Polymers and methods making and using polymers

Abstract

The present disclosure provides for polymer compositions, adhesive compositions, pressure-sensitive adhesive compositions, methods of making polymer compositions, and methods of using polymer compositions. In an aspect, the present disclosure provides for polymer compositions that have increased chain entanglements in the rubbery region of ultrahigh molecular weight polymers with improved mechanical performance such as toughness, tensile strength, creep resistance, and modulus.

Description

[0001] Thomas Horstemeyer Docket No.: 222112-2310 POLYMERS AND METHODS MAKING AND USING POLYMERS CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of US Provisional Patent Application No. 63 / 622,220 filed on January 18, 2024, and US Provisional Patent Application No. 63 / 662,465 filed on June 21, 2024, each of which is incorporated herein by reference in its entirety. STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT This invention was made with government support under Grant No.1904631 awarded The National Science Foundation. The government has certain rights in the invention. BACKGROUND Ultra-high molecular weight polyethylene (UHMWPE) has revolutionized the polymer industry, and these materials have exceptional properties, such as high abrasion, fracture resistance, and tensile strength. Various characteristics have been studied, and the characteristic of topological entanglements or crosslinks has become increasingly important in dictating material properties by behaving as physical crosslinks that cause an increase in viscosity and thermal stability and improve mechanical properties such as shear resistance, important characteristics of pressure-sensitive adhesives (PSAs). Additional research in this area may produce materials with advantageous properties. SUMMARY The present disclosure provides for polymer compositions, adhesive compositions, pressure-sensitive adhesive compositions, methods of making polymer compositions, and methods of using polymer compositions. In an embodiment, the present disclosure provides for a composition comprising: a polymer having a molecular weight of about 0.3 MDa to 10 MDa and the following structure: Thomas Horstemeyer Docket No.: 222112-2310   ] , wherein m is 1 to 100,000, n is 1 to 100,000, wherein each of are independently selected from: H, -OR1, -NRxRy, -N+(Rx)3, - 2 , - , -S(O)2Rx, -S(O)2ORx, -S(O)2NRxRy, -NRxS(O)2Ry, -NRxC(O)Ry, -C(O)Rx, -C(O)ORx, -C(O)NRxRy, -NRxC(O)ORy, -NRxC(O)NRxRy, -OC(O)NRxRy, - NRxS(O)2NRxRy, -C(O)NRxS(O)2NRxRy, catechol, a boronic acid group, or a pyridyl disulfide group, where each Rx, Ry, and Rzis independently H or linear or branched C1-18alkyl or aryl as well as -C(O)O(CH2)b-OH, -C(O)O(CH2)b-N(CH3)2, -C(O)O(CH2)bCH3,- N+(CH3)3, -C(O)O(CH2)b-OSO3–, -C(O)O(CH2)b-OSO3H , -C(O)O(CH2)b-SO3–, - C(O)O(CH2)b-SO3H, and -C(O)N(H)C((CH3)2)(CH2)bSO3–, -C(O)N(H)C((CH3)2)(CH2)bSO3H, -(CH2)b-OH, -(CH2)b-N(CH3)2, -(CH2)b-N+(CH3)3, -(CH2)b-OSO3–, -(CH2)b-OSO3H , -(CH2)b- SO3–, -(CH2)b-SO3H, and -C((CH3)2)(CH2)bSO3–, or -C((CH3)2)(CH2)bSO3H where b is 1-20 alkyl. In an embodiment, the present disclosure provides for an adhesive composition comprising the composition as described above or herein, wherein the polymer does not include chemical crosslinking. In an embodiment, the present disclosure provides for a pressure-sensitive adhesive composition comprising the composition as described above or herein, wherein the polymer is free of chemical crosslinking or has less than 5% chemical crosslinking. In an embodiment, the present disclosure provides for a method of making the polymer having a molecular weight of about 0.3 MDa to 10 MDa and of the composition described above or herein, comprising the following polymerization scheme:   ] , m n groups are independently selected from: H, -OR1, -NRxRy, -N+(Rx)3, -N+(Rx)2(Ry), -N+(Rx)(Ry)(Rz), - S(O)2Rx, -S(O)2ORx, -S(O)2NRxRy, -NRxS(O)2Ry, -NRxC(O)Ry, -C(O)Rx, -C(O)ORx, - C(O)NRxRy, -NRxC(O)ORy, -NRxC(O)NRxRy, -OC(O)NRxRy, -NRxS(O)2NRxRy, - C(O)NRxS(O)2NRxRy, catechol, a boronic acid group, or a pyridyl disulfide group, where each Rx, Ry, and Rzis independently H or linear or branched C1-18alkyl or aryl as well as - Thomas Horstemeyer Docket No.: 222112-2310 C(O)O(CH2)b-OH, -C(O)O(CH2)b-N(CH3)2, -C(O)O(CH2)bCH3,-N+(CH3)3, -C(O)O(CH2)b- OSO3–, -C(O)O(CH2)b-OSO3H , -C(O)O(CH2)b-SO3–, -C(O)O(CH2)b-SO3H, and - C(O)N(H)C((CH3)2)(CH2)bSO3–, -C(O)N(H)C((CH3)2)(CH2)bSO3H, -(CH2)b-OH, -(CH2)b- N(CH3)2, -(CH2)b-N+(CH3)3, -(CH2)b-OSO3–, -(CH2)b-OSO3H , -(CH2)b-SO3–, -(CH2)b-SO3H, and -C((CH3)2)(CH2)bSO3–, or -C((CH3)2)(CH2)bSO3H where b is 1-20 alkyl, wherein in the reaction time frame is about 3 to 5 hours or about 4 hours. BRIEF DESCRIPTION OF DRAWINGS The present disclosure may be better understood with reference to the following figures. Corresponding reference numerals designate corresponding parts throughout the figures, and components in the figures are not necessarily to scale. It will be appreciated that the drawings are provided for illustrative purposes and that the invention is not limited to the illustrated embodiment. For clarity and in order to emphasize certain features, not all of the drawings depict all of the features that might be included with the depicted embodiment. The invention also encompasses embodiments that combine features illustrated in multiple different drawings; embodiments that omit, modify, or replace some of the features depicted; and embodiments that include features not illustrated in the drawings. Therefore, it should be understood that there is no restrictive one-to-one correspondence between any given embodiment of the invention and any of the drawings. Figure 1 is a depiction of the advantages of UHMW polyacrylates synthesized via photoiniferter polymerization. (Left) Entanglements serve as physical crosslinks, mimicking the role of chemical crosslinks in conventional pressure-sensitive adhesives and improving mechanical and thermal network stability. (Right) Adhesive chemical structure and failure mechanism as a function of molecular weight. Figures 2A and 2B show (2A) Size exclusion chromatography (SEC) elugrams for poly(methyl acrylate) (PMA) with Mn= 0.25, 1.0, and 2.1 MDa and (2B) the modulus and tan ^^ until material failure in the terminal region measured using dynamic mechanical analysis (DMA) temperature ramps for PMA with Mn= 0.25, 1.0, and 2.1 MDa. Figures 3A-3I show representative stress-strain curves for poly(methyl acrylate) (PMA) of 0.25, 1.0 and 2.1 MDa at (3A) 22 °C, (3B) 30 °C, (3C) 40 °C. The (3D) Young’s modulus, (3E) tensile strength, (3F) toughness were extracted from the tensile stress-strain curves of PMA. * p ≤ 0.05, ** p ≤ 0.01, **** p ≤ 0.0001, + tensile strength at yield. Creep cycles were measured under 500 Pa of stress for PMA of 0.25, 1.0, and 2.1 MDa measured at (3G) 25 °C, (3H) 50 °C, and (3I) 100 °C. Thomas Horstemeyer Docket No.: 222112-2310 Figure 4 shows SEC data for the poly(HEA-co-BA) adhesives of 0.28, 1.3, and 2.3 MDa where the BA monomer was incorporated at 5 per 100 parts by weight of acrylate base polymer. Figures 5A-F show adhesive testing results for P(BA-co-HEA) of 0.28, 1.3, and 2.3 MDa. Time-temperature superposition master curves for P(BA-co-HEA) of (5A) 0.28 MDa, (5B) 1.3 MDa, (5C) 2.3 MDa. (5D) Peel force values from 180 ° peel test as a function of molecular weight and temperature. (5E) The maximum peak force measured during loop tack measurements as a function of molecular weight and temperature. (5F) Results from 180 ° peel tests at 25 °C after a residence time of 1 min and 24 h. Peak force values were obtained from the maximum force required to remove the sample from the substrate surface immediately after contact. Peel force values were collected after 1 min of residence time unless otherwise indicated. Dotted bars signify cohesive failure. Figure 6 shows a photoreactor system used to synthesize >20 g PMA. Figure 7 shows1H NMR spectrum of PMA of Mn0.25 MDa after purification (CDCl3). Figure 8 shows1H NMR spectrum of PMA of Mn1.0 MDa after purification (CDCl3). Figure 9 shows1H NMR spectrum of PMA of Mn2.1 MDa after purification (CDCl3). Figure 10 shows thermogravimetric analysis (TGA) thermograms for PMA of 0.25, 1.0, and 2.1 MDa. Figure 11 shows differential scanning calorimetry (DSC) temperature ramps for PMA with Mnof 0.25, 1.0, and 2.1 MDa. Figure 12 shows the strain (%) at break extracted from stress strain curves for PMA of 0.25, 1.0, and 2.1 MDa at 22, 30, and 40 °C. Strain at the instrument limit is indicated by ++. Figure 13 shows a pseudo-first-order kinetics plot obtained by1H NMR spectroscopy for the synthesis of P(BA-co-HEA) with Mnof 0.28 MDa. Figure 14 shows a pseudo-first-order kinetics plot obtained by1H NMR spectroscopy for the synthesis of P(BA-co-HEA) with Mnof 1.3 MDa. Figure 15 shows a pseudo-first-order kinetics plot obtained by1H NMR spectroscopy for the synthesis of P(BA-co-HEA) with Mnof 2.3 MDa. Figure 16 shows a number-average molecular weight (Mn) and dispersity (Đ) versus conversion plot for the synthesis of P(BA-co-HEA) with Mnof 0.28 MDa. Figure 17 shows a SEC trace for the synthesis of P(BA-co-HEA) with Mnof 0.28 MDa showing the uniform shift in molecular weight over time. Thomas Horstemeyer Docket No.: 222112-2310 Figure 18 shows a number-average molecular weight (Mn) and dispersity (Đ) versus conversion plot for the synthesis of P(BA-co-HEA) with Mnof 1.3 MDa Figure 19 shows a SEC trace for the synthesis of P(BA-co-HEA) with Mnof 1.3 MDa showing the uniform shift in molecular weight over time. Figure 20 shows a number-average molecular weight (Mn) and dispersity (Đ) versus conversion plot for the synthesis of P(BA-co-HEA) with Mnof 2.3 MDa. Figure 21 shows a SEC trace for the synthesis of P(BA-co-HEA) with Mnof 2.3 MDa showing the uniform shift in molecular weight over time. Figure 22 shows1H NMR spectrum of P(BA-co-HEA) of Mn0.28 MDa after purification (CDCl3). Labels indicate the integrations used for calculating incorporation of HEA. Figure 23 shows1H NMR spectrum of P(BA-co-HEA) of Mn1.3 MDa after purification (CDCl3). Labels indicate the integrations used for calculating incorporation of HEA. Figure 24 shows1H NMR spectrum of P(BA-co-HEA) of Mn2.3 MDa after purification (CDCl3). Labels indicate the integrations used for calculating incorporation of HEA. Figure 25 shows TGA thermograms for P(BA-co-HEA) with Mnof 0.28, 1.3, and 2.3 MDa. Figure 26 shows DSC temperature ramps for P(BA-co-HEA) with Mnof 0.28, 1.3, and 2.3 MDa P(BA-co-HEA). Figure 27 shows oscillatory frequency sweeps at 25, 75, and 145 °C showing the tan ^^ and the storage modulus for the 1.3 MDa P(BA-co-HEA). Figure 28 shows oscillatory frequency sweeps at 25, 75, and 145 °C showing the tan ^^ and the storage modulus for the 2.3 MDa P(BA-co-HEA). Figures 29A and 29B show (29A) Coating adhesives onto PET backing for preparation of 1 in. wide adhesive strips, which were used for 180° peel testing and loop tack testing on stainless-steel. (29B) Representative stainless-steel surfaces showing residue remaining from cohesive failure of the 0.28 MDa adhesive compared to clean surfaces after 180° peel testing of UHMW adhesives which failed interfacially.

[0002] Thomas Horstemeyer Docket No.: 222112-2310 DETAILED DESCRIPTION The present disclosure provides for polymer compositions, adhesive compositions, pressure-sensitive adhesive compositions, methods of making polymer compositions, and methods of using polymer compositions. Before the present disclosure is described in greater detail, it is to be understood that this disclosure is not limited to particular embodiments described, and as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting, since the scope of the present disclosure will be limited only by the appended claims. Where a range of values is provided, it is understood that each intervening value, to the tenth of the unit of the lower limit unless the context clearly dictates otherwise, between the upper and lower limit of that range and any other stated or intervening value in that stated range, is encompassed within the disclosure. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges and are also encompassed within the disclosure, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present disclosure, the preferred methods and materials are now described. As will be apparent to those of skill in the art upon reading this disclosure, each of the individual embodiments described and illustrated herein has discrete components and features which may be readily separated from or combined with the features of any of the other several embodiments without departing from the scope or spirit of the present disclosure. Any recited method can be carried out in the order of events recited or in any other order that is logically possible. Embodiments of the present disclosure will employ, unless otherwise indicated, techniques of chemistry, material science, tribo- / rheology, and the like, which are within the skill of the art. The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how to perform the methods and use the compositions, methods, and materials disclosed and claimed herein. Efforts have been Thomas Horstemeyer Docket No.: 222112-2310 made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, temperature is in °C, and pressure is at or near atmospheric. Standard temperature and pressure are defined as 20 °C and 1 atmosphere. Before the embodiments of the present disclosure are described in detail, it is to be understood that, unless otherwise indicated, the present disclosure is not limited to particular materials, reagents, reaction materials, manufacturing processes, or the like, as such can vary. It is also to be understood that the terminology used herein is for purposes of describing particular embodiments only and is not intended to be limiting. It is also possible in the present disclosure that steps can be executed in different sequence where this is logically possible. It must be noted that, as used in the specification and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. As used herein, the following terms have the meanings ascribed to them unless specified otherwise. In this disclosure, "consisting essentially of" or "consists essentially" or the like, when applied to methods and compositions encompassed by the present disclosure refers to compositions like those disclosed herein, but which may contain additional structural groups, composition components or method steps (or analogs or derivatives thereof as discussed above). Such additional structural groups, composition components or method steps, etc., however, do not materially affect the basic and novel characteristic(s) of the compositions or methods, compared to those of the corresponding compositions or methods disclosed herein. "Consisting essentially of" or "consists essentially" or the like, when applied to methods and compositions encompassed by the present disclosure have the meaning ascribed in U.S. Patent law and the term is open-ended, allowing for the presence of more than that which is recited so long as basic or novel characteristics of that which is recited is not changed by the presence of more than that which is recited, but excludes prior art embodiments. Definitions By "chemically feasible" is meant a bonding arrangement or a compound where the generally understood rules of organic structure are not violated. The structures disclosed herein, in all of their embodiments are intended to include only "chemically feasible" structures, and any recited structures that are not chemically feasible, for example in a Thomas Horstemeyer Docket No.: 222112-2310 structure shown with variable atoms or groups, are not intended to be disclosed or claimed herein. However, if a bond appears to be intended and needs the removal of a group such as a hydrogen from a carbon, the one of skill would understand that a hydrogen could be removed to form the desired bond. It is understood that “substitution” or “substituted” includes the implicit proviso that such substitution is in accordance with permitted valence of the substituted atom and the substituent, and that the substitution results in a stable compound, i.e., a compound that does not spontaneously undergo transformation such as by rearrangement, cyclization, elimination, etc. “Polymers” are understood to include, but are not limited to, homopolymers, copolymers, such as for example, block, graft, random and alternating copolymers, terpolymers, etc. and blends and modifications thereof. As used herein, “alkyl” or “alkyl group” refers to a saturated aliphatic hydrocarbon, which can be straight or branched, having 1 to 40, 1 to 20, 1 to 10, or 1 to 5 carbon atoms, where the stated range of carbon atoms includes each intervening integer individually, as well as sub-ranges. Examples of alkyl groups include, but are not limited to methyl, ethyl, n- propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, and s-pentyl. Reference to “alkyl” or “alkyl group” includes unsubstituted and substituted forms of the hydrocarbon moiety. As used herein, “halo”, “halogen”, or “halide”, refers to a fluorine, chlorine, bromine, iodine, and astatine, and radicals thereof. Further, when used in compound words, such as “haloalkyl” refers to an alkyl or alkenyl radical in which one or more hydrogens are substituted by halogen radicals. The term “unsaturated” refers to a molecule, such as a hydrocarbon or hydrocarbon moiety that includes one or more double bonds and / or triple bonds. “Aryl”, as used herein, refers to C5-C20-membered aromatic, heterocyclic, fused aromatic, fused heterocyclic, biaromatic, or bihetereocyclic ring systems. In an aspect, “aryl”, can include 5-, 6-, 7-, 8-, 9-, and 10-membered single-ring aromatic groups that may include from zero to four heteroatoms, for example, functional groups that correspond to benzene, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, triazole, pyrazole, pyridine, pyrazine, pyridazine and pyrimidine, and the like. Those aryl groups having heteroatoms in the ring structure may also be referred to as “aryl heterocycles” or “heteroaromatics”. The aromatic ring can be substituted at one or more ring positions with one or more substituents including, but not limited to, halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, alkoxyl, amino (or quaternized amino), nitro, sulfhydryl, imino, amido, phosphonate, phosphinate, Thomas Horstemeyer Docket No.: 222112-2310 carbonyl, carboxyl, silyl, ether, alkylthio, sulfonyl, sulfonamido, ketone, aldehyde, ester, heterocyclyl, aromatic or heteroaromatic moieties, -CF3, -CN; and combinations thereof. The term “aryl” also includes polycyclic ring systems (C5-C30) having two or more cyclic rings in which two or more carbons are common to two adjoining rings (i.e., “fused rings”) wherein at least one of the rings is aromatic, e.g., the other cyclic ring or rings can be cycloalkyls, cycloalkenyls, cycloalkynyls, aryls and / or heterocycles. Examples of heterocyclic rings include, but are not limited to, benzimidazolyl, benzofuranyl, benzothiofuranyl, benzothiophenyl, benzoxazolyl, benzoxazolinyl, benzthiazolyl, benztriazolyl, benztetrazolyl, benzisoxazolyl, benzisothiazolyl, benzimidazolinyl, carbazolyl, 4aH carbazolyl, carbolinyl, chromanyl, chromenyl, cinnolinyl, decahydroquinolinyl, 2H,6H- 1,5,2-dithiazinyl, dihydrofuro[2,3 b]tetrahydrofuran, furanyl, furazanyl, imidazolidinyl, imidazolinyl, imidazolyl, 1H-indazolyl, indolenyl, indolinyl, indolizinyl, indolyl, 3H-indolyl, isatinoyl, isobenzofuranyl, isochromanyl, isoindazolyl, isoindolinyl, isoindolyl, isoquinolinyl, isothiazolyl, isoxazolyl, methylenedioxyphenyl, morpholinyl, naphthyridinyl, octahydroisoquinolinyl, oxadiazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, oxazolidinyl, oxazolyl, oxindolyl, pyrimidinyl, phenanthridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenoxathinyl, phenoxazinyl, phthalazinyl, piperazinyl, piperidinyl, piperidonyl, 4-piperidonyl, piperonyl, pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolidinyl, pyrazolinyl, pyrazolyl, pyridazinyl, pyridooxazole, pyridoimidazole, pyridothiazole, pyridinyl, pyridyl, pyrimidinyl, pyrrolidinyl, pyrrolinyl, 2H-pyrrolyl, pyrrolyl, quinazolinyl, quinolinyl, 4H-quinolizinyl, quinoxalinyl, quinuclidinyl, tetrahydrofuranyl, tetrahydroisoquinolinyl, tetrahydroquinolinyl, tetrazolyl, 6H-1,2,5-thiadiazinyl, 1,2,3- thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, thianthrenyl, thiazolyl, thienyl, thienothiazolyl, thienooxazolyl, thienoimidazolyl, thiophenyl, 1,2,3-triazole, 1,2,4- triazole and xanthenyl. One or more of the rings can be substituted as defined above for “aryl”. In some aspects, a structure of a compound can be represented by a formula: , which is understood to be equivalent to a , Thomas Horstemeyer Docket No.: 222112-2310 where n is typically an integer. That is, Rnis understood to represent five independent substituents, Rn(a), Rn(b), Rn(c), Rn(d), and Rn(e). By “independent substituents,” it is meant that each R substituent can be independently defined. For example, if in one instance Rn(a)is halogen, then Rn(b)is not necessarily halogen in that instance. Discussion: The present disclosure provides for polymer compositions, adhesive compositions, pressure-sensitive adhesive compositions, methods of making polymer compositions, and methods of using polymer compositions. In an aspect, the present disclosure provides for polymer compositions that have increased chain entanglements in the rubbery region of ultrahigh molecular weight polymers (e.g., polyacrylates) with improved mechanical performance (e.g., toughness, tensile strength, creep resistance, and modulus). Additional details are provided below and in the Examples. In an aspect, polyacrylate-based adhesives of the present disclosure showed improved cohesive strength, compared to “standard” molecular weight adhesives without chemical crosslinkers (e.g., the standard molecular weight of less than 1 MDa), based on physical mechanical entanglements (not chemical entanglements) behaving as crosslinkers. Crosslinkers are usually necessary in commercial adhesives to prevent cohesive failure, which leaves surface residue. Additionally, the use of crosslinkers creates an extra step during synthesis of adhesive products and produces products which cannot be recycled. The present disclosure provides for polymer compositions that have ultrahigh molecular weights (e.g., 0.3 MDa to 10 MDa, about 1 MDa to 3 MDa) and can be used as adhesives (e.g., pressure-sensitive adhesives) that do not include or have very low levels of chemical crosslinkers (e.g., less than 5%, less than 3%, or less than 1% chemical crosslinkers) to prevent cohesive failure, but uses physical mechanical entanglements (which may be referred to as “physical crosslinking but this does not include chemical crosslinking) to prevent cohesive failure and limit or eliminate surface residue while being recyclable. The present disclosure provides for polymers that two or more monomer units, which can include (alkyl)acrylate esters (e.g., (meth)acrylate esters), which may be used alone or in combination with each other, include butyl acrylate, 2-methylbutyl acrylate, 2- ethylhexyl acrylate, isooctyl acrylate, lauryl acrylate, n-decyl acrylate, 4-methyl 2-pentyl acrylate, isoamyl acrylate, Sec-butyl acrylate, and isononyl acrylate. Examples of carboxylic acid functional monomers, which may be used alone or in combination with each other, include acrylic acid, meth acrylic acid, itaconic acid, maleic acid, and fumaric acid. Examples Thomas Horstemeyer Docket No.: 222112-2310 of other monomers that may be co-polymerized with the (meth)acrylate ester and carboxylic acid-functional monomers include ethyl acrylate, (meth)acrylamide, alpha olefins, vinyl ethers, allyl ethers, styrene, maleic acid esters, 2-hydroxyethyl (meth)acrylate, cyclohexyl acrylate, t-butyl acrylate, phenyl acrylate, isobornyl acrylate, 2-phenoxyethyl acrylate, N-vinyl pyrrolidone, N-vinyl caprolactam, and substituted acrylamides such as N-ethyl acrylamide, N-hydroxyethyl acrylamide, N- octyl acrylamide, N-t-butyl. In an aspect, present disclosure provides for polymers that have ultrahigh molecular weights (e.g., 0.3 MDa to 10 MDa, about 1 MDa to 3 MDa) that can be represented by the     following structures: . In a particular . initiation system (See polymerization process) selected to be used. The initiation system includes all chemical species as would typically be used by an expert in the field using the polymerization techniques such as: a radical polymerization, conventional radical polymerization, reversible-deactivation radical polymerization, reversible addition-fragmentation chain transfer (RAFT) polymerization, macromolecular design by interchange of xanthate (MADIX) polymerization, photoiniferter polymerization, atom transfer radical polymerization (ATRP), or stable free radical polymerization (SFRP) as well as by post-polymerization modification (e.g., by modification of monomer units that contain activated ester groups. Since each polymerization (e.g., RAFT, MADIX, SFRP, etc.) uses a different reaction method, “A” and “B” can vary. For example, ATRP uses alkyl halide initiators and transition metal catalyst with ligands. The chemical structure of those ligands, catalyst, and halide initiators varies. RAFT or photoiniferter can use many different types of end groups to control the molecular weight such as carbamates, trithiocarbonates, xanthates, and dithiobenzoates. Each one of these classes also has an assortment of variable chemistries or what we call R and Z groups. Different thermal initiators can be used as well. The same is true for each of the other types of polymerization techniques, such as those described above and herein. Addition details are provided in the Examples. Thomas Horstemeyer Docket No.: 222112-2310 Subscript m can be 1 to 100,000 or 1 to 10,000. Subscript n can be 1 to 100,000 or 1 to 10,000. Subscript q can be 2 to 20 or 2 to 10. Each of R1, R2, R3, and R4 groups can independently can be H, -OR1, -NRxRy, -N+(Rx)3, -N+(Rx)2(Ry), -N+(Rx)(Ry)(Rz), - S(O)2Rx, -S(O)2ORx, -S(O)2NRxRy, -NRxS(O)2Ry, -NRxC(O)Ry, -C(O)Rx, -C(O)ORx, - C(O)NRxRy, -NRxC(O)ORy, -NRxC(O)NRxRy, -OC(O)NRxRy, -NRxS(O)2NRxRy, - C(O)NRxS(O)2NRxRy, catechol, a boronic acid group, and a pyridyl disulfide group. Each of Rx, Ry, and Rzcan independently be H or linear or branched C1-18alkyl and aryl as well as -C(O)O(CH2)b-OH, -C(O)O(CH2)b-N(CH3)2, -C(O)O(CH2)bCH3,-N+(CH3)3, -C(O)O(CH2)b- OSO3–, -C(O)O(CH2)b-OSO3H , -C(O)O(CH2)b-SO3–, -C(O)O(CH2)b-SO3H, and - C(O)N(H)C((CH3)2)(CH2)bSO3–, -C(O)N(H)C((CH3)2)(CH2)bSO3H, -(CH2)b-OH, -(CH2)b- N(CH3)2, -(CH2)b-N+(CH3)3, -(CH2)b-OSO3–, -(CH2)b-OSO3H , -(CH2)b-SO3–, -(CH2)b-SO3H, and -C((CH3)2)(CH2)bSO3–, -C((CH3)2)(CH2)bSO3H where b can be 1-20 carbon alkyl. In an aspect, R1 and R2 are selected to be a monomer unit that is different than the monomer unit including R3 and R4. In an aspect, the polymer can include 1 to 10 or 1 to 5 additional monomer units not shown in the figure shown above, where each of the 1 to 5 additional monomer units are different than the monomer units that include R1 and R2 and R3 and R4. Also, the 1 to 5 additional monomer units are each different than one another. In an aspect, the additional monomer units can be selected from the group consisting of: (meth)acrylate esters, and (meth)acrylic acids, styrene, (meth)acrylamides. In an aspect, the polymer (that includes the additional monomer unit) can be described by one of the following structures:   , , , Thomas Horstemeyer Docket No.: 222112-2310   ] or o Subscript r can be 1 to 100,000 or 1 to 10,000. Each of R5, R6, R7, R8, R9, and R10 groups can be independently selected from: H, -OR1, -NRxRy, -N+(Rx)3, -N+(Rx)2(Ry), - N+(Rx)(Ry)(Rz), -S(O)2Rx, -S(O)2ORx, -S(O)2NRxRy, -NRxS(O)2Ry, -NRxC(O)Ry, -C(O)Rx, - C(O)ORx, -C(O)NRxRy, -NRxC(O)ORy, -NRxC(O)NRxRy, -OC(O)NRxRy, -NRxS(O)2NRxRy, - C(O)NRxS(O)2NRxRy, catechol, a boronic acid group, and a pyridyl disulfide group. Each of Rx, Ry, and Rzcan be independently selected from H or linear or branched C1-18alkyl and aryl as well as -C(O)O(CH2)b-OH, -C(O)O(CH2)b-N(CH3)2, -C(O)O(CH2)bCH3,-N+(CH3)3, -C(O)O(CH2)b-OSO3–, -C(O)O(CH2)b-OSO3H , -C(O)O(CH2)b-SO3–, -C(O)O(CH2)b-SO3H, and -C(O)N(H)C((CH3)2)(CH2)bSO3–, -C(O)N(H)C((CH3)2)(CH2)bSO3H, -(CH2)b-OH, -(CH2)b- Thomas Horstemeyer Docket No.: 222112-2310 N(CH3)2, -(CH2)b-N+(CH3)3, -(CH2)b-OSO3–, -(CH2)b-OSO3H , -(CH2)b-SO3–, -(CH2)b-SO3H, and -C((CH3)2)(CH2)bSO3–, -C((CH3)2)(CH2)bSO3H, where b can be a 1-20 carbon alkyl. In an aspect, R1 and R2 are selected to be a monomer unit that is different than the monomer unit including R3 and R4 and the monomer unit including R5 and R6 so that each monomer unit (monomer unit including R1 and R2, monomer unit including R3 and R4, and monomer unit including R5 and R6) are different monomer units. In an aspect, the polymer can be described by the following structure: q .In an aspect, R1 can be hydrogen or an alkyl group can be a –(CH2)x- group, where x is 1 to 12 or 1 to 8. Subscript m can be 1 to 100,000 or 1 to 10,000. Subscript n can be 1 to 100,000 or 1 to 10,000. Subscript q can be 2 to 20 or 5 to 20. The polymers described above and herein include physical mechanical entanglement (which can be referred to as physical crosslinking) as opposed to chemical crosslinking. In an aspect, the polymer can have a polydispersity index (Đ) of about 1.1. to 1.6 or about 1.1 to 1.3. In aspects, the polymer can have a molecular weight about 0.3 MDa to 10 MDa, about 0.3 MDa to 5 MDa, about 0.3 MDa to 3 MDa or about 1.5 MDa to 2 MDa. In a particular aspect, the polymer can have a polydispersity index (Đ) of about 1.1 to 2 or about 1.1 to 1.3 and a molecular weight about 0.3 MDa to 2 MDa. In another particular aspect, the polymer can have a polydispersity index (Đ) of about 1.2 to 1.3 and a molecular weight about 1.5 MDa to 2 MDa. In an aspect, the adhesive compositions can also include tackifiers. The tackifier can be about 0.01 to 5% or 0.01 to 10% or more as need for a particular adhesive composition. In an embodiment, the polymer can be linear or non-linear such as star-like, branched, hyperbranched, comb / brush-like, gradient copolymer, bottle brush-like, cyclic or network. A linear polymer can be defined as a macromolecular structure comprised of monomeric units covalently linked together in a sequential and unidirectional manner, forming a single continuous chain. This architecture is devoid of crosslinks, side chains and network structures that would arise from connections between polymer chains. Thomas Horstemeyer Docket No.: 222112-2310 A branched polymer can be defined as a macromolecular architecture where one or more side chains extend from the primary linear backbone. For example, this architecture can result from the incorporation of monomers with multiple reactive sites during the polymerization process. These side chains, which may vary in length, regularity, and density create a more complex heterogeneous topology compared to linear polymers. The degree of branching (DB) can be calculated by the equation: ^^^^ ൌ2^^ 2^^ ^ ^^where D represents molar equivalents branching unit, and L represents molar equivalents of the linear unit. Herein, can be defined as having a DB greater than 0 but less than 0.4. A hyperbranched polymer can be defined as a macromolecular structure characterized by tree-like topology that differentiates it from conventional branched polymers. The defining feature of hyperbranched polymers is their high DB, which is greater than 0.4 but less than 1. A star polymer can be defined as a macromolecular structure characterized by ‘arms’ extending from a central core. Star polymers have inherently more chain-ends than linear polymers. These ‘arms’, which may vary in length, regularity, and density create a more complex heterogeneous topology compared to linear polymers. In an aspect, the backbone unit can include monomer units and copolymers including the monomer units. In an aspect, the polymer can be a block copolymer, a random copolymer, a statistical copolymer, an alternating copolymer, or a gradient copolymer. A gradient copolymer is a polymer with more than one type of monomer unit where the frequency of occurrence of at least one monomer unit changes gradually along the polymer chain. A statistical copolymer is a copolymer in which the sequential distribution of the monomeric units obeys known statistical laws and is based on relative reactivities. The polymer composition can be used in an adhesive composition. The polymers composition of the adhesive composition is free (e.g., about 90% or more, about 95% or more, about 99% or more, about 100%, or 100%) of chemical crosslinking. Thus, unlike other cross-linked adhesives, the adhesive composition of the present disclosure is recyclable. The adhesive composition has improved mechanical performance in one or more of the following: toughness, tensile strength, creep resistance, and modulus compared to standard molecular weight adhesives without chemical crosslinking. In one embodiment, toughness improved by about 40% to 50% or about 45%, tensile strength improved by about Thomas Horstemeyer Docket No.: 222112-2310 75% to 90% or about 85%, and / or creep resistance improved by about 55 to 75% or about 65% when molecular weight increased by about 1 MDa. In another embodiment, modulus improved by about 26% when molecular weight increased by about 2 MDa. Pressure-sensitive adhesives are formed from viscoelastic polymers that adhere to a surface with application of minimal pressure while also preventing flow (cohesiveness), allowing for easy removal without tearing. Pressure necessary for adhesion may vary depending on the molecular weight and composition of the polymer. In one aspect, the polymer of the present disclosure can be prepared via reversible- deactivation radical polymerization in organic solvents (See, ACS Macro. Lett., 2020, 9(4), 613-618). In one embodiment, the polymeric material is prepared via photoiniferter polymerization. These materials with controlled molecular weight could also be derived through other controlled radical polymerization methods, such as atom transfer radical polymerization, and nitroxide mediated polymerization. Additionally, these materials could be derived through conventional radical, anionic, cationic, ring-opening, and ring-opening metathesis polymerization. In particular, the present disclosure provides for synthetic methods of making the polymer as provided herein by polymerizing to form the polymer. The polymerization can be a radical polymerization, conventional radical polymerization, reversible-deactivation radical polymerization, reversible addition-fragmentation chain transfer (RAFT) polymerization, macromolecular design by interchange of xanthate (MADIX) polymerization, photoiniferter polymerization, atom transfer radical polymerization (ATRP), or stable free radical polymerization (SFRP) as well as by post-polymerization modification (e.g., by modification of monomer units that contain activated ester groups). In an aspect, the polymer can be made according to the following polymerization scheme:   ] Thomas Horstemeyer Docket No.: 222112-2310 where 3 to 5 is at about 1 atm. The initiation system can be defined as a chemical moiety that, upon exposure to light, heat, electricity, redox conditions, or other stimulant, produces radicals, cations, anions or other species that react to produce polymers. The initiation system includes all chemical species as would typically be used by an expert in the field using the polymerization techniques such as: a radical polymerization, conventional radical polymerization, reversible-deactivation radical polymerization, reversible addition- fragmentation chain transfer (RAFT) polymerization, macromolecular design by interchange of xanthate (MADIX) polymerization, photoiniferter polymerization, atom transfer radical polymerization (ATRP), or stable free radical polymerization (SFRP) as well as by post- polymerization modification (e.g., by modification of monomer units that contain activated ester groups). “A” and “B” are determined based on the initiation system selected to be used. Since each polymerization (e.g., RAFT, MADIX, SFRP, etc.) uses a different reaction method, “A” and “B” can vary. For example, ATRP uses alkyl halide initiators and transition metal catalyst with ligands. The chemical structure of those ligands, catalyst, and halide initiators varies. RAFT or photoiniferter can use many different types of end groups to control the molecular weight such as carbamates, trithiocarbonates, xanthates, and dithiobenzoates. Each one of these classes also has an assortment of variable chemistries or what we call R and Z groups. Different thermal initiators can be used as well. The same is true for each of the other types of polymerization techniques, such as those described above and herein. Addition details are provided in the Examples. In addition, specific reactions for also described below, where “A” and “B” are more particularly defined. Also, in embodiments that include 1 to 10 or 1 to 5 additional monomer units, the method of making can be modified by adding a monomer corresponding to the monomer unit to be formed to the polymerization process to form the desired polymer. In another aspect, the polymer can be made according to the following polymerization scheme: Thomas Horstemeyer Docket No.: 222112-2310 is at about 1 atm. Additional details are provided below and in Examples 1 and 2. Also, in embodiments that include 1 to 5 additional monomer units, the method of making can be modified by adding a monomer corresponding to the monomer unit to be formed to the polymerization process to form the desired polymer. In particular, the polymer can be made according to the following polymerization scheme: q R1, hours or about 4 hours. The temperature can be about 20 °C to 45 °C. The pressure is at about 1 atm. Additional details are provided below and in Examples 1 and 2 In an embodiment, the polymer can be made according to the following polymerization scheme: A typical photoiniferter polymerization initiated by a trithiocarbonate is as follows. targeting Mn^ 2.00 ^ 106g / mol). Butyl acrylate (8.01 g, 62.5 mmol), hydroxyethyl acrylate (0.431 g, Thomas Horstemeyer Docket No.: 222112-2310 3.63 mmol), and trithiocarbonate iniferter (0.769 g, 2.11 ^ 10-3mmol from 1.00 mg / mL dimethylformamide (DMF) stock solution) were dissolved in dimethyl sulfoxide (DMSO) (6.35 mL, 4 M [Monomer]) in a 20 mL scintillation vial. The iniferter stock solution was stored between 2 and 6 ^C for further use. Argon was bubbled through the polymerization solution for 10 min. The reaction vessel was positioned 2.50 cm from the ultraviolet (UV) light source for an intensity of 7.0 mW / cm2, and polymerization was initiated upon irradiation. Monomer conversion was determined by1H NMR spectroscopy, monitoring the disappearance of the monomer vinyl peaks relative to DMF. Reaction aliquots were removed periodically, diluted in SEC solvent, and used to determine molecular weight through SEC analysis. Now having describe various embodiments of the present disclosure, addition featrues are described. Feature 1. A composition comprising: a polymer having a molecular weight of about 0.3 MDa to 10 MDa and the following structure:   , wherein m is 1 to 100,000, n is 1 to 100,000, wherein each of are independently selected from: H, -OR1, -NRxRy, -N+(Rx)3, - N+(Rx)2(Ry), -N+(Rx)(Ry)(Rz), -S(O)2Rx, -S(O)2ORx, -S(O)2NRxRy, -NRxS(O)2Ry, -NRxC(O)Ry, -C(O)Rx, -C(O)ORx, -C(O)NRxRy, -NRxC(O)ORy, -NRxC(O)NRxRy, -OC(O)NRxRy, - NRxS(O)2NRxRy, -C(O)NRxS(O)2NRxRy, catechol, a boronic acid group, or a pyridyl disulfide group, where each Rx, Ry, and Rzis independently H or linear or branched C1-18alkyl or aryl as well as -C(O)O(CH2)b-OH, -C(O)O(CH2)b-N(CH3)2, -C(O)O(CH2)bCH3,- N+(CH3)3, -C(O)O(CH2)b-OSO3–, -C(O)O(CH2)b-OSO3H , -C(O)O(CH2)b-SO3–, - C(O)O(CH2)b-SO3H, and -C(O)N(H)C((CH3)2)(CH2)bSO3–, -C(O)N(H)C((CH3)2)(CH2)bSO3H, -(CH2)b-OH, -(CH2)b-N(CH3)2, -(CH2)b-N+(CH3)3, -(CH2)b-OSO3–, -(CH2)b-OSO3H , -(CH2)b- SO3–, -(CH2)b-SO3H, and -C((CH3)2)(CH2)bSO3–, or -C((CH3)2)(CH2)bSO3H where b is 1-20 alkyl. Feature 2. The composition of each of the features described herein, wherein the polymer includes 1 to 5 additional monomer units in the polymer chain. Feature 3. The composition of each of the features described herein, wherein the 1 to 5 additional monomer units are selected from the group consisting of: (meth)acrylate esters, and (meth)acrylic acids, styrene, (meth)acrylamides. Feature 4. The composition of each of the features described herein, wherein the polymer including additional monomer units has one of the following structures: Thomas Horstemeyer Docket No.: 222112-2310   ]   or   wherein o is 1 of R5, R6, R7, R8, R9, and R10 groups are H, -OR1, -NRxRy, -N+(Rx)3, - N+(Rx)2(Ry), -N+(Rx)(Ry)(Rz), -S(O)2Rx, -S(O)2ORx, -S(O)2NRxRy, -NRxS(O)2Ry, -NRxC(O)Ry, -C(O)Rx, -C(O)ORx, -C(O)NRxRy, -NRxC(O)ORy, -NRxC(O)NRxRy, -OC(O)NRxRy, - NRxS(O)2NRxRy, -C(O)NRxS(O)2NRxRy, catechol, a boronic acid group, or a pyridyl disulfide group, where each Rx, Ry, and Rzis independently H or linear or branched C1-18alkyl or aryl as well as -C(O)O(CH2)b-OH, -C(O)O(CH2)b-N(CH3)2, -C(O)O(CH2)bCH3,- N+(CH3)3, -C(O)O(CH2)b-OSO3–, -C(O)O(CH2)b-OSO3H , -C(O)O(CH2)b-SO3–, - C(O)O(CH2)b-SO3H, and -C(O)N(H)C((CH3)2)(CH2)bSO3–, -C(O)N(H)C((CH3)2)(CH2)bSO3H, -(CH2)b-OH, -(CH2)b-N(CH3)2, -(CH2)b-N+(CH3)3, -(CH2)b-OSO3–, -(CH2)b-OSO3H , -(CH2)b- SO3–, -(CH2)b-SO3H, and -C((CH3)2)(CH2)bSO3–, -or C((CH3)2)(CH2)bSO3H, where b is 1-20 alkyl. Feature 5. The composition of each of the features described herein, wherein the polymer including additional monomer units has one of the following structures: or Thomas Horstemeyer Docket No.: 222112-2310 1 N+(Rx)2(Ry), -N+(Rx)(Ry)(Rz), -S(O)2Rx, -S(O)2ORx, -S(O)2NRxRy, -NRxS(O)2Ry, -NRxC(O)Ry, -C(O)Rx, -C(O)ORx, -C(O)NRxRy, -NRxC(O)ORy, -NRxC(O)NRxRy, -OC(O)NRxRy, - NRxS(O)2NRxRy, -C(O)NRxS(O)2NRxRy, catechol, a boronic acid group, or a pyridyl disulfide group, where each Rx, Ry, and Rzis independently H or linear or branched C1-18alkyl or aryl as well as -C(O)O(CH2)b-OH, -C(O)O(CH2)b-N(CH3)2, -C(O)O(CH2)bCH3,- N+(CH3)3, -C(O)O(CH2)b-OSO3–, -C(O)O(CH2)b-OSO3H , -C(O)O(CH2)b-SO3–, - C(O)O(CH2)b-SO3H, and -C(O)N(H)C((CH3)2)(CH2)bSO3–, -C(O)N(H)C((CH3)2)(CH2)bSO3H, -(CH2)b-OH, -(CH2)b-N(CH3)2, -(CH2)b-N+(CH3)3, -(CH2)b-OSO3–, -(CH2)b-OSO3H , -(CH2)b- SO3–, -(CH2)b-SO3H, and -C((CH3)2)(CH2)bSO3–, -or C((CH3)2)(CH2)bSO3H, where b is 1-20 alkyl. Feature 6. The composition of each of the features described herein, wherein the q polymer has the following structure:, wherein R1 an alkylgroup, wherein R2 is selected from composition of each of the features described herein, wherein the polymer has a molecular weight of about 1 MDa to 10 MDa. Feature 8. The composition of each of the features described herein, wherein the polymer has a molecular weight of about 1.5 MDa to 2 MDa. Feature 9. The composition of each of the features described herein, wherein q is 5 to 20. Feature 10. The composition of each of the features described herein, wherein R1 is a C1 to C12 alkyl group. Feature 11. The composition of each of the features described herein, wherein R1 is a C1 to C8 alkyl group and x is 1 to 8. Feature 12. The composition of each of the features described herein, wherein the polymer is free of chemical crosslinking or has less than 5% chemical crosslinking. Feature 13. The composition of each of the features described herein, wherein the polymer has a polydispersity index (Đ) of about 1.1. to 2 Feature 14. The composition of each of the features described herein, wherein the polymer Thomas Horstemeyer Docket No.: 222112-2310 has a polydispersity index (Đ) of about 1.1 to 1.3. Feature 15. The composition of each of the features described herein, further comprising a tackifier. Feature 16. An adhesive composition comprising the composition of each of the features described herein, wherein the polymer does not include chemical crosslinking. Feature 17. The adhesive composition of each of the features described herein, wherein the polymers are physically entangled. Feature 18. The adhesive composition of each of the features described herein, wherein the polymers are recyclable. Feature 19. The adhesive composition of each of the features described herein, wherein the polymer has a polydispersity index (Đ) of about 1.1. to 2. Feature 20. The adhesive composition of each of the features described herein, wherein the polymer has a polydispersity index (Đ) of about 1.1 to 1.3. Feature 21. The adhesive composition of each of the features described herein, wherein the adhesive is a random copolymer. Feature 22. The adhesive composition of each of the features described herein, wherein the adhesive is a statistical copolymer. Feature 23. The adhesive composition of each of the features described herein, wherein the adhesive is an alternative copolymer. Feature 24. The adhesive composition of each of the features described herein, wherein the adhesive is a gradient copolymer. Feature 25. A pressure-sensitive adhesive composition comprising the composition of each of the features described herein, wherein the polymer is free of chemical crosslinking or has less than 5% chemical crosslinking. Feature 26. The pressure-sensitive adhesive composition of each of the features described herein, wherein the polymers are physically entangled. Feature 27. The pressure-sensitive adhesive composition of each of the features described herein, wherein the polymers are recyclable. Feature 28. The pressure-sensitive adhesive composition of each of the features described herein, wherein the polymer has a polydispersity index (Đ) of about 1.1. to 3. Feature 29. The pressure-sensitive adhesive composition of each of the features described herein, wherein the polymer has a polydispersity index (Đ) of about 1.1 to 1.3. Feature 30. A method of making the polymer having a molecular weight of about 0.3 MDa to 10 MDa and of each of the features described herein, comprising the following polymerization scheme:   ] Thomas Horstemeyer Docket No.: 222112-2310 , m is 1 to 10,000, n is 1 to 10,000, wherein each of R1, R2, R3, and R4 groups are independently selected from: H, -OR1, -NRxRy, -N+(Rx)3, -N+(Rx)2(Ry), -N+(Rx)(Ry)(Rz), - S(O)2Rx, -S(O)2ORx, -S(O)2NRxRy, -NRxS(O)2Ry, -NRxC(O)Ry, -C(O)Rx, -C(O)ORx, - C(O)NRxRy, -NRxC(O)ORy, -NRxC(O)NRxRy, -OC(O)NRxRy, -NRxS(O)2NRxRy, - C(O)NRxS(O)2NRxRy, catechol, a boronic acid group, or a pyridyl disulfide group, where each Rx, Ry, and Rzis independently H or linear or branched C1-18alkyl or aryl as well as - C(O)O(CH2)b-OH, -C(O)O(CH2)b-N(CH3)2, -C(O)O(CH2)bCH3,-N+(CH3)3, -C(O)O(CH2)b- OSO3–, -C(O)O(CH2)b-OSO3H , -C(O)O(CH2)b-SO3–, -C(O)O(CH2)b-SO3H, and - C(O)N(H)C((CH3)2)(CH2)bSO3–, -C(O)N(H)C((CH3)2)(CH2)bSO3H, -(CH2)b-OH, -(CH2)b- N(CH3)2, -(CH2)b-N+(CH3)3, -(CH2)b-OSO3–, -(CH2)b-OSO3H , -(CH2)b-SO3–, -(CH2)b-SO3H, and -C((CH3)2)(CH2)bSO3–, or -C((CH3)2)(CH2)bSO3H where b is 1-20 alkyl, wherein in the reaction time frame is about 3 to 5 hours or about 4 hours. Feature 31. The method of each of the features described herein, wherein the polymerization scheme is as follows: Feature 32. The method of claim 30, wherein the polymerization is selected from: a radical polymerization, conventional radical polymerization, reversible-deactivation radical polymerization, reversible addition-fragmentation chain transfer (RAFT) polymerization, macromolecular design by interchange of xanthate (MADIX) polymerization, photoiniferter polymerization, atom transfer radical polymerization (ATRP), or stable free radical polymerization (SFRP). Feature 33. The method of each of the features described herein, wherein the polymer has a molecular weight of about 1 MDa to 10 MDa. Feature 34. The method of each of the features described herein, wherein q is 5 to 20. Feature 35. The method of each of the features described herein, wherein R1 is a C1 to C12 alkyl group. Feature 36. The method of each of the features described herein, wherein R1 is a C1 to C8 alkyl group and x is 1 to 8. Feature 37. The method of each of the features described herein, wherein the polymer is free of chemical crosslinking or has less than 5% chemical crosslinking. Thomas Horstemeyer Docket No.: 222112-2310 EXAMPLE While embodiments of the present disclosure are described in connection with the Examples and the corresponding text and figures, there is no intent to limit the disclosure to the embodiments in these descriptions. On the contrary, the intent is to cover all alternatives, modifications, and equivalents included within the spirit and scope of embodiments of the present disclosure. Example 1 Since its invention in 1953 by chemists at the Max Plank Institute, ultra-high molecular weight polyethylene (UHMWPE) has revolutionized the polymer industry and is expected to reach a market size of $3.3 billion by 2027.1-2UHMWPE can be synthesized with molecular weights up to 7.5×106Da to produce a plastic with exceptional properties, such as high abrasion and fracture resistance and tensile strength approximately eight times greater than that of high-strength-grade steel by weight.1,3These distinctive characteristics have made UHMWPE suitable as a component of hip implants, body armor, truck beds, and marine gear.1,4Given the unprecedented qualities of UHMWPE, the development of synthetic methods to produce other UHMW polymers (UHMW, >106Da) has been an area of increased attention. When seeking to elucidate the role of molecular weight on polymer properties, it would be beneficial to prepare polymers that are not only UHMW but also well- defined in terms of their dispersity and architecture. Controlled polymerization techniques allow for the synthesis of well-defined UHMW polymers, with success having been demonstrated via cationic ring-opening polymerization, atom transfer radical polymerization, and reversible addition-fragmentation chain-transfer polymerization.5–7The latter two methods are examples of reversible-deactivation radical polymerization (RDRP), where UHMWs can be targeted by employing conditions that maximize the rate of propagation relative to termination. Photo-mediated RDRP offers the benefits of spatiotemporal control and straightforward reaction conditions.6,8–14These advantages enable applications such as additive manufacturing and have been shown to eliminate the need for conditions such as high pressures or heterogeneous methods often required to reach UHMWs in other systems.7,15,16Photoiniferter polymerization is an example of a light-mediated RDRP method that uses a molecule capable of photolysis (iniferter) that can engage in initiation of polymer chains, degenerative chain transfer, and reversible termination.8,17,18Photoiniferter Thomas Horstemeyer Docket No.: 222112-2310 polymerization has been successfully applied to achieve a variety of UHMW polymers (>5 MDa) with predictable molecular weights and dispersities as low as Đ = 1.1.19Polymer mechanical properties correlate with molecular weight and have been studied for UHMW polymers prepared by recently developed synthetic methods.5,20UHMW polydioxolane (Mn>2 MDa) synthesized by cationic ring-opening polymerization was tough and ductile with ultimate tensile strength exceeding that of UHMWPE.5The mechanical properties of methacrylate-based UHMW polymer gels synthesized in ionic liquids have also been investigated.20Physical crosslinks from chain entanglements maintained the integrity of the gels, and the networks exhibited increases in ultimate tensile strength and resistance to creep at higher molecular weight.20Despite these examples, little research on the mechanical properties of UHMW acrylate-based polymers has been performed. Two types of interchain interactions are involved in thermoplastic polymer systems and contribute to their observed physical properties, namely intermolecular forces and topological entanglements.21,22Below the glass transition temperature (Tg) and at low strains, intermolecular forces are more prevalent than topological entanglements and, therefore, contribute to polymer properties to a greater extent by restricting long-range cooperative backbone mobility. As temperature rises above the Tgor strains increase, topological entanglements or crosslinks become increasingly important in dictating material properties by behaving as physical crosslinks that cause an increase in viscosity and thermal stability and improve mechanical properties such as shear resistance, important characteristics of pressure-sensitive adhesives (PSAs).23–25PSAs are capable of binding to a variety of surfaces upon application of mild pressures over short time scales and typically have a Tgbelow room temperature.25Various types of PSAs exist, including silicones, polyurethanes, epoxies, and acrylics.25Acrylic PSAs, in particular, have recently dominated the PSA market due to their high tack, transparency, and resistance to UV light, oxidation, heat, and humidity.25Designing functional PSAs requires a careful balance of tack / adhesion and cohesion.26Since cohesive failure leaves residue on the substrate, an ideal PSA would show exceptional adhesion and tack and fail interfacially. Because entanglements in commercial adhesives are insufficient in preventing cohesive failure and creep, PSAs are often crosslinked, improving cohesive strength, albeit at the expense of adhesion.25We hypothesized that increasing the molecular weight of acrylate-based polymers to UHMWs would accentuate the effects of chain entanglements to enhance cohesive strength and eliminate the need for crosslinkers in acrylate PSAs. Thomas Horstemeyer Docket No.: 222112-2310 Herein, we report the effect of molecular weight and temperature dependency on the mechanical properties of UHMW poly(methyl acrylate) (PMA) synthesized via photoiniferter polymerization. We sought to understand the influence of increased chain entanglements within the UHMW regime on the material properties that are dominated by intermolecular interactions below the Tgand topological entanglements above the Tg(Figure 1). Furthermore, we hypothesized that by leveraging the increased effect of chain entanglement within the rubbery plateau region of UHMW acrylates, the cohesive performance of PSAs could be enhanced without the addition of a crosslinker. This work provides fundamental insight into the emerging field of controlled UHMW polymers by exploring the role of chain length on polyacrylate PSA performance. Results and Discussion PMA with molecular weights (Mn) of 0.2, 1, and 2 MDa was synthesized using photoiniferter polymerization to study the effect of molecular weight within the UHMW regime on the mechanical properties of polyacrylates (Figure 6). After purification, we successfully obtained each targeted product (number-average molecular weight (Mn): 0.25, 1.0, and 2.1 MDa as determined by size-exclusion chromatography (SEC) and1H NMR spectroscopy (Figure 2A, 7-9)). The thermal properties of the three PMA polymers were measured using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) (Figure 10- 11). The minimal weight loss observed in each case up to 300 °C was likely from loss of the photoiniferter end-group,27and no appreciable difference between samples of varying Mnwas observed for T95(Table S1-S2). The Tgwas determined by DSC (Figure 11) and was essentially the same between the samples (~17-18 °C), in agreement with the Flory-Fox prediction.28Prior to mechanical testing, PMA of 0.25 and 1.0 MDa were compression molded at 125 °C for 2.5 h. Because of the exponential increase in viscosity with molecular weight, the PMA of 2.1 MDa could not be molded under these conditions. To allow flow under compression in a time-efficient manner and to avoid damage caused by long-term heat exposure, the PMA of 2.1 MDa was compression molded at 150 °C for 2.5 h. To further probe the role of chain entanglement as a function of molecular weight in the rubbery plateau region, each sample was subjected to dynamic mechanical analysis (DMA) under a 0.05% oscillatory strain (Figure 2B, Table S3-S4). An increase in the height and breadth of the rubbery plateau region was observed with an increase in molecular Thomas Horstemeyer Docket No.: 222112-2310 weight, suggesting an enhancement in the effect of chain entanglements with molecular weight. While the effect of chain entanglements was expected to be most pronounced above the Tg(~37 °C from DMA), we sought to also understand the effect of molecular weight on the mechanical behavior as the polymer softened through the Tg. Consequently, each sample was subjected to tensile testing at a strain rate of 0.5 mm / s at 22, 30, and 40 °C. All samples displayed elastomeric behavior under each condition (Figure 3A-3C). As the temperature increased, a change in material behavior was observed. The PMA of 2.1 MDa showed strain hardening before failure at all temperatures. In contrast, PMA of 1.0 MDa strain hardened at lower temperatures, but at 40 °C, this behavior was no longer observed. Finally, substantial yielding occurred for the PMA of 0.25 MDa when tested at 40 °C. We attribute these differences in elastomeric behavior to the increased effect of chain entanglements with increasing molecular weight. Young’s modulus, ultimate tensile strength, strain at break (%), and toughness were extracted from the stress-strain curves for a minimum of five samples of each polymer (Figure 3D-3F, 12, Table S5-S8). Because of the high-strain capability of PMA of 0.25 MDa, the tensile tester reached limits at 30 and 40 °C before material failure, preventing complete analysis of tensile strength and toughness. (Note: all tensile strength values were extracted from the stress-strain curves at break except for the PMA of 0.25 MDa measured at 40 °C, where the values were obtained from yield). A two-sample statistical t-test was used to compare samples of differing molecular weights at each temperature to understand the influence of molecular weight on each of the properties. Analysis revealed remarkable enhancement in modulus, tensile strength, and toughness with increasing molecular weight at 30 °C (Table S9) even though the testing temperature was below the reported Tgby DMA (~ 37 °C), showing the significance of chain entanglements within the glass transition as the polymer softens. An increase in modulus at 40 °C and tensile strength at 22 and 40 °C with molecular weight was also observed. Importantly, the improvement in the tensile strength with molecular weight was more significant at 40 °C where chain entanglements were expected to dominate compared to 22 °C (Table S9). No change in strain at break (%) at any temperature was found with molecular weight. Increasing the molecular weight of PMA to UHMWs improves performance by enhancing the modulus, tensile strength, and toughness. This is crucial as temperatures rise and the effects of chain entanglements become more significant as the PMA softens through the Tg. Thomas Horstemeyer Docket No.: 222112-2310 Unfortunately, due to a low signal-to-noise ratio, we could not further characterize the tensile properties of the PMA samples at higher temperatures. To probe the effect of molecular weight on the properties of PMA at elevated temperatures, we subjected each sample to creep cycles under 500 Pa of stress at 25, 50, and 100 °C (Figure 3G-3I). The results showed no significant effect of molecular weight on the permanent deformation after four creep cycles at 25 °C, further demonstrating that entanglements contribute less significantly to the polymer mechanical properties when temperatures are below the Tg. In contrast, at higher temperatures of 50 and 100 °C above the Tg, decreasing molecular weight led to an increase in permanent deformation. Additionally, at 25 and 50 °C, increasing molecular weight resulted in a higher elastic component, but at 100 °C, the enhanced elasticity observed in the UHMW polymers was no longer present. We attribute the stark difference in permanent deformation and elasticity of the PMA of 0.25 MDa compared to the PMA of UHMW at 100 °C to the loss of network integrity occurring at lower temperatures with decreasing molecular weight as shown by the shift in the onset of the terminal region measured by DMA. Because we detected minimal effect of molecular weight on the measured properties in the glassy region ≤ 25 °C, we propose that the entanglements play a more significant role in improving the mechanical properties relative to intermolecular forces. The tensile strength was the only property that increased with molecular weight at temperatures ≤ 25 °C. At 30 °C, the toughness and tensile strength were markedly improved with molecular weight, and the material largely retained its elasticity, allowing it to store considerable energy through elastic deformation. At elevated temperatures, the improved elasticity in UHMW samples was lost. Additionally, as molecular weight increased, the onset of the terminal region shifted to significantly higher temperatures, improving the resistance to creep. Overall, these results show that higher molecular weight enhanced modulus, tensile strength, resistance to creep, and toughness even at elevated temperatures and gives insight into the behavior of UHMW acrylates from the glassy to the rubbery states. Based on the increased effect of chain entanglements on the tensile strength of UHMW PMA, we hypothesized that UHMW polyacrylates would yield PSAs with high cohesive strength without the addition of chemical crosslinkers. To test this hypothesis, three additional acrylate polymers were synthesized using photoiniferter polymerization of butyl acrylate (BA) and 2-hydroxyethyl acrylate (HEA) (5 wt%) as soft and hard monomers, respectively.29Throughout the copolymerization, monomer consumption was monitored by1H NMR spectroscopy, and the linearity of the pseudo-first-order kinetic plot indicated Thomas Horstemeyer Docket No.: 222112-2310 constant radical concentration and steady rate of monomer consumption over time after an inhibition period (Figure 13-15). Low dispersity, a uniform shift in the SEC traces to shorter elution times, and close correlation of theoretical and experimental molecular weight suggested that the copolymerization was controlled (Figure 16-21). Analysis of the final molecular weights by SEC demonstrated that the synthesis of UHMW PSAs was successful ([Mn: 0.28 MDa, Đ: 1.1], [Mn: 1.3 MDa, Đ: 1.3], [Mn: 2.3 MDa, Đ: 1.2] (Figure 4)). After purification,1H NMR spectroscopy revealed that the targeted ratio of incorporation of BA / HEA (17.2) was achieved for all adhesives (Figures 22-24 and Table S10). Thermal analysis with TGA revealed decreasing T95with increasing molecular weight (Figure 25 and Table S11), and DSC showed that the Tgwas significantly below room temperature, a crucial characteristic for adhesives to flow onto the substrate during adhesion (Figure 26). The viscoelastic behavior of the PSAs was evaluated using oscillatory shear rheology (Figure 5A-5C). Generally, behavior at high and low frequencies gives information on debonding and bonding, respectively.26A higher tan ^^ in the low-frequency region indicated greater capacity of lower molecular weight adhesives to dissipate energy, thereby allowing flow onto the substrate. In the low-frequency range, lower molecular weights show more dramatic decreases in G´, signaling lower resistance to shear with decreasing molecular weight. Since G´ remained largely constant within the measured frequency range at 25 °C for the 1.3 and 2.3 MDa adhesives (Figure 27-28), we expanded the temperature range and horizontally translated the modulus versus angular frequency using time-temperature superposition with a reference temperature of 25 °C. Both UHMW adhesives showed a significant increase in the tan delta and a decrease in the modulus beyond 0.01 Hz, indicating longer residence time may benefit bonding. All adhesives showed G´ < 105Pa and satisfied the Dahlquist contact criterion at low frequencies, meaning sufficient surface wetting is possible.30From the results of the frequency sweep, we expected an enhancement in cohesive strength and a reduction in both adhesive strength and tack with increasing molecular weight. The adhesive properties were studied using 180° peel and loop tack tests (ASTM D3330 and ASTM D6125) (Figure 29A). Each of the adhesives was initially tested at room temperature. The adhesive of 0.28 MDa was shown to fail cohesively, but the adhesives of UHMW debonded interfacially (Figure 5D), suggesting that increasing chain entanglements could be effective in improving cohesion (Figure 29B). However, both tack and adhesion decreased with molecular weight, attributed to inhibited chain mobility with molecular weight preventing rapid surface wetting (Figure 5D). To study the effect of temperature on the Thomas Horstemeyer Docket No.: 222112-2310 cohesion, adhesion, and tack of the UHMW (1.3 and 2.3 MDa) adhesives, 180° peel and loop tack experiments were conducted at 50 and 75 °C (Figure 5D-5E). Since the 0.28 MDa adhesive showed cohesive failure or network tearing at 25 °C and we sought to understand the effect of temperature on cohesive stability in the UHMW adhesives, we did not further probe the peel and loop-tack behavior at elevated temperatures, which would only serve to promote undesirable cohesive failure more readily. An increase in peel strength was observed for both UHMW adhesives, attributed to the improved diffusion of polymer chains at elevated temperatures (Figure 5D) On the other hand, no differences outside of error were found in the peak force as a function of temperature for both the 1.3 and 2.3 MDa adhesives (Figure 5E). Higher temperatures enabled enhanced flow of the polymer under an applied force, improving the peel force of adhesion with temperature; however, since tack controls how quickly adhesives bond to surfaces with near zero application force and is a measure of the ability of an adhesive to wet a surface, we propose that the lack of improvement in tack with increasing temperature was caused by the limited capability of the UHMW polymer chains to spontaneously flow without a substantial applied force. Notably, the polymer of 1.3 MDa failed cohesively at 75 °C, leaving residue on the substrate, while the polymer of 2.3 MDa debonded interfacially, showing that by increasing the molecular weight, the thermal stability of the adhesive improves, allowing UHMW adhesives to perform well without the addition of crosslinkers in applications requiring elevated temperatures. To determine if the adhesion could be improved over time, the residence time of the samples was increased from 1 min to 24 h. An increase in the peel strength of the UHMW adhesives by 95 and 48% for the polymers of 1.3 and 2.3 MDa, respectively (Figure 5F), was observed, indicating that long-term residence is effective for UHMW polymers to adhere to surfaces. Conclusion Using the straightforward synthesis conditions of photoiniferter polymerization, PMA of UHMW was produced, and the mechanical properties were studied as a function of molecular weight and temperature. Compared to their lower molecular weight counterparts, polyacrylates of UHMW exhibited significant enhancements in modulus, tensile strength, creep resistance, and toughness. Moreover, the stabilizing effect of chain entanglements in UHMW polyacrylates significantly improved mechanical stability even at elevated temperatures. These results suggest that UHMW acrylate polymers could find application in crosslinker-free products requiring mechanical and thermal stability, greater strength, toughness, and creep resistance. We utilized the enhanced effect of chain entanglements Thomas Horstemeyer Docket No.: 222112-2310 on the material strength of polyacrylates of UHMW to design PSAs without chemical crosslinkers. As molecular weight increased, the cohesion improved. Furthermore, increasing the molecular weight enhanced the cohesive stability at elevated temperatures, showing the potential effectiveness of UHMW polymers in adhesives for applications at elevated temperatures. These results offer valuable and fundamental insights into the mechanical properties of controlled UHMW acrylate polymers and serve as a foundation for research to discover more beneficial applications of UHMW acrylates. REFERENCES for example 1 (1) Kurtz, S. M. The UHMWPE Handbook; Academic Press: San Diego, 2004, DOI: 10.1016 / B978-012429851-4 / 50000-0. (2) Fortune Business Insights. Ultra-High Molecular Weight Polyethylene Market Size Report, 2021, https: / / www.fortunebusinessinsights.com (accessed 2023-08-25). (3) Smith, P.; Lemstra, P. J.; Kalb, B.; Pennings, A. J. Ultrahigh-Strength Polyethylene Filaments by Solution Spinning and Hot Drawing. Polym. Bull.1979, 1, 733–736, DOI: 10.1007 / BF00256272. (4) The Science of Armour Materials; Crouch, I. G., Ed.; Woodhead Publishing in Materials; Woodhead Publishing, 2017, DOI: 10.1016 / B978-0-08-100704-4.02001-6. (5) Hester, H. G.; Abel, B. A.; Coates, G. W. 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Supplemental information for Example 1 Materials Methyl acrylate stabilized with monomethyl ether hydroquinone (MEHQ) (MA, Millipore Sigma, 99%) and butyl acrylate stabilized with MEHQ (BA, TCI America, 99%) were filtered through a plug of basic alumina prior to use, and 2-hydroxyethyl acrylate stabilized with MEHQ (HEA, Acros, 97%) was passed through a column of neutral alumina before use. The iniferter, 2-(dodecylthiocarbonothioylthio)-2-methylpropanoic acid (DDMAT), was synthesized from previous literature.1Dimethylsulfoxide (DMSO, Fisher, 99%), N,N- dimethylformamide (DMF, Fisher, ACS Grade), diethyl ether (Fisher, ACS grade, stabilized with BHT), acetone (Sigma-Aldrich, > 99.5%), and tetrahydrofuran (THF, Fisher, HPLC grade) were used as received. The UV photoreactor (roughly 2.5 mW / cm2) was built from eight 9 W bulbs (emission 365 nm) obtained from a UV nail gel-curing lamp. Synthetic Procedures Synthetic procedures for PMA DMSO (61.5 mL) in a 250 mL beaker. This solution was evenly divided into six scintillation vials which were each sparged on ice with Argon before initiation in the UV photoreactor. The polymerization was terminated after 4 h, and the product was purified by dilution in THF, precipitation into diethyl ether (×4), and drying at 80 °C under vacuum overnight to yield 26.3 g of an off-white solid product. Procedure for Synthesis of 1.0 MDa Poly(methyl acrylate) MA (30.0 g, 348 mmol) was combined with DDMAT (10.4 mg, 0.0285 mmol), DMSO (51.4 mL), and DMF (3.00 mL) as an internal standard for monitoring conversion in a 250 mL beaker. This solution was evenly divided into six scintillation vials which were each sparged Thomas Horstemeyer Docket No.: 222112-2310 on ice with Argon before initiation in the UV photoreactor. The polymerization was terminated after 5 h, and the product was purified by dilution in THF, precipitation into diethyl ether (×4), and drying at 80 °C under vacuum overnight to yield (25.0 g) of a transparent and colorless product. Procedure for Synthesis of 2.1 MDa Poly(methyl acrylate) MA (30.0 g, 348 mmol) was combined with DDMAT (2.13 mg, 0.00588 mmol), DMSO (52.0 mL), and DMF (3.00 mL) as an internal standard for monitoring conversion in a 250 mL beaker. This solution was evenly divided into six, 20 mL scintillation vials which were each sparged on ice with Argon before initiation in the UV photoreactor. The polymerization was terminated after 5 h, and the product was purified by dilution in THF, precipitation into diethyl ether (×4), and drying at 80 °C under vacuum overnight to yield (25.1) g of a transparent and colorless product. Synthetic procedures for P(BA-co-HEA) BA g, 62.5 , HEA g, 3.63 DMSO (6.35 mL), and DMF (0.770 mL) as an internal were a 20 mL scintillation vial. After sparging with Argon, the vial was placed in the UV photoreactor. Periodically, an aliquot was removed from the reaction to monitor conversion, and after 4 h, the reaction was terminated at 50% conversion. The synthesized product was dialyzed against acetone for 72 h to remove impurities and dried at 80 °C under vacuum overnight to yield an off-white, highly viscous product (2.60 g). Procedure for Synthesis of 1.3 MDa Poly(BA-co-HEA) BA (8.01 g, 62.5 mmol), HEA (0.421 g, 3.63 mmol), DDMAT (1.54 mg, 0.00422 mmol), DMSO (6.35 mL), and DMF (0.770 mL) as an internal standard were combined in a 20 mL scintillation vial. After sparging with Argon, the vial was placed in the UV photoreactor. Periodically, an aliquot was removed from the reaction to monitor conversion, and after 4 h, the reaction was terminated at 50% conversion. The synthesized product was Thomas Horstemeyer Docket No.: 222112-2310 dialyzed against acetone for 72 h to remove impurities and dried at 80 °C under vacuum overnight to yield a colorless solid (2.64 g). Procedure for Synthesis of 2.3 MDa Poly(BA-co-HEA) BA (8.01 g, 62.5 mmol), HEA (0.431 g, 3.63 mmol), DDMAT (0.769 mg, 0.00211 mmol), DMSO (6.35 mL), and DMF (0.770 mL) as an internal standard were combined in a 20 mL scintillation vial. After sparging with Argon, the vial was placed in the UV photoreactor. Periodically, an aliquot was removed from the reaction to monitor conversion, and after 4 h, the reaction was terminated at 50% conversion. The synthesized product was dialyzed against acetone for 72 h to remove impurities and dried at 80 °C under vacuum overnight to yield a colorless solid (2.44 g). Instrumentation Size Exclusion Chromatography (SEC) SEC was performed in DMAc with 50 mM LiCl at 50 °C and a flow rate of 1.0 mL / min. The system utilized an Agilent isocratic pump, degasser, and autosampler. The columns were a Viscogel I-series 5 μm guard column and two ViscoGel I-series G3078 mixed bed columns with molecular weight ranges of 0−20 × 103and 0−100 × 104g / mol. Detection consisted of a Wyatt Optilab T-rEX refractive index detector operating at 658 nm and a Wyatt miniDAWN Treos light scattering detector operating at 659 nm. Absolute molecular weights and dispersities were calculated using the Wyatt ASTRA software with dn / dc values acquired via offline analysis or 100% mass recovery methods. Nuclear Magnetic Resonance (NMR) Spectroscopy 1H NMR spectra for determination of monomer conversion were recorded on a Magritek Spinsolve 60 or a Varian Inova2500 MHz 2 RF channel instrument at 25 °C in DMSO-d6or CHCl3-d (Cambridge Isotopes Laboratories, Inc., 99.8%). Differential Scanning Calorimetry (DSC) Thermal analysis was performed using a TA Instruments 2500 DSC with a Fusion Cell, T4P Tzero heat flow technology, and an RSC 90 two-stage refrigerated cooling system. Before analysis, the instrument was calibrated with an indium reference material for temperature and cell constant. Samples were submitted to three heat-cool-heat cycles at a ramp rate of 10 °C / min in the range of -60 to 100 °C for PMA and -90 to 50 °C for P(BA-co- HEA). The samples were sealed in aluminum hermetic pans (DSC Consumables), and the Thomas Horstemeyer Docket No.: 222112-2310 cell was under a constant 50 mL / min N2flow rate throughout the heat-cool-heat cycles. Tgwas extracted from the third heating cycle. Thermogravimetric Analysis (TGA) TGA sample analysis was performed in a 100 ^^L platinum pan on a TA Instruments TGA 5500 with a low-mass IR furnace and autosampler. Samples were heated at a rate of 20 °C / min for PMA and 10 °C / min for the adhesives from room temperature to 600 °C under a flow rate of 25 mL / min N2. Dynamic Mechanical Analysis (DMA) DMA was performed on a TA Instruments Q800 DMA equipped with a TA Instruments Gas Cooling Accessory. Rectangular samples (1 mm × 20 mm × 6 mm) were placed in a tension clamp before measurement of the viscoelastic properties with temperature. The samples were cooled to -30 °C and equilibrated with a 5-min isotherm before ramping at 3 °C / min to 200 °C (or until the terminal region was reached) under 0.05% sinusoidal strain and a frequency of 1 Hz. Rheology A TA Instruments Discovery Hybrid Rheometer (DHR-2) was used for oscillatory shear rheology measurements. A 20 mm parallel-plate geometry with thermal control maintained the temperature for all experiments. For creep-cycling experiments, a stress of 500 Pa was applied for 200 s and 0 Pa for 100 s at 25, 50, and 100 °C. During frequency sweeps, samples were subjected to 0.5% oscillatory strain from 0.001 - 100 Hz at 25 °C. Tensile Testing An Instron MTS Criterion (Model 43) equipped with 10 kN MTS Advantage Pneumatic Grips and a Thermcraft LBO-Series temperature control oven was used for all tensile testing measurements. Sample were prepared and tested according to ASTM D638. The samples were compression molded in aluminum molds to yield testing samples following Type V dimensions of the ASTM D638 guideline. All mechanical properties were recorded using a 0.5 mm / s strain rate, specified temperature control, and 50% relative humidity for at least five specimens. Thomas Horstemeyer Docket No.: 222112-2310 Adhesive Preparation, 180 ° Peel Test, and Loop Tack Test The 180° peel tests were performed on an Instron MTS Criterion (Model 43) equipped with 10 kN MTS Advantage Pneumatic Grips and a Thermcraft LBO-Series temperature control oven at the indicated temperature and 50% relative humidity following ASTM D3330 test method A. The adhesives were coated onto 2 mil PET to form a film 15-20 ^^m thick, and the prepared tapes (1” wide) were conditioned for 24 h at room temperature and 50% humidity. The adhesives strips were adhered to the testing substrate (ASTM A666 stainless steel) using a 2 kg roller. Unless otherwise specified, samples were peeled within one minute at a rate of 5 mm / s. Peel force values were averaged over three samples and converted to N / 10 mm. Loop tack samples were tested following the ASTM 6125 standard. The adhesives were coated onto 2 mil PET to form a film 15-20 ^^m thick, and the prepared tapes (1” wide) were conditioned for 24 h at room temperature and 50% humidity. Samples were tested at a rate of 300 mm / min. Maximum load values were averaged over three samples. Table S1. Weight loss (%) from TGA at 300 °C for PMA with Mnof 0.25, 1.0, and 2.1 MDa. Table S2. T95values from TGA for PMA with Mnof 0.25, 1.0, and 2.1 MDa. Table S3. The molecular weight between crosslinks calculated using the tensile storage modulus 40 °C above the Tgfrom DMA and Equation S1. (Equation S1) ^^ᇱൌாᇲఘோ் ଶ^^ାఔ^ൌெ^Table S4. Tgcalculated from peak max tan delta of DMA temperature sweeps for PMA of various Mn. Thomas Horstemeyer Docket No.: 222112-2310 Table S5. Young’s Modulus calculated from the linear elastic portion of the stress-strain curves at various temperatures and Mn. Table S6. Strain at break (%) calculated from the stress-strain curves at various temperatures and Mn. Table S7. Ultimate tensile strength calculated at break (note: * tensile strength at yield) from the stress-strain curves at various temperatures and Mn. Table S8. Toughness calculated from the area under the stress-strain curves at various temperatures and Mn. Thomas Horstemeyer Docket No.: 222112-2310 Table S9. Percent increases in modulus, tensile strength, or toughness for statistically significant samples. and equation S2 for each of the synthesized adhesives compared to the theoretical inclusion. (Equation S2) Blue / Orange = BA / HEA Table S11. T95values for P(BA-co-HEA) with Mnof 0.28, 1.3, and 2.3 MDa. References For Supplemental Information for Example 1 1. Lai, J. T.; Filla, D.; Shea, R. Macromolecules 2002, 35, 6754-6756. It should be noted that ratios, concentrations, amounts, and other numerical data may be expressed herein in a range format. It is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. To illustrate, a concentration range of “about 0.1% to about 25%” should be interpreted to include not only the explicitly recited concentration of about 0.1 mol% to about 25 mol%, but also include individual concentrations (e.g., 1%, 2%, 3%, 4%, 5%, 10%, 15%, 20%) and the sub-ranges (e.g., Thomas Horstemeyer Docket No.: 222112-2310 0.5%, 1.1%, 2.2%, 3.3%, and 4.4%, 5.5%, 10.1%, 15.5%, 20.2%) within the indicated range. In an embodiment, “about 0” can refer to 0, 0.001, 0.01, or 0.1. In an embodiment, the term “about” can include traditional rounding according to significant figures of the numerical value. In addition, the phrase “about ‘x’ to ‘y’” includes “about ‘x’ to about ‘y’”. It should be emphasized that the above-described embodiments of the present disclosure are merely possible examples of implementations, and are set forth only for a clear understanding of the principles of the disclosure. Many variations and modifications may be made to the above-described embodiments of the disclosure without departing substantially from the spirit and principles of the disclosure. All such modifications and variations are intended to be included herein within the scope of this disclosure.

Claims

Thomas Horstemeyer Docket No.: 222112-2310 CLAIMS 1. A composition comprising: a polymer having a molecular weight of about 0.3 MDa to 10 MDa and the following structure:   ] , wherein m is 1 to 100,000, n is 1 to 100,000, wherein each of are independently selected from: H, -OR1, -NRxRy, -N+(Rx)3, -N+2, -N+, -S(O)2Rx, -S(O)2ORx, -S(O)2NRxRy, -NRxS(O)2Ry, -NRxC(O)Ry, -C(O)Rx, -C(O)ORx, -C(O)NRxRy, -NRxC(O)ORy, -NRxC(O)NRxRy, -OC(O)NRxRy, - NRxS(O)2NRxRy, -C(O)NRxS(O)2NRxRy, catechol, a boronic acid group, or a pyridyl disulfide group, where each Rx, Ry, and Rzis independently H or linear or branched C1-18alkyl or aryl as well as -C(O)O(CH2)b-OH, -C(O)O(CH2)b-N(CH3)2, -C(O)O(CH2)bCH3,- N+(CH3)3, -C(O)O(CH2)b-OSO3–, -C(O)O(CH2)b-OSO3H , -C(O)O(CH2)b-SO3–, - C(O)O(CH2)b-SO3H, and -C(O)N(H)C((CH3)2)(CH2)bSO3–, -C(O)N(H)C((CH3)2)(CH2)bSO3H, -(CH2)b-OH, -(CH2)b-N(CH3)2, -(CH2)b-N+(CH3)3, -(CH2)b-OSO3–, -(CH2)b-OSO3H , -(CH2)b- SO3–, -(CH2)b-SO3H, and -C((CH3)2)(CH2)bSO3–, or -C((CH3)2)(CH2)bSO3H where b is 1-20 alkyl.

2. The composition of claim 1, wherein the polymer includes 1 to 5 additional monomer units in the polymer chain.

3. The composition of claim 2, wherein the 1 to 5 additional monomer units are selected from the group consisting of: (meth)acrylate esters, and (meth)acrylic acids, styrene, (meth)acrylamides.

4. The composition of claim 2, wherein the polymer including additional monomer units has one of the following structures:   ] ,Thomas Horstemeyer Docket No.: 222112-2310   ] or   wherein o is 1 of R5, R6, R7,R8, R9, and groups are - - -N+(Rx)3, - N+(Rx)2(Ry), -N+(Rx)(Ry)(Rz), -S(O)2Rx, -S(O)2ORx, -S(O)2NRxRy, -NRxS(O)2Ry, -NRxC(O)Ry, -C(O)Rx, -C(O)ORx, -C(O)NRxRy, -NRxC(O)ORy, -NRxC(O)NRxRy, -OC(O)NRxRy, - NRxS(O)2NRxRy, -C(O)NRxS(O)2NRxRy, catechol, a boronic acid group, or a pyridyl disulfide group, where each Rx, Ry, and Rzis independently H or linear or branched C1-18alkyl or aryl as well as -C(O)O(CH2)b-OH, -C(O)O(CH2)b-N(CH3)2, -C(O)O(CH2)bCH3,- N+(CH3)3, -C(O)O(CH2)b-OSO3–, -C(O)O(CH2)b-OSO3H , -C(O)O(CH2)b-SO3–, - C(O)O(CH2)b-SO3H, and -C(O)N(H)C((CH3)2)(CH2)bSO3–, -C(O)N(H)C((CH3)2)(CH2)bSO3H, -(CH2)b-OH, -(CH2)b-N(CH3)2, -(CH2)b-N+(CH3)3, -(CH2)b-OSO3–, -(CH2)b-OSO3H , -(CH2)b- SO3–, -(CH2)b-SO3H, and -C((CH3)2)(CH2)bSO3–, -or C((CH3)2)(CH2)bSO3H, where b is 1-20 alkyl.

5. The composition of claim 2, wherein the polymer including additional monomer units has one of the following structures: 1Thomas Horstemeyer Docket No.: 222112-2310 to 100,000, p is 1 to 100,000, r is 1 to 100,000, q is 2 to 20, wherein each of R5, R6, R7, R8, R9, and R10 groups are independently selected from: H, -OR1, -NRxRy, -N+(Rx)3, - N+(Rx)2(Ry), -N+(Rx)(Ry)(Rz), -S(O)2Rx, -S(O)2ORx, -S(O)2NRxRy, -NRxS(O)2Ry, -NRxC(O)Ry, -C(O)Rx, -C(O)ORx, -C(O)NRxRy, -NRxC(O)ORy, -NRxC(O)NRxRy, -OC(O)NRxRy, - NRxS(O)2NRxRy, -C(O)NRxS(O)2NRxRy, catechol, a boronic acid group, or a pyridyl disulfide group, where each Rx, Ry, and Rzis independently H or linear or branched C1-18alkyl or aryl as well as -C(O)O(CH2)b-OH, -C(O)O(CH2)b-N(CH3)2, -C(O)O(CH2)bCH3,- N+(CH3)3, -C(O)O(CH2)b-OSO3–, -C(O)O(CH2)b-OSO3H , -C(O)O(CH2)b-SO3–, - C(O)O(CH2)b-SO3H, and -C(O)N(H)C((CH3)2)(CH2)bSO3–, -C(O)N(H)C((CH3)2)(CH2)bSO3H, -(CH2)b-OH, -(CH2)b-N(CH3)2, -(CH2)b-N+(CH3)3, -(CH2)b-OSO3–, -(CH2)b-OSO3H , -(CH2)b- SO3–, -(CH2)b-SO3H, and -C((CH3)2)(CH2)bSO3–, -or C((CH3)2)(CH2)bSO3H, where b is 1-20 alkyl.

6. The composition of claim 1, wherein the polymer has the following structure: q ,wherein R1 an alkyl group, wherein R2 is selected from–7. The composition of claim 1-5, wherein the polymer has a molecular weight of about 1 MDa to 10 MDa.

8. The composition of claim 1-5, wherein the polymer has a molecular weight of about 1.5 MDa to 2 MDa.

9. The composition of claim 8, wherein q is 5 to 20.

10. The composition of claim 8, wherein R1 is a C1 to C12 alkyl group.

11. The composition of claim 8, wherein R1 is a C1 to C8 alkyl group and x is 1 to 8.Thomas Horstemeyer Docket No.: 222112-2310 12. The composition of claim 1-5, wherein the polymer is free of chemical crosslinking or has less than 5% chemical crosslinking.

13. The composition of claim 1-5, wherein the polymer has a polydispersity index (Đ) of about 1.

1. to 2 14. The composition of claim 1-5, wherein the polymer has a polydispersity index (Đ) of about 1.1 to 1.

3.

15. The composition of claim 1-5, further comprising a tackifier.

16. An adhesive composition comprising the composition of any one of claims 1 to 15, wherein the polymer does not include chemical crosslinking.

17. The adhesive composition of claim 15, wherein the polymers are physically entangled.

18. The adhesive composition of claims 15 and 16, wherein the polymers are recyclable.

19. The adhesive composition of claims 15 and 16, wherein the polymer has a polydispersity index (Đ) of about 1.

1. to 2.

20. The adhesive composition of claims 15 and 16, wherein the polymer has a polydispersity index (Đ) of about 1.1 to 1.

3.

21. The adhesive composition of claims 15 and 16, wherein the adhesive is a random copolymer.

22. The adhesive composition of claims 15 and 16, wherein the adhesive is a statistical copolymer.

23. The adhesive composition of claims 15 and 16, wherein the adhesive is an alternative copolymer.Thomas Horstemeyer Docket No.: 222112-2310 24. The adhesive composition of claims 15 and 16, wherein the adhesive is a gradient copolymer.

25. A pressure-sensitive adhesive composition comprising the composition of any one of claims 1 to 15, wherein the polymer is free of chemical crosslinking or has less than 5% chemical crosslinking.

26. The pressure-sensitive adhesive composition of claim 25, wherein the polymers are physically entangled.

27. The pressure-sensitive adhesive composition of claims 25 and 26, wherein the polymers are recyclable.

28. The pressure-sensitive adhesive composition of claim 25, wherein the polymer has a polydispersity index (Đ) of about 1.

1. to 3.

29. The pressure-sensitive adhesive composition of claims 25, wherein the polymer has a polydispersity index (Đ) of about 1.1 to 1.

3.

30. A method of making the polymer having a molecular weight of about 0.3 MDa to 10 MDa and of any one of claims 1-15, comprising the following polymerization scheme:   ], m n groups are independently selected from: H, -OR1, -NRxRy, -N+(Rx)3, -N+(Rx)2(Ry), -N+(Rx)(Ry)(Rz), - S(O)2Rx, -S(O)2ORx, -S(O)2NRxRy, -NRxS(O)2Ry, -NRxC(O)Ry, -C(O)Rx, -C(O)ORx, - C(O)NRxRy, -NRxC(O)ORy, -NRxC(O)NRxRy, -OC(O)NRxRy, -NRxS(O)2NRxRy, - C(O)NRxS(O)2NRxRy, catechol, a boronic acid group, or a pyridyl disulfide group, where each Rx, Ry, and Rzis independently H or linear or branched C1-18alkyl or aryl as well as - C(O)O(CH2)b-OH, -C(O)O(CH2)b-N(CH3)2, -C(O)O(CH2)bCH3,-N+(CH3)3, -C(O)O(CH2)b- OSO3–, -C(O)O(CH2)b-OSO3H , -C(O)O(CH2)b-SO3–, -C(O)O(CH2)b-SO3H, and -Thomas Horstemeyer Docket No.: 222112-2310 C(O)N(H)C((CH3)2)(CH2)bSO3–, -C(O)N(H)C((CH3)2)(CH2)bSO3H, -(CH2)b-OH, -(CH2)b- N(CH3)2, -(CH2)b-N+(CH3)3, -(CH2)b-OSO3–, -(CH2)b-OSO3H , -(CH2)b-SO3–, -(CH2)b-SO3H, and -C((CH3)2)(CH2)bSO3–, or -C((CH3)2)(CH2)bSO3H where b is 1-20 alkyl, wherein in the reaction time frame is about 3 to 5 hours or about 4 hours.

31. The method of claim 30, wherein the polymerization scheme is as follows:

32. The method of claim 30, wherein the polymerization is selected from: a radical polymerization, conventional radical polymerization, reversible-deactivation radical polymerization, reversible addition-fragmentation chain transfer (RAFT) polymerization, macromolecular design by interchange of xanthate (MADIX) polymerization, photoiniferter polymerization, atom transfer radical polymerization (ATRP), or stable free radical polymerization (SFRP).

33. The method of claim 30 and 32, wherein the polymer has a molecular weight of about 1 MDa to 10 MDa.

34. The method of claim 32, wherein q is 5 to 20.

35. The method of claim 32, wherein R1 is a C1 to C12 alkyl group 36. The method of claim 32, wherein R1 is a C1 to C8 alkyl group and x is 1 to 8.

37. The method of claim 32, wherein the polymer is free of chemical crosslinking or has less than 5% chemical crosslinking.

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