Circular polyolefin thermosets and uses thereof

Abstract

Various diketoenamine precursors are described, including triketones, which can undergo reversible reactions with amines to form diketoenamines. Also described are polyolefins functionalized with triketones, which can undergo reversible reactions with amines to form diketoenamine functionalized and crosslinked polyolefins. Also described are diketoenamine functionalized polyolefins and diketoenamine functionalized crosslinked polyolefin networks.

Description

Attorney Docket No 077429- 1469156-023810 WO Client Ref No 2023-132-02CIRCULAR POLYOLEFIN THERMOSETS AND USES THEREOF CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of and priority to U.S. Provisional Application 63 / 603,965, filed on November 29, 2023, which is incorporated by reference.STATEMENT AS TO RIGHTS TO INVENTIONS MADE UNDER FEDERALLY SPONSORED RESEARCH AND DEVELOPMENT

[0002] This invention was made with government support under Contract No. DE-AC02-05CH11231 awarded by the United States Department of Energy and under Grant No. FA9550-22-1-0324 awarded by the Air Force Office of Scientific Research. The government has certain rights in the invention.FIELD

[0003] The present disclosure is generally in the field of polymers. More specifically, the present disclosure provides various compositions of matter that can be used for modifying plastic polymers and the resultant modified plastic polymers, which in turn can be easily recycled and reused by way of reversible reactions.BACKGROUND

[0004] Over 260M tons of plastic waste are generated annually. That amount is projected to double by 2030. Of this waste ~52M tons / year is incinerated for energy recovery and -100M tons / year is landfilled, predominantly in poor communities that will bear the burden of its toxic legacy. Marine ecosystems are similarly affected by leakage of -50M tons / year into the world’s oceans. Despite growing public awareness and concern over the impacts of plastic waste on global health, only ~40M tons / year is recycled. Current recycling practices are based on mechanical grinding, which degrades the performance and value of the recovered materials. These practices have failed to stimulate collection and re-use of materials from waste plastics. Instead, to meet growing demand, producers have increased manufacturing capacity. Notably, the EPA recorded that CO2 emissions from petrochemicals increased by ~43% between 1990-2019, from 21.6 MMT CChe to 30.8 MMT CCLe, driven by a 2-fold increase in ethylene production for polyethylene resinproduction. This rise is likely to continue unless new chemical processes and materials that bring greater circularity to polymer life cycles are discovered and developed.SUMMARY

[0005] The present disclosure overcomes many problems and disadvantages in the existing plastics industry by providing ways to reuse and recycle polymers, or to modify virgin polymers for improved recyclability. Diketoenamines have been demonstrated by the inventors to undergo selectively reversible chemistry, allowing for easy breakdown of the diketoenamines to the building blocks used initially, which can then be used in generation of additional diketoenamines. The techniques described herein take this further by incorporating diketoenamine precursors into conventional polymers through selective functionalization. Once functionalized, the polymers can undergo reversible crosslinking by way of reactions that convert the precursor-functionalized polymers into crosslinked diketoenamines, allowing for generation of strong, stably crosslinked polymer networks that can undergo de-crosslinking by way of a selectively reversible reaction of the diketoenamines back to the precursor-functionalized polymers.

[0006] The polymers useful with the techniques and compositions described herein include polyolefins commonly used in the plastics industry, such as, but not limited to, polyethylene, polypropylene, polybutylene, poly(l -pentene), poly(l -hexene), poly(l -heptene), poly(l -octene), poly (1 -decene), poly(l -tetradecene), poly(l -hexadecene), poly(l -octadecene), polynorbomene, or poly(isobutylene), among others. Other example polymers include polyolefins with branched architectures, such as those formed from branched C3-C18 monomers, as well as copolymers (e.g., block copolymers) of various monomers, including those mentioned above. In some examples, copolymers are prepared using chain shuttling reactions using two or more catalysts, which can allow for preparation of block copolymers and / or polymers with branched architectures.

[0007] The present disclosure provides various diketoenamine precursors, referred to herein as triketones (and related variations), which can undergo reversible reactions with amines to form diketoenamines, and related methods for generating such triketones. The present disclosure also provides polymers functionalized with triketones, which can undergo reversible reactions with amines to form diketoenamine functionalized and crosslinked polymers, and related methods for generating such triketone functionalized polymers. The present disclosure also provides diketoenamine functionalized polymers and diketoenamine functionalized crosslinked polymers and networks and related methods for generating such polymers and networks.

[0008] In an aspect, triketone compositions are disclosed. An example composition of this aspect comprises a functionalized triketone, such as where the functionalized triketone comprises a P-triketone moiety covalently linked to a thiosulfonate moiety. The P-triketone moiety can be a structure, with three ketone or ketone equivalent groups (e.g., =C-OH) positioned P- to one another, where two of the three ketone or ketone equivalent groups are positioned on a 5-membered or larger cyclic group. The linking group can covalently link the P-triketone moiety to the thiosulfonate moiety. The thiosulfonate moiety can be an alkyl or aryl functionalized thiosulfonate moiety. In the presence of an (9-al kenylhydroxam ate, the thiosulfonate moiety can react with and functionalize a polyolefin to generate a triketone functionalized polyolefin. Advantageously, a variety of different polyolefins can be functionalized with triketones in this way, including virgin and recycled polyolefins, including mixed polyolefins. The disclosed triketone compositions can undergo reversible reactions with amines to generate diketoenamines.

[0009] In another aspect, triketone functionalized polyolefin compositions are disclosed. An example composition of this aspect comprises a polyolefin where a plurality of the repeat units of the polyolefin are functionalized with a triketone moiety (e.g., a P-triketone moiety), such as by way of a linking group between the polyolefin and the triketone moiety. Such triketone functionalized polyolefin compositions may be termed polytopic triketone functionalized polyolefins in that various repeat units of the polyolefin may be functionalized, though such functionalized polymer may not exhibit regularity of repeat unit functionalization that may otherwise be characteristics of a block or alternating copolymer, but instead may be characterized as a random copolymer of polyolefin repeat units and functionalized polyolefin repeat units. In examples, however, the triketone functionalized polyolefin may be block or alternating copolymers of functionalized polyolefin repeat units and other repeat units. The disclosed triketone functionalized polyolefin compositions can undergo reversible reactions with amines to generate diketoenamine functionalized polyolefins and can undergo reversible reactions with polyamines to generate crosslinked polydiketoenamine functionalized polyolefin network. Example copolymers prepared by chain shuttling and useful with and / or for the disclosed techniques and compositions include, but are not limited to, ethylene propylene copolymers. Example alpha-olefin copolymers useful with and / or for the disclosed techniques and compositions include, but are not limited to, ethylene copolymerized with hexene or octene. In some examples, polyolefins useful with and / or for the disclosed techniques and compositions include those made by functionalizing polyolefin blocks of ablock copolymer, such as triblock copolymer thermoplastic elastomers (e.g., styrene-ethylene-co-butylene-styrene (SEBS) polymers).

[0010] In another aspect, diketoenamine functionalized polyolefin compositions are disclosed. An example composition of this aspect comprises a polyolefin where a plurality of the repeat units of the polyolefin are functionalized with a diketoenamine moiety, such as by way of a linking group between the polyolefin and the diketoenamine moiety. Such diketoenamine functionalized polyolefin compositions may be termed polytopic diketoenamine functionalized polyolefins in that various repeat units of the polyolefin may be functionalized, though such functionalized polymer may not exhibit regularity of repeat unit functionalization that may otherwise be characteristics of a block or alternating copolymer, but instead may be characterized as a random copolymer of polyolefin repeat units and functionalized polyolefin repeat units. In examples, however, the diketoenamine functionalized polyolefin may be block or alternating copolymers of the polyolefin repeat units and functionalized polyolefin repeat units.

[0011] In another aspect, cross-linked poly diketoenamine functionalized polyolefin network compositions are disclosed. An example composition of this aspect comprises crosslinked functionalized polyolefins, where some of the repeat units are polyolefins repeat units functionalized with diketoenamine moieties that provide the crosslinks. The polyolefins may be polytopic triketone functionalized polyolefins that are mixed and reacted with a polyamine composition such that the triketone functionalization reacts with the polyamine to generate diketoenamine crosslinks between different polyolefin molecules. Stated another way, the triketone functionalized polyolefins may be crosslinked by polyamine crosslinkers.

[0012] Without wishing to be bound by any particular theory, there can be discussion herein of beliefs or understandings of underlying principles relating to the invention. It is recognized that regardless of the ultimate correctness of any mechanistic explanation or hypothesis, an embodiment of the invention can nonetheless be operative and useful.BRIEF DESCRIPTION OF THE DRAWINGS

[0013] The foregoing aspects and others will be readily appreciated by the skilled artisan from the following description of illustrative embodiments when read in conjunction with the accompanying drawings.

[0014] FIG. 1 depicts an overview of a process for generating polytopic triketone functionalized polyolefins.

[0015] FIG. 2A depicts an overview of a process for generating polytopic diketoenamine functionalized polyolefins and FIG. 2B depicts an overview of a process for generating cross-linked polydiketoenamine functionalized polyolefin networks.

[0016] FIG. 3 provides details regarding C-H functionalization of polyolefins to access dynamic networks.

[0017] FIG. 4 provides examples of C-H functionalization of commodity polyolefins to yield diketoenamine dynamically crosslinked polyolefins.

[0018] FIG. 5 provides structural characterization of diketoenamine dynamically crosslinked polyolefins.

[0019] FIG. 6 provides an overview of diketoenamine dynamically crosslinked polyolefins mechanical properties.

[0020] FIG. 7 provides data showing melting endotherms of functionalized LLDPEs in comparison to LLDPE.

[0021] FIG. 8 provides data showing melting endotherms of functionalized LLDPE in comparison to various mol% functionalization triketone LLDPE.

[0022] FIG. 9 provides data showing melting endotherms of functionalized HDPE in comparison to HDPE.

[0023] FIG. 10 provides data showing melting endotherms of functionalized z-PP in comparison to iPP.

[0024] FIG. 11 provides data showing melting endotherms of functionalized and crosslinked LLDPEs in comparison to LLDPE.

[0025] FIG. 12 provides data showing melting endotherms of functionalized and crosslinked LLDPEs in comparison to LLDPE.

[0026] FIG. 13 provides data showing polyolefin gel permeation chromatography (GPC) results.

[0027] FIG. 14 provides data showing polyolefin gel permeation chromatography (GPC) results.

[0028] FIG. 15 provides data showing polyolefin gel permeation chromatography (GPC) results.

[0029] FIG. 16 provides data showing polyolefin gel permeation chromatography (GPC) results.

[0030] FIG. 17A and FIG. 17B provide data showing polyolefin gel permeation chromatography (GPC) results.

[0031] FIG. 18 provides an overview of amine exchange experiments.

[0032] FIG. 19 provides data showing ratio of reactive amine and impact on gel fraction.

[0033] FIG. 20 provides data showing characteristic FT-IR spectra of triketone functionalized and diketoenamine polymers.

[0034] FIG. 21 provides data showing Near Edge X-ray Absorption Fine Structure spectra.

[0035] FIG. 22 provides data showing Resonant Soft X-ray Scattering spectra.

[0036] FIG. 23 provides data showing Resonant Soft X-ray Scattering spectra.

[0037] FIG. 24 provides data showing Grazing-Incidence Wide-Angle X-ray Scattering patterns.

[0038] FIG. 25 provides data showing Grazing-Incidence Wide-Angle X-ray Scattering spectra.

[0039] FIG. 26 provides data comparing percent crystallinity determined according to different techniques.

[0040] FIG. 27 provides data showing Wide-Angle X-ray Scattering profiles for a pristine polymer, several triketone modified polymers, and several dynamic covalent polyolefin networks.

[0041] FIG. 28 provides oscillatory frequency sweep data for 0.5 mol% diketoenamine crosslinked LLDPE thin films.

[0042] FIG. 29 provides oscillatory strain sweep data for 0.5 mol% diketoenamine crosslinked LLDPE thin films.

[0043] FIG. 30 provides a plot showing stress relaxation data.

[0044] FIG. 31 provides a plot showing stress relaxation data.

[0045] FIG. 32 provides a linear-linear plot of stress relaxation data.

[0046] FIG. 33 provides a plot showing activation energy analysis.

[0047] FIG. 34 provides plots showing creep measurements.

[0048] FIG. 35 provides plots showing creep measurements.

[0049] FIG. 36 provides data for uniaxial tensile pull testing.

[0050] FIG. 37 provides data for tensile pull testing.

[0051] FIG. 38 provides data showing permanently crosslinked fraction for crosslinked and reprocessed polymer networks.

[0052] FIG. 39 provides a proton nuclear magnetic resonance spectrum for an example triketone.

[0053] FIG. 40 provides a proton nuclear magnetic resonance spectrum for an example triketone.

[0054] FIG. 41 provides a proton nuclear magnetic resonance spectrum for an example triketone functionalized linear low-density polyethylene.

[0055] FIG. 42 provides a proton nuclear magnetic resonance spectrum for an example triketone functionalized linear low-density polyethylene.

[0056] FIG. 43 provides a proton nuclear magnetic resonance spectrum for an example triketone functionalized linear low-density polyethylene.

[0057] FIG. 44 provides a proton nuclear magnetic resonance spectrum for an example triketone functionalized linear low-density polyethylene.

[0058] FIG. 45 provides a proton nuclear magnetic resonance spectrum for an example triketone functionalized linear low-density polyethylene.

[0059] FIG. 46 provides a proton nuclear magnetic resonance spectrum for an example triketone functionalized high density polyethylene.

[0060] FIG. 47 provides a proton nuclear magnetic resonance spectrum for an example triketone functionalized isotactic polypropylene.

[0061] FIG. 48 provides a proton nuclear magnetic resonance spectrum for an example triketone functionalized post-consumer polyethylene.

[0062] FIG. 49 provides a proton nuclear magnetic resonance spectrum for an example diketoenamine functionalized linear low-density polyethylene.

[0063] FIG. 50 provides a proton nuclear magnetic resonance spectrum for an example diketoenamine functionalized linear low-density polyethylene.

[0064] FIG. 51 provides a proton nuclear magnetic resonance spectrum for an example diketoenamine functionalized high density polyethylene.

[0065] FIG. 52 provides a proton nuclear magnetic resonance spectrum for an example diketoenamine functionalized isotactic polypropylene.

[0066] FIG. 53 provides a proton nuclear magnetic resonance spectrum for an example extruded triketone functionalized linear low-density polyethylene.

[0067] FIG. 54: provides a proton nuclear magnetic resonance spectrum for an example alcohol functionalized linear low-density polyethylene.

[0068] FIG. 55 provides a carbon-13 nuclear magnetic resonance spectrum for an example triketone.

[0069] FIG. 56 provides a carbon- 13 nuclear magnetic resonance spectrum for an example triketone.

[0070] FIG. 57 provides a proton nuclear magnetic resonance spectrum for l-phenyl-2-(phenylsulfonyl)ethan-l-one.

[0071] FIG. 58 provides a proton nuclear magnetic resonance spectrum for an example O-alkenylhydroxamate.

[0072] FIG. 59 provides a proton nuclear magnetic resonance spectrum for an example thiosulfonate functionalized triketone.DETAILED DESCRIPTION

[0073] Before the present disclosure is described in detail, it is to be understood that the terminology used herein is for purposes of describing particular examples and embodiments only, and is not intended to be limiting.

[0074] In this specification and in the claims that follow, reference will be made to a number of terms that shall be defined to have the following meanings:

[0075] The terms "optional" or "optionally" as used herein mean that the subsequently described feature or structure may or may not be present, or that the subsequently described event or circumstance may or may not occur, and that the description includes instances where a particularfeature or structure is present and instances where the feature or structure is absent, or instances where the event or circumstance occurs and instances where it does not.

[0076] Where a range of values is provided, it is understood that each intervening value, to the tenth of the unit of the lower limit unless the context clearly dictates otherwise, between the upper and lower limits of that range is also specifically disclosed. Each smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in that stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range, and each range where either, neither or both limits are included in the smaller ranges is also encompassed within the invention, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the invention.

[0077] The term “about” refers to a value including 10% more than the stated value and 10% less than the stated value.

[0078] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, the preferred methods and materials are now described. All publications mentioned herein are incorporated herein by reference to disclose and describe the methods and / or materials in connection with which the publications are cited.

[0079] The present disclosure relates to various compositions including triketones, triketone functionalized polyolefins, diketoenamine functionalized polyolefins, and cross-linked polydiketoenamine functionalized polyolefin networks. The disclosed compositions are useful with respect to recycling and / or functionalization of polyolefins, including mixed polyolefins, and can allow such recycled and / or functionalized polyolefins to exhibit enhanced recyclability aspects, as the recycled and / or functionalized polyolefins can be subjected to reversible crosslinking, mixing with virgin, recycled, and / or mixed polyolefins, including serving as a mixing agent to allow for normally immiscible polyolefins to be mixed with one another.

[0080] FIG. 1 depicts an overview of an example process 100 for generating polytopic triketone functionalized polyolefins in accordance with some embodiments. As illustrated a functionalized triketone 105 is reacted with an O-alkenylhydroxamate 110 to functionalize a polyolefin 115 togenerate a polytopic triketone functionalized polyolefin 120. As illustrated in FIG. 1, functionalizedtriketone 105 may have a formulaR1

[0081] Functionalized triketone 105 may represent any of a variety of triketones described herein, such as a functionalized P-triketone comprising a P-triketone moiety covalently linked to a thiosulfonate moiety. Example P-triketone moieties include, but are not limited to, those selectedindependently a ring moiety containing one or more X or C-R ring substituents. In examples, each X is independently selected from the group consisting of O, CRR, SiRR, NR, S, Se, and PR. In examples, each R is independently selected from the group consisting of hydrogen, Cl -20 alkyl, C2-20 alkenyl, C2-20 alkynyl, C3-8 cycloalkyl, Ce-14 aryl, 3- to 12-membered heterocyclyl, and 5- to 12-membered heteroaryl. Optionally, each alkyl is independently unsubstituted or substituted with a C3-8 cycloalkyl, a Ce-14 aryl, a 3- to 12-membered heterocyclyl, or a 5- to 12-membered heteroaryl. Optionally, ring X' contains up to two double bonds in the ring moiety. In examples, Z' is a substituted or unsubstituted linker moiety. Example P-triketone moieties include, but are not limitedexamples, n is 1 to 5. In examples, each Y is independently X or C-R. Example P-triketonearomatic linker, which may optionally be substituted or unsubstituted.o o

[0082] In examples, the thiosulfonate moiety has a formulaRIn examples, R' is a substituted or unsubstituted aliphatic or aromatic group. In specific examples, R' is a phenyl group or a methyl group.

[0083] The polyolefin 115 may comprise a plurality of polyolefin repeat units (PO) and may have any suitable molecular weight or average molecular weight. Polyolefin 115 may comprise or correspond to polyolefins including, but not limited to high density polyethylene (HDPE), linear low-density polyethylene (LLDPE), low density polyethylene (LDPE), isotactic polypropylene (iPP), or other polyolefins. In examples, polyolefin repeat units of polyolefin 115 include, but are not limited to, polyethylene repeat units, polypropylene repeat units, polybutylene repeat units, poly (1 -pentene) repeat units, poly(l -hexene) repeat units, poly (1 -heptene) repeat units, poly(l-octene) repeat units, poly(l -decene) repeat units, poly(l -tetradecene) repeat units, poly(l-hexadecene) repeat units, poly(l -octadecene) repeat units, polynorbornene repeat units, poly(isobutylene) repeat units. In examples, polyolefin 115 may correspond to or comprise copolymer repeat units including two or more monomers (including at least one polyolefin monomer), or branched architecture polymeric repeat units (e.g., prepared using chain shuttling). Other examples of polyolefin 115 include ethylene propylene copolymers, ethylene copolymerized with hexene or octene, and polyolefins made by functionalizing polyolefin blocks of a block copolymer, such as styrene-ethylene-co-butylene-styrene (SEBS) polymers.

[0084] Reaction of polyolefin 115, functionalized triketone 105, and O-alkenylhydroxamate 110 can generate triketone functionalized polyolefin 120, which may be a polytopic triketone functionalized polyolefin 120. In FIG. 1, triketone functionalized polyolefin 120 is depicted ascomprising polymerized polyolefin repeat units, with some of the polyolefin repeat units (PO') covalently coupled by linker moiety (Z) to a triketone moiety (TK). In examples, an amount of the polyolefin repeat units functionalized by the triketone moiety may be from 0.05 wt.% to 20%, such as from 0.05 wt.% to 0.1 wt.%, from 0.1 wt.% to 0.5 wt.%, from 0.5 wt.% to 1 wt.%, from 1 wt.% to 5 wt.%, from 5 wt.% to 10 wt.%, from 10 wt.% to 15 wt.%, or from 15 wt.% to 20 wt.%. In examples, linker moiety Z may be a thioether linker. In FIG. 1, subscript i in triketone functionalized polyolefin 120 indicates non-functionalized polyolefin repeat units, and subscript) represents triketone functionalized polyolefin repeat units.

[0085] In examples, the triketone moiety (TK) may be a P-triketone moiety. Following from the structure of the functionalized triketone 105, in the triketone functionalized polyolefin 120, thetriketone moiety may have a formulawhere X' is described above. Optionally, the triketone moiety may have a formula, where n is 1 to 5, and where each Y is independently X or C-R. Optionally, the P-triketone moiety is selected from

[0086] In examples, Z may be a substituted or unsubstituted linker moiety, such as an aliphatic or aromatic linker moiety containing at least one sulfur atom covalently linking the P-triketone moietyR1 / h,to a respective polyolefin repeat unit. Optionally, Z comprises 7- , where R is a substituted or unsubstituted divalent aliphatic moiety or a substituted or unsubstituted divalent aromatic moiety. In examples, R1may be a divalent phenyl moiety or a divalent alkyl moiety.

[0087] In some examples, a triketone functionalized polyolefin may be mixed with other compositions. As one example, a triketone functionalized polyolefin may be mixed with one or more other polyolefins. Optionally, the polyolefins may comprise the same or different polyolefin repeat units as in the triketone functionalized polyolefin. Optionally, a triketone functionalized polyolefin may be mixed with an amine, such as to generate a diketoenamine functionalized polyolefin, as described in more detail below with respect to FIG. 2A. Optionally, a triketone functionalized polyolefin may be mixed with a polyamine, such as to generate a cross-linked polydiketoenamine functionalized polyolefin network, as described in more detail below with respect to FIG. 2B. In some examples, a triketone functionalized polyolefin may be mixed with another, different, triketone functionalized polyolefin. Such a mixture may also be mixed with a polyamine, such as to generate a cross-linked polydiketoenamine functionalized polyolefin network, as described in more detail below with respect to FIG. 2B.

[0088] FIG. 2A depicts an overview of a process 200 for generating diketoenamine functionalized polyolefins in accordance with some embodiments. As illustrated a polytopic triketone functionalized polyolefin 205 is reacted with an amine 210 to generate a polytopic diketoenamine functionalized polyolefin 215. Polytopic triketone functionalized polyolefin 205 may generally correspond to triketone functionalized polyolefin 120 described above with respect to FIG. 1. Inexamples, the triketone moiety (TK) of polytopic triketone functionalized polyolefin 205 may be a P-triketone moiety. Polytopic triketone functionalized polyolefin 205 may have a formula, as shown in FIG. 2.

[0089] Upon exposure to amine 210, triketone functional groups of polytopic triketone functionalized polyolefin 205 may react to generate diketoenamine functional groups. Accordingly, polytopic diketoenamine functionalized polyolefin 215 may comprise polymerized polyolefin repeat units (PO), wherein at least some of the polyolefin repeat units (PO') are functionalized by a diketoenamine moiety (DK), which may be covalently coupled by way of a linker moiety (Z).

[0090] As above, the polyolefin repeat units may include, but are not limited to polyethylene repeat units, polypropylene repeat units, polybutylene repeat units, poly (1 -pentene) repeat units, poly(l -hexene) repeat units, poly(l -heptene) repeat units, poly(l-octene) repeat units, poly(l-decene) repeat units, poly (1 -tetradecene) repeat units, poly (1 -hexadecene) repeat units, poly(l-octadecene) repeat units, polynorbomene repeat units, or poly(isobutylene) repeat units.

[0091] Optionally, an amount of the polyolefin repeat units functionalized by the diketoenamine moiety is from 0.05 wt.% to 20%, such as from 0.05 wt.% to 20%, such as from 0.05 wt.% to 0.1 wt.%, from 0.1 wt.% to 0.5 wt.%, from 0.5 wt.% to 1 wt.%, from 1 wt.% to 5 wt.%, from 5 wt.% to 10 wt.%, from 10 wt.% to 15 wt.%, or from 15 wt.% to 20 wt.%. In examples, linker moiety Z may be a thioether linker. In FIG. 2, subscript i in polytopic diketoenamine functionalized polyolefin 215 indicates non-functionalized polyolefin repeat units, and subscript) represents diketoenamine functionalized polyolefin repeat units.

[0092] In examples, the diketoenamine moiety comprises a diketone moiety and an amino group.Example formulas for the diketoenamine moiety include, but are not limited to,As above, ring X' may be a ring moiety containing one or more X or C-R ring substituents, such as where each X is independently selected from the groupconsisting of O, CRR, SiRR, NR, S, Se, and PR, and / or where each R is independently selected from the group consisting of hydrogen, Cl-20 alkyl, C2-20 alkenyl, C2-20 alkynyl, C3-8 cycloalkyl, Ce-14 aryl, 3- to 12-membered heterocyclyl, and 5- to 12-membered heteroaryl. Optionally, each alkyl is independently unsubstituted or substituted with a C3-8 cycloalkyl, a Ce-14 aryl, a 3- to 12-membered heterocyclyl, or a 5- to 12-membered heteroaryl. Optionally, ring X' contains up to two double bonds in the ring moiety. In examples, Z is a substituted or unsubstituted linker moiety. In examples, M is an amino group. Optionally, the diketoenamine moiety is selected from, wherein n is 1 to 5, and wherein each Y is independently X or C-R. Optionally, the diketoenamine moiety is selected from[0093J In examples, Z may be an aliphatic or aromatic linker moiety containing at least one sulfur atom covalently linking the diketoenamine moiety to a respective polyolefin repeat unit. Inexamples, Z comprises, where R1is a substituted or unsubstituted divalent aliphatic moiety or a substituted or unsubstituted divalent aromatic moiety. Optionally, R1may be a divalent phenyl group or a divalent alkyl group, which may be substituted or unsubstituted.

[0094] The polytopic diketoenamine functionalized polyolefin 215 may be mixed with other compositions. For example, polytopic diketoenamine functionalized polyolefin 215 may be mixed with another, different, polytopic diketoenamine functionalized polyolefin. In examples, polytopic diketoenamine functionalized polyolefin 215 may be mixed with one or more polyolefins.Optionally, the one or more polyolefins may be miscible with the polyolefin corresponding to polyolefin repeat unit PO in polytopic diketoenamine functionalized polyolefin 215. Optionally, the one or more polyolefins may be immiscible with the polyolefin corresponding to polyolefin repeat unit PO in polytopic diketoenamine functionalized polyolefin 215. Optionally, the one or more polyolefins may be miscible with one another. Optionally, the one or more polyolefins may be immiscible with one another. In some examples, a weight ratio of the one or more polyolefins to the polytopic diketoenamine functionalized polyolefin 215 may be from 1 :99 to 2:1, such as from 1:99 to 1:90, from 1:90 to 1:80, from 1:80 to 1:70, from 1:70 to 1:60, from 1:60 to 1:50, from 1:50 to 1:40, from 1:40 to 1:30, from 1:30 to 1:20, from 1:20 to 1:10, from 1:10 to 1:5, from 1:5 to 2:1, from 2:1 to 1:1, or from 1:1 to 1:2.

[0095] FIG. 2B depicts an overview of a process 250 for generating cross-linked polydiketoenamine functionalized polyolefin networks in accordance with some embodiments. As illustrated a first polytopic triketone functionalized polyolefin 255 and a second polytopic triketone functionalized polyolefin 260 are reacted with a polyamine 265 to generate a cross-linked polydiketoenamine functionalized polyolefin network 270. Optionally, first polytopic triketone functionalized polyolefin 255 and second polytopic triketone functionalized polyolefin 260 are the same, such that cross-linked polydiketoenamine functionalized polyolefin network 270 is constructed from the same polytopic triketone functionalized polyolefins. In other examples, however, first polytopic triketone functionalized polyolefin 255 and second polytopic triketone functionalized polyolefin 260 are different. Optionally, polyamine 265 is a diamine, triamine, or other compound that includes four or more amino groups.

[0096] In examples, cross-linked polydiketoenamine functionalized polyolefin network 270 has a1I<O1VP°^formula' A 4 , where PO1is a first polyolefin repeat unit, such as of or derived from the first polytopic triketone functionalized polyolefin 255, PO1' is a first diketoenamine functionalized polyolefin repeat unit derived from the first polytopic triketone functionalized polyolefin 255, PO2is a second polyolefin repeat unit, such as of or derived from the second polytopic triketone functionalized polyolefin 260, PO2' is a diketoenamine functionalized polyolefin repeat unit derived from the second polytopic triketone functionalized polyolefin 260, DK1is a first diketoenamine moiety, DK2is a second polyketone moiety, where M represents a crosslinker of or derived from the polyamine 265. In examples, each Z is independently an aliphatic or aromatic linker moiety, optionally containing at least one sulfur atom, covalently linking a diketoenamine moiety to a respective polyolefin repeat unit. In. FIG. 2B, i indicates non-functionalized repeat units of or derived from the first polytopic triketone functionalized polyolefin 255, j represents functionalized repeat units of or derived from the first polytopic triketone functionalized polyolefin 255, k indicates non-functionalized repeat units of or derived from the second polytopic triketone functionalized polyolefin, and 1 represents functionalized repeat units of or derived from the second polytopic triketone functionalized polyolefin.

[0097] Optionally, the first polyolefin repeat units (PO1) and the second polyolefin repeat units (PO2) correspond to miscible polyolefins. Optionally, the first polyolefin repeat units (PO1) and the second polyolefin repeat units (PO2) correspond to immiscible polyolefins. Any suitable amount or fraction of the polyolefin repeat units of first polytopic triketone functionalized polyolefin 255 may be functionalized by a first triketone moiety (TK1). Any suitable amount or fraction of the polyolefin repeat units of second polytopic triketone functionalized polyolefin 260 may be functionalized by a second triketone moiety (TK2). Example amounts include from 0.05 wt.% to 20 wt.%, such as from 0.05 wt.% to 0.1 wt.%, from 0.1 wt.% to 0.5 wt.%, from 0.5 wt.% to 1 wt.%, from 1 wt.% to 5 wt.%, from 5 wt.% to 10 wt.%, from 10 wt.% to 15 wt.%, or from 15 wt.% to 20 wt.%. The first triketone moiety and second triketone moiety may independently correspond to P-triketone moieties. Optionally, Z is a thioether linker.

[0098] As above, the polyolefin repeat units may be polyethylene repeat units, polypropylene repeat units, polybutylene repeat units, poly (1 -pentene) repeat units, poly(l -hexene) repeat units, poly (1 -heptene) repeat units, poly(l -octene) repeat units, poly(l -decene) repeat units, poly(l-tetradecene) repeat units, poly (1 -hexadecene) repeat units, poly (1 -octadecene) repeat units, polynorbomene repeat units, or poly(isobutylene) repeat units, though other repeat units may be used in some examples.

[0099] Upon crosslinking by reaction with polyamine 265, the cross-linked polydiketoenamine functionalized polyolefin network 270 may include crosslinks of the form•A . In examples, the diketoenamine moieties DK1and DK2and M togetherring moiety containing one or more X or C-R ring substituents. In examples, each X is independently selected from the group consisting of O, CRR, SiRR, NR, S, Se, and PR. In examples, each R is independently selected from the group consisting of hydrogen, Cl -20 alkyl, C2-20 alkenyl, C2-20 alkynyl, C3-8 cycloalkyl, Ce-14 aryl, 3- to 12-membered heterocyclyl, and 5- to 12-membered heteroaryl. Optionally, each alkyl is independently unsubstituted or substituted with a C3-8 cycloalkyl, a Ce-14 aryl, a 3- to 12-membered heterocyclyl, or a 5- to 12-membered heteroaryl.Optionally, ring X' contains up to two double bonds in the ring moiety. In examples, Z is independently a substituted or unsubstituted linker moiety. In examples, DK1- / or DK2-Z mayindependently comprise or have a formulaor

[0100] Optionally, each Z is independently an aliphatic or aromatic linker moiety containing at least one sulfur atom covalently linking the -triketone moiety to a respective polyolefin repeat unit.R1 / h,iOptionally, Z comprises, where R is a substituted or unsubstituted divalent aliphatic moiety or a substituted or unsubstituted divalent aromatic moiety, such as a divalent phenyl or alkylmoiety. In examples, polyamine 265 is a diamine or a triamine. Any suitable polyamine may be used, without limitation.

[0101] The cross-linked polydiketoenamine functionalized polyolefin network 270 may be mixed with other compositions. For example, cross-linked polydiketoenamine functionalized polyolefin network 270 may be mixed with one or more polyolefins. Optionally, the one or more polyolefins may be miscible with the polyolefin corresponding to polyolefin repeat unit PO1or PO2. Optionally, the one or more polyolefins may be immiscible with the polyolefin corresponding to polyolefin repeat unit PO1or PO2. Optionally, the one or more polyolefins may be miscible with one another. Optionally, the one or more polyolefins may be immiscible with one another. In some examples, a weight ratio of the one or more polyolefins to the cross-linked polydiketoenamine functionalized polyolefin network 270 may be from 1 :99 to 2: 1, such as from 1 :99 to 1 :90, from 1 :90 to 1 :80, from 1:80 to 1:70, from 1:70 to 1:60, from 1:60 to 1:50, from 1:50 to 1:40, from 1:40 to 1:30, from 1:30 to 1:20, from 1:20 to 1:10, from 1:10 to 1:5, from 1:5 to 2:1, from 2:1 to 1:1, or from 1:1 to 1:2.

[0102] Aspects of the disclosure and the invention may be further understood by reference to the following non-limiting examples.EXAMPLE 1 : C-H FUNCTIONALIZATION OF POLYOLEFINS TO ACCESS REPROCES SABLE POLYOLEFIN THERMOSETS

[0103] Upcycling plastic waste into reprocessable materials with performance-advantaged properties can contribute to the development of a circular plastics economy. This Example modifies branched polyolefins and post-consumer polyethylene through a versatile C-H functionalization approach using thiosulfonates as a privileged radical group transfer functionality. Crosslinking the functionalized polyolefins with polytopic amines provided dynamic crosslinked polyolefin networks enabled by associative bond exchange of diketoenamines. A combination of resonant soft X-ray scattering and grazing incidence X-ray scattering revealed hierarchical phase morphology, in which diketoenamine-rich microdomains phase-separate within amorphous regions between polyolefin crystallites. The combination of dynamic covalent crosslinks and microphase separation results in useful mechanical properties, including a ~4.5-fold increase in toughness, a reduction in creep deformation at temperatures relevant to use, and high-temperature structural stability compared to the parent polyolefin. The dynamic nature of the diketoenamine crosslinks provides stress relaxation at elevated temperatures, which enabled iterative reprocessing of the dynamic covalent polymernetwork with little cycle-to-cycle property fade. The ability to convert polyolefin waste into a reprocessable thermoformable material with attractive thermomechanical properties provides additional optionality for upcy cling to enable future circularity.

[0104] Accumulation of plastic in the environment is a contemporary societal and ecological problem as a result of end-of-life plastic waste management that is poorly matched with the scale of global plastic production. Using plastic waste as a starting material to synthesize performanceadvantaged materials (e.g., upcy cling) has the benefit of diverting waste from landfills and lowering the dependance on petrochemical resources. Polyolefins in particular represent advantageous substrates for polymer upcycling because they account for a large fraction (>50%) of global plastic production and are particularly challenging to recycle. The C-H functionalization of polyolefins has resulted in materials that have diversified properties. Upcycling polyolefins into reprocessable substitutes for materials that are currently non-recyclable provides an approach for enhanced waste utilization.

[0105] Crosslinked polymers are robust high-volume materials with permanent covalent bonds between polymer chains which preclude reprocessing; therefore, these materials are landfilled after use. Polymer networks whose crosslinks undergo reversible exchange reactions may serve as versatile replacements for many difficult-to-recycle thermoplastics and thermosets.Polydiketoenamine (PDK) dynamic covalent networks in particular are a versatile class of materials whose chemistry can be tailored to access a range of properties, while remaining mechanically reprocessable and chemically recyclable. Dynamic covalent polymer networks, however, are often built from petrochemical resources and yield under applied strain (e g., creep) at temperatures relevant to their desired application.

[0106] Placing dynamic diketoenamine functional groups onto polyolefins can enable access to performance-advantaged reprocessable polyolefin thermosets and represents an example of upcycling plastic waste to a next generation of resilient circular polymeric materials. A challenge to placing regenerative functionality onto polyolefins post-production is the high bond strength of aliphatic C-H bonds. This has traditionally been overcome by using peroxide-mediated hydrogen atom transfer (HAT) under harsh reaction conditions, which leads to a deterioration in polymer properties (FIG. 3, Panel B). Consequently, approaches to dynamic covalent polyolefin networks through post polymerization modification have been limited and, when pursued, has yielded thermosets with partial network connectivity and a corresponding high density of plasticizing chainsdue to peroxide mediated HAT. The lack of structural control inherent to peroxide mediated HAT has convoluted studies to understand how dynamic crosslinks impact the phase behavior, crystallinity, mechanical properties, as well as reprocessability of dynamic covalent polyolefin networks (DCPNs).

[0107] An O-alkenylhydroxamate reagent has been identified whose steric demand around nitrogen and strong thermodynamic driving force for HAT result in selective and efficient functionalization, with an observed lack of chain coupling or scission events. The amide reagent was hypothesized, when combined with a triketone radical trap with fast chain-transfer kinetics, to provide a platform to access DCPNs with discrete control over polymer structure and high network connectivity (FIG. 1, Panel C). Selective placement of diketoenamine functionality can enable a more holistic understanding of structure-property-performance relationships of DCPNs and evaluation of their potential as sustainable alternatives to current single-use polyolefin thermoplastics and thermosets.

[0108] In this Example, triketone functionalized polyolefins were synthesized through amidyl radical mediated C-H functionalization by using thiosulfonates as an enabling triketone group transfer functionality. Subsequent crosslinking with a polytopic amine provided diketoenamine crosslinked DCPNs that demonstrate high network connectivity, efficient remoldability, and enhanced mechanical properties even at very low crosslinker content (~1 diketoenamine every 200 repeat units). Resonant soft X-ray scattering (RSoXS) revealed hierarchical phase behavior in the materials, where polar diketoenamine-rich domains reside in the amorphous phase between polyolefin crystallites and contribute to their improved thermomechanical properties. Dynamic crosslinks imparted resistance to creep at temperatures relevant to applications of crosslinked polyolefins, and the associative exchange of diketoenamine functional groups enabled reprocessing with little cycle-to-cycle property fade.

[0109] Results and Discussion. To add triketone groups onto polyolefins, thiosulfonates were identified as a functional group that rapidly transfers desirable functionality to alkyl radicals. When combined with the O-alkenylhydroxamate reagent (1), it was hypothesized that a custom-synthesized thiosulfonate appended with a triketone (2) can provide efficient group transfer of functionality that would enable access to DCPNs (FIG. 4, Panel A). The study was initiated using linear low-density polyethylene (LLDPE), a branched commodity polyolefin substrate relevant to plastic recycling. Triketone group transfer occurred in 30 minutes at 130 °C in chlorobenzene. ForLLDPE, stoichiometry targeting 10 mol% functionalization relative to polymer repeat unit provided P5 with 3.1 mol% of triketone on the polymer, as quantified by high temperature *HNMR. The degree of functionalization can be systematically varied, allowing for tunable functionalization between 0.1 and 3.1 mol% (1 to 18 triketones per chain on average) (P1-P5) by altering the stoichiometry of 1 and 2 relative to repeat unit (FIG. 4, Panel B). Similar levels of functionalization were observed for high density polyethylene (HDPE) (P6), whereas isotactic polypropylene (iPP) demonstrated a lower efficiency of functionalization (0.4 mol%) (P7), which is in-line with previous observations. The molecular weight distribution demonstrated minimal change after functionalization, indicating a lack of observed chain scission enabled by a high degree of regioselectivity (FIG. 4, Panel C, FIG. 13, FIG. 14, FIG. 15, FIG. 16, and FIG. 17A). We were able to translate the approach to functionalization of post-consumer polyethylene (PCPE) obtained from packaging waste at a similar efficiency to HDPE and LLDPE (P8).

[0110] With access to triketone functionalized polyolefins, an understanding of the reactivity of the polymer-bound triketones with monofunctional amines to access diketoenamines as soluble surrogates for crosslinked diketoenamine polyolefins was sought. LLDPE functionalized with 3.1 mol% triketone (P5) was heated to 130 °C in chlorobenzene in the presence of excess hexylamine, which resulted in full conversion to hexyl diketoenamine (FIG. 18). Subsequently, the potential for amine exchange was investigated. Heating the hexyl diketoenamine LLDPE in the presence of excess benzyl amine fully converted the material into a benzyl diketoenamine functionalized polymer (FIG. 18). These data provided evidence that the polymer-bound triketones can undergo dynamic covalent exchange in the presence of amines, which is necessary for realizing thermal reprocessability.[oni] With the understanding of the reactivity of polymer bound triketone, a diketoenamine DCPN was fabricated by reacting a 0.5 mol% triketone functionalized LLDPE (P2) with a tri-topic amine, tris(2-aminoethyl)amine (TREN) for 15 min in chlorobenzene at 130 °C (FIG. 4, Panel A). The stoichiometry of primary amine relative to polymer bound triketone was systematically varied to probe efficiency of crosslinking. Gel fraction increased as the equivalents of amine approached that of triketone, which reached a maximum of 85% at an equimolar concentration (FIG. 4, Panel D). This high network participation at a low density of polymer functionalization is a significant advantage over strategies that rely on peroxide-mediated polyolefin functionalization, where a high density of uncrosslinked chains act as diluents and complicate structure-property studies.

[0112] An understanding of the impact of polymer functionalization on the crystallinity was assessed by wide-angle X-ray scattering (WAXS) because functionalization typically results in defects that disrupt polyolefin crystallization and, accordingly, mechanical properties. Both LLDPE and functionalized polymers showed two primary scattering peaks at scattering vector, q, of 1.5 and 1.7 A1which correspond to the reflections of the orthorhombic crystal lattice due to the regular packing of polyethylene chains to form lamellae (FIG. 5 Panel A). The intensity of the scattering peaks decreases upon functionalization (P2) and crosslinking (DCPN-P2). The crystallinity fraction was quantitatively determined by comparing the integration of the crystalline and amorphous phases by WAXS (FIG. 5 Panel B). A significant fraction of the crystallinity was preserved for DCPN-P1 (41%) relative to LLDPE (42%), which was hypothesized as being due to the low areal density of crosslinking sites (0.1 mol%). Increasing the density of functionalization to 0.5 mol% for the formation of the DCPN-P2 showed a decrease in crystallinity to 30%. Further increasing the density of crosslinking to 2.2 mol% functionalization for DCPN-P4 resulted in a 15% crystalline material. To calculate the percent crystallinity through a complementary technique, the enthalpies of melting were determined by differential scanning calorimetry (DSC), whose trends fit with the WAXS data (FIG. 26). From these data, a lower degree of crosslinking appears to result in longer chain segments that can participate in crystallization and, thus, a higher degree of crystallinity compared to DCPNs with a higher degree of functionalization.

[0113] With the addition of polar diketoenamines into the non-polar polyolefin matrix, microphase separation was hypothesized to occur to generate more complex phase behavior, where diketoenamine domains are dispersed within the amorphous phase of the semicrystalline polyolefin (FIG. 5, Panel C). The elementally weighted distribution of microstructures in DCPN-P2 was characterized by RSoXS. RSoXS exploits X-ray radiation that is resonant with atomic electronic transition and enables the identification of not only spacing, but also elemental composition of microphase separated domains. With the triketone group being the only oxygen-containing functionality in the crosslinked material, triketone- or diketoenamine-rich domains were expected to show enhanced scattering as X-ray energies approach the characteristic absorption energy of oxygen at 537 eV, according to the Near Edge Absorption Fine Structures (NEXAFS) spectrum for the triketone functionalized polymers (FIG. 21).

[0114] Both LLDPE and triketone-modified LLDPE (P2) did not show evidence of microphase separation, indicating no phase separation of triketones was occurring in the non-crosslinked polymers (FIG. 5, Panel D, FIG. 22). After crosslinking with TREN, however, scattering wassignificantly enhanced as X-ray energy approached 537 eV. The scattering peak in the integrated spectrum indicated the clear formation of diketoenamine-rich domains with a spacing of 10-15 nm. Additionally, the spacing of diketoenamine rich domains increased as equivalents of amine crosslinker increased (FIG. 5, Panel D). Grazing-incidence wide-angle X-ray scattering (GIWAXS) showed that the relative degree of crystallinity increased as crosslinking increased for DCPN-P2 (e.g., as more TREN was added), which suggests that phase separation of diketoenamine-rich domains helps to recover the loss of crystallinity that would otherwise result from crosslinking and potentially contributes to retaining the beneficial properties of polyolefins within the DCPN (FIG. 5, Panel E, FIG. 25). Taken together, these characterizations of structure indicate that DCPNs are comprised of a complex combination of physical crystalline crosslinks, dynamic covalent chemical crosslinks, and polar triketone-rich domains, all of which contribute to material properties (FIG. 5 Panel C).

[0115] With an understanding of the chemical structure and phase behavior of DCPNs, an understand of the impact of the dynamic covalent crosslinks on mechanical properties was sought. The performance of DCPN-P2 was assessed under uniaxial strain (FIG. 6, Panel A, FIG. 35).LLDPE demonstrated typical thermoplastic behavior, with high yield stress (~18 MPa) at low strain followed by necking of the material until failure. The 0.5 mol% triketone modified LLDPE (P2) showed similar behavior, suggesting that the lower strength and higher ductility were due to the lower % crystallinity as a result of functionalization. DCPN-P2 demonstrated a clear elastic region and yield at low strain, which was attributed to the crystalline regions of the material. After yielding, DCPN-P2 demonstrated a pronounced strain stiffening behavior and elongated approximately 2.5-times its original length before fracture. The observed strain stiffening behavior was hypothesized as attributed to an interplay between the finite extensibility of polymer chains and the cooperative bond reorganization of the DCPN crosslinks that redistribute stress within the material. This material performance, which is a result of both the semicrystalline structure and dynamic covalent crosslinks, yielded a material that is 4.5-times tougher compared to the parent LLDPE material. To understand the effect of crosslinking density, 0.5 mol% functionalized DCPN-P2 and 0.1 mol% functionalized DCPN-P1 were compared. The DCPN with lower crosslinking density showed greater yield stress, higher ductility, but less strain-stiffening. Greater yield stress is consistent with less disruption of crystallinity as a result of lower percent functionalization. Higher ductility is attributed to longer network strands that increase the network extensibility at larger strains. These data indicated thatcontrolled dynamic network synthesis enabled tunable performance-advantaged properties from commodity polyolefin substrates.

[0116] Next, an understanding of how the structure of diketoenamine crosslinked polyolefins influenced the reprocessability of the bulk materials was sought by probing their stress relaxation through rheological measurements. An initial step strain was applied to DCPN-P2 at 200 °C, resulting in stress that decayed to zero over 2 h, which is consistent with bond exchange that dissipates stress at elevated temperatures (FIG. 6, Panel B). This stress relaxation was anticipated to enable reprocessing of the DCPN. The activation energy to bond exchange was extrapolated from stress relaxation time for each temperature using Arrhenius analysis (FIG. 33). DCPN-P2 exhibited an activation energy to bond exchange of 115 kJ mol-1, which is considerably higher than the activation energy of 49 kJ mol-1for diketoenamine networks comprised of TREN and a small molecule bis-triketone. The difference in activation energies may be a consequence of the reorganization energy required for crosslinkers to diffuse through hydrophobic polyolefin to access other diketoenamine-rich domains for bond exchange.

[0117] While numerous dynamic covalent networks demonstrate attractive mechanical properties under rapid deformation, the dynamic exchange of crosslinks typically results in a loss in structural integrity under ambient conditions due to creep deformation over longer time scales. To understand the creep behavior of DCPNs, a constant stress was applied to both the semicrystalline LLDPE and DCPN-P2 at 60 °C and the strain deformation was measured as a function of time (FIG. 6, Panel C, FIG. 34 and FIG. 35). These data clearly show that the diketoenamine crosslinked polyolefin creep very little and deform at a slower rate than the LLDPE, despite LLDPE having higher % crystallinity. The hierarchical organization of the DCPN, with crosslinks organized into discrete domains and separated by crystalline regions, is proposed to reduce creep compared to other dynamic covalent networks and even semicrystalline polyolefins.

[0118] To further understand the impact of dynamic chemical crosslinks upon network integrity, oscillatory temperature sweeps under uniaxial extension were conducted through the melting temperature of the materials. As expected for a thermoplastic, the modulus of LLDPE dropped quickly to zero above its melting temperature (Tm). DCPN-P2, in contrast, showed a decrease in modulus through its melting point and a plateau at ~0.1 MPa (FIG. 6, Panel D). These results indicate that the diketoenamine crosslinks support network integrity and sample shape at elevated temperatures above Tm.

[0119] To assess whether stress relaxation in the network results in reprocessability, the DCPN-P2 was cut into pieces and compression molded at 200 °C for 2 h to yield smooth, transparent films that had similar mechanical properties to the virgin material, even after 3 rounds of reprocessing (FIG. 6, Panel D, FIG. 37). To demonstrate the potential for circularity, the polymer network after three rounds of reprocessing was completely solubilized by the addition of monofunctional amine (FIG. 38). This experiment demonstrated that no permanent crosslinks were formed during iterative mechanical reprocessing and that the network can be efficiently deconstructed for subsequent reactivity.

[0120] This Example demonstrates a new class of polyolefin thermosets that are reprocessable over multiple cycles and resist creep deformation at use temperatures. Amidyl radical mediated C-H functionalization enabled the placement of triketone groups onto a variety of polyolefin substrates, including post-consumer plastic waste, which serve as precursors to diketoenamine DCPNs. The selectivity and efficiency of this approach provides high network connectivity even at low crosslinking densities, which enables an understanding of how dynamic exchange of crosslinkers contribute to material properties. Crosslinking using dynamic diketoenamines significantly improves the toughness of the material and results in improved resistance to creep compared to LLDPE.Structural characterization revealed that the changes in crystallinity, dynamic covalent exchange reactions, and phase separation contributed to the performance of the material. The ability to upcycle post-consumer plastic waste into useful reprocessable thermosets with well-defined structure and attractive thermomechanical properties is anticipated to expand the options for polyolefins to enter a more circular plastics economy.

[0121] Additional Materials and Methods . Materials. Unless otherwise noted, solvents were dried and degassed using a Pure Process Technology solvent purification system and then subsequently stored over molecular sieves (3 A) in a N2-filled glovebox. Other reagents whose syntheses are not described were purchased from commercial sources (Alfa Aesar (Ward Hill, MA), MilliporeSigma (St. Louis, MO), Oakwood Products (West Columbia, SC), Acros Organics (Geel, Belgium), and TCI America (Portland, OR)) and used without further purification. All syntheses were performed under an inert N2 atmosphere using flame-dried or oven-dried glassware unless specified otherwise or in aN2-filled glovebox. Thin layer chromatography (TLC) was performed on SiliaPlate 250 pm thick silica gel plates provided by Silicycle. Visualization was accomplished with short wave UV light (254 nm), iodine, aqueous basic potassium permanganate solution, or aqueous acidic ceric ammonium molybdate solution followed by heating. Flash chromatography wasperformed using SiliaFlash P60 silica gel (40-63 pm) purchased from Silicycle. Compounds were isolated either by manual column or by Biotage Isol era Flash Chromatography.

[0122] Polyolefin substrates used in this study (molar mass determination by comparing to polystyrene standards):LLDPE (DOW DNDA 1081NT) Mn=21 kg / mol; £> = 3.8LDPE (DOW Polyethylene 4012 Low Density) Mn= 34 kg / mol, D = 68.8HDPE from (Exxon HD6719) / n=42 kg / mol, £> = 3.3iPP (Basell Profax 6301 12 MFR) A£=62 kg / mol, £> = 5.1Post-consumer polyethylene was obtained from Highcube® recycling A =23 kg / mol, D = 7.6

[0123] Characterization. HT GPC / Tosoh EcoSEC-HT GPC. High temperature gel permeation chromatography (HT GPC) spectra were obtained using a Tosoh EcoSEC-HT GPC using TSKgel GMHHR-M columns. A solution of 1, 2, 4-tri chlorobenzene (TCB) with 200 ppm dibutylhydroxytoluene (BHT) was used as the mobile phase at a flow rate of 1 mL / min. The instrument was calibrated using polystyrene standards in the range of 580 to 5,480,000 Da. A calibration curve was created using refractive index detection against 2 mg / mL polystyrene standards in TCB with 200 ppm BHT at 140 °C. A tandem multi-angle light scattering (MALS) detector could also be employed on the HT GPC via a Wyatt DAWN 8 heated flow cell instrument.

[0124] TGA / TA Instruments Q5000 Therm ogravimetric Analyzer. Decomposition onset temperatures (Ta) of precipitated and dried polymer samples were measured by thermal gravimetric analysis (TGA) on a TA Instruments Q5000 Thermogravimetric Analyzer. Polymer samples were heated from ambient temperatures to 600 °C at a heating rate of 10 °C / min. Values of Ta (temperature at 5% weight loss) were obtained from wt% vs. temperature (°C) plots.

[0125] DSC / TA Instruments Discovery DSC. Melting-transition temperature (Tm) and glasstransition temperature (7g) of precipitated and dried polymer samples were measured using differential scanning calorimetry (DSC) on a TA Instruments Discovery DSC. Unless specifically noted otherwise, values for Tmand Tgwere obtained from a second heating scan after the thermal history was removed. Samples of 1-10 mg were heated 10 °C / min between 25 and 160 °C.

[0126] IR. Infrared (IR) spectra were obtained using a PerkinElmer Frontier FT-IR spectrometer under attenuated total reflection 32 scans were conducted.

[0127] NMR. NMR spectra were recorded using a Bruker Neo 400 MHz, or Bruker AVANCE III 600 MHz CryoProbe spectrometer. Chemical shifts 5 (ppm) are referenced totetramethyl silane(TMS) using the residual solvent as an internal standard (XH and13C). For 'H NMR: CDC13= 7.26 ppm, CD2CI4 = 6.00. For13C NMR: CD2CI4 = 73.78 ppm.

[0128] High temperature NMR (HT NMR) for polyolefin characterization was recorded on a Bruker 500 MHz spectrometer set to 110 °C with ethylene glycol standard to quantify temperature of the NMR probe - roughly 116 °C in all cases. Solvent resonance served as the internal standard H NMR: C2D2CI4 at 6.00 ppm;13C NMR: C2D2CI4 at 73.78 ppm). Delay time was set to 5 sec (dl = 5). 100 scans were required for functionalization levels of 0.5 mol% or lower.

[0129] Coupling constants (J) are expressed in hertz (Hz). 'H NMR data are reported as follows: chemical shift, multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, dd = doublet of doublets, dt = doublet of triplets, bs = broad singlet), coupling constants (Hz), and integration.

[0130] Melt Press. Polymer films 200 - 600 pm were prepared by melt-pressing using a PHI Manual Compression Press. On a steel plate was placed a Kapton film (Kapton KN .01”) (pretreated with Frekote 770-NC). A brass shim stencil was placed to control film thickness before polymer was added. Another Kapton film was placed on top followed by a second steel plate. The setup was then heated at 200 °C for 2 hours for crosslinked samples. Linear samples were heated at 150 °C for 5 minutes. Films were removed from the melt press and cooled to room temperature by rapid heat transfer to an aluminum surface.

[0131] Rheometry. Melt pressed samples were cut into discs (diameter = 8 mm). Sample thickness was measured using calipers. Samples were measured in an ARES G2 rheometer equipped with a temperature probe and tested under ambient atmospheric conditions.

[0132] Preliminary frequency sweeps and stain sweeps were completed to identify the linear viscoelastic regime for the polyolefin crosslinked diketoenamine vitrimers.

[0133] Frequency sweeps were conducted at 160 °C, significantly above the melt temperature. Oscillatory strain of 2% was applied and frequency was varied between 0.1 and 100 Hz.

[0134] Strain sweeps were conducted at 160 °C. Frequency was held constant at 1 Hz and strain was varied between 0.1 and 100% strain.

[0135] Stress relaxation was completed at 170 °C, 180 °C, 190 °C and 200 °C, 210 °C, and 220 °C significantly above melt temperature to target study of activation energy due to bond exchange rather than also probing the impacts of crystallinity. Based on preliminary data, step strain of 2% was applied to the material which then relaxed stress for 2 hours - 10 hours depending upon temperature. A constant axial force was maintained throughout testing.

[0136] Dynamic Mechanical Analysis. For tensile testing, melt pressed samples were cut into dog-bones using an ISO 527 Type 5B cutting die to standard dimensions (12 mm bridge length and 2 mm bridge width). Sample thickness at the bridge was measured using calipers. Test specimens were affixed to the TA RS A G2 DMA with a starting gap of 18 mm for consistent pulls. Care was taken to ensure that samples were aligned vertically. Samples were pulled at 0.09 mm / s which falls within the linear viscoelastic regime determined by rheological frequency sweeps and tensile tests at variable strain rates. Tensile experiments were conducted at room temperature in triplicate. Average values and standard deviations are reported.

[0137] Dynamic mechanical thermal analysis (DMTA) was performed by cutting melt pressed samples into rectangular strips 2mm width x 12 mm length. The gap was set to 8mm. Samples were analyzed under oscillatory strain of 2% as temperature was increased from 25 °C to 200 °C at a rate of 10 °C / min. Storage modulus (E’) was recorded as a function of temperature.

[0138] Wide-Angle X-ray Scattering. Wide-Angle X-ray scattering (WAXS) measurements were collected on a Xeuss 3.0 (Xenocs, France) equipped with a D2+ Metal Jet X-ray source (Ga Ka, 9.2 keV, X = 1.3414 A). Polymer fdms were pressed and adhered to the solids sample holder, aligned perpendicular to the direction of the incident beam (transmission mode), measured for 10 min at a sample-to-detector distance of 47 following calibration with a AgBeh standard. 2D images of the scattering patterns were collected on a Eiger 2R 4M hybrid photon counting detector with a pixel dimension of 75 x 75 jim2(Dectris, Switzerland). Azimuthal averages were reduced from the 2D WAXS images and plotted in the form of intensity versus scattering vector (q), where q = (4TT sin^) / z, following background and sample thickness corrections applied in the XSACT software package (Xenocs, France). ID data was analyzed to extract the percent crystallinity (%c) using:c—a, where Acis the area of the crystalline peaks and Aais the area of the amorphous halo.

[0139] The Scherrer equation was used to estimate the broadening for the 110 peaks due to crystallite thickness variation according to:L110= pcos^ey Here K is taken as a shape factor taken to be 0.9, is the wavelength of the incident beam, ft is the FWHM and 6 is the Bragg angle. Instrumental broadening was accounted for and subtracted from crystalline standards.

[0140] Small molecule synthesis. Alkenylhydroxamate (amide reagent) synthesis.OBenzene [0.7 M], 45°CS1

[0141] JV-( rt-butyl)-O-benzoylhydroxylamine (SI): To a flame dried round bottom flask with a stir bar was added benzoyl peroxide (20.0 g, 82.6 mmol, 1 equiv.), which was then dissolved in benzene (115 mL, 0.7 M). The reaction was sealed and placed under N2. A portion of tert-butylamine (21 mL, 330 mmol, 4 equiv.) was added and the reaction heated at 45 °C for 1 hour, and changed color from cloudy white color to cloudy Carolina blue. After 1 hour, a second portion of / c' / 'Z-butylamine (13.7 mL (overall 34.7 mL, 330 mmol, 4 equiv.)) was added through the septum and the reaction was let to stir overnight. Then, the reaction cooled to room temperature before it was diluted with diethyl ether, and solid ammonium salt was filtered off. To the filtrate was added acidic aqueous FeSCLin ~1M H2SO4 (50 mL); the mixture was stirred for 10 minutes. The mixture was transferred to a separatory funnel, and the layers were separated. The organic layer was washed with saturated sodium bicarbonate solution (3 X 50 mL), water (1 X 50 mL), dried over MgSCU, filtered and concentrated to afford product SI as orange / yellow oil (13.8 g, 87% yield) in accordance with reported spectral data; the compound was used directly without purification.0 1) {COCI)2,DMF, DCM.0 °C to rt2) S1, pyridine,CF3PhH, refiux

[0142] JV-(tert-butyl)-O-benzoyl-(3,5-bis-trifluoromethyl)-hydryoxyamide (S2): To a flame dried round bottom flask with stir bar was added (3,5-bis-trifluoromethyl)-benzoic acid (16.8 g, 65.1 mmol, 1 equiv.), dissolved in dichloromethane (100 mL, [0.6 M]). Catalytic dimethylformamide was added (26 pL, 97 umol, 0.005 equiv. ), and the reaction was sealed, and brought to 0°C. Oxalyl chloride was added dropwise via syringe (11.0 mL, 130 mmol, 2 equiv ), and the reaction stirred at 0°C for 15 minutes, then was let come to room temperature. The reaction was left to react until thecloudy white solution completely dissolved, forming a clear yellow solution, and continued to stir until bubbling subsided (~3 hours). Then, the reaction was carefully concentrated in vacuo to remove all excess oxalyl chloride, HC1, and CO; the resulting yellow oil was taken up in benzene (100 mL), and benzoylhydroxylamine (SI) was added (13.8 g, 71.6 mmol, 1.1 equiv.) in minimal amount of benzene (1-2 mL). Pyridine was added (11.1 mL, 137 mmol, 2.1 equiv.), the flask was equipped with a condenser, and brought to reflux overnight. At end of the reaction, the mixture allowed to cool to room temperature, diluted with diethyl ether, and pyridinium salt filtered off. Filtrate was transferred to separatory funnel, washed with 1 M hydrochloric acid (2 X 100 mL), water, dried over MgSCL, filtered and concentrated to afford product S2 as amber-colored solid (28.21 g, 99% yield). The compound was used directly in the next step without purification.

[0143] JH NMR (600 MHz, CDCh) 38.03 (s, 1H), 7.82 (d, 2H), 7.76 (s, 1H), 7.59 (t, 1H), 7.41 (t, 2H), 1.62 (s, 9H).

[0144] 13C NMR (151 MHz, CDCh) 8 167.5, 165.2, 137.5, 134.6, 131.3 (q), 129.6, 128.8, 127.89, 125.7, 123.6, 121.9, 63.8, 27.5.

[0145] 19F NMR (376 MHz, CDCh) 8 -63 0

[0146] HRMS (HESI) Exact mass calcd for C20H17F6NO3H [M+H]+, 434.1191. Found 434.1180.

[0147] JV-(tez7-butyl)-(3,5-bis-trifluoromethyl)-hydryoxyamide (S3): To a large round bottom flask with magnetic stir bar was added O-benzoylhydroxyamide S2 (28.21 g, 65.10 mmol, 1 equiv.), dissolved in ethanol (180 mL, [0.3 M]). The reaction was capped and equipped with N2 line.Hydrazine monohydrate (23.7 mL, 488 mmol, 7.5 equiv.) was added dropwise, and the reaction was heated to 40°C for 2 hours. The mixture was cooled to room temperature, then brought to 0°C. The mixture was then poured into ice water (~1.5 X volume of ethanol used), inducing precipitation of a white solid from yellow solution. The reaction was kept at 0 °C for 5 minutes after which the solid was collected by filtration, washed with cold water, washed with pentanes, and dried thoroughly on hi-vac overnight to afford hydroxyamide product S3 (18.1, 85% yield). The compound was used directly in the next step without further purification.

[0148] !H NMR (600 MHz, CDCh) 88.00 (s, 2H), 7.96 (s, 1H), 6.68 (br s, 1H), 1.49 (s, 9H).

[0149] 13C NMR (151 MHz, CDCh) 5 167.6, 138.5, 131.6, 131.3, 128.1, 123.8, 123.6, 122.0, 62.2, 27.8.

[0150] 19F NMR (376 MHz, CDCh) 8 -629

[0151] HRMS (HESI) Exact mass calcd for C13H13F6NO2H [M+H]+, 330.0929. Found 330.0918.

[0152] V-(terM>utyl)-O-(l-phenylvinyl)-(3,5-bis-trifluoromethyl)-hydryoxyainide (1): To a large, dry round bottom flask with stir bar was added copper acetate (10.02 g, 55.2 mmol, 1 equiv.), sodium sulfate (31.3 g, 221 mmol, 4 equiv.), and hydroxamic acid S3 (18.16 g, 55.2 mmol, 1 equiv.). Mixture left open to ambient atmosphere; 1,2-dichloroethane added (600 mL, [0.076 M]) to make a slurry, mixture cooled to 0 °C. The flask was covered with aluminum foil, and hood lights turned off. Pyridine added (13.4 mL, 166 mmol, 3 equiv.), mixture let come to room temperature overnight. After 24 hours, 1,1-phenylvinylboronic acid (16.32 g, 110 mmol, 2 equiv.) was added, and the reaction was let stir at room temperature under ambient atmosphere, monitored by TLC until no more product being formed (~4 days). At end of reaction, the mixture was filtered through a pad of silica gel with dichloromethane to remove solid sodium sulfate and copper acetate. The filtrate was concentrated in vacuo, and further purified by silica gel column chromatography with 2% diethyl ether / hexanes (Rf ~ 0.5 in 5% EtzO / hexanes) to give product 1 as yellow solid (15.05 g, 63% yield).

[0153] The product was stored in freezer in the dark, but could be weighed out in the light on the benchtop for future use.

[0154] Note: when boronic acid added at beginning, reaction proceeded but a large amount of boronic-acid derived homodimer seen; pre-mixing and adding in boronic acid later reduced this byproduct and increased product yield.

[0155] ’H NMR (600 MHz, CDCh) 88.06 (s, 2H), 7.82 (s, 1H), 7.33 (m, 1H), 7.27 (m, 4H), 4.83 (d, 1H), 4.76 (d, 1H), 1.69 (s, 9H).

[0156] 13C NMR (151 MHz, CDCh) 169.4, 160.6, 138.2, 132.0, 131.3-130.6 (q, CF3), 129.4, 128.3, 127.3 (d), 125.6-120.2 (q), 125.1, 123.3 (p), 87.3, 64.2, 27.5.

[0157] 19F NMR (376 MHz, CDCh) 8 -63 0

[0158] HRMS (HESI) Exact mass calcd for C21H19F6NO2H [M+H]+, 432.1398. Found 432.1387.

[0159] Triketone trap synthesis.ODCCfe9) O OH O Ji DMAP (l eq) I! i Br. 1,+f ] - OH 1 L_ DCM [0.17 M] X 1—O \ 0 °C, 24 hr Ov\(1 eq)(1.5 eq)

[0160] 2-(6-bromohexanoyl)-5,5-dimethylcyclohexane-l, 3-dione (S4): Bromohexanoic acid (1 eq, 200 mg, 1.03 mmol), dimedone (1.5 eq, 216 mg, 1.54 mmol), and DMAP (1 eq, 125 mg, 1.03 mmol) were added to a flame dried flask. Anhydrous dichloromethane (0.35 M in bromohexanoic acid, half of total reaction volume) was added via syringe to the round bottom under inert atmosphere. The reaction mixture was cooled to 0 °C. A solution of DCC (1 eq, 212 mg, 1.03 mmol) was prepared in DCM (0.35 M, half of total reaction volume). The DCC solution was added dropwise to the cooled reaction mixture over 45 minutes. The reaction was warmed to room temperature overnight. After the reaction was complete, precipitate was filtered off and washed with DCM. The filtrate was collected and combined with 2 M aqueous HC1 in a separatory funnel. The aqueous phase was extracted 2x into DCM. Combined organic layers were washed with H2O.Finally, the organic layer was dried with MgSCh and concentrated via rotoevaporation. The product was isolated via flash column chromatography in EtOAc and hexanes from 0 to 10% EtOAc over 12 column volumes. Product was isolated in 72% yield. The reaction was scaled to 5 g of hexanoic acid with comparable yields.

[0161] ’H NMR (400 MHz, CDCh) 83.44 (t, 2H), 3.07 (m, 2H), 2.56 (s, 2H), 2.38 (s, 2H), 1.92 (dt, 2H), 1.67 (m, 2H), 1.55 (m, 2H), 1.10 (s, 6H).

[0162] 13C NMR (151 MHz, CDCh) 8205.2, 197.7, 195.2, 112.0, 52.6, 46.8, 40.1, 33.6, 32.5, 30.7, 28.2, 27,8. 23.7.

[0163] HRMS Exact mass calcd for Ci4H2iBrO3[M+Na]+, 339.06. Found 339.06.O OH „SNa Sreflux Acetone / H2O, 24 hr

[0164] N-(6-(2-hydroxy-4,4-dimethyl-6-oxocyclohex-l-en-l-yl)-6-oxohexyl) benzenesulfonothioate (2): To a solution of sodium thiosulfonate (1 eq, 1.5 g, 0.79 mmol) in Acetone:H2O 97:3 (0.3 M) is added 2-(6-bromohexanoyl)-5,5-dimethylcyclohexane-l, 3-dione (1 eq, 2.5 g, 0.79 mmol). Water was included to improve the solubility of the sodium thiosulfonate salt. The reaction mixture is refluxed overnight. After the reaction was complete, the mixture was diluted with H2O and extracted 2x into EtOAc. The organic phase is dried with MgSCE and concentrated via rotoevaporation. The product was isolated via flash column chromatography in EtOAc and hexanes from 0 to 20% EtOAc over 12 column volumes. Product was isolated in 69% yield. The reaction was scaled to 6 g with comparable yields.

[0165] 'H NMR (400 MHz, CDCh) 57.95 (m, 2H),7.60 (m, 3H), 3.02 (t, 2H), 3.00 (t, 2H), 2.55 (s, 2H), 2.36 (s, 2H), 1.54 (m, 6H), 1.09 (m, 6H).

[0166] 13C NMR (151 MHz, CDCh) 5205 1, 197.7, 195.2, 144.9, 133.6, 129.3, 127.0, 11.9, 52.6, 46.8, 40.0, 35.9, 30.7, 28.4, 28.2, 28.2, 23.8.

[0167] FT-IR (neat, ATR, cm1) 2955, 2867, 1654, 1553, 1448, 1433, 1404, 1315, 1295, 1285, 1285, 1235, 1195, 1175, 1137, 1078, 1078, 1020, 997, 948, 922, 885, 835, 819, 763, 748, 735, 718, 696, 684, 599, 548, 460.

[0168] HRMS Exact mass cal cd for C20H23O5S2 [M+Na]+, 434.11. Found 433.11.

[0169] Polymer Functionalization Synthesis and Characterization. Polymer functionalization. Functionalization of Polyolefins with Triketone.O JLN,tBu 1 n A [2 M] PhCI, 30 min, 130°C LLDPE o o

[0170] Triketone Functionalization of Polyolefins General Protocol: Polyolefin was placed in a vial with distilled and degassed chlorobenzene under inert atmosphere in a glove box. The mixture was heated at 130 °C for 5 minutes to solubilize the polymer. In a glovebox, amide reagent and triketone trap were dissolved in chlorobenzene and added to the polymer-solvent mixture. The vial was sealed with electrical tape, removed from the glovebox, and placed on a pie block to heat at 130 °C and stir. After the reaction was complete (30 min), the reaction mixture was taken up into a glass pipette and quickly precipitated into a 20 mL scintillation vial % full of stirring acetone. Excellent purity was achieved when acetone was stirring rapidly enough to create a vortex. Functionalized polymer was collected via vacuum filtration and dried overnight under vacuum before characterization.

[0171] Triketone functionalized LLDPE (Pl): LLDPE (40 mg, 1.4 mmol, 1 eq) was solubilized in PhCl (0.2 mL) at 130 °C before cooling to room temperature. Amide reagent (0.0025 eq) and triketone trap (0.005 eq) were dissolved in chlorobenzene (0.5 mL, [2 M] PhCl) and added to the mixture of polymer-solvent mixture before heating at 130 °C and stirring for 30 minutes. After the reaction was complete, the reaction mixture was precipitated into a scintillation vial of stirring acetone. Functionalized polymer was collected via vacuum filtration and dried overnight under vacuum before characterization.

[0172] Percent functionalization was determined through1H NMR. Peaks corresponding to polyolefin, from 0.8 - 1.8 ppm, were integrated to a total of 400 protons. The alpha protons to the thioether that appear between 3.1-3.2 ppm are used to determine mol% functionalization relative to repeat unit. As an average of 3 trials, functionalization was determined to be 0.1 mol%.

[0173] JH NMR (500 MHz, EtD2Cl4) 83.15 (t, 2H), 2.62 (m, 3H), 2.44 (s, 2H), 1.79 (m), 1.76 (m), 1.61 (m), 1.51(bs), 1.39 (bs), 1.18 (s, 6H), 1.01 (s). IR (neat, ATR, cm1) 2915, 2847, 1670, 1560, 1472, 1462, 730, 719. GPC (TCB, 140 °C): LLDPE Mn=21 kg / mol, D = 3.8, product Mn= kg / mol, D =. TGA (°C) LLDPE Td=428, product Td=282. DSC (°C): parent Tm= 125 with 41% crystallinity (DH = 122 J / g), product Tm= 123 with 37% crystallinity (DH = 110 J / g).

[0174] Triketone functionalized LLDPE (P2): LLDPE (40 mg, 1.4 mmol, 1 eq) was solubilized in PhCl (0.2 mL) at 130 °C before cooling to room temperature. Amide reagent (0.01 eq) and triketone trap (0.02 eq) were dissolved in chlorobenzene (0.5 mL, [2 M] PhCl) and added to the mixture of polymer-solvent mixture before heating at 130 °C and stirring for 30 minutes. After the reaction was complete, the reaction mixture was precipitated into a scintillation vial of stirringacetone. Functionalized polymer was collected via vacuum filtration and dried overnight under vacuum before characterization.

[0175] Percent functionalization was determined through1H NMR. Peaks corresponding to polyolefin, from 0.8 - 1.8 ppm, were integrated to a total of 400 protons. The alpha protons to the thioether that appear between 3.1-3.2 ppm are used to determine mol% functionalization relative to repeat unit. As an average of 3 trials, functionalization was determined to be 0.5 mol%.

[0176] ’H NMR (500 MHz, EtD2Cl4) 83.15 (t, 2H), 2.62 (m, 3H), 2.44 (s, 2H), 1.79 (m), 1.76 (m), 1.61 (m), 1.51(bs), 1.39 (bs), 1.18 (s, 6H), 1.01 (s). IR (neat, ATR, cm1) 2915, 2847, 1670, 1560, 1472, 1462, 1051, 730. GPC (TCB, 140 °C): LLDPE Mn=21 kg / mol, £> = 3.8, product Mn= 21 kg / mol, D = 4.05. TGA (°C) LLDPE Td= 428, product Td= 294. DSC (°C): parent Tm= 125 with 41% crystallinity (DH = 122 J / g), product Tm= 119 with 38% crystallinity (DH = 113 J / g).

[0177] Triketone functionalized LLDPE (P3): LLDPE (40 mg, 1.4 mmol, 1 eq) was solubilized in PhCl (0.2 mL) at 130 °C before cooling to room temperature. Amide reagent (0.02 eq) and triketone trap (0.04 eq) were dissolved in chlorobenzene (0.5 mL, [2 M] PhCl) and added to the mixture of polymer-solvent mixture before heating at 130 °C and stirring for 30 minutes. After the reaction was complete, the reaction mixture was precipitated into a scintillation vial of stirring acetone. Functionalized polymer was collected via vacuum filtration and dried overnight under vacuum before characterization.

[0178] Percent functionalization was determined through1H NMR. Peaks corresponding to polyolefin, from 0.8 - 1.8 ppm, were integrated to a total of 400 protons. The alpha protons to the thioether that appear between 3.1-3.2 ppm are used to determine mol% functionalization relative to repeat unit. As an average of 3 trials, functionalization was determined to be 1.0 mol%.

[0179] 'H NMR (500 MHz, EtDzCh) 83.15 (t, 2H), 2.62 (m, 3H), 2.44 (s, 2H), 1.79 (m), 1.76 (m), 1.61 (m), 1.51(bs), 1.39 (bs), 1.18 (s, 6H), 1.01 (s). IR (neat, ATR, cm1) 2915, 2848, 1670, 1560, 1427, 1463, 1143, 730. GPC (TCB, 140 °C): LLDPE Mn=21 kg / mol, £> = 3.8, product Mn= 27 kg / mol, £> = 4.6. TGA (°C) LLDPE Td= 428, product Td= 288. DSC (°C): parent Tm= 125 with 41% crystallinity (DH = 122 J / g), product Tm= 116 with 29% crystallinity (DH = 85 J / g).

[0180] Triketone functionalized LLDPE (P4): LLDPE (40 mg, 1.4 mmol, 1 eq) was solubilized in PhCl (0.2 mL) at 130 °C before cooling to room temperature. Amide reagent (0.05 eq) and triketone trap (0.1 eq) were dissolved in chlorobenzene (0.5 mL, [2 M] PhCl) and added to themixture of polymer-solvent mixture before heating at 130 °C and stirring for 30 minutes. After the reaction was complete, the reaction mixture was precipitated into a scintillation vial of stirring acetone. Functionalized polymer was collected via vacuum filtration and dried overnight under vacuum before characterization.

[0181] Percent functionalization was determined through1H NMR. Peaks corresponding to polyolefin, from 0.8 - 1.8 ppm, were integrated to a total of 400 protons. The alpha protons to the thioether that appear between 3.1-3.2 ppm are used to determine mol% functionalization relative to repeat unit. As an average of 3 trials, functionalization was determined to be 2.2 mol%.

[0182] ’H NMR (500 MHz, EtD Ch) 53.15 (t, 2H), 2.62 (m, 3H), 2.44 (s, 2H), 1.79 (m), 1.76 (m), 1.61 (m), 1.51(bs), 1.39 (bs), 1.18 (s, 6H), 1 01 (s) IR (neat, ATR, cm1) 2915, 2848, 1669, 1555, 1463, 1278, 1041, 730. GPC (TCB, 140 °C): LLDPE Mn=21 kg / mol, £> = 3.8, product Mn= 24 kg / mol, D = 5.9. TGA (°C) LLDPE Td= 428, product Td= 284. DSC (°C): parent Tm= 125 with 41% crystallinity (DH = 122 J / g), product Tm= 112 with 27% crystallinity (DH = 79 J / g).

[0183] Triketone functionalized LLDPE (P5): LLDPE (40 mg, 1.4 mmol, 1 eq) was solubilized in PhCl (0.2 mL) at 130 °C before cooling to room temperature. Amide reagent (0.1 eq) and triketone trap (0.2 eq) were dissolved in chlorobenzene (0.5 mL, [2 M] PhCl) and added to the mixture of polymer-solvent mixture before heating at 130 °C and stirring for 30 minutes. After the reaction was complete, the reaction mixture was precipitated into a scintillation vial of stirring acetone. Functionalized polymer was collected via vacuum fdtration and dried overnight under vacuum before characterization.

[0184] ’H NMR (500 MHz, EtDiCh) 8 17.83 (bs, 1H), 3.15 (t, 2H), 2.62 (m, 3H), 2.44 (s, 2H), 1.79 (m), 1.76 (m), 1.61 (m), 1.51(bs), 1.39 (bs), 1.18 (s, 6H), 1.01 (s). IR (neat, ATR, cm1) 2919, 2850, 1665, 1549, 1469, 1305, 1276, 1042, 719. GPC (TCB, 140 °C): LLDPE Mn=21 kg / mol, D = 3.8, product Mn= 24 kg / mol, D = 5.66. TGA (°C) LLDPE Td= 428, product Td= 270. DSC (°C): parent Tm= 125 with 41% crystallinity (DH = 122 J / g), product Tm= 112 with 21% crystallinity (DH = 62 J / g).

[0185] Percent functionalization was determined through1H NMR. Peaks corresponding to polyolefin, from 0.8 - 1.8 ppm, were integrated to a total of 400 protons. The alpha protons to the thioether that appear between 3.1-3.2 ppm are used to determine mol% functionalization relative to repeat unit. As an average of 3 trials, functionalization was determined to be 3.1 ± 0.1 mol%.Reagent Loading Functionalization Polymer name (repeat unit : amide : trap) (mol%)Pl 400:1:2 (.25 mol% target) 0.1P2 100:1:2 (1 mol% target) 0.5 ± 0.04P3 50: 1 :2 (2 mol% target) 1.0 ± 0.1P4 20: 1 :2 (5 mol% target) 2.2 ± 0.2P5 10: 1 :2 (10 mol% target) 3.1 ± 0.1

[0186] Table 1. Tuning functionalization (mol%) dictated by the stoichiometry of the reagents. Percent functionalization and standard deviation is reported as the average of three trials, as determined by NMR.

[0187] Triketone functionalized HDPE (P6): HDPE (40 mg, 1.4 mmol, 1 eq.) was solubilized in PhCl (0.4 mL) at 130 °C before cooling to room temperature. Amide reagent (0.1 eq) and triketone trap (0.2 eq) were dissolved in chlorobenzene (1.0 mL, [1 M] PhCl) and added to the mixture of polymer-solvent mixture before heating at 130 °C and stirring for 15 minutes. After the reaction was complete, the reaction mixture was precipitated into a scintillation vial of stirring acetone.Functionalized polymer was collected via vacuum filtration and dried overnight under vacuum before characterization.

[0188] NMR (500 MHz, C2D2CL, 110 °C) 8 17.88 (bs, 1H), 3.14 (bs, 2H), 2.62 (m, 3H), 2.45 (bs, 2H), 1.87 - 1.47 (m, 6H), 1.40 (m), 1.23 - 1.12 (m, 100H), 1.18 (bs, 6H), 1.01 (bs). IR(neat, ATR, cm1) 2916, 2848, 1667, 1559, 1463, 1388, 1309, 1278, 1181, 1141, 1040, 719, 572, 464.GPC (TCB, 140 °C): HOPE 32 kg / mol, £> = 3.3, product Mn= 39 kg / mol, £> = 4.0 . TGA (°C) HOPE Td= 433, product Td= 246. DSC (°C): HOPE Tm= 129 with 62% crystallinity (DH = 183 J / g), product Tm= 97 with 20% crystallinity (DH = 60 J / g).

[0189] Percent functionalization was determined through1H NMR. Peaks corresponding to polyolefin, from 0.8 - 1.8 ppm, were integrated to a total of 400 protons. The alpha protons to the thioether that appear between 3.1-3.2 ppm are used to determine mol % functionalization relative to repeat unit. Functionalization was determined to be 3.4 mol%.iPP (1 eq)

[0190] Triketone functionalized iPP (P7): iPP (40 mg, 0.95 mmol, 1 eq) was solubilized in PhCl (0.2 mb) at 130 °C before cooling to room temperature. Amide reagent (41 mg, 0.1 eq) and triketone trap (73 mg, 0.2 eq) were dissolved in chlorobenzene (0.5 mL, [1 M] PhCl) and added to the mixture of polymer-solvent mixture before heating at 130 °C and stirring for 30 minutes. After the reaction was complete, the reaction mixture was precipitated into a scintillation vial of stirring acetone. Functionalized polymer was collected via vacuum filtration and dried overnight under vacuum before characterization.

[0191] *H NMR (500 MHz, CzDzCh, 110 °C) 83.15 (bs, 2H), 32.65 (bs, 3H), 82.45 (bs, 2H), (bs) 1.93 - 0.73 (m). IR (neat, ATR, cm1) 2949, 2917, 2867, 2838, 1672, 1454, 1376, 1359, 1168, 998, 973, 899, 841, 808. GPC (TCB, 140 °C): iPP Mn=62 kg / mol, £> = 5.1, product Mn= 61 kg / mol, D = 6.5. TGA (°C) LLDPE Td= 241, product Td= 251. DSC (°C): parent Tm= 143 (DH = 77 J / g), product Tm= 153 (DH = 124 J / g).

[0192] Percent functionalization was determined through1H NMR. Peaks corresponding to polyolefin, from 0.8 - 1.8 ppm, were integrated to a total of 600 protons. The alpha protons to the thioether that appear between 3.1-3.2 ppm are used to determine mol % functionalization relative to repeat unit. Functionalization was determined to be 0.4 mol%.o

[0193] Triketone functionalized PCPE (P8): PCPE (40 mg, 1.4 mmol, 1 eq.) was solubilized in PhCl (0.4 mL) at 130 °C before cooling to room temperature. Amide reagent (0.1 eq) and triketone trap (0.2 eq) were dissolved in chlorobenzene (1.0 mL, [1 M] PhCl) and added to the mixture of polymer-solvent mixture before heating at 130 °C and stirring for 15 minutes. After the reaction was complete, the reaction mixture was precipitated into a scintillation vial of stirring acetone.Functionalized polymer was collected via vacuum fdtration and dried overnight under vacuum before characterization.

[0194] Reactive extrusion. Extruded triketone functionalized LLDPE (P13): LLDPE powder (1.0 g, 36 mmol, 1 eq) was mixed with amide reagent (0.77 g, 1.8 mmol, 0.05 eq) and triketone trap (1.5 g, 3.6 mmol, 0.1 eq) in a weigh-boat for extrusion. A 5 g Xplore twin-screw extruder fitted with a 2 g adaptor was purged with N2, the heat profile was set to 130 °C and the screws were turned at 75 rpm. The mixture of powders (2.5 g) were loaded into the extruder for 120 s. The material was mixed for 5 min before extruding into a filament. The crude material was dissolved and precipitated from chlorobenzene at 130 °C into acetone at room temperature, resulting in a 0.2 mol % functionalized white flakey solid.

[0195] XH NMR (500 MHz, C2D2CI4, 110 °C) 83.55 (bs, 2H), 3.05 (bs, 2H), 2.70 (bs, 1H), 1.68 (bs), 1.43 (bs), 1.01 (bs) ppm. IR (neat, ATR, cm1) 2915, 2848, 1672, 1472, 1462, 730, 719. GPC (TCB, 140 °C) LLDPE =21 kg / mol, D = 3.6; product Mn= 20 kg / mol, D =3.5. TGA (°C) parent Td =428 °C, product 7d=396 °C. DSC (°C) parent Tm= 125 with 41% crystallinity (DH = 122 J / g), product 7,ri=124 °C, with 26% crystallinity (DH= 77 J / g).

[0196] Reactivity of Triketone Functionalized Polymers with Amines. Amine PostFunctionalization of Polyolefins General Protocol: Triketone functionalized polyolefin was placed in a vial with distilled and degassed chlorobenzene under inert atmosphere in a glove box. The mixture was heated at 130 °C for 5 minutes to solubilize the polymer. In a glovebox, amine andadditional chlorobenzene were added to the polymer-solvent mixture. The vial was sealed with electrical tape, removed from the glovebox, and placed in a pie block to heat at 130 °C and stir. After the reaction was complete, the reaction mixture was taken up into a 2 mL glass Pasteur pipette and quickly precipitated into a scintillation vial % full of stirring acetone. Excellent purity was achieved when acetone was stirring rapidly enough to create a vortex. Post-functionalized polymer was collected via vacuum filtration and dried overnight under vacuum.triketone functionalizedLLDPE

[0197] Ene-hexylamine functionalized LLDPE (P9): 2 mol % triketone functionalized LLDPE (40 mg, 1.4 mmol) was solubilized in PhCl (0.2 mL) at 130 °C before cooling to room temperature. Hexylamine (100 eq relative to triketone, 170 uL) and PhCl were added (0.5 mL) before heating at 130 °C and stirring for 10 minutes under inert atmosphere. After the reaction was complete, the reaction mixture was precipitated into a scintillation vial of stirring acetone. Functionalized polymer was collected via vacuum filtration and dried overnight under vacuum before characterization.

[0198] XH NMR (500 MHz, C2D2CI4, 110 °C) ’H NMR (500 MHz, EtCl4) 8 13.48 (bs), 3.49 (bs) 2.63 (bs), 1.91 - 0.89 (m). IR (neat, ATR, cm1) 2916, 2849, 1640, 1572, 1464, 1366, 1335, 1278, 1140, 897, 719, 628, 569, 465. GPC (TCB, 140 °C): Starting material (Pl) Mn= 24 kg / mol, D = 5.66; Mn= 18 kg / mol, £> = 4.1. TGA (°C) LLDPE Td= 428, product Td= 255. DSC (°C): parent Tm= 125 with 41% crystallinity (DH = 122 J / g), product Tm= 94 with 10% crystallinity (DH = 29 J / g).

[0199] Full conversion from triketone to hexyldiketoenamine functionalized polymer was monitored via the disappearance of the enol proton from 17- 18 ppm and the appearance of the enamine proton form 13- 14 ppm.ene-hexylamine functionalizedLLDPE

[0200] Ene-benzylamine functionalized LLDPE (P10): 2 mol% ene-hexylamine functionalized LLDPE (40 mg, 1.4 mmol) was solubilized in PhCl (0.2 mL) at 130 °C before cooling to room temperature. Benzylamine (100 eq relative to triketone, 140 uL) and PhCl were added (0.5 mL) before heating at 130 °C and stirring for 10 minutes under inert atmosphere. After the reaction was complete, the reaction mixture was precipitated into a scintillation vial of stirring acetone.Functionalized polymer was collected via vacuum filtration and dried overnight under vacuum before characterization.

[0201] ’H NMR (500 MHz, C2D2CL, 110 °C) 8 13.80 (s) 7.54 - 7.32 (m), 4.70 (s), 3.18 (s), 2.61 (bs), 2.46 (s), 1.40 (m), 1.14 (s). IR(neat, ATR, cm1) 2917, 2849, 1641, 1568, 1497, 1467, 1366, 1335, 1278, 1139, 1030, 897, 719, 696, 628, 569, 463. GPC (TCB, 140 °C): Starting material (P5) Mn= 18 kg / mol, £> = 4.1; Mn= 19 kg / mol, D = 2.4.TGA (°C) LLDPE Td= 428, product Td= 248.DSC (°C): parent Tm= 125 with 41% crystallinity (DH = 122 J / g), product Tm= 99 with 12% crystallinity (DH = 36 J / g).

[0202] Full conversion from hexyldiketoenamine to benzyldiktoenamine was monitored via the disappearance of the aliphatic alpha to nitrogen protons at 3.49 ppm and the appearance benzylic protons at 4.70 ppm.(100 eq)[2 M] PhCl, 10 min, 130 °Ctriketone functionalizedHDPE

[0203] Ene-hexylamine functionalized HDPE (Pll): 3 mol% triketone functionalized HDPE (40 mg, 1.4 mmol) was solubilized in PhCl (0.2 mL) at 130 °C before cooling to room temperature. Hexylamine (100 eq relative to triketone, 170 uL) and PhCl were added (0.5 mL) before heating at 130 °C and stirring for 10 minutes under inert atmosphere. After the reaction was complete, the reaction mixture was precipitated into a scintillation vial of stirring acetone. Functionalized polymer was collected via vacuum filtration and dried overnight under vacuum before characterization.

[0204] XH NMR (500 MHz, C2D2CL, 110 °C) 5 13.47 (s), 3.47 (s), 3.10 (s), 2.61 (m), 2,44 (s), 1.80-1.34 (m), 1.14 (s). IR (neat, ATR, cm1) 2916, 2848, 1640, 1572, 1464, 1368, 1335, 1278, 1139, 898, 719, 626, 570, 465. GPC (TCB, 140 °C): Starting material (P3) Mn=39 kg / mol, £> =4.0; product Mn= 19 kg / mol, D = 4.4. TGA (°C) HDPE Td= 433 , product Td= 246. DSC (°C): HDPE Tm= 129 with 62% crystallinity (DH = 183 J / g), product Tm= 95 with 17% crystallinity (DH = 50 J / g).

[0205] Full conversion from triketone to hexyldiketoenamine functionalized polymer was monitored via the disappearance of the enol proton from 17-18 ppm and the appearance of the enamine proton form 13-14 ppm.

[0206] Ene-hexylamine functionalized iPP (P12): 0.4 mol% triketone functionalized iPP (40 mg, 1.4 mmol) was solubilized in PhCl (0.2 mL) at 130 °C before cooling to room temperature. Hexylamine (100 eq relative to triketone, 170 uL) and PhCl were added (0.5 mL) before heating at 130 °C and stirring for 10 minutes under inert atmosphere. After the reaction was complete, the reaction mixture was precipitated into a scintillation vial of stirring acetone. Functionalized polymer was collected via vacuum filtration and dried overnight under vacuum before characterization.

[0207] ’H NMR (500 MHz, C2D2CL, 110 °C) 53.49 (bs, 2H), 3.12 (bs, 2H), 2.45 (bs, ), 2.19 (bs, 4H), 1.41 (bs), 1.02 (bs). IR (neat, ATR, cm1) 2917, 2850, 1472, 1374, 1279, 1169, 1140, 1087,1069, 1000, 864, 750, 719. GPC (TCB, 140 °C): Starting material (P4) Mn=61 kg / mol, £> =6.5; product Mn= 55 kg / mol, D = 5.4. TGA (°C) parent Td= 428, product Td= 294. DSC (°C): parent Tm= 125 with 41% crystallinity (DH = 122 J / g), product Tm= 112 with 30% crystallinity (DH = 86 J / g).

[0208] Full conversion from triketone to hexyldiketoenamine functionalized polymer was monitored via the appearance of the alpha to nitrogen proton near 3.5 ppm.

[0209] Diketoenamine crosslinked LLDPE synthesis. MultiAmine Post-Functionalization Crosslinking of Polyolefins General Protocol: Triketone functionalized polyolefin was placed in a vial with distilled and degassed chlorobenzene under inert atmosphere in a glove box. The mixture was heated at 130 °C for 5 minutes to solubilize the polymer. In a glovebox, multiamine and additional chlorobenzene were added to the polymer-solvent mixture. The vial was sealed with electrical tape, removed from the glovebox, and stirred at room temperature for 2 minutes to achieve good mixing of amine and polyolefin. Next, the reaction was stirred and heated on a pie block at 130 °C to react for 12 minutes. After the reaction was complete, the gel was removed from the vial and placed into a scintillation vial % full of stirring acetone. The remaining chlorobenzene solution was added to the vial of stirring acetone. Crosslinked polymer was collected via vacuum filtration and dried overnight under vacuum before characterization.

[0210] Diketoenamine Crosslinked LLDPE (DCPN-P1): 0.1 mol% triketone functionalized LLDPE (Pl) (40 mg, 1.4 mmol) was solubilized in PhCl (0.35 mL) at 130 °C before cooling to room temperature. TR.EN was added from a stock solution (0.3 eq relative to triketone, 0.05 uL) followed by the addition of PhCl (0.35 mL). The reaction was stirred for 2 minutes at room temperature before stirring and heating at 130 °C for 12 minutes under inert atmosphere. After the reaction was complete, the reaction mixture was precipitated into a scintillation vial of stirringacetone. Crosslinked polymer was collected via vacuum filtration and dried overnight under vacuum before characterization.

[0211] The product could not be characterized by1H NMR or GPC as crosslinks result in an insoluble material. IR (neat, ATR, cm1) 2915, 2847, 1730, 1577, 1472, 1462, 1261, 1095, 803, 730, 719. TGA (°C) parent Td= 428, product Td=319. DSC (°C): parent Tm= 125 with 41% crystallinity (DH = 122 J / g), product Tm= 124 with 37% crystallinity (DH = 109 J / g).

[0212] Diketoenamine Crosslinked LLDPE (DCPN-P2): 0.5 mol% triketone functionalized LLDPE (P2) (40 mg, 1.4 mmol) was solubilized in PhCl (0.35 mL) at 130 °C before cooling to room temperature. TREN was added from a stock solution (0.3 eq relative to triketone, 0.26 uL) followed by the addition of PhCl (0.35 mL). The reaction was stirred for 2 minutes at room temperature before stirring and heating at 130 °C for 12 minutes under inert atmosphere. After the reaction was complete, the reaction mixture was precipitated into a scintillation vial of stirring acetone. Crosslinked polymer was collected via vacuum filtration and dried overnight under vacuum before characterization.

[0213] The product could not be characterized by!H NMR or GPC as crosslinks result in an insoluble material. IR (neat, ATR, cm *) 2919, 2847, 1636, 1596, 1464, 1370, 1309, 1278, 1262, 1140, 1039, 804, 719, 668. TGA (°C) parent Td= 428, product Td= 309. DSC (°C): parent Tm= 125 with 41% crystallinity (DH = 122 J / g), product Tm= 118 with 39% crystallinity (DH = 113 J / g).

[0214] Following the Multi Amine Post-Functionalization Crosslinking of Polyolefins General Protocol, equivalents of TREN crosslinker were varied between 0 and 2 equivalents of reactive amine to triketone appended to polyolefin. Resultant vitrimer was precipitated and rinsed in acetone.

[0215] Diketoenamine Crosslinked LLDPE (DCPN-P4): 2.2 mol% triketone functionalized LLDPE (P4) (40 mg, 1.4 mmol) was solubilized in PhCl (0.35 mL) at 130 °C before cooling to room temperature. TREN was added from a stock solution (0.3 eq relative to triketone) followed by the addition of PhCl (0.35 mL). The reaction was stirred for 2 minutes at room temperature before stirring and heating at 130 °C for 12 minutes under inert atmosphere. After the reaction was complete, the reaction mixture was precipitated into a scintillation vial of stirring acetone.Crosslinked polymer was collected via vacuum filtration and dried overnight under vacuum before characterization.

[0216] The product could not be characterized byJH NMR or GPC as crosslinks result in an insoluble material. IR (neat, ATR, cm1) 2919, 2847, 1636, 1596, 1464, 1370, 1309, 1278, 1262, 1140, 1039, 804, 719, 668. TGA (°C) parent Td= 428, product Td=248. DSC (°C): parent Tm= 125 with 41% crystallinity (DH = 122 J / g), product Tm= 115 with 22% crystallinity (DH = 64 J / g).

[0217] Differential Scanning Calorimetry Thermograms were obtained.

[0218] Gel Permeation Chromatography Chromatograms. Polyolefin gel permeation chromatography (GPC) was obtained using a Tosoh EcoSEC-HT (high temperature) GPC with refractive index detection against polystyrene standards in 2 mg / mL solutions of trichlorobenzene (TCB) with 200 ppm BHT at 140 °C.

[0219] Amine exchange experiments. Soxhlet extraction. Soxhlet extraction general procedure: The gel content of DCPN-P2 was determined through Soxhlet extraction. A vitrimer sample of approximately 75 mg was placed in teabag and subsequently placed in the Soxhlet extraction apparatus in chlorobenzene 20 mL. Soxhlet extraction was carried out at 150 °C for 6 hours after finding that additional 6 hour periods did not significantly alter the gel fraction. The teabag was then removed from the apparatus, rinsed with acetone and dried on highvac overnight. Teabags were opened and the remaining mass of network was massed. Gel content was calculated as the ratio of final mass to initial mass. Control experiments were conducted on 75 mg LLDPE. The Soxhlet extractions resulted in gel fractions of 0.

[0220] Permanent crosslinking experiment: To understand whether gel fractions were due to permanent or dynamic covalent crosslinks, cleavage of the dynamic bonds was performed using the Soxhlet extraction general procedure, but this time adding 1 mL hexylamine to 20 mL of PhCl before refluxing for 6 hours. DCPN-P2 with a gel content of 85% without the presence of hexylamine showed a gel content of 0% in the presence of hexylamine.

[0221] A characteristic FT-IR Spectrum is depicted in FIG. 20.

[0222] Characterization of reaction byproducts. To determine reaction byproducts of C-H functionalization reactions, the filtrate from the synthesis of P4 (40 mg scale with respect to polymer substrate) was collected and evaporated. Byproducts were separated by flash column chromatography from 0 to 60% EtOAc in hexanes over 20 column volumes. The first spot was identified as bis-CF3 amide, the byproduct of amidyl radical mediated hydrogen atom transfer. The second spot was identified as cz / ?Aa-sulfone phenyl ketone, a byproduct of chain transfer, whichsupports a radical chain mechanism. The third isolated product was identified as unreacted thiosulfonate radical trap.

[0223] FIG. 57 provides a proton nuclear magnetic resonance spectrum for l-phenyl-2-(phenylsulfonyl)ethan-l-one. FIG. 58 provides a proton nuclear magnetic resonance spectrum for an example O-alkenylhydroxamate. FIG. 59 provides a proton nuclear magnetic resonance spectrum for an example thiosulfonate functionalized triketone.

[0224] Scattering. Resonant soft angle X-ray scattering (RSoXS) Sample preparation:Fabrication of thin film samples on X-ray transparent windows: 10 mg of P2 was dissolved in 1 mL of 1,2 di chlorobenzene and heated to 130 °C for dissolution with gentle stirring. 10 mg of TREN was dissolved in 1 mL of 1,2 di chlorobenzene using a vortex mixer. To make DCPN-P2 with various amine to triketone ratios, corresponding volumes of 1 wt.% TREN solution was pipetted to the 1 wt.% P2 solution and kept heated with gentle stirring. For R — NEE to triketone ratios of 2, 1.3, 0.9, 0.5 and 0.3, 17.6 pL, 11.44 pL, 7.92 pL, 4.4 pL, and 2.64 pL of 1 wt.% TREN solution was used.

[0225] For spin coating of the mixture solution, a PSS coated silicon substrate was prepared by spin coating a diluted 20 wt.% PSS aqueous solution on a 100mm diameter silicon wafer with spin rate of 3000 rpm using a SCS 6800 Spin Coater. The coated wafer was sliced into squares of 10 x 10 mm to serve as substrate for the spin coating of DCPN-P2. Solutions of P2 with various amine to triketone ratios was kept heated at 140 °C and 20 pL of each solution was dropped onto the PSS coated substrate while the substrate is spinning at 3000 rpm. Because the solvent 1,2di chlorobenzene does not evaporate quickly, the spinning substrate was stopped 3 seconds after dropping the DCPN-P2 solutions and transferred to a hotplate preheated to 100 °C for the evaporation of residual solvent for 30 seconds. After cooling down, the polymer film was floated on DI water by spontaneous dissolution of the intermediate PSS layer. The floating polymer film was then transferred onto the SiNx windows and annealed at 100 °C for 1 hour and kept at ambient conditions prior to testing.

[0226] Near Edge X-ray Absorption Fine Structure (NEXAFS). NEXAFS was caried out at the Advanced Light Source Beamline 11.0.1.2. The dry thin film samples on SiNx windows were directly mounted on the sample holder for characterization and the data were collected using a photodiode detector in transmission mode. The X-ray energies span from 280 - 300 eV for Carbon K edge and 520 - 550 eV for Oxygen K edge.

[0227] Resonant Soft X-ray Scattering (RSoXS). RSoXS was caried out in the same configuration as the NEXAFS characterization except for switching the detector from photodiode to Charge-coupled Device (CCD). The 2-D Small Angle X-ray Scattering patterns were analyzed using the X-ray Analysis Tools developed by Collins Research Group at Washington State University and ploted as 1-D RSoXS spectra.

[0228] GIWAXS. Sample Preparation: Briefly, 10 mg of P2 was dissolved in 1 mb of 1,2 di chlorobenzene and heated to 130 °C for dissolution with gentle stirring. 10 mg of TREN was dissolved in 1 mb of 1,2 dichlorobenzene using a vortex mixer. To make DCPN-P2 with various amine to triketone ratios, corresponding volumes of 1 wt.% TREN solution was pipetted to the 1 wt.% Pl-0.5 solution and kept heated with gentle stirring. For NH2 to triketone ratios of 2, 1.3, 0.9, 0.5 and 0.3, 17.6 pL, 11.44 pL, 7.92 pL, 4.4 pL, and 2.64 pL of 1 wt.% TREN solution was used.

[0229] For spin coating of the mixture solution, a PSS coated silicon substrate was prepared by spin coating a diluted 20 wt.% PSS aqueous solution on a 100mm diameter silicon wafer with spin rate of 3000 rpm using a SCS 6800 Spin Coater. The coated wafer was sliced into squares of 10 x 10 mm to serve as substrate for the spin coating of DCPN-P2. After cooling down, the polymer film was floated on DI water by spontaneous dissolution of the intermediate PSS layer. The floating polymer film was then transferred onto clean Si wafer and annealed at 100 °C for 1 hour and kept at ambient conditions prior to testing.

[0230] FIG. 25 shows ID GWAXS spectra in the in-plane (left) and out of plane direction (right). FIG. 26 provides a comparison of DSC and WAXS determination of percent crystallinity. FIG. 27 provides WAXS profiles. From these data, crystallite thickness (Luo), calculated from the Scherrer equation, describes the size of the ordered phase, and followed a similar trend. Pristine LLDPE possessed a Luo of 20.6 nm, which decreased to 15.5 nm for the 2.2 mol% functionalized material DCPN-P4

[0231] Data Collection. Materials Testing. Films were melt pressed at 200 °C 2 hours under 1 ton of force. Resultant films were cut into discs (diameter = 8 mm). Samples were measured in ARES G2 rheometer equipped with a temperature probe and tested under ambient atmosphere.

[0232] Frequency and Strain Sweeps. Frequency sweep: Oscillatory frequency sweeps were conducted in an ARES G2 rheometer. Diketoenamine crosslinked LLDPE (DCPN-P2) with 0.9 amine to triketone ratio was melt pressed into 200-300 um films at 200 °C. The polymer film was cut into 8 mm discs with a biopsy punch and loaded onto the rheometer between 8-mm stainlesssteel parallel plate. Frequency sweeps were conducted from 0.1 to 1000 1 / s and under constant strain of 2% to determine the linear viscoelastic regime. Testing was conducted at 160 °C to characterize melt rheology significantly above the melt temperature.

[0233] Strain sweep: Oscillatory strain sweeps were conducted in an ARES G2 rheometer.

[0234] Diketoenamine crosslinked LLDPE (DCPN-P2) with 0.9 amine was melt pressed into 200-300 um films at 200 °C. The polymer film was cut into 8 mm discs with a biopsy punch and loaded onto the rheometer between 8-mm stainless steel parallel plate. A strain sweep from 0.1 to 100% strain with a constant frequency of 1 Hz was conducted to determine the linear viscoelastic regime. Testing was conducted at 160 °C to characterize melt rheology significantly above the melt temperature of polyethylene.

[0235] Stress Relaxation. Stress relaxation was conducted in an ARES G2 rheometer under a step strain of 2%. Testing was conducted at 170 °C, 180 °C, 190 °C and 200 °C, 210 °C, and 220 °C significantly above melt temperature of the vitrimer (110 ° C). Experiments ran for 2 hours - 10 hours depending upon temperature. A constant axial force of 2N was maintained throughout testing. Of note, these experiments can alternatively be conducted in a DMA setup. To validate the experimental results, stress relaxation was also measured on a TA DHR-2 rheometer.

[0236] Creep. Creep measurements were carried out using a TA DHR-2 rheometer. LLDPE and Diketoenamine crosslinked LLDPE (P13) with 0.9 amine to triketone ratio were melt pressed into 200-300 um films. The polymer film was cut into 8 mm discs with a biopsy punch and loaded onto the rheometer between 8 mm stainless steel parallel plates. Creep measurements at the 30, 60, 90 and 120 °C were carried out with a constant IkPa stress for 1000 s.

[0237] DYNAMIC MECHANICAL THERMAL ANALYSIS (DMT A). DMT A was performed in a TA RSA G2k DMA. Samples were prepared by cutting melt pressed samples into rectangular strips 2mm width x 12 mm length. Samples were put under oscillatory strain of 2% as temperature was increased from 25 °C to 200 °C at a rate of 10 °C / min. Storage modulus (E’) was recorded as a function of temperature.

[0238] Tensile testing. Melt pressed samples were cut into dog-bones using an ISO 527 Type 5B cutting die to standard dimensions (12mm bridge length and 2mm bridge width). Sample thickness at the bridge was measured using calipers. Test specimens were affixed to the TA RSA G2k DMA with a starting gap of 18mm for consistent pulls. Samples were pulled at 0.09 mm / s (0.005 s'1)which falls within the linear viscoelastic region. This regime was determined by rheological frequency sweeps and tensile pulls at multiple strain rates. Tensile experiments were conducted at room temperature in triplicate. Average values and standard deviations are reported.

[0239] Reprocessing. Sample preparation. Polymer fdms were reprocessed by cutting fdms into small pieces. On a steel plate was placed aKapton film (Kapton KN .01”) (pre-treated with Frekote 770-NC) A brass shim stencil was placed to control film thickness before adding polymer. Another Kapton film was placed on top followed by a second steel plate. The setup was then heated at 200 °C for 2 minutes before pressing at 1000 psi for 2 hours. Films were removed from the melt press and cooled to room temperature by rapid heat transfer to an aluminum surface. Reprocessed samples were subsequently characterized.

[0240] Dynamic Mechanical Thermal Analysis (DMTA). DMTA was performed in a TA RSA G2k DMA. Samples were prepared by cutting melt pressed samples into rectangular strips 2mm width x 12 mm length. Samples were put under oscillatory strain of 2% as temperature was increased from 25 °C to 200 °C at a rate of 10 °C / min. Storage modulus (E’) was recorded as a function of temperature.

[0241] Tensile testing. Reprocessed samples were cut into dog-bones using an ISO 527 Type 5B cutting die to standard dimensions (12mm bridge length and 2mm bridge width). Sample thickness at the bridge was measured using calipers. Test specimens were affixed to the TA RSA G2k DMA with a starting gap of 18mm for consistent pulls. Samples were pulled at 0.09 mm / s which falls within the linear viscoelastic region. This regime was determined by rheological frequency sweeps. Tensile experiments were conducted at room temperature in triplicate. Average values and standard deviations are reported.

[0242] Permanent crosslinking experiment. To understand whether gel fractions were due permanent or dynamic covalent crosslinks, cleavage of the dynamic bonds was performed using the Soxhlet extraction general procedure, but this time adding 1 mL hexylamine to 20 mL of PhCl. 75 mg of polymer was used in all experiments.

[0243] NMRs of functionalized polymers and small molecules S4, 2, Pl, P2, P3, P4, P5, P6, P7, P8, P9, P10, Pll, and P12, extruded polymer P13 and an alcohol functionalized polymer were obtained and are shown in FIGS. 39-56.

[0244] Figure Captions for Example 1 :

[0245] FIG. 3 : C-H functionalization of polyolefins to access dynamic networks. Panel A:Upcy cling to dynamic polyolefin networks is a desirable but understudied approach. Panel B:Amidyl radical mediated C-H functionalization has advantages compared to peroxide mediated C-H functionalization. Panel C: Diketoeneamine dynamic covalent polyolefin networks (DCPNs) through selective C-H functionalization to access reprocessable polyolefin thermosets.

[0246] FIG. 4 : C-H functionalization of commodity polyolefins to yield DCPNs. Panel A: Reaction scheme for C-H functionalization to provide DCPNs; Panel B: Results demonstrating the ability to tune functionalization density (P1-P5) and polymer substrate (P6-P8); *indicates these were substrates for the synthesis of DCPNs; Panel C: Size-exclusion chromatography (SEC) chromatographs of triketone functionalized LLDPE compared to LLDPE demonstrate minimal change in molecular weight distribution and £>. Panel D: Gel fraction of 0.5 mol% functionalized diketoenamine crosslinked LLDPE (DCPN-P2) when varying the ratio of crosslinker to triketone. Gel fraction is calculated gravimetrically by comparing the mass of polymer before and after Soxhlet extraction.amol% refers to mol% compared to polymer repeat unitbFunctionalization mol% calculated by integration of1H NMR relative to aliphatic polyolefin protons;and D values calculated from RI detection in 1,2,4 trichlorobenzene at 140 °C. LLDPE (Mn= 21 kg mol-1£>=3.8), HOPE (Mn= 16 kg mol'1£>=18.0), iPP ( = 62 kg mol'1£>=5.1), PCPE ( = 23 kg mol'1£>=7.6).

[0247] FIG. 5 : Structural characterization of the diketoenamine dynamically crosslinked polyolefin (DCPN). Panel A: The WAXS profiles indicate scattering that corresponds to polyethylene chain packing into crystallites for LLDPE, 0.5 mol% functionalized LLDPE (P2) and the resultant DCPN (DCPN-P2). Panel B: Comparison of crystallinity (%) for 0.1, 0.5, 2.2 mol% functionalized LLDPE and the resultant DCPN shows decreases in crystallinity as functionalization increases determined by WAXS. Panel C: Proposed DCPN macrostructure is comprised of crystalline, amorphous, and crosslink-rich domains. Panel D: Diketoenamine-rich domains in DCPN-P2 were characterized by RSoXS as the number of equivalents of R — NH2 relative to triketone were increased from 0 to 1.3. Panel E: The crystallinity of DCPN-P2 was characterized by GIWAXS as the number of equivalents of R — NH2 relative to triketone were increased from 0 to 1.3.

[0248] FIG. 6 : The diketoenamine DCPN demonstrated attractive mechanical properties. Panel A: Uniaxial tensile experiments demonstrated the enhanced mechanical properties of diketoenamine DCPN-P1 and DCPN-P2. Representative stress-strain curves are shown and quantitation ofreplicate experiments are in shown in Figure S28 (strain rate = 0.005 s '); Panel B: Stress relaxation experiments at elevated temperatures demonstrate dissipation of stress over time enabled by dynamic covalent bond exchange. Panel C: Resistance to deformation increases in the diketoenamine DCPN-P2 compared to LLDPE in creep experiments; Panel C: DCPN-P2 was reprocessed three times and oscillatory temperature sweeps with a constant strain of 2% and a constant frequency of 1 Hz indicate little cycle-to-cycle property fade.

[0249] FIG. 7: Melting endotherm of functionalized LLDPEs in comparison to LLDPE. Data obtained from the 2ndheating cycle at a heating rate of 10 °C / min. Functionalization with 3 mol% triketone (P5) results in decreases in crystallinity % and melt temperature. Formation of the hexyldiketoenamine (P9) results in further decreases in crystallinity. Exchange of amine to the benzyldiketoenamine (P10) results in similar crystallinity to P5.

[0250] FIG. 8: Melting endotherm of functionalized LLDPE in comparison to various mol% functionalization triketone LLDPE. Data obtained from the 2ndheating cycle at a heating rate of 10 °C / min. As percent functionalization with triketone is increased from 0.5 mol% (P2) to 3 mol% (P5), both magnitude of the endotherm and melt temperature decrease.

[0251] FIG. 9: Melting endotherm of functionalized HDPE in comparison to HDPE. Data obtained from the 2ndheating cycle at a heating rate of 10 °C / min; the melting temperature and enthalpy of HDPE and functionalized HDPEs were analyzed. Functionalization with 3 mol% triketone (P6) results in decreases in crystallinity % and melt temperature. Formation of the hexyldiketoenamine (P11) results in further decreases in crystallinity.

[0252] FIG. 10: Melting endotherm of functionalized z-PP in comparison to iPP. Data obtained from the 2ndheating cycle at a heating rate of 10 °C / min. Both functionalization with 0.4 mol% triketone (P7) and hexyldiketoenamine (P12) result in slight decreases in crystallinity % and melt temperature compared to z-PP.

[0253] FIG. 11: Melting endotherm of functionalized and crosslinked LLDPEs in comparison to LLDPE. Data obtained from the 2ndheating cycle at a heating rate of 10 °C / min. Functionalization with 2.2 mol% triketone (P4) results in decreases in crystallinity % and melt temperature.Crosslinking with TREN to form DCPN-P4 results in further broadening of and decrease in melt temperatures.

[0254] FIG. 12: Melting endotherm of functionalized and crosslinked LLDPEs in comparison to LLDPE. Data obtained from the 2ndheating cycle at a heating rate of 10 °C / min. Functionalization with 0.5 mol% triketone (P2) results in decreases in crystallinity % and melt temperature.Crosslinking with TREN to form DCPN-P2 results in further broadening of and decrease in melt temperatures.

[0255] FIG. 13: Triketone group transfer using reagent 1 and trap 2 successfully incorporated triketone groups into the polymer scaffold of LLDPE. Triketone functionalized polymers tended to elute at shorter retention times relative to LLDPE. Changes to D appear to be small indicating limited chain coupling or scission events.

[0256] FIG. 14: Triketone group transfer using reagent 1 and trap 2 successfully incorporated triketone groups into the polymer scaffold of LLDPE. 3.1 mol% triketone functionalized polymer (P5), eluted at shorter retention times. We hypothesized that this might be due to aggregation as triketones are known to form strong hydrogen bonding interactions. Upon formation of the hexylenamine functionalized polymer (P9), Mnand D returned to values very similar to that of LLDPE suggesting that changes in MWD were likely not due to deleterious chain coupling events.

[0257] FIG. 15: Triketone group transfer using reagent 1 and trap 2 successfully enabled triketone group transfer. Triketone functionalized polymer (P6), eluted at shorter retention times. Upon formation of the hexylenamine functionalized polymer (Pll), Mnand D returned to a monomodal distribution and longer retention times.

[0258] FIG. 16: Triketone group transfer using reagent 1 and trap 2 successfully incorporated triketone groups into the polymer scaffold of iPP without significantly altering the molecular weight distribution according to GPC.

[0259] FIG. 17A: Triketone group transfer using reagent 1 and trap 2 successfully incorporated triketone groups into the polymer scaffold of post-consumer polyethylene (PCPE).

[0260] FIG. 17B Triketone group transfer using reagent 1 and trap 2 successfully incorporated triketone groups into the polymer scaffold of LLPDE in an extruder without significantly altering the molecular weight distribution according to GPC.

[0261] FIG. 18: Condensation hexylamine with P5 to form P9 indicates that triketone bound polyolefins readily condenses with amines. The hexylamine was displaced by 100 eq ofbenzylenamine to form benzyldiketoenamine indicating that polymer bound diketoenamines are capable of bond exchange.

[0262] FIG. 19: Ratio of reactive amine (R — NH2 , 3 per equivalent of TREN) was varied between 0 and 2 equivalents relative to equivalents of triketone bound to P2 to understand the impact on gel fraction. It was observed that as equivalents were increased, from 0 to 1, gel fraction increased, indicating a greater degree of network connectivity. From 1 to 2 equivalents of amine relative to triketone, gel fractions decreased. Comparing the slopes of the 0 to 1 regime to the 1 to 2 regime, the slope of the first regime was greater than that of the second.

[0263] FIG. 20: Characteristic FT-IR spectra of triketone functionalized and diketoenamine polymers. 0.5 mol% triketone modified LLDPE (P2) and 3 mol% triketone modified LLDPE (P5) show the same characteristic vibrational modes, with P5 displaying greater intensity relative to C-H stretches indicating greater degrees of functionalization. 3 mol% hexylenamine LLDPE functionalized LLDPE (P9) and 0.5 mol% diketoenamine crosslinked LLDPE (DCPN-P2) show very similar vibration modes, lending support for the formation of diketoenamine in the DCPN.

[0264] FIG. 21: NEXAFX spectra at the Carbon K edge (left) and Oxygen K edge (right). Peaks corresponding to the Oxygen K edge structures were identified at 537 eV and used to evaluate 1-D RSoXS spectra for presence of oxygen rich aggregates within the films. Peaks corresponding to the Carbon K edge structures were identified at 287 eV and used to evaluate 1-D RSoXS spectra for presence of carbon rich domains.

[0265] FIG. 22: 1-D RSoXS spectra corresponding to Oxygen K edge structures. The plots from left to right are respectively collected from LLDPE, P2, and DCPN-P2 with amine to triketone equivalence of 0, 0.5, 0.9, 1.3, and LLDPE.

[0266] FIG. 23: 1-D RSoXS spectra corresponding to Carbon K edge structures. The plots from left to right are respectively collected from LLDPE, P2, and DCPN-P2 with amine to triketone equivalence of 0, 0.5, 0.9, 1.3, and LLDPE.

[0267] FIG. 24: 2-D GIWAXS patterns for collected from LLDPE, P2, and DCPN-P2 with amine to triketone equivalence of 0.3, 0.5, 0.9, 1.3, 2.

[0268] FIG. 25: ID GWAXS spectra in the in-plane (left) and out of plane direction (right).

[0269] FIG. 26: Comparison of DSC and WAXS determination of percent crystallinity.

[0270] FIG. 27: WAXS profiles for LLDPE, triketone modified polymers (Pl, P2, & P4), and DCPNs (DCPN-P1, DCPN-P2, and DCPN-P4). (left) WAXS scattering pattern (right) zoomed WAXS scattering pattern. As functionalization increases, intensity of crystalline peaks decreases, indicating decreasing crystallinity percent.

[0271] FIG. 28: Frequency sweep for 0.5 mol% diketoenamine crosslinked LLDPE (DCPN-P2) thin films. Linear viscoelastic region is observed across all frequencies.

[0272] FIG. 29: Strain sweep on 0.5 mol% diketoenamine crosslinked LLDPE (DCPN-P2) thin films. Linear viscoelastic region observed at strains below 10%.

[0273] FIG. 30: Stress relaxation conducted on the TA DHR-2 rheometer. Initial stress is dissipated over time as dynamic covalent bonds rearrange to dissipate stress. At higher temperatures, bonds rearrange more quickly, resulting in faster stress relaxation.

[0274] FIG. 31: Stress relaxation conducted on the TA DHR-2 rheometer. Initial stress is dissipated over time as dynamic covalent bonds rearrange to dissipate stress. At higher temperatures, bonds rearrange more quickly, resulting in faster stress relaxation.

[0275] FIG. 32: Linear-linear plot of stress relaxation conducted on the TA DHR-2 rheometer. Initial stress is dissipated over time as dynamic covalent bonds rearrange to dissipate stress. At higher temperatures, bonds rearrange more quickly, resulting in faster stress relaxation.

[0276] FIG. 33: The activation energy to bond exchange was determined through Arrhenius analysis. Using the equation ln( tau*)=ln(tauo)+Ea / RT where tau* (s) is the time when initial stress relaxes to 1 / e, Eais the activation energy to bond exchange (kJ), R=8.314 J / (mol*K). Activation energy is determined from the slope of the plot.

[0277] FIG. 34: (left) Creep measurements were conducted for LLDPE. At higher temperatures, LLDPE displayed diminished resistance to creep, (right) Creep measurements were conducted on diketoenamine crosslinked LLDPE (DCPN-P2) with a 0.9:1 ratio of R — NH2 to triketone. At higher temperatures, DCPN-P2 displayed diminished resistance to creep.

[0278] FIG. 35: Creep measurements were on LLDPE were compared to diketoenamine crosslinked LLDPE (DCPN-P2) with a 0.9: 1 ratio of R — NH2 to triketone.

[0279] FIG. 36: Uniaxial tensile pulls in triplicate. All dogbones are pulled at a rate of 0.09 mm / s (0.005 s'1).

[0280] FIG. 37: Tensile pulls in triplicate after each round of reprocessing DCPN-P2.

[0281] FIG. 38: P13 with a gel content of 85% without the presence of hexylamine showed a gel content of 0% in the presence of hexylamine. Gel fractions of 0 were measured across 3 reprocessing cycles.

[0282] FIG. 39: S4, ’H NMR (400 MHz, CDC13)

[0283] FIG. 40: 2, 'H NMR (400 MHz, CDCI3)

[0284] FIG. 41: Pl,XH NMR (500 MHz, EtCU)

[0285] FIG. 42: P2,1H NMR (500 MHz, EtCU)

[0286] FIG. 43: P3, ' H NMR (500 MHz, EtCU)

[0287] FIG. 44: P4, 'H NMR (500 MHz, EtCU)

[0288] FIG. 45: P5,1H NMR (500 MHz, EtCU)

[0289] FIG. 46: P6, ’H NMR (500 MHz, EtCU)

[0290] FIG. 47: P7, ' H NMR (500 MHz, EtCU)

[0291] FIG. 48: P8,1H NMR (500 MHz, EtCU)

[0292] FIG. 49: P9,1H NMR (500 MHz, EtCU)

[0293] FIG. 50: P10,rH NMR (500 MHz, EtCU)

[0294] FIG. 51: PH, 'H NMR (500 MHz, EtCU)

[0295] FIG. 52: P12,1H NMR (500 MHz, EtCU)

[0296] FIG. 53 : P 13 ,1H NMR (500 MHz, EtCU)

[0297] FIG. 54: Alcohol functionalized LLDPE, ' H NMR (500 MHz, EtCU)

[0298] FIG. 55: S4,13C NMR (400 MHz, CDCU)

[0299] FIG. 56: 2,13C NMR (600 MHz, CDCI3)REFERENCES

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[0345] All references throughout this application, for example patent documents, including issued or granted patents or equivalents and patent application publications, and non-patent literature documents or other source material are hereby incorporated by reference herein in their entireties, as though individually incorporated by reference.

[0346] All patents and publications mentioned in the specification are indicative of the levels of skill of those skilled in the art to which the invention pertains. References cited herein are incorporated by reference herein in their entirety to indicate the state of the art, in some cases as of their filing date, and it is intended that this information can be employed herein, if needed, to exclude (for example, to disclaim) specific embodiments that are in the prior art.

[0347] When a group of substituents is disclosed herein, it is understood that all individual members of those groups and all subgroups and classes that can be formed using the substituents are disclosed separately. When a Markush group or other grouping is used herein, all individual members of the group and all combinations and subcombinations possible of the group are intended to be individually included in the disclosure. As used herein, “and / or” means that one, all, or any combination of items in a list separated by “and / or” are included in the list; for example “1, 2 and / or 3” is equivalent to “1, 2, 3, 1 and 2, 1 and 3, 2 and 3, or 1, 2 and 3”.

[0348] Every formulation or combination of components described or exemplified can be used to practice the invention, unless otherwise stated. Specific names of materials are intended to be exemplary, as it is known that one of ordinary skill in the art can name the same material differently. It will be appreciated that methods, device elements, starting materials, and synthetic methods other than those specifically exemplified can be employed in the practice of the invention without resort to undue experimentation. All art-known functional equivalents, of any such methods, device elements, starting materials, and synthetic methods are intended to be included in this invention. Whenever a range is given in the specification, for example, a temperature range, a time range, or a composition range, all intermediate ranges and subranges, as well as all individual values included in the ranges given are intended to be included in the disclosure.

[0349] As used herein, “comprising” is synonymous with “including,” “containing,” or “characterized by,” and is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. As used herein, “consisting of’ excludes any element, step, or ingredient not specified in the claim element. As used herein, “consisting essentially of’ does not exclude materials or steps that do not materially affect the basic and novel characteristics of the claim. Any recitation herein of the term “comprising”, particularly in a description of components of a composition, in a description of a method, or in a description of elements of a device, is understood to encompass those compositions, methods, or devices consisting essentially of and consisting of the recited components or elements, optionally in addition to other components or elements. The invention illustratively described herein suitably may be practiced in the absence of any element, elements, limitation, or limitations which is not specifically disclosed herein.

[0350] The terms and expressions which have been employed are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed. Thus, it should be understood that although the present invention has been specifically disclosed by examples, embodiments, and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this invention as defined by the appended claims.

Claims

WHAT IS CLAIMED IS:

1. A composition comprising:a cross-linked polydiketoenamine functionalized polyolefin network, the crosslinked polydiketoenamine functionalized polyolefin network comprising:a first polytopic P-triketone functionalized polyolefin anda second polytopic P-triketone functionalized polyolefin,wherein the first polytopic P-triketone functionalized polyolefin and the second polytopic P-triketone functionalized polyolefin are crosslinked by a polyamine crosslinker.

2. The composition of claim 1, wherein the first polytopic P-triketone functionalized polyolefin comprises polymerized first polyolefin repeat units wherein at least some of the first polyolefin repeat units are functionalized by a first P-triketone moiety and wherein the second polytopic P-triketone functionalized polyolefin comprises polymerized second polyolefin repeat units wherein at least some of the second polyolefin repeat units are functionalized by a second P-triketone moiety.

3. The composition of claim 2, wherein the first P-triketone moiety and the second P-triketone moiety are the same P-triketone moiety or are different P-triketone moieties.

4. The composition of claim 2, wherein the first polyolefin repeat units and the second polyolefin repeat units correspond to miscible polyolefins or wherein the first polyolefin repeat units and the second polyolefin repeat units correspond to immiscible polyolefins.

5. The composition of claim 2, wherein a first amount of the first polyolefin repeat units functionalized by the first P-triketone moiety is from 0.05 wt.% to 20 wt.% and wherein a second amount of the second polyolefin repeat units functionalized by the second P-triketone moiety is from 0.05 wt.% to 20 wt.%.

6. The composition of claim 2, wherein the first P-triketone moiety is covalently linked to functionalized first polyolefin repeat units by a thioether linker or whereinthe second P-triketone moiety is covalently linked to functionalized second polyolefin repeat units by a thioether linker.

7. The composition of claim 2, wherein the first polyolefin repeat units or the second polyolefin repeat units are independently selected from polyethylene repeat units, polypropylene repeat units, polybutylene repeat units, poly (1 -pentene) repeat units, poly(l-hexene) repeat units, poly(l -heptene) repeat units, poly(l-octene) repeat units, poly(l -decene) repeat units, poly(l -tetradecene) repeat units, poly(l -hexadecene) repeat units, poly(l-octadecene) repeat units, polynorbornene repeat units, poly(isobutylene) repeat units, copolymer repeat units comprising two or more polyolefin monomers, or branched architecture polymeric repeat units (e.g., prepared using chain shuttling), or wherein the first polyolefin repeat units or the second polyolefin repeat units comprises copolymers of at least one polyolefin monomer and one or more other monomers, or copolymers or triblock copolymers of repeat units including one or more of ethylene, propylene, hexene, octene, or styrene.

8. The composition of claim 2, wherein the first P-triketone moiety or the second P-triketone moiety are P-triketone moieties independently selected from, wherein ring X' is a ring moiety containing one or more X or C-R ring substituents, wherein each X is independently selected from the group consisting of O, CRR, SiRR, NR, S, Se, and PR, wherein each R is independently selected from the group consisting of hydrogen, Cl -20 alkyl, C2-20 alkenyl, C2-20 alkynyl, C3-8 cycloalkyl, Ce-14 aryl, 3- to 12-membered heterocyclyl, and 5- to 12-membered heteroaryl, wherein each alkyl is independently unsubstituted or substituted with a C3-8 cycloalkyl, a Ce-14 aryl, a 3- to 12-membered heterocyclyl, or a 5- to 12-membered heteroaryl, wherein ring X' contains up to two double bonds in the ring moiety, and wherein Z is a substituted or unsubstituted linker moiety.

9. The composition of claim 8, wherein the P-triketone moieties areindependently selected fromwherein n is 1 to 5, and wherein each Y is X or C-R.

10. The composition of claim 9, wherein the P-triketone moieties are11. The composition of claim 8, wherein Z is an aliphatic or aromatic linker moiety containing at least one sulfur atom covalently linking the P-triketone moiety to a respective polyolefin repeat unit.

12. The composition of claim 11, wherein Z compriseswhere R1is a substituted or unsubstituted divalent aliphatic moiety or a substituted or unsubstituted divalent aromatic moiety.

13. The composition of claim 1, wherein the cross-linked polydiketoenamine functionalized polyolefin network has a formula of:DK2^1IK1\ A / , wherein PO1is a first polyolefin repeat unit of the first polytopic P-triketone functionalized polyolefin, wherein PO1' is a first diketoenamine functionalized polyolefin repeat unit of the first polytopic P-triketone functionalized polyolefin, wherein PO2is a second polyolefin repeat unit of the second polytopic P-triketone functionalized polyolefin, wherein PO2' is a diketoenamine functionalized polyolefin repeat unit of the second polytopic P-triketone functionalized polyolefin, wherein DK1is a first diketoenamine moiety, wherein DK2is a second polyketone moiety, wherein M represents a crosslinker of the polyamine crosslinker, wherein each Z is independently an aliphatic or aromatic linker moiety containing at least one sulfur atom covalently linking a diketoenamine moiety to a respective polyolefin repeat unit, wherein i indicates non-functionalized repeat units of the first polytopic P-triketone functionalized polyolefin, wherein j represents diketoenamine functionalized repeat units of the first polytopic P-triketone functionalized polyolefin, wherein k indicates non-functionalized repeat units of the second polytopic P-triketone functionalized polyolefin, and wherein 1 represents diketoenamine functionalized repeat units of the second polytopic P-triketone functionalized polyolefin.

14. The composition of claim 1, wherein the polyamine crosslinker is a diamine crosslinker a triamine crosslinker, or a crosslinker including four or more amino groups.

15. The composition of claim 1, wherein the polyamine crosslinker is a substituted or unsubstituted polyvalent aliphatic or aromatic moiety containing a plurality of amino groups.

16. The composition of claim 1, further comprising one or more polyolefins mixed with the cross-linked polydiketoenamine functionalized polyolefin network.

17. The composition of claim 16, wherein the one or more polyolefins comprises a plurality of polyolefins miscible with one another or a plurality of polyolefins immiscible with one another.

18. The composition of claim 16, wherein the one or more polyolefins are miscible with a first polyolefin moiety of the first polyketone functionalized polyolefin or immiscible with the first polyolefin moiety of the first polyketone functionalized polyolefin, or wherein the one or more polyolefins are miscible with a second polyolefin moiety of the second polyketone functionalized polyolefin or immiscible with the second polyolefin moiety of the second polyketone functionalized polyolefin.

19. The composition of claim 16, wherein a weight ratio of the one or more polyolefins to the cross-linked polydiketoenamine functionalized polyolefin network is from 1:99 to 2:1.

20. A composition comprising:a polytopic diketoenamine functionalized polyolefin, the polytopic diketoenamine functionalized polyolefin comprising polymerized polyolefin repeat units, wherein at least some of the polyolefin repeat units are functionalized by a diketoenamine moiety.

21. The composition of claim 20, wherein the polyolefin repeat units are selected from polyethylene repeat units, polypropylene repeat units, polybutylene repeat units, poly (1 -pentene) repeat units, poly (1 -hexene) repeat units, poly(l -heptene) repeat units, poly(l-octene) repeat units, poly(l -decene) repeat units, poly(l -tetradecene) repeat units, poly(l-hexadecene) repeat units, poly (1 -octadecene) repeat units, polynorbomene repeat units, poly(isobutylene) repeat units, copolymer repeat units comprising two or more polyolefin monomers, or branched architecture polymeric repeat units (e.g., prepared using chain shuttling),or wherein the polyolefin comprises copolymers of at least one polyolefin monomer and one or more other monomers, or copolymers or triblock copolymers of repeat units including one or more of ethylene, propylene, hexene, octene, or styrene.

22. The composition of claim 20, wherein an amount of the polyolefin repeat units functionalized by the diketoenamine moiety is from 0.05 wt.% to 20%.

23. The composition of claim 20, wherein diketoenamine moiety is covalently linked to functionalized polyolefin repeat units by a thioether linker.

24. The composition of claim 20, wherein the diketoenamine moiety comprises a diketone moiety and an amino group.

25. The composition of claim 20, wherein the diketoenamine moiety isindependently selected fromwherein ring X' is a ring moiety containing one or more X or C-R ring substituents, wherein each X is independently selected from the group consisting of O, CRR, SiRR, NR, S, Se, and PR, wherein each R is independently selected from the group consisting of hydrogen, Cl -20 alkyl, C2-20 alkenyl, C2-20 alkynyl, C3-8 cycloalkyl, Ce-14 aryl, 3- to 12-membered heterocyclyl, and 5-to 12-membered heteroaryl, wherein each alkyl is independently unsubstituted or substituted with a C3-8 cycloalkyl, a Ce-14 aryl, a 3- to 12-membered heterocyclyl, or a 5- to 12-membered heteroaryl, wherein ring X' contains up to two double bonds in the ring moiety, wherein Z is a substituted or unsubstituted linker moiety, and wherein M is an amino group.

26. The composition of claim 25, wherein the diketoenamine moiety isselected fromwherein n is 1 to 5, and wherein each Y is independently X or C-R.

27. The composition of claim 26, wherein the diketoenamine moiety is28. The composition of claim 25, wherein Z is an aliphatic or aromatic linker moiety containing at least one sulfur atom covalently linking the diketoenamine moiety to a respective polyolefin repeat unit.

29. The composition of claim 28, wherein Z compriseswhere R1is a substituted or unsubstituted divalent aliphatic moiety or a substituted or unsubstituted divalent aromatic moiety.

30. The composition of claim 20, wherein the polytopic diketoenamine functionalized polyolefin has a formula of:\ , wherein PO is a polyolefin repeat unit, wherein PO' is a diketoenamine functionalized polyolefin repeat unit, wherein DK is a diketoenamine moiety, wherein M represents an amine linked group, wherein Z is an aliphatic or aromatic linker moiety containing at least one sulfur atom, wherein i indicates non-functionalized repeat units of the polytopic diketoenamine functionalized polyolefin, and wherein j represents diketoenamine functionalized repeat units of the polytopic diketoenamine functionalized polyolefin.

31. The composition of claim 20, further comprising one or more polyolefins mixed with the polydiketoenamine functionalized polyolefin.

32. The composition of claim 31, wherein the one or more polyolefins comprises a plurality of polyolefins miscible with one another or a plurality of polyolefins immiscible with one another.

33. The composition of claim 31, wherein the one or more polyolefins are miscible with the polyolefin moiety or wherein the one or more polyolefins are immiscible with the polyolefin moiety.

34. The composition of claim 31, wherein a weight ratio of the one or more polyolefins to the polytopic diketoenamine functionalized polyolefin is from 1 :99 to 2: 1.

35. A composition comprising:a polytopic P-triketone functionalized polyolefin, the polytopic -triketone functionalized polyolefin comprising polymerized polyolefin repeat units, wherein at least some of the polyolefin repeat units are functionalized by a P-triketone moiety.

36. The composition of claim 35, wherein the repeat units are selected from polyethylene repeat units, polypropylene repeat units, polybutylene repeat units, poly(l -pentene) repeat units, poly(l -hexene) repeat units, poly(l -heptene) repeat units, poly(l -octene) repeat units, poly(l -decene) repeat units, poly (1 -tetradecene) repeat units, poly(l -hexadecene) repeat units, poly(l -octadecene) repeat units, polynorbornene repeat units, poly(isobutylene) repeatunits, copolymer repeat units comprising two or more polyolefin monomers, or branched architecture polymeric repeat units (e.g., prepared using chain shuttling), or wherein the polymerized polyolefin repeat units comprise copolymers of at least one polyolefin monomer and one or more other monomers, or copolymers or triblock copolymers of repeat units including one or more of ethylene, propylene, hexene, octene, or styrene.

37. The composition of claim 35, wherein an amount of the polyolefin repeat units functionalized by the P-triketone moiety is from 0.05 wt.% to 20%.

38. The composition of claim 35, wherein the P-triketone moiety is covalently linked to functionalized polyolefin repeat units by a thioether linker.

39. The composition of claim 35, wherein the P-triketone moiety is selected, wherein ring X' is a ring moiety containing one or more X or C-R ring substituents, wherein each X is independently selected from the group consisting of O, CRR, SiRR, NR, S, Se, and PR, wherein each R is independently selected from the group consisting of hydrogen, Cl-20 alkyl, C2-20 alkenyl, C2-20 alkynyl, C3-8 cycloalkyl, Ce-14 aryl, 3- to 12-membered heterocyclyl, and 5- to 12-membered heteroaryl, wherein each alkyl is independently unsubstituted or substituted with a C3-8 cycloalkyl, a Ce-i4 aryl, a 3 - to 12-membered heterocyclyl, or a 5- to 12-membered heteroaryl, wherein ring X' contains up to two double bonds in the ring moiety, wherein ring X' contains up to two double bonds in the ring moiety, and wherein Z is a substituted or unsubstituted linker moiety.

40. The composition of claim 39, wherein the P-triketone moiety is selectedwherein n is 1 to 5, and wherein each Y is independently X or C-R.

41. The composition of claim 40, wherein the P-triketone moiety is selected42. The composition of claim 39, wherein Z is an aliphatic or aromatic linker moiety containing at least one sulfur atom covalently linking the P-triketone moiety to a respective polyolefin repeat unit.R143. The composition of claim 42, wherein Z comprises, where R1is a substituted or unsubstituted divalent aliphatic moiety or a substituted or unsubstituted divalent aromatic moiety.

44. The composition of claim 35, wherein polytopic P-triketone functionalized polyolefin has a formula of:'z4 , wherein PO is a polyolefin repeat unit, wherein PO' is a P-triketone functionalized polyolefin repeat unit, wherein TK is a P-triketone moiety, wherein Z is an aliphatic or aromatic linker moiety containing at least one sulfur atom, wherein i indicates non-functionalized polyolefin repeat units, and wherein j represents P-triketone functionalized polyolefin repeat units.

45. The composition of claim 35, further comprising an amine or polyamine mixed with the polytopic P-triketone functionalized polyolefin.

46. The composition of claim 35, further comprising a second polytopic P-triketone functionalized polyolefin mixed with the polytopic P-triketone functionalized polyolefin.

47. The composition of claim 46, further comprising a polyamine mixed with the polytopic p-triketone functionalized polyolefin and the second polytopic -triketone functionalized polyolefin.

48. The composition of claim 35, further comprising one or more polyolefins mixed with the polytopic P-triketone functionalized polyolefin.

49. The composition of claim 48, wherein a weight ratio of the one or more polyolefins to the polytopic P-triketone functionalized polyolefin is from 1:99 to 2:1.

50. A composition comprising:a functionalized P-triketone, the functionalized P-triketone comprising a P-triketone moiety covalently linked to a thiosulfonate moiety.

51. The composition of claim 50, wherein the P-triketone moiety is selected, wherein ring X' is a ring moiety containing one or more X or C-R ring substituents, wherein each X is independently selected from the group consisting of O, CRR, SiRR, NR, S, Se, and PR, wherein each R is independently selected from the group consisting of hydrogen, Cl -20 alkyl, C2-20 alkenyl, C2- 20 alkynyl, C3-8 cycloalkyl, Ce-14 aryl, 3- to 12-membered heterocyclyl, and 5- to 12-membered heteroaryl, wherein each alkyl is independently unsubstituted or substituted with a C3-8 cycloalkyl, a Ce-14 aryl, a 3- to 12-membered heterocyclyl, or a 5- to 12-membered heteroaryl, wherein ring X' contains up to two double bonds in the ring moiety, and wherein Z' is a substituted or unsubstituted linker moiety.

52. The composition of claim 51 , wherein the P-triketone moiety is selected, wherein n is 1 to 5, and wherein each Y is independently X or C-R.

53. The composition of claim 52, wherein the P-triketone moiety is selected54. The composition of claim 51, wherein Z' is a divalent aliphatic or aromatic linker.

55. The composition of claim 50, wherein the thiosulfonate moiety has a oformulaR, wherein R' is a substituted or unsubstituted aliphatic or aromatic group.

56. The composition of claim 55, wherein the thiosulfonate moiety has aformula57. The composition of claim 50, further comprising a polyolefin mixed with the functionalized P-triketone.

58. The composition of claim 57, wherein the polyolefin comprises repeat units selected from polyethylene repeat units, polypropylene repeat units, polybutylene repeat units, poly(l -pentene) repeat units, poly(l -hexene) repeat units, poly (1 -heptene) repeat units, poly(l-octene) repeat units, poly(l -decene) repeat units, poly(l -tetradecene) repeat units, poly(l-hexadecene) repeat units, poly (1 -octadecene) repeat units, polynorbomene repeat units, poly(isobutylene) repeat units, copolymer repeat units comprising two or more polyolefin monomers, or branched architecture polymeric repeat units (e.g., prepared using chain shuttling), or wherein the polyolefin comprises copolymers of at least one polyolefin monomer and one or more other monomers, or copolymers or triblock copolymers of repeat units including one or more of ethylene, propylene, hexene, octene, or styrene.

59. The composition of claim 57, further comprising an O-alkenylhydroxamate mixed with the functionalized P-triketone and the polyolefin.

60. The composition of claim 59, wherein the O-alkenylhydroxamate has aformula

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