CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Patent Application No. 63/355,387, filed June 24, 2022; the contents of the above-identified 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 grant number DE-AC02- 07CH11358 awarded by the Department of Energy. The government has certain rights in the invention.

BACKGROUND OF THE DISCLOSURE

[0003] Over the last half-century, polyolefins have cemented their place as the preferred materials for single-use applications due to their wide ranging and tunable material properties paired with the low cost and availability of their feedstocks. However, their strength and chemical stability result in a half-life of hundreds of years and they have accumulated in massive amounts in the environment. Ideally, a commodity material would have similar properties but with viable end-of-life options such as biodegradability or chemical recycling. [0004] Recently, there has been considerable interest in designing new polymers that have desirable material properties and sustainable end-of-life options. However, these materials are often considerably more expensive than commodity polyolefins or exhibit inferior properties. To truly match the properties of polyolefins, we envisioned designing a material that is structurally similar to polyethylene or polypropylene while possessing dispersed cleavable groups that would allow for the possibility of chemical recycling. If these cleavable groups are sufficiently spaced out, they should not impact the material properties. [0005] A number of aliphatic polyesters with extended unsaturated hydrocarbon chains have been reported. With a spacing of about 20 carbons between ester linkages, these materials often show melting temperatures below 100 °C. Recently, Mecking and coworkers demonstrated a chemically recyclable C18 polyester with tensile properties nearly identical to high-density polyethylene (HDPE) and a melting temperature of 99 °C. This class of materials often require biorefining of monomers or a multi-step synthetic route. Similar materials have also been synthesized through ring opening metathesis polymerization (ROMP) and acyclic diene metathesis (ADMET). However, each of these materials is limited to rather short unsaturated chains which disrupt crystallization and cause a decrease in the material’s melting temperature.

[0006] Grubbs and coworkers showed that using chain transfer agents, telechelic polyolefins could be synthesized via ROMP. By changing the chain transfer agent, chain-end functionality can be controlled. Functional chain transfer agents can also produce telechelic polyolefins via catalyzed chain growth polymerization. Partially dehydrogenated polyethylene has been cleaved via metathesis-mediated ethenolysis to form divinyl telechelic macromonomers as well as functionalized via cross-metathesis with acrylates. However, due to the need for stereocontrol in the polymerization, it is difficult to use these methods to form telechelic isotactic polypropylene (zPP) macromonomers. Previously, thermal degradation of zPP was used to obtain telechelic macromonomers, but this method often suffers from the decrease of melting point, poor control of molecular weight, and formation of monofunctionalized and unfunctionalized side-products. Functionality to zPP has also been introduced via copolymerization with polar monomers.

SUMMARY OF THE DISCLOSURE

[0007] The present disclosure provides, inter alia, polymeric materials, polymers, methods of making polymeric materials and polymers. The present disclosure also provides uses of the polymeric materials and polymers.

[0008] In various examples, a polymer comprises the following structure: , where R ^x is independently at each occurrence an alkenyl group or the like and z is about 3 to about 500, including all integer z values and ranges therebetween, where PG is a polymeric group and the polymeric groups, independently at each occurrence, comprise a carbon backbone and a molecular weight of about 500 g/mol to about 500,000 g/mol, including all 0.1 g/mol values and ranges therebetween. In various examples, each polymeric group independently comprises a homopolymer group, a copolymer group, or any combination thereof. In various examples, the polymeric groups are independently chosen from polyethylene groups, polypropylene groups, polybutylene groups, polystyrene groups, polytetrafluoroethylene groups, polyvinylchloride groups, polyacrylonitrile groups, polyacrylate groups, polymethacrylate groups, polyvinylacetate groups, and the like, structural analogs thereof, copolymer groups thereof, and combinations thereof. In various examples, each polymeric group independently comprises a polyalkylene group or the like. In various examples, the polymeric groups independently comprise a molecular weight (Mw and/or Mn) of about 500 g/mol to about 100,000 g/mol, including all 0.1 g/mol values and ranges therebetween and/or about 10 to about 4,000 repeat units, including all integer repeat unit values and ranges therebetween and/or a PDI of about 1.5 to about 10, including all 0.1 PDI values and ranges therebetween. In various examples, the polymeric group(s) is/are, independently, at least partially or completely atactic, isotactic, isoenriched, syndiotactic, syndioenriched, or the like, or any combination thereof. In various examples, the polymeric groups independently comprise one or more domain(s) and the domain(s) is/are, independently, crystalline, semi-crystalline, amorphous, or the like. In various examples, the polymer further comprises one or more pendant alkenyl group(s). In various examples, the polymer further comprises about 0.05 mol% to about 40 mol% pendant groups (relative to the backbone carbon-carbon double bonds), including all 0.01 mol% values and ranges therebetween. In various examples, the polymeric material comprises about 0.05 mol% to about 40 mol% (relative to the backbone carbon-carbon double bonds), including all 0.1 mol% values and ranges therebetween pendant alkenyl groups.

[0009] In various examples, a polymeric material comprises the following structure: , where PG is a polymeric group comprising a carbon backbone, CLG is a cleavable linking group, and the polymeric group(s), independently, comprise a molecular weight of about 500 g/mol to about 500,000 g/mol, including all 0.1 mol% values and ranges therebetween. In various examples, each polymeric group independently comprises a homopolymer group, a copolymer group, or any combination thereof. In various examples, the polymeric group(s) is/are independently chosen from polyethylene groups, polypropylene groups, polybutylene groups, polystyrene groups, polytetrafluoroethylene groups, polyvinylchloride groups, polyacrylonitrile groups, polyacrylate groups, polymethacrylate groups, polyvinylacetate groups, and the like, structural analogs thereof, copolymer groups thereof, and combinations thereof. In various examples, at least a portion of the polymeric group(s) comprise(s) one or more pendant group(s), each pendant group comprising one or more carbon-carbon double bond(s). In various examples, the polymeric group(s) independently comprise a molecular weight (Mw and/or Mn) of about 500 g/mol to about 100,000 g/mol, including all O. lg/mol values and ranges therebetween. In various examples, the polymeric group(s) independently comprise 10 to about 4000 repeat units, including all integer repeat unit values and ranges therebetween and/or a poly dispersity index (PDI) of about 1.5 to about 10, including all 0.1 PDI values and ranges therebetween. In various examples, the polymeric groups are independently at least partially or completely atactic, isotactic, isoenriched, syndiotactic, syndioenriched, or the like, or any combination thereof. In various examples, the polymeric group comprises one or more domain(s) and the domains are, independently, crystalline, semi-crystalline, amorphous, or the like. In various examples, the cleavable linking group, independently at each occurrence, comprises an ester group, an alkenyl group, a siloxide group, a carbonate group, an amide group, an acetal group, a ketal group, or the like, or a structural analog thereof. In various examples, the cleavable linking group, independently at each occurrence, comprises a group chosen from the following structure:

O , where R ⁴ is, at each occurrence, optionally present, and chosen from aliphatic groups and the like, and R ⁵ is, at each occurrence, optionally present, and chosen from aliphatic groups, alkyl ester groups, and the like. In various examples, the polymeric material comprises the following structure: each independently optionally present, and R ¹⁷ are independently at each occurrence, chosen from aliphatic groups and the like. In various examples, where n is about 2 to about 200, including all integer n values and ranges therebetween. In various examples, the polymeric material comprises the following structure:

R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are independently at each occurrence, chosen from aliphatic groups and the like, and PG ¹ and PG ² are independently at each occurrence a polyethylene group, a polypropylene group, a polystyrene group, or the like. In various examples, x and y are as described herein. In various examples, the polymeric material comprises the following structure: , where R ¹⁰ , R ¹¹ , R ¹² are independently at each occurrence, chosen from aliphatic groups and the like, and PG is independently at each occurrence a polyethylene group, a polypropylene group, o polystyrene group, or the like and PEST is a polyester group or the like. In various examples, x and y are as described herein. In various examples, the polymeric material is in the form of a powder, pellets, a monolith, a coating, a sheet, a film, a fiber, a solid article, a hollow article, a foam, a composite, or the like. In various examples, the polymeric material exhibits or has one or more or all of the following: a melting temperature (Tm) of about 40°C to about 250°, including all 0.1 °C values and ranges therebetween; a decomposition temperature (Td) of about 250 to about 450°C°, including all 0.1 °C values and ranges therebetween; or a glass transition temperature (Tg) of about -80 to about 200°C°, including all 0.1 °C values and ranges therebetween.

[0010] In various examples, a polymerizable polymeric material comprises the following structure: RG PG RG , where PG is a polymeric group comprising a carbon backbone, RG is a reactive group, and the polymeric group(s), independently, comprise a molecular weight of about 500 g/mol to about 100,000 g/mol, including all 0.1 g/mol values and ranges therebetween. In various examples, each polymeric group independently comprises a homopolymer group, a copolymer group, or any combination thereof. In various examples, the polymeric group is chosen from polyethylene groups, polypropylene groups, polystyrene groups, polytetrafluoroethylene groups, polyvinylchloride groups, polyacrylonitrile groups, polyacrylate groups, polymethacrylate groups, polyvinylacetate groups, and the like, structural analogs thereof, copolymer groups thereof, and any combination thereof. In various examples, the polymeric group comprises about 10 to about 1000 repeat units, including all integer repeat unit values and ranges therebetween, and/or a PDI of about 1.5 to about 10, including all 0.1 PDI values and ranges therebetween. In various examples, the polymeric group is partially or completely atactic, isotactic, isoenriched, syndiotactic, syndioenriched, or the like, or any combination thereof. In various examples, the polymeric group comprises one or more domain(s) and the domain(s) is/are, independently, crystalline, semi-crystalline, or amorphous. In various examples, the reactive groups, independently at each occurrence, comprise a hydroxyl group, an alkenyl group, an acid group or deprotonated structural analog thereof, an ester group, a thiol group, a ketone group, an amine group, alkynyl group, azide group, halide group, or the like, or a structural analog thereof. In various examples, at least one of the reactive groups further comprises a cleavable group. In various examples, the reactive groups, independently at each occurrence, comprise a group comprising the following structure:

O , where R ¹ is, independently at each occurrence, optionally present, and chosen from aliphatic groups and R ² is, at each occurrence, chosen from hydrogen group (- H), aliphatic groups, aryl groups, and the like. In various examples, the polymeric material comprises the following structure: are each independently at each occurrence, chosen from aliphatic groups and the like. In various examples, the polymeric material comprises the following structure: are independently at each occurrence, chosen from aliphatic groups, and the like, and PG is a polyethylene group, a polypropylene group, a polystyrene group, or the like.

[0011] In various examples, a method of making a polymerizable polymeric material of the present disclosure comprises: contacting one or more polymer(s) comprising a plurality of polymeric groups and a plurality of backbone carbon-carbon double bonds, one or more reactive group precursor compound(s), and one or more catalyst(s), where the polymerizable polymeric material is formed. In various examples, at least a portion of the reactive group precursor compound(s) comprise at least one carbon-carbon double bond and at least a portion of the catalyst(s) is/are chosen from olefin metathesis catalysts and the like. In various examples, at least a portion or all of the catalyst(s) is/are chosen from metal-carbene metathesis catalysts, and the like, and any combination thereof. In various examples, the polymerizable polymeric material comprises one or more carbon-carbon double bond(s), the method further comprising at least partially or completely hydrogenating the polymeric material forming a hydrogenated polymerizable polymeric material. [0012] In various examples, a method of making a polymeric material of the present disclosure comprises: subjecting one or more polymerizable polymeric material(s) to polymerizable conditions such that the polymeric material is formed. In various examples, a method further comprises forming an article of manufacture by forming one or more of the polymeric material(s).

[0013] In various examples, a method of depolymerizing a polymeric material comprises: subjecting the polymeric material to hydrolysis, alcoholysis, transesterification, alkene metathesis, or ozonolysis conditions, and, optionally, isolating at least a portion of or substantially all of the resulting products.

[0014] In various examples, an article of manufacture comprising one or more polymeric material(s) of the present disclosure. In various examples, the article of manufacture is in the form of a monolith, a coating, a sheet, a film, a fiber, a solid article, a hollow article, a foam, a composite, or the like. In various examples, the article of manufacture is a packaging article, a single-use article, a sports article, a biomedical article, an agricultural article, an automotive article, an electronic article, or the like. In various examples, the article of manufacture is biodegradable. In various examples, the article of manufacture is at least partially or substantially recyclable.

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. 1 shows an ester-linked polypropylene material.

[0017] FIG. 2 shows a two-step synthesis of bridged biphenylphenol ligands.

[0018] FIG. 3a-d shows depolymerization of zPP-co-BD (Table 1, entry 4) and repolymerization to an ester-linked polypropylene material, a) Reaction schematic and conditions, b) ’H NMR spectra, c) GPC chromatograms, and d) DSC traces for polymer intermediates and products. The NMR spectra and DSC traces are in order (as shown in the legend in FIG. 3a) from top to bottom.

[0019] FIG. 4 shows representative stress-strain curves for zPP-co-BD, zPP-co-EG, and LLDPE.

[0020] FIG. 5 shows a stress vs. strain plot for zPP-co-BD.

[0021] FIG. 6 shows a stress vs. strain plot for zPP-co-EG. DETAILED DESCRIPTION OF THE DISCLOSURE

[0022] Although claimed subject matter will be described in terms of certain examples and embodiments, other examples and embodiments, including examples that do not provide all of the benefits and features set forth herein, are also within the scope of this disclosure. Various structural, logical, and process step changes may be made without departing from the scope of the disclosure.

[0023] 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, +/-1% or less, and +/-0.1% or less of and from the specified value), insofar such variations 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.

[0024] 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.

[0025] As used herein, unless otherwise indicated, the term “aliphatic group” is a branched or unbranched (linear) hydrocarbon group or a cyclic hydrocarbon (carbocyclic) group, optionally, comprising one or more degree(s) of unsaturation. An aliphatic group may be an alkyl group. Non-limiting examples of aliphatic groups with one or more degree(s) of unsaturation include alkenyl groups, alkynyl groups, aliphatic cyclic groups, and the like. In various examples, an aliphatic group is a Ci to Ce aliphatic group, including all integer numbers of carbons and ranges of numbers of carbons therebetween (e.g., a Ci, C2, C3, C4, C5, or Ce aliphatic group). In various examples, an aliphatic group is a Ci to C20 aliphatic group, including all integer numbers of carbons and ranges of numbers of carbons therebetween (e.g., a Ci, C2, C3, C4, C5, Ce, C7, C ₈ , C9, C10, Cn, C12, C13, C14, C15, Cie, C17, Ci8, C19, or C20 aliphatic group). An aliphatic group may be unsubstituted or substituted with one or more substituent(s). Examples of substituents include, but are not limited to, halide groups (-F, -Cl, -Br, -I, and the like), aryl groups, halogenated aryl groups, alkoxide groups, amine groups, nitro groups, carboxylate groups, carboxylic acids, ether groups, hydroxyl group, and the like, and combinations thereof.

[0026] As used herein, unless otherwise indicated, the term “aryl group” refers to C5 to C30 (e.g., C ₅ , C ₆ , C ₇ , C ₈ , C ₉ , C10, Cn, C12, C13, Ci ₄ , Ci ₅ , Ci ₆ , C17, Ci ₈ , C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29, and C30) aromatic or partially aromatic carbocyclic groups, including all integer numbers of carbons and ranges of numbers of carbons therebetween. In various examples, an aryl group is an aromatic group. In various examples, aryl groups comprise polyaryl groups such as, for example, fused ring groups, biaryl groups, or the like, or any combination thereof. In various examples, the aryl group is unsubstituted or substituted with one or more substituent(s). Examples of substituents include, but are not limited to, various substituents such as, for example, hydroxyl group, halide groups (-F, -Cl, - Br, and -I), aliphatic groups (e.g., additional alkyl groups, alkenyl groups, alkynyl groups, and the like), halogenated aliphatic groups (e.g., trifluoromethyl group and the like), cycloaliphatic groups, aryl groups, halogenated aryl groups, alkoxide groups, amine groups, ether groups, carboxylate groups, carboxylic acid, ester groups, amide groups, cyano groups, nitro groups, thioether groups, silyl ether groups, isocyanate groups, and the like, and any combination thereof. In various examples, aryl groups contain one or more hetero atom(s), such as, for example, oxygen, nitrogen (e.g., pyridinyl groups and the like), sulfur, and the like, and any combination thereof. Examples of aryl groups include, but are not limited to, phenyl groups, biaryl groups (e.g., biphenyl groups and the like), fused ring groups (e.g., naphthyl groups and the like), hydroxybenzyl groups, tolyl groups, xylyl groups, furanyl groups, benzofuranyl groups, indolyl groups, imidazolyl groups, benzimidazolyl groups, pyridinyl groups, and the like.

[0027] As used herein, unless otherwise stated, the term “structural analog” refers to any polymeric material (e.g., a polymerizable polymeric material or the like) or polymer or portion thereof (such as, for example, one or more group(s) thereof or the like) or the like if one atom or group of atoms, functional groups, or substructures is replaced with another atom or group of atoms, functional groups, substructures, or the like. In various examples, the term “structural analog” refers to any group that is derived from an original polymeric material (e.g., a polymerizable polymeric material or the like) or polymer or portion thereof (such as, for example, one or more group(s) thereof or the like) or the like by a chemical reaction, where the compound is modified or partially substituted such that at least one structural feature of the compound or group is retained.

[0028] 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 other chemical 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 radicals and multivalent radicals, such as, for example, divalent radicals, trivalent radicals, and the like). Illustrative examples of groups include: [0029] The present disclosure provides polymeric materials, polymers, methods of making polymeric materials and polymers. The present disclosure also provides uses of the polymeric materials and polymers.

[0030] In an aspect, the present disclosure provides polymeric materials. A polymeric material is also referred to herein a polymerizable polymeric material. The polymeric materials comprise a polymer group and two or more reactive groups. In various examples, the polymeric materials are telechelic macromonomers. In various examples, a polymeric material is produced by a method the present disclosure (e.g., a method of any one of Statements 21 to 24 or the like). Non-limiting examples of polymeric materials (e.g., telechelic macromonomers or the like) are disclosed herein.

[0031] In various examples, a polymeric material comprises (or has the following structure): RG PG RG PQ j _{s a} polymeric group (which may also be referred to as a polymer segment or segment) and RG is a reactive group. In various examples, a polymeric material is a polymerizable polymeric material. In various examples, a polymeric material is used form (e.g., is polymerized to form) another polymer material of the present disclosure, such as, for example, a polymeric material of any one of Statements 9 to 20 or the like. In various examples, a polymeric material is formed by depolymerization of a polymeric material of the present disclosure, such as, for example, a polymeric material of any one of Statements 9 to 20 or the like).

[0032] In various examples, a polymeric material comprises (or has) the following structure: independently at each occurrence, chosen from aliphatic groups (e.g., Ci to Ce aliphatic groups and the like) and the like. In various examples, R ¹¹ and/or R ¹² are chosen from groups (e.g., forming an alpha-beta unsaturated ester group or the like), where R ¹⁴ is a Ci to C4 alkyl group or the like. In various examples, R ¹¹ and/or R ¹² is/are absent. In various examples, PG is a polyethylene group, a polypropylene group, a polystyrene group, or the like.

[0033] In various examples, a polymeric material comprises a plurality of polymer chains. In various examples, each polymer chain, independently, is a polymeric material of the present disclosure, such as, for example, a polymeric material of any one of Statements 1- 8.

[0034] A polymeric material can comprise various polymeric groups. In various examples, a polymeric group comprises a carbon backbone (e.g., comprising a plurality of carbon-carbon bonds). In various examples, a polymeric group comprises a hydrocarbon backbone (e.g., comprising a plurality of carbon-carbon bonds). In various examples, a polymeric group is inert. In various examples, an inert polymeric group is inert to routine modification at ambient temperature. In various examples, a polymeric group is linear or branched. In various examples, a polymeric group comprises (or is) a homopolymer group, a copolymer group (e.g., a random copolymer group, an alternating copolymer group, a tapered copolymer group, a graft copolymer group, a block copolymer group, or the like, or any combination thereof), or the like, or any combination thereof. Non-limiting examples of polymeric groups include polyethylene groups, polypropylene groups, polystyrene groups, polytetrafluoroethylene groups, polyvinylchloride groups, polyacrylonitrile groups, polyacrylate groups, polymethacrylate groups, polyvinylacetate groups, polyurethane groups, structural analogs thereof, copolymer groups thereof, and any combination thereof.

[0035] A polymeric group can have various molecular weights. In various examples, the polymeric group(s), independently, has/have a molecular weight (Mw and/or Mn) of about 500 g/mol to about 500,000 g/mol, including all 1 g/mol values and ranges therebetween and/or about 10 to about 1000 repeat units, including all integer number of repeat units and ranges therebetween, and/or a PDI of about 1.5 to about 10 (e.g., about 2), including all 0.1 values and ranges therebetween. In various examples, a polymeric group has a molecular weight (Mw and/or Mn) of about 500 g/mol to about 10,000 g/mol, about 500 g/mol to about 25,000 g/mol, about 500 g/mol to about 100,000 g/mol, about 1,000 g/mol to about 20,000 g/mol, or about 2,000 g/mol to about 10,000 g/mol, or about 3,000 g/mol to about 5,000 g/mol. Polymeric group molecular weight and/or PDI can be determined by methods known in the art. In various examples, polymeric group molecular weight is determined by size exclusion chromatography (SEC), gel permeation chromatography (GPC) or the like.

[0036] In various examples, a polymeric group comprises one or more domain(s). In various examples, the domains are, independently, at least partially or completely be atactic, isotactic, isoenriched, syndiotactic, syndioenriched, or any combination thereof and/or the domains are, independently, crystalline, semi-crystalline, amorphous, or the like, or both. The presence or absence of atactic, isotactic, isoenriched, syndiotactic, or syndioenriched domains, or any combination thereof can be determined by methods known in the art. In various examples, the presence or absence of atactic, isotactic, isoenriched, syndiotactic, syndioenriched, or any combination thereof is determined (e.g., measured or the like) by nuclear magnetic resonance spectroscopy (such as, for example, ¹³ C NMR or the like) or the like. The presence or absence of crystalline and/or semicrystalline and/or amorphous domains can be determined by methods known in the art. In various examples, the presence of crystalline and/or amorphous regions is determined (e.g., measured or the like) by powder x- ray diffraction (PXRD), small angle X-ray scattering (SAXS), differential scanning calorimetry (DSC), or the like, or any combination thereof.

[0037] A polymeric material can comprise various reactive groups. In various examples, a polymeric material comprises the same reactive groups or at least two different reactive groups. In various examples, a reactive group comprises at least one functional group can react (or can be converted to react) in a polymerization (such as, for example, a step-growth polymerization or the like) or the like. A reactive group may be a multifunctional group. In various examples, a reactive group comprises two or more functional groups. Non-limiting examples of functional groups include, hydroxyl group (-OH), thiol group (-SH), alkenyl groups (e.g., a group comprising one or more carbon-carbon double bond(s) (which may be a terminal and/or internal carbon-carbon double bond(s)), ketone groups (-C(=O)R), acid groups (such as, for example, carboxylic acid groups (-CO2H) or the like) (which may be protonated or unprotonated), carboxylate ester groups (-CO2R), amine groups (e.g., -NH2, - NHR, and the like), alkynyl groups, azide group, halide groups (-F, -Cl, -Br, -I, or the like), and the like, and any combination thereof. In these examples, R is an aliphatic group (such as, for example, an alkyl group or the like).

[0038] In various examples, a reactive group or the reactive groups, independently at each occurrence, comprise(s) (or is/are) a group chosen from the following structures:

O or the like. R ¹ is, at each occurrence, chosen from aliphatic groups (e.g., Ci to Ce aliphatic groups and the like) and the like, and R ² is, at each occurrence, chosen from hydrogen group (-H), aliphatic groups, (e.g., Ci to Ce aliphatic groups and the like (e.g., which comprise a reactive group, (RG)), aryl groups (e.g., which comprise a reactive group(RG)), and the like. In various examples, R ¹ is absent. In various examples, an aliphatic group is a hydroxy alkyl group (e.g., or the like). In various examples, aliphatic group of the hydroxyalkyl group (e.g., R ³ or the like) is a Ci to Ce alkyl group. [0039] In various examples, a reactive group further comprises a cleavable group (or a precursor thereof) (e.g., a cleavable group described herein). Non-limiting examples of cleavable groups include ester groups, alkenyl groups, siloxide groups (-OS1R2-O-), carbonate group, amide groups, acetal groups, ketal groups, and the like, and combinations thereof. In various examples, a reactive group is also a cleavable group (or a precursor thereof).

[0040] In various examples, a polymeric material is a telechelic macromonomer. A polymeric material may be used as a starting material in a polymerization reaction (such as, for example, a step-growth polymerization reaction or the like). In various examples, a telechelic macromonomer is suitable for polymerization (e.g., by a method of the present disclosure, such as, for example, a method of Statement 32 or 33, or the like). In various examples, a telechelic macromonomer (or any combination thereof) is suitable for polymerization in a step-growth polymerization or the like.

[0041] In an aspect, the present disclosure provides polymeric materials. The polymeric materials comprise polymer groups and cleavable linking groups. In various examples, a polymeric material is a telechelic polymer (such as, for example, telechelic polyolefins and the like). In various examples, the polymers are chemically-recyclable polymeric materials (e.g., by degradation of at least a portion of the cleavable linking groups). In various examples, a polymeric material is produced by a method the present disclosure (e.g., a method of Statement 32 or 33, or the like). Non-limiting examples of polymeric materials are disclosed herein.

[0042] In various examples, a polymeric material comprises: . PG is a polymeric group and CLG is a cleavable linking group. A polymeric group may also be referred to as a polymer segment or segment. In various examples, a CLG is (or can be) formed by polymerization of a group, such as, for example, a reactive group (e.g., an RG group) as described herein. In various examples, a CLG is cleavable (or can be cleaved) by hydrolysis, alcoholysis, transesterification, alkene metathesis, ozonolysis, or the like, or any combination thereof.

[0043] In various examples, a polymeric material comprises (or has) the following structure: are independently at each occurrence, chosen from aliphatic groups (e.g., Ci to G> aliphatic groups and the like) and the like. In various examples, n is about 2 to about 200, including all integer n values and ranges therebetween. In various examples, R ¹⁵ and R ¹⁷ are independently chosen from groups, where R ¹⁴ is an alkyl group (e.g., a Ci to C4 alkyl group) or the like. In various examples, R ¹⁵ and/or R ¹⁷ is/are absent.

[0044] In various examples, a polymeric material is a random copolymeric material. In various examples, a random copolymeric comprises (or has) the following structure:

R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently at each occurrence, chosen from aliphatic groups, and PG ¹ and PG ² are independently at each occurrence chosen from polyethylene groups, polypropylene groups, polystyrene groups, and the like. In various examples, R ¹¹ and/or R ¹² and/or R ¹⁴ and/or R ¹⁵ is/are absent. In various examples, x + y = 1 and x is 0.01 to 0.99, including all 0.005 x values and ranges therebetween. In various examples, a random copolymeric material comprises the following structure: , where R ¹⁰ , R ¹¹ , R ¹² are each independently at each occurrence, chosen from aliphatic groups, PG is independently at each occurrence chosen from polyethylene groups, polypropylene groups, polystyrene groups, and the like, and PEST is independently at each occurrence chosen from polyester groups (such as, for example, polyethylene terephthalate groups or the like) and the like. In various examples, R ¹¹ and/or R ¹² is/are absent. In various examples, x + y = 1 and x is 0.01 to 0.99, including all 0.005 x values and ranges therebetween.

[0045] In various examples, a polymeric material comprises a plurality of polymer chains. In various examples, each polymer chain, independently, is a polymeric material of the present disclosure, such as, for example, a polymeric material of any one of Statements 9 to 20. In various examples, a polymeric material comprises a plurality of polymer chains, which are, independently, linear or branched.

[0046] In various examples, a polymer is crosslinked. In various examples, a crosslinked polymer is formed using one or more polymerizable polymeric materials comprising three or more reactive groups.

[0047] A polymeric material can comprise various end groups. In various examples, an end group or end groups result from formation of the polymeric material. In various examples, a polymeric material comprises end groups independently chosen at each occurrence from hydrogen group (-H), reactive groups, silyl ether groups, and the like.

[0048] A polymeric material can comprise various molecular weights, numbers of repeat units, or PDI, or any combination thereof. In various examples, a polymeric material comprises a molecular weight of about 10,000 g/mol to about 500,000 g/mol, including all 0.1 g/mol values and ranges therebetween, and/or n is from about 2 to about 200 repeat units, including all integer number of repeat units and ranges therebetween, and/or a PDI of about 1.5 to about 10 (e.g., about 2), including all 0.1 values and ranges therebetween.

[0049] A polymeric material can comprise various polymeric groups. In various examples, a polymeric group comprises a carbon backbone (e.g., comprising a plurality of carbon-carbon bonds). In various examples, a polymeric group comprises a hydrocarbon backbone (e.g., comprising a plurality of carbon-carbon bonds). In various examples, a polymeric group is inert. In various examples, an inert polymeric group is inert to routine modification at ambient temperature. In various examples, each polymeric group independently comprises (or is) a homopolymer group, a copolymer group (e.g., a random copolymer group, an alternating copolymer group, a tapered copolymer group, a graft copolymer group, a block copolymer group, or the like, or any combination thereof), or the like, or any combination thereof.

[0050] In various examples, a polymeric group comprises one or more pendant group(s). In various examples, a polymeric group comprises one or more pendant carbon-carbon double bond(s) or the like. In various examples, a polymeric group comprises about 1 to about 20 pendant groups (e.g., resulting from 1,2-diene insertion or the like), including all integer number of pendant groups and ranges therebetween.

[0051] A polymeric material can comprise various polymeric groups. In various examples, a cleavable linking group is hydrolysable, subject to alcoholysis, subject to transesterification, subject to alkene metathesis, subject to ozonolysis, or the like). [0052] In various examples, a polymeric material is a multiblock copolymer. In various examples, a polymeric material is a block copolymer comprising one of the following structures: where PG ¹ and PG ² are, independently at each occurrence, a polymeric group, R ¹ and R ² are, independently at each occurrence, aliphatic groups.

[0053] In various examples, a polymeric material can be depolymerized. In various examples, a polymeric material can be depolymerized to form a polymeric material (e.g., a telechelic macromonomer) of the present disclosure, such as, for example, a polymeric material of any one of Statements 1 to 9 or the like).

[0054] A polymeric material can comprise various polymeric groups. In various examples, a polymeric group comprises a carbon backbone (e.g., comprising a plurality of carbon-carbon bonds). In various examples, a polymeric group comprises a hydrocarbon backbone (e.g., comprising a plurality of carbon-carbon bonds). In various examples, a polymeric group is inert. In various examples, an inert polymeric group is inert to routine modification at ambient temperature. In various examples, a polymeric group is linear or branched. In various examples, a polymeric group comprises (or is) a homopolymer group, a copolymer group (e.g., a random copolymer group, an alternating copolymer group, a tapered copolymer group, a graft copolymer group, a block copolymer group, or the like, or any combination thereof), or the like, or any combination thereof. Non-limiting examples of polymeric groups include polyethylene groups, polypropylene groups, polystyrene groups, polytetrafluoroethylene groups, polyvinylchloride groups, polyacrylonitrile groups, polyacrylate groups, polymethacrylate groups, polyvinylacetate groups, polyurethane groups, structural analogs thereof, copolymer groups thereof, and any combination thereof.

[0055] A polymeric group can have various molecular weights. In various examples, the polymeric group(s), independently, has/have a molecular weight (Mw and/or Mn) of about 500 g/mol to about 500,000 g/mol, including all 1 g/mol values and ranges therebetween and/or about 10 to about 1000 repeat units, including all integer number of repeat units and ranges therebetween, and/or a PDI of about 1.5 to about 10 (e.g., about 2), including all 0.1 values and ranges therebetween. In various examples, a polymeric group has a molecular weight (Mw and/or Mn) of about 500 g/mol to about 10,000 g/mol, about 500 g/mol to about 25,000 g/mol, about 500 g/mol to about 100,000 g/mol, about 1,000 g/mol to about 20,000 g/mol, or about 2,000 g/mol to about 10,000 g/mol, or about 3,000 g/mol to about 5,000 g/mol. Polymeric group molecular weight and/or PDI can be determined by methods known in the art. In various examples, polymeric group molecular weight is determined by size exclusion chromatography (SEC), gel permeation chromatography (GPC), or the like, or any combination thereof.

[0056] In various examples, a polymeric group comprises one or more domain(s). In various examples, the domains are, independently, at least partially or completely be atactic, isotactic, isoenriched, syndiotactic, syndioenriched, or any combination thereof and/or the domains are, independently, crystalline, semi-crystalline, amorphous, or the like, or both. The presence or absence of atactic, isotactic, isoenriched, syndiotactic, or syndioenriched domains, or any combination thereof can be determined by methods known in the art. In various examples, the presence or absence of atactic, isotactic, isoenriched, syndiotactic, syndioenriched, or any combination thereof is determined (e.g., measured or the like) by nuclear magnetic resonance spectroscopy (such as, for example, ¹³ C NMR or the like) or the like. The presence or absence of crystalline and/or semicrystalline and/or amorphous domains can be determined by methods known in the art. In various examples, the presence of crystalline and/or amorphous regions is determined (e.g., measured or the like) by powder x- ray diffraction (PXRD), small angle X-ray scattering (SAXS), differential scanning calorimetry (DSC), or the like, or any combination thereof.

[0057] A polymeric material can comprise various cleavable linking groups. In various examples, a polymeric material comprises the same cleavable linking groups or at least one or more different cleavable linking groups. Non-limiting examples of cleavable linking groups include ester groups, alkenyl groups, siloxide groups (-OS1R2-O-, where R is independently at each occurrence an aliphatic group), a carbonate group, amide groups, acetal groups, ketal groups, or the like, or any combination thereof.

[0058] In various examples, a cleavable linking group, independently at each occurrence, comprises a group chosen from the following structure:

O . R ⁴ is, at each occurrence, chosen from aliphatic groups (e.g., Ci to Ce aliphatic groups and the like) and the like, and R ⁵ is, at each occurrence, chosen from aliphatic groups (e.g., Ci to Ce aliphatic groups and the like), and the like. In various examples, R ⁴ is absent. In various examples, an aliphatic group is an alkyl ester group (e.g., o or the like). In various example, aliphatic groups of the alkyl ester group

(e.g., R ⁶ , R ⁷ , or the like) is a Ci to Ce aliphatic group. In various examples, R ⁶ is absent. In

O various examples, R ⁷ is a group, where R ⁸ and R ⁹ are each, independently, chosen from aliphatic groups (e.g., Ci to Ce aliphatic groups and the like) and the like. In various examples, R ⁹ is absent.

[0059] A polymeric material can have various forms. In various examples, a polymeric material is in the form of a powder, pellets, a monolith, a coating, a sheet, a film, a fiber, a solid article, a hollow article, a foam, a composite, or the like.

[0060] In various examples, a polymeric material exhibits or has one or more desirable qualities, properties, etc. In various examples, a polymeric material exhibits or comprises one or more or all of the following: a melting temperature (Tm), which may be measured by differential scanning calorimetry (DSC), of about 40°C to about 250°C (e.g., about 90°C to about 250°C), including all 0.1 °C values and ranges therebetween; a decomposition temperature (Td), which may be measured by thermogravometric analysis (TGA), of about 250 to about 450°C (e.g., about 300°C to about 400°C) including all 0.1°C values and ranges therebetween; or a glass transition temperature (Tg), which may be measured by DSC, ranging from -80 to 200°C, including all 0.1°C values and ranges therebetween.

[0061] In an aspect, the present disclosure provides polymers. The polymers comprise polymer groups and backbone carbon-carbon double bonds. In various examples, a polymer or polymers is/are used to form a polymeric material of the present disclosure. In various examples, a polymer or polymers is/are used as a starting material in a method of any one of Statements 21 to 24 or the like. In various examples, a polymer is produced by a method the present disclosure (e.g., a method of Statement 32 or 33, or the like). Non-limiting examples of polymers are disclosed herein.

[0062] In various examples, a polymer is used to form a polymeric material of the present disclosure, such as, for example, a polymeric material of any one of Statements 1 to 9 or in a method of any one of Statements 21 to 24. In various examples, the polymer does not comprise terminal carbon-carbon double bonds.

[0063] In various examples, a polymer comprises (or has) the following structure: . R ¹⁹ is independently at each occurrence an alkenyl group and PG is a polymer group. In various examples, y is 3 to 500, including all integer y values and ranges therebetween.

[0064] In various examples, a polymer is a multiblock copolymer. In various examples, a polymer is a block copolymer comprising (or having) one of following structures: , where PG ¹ and PG ² are, independently at each occurrence, a polymeric group.

[0065] A polymer can comprise various polymeric groups. In various examples, a polymeric group comprises a carbon backbone (e.g., comprising a plurality of carbon-carbon bonds). In various examples, a polymeric group comprises a hydrocarbon backbone (e.g., comprising a plurality of carbon-carbon bonds). In various examples, a polymeric group is inert. In various examples, an inert polymeric group is inert to routine modification at ambient temperature. In various examples, a polymeric group is linear or branched. In various examples, a polymeric group comprises (or is) a homopolymer group, a copolymer group (e.g., a random copolymer group, an alternating copolymer group, a tapered copolymer group, a graft copolymer group, a block copolymer group, or the like, or any combination thereof), or the like, or any combination thereof. Non-limiting examples of polymeric groups include polyethylene groups, polypropylene groups, polystyrene groups, polytetrafluoroethylene groups, polyvinylchloride groups, polyacrylonitrile groups, polyacrylate groups, polymethacrylate groups, polyvinylacetate groups, polyurethane groups, structural analogs thereof, copolymer groups thereof, and any combination thereof. In various examples, each polymeric group is independently a polyethylene group, a polyalkylene group (e.g., comprising, independently, Ci to Ce alkyl groups, such as, for example, a polypropylene group, a polybutylene group, or the like), or the like, or any combination thereof. In various examples, a polymeric group is a random copolymer (such as, for example, LLDPE or the like).

[0066] In various examples, a polymeric group comprises one or more pendant group(s). In various examples, a polymeric group comprises one or more pendant carbon-carbon double bond(s) or the like. In various examples, a polymeric group comprises about 1 to about 20 pendant groups (e.g., resulting from 1,2-diene insertion or the like), including all integer number of pendant groups and ranges therebetween.

[0067] In various examples, the polymeric group(s), independently, has/have a molecular weight (Mw and/or Mn) of about 500 g/mol to about 500,000 g/mol, including all 0.1 g/mol values and ranges therebetween and/or about 10 to about 1000 repeat units, including all integer number of repeat units and ranges therebetween, and/or a PDI of about 1.5 to about 10 (e.g., about 2), including all 0.1 values and ranges therebetween. In various examples, a polymeric group has a molecular weight (Mw and/or Mn) of about 500 g/mol to about 10,000 g/mol, about 500 g/mol to about 25,000 g/mol, about 500 g/mol to about 100,000 g/mol, about 1,000 g/mol to about 20,000 g/mol, or about 2,000 g/mol to about 10,000 g/mol, or about 3,000 g/mol to about 5,000 g/mol. Polymeric group molecular weight and/or PDI can be determined by methods known in the art. In various examples, polymeric group molecular weight is determined by size exclusion chromatography (SEC), gel permeation chromatography (GPC) or the like.

[0068] In various examples, a polymeric group comprises one or more domain(s). In various examples, the domains are, independently, at least partially or completely be atactic, isotactic, isoenriched, syndiotactic, syndioenriched, or any combination thereof and/or the domains are, independently, crystalline, semi-crystalline, amorphous, or the like, or both. The presence or absence of atactic, isotactic, isoenriched, syndiotactic, or syndioenriched domains, or any combination thereof can be determined by methods known in the art. In various examples, the presence or absence of atactic, isotactic, isoenriched, syndiotactic, syndioenriched, or any combination thereof is determined (e.g., measured or the like) by nuclear magnetic resonance spectroscopy (such as, for example, ¹³ C NMR or the like) or the like. The presence or absence of crystalline and/or semicrystalline and/or amorphous domains can be determined by methods known in the art. In various examples, the presence of crystalline and/or amorphous regions is determined (e.g., measured or the like) by powder x- ray diffraction (PXRD), small angle X-ray scattering (SAXS), differential scanning calorimetry (DSC), or the like, or any combination thereof.

[0069] In various examples, a polymer further comprises one or more pendant (not backbone) alkenyl group(s). In various example, the alkenyl groups result from 1,2-insertion of a diene (such as, for example, a butadiene) during polymerization. In various examples, a polymer further comprises about 0.05 mol% to about 40 mol% pendant groups (which may be relative to the backbone carbon-carbon double bonds), including all 0.01 mol% values and ranges therebetween.

[0070] In various examples, one or more polymeric material(s), one or more polymer(s), or any mixture thereof is used as a compatibilizer. In various examples, a composition (which may be a polymer blend or the like) comprises one or more polymer(s) (e.g., first polymer(s)) and one or more other polymer(s) (e.g., second polymer(s)) (such as, for example, polyethylene (e.g., semi-crystalline polyethylene, such as, for example, HDPE and the like), polypropylene, and the like, or any combination thereof).

[0071] In various examples, a polyethylene comprises, or is chosen from high density polyethylenes (HDPE), linear low-density polyethylenes (LLDPE), ultra high molecular weight polyethylenes (UHMWPE), low density polyethylenes (LDPE), very low density polyethylenes (VLDPE), polyethylene polyolefin block copolymers, and the like, and any combination thereof. In various examples, a polypropylene comprises, or is chosen from isotactic polypropylenes (iPP), impact modified polypropylenes, polypropylene fibers, biaxially oriented polypropylenes (BOPP), and the like, and any combination thereof.

[0072] In various examples, where a composition comprises polyethylene and polypropylene, the ratio of the total amount of polyethylene(s)( (PE(s)) to polypropylene(s) (PP(s)) in the composition, excluding the polymeric material(s), polymer(s), or any mixture thereof, is 10:90 (PE(s)/PP(s)) to 90: 10 (PE(s)/PP(s)) wt %, including all 0.1 ratio values and ranges therebetween. In various examples, the total amount of PE(s) and/or PP(s) in a composition is 10 to 90 wt % (e.g., 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49,

50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74,

75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, or 90 wt %), including all 0.1 wt.% values and ranges therebetween. In various examples, a composition comprises 0.2 to 10 wt

% (e.g., 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0,

2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1,

4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2,

6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3,

8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, or 10.0 wt %) of one or more polymeric material(s), one or more polymer(s), or any mixture thereof (based on the total weight of polymers/polymeric materials in the composition), including all 0.1 wt.% values and ranges therebetween (e.g., 0.2 to 5.0 wt %, 0.2 to 4.5 wt %, etc.).

[0073] In various examples, an adhesion layer between two polymer layers (such as, for example, independently, a polyethylene layer, a polypropylene layer, or a combination thereof) comprises one or more polymeric material(s), one or more polymer(s), or any mixture thereof. In various examples, a multi-layer film or sheet comprises: a first layer comprising polyethylene; a second layer comprising polypropylene; and an adhesion layer, where the adhesion layer is disposed between the first layer and the second layer, and is in direct contact with the first layer and the second layer. [0074] In various examples, a method of adhering a first layer comprising polyethylene and a second layer comprising polypropylene comprises: contacting the first layer and the second layer with an adhesive composition comprising one or more polymeric material(s), one or more polymer(s), or any mixture thereof. In various examples, an adhesive composition is in the form of a film or sheet. One of ordinary skill in the art is familiar with various techniques for applying the adhesive composition, and any art-acceptable method can be used. In various examples, an adhesive composition is applied to the first layer or the second layer by blow molding, electrospinning, melt extruding, injection molding, application through sheer force, solvent casting (e.g., spin-casting), or the like, or any combination thereof.

[0075] In an aspect, the present disclosure provides methods of making polymeric materials (such as, for example, polymeric materials comprising a polymer group and two or more reactive groups, which may be telechelic macromonomers). In various examples, the methods are based on olefin metathesis, transesterification, or the like. In various examples, a method uses an olefin metathesis catalyst to metathesize polymer backbone carbon-carbon double bonds with carbon-carbon double bonds of a carbon-carbon double bond of a reactive group precursor compound. Non-limiting examples of methods of making polymeric materials are disclosed herein.

[0076] In various examples, a method of making a polymeric material comprising a polymer group and two or more reactive groups (such as, for example, a polymeric material or any one of Statement 1 to 9) comprises: contacting one or more polymer(s) comprising a plurality of polymer groups and a plurality of backbone carbon-carbon double bonds, one or more reactive group precursor compound(s), and one or more catalyst(s), where the polymeric material is formed. A method may further comprise at least partially or completely hydrogenating the polymeric material formed by reaction of the polymer(s) and reactive group precursor compound(s). In various examples, where the polymeric material (e.g., at least a portion of or all of the reactive groups), a method further comprises hydrogenation of the polymeric material to form an at least partially or substantially (or completely) hydrogenated polymeric material.

[0077] Various polymers can be used. In various examples, the one or more the polymer(s) is/are a polymer of the present disclosure (such as, for example, a polymer of any one of Statements 25 or 26, a polymer made by a method of any one of Statements 27 to 31. It may be desirable that polymer(s) comprising a plurality of polymeric groups have a number of backbone carbon-carbon double bonds that do not substantially affect the olefin metathesis catalyst(s).

[0078] In various examples, the one or more the polymer(s) is/are formed by at least partial or substantially complete (e.g., complete) dehydration, dehydrohalogenation, dehalogenation, dehydrogenation, dehydroarylation, oxidation (such as, for example, using oxygen, an oxidation catalyst (which may be used with oxygen), nitric acid, or the like), or the like of a saturated polymer (such as, for example, a polyethylene, a polypropylene, a polystyrene, a polytetrafluoroethylene, a polyvinylchloride, a polyacrylonitrile, copolymers thereof, and the like, and combinations thereof).

[0079] Various reactive group precursor compounds can be used. In various examples, the same reactive group precursor compound or a combination of at least two or more different reactive group precursor compounds is used. In various examples, at least a portion or all of the reactive group precursor compound(s) comprise(s) at least one carbon-carbon double bond (e.g., an internal or terminal carbon-carbon double bond, or any combination thereof) and one or more reactive group(s) that is/are polymerization active (e.g., active in step-growth polymerization, or the like). In various examples, the reactive group precursor compound or compounds independently comprise at least one hydroxyl group, an alkenyl group (e.g., a group comprising one or more carbon-carbon double bond(s) (which may be a terminal and/or internal carbon-carbon double bond(s)), an acid group (which may be protonated or unprotonated), an ester group, a thiol group (-SH), a ketone group (-C(=O)R), an amine group (e.g., -NH2, -NHR, or the like), alkynyl group, azide group, halide group, or the like. In these examples, R is an aliphatic group (such as, for example, an alkyl group or the like). A reactive group precursor compound may be multifunctional and comprise one or more of these groups. Non-limiting examples of reactive group precursor compound(s) include acrylates, methacrylates, and the like, and combinations thereof. An acrylate, methacrylate, or the like, may be multifunctional and comprise two or more of the functional groups. In various examples, a reactive group precursor compound or compounds is/are chosen from hydroxyalkyl acrylates (such as, for example, C2 to Ce hydroxyalkyl acrylates or the like), hydroxyalkyl methacrylates (such as, for example, C2 to Ce hydroxyalkyl methacrylates or the like), any of which may be multifunctional, and the like, and any combination thereof.

[0080] Various catalysts can be used. In various examples, the catalyst(s) is/are chosen from olefin metathesis catalysts and the like. In various examples, an olefin metathesis catalyst is active and/or selective for internal double bonds. In various examples, a catalyst is chosen from metal-carbene metathesis catalysts, and the like, and any combination thereof. Non-limiting examples of metal-carbene metathesis catalysts include ruthenium metathesis catalysts (such as, for example Hovey da-Grubbs II catalyst (HG2) and the like), and the like, and any combination thereof.

[0081] In various examples, at least a portion or all the polymeric material(s) comprise(s) one or more carbon-carbon double bond(s) (e.g., at least a portion of or all of the reactive groups comprise one or more carbon-carbon double bond(s) or the like) and a method further comprises at least partially or completely hydrogenating the polymeric material forming a hydrogenated polymeric material. In various examples, a hydrogenating comprises contacting with a hydrogen gas, hydrogenation catalyst and hydrogen gas, diimide (HN=NH) reduction, Pd-carbon reduction, or the like, or any combination thereof. In various examples, the hydrogenation catalyst is Wilkinson’s catalyst or the like. In various examples, the hydrogenation catalyst is chosen from [Ir(COD)(PR3)(S)] ⁺ X‘, where R is independently chosen at each occurrence from Cy, S is a coordinating molecule (which may be a coordinating solvent molecule or the like) (such as, for example, pyridine, or the like or any combination thereof), and X- is an anion (which may be a non-coordinating anion) (such as, for example, PFe’, and, the like, and any combination thereof.

[0082] A method may further comprise isolation of at least a portion of, substantially all, or all of the polymeric material or hydrogenated polymeric material(s) thereof. Suitable isolation methods are known in the art.

[0083] A reaction can be performed under various reaction conditions. A reaction may comprise one or more step(s) and each step can be performed under the same or different reaction conditions as other steps. A reaction can be carried out at various temperatures. In various examples, a reaction or a particular reaction step is carried out at room temperature (e.g., from about 20 °C to about 22 °C, including all 0.1 °C values and ranges therebetween), above room temperature (e.g., at a temperature up to or about a boiling point of the solvent(s), if present) (e.g., at about 100°C or above, e.g. from about 100°C to about 400°C, including all 0.1 °C values and ranges therebetween), or any combination thereof (e.g., where each reaction step is performed at a different temperature than other steps).

[0084] A reaction can be carried out at various pressures. In various examples, a reaction or a particular reaction step is carried out at atmospheric pressure (e.g., 1 standard atmosphere (atm) at sea level), at greater than atmospheric pressure (e.g. heating in a sealed pressurized reaction vessel or the like), at below atmospheric pressure (e.g., under vacuum (e.g., from about 1 mTorr or less to about 100 mTorr or less, including all 0.1 mTorr values and ranges therebetween) and the like), or any combination thereof (e.g., where each reaction step is performed at a different pressure than other steps).

[0085] A reaction can be carried out for various times. The reaction time can depend on factors such as, for example, temperature, pressure, efficiency of the catalyst, presence and/or intensity of mixing (e.g., stirring, or the like), or any combination thereof. In various examples, reaction times range from about seconds (e.g., two seconds) to greater than about 200 hours, including all integer second values and ranges therebetween, or any combination thereof (e.g., where each step is performed at a different time as other steps).

[0086] In an aspect, the present disclosure provides methods of making polymeric materials (such as, for example, polymeric materials comprising polymer groups and cleavable linking groups). Non-limiting examples of methods of making polymeric materials are disclosed herein.

[0087] In various examples, a method of making a polymeric material (such as, for example, a polymeric material according to any one of Statements 9 to 20 or the like) comprises: subjecting one or more polymerizable polymeric material(s) of the present disclosure (such as, for example, a polymeric material of one of Statements 1 to 8 or made by a method of any one of Statements 21 to 24 or Statement 34, or the like) to conditions (e.g., polymerization conditions or the like) such that the polymeric material is formed. In various examples, at least a portion or all of the polymerizable polymeric materials are telechelic monomers. Non-limiting examples of telechelic monomers are provided herein. In various examples, the conditions result in a step-growth polymerization or the like.

[0088] In various examples, a method of making a polymeric material (such as, for example, a polymeric material according to any one of Statements 9 to 20 or the like) comprises: forming a reaction mixture comprising one or more polymeric material(s) (such as, for example, a polymeric material of any one of Statements 9 to 20 and one or more catalyst(s) (such as, for example, an olefin metathesis catalyst/catalysts, a transesterification catalyst/catalysts, or the like, or any combination thereof), where the polymeric material is formed (e.g., the polymeric material comprising a block copolymer comprising two or more blocks, where at least one block (e.g., a polymeric group or the like) is from a different starting polymeric material).

[0089] Various catalysts may be used in the reaction of the polymeric material(s). Nonlimiting examples of catalysts include transesterification polymerization catalyst(s), metal alkoxides, and the like. In various example, the conditions comprise forming a reaction mixture comprising one or more metal alkoxide(s) (such as, for example, titanium alkoxide(s) (e.g., Ti(0Bu)4 or the like) or the like) or the like, or any combination thereof.

[0090] A method may further comprise isolation of at least a portion of, substantially all, or all of the polymeric material. Suitable isolation methods are known in the art. Additionally or in the alternative, a method may further comprise forming an article of manufacture (such as, for example, an article of manufacture of the present disclosure) by forming (e.g., by molding, extrusion, blowing, casting, spinning, or the like) one or more polymeric material(s).

[0091] A polymerization can be performed under various reaction conditions. A polymerization may comprise one or more step(s) and each step can be performed under the same or different reaction conditions as other steps. A polymerization can be carried out at various temperatures. In various examples, a polymerization or a particular reaction step of a polymerization is carried out at room temperature (e.g., from about 20 °C to about 22 °C, including all 0.1 °C values and ranges therebetween), above room temperature (e.g., at a temperature up to or about a boiling point of the solvent(s), if present) (e.g., at about 100°C or above, e.g. from about 100°C to about 400°C, including all 0.1 °C values and ranges therebetween), or any combination thereof (e.g., where each reaction step is performed at a different temperature than other steps).

[0092] A polymerization can be carried out at various pressures. In various examples, a polymerization or a particular reaction step of a polymerization is carried out at atmospheric pressure (e.g., 1 standard atmosphere (atm) at sea level), at greater than atmospheric pressure (e.g. heating in a sealed pressurized reaction vessel or the like), at below atmospheric pressure (e.g., under vacuum (e.g., from about 1 mTorr or less to about 100 mTorr or less, including all 0.1 mTorr values and ranges therebetween) and the like), or any combination thereof (e.g., where each reaction step is performed at a different pressure than other steps). [0093] A polymerization can be carried out for various times. The polymerization time can depend on factors such as, for example, temperature, pressure, efficiency of the catalyst, presence and/or intensity of mixing (e.g., stirring, or the like), or any combination thereof. In various examples, polymerization times range from about seconds (e.g., two seconds) to greater than about 200 hours, including all integer second values and ranges therebetween, or any combination thereof (e.g., where each step is performed at a different time as other steps).

[0094] In an aspect, the present disclosure provides methods of making polymers (such as, for example, polymers comprising polymer groups and backbone carbon-carbon double bonds). In various examples, a polymer or polymers are used in a method of making a polymeric material (such as, for example, a method of any one of Statements 21 to 24). Nonlimiting examples of methods of making polymers materials are disclosed herein.

[0095] In various examples, a method of making a polymer comprising a plurality of backbone carbon-carbon double bonds (e.g., a polymer, such as, for example a polymer according to Statement 25 or 26) comprises: contacting one or more alpha olefin(s), optionally, one or more diene(s), and one or more catalyst(s), where the polymer comprising a plurality of backbone carbon-carbon double bonds is formed. In various examples, a polymer is formed primarily by 1,2-insertion of a diene (e.g., repeat units comprising the 1,4- insertion product is the minority of the repeat units formed by the reaction of the alphaolefins and diene(s)). In various examples, the method is a chain-growth polymerization or the like.

[0096] Various olefins can be used. In various examples, the same olefin or a combination of at least two or more different olefins is used. An olefin may be linear or branched. In various examples, the olefin(s) is/are chosen from C2 to Cx (e.g., C2, C3, C4, C5, Ce, C7, or Cs) olefins, and the like, and any combination thereof. In various examples, the olefin, the olefins, or a portion of the olefins are alpha-olefin(s). In various examples, the alpha-olefin(s) is/are chosen from C2 to Cx (e.g., C2, C3, C4, C5, Ce, C7, or Cs) alpha-olefins, and the like, and any combination thereof. Non-limiting examples of olefins include ethylene, propene, 1 -butene, 4-methyl-l -pentene, 1 -octene, and the like, and any combination thereof. [0097] Various catalysts may be used. In various examples, a single catalyst or a combination of at least two or more different catalysts is used. In various examples, the catalyst(s) is/are chosen from catalysts Table 1 of Example 1 and analogs and derivatives thereof. In various examples, an analog or derivative of a catalyst of comprises other halide ligand(s), other alkyl group(s) (e.g., number of carbons and/or placement of the substitution(s) or the like) on the bridged biphenylphenol ligands, etc. In various examples, the catalyst(s) is/are a hafnium (IV) non-metallocene complex or complexes, zirconium (IV) non-metallocene complex or complexes, or the like, or any combination thereof, comprising a bridged bisphenolate ligand, or the like, or any combination thereof. In various examples, a catalyst is a bridged bisphenolate dihalide hafnium(IV) halide complex, a bridged bisphenolate dihalide zirconium(IV) halide complex, or the like, or any combination thereof. In various examples, the catalyst(s) is/are chosen from catalysts described herein (e.g., in Table 1 of Example 1), and the like, and combinations thereof. Non-limiting examples of catalysts are described in U.S. Patent Nos. 7,126,031, 7,659,415, 9,534,070, the disclosures of which with regard to catalysts and methods of making ligands and catalysts are incorporated herein by reference in their entirety.

[0098] A method may further comprise isolation of at least a portion of, substantially all, or all of the polymer. Suitable isolation methods are known in the art.

[0099] A polymerization can be performed under various reaction conditions. A polymerization may comprise one or more step(s) and each step can be performed under the same or different reaction conditions as other steps. A polymerization can be carried out at various temperatures. In various examples, a polymerization or a particular reaction step of a polymerization is carried out at room temperature (e.g., from about 20 °C to about 22 °C, including all 0.1 °C values and ranges therebetween), below room temperature (e.g., at about 0°C or below, such as for example, from about -100°C to about 0°C, including all 0.1 °C values and ranges therebetween), above room temperature (e.g., at a temperature up to or about a boiling point of the solvent(s), if present) (e.g., at about 100°C or above, e.g. from about 100°C to about 250°C, including all 0.1 °C values and ranges therebetween), or any combination thereof (e.g., where each reaction step is performed at a different temperature than other steps).

[0100] A polymerization can be carried out at various pressures. In various examples, a polymerization or a particular reaction step of a polymerization is carried out at atmospheric pressure (e.g., 1 standard atmosphere (atm) at sea level), at greater than atmospheric pressure (e.g. heating in a sealed pressurized reaction vessel or the like), at below atmospheric pressure (e.g., under vacuum (e.g., from about 1 mTorr or less to about 100 mTorr or less, including all 0.1 mTorr values and ranges therebetween) and the like), or any combination thereof (e.g., where each reaction step is performed at a different pressure than other steps). [0101] A polymerization can be carried out for various times. The polymerization time can depend on factors such as, for example, temperature, pressure, efficiency of the catalyst, presence and/or intensity of mixing (e.g., stirring, or the like), or any combination thereof. In various examples, polymerization times range from about seconds (e.g., two seconds) to greater than about 200 hours, including all integer second values and ranges therebetween, or any combination thereof (e.g., where each step is performed at a different time as other steps).

[0102] In an aspect, the present disclosure provides methods of depolymerizing polymeric materials of the present disclosure (such as, for example, polymeric materials comprising polymer groups and cleavable linking groups). In various examples, a polymeric material is depolymerized by cleavage of at least a portion of or all of the cleavable linking groups. In various examples, the cleavage results in production of another polymeric material (such as, for example, a polymeric material comprising a polymer group and reactive groups (e.g., a polymeric material of any one of Statements 1 to 9 or the like), a polymeric material comprising a polymer groups, cleavable linking groups, and terminal reactive groups (which may be formed by incomplete depolymerization), or the like. In various examples, a polymeric material produced by a depolymerization method is used in a method of making a polymeric material (e.g., a method of Statement 32 or 33, or the like) comprising polymer groups and cleavable linking groups (e.g., a polymeric material of any one of Statements 9 to 20, or the like). Non-limiting examples of methods of making polymers materials are disclosed herein.

[0103] In various examples, a method is a method of recycling a polymeric material (such as, for example, a chemically-recyclable polymeric material) of the present disclosure. In various examples, a method is a method of recycling a polymeric material of any one of Statements 9 to 20, a polymeric material made by a method of Statement 32 or 33, or an article of manufacture of any one of Statements 35 to 44, or the like).

[0104] In various examples, a method of depolymerizing a polymeric material (e.g., a polymeric material according to any one of Statement 9 to 20 or a polymeric material made by a method of Statement 32 or 33, or the like) (such as, for example, a chemically-recyclable polymeric material) comprises: subjecting the polymeric material to hydrolysis conditions, alcoholysis conditions, transesterification conditions, alkene metathesis conditions, ozonolysis conditions, or the like, and, optionally, isolating at least a portion of or substantially all of the depolymerized product(s) (such as, for example, hydrolysis product(s), alcoholysis product(s), transesterification product(s), alkene metathesis product(s), ozonolysis product(s), or the like). In various examples, at least about 50% or more, at least about 60% or more, at least about 70% or more, at least about 80% or more, at least about 90% or more, at least about 90% or more, at least about 95% or more, or about 100% of a polymeric material is depolymerized and, optionally, isolated. In various examples, the depolymerized product(s) (such as, for example, hydrolysis product(s), alcoholysis product(s), transesterification product(s), alkene metathesis product(s), ozonolysis product(s), or the like) is/are repolymerized (e.g., as formed, without purification, etc.).

[0105] In various examples, a reaction mixture of the polymeric material (having an ester cleavable group) and a catalyst (which may be an acid catalyst or a base catalyst, or the like). In various examples, the catalyst is a metal oxide, metal alkoxide, a metal carboxylate, or the like, or any combination thereof. In various examples, the catalyst is an organic base (such as, for example, 5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD), 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU) or the like), and optionally, a polyol (e.g., a diol or the like (such as, for example, a glycol (e.g., ethylene glycol or the like), or the like. An organic base may be a nucleophilic base.

[0106] In various examples, at least a portion of or all of the depolymerized product(s) (such as, for example, hydrolysis product(s), alcoholysis product(s), transesterification product(s), alkene metathesis product(s), ozonolysis product(s), or the like) is/are used in a polymerization method (e.g., a polymerization method of the present disclosure, such as, for example, a polymerization method of Statement 32 or 33). The depolymerized product(s) (such as, for example, hydrolysis product(s), alcoholysis product(s), transesterification product(s), alkene metathesis product(s), ozonolysis product(s), or the like) may be used without further purification, or the like, or any combination thereof.

[0107] In various examples, a method provides a polymeric material of the present disclosure (e.g., a polymeric material according to any one of Statements 1 to 8, a polymeric material made by a method of any one of Statements 21 to 24, or the like), which may be as formed and/or not have been subject to purification, that exhibits substantially the same reactivity relative to the structurally same polymeric material of the present disclosure (e.g., a polymeric material according to any one of Statements 1 to 8 or a polymeric material made by a method of any one of Statements 21 to 24, or the like) not produced by the depolymerization method.

[0108] A depolymerization can be performed under various reaction conditions. A depolymerization may comprise one or more step(s) and each step can be performed under the same or different reaction conditions as other steps. A depolymerization can be carried out at various temperatures. In various examples, a depolymerization or a particular reaction step of a depolymerization is carried out at room temperature (e.g., from about 20 °C to about 22 °C, including all 0.1 °C values and ranges therebetween), above room temperature (e.g., at a temperature up to or about a boiling point of the solvent(s), if present) (e.g., at about 100°C or above, e.g. from about 100°C to about 400°C, including all 0.1 °C values and ranges therebetween), or any combination thereof (e.g., where each reaction step is performed at a different temperature than other steps).

[0109] A depolymerization can be carried out at various pressures. In various examples, a depolymerization or a particular reaction step of a polymerization is carried out at atmospheric pressure (e.g., 1 standard atmosphere (atm) at sea level), at greater than atmospheric pressure (e.g. heating in a sealed pressurized reaction vessel or the like), at below atmospheric pressure (e.g., under vacuum (e.g., from about 1 mTorr or less to about 100 mTorr or less, including all 0.1 mTorr values and ranges therebetween) and the like), or any combination thereof (e.g., where each reaction step is performed at a different pressure than other steps).

[0110] A depolymerization can be carried out for various times. The depolymerization time can depend on factors such as, for example, temperature, pressure, presence and/or efficiency of a catalyst, presence and/or intensity of mixing (e.g., stirring, or the like), or any combination thereof. In various examples, polymerization times range from about seconds (e.g., two seconds) to greater than about 200 hours, including all integer second values and ranges therebetween, or any combination thereof (e.g., where each step is performed at a different time as other steps).

[OHl] In an aspect, the present disclosure provides uses of polymeric materials of the present disclosure (such as, for example, polymeric materials comprising polymer groups and cleavable linking groups (e.g., polymeric materials of any of Statements 9 to 20 or the like). Non-limiting examples of uses of the polymeric materials are disclosed herein.

[0112] Without intending to be bound by any particular theory, it is considered that a polymeric material can be used in applications where polyethylene and/or polypropylene is/are typically used. In various examples, a polymeric materials or polymeric materials is/are used as a replacement for polyethylene and/or polypropylene in an application (e.g., process, product, or the like, where polyethylene and/or polypropylene typically used.

[0113] In various examples, an article of manufacture comprises one or more polymeric material(s) of the present disclosure (e.g., one or more polymeric material(s) of any one of Statements 9 to 20, one or more polymeric material(s) made by a method of Statement 32 or 33, or any combination thereof). In various examples, the article of manufacture is a chemically-recyclable article of manufacture. Non-limiting examples of articles of manufacture (e.g., chemically-recyclable articles of manufacture) are provided herein. In various examples, an article of manufacture is a molded article, an extruded article, a blown article, a cast article, a spun article, or the like. In various examples, an article of manufacture is in the form of a monolith, a coating, a sheet, a film, a fiber, a solid article, a hollow article, a foam, a composite, or the like.

[0114] In various examples, an article of manufacture is a packaging article, a single-use article, a sports article, a biomedical article, an agricultural article, an automotive article, an electronic article, or the like. In various examples, the packaging article is a film, a wrapping, a sheet, a textile, a net, a bag, a container, a tub, a closure, a cap, a handle, a dispenser, a filler, a protector, a pad, a fastener, or the like. In various examples, the single-use article is a bag, a container, a dispenser, a cup, a bottle, a plate, cutlery, a straw, or the like. In various examples, the sports article is fishing line or the like. In various examples, the biomedical article is a drug delivery article, a wound closure article, a wound dressing article, a surgical suture, or the like. In various examples, the agricultural article is a film, a wrapping, a sheet, a textile, a net, a twine, a string, clips, wires, stakes, a bag, a container, a tub, a closure, a cap, a handle, a dispenser, a filler, a protector, a pad, a fastener, a bottle, a lid, a pot, mulch, or the like.

[0115] In various examples, an article of manufacture is biodegradable or the like. In various examples, an article of manufacture is biodegradable within compost, or other organic matter; fresh water or salt water; landfills, or the like, or any combination thereof. In various examples, an article of manufacture is at least partially or completely biodegradable by microbial degradation, hydrolysis, photodegradation, or the like, or any combination thereof. In various examples, an article of manufacture is at least partially or completely biodegradable under aerobic conditions, anaerobic conditions, or combinations thereof.

[0116] In various examples, an article of manufacture is at least partially or substantially (e.g., completely) recyclable. In various examples, at least about 50% or more, at least about 60% or more, at least about 70% or more, at least about 80% or more, at least about 90% or more, at least about 90% or more, at least about 95% or more, or about 100% of an article of manufacture is recyclable. In various examples, an article of manufacture is at least partially or substantially completely (e.g., completely) recyclable using a method of the present disclosure (e.g., using a method of the present disclosure, such as, for example, a method of Statement 34 or the like). In various examples, an article of manufacture is at least partially or substantially completely (e.g., completely) recyclable without using mechanical recycling, chemical recycling (other than the recycling methods described herein), or any combination thereof.

[0117] The following Statements describe various examples of polymeric materials and polymers and methods of making same and uses thereof of the present disclosure and are not intended to be in any way limiting:

Statement 1. A polymeric material (which may be a polymerizable polymeric material (e.g., which may be used to form a polymeric material of any one of Statements 9 to 20)) comprising (or having) the following structure: RG PG RG , where PG is a polymeric group (which may also be referred to as a polymer segment or segment), and RG is a reactive group.

Statement 2. A polymeric material according to Statement 1, where the polymeric group is chosen from polyethylene groups, polypropylene groups, polystyrene groups, polytetrafluoroethylene groups, polyvinylchloride groups, polyacrylonitrile groups, copolymer groups thereof, any of which may be linear or branched, and the like, and combinations thereof. In various examples, a polymeric group is linear or branched. Statement 3. A polymeric material according to Statement 1 or 2, where the polymeric group(s), independently, has/have a molecular weight (Mw and/or Mn) of about 500 g/mol to about 25,000 g/mol, including all 1 g/mol values and ranges therebetween and/or about 10 to about 1000 repeat units, including all integer number of repeat units and ranges therebetween, and/or a PDI of about 1.5 to about 10 (e.g., about 2), including all 0.1 values and ranges therebetween.

Statement 4. A polymeric material according to any one of the preceding Statements, where the polymeric group is at least partially or completely atactic, isotactic, isoenriched, syndiotactic, syndioenriched, or any combination thereof.

Statement 5. A polymeric material according to any one of the preceding Statements, where the polymeric group comprises one or more domain(s) and the domains are, independently, crystalline, semi-crystalline, amorphous, or the like.

Statement 6. A polymeric material according to any one of the preceding Statements, where the reactive group(s), independently at each occurrence, comprise a hydroxyl group, an alkenyl group (e.g., a group comprising one or more carbon-carbon double bond(s) (which may be a terminal and/or internal carbon-carbon double bond(s)), an acid group (which may be protonated or unprotonated), an ester group, a thiol group (-SH), a ketone group (- C(=O)R), an amine group (e.g., -NH2, -NHR, or the like), alkynyl group, azide group, halide group, or the like. In these examples, R is an aliphatic group (such as, for example, an alkyl group or the like).

Statement 7. A polymeric material according to any one of the preceding Statements, where the reactive group, independently at each occurrence, comprises (or is) a group chosen from the following structure:

O , where R ¹ is, at each occurrence, chosen from aliphatic groups (e.g., Ci to Ce aliphatic groups and the like) and the like, and R ² is, at each occurrence, chosen from hydrogen group (-H), aliphatic groups (e.g., Ci to G, aliphatic groups and the like, which comprise a reactive group, (RG)), aryl groups (e.g., which comprise a reactive group), and the like.

Statement 8. A polymeric material according to any one of the preceding Statements, where the polymeric material comprises: are independently at each occurrence, chosen from aliphatic groups (e.g., Ci to Ce aliphatic groups and the like) and the like.

Statement 9. A polymeric material comprising: , where PG is a polymeric group (which may also be referred to as a polymer segment or segment), and CLG is a cleavable linking group (which may be formed by polymerization of a group, such as, for example, a reactive group (such as, for example, an RG group of any one of the preceding Statements or the like)).

Statement 10. A polymeric material according to Statement 9, where each polymeric group is independently chosen from polyethylene groups, polypropylene groups, polyethylene terephthalate groups, polystyrene groups, polyvinylchloride groups, polyacrylonitrile groups, copolymer groups thereof, and the like, and combinations thereof.

Statement 11. A polymeric material according to Statement 9 or 10, where the polymeric groups, independently, have a molecular weight (Mw and/or Mn) of about 500 g/mol to about 25,000 g/mol, including all 1 g/mol values and ranges therebetween, and/or about 10 to about 1000 repeat units (e.g., n), including all integer number of repeat units and ranges therebetween, and/or a PDI of about 1.5 to about 10 (e.g., about 2), including all 0.1 values and ranges therebetween.

Statement 12. A polymeric material according to any one of Statements 9-11, where the polymeric groups are independently at least partially or completely be atactic, isotactic, isoenriched, syndiotactic, syndioenriched, or any combination thereof.

Statement 13. A polymeric material according to any one of Statements 9-12, where the polymeric group comprises one or more domain(s) and the domains are, independently, crystalline, semi-crystalline, amorphous, or the like. Statement 14. A polymeric material according to any one any one of Statements 9-13, where the cleavable linking group, independently at each occurrence, comprises an ester group, an alkenyl groups, a siloxide group, (-OSiR2-O-), a carbonate group, an amide group, an acetal group, a ketal group, or the like.

Statement 15. A polymeric material according to any one of Statements 9-14, where the cleavable linking group, independently at each occurrence, comprises a group chosen from the following structure:

O , where R ⁴ is, at each occurrence, chosen from aliphatic groups (e.g., Ci to Ce aliphatic groups and the like) and the like, and R ⁵ is, at each occurrence, chosen from aliphatic groups (e.g., Ci to Ce aliphatic groups and the like), and the like.

Statement 16. A polymeric material according to any one of Statements 9-15, where the polymeric material comprises end groups are independently chosen from hydrogen group (- H), reactive groups, silyl ether groups, and the like.

Statement 17. A polymeric material according to any one of Statements 9-16, where the polymeric material has a molecular weight of about 10,000 g/mol to about 500,000 g/mol, including all g/mol values and ranges therebetween, and/or n is from about 2 to about 200 repeat units, including all integer number of repeat units and ranges therebetween, and/or a PDI of about 1.5 to about 10 (e.g., about 2), including all 0.1 values and ranges therebetween. Statement 18. A polymeric material according to any one of Statements 9-17, where the polymeric material comprises: are independently at each occurrence, chosen from aliphatic groups (e.g., Ci to Ce aliphatic groups and the like) and the like, and optionally, n is about 2 to about 200, including all integer n numbers and ranges therebetween.

Statement 19. A polymeric material according to any one of Statements 9-18, where the polymeric material is in the form of a powder, pellets, a monolith, a coating, a sheet, a film, a fiber, a solid article, a hollow article, a foam, a composite, or the like.

Statement 20. A polymeric material according to any one of Statements 9-19, where the polymeric material exhibits or has one or more or all of the following: • A melting temperature (Tm), which may be measured by differential scanning calorimetry (DSC), of about 40°C to about 250°C (e.g., about 90°C to about 250°C), including all 0.1 °C values and ranges therebetween.

• A decomposition temperature (Td), which may be measured by thermogravometric analysis (TGA), of about 250 to about 450°C (e.g., about 300°C to about 400°C) including all 0.1°C values and ranges therebetween.

• A composition may have a glass transition temperature (Tg), which may be measured by DSC, ranging from -80 to 200°C, including all 0.1°C values and ranges therebetween.

Statement 21. A method of making a polymeric material of the present disclosure (e.g., a polymeric material according to any one of Statements 1 to 9, where the polymeric material comprises reactive groups, and each reactive group may comprise a carbon-carbon double bond), the method comprising: contacting one or more polymer(s) comprising a plurality of polymeric groups and a plurality of backbone carbon-carbon double bonds, one or more reactive group precursor compound(s), and one or more catalyst(s), where the polymeric material of the present disclosure (e.g., a polymeric material according to any one of Statements 1 to 9, where the polymeric material comprises reactive groups each comprising a carbon-carbon double bond) is formed.

Statement 22. A method according to Statement 21, where the catalyst is chosen from metal - carbene metathesis catalysts, and the like, and any combination thereof.

Statement 23. A method according to Statement 21, where the polymeric material comprises one or more carbon-carbon double bond(s) (e.g., at least a portion of or all of the reactive groups comprise one or more carbon-carbon double bond(s) or the like), the method further comprising at least partially or completely hydrogenating the polymeric material forming a hydrogenated polymeric material.

Statement 24. A method according to Statement 21, where the hydrogenating comprises contacting with a hydrogen gas, hydrogenation catalyst and hydrogen gas, diimide (HN=NH) reduction, Pd-carbon reduction, or the like.

Statement 25. A polymer comprising the following structure: , where R ¹⁹ is independently at each occurrence an alkenyl group (e.g., a C3 to Ce alkenyl group (such as, for example, a C4 alkenyl group, which may comprise an internal carbon-carbon double bond) or the like), and the PG is independently at each occurrence, a polymeric group, and z is about 3 to about 500, including all integer z numbers and ranges therebetween.

Statement 26. A polymer according to Statement 25, where the polymer further comprises one or more pendant (not backbone) alkenyl group(s).

Statement 27. A method of making a polymer comprising a plurality of backbone carboncarbon double bonds (e.g., a polymer, such as, for example a polymer according to Statement 25 or 26) comprising: contacting one or more olefin(s), one or more diene(s), and one or more catalyst(s), where the polymer comprising a plurality of backbone carbon-carbon double bonds is formed.

Statement 28. A method according to Statement 27, where the olefin(s) is/are chosen from C2 to Cx (e.g., C2, C3, C4, C5, Ce, C7, or Cs) olefins, and the like, and any combination thereof. Statement 29. A method according to any one of Statements 27 or 28, where the diene(s) is/are chosen from C4 to C10 dienes, and the like, and any combination thereof.

Statement 30. A method according to any one of Statements 27-29, where in the olefin is in molar excess relative to the amount of diene.

Statement 31. A method according to any one of Statements 27-30, where the catalyst(s) is/are chosen from catalysts described herein (e.g., in Table 1 of Example 1), and the like and combinations thereof.

Statement 32. A method of making a polymeric material of the present disclosure (such as, for example, a polymeric material according to any one of Statements 9 to 20 or the like) comprising subjecting one or more polymeric material(s) (which may be telechelic monomers) of the present disclosure (such as, for example, a polymeric material according to any one of Statements 1 to 8 or made by a method of any one of Statements 21 to 24 or Statement 30, or the like) to conditions (e.g., polymerization conditions or the like) such that the polymeric material is formed; OR forming a reaction mixture comprising one or more polymeric material(s) (such as, for example, a polymeric material of any one of Statements 9 to 20 and one or more catalyst(s) (such as, for example, an olefin metathesis catalyst/catalysts, a transesterification catalyst/catalysts, or the like, or any combination thereof), where the polymeric material is formed (e.g., the polymeric material comprising a block copolymer comprising two or more blocks, where at least one block (e.g., a polymeric group or the like) is from a different starting polymeric material.

Statement 33. A method according to Statement 31, further comprising forming an article of manufacture by forming (e.g., by molding, extrusion, blowing, casting, spinning, or the like) one or more of the polymeric material(s). Statement 34. A method of depolymerizing a polymeric material of the present disclosure (e.g., a polymeric material according to any one of Statements 9 to 20 or a polymeric material made by a method of Statement 32 or 33, or the like) comprising: subjecting the polymeric material to hydrolysis, alcoholysis, transesterification, alkene metathesis, or ozonolysis conditions, or the like, and isolating at least a portion of or substantially all of the resulting products.

Statement 35. An article of manufacture comprising one or more polymeric material(s) of the present disclosure (e.g., one or more polymeric material(s) of any one of Statements 9 to 20, one or more polymeric material(s) made by a method of Statement 32 or 33, or any combination thereof).

Statement 36. An article of manufacture according to Statement 35, where the article of manufacture is in the form of a monolith, a coating, a sheet, a film, a fiber, a solid article, a hollow article, a foam, a composite, or the like.

Statement 37. An article of manufacture according to Statement 35 or 36, where the article of manufacture is a packaging article, a single-use article, a sports article, a biomedical article, an agricultural article, an automotive article, an electronic article, or the like.

Statement 38. An article of manufacture according to Statement 35, where the packaging article is a film, a wrapping, a sheet, a textile, a net, a bag, a container, a tub, a closure, a cap, a handle, a dispenser, a filler, a protector, a pad, a fastener, or the like.

Statement 39. An article of manufacture according to Statement 35, where the single-use article is a bag, a container, a dispenser, a cup, a bottle, a plate, cutlery, a straw, or the like. Statement 40. An article of manufacture according to Statement 35, where the sports article is fishing line or the like.

Statement 41. An article of manufacture according to Statement 35, where the biomedical article is a drug delivery article, a wound closure article, a wound dressing article, a surgical suture, or the like.

Statement 42. An article of manufacture according to Statement 35, where the agricultural article is a film, a wrapping, a sheet, a textile, a net, a twine, a string, clips, wires, stakes, a bag, a container, a tub, a closure, a cap, a handle, a dispenser, a filler, a protector, a pad, a fastener, a bottle, a lid, a pot, mulch, or the like.

Statement 43. An article of manufacture according to any one of Statements 35-42, where the article of manufacture is biodegradable. Statement 44. An article of manufacture according to any one of Statements 35-40, where the article of manufacture is at least partially or substantially completely (e.g., completely) recyclable.

[0118] The steps of the methods described in the various embodiments and examples disclosed herein are sufficient carry out the methods of the present disclosure. Thus, in various examples, a method consists essentially of a combination of the steps of the methods disclosed herein. In various other examples, a method consists of such steps.

[0119] The following Example is presented to illustrate the present disclosure. It is not intended to be limiting in any manner.

EXAMPLE

[0120] The following is an example of methods of polymeric materials, polymerizable polymeric materials, and polymers of the present disclosure and methods of making and using same.

[0121] Polyolefins represent the largest class of commodity materials due to their excellent material properties; however they have limited pathways to chemical recycling and are often difficult to mechanically recycle. A new catalyst for the isoselective copolymerization of propylene and butadiene capable of favoring 1,4-insertion over 1,2- insertion while maintaining good molecular weights and turnover frequencies (TOFs) was demonstrated. This isotactic propylene copolymer with main-chain unsaturation was depolymerized to a telechelic macromonomer using an olefin metathesis catalyst and 2- hydroxyethyl acrylate. After hydrogenation, the telechelic macromonomer was repolymerized to form an ester-linked polypropylene material. This polymer shows thermal and mechanical properties comparable to linear low-density polyethylene (LLDPE). Also, the telechelic macromonomer could be regenerated through the depolymerization of the ester-linked polypropylene material, which allows for the chemical recycling to macromonomer. This process provides a route to transform partially unsaturated polyolefins to chemically recyclable materials with similar properties to their parent polymers.

[0122] As an alternative approach to designing a telechelic zPP macromonomer, we envisioned copolymerizing propylene and butadiene to produce a polypropylene with unsaturation in the polymer backbone. Controlling the regioselectivity of the butadiene insertion to favor 1,4-insertion over 1,2-insertion will produce olefins incorporated directly into the main chain of the polymer which can be cleaved via metathesis with a functional acrylate. This functional telechelic zPP macromonomer would provide a route to convert the material to a chemically recyclable polyolefin (FIG. 1).

[0123] The copolymerization of ethylene and butadiene has been demonstrated with 1,4- selectivity of butadiene. However, with propylene, controlling both the selectivity and the tacticity of the material has proven to be challenging. While the polymerization of propylene and butadiene with good tacticity and 1,2-selectivity has been well demonstrated, achieving 1,4-selectivity with good molecular weight and tacticity has yet to be accomplished. Shiono and coworkers showed that some metallocene catalysts could favor 1,4-selectivity, though the molecular weight and activity often suffered significantly as the butadiene incorporation increased.

[0124] Table 1. Optimization of propyl ene-butadiene copolymerization catalyzed by hafnium complexes.

Entry Complex [BD] Temp TOF (10 ³ h’ ¹ A/„ D T _m 1,4: 1,2

(M)° (°C) (kDa) ^c ( v/ _n ) ^c (°C)' ⁷ (mol %) ^e

1 1 0.39 25 35.4 140 2.40 60 0.47:0.16 2 1 0.87 70 8.57 18.7 1.97 n.d. 1.18:0.33

3 2 0.23 70 359 13.8 2.05 110 0.13:0.07

4 2 0.37 70 206 30.4 2.56 90 0.26:0.08

Conditions: 2.5 pmol catalyst, 2 atm propylene, 2000 equivalence MAO, 100 mL toluene, 30 minutes. “Determined by weighing the mass of butadiene added. ^Determined by yield. “Determined by GPC in trichlorobenzene at 150 °C. ^Determined by DSC. “Regioselectivity of butadiene incorporation determined by ’H NMR spectroscopy.

[0125] To synthesize our target material, we started with a class of bridged biphenylphenoxide catalysts that were first reported by Symyx Technologies. These group IV non-metallocene catalysts have been shown to have excellent activity, thermal stability and incorporation of a-olefins into the polymer chain. However, these ligands often require multi- step synthesis with the installation of the pendant aromatic group in the first step before the coupling of biphenyl units. To shorten the synthesis, we designed a two-step process by first connecting two biphenol rings to form the core structure followed by a C(sp ² )-H arylation using the free alcohol as a directing group (FIG. 2).

[0126] It was found two biphenols could be linked in 65% yield using an amine base such as /PnNEt and 1,3 -dibromopropane on a multi-gram scale. Next, the ortAo-aryl group was introduced using a recently reported rhodium-catalyzed C-H arylation method published by Ye and coworkers, which resulted in a two-step synthesis with moderate overall yield. ⁷⁶ Hafnium precatalyst 2 was prepared by complexation of 2b with HfC12Bn2(Et2O)i. _x (SI). We investigated the copolymerization of propylene and butadiene with complex 1 and complex 2, which have previously been used for propylene homopolymerization. Precatalyst 1 gave good incorporation and regioselectivity of butadiene incorporation. At room temperature, approximately 0.5 mol % incorporation of 1,4-insertion of butadiene with a ~4:1 ratio of 1,4- insertion to 1,2-insertion was observed (Table 1, entry 1). However, the melting temperature of the polymer was only 60 °C. This is likely due to the incorporation of cyclic moieties that can be resulted from the reincorporation of butadiene olefins, which has been previously observed in propylene and butadiene copolymerizations. When the temperature of polymerization was increased to 70 °C, the 1,4-incorporation increased to 1.18 mol % (Table 1, entry 2). However, the polymer became amorphous with no observable melting temperature.

[0127] To improve the melting temperature of the polymer, the catalyst with ortho- mesityl groups was used which gave higher tacticity for propylene homopolymerization. It was found that complex 2 gave lower overall 1,4-incorporation under similar conditions than 1, resulting in a melting temperature that was significantly improved (Table 1, entry 3). At 0.37 M butadiene, a melting temperature of 90 °C was observed with a 1,4-incorporation of 0.26 mol % (Table 1, entry 4). This corresponds to an olefin placed approximately every 10 kDa along the polymer chain.

[0128] Next, the depolymerization of the propylene-butadiene copolymer into a telechelic macromonomer by cross-metathesis (FIG. 3) was investigated. It was found that using Hovey da-Grubbs II (HG2) as a catalyst with an excess of 2-hydroxy ethyl acrylate, zPP-co- BD could be depolymerized to telechelic macromonomer Pl. 2 -Hydroxy ethyl acrylate was chosen as the metathesis partner, so the resulting telechelic macromonomer has two pendant ethylene glycol units that should be repolymerizable in a manner similar to polyethylene terephthalate (PET). It was found with 25 equivalents of acrylate, 1 mol % of catalyst relative to the olefins in the polymer at 100 °C, full conversion to 2-hydroxy ethyl terminated macromonomer was observed.

[0129] The direct repolymerization of Pl resulted in cross-linking through the remaining acrylate functional groups. To saturate the remaining double bonds, hydrogenation using Crabtree’s catalyst [Ir(COD)(PCy3)(py)]PFe was performed neat in the polymer melt at 140 °C and 700 PSI hydrogen. After 24 hours, near full hydrogenation to P2 was observed. The polymerization of the hydrogenated, alcohol terminated telechelic macromonomer was performed neat at 180 °C with 1 mol % of Ti(OBu)4 as a catalyst under vacuum to drive off the excess ethylene glycol. After 16 hours we found the repolymerization went to full conversion, confirmed by ¹ H NMR.

[0130] This process was monitored through ¹ H NMR, GPC, and DSC (FIG. 3b-d). The initial propylene-butadiene copolymer zPP-co-BD displays characteristic signals of both internal and terminal olefins at approximately 5.5 ppm and 5.0 ppm respectively. The polypropylene segments within the copolymer have high isotacticity, indicated by the ¹³ C NMR (See SI for details). After metathesis with 2-hydroxy ethyl acrylate, the disappearance of the internal and terminal olefins can be observed, while the characteristic acrylate and 2- hydroxy ethyl signals appear at 7.1 ppm, 5.9 ppm, and 3.5 -4.5 ppm.

[0131] By GPC, the Mi of Pl is 10.5 kDa, which matches the expected molecular weight based on the spacing of the 1,4-butadiene insertions (FIG. 3 c). After hydrogenation, the disappearance of nearly all olefins is evidenced by the absence of alkenic C-H signals between 5-7 ppm, while the 2-hydroxy ethyl signals and the M _n remain unchanged. Lastly, after repolymerization, the M _n increases to 32.6 kDa which is comparable to the _n of the starting propyl ene-butadiene copolymer and a new ethylene glycol peak appears in the ’H NMR.

[0132] The thermal properties of the materials were measured by DSC. Across all transformations, the T _m of the polymers remains relatively unchanged (FIG. 3d). The initial propyl ene-butadiene copolymer shows a T _m of ca. 90 °C. After cross-metathesis then hydrogenation, the telechelic macromonomer maintains a similar T _m to the parent polymer. Finally, after repolymerization into the polypropylene-polyester hybrid material, the polymer shows a T _m of ca. 95 °C, which is comparable to both the parent propylene-butadiene copolymer as well as LLDPE.

[0133] The polymer zPP-co-EG could be depolymerized in the presence of triazabicyclodecene (TBD) and ethylene glycol back to P2-Recycled (FIG. 3a). Heating the polymer in ethylene glycol at 190 °C for 24 hours resulted in 93% conversion of ester linkages back to 2-hydroxyethyl terminated chains, determined via 'HNMR. This macromonomer was repolymerized using the same repolymerization conditions (SI).

[0134] The tensile behaviors of the parent zPP-co-BD and the hybrid zPP-co-EG are similar to each other, with yield points at approximately 7 MPa and a strain at break of 930% for zPP-co-BD and 1200% for zPP-co-EG (FIG. 4). Thus, these materials possess both thermal and mechanical properties comparable to LLDPE, the second most commonly used commodity polymer, while possessing cleavable linkages that allow for chemical recycling. [0135] It was shown that the bridged biphenylphenoxide-hafnium catalysts can copolymerize propylene and butadiene giving preferentially 1,4-insertion of butadiene while maintaining good molecular weights and activities. The partially unsaturated copolymer was depolymerized via olefin metathesis with a functionalized acrylate to yield a telechelic polypropylene macromonomer. After hydrogenation, this macromonomer was repolymerized into an ester-linked polypropylene material that showed similar mechanical and thermal properties to LLDPE. However, unlike LLDPE, it was depolymerized in the presence of base and ethylene glycol and repolymerized back into the ester-linked polypropylene material. We envision this method as a route to turn a wide range of partially unsaturated polyolefins into chemically recyclable materials that can retain their original mechanical and thermal properties. We believe that due to the increased solubility of the macromonomers, they could be depolymerized and extracted from a mixed waste stream.

[0136] General Information. All manipulations of air and water sensitive compounds were carried out under nitrogen in an MBraun Labmaster glovebox or by using standard Schlenk line technique. ’H, ¹³ C and two-dimensional NMR spectra were recorded on Bruker AVANCE III HD (U, 400 MHz) spectrometer with a BBF/’H broadband observe probe or Bruker AVANCE III HD (U, 500 MHz) spectrometer with a broadband Prodigy cryoprobe. All the NMR experiments were carried out at 25 °C for catalyst synthesis or 100 °C for polymers. All the NMR spectra were processed with MestReNova software. Chemical shifts (6) for ¹ H NMR spectra were referenced to protons on the residual solvents (7.26 ppm for CDCh, 5.32 ppm for CD2CI2, 7.16 ppm for C ₆ D ₆ , 6.00 ppm for CI2CDCDCI2 (TCE-tfe)). Chemical shifts (6) for ¹³ C NMR spectra were referenced to the deuterated solvents themselves (77.16 ppm for CDCh, 54.00 ppm for CD2CI2, 128.06 ppm for CeDe, 73.78 ppm for Q2CDCDQ2 (TCE-tfe)). NMR-spectroscopic data were reported as follows: chemical shift, multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, quint = quintet, m = multiplet, dd = doublet of doublets, dt = doublet of triplets, td = triplet of doublets, ddt = doublet of doublets of triplets, br = broad), integration and coupling constants (Hz). High resolution mass spectrometry (HRMS) analyses were performed on a Thermo Scientific Exactive Orbitrap MS system equipped with an Ion Sense DART ion source.

[0137] Flash column chromatography was performed using silica gel (particle size 40-64 pm, 230-400 mesh). High temperature gel permeation chromatography (GPC) was performed on Agilent PL-GPC 220 equipped with a refractive index (RI) detector and three PL-Gel Mixed B columns. GPC columns were eluted at 1.0 mL/min with 1,2,4- trichlorobenzene (TCB) containing 0.01 wt. % di-tert-butylhydroxytoluene (BHT) at 150 °C. The samples were prepared in TCB (with BHT) at a concentration of 1.0 mg/mL and heated at 150 °C for at least 1 hour prior to injection. GPC data calibration was done with monomodal polyethylene standards from Varian and Polymer Standards Service.

[0138] Differential scanning calorimetry (DSC) measurements of polymer samples were performed on a Mettler-Toledo Polymer DSC instrument equipped with a chiller and an autosampler. Polymer samples containing approximately 5 mg in crimped aluminum pans were prepared for each run. DSC samples were heated to 200 °C and maintained at the temperature for 10 min to erase the thermal history, followed by cooling to 25 °C and then heating back to 200 °C. The cooling and heating process were kept at a rate of 10 °C/min and in nitrogen atmosphere. The melting temperatures were obtained from the second heating cycles respectively using the STARe software.

[0139] Compression molding was carried out using a 4120 Hydraulic Unit Carver press and stainless-steel die molds. Mylar protective sheets were obtained from Carver. Uniaxial tensile elongation was carried out using a Shimadzu Autograph AGS-X tensile tester. All polymer processing was carried out on the pristine materials (i.e. no BHT, other antioxidants, or additives were added). Further experimental details are provided in the appropriate section.

[0140] Materials. Toluene for air sensitive reactions was purchased from Fisher, sparged with ultrahigh purity (UHP) grade nitrogen, passed through two columns containing reduced copper (Q-5) and alumina, and dispensed into an oven-dried Straus flask, followed by sparging with nitrogen for 2 hours and drying with molecular sieves prior to use. Propylene (Airgas, polymer grade) was purified over columns of copper Q5 and 4A molecular sieves. 1,3-Butadiene was purchased from Sigma-Aldrich and used without further purification. Methylaluminoxane (MAO) was obtained from Albemarle as a 30 wt% solution in toluene and dried at 40 °C under vacuum for at least 12 hours.

[0141] Deuterated chloroform, di chloromethane, benzene and 1,1,2,2-tetrachloroethane were purchased from Cambridge Isotope Laboratories. Deuterated chloroform, dichloromethane and benzene were degassed by three freeze-pump-thaw cycles and stored under nitrogen over 3 A molecular sieves. Molecular sieves were purchased from Strem and activated by heating at 200 °C under vacuum for 18 hours. Deuterated 1,1,2,2- tetrachloroethane was used without further purification. All other chemicals and reagents were purchased from commercial sources (Sigma-Aldrich, Oakwood Chemical, Strem, TCI, Alfa Aesar, Acros, and Fisher) and used without further purification.

[0142] Catalyst Synthesis. Synthesis of 2a.

[0143] 2,2’-Biphenol (1.86 g, 10.0 mmol), N,N-diisopropylethylamine (2.1 mL, 12 mmol), 1,3 -dibromopropane (0.51 mL, 5.0 mmol) and DMF (5 mL) were added to a 20 mL glass vial with a Teflon coated stir bar and Teflon lined cap. The vial was sealed and heated at 100 °C for 4 hours. The reaction was quenched with 1 M HC1 (10 mL) and extracted into ethyl acetate. The organic layer was washed three times with brine and then dried with sodium sulfate. The organic layer was concentrated to dryness. The resulting thick oil was recrystallized from MeOH to give 773 mg of 2a. The filtrate was collected and its volume was reduced. Upon cooling to -30 °C, a second crop of the product crystallized out affording an additional 575 mg of 2a. The two batches were combined resulting in 1.35 g (65%) of 2a. [0144] 'H NMR (500 MHz, CDCh): 6 7.35 (ddd, J= 8.2, 7.4, 1.8 Hz, 2H), 7.31 (dd, J= 7.6, 1.8 Hz, 2H), 7.26 (m, 2H), 7.19 (dd, J= 7.9, 1.7 Hz, 2H), 7.11 (td, J= 7.5, 1.1 Hz, 2H), 6.97 (ddt, J= 6.4, 3.5, 1.7 Hz, 4H), 6.92 (dd, J= 8.3, 1.1 Hz, 2H), 6.01 (s, 2H), 4.07 (t, J= 6.1 Hz, 2H), 2.08 (t, J= 6.0 Hz, 2H); ¹³ C NMR (125 MHz, CDCh): 6 154.98, 153.68, 132.45, 131.35, 129.54, 129.28, 127.42, 126.14, 122.58, 120.95, 117.08, 113.57, 65.73, 28.93; HRMS (ESI): m/z calculated for C27H25O4 [M+H] ⁺ 413.17474, found .17474. [0145] Synthesi s of 2b .

MesBr (7.5 eq) Cs ₂ CO ₃ (2 eq) tBu ₂ PCI (1 eq)

[0146] A modified literature procedure was used. ¹ Inside a glovebox, 2a (412 mg, 1.00 mmol), 2,4,6-trimethylbromobenzene (1.1 mL, 7.5 mmol), CS2CO3 (652 mg, 2.00 mmol), di- tert-butylphosphine (1 mL of 1 M solution in toluene, 1 mmol), [Rh(COD)Cl]2 (25 mg, 0.050 mmol), COD (6 pL, 0.05 mmol), Cy3PHBF4 (36 mg, 0.10 mmol) and toluene (20 mL) were added to a sealed glass bomb flask. The flask was taken outside the glovebox and heated to 150 °C for 48 hours. The reaction was cooled and 1 M HC1 was added. The organic layer was extracted by ethyl acetate and dried over sodium sulfate. The mixture was concentrated and purified by column chromatography on silica gel (eluent hexanes then 20: 1 hexanes :EtO Ac) to afford 324 mg (50%) of 2b.

[0147] ‘HNMR (500 MHz, CDCh): 8 7.35 (dd, J = 7.5, 1.8 Hz, 2H), 7.23 (dt, J = 8.1, 4.7 Hz, 2H), 7.18 (dd, J = 6.6, 2.7 Hz, 2H), 7.09 - 7.00 (m, 6H), 6.96 (s, 4H), 6.76 (d, J = 8.3 Hz, 2H), 5.47 (s, 2H), 4.01 (t, J = 5.9 Hz, 4H), 2.35 (s, 6H), 2.07 - 1.98 (m, 14H); ¹³ C NMR (125 MHz, CDCh): 6 155.39, 150.47, 137.22, 137.05, 134.30, 132.25, 130.59, 130.11, 129.27, 128.42, 128.09, 127.67, 126.25, 121.84, 120.65, 112.82, 65.33, 29.26, 21.29, 20.46; HRMS (ESI): m/z calculated for C45H45O4 [M+H] ⁺ 649.33124, found 649.33125.

[0148] Synthesis of HfBn2C12(Et2O)i. _x

Et ₂ O

HfCI ₄ + HfBn ₄ - - - ► HfCI ₂ Bn ₂ (Et ₂ O) _{1 x}

79% [0149] HfCU (322 mg, 1.01 mmol) was slurried in 10 mL Et20. The mix was cooled to -35 °C in the glovebox freezer, and then solid HfBm (538 mg, 0.991 mmol) was added. The mixture was allowed to warm to room temperature and stir for 2.5 hours. The mixture was light yellow with a small amount of colorless insoluble material. The solution was filtered through a syringe filter and the volume was reduced to approximately 2 mL, at which point crystals began to form. The solution was stored at -35 °C overnight. Light yellow crystals were isolated and dried briefly in vacuo. 'H NMR revealed the presence of 1.2 eq. Et2O per Hf (850 mg, 79%). Note: the amount of bound ether varies slightly from batch to batch and ranges from 1.0-1.5 eq. The stoichiometry for each batch should be confirmed by ^X H NMR spectroscopy.

[0150] ’H NMR (400 MHz, C ₆ D ₆ ): 5 7.39 (d, ./HH = 7.8 Hz, 2H, Ph), 7.09 (t, ./HH = 5.6 Hz, 2H, Ph), 6.84 (t, ./HH = 8.0, 1H, Ph), 3.01 (q, ./HH = 7.2 Hz, 0.7 Hz, 2H, OC Hs), 2.77 (s, 2H, HfC/LPh), 0.65 (t, ./HH = 7.2 Hz, 3H, OCH2C// ); ¹³ C NMR (100 MHz, C ₆ D ₆ ): 5 138.09, 132.30, 129.14, 124.08, 81.39, 69.75, 13.11.

[0151] HfBn2C12(Et2O)i. _x is slightly thermally unstable and somewhat light sensitive. It should be stored in the glovebox freezer when not in use and may be purified by recrystallization from Et2O at -35 °C.

[0152] Synthesi s of 2.

2: 40%

[0153] In a glovebox, 2b (32.4 mg, 50.0 pmol), HfBn2C12(Et2O)i. _x (21.6 mg, 50.0 pmol) and toluene (1.5 mL) were added to a 20 mL glass vial with a Teflon sealed cap and Teflon coated stir bar. The vial was sealed and heated outside of the glovebox at 80 °C for 1 hour. The vial was cooled to room temperature and brought back into the glovebox. 2 was filtered as a white solid resulting in 18.1 mg (40%).

[0154] ¹ H NMR (500 MHz, CD2CI2): 8 7.47 (dd, J= 7.8, 1.7 Hz, 2H), 7.35 (td, J= 7.8, 1.5 Hz, 4H), 7.25 (dd, J= 7.5, 1.8 Hz, 2H), 7.15 (s, 2H), 7.09 (ddd, J= 8.9, 7.3, 1.7 Hz, 2H), 7.05 - 6.99 (m, 4H), 6.02 (dd, J= 8.2, 1.3 Hz, 2H), 4.25 (dt, J= 10.0, 4.8 Hz, 2H), 3.99 (dt, J = 11.0, 5.7 Hz, 2H), 2.47 (s, 6H), 2.27 (s, 6H), 2.18 (s, 6H), 1.87 - 1.81 (m, 2H); ¹³ C NMR (125 MHz, CD2CI2): 6 157.30, 155.75, 140.16, 137.01, 135.88, 135.61, 133.48, 133.22, 132.97, 131.08, 131.04, 129.57, 129.48, 129.33, 128.76, 128.47, 125.57, 120.47, 79.92, 30.21, 21.98, 21.45, 20.78; HRMS (ESI): m/z calculated for C45H ₄ 3C12HfO ₄ [M+H] ⁺ 897.19984, found 897.19949.

[0155] Polymer Synthesis. In the glovebox, the catalyst was dissolved in toluene and stored in a syringe equipped with a long needle and taped with Teflon. The end of the needle was sealed by stabbing into a septum. MAO and toluene were added into a 600 mL Fischer- Porter vessel, equipped with a Teflon coated stir bar. The vessel was closed and sealed with all the valves closed. The vessel and syringe were taken out of the glovebox. The vessel was weighed and tared for measuring the mass of butadiene. Butadiene was added to the desired weight. Propylene was then added to the desired pressure. If required, the vessel was placed into an oil bath and warmed to the desired temperature. After reaching the desired temperature, the inlet of propylene was closed, and the vessel was partially vented. The toluene solution of catalyst was added. The vessel was sealed and pressurized to the desired pressure. After the desired time, the pressure was vented, and the vessel was cooled to room temperature. The reaction was quenched with a 1 : 1 mixture of 10% HCFMeOH. Acetone was added to precipitate the polymer and then the polymer was filtered and dried in a vacuum oven until constant weight.

[0156] Polymer Functionalization.

[0157] Cross-metathesis of zPP-co-BD with 2-hydroxy ethyl acrylate to give Pl ² . In a Schlenk flask, zPP-co-BD (0.1 mmol) was dissolved in dry toluene (50 mL) equipped with a Teflon coated stir bar under a nitrogen environment and heated to 100 °C until being fully dissolved. 2-Hydroxyethyl acrylate (0.29 mL, 2.5 mmol) and Hovey da-Grubbs II catalyst solution (1 mol %, 1 M in toluene) were added and stirred for 4 hours. The reaction mixture was precipitated out in acetone and stirred for at least 1 hour. The polymer was filtered, washed with acetone and dried in the vacuum oven.

[0158] Hydrogenation of Pl using Crabtree's Catalyst to give P2. Pl and Crabtree's Catalyst (1 mol %) were added into a Parr reactor. The reactor was sealed and pressurized with hydrogen gas (700 PSI) and heated at 140 °C for 24 hours. Toluene was added into the reactor glass vessel to dissolve all the polymer. The mixture was precipitated out in acetone and stirred for at least 1 hour. The polymer was filtered, washed with acetone and dried in the vacuum oven. [0159] Repolymerization of P2 using 1 mM Ti(OBu)4 to give zPP-co-EG ³ . P2 was added to a Schlenk flask under nitrogen environment. Ti(OBu)4 solution (1 mol %, 1 mM in toluene) was added and heated to 180 °C. The reaction was under vacuum and heated for 16 hours. After reaction, TCE was added to dissolve the polymer. The mixture was precipitated out in acetone and stirred for at least 1 hour. The polymer was filtered, washed with acetone and dried in the vacuum oven.

[0160] Depolymerization of zPP-co-EG using l,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD) to give P2-Recycled ⁴ . zPP-co-EG, TBD (2 wt %) and ethylene glycol (1 : 1 wt/wt) were added in a glass vial equipped with a Teflon coated stir bar and Teflon lined cap in the glovebox. The reaction was stirred at 190 °C for 24 hours outside of the glovebox. Once the reaction cooled to around 100 °C, toluene was added to dissolve the polymer. After the mixture cooled to room temperature, acetone was added to precipitate out the polymer. The mixture was sonicated, centrifuged and decanted. This process was repeated twice. The polymer was dried in a vacuum oven.

[0161] Repolymerization of P2-Recycled using 1 mM Ti(OBu)4 to give zPP-co-EG- Recycled. P2-Recycled was added to a Schlenk flask under nitrogen environment. Ti(OBu)4 solution (1 mol %, 1 mM in toluene) was added and heated to 180 °C. The reaction was under vacuum and heated for 16 hours. After reaction, TCE was added to dissolve the polymer. The mixture was precipitated out in acetone and stirred for at least 1 hour. The polymer was filtered, washed with acetone and dried in the vacuum oven.

[0162] Polymer Characterization. GPC data

[0163] Table 3. GPC data of the zPP- -BD, P 1 , P2, zPP- -EG, P2-Recycled and zPP-co- EG-Recycled for Table 1, entry 4.

Polymer M _n (kg/mol) A/ _w (kg/mol) D zPP-co-BD 30.4 77.8 2.56

Pl 10.5 21.2 2.02

P2 11.8 21.1 1.80 zPP-co-EG 32.7 147 4.52

P2-Recycled 10.9 20.6 1.89 zPP-co-EG-Recycled 31.7 347 10.9

[0164] Tensile data. The zPP-co-BD polymer sample was pressed at 110 °C for 1 minute into a film between two Mylar sheets with fast cooling. The film was cut and loaded into a stainless-steel dogbone mold (gauge length = 10 mm, gauge width = 2.6 mm, gauge thickness = 0.6 mm) and pressed on a Carver press hot plate under ~20 MPa at 110 °C for 10 minutes, with fast cooling. The sample was removed and trimmed with a razor blade. The zPP-co-EG polymer sample was loaded into a stainless-steel dogbone mold (gauge length = 10 mm, gauge width = 2.6 mm, gauge thickness = 0.6 mm) and pressed on a Carver press hot plate under ~20 MPa at 120 °C for 5 minutes, with fast cooling. The sample was removed and trimmed with a razor blade. On the tensile tester, samples were elongated with a crosshead velocity of 10 mm/min. Tensile bars were elongated until break. Results were analyzed using TrapeziumX software. FIG. 5 shows a stress vs. strain plot for zPP-co-BD. The samples were tested under ambient conditions at a rate of 100% strain/min. shows representative stressstrain curves for zPP-co-BD, zPP-co-EG, and LLDPE. FIG. 6 shows a stress vs. strain plot for zPP-co-EG. The samples were tested under ambient conditions at a rate of 100% strain/min.

[0165] Although the present disclosure has been described with respect to one or more particular embodiments and/or examples, it will be understood that other embodiments and/or examples of the present disclosure may be made without departing from the scope of the present disclosure.