reaction mixture comprises) at about 5 wt % to about 25 wt %, including all 0.1 wt % values and ranges therebetween (e.g., about 10 wt % to about 25 wt %), which may be for HDPE and iPP.Statement 48. A composition according to Statements 43-47, where the radical source(s) is / are a radical precursor (such as, for example, a small molecule that forms one or more radical(s) as a result of homolytic bond cleavage or the like) or radical precursors.Statement 49. A composition according to Statements 43-48, where the radical precursor(s) independently comprise one or more peroxide group(s), one or more azide group(s), one or more diazo group(s), one or more halogen group(s), one or more N-halo or N-xanthylamide group(s) or O-alkenylhydroxamate group(s), one or more aminoxyl radical group(s), or a structural analog thereof, or the like.Statement 50. A composition according to Statements 43-49, where the radical precursor(s) is / are chosen from organic radical precursors (e.g., peroxides (such as, for example, peracids (e.g., peroxy acetic acid, performic acid, and structural analogs thereof, and the like), peroxy esters (such as, for example, / cz7-butylperoxybenzoate, Zcz7-amylperoxy-2-ethyl hexanoate, tert-butyl peroxy acetate, and the like, and structural analogs thereof), diacyl peroxides (such as, for example, dibenzoylperoxide, dilauroyl peroxide, and structural analogs thereof, and the like), alkyl peroxides (such as, for example, 2,5-dimethyl-di-(2,5-tert-butylperoxy)hexane(DHBP), 1,1 -di( / 77-amy 1 peroxy) cyclohexane, di -Zc / V-butyl peroxi de, dicumyl peroxide, and structural analogs thereof, and the like), peroxy carbonates (such as, for example, diacetylperoxydicarbonate, di(2-ethylhexyl)peroxydicarbonate, Zc77-butylperoxy-2-ethylhexylcarbonate, and structural analogs thereof, and the like), hydroperoxides (such as, for example, hydrogen peroxide, tert-butyl -hydroperoxi de, methyl ethyl ketone peroxide, acetylacetone peroxide, and structural analogs thereof, and the like), azide compounds (such as, for example, benzenesulfonyl azide, 4-acetamidobenzenesulfonyl azide, and structural analogs thereof, and the like), diazo compounds (such as, for example, azobisisobutyronitrile, l,r-azobis(cyclohexanecarbonitrile), 4,4’ -azobi s(4-cyanoval eric acid), and structural analogs thereof, and the like), alkenylhydroxamates, and structural analogs thereof, and the like); inorganic peroxide precursors (such as, for example, ammonium persulfate, potassium peroxymonosulfate, potassium persulfate, and structural analogs thereof, and the like), halogens (such as, for example, chlorine, bromine, iodine, and the like, and structural analogs thereof, and the like), and structural analogs thereof, and the like, and any combination thereof.Statement 51. A composition according to Statements 43-50, where the composition comprises the radical precursor(s) (individually or in the aggregate) at about 0.01 weight percent (wt %) to about 10 wt % (based on the total weight of the polymers), including all 0.1 wt % values and ranges therebetween (e.g., about 3 wt % to about 5 wt %, which may be for HDPE and zPP or the like).Statement 52. A composition according to Statements 43-51, where the quencher(s) is / are chosen from 2,6-di-tert-butyl-4-methylphenol, 2,2,6,6-tetramethylpiperidinyloxyl, and structural analogs thereof, and the like, and any combination thereof.Statement 53. A composition according to Statements 43-52, where the composition comprises the quencher(s) (individually or in the aggregate) at about 0.01 weight percent (wt %) to about 10 wt % (based on the total weight of the polymers), including all 0.1 wt % values and ranges therebetween (e.g., about 3 wt % to about 5 wt %, which may be for HDPE and zPP or the like).Statement 54. A composition according to Statements 43-53, the composition further comprising one or more additive(s) (non-limiting examples of which are provided herein). Statement 55. A composition according to Statements 43-54, where the composition comprises the additive(s) (individually or in the aggregate) at about 0.1 weight percent (wt %) to about 10 wt % (based on the total weight of the polymer(s)), including all 0.1 wt % values and ranges therebetween.Statement 56. A method of making a polymer blend of the present disclosure (e.g., a polymer blend of any of Statements 12-20) comprising: blending (such as, for example, solvent blending, melt blending, ball-milling, or the like, or any combination thereof) (i) one or more copolymer(s) of the present disclosure (such as, for example, copolymer(s) of any of Statements 1-12) and / or one or more copolymer(s) made by a method of the present disclosure (e.g., copolymer(s) made by a method of any of Statements 25-37), and two or more polymers or (ii) a composition of the present disclosure (such as, for example, a composition of any one of Statements 43-55), where the polymer blend (which may be a compatibilized polymer blend, such as, for example, a compatibilized polymer blend as described herein) is formed.Statement 57. An article of manufacture comprising one or more copolymer(s) of the present disclosure (such as, for example, copolymer(s) of any of Statements 1-11, copolymer(s) made by a method of the present disclosure (such as, for example, copolymer(s) made by a method of any of Statements 25-42), copolymer(s) made using a composition of the present disclosure (such as, for example, a composition of any one of Statements 43-55), or any combination thereof) and / or one or more polymer blend(s) of the present disclosure (e.g., a polymer blend of any of Statements 12-20, polymer blend(s) made by a method of the present disclosure (such as, for example, polymer blend(s) made by a method of any of Statement 56), copolymer(s) made using a composition of the present disclosure (such as, for example, a composition of any one of Statements 43-55), or any combination thereof) and / or one or more composition(s) of the present disclosure (e.g., composition(s) according to any of Statements 21-24).Statement 58. An article of manufacture according to Statement 57, where the article of manufacture is chosen from containers (such as, for example, food storage containers, consumer product containers, water bottles (e.g., reusable water bottles and the like), and the like), plastic grocery bags, packaging, pipes, insulating panels, bathtubs, window panel doors, floors, tiles, syringes, petri dishes, specimen bottles, safety helmets, tendon prostheses, tracheal tubes, automobile components, electronic components, clothing (such as, for example, waterproof clothing, fiber form for clothing, and the like), carpets, non-stick pots and pans, eye-wear, CDs and DVDs, furniture, outdoor play equipment, toys, and the like.

[0098] The steps of the methods described in the various examples disclosed herein are sufficient to carry out methods of the present disclosure (such as, for example, to produce one or more copolymer(s) of the present disclosure and / or one or more polymer blend(s) and / or one or more composition(s)). Thus, in various examples, a method consists essentially of acombination of the steps of the methods disclosed herein. In various other examples, a method consists of such steps.

[0099] The following Example is presented to illustrate the present disclosure. The Example is not intended to be limiting in any manner.EXAMPLE

[0100] This example provides non-limiting examples of copolymers, polymer blends, copolymer compositions, methods of making copolymers, precursor polymer blend compositions, methods of making polymer blends, and articles of manufacture of the present disclosure.

[0101] One-Step Radical-Induced Synthesis of Graft Copolymers for Effective Compatibilization of Polyethylene and Polypropylene. The synthesis of copolymers from high-density polyethylene (HDPE) and isotactic polypropylene (zPP) has gained increasing attention due to its ability to improve recycling of incompatible mixed polyolefin waste feed streams. A new radical grafting process is described that yields HDPE-g-zPP copolymers from HDPE and zPP using a commercially available peroxide. Tensile testing of brittle 70 / 30 HDPE / zPP mixtures with these graft copolymers added showed promising compatibilization, improving the elongation at break of the blends from 20% up to 1080%. Detailed kinetic studies coupled with thermal and rheological characterization revealed optimized conditions for HDPE and zPP macroradical coupling and a deeper understanding of the grafting reaction. This optimization yielded HDPE-g-zPP copolymers that compatibilize HDPE and zPP blends at loadings as low as 2.5 wt %. The versatility of this macroradical grafting reaction was demonstrated by preparing an effective compatibilizer from untreated post-consumer waste plastics.

[0102] The preparation of non-reactive copolymer compatibilizers via bond formation between existing homopolymers is shown in FIG. 1. It was hypothesized that radical chemistry would be attractive for such an approach due to its synthetic simplicity, reagent availability, and potential scalability. Importantly, polyethylene and polypropylene show different reactivity when exposed to radicals. H-abstraction of HDPE typically occurs at the methylene to yield secondary macroradicals, which can recombine to form crosslinked HDPE gels, as shown in FIG. 2. Conversely, H-abstraction of zPP occurs primarily at the methine, producing tertiary macroradicals which undergo / / -chain scission, cleaving the polymer backbone into an alkene-terminated chain and another secondary macroradical, as shown in FIG. 3. It was hypothesized that, when combined, HDPE and zPP macroradicals would formpolyethylene-gzzz / / -polypropylene (HDPE-g-zPP) structures that could function as HDPE / zPP compatibilizers. It was hypothesized that recombination of HDPE and zPP macroradicals in solution could yield effective non-reactive copolymer compatibilizers, as shown in FIG. 4.

[0103] A solution-based synthesis of HDPE-g-zPP graft copolymers for HDPE / zPP compatibilization was developed. Detailed kinetic studies were conducted to monitor the grafting reaction and compatibilization over time. Finally, HDPE-g-zPP compatibilizers from waste plastics were synthesized, emphasizing the potential and versatility of this graft copolymer preparation.

[0104] Studies began by reacting homogeneous solutions of HDPE (A / n,rei = 42 kg / mol, D = 2.5) and zPP (A / n,rei = 54 kg / mol, D = 5.5) in 1, 2, 4-tri chlorobenzene (TCB) at 180 °C with 2,5-dimethyl-2,5-(di- / cz7-butylperoxy)hexane (DHBP) as the radical source. The initial reaction time was set to 7 min (equivalent to 6.0 ti / 2 as determined via Arrhenius calculations), when about 98.5% of the peroxide decomposed. A starting ratio of HDPE:zPP = 30:70 was selected to access HDPE-g-zPP copolymers with an approximately 50:50 HDPE:zPP composition. It was hypothesized that only about 50% of the starting zPP performs productive radical coupling, since zPP undergoes / -chain scission to generate a vinyl- terminated fragment and an active secondary macroradical. Additionally, an excess of zPP could inhibit polyethylene crosslinking, preventing the formation of undesired HDPE gels.

[0105] Table 1. Condition optimization for the synthesis of HDPE-g-zPP copolymers by macroradical recombination.Entry HDPE:zPP c React" tRtR* T Mn,reicDcsB,iowt%'z(wt %:wt (g / mL) (min) (ti / 2) (°C) (kg / mol) (%) %)1 30:70 0.10 7.0 6.0 180 17 7.1 480 ± 270 2e30:70 0.15 7.0 6.0 180 46 5.3 20 ± 23 30:70 0.05 7.0 6.0 180 17 5.2 220 ± 160 4 30:70 0.15 7.0 6.0 180 26 6.2 690 ± 705 30:70 0.20 7.0 6.0 180 -f-f-f6 50:50 0.15 7.0 6.0 180 27 7.5 20 ± 5 7 40:60 0.15 7.0 6.0 180 27 8.3 440 ± 130 8 20:80 0.15 7.0 6.0 180 18 5.2 690 ± 160 9 10:90 0.15 7.0 6.0 180 17 3.7 500 ± 200 10 30:70 0.15 5.0 4.3 180 26 4.2 700 ± 170 11 30:70 0.15 6.0 5.1 180 32 3.0 720± 180 12 30:70 0.15 9.0 7.7 180 20 9.2 870 ± 30 13 30:70 0.15 12.0 4.0 170 26 3.5 800 ± 120 14 30:70 0.15 10.2 3.4 170 32 3.7 880 ± 20 15 30:70 0.15 28.0 3.5 160 23 5.6 730 ± 100 16 30:70 0.15 24.1 3.0 160 23 4.7 870 ± 80aPolymer concentration (CReact) before peroxide addition, 10 mL reaction volume;breaction time in multiples of the peroxide half-life at the temperature indicated as determined via Arrhenius calculations;cnumber average molecular weight of graft copolymers determined via SEC at 150 °C in 1,2,4-trichlorobenzene relative to monodisperse polyethylene standards;dtensile testing results for a blend of HDPE / / PP = 70 / 30 + 10 wt % compatibilizer relative to polymer blend, average and standard deviation of 7-12 measurements;eno peroxide added; f reaction gelled.

[0106] These initial conditions yielded a copolymer with quantitative mass recovery, a lower A / n,rei (17 kg / mol) and larger dispersity (7.1) compared to the starting materials (Table 1, entry 1). Performing uniaxial tensile testing on the obtained graft copolymers revealed improved material properties. The graft copolymer displayed an average elongation at break (SB) of 680 ± 120% compared to SB = 60 ± 20% of a physical 30 / 70 HDPE / zPP mixture. Furthermore, the compatibilization efficacy of the product was assessed by tensile testing a 70 / 30 blend of commercial HDPE and zPP with 10 wt % loading of the graft copolymer. The compatibilized blend showed improved mechanical properties, with elongation at break at 10 wt % (sB,i0wt%) of 480 ± 270% compared to the uncompatibilized blend (SB = 20 ± 2%).

[0107] To confirm the hypothesized radical reactivity, HDPE and zPP were separately subjected to the grafting reactions. When only HDPE was treated with peroxide, the reaction mixture gelled immediately, indicating that the presence of zPP suppresses HDPE self-crosslinking. When zPP was subjected to peroxide without HDPE present, no crosslinking occurred. The copolymer’s M̄n,rel decreased from 45 kg / mol with a dispersity of 6.4 to about 18 -25 kg / mol with lower dispersities of 2.1-2.8 depending on the reaction time. This degradation experiment also provided a molecular weight estimate for the zPP grafts. A control experiment without peroxide showed no coupling, and the obtained material did not compatibilize HDPE / zPP blends (Table 1, entry 2).

[0108] Encouraged by these initial results, the solution-based macroradical recombination was optimized by systematically varying different reaction parameters. As it was hypothesized that the spatial proximity of the HDPE and zPP macroradicals in solution is important to graft formation, the reaction concentration was varied from 0.05 to 0.20 g / mL (Table 1, entries 1, 3-5). More concentrated grafting reactions yielded copolymers facilitating improved elongation at break of HDPE / zPP blends (from εB,10wt% = 220 ± 160% at 0.05 g / mL to εB,10wt% = 690 ± 70% at 0.15 g / mL). Further increasing the concentration to 0.20 g / mL led to gelation, suggesting polymer crosslinking (Table 1, entry 5). As such, the reaction proceeded with a reaction concentration of 0.15 g / mL.

[0109] Next, the feed ratio of HDPE:zPP was varied from HDPE:zPP = 50:50 to 10:90 (Table 1, entries 6-9). The more HDPE-rich feeds resulted in less effective compatibilization (εB,10wt% = 24 ± 5% at 50:50 and εB,10wt% = 440 ± 130% at 40:60). The 20:80 feed ratio yielded a copolymer with very similar compatibilization efficiency to the 30:70 feed ratio (εB,10wt% = 690 ± 160%). As the iPP feed ratio further increased, the copolymers showed less effective compatibilization (εB,10wt% = 500 ± 200%). To confirm the composition ratio of HDPE:zPP in the graft copolymers, a model graft copolymer was prepared using atactic polypropylene (aPP, M̄n,rel = 116 kg / mol, D = 2.3) instead of zPP, as aPP can be separated from HDPE after the reaction. The resulting copolymer (97 wt % recovery) was subjected to a Soxhlet extraction to separate non-grafted aPP from grafted HDPE-g-aPP.1H-NMR. analysis confirmed the isolation of an HDPE-g-aPP copolymer with a composition of 55:45 wt % HDPE:rzPP and a total yield of 69 wt %. This evidence supports the initial hypothesis that about half of the feed zPP is attached to the HDPE while the other half unproductively cleaves, validating the selection of the 30:70 HDPE:zPP feed ratio. The residual 30 wt % of unattached zPP remained in the product.

[0110] The reaction time was optimized through a kinetic investigation of the grafting reaction under standard conditions (HDPE:zPP = 30:70, 0.15 g / mL, 180 °C). Over the screened reaction time, compatibilization efficacy first increased, then plateaued and subsequently decreased, as shown in FIG. 5. The best compatibilization was found in a timeframe of 5.0 - 9.0 min (4.3 - 7.7 t1 / 2) reaching a maximum at 9.0 min (7.7 t1 / 2), which resulted in compatibilized blends with an average elongation at break of 870 ± 30% at 10 wt % loading.

[0111] Using these kinetic results, three different time frames were identified during which the obtained graft copolymers showed trends in their capability of compatibilizing HDPE / zPP blends. During the initial reaction phase (0.0 - 5.0 min / 0.0 - 4.3 t1 / 2), the compatibilization increased continuously until an elongation at break of 700 ± 170% was achieved. Then, a plateau was observed (5.0 - 9.0 min / 4.3 - 7.7 t1 / 2), during which all copolymers showed good compatibilization. Past 9.0 min (7.7 t1 / 2), the compatibilization efficacy dropped significantly. To understand the reaction progress, DSC, SEC, and melt rheology were utilized to correlate the effect of reaction time on the formation of HDPE-g-zPP copolymers and their resulting compatibilization efficacies.

[0112] Between tR = 0.0 to 5.0 min (0.0 to 4.3 ti / 2), low to moderate compatibilization was observed (εB,10wt% = 200 ± 170% to 700 ± 170%), which it was hypothesized is due to incomplete grafting of zPP on HDPE. Indeed, DSC measurements between tR = 0 - 6.0 min (0 - 5.1 t1 / 2) revealed a bimodal zPP fraction melting transition, indicating the presence of multiple zPP species. Concurrently, the melting points of HDPE (Tm,PE) and zPP (Tm,PP), as well as their respective melting enthalpies, ΔHm,PE and ΔHm,PP, decreased, as shown in FIG.6. This suggests the formation of covalent bonds between zPP and HDPE, which disturb the formation of large crystallites in both polymers. Interestingly, the decrease of Tm,PP and ΔHm,PP was more pronounced than Tm,PE and Am, PE, indicating a stronger influence of the radical reaction on the zPP than on HDPE Evidence for increased zPP grafting during this initial phase of the reaction was further supported by oscillatory parallel plate frequency sweep rheological measurements. It has been reported that long chain branched polymers exhibit increased shear thinning behavior compared to linear polymers. The shear thinning behavior was quantified by defining a relative ratio of shear viscosity (R*) as R* = η*0.1Hz / η*250Hz. Increasing R* values indicate increased long chain branching. After 1.5 min (1.3 t1 / 2), the product exhibited an R* = 13.9, which was within the R* range of the starting materials used (R*HDPE = 13.2; R*iPP = 23.7). R* increased to 141 after 5.0 min (4.3 t1 / 2), indicating more pronounced shear thinning as branching / grafting progressed, as shown in FIG. 8. The observed increase in A* was accompanied by an expected enhancement in compatibilization efficiency, as increased grafting density should yield more effective compatibilizers.

[0113] The most effective compatibilization was observed at an intermediate reaction time of tR = 5.0 - 9.0 min (4.3 - 7.7 t1 / 2), with elongations at break up to 870 ± 30% at 10 wt % loadings (Table 1, entries 1, 10-12). It was hypothesized that the maximum compatibilization measured in this range is a result of maximized grafting between zPP and HDPE while limiting / i-chain scission of grafted zPP side chains, with half of the zPP from the feed attached to the HDPE.

[0114] After 9.0 min (7.7 ti / 2) until 15.0 min (12.8 ti / 2), the obtained graft copolymers showed noticeably decreased compatibilization efficiency. Tm,PP decreased from 142.0 °C to 136.9 °C and ΔHm,PP decreased from 13 J / g to 8 J / g. The zPP melting transition was no longer bimodal, and the Tm,PP and ΔHm,PP decrease became less pronounced. As shown in FIG. 7, Mn,rel continued to decrease, while Mw,rel and dispersity increased. It was concluded that HDPE-g-zPP formation rate slowed and unwanted side reactions increased during this timeframe. Additionally, there was a sharp increase in the reaction mixture viscosity after 12 min (10.3 t1 / 2), which was attributed to crosslinking. It is believed that crosslinking was induced by / i-chain scission of grafted zPP sidechains, which decreased graft length and produced sidechain macroradicals that recombined with HDPE macroradicals. Quantitative13C-NMR spectra of a non-crosslinked reaction and the soluble fraction of a partially crosslinked reaction showed the same 30:70 HDPE:zPP ratio as the initial feed, supporting the hypothesis. If self-crosslinking of HDPE was a competitive side reaction, the HDPE:zPP ratio in the graft copolymer in NMR analysis would change after the removal of any crosslinked fractions. After 15.0 min (12.8 t1 / 2), the resulting material was further crosslinked, compromising the yield (47 wt % mass recovery). The remaining soluble fraction was not an effective compatibilizer (εB,10wt% = 170 ± 30%). In summary, this kinetic evaluation provided an understanding of the graft reaction progression, correlating DSC, SEC, and rheology measurements with the compatibilization efficiency of the graft copolymers formed at different reaction times.

[0115] This kinetic method of utilizing DSC and rheology to assess reaction progress allowed investigation of the influence of the reaction temperature on the grafting reaction. Changing the reaction temperature influences the rate of primary alkoxy radical formation, the decomposition to their respective secondary alkyl radicals, and the abstraction selectivity of the alkoxy and alkyl radicals for different hydrogens on HDPE and zPP. Thus, the ideal time frame for obtaining the most efficient graft compatibilizers is affected by the temperature. Performing kinetic series at lower temperatures of 170, 160, and 150 °C allowed the identification of the optimal reaction times for each temperature, as shown in FIG. 12 andFIG. 13. At 150 °C, none of the graft copolymers prepared efficiently compatibilized the 70 / 30 HDPE / zPP blend at 10 wt % (SB, IO wt% < 350 ± 210%). For reactions run at 170 °C, the optimal reaction time shifted to 3.4 ti / 2 - 4.0 ti / 2 (10.2 and 12.0 min) and yielded graft copolymers that achieved compatibilization with εB,10wt% = 880 ± 20% and 800 ± 120% (Table 1, entries 13-14). At 160 °C, maximum compatibilization at 10 wt % was achieved at times of 3.0 t1 / 2 to 3.5 t1 / 2 (24.1 - 28.0 min) with εB,10wt% = 870 ± 80% and 730 ± 100% (Table 1, entries 15-16).

[0116] Usually, polyolefin waste feed streams are mixtures of HDPE and zPP in varying ratios. Thus, the copolymer compatibilization efficacy was investigated for different feed ratios of HDPE / iPP = 85 / 15, 50 / 50, 30 / 70, and 15 / 85 with 10, 7.5, and 5.0 wt % of copolymer prepared at 180 °C. For 50 / 50 mixtures and more iPP-rich mixtures (30 / 70, 15 / 85), high elongations at break were obtained even at 5.0 wt %. For the HDPE-rich 85 / 15 mixture, 10 wt % copolymer compatibilized the blend effectively, but at lower loadings the compatibilization efficacy dropped significantly. None of the copolymers prepared at 180 °C efficiently compatibilized 70 / 30 HDPE / zPP blends at 5 wt % (FIG. 12, entries 1-9).Generally, the graft copolymers prepared using the procedure are more effective at compatibilizing zPP-rich HDPE / zPP blends (50 / 50-15 / 85). The 70 / 30 HDPE / zPP ratio was focused on for all further compatibilization experiments.

[0117] Compatibilization efficacy of HDPE-g-zPP copolymers prepared at 170 °C and 160 °C at lower loadings of 5 wt % and 2.5 wt % was tested. The graft copolymers from 170 °C reactions at 3.4 t1 / 2 and 4.0 t1 / 2 (10.2 and 12.0 min) achieved εB,5.0wt% = 480 ± 190% and 320 ± 190%, but failed to compatibilize at 2.5 wt % loading (FIG. 12, entries 12 and 13). The HDPE-g-zPP prepared at 160 °C and reaction times of 3.0-3.4 ti / 2 (24.1 - 28.0 min) achieved £B,5.owt% of 500 ± 230% and 440 ± 200%. The graft copolymer prepared at 3.0 t1 / 2 (24.1 min) successfully compatibilized at 2.5 wt % loadings with εB,2.5wt% = 320 ± 220%, making this graft copolymer an effective compatibilizer (FIG. 13, entries 18-19). Compared to commercial compatibilizers, the prepared HDPE-g-zPP achieved competitive elongation at break at 5.0 wt % and even showed efficacy at 2.5 wt % loading.

[0118] Furthermore, to investigate the effect of HDPE backbone chain length on compatibilization efficacy, a series of narrow-dispersity HDPEs with i. rd = 44-200 kg / mol (£) < 1.3) were prepared. After reacting the different HDPEs with commercial zPP under standard conditions, the melting transitions of the resulting graft copolymers were measured (FIG. 14, entries 5-9). The lowest molecular weight HDPE-based graft copolymer showed the lowest Tm, PP, and increasing HDPE backbone chain length increased Tm,PP, as shown inFIG. 9. As the HDPE chain length increases, the reaction mixture viscosity increases, which it is believed slowed down the macroradical grafting and led to higher Tm,PP. Initially, it was hypothesized that increasing HDPE backbone chain length would increase compatibilization efficacy, as higher molecular weight copolymers show better compatibilization. Surprisingly, the 44 kg / mol HDPE-based graft copolymer showed the most efficient compatibilization of all copolymers prepared at 10 wt % and 5 wt % with εB,10wt% = 1080 ± 50% and εB,5.0wt% = 690 ± 190%, and further also compatibilized at 2.5 wt % with εB,2.5wt% = 300 ± 250%, as shown in FIG. 10 and FIG. 14, entry 9. To explain this observation, R* was measured for this copolymer. The R* of 20.5, in a similar range to linear starting homopolymers, indicated a more linear, potentially triblock-like architecture.

[0119] This method could accommodate post-consumer waste as starting material, increasing its applicability. To demonstrate the versatility of the macroradical recombination reaction, post-consumer waste plastics without previous purification or additive removal were tested as starting materials (HDPE water jug: Mn,rel = 18 kg / mol, Đ = 7.1; zPP yogurt container: Mn,rel = 50 kg / mol, D = 6.6). This waste-based HDPE-g-zPP copolymer effectively compatibilized 70 / 30 HDPE / zPP blends at 10 wt % (εB,10wt% = 830 ± 50%) and at 5 wt % (εB,5.0wt% = 500 ± 240%), as shown in FIG. 11. These results highlight the possibility of preparing polyolefin compatibilizers directly from polyolefin waste plastics in a cheap, easy, and potentially scalable one-step synthesis.

[0120] HDPE-g-zPP graft copolymers were synthesized through a solution-based macroradical recombination reaction of homopolymers. Compared to other established processes, this synthetic route does not require copolymerization using transition metal catalysts but rather utilizes existing HDPE and zPP in combination with a commercially available peroxide. After reaction condition optimization, compatibilization of 70 / 30 HDPE / zPP blends with loadings as low as 2.5 wt % was achieved. SEC, DSC, and rheology are a diagnostic set of analytical tools to assess the reaction progress and yielded insights into the grafting mechanism. The grafting reaction can tolerate waste plastics as feedstocks without prior purification, making this process a step towards cheaper compatibilizers. A highly feasible, inexpensive, and scalable method to compatibilize polyolefin wastes was developed.

[0121] Materials. The following chemicals were purchased from commercial sources and used as received: 2,5-dimethyl-2,5-di( / cz7-butylperoxy)hexane (DHBP) (Sigma-Aldrich and Fisher Scientific, 92% purity); 1, 2, 4-tri chlorobenzene (Fisher Scientific, HPLC grade); trityl tetrakis(pentafluorophenyl)borate ([Ph3C][B(C6Fs)4]) (A2B Chem, 97% purity);bis(indenyl)zirconium dichloride (Ind2ZrC12) (Strem Chemicals, min. 98% purity); tri-z.w-butylaluminum (Al(zBu)3) (Sigma-Aldrich); methanol (Fisher Scientific, ACS grade); toluene (Fisher Scientific, ACS grade). Methyl aluminoxane (MAO) (30 wt % in toluene) was generously donated by Albemarle Corporation and dried by removing volatiles (toluene and trace trimethylaluminum) under vacuum while heating at 40 °C for at least 8 hours. HPLC grade toluene was purchased from Fisher Scientific, purified over columns of alumina and copper (Q5) and molecular sieves, collected by a Straus flask and freeze-pump-thawed three cycles prior to use. Ethylene (Matheson, Matheson purity) and propylene (Airgas, polymer grade) were purified over columns of copper Q5 and 4A molecular sieves.Pyridylamidohafnium catalyst Hf-1 and phenoxyimine titanium catalyst Ti-1 for the synthesis of narrow dispersed iPP and HDPE, respectively, were prepared according to modified procedures from the literature. The following polymers were purchased or obtained from commercial sources and used as received: polypropylene (Sigma-Aldrich, isotactic, average Mw-300 kg / mol, average Mn-55 kg / mol); Total mHDPE 5510EP (TotalEnergies One Tech Belgium); DOW HDPE Unival DMDA6400 NT7 (DOW Chemicals); INEOS zPP H02C-00 (INEOS). The post-consumer HDPE was obtained from a 1 -gallon jug of Great Value brand water, and the post-consumer zPP was obtained from a 32-ounce Chobani brand yogurt container. Commercial HDPE and iPP were used as received. Post-consumer iPP (yogurt cup) was washed with soap and water and air-dried. Post-consumer HDPE (water jug) was air-dried.

[0122] Table 2. SEC and DSC data for the polymers used.Mn,rel Mw,rel Đ Tm Polymer[kg / mol] [kg / mol] [-] [°C] Total mHDPE 5510EP 42 103 2.5 135 Sigma zPP 54 300 5.5 167DOW HDPE 27 96 3.6 131 INEOS zPP 51 355 7.0 166 HDPE Water jug 18 132 7.1 135 zPP Yogurt container 50 329 6.6 166 ᵃ Molecular weight determined via SEC at 150 °C in 1,2,4-trichlorobenzene with 0.01 wt % BHT as stabilizer relative to polyethylene standards; ᵇ Determined via DSC (second heating cycle).

[0123] Methods. ¹H and ¹³C{¹H} NMR spectroscopy was recorded on a 500 MHz Bruker AVANCE III HD spectrometer with a broadband Prodigy cryoprobe. NMR spectra were recorded at 403 K and 500 MHz (1H) or 126 MHz (13C). Chemical shifts (8) for1H NMR spectra were referenced to the residual solvent protons of 1,1,2,2-tetrachloroethane-d2 (TCE-d2, 6.00 ppm) and chemical shifts for ¹³C{¹H} NMR spectra were referenced to the deuterated solvent itself (TCE-d2, 73.78 ppm). Quantitative¹³C{¹H}-NMR spectroscopy was performed at 403 K using chromium(III) acetylacetonate as a relaxation agent (17 mg Cr(acac)₃, 25 mg polymer in 0.5 mL TCE-d2) using adjusted measurement parameters (ns = 1024, dl = 8.5 s, at = 1.5 s). All NMR spectra were processed using MestReNova.

[0124] Relative high-temperature size-exclusion chromatography (HT-SEC) was performed on an Agilent 1260 Infinity II high-temperature GPC equipped with a refractive index (RI) detector and three Agilent PL-Gel Olexis (300 x 7.5 mm) columns. The samples were prepared with a concentration of 1 mg / mL and were eluted with a flow of 1.0 mL / min at 150 °C using 1, 2, 4-tri chlorobenzene (with 0.01 wt % di -tert-butyl hydroxy toluene as stabilizer) as eluent. The SEC is calibrated against narrow polyethylene standards from Varian and Polymer Standards Service. Data analysis was performed using Agilent GPC / SEC software.

[0125] Differential scanning calorimetry (DSC) measurements of polymer samples were performed on a Mettler-Toledo polymer DSC instrument equipped with a chiller under a nitrogen atmosphere. Approximately 2-5 mg of each polymer sample was prepared in a crimped aluminum pan for each run. DSC samples were first heated from 25 °C to 200 °C and then cooled to 25 °C, followed by being heated to 200 °C. The heating and cooling rates were 10 °C / min. The melting temperatures (Tm) and enthalpies (ΔHm) were obtained from the second heating cycles, and the crystallization temperature (Tc) and enthalpy (ΔHc) from the first cooling cycles, respectively, using STARe software.

[0126] Rheological measurements were performed on a TA Instruments DHR-20 rheometer using an 8 mm parallel plate in a temperature-controlled environmental test chamber under a nitrogen atmosphere. The sample was loaded onto the bottom parallel plate at 180 °C, and the top plate was lowered to a trim gap of 1050 μm. Excess polymer material was trimmed and then the plate was lowered to a gap of 1000 μm. Complex viscosity (q*) profiles were obtained at 180 °C and 1% strain with oscillatory shear from 0.1 to 500 rad / s. Before each frequency sweep, the sample was equilibrated at 180 °C for 3 min to ensure uniform sample temperature. Each sample was tested two times.

[0127] Compatibilization of polymer blends was performed using two different methods (A) and (B). 2.1 g DOW HDPE Unival DMDA6400 NT7 and 0.9 g INEOS zPP H02C-00 (70 / 30 wt % / wt % blend) were mixed with the respective amount of graft copolymer (HDPE-g-zPP) as indicated in wt % relative to the HDPE / zPP blend. The polymer mixture was pressed into a sheet on a 4120 hydraulic unit Carver press using Mylar protective sheets in between two stainless-steel sheets for 1 min at 180 °C and a load of 1000 lbs. For method (A), the sheet was cut into 0.5 cm wide strips, and the strips were fed into an Xplore Instruments 5CC Micro Compounder at 190 °C with a screw speed of 130 s⁻¹ for 8 min under N2 protection. Then, the extruded strand was pressed into a sheet. For method (B), the sheet was cut into 3x3 cm squares, stacked, and pressed for 1 min at 180 °C and a load of 1000 lbs. Subsequently, the resulting sheet was cut into 3x3 cm squares, stacked, and pressed at 180 °C and a load of 1000 pounds for 3 min, which was repeated four more times to ensure uniform mixing. The resulting sheet was pressed into tensile testing dogbone samples using a stainless-steel dogbone die mold at 180 °C for 5 min under a load of 2000 lbs. The samples were removed from the melt press immediately after pressing and trimmed with a razor blade to give specimens with a gauge length of 10 mm, a gauge width of 2.4-2.6 mm, and a gauge thickness of 0.6-0.8 mm. Uniaxial tensile elongation measurements were performed using a Shimadzu Autograph AGS-X tensile tester under ambient conditions with a crosshead velocity of 10 mm / min until break.

[0128] Radical half-life time determination. The peroxide used was 2,5-dimethyl-2,5-(di-Zcz7-butyl peroxy )hexane (DHBP, Luperox 101, L101) supplied in technical grade (92% purity). To precisely determine reaction time as a function of peroxide half-life time (ti / 2) at different temperatures, the Arrhenius equation with literature-reported values for preexponential factor A = 8.73 × 10¹⁵ s⁻¹ and activation energy EA=155.7kJ / mol was used. Using the Arrhenius equation, the rate constant k was determined as a function of temperature.k = A • e^(-EA / R·T)The percentage of remaining peroxide after a particular reaction time was calculated as %peroxide = e^(-k·t)which was rearranged to obtain the half-life of the peroxide (the time after which 50% of the peroxide was decomposed, %peroxide = 0.5)In (0.5)t1 / 2 = -ln(0.5) / kUsing the literature-reported values for A and EA, the following rate constants k and half-life times ti / 2 were calculated for DHBP. In the manuscript, reaction times were reported in minutes and multiples of the half-life at each reaction temperature for comparability between different reaction temperatures.

[0129] Table 3. Rate constants and half-life times determined via Arrhenius equation as a function of reaction temperature.Temperature T Rate constant k [s’ti / 2 [min][°C] *]150 5.25 • IO’422.0160 1.46 • 10’37.92170 3.87 • 10’32.98180 9.84 • 10’31.17190 2.40 • IO’20.48200 5.64 • IO’20.20

[0130] Graft Copolymer Synthesis5 wt% 2,5-dimethyl-2,5-(di-fert- -butylperoxy)hexane (DHBP)150 - 180 °C, 0 - 12.8t1 / 2, 0.05 - 0.20 g / mL polymer in 1,2,4-trichlorobenzene high-density polyethylene (HDPE) + isotactic polypropylene (iPP) → HDPE-g-iPPJ

[0131] Total mHDPE 5510EP and Sigma zPP with respective amounts as indicated in Table 2 were weighed into a 20 mL septa-capped vial with a stir bar, and 10 mL 1,2,4-tri chlorobenzene were added. The mixture was degassed by sparging with nitrogen for 10 min and heated to 150-180 °C with stirring for 1.5 h to ensure proper mixing of the polymer solution. 75 mg DHBP (5 wt % relative to polymer) in 0.5 mL 1, 2, 4-tri chlorobenzene was added at once, and the reaction was heated for the indicated time spans. After the reaction, the mixture was precipitated in 500 mL cold methanol, filtered, and dried. The obtained polymer was redissolved in about 60 mL toluene at 110 °C and reprecipitated into 300 mL cold methanol. The graft copolymers were dried in a vacuum oven at 70 °C overnight prior tocompatibilization. The isolated yield for the grafting reaction was in the range of 95 - 99 wt

[0132] Control Experiments.

[0133] 1. zPP degradation control experiment5 wt% 2,5-dimethyl-2,5-(di-tert- -butylperoxy)hexane (DHBP)180 °C, 0 - 12.8t1 / 2, 0.15 g / mLpolymer in 1,2,4-trichlorobenzeneisotactic polypropyleneFor the zPP degradation control experiment, 1.5 g of Sigma zPP was weighed into a 20 mL septa-capped vial with a stir bar, and 10 mL 1,2,4-trichlorobenzene was added. The mixture was degassed by sparging with nitrogen for 10 min and heated to 180 °C with stirring for 1.5 h. 5 wt % (75.0 mg) of DHBP in 0.5 mL 1,2,4-trichlorobenzene was added at once, and the reaction was heated for the indicated time spans. After the reaction, the mixture was precipitated into 500 mL cold methanol, filtered, and dried. The polymers were dried in a vacuum oven at 70 °C overnight prior to SEC, DSC, and rheology analysis.

[0134] 2 HDPE crosslinking control experiment5 wt% 2,5-dimethyl-2,5-(di-tert- -'''-'•X'-butylperoxy)hexane (DHBP) ]180°C, 0 -3.211 / 2, 0.15 g / mL ~polymer in 1,2,4-trichlorobenzenehigh-density polyethylene (HDPE) → crosslinkedethylene (HDPE) gelsFor the HDPE crosslinking control experiment, 1.5 g of mHDPE 5510EP was weighed into a 20 mL septa-capped vial with a stir bar, and 10 mL 1,2,4-trichlorobenzene was added. The mixture was degassed by sparging with nitrogen for 10 min and heated to 180 °C with stirring for 1.5 h. 5 wt % (75.0 mg) of DHBP in 0.5 mL 1,2,4-trichlorobenzene was added at once, and the reaction was heated for the indicated time spans. Crosslinking was observed within the first 3 -4 min.

[0135] 3. aPP grafting experimentAtactic polypropylene was prepared using a modified procedure using an Ind2ZrC12 catalyst. The obtained polypropylene was completely atactic and had a number average molecular weight of 116 kg / mol with a dispersity of 2.3.5 wt% 2,5-dimethyl-2,5-(di-fert- -butylperoxy)hexane (DHBP) 180 °C, 7 min, 0.15 g / mL ] polymer in 1,2,4-trichlorobenzene / k, high-density poly- atactic poly- I HI3PE-g-aPP ethylene (l-isJPE) propylene (aPP). J'”'-',c Total mHDPE 5510EP (0.4508 g) and aPP (1.0508 g) were weighed into a 20 mL septa- capped vial with a stir bar, and 10 mL 1, 2, 4-tri chlorobenzene was added. The mixture was degassed by sparging with nitrogen for 10 min and heated to 180 °C under stirring for 1.5 h to ensure proper mixing of the polymers. DHBP (5 wt % relative to polymer, 75.0 mg) in 0.5 mL 1,2, 4-tri chlorobenzene was added at once, and the reaction was heated for 7 min. Then the reaction was precipitated into 500 mL cold methanol and filtered. The wet polymer was transferred into a Soxhlet extraction thimble and dried at 70 °C under vacuum for two days, giving 1.46 g (97.2 wt %) product. The extraction thimble was placed in a Soxhlet extraction apparatus, and the product was extracted with hexanes for 8 hours with a cycle time of about 1.5 min. Afterwards, the extraction thimble was removed and dried for two days at 70 °C, giving 1.03 g (69 wt %) of insoluble copolymer. The hexanes solution was collected, and the solvent was removed in vacuo, giving a soluble fraction of pure aPP of 0.424 g (28 wt %). The soluble and insoluble fractions were subject to 'H-NMR analysis and SEC, showing that the soluble fraction exclusively contained aPP while the insoluble fraction contained HDPE and aPP fractions, proving the covalent attachment of aPP to HDPE.

[0136] Narrow-Dispersed Starting Polymers.

[0137] Synthesis and Characterization of Starting Materials. Synthesis of narrowdispersity iPPs. Modified by the polymerization procedure described in the literature, 100 mL toluene, 10 mmol trityl tetrakis(pentafluorophenyl)borate, 10 mmol pyridyl amidohafnium catalyst Hf-1, and various amounts of Al(zBu)3 were added to a 6 oz flat-bottomed Fisher- Porter reactor (Andrews Glass) in a glovebox. The reactor was then sealed, brought out of the box, and stirred at room temperature for 10 minutes before propylene (3.5-4.0 g) was charged into the reactor. The reactor was then left stirring for 3 hours in a cold-water bath. The reactor was then vented, unsealed, and the reaction was quenched by pouring methanol into the reactor. The zPP product was then collected by filtration and was dried in a vacuum oven for hours at 70 °C.

[0138] Synthesis of narrow dispersity HDPEs. In a typical reaction, an oven-dried 2 L three-neck flask equipped with a magnetic stir bar was charged with 1 L of toluene. The vessel was sealed under nitrogen. A solution of phenoxyimine titanium catalyst Ti-1 (150 mg,186 μmol) in toluene (40 mL) was prepared and drawn into two 20 mL syringes equipped with stainless-steel needles (Hamilton, 12-inch, gauge 18, point style 2), which were sealed at the tip using a rubber septum. A solution of dried MAO (1.5 g, 25.8 mmol) in toluene (40 mL) was prepared and drawn into two 20 mL syringes equipped with stainless-steel needles (Hamilton, 12-inch, gauge 18, point style 2), which were sealed at the tip using a rubber septum. The syringes were then removed from the glovebox. The three-neck flask was submerged into a 23 °C water bath, and ethylene was sparged into the reactor at 5 psig for 2 min with vigorous stirring. The MAO solution was then injected into the flask and the resulting mixture was further sparged for 2 min. The initiator solution was then injected to start the polymerization. The reaction mixture was quenched with methanol (10 mL) while stirring after the appropriate reaction time. The polymer solution was precipitated into acidic methanol (25 mL of 37% HCl in 475 mL of methanol) and stirred for 16 h. The resulting polymers were filtered, washed with methanol, and dried under vacuum at 70 °C to constant weight.

[0139] Table 4. Molecular weights and poly dispersity for the synthetic zPPs and HDPEs used.Afn,rel" DaPolymer[kg / mol] [-]zPP 120 1.3zPP 200 1.4zPP 290 1.5zPP 420 1.9HDPE 44 1.1HDPE 73 1.1HDPE 89 1.1HDPE 110 1.3HDPE 200 1.3“ Determined via SEC at 150 °C in 1,2,4-TCB with 0.01 wt % BHT as stabilizer relative to narrow dispersity HDPE standards.

[0140] Grafting Reaction of Narrow-Dispersity and Commercial Polymers70 wt%5 wt% 2,5-dimethyl-2,5-(di-fert- -butylperoxy)hexane (DHBP) 180 °C, 7 min, 0.15 g / mL polymer in 1,2,4-trichlorobenzene narrow dispersity commercial / PR synthetic HDPEcommercial narrow dispersitymHDPE 5510EP synthetic iPPThe general procedure, as explained in the Graft Polymer Synthesis above, was employed. All polymers were analyzed using SEC, DSC, and rheology and used in the same standard tensile testing experiments. The results can be found in FIG. 14.

[0141] Although the present disclosure has been described with respect to one or more particular example(s), it will be understood that other examples of the present disclosure may be made without departing from the scope of the present disclosure.

Claims

CLAIMS:

1. A copolymer comprising:one or more first group(s) comprising a plurality of groups independently formed from one or more ethylenically unsaturated monomer(s); andone or more second group(s) independently comprising a plurality of groups independently formed from one or more ethylenically unsaturated monomer(s),with a proviso that each second group is different from one or more of the first group(s), wherein one or a plurality or all of the second group(s) is covalently bonded to one or a plurality of first segment(s).

2. The copolymer of claim 1, wherein at least about 70% by weight (wt %) of the copolymer is soluble in chlorobenzene, dichlorobenzene, trichlorobenzene, an alkyl aromatic compound, 1.1.2.2-tetrachloroethane, 1,2-di chloroethane, diphenyl ether, benzene, biphenyl, hydrocarbon solvent, tetrahydrofuran, or a structural analog thereof, or a combination thereof at a temperature of about 25 °C to about 250 °C; and / orthe copolymer comprises about 10% or less insoluble fraction in chlorobenzene,di chlorobenzene, trichlorobenzene, an alkyl aromatic compound, 1,1,2,2-tetrachloroethane, 1.2-di chloroethane, diphenyl ether, benzene, biphenyl, hydrocarbon solvent, tetrahydrofuran, or a structural analog thereof, or a combination thereof at a temperature of about 25 °C to about 250 °C.

3. The copolymer of claim 1, wherein the copolymer comprises or exhibits a melting point or melting points independently from the melting point of a highest melting point of a polymer from which a first group or a second group is formed or derived to about 100 °C lower than a lowest melting point of a polymer from which a first group or a second group is formed or derived.

4. The copolymer of claim 1, wherein the copolymer exhibits shear-thinning behavior as defined by a ratio of melt viscosity at 0.1 Hz divided by the melt viscosity at 250 Hz, wherein the ratio is about 20 to about 300.

5. The copolymer of claim 1, wherein the copolymer comprises a number-averaged molecular weight (Mn) of about 1 kDa (kDa = kilodalton(s)) to about 1,000 kDa and / or the copolymer comprises Mpof about 10 kDa to about 500 kDaand / orthe copolymer comprises 10% or more lower Mvrelative to a polymer or polymers used to make the copolymer and / or a physical blend of a polymer or polymers used to make the copolymer.

6. The copolymer of claim 1, wherein the copolymer comprises one or more linking group(s), where each linking group is covalently bonded to a first polymer group and a second polymer group.

7. The copolymer of claim 6, wherein the linking group(s) is / are chosen from:, and structural analogs thereof.

8. The copolymer of claim 1, wherein the copolymer comprises end groups independently chosen from alkyl groups and alkenyl groups.

9. The copolymer of claim 1, wherein the first group or groups and / or second group or groups independently comprise(s) a polyolefin group, a polybutadiene group, a polyester group, a polystyrene group, a long-chain aliphatic polyester group, a styrene-butadiene- styrene rubber, an ethylene propylene rubber, an ethylene propylene diene monomer copolymer, an acrylonitrile-butadiene-styrene copolymer, or a structural analog thereof.

10. The copolymer of claim 1, wherein the copolymer is a thermoplastic material, a compatibilizer, or a thermoplastic elastomer.

11. The copolymer of claim 1, wherein the copolymer is a means of compatibilizing two or more polymers, a means for improving one or more of uniaxial elongation at break, yield stress, impact resistance, and shear or compressive strength of a composition comprising two or more polymers and the copolymer compared to a same composition that does not comprise the copolymer.

12. A polymer blend comprising one or more copolymer(s) of claim 1 and one or more polymer(s).

13. The polymer blend of claim 12, wherein the one or more copolymer(s) is / are present at a concentration of about 0.05 wt % to about 20 wt %.

14. The polymer blend of claim 12, wherein the polymer(s) is / are independently chosen from polyolefins, polyesters, polybutadienes, polystyrenes, and structural analogs thereof, and copolymers comprising one or more thereof.

15. The polymer blend of claim 12, whereina first polymer or polymers and / or a second polymer or polymers is / are independently a polyolefin, a polystyrene, a copolymer of ethylene and propylene, a polyolefin copolymer, or a structural analog thereof.

16. The polymer blend of claim 12, wherein a first polymer / second polymer ratio is about 95 / 5 to about 5 / 95 (w / w).

17. The polymer blend of claim 12, wherein at least a portion, substantially all, or all of one or more or all of the polymer(s) is / are independently chosen from virgin resins, specifically synthesized polymer(s), post-production waste polymer(s), post-consumer waste polymer(s), reclaimed materials, and any combination thereof.

18. The polymer blend of claim 12, wherein the polymer blend is a monolith, a fiber, a sheet, a film, a pellet, a powder, or a foam.

19. The polymer blend of claim 12, wherein the polymer(s) independently comprise a number-averaged molecular weight (Mn) of about 1 to about 5,000 kDa.

20. The polymer blend of claim 12, wherein the polymer blend exhibits increased uniaxial elongation compared to the polymer blend without the copolymer(s).

21. A composition comprising one or more copolymer(s) of claim 1.

22. The composition of claim 21, further comprising one or more additive(s).

23. The composition of claim 22, wherein the additive(s) is / are present at about 0.1 wt % to about 10 wt %.

24. The composition of claim 21, wherein the composition is a monolith, a fiber, a sheet, a film, a pellet, a powder, or a foam.

25. A method of making one or more copolymer(s) of claim 1 comprising:contacting two or more polymers with one or more radical(s), and optionally, one or more additives and / or solvent(s); andoptionally, heating the polymers, radical(s), and, if present, additive(s) and / or solvent(s),wherein the copolymer(s) is / are produced.

26. The method of claim 25, wherein the method changes a polymer(s) melt flow behavior and introduces a degree of shear-thinning, as defined by a ratio of a melt viscosity at 0.1 Hz divided by the melt viscosity at 250 Hz, wherein the ratio is about 20 to about 300.

27. The method of claim 25, further comprising(i) forming a reaction mixture comprising the two or more polymers and optionally, one or more solvent(s) prior to contacting the reaction mixture with the radical(s); or(ii) carrying out the contacting in a melt extruder comprising the two or more polymers, the radical(s), and optionally, one or more solvent(s).

28. The method of claim 25, wherein the two or more polymers are independently chosen from polyolefins, polyesters, polystyrenes, and structural analogs thereof, and copolymers thereof.

29. The method of claim 25, wherein at least a portion, substantially all, or all of the polymers are virgin resins, specifically synthesized polymers, post-production waste polymers, post-consumer waste polymers, or any combination thereof.

30. The method of claim 25, wherein a ratio of two or more of the two or more polymers is about 95 / 5 to about 5 / 95 (w / w).

31. The method of claim 25, wherein the polymers are present at about 0.1 wt % to about 70 wt %.

32. The method of claim 25, wherein one or more or all of the radical(s) is / are independently formed from one or more radical source(s).

33. The method of claim 32, wherein the one or more radical source(s) is / are a radical precursor or precursors.

34. The method of claim 33, wherein the radical precursor comprises or the radical precursors independently comprise one or more peroxide group(s), one or more azide group(s), one or more diazo group(s), one or more halogen group(s), one or more N-halo or N-xanthylamide group(s) or O-alkenylhydroxamate group(s), one or more aminoxyl radical group(s), or one or more structural analogs thereof.

35. The method of claim 33, wherein the radical precursor or precursors is / are chosen from organic radical precursors, inorganic peroxide precursors, and any combination thereof.

36. The method of claim 33, wherein the radical precursor or precursors is / are present at about 0.01 wt % to about 10 wt %.

37. The method of claim 25, wherein the additive(s) is / are present at about 0.1 weight percent (wt %) to about 10 wt %.

38. The method of claim 25, wherein the contacting is carried out at a temperature of about 25 °C to about 250 °C.

39. The method of claim 25, wherein the contacting is carried out for about 1 minute to about 48 hours.

40. The method of claim 25, wherein the contacting is carried out for a time equivalent to a radical half-life time (t 1 / 2) of about 0.1 ti / 2 to about 20 ti / 2.

41. The method of claim 25, the method further comprising addition of one or more quencher(s).

42. The method of claim 25, wherein the copolymer(s) is / are isolated.

43. A composition comprisingtwo or more polymers;one or more radical source(s);optionally, one or more quencher(s); andoptionally, one or more solvent(s),wherein the composition is suitable to produce a copolymer or copolymers of claim 1.

44. The composition of claim 43, wherein the two or more polymers are independently chosen from polyolefins, polyesters, polystyrenes, and structural analogs thereof, and copolymers thereof.

45. The composition of claim 43, wherein at least a portion, substantially all, or all of the polymers are virgin resins, specifically synthesized polymers, post-production waste polymers, post-consumer waste polymers, reclaimed materials, or any combination thereof.

46. The composition of claim 43, wherein a ratio of two or more of the two or more polymers is about 95 / 5 to about 5 / 95 (w / w).

47. The composition of claim 43, wherein the composition comprises the two or more polymers at about 0.1 wt % to about 70 wt %.

48. The composition of claim 43, wherein the radical source(s) is / are a radical precursor or radical precursors.

49. The composition of claim 48, wherein the radical precursor comprises or the radical precursors independently comprise one or more peroxide group(s), one or more azide group(s), one or more diazo group(s), one or more halogen group(s), one or more N-halo or N-xanthylamide group(s) or O-alkenylhydroxamate group(s), one or more aminoxyl radical group(s), or a structural analog thereof.

50. The composition of claim 48, wherein the radical precursor or the radical precursors is / are chosen from organic radical precursors, inorganic peroxide precursors, and structural analogs thereof, and any combination thereof.

51. The composition of claim 48, wherein the composition comprises the radical precursor or the radical precursors at about 0.01 wt % to about 10 wt %.

52. The composition of claim 43-51, wherein the quencher(s) is / are independently chosen from 2,6-di-tert-butyl-4-methylphenol, 2,2,6,6-tetramethylpiperidinyloxyl, and structural analogs thereof, and any combination thereof.

53. The composition of claim 43, wherein the composition comprises the quencher(s) at about 0.01 weight percent (wt %) to about 10 wt %.

54. The composition of claim 43, wherein the composition further comprises one or more additive(s).

55. The composition of claim 54, wherein the composition comprises the additive(s) at about 0.1 weight percent (wt %) to about 10 wt %.

56. A method of making a polymer blend of claim 12 comprising:blending (i) one or more copolymer(s) of claim 1 and two or more polymers, wherein the polymer blend is formed.

57. An article of manufacture comprising one or more copolymer(s) of claim 1.

58. The article of manufacture of claim 57, wherein the article of manufacture is chosen from containers, plastic grocery bags, packaging, pipes, insulating panels, bathtubs, window panel doors, floors, tiles, syringes, petri dishes, specimen bottles, safety helmets, tendon prostheses, tracheal tubes, automobile components, electronic components, clothing, carpets, non-stick pots and pans, eye-wear, CDs and DVDs, furniture, outdoor play equipment, and toys.

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