Hot melt adhesive polymer blends

Abstract

Set forth herein are polymer blends of an aminated-polyolefin with poly (ethylene-co-vinyl acetate. Also set forth herein are processes of making and using the same, including using the blend as a hot melt adhesive.

Description

Attorney Docket No.: 125298.00044 INTERNATIONAL PCT PATENT APPLICATION HOT MELT ADHESIVE POLYMER BLENDS CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to, and the benefit of, U.S. Provisional PatentApplication No.63 / 669,608, filed July 10, 2024, the entire contents of which are herein incorporated by reference in their entirety for all purposes. FIELD

[0002] The present disclosure concerns thermoplastics, hot melt adhesives, polymerblends, as well as processes for making and methods of using the same, such as, but not limited to, a process for preparing a hot melt adhesive by blending aminated polyolefins with at least one or more ethyl vinyl acetate copolymers. BACKGROUND OF THE INVENTION

[0003] A hot melt adhesive (HMA) is a form of thermoplastic adhesive that is depositedonto a substrate in the melt state. After deposition, the HMA solidifies after cooling. Poly (ethylene-co-vinyl acetate) (EVA) is a random copolymer with up to 60% by weight vinyl acetate (VA) in the EVA copolymer. EVAs are used as a polymer base in certain HMAs combinations. These combinations are known as EVA-based HMAs. EVA-based HMAs are used for engineering and structural materials as well as consumer applications such as packaging, textile and book binding. See Shih, H. H.; Hamed, G., Journal of Applied Polymer Science 1997, 63 (3), 323-331.

[0004] VA content in EVA varies from 4% to 40% by weight of the EVA copolymer.EVA copolymers may vary with respect to each other with regard to their surface tension and crystalline percentage as well as other properties. Tackifiers such as hydrocarbon resins or rosin esters may be added to improve the adhesion of EVA mixtures on substrates. EVA-based HMAs generally possess limited adhesion to low surface energy substrates such as polytetrafluoroethylene (PTFE) and thermoplastics such as polyethylene and polypropylene. This limits the potential uses of EVA-based HMAs. - 1 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044

[0005] Aminated polyolefins are a class of associating polymers with uniquestimuli-responsive, adhesion and self-healing properties. See WO2019222852A1, which published November 28, 2019, and is titled NOVEL AMINE FUNCTIONALIZED POLYMERS AND METHODS OF PREPARATION, the entire contents of each of which are herein incorporated by reference in their entirety for all purposes. The amine- containing functional groups in these polymers form reversible hydrogen-bonds that impart complex and diverse polymer chain dynamics. Factors that affect chain dynamics and material properties include the association lifetime, chain mobility, association density, and other factors.

[0006] What is needed in the field to which the instant disclosure pertains is new blendsof EVA with amine-functionalized polymers (e.g., linear amine-functionalized polymers) that would be useful for adhering to low energy substrates. Set forth herein are solutions to this and other problems in the relevant field. SUMMARY OF THE INVENTION

[0007] In one embodiment, set forth herein is a polymer blend that includes an amine-functionalized polymer (APE); and a poly (ethylene-co-vinyl acetate) (EVA) co-polymer.

[0008] In a second embodiment, set forth herein is a substrate coated with a polymerblend that is disclosed herein.

[0009] In a third embodiment, set forth herein is apparel, shoes, book bindings, and / orautomotive parts that include a surface or interface coated with a polymer blend that is disclosed herein.

[0010] In a fourth embodiment, set forth herein is a kit that includes a polymer blend thatis disclosed herein and instructions for disposing the polymer blend on a substrate.

[0011] In a fifth embodiment, set forth herein is a substrate comprising a polymer blendthat is disclosed herein disposed on at least one surface or at least one interface of that substrate.

[0012] In a sixth embodiment, set forth herein is a trilayer that includes a polymer blenddisclosed herein between, and in contact with, two substrates.

[0013] In a seventh embodiment, set forth herein is a process for making a film of apolymer blend that includes mixing in a solvent an amine-functionalized polymer (APE) - 2 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 and a poly (ethylene-co-vinyl acetate) (EVA) co-polymer to form a solvent mixture; wherein the APE:EVA mass ratio is 1:3 to 10:1; casting the solvent mixture on a substrate; and drying the casted solvent mixture to form a film on the substrate.

[0014] In an eighth embodiment, set forth herein is a process for disposing a polymerblend on a substrate, wherein the process includes providing a polymer blend that is disclosed herein; heating the polymer blend above its melting temperature; disposing the polymer blend on a substrate; and cooling the polymer blend below its melting temperature.

[0015] In a ninth embodiment, set forth herein is a process for disposing a polymer blendon a substrate, that includes providing a polymer blend that is disclosed herein; and pressing the polymer blend onto a substrate at a pressure of 0.1 MPa to 100 MPa and a temperature of 40 ºC to 200 ºC.

[0016] In a tenth embodiment, set forth herein is a polymer blend made by at least oneprocess disclosed herein.

[0017] In an eleventh embodiment, set forth herein is a method of using a polymer blenddisclosed herein, wherein the method includes using the polymer blend for crack filling, as an antimicrobial agent, as an adhesive agent, as a coating, as a compatibilizer, as a stabilizer, as a metal scavenger, as a membrane, as a gasket, as a drug delivery agent, as a scavenger agent, comprising applying the amine-functionalized polymer to a substrate.

[0018] In a twelfth embodiment, set forth herein is a substrate comprising a polymerblend that is made by a process disclosed herein.

[0019] In a thirteenth embodiment, set forth herein is a trilayer that includes a polymerblend disclosed herein between, and in contact with, two substrates, wherein the trilayer is made by a process disclosed herein. BRIEF DESCRIPTION OF DRAWINGS

[0020] FIG. 1A (left) shows a T-peel test curve: peeling strength versus distance forAPE / EVA-40 blend.

[0021] FIG. 1B (right) shows the maximum peeling strength, average peeling strengthand energy density for APE / EVA-40 blends. - 3 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044

[0022] FIG. 2A (left) shows a T-peel test curve: peeling strength versus distance forAPE / EVA-40 blend from 50 wt% to 91 wt% APE.

[0023] FIG. 2B (right) shows a maximum peeling strength, average peeling strength andenergy density for APE / EVA-40 blends shown in FIG.2A.

[0024] FIG. 3 shows the maximum peeling strength, average peeling strength and energydensity for 75APE / EVA-40 blend on various substrates. For each sample substrate, there are three columns, which from left to right, read “Maximum,” “Average,” and “Energy density.”

[0025] FIG. 4 shows T-peel test results for 75APE / EVA-40 blend at varying peelingrate. For each sample peel rate, there are three columns, which from left to right, read “Max peel strength,” “Average peel strength,” and “Energy density.”

[0026] FIG. 5 shows an illustration of T-peel and lap shear tests sample preparation.

[0027] FIG. 6 shows the average peel strength of 90APE / EVA-40 blend at varyingpeeling rates on PTFE substrates.

[0028] FIG. 7 shows the average peel strength of 60APE / EVA-40 blend at 10 mm / minon varying substrates.

[0029] FIG. 8 (left) shows the dog-bone shape of the tested sample and the stretchedsample during the testing, (right) shows the stress-strain curve of 75APE / EVA and 90APE / EVA blends before and after self-healing at varying conditions.

[0030] FIG. 9 shows the T-peel displacement curves for original and repressed60APE / EVA blend on polyester substrates at rate of 10 mm min-1. The inset showed the average peel strength for the two cases. DETAILED DESCRIPTION OF THE INVENTION

[0031] A new class of linear amine-functionalized polymers (APEs) was synthesizedusing a two-step catalytic combination of hydroaminoalkylation and ring-opening metathesis polymerization (ROMP). See, for example, WO2019222834A1, which published November 28, 2019, and is titled GROUP 5 METAL COMPLEXES FOR PRODUCING AMINE-FUNTIONALIZED POLYOLEFINS; WO2019222852A1, which published November 28, 2019, and is titled NOVEL AMINE FUNCTIONALIZED POLYMERS AND METHODS OF PREPARATION; and - 4 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 WO2023092225A1, which published June 1, 2023, and is titled SUPERHYDROPHOBIC COATINGS, COMPOSITIONS AND METHODS, the entire contents of each of which are herein incorporated by reference in their entirety for all purposes.

[0032] In some embodiments, these materials have tunable viscoelastic properties thatcan be further modified through variable molecular weight. As molecular weight increases, these polymers show a liquid-like to gel and soft solid transition. These materials possess autonomous self-healing properties and adhesion to low surface energy substrates such as non-surface modified PTFE. The cohesive strength can be modified by several material characteristics including crystallinity, crosslinking, molecular weight and compatibility such as in multi-phase systems. Set forth herein are a variety of polymer blends of APE and EVA that can be used as a hot-melt and / or pressure sensitive adhesive. The polymer blends disclosed herein greatly improve cohesion and adhesion to low-surface energy substrates compared to known adhesives.

[0033] The present disclosure sets forth a method for preparing a HMA with improvedadhesive strength on low surface energy substrates such as PTFE. This HMA improves the cohesive strength of APE-based adhesives by blending EVA into the polymer blend. In the blend, two factors, the mass percentage of EVA relative to APE, and the VA content in the selected EVA, have been investigated to understand their effect on the compatibility, adhesive and cohesive strength of the system to find blend ratios suitable for different applications. Compared to APE or EVA alone, the instant disclosure sets forth HMA blends of APE and EVA that demonstrate a significant increase in adhesive strength as a bond between PTFE substrates.

[0034] Set forth herein is also a process for producing an HMA. In certain embodiments,to prepare the HMA, an amine-functionalized polymer is first mixed at a specific mass ratio of poly(ethylene-co-vinyl acetate) in a suitable solvent. This solvent mixture is cast into a film using a typical solution-casting process. After drying, the film can function as an HMA by applying it to one or more substrates followed by application of heat and pressure for a set time. - 5 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 DEFINITIONS

[0035] When referring to the compounds provided herein, the following terms have thefollowing meanings unless indicated otherwise. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as is commonly understood by one of ordinary skill in the art. If a plurality of definitions exists for a term herein, those in this section prevail unless stated otherwise.

[0036] All publications, patent applications, patents, and other references mentionedherein are incorporated herein by reference in their entirety. In case of conflict, the present application will control.

[0037] The articles “a,” “an,” and “the” as used herein not only include certain embodimentswith a single member, but also may include embodiments with more than one member.

[0038] The term “or” as used herein similarly is a Boolean “or,” unless the alternativescannot be combined without logical incompatibility. For example, an aspect “comprising a member selected from A, B, or C” should be understood as applying to embodiments comprising A and B; B and C; A and C; or A, B, and C.

[0039] The term “about” as used herein to modify a numerical value indicates a definedrange around that value. If “X” were the value, “about X” would generally indicate a value from 0.95X to 1.05X. Any reference to “about X” specifically indicates at least the values X, 0.95X, 0.96X, 0.97X, 0.98X, 0.99X, X, 1.01X, 1.02X, 1.03X, 1.04X, and 1.05X. Thus, “about X” is intended to teach and to provide written description support for a claim limitation of, e.g., “0.98X.” When “about” is applied to the beginning of a numerical range, it applies to both ends of the range. Thus, “from about 5 to 20%” is equivalent to “from about 5% to about 20%.” When “about” is applied to the first value of a set of values, it applies to all values in that set. Thus, “about 7, 9, or 11%” is equivalent to “about 7%, about 9%, or about 11%.”

[0040] The terms “comprise”, “comprising”, “include”, and “including” when used in thisspecification and in the claims are intended to specify the presence of the stated features, integers, components, or steps, but they do not preclude the presence or addition of one or more additional features, integers, components, or steps thereof. - 6 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044

[0041] The term “alkyl”, as used herein, unless otherwise specified, refers to a saturatedstraight or branched hydrocarbon. In certain embodiments, the alkyl group is a primary, secondary, or tertiary hydrocarbon. In certain embodiments, the alkyl group includes one to ten carbon atoms, i.e., C1-10alkyl. In certain embodiments, the alkyl group includes one to fifteen carbon atoms, i.e., C1-15alkyl. In certain embodiments, the alkyl group includes one to five carbon atoms, i.e., C1-5alkyl. In certain embodiments, the alkyl group includes one to six carbon atoms, i.e., C1-6alkyl. In certain embodiments, the alkyl group is selected from the group consisting of methyl, CF3, CCl3, CFCl2, CF2Cl, ethyl, CH2CF3, CF2CF3, propyl, isopropyl, butyl, isobutyl, secbutyl, t-butyl, pentyl, isopentyl, neopentyl, hexyl, isohexyl, 3-methylpentyl, 2,2-dimethylbutyl, and 2,3-dimethylbutyl. The term includes both substituted and unsubstituted alkyl groups, including halogenated alkyl groups. In certain embodiments, the alkyl group is a fluorinated alkyl group. Non- limiting examples of moieties with which the alkyl group can be substituted are selected from the group consisting of halogen (fluoro, chloro, bromo or iodo), hydroxyl, amino, alkylamino, arylamino, alkoxy, aryloxy, nitro, cyano, sulfonic acid, sulfate, phosphonic acid, phosphate, or phosphonate, either unprotected, or protected as necessary, as known to those skilled in the art, for example, as taught in Greene, et al., Protective Groups in Organic Synthesis, John Wiley and Sons, Second Edition, 1991, hereby incorporated by reference in its entirety for all purposes.

[0042] The term “cycloalkyl”, as used herein, unless otherwise specified, refers to a saturatedcyclic hydrocarbon. In certain embodiments, the cycloalkyl group may be a saturated, and / or bridged, and / or non-bridged, and / or a fused bicyclic group. In certain embodiments, the cycloalkyl group includes three to ten carbon atoms, i.e., C3-10 cycloalkyl. In certain embodiments, the cycloalkyl group includes four to ten carbon atoms, i.e., C4-10 cycloalkyl. In certain embodiments, the cycloalkyl group includes six to ten carbon atoms, i.e., C6-10 cycloalkyl. In certain embodiments, the cycloalkyl group is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, cycloheptyl, bicyclo[2.1.1]hexyl, bicyclo[2.2.1]heptyl, decalinyl, or adamantyl.

[0043] The term “cycloalkenyl”, as used herein, unless otherwise specified, refers to anunsaturated cyclic hydrocarbon. In certain embodiments, cycloalkenyl refers to mono- or multicyclic ring systems that include at least one double bond. In certain embodiments, - 7 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 the cycloalkenyl group may be a bridged, non-bridged, and / or a fused bicyclic group. In certain embodiments, the cycloalkenyl group includes three to ten carbon atoms, i.e., C3-10 cycloalkenyl. In certain embodiments, the cycloalkenyl group includes four to ten carbon atoms, i.e., C4-10cycloalkenyl. In certain embodiments, the cycloalkenyl group includes six to ten carbon atoms, i.e., C6-10 cycloalkenyl. In some embodiments, the cycloalkenyl has from 3 to 7 carbon atoms (C3-10), or from 4 to 7 (C3-7) carbon atoms.

[0044] The term “aryl”, as used herein, and unless otherwise specified, refers to phenyl,biphenyl, or naphthyl. Aryl, generally, refers to a monovalent monocyclic aromatic group and / or multicyclic aromatic group that contain at least one aromatic ring. Aryl groups are bonded to the rest of the molecule through the aromatic ring The term includes both substituted and unsubstituted moieties. An aryl group can be substituted with any described moiety, including, but not limited to, one or more moieties selected from the group consisting of halogen (fluoro, chloro, bromo or iodo), alkyl, haloalkyl, hydroxyl, amino, alkylamino, arylamino, alkoxy, aryloxy, nitro, cyano, sulfonic acid, sulfate, phosphonic acid, phosphate, or phosphonate, either unprotected, or protected as necessary, as known to those skilled in the art, for example, as taught in. In certain embodiments, the aryl group has six to ten carbons, e.g., C6-10aryl.

[0045] “Alkoxy” refers to the group –OR′ where R′ is alkyl or cycloalkyl. Alkoxy groupsinclude, by way of example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert- butoxy, sec-butoxy, n-pentoxy, n-hexoxy, 1,2-dimethylbutoxy, and the like. In certain embodiments, the alkoxy group includes 1 to five carbon atoms, i.e., C1-5alkoxy. In certain examples, the alkoxy is substituted with one or more halogens, e.g., C1-5haloalkoxy.

[0046] “Amino” refers to the radical -NH2.

[0047] “Nitro” refers to the radical -NO2.

[0048] “Carboxyl” or “carboxy” refers to the radical -C(O)OH.

[0049] “Carbonyl” refers to the radical -C(O).

[0050] “Halogen” or “halo” refers to chloro, bromo, fluoro or iodo.- 8 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044

[0051] The term “heterocycloalkyl,” “heterocyclyl,” or “heterocyclic” refers to a monovalentmonocyclic non-aromatic ring system and / or multicyclic ring system that contains at least one non-aromatic ring, wherein one or more of the non-aromatic ring atoms are heteroatoms independently selected from O, S, or N; and the remaining ring atoms are carbon atoms. In certain embodiments, the heterocyclyl or heterocyclic group has from 3 to 20, from 3 to 15, from 3 to 10, from 3 to 8, from 4 to 7, or from 5 to 6 ring atoms. In certain embodiments, the heterocyclic group has four to ten ring atoms, i.e., C4-10heterocycloalkyl. In certain embodiments, the heterocyclic group has three to ten ring atoms, i.e., C3-10heterocycloalkyl. Heterocyclyl groups are bonded to the rest of the molecule through the non-aromatic ring. In certain embodiments, the heterocyclyl is a monocyclic, bicyclic, tricyclic, or tetracyclic ring system, which may include a fused or bridged ring system, and in which the nitrogen or sulfur atoms may be optionally oxidized, the nitrogen atoms may be optionally quaternized, and some rings may be partially or fully saturated, or aromatic. The heterocyclyl may be attached to the main structure at any heteroatom or carbon atom which results in the creation of a stable compound. Examples of such heterocyclic radicals include, but are not limited to, azepinyl, benzodioxanyl, benzodioxolyl, benzofuranonyl, benzopyranonyl, benzopyranyl, benzotetrahydrofuranyl, benzotetrahydrothienyl, benzothiopyranyl, benzoxazinyl, β-carbolinyl, chromanyl, chromonyl, cinnolinyl, coumarinyl, decahydroisoquinolinyl, dihydrobenzisothiazinyl, dihydrobenzisoxazinyl, dihydrofuryl, dihydroisoindolyl, dihydropyranyl, dihydropyrazolyl, dihydropyrazinyl, dihydropyridinyl, dihydropyrimidinyl, dihydropyrrolyl, dioxolanyl, 1,4-dithianyl, furanonyl, imidazolidinyl, imidazolinyl, indolinyl, isobenzotetrahydrofuranyl, isobenzotetrahydrothienyl, isochromanyl, isocoumarinyl, isoindolinyl, isothiazolidinyl, isoxazolidinyl, morpholinyl, octahydroindolyl, octahydroisoindolyl, oxazolidinonyl, oxazolidinyl, oxiranyl, piperazinyl, piperidinyl, 4-piperidonyl, pyrazolidinyl, pyrazolinyl, pyrrolidinyl, pyrrolinyl, quinuclidinyl, tetrahydrofuryl, tetrahydroisoquinolinyl, tetrahydropyranyl, tetrahydrothienyl, thiamorpholinyl, thiazolidinyl, tetrahydroquinolinyl, and 1,3,5-trithianyl. In certain embodiments, heterocyclic may also be optionally substituted as described herein. - 9 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044

[0052] The term “heterocycloalkenyl,” refers to a monovalent monocyclic non-aromatic ringsystem and / or multicyclic ring system that contains at least one non-aromatic ring, wherein one or more of the non-aromatic ring atoms are heteroatoms independently selected from O, S, or N; and wherein the ring includes at least one double bond; and the remaining ring atoms are carbon atoms. In certain embodiments, the heterocycloalkenyl group has three to ten ring atoms, i.e., C3-10heterocycloalkyl.

[0053] The term “heteroaryl” refers to a monovalent monocyclic aromatic group and / ormulticyclic aromatic group that contain at least one aromatic ring, wherein at least one aromatic ring contains one or more heteroatoms independently selected from O, S, and N in the ring. Heteroaryl groups are bonded to the rest of the molecule through the aromatic ring. Each ring of a heteroaryl group can contain one or two O atoms, one or two S atoms, and / or one to four N atoms, provided that the total number of heteroatoms in each ring is four or less and each ring contains at least one carbon atom. In certain embodiments, the heteroaryl has from 5 to 20, from 5 to 15, or from 5 to 10 ring atoms. In certain embodiments, the heteroaryl has six to ten ring atoms, i.e., C6-10heteroaryl. Examples of monocyclic heteroaryl groups include, but are not limited to, furanyl, imidazolyl, isothiazolyl, isoxazolyl, oxadiazolyl, oxadiazolyl, oxazolyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl, thiadiazolyl, thiazolyl, thienyl, tetrazolyl, triazinyl, and triazolyl. Examples of bicyclic heteroaryl groups include, but are not limited to, benzofuranyl, benzimidazolyl, benzoisoxazolyl, benzopyranyl, benzothiadiazolyl, benzothiazolyl, benzothienyl, benzotriazolyl, benzoxazolyl, furopyridyl, imidazopyridinyl, imidazothiazolyl, indolizinyl, indolyl, indazolyl, isobenzofuranyl, isobenzothienyl, isoindolyl, isoquinolinyl, isothiazolyl, naphthyridinyl, oxazolopyridinyl, phthalazinyl, pteridinyl, purinyl, pyridopyridyl, pyrrolopyridyl, quinolinyl, quinoxalinyl, quinazolinyl, thiadiazolopyrimidyl, and thienopyridyl. Examples of tricyclic heteroaryl groups include, but are not limited to, acridinyl, benzindolyl, carbazolyl, dibenzofuranyl, perimidinyl, phenanthrolinyl, phenanthridinyl, phenarsazinyl, phenazinyl, phenothiazinyl, phenoxazinyl, and xanthenyl. In certain embodiments, heteroaryl may also be optionally substituted as described herein. In certain embodiments, a heteroaryl group refers to a monocyclic 5- or 6-membered heteroaryl group optionally substituted by a C1-3alkyl group in the carbon skeleton, where - 10 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 the 6-membered heteroaryl group contains one, two, or three nitrogen atoms and the 5-membered heteroaryl group contains an imino group optionally substituted by a C1-3- alkyl or phenyl-C1-3-alkyl group, an oxygen or sulfur atom, or an imino group optionallysubstituted by a C1-3-alkyl or phenyl-C1-3-alkyl group or an oxygen or sulfur atom and additionally a nitrogen atom or an imino group optionally substituted by a C1-3-alkyl or phenyl-C1-3-alkyl group and two nitrogen atoms, and where a phenyl ring may be fused to the abovementioned monocyclic heterocyclic group via two adjacent carbon atoms, in which the bonding takes place via a nitrogen atom or via a carbon atom of the heterocyclic moiety or a fused phenyl ring.

[0054] The term “protecting group” as used herein and unless otherwise defined refers to agroup that is added to an oxygen, nitrogen, or phosphorus atom to prevent its further reaction or for other purposes. A wide variety of oxygen and nitrogen protecting groups are known to those skilled in the art of organic synthesis. See Greene, et al., Protective Groups in Organic Synthesis, John Wiley and Sons, Second Edition, 1991, the entire contents of which are herein incorporated by reference in its entirety.

[0055] The term “amine-compatible protection group,” refers to a protecting group thatbonds to an amine group. For example, trimethylsilyl (“TMS”) and tert- butyloxycarbonyl (“BOC”)TMS are example amine-compatible protection group that bond to an amine group.

[0056] As used herein, the term “hydrophobic” means and includes any material or surfacewith which water droplets have a contact angle in air of at least 90°, as measured by a contact angle goniometer as described in ASTM D7334-08. Furthermore, as used herein, the term “superhydrophobic” means and includes any material or surface with which water droplets have a contact angle in air of at least 150°, as measured by a contact angle goniometer as described in ASTM D7334-08. Thus, a “superhydrophobic” material will also be considered “hydrophobic;” however, a “hydrophobic” material may not necessarily be “superhydrophobic” in certain embodiments. In various embodiments, the hydrophobic coatings of substrates herein can comprise a contact angle in air of at least 90° or about 90°, at least 100° or about 100°, at least 110° or about 110°, or at least 120° or about 120°, at least 130° or about 130°, at least 140° or about 140°, at least 150° or - 11 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 about 150°, at least 160° or about 160°, or at least 170° or about 170°. In various embodiments, the hydrophobic coatings of substrates herein can comprise a contact angle in air of at 120°C. In various embodiments, the hydrophobic coatings of substrates herein can comprise a contact angle in air of 110 – 130 °.

[0057] As used herein, “substrate” refers to flexible substrates; rigid substrates; andsubstrates made of, or which comprise, consist, or consist essentially of poly(tetrafluoro)ethylene (PTFE), polyolefins, metals (e.g., steel), composites, carbon fiber, releasable film, wood, fiberglass, composite materials, glass, rubber, ceramic, an adhesive film, paint, ship hulls, submarines, off-shore floating structures, fishing / aquaculture equipment, fishing / aquaculture installations, pipes / pipelines, drilling rigs, floating buoys, storage containers, any surface in contact with an aqueous environment, air / refrigeration systems and ducts, dams, bridges, and other civil constructions. In some embodiments, a substrate has a coating thereupon. In other embodiments, the substrate can be formed from any material known in the art, such as plastics, glass, fused silica, fiberglass, ceramic, metals, wood, fabrics, carbon fiber, fabrics and textiles, and the like. Examples of suitable substrates include polymer substrates, PTFE substrates, and substrates such as polydimethylsiloxane (PDMS), polyethylene terephthalate (PET), polycarbonate (PC), polyurea (PU), or combinations thereof; glass substrates; or metal substrates, such as steel (e.g., mild steel containing 0.15% to 0.23 % carbon) or aluminum alloys; or a combination thereof. Substrates may also include concrete. The substrate can be in any configuration configured to facilitate formation of a coating suitable for use in a particular application. In exemplary embodiments, the substrate can be a releasable film. In certain embodiments, the substrate is steel. In certain other embodiments, the substrate is polyethylene. In certain embodiments, the substrate is concrete. In some embodiments, the substrate is substrate can be a polyolefin, nylon, textile, plastic and / or composite, glass, wood, fibreglass, or metal.

[0058] Suitable fluoropolymers for use with the polymer blends, substrates, and / or coatings,disclosed herein include, e.g., polytetrafluroroethylene (PTFE), polyvinylfluoride (PVF), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), perfluoroalkoxy polymer (PFA), fluorinated ethylene-propylene (FEP), ethylene tetrafluoroethylene - 12 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 (ETFE) and related perfluoro elastomers. In certain embodiments, the PTFE may be porous, an unsintered film, or a thermally annealed, sintered film. Suitable poly(olefin)s for use in the instant disclosure include polypropylene (PP), polyethylene (PE), polybutadiene (PBD), polystyrene (PS), polyvinylchloride (PVC), and combinations thereof. Other fluoropolymer materials are available from Saint Gobain (https: / / www.plastics.saint-gobain.com / ). See part numbers # 128060WHT-FW and #SF00000540000C.

[0059] As used herein, a polymer with free-amine groups refers to a polymer substituted withamine groups that are not part of the polymer backbone. The amine substituents are primary or secondary amines that include at least one hydrogen that is capable of forming reversible hydrogen bonds.

[0060] As used herein, the term “repressing” refers to the second or subsequent time apolymer blend is pressed onto a substrate after the polymer blend was previously pressed on the substrate and subsequently removed (whole or partly) from the substrate. Repressing also refers to the second or subsequent time two substrates with a polymer blend therebetween are pressed together after the substrates with a polymer blend therebetween have been separated. For example, if a polymer blend adheres two substrates together and later the substrates delaminate from each other, the two substrates may be repressed back together, optionally with heat applied, to re-adhere the two substrates to each other with the polymer blend, or a residual amount of the polymer blend between the two substrates. Removing the polymer blend from the substrate can include, but is not limited to, peeling the polymer from the substrate, lifting the polymer blend off the substrate, naturally or spontaneously allowing the polymer blend to delaminate from the substrate, or scraping the polymer blend from the substrate. POLYMER BLENDS

[0061] In one embodiment, set forth herein is a polymer blend that includes an amine-functionalized polymer (APE); and a poly (ethylene-co-vinyl acetate) (EVA) co-polymer.

[0062] In some embodiments, including any of the foregoing, the APE is not a memberselected from the group consisting of a nylon polymer, a nitrile polymer, a polyurethane polymer, a polyurea polymer, a polyetheramine polymer, or a combination thereof. - 13 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044

[0063] In some embodiments, including any of the foregoing, the APE is a polymer withfree-amine groups.

[0064] In some embodiments, including any of the foregoing, the APE is an amine-functionalized polyolefin.

[0065] In some embodiments, including any of the foregoing, the APE is substituted withprimary or secondary amine substituents.

[0066] In certain embodiments, including the foregoing, the EVA has the followingstructure: , in which subscript n is from 1to 100,000; and the mass ratio of m:n is about 4% by weight to about 60% by weight. In some embodiments, m:n is 10% by weight. In some other embodiments, m:n is 15% by weight. In other embodiments, m:n is 20% by weight. In yet other embodiments, m:n is 25% by weight. In certain embodiments, m:n is 30% by weight. In certain other embodiments, m:n is 35% by weight. In some embodiments, m:n is 40% by weight. In some other embodiments, m:n is 45% by weight. In other embodiments, m:n is 50% by weight. In yet other embodiments, m:n is 55% by weight. In certain embodiments, m:n is 60% by weight.

[0067] In certain embodiments, including the foregoing, the APE has a structure thatincludes a polymer made from the following repeating units: - 14 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 m 2

[0068] In some embodiments, including any of the foregoing, the APE:EVA mass ratio is1:3 or higher.

[0069] In some embodiments, including any of the foregoing, the APE:EVA mass ratio is2:1 or higher.

[0070] In some embodiments, including any of the foregoing, the APE:EVA mass ratio is1:3 to 10:1.

[0071] In some embodiments, including any of the foregoing, the APE:EVA mass ratio is2:1 to 1,000:1.

[0072] In some embodiments, including any of the foregoing, the APE:EVA mass ratio is2:1 to 10:1.

[0073] In some embodiments, including any of the foregoing, the APE:EVA mass ratio is1:1; 3:2; 3:1, or 9:1.

[0074] In some embodiments, including any of the foregoing, the APE:EVA mass ratio is1:3, 1:1, or 3:1.

[0075] In some embodiments, including any of the foregoing, the APE:EVA mass ratio is1:2, 1:1, 1.5:1, 2.5:1, 3.5:1, 4:1, or 5:1.

[0076] In some embodiments, including any of the foregoing, the APE:EVA mass ratio is29:21; 33:22, 83:17, or 91:9.

[0077] In some embodiments, including any of the foregoing, the APE:EVA mass ratiotolerance is ± 10%. For example, in some embodiments, including any of the foregoing, - 15 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 the APE:EVA mass ratio is 3:1 ± 10%. For example, in some embodiments, including any of the foregoing, the APE:EVA mass ratio is 2:1 ± 10%.

[0078] In some embodiments, including any of the foregoing, the APE:EVA mass ratio is1:1, 3:1, 29:21; 33:17, 83:17, or 91:9; wherein the mass ratio is ± 10%, ± 9%, ± 8%, ± 7%,± 6%, ± 5%,± 4%, ± 3%,± 2%, or ± 1%.

[0079] In some embodiments, including any of the foregoing, the molecular weight of theAPE is about 1,000 kg / mol to about 100,000 g / mol.

[0080] In some embodiments, including any of the foregoing, the molecular weight of theAPE is about 40,000 g / mol to about 70,000 g / mol.

[0081] In some embodiments, including any of the foregoing, the molecular weight of theAPE is about 20,000 g / mol to about 40,000 g / mol.

[0082] In some embodiments, including any of the foregoing, the molecular weight of theAPE is greater than 70,000 g / mol.

[0083] In some embodiments, including any of the foregoing, the molecular weight of theAPE is about 10,000 g / mol. In some embodiments, including any of the foregoing, the molecular weight of the APE is about 15,000 g / mol. In some embodiments, including any of the foregoing, the molecular weight of the APE is about 20,000 g / mol. In some embodiments, including any of the foregoing, the molecular weight of the APE is about 25,000 g / mol. In some embodiments, including any of the foregoing, the molecular weight of the APE is about 30,000 g / mol. In some embodiments, including any of the foregoing, the molecular weight of the APE is about 35,000 g / mol. In some embodiments, including any of the foregoing, the molecular weight of the APE is about 40,000 g / mol. In some embodiments, including any of the foregoing, the molecular weight of the APE is about 45,000 g / mol. In some embodiments, including any of the foregoing, the molecular weight of the APE is about 50,000 g / mol. In some embodiments, including any of the foregoing, the molecular weight of the APE is about 55,000 g / mol. In some embodiments, including any of the foregoing, the molecular weight of the APE is about 60,000 g / mol. In some embodiments, including any of the foregoing, the molecular weight of the APE is about 65,000 g / mol. In some embodiments, including any of the foregoing, the molecular weight of the APE is about 70,000 g / mol. In some embodiments, including any of the foregoing, the molecular - 16 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 weight of the APE is about 75,000 g / mol. In some embodiments, including any of the foregoing, the molecular weight of the APE is about 80,000 g / mol. In some embodiments, including any of the foregoing, the molecular weight of the APE is about 85,000 g / mol. In some embodiments, including any of the foregoing, the molecular weight of the APE is about 90,000 g / mol. In some embodiments, including any of the foregoing, the molecular weight of the APE is about 95,000 g / mol. In some embodiments, including any of the foregoing, the molecular weight of the APE is about 100,000 g / mol.

[0084] In some embodiments, including any of the foregoing, the EVA has a melt indexof 40 to 60 g / min at 190 ºC.

[0085] In some embodiments, including any of the foregoing, the EVA has a melt indexof 57 g / min at 190 ºC.

[0086] In some embodiments, including any of the foregoing, the APE comprises thestructure of Formula (Ia), Formula (Ib), or both Formula (Ia) and Formula (IIb):wherein: indicates a single bond or a double bond; R1and R2are, independently, selected from the group consisting of OH, C1-15alkyl, C2-15alkenyl, C2-15alkynyl, C6-10aryl, C4-10cycloalkyl,C4-10heterocycloalkyl, a terminating end group; R3is C1-6alkyl- NR4R5; R4and R5: (a) are independently selected from the group consisting of H, C1-6alkyl, C3-10cylcoalkyl, C3-10cylcoalkenyl, C3-10heterocylcoalkyl, C3-10heterocylcoalkenyl, C6-10aryl, C6-10heteroaryl, and an amine-compatible protection group; or (b) together with the nitrogen atom to which they are attached, form a cyclic or heterocyclic group selected from the group consisting of C6-10heteroaryl, C6-10heterocycloalkyl, or C6-10heterocycloalkenyl; R1, R2, R3, R4, and R5are independently optionally substituted - 17 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 by one to six substituents selected from the group consisting of OH, C1-5alkyl, C1-5heteroalkyl, C1-5alkoxy, halo, C1-5 haloalkoxy, amino, nitro, carbonyl, and carboxyl; subscript p is, independently for each formula, an integer equal to 2 to 100,000.

[0087] In some embodiments, including any of the foregoing, the APE comprises thestructure of Formula (Ia), Formula (Ib), or both Formula (Ia) and Formula (IIb):w ere n: n ca es a s ng e on or a ou e on ; an are, n epen en y, selected from the group consisting of OH, C1-15alkyl, C2-15alkenyl, C2-15alkynyl, C6- 10aryl, C4-10cycloalkyl,C4-10heterocycloalkyl, a terminating end group; R3is C1-6alkyl- NR4R5; R4and R5are independently selected from the group consisting of H, C1-6alkyl, C3-10cylcoalkyl, C3-10cylcoalkenyl, C3-10heterocylcoalkyl, C3-10heterocylcoalkenyl, C6- 10aryl, C6-10heteroaryl, and an amine-compatible protection group; R1, R2, R3, R4, and R5are independently optionally substituted by one to six substituents selected from the group consisting of OH, C1-5alkyl, C1-5heteroalkyl, C1-5alkoxy, halo, C1-5haloalkoxy, amino, nitro, carbonyl, and carboxyl; subscript p is, independently for each formula, an integer equal to 2 to 100,000.

[0088] In some embodiments, including any of the foregoing, at least one of R4 and R5 isnot H.

[0089] In some embodiments, including any of the foregoing, the APE comprises, orfurther comprises, the structure of Formula (IIa), Formula (IIb), or both Formula (IIa) and Formula (IIb): - 18 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 R2R2wherein: indicates a single bond or a double bond; R1and R2are, independently, selected from the group consisting of OH, C1-15alkyl, C2-15alkenyl, C2-15alkynyl, C6-10aryl, C4-10cycloalkyl, C4-10heterocycloalkyl, a terminating end group; R3is C1-6alkyl- NR4R5; R4and R5: (a) are independently selected from the group consisting of H, C1-6alkyl, C3-10cylcoalkyl, C3-10cylcoalkenyl, C3-10heterocylcoalkyl, C3-10heterocylcoalkenyl, C6-10aryl, C6-10heteroaryl, and an amine-compatible protection group; or (b) together with the nitrogen atom to which they are attached, form a cyclic group selected from the group consisting of C6-10heteroaryl, C6-10heterocycloalkyl, or C6-10heterocycloalkenyl; and R1, R2, R3, R4, and R5are independently optionally substituted by one to six substituents selected from the group consisting of OH, C1-5alkyl, C1-5alkoxy, halo, C1-5haloalkoxy, amino, nitro, or carboxyl; R7is, independently in each instance, selected from the group consisting of OH, C1-5alkyl, C1-5alkoxy, halo, C1-5haloalkoxy, amino, nitro, carbonyl, and carboxyl; or wherein two R7substituents together with the carbons to which they are attached for a C4-6cycloalkyl or C4-6cycloalkenyl ring; subscripts s and t are - 19 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 independently selected from an integer of 1 to 100,000; subscript r is an integer from 0 to 6.

[0090] In some embodiments, including any of the foregoing, the APE comprises, orfurther comprises, the structure of Formula (IIa), Formula (IIb), or both Formula (IIa) and Formula (IIb): R2R2wherein: indicates a single bond or a double bond; R1and R2are, independently, selected from the group consisting of OH, C1-15alkyl, C2-15alkenyl, C2-15alkynyl, C6-10aryl, C4-10cycloalkyl, C4-10heterocycloalkyl, a terminating end group; R3is C1-6alkyl- NR4R5; R4and R5are independently selected from the group consisting of H, C1-6alkyl, C3-10cylcoalkyl, C3-10cylcoalkenyl, C3-10heterocylcoalkyl, C3-10heterocylcoalkenyl, C6-10aryl, C6-10heteroaryl, and an amine-compatible protection group; and R1, R2, R3, R4, and R5are independently optionally substituted by one to six substituents selected from the group consisting of OH, C1-5alkyl, C1-5alkoxy, halo, C1-5haloalkoxy, - 20 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 amino, nitro, or carboxyl; R7is, independently in each instance, selected from the group consisting of OH, C1-5alkyl, C1-5alkoxy, halo, C1-5haloalkoxy, amino, nitro, carbonyl, and carboxyl; or wherein two R7substituents together with the carbons to which they are attached for a C4-6cycloalkyl or C4-6cycloalkenyl ring; subscripts s and t are independently selected from an integer of 1 to 100,000; subscript r is an integer from 0 to 6.

[0091] In some embodiments, including any of the foregoing, at least one of R4 and R5 isnot H.

[0092] In some embodiments, including any of the foregoing, two R7 substituents form aC4-6cycloalkyl or C4-6cycloalkenyl ring.

[0093] In some embodiments, including any of the foregoing, the APE comprises, orfurther comprises, the structure of Formula (IIa1), Formula (IIb1), or both Formula (IIa1) and Formula (IIb1): ; 148\1\AMERICASAttorney Docket No.: 125298.00044 (IIb1)

[0094] In the above formula, indicates a single bond or a double bond. R1, R2, R8,and R9, are independently, selected from the group consisting of OH, C1-15alkyl, C2- 15alkenyl, C2-15alkynyl, C6-10aryl, C4-10cycloalkyl, C4-10heterocycloalkyl, and a terminating end group; subscripts b, c, d, x, and p, are independently selected from an integer of 1 to 100,000; subscript g is an integer from 0 to 5; and Z is H, OCF3, F, Cl, Br, I, or OCH3.

[0095] In some embodiments, including any of the foregoing, R8 and / or R9 are initiationpoint for ROMP. In certain embodiments, R8and / or R9can be another propagating polymer chain that may or may not cross-metathesize / back-bite / cross-link with another polymer chain. In certain embodiments, R8and / or R9can bond to another polymer fragment, for example, in a crosslinking fashion.

[0096] In some embodiments, including any of the foregoing, the APE comprises, orfurther comprise, the structure of Formula (IIa2), Formula (IIb2), or both Formula (IIa2) and Formula (IIb2): ;- 22 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044

[0097] In the above formula, indicates a single bond or a double bond. R1, R2, R8,and R9, are independently, selected from the group consisting of OH, C1-15alkyl, C2- 15alkenyl, C2-15alkynyl, C6-10aryl, C4-10cycloalkyl, C4-10heterocycloalkyl, and a terminating end group; subscripts b, c, d, x, and p are independently selected from an integer of 1 to 100,000; and Z is H, OCF3, F, Cl, Br, I, or OCH3.

[0098] In some embodiments, including any of the foregoing, R8 and / or R9 are initiationpoint for ROMP. In certain embodiments, R8and / or R9can be another propagating polymer chain that may or may not cross-metathesize / back-bite / cross-link with another polymer chain. In certain embodiments, R8and / or R9can bond to another polymer fragment, for example, in a crosslinking fashion.

[0099] In some embodiments, including any of the foregoing, the NR4R5 is pyrrolidine;piperidine; ; wherein Z is H, OH, OR10, OCF3, F, Cl, Br, I, SOCH3or OCH3, CH3, ; and subscript q is from 0 to 5; an represents the point of attachment of NR4R5to the polymer;wherein R10is H, C1-6alkyl, or a protecting group. In certain embodiments, q is 0. In - 23 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 certain embodiments, q is 1. In certain embodiments, q is 2. In certain embodiments, q is 3. In certain embodiments, q is 4. In certain embodiments, q is 5.

[0100] In some embodiments, including any of the foregoing, the NR4R5 is pyrrolidine;piperidine; ; wherein Z is H, OCF3, F, Cl, Br, I, or OCH3; andsubscript q is from 0 to 5; and represents the point of attachment of NR4R5to the polymer. In certain embq is 0. In certain embodiments, q is 1. In certain embodiments, q is 2. In certain embodiments, q is 3. In certain embodiments, q is 4. In certain embodiments, q is 5.

[0101] In certain embodiments, q is 0. In certain embodiments, q is 1. In certainembodiments, q is 2. In certain embodiments, q is 3. In certain embodiments, q is 4. In certain embodiments, q is 5.

[0102] In some embodiments, including any of the foregoing, NR4R5 is pyrrolidine;piperidine ; wherein Z is H, OCF3, F, Cl, Br, I, or OCH3;d represents the point of attachment of NR4R5to the polymer.[01n some embodiments, including any of the foregoing, NR4R5 isd wherein Z is H, OCF3, F, Cl, Br, I, or OCH3.[01s, including any of the foregoing, the amine-functionalizedpolymer comprises the structure of Formula (IIIa), (IIIb), or both Formula (IIIa) and (IIIb): - 24 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044(IIIb); wherein indicates a single bond or a double bond; R1and R2are, independently, selected from the group consisting of OH, C1-15alkyl, C2-15alkenyl, C2-15alkynyl, C6-10aryl, C4-10heterocycle, a terminating end group; R1and R2are independently optionally substituted by one to six substituents selected from the group consisting of OH, C1-5alkyl, C1-5alkoxy, halo, - 25 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 C1-5haloalkoxy, amino, nitro, carbonyl, and carboxyl; subscript p is from 2 to 100,000; R6is selected from the group consisting of OH, C1-5alkyl,C1-5alkoxy, halo, C1-5 haloalkoxy, amino, nitro, and carboxyl.

[0105] In some embodiments, including any of the foregoing, R6 is H, OCF3, F, Cl, Br, I,or OCH3.

[0106] In some embodiments, including any of the foregoing, the APE has the structureof Formula (IVa), Formula (IVb), or both Formula (IVa) and Formula (IVb):- 26 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 wherein R6is H, O 3; and R8ais H, C1-6alkyl, or a protecting group. In certain embodiments, R6is H. In certain embodiments, R6is OH. In certain embodiments, R6is OR8a. In certain embodiments, R6is OCF3. In certain embodiments, R6is F. In certain embodiments, R6is Cl. In certain embodiments, R6is Br. In certain embodiments, R6is I. In certain embodiments, R6is SOCH3. In certain embodiments, R6is OCH3. In certain embodiments, R6is CH3.

[0107] In some embodiments, including any of the foregoing, R6 is F, Cl, Br, or I.

[0108] In some embodiments, including any of the foregoing, R6 is F.

[0109] In some embodiments, including any of the foregoing, the EVA has the structureof Formula (V): 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 wherein subscript n is from 1 to 100,000; and subscript m is from 1 to 100,000; and the mass ratio of m:n is about 4% by weight to about 60% by weight.

[0110] In some embodiments, including any of the foregoing, the polymer blend has atleast 18% by weight VA in the compound having the structure of Formula (V).

[0111] In some embodiments, including any of the foregoing, the polymer blend has atleast 25% by weight VA by weight VA in the compound having the structure of Formula (V).

[0112] In some embodiments, including any of the foregoing, the polymer blend has atleast 40% by weight VA by weight VA in the compound having the structure of Formula (V).

[0113] In some embodiments, including any of the foregoing, the mass ratio of n:m is 3:2by weight.

[0114] In some embodiments, including any of the foregoing, the indicates a singlebond.

[0115] In some embodiments, including any of the foregoing, the indicates adouble bond.

[0116] In some embodiments, including any of the foregoing, the APE is made using atwo-step catalytic combination of hydroaminoalkylation and ring-opening metathesis polymerization (ROMP). See WO2019222834A1, which published November 28, 2019, and is titled GROUP 5 METAL COMPLEXES FOR PRODUCING AMINE- FUNTIONALIZED POLYOLEFINS, and WO2019222852A1, which published November 28, 2019, and is titled NOVEL AMINE FUNCTIONALIZED POLYMERS AND METHODS OF PREPARATION, the entire contents of each of which are herein incorporated by reference in their entirety for all purposes. See also, Leitgeb, A.; Wappel, J.; Slugovc, C., The ROMP toolbox upgraded. Polymer 2010, 51 (14), 2927-2946; also Ogba, O.; Warner, N.; O’leary, D.; Grubbs, R., Recent advances in ruthenium-based olefin metathesis. Chem. Soc. Rev.2018, 47 (12), 4510-4544, the entire contents of each of which are herein incorporated by reference in their entirety for all purposes.

[0117] In some embodiments, including any of the foregoing, the APE comprises, orfurther comprises, at least one of the following structures: - 28 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 ; ; ; ; 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 ; ; ; ; 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 ; ; ; , 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 or ; wh, than 500,000.

[0118] In some embodiments, including any of the foregoing, n:m is 3:1.

[0119] In some embodiments, including any of the foregoing, n:m is 2:1.

[0120] In some embodiments, including any of the foregoing, n:m is 1:1.

[0121] In some embodiments, including any of the foregoing, n:m is 1:2.

[0122] In some embodiments, including any of the foregoing, n:m is 1:3

[0123] In some embodiments, including any of the foregoing, the polymer blend hasadhesive properties.

[0124] In some embodiments, including any of the foregoing, the polymer blend has anaverage peeling strength of 600 N / m or greater on a PTFE substrate. - 32 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044

[0125] In some embodiments, including any of the foregoing, the polymer blend has anaverage peeling strength of 700 N / m or greater on a PTFE substrate.

[0126] In some embodiments, including any of the foregoing, the polymer blend has anaverage peeling strength of 800 N / m or greater on a PTFE substrate.

[0127] In some embodiments, including any of the foregoing, the polymer blend has anaverage peeling strength of 900 N / m or greater on a PTFE substrate.

[0128] In some embodiments, including any of the foregoing, the polymer blend has anaverage peeling strength of 1,000 N / m or greater on a PTFE substrate.

[0129] In some embodiments, including any of the foregoing, the APE monomer unitsare connected in a head to head fashion, head to tail fashion, tail to tail fashion, or any combination thereof.

[0130] In some embodiments, including any of the foregoing, the polymer blendsincludes ionomers.

[0131] In some embodiments, including any of the foregoing, the ionomer is neutralized.SUBSTRATES COATED WITH POLYMER BLENDS

[0132] In another embodiment, set forth herein is a substrate coated with a polymer blendthat is disclosed herein.

[0133] In another embodiment, set forth herein is apparel, shoes, book bindings, and / orautomotive parts that include a surface or interface coated with a polymer blend that is disclosed herein.

[0134] In another embodiment, set forth herein is a substrate comprising a polymer blendthat is disclosed herein disposed on at least one surface or at least interface.

[0135] In some embodiments, including any of the foregoing, the substrate has a coating.

[0136] In some embodiments, including any of the foregoing, the substrate has ahydrophobic coating.

[0137] In some embodiments, including any of the foregoing, the substrate is a lowenergy substrate.

[0138] In some embodiments, including any of the foregoing, the substrate is selectedfrom the group consisting of PTFE, polyethylene, polypropylene, polyolefin, nylon, textile, plastic, composite, glass, wood, fiberglass, metal, and combinations thereof. - 33 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044

[0139] In some embodiments, including any of the foregoing, the substrate is afluoropolymer selected from the group consisting of polytetrafluroroethylene (PTFE), polyvinylfluoride (PVF), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), perfluoroalkoxy polymer (PFA), fluorinated ethylene-propylene (FEP), and related perfluoro elastomers.

[0140] In some embodiments, including any of the foregoing, the substrate is PTFE.

[0141] In some embodiments, including any of the foregoing, the substrate is PTFE andwherein the PTFE is porous.

[0142] In some embodiments, including any of the foregoing, the substrate is non-surfacemodified PTFE.

[0143] In another embodiment, set forth herein is a process for recycling a polymer blenddisclosed herein, comprising removing, or allowing to be removed, the polymer blend from a substrate, dissolving the polymer blend, heating the polymer blend, or a combination thereof, and redepositing the polymer blend onto the substrate or a different substrate.

[0144] In another embodiment, set forth herein a process for repressing a polymer blenddisclosed herein, comprising disposing the polymer blend on a substrate, removing, or allowing to be removed, the polymer blend from a substrate, and repressing the polymer blend to the substrate or a different substrate.

[0145] In another embodiment, set forth herein a process for repressing a polymer blenddisclosed herein, comprising disposing the polymer blend on at least two substrates, removing, or allowing to be removed, the polymer blend from the at least two substrates, wherein the at least two substrates had residual amounts of polymer bend thereupon, pressing the at least two substrates with residual amounts of polymer blend against each other to join the residual amounts of adhesive, and melt pressing the two substrates. In some embodiments, the melt pressing was at 70 ºC. In some embodiments, the melt pressing was for about 5 minutes.

[0146] In some embodiments, including any of the foregoing, the repressing is at apressure from 0.1 MPa to 100 MPa.

[0147] In some embodiments, including any of the foregoing, the repressing is higherthan 0.5 MPa. - 34 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044

[0148] In some embodiments, including any of the foregoing, the repressing is higherthan 1 MPa.

[0149] In some embodiments, including any of the foregoing, the repressing is at atemperature at or greater than 60 ºC.

[0150] In some embodiments, including any of the foregoing, the repressing is at atemperature at or greater than 90 ºC.

[0151] In some embodiments, including any of the foregoing, the repressing is at 1 MPaat a temperature at or greater than 90 ºC.

[0152] In some embodiments, set forth herein is a process for self-healing a polymerblend disclosed herein, comprising disposing the polymer blend on a substrate, and heating the polymer blend, applying a solvent to the polymer blend, or both heating the polymer blend and applying a solvent to the polymer blend

[0153] In some embodiments, including any of the foregoing, the polymer blend iscracked or delaminated from the substrate before the heating or applying a solvent, and wherein the polymer blend is not cracked, not delaminated, or both not cracked and not delaminated after the heating or applying a solvent.

[0154] In some embodiments, including any of the foregoing, the polymer blend does notrelease volatile organic compounds (VOCs).

[0155] In another embodiment, set forth herein is a trilayer that includes a polymer blenddisclosed herein between, and in contact with, two substrates.

[0156] In some embodiments, including any of the foregoing, the two or more substatesare different substrates.

[0157] In some embodiments, including any of the foregoing, the two or more substatesare the same substrate.

[0158] In another embodiment, set forth herein is a process for making a film of apolymer blend that includes mixing in a solvent an amine-functionalized polymer (APE) and a poly (ethylene-co-vinyl acetate) (EVA) co-polymer to form a solvent mixture; wherein the APE:EVA mass ratio is 1:3 to 10:1; casting the solvent mixture on a substrate; and drying the casted solvent mixture to form a film on the substrate. - 35 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044

[0159] In some embodiments, including any of the foregoing, the APE:EVA mass ratio is1:3 or higher.

[0160] In some embodiments, including any of the foregoing, the APE:EVA mass ratio is2:1 or higher.

[0161] In some embodiments, including any of the foregoing, the APE:EVA mass ratio is1:3 to 10:1.

[0162] In some embodiments, including any of the foregoing, the APE:EVA mass ratio is2:1 to 1,000:1.

[0163] In some embodiments, including any of the foregoing, the APE:EVA mass ratio is2:1 to 10:1.

[0164] In some embodiments, including any of the foregoing, the APE:EVA mass ratio is1:1; 3:2; 3:1, or 9:1.

[0165] In some embodiments, including any of the foregoing, the APE:EVA mass ratio is1:3, 1:1, or 3:1.

[0166] In some embodiments, including any of the foregoing, the APE:EVA mass ratio is1:2, 1:1, 1.5:1, 2.5:1, 3.5:1, 4:1, or 5:1.

[0167] In some embodiments, including any of the foregoing, the APE:EVA mass ratio is29:21; 33:22, 83:17, or 91:9.

[0168] In some embodiments, including any of the foregoing, the film is disposed on thesubstrate.

[0169] In some embodiments, including any of the foregoing, the film is a hot meltadhesive.

[0170] In some embodiments, including any of the foregoing, the process includespressing the film onto another substrate and heating the film.

[0171] In some embodiments, including any of the foregoing, the film thickness is 1 µmto 1 mm.

[0172] In some embodiments, including any of the foregoing, the film thickness is 0.1mm. In some embodiments, including any of the foregoing, the film thickness is 0.2 mm. In some embodiments, including any of the foregoing, the film thickness is 0.3 mm. In some embodiments, including any of the foregoing, the film thickness is 0.4 mm. In some embodiments, including any of the foregoing, the film thickness is 0.5 mm. In some - 36 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 embodiments, including any of the foregoing, the film thickness is 0.6 mm. In some embodiments, including any of the foregoing, the film thickness is 0.7 mm. In some embodiments, including any of the foregoing, the film thickness is 0.8 mm. In some embodiments, including any of the foregoing, the film thickness is 0.9 mm. In some embodiments, including any of the foregoing, the film thickness is 1.0 mm.

[0173] In some embodiments, including any of the foregoing, the solvent istetrahydrofuran (THF).

[0174] In some embodiments, including any of the foregoing, the process furtherincludes dissolving the polymer blend in a solvent to form a second solvent mixture; casting the second solvent mixture on a substrate; and drying the casted solvent mixture to form a film on the substrate.

[0175] In some embodiments, including any of the foregoing, the process furtherincludes removing the polymer blend from the substrate and repressing the polymer blend to the substrate.

[0176] In some embodiments, including any of the foregoing, the process includesevaporating the solvent from the solvent mixture.

[0177] In some embodiments, including any of the foregoing, the process includesevaporating the solvent from the solvent mixture completely.

[0178] Also set forth herein is a thermoplastic made by a process disclosed herein.

[0179] In some embodiments, including any of the foregoing, the thermoplastic is a hotmelt adhesive. PROCESSESS OF MAKING AND USING

[0180] In some embodiments, set forth herein is a process for disposing a polymer blendon a substrate, wherein the process includes providing a polymer blend that is disclosed herein; heating the polymer blend above its melting temperature; disposing the polymer blend on a substrate; and cooling the polymer blend below its melting temperature.

[0181] In some other embodiments, set forth herein is a process for disposing a polymerblend on a substrate, wherein the process includes providing a polymer blend that is disclosed herein; heating the polymer blend above its melting temperature; applying the polymer blend on a substrate; and cooling the polymer blend below its melting temperature. - 37 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044

[0182] In some embodiments, including any of the foregoing, the process includespressing the polymer blend on a substrate.

[0183] In some embodiments, including any of the foregoing, the pressing is at a pressurefrom 0.1 MPa to 100 MPa.

[0184] In some embodiments, including any of the foregoing, the pressing is higher than0.5 MPa.

[0185] In some embodiments, including any of the foregoing, the pressing is higher than1 MPa.

[0186] In some embodiments, including any of the foregoing, the pressing is at atemperature at or greater than 60 ºC.

[0187] In some embodiments, including any of the foregoing, the pressing is at atemperature at or greater than 90 ºC.

[0188] In some embodiments, including any of the foregoing, the pressing is at 1 MPa ata temperature at or greater than 90 ºC.

[0189] In some embodiments, including any of the foregoing, the pressing is for 3minutes.

[0190] In some embodiments, including any of the foregoing, the process furtherincludes removing the polymer blend from the substrate and repressing the polymer blend back on the substrate.

[0191] In some embodiments, including any of the foregoing, the repressing is at apressure from 0.1 MPa to 100 MPa.

[0192] In some embodiments, including any of the foregoing, the repressing is higherthan 0.5 MPa.

[0193] In some embodiments, including any of the foregoing, the repressing is higherthan 1 MPa.

[0194] In some embodiments, including any of the foregoing, the repressing is at atemperature at or greater than 60 ºC.

[0195] In some embodiments, including any of the foregoing, the repressing is at atemperature at or greater than 90 ºC. - 38 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044

[0196] In some embodiments, including any of the foregoing, the repressing is at 1 MPaat a temperature at or greater than 90 ºC.

[0197] In some embodiments, including any of the foregoing, the repressing is for 3minutes.

[0198] In a ninth embodiment, set forth herein is a process for disposing a polymer blendon a substrate, that includes providing a polymer blend that is disclosed herein; and pressing the polymer blend onto a substrate at a pressure of 0.1 MPa to 100 MPa and a temperature of 40 ºC to 200 ºC.

[0199] In some embodiments, including any of the foregoing, the pressing is for 3minutes.

[0200] In some embodiments, including any of the foregoing, the pressing is higher than0.5 MPa.

[0201] In some embodiments, including any of the foregoing, the pressing is higher than1 MPa.

[0202] In some embodiments, including any of the foregoing, the pressing is at atemperature at or greater than 60 ºC.

[0203] In some embodiments, including any of the foregoing, the pressing is at atemperature at or greater than 90 ºC.

[0204] In some embodiments, including any of the foregoing, the pressing is at 1 MPa ata temperature at or greater than 90 ºC.

[0205] In some embodiments, including any of the foregoing, the process includesmelting the polymer blend.

[0206] In another embodiment, set forth herein is a polymer blend made by any one ofthe processes herein.

[0207] In another embodiment, set forth herein is a method of using a polymer blenddisclosed herein, in which the method includes using the polymer blend for crack filling, as an antimicrobial agent, as an adhesive agent, as a coating, as a compatibilizer, as a stabilizer, as a metal scavenger, as a membrane, as a gasket, as a drug delivery agent, as a scavenger agent, comprising applying the amine-functionalized polymer to a substrate. - 39 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044

[0208] In some embodiments, including any of the foregoing, the scavenger agent is forbinding pollutants during environmental remediation in marine environments, and wherein the pollutants include oil, plastic particles, or a combination thereof.

[0209] In some embodiments, including any of the foregoing, the membrane is anelectrolyte membrane or a filtering membrane for water purification.

[0210] In some embodiments, including any of the foregoing, the adhesive agent is foradhering to a substrate, and wherein the substrate is substrate is a low energy substrate.

[0211] In some embodiments, including any of the foregoing, the substrate is selectedfrom the group consisting of PTFE, polyethylene, polypropylene, polyolefin, nylon, textile, plastic, composite, glass, wood, fiberglass, metal, and combinations thereof.

[0212] In some embodiments, including any of the foregoing, the substrate is afluoropolymer selected from the group consisting of polytetrafluroroethylene (PTFE), polyvinylfluoride (PVF), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), perfluoroalkoxy polymer (PFA), fluorinated ethylene-propylene (FEP), and related perfluoro elastomers.

[0213] In some embodiments, including any of the foregoing, the substrate is PTFE.

[0214] In some embodiments, including any of the foregoing, the substrate is PTFE andwherein the PTFE is porous.

[0215] In some embodiments, including any of the foregoing, the substrate is non-surfacemodified PTFE.

[0216] In some embodiments, including any of the foregoing, set forth herein is a processfor repressing a polymer blend disclosed herein, comprising disposing the polymer blend on and between two substrates, separating the two substrates, and repressing the polymer blend between the two substrates.

[0217] In some embodiments, including any of the foregoing, some or all of the polymerblend is removed from at least one of the two substrates before or during the separating the two substrates.

[0218] In some embodiments, including any of the foregoing, the repressing is at apressure from 0.1 MPa to 100 MPa.

[0219] In some embodiments, including any of the foregoing, the repressing is higherthan 0.5 MPa. - 40 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044

[0220] In some embodiments, including any of the foregoing, the repressing is higherthan 1 MPa.

[0221] In some embodiments, including any of the foregoing, the repressing is at atemperature at or greater than 60 ºC.

[0222] In some embodiments, including any of the foregoing, the repressing is at atemperature at or greater than 90 ºC.

[0223] In some embodiments, including any of the foregoing, the repressing is at 1 MPaat a temperature at or greater than 90 ºC. ADDITIONAL EMBODIMENTS

[0224] In certain embodiments, the polymer blend herein has an amine-functionalizedpolymer APE and an EVA with 40 wt% vinyl acetate content. In some embodiments, the ratio of APE to EVA is 2:1 by weight. In some embodiments, this ratio varies by 10%. In certain embodiments, the typical MW of APE is 40-70 kg / mol. In certain embodiments, the suitable solvent for film casting to prepare the HMA is tetrahydrofuran. In certain embodiments, the film thickness is approximately 0.4 mm after solvent evaporation. In certain embodiments, the preferred substrate is a low surface energy material, such as polytetrafluoroethylene (PTFE). For application, in one embodiment, a temperature of 90 °C and pressure of 1 MPa was applied for 3 mins.

[0225] Polymer molecular weight (MW) typically is, in some embodiments, 40-70kg / mol; or 20-40 kg / mol; or greater than 70 kg / mol.

[0226] In other embodiments, the mass ratio of APE to EVA (40 wt% VA) may be 1:2,1:1, 1.5:1, 2.5:1, 3.5:1, 4:1, 5:1

[0227] In other embodiments, HMAs prepared using EVA with a lower VA content(such as 18%) leads to inferior adhesive properties due to immiscibility between APE and EVA in the blend.

[0228] In other embodiments, the temperature used for application of the HMA film to asubstrate can be 60 °C. In other embodiments, the temperature can be higher than 90 °C.

[0229] In other embodiments, the pressure can be 0.5 MPa. The pressure can be higherthan 1 MPa.

[0230] In certain polymer blends, there is no significant chemical change afterheating / cooling based on polymer rheology and IR spectroscopy before and after heating. - 41 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044

[0231] In certain embodiments, the polymer blends further include tackifiers.

[0232] Factors governing the performance of EVA-based formulations are the miscibilitybetween components and the relative ratio of the components.

[0233] Suitable amine-functionalized polymers for use in the subject disclosure include,but are not limited to, those disclosed in WO2019222834A1, which published November 28, 2019, and is titled GROUP 5 METAL COMPLEXES FOR PRODUCING AMINE- FUNTIONALIZED POLYOLEFINS; WO2019222852A1, which published November 28, 2019, and is titled NOVEL AMINE FUNCTIONALIZED POLYMERS AND METHODS OF PREPARATION; and WO2023092225A1, which published June 1, 2023, and is titled SUPERHYDROPHOBIC COATINGS, COMPOSITIONS AND METHODS, the disclosures of which are expressly incorporated by reference herein.

[0234] Suitable amine-functionalized polymers for use in the subject disclosure include,but are not limited to, those disclosed in (a) Gilmour, D. J.; Tomkovic, T.; Kuanr, N.; Perry, M. R.; Gildenast, H.; Hatzikiriakos, S. G.; Schafer, L. L., Catalytic Amine Functionalization and Polymerization of Cyclic Alkenes Creates Adhesive and Self- Healing Materials. ACS Applied Polymer Materials 2021, 3, 2330-2335; (b) Kuanr, N.; Gilmour, D. J.; Gildenast, H.; Perry, M. R.; Schafer, L. L., Amine-Containing Monomers for Ring-Opening Metathesis Polymerization: Understanding Chelate Effects in Aryl- and Alkylamine-Functionalized Polyolefins. Macromolecules 2022; (c) Yavitt, B. M.; Tomkovic, T.; Gilmour, D. J.; Zhang, Z.; Kuanr, N.; van Ruymbeke, E.; Schafer, L. L.; and Hatzikiriakos, S. G., Rheology and self-healing of amine functionalized polyolefins. Journal of Rheology,2022, 66, 1125-1137, the disclosures of each of which are expressly incorporated by reference herein.

[0235] In some embodiments, including any of the foregoing, the subject APE maycomprise, consist, or consist essentially of an amine-functionalized compound of Formula 2: - 42 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044wherein (---) indicates an optional double bond; wherein M1and M2are independently is -OH, a substituted or unsubstituted C1-15 alkyl, a substituted or unsubstituted aromatic cycle, a substituted or unsubstituted heterocycle; wherein each X1, X2, X3, and X4is independently H or CH3; wherein each Y1, Y2, Y3, Y4, Y5, Y6, Z1, Z2, Z3, and Z4is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, an amine-compatible protection group, -C(=O)R’, or -C(OR’)R’’, and wherein at least one of Y1, Y2, Y3, Y4, Y5, Y6, Z1, Z2, Z3, and Z4is -CR1R2–NR3R4; wherein each of R’, R’’, R1, R2, R3and R4is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group; wherein r = 0 or 1 and q = 0 or 1, wherein r + q = 0, 1, or 2; and wherein n is a natural number greater than 1 and less than 10,000,000,000.

[0236] In some embodiments, including any of the foregoing, the aspects of thedisclosure that pertain to block copolymers comprising: an APE compound as described above; and a polymer formed by radical or anionic polymerization, for which the functional end-groups M1and M2of the amine functionalized compound serves as an initiation point. - 43 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044

[0237] In some embodiments, set forth is a block copolymer prepared that includes anamine functionalized compound as described above; and at least one additional polymer.

[0238] In some embodiments, including any of the foregoing, the APE polymer maycomprise, consist, or consist essentially of an amine-functionalized compound of Formula 3:wherein (---) indicates an optional double bond; wherein M1and M2are independently is -OH, a substituted or unsubstituted C1-15 alkyl, a substituted or unsubstituted aromatic cycle, or a substituted or unsubstituted heterocycle; wherein each X1, X2, X3, and X4is independently H or CH3; wherein each Y1, Y2, Y3, Y4, Y5, Y6, Z1, Z2, Z3, and Z4is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, an amine-compatible protection group, -C(=O)R’, or -C(OR’)R’’, and wherein at least one of Y1, Y2, Y3, Y4, Y5, Y6, Z1, Z2, Z3, and Z4is -CR1R2–NR3R4; wherein each of R’, R’’, R1, R2, R3and R4is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group; wherein r = 0 or 1 and q = 0 or 1, wherein r + q = 0, 1, or 2; wherein n and m are natural numbers; and - 44 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 wherein the monomers are connected in a head-to-head fashion.

[0239] In some embodiments, including any of the foregoing, the APE polymer maycomprise, consist, or consist essentially of an amine-functionalized compound of Formula X:wherein (---) indicates an optional double bond; wherein M1and M2are independently is -OH, a substituted or unsubstituted C1-15 alkyl, a substituted or unsubstituted aromatic cycle, a substituted or unsubstituted heterocycle; wherein each X1, X2, X3, and X4is independently H or CH3; wherein each Y1, Y2, Y3, Y4, Y5, Y6, Y7, Y8, Y9, Y10, Y11, Y12, Z1, Z2, Z3, and Z4is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, an amine-compatible protection group, -C(=O)R’, or -C(OR’)R’’, and wherein at least one of Y1, Y2, Y3, Y4, Y5, Y6, Z1, Z2, Z3, and Z4is -CR1R2–NR3R4; wherein each of R’, R’’, R1, R2, R3and R4is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group; wherein r = 0 or 1 and q = 0 or 1, wherein r + q = 0, 1, or 2; wherein n and m are natural numbers; - 45 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044

[0240] In some embodiments, including any of the foregoing, the APE polymers maycomprise, consist, or consist essentially of an amine-functionalized compound of Formula 6:(Formula 6) wherein (---) indicates an optional double bond; wherein each X1, X2, X3, and X4is independently H or CH3; wherein each Y1, Y2, Y3, Y4, Y5, Y6, Z1, Z2, Z3, and Z4is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, an amine-compatible protection group, -C(=O)R’, or -C(OR’)R’’, and wherein at least one of Y1, Y2, Y3, Y4, Y5, Y6, Z1, Z2, Z3, and Z4is -CR1R2–NR3R4; wherein each of R’, R’’, R1, R2, R3and R4is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group; and wherein r = 0 or 1 and q = 0 or 1, wherein r + q = 0, 1, or 2.

[0241] In some embodiments, including any of the foregoing, the at least one of X1, X2,X3, X4, Y1, Y2, Y3, Y4, Y5, Y6, Z1, Z2, Z3, Z4, R’, R’’, R1, R2, R3, and R4 serves as aninitiation point for subsequent synthesis of polymeric bristles or brushes.

[0242] In certain embodiments, including any of the foregoing, Y3 or Y4 is -CR1R2–NR3R4; wherein R3or R4are each, independently, a substituted or unsubstituted aryl. In some embodiments, either q or r is 0. In some embodiments, q is 0 and r is 1. In some other embodiments, q is 1 and r is 0. - 46 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044

[0243] In certain embodiments, including any of the foregoing, the compound of formula2 comprises Y3or Y4as -CR1R2–NR3R4; wherein R3or R4are each, independently, a substituted or unsubstituted phenyl. In some embodiments, either q or r is 0. In some embodiments, q is 0 and r is 1. In some other embodiments, q is 1 and r is 0.

[0244] In certain embodiments, including any of the foregoing, the compound of formula6 comprises Y3or Y4as -CR1R2–NR3R4; wherein R3or R4are each, independently, a substituted or unsubstituted benzyl. In some embodiments, either q or r is 0. In some embodiments, q is 0 and r is 1. In some other embodiments, q is 1 and r is 0.

[0245] In certain embodiments, including any of the foregoing, the compound of formula2 comprises Y3or Y4as -CR1R2–NR3R4; wherein R3or R4are phenyl. In some embodiments, either q or r is 0. In some embodiments, q is 0 and r is 1. In some other embodiments, q is 1 and r is 0.

[0246] In certain embodiments, including any of the foregoing, the compound of formula6 comprises Y3or Y4as -CR1R2–NR3R4; wherein R3or R4are benzyl. In some embodiments, either q or r is 0. In some embodiments, q is 0 and r is 1. In some other embodiments, q is 1 and r is 0.

[0247] In certain embodiments, including any of the foregoing, the compound of formula2 comprises Y3or Y4as -CR1R2–NR3R4; wherein R3and R4are both phenyl. In some embodiments, either q or r is 0. In some embodiments, q is 0 and r is 1. In some other embodiments, q is 1 and r is 0.

[0248] In certain embodiments, including any of the foregoing, the compound of formula6 comprises Y3or Y4as -CR1R2–NR3R4; wherein R3and R4are both benzyl. In some embodiments, either q or r is 0. In some embodiments, q is 0 and r is 1. In some other embodiments, q is 1 and r is 0.

[0249] In some embodiments, Y3 or Y4 is CH2-NH-Ph. Herein Ph is phenyl. In someother embodiments, q is 1 and r is 0. - 47 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044

[0250] In some embodiments, Y3 or Y4 is CH2-NH-Ph-F. Herein Ph is phenyl. In someother embodiments, q is 1 and r is 0.

[0251] In some embodiments, Y3 or Y4 is CH2-NH-Ph-OH3. Herein Ph is phenyl. In someother embodiments, q is 1 and r is 0.

[0252] In some embodiments, the APE is or includes, or further includes:; ; ; \AMERICASAttorney Docket No.: 125298.00044 ; ; ,, . , n is less than 100,000.

[0253] In some embodiments, including any of the foregoing, the APE polymer maycomprise, consist, or consist essentially of an amine-functionalized compound of Formula XI: - 49 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 engthof the resulting copolymer relative to a homopolymer of amine monomers.

[0255] The compounds of Formula XI are formed from a structure that has two cyclicalkenes that can ring-open. See the reaction scheme below. One is more strained and thus more reactive, therefore becoming predominantly incorporated into the polymer backbone. The second cyclic alkene may remain after the reaction (as seen in the ‘n’ unit) or may ring-open and cross-link with another polymer chain (see ‘o’ unit):

[0256] In some embodiments, the APE polymer is or includes:. 1104824148\1\AMERICASAttorney Docket No.: 125298.00044

[0257] In some embodiments, the APE polymer is or includes:.

[0258] In some eg, the co-polymerscomprising a mixture of different amine-functionalized monomer units of Formula 5:wherein M1and M2are, each, selected from -OH, a substituted or unsubstituted C1-15 alkyl, a substituted or unsubstituted aromatic cycle, a substituted or unsubstituted heterocycle; wherein each of X1, X2, X3, and X4is independently H or CH3; wherein each of Y1, Y2, Y3, Y4, Y5,Z1, and Z2is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, an amine-compatible protection group, -C(=O)R’, or -C(OR’)R’’; wherein each of R’, R’’, Ra, R1, R2, R3and R4is independently H, a substituted or unsubstituted linear or cyclic alkyl or alkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocycle, or an amine-compatible protection group; or wherein R’ or R’’ is -CR1R2–NR3R4, - 51 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 wherein r = 0 or 1 and q = 0 or 1, wherein r + q = 0, 1, or 2; and wherein n is a natural number greater than 1. In some embodiments, n is less than 100,000.

[0259] In embodiments, the APE polymer may comprise, consist, or consist essentially ofan amine-functionalized compound of:, wherein subscript n is an integer greater than 1 and less than 100,000,000,000. In some embodiments, n is less than 100,000.

[0260] In embodiments, the APE polymer may comprise, consist, or consist essentially ofan amine-functionalized compound which includes as a portion of the polymer the following structure:, wherein subscript n is an integer an integer greater than 1 and less than 100,000,000,000. In some embodiments, n is less than 100,000. KITS

[0261] In another embodiment, set forth herein is a kit that includes a polymer blend thatis disclosed herein and instructions for disposing the polymer blend on a substrate. - 52 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 EXAMPLES

[0262] Chemicals were commercially purchased unless specified otherwise. Unlessstated otherwise, the APE used in the Examples below was prepared according to a two- step catalytic sequence of hydroaminoalkylation followed by ROMP as detailed in U.S. Patent No. US 11,555,107 B2, the entire contents of which are herein incorporated by reference in its entirety. See the synthesis for the N-methyl aniline substituted APE in FIGs.1-3, section 4.3, column 35, line 50 through column 36, line 67, of US 11,555,107; also section 4.8.1, column 50, lines 10-56.

[0263] Molecular characteristic of EVA-40 was as follows for the following Examples.Polymer ^^ ^^ (kg / mo ^^ ^^^^ l) ^^^^ (kg / mol) ^^^^^^EVA-40 55.1 106.5 1.93EXAMPLE 1 - ADHESION TESTING

[0264] Adhesive testing was performed to determine the effect of polymer blend ratio onadhesion performance and evaluate adhesive candidate polymer blends for use with a polytetrafluoroethylene (PTFE) substrate. All tests were performed at peeling rate of 10 mm / min.

[0265] FIG. 1 shows a sample peeling test curve for each of the APE and APE / EVA-40polymer blends. Herein EVA-40 means EVA with 40% by weight vinyl acetate.

[0266] Peeling strength is the force measured to separate the structure normalized by thesample width. The structure in this case is a polymer blend of APE:EVA on a PTFE substrate. This gives comparable results for samples with different widths. From the curve in FIG.1, three parameters were calculated from the peeling test curve: maximum strength, average strength and energy density. The maximum strength was defined as the maximum peeling strength in the overall peeling curve. Energy density measured the energy required to create two surfaces out of one per unit area. Average strength and energy density are calculated using equation 4 and 5. ∑ ^^2^^ (4) ^^1^^ 1104824148\1\AMERICASAttorney Docket No.: 125298.00044

[0267] Where ^^1 is the position where maximum strength happens, ^^2 is the end of thetest, F is the force measured to separate the sandwiched structure, W is the width of the sample and n is the number of measured points from position ^^1to ^^2. ^^ ^ ∫2^ ^^^^^^^^^^^ ^^^^^^^^^^^^^^ =^(5) ^ 0^^^^^^^

[0268] Where L is the leng

[0269] Four replicates werethe average resultsshown in FIG.1.

[0270] APE alone (i.e., APE1) shows cohesive failure where the crack formed at the tipof the sample and propagated within the adhesive itself. The cohesive failure is represented in the curve as a smooth increase in peeling strength before reaching a plateau referred as average strength.

[0271] EVA-40 did not show adhesion on PTFE so the peeling strength is 0.

[0272] Adding 25% of EVA-40 to APE (3:1 APE:EVA; labeled 75APE in FIGs. 1A and1B) dramatically increased the average peeling strength to 800 N / m from 30 N / m and maintained the cohesive failure. A 1:1 APE:EVA sample (labeled 50APE1 in FIGs.1A and 1B) showed a decrease in the peeling strength compared with 3:1 APE:EVA and transited to an adhesive failure region that is indicated by the zig-zag shape in the peeling curve. The adhesive performance was better than APE itself.25APE / EVA-40 (1:3 APE:EVA) also had an adhesive failure with even lower adhesion performance than pure APE. See FIGs.1A and 1B. EXAMPLE 2 - ADHESION TESTING

[0273] Polymer blend ratios between 50APE (1:1 APE:EVA) through 75APE (3:1APE:EVA) and above were evaluated. Four polymer blend sample were prepared as follows: 58APE (29:21 APE:EVA), 66APE (33:17 APE:EVA), 83APE (83:17 APE:EVA) and 91APE (91:9 APE:EVA). The numbers, 58, 66, 83, and 91, represented the percent APE in the mass ratio of APE:EVA. The peel strength for each polymer blend was measured at the same peel rate. APE was used for the APE polymer.

[0274] FIG. 2A shows data for each of the blends.

[0275] Adhesive to cohesive failure transition occurred between 58 wt% APE to 66 wt%APE. In the adhesive failure regime, increasing the APE content increased the maximum, - 54 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 average peel strength and energy density. Starting from 66APE (33:17 APE:EVA), cohesive failure of the T-peel sample occurred. However, the cohesion strength of the blend is higher than the yield strength of the PTFE which leads to the plastic deformation of the PTFE. The high plateau of peel strength for 66APE shown in FIG.2A is a result of the stretching in PTFE film alone. FIG.2B shows certain embodiments with maximum performance as a function of mass ratio.

[0276] With increasing APE content beyond 66 wt%, a decrease in peel strength wasobserved as cohesive force of the blend is lowered with lower EVA content. A steeper drop in peel performance occurred between 75APE and 83APE. With this, the design window for APE / EVA-40 blends to reach relative high peel performance will, in some examples, be between 66 to 75 wt% APE. EXAMPLE 3 - T-PEEL TEST ON DIFFERENT SUBSTRATES

[0277] The adhesion performance of 75APE polymer blend (3:1 APE:EVA) on othersubstrates is shown in FIG.3 with the substrate listed in increasing surface energy. With all the substrates, relative high peel performance in cohesive failure regime was observed. Without being bound by theory, peel performance should be a function of adhesive cohesion strength if the failure occurs in cohesive failure regime. However, peel strength on ultra-high molecular weight polyethylene (UHMWPE) and nylon showed around 25% decrease compared with other substrates. This may be due to the difference in strength (young’s modulus and yield strength) of the substrates. Substrates with higher peeling strength showed a strained behavior, likely indicating the participation of substrate deformation in peel strength measurement. EXAMPLE 4 – PEELING RATE EFFECT ON T-PEEL TEST

[0278] The effect of different peeling rates on peeling performance of 3:1 (APE:EVA)was assessed with results shown in FIG.4. With increasing peeling rate, the peeling performance gradual increased until, and including, 90 mm / min where a transition to adhesive failure occurred and led to a significant decrease in the peeling strength. Starting from 70 mm / min, the PTFE substrates started to yield. Therefore, the results for 70 mm / min and 90 mm / min have contributions from both yielding the PTFE and - 55 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 destroying the adhesion-substrate interface. However, this blend is considered strong enough for application on this PTFE substrate with peeling rate below 90 mm / min. EXAMPLE 5 - MAKING APE:EVA POLYMER BLENDS

[0279] The APE amine-functionalized polymer investigated herein was preparedaccording to a two-step catalytic sequence of hydroaminoalkylation followed by ROMP as detailed in U.S. Patent No. US 11,555,107 B2. See the synthesis for the N-methyl aniline substituted APE in FIGs.1-3, section 4.3, column 35, line 50 through column 36, line 67, of US 11,555,107; also section 4.8.1, column 50, lines 10-56. The aminated polyethylene (APE) features a poly(cyclooctene) backbone functionalized with an N- methyl aniline derivative. The molecular characteristics of this APE variant is shown in Table 1.

[0280] APE and APE2 are each a poly(N-(oct-4-en-1-ylmethyl)aniline) polymer ofdifferent molecule weights and polydispersity, as detailed in Table 1, below.

[0281] Two EVAs, one with 18 wt% and the other with 40 wt% of vinyl acetate content,were used to investigate their effect on the adhesive performance of the resulting blends. Samples are abbreviated as EVA-18 and EVA-40, with the number indicating the weight percentage of vinyl acetate content. The melt index is 8 g / 10min and 57 g / 10min at 190 ℃ for EVA 18 and EVA-40 respectively.

[0282] Molecular characteristic of EVA-40 was as follows.Polymer ^^ ^^ (kg / mol) ^^ ^^ (kg / mol) ^^^^^^^^^^ ^^EVA 40 551 1065 193molecular characteristics. Polymer ^^^^^^ (kg / mol) ^^ ^^^^ (kg / mol) ^^^^^^^^detection gel permeation chromatography (GPC). PDI is polydispersity index. - 56 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 EXAMPLE 6 - BLEND PREPARATION BY SOLUTION CASTING

[0285] The hot melt adhesive (HMA) was prepared by the blending of APE with EVA intetrahydrofuran (THF) followed by drop-casting onto a PTFE mold. The drop-casted sample was dried overnight under ambient conditions then was transferred to a vacuum oven at 40 ℃ for at least 12 hours to ensure complete solvent evaporation. Polymer blend samples were then collected, and melt processed to make films with desired thickness.

[0286] Polymer blends with variable proportion by weight of APE to EVA were preparedto investigate effect of APE / EVA amount on the blend performances. EXAMPLE 7 - DIFFERENTIAL SCANNING CALORIMETRY

[0287] Thermal properties were explored via differential scanning calorimetry (DSC) ona TA instrument DSC 25. For each testing, 5 mg to 10 mg sample was prepared in a standard aluminum pan. A heat-cool-heat cycle from -60 ℃ to 150 ℃ at a rate of 10 ℃ / min was performed to first erase the thermal history and to capture the glass transition temperature (^^^^), melting peak (^^^^) and crystallization temperature (^^^^). DSC was used to confirm the miscibility of components. EXAMPLE 8 - RHEOLOGICAL MEASUREMENT

[0288] Linear viscoelasticity was characterized using an Anton Paar MCR 702 with an 8mm partition plate for two EVA samples and APE / EVA-18 blends. MCR 302e with a Peltier bottom plate and 8 mm parallel was used for APE and APE / EVA-40 blends. Frequency sweep tests were performed at temperatures from 90℃ to -10℃ for APE samples, 110 ℃ to 50 ℃ for EVA-40 and its blends, and from 150 ℃ to 90 ℃ for EVA- 18 and its blends. The strain used in the testing was within the linear viscoelasticity range for all samples.

[0289] Extensional testing was characterized using Anton Paar MCR 302e with SERfixture. The tested samples were prepared by melt-pressing the solvent casted sample into a film and then cutting it into 3 mm x 15 mm rectangular strips with thickness 1 mm. Sample strips were extended at Hencky strain rates from 0.4 s-1 to 8 s-1 at room temperature with three replicates for each rate. - 57 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 EXAMPLE 9 - ADHESION TESTING

[0290] Adhesion tests (T-peel and lap-shear tests) were done on a Dynamic mechanicalanalyzer (RSA G2, TA instruments) in axial mode equipped with a tensile fixture. Test species were prepared by melt-pressing the solvent-casted sample between two substrates on a hot plate at 90 ℃ and for 3 mins with 1 kg weight. The illustration for the specimen along with its dimensions were shown in FIG.5. FIG.5 shows how the measurement is done. After equilibrium at room temperature for at least one hour, the specimen was then cut into strips and were ready for testing. During the test, the tensile fixture moved at a constant rate (peeling rate) and the force required to separate the sample was recorded along with the displacement. For each sample and rate, four replicates were performed.

[0291] Substrates used in this study is a sintered PTFE film with a thickness of 0.14 mmfrom Cole-Parmer. The film is a smooth, non-surface treated and chemically resistant substrate which is designed for applications such as surface protection and corrosion resistance. Substrate films used for testing were cleaned with THF prior to the hot melt process. EXAMPLE 10 - CONTACT ANGLE MEASUREMENT

[0292] Contact angle of three standard fluids (water, ethylene glycol and dimethylsulfoxide (DMSO)) on test surfaces were measured using tensiometer Attention Theta Flex (Biolin Scientific). An average of left-side and right-side contact angle was measured after ~ 5 ^^L fluid was supplied onto the test surface using a sessile droplet.Measurements were taken at three to four different spots on each film to calculate the average and uncertainty.

[0293] Test surfaces were prepared by melt-pressing the samples between two PTFEfilms and then swiftly removing one PTFE film to obtain a smooth surface before the testing. EXAMPLE 11 – PEELING RATE EFFECT ON T-PEEL TEST

[0294] The effect of different peeling rates on peeling performance of 90APE / EVA-40blend on PTFE substrates was assessed with results shown in FIG.6.

[0295] FIG. 6 shows the average peel strength of 90APE / EVA-40 blend at varyingpeeling rates on PTFE substrates. - 58 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044

[0296] With increasing peeling rate, the peeling performance gradually increased until,and including, 390 mm / min.

[0297] This Example shows that with 90APE / EVA, it is possible to obtain high strengthswith very high peel rates up to 390 mm / min. EXAMPLE 12 - T-PEEL TEST ON DIFFERENT SUBSTRATES

[0298] The average peel strength of 60APE / EVA-40 blend at 10 mm / min on varyingsubstrates is shown in FIG.7. In FIG.7, CFRP is carbon fiber reinforced polymer. EXAMPLE 13 – STRETCH TESTING

[0299] FIG. 8 (left) shows the dog-bone shape of the tested sample and the stretchedsample during the testing, (right) shows the stress-strain curve of 75APE / EVA and 90APE / EVA blends before and after self-healing at varying conditions. The conditions were no heating; 30 ºC heating for 3 hours; 30 ºC heating for 21 hours; and 40 ºC heating for 3 hours. FIG.8 demonstrates that the polymer blend can maintain the self-healing evidenced by the APE alone, however it takes longer and may require heat. EXAMPLE 14 - ADHESION TESTING

[0300] Adhesive testing was performed to determine the effect of repressing polymerblends on adhesion performance. All tests were performed at peeling rate of 10 mm / min.

[0301] At the end of the peeling experiments, after disposing the polymer blend onsubstrate, and removing the polymer blend; the two substrates with residual adhesives were re-assembled by joining where they were initially bonded, and melt pressing at 70 ℃ for 5 mins.

[0302] FIG. 9 shows the T-peel displacement curves for original and repressed60APE / EVA blend on polyester substrates at rate of 10 mm min-1. The inset showed the average peel strength for the two cases. FIG.9 demonstrates that the polymer blend can reversibly bond, i.e., stick and re-stick.

[0303] The embodiments and examples described above are intended to be merelyillustrative and non-limiting. Those skilled in the art will recognize or will be able to ascertain using no more than routine experimentation, numerous equivalents of specific - 59 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 compounds, materials and procedures. All such equivalents are considered to be within the scope and are encompassed by the appended claims. - 60 - 1104824148\1\AMERICAS

Claims

Attorney Docket No.: 125298.00044 Claims 1. A polymer blend comprising:an amine-functionalized polymer (APE); and a poly (ethylene-co-vinyl acetate) (EVA) co-polymer.

2. The polymer blend of claim 1, wherein the APE is not a member selected from the groupconsisting of a nylon polymer, a nitrile polymer, a polyurethane polymer, a polyurea polymer, a polyetheramine polymer, or a combination thereof.

3. The polymer blend of claim 1 or 2, wherein the APE is a polymer with free-aminegroups.

4. The polymer blend of any one of claims 1-3, wherein the APE is an amine-functionalizedpolyolefin.

5. The polymer blend of any one of claims 1-4, wherein the APE is substituted with primaryor secondary amine substituents.

6. The polymer blend of any one of claims 1-5, wherein the APE:EVA mass ratio is 1:3 orhigher.

7. The polymer blend of any one of claims 1-6, wherein the APE:EVA mass ratio is 2:1 orhigher.

8. The polymer blend of any one of claims 1-7, wherein the APE:EVA mass ratio is 1:3 to10:

1.

9. The polymer blend of any one of claims 1-8, wherein the APE:EVA mass ratio is 2:1 to1,000:

1.

10. The polymer blend of any one of claims 1-9, wherein the APE:EVA mass ratio is 2:1 to10:

1.

11. The polymer blend of any one of claims 1-10, wherein the APE:EVA mass ratio is 1:1;3:2; 3:1, or 9:

1. - 61 - 1104824148\1\AMERICASAttorney Docket No.: 125298.0004412. The polymer blend of any one of claims 1-11, wherein the APE:EVA mass ratio is 1:3,1:1, or 3:1.

13. The polymer blend of any one of claims 1-12, wherein the APE:EVA mass ratio is 1:2,1:1, 1.5:1, 2.5:1, 3.5:1, 4:1, or 5:1.

14. The polymer blend of any one of claims 1-13, wherein the APE:EVA mass ratio is 1:1,3:1, 29:21; 33:17, 83:17, or 91:9.

15. The polymer blend of any one of claims 1-14, wherein the APE:EVA mass ratio is 1:1,3:1, 29:21; 33:17, 83:17, or 91:9; wherein the mass ratio is ± 10%, ± 9%, ± 8%, ± 7%,± 6%, ± 5%,± 4%, ± 3%,± 2%, or ± 1%.

16. The polymer blend of any one of claims 1-15, wherein the APE:EVA mass ratio is 3:1 ±10%.

17. The polymer blend of any one of claims 1-16, wherein the APE:EVA mass ratio is 2:1 ±10%.

18. The polymer blend of any one of claims 1-17, wherein the molecular weight of the APEis about 1,000 kg / mol to about 100,000 g / mol.

19. The polymer blend of any one of claims 1-18, wherein the molecular weight of the APEis about 40,000 g / mol to about 70,000 g / mol.

20. The polymer blend of any one of claims 1-19, wherein the molecular weight of the APEis about 20,000 g / mol to about 40,000 g / mol.

21. The polymer blend of any one of claims 1-20, wherein the molecular weight of the APEis greater than 70,000 g / mol.

22. The polymer blend of any one of claims 1-21, wherein the EVA has a melt index of 40g / min to 60 g / min at 190 ºC.

23. The polymer blend of any one of claims 1-21, wherein the EVA has a melt index of 57g / min at 190 ºC.

24. The polymer blend of any one of claims 1-23, wherein the APE comprises the structureof Formula (Ia), Formula (Ib), or both: - 62 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044indicates a single bond or a double bond; R1and R2are, independently, selected from the group consisting of OH, C1-15alkyl, C2-15alkenyl, C2-15alkynyl, C6-10aryl, C4-10cycloalkyl, C4-10heterocycloalkyl, and a terminating end group; R3is C1-6alkyl-NR4R5; R4and R5are independently selected from the group consisting of H, C1-6alkyl, C3-10cylcoalkyl, C3-10cylcoalkenyl, C3-10heterocylcoalkyl, C3-10heterocylcoalkenyl, C6-10aryl, C6-10heteroaryl, and an amine- compatible protection group; or R1, R2, R3, R4, and R5are independently optionally substituted by one to six substituents selected from the group consisting of OH, C1-5alkyl, C1-5heteroalkyl, C1-5alkoxy, halo, C1-5 haloalkoxy, amino, nitro, carbonyl, and carboxyl; subscript p is, independently for each formula, an integer equal to 2 to 100,000.

25. The polymer blend of claim 24, wherein at least one of R4 and R5 is not H.

26. The polymer blend of claim 24 or 25, wherein at least one of R4 and R5 is H.

27. The polymer blend of any one of claims 1-26, wherein the APE comprises or furthercomprises the structure of Formula (IIa), Formula (IIb), or both: - 63 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 R2R2wherein: indicates a single bond or a double bond; R1and R2are, independently, selected from the group consisting of OH, C1-15alkyl, C2-15alkenyl, C2-15alkynyl, C6-10aryl, C4-10cycloalkyl, C4-10heterocycloalkyl, a terminating end group; R3is C1-6alkyl-NR4R5; R4and R5: are independently selected from the group consisting of H, C1-6alkyl, C3-10cylcoalkyl, C3-10cylcoalkenyl, C3-10heterocylcoalkyl, C3-10heterocylcoalkenyl, C6-10aryl, C6-10heteroaryl, and an amine- compatible protection group; and - 64 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 R1, R2, R3, R4, and R5are independently optionally substituted by one to six substituents selected from the group consisting of OH, C1-5alkyl, C1-5alkoxy, halo, C1-5 haloalkoxy, amino, nitro, or carboxyl; R7is, independently in each instance, selected from the group consisting of OH, C1-5alkyl, C1-5alkoxy, halo, C1-5haloalkoxy, amino, nitro, carbonyl, and carboxyl; or wherein two R7substituents together with the carbons to which they are attached form a C4-6cycloalkyl or C4-6cycloalkenyl ring; subscripts s and t are independently selected from an integer of 1 to 100,000; subscript r is an integer from 0 to 6.

28. The polymer blend of claim 27, wherein at least one of R4 and R5 is not H.

29. The polymer blend of claim 27 or 28, wherein two R7 substituents form a C4-6cycloalkylor C4-6cycloalkenyl ring.

30. The polymer blend of any one of claims 24-29, wherein the APE comprises or furthercomprises the structure of Formula (IIa1), Formula (IIb1), or both: ;- 65 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 wherein:indicates a single bond or a double bond R1, R2, R8, and R9, are independently, selected from the group consisting of OH, C1-15alkyl, C2-15alkenyl, C2-15alkynyl, C6-10aryl, C4-10cycloalkyl, C4-10heterocycloalkyl, and a terminating end group; subscripts b, c, d, x, and p, are independently selected from an integer of 1 to 100,000; subscript g is an integer from 0 to 5; and Z is independently H, OCF3, F, Cl, Br, I, or OCH3.

31. The polymer blend of any one of claims 24-30, wherein the APE comprises or furthercomprises the structure of Formula (IIa2), Formula (IIb2), or both: - 66 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 ; where : indicates a single bond or a double bond R1, R2, R8, and R9, are independently, selected from the group consisting of OH, C1-15alkyl, C2-15alkenyl, C2-15alkynyl, C6-10aryl, C4-10cycloalkyl, C4-10heterocycloalkyl, and a terminating end group; subscripts b, c, d, x, and p are independently selected from an integer of 1 to 100,000; and Z is independently H, OCF3, F, Cl, Br, I, or OCH3. - 67 - 1104824148\1\AMERICASAttorney Docket No.: 125298.0004432. The polymer blend of any one of claims 24-31, wherein NR4R5 is pyrrolidine; piperidine;; wherein Z is independently H, OH, OR10, OCF3, F, Cl, Br, I,SOCH3, OCH3, or CH3; and subscript q is from 1 to 5; and represents the point of attachment of NR4R5to the polymer;wherein R10is H, C1-6alkyl, or a protecting group.

33. The polymer blend of any one of claims 24-32, wherein NR4R5 is independently; wherein Z is H, OCF3, F, Cl, Br, I, orOCH3; and subscript q is from 1 to 5; and represents the point of attachment of NR4R5to the polymer.

34. The polymer blend of claim 33, wherein q is 1.

35. The polymer blend of any one of claims 24-34, wherein NR4R5 is independentlypyrrolidine; piperidine ; wherein Z is H, OCF3, F, Cl, Br, I,or OCH3; and represents the point of attachment of NR4R5to the polymer.- 68 - 1104824148\1\AMERICASAttorney Docket No.: 125298.0004436. The polymer blend of any one of claims 24-35, wherein NR4R5 is independentlyd wherein Z is H, OCF3, F, Cl, Br, I, or OCH3.37.e of claims 1-36, wherein the amine-functionalized polymercomprises, or further comprises, the structure of Formula (IIIa), (IIIb), or both: a) 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 (IIIb); wherein indicates a single bond or a double bond; R1and R2are, independently, selected from the group consisting of OH, C1-15alkyl, C6-10aryl, C4-10heterocycle, and a terminating end group; R1and R2are independently optionally substituted by one to six substituents selected from the group consisting of OH, C1-5alkyl, C1-5alkoxy, halo, C1-5haloalkoxy, amino, nitro, carbonyl, and carboxyl; subscript p is from 2 to 100,000; R6is selected from the group consisting of OH, C1-5alkyl,C1-5alkoxy, halo, C1-5haloalkoxy, amino, nitro, and carboxyl.

38. The polymer blend of claim 37, wherein R6 is H, OCF3, F, Cl, Br, I, or OCH3.

39. The polymer blend of any one of claims 1-38, wherein the APE has, or further comprises,the structure of Formula (IVa), (IVb), or both: 1104824148\1\AMERICASAttorney Docket No.: 125298.0004440. The polymer bleno cam , w eren s , , r, or .

41. The polymer blend of claim 40 or 41, wherein R6 is F.

42. The polymer blend of any one of claims 1-41, wherein the EVA has the structure ofFormula (V):(V); wherein subscript n is from 1 to 100,000; and subscript m is from 1 to 100,000; and the weight ratio of m:n is about 4% by weight to about 60% by weight. - 71 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 43. The polymer blend of claim 42, comprising at least 18% by weight VA in the compoundhaving the structure of Formula (V).

44. The polymer blend of claim 42 or 43, comprising at least 25% by weight VA by weightVA in the compound having the structure of Formula (V).

45. The polymer blend of any one of claims 42-44, comprising at least 40% by weight VA byweight VA in the compound having the structure of Formula (V).

46. The polymer blend of claim 45, wherein the ratio of n:m is 3:2 by weight.

47. The polymer blend of any one of claims 1-46, wherein the APE is made using a two-stepcatalytic combination of hydroaminoalkylation and ring-opening metathesis polymerization (ROMP).

48. The polymer blend of any one of claims 1-47, wherein the APE comprises, or furthercomprises, at least one of the following structures: ; ; ERICASAttorney Docket No.: 125298.00044 ; ; ;- 73 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 ,weren n an m are,n epenen y, a naura numer greaer an an ess an 500,000.

49. The polymer blend of any one of claims 1-48, wherein the polymer blend has adhesiveproperties. - 74 - 1104824148\1\AMERICASAttorney Docket No.: 125298.0004450. The polymer blend of any one of claims 1-49, wherein the polymer blend has an averagepeeling strength of 800 N / m or greater on a PTFE substrate.

51. The polymer blend of any one of claims 1-50, wherein the APE monomer units areconnected in a head to head fashion, head to tail fashion, tail to tail fashion, or any combination thereof.

52. The polymer blend of any one of claims 1-51, further comprising ionomers.

53. The polymer blend of claim 52, wherein the ionomer is neutralized.

54. A substrate coated with the polymer blend of any one of claims 1-53.

55. Apparel, shoe(s), book binding, or automotive part, comprising a surface or interfacecoated with the polymer blend of any one of claims 1-53.

56. A kit comprising a polymer blend of any one of claims 1-53 and instructions fordisposing the polymer blend on a substrate.

57. A substrate comprising the polymer blend of any one of claims 1-53 disposed on at leastone surface or at least interface.

58. The substrate of claim 57, wherein the substrate is a low energy substrate.

59. The substrate of claim 57 or 58, wherein the substrate is selected from the groupconsisting of PTFE, polyethylene, polypropylene, polyolefin, nylon, textile, plastic, composite, glass, wood, fiberglass, metal, ultra-high molecular weight polyethylene (UHMWPE), carbon fiber reinforced polymer, polyester, and combinations thereof.

60. The substrate of claim 57, wherein the substrate is copper (Cu).

61. The substrate any one of claims 57-60, wherein the substrate is a fluoropolymer selectedfrom the group consisting of polytetrafluroroethylene (PTFE), polyvinylfluoride (PVF), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), perfluoroalkoxy polymer (PFA), fluorinated ethylene-propylene (FEP), and related perfluoro elastomers.

62. The substrate of any one of claims 57-61, wherein the substrate is PTFE.- 75 - 1104824148\1\AMERICASAttorney Docket No.: 125298.0004463. The substrate of any one of claims 57-62, wherein the substrate is PTFE and wherein thePTFE is porous.

64. The substrate of any one of claims 57-63, wherein the substrate is non-surface modifiedPTFE.

65. The substrate of any one of claims 57-64, wherein the polymer blend does not releasevolatile organic compounds (VOCs).

66. A trilayer comprising the polymer blend of any one of claims 1-53 between, and incontact with, two substrates.

67. The trilayer of claim 66, wherein the two or more substates are different substrates.

68. The trilayer of claim 67, wherein the two or more substates are the same substrate.

69. A process for making a film of a polymer blend, comprising:mixing in a solvent an amine-functionalized polymer (APE) and a poly (ethylene- co-vinyl acetate) (EVA) co-polymer to form a solvent mixture; wherein the APE:EVA mass ratio is 1:3 to 10:1 casting the solvent mixture on a substrate; and drying the casted solvent mixture to form a film on the substrate.

70. The process of claim 69, further comprising removing the film from the substrate.

71. The process of claim 69 or 70, further comprising using the film as a hot melt adhesive.

72. The process of any one of claims 69-71, further comprising pressing the film ontoanother substrate and heating the film.

73. The process of any one of claims 69-72, wherein the film thickness is 1 µm to 1 mm.

74. The process of claim 73, wherein the film thickness is 0.4 mm.

75. The process of any one of claims 69-74, wherein the solvent is tetrahydrofuran (THF).

76. The process of any one of claims 69-75, comprising evaporating completely the solventfrom the solvent mixture. The process of any one of claims 69-74, further comprising - 76 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044 dissolving the polymer blend in a solvent to form a second solvent mixture; casting the second solvent mixture on a substrate; and drying the casted solvent mixture to form a film on the substrate.

77. The process of any one of claims 69-76, further comprising removing the polymer blendfrom the substrate and repressing the polymer blend to the substrate.

78. A thermoplastic made by the process of any one of claims 69-77.

79. The thermoplastic of claim 78, wherein the thermoplastic is a hot melt adhesive.

80. A process for disposing a polymer blend on a substrate, comprisingproviding a polymer blend of any one of claims 1-53; heating the polymer blend above its melting temperature; disposing the polymer blend on a substrate; and cooling the polymer blend below its melting temperature.

81. The process of claim 80, further comprising pressing the polymer blend on a substrate.

82. The process of claim 80 or 81, wherein the pressing is at a pressure from 0.1 MPa to 100MPa.

83. The process of any one of claims 80-82, wherein the pressing is higher than 0.5 MPa.

84. The process of any one of claims 80-83, wherein the pressing is higher than 1 MPa.

85. The process of any one of claims 80-84, wherein the pressing is at a temperature at orgreater than 60 ºC.

86. The process of claim 85, wherein the pressing is at a temperature at or greater than 90 ºC.

87. The process of claim 86, wherein the pressing is at 1 MPa at a temperature at or greaterthan 90 ºC.

88. The process of any one of claims 80-87, wherein the pressing is for 3 minutes.

89. The process of any one of claims 80-88, further comprising removing the polymer blendfrom the substrate and repressing the polymer blend back on the substrate. - 77 - 1104824148\1\AMERICASAttorney Docket No.: 125298.0004490. The process of claim 89, wherein the repressing is at a pressure from 0.1 MPa to 100MPa.

91. The process of any one of claims 89-90, wherein the repressing is higher than 0.5 MPa.

92. The process of any one of claims 89-91, wherein the repressing is higher than 1 MPa.

93. The process of any one of claims 89-92, wherein the repressing is at a temperature at orgreater than 60 ºC.

94. The process of claim 93, wherein the repressing is at a temperature at or greater than 90ºC.

95. The process of claim 94, wherein the repressing is at 1 MPa at a temperature at or greaterthan 90 ºC.

96. The process of any one of claims 89-95 wherein the repressing is for 3 minutes.

97. A process for disposing a polymer blend on a substrate, comprisingproviding a polymer blend of any one of claims 1-53; and pressing the polymer blend onto a substrate at a pressure of 0.1 MPa to 100 MPa and a temperature of 40 ºC to 200 ºC.

98. The process claim 97, wherein the pressing is for 3 minutes.

99. The process of claim 97 or 98, wherein the pressing is higher than 0.5 MPa.

100. The process of any one of claims 97-99, wherein the pressing is higher than 1MPa.

101. The process of any one of claims 97-100, wherein the pressing is at a temperatureat or greater than 60 ºC.

102. The process of claim 101, wherein the pressing is at a temperature at or greaterthan 90 ºC.

103. The process of claim 102, wherein the pressing is at 1 MPa at a temperature at orgreater than 90 ºC. - 78 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044104. The process of any one of claims 97-103, further comprising melting the polymerblend.

105. The process of any one of claims 97-104, further comprising removing thepolymer blend from the substrate and repressing the polymer blend back on the substrate.

106. The process of claim 105, wherein the repressing is at a pressure from 0.1 MPa to100 MPa.

107. The process of any one of claims 97-106, wherein the repressing is higher than0.5 MPa.

108. The process of any one of claims 97-107, wherein the repressing is higher than 1MPa.

109. The process of any one of claims 97-108, wherein the repressing is at atemperature at or greater than 60 ºC.

110. The process of claim 109, wherein the repressing is at a temperature at or greaterthan 90 ºC.

111. The process of claim 110, wherein the repressing is at 1 MPa at a temperature ator greater than 90 ºC.

112. A method of using the polymer blend of any one of claims 1-53, comprising usingthe polymer blend for crack filling, as an antimicrobial agent, as an adhesive agent, as a coating, as a compatibilizer, as a stabilizer, as a metal scavenger, as a membrane, as a gasket, as a drug delivery agent, as a scavenger agent, comprising applying the amine- functionalized polymer to a substrate.

113. The method of claim 112, wherein the scavenger agent is for binding pollutantsduring environmental remediation in marine environments, and wherein the pollutants include oil, plastic particles, or a combination thereof.

114. The method of claim 112, wherein the membrane is an electrolyte membrane or afiltering membrane for water purification. - 79 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044115. The method of claim 112, wherein the adhesive agent is for adhering to asubstrate, and wherein the substrate is a low energy substrate.

116. The method of any one of claims 112-115, wherein the substrate is selected fromthe group consisting of PTFE, polyethylene, polypropylene, polyolefin, nylon, textile, plastic, composite, glass, wood, fiberglass, metal, and combinations thereof.

117. The method of any one of claims 112-116, wherein the substrate is afluoropolymer selected from the group consisting of polytetrafluroroethylene (PTFE), polyvinylfluoride (PVF), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), perfluoroalkoxy polymer (PFA), fluorinated ethylene-propylene (FEP), and related perfluoro elastomers.

118. The method of any one of claims 112-117, wherein the substrate is PTFE.

119. The methods of any one of claims 112-118, wherein the substrate is PTFE andwherein the PTFE is porous.

120. The methods of any one of claims 112-119, wherein the substrate is non-surfacemodified PTFE.

121. A process for recycling a polymer blend of any one of claims 1-53, comprisingremoving, or allowing to be removed, the polymer blend from a substrate, dissolving the polymer blend, heating the polymer blend, or a combination thereof, and redepositing the polymer blend onto the substrate or a different substrate.

122. A process for repressing a polymer blend of any one of claims 1-53, comprisingdisposing the polymer blend on a substrate, removing, or allowing to be removed, the polymer blend from a substrate, and repressing the polymer blend to the substrate or a different substrate.

123. The process of claim 122, wherein the repressing is at a pressure from 0.1 MPa to100 MPa.

124. The process of any one of claims 122-123, wherein the repressing is higher than0.5 MPa. - 80 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044125. The process of any one of claims 122-124, wherein the repressing is higher than 1MPa.

126. The process of any one of claims 122-125, wherein the repressing is at atemperature at or greater than 60 ºC.

127. The process of claim 126, wherein the repressing is at a temperature at or greaterthan 90 ºC.

128. The process of claim 127, wherein the repressing is at 1 MPa at a temperature ator greater than 90 ºC.

129. A process for self-healing a polymer blend of any one of claims 1-53, comprisingdisposing the polymer blend on a substrate, and heating the polymer blend, applying a solvent to the polymer blend, or both heating the polymer blend and applying a solvent to the polymer blend130. The process of claim 129, wherein the polymer blend is cracked or delaminatedfrom the substrate before the heating or applying a solvent, and wherein the polymer blend is not cracked, not delaminated, or both not cracked and not delaminated after the heating or applying a solvent.

131. A process for repressing a polymer blend of any one of claims 1-53, comprisingdisposing the polymer blend on and between two substrates, separating the two substrates, and repressing the polymer blend between the two substrates.

132. The process of claim 131, wherein some or all of the polymer blend is removedfrom at least one of the two substrates before or during the separating the two substrates.

133. The process of claim 131 or 132, wherein the repressing is at a pressure from 0.1MPa to 100 MPa.

134. The process of any one of claims 131-133, wherein the repressing is higher than0.5 MPa.

135. The process of any one of claims 131-134, wherein the repressing is higher than 1MPa. - 81 - 1104824148\1\AMERICASAttorney Docket No.: 125298.00044136. The process of any one of claims 131-135, wherein the repressing is at atemperature at or greater than 60 ºC.

137. The process of claim 136, wherein the repressing is at a temperature at or greaterthan 90 ºC.

138. The process of claim 137, wherein the repressing is at 1 MPa at a temperature ator greater than 90 ºC. - 82 - 1104824148\1\AMERICAS

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